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Chapter 21: Optical Properties

ISSUES TO ADDRESS...
• What happens when light shines on a material?
• Why do materials have characteristic colors?
• Why are some materials transparent and others not?
• Optical applications:
-- luminescence
-- photoconductivity
-- solar cell
-- optical communications fibers

Chapter 21 - 1
Optical Properties
Light has both particulate and wavelike properties
– Photons - with mass

hc
E  h 

E  energy
  wavelength
  frequency
h  Planck' s constant (6.62 x10 34 J  s)
c  speed of light (3.00 x 10 8 m/s)

Chapter 21 - 2
Refractive Index, n
• Transmitted light distorts electron clouds. electron
no cloud
transmitted
transmitted + + distorts
light light

• Light is slower in a material vs vacuum.


c (velocity of light in vacuum)
n = refractive 
index v (velocity of light in medium)

--Adding large, heavy ions (e.g., lead


• Note: n = f ()
can decrease the speed of light.
--Light can be Typical glasses ca. 1.5 -1.7
"bent" Plastics 1.3 -1.6
PbO (Litharge) 2.67
Diamond 2.41
Selected values from Table 21.1,
Callister 7e.
Chapter 21 - 3
Total Internal Reflectance
n > n’

n’(low) 1'
n sin 
n (high) 
n sin 
i  incident angle
c i  refracted angle
c  critical angle
1

c occurs when i  90


for i  c light is internally reflected
Chapter 21 - 4
Example: Diamond in air

n sin  2.41 sin 90  1


   
n sin  1 sin c sin c

1
sin c  c  24.5
2.41

• Fiber optic cables are clad in low n material for this


reason.

Chapter 21 - 5
Light Interaction with Solids
• Incident light is either reflected, absorbed, or
transmitted: Io  IT  I A  IR  IS

Reflected: IR Absorbed: IA
Transmitted: IT
Incident: I0
Scattered: IS
• Optical classification of materials:
Transparent Adapted from Fig. 21.10, Callister
Translucent 6e. (Fig. 21.10 is by J. Telford,
with specimen preparation by P.A.
Opaque Lessing.)

single polycrystalline polycrystalline


crystal dense porous
Chapter 21 - 6
Optical Properties of Metals:
Absorption
• Absorption of photons by electron transition:
Energy of electron
unfilled states
to n
o E = h required!
ph
ent h 
i d
Inc rgy
Io e ne
of filled states
Planck’s constant freq.
of
(6.63 x 10-34 J/s) incident
Adapted from Fig. 21.4(a), Callister 7e.

light
• Metals have a fine succession of energy states.
• Near-surface electrons absorb visible light.
Chapter 21 - 7
Light Absorption

I  t
e   linear absorption coefficient [ ] cm1
I0 t  sample thickness

I 
ln      t
 I0 

Chapter 21 - 8
Optical Properties of Metals:
Reflection
• Electron transition emits a photon.
Energy of electron
IR unfilled states
“conducting” electron
re-emitted E
photon from
material surface
filled states

Adapted from Fig. 21.4(b), Callister 7e.

• Reflectivity = IR/Io is between 0.90 and 0.95.


• Reflected light is same frequency as incident.
• Metals appear reflective (shiny)!
Chapter 21 - 9
Reflectivity, R
• Reflection
– Metals reflect almost all light
– Copper & gold absorb in blue & green => gold
color 2
 n  1
R    reflectivi ty
 n  1
2
• Example: Diamond  2.41  1 
R    0.17
 2.41  1

 17% of light is reflected

Chapter 21 - 10
Scattering
• In semicrystalline or polycrystalline materials

• Semicrystalline
– density of crystals higher than amorphous
materials  speed of light is lower - causes light to
scatter - can cause significant loss of light

• Common in polymers
– Ex: LDPE milk cartons – cloudy
– Polystyrene – clear – essentially no crystals

Chapter 21 - 11
Selected Absorption: Semiconductors
• Absorption by electron transition occurs if h > Egap
Energy of electron

unfilled states
blue light: h = 3.1 eV
red light: h = 1.7 eV

incident photon
Egap
energy h

Io filled states
Adapted from Fig. 21.5(a), Callister 7e.

• If Egap < 1.8 eV, full absorption; color is black (Si, GaAs)
• If Egap > 3.1 eV, no absorption; colorless (diamond)
• If Egap in between, partial absorption; material has a color.
Chapter 21 - 12
Wavelength vs. Band Gap
Example: What is the minimum wavelength absorbed

by Ge?
Eg = 0.67 eV
hc (6.62 x 1034 J s)(3 x 108 m/s)
c    1.85 m
Eg 19
(0.67eV)(1.60 x 10 J/eV)

note : for Si Eg  1.1 eV  c  1.13 m


If donor (or acceptor) states also available this provides other
absorption frequencies

Chapter 21 - 13
Color of Nonmetals
• Color determined by sum of frequencies of
-- transmitted light,
-- re-emitted light from electron transitions.
• Ex: Cadmium Sulfide (CdS)
-- Egap = 2.4 eV,
-- absorbs higher energy visible light (blue, violet),
-- Red/yellow/orange is transmitted and gives it color.
• Ex: Ruby = Sapphire (Al2O3) + (0.5 to 2) at% Cr2O3
-- Sapphire is colorless
Transmittance (%)
80
(i.e., Egap > 3.1eV) sapphire
70
-- adding Cr2O3 : ruby
60
• alters the band gap
50
• blue light is absorbed 40
wavelength,  (= c/)(m)
• yellow/green is absorbed 0.3 0.5 0.7 0.9
Adapted from Fig. 21.9, Callister 7e. (Fig. 21.9
• red is transmitted adapted from "The Optical Properties of Materials" by
• Result: Ruby is deep A. Javan, Scientific American, 1967.)

red in color. Chapter 21 - 14


Luminescence
• Luminescence – emission of light by a material
– material absorbs light at one frequency & emits at
another (lower) frequency.
Conduction band

How stable is the trapped state?


trapped • If very stable (long-lived = >10-8 s) =
Eg states
Eemission phosphorescence
• If less stable (<10-8 s) = fluorescence
activator
level Example: glow in the dark toys.
Charge them up by exposing them to
Valence band the light. Reemit over time. --
phosphorescence
Chapter 21 - 15
Photoluminescence
Hg

uv

electrode electrode

• Arc between electrodes excites mercury in lamp to higher


energy level.
• electron falls back emitting UV light (i.e., suntan lamp).
• Line inner surface with material that absorbs UV, emits visible
Ca10F2P6O24 with 20% of F - replaced by Cl -
• Adjust color by doping with metal cations
Sb3+ blue
Mn2+ orange-red
Chapter 21 - 16
Cathodoluminescence
• Used in T.V. set
– Bombard phosphor with electrons
– Excite phosphor to high state
– Relaxed by emitting photon (visible)
ZnS (Ag+ & Cl-) blue
(Zn, Cd) S + (Cu++Al3+) green
Y2O2S + 3% Eu red

• Note: light emitted is random in phase & direction


– i.e., noncoherent

Chapter 21 - 17
LASER Light
• Is non-coherent light a problem? – diverges
– can’t keep tightly columnated

• How could we get all the light in phase? (coherent)


– LASERS
• Light
• Amplification by
• Stimulated
• Emission of
• Radiation
• Involves a process called population inversion of
energy states

Chapter 21 - 18
Population Inversion
• What if we could increase most species to the excited
state?

Fig. 21.14, Callister 7e.

Chapter 21 - 19
LASER Light Production
• “pump” the lasing material to the excited state
– e.g., by flash lamp (non-coherent lamp).

Fig. 21.13, Callister 7e.

– If we let this just decay we get no coherence.


Chapter 21 - 20
LASER Cavity
“Tuned” cavity:
• Stimulated Emission
– One photon induces the
emission of another
photon, in phase with the
first.
– cascades producing very
intense burst of coherent
radiation.
• i.e., Pulsed laser

Fig. 21.15, Callister 7e.

Chapter 21 - 21
Continuous Wave LASER
• Can also use materials such as CO2 or yttrium-
aluminum-garret (YAG) for LASERS
• Set up standing wave in laser cavity –
– tune frequency by adjusting mirror spacing.
• Uses of CW lasers
1. Welding
2. Drilling
3. Cutting – laser carved wood, eye surgery
4. Surface treatment
5. Scribing – ceramics, etc.
6. Photolithography – Excimer laser

Chapter 21 - 22
Semiconductor LASER
• Apply strong forward
bias to junction.
Creates excited state
by pumping electrons
across the gap-
creating electron-hole
pairs.

electron + hole  neutral + h

excited state ground state


photon of
Adapted from Fig. 21.17,
light Callister 7e.

Chapter 21 - 23
Uses of Semiconductor LASERs
• #1 use = compact disk player
– Color? - red
• Banks of these semiconductor lasers are used as
flash lamps to pump other lasers
• Communications
– Fibers often turned to a specific frequency
(typically in the blue)
– only recently was this a attainable

Chapter 21 - 24
Applications of Materials Science
• New materials must be developed to make new &
improved optical devices.
– Organic Light Emitting Diodes (OLEDs)
– White light semiconductor sources

Fig. 21.12, Callister 7e.


Reproduced by
arrangement with Silicon
Chip magazine.)

• New semiconductors
• Materials scientists
(& many others) use lasers as tools.
• Solar cells

Chapter 21 - 25
Solar Cells
• p-n junction: • Operation:
-- incident photon produces hole-elec. pair.
P-doped Si -- typically 0.5 V potential.
conductance Si -- current increases w/light intensity.
electron creation of
Si P Si hole-electron
light pair
Si - - -
n-type Si
p-n junction -
n-type Si p-type Si +
p-n junction + + +
P-type Si
• Solar powered weather station:
hole Si

Si B Si
Si
B-doped Si polycrystalline Si
Los Alamos High School weather
station (photo courtesy
P.M. Anderson)

Chapter 21 - 26
Optical Fibers
• prepare preform as indicated in Chapter 13
• preform drawn to 125 m or less capillary fibers
• plastic cladding applied 60 m

Fig. 21.20, Callister 7e.

Fig. 21.18, Callister 7e. Chapter 21 - 27


Optical Fiber Profiles
Step-index Optical Fiber

Fig. 21.21, Callister 7e.


Graded-index Optical Fiber

Fig. 21.22, Callister 7e.


Chapter 21 - 28
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.
Chapter 21 - 29
ANNOUNCEMENTS
Reading:

Core Problems:

Self-help Problems:

Chapter 21 - 30

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