Optical Properties of Materials

Nature of Light
Light is an electromagnetic wave or photon. The magnetic and the electric
field are perpendicular to each other. The velocity of light is c = 3 x 108 m/s

1
c=
ε oµo
Speed of light related to
electric permittivity and
magnetic permeability
 Photons
EE == hhνν == hh cc // λλ
h: Planck’s constant
6.63x10-34 J-s
UV 100-400 nm 12.4 - 3.10 eV
Violet 400-425 nm 3.10 - 2.92 eV
Blue 425-492 nm 2.92 - 2.52 eV
Green 492-575 nm 2.52 - 2.15 eV
Yellow 575-585 nm 2.15 - 2.12 eV
Orange 585-647 nm 2.12 - 1.92 eV
Red 647-700 nm 1.92 - 1.77 eV
Near IR 10,000-700 nm 1.77 - 0.12 eV
 Electromagnetic Radiation and the Visible Spectrum
If absorbance occurs in one region of the
color wheel the material appears with the
opposite (complimentary color). For example:
a material absorbs violet light Red Violet
→ Color = Yellow
a material absorbs green light
→ Color = Red Orange Blue

a material absorbs violet, blue & green

→ Color = Orange-Red
Yellow Green
a material absorbs red, orange & yellow
→ Color = Blue

E =
hc
=
( ) (
4.1357 x 10-15 eV-s × 2.998 x 108 m.s −1 )
λ λ
1240
E (eV) = nm
λ
 Light Interaction with Solids
Incident light is either reflected, absorbed, or transmitted:
Io = IT + I A + IR
Reflected: IR Absorbed: IA
T+A+R=1
Transmitted: IT

Incident: Io T = IT /I0 Transmissivity

A = IA /I0 Absorptivity
Optical classification of materials:
R = IR /I0 Reflectivity
Transparent
T~1 : Transparent
Transluscent
T~0 : Opaque
Opaque
Optical
Opticalphenomena
phenomenainvolve
involve
interactions
interactionsbetween
betweenlight
light
and
andatoms,
atoms,ions,
ions,and/or
and/orelectrons.
electrons.
 Optical Properties & Band Structure
• Reflection
– Scattering at an interface between two materials w/ different n

• Absorption
– Electronic Polarization
– Electron excitation to defect levels in the band gap
– Electron excitation across the band gap

Conduction
empty Band
empty

empty Valence
filled filled filled Band
Metal Semiconductor Insulator
Absorption
Absorption 1. Electronic polarization metals

2. Band transition Insulators and semiconductors

hν > Eg
Visible light: 0.4 ~ 0.7µm in wavelength or
3.1 ~ 1.8eV
Optical
OpticalProperties
PropertiesofofMetals
Metals

Absorption of photons by electron

transition:
Metals have a fine succession of energy states.
∆∆E=h
E=hνν Near-surface electrons absorb visible light.

Photons are used to excite the electrons to higher states (absorbed within
0.1µm and remitted in the form of visible light).
Optical
OpticalProperties
PropertiesofofMetals
Metals

Reflection: Electron transition

emits a photon.

re-emitted photon
• Reflectivity = IR/Io is between 0.90 and 0.95. from material
• Reflected light is same frequency as incident. surface
• Metals appear reflective (shiny)!
For visible light
RRisisabout
about0.9~0.95
0.9~0.95
Absorption and Reflectivity in Metals
Metals have a fine succession of energy states.
Near surface electrons absorb visible light. Absorption of photons by electron transitions.
Electron transition emits a photon.
Reflectivity = IR/IO is between 0.90 and 0.95.
Reflected light is same frequency as incident. Metals appear reflective (shiny)!

EE==hhνν ==hhcc//λλ
Incident photon energy
h = Planck’s constant
(6.63x10-34J.s-1)
 Why are Metals Shiny?
• Metals Eg = 0 eV
• All light with λ above X-ray wavelengths absorbed by continuous # of
unoccupied states above Ef.
• Light is reemitted with exact energy of absorption as electrons fall
back into lowest state. Metals appear reflective as the light we see is
reemitted.

Ef

absorption emission
 Optical Properties of Ceramics
• What if the band gap is very large?
EGAP > Elight - there will be no absorption

What is the minimum value of Eg that that will let all visible light
pass?

Egap> hυ=hc/λ for λ = 0.4 µm (min. visible

wavelength)

Answer: Egap> 3.1eV

For ceramics with a large band gap - no absorption

(Most insulating ceramics should be transparent!)
Optical Selected Absorption:
OpticalProperties
PropertiesofofNonmetals
Nonmetals
Insulators/Semiconductors
• Absorption by electron transition occurs if hν > Egap
Energy of electron

unfilled states
blue light: hν= 3.1eV
red light: hν= 1.7eV

Egap
incident photon energy hν

Io filled states

• If Egap < 1.8eV, full absorption; color is black (Si, GaAs)

• If Egap > 3.1eV, no absorption; colorless (diamond)
• If Egap in between, partial absorption; material has a color.
 Band to Band Transitions
Optical
OpticalProperties
PropertiesofofNonmetals
Nonmetals Optical Properties of
•We can examine the relationship between Semiconductors
bonding (spatial and energetic overlap) and
optical properties by considering the band-gaps of
those compounds which adopt the Sphalerite/
Diamond structure, with all ions in tetrahedral
coordination
•(see figure to the right).

•Since electronic transitions from the valence to

conduction band span a fairly large range of
energies, semiconductors act as sort of a long
pass filter (only reflecting light with energy less Band Gap (eV) Color Example
than the band gap). This can give rise to only > 3.0 White ZnO
certain colors. 3.0-2.5 Yellow CdS
2.3-2.5 Orange
1.8-2.3 Red HgS
< 1.8 Black CdSe
Selected Absorption: Insulators/Semiconductors
Absorption by electron transition occurs if hν > Egap
If Egap < 1.8eV, full absorption; color is black (Si, GaAs)
If Egap > 3.1eV, no absorption; colorless (diamond)
If Egap in between, partial absorption; material has a color.

EE==hhνν ==hhcc//λλ
Incident photon energy
h = Planck’s constant
(6.63x10-34J.s-1)
Can a light with a larger wave length interacts with a material with
a large band gap?
Yes! through impurities.

Generate
heat

' − βx
I =Ie
'
T 0

β: absorption coef.
 Color of NonMetals
• Color determined by sum of frequencies of
--transmitted light, Red Violet
--re-emitted light from electron transitions.
• Ex: Cadmium Sulfide (CdS) Orange Blue
-- Egap = 2.4eV,
-- absorbs higher energy visible light (blue, violet),
Yellow Green
-- Red/yellow/orange is transmitted and gives it color.
• Ex: Ruby = Sapphire (Al2O3) + (0.5 to 2) at% Cr2O3
-- Sapphire is colorless
Transmittance (%)

(i.e., Egap > 3.1eV) 80

sapphire
-- adding Cr2O3 : 70
• alters the band gap Ruby
• blue light is absorbed 60
• yellow/green is absorbed 50
• red is transmitted wavelength, λ (= c/ν)(µm)
40
• Result: Ruby is deep
0.3 0.5 0.7 0.9
red in color.
Adapted from Fig. 21.9, Callister 6e. (Fig. 21.9 adapted from "The Optical
Properties of Materials" by A. Javan, Scientific American, 1967.)
COLORS in Ceramics
Color is determined by sum of frequencies of (a) transmitted light and (b)
re-emitted light from electron transitions. Color is the result of the
combination of wavelengths that are transmitted
Absorbed radiation can be reemitted as excited electrons drop back into
original positions - not necessarily the same frequency as that absorbed
Small differences in composition can lead to large differences in
appearance. Specific impurities can introduce electron levels within the
band-gap - leads to color
For example, high-purity single-crystal Al2O3 is colourless sapphire
If we add only 0.5 - 2.0% of Cr2O3 we find that the material looks red ruby
The Cr substitutes for the Al and introduces impurity levels in the band gap
of the sapphire. These levels give strong absorptions at:
400nm (green) and 600nm (blue) leaving only red to be transmitted
 Beryl
Be3Al2Si6O18

Saphire
Be3Al2SiO6
Color in Extended Inorganic Solids: Absorption

Intra-tomic (Localized) excitations

Cr3+ Gemstones (i.e. Cr3+ in Ruby and Emerald)
Blue and Green Cu2+ compounds (i.e. malachite, turquoise)
Blue Co2+ compounds (i.e. Al2CoO4, azurite)
Charge-transfer excitations
Fe2+ → Ti4+ in sapphire
Fe2+ → Fe3+ in Prussian Blue
O2- → Cr6+ in BaCrO4
Valence to Conduction Band Transitions in Semiconductors
WO3 (Yellow)
CdS (Yellow) & CdSe
HgS (Cinnabar - Red)/ HgS (metacinnabar - Black)
Intraband excitations in Metals
Strong absorption within a partially filled band leads to metallic lustre or black coloration
Most of the absorbed radiation is re-emitted from surface in the form of visible light Æ
high reflectivity (0.90-0.95)
Intra-tomic (Localized) excitations
A similar technique is used to colour glasses or pottery glaze by adding impurities
into the molten state:
Cu2+: blue-green, Cr3+: green
Co2+: blue-violet, Mn2+: yellow
Example:
If we take one mineral, beryl, and add different impurities, we get different colors:
Beryl containing iron (Fe):
Aquamarine = Fe++, beryl is blue
Heliodor = Fe+++, yellow
Green beryl : due to mixtures of Fe2+ and Fe3+
Beryl containing Manganese(Mn):
Morganite : Mn++ is pink
Red beryl : Mn+++ is red
Beryl containing Chromium(Cr):
Emerald = emerald green : Cr+++
From the above examples it is clear that the oxidation state (e.g., Fe2+ vs. Fe3+)
also affects the color! . If impurity ions produce color, the color can be changed if
the oxidation state can be changed.
Charge-transfer excitations
Charge transfer can only occur in compounds that have at least two elements in
different and variable oxidation states.
Charge transfer can produce very intense colors in gems and minerals. The term
charge transfer refers to the process where electrons are swapped between
elements.
Examples of elements that can participate in charge transfer are:
Fe2+ and Fe3+ ; Ti3+ and Ti4+ ; Mn2+ and Mn3+ and Mn4+ etc.
Furthermore, a crystal can contain mixtures of these elements (e.g,. Mn and Fe)
and these can participate in charge transfer. Energy is absorbed from visible light
to transfer electrons from one atom to another.
For example:
A crystal contains metals (M) in two oxidation states: M2+ and M4+ . M2+ can loose
an electron and become M3+ . M4+ can accept the electron (from above) and
become M3+.
Thus, the crystal can exist with M3+ plus M3+ or M2+ plus M4+. As you can see,
these pairs are interchangeable by movement of an electron.
Optical
OpticalProperties
PropertiesofofNonmetals
Nonmetals
The index of refraction n of a material is defined as the ratio of the velocity
in a vacuum c to the velocity in the medium ν

Refraction: nn == c/v
c/v The speed of light is smaller in the materials
Index of refraction
ε: permittivity The larger atoms or ions
v = 1 / εµ µ: permeability the smaller ν and larger n
n is the same for all directions for cubic
c εµ structures. For an anisotropic structure,
n= = = ε rµ r ≈ ε r n is higher in the direction of higher
v ε0µ 0 density of ions.

Dielectric constant Relative magnetic permeability

ε = permittivity
Since most of the substances µ = permeability
are only slightly magnetic, µr ~ 1 o - “in a vacuum”
r - “relative”
 REFRACTION -OVERVIEW
• Transmitted light distorts electron clouds. electron
no cloud
transmitted transmitted
+ light + distorts
light

• Result 1: Light is slower in a material vs vacuum.

speed _ of _ light _ in _ vacuum
Index_of_refraction = n =
speed _ of _ light _ in _ a _ material
Material n
--Adding large, heavy ions (e.g., lead Lead glass 2.1
can decrease the speed of light. Silica glass 1.46
--Light can be Soda-lime glass 1.51
"bent" Quartz 1.55
Plexiglas 1.49
Polypropylene 1.49
Selected values from Table 21.1,
Callister 6e.

• Result 2: Intensity of transmitted light decreases with distance traveled (thick

pieces less transparent!)
Refraction is the bending of the path of a light wave as it passes from one material to
another material.
The refraction occurs at the boundary and is caused by a change in the speed of the
light wave upon crossing the boundary.
The tendency of a ray of light to bend one direction or another is dependent upon
whether the light wave speeds up or slows down upon crossing the boundary.

Like any wave, the speed of a light wave is dependent upon the properties of the medium.
In the case of an electromagnetic wave, the speed of the wave depends upon the optical
density of that material.
The optical density of a medium is not the same as its physical density. The physical
density of a material refers to the mass/volume ratio. The optical density of a material
relates to the sluggish tendency of the atoms of a material to maintain the absorbed
energy of an electromagnetic wave in the form of vibrating electrons before reemitting it
as a new electromagnetic disturbance. The more optically dense which a material is, the
slower that a wave will move through the material.
 For most ceramics, µr = 1
(only slightly magnetic)

n ≅ εr
For transparent materials - there is a
relationship between index of
refraction and dielectric constant!
(The electrical properties and the
optical properties of a material are
related!)
The table below lists index of refraction values for a variety of medium. The materials listed
at the top of the table are those through which light travels fastest; these are the least optically
dense materials. The materials listed at the bottom of the table are those through which light
travels slowest; these are the most optically dense materials. So as the index of refraction
value increases, the optical density increases, and the speed of light in that material
decreases.
Material Index of Refraction
Vacuum 1.0000 <--lowest optical density

Air 1.0003

Ice 1.31

Water 1.333

Ethyl Alcohol 1.36

Plexiglas 1.51

Crown Glass 1.52

Light Flint Glass 1.58

Dense Flint Glass 1.66

Zircon 1.923

Diamond 2.417

Rutile 2.907

Gallium phosphide 3.50 <--highest optical density

 Reflectivity
Reflectivity R=IR /I0 Reflectivity
Reflection occurs at the interface between two materials and is 2
therefore related to index of refraction  n2 − n1 
Reflectivity, R = IR/I0, where the I’s are intensities R =  
Assuming the light is normally incident to the interface: where n1  n2 + n1 
and n2 are the indices for the two materials
Typical glass: R=0.05
Semiconductor with n=3: R=0.25
n1 n2
I0 IR If 1 is air
2
n1  n2 − 1 
R =  
n2  n2 + 1 

So, large n, larger R (brighter)

Lenses coated with MgF2 to reduce reflection loss!
Some lenses have multiple coatings for different wavelength
 Emission of Light
The optical properties of extended solids are utilized not only for their color,
but also for the way in which they emit light.

Luminescence – Emission of light by a material as a consequence of it

absorbing energy. There are two categories:
Fluorescence: Emission involves a spin allowed transition (short excited state
lifetime)
Phosphorescence: Emission involves a spin forbidden transition (long lived excited
state).

Luminescence can also be classified according to the method of excitation:

Photoluminescence: Photon excitation (i.e. fluorescent lights)
Cathodoluminescence: Cathode rays (TV & Computer displays)
Electroluminescence: Electrical injection of carriers (LED’s)
 Application: LUMINESCENCE
• Process: Energy of electron Energy of electron

unfilled states
unfilled states
emitted light
Incident radiation Egap Egap

filled states filled states

electron re-emission
transition occurs occurs
Adapted from Fig. 21.5(a), Callister 6e.

• Ex: fluorescent lamps

glass “white” light

coating UV
e.g., β-alumina radiation
Ex: Picture on TV- inside of screen is coated
doped with material that fluoresces when impinged on
w/Europium by electron beam
 Application: PHOTOCONDUCTIVITY
• Description:

+ +
Energy of electron
Energy of electron

unfilled states
unfilled states

semi Incident conducting

Egap
conductor: Egap
radiation electron
filled states
filled states

- -
A. No incident radiation: B. Incident radiation:
little current flow increasedcurrent flow

• Ex: Photodetector (Cadmium sulfide)

Optical
Optical Communication
Communication Application: FIBER OPTICS

2 optical fibers (0.1kg) can transmit 24000 calls (equivalent to 33tons of copper wires)

High-purity glass
(5~100µ)
Human hair
Step-Index Near the interface, longer travel distance
Step-IndexDesign
Design
Broader
output

• Design with stepped index of refraction (n):

core: silica glass input pulse total internal reflection output pulse
w/higher n
intensity

intensity
cladding: glass
w/lower n
∆n enhances shorter path
internal reflection time longer paths time
broadened!
 Near the surface, light travels faster.
Graded-Index
Graded-IndexDesign
Design

Sharper
output

B2O3 or GeO2

• Design with parabolic index of refraction

core: Add graded input pulse total internal reflection output pulse
impurity distrib.
to make n higher in
intensity

intensity
core center

cladding: (as before) shorter, but slower paths

time longer, but faster paths time
less
broadening!
• Parabolic = less broadening = improvement!
 SUMMARY
• When light (radiation) shines on a material, it may be:
--reflected, absorbed and/or transmitted.
• Optical classification:
--transparent, translucent, opaque
• Metals:
--fine succession of energy states causes absorption and reflection.
• Non-Metals:
--may have full (Egap < 1.8eV) , no (Egap > 3.1eV), or partial absorption (1.8eV <
Egap = 3.1eV).
--color is determined by light wavelengths that are transmitted or re-emitted from
electron transitions.
--color may be changed by adding impurities which change the band gap
magnitude (e.g., Ruby)
• Refraction:
--speed of transmitted light varies among materials.