Characterization techniques

By: Sandeep Nagar

X-ray Diffraction
Since X-rays have the wavelengths of the same order of magnitude as the space between crystal
lattice of the order of few !" hence X-ray diffraction X#$" has proven a vital tool to study the
crystal structure of materials% &he ma'or advantage of this technique is that its non-destructive
method% &he X#$ methods which were originally designed for bul( materials are modified
slightly to study thin films% )or e*ample+ on account of the strong penetrating power of the
*-rays+ Source is (ept at a grazing incident angle of ,-- degrees so that X-rays do not reach
through the substrates and give information only about the thin films grown on the substrate%
.nformation related to the crystal structure of the films+ including lattice constants+ grain size+
preferred orientation of polycrystals+ defects+ stress+ etc% can be determined from the *-ray
diffraction measurement%
X-rays are electromagnetic waves% /lectrons with sufficient energy dislodge the inner core-shell
electrons of the target material% 0ost of the (inetic energy of the electrons stri(ing the target is
converted into heat+ less than ,1 being transformed into X-rays% Characteristic X-ray spectra are
produced by de-e*citation of these electrons from higher e*cited levels to their ground states%
&hese spectra consist of several components+ the most common being
k

and
k

% &he
k

line which is always present with

k

+ at a slightly shorter wavelength+ is filtered out

using an absorbing film% &he specific wavelengths are characteristic of the target material Cu+
)e+ 0o+ Cr"% )iltering foils of atomic number one or two less than the target material or crystal
mono-chromaters are required to produce monochromatic X-rays needed for diffraction% Copper
is the most common target material for X-ray diffraction+ with Cu 2
3
radiation 4 ,%56 !% &hese
X-rays are collimated and directed onto the sample% 7s the target and detector are rotated+ the
intensity of the reflected X-rays is recorded% 8e have above mentioned used Cu source for our
investigation%
.ncident monochromatic X-rays are diffracted by crystals as a result of scattering process in
which *-rays are scattered by the electrons of the atoms positioned in the lattice+ without change
in their wavelength% 7s the wavelength of X-rays is close to atomic size X-rays are ideal source
to study the structure of lattice% $ue to periodicity in the arrangement of atoms in a crystal+ the
diffracted *-rays interfere constructively or destructively with each other depending on the path
difference% 8%9% Bragg formulated the condition for constructive interference as:
-d sin=n
where+ d is the spacing between two ad'acent atomic planes+ is the angle between the atomic
plane and the incident *-rays+ n is the order of diffraction ma*imum+ and is the wavelength of
the *-rays% &he resulting diffraction pattern comprising both the positions and intensities of the
diffraction effects is a fundamental physical property of the substance% 7nalysis of diffraction
spectra gives complete information about size+ shape and orientation of the unit cell of the
crystalline material%
&he finite size of the crystallites has a mar(ed effect on the X-ray diffraction line widths which is
signified by Scherrer formula :B% $% Cullity and S% #% Stoc(+ /lements of X-#ay $iffraction+ ;rd
/d%+ <rentice =all+ New >ersey -??,"@:
crystallite=
n

hkl
cos
% 8here

hkl
is the full-width-half-ma*imum )8=0" of diffraction pea( signified by :h(l@
values" at degrees+ which originated as a result of X-rays of wavelengths being incident on
the crystal lattice and n is a shape dependent constant ?%A for spheres"% 8ith reduction in the
particle size+ observed X-ray diffraction lines broaden significantly% .t is important to subtract the
instrumental line width from the observed line width to get a correct estimate of broadening due
to small particle size% .n the case of amorphous materials+ C-ray diffraction pattern shows a very
broad hump signifying a very short range order in the material%
Scanning Electron microscopy
&he scanning electron microscope S/0" is a variety of electron microscope that uses
high-energy beam of electrons to scan the sample surface in a raster pattern to obtain image%
#esolution of the image depends on the energy of the electrons used% .n conventional S/0+
source of electrons is a tungsten or lanthanum he*aboride 9aB
B
" filament which is heated up to
produce electrons thermoionic emission"% &ungsten is used as filament because it has the highest
melting point and lowest vapor pressure of all metals+ thereby allowing it to be heated for
electron emission% &here is another method through which electrons can be produced i%e field
emission )/"% 7 high voltage applied between a pointed cathode and a plate anode causes
current to flow% &he field emission tip is generally made of a single crystal tungsten wire
sharpened by electrolytic etching%
&he accelerated electron beam+ which typically has an energy range in 2eC because
corresponding wavelength is in nm+ thus enabling us to resolve nm sized surface features"+ is
focused by one or two condenser lenses into a beam with a very fine focal spot size , to 5 nm"%
&he beam passes through pairs of scanning coils in the ob'ective lens+ which deflect the beam in
a raster fashion over a pre-defined rectangular area of the sample surface% &he ob'ective lens
does the final focusing of the beam onto the sample% 7t each beam spot+ the number of secondary
and bac(-scattered electrons reaching the detector is counted and is used for determining the
relative intensity of the pi*el representing that point in the final image% &he higher the atomic
number of the specimen material+ the greater is the number of bac(-scattered electrons that reach
the detector+ giving rise to a higher intensity in the image% &he image contrast gives us a direct
indication of electron density of the scanned area% &his whole assembly is maintained under a
high-vaccum chamber to avoid deflection of electrons by gas molecules%
S/0 imaging requires sample to be conductive as non-conductive and semi-conductive samples
will accumulate charge on the surface results in degradation of image contrast% &o overcome this
problem either the samples are coated with a conductive thin layer without damaging the
physical features of the surface"+ or charge compensation techniques are used within the vaccum
chamber%
Transmission Electron Microscope (TEM)
S/0 gives the information about surface features of a material but sometimes a more detailed
bul( picture is needed especially about the crystal structure as this information combined with
chemical nature+ reveals almost all properties of the material% )or this reason+ &/0 is used for
material investigation% &/0 employs electronically transparent sample for investigation of
crystal structures+ orientations and chemical compositions in phases+ precipitates and
contaminants through diffraction pattern%
&/0 and an optical microscope wor(s very similar% &hey have vastly different resolving powers
owing to the fact that they employ different wavelengths of radiations resolution of a
microscope depends on probing wavelength"+ but the wor(ing principle is almost the same%
Dptical microscopes employ glass lenses which bend light as per their refractive inde*+ whereas
electron microscopes use electromagnetic lens since electrons can be bent using electromagnetic
force% .n both case+ a source emits the radiation and a condenser lens assembly focuses the beam
onto the specimen% &he imaging system consists of an ob'ective lens that focuses the beam after
it has traversed through the specimen+ and forms an intermediate image% &his intermediate image
is in turn magnified by a pro'ector lens assembly to form a magnified final image% 7 schematic
diagram of a &ransmission /lectron 0icroscope &/0" is shown in )igure%
.n $iffraction mode+ Bragg angle can be calculated using the e*pression:
tan ( -E)=
R
L
8here+ # is the distance of a particular spot from the central bright spot and 9 is the distance
between the specimen and the diffraction plane (nown as lens constant"% Fsisng braggGs law+
these angles are converted to their respective
d
hkl
values and final e*pression comes out to be:
Rd=L
0aterial preparation is an important aspect of &/0 investigation since specimen needs to be
electronically transparent and hence preferably 'ust few hundreds of nanometers thic(% 8e have
used .on beams in a dual beam S/0 system to ma(e our samples for their investigation in &/0%