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Pilani Campus

Semiconducting nanoparticles: synthesis

and properties
27/02/2017
Discussed topic

Electron microscopy: TEM and SEM

Scanning probe microscope: AFM and STM

Todays discussion

Semiconducting nanoparticles: Synthesis and properties

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Semiconducting materials??

Intermediate electrical conductance of metal and insulator

Electrical conductance increases with increasing temperature
Intrinsic semiconductor and Doped semiconductor

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Semiconducting materials??

both holes and

Major carrier is Major carrier is
electrons contri- electron
bute to electrical hole
conduction

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Which are Semiconducting
materials?
Semiconducting materials??

Group Examples

IV Diamond, Si, Ge, SiC, SiGe etc.

III-V AlSb, AlAs, BN, GaN, InAs, InGaP etc

II-VI CdSe, ZnO, CdZnTe etc.

IV-VI PbTe, SnS2 etc.

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Quantum dots

Nanoparticles

Insulator
Metal Organic
Semiconductor

QD refers to the semiconductor particles

Nanocrystals is the general term for any inorganic

entity in the nano-range

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Quantum dots

Electronic Structure of Nanocrystals

I. Quantum confinement
II. Quantum size effect

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Band theory of solids
Formation of a band of N molecular
orbitals of successive addition of N atoms
spread the range of
energies covered by the
molecular orbitals
N molecular orbitals
(from N atoms) covering
a band of finite width
the lowest energy orbital
of this band is fully
bonding and the highest
energy orbital is fully
anti bonding
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Band theory of solids (cont.)

I. HOMO moves up in energy

while the LUMO moves down
in energy; as a result energy
of transition decreases

II. The energy diff. between

HOMO and LUMO level
decreases and eventually
it becomes smaller than
thermal energy

III. At this stage, the levels

are considered to be merged
to form bands.

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Band theory of solids (cont.)

IV. In the case of the infinite ring containing solid, the gap reduces to
zero and the top of the valence band touches the bottom of the
conduction band; this is just like metal.

V. When the gap cannot reduce zero, we obtain situations categorized

as semiconductors or insulators

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Band theory of solids (cont.)

A band formed from

overlap of s orbitals is
called an s band

If the atoms have p

orbitals available, then
the same procedure
leads to a p band

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Band theory of solids (cont.)

Fermi Level: It is the highest energy level that an electron can reach or
occupy in a material at absolute zero temperature. In simple words, it is
one of the energy levels in a semiconductor above which all energy
levels are unoccupied or vacant at absolute temperature.

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Band theory of solids (cont.)

The material is insulator at T= 0 and the material is

semiconductor at T>0
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Band theory of solids (cont.)

Conduction band
Conduction band Conduction band

Ef
Energy

Band gap
Valence band
Valence band
Valence band

Insulator Semiconductor Conductor

Sharma A. et al. Nanotechnology. 2012, 2: 73-76. BITSPilani, Pilani Campus

When quantum confinement?
I. When an electron gets excited
due to thermal excitations, an e-
h+ pair is created

II. The e-h+ pair can be bound

when they approach each other at
a finite distance.

III. This bound pair is called exciton, which is delocalized throughout

the crystal.
IV. The Bohr radius of the exciton can be given as:
a = h2 / [1/me + 1/mh] { = dielectric const}
IV. Quantum size effects is manifested when the length of the
nanocrystal (d) is comparable to the exciton radius
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Characteristics of excitons

I. An exciton is a bound state of an electron

and hole which are attracted to each other by
the electrostatic Coulomb force
II. It is electrically neutral, exists in semi-
conductor, insulators etc.

III. The exciton has slightly less energy than the unbound e- and hole
IV. The recombination of the e-h+ is limited by resonance stabilization
due to the overlap of the electron hole pair wave functions, resulting in
an extended lifetime of the exciton
V. In a bulk semiconductor, the size of the crystal is much larger than
the exciton Bohr radius and hence the exciton is free to move
throughout the crystal.
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Quantum confinement

I. When the size of the semiconductor crystal becomes comparable or

smaller than the exciton Bohr radius, the quantum dots are in a state
of quantum confinement. As a result of quantum confinement, the
energy levels in a quantum dot are discrete as opposed to being
continuous in a bulk crystal.

Bulk semiconducting crystal Semiconducting QD

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Quantum confinement
Density of states (E)

Quantum Quantum
Bulk 2D film
wire dot

n=4
n=4 n=4
n=3 n=3
n=3 n=2 n=2
n=2 n=1
n=1 n=1

Energy
Quantization of the electronic density of states as a result of
variation in the dimensionality of materials
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Quantum confinement

II. The energy associated with an electron equivalent to conduction

band energy level is given by ,
Ee = h2n2/8meL2
Similarly, for hole, Eh = h2n2/8mhL2

III. The energy increases as one goes higher in the quantum number.
Since the electron mass is much smaller than that of the hole, the
electron levels are separated more widely than the hole levels.

IV. The energy levels are affected by the diameter of the semiconductor
particles

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Quantum confinement

VI. Due to the presence of discrete energy levels in a QD, there is a

widening of the energy gap between the highest occupied electronic
states and the lowest unoccupied states as compared to the bulk
material. As a consequence, the optical properties of the semiconductor
nanoparticles also become size dependent.

UV-VIS spectra of bulk CdS

and 5 nm CdS nanoparticle

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The totality: semiconducting NPs
I. Nanoparticles of semi conducting materials have all three
dimensions in the range of 120 nm and possess novel electronic,
magnetic, catalytic and optical properties.
II. This is due to their large surface-to-volume ratio and their reduced
size. As the diameter of the particle approaches the exciton Bohr
diameter, the charge carriers become confined in three dimensions
with zero degrees of freedom.
III. As a result of the geometrical constraints, the electron feels the
particle boundaries and responds to particle sizes by adjusting its
energy.
IV. This phenomenon, known as the quantum size effect, causes the
continuous band of the solid to split into discrete, quantized levels
and the bandgap to increase.
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Synthesis of semiconductor QD

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Conclusions

Semiconducting nanoparticles

Next class
Semiconducting nanoparticles: Syntheses,
properties, characterization and applications

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