Chirality in amorphous and crystalline materials - experimental aspects David Avnir
MIT 3.071 Amorphous Materials · Amorphous Materials 12: Optical Properties ... Transition metal or...
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MIT 3.071 Amorphous Materials 12: Optical Properties
Juejun (JJ) Hu
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After-class reading list
Fundamentals of Inorganic Glasses Ch. 19
Introduction to Glass Science and Technology Ch. 10
3.024 wave optics
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What's so special about ?
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Refraction
Leeuwenhoek Microscope
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Transparency
Global submarine optical fiber networks 5
Image of underwater optical fiber network removed due to copyright restrictions. See The Fiber Optic Association, Inc. website.
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Color
Palau de la Musica Catalana, Barcelona 6
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Maxwell Equations (‘macroscopic’ differential form)
Gauss’s Law:
Gauss’s Law for magnetism:
Faraday’s Law:
Ampere’s Law:
fD
0B
BE
t
f
DH J
t
James C. Maxwell (1831-1879)
H Magnetic field B Magnetic induction E Electric field D Electric displacement Jf Free current density f Free charge density
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Constitutive relations in amorphous materials
General form for non-bianisotropic media:
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)
0D E P 0 0B H Mm m
0P E mM H
0 0(1 ) rD E E E
0 0 0) ~(1 m rB H H H Hm m mm m Non-magnetic
media
Linear media
~ 1r r rn m Non-magnetic media
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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)
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Kramers-Kronig (K-K) relation
w / w0
a (w) nr (w) -1
Refractive index and optical absorption
are not independent quantities!
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Refractive index of glasses
Wavelength/frequency dependent (Lorentz oscillators)
l
n
IR Visible Static UV X-ray
1 Electronic polarizability Atomic/ionic polarizability
a Electronic absorption
Atomic/ionic absorption
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Chromatic dispersion of glasses
Prism dispersive spectrometer
Chromatic aberration
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Chromatic dispersion of glasses
Abbe number (V-number): D, F and C spectral lines: 589.3 nm, 486.1 nm and 656.3 nm
l
n
Visible Static UV X-ray
1
Normal dispersion
IR
0dn
dl
0dn
dl
Anormalous dispersion
( ) ( )1D D F CV n n n
D F C
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Chromatic dispersion of glasses
Abbe number (V-number): ( ) ( )1D D F CV n n n
Crown glass (“K”)
Soda-lime silicates Low index Low dispersion
Flint glass (“F”)
Lead glasses High index High dispersion
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Diagram of Zeiss Hasselblad Sonnar Superachromat lens removed due to copyright restrictions.
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Optical loss in silica glass
( ) 10
0
dB 10 logI
PI
( )
0
exp I
dI
a
11 dB cm 0.23 cm( )1010 log 0.5 ~ 3.0 dB
The Nobel Prize in
Physics 2009
Charles Kuen Kao
Prize motivation: "for groundbreaking
achievements concerning the
transmission of light in fibers for optical communication"
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Optical loss / attenuation mechanisms
Semiconductor optoelectronics
Soda-lime glass in the infrared
Transparent ceramics
Fiber-optic glasses
Electronic absorption
Absorption induced by electronic transitions
Phonon absorption
Absorption resulting from atomic / ionic
vibrations
Defect scattering
Scattering by crystalline grains, grain boundaries, micro-voids, etc.
Rayleigh scattering
Scattering due to density, structure or composition
fluctuations
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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 Rayleigh scattering
• Density fluctuation • Structural moieties
Color codes: Atomic/ionic absorption Electronic absorption Scattering
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Electronic absorption in amorphous solids
E
DOS
Conduction band
Valence band
Mobility edge
Mid-gap states
Urbach tail h
1
2
3
4 1. Band-to-band transition 2. Urbach bandtail absorption 3. Defect state absorption 4. Free carrier absorption
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Electronic absorption in amorphous solids
E
DOS
h
1
2
3
4
( )1 2
TEa w w
ET : Tauc gap
ET = 2.1 eV
1. Band-to-band transition
Band-to-band
transition
A. Stern, Photodiodes – World Activities in, 267 (2011).
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Electronic absorption in amorphous solids
E
DOS
h
1
2
3
4
A. Stern, Photodiodes – World Activities in, 267 (2011).
1. Band-to-band transition 2. Urbach bandtail absorption
Urbach tail absorption
( )expU g UE Ea a w
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Electronic absorption in amorphous solids
E
DOS
h
1
2
3
4
( )expU g UE Ea a w
L. Ley, The Physics of Hydrogenated Amorphous Silicon, 141 (1984).
1. Band-to-band transition 2. Urbach bandtail absorption
A: band-to-band B: Urbach tail C: Dangling bonds
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Electronic absorption in amorphous solids
E
DOS
h
1
2
3
4 1. Band-to-band transition 2. Urbach bandtail absorption 3. Defect state absorption
L. Ley, The Physics of Hydrogenated Amorphous Silicon, 141 (1984).
A: band-to-band B: Urbach tail C: Dangling bonds
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Electronic absorption in amorphous solids
E
DOS
h
1
2
3
4 1. Band-to-band transition 2. Urbach bandtail absorption 3. Defect state absorption 4. Free carrier absorption
Absorption coefficient (cm-1)
Band-to-band: > 103 Bandtail and defect states:
1 – 103 FCA: generally weak in
amorphous solids
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Vibrational absorption
Atomic spacing
Energy
Harmonic oscillator
k mw
Compound or functional
group
Primary absorption bands (mm)
O-H 2.92
S-H 4.01, 3.65, 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
J. Optoelectron. Adv. Mater. 3, 341 (2001)
m m
k Atom Atom
Bond
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Sources of Rayleigh scattering in glass
Local density fluctuation
p : photoelastic constant
b : isothermal compressibility
Concentration scattering Local composition fluctuation
in multi-component glasses
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1Aa l 3 8 2
1
8
3B fA n p k T b
Einstein-Smoluchowski scattering:density fluctuation of atmosphereAnn. Physik 33, 1275 (1910);
Ann. Physik 25, 205 (1908); J. Appl. Phys. 55, 4052 (1984).
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Intrinsic optical loss spectrum in glass lo
g(a
)
log(l)
( ) ( ) ( )4
1 221 2 1 exp expt A CB CA B lla l Total loss:
Phonon absorption
limited
Rayleigh scattering
limited Minimum
loss window
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Total optical loss in glasses
SiO2
BaF2-GdF4-ZrF4
CaF2-BaF2-YF3-AlF4
GeS3
Electron. Lett. 17, 775 (1981). SiO2
Concentration scattering is not taken into account, resulting in unrealistically low loss values
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Transparent glass coloring: absorption
Transition metal or rare earth ion additives
Green tint due to Fe2+ ions
oxidation
reduction
+2+ 3 F Fee
Glass decolorization:
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Examples of color glasses with ion additives
Cobalt blue
Chromium green
Room light UV illumination
Uranium glass (Vaseline glass)
Manganese amethyst
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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
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Striking colors
Coloring of glass via heat treatment Example: gold-ruby striking
Annealing at 500 – 700 °C
Melt at 1400 °C and quench Nature 407, 691 (2000)
Au+
O2-
Au+ Unfired Fired
Au nanoparticles (dia. 5 – 60 nm)
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Photochromic and electrochromic glasses
Optical or electrical control of redox state of ions Carrier injection into transparent conductors to modulate FCA
2 5Nb O Li ex x
2 5Li Nb Ox
Bleached transparent
Colored brown-gray
Nature 500, 323 (2013)
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Photochromic and electrochromic glasses
Optical or electrical control of redox state of ions Carrier injection into transparent conductors to modulate FCA
Nature 500, 323 (2013) 34
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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
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