Summer Training Report

On

LASER DIODES AND PL CHARACTERIZATION OF LASER

STRUCTURE

At

Solid State Physics Laboratory

Defence Research and Devolopment Organization
Timarpur, Lucknow Road, Delhi-110008

in partial fulfillment of the degree

Bachelor of Technology
In

Electrical and Electronics Engineering

IDEAL INSTITUTE OF TECHNOLOGY

DR.APJ ABDUL KALAM TECHNICAL UNIVERSITY, LUCKNOW

Submitted By
AYUSH CHANDRA
1502821004

Under the Guidance of

ABHISHEK SHARMA (SCIENTIST D)

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 DECLARATION

This is to certify that Summer Training Report entitled LASER DIODES AND PL
CHARACTERIZATION OF LASER STRUCTURE which is submitted by Ayush Chandra in
partial fulfillment of the requirement for the award of degree B.Tech. in Department of Electrical
And Electronics Engineering of Dr. A. P. J. Abdul Kalam Technical University, is a record of the
candidate own work carried out by him under my/our supervision. The matter embodied in this
report is original and has not been submitted for the award of any other degree. I hereby declare
that this submission was his own work and that, to the best of his knowledge and belief, it
contains no material previously published or written by another person nor material which to a
substantial extent has been accepted for the award of any other degree or diploma of the
university or other institute of higher learning, except where due acknowledgment has been made
in the text.

SIGNATURE

ABHISHEK SHARMA
(SCIENTIST D)

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 ACKNOWLEDGEMENT

I record my sincere thanks to the Director Mr. R. K. Sharma, Solid State Physics Laboratory,
Defence Research and Development Organisation for providing me an excellent opportunity to
undergo training in his esteemed organization through which I could gain an exposure to the
Research and Development environment and getting acquainted with the Laser technologies.

I would sincerely like to thank Dr. Alok Jain, Scientist ‘G’, Head, LASER Division for
permitting me to work in his division and making me aware of recent trends and technologies in
semiconductor laser diodes.

I wish to express my deep sense of gratitude and obligation to, Mr. Abhishek Sharma, Scientist
‘D’ for his valuable guidance. I would also like to thank , Dr. Pramod Kumar, for their valuable
guidance in making report and contribution in lab work. I express my thanks to all the members
of LASER group for providing me support and their constant encouragement during training.

Last but not the least, I would like to thank the library staff for allowing me to access the library
and it’s valuable material.

AYUSH CHANDRA
ROLL NO:(1502821004)

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 ORGANISATION PROFILE

Defence Research & Development Organisation (DRDO) works under Department of

Defence Research and Development of Ministry of Defence. DRDO dedicatedly working
towards enhancing self-reliance in Defence Systems and undertakes design & development
leading to production of world class weapon systems and equipment in accordance with the
expressed needs and the qualitative requirements laid down by the three services.

DRDO is working in various areas of military technology which include aeronautics, armaments,
combat vehicles, electronics, instrumentation engineering systems, missiles, materials, naval
systems, advanced computing, simulation and life sciences. DRDO while striving to meet the
Cutting edge weapons technology requirements provides ample spinoff benefits to the society at
large thereby contributing to the nation building.

Vision
Make India prosperous by establishing world-class science and technology base and provide our
Defence Services decisive edge by equipping them with internationally competitive systems and
solutions.

DRDO have many research and development labs spread across the country. The different R&D
labs are meant to work on different projects.one of the lab of DRDO is SSPL (solid state physics
laboratory) ,which is located in Timarpur ,Delhi.

Solid State Physics Laboratory (SSPL), one of the establishments under the Defence R&D
Organization (DRDO), Ministry of Defence, was established in 1962 with the broad objective of
developing an R&D base in the field of Solid State Materials, Devices and Sub-systems.The
Laboratory has a vision to be the centre of excellence in the development of Solid State
Materials, Devices and has a Mission to develop and characterize high purity materials and solid
state devices and to enhance infrastructure, technology for meeting the futuristic challenges.

The major activities at SSPL include development of semi-conductor materials, Solid-state

devices, Electronic components and investigation of Solid-state materials/devices. One of the
thrust areas is the development of semiconductor Laser diodes. Recently development includes
the fabrication of the Pulsed Laser Diode, CW Laser Diode, Laser Diode Array at SSPL.

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 CONTENTS
1. List of figures………………………………………………………………… 6
2. List of tables………………………………………………………………….. 7
3. Lasers…………………………………………………………………………. 8
3.1 Laser Construction…………………........................................................... 8
3.2 Properties of Laser………………………………………………………… 10
3.3 Types of Emission………………………………………………………… 13
3.4 Types of Laser…………………………………………………………….. 17
3.5 Applications of Laser……………………………………………………… 18
4. Semiconductor Lasers…………………………………………………………. 22
4.1 Direct and Indirect Gap Semiconductors………………………………….. 22
4.2 Semiconducting Materials………………………………………………… 24
4.3 Doped Semiconductors……………………………………………………. 25
4.4 Semiconductor Laser Diodes……………………………………………… 27
28
5. Photoluminescence…………………………………………………………… 35
5.2 Basic Mechanism…………………………………………………………. 37
5.3 Photoluminescence Spectroscopy………………………………………… 42
5.4 Forms of Photoluminescence…………………………………………….. 44
5.5 Applications of Photoluminescence……………………………………… 45
6 . PL Chracterization of Laser Structure………………………………………… 49
6.1 Particle in an infinite potential well………………………………………. 49
6.2 Particle in a Square Finite Well ………………………………………….. 52
6.3 Conclusion……………………………………………………………….. 54

7. Appendix……………………………………………………………………… 55
8. Bibliography…………………………………………………………………... 59

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 LIST OF FIGURES

1. Figure 1.1 Laser Structure

2. Figure 1.2 Spatial and Temporal Coherence
3. Figure 1.3 Spontaneous Emission
4. Figure 1.4 Stimulated Emission
5. Figure 1.5 Absorption Spectra
6. Figure 1.6 Laser Range Finder
7. Figure1.7 Typical image for proximity fuze.
8. Figure 1.8 typical image for dazzler
9. Figure 2.1 Comparison between insulator, semiconductor and conductor
10. Figure 2.2 Direct and Indirect Gap Semiconductor
11. Figure 2.3 Semiconductor Laser
12. Figure 2.4 Semiconductor Laser Structure
13. Figure 2.5 Double Hetrostrucutre
14. Figure 2.6 Quantum well Structure
15. Figure 2.7 Density of States
16. Figure 2.8 Quantum well Laser
17. Figure 3.1 Mechanism of Photoluminescence
18. Figure 3.2 and 3.3 Excitation and Emission Spectra
19. Figure 3.4 Radiative Transition
20. Figure 3.5 Possiblities of radiative or non radiative transition
21. Figure 3.6 CW Photoluminescence setup
22. Figure 3.7 The structure of hexaphenylsilole (HPS) and PL spectra of compound
23. Figure 3.8 structure of a triphenylamine–boradiazaindacene (BODIPY) derivative.
24. Figure 4.1 Infinte Potential well
25. Figure 4.2 Finite Potential Well
26. Figure 4.3 Actual PL Spectra
27. Figure 5.1 Graph for Valence band
28. Figure 5.2 Graph for Conduction Band

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 LIST OF TABLES

1. TABLE 1 semiconducting materials with their general specifications

2. TABLE 2 Summary of wavelengths of the finite potential well

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 LASERS

Laser is one of the most significant contributions of the last century to science. The word ‘laser’
is now being used as any other common English word to mean a highly powerful, extremely
intense, deep-penetrating and piercing beam of light which can do extraordinary things. Laser
has, for a long time, been a fascinating subject stretched to unimaginable levels of exaggeration
and fantasy by fiction-writers and movie makers.

Laser is the acronym for Light Amplification by Stimulated Emission of Radiation. Laser is a
device that can amplify light and produce a highly directional, intense, monochromatic and
coherent beam. The dimensions of laser device can range from the size of tiny grain to that of
large building. The output power can be from 10-9 to 1020 Watts with wavelengths from
microwave to the soft X-ray regions in the electromagnetic spectrum and frequencies from 1011
Hz to 1017 Hz. The pulse energy of laser can be as high as 1017 having a pulse duration as short
as 6x10-15 seconds.

1.1 LASER CONSTRUCTION

The laser is an optical oscillator. It comprises a resonant optical amplifier whose output is
feedback into its input with matching phase. In the absence of such an input there is no output so
that the feedback signal is also zero. However this is an unstable situation. The presence at the
input of even a small amount of noise is unavoidable and may initiate the oscillation process.
The input is amplified and the output is fed back to the input where it undergoes further
amplification. The process continues indefinitely until a large output is produced. Saturation of
the amplifier gain limits further growth of the signal, and the system reaches a steady state in
which an output signal is created at the frequency of the resonant amplifier.

Two conditions must be satisfied for oscillation to occur

• The amplifier gain must be greater than the loss in the feedback system so that net gain
is incurred in a round trip through the feedback loop.

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 • The total phase shift in a single round trip must be multiple of 2p so that the feedback
input phase matches the phase of the original input.

If these conditions are satisfied, the system becomes unstable and oscillation begins. As
the oscillation power grows, however, the amplifier saturates and the gain diminishes
below its initial value. A stable condition is reached when the reduced gain is equal to
the loss.

The useful output is extracted by coupling a portion of the power out of the oscillator. In
summary, an oscillator comprises:
• An amplifier with a gain-saturation mechanism
• A feedback system
• A frequency-selection mechanism
• An output coupling scheme

Lasers are used in a great variety of scientific and technical applications including

communications, computing, image processing, information storage, holography, lithography,

materials processing, geology, metrology, rangefinding, biology and clinical medicine.

Figure 1.1 Laser Structure

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1.2 PROPERTIES OF LASERS
The main characteristics of lasers are:

• Coherence (Spatial and Temporal).

• Brightness and Intensity
• Monochromaticity

1.2.1Coherence

Coherence is measure of the ability of different wavefronts or parts of wavefronts, to interfere or

intermingle with each other, when the wavefronts are combined, as in an interferometer. As
such, coherence can also be termed as the measure of the ability of two photons to interfere or
intermix with each other. There are two types of coherence which are as follows:-

• Spatial coherence
• Temporal coherence

1.2.1.1 Spatial Coherence

Spatial Coherence is also known as ‘Transverse Coherence’. Spatial or Transverse coherence

indicates how far apart from each other, can the two sources of light or two portions of the same
source can be located in a direction transverse to the direction of observation so as to get the
property of coherence over a number of observation points.Let us consider that the two sources
are separated by distance S, in the transverse direction to the direction of observation. Let them
be at distance R from the point of observation as shown belowThe Spatial coherence length L is
the transverse distance between points P and Q where the two sources cease to exhibit the effects
of interference.

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 Figure 1.2 Spatial and Temporal Coherence

1.2.1.2 Temporal Coherence

Temporal Coherence is related to phase difference, maintained over a specific time or distance,
of propagation and is manifested by interference effects. Good spectral purity, which is nothing
but a small bandwidth, gives a high degree of temporal coherence. Interference of light beams, as
a result of temporal coherence, can be illustrated with Michelson’s interferometer experiment
shown A parallel beam of light from the source S is made to split by the beam divider BD. The
two parts, so split, propagate in two different directions. After traversing their individual paths,
the two beams are recombined with the help of mirrors M1 and M2, in order to create an
interference pattern, near the point E.

Visibility or contrast of interference fringes is

V=(Imax-Imin)/(Imax+Imin)

where Imax and Imin are minimum and maximum observed intensities respectively Laser light has
a very high degree of temporal coherence, whereas conventional light has a poor temporal
coherence. Also the path difference in the two beams in Michelson’s experiment may be a few
centimeters. This path difference is also known as ‘Coherence Length’ of the source of light.

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1.2.2 Brightness and Intensity
Brightness of a source of light is the power emitted per unit area per unit solid angle.Let ∂A be
the elemental surface area at a point O of the source of light. The power ∂P emitted by area ∂A
into a solid angle ∂S, arounf the direction OO’

∂P=BcosΘ∂A∂S

Where ,Θ is the angle between OO’ and the normal n to the surface.The quantity B is called the
brightness of the source, at the point O, in the direction OO’.The factor cosΘ indicates the
physical importance in the projection of ∂A is a plane which is orthogonal to the OO’ direction.

Laser beams are the brightest of sources. They are extremely intense too.

1.2.4 Monochromaticity
One of the special characteristics of a beam having temporal coherence is spectral purity or
monochromatictiy. The high spectral purity of laser is due to the ability of the optical resonator
to oscillate only a very small no of resonant modes. The design of the optical resonator or cavity
makes most of the cavity resonant modes to fall outside the gain-curve such that only a few find
the gain available to compensate for the losses. Reduction of modes in the cavity can be used to
decrease the bandwidth of laser lower than a nanometer.

The output from a laser scheme is very nearly perfect to givw us a sine wave with very small
bandwidth of about one Khz/sec. The output from a stable gas laser, locked to the centre of the
absorption line has a bandwidth Δf approximately equal to 500 Hz which means that Δl=10-8 at
at l=6000A0

1.3 TYPES OF EMISSION

Basically there are 3 types of emission which are as follows:

• Spontaneous emission
• Stimulated emission
• Absorption

1.3.1 Spontaneous Emission

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Consider that there are two levels of energy E1 and E2 in a material where
E2>E1
Now consider atom of material is at energy level E2. The atom at this level is more
unstable as compared to that at the ground level. Naturally there is a tendency for the
atom to come back to or decay into ground level.When decay occurs the atom releases
some amount of energy. When this energy is released in the form of electromagnetic
waves we call it spontaneous emission of energy.The frequency f of the radiated wave is
F=(E2-E1)/h
hf= (E2-E1)

Figure 1.3 Spontaneous Emission

An atom can decay not only through a raidative emission; it can also decay in a non-
radiative manner. In the non-radiative transition, the difference in energy levels E2 and
E1 can be experienced in reigons other than electromagnetic. Consider at a given time t,
there are N2 number of atoms per unit volume in a specific material which is at energy
level E2. The rate, at which the decay of these atoms takes place, in spontaneous
emission, is given by

(dN2/dt) Spontaneous=-AN2
A is called Einstein’s Constant
The lifeline L of Spontaneous emission is given by:
L=1/A
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The photon, thus emitted due to spontaneous emission has no correlation of phase,
direction etc with the photon, which is absorbed.

1.3.2 Stimulated Emission

Consider that the atom is initially at energy E2 with an electromagnetic wave of

frequency f is incident on a specific material. This wave has the same frequency as that of
the atom. There is a high degree of probability that this wave will force the atom to
undergo a change from energy level E2 to energy level E1. Here the difference in energy
(E2-E1), is received in the form of an electromagnetic wave which adds to the incident
wave.In this case, the atom is already in the excited state E2. Before it could come to the
ground state, due to spontaneous emission process, if it is irradiated with a photon, whose
energy is exactly equal to E2-E1, the incident photon will stimulate the excited atom to
emit one photon of exactly the same energy as that of the incident photon.

Figure 1.4 Stimulated Emission

Hence two photons will be emitted in this process. This phenomenon is known as
stimulated emission. Here the emitted photons have the same frequency, phase, direction
and polarization, as that of the incident photon.Thus amplification of radiation takes place
by the stimulated process.

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 Stimulated emission is the nerve centre of laser action. In mediums having a large
number of atoms such as solids, liquids and gases, stimulated emission can be gainfully
applied.

The rate of transition from E2 to E1 in stimulated emission is given by

(dN2/dt)=-W21N2
W21 is the probability of stimulated transition which depends on the particular type of

transition but it also depends upon the intensity of the incident electromagnetic wave.

For a plane electromagnetic wave, it can be written that

W21=Φ*C21

Where Φ is the photon flux density of the incident wave and C21 is the quantity denoting
the dimension of the area

1.3.3 Absorption
Suppose the atom is at energy level E1. If this is the ground level, the atom remains as such

since this level is stable. The atom will remain in this state inless and until an external stimulus

acts on it.

Figure 1.5 Absorption Spectra

Assume that an electromagnetic wave of frequency f is incident to the material. Here , there is a

possibility that the energy level of the atom is raised level E2. The difference (E2-E1), required

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by the atom to decay, is obtained from the energy of the incident electromagnetic wave. This is

called absorption.

The equation shown below defines the rate of absorption as

(dN2/dt)=-W12N1

Where , N1 is the number of atoms per unit volume, which at a given time, are all at energy level
E1

In case of absorption also, we can write

W12=Φ*C12

1.4 TYPES OF LASER

For simplification we have 3 Types of lasers which are as follows

• Solid state laser

❖ Ruby Laser
❖ Nd-YAG Laser
❖ Alexandrite Laser
❖ Fibre Glass Laser

• Liquid lasers
❖ Pulsed dye lasers pumped by flash lamps
❖ Tunable pulsed dye lasers pumped by other lasers
❖ Tunable continuous wave lasers
❖ Mode locked dye lasers
• Gas lasers
❖ Helium Neon Laser
❖ Carbon Dioxide Laser
❖ Excimer Laser
❖ Nitrogen Laser

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1.5 APPLICATIONS OF LASER

There are various applications of Lasers in a wide range of fields. Some of the fields are briefly
described below which have the application of Lasers.

Manufacturing
Lasers are widely used in manufacturing, e.g. for cutting, drilling, welding, cladding, soldering
(brazing), hardening, ablating, surface treatment, marking, engraving, micromachining, pulsed
laser deposition, lithography, alignment, etc. In most cases, relatively high optical intensities are
applied to a small spot, leading to intense heating, possibly evaporation and plasma generation.
Laser-aided manufacturing often allows one to produce the essentially same parts with higher

quality and/or lower cost. Also, it is often possible to realize entirely new part designs or the use
of new materials. For example, automobile parts are increasingly made of light materials such as
aluminum, which require tentatively more laser joining operations.

Medical Applications
There is a wide range of medical applications. Often these relate to the outer parts of the human
body, which are easily reached with light; examples are eye surgery and vision correction,
dentistry, dermatology (e.g. photodynamic therapy of cancer), and various kinds of cosmetic
treatment such as tattoo removal and hair removal.

Lasers are also used for surgery (e.g. of the prostate), exploiting the possibility to cut tissues
while causing minimal bleeding. Some operations can be done with endoscopic means; an
endoscope may contain an optical fiber for delivering light light to the operation scene and
another fiber for imaging, apart from additional channels for mechanical instruments.

Military Applications

There are a variety of military laser applications. In relatively few cases, lasers are used as
weapons; the “laser sword” has become popular in movies, but not in practice. Some high-power
lasers are currently developed for potential use as directed energy weapons on the battle field, or
for destroying missiles, projectiles and mines.

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In other cases, lasers function as target designators or laser sights (essentially laser
pointers emitting visible or invisible laser beams), or as irritating or blinding (normally not
directly destroying) countermeasures e.g. against heat-seeking anti-aircraft missiles. It is also
possible to blind soldiers temporarily or permanently with laser beams, although the latter is
forbidden by rules of war.There are also many laser applications which are not specific for
military use, e.g. in areas such as range finding, LIDAR, and optical communications.

Laser range finder(LRF):

Pulsed laser range finders (LRFs) enable accurate and instantaneous distance measurement of
non-cooperative targets from several tens of meters to several tens of kilometers. These work on
the echo principle very much like radars in which the time taken to receive the reflected pulse
from the target is measured and converted to the range since the velocity of light is constant and
known. Laser range finders are highly compact owing to the small emitting apertures required to
produce a collimated beam at optical wavelengths. The LRFs are widely used for surveying,

bothin civilian and defence applications. Military range finder systems are built to stringent
standards for reliable operation in harsh environments and play a vital role in providing target
range information for fire control applications. IRDE is engaged in the design and development
of military laser range finder systems for over four decades. Several systems have been
introduced into the Services which include LRF for T-55 tank and MBT Arjun.

Figure 1.6 Laser Range Finder

Proximity fuses

A proximity fuze is a fuze that detonates an explosive device automatically when the distance to
the target becomes smaller than a predetermined value. Proximity fuzes are designed for targets

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such as planes, missiles, ships at sea and ground forces. They provide a more sophisticated
trigger mechanism than the common contact fuze or timed fuze.

British military researchers Sir Samuel Curran and W. A. S. Butement developed a proximity
fuze in the early stages of World War II under the name VT, an acronym of "Variable Time
fuze".The system was a small, short range, Doppler radar that used a clever circuit. The
development of proximity fuses was assigned to SSPL in year 1966.

Figure1.7 Typical image for proximity fuze.

DAZZLER (Weapon)

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 Figure 1.8 Dazzler

A dazzler is a directed-energy weapon intended to temporarily blind or disorient its target with
intense directed radiation. Targets can include sensors or human vision. Dazzlers emit infrared or
invisible light against various electronic sensors, and visible light against humans, when they are

intended to cause no long-term damage to eyes. The emitters are usually lasers, making what is
termed a laser dazzler. Initially developed for military use, non-military products are becoming
available for use in law enforcement and security.

Weapons designed to cause permanent blindness are banned by the 1995 United
Nations Protocol on Blinding Laser Weapons. The dazzler is a non-lethal weapon intended to
cause temporary blindness or disorientation and therefore falls outside this protocol.

SEMICONDUCTOR LASERS

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2.1 SEMICONDUCTORS
A semiconductor is a crystalline or amorphous solid whose electrical conductivity is typically
intermediate between that of a metal and an insulator and can be changed significantly by
altering the temperature or the impurity content of the material, or by illumination with light. The
unique energy-level structure of semiconductor materials leads to special electrical and optical
properties. Electronic devices principally make use of silicon (Si) as a semiconductor material,
but compounds such as gallium arsenide (GaAs) are of utmost importance to photonics.

2.1 Energy Bands in Semiconductors

Atoms of solid-state materials have a sufficiently strong interaction that they cannot be treated as
individual entities. Valence electrons are not attached (bound) to individual atoms; rather, they
belong to the system of atoms as a whole. The solution of the Schrodinger equation for the
electron energy, in the periodic potential created by the collection of atoms in a crystal lattice,
results in a splitting of the atomic energy levels and the formation of energy bands .Each band
contains a large number of finely separated discrete energy levels that can be approximated as a
continuum. The valence and conduction bands are separated by a “forbidden” energy gap of
width E, called the bandgap energy, which plays an important role in determining the electrical
and optical properties of the material.

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 Figure 2.1 Comparison between insulator, semiconductor and coductor

Materials with a filled valence band and a large energy gap ( > 3 eV) are electrical insulators;
those for which the gap is small or nonexistent are conductors (see Fig. 2.1). Semiconductors
have energy gaps that lie roughly in the range 0.1 to 3 eV Electrons and Holes. In accordance
with the Pauli exclusion principle, no two electrons can occupy the same quantum state. Lower
energy levels are filled first. In elemental semiconductors, such as Si and Ge, there are four
valence electrons per atom; the valence band has a number of quantum states such that in the
absence of thermal excitations the valence band is completely filled and the conduction band is
completely empty. Consequently, the material cannot conduct electricity. As the temperature
increases, however, some electrons will be thermally excited into the empty conduction band
where there is an abundance of unoccupied states. There, the electrons can act as mobile carriers;
they can drift in the crystal lattice under the effect of an applied electric field and thereby
contribute to the electric current. Furthermore, the departure of an electron from the valence
band provides an empty quantum state, allowing the remaining electrons in the valence band to
exchange places with each other under the influence of an electric field.
Concept of Effective Mass
Near the bottom of the conduction band, the E-k relation may be approximated by the Parabola
where E, is the energy at the bottom of the conduction band and m, is a constant representing the
effective mass of the electron in the conduction band.

E=EC +(h/2p)k2/(2*m*c)

Similarly, near the top of the valence band,

E=EC –(h/2p)k2/(2*m*c)

where E, = E, - E, is the energy at the top of the valence band and m, is the effective mass of a
hole in the valence band. In general, the effective mass depends on the crystal orientation and the
particular band under consideration.

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2.2 Direct and indirect gap semiconductors

Figure 2.2 Direct and Indirect Gap Semiconductor

Semiconductors for which the valence-band maximum and the conduction-band minimum
correspond to the same momentum (same k) are called direct-gap materials.Semiconductors for
which this is not the case are known as indirect-gap materials. The distinction is important; a
transition between the top of the valence band and the bottom of the conduction band in an
indirect-gap semiconductor requires a substantial change in the electron’s momentum. As is
evident in Fig. 2.2, Si is an indirect-gap semiconductor, whereas GaAs is a
direct-gap semiconductor. It will be shown subsequently that direct-gap semiconductors such as
GaAs are efficient photon emitters, whereas indirect-gap semiconductors such as Si cannot be
efficiently used as light emitters.

2.3 SEMICONDUCTING MATERIALS

Basically there are 4 types of semiconducting materials which are as follows:-

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 Table 1 semiconducting materials with theit general specifications
• Elemental semiconductors
• Binary semiconductors

Material Band gap energy Bandgap Energy Type

Wavelength
Ge 0.66 1.88 Indirect
Si 1.11 1.15 Indirect
AIP 2.45 0.52 Indirect
AlAs 2.16 0.57 Indirect
AlSb 1.58 0.75 Indirect
InAs 0.34 3.64 Direct
GaAs 1.42 0.87 Direct
• Ternary semiconductors
• Quaternary semiconductors

2.3.1 Elemental semiconductors

Several elements in group IV of the periodic table are semiconductors. Most important are
silicon (Si) and germanium (Ge). At present most commercial electronic integrated circuits and
devices are fabricated from Si. However, these materials are not useful for fabricating photon
emitters because of their indirect bandgap. Nevertheless, both are widely used for making photon
detectors.

2.3.2 Binary Semiconductors

Compounds formed by combining an element in group III, such as aluminum (Al),gallium (Gal,
or indium (In), with an element in group V, such as phosphorus (P),arsenic (As), or antimony
(Sb), are important semiconductors. There are nine such III-V compounds. The bandgap energies
and the lattice constants of these compounds are also provided. Various of these compounds are
used for making photon detectors and sources (light-emitting diodes and lasers). The most
important binary semiconductor for optoelectronic devices is gallium arsenide (GaAs).
Furthermore, GaAs is becoming increasingly important (relative to Si) as the basis of fast

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electronic devices and circuits.Compounds using elements from group II (e.g., Zn, Cd, Hg) and
group VI (e.g., S,Se, Te) of the periodic table also form useful semiconductors, particularly at
wavelengths shorter than 0.5 pm and longer than 5.0 pm, as shown in Fig. 15.1-6. HgTe and
CdTe, for example are nearly lattice matched, so that the ternary semiconductor Hg,Cd, -XTe is
a useful material for fabricating photon detectors in the middle infrared region of the spectrum.
Also used in this range are IV-VI compounds such as Pb,Sn, -XTe and Pb,Sn, -,Se. Applications
include night vision, thermal imaging, and long-wavelength lightwave communications.

2.3.3 Ternary Semiconductors

Compounds formed from two elements of group III with one element of group V (or one from
group III with two from Group V) are important ternary semiconductors. (AI.Ga i -xlAs, for
example, is a ternary compound with properties intermediate between those of AlAs and GaAs,
depending on the compositional mixing ratio x (where x denotes the fraction of Ga atoms in
GaAs replaced by Al atoms). The bandgap energy E, for this material varies between 1.42 eV for
GaAs and 2.16 eV for AlAs, as x is varied between 0 and 1. The material is represented by the
line connecting GaAs and AlAs in Fig. 15.1-5. Because this line is nearly horizontal, Al.Ga, -,As
is lattice matched to GaAs (i.e., they have the same lattice constant). This means that a layer of a
given composition can be grown on a layer of different composition without introducing strain in
the material. The combination Al,Ga, ,As/GaAs is highly important in current LED and
semiconductor laser technology.

2.4.4 Quaternary Semiconductors

These compounds are formed from a mixture of two elements from Group III with two elements
from group V. Quaternary semiconductors offer more flexibility for the synthesis of materials
with desired properties than do ternary semiconductors, since they provide an extra degree of
freedom. An example is provided by the quaternary (In t -,Ga,)(As i -,P,,), whose bandgap
energy E, varies between 0.36 eV (InAs) and 2.26 eV (Gap) as the compositional mixing ratios x
and y vary between 0 and 1. The shaded area in Fig. 15.1-5 indicates the range of energy gaps
and lattice constants spanned by this compound. For mixing ratios x and y that satisfy y = 2.16(1
- x), (In, -,Ga,)(As,-,P,,) can be very well lattice matched to InP and therefore conveniently
grown on it. These compounds are used in making semiconductor lasers and detectors.

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2.6 DOPED SEMICONDUCTORS
The electrical and optical properties of semiconductors can be substantially altered by adding
small controlled amounts of specially chosen impurities, or dopants, which alter the
concentration of mobile charge carriers by many orders of magnitude. Dopants with excess
valence electrons (called donors) can be used to replace a small proportion of the normal atoms
in the crystal lattice and thereby to create a predominance of mobile electrons; the material is
then said to be an n-type semiconductor. Thus atoms from group V (e.g., P or As) replacing
some of the group IV atoms in an elemental semiconductor, or atoms from group VI (e.g., Se or
Te) replacing some of the group V atoms in a III-V binary semiconductor, produce an n-type
material. Similarly, a p-type material can be made by using dopants with a deficiency of valence
electrons, called acceptors. The result is a predominance of holes. Group-IV atoms in an
elemental semiconductor replaced with some group-III atoms (e.g., B or In), or group-III atoms
in a III-V binary semiconductor replaced with some group-II atoms (e.g., Zn or Cd), produce a p-
type material. Group IV atoms act as donors in group III and as acceptorsin group V, and
therefore can be used to produce an excess of both electrons and holes in III-V materials.
Undoped semiconductors (i.e., semiconductors with no intentional doping) are
referred to as intrinsic materials, whereas doped semiconductors are called extrinsic materials.
The concentrations of mobile electrons and holes are equal in an intrinsic semiconductor, n = p =
n i, where n i increases with temperature at an exponential rate. The concentration of mobile
electrons in an n-type semiconductor (called majority carriers) is far greater than the
concentration of holes (called minority carriers), i.e., n x=- p. The opposite is true in p-type
semiconductors, for which holes are majority carriers and p Z+ n. Doped semiconductors at room
temperature typically have a majority carrier concentration that is approximately equal to the
impurity concentration.

2.7 SEMICONDUCTOR LASER DIODES

SSPL is a premier DRDO lab working in the field of semiconductor devices. High power
semiconductor laser diodes are being developed here for various strategic applications. The

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advantage of Semiconductor laser diodes is their low cost and wide applications. A laser diode is
formed by growing a very thin layer on the surface of a crystal wafer. The crystal is doped to
produce an n-type region and a p-type region, one above the other resulting in a p-n junction, or
diode. A laser diode is powered by injecting electric current and therefore, they are sometimes
referred to as injection laser diodes. Laser diodes have many applications. Laser diodes find a
wide use in telecommunications easily modulated and easily coupled light sources for fiber
optics communication. They are used in various measuring instruments such as rangefinders.
Another common use is in barcode readers. Infrared and red laser diodes are used in CD players,
CD ROM sand in DVD technology. Violet lasers are used in HD DVD and Blu-ray Technology.
These along with various others are numerous applications of laser diodes.

2.7.1 Principle of Semiconductor Diode lasers

Although made from solid materials, semiconductor diode lasers differ considerably from atomic
lasers, both in respect of energy level structures and pumping mechanisms.
In contrast to the single energy levels observed in isolated atoms, electrons in semiconductors
occupy broad bands of energy levels. Each band consists of a large number of closely packed
energy levels. As with any semiconductor p-n junction diode, forward electrical bias causes the
two species of charge carriers, holes and electron, to be "injected" from opposite sides of the p-n
junction into the depletion region. When an electron and a hole are present in the same region,
they may recombine or "annihilate" with the result being spontaneous emission. Spontaneous
emission is necessary to initiate laser oscillation, but it is one among several sources of
inefficiency once the laser is oscillating. In the absence of stimulated emission conditions,
electrons and holes may coexist in proximity to one another, without recombining, for a certain
time, termed the "upper-state lifetime" or "recombination time" (about a nanosecond for typical
diode laser materials), before they recombine. Then a nearby photon with energy equal to the
recombination energy can cause recombination by stimulated emission. This generates another
photon of the same frequency, travelling in the same direction, with the same polarization and
phase as the first photon. This means that stimulated emission causes gain in an optical wave (of
the correct wavelength) in the injection region, and the gain increases as the number of electrons
and holes injected across the junction increases. As in other lasers, the gain region is surrounded
with an optical cavity to form a laser. The two ends of the crystal are cleaved to form perfectly

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smooth, parallel edges, forming a Fabry-Perot resonator. Photons emitted into a mode of the
waveguide will travel along the waveguide and be reflected several times from each end face
before they are emitted. As a light wave passes through the cavity, it is amplified by stimulated
emission, but light is also lost due to absorption and by incomplete reflection from the end facets.
Finally, if there is more amplification than loss, the diode begins to “laser”.

Figure 2.3 Semiconductor Laser

2.7.2 Structure of Laser

The length of a semiconductor laser in the axial direction of the laser is usually about 0.2 to 1
mm. The material providing the gain I uniform over that length. In one of the two transverse
directions of a double heterostructure device, the additional materials of the semiconductors are
grown in layers of varying thickness ranging between 5 to 1000 nm, in order to build the
heterojunction. The extra layers are used to confine the recombination region of electrons and
holes; to minimize the generation of excess heat, and also to confine the optical beam.

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 Figure 2.4 Semiconductor Laser Structure

In other lateral direction, material boundaries are fabricated using lithographic techniques to
width, of the order of a few microns, to confine and to guide the electrical current and the optical
beam. The heterojunction is grown upon a substrate material such as GaAs or InP with a
metalized layer under the substrate, to cater for electrical contact. Above the heterojunction,
there is another metalized layer, which is also for electrical contact.
The density of the current flowing in a direction normal to the plane of the junction is of the
order of 800 ampere per centimeter square whereas, the maximum current that can be used
before the occuance of thermal damage is of the order of 50 milliamperes. Therefore, the current
must be confined to the lateral direction in the plane of the junction; by having a narrow
electrical contact that minimizes the size of the region when current flows.

2.7.3 Types of Semiconductor Lasers

There are various types of semiconductor laser structures which are classified below:-

• Homojunction lasers
• Double heterostructure laser
• Quantum well lasers
• Single mode lasers
• Multi mode operation

2.7.3.1 Homojunction lasers

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In homojunction lasers, a single junction of the n and p-doped materials is used. In these lasers,
considerable amount of heat is dissipated and there the gain gets tapered off in directions away
from the junction. As a result, these devices can effectively operate only at very low temperature,
which can be well below ambidient temperature.

2.7.3.2 Double heterostucture semiconductor

Figure 2.5 Double Heterostructure

When current flows through these layers, most of the energy deposition takes place in the active
region of the junction where the electrons are let in and the gain is produced. This is so because,
that is the area where the highest electrical resistance occurs. Thus, by having additional layers,
we get many desired additional features without extra loss of heat. Also it has been demonstrated
in the green and blue in the region around 0.5μm by using zinc, cadmium, selenium and sulphur.
These lasers have just about come to the commercial world. A semiconductor laser has a gain
coefficient between 5000 and 10,000 m-1. Hence the gain per pass is large enough, even for a
gain length of 1mm or less, to overcome the large inherent distributed loss, which is of the order

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of 2000 m-1 within the gain medium. The gain bandwidth is of the order of 20 nm, which
corresponds to the emission linewidth of the recombination radiation. There is a homogeneous
recombination emission broadening within the laser gain.

2.7.3.3 Quantum well Lasers

Concept of quantum well, quantum wire and quantum dots

A quantum well is a double heterojunction structure consisting of an ultra thin
(250 nm) layer of semiconductor material whose bandgap is smaller than that of the surrounding
material (Fig. 2.6). An example is provided by a thin layer of GaAs surrounded by AlGaAs

Figure 2.6 Quantum well Structure

The sandwich forms conduction- and valence band rectangular potential wells within which
electrons and holes are confined: electrons in the conduction-band well and holes in the valence-
band well. A sufficiently deep potential well can be approximated as an infinite potential well.
The energy levels E, of a particle of mass m (m, for electrons and m, for holes) confined to a
one-dimensional infinite rectangular well of full width d are determined by solving the time-
independent Schrodinger equation.

(h/2p)2(qp/d)2/2m
q = 1,2,... .

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As an example, the allowed energy levels of electrons in an infinitely deep GaAs well mc, =
O.O7m,) of width d = 10 nm are Eg = 54,216,486,. . . meV (recall that at T = 300 K, k,T = 26
meV). The smaller the width of the well, the larger the separation between adjacent energy
levels. In the quantum-well structure shown in electrons (and holes) are confined in the x
direction to within a distance dl (the well thickness). However, they extend over much larger
dimensions (d2, d, x=- d,) in the plane of the confining layer. Thus in the y-z plane, they behave
as if they were in bulk semiconductor. The energy-momentum relation is

E=Ec+(h/2p)2k12/2mc+ (h/2p)2k22/2mc+ (h/2p)2k32/2mc

where k, = qlr/di, k, = q2r/d2, k, = q3r/d3, and ql, q2, q3 = 1,2,. . . . Since d,+z d,, d,, k, takes on
well-separated discrete values, whereas k, and k, have finely spaced discrete values which may
be approximated as a continuum.

Figure 2.7 Density of States Figure 2.8 Quantum well Laser

A semiconductor material that takes the form of a thin wire of rectangular cross section,
surrounded by a material of wider bandgap, is called a quantum-wire structure. The wire acts as
a potential well that narrowly confines electrons (and holes) in two directions (x, y). Assuming
that the cross-sectional area is d,d,, the energy-momentum relation in the conduction band is

E=Ec+Eq1+Eq2+(h/2p)2k2/2mc

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 Eq1= (h/2p)2 (qp/d1)2/2mc

Eq2= (h/2p)2 (qp/d2)2/2mc

q1,q2 = 1,2,... .

and k is the wavevector component in the z direction (along the axis of the wire).
Each pair of quantum numbers (ql, q2) is associated with an energy subband with a
density of states e(k) = l/p per unit length of the wire and therefore l/pd,d2 per
unit volume. The corresponding density of states (per unit volume), as a function of energy, is

𝟏
𝒎𝒄
𝒅𝟏 𝒅𝟐 )(√
𝝆(𝑬) = 𝟐𝝅𝒉
𝑬𝒄 > 𝑬𝒄 + 𝑬𝒒𝟏 + 𝑬𝒒𝟐
√𝑬 − 𝑬𝒄 − 𝑬𝒒𝟏 − 𝑬𝒒𝟐
{ 𝟎

In a quantum-dot structure, the electrons are narrowly confined in all three directions within a
box of volume d,d,d,. The energy is therefore quantized to

E= + Eql + Eq2 + Eq3

where
Eq1= (h/2p)2 *(qp/d1)2/2mc

Eq2= (h/2p)2 *(qp/d2)2/2mc

Eq3= (h/2p)2 *(qp/d3)2/2mc

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In quantum-well lasers, the active layer is made thinner than 10 nm. So , the electronic and the
optical properties are drastically altered owning to the reduced dimensionality of the motion of
free electrons, from the three- dimensional nature to two dimensional.We can also vary the
spacing of the band- gap in semiconductor materials, and with that, vary the wavelength for
recombination emission. This can be done by introducing other selected atoms into the
semiconductor to replace the atoms of the original material, at sites that are randomnly located.
These other atoms must be somewhat identical, in size, to those of the original atoms so that the
integrity of the crystal lattice is maintained

PHOTOLUMINECSENCE

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Photoluminescence (abbreviated as PL) is light emission from any form of matter after the
absorption of photons (electromagnetic radiation). It is one of many forms of luminescence (light
emission) and is initiated by photoexcitation (i.e. photons that excite electrons to a higher energy
level in an atom), hence the prefix photo-Following excitation various relaxation processes
typically occur in which other photons are re-radiated. Time periods between absorption and
emission may vary: ranging from short femtosecond-regime for emission involving free-carrier
plasma in inorganic semiconductors up to milliseconds for phosphorescent processes in
molecular systems; and under special circumstances delay of emission may even span to minutes
or hours.

Observation of photoluminescence at a certain energy can be viewed as an indication that an

electron populated an excited state associated with this transition energy. While this is generally
true in atoms and similar systems, correlations and other more complex phenomena also act as
sources for photoluminescence in many-body systems such as semiconductors. A theoretical
approach to handle this is given by the semiconductor luminescence equations.

3.1 BASIC MECHANISMS OF PHOTOLUMINESCENCE

The phenomena which involve absorption of energy and subsequent emission of light are
classified generically under the term luminescence. Phosphors are luminescent materials that
emit light when excited by radiation, and are usually microcrystalline powders or thin-films
designed to provide visible color emission. After decades of research and development,
thousands of phosphors have been prepared and some of them are widely used in many areas.
Excitation by absorbance of a photon leads to a major class of technically important luminescent
species which fluoresce or phosphoresce. In general, fluorescence is “fast” (ns time scale) while
phosphorescence is “slow” (longer time scale, up to hours or even days). For convenience, the
topic of photoluminescence (PL) will be broadly divided into that based on relatively large-scale
inorganic materials, mainly exhibiting phosphorescence, and that of smaller dye molecules and
small-particle inorganic (“nanomaterials”), which can either fluoresce or phosphoresce. Their
applications differ. For many of the derived technical applications, it is irrelevant whether the
luminescence is fluorescence or phosphorescence. Either way the current range of applications is
extensive, and in one case has been recognized by the award of a Nobel Prize, in 2008.

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 Figure 3.1 Mechanism of Photoluminescence

3.1.1 Excitation and Emission Spectra

These spectra are generated by an instrument called a spectrofluorimeter, which comprised two
spectrometers: an illuminating spectrometer and an analyzing spectrometer. First, the dye sample
is strongly illuminated by a color of light that is found to cause some fluorescence. A spectrum
of the fluorescent emission is obtained by scanning with the analyzing spectrometer using this
fixed illumination color. The analyzer is then fixed at the brightest emission color, and a
spectrum of the excitation is obtained by scanning with the illuminating spectrometer and
measuring the variation in emission intensity at this fixed wavelength. For the purpose of
designing filters, these spectra are normalized to a scale of relative intensity.

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 Figure 3.2 Excitation and Emission Spectra

These color spectra are described quantitatively by wavelength of light. The most
common wavelength unit for describing fluorescence spectra is the nanometer (nm).The colors
of the visible spectrum can be broken up into the approximate wavelength values

Violet and indigo 400−450 nm

Blue and aqua 450−500 nm
Green 500−570 nm
Yellow and orange 570−610 nm
Red 610 to approximately 750 nm

In practical applications, phosphors are often excited by cathode rays, X-rays, or UV emission of
a gas discharge, which correspond to applications in displays, medical imaging and lighting,
respectively, such as cathode-ray-tube (CRT) color TV, X-ray fluorescent screens, and
fluorescent lamps. Energy transfer mechanism from one dopant (sensitizer) to another
(luminescent center) is sometimes used to enhance the sensitivity of a phosphor. Earlier, several
researchers have tried to sensitize this phosphor by co-doping with different rare earth metals.

Energy transfer between pairs of rare earth ions at dilution level below the self quenching limits

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has been known to take place generally through multipolar interaction like dipole–dipole
interactions or dipole–quadrupole interactions [2–4]. The use of energy transfer or metal
enhancement effects has been applied in assays and in sensing with molecular fluorophores for
sometime. These effects are also observed in nanoparticles and such approaches might lead to
even more robust and flexible analytical methods for nanoscale inorganic phosphors. When
absorption of UV or even visible light leads to emission, one speaks of optical excitation of
luminescence. This process takes place in, e.g., fluorescent lamps and phosphor-converted LEDs,
in which phosphors are used to at least partly change the wavelength of the radiation emitted by
the LEDs.

3.1.2 Radiative Transition

There are several possibilities of returning to the ground state. The observed emission from a
luminescent center is a process of returning to the ground state radiatively. The luminescence
quantum efficiency is defined as the number of photons emitted divided by the number of
photons absorbed, and in most cases is equal to the ratio of the measured lifetime to the radiative
lifetime of a given level. The processes competing with luminescence are radiative transfer to
another ion and nonradiative transfers such as multiphonon relaxation and energy transfer
between different ionsor ions of a similar nature. The last transfer is also named cross-relaxation.
shows the configurational coordinate diagram in a broad band emission. Assumption is made on

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an offset between the parabolas of the ground state and the excited state. Upon excitation, the

electron is excited in a broad optical band and brought in a high vibrational level of the excited
state. The center thereafter relaxes to the lowest vibrational level of the excited state and give up
the excess energy to the surroundings. This relaxation usually occurs nonradiatively. From the
lowest vibrational level of the excited state, the electron returns to the ground state by means of
photon emission. Therefore, the difference in energy between the maximum of the excitation
band and that of the emission band is found. This difference is called the Stokes shift .The
radiative transfer consists of absorption of the emitted light from a donor molecule or ion by the
acceptor species. In order to that such transfer takes place, the emission of the donor has to
coincide with the absorption of the acceptor. The radiative transfer can be increased considerably
by designing a proper geometry.

Figure 3.4 Radiative Transition

3.1.3 Non Radiative Transition

The energy absorbed by the luminescent materials which is not emitted as radiation is dissipated

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to the crystal lattice. It is crucial to suppress those radiationless processes which compete with
the radiation process. In order to understand the physical processes of nonradiative transitions in
an isolated luminescent center, the configurational coordinate diagrams are presented in Fig. 3.5.
In Fig. 3.5a, there is a Stokes shift between the ground state and the excited state. The relaxed-
excited state may reach the crossing of the parabolas if the temperature is high enough. Via the
crossing, it is possible for electrons to return to the ground state in a nonradiative manner. The
energy is given up as heat to the lattice during the process. In, the parabolas of ground state and

excited state are parallel. If the energy difference is equal to or less than four to five times the
higher vibrational frequency of the surrounding, it can simultaneously excite a few high-energy
vibrations, and therefore is lost for the radiation of phonons. This is called multiphonon
emission. In a three-parabola diagram as shown in Fig. 2.4c, both radiative and nonradiative
processes are possible. The parallel parabolas (solid lines) from the same configuration are
crossed by a third parabola originated from a different configuration. The transition from the
ground state to the lower excited state (solid line) is optically forbidden, but it is allowed to
transit to the upper excited state (dash line). Excitation to the transition allowed parabola then
relaxes to the relaxed excited state of the second excited parabola. Thereafter, emission occurs
from it.

Figure 3.5 Possiblities of radiative or non radiative transitions

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3.2 PHOTOLUMINESCENCE SPECTROSCOPY
Photoluminescence spectroscopy is a useful technique for the study and characteristics of
materials and dynamical processes occurring in materials. The radiative emission of photons is in
some ways the inverse of the absorption of photons. Photoluminescence is characterized as
spectroscopic techniques. It involves measuring the energy distribution of emitted photons after
optical excitation.

There are various types of PL Spectroscopy which are as follows:

• Time Resolved PL Spectroscopy- It Provide information regarding recombination

kinetics, surface recombination and transport dynamics etc but is sensitive to wave
function
• Spatially Resloved PL Spectroscopy- it is sensitive to sample inhomogeneties and
transport
• Time and Spatially Resolved PL Spectroscopy
• Near Field Scanning Microscopy- utilizes to measure surface topology of
semiconductor nanostructure

Photoluminescence spectroscopy has been widely recognized for many years as a useful tool for
characterizing the quality of semiconductor materials as well as elucidating the physics which
may accompany radiative recombination. Characterization studies of semiconductors commonly
quote results of X- Ray diffraction, reflection, high- energy electron diffraction(RHEED)
oscillation, transmission electron microscopy. Each of these characterization techniques is useful
in determining specific aspects concerning the material, and so one of them alone is capable of
fully characterizing all relevant properties of a semiconductor. In this regard, PL is useful in
quantifying, optical emission efficiencies, composition of the material, impurity content and
layer thickness.

3.2.1 CW Photoluminescence
Excitation of non equilibrium population of electrons and holes is most commonly achieved by
using a laser. Lasers are used for excitation to allow localized spatial resolution, well defined
penetration depth, and a monoenergetic initial distribution of electrons and holes. The

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penetration depth is defined as the point at which 90% of non reflected radiation is absorbed by
the sample, and for the semiconductors the penetration depths are typically sub-micron for above
gap light. The large dielectric constant of most semiconductors results in relatively large Fresnel
reflection losses. At normal incidence the reflection of laser light is 35% for Si and 30% for
GaAs. The resulting PL is then collected from the same sample surface as the surface excited by
the incident excitation radiation. This generic experimental set-up allows for separate focusing of
the laser excitation and imaging of the PL. Spectral resolutions of 0.1 A are easily attainable with
commercially available instruments. It is also possible to measure PL spectra with a Fourier
transform instrument (FTIR). However these instruments have more commonly been utilized in
infrared spectroscopy. PL is detected by a photomultiplier tube(PMT) after being spectrally
dispersed by a spectrometer. For GaAs photocathode are most of the spectrum out of 900nm, the
S-20 response PMTs with a GaAs photocathode are most suitable because of their relatively high
quantum efficiency and flat spectral response. In order to detect PL from Si, a different detector
is required since PMTs are barely able to cover the spectral range near the Si bandgap, S-1 type
PMTs are suitable for detecting PL out to 1200nm, but their quantum efficiency and spectral
response are lower and decreases rapidly.

Figure 3.6 CW Photoluminescence setup

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3.5 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.

Fluorescence

When the chemical substrate undergoes internal energy transitions before relaxing to its ground
state by emitting photons, some of the absorbed energy is dissipated so that the emitted light
photons are of lower energy than those absorbed. One of such most familiar phenomenon is
fluorescence, which has a short lifetime (10-8 to 10-4 s).

Phosphorescence

Phosphorescence is a radiational transition, in which the absorbed energy undergoes intersystem

crossing into a state with a different spin multiplicity. The lifetime of phosphorescence is usually
from 10-4 - 10-2 s, much longer than that of Fluorescence. Therefore, phosphorescence is even
rarer than fluorescence, since a molecule in the triplet state has a good chance of undergoing
intersystem crossing to ground state before phosphorescence can occur.

3.6 APPLICATIONS OF PHOTOLUMINESCENCE

Detection of ACQ or AIE properties

Aggregation-caused quenching (ACQ) of light emission is a general phenomenon for many

aromatic compounds that fluorescence is weakened with an increase in its solution concentration
and even condensed phase. Such effect, however, comes into play in the solid state, which has
prevented many lead luminogens identified by the laboratory solution-screening process from
finding real-world applications in an engineering robust form.Aggregation-induced emission

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(AIE), on the other hand, is a novel phenomenon that aggregation plays a constructive, instead of
destructive role in the light-emitting process, which is exactly opposite to the ACQ effect.

Figure 3.7 The structure of hexaphenylsilole (HPS) and PL spectra of compound

containing AIE

The emission color of an AIE luminogen is scarcely affected by solvent polarity, whereas that of
a TICT luminogen typically bathochromically shifts with increasing solvent polarity. However, it
shows different patterns of emission under different excitation wavelengths. At the excitation
wavelength of 372 nm, which is corresponding to the BODIPY group, the emission intensity
increases as water fraction increases. However, it decreases at the excitation wavelength of 530
nm, which is corresponding to the TPE group. The presence of two emissions in this compound
is due to the presence of two independent groups in the compound with AIE and ACQ
properties, respectively.

Detection of luminescence with respect to molarity

At the excitation wavelength of 329 nm, as the molarity increases, the emission intensity
decreases. Such compounds whose PL emission intensity enhances at low concentration can be a
good chemo-sensor for the detection of the presence of compounds with low quantity.

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 Figure 3.8 structure of a triphenylamine–boradiazaindacene (BODIPY) derivative.

Band gap determination

Band gap is the energy difference between states in the conduction and valence bands, of the
radiative transition in semiconductors. The spectral distribution of PL from a semiconductor can
be analyzed to nondestructively determine the electronic band gap. This provides a means to
quantify the elemental composition of compound semiconductor and is a vitally important
material parameter influencing solar cell device efficiency.

Impurity levels and defect detection

Radiative transitions in semiconductors involve localized defect levels. The photoluminescence

energy associated with these levels can be used to identify specific defects, and the amount of
photoluminescence can be used to determine their concentration. The PL spectrum at low sample
temperatures often reveals spectral peaks associated with impurities contained within the host
material. Fourier transform photoluminescence microspectroscopy, which is of high sensitivity,
provides the potential to identify extremely low concentrations of intentional and unintentional
impurities that can strongly affect material quality and device performance.

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Recombination mechanisms

The return to equilibrium, known as “recombination”, can involve both radiative and
nonradiative processes. The quantity of PL emitted from a material is directly related to the
relative amount of radiative and nonradiative recombination rates. Nonradiative rates are
typically associated with impurities and the amount of photoluminescence and its dependence on
the level of photo-excitation and temperature are directly related to the dominant recombination
process. Thus, analysis of photoluminescence can qualitatively monitor changes in material
quality as a function of growth and processing conditions and help understand the underlying
physics of the recombination mechanism.

Surface structure and excited states

The widely used conventional methods such as XRD, IR and Raman spectroscopy, are very often
not sensitive enough for supported oxide catalysts with low metal oxide concentrations.
Photoluminescence, however, is very sensitive to surface effects or adsorbed species of
semiconductor particles and thus can be used as a probe of electron-hole surface processes.

Limitations of photoluminescence spectroscopy

Very low concentrations of optical centers can be detected using photoluminescence, but it is not
generally a quantitative technique. The main scientific limitation of photoluminescence is that
many optical centers may have multiple excited states, which are not populated at low
temperature.The disappearance of luminescence signal is another limitation of
photoluminescence spectroscopy. For example, in the characterization of photoluminescence
centers of silicon no sharp-line photoluminescence from 969 meV centers was observed when
they had captured self-interstitials.

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 PL CHRACTERIZATION OF LASER STRUCTURE

Photoluminescence characterization of laser epitaxial structures is carried out by excitation of

sample using a suitable photon source. Electron and hole pairs are generated in the material and
diffuse towards the active region i.e. quantum well. Electron and hole recombine there and
luminescence radiation is generated from the sample. This radiation is collected at a detector
using a monochoromator. Carriers in the quantum well active region behaves in a similar manner
as the particle behaves in a 1 dimensional box. Therefore we need to study these concepts which
are explained below.

4.1 PARTICLE IN AN INFINTE POTENTIAL WELL

According to De-Broglie concept it associates a wave with every material particle traveling with
momentum p. The wavelength of the wave is

ldB =h/p

The classical analog of a particle in a box is a string that is fixed at both ends. When such a string

is plucked, the amplitude of the oscillations at the fixed ends is zero. Hence we find that

nldb/2=nh/2p=L n=1,2….

Solving for p we get

P=n*h/2L

The particle feels no potential energy so all its energy is in the form of kinetic energy. As a result
E=p2/2m
Substituting for p, we get

En=n2h2/8mL2, n=1,2,…

Now we analyze this problem quantum mechanically. The Schrodinger equation is

(dH/dx)*y(x) = E*y(x)

Where V(x)=infinite in regions 1 and 2 and V(x)=0 in region 2. The results are in no way

affected if in region 2 of the potential is V because it only has the effect of altering the zero of

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energy and so without of generality we will assume that V = 0 within the box.

d2y/dx2=ky
where k=√𝟐𝒎𝑬/𝒉𝟐

The general solution to this differential equation is

y(x)=Acos(kx)+Bsin(kx)

where A and B are constants.

The boundary conditions that the wave function should satisfy are

Y(0)=0

Y(L)=0

The first of these conditions implies that A=0. The second condition yields Bsin(kL)=0 which
implies that

kL=np, n=1,2,3…

k=np/L.

Hence

E=n2h2/8mL2, n=1,2,3

Yn=Bsin(npx/L)

Where h is Planck’s constant

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 Figure 4.1 Infinite Potential well

We know that according to the normalization condition on the wave function yields B
𝑳 𝒂
𝒏𝝅𝒙
∫ 𝝋𝟐 𝒅𝒙 = ∫ 𝑩𝟐 𝒔𝒊𝒏𝟐 ( )𝒅𝒙 = 𝟏
𝟎 𝟎 𝑳

B=√𝟐/𝑳

The minimum uncertainty in the momentum from the Heisenberg relation is

Δp=h’/2L

E=h’2/4Ml2

a result that agrees with that quantitative result

The expectation value is defined of an operator is defined as

̂ 𝒑𝝋𝒅𝝉/ ∫ 𝝋 ∗ 𝝋𝒅𝝉)
<Op>=(∫ 𝝋 ∗ 𝑸

The expectation value of the position for a particle in the nth state of a particle in a box would
hence be
𝟐 𝒍 𝒏𝝅𝒙 𝒏𝝅𝒙 𝟐 𝒍 𝒏𝝅𝒙 𝒏𝝅𝒙
<x>= 𝒍 ∫𝟎 𝒔𝒊𝒏( )𝒑̂ 𝒔𝒊𝒏 ( ) 𝒅𝒙 = ∫𝟎 𝒔𝒊𝒏 ( ) (−𝒊𝒉′ )(𝒅/𝒅𝒙)𝒔𝒊𝒏 ( ) 𝒅𝒙
𝑳 𝑳 𝒍 𝑳 𝑳

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4.2 Finite Potential Well
Consider the potential shown the particle has energy E, less than V0 and is bound to the well.

Region 1

x<= -L/2, V(x)=V0

-h2/2m d2y/dx2+V0y=Ey

d2y/dx2=k2y

k2=2m/(h/2p)2 (V0-E)>0

k=√2𝑚/(ℎ/2𝜋)2 (𝑉 − 𝐸)

Where h is Planck’s constant

the solutions to this differential equation are:

y=Bekx+De-kx, but sincey ->0 as x->-infinite, D=0

we get y=Bekx for region 1….

Region 3

x >=L/2, V(x)=V0

similarly to region 1, the solutions are:

y=D’ekx+Ae-kx, but sincey ->0 as x->infinite, D’=0

we get y=Aekx for region 3….

Region 2

-L/2<=x<=L/2, V(x)=0, substituting into TISE:

-(h/2p)2/2m*d2y/dx2+0=E*y

d2y/dx2=-2*m/h2Eψ

d2y/dx2=-k2ψ with k=√𝟐 ∗ 𝒎 ∗ 𝑬/𝒉𝟐

ψ=Ccos(kx) for even parity(n odd)

and ψ=Dsin(kx) for odd parity(n even)

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 Wavefunction Region Wavefunction
y=Bekx 1 y=B’ekx
ψ=Ccos(kx) 2 ψ=Dsin(kx)
y=Aekx 3 y=A’e-kx

Table 2: Summary of wavelengths of the finite potential well

Clearly for parity +1 Clearly for parity-1

B=A B’=-A’

So, at x=L/2, for even parity

….and equating ψ Ccos(KL/2)=-Ae-kL/2

….And equating dψ/dx -Cksin(KL/2)= -Ake-kL/2

Therefore

k/K=tan(kL/2)………….(Positive parity)

k/K=tan(p/2+kL/2)………(Negative parity)

now to determine energy E; so we should solve them numerically as these are transcendental,
using dimensionless parameters, η andζ

η=kL/2=L/2 √𝟐 ∗ 𝒎 ∗ 𝑬/𝒉𝟐 (Argument of trigonometric function)

ζ0= L/2√(𝟐 ∗ 𝒎 ∗ 𝑽𝟎 /𝒉𝟐 ) (Potential Strength parameter )

k2=2m/(h/2p)2 (V0-E)=2*m/h’2V0-k2

k2=K2{ζ02(2/L)21/K2-1}

k2/K2={ζ02/η2-1}

tan(η)=√−𝟏 + 𝜻𝟐𝟎 /𝜼𝟐

-cot(η)= √−𝟏 + 𝜻𝟐𝟎 /𝜼𝟐

If we solve these equations for η we will obtain energy values En for our finite well with the help
of a MATLAB program given at the appendix

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Also we can superimpose a plot of √−𝟏 + 𝜻𝟐𝟎 /𝜼𝟐 onto plots of tan(η) and–cot(η) to graphically
solve two equations. Therefore the values of η corresponding to energy levels are shown in the
next chapter.

Figure 4.2 Finite Square Well

CONCLUSION
In the following above experiment we are considering a GaAs laser structure of 8nm where we
have done 30% cladding of Al in valence band and 70% cladding of Al in conduction band. Now
when electron hole recombination takes place we obtain the photon of corresponding wavelength
of 839 nm with 30% band gap.

The corresponding values obtained through our MATLAB Program for our laser structure are as
follows:-

We know that the energy band gap for GaAs is determined by the following formula:

Egb=1.425+1.2475*x;
=1.7993
Where x is band gap of laser structure
Therefore ΔEc=(Egb-1.425)*.7*e;
ΔEv=(Egb-1.425)*.3*e;
Where ΔEc andΔEv are the respective changes in energy band gap of valence and
conduction band

1.For conduction band

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 η= 1.1376 and 2.1965 where η=kL/2=L/2 √𝟐 ∗ 𝒎 ∗ 𝑬/𝒉𝟐 , defined as argument of
trigonometric function Ec=0.0462 and 0.1721 ,where Ec is energy in conduction band.

ΔEc=4.1916*10-20

Potential strength parameter ζ=2.7101 where ζ0= L/2√(𝟐 ∗ 𝒎 ∗ 𝑽𝟎 /𝒉𝟐 )

1. For valence band

η=1.2871 and 2.5529 and 3.7563 where η=kL/2=L/2 √𝟐 ∗ 𝒎 ∗ 𝑬/𝒉𝟐

Ev=0.088 and 0.0346 and 0.0719

ΔEv=1.7964*10-20

Potential strength parameter ζ=4.5980 where ζ0= L/2√(𝟐 ∗ 𝒎 ∗ 𝑽𝟎 /𝒉𝟐 )

Total energy obtained=1.4800 eV

Wavelength of photon=839nm

Hence now we have got the following result from the mathematical model of laser structure
designed in MATLAB. Now we would compare the result from the actual PL Spectra we
obtained

Figure 4.3 Actual PL Spectra Obtained

APPENDIX

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Matlab Program for Determination of Energy values of conduction band
and valence band of laser structure of AlGaAs and its corresponding
wavelength.
clc ,clear all;
me=9.1*10^-31;
h=6.63*10^-34;
h=h/(2*pi);
e=1.6*10^-19;
l=80*10^-10;
z=0.3;
eg=1.425;
Egb=1.425+1.2475*z;

%valence band
v=(Egb-1.425)*.3*e;
m=0.45*me;
a=((2*m)/(h^2))*v;
b=sqrt(a);
c=(l/2)*b;

%conduction band
m1=0.067*me;
v1=(Egb-1.425)*.7*e;
a1=((2*m1)/(h^2))*v1;
b1=sqrt(a1);
c1=(l/2)*b1;
i=1;
k=1;
i1=1;

for n=0:0.00001:5
f=(((c^2)/(n^2))-1);
d(i1)=sqrt(f);

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p(i1)=tan(n);
o(i1)=-cot(n);
f1=(((c1^2)/(n^2))-1);
d1(i1)=sqrt(f1);

%if condition for valence band

if abs(d(i1)-p(i1))<0.0001
g(i)=n;
i=i+1;
elseif abs(d(i1)-o(i1))<0.0001
g(i)=n;
i=i+1;
end
%if condition for conduction band
if abs(d1(i1)-p(i1))<0.0001
j(k)=n;
k=k+1;
elseif abs(d1(i1)-o(i1))<0.0001
j(k)=n;
k=k+1;
end
i1=i1+1;
end
E1v=(2*g(1)^2*h^2)/(m*l^2);%energy of valence band
E1v=E1v/e

E1c=(2*j(1)^2*h^2)/(m1*l^2);%energy of conduction band

E1c=E1c/e

E=E1v+E1c+eg
s=3*10^8;
lambda=(h*2*pi*s/E/e)*10^10
%plot for conduction band
k1=1;
k2=1;

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for i=1:1:length(g)-1
if g(i+1)-g(i)>0.1
Ev(k1)=(2*g(i+1)^2*h^2)/(m*l^2);
Ev(k1)= Ev(k1)/e;
k1=k1+1;
end
end
for i=1:1:length(j)-1
if j(i+1)-j(i)>0.1
Ec(k2)=(2*j(i+1)^2*h^2)/(m1*l^2);
Ec(k2)=Ec(k2)/e;
k2=k2+1;
end
end
Ec=[E1c Ec]
Ev=[E1v Ev]
n=0:0.00001:5;
figure (1)

plot(n,d)
hold on
plot(n,o)
plot(n,p)
axis ([0 4.6 0 10])
xlabel('neeta')
ylabel('d')

title('valence')
%plot for valence band
figure (2)
plot(n,d1)
hold on
plot(n,o)
plot(n,p)
xlabel('neeta')
axis ([0 3 0 10])

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ylabel('d1')

title('conduction')

Figure 5.1 graph for valence band

Figure 5.2 graph for conduction band

REFERENCES

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1. Laser System and Applications - KR. Namibiar
2. Laser In Bioscience, Industry And Defence- Narain Mansharamani
3. Semiconductor Laser Fundamentals- W.W Chow And S.W Koch
4. Understanding Photonics- Salech AND Teich
5. Understanding Lasers Fundamentals, An Entry Level Guide-J.Mech
6. https://en.wikipedia.org/wiki/photoluminesence
7. www.springer.com/cda/content/document/cda.1/9783642343117.c2
8. Photoluminescence Spectroscopy Of Crystaline Semiconductors- G.D Gilliland

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