MSthesis Raja July2002

GROWTH AND CHARACTERIZATION OF BaZrO 3
THIN FILMS FOR MICROWAVE COMMUNICATION

APPLICATIONS
A Thesis
Submitted for the Degree of
Master of Science
in the Faculty of Engineering
By
V. RAJASEKARAKUMAR
MATERIALS RESEARCH CENTER

INDIAN INSTITUTE OF SCIENCE
BANGALORE- 560012
INDIA
JULY 2002
Dedicated to my Parents
Mr. D. Vadapoo & Mrs. S. Selvam Lashmi

Abstract
It has been well established that ZrT iO4 thin film is a potential candidate for the
fabrication of microwave communication application devices such as oscillators,
band pass filters, etc. Relatively new material BaZrO3 has attracted researchers
with the expectation that it will yield better devices than ZrT iO4 based devices.
Hence, the present research work was carried out to grow the high quality BaZrO3
(BZ) thin films by pulsed laser ablation technique. By changing different growth
parameters and annealing conditions we were able to grow good quality thin films
with different microstructures. The crystallographic features of the films were
determined from the X-ray diffraction. An attempt has been made to understand
the basic properties such as, dielectric response, charge transport under low and
high applied electric fields.
Chapter 1 is an introduction to BaZrO3 thin films. The necessary properties

of a material to be a microwave dielectric material, the materials in the same
family, the different thin film growth techniques are dealt with in detail.
Chapter 2 describes the experimental procedure involved in the growth and

characterization of BZ thin films using pulsed laser ablation technique. Details
include the setup design for PLD growth, material synthesis for ceramic targets,
i
Abstract
deposition conditions for thin film growth and basic characterization methods
used to study the grown BZ thin films.
Chapter 3 describes the growth and structural properties of the BZ thin films
for different processing parameters. The process parameters such as substrate
temperature, deposition pressure, annealing temperature, annealing time were
correlated with structure and electrical properties of the BZ thin films. Two
kinds of films were grown, one at lower substrate temperature and subsequently
annealed (ex-situ) at higher temperatures, and the other one was grown directly
at higher substrate temperatures (in-situ). Both in-situ and the ex-situ grown
films had the tendency to enhance the perovskite phase at higher temperatures
and there were no secondary phases observed. The effect of the processing para-
meters such as annealing temperature, annealing time, deposition pressure over
the grain size and the stress along the (110) direction of the ex-situ BZ thin films
has been discussed. The cross sectional Scanning Electron Microscopy (SEM) pic-
tures revealed that both the in-situ and ex-situ grown films had the multigrain
structures.
Chapter 4 describes the interface analysis carried out by Secondary Ion Mass
spectroscopy (SIMS). It has given a complete coverage about the interface of
the BZ thin film with high resolution in the order of nanometer. A very sharp
interface has been observed in the in-situ annealed BZ thin films and there was no
diffusion of platinum electrode in to the film, whereas the inter-diffusion of film
and the platinum has been observed in ex-situ grown thin films. The segregation
of zirconium oxide has been observed in the interface of ex-situ annealed BZ
thin film and which has also dissociated on higher annealing temperatures. The
diffusion of platinum into the film has caused an increase of leakage current in the
ii
Abstract
ex-situ annealed thin films. The diffusion length of the platinum into the film was
found to be higher at higher annealing temperatures. The diffusion curve, which
follows a Gaussian nature, is not a perfect Gaussian in the case of interdiffusion
of BZ thin films as the tail of the Gaussian is dominated by pinholes.
Chapter 5 describes the ac electrical properties of BZ thin films in detail. The

dielectric constant ( ) and the dielectric losses (tanδ) were measured up to the
frequency of 100kHz at different temperatures. Both dielectric constant ( ) and
the dielectric losses (tanδ) exhibited gradual decrease with increasing tempera-
ture. At 100kHz the room temperature dielectric constant was found to be 23.5
with a dissipation factor 0.02. The dielectric response obeyed the universal law.
The dc conductivity was foundto dominate at higher temperatures leading to the
dispersion in dielectric loss in that region. The complex modulus and complex
impedance studies revealed the presence of single parallel RC equivalent circuit.
The Arrhenius plot of ac conductivity with temperature has given the activation
energy of 1.83eV at low frequency and high temperatures.
Chapter 6 describes the dc electrical properties of the BZ thin films in detail.

Films of BZ exhibited a space charge limited dc leakage current. The linearity in
the I-V plot was observed in the low voltage region. The onset voltage (VTFL)
of trapped filled limited region in the I-V curve showed an increasing and de-
creasing trend with temperature. This unusual behavior of VTFL was explained
by considering the dynamical equilibrium between the thermally generated and
injected charge carriers.
Chapter 7 gives the summary of the work and suggestions for the future work
of BZ thin films.
iii
Abstract
Acknowledgements
It is with profound gratitude that I acknowledge my research mentor, Prof. S.

B. Krupanidhi for his wonderfully fabulous contributions that had an oceanic
impact to this research work and my life. It was the divineness of this respected
master that accepted my candidature and empowered the sleeping potential in
me. In his guidance, I not only experienced grace and blessings but inspiration
too. Through his immense faith and trust on me, I was moved beyond my earlier
self and state of mind. If one could feel grace in just visualizing Mother Theresa,
I feel goodness in this person. The beautiful space of freedom that is born out
of his care for others, nurtured my individuality, increasing my confidence level
and abilities beyond believable growth rates. Numerous are the occasions where
this mentor’s actions touched and moved my heart. If Gandhi was a stand for
honesty and non-violence, this person was a stand for his students’ all-rounded
growth. On the contrary to a common phenomena experienced in any relation
that, the longer one stays, one discovers the shortcomings, every new day of the
year only increased my admiration for him. Standing inside this experience of
trust and empowerment I enjoyed, caused by this meaningful coincidence in my
life, my heart longs for ways to forward my thanks. God has simply come to me
in the form of this mentor. A gift from the heavens that my heart will never
forget for life.
It is with heart felt thankfulness that I acknowledge my department Chairman

Prof. K. Chattopadhyay for his care and his mission to serve students. It is
difficult to find words to express how this person’s courageous contribution shifted
my life. I am truly grateful to him for the precious quality of his priceless and
timely help.
iv
Abstract
I am thankful to Mr. Krishna who helped me in getting XRDs and Mr. Kurulinga,
Mr. Samphilip, Mr. Kannan and Mr. Sathya narayanan for their help in the
regard of using SEM facilities.
I profusely thank my lab seniors Dr. Bharadwaja, Dr. Sanjeeb Saha, Dr. Sudipta
Bhattacharya, Mr. Victor and Mr. Apurba Laha for their good heartedness in
making this thesis a success. I thank my other lab mates Mr. Venkateswaralu,
Dr. Thirumalvalavan, Mr. Sameer, Mr. Chayan, Mr. Tripati, Mr. Ranjith,
Mr. Sandip, Mr. Asis, Mr. Dhanajaya, Mr. Manjunatha, Mr. Sheshank,
Mr. Sivaraman, Mr. Vinayak, Mr. Srinivas and Miss. Deepika for their timely
help. My special thanks to Miss. Vanaja rajan for her kind help in all aspects.
The lab was simply a great place to be. I almost felt like home in this lab for
the home being designed in here out of kindness and team spirit and mutual
empowerment and support. The disciples of this temple, FTFD are special for
their good intension to generate knowledge and apply it to serve mankind through
knowledge sharing and knoweldge creation.
I am thankful to Mr. Sathya, Mr. Balaji, Mr. Sudhir, Mr. Kottada, Mr.
Mahendran, Mr. L. Saravanan, Mr. Jeyakumar, Mr. Sudahar for their kind
help.
I am thankful to my departmental staffs Mrs. Tharakeswari, Mrs. Indiara, Mr.

Jeyadev, Mr. Prakash, Mr. Zaheer and Mr. Raju for their timely help.
The success of my research is also sourced by the set of good friends I have.
On contary to the common phenemena where one doubts when loves us, be-
ing with my friends inspired me into believing the reverse: doubt hatred and
question indifference. The love and detailed care and the unselfishness of my
vi
Abstract
friends brings peace of my conscious mind to my subconscious mind too, al-

lowing me to be free of internal disturbances during external challenges and
problems. It is the truthfulness and and pureness and selflessness and love of
my friends Balu, Inbam, Kannadasan, Anand, Savio, Senthil, Rajagopal, Stalin,
Velan, Karthikeyan, Thirunavukkarasu, Vinodh, Kathiresan, Nagaraj, Subra-
mani, Sashisankar, Sashikumar, Hari, Kothandaraman, Senthilkumar, Dharmen-
dar, Babu, Ravi, Sudharsan, Yogesh, Sanjay, Ghaja and P. Sudha, Shivi, Tamil,
Lavanyah, Subbulakshmi, Subashini, Viji, Viji.L that seeds a unshakable desire
to build character - not only mine, but of IISc and India too, for I think that
alone can In the space of empowerment they provide, I doubt my incapablities.
It is not the equality of arms that binds us, but trust and divine love.
I wish to thank the Indian Institute of Science campus, for it’s one of the most
beautiful gifts I enjoyed. To site an example, it was here at IISc my life took a new
direction when I interacted with Dr.APJ Abdul Kalam during 2 day workshop
on ’Bridging Science to Humanity’ at IISc.
I owe multiple life times for my parents. My mother is an embodimentment

of selfness all instants ever in her care and supreme love for me. From her I
understand the meaning of selfless care. And till date I have never found an
energy that is marvelous than this feeling of oneness. The fruit of her true love
is seen in her desire to bless me and pray for our world, not just because she
wishes me to live in a beautiful and harmonious world, but she is Goddess. Her
boundless prayers made all the obstacles in to pieces. Through her I understand
the real meaning of prayers.
My father is my ever loving inspiration and model for my life. His detailed care is
beyond my comprehension. But for this powerful man, I would not be. The way
vii
Abstract
I think, the way I act, the ideologies I have, the principles I follow, the objectives
and ambitions I desire to achieve in my life, all sparked by this powerful man,
My FATHER. He is the best friend I have ever had, the best philosopher who
enlightens the source of light where I get power and the God whom I pray. And
the credits for all those acknowledgements I have received for my selfness actions
only belong to my parents.
As one of the ways to honor my mother, I dedicate my life to work for the
betterment of mankind. And I know the world shall be different in the nearest
future from now, as I know the limitless energy I harness from this divine oneness
will cause. The unmovable faith and support given by my sisters Poovathy and
prabha and brothers Sundar and Gunam could not be expressed in simple words.
At the toughest times of difficulties and frustrations their presence and thoughts
boosted my confidence and my peace of mind. Miles of separation has been
bridged by their great thoughts. My sincere thanks and gratitude to all my
friends in the department and also from outside, from whom I got lot of helps
either directly or indirectly. I could not accommodate all their names in this
limited space.
And one of the ways of thanking the education I received at Indian soil, and the
indirect care offered by every Indian offered me as scholarship, and the peace and
respect that every Indian gave me (in contrast to the violence and discrimination)
I dedicate my life to join hands with Dr.APJ Abdul Kalam and every dedicated
Indian to have an awakened super power India in place by tomorrow!!!
I commit myself to ”Arise, Awake and stop not till even after the goal is reached”.
viii
Contents
Abstract i
1 Introduction 1
1.1 What is the driving force? . . . . . . . . . . . . . . . . . . . . . . 1
1.2 Microwave passive components . . . . . . . . . . . . . . . . . . . . 1
1.3 Material requirements for microwave dielectrics . . . . . . . . . . 2
1.4 Objectives . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 2
1.5 Dielectric resonator materials . . . . . . . . . . . . . . . . . . . . 2
1.6 Issues involved in BZ integration . . . . . . . . . . . . . . . . . . 3
1.7 Processing of BZ thin films . . . . . . . . . . . . . . . . . . . . . . 5
References 7
2 Experimental 10
2.1 Laser Setup . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 10
ix
CONTENTS
2.2 The excimer Laser source . . . . . . . . . . . . . . . . . . . . . . . 13
2.2.1 Principle . . . . . . . . . . . . . . . . . . . . . . . . . . . 15
2.2.2 Excimer discharge design . . . . . . . . . . . . . . . . . . . 15
2.2.3 Beam characteristics . . . . . . . . . . . . . . . . . . . . . 15
2.3 Target preparation . . . . . . . . . . . . . . . . . . . . . . . . . . 17
2.4 The substrate . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 20
2.5 Deposition conditions . . . . . . . . . . . . . . . . . . . . . . . . . 20
2.6 physical characterization . . . . . . . . . . . . . . . . . . . . . . . 22
2.6.1 Structural analysis . . . . . . . . . . . . . . . . . . . . . . 22
2.6.2 Composition analysis . . . . . . . . . . . . . . . . . . . . . 22
2.6.3 Thickness measurement . . . . . . . . . . . . . . . . . . . 24
2.6.4 Micro structure and surface morphology . . . . . . . . . . 25
2.7 Interface Analysis . . . . . . . . . . . . . . . . . . . . . . . . . . . 26
2.8 Electrical Characterization . . . . . . . . . . . . . . . . . . . . . . 26
2.8.1 Dielectric Properties . . . . . . . . . . . . . . . . . . . . . 27
References 27
3 Growth and Structural Characterization 29
3.1 Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 29
x
CONTENTS
3.2 Crystallographic Structural Characterization . . . . . . . . . . . . 30
3.2.1 In-situ crystallization . . . . . . . . . . . . . . . . . . . . . 30
3.2.2 Ex-situ crystallization . . . . . . . . . . . . . . . . . . . . 30
3.2.3 Effect on Grain Size . . . . . . . . . . . . . . . . . . . . . 35
3.2.4 Effect on stress . . . . . . . . . . . . . . . . . . . . . . . . 37
3.3 Microstructural Analysis . . . . . . . . . . . . . . . . . . . . . . . 39
3.3.1 In-situ crystallization . . . . . . . . . . . . . . . . . . . . . 39
3.3.2 Ex-situ crystallization . . . . . . . . . . . . . . . . . . . . 39
3.4 Compositional Analysis . . . . . . . . . . . . . . . . . . . . . . . . 42
3.5 Conclusions . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 43
References 43
4 Secondary Ion Mass Spectrometry (SIMS) Analysis 45
4.1 Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 45
4.2 Elements of SIMS . . . . . . . . . . . . . . . . . . . . . . . . . . 47
4.3 Capabilities . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 47
4.4 Forms of practical SIMS . . . . . . . . . . . . . . . . . . . . . . . 49
4.4.1 Static SIMS (S-SIMS) . . . . . . . . . . . . . . . . . . . . 49
4.4.2 Dynamic SIMS (D-SIMS) . . . . . . . . . . . . . . . . . . 49
xi
CONTENTS
4.4.3 Bulk contamination/ composition studies . . . . . . . . . . 50
4.5 Sputtering . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 51
4.5.1 General background . . . . . . . . . . . . . . . . . . . . . 51
4.5.2 Total yield systematics and linear cascade predictions . . . 51
4.5.3 Multicomponent materials . . . . . . . . . . . . . . . . . . 52
4.6 Basic characteristics of SIMS . . . . . . . . . . . . . . . . . . . . . 54
4.6.1 Sensitivity and quantification . . . . . . . . . . . . . . . . 54
4.6.2 Mass interferences . . . . . . . . . . . . . . . . . . . . . . 56
4.6.3 Pre-equilibrium effects . . . . . . . . . . . . . . . . . . . . 58
4.6.4 Detection/resolution limits and ion bombardment induced

mixing . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 58
4.6.5 Charging Problem . . . . . . . . . . . . . . . . . . . . . . 60
4.6.6 Miscellaneous . . . . . . . . . . . . . . . . . . . . . . . . . 62
4.7 Quantification of depth profiles . . . . . . . . . . . . . . . . . . . 64
4.7.1 General remarks . . . . . . . . . . . . . . . . . . . . . . . 64
4.7.2 Time-to-depth conversion . . . . . . . . . . . . . . . . . . 64
4.8 Results and Discussions . . . . . . . . . . . . . . . . . . . . . . . 65
4.8.1 Effect of in-situ annealing and ex-situ annealing . . . . . . 67
4.8.2 Effect of ex-situ annealing temperature . . . . . . . . . . . 70
xii
CONTENTS
4.8.3 Effect of Oxygen pressure . . . . . . . . . . . . . . . . . . 74
4.8.4 Interdiffusion of platinum . . . . . . . . . . . . . . . . . . 77
4.9 Summary . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 79
References 80
5 AC Electrical Properties 81
5.1 Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 81
5.2 Theory involved . . . . . . . . . . . . . . . . . . . . . . . . . . . . 82
5.2.1 Different types of polarization relaxations . . . . . . . . . . 82
5.2.2 Complex electrical characterization . . . . . . . . . . . . . 89
5.2.3 AC conduction studies . . . . . . . . . . . . . . . . . . . . 90
5.3 Dielectric response . . . . . . . . . . . . . . . . . . . . . . . . . . 91
5.3.1 Dielectric impedance spectroscopy . . . . . . . . . . . . . . 98
5.3.2 AC Conductivity . . . . . . . . . . . . . . . . . . . . . . . 102
5.3.3 Summary . . . . . . . . . . . . . . . . . . . . . . . . . . . 106
References 107
6 DC Electrical Properties 110
6.1 Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 110
xiii
CONTENTS
6.2 High Field Phenomenon . . . . . . . . . . . . . . . . . . . . . . . 110
6.2.1 Schottky conduction process . . . . . . . . . . . . . . . . . 110
6.2.2 Poole-Frenkel conduction process . . . . . . . . . . . . . . 113
6.2.3 Tunnel Effect . . . . . . . . . . . . . . . . . . . . . . . . . 113
6.2.4 Space charge limited conduction process . . . . . . . . . . 114
6.3 Analysis of experimental results . . . . . . . . . . . . . . . . . . . 118
6.3.1 comparison with the Schottky conduction mechanism . . . 118
6.3.2 Comparison with the Space charge controlled conduction

mechanism . . . . . . . . . . . . . . . . . . . . . . . . . . . 119
6.3.3 Conclusions . . . . . . . . . . . . . . . . . . . . . . . . . . 125
References 125
7 Summary and Future Work 128
7.1 Summary . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 128
7.2 Future work . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 130
xiv
List of Figures
2.1 Schematic diagram of the Pulsed laser ablation Process. . . . . . . 11
2.2 The excimer laser transition inside a KrF laser. . . . . . . . . . . 13
2.3 Schematic diagram of a excimer laser discharge circuit design. . . 14
2.4 A typical beam profile from a KrF excimer laser source (A) 3D
beam Profile (B) Horizontal cross Section (C) Vertical cross section
[2]. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 16
2.5 Flowchart for target preparation. . . . . . . . . . . . . . . . . . . 19
2.6 Schematic diagram showing the principle of EDAX measurement. 23
2.7 Schematic diagram of the Filmetrics thickness measurement system. 24
3.1 X-ray diffraction pattern of in-situ crystallized BZ thin films grown

with an energy fluence 3J/cm2 , at 50 mT orr oxygen pressure and
at different substrate temperatures 550◦ C, 600◦ C, 650◦ C along with
the powder data. . . . . . . . . . . . . . . . . . . . . . . . . . . . 31
xv
LIST OF FIGURES
3.2 Effect of annealing temperature on the crystallization of ex-situ

BZ thin films. The films were deposited at 400◦ C with an oxygen
partial pressure of 20mT orr and post annealed for 90 minutes. . . 32
3.3 Effect of annealing time on the crystallization of ex-situ BZ thin

films. The films were deposited at 400◦ C with an oxygen partial
pressure of 50 mT orr and post annealed at 775◦ C. . . . . . . . . 33
3.4 Effect of oxygen partial pressure during deposition on the crystal-

lization of annealed BZ thin films. The films were deposited at
400◦ C and were post annealed at 775◦ C for 60 minutes. . . . . . . 34
3.5 Effect of processing parameters on grain size of BZ thin films. The

films were deposited at 400◦ C. a) Effect of annealing temperature
b) Effect of annealing time c) Effect of deposition pressure. . . . . 36
3.6 Effect of processing parameters on stress of BZ thin films. The

films were deposited at 400◦ C. a) Effect of annealing time b)
Effect of annealing temperature c) Effect of deposition pressure. . 38
3.7 SEM photographs of in-situ BZ thin films. a) cross sectional view.

b) surface morphology. . . . . . . . . . . . . . . . . . . . . . . . . 40
3.8 SEM photographs of ex-situ BZ thin films. a) cross sectional view.

b) surface morphology. . . . . . . . . . . . . . . . . . . . . . . . . 41
3.9 Spatial variation of composition of BZ thin films grown at 650◦ C

with an oxygen partial pressure of 50mT orr at the fluence of 3J/cm2 . 42
4.1 schematic diagram of SIMS . . . . . . . . . . . . . . . . . . . . . 48
xvi
LIST OF FIGURES
4.2 As-measured signal intensity V s elapsed errosion time of a BZ thin

film. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 65
4.3 The crater depth for the BZ thin film which was measured using
the Sloan 3030 surface profilometer . . . . . . . . . . . . . . . . . 66
4.4 Depth profile of BZ film deposited at 50mT orr oxygen pressure

and in-situ annealed at 650◦ C. . . . . . . . . . . . . . . . . . . . . 67

with substrate temperature 400◦ C and ex-situ annealed at 650◦ C
for 90 minutes. . . . . . . . . . . . . . . . . . . . . . . . . . . . . 68

with the substrate temperature 400◦ C and ex-situ annealed at
600◦ C for 90 minutes. . . . . . . . . . . . . . . . . . . . . . . . . . 70

for 90 minutes. . . . . . . . . . . . . . . . . . . . . . . . . . . . . 71

for 90 minutes. . . . . . . . . . . . . . . . . . . . . . . . . . . . . 72
4.9 Depth profile of the BZ film deposited at 20 mT orr. . . . . . . . . 74
4.10 Depth profile of the film deposited at 50 mT orr. . . . . . . . . . . 75
4.11 Depth profile of the film deposited at 100 mT orr. . . . . . . . . . 76
xvii
LIST OF FIGURES
5.1 The theoretical frequency dispersion curve of a typical ‘Debye’

type dielectric. Both the dielectric constant and the dielectric loss
factor are denoted. . . . . . . . . . . . . . . . . . . . . . . . . . . 84
5.2 The theoretical frequency dispersion for ‘Maxwell-Wagner’ polar-

ization. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 86
5.3 Theoretical frequency dispersion of ‘χreal ’ and ‘χimaginary ’ accord-

ing to ‘Jonscher’s law’. . . . . . . . . . . . . . . . . . . . . . . . . 88
5.4 Plot of the real part of dielectric constant as a function of frequency

at various temperatures. . . . . . . . . . . . . . . . . . . . . . . . 91
5.5 Plot of dielectric loss ( ) as a function of frequency at various

temperatures. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 92
5.6 Plot of the real part of dielectric constant as a function of temper-

ature at various frequencies. . . . . . . . . . . . . . . . . . . . . . 93
5.7 Dissipation factor as a function of frequency in BZ thin films. . . 94
5.8 T anδ vs.temperature in BZ thin films. . . . . . . . . . . . . . . . 95
5.9 Plot of n(T) as a function of temperature calculated from the the-

oretical fits of the experimental data. . . . . . . . . . . . . . . . . 96
5.10 Plot of a(T) as a function of temperature calculated from the the-

oretical fits of the experimental data. . . . . . . . . . . . . . . . . 97
5.11 The imaginary part of the modulus Z plotted as a function of

frequency for different temperatures. . . . . . . . . . . . . . . . . 99
5.12 Complex impedance plane plot of BZ thin films. . . . . . . . . . . 100
xviii
LIST OF FIGURES
5.13 The imaginary part of the modulus M plotted as a function of

frequency for different temperatures. . . . . . . . . . . . . . . . . 101
5.14 AC conductivity as a function of frequency for BZ thin films. . . . 103
1000
5.15 AC conductivity vs. T
in BZ thin films. . . . . . . . . . . . . . 104
1000
5.16 AC conductivity vs. T
with the calculation of activation energy
in BZ thin films. . . . . . . . . . . . . . . . . . . . . . . . . . . . 105
6.1 The ln(J/T 2 ) vs. E 1/2 plot for room temperature. . . . . . . . . . 119
1
6.2 The ln(J) ∼ E 2 plot at different temperatures. . . . . . . . . . . 120
6.3 The I ∼ V curves of a BZ thin films at different temperatures. . . 121
6.4 The Lampert triangle in the J-V plot at room temperature. The
slopes of the three arms of the triangle are indicated. . . . . . . . 122
6.5 The Arhenious plot of the high field conductivity of the BZ thin
films. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 123
6.6 The variation of VT F L with temperatures. . . . . . . . . . . . . . . 124
xix
List of Tables
2.1 List of Deposition conditions. . . . . . . . . . . . . . . . . . . . . 21
xx
Chapter 1
Introduction
1.1 What is the driving force?
Number of subscribers and usage of mobile communication in day today life

is increasing in an exponential way. This motivated researchers towards the
microwave dielectric materials.
1.2 Microwave passive components
♦ Dielectric resonators
♦ Phase shifters
♦ Phased array antennas
♦ Bandpass filters
♦ Transmission lines
♦ Coplanar waveguides [1]
1
CHAPTER 1. INTRODUCTION
1.3 Material requirements for microwave dielectrics
♣ High dielectric constant ( r )

♣ Low loss tangent/ High quality factor
Q = (tanδ)−1
♣ Very low temperature coeff. of resonance
T Cω = −( 12 T C + αL )
High r =⇒ Miniaturization
Low loss and Stability (f,TC) =⇒ Improved performance [1, 2]
1.4 Objectives
♦ Identify extrinsic loss mechanisms of thin films as a function of frequency, tem-

perature, and processing conditions.
♦ Fabricate low-loss frequency-agile paraelectric for microwave wireless communi-
cation devices by controlling the composition, defect structure, and metalization.
♦ Quantitative PLD process characterization and optimization for high quality
thin film production.
1.5 Dielectric resonator materials
A number of material have been developed as microwave dielectrics in the past

decade [3]- [7]. In general, the materials utilized for these devices are paraelectric,
so that the microwave dielectric properties are determined by the combination of
ionic and electronic polarization in materials. Among them the contribution of
2
1.6. ISSUES INVOLVED IN BZ INTEGRATION
electronic polarization can be ignored compared with ionic polarization, because

tanδ caused by electronic polarization is extremely low in the microwave range. In
the 1960’s infrared dielectric dispersion was vigorously investigated for perovskite
families [8, 9] . These investigations have made it clear that dielectric losses at
microwave frequencies can be estimated by the dispersion parameters obtained
from the analysis based on the classical dispersion theory. As dielectric losses in
ceramics are subjected to the influence of slight differences in crystal structures[5]
and impurities [6], it is important to investigate the inherent tanδ in ceramics
from dispersion theory. Some of the dielectric resonator materials are follows:
Ba(Zn1/3 T a2/3 )O3
(Zr, Sn)T iO4
Ba(Zn, T a)O3 − BaZrO3
Ba(Zn1/3 N b2/3 )O3 [2]
However, the dielectric behavior of BaZrO3 is not yet revealed extensively, though
its a good mircrowave dielectric material.
1.6 Issues involved in BZ integration
BZ capacitor is used in metal-insulator-metal configuration where the storage

poly-silicon electrode is replaced by metal electrode. Although the BZ capacitor
can provide sufficient cell capacitance for the microwave devices, many issues
regarding the material still remain to be addressed. The key issues of BZ capacitor
are barrier height between metal/electrode and BZ dielectric, thickness dependent
dielectric constant, crystallization temperature after BZ thin film deposition, the
barrier layer between storage electrode, interfacial effects and poly-Si plug and
3
its resistance to oxidation during crystallization and electrode formation.
Even though the material has been identified as microwave material [2], there
is no much work on BZ thin films upto now. The dc leakage current study is
extremely important for the microwave dielectric thin films as they degrade the
device with higher leakage current. So, one should know the origin for the high
leakage current and how to minimize this effect to get a very good device. The
leakage current behavior of BZ thin films has been attributed by space-charge
limited conduction in our case.
The dielectric constant of the dielectric materials is known to be dependent on

the thickness of the dielectric films [10]. As the dielectric film thickness decreases,
the dielectric constant decreases as given below.
0 rA
C= (1.1)
d
This can be explained by the lower dielectric constant of the film/electrode inter-
face depletion layer which comes into effect at very low thickness. The deposited
oxide dielectric layer requires a high temperature annealing in oxygen environ-
ment in order to achieve good crystallinity. Crystalline dielectric films were found
to have a higher dielectric constant and lower leakage current density [11]. During
high temperature annealing in oxygen ambient, considerable amount of oxygen
penetrates the storage Pt electrode, resulting in oxidizing the poly-Si at the in-
terface between plugged poly Si and dielectric thin film. So, the barrier layer to
block the oxygen penetration is needed between Pt electrode and plugged Poly-Si.
The barrier layers should have resistance to oxygen penetration at high anneal-
ing temperatures. TiN/Ti commonly used in current metalization scheme, which
is not proper because it loss it’s barrier property around 500◦ C. The electrode
4
1.7. PROCESSING OF BZ THIN FILMS
formation is also a key issue in the fabrication process since it determines the
surface area of capacitor. A vertical etching profile of the storage node offers
a larger area of capacitances [11]. Presently, the Pt electrode is found to have
superior leakage characteristics as well as the highest capacitance [12]- [14]. But
Pt being a very difficult material to etch. The other proposed electrode materi-
als are Ru, Ir, RuO2 , IrO2 , BaRuO3 , SrRuO3 , Y Ba2 Cu3 O7 , (La, Sr)CoO3 . How-
ever, these electrodes based some oxide thin films capacitors suffers from higher
leakage current and lower dielectric constant [15, 12]. So, one should fully un-
derstood the above mentioned issues before mass production of BZ thin film
dielectrics.
1.7 Processing of BZ thin films
The main objectives to obtain a film with

1. Large uniform surface area
2. High purity
3. Good stoichiometry
4. High density
5. Good adhesion
6. Good electrical properties with processing at low temperatures and in the high
rate.
The thin films deposition techniques are classified as follows: Physical vapor de-
position (PVD), Chemical vapor deposition (CVD) and chemical solution deposi-
tion. RF- magnetron sputtering, ion-beam sputtering, Plasma enhanced RF sput-
tering, multi ion beam reactive sputtering, Electron cyclotron Resonance (ECR)
5
plasma enhanced RF sputtering,Pulsed excimer laser deposition (PLD) and mole-

cular beam epitaxy (MBE) are classified as PVD. Where, metal organic chemi-
cal vapor deposition (MOCVD), low pressure MOCVD, ECR-MOCVD,CVD are
classified as CVD. metal organic decomposition, Sol-gel are classsified as solution
deposition techniques [18, 19].
Each techniques has its own merits and drawbacks. RF magnetron sputtering has
its draw back in having stringent conditions for maintaining stoichiometry in the
deposited films. But large area coatings and commercial scale of productions are
its advantages. CVD, MOCVD, CSD the chemical depositions offers a large area
of uniform depositions, but it requires high temperature processing. Pulsed laser
ablation offers good stoichiometry films with lower processing temperature but
the draw back is small area deposition for a stationary substrate. For the appli-
cation of microwave communication, the dielectric material must have a very low
leakage current to maintain favorable retention characteristics, and in the case of
topography for three-dimensional device cells have the ability for excellent step
coverage. Rf-sputtering deposition has the advantage to deposit low temperature
processing, where the thermal effect is the main constrain. However, the as de-
posited films are mostly in the amorphous phase, and high temperature annealing
process is necessary to get crystallinity. In comparison to other techniques, PLD
offers a better stand in terms of BZ thin film quality and easy to grow. List of
advantages of PLD in BZ thin film processes are
1. Very good control over the composition stoichiometry of the film.
2. Maintaining a wide range of substrate temperature is possible.
3. A very good range of operating pressure is possible (10−5 to 10−1 Torr).
4. Large area of uniformity can obtain by using a movable target geometry.
5. The deposition process is so clean due to the very small distance between the
6
1.7. PROCESSING OF BZ THIN FILMS
target and the substrate.

6. We can have very good control over the deposition rate.
Due to the above advantages PLD was opted for the deposition of BZ thin films in
this work. Regarding the effect of processing parameters on the crystallinity and
structural characteristics as well as electrical properties and interfacial properties
have been studied in this work.
7
References
[1] Kikuo Warkino, Toshio Nishikawa, Youhei Ishikawa and Hiroshi Tamura,
Br.ceram. Trans. J., 89, 39 (1990).
[2] Koichi Fukuda and Ryozo Kitoh, J. Am. Ceram. Soc., 77[1], 149 (1994).
[3] H. M. O’Bryan, Jr., J. Thomson, Jr., and J.K. Plourde, J. Am. Ceram.
Soc., 57[10], 450 (1974).
[4] S. Nomura, K. Toyama, and K. Kaneta, Jpn. J. Appl. Phys., 21[10], L624
(1982).
[5] S.Kawashima, M. Nishida, I. Ueda, and H. Ouchi, J. Am. Ceram. Soc.,

66[6], 421 (1983).
[6] K. Wakino, K. Minai, and H. Tamura, J. Am. Ceram. Soc., 67[4], 278
(1984).
[7] S. B. Desu and H. M. O’Bryan, J. Am. Ceram. Soc., 68[10], 546 (1985).
[8] W. G. Spitzer, R. C. Miller, D. A. Kleiman, and L. E. Howorth, Phy. Rev.,

126[5], 1710 (1962).
8
REFERENCES
[9] C. H. Perry, D. J. McCarthy, and G. Rupprecht, Phys. Rev., 138[5A],

A1537 (1965).
[10] T. Kuroiwa, Y. Tsuenemu, T. Horikawa, T. Makita, J. Tanimura, N.

Mikami, and K. Sato, Jpn. J. Appl. Phys. 33, 5187(1994).
[11] T. Horikawa, N. Mikami, T. Makita, J. Tanimura, M. Katoaka, K. Sato,

and M. Nuroshita, Jpn. J. Appl. Phys., 32, 4126(1993).
[12] C. S. Hwang, et.al., J. Appl. Phys. 83, 3703 (1998).
[13] J. F. Scott. Annu. Rev. Mater. Sci. 328, 79 (1998).
[14] J. F. Scott, M. Azuma, C. A. Araujo, L. D. McMillan, M. C. Scott, and T.

Roberts, Integrated Ferroelectrics 4, 61(1994).
[15] S. Yamamichi, P-Y. Lesaicherre, H. Yuamaguchi, K. Takemura, S. Son, H.

Yabuta, K. Sato, T. Tamura et al., IEDM Tech, Dig., 119 (1995).
[16] K. Abe, N. Yanase, S. Komatsu, K. Sano, N. Fukushimo, and T. Kawakubo,

IEICE Trans. Electron. E81-C, 505(1998).
[17] C. S. Hwang, B. T. Lee, C. S. Kang, J. W. Kim, K. H. Lee, H-J. Cho, H.

Horii, W. D. Kim, S. I. Lee, Y. B. Roh and M. Y. Lee, J. Appl. Phys. 83,
3703(1998).
[18] W. J. Lee, I. K. Park, G. E. Jiang. and H.G. Kim, Jpn. J. Appl. Phys. 34,
196 (1995).
[19] T. Horikawa, J. Tanimura, T. Kawahara, M. Yamamuka, M. Tarutani, and

K.Ono, IEICE Trans. Electron. E81-C4, 497(1998).
9
Chapter 2
Experimental
2.1 Laser Setup
Pulsed laser ablation is one of the most important Physical vapor deposition
techniques for the fabrication of multi component oxide thin films. A schematic
diagram of the laser ablation setup is shown in Fig.2.1. A KrF Pulsed laser
(Lambda Physik Model Compex 201) was used for the deposition Process. The
laser used was 248nm with a pulsed width of 20 nano seconds, which could produce
a maximum energy output of 600 mJ. The laser could be operated in the frequency
range of 1-10 Hz. The laser beam was collimated using a slit to use the uniform
region of the beam and condensed using a quartz Plano-convex lens of 50 cm focal
length. The lens was fixed on a horizontal movable mount, so that the beam could
be desirably focused to achieve the required energy density. The beam energy
density (fluence) at the target was calculated using the following relation:
10
2.1. LASER SETUP
Stepper motor
drive
Quartz
vacuum port
UV Grade lens
KrF
Excimer
Laser
27kV
10Hz
248 nm
600mJ
Thermocouple Rotating target
connected to
temperature
controller
Substrate holder and

heater assembly
Deposition Chamber
Figure 2.1: Schematic diagram of the Pulsed laser ablation Process.
11
CHAPTER 2. EXPERIMENTAL
Ef romlaser f 2
Fontarget = 2
·( ) (2.1)
a f −d
Here, ‘f ’ is the focal length of the lens, ‘d’ is the lens to target distance and ‘a’ is
the area of cross section of the laser beam coming from the source.We can get an
accurate value of the energy density or fluence (J/cm2 )using the Eqn. 2.1. The
laser was allowed inside the chamber through a vacuum port. The chamber was
evacuated using a diffusion pump and rotary pump combination. The backing line
connecting the rotary and the diffusion pump was measured using a convectron
gauge (Granville Phillips). The pressure inside the chamber also measured using
the same type of gauge to measure the range from atmospheric to 1 × 10−4 Torr
and an ionization gauge (Granville Phillips)was used for the range of 1 × 10−4
to 1 × 10−6 Torr. All the gauges were connected to the single readout (Granville
Phillips Model 307), which automatically switched on the ionization gauge as
soon as the vacuum level crossed a value 1 × 10−3 Torr. All the vacuum gauges
were calibrated according to the product manufacturer’s manual for the accurate
measurement of the vacuum. The ion gauge was degassed from time to time to
eliminate contamination and adsorbed gases. Prior to each deposition process
a base pressure of 1 × 10−6 Torr was satisfactorily achieved and then flushed
continuously with high pure oxygen (99.999 %) to a pressure of 1 × 10−3 Torr.
This process removed the unwanted residual gas to a certain instant.
12
2.2. THE EXCIMER LASER SOURCE
Figure 2.2: The excimer laser transition inside a KrF laser.
2.2 The excimer Laser source
We have used a commercially available laser source manufactured by lambda Physik

(model COMPEX 201). The operating principle and the internal design are de-
scribed in this section.
13
Figure 2.3: Schematic diagram of a excimer laser discharge circuit design.
14
2.2. THE EXCIMER LASER SOURCE
2.2.1 Principle
The output from an excimer laser is derived from a molecular gain medium. The
lasing action takes place between a upper electronic state and a repulsive ground
electronic state. Due to the repulsive ground state, the excimer molecule can
dissociate rapidly on the order of a vibrational period 10−13 s [1], as it emits a
photon during transition from upper state to the ground state. The life time in the
upper bound state was more than the life time in the lower bound state, which
led to the population inversion and therefore high gain are so easily achieved.
Fig.2.2 shows a typical molecular potential energy diagram of an excimer system.
2.2.2 Excimer discharge design
The schematic of an electric discharge design is shown in Fig.2.3. The minimum

requirement for the discharge is to deliver a peak power of 108 - 109 W to the
discharge region. Typically, the following events occur. The storage capacitors
are charged to at most 40kV . The thyratron switch is fired and the energy is then
transferred to the peaking capacitors over a time of approximately 100ns. When
the peaking capacitors become sufficiently charged, the energy is transferred to
the discharge region with a time duration of 20- 50ns [1].
2.2.3 Beam characteristics
A homogeneous uniform laser output is required for good-quality deposition

process. This is very much important while depositing multi-component thin
films. Poor beam quality can result in non stoichiometric and also the formation
15
Figure 2.4: A typical beam profile from a KrF excimer laser source (A) 3D beam
Profile (B) Horizontal cross Section (C) Vertical cross section [2].
16
2.3. TARGET PREPARATION
of undesirable droplet.
To obtain a high quality uniform laser output, the discharge laser gas is ionized
uniformly throughout the chamber. To ensure the homogeneous ionization the
laser gas is pre-ionized before the actual discharge. The pre-ionization is achieved
by the UV light, which is generated from a spark gaps (pre-ionization pins) that
run along the length of the electrodes. Because of the UV light is strongly
absorbed by the laser gas, the penetration depth of the UV photons is limited
and this put a limitation of the effectiveness of the pre-ionization.
A typical beam profile from a fluorine optimized electrode has been shown in
fig.2.4. It could be seen that the beam was homogeneous in the central region of
the cross section. The overall profile was close to a Gaussian profile. The energy
density was higher in the central part and decayed towards the edges. Since there
was a threshold energy required for ablation, sometimes a rectangular slit was
used in front of the laser window to allow only the central part of the beam [1].
2.3 Target preparation
Highly dense pellets of (BaZrO3 ) were prepared by conventional ceramic process-

ing. A flow chart depicting the fabrication of the pellets is given in fig.2.5. Start-
ing powder of BaCO3 , and ZrO2 (99.99 % purity Aldrich Chemicals)were used
for the solid state reaction. The solid state reaction is given by Eq.(2.2).
BaCO3 + ZrO2 −→ BaZrO3 + CO2 (2.2)
Initially the powders were packed with acetone in an agate jar and ball milled
17
for 3 12 hours(hrs). The drying was carried out in an electrically heated drying
oven for 12 hrs at 75◦ C. The dried powders were mixed well in a mortar and
pestle and placed in a alumina crucible. Calcination was done at 1150◦ C for 10
hrs. at a heating rate of 3◦ C/min. The cooling rate was the same as heating
rate. The calcined powder was again ball milled and dried as the earlier process.
Polyvinyl alcohol (PVA)was used as a binder and was added 5% by weight to
the powder. The powder was then pressed into pellets in a hydraulic press using
a 20 mm die. The load used was 80 Kilo Newton. The pressed pellets were
placed on a platinum foil in furnace for the sintering process. The green pellets
were kept at 400◦ C for binder removal and then ramped at a rate of 2◦ C/min
to 1550◦ C and sintered for 2hrs. Then cooling was taken place at the same
ramp rate up to the 50◦ C. Then the top and bottom surfaces of the pellet were
ground cleaned and polished to ensure proper surface finishing. Polishing the
surface was necessary to enhance the ablation properties, which depends on the
surface roughness. The crystallographic structure of the pellets were determined
from X-ray diffraction pattern. The composition of the target were obtained by
using energy dispersive spectroscopy method in a scanning microscope and the
stoichiometry was confirmed.
18
2.3. TARGET PREPARATION
BaCO 3
Drying
Ball Mill
ZrO2
Ball Mill Calcination Mixing
Binder
Drying Addition Air Dry
Sintering Binder
Removal Pressing
Characterization
Surface BZO
Grinding Target
Figure 2.5: Flowchart for target preparation.
19
2.4 The substrate
The substrates used for the deposition were commercially available platinum
coated silicon wafer.The actual configuration included a Ti layer above the SiO2
and Si to act as a buffer layer for the platinum. The platinum layer was 150nm
thick and the final configuration was P t/T iO2 /SiO2 /Si.
Since substrate wafers were subjected to physical handling during the process of
cutting, lapping,polishing and packaging, a large amount of molecular contami-
nation was present in the wafers. The list of such contaminants were airborne
bacteria, grease and wax from cutting tools and from physical handling, abrasive
particulate as well as a variety of plasticizers which come from the containers and
wrapping in which wafers are shipped. Removal of these contaminants was our
primary aim for the substrate cleaning [4].
The substrates were first cleaned by boiling in de-ionized water to remove any
residual ions and then boiled in trichloroethylene (TCE) to remove surface oil
contamination. The solvent TCE was removed by boiling in acetone and the
substrate was again washed in de-ionized water. The substrate were then dipped
in boiling isopropanol(IPA) and finally dried under dry gas blown through a
nozzle.
2.5 Deposition conditions
The target was mounted on a stainless steel holder and was kept at an angle of 45◦
with respect to the laser beam. The target was glued to a copper packing plate
with silver paste. The copper plate acted as a sink for the generated heat during
20
2.5. DEPOSITION CONDITIONS
the laser ablation. The target was rotated at a frequency other than the laser was
operated, to avoid the ablation from the same part of the target. The rotational
motion of the target was controlled by an external DC variable power drive. The
operating pressure was 20-100 mT orr and the environment was ultra high purity
oxygen. The base pressure of the chamber was 10−5 Torr. The substrate was kept
on a stainless steel substrate holder which had two cartridge heaters inserted in to
it and that were heated up electrically. An external ac power source was used for
the heater and it was controlled by a TOHO digital temperature controller. The
deposition was done for 20-40 min. The complete list of the deposition conditions
is given in Table 2.1.
Table 2.1: List of Deposition conditions.
Deposition Conditions
Base pressure : 1 × 10−5 Torr
Deposition pressure : 20 − 100mT orr
Fluence : 3-4 J/cm2
Target to substrate distance : 30mm
Deposition temperature : 25 - 650◦ C
21
2.6 physical characterization
2.6.1 Structural analysis
The crystallographic structure of the films were determined from X-ray diffrac-
tion(XRD) patterns by using Phillips system, which employed CuKα radiation.
The patterns were compared with the standard patterns. The grain size of the
films were determined from the Scherrer formula given by
Csize = (k × λ)/(B × cosθ) (2.3)
where k is a constant (0.94 for scherrer), λ is the wavelength of X-ray being used,
B is the FWHM (Full width half maximum) of the peak. The determined grain
sizes were compared for films grown under various processing conditions.
2.6.2 Composition analysis
The composition of the films were determined by the energy dispersive X-ray
analysis (EDAX, Oxford Instruments) coupled with the SEM machine. The tech-
nique uses in EDAX is resolving the emitted X-ray from the samples in terms of
energy. The schematic of an EDAX system is given in Fig.2.6. The incident elec-
tron beam on the sample generates X-rays due to atom-field interaction between
the high energy electron beam and the sample.The current which flows between
the electrodes, when an X-ray enters the detector lasts for an extremely short time
(less than 1µs) and is normally referred to as a pulse. Each pulse is amplified
and then passed to a multi channel analyzer(MCA). The MCA thus effectively
22
2.6. PHYSICAL CHARACTERIZATION
Incident electron
beam
Cathodoluminescence
(Visible light) Auger
electron
Characteristic
x-ray Secondary
electrons
Heat
Backscattered
electrons
Specimen Inelastically
current Elastically
scattered scattered
Transmitted
electrons electrons electrons
Detector Electronic
components MCA
Charge
Pulse
Digital Energy
X-ray signal
Electron
column
Sample
Figure 2.6: Schematic diagram showing the principle of EDAX measurement.
collects a histogram of the energies of all the X-rays arriving at the detector. The
beam current, accelerating voltage, geometry of the system and concentration of
the constituent elements are having the influence on the intensity of the X-ray
signal. The energy of the characteristic X-ray is given by Mosley’s law
E ≡ C1 (Z − C2 ) (2.4)
Where Z is the atomic number, C1 and C2 are constants. From the energy
location of the peaks in the spectrum, software routines sort out the elements
present at the particular point of the sample by comparison with the tabulated
characteristic energy values. To avoid charge buildup, the sample was prepared
23
by coating a thin conducting layer of gold by sputtering. The Ba/Zr ratios were
used as standards and the film composition was normalized with respect to the
ratio.
2.6.3 Thickness measurement
Spectrometer/ Light Source Unit

To computer
Light source Spectrometer parallel port
output input
Fibre optic
coaxial cable
Spring loaded Stage arm

set screw
Sample
(face up)
Figure 2.7: Schematic diagram of the Filmetrics thickness measurement system.
For thickness measurement, we used a FILMETRICS F20. This system worked

on the basis of interferometric principle. The sample was irradiated by a poly-
chromatic light, and the reflectance of the sample for various wavelengths were
analyzed by a spectro photometer built inside the system. The reflectivity of
24
2.6. PHYSICAL CHARACTERIZATION
the sample was dependent on two inputs, the substrate and the sample refrac-
tive index at any given wavelength. Refractive indices for other wavelengths was
calculated by the instrument (the software) by using the Cauchy’s wavelength
dispersion relation, which was very well valid for all solids [3]. Schematic dia-
gram of the measurement setup is shown in Fig.2.7. An alternative and accurate
way of measurement was done by imaging the film cross-section in a scanning
electron microscope. The cursors available on the screen were positioned visually
at the film surface and the film substrate interface. The distance between the
cursors generated the film thickness accurately within an error of few nanome-
ters. The thickness has been measured accurately using SIMS (Secondary ion
mass spectroscopy) profile also.
2.6.4 Micro structure and surface morphology
Scanning electron microscopy (SEM, Oxford Instruments) were used to determine

the microstructure of the films. Fine beam of electrons is scanned across the
specimen by the scan coils, while a detector counts the number of low energy
secondary electrons, or other radiation, coming from each point on the surface.
At the same time the spot of a cathode ray tube (CRT) is scanned across the
screen. The electron beam and the CRT spot are both scanned as a raster. The
mechanism by which the image is magnified have no lenses at all. The raster
scanned by the electron beam on the specimen is made smaller than the raster
displayed on the CRT. A thin layer of (∼ 100Å) gold was deposited by sputtering
on the films to avoid charge build up. The top view and the cross sectional view
of the microstructures were taken.
25
2.7 Interface Analysis
Interface of the BZ films and the substrate have been studied by the Secondary
ion mass spectrometry (SIMS). This is the powerful tool for depth profiling,
impurity detection, diffusion studies, layer thickness and composition determi-
nation. The technical and application details has described elaborately in the
chapter[4].
2.8 Electrical Characterization
Circular gold electrodes were deposited on the films by using an evaporation

system. The diameter and the thickness of the electrodes were 150-200nm and
500-600 µm respectively. The two probe method was employed for the electrical
characterization of the films in AC and DC fields. The platinum substrate itself
acted as the bottom electrode and the gold electrode was employed as the top
electrode. In order to understand the influence of temperature on the electrical
properties of the films, they were mounted on a smooth surfaced stainless-steel
holder contains a set of parallel connected heating cartridges. The temperature of
the film holder was monitored and controlled with a combination of temperature
controller (Eurotherm 847) and a K-type thermocouple. All measurement instru-
ments were interfaced using GPIB card and GPIB connectors attached with the
computer. The interface was done through a software program Test point (CEC
Instruments).
26
2.8. ELECTRICAL CHARACTERIZATION
2.8.1 Dielectric Properties
Frequency domain measurements
To understand the type of dielectric relaxation phenomenon in the Barium Zir-

conate thin films, frequency dependent studies of dielectric constant and dissipa-
tion factors along with impedance analysis technique were employed for a range
of temperatures 30 to 300◦ C. Dielectric properties of paraelectric thin films were
studied using an LCZ meter (Keithley 3330) interfaced with a computer over a
frequency range of 100Hz to 100kHz. A programmable voltage source (keithley
230) was used in conjunction with the LCZ meter for capacitance- voltage mea-
surements. The combination provided dielectric measurements as a function of
frequency, applied voltage and temperature. Software programmes helped to do
the dielectric measurement with high accuracy and fast acquisition rates.
Leakage current characterization
A keithley source measure unit (model SMU 236) was used for all dc measure-
ments. The system could act as a constant voltage source and measured the
current flowing through the circuit to an accuracy of 1 × 10−14 A. During I-V
measurement the dc voltage was applied in steps of 0.1 V with a holding time
of 150 sec at each step to ensure the equilibrium of leakage current at each volt-
age increment. The breakdown was complete when the sample current reached a
value of 100mA.
27
References
[1] S. M. Green, A. Piquein ‘Pulsed Laser Ablation of Thin Films’, edited by

D.B.Chrisey and G. K. Hubler, John Willey and Sons, Canada, (1994).
[2] The Specification table of COMPEX 201 laser source from Lambda
Physik.
[3] S. B. Desu, Proc. Mater. Res. Soc.: ‘F erroelectricthinf ilm’, 361, 3,

(1995).
[4] S. K. Gandhi, VLSI Fabrication Principles (John Willey and Sons USA
1983).
28
Chapter 3
Growth and Structural

Characterization
3.1 Introduction
Thin films processing parameters and microstructure properties have the practical
importance in terms of functional macroscopic properties. The macroscopic prop-
erties of the deposited films strongly depend in the deposition characteristics and
can be controlled by changing the process parameters. The pulsed laser deposition
(PLD) has given good stoichiometric which is one of the most essential properties
for the oxide thin films. Processing parameters, thickness of the films, interfa-
cial layer and electrodes play their role in controlling the macroscopic functional
properties. In this chapter, the influence of different processing parameters on
structure of the BZ thin films are discussed. Several processing parameters were
considered such as oxygen partial pressure, substrate temperature, laser fluence,
29
CHAPTER 3. GROWTH AND STRUCTURAL CHARACTERIZATION
mode of crystallization (in-situ/ ex-situ) to examine crystallographic structures,

microstructure and compositional evolutions in BZ thin films.
3.2 Crystallographic Structural Characterization
3.2.1 In-situ crystallization
Substrate temperature dependence
The X-ray diffraction patterns of BZ thin films deposited at various substrate

temperatures, at a fixed oxygen partial pressure 50 mT orr is shown in the Fig.3.1.
The films that were deposited at 400◦ C showed the amorphous phase. As the
substrate temperature increased to 550◦ C, the presence of perovskite phase has
evolved. Further increase in substrate temperature enhance the orientation along
(110) direction with the orientation along (111) and (211) directions at 600◦ C.
The presence of perovskite phase further enhanced and the orientation restricted
to (110) and (111) direction with the absence of orientation in (211) direction at
the substrate temperature of 650◦ C.
3.2.2 Ex-situ crystallization
1. Annealing temperature dependence
Fig.3.2 shows the effect of annealing temperature on the crystallinity of BZ thin

films. All the films were annealed at different temperatures keeping the annealing
30
3.2. CRYSTALLOGRAPHIC STRUCTURAL CHARACTERIZATION
time (90 min) and deposition pressure (20 mTorr) as constant. The increasing of
annealing temperature enhanced the orientation of the films as shown in fig.3.2.
*
(110)
(211)
(111)
(220)
(200)
* PtKβ
PtK α
* 0
650 C
Intensity (arb. unit)
* 0
600 C
0
* 550 C
pow
20 30 40 50 60
2θ
Figure 3.1: X-ray diffraction pattern of in-situ crystallized BZ thin films grown
with an energy fluence 3J/cm2 , at 50 mT orr oxygen pressure and at different
substrate temperatures 550◦ C, 600◦ C, 650◦ C along with the powder data.
31
90 min_ 20 mTorr
(200)
(110)
PtK β
(211)
(220)
PtK β
PtK α
Intensity(arb.unit)
0
800 C
0
775 C
0
750 C
20 30 40 50 60
2θ
Figure 3.2: Effect of annealing temperature on the crystallization of ex-situ BZ

thin films. The films were deposited at 400◦ C with an oxygen partial pressure of
20mT orr and post annealed for 90 minutes.
2. Annealing time dependence
Fig.3.3 shows the effect of annealing time on the crystallinity of BZ thin films. All
the films were annealed at constant temperature (775◦ C) and constant deposition
pressure (50 mTorr). Increase in annealing time increased the orientation towards
(110) and (200) directions. The phase evolution on increasing the annealing time
32
was not as good as on increasing annealing temperature, which has been observed
from the corresponding peak heights.
0
775 C_50 mTorr
(110)
(200)
PtK β
(211)
(220)
PtK α
Intensity (arb.unit)
90min
75min
60min
45min.
30 min
20 30 40 50 60
2θ
Figure 3.3: Effect of annealing time on the crystallization of ex-situ BZ thin films.
The films were deposited at 400◦ C with an oxygen partial pressure of 50 mT orr
and post annealed at 775◦ C.
33
0
775 C_60 min
PtK α
(110)
(200)
PtK β
(211)
Intensity (arb.unit)
100 mTorr
50 mTorr
20 mTorr
20 30 40 50 60
2θ
Figure 3.4: Effect of oxygen partial pressure during deposition on the crystalliza-
tion of annealed BZ thin films. The films were deposited at 400◦ C and were post
annealed at 775◦ C for 60 minutes.
3. dependence on deposition pressure
Effect of oxygen partial pressure on the crystallinity during deposition and post
annealing of BZ thin films, is shown in fig.3.4. In this case the films were deposited
at different oxygen partial pressure ( 20 mTorr, 50 mTorr and 100 mTorr) and
ex-situ annealed at constant temperature (775◦ C) with the annealing time of
34
60 minutes. From the fig.3.4 we can clearly see the orientation towards (110)
direction has comparatively enhanced with the suppression of the orientation
towards (200) direction. We have not observed any secondary phase formation
which is one of the main problem while processing oxide thin films.
3.2.3 Effect on Grain Size
The effect of grain size has been found out using Sherrer’s formula as follows[3].
0.9λ
d= (3.1)
βcos(θ)
where,
d= Particle size
β= Full width half maxima of the particular orientation peak. λ= Wavelength
of the X-ray used
θ= Angle corresponding to the corresponding peak
In this study, the calculation of grain size has been restricted by the analysis
of (110) orientation only. Fig.3.5 a, b, c shows the grain size as a function
of annealing temperature, annealing time and deposition pressure respectively.
There were no significant changes in the grain size according to the processing
parameters in the limit which has been shown in the fig.3.5. It has been noted
that the average grain size was ∼ 0.15µm.
35
0.2 0.2
a) 20 mTorr_90 min b) 0
775 C_50 mTorr
Grain size (µm)

Grain size (µm)
0.15
0.15
0.1
0.1
750 760 770 780 790 800
30 40 50 60 70 80 90
0
Annealing temperature( c) Annealing time(min)
c) 0
775 C_60 min.
0.2
Grain size (µm)
0.15
20 40 60 80 100
Pressure (mTorr)
Figure 3.5: Effect of processing parameters on grain size of BZ thin films. The
films were deposited at 400◦ C. a) Effect of annealing temperature b) Effect of
annealing time c) Effect of deposition pressure.
36
3.2.4 Effect on stress
The effect of stress with various processing parameters has been studied using the
following formula with the restriction of orientation in the (110) direction [3, 4].
E(da − d0 )
Stress = (3.2)
2d0 υ
where,
E= modulus of elasticity
υ= Poisson’s ratio
d0 = Actual d spacing value ( from JCPDS)
da = XRD d spacing value
The fig.3.6 a, b, c shows the dependence of stress as a function of annealing

time, annealing temperatures and deposition pressure. There were no significant
changes observed in the stress of the BZ thin films within the working range as
shown in the figure after taking the apparatus displacement error in to account.
The stress which we have observed was a compressive stress in all the cases witin
the working range of the parameters. The observed stress range was within 30 to
60 Giga Pascal.
37
-40
0 -30
a) 775 C_50mTorr
b) 90min._20 mTorr
-45 -35
-40
-50
Stress (Gpa)
Stress(GPa)
-45
-55
-50
-60
-55
-65
-60
30 40 50 60 70 80 90
750 760 770 780 790 800
Annealing Time (min) 0
Temperature( C)
-50
c) 0
775 C_60min.
-51
-52
-53
Stress (GPa)
-54
-55
-56
-57
-58
20 40 60 80 100
Pressure (m torr)
Figure 3.6: Effect of processing parameters on stress of BZ thin films. The films
were deposited at 400◦ C. a) Effect of annealing time b) Effect of annealing
temperature c) Effect of deposition pressure.
38
3.3. MICROSTRUCTURAL ANALYSIS
3.3 Microstructural Analysis
3.3.1 In-situ crystallization
Fig.3.7 a, shows the cross sectional SEM picture of an in-situ crystallized BZ thin
films. The cross sectional microstructure of the films accompanied by densifi-
cation of granular growth across the thickness of the films. The availability of
sufficient energy due to the enhancement in mobility of atoms at high substrate
temperatures during in-situ crystallization process enhances the effects via nucle-
ation for multi grains in the films [1]. Fig.3.7 b, shows the surface morphology of
an in-situ crystallized films.
3.3.2 Ex-situ crystallization
Fig.3.8 a shows the cross sectional SEM picture of an ex-situ crystallized BZ

thin films. From the picture, the ex-situ grown films showed fine grain structures
across the thickness of the films. Fig.3.8 b shows the surface morphology of a
ex-situ crystallized BZ thin films. The ex-situ grown films showed the uniform
distribution of particles in the surface with very fine grain structure and less
porosity.
39
Figure 3.7: SEM photographs of in-situ BZ thin films. a) cross sectional view.
b) surface morphology.
40
3.3. MICROSTRUCTURAL ANALYSIS
Figure 3.8: SEM photographs of ex-situ BZ thin films. a) cross sectional view.
b) surface morphology.
41
3.4 Compositional Analysis
1.4
Ba/Zr
1.2
1.0
Ratio
0.8
0.6
0 1 2 3 4 5
Distance (mm)
Figure 3.9: Spatial variation of composition of BZ thin films grown at 650◦ C with
an oxygen partial pressure of 50mT orr at the fluence of 3J/cm2 .
Semiquantitative analysis was carried out using the EDAX method to determine
the composition of the BZ films [2]. The fig.3.9 shows the spatial variation of Ba
and Zr in a BZ thin films which has been deposited at 650◦ C. We have got the
consistent in stoichiometry of the BZ thin films which were deposited at different
substrate temperatures.
42
3.5. CONCLUSIONS
3.5 Conclusions
1. The processing parameters such as substrate temperature, deposition pressure,

annealing temperature and annealing time had its influence in crystallinity and
microstructural properties of the BZ thin films.
2. The in-situ and ex-situ annealed films had the tendency to enhance the per-
ovskite phase at higher temperatures.
3. The phase evolution on increasing the annealing time was not as good as on
increasing annealing temperature, which has been observed from the correspond-
ing peak heights.
4. There were no secondary phases observed in in-situ and ex-situ BZ thin films.
5. The effect of the processing parameters over the grain size and the stress along
the (110) direction has been discussed.
6. The cross sectional SEM pictures revealed that the in-situ and ex-situ films
had the multi grain structures.
7. There was no considerable variation in stoichiometry of the BZ thin films
which were deposited at different substrate temperatures.
43
References
[1] Zian Kighelman, Dragan Damjanovic, and Nava Sette, J.Appl.Phys., 89,
1393 (2001).
[2] S. Otsubo, T. Maeda, T. Minamikawa, Y. Yonezawa, A. Morimoto, T.

Shimizu, Jap.J.Appl.Phys., 29, L133, (1990).
[3] B. D. Cullity, Elements of X-ray Diffraction (Addision-Wesley, Reading,

MA, 1977).
[4] A. J. Perry, J. Vac. Sci. Technol. A8, 1109 (1990).
44
Chapter 4
Secondary Ion Mass

Spectrometry (SIMS) Analysis
4.1 Introduction
Secondary ion mass spectrometry, henceforth abbreviated to SIMS, works under

the principle of sputtering. When energetic (≥ 0.1keV atom−1 ) ions, atoms or
molecules impinge upon a solid, it inevitably leads to the ejection of particles out
of the target from near (∼ 1nm) the point of impact. This form of erosion goes
under the name of sputtering. As the liberated species stem from very shallow
depth (< 1nm), these carry information about the (local instantaneous) composi-
tion of the target surface. By continuing bombardment with primary species for a
prolonged time an increasingly deeper sputter crater develops. Consequently, the
sputtered secondary species will then reflect the composition inside the target.
By dynamically registering the number of ejection per unit time, as a function
45
CHAPTER 4. SECONDARY ION MASS SPECTROMETRY (SIMS) ANALYSIS
of time, one thus obtain a depth distribution for those species which is known
as sputter-depth profiling. In the case of SIMS the sputtering by primary ions
serves two purposes simultaneously, namely to generate emission from the target
surface for in-flight analysis and to peel the surface off.
In SIMS the secondary species to be analyzed are charged. This has the advantage
that standard,well-established and reliable, spectrometric methods can be applied
to discriminate on mass (or rather mass over charge ratio). Given a sufficiently
good mass resolution, in principle a perfect mass separation is possible and then
a unique identification for all ejected elemental and poly-atomic ions is possible.
Hence SIMS allows for the detection of all elements and their isotopes. It’s a rare
feature for surface sensitive analytical techniques. Of course practical restrictions
make the true situation less roseate. A considerable disadvantage of SIMS is
that often only a minute fraction of the sputtered particles leave the surface in
a charged state. Techniques related to SIMS have been developed to circumvent
this problem by post-ionization of the ejected neutrals prior to detection, the so
called Secondary Neutral Mass Spectrometries (SNMS), but with only limited
success. Another problem in SIMS lies in the fact that the primary species are
ions. This leads to charge-up of insulating surfaces, thereby creating difficulties
that can only be overcome at some sacrifice. Neutral primaries are occasionally
used, in Fast Atom Bombardment (FAB)-SIMS, but the drawbacks of low(er)
intensity and more difficult focusability/ positioning generally do not outweigh
the advantage over conventional and convenient ion beams.
46
4.2. ELEMENTS OF SIMS
4.2 Elements of SIMS
(a) One(or more)primary ion source(s)

(b) A primary beam selector (more precisely, a purifying energy and/or mass
filter)
(c) Focus and deflection stage(s)
(d) Target chamber with loadlock and holder
(e) A secondary ion energy discriminator
(f) The mass analyzer
(g) The detector (assembly)
(h) Data storage and manipulation facilities
4.3 Capabilities
The capabilities of SIMS are diverse, and include:

• depth resolution of 20 − 50Å with sputter rates down to 1Å/sec
• profiling to a depth of 8µ
• excellent detection sensitivity with wide dynamic range
• complete coverage of the periodic table
• quantification with appropriate standards
• ability to perform imaging to determine the spatial distribution of species or
map devices on a 2 − 5µ scale
• mass spectra acquisition up to 500 amu
• isotopic measurements.
47
Figure 4.1: schematic diagram of SIMS
48
4.4. FORMS OF PRACTICAL SIMS
4.4 Forms of practical SIMS
The three most important form of practical SIMS are, namely:
4.4.1 Static SIMS (S-SIMS)
Static SIMS, where the presence of molecules/ adsorbates at the very surface
is the subject of analysis. Characteristic for S-SIMS are a low primary beam
density(∼ pAcm−2 , in order to avoid excessive damage/ distortion to the surface
impurity population) and a large analyzed area (∼ cm2 , in order to get reasonable
statistics in spite of the low fluence). Bombardment energy and ion-type is not
too important, since subsurface damage and primary species incorporation are
of no concern, and are chosen at convenience. Because of the low ion flux, even
charge-up problem are usually not very severe.
4.4.2 Dynamic SIMS (D-SIMS)
Dynamic SIMS, where the depth distribution of impurities in the ∼ 10nm−10µm

range has the main interest. Characteristic for D-SIMS is a more intense primary
beam (∼ 0.1mAcm−2 ) usually well focused to allow for rastering over a small
area (∼ 10−3 cm2 , in order to get a reasonable erosion rate combined with a flat
sputter crater bottom of which only a central part (∼ 10%) actually contributes
to the analysis to avoid redeposition off the crater walls). The type and energy
of the impinging species are now of foremost importance as during depth pro-
filing previously implanted primaries will be encountered and may influence the
secondary ion’s formation and survival probability. Attainable detection limits
49
and depth resolution depend on the sputter yield and the damage or disturbance
to the original profile inflicted by bombardment/ erosion. So the primary beam
parameters must be optimized in accordance with the (anticipated) analytical
requirements for the particular sample.
4.4.3 Bulk contamination/ composition studies
This is the studies, where one aim is to establish the presence of impurities, or
set upper limits to their concentration level, in solids. Characteristic here is the
strive for maximum secondary species intensity, i.e. high density energetic (more
or less focused) primary beams (in order to get the highest possible sensitivity).
Achievable detection limits are typically in the ppm to ppb regime, but vary
considerably with impurity. A completely different application is found in the
fields of geology/astronomy/geography. Isotopic abundances vary slightly with
origin over the earth’s crust and the isotopical composition of extraterrestrial
rock may differ significantly from that encountered here. So SIMS may provide
a means of locating or assigning a specimen. Clearly the requirements differ
somewhat from those in impurity detection and a better primary beam definition
is usually required.
Imaging SIMS can be considered a particular version of S-SIMS. Here the two
dimensional distribution of one or more elements over part of the surface ( lateral
dimensions typically (∼ 0.1mm) is probed. This requires a very finely focused
primary ion beam or an excellent secondary ion beam in optical system that
accurately preserves the position (i.e. origin of ejection). For a surface mapping
a fairly low fluence is needed. By continuing erosion, extension, extension to
D-SIMS, that is including depth to obtain a full three dimensional profile. The
50
4.5. SPUTTERING
poor statistics per datum, in particular for dilute impurities, is the main limiting
factor. Imaging SIMS has been applied with remarkable success to biological
samples, where specimen preparation is a key issue, and also to semiconductor
devices, as well as grainy samples like metal alloys, ceramic compounds, thin films
etc.
4.5 Sputtering
4.5.1 General background
The bombarding primary ion beam sputters out, secondary ions, ionic clusters,
atoms, molecules, atomic clusters, elctrons and photons. The secondary particles
have kinetic energies in the range from Zero to several hundred eV [1]. Primary
beam species used in SIMS include Cs+ ,O2+ ,O, Ar+ , and Ga+ at energies between
1 and 30 keV. Primary ions are implanted and mix with sample atoms to depths
of 1 to 10nm. Sputter rates in typical SIMS experiments vary between 0.5 and
5nm/s. Sputter rates depend on primary beam intensity, sample material, and
crystal orientation.
4.5.2 Total yield systematics and linear cascade predic-

tions
Trends in total yield (i.e. number of target atoms out per elemental ion in) data
for poly crystalline and amorphous elemental targets, for which the most extensive
information is available, will be discussed. (i) It appears that the total sputtering
51
yield (Y) varies rather smoothly with incident ion Energy Ei , first increasing to
a broad maximum and gradually dropping to zero again for very high energy
(MeV). Only at very low Ei (∼ 0.1 − 0.5keV ), above but near the onset of
observable sputtering, is a steep increase with energy found. (ii)The dependence
of yield (Y) on ion type (i.e. atomic number Zi ) is fairly weak, especially at low
energy, although it becomes slightly more pronounced for heavier mass target
atoms and towards very light projectiles. (iii) The yield increases with angle of
incidence θi , defined relative to the surface normal, to a maximum usually around
60 − 80◦ and then drops steeply to zero for near-glancing incidence (θi ∼ 90◦ )
because of particle and energy reflection. The variation is most prominent for
light ions. (iv) Target element (Zi ) dependence. The magnitude of Y, for a given
beam condition (Zi , Ei , θi ), oscillates wildly as a function of target species. The
most successful attempt to capture these observations in a single model, and
certainly the most comprehensive theory to date, stems from Sigmund [2]. He
used a linearized Boltzmann transport equation to describe the collision cascade
in a random (semi-) infinite solid. Then the sputtering yield can be expressed
as the product of a material parameter, comprising the angle, depth, and energy
averaged escape probability for a target atom to escape from the surface and the
energy deposited by the impinging ion at the surface as target atom motion.
4.5.3 Multicomponent materials
At this stage it becomes time to address multicomponent targets as these are

the most common. Unfortunately there exist hardly any systematics, general
trends or scaling laws. Also it is not even clear whether or not metal alloys, com-
pound semiconductors and insulators/glasses/salts may be treated on the same
52
4.5. SPUTTERING
theoretical footing or must be regarded as distinct classes. The major difficul-

ties lies in the non-stoichiometric removal of surface atoms leading to changes in
surface composition depending on ion type, energy, angle of incidence and even
target temperature. After prolonged bombardment equilibrium must eventually
be reached. That is, the spatial sputtering yields of the constituent atoms then
reflect exactly the bulk composition. Note that this need not apply to the sur-
face itself, which may still be, e.g., enriched in the component with the lowest
elemental sputtering yield. This is a serious problem in sputter-depth profiling
employing on-target surface sensitive analytical techniques. Onset of equilibrium
may require removal of tens (to hundreds) of nanometres of target material. En-
richment or depletion may be caused by various discriminable mechanisms. Ion
bombardment leads to chemical bond breaking through relocation. Then either
recombination, possibly even resulting in new compounds, occurs or even desorp-
tion when volatile species are involved. In ionic crystals, e.g. the alkali halides,
electronic processes invoked by the ion (for example, interatomic Auger decay)
may neutralize surface target atoms followed by thermal release (of the halogen).
Similar processes occur under electron or photon irradiation. Other mechanisms,
following from the mass dependent energy partitioning in the cascade and ther-
mal and/or radiation (defect) induced segregation and diffusion, also contribute
to the non-stoichiometric surface composition.
Total yield measurements under steady-state conditions have mainly been re-
ported for (metal-)oxides, alkali halides and some binary metal alloys. These
limited data suggest a smooth Ei , θi and Zi dependence and a pronounced varia-
tion with target material, akin to the results discussed for elemental targets. For
binary metal but also, e.g., SiGe Alloys,Ax B1−x , the total atom yield lies between
53
xYA + (1 − x)YB and YB for YA > YB ,
where YA,B are the elemental target yields, and the surface becomes enriched in B.
For oxides, M On , the total atom yield is commonly found to be comparable with
or to exceed the pure element M yield (except Al2 O3 and MgO) and the surface
becomes oxygen depleted (except under oxygen ion bombardment of course).
4.6 Basic characteristics of SIMS
Armed with a fair knowledge of sputtering processes we can easily understand

most of the characteristics that are so typical for SIMS and the consequences
these have for practical implementation. At some length the more important
ones will be discussed in the following.
4.6.1 Sensitivity and quantification
The secondary ion escape probability strongly depends on the local electronic
environment at the origin of ejection. A different matrix automatically implies a
different secondary ion yield for a given species. Consequently, compositional gra-
dients (as in GaAs/AlGaAs multilayer structures), background gas ad/absorption
and even a high level of impurity contamination (≥ 1%) all affect the secondary
ion yield. This has two immediate consequences, namely (i) absolute and a priori
quantification becomes virtually impossible and the best one may hope for is a
possible calibration against ‘standards’. (ii) a rather good vacuum is required
during the measurements. Also the secondary ion escape probability strongly
depends on the type of species ejected for a given matrix. As a consequence, the
54
4.6. BASIC CHARACTERISTICS OF SIMS
fact that a high secondary ion intensity is seen for impurity X and a low one for
species Y does not indicate anything whatsoever about their relative concentra-
tions (e.g. for Ba contaminated Au the positive elemental ion intensities during
Ar+ bombardment are such that one can obtain a ppm detection limit for bar-
ium but it is improbable to get any signal intensity around mass 197, i.e. gold!).
Under noble gas bombardment, usually the ionized fraction for a given emitted
species is typically only of the order of 10−3 , but it may range from 10−7 or worse
to 0.1 and even higher. Needless to say this will affect the detection efficiency
enormously.
The problem of low to modest sensitivity can be alleviated in many cases by the
selection of a suitable primary ion type. It is possible to enhance the positive
(negative) secondary ion yield by raising (lowering) the work function ϕ. This
can be achieved by saturating the near-surface region e.g. with respectively oxy-
gen and caesium. This naturally accompanies prolonged bombardment with O2+
(occasionally O− ) or Cs+ . This particular solution has been adopted in SIMS in-
struments for over a decade. In that time the sources for such ions have matured
considerably. Yet the reactive/aggressive nature of these two species make the
sources much more maintenance-prone than, e.g., noble gas ion ones. A partial
solution, at least for positive secondary ion yield enhancement, is to use noble
gas ions in combination with oxygen gas flooding of the target. Of course care
has to be taken to avoid back stream of oxygen to the source(e.g. by differen-
tial pumping). Note that at large off-normal bombarding angles the increased
sputtering yield, in combination with primary ion refection(for angles θi > 60◦ ),
will obstruct the build up of an altered near surface region by O2+ or Cs+ bom-
bardment. Additional oxygen flooded may then still be of good service with
the former, no improvement is possible with the later. In surface contamination
55
studies where the total fluence used is low (S-SIMS) the sensitivity cannot be
improved by proper selection of primary ion type. Finally, it must be stressed
that oxygen-covering or oxygen-loading of a target will only be efficient for those
samples that allow oxidation to some extent (i.e. not for the aforementioned
Au) and this inevitably leads to some reduction in the erosion rate. Yet oxygen
gas flooding and/or oxygen ions or, alternatively, cesium ions are very helpful
in making SIMS a technique that potentially can detect almost any element in
almost every matrix and set limits to impurities typically on a ppm level or better
(although sometimes instrumental design factors are inhibitive for certain con-
taminant/target combinations). The fee for this unique asset is the (extremely)
difficult quantization.
4.6.2 Mass interferences
In SIMS, the detection is carried out by using the principle of mass over charge
ratio. In addition we know that poly-atomic species (clusters) are also ejected
during sputtering. As an example the, so-called, secondary ion mass spectrum of
silicon bombarded with O2+ has been taken. Obviously the signal intensities with
different ‘composition’ but with identical ‘nominal’ mass (in amu) may interfere,
unless mass resolution is very good indeed. Famous examples in a silicon matrix
are the 29 Si,30 Si,16 O and 75 As+ ions or the pair 31 P/30 SiH which require a mass
resolution M/∆M in excess of 3000. This example shows at the same time that
the existence of more than one isotope for a particular element is neither a curse
nor a blessing. On the one hand interference may be excluded by selecting the
proper isotope (although rare ones are to be avoided in general). On the other
hand, more isotopes open up the path to more interfering combinations.
56
Light elements suffer least from interferences (although the detection limit for 10 B
in Si is ultimately determined by the 10 B + /30 Si3+ interference, even though 30
Si
has only 3% natural abundance and multiply-charged ion survival is rare!). At
masses above 100 one should (always) implicitly assume(some) mass interference.
A modest resolution secondary ion mass spectrum will enable some cross-checks
against natural isotopic abundance for the element of interest and when large
deviations are observed this generally signals, yet does not identify, mass inter-
ference. Background gases in a non-uhv system are typically H2 , N2 , CO2 and
O2 , sometimes also accompanied by some higher hydrocarbons from pump oils
etc. That is, low-mass containing species with usually a fair sticking probability
on the sputtered target. Interferences with clusters containing one (or more) of
these atoms will be the result.
A high mass resolution can be obtained but usually at the expense of sensitivity
and often also by sacrificing long-term stability/reproducibility of the instrument.
The one exception is the Time-of-Flight (TOF-)SIMS design, but this approach
is limited to very-near surface studies. For selected cases the use of different
primary ions and/or secondaries may help in minimizing interference problems
(e.g. 75
As+ /SiO2+ is a severe problem with O2+ bombardment of silicon but
75
detecting the negative ions As− or28 Si75 As− , using Cs+ , largely nullify the
problem. A more widely applicable remedy derives from the difference in energy
distributions of elemental and cluster ions. The kinetic energy distribution of a
cluster ion is more confined to lower energies because the dissociation probability
becomes high upon forceful ejection. So by restricting the analysis to ions that
have been ejected at sufficiently high energy one discriminates efficiently against
interfering ‘clusters’. Usually a lower limit of 10-25 eV will do , occasionally a
(much) higher value is required. Finally we note that this method is occasionally
57
inoperative because of ionization/neutralization particulars causing an abnormal

kinetic energy distribution and for highly asymmetric clusters (e.g. SiH, WO etc.)
because there the energy transfer upon ejection is mainly to the heavy partner
and hardly any ends up in the centre-of-mass to evoke dissociation.
4.6.3 Pre-equilibrium effects
At any interface an altered layer is built up during bombardment, owing to inci-

dent particle incorporation. In turn this modifies the erosion rate and secondary
ion survival probability. These effects will be less important for high sputtering
yield materials and grazing ion incidence. And of course at lower energies steady
state conditions are reached quicker. An additional problem affecting the analysis
in the initial stages of depth profiling lies in presence of surface contamination
by ad/absorbed species. Although this contamination may be confined to the
very near surface region (≤ 1nm), it can be mixed into the target during ion
bombardment and eventually exert influence to considerably larger depths.
4.6.4 Detection/resolution limits and ion bombardment

induced mixing
In dynamic SIMS one always has to compromise between attainable detection

and resolution limits. This does not hold for static SIMS, where the boundary
condition of a virtually unperturbed surface dictates the admissible primary ion
fluence. When enough material is available one may depth profile under various
conditions to get the best of both worlds, but every so often the analytical problem
at hand does not allow for this simple solution.
58
Obviously a good detection limit and a high secondary ion sensitivity are inter-
related. In general, the higher the erosion rate the better the sensitivity. So high
current, high energy primary ion beams appear ideal. Unfortunately, with the
energy not only the sputter yield but also the penetration depth and cascade vol-
ume (i.e. the extent of bombardment, induced damage/relocation/disturbance in
the target) go up. All this adversely affects resolution. Following Hofmann [3]
one may distinguish three sources contributing to the attainable depth resolution,
namely:
(i)Instrumental factors
Here erosion inhomogeneities caused by non-uniform irradiation of the analyzed

area feature most prominently. The resolution deterioration ∆z is linearly pro-
portional to the eroded depth z, until redeposition becomes important at very
large depths where it becomes constant.
(ii)Sample characteristics
Intrinsic surface roughness, but also poly-crystallinity and/or multiple phases

.
(i.e. compositional differences across the target) all introduce local variation ∆ z
.
of the mean erosion <z> rate. The accompanying deterioration of resolution is
.
proportional to ∆z/<z> and depends on depth like z 1/2 or z depending on grain
size.
59
(iii)Particle-solid interaction particulars
It is assumed that the incident ion bombardment leads to a complete and uniform
redistribution of all particles within the collision cascade volume(Simple model of
ion beam mixing stems from Liau et al ) [4]. In addition, this is taken to extend
to equal depth for all individual impacts and furthermore that erosion proceeds
perfectly homogeneously. The implications of this model will be elucidated for
the case of a dilute delta (or monatomic plane) impurity distribution embedded
at the depth zδ in a target profiled with SIMS. Before the erosion front comes
within the ‘disruption depth’ RD of that layer no mixing occurs, but once a depth
zδ −RD has been reached suddenly all impurity atoms are mixed backwardly up to
the surface. The corresponding secondary ion signal intensity abruptly increases
from zero (or background level) to a maximum many decades higher. Upon
continuing bombardment, endless forward mixing takes place and the perceived
concentration decreases exponentially with a characteristic decay length equal to
RD (after conversion from time-to-depth). In fact this applies to any confined
distribution (that is extending to some maximum depth zmax > RD ). From
some starting concentration C, the loss of layer of thickness dz and mixing in
of an undoped layer dz into the disrupted depth zone leads to a new average
concentration C[1 − dz /RD ], so the differential equation dC(z)/dz = −C(z)/RD
holds, leading to the said exponential behaviour[5].
4.6.5 Charging Problem
The fact that the primary beam is charged may lead to problems when examining
insulators. Charge-up of the sample may occur and this in turn will affect the
60
impact parameters of the primary beam (Ei , θi , position), as well as those of the
ejected species (energy distributions); consequently it has to be avoided whenever
possible. Simple remedies like a very low primary ion current or sample heating
to improve its conductivity are unattractive for reasons of loss of sensitivity and
diffusion-induced profile alteration [6]. There are two fairly widely applicable
solutions, namely:
(A) Coating the surface with a thin (∼ 30nm) metallic layer, combined with
negative primary ions (often O)for analyzing positive secondary ions. In principle,
negative primary ions induce negative charge-up; but during ion bombardment
electrons are liberated from almost any target and relatively efficiently from a
metal. The energy distribution of these secondary electrons typically peaks at a
few eV and only a minute fraction receives energies in excess of 10-15 eV, so the
electrons can drift away from the point of impact and land elsewhere. As soon
as the ion-irradiated and exposed insulating target becomes positively charged to
more than a few volts, either the electrons return rather than escape, or electrons
freed by stray primary beam species from the metalized rim/surroundings of the
sputter crater/rastered area aid in near-neutralization. Occasionally a diaphragm
can replace the coating.
(B) Exposing the target continously to a flux of thermal electrons (from a hot
filament) or a beam of energetic (∼ 0.1 − 1keV ) electrons (from an e-gun) works
reasonably well in the absence of any target bias and when positive primary ions
are utilized. Thermal electrons can only be used in the absence of high extrac-
tion fields, so energetic beams are preferred. At too high energy (≥ 1 − 2keV )
, however, surface charge compensation becomes incomplete owing to electron
penetration. Also, the beam current must be tuned to each new target material,
61
a problem in insulating multilayer samples. Finally, defocusing or rastering over

an area in excess of the ion irradiated area is usually necessary.
4.6.6 Miscellaneous
A few aspects need brief mentioning. These could not properly be incorporated
in one of the previous subsections, so have been gathered here. This does not
imply any relation, however!
Different isotopes of an element do not entirely have identical ion formation/

survival probabilities. The reason for this lied in the effectively slightly different
velocity distribution accompanying a given energy distribution. The effect can be
usually ignored, but must be taken into account when one tries to study isotopic
abundance differences.
We have been rather jubilant about the role of oxygen flooding in SIMS, its
positive role in enhancing the positive secondary ion yield, in minimizing the pre-
equilibrium regime and in reducing surface topography development. There are,
however, some negative points that put the advantages in a proper perspective,
namely:
(i) The addition of relatively light mass atoms to the target potentially increases
the possibility of mass interference with heavy secondaries of interest.
(ii) The oxidation reduces the erosion rate and according to some theories (and
experiments) the enhanced ion flux needed to profile to a given depth leads to an
increase in broadening by mixing, but the reverse may equally well apply [7].
(iii) Matrix effects may be reduced in favourable cases for multilayer samples but,
62
owing to large oxygen retention differences between material results, may equally
well be changing for the worse.
(iv) The formation of an insulating oxidized top layer on the target may lead to
charging effects, which in turn may cause impurities to (field) migrate away from
the surface and move to the oxide/bulk interface.
The latter constitutes the most devastating manifestation of a SIMS artefact

know to date, causing redistribution of impurities over microns. Luckily it is quite
rare; but even in the presence of an electric field, the chemical gradient can cause
migration of mobile impurities [8]. Here the lesser affinity of oxygen, as compare
to the matrix atoms, provides a ‘thermodynamic’ driving force which invokes site
exchange between minority and majority species. This amounts effectively to
diffusion of the former into the bulk. Similar processes may accompany nitridation
of the surface.
Detection limit of several substances will be affected strongly by their presence

as a component of the residual gases in the instrument. This typically includes
hydrogen, carbon, nitrogen and oxygen, which may stem from cracked pump oil
or become introduced during sample exchange via a load lock. It is simple to
summarize the problem.
Modern integrated circuit technology favours continuously decreasing lateral di-

mensions. For on-chip SIMS analysis (e.g. to locate or examine failures) this
would require a reduction in raster area size. This conflicts with reasonable de-
tection limits and/or depth resolution as we will show here. Consider an analyzed
area of 1×1µm2 . A reasonable sampling period should be such that no more than
10nm of material is removed in between data points (depth dimension becomes
smaller too)[9].
63
4.7 Quantification of depth profiles
4.7.1 General remarks
In this section we will discuss quantification of the raw SIMS data, i.e. conversion
of (time-dependent) signal intensity Ii (t) for a given ionic species i ejected from
a matrix M into a concentration (depth distribution) Ce (z) for the corresponding
impurity element ‘e’. Note that e and i are not necessarily related directly. For
example, with Cs+ primary ion it is often advantageous to monitor the 75
As28 Si
cluster for arsenic impurities in silicon, whiles for zinc in indium phosphide (InP)
64
even the positive Zn133 Cs+ secondary cluster ion gives good results. In the
latter case one detects only one isotope, a common situation, so that a further
abundance correction is necessary to arrive at the total element concentration.
Almost all quantification methods apply to dilute impurities, for which the as-
sumption of a linear dependence between signal intensity and concentration is
valid.
4.7.2 Time-to-depth conversion
The crater depth for the sample BZ thin film was measured using the Sloan 3030
surface profilometer, in which a diamond tipped stylus of diameter 25µ with an
impressed force of 0.1N was made to slide over the coated surface. This provided
the depth of the primary ion effected crater and was used as a calibrator to assess
the depth profiles in other samples taken for the study. The depth profiles were
obtained as a function of sputtering time which can be converted into depth by
means of the crater depth obtained from the surface profilometer.
64
4.7. QUANTIFICATION OF DEPTH PROFILES
4.8 Results and Discussions

Fig.4.2 shows the SIMS profile, which shows the as measured signal intensity of
a BZ thin film as a function of Sputter time.
5
10
2 -> 16O
4 -> 195Pt
1 3 -> 90Zr
1 -> 138Ba
4
10
3
2
10
3
[C/S]
2
10 4
1
10
0
10
0 500 1000 1500 2000 2500
Sput.Time:[S]
Figure 4.2: As-measured signal intensity V s elapsed errosion time of a BZ thin

film.
65
Figure 4.3: The crater depth for the BZ thin film which was measured using the
Sloan 3030 surface profilometer
.
66
4.8.1 Effect of in-situ annealing and ex-situ annealing
5
10
1 -> 138Ba
2 2 -> 16O
3 -> 90Zr
4
10
1
* 4 -> 195Pt
2 *
3
10 *
3
[C/s]
2
10 4
4
1 3
10
1
Tp
0
10
0.0 0.1 0.2 0.3 0.4 0.5 0.6 0.7
Thickness (µ m)
Figure 4.4: Depth profile of BZ film deposited at 50mT orr oxygen pressure and
in-situ annealed at 650◦ C.
67
5
10
1 -> 138Ba
2 -> 16O
3 -> 90Zr
1 4 -> 195Pt
4
2
10
2
3
10 4
3
[C/s]
2
10 4
1
1
10
0
10
0.0 0.1 0.2 0.3 0.4 0.5 0.6 0.7
Thickness (µ m )
Figure 4.5: Depth profile of BZ film deposited at 50mT orr oxygen pressure with
substrate temperature 400◦ C and ex-situ annealed at 650◦ C for 90 minutes.
68
Conclusions:
A) Fig.4.4 shows the SIMS profile of an in-situ annealed film at 650◦ C which has
deposited in 50 mTorr Oxygen pressure, which leads to the following conclusions.
1. The interface is sharp and almost no diffusion of Ba and Zr in to platinum
layer when compared to the thickness of the platinum layer.
2. The peaks observed in all elements (Ba, Zr,O) reveals that there is a fixed
proportion of the constituent species of the expected phase. So the film growth
at the interface is good. Moreover, the stoichiometry and sputtering rate are
different at the interface which has lead to humps in the region.
3. Oxygen concentration increases after platinum layer because we have an in-
terface of (P t/T iO2 /SiO2 /Si) in our substrate.
4. Tp shows the thickness of the platinum layer (0.18µm)
B) Fig.4.5 shows the SIMS profile of an ex-situ annealed film at 650◦ C which has
deposited in 50 mTorr Oxygen pressure with substrate temperature of 400◦ C,
which lead to the following conclusions.
1. The interface is not sharp and all the elements are interdiffused.
2. The flat nature which causes the compound formation along the interface is
observed from the profile.
69
4.8.2 Effect of ex-situ annealing temperature
5
10
1 -> 138Ba
2 -> 16O
# 3 -> 90Zr
4 -> 195Pt
1
4
10
* 2
4
2
3
10
3 *
[C/s]
2
10 4
1
1
10
0
10
0.0 0.2 0.4 0.6 0.8 1.0
Thickness (µ m)
the substrate temperature 400◦ C and ex-situ annealed at 600◦ C for 90 minutes.
70
5
10
1 -> 138Ba
2 -> 16O
3 -> 90Zr
1 4 -> 195Pt
4
2
10
2
3
10 4
3
[C/s]
2
10 4
1
1
10
0
10
0.0 0.1 0.2 0.3 0.4 0.5 0.6 0.7
Thickness (µ m )
71
5
10
1-> 138Ba
2-> 16O
3-> 90Zr
4-> 193Pt
4
10 1
3
10
2
[C/s]
3
2
10
4
1
10
0
10
0.0 0.5 1.0 1.5
Thickness (µ m)
72
Conclusions:
A) Fig.4.6 shows the SIMS profile of a ex-situ annealed BZ thin film at 600◦ C
and the following conclusions are arrived from the profile.
1. In the (∗) region both Zr and Oxygen have a uniform rise, whereas Ba falls
down suddenly (Zirconium Oxide have formed or segregated).
2. Hump in the ∗ region due to interface effects.
3. Flat nature was observed in the region //. It has given the conclusion of
compound formation (ZrO2 ) at the interface, a flat nature reveals that we have
constituents species of definite proportion.
4. In area there is a hump in oxygen, that due to T iO2 interface.
B) Fig.4.7 shows the SIMS profile of a ex-situ annealed BZ thin film at 650◦ C.
The details which we can get from the profile are
1. The flat nature has reduced than the film which has annealed at 600◦ C, which
may be due to dissociation and redistribution of Zirconium oxide.
2. The interdiffusion has been take place and the diffusion length is compara-
tively higher than the film annealed at 600◦ C.
C) Fig.4.8 shows the SIMS profile of a BZ thin film which has annealed at 775◦ C.
One can get the conclusion as follows from that profile
1. In this the formation of ZrO2 is almost nill. (i.e) the flat region found was
almost not there.
2. The oxygen content is found to be more at the interface. It’s due to high tem-
perature annealing, and the dissociation and redistribution of Zirconium oxide.
3. Platinum layer has diffused in to BZ films. It clearly shows interdiffusion and
merging which has been taken place in the interface.
4. The flatness observed has almost disappeared in this case, which due to the
73
redistribution of ZrO2 at higher temperatures.
4.8.3 Effect of Oxygen pressure
5
10
1 -> 138Ba
2 2 -> 16O
3 -> 90Zr
*
4 -> 195Pt
1
4
10
2
4
*
3
10 *
3 *
[C/s]
2
10
4
1
1
10
0
10
0.0 0.2 0.4 0.6 0.8
thickness( µ m)
Figure 4.9: Depth profile of the BZ film deposited at 20 mT orr.
74
5
10
1 -> 138Ba
2 2 -> 16O
3 -> 90Zr
4 -> 195Pt
4
10 1
3
10
2
1 *
[C/s]
3 3
2
10
4
1
10
0
10
0.0 0.2 0.4 0.6 0.8 1.0 1.2 1.4 1.6
Thickness(µ m)
Figure 4.10: Depth profile of the film deposited at 50 mT orr.
75
5
10
1 -> 138Ba
2 2 -> 16O
1 3 -> 90Zr
4
10 4 -> 195Pt
4
3
2
10
3
[C/s]
2
10
4
1
1
10
0
10
0.0 0.2 0.4 0.6 0.8 1.0 1.2 1.4
Thickness (µ m)
Figure 4.11: Depth profile of the film deposited at 100 mT orr.
76
Conclusions:
Effect of partial pressure:
A. Fig.4.9 shows the SIMS profile of BZ thin film deposited at 20mT orr and
ex-situ annealed at 775◦ C.
B. Fig.4.10 shows the SIMS profile of a BZ thin film which has been deposited at
50mT orr oxygen pressure and ex-situ annealed at 775◦ C.
C. Fig.4.11 shows the SIMS profile of a BZ thin film which has been deposited at
100mT orr and ex-situ annealed at 775◦ C. The following conclusions are arrived
from the profiles.
1. At the end of the interface, that is almost the end of Platinum depth (marked
as *), there is a rise in all the element which is almost in a fixed proportion. But,
really Ti,Zr,Pt are hiked in this right interface zone and the counts are not due
to Ba species. It’s due to the mass interference. The sum of masses of Ti and Zr
will equal that of Ba.
2. The profiles doesn’t show any significant variation as a function of oxygen
partial pressure other than the increase of oxygen content at the interface.
4.8.4 Interdiffusion of platinum
1. In in-situ annealed thin film there is no diffusion when compared to thickness

of platinum layer.
2. On increasing of ex-situ annealing temperature diffusion of platinum elec-
trode has enhanced. The diffusion length for the films which have annealed at
77
600◦ C, 650◦ C, 775◦ C are 0.161µm, 0.190µm, 0.386µm respectively. The high tem-
perature processed film have high diffusion length.
3. No variation in diffusion of platinum under oxygen partial pressure, the diffu-
sion length falls around 0.18µm.
Since the diffusion length of the platinum is comparable with the thickness of plat-
inum layer, the diffusion of platinum, cannot be assumed as thin layer diffusion.
Moreover the diffusion coefficient of platinum in to the film was not determined
because a thin film cannot be assumed as a solid medium. The fail of Gaussian
distribution of interdiffusion of thin films is mainly dominated by pin holes etc.,
which is also observed in our samples. Since the interdiffusion of thin films is not
well understood, the diffusion coefficient of platinum was not determined.
78
4.9. SUMMARY
4.9 Summary
SIMS analysis has given a complete information regarding the interface studies
to a high resolution of almost 1nm. The profiles obtained for in-situ and ex-situ
annealed BZ films clears that in-situ annealed films have a very sharp interface
and diffusion of platinum electrode into the film is not found. Whereas in the
case of ex-situ annealed films there is an interdiffusion of both the film and the
platinum. Moreover in the ex-situ annealed films the segregation of Zirconium
oxide is found and which has also dislocated on higher annealing temperatures.
The formation of zirconium oxide on ex-situ annealed films has also affected
the electrical characteristics of the films. Moreover the platinum diffusion into
the film has caused an increase of leakage current in the ex-situ annealed films.
Interdiffusion of thin films is not well understood and it mainly depends on the
quality of the film and the interface. The diffusion curve which follows a Gaussian
nature is not a perfect Gaussian in the case of interdiffusion of BZ thin films. The
tail of the Gaussian is dominated by pinholes etc., so causes wider tail. Hence
the diffusion coefficient of platinum into the thin film was not done in this work.
Whereas the diffusion length of the platinum into the film is found to be higher
on higher annealing temperatures as expected. Due to the presence of oxide
interfaces (P t/T iO2 /SiO2 /Si) in the substrate the diffusion of the constituent
atoms (Ba,Zr,O) present in the film is not well enhanced even on higher annealing
temperatures.
79
References
[1] P. C. Zalm, Surface Interfae Anal 11, 1 (1988).
[2] P. Sigmund, Phys Rev 184, 383 (1969).
[3] S. Hofmann, Prog Surface Sci 36, 35 (1991).
[4] Z. L. Liau, B. Y Tsaur and J. W. Mayer, J Vac Sci Technol 16 121 (1979).
[5] H. H. Andersen, Appl Phys 18, 131 (1979).
[6] T. Kolber, K. Piplits, S. Dreer, E.Mersdorf, R. Haubne, H. Hutter, Appl

Surf Sci 167 79 (2000).
[7] M. Meuris, W. Vandervorst and J. Jackman, J Vac Sci Technol A9 1482

(1991).
[8] C. J. Vriezema and P. C. Zalm, Surface Interface Anal 17 875 (1991).
[9] A. J. Walker, M. T. Borchert, C. J. Vriezema and P. C. Zalm, Appl Phys

Lett 57 2371 (1990).
80
Chapter 5
AC Electrical Properties
5.1 Introduction
The knowledge of the ac electrical properties of the BZ thin films is essential,

because these properties directly determine the performance of the device. The
ac electrical measurements consists of the frequency domain response of a system
to an alternating sinusoidal signal. The microstructure has vital role in control-
ling the macroscopic properties such as conductivity and dielectric phenomenon
of the electronic materials. To estimate the influence of grain, grain boundary
and electrode on the charge transport phenomenon in materials, the electrical
impedance analysis is a powerful tool [8]. To improve the quality of the device
performance, understanding the effect of microstructure in thin films is neces-
sary. In the present chapter, we studied the dielectric response characteristics,
ac electrical properties in terms of impedance analysis and conductivity measure-
ments of BZ thin films in the frequency domain. The measurements have been
81
CHAPTER 5. AC ELECTRICAL PROPERTIES
carried out using a metal/insulator/metal sandwich structure with the BZ thin

film between the top Au electrode and the bottom Pt electrode.
5.2 Theory involved
5.2.1 Different types of polarization relaxations
The polarization of the sample which includes the polarization of grain and grain
boundaries and can be divided into three categories as follows:
1) Debye type relaxation.
2) Maxwell-Wagner polarization
3) Universal frequency response
1. Debye type relaxation
Small displacement in the ions cause the dipole moment. There are two kinds of
motions of these dipoles. 1) The dipole can be stretched 2) They can rotate an
axis. The situation becomes equivalent to a forced vibration problem while an
AC field is applied. These ions have a finite inertia, and a restoring force by which
the ion is bound to its original position. The square root of the ratio of the force
constant(k) to its inertia gives the natural frequency of the system.This gives a
measure of the time that an isolated dipole takes to respond to a time varying
signal. There are some dissipative forces that could hinder the motion of the
ions. Debye explain the origin of these dissipative forces by assumed a diffusion
controlled movement of the ions considering the sample as a dilute ionic gaseous
medium [2]. If the frequency of the AC electric field is much lesser than the natural
82
5.2. THEORY INVOLVED
frequency of the dipole, the response of the dipoles will be immediate, but since
there are dissipative forces present, they will dominate the overall polarization
response. The corresponding frequency dependence is called Debye relaxation.
The mathematical expression of pure ’Debye’ type response is as below
mẍ + γ ẋ + ω02 x = eE (5.1)
where,
E =⇒ The instantaneous electric field
m =⇒ Analogous to the inertia of the dipole
x =⇒ The separation between the centers of positive and negative charges
ẋ =⇒ The velocity of the moving charge
γ =⇒ The constant that determine the dissipative force
ω0 =⇒ The natural frequency of vibration
eE =⇒ The force acting on each ion of the dipole
mẍ =⇒ The inertial force
γ ẋ =⇒ The dissipative force
ω02 x =⇒ The restoring force
The ratio of the complex polarization to the complex electric field is called as the
complex susceptibility. The real part of the dielectric susceptibility is responsible
for the capacitance and the imaginary part of it is responsible for the dielectric
loss. The generalized equation according to the impedance of a series RC circuit
is as given below,
N q2 1 ωγ
χcomplex (ω) = [ ω 2 2 −j 4 ] (5.2)
0 ω02 + ( ω0 ) γ ω0 + ω 2 γ 2
83
A typical frequency dependence of the real and imaginary parts of the suscepti-
bility of a ’Debye dielectric’ is shown in the figure 5.1.
log ε real log εimag
log ω
Figure 5.1: The theoretical frequency dispersion curve of a typical ‘Debye’ type
dielectric. Both the dielectric constant and the dielectric loss factor are denoted.
84
2. Maxwell-Wagner polarization
This model is useful for the samples which have the polycrystalline nature. Most
of the real sample fall under this category. Therefore, they consist of grain and
grain boundaries. Both grain and grain boundaries can be assumed to be a
parallel combination of an ideal capacitor and a pure resistor. The net dielectric
response would be as if there are two such elements in series, as shown in figure
5.2. If the impedance of the sample is calculated assuming such an equivalent
circuit, then the equivalent capacitance at high frequency limit would be [5]:
C1 C2
Chigh = (5.3)
C1 + C2
Here there is no contribution from the resistivity part and at the low frequency
limit, the capacitance would be greater than the series equivalent capacitance of
the two elements
R1 R2
Clow = ( )2 C1 + ( )2 C2 (5.4)
R1 + R2 R1 + R2
It could be seen that, the excess capacitance is due to the presence of the inter-
face between the grain and the grain boundary. This results in another type of
polarization named as ’Maxwell- Wagner’ polarization.
85
C2
C1
R1
R2
C(0)
Creal tanδ
C1C.C 2
1 .C 2
1+
CC C
1 +2C 2
logω ωp
Figure 5.2: The theoretical frequency dispersion for ‘Maxwell-Wagner’ polariza-

tion.
86
3. The Universal frequency response
This is the most generalized model that could explain the dielectric response of
almost all kind of materials. This model was first given by Jonscher [3]- [7] and
used to call it as Jonscher’s model.The theoretical frequency dispersion of real and
imaginary part of the susceptibility is given in figure 5.3 according to ’Jonscher’s
law’.
The complex dielectric constant as a function of frequency ω, can be found out

using the following relation according to Jonscher’s model,
∗ σ a(T ) n(T )−1

= −i = ∞ + + (iω ) (5.5)
i oω o
where is real part of the dielectric constant, is imaginary part of the dielectric
constant, ∞ is high frequency value of the dielectric constant, n(T) is a weakly
temperature dependent exponent, which determine the correlation between dif-
ferent dielectric transitions, and a(T) determine the strength of the polarizability.
Thus
n(T )π n(T )−1
= ∞ + sin( )ω a(T )/ o , (5.6)
2
σ n(T )π n(T )−1
= + cos( )ω a(T )/ o , (5.7)
oω 2
Where the first term in Eqn. 5.6 gives the lattice response and that in Eqn. 5.7
gives the dc conduction part. The second term in both the equations gives the
charge carrier contribution to the observed dielectric constant. We can see the
corelation between theoretical and experimentally obtained results revealing the
behavior of the theoretical parameters such as n(T ), a(T ) and σ as function of
temperature.
87
χ im
(n - 1)π
log χ tan log χ im
real 2
χ real
log ω
Figure 5.3: Theoretical frequency dispersion of ‘χreal ’ and ‘χimaginary ’ according

to ‘Jonscher’s law’.
88
5.2.2 Complex electrical characterization
In order to aid microstructural interpretation with the object of optimizing the

electrical properties, complex electrical characterization of materials could be an-
alyzed in terms of the following possible parameters, namely complex impedance
(Z ∗ ), complex admittance (Y ∗ ), complex modulus (M ∗ ) and complex dielectric
constant ( ∗ ).All these four imitances are interrelated with one another:
M ∗ = jωCo z ∗ (5.8)
∗
= (M ∗ )−1 (5.9)
Y ∗ = (Z ∗ )−1 (5.10)
Y ∗ = jωCo σ ∗ (5.11)
where ω is the angular frequency, and C0 is the vacuum capacitance of the mea-
suring cell and electrodes with an air gap in place of the sample.
When the relaxation of different processes differs as a consequence of different ca-

pacitive components, the complex impedance is used to understand them. Com-
plex modulus or permittivity plane plots are used to represent the response of
dielectric systems. Complex impedance plots of Z Vs Z (where Z and Z are
the real and imaginary parts of the complex impedance, respectively) are useful
for determining the dominant resistance of the sample. However, these are in-
sensitive to smaller resistances. Similarly, complex modulus plots are useful in
determining the smallest capacitances. Sinclair and West [8]-[9] therefore sug-
gested the combined use of impedance and modulus spectroscopic plots. The
advantage of this technique is that M and Z (the imaginary parts of modulus
and impedance respectively) peaks for a particular resistance-capacitance (RC)
89
combination should be coincident on the frequency scale (ideal scale). Hence the
power of the combined use of impedance and modulus spectroscopy is that the
Z plot highlights phenomena with the largest resistance, whereas M picks out
those with the smallest capacitances [8].
5.2.3 AC conduction studies
AC conductivity studies is an important part of the dielectric studies. The ac

conductivity σac relates to the dielectric loss through the relation:
σac = ω 0 tan(δ) (5.12)
where 0 is the permeability of free space, the relative dielectric constant, ω

is the angular frequency, and tan(δ) is the dissipation factor.Ac conductivity
occupied a major part of the research in conductivity of dielectrics. The power
law for the frequency dependent ac conductivity is given by the following relation
[5]
σ(ω) = σ0 (T ) + Aω n (5.13)
where ω is the frequency of measurement, σ(ω) is the measured conductivity,

σ0 (T ) is the frequency independent dc part and 0 ≤ n ≤ 1. There has been several
theories to explain the power law dependence of ac conductivity on frequency. It
is suggested that in ionic samples, ionic charge hopping lead to the observed
power law dependence, while in non-ionic samples it is attributed to the hopping
of electron within the impurity band between occupied and unoccupied donor
sites [5]. We can see the resemblance of our experimental results with the above
theories later.
90
5.3. DIELECTRIC RESPONSE
5.3 Dielectric response
The dielectric measurements as function of frequency for different temperatures

is shown in Fig.5.4 and Fig.5.5. At 100kHz, the room temperature dielectric
constant ( ) was found to be around 23.5 with a dissipation factor of 0.03. There
90
80
T= 30
70 T= 60
T= 75
60
T= 100
T= 125
50 T= 150
T= 175
T= 200
40
T= 225
ε'
T= 250
T= 275
30 T= 300
20
2 3 4 5
10 10 10 10
Frequency (Hz)
Figure 5.4: Plot of the real part of dielectric constant as a function of frequency
at various temperatures.
was a gradual decrease in the dielectric constant with frequency. It dropped by
91
19% of its initial value in a frequency interval of 100Hz to 100kHz. At high

I
frequencies the value of decreased with temperature while a cross over was
I
observed, where the values of at lower frequencies were found to increase with
I
temperature. The decrease of with temperature at high frequencies was obvious.
T= 125
T= 150
100 T = 175
T= 200
T= 225
T= 250
T= 275
T= 300
10
ε''
0.1
2 3 4 5
10 10 10 10
Frequency(Hz)
Figure 5.5: Plot of dielectric loss ( ) as a function of frequency at various tem-

peratures.
It was also seen that, there was a sudden drop in the dielectric constant at a
frequency range of 100Hz − 10kHz, at temperatures above 200◦ C. The slope of
92
the ‘ Vs ω’ curve at the range of frequency 100Hz − 10kHz was found to be

0.24, and was almost constant at all temperatures.
80 0.1K
1K
10K
100K
70
60
ε'
50
40
30
20
0 50 100 150 200 250 300
0
Temp( C)
Figure 5.6: Plot of the real part of dielectric constant as a function of temperature
at various frequencies.
However the frequency at which this was found, increased with increasing tem-
perature. This type of behavior could be indicated either pure ’Debye’ type or
’Maxwell- Wagner’ relaxation, where this type of sudden decrease in ‘ ’ while
increasing the frequency. But the slopes of the ‘ Vs ω’ and also the ‘ Vs ω’
93
ruled out the possibilities of a pure ‘Debye’ character.
The low frequency dispersion observed in the dielectric constant, was most proba-
bly due to the low frequency space charge accumulation effect. The phenomenon
of the dispersion in the dielectric constant, which was increased with increas-
2.0
100
125
150
175
200
1.5 225
250
275
300
1.0
tanδ
0.5
0.0
2 3 4 5
10 10 10 10
frequency (Hz)
Figure 5.7: Dissipation factor as a function of frequency in BZ thin films.
ing temperature and extended to higher frequency region had been explained by
considering the hopping of electronic charges present in the sample [10], [11].
94
There are some reports that some ionic compounds do exhibit the low frequency
dispersion, which proved that mobile ions could also result in the same type of
frequency dependence [12].
The comparison of Figs.5.4 and 5.5 with Fig.5.1 ruled out the possibilities of pure
‘Debye’ character and at the same time the comparison of Figs.5.4 and 5.5 with
Fig. 5.2 ruled out the possibilities of pure ‘Maxwell- Wagner’ characteristics.
2.0 0.1k
1k
10k
100k
1.5
1.0
tanδ
0.5
0.0
0 50 100 150 200 250 300

0
Temperature( C)
Figure 5.8: T anδ vs.temperature in BZ thin films.
95
In fact, the dispersion was found to be consistent with the universal power law
relation given by Jonscher (Equ.5.3), which was derived from the many body
interaction model [5]. The frequency dispersion in the imaginary component was
0.9
Experimental data
Linear fit
0.8
0.7
n(T)
0.6
0.5
0.4
0 50 100 150 200
0
T ( C)
Figure 5.9: Plot of n(T) as a function of temperature calculated from the theo-
retical fits of the experimental data.
found to increase with increase in temperature and consequently led to a linear

region in the log-log plot. The strong dependence of the dissipation factor on
the frequency at high temperatures as like in Fig.5.7 suggested an influence of dc
96
II
conductivity on .
The real part of dielectric constant decreased with increasing temperature in

the low frequency region and it was found to increase with the temperature in
the high temperature region as in Fig.5.6. This suggested that an extrinsic effect
such as charge carrier contribution has been responsible for the observed dielectric
response.
Experimental data
Linear fit
1E-6
a(T)
1E-7
1E-8
0 50 100 150 200 250
0
T ( C)
Figure 5.10: Plot of a(T) as a function of temperature calculated from the theo-
retical fits of the experimental data.
97
The verification of Jonscher’s model was done by a successful fitting of the ex-
perimental dielectric data to the dielectric dispersion relation given in Eq.5.6 and
Eq.5.7.
The parameters n(T) and a(T) calculated from the theoretical fittings have been
plotted as a function of temperature and is given in Fig.5.9 and Fig.5.10. The
thermal energy of the system increases with increase in temperature causes in-
creasing the disorder. The parameter n(T) determined the correlation between
individual dielectric transitions in the many- body interaction model as proposed
by Jonscher[5].
It was expected to decrease, which was in agreement to that observed from Fig.5.9.
This predicted that we would arrive at a much more uncorrelated system at higher
temperatures. An increase in the value of a(T) by increasing temperature sug-
gested an increasing contribution of the charge-carrier term in Eq.5.7 and conse-
quently led to a higher dispersive character, which was observed in Fig.5.5. At
lower frequencies and higher temperatures, the dc conductivity term dominated
and gave a slope of -0.59, which was indeed consistent with the data shown in
Fig.5.10.
5.3.1 Dielectric impedance spectroscopy
To analyze the ac response of polycrystalline materials one can use the complex
impedance and complex electric modulus formalisms. This has been discussed by
Almond et. al[13]. The advantage of the complex electric modulus formalism is to
discriminate against high capacitance namely grain boundary/electrode interfaces
and highlight the bulk effects. In polycrystalline materials it was shown that
98
Z ∝ R and M ∝ 1c . The impedance formalism with frequency might emphasize

inter granular conduction process and the electric modulus formalism would be
dominated by the bulk grain effect.The Fig. 5.12 show the complex impedance
(Cole-Cole) plot for the BZ films measured at different temperatures. Fig.5.11 and
7
2.0x10
T= 125
T= 150
T= 175
7 T= 200
1.5x10
T= 225
T= 250
T= 275
T= 300
7
1.0x10
Z (Ω )
''
6
5.0x10
0.0
2 3 4 5
10 10 10 10
Frequency (Hz)
Figure 5.11: The imaginary part of the modulus Z plotted as a function of

frequency for different temperatures.
Fig.5.13 show the variation of Z and M with frequency at various temperatures

for BZ thin films (700 nm thick).The fig.5.13 is found to show peaks at different
99
frequencies with variations in temperature.
Further the peak maxima were found to shift towards the towards the high fre-
quency side with increasing temperature. This relate the response to a single
RC combination, which in this case has been attributed to the bulk. The effects
of other components, such as the grain boundary interface and electrode/film
interface was negligible.
7
2.0x10
7
1.5x10
7
Z (Ω )
1.0x10
''
T= 125
T= 150
T= 175
6
5.0x10 T= 200
T= 225
T= 250
T= 275
T= 300
0.0
0 6
1x10
6
2x10 3x10
6 6
4x10
6
5x10
'
Z (Ω )
Figure 5.12: Complex impedance plane plot of BZ thin films.
100
The whole contribution of the dielectric characteristics to be confined to the film

bulk and its intrinsic behavior. The time domain measurements obtained by
Waser[14] also suggested results, which could only be related to the bulk and
hence showed no effect of the type of electrode on the film. The peak frequencies
were not coincident from Z Vs frequency and M Vs frequency denoting non-
Debye type relaxation phenomenon.
-5
1.5x10
0
T= 125 C
0
T= 150 C
0
T= 175 C
0
T= 200 C
0
T= 225 C
0
T= 250 C
0
-5
T= 275 C
1.0x10 0
T= 300 C
M''
-6
5.0x10
0.0
2 3 4 5
10 10 10 10
Frequency (Hz)
Figure 5.13: The imaginary part of the modulus M plotted as a function of

frequency for different temperatures.
101
In general, even in single crystal, the location Z and M peaks will not be
found at the same frequencies. This has led to the hypothesis of distribution of
relaxation times and uncertainty about the physical interpretation of the peak
frequency. The probable interpretation for such asymmetric behavior in real
materials largely determined by the Jonscher’s power law [5].
5.3.2 AC Conductivity
For the better understanding of electrical charge transport behavior in pulsed

laser ablated BZ thin films, the frequency and the temperature dependence of the
ac conductivity was investigated. AC conduction in dielectric materials always
has a subject of interest due to its universality.
The universal behavior has been found to follow the power law governed by
the Eqn.5.13. Fig.5.14 shows the ac conductivity of the BZ thin films. The
ac conductivity measured at low frequencies and higher temperatures had less
dependence on the frequency. The results has given the validity of the power law
in the case of BZ thin films.
102
T= 100
T=150
T= 175
-7
T= 200
10 T= 225
T= 250
T= 275
T= 300
-8
10
-1
σ ac (Ω .cm)
-9
10
-10
10
2 3 4 5
10 10 10 10
Frequency(Hz)
Figure 5.14: AC conductivity as a function of frequency for BZ thin films.
Fig.5.15 and Fig.5.16 show the AC conductivity as a function of the absolute

1000
temperature for different frequencies. The slope of the plot of n(σ) Vs T
ap-
parently gave the value of the activation energy (Ea ) for the mechanism where T
was the absolute temperature.
103
-7
10
100kHz
10
-8 10kHz
LnσT(ω) (S.cm )
-1
-9
1kHz
10
0.1kHz
-10
10
1.5 2.0 2.5 3.0 3.5
-1
1000/T (K )
1000
Figure 5.15: AC conductivity vs. T
in BZ thin films.
The value of the slope calculated at higher temperature side was around 1.8eV .
In this case the conduction process was dominated by the grain boundary inter-
face. Hence the increase in the value of activation energy reflecting the effect of
grain boundary interface, in increasing the barrier for charge transfer. The oxy-
gen vacancy mobility might be significant at high temperatures. The obtained
activation energy in the high temperature region can be responsibility of the
motion of oxygen vacancies. It was observed that grain boundary act as back
104
to back Schottky barriers impeding the motion of charges leading to a higher

value of activation energy in the range of 1.62eV by Vollmann et al. [15], [16]
On the other hand, activation energies calculated in the lower temperature re-
gion reflected lower values around 0.34eV , exhibiting a probable difference in the
conduction process.
1E-7
100kHz
1E-8 10kHz
LnσT(ω) (S.cm )
-1
1kHz
1.8
1E-9
3
eV
0.1kHz
1E-10
2.0 2.5 3.0 3.5

-1
1000/T (K )
1000
Figure 5.16: AC conductivity vs. T
with the calculation of activation energy
in BZ thin films.
105
5.3.3 Summary
The dielectric response of BZ thin films were studied in the frequency domain. In
this study, starting from microstructure and relating it to the electrical charac-
teristics, the pulsed laser ablated BZ thin films showed consistency in properties.
The following conclusions may be drawn from the above analysis:
1. Dielectric response of the BZ thin films was ruled out the possibilities of pure
Debye and Maxwell-Wagner type polarization. It was found to obey Jonscher’s
Universal law and it was showing low frequency dispersion in and . The dis-
persion was found to increase with increasing temperature. The phenomenon was
related to the charge-carrier contribution, which was dominant at low frequencies
and high temperature.
2. The dc conductivity σdc was found to dominate at high temperatures leading
to a high degree of dispersion in . The slope of log-log plot of Vs. frequency
was found to be around 1 at high temperatures indicating the domination of dc
conduction.
3. The numerical fit of the obtained data using Jonscher’s equation was used
to obtain values of the parameters n(T) and a(T), which showed variation with
temperature. The parameter n(T) determined the correlation between dielectric
transitions in the many body interaction model which was proposed by Jon-
scher.It was found to decrease with increase in temperature, signifying a decrease
in the correlation between each individual transition. The increase of a(T) with
temperature suggested an increasing influence of charge carriers.
4. Complex impedance spectroscopy was used to analyze the complex modulus
and complex impedance of the BZ thin films. Analysis showed a representative
analogous circuit consisting of single RC of bulk connected in parallel.
106
5. The ac conductivity Vs frequency plots showed power law dependency. The

1000
ac conductivity Vs T
showed that at low frequency and high temperatures had
1000
a linear dependence of the Arrhenius plot with T
with the activation energy in
the range of 1.83eV . At low temperatures and high frequencies the temperature
dependence of log(σac ) was much reduced giving a lower value of activation en-
ergy around 0.34eV .
6. The high temperature dc conduction contribution has been attributed to oxy-
gen vacancy motion .
The above conclusions have been drawn from a step by step analysis of the ob-
served features in the obtained dielectric response of the pulsed laser ablated BZ
thin films and where consistent with each other.
107
References
[1] D. C. Sinclair and A. R. West, J. Appl. Phys., 66, 3850, (1989).
[2] P.Debye in ‘Polar Molecules’, Dover Publications, (1945).
[3] A. K. Jonscher, Nature 267, 673 (1977).
[4] A. K. Jonscher, Nature 253, 231 (1977).
[5] A. K. Jonscher, Dielectric Relaxation of Solids, (Chelsea Dielectric Press,

London, 1983).
[6] A. K. Jonscher, Phys. Stat. Sol.(B) 83, 585, (1977).
[7] A. K. Jonscher, Phys. Stat. Sol.(B) 84, 159, (1977).
[8] D. C. Sinclair and A. R. West, J. Appl. Phys. 66, 3850 (1989).
[9] D. C. Sinclair and A. R. West, J. Mater. Sci. 29, 6061 (1994).
[10] M. Pollak and T. H. Geballe, Phys. Rev., 122, 1742, (1961).
[11] Abhai Mansingh, Bull. Mater. Sci., 2, 325, (1980).
[12] P. Doerenbos, H. W. den Haetog, R. Kruizinga and S. Vrind, Phys. Rev.

B, 35, 5774, (1987).
108
REFERENCES
[13] D. P. Almond and A. R. West, Solid State Ionics. 11, 57, (1983).
[14] R. Waser, Science and technology of Electroceramic Thin films, edited by O.

Auciello R. Waser (Nato Asi Series, Kluwer Academic Publishers, Nether-
lands, 1995), p.223.
[15] M. Vollmann and R. Waser, J. Amer. Ceram. Soc. 77, 235 (1994).
[16] M. Vollmann, R. Hagenbeck, R. Waser, J. Amer. Ceram. Soc. 80, 3301

(1997).
109
Chapter 6
DC Electrical Properties
6.1 Introduction
The dc leakage current study is essential for the microwave dielectric thin films
as they degrade the device with higher leakage current. The films give interest-
ing electrical properties when subjected to both low and high field regime. A
prior knowledge of the conduction mechanism guides a technologist to tailor the
property of a device according to the desired performance.
6.2 High Field Phenomenon
6.2.1 Schottky conduction process
The Schottky conduction process means the thermionic emission of electrons from
the cathode in to the insulator. For insulator it has been found to be analogous
110
6.2. HIGH FIELD PHENOMENON
to thermionic emission of electrons from a metal into a vacuum. The potential

difference set up at the cathode- insulator interface due to the difference in their
work functions determine the emission rate. This type of potential barrier is set
up when the work function of the metal is higher than that of the insulator [1, 2].
The emission rate of electrons from the cathode in to the insulator depends on
temperature and the external voltage applied between them. By an escaping
electron from the metal surfaces, the surface becoming polarized and it leads to
an attractive force on the electron which is called as image force [3]. Due to the
presence of image force the net potential difference between the electrode and the
insulator would decrease [3], and this is called as the image force lowering of the
barrier [4]. The current voltage relationship of a Schottky barrier is given by the
Richardson-Schottky law as given below.
φ0 − ∆φ
J = AT 2 exp(− ) (6.1)
κT
where, ‘J’ is the current density, ‘A’ is the Richardson constant, ‘φ0 ’ is the inter-
face potential without the presence of any excess charge on the surface, ‘∆φ’ is
the lowering of the interface potential due to the image force, ‘κ’ is the Boltzmann
constant and ‘T’ is the absolute temperature.
The Richardson constant is given by the following equation,
4πem(κT )2
A= (6.2)
h2
where, ‘e’ is the charge of electron, ‘m’ is mass of electron and ‘h’ is the Planck’s
constant. The value of A takes 120 when J expressed in Acm−2 [4].
111
CHAPTER 6. DC ELECTRICAL PROPERTIES
The expression for ∆φ is given by,
e3 1 1 1
∆φ = ( ) 2E2 ≡ β E2 (6.3)
s
4πK ∗ 0
where, ‘K ∗ ’ is the high frequency dielectric constant and ‘E’ is the applied electric
field.
The eqn.6.1 and 6.3 gives the following relation,
1
2 φ0 βs E 2
J = AT exp(− )exp( ) (6.4)
κT κT
According to Schottky, the current at any given temperature increases exponen-

tially with the square root of the voltage instead of saturate at the Richardson
current. One of the verification for Schottky emission is a linear dependance of
1 βs
lnJ on E 2 . The slope of the straight line should be equal to κT
and from this we
can calculate the high frequency dielectric constant (K ∗ ), which should fit well
with the experimental results. The one more verification of Schottky emission
would be to calculate the activation energy. The plot between ln( TJ2 ) vs. 1000
T
should be of linear nature and its slope should give the value of the activation
energy. The net activation energy would be given by the following eqn.
e3 1 1
∆E = φ0 − ∆φ ≡ φ0 − ( ) 2E2 (6.5)
4πK ∗ 0
From this equation one can get the value of the interfacial potential (φ0 ) at zero
bias and the net activation energy should decline with hike in applied electric
field.
112
6.2.2 Poole-Frenkel conduction process
The Poole-Frenkel effect is lowering of a coulombic potential barrier when it

interacts with an electric field [4]. This process is the bulk analog of the Schottky
effect at an interfacial barrier. The current density in this case is given by:
1
βP F E 2
J = J0 exp( ) (6.6)
κT
where, ‘J0 ’ is the low field current density. In Poole-Frenkel conduction the plots
1
of ln( EJ ) vs. E 2 at constant temperature and ln( EJ ) vs. 1
T
at constant electric
field would be linear if it’s the dominating conduction mechanism [5], [6].
6.2.3 Tunnel Effect
If the barrier (sample) between the electrodes is very thin (< 50Å), the wave
function has a nonzero value at the opposite interface. In this case, there is a
finite probability that the electron can pass from one electrode to the other by
penetrating the barrier. When the electron passes from one electrode to the other
electrode by this process is called as tunneling.
The generalized formula gives the relationship connecting the tunnel current den-
sity with the applied voltage for a barrier of arbitrary shape as [4]
2 1
I = I0 { φexp(−Aφ ) − ( φ + eV )exp[−A( φ + eV ) 2 ]} (6.7)
where,
4πβ∆L 1
A= (2m) 2
h
113
and
e
I0 =
2πh(β∆L)2
∆L= width of the barrier at the Fermi level at the negatively biased electrode.
φ= the average height of the barrier from the Fermi level at the negatively biased
electrode.
h= Plank’s constant.
m= mass of the electrons.
e= charge of an electron.
β= a function of barrier shape and is usually approximated to unity.
The above equation is valid at T = 0K. The generalized formula connecting the
tunnel current J(V, T ) at T = 0K to the tunnel current J(V, 0) at 0K is given by
J(V, T ) πBκT
= (6.8)
J(V, 0) sin(πBκT )
A
where, B = 1
2φ 2
6.2.4 Space charge limited conduction process
Space charge limited conduction (SCLC) in thin films was observed if the elec-
trode contacts showed ohmic in the conduction properties. The electrons would
diffuse from metal into the insulator while they are in contact if the work function
of the metal is lower than that of the insulator [4]. This would build up a space
114
charge layer adjacent to the interface. This layer would act as source of charge
that is necessary to sustain the steady state current flow. In the other side, the
anode would also drain out some amount of charges. For highly insulating sample
and a highly injecting contact, there would be an accumulation of charges in the
sample. This would lead a steady state saturation condition, in which sample
would possess a net charge. The amount of charge stored in the sample would be
given by:
Q = CV (6.9)
where, ‘Q’ is the charge stored in the sample, ‘C’ is the capacitance of the sample
and ‘V’ is the voltage applied across the two electrodes. The motion of these
charges (space charge controlled current) would be given by [7]:
Q CV µE CµV 2
J = ( ).υdrif t = = (6.10)
L L L2
where, ‘µ’ is the carrier mobility.
The capacitance of such a system would be different from the geometric capac-
itance because the actual charge distribution inside the sample would be within
half of the thickness of the sample, and the real expression would be:
9 µV 2
J= (6.11)
8L3
The eqn.6.11 is called as the space charge controlled current equation.
Actually in real material there would be the traps distributed within the forbidden
gap of the solid. If the insulator contain traps, a large fraction of the injection
space charge will condense therein, which means the free carrier density will be
115
much lower than in a perfect one. Since the number of traps are finite, the traps
get filled completely with the injected electrons at certain voltage called as trap
filled limit voltage (TFLV). Beyond the TFL voltage, any further extra injected
charge would appear in the conduction band without getting trapped. So, the
current would follow the trap free square law given by the space charge equation
directly from the linear region. According to Lampert [8], there should be a
triangle formed by the linear region, the trap filled limit and the trap free square
law. This triangle is called as Lampert triangle.
At low temperature, only the lowest energy states would be occupied, and most
of the higher energy levels would be empty. At high temperatures, those energy
levels also would be significantly populated, and the trap filling would occur over
a range of voltages rather than at a fixed voltage. The voltage VT F L at which the
TFL occurs would be given as below [8]:
eNt L
VT F L = (6.12)
2
where, ‘L’ is the thickness of the films and ‘Nt ’ is the total deep trap concentration.
The traps located above the Fermi level are called as the shallow traps. The trap
levels would be approximately given by Maxwell-Boltzmann statistics, and the
shallow trap controlled current would be given by the following equation:
9µ θV 2
J= (6.13)
8L3
where, the value of ‘θ’ would be given by:
116
Nc Et − Ec
θ= exp(− ) (6.14)
gNt κT
where, ‘Nc ’ is the number of states in the conduction band, ‘Nt ’ is the total
number of the shallow trap level, ‘g’ is a degeneracy factor, ‘Et ’ is the energy of
the traps in the energy band, ‘Ec ’ is the energy of the bottom of the conduction
band, ‘κ’ is the Boltzmann constant, and ‘T’ is the absolute temperature in
Kelvin.
In amorphous or polycrystalline structures, which are characteristic of thin films

insulators, a distribution of trap level is to be expected, rather than a discrete level
of traps. Rose [9] has treated the space charge limit conduction in the presence of
a distribution of trap levels that decreases as a function of exponential in density
with increasing energy below the conduction band and is given by:
E
Nt = Aexp(− ) (6.15)
κTc
where ‘E’ is the energy measured from the bottom of the conduction band, and
‘Tc ’ is the characteristic temperature greater than the temperature at which the
currents are measured.
117
6.3 Analysis of experimental results
6.3.1 comparison with the Schottky conduction mecha-

nism
The result of the I-V measurements on a BZ thin films at various temperatures is

shown in Fig.6.3. The plot ln(J/T 2 Vs. E 1/2 ) is to give a straight line instead it
wasn’t (fig.6.1) and the dielectric constant calculated from the Schottky equation
did not match with high frequency dielectric constant. The activation energy
was comparable to the Schottky potential barrier at the interface [10]. The other
features except than activation energy were contradictory to the Schottky theory.
According to the Schottky theory the current should always have to increase
exponentially with square root of the applied voltage. Schottky emission is an
electrode limited phenomenon, it shouldn’t reflect any bulk like characteristics.
1
For the further check for the Schottky conduction, we have plotted ln(J) ∼ E 2 ,
which has been shown in fig.6.2.
The possibilities of the conduction mechanism governed by Schottky theory was

ruled out. The Schottky emission might be present in the sample, but that might
have been screened by some bulk mechanism.
The Poole-Frenkel conduction would have the similar characteristics in the I-V
plot to the Schottky emission and is bulk limited phenomenon. Using fig.6.6 the
calculated dielectric constant didn’t match with the BaZrO3 bulk value.
118
6.3. ANALYSIS OF EXPERIMENTAL RESULTS
4.13994E-8
2.78947E-10
ln(J/T )
2
1.87953E-12
0 2
1x10
2
2x10
2
3x10
2
4x10
2
5x10
1/2
E
Figure 6.1: The ln(J/T 2 ) vs. E 1/2 plot for room temperature.
6.3.2 Comparison with the Space charge controlled con-

duction mechanism
The I-V characteristics of the observed results from the BZ thin films were obeyed
to the Space charge conduction mechanism after incorporating a certain number
of corrections.
119
0
2 T= 125 C
10 0
T= 150 C
0
T= 175 C
0
T= 200 C
-2
10
lnJ (A/cm )
2
-6
10
-10
10
0.0 2
2.0x10 4.0x10
2 2
6.0x10
2
8.0x10
1/2 1/2
E [(V/cm) ]
1
Figure 6.2: The ln(J) ∼ E 2 plot at different temperatures.
120
Low field region
In the low field region, the number density of the excess injected charges would
be very small compared to the already existing bulk charge carriers. At the time
of this situation, the excess charge carriers are completely masked by the bulk
generated charge carriers, and there would not be any effect of the excess injected
charges in the interior of the sample.
1E-4
0
T= 100 C
0
T= 125 C
1E-5 0
T= 150 C
0
T= 175 C
0
T= 200 C
1E-6
1E-7
Current (amp)
1E-8
1E-9
1E-10
1E-11
1 10
voltage (V)
Figure 6.3: The I ∼ V curves of a BZ thin films at different temperatures.
121
0.1
1E-3
1E-5
logJ
0
2.
7.1
1E-7
8
0.9
1E-9
0.1 1 10
logV
Figure 6.4: The Lampert triangle in the J-V plot at room temperature. The
slopes of the three arms of the triangle are indicated.
This is called as Ohmic relaxation [11], and in the low field region, the transit
time of the charges is longer than the Ohmic relaxation time[12], so that the
effect of any excess charge in the sample would get completely masked within
few nanometer distance from the charge. At higher applied fields, the number of
ejected charge increases and the current would be controlled by the field produced
by these excess charges, called space charges.
Beyond the crossover voltage, where the linear to space charge controlled region
occurs, the current should follow the square law dependence of voltage [7]. In our
samples, the situation was far different from the inherent assumption
122
1E-7
2.6
ln(J) (A/cm )
2e
2
0.28 eV
1E-8
2.0 2.2 2.4 2.6 2.8
1000/T (1/K)
Figure 6.5: The Arhenious plot of the high field conductivity of the BZ thin films.
made in the eqn.6.10. In the space charge equation, the effect of traps had been
neglected, which is inevitable in any sample. The trap distribution of electrons
among the trap levels would follow the eqn.6.15. Lampert [8], has described the
effect of traps on the space charge conduction within insulators. According to
Lampert, there should be a triangle called as Lampert triangle formed by the
linear region, the trap filled limit and the trap free square law as shown in fig.6.4.
The slopes of the three regions are 0.98, 7.1 and 2 respectively. The trap filled
123
limit was seen to exhibit a very dramatic increase in current, as was explained
by Lampert. However, the trap filled limit became more smoothened at higher
temperatures. The smoothening of the trap filled limit could be associated with
the distribution of traps.
Trap filled voltage
16
12
VTFL (V)
50 100 150 200

0
Temperature ( C)
Figure 6.6: The variation of VT F L with temperatures.
124
In our sample, the trap free voltage at room temperature was seen to be 3.2
Volts, and it has increased upto 125◦ C as shown in fig.6.6. But above 125◦ C till
200◦ C, the decreasing trend was more prominent. According to the pure space
charge law, the trap filled voltage should have increased with temperature. The
decrease in VT F L was not predicted from the equilibrium distribution of electrons.
At high temperature, there must have been some additional source of electrons
that could fill all deep traps at a lower voltage. These electrons were only available
at higher temperatures and too the capturing of electrons in the deep trap sites
might be a rate limited process, so that, at lower temperatures, the trapping was
not completed. At higher temperatures, the trapping rate also increased, so that
even at a lower voltage, the trapping of electrons were completed, and VT F L was
decreased. At still higher temperatures, there was a saturating trend observed in
VT F L , which indicated that the equilibrium state was approached gradually. The
arhenious plot of the high field conductivity has been shown in fig.6.5. It was
seen that the activation energy was having a value of 2.62 eV at 1.5 Volt.
6.3.3 Conclusions
1) The BZ thin films exhibited a space charge limited dc leakage current.

2) The oxygen vacancy motion is usual in oxides thin films.
3) The onset of (VT F L ) of trapped filled limited region in the I − V curves showed
increasing trend upto 125◦ C and decreasing trend in the temperature region above
125◦ C. This unusual behavior of VT F L was explained by considering the dynam-
ical equilibrium between the thermally generated and injected charge carriers.
125
References
[1] W. Schottky, Z. Physik, 113, 367 (1939).
[2] H. K. Henisch, ”Rectifying Semiconductor contacts,” Oxford University

Press, Fair Lawn, N.J. (1957).
[3] W. Schottky, Z. Physik, 15, 872 (1914).
[4] J. G. Simmons in ”Hand book of thin films”, edited by L. Meissel and R.

Glang, McGraw Hill, 1970.
[5] J. Frenkel, Phy. Rev. 54, 647 (1938).
[6] J. G. Simmons, Phy. Rev. 155, 657 (1967).
[7] N. F. Mott and R. W. Gurney, in ’Electronic Processes in Ionic Crystals’,

2nd ed., chap.V, Oxford University Press, Flair Lawn, N. J. 1948.
[8] M. A. Lampert in ’Current Injection in Solids’, Academic Press. 1971.
[9] Rose. A., Phys. Rev., 97, 1538 (1955).
[10] C. A. Mead in ’Basic Problems in Thin Film Physics’, edited by R. Niede-

mayer and H. Mayer, p674, Vandenhoec and Ruprecht, Goettingen (1966).
126
REFERENCES
[11] R. H. Bube in ’Electons in solids’, Academic Press (1992).
[12] K.C. Kao and W. Hwang in ’Electrical Transport in Solids’, Pergamon

Press(1981).
127
Chapter 7
Summary and Future Work
7.1 Summary
Thin films of barium zirconate (BaZrO3 ) were grown by pulsed laser deposition
(PLD) technique . The films showed reproducible structural as well as electri-
cal properties. The stochimetric of the deposited films were same as the target
used for the ablation. The processing parameters such as substrate temperature,
deposition pressure, annealing temperature, annealing time were correlated with
structure and electrical properties of the BZ thin films. Two kinds of films were
grown, one at lower substrate temperature and subsequently annealed (ex-situ )
at higher temperatures, and the other one was grown directly at higher substrate
temperatures (in-situ). Both in-situ and the ex-situ grown films had the ten-
dency to enhance the perovskite phase at higher temperatures and there were no
secondary phases observed. The effect of the processing parameters such as an-
nealing temperature, annealing time, deposition pressure over the grain size and
128
7.1. SUMMARY
the stress along the (110) direction of the ex-situ BZ thin films has been discussed.
The cross sectional Scanning Electron microscopy (SEM) pictures revealed that
the in-situ and ex-situ grown films had multi grain structures.
Secondary Ion Mass spectroscopy (SIMS) analysis has given a complete coverage
about the interface of the BZ thin films with higher resolution in the order of
nanometer. A very sharp interface has been observed in the in-situ annealed BZ
thin films and there was no diffusion of platinum electrode in to the film, whereas
the interdiffusion of film and the platinum has been observed in ex-situ grown thin
films. The segregation of zirconium oxide has been observed in the interface of
ex-situ annealed BZ thin films and which has also dissociated on higher annealing
temperatures. The diffusion of platinum into the film has caused an increase of
leakage current in the ex-situ annealed thin films. The diffusion length of the
platinum into the film was found to be higher at higher annealing temperatures.
The diffusion curve which follows a Gaussian nature is not a perfect Gaussian in
the case of interdiffusion of BZ thin films and the tail of the Gaussian is dominated
by pinholes.
The dielectric constant( ) and the dielectric losses (tanδ) were measured upto
the frequency of 100kHz at different temperatures. Both the dielectric constant
( ) and the dielectric losses (tanδ) exhibited gradual decrease with increasing
temperature. At 100kHz the room temperature dielectric constant was found to
be 23.5 with a dissipation factor 0.02. The dielectric response obeyed the universal
law. The dc conductivity was found to dominate at higher temperatures leading
to the dispersion in dielectric loss in that region. The complex modulus and
complex impedance studies revealed the presence of single parallel RC equivalent
circuit. The Arrhenius plot of ac conductivity with temperature has given the
129
CHAPTER 7. SUMMARY AND FUTURE WORK
activation energy of 1.83 eV at low frequency and high temperatures.
Films of BZ exhibited a space charge limited dc leakage current. The linearity

in the I-V plot was observed in the low voltage region. The onset voltage (VT F L )
of trapped filled limited region in the I-V curve showed an increasing and de-
creasing trend with temperature. This unusual behavior of VT F L was explained
by considering the dynamical equilibrium between the thermally generated and
injected charge carriers.
7.2 Future work
The present study gave us some basic ideas about the film growth process and
optimization. The studies of electrical properties (ac and dc) gave us the overall
understanding of charge transport processes in the BZ thin films at different
working temperatures. Study of interfacial properties through Secondary ion
Mass Spectroscopy (SIMS) gave us clear informations about the interface with
different process parameters. However, there are certain issues that need for the
better understanding of the structural and electrical properties as well as the
interfacial characteristics to make the material upto the end product. The future
work are to be extended in the following directions:
1. The ac electrical studies can be extended into the microwave frequency regime
to understand the material behavior.
2. The BZ thin films could be grown on different substrates and the substrate
with different orientations to correlate structure with the electrical properties.
The cross sectional TEM and the glancing angle XRD studies could be useful to
get more informations about the substrate and the film orientation.
130
7.2. FUTURE WORK
3. The diffusion studies through SIMS could be done on the epitaxial BZ thin
films and correlate with the leakage current behavior, for the better understanding
of the leakage current mechanism.
4. Correlating the cross sectional TEM and the SIMS profile results can lead to
a better understanding of growth process, as well as defect chemistry.
5. Studies related to the formation and mobility of protonic charge carriers will
be useful in proton conductors.
6. The usage of different metal and conducting oxide electrodes can enhance the
device performance.
131

MSthesis Raja July2002

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GROWTH AND CHARACTERIZATION OF BaZrO 3

THIN FILMS FOR MICROWAVE COMMUNICATION

MATERIALS RESEARCH CENTER

Mr. D. Vadapoo & Mrs. S. Selvam Lashmi

Chapter 1 is an introduction to BaZrO3 thin films. The necessary properties

Chapter 2 describes the experimental procedure involved in the growth and

Chapter 5 describes the ac electrical properties of BZ thin films in detail. The

Chapter 6 describes the dc electrical properties of the BZ thin films in detail.

It is with profound gratitude that I acknowledge my research mentor, Prof. S.

It is with heart felt thankfulness that I acknowledge my department Chairman

I am thankful to my departmental staﬀs Mrs. Tharakeswari, Mrs. Indiara, Mr.

friends brings peace of my conscious mind to my subconscious mind too, al-

I owe multiple life times for my parents. My mother is an embodimentment

1.1 What is the driving force? . . . . . . . . . . . . . . . . . . . . . . 1

1.2 Microwave passive components . . . . . . . . . . . . . . . . . . . . 1

1.3 Material requirements for microwave dielectrics . . . . . . . . . . 2

1.5 Dielectric resonator materials . . . . . . . . . . . . . . . . . . . . 2

1.6 Issues involved in BZ integration . . . . . . . . . . . . . . . . . . 3

1.7 Processing of BZ thin films . . . . . . . . . . . . . . . . . . . . . . 5

2.1 Laser Setup . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 10

2.2 The excimer Laser source . . . . . . . . . . . . . . . . . . . . . . . 13

2.2.2 Excimer discharge design . . . . . . . . . . . . . . . . . . . 15

2.2.3 Beam characteristics . . . . . . . . . . . . . . . . . . . . . 15

2.3 Target preparation . . . . . . . . . . . . . . . . . . . . . . . . . . 17

2.4 The substrate . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 20

2.5 Deposition conditions . . . . . . . . . . . . . . . . . . . . . . . . . 20

2.6 physical characterization . . . . . . . . . . . . . . . . . . . . . . . 22

2.6.1 Structural analysis . . . . . . . . . . . . . . . . . . . . . . 22

2.6.2 Composition analysis . . . . . . . . . . . . . . . . . . . . . 22

2.6.3 Thickness measurement . . . . . . . . . . . . . . . . . . . 24

2.6.4 Micro structure and surface morphology . . . . . . . . . . 25

2.7 Interface Analysis . . . . . . . . . . . . . . . . . . . . . . . . . . . 26

2.8 Electrical Characterization . . . . . . . . . . . . . . . . . . . . . . 26

2.8.1 Dielectric Properties . . . . . . . . . . . . . . . . . . . . . 27

3 Growth and Structural Characterization 29

3.2 Crystallographic Structural Characterization . . . . . . . . . . . . 30

3.2.1 In-situ crystallization . . . . . . . . . . . . . . . . . . . . . 30

3.2.2 Ex-situ crystallization . . . . . . . . . . . . . . . . . . . . 30

3.2.3 Eﬀect on Grain Size . . . . . . . . . . . . . . . . . . . . . 35

3.2.4 Eﬀect on stress . . . . . . . . . . . . . . . . . . . . . . . . 37

3.3 Microstructural Analysis . . . . . . . . . . . . . . . . . . . . . . . 39

3.3.1 In-situ crystallization . . . . . . . . . . . . . . . . . . . . . 39

3.3.2 Ex-situ crystallization . . . . . . . . . . . . . . . . . . . . 39

3.4 Compositional Analysis . . . . . . . . . . . . . . . . . . . . . . . . 42

4 Secondary Ion Mass Spectrometry (SIMS) Analysis 45

4.2 Elements of SIMS . . . . . . . . . . . . . . . . . . . . . . . . . . 47

4.4 Forms of practical SIMS . . . . . . . . . . . . . . . . . . . . . . . 49

4.4.1 Static SIMS (S-SIMS) . . . . . . . . . . . . . . . . . . . . 49

4.4.2 Dynamic SIMS (D-SIMS) . . . . . . . . . . . . . . . . . . 49

4.4.3 Bulk contamination/ composition studies . . . . . . . . . . 50

4.5.1 General background . . . . . . . . . . . . . . . . . . . . . 51

4.5.2 Total yield systematics and linear cascade predictions . . . 51

4.5.3 Multicomponent materials . . . . . . . . . . . . . . . . . . 52

4.6 Basic characteristics of SIMS . . . . . . . . . . . . . . . . . . . . . 54

4.6.1 Sensitivity and quantification . . . . . . . . . . . . . . . . 54

4.6.2 Mass interferences . . . . . . . . . . . . . . . . . . . . . . 56

4.6.3 Pre-equilibrium eﬀects . . . . . . . . . . . . . . . . . . . . 58

4.6.4 Detection/resolution limits and ion bombardment induced

4.6.5 Charging Problem . . . . . . . . . . . . . . . . . . . . . . 60

4.7 Quantification of depth profiles . . . . . . . . . . . . . . . . . . . 64

4.7.1 General remarks . . . . . . . . . . . . . . . . . . . . . . . 64

4.7.2 Time-to-depth conversion . . . . . . . . . . . . . . . . . . 64

4.8 Results and Discussions . . . . . . . . . . . . . . . . . . . . . . . 65

4.8.1 Eﬀect of in-situ annealing and ex-situ annealing . . . . . . 67