C. Optical Properties of Materials: Objectives
C. Optical Properties of Materials: Objectives
AUG
Contents Objectives
• light (9.1)
• What happens when light shines
• refractive index, n (9.2)
on a material?
• dispersion, n(l) (9.3)
– vg, Ng, zero dispersion (9.4) • colors of materials
• principles • Why are some materials
– Snell (9.6): direction transparent and others not?
– Fresnel (9.7): amplitudes, phases • Optical applications:
• losses & origins
– optical fibers
– n-jK, er'-jer", k'-jk" (9.8)
– lattice absorption (9.9) – optical amplification
– VB CB absorption (9.10) – luminescence, phosphors
– scattering (9.11) – nanostructures
• case studies
– optical fibre (9.12)
– luminescence, phosphor (9.13)
Reference: S.O. Kasap (3rd,4th Ed.) Chap. 9; RJD Tilley (Understanding solids, 2nd Ed) Chap. 14.
Optcal Properties 2102308 1
(L0)
9.1 Light
• optical properties of matter describe the interaction of light with matter
• types of interactions: scattering, reflection, absorption, transmission, diffraction…
• properties of light: wave-particle duality
– for propagation & scattering, light = EM wave
– for absorption & emission, photons = particle
• visible light has energy ~1.8-3.1 eV, wavelength ~400-700 nm (visible spectrum) vs.
• a much wider electromagnetic spectrum (Fig./Table 14.1) (L1)
• wavelength l of interest: 10 nm (X-rays) – 100 mm. Selected applications:
– germicide/cosmetic: 300-400 nm (UV)
– display: 400-700 nm (VIS)
– optical communication: 1.3 and 1.55 mm (IR)
• light is an oscillating electromagnetic (EM) field where electric component E ⊥ to
magnetic component B, both of which ⊥ to propagation direction k (Fig. 9.1) (L2-L3)
– simplest description: monochromatic light travelling in space in 1D (Fig. 9.2)
– more complete description must be in 3D (Fig. 9.3)
• light can be generated by electrons in atoms, molecules, solids (crystals) dropping
from high to low energy levels/bands (L4-L5). Other courses explain the principle of
light generation by semiconductor devices (2102385, SKJ), and lasers (2102589, SPY)
light-related vocabularies:
- monochromatic: single or very narrow
monochromatic plane wave:
range of l (red laser yes, the sun no)
time space
phase - coherent: photons constituting light
in 1D: Ex Eo cost kz o beam are in phase (laser yes, LED no)
- polarization: direction of E field,
k is propagation constant or wavenumber light sources can be (*) unpolarized,
(a) plane polarized, (b) elliptically
E polarized, (c) circularly polarized,
T f 1/ T
t time
2 / T
z space
k 2 / l
l
*
Optcal Properties 2102308 4
(L3)
- propagation
monochromatic plane wave propagates in space at velocity v
1D (far from source) for any given plane, the phase
t kz o
plane wave
is a constant which moves dz at
“planes” every dt phase velocity:
dz
v lf
dt k
f 1/ T
2 / T
k 2 / l
3D (close to source)
spherical wave
E r ,t Eo cost k r o
(smooth)
A
T
R
Cloaking Transmission
filled states
• Metals have fine succession of energy states. • Metals appear reflective (shiny) because
• Near-surface electrons absorb visible light. • Reflectivity = IR/Io is ~ 0.90-0.95.
(reflected light same frequency as incident)
Colors
Pd Au Color of metals dictated by interfacial
property (metal/insulator interface) called
Transmission (none) “surface plasmon resonance (SPR)”
since IA + IR ~ 1 IT ~ 0; therefore, all metals are opaque (except thin foil < 100 nm, transmit visible light)
Optcal Properties 2102308 10
Light interaction with non-metals (I3)
Luminescence
incident photon (re-emitted light)
energy hn
• If EG < 1.8 eV, full absorption; color is black ([email protected], [email protected] eV)
• If EG > 3.1 eV, no absorption; colorless ([email protected], glass@9 eV), transparent (!), see (I5)
• If EG in between or has impurity level, partial absorption; material has a color.
Optcal Properties 2102308 11
(I4)
Light-Matter Interaction: Results LDR
• Ex. 2 (Insulator)
The Hope Diamond = C (+ % B)
- Egap = 5.6 eV
- luminesce after UV exposure (l<220nm) (1.88 eV)
- phosphorescence
(re-emission occurs with delay time > 1 s)
Origin of color:
Boron (0-8 ppm depends on position, av. 0.36 ppm)
http://nhminsci.blogspot.com/2012/05/hope-diamond-blue-by-day-red-by-night_22.html
Refraction (qi ≠ 0): a change in propagation direction of a wave when it changes a medium
Optcal Properties 2102308 14
• refractive index (n) measures how much light slows down in a material, with respect
to vacuum. Speed of light in i) vacuum = c, ii) material = phase velocity v (), ∴ n
• materials slow down light due to light-matter interaction: atoms/molecules/grains in
optical/dielectric materials are polarized by the electric field component of light E
(Reminder: polarization mechanisms), Fig. A (R1)
• propagation of light (E) in a material is effectively delayed (phase lag) wrt. vacuum
• (from ) material permittivity er stronger dipoles (drag ) delays
• atoms/molecules in medium are polarized at the same frequency as E, hence the
frequency of light does not change, but other wave propagation & parameters do
change, Table A (R1). Typical wavefronts in films, Fig. B (R1)
• n is not a constant, but can change with
incident direction, especially in some 1 c c
crystals (birefringent) which show v
e re o m r mo e r mr er
optical anisotropy (9.14) (R2,R3) c
n er
• n is not a constant, but can change with v optical materials are
incident wavelength, thus n(l), see non-magnetic (mr ≅ 1)
example (R4), for details next section
9.3 Dispersion
Fig. A
Orientational,
er'
n er Dipolar
n (l ) e r ( f )
Ionic
Electronic
er''
er' = 1
ƒ
10-2 1 102 104 106 108 1010 1012 1014 1016
Radio Infrared Ultraviolet light
Table A: Wave propagation parameters Fig. B Wave travelling into optical films
vacuum medium
f f
c = lof v = lf
lo l lo/n
ko k = nko
c lo f lo 2 / l k
n
v lf l 2 / lo ko - Estimate n in Film 1, Film 2
- Film 1 is lossy, 2 lossless
Optcal Properties 2102308 17
(R2)
Optical anisotropy (9.14)
- most non-crystalline materials (glasses, liquids) and all cubic crystals are optically
isotropic (they “look” the same in all directions)
- crystals are different: n of crystals depend on direction of electric field in the
propagating light beam
- Optically anisotropic crystals are called bi-refringent because incident light beam
may be doubly refracted (Figs. 9.25, 9.26)
Uniaxial - Positive no ne
Ice 1.309 1.3105
ne no Quartz 1.5442 1.5533
Rutile (TiO2) 2.616 2.903
ANISOTROPIC
Uniaxial - Negative no ne
Calcite (CaCO3) 1.658 1.486
no ne Tourmaline 1.669 1.638
Lithium niobate (LiNBO3) 2.29 2.20
wiki/Birefringence
Biaxial n1 n2 n3
Mica (muscovite) 1.5601 1.5936 1.5977
Table 9.3 Principal refractive indices of some optically isotropic and anisotropic crystals
(near 589 nm, yellow Na-D line).
Optcal Properties 2102308 19
(R4)
n er
n (l ) e r ( f )
• Examples ?
=
er Material er(LF) er(LF)] n (optical)
Diamond 5.7 2.39 2.41 (at 590 nm)
Si 11.9 3.44 3.45 (at 2.15 mm)
SiO2 3.84 2.00 1.46 (at 600 nm)
Dielectric resonance How are these measured in practice?
electronic LF: kHz; e.g. by C-V measurement
dipolar HF: (Optical) 1015 Hz; Snell’s
- dispersion relations: interrelations of wave properties (l, f, v, n), most importantly n(l) ()
- dispersion occurs when pure plane waves of different wavelengths have different propagation
velocities, so that a wave packet of mixed wavelengths tends to spread out in space ()
- brief physics of dispersion (D1)
- the cause: imperfect light sources, they all have finite width l, or FWHM (D2)
- the effect: group velocity and group index (9.4) (D3)
- the results: pulse spread (), poor system performance (bit-error rate, BER )
- the remedy: zero dispersion (D4)
≠
dispersion in prism causes different
colors to refract at different angles, splitting
white light into a rainbow of colors
Optcal Properties 2102308 21
(D1)
Brief Physics of dispersion relation
n2 e r dispersion relation in a material with a single polarization
mechanism with a single resonant wavelength lo
N e
er 1
eo l2
e pinduced /
n l 1
2
l2 l2o
Ze 2
Ze x
pinduced
me 02 2
- in real crystals, atoms interact very complicated. In general, a material can have polarization
mechanisms each with a different resonance frequency. This leads to a semi-empirical dispersion
relation:
B1l2 B2 l2 B3l2
n (l ) A 2
2
2 2
l C1 l C2 l C3
B1,2,3, C1,2,3 : Sellmeier coefficients
Sources: Batop.com, Wiki
l 0.2767 [l in mm]
Dispersion occurs when pure plane waves of different wavelengths have different propagation velocities, so that
a wave packet of mixed wavelengths tends to spread out in space. (Wiki)
Light sources:
- broadband: Sun, incandescent – for general lighting
- narrowband: light-emitting diodes (LEDs), (LDs) – for communication
Dispersion occurs when pure plane waves of different wavelengths have different propagation velocities, so that
a wave packet of mixed wavelengths tends to spread out in space. (Wiki)
Information:
phase travels @ phase velocity (v)
Emax travels @ group velocity (vg)
Note that eyes/detectors measure intensity (E2)
v = c/n and = vk
vg =d /dk
E in vacuum: n = 1 (l independent)
v = c and = ck
vg = d /dk = c = phase velocity for all l’s
x
in a medium: n > 1 (l dependent)
c d c
v vg
E2 nl dk n l dn
dl
c
x vg Ng group index
Ng
Optcal Properties 2102308 24
The remedy: eliminate / minimise? (D4)
group index
dn
nl
dl
c ct g
Ng
vg L
Zero-dispersion dN g c dt g
dl L dl
dt g 1 dN g
Ldl c dl
Ex. 9.6: find the phase velocity, group index, and group velocity of light (1300 nm) travelling in a
pure silica glass.
n = 1.447 v = 2.07 108 m/s
Ng = 1.462 vg = 2.052 108 m/s
Optcal Properties 2102308 25
9.6 Snell’s law and TIR
Requirement for wave propagation = Trigonometry:
Constructive interference: wavefronts for
reflected and refracted (transmitted) waves
must be in phase with incidence wave
i&t =
n1 > n2
=
i&r
n2
sin 2 q i 1
q c sin 1 l n2
n1
penetration depth = 1/
Optical Fiber
Digital signal
Emitter Photodetector
Information Information
t Input Output
TIR n2
q q
Fiber axis
Core
n1
Light
ray Cladding n2
- the results (mainly reflection coefficients) are plotted in two example cases:
- internal reflection, when n1 > n2, see (F2)
- external reflection, when n1 < n2, see (F3)
- human eyes (and optical detectors) sense intensity (E2), not the magnitude of the
optical field (E), hence appropriate to plot reflectance and transmittance (F4)
- the equations provide mathematical guideline to the designs of some important
normal-incidence (qi = 0°) applications:
- low-reflection coating: aims to absorb all incident radiation, useful in solar cells
and photodetectors, see anti-reflection coating (ARC) (F6)
- high-reflection coating: aims to reflect all incident radiation, useful as mirrors,
see quarter wave stack (F7)
- various optical filters: low-pass, high-pass, bandpass (similar in principle to
electronic filters)
y
E t, Transmitted wave
y
kt
Evanescent n
2
wave qt = 90
o
qt
Et,
z E t,
n >n
x into paper Ei, ki qi qr E i, qi qr E r,
1 2
E r,
kr kr
E i, E i ,
Er, E r,
Governing
(a) qi <principles:
qc then some of the wave is (b) qi > qc then the incident wave suffers
A. Snell’s
transmitted law:dense
into the less n1 sin q1 n2 sin
medium. q2internal reflection. There is a decaying
total
Some of the wave is reflected. n wave into medium
evanescent n2
B. electromagnetism: B E// and B// E
c c
C. Boundary conditions:
Etangential (1) = Etangential (2)
n2
→ qi = qr and n Btangential (1) = Btangential (2); for non magnetic media
n1
Er , cos q i n 2 sin 2 q i Er , // n 2 sin 2 q i n 2 cos q i
/ r r// /
Ei , cos q i n sin q i 2 2 Ei , // n 2 sin 2 q i n 2 cos q i
Et , 2 cos q i Et , // 2n cos q i
/ t t // /
Ei , cos q i n 2 sin 2 q i Ei , // n 2 sin 2 q i n 2 cos q i
r 1 t ; r// nt // 1
(+, real)
(–, real)
= 0 @ qi = 0 (+, real)
Transmitted light in both internal and external reflection does not experience
phase shift (t is always +ve, qi < qc)
(main concern is reflected light for propagation)
Optcal Properties 2102308 31
Reflectance (R) and Transmittance (T) (F4)
2 2
Er , Er , //
R r and R// r//
2 2
2 2
Ei , Ei , //
2 2
n2 Et , n n2 Et , // n2
T 2 t and T//
2 2
2 2
t //
n1 Ei , n1 n1 Ei , // n1
Ex. 9.9
air glass Find reflection coefficients and reflectance in
each case
1 n 1.5
air/ARC = ARC/semic.
note: k k jk
c l f l 2 / l k N n – jK
n o o ko ko
v lf l 2 / lo ko
R,T A
(linear) Absorption Coefficient n refractive index k ko
K absorption index k ko
Lossless: E Eo exp j t kz Plane wave (extinction coefficient)
Lossy:
E Eo exp j t k jk z
Eo exp k z exp j t k z k' describes propagation:
phase velocity v = /k'
I E exp 2k z
2
Intensity:
lossless: k 0, n e r
EG
lossy: n jK e r' je r''
photon
energy n 2 K 2 e r' and 2nK e r''
EXP. determine R(l)
R
1 N
2
n – 1 K 2
2
n 12 K 2
from reflectance measurement at
normal incidence as a function of freq. 1 N
& get n – jK (l) from 9.7 (Fresnel)
Optical constants (n and K) can also be found from ellipsometry (a kind of reflection measurement, see
JA Woollam.com), the principle is based on polarization and angle of incidence (Fresnel’s equations)
Optcal Properties 2102308 38
(L3)
Setup for (n,K) measurements
Io z
photodetector
broadband lightsource
l beamsplitter (50:50)
It
monochromator
Ir material under test
Ir / Io , R It / Io
l , photon energy l , photon energy
R
R (n,K) K
n (k", K)
n
Ex
k Propagation
direction
z
Lattice absorption through a crystal. The field in the EM wave oscillates the ions, which
consequently generate "mechanical" waves in the crystal; energy is thereby transferred from
the wave to lattice vibrations.
Si 1.12 1.11 I
GMT
https://bilimfili.com/hiperfizik/hbase/atmos/blusky.html#c1 GMT + 7
wavelength (mm)
- Not shown, below 500 nm, sharply since photons excite electrons from VB CB (9.10)
- loss @ 1.5 mm (dB/km): 0.2 in 1979, now = 0.16, intrinsic limit. (Source: Tilley 2011)
Optcal Properties 2102308 46
Plastic optical fiber (POF) (A1)
Material
PMMA: Poly (methyl methacrylate)
(C5O2H8)n
Other names:
Acrylic glass, Plexiglas
Speed:
- light in space: c=3x108 m/s
- light in glass: 0.67c
- electrons in Cu: 0.01c
- electrons in Si: 0.001c
(vsat = 107 cm/s at 300 K)
Optcal Properties 48
Erbium doped fiber amplifier (EDFA) (A3)
- active region of EDFA system consists of 30-m section of fiber doped with Er3+ (Fig. 14.35a)
- how it works: weak optical signal enters (1), and after being pumped by laser diodes (LD) (2),
leaves as output (3) with increased intensity: input (1) + pump (2) output (3)
- material: Erbium (III) ion (Er3+), not atom. The electronic structure of Er3+ is [Xe] 4f11, the 4f-
shell is well shielded (by the outer 5s, 5p shells) from the environment (SiO2), thus energy levels
(not bands): ground state 4I15/2 (GS), and next 2 excited states 4I13/2, 4I11/2 (Fig. 14.35b)
- physics: LD 980nm shone (4) Er3+ excited from 4I15/2 to 4I11/2, but (5) quickly relaxes by non-
radiative radiation to 4I13/2 and stays there for a long time, when an input photon (1) l1480 nm
arrives, it entices the excited Er3+ (at 4I13/2) to return to GS by stimulated emission (6), think laser.
Thus, 1 photon in, 2 photons out. Gain!
- effectively, power transfers from LD (2) (5)
to output (3), which is an amplified version
of input (1)
(1) (3)
(4) (7)
(6)
(2)
(a) (b)
Incident Incident
light electrons
Heat Heat
(a) Photoluminescence (b) Cathodoluminescence
Phosphor
Activators or
luminescent centers
Al O
(e.g. Cr3+) 2 3
: Cr3+
Incident
light
Host matrix (e.g. Al2O3)
(c) A typical phosphor = host + activators
Photoluminescence, cathodoluminescence and a typical phosphor
halophosphate
Ca10F2P6O24 : (Cl−,Sb3+,Mn2+)
[1D]
h2
[1D] : En * 2
n2 [2D] [3D]
8m a
h 2 nx2 n y nz2
2
[3D] : E (nx , n y , nz ) * 2
2 2
8m a b c
Optcal Properties 2102308 54
(M5)