CHAPTER 4: CHARACTERIZATION TECHNIQUES

FOR NANOMATERIALS

90
 CHAPTER 4

CHARACTERIZATION TECHNIQUES FOR

NANOMATERIALS

4.1 Introduction

Nanomaterials behave differently as the size changes with respect to the bulk.

It is necessary to characterize physical, structural and optical properties of a

material to qualify as nanomaterial. Various characterization techniques are

used to know the characteristics of the nanomaterials.

4.2 Characterization techniques

Characterization techniques are classified as:

a) Chemical characterization

b) Structural characterization

4.2.1 Chemical characterization techniques

To study the internal chemical structural details, chemical characterization is

done.

i) Optical Spectroscopy:

a) Optical absorption spectroscopy (OAS)

b) Photoluminescence (PL)
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c) Fourier Transform Infrared Spectroscopy (FTIR)

d) Raman Spectroscopy

ii) Electron Spectroscopy:

a) Energy Dispersive X-ray Spectroscopy (EDS)

b) X-ray Photoelectron Spectroscopy (XPS)

c) Auger Electron Spectroscopy (AES)

d) Ultraviolet photoelectron spectroscopy (UPS)

iii) Ionic Spectrometry

iv) Rutherford Backscattering Spectrometry (RBS)

v) Secondary Ion Mass Spectrometry (SIMS)

4.2.2 Structural characterization techniques

Variation in the size of nanoparticle determines the optical properties of the

material.Simillarly, for different applications of the nanomaterial, the information

about the shape, lattice constants and crystallinity are important. To know the

size, shape, lattice constants and crystallinity of the material, structural

characterization is done. The techniques are [1,2]:

i) X-ray diffraction technique

ii) Electron microscopy:

a) Scanning Electron Microscopy (SEM)

b) Transmission Electron Microscopy(TEM)/High Resolution (HR)TEM with

Selected Area Electron Diffraction(SAED)

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c) Small Angle X-ray Scattering (SAXS)

d) Environmental Transmission Electron Microscopy (ETEM)

e) Scanning Probe Microscopy(SPM):

i) Atomic Force Microscopy (AFM)

ii) Scanning Tunneling Microscopy (STM)

iii) Dynamic light Scattering

4.3 Characterization techniques adopted in the present work

4.3.1 Chemical Characterizations:

4.3.1(a) Optical Spectroscopy:

Optical spectroscopy uses the interaction of light with matter as a function of

wavelength or energy in order to obtain information about the

material.Absorption or emission experiments with visible and UV light tend to

reveal the electronic structure. Vibrational properties of the lattice (i.e.,

phonons) are usually in the IR and are studied either using IR absorption or

Raman spectroscopy. Optical spectroscopy is attractive for materials

characterization because it is fast, nondestructive and of high resolution.

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(i) Optical Absorption Spectroscopy

UV-visible spectroscopy

This technique involves the absorption of near-UV or visible lightAbsorption

spectroscopy is employed to determine the presence of a particular substance

in a sample and, in many cases, to quantify the amount of the substance

present [3], When organic compounds absorb UV or visible light,energy from

the light is used to promote an electron from a bonding or non-bonding orbital

into one of the empty anti-bonding orbitals. In each possible case, an electron

is excited from a full orbital into an empty anti-bonding orbital. Each jump takes

energy from the light, and a big jump needs more energy than a small one.

Figure 4.1 showing the possible electron jumps that light may cause.

Figure 4.1 Possible electron jumps [http://www.chemguide.co.uk/analysis/uvvisible/

theory.htmlj

Each wavelength of light has a particular energy associated with it. If that

particular amount of energy is just right for making one of these energy jumps,
94
then that wavelength will be absorbed its energy will have been used in

promoting an electron.

The relationship between the frequency of light absorbed and its energy

E=hv (4.1)

Where, E is the energy of each quanta of light, h is the Planck’s constant and v

is the frequency of light For higher energy jump, light of a higher frequency is

to be absorbed.

UV-visibJe spectrophotometer measures both intensity and wavelength. It is

usually applied to molecules and inorganic ions in solution. For each

wavelength of light passing through the spectrometer, the intensity of the light

passing through the reference cell is measured. This is usually referred to as l0

.The intensity of the light, I passing through the sample cell is also measured

for that wavelength. If l is less than l0l then obviously the sample has absorbed

some of the light.

The Beer-Lambert Law gives, the relationship between A (the absorbance) and

the two intensities is given by:

I0
A=log10
1
(4.2)

An absorbance of 0 at some wavelength means that no light of that particular

wavelength has been absorbed. An absorbance of 1 happens when 90% of the

light at that wavelength has been absorbed that means that the intensity is 10%

95
of what it would otherwise be. A spectrophotometer can be either single beam

or double beam.

Shown in the figure 4.2, a single beam UV-visible spectrophotometer.

Figure 4.2 Schematic of single beam UV-visible Spectrophotometer [http://n elchem.

kaist ac kr/vt/chem-ed./spec/uv-vis/uv-vls.htm],

The basic parts of a spectrophotometer are a light source, a holder for the

sample, a diffraction grating in a monochromator or a prism to separate the

different wavelengths of light, and a detector. The radiation source is often a

tungsten filament (300-2500 nm), a deuterium arc lamp, continuous over the

ultraviolet region (190-400 nm), xenon arc lamps, continuous from 160-2,000

nm; or more recently, light emitting diodes (LED) for the visible wavelengths [4],

The detector is typically a photomultiplier tube, a photodiode, a photodiode

array or a charge-coupled device (CCD).Single photodiode detectors and

photomultiplier tubes are used with scanning monochromators, which filter the

light so that only light of a single wavelength reaches the detector at one time.

The scanning monochromator moves the diffraction grating to "step-through"

each wavelength so that its intensity may be measured as a function of

wavelength. Fixed monochromators are used with CCDs and photodiode

96
arrays. As both of these devices consist of many detectors grouped into one or

two dimensional arrays, they are able to collect light of different wavelengths on

different pixels or groups of pixels simultaneously.

In a single beam spectrophotometer the light passes through the sample cell. I0

must be measured by removing the sample. In a double-beam instrument, the

light is split into two beams before it reaches the sample. One beam is used as

the reference; the other beam passes through the sample. The reference beam

intensity is taken as 100% Transmission (or 0 Absorbance), and the

measurement displayed is the ratio of the two beam intensities. Some double­

beam instruments have two detectors (photodiodes), and the sample and

reference beam are measured at the same time shown in figure 4.3. In other

instruments, the two beams pass through a beam chopper, which blocks one

beam at a time. The detector alternates between measuring the sample beam

and the reference beam in synchronism with the chopper. There may also be

one or more dark intervals in the chopper cycle. In this case the measured

beam intensities may be corrected by subtracting the intensity measured in the

dark interval before the ratio is taken.

Figure 4.3 Schematic of a dual-beam UV-visible spectrophotometer[Available at

http://www.fiie8.chem.vt.edu/chem-ed/spec/uv-vis/dualbeam.html]
97
The Tauc’s plot is used to determine optical bandgap. Tauc plot shows the

quantity hv (the photon energy) on the abscissa and the quantity (ahv)r on the

ordinate, where a is the absorption coefficient of the material [5]. The value of

the exponent r denotes the nature of the transition; for example, r = 14 for

indirect transitions [5], The resulting plot has a distinct linear regime which

denotes the onset of absorption. Thus, extrapolating this linear region to the

abscissa yields the energy of the optical bandgap of the material. However, if

the material does not have a single phase, it will likely not have a single distinct

absorption onset, which corresponds to a more gradually sloping curve in the

Tauc’s plot.

(ii) Photoiuminescence Spectroscopy:

Photoluminescence (PL) is a process in which a substance absorbs photons

(electromagnetic radiation) and then re-radiates photons. Quantum

mechanically, this can be described as an excitation to a higher energy state

and then a return to a lower energy state accompanied by the emission of a

photon.

If a light particle (photon) has an energy greater than the band gap energy,

then it can be absorbed and thereby raise an electron from the valence band

up to the conduction band across the forbidden energy gap. In this process of

photoexcitation, the electron generally has excess energy which it loses before

coming to rest at the lowest energy in the conduction band. At this point the

electron energy eventually falls back down to the valence band. As this
98
happens, the energy it loses is converted back into a luminescent photon which

is emitted from the material. Thus the energy of the emitted photon is a direct

measure of the band gap energy, Eg. The process of photon excitation followed

by photon emission is called photoluminescence [6].

There are many types of photoluminescent process:

a) Resonant radiation:\Nhen a photon of a particular wavelength is absorbed

and equivalent photon is immediately emitted.This process is extremely fast

about 10ns, and no significant transition of the internal energy of the chemical

substrate between absorption and emission occurs.

b) FluorescencelNhen the chemical substrate undergoes internal energy

transitions before re-emitting the energy from the absorption.This process is

also fast, but some of the original energy is dissip'ated so that the emitted light

photons are of lower energy than those absorbed.

c) Phosphorescence: In phosphorescence the energy from absorbed photons

undergoes intersystem crossing into a state of higher spin multiplicity, generally

a triplet state. When the energy is trapped in the triplet state, transition back to

the lower singlet energy states is forbidden quantum mechanically. This leads

to a slow process of radiative transition back to singlet state that last from

minutes to hours [7].The lifetime of phosphorescence is usually from 10^-10~2s,

much longer than that of Fluorescence [8].Therefore, phosphorescence is even

rarer than fluorescence, since a molecule in the triplet state has a good chance

of undergoing intersystem crossing to ground state before phosphorescence

can occur.

99
A spectrometer is an instrument used for measuring the intensity of light as a

function of wavelength. Spectrometers usually contain a diffraction grating (or

prism) to disperse the light, thereby spreading out the light of differing

wavelengths into different positions. The spectrometer unit has an internal CCD

(charged coupled device) silicon detector, essentially a digital camera detector,

to measure the light intensity at various positions along its length. From the

emission patterns, photoluminescence spectroscopy is used in other fields of

analysis, especially semiconductors.

a) Band gap determination

Band gap is the energy difference between the lowest state in the conduction

and the highest state in the valence bands, in semiconductors. The spectral

distribution of PL from a semiconductor can be analyzed to nondestructively

determine the electronic band gap and this provides a means to quantify the

elemental composition of compound semiconductor [8],

b) Impurity levels and defect detection

Radiative transitions in semiconductors involve localized defect levels. The

photoluminescence energy associated with these levels can be used to identify

specific defects, and the amount of photoluminescence can be used to

determine their concentration .The PL spectrum at low sample temperatures

often reveals spectral peaks associated with impurities contained within the

host material. Fourier transform photoluminescence microspectroscopy, which

is of high sensitivity, provides the potential to identify extremely low

concentrations of intentional and unintentional impurities [8].

100
c) Surface structure and excited states

Photoluminescence, is very sensitive to surface effects or adsorbed species of

semiconductor particles and thus can be used as a probe of electron-hole

surface processes [8].

d) Recombination mechanisms

Recombination mechanism, can involve both radiative and non-radiative

processes. The quantity of PL emitted from a material is directly related to the

relative amount of radiative and non-radiative recombination rates. Non-

radiative rates are typically associated with impurities and the amount of

photoluminescence and its dependence on the level of photo-excitation and

temperature are directly related to the dominant recombination process

[8].When samples is exposed to photons, the photoexcitation of electrons from

the valence band to conduction band occurs and, the electrons losses excess

energy through non-radiative relaxation before falling to the lowest energy in

the conduction band. The electrons may radioactively recombine with holes of

the valence band and if the sample is completely free of impurities i.e. pure an

exciton gets formed between these two carriers with a small binding energy.

The characteristic of the energy levels is the energy of the emitted photons due

to band-to-band transition, an exciton recombination or any other possible

transitions [9].

If the sample is impure or doped, radiative recombination also may occur via

shallow donor or acceptor levels. In case of impure sample three types of

transition may occur, conduction band to acceptor level, donor level to valence

band and donor level to acceptor level.

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Thus, analysis of photoluminescence pattern can give information about the

impurity, energy transfer, bandgap of the material.

4.3.1(b) Energy Dispersive X-ray Spectroscopy (EDS)

Energy Dispersive Spectrometry (EDS) was first introduced in the late 1960s,

when solid state detectors were first interfaced to microanalyzers [10]. The

chemical composition of the sample is done by energy dispersive X-ray

spectroscopy (EDS). EDS systems are typically integrated into either an SEM

or EPMA instrument. EDS systems include a sensitive X-ray detector, a liquid

nitrogen is use for cooling, and software to collect and analyze energy spectra.

The detector is mounted in the sample chamber of the main instrument at the

end of a long arm, which is itself cooled by liquid nitrogen.ln all EDS all photons

emitted by the sample are collected and measured simultaneously by a solid

state X-ray detector. The common EDS detector is a lithium- drifted silicon,

Si(Li) [1]. The detectors made of Si(Li) crystals that operate at low voltages to

improve sensitivity, but recent advances in detector technology make available

so-called "silicon drift detectors" that operate at higher count rates without liquid

nitrogen cooling [11],Figure 4.4 is a schematic representation of EDS.

An EDS detector contains a crystal that absorbs the energy of incoming X-rays

by ionization, yielding free electrons in the crystal that become conductive and

produce an electrical charge bias. The X-ray absorption thus converts the

energy of individual X-rays into electrical voltages of proportional size , the

electrical pulses correspond to the characteristic X-rays of the element [11],

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Figure 4.4 Schematic of Energy Dispersive Spectroscopy [http://serc. carleton. edu/

research_education/.../eds.html]

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vviicii u id cicoiMjii ucai 11 n On i me ouui oc oil ir\co me oai i ipic, vanuuo i

in sample occurs and these are the characteristics of the elements present and

an be used for elemental identification.

When an electron approaches the atom it gets deccelerated due to coulombic

fi^lrl Thic* mot il+o ir» r% Iapo r\f anorrn/ r\f +he» ortH ^p/arpw or>r\<aoro no
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photon , referred to as bremsstrahlung or ‘ breaking radiation’. This radiation

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Wl IIWII l*J |JI IWWI lw» VI 1411 W I ui y • W \J till II IU WIIWI^jT Ml UIV VI l^ll IMI VlUVll WI I , UJ Mil

electron can lose any energy, from zero to the energy of primary electrons. The

ohorootorictio Y.rov/c omittoH W

WliWIVlYtVliWllW / ' i 14 j V VIIIIUVVI
h\i otonne
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will
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smoothly varying photon intensity. From the X-ray lines the atom can be

identified.The intensities of these lines is related to concentrations of the

emitting species in the sample [1],

EDS has certain limitations, the energy peak overlaps among different

elements, particularly those corresponding to X-rays generated by emission

from different energy-level shells (K, L and M) in different elements. Particularly

at higher energies, individual peaks may correspond to several different

elements; in this case, the user can apply deconvolution methods to try peak
103
separation, or simply consider which elements make "most sense" given the

known context of the sample [11]. EDS cannot detect the lightest elements,

typically below the atomic number of Na for detectors equipped with a Be

window. Polymer-based thin windows allow for detection of light elements,

depending on the instrument and operating conditions.

4.3.2 Structural Characterization

4.3.2 (a) X-ray Diffraction Technique

X-ray Diffraction (XRD) is one of the classical methods for identification and

characterization of crystalline solids. Each crystalline solid has its unique

characteristic X-ray powder pattern which is used as a” fingerprint” for its

identification. The method is based on the diffraction of X-rays by the sample in

different directions.Waves of wavelength comparable to the crystal lattice

spacing are strongly scattered (diffracted).

The X-ray source is Cu X-ray having a wavelength of Cu Ka lines, 1.54 °A The

diffracted rays aredetected by a detector placed on the opposite side shown in

figure 4.5.The X-ray source, sample and the detector are placed in a particular

configuration given by the Bragg-Brentano geometry that gives a 0-20 scan.

The source is stationary and the sample and the detector are mobile.When the

sample moves by an angle 0, the detector moves by angle 20. The rotation rate

is kept at 1°/min and the sample is scanned for 10°-80° scan. The sample is

loaded on a soda glass substrate [3].

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 Figure 4.5 X-ray Diffractometer[http://epswww.unm.edu/xrd/xrdclass/01-XRD-lntro.pdf]

Figure 4.6 Schematic of an X-ray diffractometer[http://epswww.unm.edu/xrd/xrdclass/01-

XRD-lntro.pdf]

The schematic of X-ray diffractometer is shown in figure 4.6.The angle and

intensities of the diffracted X-rays are used to perform crystallographic studies.

The intensity of the diffracted X-rays is measured as a function of the diffraction

angle 20 (Fig.4.7).The intensities of the spots provide information about the

atomic basis. The sharpness and shape of the spots are related to the

perfection of the crystal [12],

105
The structure of the material can be obtained from intensity Vs 20 plot.

(i) The presence or absence of a certain set of planes gives us the crystal

structures.

(ii) The shift of the peaks from its original positions in case of bulk crystals

gives the strains in the material.

20(Degrees)

Figure 4.7 X-ray Diffraction Pattern

Although the method of X-ray diffraction is quantitative, in general,it is used for

qualitative analysis. This form of analysis, extends to all crystalline solids

including ceramics, metals, insulators, organic, polymers, thin film powders etc.

X-ray diffractometers can be used either for single crystals or for powders.

While single crystal diffractometers are used for the study of molecular

structure, powder diffractometers are used for analysis of phases, though the

latter can also be used to derive molecular information [1],

Two approaches are generally used for the analysis of X-ray diffraction data.

i) Laue equations: In Laue equations, diffraction from one-dimensional

crystal may be treated in the same way as the diffraction by an optical grating.
106
Upon projection, the grating is like an array of points similar to a crystal. The

diffraction condition is again, nA=dSin0. In a crystal arrangement of atoms is

periodic in all three directions and three independent laue equations can be

written.The three equations have to be satisfied simultaneously for diffraction to

occur [1],

(ii) Bragg’s law: In Bragg’s law, a crystal is viewed as a plan containing

several lattice points. When X-rays are incident on a crystal, different lattice

planes causes simultaneous reflections of the X-ray beam. These simultaneous

reflections may cause constructive or destructive interference depending on the

angle of incidence of X-rays, interlayer separation, wavelength of X-rays. The

reflection being equal to the angle of incidence as shown in fig. 4.8.The

reflected beams are in phase when the path length between the beams is an

integral multiple of the wavelength.The planes of light travelling after reflection

will be in phase only when this condition is satisfied. This means that distance

ABC=nA or 2dSin0=nA. But for all other angles other than © destructive

interference occurs. Few specific directions along which the interference is

constructive are given by the Braggs law [1],

2dsin0 = nA (4.3)

Where d is the separation between the planes of the crystal,0 is the angle of

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

For all angle other than 0, destructive interference will occur leading to

cancellation of the intensity. For crystals containing thousands of such planes,

Bragg’s law imposes severe restrictions on 0 and the cancellation of intensities

107
is usually complete. However, in cases where number of diffraction planes is

limited, diffraction peak will broaden.

Figure 4.8 Bragg’s Law

Homogeneous and inhomogeneous strains can be characterized by studying

the diffraction peak positions of the XRD [2]. The shift in the peak positions is

due to homogeneous strain that leads to change of lattice constants and the

change in the d -spacing can be calculated.

Due to inhomogeneous stains broadening of the diffraction peaks are observe

that increases with increase in Sin0. Peak broadening is also caused by the

finite size of crystallites, in this case the broadening is independent of sin0.

From peak shapes contribution of crystallite size and inhomogeneous strain to

the peak width can be determined. The crystallite size D, can be estimated

from the peak width by Debye Schemer’s formula [13]

K?>
D= (4.4)
PCos8

108
Where p is the Full Width at Half maximum in radians, 9 is the peak position, D

is the average grain size, A is the wavelength of incident X-ray, K is the

Schemer’s constant, having value 0.9.

The accuracy of size by Schemer’s formula is limited to the cases where

instrument and stress-related broadening are negiigible.The lattice strain on

the particles is obtained by using the formula [5] between strain and particle

size,given by,

pcos© 1 t|Sm8
ADA, = “ + —— (4.5)
' #

Where p is the Full Width at Half maximum in radians, 0 is the peak position D

is the average grain size, A is the wavelength of incident X-ray, n is the effective

strain.The strain is determine from the slope of the plot between pcos0 / A and

sin0/A .whereas average particle size is obtained from the inverse of the y-axis

intercept obtained by extrapolating the above mentioned plot.

Indexing a diffraction pattern (also called a diffractogram or spectrum) involves

determining the lattice constant and structure and labeling each peak with its

appropriate hkl designation. In Bragg’s law, d can be in terms of lattice

parameter a0 and then the equation becomes

nX = 2dSine = 2 Sine (4.6)

The structure factor calculations give the relationship for allowed reflections for

cases of FCC and BCC structures [14].

109
4.3.2(b) Scanning Electron Microscope (SEM)

The first Scanning Electron Microscope was debuted in 1942 and commercially

produced in 1965.SEM is popular because of its versatility, various modes of

imaging, ease of sample preparation, possibility of spectroscopy and diffraction

as well as easy interpretation of the images. The best image resolutions is in

the range of 0.5 nm [1], SEM images have a characteristic three dimensional

appearance and can be used to judge structure [15],

In SEM, a monochromatic electron beam with a very fine spot size of ~ 5nm

and having energy from a few hundred eV to 50 KeV 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. The information is derived from the surface of the sample.

The schematic of SEM is shown in the figure 4.9. SEM consists of an electron

gun at the top, the "Virtual source” that produces a stream of monochromatic

electrons. The stream is then condensed by the first condenser lens(usually

controlled by the “coarse probe current knob”). This lens is used to form beam

and also to limit the amount of current in the beam. The condenser aperture

along with the first condenser lens works to eliminate the high-angle electrons

from the beam. The second condenser lens forms electrons into a thin, tight,

coherent beam and is usually controlled by the “fine probe current knob”. The

objective aperture further eliminates high-angle electrons from the beam. A set

no
of coils “scan “ or sweep the beam in a grid like fashion, dwelling on points for a

period of time determined by the scan speed. The last objective lens, focuses

the scanning beam onto the part of the specimen desired. The beam of

electrons strikes the sample and interactions occur inside the sample and are

detected by various instruments. The instruments count the number of

interactions and display a pixel on a CRT whose intensity is determined by this

number of interactions. Then beam moves to the next dwell point. This process

is repeated until grid scan is finished and then repeated, the entire pattern cab

be scanned 30 times per second [15].

Figure 4.9 Schematic of Scanning Electron Microscope [www.unl.edu/CMRAcfem/

semoptic.html]

In SEM, high spatial resolution microanalysis of materials is possible. The

spatialresolution of the analysis is made possible by the small dimensions of

excitation beam, of the order of a few nanometer [1], The electron beam

causes various excitations in the sample that are the characteristic of the

elements present in the material. Characteristic X-rays emitted by the sample

in
as a result of core hole decay is used for elemental identification .The intensity

of the signal can be use for quantitative analysis.

Microanalysis is done in two ways namely, “energy dispersive spectroscopy”

(EDS) and “wavelength dispersive spectroscopy”( WDS).EDS corresponds to

energy analysis and WDS corresponds to wavelength analysis.WDS is more

time consuming and cumbersome than EDS but improved energy resolution is

possible in comparision to EDS[1].

4.3.2(c) Transmission Electron Microscopy (TEM) &Selected Area

Electron Diffraction (SAED)

The first TEM was built by Max Knoll and Ernst Ruska with resolving power

greater than that of light, in 1933 and the first commercial TEM in 1939.TEM is

used to reveal the internal structure of materials. Magnifications of greater the

300k is possible in all TEM. Latest TEM has magnification of 50 million times.

Figure 4.10 is the schematic of Transmission electron microscope. The four

basic components of TEM microscope are (i) an electron gun, that emits a

beam of monochromatic electrons as the illumination source, (ii) a set of

condenser lenses to focus the illumination onto specimen,(iii) an objective lens

used to form first image of the specimen,(iv)a series of magnifying lenses to

create the final magnified image [16].

112
 Figure 4.10 Schematics of TEM [www.indepthinfo.com/.../electron-microscope]

Electrons are emitted by heating a filament (thermionic emission, tungsten or

LaB6 filament) or from an unheated filament that has an extremely high

potential gradient placed across the filament (field emission, fine-tipped single -

crystal tungsten) [16],The stream of monochromatic electrons move along the

optical axis of the microscope are focused to a small , thin, coherent beam by

the use of condenser lenses.The beam is restricted by the condenser aperture,

knocking out high angle electrons.The beam then strikes the specimen and

parts of it are transmitted.This transmitted portion is focused by the objective

lens into an image.The objective aperture enhances the contrast by blocking

out high-angle diffracted electrons, whereas the selected area aperture enables

to examine the periodic diffraction of electrons by ordered arrangements of

atoms in the sample. The image is then passed down the column through the

intermediate and projector lenses. The image strikes the phosphor image

113
screen and light is generated, allowing the user to see the image.The darker

areas of the image represent those areas of the sample that fewer electrons

were transmitted through .The lighter areas of the image represent those areas

of the sample that more electrons were transmitted through [15],

There are two image modes of TEM, Bright field mode and Dark field mode.ln

Bright field (BF) image mode an aperature is placed in the back focal plane of

the objective lens that allows only the direct beam to pass through [15].The

image results from weakening of the direct beam by its interaction with the

specimen Therefore, mass-thickness and diffraction contrast contribute to

image formation. Thick areas, that are areas in which heavy atoms are

enriched, and crystalline area appear dark contrast. The image is interpreted by

the simultaneous occurrence of the contrast-forming phenomena [16]. In dark

field image mode, the direct beam is blocked by aperature while one or more

diffracted beams are allowed to pass the objective aperature. As the diffracted

beams strongly interacted with the specimen, useful informations about planar

defects, stacking faults or particle sizes can be obtain.

In the TEM the electrons pass through the sample as it is thin.The electron

that pass through the sample is classified into three categories: the unscattered

electrons, the elastically scattered electrons and the inelastically scattered

electrons.The unscattered electrons pass right through the sample after

inciding with the sample without any interaction with the sample atoms and

transmission of these electrons is inversely proportional to the thickness of the

sample.So, thicker parts of the sample appear darker while the thinner part of

the sample appear lighter [17].The incident electrons that are deflected due to
114
their interaction with the sample but do not loss any energy , gives elastically

scattered electrons.The incident electrons are scattered during elastic

interaction and are scattered according to Bragg’s law .The scattered electrons

are collated by magnetic lenses and it form a pattern of diffraction spots.These

diffraction pattern gives information about orientation and atomic arrangement

in the area probed.This mode of operation is known as Selected Area Electron

Diffraction (SAED) [17].

When the incident electrons lose energy due to their interaction with the sample

atoms, the inelastically scattered electrons are generated.The inelastic loss of

energy by the incident electrons is the characteristic of the element of the

sample and this confirms the composition and also provide the bonding

information of the examined sample region [17].

4.3.2(d) High Resolution TEM (HRTEM)

HRTEM is useful for direct atomic level study like interface, dislocation, defects,

etc.lt allows imaging of the crystallographic structure of specimen at an atomic

scale [15].The highest resolution is 0.08nm.HRTEM is an imaging mode of

TEM.

In HRTEM, image is formed by the phase contrast due to interference in the

image plane of the electron wave with itself [18].The contrast formation in high

resolution TEM (HRTEM) can be explained by the wave nature of electrons. In

HRTEM, a virtually planar electron wave is transmits a thin specimen

(thickness < 20 nm), in most cases a crystal. During transmission the incident

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electron wave is scattered (or diffracted in the case of a crystal) at the

potentials of the atoms, and thereby the phase of the-electron wave is changed.

At the exit surface of the specimen the object wave is formed, which carries

direct and highly resolved information on the object. The object wave is

magnified in the electron microscope and during this process the wave suffers

additional phase shifts due to imperfect lenses (aberrations). Finally, the image

recorded on film plates or digital cameras is an interference pattern of the

image wave, which itself and it contains essentially phase contrast with all the

microscopic aberrations included. As the phase of the electron wave carries the

information about the sample and generates contrast in the image, and so

known as phase-contrast imaging. A single recorded image in HRTEM consists

of electron intensities only the phase of the wave and hence an important

information on the object is lost [19]. In conventional HRTEM, image

interpretation is performed by an iterative procedure by comparing numerically

simulated images with images acquired at the electron microscope. The

computer-simulated images are based on atomic model structures, including all

imaging parameters that need to be known as precisely as possible. The

resolution limit of the structure analysis is determined by the point resolution of

the microscope which is the optical resolution of the objective lens [19].

Each imaging electron interacts independently with the sample. Above the

sample, the wave of an electron can be approximated as a plane wave incident

on the sample surface. As it penetrates the sample, it is attracted by the

positive atomic potentials of the atom cores, and channels along the atom

columns of the crystallographic lattice (s-state model). At the same time, the
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interaction between the electron wave in different atom columns leads to Bragg

diffraction.As a result of the interaction with the sample, the electron exit wave

right below the sample <pe(x,u) as a function of the spatial coordinate x is a

superposition of a plane wave and a multitude of diffracted beams with different

in plane spatial frequencies u (high spatial frequencies correspond to large

distances from the optical axis). The phase change of cpe (x,u) compared to the

incident wave peaks at the location of the atom columns. The exit wave now

passes through the imaging system of the microscope where it undergoes

further phase change and interferes as the image wave in the imaging plane

(photo plate or CCD).It is important to realize that the recorded image is NOT a

direct representation of the samples crystallographic structure. For instance,

high intensity might or might not indicate the presence of an atom column in

that precise location. The relationship between the exit wave and the image

wave is a highly nonlinear one and is a function of the aberrations of the

microscope. It is described by the contrast transfer function [18].

The phase contrast transfer function (CTF) is a function of limiting apertures

and aberrations in the imaging lenses of a microscope. It describes their effect

on the phase of the exit wave <pe(x,u) and propagates it to the image wave.

Following Williams and Carter,[20] if we assume the weak phase object

approximation (WPOA) holds (thin sample) the contrast transfer function (CTF)

becomes

CTF(u)=A(u)E(u)sm(z(u)) (4.7)

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Where A(u) is the aperture function, E(u) describes the attenuation of the wave

for higher spatial frequency u, also called envelope function. ^ (u) is a function

of the aberrations of the electron optical system.

The last, sinusoidal term of the CTF will determine the sign with which

components of frequency u will enter contrast in the final image. If one takes

into account only spherical aberration to third order and defocus, x is

rotationally symmetric about the optical axis of the microscope and thus only

depends on the modulus u = |t/|, given by

Z(u)=jCsA3U4-My%u2 (4.8)

WhereCs is the spherical aberration coefficient, A is the electron wavelength,

and Af is the defocus. In TEM, defocus can easily be controlled and measured

to high precision. Thus one can easily alter the shape of the CTF by defocusing

the sample. Contrary to optical applications, defocusing can actually increase

the precision and interpretability of the micrographs.

The aperture function cuts off beams scattered above a certain critical angle

(given by the objective pole piece for ex), thus effectively limiting the attainable

resolution. However it is the envelope function E(u) which usually dampens the

signal of beams scattered at high angles, and imposes a maximum to the

transmitted spatial frequency. This maximum determines the highest resolution

attainable with a microscope and is known as the information limit. E(u) can be

described as a product of single envelopes:

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 E(ii)=EXu)EXu)Ed{u)Ev(u)ED{u) (4.9)

Where,Es(u) is angular spread of the source ,Ec(u) is chromatic aberration,

Ed(u) is specimen drift ,Ev(u) is specimen vibration ,ED(u) is detector

Specimen drift and vibration can be minimized relatively easily by a suitable

working environment. It is usually the spherical aberration Cs that limits spatial

coherency and defines Es(u) and the chromatical aberration, together with

current and voltage instabilities that define the temporal coherency in Ec(u).

These two envelopes determine the information limit [18].

One of the demerit with HRTEM is that image formation relies on phase-

contrast. The image is influenced by strong aberrations of the imaging lenses in

the microscope. One major aberration is caused by focus and astigmatism,

which often can be estimated from the Fourier transform of the HRTEM image.

Some of the techniques described above are adopted for characterising the as-

synthesised samples and those results obtained are presented in the next

chapter.

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