Luminescence basics

• Types of luminescence
– Cathodoluminescence: Luminescence due to recombination of EHPs created
by energetic electrons. Example: CL mapping system
– Photoluminescence: Luminescence due to recombination of EHPs created by
energetic photons. Example: PL mapping system
– Electroluminescence: Luminescence due to recombination of EHPs created by
injected electrons and holes. Example: LEDs, Lasers
– Chemiluminescence: Luminescence due to recombination of EHPs created by
chemical energy. Example: Luminescence in deep sea-water fishes
• Emission wavelength is hc/(E1-E2), where E1 and E2 are the initial
(higher energy) and final (lower energy) states
• Visible range: 0.4 – 0.7 m corresponding to energy of 3.1 – 1.77 eV
We are lucky that common
semiconductors have bandgaps which
cover entire visible range, so solid
state light emitting devices are very
useful
ELECT 871 10/06/03
 Photo-Luminescence measurement system
• An UV laser is used as the
excitation source
• The chopper is used for
averaging to reduce noise
• The cryostat helps to go to
lower temperature
• The monochromator helps to
select wavelength of the
luminescent light
• The detector converts light
signal into electrical signal
with a large gain
• The power meter is used to
measure the electrical signal
for each wavelength and
give an output of intensity
vs. wavelength
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 Hydrogenic model of doping impurities
• For acceptors the effective mass EC
is higher than donors so the ED
acceptor energies are higher EA
• When the concentration of EV
impurity increases so that the
average distance between atoms Radius: r  0.529n 2 (m0 / m* )
is twice the orbital radius of an
excited state then they produce For GaN r = 22.85 Å
banding 13.6 m*
• Donor and acceptor energies Energy: ED  2 2
usually increase for higher n  m0
bandgap as effective mass For GaN ED = 33.15 meV
increases. This explains why (Similar calculation for Ea)
activation energy for p-GaN is Values calculated for effective
lower than in p-AlGaN mass of 0.22 me and n = 1
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 Hydrogenic model for excitons
Exciton definition: An electron in the conduction band and a hole in the valence band
coming together in real space and revolving around their common center of mass is called an
excitonic pair or simply exciton
• Excitonic transitions are only observed for very pure material and at low
temperature. At higher temperature the excitonic pair breaks down due to thermal
energy. At higher impurity level the ionized impurity screens the electric field and
formation of excitons becomes difficult.
• Excitons do not contribute to the carrier conduction as it does not have a net charge
• Excitons can be either free, or bound to neutral or charged donors and acceptors
Bound exciton
*
m
13.6 red 1
bind
Eex  2
Donor or acceptor
n m0  2

bound excitons r  0.529n2 (m0 / mred )
DoX AoX have lower energy
corresponding to 1 1 1
the binding energy where

  
mred me mh
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 Radiative transitions in semiconductors
• Process 1: Intraband
transition 1

• Process 2: Band-to-band
transition excitons

• Process 3: Excitonic
shallow donors

transition
• Process 4: Valence band to
donor transition
• Process 5: Conduction
band to acceptor transition
• Process 6: Shallow donor
to shallow acceptor
transition
5 Deep donors
3 6
4
2
Deep acceptors
shallow acceptors
Others: Donor to conduction
band, acceptor to valence band
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 Intraband and interband transitions
Process 1: Intraband transitions

Hot electrons relax their energy mainly by

emitting phonons, but sometimes under
phonon’s or/and other electron’s assistance
can also emit photons. This mechanism is
truly rare as many particles are involved
K
Process 2: Band-to-band transitions Direct Indirect
Peak of the emission spectrum   hc/Eg

Direct bandgap: a ( E )  A0 ( E  Eg )1/2

A( E  E g  E p ) 2
Indirect bandgap: a E  
  Ep 
exp    1
a = absorption coefficient,  KT 
Ep is the phonon energy. Intensity proportional to a
+ve and –ve signs are for absorption and emission
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 Other radiative transitions
Process 3: Excitonic transitions
For free excitons: hv=Eg - Eexbind
1
For bound excitons: hv = Eg - Eex bind – Eb
Eb is the energy binding the exciton to the
donor or acceptor excitons
shallow donors
Process 4 and 5: Free-bound transitions
5 Deep donors
4
For Doh: hv = Eg - ED 3 6
2
For Aoe: hv = Eg - EA Deep acceptors
shallow acceptors

Process 6: Donor-acceptor pair

transitions 2
e
hv(r )  Eg  ( E A  ED ) 
4r
where r is the distance between the donor and acceptor
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 Variation of PL with temperature and doping
• With increase in temperature:
– Lattice spacing increases so bandgap reduces, peak shift to higher
wavelength
aT 2
Eg (T )  Eg (0) 
T 
– Full width at half maximum increases due to increased lattice
vibrations
– Peak intensity usually reduces
• As doping increases
– PL peak blueshifts due to band filling
– FWHM can increase due to thicker band of states from which
transition can be made
– Intensity will also increase by enhancing the probability of
radiative recombination
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 Variation due to other factors
• Strain: Bandgap varies
with strain as the lattice
spacing changes
• Electric field: Reduction
in effective bandgap due
to enhanced probability
of tunneling
• Excitation intensity:
Variation of the
luminescence peak
energy, same effect as
increasing doping
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 GaN PL spectrum
PL variation with temperature
Typical room temperature PL of GaN

• I2 is the neutral donor bound recombination. A

and B are free exciton lines associated with the
A and B hole bands
• D0A0 is donor-acceptor (residual, background)
pair recombination
• The “LO” refers to phonon replicas of the
particular transitions, at multiples of 29 meV
lower energies ELECT 871 10/06/03
 Variation with Al alloy composition in AlGaN

• For bulk AlGaN the bandgap variation is accurately reflected in the

PL spectrum, however it is not true for AlGaN/GaN heterostructures
where due to stark effect there is a red shift. So Al composition
calculated from PL peak position is NOT totally accurate
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 PL spectrum for non-polar QW

• With increasing well width

– The intensity increases due to increased confinement
– The peak position shifts to lower energy due to reduction in quantum size effect (QSE)
i.e. splitting of energy levels in a QW
– The full width at half maximum (FWHM)  also decreases ELECT 871 10/06/03
 Nitride QW PL spectrum

Electron and hole

wave-functions
for non-polar
material Electron and hole
wave-functions for
polar material due to
built-in electric field

• With increase in well thickness

– Intensity decreases due to reduced overlap due to quantum confined stark
effect (QCSE)
– Energy decreases due to quantum size effect (QSE), and by lowering of
energy gap between the energy states
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 PL as indicator of material quality
• Better quality of epilayer
50000
means higher intensity B1098
B1025
and narrower FWHM 40000 B1001

PL intensity (a.u.)
• Also true for quantum
30000 SL buffered Al.2Ga.8N: 4.5 m
wells where the interface
fluctuations controls the 20000
SL buffered Al.2Ga.8N: 2.1 m
FWHM of PL peaks 10000
• AlGaN epilayers grown conventional Al.2Ga.8N: 1.2 m
0
on superlattice (SL)
buffered GaN layers 260 280 300 320 340 360 380 400 420

produces the best quality Wavelength (nm)

ELECT 871 10/06/03

 X-Ray generation and measurement set up
E  h  hc / 
• a copper target X-ray tube
produces an X-ray beam with
the principle wavelengths:
• Cu K-alpha1: 1.5405Å
(transition from 2s to 1s,
used for HRXRD)
• Cu K-alpha2: 1.5443Å
(transition from 2p to 1s)

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 The Diffraction condition
• Bragg’s law gives the Bragg’s condition
correlation between the k
minimum distance k
k’
between parallel planes d
and the angular position
of the X-Ray peak in the
two theta-omega scan

Points to note:
The minimum distance between planes (k1, k2, k3) in d  a
a cubic lattice is given by k12  k22  k32
Distance between planes (k1, k2, k3) in hexagonal
lattice is given by 1 4  k12  k1k2  k22  k32
   2
 c
d k21 ,k2 ,k3 3 a 2

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 Symmetric and asymmetric scan types
Symmetric scan:(002)
• Symmetric scans can give us (004) diffraction
information regarding c/c (assuming
a/a = 0), and the length of a period
and total length of superlattice layers
• It can also give us information about Assymetric scan:
the quality of the material (102), (104), (114) etc.
• Two basic types of symmetric scans: Low angle of
incidence
– Omega-two theta scan
– Omega scan or rocking curve
• Asymmetric scans are useful for High angle of
incidence
getting a/a and reciprocal space maps
used to determine crystalline quality
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 The omega - two theta scan
k
ki kf

k
ki kf

• Source fixed, but if sample rotates ,

then detector rotates 2 
• The magnitude of k changes, not its
orientation w.r.t sample normal
• The intensity of peaks usually
proportional to the thickness of the
layers
• The - 2 scans give the composition of
the respective layers in the entire
structure ELECT 871 10/06/03
 The omega scan or rocking curve
k
ki kf

k
ki Normal
kf

• The source is fixed, the detector is fixed but the sample is rocked
around the Bragg peak slightly
• The magnitude of the k remains same, but its orientation w.r.t
sample normal changes
• The FWHM of the rocking curve gives is an important indicator
of the material crystalline quality
ELECT 871 10/06/03
 GaN/InGaN multi quantum well XRD
• The distances between the
main satellite peaks X-ray spectra of InGaN/GaN MQW
(marked by numbers) are
proportional to the width
of the one repeat, while
the distances between the
smaller peaks are related
to the total thickness of
the superlattice
• The main satellite peaks
become sharper for larger
quantum well due to
stricter conditions for
interference
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 Reciprocal space maps for crystalline quality

• For symmetric scans q is always perpendicular to the

sample surface. q is varied to measure c lattice constant
• AlGaN in (a) and (b) are pseudomorphic but (b) has
much worse quality. AlGaN in (c) is not pseudomorphic
as it does not have the same q
ELECT 871 10/06/03