Module 3

Functional Materials
&
Deposition techniques
 What are nanomaterials?

Materials are observed in our day to day

life is three dimensional (3D)

If any one of the dimensions is in between

100 nm to 1 nm dimension. We call them
NANOMATERIALS
3
§ Introduction to Nanomaterials
• A nanoparticle is an entity with a width of a few nanometers to a few
hundred, containing tens to thousands of atoms. Their defining
characteristic is a very small feature size in the range of 1-100 (nm).

• Nano size:
One nanometre is a millionth part of the size of the tip of a needle.
1 nm = 10-6 mm = 10-9 m
Table 1. Some examples of size from macro to molecular
Size Examples Terminology
(nm)
0.1-0.5 Individual chemical bonds Molecular/atomic
Bulk Gold
0.5-1.0 Small molecules, pores in Molecular
zeolites
1-1000 Proteins, DNA, inorganic Nano
nanoparticles From: USDA’s
103-104 living cells, human hair Micro roadmap of
nanotechnology.
>104 Normal bulk matter Macro
4
Link
Categories of Nanomaterials

6
• Nanomaterials show unusual
⮚ Mechanical
⮚ Electrical
⮚ Optical
⮚ Magnetic properties.

Hence it has potential applications in

⮚ Different industries
⮚ Biomedical
⮚ Electronic applications.
⮚ For example, long lasting medical implants of
biocompatible nanostructured ceramic and
carbides,
⮚ Biocompatible coating
⮚ Drug delivery
⮚ Protection coatings
⮚ Composite materials
⮚ Anti fogging coatings for spectacles and car
windows etc. 7
 What makes these nanomaterials so different and so intriguing?
⮚ Deviation from the reduced size and dimensionality of the nanometer-sized
building blocks (crystallites), the numerous interfaces between adjacent
crystallites, grain boundaries and surfaces
⮚ These building blocks have different crystallographic orientation that may
lead to incoherent or coherent interfaces between them
⮚ Lead to inherent heterogeneous structure on a nanometer scale.
⮚ Grain boundaries make up a major portion of the material at nanoscales,
and strongly affect properties and processing.
⮚ Surfaces and interfaces- half or more than half atoms near to interfaces
⮚ Hence, surface properties such as energy levels, electronic structure,
and reactivity are different from bulk materials

8
 BAND GAP IN NANO AND BULK MATERIALS

⮚ Band Gap

9
10
 Gold : Bulk vs. Nano
Bulk Gold Nano Gold
1 Lustrous–they have a shiny surface Are never gold in colour but found in a
when polished range of colours
2 Malleable–they can be hammered, bent Size & Shape of the nanoparticles
or rolled into any desired shape determines the colour
3 Ductile–they can be drawn out into wires For example, Gold particles in glass
25 nm > red reflected
50 nm > green reflected
100 nm > orange reflected
4 Is metallic, with a yellow colour when in Are not “metals” but are semiconductors
a mass (Band gap energy = 3.4 eV)
5 Good conductors of heat and electricity Are very good catalysts
6 Generally have high densities
7 Have high melting point (~1080oC) Melts at relatively low temp (~940º C)
8 Are often hard and tough with high
tensile strength
9 Having high resistance to the stresses
of being stretched or drawn out
10 Not easily breakable
11 Inert-unaffected by air & most reagents
11
 Size and shape dependent colors of Au and Ag nanoparticles
Gold NPs in Glass Silver NPs in Glass
25 nm
100 nm
Sphere
Sphere
reflected
reflected

50 nm 40 nm
Sphere Sphere
reflected reflected

100 nm
100 nm prism
Sphere reflected
reflected

12
12
 Size and shape dependent colors of Au and Ag nanoparticles

Note: nanomaterials scatter visible light rather than absorb

⮚ Distance between particles also effects colour

Surface plasmon resonance: Excitation of surface plasmons by light (visible

or infra red) is denoted as a surface plasmon resonance
Localized surface plasmon resonance (LSPR) for nanometer-sized metallic structures
13
13
 Nanoparticles preparation:
❖ Top-down approaches
⮚ High-energy ball milling/Machining
⮚ Chemical Oxidation Process (CNTs to QDs)
⮚ Electrochemical Oxidation Process (Graphite rod to QDs)
⮚ Lithography (photo- and electrochemical)
⮚ Etching/Cutting
⮚ Coating
⮚ Atomization
❖Bottom-up approaches
⮚Gas Condensation Processing (GCP)/Aerosol Based Processes
⮚ Chemical Vapour Condensation (CVC)
⮚ Atomic or Molecular Condensation
⮚ Laser ablation
⮚ Supercritical Fluid Synthesis
⮚Wet Chemical Synthesis of nanomaterials (Sol-gel process)
⮚ Precipitation method
⮚ Spinning
⮚ Self-Assembly
14
⮚ DNA Origami
 Schematic representation of the principle of mechanical milling
High-energy_ball_milling

WC coated
50 µm powder ball

Ball_mill

220px-8000M_Mixer_Mill_%28open%29_incl_accessories

15
 Mineral, ceramic processing, and powder metallurgy industry

❖ Procedure of milling process

⮚ Particle size reduction, solid-state alloying, mixing or blending, and
particle shape changes
⮚ Restricted to relatively hard, brittle materials which fracture and/or

deform and cold weld during the milling operation

⮚ To produce nonequilibrium structures including nanocrystalline,

amorphous and quasicrystalline materials
⮚ Users are tumbler mills, attrition mills, shaker mills, vibratory mills,
planetary mills etc
⮚ Powders diameters of about 50 µm with a number of hardened steel or
tungsten carbide (WC) coated balls in a sealed container which is
shaken or violently agitated. The most effective ratio for the ball to
powder mass is 5 : 10. 16
• Shaker mills (e.g. SPEX model 8000) uses small batches of powder
(approximately 10 cm3 is sufficient

❖ Advantage: High production rates

❖ Limitation
⮚ Severe plastic deformation associated with mechanical attrition due to
generation of high temp in the interphase, 100 to 200 oC.
⮚ Difficulty in broken down to the required particle size
⮚ Contamination by the milling tools (Fe) and atmosphere (trace
elements of O2, N2 in rare gases) can be a problem (inert condition
necessary like Glove Box)(Fe <1-2% and Trace elements<300 ppm)
⮚ Protective coating to reduce milling tools contamination (MTC)
increases cost of the process
⮚ Working duration (>30 h) increases MTC (>10%)
17
18
• Sol/gel transition controls the particle size and shape. Calcination of
the gel produces the product (eg. Oxide).
• Sol-gel processing > hydrolysis and condensation of alkoxide-based
precursors such as Si(OEt)4 (tetraethyl orthosilicate, or TEOS).
• The reactions are as follows:
MOR + H2O → MOH + ROH (hydrolysis)
MOH+ROM→M-O-M+ROH (condensation)
• If the aging process of gels exceeds 7 days it is critical to prevent the
cracks in gels that have been cast
• Steps are:
Sol Gel Ageing Drying Dehydration
Densification & Decomposition Product

19
20
 ❖ Advantages
• Synthesizing nonmetallic inorganic materials like glasses, glass ceramics or
ceramic materials at very low temperatures compared to melting glass or
firing ceramics
• Monosized nanoparticles possible by this bottom up approach.

❖ Disadvantages
• Controlling the growth of the particles and then stopping the newly
formed particles from agglomerating.
• Difficult to ensure complete reaction so that no
unwanted reactant is left on the product
• Completely removal of any growth aids
• Also production rates of nanopowders are very slow by this process

21
 Principle and applications
of X-Ray Diffraction (XRD) technique
XRD is a versatile, non-destructive characterization technique widely used in materials science
and engineering for identifying known/ unknown crystalline materials.

XRD works by irradiating a material with incident X-rays, and then measuring the intensities
and diffracting angles of the X-rays that leave the material.

XRD is also used to determine structural properties like lattice parameters, strain, grain size,
epitaxy, phase composition, preferred orientation, to measure thickness of thin films and
multi-layers and to determine atomic arrangement.

XRD also yields information on how the actual structure deviates from the ideal one, owing to
internal stresses and defects.

22
Constructive and Destructive Interference of Waves

Constructive Interference Destructive Interference

In Phase Out of Phase
 Bragg model of diffraction

Crystals are regular arrays of atoms/ ions / molecules. Hence X-rays are diffract periodically by
them.

The diffracted X-rays either can form destructive or constructive interferences.

The arrangement of the atoms/ ions/ molecules can be determined by Bragg’s law:
equated as
nλ = 2dsinθ

where “n” is an integer, and “λ” is the beam wavelength, “d” is the spacing between diffracting
planes and “θ” is the incident angle.

Constructive interference Destructive interference

24
As per the law the diffractions are associated with the set of periodically spaced planes
consist of respective sets of atoms.

Orientation of a particular set of planes is identified by its three Miller indices (h, k, l), and
their spacing (or inter-planar distance) is noted by “d”.

X-rays are used to produce the diffraction pattern because their wavelength, λ, is often the
same order of magnitude as the spacing “d” between the crystal planes (1-100 Ǻ).
Deriving Bragg’s Law: nλ = 2dsinθ
X-ray 1
Constructive interference X-ray 2
occurs only when

n λ = AB + BC AB+BC = multiples of nλ

AB=BC

n λ = 2AB

Sinθ=AB/d

AB=dsinθ

n λ =2dsinθ

λ = 2dhklsinθhkl
What is X-ray Diffraction ?
Modern X-ray Diffractometer

X-ray Tube Detector

2


Sample stage
 Planes in Crystals-2 dimension
λ = 2dhklsinθhkl
Different planes have different spacings

To satisfy Bragg’s Law, θ must change as d

changes e.g., θ decreases as d increases.

z
z z c
c c
(110)
a y y y
b a
Intensity (relative)

x a b b
x x (211)

(200)

Diffraction angle 2

Diffraction pattern for polycrystalline -iron (BCC)

SCXRD

28
XRD patterns for 3 different forms of SiO2

▪ These three phases of SiO2 are

chemically identical.
▪ The amorphous glass does not
have long-range atomic order and
therefore produces only broad
pattern.
▪ Cristobalite form polycrystalline
structure.
▪ Quartz form single crystal structure. 29
Calculation of Crystallite Size using p-XRD data
Crystallites smaller than ~120 nm create broadening of diffraction peaks. This peak broadening
can be used to quantify the average crystallite size of nanoparticles using the Scherrer equation
- used for nanoparticles characterization. Must know the contribution of peak width from the
instrument by using a calibration curve

Scherrer equation can be written as:

o τ is mean size of ordered (crystalline) domains, which may be smaller or equal to grain size;
o K is a dimensionless shape factor, with a value close to unity. The shape factor has a typical
value of about 0.9, but varies with the actual shape of the crystallite;
• β is the line broadening at half the maximum intensity (FWHM), after
subtracting the instrumental line broadening, given in radians
• λ is the X-ray wavelength
• θ is the Bragg angle.
• This quantity is also
denoted as Δ(2θ)
Fig. Simulated p-XRD
patterns for wurtzite CdS
spherical particles of different
sizes from 1 μm to 1 nm. The
inset shows the 1, 2, and 5
nm XRD patterns on an
expanded y-axis scale for
clarity.
 XRD Numericals
Q. 1. In a NaCl crystal, there is a family of planes 0.252 nm apart. If the first-order
maximum is observed at an incidence angle of 12.8823°, what is the wavelength of the
X-ray scattering from this crystal?
Ans.: Use the Bragg equation nλ = 2dsinθ to solve for θ.
For the first-order, n=1. Then λ = 2dsinθ/n = 2dsinθ/1
λ = 2(0.252×10−9 m)sin(12.8823°)/1
= 0.504*0.31068 = 1.57×10−10m or 0.157 nm.

Q. 2. Estimate the crystallite size of the given nanomaterial using p-XRD data:
Peak position 2θ = 21.61o, FWHM of sample = 2.51o, k = 0.9 and λ = 1.5406 Å (degree to
radian = Degree × π/180).
Ans.: 2θ = 21.61o (θ = 10.805o) and FWHM = 2.51o (0.043825 radian)
Crystalline grain size calculation by Scherrer’s equation: k*λ/β*cosθ
k = 0.9, λ = 1.5406 Å (0.15406 nm), β = FWHM in radian and 2θ = Bragg’s angle in o obtained from
p-XRD data.
Crystallite size = (0.9*0.15406)/(0.043825*0.982257) nm = 3.22 nm

31
Overview of Scanning Electron Microscopy (SEM)

32
Limitations of using Light Microscope (LM):
▪ LM has a magnification of 1000x with a resolution of 200 nm.
▪ Resolving power of LM is limited by the number and quality of the lenses but also by the
wavelength of the light used for illumination.
▪ Using light with a short wavelength (blue or ultraviolet) gave a small improvement.
▪ Immersing the specimen and the front of the objective lens in a medium with a high refractive
index (oil) gave another small improvement leading upto 100 nm.

33
34
Signals of Interest

BSE: Elastic scattering

SE: Inelastic scattering

Auger electron:
Xray:

35
 Signals of Interest
Secondary electrons are primarily used for topographical images because they are generated
closer to the surface of the sample. A secondary electron is emitted because of inelastic
scattering, or interactions that involve energy transfer from a primary beam electron to an
atom in the sample. The energy of secondary electrons is defined as being less than 50 eV.
Images collected with secondary electrons will also possess the best lateral resolution due to
the relatively small interaction volume that is approximately the size of the beam diameter.

Elastic scattering at high angles (> 90°) results in the emission of backscattered electrons
above the surface of the sample. When the primary beam approaches the nucleus of an atom
in the sample, the positive charge causes a deflection of the fast electron causing it to be
remitted from the surface. The yield of backscattered electrons depends upon the average
atomic number wherein heavier elements, possessing more positive charge, result in higher
yield. Therefore, the contrast in images acquired with backscattered electrons provides
information on surface composition.

Characteristic X-rays are emitted when an ionized atom relaxes to a ground state by filling an
inner shell electron hole with an electron from a higher orbital. The energy difference between
the two electron shells is equivalent to the characteristic X-ray energy and can be used to
fingerprint the specific element that it originated from. Compared to backscattered electrons,
characteristic X-rays that result from inelastic scattering allow for precise identification of
elements present in the sample. In addition to the characteristic X-ray peaks that are observed
in EDS data, a continuum (background) signal is generated by the deceleration of incident
electrons as they interact with the sample.

36
SEM basics
o Imagine yourself alone in an unknown darkened room with only a fine beam torch. You
might start exploring the room by scanning the torch beam systematically from side to
side gradually moving down so that you could build up a picture of the objects in the
room in your memory.
o SEM uses an electron beam instead of a torch, an electron detector instead of eyes
and a fluorescent screen and camera as memory.
▪ Accelerated electrons behave in vacuum just like light. They travel in straight lines and
have a wavelength which is about 100 000 times smaller than that of light.
▪ Furthermore, electric and magnetic fields have the same effect on electrons as glass
lenses and mirrors have on visible light.
▪ The first electron microscope used two magnetic lenses and later added a third lens to
achieve a resolution of 100 nm, twice as good as that of the light microscope.
▪ Now, the electron microscope uses five magnetic lenses in the imaging system, a
resolving power of 0.1 nm at magnifications of over 1 million times.
Essential components of SEM
1. Electron gun as Source
2. Electron Lenses
3. Sample Stage
4. Detectors for all signals of interest
5. Display/Data output devices
6. Infrastructure Requirements: (a). Power Supply, (b). Vacuum System, (c). Cooling system, (d).
37
Vibration-free floor and (e). Room free of ambient magnetic and electric fields.
Vacuum
38
1. Electron gun as Source:
Electron gun consists of 3 important
components:
(i). Filament made from hair-pin shaped
Tungsten (or Lanthanum Hexaboride)
functioning as Cathode. Voltage applied
to the filament heats it up to 2700 oC;
(ii). Wehnelt cylinder (also known as
grid cap or cylinder) made from
platinum or tantalum foil. It is used for
focusing and controlling the electron
beam and has the shape of a hollow
cylinder. The bottom side of the cylinder
has an opening at its centre with 200 to
1200 μm diameter; and
(iii). Anode, which is positive with
respect to the filament, forms powerful
attractive forces for electrons. This
causes electrons to accelerate (several
hundred thousand km/sec) toward the
anode. Some accelerate right by the
anode and down by the column onto These 3 components together form a triode electron
the sample. gun which is a very stable source of electrons.39
2. Electron lenses - Magnification and resolution
o Magnification is entirely determined by electronic circuitry that scans the beam over the
specimen (and simultaneously over fluorescent screen of monitor where the image appears).
o Magnification can be as high as 3,00,000x. Increasing the magnification is achieved by
reducing the size of the area scanned on the specimen.
o Resolution of 1 nm can be attained depending on:
a) Diameter of electron beam on the specimen surface
b) Specimen properties
c) Specimen preparation technique
d) Instrumental parameters such as
i. beam intensity
ii. accelerating voltage
iii. scanning speed
iv. distance from the last lens to specimen (referred to as the working distance) and
v. angle of the specimen surface with respect to the detector.
3. Sample stage: What happens to the specimen during electron bombardment?
Electron beam scan the specimen in a rectangular spot less than 4 nm in diameter.
a) Specimen itself emits secondary electrons.
b) Some of the primary electrons are reflected (back-scattered electrons).
c) Electrons are absorbed by the specimen.
d) Specimen emits X-rays, and sometimes emits photons (light).
All these phenomena are interrelated and depends on the specimen topography, its chemical
state and atomic number. The number of backscattered electrons, secondary electrons and
absorbed electrons at each point of the specimen depends on the specimen’s topography
40
to a
much greater extent than the other properties mentioned above.
Specimen orientation and manipulation
o SEM image quality depends on specimen orientation and distance from detectors and lens.
o Specimen stage allows the specimen to be moved in a horizontal plane (X and Y direction)
and up and down (Z direction) and rotated and tilted as required. These movements are
often motorized and controlled by the PC.
o SEM models differ in size of their specimen chambers allowing various sizes of specimens to
be introduced and manipulated. Maximum specimen size also determines the price because
larger the specimen chamber, larger the goniometer movement needed and larger the
pumping system needed to maintain a good vacuum.
o The simplest model accepts specimens of a few cm in diameter and can move them 50 mm
in the X and Y directions. Largest chamber accepts samples up to 200 mm in diameter and
can move them 150 mm in each direction.
o All models allow samples to be tilted up to high angles and rotated through 360o.
o There are special stages for heating, cooling and straining specimens.
4. Detectors for all signals of interest
▪ Detectors for backscattered electrons and secondary electrons are either a scintillation
detector or a solid state detector.
▪ In the case of scintillation detector, electrons strike a fluorescent screen, which then emits
light that is amplified and converted into an electrical signal by photomultiplier tube.
▪ In the case of solid state detector, it works by amplifying the minute signal produced by the
incoming electrons in a semiconductor device.
▪ Amplified signal of the electron beam is also impacted on a cathode ray tube. Both the beam
in the microscope and the one in the CRT are scanned at the same rate and the41 1-to-1
5. Display/Data output devices
o SEM is usually equipped with two image monitors, one for observation by operator and
other a high resolution monitor, equipped with ordinary photo camera (or Polaroid)
o To facilitate the observation and correct choice of the parameters mentioned above, SEM
have an image store in which the image is built up scan by scan and displayed at TV speed so
that there is a steady, flicker-free image on the viewing monitor.
o Digital images are stored electronically for subsequent enhancement and analysis.
o Since the SEM image is electronically produced, it can be subjected to contrast
enhancement, inversion (black becomes white), mixing of images from various detectors,
subtraction of the image from one detector from that produced by a different detector,
colour coding and image analysis.
o All these techniques may be applied if it suits the primary aim of extracting the best possible
information from the specimen.
6. Importance of Vacuum in SEM column:
• In SEM, the column through which electron beam passes through must always be at vacuum.
• If the sample is in a gas filled environment, the electron beam cannot be generated or
maintained because of a high instability in the beam. Also, gases could react with the
electron source, causing it to burn out, or cause electrons in the beam to ionize, which
produces random discharges and leads to instability in the beam.
• Transmission of beam through electron optic column would also be hindered by the presence
of other molecules from the sample or the microscope itself, and could form compounds and
condense on the sample. This would lower the contrast and obscure detail in the image.
42
• Sufficiently low vacuum in SEM column is produced by either an oil diffusion pump or a
Strengths of SEM
▪ Gold as conductive coating: A heavy element like gold is preferred for use as conductive
coating as it gives a good yield of secondary electrons and thereby a good quality image. In
addition, it gives a fine grain coating and is easily applied in a sputter coater. The layer
required to ensure a conducting layer is quite thin (about 10 nm).
▪ Operational features: Most SEM models are easier to operate, with user-friendly interfaces,
minimal sample preparation and rapid data acquisition (less than 5 min/image).
▪ SEM generate data in digital formats, which are highly portable.

Limitations of using SEM:

o Sample condition: Must be solid and stable in a vacuum to order of 10-5~10-6 torr. Samples
likely to outgas at low pressures (rock sample saturated with hydrocarbons, wet samples such
as coal, organic materials or swelling clays) are unsuitable for examination in conventional
SEM. However, they can be measured using "low vacuum" SEM.
o SEM cannot measure samples that fail to withstand the electron bombardment.
o If the specimen contains any volatile components such as water, it need to be removed using
a drying process (or can be frozen solid).
o Non-conducting specimens will charge up under electron bombardment, and hence an
electrically conductive coating must be applied to electrically insulating samples for study in
conventional SEM, unless the instrument is capable of operation in a low-vacuum mode.
o Detector type: Solid state x-ray detector (EDS) cannot detect elements with A.N. less than 11
(Na). While EDS is very fast and easy to utilize, they have relatively poor energy resolution
43
 Information from SEM

Scanning electron microscopy (SEM) provides information about

▪ sample's morphology,
▪ sample’s topography,
▪ and the sample’s composition.

It can reveal details about the

➢ surface structure,
➢ elemental makeup,
➢ and the crystalline structure of materials.

SEM also allows for the observation of

✓ particle size,
✓ shape,
✓ and distribution,
making it useful in various fields like nanotechnology and materials science

44
Conducting Polymers
 CONDUCTING POLYMERS
[Link]

The Nobel Prize in Chemistry 2000

The Nobel Prize in Chemistry 2000 was awarded jointly to Alan J. Heeger, Alan G.
46
MacDiarmid and Hideki Shirakawa "for the discovery and development of conductive
 Conducting Polymers
A conducting polymer is an organic polymer that can
conduct electricity, act as a semiconductor, or a conductor.
The most widely studied organic polymers are
Polyacetylene, polyaniline (PANI), polypyrroles,
polythiophenes, and polyphenylene vinylenes.
 Conducting polymers
Electrical conductivity of conducting polymers ranges from insulators (10-10
S/cm) to semiconductor (~10-5 S/cm) to those near (104 S/cm) to good
conductor such as copper (5 x 105 S/cm).

Polymers Electrical conductivity (ohm-1 m-1)

Phenol- 10-9 – 10-10
formaldehyd
e
PMMA <10-12
Nylon-6,6 10-12 – 10-13
PS <10-14 σ*
PE 10-15 – 10-17
PTFE <10-17

σ
Advantage of conducting polymer is that they can Energy diagram of polym
be fabricated into light, flexible sheets. which has saturated bac
bone PTFE, PE, PS
48
▪ Conducting polymers (CPs) are extensively conjugated molecules:
they have alternating single and double bonds. In these molecules,
electrons are able to move from one end of the polymer to the
other through the extended p-orbital system.
▪ Hence CPs are known to be either semiconductors or conductors
giving them unique optical and electrical properties.
▪ Most polymers are poor conductors due to non-availability of large
number of free electrons in the conduction process.
▪ However, conducting polymers are synthesized which possess
electrical Conductivity similar to metal conductors.
Energy bands

50
 Criteria for polymers to be conducting
The polymer should be in extensive conjugation
and
Certainly, if polymer has to conduct electricity it should have e- in
conduction band i.e in Lowest Unoccupied Molecular Orbital (LUMO)
or
It should have positive hole in valence band i.e Highest Occupied
Molecular Orbital (HOMO)

Factors that affect the conductivity

1. Density of charge carriers
2. Their mobility
3. The direction
4. Presence of doping materials (additives that facilitate the polymer
conductivity in a better way)
5. Temperature
 Conducting polymer
Different Types:
(1) Intrinsically conducting polymers (ICP)
(2) Doped Conducting polymers
(3) Extrinsically conducting polymers (ECP)

Conducting
polymers

Intrinsic Doped Extrinsic

52
1. Intrinsically Conducting Polymers
Polymer consisting of alternating single and double bonds is
called conjugated double bonds.
In conjugation, the bonds between the carbon atoms are
alternately single and double. Every bond contains a localised
“sigma” (σ) bond which forms a strong chemical bond.
In addition, every double bond also contains a less strongly
localised “pi” (π) bond which is weaker.
Conjugation of sigma and pi-electrons over the entire
backbone, forms valence bands and conduction bands.
Eg: Poly-acetylene polymers like poly-p-phenylene, polyaniline,
polypyrrole
 Intrinsic Conducting Polymers (ICP)
ICP are conjugated polymers (i.e) alternate single and double
bond.
Eg. Polyacetylene

Polypyrrole

Polydialkylfluorene

54
 Intrinsic Conducting Polymers (ICP)

Polyaniline (PANI) Polyazomethine

Poly-p-phenylene

Poly-p-phenylenesulphide

Polyanthrylene

Polythiophene Polyphenylvinylidene
Poly(3,4-ethylene-dioxythiophene) (PEDOT) 55
 Intrinsic Conducting Polymers (ICP)
Hybridization of carbon in polyacetylene – sp2 σ*
Equivalent to
conduction band π*

Equivalent to
Conjugated π-bond - valence band π
delocalized π e-
σ
σ-bond for mechanical strength and delocalized π e- Relative energies of
for electrical and optical properties MOs of bonding and
antibonding of σ and π
bonds of polyacetylene

56
 Intrinsic Conducting Polymers (ICP)
Overlapping of orbitals over entire backbone (i.e) extended delocalization
results in formation of valence bands as well as conduction bands.

57
 Intrinsic Conducting Polymers (ICP)
ICP – possess low conductivity
10-5 Ω-1 cm-1

Energy gap between valence

and conduction band of ICPs in
the range of semiconductors

Conductivity of ICPs - in the

range of semiconductors

Thus, ICPs are semiconductors

58
 Intrinsic Conducting Polymers (ICP)

Conductivity of semiconductors usually increased by doping. Because

doping increases concentration of charge carrier (e- or positive hole)

Like semiconductors - conductivity of ICPs can increased by creating

either positive or negative charge on the polymer backbone by oxidation
or reduction. This is called doping.

Like p- and n-doping in semiconductors - positive charge on ICP is p-

doping and negative charge on ICP is n-doping

ICPs have low ionization potential and high e- affinity i.e it can be easily
oxidized or reduced.

59
DOPED CONDUCTING POLYMERS

60
2. Doped Conducting Polymers
It is obtained by exposing a polymer to a charge transfer agent in either
gas phase or in solution. ICPs possess low conductivity (10-10/[Link]), but
they possess low ionisation potential and high electron affinity. So they can
be easily oxidised or reduced.
DOPING:
The conductivity of ICP can be increased by creating positive charges
(oxidation) or by negative charges (reduction) on the polymer backbone. This
technique is called DOPING .
In otherwords….
The polymer structure has to be disturbed - either by removing
electrons from (oxidation), or inserting them into (reduction), the
material. The process is known as Doping.
There are two types of doping:
1. Oxidation with halogen (or p-doping).
2. Reduction with alkali metal (called n-doping).
 Intrinsic Conducting Polymers (ICP)
Doping, increases electrical conductivity of ICP dramatically

addition of e- (charge
carrier)
to conduction band (n-
doping)

π-bond e- removal e- from

valence bands (p-doping)

62
(i) p-Doping:
It involves treating an intrinsically conducting polymer with a
Lewis acid which leads to oxidation process and positive charges
on the polymer backbone are created.
Some of the p-dopants are I2, Br2, AsF5, PF5 etc.

2(C2H2)n + 3I2 2[(C2H2)n+ I3-

polyacetylene Lewis acid

(ii) n-Doping:
It involves treating an ICP with a Lewis base which leads to
reduction process and negative charges on the polymer backbone
are created.
Some of the n-dopants are Li, Na, Ca, FeCl3, naphthylamine etc.
_
…-CH=CH-CH=CH-… + C10H7NH2 …-CH=CH-CH=CH- + C10H8
I
+NH
 p-Doped Intrinsic Conducting Polymers
When polyacetylene doped with Lewis acid – oxidation takes
place and positive charge created on polymer backbone.
p-dopant – I2, Br2, AsF5, PF6, naphthylamine etc.

Conductivit
y of
polyacetyle
ne
Vs
I2
concentrati
on

64
 p-Doped Intrinsic Conducting Polymers
The I2 molecule attracts e- from the polyacetylene chain and becomes I3ֿ.
The polyacetylene molecule, now positively charged with unpaired e-
termed as radical cation or polaron.

Lone e- of polaron moves easily along the double bond.

Positive charge is fixed by electrostatic attraction to the iodide ion.

65
• In p-type doping, the dopant (Iodine, I2) attracts an
electron from the polyacetylene chain to form (I3-) leaving
a positive soliton (carbenium ion) in the polymer chain
that can move along its length.
• The lonely electron of the double bond, from which an
electron was removed, can move easily.
• As a consequence, the double bond successively moves
along the molecule, and the polymer is stabilized by
having the charge spread over the polymer chain.

Doping in Trans-Polyacetylene 66
Mechanism of Conduction in Polyacetylene

67
67
 n-Doped conducting polymers
ICP with Lewis base – reduction takes place and negative charge created
on polymer backbone.

n-dopant – Li, Na, Ca, sodium naphthalide etc.

68
Conductivity Mechanism in Polyacetylene:
• The mechanism followed by polyacetylene for the transfer of charge from one
chain to another is called intersoliton hopping.
• What is a soliton? The soliton is a charged or a neutral defect in the
polyacetylene chain that propagates down the chain, thereby reducing the
barrier for interconversion.
• In n-type doping (This can be
done by dipping the film in
THF solution of an alkali
metal) soliton is a resonance-
stabilized polyenyl anion of
approximately 29-31 CH
units in length, with highest
amplitude at the centre of the
defect.
• The solitons (anions)
transfer electrons to a neutral
soliton (radical) in a
neighboring chain through an
isoenergetic process.
• The charged solitons are
responsible for making
polyacetylene a conductor.69
69
 Polyaniline (PANI)

➢ Polyaniline is a conducting polymer of the semi-

flexible rod polymer family.
➢ Polyaniline was discovered over 150 years ago.
➢ In 1980 polyaniline has captured the intense
attention of the scientific community, this interest is
due to the rediscovery of high electrical conductivity.
➢ Polyaniline is one of the most studied conducting
polymer of the past 50 years.
polyaniline synthesis
72
 Properties of Polyaniline

• Polyaniline’s electrical properties can be reversibly controlled by charge-

transfer doping and protonation.

• Polyaniline is environmentally stable and inert (noble) where stainless

steel is corroded.

• Polyaniline is applicable to electrical, electrochemical, and optical

applications.

• Polyaniline is currently used in cell phones and calculators, and other

LCD technology.
 3. Extrinsically Conducting Polymers
These are those polymers whose conductivity is due to the presence of
externally added ingredients in them.
Two types:
(1) Conductive element filled polymer:
It is a resin/polymer filled with carbon black, metallic fibres, metal
oxides etc. Polymer acts as a binder to those elements.

These have good bulk conductivity and are low in cost, light weight,
strong and durable. They can be in different forms, shapes and sizes.

(2) Blended Conducting Polymers:

It is product obtained by blending a conventional polymer with a
conducting polymer either by physical or by chemical change.
Such polymers can be processed and possess better physical,
chemical and mechanical strength.
APPLICATIONS OF CONDUCTING POLYMERS
anti-static substances for photographic film

Corrosion Inhibitors

Compact Capacitors

Anti Static Coating

Electromagnetic shielding for computers

"Smart Windows"

Transistors

Light Emitting Diodes (LEDs)

Lasers used in flat televisions

Solar cells

Displays in mobile telephones and mini-format television screens 76

 Chemistry of display devices specific to OLEDs
An organic light-emitting diode (OLED or organic LED), also known
as organic electroluminescent (organic EL) diode, is a light-emitting diode
(LED) in which the emissive electroluminescent (EL) layer is a film of organic
compound that emits light in response to an electric current.

77
 Working principle of OLEDs

⮚ The holes lie in the valence band, while the free electrons are in the conduction
band of material.
⮚ When there is a forward bias in the p-n junction, the electron which is a part of the
n-type semiconductor material would overrun the p-n junction and join with the
holes in the p-type semiconductor material. Therefore, regarding the holes, the free
electrons would be at the higher energy bands.
⮚ When this movement of free electron and hole takes place, there is a change in the
energy level as the voltage drops from the conduction band to the valance band.
⮚ There is a release of energy due to the motion of the electron.
⮚ In standard diodes, the release of energy in the manner of heat. But in LED the
release of energy in the form of photons would emit light energy.
⮚ This entire process is known as electroluminescence, and the diodes are known
as a light-emitting diode.
 Deposition Techniques
Deposition methods refer to techniques used to apply a thin layer of material
onto a substrate. These methods are crucial in various industries, including
semiconductors, medical devices, and coatings. There are two main categories:
Physical Vapor Deposition (PVD) and Chemical Vapor Deposition (CVD)

79
 Physical Vapour Deposition
o This is a process of depositing some material by atom by atom or
molecule by molecule or ion by ion.

Applications:
1. This process is widely used to produce decorative coatings on plastic
parts those are resembling shiny metal.

2. Many automobile parts are plastic with a PVD coating of aluminium.

3. A lacquer coating is applied over the decorative coating to provide

corrosion protection.

4. This process is also used to apply relatively thick (1mm) coatings of

heat resistant materials on jet engine parts, A special alloy of
chromium, aluminium and yttrium is used for this type of coating. 2
 PVD: – 1. Thermal Evaporation Method
How easy is it to vaporize a metal?

Al and Au are quite usable in thermal evaporation system with heated

crucible, for they can be melt in crucible and generate enough quantity of
vapours.
However, W and Ti are not suitable for their low vapour pressure.
Typical deposition rates in industry is around 0.5 µm/min (~8 nm/s, for Al) 3
 PVD: 2 – Sputtering Method
Sputtering :
A popular method for adhering thin films onto a substrate.
Sputtering is done by bombarding a target material with a charged gas (typically
argon) which releases atoms in the target that coats the nearby substrate.
It all takes place inside a magnetron vacuum chamber under low pressure.
1. High technology coatings such as ceramics, metal alloys and organic and inorganic
compounds are applied by sputtering.
2. The substance to be coated is connected to a high voltage DC power supply.
3. When the vacuum chamber has been pumped down, a controlled amount of argon or
another gas is introduced to establish a pressure of about 10-2 to 10-3 torr.
4. On energizing current supply, plasma is established between the work and the
material to be coated.
5. The sputtering gas is often an inert gas such as argon. For efficient momentum
transfer, the atomic weight of the sputtering gas should be close to the atomic
weight of the target, so for sputtering light elements neon is preferable, while for
heavy elements krypton or xenon are used. Reactive gases can also be used to
sputter compounds.
 PVD: 2 – Sputtering Method
Sputtering is a process whereby particles are ejected from a solid target material due to
bombardment of the target by energetic particles.

Sputtering is done either using DC voltage (DC sputtering) for metals or using AC voltage
(RF sputtering) for dielectric materials and polymers.
The gas atoms are ionized and they
bombard the material to be coated.

The energy of imposing ions cause

atoms of the target material to be
sputtered off and they are transported
through the plasma to form a coating.

Direct current sputtering is used when

the target is electrically conductive.

Radio-frequency sputtering, which uses

a RF power supply is used when the
target is a non conductor such as
polymer. Figure : PVD by sputtering proces6s
 PVD: 2 – Sputtering Method
Plasma is a “state of matter similar to gas in which a certain portion of the particles are
ionized”
• The main principle is to build a vaccum chamber and fill with Argon

• By adding a high voltage, the argon will arc to plasma state

• The argon ion (Ar+) will move toward to cathode with high speed and sputter the
target material (use target as cathode).

• The target atom or molecular will be hit to substrate surface and condense as a
film.

• Instead of heat melting in evaporation method, the plasma Ar+ ion hit and sputter
the target is the main mechanism in plasma sputtering method.

• The target atom is knocked out by Ar+ ion, the knock force is so big and can
accelerate target atom a high speed. With such velocity, the target atom can hit
and attach to substrate surface deeply.

• The film density is good compared to thermal evaporation.

 PVD: 2 – Sputtering Method

Applications of Sputtering method:

o This method is used in VLSI fabrication

(Very-large-scale
integration (VLSI) is the process of creating an integrated circuit (IC) by
combining hundreds of thousands of transistors or devices into a single chip)

o Sputtering is used extensively in the semiconductor industry to deposit thin films of

various materials in integrated circuit processing.
o Thin antireflection coatings (MgF2 and Fluoropolymers; mesoporous silica materials;
titanium nitride and niobium nitride) on glass for optical applications are also
deposited by sputtering.
o An important advantage of sputter deposition is that even materials with very high
melting points are easily sputtered while evaporation of these materials in a resistance
evaporator or Knudsen cell is problematic or impossible. Sputter deposited films have
a composition close to that of the source material.

9
Sputtering offers the following advantages over other PVD methods used in
VLSI fabrication:
1) Sputtering can be achieved from large-size targets, simplifying the deposition of
thins with unifrom thickness over large wafers;
2) Film thickness is easily controlled by fixing the operating parameters and simply
adjusting the deposition time;
3) Control of the alloy composition, as well as other film properties such as step
coverage and grain structure, is more easily accomplished than by deposition
through evaporation;
4) Sputter-cleaning of the substrate in vacuum prior to film deposition can be
done;
5) Device damage from X-rays generated by electron beam evaporation is
avoided.

Sputtering, however, has the following disadvantages too:

1) High capital expenses are required;

2) The rates of deposition of some materials (such as SiO2) are relatively low;
3) Some materials such as organic solids are easily degraded by ionic
bombardment;
4) Sputtering has a greater tendency to introduce impurities in the substrate than
deposition by evaporation because the former operates under a lesser vacuum range
than the latter.
 PVD – 3 - Ion Implantation Method
Ion implantation is not a true deposition process, but a surface
modification technique used to dope semiconductors or other
materials by accelerating ions into a target material. Unlike deposition,
which adds a layer of material, implantation involves directly injecting ions
from an ion source into the crystal lattice of a substrate. This alters the
substrate's surface properties, such as electrical conductivity, by precisely
controlling the concentration and depth of the implanted dopant ions.
The process involves several steps:
[Link]: Ions are created from source materials
(e.g., gaseous elements).
[Link]: These ions are then accelerated to
high velocities using strong electric/magnetic fields.
[Link] Selection: An analysis magnet separates the
ions by their mass-to-charge ratio.
[Link]: The selected, high-energy ions are
directed at a target wafer or substrate.
[Link] Loss: The ions collide with the host atoms of
the substrate, losing energy and coming to rest at a
specific depth within the material.
89
12
13
 PVD – 3 - Ion Implantation Method
1. A third variation of the PVD process is ion implantation method

2. Metal is evaporated thermally and plasma is established to ionize

the evaporating species
3. Evaporant ions bombard the substrate with energy

4. They physically implant into the substrate to produce

an extremely strong coating bond.

5. Sputter and ion plated coatings are used in design for very thin
films for electrical, optical and wear-resistant applications.

6. The wear properties of tools are widely enhanced by hard thin

film coatings.
11
 Applications
1. This process is widely used to produce decorative coatings on
plastic parts those are resembling shiny metal.

2. Many automobile parts are plastic with a PVD coating of

aluminium.

3. A polish coating is applied over the decorative coating to provide

corrosion protection.

4. This process is also used to apply relatively thick (1mm) coatings

of heat resistant materials on jet engine parts;

- A special alloy of chromium, aluminium and yttrium is used for

this type of coating.
 Chemical vapour deposition
Chemical vapour deposition or CVD is a generic name for a group of processes
that involve depositing a solid material from a gaseous phase and is similar in
some respects to physical vapour deposition (PVD).

PVD differs in that the precursors are solid, with the material to be deposited
being vaporised from a solid target and deposited onto the substrate

Precursor gases (often diluted in carrier gases) are delivered into the reaction
chamber at approximately ambient temperatures. As they pass over or come
into contact with a heated substrate, they react or decompose forming a solid
phase which and are deposited onto the substrate. The substrate temperature is
critical and can influence what reactions will take place.

Eg. Ni(CO)4 for the deposition of Ni 16

Chemical Vapour Deposition

17
CVD Apparatus
A CVD apparatus will consist of several basic components:
Gas delivery system – For the supply of precursors to the reactor chamber

Reactor chamber – Chamber within which deposition takes place

Substrate loading mechanism – A system for introducing and removing substrates,
mandrels etc

Energy source – Provide the energy/heat that is required to get the precursors to
react/decompose.

Vacuum system – A system for removal of all other gaseous species other than those
required for the reaction/deposition.

Exhaust system – System for removal of volatile by-products from the reaction
chamber.

Exhaust treatment systems – In some instances, exhaust gases may not be suitable for
release into the atmosphere and may require treatment or conversion to safe/harmless
compounds.

Process control equipment – Gauges, controls etc to monitor process parameters such
as pressure, temperature and time. Alarms and safety devices would also be included
18
in this category
Advantages of CVD over PVD:

One of the primary advantages is that CVD films are generally quite
conformal, i.e., that the film thickness on the sidewalls of features is
comparable to the thickness on the top.
In, contrast, physical vapor deposition (PVD) techniques, such as sputtering
or evaporation, generally require a line-of-sight between the surface to be
coated and the source
Another advantage of CVD is that, in addition to the wide variety of
.
materials that can be deposited, they can be deposited with very high purity.
This results from the relative ease with which impurities are removed from
gaseous precursors using distillation techniques.

Other advantages include relatively high deposition rates, and the fact that
CVD often doesn’t require as high a vacuum as PVD processes
20
CVD also has a number of disadvantages:

1. The precursors need to be volatile at near-room temperatures.

2. CVD precursors can also be highly toxic (Ni(CO)4 ), explosive (B2H6), or corrosive (SiCl4).

3. The byproducts of CVD reactions can also be hazardous (CO, H2, or HF).

4. Some of these precursors, especially the metal-organic precursors, can also be quite
costly.

5. The other major disadvantage is the fact that the films are usually deposited at
elevated temperatures. This puts some restrictions on the kind of substrates that can
be coated.

6. More importantly, it leads to stresses in films deposited on materials with different

thermal expansion coefficients, which can cause mechanical instabilities in the
deposited films.

7. All surfaces in the reaction chamber get coated.

8. Separate process and reaction must be developed for each coating. Some of the gases
are toxic and dangerous. 21
 Applications of CVD
1. A newer process known as plasma assisted chemical vapour deposition. This
process is used to apply diamond and diamond like carbon coatings.
2. used largely in the production of semiconductors
3. Silicon carbide barrier coatings are applied on plastic films and
semiconductors.
4. Chemical Vapour Deposition is used to produce bulk shapes of high purity
silicon carbide. Reactants are deposited on a chamber wall to a thickness in
terms of millimeters.

5. Thin-film coatings are key to the manufacture of many electronic devices. They
involve the application of dopant, sealant and other microelectronic paste.
6. Thermal evaporation is a low cost process, but all these processes are normally
batch processes because of vacuum chamber requirements.
7. CVD is also used to produce synthetic diamonds.
22