MSE 432- Optical properties of materials

Luminescence
Dr. Amr Hessein
2021-2022
❑Contents
❑Quantum Theory of Optical Transition in Atoms
▪ Absorption
▪ spontaneous emission
▪ Stimulated emission
▪ Einstein relations
▪ Quantum Transition Rates
❑Luminescence
▪ Interband luminescence: Direct gap materials and Indirect gap materials
❑Carrier Recombination Mechanisms
❑ Radiative recombination mechanisms
❑ Non-radiative recombination
❑Photoluminescence
❑Electroluminescence
▪ LED
▪ LASER

2
❑Quantum Theory of Optical Transition in Atoms
➢ The quantum theory of radiation assumes that light is emitted or absorbed whenever an atom makes a
jump between two quantum states.
➢ Absorption occurs when the atom jumps to a higher level, while emission corresponds to the process
in which a photon is emitted as the atom drops down to a lower level.

➢ Conservation of energy requires that the frequency ν of the photon satisfies:

3
❑Quantum Theory of Optical Transition in Atoms
➢ There are three main transition processes in atoms:
1- Spontaneous Emission
2- Absorption
3- Stimulated Emission
1- Spontaneous Emission
➢ Statistical physics tells us that atoms in excited states have a natural tendency to de-excite and lose
their excess energy. Thus, the emission of a photon by an atom in an excited state is a spontaneous
process.

➢ Spontaneous emission is the radiation of light by atoms in excited states

and each type of atom has a characteristic emission spectrum determined by
its energy levels.
➢ The photon emission rate is therefore proportional to the number of atoms in
the excited state (N2)

4
❑Quantum Theory of Optical Transition in Atoms
1- Spontaneous Emission

➢ So that the number of the atoms in the excited state decays exponentially with a time constant τ due to
spontaneous emission.
➢ The value of τ for a transition can range from about 1 ns to several milliseconds.

5
❑Quantum Theory of Optical Transition in Atoms
2- Absorption
➢ The atom is promoted to an excited state by absorbing the required energy from
a photon.
➢ This promotes an electron from level 1 to level 2. Unlike emission, it is not a
spontaneous process.
➢ The electron cannot jump to the excited state unless it is stimulated by an
incoming photon.

➢ The photon absorption rate is therefore proportional to the number of atoms in the lower state (N1) and
the spectral energy density u(ν).

6
❑Quantum Theory of Optical Transition in Atoms
3- Stimulated Emission
➢ Einstein realized that the analysis was not complete, and introduced a third type of transition called
Stimulated emission.
➢ In this process, the incoming photon field can stimulate downward emission transitions as well as
upward absorption transitions.

➢ The stimulated emission rate is therefore proportional to the number of atoms in the higher state (N2)
and the spectral energy density u(ν).

➢ Stimulated emission is a coherent quantum mechanical effect, in which the photons

emitted are in phase with the photons that induce the transition 7
❑Quantum Theory of Optical Transition in Atoms
➢ The three Einstein coefficients introduced above are not independent parameters: they are all related
to each other. If we know one of them, we can work out the other two.
➢ In these steady state conditions, the rate of upward transitions due to absorption must
exactly balance the rate of downward transitions due to spontaneous and stimulated
emission.

➢ Since the atoms are in thermal equilibrium with the radiation

field at temperature T

“Einstein Relations”

8
❑Quantum Theory of Optical Transition in Atoms

➢ Remarks

1. The probabilities for stimulated absorption and emission are the same. i.e. Einstein
coefficients tells us that transitions that have a high absorption probability will also have a high
emission probability, both for spontaneous processes and stimulated ones.
2. The relationships between the Einstein coefficients have been derived for the case of an atom in
equilibrium with black-body radiation. However, once we have derived the interrelationships,
they will apply in all other cases as well
3. Einstein Relations are very useful, because we then only need to know one of the coefficients to
work out the other two. For example, we can measure the radiative lifetime (τ) to determine A21 ,
9
and then work out the B coefficients.
❑Quantum Theory of Optical Transition in Atoms
➢ An important application of the Einstein coefficients is in the analysis of optical amplification in a LASER
(Light Amplification by Stimulated Emission of Radiation) medium.
➢ This is achieved when the rate of stimulated emission exceeds the rate of absorption, so that the light
intensity increases rather than decreases as it propagates through the medium

➢ this condition can be written as:

or we must have

➢ Which describes a non-thermal distribution in which the weighted population of the upper level exceeds
that of the lower level.
➢ This condition is called population inversion, and is a necessary requirement for LASER operation.
10
11
❑Quantum Theory of Optical Transition in Atoms
4- Quantum Transition Rates
➢ The light–matter interaction is described by transition probabilities (Wij), which can be
calculated by using Fermi’s golden rule:
2𝜋
𝑊𝑖→𝑗 = |𝑀𝑖𝑗 |2 𝑔(ℏ𝜔)
Where ℏ
Mij→is the electric-dipole matrix element that contain the parameters of the initial and final quantum
states such as the angular quantum number and angular momentum.
g(hν) → is the density of states.

➢ This leads to the notion of electric-dipole selection rules. These are rules about the quantum
numbers of the initial and final states. If the states do not satisfy the selection rules, then the
electric-dipole transition rate will be zero.

12
❑Quantum Theory of Optical Transition in Atoms
4- Quantum Transition Rates

➢ Allowed transitions:
Are the transitions those obey the electric-dipole selection rules have high transition
probabilities, and therefore short radiative lifetimes, typically in the range 1–100 ns.

➢ Forbidden transitions:
Are the transitions those do not obey the electric-dipole selection rules and by
contrast have low transition probabilities, and therefore slow radiative rate, typically
ranging from milliseconds to days, the excited state is said to be metastable

➢ The different timescales for allowed and forbidden transitions lead to another general
classification of spontaneous emission as fluorescence and phosphorescence, respectively.

13
❑Quantum Theory of Optical Transition in Atoms
4- Quantum Transition Rates
➢ The electric-dipole selection rules for a single electron in a hydrogenic system with
quantum numbers l, m, s, and ms are:

s→ spin quantum number

ms→ spin angular momentum

➢ The spin selection rules follow from the fact that the photon
does not interact with the electron spin, and so the spin
Grotrian diagram 14
quantum numbers never change in the transition.
❑Quantum Theory of Optical Transition in Atoms
4- Quantum Transition Rates
➢ The selection rules can be generalized to many-electron atoms with quantum numbers (L, S,
J) as follows:

L→ orbital angular momentum

J→ angular momentum
S→ spin angular momentum
15
❑Luminescence
➢ Luminescence
It is the radiative emission process in solids in which electrons in an
excited state drop to lower levels by emitting photons.

➢ Luminescence is the reverse process of absorption.

➢ Atoms emit light by spontaneous emission when electrons in excited states drop
down to a lower level by radiative transitions.

➢ Luminescence can occur by a number of mechanisms:

▪ Photoluminescence: Fluorescence, Phosphorescence,
▪ Electroluminescence
▪ Cathodoluminescence,
▪ Chemiluminescence: Bioluminescence, Electrochemiluminescence
▪ Mechanoluminescence: Piezoluminescence, Fractoluminescence.
➢ we mainly consider just two or three mechanisms 16
❑Luminescence
➢ Photoluminescence
It is the re-emission of light after absorbing a photon of higher energy.

➢ Electroluminescence
It is the emission of light caused by running an electrical current through the
material..

➢ The physical processes involved in both photoluminescence and

electroluminescence are:
1. Depend on the energy relaxation mechanisms in the solid.
2. the shape of the emission spectrum is affected by the thermal
distributions of the electrons and holes within their bands.

➢ For example: The photon cannot be emitted unless the lower level for the
transition is empty, i.e. injecting hole

17
❑Luminescence
➢ The spontaneous emission rate for radiative transitions between two levels is determined by the
Einstein A coefficient and the population of the upper level.

solving

➢ Remarks
➢ the Einstein A coefficient is directly proportional to the B coefficient. This means that transitions which have large
absorption coefficients also have high emission probabilities and short radiative lifetimes.
➢ A transition might have a high emission probability, but no light will be emitted unless the upper level is populated.
So that the luminescent intensity at frequency ν as:

➢ This contrasts with the absorption spectrum, where photons can be absorbed to any state
within the excited state band, no matter how far it is above the bottom of the band. 18
❑Luminescence
➢ The alternative pathway between the excited state and ground state bands is non-radiative relaxation.
The electron might, for example, lose its excitation energy as heat by emitting phonons, or it may
transfer the energy to impurities or defects called ‘traps

➢ If these non-radiative relaxation processes occur on a faster time

scale than the radiative transitions, very little light will be emitted.

➢ The luminescent efficiency ηR (sometimes also called the quantum

efficiency) can be calculated by

19
❑Luminescence: Interband Luminescence
➢ Interband luminescence occurs in a semiconductor when an electron that has been excited
into the conduction band drops back to the valence band by the emission of a photon
(electron-hole recombination) Metals has no bandap→ no luminescence is observed
1- Direct gap materials
➢ The optical transitions between the valence and conduction bands of
typical direct gap semiconductors are dipole-allowed. This implies
through the radiative lifetime will be short, with typical values in the
range 10−8 – 10−9 s. The luminescent efficiency is therefore expected
to be high
➢ Since the momentum of the photon is negligible compared to the
momentum of the electron, the electron and hole that recombine must
have the same k vector. Therefore, the transition is represented by a
downward vertical arrow on the band diagram,
➢ The emission takes place near k = 0, and corresponds to a photon of
energy Eg.
➢ No matter how we excite the electrons and holes in the first place, we
20
always obtain luminescence at energies close to the band gap
❑Luminescence: Interband Luminescence
2- Indirect gap materials
➢ Conservation of momentum requires that a phonon must either be
emitted or absorbed when the photon is emitted

➢ The requirement of emitting both a phonon and a photon during the

transition makes it a second-order process, with a relatively small
transition probability.
➢ The radiative lifetime is therefore much longer than for direct
transitions. That this makes the luminescent efficiency small,
because of the competition with non-radiative recombination.
➢ indirect gap materials are generally bad light emitters and are only
used when there is no alternative direct gap material available in the
desired emission region

21