Chapter 14

Optical Properties
of Materials
A. ELECTROMAGNETIC RADIATION F21.1 F21.2

In the classical sense, electromagnetic radiation is

considered to be wave-like （ wave ） , consisting of
electric and magnetic field components that are
perpendicular to each other and also to the direction of
propagation.
All electromagnetic radiation traverses a vacuum at the sa
me velocity, namely, 3×108m/s. This velocity, c, is related t
o the electric permittivity of vacuum Є0 and the magnetic p
ermeability of a vacuum 0 through
1
c (21.1)
 0 0

c  v (21.2
)
Frequency: hertz (Hz), and 1 Hz=1 cycle per second
 From a quantum-mechanical perspective, rather than
consisting of waves, radiation composed of groups or
packets of energy, which are called photons （ particle ）
. Energy E of a photon.
hc
E  hv  (21.3)

h: Planck’s constant, 6.63×10-34 J-s

B. LIGHT LINTERACTIONS WITH SOLIDS

When light proceeds from one medium into another ，
the intensity I0 of the beam incident equal the sum of
the intensities of the transmitted absorbed, and
reflected beams, denoted as IT, I A and IR
I0 = IT + IA+ IR (21.4)
Radiation intensity: watts per square meter
T+A+R=1 (21.5)

where T, A, and R represent, (IT/I0), (IA/I0), (IR/I0).

Transparent: transmitting light with relatively little absorpti
on and reflection
Translucent: light is transmittd diffusely; light is scattered
within the interior, to the degree that objects are not clearl
y distinguishable.
Opaque: impervious to the transmission of visible light
 bulk metals: opaque throughout the entire visible
spectrum; all light radiation is either absorbed or
reflected. Electrically insulating materials: can be
made to be transparent. Semiconducting materials:
transparent or opaque.

C. ATOMIC AND ELECTRONIC INTERACTIONS

C-1. ELECTRONIC POLARIZATION
A rapidly fluctuating electric field interacts to induce
electronic poarization, or to shift the electron cloud rel
ative to the nucleus of the atom. Two consequences:
(1) some of the radiation energy may be absorbed, a
nd (2) light waves are retarded in speed （ refractio
n）.
C-2. ELECTON TRANSITIONS

For an isolated atom F21.3

E  hv (21.6)

h: Planck’s constant
• the energy states for the atom are discrete, only specific
ΔE’s exist between the energy levels; only photons of freq
uencies corresponding to the possible ΔE’s for the atom c
an be absorbed by electron transitions.
• all of a photon’s energy is absorbed in each excitation ev
ent.
• stimulated electron cannot remain in an excited state ind
efinitely; after a short time, it falls or decays back into its gr
ound state (or unexcited level)
• for solid materials: electron band structure
C-3. OPTICAL PROPERTIES OF METALS F18.4 F21.4

Metals are opaque because the incident radiation having

frequencies within the visible range excites electrons into
unoccupied energy states above the Fermi energy.incident
radiation is absorbed
Within a very thin outer layer, usually less than 0.1m (only
metallic films thinner than 0.1m are capable of transmitting
visible light.).
Metals are opaque to all electromagnetic radiation, from
radio waves, into about the middle of the ultraviolet
radiation. (Metals are transparent to high frequency (x-and
r-ray) radiation.)
 Most of the absorbed radiation is reemitted from the surfac
e in the form of visible light of the same wavelength, which a
ppears as reflected light.
The reflectivity for most metals is between 0.90 and 0.95;
some small fraction of the energy from electron decay proces
ses is dissipated as heat.
The perceived color is determined by the wavelength distr
ibution of the radiation that is reflected. A bright silvery appe
arance when exposed to white light indicates that the metal i
s highly reflective over the entire range of the visible spectru
m,e.g., aluminum and silver. Copper and gold appear red-or
ange and yellow: some of the energy associated with light ph
otons having short wavelengths is not reemitted as visible lig
ht.
C-4. OPTICAL PROPERTIES OF NONMETALS F18.4

Nonmetallic materials may be transparent to visible light

：
reflection, absorption, refraction and transmission.

D. REFRACTION T21.1

Index of refraction n: the ratio of the velocity in a vacuum c

to the velocity in the medium v, c
n (21.7
v
)
The magnitude of n depends on the wavelength of the
light. (Thus, e.g., dispersion or separation of a beam of
white light by a glass prism.) 1
c (21.1)
 0 0
1
v (21.8)

Є and : permittivity and permeability of the pa
rticular substance.
c 
n    r r (21.9)
v  0 0

Io and IR : intensities of the incident and reflecte

d beams, if the light is normal (or perpendicular)
to the interface

Єr, r: dielectric constant and the relative magnet

ic permeabilety, since most substances are only sli
n   r (21.10)
ghtly magnetic, r 1,
The retardation of electromagnetic radiation in a me
dium results from electronic polarization: generally
, the larger an atom or ion, the greater will be the
electronic polarization, the slower the velocity, an
d the greater the index of refraction. Index of ref
raction for soda-lime glass:1.5; Highly leaded glass
es containing 90 wt ％ PbO:2.1. crystalline ceramics
that have cubic crystal structures, and for glasses,
the index of refraction is independent of crystallog
raphic direction (i.e., it is isotropic). Nocubic c
rystals, have an anisotropic n; the index is greates
t along the directions that have the highest density
E. REFLECTION
When light radiation passes from one medium into another
having a different index of refraction, some of the light is
scattered at the interface reflectivity R

IR
R (21.11)
I0

Io and IR : intensities of the incident and reflected beams, if the

light is normal (or perpendicular) to the interface
2
 n2  n1 
R   
(21.12)
 n2  n1 
n1 and n2 : indices of refraction of the media. If the
incident light is not normal to the interface, R will depend
on the angle of incidence. When light is transmitted
from a vacuum or air into a solid s

ns  1 2
R( ) (21.13)
ns  1
The index of refraction of air is very nearly unity. The higher
the index of refraction of the solid, the greater is the reflectivity.
The reflectivity vary with wavelength. Reflection losses for
lenses and other optical instruments are minimized significantly
by coating the reflecting surface with very thin layers of
dielectric materials such as magnesium fluoride (MgF2).
F.ABSORPTION F21.5
Nonmetallic materials may be opaque or transparent to visible
light; and, if transparent, they often appear colored . Light
radiation is absorbed by two basic mechanisms:
•electronic polarization (Section 21.4): important only at light
frequencies in the vicinity of the relaxation frequency of the
constituent atoms.
•valence band-conduction band electron transitions: depends on
the electron energy band structure.
absorption of a photon of light by the promotion or excitation
of an electron from the nearly filled valence band, across the
band gap, and into an empty state within the conduction band.

hc ＞ E
hν ＞ Eg(21.14) λ
(21.15)
g
The maximum band gap energy Eg (max) for which absorption of
visible light is possible
hc
E g  max  
 (min)


 4.13 10 15
eV s (3  108 m / s ) (21.16a)
4 107 m
 3.1eV F21.5
No visible light is absorbed by nonmetallic materials having band
gap energies greater than about 3.1eV; these materials, if of high
purity, will appear transparent and colorless.
The minimum band gap energy Eg (min) for which there is
absorption of visible light is a
hc
E g  max  
 (min)


 4.13 10 15

eV s (3 108 m / s )
 1.8eV
7
7  10 m
All visible light is absorbed for those semiconducting
materials that have band gap energies less than about
1.8eV; these materials are opaque. Only a portion of
the visible spectrum is absorbed by materials having b
and gap energies between 1.8 and 3.1 eV; consequently,
these materials appear colored.

Every nonmetallic material becomes opaque at some wave

length, which depends on the magnitude of its Eg. For
example, diamond, having a band gap of 5.6 eV, is opaq
ue to radiation having wavelengths less than about 0.2
2m.
If impurities or other electrically active defects are present,
electron levels within the band gap may be introduced (such as
the donor and acceptor levels (Section 18.11), except that they
lie closer to the center of the band gap), the electromagnetic
energy that was absorbed by electron excitation must be
dissipated, several mechanisms:
•direct electron and hole recombination
F21.5
electron  hole  energy (E ) (21.17)

• multiple-step electron transitions:one possibility, (Figure 21

.6b) emission of two photons; alternatively, generation of a p
honon (Figure 21.6c) F21.6
 The intensity of transmitted or nonabsorbed radiati
on I’T continuously decreases with distance x
 X
I 'T  I '0 e (21.18)

I’0 :intensity of the nonreflected incident radiati

on. : absorption coefficient (in mm-1), Materials
that have large  values are considered to be highl
y absorptive.
G. Transmission F21.7
I T  I 0 (1  R ) 2 e  l (21.19)

It is assumed that the same medium exists outside both front

and back faces. R, A, and T depends on light wavelength
H. COLOR F21.8 F21.9
Transparent materials appear colored, the color discerned is a
result of the combination of wavelengths that are transmitted. If
absorption is uniform for all visible wavelengths, the materials
appears colorless; e.g., high-purity inorganic glasses and high-
purity and single-crystal diamonds and sapphire.

Fraction of the visible light having energies greater than Eg is

selectively absorbed (by valence band conduction band electron
transitions.) some of this absorbed radiation is reemitted as the
excited electrons drop back into their original, lower-lying
energy states. It is not necessary that this reemission occur at the
same frequency as that of the absorption. As a result, for
semiconducting materials the color depends on the frequency
distribution of both transmitted and reemitted light beams.
 Fro example, cadmium sulfide (CdS) has a band gap
of about 2.4eV; it absorbs blue and violet portio
ns, some of this energy is reradiated as light ha
ving other wavelengths. Nonabsorbed visible ligh
t consists of photons having energies between abo
ut 1.8 and 2.4eV. Cadmium sulfide takes on a yell
ow-orange color
• Ceramics, specific impurities also introduce electron levels
within the forbidden band gap, photons having energies less
than the band gap may be emitted as a consequence of
electron decay processes involving impurity atoms or ions.

F3.17 F20.20
For example, high-purity and single-crystal aluminum
oxide or sapphire is colorless. Ruby, which has a b
rilliant red color, is simply sapphire to which has
been added 0.5 to 2% of chromium oxide (Cr2O3). Cr3+
ion substitutes for the Al 3+ ion in the Al2O3 crysta
l structure and introduces impurity levels within th
e wide energy band gap of the sapphire. Nonabsorbed
or transmitted light mixed with reemitted light impa
rts to ruby its deep-red color.
Inorganic glasses are colored by incorporating tran
sition or rare earth ions while the glass is still
in the molten state: blue-green; Co 2+ , blue-violet
; Cr3+, green; Mn2+, yellow; and Mn3+ , purple. The
se colored glasses are also used as glazes ( 釉料 ),
decorative coatings ( 彩色鍍層 ) on ceramic ware
( 陶瓷器件 ).
I. OPACITY AND TRANSLUCENCY IN INSULATORS
Many dielectric materials that are intrinsically transparent may be
made translucent or even opaque because of interior reflection and
refraction: multiple scattering events. Opacity results when the
scattering is so extensive. F21.10
Internal scattering: •polycrystalline specimens in which the index
of refraction is anisotropic normally appear translucent. Both
reflection and refraction occur at grain boundaries.
• scattering of light also occurs in two-phase materials
• The greater difference in the refractive index difference, the
more efficient is the scattering
Residual porosity in the form of finely dispersed
pores. Also effectively scatter light radiation.

For intrinsic polymers (without additives and impu

rities), the degree of translucency is influenced
primarily by the extent of crystallinity. Some sc
attering of visible light occurs at the boundaries
between sperulites and between crystalline and amo
rphous regions, as a result of different indices o
f refraction. For highly crystalline specimens: t
ranslucency, even opacity. Highly amorphous polym
ers are completely transparent.
J. APPLICATIONS OF OPTICAL PROPERTIES
J-1. LUMINESCENCE
Some materials are capable of absorbing energy and
then reemitting visible light in a phenomenon calle
d luminescence. Energy is absorbed when an electro
n is promoted to an excited energy state; visible l
ight is emitted when it falls back to a lower energ
y state if 1.8eV<hv<3.1eV. The absorbed energy may
be supplied as higher-energy electromagnetic radiat
ion (ultraviolet light) high energy electrons, or b
y heat, mechanical, or chemical energy. Luminescen
ce is classified according to the delay time betwee
n absorption and reemission events.
If reemission occurs for times much less than one second: fl
uorescence; for longer times: phosphorescence; e.g., sulfid
es, oxides, tungstates, and a few organic materials. Ordina
rily, pure materials do not disply these phenomena, and to i
nduce them, impurities in controlled concentrations must be
added.

Luminescence applications:

• fluorescent lamps: glass housing, coated on the inside

with tungstates or silicates. Ultraviolet light is generated
from a mercury glow discharge, which causes the coating
to fluoresce and emit white light.
• television screen: inside of the screen is coated
F18.19
with a material that fluoresces as an electron
beam inside the picture tube very rapidly
traverses the screen
• Detection of x-rays and υ-rays
• light-emitting diodes(LEDs) : some p-n rectifying
junctions, (Section 18.15), may also be used to generat
e
visible light: electroluminescence. Such diodes that
luminesce visible light are the familiar light-emitting
diodes(LEDs), which are used for digital displays. The
characteristic color of an LED depends on the particula
r
#60 Fig.6
semiconducting material that is used.
•White light LED#2 #3 #4 #5
Lighting:photoluminescence.#24 #25
J-2. PHOTOCONDUCTIVTTY
The conductivity of semiconducting materials depends on: number of
free electrons in the conduction band and number of holes in the
valence. Photon-induced electron transitions: when a specimen of a
photoconductive materials is illuminated, the conductivity increases:
photoconductivity.

Applications: photographic light meters. (cadmium sulfi

de is commonly utilized) sunlight be directly converted
into electrical energy solar cells, empoly semiconductor
s. Reverse of that for the light-emitting diode. A p-n
junction is used in which potoexcited electrons and hole
s are holes are drawn away from the junction, in opposit
e directions, and become part of an external current.
Electron transitions heretofore discussed: spontaneous (without
any external provocation.) random times, incoherent.
Laser: coherent light generated by electron transitions initiated
by an external stimulus. “laser” light amplification by
stimulated emission of radiation. solid-state ruby laser. Ruby
single crystal of Al2O3 (sapphire) added of 0.05% Cr 3+ ions.
The ruby laser is in the form of a rod, the ends of which are flat,
parallel, and highly polished. Both ends are silvered such that
one is totally reflecting and the other partially transmitting.

Photons of 0.56m from the xenon lamp excite electro

ns from the Cr3+ ions into higher energy states. So
me fall back directly; other electrons decay into a
metastable intermediate state, where they may reside
for up to 3 ms 3ms is a relatively long time, a larg
e number of these metatable states may become occupi
 B
Intensity(a.u.)

350 400 450 500 550 600

Wavelength(nm)
Phosphor
Excitation spectra of CaS:Eu powders
Intensity(a.u.)

Blue LED chip

500 550 600 650 700 750

Wavelength(nm)
Emission spectra of CaS:Eu
Ι. Introduction to Phosphors
01

A.Phosphors: luminescence conversion materials 02

material (powders) that emit visible light when

irradiated with shorter wavelength light (UV or blue)

Beta-SiAlON:Eu Alpha-SiAlON:Eu CaSiAlN3:Eu

B. Applications
(a)White light LED Lighting

(b)Back light source of flat panel display

LED For TV Backlight
C. Chemical Composition: Host Lattice ： activator
(doping)

Oxides (conventional):
•Y2O3 ： Eu+3
•Y3Al5O12 ： Ce+3 (YAG)
•Tb3Al5O12 ： Ce+3

Nitrides and Oxynitrides (newly developed):

•Ca2Si5N8 ： Eu+2
•Ca2Si2N2O2 ： Eu+2
• Ca-α-SiAlON ： Eu+2
• Y-α-SiAlON ： Ce+3
D. Features of Nitride and Oxynitride Phosphors
(compared to oxide phosphors)
 Potential advantages Fig 6
• high thermal and chemical stability
• high emission intensity (or high quantum yield)
• long wavelength( orange-red) emission, improving
color rendering index, which are usually difficult to
be achieved by other phosphors.

More difficult to be synthesized

․more severe synthesis conditions, e.g., high reaction
temperature, high N2 pressure, long reaction time or
use of moisture or oxygen sensitive starting
materials.
Fundamentals of luminescence

Fig.2 The Jablonski diagram: (1) light absorption, (2) vibrational relaxation, (3) internal conversion (IC),
(4) intersystem crossing (ISC), (5) radiative transition, and (6) nonradiative transition.
Typical photoluminescence excitation (ìmon ) 649 nm) and emission (ìex ) 460 nm)
spectra of Ca0.98Eu0.02AlSiN3 (a) and the schematic picture of the influence of the envi
ronment of a Eu2+ on the positions of electronic states (b).