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Nanoscience and Nanot
194
oftenly found than hep. Studies regarding crystal structure are important beg
certain properties of nanostructures depend on their crystal structure.
Table 8.1: Crystal systems and Associated Space Groups in 2)
Us. System Parameters
ae
| 1, [Oblique az b= 90°
I lor (a = b, 7 # 90°, 120°)
| 2. [Rectangular az b, y= 90°
| 3. [Square la=b, y=90°
| 4. |Hexagonal ja =b, 7 =120°
Table 8.2 : Crystal systems and Associated Space Groups in 3D
is. System Parameters No. of Space Groups
| No. (Symmetry elements)
ii. [triclinic laxbec; aeBey 2
\2.__ [Monoclinic lazbec; a=y=90°%B 13
|3.__lOrthorhombie la bec; a=B=7=20° 59
\4.__ \Tetragonal ja=bec; = 90° 68.
|5.__[Trigonal la=b=c; 71 <120° # 90° 25
\6.__|Hexagonal la=bec; = 90°, 7 =120° 21
{z__ Tcubic la=b=c;a=B=7=90° 36
8.3. X-RAY CRYSTALLOGRAPHY
The atomic and molecular structure of a crystal can be determined by the.
technique of X-ray crystallography. A collimated beam of X-rays is directed at the
crystal and the atoms of the crystal cause diffraction of X-rays into many specific
directions (Fig. 8.1). By measuring the angles and intensities of these diffracted
beams, a three dimensional (3D) picture of the density of electrons within the crys!
can be formed. This provides information regarding the mean positions
the atoms in the crystal, their chemical bonds, their disorder etc. X-rays %
diffracted by various planes of atoms in crystal because their wavelength 2 is of
onder of inter planar separation d in the crystal. The wavelength of X-rays is #1
40.
nm
E
where E is the energy of X-rays in KeV,
‘The specular or coherent or Bragg reflection of
: Xx
the crystal is governed by the Bragg's law which is
2dsin® =n),
-rays from successive plan
Scanned with CamScanr yization Techniques-|
le that the X. 195
«pore is aa 7 ¢ X-ray beam makes with the plane of atoms and n ig
ee penned
sgt ael2 an
Usually the beam is kept fixed in direction and the
sod PANEE of angles to record the X-ray diffraction s
Incident i
beam oe
crystal is rotated through a
can,
dsin@ — dsino
Fig. 8.1. Scheme of Bragg's Ditfraction
The crystal planes are denoted by indices h, k, J called the Miller indices. The
interplanar separation d in simple cubic crystals, is given by
d= S. (3)
Vee +P
where a is the lattice constant of cubic crystal. The planes with higher h, k, J
values are closer together and hence have larger Bragg diffraction angles 0. The
"lative amplitudes of X-ray lines from different crystallographic planes help in
identifying the type of structure. For a bec lattice, diffraction peaks are observed only
for planes for which (h+k+l) is an even integer whereas for fcc lattice, diffraction
Peaks are observed when either h, k, / are all odd integers or all even integers.
Xray spectra are recorded for rotations of the erystal around the mutually
Perpendicuiar planes of the crystal to provide comprehensive information on various
“ystallographic planes. : ‘ :
Fourier transforms are used to find the positions of atoms in the unit cell. This,
iretdure identifies the space group associated with the structure and morte the
“sth of lattice constants a, b, ¢ of the unit cell and also the values of angles a, y
“ween them,
init? Widths of the Bragg peaks of the X-ray scan of a
deg tion on the average grain size of the sample, noe of grain size.
“stron Microscope (TEM) is needed for the actual determination
: i the outgoing
“"Y crystallography is a form of elastic scattering beens iva hact
7 V8 have the same energy and wavelength as the incoming x ‘
hod for characterizing the atomic structure of new materials.
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sample provides
a transmission
_ 196
8.4. DEBYE-SCHERRER METHOD :
od of X-ray diffraction is
Nanoscience and Nanotech
suitable for samples: in powder form,
i ‘ in pow a4
aan a very fine walled glass tube. A monochromatic (inl welengdy
a ie directed onto the sample. The tube can De ro Out the
ee ig, 8.2b), The conical pattern of X-rays emerging fy
re i tion pattern (fi a :
eee sin@ =nd), is incident on the film strip in arcs as shown
e
fig. 8.2c. The Bragg angle is
Ss
oe
where S is the distance between the two corresponding reflections the ae and gE
is the radius of the film cylinder. The advantage of this metho s oH all the
Bragg angles can be determined simultaneously by exposing the powdered sample
with the X-ray beam only once. Debye-Scherrer method is also used for sample
identification. This technique has been widely used to obtain the structures of
powders of nanoparticles.
Fig. 82. Debye-Scherrer powder diffraction technique (a) sketch of the apparatus (b) an X-ray beam trajectory
the Bragg angle 0, (c) images of arcs of the diffraction beam cone on the film plate
Crystals that have the same crystal structure but different lattice constants
called isomorphic erystals. X-ray crystallography is used to study such crystal
The chief advantages of this method are :
> simplicity of sample preparation
> high rate of measurement
» the ability to analyze mixed phases such as soil samples
> “in situ” (ce. during the growth) structure determination.
Uses of Debye-Scherrer method may be summarized as follows :
> For sample identification
> To obtain the structures of powders of nanoparticles
> To study isomorphic crystals.
Scanned with CamScanner 8.7. INCREASE IN WIDTH OF XRD PEAKS OF NANOPARTICLES
If in the intensity versus angle plot (ie., diffraction pattern) of X-rays, the
diffraction peak is not sharp like a 5-peak, then the peak (or line) is said to be
broadened. Full width at half maximum (FWHM) is typically used as a measure of
the broadening of the peak (fig. 8.4).
Intensity
Diffraction angle 20 ——__»
Fig. 8.4,
In X-ray diffraction (KRD), line broadening can result from many sources. These
sources may be classified into two categories :
Sources of Peak broadening
Instrumental broadening Sample broadening
(broadening from an imperfect) (broadening from an imperfect)
diffractometer sample i
The actual line broadening is the combined effect of these two factor
Instrumental broadening has to be subtracted to get the broadening effects due ®
the sample. These effects are interdependent in the sense that any imperfection
one will in turn affect to all the imperfections of the other.
Scanned with CamScanner gon TOCHNTIOS
cae trumental Broadening :
jn j i
git sources of instrumental broadening of XRD peaks are as follows :
‘ the source of radiation (¢.g., X-rays) has a finite
@ s rfectly sharp spot or line
201
physical size i.e., not being a
4g) radiation (eg. X-rays) not being perfectly monochromatic,
instead have a
range of wavelengths 84, about mean wavelength i.
gi the active diffracting volume within the sample is finite and therefore
diffraction occurs away from the true centre of the diffractometer
(iv) incident or diffracted beams may have axial divergence
() the configuration of the defining slits used in the diffractometer
(vi) any misalignment of the diffractometer.
‘The instrumental contribution to line broadening is measured by using a nearly
parte sample whose broadening contribution is negligible as compared to
instrumental broadening. Materials suitable for this purpose are : LaBg, BaF) and
KCl.
87.2, Broadening due to Sample Imperfection
The imperfections of the sample that contribute to the increase in width of XRD
peaks are :
() crystallite/domain diffracting size : The broadening of XRD peaks is
associated to the reduction of crystallite size because of the broken ligand at
the surface of nanoparticles. When particle size is reduced, the ratio of
disordered atoms at the surface of particles with the ordered atoms in the
centre of nanoparticles is higher than in large particles (bulk). This is
reflected at the XRD patterns as a peak broadening and a reduction of
intensities of all peaks. i
Gi) crystal lattice distortion (micro strain) due to dislocations and concentration
gradients. It should be noted that macro strains (arising from pulling a
Specimen) will result in peak shift but not in peak broadening,
i) structural ‘mistakes’ such as stacking faults, twin faults or layer mistakes
(vy Concentration gradients in non stoichiometric compounds. acini Bea
i i eter's broadening Bj, is
Fist of all by using a nearly perfect sample, diffractom sed eanipleend
deter A ted by taking the desired samp!
2, Ted. The measurement is then repeal ey. sample, Bins is subtracted
bon 18 obtained. To get broadening due to imperfect 5 :
‘otal. If the line profile is Gaussian, then
2 pt Be
Prcmple =B ‘total Bins
| Whe
"eB Tepresents the line width.
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Nanoscience and Nanotect,
202 .
ORMULA
ae ne is a relation between the sete ef ane
ticles crystallites in a solid and the line widtl ae re Pn in,
diffraction pattern. It was given by Paul Scherrer and is ieee or the leterm 5
of size of the particles of erystals in powder form. It is eae ae Its
not applicable to grains larger than about 0.1 to 0.2 ym. This formula gives q, f
lowest possible value of particle size. Scherrer's equation is
: Kh
= Bcos of
where,
+ = mean size of the crystallite domains, which may be smaller or equal tot:
grain size
K= dimensionless shape factor close to unity. Its typical value is 0.9 but varies
with the actual shape of the crystallite
i. = wavelength of radiation (X-rays)
§ = line width (in radians) at half the maximum intensity (i.e., FWHM), afte
subtracting the instrumental line broadening
8 = Bragg angle in degrees.
The most important factor for broadening of XRD peaks besides instrument!)
broadening and crystallite size are the inhomogeneous strain and erystal lattice
imperfections. These imperfections include dislocations, stacking faults, twinnine
micro stresses, grain boundaries, sub-boundaries, coherency strain, chemo)
heterogeneties, and crystallite smallness. If all of these other contributions for b*
width were zero, then the line (or peak) width would be solely determined by
crystallite size and the scherrer formula would come into picture. If the ee
contributions to the peak width are non zero, then the crystallite size can be
than that predicted by the Scherrer formula,
Scanned with CamScanner 9.5. TRANSMISSION ELECTRON MICROSCOPE
Electrons can be produced, focussed, accelerated to high energies and converted
into a collimated beam easily. These highly energetic electrons have wavelengths of
the order of picometers (10712 m). A transmission electron microscope (TEM) uses
energetic beam of electrons to provide topographical, morphological, compositional
and crystallographic information on samples or specimens. The first TEM was built
by Max Knoll and Ernst Ruska in 1931.
In the TEM experiments a focussed beam of electrons is transmitted through
ultra-thin specimen under ultra-high vacuum (= 1074 Pa), interacting with the
atoms of the specimen as it passes through it. An image is formed from a
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zation Techniques-HI Optical and Electron Micros.
copy
_ praction of the electrons transmitte
inter : itted through th, n ‘
ified and focussed onto an imaging device, such ono nn image is
rf photographic ha or itis detected by a sensor like a change yore 8 &
, sea ;
(cc). TEM has a higher resolution (=0.05 nm) due to nail do's a
wavelength of electrons. This enables TEM to capture fine denne ee, rose
2s single column of atoms. ——
Is even as small
TEMs produce high resolution,
two-dimensional images which gives it a wide
\ Ah r ages
ce b : ges which gives it a wide
dustry applications, It i j i
1 e and ations. It is a ma; dl
in physical, chemical and biological sciences, ne een eek
Electron gun
Electron beam
Condenser lens
x
ZZ, Sample
za
Objective lens
Phosphor screen
Image of sample
tie (b) Image formation
] ae 9.6. Transmission Electron Microscope oat! an enes
Principle : A transmission electron microscope ears r igh ig pa
source (tungsten filament or La source). Materials WTO ced for the gun
uch as tungsten, or those with a low work function ( aro) Vy and it emits eletrons
Slement. The electron gun is given a high voltage (OTT are focussed by an
onic emission or by field electron emission.
y the
i ron -setor) lens, and finally produce
Sicetive lens, are amplified by a magnifying Corio
ving tional TEM is shown in
“sired image on a screen. The basic principle of a onmven
‘ .6 (b).
1 96 a) and ite ray diagram is shown in Be: ® re Blectrostatic fields also
The jpulate the electron ‘ ing deflections
uch amma svi ag fee ie
ee , Imag
an’ tise to a shift in the path of the beam
, tent. The observed image
interact with and absorb electrons 10 2 MEF ST oy the phase of
cea ’® upon the amplitude of electrop he
“etrong,
Scanned with CamScanner 228 Nanoscience and Nanotech =
The most common mode of operation for a TEM is the bright field j bn
mode. The contrast is formed directly by occlusion and absorption of. electrong ing y
sample. Thicker regions of the sample, or regions with a higher stoma number "
absorb more and hence appear dark, while regions with no samp) ea ae beam Ph
will appear bright. Hence the name bright field imaging given to this mode, ny
image is formed due to undeviated transmitted electron beam.
Another mode of operation of TEM i.e., diffraction image observation re
is the one in which the contrast is produced by the Brage scattering (diffraction
electrons by the atoms of the crystalline sample. This method can be used foe
identification of lattice defects in crystals. The position and type of the defect can by
accurately determined. This mode is referred to as the selected area electron
diffraction (SAED) mode. :
‘The magnification of the TEM is due to the ratio of the distances between the
specimen and the objective lens image plane. TEM has ability to change
magnification simply by modifying the amount of current that flows through the
coil, quadrupole or hexapole lenses. Higher resolution imaging requires thinner
samples and higher energies of incident electrons. For best results, the film thickness
should be of the order of mean free path of electrons in the sample.
Much thinner films exhibit too little scattering to provide useful images, and in
thick films, multiple scattering events dominate making the image blurred and
difficult to interpret. Image processing can be used to increase the information
obtainable from a TEM image.
Applications
Transmission electron microscopes (TEMs) find application in cancer research,
virology, material science, nano-technology and semiconductor research. Lattice
structure of the material can be determined by TEM. The shape of the sample can
be determined from the image. TEMs can be used to detect flaws, fractures.and
damages to micro-sized objects. Imaging capabilities of TEM are aided
(complemented) by diffraction patterns for structural studies and spectroscopi¢
techniques for chemical analysis, :
Advantages
1, Transmission electron microscopes (TEMs) provide most _powertil
magnification of one million times or more.
2. It has wide range of a
ficlde plications in educational, scientific and industrial
TEM can provide information on element and compound structure.
4, It forms detailed and high quality image of samples, It produces bight
resolution images.
Scanned with CamScanner sion Techniques! Optical and Electron Microscopy
Basy operation.
o
Yield information of surface features, shape, size and structur
e.
6
prawbacks ‘
1 ‘TEMs are large and very expensive.
5 Extensive sample preparation is required to produce a sample thin enough
| “ao to 100 nm) to be electron transparent, Producing thin samples is ait
| difficult and these may not represent the larger object to which they belong,
4g. TEM analysis is a relatively time consuming process and requires special
training.
The sample may be damaged by the electron beam.
4
5, TEMhasa relatively small field of view. Thus ata time a very small portion of
the specimen is observed.
6. Thestructure of the sample may get changed during the sample preparation
process.
7. Complicated contrast mechanisms which makes image interpretation
difficult.
96. SCANNING ELECTRON MICROSCOPE
The scanning electron microscope (SEM) is a tool for the characterization of
nano-structures. A scanning electron microscope produces images of a sample by
scanning it with a focussed beam of electrons. The image consists of the variation as
2 function of the probe position, of some signal generated by the sample under the
probe. The interaction of the electrons with the atoms of the sample produce various
signals which contain information about the surface topography of the sample and
also about the composition of the sample. Various signals produced by a scanning
electron microscope are :
1. 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.
aie specimen in SEM should be completely dry. The samples in an SEM can be
| or bulk specimens of any size that will fit within the specimen chamber.
aay ee can be studied in low vacuum, high vacuum, wet conditions and at a wide
Smples low or elevated temperatures. Both conductive and non-conductive
-»'¢s can be studied with the help of a SEM.-A scanning electron microscope can
a resolution better than 1 nm. A very narrow electron beam used in SEM
(rages). a large depth of field of scanning electron microscope micrographs
Scanned with CamScanner inoscience and Né
280 Nat anotechnotog,
Construction
The basic principle of a S ig. 9.7(a) and its schematic diagram
EM is shown in Fi vit
is shown in Fig. 9.7(b). It consists of an electron gun et os a tungsten flan
cathode from which electrons are thermionically i a mn nes n i ual at
making cathodes because of its high melting point and Jow vapour P} °. The Inn
Cae electron detector
cost also goes in favour of tungsten.
Flectron gu"
+~ Electron beam
First condenser lens ~f
Spray aperture}
Second condenser lens ig
<> Xray detector
Deflection coils
Electron gun a =
Final lens aperture 44 Se jective
. ae Backscatter |
Sample
Caecea? ‘Secondary
electron detector
Zig secondary Betrons LI
‘Sample Vacuum pump
)
Fig. 9.7. Scanning Electron Microscope
Ww
‘A set of condenser lenses is used to focuss the electron beam into a narrow spot
Pairs of scanning coils or deflector plates are used to deflect the electrons into x or?
direction so that the electron beam scans the sample in a raster fashion over ¢
rectangular area of sample surface. Rectangular pattern of image capture and
reconstruction is called raster scanning. A number of detectors such a5
secondary electron detector, X-ray detector, backscatter electron detector etc. are
also a part of the scanning electron microscope, These detectors are used to receive
various signals emitted from a scanning electron microscope when an energeti¢
beam of electrons falls over the specimen,
Working
_ A scanning electron microscope combines tho ease of operation of an optic
microscope and the analysis capacities of a TEM. In a typical scanning elect
mieroneope, an electron beam is thermionically emitted from an electron gun fitted
vibe haneien filament cathode, This cathode is electrically heated for th?
F of electrons. The low energy (0.2 keV to 40 keV) electron beam is focuss®
y one or two condenser lenses to a spot of 0.4 nm to 5 nm in diameter. This focuss™
Scanned with CamScanner t
Peper Jo
zation Techniques-l! Optical and Electron Microscopy
electrons is then passed through a s >
am 0 i throu stem of magneti :
wereaion of beam in the x and y directions. ‘Thus a rectangular aren ont for the
spe sample 38 scanned by the electron beam. The resulti ei of the surface of
> of the intensity of the signal being emitted from eéatined ates aii
‘she enerey exchange between electron beam and imen gives i
reflection of high energy electrons by clastic a a bes
ns by inelastic scattering and the emission of electromagnetic radiation (ie,
df) The various interactions between electron beam and sample and the signals
tance therein are shown in Fig, 9.8. Now we discuss various detection modes of
i canning 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)
Sreondary electrons that are ejected from the K-shell of the specimen atoms by
Stlastic 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 an produce very high resolution images of a sample surface. Secondary
electrons are detected by an Everhart-Thornley detector, which is a type of
