Ch4 Optical Properties
Ch4 Optical Properties
Key Observations:
• If the frequency,𝞶 of the light used is less than a critical value 𝝼0 ( i.e. 𝞶 < 𝝼0 ),
irrespective of its intensity and duration of illumination and voltage V(small) applied,
there is no current for a particular material of the cathode..
• If the frequency,𝞶 of the light used is more than a critical value 𝝼0 ( i.e. 𝞶 > 𝝼0 ),
irrespective of its intensity and duration of illumination, for zero applied voltage(i.e.
V=0) there is non zero current for a particular material of the cathode.
• The current is observed almost as instantaneously as the illumination is applied i.e.
almost no delay.
• If the frequency,𝞶 of the light used is more than or equal to a critical value 𝝼0 ( i.e.
𝞶 ≥ 𝝼0 ), irrespective of its intensity and duration of illumination, the current becomes
zero for a particular reverse or negative applied voltage 𝑉0 across the electrodes for a
particular material of the cathode.
• If the frequency,𝞶 of the light used is more than or equal to a critical value 𝝼0 ( i.e.
𝞶 ≥ 𝝼0 ), the current becomes almost saturated at a particular value after sufficient
forward or positive applied voltage 𝑉 across the electrodes for a particular material of
the cathode for a particular intensity of light used.
• If the frequency,𝞶 of the light used is more than or equal to a critical value 𝝼0 ( i.e.
𝞶 ≥ 𝝼0 ), irrespective of its intensity and duration of illumination, the value of the
reverse or negative applied voltage 𝑉0 across the electrodes at which the current
becomes zero for a particular material of the cathode depends on the frequency of light
used.
• If the frequency,𝞶 of the light used is more than or equal to a critical value 𝝼0 ( i.e.
𝞶 ≥ 𝝼0 ), the current value at which it becomes almost saturated after sufficient
forward or positive applied voltage 𝑉 across the electrodes for a particular material of
the cathode depends only the intensity of light used and not on the frequency of light
used.
• The critical frequency value 𝝼0 is dependent on the material of the cathode.
• The maximum kinetic energy of any emitted electron is dependent on the material of
cathode and frequency of light used not on the intensity of light. This relation is given
1
by 𝐾𝐸𝑚𝑎𝑥 = 2 𝑚𝑒 𝑣𝑒2 = 𝑞𝑉0 = ℎ𝞶 − ɸ0 = ℎ(𝞶 − 𝞶0 ) where ɸ0 is work function of the
cathode metarial.
• Angular distribution of the photoelectrons is highly dependent on polarization of the
incident light, as well as the quantum properties such as atomic and molecular orbital
symmetries and the electronic band structure of the material of the cathode.
Fig. IV curve for different intensity but same frequency of light having 𝞶 ≥ 𝝼0 and for a
specific cathode material
Fig. IV curve for different frequency of light all having 𝞶 ≥ 𝝼0 with same intensity for a
specific cathode material
Fig. Maximum possible kinetic energy Vs frequency of light curve for different cathode
material at same intensity of light
Note:
All these observations were not explained by the classical wave theory as according to it there
should be photoemission once the energy accumulated given by the product of intensity and
time duration of illumination crosses the work function of the material irrespective of the
frequency of light used.
Explanations:
• Light is coming in the form of collection of photons with each such photon having
energy 𝐸 = ℎ𝞶 i.e. energy of the individual photons depend only on the frequency, not
on intensity and energy of EM waves is quantized or discrete.
• More intensity only means more number of such photons with the same individual
energy.
• One such photon interact with only one electron in the material and it is like inelastic
collision of particles.
• If 𝐸 ≥ ɸ0 𝑜𝑟 𝞶 ≥ ν0 then after collision the photon comes to rest i.e. it gets absorbed
in the material and the electron collided with it receives the entire energy
instantaneously and comes out of the material with kinetic energy, 𝐾𝐸𝑚𝑎𝑥 = ℎ𝞶 − ɸ0
in all possible direction.
• The direction of emitted photons
electron depends on polarization of the incident light, as well
as the quantum properties such as atomic and molecular orbital symmetries and the
electronic band structure of the material of the cathode very much like how orientation
of particles after collision depends on initial orientation of particles before collision.
• Some of the emitted electrons which are properly aligned can reach the anode due to
their kinetic energy causing current in the circuit even without applying any external
voltage i.e. V=0. So in order to collect maximum number of the electrons emitted by
the cathode, irrespective of its direction of ejection, we need the anode area to cover
maximum portion of the front side of the cathode.
• If we apply a forward voltage or positive voltage at anode, then it applies additional
attractive force on the emitted electrons to go towards it. As a result the misaligned
electrons also moves towards anode and ultimately reach anode causing an increase in
current. If sufficient positive voltage is applied then all the electrons emitted from
cathode will be collected at anode and current will reach a maxima or saturation
provided the distance between the electrodes is small enough so that the transit time of
such electrons between the electrodes does not create any limitation on the rate of
electrons (i.e. current) reaching the anode.
• If we apply a reverse voltage or negative voltage at anode, then it applies repulsive
force on the emitted electrons to get repelled by it. As a result some of the properly
aligned electrons also moves away from reaching the anode causing a decrease in
current. If sufficient negative voltage, 𝑉0 is applied then all the electrons emitted from
cathode will be effectively repelled by the anode so that no electron reach the anode
causing current to become zero. This voltage can be found from the relation,
1
𝑞𝑉0 = 𝐾𝐸𝑚𝑎𝑥 = 2 𝑚𝑒 𝑣𝑒2 = ℎ𝜈 − ɸ0 = ℎ(𝜈 − 𝜈0 )
• For 𝐸 ≥ ɸ0 , if more intensity light used than more no of electrons will come out
causing more no of electrons to reach anode thereby increasing the current.
• If 𝐸 < ɸ0 or 𝞶 < ν0 , the photon is unable to transfer the required energy to the electron
to come out of the material and hence no current irrespective of the intensity of light
and also the applied voltage between the electrodes. Note that here we want the applied
external voltage source to be in volt range only, not very high as kilo volt or more type
of voltage may result tunneling(another different mechanism to eject electron from
metallic surface) of electron from cathode to anode as these electrodes are separated by
a small distance.
Q. How many photons are there in 1mW He-Ne laser(wavelength 633 nm) of length 1m?
ℎ𝑐 1240 1240
Sol: Energy per photon associated with this laser = ℎ𝞶 = = eV = x1.6x10−19 J
𝞴 633 633
Power of the laser is 1mW i.e. the laser emits 1 mJ energy in 1 sec.
Velocity of EM wave is 3x108 m/sec i.e. within 1 sec the laser covers a distance of 3x108 m
So for this laser,
3 x108 m distance contains energy = 1mJ
10−3
1m distance contains energy = 3×108 J
633×10−3
No of photons in 1m of the laser = 3×108 ×1240×1.6×10−19 =
ℎ𝑐 1240 1240
Energy per photon of the light = ℎ𝜈 = = eV = x1.6x10−19 J
𝜆 250 250
20×10−3 ×250
Current density, J= 1240 ×1.6×10−19 × 1.6 × 10−19 A cm−2
Electronic Polarization:
• Electric field associated with EM waves interacts with the electron cloud surrounding
each atom within its path in such a way as to induce electronic polarization, or to shift
the electron cloud
relative to the nucleus
of the atom with each
change in direction of
electric field
component.
• Consequences are :
i) Some of the radiation
energy may be
absorbed or wasted as
lattice vibrations (heat),
local vibrations of the
ions etc.
ii) Light waves are retarded in velocity as they pass through the medium i.e. refraction
takes place.
• Polarization is mainly observed in dielectric materials and hence di-electric materials
are mostly transparent.
[NOTE: SOLID FORMATION AND ITS BAND STRUCTURE:
• For solid formation, many initially independent atom comes close enough to each other
in order to form bonds.
• There is attraction of electron cloud of one with nucleus of the other and repulsive force
between two nucleus and also between two electron clouds.
• But initially attractive force dominates and they comes closer to each other.
• When these attraction force comes into effect from that moment the initially
independent atoms no longer remain independent electronic system but a part of a
common electronic system.
• So this disturbs the atomic orbitals and slowly the atomic orbitals (mostly the outermost
shell orbitals) start to split in order to accommodate more quantum states in the new
common electronic system following Pauli’s exclusion principle.
• Splitting of orbitals starts from the outermost shell as they are influenced by other atoms
first.
• At the optimum interatomic distance, which is known as bond length, the total attractive
force is balanced by the total repulsive forces and the overall potential energy of the
system becomes minimum possible and the material reaches equilibrium or the solid
has formed.
• In this moment the outer shell usually splits into two zone where the energy levels are
very closely spaced as if they can be considered continuous compared to the atomic
orbitals spacing and generally these regions are called conduction band and valence
band.
• Based on material, the spacing between the conduction band and valence band varies.]
Q. What are critical values of the band gap energy of any non metallic material to ensure that
it is completely transparent or completely opaque to visible light (390nm-770nm) ?
Solution:
ℎ𝑐 1240
For, 𝐸𝑔,𝑚𝑎𝑥 = 𝜆 = eV = 3.18 eV i.e. any non metallic material with band gap energy
𝑚𝑖𝑛 390
more than 3.18 eV are not able to absorb any portion of visible light for electronic transitions.
• These non metals are completely transparent to visible light and also they appear
colourless provided they are pure.
ℎ𝑐 1240
For, 𝐸𝑔,𝑚𝑖𝑛 = 𝜆 = eV = 1.61 eV i.e.
𝑚𝑎𝑥 770
any non metallic material with band gap energy less than 1.61 eV are able to absorb all portion
of visible light for electronic transitions.
• These non metals are completely opaque to visible light but their reflectivity depends
on possible transitions from excited state to ground states based on its E-K diagram.
• The colour of these non metals basically depends on the reflected spectrum.
• Only a portion of the visible spectrum is absorbed by the materials having band gap
energies between 1.61 eV and 3.18 eV and making those materials appear to be of
certain color.
• For Direct band gap non metal materials, after absorption, the extra energy above
bottom of conduction band is released in terms of phonon(change in K) emission/lattice
heat generation/ Reststrahlen absorption and the rest band gap energy is expensed most
favorably in terms of photon (for same K value) emission as in pure state there are no
possible energy level in between to act as intermediate level for necessary change of K
for such energy transitions.
• So the frequency or wavelength corresponding to band gap is most abundant in reflected
spectrum causing the non metal to be of that particular color provided it lies in visible
range. Otherwise it will appear dark black.
• For Indirect band gap non metal materials, after absorption, the extra energy above
bottom of conduction band is released in terms of some phonon emission and the rest
band gap energy is also expensed in the form of another phonon(typically known as
high energy optical phonon) as both transition must associate related K change also.
• These non metals are mostly dark black in their purest form as all absorbed photon is
released in the form of lattice heat only i.e. no reflection.
• Most of the material in their natural state involves impurity and crystal defects which
introduce some allowed energy levels in between forbidden band also and such
electronic transitions are seen to be more favorable to occur through those intermediate
states and based on the position of these defects states in the E-K diagram determines
its reflective property or color.
So optical properties of indirect band gap materials generally somewhat can be
controlled by manufacturer by introducing suitable impurity or defects.
Absorption in general:
• When an EM wave incident on any material(metal/non metal), the intensity of the net
absorbed radiation is dependent on both the character of the medium and the path length
travelled within.
• The intensity of transmitted or non absorbed radiation continuously decreases with
distance x that the light traverses as
• For an incident beam of intensity 𝐼𝑜 that impinges on the front surface of a specimen of
thickness l and absorption coefficient, the transmitted intensity at the back face 𝐼𝑇 is
𝐼𝑇 = 𝐼𝑜 (1 − 𝑅)2 𝑒 −𝛽𝑙 where R is the reflectance
assuming that the same medium exists outside both front and back faces. It is known as
Bouguer’s law.
By incorporating this total loss of intensity inside the specimen as 𝐼𝐴 , the general
relation between incident, reflected, transmitted and absorbed intensity can be given as
𝐼0 = 𝐼𝐴 + 𝐼𝑅 + 𝐼𝑇
Transmission of light through a material: Refraction
• When band structure allows EM waves to transmit through a material, the electric field
of that EM wave tries to polarize the atoms or molecules of the medium at the frequency
of the wave along its path.
• Propagation of the wave can be considered to be propagation of this polarization
process along its way and the field and the induced dipole moments get coupled.
• As the travelling electric field is oscillating so the electron cloud of the induced dipole
also oscillates at same frequency. (Nucleus also oscillates at same frequency but as it is
bulkier than electrons so it has less amplitude and can be neglected.) The oscillating
electron clouds produce another travelling EM wave whose oscillating electric field
interfere with the original electric field resulting a slower resultant wave packet and its
amplitude also changes.
• So propagation of the EM wave gets delayed and also changes direction of propagation
by the polarization mechanism i.e. refraction takes place.
• More polarization means more coupling and hence more refraction.
• The relative permittivity of any material is an indicator of how much it can get polarized
and hence it is related to measure of extent of refraction i.e. refractive index, η also.
• We know speed of EM waves in any
1
medium is, 𝑐 = and in vacuum
√𝜇𝜖
1
𝑐𝑜 = and refractive index
√ 𝜇𝑜 𝜖𝑜
𝑐𝑜 √𝜇𝜖
is, 𝜂 = = = √ 𝜇𝑟 𝜖 𝑟
𝑐 √ 𝜇 𝑜 𝜖𝑜
• If electric fields is switched off then equation of motion that drives the system,
𝑑2 𝑥
−𝛽𝑥 = 𝑍𝑚𝑒 𝑑𝑡 2
𝛽 1⁄
• The solution is 𝑥(𝑡) = 𝑥𝑜 cos(ꞷ𝑜 𝑡) where ꞷ𝑜 = (𝑍𝑚 ) 2
𝑒
• So the electron cloud executes simple harmonic motion about the nucleus with a natural
or resonance frequency, ꞷ𝑜 which will eventually die out due to EM radiation loss of
accelerating charge when they are disturbed by any momentary field leaving it at any
non equilibrium position i.e. non zero net dipole moment condition.
Note: By this DC electric field calculation we have just defined or introduced the
concept of or what is meant by resonance frequency of the material.
• Now, consider the realistic condition of an oscillating field associated with the
incoming EM waves i.e. 𝐸 = 𝐸𝑜 exp(jꞷt)
• Equation of motion in the continuous presence of the field is now
𝑑2 𝑥
𝑍𝑚𝑒 2 = −𝑍𝑒𝐸𝑜 exp(jꞷt) − 𝛽𝑥
𝑑𝑡
• The solution is
𝑒𝐸 exp(jꞷt)
• 𝑥(𝑡) = − 𝑚 𝑜(ꞷ2 −ꞷ2 )
𝑒 𝑜
𝑃𝑖𝑛𝑑 𝑍𝑒 2
• Now, 𝑃𝑖𝑛𝑑 = 𝑍𝑒𝑥(𝑡) ⇒ 𝑃𝑜𝑙𝑎𝑟𝑖𝑧𝑎𝑏𝑖𝑙𝑖𝑡𝑦, 𝛼𝑒 = =𝑚 2 2
𝐸 𝑒 (ꞷ𝑜 −ꞷ )
• i) Activator excitation: The electrons from ground state of activator i.e. E1 may get
transferred to some excited state, E2 upon receiving energy from the source.
• Soon it falls to a lower energy level 𝐸2′ nonradiatively i.e. through lattice heat
generation.
• Then spontaneously from 𝐸2′ it falls to a even lower energy level 𝐸1′ by emitting visible
light.
• Again very quickly, from 𝐸1′ it comes to ground state E1 non radiatively.
• Definitely there is a difference between absorbed frequency for excitation and emitted
radiation frequency i.e. 𝜈𝑒𝑥 − 𝜈𝑒𝑚 which is known as Stoke’s shift.
• The exact delay between absorption and emission depends on band structure(E-K
diagram) but generally not very high.
• ii) Host excitation: There may be different types of host excitation mechanisms but in
all, the host matrix first absorbs the energy from the source and transfers the valence
electrons to some excited state. From that it comes to bottom of conduction band, 𝐸𝑐 non
radiatively.
• a) From 𝐸𝑐 the electron may come to some activator energy(donor) level in between
non radiatively and then transfer radiatively to another activator energy (acceptor) level
and finally going to original ground state non radiatively i.e. radiative transfer occurs
between two activator states.
• b) From 𝐸𝑐 the electron may come to an activator energy(recombination) level in
between radiatively and then going to original ground state non radiatively i.e. radiative
transfer occurs between bottom of conduction band and an activator state.
• c) From 𝐸𝑐 the electron may come to an activator energy(recombination) level in
between non radiatively and then going to original ground state radiatively i.e. radiative
transfer occurs between an activator state and top of valence band.
• Amount of delay between absorption of energy from source and release of light for
these above three process may vary for different materials based on band structure.
• d) From 𝐸𝑐 the electron may come to an activator energy(trap) level in between non
radiatively(capture) and then again can gain energy from lattice vibration to move back
to 𝐸𝑐 (decapture) and then from 𝐸𝑐 it can go to ground state following any of the above
three radiative mechanisms. In fact this capture-decapture between 𝐸𝑐 and trap level
may happen multiple times, in which case, considerable amount of delay occurs
between absorption of energy from source and release of light.
iv) LASER:
• Laser is an acronym for light amplification by stimulated emission of radiation. It is in
fact can be thought of as a special application of luminescence.
• All of the light emission we have mentioned so far, by luminescence or incandescence,
is spontaneous. It happened just due to randomly occurring natural effects and hence
these transition events occur independently of one another and at random times,
producing radiation that is incoherent i.e. the emitted light waves are out of phase with
one another.
• Unlike most radiation processes, such as, which produce incoherent light, the light
produced by laser emission is coherent.
• Stimulated emission refers to electron transitions that are initiated by the presence of
other photons.
• Einstein showed that an incident photon with E ≥ 𝐸𝑔 is equally likely to cause
stimulated emission of light as to get absorbed itself and the emitted light in such case
has the same frequency and phase as the incident light i.e. coherent.
• Normally, as there are very few excited electrons compared to ground-state electrons,
so we get predominantly absorption.
• If we could arrange for more excited than non-excited electrons, then we would get
mostly stimulated emission.
• To achieve this condition practically, we need a photoluminent material whose
significant no of radiative transfer occurs between an activator state and top of valence
band and the radiation takes a sufficiently long time(msec or more for
phosphorescence) to occur.
• When such material will be illuminated by sufficiently intense light beam so that a
number of excited electrons will occupy the activator states compared to ground states
before any transition from those activator states to ground state starts. Now as soon as
radiative transition starts through those activator states the emitted photons encourages
all other electrons in those states to simultaneously make those radiative transition
causing coherent light to come out i.e. by choosing the material with proper relaxation
time and proper intensity external illumination all the non coherent radiation which
would have occur naturally are forcefully converted into coherent light which is known
as LASER.
• Lasers are useful in many applications such as welding, metal cutting, heat treatment,
surgery, mapping, reading compact disks, etc. e.g. Ruby (single crystal of sapphire(
Al2O3) doped with 0.05% of Cr2O3) , yttrium aluminium garnet (Y3Al5O12 – YAG)
doped with neodymium(Nd), CO2 gas, He-Ne gas, some semi-conductors like GaAs
and InGaAsP etc.