Course name:

Growth and Characterization of Nano-

electronic Materials (EE728)
Instructor: Apurba Laha
Department of Electrical Engineering, IIT Bombay
Contact: Tel: 022-2576 9408, email: laha@ee.iitb.ac.in
 Lecture 32, 33

Metrology: Semiconductor Materials

and Devices

Introduction to Photoluminescence Spectroscopy

LED basics

Source: wikipedia.org
 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 light energy obtained from
chemical energy. Example: Luminescence in deep sea-water fishes, Mg
burning in air
𝒉𝒄
• Emission wavelength  = , where E1 and E2 are the initial (higher
𝑬𝟏 −𝑬𝟐
energy) and final (lower energy) states
• Visible range: 0.4 – 0.7 μm corresponding to energy of 3.1 – 1.77 eV

We are lucky that some semiconductors have

bandgaps which cover entire visible range, so solid
state light emitting devices are very useful
Photoluminescence Spectroscopy
 Contactless, nondestructive method to probe the electronic
structure of materials
 Bandgap Determination.
 Impurity Levels and Defect Detection
 Recombination Mechanisms

photo-excitation
emission of light, or luminescence

Forms of photoluminescence
Resonant radiation
In resonant radiation, a photon of a particular wavelength is absorbed and an equivalent
photon is immediately emitted, through which no significant internal energy transitions of
the chemical substrate between absorption and emission are involved and the process is
usually of an order of 10 nanoseconds.
 Photo-Luminescence measurement system
 An laser is used as the excitation
source
 The chopper is used for averaging to
reduce noise
 The cryostat helps to go to a 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
 Hydrogenic model of doping impurities
 For acceptors the effective mass is higher
than donors so the acceptor energies are
higher
 When the concentration of impurity
increases so that the average distance The simple model for a hydrogen atom can be used to
describe the behavior of an impurity in a semiconductor.
between atoms is twice the orbital radius of
an excited state then they produce band Thus the ionization energy of a hydrogen atom

 Donor and acceptor energies usually

increase for higher bandgap as effective
mass increases. This explains why activation Corresponding radius of the lowest orbit of the electron
energy for p-GaN is lower than in p-AlGaN around the hydrogen nucleus

In general
r=

For GaN Ed = 33.15 meV

Example: for GaN, r = 22.85 A (Similar calculation for Ea)

Values calculated for effective mass of 0.22 me and n = 1

Hydrogen model_ionization
 Hydrogenic model for excitons
What is exciton?
Excitons are bound states between an electron excited into the conduction band and the hole
that remains in the valence band, with the coulomb interaction being responsible for the
binding energy.
The simplest mathematical description of such an excitonic state is given by hydrogen
model. The possible energy state En,K of the bound electron-hole pair are essentially the
Bohr Eigen states

𝝁 ∗ 𝒒𝟒 𝟏 ħ𝟐 𝑲𝟐 1
𝑬𝒏,𝑲 = 𝑬g − −
𝟑𝟐𝝅𝟐 ħ𝟐 𝜺𝟐 𝜺𝒐𝟐 𝒏𝟐 𝟐 𝒎𝒆∗ + 𝒎𝒉∗ 𝜇∗
The gap energy Eg appears as an additive term because the zero of energy usually taken to be the
top of valence band edge

The electron mass (me*) is replaced by the reduced effective mass * derived from the
effective masses of electron (me*) and hole (mh*)

The dielectric constant 0of the vacuum is replaced by semiconductor materials , to

take into account screening by surrounding dielectrics
 Excitons
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
 Radiative transitions in semiconductors
 Process 1: Intraband transition
 Process 2: Band-to-band transition
 Process 3: Excitonic transition
 Process 4: Valence band to donor
transition
 Process 5: Conduction band to acceptor
transition
 Process 6: Shallow donor to shallow
acceptor transition
 Others: Donor to conduction band,
acceptor to valence band
 Intraband and interband transitions
Process 1: Intraband transitions
Transition between the energy levels within
the same energy band (Conduction or valence)

Process 2: Band-to-band transitions

Peak of the emission spectrum

Direct bandgap:

Indirect bandgap:

 = absorption coefficient

Ep is the phonon energy. Intensity proportional to 

+ve and –ve signs are for absorption and emission

 Other radiative transitions
Process 3: Excitonic transitions
bind
For free excitons: hv = Eg - Eex
bind
For bound excitons: hv = Eg – Eex – Eb

Eb is the energy binding the exciton to the

donor or acceptor

Process 4 and 5: Free-bound transitions

Process 6: Donor-acceptor pair transitions

where r is the distance between the donor and acceptor

Variation of PL with temperature and doping
With increase in temperature:
 Lattice spacing increases so bandgap reduces, peak shift to higher wavelength

 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
 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
 Typical GaN PL spectra

 band-edge (NBE) band at

3.5013 eV
 Shoulder at higher energy of
3.509 eV and another at lower
energy of 3.496 eV

The inset exhibits three emission lines. The shallow neutral donor-bound (DoX) and
free exciton (FXA and FXB). The bound exciton (DoX) level exist 5.7 meV below the
free exciton (FXA) energy. The splitting of FXA and FXB levels is 6.6 meV
 Excitonic transistion: Impact of temperature

GaN, Wurtzite. The absorption coefficient versus GaN, Wurtzite. The absorption coefficient versus
photon energy for GaN layer grown on sapphire. photon energy for GaN layer grown on sapphire.
T = 77 K T = 293 K