Introduction to Nanoscience

and Technology

An advanced elective course for 3rd and 4th year

undergraduates and research scholars

Instructor : Somnath Biswas, M. Tech., Ph. D. 1

 Introduction

Nano : Greek for dwarf, means one billionth

Measurement at this level is in nanometers (nm)----billionths of a meter.

Nanoscience and nanotechnology refer to the control and manipulation of mater
at nanometer dimensions, typically 1 nm to 20 nm range.

Nanotechnology builds on the ability to control or manipulate at the atomic
scale.

Nanotechnology creates and uses structures that have novel properties
because of their small size.

When we go nano, the interactions and physics between atoms display exotic properties
that they dont at larger scales.
How exotic ? you ask ?

Well, at this level atoms leave the realm of classical physical properties behind, and
venture into the world of quantum mechanics.
Physical intuitions fail miserably in the nanoworld....you see all kinds of unusual effects.
For example, even our everyday electrons act unusual at the nano level. Its like throwing
a tennis ball at a garage door and having the ball pop out the other side.
----Mark Reed, a nanoelectronics scientist at Yale University
2
Fig. 1. Size comparisons, from you all the way down to the hydrogen atom (Booker & Boysen). 3
Fig. 2. 2005 breakdown of nanotech expenditure among different US government
departments. The National Science Foundation projects that nanotech will be a $1 trillion
industry by 2015-----thats 10% of the GDP (2005) of the United States (Booker &
Boysen).
4
The realm of nanoscience is not new-----stained glass windows found in medieval churches
contain different-sized gold nanoparticles incorporated into the glass, the specific size of the
particles creates orange, purple, red or greenish colors. Einstein, as part of his doctoral
dissertation, calculated the size of a sugar molecule as one nanometer. Loosely considered,
both mediaeval glass workers and Einstein were nanoscientists.
Whats new about current nanoscience is its aggressive focus on developing applied
technology ---and the emergence of the right tools for the job.

Fig. 3. Faradays gold preserved in Royal

institution. From the page,
http://www.rigb.org/rimain/heritage/faradaypag
e.jsp

Fig. 4. The Lycurgus Cup made from glass appears red in transmitted light and
green in reflected light. The glass contains 70 nm particles as seen in the 5
transmission electron micrograph. From the site, http://www.thebritishmuseum.ac.uk.
Fig. 5. The complexity of integrated circuits as seen in the evolution of intel
microprocessors (T. Pradeep).

6
Nanostructured materials (thermodynamically) :
 Distribution of extremely small particles or pores at a nanometer scale forms a
nanostructure in preponderance contribution of the surface atoms or surface
interface energy in a high-energy metastable structure. It can be classified into three
groups.
Nanocrystalline

Nanostructure
Amorphous Microporous/Mesoporous
 In case, it is crystalline, called a nanocrystalline material, characterized by small
crystallite size of the order of few nanometer (usually 2 to 20 nm). Crystallites are
separated by their high angle grain or interphase boundaries.

Fig. 6. A model distribution of surface (open) and core (closed circles) in a nanocrystalline
solid (Glieter, Prog. Mater. Sci. 1989). 7
Fig. 7. Fraction of atoms in grain boundaries in a nanophase material as a function of
average grain diameter. The grain boundary is taken to be (a) 0.5 nm and (b) 1.0 nm, i.e.
equivalent to 2 to 4 atomic planes (Siegel 1990).

 20 - 40 % atoms are present at the grain boundaries. They govern the structure
and modify properties.
 Nanostructure has larger entropy, enthalpy and Gibbs's free energy.
 Nanocrystals consist of two structural components

Crystalline (C)

Intercrystalline (IC)
8
The IC region often assumes

A lower atomic density

A lower coordination number

A lower symmetry, and

An enhanced interatomic distance
Surface atoms do not have regular positions, a redistribution occurs to attend an
equilibrium configuration.
The interest in nanomaterials stems from the fact that the physical properties
exhibited by these materials are markedly different from those of their bulk
counterparts. There are two kinds of nanostructure-induced effects :

Surface or interface effects

Size effects or effects due to spatial confinement
Novel magnetic and electrical properties in magnetic nanomaterials :

Superparamagnetism,

Exchange anisotropy,

Surface anisotropy (orientation disorder of surface spins)

Spin relaxation

Coulomb blocked,

Variation of coercivity with particle size,
9

Magnetoresistance (MR)
 Superparamagnetism in small particles
Paramagnetism at temperatures below TC (ferro/ferrimagnet) or below TN
(antiferromagnet).
It is the magnetic analogue of Brownian motion. E is the energy cost per atom to align its
A
magnetization from one crystallographic
From Stoner-Wolforth theory, direction to another. It is a special case of
magnetic anisotropy. The spin-orbit
Magnetocrystalline anisotropy, EA = Kasin2 coupling is the primary source of EA.

Ka = magnetocrystalline anisotropy constant

= angle between the magnetization direction and the easy axis of magnetization in the particle.
Thermal energy = kT
TB = Blocking temperature
k = Boltzmann constant = 1.38 x 10-23 m2kgs-2K-1 (JK-1)

It depends on particle size,

anisotropy energy and the
time scale of the measuring
technique.
Relaxation time, t = t0 exp (-Ka/kT)
t0 is a constant related to the gyromagnetic precession and is estimated to be 10 -10 s.

Above TB, Hc = 0 and Mr = 0 because the thermal effect allows the magnetization to flip
between easy directions, surpassing the energy barrier even in the absence of any
external magnetic field. 10
Exchange anisotropy
It occurs due to the presence of an antiferrromagnetic material adjacent to a
ferromagnetic one when the magnetization at the surface of the antiferromagnetic material
is not completely compensated. Basically, it is the result of the exchange interaction
between the ferromagnetic and antiferromagnetic components.
Surface anisotropy
Surface anisotropy arises due to symmetry rupture around surface atoms, which in
turn occurs because the environment of a magnetic atom is significantly different at the
surface or near a grain boundary and in the bulk. The surface or interface effects therefore
modify exchange interactions, moment sizes, moment orientation and hence the spin
structure of the surface.
Surface anisotropy energy = Ks S Ks = surface anisotropy energy constant
S = surface area
It depends upon the orientation of the spontaneous magnetic moment as referred to the
surface (crystal face) and also depends upon the surface orientation as referred to
crystallographic axes.
Spin relaxation
In very small particles, spin relaxation occurs below a critical temperature.
= 0 exp (-EA/kT) 11
 Coulomb blocked
In granular materials, electrical conduction is chiefly by tunneling, i.e., electrons are
transferred from one particle to the next across the tunneling barrier.
The energy required to transfer a charge Q from one particle
to the other is
E = Q2/2C
where C = 40r is the capacitance of the particle assuming
e- it to be spherical, r = diameter of the particle and
0 = permittivity of free space.
Elementary charging energy EC = e2/2C, r = 5-10 nm, So, EC is large.
Hence, in order to make tunneling of an electron energetically favourable, the
energy eV (V is the emf of the voltage source) supplied by the voltage source has to
be larger than EC.
Variation of coercivity with particle size
Hc is highly sensitive to the surface states and varies with particle size. When the
particle size approaches the size of an ideal single domain, Hc increases due to
contributions from surface and shape anisotropies. If reduced further, Hc decreases,
because on reversing the direction of the external magnetic field, the magnetization
reversal of the particle is initiated at the surface.
In core-shell morphology, strain can increase Hc, e.g., surface is more oxidized than
core. The effect is drastic is case of ferromagnetic metallic particles passivated with 12
an oxide (generally antiferromagnetic) layer.
 Giant magnetoresistance (GMR)
GMR is a quantum mechanical phenomenon. Mathematically magnetoresistance (MR)
is defined as
Longitudinal MR
R (H,T) R (0,T)
MR = Transverse MR
R (0,T) +/- MR
Basically it is the variation of resistance of a material in the presence of a magnetic field.
In an ordinary periodic lattice, resistance arises due to
 Defects present in the lattice MR depends on (hkl)
Magnetostriction
 Phonon interaction
At low temperature, there is spin flipping, which contributes to electron scattering.
When a magnetic field is applied , the path of the electrons inside the lattice becomes
helical. A longer path length increases the scattering probability, which increases the
resistivity. In magnetic materials the major contribution to the resistance is the
electromagnetic interaction between conduction electron spins and magnetic moment of
the lattice.
GMR arises in :
 Multilayered thin films, e.g., Co/Cu, Fe/Cr, Co/Cr, etc.
 Granular materials, e.g., Co-Al-O alloy, Co:Al2O3, ABO3
perovskites, Fe/Ni/Co doped MnO, etc. 13
 Ferromagnetic layer
Non-magnetic layer
Ferromagnetic layer

Fig. 8. Magnetic structure in a GMR multilayer system.

Antiferromagnetic
outerpart
Ferromagnetic core

Fig. 9. Core-shell structure in a granular GMR material.

In both the systems, the application of an external magnetic field causes a drastic
change in the resistance of the sample. This large variation of resistance due to the
presence of an external magnetic field is called GIANT MAGNETORESISTANCE.

In multilayered systems the GMR property can be understood by taking into account
the conduction electrons scattering probability, whereas in granular materials, it
originates from spin dependent tunneling effect.
14
 Fig. 10. A model structure of composite films of granular GMR materials.
M = Global magnetization
Ms = Saturation magnetization
GMR ( M/Ms ) 2 = < cos > 2 = Angle between the magnetic
moment of a granule and the external
field.
< cos > = Average value of cos.
In a system of random distributions,
ij = Relative angle between magnetic axes
< cos ij > = < cos > 2 of uncorelated magnetic granules.
Several theoretical studies have been done on the spin dependent mechanism of GMR in this
type of composite granular films. Pogorelov et. al. (Phys. Rev. B 58 (1998) 425) have
introduced a microscopic theory of granular GMR and have shown that the spin dependent
conductance in granular systems can be sensitive to the short range magnetic order in addition
to the long range order. 15
 Electron microscopy

Resolution : A measure of the capacity of the instrument to distinguish two closely

spaced points as separate points, given in terms of distance.
Resolving power : The resolution achieved by a particular instrument under
optimum conditions.
Microscope : illumination source, a condenser lens to converge the beam on to the
sample, an objective lens to magnify the image, and a projector lens to project the
image onto an image plane which can be directly seen, photographed or stored.

Electron microscope : High energy electron beam is used as the

source for illumination of the sample and electromagnetic lenses
are used.
Scanning : A monochromatic electron beam is passed over the
surface of the specimen, which induces various changes in the
sample. The resulting particles from the sample are used to
create an image of the specimen. SEM has a large depth of field.
Transmitting : The probe beam passed through the specimen is
differentially refracted and absorbed.

16
The deBroglie wavelength associated with a high energy electron beam,

= h/p = h/mv
h = Planks constant, m = rest mass of electron, v = velocity of electrons,
An electron of charge e (1.6 x 10-19 C) and m (9.11 x 10-28 g) when passing through a
potential difference of V volts, acquires a kinetic energy of
mv2 = eV

v = (2eV/m)1/2

= (h2/2meV)1/2 (in nm) = 1.23/V1/2 (volts)

= 1.23/(V + 10-6V2) nm
Abbe criterion : The smallest resolvable distance between objects is about half the
wavelength of the light used. The maximum magnification that can be used is equal
to the resolving power of eye divided by the resolving power of the microscope.
Raleigh criterion : A real object presents a point as a disk in the image plane. The
diameter of the disk is equal to the angular aperture of the lens. If two points are
placed close to each other, the closest distance at which they appear to be separated
in the image is about the half the width of the disks. 17
 d = 0.61/ nsin
n = refractive index of the medium, = semi-circular aperture of the lens,
nsin = numerical aperture of the lens

Electron beam induced processes in the sample-

Particle and
photon emissions

Electron emission processes include elastic and inelastic scattering, and the emission
of secondary electrons and Ager electrons.
18
 X-rays and Ager electron emission processes

X-rays : = 10-5 to 100

Bremsstrahlung
process

19
 Scanning electron microscope (SEM)

Vaccum : 10-6 Torr

20
Fig. 11. A schematic diagram of a SEM
Electrons are confined Thermionic emitter :
and focused by the e.g., tungsten filament
grid cap.
Brightness ~
Current/area. solid angle
LaB6 based,

Field emission (FESEM)

type :
Cold field emitter (CFE)-
<310> tungsten tip
Schottky field emitter
(SFE)- ZrO2 coated tip

Fig. 12. Schematic of an electron gun. The gun is normally operated at a constant emission
current, which implies regulation of the current supplied to the filament.
21
 f = 1/p + 1/q

M = q/p
m = p/q

f = kV/(NI)2

k = constant
V = accelerating
voltage
N = number of turns
of the coils
I = current

Fig. 13. (a) Schematic of an electromagnetic electron lens, (b) illustration of the concept
of magnification. In EMs, there are two kinds of lenses, (i) the condenser lens has a
large bore giving a long focal length, while (ii) the objective lens has a strong field of
short axial extent giving a short focal length, resulting in high magnification.
22
 Lens aberrations

Disk of least confusion

ds = Cs 3 dc = Cc (E/ Eo)

Half diameter of Airy disk

dd = 0.61 /

Fig. 14. Various aberrations of electromagnetic lenses, (a) Spherical aberration,

(b) Chromatic aberration, (c) aperture diffraction, and (d) astigmatism.
23
The focus is dependent Magnification is not produced
upon the size of the by a magnification or enlarging
electron beam. lens but rather by taking
The smaller the spot on advantage of the differential
the sample, the better is between the size of the scan
the focus. pattern on the sample and the
size of the CRT.

The smaller the area scanned,

the higher is the magnification,
the lesser is the distance
between the raster points, and
smaller is the amount of
current needed to shift the
beam from point to point.

Fig. 15. Schematic of an SEM. The electron beam is scanned by a set of scan coils and
the secondary electrons are detected by the detector. By applying a negative potential
to the Faraday cage, the secondary electrons can be rejected completely.
Back scattered electrons high energy (~ keV) Solid state diode detector
Secondary electrons low energy (~ eV) Everhart-Thornley detector (gain ~ 106 , high band
width)
Low voltage SEM (highly surface sensitive due to reduced interaction volume, avoids damage and
charging effect, no need of metallic coating) Channel plate detector
ULV-SEM applying a negative bias to the sample 24
SEM resolution ~ 0.5 nm
Depth of field

25
Typical SEM micrographs

26
 Microanalysis
EDS : Energy dispersive spectroscopy

EDS detectors : lithium drifted Si,

high purity Ge, etc.

27
WDS : Wavelength dispersive spectroscopy

n = 2dsin

is the wavelength of X-ray and is the angle of incidence.

WDS detectors : gas proportional counters (90% Ar, 10% methane)

28
Improved energy resolution, but cumbersome and time consuming. In EDS, a signal from the
detector is proportional to both the energy and intensity of the X-rays. In WDS, the wavelength
and intensity of the X-rays are determined separately.

Since, sin (max) = 1, max = 2d

Therefore, the crystal puts a limit on the range of elements covered.

When ~ 90, the detector has to sit at the X-ray source, when ~ 0, the movement of the
crystal near the specimen is a problem.
In order to diffract the low energy X-rays emitted by Be, B, C and N, it is necessary to use
crystals of large d values.
Most of the measurements of long wavelength X-rays are done by layered synthetic
microstructures. These contain evaporated alternate layers of heavy and light elements. The
thickness of the layers can be easily controlled.
Langmuir-Blodgett films : interlayer spacing can be changed by varying the chain length of the
monolayer.

29
The spatial resolution of SEM is affected by the beam size. The beam causes interaction with
the sample and the region of interaction exceeds the physical dimension of the beam itself.
The spatial extent increases laterally as well as depth-wise, and this interaction volume
depends on the material and also on the beam energy.

Fig. 16. Universal attenuation length data of materials as a function of electron

kinetic energy. At low kinetic energies, the electrons are sensitive to only a few
monolayers of the material.
30
Low energy SEM
 Transmission electron microscope (TEM)

Fig. 17. Two kinds of image collection : (a) bright field, and (b) dark field. In bright
field, the transmitted beam is used for imaging. In dark field, the diffracted beam is
used for imaging.
TEM resolution, d Cs1/4 3/4 ~ 0.1 nm 31
 Elastic scattering (no energy change)
Electron beam Mater
Coherent In-coherent
(with phase relation) (without phase relation)

Inelastic scattering (energy change)

32
Elastic scattering occurring from well-ordered arrangements of atoms as in a crystal,
results in coherent scattering, giving spot patterns. This can be in the form of a ring in
polycrystalline materials.
Inelastic scattering also give regular patterns as in the case of Kikuchi patterns.
Inelastic processes give characteristic absorption or emission, specific to the
compound, element or chemical structure Electron energy loss spectroscopy
(EELS)

33
 Scanning transmission electron microscope (STEM)
Probe beam has Rastering of the beam ~
to be small & EDX mapping, EELS &
bright. annular dark-field
FE sources : (ADF) imaging.
beam < 1 nm Ability to image atoms
Scanning coils using ADF.
are inside the
objective lens.

The electrons pass through the specimen, but, as in SEM the electron optics focus the
beam into a narrow spot which is scanned over the sample in a raster. By using a
STEM and a high-angle detector, it is possible to form atomic resolution images where
the contrast is directly related to the atomic number. This is in contrast to the
conventional high resolution EM techniques, which uses phase-contrast, and therefore
produces results which need interpretation by simulation.
34
STEM resolution ~ 0.05 nm
In the fixed-beam TEM, electrons scattered by the irradiated sample are collected over a
narrow solid angle and focused by the objective lens onto the image plane. The elastically
scattered electrons, i.e., those which have changed their direction but not lost any energy
on interaction with the specimen, interfere with the unscattered electrons to produce a
phase contrast image . The inelastically scattered electrons, i.e., those which have changed
both direction and energy on interaction with the specimen, generate a diffuse
background image that is in some EMs eliminated by an energy filter.

In the STEM, the objective lens focuses the electron beam onto an atomic scale sample
volume. All scattered electrons can then be collected by a variety of detectors placed
behind the specimen and their information exploited to the fullest extent. An image is
generated simply by moving the focused beam step by step over the specimen. Hence a
STEM image may be considered as a collection of individual scattering experiments.
Various types of signals discriminated in scattering angle and/or energy loss yield different
structural and chemical information and may be captured simultaneously in different
channels. This simultaneous and controlled acquisition of information lends itself to
quantitative analyses that are difficult to realize with other instruments. In addition, as
there is no limitation of the solid angle and the energy loss interval over which the
scattered electrons may be collected, 60-100% of them contribute to the image. This
provides a unique opportunity to image beam-sensitive biomolecules at low dose.

35
36
 Scanning probe microscopy (SPM)
A probe of nanometer dimension is used to investigate a material.
 Scanning tunneling microscopy (STM)
 Atomic force microscopy (AFM) Techniques for viewing surfaces at the atomic level.
 Magnetic force microscopy (MFM)

STM : It probes the density of states (DOS) of a material using tunneling current.

Lateral resolution ~ 0.1 nm Constant current &

Depth resolution ~ 0.01 nm constant height
modes
Ultra-high vacuum, air, liquid
and gas ambients,
0 K to few hundred C.

Quantum tunneling : When a conducting tip is brought very near to the surface to be examined, a bias
applied between the two can allow electrons to tunnel through the vacuum between them. The resulting
tunneling current is a function of tip position, applied bias and the local DOS of the sample. 37
 STM stylus head Gold (100) surface

Scanning tips : Tungsten, platinum-iridium, gold,

carbon nanotubes

First, a voltage bias is applied and the tip is brought close to the sample by some coarse sample to tip
control. Fine control of the tip in all three dimensions when near the sample is typically piezoelectric,
maintaining tip-sample separation W typically in the 4-7 range, which is the equilibrium position
between attractive (3<W<10 ) and repulsive (W<3 ) interactions. In this situation, the voltage bias
will cause electrons to tunnel between the tip and sample, creating a current that can be measured.
Once tunneling is established, the tips bias and position with respect to the sample can be varied and
data is obtained from the resulting changes in current due to the changes in surface height and DOS in
the sample.
Components : Scanning tip, piezoelectric controlled height and x,y scanner, sample-to-tip control,
vibration isolation system, computer controls
Constant current & constant height modes 38
 Atomic force microscopy (AFM)
AFM : One of the foremost tools for imaging, measuring and manipulating matter at the nanoscale.

Resolution ~ fraction of a nm
Probe : Si, Si3N4
Forces : Mechanical contact force,
van der Waals forces, capillary forces,
chemical bonding, electrostatic forces,
magnetic forces, Casimir forces,
solvation forces, etc.

39
Beam deflection detection Glass surface

Laser deflection/ Interferometry/

Capacitive sensing/piezoresistive
cantilever NaCl crystal
Modes of operation :
Static Contact mode
Dynamic Tapping mode
Modifications : Scanning thermal microscopy,
photothermal microspectroscpy, etc.

40
 Magnetic force microscopy (MFM)
Resolution ~ 30 nm
Electromagnetic tip

10-20 nm

Single crystal Si,

Si3N4, SiO2, etc. with
a thin coating of Ni,
Co, etc.

) H
F = o (m.

m is the magnetic moment of the tip

(approx. as a point dipole),
H is the magnetic stray field from the
surface, and o is the magnetic
permeability of free space.

MFM image showing the bits of

a hard disk. Field of view 30m.

Static (DC) mode : z = Fz/k

Dynamic (AC) mode : f = fr fn = -fn (Fz/z) /2k
41
Lift height method
Calculating forces acting on magnetic tips

Analytically, the magnetostatic energy (U) of the tip-sample system can be calculated in one of two ways :
One can either compute the magnetization (M) of the tip in the presence of the magnetic stray field (H) of
the sample or compute the magnetization of the sample in the presence of the magnetic stray field of the
tip (whichever is easier) then, integrate the (dot) product of the magnetization and stray field over the
interaction volume as

and compute the gradient of the energy over distance to obtain the force F. Assuming that the cantilever
deflects along the z-axis, and the tip is magnetized along a certain direction (e.g. the z-axis), then the
equations can be simplified to

Since the tip is magnetized along a specific direction, it will be sensitive to the component of the
magnetic stray field of the sample which is aligned to the same direction.

Advantages
1. The sample does not need to be electrically conductive.
2. Measurement can be performed at ambient temperature, in ultra high vacuum (UHV), in liquid environment, and
at different temperatures.
3. Measurement is nondestructive to the crystal lattice or structure.
4. Long-range magnetic interactions are not sensitive to surface contamination.
5. No special surface preparation or coating is required.
6. Deposition of thin non-magnetic layers on the sample does not alter the results.
7. Detectable magnetic field intensity H, is in the range of 10 A/m
8. Detectable magnetic induction B, is in the range of 0.1 gauss (10 microteslas).
9. Typical measured forces are as low as 10-14 N, with the spatial resolutions as low as 20 nm. 42
10. MFM can be combined with other scanning methods like STM.
Limitations

1. The recorded image depends on the type of the tip and magnetic coating, due to tip-sample
interactions.
2. Magnetic field of the tip and sample can change each other's magnetization, M, which can result
in nonlinear interactions. This hinders image interpretation.
3. Relatively short lateral scanning range (order of hundreds micrometers).
4. Scanning (lift) height affects the image.
5. Housing of the MFM system is important to shield electromagnetic noise (Faraday cage), acoustic
noise (anti-vibration tables), air flow (air isolation), and static charge on the sample.

43
1982 - Scanning tunneling microscope (STM)
 Tunneling current between tip and sample is used as the signal
 Both the tip and sample must be electrically conductive

1986 - Atomic force microscopy (AFM)

 Forces (atomic/electrostatic) between the tip and sample are sensed from the deflections of a
flexible lever (cantilever)
 The cantilever tip flies above the sample with typical distance in the order of tens of nanometer.

1987 - Magnetic force microscopy (MFM)

 Derives from AFM in which the magnetic forces between the tip and sample are sensed
 Image of the magnetic stray field obtained by scanning the magnetized tip over the sample surface
in a raster-like fashion

Yttrium Iron garnet films Co magnetic elements

44
Fig. 18. MFM micrograph of a hard disk showing how bits of information are written on a
magnetic memory. One can see the evolution of size of magnetic domains which caused the
commercialization of nanomaterials.

45
Lattice of magnetic dipoles Magnetic domains of garnet films
Magnetic domains of yttrium iron garnet YIG domains reorganization Fe based metallic glass

Magnetic domains in a TbGdFeCo film

46
Magnetic structures of permalloys
 Confocal laser scanning microscopy (CLSM or LSCM)

Optical images with depth selectivity : conventional microscope "sees" as far

into the specimen as the light can penetrate, while a confocal microscope only
images one depth level at a time.

Optical sectioning : It is able to acquire in-focus images

from selected depths.
Opaque specimens surface profiling
Non-opaque Interior structure imaging
It achieves a controlled and highly limited depth of focus.

47
48
 Near field scanning optical microscopy (NSOM or SNOM)
This scanning probe technique breaks the far field resolution limit by exploiting the properties of evanescent
waves (exciting and collecting diffraction in the near field). The detector is placed very close to the specimen
surface (smaller than wavelength). It has high spatial, spectral and temporal resolving power. The resolution of
the image is limited by the size of the detector aperture and not by the wavelength of the illuminating light.
Lateral resolution 20 nm
Vertical resolution 2-5 nm
Refractive index, local stress and chemical structure can be studied.

Fig. 19. Sketch of (a) a typical metal coated Fig. 20. Apertured modes of operation, (a)
tip and (b) a sharp uncoated tip. illumination, (b) collection, (c) illumination
collection, (d) reflection, and (e) reflection collection.

It involves the use of a sub-wavelength metal coated optical aperture at the tip of a sharp pointed probe, and a
feedback mechanism to maintain a constant distance of a few nanometers between the sample and the probe.
NSOM makes use of evanescent or non propagating fields that exists only near the surface of the object, carrying
the high frequency spatial information about the object and have intensities that drop off exponentially with
distance from object.
49
Aperture and non-aperture modes
Fig. 21. Apertureless modes of operation, (a) photon
tunneling (PSTM) by a sharp transparent tip, (b) PSTM by
sharp opaque tip on smooth surface, and (c) Scanning
interferometric apertureless microscopy (SIAM) with double
modulation.
Fig. 22. Block diagram of an apertureless reflection-back to
the fibre NSOM setup with shear force distance control and
cross polarization : (1) Beam splitter and cross polarizers,
(2) shear-force arrangement, (3) Sample mount on a piezo
stage.

Feedback mechanisms : constant force feedback and shear force feedback.

Contrast enhancing mechanisms : By using the change in the polarization of light or the intensity of the light
as a function of the incident wavelength, it is possible to make use of contrast enhancing techniques such as
staining, fluorescence, phase contrast and differential interference contrast.
Instrumentation : Light source, feedback mechanisms, the scanning tip, the detector and the piezoelectric
sample stage.
Light source : Laser focused into an optical fiber through a polarizer, beam splitter and a coupler.
Scanning tip : Depending upon the operation mode, usually a pulled or stretched optical fiber coated with
metal except at the tip or just a standard AFM cantilever with a hole in the center of the pyramidal tip.
Detectors : Avalanche photodiode, PMT tube or CCD.

50
 Secondary ion mass spectrometry (SIMS)
It analyzes the composition of solid surfaces and thin films by sputtering the surface of the specimen with a
focused primary ion beam and collecting and analyzing ejected secondary ions. These secondary ions are
measured with a mass spectrometer to determine the elemental, isotopic, or molecular composition of the
surface. SIMS can detect elements present in the parts per billion range.

Pressure < 10-6 mbar

Fig. 23. Typical schematic of a dynamical SIMS instrument. High energy ions are supplied by an ion gun (1 or
2) and focused on to the target sample (3), which ionizes and sputters some atoms off the surface. These
secondary ions are then collected by ion lenses (5) and filtered according to atomic mass (6), then projected
onto an electron multiplier (7, top), Faraday cup (7, bottom), or CCD screen (8). 51
Primary ion sources : (i) generated with duoplasmatrons or by electron ionization, e.g., Ar+, Xe+, O-, O2+, SF5+,
C60+. The beam is roughly focused but contains high ion current.
(ii) Surface ionization source Caesium atoms vaporize through a porous tungsten plug and are ionized (Cs+) during
evaporation. Depending on gun design, fine focus or high current can be obtained.
(iii) Liquid metal ion source (LMIS) The liquid metal covers a tungsten tip and emits ions under influence of an intense
electric field, e.g., elemental gallium, and gold, indium and bismuth alloys. The LMIS provides a tightly focused ion beam
(<50 nm) with moderate intensity and is additionally able to generate short pulse ion beams.
Mass analyzers : (i) Sector - it uses a combination of an electrostatic analyzer and a magnetic analyzer to separate the
secondary ions by their mass to charge ratio.
(ii) Quadrupoles it separates the masses by resonant electric fields, which allow only the selected masses to pass through.
(iii) Time of flight analyzer it separates the ions in a field-free drift path according to their kinetic energy. It requires
pulsed secondary ion generation using either a pulsed primary ion gun or a pulsed secondary ion extraction. It is the only
analyzer type able to detect all generated secondary ions simultaneously.
Detectors : Faraday cup with an electron multiplier, micro-channel plate detector, etc, in combination with a fluorescent
screen, and signals are recorded either with a CCD camera or with a fluorescence detector.
Static SIMS mode process involved in surface atomic monolayer analysis, usually with a pulsed ion beam and a time of
flight mass spectrometer.
Dynamic SIMS mode process involved in bulk analysis, closely related to the sputtering process, using a DC primary ion
52
beam and a magnetic sector or quadrupole mass spectrometer.
 Focused ion beam (FIB)
It is used for site-specific analysis, deposition, and ablation of materials.

Ga+ are accelerated to an energy of 5-50 keV and focused onto the sample by electrostatic lenses.
The operation is similar to SEM, but instead of electrons, ions are used which can be operated at low beam
currents for imaging or high beam currents for site specific sputtering or milling.
Low beam currents : imaging with resolution ~ 5 nm
High current : precision milling down to submicron scale.
If the sample is non-conductive, a low energy electron flood gun can be used to provide charge
neutralization. In this manner, by imaging with positive secondary ions using the positive primary ion
beam, even highly insulating samples may be imaged and milled without a conducting surface coating, as
would be required in a SEM.
Usage in electronic industry : defect analysis, circuit modification, mask repair and TEM sample
preparation of site specific locations on integrated circuits. 53
 FIB technology

MCP : micro channel plate detector

Block diagram and real FIB 54
The most fundamental difference between FIB and focused electron beam techniques such as SEM,
STEM, etc., is the use of ions instead of electrons, and this has major consequences for the interactions
that occur at the sample surface. The most important characteristics and the consequences for the sample
interaction are,

Ions are larger than electrons :

 Because ions are much larger than electrons, they cannot easily penetrate within individual atoms of
the sample. Interaction mainly involves outer shell interaction resulting in atomic ionization and breaking
of chemical bonds of the substrate atoms.
 The penetration depth of the ions is much lower than the penetration of electrons of the same energy.
 When the ion has come to a stop within the material, it is caught in the matrix of the material.

Ions are heavier than electrons :

 Because ions are far heavier than electrons, ions can gain a high momentum. For the same energy, the
momentum of the ion is about 370 times larger.
 For the same energy, ions move a lot slower than electrons. However, they are still fast compared to the
image collection mode and in practice this has no real consequences.
 The magnetic lenses are less effective on ions than they would be on electrons with the same energy. As
a consequence the focused ion beam system is equipped with electro-static lenses and not with magnetic
lenses.

In summary, ions are positive, large, heavy and slow, whereas electrons are negative, small, light and fast.
The most important consequence of the properties listed above is that ion beams will remove atoms from
the substrate and because the beam position, dwell time and size are so well controlled it can be applied to
remove material locally in a highly controlled manner, down to the nanometer scale.
55
When the high-energy Ga ions strike the sample, they will sputter atoms from the surface. Ga
atoms will also be implanted into the top few nanometers of the surface, and the surface will be
become amorphous. Because of the sputtering capability, the FIB is used as a micro-machining tool,
to modify or machine materials at the micro- and nanoscale. The common smallest beam size is 2.5-
6 nm. FIB tools are designed to etch or machine surfaces, an ideal FIB might machine away one
atom layer without any disruption of the atoms in the next layer, or any residual disruptions above
the surface.

Gas assisted deposition process Gas assisted etching process

e.g., W(CO)6 precursor
56
McMaster University name and logo SEM image of a thin TEM sample Example of a 3D nanostructure that
"tattooed" in two sizes on a hair. milled by FIB. can be obtained

FIB secondary electron FIB secondary ion

image image
Enhanced and selective etching
FIB secondary electron images show intense grain orientation contrast. As a result,
grain morphology can be readily imaged without resorting to chemical etching. FIB
secondary ion images also reveal chemical differences, and are especially useful in
corrosion studies, as secondary ion yields of metals can increase by three orders of
magnitude in the presence of oxygen, clearly revealing the presence of corrosion.

In an electronic device structure, the Ga beam could be used to cut unwanted electrical connections, and/or to deposit
conductive material in order to make a connection. The high level of surface interaction is exploited in patterned doping
of semiconductors. FIB is also used for maskless implantation. 57
The FIB is also commonly used to prepare samples for the TEM. The TEM requires very thin
samples, typically ~100 nanometers. Other techniques, such as ion milling or electropolishing can be
used to prepare such thin samples. However, the nanometer-scale resolution of the FIB allows the
exact thin region to be chosen. This is vital, for example, in integrated circuit failure analysis. If a
particular transistor out of several million on a chip is bad, the only tool capable of preparing an
electron microscope sample of that single transistor is the FIB.
Wien Filter :The principle of a Wien filter is based on the equilibrium of the opposite forces induced
by perpendicular electrostatic and a magnetic field acting on accelerated particles. The proper mass
trajectory remains straight and passes through the mass selection aperture while the other masses are
stopped.

Au-Si, Au-Ge and

Au-Si-Ge sources Larger ions can be
providing Si, Cr, Fe, used to make rapid
Co, Ni, Ge, In, Sn, milling before refining
Au, Pb and other the contours with
elements. smaller ones. The user
also benefits from the
possibility to dope his
sample with elements
with suitable alloy
sources.

58
Mass selection in the FIB column Wien filter set up in FIB
X-ray photoelectron spectroscopy (XPS/ESCA)

59
XPS is used to measure :
 Elemental composition of the surface (top 110 nm usually)
 Empirical formula of pure materials
 Elements that contaminate a surface
 Chemical or electronic state of each element in the surface
 Uniformity of elemental composition across the top surface (line profiling or mapping)
 Uniformity of elemental composition as a function of ion beam etching (depth profiling)
XPS detects all elements with an atomic number (Z) of 3 (lithium) and above. It cannot detect hydrogen (Z = 1)
or helium (Z = 2).
Detection limits for most of the elements are in the parts per thousand range. Detections limits of parts per
million (ppm) are possible, but require special conditions: concentration at top surface or very long collection
time (overnight).

60
Fig. 23. Wide scan survey spectrum for all elements
Example of a "High Energy Resolution XPS Spectrum"
also called High Res spectrum. This is used to decide what
chemical states exist for the element being analyzed. In this
example the Si (2p) signal reveals pure Silicon at 99.69 eV, a
Si2O3 species at 102.72 eV and a small SiO2 peak at 103.67 XPS analysis of surface chemistry of plutonium
eV. The amount of Si2O at 100.64 eV is very small. oxides exposed to water

61
 Auger electron spectroscopy (AES)

Ekin = ECorestate EB EC

Fig. 24. Two views of the Auger process. (a) illustrates sequentially the steps involved in Auger de-excitation. An
incident electron (or high energy particles) creates a core hole in the 1s level. An electron from the 2s level fills in
the 1s hole and the transition energy is imparted to a 2p electron which is emitted. The final atomic state thus has
two holes, one in the 2s orbital and the other in the 2p orbital. (b) illustrates the same process using spectroscopic
notation, KL1L2,3.
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Surface sensitivity in AES
arises from the fact that
emitted electrons usually
have energies ranging from
50 eV to 3 keV and at these
values, electrons have a
short mean free path in a
solid. The escape depth of
electrons is therefore
localized to within a few nm
of the target surface, giving
AES an extreme sensitivity
to surface species.

Fig. 25. AES experimental setup using a cylindrical mirror analyzer (CMA). An electron beam is focused onto a specimen
and emitted electrons are deflected around the electron gun and pass through an aperture towards the back of the CMA.
These electrons are then directed into an electron multiplier for analysis. Varying voltage at the sweep supply allows
derivative mode plotting of the Auger data. An optional ion gun can be integrated for depth profiling experiments.

Since the intensity of the Auger

peaks may be small compared to
the noise level of the background,
AES is often run in a derivative
mode which serves to highlight
the peaks by modulating the
electron collection current via a
small applied AC voltage.

Fig. 26. Auger spectrum of a copper nitride film in derivative mode plotted as a function of energy. Different peaks for Cu
and N are apparent with the N KLL transition highlighted 63
 X-ray diffraction (XRD) techniques
XRD is a versatile, non-destructive technique that reveals detailed information about the chemical composition
and crystallographic structure of natural and engineered materials.
Crystal lattice : A crystal lattice is a regular three-dimensional distribution (cubic, orthorhombic, etc.) of atoms in
space. These are arranged so that they form a series of parallel planes separated from one another by a distance d,
which varies according to the nature of the material. For any crystal, planes exist in a number of different
orientations each with its own specific d-spacing.
Constructive interference : When a monochromatic X-ray beam with wavelength is projected onto a crystalline
material at an angle , diffraction occurs only when the distance traveled by the rays reflected from successive
planes differs by a complete number n of wavelengths.
Braggs Law : By varying the angle , the Bragg's Law conditions are satisfied by different d-spacings in poly-
crystalline materials.

2d sin = n

Based on the principle of X-ray diffraction, a wealth of structural, physical and chemical information about the
material investigated can be obtained. A host of application techniques for various material classes is available,
each revealing its own specific details of the sample studied.
64
Plotting the angular positions and intensities of the resultant diffracted peaks of radiation produces a pattern, which is
characteristic of the sample. Where a mixture of different phases is present, the resultant diffractogram is formed by
addition of the individual patterns.

When crystallites are less than ~100 nm in size, appreciable broadening in the XRD lines will
occur. These regions may in fact correspond to the actual size of the particles. At other times,
however, these regions form domains in the larger particles.
Debye-Scherrers equation,
Particle size, D

D = 0.89 / cos

= FWHM (in radians)

= Diffraction angle
= X-ray wavelength

65
Fig. 27. Diffraction patterns of nanocrystalline Si showing broadening because of reduction in particle size.
Debye-Scherrers formula is valid only when the diffracting material is stress free. In those cases where both stress and
particle size lead to broadening of the diffraction peaks, a more comprehensive method must be used to separate the
contributions. The most common method of strain/size analysis utilizes the fact that the broadening from the two different
sources have different angular relationships. For example, the size broadening as described earlier has a 1/cos relationship
while the strain follows a tan function. Finally, the instrument also contributes to the broadening.

Fig. 28. Plot of the peak widths (FWHM) for Al2O3 and ZrO2 in a partially sintered composite at various diffraction angles.
By use of a least square fit, the particle size and stain can be computed.

Total broadening, bt
bt2 = {0.89 / cos}2 + {4 tan}2 + b02

= FWHM (in radians)

= strain
= Diffraction angle
= X-ray wavelength 66
 Dynamic light scattering (DLS) techniques
Quasi-elastic light scatterning (QELS) or Photon correlation spectroscopy : It is used to determine the size
distribution profile of small particles in suspension or polymers in solution. It can also be used to probe the
behavior of complex fluids such as concentrated polymer solutions. It is one of the foremost techniques used to
measure the radius of a particle in a medium.
The motion of particles of micron or lower size is uncorrelated, i.e., they are random. As light scatters from such
particles, there will be a shift in the phase of the scattered light which is random and as a result, when the
scattered light rays from several particles are added together, constructive or destructive interference occurs.
What we get is time-dependent fluctuation in the intensity of the scattered light.
The scattering of light from particles undergoing Brownian motion also leads to a Doppler shift of radiation,
modifying the wavelength of the light.
Set up : A laser light beam is sent through a suspension containing particles. The sample has to be inhomogeneous
in one of the several ways (such as due to the presence of particles, micelles, proteins, acoustic waves, etc.). The
scattered light is received by a fast detector.
If the intensity of light is measured as a function of the scattered direction, it is called the static light scattering. If
the correlation of light intensity is measured as a function of time, it is called dynamic light scattering.
In summary, when the electric field of the light interacts with the molecules in the medium, an oscillating electric
field is induced. The interaction leads to a shift in the frequency of the light and angular distribution of the
scattered light, both of which are related to the size. If one assumes that the particles are in Brownian motion, one
can apply the Stokes-Einstein equation and get the radii of the suspended particles :

a = kT/6D

where k is Boltzmann constant, D is the diffusion coefficient, is the viscosity and T is the absolute temperature.
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 Vibrational spectroscopies
Infra red (IR) spectroscopy : IR spectroscopy is the subset of spectroscopy that deals with the infrared region of the
electromagnetic spectrum. It covers a range of techniques, the most common being a form of absorption
spectroscopy. As with all spectroscopic techniques, it can be used to identify compounds or investigate sample
composition. A common laboratory instrument that uses this technique is an infrared spectrophotometer.

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69
Raman spectroscopy : This technique is used to study vibrational, rotational, and other low-frequency modes in a system. It
relies on inelastic scattering, or Raman scattering, of monochromatic light, usually from a laser in the visible, near infrared,
or near ultraviolet range. The laser light interacts with phonons or other excitations in the system, resulting in the energy of
the laser photons being shifted up or down. The shift in energy gives information about the phonon modes in the system.
Infrared spectroscopy yields similar, but complementary, information.

Fig. 29. Energy level diagram showing the states involved in Raman signal. The line thickness is roughly proportional to the
signal strength from the different transitions.
The Raman effect occurs when light impinges upon a molecule and interacts with the electron cloud and the bonds of that
molecule. The incident photon excites the molecule into a virtual state. For the spontaneous Raman effect, the molecule
will be excited from the ground state to a virtual energy state, and relax into a vibrational excited state.
Two series of lines exist around this central vibrational transition. They correspond to the complimentary rotational
transition. Anti-Stokes lines correspond to rotational relaxation whereas Stokes lines correspond to rotational excitation.
A change in the molecular polarization potential or amount of deformation of the electron cloud with respect to the
vibrational coordinate is required for the molecule to exhibit the Raman effect. The amount of the polarizability change
will determine the Raman scattering intensity, whereas the Raman shift is equal to the vibrational level that is involved.
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