MIT 3.

071
Amorphous Materials
12: Optical Properties

Juejun (JJ) Hu

1
After-class reading list

 Fundamentals of Inorganic Glasses

 Ch. 19
 Introduction to Glass Science and Technology
 Ch. 10
 3.024 wave optics

2
What's so special about ?

3
Refraction

Leeuwenhoek
Microscope

Image courtesy of Jeroen Rouwkema

on Wikimedia Commons. License: CC
BY-SA. This content is excluded from
our Creative Commons license. For
more information, see
http://ocw.mit.edu/help/faq-fair-use/.
 Transparency

Image of underwater optical fiber network removed due to copyright restrictions. See The Fiber Optic Association, Inc. website.

Global submarine optical fiber networks 5

 Color

Image courtesy of Josep Renalias on Wikimedia Commons. License: CC BY-SA. This content is excluded
from our Creative Commons license. For more information, see http://ocw.mit.edu/help/faq-fair-use/.

Palau de la Musica Catalana, Barcelona 6

Maxwell Equations (‘macroscopic’ differential form)

 Gauss’s Law:   D   f

 Gauss’s Law for magnetism:   B  0

B
 Faraday’s Law:   E  
t
D James C. Maxwell
 Ampere’s Law:   H  J f  (1831-1879)
t Image is in the public domain.
Source: Wikimedia Commons

H Magnetic field B Magnetic induction

E Electric field D Electric displacement
Jf Free current density f Free charge density
7
Constitutive relations in amorphous materials
 General form for non-bianisotropic media:
D  0E  P B  m0 H  m0 M
 Most amorphous materials are isotropic
 E and D (or B and H) always align in the same direction
 In most non-magnetic glasses, mr is close to 1 (m = m0)

P  0 E M  m H Linear media

D   0 (1   ) E   0 r E   E
Non-magnetic
B  m0 (1  m ) H  m0 mr H  m H ~ m0 H media
n mr  r ~  r  1   Non-magnetic media
8
Refractive index of glass: general trends
 Addition of heavy elements increases index
 Lead-containing glasses
 Addition of alkali oxides
increases index
 NBOs have larger
polarizability than
BOs
 Fictive temperature
(density) dependence

Rawson, Properties and Applications of Glasses (1980)

9
Kramers-Kronig (K-K) relation

Refractive index and

optical absorption
are not independent
a (w) quantities!
nr (w) -1

w / w0
10
Refractive index of glasses
 Wavelength/frequency dependent (Lorentz oscillators)
a Atomic/ionic
Electronic absorption
absorption

n
Atomic/ionic polarizability
1 Electronic polarizability

l
X-ray UV Visible IR Static
11
Chromatic dispersion of glasses

Prism dispersive spectrometer

© PASCO Scientific. All rights reserved. This content is
excluded from our Creative Commons license. For more
information, see http://ocw.mit.edu/help/faq-fair-use/.

Chromatic aberration

12
Chromatic dispersion of glasses
VD  ( nD  1) ( nF  nC )
 Abbe number (V-number):
 D, F and C spectral lines: 589.3 nm, 486.1 nm and 656.3 nm

F D C

Normal dn
0
n
dispersion d l

 0 Anormalous
dn
1 dl dispersion

l
X-ray UV Visible IR Static
13
 Chromatic dispersion of glasses
 Abbe number (V-number): VD  ( nD  1) ( nF  nC )

Crown glass (“K”)

 Soda-lime silicates
 Low index
 Low dispersion

Flint glass (“F”)

 Lead glasses
 High index
 High dispersion

Image courtesy of Bob Mellish on Wikimedia Commons. License: CC BY-SA. This content is excluded
from our Creative Commons license. For more information, see http://ocw.mit.edu/help/faq-fair-use/.
14
Diagram of Zeiss Hasselblad Sonnar Superachromat lens removed due to copyright restrictions.

15
Optical loss in silica glass
 I 
P ( dB )  10  log10  
 I0 
10  log10 ( 0.5 ) ~ 3.0 dB
The Nobel Prize in
Physics 2009
Charles Kuen Kao
Photo © U. Montana. All rights reserved.
This content is excluded from our Creative
Commons license. For more information,
see http://ocw.mit.edu/help/faq-fair-use/.
Prize motivation:
"for groundbreaking
I achievements
 exp ( a d ) 
I0 concerning the
transmission of light
in fibers for optical
1 dB cm  0.23 cm 1
communication"
16
Optical loss / attenuation mechanisms

Semiconductor Soda-lime glass Transparent Fiber-optic

optoelectronics in the infrared ceramics glasses

Electronic Phonon Defect Rayleigh

absorption absorption scattering scattering
Absorption Absorption Scattering by Scattering due to
induced by resulting from crystalline grains, density, structure
electronic atomic / ionic grain boundaries, or composition
transitions vibrations micro-voids, etc. fluctuations

17
Optical loss mechanisms in glasses
 Extrinsic absorption (impurities or dopants)
 Transition metal or rare earth ions
 Vibrational absorption
 Intrinsic attenuation
 Band-to-band transitions
 Urbach tail absorption
 Mid-gap defect state absorption
 Free carrier absorption (FCA)
 Phonon (vibrational) absorption
Color codes:
 Rayleigh scattering Atomic/ionic absorption
• Density fluctuation Electronic absorption
Scattering
• Structural moieties

18
Electronic absorption in amorphous solids

E 4 1 1. Band-to-band transition
Conduction band
3 2. Urbach bandtail absorption
3. Defect state absorption
Urbach tail h 4. Free carrier absorption
Mid-gap states
2 Mobility edge

Valence band

DOS

19
Electronic absorption in amorphous solids

E 4 1 1. Band-to-band transition
3 (a w )  w  ET
12

h ET : Tauc gap

2
Band-to-
band
transition

DOS
ET = 2.1 eV
A. Stern, Photodiodes – World
Activities in, 267 (2011).

20
Electronic absorption in amorphous solids

E 4 1 1. Band-to-band transition
3 2. Urbach bandtail absorption

a  aU exp ( w  Eg ) EU 
h

Urbach tail
absorption
DOS

A. Stern, Photodiodes – World

Activities in, 267 (2011).

21
Electronic absorption in amorphous solids

E 4 1 1. Band-to-band transition
3 2. Urbach bandtail absorption

a  aU exp ( w  Eg ) EU 
h

A: band-to-band
DOS B: Urbach tail
C: Dangling bonds
L. Ley, The Physics of Hydrogenated
Amorphous Silicon, 141 (1984).

22
Electronic absorption in amorphous solids

E 4 1 1. Band-to-band transition
3 2. Urbach bandtail absorption
3. Defect state absorption
h

A: band-to-band
DOS B: Urbach tail
C: Dangling bonds
L. Ley, The Physics of Hydrogenated
Amorphous Silicon, 141 (1984).

23
Electronic absorption in amorphous solids

E 4 1 1. Band-to-band transition
3 2. Urbach bandtail absorption
3. Defect state absorption
h 4. Free carrier absorption

2
Absorption coefficient (cm-1)
 Band-to-band: > 103
 Bandtail and defect states:
1 – 103
DOS  FCA: generally weak in
amorphous solids

24
Vibrational absorption
Atom Atom Compound Primary
k Harmonic oscillator
or functional absorption
m m w k m group bands (mm)
Bond O-H 2.92
4.01, 3.65,
Energy S-H
3.11, 2.05
Ge-H 4.95
P-H 4.35
As-H 5.02
Si-O 9.1 – 9.6
Ge-O 12.8
H2O 6.3, 2.8
Atomic spacing J. Optoelectron. Adv. Mater. 3, 341 (2001)

25
Sources of Rayleigh scattering in glass

 Local density fluctuation

8
a  A1 l 4 A1   3 n8 p 2 b k BT f
3
 p : photoelastic constant
 b : isothermal compressibility
 Concentration scattering
 Local composition fluctuation
in multi-component glasses
Einstein-Smoluchowski scattering:
Ann. Physik 33, 1275 (1910); density fluctuation of atmosphere
Ann. Physik 25, 205 (1908); Image courtesy of RoyalShot.com on photovaco. License: CC BY.

J. Appl. Phys. 55, 4052 (1984).

26
 Intrinsic optical loss spectrum in glass

Rayleigh Phonon
scattering absorption
limited limited
log(a)

Minimum
loss window

log(l)

Total loss: a t  ( A1  A2 ) l  B1 exp ( B2 l )  C1 exp ( C2 l )

4

27
Total optical loss in glasses

Electron. Lett.
SiO2 17, 775 (1981).

SiO2

CaF2-BaF2- GeS3
YF3-AlF4
Concentration scattering is not
taken into account, resulting in BaF2-GdF4-ZrF4
unrealistically low loss values

28
Transparent glass coloring: absorption
 Transition metal or rare earth ion additives

Image © Vitraž. All rights reserved. This

content is excluded from our Creative
Commons license. For more information,
see http://ocw.mit.edu/help/faq-fair-use/.

Green tint due to Fe2+ ions

Glass decolorization:


oxidation
Fe 2+   Fe3+
reduction

29
Examples of color glasses with ion additives

Cobalt Chromium
blue green

Uranium glass
(Vaseline glass)

Manganese
Room light UV illumination amethyst
Various images © unknown. All rights reserved. This content is excluded from our Creative
Commons license. For more information, see http://ocw.mit.edu/help/faq-fair-use/.
30
Transparent glass coloring: scattering
 Precipitation of small crystals or metal nanoparticles
 Rayleigh scattering by nanocrystals
 Plasmon resonance of metal nanoparticles

Opalescent glass: nanocrystals Lycurgus Cup: Au-Ag nanoparticles

Cryolite glass image © unknown. All rights reserved. This Images of the Lycurgus Cup courtesy of The British Museum.
content is excluded from our Creative Commons license. For
more information, see http://ocw.mit.edu/help/faq-fair-use/.

31
Striking colors
 Coloring of glass via heat treatment
 Example: gold-ruby striking
Annealing at 500 – 700 °C

O2-
Unfired
Au nanoparticles
Fired
(dia. 5 – 60 nm)
Au+ Au+

Melt at 1400 °C and quench

Nature 407, 691 (2000)
32
 Photochromic and electrochromic glasses
 Optical or electrical control of redox state of ions
 Carrier injection into transparent conductors to modulate FCA

Bleached
transparent

Nb 2 O5  x Li   x e 

Li x Nb 2 O5
Colored
brown-gray

Nature 500, 323 (2013)

'Smart glass' diagram © Heliotrope Technologies. All rights reserved. This content is excluded from
our Creative Commons license. For more information, see http://ocw.mit.edu/help/faq-fair-use/. 33
Photochromic and electrochromic glasses
 Optical or electrical control of redox state of ions
 Carrier injection into transparent conductors to modulate FCA

Photo of heat- and light-blocking film on glass © Anna Llordés, Lawrence Berkeley National Lab. All rights reserved. This
content is excluded from our Creative Commons license. For more information, see http://ocw.mit.edu/help/faq-fair-use/.

Nature 500, 323 (2013)

34
Summary
 Refraction
 Microscopic origin of refraction and chromatic dispersion
 Composition dependence of refractive indices
 Abbe number
 Attenuation
 Optical loss mechanisms in general materials
 Optical loss mechanisms in glasses
 Electronic, vibrational, and scattering losses
 Coloring
 Ion additives
 Scattering by nanoparticles

35
MIT OpenCourseWare
http://ocw.mit.edu

3.071 Amorphous Materials

Fall 2015

For information about citing these materials or our Terms of Use, visit: http://ocw.mit.edu/terms.