9.6.

SCANNING ELECTRON MICROSCOPE

"The scanning olectron microscope (SEM) is a tool for the character1zation
nano-glructures, A scanning of
clectron microscope produces images of a sample
SCANning with a focussed beamof electrons. The image
il by
n function of the probe cons1sts of the variation as
position, of some
probe The nteraction of the electrons withsignal generated by the sample under the
the atoms of the sample produce
RI6nals which contain information about the surface various
nlso about lhe composition of the sample. topography of the sample and
Various signals produced by a scanning
electron microscope are :
Secondary electrons (SE)
2 Reflected or back scattered electrons (BSE)
3. Photons of characteristic X-rays or light
4.
Absorbed current (i.e., specimen current) and transmitted electrons.
The specimen in SEM should be completely dry. The samples in an SEM can be
sobd or bulk specimens of any size that will fit within the specimen chamber
Specimenscan be studied in low vacuum,high vacuum, wet conditions and at a wide
range of very low or elevated temperatures. Both conductive and non-conductive
samples can be studied with the help of a SEM.Ascanning electron microscope can
achieve a resolution better than 1nm. A very narrow electron beam used in SEM
results in a large depth of field of scanning electron microscope micrographs
(images).
 230
9.7(a) and its schematic
Construction
principle
shown in Fig.
of a SEM is an electron gun
fitted with a tungsten diagram
filamentfor
The basic 9.7b). It consists of thermionically emitted. Tungsten is suitable
Fig. low vapour pressure. The low
Is shown in which electrons are melting point and
cathode from because of its high
making cathodes favour of tungsten.
in
cost also goes Electron gun
Electron beam

First condenser lens

Spray aperture

Second condenser lens

X-ray detector
Deflection coils
Electron gun Final lens aperture
Objective lens
electron beam Backscatter
electron detector
Condenser lens
Sample
Detector Secondary
electron detector
Secondary Electrons
Vacuum pump
H Sample (b)
Microscope
Fig. 9.7. Scanning Electron
(a)

electron beam into a narrow ens

set of condenser lenses is used to focuss the
A the electrons into a
coils or deflector plates are used to deflect
Pairs of scanning
sample in a raster fashion ovOr
direction so that the electron beam scans the
rectangular area of sample surface. Rectangular pattern of image capture and
such
reconstruction is called raster scanning. A number of detectors
secondary electron detector, X-ray detector, backscatter electron detector ete axe
also a part of the scanning electron microscope. These detectors are used to receive
various signals emitted from a scanning electron microscope when an energetic
beam of electrons falls over the specimen.
Working
A scanning electron microscope combines the ease of operation of an optical
microscope and the analysis capacities of a TEM. In a typical scanning electron
microscope, an electron beam is thermionically emitted from an electron gun fitted
with a tungsten filament cathode. This cathode is electrically heated for the
emission of electrons. The low energy (0.2 keV to 40 keV) electron beam is focussed
byone or two condenser lenses to a spot of 0.4 nm to 5 nm
in diameter. This focussed
 Characterization Techniques-Il Optical and Electron Microscopy 231
beam of electrons is then passed through a svstem of
deflection of beam in the x and y directions. Thusa rectangular magnetic lenses used for the
the sample is scanned by the electron beam. area of the surface of
The resulting image is a distribution
map of the intensity of the signal being
emitted fromn scanned area.
The energy exchange between electron beam and the specimen gives rise
to the
reflection of high energy electrons by elastic scattering. emission of secondary
electrons by inelastic scattering and the emission of electromagnetic radiation (.e.,
X-rays). The various interactions between electron beam and sample and the sIgnals
produced therein are shown in Fig. 9.8. Now we discuss various detection modes of
an scanning electron microscope one-by-one.
1. Secondary Electron Imaging (SEI) : This is the standard detection mode
of an scanning electron microscope. This mode collects low energy (< 50 eV)
secondary electrons that are ejected from the K-shell of the specimen atoms by
inelastic scattering interactions with beam electrons. These electrons originate
within a few nanometer from the sample surface. This is why SEM operation in the
SEI mode can produce very high resolution images of a sample surface. Secondary
electrons are detected by an Everhart-Thornley detector, which is a type of
scintillator photo-multiplier system. Steep surfaces and edges tend to be brighter
than flat surfaces, which results in images with a well defined, three-dimensional
appearance. Using the secondary electrons, image resolution of less than 0.5 nm
is possible. The brightness of the signal depends on the number of secondary
electrons reaching the detector. B a cs
k cattere
edlectrons
Characteristic

X-rays
Incident electrons
Secondary
electrons
(Primary electrons)
Auger
Photons electrons

Surface
+2 um
Specimen interaction volume

Sample

Fig. 9.8. Electron beam interaction and signals produced

2. Back Scattered Electron (BSE) Imaging : Back scattered electrons (BSE)

and are reflected or
are high energy electrons that originate in the electron beam scattering
back scattered out of the specimen interaction volume by elastic
emerge from
interactions with atomns of the specimnen. Back scattered electrons
the BSE resolution is
deeper locations within the specimen and consequently
 Nanoscence and Nanotechnology

Heavy elemnents (i.e., high value of atomic

electron images.strongly than light elements, therefore BSE
232
secondary
poorer than scatter electrons more between areas with different chemical
number D back contrast either of scintillator or of
detect detectors are
are used to Back scattered electron (i.e., surface) contrast is produced by
compositions. topographic of the specimen using an
Strong
semiconductor type. electrons from one side scattered electrons are used in
scattered
collecting backdirectional BSE detector. Back spectra as BSE signal intensity
asvmmetrical characteristic X-ray
SEM along with the the specimen. BSE images can provide
analytical of sample. Back scattered
to atomic number Z of the
1s strongly
related
chemical composition
crystallographic structure of the
information about the the
also be used to determine detecting back scattered electrons.
electrons can studied by
specimens can be
specimen. Thick Characteristic X-rays are emitted when the electron
Characteristic X-ray : from the sample and a highes
3. electron
removes an inner shell (K, L, M,...) into the vacancy and difference
beam of the outer shell
jumps composition
energy electron from any These X-rays are useful in determin1ng the
energy is released as X-rays. the sample.
elements in atoms excited by hiok
and abundance of emission of light when
Cathodoluminescence : The Cathodoluminescence Hi
4. ground state, is called
their valence band electrone
energy electrons return to beam in an SEM can cause
energy electrons in the electron semiconductor material leaving behind holes, In
to jump into conduction band in a
recombination of the electron-hole pairs (EHPs) will result
direct band gap material, Cathodoluminescence detectors either collect
in cathodoluminescence. In the SEM,
emitted by the specimen or can analyse the wavelengths emitted by the
all light Cathodoluminescence emitted
specimen and display an image of the distribution of
by the specimen in real colour.
Magnification : In an scanning electron microscope (SEM), the magnification
the raster
results from the ratio of the dimensions of the raster on the specimen and
on the display device. Keeping display screen at a fixed size, higher magnification
results from reducing the size of the raster on the specimen and vice-versa. The
magnification is controlled by the current supplied to the x, y scanning coils or to the
voltage supplied to the x, y deflector plates. Image magnification in an scanning
electron microscope does not depend upon the power of the objective lens.
Resolution
The spatial resolution of the SEM depends on the size of the electron spot,
which in turn depends on both the wavelength of the electrons and the electron
optical system that produces the scanning beam. The resolution is also limited by
the volume of the specimen material that interacts with the
electron beam (i.e.,
interaction volume). The spot size and the interaction volume are both large
compared to the distances between atoms, so the resolution of the
high enough to image individual atoms. SEM is not
 Characterization Techniques-l Optical and Electron Microscopy 233
Applications
In addition to
SEM can detect andtopographical, morphological and compositional
analyse surface fractures. provide information
structures, examine surface contaminations, information.
in micro
a
compos1tions, provide qualitative chemical reveal spatial variations in chemical
analysis
structures. SEM can be used for the study of and identify crystalline
research tool in life sciences, biology. parasites, SEMs can also be used as
physical sciences etc. medical and forensic science.
of semiconductor and Scanning electron mnetallurgy.
microscopes can be used for the production
microchips for computer
samples several centimeters in size and is industry. The SEM can observe bulk
applications than the TEM. consequently more flexible in its
Advantages
1.
Wide array of
2. applications.
Detailed 3D and topographical imaging. Can image
objects. comparatively bulky
3 Fast and easy
operation.
4.
Versatile information obtained from different
5.
Sample preparation is easy compared to TEM. detectors.
6. Data can be generated in digital
form.
7.
Interpretation of images is easy.
Drawbacks
1. SEMs are expensive, large and must be kept in an area free of
any possible
electric, magnetic or vibration interference.
2 Maintenance cost is high.
3. Special training is required to operate SEM.
4. There is risk of radiation exposure in it due to scattered
electrons.
5. SEMs are limited to solid, inorganic samples small enough to fit
vacuum chamber that can handle moderate vacuum pressure. inside the
6. Resolution limited to few nm.
7. Details on the atomic level can not be observed.
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12.13. STRUCTURE OF CARBON NANOTUBES
Carbon nanotubes are formed with a variety of structures with dittercnt
properties. The carbon nanotubes are not actually made by rolling graphite sheets
(graphene) but conceptually, different structures can be explained by consideratio
of the way graphene sheets might be rolled to form tubes. Ananotube caninbefig.lorne
12..
when a graphene sheet is rolled up about the axis Tof the tube as shown
The way the graphene sheet is wrapped is represented by a pair of indices (7, m).
T

(n, o) zigzag

Ch =na, t may
chiral

(n, n) armchair

basis vectors a and a2, the axis vector T,

Fig. 12.7. Graphite sheet showing the
right angles to T
and the circumferential vector Ch at
 Nanoscience and Nanotechnolo
vectors along two
292
m
denote the
number of unit directions in the
integers n and graphene.
The crystal lattice of
honeycomb circumferential vector and it is at right angles to the
the
The Ch is called and is also called the chiral vector. The
+m az.
vector T. Here Ch =naj
axis chiral indices. Here a and a2 are the unit
called
n and mare therefore,
indices
real space.
vectors of graphene in is its chirality. It represents the
An important
characteristic of nanotube twist
of the tube.
are rolled with respect toA
how the tubes
"Chirality refers to
of the T vector in the graphitic plane".
direction
nanotube structures constructed by roll1ng the graphite sheot
Three examples of orientations in the graphitic plane are shown i
about the T vector having different bonds of the carbe
the carbon-carbon (C-C)
fig. 12.8. When T is parallel to structure shown in fig. 12.8a. In this structis ee
hexagons. we get the "armchair"
both the indices m and n are equal.

Armchair (m = n) Zigzag (n, 0) Chiral (n, m)

(a) b) (c)
Fig. 12.8

The tubes shown in fig. 12.8b and fig. 12.8c,

and the chira! carbon are respectively known as zigzag
nanotubes. These are formed by rolling about a T
having d1ferent orientations in the graphitic vector
Zigzag and armchair CNTs are plane, but not parallel to C-C bonds.
chiral nanotubes. mzn. Thus we havecollectively called non-chiral nanotubes. In
 293
Nanotechnology in Carbon Materials
non chiral
(n, 0) i.e., m =0-> zigzag NTs
(2, n) i.e., m=n’ armchair NTs
and (n, m) i.e.. m*n>chiral NTs
inherently chiral because they
Fullerenes such as C76. C7s. Cgo and Cs4 are
are D, symmetric.
structure, we would see a spiral1ng row ol
When we observe the nonotube of chiral
atoms. Generally nanotubes are closed at both ends, which involves the
carbon arrangement on each end of the tube. CNTs are
introduction of a pentagonal topological
with each end attached to half of a large fullerene like structure.
essentially cylinders are found at the ends of the tubes.
carbon nanotubes, metal particles
In single-walled of the metal particles in their formation.
which is evidence for the catalytic role
Zigzag (n, 0)

(8,0) (9,0) (10,0)|

(0.0)H0) (2,0) (3,0) (4,0) (5,0) (6,0) (7,0)
(10,1)
(1.1) 2,1) | (3,1) (4,1) (5,1) (6.1) (7.1) (8.1) 9,1)
(9,2) (10,2)
(2,2)6,2) (4.2) (5.2) (6.2) (7,2) | (8,2)
(7,3) (8,3) (9,3)
(3,3) [(4,3) (5,3) (6,3)
(8,4) (9,4)
(4,4)) G,1) (6,4) (7,4)
(5,5) 6.5) (7,5) (8,5)

(6,6) 6) (8,6)

(7,7) Armchair (n, n)

Fig. 12.9.

angle between the chiral vector Ch and the

as the
The chiral angle 0 is defined
(0 -0) or between Ch and d. It is given by
zig-zag direction
Zig-zag :0 =0°
(2n +m)
COs.
Ch .41 Arm chair :0 =30°
IC,lajl 2 von'. +m + mn) Chiral : 0°<0<30°
If 0 is iimited to
tan9 the range 0<0 <30°.
(2n +m)
294 Nanoscionce and Nanotechnology

of an ideal
nanotube can be calculated from its (n, m) indices as
The dameter
follows
d-"vn' +m'+ nm)

Most of the properties of single-walled nanotubes (SWNTs) change significantl,

dependence is non-monotonic. Their band gan o
With the (n, m) values and this conductivity can show metallic
0 to 2 eV and their electrical
Vary from
semiconducting behaviour.
 SEM V/S TEM
" Ln sEM is based on soattered TEM ÍS based ow transmitted
electrons electrons
" The scattered electrons n SEM ln TEM, electrons art directy
produced the image of the sample pointed toward the sanple.
after the microscope collects and
counts the soattered electrons.
TEM Seeks to see what is inside
SEM focuses on the samples
surface and its conposition. or beyond the surface.
SEM shows the sample bit by TEM shows the sample as a
whole.
bit
SEM provides
TEM delivers atwo-dimensioal
three pícture.
dimensional image TEM has p to a50 milion
SEM OWy offers 2 milion asa magnification
maximn Level of The resolution of TEM is 0.5
magnification. angstroms
SEM has 0.4 nanometers.
 Salvothermal synthesis is a specialized method used in materials science and
chemistry to produce certain types of materials, particularly crystals and
ceramics. It is a variation of the hydrothermal synthesis method, which
involves the use of high-temperature and high-pressure conditions to
promote the growth of crystalline materials. Salvothermal synthesis is
specifically used when the desired material is not stable or difficult to
synthesize under conventional hydrothermal conditions.
Here's an overview of salvothermal synthesis:

1. Principle: Salvothermal synthesis typically involves subjecting a mixture of

reactants, often in powder form, to high temperatures and pressures inside a
specialized autoclave or reaction vessel. The term "salvothermal" combines
"salvo" (meaning sudden or intense) with "thermal," emphasizing the high
temperature aspect of the process.
2. Temperature and Pressure: Salvothermal synthesis is carried out at
temperatures well above the boiling point of the reaction solvent (usually
water) and at pressures significantly higher than atmospheric pressure. This
elevated temperature and pressure create an environment where reactions
that may not occur under standard conditions can take place.
3. Reaction Medium: The reaction medium in salvothermal synthesis is typically
water or another solvent, depending on the specific requirements of the
reaction. Water is often chosen because of its availability and its ability to act
as a reactant or participate in reactions.
4. Applications: Salvothermal synthesis is employed to produce a wide range of
materials, including ceramics, superconductors, semiconductors, and certain
types of crystals. It is particularly useful for materials that require high
temperature conditions to form or are unstable under ambient conditions.
5. Advantages: Salvothermal synthesis offers advantages like controlled crystal
growth, the ability to synthesize unique phases, and the possibility of tailoring
material properties by adjusting reaction conditions. It is especially valuable
for producing high-quality single crystals for scientific research and various
technological applications.
6. Challenges: Performing salvothermal synthesis can be challenging due to the
high-temperature and high-pressure conditions involved. Precise control of
these conditions is crucial to achieving the desired material properties and
crystal structures.
7. Safety Considerations: Due to the extreme conditions involved, safety
precautions are essential when conducting salvothermal synthesis. This
includes using specialized equipment designed to handle high temperatures
and pressures and taking appropriate measures to prevent accidents.
In summary, salvothermal synthesis is a specialized technique used in
materials science to produce materials that are challenging to synthesize
under standard conditions. By subjecting reactants to high temperatures and

pressures in a controlled environment, researchers can obtain unique materials

with tailored properties for various applications.
 Canbon lano Td.es
Defnahon nllotopu hat
Alano tubs ès (abon
corbon
Cabon (orbon nanchu
atom.
Aessenbles atbe d carbon breal,
dlficall to
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ate stll ight Bucky
but thay
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shape. shuctwe
into ylinducal ae hollow
nono tubtless
nano tbes. Tnside
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has diameleA ef
The Manotube

Types of CNTS
There ae
walled casbon navotubes
* Sige
* Multi walled anbon hanotube
 Sngk walled carbon Nanotabes
Tts Aupauontd as [SwCNI]
C

hey exist in a one dinonioval shuctwe. S

Some of the example swcNT m

h
d amclai.
The SwCNT
aNOnol a nm
SwCNT dianetes is
A nanowve s they exut
also knoun as
They re
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vaious fom o to vo le(t)
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theyshow both
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 CanbLon Aleunolues | Mn(ND
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he inner
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The angth
 Photonic crystais continue to be an active area of research and development, with
ongoing efforts to design and engineer novel structures for advanced optical and
photonic devices with applications in telecommunications, sensing, imaging, and more.
Plasmon wavequides, also known as surface plasmon wavequides or plasmonic
wavequides, are specialized optical wavequides that quide and confine surface plasmon
polaritons (SPPs) on the interface between a metal and a dielectric material. Surface
plasmon polaritons are collective electron oscillations coupled to electromagnetic
waves, and they enable the localization and manipulation of light at the nanoscale.
Plasmonic waveguides have various applications in photonics, sensing, and integrated
optics. Here are key features and applications of plasmon wavequides:

Features of Plasmon Waveguides:

1. Surface Plasmon Polaritons (SPPs): Plasmon waveguides rely on the interaction

between photons and SPPs. SPPs are surface electromagnetic waves that propagate
along the interface between a metal (e.g. gold or silver) and a dielectric material (e.g.
glass or semiconductor).
2. Subwavelength Confinement: Plasmonic waveguides offer subwavelength
confinement of light due to the high localization of SPPs at the metal-dielectric
interface. This property allows for miniaturized photonic devices and enhanced light
ma tor interactions
3. Propagation Losses: SPPs are subject to propagation losses, primarily due to the ohmic
losses associated with the metal. These losses can limit the propagation distance of
SPPs, making it essential to engineer plasmonic waveguides for low-loss operation.
4. Dispersion Properties: The dispersion of SPPs depends on the properties of the metal
and the dielectric. Plasmonic waveguides can exhibit unique dispersion relations,
allowing for control over the group velocity and phase velocity of guided modes.
5. Mode Profile Control: By varying the geometry and materials of the waveguide
structure, one can control the mode profile of plasmonic waveguides, tailoring their
properties for specific applications.
 Quantum Nanostructures:
Quantum Wells,
Dots Wires and
3.13. NANODOTS AND
Quantum dots QUANTUM DOTS
(or
87

nanodots
nanostructure materials
directions. Due to this in which
or nanocrystals)
electron motion is
are zero dimensional

lovels. As a result,
total confinement, electrons confined along all the three
in them can
discrete). All the three energy of
electrons have only
which quantum
in
dimensions quantum quantum
of dots is also discrete energy
dots lie in the range 1quantized (i.e.
mechanical effects
nanodots given to them. Since they play their role, hence the name to 100 nm in
they are
sometimes possess discrete energy levels likequantum dot or
referred
emission properties under to as artificial atoms. As atoms, hence
suitable conditions, hence they are quantum dots have light
nanoparticles. also called
fluoroscent
Quantum dots are those
semiconductor nanoparticles that are in "quantum size
dimensions are nanoparticles, the quantum size regime is obtained regime".
smaller than the exciton Bohr radius (which is a when their
For
length for semiconductor
Bohr radius is 5.4 nm. Somaterials). For example, for CdS characteristic
nm, are called CdS CdS nanoparticles with all the nanoparticles the excition
quantum dots, For GaAs the excition dimensions
Hence GaAs nanoparticles Bohr
less than 5.4
with all the dimensions less than radius is 11.3 nm.
GaAs quantum dots. 11.3 nm, are termed as
In case of metal
nanoparticles
are not so easy as in case of
the conditions for defining
quantum size regime
we have to semiconducting nanoparticles. For
calculate the density of the electronic states in metal nanoparticles,
nanoparticles. For gold terms of volume of
nanoparticles
gold nonoparticles with size less the quantum size regime begins at 2 nm. Thus
than 2 nm are called gold quantum
Quantum dots are a class of dots.
and bulk forms of the matter. Due materials
to the
intermediate in size between molecules
possess many size dependent properties.phenomenon of quantum confinement, they
Since different materials can have different
electrical potential energies, hence
quantum dots can be produced by combining materials with
properties. Quantum wells can be formed by growing GaAs layer different electrical
on AlGaAs. These
materials have different band gaps. If length, breadth and thickness of the quantum
well lie in the nanorange, then the
nanostructure that we have is essentially a
nanodot. If this nanodot exhibits quantum properties, then it is
called a
dot. Thus a quantum dot can also be a nanodot, but the reverse is not quantum
true.
necessarily
Quantum dots are composed of several tens to a few thousand atoms. Due to
their unique electrical properties, quantum dots find applications in several areas
such as solar cells, transistors, LEDs, medical imaging and quantum computing
etc.
 Quant wm dol wses
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