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Topics in Applied Physics

Volume 100

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Topics in Applied Physics
Topics in Applied Physics is a well-established series of review books, each of which presents a
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Giacomo Messina Saveria Santangelo (Eds.)

Carbon
The Future Material for
Advanced Technology Applications

With 245 Figures, 6 in Color, and 24 Tables

123
Giacomo Messina
Saveria Santangelo
Faculty of Engineering
Department of Mechanics and Materials
University Mediterranea of Reggio Calabria
89060 Reggio Calabria, Italy
messina@ing.unirc.it
santange@ing.unirc.it

Library of Congress Control Number: 2006924284

Physics and Astronomy Classification Scheme (PACS):


81.05.Uw, 81.07.-b, 60., 70., 80.

ISSN print edition: 0303-4216


ISSN electronic edition: 1437-0859
ISBN-10 3-540-29531-3 Springer Berlin Heidelberg New York
ISBN-13 978-3-540-29531-0 Springer Berlin Heidelberg New York
This work is subject to copyright. All rights are reserved, whether the whole or part of the material is concerned,
specifically the rights of translation, reprinting, reuse of illustrations, recitation, broadcasting, reproduction on
microfilm or in any other way, and storage in data banks. Duplication of this publication or parts thereof is
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permission for use must always be obtained from Springer. Violations are liable for prosecution under the German
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Springer is a part of Springer Science+Business Media

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© Springer-Verlag Berlin Heidelberg 2006


Printed in Germany
The use of general descriptive names, registered names, trademarks, etc. in this publication does not imply, even in
the absence of a specific statement, that such names are exempt from the relevant protective laws and regulations
and therefore free for general use.
Typesetting: DA-TEX · Gerd Blumenstein · www.da-tex.de
Production: LE-TEX Jelonek, Schmidt & Vöckler GbR, Leipzig
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Printed on acid-free paper 57/3100/YL 543210
To Lorenzo Maria, my adored son,
with love
Saveria

To my sons Gloria and Alfonso,


with love
Giacomo
Preface

Carbon is a surprisingly versatile element, able to hybridise in three differ-


ent states, sp1 , sp2 and sp3 . The changes in local bonding of carbon atoms
account for the existence of extremely diverse allotropic phases, exhibiting
a quite broad range of physical and chemical properties. This element can
crystallise as diamond (sp3 hybridisation) or graphite (sp2 hybridisation)
and give rise to many noncrystalline phases (generally containing a mixture
of sp1 , sp2 and sp3 hybridisations), such as fullerenes, carbon nanotubes and
disordered, nanostructured and amorphous carbons.
Strong tetrahedral σ bonds are responsible for the extreme physical prop-
erties of diamond, a wide gap semiconductor having the largest bulk modulus
of any solid, the highest atom density, the largest room-temperature thermal
conductivity, the smallest thermal expansion coefficient and the largest limit-
ing electron and hole velocities of any semiconductor. Graphite, whose sheets
(graphenes), featured by strong intralayer trigonal σ bonding, are held to-
gether by weak interlayer van der Waals’ forces, is an anisotropic metal.
These two crystalline allotropic forms of carbon have been known and
utilised for centuries, together with other carbonaceous materials, generically
identified as coals. The use of hydrocarbons and organic materials is more
recent. The true turning point in the use of carbon as a material for advanced
technology applications, however, occurs only in the second half of the last
century.
In 1953, the discovery, at Union Carbide Co., of the possibility of grow-
ing diamond films by chemical vapour deposition (CVD), at low pressures,
opened the way to the development of low-cost deposition techniques. The
growth of CVD diamond films at subatmospheric pressures, firstly reported
by Derjaguin and Fedoseev in 1967 and later implemented by Matsumoto’s
group, opened new perspectives in technological applications of diamond.
The enthusiasm for these achievements caused further efforts to be addressed
to the development of low-temperature CVD techniques and stimulated the
search for alternative growth methods, such as the QQC process, based
on a multiplexed laser–solid interaction, announced in the 1990s by QQC
Inc. (USA).
Around 1969, Aisenberg and Chabot demonstrated that carbon films with
properties ranging between those of diamond (diamond-like carbon, DLC)
VIII Preface

and those of graphite (graphite-like carbon, GLC) can be deposited by the


use of energetic carbon species. The term amorphous carbon (a-C) identifies
a carbon matrix with any possible mixture of sp1 -, sp2 - and sp3 -hybridised
sites and no crystalline long-range order. Indeed, a wide nomenclature for
the classification of these films does exist. Hydrogenated amorphous carbon
(a-C:H) denotes an a-C film containing up to even 60% hydrogen. The term
DLC, initially introduced to identify exclusively a-C films with hardness and
transparency properties close to those of diamond, is nowadays commonly
used to designate a larger class of materials, including both hydrogen-free and
hydrogenated a-Cs, containing a significant fraction of sp3 hybridised carbon
sites and exhibiting a wide spectrum of properties and potentialities. Finally,
the name tetrahedral amorphous carbon (ta-C) is attributed to hydrogen-
free a-Cs containing up to 95% sp3 sites, sometimes also termed amorphic
diamond (a-D), whose correspondent hydrogenated form is known as ta-C:H.
In 1985, spectrometric measurements on interstellar dust led to the discov-
ery of new allotropic forms of carbon, consisting of pentagonal and hexagonal
rings arranged to form closed-cage molecules. However, the scientific interest
in fullerenes, started only in 1990 after the invention of the method for their
production in macroscopic amounts, was really fuelled by the awarding of the
Nobel Prize in chemistry for this discovery in 1996.
In 1989, Liu and Cohen theoretically predicted the existence of a crys-
talline β-C3 N4 phase with bulk modulus and hardness higher than diamond.
The attempts of synthesising such a hypothetical superhard compound drew
attention upon carbon nitride (CN). In spite of the lack of any agreed success
on this direction, in the last years the interest in amorphous CN compounds
has been renewed, due to the wide range of possible applications.
The observation, in 1993, of single-walled carbon nanotubes (SWCNTs),
consisting of single graphene sheets wrapped into hollow cylinders having
nanometer-sized diameter, followed to the discovery, about two years ear-
lier, of multiwalled carbon nanotubes (MWCNTs), comprising up to tens of
coaxial cylinders, caused enormous interest in many fields of research.

The exciting discoveries of the last decades have given great impulse to
the research on carbon-based materials, offered new opportunities and issued
new challenges. The lengthy history of diamond as a material for advanced
technology began in the 1920s with the development of photoconductive UV
detectors, followed in the 1940s by the fabrication of ionising radiation detec-
tors, both based on the use of geological diamonds. In 1979, the experiments
of Himpsel, followed by those of Pate in 1986, demonstrated the high quantum
efficiency for photoelectron emission from natural diamond crystals, starting
the consideration of diamond as an emitting material in cold cathode sources
and devices. Nowadays, a great variety of technological applications in fields
as diverse as mechanics, lithography, optics, chemistry, electronics, takes full
advantage of the extraordinary properties of higher and higher quality syn-
thetic diamond films, achieved thanks to the continuous advances in prepara-
Preface IX

tion methods. Surprisingly, however, there are even manifold applications of


“damaged diamond”. These benefit from the dramatic modifications of elec-
trical, mechanical, optical and chemical properties induced on virgin material
by ion-beam exposure. The realisation of ohmic contacts in diamond-based
electronic devices and the production of microstructures on single-crystal
diamond membranes for micromachining exploit the local complete graphiti-
sation process. Partial graphitisation, instead, is employed for the realisation
of electrodes for electrochemistry and of conductive patterns on diamond.
The cheaper production costs, along with the significant fraction of sp3
bonding conferring on DLC many of the profitable properties of diamond,
make it a valuable material for widespread technology applications. The first
exploitation of DLC has been as a hard protective coating. During the last 30
years, taking advantage of its low friction, the use of DLC as coating has been
enlarged to the solid lubricant technology. Its good blood compatibility sug-
gests of extending its utilisation as biomaterial in blood-contacting-devices.
Nowadays, DLCs coat a surprisingly large number of unexpectedly different
objects, spanning from microelectromechanical devices to dental prostheses,
from optical windows to razor blades, from orthopedic pins and screws to car
parts, from medical guide-wires to disks, heads and slides used in magnetic
storage technology.
Recently, there has been considerable interest in the application of low-
threshold field-emitting carbon films for cold cathode devices and flat panel
displays. The interest in amorphous hydrogen-free and hydrogenated CN
compounds is, instead, mainly concerned with their possible application as
electrodes, IR detectors and gas sensors. Group-IV carbon-based binary al-
loys, like amorphous silicon and germanium carbon-alloys, are used for opto-
electronic devices and for the construction of solar cells.
Fullerenes, whose family comprises a large variety of isomers, are used as
sorbents, as superconductors, as chromatographic stationary phases, as mate-
rials for building optical and electronic devices, hydrogen cells, photosensitive
elements and electrochemical sensors. Thanks to their astonishing properties,
fullerenes and their derivatives appear to be a good alternative to polymer
molecules currently used in nanolithography, as well as promising candidates
as antioxidants, neuroprotectors and inhibitors of bacterial growth.
The unique structural features of SWCNTs and MWCNTs are reflected
in their singular optical, electronic and mechanical properties. Thanks to the
wide variety of geometrical-structure-dependent behaviours, CNTs possess
great potential in many research fields, spanning from physics to chemistry,
from engineering to materials science, from biology to life science. Although
gaining the control of diameter and chirality of CNTs still represents the
goal needed for the defect-free CNT production and the full success of the
CNT-based technological applications, they are presently regarded as build-
ing blocks for various nanoscale devices. Current applications relate to mainly
electronic devices, such as field emitters, transistors and sensors, while one of
X Preface

the future challenges consists in the creation of highly integrated CNT-based


cicuits. The recent fabrication of the world’s smallest motor based on CNTs
has opened the way to nanoelectromechanical systems, while the realisation
of the first AFM tip using CNTs has laid the foundations for a real revolution
in high-resolution imaging techniques.

It appears now clear that carbon-based materials constitute a topic of


huge scientific interest and great strategic importance in an interdiscipli-
nary approach spanning applied physics, materials science, biology, mechan-
ics, electronics and engineering. Development of current materials, advances
in their applications and discovery of new forms of carbon are the themes
addressed by the frontier research in these fields.
The book covers all the fundamental topics concerned with amorphous
and crystalline carbon-based materials, such as synthetic diamond, diamond-
like carbon, carbon alloys, carbon nanotubes and cluster-assembled materi-
als. The latest scientific results and developments in the various technological
application areas of these materials are reviewed. Both theoretical and exper-
imental aspects related to their optical, electrical, elastic, thermomechanical,
structural, vibrational and electronic properties are extensively discussed.
The contributions discuss subjects of great currency and huge scientific
and technological interest, such as the use of carbon-based materials for en-
ergy storage, for fabrication of sensors operating in harsh environments and
as biocompatible coatings for medical implants. A broad spectrum of both
well-assessed and still controversial as well as newly developed aspects con-
cerning growth and characterisation techniques are addressed, ranging from
modelling of deposition processes to semiempirical methods for its control
and optimisation, from investigation of diamond-nucleation and nanotube-
growth mechanisms to more comprehensive explanation of the origin of the
Raman features commonly regarded as the fingerprint of amorphous carbons.
An accurate picture is drawn of both the present developments in research
on carbon and the future prospects that may constitute a reference point for
a new generation of researchers, who accept the challenge issued by the scien-
tific community in this fascinating field. The volume, comprising 24 contribu-
tions, is the first comprehensive state-of-the-art review of this fast-evolving
field of research. Its preparation, to which many of the most world-famous
researchers engaged in the field have contributed, has acted as a friendly and
cooperative opportunity to share the latest outstanding and exciting results
in the hot topics of research on carbon. The 75 contributors, most of whom
often promote scientific events and organise international meetings on carbon
and related subjects, belong to a multitude of disciplines. This witnesses the
interdisciplinary nature of the fundamental and technology-centred studies
of carbon, a material entering everyday life, on which worldwide attention is
focused for its extraordinary future potential.
The contributions are presented in alphabetic order because any classifi-
cation relative to material kind (diamond, carbon alloys, carbon nanotubes,
Preface XI

etc.) or to contribution type (fundamental studies, technological applications,


etc.) or subject (growth techniques, characterisation tools, etc.) might be re-
ductive for the reader. Most of the contributions, in fact, deal with aspects
common to more than one of these topics.
We end this preface by acknowledging all the scientists who participated
enthusiastically and painstakingly to the realisation of this volume and to
the Springer staff for the valuable assistance provided.

Reggio Calabria, Giacomo Messina


26 August 2005 Saveria Santangelo
Contents

Aid of Scaling Laws in the Achievement of a Well-Controlled


Film Deposition Process
Giacomo Messina, Saveria Santangelo . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1
A Spectroscopic Approach to Carbon Materials for Energy
Storage
Giuseppe Zerbi, Matteo Tommasini, Andrea Centrone,
Luigi Brambilla, Chiara Castiglioni . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 23
1 Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 23
1.1 Carbon-Based Materials . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 24
2 Prototypical Lattices in Three, Two and One Dimensions . . . . . . . . . 26
2.1 Diamond . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 26
2.2 Graphite . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 28
2.3 Polyacetylene . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 29
2.4 Polyynes . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 32
3 A Spectroscopic Approach to Disordered Carbon Materials . . . . . . . 33
3.1 1D Systems – Saturated Carbon Materials . . . . . . . . . . . . . . . . . 33
3.2 Polyconjugated Polymers . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 34
3.3 2D sp2 Systems . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 35
4 Edge Effects in Graphitic Domains for Structure Diagnosis . . . . . . . 36
5 Approaching the Structure of Carbonaceous Materials by
Vibrational Spectroscopy: Imagination and Reality . . . . . . . . . . . . . . 41
5.1 Carbon-Based Materials for Hydrogen Storage . . . . . . . . . . . . . . 44
6 Conclusions . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 47
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 48
Index . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 52
Biocompatibility, Cytotoxicity and Bioactivity of Amorphous
Carbon Films
Sandra E. Rodil, René Olivares, Higinio Arzate, Stephen Muhl . . . . . . . 55
1 Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 55
2 Experimental Details . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 58
2.1 Film Deposition . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 58
2.2 Film Characterization . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 58
2.3 Cell Preparation . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 59
XIV Contents

2.4 Cytotoxicity Test . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 59


2.5 Bioactivity . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 60
2.5.1 Morphological Assay . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 60
2.5.2 Protein Synthesis . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 60
3 Results . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 62
3.1 Film Properties . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 62
3.2 Cytotoxicity . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 64
3.3 Bioactivity . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 65
3.3.1 Morphological Analysis . . . . . . . . . . . . . . . . . . . . . . . . . . . . 65
3.3.2 Proteins . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 65
4 Discussion . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 71
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 73
Index . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 75
Characterisation of the Growth Mechanism during PECVD
of Multiwalled Carbon Nanotubes
Martin S. Bell, Rodrigo G. Lacerda, Kenneth B.K. Teo,
William I. Milne . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 77
1 Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 77
2 Production of Carbon Nanotubes . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 82
3 Plasma Composition during PECVD . . . . . . . . . . . . . . . . . . . . . . . . . . . 84
4 Characterisation of the Growth Mechanism . . . . . . . . . . . . . . . . . . . . . 85
5 Conclusion . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 89
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 90
Index . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 92
Correlation Between Local Structure and Film Properties
in Amorphous Carbon Materials
Giovanni Fanchini, Alberto Tagliaferro . . . . . . . . . . . . . . . . . . . . . . . . . . . . 95
1 Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 95
2 Electronic States in Carbon . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 95
3 Hybridisation and Local Structure . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 96
4 The Various Forms of Amorphous Carbon . . . . . . . . . . . . . . . . . . . . . . 97
5 Phase Matching and Its Effects on Materials . . . . . . . . . . . . . . . . . . . . 99
6 Optoelectronic and Mechanical Properties . . . . . . . . . . . . . . . . . . . . . . 102
7 Conclusion . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 103
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 104
Index . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 104
Defects in CVD Diamond Films from Their Response
as Nuclear Detectors
Marco Marinelli, Enrico Milani, Aldo Tucciarone, Gianluca Verona
Rinati . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 107
1 Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 107
2 CVD Diamond Nuclear Detectors: Realization and Physics . . . . . . . 108
Contents XV

3 Analysis of the Charge Collection Spectrum . . . . . . . . . . . . . . . . . . . . 111


3.1 Qualitative Analysis . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 111
3.2 Quantitative Analysis: The General Model . . . . . . . . . . . . . . . . . 115
3.3 The Use of Detector Thickness . . . . . . . . . . . . . . . . . . . . . . . . . . . 117
3.4 The Use of Penetration Depth . . . . . . . . . . . . . . . . . . . . . . . . . . . . 119
4 Time-Domain Analysis . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 123
4.1 The Background . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 123
4.2 Qualitative Analysis . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 125
4.3 Quantitative Analysis: Computer Simulation . . . . . . . . . . . . . . . 126
5 Temperature Effects: Depumping . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 129
6 Conclusion . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 133
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 133
Index . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 135
Effects of Nanoscale Clustering in Amorphous Carbon
J. David Carey, S. Ravi P. Silva . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 137
1 Introduction and Bonding in Carbon . . . . . . . . . . . . . . . . . . . . . . . . . . . 137
2 Disorder in Amorphous Carbon . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 139
3 Intracluster Effects in Amorphous Carbon . . . . . . . . . . . . . . . . . . . . . . 142
4 Intercluster Interactions in Amorphous Carbon . . . . . . . . . . . . . . . . . . 147
5 Field Emission from Amorphous Carbon . . . . . . . . . . . . . . . . . . . . . . . 148
6 Conclusions . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 150
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 150
Index . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 151

Elastic and Structural Properties of Carbon Materials


Investigated by Brillouin Light Scattering
Marco G. Beghi, Carlo S. Casari, Andrea Li Bassi, Carlo E. Bottani . . 153
1 Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 153
2 Experimental Technique . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 156
3 Derivation of the Elastic Constants . . . . . . . . . . . . . . . . . . . . . . . . . . . . 158
4 Brillouin Scattering from Carbonaceous Materials . . . . . . . . . . . . . . . 161
5 Ultra-Thin Carbon Films . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 162
6 Nanotubes . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 166
7 Conclusions . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 170
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 170
Index . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 173
Electrical Resistivity and Real Structure of Magnetron-
Sputtered Carbon Films
Alexei A. Onoprienko . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 175
1 Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 175
2 Experimental . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 176
3 Results and Discussion . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 177
3.1 Substrate Temperature Effects . . . . . . . . . . . . . . . . . . . . . . . . . . . . 177
XVI Contents

3.2 Substrate Bias Effects . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 181


4 Conclusion . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 184
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 185
Index . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 186
Formation, Atomic Structures and Properties of Carbon
Nanocage Materials
Takeo Oku, Ichihito Narita, Atsushi Nishiwaki, Naruhiro Koi,
Katsuaki Suganuma, Rikizo Hatakeyama, Takamichi Hirata, Hisato
Tokoro, Shigeo Fujii . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 187
1 Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 187
2 Synthesis Methods . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 189
3 Fullerene Clusters and Metallofullerenes . . . . . . . . . . . . . . . . . . . . . . . . 190
4 Onions and Nanotubes . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 196
5 Carbon Nanocapsules . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 200
6 Properties of Carbon Nanomaterials . . . . . . . . . . . . . . . . . . . . . . . . . . . 204
6.1 Photoluminescence of Carbon Nanocapsules . . . . . . . . . . . . . . . . 204
6.2 Magnetic Properties of Carbon Nanocapsules . . . . . . . . . . . . . . . 205
6.3 Possibility of H2 Gas Storage in Carbon Nanocages . . . . . . . . . 207
6.4 One-Dimensional Self-Organization of Nanocapsules . . . . . . . . . 209
7 Conclusion . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 212
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 212
Index . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 215
Hard Amorphous Hydrogenated Carbon Films and Alloys
Fernando L. Freire Jr. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 217
1 Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 217
2 Film Growth and Chemical Composition . . . . . . . . . . . . . . . . . . . . . . . 220
3 Film Microstructure . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 224
4 Mechanical and Nanotribological Properties . . . . . . . . . . . . . . . . . . . . 229
5 Conclusion . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 234
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 235
Index . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 237
Ion Microscopy on Diamond
Claudio Manfredotti . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 239
1 Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 240
2 IBIC . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 241
3 Lateral IBIC . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 246
4 IBIL . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 251
5 XBIC . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 257
6 Conclusions . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 263
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 264
Index . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 265
Contents XVII

Measurements of Defect Density Inside CVD Diamond Films


Through Nuclear Particle Penetration
Renato Potenza, Cristina Tuvé . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 267
1 Diamond as Radiation Detector . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 267
1.1 Properties of Diamond . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 267
1.2 Lattice Defects in Synthetic Diamond Crystals . . . . . . . . . . . . . 269
1.3 Application of Diamond to Beam and Beam Profile Monitoring271
2 Mechanism of Conduction in Circuits Including Diamond . . . . . . . . . 273
2.1 Modified Hecht’s Model for Charge Transport Inside Diamond 275
2.1.1 Absorption of Carriers During Their Transport Along
the Electric Field Lines . . . . . . . . . . . . . . . . . . . . . . . . . . . . 275
2.1.2 Edge Effects . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 276
2.2 Effect of Nonuniform Bragg’s Deposit of Charge into Diamond 278
2.3 Nonuniform Distributions of Charge and Defects . . . . . . . . . . . . 279
3 Charge Collection Efficiencies of Diamond Detectors
Under Ion Bombardment . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 280
3.1 Experimental Procedure to Measure the Charge Collection
Efficiencies . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 282
3.2 Corrections to the Efficiencies η± Needed to Into Take
Account the Pulse Height Defect of Diamond for Detectors
Heavy Ionizing Particles . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 283
4 Conclusions . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 285
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 285
Index . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 286
Laser Ablation-Deposited CNx Thin Films
Enza Fazio, Enrico Barletta, Francesco Barreca, Guglielmo Mondio,
Fortunato Neri, Sebastiano Trusso . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 287
1 Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 287
2 Experiments . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 288
3 Results and Discussion . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 289
4 Conclusion . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 300
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 301
Index . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 302
Modeling of the Transport Properties of Diamond Radiation
Sensors
Stefano Lagomarsino, Silvio Sciortino . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 303
1 Models of the Polycrystalline Diamond Band Gap . . . . . . . . . . . . . . . 303
1.1 Band A . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 304
1.2 Trapping Centers . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 304
1.3 Carrier Lifetimes and Charge Collection Distance . . . . . . . . . . . 305
1.4 Location of the Trapping and Recombination Centers in the
Diamond Band Gap . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 306
1.5 Unipolar Conduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 308
XVIII Contents

2 A General Model for Transport Properties of pCVD Diamond:


Underlying Assumptions . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 309
3 Conductivity Under Exposure to Ionizing Radiation . . . . . . . . . . . . . 311
4 Thermal Relaxation of Uniform Trap Level Distributions . . . . . . . . . 316
4.1 Radiation Induced Conductivity Transient at Different
Fading Times . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 317
4.2 Persistent Radiation-Induced Conductivity . . . . . . . . . . . . . . . . . 319
5 Conclusions . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 323
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 325
Index . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 326
Nucleation Process of CVD Diamond on Molybdenum
Substrates
Giuliana Faggio, Maria G. Donato, Stefano Lagomarsino, Giacomo
Messina, Saveria Santangelo, Silvio Sciortino . . . . . . . . . . . . . . . . . . . . . . . 329
1 Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 329
2 Experimental . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 330
3 Results and Discussion . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 331
3.1 Raman and Photoluminescence Analysis . . . . . . . . . . . . . . . . . . . 331
3.1.1 Discontinuous Samples . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 332
3.1.2 Continuous Samples . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 334
3.2 Statistical Study of the Nucleation Process . . . . . . . . . . . . . . . . . 336
4 Conclusions . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 340
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 341
Index . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 343
Optical Characterisation of High-Quality Homoepitaxial
Diamond
Maria G. Donato, Giuliana Faggio, Giacomo Messina, Saveria
Santangelo, G. Verona Rinati . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 345
1 Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 345
2 Experimental . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 348
3 Results . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 348
3.1 Optical and SEM Characterisation . . . . . . . . . . . . . . . . . . . . . . . . 348
3.2 Raman Characterisation . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 350
3.2.1 First-Order Raman Scattering . . . . . . . . . . . . . . . . . . . . . . 350
3.2.2 Second-Order Raman Scattering . . . . . . . . . . . . . . . . . . . . . 351
3.3 Photoluminescence Characterisation . . . . . . . . . . . . . . . . . . . . . . . 352
4 Discussion and Conclusions . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 355
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 357
Index . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 358
Contents XIX

Pulsed Laser Deposition of Carbon Films: Tailoring Structure


and Properties
Paolo M. Ossi, Antonio Miotello . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 359
1 Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 359
2 Experimental Details . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 361
3 Results . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 362
3.1 Low-Pressure Deposited Films . . . . . . . . . . . . . . . . . . . . . . . . . . . . 362
3.2 High-Pressure Deposited Films . . . . . . . . . . . . . . . . . . . . . . . . . . . 367
4 Discussion . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 373
4.1 Low-Pressure Deposited Films . . . . . . . . . . . . . . . . . . . . . . . . . . . . 373
4.2 High-Pressure Deposited Films . . . . . . . . . . . . . . . . . . . . . . . . . . . 376
5 Conclusions . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 377
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 378
Index . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 379
Raman Spectra and Structure of sp2 Carbon-Based
Materials: Electron–Phonon Coupling, Vibrational Dynamics
and Raman Activity
Chiara Castiglioni, Fabrizia Negri, Matteo Tommasini, Eugenio Di
Donato, Giuseppe Zerbi . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 381
1 Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 381
2 Raman Spectra of Polyconjugated Materials . . . . . . . . . . . . . . . . . . . . 383
3 Electron–Phonon Coupling and Raman Features . . . . . . . . . . . . . . . . 385
3.1 Electron–Phonon Coupling in Polyacetylene . . . . . . . . . . . . . . . . 385
3.2 Electron–Phonon Coupling in Graphenes . . . . . . . . . . . . . . . . . . 390
3.3 Electron–Phonon Coupling in Carbon Nanotubes . . . . . . . . . . . 395
4 Conclusions . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 399
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 400
Index . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 402
Raman Spectroscopy and Optical Properties of Amorphous
Diamond-Like Carbon Films
Leonid Khriachtchev . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 403
1 Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 403
2 Experimental Details . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 404
3 Raman Diagnostics . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 405
4 Effects Induced by Interference of Light . . . . . . . . . . . . . . . . . . . . . . . . 409
5 Optical Characterization . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 413
6 Some Applications . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 416
7 Conclusions . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 418
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 419
Index . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 420
XX Contents

Raman Spectroscopy of CVD Carbon Thin Films Excited by


Near-Infrared Light
Margit Koós, Miklós Veres, Sára Tóth, Miklós Füle . . . . . . . . . . . . . . . . . 423
1 Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 423
1.1 The Raman Effect . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 423
1.2 Raman Spectra of Carbon Materials . . . . . . . . . . . . . . . . . . . . . . 426
2 Infrared Excited Raman Spectroscopy of Amorphous Carbon Thin
Films . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 429
2.1 a-C:H Thin Films Prepared from Benzene . . . . . . . . . . . . . . . . . 429
2.2 a-C:H Thin Layers Prepared From Methane . . . . . . . . . . . . . . . . 438
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 443
Index . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 444
The Role of Hydrogen in the Electronic Structure of
Amorphous Carbon: An Electron Spectroscopy Study
Lucia Calliari, Massimiliano Filippi, Nadhira Laidani, Gloria
Gottardi, Ruben Bartali, Victor Micheli, Mariano Anderle . . . . . . . . . . . 447
1 Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 447
2 Experimental . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 449
2.1 Hydrogen Incorporation in the Structure of a-C . . . . . . . . . . . . 449
2.2 Temperature-Induced Hydrogen Evolution from a-C:H . . . . . . . 450
3 Hydrogen Incorporation in the Structure of a-C . . . . . . . . . . . . . . . . . 450
4 Temperature-Induced Hydrogen Evolution from a-C:H . . . . . . . . . . . 455
5 Concluding Remarks . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 459
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 461
Index . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 462
UV-Induced Photoconduction in Diamond
Emanuele Pace, Antonio De Sio, Salvatore Scuderi . . . . . . . . . . . . . . . . . . 463
1 Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 463
2 Overview . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 464
3 Properties of Diamond . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 467
4 Synthesis of Diamond . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 468
5 Experimental Methods . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 470
6 Electro-Optical Properties . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 472
6.1 Polycrystalline Diamond Detectors . . . . . . . . . . . . . . . . . . . . . . . . 474
6.2 Single-Crystal Diamond Detectors . . . . . . . . . . . . . . . . . . . . . . . . 481
7 Single-Pixel Detectors . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 485
7.1 Photodetectors . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 485
7.2 Photoconductor . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 485
7.3 Photodiode . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 487
8 Pixel Array Detectors . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 489
9 Applications . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 491
9.1 UV Lasers . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 493
9.2 Photolithography . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 494
Contents XXI

9.3 Space Astronomy . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 495


10 Conclusions . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 497
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 498
Index . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 503
Vibrational Spectroscopy in Ion-Irradiated Carbon-Based
Thin Films
Giuseppe Compagnini, Orazio Puglisi, Giuseppe A. Baratta, Giovanni
Strazzulla . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 505
1 Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 505
2 Irradiation of Crystalline Carbon and Carbon Alloys . . . . . . . . . . . . . 506
3 Irradiation of Hydrocarbons (Oligomers, Polymers and Frozen
Gases) . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 510
4 Irradiation of sp-Rich Amorphous Carbon Phases . . . . . . . . . . . . . . . 513
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 518
Index . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 519

Index . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 521
Aid of Scaling Laws in the Achievement
of a Well-Controlled Film Deposition Process

Giacomo Messina and Saveria Santangelo

Dipartimento di Meccanica e Materiali, Università “Mediterranea” di Reggio


Calabria, Località Feo di Vito, I-89060 Reggio Calabria, Italy, and INFM, Unità
di Ricerca di Roma “Tor Vergata”
santangelo@ing.unirc.it

Abstract. Scaling laws are profitably applied in all the scientific disciplines. Ap-
proximated solutions constitute a valuable aid for the analysis of complex systems
and physical processes and, generally, for handling problems involving many vari-
ables. We indicate the path for deriving a scaling law for the growth parameters,
referring to the synthesis of hydrogenated amorphous carbon-nitrides (a-CN:H)
by reactive sputtering as an example. Thanks to its generality, the semiempirical
method utilised here can be applied to all carbon-based materials and all deposition
techniques. We demonstrate the existence of an analytical dependence of the film
physical properties, as resulting from Raman analysis and Rutherford backscatter-
ing measurements, on a single dimensionless combination of the growth parame-
ters. We give an empirical rule for tailoring the film characteristics through specific
changes of the deposition conditions. We thus achieve the capability of easily pre-
dicting and controlling the final issue of the synthesis process.

1 Introduction
The search for approximated solutions, which are useful for describing the
behaviour of complex systems and processes, is a topic common to all the
scientific disciplines. In this context, the majority of efforts are generally de-
voted to the derivation of scaling laws, which play a key role in handling
problems involving a great number of variables. In the last years, a semi-
empirical method [1], based on a modified application of the theorem on
“physically similar systems” of dimensional analysis [2], has been proposed
as a physical approach to approximation [3, 4, 5]. According to this method,
dimensionless variable combinations (‘Q-arguments’), aimed at describing ef-
fectively the process, are generated. These combinations can be regarded as
the only independent variables and represent scaling laws for the variables
involved. Once the problem is reformulated in terms of Q-arguments, practi-
cal approximants to the physical laws governing the process are derived by a
fitting procedure to the experimental data. The process issue is, hence, finally
described by analytical functions depending on few parameters, rather than
on the many variables initially present.
Scaling laws constitute a quite helpful tool for practically controlling and
easily improving complex systems whose behaviour depends on several mech-
G. Messina, S. Santangelo (Eds.): Carbon, The Future Material for Advanced Technology Ap-
plications, Topics Appl. Phys. 100, 1–21 (2006)
© Springer-Verlag Berlin Heidelberg 2006
2 Giacomo Messina and Saveria Santangelo

anisms of different nature. They are, hence, profitably utilised in a very wide
variety of fields [6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19], ranging from
biology to engineering, from space science to chemistry, from medicine to
materials science, from genetics to physics. They also offer a valuable aid in
studying complicated processes, such as film deposition [20, 21, 22, 23, 24],
whose evolution and final issue are determined by manyfold concomitant fac-
tors. Finding the scaling laws for the growth process allows us to achieve a
full control of it, with the consequent possibility of optimising the preparation
technique. Once the capability of tailoring the film characteristics is acquired,
high-quality films can be straightforwardly synthesised [5, 25, 26, 27, 28]. The
derivation of scaling laws, however, generally represents a difficult task whose
success strongly depends on how the process is modelled. For this the reason,
it must be faced in the more general context of the process approximation
and requires a deep understanding of the mechanisms involved.
This contribution, where the film growth approximation is addressed, in-
tends to furnish the experimentalist with a powerful tool for acquiring the
capability of readily predicting and easily driving the deposition issue, on the
basis of the empirically gained know-how. By application to the previously
developed method [1], a scaling law for the film growth process is derived
and approximated solutions are therein attained. The preparation of hydro-
genated amorphous carbon–nitrides by reactive sputtering is considered as an
example. Nonetheless, the general method utilised can be extensively applied
to all growth techniques and materials. We investigate the influence of the
deposition conditions on the physical properties of the grown films. By deriv-
ing the relationships approximating the physical laws governing the process,
empirical rules are achieved for driving it and tailoring the synthesised film
characteristics through specific changes of the growth conditions. We use Ra-
man spectroscopy and Rutherford backscattering analysis, but the results of
any other postgrowth diagnostic technique could be employed for deriving the
scaling law by the use of the same operative procedure. In particular, experi-
mental details are given in Sect. 2. The operative scaling law derivation pro-
cedure we develop and our outstanding results obtained are briefly reviewed
in Sect. 3. In Sect. 4, the very simple model of the reactive-sputtering growth
process, utilised for the scaling law derivation, is illustrated. From the discus-
sion, a deeper insight is achieved on the role played by internal microscopic
variables in determining the final issue of the a-CN:H film sputter-deposition.
Conclusions are briefly given in Sect. 5.

2 Experimental
Two sets of a-CN:H films are prepared by graphite sputtering in N2 –H2 –
He–Ar atmosphere using a conventional 13.56 MHz diode system. Samples of
series ‘D’ are utilised for deriving the scaling law. Samples of series ‘T’ are
deposited afterwards, with the purpose of testing its validity. The deposition
Scaling Laws for Film Deposition 3

Table 1. Values of the dimensionless argument Q corresponding to the growth


conditions of a-CN:H films utilised for deriving (series ‘D’) and testing (series ‘T’)
the scaling law. ΦN2 and ΦH2 indicate the reactive-gas (N2 and H2 ) flow rates, while
ΦHe and ΦAr standing for the inert-gas (He and Ar) flow rates. Note that flow rates
of inlet gases, chamber pressure (p) and rf power (W ) are varied so that at least
the value of one of these parameters is different from one deposition to another

Film Q ΦN2 ΦH2 ΦHe ΦAr p W


# sccm sccm sccm sccm mTorr W
D1 0.036 20.0 7.0 30.0 70.0 20 300
T1 0.079 8.4 3.0 70.0 30.0 38 300
D2 0.169 10.0 5.0 30.0 70.0 21 300
D3 0.347 10.0 7.0 30.0 70.0 25 300
D4 0.434 10.0 7.0 30.0 70.0 20 300
T2 0.578 10.0 7.0 30.0 70.0 20 400
D5 0.603 7.0 5.0 30.0 70.0 21 300
D6 0.715 4.2 3.0 70.0 30.0 38 220
T3 0.865 3.0 2.2 70.0 30.0 38 180
D7 0.974 4.2 3.0 70.0 30.0 38 300

temperature is 100 ◦ C, while the gas flow rates (ΦN2 , ΦH2 , ΦHe , ΦAr ), chamber
pressure (p) and rf power (W ) vary as indicated in Table 1.
The film stoichiometry is investigated by Rutherford backscattering (RBS)
and elastic recoil detection analysis (ERDA) measurements. Raman spec-
troscopy is employed for studying bonding and structural properties. Details
about film deposition and analysis, including spectra fitting and interpreta-
tion, can be found in [29, 30, 31, 32, 33].

3 Results
3.1 Film Properties

Figure 1 shows the Raman spectra of the films considered. As discussed [31,
32], the shape evolution of the D band and G bands reflects the structural and
bonding modifications, produced by the film stoichiometry changes. The most
meaningful parameters derived from Raman analysis are shown in Table 2
together with the film chemical composition.
Since six deposition parameters are independently varied during the
preparation of the samples, the representation of these results leads to hyper-
surfaces in 7-dimensional spaces. In principle, projecting such hypersurfaces
could indicate the role of each growth variable. Nevertheless, the simulta-
neous variation of the remaining deposition parameters actually causes a
confused spreading of the projected points, with a consequent lack of a clear
correlation with the changes in film stoichiometry and related properties.
4 Giacomo Messina and Saveria Santangelo

Fig. 1. Raman spectra of a-CN:H


films belonging to (a) series D, used
for deriving, and (b) series T, used
for testing scaling law. Excitation
energy is 2.41 eV. Spectra decompo-
sition results are shown in case of
sample D6, as an example. Dotted
and dashed lines represent the best
fits to spectrum and D band and
G band, respectively

This, as demonstrated in Fig. 2, where the G band frequency position (ωG )


is plotted as a function of rf power and chamber pressure, hinders us from
guessing the possible effect of any variation of the growth conditions on the
film characteristics.

3.2 Operative Scaling Law Derivation Procedure

A simpler picture might derive from finding a dependence of Raman de-


scriptive parameters on a limited number (L) of dimensionless arguments
in place of the initial N (L) growth variables. The search for such argu-
ments is pursued through a semiempirical method [1], based on an extended
application of the theorem on “physically similar systems” of dimensional
analysis [2]. A two-way and trial-and-error approach (Fig. 3), involving the
repeated comparison with the experimental data, is utilised in place of the
standard one-way and necessary procedure. After replacement of dimension-
Scaling Laws for Film Deposition 5

Table 2. Results of the structural and compositional analysis carried out on the
films. Samples are listed in increasing order of Q. ωG and ID /IG stand for G band
frequency position and D/G intensity ratio measured in the Raman spectra, respec-
tively. LC denotes the average size of Csp2 clusters estimated from ID /IG values [34].
The film C, H and N contents, as well as O contamination, resulting from ERDA
and RBS measurements, are reported

Film ωG ID /IG LC C content H content N content O content


# cm−1 nm % % % %
D1 1575.2 0.89 1.27 69.9 19.6 7.0 3.5
T1 1575.1 1.18 1.46 75.8 12.9 7.6 3.7
D2 1575.0 1.03 1.37 73.5 15.4 7.4 3.7
D3 1574.1 0.91 1.29 74.6 14.2 7.5 3.7
D4 1573.6 0.96 1.32 71.4 17.9 7.1 3.6
T2 1573.2 0.91 1.29 71.4 17.9 7.1 3.6
D5 1572.3 0.94 1.31 74.6 14.2 7.5 3.7
D6 1569.9 1.06 1.39 73.0 16.1 7.3 3.6
T3 1563.9 1.20 1.48 79.4 8.7 7.9 4.0
D7 1563.3 1.23 1.50 79.0 7.2 9.8 4.0

Fig. 2. Dependence of the G band frequency position (ωG ) on rf power (W ) and


chamber pressure (p). The ωG points shown are obtained by projecting the 7-
dimensional ωG hypersurface. Their confused spreading in the W, p, ωG space is
due to the simultaneous variation of the flow rates of the inlet gases
6 Giacomo Messina and Saveria Santangelo

Fig. 3. Scheme of the flow chart used for deriving the scaling law Q. Stage 1: ini-
tialisation and testing of the argument Q. Stage 2: definition of a new argument as
power product of further dimensionless variable combinations Qk . M represents the
maximum number of arguments Qk entering the new formulation of Q. Stage 3: ad-
justing of the exponents αk and testing of the scaling law. The experimental data
are approximated to a suited function of Q and exponent adjusting is pursued, in
a sufficiently high iteration number I, by minimising the standard deviation σ

ate Raman descriptive parameters with appropriate dimensionless Raman


arguments, arbitrary dimensionless combinations (Q1 , Q2 , ..., QL ) of the
growth parameters (G1 , G2 , ..., GN ) are generated on the basis of physical
considerations, by the aid of dimensional analysis.
The operative procedure [35] followed comprises three stages:
Stage 1. A dimensionless argument Q1 is firstly generated (argument Q
initialisation). Assuming that the Raman argument R depends on Q, the
experimental data are approximated to a suited function of Q. If the stan-
dard deviation σ does not exceed the prior-established maximum allowed
value σmax (argument Q testing), combination Q1 represents the scaling law
searched for.
Stage 2. If not, a new dimensionless argument Q2 is generated (new ar-
gument Q definition), and R is assumed to depend on Q1 and Q2 through
the power product Q1 Qα 2 (exponent initialisation).
Scaling Laws for Film Deposition 7

Fig. 4. Progressive process picture simplification achieved during the various stages
of the scaling law derivation. The dependence of the dimensionless Raman variables
α β
Ω (a–c) and ID /IG (d–f ) on arguments Q1 , Q1 Qα 2 and Q1 Q2 Q3 (where Q1 =
−1 −1 −1 −1
W · p · Φrg , Q2 = ΦAr · Φ and Q3 = ΦN2 · ΦH2 ). The numerical value, −2/3, of
exponent α is empirically determined by separately minimising the data spread in
plots (b) and (e). The numerical value, −3, of exponent β is attained by analogous
procedure from plots (c) and (f ). As the scaling law derivation progresses, Ω and
ID /IG points progressively order, so they finally show clear trends. The dashed
lines represent the best fits to the (c) Ω and (f ) ID /IG data relative to samples of
series D

Stage 3. A new function of Q is chosen for approximating the experimental


data. The value of the exponent α is optimised (exponent adjusting) by min-
imising the corresponding standard deviation σ(α). If σ(α) ≤ σmax (scaling
law testing), the procedure is stopped. The combination so attained repre-
sents the scaling law for the growth parameters. Otherwise, stages 2 and 3
β
are repeated. A further argument Q3 is generated and the form Q1 Qα 2 Q3
hypothesised for the scaling law. If σ(β) ≤ σmax , the procedure is stopped
and the effective dependence of the argument R on the growth parameters
involved is determined. The same procedure as for R has to be followed for
any other Raman argument R and/or for the film fractional content of any
composing element ξ (with k ξk = 1). However, in principle, the introduc-
tion of different arguments (Q1 , Q2 , ...) is necessary and different exponents
(α , β  , ...) are, as a consequence, attained.
8 Giacomo Messina and Saveria Santangelo

3.3 Choice of Q-arguments

According to the procedure of Sect. 3.2, the G band frequency position is


first replaced with the dimensionless argument Ω = (ωsp2 − ωG )/ωsp2 (where
ωsp2 = 1575 cm−1 is the value, ωG tends to in disordered CN-alloys with low C
contents [31]) and the D/G intensity ratio (ID /IG ) is considered in place of the
average size of Csp2 clusters (LC ). Suitable dimensionless combinations of the
deposition variables are then generated on the basis of the current assessments
on the synthesis of C-based films [36, 37, 38, 39, 40, 41, 42, 43, 44, 45, 46].
It is worth noting that the same procedure as for Ω is independently
followed for ID /IG , as well as for the fractional film N-content (ξN = 0.070 −
−0.098). However, since both Raman arguments reflect the features of C-
nanostructures, that, in turn, are strongly influenced by the N-incorporation
level, the same arguments are tentatively considered and successfully tested
by comparison with the experimental Ω, ID /IG and ξN data.
The first argument introduced,

Q1 = W · p−1 · Φ−1
rg

(where Φrg = ΦN2 + ΦH2 stands for the reactive gas flow rate), ideally relies
on impact ion energy for depositions operated in reactive atmosphere [24]. It
is chosen with the purpose of taking into account the significant role played
by impact ion energy in determining the film characteristics [37, 39, 40, 46]. It
has been demonstrated [24] that, if the films are prepared by changing solely
W , p and Φrg , the choice of Q1 as a scaling law for the growth parameters
allows stopping the procedure at stage 1. In the presence of a larger number
of independently varying deposition variables instead, Q1 introduces only a
partial simplification (Fig. 4a,d), calling for the successive stage running.
Hence, a second argument,

Q2 = ΦAr · Φ−1

(where Φ = Φrg + ΦHe + ΦAr denotes the flow rate of all inlet gases), is
generated. The introduction of Q1 is intended to take into account the strong
influence exerted by the changes of Ar gas fraction on the deposition rate
and C-atom nanostructure formation [47, 48, 49, 50]. The comparison with
the experimental data in stage 3 (Fig. 4b,e) shows that the combination
W · p−1 · Φ−1
rg · (ΦAr · Φ
−1 −2/3
) remarkably reduces the spread of both Ω and
ID /IG points.
Trying to further simplify the process picture, stages 2 and 3 are repeated.
A third argument,

Q3 = ΦN2 · Φ−1
H2 ,

ideally taking into account the antagonist action carried out by N2 against H2
in surface reactions involving growth precursor species [51, 52, 53], is finally
generated.
Scaling Laws for Film Deposition 9

3.4 The Scaling Law for the Growth Conditions

At the end of the above described procedure, the scaling law,


−2/3
Q = W · p−1 · Φ−1
rg · ΦAr · Φ2/3 · Φ−3 3
N2 · ΦH2 (1)

(with rf power, chamber pressure and gas flow rates expressed in W, mTorr
and sccm, respectively), is derived. This law is able to effectively account
for the variations of the fractional film N-content and of considered Raman
arguments with the growth conditions.
At this stage, (1) actually accounts for all the changes of ξN , Ω (Fig. 4c)
and ID /IG (Fig. 4f) produced by the variations of W , p, ΦAr , Φ, ΦN2 and ΦH2
in the ranges 220−−300 W, 20−−38 mTorr, 30−−70 sccm, 107−−127 sccm,
4−−20 sccm and 3−−7 sccm (under which the films of series D are prepared).
In order to further test the effectiveness of Q, a new series of samples is
prepared. The deposition parameters of these films (series T) are chosen so
as to obtain values of Q falling within the range investigated (even if a wider
range is actually considered for some of the growth variables). The ξN , Ω and
ID /IG points relative to additional samples line up along the curves drawn
by points relative to films of series D, confirming the validity of the scaling
law derived. This is demonstrated in Fig. 5 for the film N-content (xN ) and in
Figs. 6 and 7 for the dimensionate Raman variables ωG and LC . Argument Q,
therefore, finally turns out to be able to account for all the changes of xN ,
ωG and LC produced by the variations of W , p, ΦAr , Φ, ΦN2 and ΦH2 in
the ranges 180 − −400 W, 20 − −38 mTorr, 30 − −70 sccm, 105 − −127 sccm,
4 − −20 sccm and 2 − −7 sccm.

3.5 Resulting Simplification of the Process Picture

As demonstrated in Fig. 4, a progressive process picture simplification is


achieved once the problem is reformulated in terms of Q-arguments. This
result is of crucial importance for the achievement of a well-controlled depo-
sition process.
First, ξN , Ω and ID /IG points, initially covering 7D hypersurfaces as an
effect of the variation of W , p, ΦAr , Φ, ΦN2 and ΦH2 , now line up along
2D curves. The reason is that, as shown, ξN , Ω and ID /IG depend on the
growth parameters through a single dimensionless combination of them. In
second place, by fitting such curves to proper functions, the dependence of
ξN , Ω and ID /IG (i.e., of xN , ωG and LC ) on the deposition variables can be
explicitly determined. The choice of the functions approximating the physical
laws governing the process is, to some extent, arbitrary. Nevertheless, the film
N-content is satisfactorily fitted to

xN (%)  7.26 + 0.85 exp[((Q/0.8)0.1 )].


10 Giacomo Messina and Saveria Santangelo

Fig. 5. Dependence of film N content (xN ) on the dimensionless argument Q. Open


and filled symbols refer to a-CN:H films utilised for deriving (series D) and testing
(series T) the scaling law, respectively. The dashed line represents the physical
approximant, xN  7.26 + 0.85 exp[((Q/0.8)0.1 )], to the data

The frequency position of the G band and average size of Csp2 clusters of
the films under study are well reproduced by the analytical functions

ωG (cm−1 )  1565.8 − 3.0Q + 9.5 exp[−(Q/0.8)8]


and
LC (nm)  1.49 − 7.59Q2 exp(−5.49Q2),

whose form, empirically demonstrated by fitting the experimental data, is


theoretically inferred from extremely simplified models [54] that account for
the influence of the microscopic growth variables on the deposition process.
Finally, if the growth parameters are scaled within the ranges above indicated,
according to (1), the N-incorporation level into the film and the features of
the resulting C-nanostructures do not correspondingly undergo significant
changes. In other words, xN , ωG and LC are invariant for all the simultaneous
variations of W , p, ΦAr , Φ, ΦN2 and ΦH2 leaving Q unchanged. This further
implies that the same xN , ωG and LC can be obtained even starting from
different configurations, provided that the deposition parameters selected
give the same value of Q.
Once a clear correlation is established between variations of the growth
conditions and corresponding changes of the film physical properties, the
final issue of sample preparation can be foreseen and, besides, the a-CN:H
characteristics can be tailored by properly tuning the deposition parameters.
Scaling Laws for Film Deposition 11

Fig. 6. Dependence of the G band frequency position (ωG ) on the dimensionless


argument Q. Symbols are the same as in Fig. 5. The dashed line represents the
physical approximant, ωG  1565.8 − 3.0Q + 9.5 exp[−(Q/0.8)8 ], to the data. Note
that ωG data are the same as shown in Fig. 2. The comparison between the two plots
clearly demonstrates the simplification attained after the problem reformulation in
terms of argument Q

Fig. 7. Dependence of the Csp2 cluster average size (LC ) on the dimensionless
argument Q. Symbols are the same as in Fig. 5. The dashed line represents the
physical approximant, LC  1.49 − 7.59Q2 exp(−5.49Q2 ), to the data

4 Discussion
4.1 Reason for the Scaling Law Existence

The presented results clearly show that, in the films considered, stoichiome-
try and related structural properties are determined by the six independent
deposition parameters through a single combination of them. The existence
12 Giacomo Messina and Saveria Santangelo

Fig. 8. Average film growth rate as a function of the dimensionless argument Q.


Symbols are the same as in Fig. 5; a line is drawn as a visual help

of such an effective combination suggests the possibility that, upon variation


of the growth conditions, a mutual compensation takes place between the
effects generated on film composition and C-nanostructures by the physical
agents (impact ion energy of precursor species, influence of sputtering gas
and antagonism of H2 and N2 in surface reactions), which arguments Q1 , Q2
and Q3 are related to. For instance, the simultaneous increase of rf power and
flow rate of sputtering gas will reflect onto higher impact energy of the pre-
cursor species and improved sputtering efficiency. The former factor favours
C-enrichment of the growing layer, while, contrarily, the latter hinders C-
deposit due to the etching process carried out by Ar-atoms. Analogously,
raising the nitrogen flow rate, while simultaneously decreasing chamber pres-
sure, will cause a N-incorporation enhancement and, again, an impact ion
energy increase. The former agent promotes the formation of nucleation cen-
tres for Csp2 clusters, while the latter, conversely, favours the development
of tetrahedrally bonded C-phase. Therefore, in both the cases, as a balance
of the opposite effects generated by the variation of the microscopic variables
involved into the growth process, the stoichiometry and the structural and
bonding properties of the deposited film may finally undergo no appreciable
change.
The cited examples allow us to qualitatively understand the reason for
the existence of scaling law (1) and the related invariance of the film charac-
teristics. Below, an alternative path for deriving the scaling law is proposed,
based on the formulation of a simple theoretical model of the growth process.
In this frame, the changes undergone by the microscopic variables internally
ruling the film deposition are correlated with the variations externally carried
out on the growth parameters, so as the scaling law existence is semiquanti-
tatively explained.
Scaling Laws for Film Deposition 13

4.2 Modelling of the Growth Process

It is important to remember that an approximate, rather than an exact solu-


tion to the complex problem of film deposition by reactive sputtering is here
searched for. This concept should guide the reader in the present subsection,
where an extremely simplified model is proposed.
An exhaustive discussion about the mechanisms involved in a-C-based
film growth can be found in [46]. Here, far from regarding all the variables
actually governing the film deposition, the discussion is limited to those pa-
rameters whose variation (Table 1) is responsible for the property changes
observed in the samples under study (Table 2).
As commonly established [36, 37, 38, 39, 40, 41, 42, 43, 44, 45, 46], impact
ion energy and amount of C-species trapped into the growing layer have a
relevant influence in the synthesis of a-C films. Since in a-CN:H preparation
the C-deposit is controlled by the irreversible surface reactions, the average
energy with which the N- and H-containing precursor species (CHx , C2 Hx ,
CNx , C2 Nx , Hx CN, . . . [55, 56, 57, 58]) impinge onto the substrate does enter
the problem. On the basis of these assessments, it has been demonstrated [24]
that the dimensionless combination of the deposition variables, which are able
to account for the modifications of the characteristics, featuring sputtered a-
CN:H films prepared by varying only W , p and Φrg , can be written as a
power product of impact energy of radicals containing reactive species (Ei,r )
and deposition flux towards the substrate (FC→s ),

Q = (Ei,r )a · (FC→s )c , (2)

with a and c exponents to be empirically determined. Having elementarily


modelled FC→s under proper assumptions [24], combination (2) simplifies to
W · p−1 · Φ−1
rg , i.e., to argument Q1 . However, in present case, because of the
variation of a larger number of growth parameters, FC→s requires a different
and more sophisticated modelling.
As known, in addition to impact ion energy, the structural and bond-
ing properties of a-C based materials largely depend on the deposition
rate [48, 49, 50], which, in turn, in film preparation by sputter techniques,
is strongly influenced by the sputtering gas action. The sputtering gas exerts
a twofold action, resulting in simultaneous competing deposition and etching
processes [59, 60], which alternatingly prevail depending on the changes made
in the growth conditions. Such an alternation is evidenced, as in present case
(Fig. 8), by a nonmonotonic variation of the film growth rate. The reason
for this competition is that, as the sputtering gas fraction increases, on one
hand, sputtering efficiency improves and C-flux towards the plasma enhances.
Meanwhile, on the other hand, high-energy Ar-atoms etch the growing film
layer causing a diminishing deposition rate.
Then, nitrogen and hydrogen bring about a competitive action in sur-
face reactions [51, 52, 53]. The antagonism between the two reactive gases
14 Giacomo Messina and Saveria Santangelo

is due to the different sticking coefficients of N- and H-containing precur-


sor species. Radicals having energy enough penetrate into the growing layer,
while the remaining ones stick to its surface and form an adsorbate layer.
Nitrogenated radicals possess, on average, lower impact energies, i.e., higher
sticking coefficients, sn . They are, hence, generally adsorbed onto the growing
layer [38]. Contrarily, more energetic hydrogenated radicals (to which lower
sticking coefficients, sh , pertain) penetrate into the growing layer with con-
sequent densification [46]. This reflects onto the local C-bonding and film
stoichiometry. Since terminal Cspx Nspy groups act as nucleation centres for
Csp2 phase [31, 33], the adsorption of nitrogen promotes the film clusteri-
sation degree enhancement. The penetration of hydrogen, instead, favours
the formation of hydrocarbon groups Csp3 Hx [31, 33, 61]. In addition, since
hydrogen is preferentially released in ion-induced desorption (dehydrogena-
tion) [46], H-adsorption promotes the film C-enrichment. N-incorporation,
instead, progresses at expense of the film C-content (see [61] in this book at
p. 221). Therefore, any variation of the ratio sn /sh results in changes of film
stoichiometry, as well as of the nature of nanostructures formed by C-atoms.
These are the reasons why a comprehensive model of FC→s , besides to
the role of the permanence time (trg ) of reactive gases into the chamber [24],
should primarily take into account the action of the fluxes of Ar-atoms to-
wards target (FAr→t ) and substrate (FAr→s ), as well as of the flux of reactive
gases towards the substrate (Frg→s ). The effects should be, then, further
considered of the antagonism between N2 and H2 , ruled by the ratio (sn,h )
between the sticking coefficients of nitrogenated and hydrogenated radicals.
FAr→t feeds the C-flux towards the plasma, favouring C-deposit. Contrar-
ily, being responsible for the simultaneous etching process, FAr→s hinders
deposition. Acting on the precursor species formation, Frg→s controls C-
incorporation into the growing layer. Finally, sn,h decides the type of growth

Table 3. Proportionality relationships between microscopic (internal) growth vari-


ables and measurable (external) deposition parameters. Ei,r denotes the average
impact energy of radicals containing reactive species. FAr→s and FAr→t respectively
indicate fluxes of Ar atoms towards substrate and target. Frg→s stands for flux of
reactive gases towards the substrate. Finally, trg denotes the permanence time of
reactive gases into the deposition chamber, while sn,h indicates the ratio, sn /sh ,
between sticking coefficients of nitrogenated to hydrogenated precursor species

Internal variable Proportionality with external parameters From refs.


Ei,r W 1/2 · p−1 · Φ−1
rg · Φ [36], [41], [46]
FAr→t W 3/4 · p1/4 · ΦAr · Φ−1 [36], [46], [62]
FAr→s W 1/4 · p3/4 · ΦAr · Φ−1 [54]
Frg→s W 1/4 · p3/4 · Φrg · Φ−1 [54]
trg p · Φ−1 [24]
sn,h ΦN2 · Φ−1
H2 [54]
Scaling Laws for Film Deposition 15

precursors incorporated. Accordingly, the flux of precursor species reaching


and sticking to the substrate is here modelled as:

FC→s ∝ (FAr→t )b · (FAr→s )−d · (Frg→s )f · (trg )h · (sn,h )−l , (3)

with b, d, f , h and l positive exponents to be empirically determined. FAr→s


and sn,h enter expression (3) with negative exponents, which ideally take
into account the hindering action, carried out by etching process and N-
incorporation, against C-deposit. Such a novel expression generalises that
previously derived [24].

4.3 Physical Meaning of the Scaling Law

As accurately discussed in [54], in a-CN:H preparation by rf diode systems,


under the deposition conditions of Table 1, the above-considered microscopic
process variables are related to the macroscopic growth parameters through
the proportionality relationships reported in Table 3. Replacing such expres-
sions in (2) and (3) allows us to write Q explicitly in terms of measurable
and externally tunable parameters. The latter enter the expression of Q con-
sequently obtained with the exponents reported in Table 4. The numerical
values of these exponents can be empirically determined through the experi-
mental data fitting, so as to finally obtain:
−2/3 −3
(W 2/3 · p−4/3 · Φ−4/3
rg · Φ4/3 ) · (W 1/3 · p1/3 · ΦAr · Φ−2/3 · Φ1/3 3
rg · ΦN2 · ΦH2 ).

4/3
This product, whose first term corresponds to Ei,r , while the second being
a power of FC→s , gives combination (1).
All the deposition parameters but ΦAr enter both the two microscopic
factors singled out within the expression of Q, and, what is more, each of
them influences more than one internal variable. Hence, varying the growth
conditions causes many microscopic variables to change simultaneously and,
sometimes, the opposite effects, which are produced by these changes on film
stoichiometry and the nature of C-nanostructures, to compensate each other.
For this reason the film properties may appear insensitive to the changes of
the deposition conditions or, more generally, their modifications may be not
readily foreseeable.

4.4 The Scaling Law for the Microscopic Growth Variables

Once the exponents, with which the external deposition parameters enter
combination obtained by replacing (3) in (2), have been empirically deter-
mined, the explicit relationship between Q and the microscopic growth vari-
ables can be further derived by the aid of relationships of Table 4, so we
finally attain

Q = (Ei,r )4/3 · (FAr→t )5/6 · (FAr→s )−3/2 · (Frg→s )1/3 · (trg ) · (sn,h )−3 . (4)
16 Giacomo Messina and Saveria Santangelo

Table 4. Exponents with which the deposition parameters enter (2), as explic-
itly written, in terms of measurable parameters, after replacement of relationships
reported in Table 3. W and p denote rf power and chamber pressure, while Φrg
and ΦAr indicate the flow rates of reactive gases and sputtering gas, respectively. Φ
stands for the flow rate of all the inlet gases. ΦN2 and ΦH2 denote N2 and H2 flow
rates
Deposition parameter Corresponding exponent Numerical value
W a/2 + (3b − d + f ) · c/4 1
p −a + (b − 3d + 3f + 4h) · c/4 −1
Φrg −a + f c −1
2
ΦAr c · (b − d) −
3
2
Φ a − c · (b − d + f + h)
3
ΦN2 −lc −3
ΦH2 lc 3

As hypothesised, Q depends inversely on FAr→s and sn,h . This finding indi-


rectly confirms the property of the assumptions on which the model for-
mulated is based. In particular, (4) demonstrates that, as hypothetically
supposed by expression (3), manifold factors may simultaneously influence
FC→s . Favouring and feeding the precursor species formation, longer trg and
larger Frg→s make more intense the carbonaceous flux towards the substrate.
FAr→t assists C-flux towards the plasma, thus its increase results in film
C-enrichment. Contrarily, raising FAr→t , as a result of etching enhancement,
hinders the development of the growing layer. The balance between the simul-
taneous deposition and etching processes determines the film growth rate [61].
However, all the internal deposition variables cooperatively participate in the
occurrence of these processes. This is clearly demonstrated in Fig. 8, where
the average deposition rate, as deduced from the results of joint IR and
RBS film-thickness measurements [54], is plotted as a function of Q. A non-
monotonic trend is obtained, as expected. Finally, since the incorporation
of nitrogen progresses at the expense of film C-enrichment [61], contrarily
promoted by hydrogen due to the preferential desorption from the surface
adsorbate layer, decreasing sn and/or increasing sh , i.e., lowering sn,h , ulti-
mately results in films with higher C-contents.
Combination (1) provides the rules according to which the external de-
position parameters, W , p, ΦAr , Φ, ΦN2 and ΦH2 , can be scaled, within the
ranges considered, with no significant changes in film stoichiometry and na-
ture of C-nanostructures. Correspondingly, (4) can be regarded as the scaling
law for the internal growth variables, Ei,r , FAr→t , FAr→s , Frg→s , trg and sn,h .
Scaling Laws for Film Deposition 17

The existence of the latter reflects onto (and, thus, explains fully and defi-
nitely) the existence of the former.

4.5 A Figure of Merit for a-CN:H Film Deposition

It is finally important to point out another relevant outcome emerging from


the search for an approximated solution to the a-CN:H film growth process.
According to expression (2), in order to increase Q it is sufficient that only
one of the two factors, that Ei,r - or that FC→s -related, increases due to vari-
ations in the growth conditions. On one hand, as known, increasing impact
ion energy gives rise to higher sp3 /sp2 C-bonding (i.e., fourfold-/threefold-
coordinated C-atom) fractions. On the other hand, enhancing FC→s allows
the deposition of C-richer films. Since all the elements in the films exhibit a
coordination number lower than C (Nsp1 is 1- or 2-coordinated [63]; Nsp2 , if
present, is 2- or, in very few cases, 3-coordinated [64]; H is 1-coordinated), the
increase of relative C-content causes similarly the enhancement of the film
average coordination number (χav ). As evidenced by the G band downshift
(Fig. 6), films with improved characteristics are actually obtained at higher
Q values. Hence, Q can be regarded as a “figure of merit” for hydrogenated
amorphous carbon–nitride growth by sputtering.
When deposition is operated in the low Q regime, the N-incorporation
level remains roughly constant (Fig. 5). Under this condition, the slow ωG
variation (Fig. 6) reflects the C-bonding evolution produced by the forma-
tion of different hydrocarbon groups [29, 31, 33]. Porous, softer and H-richer
films are attained, with Csp2 cluster islands exhibiting progressively smaller
dimensions going towards lower Q (Fig. 7). By operating at higher Q val-
ues, instead, the enhanced terminal Cspx Nspy group formation promotes
the Csp2 matrix development and hinders H-incorporation [29, 31, 33]. Corre-
spondingly, LC gradually increases, while ωG drops as an effect of the changed
film stoichiometry and related χav increase.

5 Conclusion
The results of Raman analysis and Rutherford backscattering measurements
performed on a-CN:H films, prepared by graphite sputtering in N2 –H2 –He–Ar
atmosphere, are utilised for the derivation of a scaling law for the deposition
parameters. This is accomplished by means of a semiempirical approach,
based on an extended application of theorem on “physically similar systems”
of dimensional analysis.
The influence of the growth conditions on the film stoichiometry as
well as on the resulting features of the nanostructures formed by C-atoms
is investigated. By elementarily modelling the reactive sputtering process,
the crucial role played by the variables internally ruling film deposition is
18 Giacomo Messina and Saveria Santangelo

clarified. We demonstrate that impact energy of radicals containing reac-


tive species (Ei,r ), fluxes of Ar-atoms towards substrate (FAr→s ) and tar-
get (FAr→t ), flux of reactive gases towards the substrate (Frg→s ), perma-
nence time of reactive gases into the deposition chamber (trg ) and ratio be-
tween sticking coefficients of nitrogenated to hydrogenated precursor species
(sn,h ) enter in determining the film properties through their combination
−3/2
Q = Ei,r · FAr→t · FAr→s · Frg→s · trg · s−3
4/3 5/6 1/3
n,h . Such a combination represents the
scaling law for the process on a microscopic scale. In the frame of the growth
process approximation, the changes undergone by the internal variables are
therewith correlated with the variations externally operated on rf power (W ),
chamber pressure (p) and flow rate of all the inlet gases (Φ), of sputtering-gas
(ΦAr ) and of reactive gases (Φrg = ΦN2 + ΦH2 ). As a result, the scaling law,
−2/3
Q = W · p−1 · Φ−1rg · ΦAr · Φ2/3 · Φ−3 3
N2 · ΦH2 , for the measurable and externally
tunable deposition parameters is derived.
The argument Q is then shown capable of accounting for all the changes
of the film N-content (xN ), of the frequency position of the G band (ωG )
and of the average size of Csp2 clusters (LC ), produced by the variations
of W , p, ΦAr , Φ, ΦN2 and ΦH2 in the ranges 180 − −400 W, 20 − −38 mTorr
(2.7−−5.1 Pa), 30−−70 sccm, 105−−127 sccm, 4−−20 sccm and 2−−7 sccm.
By fitting the experimental data relative to the films under study, the physical
approximants xN (%)  7.26 + 0.85 exp[((Q/0.8)0.1 )], ωG (cm−1 )  1565.8 −
3.0Q + 9.5 exp[−(Q/0.8)8 ] and LC (nm)  1.49 − 7.59Q2 exp(−5.49Q2) are
attained. These represent the empirical rules whose knowledge is required
to be able to tailor the film characteristics through specific changes of the
deposition conditions.

Acknowledgements

We wish to thank Prof. A. Tagliaferro and Dr. G. Fanchini of the Physics


Department, Polytechnics of Torino, who kindly provided a-CN:H samples.

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Index
a-C:H:N, 1–5, 10, 11, 13, 14, 16, 17 hydrogenated amorphous carbon-
sp2 -bonded clusters, 5, 10, 18 nitrides, 1
cluster size, 5, 8, 10, 11, 18
sp3 /sp2 bonding ratio, 17 microscopic growth variables, 12–15

approximated solutions, 1, 2, 10, 11, 13 nitrogen incorporation, 10, 12–17

physical approximants, 1, 10, 11, 18


carbon coordination, 17
process approximation, 2, 13–15, 18
threefold and fourfold coordination,
process modelling, 13–15
17
Q-arguments, 1, 6, 8, 9
dimensionless arguments, 4–6, 8
Raman dimensionless arguments, 6–8
figure of merit for growth process, 17 Raman spectroscopy, 1–3, 17
film stoichiometry, 3, 11, 12, 14–17 reactive sputtering, 2, 13

G band, 3, 4, 8, 10, 11, 17, 18 scaling laws, 1, 2, 15, 17, 18


derivation method, 1, 4, 7–9, 17
hydrogen desorption, 14, 16 validity range, 9
A Spectroscopic Approach to Carbon
Materials for Energy Storage

Giuseppe Zerbi1,2 , Matteo Tommasini1,2 , Andrea Centrone1,2 ,


Luigi Brambilla1,2 , and Chiara Castiglioni1,2
1
Dipartimento di Chimica, Materiali e Ingegneria Chimica “G. Natta”,
Politecnico di Milano, Piazza Leonardo da Vinci 32, I-20133 Milano, Italy,
and INSTM, Unità di Ricerca di Milano
2
Centro d’Eccellenza “Nano-Engineered MAterials and Surfaces” (NEMAS),
Politecnico di Milano, Via Ponzio 34/3, I-20133 Milano, Italy
giuseppe.zerbi@polimi.it

Abstract. In this Chapter we present the contribution offered by vibrational spec-


troscopy in the characterization of carbon-based materials. The necessary concep-
tual tools will be introduced in Sect. 2 and Sect. 3; the basic structural and dynam-
ical properties of the different crystalline or ordered aggregation forms of carbon
will be described. With such a background we pave the way to the spectroscopic
characterization (Raman and infrared) of disordered carbon materials, such as those
recently proposed for hydrogen storage. The application of the concepts and data
described to the field of new carbon materials for energy storage is presented.

1 Introduction

Carbon-based materials are at present of great technological relevance as pos-


sible substances that are capable of storing hydrogen as new energy vectors
in the automotive field. In the past few years the interest in carbon-based
materials for energy storage has reached very high levels as a consequence
of the news reported by some laboratories [1, 2, 3] that such materials could
absorb, even at room temperature, astonishingly large amounts of gaseous
hydrogen. If these reports were true the “energy problem” which plagues hu-
manity could have been easily and happily solved. Unfortunately, the data on
hydrogen absorption reported were not reproduced by other authors and were
later shown to be unacceptable [4, 5, 6]. Moreover, many other papers report
little or negligible hydrogen absorption in different carbon nanostructures
(for a general discussion and a list of references see [7]).
We became concerned with the failure of the many attempts to squeeze,
in a reversible way, hydrogen inside some kind of carbonaceous materials
and noticed that most of the experiments were not based on some sort of
rationale in the choice of the materials. Indeed, the physics of the absorption
necessarily must be strictly related to the yet unknown structure, at the
molecular level, of such carbon-based materials. On the other hand, it is well
known that the knowledge, at the molecular level, of amorphous carbon-based

G. Messina, S. Santangelo (Eds.): Carbon, The Future Material for Advanced Technology Ap-
plications, Topics Appl. Phys. 100, 23–53 (2006)
© Springer-Verlag Berlin Heidelberg 2006
24 Giuseppe Zerbi et al.

materials cannot be easily obtained because they are generally insoluble and
noncrystalline solids.
The above observations have inspired a group of laboratories to take a
“molecular approach” to the problem of hydrogen absorption [8]. The project
focussed on producing carbon-based materials of suitable structure by syn-
thesis in controlled situations [8, 9], followed by a molecular characteriza-
tion [10] and the development of first-principle calculations that may guide
the interpretation of the experimental data [11, 12, 13, 14]. Two classes of
polyaromatic compounds were considered (for a general discussion see [15]),
namely 1. polyaromatic dendrimers and 2. carbon-based materials (PAH)
obtained from a controlled graphitization [9] of structurally well-character-
ized and monodisperse polyaromatic precursors. Details on these studies are
reported in Sects. 4 and 5 of this Chapter.
Again, such research turned out to be unsuccessful since the amount of
hydrogen absorbed is still hopelessly small and sometimes negligible. This
poses the basic scientific demand (of general interest) to relate the molecular
nature and the electronic properties of the hydrogen molecule to the fact that
it can indeed wander inside a carbon cage, but it does not find the conditions
to stick inside such a cage.
We believe that the approach to the problem must systematically proceed
first with the understanding of both the ordered and disordered structures
the carbon atoms are able to generate. The structures must be identified by
means of experimental physical techniques, which are obviously many when
the carbon materials are crystalline and ordered, while they reduce to a few
techniques, sometimes vague, when the materials become disordered. First-
principle calculations may provide the clue, or a hint, to the understanding of
such structural data. This line of thought inspires the discussion that follows
in this Chapter.
Our approach aims at presenting how molecular and lattice dynamics
(and, by consequence, infrared and Raman spectroscopy) can play a role in
the field of carbon-based materials. We wish to present the state of the art
and the recent development of molecular dynamics and vibrational infrared
and Raman spectroscopy (theory and experiments) (i) as a probe of ordered
and disordered carbon-based materials and (ii) as a probe of hydrogen pushed
into the interatomic spaces in such carbon-based materials.

1.1 Carbon-Based Materials

The definition of “carbon-based materials” is indeed quite vague, and we shall


try to draw some boundaries dictated by the kind of analysis we are going to
discuss. In the formation of any kind of covalently bonded network of carbon
atoms, each carbon may act in one of its three states of hybridization, namely
Csp3 , tetrahedral, Csp2 , plane trigonal and Csp, linear. The duty of organic
chemistry is to strictly control the reaction process directing carbon atoms
to preassigned positions in a given molecule under construction and with a
A Spectroscopic Approach to Carbon Materials for Energy Storage 25

preassigned hybridization state (hence in a given valence state). The molecu-


lar architecture and the derived physical and chemical properties follow from
the result of the reaction process.
Recently physics has moved into the field of carbon and proposed very
interesting and potentially useful new ways to obtain networks of carbon
atoms generated by collisions of carbon atoms subjected to welldefined ki-
netic and thermodynamic conditions [16]. Various kinds of diamond-like or
graphite-like materials have been produced which show very interesting new
mechanical and electrical properties. The precise control of the physical con-
ditions have also allowed for the generation of structurally ordered carbon
networks like fullerenes [17] and carbon nanotubes [18], which are at present
matter of strong interest in science and technology.
While a whole set of physical techniques of characterization can be ex-
ploited in the case of simple organic materials practically in any physical
phase, the chore of structural characterization, at the so-called molecular
level, of structurally highly disordered, insoluble and sometimes unstable sys-
tems becomes an exciting challenge to physics and chemistry. We review and
discuss some of the aspects of the role of molecular dynamics and vibra-
tional infrared and Raman spectroscopy and its achievements in the study of
disordered carbon-based materials.
A warning is necessary at the beginning of this Chapter. Our whole ex-
perience in molecular and lattice dynamics and spectroscopy has developed
based on a molecular approach [19, 20]. In this approach, the vibrating ob-
jects are made with atoms of a known mass, connected by valence bonds
in a given chemically acceptable architecture and subjected to an intra- or
intermolecular potential which can be conveniently described by a “valence
force field” originating from electrons building up the chemical bonds. Inter-
molecular interactions will generally be represented by some kind of Van der
Waals forces [21, 22, 23]. In other words, we will stick as much as possible to
a molecular modelling of both our ordered or disordered systems made up by
carbon atoms.
Our chemical background allows us, when nature makes it possible, to
look at the systems as infinite lattices or as finite systems. Consideration of
finite systems opens the window to the very rich class of oligomeric molecules
which have been made (or can be made on purpose) by chemists as models
of larger, but chemically extremely similar systems. Consideration of the
dynamics of finite (even if very large) molecules [24] does not allow us to
overlook the existence of surface effects (or end effects), which may affect, to
different extents, the electronic properties, the dynamics and the spectra of
the systems studied. As a typical case of identification of end effects we quote
the case of the spectra of the oligomers of pyrrole up to polypyrrole [25].
The examples presented in this Chapter witness the relevance of oligomers
in such a kind of studies. The striking case is that of the use of infrared
spectroscopy on a series of polymethylene chains, CH3 –(CH2 )n –CH3 , which
26 Giuseppe Zerbi et al.

has allowed plotting, with great accuracy, all the phonon dispersion curves
of polyethylene considered as a one-dimensional lattice [26, 27]. This goal has
never been reached by any, even modern, neutron scattering experiments.

2 Prototypical Lattices in Three, Two


and One Dimensions
In the introductory paragraph we referred to the three states of hybridiza-
tion of carbon atoms as basic units that can generate ordered or disordered
networks uniquely made up by carbon atoms. Before proceeding we feel it
necessary to introduce in the discussion some additional “basic lattices” that
will be encountered later in our discussion. Let us consider the extreme struc-
tures of various ordered organizations of carbon atoms all in a unique state
of hybridisation.

2.1 Diamond

The ordered linking of Csp3 generates diamond, which has been treated by
hundreds of papers from solid state physics to applied industrial technol-
ogy [28]. Diamond is an indirect band-gap material with an energy gap of
5.49 eV. In diamond Csp3 atoms are joined by single σ bonds. The three-
dimensional (3D) lattice of diamond consists of two interpenetrating face-
centered cubic lattices, displaced one from the other by 1/4 of the principal
diagonal of the cube. Each atom of one lattice is at the centre of a tetrahe-
dron formed by its four neighbours of the other lattice. The crystallographic
translational unit cell contains eight atoms and displays the whole cubic sym-
metry Oh . The smallest translational unit cell (primitive cell) contains only
two atoms. These two atoms generate six branches in the phonon dispersion
relation [29]. The phonons that propagate along the symmetry directions of
the first Brillouin zone belong to well-defined symmetry species and determine
the number of phonon branches experimentally observed (by neutron scatter-
ing) along a chosen symmetry direction. At Γ the three optical branches are
triply degenerate (F2g symmetry), while the triply degenerate translational
mode at ν = 0 is of F2u symmetry.
For our kind of discussion most of the dynamic properties of diamond are
already available [30, 31]. Accurate phonon dispersion curves are available,
and they have been nicely accounted for by a six-parameter valence force field
refined by least squares fitting over an extremely large number of phonon
frequencies derived from neutron scattering data [29]. As seen in Table 1, the
statistical dispersions of the calculated valence force constants are generally
very small, thus supporting the physical meaning of the calculated numbers.
The information we feel relevant for this Chapter derives from the values
of the valence force constants reported in Table 1:
A Spectroscopic Approach to Carbon Materials for Energy Storage 27

Table 1. Six-parameter valence force field and relative uncertainties for diamond
crystal. Units: stretching and stretching–stretching force constants are expressed in
(mdynes/Å), bending and bending–bending in (mdyne Å/rad2 ), stretching–bending
in (mdyne/rad)

KR = 3.831 ± 0.023
HΛ = 0.872 ± 0.121
FR = 0.164 ± 0.017
FRΛ = 0.392 ± 0.012
FΛ = −0.015 ± 0.010
FΛ = 0.173 ± 0.043

(i) The diagonal and off-diagonal valence force constants are fully compara-
ble with those derived from similar studies of n-alkane chains and poly-
ethylene [26, 27], thus showing that the ‘chemistry’ of the C–C bonds is
very similar (as expected) in the two classes of materials.
(ii) The intramolecular potential for σ-bonded C–C systems is very localized
mostly to its first neighbour, and it feels only a slight perturbation by
the second neighbour (FΛ = 0.173 ± 0.043 mdyne Å/rad2 ). This is
again in agreement with the finding of molecular dynamics of n-alkane
chains [26, 27], of the lattice dynamics of polyethylene [32] and of similar
simple polyolefins [33].
The highest optical frequency of F2g symmetry is observed in the Raman
spectrum at 1338 cm−1 . For a perfect crystal no other one-phonon transitions
are predicted to be observable in the optical spectra. However, as soon as the
crystal contains defects, the translational symmetry is broken and many of
the lattice modes gain some dipole moment change, thus giving rise to weak
absorption bands in the infrared. One-phonon and two-phonon densities of
states are available both from calculations and experiments [29].
Oligomeric molecules for diamond were not known for quite a while. The
first cage molecule, adamantane [34], was discovered in 1933 and only recently
has research on nanostructured materials revealed that a whole class of oligo-
adamantanes or diamondoids can be obtained from petroleum [35, 36, 37].
Their physical properties are under intense study, and their molecular dy-
namics and spectra are in too early a stage to teach us something relevant
for the understanding of ‘end effects’ of finite diamond lattices. Contrary to
what we will discuss below for Csp2 and Csp systems, we expect that the
28 Giuseppe Zerbi et al.

dynamical perturbations by the end effects for diamond will die off quickly
moving into the crystal because only the nearest neighbours are involved in
the vibrations, as mentioned above.

2.2 Graphite

Next we consider Csp2 , which can form a two-dimensional (2D) lattice of


graphite or a one-dimensional (1D) lattice as in the case of polyacetylene. In
such a state of hybridization each carbon atom must be linked to its neigh-
bours with three σ bonds in a trigonal planar geometry and with one π bond
located at either side of the plane of the σ bonds. Because of the existence of
a large set of interacting 2pz orbitals, a whole new physics has been developed
in order to account for the delocalization in 2D or 1D lattice of such electrons
and for the variety of new physical processes that are generated. The first
consequence of such delocalization is that the intramolecular interactions of
π electrons extend over large distances as revealed in many experiments and
as indicated by first-principle calculations.
The prototypical case of a Csp2 lattice in 2D is graphite, which at present
is matter of active theoretical and experimental studies. Graphite is a layered
material consisting of superimposed sheets made up by carbon atoms in sp2
hybridization. Each sheet has a honeycomb structure that can be viewed as
the limiting case of a polycondensed aromatic system of infinite size. The in-
termolecular interactions between layers are of Van der Waals type, whereas
the bonds within each layer are covalent σ and π bonds. The π component
gives rise to an extended 2D polyconjugated system with a peculiar semi-
metallic electronic structure [38, 39, 40]. The Fermi surface degenerates to a
point in reciprocal space, named K. This is the corner of the hexagon that
defines the first Brillouin zone (six equivalent K points are therefore present).
The conduction properties of graphite and related compounds such as nano-
tubes [18] are given by the Bloch electrons in the vicinities of the K point.
Similarly to what happens in polyacetylene and its oligomers [41] (which will
be discussed below), a strong electron–phonon coupling is present in graphite
also [42]. This is responsible for the Kohn anomaly recently demonstrated in
graphite [43]. The coupling of π → π ∗ electronic transitions with phonons
allows us to successfully use resonant Raman spectroscopy to characterize
graphite and the related compounds. In particular, for graphite a peculiar
phonon with wavevector K (named A phonon) is normally Raman-silent
since it does not satisfy the q = 0 selection rule. Because of the strong elec-
tron–phonon coupling of the A phonon [42, 43], as soon as the q = 0 selection
rule is removed (by the presence of defects and/or confinement such in mi-
crocrystalline graphite [44, 45]) the A phonon becomes resonantly activated
in the Raman [13, 46, 47]. This gives rise to the so-called D band of defective
graphite and related compounds, observed in the Raman in the 1300 cm−1
frequency range [41]. Moreover, the frequency of the D band shows a disper-
sion with respect to the energy of the laser in resonance condition [13, 44, 45].
A Spectroscopic Approach to Carbon Materials for Energy Storage 29

It has been recently proposed [42, 43] that the coupling of π → π ∗ electronic
transitions with the A phonons (with a wavevector close to the K point)
is ultimately responsible of the observed D peak behaviour. The interested
reader can found additional information about the phonon structure and the
electron–phonon coupling in graphite and nanotubes in the Chapter by Cas-
tiglioni et al. (pp. 381–402).

2.3 Polyacetylene

The simplest 1D lattice made up by a linear sequence of Csp2 is polyacety-


lene (PA), (−CH=CH−)n , which appeared in modern soft matter physics and
chemistry only relatively recently, and in the year 2000 generated a Nobel
Prize in chemistry to Shirakawa, McDiarmid and Heeger. For sake of simplic-
ity, with the acronym PA we refer here to the most stable, and most known,
form of PA, namely trans-polyacetylene as obtained from thermal isomeriza-
tion of cis-polyacetylene (which is the form chemistry provides first during the
synthesis) [48,49,50]. The molecular structure of trans-polyacetylene has been
the subject of many works. The best oriented samples were obtained by the
Durham route with a very high draw ratio [51], which has also been improved
by a modification of the original preparation of the Shirakawa polymer which
reached a draw ratio of 6.5 and which shows a very high anisotropic electrical
conductivity when doped (up to 105 Ω−1 cm−1 , almost like copper) [52].
Polyacetylene, in a first approximation, can be considered a 1D lattice
with a band gap Eg ≈ 1.4 eV consisting of a translational unit (−CH=CH−)
that repeats itself in a linear zig-zag polymer chain. The existence of a band
gap tells us that PA is not a metal, but is instead a semiconductor. Accepting
the language of chemistry, PA is a long polyene chain with conjugated π elec-
trons, while physics describes PA as a dimerized Peierls-distorted sequence
of CH units.
Because of strong electron delocalization, short-chain polyene molecules
(including the large class of carotenoids [53]) become extremely interesting
models for understanding physical properties of PA. Figure 1 shows the vi-
bronic spectra of a series of conjugated oligoenes where (in a one-electron
picture) the strong dependence of the HOMO–LUMO energy gap with the
number of conjugated double bonds appears clearly. By increasing the num-
ber of conjugated double bonds, the Kuhn’s limit of a metallic system is not
reached, but the energy gap opens at a certain length of the chain because
Peierls distortion sets in [54].
As discussed in several review articles, in these polyconjugated 1D systems
the motions of electrons are strongly coupled with the nuclear motions. It has
been shown that for specific normal modes (which can be found by lattice
dynamics calculations) a strong electron–phonon coupling takes place [56],
which strongly enhances the Raman cross section, thus generating an ex-
tremely strong and characteristic scattering line in the frequency range of
the skeletal stretching, near 1500 cm−1 [56]. The molecular approach taken
30 Giuseppe Zerbi et al.

Fig. 1. UV–Vis absorption spectra of oligoenes of increasing chain lengths (n =


3, 5, 6, 8, 10 represents the number of double C=C bonds). Horizontal axis is
wavelengths (nm), left vertical axis is the absorbance (10−3 units) for n = 3, 5, 6;
right vertical axis is the absorbance for n = 8, 10. Taken from [55]

in this work has brought to the interpretation of the electron–phonon coupling


and Raman enhancement in terms of the so-called R− mode1 [57], which can
be related to the approach presented by the school of Horovitz [58, 59].
The electron–phonon coupling depends on the HOMO–LUMO energy
gap, hence on the effective conjugation length (ECL) of the molecule. In
the dynamical treatment in terms of a molecular model, such a mode is indi-
cated by R− . It has been shown experimentally and accounted for by theory
and first principle calculations that the frequency and the intensity of the
R− mode is conjugation length-dependent. Since a real sample of PA from
any reaction process consists of a mixture of molecules (or chain segments)
with varying ECL, by selecting various exciting laser lines in a Raman exper-
iments it is possible to match the energy gap of various effective conjugation
lengths (resonance condition), thus enabling us to probe the “conjugational
polydispersivity” of any real sample [56].
At present, a reliable valence force field for PA is available [41]. Obviously
the use of such a force field for shorter oligomeric models has to consider that
the effective electron–phonon coupling is a function of the conjugation length,
as clearly shown experimentally and theoretically in the case of a series of
polyenals CH2 =CH–(CH=CH)n −CHO [60].
PA can be considered a prototypical system of a very large class of poly-
conjugated 1D systems (oligomers and polymers). While PA is very unsta-
1
The symbol R− replaces for typographical restrictions the symbol commonly
used in the previous literature, namely the letter “ya” of the Cyrillic alphabet.
A Spectroscopic Approach to Carbon Materials for Energy Storage 31

ble, other 1D systems are chemically stable and can be suitably treated
for attaining technologically relevant properties, such as electrical conduc-
tivity, electrochromism, photochromism, electroluminescence, photoconduc-
tivity, nonlinear optical responses, etc. [49, 50, 61]. Of particular interest in
this discussion are the 1D lattices made up by aromatic rings (e.g., polypara-
phenylene (PPP) [62], polyparaphenylene vinylene (PPV) [63, 64], polythio-
phenes [65,66], rylenes [67] and, more recently, functionalized acenes [68,69]).
For a review on the vibrational properties of polyconjugated systems see [70].
At this point of our analysis we need to highlight a structural feature
that strongly determines π electron delocalization in these polyconjugated
systems. Conjugation means a distribution of π electrons along the carbon
skeleton that is made possible through the overlapping of adjacent 2pz or-
bitals, which exist in this class of molecular systems. Maximum coupling takes
place when the two adjacent 2pz orbitals are parallel and any rotation about
the single C–C bond decreases the extent of overlapping. In more technical
structural words, if ϕ is the dihedral angle of the two 2pz orbitals about
the single C-C bond, coupling is maximum at ϕ = 0◦ and is minimum at
ϕ = 90◦ . A cosine law may be guessed for the extent of overlapping as func-
tion of ϕ; the consequent electronic and dynamical properties derive from the
ϕ dependence. In turn, the value of ϕ depends on the conformation of the
system [71].
The geometrically driven coupling of 2pz orbitals allows us to classify poly-
conjugated systems as ‘flexible’ (F) and ‘rigid’ (R). Typical cases are PPP
and PPV, which are certainly F, while the classes of rylenes, linear polyacenes
and generally of ladder polyconjugated polymers and, finally, graphite and
its oligomers can be classified as R molecules. The conformational structure
of F molecules in the solid is the result of energy minimization of inter- and
intramolecular interactions, which may change dramatically when the sys-
tem is dissolved in various solvents or it is mixed in a blend with another
material. Innumerable are the calculations presented in the literature, with
increasingly sophisticated theoretical approaches, which try to evaluate the
various intramolecular contributions that give rise to the potential barrier
supervising the intramolecular conformational flexibility of F systems. The
weakness of such calculations lies in the fact that they can easily treat mole-
cules isolated in vacuo, but have a much harder time dealing with the reality
of systems which do interact in three dimensions (either as crystals or in
liquid and solution states).
For R molecules one can safely think, in a first approximation, that the
electronic properties (and the many relevant consequent physical properties)
remain constant per each given chain length; on the contrary for F systems,
even for a fixed chain length, the conformational flexibility becomes a puzzle
in the effort of rationalizing structure and properties of a given system. Bond
length alternation (BLA) loses its precise meaning, and necessarily the con-
cept of a torsional dependent effective BLA (EBLA) needs to be introduced.
32 Giuseppe Zerbi et al.

In polyconjugated systems intramolecular 2pz –2pz coupling has been con-


sidered mostly for a single molecule in vacuo (as in most of the cases con-
sidered by first-principles calculations). Nowadays increasing importance is
being given to intermolecular 2pz –2pz interactions mostly in the case of R sys-
tems. Indeed self-assembling in solution and formation of liquid crystal phases
have been recently considered for flat rigid oligomeric molecules that show in-
teresting properties (e.g., intermolecular electrical conductivity), which occur
because of intermolecular 2pz –2pz interactions [72, 73, 74].

2.4 Polyynes

The last structural unit to be considered is the linear repetition of Csp units
named by chemists as polyynes, (−C≡C−)n . Not much is known on the
dynamical and spectroscopic properties of polyynes, and their chemistry has
enjoyed a recent revival of which spectroscopy will certainly profit; see, for
instance, [75, 76].
Depending on the hybridization state of the terminal carbon atoms, fi-
nite linear carbon chains can in principle consist of alternating single and
triple bonds, or consecutive double bonds (cumulenes). The first case is
typical of H−(C≡C)n −H linear structures (terminal carbons in sp state),
whereas the cumulenic case is typical of H2 Cn H2 structures (terminal car-
bons in sp2 state). The molecules of allene and acetylene are the first in the
series of cumulenes and polyynes, respectively. We have seen that in poly-
acetylene the Peierls distortion sets in, giving an alternate structure of single
and double bonds. It is likewise reasonable to suppose a similar behaviour
also for an infinite linear chain of carbon atoms. Under this regard, for the
infinite linear chain, the cumulenic structure is expected to be less stable
than the alternance of single and triple bonds (acetylenic structure). In fact,
ring-shaped clusters of carbon atoms have been theoretically studied show-
ing signatures of Peierls distortion and Kohn anomaly and softening of the
dimerization phonon [77], similarly to polyacetylene. Recently, thanks to a
new synthetic procedure [78, 79], solutions of a distribution of linear carbon
chains H−(C≡C)n −H (3 < n < 8) have become available for Raman and
SERS characterization [80]. While the Raman/SERS data for each single
and isolated chain length are not yet available, the theoretical analysis of the
experimental data (through density functional theory calculations) shows a
definite softening of the most active vibration in the Raman with respect
to the increasing length of the linear chain. This is consistent with previous
independent theoretical studies [77].
A Spectroscopic Approach to Carbon Materials for Energy Storage 33

3 A Spectroscopic Approach to Disordered Carbon


Materials
In the previous section we considered carbon-based materials that possess
a highly ordered and well-defined structure. Single crystals with supposedly
perfect structure have been produced and carefully studied for diamond and
graphite. The structure of trans-polyacetylene is sufficiently well known, while
an ‘infinite’ polyyne chain has not yet been obtained. Moving into the world
of real materials, we must accept the unavoidable existence of structural small
or large defects, and the coexistence, in a given solid material, of amorphous
(or disordered) and crystalline domains; sometimes the system is fully dis-
ordered. Following our line of thought we consider it an unavoidable step
in the structural analysis of carbon-based materials to dwell on our present
knowledge of the structure of these systems. In other words, first we need
to know how to handle a few structural defects. Then one can proceed from
slightly disorded to fully amorphous systems.

3.1 1D Systems – Saturated Carbon Materials

The understanding of defects in 1D systems received a great deal of attention


during the golden age of chemistry and physics of classical polymers which,
in most of the cases, consist of σ-bonded carbon atoms in sp3 hybridization
(and this makes life easier). All conceivable theoretical and experimental tech-
niques have been applied to understand the conformational structure and the
corresponding physico-chemical and mechanical behaviour of common poly-
mers such as polyethylene, polypropylene, polytetrafluoroethylene, etc., in
their ideally perfect or defect-containing structures. The energies necessary
for generating conformational defects labelled as G (gauche), T (trans) and
of their combinations (GG, GTG, GTG , GGTGG, etc.) have been evalu-
ated, and physical tools to detect them in the various polymers have been
developed. In a similar way, chemical defects as well as stereochemical defects
have been treated. From the viewpoint of molecular and lattice dynamics of
polymers as 1D systems, a considerable effort has been made to offer vi-
brational spectroscopies (infrared and Raman) as useful tools for identifying
such defects in real polymeric materials [81, 82]. Necessarily in disordered
lattices of any dimension, the overall symmetry of the system is lost, group
theory becomes useless, phonons become very perturbed and all vibrational
transitions may become spectroscopically active. The concept of vibrational
density of states g(ω) for a disordered system becomes then essential, and nu-
merical tools were developed for the calculation of the vibrational eigenvalues
of extremely large dynamical matrices [82, 83].
As shown in Sect. 2.1, for Csp3 systems intramolecular interactions are
very localized and die off as soon as the second neighbour. This situation
makes the calculation of 1D systems with defects much simpler and faster,
34 Giuseppe Zerbi et al.

since the dynamical matrices turn out to be practically band matrices with
a very few codiagonals. One can then afford huge calculations in reasonably
short computer times [84]. We remind the reader that the comparison of
the calculated g(ω) with the experimental spectrum suffers of an extremely
relevant limitation, namely g(ω) is not transition-moment-weighted in the
infrared or in the Raman, and we have no ground to predict whether a given
strong singularity or a weak feature in the calculated g(ω) may give rise
to a strong or weak transition in the vibrational spectra. Correlations with
some known model molecules, with the results from ab initio calculations
and with the studies on infrared and Raman intensities [85, 86] on simple
systems turned out to be of help for the analysis of real systems. The dynam-
ical situations previously elaborated by solid state physics for very simple
defect-containing 3D inorganic lattices [87, 88] have been found also for or-
ganic 1D classical polymers. Depending on the atomic masses, geometry and
vibrational potentials, highly localized out-of-band or gap modes as well as
strongly collective resonance modes have been calculated and identified as
originating from defects in 1D polymers [82, 83].
From the study of localized and/or quasi-localized modes, spectroscopic
signals correlated with specific defects have been identified and widely used
in the diagnostic analysis of the conformational, chemical and stereochem-
ical disorder of a given real classical organic polymer system of industrial
relevance. The spectra of disordered 1D classical polymers have been treated
in the literature and have been used for detailed structural analysis of the
simplest polymers of industrial relevance, such as polyethylene, polytetraflu-
oroethylene and polyvinylchloride [82, 83].

3.2 Polyconjugated Polymers

The problem becomes more complex when moving to sp2 polyconjugated


systems. As discussed in Sect. 2.3, because of delocalization, interactions
extend to large intramolecular (and, who knows, intermolecular) distances.
EBLA must be considered because of the torsional flexibility of F systems,
cross links as well as Csp3 may truncate delocalization, and many other
chemical and structural impurities of unknown type may occur. It has to be
remembered that even the simplest PA in a real sample is thought (but never
unquestionably shown) to contain cross links and CH2 defects that strongly
perturb delocalization.
As to the knowledge of the interaction distance along the 1D polyconju-
gated chain, great expectations were put in first-principle calculations which
necessarily must take into account the molecular reality of the systems in
one, two and three dimensions. Affording such enormous calculations re-
quires powerful computing capabilities; on the other hand, data from sim-
plistic approaches may lead to wrong conclusions. As a simple example we
quote the problem tackled a few years ago on the effect on delocalization by a
CH2 group separating two sections of polyene chains. Old-fashioned simplified
A Spectroscopic Approach to Carbon Materials for Energy Storage 35

quantum mechanical calculations (CNDO, MNDO) have indicated that CH2


completely breaks conjugation and builds a huge barrier to the tunnelling of
π electrons through the barrier [89].
Concerning the experimental indication of long range interactions in 1D
polyconjugated systems we consider of extreme interest the experiments
on nonlinear optics of a series of polyacetylene-like chains with growing
lengths [90, 91] from which the final answer is that certainly conjugated dou-
ble bonds interact at least up to ≈ 60 neighbours [91].

3.3 2D sp2 Systems

For graphitic-like systems the issue of local and/or collective normal modes
needs to be updated. We neglect in this discussion the case of defects due
to the chemical synthesis of the material, namely chemical groups or atoms
(functional groups) dangling from the main graphitic lattice or stemming out
of the peripheral bonds. When the ideal view of an infinite graphite lattice is
abandoned and a real graphitic domain is considered, the number of atoms
at the periphery becomes sizeable, no matter of the shape of the domain.
Dynamics tells us that the normal modes at the periphery are many and
may behave like gap modes (highly localized or quasi-resonance modes) or
resonance modes (collective motions) depending on the dynamical conditions
which define the intramolecular coupling and depending on their energies
which may occur away, near or inside a phonon branch [82, 83]. The sec-
ond kind of possible defects of a lattice of graphite is the distortion of the
sp2 skeleton by some kind of strain induced during the chemical reaction.
In this case the work of imagination becomes almost free to conceive many
kinds of either small or large defects. The simplest case is consideration of
a few Csp3 atoms which necessarily generate localized or extended corruga-
tion; one can go further by introducing strained rings or even holes where
dangling bonds are lingering ready to react. Our fundamental questions are
the following:
(i) Is there any unquestionable experimental direct evidence of such corru-
gated structures?
(ii) Assuming that corrugations and wrinkles occur, where and how could
one locate their normal modes in infrared and/or Raman and/or neutron
scattering spectroscopies?
Efforts have been made to work out theoretical models [92,93,94], but match-
ing with unquestionable experimental data has yet to be found. In the opin-
ion of the writers, plenty of work still needs to be done on the dynamics
and experimental spectra of these systems in order to provide clear relation-
ships between the structures and the relative signatures in the infrared and
Raman. From the viewpoint of molecular vibrational dynamics-high-energy
local modes (such as C–H stretchings) arising as defects from boundaries or
holes, in a first approximation, can be overlooked and the attention should
36 Giuseppe Zerbi et al.

be focused on C–C stretchings, C–H in-plane bendings, CCC bendings and


CCCC out-of-plane modes (from 1600 cm−1 downward). These modes may
be generated by the defects, which are necessarily coupled to the phonons of
the main lattice, thus generating collective resonance modes.
It is obvious that in- and out-of-plane motions in harmonic approximation
for a planar graphitic-like lattice are orthogonal and no coupling takes place.
From previous experience with aromatic molecules [95, 96], we know that
when corrugating defects are introduced such separation is lost, all modes
can couple and the intensities are shared between two or among several cou-
pled modes (just as expected for resonance defect modes). Since, in absence
of chemical substitution (i.e., in absence of highly polar bonds) the vibrations
of the CC skeleton cannot generate large transition dipole moments, char-
acteristic signals in infrared are not likely to occur. On the other hand, CC
bonds are highly polarizable and their stretching may show up in the Raman
spectra as weak features. Calculations of transition moments in the infrared
and cross sections in the Raman may be the clue to locate meaningful and
characteristic vibrational transitions that may provide a partial picture of the
disorder inside the carbon systems under discussion in this Chapter. There
are no studies that have clearly shown the activation in the Raman of vibra-
tions localized on sp3 -induced corrugations. It has to be considered that in
any case the Raman spectra of defective graphite has a strong band around
1300 cm−1 , the so-called D band. The spectral region is unfortunately too
close to the usual frequencies found for the C–C stretching vibrations char-
acteristic of a sp3 carbon system. Therefore the future search for Raman
signatures of skeletal sp3 -induced corrugations in graphitic domains has nec-
essarily to take into account the fact that for visible laser excitation the
Raman cross section originating from the sp2 component overrides the Ra-
man cross section originating from any sp3 -induced corrugation. This is why
recent Raman investigations on such graphitic systems have been pursued
using UV excitations. In the following section we will focus on the D band
and its behaviour, and we will introduce a theoretical explanation of the Ra-
man signal that is based on model molecules mimicking confined sp2 regions
of graphite.

4 Edge Effects in Graphitic Domains


for Structure Diagnosis
A clean contribution to the study of carbon materials supposed to consist
of graphitic domains is given by the class of polycyclic aromatic hydrocar-
bons (PAHs) that have been recently made available from new synthetic
processes [15]. The electronic and vibrational spectra of PAH molecules with
well-defined shape (hence symmetry) and size have been studied, revealing
many interesting aspects related to the confinement of π electrons in two-di-
mensional domains with a size in the nanometer range [41]. The fundamental
A Spectroscopic Approach to Carbon Materials for Energy Storage 37

(a) (b)

Fig. 2. (a) Raman frequencies of G and D line of a microcristalline graphite sample,


as obtained with different exciting laser energies (from [44, 45]); (b) Modeling of
the Raman frequency dispersion of a disordered graphite sample, according to [13]

understanding of the resonant Raman spectroscopy of PAHs [14] opens the


way to the interpretation of the multiwavelength Raman spectra of nanostruc-
tured graphitic materials. In particular, it becomes possible to effectively use
the D band as a powerful diagnostic tool for obtaining information about
the distribution of domains in a nanostructured graphitic material. Disor-
dered and nanostructured graphite is a very wide class of materials (ranging
from annealed amorphous carbons, microcystalline graphites, graphite fibers
and whiskers, and carbons obtained from controlled pyrolysis of molecular
precursors). All these materials are characterized by the presence of a non-
negligible amount of sp2 carbons that give rise to islands that can be cor-
related (in terms of structure and also in terms of their Raman response)
to an ideally perfect crystal of graphite. Their first-order spectra show two
main signatures: first, a band located at about 1580 cm−1 , which is known
as the graphite (G) band, since it is the only feature observed in the first-
order Raman spectrum of highly ordered crystalline graphite. The second
band (D band) appears at about 1350 cm−1 and it is a characteristic feature
of disordered samples of graphite (e.g., nanocrystalline and microcrystalline
graphites) and amorphous carbon materials containing sp2 graphitic islands.
The fundamental experiments made by Pócsik et al. [44, 45] on microcrys-
talline graphites and those performed by Ferrari et al. [97, 98] on films of
amorphous carbons showed a marked resonance behavior and frequency dis-
persion of the D line when changing the energy of the exciting laser line used
in the Raman experiments. This behaviour is illustrated in Fig. 2.
The presence of the G band can be immediately related to the existence
of structures like graphite in the samples (it corresponds to the Raman active
E2g phonon at the Γ point in the first Brillouin zone of graphite). On the
other hand, the understanding of the physical mechanism lying behind the
activation of the disorder induced D band has been a matter of debate in the
38 Giuseppe Zerbi et al.

literature. An original interpretation of the origin of the D line in graphitic


materials has been proposed based on a molecular approach [99] built on the
spectroscopic data obtained from a wide series of samples of PAHs identified
as realistic models of nanosized sp2 domains in disordered carbon materials.
The correlation experimentally found between the Raman bands of
graphite and the Raman-active modes of PAHs has been confirmed and ra-
tionalized on the basis of quantum chemistry [14]. In particular, the analysis
of the theoretical results clarifies the origin of the large Raman cross section
for the few (D) bands near 1300 cm−1 observed (and calculated) for all the
PAHs examined. The relevant fact is that the existence of nonequivalent C–C
bonds in PAHs is essential for the activation of normal modes in the D-band
region. The existence of nonequivalent C–C bonds is the very consequence of
the confinement of π electrons in a domain of a few nanometers.
The extension of these fundamental findings on PAHs to nanostructured
graphite is straightforward: nanosized sp2 clusters of condensed aromatic
rings have to be associated to some equivalent PAHs characterized by a sim-
ilar structural relaxation driven by the confinement of π electrons in a finite
domain. The spectroscopic signature of this relaxation is just the appearance
of the D line in the Raman spectrum. Because of the effects of conjugation,
the optical absorption of these nanodomains (thus the resonant Raman condi-
tion) are size-dependent. In particular, a decreasing trend of the energy of the
lowest optical transition is found while increasing the size of the nanodomain
(graphite being a zero-gap material corresponding to the limiting case of infi-
nite size). On the other hand, because of the strong electron–phonon coupling
(see the Chapter by Castiglioni et al. in this book, pp. 381–402) it turns out
that also the frequency of the vibrational mode in the D-band region for
each nanodomain is size-dependent. In other words, the vibronically coupled
π → π ∗ optical excitations in graphitic nanodomains are size-dependent be-
cause of π-conjugation; this fact induces a size dependence also on the vibra-
tional frequency of the Raman-active vibrations (in the D-band region) via
a strong and vibration-selective (A phonon) electron–phonon coupling [42].
The consequence for multiwavelength resonant Raman spectroscopy of the
D band of nanostructured graphite is dramatic: For each given laser only
the nanodomains characterized by a suitable optical gap (i.e., size) are con-
tributing to the signal in the D region; moreover their vibrational frequency
for the above reasons will be size-dependent. In particular, a softening of the
D-band frequency is found for an increasing size of the nanodomains. This
explains the increase of the D-band frequency with respect to the energy of
the resonating laser line found in the experiments carried out by Pócsik et
al. [44, 45].
This kind of behaviour of the D band in the multiwavelength Raman
spectra of nanostructured graphite closely resembles the behaviour of the
ECC band in polyacetylene and related 1D polyconjugated compounds. It is
not by accident that the ECC vibration is characterized by a strong electron–
A Spectroscopic Approach to Carbon Materials for Energy Storage 39

phonon coupling that drives a gap opening through the Peierls distortion
exactly as the relaxation of the geometry of graphite along the D-band phonon
(A phonon) induces a gap opening at the K point at the border of the first
Brillouin zone [42].
The case of microcrystalline graphite could at first seem fairly different,
since no apparent presence of sp2 nanodomains can be foreseen. Recent stud-
ies carried out through STM and Raman spectroscopy [100] show that in
this case the variety of different π electron confinement situations does not
come from a plethora of nanodomains, but more precisely from the peculiar
electronic structures close to the edges of the graphitic planes. Such edge
electronic states can be mapped by STM and, thanks to ab initio calcula-
tions, they can be correlated with the frontier orbitals of model molecules
such as rylenes, whose Raman spectra show precisely the expected behavior
in a Pócsik diagram [100]. According to STM measurements, such edge states
extend for a few nanometer far from the edge and are extremely sensitive to
the topology of the edge [100].
The theoretical analysis illustrated above allows us to discuss the multi-
wavelength Raman behaviour of two pyrolyzed materials obtained in different
conditions from a molecularly well-defined precursor [9]. Figure 3 illustrates
the experimental results and the comparison with the outcome from a model
of the resonant Raman response produced by a distribution of graphitic nan-
odomains (according to the method described in [13]).
In Fig. 3a we can observe that in the case of the sample pyrolysed at
800◦ C, the frequencies of the D line undergo shifts with the energy of the
exciting laser. The observed frequencies follow the empirical law experimen-
tally determined by Pócsik et al. [44, 45]. As illustrated by the simulation
reported in Fig. 3a, it is possible to predict this behavior using as input of
the model [13] a homogeneous distribution of nanodomains ranging from very
small size (6 carbons) up to a large size (384 carbons).
A completely different behavior is experimentally found for a sample ob-
tained from the same precursor but pyrolysed at a lower temperature (600◦ C,
see Fig. 3b). In this case one does not observe frequency shifts with laser ex-
citation in the visible range. The behavior is markedly different from that of
disordered graphite, and it can be correctly predicted only if a different dis-
tribution of nanodomains is used as input in modeling the Raman response.
In particular, the observed behaviour is found when domains containing at
least 150 carbon atoms are selected in the model of the Raman response (see
Fig. 3b). Accordingly, we can conclude that this sample is structurally more
controlled and it keeps memory of the precursor molecule. This is consistent
with the milder pyrolysis conditions (600◦ C as opposed to 800◦ C).
40 Giuseppe Zerbi et al.

(a)

(b)

Fig. 3. Multiwavelength Raman spectra of a pyrolytic carbon sample obtained


from hexaphenylbenzene (HPB) pyrolysed at 800◦ C (a) and 600◦ C (b) [9]. Com-
parison with Pócsik data [44,45] and with the results from a modeling of the Raman
response according to [13]. The Raman frequencies of the D peak are reported in
a Pócsik diagram [44, 45] for the three excitations used (1.96, 2.41, 2.71 eV, corre-
sponding, respectively, to the red, green and blue spectra represented) to compare
with the dispersion of the D peak of microcrystalline graphite
A Spectroscopic Approach to Carbon Materials for Energy Storage 41

5 Approaching the Structure of Carbonaceous Materials


by Vibrational Spectroscopy: Imagination and Reality
It is well known that experimental solid state physics has tremendously con-
tributed to the development of the field of carbon-based materials by invent-
ing various techniques (e.g., arc discharge, chemical vapour deposition, laser
ablation, plasma-assisted vapour deposition, molecular beam deposition, etc.)
for the generation of clusters of carbon atoms that are then deposited onto
a surface. The physical properties of such deposits are of relevant interest in
modern technology. These pioneering works have also generated well-defined
and important molecules such as fullerene, fulleroids and nanotubes. All these
techniques are discussed in detail in specialized publications.
Our previous lengthy systematic approach towards the understanding of
the structure of disordered carbon-based materials is aimed at discovering
the structural reason why hydrogen cannot be ‘adsorbed’ in such systems.
Necessarily when a hydrogen molecule enters such complicated structures it
must find a ‘cavity’ where weak interatomic interactions favour its settling
inside the cavity itself. The description of the amorphous surrounding may
be represented by the following two extreme cases.
(i) Amorphous carbon materials with a different degree of local organiza-
tion, such as the models proposed in [101] or [102], are the results of
sophisticated large-scale atomistic simulations. The systems consist of a
large variety of structural entities that find carbon atoms bonded to each
other in various disordered and irregular geometries (quite often away
from their canonical states of hybridization). During the numerical cal-
culations the system may have reached a minimum energy structure as
a balance of all sorts of internal strains and stresses. In these models we
find a whole variety of strained small rings, cross links, curled chains of
various lengths; necessarily a random distribution of voids (or cavities) of
various sizes occurs in such materials. If this is the ‘real’ disorder of the
materials we are considering, spectroscopy can give little help in charac-
terizing the system, since all possible kinds of vibrational motions may
occur, thus generating a very broad vibrational spectrum with no partic-
ular features. Fortunately, the system may evolve locally towards islands
of more stable forms of aggregation, characterized by carbon atoms in
a given hybridization state. These can be considered as clusters of di-
amond, graphite, or segments of polyacetylene or polyyne. In this case
spectroscopic signatures should be found, and are indeed found, which
nicely correlate with the known spectroscopic behaviour of the parent
crystalline systems [103, 104, 105] as discussed in the previous pages of
this Chapter. By suitable annealing such metastable systems may evolve
towards graphitisation [97, 98].
(ii) An alternative picture is to consider a graphitic system consisting mostly
of intermingled graphitic nanodomains with holes and imperfections em-
42 Giuseppe Zerbi et al.

(I) (II) (III)

Fig. 4. Sketches of the chemical structures of HPB (I ), HBC (II ) and halogenated
HPB (III )

bedded in ‘amorphous’ surroundings. This has been the inspiring idea un-
derlying the project denominated “Molecular Approach to Carbon based
Materials for Energy Storage” – MAC-MES [8].
While materials obtained from vapour phase deposition, arc discharge,
etc., and also simply as carbon soot, etc., may possess a structure as in (i)
(which we already know does not adsorb hydrogen), systems as in (ii) were
obtained only recently and provided new spectroscopic probes for the explo-
ration of their structure and of their capability to adsorb hydrogen [7,8,9,10].
As a contribution towards a systematic understanding of the structural fea-
tures of disordered carbon-based materials, we have recently reported on
the infrared and Raman spectra of materials obtained from thermodynam-
ically controlled pyrolytic processes of model aromatic molecules suitably
selected and prepared as precursors of structurally controlled graphitic ma-
terials. Hexa-phenyl-benzene (HPB, (I) in Fig. 4) has been taken as the most
relevant precursor molecule to be pyrolyzed at various temperatures under
controlled conditions [10].
The concepts underlying our work were the following: It was previously
shown [15] that polyphenyl precursors, with appropriate topology, can be
smoothly transformed into flat polycyclic aromatic hydrocarbons by an in-
tramolecular cyclodehydrogenation. Typical is the case of HBC, which when
treated with FeCl3 , produces hexa-pery-hexabenzocoronene ((II) in Fig. 4).
It was thought that a pyrolytic treatement may cause two main processes:
(a) intramolecular dehydrogenation thus generating molecules of type II, and
(b) intermolecular dehydrogenation coupling various HBC units which could
then undergo intramolecular dehydrogenation as in (a). Suitable halogena-
tion (with halogen X, X=Cl, Br, I) in para position of each benzene ring in
HPB ((III) in Fig. 4) could favour the intermolecular linking with elimination
of the corresponding acid HX before entering the process as in (a). Pyrolysies
were carried out at 450, 500, 600 and 800◦ C for various lengths of time (from
1 to 5 days). The typical morphology of the carbonaceous graphitic material
obtained is given in Fig. 5.
A Spectroscopic Approach to Carbon Materials for Energy Storage 43

First, from the observation of dominant G and D lines in the Raman


spectra, it was verified that the systems obtained were mostly graphitic (see
Sect. 4). Then the chemical structure of the boundaries of the graphitic do-
mains obtained were studied in terms of the dynamics and spectra of the
peripheral C–H bonds, which show localized out-of-plane deformation modes
(decoupled from the skeletal modes). These modes become specific of the lo-
cal chemical structure as given in Table 2 [10]. As an example of application
of these spectroscopic correlations, we show the structural evolution of the
boundaries of the graphitic domains as revealed by the infrared spectra of
HPB heated at 450, 500 and 600◦C (Fig. 6).

Table 2. Top: description of SOLO, DUO, TRIO and QUATRO structures. Bot-
tom: patterns of absorption bands in the infrared to be associated to specific sets
of adjacent aromatic C–H groups belonging to “fused” benzene rings (frequency
ranges are given in cm−1 )

SOLO 860–910 – –
DUO 800–810 810–860 –
TRIO 750–770 770–800 800–810
QUATRO 730–750 750–770 –

A further interesting structural observation has been derived from these


studies. Let us assume that during the pyrolysis HPB molecules are not
broken up, but are only forced to ‘condense’ and/or link to each other. Ideally
we can construct two main repeating ‘motives’, which show borders we label
as ‘regular’ (reg) and ‘irregular’ (irreg, see Fig. 7). In absence of any region-
selective reactions, simple statistical reasoning shows that the growing of reg
structures becomes less and less probable favouring the formation of irreg
structures. As shown in Fig. 7, irreg clusters necessarily contain ‘holes’ where
six atoms are missing and are replaced by six hydrogens. Whenever the size of
the clusters increases, the relative population of TRIO structures decreases in
favour of SOLO and DUO. In principle, we can distinguish reg or irreg clusters
by the relative population of SOLO and DUO, namely for reg structures the
ratio (number of DUO/number of SOLO) is always one. For irreg structures
with holes, the population of SOLO is larger than the population of DUO. As
an example, we compare in Fig. 6 the infrared spectra of HPB heated for one
day at 450, 500 and 600◦ C. The SOLO and DUO bands increase relative to
44 Giuseppe Zerbi et al.

Fig. 5. SEM images of HPB-800-1d at increasing magnifications

Fig. 6. Infrared spectra of HPB pyrolysed at increasing temperatures (450, 500,


600◦ C)

the TRIO band, thus indicating that the sizes of the clusters have increased.

5.1 Carbon-Based Materials for Hydrogen Storage

The last question which needed to be answered is whether the graphitic mate-
rials suitably prepared as described previously in Sect. 5 were able to adsorb
hydrogen. Experiments were done with the usual techniques [4, 5]. In addi-
tion, a spectroscopic method based on Raman scattering was developed that
provides many interesting details on the physics of the ‘adsorption’ of hydro-
gen in these materials [7]. A special cell for Raman scattering experiments
A Spectroscopic Approach to Carbon Materials for Energy Storage 45

Fig. 7. Examples of regular and irregular structures with different relative


TRIO/SOLO/DUO weigths: (a) regular, TRIO/SOLO/DUO = 5/2/2; (b) irregu-
lar, TRIO/SOLO/DUO = 2/1/1; (c) regular, TRIO/SOLO/DUO = 5/2/2; (d) ir-
regular, TRIO/SOLO/DUO = 2/2/1

Fig. 8. Raman spectra of hydrogen adsorbed on a pyrolysed carbon (HPB-550-3d)


recorded at 40 ± 2 K at pressures ranging from 4 to 62.5 bar (from [7])
46 Giuseppe Zerbi et al.

Fig. 9. The effect of a uniform static electric field along the bond axis of the
hydrogen molecule. The field is generated by the array of point charges depicted
in the top-left panel. Comparison with the polarization effects on the bond lengh,
vibrational frequency and infrared absorption induced by the benzene molecule.
Data from [106], according to density functional calculations (B3LYP/6-311G**).
Notice that these calculations show only the softening (downshift of the vibrational
frequency) of the H–H bond induced by interactions with aromatic carbon atoms.
Actually the theory of the interaction also predicts an upward shift [7], as also
revealed experimentally in the Raman spectrum of H2 under pressure (see Fig. 8)

was designed and built; this cell is capable of operating at very low temper-
ature (40 K) and both in high vacuum or high pressure (up to 100 bars)
with relatively high resolution. We could easily record the vibrorotational
and rotational Raman spectra of hydrogen as function of temperature and
pressure in absence or in presence of carbon-based materials described in (i)
and (ii) in Sect. 5. Typical Raman spectra of hydrogen adsorbed on a pyrol-
ysed carbon are shown in Fig. 8. As discussed in [7], we do observe signatures
of interaction of hydrogen with carbon materials both in cases (i) and (ii) for
a small relative amount of the total hydrogen introduced in the cell. Clear
indications are found that no charge transfer phenomena are involved in the
interaction with the absorbing material (contrary to [3]), but only a simple
physisorption takes place; no indication of chemisorption has been noticed.
A Spectroscopic Approach to Carbon Materials for Energy Storage 47

The lesson we learned from these studies is that hydrogen does not find
the suitable energetic and sterical conditions to be squeezed into the ‘cavi-
ties’ of any carbon-based materials (so far known or tested), including carbon
nanotubes, even at low temperatures and high pressures. This information
from experiments weakens the validity of several theoretical elaborations pre-
sented in the literature. From our side, attempts at understanding such failure
consisted first in the application of classical potentials for describing the in-
teraction of H2 with carbons. It turned out that the the potential function
is extremely flat with a very shallow potential minimum, which indicates a
very weak interaction with the surrounding carbon atoms within the cavity.
Next, a quantum mechanical modelling of the interaction of the hydrogen
molecule with its surrounding has been attempted; interatomic distances, vi-
brational frequencies, infrared and Raman vibrational intensities have been
calculated for hydrogen interacting with benzene (taken as a model of aro-
matic carbons). The results from this computation have been compared with
the results obtained by acting on the hydrogen molecule with a static electric
field mimicking the interacting carbon substrate (see Fig. 9 and [106]). The
final relevant information which derives from these works is that in order to
keep hydrogen inside the cavity, a stronger interaction, which may induce
a larger dipole in the H–H bond, has to be obtained by introducing highly
polarizing atoms in the cavity. The idea was empirically conceived during the
synthetic part of the work, and precursors containing various nitrogen atoms
were prepared and then pyrolyzed [9, 10]. Unfortunately, no real positive re-
sults were obtained on these materials.
The results from these studies have suggested to set aside the idea that
carbon cages (of the average size existing in the material discussed in the
previous pages) may be able to store hydrogen. Smaller carbon cages or
new cavities with highly charged atoms (i.e., those that are strongly po-
larizing) should be conceived. Recently a whole new class of more ordered
organic/inorganic materials with tailored cages has been synthesized [107],
and the Raman spectra of deuterium adsorbed in one of these materials has
been obtained and studied [108]. It is very pleasing to realize that from an in-
terdisciplinary collaboration between chemists, physicists and spectroscopists
new routes for future studies on hydrogen storage have been indicated.

6 Conclusions
We hope the reader has developed a feeling about the complexity and the
yet unsolved problem in understanding the structural properties of the car-
bon-based materials that are now being considered as relevant for technolog-
ical applications. Basically we suggest that, so far, hydrogen cannot yet be
stored in a useful amount for automotive applications in the carbon-based
materials presently available. However, new hopes arise with new classes of
48 Giuseppe Zerbi et al.

organic/inorganic cage molecules. The problem of hydrogen storage has mo-


tivated the development and use of the physical techniques presented here,
which may find a broader application in the field of the characterization of
materials.

Acknowledgements

We acknowledge all the members of the MAC-MES consortium [8] for fruit-
ful exchange of ideas and constructive collaboration. In particular, we thank
Prof. K. Müllen and Dr. C. Mathis for their contributions in the field of
graphenes and Dr. L. Gherardi of Pirelli Labs for many discussions on
hydrogen absorption. Part of this work was supported by a grant from
MURST – Italy (FIRB project “Carbon-based micro- and nanostructures”,
RBNE019NKS) and by the MAC-MES contract (European Commission,
Fifth Framework Programme, Research Project “MAC-MES: Molecular Ap-
proach To Carbon Based Materials for Energy Storage” – G5RD-CT2001-
00571).

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Index
sp2 -bonded clusters, 38 defects, 27, 28, 33–35
density functional theory (DFT), 32
annealing, 41 diamond, 26, 41
diamond-like carbon (DLC), 25
bond length alternation (BLA), 31 dispersion
effective BLA (EBLA), 31, 34 phonon dispersion, 26

confinement, 28, 36, 38, 39 effective conjugation coordinate theory


conjugation length, 30 (ECCT), 38
effective conjugation length (ECL), electron–phonon coupling, 28, 30, 38
30
cumulene, 32 first principle calculations, 24, 28, 30,
32, 34
D band, 36–38 fullerene, 25, 41
D-band dipersion, 37
D-band, 38 G band, 37
A Spectroscopic Approach to Carbon Materials for Energy Storage 53

graphite, 28, 41 Peierls distortion, 29, 32, 39


graphite-like carbon (GLC), 25 polyacetylene (PA), 28, 29, 32, 41
graphitization, 41 polyconjugated systems, 31
polycyclic aromatic hydrocarbons
HOMO–LUMO gap, 29, 30 (PAHs), 36–38, 42
hydrogen adsorption, 42, 44, 45 polymers, 29, 30, 33, 34
hydrogen desorption, 42 polyconjugated polymers, 30, 31, 34
hydrogen storage, 44 polymethylene, 25
polyyne, 32, 33, 41
infrared (IR) spectroscopy, 24, 25,
pyrolytic carbons, 37, 42
33–36, 42

Kohn anomaly, 28, 32 quantum chemistry, 38

lattice dynamics, 24, 27, 29, 33 Raman scattering, 35


Raman cross section, 29, 36
molecular approach, 24, 29, 38 Raman intensity, 34
molecular dynamics, 24, 27, 33, 35 resonant Raman scattering, 28, 30
multiwavelength Raman spectroscopy selection rules, 28
(MWRS), 37–40 Raman spectroscopy, 24–28, 32–36, 42
nanotubes, 25, 28, 41
surface enhanced Raman spectroscopy
oligomers, 25, 27, 28, 30–32 (SERS), 32

Pócsik diagram, 37, 39, 40 valence force field, 25–27, 30


Biocompatibility, Cytotoxicity and Bioactivity
of Amorphous Carbon Films

Sandra E. Rodil1 , René Olivares2 , Higinio Arzate2 , and Stephen Muhl1


1
Instituto de Investigaciones en Materiales, Universidad Nacional Autónoma de
México, Circuito Exterior s/n, CU, MEX-04510 México D. F.
2
Facultad de Odontologı́a, Universidad Nacional Autónoma de México, Circuito
Exterior s/n, CU, MEX-04510 México D. F.
ser38@zinalco.iimatercu.unam.mx

Abstract. In this work we investigate the possibility of using an amorphous car-


bon layer as a bioactive coating that promotes bone ingrowth for medical implants
in direct contact with bone. The initial step was to confirm the tissue compatibil-
ity of the amorphous carbon coatings by studying cellular adhesion, proliferation
and viability with human osteoblasts and fibroblasts, cultured on the carbon sur-
face. To investigate the bone-bonding capabilities of the sputtered a-C coatings,
“in vitro” mineralisation studies were performed. For the biomineralisation assays,
human osteoblasts were grown on a-C samples for periods up to 14 days, leading
to the formation of mineralised structures that were morphologically and biochem-
ically investigated by the scanning electron microscope and X-ray microanalysis,
respectively.

1 Introduction

There is an increasing interest in the development of novel coatings or sur-


face modification treatments to improve the bone-bonding ability of metal
implants [1]. An essential condition for an artificial material to bond directly
to living bone is the formation of bone-like apatite on its surface. Direct bone-
implant joint formation is important since if the ingrowing bone is separated
from the implant by an intervening soft tissue layer, excessive micromove-
ments in the interface may occur. These micromovements are known to pro-
duce negative reactions such as destruction of the surface oxide layer and wear
of the implant surface, and these can be accompanied by corrosion and wear
debris accumulation, causing the subsequent failure of the implant [2]. The
parameters that are important for long-term implant life include the biocom-
patibility of the chosen implant material, the surface chemistry and physics,
the macro- and microstructure, the surgical implant procedure, the time and
mode of implant loading and the implantation bed itself. Therefore, the bio-
compatibility of an implant is only one of parameters influencing the tissue
response to an implant material; other factors must be satisfied for a device
to be suitable for implantation. Particularly, for bone ingrowth many factors
have been shown to be important: (a) mechanical factors, such as micro-
motion and loading; (b) geometrical factors: the surface of ingrowth fixation
G. Messina, S. Santangelo (Eds.): Carbon, The Future Material for Advanced Technology Ap-
plications, Topics Appl. Phys. 100, 55–75 (2006)
© Springer-Verlag Berlin Heidelberg 2006
56 Sandra E. Rodil et al.

implants must have a geometry that accommodates the bone ingrowth, and
therefore noncemented porous coated implants have been proposed where
the pore size and the interface gap play major roles; and (c) materials fac-
tors: the composition of the surface layer is a very important determining
factor [3]. Porous coatings on titanium (Ti) and cobalt–chrome (Co–Cr) al-
loys are the most commonly used materials for odontological and orthopedic
implants. However, the failure rates today demonstrate that there is still
scope for improvement [4]. Other potential implant materials include mostly
ceramics, such as, hydroxyapatite [5], tricalcium phosphate [6] and carbon-
based ceramics (pyrolitic carbon, glassy carbon) [7]. All have been shown
to be conducive to bone ingrowth (osteoinductive), but they have not been
used for load-bearing implants due to strength concerns. Here is where the
surface modification comes into play; by modifying the surface chemistry of
an implant, it is possible to retain the mechanical and geometrical conditions
needed to assure the long-term stability of the implant, together with enhanc-
ing a particular biological response such as bone ingrowth [8]. Both pyrolitic
and glassy carbon have been shown to be osteoinductive, but they are not me-
chanically stable. Therefore carbon-based coatings having graphite-like prop-
erties deposited on mechanically stable substrates are interesting systems to
evaluate for their potential to enhance bone ingrowth. Amorphous carbon
(a-C) and diamond-like carbon (DLC) films are known as bioinert materials
with no toxic reactions with living organism [9, 10]. Furthermore, the combi-
nation of high hardness, low coefficient of friction, high wear and corrosion
resistance, with the bioinert character is a good reason for selecting carbon
films as a surface finish on biomedical implants. Previous studies have shown
that these films exhibited good compatibility with different cell types, includ-
ing macrophages, fibroblasts, human myeloblasts and human embryo kidney
cells [11, 12, 13, 14, 15, 16]. They have also shown excellent haemocompati-
bility, reduced platelet adhesion, activation and aggregation, which are good
indicators of reduced thrombus formation [17, 18, 19]. Another important fac-
tor in favor of the amorphous carbon films as a biocompatible surface is that
their properties (surface energy, electrical conductivity, tribological proper-
ties, etc.) can be tailored by the deposition conditions or doping/bonding
using additional elements to induce specific biological responses [20, 21]. To-
day, two main biomedical applications of carbon-based coatings can be seen:
those of DLC in blood-contacting devices (stents and heart valves); and the
use of DLC to reduce wear in load-bearing joints. Coronary artery stents
and heart valves are affected by platelet activation due to blood contact with
the biomaterial or the release of metallic ions. This activation is an impor-
tant trigger for thrombosis. To solve this situation, the use of coatings on
metallic stents and heart valves has been suggested. Of these coatings, car-
bon coating is the most frequently used. In vitro studies [22, 23] have shown
that DLC significantly reduces the release of metal ions and diminishes the
platelet activation, therefore lower rates of acute and subacute thrombosis
Biocompatibility, Cytotoxicity and Bioactivity 57

are expected. Although, recent clinical trials showed no statistical differences


between metal bare and coated stents [24, 25, 26]. While, for coated heart
valves, clinical trials have demonstrated that the most bio-haemocompatible
material is pyrolitic carbon, either as a solid or a coating [27, 28]. On the
other hand, the use of diamond-like carbon for orthopedic implants has been
motivated by the low coefficient of friction, high wear resistance and hardness
of the films. These properties are needed to improve the lifetime of total hip
or knee replacements. The standard design of a hip replacement comprises a
metal or sometimes a ceramic head running against an ultra-high-weight poly-
ethylene acetabular cup. This can last for up to 15 years, which is not enough
for young, active patients, and moreover, early failures are usually reported.
The failure is mainly a consequence of generation of polyethylene wear debris
resulting from the relative movement of the femoral head and the acetabular
cup. Thus, coatings to prevent such wear have been suggested and DLC is one
of the potential candidates [29, 30]. Minor applications of carbon films in the
biomedical field include coating of polymer-based medical products, such as
catheters, drainage tubes or polymer contact lenses [31]. Not much research
has focused on studying the bone-related cell responses of amorphous carbon
films. The studies of the bone-forming activity have been performed on cell
populations extracted from bone tissue: osteoblasts. Du et al. [32] studied
the morphological behavior of osteoblast on DLC and amorphous carbon ni-
tride deposited on silicon substrates, showing that cells were able to attach,
spread and proliferate on the surfaces without apparent impairment of cell
physiology. However, the ability of carbon surfaces to promote bone growth
or biomineralization has not been studied. The formation and maintenance of
viable bone in close proximity to the surface of biomaterials are essential for
the stability and clinical success of noncemented orthopedic/dental implants.
The osteoblast is the cell type responsible for the deposition of bone within
the interfacial zone between the implant and host tissue. A better knowledge
of the osteoblasts’ function could enhance current understanding of the cellu-
lar/molecular events that occur at the tissue–implant interface, and with this
information one could produce biomaterials engineered to elicit specific re-
sponses, such as enhanced osteoblastic mineral deposition. The bone-forming
activity of osteoblasts entails an initial phase of attachment, proliferation, dif-
ferentiation and extracellular matrix synthesis, and a second phase of bone
matrix mineralization. Mineralization in osteoblasts, cultures in vitro can be
demonstrated in two main ways: detection of calcium and phosphate deposits
in the cell layer or detection of bone-matrix proteins that are known to regu-
late “ex novo” bone formation. For example, bone sialoprotein is specifically
expressed by osteoblasts depositing bone ex novo [33]. Osteoblasts cells are
anchorage-dependant, and their development depends strongly on the ini-
tial cellular attachment [34]. In this paper we investigate cellular adhesion
and subsequent cellular functions: proliferation and deposition of a miner-
alized matrix. The cellular adhesion and proliferation in conjunction with
58 Sandra E. Rodil et al.

viability tests constitute the best combination of cytotoxicity–biocompatibil-


ity tests, while the analysis of the production of mineralized matrix on the
implant materials represents the most appropriate bioactivity test for bone-
bonding applications. The bioactivity was monitored by direct observation
of the morphology of the deposited mineralized matrix, as well as the ex-
pression of some biochemical parameters of osteoblastic phenotypes: alkaline
phosphatase (ALP) activity and bone sialoprotein (BSP).

2 Experimental Details
Two sets of experiments were realized to evaluate the biocompatibility and
bioactivity of the a-C coatings. In the first set, we studied the cytotoxicity us-
ing 1 cm2 stainless steel (AISI316L) squares as substrates. From profilometer
measurements the surface roughness was between 0.05–0.1 µm with randomly
distributed scratches. The second set, used to evaluate the bioactivity, was of
stainless steel discs of 15 mm in diameter: the same size as that of the wells
in the culture plates. The surface of the discs was sand-blasted with SiO2
particles to obtain a uniform average roughness of 2 µm. In an earlier study
we confirmed that human osteoblast attachment on amorphous carbon films
was enhanced on substrates with an average surface roughness greater than
1 µm [35].

2.1 Film Deposition

Prior to deposition, the substrates were ultrasonically cleaned in acetone


and isopropanol for 30 min, respectively, and then air-dried. A thin layer of
titanium was deposited as an interface layer to increase the adhesion between
the amorphous carbon film and the stainless steel (SS) substrate. The Ti layer
was deposited using a pulsed magnetron sputtering system using argon as the
precursor gas and a high-purity, 99.99%, Ti target. The a-C were deposited
using a high purity hollow cathode graphite target, 7 cm2 , in a DC magnetron
sputtering system and an argon plasma. The Ti/SS substrates were initially
cleaned by an argon plasma for 10 min. The base pressure prior deposition
was less than 2 · 10−4 Pa and the carbon films were deposited at 4 Pa using
0.4 A and argon flow rate of 20 sccm for 5 min, giving a film thickness of
150 nm. For the characterization of the film properties, a-C films under the
same conditions were deposited on silicon and quartz substrates. All layers
were deposited at room temperature.

2.2 Film Characterization

The films deposited on silicon substrates were used to obtain the thickness us-
ing a DEKTAK profilometer. The optical absorption in the ultraviolet–visible
Biocompatibility, Cytotoxicity and Bioactivity 59

range was measured for the samples deposited on quartz using an UV–VIS
UNICAM spectrometer in the range 1.5–3.5 eV. Spectroscopic ellipsometry
was also used to study the optical properties and thickness of the films.
The energy range was 1.5–5 eV, and the ellipsometric parameters were ob-
tained using a Jobyn Yvon photoelastic modulated ellipsometer. The optical
constants were obtained by fitting spectroscopic ellipsometry measurements
with a two-oscillator Tauc–Lorentz model [36]. Surface composition was in-
vestigated with X-ray photoelectron spectroscopy using a Thermo Scientific
Multilab and Al Kα-radiation.

2.3 Cell Preparation

Human alveolar bone-derived cells (HABDC) were obtained by a conventional


explant technique [37]. The cells were cultured in 75 cm2 flasks in a standard
culture medium composed of: Dulbecco’s Modified Eagle’s Medium (DMEM),
supplemented with 10% fetal bovine serum (FBS) and antibiotic solution
(Streptoycin 100 mg/ml and penicillin 100 U/ml, Sigma Chem Co.). The cells
were incubated in a 100% humidified environment at 37◦ C in an atmosphere
of 95% air and 5% CO2 .

2.4 Cytotoxicity Test

The cytotoxicity was evaluated on the a-C films, the SS substrate, the Ti coat-
ing and a plastic positive control. All samples were sterilized by autoclave.
The cytotoxicity study include three different tests: adhesion after 24 h, prolif-
eration and viability up to 7 d. The HABDCs were plated at an initial density
of 1 · 104 /well and left to adhere for 3 h. After this time, 600 µl of the culture
medium were added. For the adhesion tests the cells were kept for 24 h and for
the proliferation and viability assays the cells were left in the culture plates
for 1, 3 and 7 d. The experimental and control cultures were treated every
2 d with fresh media. To determine the number of attached cells, we followed
the same procedure in each case; that is, after incubation, the unattached
cells were removed with a phosphate buffered saline solution (PBS) and the
attached cells were fixed with 3.5% paraformaldehyde. The evaluation of the
number of attached cells was performed by staining the cellular membranes
and measuring the optical density at the corresponding color. To perform the
staining, the fixed cells were incubated with 0.1% toluidine blue dye for 3 h.
The dye was extracted with sodium dodecyl sulfate (SDS) and the optical ab-
sorption measured with a microplate enzyme-linked immune assay (ELISA)
reader at 600 nm. The number of cells was then determined by correlating the
absorbance of the experimental samples with a standard correlation curve.
For the proliferation test we followed the same procedure for each incubation
time. On the other hand, for the cell viability the conversion of the yellow
dye (3-[4,5-dimethylthiazolyl-2-y]-2,5-diphenyltetrazolium bromide, MTT) to
60 Sandra E. Rodil et al.

blue formazan was used as a marker of cell viability or cell enzymatic activ-
ity (mitochondrial). The cells were plated and incubated as described above.
After each term 10 µl of MTT were added and incubated for 3 h. Then,
the supernatant was removed and 600 µl of dimethyl sulfoxide (DMSO) were
added to each well. After 60 min of slow shaking the absorbance was read at
570 nm which gives a reading directly proportional to the number of viable
cells.

2.5 Bioactivity

Evaluation of the biomineralization consisted of the morphological examina-


tion of the mineralized extracellular matrix and the evaluation of a selection
of proteins involved in the bone-formation process.

2.5.1 Morphological Assay

The samples (a-C, Ti, SS and positive control) were cultured in the same
way as for the proliferation assay until they reached confluence. Then, we
added the mineralization medium: 50 µg/ml of ascorbic acid, 10 mM of
β-glycerophosphate and 100 nM of dexamethasone. These compounds are
known to accelerate the mineralization process. The media was changed every
2 d. Biomineralization was evaluated after 7, 14 and 21 d. Following culti-
vation the samples were prepared for observation in the scanning electron
microscope (SEM) in the following way: cell cultures were fixed with 4%
formaldehyde in 0.1 M phosphate buffer solution (pH 7.3), then dehydrated
in graded ethanol and finally sputter-coated with gold. The microscope was
a CAMBRIDGE-LEICA STEREOSCANN 440 SEM.

2.5.2 Protein Synthesis

Alkaline Phosphatase Activity

In this case, the cells were incubated in the culture medium, i.e., no min-
eralization medium was added, for 3, 7 and 14 d. The alkaline phosphatase
activity was determined in cell lysates, obtained by treatment of the cultures
with 0.1 Triton X100 in PBS. The lysates were analyzed by measuring the
release of p-nitrophenol from p-nitrophenyl phosphate in an alkaline buffer
solution, and the colorimetric determination of the product (p-nitrophenol).
Alkaline phosphatase catalyzes the cleavage of a phosphate group from a va-
riety of compounds, including p-nitrophenyl phosphate, which is colorless.
However, one product, p-nitrophenol, is yellow in basic solutions. The ap-
pearance and intensity of yellow color thus indicates the degree to which the
substrate has been acted upon by the enzyme. Normalizing the results to
the time and the total protein concentration gave us information about the
Biocompatibility, Cytotoxicity and Bioactivity 61

specific activity of the ALP in each of the surfaces. The total protein con-
tent of the lysates was determined using a commercially available kit (Macro
BCA, Pierce Chemical Co.). The ALP activity is reported as nanomoles of
p-nitrophenol produced per minute normalized to the milligrams of total
protein content (nmol min−1 mg protein−1 ). The samples were produced in
triplicate and the measurements repeated at least three times, giving a total
of nine data values for each incubation period.

Western Blot Analysis of Bone Sialoprotein

Similarly, the HABDCs were plated on surfaces in triplicate at an initial den-


sity of 1 · 104 /well in a culture medium in 24-well culture plates; control cells
were cultured directly on tissue culture polystyrene. The cells were cultured
for 7 and 14 d. Western blots allowed us to determine the molecular weight of
the protein and to measure the relative amounts of the protein present in the
different samples. The proteins were separated by gel electrophoresis. The
proteins were transferred to a sheet of special blotting paper called nitrocel-
lulose. The proteins retained the same pattern of separation they had on the
gel. The blot was incubated with a generic protein (such as milk proteins)
to bind to any remaining sticky places on the nitrocellulose. An antibody
was then added to the solution which is able to bind to its specific protein.
The antibody has an enzyme (e.g., alkaline phosphatase or horseradish per-
oxidase) or dye attached to it that cannot be seen at this time. The location
of the antibody is revealed by incubating it with a colorless substrate that
the attached enzyme converts to a colored product that can be seen and
photographed. The bandwidth is proportional to the quantity of the protein,
so the analysis gives us a qualitative assessment of the protein content. The
relative level of the protein was assessed by measuring the integrated density
of all pixels in each band, excluding the local background and normalizing to
the area of the reference. The results are expressed as intensity per mm2 .

Bone Sialoprotein Inmunofluorescence

For this test, the cells were culture for 14 and 21 d in the culture medium.
After the incubation period, cells were fixed using 4% paraformaldehyde for
15 min. After washing with PBS they were processed for immunofluorescence:
cells were permeabilized with 0.5% Triton X-100 in PBS for 15 min followed
by blocking with 1% ovalbumin in PBS for 30 min. A primary monoclonal
antibody to BSP was used, followed by corresponding Alexa Fluor 488 (green
fluorescence) conjugated goat secondary antibody. The samples were exam-
ined by epifluorescence under a conventional fluorescence microscope.
62 Sandra E. Rodil et al.

Fig. 1. (a) Absorption coefficient determined by three different techniques: analy-


sis of reflectance and transmittance spectra, photothermal deflexion spectroscopy
and ellipsometry spectroscopy. (b) Refractive index and extinction coefficient as a
function of energy

3 Results
3.1 Film Properties

Because of the diversity of properties that amorphous carbon films exhibit,


it is very important to perform as complete as possible a characterization of
the type of film used. The results of this evaluation for the present study are
described below. The average surface roughness remained nearly constant at
2 µm after coating the substrate. In a previous paper, we reported the energy
loss spectra of amorphous carbon films [38] deposited by magnetron sputter-
ing and demonstrated that the films are nearly 100% sp2 bonded, although
a quantitative sp2/sp3 fraction could not be obtained since the π peak was
Biocompatibility, Cytotoxicity and Bioactivity 63

Fig. 2. Visible Raman spectra. Results of the decomposition using two Gaussian
peaks for G and D

too wide, indicating that more than one configuration was present and thus
impeding the area calculation [39]. It is well known that the optical and elec-
trical properties of amorphous carbon depend not only on the quantity of
sp2 bonds but also on their distribution or configuration. The optical mea-
surements showed that the films were highly absorbing for energies above
1 eV, having a Tauc optical gap of about 1 eV. The absorption coefficient
as a function of the energy, as determined by three independent techniques,
is shown in Fig. 1a. The E04 falls below the measured range, and therefore
we only report the√Tauc gap that results from an extrapolation to zero of
the line fitting the α × energy vs. energy spectra in the high energy range.
Typical data of the refractive index and extinction coefficient are shown in
Fig. 1b. The existence of the small gap is in agreement with a small degree of
clustering of the sp2 phase detected by the analysis of the Raman spectrum,
shown in Fig. 2 together with the results of the decomposition of the Raman
spectra into two Gaussians: D and G peaks. The XPS analysis demonstrated
that the surface composition consisted predominantly of carbon, and oxygen
as a surface contaminant (Fig. 3). We checked for the presence of metal atoms
from the substrate or the Ti coating but no signal was found, indicating that
the a-C film completely and uniformly covers the substrate.
According to this characterization we can conclude that the films were uni-
formly deposited on the rough stainless steel substrates, copying the surface
topography. The physical and structural properties, optical gap, refractive
index and bonding characteristics of the films suggest that the films used for
this investigation are graphite-like amorphous carbon films.
64 Sandra E. Rodil et al.

Fig. 3. XPS spectra of the sample, general view

3.2 Cytotoxicity

In vitro methods provide a necessary and useful adjunct to “in vivo” studies
for selecting materials as candidates for implants or biomaterials. This study
includes two stages; the first, cytotoxicity tests, is carried out to detect any
toxic effects of the potential materials. The second stage allows a more thor-
ough evaluation of the biocompatibility of the material in relation to its end
use, in our case the biomineralization tests. The cytotoxicity of amorphous
carbon films has been tested with different cell lines, and in general it is cat-
alogued as a biocompatible material. However, considering the differences in
film properties and the importance to test the material using cells specific
for the proposed application of the medical device, we decided to evaluate
the cytotoxicity using primary human osteoblasts on the sputtered a-C films.
Toxicity in vitro is a negative or deleterious effect that induces changes in the
cellular response, such as cell death, reduced cell adhesion and proliferation,
altered cellular morphology, and inhibition of biosynthetic functions. All of
these processes were evaluated. Cell death was not observed during the pe-
riod of evaluation up to 7 d. The cellular adhesion, on the other hand, which
is very important for this specific type of cells, was actually improved by the
films in comparison to either the stainless steel substrate, the Ti coating and
the positive control. This is observed in Fig. 4, in which we plot the number
of attached cells after 24 h on each surface. The a-C had the highest number
of attached cells compared to all other materials (ANOVA p < 0.05). Cell
proliferation was evaluated for periods up to 7 d. Figure 5 shows that the
number of cells increased as a function of the incubation time for all sur-
faces. The number of cells on the a-C films doubled at three d of incubation,
while the doubling time for the Ti films was about 7 d. On the stainless
steel the number of cells remained constant at about 1.2 · 104 even after 7 d.
Biocompatibility, Cytotoxicity and Bioactivity 65

These results were further confirmed by the cell viability assay (MTT test),
which is very important since the combined proliferation/metabolic test is a
way of providing information about the cell growth and metabolic activity
of the cells. The results of the MTT assay (Fig. 6) are presented as the opti-
cal absorbance at 570 nm. We found high levels of MTT conversion (higher
absorbance, high metabolic activity), compare to the control, for Ti and a-
C films, and this increased with time. This increment reflects the increased
number of cells on the surfaces and therefore confirms that there are a greater
number of both dividing and metabolically active cells. In accordance to the
lower proliferation rate measured for the SS substrate, the enzymatic activity
of the osteoblasts cells on SS is lower. Finally, scanning electron microscopy
allowed the observation of the cell morphology. Osteoblasts with dorsal ruf-
fles close to each other connected by filopodia, attached and spread on the
substrate were observed during the different incubation times (not shown).
The results of the cytotoxicity tests suggested that the amorphous carbon
and titanium coatings have no negative affect on cell adhesion, viability and
proliferation. The cell number and absorbance values obtained for a-C and Ti
resulted significantly higher with respect to the positive control and the SS
substrate, indicating the absence of toxic effects. Morphologically, the cells
were in good condition and well attached to the surfaces.

3.3 Bioactivity
3.3.1 Morphological Analysis
Secondary electron image examination at 14 and 21 d of cultured osteoblasts
on the surfaces revealed a continuous cell multilayer and an extracellular
matrix that completely covered the surface. Figure 7 shows the images at
different magnifications for the a-C surfaces at 14 and 21 d. Figure 8 shows
corresponding images for SS and Ti coatings. The extracellular matrix was
composed of both noncollagenous and collagenous components, with small
(< 1µm) spherical structures or mineral deposits. These mineral deposits
were seen interspersed among the osteoblast cell layer or within the fibrillar
matrix. The images are similar to those reported in other works [40, 41, 42],
although the incubation periods used in our work are relatively shorter. By
comparing Figs. 7 and 8 we can observe that similar results were obtained
for the SS substrate, a-C and Ti coatings. Therefore, by simple morpholog-
ical analysis of the mineralization process it is impossible to determine any
substrate-dependent effect, emphasizing the importance of making quantita-
tive measurements, such as those obtained by the analysis of specific proteins.

3.3.2 Proteins
Chemical reactions in living organisms occur rapidly at moderate tempera-
tures and under mild conditions primarily because of the catalytic action of
66 Sandra E. Rodil et al.

Fig. 4. Number of attached cells after 24 h of incubation for the SS substrate, a-C
and Ti coatings and the plastic culture dish

a-C
24000
SS
Ti
Control
Number of Cells

20000

16000

12000

8000
0 1 2 3 4 5 6 7
Days
Fig. 5. Osteoblast proliferation for 1, 3 and 7 d of incubation. The initial plated
cells was 1 · 104 per surface

specialized proteins called enzymes. Each step in the chain of a biochemical


reaction is usually catalyzed by a specific enzyme. A large number of proteins
are involved in preparing the matrix for mineralization: phosphatases that
regulate extracellular phosphate concentrations, kinases that regulate matrix
protein phosphorylation and metalloproteinases that degrade the extracellu-
lar matrix. In order to mineralize, osteoblasts express these compounds into
the extracellular matrix, specifically alkaline phosphatase, bone sialoprotein,
osteocalcin and osteopontin. The rate of an enzyme-catalyzed reaction may
be measured by (a) the disappearance of substrate, which is the substance
acted upon by the enzyme and changed to the product, or (b) the appear-
Biocompatibility, Cytotoxicity and Bioactivity 67
2.0
a-C
1.8 SS
Ti
Absorbance at 570 nm

1.6 Control

1.4

1.2

1.0

0.8

0.6
3 4 5 6 7
Days
Fig. 6. Cell viability (MTT test) expressed as the absorbance at 570 nm

ance of the product. The ALP activity was measured by the product quan-
tity as described above. The levels of this enzyme in the various surfaces
are shown in Fig. 9, as a function of the incubation time. ALP plays a vital
but yet undefined role in bone mineralization. It is thought to regulate phos-
phate transport. The enzyme is glycosylated and attached to the cytoplasmic
membrane on its external surface, where it interacts with extracellular ma-
trix proteins. The results showed that all the cultures presented a significant
induction of the ALP activity, which is in some way expected since we use os-
teoblasts, which produce high ALP concentrations. However, the activity was
significantly higher for the amorphous carbon coatings compared to the other
surfaces (ANOVA p < 0.05). An increase in the activity and expression of
ALP is a strong marker of both the osteoblast phenotype and mineralization.
The other bone-related protein investigated in this work was bone sialo-
protein (BSP), a phosphorylated glycoprotein. BSP is a major structural pro-
tein of the bone matrix that is specifically expressed by fully differentiated
osteoblasts. The expression of BSP is normally restricted to mineralized con-
nective tissue of bones and teeth, where it has been associated with mineral
crystal formation and is considered a potent nucleator of hydroxyapatite.
Western blot analysis was performed to determine the expression of bone
sialoprotein on the surfaces. Semiquantitative information about the level
of BSP expression was obtained by densitometric studies, and both images
are shown in Fig. 10. BSP was expressed on all surfaces after 7 and 14 d
of culture. For a-C, SS and Ti we observed a progressive increase in BSP
expression with time, while in the tissue plastic control, the level decreased.
Remarkably, the level of BSP expression was much higher on a-C than in any
other surface.
Because of the difficulty in analyzing the samples to obtain the compo-
sition of the mineralized matrix, particularly of the small spherical nodules,
68 Sandra E. Rodil et al.

Fig. 7. SEM images of the mineralized matrix in the amorphous carbon surfaces
after A, B 14 d. C and D 21 d. Bar: A 2µm, B 10µm, C 2µm, D 30µm
Biocompatibility, Cytotoxicity and Bioactivity 69

Fig. 8. SEM images of the mineralized matrix in the SS substrate after A 14 d, B


21 d. SEM images of the mineralized matrix in the Ti coatings after C 14 d and D
21 d. Bar: A, 10 µm; B, 2 µm; C, 30 µm; D, 2 µm
70 Sandra E. Rodil et al.

Fig. 9. Alkaline phosphatase (ALP) activity

Fig. 10. Western blot analysis of bone sialoprotein (top) and densitometric analysis
of the bands, showing the intensity per µm2 (bottom)
Biocompatibility, Cytotoxicity and Bioactivity 71

we determined the distribution of bone sialoprotein on the surfaces by im-


munofluorescence labeling. This technique allowed us to confirm that the
small nodules shown in the SEM images corresponded to mineral deposits
containing high concentrations of BSP. Figure 11 shows the different images
of the BSP distribution on the a-C coating, and similar images were obtained
for the other surfaces (not shown). An important proportion of the cells were
immunoreactive to BSP for all the time periods (14 and 21 d). BSP was
present in both the cell layer and the extracellular matrix. Active osteoblasts
contain BSP in a large juxtanuclear mass reminescent of the Golgi region, so
the underlying cellular layer was clearly seen. However, fluorescence intensity
was stronger in the spherical nodules that appeared at 14 d of incubation
and grew into big mineral deposits, forming large mineralized layers, as those
observed in Figs. 9d and 7a by SEM.

4 Discussion
The present study describes an in vitro model to study the response of human
osteoblasts to well-characterized a-C coatings in comparison with titanium
coatings and the stainless steel substrates. We performed both short- and
medium-term studies to determine the cytotoxicity and the biomineraliza-
tion of the different surfaces. We observed an enhanced cellular adhesion and
proliferation/viability on the a-C coatings, demonstrating the biocompatibil-
ity of the material. Moreover, we demonstrated the formation of a calcified
matrix with bone sialoprotein and alkaline phosphatase being expressed.
By comparison between the different surfaces, we showed that osteoblast
cells respond differently to biomaterial in both short- and medium-term cul-
tures. The SEM examination of the osteoblast cultures in the presence of
β-glycerophosphate, dexamethasone and ascorbate revealed the formation of
a stratified matrix mixed with cell layers and the mineralized nodules. The
ALP activity and Western blot were performed to determine the time de-
velopment and levels of two important proteins, ALP and BSP, associated
with the mineralization process. Our results showed different responses to the
biomaterial, and in both cases the amount of protein expressed on the a-C
surfaces was larger, suggesting that the film properties promote the differen-
tiation and mineralization of human osteoblast.
A good correlation between proliferation and mineralization results was
obtained. It is well established that proliferation stops when the mineraliza-
tion process is initiated [43] and that mineralization initiates once the cells
have formed a certain amount of extracellular matrix. This is clearly reflected
in our results. Figure 4 shows that cell proliferation attained a saturation level
at about 7 d, after which the ALP activity increased dramatically (Fig. 9).
This was important to establish the moment at which the mineralization
medium should be added to the culture, since once the culture medium is
72 Sandra E. Rodil et al.

Fig. 11. Distribution of the bone sialoprotein on the amorphous carbon surfaces
after A, B 14 d. C, D 14 d. A, C and B 10X; D 20X
Biocompatibility, Cytotoxicity and Bioactivity 73

rich in phosphate ions, mineralization will occur, but without the appropri-
ate matrix, the mineralization obtained is dystrophic and does not necessarily
resemble the bone formation in vivo.
Human osteoblast cultures may be regarded as a potential in vitro model
to study biomaterial/bone tissue interactions. However, in order to deter-
mine the differences between biomaterial-induced responses, morphological
analysis of the cell layers grown on the surface is not sufficient. If possible,
structural characterization of the mineral deposits must be performed, but
standard immunofluorescence or staining techniques are more appropriate to
quantitatively compare the response of the osteogenic cells to the different
materials.
In conclusion, we have shown that graphite-like amorphous carbon is a
potential candidate for further research as a bioactive coating to induce bone
formation. Many issues must still be investigated, for example, film proper-
ties, and more important, film–substrate adhesion must be improve to the
point that no failure is possible in long-term applications. Mechanical tests
associated with the torque resistance that the coating should support during
the insertion of the implant into the bone must be performed. Similarly, other
biological tests, such as genotoxicity and in vitro bone growth, need to be
carried out.

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Index
a-C, 55 G band, 63
sp3 /sp2 bonding ratio, 62
haemocompatibility, 56, 57
alkaline phosphatase (ALP), 58–61, 66, hardness, 56, 57
67, 70, 71
mineralization, 57, 60, 64–67, 71
bioactivity, 55, 58, 60, 65, 73 MTT test, 65, 67
biocompatibility, 55–58, 64, 71
biomaterials, 57, 64, 73 optical properties, 59
biomedical implants, 55–57, 64, 73
bone sialoprotein (BSP), 57, 58, 61, 66, proliferation, 57, 59, 64, 65, 71
67, 70–72
Raman spectroscopy, 63
coatings, 56–58, 67, 71–73
refractive index, 63
bioactive coatings, 55
biomedical coatings, 57
scanning electron microscopy (SEM),
cytotoxicity, 58, 59, 64, 65, 71
60, 65, 68, 69, 71
D band, 63
diamond-like carbon (DLC), 56, 57 tribological properties, 56

electrical properties, 63 viability, 58, 59, 65, 71

friction coefficient, 56, 57 wear resistance, 56, 57


Characterisation of the Growth Mechanism
during PECVD of Multiwalled Carbon
Nanotubes

Martin S. Bell1 , Rodrigo G. Lacerda2, Kenneth B.K. Teo1 , and


William I. Milne1
1
Engineering Department, University of Cambridge, Cambridge CB2 1PZ, UK
msb39@eng.cam.ac.uk
2
Universidade Federal de Minas Gerais, Departamento de Fı́sica, BR-30123-970
Belo Horizonte, MG, Brasil

Abstract. The growth mechanism of multiwalled carbon nanotubes has been a


subject of considerable research interest. Published results show that nanotubes
may be formed by a variety of methods using different combinations of carbon-
rich gases and etchant gases. We present an overview of different forms of carbon,
showing how nanotubes relate to other carbon structures and how they may be
produced. The use of plasma-enhanced chemical vapour deposition (PECVD) for
growing vertically aligned nanotubes for electronic device applications is reported,
including an analysis of the species present in the plasma during PECVD. It is
shown that the presence of a reactive species such as ammonia suppresses decom-
position of carbon feedstock gas and favours the formation of carbon nanotubes. It
is further shown that gas-phase reactions remove excess carbon, allowing the pro-
duction of nanotubes without unwanted amorphous carbon deposits, which is es-
sential for electronic applications. Plasma analysis is used to determine an optimum
carbon-source to etchant gas ratio, which is verified by postdeposition analysis.

1 Introduction
Carbon is a fascinating material due to the ability of carbon atoms to bond
with each other in different ways, giving rise to materials as varied as dia-
mond and graphite. Carbon has six electrons, arranged as (1s)2 (2s)2 (2p)2 .
It forms covalent bonds with other carbon atoms, using the outer four elec-
trons. To form these bonds, one of the 2s electrons is promoted to a 2p level.
The hybridisation of these electron orbitals allows carbon to form different
structures.
In diamond, sp3 hybridisation produces four identical and very strong
bonds. Each atom bonds to four others, giving rise to a tetrahedral structure,
symmetric in three dimensions.
In graphite, the remaining 2s electron hybridises with two of the 2p elec-
trons, giving three sp2 orbitals, which are located in an (x, y) plane, separated
by 120◦ . The remaining 2p electron orbital is perpendicular to this plane,
hence it is known as a pz orbital. The sp2 orbitals form strong σ-bonds be-

G. Messina, S. Santangelo (Eds.): Carbon, The Future Material for Advanced Technology Ap-
plications, Topics Appl. Phys. 100, 77–93 (2006)
© Springer-Verlag Berlin Heidelberg 2006
78 Martin S. Bell et al.

A
B
Fig. 1. AB stacking in graphite

Fig. 2. C60 molecule

tween the carbon atoms in the plane. Graphite consists of a series of these
parallel “graphene” planes.
The pz (or π) orbital perpendicular to the plane provides a weak van der
Waals bond that binds the planes together. The weakness of these π-bonds
allows the graphene planes to be easily separated. In high-quality “Bernal”
graphite, the graphene sheets are stacked ABAB. . . (Fig. 1).
These graphene sheets have an interlayer spacing of approximately
0.334 nm. The presence of defects in the graphene sheets gives rise to a larger
interlayer spacing (≈ 0.35 nm), and to a random rotation of the graphene
layers with respect to one another. This less-crystalline form is known as
turbostratic graphite.
A third structure observed in carbon is C60 , also known as “buckmin-
sterfullerene” after the architect Buckminster Fuller, who is famous for his
geodesic dome designs. The C60 molecule is an icosahedral structure made
up of 20 hexagons and 12 pentagons (Fig. 2). Each carbon atom is joined to
Growth Mechanism During PECVD of Multiwalled Carbon Nanotubes 79

a2
a1

Fig. 3. Unit vectors in the graphene plane

three others, so it is predominantly σ-bonded, like graphite. There are similar


molecules containing more carbon atoms (e.g., C70 ).
The discovery of C60 in 1985 [1] may be identified as the first key step
along the path which led to the synthesis of carbon nanotubes. Carbon nano-
tubes themselves were identified in 1991 [2].
A single-walled nanotube is simply a graphene sheet rolled up into a
cylinder. The dangling bonds at the extremities of the sheet join together,
completing the cylinder. The size of the nanotube and its electrical properties
are determined by the “chiral vector”, which links the two points in the
graphene sheet that join up to complete the nanotube. The chiral vector is
defined as c = ma1 + na2 , where a1 and a2 are the unit vectors in the
graphene plane (Fig. 3).
The nanotube, of course, requires not just sides but a cap at the end
to eliminate the dangling bonds. The cap is an icosahedral structure made
up of pentagons and hexagons, like a C60 molecule. A nanotube is classified
according to its chiral vector, and referred to as an (m, n) tube. There are
two special cases that exhibit particularly high symmetry. These are known
as “armchair” and “zig-zag” nanotubes. For an armchair nanotube, n = m,
whilst for a zig-zag tube, n = 0. In these cases, the chiral vector is perpen-
dicular to the nanotube axis (Fig. 4). For the two specific nanotubes shown,
the cap in each case is half of a C60 molecule.
More generally, if n = 0, and n = m, a “chiral” nanotube is formed, where
the hexagons are arranged helically around the nanotube. Single-walled nano-
tubes typically have diameters in the range 1–5 nm. They may be metallic
(0 eV band gap) or semiconducting (typically 0.4–0.7 eV band gap) depend-
ing upon the chiral vector. The band gap is also inversely proportional to the
diameter [3, 4, 5].
A multiwalled nanotube consists, in essence, of a series of concentric single
walled nanotubes. As discussed above, the interlayer spacing in well-ordered
ABAB graphite is 0.334 nm. For the ABAB structure to be replicated in a
multiwalled nanotube would require successive nanotube circumferences to
80 Martin S. Bell et al.

Fig. 4. “Armchair (5,5)” and “zig-zag (9,0)” nanotubes (top and bottom, respec-
tively)

differ by an integer multiple of (2π × 0.334 nm), as well as requiring well-


ordered individual nanotubes.
Measurements have shown that the intershell spacing in multiwalled nano-
tubes can range from 0.34 to 0.39 nm, with the spacing decreasing as nano-
tube diameter increases [3, 6]. The geometrical constraints in forming the
seamless graphene cylinders cause the layers to be uncorrelated with respect
to one another. Multiwalled nanotubes therefore resemble the less-ordered
turbostratic form of graphite rather than the higher-quality Bernal form.
Multiwalled nanotubes typically have outer diameters in the range 50–
100 nm. Electrical conduction can take place within each of the individual
shells of a multiwalled nanotube. However, if a multiwalled nanotube is con-
tacted on the outside, the electric current is conducted through its outermost
shell only [7]. Where conduction occurs through this outer shell, the band
gap approaches 0 eV due to the relatively large diameter and the nanotube
acts as a metallic conductor.
Before we go any further, it is worth mentioning a related structure,
namely carbon nanofibres. Carbon nanofibres are another kind of graphitic fil-
ament, which differ from nanotubes in the orientation of the graphene planes.
The graphene planes in a carbon nanotube are parallel to the nanotube axis;
in a nanofibre, the graphene layers are not parallel to the axis, but are rather
arranged in a stacked form (layers perpendicular to the fibre axis) or herring-
bone form (layers at an angle to the axis). These nanofibres are illustrated
in Fig. 5, with the nanofibre axis indicated by an arrow in each case.
Nanofibres have many useful properties in common with carbon nano-
tubes and share some potential applications. They do not, however, share all
of the beneficial properties of nanotubes that derive from their structure.
When carbon nanotubes were discovered, it was realised that because
the graphene planes are parallel to the filament axis, they would inherit
Growth Mechanism During PECVD of Multiwalled Carbon Nanotubes 81

Fig. 5. “Stacked” and “herringbone” nanofibres (top and bottom, respectively)

several important properties of graphite. In particular, a nanotube exhibits


high electrical conductivity, thermal conductivity and mechanical strength
along its axis. As there are very few open edges and dangling bonds in the
structure, nanotubes are also very inert, and species tend to be physically
adsorbed onto the graphene walls rather than react with them. As carbon
nanotubes are completely covalently bonded, they can be excellent electrical
conductors which do not suffer from electromigration, a limiting factor for
metals.
Carbon nanotubes have been investigated for a wide range of applications.
A nanotube can behave as a high-aspect-ratio electrical conductor with mi-
cron-scale length and nanometre-scale diameter. Structures of this type are
highly desirable as field emission tips for applications such as field emission
displays [8, 9], X-ray tubes [10], electron sources for microscopy and lithogra-
phy [11], gas discharge tubes [12] and vacuum microwave amplifiers. The high
aspect ratio and small diameter of the nanotube is also useful for scanning
probe tips [13, 14].
Semiconducting single-wall carbon nanotubes have been investigated for
use as transistors or logic elements [15, 16]. The electronic properties of the
carbon nanotubes are highly sensitive to adsorbed species [17, 18], which is a
challenge for logic circuits, requiring the nanotubes to be suitably encapsu-
lated. However, this sensitivity may be utilized in chemical or biological sen-
sors for gas detection. The coherent nature of electron transport in crystalline
nanotubes makes these structures potentially suitable for spin-electronic de-
vices [19].
Carbon nanotubes may also be used as electromechanical sensors as their
electrical characteristics change in response to mechanical deformation of
their structure [20]. Conversely, nanotubes can mechanically deflect under
electric stimulation (e.g., due to charge induced on the nanotubes) making
them useful as cantilevers or actuators [21, 22].
Aside from applications which exploit the properties of individual nano-
tubes, there are a further range of applications which utilise the large surface
82 Martin S. Bell et al.

area to volume ratio of carbon nanotubes and nanofibres when manufactured


in bulk. One interesting application for these structures is as electrodes in
electrochemical supercapacitors [23, 24]. It has been shown that such struc-
tures could lead to higher charge storage than conventional capacitors and
batteries [21, 25]. The high electrical conductivity and relative inertness of
nanotubes also make them potentially useful as electrodes in electrochemical
reactions [26, 27]. Nanotubes can support reactant particles in catalytic con-
version reactions [28, 29]. It has been proposed that hydrogen could be stored
amongst and inside nanotubes/nanofibres for fuel cell applications [29, 30],
although results show that the amount of hydrogen stored is not as high as
originally anticipated [31]. The use of nanotubes and nanofibres as filters or
membranes for molecular transport has also been proposed [32].
Nanotubes and nanofibres can be added to polymers to improve their
strength and stiffness, and can also add electrical conductivity to polymer-
based composite systems [33, 34], which has proved useful in the automobile
industry for the electrostatic painting of components. Carbon nanotubes are
ideal reinforcing fibres for composites due to their high aspect ratio and
axial strength [35]. Single-wall carbon nanotubes are preferred to multiwall
nanotubes because the inner layers of the multiwall nanotubes contribute
little under structural loading, and thus would reduce the stiffness for a given
volume of nanotubes [35, 36].

2 Production of Carbon Nanotubes


There are a number of known methods for producing carbon nanotubes.
Between them it is possible to produce nanotubes with differing properties
and in different forms. The most common methods used for the production
of nanotubes are arc discharge [37, 38], laser vaporisation [39] and chemical
vapour deposition.
The first nanotubes were produced in an arc discharge arrangement [2].
In a typical arc discharge apparatus, two graphite electrodes are held a short
distance apart inside a vacuum chamber. The chamber is held at high vac-
uum and a flow of helium is supplied. A DC voltage is applied across the two
electrodes, and a large arc current flows, removing carbon atoms from the
anode in the process. The position of the anode is adjustable so that as the
anode is consumed, the gap between the two electrodes can be held constant.
A carbon deposit forms on the cathode; this deposit contains nanotubes as
well as larger carbon nanoparticles. In a high-quality arc discharge, the de-
posit can contain 70% nanotubes. These nanotubes typically exhibit a good
crystalline structure and are very straight, due to the very high temperatures
(3000◦ C) developed during the arc discharge. However, in order to make use
of these nanotubes in an electronic device, they must be separated from the
cathode, purified and manipulated onto a substrate.
Growth Mechanism During PECVD of Multiwalled Carbon Nanotubes 83

Like arc discharge, laser vaporisation is a short-duration, high-temper-


ature technique for nanotube production. A graphite target is heated to
around 1200◦C in a horizontal furnace whilst an inert gas flows across it.
A high-power laser is then used to vaporise the graphite target. The vapor-
ised material is carried by the gas onto a cooled collector, where it condenses.
As with arc discharge, the material contains a mixture of nanotubes and
nanoparticles, and once again the material must be separated, purified and
manipulated in order to fabricate devices. Laser vaporisation can produce
up to 90% nanotubes, however, unlike arc discharge, its use is limited to
small-scale production.
In both of these cases, a block of solid graphitic carbon is heated to
a very high temperature and carbon atoms are separated from the block,
reassembling either on the cathode in the case of arc discharge or on a cooled
collector in the case of laser vaporisation. It is during this reassembly that
the highly ordered nanotubes are formed.
Catalytic chemical vapour deposition is very different. Instead of begin-
ning with a block of carbon, the feedstock is a hydrocarbon gas, which dissoci-
ates either thermally (thermal CVD) or in the presence of a plasma (plasma-
enhanced CVD). Once again, the dissociated carbon atoms self-assemble into
highly ordered nanotubes; however, in this case the nanotubes form on a
substrate, which may be made of any material which can withstand the de-
position temperature (e.g., silicon or glass). The self-assembly is facilitated
by catalyst nanoparticles deposited on the substrate surface, which seed the
nanotube growth. These catalyst nanoparticles determine both the location
and diameter of the nanotubes formed. This ability to deposit nanotubes
selectively based upon the location of catalyst particles opens the door to
lithography and a range of possibilities for direct deposition of nanotube de-
vices.
Thermal CVD requires high temperatures (800–1000◦C) and has two dis-
advantages. First, the nanotubes produced are not just randomly oriented,
but also they are not straight. Second, the high temperature rules out the
use of many desirable substrate materials (e.g., glass).
Plasma-enhanced CVD (‘PECVD’) is a technique used extensively in the
semiconductor industry to allow CVD at lower temperatures. In this case, en-
ergy in the plasma replaces some of the heat energy, allowing gas dissociation
and nanotube formation to take place at lower temperatures (600–700◦C).
PECVD has a further advantage: the electric field aligns the nanotubes dur-
ing growth [40, 41]. There are a number of different techniques available for
creating the plasma. These include rf-PECVD [42], microwave PECVD [43],
inductively coupled PECVD [26] and DC glow discharge PECVD [44].
For an electronic device, it is essential to be able to make good electrical
contact to the nanotubes. Silicon is often selected as an appropriate substrate.
Also, for an electronic device, it is important that the synthesis of nanotubes
is performed without the deposition of amorphous carbon (“a-C”), which
84 Martin S. Bell et al.

prevents the formation of nanotubes by poisoning the growth catalyst and


can cause short circuits on the substrate surface. One method that has been
shown to prevent the deposition of a-C is to combine the carbon source (a
hydrocarbon gas) with a hydrogen-rich gas (typically NH3 or H2 ), which
produces reactive species in the plasma that remove any excess carbon.

3 Plasma Composition during PECVD


We have seen that we can form carbon nanotubes using several different
techniques. In the case of arc discharge and laser vaporisation, carbon is
liberated from a graphite source before reassembling in nanotube form. In
the case of CVD, it is not clear if carbon itself is present in the chemical
vapour, or if carbon is extracted from hydrocarbon molecules in a reaction
at the surface of the metal catalyst.
Different conditions for nanotube synthesis yield different results: Under
certain conditions we get well-defined nanotubes; at other conditions we get
amorphous carbon. What is the mechanism that determines this? In order to
answer these questions, we conducted an analysis of the plasma composition
during PECVD of carbon nanotubes [45].
Multiwalled carbon nanotubes were grown using a DC glow discharge
PECVD setup with the substrate located on a resistively heated graphite
stage. It has been reported that C2 H2 is the most efficient carbon feedstock
for the growth of carbon filaments [46], and we selected C2 H2 to be the carbon
feedstock gas for our carbon nanotube growth. NH3 was added to generate
reactive species, which have been shown to help prevent formation of a-C.
The gases were fed into the chamber through a metal pipe that acted as an
anode for the plasma discharge. A DC plasma was generated between this
pipe and the tungsten heaters within the graphite stage. The chamber was
maintained at vacuum using a rotary pump.
Si substrates coated with a thin catalyst film were placed on the graphite
stage and heated to 520◦ C in NH3 . At this temperature, the thin film cat-
alyst agglomerates into particles suitable for seeding nanotube growth. The
DC plasma was then initiated and C2 H2 added into the gas flow as the carbon
feedstock. The temperature was maintained at 650◦C throughout the deposi-
tion, and the chamber pressure was maintained at 5.3 mbar. The plasma DC
bias was maintained at 600 V, with current typically around 100 mA. The
volume flow-rate proportion of C2 H2 in the NH3 :C2 H2 plasma was varied
between 0% and 70% whilst maintaining other parameters at their standard
settings.
Mass spectrometry was performed on species extracted 15 mm from
the graphite stage. Neutral molecules were extracted from the plasma and
analysed using residual gas analysis (RGA). Positive ions were extracted and
analysed using secondary-ion mass spectrometry. An RGA mass spectrum
Growth Mechanism During PECVD of Multiwalled Carbon Nanotubes 85

Fig. 6. RGA and positive ion mass spectra (top and bottom, respectively)

for neutral species and a mass spectrum for positive ion species at 23% C2 H2
are shown in Fig. 6.
The species in the RGA spectrum are consistent with the cracking pat-
terns of C2 H2 (base peak at amu 26) and NH3 (base peak at 17 amu) and also
indicate the presence of H2 , HCN, H2 O, N2 and CO2 [47]. This is consistent
with data reported by other authors [48]. The dominant ions detected were
NH+ + + + +
3 and C2 H2 . Other detected species were NH2 , NH4 , HCN and C2 H .
+

4 Characterisation of the Growth Mechanism


The results obtained by growing carbon nanotubes in this particular config-
uration have previously been reported [49]. It was demonstrated that well-
aligned nanotubes were grown for C2 H2 concentrations between 4–20%, that
at 29% C2 H2 the nanotubes became more obelisk-like, and that by 38% there
are no longer any tubes at all. These results are shown in Fig. 7. It was also
reported that the nanotube growth rate peaked at around 20% C2 H2 content.
This growth condition gave a clean, a-C-free substrate [50].
We first investigated the nature of the carbon precursor for the formation
of nanotubes. We were unable to detect C2 , CH4 or other higher carbon
species even after acquiring data for a prolonged period, and thus concluded
that C2 H2 is the dominant precursor for nanotube formation. This conclusion
is supported by other authors [51], who have detected the presence of C2 H2
86 Martin S. Bell et al.

Fig. 7. Scanning electron microscope images of carbon nanotubes grown at different


gas ratios

catalyst C xH y
particle C

C C

C C C xH y catalyst
Cx Hy
particle
barrier layer barrier layer

(a) weak interaction (b) strong interaction

Fig. 8. Growth models

in a CH4 /H2 /NH3 plasma yielding nanotubes. For this to be the case, our
growth model must include a reaction at the catalyst surface to extract carbon
from C2 H2 .
The catalyst takes the form of a transition metal (Fe, Ni, Co or Mo), which
may be applied chemically from a solution containing the catalyst [52] or
directly by using techniques such as thermal evaporation, ion beam sputter-
ing [53] or magnetron sputtering [54]. For our experiment we used magnetron
sputtering to give us a well-controlled Ni film.
When heat is applied to the substrate bearing the film, the increased sur-
face mobility of the catalyst atoms causes the film to coalesce into nanoclus-
ters [55]. The thickness of the catalyst film, temperature and time determine
the size of these nanoclusters [49, 56, 57].
There is a further consideration with respect to the catalyst layer. This
is the chemical interaction between the catalyst and substrate when heat is
applied. If there is a reaction, the catalyst material will dissipate, ending its
usefulness for seeding nanotube growth. This is a problem when using Si as
a substrate with transition metals, as they would diffuse into the substrate
Growth Mechanism During PECVD of Multiwalled Carbon Nanotubes 87

at the temperatures used. In order to eliminate this problem, a thin diffusion


barrier of SiO2 was sputtered onto the Si substrate before the metal catalyst
layer was deposited.
Depending upon the strength of the interaction between the catalyst metal
and the barrier layer upon which it is deposited, two different growth models
have been proposed [58]. These two models are illustrated in Fig. 8. In each
case, carbon is extracted from the hydrocarbon feedstock gas and diffuses
through the catalyst particle before taking its place in the forming nanotube.
The growth model when there is weak interaction between the catalyst par-
ticle and the barrier layer is known as “tip growth”, as the catalyst particle
stays at the tip of the nanotube. The model when there is strong interaction
is known as “base growth”, as the catalyst particle remains anchored to the
barrier layer at the base of the nanotube. For nickel on SiO2 , interaction is
weak, indicating tip growth. Indeed, bright catalyst particles can clearly be
seen at the tips of the nanotubes in Fig. 7.
These growth models are widely accepted in the nanotube community,
but there is a puzzle concerning the diffusion of carbon through the catalyst
particle. The temperatures achieved during PECVD are well below the melt-
ing point of the catalyst metals, yet it is thought that the catalyst particle
must be in the liquid phase for this diffusion to take place. An explanation for
this is that the saturation of the metal with carbon atoms causes a significant
decrease in the melting point for the catalyst particles, allowing the particle
to melt and the diffusion to take place [59].
Figure 7 shows that varying the gas ratio produces different structures,
with carbon nanotubes deposited at low C2 H2 ratios and a-C deposited at
high C2 H2 ratios. In order to understand why this is the case, we must ex-
amine the role of NH3 in the plasma. The production of a-C-free nanotubes
requires a controlled deposition of carbon, which can then self-assemble into
an energetically favoured nanotube form. This controlled deposition rate is
achieved through the combination of two reactions: the dissociation of a
carbon-rich gas (in our case C2 H2 ) and the removal of excess carbon that
would otherwise lead to amorphous carbon deposits.
It has been widely reported that atomic hydrogen is the active species
for the removal of excess carbon. Both H2 and NH3 have been reported to
act as sources for atomic hydrogen through electron impact dissociation in
plasma [51, 60]. Generation of H from an NH3 :C2 H2 DC plasma has also
been shown in simulations [61]. It has further been shown that NH3 is a
more effective generator of atomic hydrogen than H2 [51]. NH3 therefore has
a key role in removing any excess carbon through the generation of reactive
species which combine with and carry away carbon atoms.
The efficacy of NH3 in nanotube production has been further attributed
to the preferential decomposition of NH3 suppressing the decomposition of
C2 H2 . This is because the chemical bonds that hold the NH3 molecule to-
gether are weaker than those which hold C2 H2 together. It has also been
88 Martin S. Bell et al.

Fig. 9. H2 RGA signal for varying gas ratio

Fig. 10. HCN RGA signal for varying gas ratio

suggested that nitrogen is incorporated into catalyst particles, forming ni-


trides and changing the composition of the catalyst surface [62]. This may
also help to explain the diffusion puzzle. We can clearly see the preferential
decomposition of NH3 in our RGA data. A graph of the RGA signal for H2
for varying gas ratio is shown in Fig. 9.
H2 is generated by the decomposition of both NH3 and C2 H2 . To the
left of the figure, where the plasma is predominantly NH3 , the amount of H2
increases as NH3 increases. In this region, the H2 is derived from decompo-
sition of NH3 . To the right of the figure, where the plasma is predominantly
Growth Mechanism During PECVD of Multiwalled Carbon Nanotubes 89

C2 H2 , the amount of H2 increases as C2 H2 increases. In this region, the H2


is derived from the decomposition of C2 H2 .
At high NH3 ratios, NH3 decomposes preferentially over C2 H2 . This
causes the C2 H2 to decompose slowly, generating the small amounts of car-
bon necessary for nanotubes to self-assemble. At high C2 H2 ratios, there
is insufficient NH3 to effectively suppress C2 H2 decomposition, resulting in
high levels of carbon generation and deposition of excess carbon as a-C. NH3
therefore has two key roles in the formation of carbon nanotubes: not only
does it generate atomic hydrogen species to remove any excess carbon, but
it also suppresses the decomposition of C2 H2 , limiting the amount of carbon
generated in the first place.
Our observed minimum in H2 is close to our previously reported peak
in clean nanotube growth rate at around 20% C2 H2 . At this ratio, carbon-
removing species are at a minimum and C2 H2 decomposition is low, giving
rise to controlled deposition of clean nanotubes. Interestingly, ion intensities
peak at around 40% C2 H2 , where a-C is deposited. The optimum condition
for nanotube growth is therefore not the condition of maximum ion inten-
sity. This contrasts with most thin film growth, where the condition with
maximum ionisation is preferred.
Further work [63] has shown that the plasma during the nanotube depo-
sition is sufficiently energetic for endothermic ion-molecule reactions to take
place. In many applications, these reactions can and have been ignored as
they require significant pressures and ion energies. However, in this case the
high pressure and DC bias present the perfect condition for these reactions.
The process for the removal of excess carbon by atomic hydrogen species
should give rise to products including both carbon and hydrogen. The princi-
pal reaction product we detected in our RGA data was HCN. A graph of the
RGA signal for HCN with varying gas ratio is shown in Fig. 10. This shows
that HCN is generated where both C2 H2 and NH3 are in abundance.
The Figure also shows that a purely NH3 plasma does not generate signif-
icant HCN. This confirms that the reactions that remove excess carbon are
predominantly taking place in the gas phase. If there was a strong surface
reaction, we would see HCN arising from reactions between the active species
and the graphite stage, even in the absence of C2 H2 .

5 Conclusion
We have shown that carbon nanotubes have many exciting features and po-
tential applications. Nanotubes can be made using several different tech-
niques, and PECVD is particularly suitable for the fabrication of electronic
devices.
During PECVD, carbon is extracted from C2 H2 in a gas-phase reaction
at the catalyst surface, where it self-assembles into nanotube form. We have
90 Martin S. Bell et al.

explained why varying the gas ratio during deposition yields different struc-
tures and shown that there is an optimum ratio for clean nanotube growth.
This enables the fabrication of a-C-free devices for electronics applications,
which we believe opens up an enormous range of potential applications.
A vast amount of research effort has been conducted into carbon nano-
tubes, and we have an increasingly clear understanding of their properties
and how these can be manipulated to give desirable devices. Whilst nano-
tubes have made only limited forays into commercial products to date, we
believe that over the next decade the remarkable promise they have shown
in the research arena will be realised in the wider world.

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Index
a-C, 83 C60 , 78, 79
C70 , 79
arc discharge, 82
catalytic chemical vapour deposition
buckminsterfullerene, 78, 79 (CVD), 83
Growth Mechanism During PECVD of Multiwalled Carbon Nanotubes 93

chemical vapour deposition (CVD), 83 chiral vector, 79


chiral vector, 79 growth mechanism, 85
multiwalled nanotubes (MWNTs),
glow discharge, 84 77, 79, 82, 84
graphene, 78–80 single-walled nanotubes (SWNTs),
79, 81, 82
laser vaporisation, 82
zig-zag nanotubes, 79, 80
mass spectrometry, 84, 85
plasma, 83
nanofibres, 80, 82 plasma-enhanced chemical vapour
herringbone nanofibres, 81 deposition (PECVD), 77, 83, 84,
stacked nanofibres, 81 87, 89
nanotubes, 77–85, 87–89
armchair nanotubes, 79, 80 residual gas analysis (RGA), 84, 85, 88,
chiral nanotubes, 79 89
Correlation Between Local Structure and Film
Properties in Amorphous Carbon Materials

Giovanni Fanchini1,2 and Alberto Tagliaferro2


1
Present address: Ceramics and Material Engineering Dept., Rutgers University,
607 Taylor Road, Piscataway, NJ-08854, USA
2
Dipartimento di Fisica and LAQ Intese, Politecnico di Torino, Via Duca degli
Abruzzi 24, I-10129 Torino, Italy
alberto.tagliaferro@polito.it

Abstract. A discussion of the various amorphous carbon and amorphous hydro-


genated carbon films is presented. A link between sp2 , sp3 and H contents and the
mechanical and optoelectronic properties is established using some characteristic
lengths of the structure defined in a previous paper. These lengths describe the
average size of the sp2 agglomerates, the distance between such agglomerates, the
decay length of π states and the accommodation length of sp2 clusters in the sp3
network.

1 Introduction
Several of the Group IV elements have a crucial role in our life. If silicon
and its semiconductor relatives are at the basis of the modern life, carbon
is the basis of life itself. Moreover, carbon in its various forms and alloys
has a relevant role in the various aspects of modern life, too. Diamond is
coveted because of its appealing appearance and emotional value. Graphite
is used in mechanical applications. Carbon-based fuels are still running the
world, and plastics and polymers are everywhere around us. Even the more
“humble” amorphous forms of carbon have crucial importance in modern
life. For instance, amorphous carbon is a protective layer in the majority of
computer hard disks. Amorphous carbon can be grown at room temperatures
in thin film form, even on curved layers. It can be alloyed with other elements
(H, N, Si) to obtain materials having different properties. The present work
aims at providing a better understanding of the role and perspectives of
the various types of amorphous carbon and hydrogenated amorphous carbon
films. This work is based on the correlation between local structure and film
properties.

2 Electronic States in Carbon


The peculiarity of the carbon atom that determines its multiform impact on
reality is its ability to form either σ- or π-bonds. It is customary to describe
G. Messina, S. Santangelo (Eds.): Carbon, The Future Material for Advanced Technology Ap-
plications, Topics Appl. Phys. 100, 95–105 (2006)
© Springer-Verlag Berlin Heidelberg 2006
96 Giovanni Fanchini and Alberto Tagliaferro

molecular orbitals as a superposition of atomic orbitals pertaining to neigh-


bouring ions [1]. In this light, σ orbitals arise from the hybridisation of 2s
and 2p carbon atomic orbitals. If the p states (px , py , pz ) of the neighbouring
ions mix with their s states, we have four bonding and four antibonding σ
orbitals and the so-called sp3 hybridisation. This type of hybridisation can
be found, for instance, in diamond crystals.
If the s states mixes with two corresponding p states for each atom we
have three bonding and three antibonding σ orbitals. The remaining p states
hybridise to form a π state. This is the sp2 hybridisation, of which graphite
is a typical example.
Finally, if the s states mix with one p state for each neighbouring atom, we
have two bonding and two antibonding σ orbitals and two additional π states.
This is the sp1 hybridisation and is found, for instance, in acetylene.
The σ and π orbitals have very differently shaped electron clouds. σ or-
bitals have the highest density of the electron cloud along the axis connecting
the two neighbouring nuclei and form a strong, almost always covalent, bond
between the ions. Each π orbital has its electron cloud formed by two lobes
symmetric with respect to a plane containing the axis connecting the two
nuclei and absent on such plane. The π-bonds formed between two nuclei are
generally quite weak. Hence the energy spacing between π-bonding and anti-
bonding states is much lower than that between σ-bonding and antibonding
states. Although this is the situation for a pair of carbon ions, things can
be quite heavily modified if the collection of ions is enlarged. In such a case,
several additional effects come into play due to the delocalisation of π or-
bitals. For instance, if we analyse a benzene ring, we found that all π orbitals
arising form the six carbon ions have merged to form a delocalised orbital
containing all π electrons. This orbital now forms a strong additional bond
between all atoms of the ring. It becomes very costly in term of energy to
break a single π-bond, as it is fused with the others so that the structure is
overall much more stable. π orbitals have other peculiar properties that are
of relevance in organic chemistry and in life itself. For instance, the resonance
plays a relevant role in determining the properties of aromatic and aliphatic
structures. However, we will focus on this and other peculiarities only if they
will become relevant to our discussion.

3 Hybridisation and Local Structure


In the previous paragraph we reviewed the various type of hybridisations.
Here we analyse how the hybridisation affects the local and the overall struc-
tures of carbon materials. We will start our discussion from the viewpoint lo-
cal structure, i.e., of the distribution of neighbouring carbon ions. Obviously,
the spatial orientation of the various bonds is determined by the minimisa-
tion of the free energy of the system. Hence, different medium- and long-range
structures can be found, even if the local structure remains almost the same.
Correlation Between Local Structure and Film Properties 97

sp3 hybridisation leads to a tetrahedral local structure, in which the ref-


erence carbon ion is placed in the centre of the tetrahedron and the four
bonds connect it with the vertexes of the tetrahedron where the neighbour-
ing ions sit. The resulting structure is tridimensional, and by the repetition of
this block the diamond structure is built. The distance between neighbouring
atoms in diamond is 0.154 nm.
sp2 hybridisation leads to three σ-bonds lying in the same plane and form-
ing 120◦ angles between any two of them. The repetition of this block leads
to a bidimensional planar structure based on hexagonal blocks: the graphene
sheet. The distance between neighbouring atoms is 0.142 nm, shorter than
in diamond. This is due to the presence of π orbitals that strengthen the
bond between neighbouring ions. In-plane bonding is hence determined by a
concurrence of σ and π orbitals. We would like to focus on the point that
undistorted sp2 hybridised structures tend to be bidimensional. The out-of-
plane bonding between graphene sheets in graphite is due to weak Van der
Waals forces, and this justifies the prompt delamination of graphite.
sp1 hybridisation leads to two σ bonds lying on a line, which can be
straight or kinked depending on the case [1]. The presence of foreign atoms
can modify this picture. For instance, monovalent H or F become bond ter-
minators and can lead to linear structures (such as polymeric chains), even
for sp2 hybridised ions.

4 The Various Forms of Amorphous Carbon


In the previous paragraphs we have very briefly discussed crystalline struc-
tures and polymers. Now we move on to the field of our interest, i.e., amor-
phous structures, in the attempt to clarify a few items. The misuse of the term
diamond-like carbon is quite common in literature. So we will spend a few
lines to detail and justify the categorisation we make use of. As it is custom-
ary to enlarge the phrase amorphous carbon to encompass hydrogenated films
too, we will extend our classification to such films. In amorphous carbons the
various hybridisations (sp3 , sp2 , sp1 ) are present in different amounts and
in different spatial arrangements. It is customary [2] to disregard the role
of sp1 states. In this general discussion we will stick to this point of view,
but it should be remembered that each sp1 hybridised carbon ion provides
the same amount of π and σ states and hence even limited quantities of sp1
hybridised atoms might have an impact on the properties. An interesting
point on which we will elaborate later is that at a given sp3 /sp2 ratio (i.e.,
a given percentage of sp3 hybridised atoms) we can obtain films having dif-
ferent properties since the spatial arrangement of the sp2 and sp3 hybridised
ions can be different. Although one may naively think that a statistical dis-
tribution in space of hybridisations is possible among the various atoms of a
structure, it is by far not energetically favourable [3]. It was shown quite a
while ago that the system is stabilised if sp2 hybridised ions are clustered [3].
98 Giovanni Fanchini and Alberto Tagliaferro

The form of these clusters can be different depending upon the case, ranging
from conglomerates of benzene-like rings to linear chains [2].
Most of the amorphous carbon materials that we will discuss below can
be considered as multiphase systems, in which sp3 - and sp2 -coordinated re-
gions coexist. The fact that sp2 regions are basically bidimensional while
sp3 ones are tridimensional has interesting consequences on the structure
of amorphous carbons. In fact, the sp3 fraction needed to reach percolation
threshold in the sp3 phase (∼ 0.3) is much lower than that needed for per-
colation of the sp2 phase (∼ 0.8 [4]). Hence, in most cases, the sp3 regions
are interconnected in an overconstrained network that hosts sp2 coordinated
clusters. The sp3 network will constitute the (more or less rigid, following
H incorporation in it) backbone of the material, strongly affecting its me-
chanical properties. Only in very special cases (glassy carbon) the material
backbone is made by sp2 network in which sp3 regions are dispersed.
Nonhydrogenated films can be labelled as follows [5]:
– Glassy carbon (GC). They have such a high sp2 content that the various
sp2 regions are made of entangled and interconnected benzene-like rings.
The spare sp3 regions are diluted in the network and have a negligible
effect on the material properties. The fact that sp2 regions are entangled
leads to mechanical properties (hardness, . . . ) different from those of
graphite [2].
– Tetrahedral amorphous carbon (ta-C). ta-C films are highly con-
strained sp3 -rich films having mechanical properties close to those of di-
amond. sp2 regions are mainly formed by sp2 paired up or diluted in the
sp3 matrix.
– Amorphous carbon (a-C). This broad class contains all films that have
properties and characteristics intermediate between the previous ones.
The inclusion of hydrogen affects the structure and the properties of the
films in many ways. Generally speaking, it decreases the local coordination
number [6] and hence makes the structure more “floppy”. The floppiness
or rigidity of the material obviously correlates with the amount of hydrogen
and its spatial distribution. As an sp3 -coordinated region has a higher average
coordination number than an sp2 -coordinated one, a higher hydrogen content
is needed to bring it to floppiness. A role is played by the number and spatial
distribution of the sp2 sites. Benzene-like rings are rigid and can be distorted
to a high cost in energy as a collection of bonds has to be distorted [7].
Basically, all hydrogenated amorphous carbon films can be assigned to
one of the following categories:
– Tetrahedral hydrogenated amorphous carbon (ta-C:H). ta-C:H
have a limited hydrogen (20–25 at %) and high (> 2) sp3 /sp2 ratio
coupled with a small amount of sp2 inclusions [2], which are probably
organised more in chains than in rings. This structure leads to mechan-
Correlation Between Local Structure and Film Properties 99

ical properties closer to those of diamond than for all other types of
hydrogenated amorphous carbon.
– Diamond-like hydrogenated amorphous carbon (DLHC). DLHC
originally bore the name of diamond-like carbon (DLC), although some
authors still apply this term to all type of amorphous hydrogenated car-
bon, generating quite a deal of confusion in the reader. Compared to
ta-C:H films, these have lower sp3 /sp2 ratios (∼ 1) and similar hydrogen
contents. The larger sp2 content is organised in larger clusters, which
require larger distortions of the sp3 network to be accommodated.
– Graphite-like hydrogenated amorphous carbon (GLHC). Although
the hydrogen content is similar to that of the previous two categories, the
sp3 /sp2 ratio is much lower (< 0.5). The average coordination number is
reduced close to the floppiness limit [5].
– Polymer-like hydrogenated amorphous carbon (PLHC). These
films are hydrogen rich (> 40 at %), and their sp2 phase is mainly or-
ganised in chains. These features lead to a floppy system.
The careful reader has surely noticed that some combination of H, sp3 ,
2
sp values are intermediate between the various classes. Our categorisation
is aimed at usefulness and to have a limited number of classes. Hence it can-
not be exhaustive and does actually leave some shadowed regions. Materials
belonging to those regions have properties and characteristics bridging those
of neighbouring classes.

5 Phase Matching and Its Effects on Materials


If we attempted to compare the medium- and long-range structures of the
amorphous carbon films grown around the world, we would probably find that
all of them are more or less different. This might suggest that the quest for
general rules to help in understanding and maybe predicting film properties
might be without hope. Nevertheless, it has been shown that by developing
a few simple concepts [5] a reasonable understanding of film properties can
be achieved.
Let us review the basics of that model and later expand its consequences
to encompass mechanical properties too. As most of the optoelectronic prop-
erties of amorphous carbon films are determined by π states [2], it is crucial
to focus on those aspects of the structure that affect the spatial and energy
distribution of these states. In particular, it is crucial to analyse the role of
“phase matching”, i.e., the distortions induced in the local bonding at the
boundaries between sp3 and sp2 regions. In order to describe these effects
the following parameters were defined (see Fig. 1) [5]:
Lc is the diameter of a given sp2 cluster, assumed for sake of simplicity to
be planar and circular in shape. However, the general features of the
discussion will hold for chain-like clusters too.
100 Giovanni Fanchini and Alberto Tagliaferro

Fig. 1. Characteristic lengths in amorphous carbon films [5]

Lc−c is the distance between the borders of two neighbouring clusters.


Lπ is the distance from the cluster border at which the π wavefunction
becomes negligible. We can roughly estimate this parameter to be of
the order of a few tenths of nanometres [2].
Before the definition of the last parameter, let us hypothesise that we insert an
sp2 cluster in a fully sp3 -coordinated network. The structure of the sp3 region
near the inclusion needs to be modified in order to accommodate the cluster.
If we go far enough, however, no effect of the inclusion on the sp3 structure
will be detected:
Lac is the “accommodation length”, i.e., the maximum distance from the
cluster at which the modification induced in the sp3 network is present.
In most cases these modifications consist in distortions of the bonds,
which can be labelled as structural disorder [2]. For a given cluster size
the actual value of Lac depends on the rigidity of the sp3 network, which
is correlated to the local coordination number [1].
The detailed discussion of the cases that can arise by varying the relative
values of the various lengths is reported in [5]. Here we will briefly discuss
the various form of amorphous carbon in the light of these parameters. As
said in the previous paragraphs, in most cases the backbone of the material
is constituted by the (more or less hydrogenated) interconnected sp3 phase.
The various possibilities are described in Fig. 2:
1. Noninteracting clusters (Fig. 2a). When the sum 2Lac of the accommo-
dation distances of two neighbouring clusters is lower than their distances
Lc−c, the two clusters have neither direct nor indirect interaction. The
sp2 clusters behave almost like an ensemble of independent molecules em-
bedded in a medium instead of dispersed in vacuum. π states are localised
in the clusters, and π and π ∗ bands are made of localised states [5].
2. Overlapping accommodation regions (Fig. 2b). The interaction between
clusters is indirect since the distortions due to phase matching affect the
energetic distribution of π states [8]. π and π ∗ bands are still made of
localised states, but their shape is distorted [5].
Correlation Between Local Structure and Film Properties 101

Fig. 2. The various local structures (see text) [5]

3. Overlapping π states (Fig. 2d). When the sp2 content approaches the
value for sp2 phase percolation, we reach a condition in which the π states,
whose wavefunction decays outside the clusters, overlap. Part of the π and
π ∗ bands is made of localised states, and part is made of extended (better:
overlapping) ones [5].
4. Percolating sp2 phase (Fig. 2c). When the sp2 regions percolate they
become the interconnected backbone of the material. The sp3 inclusions
will not even affect the mechanical properties. π and π ∗ bands are made
of extended states, and their differences from graphite ones are mainly
due to disorder [5].
In order to better understand the implication of what we have just dis-
cussed, we note that the presence of hydrogen in the sp3 network reduces
its local average coordination number and the backbone rigidity [9]. This
should help in understanding why we attribute PLHC to case 1 above. The
high hydrogen content of the sp3 phase strongly reduces Lac and the distor-
tions related to phase matching at the boundaries between sp2 clusters and
hydrogenated sp3 backbone. For GLHC a similar discussion can be made, al-
though the decrease in the average coordination number has to be attributed
more to the high sp2 amount [10] than to the relatively low H content. How-
ever, the higher sp2 content leads to larger cluster sizes and this affects the
optoelectronic properties (see below). In DLHC films, because of the low
hydrogen content and the relatively high sp3 content, the accommodation
regions highly overlap (case 2). The low sp2 content prevents case 3 from
occurring. In ta-C:H we have a similar situation, although sp2 clusters have
a more likely aliphatic rather than aromatic character [2].
In nonhydrogenated films, the absence of hydrogen increases, at a given
sp3 /sp2 ratio, the local coordination number and Lac with respect to hy-
drogenated films. Both ta-C and a-C can then be fitted in case 3. How-
ever, the large difference in the sp3 content leads to a large difference in the
102 Giovanni Fanchini and Alberto Tagliaferro

2Lac /Lc−c ratio and the local coordination number. As a consequence, the sp3
phase of ta-C is much more distorted. Finally, GC can be attributed to case
4 because of its very high sp2 content, which leads to sp2 phase percolation.

6 Optoelectronic and Mechanical Properties

We have already noticed that in amorphous carbon films the optoelectronic


properties are mainly determined by the π states and the mechanical ones
by the backbone (usually the sp3 phase). We will now analyse more in detail
how the peculiarities of the structure of each type of film will reflect on its
properties.
GC. The percolation of the sp2 phase would suggest that the mechan-
ical properties will be close to that of graphite. The fact that the
graphene strips [11] are entangled prevents delamination and gives
a certain, although limited, hardness [2] to the material. The op-
toelectronic properties differ from those of graphite because the
long-range order of graphene sheets and the consequent semimetal-
lic behaviour are absent. Nevertheless, the graphene strips have
macroscopic size so that their optical gap is in the far infrared,
making the material optically black. Because of the presence of π
and π ∗ extended states close in energy [5], the electrical conduc-
tivity is high and is weakly dependent on temperature.
ta-C. The high sp3 content and the absence of hydrogen give rise to a
rigid backbone so that the mechanical properties of this material
are close to those of diamond [12, 13]. Still the optical properties in
the visible range are determined by the highly distorted sp2 inclu-
sions, and the absorption coefficient has a rather slow increasing
trend as photon energy is increased [14]. The high level of distor-
tions also leads to a high spin density [14]. Although the optical
gap can reach high values because of the spread of energy levels
of sp2 inclusions due to distortions, the electrical conductivity is
much higher than in other materials having similar gaps and no
π states.
a-C. The presence of a rich sp2 phase with medium-sized (up to a
few nanometres) sp2 inclusions reduces the distortions of the pre-
vious cases and leads to intermediate properties. The fact that
sp2 clusters are smaller than in GC opens the optical gap [2] and
makes electronic conductivity lower and with a higher activation
energy [15]. The lack of long-range entanglement makes the mate-
rial softer with mechanical properties of no relevance [11, 12]. The
high cluster density leads to a high ESR signal, even in absence of
relevant distortions.
Correlation Between Local Structure and Film Properties 103

ta-C:H. The presence of H makes the sp3 backbone less overconstrained


(i.e., rigid) than in ta-C. This decreases distortions and degrades
the mechanical properties with respect to ta-C, although they re-
main the highest in the a-C:H class [13, 16]. Less distortions in the
sp2 clusters lead to steeper absorption coefficient trends in the vis-
ible region, even if a higher sp2 content is present [17]. Electronic
properties are improved, and in some cases photoconductivity is
detected [18]. The ESR signal is reduced with respect to ta-C and
DLHC as a consequence of the less distorted sp2 clusters [5].
DLHC. Despite the presence of hydrogen these materials are highly dis-
torted because of the size of the clusters and rigidity of the
sp3 backbone. This leads to the better mechanical properties
among “non-ta-C:H” hydrogenated amorphous carbon films [15].
Distortions also have a crucial impact on optical properties, reduc-
ing the optical gap, and ESR signal, giving rise to a very large spin
density [5]. Electrical conductivity is higher than in ta-C:H [15, 18]
because of the higher sp2 content, which leads to a reduced distance
between sp2 regions, and the greater size and higher distortions of
the sp2 phase that reduce the gap [5, 19].
GLHC. The larger amount of sp2 content compared to the previous case
deteriorates mechanical properties [15]. Despite such sp2 increases,
the optical gap increases because distortions are reduced [2]. The
reduction in distortions greatly reduces the spin density too [5, 20].
PLHC. The relevant hydrogen content leads to floppy materials with me-
chanical properties of no interest [15]. The transparency of the hy-
drogenated sp3 phase and the limited size of sp2 inclusions, mainly
arranged in chains, highly increases the optical gap [2]. These ma-
terials become almost insulating [2, 19] but highly photolumines-
cent [2] because the absence of distortions prevents nonradiative
recombination paths to proliferate [2]. The spin density is orders
of magnitude lower than in the other cases [5].

7 Conclusion
We have discussed the various types of amorphous carbon and the role of the
main structural parameters in determining their properties. The overall pic-
ture was obtained by using a few simple parameters (cluster size, distance be-
tween neighbouring clusters, decay length of π states, accommodation length
of sp2 clusters) previously introduced in [5]. We have established a quali-
tative link between structure and mechanical and optoelectronic properties.
The present paper will, of course, be more useful if a link between deposition
methods and parameters and local structure could be established. However,
as such link is thoroughly discussed in [2], we address the reader to that paper
to find information on this aspect.
104 Giovanni Fanchini and Alberto Tagliaferro

References
[1] R. McWeeny: Coulson’s Valence (Oxford University Press, Oxford, UK 1979)
96, 97, 100
[2] J. Robertson: Mater. Sci. Eng. R 37, 129 (2002) 97, 98, 99, 100, 101, 102, 103
[3] J. Robertson, E. P. O’Reilly: Phys. Rev. B 35, 2946 (1987) 97
[4] J. Robertson: Phil. Mag. B 76, 335 (1997) 98
[5] G. Fanchini, S. C. Ray, A. Tagliaferro: Diam. Rel. Mat. 12, 891 (2003) 98,
99, 100, 101, 102, 103
[6] J. C. Philips: J. Non-Cryst. Solids 34, 153 (1979) 98
[7] J. Robertson: Diam. Rel. Mat. 4, 298 (1995) 98
[8] G. Fanchini, A. Tagliaferro: Appl. Phys. Lett. 85, 730 (2004) 100
[9] F. Jansen, J. C. Angus: J. Vac. Sci. Technol. A 6, 1778 (1988) 101
[10] J. Robertson: Phys. Rev. Lett. 68, 220 (1992) 101
[11] J. Robertson: Adv. Phys. 35, 17 (1986) 102
[12] G. M. Pharr, D. L. Callahan, S. D. McAdams, et al.: Appl. Phys. Lett. 68,
779 (1996) 102
[13] A. C. Ferrari, J. Robertson, M. G. Beghi, C. E. Bottani, et al.: Appl. Phys.
Lett. 75, 1893 (1999) 102, 103
[14] K. B. K. Teo, A. C. Ferrari, G. Fanchini, S. E. Rodil, et al.: Diam. Rel. Mat.
11, 1086 (2002) 102
[15] P. Koidl, C. Wagner, B. Dischler, J. Wagner, et al.: Mat. Sci. Forum 52, 41
(1990) 102, 103
[16] M. Weiler, S. Sattel, K. Jung, H. Ehrhardt, et al.: Appl. Phys. Lett. 64, 2797
(1994) 103
[17] S. Sattel, J. Robertson, H. Ehrhardt: J. Appl. Phys. 82, 4566 (1997) 103
[18] A. Ilie: Diam. Rel. Mat. 10, 208 (2001) 103
[19] D. Dasgupta, F. Demichelis, A. Tagliaferro: Phil. Mag. B 63, 1255 (1991) 103
[20] F. Giorgis, A. Tagliaferro, M. Fanciulli: Amorphous Carbon: State of the Art
(World Scientific, Singapore 1998) p. 143 ff 103

Index
π states, 95–97, 99, 100, 102, 103 ta-C:H, 98
σ states, 95–97
a-C, 98 accommodation length, 100, 101, 103
sp2 -bonded clusters, 95, 98–103 amorphous carbon, 95, 98
cluster size, 103 characteristic lengths, 99, 100
distorted clusters, 102, 103
carbon coordination, 98–101
undistorted clusters, 97
cluster–cluster interaction, 100
sp1 hybridisation, 96, 97 clustering, 97
sp2 hybridisation, 96, 97
sp3 backbone, 98–103 diamond, 96, 97
sp3 hybridisation, 96, 97 diamond-like carbon (DLC), 97, 99
sp3 /sp2 bonding ratio, 97–99, 101 disorder, 100, 101
ta-C, 98 distortions, 98–103
Correlation Between Local Structure and Film Properties 105

electrical conductivity, 102, 103 mechanical properties, 98, 99, 101–103


electron spin resonance (ESR)
ESR signal, 102, 103 optical gap, 102, 103
electronic properties, 95 optical properties, 102
optoelectronic properties, 99, 101–103
floppiness, 98
percolation, 98, 101, 102
glassy carbon, 98 percolation threshold, 98
graphene, 97, 102 photoconductivity, 103
graphite, 96, 97
rigidity, 98, 100
hydrogenated diamond-like carbon
(DLC:H), 99 spin density, 102, 103
hydrogenated graphite-like carbon
(GLC:H), 99 tetrahedral amorphous carbon, 98
hydrogenated polymer-like carbon tetrahedral hydrogenated amorphous
(PLC:H), 99 carbon, 98
Defects in CVD Diamond Films from Their
Response as Nuclear Detectors

Marco Marinelli, Enrico Milani, Aldo Tucciarone, and Gianluca Verona


Rinati

Dipartimento di Ingegneria Meccanica, Università di Roma “Tor Vergata”,


Via del Politecnico 1, I-00133 Roma, Italy
milani@ing.uniroma2.it

Abstract. CVD diamond films can be used to realize nuclear detectors with out-
standing working capability in harsh environments. Since efficient particle detection
requires high drift lengths of the carriers produced by the ionizing particle, the pres-
ence of defects severely limits the performance of these detectors. This is a major
issue because the fabrication technology of CVD diamond is much less advanced
than that of more conventional materials like silicon. The different kinds of defects
in CVD diamond and their influence on the detector response are discussed. The
connections between the microscopic structure of CVD diamond and the priming
(or pumping) effect, which is widely used to increase CVD diamond detector per-
formance, are elucidated. The analysis of the response of CVD diamond-based de-
tectors is used to extract qualitative and quantitative information on the properties
of defects limiting the free movement of charge carriers in the detector (e.g., carrier
type for which the traps are active, activation energies, geometrical distribution in
the film, etc.).

1 Introduction

Diamond’s extreme properties [1] extend over different areas (electrical, me-
chanical, thermal, etc.). As a consequence, applications in many fields could
in principle benefit from the utilization of diamond as the primary material
for device realization. The use of natural samples is almost always not feasi-
ble, because of their cost and lack of standard properties. Diamond crystals
grown by high-pressure, high-temperature methods (HPHT), on the other
hand, generally have small dimensions and contain significant amounts of
impurities. For this reason, the demonstration in 1986 of the possibility to
grow diamond films by chemical vapor deposition (CVD) by exciting a plasma
in a hydrogen/hydrocarbon gas mixture at low pressure (about 100 mbar)
and relatively low temperatures (about 750◦ C) using silicon wafers as the
growth substrate created very high expectations. As is often the case, the ini-
tial enthusiasm cooled down when it was realized that the new technique had
some limitations, especially in terms of reproducibility and quality. Therefore,
while in some areas CVD diamond devices are now commercially available, for
many applications the growth technique is still not adequate. In particular,
electronic applications of CVD diamond are severely limited by the polycrys-
G. Messina, S. Santangelo (Eds.): Carbon, The Future Material for Advanced Technology Ap-
plications, Topics Appl. Phys. 100, 107–135 (2006)
© Springer-Verlag Berlin Heidelberg 2006
108 Marco Marinelli et al.

tallinity of the grown films and by their impurity content, so that they are
particularly demanding in terms of sample quality (the so-called electronic
grade diamond). The presence of grain boundaries and of traps limits the
mean free path of charge carriers, thus strongly affecting the amplitude and
the homogeneity of the response of CVD diamond-based electronic devices.
We will review here some experimental techniques that can be used to
investigate the type and distribution of electrically active defects in CVD
diamond films, using the response of nuclear particle detectors built using
these films. The information provided by these techniques is reported for
high-quality polycrystalline CVD diamond films grown in our laboratories.
Clearly, other samples will give different results, but the approach that we
present here can be used on any sample.
Special attention will be devoted to the so-called pumping or priming
effect, i.e., the increase in the detector response after preirradiation with ion-
izing radiation, a phenomenon which is characteristic of diamond detectors.
Although the pumping process is reversibile (by annealing or by exposure to
strong visible light sources), the pumped state remains stable over at least
several weeks at room temperature, provided that the sample is not exposed
to strong light sources. Exposure to normal ambient light results in no mea-
surable depumping on this time scale. The proposed experiments will disclose
the physical grounds of the pumping process and discriminate its effect on
electron and hole motion in the detection process. Besides their scientific in-
terest, these techniques could be of practical interest since the knowledge of
defect properties and of the defect distribution could be very useful in under-
standing how changes in the growth parameters (gas composition, substrate
temperature, pregrowth nucleation process, etc.) affect the structure of the
films, thus in principle allowing researchers to obtain more efficient devices.

2 CVD Diamond Nuclear Detectors:


Realization and Physics
A detailed description of the various techniques to grow CVD diamond films
is beyond the scope of this contribution. For short reviews the reader may
refer to refs. [2, 3, 4, 5]. In the following we will give only the basic information
necessary to understand the content of the rest of the article.
In low-temperature CVD growth, carbon is fed in the growth reactor,
generally in the form of hydrocarbons (e.g., CH4 ) strongly diluted in H2
atmosphere. Some sort of energy is then transmitted to the gas mixture
to create a plasma. Under appropriate conditions (gas composition, plasma
temperature and pressure) if a substrate (e.g., a silicon or molybdenum slab)
is exposed to the plasma, a thin film of diamond is obtained. A pretreatment
(such as scratching) of the substrate surface is required to promote diamond
nucleation.
Defects in CVD Diamond Films 109

Fig. 1. SEM image of a cross section of a CVD diamond film showing the columnar
nature of the growth

The standard deposition conditions used for the films grown in the Roma
Tor Vergata University laboratories (to which we will often refer in the follow-
ing) are as follows. The reactor is a NIRIM-type microwave tubular reactor,
suitably modified to increase film quality [6]. The gas mixture is 1% CH4
in H2 at a pressure of about 130 mbar, with a substrate temperature of
about 700–750◦C. The substrates are 0.5 mm thick silicon slabs, pretreated
by scratching. The growth rate is about 0.7 µm/h. The high crystalline qual-
ity of these films is demonstrated by their excellent Raman spectra and very
low luminescence background [7].
The heteroepitaxial nature of CVD diamond growth on silicon substrates,
and the fact that nucleation takes places in the form of randomly oriented
seeds, leads to the growth of polycrystalline films. A peculiar characteristic
of these films is their so-called columnar growth, well-evidenced visually in
Fig. 1, which shows a scanning electron microscope view of a cross section of
a CVD diamond film. As the thickness increases during the growth, some of
the grains stop growing, while others become bigger and bigger, so that grain
size increase from the diamond–substrate interface to the growth surface. On
the growth surface of a CVD diamond film therefore, the grain dimension
is roughly proportional to the film thickness. For films in the 10–200 mm
thickness range surface grain size is typically about 1/4 to 1/3 of film thick-
ness. Obviously all film properties which depend on the presence of grain
boundaries are not uniform along the film cross section.
110 Marco Marinelli et al.

The realization of a nuclear particle detector from a CVD diamond film


is very simple: it is sufficient to deposit on both sides of the film a metal
contact [8] and apply to these contacts an appropriate voltage so as to create
an electric field inside the film perpendicular to the film surface. Since the
detector has the geometry of a thin slab, a so-called parallel plate detector is
obtained. In the following, “positive” bias (or polarity) will refer to the case
of the contact on the film growth surface being at a higher voltage than the
contact on the Si substrate, the opposite being referred to as “negative” bias.
Typically, a 1 V/µm electric field is applied.
The working principle of the device is as follows. The nuclear particle
creates in the detector a (generally) great number of electron–hole pairs, and
the electric field drives the generated carriers towards the two electrodes,
according to charge sign. In the presence of trapping centers, the electron
and hole will not necessarily reach the electrodes, and we will call lc the total
distance that the electron and hole move apart (clearly, lc ≤ D, D being
the detector thickness). Using Ramo’s theorem [9, 10], each electron–hole
pair created by an ionizing particle induces in the measuring circuit a charge
qc = elc /D, e being the electronic charge. The amplitude of the voltage pulse
measured by the external circuit is proportional to the total collected charge
Qc (i.e., the sum of qc over all electron–hole pairs produced by the ionizing
particle). The ratio η = Qc /Q0 between Qc and the total charge Q0 generated
by the ionizing particle in the detector is the detector’s efficiency, one of the
most widely used parameters to identify the detector performance.
Introducing Le and Lh as the average of the distances le and lh (with
le + lh = lc ) that charge carriers move apart from the generation point, we
obtain:
Le + Lh
η= . (1)
D
The experimentally accessible information is η, since the detector output is
proportional to Qc , but like Le and Lh it depends on the system geometry
through the sample thickness (i.e., interelectrode spacing) and the penetra-
tion depth of the ionizing particles. The physically relevant parameters, re-
lated to the defect distribution, are the mean free distances λe = µe τe E and
λh = µh τh E, where µ is the carrier mobility, τ is the time before the carri-
ers being trapped and E is the applied electric field. The charge collection
distance (CCD) is defined as the sum of the mean free distance of charge
carriers within the material:
δ = λe + λh . (2)
A direct relationship between the experimentally accessible information (η)
and the intrinsic material properties (λe and λh ) can be obtained through
the Hecht theory [11]:
Le + Lh [λ2 e−D/λh (eG/λh − 1) + λ2e e−D/λe (eG/λe − 1)]
η= − h , (3)
D DG
Defects in CVD Diamond Films 111

where G is the penetration depth of the particles to be detected. Assuming


λe = λh = δ/2, (3) becomes

δ δ 2 (1 − e−2G/δ )(1 − e2(G−D)/δ )


η= − . (4)
D 4DG
Equations (3) and (4) or their approximate (for λe , λh  D) counterpart
η  δ/D are often used to get an estimate of δ from efficiency measurement.
However, they are valid only in the case of uniform distribution of the charge
created by the ionizing particle along the penetration path, and homogeneous
trap distribution, which is not the case of polycrystalline CVD diamond. We
will see in a later section how to extend this formula to the general case.
Obviously, the Hecht formula tends to saturate, so that η → 1 for δ → ∞.
A peculiar feature of CVD diamond particle detectors is the increase in
their efficiency after irradiation with ionizing radiation, a process called prim-
ing or pumping. The increased efficiency is believed to be due to a saturation
of deep traps [12], leading to increased carrier mean free paths. Typically,
irradiation with X-rays or β-particles is used to reach the pumped state.
In addition to the increase in efficiency, pumping greatly extends the tem-
perature region in which the detector can be operated without significant
performance degradation [13, 14]. Ion Beam Induced Current measurements
showed that in CVD diamond samples the collection efficiency is not homo-
geneously distributed, and pumping increases the size of the high collection
efficiency regions, making the response spatially more homogeneous [15].
In CVD diamond particle detectors a crucial role is played by their thick-
ness. Because of the columnar nature of CVD diamond growth, the crystal
quality is much worse close to the substrate interface than at the growth
surface. In particular, the CCD has been found to increase with film thick-
ness [8, 16]. CCDs up to about 300 µm have been reported [17] in millimeter-
thick synthetic diamond after removing about half of the sample thickness
from the poor-quality substrate side.

3 Analysis of the Charge Collection Spectrum

3.1 Qualitative Analysis

As reported in the previous section, each particle impinging on the detector


produces a signal connected to the CCD of the detector. Because of inho-
mogeneities in the density of defects, electric field distribution, etc., different
particles will give signals of different amplitudes. The statistical distribution
of the amplitudes of the pulses generated by the incoming radiation is re-
ferred to as the charge collection spectrum (see Fig. 2 for a typical spectrum
of our detectors in the as-grown and pumped states), easily generated using
a multichannel analyzer. Its average value gives the the average amplitude of
112 Marco Marinelli et al.

Fig. 2. Typical collection spectra of a high-quality CVD diamond detector in the


as-grown (left peak ) and pumped (right peak ) states. Solid lines are Monte Carlo
simulations

the response (that is, the induced charge and therefore the detector’s average
efficiency and CCD), while its width gives the inhomogeneity of the response
(i.e., the energy resolution). The spectrum is reported as a function either of
the channel number in the multichannel analyzer or (when the multichannel
scale has been calibrated through the response of a silicon detector, which
has 100% efficiency) of the efficiency or of the “collected energy”, simply
defined as Ec = ηEd , Ed being the energy deposited by each particle in the
detector. (For example, 241 Am α-particles deposit all their 5.5 MeV energy in
the detector provided the detector thickness exceeds their penetration depth
G  14 µm.) From Fig. 2 it is clear that even very high quality polycrys-
talline CVD diamond detectors cannot be compared to Si-based ones, either
in terms of efficiency (100% for a silicon detector) or especially in terms of
energy resolution (in the case of silicon detectors the FWHM of the charge
collection spectrum is well below 1% of the peak position).
The spectra reported in Fig. 2 show that in this case priming changes not
only the position of the peak, but also its shape, from a right-asymmetric
(positive skewness) to a left-asymmetric (negative skewness) one, with a sort
of cut-off at high efficiency values. This behavior can be related to the dif-
ferent distribution of the two factors limiting the response of CVD diamond
particle detectors, namely in-grain defects and grain boundaries. Because of
the columnar growth, the latter strongly increase in concentration towards
the substrate side of the sample, while the former ones can be considered to be
homogeneously distributed. If we assume that priming only acts on in-grain
defects, we have a qualitative explanation of the spectra [18]. In the as-grown
state the response is limited by the homogeneously distributed in-grain de-
Defects in CVD Diamond Films 113

fects (hence the positive skewness), since the low average efficiency implies
that the generated charges do not reach the grain boundary region close to
the substrate. Indeed, the detector used in Fig. 2 is D = 115 µm thick, while
the charges are generated within the penetration depth G  14 µm of the
5.5 MeV α-particles used. From from η  δ/D we have therefore δ  6 µm,
so that G + δ  D. After priming, the increase in efficiency is due to the
deactivation by priming of the in-grain defects, creating a “defect-free” layer
before the grain boundary region located close to the diamond–silicon inter-
face, which produces the high efficiency cut-off.
A Monte Carlo simulation quantitatively support this view [18], since
both the primed and unprimed charge collection spectra can be perfectly
reproduced considering that only in-grain defects can be deactivated by
priming. In-grain defects are modelled by a homogeneous distribution of
random trapping centers, and grain boundaries by a density distribution
D(x) = A exp(−x/b), where x is the distance from the diamond–substrate
interface normalized to the thickness of the sample, and A, b are parameters.
The MC simulated response curves shown in Fig. 2 are obtained including
in the simulation both in-grain defects and grain boundaries in the as-grown
case, and only grain boundaries, with the same distribution utilized in the
former curve, in the primed case. It is not possible to reproduce the left-
asymmetric primed curve without introducing a grain boundary distribution
strongly peaked at the substrate side as required by the columnar growth.
The negative skewness appears, therefore, to be characteristic of high crys-
talline quality samples where in-grain defects are substantially inactivated by
pumping, leading to high values of η. In the following, the average efficiency
calculated from the charge collection spectrum will be referred to simply as
the efficiency. To effectively separate the contribution of in-grain traps and
grain boundaries, the film thickness must be substantially higher than both
the extension of the grain boundary region (otherwise the grain boundary
defects dominate the in-grain traps even in the as-grown state) and the pene-
tration depth of the radiation (otherwise the carriers would be generated over
the whole sample thickness, and even in the as-grown state would “sample”
in their motion the grain boundary region).
More evidence can indeed be collected varying the detector thickness. For
thin samples, where the grain size is comparable to (or smaller than) the mean
free path due to in-grain defects, only a moderate effect is to be expected from
the pumping process, since grain boundaries are the main obstacle to high
CCD values even in the as-grown state. As the film thickness (i.e., grain size)
increases, however, substantial improvements in the efficiency and CCD of
the detectors can be anticipated on the basis of the model because of the
saturation of in-grain defects.
Figure 3 shows the charge collection efficiency under positive bias of sev-
eral films grown in the same conditions (i.e., same crystal quality) with thick-
ness from about 20 µm (i.e., just above the penetration depth of 5.5 MeV
114 Marco Marinelli et al.

Fig. 3. Experimental efficiency data in the as-grown and pumped state for positive
bias polarization. The solid lines are the best fits obtained with the extended Hecht
model (see Sect. 3.3)

Fig. 4. Collection spectra for positive and negative bias in the pumped state and
in the as-grown state (inset)

α-particles) to about 160 µm [19]. The curves relative to the as-grown and
pumped states show a markedly different behavior. The initial efficiency in-
crease with thickness in as-grown samples is followed for D > 40 µm by a de-
crease roughly following a 1/D law, while in the pumped state the efficiency
steadily increases up to a thickness of 100 µm, and then slightly decreases.
Defects in CVD Diamond Films 115

A quantitative explanation of the data in Fig. 3 will be presented in


next section, but we can understand them qualitatively [19, 20]. For very low
thickness values (D < 40 µm) the microgranularity of the substrate interface
layer prevents significant drift lengths of the carriers, so that the efficiency
is very low. Since priming does not act on grain boundary traps, the as-
grown and pumped η(D) curves are superimposed. As the film thickness
increases, so does the grain dimension, and the free path of carriers sharply
increases until eventually (D > 40 µm) the grain size becomes larger than
the mean free path due to in-grain defects. Now grain boundaries play a
minor role and the effect of pumping, which partly saturates in-grain traps,
becomes increasingly evident. In the normal state the CCD is limited by the
substantially homogeneous distribution of in-grain defects, as demonstrated
by the 1/D decrease law of η: the approximation η  δ/D is indeed valid
(δ  D), correctly leading to a δ value independent from thickness, with a
value close to 10 µm. In the pumped state, when grain boundaries still play
a role because of the partial deactivation of in-grain traps, the increase in
grain size (i.e., δ) compensates thickness variation in (4), leading to a more
pronounced increase of η. Eventually, of course, the efficiency must reach a
limiting value.
Another procedure that allows us to extract valuable information from
the collection spectrum is to make the measurement both in positive and in
negative polarity. Indeed, the geometry of the detection process may not be
symmetric between the two contacts, e.g., because the ionization produced
in the detector is not uniform, or because of the columnar structure of the
film. As a consequence, the contribution of the two type of carriers (flowing
towards opposite electrodes) to the signal will not be the same. Compari-
son of the collection spectra measured under both positive and negative bias
could give information on the contribution of each type of carrier. Consider
the idealized situation in which λh is comparable to film thickness, λe  λh ,
and the penetration depth of the ionizing particles is small (G  D). Practi-
cally no signal would be observed under negative bias, since neither electrons
(having negligible mean free path) nor holes (blocked by the negative contact)
would move in the detector, while a strong signal due to holes would be de-
tected under positive bias. Figure 4 reports typical detection spectra obtained
irradiating our CVD diamond detectors with 5.5 MeV α-particles, both in
the as-grown and pumped states for each polarization. In the as-grown state
the efficiency does not change substantially with bias polarity, while in the
pumped state the efficiency is much higher in positive polarity. As discussed
in [21, 22], this implies that in the as-grown state λe ≈ λh , and that λe does
not change with the pumping procedure, while λh strongly increases.

3.2 Quantitative Analysis: The General Model

We pointed out that (3) is only valid when the distribution of the charge
created by the ionizing particle along the penetration path and the trap
116 Marco Marinelli et al.

distribution are uniform. Because of the columnar growth of polycrystalline


CVD diamond, and the Bragg distribution of the energy released by a ionizing
particle, both these requirements are not fulfilled in our case.
Following [19], we now extend the Hecht theory to take into account
inhomogeneous CVD diamond samples and nonuniform ionization profiles.
We will then apply this model to extract information on the inhomogeneous
defect distribution and on the defect properties from the detector response.
The shape of the electron and hole trap distribution, as a function of the
distance x from the growth surface, is taken as:
1
we,h (x ) = + b · e(x −D)/c , (5)
λe,h

where the first term on the right refers to the in-grain defects (i.e., the in-
trinsic properties of diamond crystals), while the second terms models grain
boundaries (i.e., the columnar nature of the film).
The mean distances covered by charge carriers from the generation points,
lh and le , depend on the distance x of the generation point from the top
electrode and can be defined by considering the probability P that a charge
carrier moves at least through a distance s. In a positive bias configuration:
s s
− w (x +s  ) ds  − w (x −s  ) ds 
Ph (x, s) = e 0 h Pe (x , s) = e 0 e (6)

 D−x  x
lh (x) = Ph (x, s) ds le (x) = Pe (x, s) ds (7)
0 0

in which the integration limits take into account that s cannot exceed the
distance of the charge generation point from the corresponding collection
electrode.
The average drift distances Le and Lh of all the charge carriers generated
by an ionizing particle are calculated by averaging le (x) and lh (x) over the
distribution function u(x) of the generation points:

Lh = lh u(x) , Le = le u(x) . (8)

For analytical treatment, the Bragg ionization distribution u(x) can usu-
ally be very well approximated by the exponential function u(x) = A+B ex/C
with a cut-off at the penetration depth G. In the case of 5.5 MeV α-particles,
for example, the above formula works fine using as parameter values (obtained
by the nuclear physics simulation program SRIM [23]) A = 267.7 keV/µm,
B = 11.17 keV/µm, C = 3.45 µm and G = 13.54µm. After calculating Lh
and Le using (5)–(8), the efficiency η can be finally derived from (1). Obvi-
ously, in the case of a negatively polarized detector, the role of electrons and
holes must be exchanged.
Defects in CVD Diamond Films 117

Combining (1), (5)–(8), therefore, the quantitative relationship between


the intrinsic properties λe and λh and the experimentally accessible quantity η
can be derived. Clearly, η depends on a number of intrinsic properties of the
film (λe , λh , b and c) in a very complicated way. Direct inversion of the
equations to extract these parameters from the measured η values is not
possible. Rather, it is possible to measure η as a function of other quantities
such as the penetration depth G of the radiation, or the sample thickness D
(from which λe , λh , b and c do not depend) and to fit the obtained curves
with the above proposed formulae.

3.3 The Use of Detector Thickness

As an example, we will now apply this model to the analysis of the η(D)
curves reported in Fig. 3. Since CVD diamond properties are different in
the as-grown an pumped state, in principle we should consider four fitting
parameters for each of the two η(D) curves. However, we have seen that (at
least for the films used in [18, 19, 20, 21, 22]) in the as-grown state λe ≈ λh ,
and only λh significantly increases after pumping. Moreover, the pumping
procedure does not influence the grain-boundary defects (described through
the b and c parameters in (5)) [18, 19]. Therefore the trap distribution in
CVD diamond can be described with good approximation by four parameters
only. These are b, c, λe whose values are the same both in the as-grown and
pumped state, and the λh value in the pumped state (in the as-grown state
λh is substantially equal to λe ). A reduced number of parameters obviously
puts more constraints on the fit, therefore increasing its reliability.
The simultaneous fit of both the η(D) data sets in Fig. 3 with the theory is
represented by the continuous lines, and the corresponding fitting parameters
are reported in Table 1. The goodness of the fit is an indirect proof that the
assumptions made are substantially correct, so that the charge collection
distance δ = λe + λh increase after pumping from 14 µm to 62 µm is really
due only to the large variation of λh , λe being by hypothesis unaffected by
priming. In the case of negative bias the η(D) values are very similar to
those measured under positive bias in the as-grown state, irrespective of the
sample being in the normal or primed state. In this case, in fact, the increase
in λh with pumping does not strongly affect η because holes can only move
an average distance G/2 (roughly equal to λe ) before being stopped by the
negative contact.

Table 1. Best-fit parameters for the efficiency vs. thickness curves in Fig. 5

λh λe b c
µm µm µm−1 µm−1
As-grown 7 7 1.1 10
Pumped 55 7 1.1 10
118 Marco Marinelli et al.

Fig. 5. Charge collection distances for the as-grown and pumped state obtained
with the homogeneous Hecht model (solid lines) and with the extended Hecht model
(dashed lines)

An interesting result is the identification of the strongly defective region


near the Si–D interface, due to the columnar growth. We can divide CVD
diamond film in two regions, a “homogeneous” one where the action of uni-
formly distributed in-grain defects predominates on grain boundaries, and an
“inhomogeneous” one, closer to the substrate, where the opposite is true. The
borderline between them depends on the values of the b and c parameters,
and, from (5), corresponds to a distance yB = D − xB from the substrate
interface, where
1 1
+ = 2b · e(xB −D)/c = 2b · e−yB /c . (9)
λh λe
A value yB = 26 µm was obtained from the data reported in Table 1, in the
pumped state. When D = yB grain boundaries are always dominant over in-
grain defects, and no effect of pumping is expected at all. This is confirmed
by measurements performed on films of thickness lower than about 30 µm.
In literature the CCD values for CVD diamond films are often derived
from efficiency measurements using (5), i.e., the homogeneous Hecht model.
Despite being widely used, this procedure is clearly incorrect. In the general
model the δ value is correctly treated as an intrinsic property of the material,
and as such is independent of film thickness. As a consequence, the plot of δ
as a function of the film thickness D is given by a constant value (continuous
lines in Fig. 5). The dependence of η on D is due to the different relevance of
in-grain and grain boundary defects for films of different thickness, according
to (5). The analysis of the η(D) curves by the homogeneous model is totally
different. Since in (4) there would be no adjustable parameters, the η(D)
Defects in CVD Diamond Films 119

curves simply cannot be fitted. The only way to obtain δ would require a
point-to-point efficiency data conversion by means of (4), however, obtain-
ing a nonphysical, variable δ value (dashed line in Fig. 5). This value tends
to the correct one, obtained by the inhomogeneous model, only for D high
enough to make the influence of grain-boundaries negligible with respect to
in-grain defects. As in the pumped state in-grain defects are partially filled,
the asymptotic value of the CCD is higher for the pumped state than for the
as-grown one.

3.4 The Use of Penetration Depth

Another way to highlight the different action of in-grain and grain boundary
defects, besides varying the film thickness, would be, of course, to change
the penetration depth G of the detected particles for a given film, and use
the method outlined above to fit the η(G) curves. For such an experiment
to be meaningful, G should be varied in a wide region (for example, 0.1<
G/D < 0.8) so that a variable energy beam source would be necessary (Van
De Graaf generator, tandem accelerator, etc.). Some results can be found
in [24, 25], but to limit ourselves to techniques which only require normal
laboratory equipment, we will here discuss a simpler use of the penetration
depth, which requires a more limited range of values for G and can still
provide useful information. We will no longer be able to reconstruct the trap
distribution, but could quantitatively evaluate the mean free distances λe and
λh .
When the film thickness is significantly higher than both the penetration
depth and the carrier mean free path, the grain boundaries will have no
effect at all on the detector response, which only depends on G, λe and
λh . Varying G, the contribution of one type of carrier (depending on bias
polarity) gradually decreases as the penetration depth of the incident particles
is reduced, so that the η(G) curves for the two polarities depend on the mean
free path of each carrier type in a different way, allowing us to separately
extract the desired information.
To control the α-particle penetration depth in the CVD diamond, two
different approaches have been proposed [22]. The obvious way is to vary the
energy of the incident particles (variable energy method, VEM) by using an
absorbing layer of appropriate thickness. Air can be used as the absorber
for 5.5 MeV α-particles, since their energy is halved by a 2.5 cm layer, and
the source-to-sample distance can therefore be easily controlled. As an alter-
native, the incidence angle θ of the α-particles with respect to the sample
surface can be varied, the system being kept in vacuum to leave the incident
energy of the particles at 5.5 MeV (variable incidence method, VIM). In this
case, G is reduced by a factor cos θ with respect to the normal incidence
value G0 = 13.54 µm. A particle incidence angle in the 0◦ –80◦ range can be
controlled with a beam collimator, corresponding to 0.17 < cos θ < 1. The
beam divergence prevents reaching significantly higher incidence angles.
120 Marco Marinelli et al.

Fig. 6. Efficiency curves as a function of the penetration depth G for air measure-
ments in positive (square) and negative (circle) bias polarity; (a) in the pumped
state, (b) in the as-grown state. Solid lines are the fit curves

In Figs. 6b and 7b the η(G) curves are reported when the sample is
in the as-grown state using VEM and VIM, respectively. The same curves
are plotted for the pumped state in Figs. 6a and 7a. Although VEM and
VIM techniques lead to qualitatively similar behaviors, at lower penetration
depths (i.e., thicker absorbing layer) the energy released in the sample by the
ionizing radiation is reduced in the VEM case, and the spectrum is shifted to
the lower energy side, partly overlapping with the noise shoulder. The signal-
to-noise ratio decreases, eventually making measurements impossible. In the
VIM measurements the total energy released by the impinging particles is
constant for all the θ values, so that both the shape and the peak position of
the spectra are not greatly affected. Lower penetration depths can be reached
with approximately constant error bars on the efficiency measurements using
VIM.
In the analysis of the curves, (5)–(8) can be simplified because grain
boundaries play no role. Equation (5) becomes we,h = 1/λe,h and (6)–(8) can
Defects in CVD Diamond Films 121

Fig. 7. Efficiency curves as a function of the penetration depth G for tilt measure-
ments in positive (square) and negative (circle) bias polarity (a) in the pumped
state, (b) in the as-grown state. Solid lines are the fit curves

Table 2. Transformations of the parameters A, B, C and G used in the fits of


Figs. 6 and 7

Normal incidence VEM VIM


A (keV/µm) A0 = 267.7 A0 A0 G0 /G
B (keV/µm) B0 = 11.17 B0 e[(G0 −G)/C0 ] B0 G0 /G
C (µm) C0 = 3.45 C0 C0 G/G0
G (µm) G0 = 13.54 G (from SRIM) G (from SRIM)
122 Marco Marinelli et al.

be analytically calculated. For positive bias [22] we have Ph (s) = exp(−s/lh ),


Pe (s) = exp(−s/le ) and

lh (x) = λh (1 − e−(D−x )/λh ), le (x ) = λe (1 − e−x /λe ). (10)

Averaging over all the electron–hole pairs, using the energy density u(x) =
A + B exp(x/C) (with a cut-off at the penetration depth G), the efficiency η
for positive polarization one finds:

Le + Lh λe + λh 1
η= = −
D D D[AG − BC(eG/C − 1)]
  
e(1/C −1 /λe )/G − 1 −D/λh e
(1/C +1/λh )/G
−1
× BC λe + λh e
1 − C/λe 1 + C /λh

+ A[−λ2e (e−G/λe − 1) + λ2h e−D/λh (eG/λh − 1)] , (11)

while for negative polarization the role of electrons and holes is to be ex-
changed. In the standard case (normal incidence in vacuum) the parameters
A = A0 , B = B0 , C = C0 and G = G0 (Table 2) were calculated by fitting the
SRIM-simulated Bragg energy distribution with the function u(x) described
in the previous section. When the α-particle penetration depth changes, the
function u(x) is modified, leading to suitable changes of the parameters A,
B, C and G as reported in [22] (see Table 2).
The η(G) curves relative to both positive and negative polarization can
be simultaneously fitted by (9) using the proper transformations of A, B,
C and G (Figs. 6 and 7) and the very same values of λe and λh for all
four curves (Table 3) to increase the fitting constraints. Consistent values
of the two fitting parameters are obtained from the two methods, the lower
errors in VIM confirming the superior accuracy of this method as compared
with VEM. The pumping process is much more effective on hole conduction,
since λh becomes much greater than λe after pumping, in contrast with the
situation before pumping, when λe  λh .

Table 3. Best-fit parameters for the efficiency vs. penetration depth curves in
Figs. 6 and 7

VEM VEM VIM VIM


(as-grown) (pumped) (as-grown) (pumped)
λe (µm) 8.6 ± 1.0 8.3 ± 1.3 8.6 ± 0.6 8.4 ± 1.0
λh (µm) 8.1 ± 1.0 36.1 ± 1.5 6.8 ± 0.6 37.6 ± 1.1
Defects in CVD Diamond Films 123

4 Time-Domain Analysis
4.1 The Background

As a direct consequence of Ramo’s theorem, the charge induced by a single


generated carrier in the measuring circuit in a time dt is dq = edx/D =
(ev/D)dt, where v is the drift velocity of the carrier. Therefore the time
evolution of the detector signal reflects the dynamics of carriers generated by
the ionizing radiation in the detector. Carrier dynamics are in turn related
to the nature and concentration of the traps present in the film. That is why
a deep insight on the dynamics of charges generated in the detector and the
identity of defects existing in CVD diamond can be obtained from the time
development of single pulses.
Zanio et al. [26] and Martini and McMath [27] showed how this time
behavior changes when detrapping and/or trapping events occur in the de-
tector, and applied this analysis to conventional Si detectors. This analysis
was then extended [21, 28] to describe the more complex behavior of CVD
diamond detectors.
In the original model of Martini and McMath, a single kind of defect is
considered, i.e., the situation found in Si detectors, and a single carrier type
(the ionizing radiation was a focused γ-ray beam directed close and parallel
to one of the electrodes, so that only one type of carrier was free to move
towards the opposite electrode, contributing to the output signal of the de-
tector according to Ramo’s theorem). In the absence of trapping defects the
total distance traveled by a single electron–hole pair (before being collected
at the electrodes) amounts exactly to D. In this case the detector’s efficiency
is 100%. If deep traps are present in the detector, which capture a fraction
of the carriers and do not allow their thermal release (detrapping), the col-
lected charge and the efficiency are accordingly reduced, but the collection
process is still completed within the transit time. When shallow traps are
involved, 100% efficiency may still be achieved, but the time response is now
slower because carriers experiencing trapping–detrapping have their motion
delayed by a time on the order of the detrapping time constant, so that the
charge collection process extends beyond TR . A so-called slow component
appears, as opposed to the fast one due to the ballistic motion of untrapped
carriers. For a 100 µm thick diamond detector working under an external
field E = 104 V/cm, TR = D/v ≈ D/mE ≈ 1 ns, so that in most cases
the fast component is not experimentally accessible because of the response
time of the instrument used to trace pulse shapes. Charge collection for the
slow component is ruled by the detrapping time constant, which can be much
longer than a few nanoseconds, so that it can be experimentally measured.
For t < TR no charge reaches the electrode, and an analytical solution for
the rate equation exists [27]. Unfortunately, the time evolution of the slow
component cannot be calculated analytically even in this simple case involv-
ing a single type of trapping centers and a single type of carriers generated
124 Marco Marinelli et al.

Fig. 8. Time evolution of the pulses measured in the as-grown state for positive
and negative polarities

Fig. 9. Time evolution of the pulses measured in the pumped state for positive
and negative polarities

at one electrode. For diamond detectors under α- or β-particle irradiation,


the released charge Q0 is not concentrated at one electrode but is distrib-
uted along the particle penetration depth, ranging from several microns to
the whole sample thickness. Consequently, both electrons and holes can in
principle contribute to charge collection. In addition, we will show in the
following that more than a single type of defect must be introduced to ex-
plain experimental results in the case of CVD diamond detectors. A computer
simulation can be used to quantitatively describe trapping–detrapping effects
once a qualitative picture of the trapping centers present in the detectors is
available.
Defects in CVD Diamond Films 125

4.2 Qualitative Analysis

The experimental time evolution of a diamond detector output before pump-


ing, i.e., in the as-grown state, is reported in Fig. 8 for positive and negative
field polarity [21]. The pulses have different amplitudes, reflecting the width
of the charge collection spectrum, but similar amplitudes are observed for
positive and negative polarity. In all cases the saturation value is immedi-
ately reached, the collected charge being constant after the 10 ns rise time
of the digital oscilloscope. This implies that once trapped by a defect, elec-
trons and holes are not detrapped, so that the defects limiting the detector’s
response in the as-grown state can be identified as deep ones. No significant
difference is observed between positive and negative polarity because CCD
(and therefore both electron and hole mean free paths before trapping) is
lower (see below) than the penetration depth G  15 µm of 5.5 MeV α-
particles in diamond. As a result, the growth surface boundary plays a very
limited role. Further, since the film thickness D d, the substrate interface
boundary plays no role at all. Therefore, even if electrons and holes should
have different mean free paths, no difference would be observed between neg-
ative and positive polarity. In principle only one kind of traps for electrons
and holes is necessary to explain the behavior in the as-grown state.
This picture changes when examining the pulse shapes for the same sam-
ple in the pumped state (Fig. 9). No significant effect of pumping is found
in the case of negative polarity. A dramatic change, on the other hand, can
be seen for positive field polarity. Not only is the amplitude of the pulses
greatly enhanced, reflecting the large increase of efficiency due to pumping,
but a significant slow component develops, breaking the symmetry between
positive and negative polarity.
It appears, therefore, that pumping saturates most of the deep defects
responsible for hole trapping without detrapping, leading to a greatly en-
hanced mean free path of holes in the pumped state, while not significantly
affecting electron traps [21, 29]. Thus, shallower defects existing in a lower
concentration than saturated, deeper ones, now become important. Since
they allow detrapping, they do not limit the overall amplitude of the pulse,
but slow down the charge collection process. For negative polarity, the lim-
ited changes in the pulse amplitude and shape with respect to the as-grown
state show that no significant saturation of electron traps occurs. Holes are
in principle substantially free to move, but since 5.5 MeV α-particles only
ionize within their penetration depth G  15 µm (much less than the hole
mean free path), holes can move only a few microns before being collected
at the surface electrode. They therefore cannot give a great contribution to
charge collection according to Ramo’s theorem, nor can they be trapped and
detrapped since their mean free path is now much higher than the real path
to the electrode. Therefore the slow component substantially does not show
up, and at the same time the fast one does not increase significantly with
respect to the as-grown case.
126 Marco Marinelli et al.

4.3 Quantitative Analysis: Computer Simulation


A computer simulation can be developed [21] to calculate, according to this
model, the pulse shape Q(t) in a discrete time approximation. For each carrier
type, the detector thickness D is divided into N laminae, the transit time
of a carrier in each lamina being ∆t = D/N v = TR /N , where v is the drift
velocity. For each carrier type (electrons and holes) deep (type-A) and shallow
(type-B) defects are taken into account, having trapping time constants τA+ ,
τB+ and detrapping time constants τAD , τBD , respectively. Carriers can be free,
ni (tj ) being the number of free carrier in the i-th lamina at time tj , or
trapped in each of the two trapping centers, nAi (tj ), nBi (tj ) being their
corresponding numbers. In the time interval ∆t = tj − tj−1 , free carriers
either move to the next layer contributing by ev∆t/d = e/N to the induced
charge, or are trapped in either defect. In the same time interval, trapped
carriers can be released and move to the next layer or remain trapped. We
have therefore at first order approximation in ∆t:
 
1 1
ni (tj ) = ni−1 (tj−1 ) − ni−1 (tj−1 )∆t + (12)
τA+ τB+
∆t ∆t
+ nA(i−1 ) (tj−1 ) D + nB(i−1 ) (tj−1 ) D ,
τA τB
∆t ∆t
nAi (tj ) = nAi (tj−1 ) − nAi (tj−1 ) D + ni (tj−1 ) + , (13)
τA τA
∆t ∆t
nBi (tj ) = nBi (tj−1 ) − nBi (tj−1 ) D + ni (tj−1 ) + , (14)
τB τB
(release and trapping of a carrier in a single time interval ∆t and other
second-order effects can be neglected for sufficiently large N values). The
total charge induced by each type of carrier is then
e
Q(tj ) = Q(tj−1 ) + + ni (ti ). (15)
N i

This procedure is repeated twice (for electrons and holes, respectively), and
the results are summed. Direct recombination effects have been neglected
since electrons and holes rapidly separate under the external electric field, and
the concentration of charges generated along the α-particle track is estimated
to be lower than that of trapping centers. The simulation parameters are the
+ + D D + + D
carriers’ velocity v and the time constants τeA , τeB , τeA , τeB and τhA , τhB , τhA ,
D
τhB for electrons and holes, respectively. However v only defines the value of
∆t, i.e., the time scale of the process. In fact, all time constants only appear
in (12)–(14) through their ratio with ∆t, so that their values are relative to
∆t. A reasonable value v = 5 · 106 cm/s [8] has been chosen, resulting in
TR = d/v = 2 ns.
According to the qualitative discussion reported in the previous section,
+
there are no type-B defects for electrons (i.e., τeB = ∞). Also, type-A defects
Defects in CVD Diamond Films 127

Fig. 10. Comparison of measured pulses with the simulation based on the trap-
ping–detrapping model in the as-grown and pumped states

do not allow detrapping (τeA D D


, τhA = ∞). Only τeA + +
, τhA +
and τhB D
, τhB must
therefore be determined. Since the CCD is more easily visualized in terms
of carrier mean free path, the trapping time constants are transformed into
+ + +
the mean free paths λeA = vτeA , λhA = vτhA , λhB = vτhB due to type-A or
type-B defects for electrons and holes, respectively. In contrast to the time
constants, the mean free path values do not depend on the arbitrary choice of
∆t (which cancels out in the product with the corresponding time constant),
and are therefore real ones.
In Fig. 10 simulated pulses are compared with experimental ones for posi-
tive polarity (the negative polarity case is a trivial one, since the slow compo-
nent is always very small). Because of the scaling property of the pulses [21],
a single pulse for the as-grown and pumped states has been selected, cho-
sen in the middle of the efficiency distribution determined by the α-particle
collection spectra (about 8% in the as-grown state and 40% in the pumped
state).
To find the best agreement with the measured pulses, the as-grown, pos-
itive polarity curve alone is simulated first. As discussed above, the lack of a
slow component means that the density of deep (A) traps for holes is much
higher than that of shallow (B) traps, so that the only parameters to be
determined are in this case λeA and λhA , the value of λhB being almost ir-
relevant. When, as in the present case, the efficiency is so low that the total
CCD is lower than the penetration depth of α-particles, the only accessible
information is the sum of electron and hole mean free paths and not their
separate values. Setting λeA = λhA , the as-grown state pulse is simulated
using λeA = λhA  4.5 µm (δ = 9 µm), corresponding to τeA + +
= τhA = 0.09 ns
with the chosen value for v. The pulse measured in the pumped state has
then been simulated, introducing also shallow (detrapping) hole traps (i.e.,
λhB ) and, as already argued in the preceding section, a substantially lower
128 Marco Marinelli et al.

Table 4. Parameter values used in the simulation of Fig. 10

As-grown Pumped
λeA (µm) 4.5 4.5
λhA (µm) 4.5 50
λhB (µm) 35 35
D
τhB (ns) 200 200

concentration of effective deep hole traps (i.e., a higher value for λhA ) as a
consequence of pumping. The concentrations of deep electron traps (i.e., λeA )
is kept unaltered. In order to reproduce the experimentally observed ampli-
tude ratio between fast and slow components, it turns out that λhA = 50 µm
+
(i.e., τhA = 1 ns), so that the pumping process reduces the density of effective
hole deep trapping centers by one order of magnitude, while λhB = 35µm (i.e.,
+
τhB = 0.7 ns), much higher than the 4.5 µm as-grown value of λhA , which
confirms the validity of the initial assignment λeA = λhA  4.5 µm based
upon neglecting hole type B traps in the simulation of the as-grown pulse.
The parameter values used are summarized in Table 4.
In agreement with the model, in thin films (D < 35 µm) a significant slow
component is not detected even after pumping, since holes are trapped at the
highly defective region close to the film–substrate interface before travelling
distances much in excess of 10 µm.
D
The time evolution of the slow component is well described when τhB
= 200 ns. A rough estimate of the activation energy ED of shallow defects
D
responsible for hole trapping and detrapping can be made since 1/τhB =
12 −1
s exp(−ED /kT ). Using s ≈ 10 s for the attempt frequency s (to which
ED is anyway relatively insensitive), we obtain ED  0.3 eV.
A more quantitative evaluation of ED can be obtained by measuring the
thermally activated detrapping time constant at various temperatures [28].
The slope of the linear dependence of ln(τD ) on 1/T gives then the activation
energy ED . Using the estimated value ED  0.3 eV, we see that a 20% de-
crease in T is expected to increase τ D by a factor of 15. Temperatures ranging
from about −40◦C to about 20◦ C should therefore correspond to values of τ D
in the range 200–3000 ns, well accessible experimentally. This temperature
range is easily covered using Peltier elements. In Fig. 11 the pulse shapes of
the detector in the pumped state and under positive bias are reported, mea-
sured at various temperatures and normalised to unit amplitude for better
comparison. The systematic speed-up of the response with temperature con-
firms that the slow component is due to thermally activated detrapping from
relatively shallow defects. Similar curves are obtained under negative bias.
In the normal state the slow component is strongly reduced, as expected, its
residual being attributed to an incomplete “depumping” process.
In Table 5 the values of ED calculated by fitting the τ D (T ) curves with (1)
are reported in all four cases (positive and negative polarity, as-grown and
Defects in CVD Diamond Films 129

Fig. 11. Pulses measured in the pumped state for positive polarity at temperatures
−40◦ C, −30◦ C, −15◦ C, 0◦ C, 20◦ C (from slowest to fastest). The amplitudes are
normalised to unity

Table 5. Values of the activation energy of shallow traps calculated from the
temperature dependence of the detrapping time constant

As-grown+ As-grown− Pumped+ Pumped−


EA (meV) 280 370 340 337

pumped state). A value ED = (0.35 ± 0.02) eV is found, with the exception of


the case of positive polarity in the normal state, probably as a consequence
of an imperfect temperature control.

5 Temperature Effects: Depumping

The method described in the previous section is not suitable to measure the
activation energy of deep traps, since temperatures should be raised beyond
the working range of the detector to have measurable detrapping times. To
circumvent this problem, the α-particle response of a diamond film was re-
cently measured [30,31] after successive annealing steps performed at different
temperatures in the 180–230◦C range. The measurement is therefore carried
out at room temperature, and only the annealing treatment is performed at
temperatures beyond those at which the detector works properly.
If before each annealing curve at a given temperature the sample is driven
to its fully pumped state, the effect of thermal annealing is to promote
thermal detrapping of carriers from occupied trapping centers, i.e., a par-
tial depumping. The increase in the number of active (i.e., not filled) traps
lowers the carrier mean free path before trapping, and the detector efficiency.
130 Marco Marinelli et al.

Table 6. Detrapping time constants τ for the various annealing temperatures, as


extracted from the fit of curves reported in Figs. 12 and 13

T (◦ C) τ (h)
Deeper trap 180 373
(Fig. 13) 190 159
206 71.1
220 14.7
228 6.9
Shallower trap 125 140
(Fig. 14) 138 48.7
165 4.5

With reference to type-A and type-B traps for holes discussed above, let nA
and nB be their concentrations, respectively. The total number per unit vol-
ume n∗A of active (not filled) type-A defects after an annealing step depends
on the annealing time t as n∗A (t) = nA (1 − e−t/τ ), where τ is the detrapping
time constant.
The collection distance of holes depends therefore on nA and nB as
1
λh (t) = , (16)
σA nA (1 − e−t/τ ) + σB nB
where σA and σB are the capture cross sections of type-A and type-B defects,
respectively. Introducing λh0 and λh∞ as the hole charge collection distances
in the fully pumped and completely depumped state, respectively, we have
λh0 = λh (t = 0) = 1/σB nB , and λh∞ = λh (t = ∞) = 1/(σA nA + σB nB ).
Substituting back in (16), we obtain
λh0
λh (t) = . (17)
1 + (λh0 /λh∞ − 1) · (1 − e−t/τ )
It is therefore possible to calculate the activation energy EA by extracting
τ from the λh (t) dependence and using 1/τ = s exp(−ED /kT ), provided
we calculate λh from the detector efficiency η using, e.g., the VIM or VEM
techniques discussed above. Since we are interested in λh only (pumping
only acts on hole traps), a simplified procedure can be used, consisting in
performing the α-particle irradiation at a single high incidence angle (80◦ )
with respect to the detector’s surface normal [30, 31].
The λh (t) curves were obtained at five different temperatures ranging
from 180◦ C to 228◦ C, as reported in Fig. 12. Equation (17) fits these curves
very well, exception made for the first point in each curve. The fast decrease
of about 5 µm in the value of λh observed in each first annealing step can be
attributed to the existence of other traps with lower activation energy, i.e.,
shorter time constants, that are not resolved in this temperature range and
time scale. To isolate the contribution of the first (deeper) trapping center, the
Defects in CVD Diamond Films 131

Fig. 12. Time evolution of the thermal depumping for the deeper defect. Annealing
temperatures are 180◦ C (), 190◦ C (), 206◦ C (•), 220◦ C () and 228◦ C ()

Fig. 13. Time evolution of the thermal depumping for the shallower defect. An-
nealing temperatures are 125◦ C (), 138◦ C (•) and 165◦ C ()

experimental data were first fitted with (17) considering only data with t >
1 h, when the initial drop is completed. The second (shallower) defect clearly
requires lower annealing temperatures to be investigated (see below). The
best-fit time constants for each temperature, cycle are reported in Table 6.
Plotting (Fig. 14) the detrapping time constants in logarithmic scale as a
function of the inverse of the annealing temperature a good linear trend
is observed, confirming the validity of the adopted model. The activation
energy of the defect is Ea1 = 1.62 ± 0.15 eV with an attempt frequency
s01 = 3.5 · 1011 Hz.
A similar procedure was employed to investigate the lower energy defects,
using a 125–165◦C temperature region. More careful experimental procedures
132 Marco Marinelli et al.

Fig. 14. Detrapping time constant τ as a function of the inverse of the annealing
temperature. The activation energies are calculated through the best fits (solid
lines) with 1/τ = s exp(−ED /kT )

Fig. 15. Decay of the detector efficiency after two hours annealing time vs. the
annealing temperature

should be adopted because of the smallness of the effect observed [31]. The
results are reported in Fig. 13 and the best-fit time constants reported in
Table 6 were extracted. At these temperatures the detrapping time constant
of the deeper traps would be, as calculated from the τ values in Table 6,
on the order of months, so that there is no “mixing” of the two effects. The
activation energy of these shallower traps is (Fig. 14) Ea2 = 1.33 ± 0.06 eV,
s02 = 5.7 · 1010 Hz.
Defects in CVD Diamond Films 133

The existence of two traps involved in the pumping–depumping mecha-


nism is evidenced, plotting (Fig. 15) the ratio λh (t = 2h)/λh (t = 0) as a
function of the annealing temperature. The double step shows that a first
kind of trap produces a moderate detrapping in a 2 hour time scale at tem-
peratures around 130◦ C, while another, deeper one comes into play in the
same time scale only at a temperature of about 210◦ C. A plateau exists in
between, when the first trap has been fully depumped after two hours while
detrapping from the other one is not yet effective on this time scale.

6 Conclusion
There is a great variety of experimental techniques that allow us to extract
information on the properties of defects present in CVD diamond films. We
reviewed here a number of them, characterized by the fact of being based
on the analysis of the response of nuclear detectors built from the samples
to be analyzed to irradiation with ionizing particles. Both the realization
of nuclear detectors from the films and the setup of the experiments are
relatively simple. Since basically all these techniques make use of the response
of a solid state nuclear detector, which depends on carrier dynamics, they
can only give information on electrically active defects, i.e., defects acting as
traps for electrons and holes. Within this field, however, they are a simple and
powerful tool to obtain information ranging from the type and distribution
of defects in the film to their activation energy, the type of carriers on which
they act, the trapping and detrapping times, and the mean free paths of the
carriers.

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Defects in CVD Diamond Films 135

Index
activation energy, 128–132 fast component, 123, 128

carrier mobility, 110, 116 Hecht theory, 110, 111, 114, 116, 118
charge collection distance (CCD), 110, high-pressure high-temperature
117, 118, 130 (HPHT), 107
charge collection spectrum, 111–113,
125 Monte Carlo simulation, 113
chemical vapour deposition (CVD),
penetration depth, 112
107–112
polycrystalline diamond, 108, 109, 112,
columnar growth, 109, 111–113, 115,
116
116, 118
Ramo’s theorem, 110, 123–125
defects, 108
defects distribution, 108, 110–113, slow component, 123–125, 127–129
115–117, 119, 133
grain boundaries, 108, 109, 112, 113, time constant, 123, 126, 128–132
115, 116, 118–120 trap, 108
grain boundaries distribution, 112, depumping, 108, 128, 129
113, 116, 118 priming, 108, 111–113, 115, 117
in-grain defects, 112, 113, 115, 116, pumping, 108, 111, 113, 115, 117,
118, 119 122, 124, 125, 128–130
in-grain defects distribution, 112, trapping, 110, 113, 123–131
113, 115, 118
detector efficiency, 110 variable energy method (VEM),
detectors, 108 119–122, 130
detrapping, 123–129, 131 variable incidence method (VIM),
diamond, 107 119–122, 130
Effects of Nanoscale Clustering in Amorphous
Carbon

J. David Carey and S. Ravi P. Silva

Nanoelectronics Centre, Advanced Technology Institute, School of Electronics and


Physical Sciences, University of Surrey, Guildford, GU2 7XH, UK
David.Carey@surrey.ac.uk

Abstract. In this review the effects of clustering associated with the sp2 and sp3
phases of amorphous carbon thin films are examined. We highlight that many of
the optical and electronic properties of these films can be explained by considera-
tion of disorder in the sp2 phase. Within the context of topological and structural
disorder, we explain the variation of the visible Raman line width, Raman shift,
Tauc gap and Urbach energy as a function of deposition conditions. We further
go on to describe how intra-sp2 cluster interactions are responsible for the narrow-
ing of the electron paramagnetic resonance line width with increasing spin density
and how this intracluster interaction can be extended to the intercluster transport
properties, in particular, for electron field emission from the films. We also examine
how the mechanical properties of carbon films are affected by clustering which can
be enhanced by thermal annealing.

1 Introduction and Bonding in Carbon


Crystalline carbon is unique amongst the elements of the periodic table, be-
ing able to form one of the hardest naturally occurring materials, diamond,
and also one of the softest, graphite. From an electronic point of view these
two materials possess, respectively, a 5.5 eV energy band gap and a zero band
gap, making the electronic properties vary between those found in an insula-
tor and those of a semimetal. This very different behaviour can be traced to
the bonding and the bond hybridization that are present (Fig. 1). In the case
of sp3 hybridization, four σ bonds, arranged at 109.5◦ to each other, allow
for the tetrahedral bonding of diamond. These four bonds are responsible
for the high hardness and large energy band gap. By contrast, in the case
of sp2 -hybridised carbon there are three σ bonds bonding in-plane to three
other carbon atoms at 120◦ to each other. In addition, there is one pz or-
bital perpendicular to the plane of the threefold bonding. This anisotropy in
the bonding distinguishes the in-plane electronic properties of graphite from
the properties perpendicular to the basal plane. Whilst there is a strong in-
plane interaction, the weaker out-of-plane interactions are responsible for the
lubricant properties of graphite.
These bond hybridizations are not restricted to the crystalline forms of
carbon and are available to form amorphous carbon films (Fig. 1), which have

G. Messina, S. Santangelo (Eds.): Carbon, The Future Material for Advanced Technology Ap-
plications, Topics Appl. Phys. 100, 137–152 (2006)
© Springer-Verlag Berlin Heidelberg 2006
138 J. David Carey and S. Ravi P. Silva

Fig. 1. A schematic representation of different types of hybridised bonding and


the resultant crystalline and model amorphous structures

a wide range of properties, some of which are presented in Table 1. It is im-


portant at the outset to distinguish between the different types of amorphous
carbon. For example, from Table 1 the physical and electronic properties of
tetrahedral amorphous carbon (ta-C) are very different from hydrogenated
diamond-like carbon (DLC:H), even though they both have a similar sp3
fraction. In the case of the former, the sp3 content is mainly made up of
C–C bonds, which results in a high-hardness thin film, whereas in the latter
the sp3 content also contains C–H bonding in addition to C–C bonding. In
this review the terms amorphous carbon, a-C, and hydrogenated amorphous
carbon, a-C:H, will be used as generic terms for disordered carbon, either H-
free or H-containing. For specific types of films, terms such as diamond-like
carbon or polymer-like carbon will be used [1].
One of the main driving forces for the technological use of amorphous
carbon thin films is the ability to grow thin films over large area, at low tem-
peratures with excellent uniformity. The low-temperature deposition, often
performed using plasma-enhanced chemical vapour deposition (PECVD), al-
lows the growth onto nonconventional substrates such as organics or glass
substrates. The excellent uniformity of the physical and electronic properties
is also matched by the mirror-smooth quality of the films. Extensive atomic-
force microscopic studies of a-C and a-C:H films have shown that they typ-
Effects of Nanoscale Clustering in Amorphous Carbon 139

Table 1. Physical properties of different forms of a-C thin films

Category sp3 Optical bandgap H Density Hardness


% eV at. % g cm−3 GPa
Polymer-like a-C PAC 60–80 2.0–5.0 40–65 0.6–1.2 Soft
Graphitic-like a-C GAC 0–30 0.0–0.6 0–40 1.2–2.0 Soft
Diamond-like a-C DLC 40–60 0.8–4.0 20–40 1.5–3.0 20–40
Tetrahedral a-C ta-C 65–90 1.6–2.6 0–30 2.5–3.5 40–65

ically have a rms roughness of less than 1 nm. This makes a-C films ideal
for microelectromechanical systems and for hard disk coatings. In addition,
a-C is believed to exhibit excellent biocompatibility and a-C-coated surgical
implants have been demonstrated. Less success has been forthcoming in the
development of active electronic applications of a-C and a-C:H films [2], and
as a consequence it is necessary to examine the electronic properties and the
effects of disorder and localization at a nanometer level. To that end, this ar-
ticle first deals with the physics of the disorder associated with the sp2 phase
and then extends the discussion to the intercluster transport properties of
the films. Finally, field emission from the carbon system is discussed.

2 Disorder in Amorphous Carbon


Amorphous carbon can be considered as a disordered mixed-phase material
consisting of a conductive sp2 phase, embedded in a less conductive sp3 ma-
trix. The sp2 -hybridised carbon atoms are usually in the form of nanometer-
sized clusters, mainly in the form of rings or olephinic chains. These sp2
clusters give rise to occupied π and unoccupied π ∗ bands with the separation
between the bands being related to the size of the cluster. The sp3 com-
ponent tends to be in the form of aliphatic chains of C atoms with C–C
and C–H bonding being present. The optoelectronic properties of a-C and
a-C:H films can be described in terms of transitions between the occupied π
states to the unoccupied π ∗ states. Previous studies have shown [3] that it is
possible to represent the occupied π and unoccupied π ∗ bands by Gaussian
functions centred at Eπ(π∗ ) . The σ and σ ∗ states, which are associated with
sp3 C bonding, lie further separated from each other. By deposition on suit-
able transparent substrates, such as Corning glass, it is possible to extract
the parabolic Tauc gap and the exponential Urbach energy.
• The Tauc band gap corresponds to optical transitions between extended
states, and for the a-C system in the absence of disorder, the Tauc gap
is given by the separation between the π–π ∗ bands with a magnitude of
2 Eπ . The larger the average size of the sp2 cluster, the smaller the Tauc
gap.
140 J. David Carey and S. Ravi P. Silva

• An alternative band gap that is sometimes employed is to measure the


energy at which the absorption coefficient is 104 cm−1 ; this is known as
the E04 gap. Values associated with the E04 gap tend to be larger than
the Tauc gap, as the absorption at 104 cm−1 tends to occur in states
beyond the π and π ∗ band edges. E03 and E05 gaps are also sometimes
quoted in the literature.
• Transitions between extended-to-localised states in amorphous semicon-
ductors are usually characterised by the Urbach energy, E U . The value of
E U is found by fitting an exponential function to the slope of the absorp-
tion edge and has been used as a measure of disorder in other material
systems. For example, in the case of low defect density a-Si:H, the valence
band tail has an exponential slope of about 45 meV, whereas the slope
of the conduction band is 25 meV. In this manner the observed Urbach
energy of 55 meV for a-Si:H is mainly associated with the valence band
and with low-lying defect states.
Fanchini and colleagues have, however, suggested that while the experi-
mentally observed values can be extracted, the validity of this approach for
this dual mixed-phase system may be too simplistic. As a result, care must be
exercised in the interpretation of the Tauc band gap and the Urbach energy
that are obtained [4]. A second measure of disorder, based upon bond angle
distortion, is the full width half maximum of the Raman active G band, Γ G .
This Raman signal is found at around 1580 cm−1 and originates from the E 2g
vibration between sp2 C bonds [5]. Several complementary optical [6,7,8] and
Raman studies [7, 9] have revealed that as the Tauc gap increases the Urbach
energy increases monotonically, but that the width of the G band undergoes
a maximum of about 1.5 eV (Fig. 2).
In this respect, if the Urbach energy and the width of the G band are
valid measures of disorder in the a-C:H system, then they must measure
different aspects or types of disorder. Robertson previously proposed that the
Urbach energy is a measure of an inhomogeneous disorder associated with
different sp2 cluster sizes, whereas the G band width has been attributed to
a homogeneous disorder associated with bond angle disorder [10]. However,
such an interpretation is unable to explain:
(i) why the largest values of E U are observed at the highest Tauc gaps
(Fig. 2a), since the cluster sizes are smallest there is only a small limited
number of different cluster conformations possible;
(ii) the observation of a maximum in the G-band line width with Tauc gap
(Fig. 2b);
(iii) why the G-band position is also dependent on the excitation wave-
length, with the G-band position tending to saturate at ∼ 1600 cm−1
for excitation wavelengths below 350 nm and the peak shifting to lower
energies at longer wavelengths, as shown in Fig. 3a;
Effects of Nanoscale Clustering in Amorphous Carbon 141

Fig. 2. Variation of (a) Urbach energy and (b) linewidth of Raman G band for
different a-C films as a function of optical Tauc gap. The different symbols refer to
different sets of films (see [2])

(iv) the observation that the G-band line width depends on the excitation
wavelength with the narrower values of Γ G observed at increasing ex-
citation energy as seen in Fig. 3b.
Since the Raman spectra are a result of resonant excitation of sp2 clusters,
dispersion of the G peak reflects excitation of clusters with different band
gaps. The saturation of the G-band position at ∼ 1600 cm−1 in Fig. 3a
reflects the maximum possible Raman shift for C atoms bonded in sp2 rings.
The observation of dispersion of the Raman line width implies that there is an
inhomogeneous distribution present in the bond angle disorder. Furthermore,
the reduction of the G width with increasing excitation energy implies that
there is a narrower distribution of higher-gap sp2 states, in contradiction with
the proposal that there must be a larger distribution of sp2 states required for
the large Urbach energy. The increase in the Urbach energy with increasing
π–π ∗ separation and small numbers of possible sp2 cluster configurations,
coupled with the dispersion in the G line width have lead Fanchini and
Tagliaferro to conclude that the Urbach energy in amorphous carbon is not
a good measure of disorder [11]. Furthermore, they went onto propose two
types of disorder:
(i) A structural disorder associated with clusters of the same size but with
different amounts of distortion. This type of inhomogeneous disorder
would increase the Urbach energy as well as broaden the G-band line
width.
(ii) A topological disorder arising from undistorted clusters but of different
sizes. This would also broaden the Urbach energy but have no effect on
the G line width.
142 J. David Carey and S. Ravi P. Silva

Fig. 3. Variation of (a) G-band Raman shift and (b) G-band linewidth for a series
of polymer-like a-C:H films (), diamond-like a-C:H () and graphitic carbon (•)
thin films as a function of Raman excitation wavelength (see [5])

As a consequence, the differences between distorted and undistorted sp2


clusters needs to be explored. The location of the sp2 clusters in the energy
gap depends on two factors: whether they consist of even or odd numbers of
carbon atoms and whether they are distorted. Undistorted even-numbered
clusters will give rise to states near the Fermi level (E F ) only if they are
sufficiently large. This differs from the case of odd-numbered clusters, which
can give rise to gap states even if composed of a small number of atoms. In
general, distorted clusters give rise to states that are closer to E F than undis-
torted clusters. One method that is able to distinguish between the different
types of cluster is to measure the density of unpaired electron spins arising,
for example, from odd-numbered clusters. Such states can be measured by
electron paramagnetic resonance (EPR), also called electron spin resonance
(ESR). A high concentration of paramagnetic defects (1020 cm−3 ) is typically
found in films deposited under energetic conditions. Such energetic conditions
include samples deposited on the driven electrode of a PECVD system [12].
Low defect densities, typically ∼ 1017 cm−3 , tend to be found under less
energetic conditions [13]. The term “defect” is a misnomer since the ESR
active species are generally agreed to result from different configurations of
sp2 clusters. In this manner, ESR can give a measure of the density of sp2
states at the Fermi level, provided that a majority of these states have a net
unpaired electron spin present. It should be noted that ESR spin densities
do not themselves measure the sp2 content.

3 Intracluster Effects in Amorphous Carbon


Several studies have examined the variation of spin density with deposition
conditions, though rarely in terms of relating spin density to localisation of
Effects of Nanoscale Clustering in Amorphous Carbon 143

Fig. 4. Variation of (a) spin density and (b) peak-to-peak linewidth with negative
self-bias for three series of a-C:H films (see [2])

the wavefunction [2]. The variation of the spin density, N s , and peak-to-peak
line width, ∆B pp , with negative self-bias for three different series of films are
shown Fig. 4.
It is evident that the spin density rises from a low value of ∼ 1017 cm−3
and tends to saturate at 1020 cm−3 . The ESR line width initially increases, of-
ten as the spin density increases, but at higher biases the line width decreases.
In this regime the line shape of the ESR signal is Lorentzian. Furthermore,
in these high-bias conditions, the spin densities are typically ∼ 1020 cm−3 ,
corresponding to ∼ 1 at. % of the film. As a result, the ESR signal can be
considered as originating from a dilute paramagnetic material. Abragam’s
formulism may be used to calculate the contribution to the peak-to-peak line
width, ∆B pp , from the dipole–dipole interaction between like spins [14]. Such
a broadening mechanism will produce a Lorentzian ESR line shape, which
is consistent with the ESR line shapes observed. Assuming a spin concen-
tration N s , measured in cm−3 , the contribution to the dipolar interaction
∆B pp , measured in mT, can be given as [12]

4π2
∆B pp = g µB N s . (1)
9

Barklie et al. applied (1) for a typical C-related g value of 2.0025 to ob-
tain the expression ∆B pp = 8.12 × 10−21 N s . The variation of ∆B pp against
N s directly for the same three data sets reported in Fig. 4, as well as the
predicted line width (dashed line) based solely on dipolar broadening us-
ing (1) is shown in Fig. 5. It is apparent that significant reductions in ∆B pp
are observed at high spin densities, indicating an additional mechanism is
responsible for reductions in the line width. This additional interaction is
due to the motional averaging of the electron wavefunction within the sp2
144 J. David Carey and S. Ravi P. Silva

Fig. 5. Variation of peak-to-peak linewidth with spin density for a data in Fig. 4.
The dashed line represents the predicted dipolar contribution to the linewidth based
on (1)

cluster. As the sp2 cluster increases in size, the probability of the electron
being associated with a particular atom decreases. This spreading or delo-
calization of the wavefunction as the cluster size increases is accompanied by
a general reduction in the Tauc gap. Further evidence of delocalization can
also be found in an examination of the spin resonance relaxation times. The
spin–lattice relaxation time, T1 , decreases from 3 × 10−5 s for polymer-like
films down to 2 × 10−7 s for DLC films, which implies a greater interaction
between the spin system and lattice [12]. At the same time, the spin–spin
relaxation times increase, reflecting a change in the exchange frequency. It
has been reported that in films with a high sp2 content that the exchange
frequency is approximately ∼ 1010 rad s−1 .
In addition to the concentration of the sp2 clusters, the size of the sp2
clusters is therefore an important feature of this description. Indeed, there
have been attempts to infer the cluster size and shape using visible Raman
spectroscopy [15]. As a result, considerable interest was generated by the
report [16] of an apparent anisotropy in the ESR signal of defects in DLC
films measured at high frequency and low temperature. A fully amorphous
material with a single spin 12 paramagnetic centre should exhibit a single
isotropic line. In [16] it was proposed that the ESR signal could be assigned
to the sum of an anisotropic powder spectrum with axial g values of g ∼
2.005 and g⊥ ∼ 2.0025, and one symmetric unresolved line with g = 2.0025.
From previous ESR studies of nanocrystalline graphite, it is known that the
Effects of Nanoscale Clustering in Amorphous Carbon 145

g tensor is anisotropic and the g values depend on the average crystallite size.
A value of g of 2.005 was associated [17] with a crystallite of a size less than
7.5 nm. In this way, it was believed that ESR was providing a way to quantify
the size of the nanoclusters. This is an extremely attractive feature since it
has been proposed that the ratio of the intensities of the G and D Raman
bands (the D band being located at 1350 cm−1 and associated with the A1g
breathing mode of 6-fold sp2 rings) can be related to the in-plane correlation
length of disordered graphite. The reason that no anisotropy was observed
at the more conventional 9 GHz room-temperature measurement was due
to the strong exchange narrowing. Unfortunately, in this analysis the role of
demagnetizing fields, which at room temperature and “low” magnetic fields
are negligible, but must be included when operating at 4 K and especially at
higher resonance fields, required at the higher microwave frequencies [18, 19].
When demagnetizing fields are taken into account, an apparent anisotropy of
the resonance can occur since the demagnetizing field results in an effective
shift downwards of the effective g value when the applied Zeeman magnetic
field is perpendicular to the film and results in an up-shift when the applied
field is parallel to the plane.
Apart from changes in deposition conditions, such as self-bias or the ad-
dition of N, nanoclustering within a-C films can be adjusted via thermal an-
nealing. Siegal et al. annealed nonhydrogenated a-C films produced by pulsed
laser ablation and reported the presence of regions 3–5 nm in size which were
5–10% more dense that the surrounding regions [20]. The as-deposited films
has stresses of 5–7 GPa and a film density of 3.0 g cm−3 , but near-complete
stress relief had occurred and the density had dropped to 2.8 g cm−3 with
thermal annealing to 600◦ C. Over the same annealing temperature range
the optical transparency of the film decreased, demonstrating that cluster-
ing of the sp2 within the film has occurred. By considering different bonding
topologies on the basis of Raman spectroscopy, Siegal et al. concluded that
the as-grown films consist of small and isolated sixfold clusters, but that
above annealing temperatures of 300◦ C the fraction of five-membered rings
begins to increase. The presence of five-membered rings was attributed to
the newly formed π-bonded atoms, rather than a reduction in the popula-
tion of the six-membered rings themselves. Despite the reduction in the film’s
density, nanoindentation measurements showed that the nanocomposite films
were 15% harder than the as-deposited films.
Computational studies showed that within this nanocomposite film, the
residual stress consists of an inhomogeneous stress distribution where the
three-fold coordinated atoms are under tensile stress, but that the four-fold
atoms are under a smaller compressive stress [21]. During annealing small re-
gions of high stress relax, leading to the preferential generation of three-fold
coordinated atoms. The stress relief is as a result of fourfold sp3 C bonds being
replaced by threefold sp2 C bonds. This change to the shorter sp2 C bond is
irreversible under normal conditions. If the near-zero stress is achieved due to
146 J. David Carey and S. Ravi P. Silva

high temperature annealing, care must the exercised to prevent an excessive


thermal stress being introduced into the film on cooling back to room tem-
perature. The thermal stress can be eliminated by growing the film at above
room temperature, which introduces some tensile stress. Further evidence of
the formation of clustering in ta-C films was reported in the fluctuation mi-
croscopy studies recently undertaken by Chen et al. [22]. Annealing up to
600◦ C resulted in the increase in locally ordered regions, but the formation
of graphitic ordering did not occur until annealing to 1000◦ C. Much of the
research for stress relief in hard a-C films, especially ta-C films, is driven by
the development of carbon-based microelectromechanical systems.
Evidence for mixed-phase components in a-C has also been obtained by
examining the proton and 13 C relaxation times using nuclear magnetic res-
onance (NMR). Jäger et al. used cross-polarization 13 C NMR to measure
the effects on the proton relaxation times in different environments of films
deposited from acetylene and benzene [23]. A two-component 1 H spin–lattice
relaxation with time constants of 14 and 120 ms was found and interpreted
as being due to the presence of two differently relaxing proton systems. The
shorter relaxation time originates from CH groups in the sp2 and sp3 matrix
and the longer T1 time originating from short CH2 polymer units with an sp3
configuration. In this description the two environments are separated by re-
gions of nonhydrogenated sp2 C. It is was further found that for films grown
by rf glow discharge from benzene at a self-bias voltage of −200 V, the proton
relaxation time of ∼ 10 ms was virtually independent of temperature. This
temperature independence of the shorter T1 component was interpreted in
terms of nuclei being relaxed via spin diffusion to paramagnetic centers. It is
therefore the degree of electron aggregation or clustering around these para-
magnetic centers that determines the proton relaxation. The influence of spin
diffusion to paramagnetic centers as an explanation of the temperature inde-
pendence of the spin–lattice relaxation times implies that an understanding
of the factors that affect the spin density and line width are important.
Tamor et al. estimated from NMR measurements the protonated and
nonprotonated C concentration with either sp2 or sp3 hybridisation [24]. At
a self-bias of −500 V, the H content was estimated to be 36 at. % and the
fraction of protonated sp3 C atoms to be 0.16, nonprotonated sp3 C atoms to
be 0.20, protonated sp2 C atoms to be 0.25, and nonprotonated sp2 C atoms
to be 0.37. For a film density of 1.7 g cm−3 , this result suggests there are
5.1 × 1022 sp2 C atoms cm−3 in the film. If the signal observed from ESR
is associated with sp2 C centers, then for a value of N s of 1020 cm−3 , this
corresponds to 1 spin per 510 sp2 C atoms, or equivalently to 1 spin per 300
atoms of nonprotonated sp2 C atoms. If these spins were randomly distributed
throughout the film, cooperative effects, such as exchange, should not occur.
Since exchange effects have been attributed to films grown at high bias, the
combined use of NMR and ESR confirms and quantifies the clustering of the
sp2 phase has taken place.
Effects of Nanoscale Clustering in Amorphous Carbon 147

4 Intercluster Interactions in Amorphous Carbon


The increase in intracluster delocalization also manifests itself in changes that
can be associated with intercluster interactions. Various transport studies of
a-C films reveal a commonality in behaviour with high resistivity associated
with samples with large Tauc gap. The resistivity decreases as the Tauc gap
decreases and the conductivity associated with various mechanisms such as
variable range hopping in the more conductive DLC films [1]. In the case of re-
sistive polymer-like amorphous carbon, the conductivity has been attributed
to a space charge-induced current mechanism [1]. Improvements in the con-
ductivity have also been reported with nitrogen incorporation and attributed
to a weak “doping” effect [25] or to a reduction of the band gap through
graphitization [26]. In terms of post-deposition processing, transport studies
of annealed films also reveal an improvement in the conductivity. However,
this is almost always accompanied by significant modification to the structure
of the film at a microscopic level. In this respect furnace annealing results in
an improvement in electrical properties but is accompanied by global changes
to the film. Ion implantation as a method of injection of thermal energy is
therefore an alternative process to modify the film properties in a highly
controlled manner with precise depth control by the correct choice of ion
species, ion energy and dose. Using high-dose B+ implantation into polymer-
like films, it is possible to reduce the low-field resistivity from 2 × 1014 Ω cm
(unimplanted) to 6 × 1012 Ω cm (2 × 1014 B+ cm−2 ). Over the same range the
Tauc gap remained constant at about 2.6 eV, indicating that no significant
increase in the mean sp2 cluster size has occurred. For doses greater than
2 × 1014 cm−2 , a fall in the optical gap finally ends with a total collapse to
0.2 eV at a high dose (2 × 1016 B+ cm−2 ), and the resistivity concomitantly
decreases to 5 × 106 Ω cm. The improvement in the electrical characterization
has been attributed to improvements in the cluster–cluster interaction via a
hopping related mechanism (Fig. 6).
During low-dose implantation, localized heating results in localized sp2
clusters, which remain small (as evidenced by the absence of a reduction in
the Tauc gap). Before the formation of damage cascades, the concentration
of the induced sites will be proportional to the ion dose. This nanoclustering
of the sp2 sites, which maintains the wide gap, increases the conductivity by
decreasing the hopping distance. At higher doses, nanostructuring of the bulk
of the film occurs and the band gap decreases. As a result, ion implantation
demonstrates that it is possible to improve the conductivity without inducing
extensive graphitizing of the film.
Further evidence for the idea of dielectric inhomogeneity of conductive
sp2 clusters embedded in a more insulating matrix can be found in the high-
resolution scanning tunneling microscope (STM) for a DLC film, where the
STM results show that there are nanometer-sized regions of higher conduc-
tivity surrounded by other regions of lower conductivity [2]. Similar localized
regions of conductivity have also been recently reported in an STM study of
148 J. David Carey and S. Ravi P. Silva

Fig. 6. Schematic of how the different bias growth conditions can give rise to a
change in the size and concentration of sp2 clusters

sulphur-containing ultrananocrytalline diamond (UNCD) films [27]. UNCD


films consist of nanometer-sized grains surrounded by graphitic grain bound-
aries. The surface density of states was determined from the normalized dif-
ferential conductivity, which for sulphur-rich films showed an oscillatory be-
haviour. In UNCD films, it was reported that the sulphur acts both to dope
the films but also to introduce localized defects. In both cases increasing the
concentration and size of the clusters results in improved localized electrical
conductivity. This is an important result since conventional “large-area” con-
tacts used in current–voltage characteristics would mask the localized nature
of the conductivity.

5 Field Emission from Amorphous Carbon


The implication of this “dielectric inhomogeneity” can also be extended to
examine the field-induced electron emission from a-C:H films. Application
of an applied electric field can result in electron emission from the surface.
In the case of PAC, films it has been reported [28] that the threshold elec-
tric field for emission exhibited a dependence with the film thickness with
a minimum threshold observed for a thickness of 65 nm. This behavior was
attributed to the effects of internal high electric field effects within the film
and the absence of any significant screening of the applied electric field. Such
an explanation is possible when one considers that the electric field from
the anode will terminate on the “more conductive” sp2 clusters. At a low
density (∼ 1017 cm−3 ) screening of the bulk of the film will not occur. In
Effects of Nanoscale Clustering in Amorphous Carbon 149

such a situation the controlling step in the electron emission process is at


the film/substrate. A different situation will result for films grown at higher
biases when the defect density increases. For two films deposited at −90 V
and −265 V self-bias, it was observed [29] that there was little dependence
on the film thickness and the lowest threshold field was reported for the film
grown at the highest bias, consistent with the model presented in Fig. 6.
Here, the film with the largest bias has the greatest intercluster interactions
since the clusters are larger and the cluster–cluster separation will be the
lowest. This gives rise to an emission mechanism that is dominated by the
front surface properties of the film. Furthermore, the local electric field in the
neighbourhood of the clusters is enhanced, resulting in lower than predicted
threshold fields for emission.
Finally, it has been reported in several studies that the onset of stable
field emission, often in more resistive samples, occurs only after several volt-
age cycles [30,31]. This conditioning behaviour often results in lower threshold
fields. It has been shown that it is possible to condition a PAC film by current
stressing, by intentionally passing a current of suitable magnitude through
the film [31]. Mercer et al. performed a similar experiment using a scanning
tunneling microscope tip to generate a highly spatially localized electric field
and effectively current stress ta-C films [32]. They observed that after ramp-
ing the tip–sample bias and current, nanostructures of about 100 nm in extent
form. By using high-resolution spatially-resolved electron energy loss spec-
troscopy (EELS), they showed that the predominant bonding configuration
changes from predominately fourfold coordinated C to threefold coordination.
Changes in the sp2 bonding have also been reported for heavy ion irradiation
of S-doped UNCD films [33]. High-energy (GeV/amu) Fe and Si ions were
used, and it was reported that there was a reduction in the threshold field af-
ter implantation for irradiated films and this improvement in threshold field
was accompanied by changes in the sp2 phase as inferred from by Raman
spectroscopy. The net effect of the conditioning, current stressing or heavy
ion treatment is to generate conductive sp2 -rich areas or filaments through
localized Joule heating. These conductive regions can then be viewed as ei-
ther isolated sp2 clusters or a continuous sp2 network that can lead to high
field enhancement factors, which result in reduced threshold fields.
Further evidence of the importance of the sp2 phase in field emission
comes from a comparative study of the threshold field with the ratio of the
I D /IG bands found in Raman spectroscopy. For a range of different types of
a-C films (including ta-C, ta-C:N, ta-C:H and DLC films [16] and S-doped
UNCD films [34]), it was observed that the threshold field is correlated with
the in-plane correlation length, suggesting sp2 cluster sizes of around 1–2 nm.
The in-plane correlation length is inferred from the ratio of the intensities of
D and G Raman bands.
150 J. David Carey and S. Ravi P. Silva

6 Conclusions
In conclusion, the disorder inherent in amorphous carbon films plays a major
role in determining the electronic properties. An understanding of the role
of disorder is important. PAC films have small clusters with a small distri-
bution of cluster sizes and are dominated by topological disorder in which
the Urbach energy is not a good measure of disorder and topological disorder
dominates. In DLC films a reduction in the Tauc gap and blue shift of the
G-band implies a higher concentration of larger clusters is present. Further-
more, the increase in spin density (1020 cm−3 ) coupled with the increase in
the G band width implies more distorted clusters are present. At the higher
spin density the ESR line width is no longer determined by the dipole inter-
action, with intracluster exchange interactions determining the line width.
In this regime, both topological and structural disorder are present and can
effect the stress in the film. The disorder is dominated by structural disorder
with little topological disorder, thereby reducing the line width of G band.
The clustering can be adjusted by thermal annealing or ion implantation. In
addition, the sp2 phase plays an important role in the field emission from
these films.

Acknowledgements

The authors acknowledge funding from the EPSRC, and JDC acknowledges
the funding of an Advanced Research Fellowship from the EPSRC.

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Index
a-C, 137, 149 cluster size, 139–141, 144, 147
a-C:H, 138 distorted clusters, 142
2
sp -bonded clusters, 137, 139, 142 intercluster interaction, 137, 147
152 J. David Carey and S. Ravi P. Silva

intracluster interaction, 137, 142, 150 G band, 140, 141


undistorted clusters, 142 G-band, 150
sp2 -chains, 139 G-band, 145, 149
sp2 -rings, 139, 141, 145 graphite-like carbon (GLC), 139, 142
five-fold rings, 145 graphitization, 147
six-fold rings, 145
ta-C, 138, 149 hydrogenated diamond-like carbon
ta-C:H, 149 (DLC:H), 138, 142, 149
ta-C:N, 149
nitrogen incorporation, 147
amorphous carbon thin films, 137
optical properties, 137
cluster-cluster interaction, 147
plasma-enhanced chemical vapour
cluster-cluster separation, 149
deposition (PECVD), 138, 142
clustering, 137, 145, 146
polymer-like carbon (PLC), 138, 139,
142, 144, 147
D band, 145, 149
D/G-band intensity ratio, 145, 149 Raman spectroscopy, 137, 140–142,
defects, 142, 144, 148 144, 145, 149
diamond-like carbon (DLC), 138, 139,
144, 147, 149, 150 scanning tunneling microscopy (STM),
disorder, 137, 139–141, 150 147
homogeneous disorder, 140
inhomogeneous disorder, 140, 141 Tauc gap, 137, 139–141, 144, 147, 150
tetrahedral amorphous carbon, 139
electron paramagnetic resonance
(EPR), 142 ultrananocrytalline diamond (UNCD),
electron spin resonance (ESR), 142–144, 148, 149
146, 150 Urbach energy, 137, 139–141, 150
Elastic and Structural Properties of Carbon
Materials Investigated by Brillouin Light
Scattering

Marco G. Beghi, Carlo S. Casari, Andrea Li Bassi, and Carlo E. Bottani

NEMAS-Center for “Nano-Engineered MAterials and Surfaces”, and


Dipartimento di Ingegneria Nucleare, Politecnico di Milano, Via Ponzio 34/3,
I-20133 Milano, Italy
marco.beghi@polimi.it

Abstract. Brillouin light scattering (BS) is a nondestructive technique exploited


to investigate collective excitations in solids: acoustic phonons, spin waves, magnons
and density fluctuations. In particular, it permits users to characterize dynamical
structural and nanomechanical properties of materials through the detection of ther-
mally excited surface and bulk acoustic phonons. This gives access to information
about both surface and bulk structural properties in the spatial range from a few
nanometers to several hundred nanometers. Here we show how BS has been widely
and successfully used to study various carbon-based materials ranging from ultra-
thin tetrahedral amorphous carbon films to carbon nanotubes. These materials are
interesting for both technological applications and fundamental research.

1 Introduction
Carbon-based materials are currently exploited, or being considered, for a
variety of applications. Suitable characterization techniques are therefore
needed in order to investigate a wide spectrum of properties, in particular
mechanical and structural properties are of paramount interest to study struc-
tural materials and films for coating applications. Brillouin scattering (BS)
permits us to characterize dynamical structural and mechanical properties of
materials through the detection of thermally excited surface and bulk acoustic
waves. This gives access to information about both surface and bulk struc-
tural properties at the mesoscale (from a few nanometers to several hundred
nanometers). Here we show how BS has been widely and successfully used
to study a large variety of carbon-based novel materials, of interest for both
technological applications and fundamental research aspects.
Inelastic scattering of visible light is a contactless, nondestructive mea-
surement technique that can be employed to investigate various types of
collective excitations in solids. Measurements are performed by illuminat-
ing a sample with a focused laser beam and analyzing the spectrum of the
scattered light. Most of the light is elastically scattered and remains at the
laser frequency, while the light that interacts with some kind of excitation
undergoes a frequency shift.
G. Messina, S. Santangelo (Eds.): Carbon, The Future Material for Advanced Technology Ap-
plications, Topics Appl. Phys. 100, 153–174 (2006)
© Springer-Verlag Berlin Heidelberg 2006
154 Marco G. Beghi et al.

In Raman scattering a photon interacts with a single optical phonon, i.e.,


an oscillation of local, atomic degrees of freedom, and thus provides infor-
mation mainly on local order at an atomic scale. In carbonaceous materials
Raman scattering involves frequency shifts in the 102 –103 cm−1 range, i.e.,
phonons of frequencies ranging from a few THz to one hundred THz. In
BS a photon interacts with an acoustic phonon having wavelength of the
same order of the optical wavelength, i.e., a bulk or surface acoustic wave of
submicron wavelength [1, 2, 3, 4, 5]. The involved frequency shifts are the fre-
quencies of the acoustic waves of such wavelengths; they depend on material
properties and on the type of acoustic mode, and typically lie in the GHz
to one-hundred GHz range, i.e., a fraction to a few cm−1 . These frequencies
are determined by the elastic properties at the wavelength scale, and thus
provide information on material properties at such a scale.
Interactions with single phonons, i.e., traveling excitations, give Stokes–
anti-Stokes doublets: couples of down-shifted and up-shifted peaks, at well-
defined frequencies. Interactions can also occur with nontraveling excitations
(quasi-elastic scattering), or involving more phonons (multiphonon Raman
scattering). Both these mechanisms give a single broad peak centered at null
frequency shift, having width typically comparable to the Brillouin shifts [6].
Other techniques to measure the characters of acoustic waves, like quan-
titative acoustic microscopy [7] and the so-called laser acoustic technique [8]
are based on the excitation of acoustic waves, respectively by a piezoelectric
transducer and by a laser pulse, and on the observation of their propagation
over millimeter distances. Such techniques typically operate in the tens to
hundreds of MHz frequency range. BS measurements do not involve the ex-
citation of acoustic waves, but exploit the spontaneous thermal fluctuations
of the acoustic modes. The amplitude of these fluctuations is small and re-
quires longer measurement times (tens of minutes up to some hours), but
the acoustic modes are observed at higher frequencies (tens of GHz) and lo-
cally. Light scattering occurs in the focusing spot of the laser and does not
imply acoustic wave propagation over macroscopic distances. These charac-
teristics qualify BS as a nondestructive, contactless testing technique that is
also applicable to small samples.
BS can occur by interaction with either bulk acoustic waves, in transpar-
ent or semitransparent media, or surface acoustic waves (SAWs), at the sur-
face of any kind of material. Bulk waves are characterized by their wavevec-
tor k, while SAWs have a wavevector k parallel to the surface. When acoustic
waves are detected, their velocity is measured: the wavevector is determined
by the scattering geometry (see Sect. 2), the circular frequency ω is measured
from the spectrum, and the acoustic velocity v = ω/k or v = ω/k is immedi-
ately obtained. In homogeneous solids the acoustic velocities are independent
of wavelength, while they depend on the mode polarization and, in anisotropic
media, on the propagation direction. At the surface of a homogeneous solid
only one type of SAW exists: the Rayleigh wave, of velocity v R . The dis-
Brillouin Light Scattering 155

placement field of this type of wave decays exponentially with depth, the
decay length being of the same order of the wavelength 2π/k . The Rayleigh
wave can be considered the prototype of the various SAW types. In layered
solids, beside a Rayleigh wave modified by the layered structure, other types
of SAWs can be present, depending on layer thickness and properties: Sezawa
waves, Love waves, pseudo surface waves [9]. Differently from homogeneous
solids, layered media have an intrinsic length scale; consequently, the veloc-
ity of all the modes supported by layered structures generally depends on
wavelength, and the dispersion relation v(k ) can be measured. In particular,
for a single supported film of thickness h on a homogeneous substrate, the
velocity of SAWs is a function of the nondimensional product k h [2, 3].
The acoustic properties of materials or of layered structures are the direct
outcome of BS measurements. The acoustic properties are of direct interest
only for specific applications, but they provide a useful tool to probe other
properties, namely the elastic properties, which are of interest in various
cases, like, e.g., for coatings. Indentation techniques directly give the hard-
ness, and instrumented indentation supplies one combination of the elastic
moduli [10, 11]. However, also in the simplest case, the isotropic medium, the
full characterization of the elastic properties requires two independent para-
meters, to be chosen among Young’s modulus E, shear modulus G, bulk mod-
ulus B, Poisson’s ratio ν, or among the elements Cij of the elastic constants
tensor. Any pair of these parameters uniquely determines all the others.
BS can be exploited to measure these parameters. This Chapter is mainly,
although not exclusively, devoted to a discussion of the measurement and data
analysis techniques. The velocity of bulk acoustic waves is easily computed as
a function of the mass density ρ and the elastic constants Cij of the material
supporting them. The velocity of SAWs in layered media can be computed
as a function of the material properties and the thickness of all the layers.
The properties of the layer(s) can be derived by fitting the computed dis-
persion relations to the measured ones. In reality the available information
is generally not sufficient to derive all the mentioned properties; the most
frequent applications concern either bulk nonmetallic samples or single sup-
ported films. In the first case the mass density is independently measured and
the elastic constants are obtained [4, 12, 13, 14]. In the second case one ex-
ploits the substrate properties and values of film thickness and mass density
independently obtained, e.g., by X-ray reflectivity measurements, to derive
the film elastic constants [5, 15, 16, 17, 18]. It can be noted that, since the
probed acoustic wavelengths are submicrometric, in films having thickness of
a few micrometers the bulk waves are fully present and measurable (if the
material is sufficiently transparent), while SAWs are entirely confined within
the film, and are unaffected by its finite thickness. In other words, from the
point of view of BS, films having thickness above a couple of microns are
indistinguishable from a semiinfinite medium [19, 20], except for the acoustic
modes having a wavevector normal to the surface [21].
156 Marco G. Beghi et al.

Fig. 1. Scheme of the experimental set-up for Brillouin scattering experiment in


the backscattering configuration. Sp: specimen; θi : incidence angle; M: mirror; L1–
L4: lenses; P: pinhole for spatial filtering; FP: Fabry–Perot interferometer (a single
interferometer is shown, for clarity, instead of the tandem multipass interferometer
actually exploited); D: light detector

In the following sections the experimental and data analysis techniques


are first discussed. A general overview of the applications of BS to various
types of carbonaceous materials is then presented. Two specific cases are
finally reviewed in more detail to show the potential of the technique: the
measurement of the elastic constants of ultra-thin (down to 2 nm) tetrahedral
amorphous carbon films of high density and stiffness, and the characterization
of single-walled nanotubes (SWNT).

2 Experimental Technique

As mentioned above, BS measurements are performed illuminating a sam-


ple with a focused laser beam, collecting the scattered light and analyzing its
spectrum. The incidence and collection directions define the scattering geom-
etry. In the backscattering configuration the two directions coincide and are
at an angle θi from the normal to the specimen surface (Fig. 1). This config-
uration is the most common one, since it has some advantages: it maximizes
the acoustic wavevector k, and it exploits the same lens to focus the incident
laser beam and to collect the scattered light, instead of needing two separate
optics.
In the scattering event, energy conservation has the form

Ω s = Ω i ± ω, (1)

where Ω i and Ω s are the circular frequencies of the incident and scattered
light, respectively. The + and − signs refer to anti-Stokes (phonon annihi-
lation) and Stokes (phonon creation) events, respectively. The spectrum of
scattered light is dominated by the light at the same incident frequency Ω i ,
Brillouin Light Scattering 157

elastically scattered by static inhomogeneities. As indicated by (1) it also


contains one or more doublets, symmetric with respect to Ω i . In scattering
by bulk waves, wavevector conservation has the form

q s = q i ± k, (2)

where q i and q s are the wavevectors (in the material) of the incident and
scattered light; the sign refers again to anti-Stokes and Stokes events. In
scattering by SAWs the absence of translational invariance in the depth di-
rection leads to the nonconservation of the wavevector component in that
direction: (2) holds only for the two components parallel to the surface, in
the form

q s = q i ± k . (3)

Obviously, Ω i = (c/n) |q i | and ω = v |k|, where v is the velocity of the acoustic


wave and (c/n) is the velocity of light in the material, c being its velocity
in vacuum and n being the refractive index. Since (2) and (3) imply that
|k| and k  are at most of the same order of |q i | and q i , it follows that
ω/Ω i is at most of the same order of the ratio v/(c/n)  1. This means that
Ω s  Ω i and, accordingly, |q s |  |q i |: the modulus |q i | = n (2π/λ0 ) being
determined by the laser wavelength λ0 , in a given experiment the probed
acoustic wavevector is fully determined by incidence and scattering direc-
tions. For backscattering by bulk waves, |q i | = 2 (2π/λ0 ) n. This marks a
difference with the other techniques to measure the acoustic properties [7, 8]:
in these techniques the experiment selects the frequency, and the wavelength
is determined by the material properties. Consequently, hard materials, which
are acoustically fast, are probed at longer wavelength. In BS experiments the
acoustic wavelength is instead selected, irrespective of the material proper-
ties, and the latter determine the acoustic frequency.
It must be remembered that Snell’s law means that upon refraction the
parallel component of the optical wavevector remains unchanged. Conse-
quently, q i and q s are completely determined by the incidence and scatter-
ing angles θi and θs , and are independent of the refractive index n. Therefore
the analysis of surface Brillouin scattering (SBS) results does not require the
value of n. In backscattering
 
k  = 2 |q i | sin θi = 2 2π sin θi , (4)
λ0
and the relative difference |Ω s − Ω i | /Ω i = |q s − q i | /q i reaches its maximum
value (for scattering by SAWs) 2 (v SAW /c) sin θi , which is, for any material,
well below 10−4 , down to below 10−6 . A typical experimental set-up for this
scattering configuration is presented in Fig. 1. The laser beam is directed
onto the specimen by a small mirror and focused onto the specimen surface
by a lens, which also collects the scattered light. Spatial filtering by a pinhole
158 Marco G. Beghi et al.

is typically needed, and the filtered scattered beam goes to the spectrometer.
A more complete analysis would consider the finite collection solid angle:
the lens collects all the scattered wavevectors belonging to a cone around
the nominal backscattering direction q s = −q i . Computation of the average
exchanged wavevector leads to a correction to (4) [3, 22].
The analysis of Brillouin spectra is difficult because the doublets to be
measured (1) have, as noted above, a very small relative frequency shift ω/Ω i
from the elastic peak at Ω i , whose intensity is larger by several orders of mag-
nitude. Diffraction gratings are not sufficient, and surface Brillouin spectra
became observable with the introduction of the tandem multipass Fabry–
Perot interferometer [1, 23, 24]. The interferometer is operated as a narrow-
bandwidth, high-contrast tunable band-pass filter [2, 25], and light is finally
detected by a photomultiplier, operated in the single-photon counting mode.

3 Derivation of the Elastic Constants


A Brillouin spectrum gives the velocities v = ω/k and/or v = ω/k of the
bulk and surface acoustic waves which give spectral doublets. SAWs are of
particular interest for supported films. Since the value of k is determined by
the incidence angle (4), a set of measurements at different incidence angles
allows us to measure several points of the dispersion relation v SAW (k ). The
bulk wavevector |k| is instead independent of the incidence angle (except at
most for anisotropy effects), but this is not a limitation because, since bulk
wave velocities do not depend on |k|, the measurement of a dispersion relation
is not needed.
In the simplest case, the isotropic medium, longitudinal
 and transverse

bulk waves exist. Their velocities are simply given by C11 /ρ and C44 /ρ,
respectively, and the two moduli are immediately obtained if both types of
waves give measurable spectral peaks and if the mass density is known. In
an isotropic medium the whole tensor of the elastic constants is completely
determined by only two independent quantities, and the elastic behavior of
the material is thus fully characterized. In anisotropic media (single crys-
tals) the number of independent elastic constants is higher, and there are
generally three different bulk waves, because the two different transverse po-
larizations are no longer equivalent. The velocities of these waves have more
complex expressions, functions of the propagation direction. In the case of
bulk crystals the complete elastic characterization depends on the specific
crystal symmetry and typically needs measurements with different directions
of k, possibly requiring crystals with different cuts. The behavior of bulk
waves has to be kept in mind also for the analysis of films, because, as noted
in Sect. 1, for film thicknesses above about one micrometer, data analysis can
be performed as for a semi-infinite medium; this also means that in this case
a precise knowledge of film thickness is not required.
Brillouin Light Scattering 159

In the case of a semi-infinite medium, either isotropic or anisotropic, only


one type of SAW generally exists: the already-mentioned Rayleigh wave. It is
a true surface wave, meaning by this that its velocity is lower than that of any
bulk wave, that its displacement field vanishes at increasing depth (for the
Rayleigh wave it declines exponentially) and that its energy flow (the acoustic
Poynting vector) is strictly parallel to the surface. In the case of layered
media other types of SAWs can exist [9, 26, 27, 28]. Considering in particular
a single supported film, the Rayleigh wave generally exists, modified by the
presence of the film (modified Rayleigh wave, MRW) but preserving its main
character. If the film is acoustically slower than the substrate it can act as a
waveguide, supporting guided modes (Sezawa waves), which are reminiscent
of the acoustic modes in free-standing plates (Lamb waves) and have the
character of true surface waves. Both the Rayleigh and the Sezawa waves are
polarized in the sagittal plane, defined by the propagation direction and the
normal to the surface. Transverse waves, polarized in the surface plane (Love
waves) also exist.
Along a stress-free boundary pseudo surface waves (PSAWs) can also
exist. They do not have the character of true surface waves: their velocity is
not lower than that of any bulk wave, and they radiate part of their energy
towards the interior of the medium; accordingly, their displacement field does
not vanish at infinite depth. However, when their displacement field is still
mainly confined in the vicinity of the surface and the rate at which they
lose energy towards the bulk is low, they resemble to true SAWs, and in
BS measurement they give doublets exactly as true SAWs. Of particular
importance in the case of films acoustically faster than the substrate is the
wave called “leaky longitudinal surface wave” or longitudinal resonance: it is
a PSAW that, at the surface, is longitudinally polarized.
The velocities of all these waves can be computed, as functions of the
mass density and the elastic moduli of all the layers, and of the thickness of
the layers (of the product k h for a single supported film). If the dispersion
relation v SAW (k ) is measured for a set of values of k , obtaining a set of
values {vi meas. }, the same set of velocities can be computed as function of
some free parameter, namely the elastic moduli Cj , obtaining the values
{vi comp.(Cj )}. The free parameters Cj are then identified by a standard least
squares minimization procedure. The sum of squares is computed:
  vi comp. (Cj ) − vi meas. 2
χ2 (Cj ) = , (5)
i σi
where the general case has been considered, in which the variances σi of each
vi meas. can be individually estimated. Following standard estimation theory,
the minimum of χ2 (Cj ) identifies the most probable values (C j ) of the para-
meters in the (Cj ) space, and the isolevel curves of the ratio χ2 (Cj )/χ2 (C j )
identify the confidence region at any predetermined confidence level [17, 29].
If the minimum of χ2 (Cj ) is well defined, the isolevel curves identify a lim-
ited region in the (Cj ) space, resulting in a rather precise measurement of
160 Marco G. Beghi et al.

the Cj parameters [16, 17, 18]. In other cases the function χ2 (Cj ) has rela-
tively low values in a broad region [30]; for instance, in a two-dimensional
(Cj ) space, it can have the shape of an elongated valley [31]. In such cases
precise measurements of the Cj parameters are not achieved, although in
some cases a combination of the parameters exists, which is identified with a
better precision than the individual parameters [18].
The information that can be obtained on the Cj moduli depends obviously
on the amount of information available from the dispersion relations. If only
the modified Rayleigh wave is observed, the Cj parameters are generally not
identified with good precision, but if further acoustic modes are observed, ei-
ther Sezawa waves [32] or longitudinal guided modes [33, 34], the precision of
the measurement of the Cj moduli increases significantly [15,16,18,29,31,35].
In particular, in isotropic materials the longitudinal guided mode has a
wavevector parallel to the surface, and the same velocity of the longitudi-
nal bulk wave: without needing the value of the refractive index, it directly
supplies the value of the C11 elastic constant [33].
The information that can be derived when only the modified Rayleigh
wave is detected was assessed by a sensitivity analysis [36]. For the repre-
sentative model case of an isotropic film on a silicon substrate, it was found
that the modified Rayleigh wave velocity is indeed sensitive to the values of
the Young modulus E and the shear modulus G, but very slightly sensitive
to the Poisson’s ratio ν, the bulk modulus B and the C11 elastic constants.
This means that both E and G can be determined with good precision, and
that a similar precision cannot be achieved for ν, B and C11 . This is not con-
tradictory with the fact, remembered above, that in an isotropic medium the
values of two elastic constants are sufficient to determine all the others. The
moduli ν, B and C11 , viewed as functions of E and G, are functions charac-
terized by steep slopes. Consequently, even a small region in the (E, G) plane,
corresponding to a good identification of these two parameters, corresponds
to wide intervals of ν, B and C11 , corresponding to a poor identification of
their values. For Poisson’s ratio ν the interval can be numerically not very
wide, but easily covers a substantial fraction of the range (0, 0.5) which is
the meaningful range for this parameter. The same analysis showed that the
sensitivity to the film thickness and mass density is not high. This is an
interesting result, as it means that, for the precise measurement of the elas-
tic moduli, extremely accurate values of thickness and mass density are not
crucial.
It must be remembered that not all the (E, G) plane is physically mean-
ingful. Since ν = E/2G − 1, in the (E, G) plane the ν = const lines are
straight lines through the origin, and the ν = 0.5 and ν = 0 lines are the
G = E/3 and G = E/2 lines. These lines delimit the triangle that is fully
meaningful. The condition ν ≤ 0.5 is required for thermodynamic stability;
the condition ν ≥ 0 is not strictly required (thermodynamic stability only
requires ν ≥ −1), but is violated only in extremely rare and peculiar cases.
Brillouin Light Scattering 161

4 Brillouin Scattering from Carbonaceous Materials


BS has been extensively used to characterize carbonaceous materials, al-
though in several cases their scattering cross section seems to be relatively
low. In the case of diamond this possible limitation is overcome by the high
thermal conductivity, by which the samples can withstand a high incident
laser power without being damaged. In other cases long measurement times
allow researchers to reach a sufficient counting statistics also with weak sig-
nals, but for some types of “diamond-like carbon” the scarcity or absence of
published BS measurements is probably to be ascribed to the low scattering
cross section. A synthetic overview of published BS results is given here.
In crystalline graphite the elastic constants had already been measured
by ultrasonic techniques, but these techniques had proven to be unable to
reliably measure C44 , due to dislocation motion at the achievable ultrasonic
frequencies. Attempts to avoid this problem had been made by performing
measurements on graphite irradiated to pin the dislocations. BS avoids this
problem by operating in a much higher frequency range. The values of C44
obtained by BS by different authors [37, 38] are in reasonable agreement
among them, and similar to the values obtained from neutron scattering, but
significantly higher than those found by ultrasonic techniques. The remaining
difference among the BS results can be ascribed to crystallite size effects [39].
If the crystallites are not much larger than the acoustic wavelength, and
the measurement spot encompasses several, not perfectly aligned crystallites,
their boundaries have a significant influence on propagation properties [38].
If instead the crystallites are much larger than the the acoustic wavelength
and the measurement spot, the boundaries have no effect [37, 39].
In crystalline diamond the most accurate measurements were performed
by Grimsditch’s group, who also reviewed previous works [4, 13]. They mea-
sured with great precision the elastic constants of natural composition dia-
mond and isotopically enriched diamond [13], finding, for natural composition
diamond, C11 = 1080.4 GPa, C12 = 127 GPa and C44 = 576.6 GPa. These
values correspond to a bulk modulus B = 444.8 GPa. The temperature de-
pendence of these moduli was also measured [14], finding a decrease of only
8% for temperatures up to 1600 K.
Various measurements have been performed on CVD polycrystalline di-
amond films. Measurements on 400 µm thick films, in which the crystallite
size is much larger than wavelength, give values of the elastic moduli in
agreement with those found for crystalline diamond, with a Rayleigh velocity
v R = 10326 ± 470 m/s, consistent with the (110) texture of the film [40].
Measurements on different films give results that depend significantly on
film quality [20]. Exploiting a peculiar Brillouin scattering configuration and
known values of the stress coefficients for diamond single crystals, Krüger
et al. were able to evaluate the internal stresses in CVD diamond [41]. They
found stresses up to several GPa, without a clear difference between the nu-
cleation side (nanocrystalline) and the growth side (microcrystalline).
162 Marco G. Beghi et al.

The ability of BS to perform measurements on submillimeter-sized sam-


ples was exploited to measure the elastic constants for two types of materials
that can be obtained only in small samples: fullerite fcc crystals [19] and the
hard amorphous carbon phases which can be synthetized, at high tempera-
tures and pressures, from fullerite [42]. In the latter case BS found, for both
bulk acoustic waves and SAWs, velocities that approach those of diamond,
up to around 90% of diamond values [42].
Hydrogenated amorphous carbon films were characterized by BS [43].
Measurements performed in conjunction with nanoindentation [44] were an-
alyzed with an a priori assumption about the value of Poisson’s ratio, while
in other cases [34] such an assumption was not needed. Films of non-
hydrogenated amorphous carbon, with different fractions of sp3 bonding,
were characterized by various authors [33, 34, 45]. In these works, besides
the Rayleigh wave, other surface or pseudo surface acoustic modes could be
measured. For films acoustically slower than the substrate it was a Sezawa
wave [45], while for films acoustically faster than the substrate it was a pseudo
surface mode, the so-called longitudinal guided mode [33, 34]. In both cases
the additional information coming from the second mode allowed a better
determination of the elastic constants. Ultra-thin films (down to 2 nm) of
tetrahedral amorphous carbon films of high density and stiffness only perturb
the Rayleigh wave of the substrate, without adding other modes; nevertheless
this perturbation could be measured, allowing researchers to characterize the
ultra-thin films, as reviewed in the next section.
The characterization by BS of low-density nanostructured carbon films
deposited by low-energy cluster beam deposition was also possible [46], de-
spite the relatively high porosity and roughness of such films. At least for
some types of such films acoustic phonon propagation is supported, and their
detection is possible for films deposited on highly reflective aluminum sub-
strates.
Single-walled nanotubes (SWNT) are a peculiar type of carbon material.
BS from aligned nanotubes could be detected, allowing a characterization of
the graphene sheet forming the tube wall, as reviewed below.

5 Ultra-Thin Carbon Films


Ultra-thin diamond-like carbon films, of thickness down to 2–5 nanometers,
have been developed as protective coatings of magnetic hard disks and the
corresponding reading/writing head. The distance between the recording
head and the magnetic material has to be decreased, in order to further
increase the storage density [47], and a reduction of the thickness of the
protective coatings of the disk and the head is required. Carbon coatings
are already a current choice to provide protection against corrosion, graft-
ing sites for the lubricant molecules and mechanical protection [47]. In order
Brillouin Light Scattering 163

to achieve a storage density of 100 Gbit/in2 , coatings having thickness re-


duced to 2–5 nanometers, but maintaining the peculiar properties of thicker
diamond-like films, are needed; coatings of even lower thickness are currently
being investigated. The characterization of such thin films is a challenging
task. The measurements achieved by BS are discussed here. With thicker
films the influence of film properties on the modified Rayleigh wave velocity
is higher: several cases in which the film properties could be determined were
mentioned above. Ultra-thin films induce instead only a small perturbation of
the wave velocity, which remains mainly determined by the substrate prop-
erties. The ability to detect these perturbations and to interpret them is a
good proof of the potential of the technique.
Ultra-thin carbon films are amorphous, and therefore isotropic: as already
noted, only two independent parameters are sufficient to fully characterize
their stiffness. For ultra-thin films their measurement becomes difficult. Me-
chanical characterization is often performed by instrumented indentation,
which directly gives the hardness, and one combination of the elastic mod-
uli [10,11]. However, when the film thickness is reduced to tens of nanometers
or even less, the requisite that indentation depth be significantly smaller than
film thickness cannot be met, and the results are determined by the substrate
rather than by the film. Other means have then to be exploited to measure
the elastic moduli. As discussed above, SBS, allowing the measurement of
acoustic waves of wavelength down to a quarter of a micron, is a precious
tool.
We review here BS measurements performed on tetrahedral amorphous
carbon (ta-C) films deposited using an S-Bend Filtered Cathodic Vacuum
Arc (FCVA) with an integrated off-plane double bend (S-Bend) magnetic
filter; the deposition chamber was evacuated to 10−8 Torr. This deposition
method proved able to deposit ta-C films with particle area coverage of less
than 0.01% and uniform thickness [48]. Samples of thickness ranging from
2 to 8 nm were considered, together with a bare silicon substrate, which is in
reality covered by a thin layer of native oxide due to exposure to air.
The thickness and mass density of the films were obtained by X-ray reflec-
tivity measurements, performed on a Bede GXR1 reflectometer with CuKβ
radiation. Reflectivity curves for supported films typically consist of a critical
angle peak, followed by a long decay. Superposed on this decay are oscilla-
tions (interference fringes) due to the interference of waves reflected from the
surface and the substrate interface. Usually, the density is directly derived
from the critical angle [48]. However, for thickness below about 20 nm the
X-ray evanescent wave reaches the substrate; consequently, the critical angle
turns out to be determined by the substrate rather than by the film. The film
density must then be derived by a fit of the whole experimental reflectivity
curve to a simulated scattering curve computed from model structures [49];
this was performed by the Bede REFS-MERCURY code [50]. For low thick-
ness the interference fringes on the decay become wider, and their number is
164 Marco G. Beghi et al.

reduced. However, comparison of the reflectivity profiles from the bare sili-
con and from the coated samples shows evidence of at least one broad fringe,
from which the thickness can be measured.
It is known from measurements on thicker ta-C films [51] that in this kind
of films the properties can have a gradient in proximity of the outer surface
and the inner interface, the mass density declining when approaching the
two surfaces. Also in these nanometric films the X-ray measurements gave
indications of such a gradient: the fit to the experimental reflectivity curve
improved if a three-layer model was considered, with thin layers of lower
density on the two sides of the main carbon film. However, adopting such a
three-layer model the individual layer properties could not be identified with
good precision. Furthermore, characterization of the elasticity of a three-layer
model requires six independent parameters, and their identification would
remain an undetermined problem. In order to avoid these complexities, both
the X-ray and SBS results were interpreted in a consistent way, modeling the
films as single homogeneous equivalent films, with a sharp interface with the
substrate.
SBS measurements were performed at room temperature exploiting the
514.5 nm line of an Argon ion laser and a 3 + 3 passes tandem interferome-
ter [2], the type of spectrometer most commonly adopted in Brillouin spec-
trometry. Measurements were performed in backscattering, with incidence
angle ranging from 30◦ to 70◦ . SAW propagation was along the [100] direc-
tion on the (001) face of the Si substrate. The incident light was p-polarised,
the scattered light being collected without polarisation analysis. The incident
power on the specimen was around 100 mW, focused into a spot of the order
of 103 µm2 ; irradiation did not induce film modifications.
Films of such low thickness do not alter the spectrum of SAWs of the
substrate: the Rayleigh wave undergoes a slight modification of its velocity,
but remains the only type of SAW supported by this structure. As indi-
cated in Sect. 3, its velocity was computed [9] as a function of the elas-
tic constants and mass density of both the film and the substrate, of film
thickness and of the wavevector k . The anisotropy of crystalline silicon was
fully taken into account; accepted values of its properties (C11 = 166 GPa,
C12 = 63.9 GPa, C44 = 79.6 GPa, ρ = 2.33 g/cm3 [52]) were adopted. The
film thickness and mass density were obtained by X-rays, as indicated above,
and the SAW wavevector k was determined by the laser wavelength and
the scattering geometry. The Rayleigh wave velocity remained thus a func-
tion of the unknown elastic constants of the film. The film being isotropic,
the elastic properties were represented, as indicated in Sect. 3, by the (E, G)
couple of moduli. The velocity for each value of k is computed (see (5)) as
vi comp. (E , G), obtaining a sum of squares χ2 (E, G) whose minimum identifies
the most probable values of E and G, and whose isolevel curves identify the
confidence regions.
Brillouin Light Scattering 165

Fig. 2. 90%, 95% and 99% confidence regions, having a valley shape, obtained
fitting DLC films dispersion relation in the E, G plane. Continuous lines: ν = 0
and ν = 0.5 physical limits and ν = 0.1, 0.2, 0.3, 0.4 isolevel lines; dashed lines:
B = 100, 200, 300, 445 GPa isolevel lines. The line B = 445 GPa = B diam is taken
as the physical upper bound delimiting the acceptable part of the confidence regions

The χ2 (E, G) function turns out, in this case, to have the shape of a
valley that extends from the neighborhood of the ν = 0.5 line into the region
in which ν < 0. The bottom of this “valley” is relatively flat and does not
reliably identify a small region in the (E, G) plane; instead, it identifies a
“strip” running through wide ranges of E and G, and also of B and ν. In order
to delimit the range of acceptable results, only the part of any confidence
region is considered that corresponds to positive values of Poisson’s ratio
(see Sect. 3) and to values of bulk modulus B below a predetermined upper
limit. The bulk modulus of diamond, B diam = 445 GPa, was adopted as
physically plausible upper limit for B.
The confidence regions run across the region delimited by these accept-
ability limits, meaning that ν and B remain essentially undetermined, while
the part of the confidence region compatible with these limits corresponds
to reasonably well defined intervals of E and G. The acceptable part of the
confidence regions must be seen as the meaningful information that can be ob-
tained from the SBS measurements. Further resolution within the confidence
regions does not have real significance. The values of the elastic constants
corresponding to the center of the 90% confidence region allow us to fit the
measured dispersion relations, as shown in Fig. 2. The dispersion relations
computed by the most probable parameter values are compared to the mea-
sured ones in Fig. 3.
166 Marco G. Beghi et al.

Fig. 3. Measured and computed dispersion relations for six thin films on silicon
substrate. Dispersion relations presented as function of the nondimensional product
k h are independent from film thickness and depend only on film properties. From
bottom to top: ∗ and ×, two films of native silicon oxide of different thickness and
indistinguishable properties (they fall on the same line);  and , two DLC films of
3.5 nm and 4.5 nm thickness, of very similar properties (they fall on nearby lines);
◦, DLC film of 15 nm thickness. , DLC film of 8 nm thickness, stiffer than all the
other films

6 Nanotubes
Single-wall carbon nanotubes (SWNT) can be thought as formed by warping
a single graphitic layer into a cylindrical object [53]. Beyond possessing unique
electronic properties, depending on the symmetry, or chirality, of the carbon
lattice, nanotubes also attract much attention because they are expected to
be very strong and to have high elastic moduli.
The Young’s modulus of a carbon nanotube was estimated observing by
transmission electron microscopy (TEM) the vibrations of the free end of
a nanotube clamped at the other end [54], and by observing the nanotube
bending by an atomic force microscope (AFM) [55]. These estimates (val-
ues up to 1.25 TPa) are consistent with the exceptionally high values of the
Young’s modulus measured for a graphene sheet, i.e., about 1 TPa; such val-
ues imply very high stiffness-to-weight ratios. Acoustic vibrational properties
are strictly related to elastic properties of SWNT, and acoustic vibrational
modes in carbon nanotubes have been calculated both by ab initio calculation
(lattice dynamics, e.g., [56]) and by continuum elastic models [57]. AFM and
TEM measurements, beside being destructive, suffer from lack of precision in
determining the SWNT diameter, length, temperature and vibrational fre-
Brillouin Light Scattering 167

Fig. 4. Left: AFM image of the (top) oriented SWNT sample surface, and of the
(bottom) nonoriented SWNT sample surface. Square area is 1 µm × 1 µm, z range
is 1 nm. Right: scattering geometry with respect to the nanotube direction

quency; furthermore, the tendency of SWNT to form bundles complicates the


analysis.
Dynamic light scattering from longitudinal acoustic modes in aligned
SWNT, with a wavelength of the order of hundreds of nm, has been measured
by means of Brillouin spectroscopy; a model for the description of the phe-
nomenon and for the calculation of the scattered intensity was also proposed.
The model is based on a shell mechanical model and a surface elasto-optic
effect coupling the incident light to the tube thermal strains [58,59]. The sam-
ple was a free-standing film of aligned SWNT, produced by the laser-oven
method, purified and aligned with a strong magnetic field [60]. SWNT are
present in bundles or ropes, with a preferential orientation, as shown in Fig. 4.
SWNT have instead a complete random orientation in nonaligned samples.
The typical tube free length is on the order of several hundreds nanometer.
BS measurements were performed exploiting the λ0 = 514.5 nm line of an
Ar+ ion laser. The incident light was p-polarized, with a power of 40 mW;
the scattered light, collected without polarization analysis, was analyzed by
a Sandercock interferometer with a free spectral range of 100 GHz. Mea-
surements were performed in backscattering, with the scattering geometry
shown in Fig. 4: the scattering plane (determined by the scattering wavevec-
tor k = q s − q i and the normal z to the sample surface), the sample surface
plane and the nanotube direction x ; α is the angle between the SWNT direc-
tion and the scattering plane xz; θi is the incidence angle, between incident
light q i and z; β is the angle between x and q i (cos β = sin θi cos α). The
incidence angle θi was varied in the range 30◦ –70◦ in order to vary the scat-
tering wavevector k; measurements were performed with α = 0◦ and α = 90◦
(scattering plane parallel and perpendicular to the nanotube direction).
168 Marco G. Beghi et al.

Fig. 5. (a) Brillouin spectra for the oriented SWNT sample along the tube direction
(α = 0◦ ; θi = 30◦ , 70◦ ), and perpendicularly to the tube direction (α = 90◦ ;
θi = 30◦ ). (b) Brillouin spectrum of a nonaligned SWNT (θi = 50◦ )

The experimental results show that scattering does not occur from SAWs
as in thin films, but from longitudinal acoustic modes of the single tube, hav-
ing a wavevector k ph parallel to the tube axis. In spectra from the oriented
SWNT sample (θi = 30◦ , 70◦ ), with α = 0◦ , a broad peak is detected at
about 45 GHz (Fig. 5), and its position is independent of the incidence angle.
When the scattering plane is instead perpendicular to the SWNT direction
(α = 90◦ ), the feature disappears (Fig. 5). A spectrum from a randomly
oriented SWNT sample is also shown (θi = 50◦ ), with a broad feature at
about 40 GHz. This feature does not change as the sample is rotated by 90◦
(α = α + 90◦ ), showing the in-plane isotropy of the film. The absence of
scattering from aligned tubes for α = 90◦ and the peak shift and width for
α = 0◦ confirm the relative independence between the tube bundles, and that
the material is not an effective medium where acoustic waves can propagate
in all directions, at least at the scale of the laser wavelength λ0 .
A cylindrical shell model provides an adequate description for this scatter-
ing phenomenon. For a long cylindrical thin shell the elastodynamic equations
can be written in cylindrical coordinates (x , r, φ) and a membrane approx-
imation can be used [61]. This model, described by 2D stress conditions and
membrane elastic constants having the dimension of a force per unit length,
is precise enough to describe thermally excited modes along the tube axis,
Brillouin Light Scattering 169

with frequency in the range 1–100 GHz, responsible for the observed BS. The
elastodynamic equations admit plane wave solutions traveling along the axial
direction with wavevector k ph , i.e., ux = A u0 exp[i(k ph x  − ωt + mφ)], with
m an integer. The mode frequency ω depends on the 2D Young’s modulus
E 2D , the surface density ρ2D , the Poisson’s ratio ν, and the SWNT radius R.
For an infinitely long tube these are the appropriate solutions; for tubes of
finite length L the proper boundary conditions affect the form of the solution
and the corresponding frequencies. A surface elasto-optic effect is assumed,
coupling the light to the tube thermal phononic strains and producing a
fluctuating surface polarization density that radiates the scattered photons.
The intensity of the light scattered by a single tube is related to the Fourier
transform of the dielectric susceptibility tensor and to the polarization of the
incident light.
It results from the computed cross section that, in backscattering, only
longitudinal modes with m = 0 contribute to the scattered intensity, provided
that the component k = (4π/λ0 ) cos β = (4π/λ0 ) sin θi cos α of the scattered
wavevector k parallel to the tube is not zero (there must be a nonvanish-
ing component of transferred wavevector, i.e., the scattering plane must not
be perpendicular to the SWNT orientation). In the case of an infinite tube
(L  2π/k ph ) the cross section is nonzero only if the parallel wavevector is
conserved (k = k ph ). This would be a coherent “line Brillouin scattering”,
with only one longitudinal wave (determined by the selected value of k ph )
contributing to the scattered intensity, and the corresponding peak position
depending on the incidence angle (dispersion of the modes). Instead, in the
measurements published in [58], the θi dependence of the peak position is
negligible, because the free SWNT length is of the order of 1 µm or less:
the tubes cannot be considered as infinite with respect to the wavelength
(λ = λ0 /2 cos β  L) of the modes selected by BS. Thus, all longitudinal
modes (fixed end boundary conditions) with m = 0 contribute to scattering,
due to confinement effects, with relative weights given by the computation.
This kind of scattering is often called low-frequency Raman scattering. Con-
tributions from tubes of different lengths (0.5–1.5 µm) were considered, and
assuming ρ2D = 7.6 × 10−7 kg/m2 , R = 6 × 10−10 (by Raman spectroscopy
measurements) and ν = 0.2, a feature with a shape similar to that observed
was obtained, independent of the scattering angle. The broadening of the peak
can be related to length and orientation distributions, tube interactions, and
real boundary conditions. The 2D Young’s modulus can be estimated by fit-
ting the computed peak position to the measured one and a value E 2D = 100
N/m is obtained, on the order of magnitude of the C–C atomic force constant
in a graphite plane [62]. Taking into account the thickness of a graphite layer,
the estimated E 2D value corresponds to a Young’s modulus for the curved
graphitic sheet of the order of 1 TPa, compatible with known values of C11
for graphite [37].
170 Marco G. Beghi et al.

7 Conclusions
We have presented Brillouin scattering (BS) as a nondestructive, contact-
less, powerful characterization technique capable of studying structural and
mechanical properties of bulk materials, thin films and nanostructures. In
particular elastic properties are accessible through the observation of ther-
mally excited acoustic modes propagating in the medium. The experimental
technique and the derivation of the elastic constants have been described to-
gether with some results on different carbon materials in order to show the
capabilities of this technique. In conclusion, BS turns out to be an interesting
tool which proved to be able to characterize a wide variety of materials, and
namely carbon-based materials.

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Index
ta-C, 162, 163 graphite, 161

acoustic phonon, 154 hydrogenated amorphous carbon, 162


acoustic waves, 153
acoustic wave velocity, 154, 155, 157, inelastic scattering, 153
159, 160, 163
surface acoustic waves (SAWs), 154, light scattering, 154
155, 157–159, 162, 164, 168 low-frequency Raman, 169
pseudo surface waves (PSAWs), 159
SAW velocity, 154, 155, 159 mechanical properties, 153
amorphous carbon thin films, 163
nanostructured carbon, 162
Brillouin scattering, 153–159, 161–164, nanotubes, 166
167–170 single-walled nanotubes (SWNT),
surface Brillouin scattering, 157, 166, 167
163–165 single-walled nanotubes (SWNTs),
156, 162, 167–169
diamond, 161
diamond-like carbon (DLC), 162, quasi- elastic scattering, 154
164–166
dispersion, 166 Raman scattering, 154
Rayleigh wave, 154, 155, 159, 162, 164
elastic constants, 155, 156, 158, modified Rayleigh wave, 159, 160
160–162, 164, 165, 168 modified Rayleigh wave velocity,
elastic moduli, 155, 159–161, 163, 166 160, 163
elastic properties, 154, 155, 170 Rayleigh wave velocity, 154, 161, 162,
elastic scattering, 153 164

fullerite, 162 Sezawa wave, 155, 159, 160, 162

graphene, 162 ultra-thin carbon films, 156, 162–166


Electrical Resistivity and Real Structure
of Magnetron-Sputtered Carbon Films

Alexei A. Onoprienko

Institute for Problems of Materials Science, National Academy of Sciences of


Ukraine, 3 Krzhyzhanovsky St., UA-03142 Kiev, Ukraine
onopr@materials.kiev.ua

Abstract. The resistivity and structure of DC magnetron-sputtered carbon films


is studied. The film structure is examined by Raman spectroscopy, transmission
electron microscopy, and electron diffraction. The films reveal prominent resistivity
anisotropy relating to film structure. In the range of deposition temperatures 20–
450◦ C, ordered regular aromatic rings and graphite-like clusters form. In the range
450–650◦ C, the growth mechanism changes and graphite phase forms directly on
the substrate. Annealing of films in the range 50–300◦ C results in transformation of
distorted aromatic rings into regular ones, and in ordering them without formation
of graphite fragments. Further increase in the annealing temperature causes little
changes the film structure. Ion bombardment in the range of substrate bias voltage
−20 ≤ V bias ≤ −150 V decreases cluster size and results in disordering in their
internal structure. At V bias > −150 V the cluster structure tends to be more
ordered towards graphitization. The results obtained open the way for deposition
of carbon films with controllable electrical properties.

1 Introduction
The great interest in diamond and diamond-like carbon (DLC) films as
promising materials for microelectronics stems from their specific electrical
properties. However, when using diamond films, problems arise connected
with their polycrystalline structure. Diamond films have a well-developed
net of grain boundaries that affect the electrical properties of films. In this
respect DLC or amorphous carbon (a-C) films are preferable since they are
smooth and do not contain well-developed grain boundaries.
In many studies [1, 2, 3, 4, 5, 6, 7, 8, 9], it has been shown that the substrate
temperature and energy of carbon species constituting the growing film are
the parameters that govern the structure and properties of carbon films the
most. Depending on the deposition method and conditions, the carbon films
can be deposited with a variety of properties ranging from diamond-like to
graphite-like. The film resistivity, being a structure-sensitive property, is also
dependent on deposition conditions. However, in spite of the fact that a num-
ber of works deal with the effects of deposition [1,2,3,4,5] and heat treatment
temperature [10, 11, 12, 13] and ion energy [5, 6, 7, 8, 9] on the microstructure
and properties of a-C films prepared by various techniques, there do not
seem to be any systematic studies on the electrical resistance of a-C films.
G. Messina, S. Santangelo (Eds.): Carbon, The Future Material for Advanced Technology Ap-
plications, Topics Appl. Phys. 100, 175–186 (2006)
© Springer-Verlag Berlin Heidelberg 2006
176 Alexei A. Onoprienko

Fig. 1. Schematic draw of specimen with Ni contacts (1–1 and 2–2 ) and carbon
film for resistance measurements

In the aforementioned studies, the electrical resistance was measured only as


a subsidiary parameter along with other properties of a-C films. Moreover,
in all of them the resistance (or conductivity) was measured only in one di-
rection: either parallel or perpendicular to the substrate surface. Conversely,
in our previous study [14] we reported, for the first time, the phenomenon
of prominent resistivity anisotropy in a-C films deposited by DC magnetron
sputtering, the extent of which depends on deposition temperature.
The present study focuses on the relationship between structure and
electrical resistivity evolution with substrate temperature and ion bombard-
ment (IB) intensity of carbon films, which may favour understanding the
mechanism of film microstructure formation. Electron diffraction (ED) and
Raman scattering were chosen as the methods sensitive to the structure.
These studies were supplemented by measurements of film resistivity and by
transmission electron microscopy (TEM).

2 Experimental
The a-C films were sputter-deposited using a planar DC magnetron system
of balanced type with graphite target, and argon at pressure of 1 Pa as a
sputtering gas. As substrates, cleavages of NaCl single crystals (for electron
diffraction and electron microscopic studies) and polished platelets of Si–Ti–
Al–O ceramics (for Raman spectroscopy and resistance measurements) were
used. For resistance measurements, specially configured 150 nm thick nickel
film contacts (1–1 and 2–2 , Fig. 1) were magnetron sputter-deposited onto
substrates before (1–1 ) and after (2–2 ) C-film deposition.
Three series of specimens were prepared for study. In one series, films
were deposited onto substrates preheated to a given temperature in the range
20 − 650◦C. In the second series, the carbon films were deposited onto sub-
strates approximately at room temperature followed by annealing for 1 h in
a vacuum of 1.3 × 10−3 Pa at different temperatures in the range 50–650◦C.
During deposition in the above two series, the substrates were at a floating
potential of approximately V bias  −20 V. In the third series, carbon films
Resistivity and Structure of Magnetron-Sputtered Carbon Films 177

were deposited onto substrates at room temperature, but DC negative bias


voltage in the range V bias = −25 V to −175 V was applied to lower metal
contacts (1–1 in Fig. 1) during film deposition. It has to be noted that carbon
films in all series were deposited at low magnetron power in order to prevent
uncontrollable heating of the substrates by plasma radiation [15].
The resistance of C-films was measured in two directions: parallel (R )
and perpendicular (R⊥ ) to substrate surface (see Fig. 1). Film resistivities
ρ and ρ⊥ were calculated from the measurements of R and R⊥ , the surface
area and thickness of carbon film between respective metal contacts. The
resistivity anisotropy coefficient was defined as κ = ρ⊥ /ρ .
The film thickness was measured with an optical interferometer, 400–
600 nm, on ceramic substrates. Thickness of the films deposited onto NaCl
for TEM and ED was 60–80 nm. Raman scattering was induced by the λ =
514.5 nm line of argon laser. The recorded spectra were fitted to the sum of
two Gaussian-shape lines (G band centered at approx. 1580 cm−1 and the
D band centered at approx. 1360 cm−1 ) and a linear background term.

3 Results and Discussion


3.1 Substrate Temperature Effects

Figure 2a shows the dependence of logarithm ρ⊥ on the substrate temperature


during deposition (T dep) and annealing (T ann ) temperature (T ann ). As seen,
ρ⊥ decreases with increase in both T dep and T ann , but this change is not
large.
At the same time, those dependencies for ρ exhibit an essentially different
character (Fig. 2b). An increase in T dep results in immediate decrease in ρ at
T dep ≥ 50◦ C. It decreases with temperature change up to T dep ≈ 400◦C, but
with further increase in T dep up to 650 ◦C it remains unchanged. Contrary to
this, a-C films deposited at room temperature and further annealed exhibit
constancy of ρ in the range T ann = 50 to 300◦ C, and only at T ann > 300◦ C
does ρ decrease with the increase in annealing temperature.
In Fig. 2c the dependence of the logarithm of resistivity anisotropy coef-
ficient on T dep and T ann is shown. For films deposited at different values of
T dep, κ increases in the range of deposition temperatures 20–400◦C and then
slightly decreases at higher deposition temperatures. For films deposited at
room temperature and annealed at different temperatures, κ is nearly con-
stant in the range 50–300◦C and then it increases with further increase in
T ann .
In Fig. 3a the dependence of integral intensity ratio I D /I G of D and
G peaks on the T dep and T ann is shown. For films deposited at different
substrate temperatures, I D /I G increases in the range 20–400◦C and then de-
creases with further increase in T dep. For films deposited at room temperature
and then annealed, the intensity ratio I D /I G increases rapidly with increase
178 Alexei A. Onoprienko

Fig. 2. Carbon film resistivity ρ⊥


(a), ρ (b), and resistivity aniso-
tropy coefficient κ = ρ⊥ /ρ (c) as
a function of (1) deposition and
(2) annealing temperatures

in annealing temperature in the range 50–300◦C, but then it increases at a


lower rate.
Figure 3b shows the dependence of the G-peak position on temperatures
T dep and T ann. With increase in temperature of deposition or annealing, the
G-peak position shifts towards higher frequencies in both cases.
Electron diffraction revealed that carbon films deposited at room tem-
perature and then annealed in the range 50–650◦C were amorphous, and
ED patterns consisted of three–four diffused halos corresponding to d ∼ =
0.30, 0.20, 0.16, 0.11 nm that are close to the interplanar distances of a
graphite (0.338, 0.212, 0.169, 0.115 nm, respectively). The carbon films de-
posited at substrate temperatures in the range 20–400◦C were also amor-
phous. Only at T dep > 500◦ C were halos transformed into broadened diffrac-
tion lines peculiar to the structure of polycrystalline graphite.
The observed anisotropy and the character of changing electrical resis-
tance in carbon films studied can be explained in terms of C-film microstruc-
ture. In accordance with the model proposed earlier [14], upon magnetron
sputtering the C-films form with predominantly sp2 -bonds that are distrib-
Resistivity and Structure of Magnetron-Sputtered Carbon Films 179

Fig. 3. Integral intensity ratio


I D /I G (a) and G-peak position
(b) as a function of (1) deposition
and (2) annealing temperatures

uted chaotically within the film volume. ED shows that films deposited at
low (room) temperature are amorphous. However, the presence of a D peak
in the Raman spectra indicates that a-C films contain aromatic rings [16].
At the same time, the coefficient of resistivity anisotropy κ ∼ = 1 for such
films (Fig. 2c) is peculiar to isotropic structure. On the basis of this, it can
be assumed that aromatic rings that form within the structure of C-films
at low temperature are strongly distorted and mutually disordered. Such a
model of a-C film microstructure is justifiable since there is information that
C-films deposited by DC magnetron sputtering and laser ablation of graphite
at low temperature also contain distorted fivefold and sixfold rings [17, 18].
As deposition temperature increases in the range 20–400◦C, the formation of
regular (nondistorted) aromatic rings becomes more probable and ordering
of them into sp2 -bonded clusters takes place. This is supported by growth of
I D /I G (Fig. 3a) in this temperature range because, as pointed out in [16],
the intensity of the D peak increases with the number of aromatic rings with
sixfold symmetry and degree of ordering them. The number of sp2 -bonded
clusters increases with an increase in T dep, and the film forms with a more
graphite-like structure, which is indicated by increase in κ (Fig. 2c). Shift-
ing of the G-peak position towards higher frequencies with increase in T dep
(Fig. 3b) also indicates graphitization of the a-C film. The graphitization of
180 Alexei A. Onoprienko

C-films deposited by various techniques at elevated substrate temperatures


was also observed in [2, 4, 18, 19].
Since electron diffraction patterns from C-films deposited at different sub-
strate temperatures in the range 20–400◦C are similar (halos), it is clear that:
(i) the short-range atomic order in a-C films with a structure based on sp2
bonding remains unchanged, and (ii) the sizes of graphite-like clusters are
so small that structural changes within the clusters are below the sensitiv-
ity limit of the method used (ED). The graphite crystallites of very small
size (nanocrystallites) have been also detected in electron microscopic and
scanning tunnelling microscopic examination of a-C films deposited by DC
magnetron sputtering and laser-arc evaporation at elevated substrate tem-
peratures [17, 20].
Further increases in T dep over 400◦C results in direct nucleation and
growth of a fine-grained graphite phase onto the substrate. This is indicated
by ED patterns, which contain broadened lines peculiar to a polycrystalline
graphite phase, and also the temperature dependence of ratio I D /I G and G-
peak position at elevated temperatures (Figs. 3a, 3b). Nucleation and growth
of graphitic films at high temperatures is supported also by near constancy
of the resistivity anisotropy coefficient at T dep ≥ 450◦ C (Fig. 2c).
The nature of changes in the microstructure of a-C films annealed at var-
ious temperatures differs from that of films deposited at different substrate
temperatures. As seen from Fig. 2a, the dependence of ρ⊥ on temperature
and the respective values of resistivity are virtually the same for both de-
position and annealing. This means that structural changes are similar in
films of both types in the direction perpendicular to substrate surface. At
the same time, annealing in the range 50–300◦C does not appreciably change
ρ , but its absolute value remains higher than for films deposited at the same
temperatures. Only at T ann > 300◦ C does ρ decrease (Fig. 2b). Accord-
ingly, the dependence of κ on T ann is different: up to 300◦ C coefficient κ is
nearly constant and then changes similarly to the case of film deposition at
various temperatures. The ratio I D /I G increases with increase in T ann up to
∼ 300◦ C and then changes little (Fig. 3a). This indicates that postdeposition
annealing also results in changing a-C film microstructure towards graphiti-
zation. However, in contrast to the films deposited at various temperatures,
in this case only transformation of distorted aromatic rings into regular ones
occurs. This process is the most intense in the annealing temperature range
50–300◦C. An increase in the number of regular aromatic rings in the film
structure, in accordance with ideas stated in [16], should give an increase in
D-peak intensity and a shift of G-peak position towards higher frequencies,
as actually observed in Figs. 3a, 3b. However, lengthy graphite fragments
do not form in this case, and it is only at T ann > 300◦ C that the forma-
tion of graphite-like fragments seems to occur, reflected in the corresponding
variation of κ with temperature (cf. Fig. 2c). Since the energy required for
structure rebuilding with cluster formation is higher than for their formation
Resistivity and Structure of Magnetron-Sputtered Carbon Films 181

during deposition, then the microstructure of a-C films changes little with
further increase in T ann, corresponding to the dependence for κ and I D /I G
in that temperature range. This conclusion is also supported by the results
of the electron diffraction study: even after annealing at 650◦ C the respective
ED pattern contain very diffused halos.

3.2 Substrate Bias Effects

In this set of experiments NaCl single-crystal cleavages with Ni contacts


(1–1 in Fig. 1) were used as substrates, and DC bias voltage in the range
V bias = −25 V to −175 V was applied to contacts during film deposition.
Because NaCl is essentially a low-conductivity material, such a configuration
resulted in bombardment with ions of growing film on contacts and in a close
vicinity of contacts, while areas far from contacts were not subject to ion
bombardment (IB) [21].
In Figs. 4a, 4b the TEM micrographs of carbon film deposited at V bias =
−175 V are shown for the areas in which the film was subject and was not
subject to IB, respectively. As can be seen, the microstructures of these parts
of the C-film are quite different. The C-film area grown without the IB con-
sists of round-shaped partially faceted “grains” (Fig. 4b), whereas the film
area grown under intense IB consists of elongated “grains” with clearly seen
internal structure (Fig. 4a). ED patterns from both areas are similar and
coincide with those for amorphous carbon films. However, in some cases ED
patterns taken from film areas affected by intense IB contained an additional
halo with d ∼= 0.30 nm that is close to the d-spacing of graphite (002) basal
plane. Note that such a prominent difference in film structure was observed
only at V bias > −100 V.
Raman spectra were taken from the area in the middle between the con-
tacts for the films grown at different values of substrate bias [21]. Analysis
of Raman spectra recorded for the films deposited at different V bias revealed
a nonmonotonous dependence of I D /I G on bias voltage (Fig. 5). The I D /I G
ratio increases with increased bias voltage and reaches a maximum value at
V bias ≈ −150 V, and then drops to the initial level at −175 V. It was not
possible to investigate the dependence of resistivity anisotropy of C-films on
V bias due to particularities of the film microstructure and variation of the
thickness of such films caused by the IB [21].
Only the ρ⊥ resistivity of these films could be measured. The ρ⊥ values
of C-films deposited at different V bias are listed in Table 1. From these data
one can see that the IB results in an increase of ρ⊥ by more than an order
of magnitude.
Based on the interpretation of Raman spectra developed in [16, 22, 23], it
is possible to assert that the increase in I D /I G with increasing bias voltage
in the range of −25 < V bias < −150 V indicates the bond-angle disorder
of internal structure of graphite-like clusters along with a decrease in their
size. This is indicated also by an increase in film resistivity ρ⊥ in this V bias
182 Alexei A. Onoprienko

Fig. 4. TEM micrographs of carbon films subject to (a) and not subject to (b) in-
tense IB during deposition

Fig. 5. Integral intensity ra-


tio I D /I G as a function of
substrate bias voltage V bias
Resistivity and Structure of Magnetron-Sputtered Carbon Films 183

Table 1. Resistivity values for C-films deposited in different bias conditions

Substrate bias V bias Resistivity ρ⊥


V Ω · cm
Floating 1.5 × 104
−100 1.2 × 105
−150 2.9 × 105
−175 2.2 × 105

range. An increase of V bias over −150 V results in a decrease in I D /I G and


simultaneously in a decrease in film resistivity ρ⊥ (drop-down branch on the
plot in Fig. 5, and data in Table 1). The critical value of V bias ∼
= −150 V for
maximum resistivity in our work is close to that found in [6, 24] for maximum
values of various film properties (optical gap, atomic density, etc.).
The effect of a decrease in both I D /I G and ρ⊥ with increasing IB inten-
sity (above V bias = −150 V) relates to a certain bond-angle ordering within
the graphite-like clusters (i.e., their graphitization) and to some increase of
their size. A similar dependence of I D /I G on V bias was observed during a-C
film deposition by ion-beam sputtering of a graphite target with simultaneous
bombardment by argon ions of the growth surface [25]. It was revealed that
at low ion energy both film density and sp3 concentration are low. The max-
imal value of the film density and the minimal size of film-forming clusters
were achieved at about 100 eV. A further increase in the ion energy promoted
the decrease of film density, and the appearance and increase in the size of
graphite regions together with local microstructural ordering within them.
The most probable reason for these effects could be the development of lo-
cal high-temperature spikes caused by the collision cascades arising during
enhanced IB [26].
TEM investigations of our films allow us to assume that the dense, round-
shaped or partially faceted “grains,” observable in Fig. 4b, are the cross-
sections of the columns disposed normally to the substrate, which form the
film in the area where the IB is almost absent. The “grains” observable in
micrographs taken from a-C film area subject to intense IB also have colum-
nar structure (Fig. 4a), but in contrast to Fig. 4b, these columns are strongly
tilted to the substrate. As it follows from the micrographs, the column width
in Fig. 4a is approximately equal to the diameter of the columns in Fig. 4b.
This means that the columns from both areas are similar. At the same time,
on some of ED patterns from an area of film subject to intense IB the halo
appeared with d -spacing of about 0.30 nm, which is close to (002) d -spacing
of graphite. This halo was never observed in ED patterns from film that was
not subject to IB. The (002) reflection in the transmission ED pattern indi-
cates that the graphite-like planes are arranged nearly parallel to the electron
beam, i.e., these planes are perpendicular to the substrate. In other words,
the “c-axis” of graphite-like clusters forming the columns that are arranged
184 Alexei A. Onoprienko

along the substrate (columns in Fig. 4a) is parallel to the substrate surface,
whereas the graphite-like clusters forming the columns arranged perpendic-
ular to the substrate (Fig. 4b) have “c-axis” directed perpendicular to the
substrate surface.

4 Conclusion
On the basis of the results obtained, it is possible to deduce what follows.
Magnetron-sputter deposition at low temperature results in the formation of
amorphous carbon films with predominantly sp2 bonds between atoms. The
microstructure of such films consists of chaotically displaced and distorted
aromatic rings and graphite fragments. This structure is close to an isotropic
one, so there is virtually no resistivity anisotropy. As the deposition temper-
ature is raised in the range 20–450◦C, more regular sixfold aromatic rings
and graphite-like clusters form on the substrate. The extent of aromatic ring
ordering and cluster growth is greatest at T dep ∼ 450◦C. Graphitization of
the film occurs mainly in the direction parallel to the substrate surface that
is indicated by electron diffraction patterns and the dependence of resistivity
on the deposition temperature. An increase in deposition temperature above
450◦ C results in changing the formation mechanism for carbon films, and the
nuclei of the graphite phase form directly on the substrate. Increasing the
temperature in the range 450–650◦C also results in growth of clusters with
an ordered inner structure. This is evidenced by the drop in the dependence
of I D /I G on deposition temperature, the appearance of ED patterns peculiar
to fine-grained polycrystalline graphite, and the stabilization of the resistivity
anisotropy coefficient at maximum level.
Annealing in the range 50–300◦C of a-C films deposited at room temper-
ature results in the intense transformation of distorted aromatic rings into
regular ones, and in ordering them in the substrate plane without formation
of graphite fragments. Further increase in the annealing temperature up to
650◦ C has little influence on the structural changes in film, and graphite-like
clusters do not form in this case. This inference is supported by the depen-
dencies for ρ and κ, and the absence of “graphite” lines in the ED patterns
over the entire annealing temperature range studied.
Ion bombardment of growing C-film affects its structure and therefore
resistivity. In the range of substrate bias voltage −20 < V bias < −150 V
the size of graphite-like clusters within C-films decreases and simultaneously
increases their internal structural disorder. At V bias > −150 V the clus-
ter structure tends to be more ordered towards its graphitization. The mi-
crostructure of C-films is of columnar type, and columns are built of packs of
graphite-like clusters that are ordered somehow within the columns. When
the intensity of IB is low (or absent) the c-axis of these clusters is oriented
predominantly perpendicular to the growth surface, while the enhancement
of the IB promotes the reorientation of the c-axis predominantly along the
Resistivity and Structure of Magnetron-Sputtered Carbon Films 185

growth surface. The observed variations in C-film resistivity occur according


to film microstructure changes.

References
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(1996) 175, 180
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[4] B. K. Tay, X. Shi, E. J. Liu, et al.: Thin Solid Films 346, 155 (1999) 175, 180
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175
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176, 178
[15] A. A. Onoprienko, V. V. Artamonov, I. B. Yanchuk: Surf. Coat. Tech. 200,
4174 (2006) 177
[16] A. C. Ferrari, J. Robertson: Phys. Rev. B 61, 14095 (2000) 179, 180, 181
[17] B. Marchon, M. Salmeron, W. Siekhaus: Phys. Rev. B 39, 12907 (1989) 179,
180
[18] S. Bhargava, H. D. Bist, A. V. Narlikar, et al.: J. Appl. Phys. 79, 1917 (1996)
179, 180
[19] M. A. Capano, N. T. McDevitt, R. K. Singh, F. Qian: J. Vac. Sci. Technol. A
14, 431 (1996) 180
[20] I. Alexandrou, H. J. Scheibe, C. J. Kiely, et al.: Phys. Rev. B 60, 10903 (1999)
180
[21] L. R. Shaginyan, A. A. Onoprienko, V. F. Britun, V. P. Smirnov: Thin Solid
Films 397, 288 (2001) 181
[22] S. Fujimaki, M. Kitoh, K. Furusawa, et al.: Diamond Films and Technol. 2, 17
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186 Alexei A. Onoprienko

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Index
a-C, 175, 176, 181 graphitization, 175, 179, 180, 184
sp2 -bonded clusters, 179–181, 183
ion bombardment (IB), 176, 181–184
annealing, 175–180, 184
magnetron sputtering, 176
clustering microstructure, 175, 176, 178–181, 183,
graphite-like clusters, 175, 180, 181, 184
183 graphite-like structure, 179, 183
D band, 177, 179, 180
D/G band intensity ratio, 177, 179–184 Raman spectroscopy, 176, 179–181
diamond-like carbon (DLC), 175 resistivity, 175–178, 180, 181, 183
resistivity anisotropy, 175–181, 184
electron diffraction (ED), 176–181, 183,
184 substrate bias, 181

G band, 177–180 transmission electron microscopy


graphite-like carbon (GLC), 175 (TEM), 176, 177, 181–183
Formation, Atomic Structures and Properties
of Carbon Nanocage Materials

Takeo Oku1 , Ichihito Narita1 , Atsushi Nishiwaki1 , Naruhiro Koi1 ,


Katsuaki Suganuma1 , Rikizo Hatakeyama2,
Takamichi Hirata2 , Hisato Tokoro3, and Shigeo Fujii3
1
Institute of Scientific and Industrial Research, Osaka University, Mihogaoka 8-1,
Ibaraki, Osaka 567-0047, Japan
2
Graduate School of Engineering, Tohoku University, Sendai 980-8579, Japan
3
Hitachi Metals Co. Ltd., Advanced Electronics Research Laboratory, Mikajiri
5200, Kumagaya, Saitama 360-0843, Japan
oku@sanken.osaka-u.ac.jp

Abstract. Various carbon nanocage fullerene materials (clusters, metallofullerenes,


onions, nanotubes, nanohorns and nanocapsules) were synthesized by electron-beam
irradiation, chemical reaction, hybrid arc discharge, and self-organization. Atomic
structures and structural stability of these materials were investigated by high-
resolution electron microscopy, molecular dynamics, and molecular orbital calcu-
lations. Photoluminescence as well as magnetic and electronic properties of these
fullerene materials were also investigated. The present work indicates that the new
carbon nanocage fullerene materials with various atomic structures and properties
can be produced by various synthesis methods, and a guideline for designing the
carbon fullerene materials is summarized.

1 Introduction
Carbon has various hollow-cage nanostructures such as C60 , giant fullerenes,
nanocapsules, onions, nanopolyhedra, cones, cubes, and nanotubes [1, 2, 3,
4, 5, 6, 7]. These C structures show different physical properties, and have
the potential of studying materials of low dimensionality within an isolated
environment. In particular, cluster-included fullerene materials are intrigu-
ing for both scientific research and device applications such as cluster pro-
tection, cluster separation, nano-ball bearings, nano-electronic–magnetic de-
vices, gas storage, and biotechnology [8, 9, 10, 11, 12, 13, 14]. By controlling
of the size, layer numbers, helicity, compositions, and included clusters, the
cluster-included C nanocage structures with band-gap energy of 0–1.7 eV and
nonmagnetism are expected to show various electronic, optical, and magnetic
properties such as Coulomb blockade, photoluminescence, and superparamag-
netism, as shown in Fig. 1a. Possible applications of the C fullerene materials
are also shown in Fig. 1b.
The direction of the research on carbon nanocage materials is threefold.
The first is to prepare the new C nanocage fullerene materials. In the present
G. Messina, S. Santangelo (Eds.): Carbon, The Future Material for Advanced Technology Ap-
plications, Topics Appl. Phys. 100, 187–216 (2006)
© Springer-Verlag Berlin Heidelberg 2006
188 Takeo Oku et al.

Fig. 1. (a) Structures and properties of C fullerene materials. (b) Applications and
future of C fullerene materials
Carbon Nanocage Materials 189

work, various methods such as electron-beam irradiation, chemical reaction,


hybrid arc discharge, and self-organization techniques were selected for the
formation of the fullerene materials. Nanocapsules and onions are expected to
form at low temperatures compared to the ordinary arc-discharge method.
Au clusters were selected for the C nanocapsule formation. Arc-discharge,
electron-beam irradiation and chemical synthesis techniques were applied for
the fullerene formation. One-dimensional carbon nanocage arrangement was
also tried by using self-organization of metal nanoparticles with a size below
10 nm. Gold colloids have been used for the formation of single-electron tran-
sistors [15, 16]. In the present work, Au nanoparticles were selected because
of easy control of cluster size [17]. Fabrication of one-dimensional Au nan-
odots and nanowires encapsulated in carbon nanocage structures was tried
by annealing the one-dimensional self-organized nanoparticles on carbon thin
films.
The second direction is to understand the formation mechanism and mi-
crostructure of these C nanocage fullerene materials from high-resolution elec-
tron microscopy (HREM), which is a powerful method for structure analysis
at the atomic scale [18, 19, 20]. Energy dispersive spectroscopy (EDS) was
carried out for composition analysis the fullerene materials. In order to con-
firm the atomic structure proposed by HREM, theoretical calculations by
molecular mechanics, molecular dynamics, and molecular orbital calculations
were carried out. The third direction is to understand the various properties
of the C nanocage materials. Photoluminescence (PL), electronic properties
and magnetic properties of these fullerene materials were investigated. Down-
sizing of these materials is expected to show the various properties [21]. These
studies will give us a guideline for design and synthesis of the fullerene ma-
terials, which are expected for the future nanoscale devices.

2 Synthesis Methods
Carbon nanocapsules and clusters were produced by the following method [22,
23]. β-SiC nanoparticles (Sumitomo Cement), were dispersed in deionized
water with polyvinyl alcohol (PVA-706, Kuraray) at 60◦ C. This polymer is
a copolymer of polyvinyl alcohol and polyvinyl acetate. The solution with
clusters and polyvinyl alcohol was dried in a drying oven prior to loading
into the vacuum chamber. The annealing chamber was first evacuated to
1 × 10−6 Pa, and the samples were annealed at 400–800◦C for 30 min in an
Ar atmosphere of 0.12 MPa.
Commercially available a-Fe2 O3 (hematite, 99.7%) and graphite carbon
(99.5%) powders were also used as starting materials [24, 25]. Their particle
sizes were 30 nm and 5 µm, respectively, which were measured by using a
particle counter (HORIBA LA-920). Samples for Fe nanoparticles coated with
C nanolayers were prepared by annealing mixtures of a-Fe2 O3 and C powders
at 1000◦C for 2 h in the same manner. Ratios in weight of a-Fe2 O3 to B
190 Takeo Oku et al.

were varied from 7 : 3 to 3 : 7. Those of a-Fe2 O3 to C were from 8 : 2


to 5 : 5. Each mixture was mixed in a V-shape mixer. The temperature
elevation rate was 3◦ C min−1 at annealing. For the formation of carbon
onions, amorphous carbon produced from with polyvinyl alcohol (PVA-706,
Kuraray) was used [26, 27].
Carbon nanocapsules were also prepared by a direct current and radio-
frequency (DC-RF) hybrid arc discharge using pair anodes in order to en-
hance the Ge and Si evaporation [28, 29]. A graphite hollow cylinder (0.6 cm
in diameter, 30 cm in length) is used for the main DC arc discharge. The
gap distance between the main discharge electrodes is approximately 0.4 cm.
A subanode of a carbon cylinder (1.5 cm in diameter, 10 cm in length) with
the semiconductor (Si or Ge) powder is used, and a main anode of a carbon
rod is partially mixed with the semiconductor powder. The DC arc discharge
is initiated between a cathode electrode and the pair anodes. An RF antenna
of water-cooled spiral copper pipe is installed 3 cm above the arc point to
generate auxiliary plasma produced by an RF discharge around the DC arc
plasma. When RF power is applied to an antenna through a matching circuit,
the antenna DC current is also generated. The experimental parameters are
as follows: DC arc current, 100 A; subanode current, 80 A; RF power, 600 W
(13.56 MHz); helium gas pressure, 100 Torr. A detailed illustration of the
apparatus was provided in the previous work. The plasma produced by this
DC-RF hybrid discharge is much more voluminous than that by the ordinary
DC arc discharge.
Au nanoparticles (ULVAC) with a size of ca. 5 nm are selected in the pres-
ent work for the one-dimensional positioning of carbon nanocapsules [30, 31].
The surface of these nanoparticles was stabilized by α-terpineol (C10 H18 O)
in toluene solution. The solution with Au nanoparticles was dispersed on
holey carbon grids with thickness ca. 15 nm (Oken Syoji.). After drying
the specimens, they were loaded into the vacuum chamber, and annealed at
∼ 200–400◦C for 30 min in vacuum of ca. 7 × 10−4 Pa.

3 Fullerene Clusters and Metallofullerenes


Hollow carbon clusters with diameters in the range of 0.7–1.0 nm are often
on the carbon nanocapsules. Two of the carbon clusters are shown in Figs. 2a
and 2b. The size of the carbon cluster in Fig. 2a is in the range of 0.5–0.7 nm,
which corresponds to that of C36 [32,33]. The high-resolution image of Fig. 2b
also shows a carbon cluster with the size of 0.7–0.8 nm, and the number of
carbon atoms would be ∼ 70 (C70 ) [1], which could be estimated from the size
of the cluster. In addition, dark contrast is observed inside the cluster, which
would indicate the existence of several atoms inside the carbon cluster. The
carbon cluster is directly connected at the step edge of the graphite sheets,
which results in the stabilization of the carbon cluster. These C36 and C70
carbon clusters have elliptical structures [1,32,33], which agrees well with the
Carbon Nanocage Materials 191

Fig. 2. HREM images of (a) C36 and (b) C70 clusters. Atomic structural models
of (c) C36 and (d) C70 clusters

present high-resolution observation. Structure was optimized by molecular


orbital method using MOPAC software (Fujitsu).
The possibility of direct detection of doping atoms in C60 solid clusters
by HREM was investigated using calculated residual indices (RHREM ) and
difference images [1, 34, 35]. The light element nitrogen (Z = 7) and heavy el-
ement rubidium (Z = 37) were selected as doping atoms in the present work.
It was reported that nitrogen atoms were included at the center of the C60
clusters [36], which was detected by electron paramagnetic resonance [37].
It was also reported that Rb atoms were doped at the octahedral sites of
C60 solid clusters, which were determined by X-ray diffraction [38]. Based on
the crystal structure of C60 solid clusters, difference images between C60 and
doped C60 (C60 /doped C60 ) were calculated for image analysis using residual
indices. HREM images of C60 doped with nitrogen (N) and rubidium (Rb)
atoms were calculated as functions of accelerating voltage of microscope,
crystal thickness, and defocus values. The structure models and calculated
images are shown in Fig. 3. Difference images of N@C60 /C60 and RbC60 /C60
showed N and Rb atomic positions clearly at high accelerating voltage and
large crystal thickness. RHREM values of RbC60 are strongly dependent on
accelerating voltage and crystal thickness, which would be due to the dynam-
ical diffraction effect of Rb atoms. Defocus values also influence the RHREM
192 Takeo Oku et al.

Fig. 3. Structural models of C60 , N@C60 , and Rb@C60 , and HREM simulated
images

values, and the Scherzer defocus would be the best for atomic detection. The
present work indicates that the doping atoms at the inside and interstitial
site of C60 solid clusters could be detected by HREM with difference images
and RHREM values.
Various types of endohedral C clusters have been discovered and investi-
gated. Metallofullerenes, which have atoms (such as La, Y, Sc, Li, Na, N, and
other lanthanoids) inside the C60 , C82 , C84 , and other giant fullerenes, are ex-
pected as superatoms with various structures and physical properties [39, 40].
In addition, encapuslation of Sc [41], La [42], Ba [43], Ca [40, 44], Eu [45],
Gd [46], Y [47], Sm [47] and Tb [47] atoms inside the C74 cluster have been
reported.
Silicon (Si) atoms have also been successfully introduced in carbon clus-
ters by using the DC-RF hybrid arc discharge. Mass analysis of the soot
indicated high-yield production of C74 [48] and existence of Si@C74 [28], as
shown in Fig. 3a. The C74 fullerene has D3h symmetry satisfying the isolated
pentagon rule, and the possibility of inserting a Si atom inside the C74 cage
was investigated by using ab initio molecular dynamics simulation [49].
Hollow carbon clusters with diameters of ∼ 0.8 nm are often observed on
carbon nanotubes and nanocapsules. A HREM image of a carbon cluster on
a carbon nanotube is shown in Figs. 3b and 3c is an enlarged image of the
carbon cluster. The carbon cluster has an elliptical structure, and the size is
∼ 0.8 nm, which agrees well with the size of Si@C74 [50]. Dark contrast is
often observed in the carbon clusters. This indicates the existence of Si atoms
inside the carbon clusters, which was also supported by the mass spectra
analysis.
Carbon Nanocage Materials 193

Fig. 4. (a) Mass spectra of the soot indicated high-yield production of C74 .
(b) HREM image of Si@C74 on a carbon nanotube. (c) Enlarged HREM image
of the Si@C74 cluster. Calculated HREM images of (d) C74 and (e) Si@C74 clus-
ters, as a function of defocus values, respectively
194 Takeo Oku et al.

Table 1. Calculated values for carbon clusters


Total steric energy Heat of formation εHOMO εLUMO Energy gap
kcal kcal kcal kcal
mol mol · atom mol mol · atom
eV eV eV
C60 179 2.98 811 13.5 −1.527 1 0.606 4 2.133 5
C70 177 2.53 886 12.7 −1.503 9 0.454 1 1.958 0
C72 197 2.74 928 12.9 −1.399 6 0.572 9 1.972 5
C74 170 2.30 950 12.8 −0.468 3 −0.369 8 0.098 5
Si@C74 168 2.24 994 13.3 −0.564 9 −0.466 6 0.098 3
C76 182 2.39 937 12.3 −1.106 3 0.272 8 1.379 1

The cluster structures are calculated theoretically, and the structure mod-
els of the C74 and Si@C74 are shown in Figs. 4d and 4e, respectively. The
structures are optimized by molecular orbital calculations using PM3. Based
on the projected structure models, image calculations on the C74 and Si@C74
clusters were carried out for various defocus values to investigate the imaging
condition of the HREM images, as shown in Figs. 4d and 4e, respectively. The
Scherzer defocus value of the present 300 kV electron microscope is ∼ 41 nm.
The experimental data agree well with HREM images calculated at the de-
focus values in the range of −40 to −50 nm, which indicates the observed
HREM images were taken close to the Scherzer defocus.
Electronic structures of C74 , Si@C74 , and a single Si atom were investi-
gated by DV-Xa, as shown in Figs. 5a–c, respectively. Calculated results for
the structural stability and electronic structure are listed in Table 1. The
C60 shows a large energy gap between the highest occupied molecular orbital
(HOMO) and the lowest unoccupied molecular orbital (LUMO). Although
the HOMO–LUMO gap of C60 is calculated to be 2.134 eV, the energy gaps
of C74 and Si@C74 are 0.099 and 0.098, respectively. The energy gap of a
single Si atom was also calculated to be 0.452 eV. The C2p orbital is strong
around the energy gap for C60 and C74 , and the Si3p orbital shows the density
of states (DOS) around the energy gap for Si@C74 . The Si@C74 cluster in
Fig. 4b is directly connected on the carbon {002} sheets, which would result
in the stabilization of the carbon cluster. Total energies of the C clusters were
calculated as listed in Table 1, and 60–76 total steric energy of the Si@C74
was the lowest in the present calculation, which indicates that the insertion
of the Si atom into the C74 cluster stabilizes the structure. Heat of formation
per carbon atom for the Si@C74 is almost the same as that of C60 cluster,
which indicates the structure is fairly stable.
It has been reported that the energy gap of C74 clusters is small (∼ 0.2 eV)
compared with the ordinary C60−80 fullerenes [19]. In the present work,
the energy gaps of the C74 and Si@C74 were calculated to be 0.0985 and
0.0983 eV, respectively. Although the Si3d orbital affects the energy levels
of the C74 , the Si@C74 shows almost the same HOMO–LUMO gap. For the
metallofullerenes such as Sc@C74 , La@C74 , Ca@C74 , Eu@C74 , and Gd@C74 ,
Carbon Nanocage Materials 195

Fig. 5. Energy level diagram and density of states of (a) C74 , (b) Si@C74 , and
(c) a single Si atom
196 Takeo Oku et al.

encapsulated atoms are ionized and change the electronic states. In the pres-
ent work, the energy gap of a single Si atom is calculated to be 0.452 eV,
as shown in Fig. 5c, and electronic state of the Si atom is isolated by the
C74 cluster. The Si atom would keep the original electronic state inside the
C74 cluster, which would be interesting for investigation of atomic properties
of Si.

4 Onions and Nanotubes


Carbon was formed from polyvinyl alcohol after annealing at 400◦ C in Ar,
and the carbon matrix was found to have an amorphous structure from the
HREM image, as shown in Fig. 6a. The amorphous carbon was irradiated by
an electron beam for 20 min under a beam current of 100 A/cm2 at 1250 kV.
This beam current is ∼ 20 times higher compared to that of the ordinary
HREM observation. Graphitization of amorphous carbon is observed, which is
confirmed by the lattice fringes of carbon layers with a spacing of ∼ 0.34 nm,
as shown in Fig. 6b. Two carbon onions were produced from amorphous
carbon as shown in Fig. 6b. Lattice fringes of the carbon {002} planes are
observed.
Figure 6c is an HREM image of tetrahedral carbon onion produced from
that of Fig. 6b [27]. By electron-beam irradiation for 10 min on the onions
of Fig. 6b, a carbon onion with tetrahedral structure was formed as shown
in Fig. 6c. The edge lengths of the first and second internal shell of the
tetrahedral carbon onion are approximately 0.8 and 1.4 nm, respectively.
The distance between onion layers is 0.35 nm. Although a similar structure
consisting of C264 @C660 @C1248 was calculated [15], the size of the present
tetrahedral carbon onion is smaller compared to the C264 .
Figure 6d is a six-layered onion structure, and the outside is calculated to
be C2160 from the equation 60n2 (n is the number of the shell). The lattice
fringes of the carbon {002} planes are smeared at the edges of the onions with
pentagonal carbon bonding, as indicated by arrows. “Atom clouds” [51, 52],
which have vague contrast, are also observed at the vertices of onion edges as
indicated by arrows. The carbon “vibration” was also observed at the surface
of the onions. The shell structure is not perfect, but has some defects. The
same onion after 60 s is shown in Fig. 6e. Change of the vertices into spherical
structure is observed on the onion surface. At the center of the onion, there
would be a C28 cluster from the size of ∼ 0.4 nm. Although this structure
would be unstable, the C28 cluster would be stabilized by compressive tension
of outer onion. The structure model is proposed as shown in Fig. 6f.
At the center of the onion in Fig. 6c, there would be a tetrahedral carbon
cluster and the basic arrangements of carbon atoms are proposed, as shown
in Fig. 7a. Each vertex consists of a hexagonal ring (as indicated by a star
mark), and three pentagonal rings exist around the vertex along the edge.
Other parts consist of only hexagonal rings. Edge lengths of the C84 and
Carbon Nanocage Materials 197

Fig. 6. (a) HREM image of as-prepared amorphous carbon. (b) Two carbon onions
produced from amorphous carbon (a) by electron-beam irradiation for 20 min.
(c) Tetrahedral carbon onion produced from (b) by electron-beam irradiation for
30 min. (d) HREM images of onion structures. (e) Six-layered carbon onion; 60 s
after (d). (f ) Structure model of C24 @C84
198 Takeo Oku et al.

Table 2. Calculated values for tetrahedral carbon onions


C84 Td C168 C276 C408 C84 @C276 C84 D2
(No. 20) (No. 22)
Calculation method PM3 PM3 MM3 MM3 MM3 PM3
Layer number 1 2 3 4 1, 3 –
Edge length (nm) 0.8 1.0 1.4 2.0 1.4 –
Interatomic distance of
pentagonal rings (nm) 0.1445 0.1444 0.1399 0.1399 – 0.1438
Interatomic distance of
hexagonal rings (nm) 0.1452 0.1429 0.1407 0.1406 – 0.1464
Total steric energy
(kcal/mol) 362 395 389 345 823 335
Total steric energy
(kcal/mol · atom) 4.31 2.35 1.41 0.85 2.29 3.99
Heat of formation
(kcal/mol) 991 1413 – – – 967
Heat of formation
(kcal/mol · atom) 11.8 8.41 – – – 11.5

C276 in optimized structures are 0.8 and 1.4 nm, respectively. The total num-
bers (N ) of carbon atoms of the present tetrahedral onions are represented
by the equation N = 12(n + 2)2 − 24 (n = 1, 2, ...). Edge lengths of the C84
and C276 agree with the first and second internal shells of tetrahedral carbon
onion in the HREM image, respectively. Steric energy by molecular mechan-
ics calculations and heats of formation by semiempirical molecular orbital
calculations on tetrahedral carbon clusters are summarized in Table 2.
On the basis of the projected structure model of Fig. 7c, image calcu-
lations on the C84 @C276 cluster were carried out for various defocus values
to investigate the cluster structures. The smallest tetrahedral onion in the
HREM image in Fig. 6c agrees well with the calculated images of C84 @C276
in Fig. 7c. In this optimized model, the distance between layers is close to
the observed value of 0.35 nm. Further refinement has to be carried out in
which the van der Waals interaction is considered. Energy levels and density
of states of C84 were calculated, as shown in Fig. 7b. Energy gaps of C60 ,
C84 , and C168 clusters were calculated to be 2.13, 2.06, and 1.44 eV, respec-
tively. The experimental energy gap of C60 is 1.7 eV [53]. Since the difference
between the present calculation and the experimental data is approximately
0.4 eV, the energy gap of a C84 cluster would be approximately 1.6 eV, which
is a little smaller compared to that of the C cluster. The increase of numbers
of the 60 carbon atoms decreased energy gaps of the clusters, as calculated
for C186 (1.44 eV). In addition, DOS for C186 is broader than that of C84 .
The formation mechanism can be described with three effects: cutting of car-
Carbon Nanocage Materials 199

Fig. 7. (a) Proposed structure models of tetrahedral carbon onions: C84 , C168 , C276
and C408 (◦, pentagonal ring; , vertex (hexagonal ring)). (b) Energy level diagram
and density of states for C84 . (c) Structure model and (d) calculated HREM images
of C84 @C276 onion as a function of defocus values

bon bonds by electron irradiation, knock-on of carbon atoms, and increase of


sample temperature. In the present work, bonding cuts and knock-on effects
would be important. These effects cause fluidization of the structure, which
provides a spherical structure by the surface tension. In Fig. 6b, two onions
were observed and their collision would occur during onion formation. The
onion would be formed from the outside because C84 is too unstable to be
fabricated, compared to C60 and related giant fullerenes. The outsidemost
layer would be formed first, and inside layers would be formed gradually. In
the end, the number of remaining carbon atoms is important to construct
the structure at the center of the onion, so that C84 would be formed in the
present work. Concerning the shape and the size of the onion, the center of
the onion would be C84 , and the onion would have any effect from the carbon
200 Takeo Oku et al.

layer located outside. There are two important theorems of the Euler rule [54]
and the isolated pentagon rule (IPR) [55] in the formation of the fullerene.
Even if the closed fullerene size becomes larger, the number of pentagonal
rings is always 12 by the Euler rule. Pentagonal rings do not adjoin to others
based on the IPR rule when the size becomes bigger than C60 . There are
24 structural isomers in C84 [56], and C84 D2 and C84 D2d with the ratio of
2 : 1 are the main structural isomers. The first inside shell of the tetrahedral
carbon onion is equivalent to the C84 Td structural isomer. Heats of forma-
tion of C84 D2 and C84 D2d by the PM3 calculation are 967 and 968 kcal/mol,
respectively. This means that a spherical structure is more stable than the
tetrahedral structure (heat of formation 994 kcal/mol), and the Stone–Wales
transformation [57] would be introduced during the growth of C84 Td to sat-
isfy the Euler rule and the IPR rule. The position of the pentagonal ring
can be moved by this transformation keeping the fullerene size. Although
this tetrahedral structure (C84 Td ) might transform into spherical structure
(C84 D2 and C84 D2d ), the energy barrier between them would prevent the
transformation. The barrier would be the van der Waals force from outside
shell and distortion due to the collision of two onions.
The smallest carbon nanotube with a diameter of 0.4 nm was reported
in [58]. They showed a HREM image of the multiwalled carbon nanotube,
and they proposed an atomic structure model of C20 for the cap structure.
However, the nanotube was not an isolated single-walled nanotube.
Figure 8a is an HREM image of isolated carbon mininanotube on the
carbon layers. The diameter and length of the nanotube are 0.5 and 3.1 nm,
respectively. Figure 8b is a proposed atomic structure model of carbon mini-
nanotube C180 . The size of the C180 agrees well with the observed image of
Fig. 8a. The cap of the nanotube consists of a part of the structure of a C36
cluster, which are indicated by dark gray. Figure 8c is a 30◦ -rotated model
of Fig. 8b along the nanotube axis. The atomic structure model of the C180
carbon mininanotube along the nanotube axis is shown in Fig. 8d. Carbon
atoms corresponding to C36 clusters are indicated by dark gray. A structure
model of C36 is also shown in Fig. 8e. The distortion of the mininanotube
would be mitigated by the surface of the carbon layers, which may stabilize
the cap structure.

5 Carbon Nanocapsules
Although many carbon nanocapsules with various elements and compounds
have been prepared by an ordinary arc-discharge method, a few nanocapsules
filled with Ge and SiC have been reported.
A HREM image of Ge nanoparticles encapsulated in graphite sheets is
shown in Fig. 9a. In Fig. 9b, the Ge nanoparticle is surrounded by one to three
graphite sheets. Figure 9c is a HREM image of a Ge nanowire encapsulated
in a carbon nanotube with one to two graphite sheets. The diameter is 10 nm,
Carbon Nanocage Materials 201

Fig. 8. (a) HREM image of carbon mininanotube on the carbon layers. (b) Pro-
posed atomic structure model of carbon mininanotube C180 . (c) 30◦ -rotated model
of (b) along nanotube axis. (d) Structure model of C180 carbon mininanotube along
nanotube axis. (e) Structure model of C36
202 Takeo Oku et al.

Fig. 9. (a) HREM image of Ge nanoparticles encapsulated in carbon sheets. (b) En-
larged image of the nanocapsule. (c) Ge nanowire encapsulated in carbon nano-
tube. HREM images of (d) carbon nanocapsules with SiC nanoparticles, (e) car-
bon nanocapsule and nanohorn. (f ) Enlarged image of SiC cluster encapsulated in
carbon cage

and the length is 70 nm. The Ge nanowire has microtwin structures, and the
growth direction of the nanowire is < 111 > of Ge [29].
A HREM image of carbon nanocapsules with SiC nanoparticles is shown
in Fig. 9d. SiC nanoparticles with sizes of 6–10 nm are observed. All SiC
nanoparticles are encapsulated in graphite sheets, and the number of graphite
sheets was in the range of three to ten layers. A HREM image of the carbon
nanocapsule and nanohorn is shown in Fig. 9d. Five to six graphite layers are
observed around the nanoparticle, and the size of the carbon nanocapsule is
Carbon Nanocage Materials 203

Fig. 10. Structure models for carbon nanohorns. Three and five pentagonal C rings
are introduced for model (a) C67 and (b) C74 , respectively. (c) Density of states
for C74 nanohorn

4 nm. Lattice fringes with a distance of 0.25 nm, which corresponds to the
distance of the {111} planes of β-SiC, are observed in the cluster. A car-
bon nanohorn with three graphite sheets is observed. The tip of the cage is
smeared. Figure 9e is a HREM image of a carbon nanocapsule filled with a
SiC nanocluster of size 2 nm.
In this work, a special DC-RF arc-discharge method was used, which re-
sults in their formation. The SiC nanoparticles would be formed by reaction of
Si and C atoms in the arc plasma. The DC-RF arc-discharge plasma would
be effective for the formation of semiconductor nanoparticles encapsulated
in graphite sheets. In the present work, the sizes of the semiconductor Ge
and SiC nanoparticles were reduced down to 10 nm, which indicates that
the widening of the band-gap energy is expected by quantum size effects,
and peculiar optical properties will be expected. Ge nanowires encapsulated
in carbon nanotubes are also expected as one-dimensional devices. Si ox-
ide and Ge oxide layers are not observed at the surface of the SiC and Ge
nanoparticles, which indicates that the carbon nanocapsules are effective for
cluster protection against oxidation in air. Figure 10 show structure models
for carbon nanohorns observed in Fig. 9e. Three and five pentagonal C rings
are introduced for model Figs. 10a and 10b, respectively, and the model in
Fig. 10b is equivalent to the previously proposed model [59].
Heats of formation of the C67 and C74 clusters were calculated to be
22.18 and 20.53 kcal/mol · atom, and the stability of C74 is higher than that
of C67 . DOS of C74 nanohorns were calculated, as shown in Fig. 10c. Energy
level diagram of C74 nanohorn shows narrow energy gaps of 0.49 eV between
the HOMO–LUMO gap. Carbon nanohorns are expected as catalytic elec-
204 Takeo Oku et al.

Fig. 11. (a) HREM image of carbon nanocapsules with SiC cluster. (b) Photolumi-
nescence spectrum of (a). (c) HREM image of surface of carbon nanocapsule with
SiC together with calculated image based on the proposed interfacial model (d)

trode materials for fuel cells in next generation, which separate hydrogen
and electrons from methanol [8].

6 Properties of Carbon Nanomaterials


6.1 Photoluminescence of Carbon Nanocapsules

SiC nanoparticles prepared with polyvinyl alcohol were annealed at 500◦ C in


an Ar atmosphere. The particle size of SiC is in the range of 5–50 nm. All the
SiC particles are surrounded by graphite sheets, and the number of graphite
sheets is in the range 1–6. An enlarged HREM image of a carbon nanocap-
sule is shown in Fig. 11a. Lattice fringes with a distance of 0.25 nm, which
corresponds to the distance of {111} planes of β-SiC, are observed in the
nanoparticle. Two {002} planes of graphite grow on the β-SiC nanoparticle.
Carbon Nanocage Materials 205

The PL spectrum of the carbon nanocapsules encasing SiC clusters is


shown in Fig. 11b [12]. A luminescence peak is observed at 382 nm, which
corresponds to ∼ 3.2 eV. The bulk SiC has an energy gap of 3.00 eV. The
present carbon nanocapsules with SiC clusters have higher energy compared
to the bulk SiC, which would be due to the quantum size effect of SiC as
shown in Fig. 11a. A HREM image of the surface of a carbon nanocapsules
with SiC nanoparticle is shown in Fig. 11c. Carbon {002} planes grow epi-
taxially on the SiC {111}, but disordered carbon structure is observed on
the SiC {200}. Epitaxial growth of carbon {002} on the β-SiC {111} planes
was often observed at the nanocapsule/nanoparticle interfaces in the pres-
ent work. A similar epitaxial relationship was observed at the carbon/β-SiC
in previous study [60]. The information on atomic arrangement at the car-
bon/SiC interface was obtained from the HREM images in the present work,
and two structural models of the carbon/SiC interface were constructed, as
shown in Fig. 11d. In Fig. 11d, carbon atoms that belong to the SiC structure
connect with carbon atoms of the graphite. From the present high-resolution
observation, the carbon {002} is parallel to the SiC {111}, and carbon [1,−1,0]
is nearly parallel to SiC [0,1,−1]. (If the incidence is parallel to carbon [0,1,0],
two-dimensional lattice fringes should be observed.) The distance between
the SiC crystal and graphite layer was assumed to be 0.335 nm, which is the
same as that of graphite {002} planes. Based on these models, HREM images
are calculated as shown in Fig. 11c as an inset. In the observed images, the
distance between the dark contrast of the first carbon layer and the top of
the SiC crystal is almost the same as that of carbon {002}, which indicates
that carbon atoms of the graphite-type structure directly connect with car-
bon atoms that belong to the SiC structure. Graphitization of amorphous
carbon on SiC {111} planes would be easier compared to the SiC {200}. It is
believed that the carbon surface of SiC would have a low activation energy
for graphite growth, which results in the heterogeneous nucleation growth of
graphite.

6.2 Magnetic Properties of Carbon Nanocapsules

Magnetic nanoparticles are suitable for potential applications like high-den-


sity magnetic recording media [61], magnetic fluids [62], electromagnetic wave
absorbing materials [63], magnetic carriers in clinical cures, and other novel
magnetic devices. Iron (Fe) or Fe-based alloy nanoparticles have an advan-
tage of high saturation magnetization for these applications, whereas deteri-
oration by oxidation has kept them from practical usage. To overcome this
problem, nanocoating techniques for the metal nanoparticles have been re-
ported [24, 25].
Carbon nanocapsules encapsulated Fe are shown in Fig. 12a. Fe nanopar-
ticles with 100–200 nm diameters are observed as shown in Fig. 12a. An
EDX spectrum of the nanoparticles confirmed that they are Fe nanoparticles.
HREM makes it clear that the Fe nanoparticles are coated with well-oriented
206 Takeo Oku et al.

Fig. 12. Morphology of C-coated Fe particles. (a) TEM image of C wire with Fe
particle. (b) Microstructure of coating layers encapsulating Fe particle. (c) Mag-
netic hysteresis loops of C-coated Fe particles with maximum DC applied field of
0.8 MAm−1 . (d) Dependence of magnetization on temperature for commercially
available carbonyl Fe, BN-coated Fe and C-coated Fe particles. Magnetization at
each temperature is normalized with reference to that at 25◦ C

layers of ∼ 5 nm in thickness (Fig. 12b). The spacings of the lattice fringes


in the layers revealed that the crystal structure is graphitic carbon with the
spacing of 0.34 nm of {002} plane. The C-coated Fe nanoparticles also grew
nanotubes of 50–100 nm in diameter, ∼ 1 µm in length, and ∼ 10 nm in wall
thickness (Fig. 12a). Detailed observation of these tubes reveals that they
have a multiwalled structure with something like joints inside. Multiwalled
carbon nanotubes have been formed with diameters in the range from 1.4 nm
to at least 100 nm [64,65]. So, the carbon nanotubes in this sample have large
diameters.
The magnetic properties of C-coated Fe nanoparticles in Fig. 12c were
measured at room temperature. A magnetic field higher than 0.6 MAm−1
must be applied in order to saturate magnetizations, because the demag-
Carbon Nanocage Materials 207

netizing factor of Fe nanoparticles would be larger than that of bulk Fe.


Coercivities are very low, so the samples exhibit soft magnetic properties.
Magnetization (Ms ) and coercivity (Hc ) values of the sample were measured
to be 193 Am2 kg−1 and 1.1 kAm−1 under an applied field of 1.6 MAm−1 .
The Ms value is 87% of the value of bulk Fe [66]. Ms values of Fe or Co
nanoparticles with C nanocoatings have been reported to be 40–60% of those
of the bulk metals, and the Hc values are around several hundred oersteds
(∼ 20 kAm−1 ) [67, 68]. In particular, the C-coated Fe nanoparticles in this
work have much higher Ms values than the reported values. The Hc values of
the C-coated Fe nanoparticles are lower as well. Herzer showed that the Hc
of soft magnetic metal particles depends on the particle size [69]. Lower Hc
values would be due to large particle sizes. The particle sizes in this work are
100–500 nm, about ten times larger than reported nanoparticle sizes. Con-
sidering that coercivity disturbs soft magnetic properties, it is obvious that
this C-coated Fe nanoparticles is excellent as soft magnetic materials.
In order to investigate resistance to oxidation, Ms values were measured,
heating the C- and BN-coated Fe nanoparticles from 27◦ C to 800◦C in air
(Fig. 12d). Commercially available carbonyl Fe powders, which have an av-
erage diameter of 3 mm, were also measured as a reference. The Ms values of
all three samples decrease gradually as temperature increases, and fall to zero
abruptly at elevated temperatures. The Ms of the carbonyl Fe disappears at
∼ 600◦ C. The BN- and C-coated Fe samples still keep their Ms at more than
60% of the initial value even at 600◦ C, and decrease to zero at ∼ 800◦ C. As
the Curie temperature of magnetite (Fe3 O4 ) is 587◦ C (‘T1’ in Fig. 12d), the
degradation of Ms in carbonyl Fe could be explained as oxidation and trans-
formation of Fe into Fe3 O4 . The temperature of ∼ 800◦ C coincides with the
Curie temperature of iron (767◦ C, indexed as ‘T2’ in the figure). Accordingly,
the BN- and C-coated Fe nanoparticles exhibit resistance to oxidation.

6.3 Possibility of H2 Gas Storage in Carbon Nanocages

Clean hydrogen energy is expected as substitute for oil energy in twenty-first


century. LaNi5 H6 is already used as H2 gas storage material. However, the H2
gas storage ability is only 1 wt. % because of large atomic number of La and
Ni. On the other hand, fullerene materials, which consist of light elements
such as boron, carbon, and nitrogen, would store more H2 gas compared to
the metal hydrides. It was reported that H2 gas was stored in alkali-doped
carbon nanotubes under ambient pressure and moderate temperature [70].
Collision between C60 and alkali-metal ions was also calculated to investigate
a possibility of Li@C60 by molecular dynamics calculations [71]. Here, the
possibility of H2 gas storage in fullerene materials was investigated.
The condition of H2 gas storage into C60 cage and H2 gas discharge
from C60 were calculated by molecular dynamics software (MASPHYC). The
conditions were set as follows: pressure (p) and temperature (T ) are con-
stant, or volume (V ) and temperature are constant. H2 gas storage into C60
208 Takeo Oku et al.

Fig. 13. (a) Molecular dynamics calculation of H2 gas storage in C60 cage.
(b) Atomic structure models of C186 nanotube. (c) Structure models wherein the
H2 molecule passes from pentagonal and hexagonal rings of C60 . (d) Structural
model of H atom chemisorbed on C60
Carbon Nanocage Materials 209

cages is shown in Fig. 13a. This model is calculated under the condition of
V = 8.0 × 10−27 m3 and T = 150 K. The H2 molecules pass through the
hexagonal rings of C60 cage at 20 ps. After introducing H2 molecule into the
C60 cluster at 40 ps, H2 is stored and stable in C60 . The condition of H2 gas
discharge from C60 is similar to that of H2 gas storage, which is as follows:
T = 300 K and p = 0.15 GPa. Although electronic structure calculation of
hydrogen in C60 was reported [72], the present work showed the molecular
dynamics of H2 molecule storage in C60 cluster.
The H2 molecules are considered to enter from the cap of nanotubes,
where the curvature is finite, as shown in Fig. 13b. The possibility of H2 gas
storage in C nanotubes was investigated by using first-principle calculations.
In the present work, C60 was used to calculate the end-cap structure of the
nanotube. In this case, only cap structures should be in the calculations. In
the nanotubes, H2 molecule would invade from the cap of tube in the same
way because of coulomb barriers of the tube wall. C60 clusters would have
energy barriers for H2 molecules to pass through pentagonal and hexagonal
rings. Figure 13c shows structure models wherein the H2 molecule passes
from pentagonal and hexagonal rings of C60 . Single-point energies were cal-
culated with changing set points of H2 molecule from the center of the cage
at intervals of 0.1 nm. Energy barriers were calculated for H2 molecules to
pass through pentagonal and hexagonal rings, and they are 23 eV and 16 eV,
respectively [73].
Figure 13d is a structural model of hydrogen atoms chemisorbed on a
C60 cluster. Atoms bonded with hydrogen are moved outside from the clus-
ters. The hydrogenated energies for C60 H and C60 H2 were calculated to be
−0.18 and 0.6 eV, respectively [74]. Hydrogen bonding with a carbon atom
of C60 is more stable than C60 . When two hydrogen atoms were chemisorbed
on carbon clusters, energies of carbon clusters increased.
To investigate stability of H2 molecules in clusters, energies were calcu-
lated for H2 molecules placed in the center of a C60 cluster, as summarized
in Table 3. Structural models are shown in Fig. 13e. When more than 22 H2
molecules were introduced in C60 , hydrogen atoms chemisorbed inside the
cluster [75]. When more than 26 H2 molecules were introduced in the C60
clusters, 22 H2 molecules were in the cluster and 8 hydrogen atoms chemi-
sorbed inside the clusters and the C–C bond was broken.

6.4 One-Dimensional Self-Organization of Nanocapsules

The recent speed-up of ultra-large scale integrated circuits (ULSI) of semi-


conductor devices is based on the minimization of the design rule. New prop-
erties are also expected by the formation of low dimensional arrays of quan-
tum dots. The photolithography technique is used for the formation of these
nanostructures, and the ULSI with 0.07 µm rule will be produced in 2009 [76].
However, the limit of the design rule is reported to be 0.05 µm (= 50 nm) by
using extreme ultraviolet lithography [77]. It is believed that establishment
210 Takeo Oku et al.

Table 3. Energy of C60 cluster with hydrogen. A C–C bond was broken in case of
8 chemisorbed hydrogen atoms (∗ )

Introduced Optimized Heat of formation Hydrogen atoms Hydrogen storage


H2 H2 (eV) chemisorbed (wt. %)
inside cluster
0 0 35.21 0 0
20 20 127.54 0 5.6
22 22 143.01 0 6.1
25 25 164.87 4 6.9
26 26 169.63 8 (∗ ) 7.2
30 24 165.59 4 6.7

of nanostructure-formation techniques by self-organization of nanoparticles


is worth pursuing in order to overcome the lithography limit. Spontaneous
formation of well-organized nanostructures is intriguing for both scientific
research and future electronic-device application. However, dimensionality of
this self-organization has been two and three [78, 79], and one-dimensional
self-organization has been needed for the formation of “nanowiring” for the
future ULSI devices.
Gold nanoparticles and nanowires encapsulated in carbon nanocap-
sules and nanotubes were spontaneously formed from one-dimensional self-
organized gold nanoparticles on carbon thin films by annealing at low temper-
atures of 200–400◦C, as shown in Figs. 14a–c [30, 31]. The gold crystals inside
the nanotubes are distorted by the crystal growth of the nanowires, as shown
in Figs. 14d and 14e. Lattice expansion and reduction are observed parallel
and perpendicular to the growth axis, respectively. It is believed that the dis-
tortion of the nanowire would be due to the coalescence of nanoparticles along
the growth direction at the low temperatures. A conductivity (dI/dV ) curve
of a single carbon nanocapsule with Au nanoparticles is shown in Fig. 14f,
which indicates the V-shape behavior with the gap of ∼ 0.5 V [80]. This would
be due to the disordered carbon layers at the carbon/Au interface as shown
in Fig. 14g.
A schematic illustration of self-organized Au nanoparticles, carbon nano-
capsules, and carbon nanotube is shown in Fig. 14h. For the one-dimensional
positioning, adhesive force due to the step edge and substrate are mainly
used. The ordinary ordering mechanism for nanoparticle self-organization is
due to the internanoparticle force by α-terpineol and adhesion by the sub-
strate. The width of the one-dimensional line could be controlled by the
interactive force of α-terpineol. The present result indicates that the one-
dimensional arrangement is strongly dependent on the atomic step edge of
the substrate. The difference in the formation of carbon nanocapsules and
nanotubes would be due to the distance between the gold nanoparticles. Al-
though the atomic step edge is formed by the common sample preparation
Carbon Nanocage Materials 211

a b c

2nm
2nm

1-11 e
d 200
C

5nm
000 Au

11-1

㨪5%
g
dI/dV (arb. units)

(f) 0.5 V

Au
-0.5 -0.25 0 0.25 0.5 1nm
Sample bias (V)
(h) ǩ-terpineol
1D arrangement of CNC

Au
3nm
a-carbon 15nm
graphite layers

Au
ǩ-terpineol 5nm

Au Au
3nm

͠
a-carbon 15nm amorphous carbon
200-400
CNT with Au nanowire
1D model
graphite layers
C layer 10nm
Au
Au
3nm
amorphous carbon
a-carbon 15nm

Fig. 14. (a) Low-magnification image of one-dimensional self-organized carbon


nanocapsules with Au nanoparticles on amorphous carbon film. (b) Alternate
arrangement of different size of carbon nanocapsules with gold nanoparticles.
(c) HREM image of Au nanowire in carbon nanotube. (d) Fourier transform of
nanotube. (e) Structure model of Au{111}/C{002} interface. (f ) Conductivity
curve of a single carbon nanocapsule with Au nanoparticle. (g) Enlarged HREM
image of carbon/Au interface. (h) Schematic illustration of one-dimensional self-
organized Au nanoparticles, carbon nanocapsules and carbon nanotube
212 Takeo Oku et al.

technique in the present work, the atomic step could be controlled by or-
dinary lithography techniques such as electron beam, and is expected as a
nanofabrication technique for future electronic devices. The present result is
expected as a future fabrication technique for self-assembled ULSI nanowires
and quantum dots protected by nanocapsules and nanotubes at scales beyond
the limits of current photolithography.

7 Conclusion
Various C fullerene materials were synthesized by polymer pyrolysis, chem-
ical reaction, DC-RF hybrid arc discharge, and electron-beam irradiation.
Atomic structure and formation mechanisms were investigated by HREM,
and structural models were proposed. Measurements of PL and magnetic
properties of C nanocapsules showed a higher energy shift of luminescence
and good soft magnetic properties. The present work indicates that the new
C fullerene materials with various atomic structures and properties can be
produced by various synthesis methods, and are expected to be the future
nanoscale devices.

Acknowledgements

The authors would like to thank T. Hirano, M. Kuno, H. Kitahara, K. Hiraga,


E. Aoyagi, H. Kubota for their useful discussion, experimental help, and
collaborative work.

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Index
atomic structures, 187 C74 :Si, 192–195
C76 , 194
C168 , 198, 199 C82 , 192
C180 , 200, 201 C84 , 192, 198, 199
C186 , 198 C84 :C24 , 197
C20 , 200 C84 D2 , 198, 200
C2610 , 196 C84 D2d , 200
C264 , 196 C84 Td , 198
C276 , 198, 199 C84 Td , 200
C276 :C84 , 198, 199 carbon clusters, 194
C28 , 196 endohedral clusters, 192
C36 , 190, 200
C408 , 198, 199
fullerene, 187–192
C60 , 187, 191–194, 198, 200
fullerene materials, 188, 189, 207
C60 :Li, 207
giant fullerene, 192, 199
C60 :N, 192
C60 :Rb, 192
C60 with hydrogen, 207–211 graphitization, 205
doped C60 , 191
C67 , 203 high-resolution electron microscopy
C70 , 190, 194 (HREM), 191, 192
C72 , 194 highest occupied molecular orbital
C74 , 192–195, 203 (HOMO), 194
C74 :Ca, 194 HOMO-LUMO gap, 194, 203
C74 :Eu, 194 hybrid arc-discharge, 187, 189, 190,
C74 :Gd, 194 192, 203
C74 :La, 194 hydrogen storage, 207–209, 211
216 Takeo Oku et al.

lowest unoccupied molecular orbital mininanotube, 200


(LUMO), 194 multi-walled nanotubes (MWNTs),
200
metallofullerene, 187, 190, 192 multiwalled nanotubes (MWNTs),
molecular dynamics, 207 206
nanocages, 187, 189, 207 single-walled nanotubes (SWNTs),
nanocage materials, 189 200
nanocapsules, 187, 190, 192, 200, nanowires, 200, 203, 210, 211
202–205, 207–211
self-organization, 187, 209 onions, 187, 196–199
one-dimensional self-organization, tetrahedral onions, 196–198
209
nanohorns, 187, 202, 203 photoluminescence (PL), 187, 189, 204
nanoparticles, 210
gold nanoparticles, 210, 211 SiC, 200, 202–205
nanostructures
hollow-cage-nanostructures, 187 ultra-large scale integrated circuits
nanotubes, 187, 192, 196, 201–203, 208, (ULSI), 209
210, 211 self-assembled ULSI, 212
Hard Amorphous Hydrogenated Carbon Films
and Alloys

Fernando L. Freire Jr.

Pontifı́cia Universidade Católica do Rio de Janeiro, Departamento de Fı́sica


Rua Marquês de São Vicente 225, Rio de Janeiro, BR-22452-900, RJ, Brazil
lazaro@vdg.fis.puc-rio.br

Abstract. Hard hydrogenated amorphous carbon films are presently being used
in a wide variety of applications as protective coatings. The properties of the car-
bon films are essentially controlled by the ratio between the number of carbon
atoms in sp2 and sp3 hybridization states. The properties of the films, which are
closely related to the film microstructure, can be tuned by the deposition tech-
nique employed and by the growth conditions, with the energy of the impinging
species playing the main role in the control of the carbon bonding hybridization.
Another way to improve the properties of carbon films is through the incorpora-
tion of several elements. In this work, the attention is focused on films deposited
by plasma-enhanced chemical vapor deposition, discussing the effects of nitrogen
and fluorine incorporation on the film microstructure and on the mechanical and
tribological properties.

1 Introduction
Amorphous carbon films are nanostructured materials made of clusters of
sp2 -hybridized carbon atoms, with a typical size of a few nanometers, con-
nected to each other by sp3 -hybridized carbon atoms. The electronic and op-
tical properties of these materials are mainly controlled by the size of the sp2
clusters, while the mechanical properties are given by the degree of intercon-
nectivity of the amorphous skeleton, i.e., the fraction of sp3 -hybridized carbon
atoms present in the matrix [1]. Film properties can be tuned by choosing
the deposition technique with the appropriated deposition conditions. Among
the different deposition parameters, the energy of the impinging ions plays
the more important role and controls the sp2 /sp3 -hybridized carbon atoms
ratio. The subplantation model suggests that the deposition of hyperthermal
carbon species is a shallow implantation process, where the incorporation of
carbon species in subsurface layers followed by internal stresses is the dom-
inant mechanism, responsible for the formation of a sp3 -carbon-rich dense
phase, the diamondlike phase [2]. Recently, this model was improved with
the inclusion of the role of the interstitials, which are physically and ener-
getically different from the bulk sp2 and sp3 carbon atoms [3]. In this way,
films with properties typical of polymers, graphite or diamond can be syn-
thesized. Carbon films are used in a wide variety of applications as protective

G. Messina, S. Santangelo (Eds.): Carbon, The Future Material for Advanced Technology Ap-
plications, Topics Appl. Phys. 100, 217–238 (2006)
© Springer-Verlag Berlin Heidelberg 2006
218 Fernando L. Freire Jr.

coatings. In particular, films deposited by magnetron sputtering, plasma-en-


hanced chemical vapor deposition (PECVD) and filtered cathodic vacuum
arc (FCVA) are used as overcoats for biomedical implants [4], computer hard
disks [5] and as spacer tools for electron guns of cathode ray tubes [6].
The incorporation of hydrogen in the amorphous skeleton also plays an
important role. The amorphous hydrogenated carbon films (a-C:H) can be
deposited by both sputtering and PECVD techniques in a large range of
sp2 /sp3 -hybridized carbon atom ratios. The hydrogen content in these films
can vary from 0 to 50 at. %. Depending on the deposition conditions, sub-
strate bias voltage, substrate temperature, and pressure and gas precursor
atmosphere, they can be either diamond-like (sp3 -rich films) or graphitic-like
(sp2 -rich films). However, a-C:H films with high H content and high frac-
tions of carbon atoms with sp3 hybridization have a polymeric character. It
was shown that the subplantation model could also be applied to describe
the mechanisms of a-C:H growth by PECVD. In fact, the internal stress and
hardness of a-C:H films deposited by rf-PECVD in pure methane atmosphere
show a dependence with the self-bias voltage that is well described by the
subplantation model [7].
One of the ways of changing, in a controlled way, a-C:H film properties
is through the incorporation during the film growth of different elements,
such as nitrogen (N), fluorine (F), silicon (Si) and many metals, for example,
titanium (Ti). The incorporation of Si, for example, seems to stabilize sp3 -
carbon bonds and to improve the thermal stability of a-C:H films [8]. On the
other hand, the incorporation of one or more of these elements can induce
the formation of new nanostructured materials, as the fullerene-like carbon
films, films with strongly interacting curved graphene planes. The fullerene-
like structure results from the curving of the graphene planes induced by
nitrogen incorporation and is similar to that found in carbon nanotubes and
fullerenes [9]. In recent years, an important fraction of the research effort was
dedicated to the study of nitrogen incorporation on carbon films [10]. The
main reason of this effort was the intention to synthesize the C3 N4 , proposed
by Liu and Cohen [11], to have mechanical properties comparable to those
of crystalline diamond. In spite of this, no clear experimental evidence of
the formation of C3 N4 has been presented until now [12]. Nitrogen incor-
poration into a-C:H films was found to modify the structure [13] and the
mechanical properties [14] of these films, as well as their electrical and opti-
cal properties [15]. In fact, the fraction of carbon atoms in sp3 hybridization
state decreases upon nitrogen incorporation [16]. In terms of the mechanical
properties, a reduction on the internal compressive stress was observed, with
minor changes in the mechanical hardness [14]. Concerning the modification
of electrical and optical properties, it was found that nitrogen could electron-
ically dope a-C:H films, with the simultaneous reduction of the electronic
defect density [15]. This reduction makes possible the use of a-C:H:N films as
Hard Amorphous Hydrogenated Carbon Films and Alloys 219

a semiconductor material. In addition, a-C:H:N films deposited by PECVD


showed a promising performance as electron field-emitters [17].
The incorporation of fluorine in a-C:H films has also attracted inter-
est [18]. In spite of the lubricant properties of poly(tetrafluoroethylene)
(PTFE) the recent research on the fluorine incorporation into a-C:H films
was mainly motivated by its electrical properties. In fact, to improve the
switching performance of future ultra-large scale integrated circuits (ULSI),
insulator films with dielectric constants less than that of SiO2 are needed to
reduce the capacitance of interlayer insulators [19]. Fluorinated amorphous
carbon (a-C:H:F) films have been proposed as possible candidates due to
their dielectric constant [20]. These films can be plasma deposited in a wide
compositional range, the film fluorine content being determined primarily by
the atmosphere during deposition [21]. It has been found that the dielectric
constant decreases with the increase of the F/H ratio of the precursor at-
mosphere for films deposited by PECVD [22]. Notwithstanding the interest in
the dielectric properties of fluorinated amorphous carbon films, few attempts
to combine the mechanical properties of a-C:H films with the tribological
characteristics of PTFE have been made. The effect of fluorine incorpora-
tion on the mechanical [23] and tribological [24] properties of a-C:H films
has received more attention only in the last few years. As expected, fluorine
incorporation increases the surface hydrophobicity and reduces the friction
coefficient [25]. Besides, the effect of ionic bombardment during a-C:H:F film
growth has not been investigated in detail [26].
Up to now, only a few studies have concentrated on the simultaneous
incorporation of F and N into a-C:H films [27]. They were focused to the
structural characterization and the electrical properties of the films [28]. In
a recent investigation, it was shown that N atoms were incorporated into the
aromatic rings and as electronegative groups directly bonded to sp2 -carbon
in a-C:H:F films deposited by PECVD [29]. The incorporation of nitrogen,
which occurs at the expense of carbon atoms, induces modifications on the
surface hydrophobicity and friction behavior of the films, indicating a route
to control the surface wettability of these films [30].
In this review, a comparative study of the incorporation of N and F into
a-C:H films deposited by PECVD using CH4 –N2 and CH4 –CF4 mixtures
as precursor atmospheres is presented. The effects on the film microstructure
and mechanical properties will be discussed emphasizing the role of the energy
of the bombarding species. Tribological properties will also be discussed, as
well as the thermal stability of those films. Results of an investigation on the
incorporation of N into a-C:H:F films deposited by PECVD using CH4 –CF4 –
N2 mixtures as precursor atmospheres will also be presented, with special
attention to the tribological properties of a-C:H:F:N films.
220 Fernando L. Freire Jr.

Fig. 1. Nitrogen and fluorine content in a-C:H:N and a-C:H:F films as a function
of the methane partial pressure

2 Film Growth and Chemical Composition

a-C:H:N and a-C:H:F films were deposited by the plasma-assisted decompo-


sition of CH4 –N2 and CH4 –CF4 mixtures, onto Si substrates mounted on the
water-cooled copper cathode feed by an rf power supply (13.56 MHz). In this
method, the capacitive coupling allows the development of an average in time
DC negative potential at the powered electrode, the self-bias potential, V b ,
which extracts and accelerates ions from the plasma towards the powered
electrode. For deposition chamber pressure around 10 Pa, the mean energy
of those ions is around (1/3)eV b , where e is the electron charge [1]. Results
obtained from two series of films will be presented. In the first set of samples,
during the deposition V b was kept fixed at −350 V, while the CF4 and N2
pressures were changed from 0 to 80% and 0 to 50%, respectively. For the
second series, V b ranged from −100 V to −700 V with the N2 partial pres-
sure fixed at 40% of the total pressure for a-C:H:N films, while the partial
pressure of CF4 was 67% in the case of a-C:H:F film deposition. For the sake
of comparison, a-C:H films were deposited in pure methane atmosphere in
the same range of self-bias voltage. The desired V b value was adjusted by
changing the rf power in the range of 10–80 W. The total gas inlet flux was
fixed at 3 sccm. The pressure in the deposition chamber was 10 Pa. A 10 nm
thick a-C:H buffer layer was deposited without breaking the vacuum prior to
the deposition of the film in order to enhance the film adhesion. Without the
buffer layer, the a-C:F:H films peel off. Details of the experimental apparatus
can be found elsewhere [23]. The film composition was determined by ion
beam analysis (IBA): Rutherford backscattering spectrometry (RBS), elastic
recoil detection analysis (ERDA) and nuclear reaction analysis (NRA) [31].
Hard Amorphous Hydrogenated Carbon Films and Alloys 221

Fig. 2. Deposition rate of a-C:H:N and a-C:H:F films as a function of the methane
partial pressure

The chemical compositions of the films deposited while changing the pre-
cursor atmosphere are shown in Fig. 1, where the nitrogen and fluorine con-
tent of a-C:H:N and a-C:H:F films, respectively, were plotted as functions
of the partial pressure of methane. An increase of the F and N content in
the films occurs upon the the increase of the partial pressure of CF4 and
N2 . While in the case of a-C:H:N films the nitrogen incorporation occurs at
the expenses of the carbon content of the films, the hydrogen concentration
remaining constant within experimental errors around 20 at. %, in the case
of a-C:H:F films the incorporation of fluorine occurs at the expenses of the
hydrogen content, which decreases from 19 at. % to 1 at. %, in the range of
partial pressures considered in Fig. 1. The observed upper limits for the incor-
poration of nitrogen and fluorine in the films have different reasons and can
be understood with the help of Fig. 2, where the deposition rates of a-C:H:N
and a-C:H:F films are plotted as functions of the methane partial pressure.
The a-C:H:N deposition rate presents a sharp decrease when nitrogen par-
tial pressure increases, while the deposition rate of a-C:H:F films increases
by a factor of 2 when the partial pressures of CF4 increases from 0 to 80% of
the total pressure. For higher CF4 partial pressures, no film deposition but
substrate erosion occurs. It is important to note that for both a-C:H:N and
a-C:H:F film deposition, in order to keep V b constant at −350 V, the power
applied to the plasma is almost constant in the entire range of partial pres-
sures (CF4 or N2 ) studied, around 50 W. The deposition rate reduction due
to nitrogen incorporation observed in a-C:H:N film deposition was attributed
to the onset of a kind of chemical sputtering process arising from energetic
N+2 ion bombardment of the film growing surface [32]. In fact, it was found
that low-energy N+ 2 ion bombardment of pure amorphous carbon results in
222 Fernando L. Freire Jr.

carbon atom removal, at a rate of about 0.5 C atom per N+ 2 ion [33]. However,
there is no justification for the absence of the symmetric situation in carbon–
nitrogen film deposition process, i.e., nitrogen atoms being sputtered out by
carbon-carrying ions. We must consider both processes in the simulation of
ion beam deposition of carbon–nitrogen films. Besides, the possibility of N2
evaporation during film growth must be included. This situation is likely to
occur since N-atom subsurface penetration must favour N–N bond formation
with N atoms already in the film. The formation of other volatile species, such
as CN can also occur. These mechanisms are increasingly more probable for
deposition conditions that result in increasing nitrogen contents, reducing
the deposition rates. Therefore, the growth kinetics of carbon–nitrogen films
may be pictured as a competition between aggregation and erosion resulting
from the impinging of different species on the film-growing surface [34].
The increase of the deposition rate of a-C:H:F films with higher CF4 par-
tial pressure can be explained as follows: the growth of a-C:H films is mainly
due to the physisorption of hydrocarbon radicals onto the surface followed
by chemisorption of such radicals induced by energetic processes such as ion
bombardment. The existence of dangling bonds at the surface is expected
to enhance the sticking probability of carbon-carrying radicals [35]. As the
partial pressure of CF4 increases, the hydrogen concentration in the plasma
decreases together with the increase of the fluorine concentration. Fluorine
atoms can react on the surface by chemically eroding H from hydrocarbon
radicals, forming volatile HF and leaving a dangling bond on the surface. In
fact, a similar mechanism for dangling bond formation during the deposition
of a-C:H films has been reported [36]: atomic hydrogen chemically erodes hy-
drogen bonded on the surface of the growing film, leaving a dangling bond and
enhancing the sticking probability of CH3 radicals by a factor of 100. The hy-
drogen erosion induced by fluorine atoms is expected to be more efficient than
that induced by hydrogen atoms due to their much higher electronegativity.
In this way, the higher the CF4 concentration, the higher the probability of
hydrocarbon radicals sticking onto the surface. Besides, the higher the CF4
partial pressure, the higher the probability for large molecule formation in
the gas phase due to the agglomeration of CFx radicals [37], providing a new
channel for the formation of a fluorinated film up to the limit where there
are not enough hydrocarbon radicals to prevent F-induced substrate etching,
which occurs for CF4 partial pressure higher than 80%.
The a-C:H:N film composition is almost constant, within experimental
errors, for samples deposited in CH4 –N2 mixtures with N2 partial pressure
of 40% and with V b in the range of −100 V to −700 V. The nitrogen con-
tent is around 12 at. %, while the hydrogen content is typically 20 at. %. On
the contrary, fluorine and hydrogen contents in a-C:H:F films show a strong
dependence with the self-bias voltage, as shown in Fig. 3. An increase of the
fluorine content for higher V b was observed. Since the sum of the fluorine and
hydrogen concentrations is roughly constant around 20 at. %, these results
Hard Amorphous Hydrogenated Carbon Films and Alloys 223

Fig. 3. Fluorine and hydrogen content in a-C:H:F films as a function of the self-bias
voltage

Fig. 4. Deposition rate as a function of the self-bias voltage

suggest that fluorine is incorporated by substituting hydrogen. On the other


hand, the deposition rate increases with the increase of V b , as one can see
in Fig. 4. It can be understood as a result of the higher degree of plasma
dissociation due to the higher power needed to achieve higher V b . Also, the
contribution to a higher generation rate of nucleation sites on the film surface
due to the more energetic ion bombardment should be taken into account.
224 Fernando L. Freire Jr.

Fig. 5. Atomic density of a-C:H:N and a-C:H:F films as a function of the methane
partial pressure

3 Film Microstructure
The influence of the nitrogen and fluorine incorporation on the film micro-
structure was usually investigated following a multitechnique approach. Ra-
man and X-ray photoelectron (XPS) spectroscopies [38], as well as, infrared
absorption spectroscopy (IR), electron energy loss spectroscopy (EELS) [16]
and thermal-induced gas effusion experiments were used to probe film mi-
crostructure [39]. The atomic density can be evaluated by combining the
areal atomic density provided by IBA and the thickness of the samples, de-
termined by stylus profilometry [31].
The modifications in the film microstructure are illustrated by the results
of the atomic density presented in Fig. 5. In this range of nitrogen incorpora-
tion, the atomic density remains constant, but for fluorine content higher than
15 at. % (corresponding to a-C:H:F films deposited in a CH4 –CF4 atmosphere
with 33% of partial pressure of methane) the atomic density decreases from
1.3 to 1.1 × 1023 atoms/cm3 , indicating the occurrence of structural modifi-
cations in these films. As will be discussed in more detail below, this more
opened and relaxed structure has a polymeric character.
Three representative Raman spectra obtained from films deposited at the
same V b (−350 V) are shown in Fig. 6. The two spectra at the bottom
part of the figure obtained from a-C:H and a-C:H:N films are typical of a
diamond-like film, while the one at the top, obtained from a film with fluo-
rine content of 19 at. %, has a larger luminescence background, characteristic
of a polymer-like material [21]. The main features of the Raman spectra are
the two partially overlapping bands characteristic of all a-C:H films. They
are usually referred as the D (disorder) and the G (graphite) bands. The first
Hard Amorphous Hydrogenated Carbon Films and Alloys 225

Fig. 6. Raman spectra obtained from a-C:H, a-C:H:N (11 at. % of N) and a-C:H:F
(19 at. % of F) films. The position of the D and G bands are indicated by arrows

band, centered at around 1370 cm−1 , corresponds to the so-called D band


and is associated with disorder-allowed zone edge modes of graphite that be-
come Raman active due to the lack of long-range order [40]. The second one,
which peaks around 1550 cm−1 , is known as the G band and is attributed to
E 2g -symmetry optical modes occurring at the Brillouin-zone center of crys-
talline graphite [40]. This band is usually observed in the Raman spectra
of the a-C:H films as well as in ta-C films, but it may peak at slightly dif-
ferent energies in the two forms of amorphous carbon, depending on their
sp3 fractional content [41]. No other band besides the second-order Raman
was observed in the spectra. We can interpret the Raman results according
to the approach adopted by Dillon et al. for the analysis of the spectra ob-
tained from a-C films [42]. Recently, Ferrari et al. discussed in details the
Raman results obtained from carbon nitride films. This work is also taken
into account in the present analysis [43]. It was proposed that both the in-
crease in the ratio of the intensities of the D and G bands (I D /I G ) together
with the shift to higher frequencies of the position of the maximum and the
decrease of the width of the G band are indications of an increase in the
size of the sp2 -hybridized carbon domains. To obtain the evolution of these
226 Fernando L. Freire Jr.

Fig. 7. (a) I D /I G intensity ratio and (b) sp2 fraction as functions of the incorpo-
rated nitrogen. The lines are eye-guides only

bands against the changes in the film composition, the Raman spectra were
decomposed using two Gaussian functions, after the removal of the lumines-
cence background by means of a polynomial best-fit procedure [44]. In the
case of a-C:H:F films, a continuous shift of the position of the maximum of
the G band from 1538 to 1556 cm−1 (typical fitting errors of 5 cm−1 ) and
an increase of the I D /I G ratio by a factor of 2 was observed, together with
a decrease of the G bandwidth.
The Raman results obtained from the a-C:H:N films show a similar
trend [13]. These results are presented in Fig. 7, together with the sp2 fraction
as a function of the nitrogen content in the films.
The G band position shifts from 1538 to 1550 cm−1 and the G band-
width reduces from 165 to 153 cm−1 , while I D /I G increases by 60% upon
nitrogen incorporation up to 11 at. %. These results are interpreted as being
due to an increase of the size of the sp2 clusters. The increase of the fraction
of sp2 -hybridized carbon atoms measured by EELS (Fig. 7b) supports this
interpretation.
The increase of CF4 and N2 partial pressures, and consequently the in-
corporation of F and N, induces an increase in the size of the sp2 -hybridized
carbon domains. However, it should be pointed out that visible Raman spec-
troscopy is 50–230 times more sensitive to sp2 sites than to sp3 sites [45]. In
this way, the above analysis cannot completely describe the structural mod-
ifications induced by changing the deposition conditions. To this aim, more
information can be obtained, perhaps, from the evolution of the luminescence
background, underlying the a-C:H:F Raman spectra. In fact, while the lumi-
nescence intensity is negligible in the spectra obtained from a-C:H:N films or
a-C:H:F films with fluorine contents up to 14 at. %, it increases in films with
greater fluorine contents. The increase in the luminescence background has
Hard Amorphous Hydrogenated Carbon Films and Alloys 227

Fig. 8. XPS spectrum obtained


from an a-C:H:F film with 20
at. % of F. The main features of
the spectrum are indicated by ar-
rows

been discussed in terms of a structural rearrangement towards a polymer-like


structure [21], and this interpretation is reinforced by both the reduction of
the a-C:H:F film density upon fluorine incorporation and the XPS identifi-
cation of C–F2 bands, characteristic of fluorinated polymers, observed in the
films containing about 20 at. % of fluorine. The C1s XPS spectrum shown in
Fig. 8 can be fitted using four bands: C–C and C–H at 285.1 eV, C–CF at
287.1 eV, C–F at 289.3 eV and C–F2 at 291.5 eV [38]. The fluorine peak at
around 690 eV does not provide any information about the different chemical
bonds. XPS spectra taken from films deposited at lower CF4 partial pressure
are not shown in this figure. However, they show that higher CF4 partial
pressures lead to a relative increase in the intensity of fluorinated carbon
peaks. In fact, only for films with 20 at. % of fluorine, we observed the bands
corresponding to both C–F and C–F2 bonds. These trends are in good agree-
ment with the infrared results, which show an increase in the intensity of the
C–Fx bands when the fluorine content increases [23].
As discussed above, the ionic bombardment during a-C:H film growth
controls the final film properties. According to mass spectrometry measure-
ments in CH4 and CF4 low-power rf capacitively coupled plasmas, the main
ionic species in our plasmas are expected to be CF+ +
3 and CH3 ions [46]. In
+
the case of N2 plasma, N2 is the more important ionic species [47]. For V b on
the order of several hundred volts, these molecular ions promptly break up
upon colliding with the film surface. From simple mechanical arguments, it is
possible to show that the energy sharing between the atoms is proportional
to the mass ratio of the atom and the molecule. Clearly, for CH+ 3 ions this
energy is almost totally concentrated in the carbon atom, while for CF+ 3 ions
it is more equally divided between all atoms. In a few words, the CF+ 3 bom-
bardment is much less effective than that due to CH+ 3 or even N +
2 ions. In
the case of CF4 –CH4 atmospheres, when the methane partial pressure in the
plasma is reduced, the efficiency of the ionic bombardment is also reduced,
resulting in films with polymeric character.
228 Fernando L. Freire Jr.

Fig. 9. Atomic density as a func-


tion of V b

Fluorinated a-C:H films were also investigated by thermal-induced gas


effusion [39]. A structural transition from diamond-like to polymer-like films
as a result of the incorporation of fluorine could be inferred from the effusion
spectra. At low fluorine contents (up to 10 at. %) the material is relatively
compact and the effusion of hydrogen-related species (hydrogen molecules
and hydrocarbons) dominates. As the fluorine content is increased, hydro-
gen-related effusion is progressively substituted by the effusion of CF4 -related
species, confirming that fluorine atoms substitute hydrogen ones in the amor-
phous network. For high enough fluorine concentrations a strong change in
the effusion characteristics indicates that an interconnected network of voids
is present. Strong effusion of CF4 -related species is consistent with a surface
desorption process and can only be observed when CF2 and CF3 bonds are
present in the film microstructure and the void dimensions are large enough,
i.e., for films with the highest fluorine contents.
Thermal-induced gas effusion experiments are also used to study the ther-
mal stability of the films. Gas evolution experiments performed on a-C:H:N
films showed that any possible application for such films is limited to temper-
atures below 300◦ C. Above this temperature H and N losses provoke severe
structural changes [48]. These results confirm a previous study performed on
films annealed in vacuum, which reveals a decrease in thermal stability when
the amount of nitrogen incorporated in the film increases [49]. It was shown
that a-C:H films deposited by PECVD are thermally stable up to 450◦C, com-
pared with the 350◦C determined for a-C:H:N films with 8 at. % of N. The
thermal stability of a-C:H:F was also studied and the incorporation of fluo-
rine in the amorphous skeleton reduces the thermal stability of the films [50].
Concerning the application of a-C:H:F films as interconnect dielectric mate-
rials, the thermal stability of low-κ materials is of major importance since
they are submitted to thermal annealing during subsequent integrated circuit
manufacturing steps. Among other requirements, such as gap-fill capability,
adhesion and minimal moisture absorption, thermal stability up to 400◦ C is
necessary. However, despite some claims that plasma-deposited carbon flu-
Hard Amorphous Hydrogenated Carbon Films and Alloys 229

orinated films are thermally stable at those temperatures, the usefulness of


a-C:H:F films have yet to be proved by integration in an ULSI structure.
The effects of the self-bias voltage are illustrated in Fig. 9, where the film
density of a-C:H, a-C:H:N and a-C:H:F films are presented as functions of
V b . Our results for low-V b depositions correspond to low-density films. Also,
these films present high luminescence Raman background, while IR results
show important contents of CHn groups. These features are characteristic of
a polymer-like structure, with high concentration of saturated sp3 carbons.
As the self-bias is increased, the film properties change. Within the self-bias
range from −100 V to −300 V, the most remarkable structural changes occur.
They can be identified by the densification of the structure as a result of the
higher generation rate of nucleation sites on the film surface due to the more
energetic ion bombardment. These films have a diamond-like character, with
high hardness and high internal stress. Films deposited at higher V b have a
slightly lower density.

4 Mechanical and Nanotribological Properties


The study on the nanometer scale of the physical phenomena related to the
interaction of surfaces in contact and in relative motion, nanotribology, was
made possible with the invention of the atomic force microscope in 1986 [51].
These phenomena are extremely important in situations like manipulation
of atoms and molecules in surfaces, as well as in the operation of electrome-
chanical devices. In the last decade, with the development of friction force
microscopy, the study of wear and friction properties of materials has received
increasing attention [52]. In spite of that, the study of the lubricant and tri-
bological properties of carbon-based films and other carbon-nanostructured
materials is still in the beginning [53]. The friction and wear measurements
at nanometer scale that are discussed in this section were carried out us-
ing an atomic force microscope (AFM) operated in the lateral force mode.
During the experiments the temperature and the relative humidity were kept
constant at 23◦ C and 40%, respectively. The cantilever normal force was ob-
tained by multiplying the measured cantilever bending by its normal bend-
ing constant. In order to obtain the absolute values of the friction coeffi-
cients, the cantilever bending constant was calibrated using the formula of
Neumeister et al. [54], while the AFM was calibrated with the method pro-
posed by Liu et al. [55].
In this section we present both the internal stress and film hardness re-
sults. The internal stress determination was made by measuring the curvature
of the substrate by means of stylus profilometry and by applying Stoney’s
equation, as described in detail elsewhere [56]. The hardness of the films was
measured employing a nanoindenter. The film hardness was obtained accord-
ing to the Oliver and Pharr method [57].
230 Fernando L. Freire Jr.

Fig. 10. (a) Compressive internal stress and (b) hardness as functions of the
incorporated nitrogen

The discussion in the previous section shows that a-C:H:N films with up
to 11 at. % of nitrogen retained their diamond-like properties, despite the pro-
gressive graphitization induced by nitrogen incorporation. The compressive
internal stress and hardness are presented in Fig. 10 for a-C:H:N films. It is
well known that the high internal compressive stress observed in a-C:H films
may be viewed as a result of the material overconstraining. This means that
the relatively high carbon sp3 fraction observed in hard a-C:H films causes
the mean atomic coordination number to be higher than the ideal value pre-
dicted for a fully constrained network [58]. In this scheme, any stress relief
process may be strongly coupled to a reduction of the coordination number.
In the case of a-C:H:N films, the important decrease in the internal compres-
sive stress upon nitrogen incorporation (Fig. 10a) is conceived as a combina-
tion of the chemical composition, since nitrogen atoms admit a coordination
number equal to 3 at most, and hybridization states. Besides the nitrogen
incorporation itself, which occurs at the expense of the carbon content, the
sharp increase in the fraction of carbon atoms in sp2 -hybridization state is
a source of decrease in the mean coordination number. Thus, for 9 at. % of
nitrogen content in a-C:H:N films, the hardness shows only a slight reduction
(Fig. 10b), while the internal stress is reduced by a factor of two [14].
The film hardness and the internal stress of a-C:H:F films were shown
in Fig. 11. Fluorine-poor films present high hardness and high compressive
internal stress, which is typical of diamond-like materials. As the amount of
incorporated fluorine increases, the magnitudes of these quantities decrease.
Films with fluorine content of 22 at. % are nearly stress-free and their hard-
ness was reduced by a factor of 3 when compared to a-C:H films. This hard-
ness is still more than a factor of 10 higher than the values obtained for
PTFE. Further incorporation of fluorine leads to soft films with slightly ten-
Hard Amorphous Hydrogenated Carbon Films and Alloys 231

Fig. 11. (a) Compressive internal stress and (b) hardness as functions of the in-
corporated fluorine

Fig. 12. Contact angle as a function of the fluorine content of the films

sile stress. The reduction of the internal stress in a-C:H:F can be explained
by the more relaxed and less dense polymeric structure of these films [23].
The hydrophobicity of these films was investigated by contact angle mea-
surements. The results indicate an increase in the contact angle as the fluorine
content of the films increases (Fig. 12). The increase in the contact angle in
fluorinated amorphous carbon materials was attributed not only to a higher
incorporation of fluorine but mostly to the presence of CFn groups on the
surface [59]. In fact, the fluorine richest films have a F/C ratio of only 0.5
232 Fernando L. Freire Jr.

Fig. 13. Friction coefficient as a function of the contact angle

but present contact angles of 95◦ . On the other hand, PTFE has a F/C ratio
of 2 and presents contact angles in the range 104–111◦ [25].
From the results presented in Fig. 13, the importance of the surface wet-
tability on the friction mechanism is clear. In this figure, the friction co-
efficients were plotted as function of the contact angle and show a nearly
linear decrease. This result is in good agreement with previous observation
of the influence of the surface hydrophobicity on the friction forces for a-C:H
films [60].
The importance of the nitrogen incorporation to surface hydrophobicity
and friction processes was also verified when the nitrogen incorporation into
fluorinated carbon films was studied [27]. In Fig. 14, the friction coefficients
and the contact angles were plotted as functions of the nitrogen content in the
films. It is clear from the figure that the friction coefficient and the contact
angle have an opposite tendency.
The observed correlation between the contact angle and the friction co-
efficient reinforce the importance of the capillary condensation kinetics in
the friction process that occurs at nanometer scale: the greater the surface
hydrophobicity, the less important is the water vapor condensation for the
nanoscale friction process. In a recent publication [61], it was suggested that
the sliding friction forces are determined by two competitive processes. De-
pending on the surface wettability, one of the processes can dominate. The
first one is the thermally activated stick and slip behavior, and friction is
due to the cohesive forces between the two surfaces in contact. The second
contribution comes from the formation of capillaries at the nanoasperities
contact points between tip and film surface due to water vapor condensa-
tion, which must be taken into consideration especially for measurements
performed in air. In fact, the role of the water condensation was investigated
Hard Amorphous Hydrogenated Carbon Films and Alloys 233

80
)
o
Contact angle (

72

64

56

0.24
Friction coefficient

0.20

0.16

0.12
0 5 10 15 20
Nitrogen content (at.%)
Fig. 14. Contact angle (upper part) and friction coefficient (lower part) as functions
of the nitrogen content in the films. The a-C:H:F:N films are represented by black
dots, while the open dots correspond to values measured in a-C:H films deposited
in pure methane atmosphere

from the velocity dependence of the friction force, and the results revealed
the importance of the surface energy [25]. In this case, the kinetics of cap-
illary condensation of water vapor in the contact area causes a decrease of
friction with increasing velocity, since for higher scanning velocities there is
no time for capillary formation [61]. In the case of hydrophilic surfaces, this
mechanism can predominate.
Nano- and microscale wear behavior of a-C:H, a-C:H:N and a-C:H:F films
deposited by PECVD have been studied with the use of atomic force mi-
croscopy and the sliding sphere test [62]. At the nanometer scale, the wear
depth is observed to increase linearly with the increase of the tip surface nor-
mal force. An analysis of the minimum force necessary to scratch the surface,
obtained by extrapolating the wear versus load force curve, as well as the
wear rates and the scratch depth test results, show that the wear is strongly
related to the film hardness and microstructure. This fact has been observed
either in a very low force regime, in the range of µN using the AFM, or with
234 Fernando L. Freire Jr.

Fig. 15. Wear rate and critical force to scratch the films as functions of the
hardness. For sake of comparison, the wear rate obtained for the Si substrate is
20 × 103 mm3 /Nm. The lines are only eye-guides

forces in the range of mN with a sphere abrasion equipment, since a similar


trend is observed in both scales. Even though the range of forces and the
wear process in both tests are quite different, we are led to the conclusion
that the hardness of the films plays the dominant role in determining their
wear performance in both nano- and microscales [62]. From Fig. 15, it is seen
that the wear rate of the polymeric a-C:H:F film is higher than the values
obtained for the a-C:H film. The results show that when the film hardness
decreases, an increase in the wear rate, as determined by a sphere test, is
observed. At the micrometer scale, the hardness of the films appears to be
the dominant factor in determining the wear resistance. In this figure we also
plot the critical force to scratch the film surface using the AFM tip as a func-
tion of the film hardness. In this last set of data, the hardness also appears
as a good parameter to present the data.

5 Conclusion

We found that a-C:N:H films with up to 11 at. % of N retained their diamond-


like properties, despite the progressive graphitization induced by nitrogen in-
corporation. In this case, the reduction of the internal stress without substan-
tial changes in the film hardness was attributed to the reduction of network
connectivity. On the other hand, the increase of the fluorine content results
in polymer-like films, with smaller internal stress and hardness. A structural
Hard Amorphous Hydrogenated Carbon Films and Alloys 235

transition from diamond-like to polymer-like films as a result of the incorpo-


ration of fluorine could be inferred. As a general rule, films deposited with
low values of self-bias voltage result in polymeric materials. In which concerns
the fiction properties, surface hydrophobicity plays an important role in the
friction properties. One can control the friction behavior of a-C:H films and
their alloys by changing the surface energy via the incorporation of fluorine
(increases the surface hydrophobicity) or nitrogen (reduces the surface hy-
drophobicity). In this way, the friction coefficient and the contact angle have
an opposite tendency. On the other hand, the wear rate is nearly independent
of the chemical composition of the film, but is directly proportional to the
film hardness.

Acknowledgements

The author is very grateful for the fruitful discussions with D.F. Frances-
chini, G. Mariotto, R. Prioli, L.G. Jacobsohn and M.E.H. Maia da Costa.
This work is partially supported by the Brazilian agencies: Fundação de Am-
paro à Pesquisa do Estado do Rio de Janeiro (FAPERJ), Conselho Nacional
de Desenvolvimento Cientı́fico e Tecnológico (CNPq) and Coordenação de
Aperfeiçoamento de Pessoal de Nı́vel Superior (CAPES).

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(Ed.): Encyclopedia of Nanoscience and Nanotechnology (American Scientific,
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Index
a-C:H, 218–220, 222–224, 227–230, atomic force microscopy (AFM), 229,
232–234 233, 234
a-C:H:F, 219–224, 226, 228–234
a-C:H:F:N, 219, 233 carbon coordination, 230
a-C:H:N, 218, 220–224, 226, 228–230, coatings
233 protective coatings, 218
sp2 -bonded clusters, 217
D band, 224, 225
cluster size, 226 D/G band intensity ratio, 225, 226
density, 224, 227–229
annealing, 228 diamond, 217
238 Fernando L. Freire Jr.

diamond-like carbon (DLC), 218, 224, nanotribology, 229


228–230, 234 nanotubes, 218
diamondlike carbon (DLC), 217 nitrogen incorporation, 217–219, 221,
224, 226, 228, 230, 232, 234
electrical properties, 218, 219
electron energy loss spectroscopy optical properties, 218
(EELS), 224, 226
plasma-enhanced chemical vapour
fluorine incorporation, 217–219, 223, deposition (PECVD), 218, 219,
224, 226–228, 230, 231 228, 233
friction coefficient, 219, 229, 232, 233 polymer-like carbon (PLC), 224,
fullerene, 218 227–229, 234
polymers, 217
G band, 224, 225
graphene, 218 Raman spectroscopy, 224–226, 229
graphite, 217
silicon incorporation, 218
graphite-like carbon (GLC), 218
subplantation model, 217, 218
graphitization, 230, 234
thermal stability, 218, 219, 228
hardness, 218, 229–231, 233, 234 thermal-induced gas effusion, 228
hydrogen incorporation, 218 tribological properties, 217, 219, 229
hydrophobicity, 219, 231, 232, 235
ultra-large scale integrated circuits
infrared (IR) spectroscopy, 224, 227, (ULSI), 219, 229
229
internal stress, 217, 218, 229–231, 234 wear resistance, 229, 233, 234
ion beam analysis (IBA), 220, 224 wettability, 219, 232

mechanical properties, 217–219, 229 x-ray photoemission spectroscopy


microstructure, 217, 219, 224, 228, 233 (XPS), 224, 227
Ion Microscopy on Diamond

Claudio Manfredotti

Dipartimento di Fisica Sperimentale and Centro d’Eccellenza “Nanostructured


Interfaces and Surfaces” (NIS), Università di Torino, Via P. Giuria 1, I-10125
Torino, Italy
manfredotti@to.infn.it

Abstract. Because of its physical properties (strong radiation hardness, wide en-
ergy gap with a consequent extremely low dark current, very large electron and
hole mobility) diamond is a very good candidate for nuclear particle detection, par-
ticularly in harsh environments or in conditions of strong radiation damage. Being
commonly polycrystalline, diamond samples obtained by chemical vapour deposi-
tion (CVD) are not homogeneous, not only from the morphological point of view,
but also from the electronic one. As a consequence, as it was indicated quite early
starting from 1995, charge collection properties such as charge collection efficiency
(cce) are not uniform, but they are depending on the site hit by incoming particle.
Moreover, these properties are influenced by previous irradiations which are used in
order to improve them and, finally, they are also dependent on the thickness of the
sample, since the electronic non uniformity extends also in depth by affecting the
profile of the electrical field from top to bottom electrode of the nuclear detector
in the standard “sandwich” arrangement. By the use of focussed ion beams, it is
possible to investigate these non uniformities by the aid of techniques like IBIC
(Ion Beam Induced Charge) and IBIL (Ion Beam Induced Luminescence) with a
space resolution of the order of 1 µm. This relatively new kind of microscopy, which
is called “ion microscopy”, is capable not only to give 2D maps of cce, which can be
quite precisely compared with morphological images obtained by Scanning Electron
Microscopy (generally the grains display a much better cce than intergrain regions),
but also to give the electric field profile from one electrode to the other one in a
“lateral” arrangement of the ion beam. IBIL, by supplying 2D maps of luminescence
intensity at different wavelength, can give information about the presence of spe-
cific radiative recombination centers and their distribution in the material. Finally,
a new technique called XBIC (X-ray Beam Induced Charge), which makes use of
very collimated (to 0.1 µm) x-ray beams from high energy electron synchrotrons,
opens new ways to map cce with a less damaging radiation and with a better en-
ergy resolution. In this paper we resume recent and less recent work carried out by
our group by using these techniques, a work that has been undertaken afterwards
also by other research groups in the world. In particular, topics such as the better
homogeneity obtained by “priming” and the effects of “light priming”, together
with a certain “complementarity” between IBIC and IBIL maps, giving evidence
that radiative recombination centers along the grain boundaries or in damaged re-
gions are important in affecting cce, will be presented and discussed in some details.
The conclusion is that ion microscopy is a powerful and essentially unique method
for the investigation of diamond and other semiconductor materials proposed for
nuclear detection.

G. Messina, S. Santangelo (Eds.): Carbon, The Future Material for Advanced Technology Ap-
plications, Topics Appl. Phys. 100, 239–265 (2006)
© Springer-Verlag Berlin Heidelberg 2006
240 Claudio Manfredotti

1 Introduction
Ion microbeams [1] represent a powerful tool for investigating the physical
and chemical properties of solids. Even if the spatial resolution is still lower
than for electron microscopy (SEM, TEM), the types of measurement with
ions (protons, helium) are wider and their accuracy is much better. In effect,
ion microbeams in the energy range between 2 and 10 MeV or more allow
for: (1) trace elements analysis and chemical composition measurements down
to ppma range [2] and below (particle-induced X-ray emission, PIXE), due
to the absence of bremsstrahlung radiation background; (2) measurement of
transport properties [3] of semiconductors (charge collection distance or drift
length, mobility-trapping time product) and for the acquisition of the rele-
vant maps over regions as wide as 2 mm or more (ion beam-induced charge,
IBIC); (3) measurement and mapping of luminescence properties [4] down to
a thickness of 100 µm or more, with respect to 1 µm depth reached by CL (ion
beam-induced luminescence, IBIL); (4) measurement of doping levels down
to 1 ppma with a depth resolution of 1 nm (Rutherford, RBS backscattering)
or light elements distribution profiles with the same resolution (elastic recoil
diffusion, ERD). The precise definition of the range, the very low Coulomb
scattering and lateral straggling keep the spatial resolution at the same level
as the ion spot diameter, while the possibility of getting a trigger signal
allows for the realization of time-resolved measurements, which give infor-
mation about time behaviour of the measured parameter, such as radiative
recombination lifetime with IBIL. The number of charges released by ions is
so large to allow for the possibility of getting a map just in one pass over
the selected area without getting problems with radiation damage, which,
of course, is heavier with ions than with electrons. Even if this technique is
much younger than electron microscopy, there are now on the market ap-
paratuses which are technologically advanced and which are to some extent
as user-friendly as SEM or TEM. In this paper we shall concentrate only
on IBIC and IBIL measurements on diamond, both CVD and natural, be-
cause diamond is a very interesting material for the realization of nuclear and
other kinds of detectors (very large resistivity, complete depletion over thick
regions at low voltages, extremely high resistance to radiation damage). Still,
diamond has the problem of being mainly polycrystalline and, as it will be
shown, this structural property is reflected in material nonhomogeneity with
respect to radiation response or charge collection efficiency (CCE). Change
collection efficiency is defined as the fraction of generated charges which are
contributing to the current pulse released by the nuclear particle or by some
ionising radiation crossing the sample. IBIC [5, 6, 7, 8] represents, in fact, the
only simple way to map CCE over suitable region sizes, while with IBIL it
is possible to select the regions which limit CCE by giving rise to a strong
radiative recombination, which characterizes by its blue light emission the
luminescence properties of the purest, detector grade, diamond.
Ion Microscopy on Diamond 241

Fig. 1. The proton microbeam set up at AN-2000 electrostatic accelerator in Leg-


naro National Laboratories (LNL) of National Institute for Nuclear Physics (Italy)

2 IBIC
There are more than 50 ion microbeam apparatuses around the world and
many of them are in Europe. One such apparatus, that at the National Labo-
ratories of Legnaro, Italy, National Institute for Nuclear Physics, is illustrated
in Fig. 1, which shows the last part of AN-2000 electrostatic accelerator [6]
with the focusing system (three quadrupoles) and the scattering chamber.
The spot diameter can be reduced down to about 1 µm, and the scanned
area can be as large as 2 mm × 2 mm, but is typically much lower (400 µm
× 400 µm). With a dwell time of few ms, the time taken for a full image
258 × 258 pixels is on the order of few minutes. Beam intensities are kept
very low, much less than a fA. By limiting the counting rate to 100 cps, for
instance, it is possible to get one event per pixel. At larger counting rates
local trapping may create space charge in the pixel and reduce the charge
collection efficiency.
Some details of the scattering chamber are shown in Fig. 2. Several ports
at the periphery can be used for signal outputs related to the collected
charge (IBIC), induced luminescence (IBIL, with monochromator and photo-
tube), charateristic X-rays revealed by a Si(Li) detector suitably cooled by a
liquid nitrogen dewar (PIXE), ions backscattered from the sample as revealed
by a Si surface barrier detector (RBS). Downstream a similar detector may
be used for scanning transmission ion microscopy (STIM) and other similar
detectors may be used for other techniques (a Faraday cup can be used for
detection of secondary electrons to obtain secondary electrons ion microscopy
242 Claudio Manfredotti

Fig. 2. Details of the scattering chamber used in LNL for IBIC/IBIL measurements

(SEIM) images. A scintillator is used to detect beam position and to align


the samples under investigation.
An IBIC setup is schematically shown in Fig. 3. The acquisition is carried
out event-by-event in a file (x, y, collected charge) giving the possibility to
replay the events in order to follow some specific behaviour (polarization, for
instance). IBIC could be used both in standard frontal geometry and also in
“lateral” geometry [9, 10], on a cross section of the sample (Fig. 4). There
are a number of important advantages for lateral IBIC. First, carriers are
immediately swept apart by the electrical field and plasma recombination is
avoided. In addition, CCE can be profiled as a function of depth, giving in-
formation concerning different regions in inhomogeneous samples, like CVD
diamond. Third, some CCE loss under the electrodes can be suitably mon-
itored. Finally, profiles of the electrical field could be obtained under some
reasonable assumptions. The drawbacks of obtaining a cross section of the
sample, of getting in general large dark currents and some fringing field ef-
fects, are overcome in CVD diamond by cleaving the sample (dark currents
remain very low) and by using protons of a suitable energy in order to place
the Bragg’s peak at a depth large enough to be sure to have a real bulk
electric field.
In frontal IBIC [7,11] it is possible to obtain CCE maps with the maximum
contribution given by carriers generated at the depth of Bragg’s peak, which
ranges from 25 µm (2 MeV protons) up to more than 100 µm for 9 MeV
protons (shorter thicknesses are reached with few MeV helium ions). Frontal
IBIC may present some problems in thicker CVD diamond samples with drift
lengths of both carriers much longer than thickness. In effect, with respect
Ion Microscopy on Diamond 243

Fig. 3. Layout of a typical IBIC experiment

Fig. 4. Description of the geometry of irradiation and signal collection in a lateral


IBIC measurement. In frontal IBIC the microbeam hits one of the two electrodes

to the minimum ionising particles (mips), as may be defined for almost all
the particles coming out from high-energy experiments, ionisation density is
more than 100 times larger (0.7 MeV/mm for mips and 80 MeV/mm for
2 MeV protons, on average). Taking into account the lateral diffusion of
charge, created by δ-rays, assuming carrier lifetimes in diamond on the order
of 0.1 ns, the ionisation given by low energy protons can give rise to an
244 Claudio Manfredotti

Fig. 5. A frontal IBIC map carried out on a CVD diamond sample biased at
+600 V (front electrode) together with the relevant multichannel pulse spectrum.
The proton energy is 2 MeV. The electrode diameter is 2 mm. Previous X-ray
priming of the sample amounted to 10 Gy

instantaneous carrier density on the order of 1013 –1015 cm−3 , which is much
larger than the equilibrium one (about 105 cm−3 ) in diamond. Mips create
much more energetic δ-rays, and local ionisation density along the track is
lower by some orders of magnitude. With respect to mips, it is expected that
frontal IBIC maps could be affected by polarization effects, even if priming
with X-rays is used in order to fill the traps and make the response of the
sample more homogeneous.
One example is given in Fig. 5, which shows a CCE map together with the
relevant multichannel spectrum obtained on a CVD diamond detector 600 µm
thick in which a charge collection distance (CCD) of 75 µm was measured by
using mips. CCD, which is defined as the average distance between electrons
and holes, as averaged over the thickness of the sample, is obtained simply
by multiplying the average CCE by the thickness. It has been proved by the
“linear model” that it increases linearly from the back to the growth face of
the sample. In our case, even if the average CCE is between 10 and 15%,
in agreement with data obtained with mips, the spatial distribution is very
inhomogeneous, with large regions of the sample in which, because of strong
polarization, no events were recorded. In fact, after 2 hours of measurement,
the event rate dropped down to zero, while it started at more than 100 cps.
The homogeneity of the response [12] is quite important in tracking appli-
cations, since the precise event position is reconstructed as a center of mass
Ion Microscopy on Diamond 245

Fig. 6. A frontal IBIC map carried out on the same CVD diamond sample biased
at −600 V (front electrode) and under illumination, together with the relevant
multichannel pulse spectrum. The scan region is the same as in Fig. 5

by means of the collected charge in nearby strips or pixels and, if CCE is not
uniform, the position is badly reconstructed. In IBIC maps there are small
regions with CCE as large as 30–35%, which should correspond to CCD val-
ues of about 200 µm, the best it is possible to get in similar samples. As a
matter of fact, these regions are corresponding to almost perfect diamond
monocrystals, as evidenced in maps obtained on thin samples by X-rays.
By illuminating the sample with blue light (400 nm) or with white light
and by switching the polarity to negative bias (Fig. 6) the situation changes
drastically: high-efficiency spots are still there, but now the large “blind” re-
gion among these spots has got CCE values of about 10%, i.e., CCD values of
60 µm, close to those obtained by mips. If these regions are disordered regions
with grain boundaries and dislocations, with a lot of filled dangling bonds
and a distributed space charge with very low electric fields, now this opti-
cally induced detrapping eliminates, at least partially, this space charge and
the relevant polarization and thereby improves CCE. Since these data were
obtained by 2 MeV protons (25 µm penetration depth) and with a negative
bias voltage applied at the front electrode, we can immediately attribute this
beneficial effect to electrons, which are giving the main contribution to the
charge signal according to Ramo’s theorem. In fact, this theorem states that
a charge contributes with the fraction of the covered path with respect to the
extension of the electrical field (sample thickness in this case, as evidenced
by lateral IBIC and discussed in the next section).
246 Claudio Manfredotti

Fig. 7. Lateral IBIC CCE profile on a cross section of a CVD diamond sample
200 µm thick. Bias voltage (+400 V) is applied at the growth side (left). The
profile was averaged over a region 450 mm wide. Black squares are the experimental
data, the continuous line is the fit, empty and filled circles are holes and electrons
contributions, respectively

Fig. 8. Lateral IBIC CCE profile on a cross section of the same CVD diamond
sample 200 µm thick. Bias voltage (−400 V) is applied at the growth side (left).
For symbols see Fig. 7

3 Lateral IBIC
Lateral IBIC [9,10,13,14,15] has been used in order to test the “linear model”
and to throw some light on the electric field depth distribution, which is gen-
erally assumed to be uniform. Moreover, from CCE depth profiles obtained
Ion Microscopy on Diamond 247

now without polarization effects and therefore in conditions not different


from the mips case, it is possible to evaluate CCD from experimental data
and compare it with data obtained with mips. In order to do this, charge
collection distance or charge collection length should be better defined as
drift length µτ E, i.e., the product of (mobility)×(trapping time)×(electric
field), which is a local value and can be diversified for the two carriers. Then
the average value of the sum of µτ E for electrons and holes over the sam-
ple thickness, taking into account that ionisation for mips is uniform, can
be compared with CCD. This is what will be done in what follows. We can
start from CCE distributions (Figs. 7 and 8) for positive and negative bias
voltages, respectively (the voltage is applied on the left, which is also the
growth side) in the case of a sample 200 µm thick. It can be observed that
these distributions do depend on the bias voltage polarity, essentially because
mobility lifetimes are different for the two carrier types and also because the
electric field distribution is different due to the electric contacts. In effect, by
looking at both curves, one observes that peak CCE is closer to the negative
contact. This means, by Ramo’s theorem, that the main contribution in this
case is given by electrons, which have at their disposal a much longer path
towards the anode. It is possible to express CCE by Ramo’s theorem as a
double path integral for each carrier as a function of hit point of the beam and
to obtain CCE distribution in terms of µτ E depth distribution separately for
each carrier. In order to reduce the number of parameters, one can make a
more physical “linear model” assumption in terms of a linear dependence of
µτ on depth, increasing from the back (substrate) side, a constant ratio of
µτ between the two carriers and a suitable parametrization of the electrical
field with as few parameters as possible [3]. Apart from electrical field, all
the other parameters are kept constant for all the bias voltages investigated
(seven in total).
From Figs. 7 and 8 it can be deduced that effectively the largest con-
tribution to CCE (about ten times) is given by electrons, which display an
almost uniform value of µτ of about 5 × 10−7 cm2 V−1 , with a resulting fit
to experimental data that can be considered quite good (not only in this,
but also in all the other cases). The electric field distribution is, however,
different, with a peak at the positive front side and a much more penetrating
behaviour in the case of a negative front side.
The effect of the electric field is that of giving a similar behaviour to
drift lengths of both carriers (Fig. 9), with an average value of 100 µm for
electrons at −400 V and with a decay at both electrodes. The final result is
to get a combined drift or mean collection length, averaged over the sample
thickness and defined here as Le + Lh , similar to CCD and symmetric with
respect to the bias voltage (Fig. 10). The same behaviour resulted from mips
data, with a quite close value of 50 µm for CCD at 200 V, i.e., at an ohmic
electrical field of 1 V/µm and of 100 µm at 2 V/µm. Apart from the details
of the deconvolution of CCE in terms of different contributions of electrons
248 Claudio Manfredotti

Fig. 9. Electron and hole drift lengths (L) as a function of depth derived from
previous figure, together with the profile of the electric field

Fig. 10. Behaviour of mean collection length L for electrons (filled circles), holes
(open circles) and both carriers (filled squares) as a function of bias voltage obtained
by simulating the behaviour of a mip

and holes, this result is given directly from figures like Figs. 7 and 8, and it
proves the validity of lateral IBIC in deriving CCE depth distributions.
In the same way, it is possible to observe the effect of priming or pumping
(see [16] at p. 93), i.e., with irradiations of the sample with X-rays or high-
energy electrons, in order to stabilize the performances of the detector. After
a priming dose of 46 Gy (Fig. 11), the CCE profile has a higher and broader
peak and it is much improved in the right part at lower values of CCE.
This is an average over a cross section region of 450 µm. By considering now
the single paths connecting the two electrodes (called here “columns”), one
Ion Microscopy on Diamond 249

Fig. 11. Lateral IBIC CCE profiles on a cross section of the same CVD diamond
sample 200 µm thick, as obtained before (top) and after (bottom) a priming dose
of 46 Gy. Bias voltage (−300 V) is applied at the growth side (left)

obtains distributions of CCE like those reported in Fig. 12, which measures
the average increase of CCE or CCD given by priming.
Since peak efficiency increases from 0.153 to 0.283 after priming, the im-
provement amounts to a factor 1.8, which is exactly the same as that obtained
with mips [16]. What can be observed in more detail is that this improvement
is really “local”, as clearly shown in Fig. 13, which refers to the detailed ef-
ficiency profile obtained along the border of the top (or front) electrode and
derived from the averages along the “columns”, as it was for Fig. 12.
The exact comparison with the results concerning uniformity of CCE
obtained by mips, which have been here simulated by starting from CCE
profiles across the sample, will be reported in what follows. It is clear that
in our case we got uniformity along a line, while with mips the uniformity
refers to an area, which is, of course, impossible to obtain by our approach.
However, it has to be noted that the nonuniformity, obtained as a standard
deviation from fits reported in Fig. 12, is decreased by priming from 32.7% to
250 Claudio Manfredotti

Fig. 12. Distributions of CCE as obtained from the same data as Fig. 11 and
averaged over the different straight lines connecting the two electrodes (called
“columns”): these distributions simulate CCE as viewed from mips with hit points
along a straight line (the border of top electrode). The fit has been obtained with
two Gaussian curves for the nonirradiated or unprimed case (mean 0.153, FWHM
0.059 for the first peak, mean 0.283 and FWHM 0.035 for the second one) and one
Gaussian line for the primed case (mean 0.292, FWHM 0.077)

Fig. 13. Profile of CCE as viewed by mips along a segment of top electrode, for
the primed and unprimed case

22.2%. This result confirms those reported more qualitatively in Figs. 5 and 6:
the improvement is due to the strong increase of the number of pixels showing
CCE values around 10–15%, but also to the analogous increase around 30%
of CCE. It is confirmed that, as observed in Figs. 5 and 6, those regions were
already present in a smaller number in the nonirradiated sample.
Ion Microscopy on Diamond 251

Fig. 14. Layout of IBIL apparatus, with ellipsoidal mirror, the monochromator
and the phototube

4 IBIL
With the same proton microbeam, it is also possible to carry out IBIL mea-
surements [3, 4, 17, 18, 19] and to map the luminescence efficiency produced
by the beam itself. When, as occurs in diamond, the radiative recombinations
are important and at least comparable with the nonradiative ones, IBIL maps
are indicative of regions with lower CCE. As a consequence, by the examina-
tion of the relevant wavelength spectra, it is possible to infer which are the
recombination centers responsible for the low values of CCE.
A IBIL schematic setup is given in Fig. 14. The microbeam enters a
small hole (diameter of 1 mm) of an ellipsoidal metal mirror, which allows
for the beam scanning, and the light is collected by a vacuum light guide
without dispersions or absorptions (two photos of mirror and monochromator
in Fig. 15).
With a 0.25 m focal length monochromator it is possible to reach a good
wavelength resolution in the interval 300–900 nm, which is also the region of
the maximum quantum efficiency of the phototube. Two retractable mirrors
give the possibility of also carrying out panchromatic images. With respect
to standard cathodoluminescence (CL), the electronic chain works in pulse
conditions: the signal from the phototube is amplified by a gated amplifier
(gate of 70 ms at each microbeam position), and the pulses are collected and
simply counted (no pulse height analysis is carried out) until the beam moves
to the next position. Taking into account the microbeam intensities, which
are here much higher than for IBIC (about 700 pA), the luminescence effi-
ciency of the sample, the solid angle viewed by the mirror, its reflectivity, the
optical band pass, etc., we are led to the conclusion that we are just counting
the photons, i.e., one event per pixel and no pile-up problems. As a conse-
quence, the maps are intended to be maps in photon number, instead of CCE
or electron number as in IBIC. In any case, the map signals are not to be
quantitatively related by a direct proportionality to the luminescence inten-
252 Claudio Manfredotti

Fig. 15. Photographs of parts of IBIL apparatus

sity coming from the relevant pixels. The advantages with respect to CL are
that the luminescence is a real bulk luminescence, i.e., it comes mainly from
a defined depth due to the Bragg’s peak and time-resolved measurements can
be carried out by this approach.
An example of the complementarity between IBIC and IBIL maps is given
in Fig. 16. The maps were carried out on the same sample cross section (and
therefore are to be quoted as lateral). As expected, IBIC CCE is higher in the
upper part of the map, which is on the growth side and contains larger and
better quality grains, while IBIL is higher in the bottom region, in which the
grains are smaller and the defective regions are wider. Of course, there are
exceptions, such as the big luminescent region at the center-left extending
towards the upper contact, as there are regions completely white, in which
Ion Microscopy on Diamond 253

Fig. 16. Top: Lateral IBIC maps on a cross section of a CVD diamond sample
600 mm thick. The growth side is on the top, the region is about 400 mm wide.
Proton energy 2 MeV. Bottom: Lateral IBIL map on the same cross section. The
substrate side is more visible at the bottom. Proton energy 2 MeV

Fig. 17. Frontal IBIL spectra on a CVD diamond sample of good electronic quality.
The spectra are decreasing in intensity at increasing proton doses. Proton energy
2 MeV

both CCE and luminescence are low or absent. It could also be that the two
maps, which were carried out without moving the sample, the scan size and
the beam position (but, of course, focusing or collimation had to be changed
because of higher intensity needed by IBIL) are not exactly coincident and
that the complementarity could be better than what “rigidly” observed.
It is suggested that IBIL maps are indicative of the “non-detector quality”
regions present in the sample; what therefore are the defects responsible for
the worsening of CCE? The answer is clearly given in Fig. 17, which reports
254 Claudio Manfredotti

Fig. 18. Frontal IBIL spectrum on a CVD diamond sample of bad electronic qual-
ity. The spectra are decreasing in intensity at increasing proton doses. Proton energy
2 MeV

a wavelength spectrum obtained on a CVD diamond sample of good quality:


the presence of the blue A-band at about 440 nm (2.8 eV), attributed to
dislocation networks, is indicative of the facts that the main contribution
to the decrease in CCE is given by the disordered regions in which a lot of
dislocations are present and that these regions occupy the space between the
“good grains” (the other band at 515 nm, 2.41 eV is the H3 center, probably
created by irradiation itself). The IBIL spectra were taken subsequently and
it is seen that radiation damage probably converts radiative regions to non-
radiative ones (or also creates vacancies in N–N groups that decorate A-band
regions by converting them in H3 centers, which are believed to be N–V–N
centers).
Figure 18 shows the same spectra for a non-detector quality CVD diamond
sample. It appears that there is another broad band at about 600 nm, which
also strongly decreases as a function of radiation damage.
The damage-induced decay of the A-band is shown in Fig. 19, which
reports the area under the peak as a function of proton dose. The decay is
observable after doses on the order of 1015 p/cm2 , which are obtained in few
minutes of measurement. The decay seems to be exponential with the dose,
which could suggest some kind of “positive reaction”, i.e., the presence of
damage itself seems to facilitate the production of damage.
The problem of attributing the space distribution of the luminescent cen-
ters can be solved also by CL maps, which display a better spatial resolution,
as shown in Fig. 20. There are – for the same cross section of the sample to
which Fig. 17 refers – respectively a SEM secondary electron image, and three
CL images (panchromatic and monochromatic at 440 nm and 600 nm). Apart
from the consideration that CL, which is more sensitive to dislocations, gives
a brighter image of the columnar structure of CVD diamond cross section, it
Ion Microscopy on Diamond 255

Fig. 19. Decay of intensity of blue A-band at 433 nm as a function of proton dose

Fig. 20. SEM micrograph (secondary electrons) and three CL maps of a cross
section of a CVD diamond sample of good electronic quality (monochromatic at
440 nm, at 600 nm and panchromatic)
256 Claudio Manfredotti

Fig. 21. SEM micrographs (secondary and backscattered electrons) and two CL
frontal maps on a sample of bad electronic quality

can be clearly observed that luminescence at 440 nm (blue A-band) gives the
main contribution also in this case, while the luminescence at 600 nm, apart
from some spots, is not spatially well correlated with dislocated regions.
A better view is given in Fig. 21, in which single grains have a sharper
appearance. Here a micrograph by backscattered electrons is also included,
since it gives a sharper identification of single-crystal grain dimensions in
depth. It can be observed that while the luminescence at 440 nm repro-
duces exactly the borders of the two main squared grains at the center of
the image, the luminescence at 600 nm is much broadly distributed in the
volume of the sample. According to our interpretation, this band is due N–
V complexes distributed in the sample and created by lower temperatures
at which the mobility of the species at the surface is lower. These centers
should be responsible for the short CCD of holes in non-detector quality dia-
mond: when filled during priming, they could allow for a longer CCD of holes
themselves. These should be therefore mainly in-grain centers. Centers re-
sponsible for A-band luminescence are certainly intergrain centers, and they
could be responsible for electron recombination, which is mainly radiative.
By illuminating the sample at around 400–440 nm, these centers are emptied
and the space-charge, due to electron capture, disappears, strongly improving
CCD of electrons, which are now able to reach CCD values above the grain
dimensions and to overcome grain boundaries.
Ion Microscopy on Diamond 257

Fig. 22. The ID21 beam line of ESRF and the scanning X-ray microscope, with a
layout of XBIC

5 XBIC

The recent availability of X-ray microbeams has opened the possibility of


carrying out IBIC measurements (referred here as XBIC) with a much bet-
ter spatial resolution [20, 21]. This turned out to be possible at ID21 line
at ESRF of Grenoble (see Fig. 22, which shows in some detail the scanning
X-ray microscope (SXM)). The nominal diameter of the X-ray spot is well
below 1 µm in this case, the measurements are carried out in air, pixel size is
1 µm and the dwell time of the beam in each pixel can be varied from 100 to
400 ms. Time-resolved measurements were not possible due to the very tight
time structure of the beam, and therefore the measurements were carried
out in current by using a picoamperometer. The nominal photon intensity at
5.5 KeV was about 108 photons/s. The synchronous acquisition of the pho-
tocurrent signal and of the signal coming from the sample micropositioning
system allowed for image formation on a pixel-by-pixel basis as in proton
IBIC. There are two main differences, however, with respect to IBIC: one is
related to the different energy loss of electrons and protons and the other to
the output signal.
With respect to 2 MeV protons, 5.5 KeV X-rays display a much lower en-
ergy loss (Fig. 23) and an exponential absorption, which lets them penetrate
thicknesses of much more than 100 µm. As a consequence, carrier generation
may be assumed to be roughly uniform across the sample for thicknesses on
the order of 100 µm. Space charge and polarization problems are experimen-
tally absent in XBIC. The photocurrent is a DC signal which may include
gain, and carrier generation represents a strong perturbation with respect to
258 Claudio Manfredotti

Fig. 23. Energy absorption coefficient for 5.5 KeV X-rays and percent stopping
power of 2 MeV protons as a function of depth in diamond

Fig. 24. XBIC map of a diamond sample (the same as in Figs. 5 and 6): X-ray
energy, 5.5 KeV, bias voltage +200 V applied at the back side (substrate). The
small square indicates a 100 × 100 µm2 region over which the maps and spectra of
Figs. 25 and 26 were obtained

the IBIC proton case, even if also with protons the local perturbation is not
small. In any case, the photocurrent is another way to get CCE values, and it
will reported in effect as photoconductive gain with respect to dark current
in arbitrary units, since quantitative estimates of CCE are not possible.
An example of an XBIC map is given in Fig. 24, which refers to the same
sample as Figs. 5 and 6. The circular electrode is clearly visible, and the black
spot at the center is due to a drop of silver paste used for gluing the wire to
Ion Microscopy on Diamond 259

Fig. 25. XBIC photocurrent maps obtained at different (positive and negative)
bias voltages over the region indicated by a square in Fig. 24

the electrode. The nonuniformity of the current is due to the nonhomogeneity


of the electronic properties of the sample, being the electrode, as observed
by an optical microscope, perfectly smooth.
An idea of the much better spatial resolution achievable is given in Fig. 25,
which shows the maps at different negative and positive bias voltages obtained
in the small square indicated in the previous figure. “Grains” of dimensions
much smaller than 20 µm are visible in particular at low bias voltages, while
the overall uniformity and the average photocurrent increases with bias volt-
age.
It seems that uniformity is better at positive bias; in effect this observation
is confirmed by Fig. 26, which reports the “multichannel spectra” of the
photocurrent obtained by sampling during the dwell time. These spectra are
displayed here in terms of numbers of pixels instead of counts, in order to
make a better comparison in terms of uniformity. Since the bias is applied on
the back side with respect to the incoming beam and since X-ray absorption
is much larger in the first 100 µm (Fig. 23), it can be assumed that the
main contribution is given by electrons, which have at their disposal a much
longer path. This conclusion is in agreement with what was reported for the
same sample in the discussion concerning lateral IBIC. In effect, the spectra
of Fig. 26 are narrower at positive bias voltages with respect to negative
ones, and this means that spatial uniformity is better, even if the mean
photocurrent is larger at negative bias. The logarithmic grey scale used in
these figures is used to improve the contrast between nearby regions in order
to observe “structures” given by the photocurrent signal and to obtain a
better correspondence with the morphology of the material. Since the sample
is quite thick (0.6 mm) and since also since the penetration depth of X-rays is
quite large, this correspondence is not easily seen (and in effect it can be and
it has been observed in much thinner samples). However, with respect to a
colour-based IBIC map, a map graphically obtained with a suitably selected
logarithmic grey scale can give a detailed and more visible structure (Fig. 27,
260 Claudio Manfredotti

Fig. 26. XBIC photocurrent spectra of the maps reported in Fig. 25

which has been obtained with the same data of Fig. 6, in which grains of a
clear geometrical structure make their appearance).
One question could be given by the different “grain” size observed in XBIC
with respect to IBIC maps. This could be related to the shorter penetration
depths of protons in IBIC with respect to X-rays in XBIC and to the larger
grain sizes at the growth side of the sample.
As already stated, one of the main applications of IBIC/XBIC is the
investigation of the uniformity of the electric response in terms of CCE. It
Ion Microscopy on Diamond 261

Fig. 27. IBIC map obtained from the same data as Fig. 6 by a suitably selected
grey scale

is possible to quantitatively define the uniformity vj by dividing the selected


area in bins of square size and by calculating the fluctuations between the
average values in the bins and the average value over the total area, according
to the following equation:

i (sij − s)
1 2
vj = 1 − , (1)
s Nj

where s is the overall average signal, sj  is the average signal of the ith
bin of bin size j and Nj is the number of bins of bin size j (j indicates the
square root of the bin area).
This exercise is presented in Fig. 28 for the central bottom region, 480 ×
480 µm2 wide, of Fig. 27. The results, which are compared with the results
obtained by a similar exercise carried out on an XBIC map of the same size
and on the same sample, are reported in Fig. 29. It is seen that there is a
relatively good agreement between the two, even if the selected regions are
not the same.
It has to be noted that in the case of IBIC the homogeneity has been
improved by blue light illumination (Fig. 6 and the relevant part of the dis-
cussion in Sect. 3). These results are also in agreement with those obtained
directly by mips in a much more cumbersome way (see [16] at p. 162) by
placing two position-sensitive detectors (two couples of silicon strip detector
with crossed strips), by triggering the event and by reconstructing the track
across the diamond detector by a suitable analysis of the event. It has also
262 Claudio Manfredotti

Fig. 28. IBIC maps of a region 480 × 480 mm2 wide, in which CCE has been
averaged over bins of increasing surface areas

Fig. 29. Efficiency uniformity, as defined by (1), as a function of bin size, obtained
in the same way from XBIC and IBIC maps

been noticed that X-ray priming improves homogeneity: this was not possible
to obtain by frontal IBIC, because of the polarization effect, but it has been
observed by lateral IBIC by a suitable “simulation” of a mip.
This result, obtained by following the lines depicted in the illustration of
Fig. 12, is shown in Fig. 30. These results prove that, at low size bins at least,
effectively priming improves CCE uniformity.
Ion Microscopy on Diamond 263

Fig. 30. Efficiency uniformity, as defined by (1), as a function of a linear bin size,
obtained from lateral IBIC maps as reported in Fig. 12, both for a primed and an
unprimed state

6 Conclusions

A new kind of ion microscopy, applied in this case to qualify CVD diamond
as a nuclear detector, or even simply as an electronic material, has been
described both in terms of capabilities and of specific results obtained on
samples of different quality. IBIC and IBIL can be used together with other
beam techniques like PIXE, ERD or RBS in order to make a correlation with
chemical impurities. The direct comparison between IBIC and IBIL maps
leads to the conclusion that the morphologically polycrystalline CVD dia-
mond is in effect also “electronically” polycrystalline, i.e., the largest values
of CCE and CCD are found in the central part of specifically “good” single
crystal grains or columns and that the main defects responsible for the low
CCE values found in CVD diamond are due to the radiative recombination
defects, which are distributed along the grain boundaries. The specific con-
tribution of the two carriers types to CCE can be separated by lateral IBIC
and the profile of the electrical field across the sample can be suitably calcu-
lated, by putting in evidence the still unsatisfactory quality of the electrical
contacts. The effects both of standard priming and of blue light illumina-
tion have been also evidenced in terms of improvement of the homogeneity
of the response, both at the surface and along the thickness of the sample.
Time-resolved IBIC and IBIL may supply in the future even more powerful
methods of investigation of CVD diamond, both in terms of material and of
a specific detector. Improvements are under way in order to obtain a value of
lateral resolution better than 1 mm and may be to reach a value of the order
of 100 nm, by a more accurate design of focusing quadrupoles. If this will be
the case, ion microscopy could enter the class of more standard and much
more widely used electron microscopies, even if the experimental apparatus is
264 Claudio Manfredotti

much more cumbersome. In any case, it must be emphasized that the amount
of information given by this kind of microscopy and the variety of techniques
which can be applied is much wider, as exemplified in this work.

Acknowledgements

The author acknowledges the important and direct contributions given by


E. Vittone, A. Lo Giudice, F. Fizzotti, P. Olivero and C. Paolini, during
various periods of IBIC, IBIL and XBIC measurements from 1995 to 2004,
concerning data acquisition, analysis and interpretation. Many IBIC measure-
ments reported in this review were carried out at Ruder Boskovic Institute
in Zagreb (Croatia), with the professional help of M. Jaksic, S. Fazinic and
I. Bogdanovic.

References
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Nuclear Microprobe (Wiley, New York 1996) 240
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(1994) 240
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Index
cathodoluminescence (CL), 251 lateral IBIC, 242, 243, 245–250, 253,
charge collection distance (CCD), 244, 259, 262, 263
245, 247, 249, 256, 263 ion beam induced luminescence (IBIL),
charge collection efficiency (CCE), 240, 240–242, 251–256, 263
242, 244–254, 258, 260, 262, 263 frontal IBIL, 253, 254, 256
CCE maps, 242, 244 IBIL maps, 251–253, 255, 256, 263
CVD diamond, 242, 244, 254, 263 lateral IBIL, 252, 253
ion beam-induced charge (IBIC), 240
detectors, 240, 241, 244, 248, 253, 254, ion beam-induced luminescence (IBIL),
256, 261, 263 240

ion beam induced charge (IBIC), Ramo’s theorem, 245–247


241–243, 245–252, 257, 258, 260,
261, 263 X-ray beam induced charge (XBIC),
frontal IBIC, 242–244, 262 257–263
IBIC maps, 244, 245, 252, 259–263 XBIC maps, 258–262
Measurements of Defect Density Inside CVD
Diamond Films Through Nuclear Particle
Penetration

Renato Potenza and Cristina Tuvé

INFN and Dipartimento di Fisica e Astronomia, Università di Catania,


Via S. Sofia 64, I-95123, Catania, Italy
Cristina.Tuve@ct.infn.it

Abstract. Fast nuclear particles (light or heavy ions), passing through a diamond
film, deposit energy by ionization. It is possible to collect the developed charges by
applying an electric voltage through both sides of the film. Experimental results
show that the positive hole charges and the negative electron charges have very
different mean free paths inside a real diamond film. Holes travel more deeply than
electrons, so that the charges collected under a given voltage and under the oppo-
site one are very different, as a suitable “two fluid” microscopic model of electrical
conduction of the film can show. Furthermore, using fast particles of different pene-
tration produced by a Tandem accelerator, it is possible to obtain a “photograph” of
the differential charge collection, which can show the distribution of charge produc-
tion (through the Bragg’s ionization curve) and destruction (through the defects,
and therefore on defect density along the particle path). Minimization of this defect
density allows us to optimize the deposition procedure of CVD diamonds.

1 Diamond as Radiation Detector


1.1 Properties of Diamond

Diamond is a solid with a density ρ = 3.51 g/cm3 . It shows a gap of 5.47 eV


between valence and conduction bands, compared to that of 1.12 eV of sil-
icon (Fig. 1). So, while silicon can be called a semiconductor, diamond is
intrinsically an insulator. Its resistivity at room temperature is in fact ρD >
1012 Ω cm, more than 4 · 106 times that of pure silicon (ρSi = 2.3 · 105 Ω cm [1])
and more than 5 · 1017 times that of a good conductor such as copper with
ρCu = 1.7 · 10−6 Ω cm. Diamond does not need doping to act as a nuclear
detector. There is no need of an artificial depletion region; it is always totally
depleted. It simply does not conduct in both directions, unless an ionizing
particle crosses it. In this case electron–hole pairs are formed in the bulk of
the material, and they can become carriers of electric charge for a short time
and can give rise to a pulse like in other solid state detectors, but with the
characteristic property of an insulator. That is, a pulse can be produced both
for positive or negative polarization of the crystal. The mean energy required
to create an electron–hole pair in diamond is  = 13.3 eV, while in silicon it
is only 3.6 eV (Fig. 1). The minimum energy resolution width of a detector is
G. Messina, S. Santangelo (Eds.): Carbon, The Future Material for Advanced Technology Ap-
plications, Topics Appl. Phys. 100, 267–286 (2006)
© Springer-Verlag Berlin Heidelberg 2006
268 Renato Potenza and Cristina Tuvé

Fig. 1. Gap and pair production energies in diamond and silicon

given by the statistical fluctuations in the number of carrier pairs N c created


by the passage of the ionizing particle. That is:

∆E ∆N c 1 
= = √ =√ , (1)
E Nc Nc E
where N c = E/ and assuming valid Poisson’s statistics. E means here the
energy released by the particle into the detector. Since  is rather higher for
the diamond, it is certainly worse than the silicon as a radiation detector
from the point of view of the energy resolution. Diamond has, however, a
great advantage and conversely a great disadvantage with respect to silicon.
The advantage consists in its much stronger hardness to radiation damage.
The disadvantage is given by the fact that good natural diamonds cost a great
deal and that synthetic ones have an energy resolution much worse than fore-
seen by (1) because lattice defects cause independently both an increase of
the dispersion ∆N c and a decrease of the value of N c with respect to the the-
oretical ones. The radiation hardness of diamond has been extensively tested
through charged particle bombardment [2] and in some cases also through
neutron bombardment [3]. The results obtained with charged particles are all
in agreement and show that diamond, instead of being damaged, is in many
cases improved by the bombardment. This effect is called pumping and is
obtained by irradiation for a given time with ionizing particles, frequently
β-particles. It is discussed in another paper in this volume [4] and seems to
Defect Density Measurements Inside CVD Diamond Films 269

graphite diffuse crystal defects

a)

b)

-1
2.4 cm

c) 1320.0 1332.5 1345.0

0 2000 4000 6000


-1
Wavenumber shift (cm )

Fig. 2. Raman spectra of different diamond specimens in order of increasing purity


of the CH4 –H2 vapour mixture

be due to the saturation of some type of lattice defects by means of the many
electrons and holes produced by a strong flux of ionizing particles. Neutron
effects are still under study, but also for them diamond seems to be sufficiently
hard. In effect recent measurements [5] suggest that diamond detectors could
advantageously replace silicon detectors as neutron flux monitors in the core
of the experimental nuclear fusion reactor at JET, Culham, U.K., due to the
much longer life of diamond with respect to silicon detectors of comparable
volumes.

1.2 Lattice Defects in Synthetic Diamond Crystals

Lattice defects in diamonds can be detected using Raman scattering tech-


niques. Figure 2 shows some results obtained on synthetic diamonds grown
by chemical vapour deposition (CVD), that is, condensation of carbon from
a CH4 (1%)–H2 (99%) gas mixture [4] onto silicon crystal substrates. Let this
technique be called CVD heteroepitaxial growth (polycristalline, pCVD). As
one can see in the figure, the Raman spectra clearly detect the presence of
graphite, the allotropic crystalline state of the carbon, the presence of diffuse
lattice defects and impurities, and, of course, the sharp peak produced by
diamond at ∆k = ∆(1/λ) = 1332.7 ± 1.2 cm−1 .
Both graphite and diffuse crystal defects can be decreased, improving the
purity of the vapour mixture so as to avoid as much as possible nitrogen and
oxygen. The spectra in Fig. 2 are taken in conditions of increasing purity.
270 Renato Potenza and Cristina Tuvé

350

300 Negative
bias
250
Counts

200 Positive
bias
150

100

50

0
0 20 40 60 80
h (%)
Fig. 3. Pulse height efficiency η = Qc /Q 0 of a “pure” diamond specimen for α-
particles of 5.5 MeV. Qc is the collected charge and Q0 is the charge really produced
inside the diamond. This has been subject to β-irradiation before being used.

Fig. 4. Scheme of the circuit in which the diamond sensor is inserted. The reported
case is that of positive polarization of the diamond (Au electrode is positive)

One can note that in the specimen in the spectrum (c) there are no more
defects or impurities detectable with Raman technique, that is, the specimen
can be considered “pure”. Only these specimens will be considered as nuclear
detectors in this paper. However, they contain still many defects which in-
fluence their quality as nuclear radiation detectors, as Fig. 3 shows for the
spectra produced by 241 Am α-particles in a similar diamond specimen for
both polarizations.
The spectra are reported in Fig. 3 as functions of the charge collection
efficiency:
Qc ph meas
η= = , (2)
Q0 ph max
Defect Density Measurements Inside CVD Diamond Films 271

where Qc is the charge detected in the external charge-sensitive electrical


circuit, and Q0 is the charge produced inside the diamond by the passage
of the ionizing particle, so that phmeas and phmax refer to the measured
and maximum obtainable pulse height, respectively. To detect the spectra in
Fig. 3 and all the other ones with which this paper will deal, it is necessary
to adapt the diamond crystals to an external electrical circuit. To do this one
must distinguish between the substrate side of the diamond crystal, where it
is in contact with the semiconductive silicon substrate, and the growth side,
where the free CVD diamond surface appears. Figure 4 shows the schematic
drawing of a pCVD diamond inserted in the circuit which allows us to record
the electrical signals produced by the passage of a nuclear particle. A thin
(500 Å) gold deposit, sometimes done above a first, also thin (100 Å) titanium
deposit, assures electrical contact on the growth side.
The silicon substrate itself assures the contact on the substrate side.
A charge-sensitive amplification chain allows us to record the signals from
the diamond. The bias voltage is applied to the growth side, so that pos-
itive or negative polarization means that the growth surface, that is, the
gold electrode, is respectively positive or negative with respect to the silicon
substrate. Figure 4 reports the case of positive polarization, as one can see
from the indicated directions of electron and hole motion. Referring again to
Fig. 3, remembering that for a silicon detector η ≈ 1 with very good approx-
imation, one clearly sees that the spectra produced by the diamond detector
not only show mean values of the pulse heights significantly less than the
maximum possible and in any case much less then those from equivalent sil-
icon detectors, but also that the widths of the spectra are very large, though
the specimen could be considered “pure”, that is, detector grade, from the
point of view of a Raman spectrum. The resolution widths are much larger
than the minimum foreseen by (1). So one must conclude that the influence
of crystal defects is still large as it concerns the qualities of a detector and,
since the Raman spectrum is already flat, these defects can be detected by
now essentially using other probes. The proposal is to use as probes the same
nuclear particles one would like to detect.

1.3 Application of Diamond to Beam and Beam Profile


Monitoring

Before discussing in more detail how to use nuclear radiation to measure the
defect distribution in “pure” diamond crystals, it is worthwhile to discuss
how these diamonds behave when bombarded with very high nuclear particle
intensities, say I > 1 pnA = 6.25 · 109 p/s, that is, intensities for which the
crystal cannot resolve each single particle from the others within its intrinsic
resolving time τ r ≈ 1 ns. In this case the response of the detector is a direct
current in the external circuit, where the charge-amplifying chain is replaced
by a direct current amplifier. If the gold contacts (see Fig. 4) are designed
in the form of a network of pixels, the insulating properties of the diamond
272 Renato Potenza and Cristina Tuvé

assure that each pixel collects, without detectalbe cross-over among pixels,
the current produced in the cylindrical column traced along electric field lines
between the gold pixel on one side and its projection on the substrate on the
other side. So such a pixel detector bombarded by a beam of particles from
an accelerator impinging along the electrical field lines inside the diamond
can give very good information about the beam profile after an easy internal
calibration made by moving the detector so that the same part of the beam
can impinge on different pixels. Using such a direct current amplification cir-
cuit, we obtained the results shown in Fig. 5 [6]. In that figure the response
of a diamond detector is compared with the measurement of the intensity
of a 26 MeV proton beam in the Faraday cup at the end of the pipe of the
15 MV Tandem accelerator of the National Southern Laboratories (LNS)
of National Institute of Nuclear Physics (INFN) in Catania (Italy). As can
be seen in Fig. 5, the diamond follows instantaneously, in the time scale of
the figure, the changes of beam intensity. Moreover, the fluctuations in the
measurement are much less for the diamond, as seen from the fact that the
electron–hole current is much larger than the original proton current. Taking
into account the amplification factor of the circuit, it was estimated that the
ratio between proton and related electron–hole currents was 1/23 000 [6], so
that possible influence from secondary electron emission, which is a cause
of detectable error in the measurements of currents with Faraday cup, is ab-
solutely negligible. The diamond used in these measurements was only 50 µm
thick, so that a simple calculation, taking into account that 26 MeV protons
lose 0.33 MeV in passing through and remembering the energy required per
carrier pair, tells us that the charge collection efficiency at the used polariza-
tion voltage, 150 V, is about 60%. Other less rough evaluations through the
so-called restricted energy loss [7] or the computation through the standard
electron–hole pair number produced by minimum ionizing particles (MIP) [8]
give the same values within a 10% variation. As will be seen below, because
the protons pass over the diamond, there is almost no difference between the
efficiency for positive or negative polarization. This is again confirmation that
pCVD diamonds have efficiency significantly less than 1, which is different
from that of silicon detectors. The diamond detector we used is transparent
to low-energy protons and also to other low-energy ions of intermediate mass.
This means that if one removes by lapping the substrate and makes a second
gold–titanium contact on the substrate side of the diamond, the new detec-
tor offers a very good measurement of beam intensity and profile without
appreciably perturbing the beam itself, which can be monitored continuously
during the applications.
This is very important, e.g., in medical applications of nuclear radiation or
in monitoring fast neutron fluxes in the cores of nuclear reactors, particularly
fusion reactors. And this quality is well exploited by the high hardness to
radiation, proved by the fact that the diamond specimen used in [6] lasted
several hours under a current of 10 pnA of 26 MeV protons, that is, a fluence
Defect Density Measurements Inside CVD Diamond Films 273

Diamond
sensor

TANDEM
26 MeV protons Accelerator

5 mm Collimator
Faraday
cup
A

to pump

0.06
Diamond detector
current (µA)

0.04

0.02

0.00

0.2 Faraday cup


current (pA)

0.1

0.0

560 630 700 770 840 910


t (sec)

Fig. 5. Intensity vs. time (bottom) for a 27 MeV proton beam from the 15 MV
Tandem accelerator of LNS in Catania (Italy), measured simultaneously through a
diamond detector and the Faraday cup shown at the top

φ ≈ 1015 p/cm2 , without any sign of deterioration, whereas a good silicon


detector would have been damaged by a fluence one hundredth as large [2, 3].

2 Mechanism of Conduction in Circuits Including


Diamond
Let us consider the electrical circuit of Fig. 4 containing a diamond. Call V

the applied voltage, and let 2Q0 = Q+ 0 − Q0 = 2N c e be the charge produced
at a point x by the passage of a particle through the diamond. Let dU =
−Q+ 0 dV = −Q0 Edx be the energy gained by the charge Q0 during its
+ +

movement along a length dx parallel to the field E. The work needed to supply
this energy is done by the electromotive force of the generator, which moves
the induced charge of opposite sign dQ− ind in the external circuit, maintaining
a constant applied voltage V = EL, where L is the thickness of the diamond.
This work is given by dW = −V dQ− ind = −ELdQind .

274 Renato Potenza and Cristina Tuvé

Taking the x-axis going from the substrate to the growth side of the
diamond, one has:

−dU = Q+
0 Edx = −dW = ELdQind . (3)

That is,

dx v+ µ+
dQ− +
ind = Q0 = −Q+
0 dt = −Q+
0 Edt, (3a)
L L L
from which:

d+ E + +
−Q−
ind = − dQ− +
ind = Q0
c
≤ Q+
0 µ τ c ≤ Q+
0, (3b)
L L
and three similar equations with the appropriate signs for the negative charge
Q− −
0 , where Qi → −Qi and all the superscripts + → −. In (3b) and its
+

equivalent d± ± ± ±
c ≤ λc = µ τ c E ≤ L are the mean actual distances, in a
crystal of finite thickness, covered by the charges Q± 0 travelling inside under
the action of the applied field and subject to: (i) absorption from donor
or acceptor defects along the path, which is responsible for the finite λ± c ,
the charge collection distances of the carriers in that crystal; (ii) abrupt
interruption of the path for the surviving carriers able to reach the contacts,
which makes d± ± ±
c ≡ dc (x) < λc near the contacts themselves. Strictly related
to the λ±c are the mobility µ+
= v + /E and the charge collection time τ + c .
Equations (3), (3a) and (3b) are expression of the so-called Ramo’s theorem,
demonstrated by S. Ramo in 1939 [9].
Noting that when an ionizing particle passes through a solid state detector

it is always, at a given x, Q+0 = −Q0 ≡ Q0 ≡ Q0 (x), one can now define the
corresponding collected charge as

− − d−
c (x) d+
c (x)
ind − Qind = −Q0
Qc (x) = Q+ + Q+
0 (4)
L L
(d− +
c + dc )
= Q0 ≤ Q0 (x),
L
and the charge collection efficiency at the same x (see (2)) as:

Qc (d− + d+
c ) (λ− + λ+
c )
η(x) = = c < c . (5)
Q0 L L

It is clear that if the mean free paths λ±


c are both equal to or bigger
than L, taking into account the interruptions of carrier paths at contact
surfaces, where moving and induced charges neutralize each other, one has:
+x
−Q−
ind = Q0 ,
L
Defect Density Measurements Inside CVD Diamond Films 275

and

− (L − x)
ind = −Q0
Q+ .
L
As a result, Qc = Q0 , from (4), as happens in the depletion barriers of all
good semiconductors such as silicon. When, on the other hand, acceptor or
donor defects present in the material forbid long free paths for charge carriers,

then not only is Qc < Q0 , but also it can happen that λ+ c = λc . This is just
the case of the pCVD diamonds, as various recent results show [4, 10, 11]. Of
course, the charge collection efficiency η for a whole crystal is a mean value
of η(x), as said below.

2.1 Modified Hecht’s Model for Charge Transport Inside


Diamond

This section follows, with modifications, the treatment given in [12].

2.1.1 Absorption of Carriers During Their Transport Along


the Electric Field Lines

Because of the finiteness of the specimen, the values of the d± c (x)’s which
appear in (5) are less than those of the mean free paths λ±c . If the specimen
can be considered infinite, that is, L  λ±
c , then edge effects can be neglected
and the d± ± ±
c ’s reduce to the λc . To compute the values of the dc ’s in a
finite specimen it is, however, possible to start from the situation in the
infinite specimen. The general expression of a mean free path for particles in
a medium is given by
1
λ±
c = (6)
N ± σ±
where σ is the cross section of the absorption centres and N is their con-
centration (volume−1 ). There is no need that the values of σ or the N be
the same for electrons and holes, so it will be assumed that N + = N − and
σ + = σ − . There is also no need that they be constant with position inside the
specimen, so that in general λ± ±
c ≡ λc (x, y, z). However, it is useful to assume
±
for the moment that λc = const. Now, referring to Fig. 4 with the direction
of the x-axis going from bottom to top, as shown also in Fig. 6, that is, from
substrate to growth side of the diamond along the lines of the applied field,

assume that an incident particle creates at the level x, N + c (x, 0) = N c (x, 0)
carriers of both signs. Following the definition of the absorption cross sec-
tion σ, one has that after a displacement
of a given type of carriers
± ± − 

N± ±
= N±
(−N d σ ) ±
c (x,
) = N c (x, 0)e c (x, 0)e , (7)
λc
276 Renato Potenza and Cristina Tuvé

because at every

dN ± 1
c
= − ± N± ± ±
c (x,
) = −p (x,
)N c (x,
), (7a)
d
λc

where 1/λ± c is just the constant probability of absorption per unit length
p± (x,
) for positive or negative carriers, constant here since one is speaking
of infinite homogeneous specimens. Note that N ± c (x,
) is just the number
of surviving carriers at a depth
away from the point at coordinate x. To
compute the mean free path of the carriers inside an infinite and homogeneous
medium, one can write:
∞ ±  ∞ − λ±

N (x,
)d

e c d

λ = 0∞ ± = λ±
c
= 0 c . (7b)
∞ − λ±

0 N c (x,
)d
e c d

2.1.2 Edge Effects

Trying now to compute the charge collection distances d± c for finite specimens,
one must note that carriers that succeed in reaching the edges of the specimen,
that is, the surfaces at
= x moving towards the substrate side, or
= L − x
moving in the other direction, do not proceed anymore since they are all
absorbed at these values of
. So the mean value of the path length becomes:
 ap± 
± ∞ ±
0

N ±
c (x,
)d
+ ap ap± N c (x,
)d


c = ∞ ±
0 N c (x,
)d

 ap± − 
± ∞ − 
±
0
e λc
d
+ a±
p ap± e λc
d

= ∞ − ±
0 e λc
d

 ±
ap


= λ± < λ±
±
c 1−e λc
c , (8)

where a± p can take the value of x or L − x depending on both the type



+ = a− = L − x and
of carriers and the polarization p. More precisely, a+
+ −
a− = a+ = x, where subscripts refer to polarizations and superscripts to
carriers. Because of the dependence of the a± ±
p on x, the dc depend on x also
in this simple model of finite homogeneous specimens. The total number of
carriers that succeed in escaping absorption in diamond is just:

1 ∞ ± ±
N c (x,
)d
≡ Np> .
λ±
c ap ±
Defect Density Measurements Inside CVD Diamond Films 277

That is,
 a±
± 1 p
Np> = N ± (x, 0) − N±
c (x,
)d

Λ± 0

 ∞  a±
1 1 p
≡ N±
c (x,
)d
− N±
c (x,
)d
. (8a)
Λ± 0 Λ± 0

Λ± is a normalization constant, equal to λ± c only for infinite homogeneous


media; its value depends on the definition of p± (x,
) outside the edges of the
specimen. p± (x,
) has, in fact, physical meaning only inside the specimen,
but it can be convenient to extrapolate it outside. How to do the extrapolation
does not matter, because of the appearance in (8) of Λ± , which depends on
p± (x,
) in order to compensate for different arbitrary choices of the nonphys-
ical part. If the charge Q0 were all produced at the point x then substitution
of (8) in (5) would give the charge collection efficiency η. But when an ioniz-
ing particle impinges on the detector, charges are produced all along a path
which begins at the entrance edge and goes through up to the end of the
range R, or even passes over the detector if the particle energy is sufficiently
high. So, in the simple case actually being discussed, the charge produced
between x and x + dx inside the detector, neglecting the nonuniform deposit
due to Bragg’s distribution, is given by

dQ0 (x) Q0,tot Q0,tot


= = = const, (9)
dx min[Rcosθ, L] min[G, L]

where G is the penetration depth of the particle along the lines of the electric
field and θ is the angle of incidence on the growth surface. One obtains, using
(5), (8) and (9):
 min[G,L]
Qc,tot 0
η(x) dQ
dx dx
η= =  min[G,L] dQ
Q0,tot
0 dx dx

 min[G,L] (d+ −
c (x)+dc (x)) Q
0,tot
0 L · min[G,L] dx
=
Q0,tot
   
 min[G,L] + (L−x)
− +  min[G,L] − − x−
0
λc 1 − e λc
dx + 0 λc 1 − e λc
dx
=
L · min[G, L]

 L−min[G,L]   min[G,L]

− − L+ − −
− 2
−e + (λc ) 1 − e
+
− (λ+
c )
2
e λc λc λc
(λ+
c + λc )
= − ,
L L · min[G, L]
(10)
278 Renato Potenza and Cristina Tuvé

for positive polarization (the case reported in Fig. 4); for negative polarization

λ+c and λc interchange between each other to give η− . When it happens that

− (λ+
c + λc ) δ
λ+
c = λc = ≡ ,
2 2
(10) reduces to the original Hecht formula [13]:


δ δ  −
2min[G,L]
 2(min[G,L]−L)
η= 1− 1−e δ 1+e δ . (10a)
L 4G
However, there is an enormous difference between (10) and (10a). Equa-
tion (10), in fact, foresees different efficiencies of the same detector for the
same particles when the polarization is reversed, that is, when the growth
side is positive or negative with respect to the substrate side, due to the
− −
different values of λ+ +
c and λc . If one supposes for a moment that λc > λc ,
the efficiency for low penetrating particles in negative polarization is defi-
nitely less than that in positive polarization. In fact, when the particles have
G  λ± c < L, either because they have low energy or because they impinge
with high incident angle, in positive polarization one has
 
− L+
+ −  
λc e λc
+ λc
(λ+ + λ−
c ) λ+ − L+
η+ ≈ c − = c 1 − e λc ,
L L L
and in negative one has
 
− L−
− +  
λc e λc
+ λc
(λ− + λ+c ) λ− − L−
η− ≈ c − = c 1 − e λc < η+ ,
L L L

provided that L > λ+
c > λc .

2.2 Effect of Nonuniform Bragg’s Deposit of Charge into Diamond


The nonuniform production of charge carriers inside the diamond due to the
Bragg’s curve B(s) of specific energy loss along the trajectory of the particle
is easily taken into account by changing (9) to
dQ0 (x)  x
= B[x(s)] = B , (9a)
dx cosθ
where θ the incidence angle as above. Equation (10) becomes
 min[G,L]
Qc,tot η(x) dQ dx
η− = = 0  min[G,L] dx
Q0,tot dQ
dx
0 dx
 min[G,L] (d+ −
c (x) + dc (x)) dQ0,tot
0 L dx dx
= , (10b)
Q0,tot
and η+ and η− can be computed numerically.
Defect Density Measurements Inside CVD Diamond Films 279

Fig. 6. Schematic representation of in-grain and grain-boundary defects in diamond

2.3 Nonuniform Distributions of Charge and Defects

In finite and inhomogeneous diamond crystals the measurement of charge


collection efficiency for both polarizations of the crystal is a very powerful tool
to obtain the distribution of defects responsible for the quality of the crystal,
and consequently to allow the optimization of the growth parameters of the
crystals themselves. In such specimens the probabilities of disappearance of
carriers p± (x,
) in (7) is no longer constant. So the solution to (7a) becomes
the more general:

− p(x,)d
N±c (x,
) = N ±
c (x, 0)e 0 , (11)

and the collection distances become:


 a± 
± ∞ ±
0
p

N ±
c (x,
)d
+ ap a± N c (x,
)d

±
dc = ∞ ± p

0 N c (x,
)d

 a±  ∞ 
− p± (x,)d − p± (x,)d
0
p

e 0 d
+ a±
p a± e 0 d

= ∞  p
, (12)
− p± (x,)d
0
e 0 d

formally identical to (8).


The probability of disappearance p± (x,
)d
of a given carrier in the path
between
and
+ d
is, of course, proportional to the product N ± σ ± of (6).
Assuming that the cross sections for the various processes that give rise to
the absorption of a given type of carriers are constant at every point inside
the diamond, p± (x,
) is directly proportional only to the local concentrations
of defects N ± . Now, these last can be divided into two types [4], as shown
in Fig. 6: those distributed all along the diamond (the so-called in-grain
defects), which depend on the impurities and on random accumulations of
vacancies, and those which depend on the mismatch between the reticular
constants of diamond and of the substrate, which are located preferentially
in the columnar structure [4], that is, in the first part of the deposit, near the
280 Renato Potenza and Cristina Tuvé

substrate surface (border-grain defects). As said below, the in-grain defects


seem to affect the two types of carriers differently, with a greater influence on
the electrons, while the border-grain ones, being essentially structural defects,
less dependent on impurities in the crystal, seem to affect both carriers in
a similar way. So a suitable way to write the probability of disappearance
seems to be:
1 1 − (x∓)
p± (x,
) = + e Λ p = ±1, (13)
λ±
g λb

where p = ±1 is the polarization given to the crystal, assuming that the con-
centration of border-grain defects goes down exponentially from substrate to
growth surface. Now, substituting N ± (x, 0) with B(x) (9a) and using p± (x,
)
given by (13) in (11), one can finally compute numerically the correct charge
collection efficiency η± for positive and negative polarizations of a diamond
specimen bombarded with different penetrating particles. The integration
must be done numerically because (11), with the mentioned substitutions,
contains combinations of Γ and γ incomplete functions [14]. One can expect
that also in specimens considered pure from the point of view of Raman
scattering the two curves η± vs. G should be significantly different since the
defects still influence the quality of the diamond, as shown, e.g., by energy
resolution. So, the comparison of the results of the measurements of the η’s
in both polarization states can give much better information about the dis-
tribution of defects inside the diamond than Raman effects, as shown in the
next section.

3 Charge Collection Efficiencies of Diamond Detectors


Under Ion Bombardment
The results of typical measurements of mean charge collection efficiencies η±
(for positive and negative polarization) in thin pCVD diamond detectors are
reported in Figs. 7 and 8. In the first case the employed method shows a spec-
imen that is sufficiently good. In fact, the theoretical curves computed with
the simple model of (10) with uniform distribution of defects (mirrored by
the constant values of p(x,
) = (λ±c )
−1
) are very near to the curve computed
with the complete model; the length Λ in the exponent of (13) is large, so that
the defects are almost uniformly distributed. This specimen is practically the
best that one can hope to obtain from the technique of pCVD, though it is
still not satisfactory as a detector, because of the big difference between λ+ c
and λ− c and the fact that the resolution width is still on the order of 35% in
both states of polarization (compare with Fig. 3). The efficiencies reported in
Fig. 8 denote a worse specimen. The efficiency for G > L is low (on the order
of 5%), the curves given by (10) are very different from those given by the
complete model and the defect density is high in the uniform terms as in the
Defect Density Measurements Inside CVD Diamond Films 281

Fig. 7. Charge collection efficiency of a first 55µm thick diamond detector bom-
barded with 12 C at various energies. The penetration depths of 12 C particles are
also shown. Upward pointing triangles: positive polarization; downward pointing
triangles: negative polarization. Theoretical curves: (a) simple model (10) with

λ+c = 17 µm and λc = 0.5 µm; (b) same model with account of Bragg’s curve; (c)

complete model (13) with λ+ g = 33 µm, λg = 0.8 µm, λb = 25 µm and Λ = 37 µm

exponential one. As is said below, these different results can be associated


with different values of the parameters of the reactor in which the CVD dia-
monds are produced and can be used to optimize these parameters. However,
the best results for thin specimens (L < 300 µm) are not much better than
those of the diamond represented in Fig. 7. At this point it seems useful to
pay attention to some interesting characteristics of the complete model that
can be seen in Figs. 7 and 8. First, the simple model gives efficiencies that
change smoothly from those at G ≈ 0 to those at G > L, where both η’s
become equal.
The complete model instead gives a cross between η+ and η− at G ≈ L,
after which both η’s tend to the same asymptotic value as well. This value is
about the mean between those at low penetrations. The figures clearly show
this effect, which is produced by the nonuniform production of charge given
by Bragg’s curve. It is essentially an edge effect due to the fact that the
Bragg’s peak moves towards the substrate edge, so that the efficiencies again
feel the influence of the different values of the λ±
c . Second, we must note that
the points at the lowest measured values of the penetration G for positive
polarization are systematically higher than foreseen by the best fitted curves.
As said below, this depends on the fact that, for crystals with a large number
of defects, though not visible in Raman spectroscopy, a non-negligible pulse
282 Renato Potenza and Cristina Tuvé

penetration depth (µm)


10 20 30 40 50 60
20
positive bias
negative bias
simple model
15 Bragg curve
defects
c
η(%)

10

5 a

b
0
0 10 20 30 40 50 60 70 80 90 100

Beam Energy (MeV)


Fig. 8. Same as Fig. 7 for a second 55µm thick diamond detector. Theoretical

curves: (a) simple model (10) with λ+c = 3.7 µm and λc = 0.05 µm; (b) same
model with account of Bragg’s curve; (c) complete model (13) with λ+
g = 13 µm,
λ−
g = 0.3 µm, λb = 0.33 µm and Λ = 8 µm

height defect is to be foreseen and a correction must be introduced into these


data, which can be considered only rough data.

3.1 Experimental Procedure to Measure the Charge Collection


Efficiencies

The experimental setup for bombardment with 12 C or other accelerated ions


is similar to that shown in Fig. 5 and reported in Fig. 9. A collimated beam of
accelerated ions (typically I ≈ 1–3 pnA) from the 15 MV Tandem accelerator
of the LNS in Catania impinged on a ≈ 300µg/cm2 thick gold target. The
machine voltage varied between 6.8 MV and 14 MV. These values allowed
the energy of the ions to be varied between a minimum of 18 MeV for 6 Li
to a maximum of 110 MeV for 16 O; for 12 C in particular the energy was
varied between 22 MeV and 91 MeV. Scattered ions were detected either
through a silicon detector placed at θ = −20◦ with respect to the beam or by
diamond detectors placed at +20◦ ≤ θ < +30◦ at the other side of the beam.
The calibrations were done with respect to Si detector. Target and detectors
were contained in a high-vacuum scattering chamber. Pulses from Si and
diamond detectors were amplified through conventional charge preamplifiers
followed by amplifiers, converted to digital signals and registered on disc to
be analyzed off-line afterwards. The setup used for irradiation with the 5.4
MeV α-particles from an 241 Am source was, of course, simpler in that the
Defect Density Measurements Inside CVD Diamond Films 283

Fig. 9. Experimental setup for bombardment of di-


amond detectors with ions accelerated by the Tan-
dem accelerator at LNS in Catania (Italy)

experiment was done in air and the energy of the α-particles was varied
by simply changing and carefully measuring the distance between the Am
source and the detectors, that is, using air as the absorber. The electronics
were essentially the same.

3.2 Corrections to the Efficiencies η± Needed to Into Take


Account the Pulse Height Defect of Diamond for Detectors Heavy
Ionizing Particles

Figure 10 reports the charge collection efficiencies measured for the same
diamond specimen with α-particles and with 12 C of various penetrations G
in their lower range. The efficiencies measured with α-particles are definitely
higher than those obtained with carbon at the same penetration. Moreover,
there is a difference ∆η asymp ≈ 15% between the asymptotic values of efficien-
cies for α-particles and 12 C. The best hypothesis seems that this difference is
a measure of the pulse height defect in diamond between differently ionizing
particles. As is well known [15, 16], every detector is subject to the phenom-
enon of pulse height defects. It consists essentially in the fact that when the
local charge density produced by the ionizing particle in its passage is too
high, a spatial charge forms, which lowers the local electric field. This last
becomes less effective in separating rapidly carriers of opposite signs, so that
they can recombine, with a consequent reduction of the output pulse. The
reduction of the local field depends on the angle θ between the incident parti-
cle and the applied electric field, because when the electric field is just along
the line of production of carriers, these last tend to pack together, making
recombination easier.
The pulse height defect ∆E shown by a given diamond detector for given
incident ions of energy E0 can be defined empirically as the absolute value of
the difference between the mean signal actually given by the detector hit by
284 Renato Potenza and Cristina Tuvé
40
Pos Neg
35
α 0°
60°
30 75°
α
25
Efficiency (%)

α asymptotic

20 asymptotic
12C pulse height defect
15

10 12C asymptotic
α
5 12C

0
0 5 10 15 20 25 30

Penetration depth (µm)

Fig. 10. Efficiencies at low penetrations of a 130µm thick diamond in positive (full
symbols) and negative (empty symbols) polarization for α-particles and 12 C ions at
various angles of incidence

those ions and the mean signal expected for α-particles that can create the
same charge inside the detector, that is:
Q0
∆E = |η ion − η α |, (14)
e
where Q0 can be computed from the Bethe–Bloch energy loss formula [7] or
obtained experimentally from measurements with a silicon detector, making
allowance for the different values of  in (1). The value of ηα can be ob-
tained by fitting appropriate curves from (5) (using (12) and (13) in it) to
the points taken for positive and negative polarizations at low penetration
for α-particles and allowing these curves to cross just at G = L. The implicit
assumption under this definition is that the pulse height defect for light par-
ticles is negligible. A preliminary study of this phenomenon has shown [17]
that the pulse height defect ∆E defined as above can be well represented by
an empirical formula with the form of a power law in the energy E ≤ E 0 lost
inside the specimen:

∆E = AE b (1 − e−c · cosθ ), (15)

where b = 1.2 (as in silicon detectors [15]) is the same for all particles and
diamond detectors, while A and c depend on both the detector and the inci-
dent particle. A can be usefully derived from the ∆η asymp between η±,α and
η ±,ion ion at about the energy for which G = L; that of c from, e.g., η +,ion
vs. θ at constant E.
Defect Density Measurements Inside CVD Diamond Films 285

4 Conclusions
With the application of the corrections foreseen in Sect. 3.2, the model is com-
plete and is applicable to various types of detector-grade pCVD diamond, as
defined in Sect. 1.2. Using this model means: (i) bombard diamond detectors
under test in both states of polarization with α-particles in order to know
their maximum charge collection efficiencies. (ii) If the maximum available
energy of α-particles gives G > L it is enough to do measurements of η±,α ,
changing either the incident energy or the incident angle: where ∆E = 0
changing the incidence angle does not affect the ηα ’s. (iii) If α-particles can-
not penetrate the whole thickness L of the diamond, use penetrating ions from
an accelerator; measure always both rough η± , compute the pulse height de-
fect, if any, and correct the rough data as said above. At this point fitting
to the points giving the η ±,corr ’s vs. G the curves computed from (5), (12)
and (13) will give a reliable measurement of the defect distribution inside the
specimen, allowing one to compare diamonds obtained by different methods.
That is: pCVD without and with lapping from the substrate side; as-grown or
pumped CVDHG diamonds [4] (pumping improved the values of η+ increas-
ing λ+g in (13)); eventually also some new CVD diamonds grown on natural
diamond (homoepitaxial growth). It remains to explore the consequences of a
given defect distribution on the behaviour of diamond as a beam profile mon-
itor, mainly to see how it is possible, from a priori knowledge of the defect
density, to foresee the current amplification factor that one must expect.

References
[1] M. Friedl: Diamond Detectors for Ionizing Radiations, Diploma thesis, Uni-
versity of Technology, Vienna (1999) 267
[2] D. Meier, (RD42 Collaboration): Nucl. Instr. Meth. Phys. Res. A 426, 173
(1999) 268, 273
[3] D. Husson, (RD42 Collaboration): Nucl. Instr. Meth. Phys. Res. A 388, 421
(1997) 268, 273
[4] M. Marinelli, E. Milani, A. Tucciarone, G. V. Rinati: in Chap. 6 268, 269,
275, 279, 285
[5] M. Angelone, M. Pillon: EFDA Fusion Newsletter 2004/1, 8 (2004) 269
[6] M. Marinelli, E. Milani, A. Paoletti, A. Tucciarone, G. V. Rinati, S. Albergo,
V. Bellini, V. Campagna, C. Marchetta, A. Pennisi, G. Poli, R. Potenza, F. Si-
mone, L. Sperduto, C. Sutera: Diamond Relat. Mater. 10, 706 (2001) 272
[7] P. D. Group: Review of particle physics, Phys. Lett. B 592, 1 (2004) 272, 284
[8] O. Madelung, et al. (Eds.): Kristall und Festkörperphysik, Band 22, Halbleiter,
Landolt–Bornstein and Zahlenwerte und Funktionen Halbleiter (Springer,
Berlin, Heidelberg 1987) 272
[9] S. Ramo: Proc. of the I.R.E. 27, 584 (1939) 274
[10] M. Marinelli, E. Milani, A. Paoletti, A. Tucciarone, G. V. Rinati, M. Angelone,
M. Pillon: Diamond Relat. Mater. 10, 645 (2001) 275
286 Renato Potenza and Cristina Tuvé

[11] C. Tuvé, V. Bellini, R. Potenza, C. Randieri, C. Sutera, M. Marinelli, E. Milani,


A. Paoletti, G. Pucella, A. Tucciarone, G. V. Rinati: Diamond Relat. Mater.
12, 499 (2003) 275
[12] G. Pucella: Phd thesis, Rome (2003) 275
[13] K. Hecht: Z. Phys. 77, 235 (1932) 278
[14] I. S. Gradshteyn, I. M. Ryzhik: Table of Integrals, Series and Products (Aca-
demic, New York 2000) 280
[15] E. C. Finch, M. Asghar, M. Forte, G. Siegert, J. Greif, R. Decker: Nucl. Instr.
Meth. Phys. Res. 142, 539 (1977) 283, 284
[16] M. Ogihara, Y. Nagashima, W. Galster, T. Mikumo: Nucl. Instr. Meth. Phys.
Res. A 251, 313 (1986) 283
[17] G. Pucella, et al.: private communication 284

Index
charge collection efficiency (CCE), defects in diamond, 269, 270
280–285 diamond detectors, 267–273, 277, 278
chemical vapour deposition (CVD), 269 transport in diamond, 273–279
CVD heteroepitaxial growth Hecht’s model, 275
(pCVD), 269
defects Hecht theory, 275, 278
defects distribution, 279, 280
diamond Ramo’s theorem, 274
Laser Ablation-Deposited CNx Thin Films

Enza Fazio1 , Enrico Barletta1 , Francesco Barreca1, Guglielmo Mondio1 ,


Fortunato Neri1 , and Sebastiano Trusso2
1
Dipartimento di Fisica della Materia e Tecnologie Fisiche Avanzate, Universitá
di Messina, Salita Sperone 31, I-98166 Messina, Italy
fazio@ortica.unime.it
2
CNR – Istituto per i Processi Chimico-Fisici sezione di Messina, Via La
Farina 237, I-98123, Messina, Italy

Abstract. Amorphous CNx thin films were deposited at room temperature by


pulsed laser ablation of graphite targets in a controlled atmosphere using both N2
and N2 /Ar gas mixtures. The structural and electronic properties of the samples
were investigated by means of X-ray photoelectron, reflection electron energy loss
and Raman spectroscopy. Nitrogen contents as high as 32% have been estimated.
The overall results show a progressive transformation of the C–C sp3 bonds into
sp2 hybridized C–N ones with the development of sp2 carbon clusters upon increas-
ing the gas pressure values. By means of fast photography measurements, different
regimes of the laser-induced plasma expansion dynamics have been evidenced. The
results indicate that the electronic and structural properties of the laser ablation-
deposited CNx films depend strongly on the regime under which the plasma expan-
sion takes place, not simply on the overall nitrogen content. In this respect the role
played by the gas composition and pressure are of fundamental importance.

1 Introduction
Carbon nitride materials have been the focus of considerable experimental
and theoretical attention since Liu and Cohen proposed that β-C3 N4 should
have a hardness comparable to that of diamond [1]. Subsequent calculations
have shown that other crystalline C3 N4 structures should have stability com-
parable to or greater than that of β-C3 N4 , and that many of these struc-
tures should be very hard (e.g., the cubic form). The only exception is repre-
sented by the energetically most stable form, rhombohedral C3 N4 , which has
a graphite-like structure and is expected to be quite soft [2, 3]. From the ex-
perimental point of view, most of the thin films deposited with very different
preparation techniques have been shown to have an amorphous or disordered
phase although there are several reports of crystalline phases dispersed in
the amorphous matrix [4, 5]. Nevertheless, nonstoichiometric carbon nitride
thin films have also shown promising technological applications in the fields
of optical and electronic engineering due to their peculiar mechanical, optical
and electronic properties, which can be tailored as a function of the nitrogen
content x [6]. The effect of nitrogen insertion on the structure of amorphous
carbon thin films is not yet completely and easily interpreted due to the va-
riety of different local chemical environments allowed for nitrogen atoms in
G. Messina, S. Santangelo (Eds.): Carbon, The Future Material for Advanced Technology Ap-
plications, Topics Appl. Phys. 100, 287–302 (2006)
© Springer-Verlag Berlin Heidelberg 2006
288 Enza Fazio et al.

such a structural context. Usually, five possibilities based on different nitro-


gen bonding configurations are considered: incorporation in aromatic rings,
sp with one carbon neighbour, sp2 with two or three carbon neighbours and
sp3 with three carbon neighbours. The identification of such different local
chemical environments has been generally performed by means of different
spectroscopic techniques such as X-ray photoemission spectroscopy (XPS),
reflection electron energy loss (REELS), Fourier transform infrared (FTIR)
and Raman spectroscopy [7, 8, 9, 10, 11, 12, 13, 14, 15].
Many different preparation techniques can be adopted to deposit CNx
thin films [16, 17, 18, 19]. Their properties vary considerably, depending both
on the technique adopted and the deposition parameters for a given tech-
nique. Among others, pulsed laser ablation (PLA) has been widely used due
to its particular characteristics: the production of high-energy species and
great flexibility in the control of several deposition parameters (laser fluence
and wavelength, target composition, substrate temperature, target–substrate
distance and the possibility of performing the process in an inert or a reactive
background-controlled atmosphere) [20, 21, 22].
Since the PLA technique involves high-energy species, one can expect to
observe interesting, from an application point of view, C–N stoichiometries
and structural configurations, even for materials deposited at room temper-
ature (RT). For this reason, in this work we report the studies on CNx thin
films deposited at RT by means of pulsed laser ablation of graphite targets in
a controlled nitrogen atmosphere. The effects of the gas pressure and compo-
sition were also taken into account by depositing some samples in the presence
of a N2 /Ar gas mixture. Indeed, generally, there is a heavy correlation be-
tween plasma dynamics and the structural properties of the deposited film,
thus the study of characteristics of the plasma can contribute to a better un-
derstanding and control of the deposition process itself. The dynamics of the
expansion laser-induced plasma were investigated by means of fast photogra-
phy measurements, while the stoichiometry and the structure of the samples
were obtained by means of optical and electronic spectroscopy.

2 Experiments
Carbon nitride thin films were grown in a high vacuum chamber with a resid-
ual pressure down to approximately 1 × 10−4 Pa. High-purity graphite targets
were ablated by focusing the beam of a KrF excimer laser (wavelength 248 nm,
pulse width 25 ns, repetition rate 10 Hz) onto the surface with an incident an-
gle of 45◦ , and the estimated energy density was 2 J/cm2 . The samples were
deposited onto crystalline silicon and Corning 7059 glass substrates kept at
room temperature and placed at 40 mm from the target, which is positioned
on a rotating holder in order to avoid craterization phenomena. A mass flow
controller was used to introduce high-purity nitrogen gas during the depo-
sition process, reaching partial pressure values up to 66.7 Pa. Moreover, two
Laser Ablation-Deposited CNx Thin Films 289

samples were grown in a N2 /Ar gas mixture with a total pressure of 13.3 and
66.7 Pa and a N2 /Ar partial pressure ratio of 1/9 and 1/49, respectively.
The investigation of both the stoichiometry and the structural proper-
ties of the samples were performed by means of XPS, REELS and Raman
spectroscopy. In particular, REELS and XPS measurements were carried out
using a VG ESCALAB vacuum system. REEL spectra were obtained by a
VG LEG61 electron gun in conjunction with a VG CLAM 100 hemispherical
analyzer. The primary electron energy was Ep = 2.5 keV, and the incidence
angle α was about 40◦ from the normal to the sample surface. The gun cur-
rent was about 10 µA, and the pass energy of the analyzer was set to 7.5 eV.
The acceptance angle β of the analyzer was about 3◦ . The same analyzer,
with the same pass energy, was used to measure X-ray photoelectron spec-
tra excited by the Al Kα radiation (1486.6 eV) of a conventional twin-anode
Al/Mg Kα source. To take into account any possible charging effects, a tiny
silver paint droplet has been deposited on the sample surface for referencing
the binding energy scale to the Ag 3d5/2 line. The relative concentrations of
nitrogen and carbon atoms were estimated by the areas under the N1s and
C1s peaks weighted by the relative sensitivity factors. Raman scattering mea-
surements were performed by means of an U1000 Jobin Yvon monochromator
coupled with an Olympus BX-40 microscope. The 514.5 nm line of an Ar+
laser was focused on the sample surface through the 100× objective of the
microscope. The backscattered radiation was collected by the same micro-
scope optics and dispersed by a 1000 mm double monochromator, equipped
with two holographic gratings (1800 lines/mm). The dispersed radiation was
detected by means of a LN2 -cooled CCD sensor. During the film deposition
process, the light emitted from the laser-induced plasma was collected at a
right angle with respect to the plume expansion direction by means of an
optical system. A fast intensified charge-coupled device (Andor Technology
iStar iCCD) with a variable gate (∆t ≥ 2 ns) was used to detect the optical
emissions from the plasma and then to acquire the images of the expanding
plasma. A time gate of 2 ns was adopted in the initial stage of the expansion
and then progressively increased up to 50 ns to acquire the images of the
expanding plasma at different time delays after the laser pulse arrival.

3 Results and Discussion


The chemical bonding states and the relative atomic contents in CNx thin
films were investigated by means of X-ray photoelectron spectroscopy and
low-energy reflection electron energy loss spectroscopy. In fact, in the case
of CNx materials, these spectroscopic techniques are thoroughly sensitive to
local coordinations of carbon and nitrogen atoms. In particular, changes in
the carbon microstructure can be well evidenced from the modifications oc-
curring in both the subband structures and the chemical shifts of the C1s
290 Enza Fazio et al.

Fig. 1. Behavior of the nitrogen N/C ratio as a function of the gas pressure for
samples grown in pure nitrogen atmosphere. Line is a guide for the eye

and N1s core level photoemission peaks. Taking into account both the ex-
perimentally determined and the literature-reported sensitivity factors [23],
a compositional analysis was performed and the N/C atomic ratio x was ob-
tained from the integrated areas of the carbon and nitrogen photoelectron
peaks. In Fig. 1 is shown the compositional parameter x as a function of the
nitrogen partial pressure. The results (see also Table 1) show that, under
the ablation conditions chosen, increasing P N2 up to 13.3 Pa, the nitrogen
content reached a value close to x = 32 % and then decreased down to about
17% at P N2 = 66.7 Pa.
In Fig. 2a are shown the C1s XPS lineshapes of some of the investi-
gated samples grown at different pure nitrogen partial pressures: a clear
modification is evident. The effects of the increasing gas pressure are an
asymmetric broadening and a shifting towards higher binding energies of the
C1s peak, with respect to the position observed for pure carbon systems
(284.5 eV). These effects, also evident for the lowest nitrogen partial pressure
(P N2 = 0.1 Pa), indicate the occurrence of changes in the carbon chemical
bonding structure due to the formation of nitrogen–carbon bonds. It is not
possible to unambiguously deconvolve the C1s core level photoelectron peak
since an accurate determination of the different contributions is difficult to
give. Nevertheless, it is quite well established that the main contribution de-
tected at 284.5 eV is attributed to pure carbon (C–C bonds in a-C network),
while the asymmetry on the high binding energy side depends on the lo-
cal environment of the carbon atoms into C–N sp3 and C–N sp2 bonding
coordinations located at 286 eV and 287 eV, respectively [24].
Laser Ablation-Deposited CNx Thin Films 291

Fig. 2. Experimental C1s and N1s XPS spectra of CNx films grown at different
nitrogen partial pressures

In Fig. 2b are shown both the experimental and the numerically fitted N1s
XPS spectra of CNx films. To check the bonding states of carbon in the sam-
ples, the N1s peak was deconvolved by using two Gauss–Lorentzian bands
positioned around 398.5 eV and 400 eV [21]. These two bands are assigned
to different nitrogen bonding states in C–N bonds and, more precisely, to
N bonded to sp3 -hybridized C and to N bonded to sp2 -hybridized C, respec-
tively. Nitrogen–carbon triple bonds have been excluded due to the absence
of their characteristic resonance at about 2200 cm−1 in the infrared trans-
mission spectra. Overall, the results of the fitting procedure show that the
400 eV N1s photoemission peak exhibits a slight, but definite, growth upon
increasing the nitrogen partial pressure.
The XPS results, by themselves, do not give a complete information about
the carbon–carbon bond reorganization, nevertheless, combining them with
REELS data, an estimate of the various C–N and C–C bonding types con-
centration can be obtained. In the following, according to the literature [25],
the short notations [C–Csp2 ], [C–Csp3 ], [N–Csp2 ] and [N–Csp3 ] have been
used to indicate the concentrations of different bonds type in a-CNx .
From the analysis of energy loss spectra [10, 12], the low-energy plasmon
Eπ is known, and a shift of the main plasmon peak towards lower energies
292 Enza Fazio et al.

Table 1. Results of XPS and REELS spectra analysis: x(%) is the relative nitrogen
content with respect to carbon, [N–Csp2 ] (%) and [N–Csp3 ] (%) are the fractional
contributions to the C–N bond, Ep (eV) and Eπ (eV) are the high- and low-energy
plasmons, ρ is the calculated mass density, and sp2 and sp3 are the relative fraction
of sp2 and sp3 bonds

Sample P N2 /P A x [N–Csp2 ] [N–Csp3 ] Ep Eπ ρ sp2 sp3


# Pa % % % eV eV g cm−3 % %
22 0.0/– 0.0 0.0 0.0 26.9 5.1 2.61 50.5 49.5
40 0.1/– 2.7 1.4 1.3 27.1 5.2 2.65 53.7 46.3
37 1.3 8.6 5.1 3.5 26.7 4.9 2.57 53.8 46.2
47 1.3/12.0 9.0 6.0 2.9 – – – – –
49 1.3/65.0 3.0 1.8 1.3 21.8 5.3 1.71 75.6 24.4
42 6.5 7.3 5.1 2.2 26.2 5.2 2.46 61.5 38.5
24 12.8/– 25.0 12.0 13.0 24.0 4.2 2.05 58.8 41.2
45 13.3/– 32.0 24.4 6.7 23.7 4.4 1.99 67.7 25.6
39 17.0/– 11.9 9.2 2.7 26.1 5.0 2.44 60.6 39.4
38 26.6/– 12.2 8.5 3.7 25.5 4.8 2.32 58.0 42.0
48 66.7/– 16.0 14.1 3.5 23.4 5.4 1.96 90.1 9.9

(from 26.9 to 24.0 eV) is also evident, increasing the x values (see Table 1).
Applying the Drude formula, this trend can be related to a reduction of
the valence electron density and interpreted in terms of a reduction of mass
density ρ of the samples. Moreover, to simplify, we assume that our samples
are essentially built up by only threefold and fourfold coordinated carbon
atoms bonded to other carbon or nitrogen atoms. So, we can state:

[N–Csp2 ] + [C–Csp2 ] + [N–Csp3 ] + [C–Csp3 ] = 1, (1)

where the concentrations of N–Csp2 and N–Csp3 bonds are known from the
XPS quantitative analysis of the N1s photoemission peaks, while the total
concentration of the C–Csp2 bonds can be calculated by applying the Drude
formula to the low-energy plasmon resonance Eπ ,
Eπ2
[Csp2 ] = [C-Csp2 ] + [N-Csp2 ] = 7.25 × 1020 , (2)
sNC
where NC is the density of carbon atoms and s = 0.28 is a static screening
factor which takes into account the screening effects on the π electrons due
to the remaining σ electrons [10, 26, 27]. Thus, using the previous relations
(1) and (2), it is possible to calculate the remaining bond fraction [C–Csp3 ].
All the results (see Table 1) show the continuous growth of the sp2 bond
fraction and the contemporary decrease of the sp3 one with an increase of
the nitrogen partial pressure (see Fig. 3a). Moreover, both [N–Csp3 ] and [N–
Csp2 ] slightly increase at the same rate. This behavior indicates a progressive
material graphitization which proceeds at expense of the [C–Csp3 ] concen-
tration. It seems that nitrogen could preferentially substitute carbon atoms
Laser Ablation-Deposited CNx Thin Films 293

Fig. 3. Behavior of the partial contributions [N–Csp2 ], [N–Csp3 ], [C–Csp2 ] and


[C–Csp3 ] as a function of the gas pressure

bonded in a fourfold coordination, inducing an increase of the graphitic is-


lands of the samples. From Fig. 3b is also evident a slow and smooth variation
of the estimated mass density ρ. The density values of our samples are not
comparable to those reported in literature for CNx samples with low nitro-
gen content [28, 29]. Nevertheless, in our opinion, the bonding configurations
present in the CNx films are strongly dependent not only on the nitrogen
content, but also on the starting sp3 /sp2 bonding ratio, which, in turn, is
determined by the samples preparation conditions.
Additional details about the change in the carbon bonding structure were
also evidenced by the evolution of the D and G bands in vibrational Raman
spectra. In fact, visible Raman spectroscopy is sensitive to the carbon sp2
phase due to the resonance with π–π ∗ transitions which occurs in sp2 do-
mains while σ–σ ∗ transitions, occurring in both sp2 and sp3 domains, are
in resonance with UV light. Then, visible Raman spectroscopy can only in-
directly probe the evolution of an sp3 phase through the evolution of the
sp2 one. In particular, the sp3 /sp2 bonding ratio can be indirectly evaluated
from the ratio between the intensity of the two contributions (the so-called
D and G bands). Indeed, the G band is connected with the relative motion of
sp2 carbon atoms, while the D peak is related to the breathing mode of the
aromatic rings [30]. The evolution of the D band is indicative in microcrys-
talline graphite of a disordering process which produces smaller and smaller
crystalline domains, while in diamondlike carbon system its appearance is re-
lated to the development of an sp2 phase with the creation of sixfold aromatic
rings.
294 Enza Fazio et al.

PN =0.1 Pa PN =6.5 Pa
2 2
Intensity (arb. un.)

P =66.7 Pa
N
PN =17 Pa 2
2

1100 1300 1500 1700 1100 1300 1500 1700


Raman Shift (cm−1)

Fig. 4. Raman spectra of CNx films grown at different nitrogen partial pressures.
The dashed lines represent the fitting of the D and G peaks

The Raman spectra of some samples grown at different nitrogen partial


pressures are shown in Fig. 4. The spectra are characterized by a broad asym-
metric band near 1550 cm−1 (G band), with a shoulder at 1300–1400 cm−1
(D band), typical of diamond-like carbon systems. Raman spectra were de-
convoluted using a Breit–Wigner–Fano (BWF) lineshape for the G peak plus
an additional Gaussian line for the D peak [31]. The BWF lineshape is de-
scribed by:

[1 + 2(ω − ω0 )/QΓ ]2
I(ω) = I0 , (3)
1 + [2(ω − ω0 )/Γ ]2
where I0 is the peak intensity, ω0 is the peak position, Γ is the full width half
maximum (FWHM) and Q−1 is the BWF coupling coefficient. The maximum
of the BWF line used to account for Raman contribution at around 1300 cm−1
due to its asymmetric line-shape lies at:
Γ
ωmax = ω0 + , (4)
2Q
where the peak position ωmax is lower than the line position of the undamped
mode peaked at ω0 if Q value is negative.
The positions, the linewidths and the intensities of the G and D bands
were deduced from the fitting procedure (see Table 2). It is evident that
Laser Ablation-Deposited CNx Thin Films 295

Fig. 5. Variation of I D /I G ratio of the Raman spectra vs. the gas pressure for
samples grown in pure nitrogen atmosphere. The line is a guide to the eye

Table 2. Results of the deconvolution procedure performed on the Raman spectra


and sp3 /sp2 bonding ratio as determined by REELS analysis

Sample P N2 /PA x I D /I G ωG γG sp3 /sp2


# Pa % cm−1 cm−1
40 0.1/– 2.7 0.21 1548 250.0 0.86
37 1.3/– 8.6 0.32 1545 230.0 0.86
47 1.3/12.0 9.0 0.32 1574 188.3 –
49 1.3/65.0 3.0 0.30 1548 187.8 0.32
42 6.5/– 7.3 0.34 1555 217.3 0.63
45 13.3/– 32.0 0.48 1563 181.7 0.38
39 17.0/– 11.9 0.49 1575 162.8 0.65
48 66.7/– 16.0 0.57 1583 144.7 0.11

with increasing nitrogen partial pressure, the D band intensity increases and
the G band position shifts towards higher frequencies, while its linewidth
decreases. In Fig. 5 the I D /I G ratio increasing behaviour is evident, even at
relatively low nitrogen gas pressures.
As reported above, the I D /I G values can be used only to indirectly esti-
mate the sp3 content. However, the values obtained from REELS and XPS
results are in good agreement with Raman ones. In fact, at the lowest nitro-
gen partial pressure, the films present a higher sp3 /sp2 bonding ratio and,
correspondingly, low I D /I G values (the structure is characterized by olefinic
groups [32]). Upon increasing the nitrogen partial pressure, the sp3 /sp2 ratio
decreases and, correspondingly, the I D /I G ratio increases (see Table 2). Such
296 Enza Fazio et al.

behavior is consistent with a transformation of sp3 bonded carbon atoms into


sp2 ones, induced by the higher nitrogen partial pressure values. Clustering
of sp2 sites gives rise to ordering and aromatic ring development, which in
turn increase the D band intensity.
As can be seen from Fig. 1, the nitrogen content steadily increases with
the nitrogen pressure, but above a certain value, it drops drastically. Nev-
ertheless, the I D /I G value shows a monotonic increase with the pressure.
It is well known that in PLA experiments the plasma expansion dynam-
ics is strongly affected by the pressure and by the chemical nature of the
gas through which the expansion takes place. Thus, the observed structural
properties of the films cannot be simply dependent on the nitrogen gas pres-
sure but, more generally, on the expansion dynamics also. To investigate this
important aspect, we prepared a set of samples in a nitrogen/argon gaseous
mixture, keeping fixed the nitrogen partial pressure.
Just after the arrival of the laser pulse on the target surface, a plasma
ball develops and starts to expand along the normal to the target surface.
When such an expansion takes place in a background gas, as happens in the
deposition of CNx thin films, a shock wave can develop if some conditions
are fulfilled. Indeed a shock wave, due to the supersonic expansion of the
plasma in the gas, develops if the mass of the removed material is lower than
the mass of the gas surrounding the plasma and if the pressure driving the
moving front of the plasma is greater than the pressure of the gas at rest.
Useful information about the expansion dynamics can be obtained by means
of time-resolved fast photography of the expanding plasma. The appearance
of a bright edge at the contact front between the plasma and the surrounding
gas is, in fact, indicative of the development of the shock wave. Moreover, the
position R of the front edge of the plasma as function of the time t, after the
arrival of the laser pulse, can be obtained from these images. The expansion
of the shock wave front as a function of time is given by the following relation:
 1/5
E
R = ξ0 t2/5 , (5)
ρ0

where ξ is a factor related to both geometrical and thermodynamical quanti-


ties, E is the plume energy, and ρ0 the density of the gas at rest [33]. Usually,
three expansion regimes are observed: a first stage, where interaction with
the gas weakly affects the expansion, in which the plasma expands linearly
with time, then a shock wave develops and finally the plasma expands as a
sound wave. Eventually the plume stopping can also be observed. In Fig. 6
the position of the moving front of the plasma is reported as a function of
time for different ambient gas and pressure conditions, as obtained from the
time-resolved images of the expanding plasma, not shown here. In particular,
experiments were performed at three pure nitrogen pressures (i.e., 1.3, 13.3
and 66.7 Pa) and two N2 /Ar mixtures (i.e., 13.3 and 66.7 Pa with P N2 /P A ra-
tios of 1/9 and 1/49, respectively). As can be seen from Fig. 6, at a pressure
Laser Ablation-Deposited CNx Thin Films 297

Fig. 6. Variation of the position R of the plume front edge as a function of time.
Open symbols refer to expansion in different pure nitrogen pressure, while solid ones
to expansion in mixed N2 /Ar atmosphere

of P N2 = 1.3 Pa the expansion dynamics is weakly influenced by the back-


ground gas: initially a linear behavior holds and only at longer delay times
deviation from this behavior can be envisaged. Interaction with the gas be-
comes more and more effective as the nitrogen pressure is increased, and a
slowing down of the plume can be clearly observed. Similar results have been
obtained for the two experiments performed in the mixed N2 /Ar atmosphere.
In this case the slowing down of the plume is evident also at the total pressure
of 13.3 Pa. Argon atoms thus are more efficient in limiting the expansion of
the plasma with respect to the nitrogen molecules. When data reported in
Fig. 6 were fitted with relation (5) a good agreement could be obtained only
in a limited time range. Arnold et al. [34] proposed an analytical model that
could describe the whole expansion process in terms of the above reported
temporal stages. The transitions from a temporal stage to the following one
are also taken into account. The experimental data are expressed in terms of
the following dimensionless variables:
 −1/3  −1/3
2E 2E
R̃ = R t̃ = tvs , (6)
P P
where E is the plume energy, P the pressure of the gas and vs the velocity
of the sound in the undisturbed gas. When the R − t experimental data are
transformed using relations (6), all the curves showed in Fig. 6 collapse onto
298 Enza Fazio et al.

Fig. 7. Plot of the distance vs. time in dimensionless variables for pure nitrogen
atmosphere and for the nitrogen/argon gaseous mixture case (inset)

a single master curve as shown in Fig. 7. The experimental data describing


the expansion in pure nitrogen gas show two distinct slopes as a function
of t̃ : (i) a linear behavior typical of a free expansion regime and (ii) a region
where a R ∝ t−1/3 relation holds. In the inset is shown the same plot, but
for the experiments performed in the N2 /Ar mixtures. It can be clearly seen
that the shock wave regime is present for all the mixtures.
In Fig. 8 we report the XPS (Fig. 8a) and Raman (Fig. 8b) spectra of
the samples deposited in nitrogen/argon gaseous mixture. Comparing these
results with those obtained for the corresponding samples deposited at the
same pressure but in an all nitrogen atmosphere, the following effects are
evident: (i) a growth of the concentration of the N atoms bonded to sp2 -
hybridized C and (ii) a blue-shift of the G band position with a decrease
of its linewidth, while the D band intensity remains almost constant. The
relevant nitrogen content x and the I D /I G ratio are reported in the tables.
A clear correlation between the stoichiometry and the structure of the
growing films and the plasma expansion regimes emerges from these results.
In fact, concerning the samples grown in a pure nitrogen atmosphere, increas-
ing P N2 up to 13.3 Pa, the N/C content reaches a value close to 31.2% and the
I D /I G ratio increases: a progressive development of the sp2 carbon clusters
is induced. Nevertheless, the further increase of P N2 up to 66.7 Pa does not
induce an increase in nitrogen content, since the N/C ratio is less than 20%.
A further transformation of sp3 bonded carbon atoms into sp2 ones, as well
Laser Ablation-Deposited CNx Thin Films 299

Fig. 8. XPS (a) and Raman (b) spectra of the samples deposited in nitrogen/argon
gaseous mixture

as a clustering process of the sp2 domains are observed. In such a case the
dynamics of the plasma expansion plays a crucial role. As observed from the
fast photography, the dynamics of the expanding plasma changed from a free
expansion behavior at low pressure to a shock wave formation at the higher
pressures and, in the late stage, plume stopping has also been observed. In
such a case the reduced nitrogen content in the films upon raising the pres-
sure up to 66.7 Pa is a consequence of the reduced flux of species reaching
the substrates, due to the increased collision rate between the plasma species
and the nitrogen molecules. The observed increase of the I D /I G ratio can be
understood if the reduction of the kinetic energy of the species impinging on
the substrates is considered.
Concerning the sample deposited in the nitrogen/argon atmosphere, at
13.3 Pa with 1/9 N2 /Ar, the dynamics of the expansion plasma are different
from the ones observed at the same total pressure, but in pure nitrogen. In our
case, in the mixed gaseous mixture the nitrogen content drops rapidly from
27% down to 3% as argon atoms are introduced in the chamber, even though
the total nitrogen gas content is kept constant. Thus, the reduction of the
nitrogen content has been explained considering the plasma dynamics, and
300 Enza Fazio et al.

it is expected that the reduction of the kinetic energy of the species should
produce an increase of the I D /I G ratio. On the contrary, it remains constant
for both the samples with values comparable to the one estimated for sample
grown at 1.33 Pa in a pure nitrogen atmosphere. Really, it is important to
remark that the nitrogen content of the two films is very low (from 9% down
to 3%) so that the increase of sp2 carbon phase due to the nitrogen content
can be expected to be very low. Thus, the structures of the films are more
dependent on the dynamics of the plume expansion rather than on the total
pressure at which they are deposited. In this respect the nature of the gas
mixture must be taken into account.

4 Conclusion
In summary, CNx thin films have been deposited by means of pulsed laser
ablation at different N2 and N2 /Ar mixed partial pressures. In particular, the
results obtained can be summarized as follows. Concerning the samples grown
in pure nitrogen atmosphere, the nitrogen content increases upon increasing
the nitrogen partial pressure up to 13.3 Pa, but when it is raised to 66.7 Pa,
its value decreases. The nitrogen introduction in the amorphous carbon ma-
trix has been found to induce an increase in the total threefold-coordination
fraction with a contemporaneous lowering of the C–C fourfold-coordination
concentration, as evidenced by the XPS and REELS measurements.
Nevertheless, as shown by the Raman spectroscopy results, the growth
of graphitic domains has also been observed when nitrogen content in the
films decreases, as happens for the samples deposited at the highest partial
pressures. This behavior is explained in terms of the reduction of the kinetic
energy of the depositing species, i.e., it involves the plasma expansion dynam-
ics. Changes of the expansion dynamics from a linear expansion to a shock
wave formation and, finally, to the stopping of the expansion were observed.
The decrease of the nitrogen content in the films above a certain nitrogen
pressure have been related to the transition from the free expansion to the
shock wave formation transition.
Samples grown in N2 /Ar gaseous mixture show a nitrogen content as
low as that of the sample deposited in 1.33 Pa of pure nitrogen gas. Also
the trend of the structural properties, as evaluated from the I D /I G ratio,
is similar, even though, considering the total pressure at which they were
deposited, higher values should be expected. All these results reveal that
the structure of laser ablation-deposited carbon–nitrogen thin films depends
strongly on the dynamics of the expansion plasma regime, not simply on
the overall nitrogen content, and in this respect the role played by the gas
composition and pressure is of paramount importance.
Laser Ablation-Deposited CNx Thin Films 301

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Index
sp3 /sp2 bonding ratio, 293, 295 G band, 293, 294, 298

carbon chemical bonding, 290 plasma


carbon coordination, 291 plasma expansion, 296, 299
threefold and fourfold coordination, plasma plume
292, 296 plume stopping, 297
chemical shift, 290 pulsed laser ablation (PLA), 288, 296,
CNx thin films, 289, 290, 296, 298 299
core level photoelectron peak, 290
Raman spectroscopy, 288, 289, 293–295,
D/G band intensity ratio, 295 298–300
D/G band intensity ratio, 295, 298–300 reflection electron energy loss spec-
density, 293 troscopy (REELS), 288–292, 295,
diamond-like carbon (DLC), 294 300
diamondlike carbon (DLC), 293
D band, 293, 294, 296, 298 shock wave, 296, 298–300

fast photography, 287–289, 296, 299 X-ray photoemission spectroscopy


free expansion regime, 297 (XPS), 288, 291, 292, 295,
298–300
graphite-like carbon (GLC), 287 x-ray photoemission spectroscopy
graphitization, 292, 293, 299 (XPS), 289–291
Modeling of the Transport Properties
of Diamond Radiation Sensors

Stefano Lagomarsino and Silvio Sciortino

Dipartimento di Energetica, Università di Firenze, Via S. Marta 3, I-50139


Firenze, Italy, and INFM, Unità di Ricerca di Firenze
sciortino@fi.infn.it

Abstract. A fully quantitative model of electronic transport in polycrystalline


chemical vapour deposited (pCVD) diamond sensors is presented, predicting the
conductivity behavior of diamond devices during and after exposure to ionizing
radiation. The model takes into account a widely adopted qualitative picture of the
diamond band gap, based on two distributions of defect levels: a mid-gap group
of recombination centers and a distribution of traps closer to one of the band
edges. Analytical expressions for the radiation-induced currents (RIC) and persis-
tent radiation-induced currents (PIC) are derived from the solutions of a complete
set of rate equations, and the experimental data are well fitted by assuming the
distribution of the trap centers to be formed from the superposition of several uni-
form bands, with different cross sections, energies and concentrations. The model is
validated against experimental data from a set of diamond detectors whose charge
collection distance ranges over an order of magnitude (from 15 µm to 250 µm),
i.e., from highly defective to the state-of-the-art material. A rationale is then pro-
posed for the relationship between material quality and trap parameters, also with
regard to the changes in the material properties caused by high irradiations of fast
neutrons.

1 Models of the Polycrystalline Diamond Band Gap


The simplest model for carrier kinetics in a wide band-gap material which
can explain and reproduce the experimental data involves an active trap and
a recombination center [1]. Deeper trap centers can also be introduced which
are not active at the temperature of interest, i.e., whose activation energy is
far higher than the Boltzmann factor kT . These centers can play a role only
in the neutrality condition of the material, which is an underlying assumption
of almost all the works found in literature, and in determining the position
of the Fermi level at thermodynamic equilibrium.
This picture is obviously oversimplified in the case of crystalline diamond
with a band gap as high as 5.5 eV and a considerable variety of possible
defect centers. The effort to take into account a competition between different
trapping centers in an insulator material is due to Chen et al. [2], whilst
McKeever et al. [3] have reviewed the main models proposed to describe
thermally and optically stimulated luminescence phenomena.

G. Messina, S. Santangelo (Eds.): Carbon, The Future Material for Advanced Technology Ap-
plications, Topics Appl. Phys. 100, 303–327 (2006)
© Springer-Verlag Berlin Heidelberg 2006
304 Stefano Lagomarsino and Silvio Sciortino

Nevertheless, a two-level model allows us to introduce basic concepts


and describe processes which will be generalized in the following sections
to a more satisfying model. This generalization is based on the experimental
data collected for several years on polycrystalline chemical vapour deposited
(pCVD) diamond. In this section, we give a short review of some relevant
models presented so far, resulting in a commonly accepted qualitative de-
scription of the band-gap structure of the highest quality pCVD diamond. In
Sects. 1.4 and 1.5 we will introduce experimental facts which will be useful
to develop a mathematical model of the carrier kinetics. The assumptions
on which the model is based will be reviewed in Sect. 2. The model will be
tested on pCVD diamond devices, specially prepared as ionizing radiation
detectors. Radiation-induced conductivity will be considered in Sect. 3, and
thermal relaxation of trapped carriers in Sects. 4 and 4.1. In Sect. 4.2 persis-
tent (radiation-induced) current will be treated in detail. The quality of the
samples, their performances and the effect of neutron irradiation will be ex-
plained in terms of the obtained values of the trap and recombination center
parameters.

1.1 Band A

Donor–acceptor pair recombination (DAP) has been extensively studied in


natural and synthetic high-pressure high-temperature (HPHT) diamond [4]
as well as in thin diamond films [5]. In those works DAP is ascribed to
recombination between levels due to boron and nitrogen, i.e., the extrinsic
impurities more easily incorporated in the diamond lattice. DAP is related to
well-known luminescence broad bands [6], from 1.8 eV to about 3.2 eV. Con-
versely, a broad band peaking at 2.8 eV, commonly referred to as band A, is
believed to be originated by dislocations [5], possibly including sp2 -like struc-
ture [7]. Band A is generally prominent in the cathodoluminescence spectra in
high-quality pCVD diamond [8]. Moreover, sharp photoluminescence peaks
are less observed in higher quality samples, due to the absence of nitrogen
and other impurities [9].
As can be expected, the band A emission disappears in some single-crystal
CVD (scCVD) diamond films, also if it is observed in homoepitaxial diamond
films with nonepitaxial crystallites [7]. Manfredotti et al. [10] have suggested,
by photoconductivity (PC) and electroluminescence measurements, that the
defect levels related to band A act as a recombination center inside the dia-
mond band gap.

1.2 Trapping Centers

Many conductivity investigations [11, 12] support the existence of acceptor


states close to the valence band, probably related to grain boundaries. Gonon
et al. [12] proposed a trapping/recombination mechanism governing the ther-
mally stimulated conductivity (TSC) and UV photoconductivity. According
Modeling of the Transport Properties of Diamond Radiation Sensors 305

to their scheme, acceptor states at 1 eV from the valence band (VB), partially
filled in their initial state, are responsible for the conduction of unirradiated
samples. As electron–hole pairs are generated by UV illumination, electrons
are trapped on levels located at 1.9 eV below the conduction band (CB).
During thermal annealing carriers are released from the deep electron trap
to the CB and return to the initial electron state. A similar mechanism has
been suggested by Vittone et al. [13], relying on thermoluminescence (TL)
characterization. Diamond samples are exposed here to α-radiation and then
illuminated by visible light. Finally, the TL glow curve is recorded. Optical
fading of the TL signal starts at about 550 nm and is nearly full at 500 nm. In
order to explain this effect, the authors assume the existence of an electron
trapping band at half band gap and a hole trapping level with activation
energy in the range 0.98–1.13 eV above the VB. These traps are first satu-
rated (primed) by exposure to an α-source, then illuminated. On reaching the
wavelength of 550 nm, light photons have enough energy to release trapped
electrons, which tend to annihilate the still trapped holes. Souw et al. [14] in-
dependently propose a qualitative model with a defect band close to the VB,
and a defect band close to half band gap, negatively and positively charged,
respectively, at thermal equilibrium. Under these hypotheses they explain
their photoconductive (PC) measurements from red to over band-gap UV
and backwards. They observe that only holes contribute to the PC signal in
their samples.
Conversely, Nebel et al. [15, 16] report that nominally undoped pCVD
diamond is an n-type semiconductor, but in this case the investigated samples
yield a high concentration of nitrogen (∼ 1018 cm−3 ). They also propose a
qualitative model of amorphous carbon-like density of states present at grain
boundaries.
In conclusion, there is plenty of experimental evidence of distributions of
deep and shallow traps close to the band edge and recombination bands close
to the mid-gap. Whether the traps are close to the valence or conduction
band edge it is not well assessed. In the following we will try to give a math-
ematical treatment of the carrier kinetics independent from this choice. We
will consider hole traps close to the VB edge, but our conclusions will hold
as well for the opposite situation.

1.3 Carrier Lifetimes and Charge Collection Distance

A theoretical model on natural diamond, based on transient conductivity


measurements, has been proposed by Pan et al. [17, 18], to relate the defect
levels inside the band gap to the carrier lifetimes. They introduce a deep
donor level, acting as a recombination center for holes and electrons, which
they tentatively attribute to an impurity concentration of 20 ppm of nitrogen
in different aggregate forms. Two additional trap mechanisms for holes and
electrons are considered, by means of two decay times τ p and τ n . This model
fits very well to the experimental data, yielding the concentration, N r ∼
306 Stefano Lagomarsino and Silvio Sciortino

1018 cm3 , and cross-section values of the recombination center σ p = 1.4 ×


10−16 cm2 and σ n = 3.1 × 10−14 cm2 , for holes and electrons, respectively.
The lifetime of the carriers is on the order of hundreds of picoseconds.
Such a high density of defects is believed to limit the charge collection
distance (CCD) in natural IIa diamond to values of 20 to 50 µm [19]. The
CCD is defined as the average distance electrons and holes move apart un-
der the influence of the external electric field, before they are trapped in the
diamond material or reach the electrodes, and it is used as a major figure
of merit of pCVD diamond detectors and of the material itself. In pCVD
diamond the content of impurities can be strongly reduced with respect to
natural or HPHT synthetic diamond. Indeed, pCVD diamond from produc-
tion reactors now “regularly” exhibits 300 µm charge collection distance [20],
a value which is believed to be mainly limited by grain boundaries.

1.4 Location of the Trapping and Recombination Centers


in the Diamond Band Gap

In order to test the outlined picture of two distributions of defect levels, and
to locate their position inside the diamond band gap, we performed a set
of CCD measurements on a state-of-the-art pCVD diamond after exposure
to light [21]. We illuminated with photons of different energies a diamond
device produced by De Beers Industrial Diamonds (DEBID) for the RD42
collaboration (sample CDS88) [22]. The diamonds were metallized with a
single electrode on one side and 256 narrow strips on the other side. The
strips had a width of 25 µm and a pitch of 50 µm, which allowed the radiation
to penetrate the material. All the strips were shorted to form a single electric
contact. The sample was exposed to light starting from two different initial
states:
– (P) “pumped” state, obtained by irradiating the sample with a 10 mCi
β-radiation source to an absorbed dose of about 1 Gy. A rise of the ra-
diation-induced current of the sample occurs due to passivation of deep
traps, a phenomenon which is commonly referred to as “pumping”. No-
tably, a dose one tenth as large is high enough to obtain an increase in
CCD, measured off-line, from about 150 µm to 230 µm. This effect can
endure for months in a dark environment at room temperature.
– (D) “depumped” state, obtained by exposing the sample to a continuous
light source such as a halogen lamp. This procedure reset the CCD of the
sample to the initial value, about 150 µm.
We divided the band gap into twelve intervals ∆Ei = [Ei , Ei+1 ], and exposed
the sample to photons with energy spread ∆Ei . Then, we measured the CCD
under exposure to relativistic β-particles, which is the standard method to
test the collection efficiency for minimum ionizing particle (MIP) detection.
The measurements were performed according to the following scheme for each
energy interval ∆Ei :
Modeling of the Transport Properties of Diamond Radiation Sensors 307

Fig. 1. Measured CCD in the depumped (dashed line) and pumped state (solid
line) as a function of the photon energy of the applied luminous exposure. Model of
the trapping–detrapping mechanisms. The fat arrows indicate the main transitions
during the pumping and depumping processes. A tentative evaluation of the extent
and position of the defects bands is also indicated

1. First, we set the sample in the P state, then we expose it to photons of


energies in ∆Ei , finally we measure the CCD.
2. First, we set the sample in the D state, then we expose to photons of
energies in ∆Ei , then we measure the CCD.
The outcome of these measurements is presented in Fig. 1.
The band gap appears to be divided into four regions (I–IV in the figure):
– Starting from the D state, photons of energy in II and IV are able to
pump (at least partially) the sample while photons of energy in I and III
do not change the state of the sample.
– On the other hand, starting from the P state, photons corresponding to
region III completely depump the sample.
Notably, the energies of region I and III are complementary, in the band
gap, to those of region IV and II, respectively, in the sense that, if photons
of energy E tend to pump diamond, photons of energy (Egap − E) tend to
depump it, and vice versa. This is true except for region I, whose photons
does not affect the P state of diamond. We ascribe this fact to a small capture
cross section for these photons of the centers responsible for the P state.
These considerations lead to the conclusion that pumping/depumping
processes are ruled by the filling or emptying of two bands of levels, one for
each pair of regions: zone II and III relative to the band closer to mid-gap,
zone I and IV to the other one. Photons with pumping energies fill directly
one of the bands, leaving a free carrier (hole or electron) which is trapped
by the other one. Depumping photons, on the other hand, empty one of the
bands, and the released carriers recombine in the other. We will assume, in
the following, that the shallowest trap distribution is closer to the VB, but all
our considerations hold as well when the positions are reversed with respect
to half band gap.
308 Stefano Lagomarsino and Silvio Sciortino

In order to assure neutrality, the two bands have to be either neutral or


oppositely charged. The depumped state most likely corresponds to charged
bands, because the capture cross sections of charged centers tend to be higher
than those of the neutral ones [23].
In conclusion, there is experimental evidence supporting the picture of
two bands, a deep donor and a deep acceptor center distributions, with the
Fermi level situated somewhere in between, so that the two distributions are
charged at thermal equilibrium (depumped state).
We will refer to the deep donor distribution as “band A” because it has
a maximum density in the region where the luminescence band A is peaked.
This assumption is in agreement with the suggestion of Manfredotti et al. [10],
that this band acts as a recombination center. We also denote the deep ac-
ceptor center as “band B”.
The boundaries of the regions I–IV suggest that band A ranges from about
1.7 to 2.7 eV, where it has a maximum concentration [21], while band B is
extended up to 1.7 eV. These values of energy are confirmed by photocon-
ductive responsivity measurements performed on the same sample. The lower
limit of band B is not detected by this method, but it can be studied in detail
with thermal spectroscopy methods (TSC or TL) or with the combined analy-
sis of radiation-induced currents (RIC) [24] and persistent radiation-induced
currents (PIC) [25], developed by the authors and presented in Sects. 4.1
and 4.2.

1.5 Unipolar Conduction

As discussed before, it has been reported by several authors that the transport
properties in the pCVD diamond material are due mainly to one type of
carrier. This consideration, which is essential for the subsequent development
of the model, has to be treated in more detail. It has been found by the
RD42 CERN collaboration [26] that the collection efficiency of CVD diamond
detectors can be strongly incremented by removing the material from the
substrate side (linear model). This is due to the poorer quality of the CVD
diamond film near the substrate. As the removed thickness increases, the
charge collection distance, after reaching a maximum, begins to decrease,
being limited by the film thickness. As the thickness L tends to zero, the plot
of the CCD vs. L tends to approach a straight line crossing the origin.
If conduction were due to both types of carriers, the straight line would
have a form CCD = L (all the carriers reaching the contacts). On the contrary,
if only one type of carrier contributes, then CCD = L/2, i.e., only holes or
electrons reach the contacts, whilst the carriers of the other type are trapped
in the vicinity where the pair is created. In intermediate cases CCD ≈ L for
small L values, and its derivative approaches 1/2 for higher L values.
We fitted the data reported by the RD42 collaboration [26], as shown in
Fig. 2, making use of the expression for the CCD calculated by assuming that
the CCD is linearly increasing from the substrate to the growth side. The best
Modeling of the Transport Properties of Diamond Radiation Sensors 309

Fig. 2. Simulation of the CCD (d) vs. material thinning at different dn /d values.
A two-carrier model yields values very distant from the experimental points. Pure
single-carrier conduction is quite better. The best fit is given when the electrons
contribute for only 5% to the collected charge. Modified from a cited reference [26]

fit of the experimental data, as shown in Fig. 2, is obtained assuming that


one carrier contributes to conductivity for only 5%. Hence, in the following,
we will assume conductivity to be proportional to the hole concentration,
which is the choice anticipated in the previous sections.

2 A General Model for Transport Properties of pCVD


Diamond: Underlying Assumptions
Any theoretical modeling of transport properties of a semiconductor material
requires the solution of a complete set of rate equations for the populations of
both the defect levels and the conduction/valence bands. Unfortunately, the
presence of two distributions of levels in the diamond band gap, both with a
spread in energy and, presumably, capture cross section, can make it impos-
sible to find a simple, analytical solution for the rate equations of the system.
Nevertheless, a few assumptions listed below make the system analytically
solvable and permit us to relate the radiation induced conductivity (RIC) to
the structure of the diamond band gap.
1. The centers of band B are purely hole traps, as discussed in Sects. 1.4 and
1.5, and their capture cross sections for electrons are negligible.
2. Band B is decomposable in several (m) components with different capture
cross sections for holes (σi , with 1 ≤ i ≤ m) and distinct trap concentra-
tions per unit volume (Ni , 1 ≤ i ≤ m).
310 Stefano Lagomarsino and Silvio Sciortino

3. The capture cross sections for electrons (σnr ) and for holes (σpr ) take con-
stant values over the entire band A.
These three assumptions alone make it possible to solve analytically the rate
equations of diamond under irradiation.
A further assumption, the unipolar conduction approximation, whose va-
lidity is assessed by the linear model (Sect. 1.5), makes it possible to relate
directly the hole density in the VB to the conductivity of diamond. This
hypothesis is expressed as:
4. The capture cross section for electrons of the A centers is much higher
than that for holes: σnr  σpr ≡ σr .
The validity of the inequality above is based on the assumption, discussed
in Sect. 1.4, that A centers are positively charged when empty of electrons.
Moreover, assumption 4 is strongly suggested by comparison with the re-
sults reported by Pan et al. [17, 18] on conductivity of natural IIa diamond,
discussed in Sect. 1. The authors of the cited work report two orders of mag-
nitude of difference between σnr and σpr = σr for the recombination centers.
In Sect. 3 a model of RIC is developed, based on assumptions 1–4.
Moreover, the decay of the current after irradiation (persistent radiation-
induced conductivity or PIC) is also related to the presence of several com-
ponents of band B. This phenomenon is accounted for by hypotheses 1 and 2
and by the further assumptions:
5. Each component of band B has a spread in energy, and the density of
levels per unit energy di /dE is assumed to be constant in the energy
interval of interest.
6. The energy limits of each component of band B are different and range
from E1i to E2i (i = 1, . . . , m).
7. Retrapping terms are considered to be negligible with respect to recom-
bination during thermal release of carriers from band B (first-order ki-
netics [3]).
We will sometimes refer to the slow carrier release from the traps caused
by thermal energy as thermal fading. Then, the validity of assumption 5 is
based on the fact that, in a range of 1–105 s (the range of our measured
fading times) the width of the energy interval emptied by thermal fading is
only about 5 × kT log 10, i.e., 0.25 eV. It is quite reasonable to assume that
the density of levels is constant on this interval.
In the following sections, we will develop a model of PIC based on as-
sumptioins 5–7 and also relate these hypotheses to the partial depumping of
RIC after thermal fading. In this context, assumption 7 will be justified by
an a posteriori consideration (Sect. 4.1). The picture of the diamond band
gap derived from assumptions 1–7 is represented in Fig. 3, by the schematics
on the left.
Modeling of the Transport Properties of Diamond Radiation Sensors 311

Fig. 3. Schematic representation of the observed radiation-induced current be-


haviour and of the trap states model of the pumping process, from the depumped
state (left) to the pumped state (right)

3 Conductivity Under Exposure to Ionizing Radiation


We consider here a pCVD diamond detector with an externally applied volt-
age bias and assume that it is depumped, i.e., it has been reset by irradiation
with visible light of proper wavelength [13] or heated [11]. By exposing the
depumped device to a continuous source of ionizing radiation (e.g., X- or β-
radiation), we can observe a typical rise of the induced current from an initial
level to a saturation level, with a time response dependent on the dose rate.
The increase of the induced current is believed to be due to a progressive
filling of traps that are responsible for the degradation of carrier lifetimes.
Different samples not only show a different rise time or saturation level, pre-
sumably dependent on the concentration of defects, but also a quite different
shape of the rise current, probably related to the details of the defect dis-
tributions. As an example, Fig. 4 shows a comparison among the responses
of five samples of different quality, exposed to β-radiation. The figure plots
the sensitivity of the samples as a function of absorbed dose, defined as the
induced current density divided by the product of the dose rate and the elec-
tric field. This quantity is proportional to the product of the lifetime and
the mobility of the carriers, and it is directly related to the quality of the
material. The considerable difference in sensitivity and time response of the
five devices is clearly observable.
Starting from the hypotheses introduced at the beginning of Sect. 2, we
can explain the details of the conductivity increase in terms of differences in
concentration and cross section of the components of band A and B. We
will denote with Nr and σr the concentrations and the capture cross sections
for holes of the A recombination levels, and with N1 , . . . , Nm , σ1 , . . . , σm ,
the same quantities relative to the m components of band B. The terms
{q1 (t), . . . , qm (t)} and qr (t) represent the numeric concentrations of charged
centers, i.e., the concentrations of empty centers (both A and B centers are
neutral when filled with electrons and holes, respectively). The generating
factor of the betas is denoted by g. The concentration of holes and their
312 Stefano Lagomarsino and Silvio Sciortino

Fig. 4. The sensitivity of five samples as a function of absorbed β-radiation dose.


CDS92, P13 and P16 are DEBID detectors; F56 and F58 were produced in Florence
by pulsed DC glow-discharge under similar deposition conditions. P13 and P16
were cut from the same wafer. P16 as well as F56 were irradiated at a fluence of
2 × 1015 MeV equivalent n/cm2

thermal velocity are indicated by p and vp , respectively. The rate equations


for the VB and for the components of band B are the following:
m 
dp
=g−p qi (t)vp σi + (Nr − qr (t)) vp σr . (1)
dt
i=1
dqi
= −pqi (t)vp σi . (2)
dt
In pCVD diamond, even under irradiation, the free carrier concentration is
very much lower than the population of the defect centers (∼ 104 cm−3 free
carriers generated by a dose rate of 1 Gy/min against no less than 1012 cm−3
capture centers). As a consequence:
dp dqi
 . (3)
dt dt
Inequality (3) justifies the “quasi-equilibrium (QE) approximation” [1], from
which we can set dp/dt = 0 in (1). Accordingly, the neutrality condition can
be written:

m
qi (t) = qr (t) + p − n ∼
= qr (t). (4)
i=1

In the single-carrier hypothesis 4 (Sect. 2, p. 310), the hole concentration p


is proportional to the current I:
I
p= , (5)
eµSE
Modeling of the Transport Properties of Diamond Radiation Sensors 313

where µ is the hole mobility, e the elementary charge, S the metallization


area and E the electric field strength. If we denote the total charge collected
by:
 t
Q= I(t ) dt ,
0

we can solve each (2) in terms of Q, as follows:


 
vp
qi (Q) = Ni × exp − σi Q . (6)
eµSE
Substituting (4), (5) and (6) in the rate (1), and setting dp/dt = 0 (QE
approximation), we obtain for I the expression:
  −1
eµSEg m
vp
I(Q) = × Nr σr + Ni (σi − σr ) exp − σi Q , (7)
vp i=1
eµSE

with the neutrality condition derived from (4) calculated at t = 0:



m
Ni = Nr . (8)
i=1

Equation (7) is a simple, analytical expression of the instantaneous cur-


rent I in terms of the overall collected charge Q. This theoretical expression
can be fitted to the measured current I, by varying the trap parameters Ni
and σi , together with Nr and σr , which are the corresponding quantities for
the recombination center.
A qualitative interpretation of the behaviour of the induced current is
shown in Fig. 3. At the beginning of the process, electrons and holes are
trapped by centers A and B , respectively. As a stationary condition is at-
tained, some A levels remain charged, while holes are mainly trapped in
neutral A levels, thus providing charged recombination states for the gen-
erated electrons. A small amount of charged B levels, necessary to satisfy
the neutrality condition, are mantained by thermal relaxation, which is not
taken into account by our model at this stage. Analysis of (7) reveals that,
if, most likely, the charged traps have a cross section for holes greater than
that of the neutral recombination center, then the induced current increases
monotonically with the absorbed dose.
Expression (7), with a suitable choice of the number m of components of
band B, accounts for the current rise of a number of pCVD diamond samples
of different qualities, grown with different deposition methods. It also allows
the interpretation of the response degradation due to high fluences of neutron
irradiation, in terms of structural modifications of bands A and B.
As an example, in Table 1 and Fig. 5 we report the results of the analysis
of RIC curves for five samples, three (CDS92, P13 and P16) grown by DEBID,
314 Stefano Lagomarsino and Silvio Sciortino

Fig. 5. Schematic plot of the trap parameters of the samples under study, deduced
from the analysis of the radiation-induced currents

presumably by microwave plasma-enhanced CVD, two (F56 and F58) grown


by the authors at the University of Florence, by pulsed DC glow-discharge
CVD [27]. The deposition conditions of F56 and F58 were very similar. Two
of the samples (P16 and F56) were irradiated with fast neutrons at a fluence
of 2 × 1015 /cm2 (1 MeV equivalent). Samples P13 and P16 were cut from
the same wafer, the difference between them being most likely due to the
irradiation of P16.

Table 1. Values of CCD, concentration and capture cross section of the


recombination centers, obtained for the samples under study

Manufacturer Sample CCD (µm) σr (10−16 cm2 ) Nr (1015 cm−3 )


DEBID CDS92 245 5.5 2.3
P13 140 5 5
P16 851 5 1 5 1
Univ. of Florence F58 14 0.6 18
F56 192 25 43
1
Measured after neutron irradiation
2
Measured before neutron irradiation

Figure 6 shows the best fit of the RIC curve of sample P16. The measure-
ments fit very well to the theoretical expression, with a χ2 on the order of
some units. From Table 1 and Fig. 5 it is possible to recognize some interest-
ing features of pCVD diamond. As far as the commercial (DEBID) samples
are concerned:
Modeling of the Transport Properties of Diamond Radiation Sensors 315

Fig. 6. Best fit of the model to the radiation-induced current of sample P16

(a) The capture cross section of the mid-gap A centers has about the same
value for all samples, i.e., there is a substantial