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CHEM F343: Inorganic Chemistry

III
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 Photoconduction in Semiconducting Materials

Photoconduction occurs in semiconducting materials if

the semiconductor is part of an electrical circuit
If the energy of the incoming photon is sufficient, an
electron is excited into the conduction band or a hole is
created in the valence band and they carry a charge
through the circuit.

The maximum wavelength of the incoming photon

required to produce photoconduction is related to the
energy gap in the semiconducting material,
λmax = hc/Eg

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Photoconduction in Semiconducting Materials

This principle for

photodetectors or
“electric eyes” that
open or close doors or
switches when a beam
of light focused on a
semiconducting
material is
interrupted

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 Semiconducting Materials: Solar Cells

Solar cells also used the absorption of light to

generate voltage
Essentially the charge carriers generated by
optical absorption are separated and this leads
to the development of a voltage
This voltage causes a current flow in an
external circuit
Solar cells are p-n junctions designed so that
photons excite es into the conduction band

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 Semiconducting Materials: Solar Cells

The es move to the n-side of the junction, while

holes move to the p-side of the junction
This movement produces a contact voltage due
to the charge imbalance
The junction device is connected to an electric
circuit, the junction acts as a battery to power the
circuit.
Solar cells make use of antireflective coatings
so that maximum key elements of the solar
spectrum are captured

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 LEDs
The light that is absorbed by a direct band gap
semiconductor causes es to be promoted to the
conduction band
When these es fall back into the valence band gap, they
combine with the holes causing emission of light
Many semiconductors solid solutions can be used so as
to have different band gaps, producing LEDs of
different colors
This phenomenon is also used in light-emitting diodes
and semiconductor lasers

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 Selective Absorption, Transmission or
Reflection: F centers
Electron or hole traps, called F-centers, can also be
present in crystals
When fluorite (CaF2) is produced there is an excess Ca
observed. As a result a fluoride ion vacancy is produced
To maintain electrical neutrality, an electron is trapped
in the vacancy, producing energy levels that absorb all
visible photons
Polymers-particularly those containing an aromatic ring
in the backbone can have covalent bonds that produce
an energy level structure that causes selective
absorption
For this reason, chlorophyll in plants appears green and
hemoglobin in blood appears red
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 Characterization techniques

1. XPS
2. DLS
3. XRD
4. TEM

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X-rays-Inner Electron Shell Interactions:
What are X-rays?

X-rays, which have somewhat lower energy than gamma

rays, are produced when es in the inner shells of an
atom are stimulated
The stimulus could be high energy es or other x-rays
When stimulation occurs, x-rays of a wide range
energies are emitted
Both a continuous and characteristic spectrum is
produced

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X-rays-Inner Electron Shell Interactions:
Continuous Spectrum

Suppose that a high energy e strikes a material

As the e decelerates, energy is given up and emitted as photons
Each interaction, however, may be more or less severe, so the e gives up
different fraction of energy each time and produces photons of different
wavelengths
A continuous spectrum is produced

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4/26/2024
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 X-rays-Inner Electron Shell Interactions:
Continuous Spectrum

If the e were to lose all of its energy in one impact,

the minimum wavelength of the emitted photons would
be equivalent to the original energy of the stimulus
The minimum wavelength of X-rays produced is called
the short wavelength limit, λswl

The short wavelength limit decreases, and the number

and energy of the emitted photons increase, when the
energy of the stimulus increases

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 X-rays-Inner Electron Shell Interactions:
Characteristic Spectrum

The incoming stimulus may also have sufficient

energy to excite an e from an inner-energy level
into an outer-energy level

The excited e is not stable and to restore

equilibrium, es from a higher energy level fill the
empty inner level. This process leads to the emission
of a characteristic spectrum of x-rays that is
different for each type of atom

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 X-rays-Inner Electron Shell Interactions:
Characteristic Spectrum
The characteristic spectrum is produced because there
are discrete energy differences between any two
energy levels.
Then an e drops from one level to a second level, a
photon having that particular energy and wavelength is
emitted.

We typically refer to the energy levels by the K, L,

M…. Designation.

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4/26/2024
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 X-rays-Inner Electron Shell Interactions:
Characteristic Spectrum

If an e is excited from the K shell, es may fill that

vacancy from any outer shell
Normally, es in the closest shells fill the vacancies
Thus photons with energy ΔE = EK – EL (Kα x rays) or
ΔE = EK – EM (Kβ x rays) are emitted
When an e from the M shell fills the L shell, a photon
with energy ΔE = EL – EM (L α, x-rays) is emitted; it has a
long wavelength of low energy
Note that we need a more energetic stimulus to
produce Kα x-rays than that required for Lα x-rays

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X-rays-Inner Electron Shell Interactions: Characteristic
Spectrum Shows the Identity of the Elements

As a consequence of the emission of photons having a

characteristic wavelength, a series of peaks is
superimposed on the continuous spectrum
The wavelengths at which these peaks occur are unique to
the type of atom
Thus, each element produces a different characteristic
spectrum, which serves as a fingerprint for that type of
atom
If we match the emitted characteristic wavelengths with
those expected for various elements, the identity of the
material can be determined

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 X-rays-Inner Electron Shell Interactions:
Characteristic Spectrum Determines the Percentage
of the Elements
The intensity of the characteristic peaks can also be
measured.
By comparing the measured intensities with standard
intensities, we can estimate the percentage of each
type of atom in the material and hence we can
estimate the composition of the material
The energy or wavelength of X-rays emitted when an
e beam impacts a sample (such as that in a scanning or
TEM) can be analyzed to get chemical information of
the make up of a sample
This technique is known as energy dispersive x-ray
analysis
It is also used in XRD

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Design a filter that
preferentially absorbs
Kβ x-rays from the
nickel spectrum but
permits Kα x-rays to
pass with little
absorption. This type
of filter is used in x-
ray diffraction (XRD)
analysis of materials
For nickel, Kα (Å) is
1.660 and Kβ (Å) is
1.500, then Kβ is
almost completely
absorbed

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What is XPS?

X-ray Photoelectron Spectroscopy (XPS), also

known as Electron Spectroscopy for Chemical
Analysis (ESCA) is a widely used technique to
investigate the chemical composition of surfaces.

X-ray Photoelectron spectroscopy, based on the

photoelectric effect, was developed in the mid-1960’s
by Kai Siegbahn and co-workers at the University of
Uppsala, Sweden.

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XPS technique

Irradiate the sample surface, hitting the core electrons (e-) of the
atoms.

The X-Rays penetrate the sample to a depth on the order of a

micrometer.

Useful e- signal is obtained only from a depth of around 10 to 100

Å on the surface.

The X-Ray source produces photons with certain energies:

MgK photon with an energy of 1253.6 eV
AlK photon with an energy of 1486.6 eV

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XPS technique
Electrons are extracted
only from a narrow solid
X-ray Beam angle

X-ray penetration
depth ~1mm.
Electrons can be 10 nm
excited in this
entire volume

X-ray excitation area ~1x1 cm2. Electrons

are emitted from this entire area

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Binding energy
➢ An electron near the Fermi level is far from the nucleus,
moving in different directions all over the place, and will not
carry information about any single atom.
Fermi level is the highest energy level occupied by an
electron in a neutral solid at absolute 0 temperature.
Electron binding energy (BE) is calculated with respect to
the Fermi level.
➢ The core e-s are local close to the nucleus and have binding
energies characteristic of their particular element.

Valence e-

Core e-
Atom

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Binding energy

The Binding Energy (BE) is characteristic of the core electrons for each
element. The BE is determined by the attraction of the electrons to the
nucleus. If an electron with energy x is pulled away from the nucleus, the
attraction between the electron and the nucleus decreases and the BE
decreases. Eventually, there will be a point when the electron will be free of
the nucleus.

This is the point with 0 energy

of attraction between the
electron and the nucleus. At
this point the electron is free
0 B.E.
from the atom.

x
These electrons are attracted
p+
to the proton with certain
binding energy x

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What is X-ray?

Ejected Photoelectron
Incident X-ray
Free
Electron
Conduction Band Level XPS spectral lines are
Fermi identified by the shell from
Level
which the electron was ejected
Valence Band
(1s, 2s, 2p, etc.).
2p L2,L3 The ejected photoelectron
2s L1
has kinetic energy:
KE = hv-BE-
1s K Following this process, the
atom will release energy by
the emission of an Auger
Electron.

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Binding energy equation

BE = hv - KE - spec
Where: BE = Electron Binding Energy
KE = Electron Kinetic Energy
spec= Spectrometer Work Function

The binding energy scale was derived to make uniform

comparisons of chemical states straight forward.

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XPS instruments

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XPS spectrum

O 1s

O Auger

O because
of Mg source

C O 2s
Al
Al

Sample and graphic provided by William Durrer, Ph.D.

Department of Physics at the Univertsity of Texas at El Paso BITSPilani, Pilani Campus
XPS Study of C3N4/AuPd

Pd(0) - Pd 3d5/2 = 335.3 eV and Pd 3d3/2 340.6 eV

Pd(II) - Pd 3d5/2 = 337.4 and Pd 3d3/2 342.6 eV
Au 4d5/2 = 334.2 eV

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DLS instrument

Ref: Horiba slides, http://www.horiba.com/fileadmin/uploads/Scientific/Documents/PSA/Webinar_Slides/TE012_V2.pdf

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What is DLS?

❖ Dynamic light scattering refers to measurement

and interpretation of light scattering data on a
microsecond time scale.

❖ Dynamic light scattering can be used to

determine
• Size distribution
• Particle/molecular size
• Relaxations

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DLS Optics

Particles in suspension undergo Brownian motion

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Size calculation

q = 4πn/λ{Sin(θ/2)}

τ = Dmq2

τ = decay constant
Dm = diffusion coefficient
q = scattering vector
n = refractive index
Dh = KBT/3πηDm λ = wavelength
θ = scattering angle
Dh = hydrodynamic diameter
η = viscosity
kB = Boltzman’s constant

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Hydrodynamic Diameter

DLS gives the diameter of a sphere that moves the same

way as your sample

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The powder method

 = 2dSin
d= a
h +k +l
2 2 2

4a sin 
2 2
 = 2 2 2
2

h +k +l
2
4a
(h + k + l ) = 2 sin 
2 2 2 2


(h + k + l )  sin 
2 2 2 2

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BRAGG’s law cont.
Bragg’s law: 2d Sin = n
▪ n is an integer and is the order of the reflection
▪ For Cu K radiation ( = 1.54 Å) and d110= 2.22 Å

n Sin 
1 0.34 20.7º First order reflection from (110)
Second order reflection from (110)
2 0.69 43.92º
Also written as (220)
a
d 220 =
a d 220 1
d hkl =
8 =
d110 2
h +k +l
2 2 2
d110 =
a
2
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Peak properties

• Peak position: inter planar spacing

• Peak intensity: number of atoms on plane

• Peak width: number of planes

• Peak broadening: non-uniform lattice parameter

(imperfections, lattice strains) and instrumental error

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 Extinction Rules for different Bravais lattices

Reflections which Reflections

Bravais Lattice
may be present necessarily absent
Simple SC all None
Body centered BCC (h + k + l) even (h + k + l) odd
Face centered FCC h, k and l unmixed h, k and l mixed
Allowed reflection planes

Permitted Reflections

Simple Cubic (100), (110), (111), (200), (210), (211), (220),

(300), (221) ………
BCC (110), (200), (211), (220), (310), (222)….
FCC (111), (200), (220), (311)…..

Allowed reflection planes from

different Bravais lattices

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Crystal structure determination

Peak position: determination of crystal structure

2→  Intensity Sin Sin2  ratio
1 21.5 0.366 0.134 3
2 25 0.422 0.178 4
3 37 0.60 0.362 8
4 45 0.707 0.500 11
5 47 0.731 0.535 12
6 58 0.848 0.719 16
7 68 0.927 0.859 19

FCC
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Powder diffraction pattern

111

311
220
200

Radiation:
331

422
420
222

400

Cu K,  =1.54 Å

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Analysis

Peak position: determination of crystal structure

n 2  Sin Sin2  ratio Index

1 38.52 19.26 0.33 0.11 3 111
2 44.76 22.38 0.38 0.14 4 200
3 65.14 32.57 0.54 0.29 8 220
4 78.26 39.13 0.63 0.40 11 311
5 82.47 41.235 0.66 0.43 12 222
6 99.11 49.555 0.76 0.58 16 400
7 112.03 56.015 0.83 0.69 19 331
8 116.60 58.3 0.85 0.72 20 420
9 137.47 68.735 0.93 0.87 24 422

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Analysis
Peak position: determination of crystal structure
FCC; wavelength=1.54056Å
S1 () sin2 h2+k2+l2 sin2/ h2+k2+l2 Lattice Parameter, a (Å)
(mm)
38 19.0 0.11 3 0.037 4.023
45 22.5 0.15 4 0.038 3.978
66 33.0 0.30 8 0.038 3.978
78 39.0 0.40 11 0.036 4.039
83 41.5 0.45 12 0.038 3.978
97 49.5 0.58 16 0.036 4.046
113 56.5 0.70 19 0.037 4.023
118 59.0 0.73 20 0.037 4.023
139 69.5 0.88 24 0.037 4.023
168 84.9 0.99 27 0.037 4.023
Constant; so it is FCC
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 Peak width: determination of crystallite size
Peak width (B) is inversely proportional to
K
B(2 ) =
crystallite size (L)

L cos K is a dimensionless shape factor, with a value

close to unity (about 0.9). It varies with the
actual shape of the crystallite

 of K
Target Metal
radiation (Å)
Mo 0.71
Cu 1.54
Co 1.79
Fe 1.94
Cr 2.29
X-ray Instrument

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 Transmission electron microscope (TEM): The instrument

laser diode

electron source

first condenser lens

multiple segmentphotodiode second condenserX, lens
Y piezoelectric
(position sensitive detector) scanner
condenser aperture mirror
objective condenser lens

objective aperture
microcondenser lens OpticalScanning
(light)
specimen (thin) probe
microscope
selected areaobjective
aperture lens
light beam
objective imagingZlens
piezoelectric
scanner microscope
specimen diffraction lens
intermediate lens
first projector lens
light source second projector lens cantilever

Optical (light)sample
microscope Scanning projector
probe microscope
chamber Charged particle microscope
(stationary)

fluorescent screen
What can we study in a TEM?

• Topography and morphology

• Chemistry
• Crystallography
• Orientation of grains
TEM is better in terms of resolution and ability of investigating internal
structure. Electron diffraction is also possible to investigate crystal
structure. Sample for TEM must be very thin and the information in
the depth direction is quite limited.
Samples for SEM is not so limited about the size in the three
dimensional direction. SEM image can record focused information
even when the sample has large dimension in the thickness direction.
Relatively thick sample can also be observed at a time.

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