1

1
ISSUES TO ADDRESS...
What happens when light shines on a material?
Why do materials have characteristic colors?
Optical applications:
luminescence
photoconductivity
solar cell
optical communications fibers
Why are some materials transparent and others not?
Optical Properties of Materials
2
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
for visible light: 400 nm (blue) to 800 nm (red)
2
3
Refractive Index, n
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.

Polarizable ions (e.g., lead) are most effective in decreasing the speed of light.
Light is slower in a material vs vacuum.
n = refractive index
+
no
transmitted
light
transmitted
light
+
electron
cloud
distorts
Note: n is a function of the wavelength of light
4
Total Internal Reflectance
|
|'
=
' sin
sin
n
n
n(low)
n (high)
n > n
1
|
c
|
'
1
|
reflected internally is light for
90 when occurs
c i
i c
| > |
= |' |
angle critical
angle refracted
angle incident
= |
= |'
= |
c
i
i
3
5
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
6
Optical Fibers
prepare preform by extrusion
preform drawn to 125 m or less capillary fibers
plastic cladding applied 60 m
4
7
Optical Fiber Profiles
Step-index Optical Fiber
Graded-index Optical Fiber
8
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:
single
crystal
polycrystalline
dense
polycrystalline
porous
Transparent
Translucent
Opaque
Incident: I
0
Absorbed: I
A
Transmitted: I
T
Scattered: I
S
Reflected: I
R
5
9
Absorption of photons by electron transition:
Metals have a fine succession of energy states.
Near-surface electrons absorb visible light.
Optical Properties of Metals: Absorption
Energy of electron
I
n
c
i
d
e
n
t

p
h
o
t
o
n
Plancks constant
(6.63 x 10
-34
J/s)
freq.
of
incident
light
filled states
unfilled states
AE = hv required!
I
o
o
f

e
n
e
r
g
y

h
v
10
Light Absorption
t
I
I
ln
0
o =
(

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

t
Beers Law: A = lC
6
11
Reflectivity = I
R
/I
o
is between 0.90 and 0.95.
Reflected light is same frequency as incident.
Metals appear reflective (shiny)!
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
12
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
7
13
Scattering
Occurs especially in semicrystalline & polycrystalline materials
Semicrystalline mixture of crystalline and amorphous phases
density of crystals higher than amorphous materials
speed of light is lower
causes light to change direction = scatter
can cause significant loss of light during transmission
Common in polymers
Ex: Polyethylene milk bottles cloudy because of crystalline regions
Plexiglass (polymethylmethacrylate) clear essentially no crystals
14
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.
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
8
15
Wavelength vs. Band Gap
1.85 m = 1850 nm = 18,500 = 5400 cm
-1
= infrared
If donor (or acceptor) states also available, this provides other
absorption frequencies
E
g
= 0.67 eV
e.g.: What is the minimum wavelength absorbed by Ge?

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)
s
1.85

m
note: for Si E
g
=1.1eV
c
s1.13

m
16
Color determined by sum of frequencies of
transmitted light + re-emitted light from electron transitions.
Ex: Cadmium Sulfide (CdS)
Egap = 2.4 eV = 516 nm = 5160 = green
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 :
alters the band gap
blue light is absorbed
yellow/green is absorbed
red is transmitted
Result: Ruby is deep red in color.
40
60
70
80
50
T
r
a
n
s
m
i
t
t
a
n
c
e

(
%
)
ruby
sapphire
0.3 0.5 0.7 0.9
wavelength, (m)
9
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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
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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
10
19
Cathodoluminescence
Used in T.V. set
Bombard phosphor with electrons
Electrons excite phosphor to high state
Excited state relaxed by emitting photon (visible)
ZnS, doped with Ag
+
+ Cl
-
blue
(Zn,Cd)S, doped with Cu
+
+ Al
3+
green
Y
2
O
2
S, doped with 3% Eu red
Note: light emitted is random in phase & direction
i.e., noncoherent
20
Laser Light
Non-coherent light diverges and cant be 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
11
21
Population Inversion
What if we could increase most species to the excited state?
22
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.
12
23
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
24
Continuous Wave Lasers
Can also use materials such as CO
2
or
yttrium-aluminum-garnet (YAG) for lasers
Set up standing wave in laser cavity
tune frequency by adjusting mirror spacing.
Uses of CW lasers
Welding
Drilling
Cutting laser carved wood, eye surgery
Surface treatment
Scribing ceramics, etc.
Photolithography Excimer laser
13
25
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 Lasers
26
Types of Lasers
14
27
Uses of Semiconductor Lasers
#1 use = CD & DVD players
Color? - red Blue-Ray? - blue (duh)
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
28
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
15
29
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
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
30
Spatial Separation of Hole-Electron Pairs
How to prevent recombination of photogenerated electrons and holes?
Usually accomplished by band bending, e.g., p-n heterojunction:
before contact
p-type
n-type
Fermi
level
after contact:
band bending
h
+
e-
after photon:
spatial charge separation
16
31
Grand Challenge: Solar-Power Paint
Solar-Driven Photocatalytic Water Splitting:
glass or
plexiglass
photocatalyst
suspension
H
2
separating
membrane
H
2
H
2
O
2
There remain critical unsolved materials challenges There remain critical unsolved materials challenges
before any practical device. before any practical device.
32
Past History of Photochemical Water Splitting
Expensive. Pt / RuO
2
for H
2
& O
2
production.
Works reasonably well.
Nanocluster catalysts
(post-charge separation)
Long neglected.
S/Se corrosion limited.
Light harvesting problematic.
First proposed by Nozik.
Oxide-Sulfides/Se mostly
(Kamat, Lee, ).
Oxide p-n Heterojunctions
WO
3
or Fe
2
O
3
/ Si multilayer.
Very powerful for light
harvesting.
I
3

/I

relatively robust.
35 years of effort.
Band gap tuning
via soln. potential.
Description Limitations &
Unsolved Problems
Class of Device
Modest Quantum Yield.
Usually requires applied potential. Often
stability issues.
Composite Devices/
Hybrid Photoelectrodes
Dyes die after 10
6
photons.
Very corrosive in practice.
Dye Sensitization
Corrosion limited (even Si).
No robust resolution.
Small Band Gap Semiconductor-
Solution
Heterojunctions
17
33
Pt / Titania Nanocomposites
2H
2
O+ O
2
2H
+
H
2
Pt
e
t
h
t
VB

+
+
CB
4OH

Hydrogen Evolution rates for

various Photocatalysts (l/hr)
Pt/TiO
2
7.7
Pd/TiO
2
6.7
Rh/TiO
2
2.8
Ru/TiO
2
0.2
Sn/TiO
2
0.2
Ni/TiO
2
0.1
TiO
2
<0.1
Toshima, J . Phys. Chem. 1985, 89, 1902
Cf. also: Subramanian, V.; Wolf, E. E.; Kamat, P. V. J . Am. Chem. Soc. 2004, 126, 4943.
34
Existing Systems: Almost completely Metal Sulfides/Selenides
(due to visible light absorption).
Critical Problem: Long term stability of photocatalysts.
Most semiconductors are NOT long-term stable
in water during photolysis.
Potential solution: Oxides are the thermodynamically stable state,
but most oxides do not absorb visible light.
What is needed: Band gap engineering of Oxide-Oxide Interfaces
to create new absorbance mechanisms.
This is an exploratory materials effort, not a device project. This is an exploratory materials effort, not a device project.
Key Issues in
Photochemical Water Splitting
18
35
Heterostructured Photoelectrodes
Type II
Staggered Offset
Heterostructure
Type I
Straddled
Heterostructure
Type III
Broken
Heterostructure
h+
e-
(p n, p i, or n i
Heterojunctions)
Type II inter-junction optical transition: emergent property on nanoscale.
Equivalent to Charge Transfer transitions in molecular systems.
Has an oxides stability BUT ALSO a small effective band gap.
36
Light Absorbance Lessons from MBE:
Engineered Oxide Band Gaps
2H
+
+2e
-
H
2
-0.421
+0.815
2H
2
O+4h
+
4H
+
+O
2
-2
-1
0
1
2
3
4
5
P
o
t
e
n
t
i
a
l

/

V



(
v
s
.

N
H
E
,

p
H

7
)
conduction band too stable,
no water splitting
2.2
F
e
2
O
3
2.1
C
d
O
S
n
O
2
3.5
band gaps too big band gaps too big
inefficient: UV only inefficient: UV only
T
a
2
O
5
4.0
3.1
N
b
2
O
5
Z
n
O
3.2
A
n
a
t
a
s
e
T
i
O
2
3.2
3.4
C
a
T
i
O
3
3.5
K
T
a
O
3
3.2
S
r
T
i
O
3
2.6
I
n
T
a
O
4
I
n
T
a
O
4
A
n
a
t
a
s
e
T
i
O
2
1.7
example of example of
hetero hetero- -oxide oxide
gap gap
C
d
S
2.4
N
O
N
-
O
X
I
D
E
S
19
37
Lateral SL by
MBE step-
flow growth:
50-100 nm
SrTiO
3
LaMnO
3
Goal: Create new visible absorption by staggered Type-2 oxide
heterojunctions. Requires high density of red-ox active interfaces.
SrTiO
3
SrMnO
3
SrCrO
3
SrCoO
3
ABO
3
CDO
3
red-ox
oxide
heterojunction
LaMnO
3
LaScO
3
LaNiO
3
KVO
3
Digital Superlattice for Band Structure Engineering
Vertical SL
by multi-
layer MBE:
New Abs.
New valence-to-conduction band
transition: solid-state analog to
molecular Charge-Transfer
transitions.
Eckstein
38
2 nm
LMO
LMO
LMO
LMO
SMO/STO multilayer
STMO/STO multilayer
LMO/STO multilayer
Z-contrast image
STO = SrTiO
3
SMO = SrMnO
3
LMO = LaMnO
3
Ti
L
23
Mn
L
23
La
M
45
O
K-edge
E
E
L
S

l
i
n
e

s
c
a
n
Electron Energy-loss Spectrum
Complex Interfacial Designer Structures
Eckstein, Zuo with Wen, Petrov (FS-MRL staff)
20
39
Designer Materials: Meta-Materials
Band structure control by nano-scale engineering
New visible absorption in vertical short period superlattices.
LaMnO
3
(LMO) / SrTiO
3
(STO) superlattices: N X N, N = 1, 2, 4, 8 ML.
Absorption spectrum different from simple sum of components.
1 X 1 is most different; spectra approach simple sum for large N.
New properties, not found in parent phases, arise at heterojunctions.
absorption of N x N vertical superlattices absorption of SrTiO
3
Photon Energy (eV)
A
b
s
o
r
b
a
n
c
e
0
2
4
6
8
10
1 2 3 4 5
620nm 413nm 310nm
Solar Spectral Range
0
5000
1 10
4
1.5 10
4
2 10
4
2.5 10
4
3 10
4
3.5 10
4
4 10
4
0
5000
1 10
4
1.5 10
4
2 10
4
2.5 10
4
3 10
4
3.5 10
4
0.5 1 1.5 2 2.5 3 3.5
p
s
u
p
e
r
l
a
t
t
i
c
e

o
p
t
i
c
a
l

c
o
n
d
u
c
t
i
v
i
t
y
m
o
d
e
l

o
p
t
i
c
a
l

c
o
n
d
u
c
t
i
v
i
t
y
energy (eV)
1x1
2x2
3x3
8x8
dielectric model
New absorption
feature
Shifted
absorption
edge
Eckstein
40
620nm 413nm 310nm 620nm 413nm 310nm
Lets compare optical absorption spectra engineered in
superlattices made from LaMnO
3
(LMO) and SrTiO
3
(STO).
Lateral Superlattices vs. Vertical Superlattices
3-D nanostructure of superlattice changes the optical absorption!
Designer Materials: Meta-Materials
Band structure control by nano-scale engineering
Eckstein
21
41
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.
SUMMARY