UNIT –V: Materials Science

Crystal planes:
A system of parallel and equidistant planes which can be imagined to pass through
the atoms in a space lattice such that they include all the atoms in the crystal are called
crystal planes. The position and direction of parallel planes in a crystal are represented by
Miller indices.

Miller Indices (h k l):

“Miller i nd i ces ar e t h r e e s m a l l e s t i nt eger s w h i c h h a v e t h e s a m e r a t i o a s
t h e reciprocals of the intercepts of the plane concerned on the three coordinate axes”.
Miller indices are generally written as (h k l).

Steps to find Miller Indices for a given crystal plane:

1. Find the intercepts made by the plane w.r.t X, Y & Z axes in terms of length of the
basis vectors, say x = n1a, y = n2b & z = n3c.
2. Express intercepts as ratios, say x/a = n1, y/b = n2 & z/c = n3.
3. Find the reciprocal of the ratios, say a/x = 1/n1, b/y = 1/n2, c/z = 1/n3.
4. Express above reciprocals to the smallest whole numbers by multiplying with L.C.M
of denominator.
Then a/x = h, b/y = k, c/z = l.

Examples:
1) Find Miller indices of the plane if it makes intercepts 1a,2b and 3c.
Solution: Here x = 1a, y = 2b, z = 3c
x/a = 1, y/b = 2, z/c = 3 a/x = 1,
b/y = ½, c/z = 1/3
Multiplying by 6 we get a/x = 6, b/y = 3, c/z = 2
Therefore Miller indices are (h k l) = (6 3 2)
2) Find Miller indices of the planes ABCD,BGDE and AEG given in figure below.

Solution: For the plane ABCD x = 1a, y = ∞b, z = ∞c

x/a = 1, y/b = ∞, z/c = ∞
a/x =1, b/y = 0, z/c = 0
Therefore ( h k l ) = ( 1 0 0 )

For the plane BGDE x = ∞a, y = 1b, z = 1c

x/a = ∞, y/b = 1, z/c = 1
a/x =∞, b/y = 1, z/c = 1
Therefore ( h k l ) = ( 0 1 1 )

For the plane AEG x = 1a, y = 1b, z = 1c

x/a = 1 y/b = 1, z/c = 1
a/x =1 b/y = 1, z/c = 1
Therefore (hkl)=(111)

3) Sketch the plane with (h k l) = (1 2 3) in a cubic unit cell.

Solution: For the plane (h k l) = (1 2 3),
∴ x = 1a ,y = b/2, z = c/3
It is shown in the figure.
 4) Sketch the plane with (h k l) = ( 1 1 0) in a cubic unit cell.
Solution: (h k l) = ( 1 1 0)
Here h = a/x = 1 implies x = 1a, k = b/y = 1 implies y = -1b, l = c/z = 0
implies z = ∞c i.e. plane is parallel to Z-axis.

This plane is shown in the figure.

Expression for interplanar spacing in terms of Miller Indices:

Let ABC be one of the parallel planes represented by Miller indices (h k l). Let OA = x,
OB = y and OC = z which are the intercepts made by ABC w.r.to X,Y & Z axis respectively.

Let another plane abc parallel to this plane passes through the origin of the coordinate
system O.
Draw a perpendicular OP to the plane ABC from O. Here OP = d = Interplanar
distance.

Let α, β and γ be the angles made by OP w.r.to X,Y& Z axis respectively.

From right angled triangle OPA, cosα = OP/ OA = d(hkl) / x,

From right angled triangle OPB, cosβ = OP/ OB = d(hkl) /y

From right angled triangle OPC, cos γ = OP/ OC = d(hkl) /z.

Here cosα, cosβ & cos γ are direction cosines of line OP.
For a Cartesian system of coordinates, cos2α + cos2β + cos2 γ = 1,

i.e. (d(hkl) / x)2 +( d(hkl) / y) 2 + (d(hkl) / z)2 = 1

(or)
1
d hkl =
1 1 1
2
+ 2+ 2
x y z
By convention of Miller indices, (h = a/x, k = b/y, l = c/z).
Substituting 1/x= h/a, 1/y = k/b, 1/z= l/c in the above relation we get,

d =

For cubic system, a = b = c.

a
d =
√ℎ + 𝑘 + 𝑙

• X-ray diffraction:
Inter atomic distances in a crystal are of the order of the wavelength of X- rays
i.e. (1 – 10 Å). Hence, when X-rays pass through a crystal, the radiation undergoes
diffraction. Thus a crystal acts as three dimensional grating for X-rays diffraction.

Bragg's law:
Bragg derived a relation between wavelength of X-rays, angular position of scattered

beam and separation of atomic planes in crystals.

Bragg’s law can be derived as follows.

In figure given below XY and X’ Y’ are two parallel crystal planes with interplanar

spacing ‘d’. Let two parallel X-rays AO & A’O’ be incident on crystal planes with angle of

glancing ‘θ’. The scattered X-rays OB & O’B’emerges at an angle ‘θ’ w.r.to the planes.

Draw perpendiculars OM and ON from O to the ray A O B .

 Here OO = d → Interplanar spacing

Triangles OO’M and OO’N are right angled triangles with

∟MOO’ = θ = ∟NOO’.

From the figure, path difference between the rays AO & A’O’ is, δ = MO +O N.

The rays will interfere constructively, if the path difference is an integral multiple of
wavelength.
i.e. δ = nλ where n =1, 2, 3…
∴ MO +O N = nλ ……………(1)
From right angled triangle OO’M ,
O M= d Sinθ
Similarly, from right angled triangle OO’N,
O N = d Sinθ
Substituting these values in equation (1), we get
2 d Sinθ = nλ
This is Bragg’s law of X-ray diffraction.
Powder X-Ray diffraction (PXRD) Pattern:
Quantitative determination of different crystalline forms and identification of the phases
of compounds that exist in solid samples can be determined by the versatile Powder X- ray
diffraction (PXRD) technique.
PXRD is a widely used characterization technique to know the phase of samples,
crystallite size and degree of crystallinity. X-rays when interact with a crystalline structure whose
atomic distances are same as wavelength of the wave, the diffraction occurs. Whenever the
diffracted ray satisfies the Bragg’s law, constructive interference takes place. Each diffracted X-
ray beam has a particular intensity & width, w h i c h depends on the nature and arrangement of
the crystallographic planes, domain size, orientation of domains and micro strain in the sample.

Schematic diagram of powder X-ray diffractometer

Figure shows the schematic diagram of XRD diffractometer. The main components of X-
ray diffractometer are X-ray tube, primary optics, goniometer or sample stage, secondary optics
and detector. Suitable slits are used to collimate the X-ray beam in the primary and secondary
side before and after diffraction.

 Phase identification by PXRD data:

A powder X-ray diffraction (PXRD) pattern is a plot of the intensity of X-rays scattered
at different angles (2θ) by a sample. Each diffraction peak is attributed to the scattering from a
specific set of parallel planes of atoms. Each powder diffraction pattern is characterized by a
unique distribution of both positions and intensities of Bragg peaks. Every individual crystalline
compound has its own “fingerprint” of PXRD pattern which enables the utilization of powder
diffraction data in phase identification.
 Typical PXRD pattern of a sample
In qualitative phase identification, the digital PXRD data is compared with other patterns
of standard available database. By quantitative analysis of PXRD data, it is possible to determine
the amounts of crystalline phases present in a mixture.

 Determination of crystal structure (PXRD method):

𝑛𝜆
From Bragg's law, 𝑆𝑖𝑛𝜃 = (a= lattice constant)
2𝑑

But interplanar spacing, d =

√
2 2 2
∴ 𝑆𝑖𝑛𝜃 = 𝑛𝜆 ℎ 2𝑎
+𝑘 +𝑙

2 2 2 2
𝜆 (ℎ +𝑘 +𝑙 )
∴ 𝑆𝑖𝑛2 𝜃 =
For 1st order diffraction, n = 1.
4𝑎2
If we have two reflection angles θ1 and θ2 from two set of planes, then we can write
𝑆𝑖𝑛 𝜃 (ℎ + 𝑘 + 𝑙 )
=
𝑆𝑖𝑛 𝜃 (ℎ + 𝑘 + 𝑙 )
where (h1 k1 l1) and (h2 k2 l2) are the Miller indices of the two set of planes.
➢ For BCC structure, the first two principal diffracting planes are (110) & (200).
𝑆𝑖𝑛2 𝜃1 12 + 12 + 02
= = 0.5
𝑆𝑖𝑛2 𝜃2 22 + 02 + 02
➢ For FCC structure, the first two principal diffracting planes are (111) & (200).
𝑆𝑖𝑛2 𝜃1 12 + 12 + 12
= = 0.75
𝑆𝑖𝑛2 𝜃2 22 + 02 + 02

𝑆𝑖𝑛2 𝜃1
Thus by measuring the ratio of for two Principal planes, we can conclude whether the
𝑆𝑖𝑛2 𝜃2
crystal belongs to BCC or FCC structure.
Nanomaterials:
Nanomaterials have emerged as an amazing class of materials with at least one dimension
in the range of 1 to 100 nm. Nanotechnology is the science that deals with matter at the scale of
nano meter (10-9 m), and is also the study of manipulating matter at the atomic and molecular
scale.
The properties of matter at the nanoscale level are substantially distinct compared to bulk
counterparts. Size-dependent effects become more prominent at the nanoscale. For example,
Gold solution appears yellow when in the bulk and it appears purple or red at the nanoscale level.
At the nanoscale, the electronic properties are substantially changed compared to bulk materials.

Quantum confinement:
When the size or dimension of a material is continuously reduced to a very small size,
the properties remain the same at first, but when the size drops below 100 nm, dramatic changes
in properties can occur. In Nano Crystals, the Electronic energy levels are not continuous as in
the bulk but are discrete (finite density of states), because of the confinement of the electronic
wave function to the Physical dimensions of the particles. This phenomenon is called Quantum
confinement.
Quantum effects can begin to dominate the behavior of matter at the nanoscale
affecting the optical, electrical and magnetic behavior of materials. Quantum confinement
is responsible for the increase of band gap which is tightly related with the optical and
electronic properties of the materials. Materials reduced to the nanoscale can suddenly
show very different properties compared to what they show on a macroscale. For instance,
opaque substances become transparent (copper); inert materials become catalysts
(platinum); stable materials turn combustible (aluminum); solids turn into liquids at room
temperature (gold); insulators become conductors (silicon).

High surface area to volume ratio:

Another important aspect of nanomaterials is surface area. When compared to the same
mass of material in bulk form, nanoscale materials have a relatively larger surface area. This
can make materials more chemically reactive, and affect their strength or electrical properties.
The surface area to volume ratio increases as the radius of the sphere decreases and vice
versa. It also means that when a given volume of material is made up of smaller particles, the
surface area of the material increases. Therefore, as size decreases, a greater proportion of the
particles are found at the surface of the material.
For example, if size is 30 nm, then only 5% of its particles lie on the surface; at 10 nm,
20% of its particles are on the surface; and at 3 nm, 50% of its particles are on the surface.
 Therefore, materials made of nanoparticles have a much greater surface area per unit volume
compared with the materials made up of bigger particles. This leads to nanoparticles being more
chemically reactive. As chemical reactions occur between particles that are on the surface, a
given mass of nanomaterial will be much more reactive than the same mass of bulk material.
This means that materials that are inert in their bulk form are reactive when produced in the
nanoparticle form.

Synthesis of nanomaterials:
Two main approaches are used for the synthesis of nanomaterials (1) Top-down approach
(2) Bottom-up approach.
In top-down approach, bulk materials are divided to produce nanostructured materials
by applying an external force. Top-down methods include mechanical milling, laser ablation,
etching, sputtering, and electro-explosion, etc...

In the bottom-up method, nanoparticles are produced starting from atoms of gas or
liquids based on atomic transformations or molecular condensations.
Applications of Nano materials
Since reducing the grain size to nanometer-dimensions provides increased strength and
hardness, super tough and superstring ceramics can be synthesized. Such super ceramics find
use in several engineering applications such as high efficiency gas turbines and in aerospace
and automotive components.
The increased diffusion rates in nanocrystalline metals and ceramics is used to make gas
sensors and fuel cells capable of operation at much lower temperature.
Aerosols, which are fine dispersions of a solid material in a gas, are used in agriculture,
forestry and military technologies.
Carbon Nano tubes (CNTs) and graphene are highly acknowledged members of the
carbon based nanomaterials family and they have been extensively explored for various
applications due to their high surface areas, rapid charge transfer properties and high
mechanical strength. Carbon quantum dots have received great attention in the fields of sensing,
nanomedicine, and bio imaging.
Layered metal-oxide-based materials are being explored as electrode materials in energy
conversion and storage devices. Semiconductor metal oxide materials are being tuned on the
nanoscale to enhance their performance for catalyzing water to produce clean energy.
Nanoparticulate thin films possessing desirable electronic qualities are of great interest
in microelectronics.
Semiconductor nanoparticles hold the potential for making more efficient solar cells,
optical transitions, spatial light modulations and other devices depending on non-linear optical
properties
Nanotech organic films will be the data storage medium of the near future using micro
electro-mechanical systems (MEMS). Information will be stored in clusters of molecules within
the inexpensive films.
Another application of nanoparticles is in pharmaceuticals. Biotech companies are
building fullerenes into molecules that will attach to and deactivate HIV molecules, blow up
cancer cells and repair neurological damage in a nerve illness.
Much more progress is anticipated, with nanomaterials being introduced into next-
generation devices to cope with future high energy demands and playing a more active role in
biosensors and nanomedicine to fight against existing and novel diseases.
Scaling laws in Miniaturization:
In nanotechnology the devices have dimensions of the order of nanometers. A study of
the scaling laws helps to get an idea of the magnitude of physical quantities involved in such
devices. Scaling is strictly dependent on the size of the physical objects such as the scaling in
geometry. It is assumed that the physical properties themselves do not change with the decrease
in size which is strictly not correct. With the reduction in size the laws of quantum mechanics
begin to operate and might give rise to a behavior not predicted by scaling laws. Scaling laws
are simple observations about how physics works on different sizes. The behavior of
force, strength, speed, among other things as a material or device is scaled down (from meter/
milli/ micro/ nano/ pico), or up. These trends cannot be generalized because they vary between
materials.

Scaling in dynamics:
In dynamics, the scaling effects can be determined using the laws of motion. The
important quantities which are involved in dynamical problems are mentioned below.
 Displacement scales as l1 (i.e. s ∝ l1),
 Velocity as lt-1 (i.e. v ∝ l1t-1) and
 Acceleration as lt -2 (i.e. a ∝ l1t-2)
 Mass scales as l3 and force is mass times the acceleration, dynamic force scales as l 4t-2
(i.e. F ∝ l4t-2)

Scaling in Electricity:
  Capacitance, C = Aε / d ∝ l2 / l
Thus, capacitance scales as l1. ( i.e. C ∝ l1)
 Electrostatic potential energy ( U = ½ CV2) scales as l3. ( i.e. U ∝ l3)
 Electrostatic force scales as l2. ( i.e. F ∝ l2)

The scaling law can be very nicely used even for actuators of macroscopic size. One
example can explain the principle. Consider an actuator with a characteristic length L based upon
electrostatic force and let the force it can develop be F. Now the actuator is miniaturized and
scaled down by a factor n. Since length scale is reduced by a factor n, the volume of the
miniaturized device will be n-3 times the volume of the original actuator. Next n3 numbers of
these miniaturized actuators are placed inside a volume equal to that of the original device and
arrangement is made so that all these n3 numbers of actuators act in parallel. Since the size of
each device is reduced by a factor n, each one will develop a force F/n2 as electrostatic force
scales as l2. The n3 numbers of these actuators, which act in parallel, will develop a total force n 3
× F/n2 = nF. Suppose n ∼ 1000, almost 1000 times larger force can be generated by the composite
actuator. This principle of miniaturized and massively parallel systems is employed by nature in
many situations and the muscles are nothing but massively parallel miniaturized protein
molecules acting on the basis of electrostatic force.

Atomic Force Microscope (AFM)

Atomic Force Microscopes (AFM) are extremely versatile tools that are widely used for
topographical measurements and imaging applications.
 An AFM uses a cantilever with a very sharp tip to scan over a sample surface. As the tip
approaches the surface, the close-range, attractive force between the surface and the tip cause the
cantilever to deflect towards the surface. However, as the cantilever is brought even closer to the
surface, such that the tip makes contact with it, increasingly repulsive force takes over and causes
the cantilever to deflect away from the surface.

Detection Method: A laser beam is used to detect cantilever deflections towards or away from
the surface. By reflecting an incident beam off the flat top of the cantilever, any cantilever
deflection will cause slight changes in the direction of the reflected beam. A position-sensitive
photo diode (PSPD) can be used to track these changes. Thus, if an AFM tip passes over a
raised surface feature, the resulting cantilever deflection (and the subsequent change in
direction of reflected beam) is recorded by the PSPD.

Imaging: An AFM images the topography of a sample surface by scanning the cantilever over a
region of interest. The raised and lowered features on the sample surface influence the deflection
of the cantilever, which is monitored by the PSPD. By using a feedback loop to control the height
of the tip above the surface—thus maintaining constant laser position—the AFM can generate an
accurate topographic map of the surface features.

Modes of operation: AFM has three differing modes of operation. These are contact mode,
tapping mode and non-contact mode.
In contact mode, the tip contacts the surface through the adsorbed fluid layer on the
sample surface. The detector monitors the changing cantilever deflection and the feedback circuit
adjusts the probe height to maintain a constant force and deflection on the cantilever.
In tapping mode, the cantilever oscillates at or slightly below its resonant frequency. The
amplitude of oscillation typically ranges from 20 nm to 100 nm. The tip lightly “taps” on the
sample surface during scanning, contacting the surface at the bottom of its swing. The feedback
circuit adjusts the probe height to maintain a constant amplitude of oscillation.
In non-contact mode, the cantilever oscillates near the surface of the sample, but does not
contact it. The oscillation is at slightly above the resonant frequency.