MSE 432- Optical properties of materials

Optical Coefficients of Materials

Dr. Amr Hessein
2021-2022
❑Contents
1. Classification of Optical processes
2. Optical Coefficients
3. The complex Refractive Index and Dielectric Constant
4. Optical Materials
5. Solved Examples and Tutorials

2
1. Classification of Optical processes

3
2. Optical Coefficients
1- The Coefficient of Reflection (Reflectivity).

Reflectivity (R) is defined as the ratio of the reflected power to the power incident on the surface.
2- The coefficient of transmission or (transmissivity).

Transmissivity (T) is defined as the ratio of the transmitted power to the incident power.

If there is no absorption or scattering:

3- The refractive index

The refractive index (n) is defined as the ratio of the velocity of light in free space c to the velocity of
light in the medium v

The refractive index depends on the frequency of the light beam.

This effect is called Dispersion 4
2. Optical Coefficients
4- The absorption coefficient

The absorption coefficient (α) is defined as the fraction of the power absorbed in a unit length of
the medium [α~ m-1 or cm-1]

➢ Beer’s law:

where I0 is the optical intensity at z = 0

➢ The absorption coefficient is a strong function of frequency, so that optical

materials may absorb one colour but not another.

5
2. Optical Coefficients
4- The absorption coefficient

For a strongly absorbing medium (i.e. αl >>1), multiple reflections are negligible

𝑅1 = 𝑅2 = 𝑅

The (1 − R)2 term accounts for the exponential factor gives the
the transmission of the front and decrease in intensity due to the
back surfaces absorption
6
2. Optical Coefficients
4- The absorption coefficient

If the medium is transparent, i.e. α = 0,

for incoherent light

while for coherent light, the transmission will oscillate as

the wavelength is changed due to the formation of bright
and dark interference fringes.

7
2. Optical Coefficients
5- optical density (O.D.)

This is sometimes called the absorbance (A), and is defined as

where l→ is the length of the absorbing medium

By substitute from: 𝐼 𝑙 = 𝐼0 𝑒 −𝛼𝑙

8
3. The complex Refractive Index
➢ The complex refractive index (𝑛)
ധ is defined through the equation:

Where
𝑐
n→ is the same as the normal refractive index (𝑛 = 𝑣)
κ → is called the extinction coefficient (Sometimes called molar extinction coefficient and written as ε ~
M-1 cm-1)

➢ the extinction coefficient that is directly related to the absorption coefficient α of the medium:

λo→ is the vacuum wavelength of the light

➢ Thus, if n is complex, then ϵr must also be complex.

9
3. The complex Refractive Index
➢ using the standard result derived from Maxwell’s equations:

➢ The reflectivity depends on both n and κ and is given by:

At normal incidence

➢ In a transparent material such as glass in the visible region of the spectrum, the
absorption coefficient is very small. So that, κ and ϵ2 are negligible, and hence that both n
and ϵr may be taken as real numbers. 10
4. Optical Materials
➢ The solid-state materials can be loosely classified into five general categories according to on
the optical properties:
1. Crystalline Insulators and Semiconductors
2. Glasses
3. Metals
4. Molecular Materials
5. Doped Glasses and Insulators.

11
4. Optical Materials
❑ How do the optical properties of a solid differ from those of its constituent atoms or
molecules?
➢ The differences between the condensed phase (solid-state phase) and the atoms or even low
condensed states such as gaseous or liquid state can be attributed to five aspects that make the
physics of the solid state interesting and different:
1. Crystal Symmetry
2. Electronic Bands
3. Vibronic Bands
4. The Density of States
5. Delocalized States and Collective Excitations.

12
4. Optical Materials
1. Crystal symmetry
[The point group symmetry (and also space group) refers to the group of symmetry operations that
leaves the crystal invariant. Due to the lower symmetry of some crystals we expect to find other
effects in the solid state such as Optical anisotropy].

https://crystalsymmetry.files.wordpress.com/2014/08/poster_23
13
0_the_space_group_list_project_230_dina0_c-2.pdf
4. Optical Materials
2. Electronic Bands
[This causes the observation of broad bands of absorption and emission rather than
discrete lines].

3. Vibronic Bands
[The coupling between electronic states of the atoms or molecules in a solid with the
vibrational modes of the crystal has the effect of broadening the absorption and emission
lines of the atoms into continuous bands]. 14
4. Optical Materials
4. The Density of States
➢ This continuum of states leads to continuous absorption and emission.
➢ Knowledge of g(E) is crucial for calculating the absorption and emission spectra due to
interband transitions.

15
4. Optical Materials
5. Delocalized states and collective excitations.
➢ In solids, the electron states to spread over many atoms (delocalized electron waves ) and
can move freely throughout the whole crystal and interact with each other in a way that
is not possible in atoms.
➢ The delocalization also allows collective excitations (quasiparticles) of the whole
crystal rather than individual atoms.
➢ Two examples: the excitons formed from delocalized electrons and holes in a
semiconductor, and the plasmons formed from free electrons in metals and doped
semiconductors]

Plasmons 16
Exciton
4. Optical Materials
➢ The microscopic models used to explain the optical phenomena are generally classified into
one of the following three general categories:
1. Classical Model
2. Semi-classical Model
3. Fully Quantum Model

1. Classical Model
➢ In the classical approach we treat both the medium and the light according to classical
physics.

Classical Electromagnetic Wave The dipole oscillator model 17

4. Optical Materials
1. Classical Model
(i) The Atomic Oscillators
➢ The electrons are held to the heavy nucleus in a stable orbit by springs which represent the restoring
forces due to the binding between them.
➢ The natural resonant frequency ω0 of the atomic
dipoles is given by:

➢ Thus, Each atom has a series of characteristic resonant frequencies which we now know to
18
correspond with the quantized transition energies.
4. Optical Materials
1. Classical Model
(i) The Atomic Oscillators
➢ If ω of the external electromagnetic wave coincides with one of the
natural frequencies of the atom (ω = ω0), then we have a resonance
phenomenon. This induces very large amplitude oscillations, and
transfers energy from the external wave to the atom (i.e. The atom
can therefore absorb energy from the light wave)
➢ If ω does not coincide with any of the resonant frequencies, then the
atoms will not absorb, and the medium will be transparent.

➢ In this situation the light wave drives non-resonant oscillations of the atoms at its own
frequency ω but with a phase lag. This implies that the propagation velocity is smaller
than in free space which is characterized by the refractive index (can be considered as a
repeated elastic scattering process).
19
4. Optical Materials
1. Classical Model
(ii) The Vibrational Oscillators
➢ A polar molecule is one in which the charge cloud of the electrons
that form the bond sits closer to one of the atoms than to the other [
such as ionic molecules as Na+Cl−, covalent molecules as Water
H2O].
➢ The polar molecule as assumed consists of two charged atoms bound
together in a stable configuration, with the spring representing the
molecular bond between them.

➢ The charged atoms can vibrate about their equilibrium positions and induce an oscillating
electric dipole with natural frequency ω0.
➢ The vibrations occur at infrared frequencies and are associated with strong absorption lines
in the infrared spectral region. 20
4. Optical Materials
1. Classical Model
(ii) The Vibrational Oscillators
➢ In a crystalline solid formed from the condensation of
polar molecules, the atoms are arranged in an alternating
sequence of positive and negative ions. The ions can
vibrate about their equilibrium positions, and this
produces oscillating dipole waves (lattice vibrations).

➢ light–matter interaction is associated with the excitation

of phonons which are quantized lattice vibrations.

➢ we can treat the two types of dipole oscillators “bound electron oscillators and
vibrational oscillator” separately because the resonances occur at very different
frequencies.
21
4. Optical Materials
1. Classical Model
(iii) The free electron Oscillators
➢ Metals and doped semiconductors, by contrast, contain significant numbers of free electrons.
➢ The dipole oscillator model to free electron systems is generally called the Drude–Lorentz model

➢ A plasma consists of a gas of charged particles in dynamic equilibrium. The particles are in constant motion, and
this can create local charge fluctuations (Plasma Oscillation).
22
➢ The quasi-particles that correspond to these quantized plasma oscillations are called plasmons
4. Optical Materials
2. Semi-classical Model
➢ In semi-classical models we apply quantum mechanics to the medium atoms, but treat the
light as a classical electromagnetic wave.

Classical Electromagnetic Wave Energy Levels Quantization

23
4. Optical Materials
3. Fully quantum Model
➢ This is the realm of quantum optics, where both the atoms and the light are treated quantum
mechanically.

The light is a beam of photons Energy Levels Quantization

24
4. Optical Materials: Examples
1. Crystalline Insulator
➢ Sapphire has a high transmission in the wavelength range 0.2– 6 µm, which explains why it appears
colorless and transparent to the human eye.
➢ Within the transparency range (0.2– 6 µm) the
absorption coefficient is very small, and the
refractive index may be taken to be real with no
imaginary component (n ~1.77).
➢ The transmission coefficient in the transparency
range is determined by the reflectivity of the surfaces
(α = 0).

➢ The dip in the transmission in the infrared spectral

region around 3 µm, and the sharp drop in the
transmission for λ > 6 µm is caused by vibrational Transmission spectrum of a sapphire
(Al2O3) crystal of thickness 3 mm. 25
absorption
4. Optical Materials: Examples
1. Crystalline Insulator
➢ The transmission drops sharply in the ultraviolet spectral region for λ < 0.2 µm due to absorption by
bound electrons.
➢ The onset of the absorption is called the
fundamental absorption edge. The wavelength
of the fundamental edge is determined by the
band gap of the insulator.

λ < 0.2 µm → bandgap >6.2 eV

Transmission spectrum of a sapphire

(Al2O3) crystal of thickness 3 mm. 26
4. Optical Materials: Examples
2. Semiconductor
➢ The optical properties of semiconductors are conceptually similar to those of insulators, except that the
electronic transitions occur at longer wavelengths (Lower energy).
➢ The short wavelength edge occurs beyond 700 nm

λ ~ 700 nm → bandgap ~ 1.77 eV

➢ Hence no visible light is transmitted through the
crystal, and it has a dark metallic appearance to the
eye.
➢ At wavelength> 700 nm, The maximum
transmission is around 60% which is again mainly
limited by the surface reflectivities.
Transmission spectrum of a CdSe
crystal of thickness 1.67 mm 27
4. Optical Materials: Examples
2. Semiconductor
➢ The upper limit of the transmission range is determined by the lattice absorption, as for insulators, and
also by free carrier absorption ( thermal excitation of free electrons).
➢ The short wavelength edge occurs beyond 700 nm

➢ Note that, the refractive index increases as the

band gap wavelength gets larger Transmission spectrum of a CdSe
crystal of thickness 1.67 mm 28
4. Optical Materials: Examples
3. Glasses
➢ Most types of glass are made by fusing sand (silica: SiO2) with other chemicals.
➢ Pure fused silica is an insulator, and shows all the characteristic features of insulators
▪ It is transparent in the visible region ( from ~200 nm in the ultraviolet to beyond 2000 nm in the
infrared.),
▪ absorbs in the ultraviolet due to the electronic transitions of the SiO2 molecules,
▪ absorbs in the infrared due to vibrational absorption.

29
4. Optical Materials: Examples
3. Glasses
➢ Fused silica is used extensively in the fibre-optics industry
➢ This variation of the refractive index with wavelength (dispersion) changes
by less than 1% over the whole visible spectral region.

➢ They are not crystalline solids, and therefore do not exhibit the optical
anisotropy that is characteristic of some crystals.

➢ Chemicals ( Oxides, metals or semiconductor nanoparticles) are commonly

added to silica during the fusion process to produce a whole range of other
types of glasses

30
4. Optical Materials: Examples
4. Metals
➢ The characteristic optical feature of metals is that they are shiny. This is a consequence of their very
high reflection coefficients. Metals used for producing mirrors
➢ The high reflectivity (~100% in the infrared, >80% throughout
the whole visible region) is caused by the interaction of the
light with the free electrons that are present in the metal.
➢ The reflectivity then drops sharply in the ultraviolet. The
plasma frequency usually corresponds to a wavelength in the
ultraviolet spectral region.
➢ This general behavior is observed in all metals. There is strong
reflection for all frequencies below a characteristic cut-off
frequency called the plasma frequency.
➢ Some metals have characteristic colours. Copper, for example, has a pinkish colour,
while gold is yellowish. These colours are caused by interband electronic transitions
that occur in addition to the free carrier effects that cause the reflection. 31
4. Optical Materials: Examples
5. Doped insulators and glasses
➢ Rubies consist of Cr3+ ions doped intoAl2O3
(sapphire).
➢ The presence of the chromium ions produces two
strong absorption bands, one in the blue spectral
region and the other in the yellow/green region.
➢ These two absorption bands give rubies their
characteristic red color

➢ The color of doped glass can be controlled in two

different ways:
➢ The composition of the dopant (e.g. CdxZn1-xSe)
➢ The size of the semiconductor crystallites

32
→This equation used to calculate the reflectivity of the air-medium interface
Ans.:
Ans.: 521 nm