Electronic Transitions Optical Effects in Semiconductors UV-visible Spectroscopy UV Visible Spectroscopy Photoluminescence

CH8. Optical Characterizations CH8.
Optical Characterizations
15
th
week
Electronic Transitions
Optical effects in semiconductors
UV-visible spectroscopy UV visible spectroscopy
Photoluminescence
wipark@hanyang.ac.kr wipark@hanyang.ac.kr
http://mse.hanyang.ac.kr/SNE/ http://mse.hanyang.ac.kr/SNE/
The Electromagnetic Spectrum The Electromagnetic Spectrum
Electronic Transitions in Formaldehyde Electronic Transitions in Formaldehyde
Electronic Transitions and Spectra Electronic Transitions and Spectra
Atoms
Molecules
Semi- Semi-
conductors ?
Introduction to semiconductors Introduction to semiconductors
Semiconductor a solid-state material in which, in contrast to metals and
insulators, electrical conductivity is sensitive to temperature,
illumination and magnetic field These properties stemfromthe fact that in illumination and magnetic field. These properties stem from the fact that in
semiconductors the valence band and the conduction band are separated by an
energy gap, the width of which rarely exceeds ~ 3.5 eV.
The most common semiconductors: Si, GaAs
Band structure
A semiconductor, by virtue of its name, is such due the intermediate
magnitude of its conduction; it lies between that of a conductor and that of magnitude of its conduction; it lies between that of a conductor and that of
an insulator.
Semiconductors: electronic properties Semiconductors: electronic properties
Band structure
Fig.2 Band structure of
semiconductors
Fig.1 Band structure of semiconductors, metals and
insulators at T=0 (upper figure) and T>0 (lower figure)
Semiconductors: electronic properties Semiconductors: electronic properties
Electron transitions between bands
When the temperature rises above zero some of the electrons in the valence band
can surmount the energy gap and populate the conduction band; they leave behind gy g p p p ; y
a missing electron or hole. Likewise, electrons in the conduction band can fall
back into the valence band, giving off the difference in energy, typically E
g
, as
photon. p
Fig.3 Direct band gap in a
semiconductor
Fig.4 Indirect band gap
in a semiconductor
Optical effects in semiconductors Optical effects in semiconductors
When a solid sample is radiated by flux of electromagnetic radiation, part of the
radiation is reflected, part is absorbed and part is transmitted through the
sample.
I I I I
A T R tot
I I I I + + =
x
e R I x I
o
= ) 1 ( ) (
T
e R I x I = ) 1 ( ) (
0
2
) 1 ( k n +
2
) 1 (
) 1 (
k n
k n
R
+ +
+
=
Fig.5 Reflection I
R
, absorption A
o
, transmission T
R
of monochromatic radiation F with wavelength .
R: reflectivity
n: index of reflection
k: extinction coefficient
(imaginary component of n)
g
(imaginary component of n)
UV-visible spectroscopy UV-visible spectroscopy
Measuring system:
Fig.6 Schematic presentation of the system
Fig.7 Optical characterization system
UV-visible spectroscopy UV-visible spectroscopy
Dispersion Devices Dispersion Devices
Monochromator
The monochromator selects a narrow band A of wavelength from a source of
di i Th l b d i d l h hi h b i d radiation. The spectral band is centered at a wavelength which can be varied.
Depending on the resolution desired and the spectral region to be covered, one
uses a prism or gratings.
Prism
Non-linear dispersion
Temperature sensitive
Diffraction grating
Linear Dispersion
Different orders
Diffraction grating
e e o de s
Detectors Detectors
Photomultiplier Tube Detector
Hi h iti it t l li ht l l High sensitivity at low light levels
Cathode material determines spectral
sensitivity
Good signal/noise Good signal/noise
Shock sensitive
The Photodiode Detector
Wide dynamic range
Very good signal/noise at high light
levels
Solid-state device
Schematic Diagram of a Photodiode Array Schematic Diagram of a Photodiode Array
Same characteristics
as photodiodes
Solid-state device
Fast read-out cycles
Holmium Perchlorate Solution Holmium Perchlorate Solution
Photoluminescence Photoluminescence
Schematic presentation of the photoluminescence (PL) process Schematic presentation of the photoluminescence (PL) process.
Narrow band stimulated emission at wavelengths tunable with the size of the
nanocrystal can be observed as expected from the quantum size effect
nanocrystal can be observed, as expected from the quantum size effect.
Photoluminescence
In order to excite an electron, the photon energy has to be
larger than energy gap of the semiconductor.
Intensity of emitted light: ] / ) ( exp[ ) (
2
T K E h E h I
B g g
v v v
Crystal defects may lower the photoluminescence intensity.
G N hi fil PL l i h GaN thin film PL plot with
progressive diminution of
defect density from a to g.
HRTEM images of nanocrystalline semiconductors HRTEM images of nanocrystalline semiconductors
Fig.11 High Resolution TEM plain-view images of nanocrystalline PbSe
Quantum confinement effect Quantum confinement effect
Blue shift takes place when semiconductor nanocrystallites exhibit a systematic
shift toward higher energy (larger energy gap), that is, lower wavelength (blue
shift) with decreasing particle size. shift) with decreasing particle size.
v
hc
h E
g
= =
g
Fig.12 UV-vis optical absorption spectra
of ZnS nanocrystallites (size in nm).
Fig.13 Experimental and calculated band gap
versus size of ZnS nanocrystallites.
Physics in nanostructures Physics in nanostructures
Quantum confinement
When the size of a nanostructure approaches the size of an exciton
(bound electron-hole pair) in the material, the exciton is confined
and its energy changes and its energy changes.
Think particle-in-a-box
Need to understand quantum mechanics
From Schrodingers wave equation
Schrodingers wave equation: describes the space- and time-dependence of
quantum mechanical systems
( ) 0 ) ( ) (
2 ) (
2 2
2
= +
c
c
x x V E
m x
Time-independent Schrodinger equation

( ) ) ( ) (
2 2
cx

Meaning of Wave function (x, t): Probability amplitude, ie, the probability
fi d i l i i to find a particle in x at time t
General soultions:
| |
) ( 2 V E
In case of E-V(x) > 0:
I f E V( ) 0
|
|
.
|
\
|

=
) ( 2 V E m
k
ikx ikx
Be Ae x

+ = ) (
kx kx
B A

+ ) (
|
|
|
|

=
) ( 2 E V m
k
In case of E-V(x) < 0:
In case of V(x) = 0:
kx kx
Be Ae x + = ) (
ikx ikx
Be Ae x

+ = ) (
|
|
.
\
=
k
|
|
|
|
=
mE
k
2
( )
Be Ae x + ) (
|
|
.
\

k
Infinite potential well Infinite potential well
Particle in a box
x
mE
x
x
0 ) (
2 ) (
2 2
2
= +
c
c

In the region II
Region I Region II Region III
kx B kx A x
Be Ae x
x
ikx ikx
cos sin ) (
) (
+ =
+ =
c

|
|
.
|
\
|
=
2
2
mE
k
V(x) in the region II = 0
Boundary condition
0 ) ( ) 0 ( = = = = L x x
(x) in the region I and III = 0
Normalization condition
| | x nt 2
1 ) ( ) (
*
=
}

dx x x |
.
|
\
|
=
L
x n
L
x
t
sin
2
) (
Infinite potential well Infinite potential well
|
|
| x nt 2
|
.
|
\
|
=
L
x n
L
x
t
sin
2
) (
n=3
2
n=1
n=2
From 1D to 3D From 1D to 3D
1D confinement: 2D nanomaterials
2D confinement: 1D nanomaterials
3Dconfinement: 0D nanomaterials
Observation of Confinement in Quantum Dots Observation of Confinement in Quantum Dots
Size Decreasing
vary energy of wide range for single material system (vs. using composition
variations))
more accurately:
Possible applications as
biological labels
LEDs/lasers
LEDs/lasers
single photon sources
Applications of semiconductor nanomaterials Applications of semiconductor nanomaterials
Quantum dot lasers Q
Quantum dot detectors
Single-electron transistors
h i l Photonic crystals

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CH8. Optical Characterizations CH8.

Time-independent Schrodinger equation

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