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ISSUES TO ADDRESS...

What happens when light shines on a material?


Why do materials have characteristic colors?
Optical applications:
-- lasers
-- optical communications fibers
Why are some materials transparent and others not?
Chapter 16: Optical Properties

Optical Properties
Light has both particulate and wavelike properties
Photons

= v = A
hc
h E
m/s) 10 x (3.00 light of speed c
) s J 10 62 . 6 ( constant s Planck'
frequency
wavelength
energy
8
34
=
=
= v
=
= A

x h
E
Important numbers:
Our Eyes Can ONLY see:

0.4 to 0.7 m
1.65 eV to 3.1 eV
4.3x10
14
to 7.5x10
14
Hz

I
0
= I
T
+ I
R
+ I
A

1= T + R+ A
Monochromated light
Reflected
Raman scattering
Transmitted
Rayleigh scattering
v, I
0
v, I
v
scat
v ~
Incident light is either reflected, absorbed, or
transmitted:
S R A T o
I I I I I + + + =
Light Interaction with Solids
Optical classification of materials:
Adapted from Fig. 21.10, Callister
6e. (Fig. 21.10 is by J. Telford,
with specimen preparation by P.A.
Lessing.)
single
crystal
polycrystalline
dense
polycrystalline
porous
Transparent
Translucent
Opaque
Incident: I
0

Absorbed: I
A

Transmitted: I
T

Scattered: I
S

Reflected: I
R


Two main phenomena:

Electronic Polarization

+

Electronic Transitions
Refractive Index, n
Note: n = f ()
Typical glasses ca. 1.5 -1.7
Plastics 1.3 -1.6
PbO (Litharge) 2.67
Diamond 2.41
medium) in light of (velocity
vacuum) in light of (velocity
v
c

Transmitted light distorts electron clouds.


Light is slower in a material vs vacuum.
n = refractive index
+
no
transmitted
light
transmitted
light
+
electron
cloud
distorts
Selected values from Table 21.1,
Callister 7e.
--Adding large, heavy ions (e.g., lead
can decrease the speed of light.
--Light can be
"bent"
Index of Refraction
n =
v
vac
v
sol
n =
sini
sin r
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Relationship Between Dielectric and Optical Properties
' ' k
e
= 2nk =
e
2
N
c
0
m
e
ef
e
0
2
e
2
( )
2
+ f
2
e
2
' k
e
= n
2
k
2
= 1+
e
2
N
c
0
m
e
e
0
2
e
2
e
0
2
e
2
( )
2
+ f
2
e
2
n =
1
2
' k
e
2
+ ' ' k
e
2
( )
1 2
+ ' k
e
k =
1
2
' k
e
2
+ ' ' k
e
2
( )
1 2
' k
e
For insulators
n = ' k
e

R =
n 1
( )
2
n +1
( )
2
Question: Is n a function of frequency??

' k
e
~ n
2
=1+
e
2
N
c
0
m
e
1
e
0
2
e
2
( )
Answer ??????
As e approaches e
0
n ?????


Origin is Electronic Polarizations
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Convince
yourself
that in general
there is a
relationship
between
ion size
and n.
Light Absorption
t
I
I
ln
0
o =
(

t
I
I
o
= e
0
thickness sample
cm ] [ t coefficien absorption linear
1
=
= = o

t
Relationship between
Dielectric and Optical
Properties
Ionic
polariz.
Band
gap!
Transparency
window
Q u i c k T i m e a n d a
T I F F ( U n c o m p r e s s e d ) d e c o m p r e s s o r
a r e n e e d e d t o s e e t h i s p i c t u r e .
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IR Adsorption Edge
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Absorption of photons by electron transition:
Metals have a fine succession of energy states.
Near-surface electrons absorb visible light and
then re-emit it at same wavelength.
Optical Properties of Metals:
Absorption
Energy of electron
Plancks constant
(6.63 x 10
-34
J/s)
freq.
of
incident
light
filled states
unfilled states
AE = hv required!
I
o
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
Absorption by electron transition occurs if hv > Egap
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.
Adapted from Fig. 21.5(a), Callister 7e.
Selected Absorption: Semiconductors
incident photon
energy hv
Energy of electron
filled states
unfilled states
E
gap

I
o

blue light: hv = 3.1 eV
red light: hv = 1.7 eV
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c
=
hc
E
g
=
(6.62 x 10
34
J s)(3 x 10
8
m/s)
(0.67eV)(1.60 x 10
19
J/eV)
s1.85m
note: for Si E
g
=1.1eV
c
s1.13 m
Wavelength vs. Band Gap
If donor (or acceptor) states also available this provides other
absorption frequencies
E
g
= 0.67 eV
Example: What is the minimum wavelength absorbed
by Ge?
Color
You need selective absorption. What is left over, plus what
is re-emitted by crystal is the color you see.
Two examples:
a) CdS Band gap = 2.4 eV.
What light will be absorbed? Red or blue?
What is not absorbed is what you see.
b) Sapphire vs Ruby
When you add impurities to an insulator you can create levels
in the band gap that in turn selectively absorb some frequencies
but not others giving rise to color.



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.
Color of Nonmetals
Ex: Ruby = Sapphire (Al2O3) + (0.5 to 2) at% Cr2O3
-- Sapphire is colorless
(i.e., Egap > 3.1eV)
-- adding Cr2O3 :
introduces localized
levels in forbidden gap
blue light is absorbed
yellow/green is absorbed
red is transmitted
Result: Ruby is deep red in color.
40
60
70
80
50
0.3 0.5 0.7 0.9
T
r
a
n
s
m
i
t
t
a
n
c
e

(
%
)

ruby
sapphire
wavelength,
(= c/v)(m)
Ligand Field Theory
Example: transition metal cation in
sapphire.
}
Scattering
I
T
I
0
= exp o
s
x ( )
o
s
= Q
s
N
s
t r
s
2
Q
s
= const ( )
r
s

|
\

|
.
|
4
n
matri x
2
n
scatt er
2
( )
2
1) r <<
2 limiting cases:
2) r >>
Q
s
= 2
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f
p
=
4
3
t r
s
3
N
s
Then : N
s
=
3 f
p
4tr
s
3

o
s
= Q
s
N
s
t r
s
2
=
3 f
p
4tr
s
3
Q
s
t r
s
2
=
3 f
p
4tr
s
Q
s

o
s
=
3 f
p
4tr
s
Q
s
= const
( )
f
p

r
s
3

4
n
matrix
2
n
scatter
2
( )
2

Q
s
= const
( )

r
s

|
\

|
.
|
4
n
matrix
2
n
scatter
2
( )
2
Revisit 2 regimes:
1) r <<
2) r >>
Q
s
= 2

o
s
= Q
s
N
s
t r
s
2
=
3 f
p
4tr
s
3
Q
s
t r
s
2
=
3 f
p
4tr
s
Q
s
=
6 f
p
4tr
s
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o
s
= const
( )
r
s
3
Like
a bat
outta hell

o
s
=
const.
r
s
I
T
I
0
= exp o
s
x ( )
3 Examples
Milk
Paint.
Weather
Rain
Humid day in summer
Fog
So why is the SKY blue???
Because of Rayleigh scattering
LASER Light
Is non-coherent light a problem? diverges
cant keep tightly collimated

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
Population Inversion
What if we could increase most species to the excited
state?
Fig. 21.14, Callister 7e.
Population Inversion
Fig. 21.14, Callister 7e.
X X X X X X X
Very rapid
Much slower
and all
together now!!
Electrons
like
birds
on a
wire
First
you
need
to
pump
electrons
into
conduction
band
LASER Light Production
pump the lasing material to the excited state
e.g., by flash lamp (non-coherent lamp).
If we let this just decay we get no coherence.
Fig. 21.13, Callister 7e.
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.
Total Internal Reflectance
|
|
'
=
'
sin
sin
n
n
n(low)
n (high)
n > n
1
|
c
|
'
1
|
angle critical
angle refracted
angle incident
= |
= |
'
= |
c
i
i
reflected internally is light for
90 when occurs
c i
i c
| > |
= |
'
|
Example: Diamond in air
Fiber optic cables are clad in low n material for this
reason.

5 . 24
41 . 2
1
sin
sin
1
sin
90 sin
1
41 . 2
sin
sin
= | = |
|
=
|
=
|
|
'
=
'
c c
c c
n
n
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.
Optical Fiber Profiles
Step-index Optical Fiber
Graded-index Optical Fiber
Fig. 21.21, Callister 7e.
Fig. 21.22, Callister 7e.
When light (radiation) shines on a material, it may be:
-- reflected, absorbed, scattered, and/or transmitted.
Optical classification:
-- transparent, translucent, opaque
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 localized energy levels (e.g., Ruby)
Refraction:
-- speed of transmitted light varies among materials.
-- refraction and reflection are due to electronic polarizations
-- The latter are proportional to the size of the ions.
SUMMARY
From here on optional.
From here on optional..
Apply strong forward
bias to junction.
Creates excited state
by pumping electrons
across the gap-
creating electron-hole
pairs.
electron + hole neutral + hv
excited state
ground state
photon of
light
Semiconductor LASER
Adapted from Fig. 21.17,
Callister 7e.
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

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




New semiconductors
Materials scientists
(& many others) use lasers as tools.
Solar cells
Solar Cells
p-n junction: Operation:
-- incident photon produces hole-elec. pair.
-- typically 0.5 V potential.
-- current increases w/light intensity.
Solar powered weather station:
polycrystalline Si
Los Alamos High School weather
station (photo courtesy
P.M. Anderson)
n-type Si
P-type Si
p-n junction
B-doped Si
Si
Si
Si Si B
hole
P
Si
Si
Si Si
conductance
electron
P-doped Si
n-type Si
p-type Si
p-n junction
light
+
-
+ + +
- - -
creation of
hole-electron
pair
Luminescence
Luminescence emission of light by a material
material absorbs light at one frequency & emits at
another (lower) frequency.
activator
level
Valence band
Conduction band
trapped
states
E
g

E
emission

How stable is the trapped state?
If very stable (long-lived = >10
-8
s) =
phosphorescence
If less stable (<10
-8
s) = fluorescence

Example: Glow in the dark toys.
Charge them up by exposing them to
the light. Reemit over time. --
phosphorescence
Photoluminescence
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
Ca
10
F
2
P
6
O
24
with 20% of F
-
replaced by Cl
-

Adjust color by doping with metal cations
Sb
3+
blue
Mn
2+
orange-red
Hg
uv
electrode electrode
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
+
+Al
3+
) green
Y
2
O
2
S + 3% Eu

red

Note: light emitted is random in phase & direction
i.e., noncoherent
Continuous Wave LASER
Can also use materials such as CO
2
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
Reflectivity = I
R
/I
o
is between 0.90 and 0.95.
Reflected light is same frequency as incident.
Metals appear reflective (shiny)!
Adapted from Fig. 21.4(b), Callister 7e.
Optical Properties of Metals:
Reflection
Electron transition emits a photon.
re-emitted
photon from
material surface
Energy of electron
filled states
unfilled states
AE
I
R

conducting electron
Metals

m
d
2
o
dt
2
|
\

|
.
|
= eE
0
expiet

o =
eE
0
m
e
e
2
expi et
( )
No damping - no restoring force
viz. free electrons in a metal

' k 1=
P
c
0
E

P = N
f
eo
Polarization of all N
f
free electrons

' k 1=
P
c
0
E

' k
e
e
( )
=1
e
2
Z
eff
N
f
c
0
m
e
e
2
No restoring force, e
o
= 0, and no friction, f = 0, then:


'
k
e
e
( )
= 1+
Z
i
e
2
N e
0
2
e
2
( )
c
0
m
e
e
0
2
e
2
( )
2
+ f
2
e
2
{ }
At low frequencies, the second term is > 1 and n is negative
which is the same as saying the wave is reflected.

At high frequencies, the second term < 1, and n is positive,
i.e. real but less than one.

e
plasma
2
=
e
2
Z
eff
N
f
c
0
m
e
Polarization of all N
f
free electrons
Z
eff
is effective # of free electrons/atom
Reflectivity, R
Reflection
Metals reflect almost all light
Copper & gold absorb in blue & green => gold
color
ty reflectivi
1
1
2
=
|
.
|

\
|
+

=
n
n
R
17 . 0
1 41 . 2
1 41 . 2
2
=
|
.
|

\
|
+

= R
reflected is light of % 17
Example: Diamond