4.

Optical properties of materials

Insulating media (dielectric) : Lorentz model Conducting media (Metal, in free-electron region) : Drude model Conducting media (Metal, in bound-electron region) : Drude-Sommerfeld model Extended Drude model (Lorentz-Drude model)

D( ) = 0 r ( ) E ( )

(spatially local response of media)

r ( )

: relative dielectric constant = relative permittivity = dielectric function

Lets start from Maxwell equations

(external )

(external )

Flux densities in a medium Total electric flux density = Flux from external field + flux due to material polarization

= permittivity of material in most of optical materials.

Ampere-Maxwells Law

Stokes theorem (very general)

Faradays Law (Faraday 1775-1836)

EM wave Equation in bulk media (, )

: EM wave equation in bulk media without net charge ( =0 and =0)

EM waves in dispersive media : =(), =()

Relation between E and P (J) is dynamic: In ideal case, assuming an instantaneous response,

But, in real life,

Response to E is DISPERSIVE

P(r,t) results from response to E over some characteristic time : Function x(t) is a scalar function lasting a characteristic time

Convolution theorem

Therefore, the temporally dispersive response of a medium induces a frequency dependence in permittivity.

A. Propagation in insulating media (dielectric : P, J = 0)

Consider a linear, homogeneous, isotropic medium .

Note 3 : In inhomogeneous media:

: all the materials properties resulting from P

2 E 1 2 E E = 0 0 r 2 = r 2 2 t c t
2

: EM wave equation in insulating media (dielectric) ( linear, homogeneous, isotropic, J=0, =0 , and =0)

The wave equation is satisfied by an electric field of the form of:

E = E0 exp i k r t

k = r
2

2
c
2

(dispersion relation), where r = 1 + ( )

B. Propagation in conducting media (free-electron region: J, P = 0)

Consider an ideally free electron (not bounded to a particular nucleus) Drude model

linearly proportional to E:

J=E

is the conductivity

1 2E E E= 2 2 + c t 0 c 2 t
2

: EM wave equation in conducting media (free-electron region) ( linear, homogeneous, isotropic, P=0, =0 , and =0)

The wave equation is satisfied by an electric field of the form of:

E = E0 exp i k r t

2 2 k = 1+ i = r ( ) 2 (dispersion relation) 0 c 2 c ( ) r ( ) = 1 + i
2

C. Propagation in conducting media (bound-electron region: J, P = 0)

Consider a bounded electron (not ideal free-electron due to interband transition) Modified Drude model Quasi-free-electron model Drude-Sommerfeld model

For the noble metals* (e.g. Au, Ag, Cu), the filled d-band close to Fermi surface causes a residual polarization, Pb, due to the positive back ground of the ion cores.
*In physics the definition of a noble metal is strict. It is required that the d-bands of the electronic structure are filled. Taking this into account, only copper, silver and gold are noble metals, as all d-like band are filled and don't cross the Fermi level.

Cu29 : 1s2 3d10 4s1

Ag47 : 1s2 4d10 5s1

Au79 : 1s2 5d10 6s1

Al13 : 1s2 3s2 3p1 (different)

*Interband transition : excitation of electrons from deeper bands into the conduction band

Pb = 0 b E P E Pb induces internal current density : J b = b = 0 b t t

Pb
also linearly proportional to E:

2 Pb J 1 2 E 1 2E E = 2 2 + 0 2 + 0 = 2 2 + 0 Jb + J t t c t t c t
2

1 2 E b 2 E E : EM wave equation in conducting media (bound-electron region) E= 2 2 + 2 2 + c t c t 0 c 2 t ( linear, homogeneous, isotropic, =0 , and =0)
2

The wave equation is satisfied by an electric field of the form of:

E = E0 exp i k r t

2 2 k = 1 + b + i = r ( ) 2 0 c 2 c ( ) r ( ) = + i [ = 1 + b ( )]
2

Now, how to determine

(), (), and b() ?

Microscopic origin of -response of matter

Professor Vladimir M. Shalaev, Univ of Purdue

Classical Electron Oscillator (CEO) Model = Lorentz model

Applied external electric field No external field Ex

Electron cloud

+
The equation of motion of the oscillating electron, d2r dr m 2 = Fr (r ) + F (v ) + FE ( E ) = C r m e Ex dt dt m : effective mass of each electron 1 = : dampling constant (or, collision frequency) ( is known as the relaxation time of the free electron gas) ( is typically 100 THz = 1014 Hz)

r(t)

Ex

FE

Fr

r(t)

A.

() of insulating media (dielectric : P, J = 0)

A. Insulator

A. Insulator

A. Insulator

A. Insulator (single atomic gas)

Assume j s are the same for all atoms

( ) = N j

A. Insulator (single atomic gas)

A. Insulator (single atomic gas)

A. Insulator (realistic gas with different atoms)

A. Insulator (solids)

A. Insulator (solids)

Local field at an atom

- !

A. Insulator (solids)

e2 1 2 j = m 2 i o j

The Polarizability of a solid with volume V given by the Clausius-Mossotti relation is

solid

r rembed = V N j j = V 0 embed r + 2 r j
3

embed =V embed + 2

embed = ( 4 a ) if the medium is a sphere with radius a. + 2 embed

A. Insulator (solids)

For a simple case when Cj = C for all atoms in solid,

N = 1 N
j j j 1 3 j j

where
j

e2 1 2 j = m 2 i o j

and 2 = j

Cj m

C m

Ne 2 1 N = = 1 1 3 N m o C Ne 2 2 m 3m i 0
2 p C Ne 2 2 ( ) = 2 , where o m 3m o 0 2 i

This is the same form as the single atomic gasses, except the different definition of 0.

In general when Cj are not identical,

( ) =
j

2 f j p
2 j

2 i j

fj

is the oscillation strength (the fraction of dipoles having j.

B. Drude model

B.

() in free-electron region: Drude model = Free-electron model

Drude model : Lorenz model (Harmonic oscillator model) without restoration force (that is, free electrons which are not bound to a particular nucleus)

The equation of motion of a free electron (not bound to a particular nucleus; C = 0), d2r m dr m 2 = C r eE dt dt
Lorentz model (Harmonic oscillator model)

If ====> m C=0

dv + m v = e E dt

( =

: relaxation time 1014 s )

Drude model (free-electron model)

C A The current density is defined : J = N e v 2 = s im 2 m

dv m + m v = e E dt

N e2 dJ +J = E dt m

B. Drude model

N e2 dJ +J = E dt me
Assume that the applied electric field and the conduction current density are given by : E(r ) = E0 ( r ) exp ( i t ) J (r ) = J 0 (r ) exp ( i t )
Local approximation to the current-field relation

Substituting into the equation of motion we obtain : d J 0 exp ( i t ) dt

+ J 0 exp ( i t ) = i J 0 exp ( i t ) + J 0 exp ( i t )

N e2 = E0 exp ( i t ) me Multiplying through by exp ( +i t ) : N e2 ( i + ) J 0 = E0 , me

or equivalently

N e2 ( i + ) J = E me

 N e2 ( i + ) J = E me
N e2 For static fields ( = 0 ) , J = E = 0 E , where m For the general case of an oscillating applied field : 0 J = E = ( ) E , 1 ( i / ) 0 N e2 / m ( ) = : dynamic conductivity = 1 ( i / ) i

B. Drude model

N e2 0 = : static conductivity m

r ( ) = 1 + i

0 c 2 0 0 c 2 0 i 0 c 2 0 r ( ) = 1 + i =1+ i = 1 2 +i i 1 ( i / ) 1 ( i / ) N e2 2 N e2 2 2 The plasma frequency is defined , p = 0 c 0 = c 0 = m 0 m N e2 , = r ( ) = 1 2 + i m 0

2 p 2 p

( ) 0

B. Drude model

Note : Dynamic conductivity ()

r ( ) = 1 + i ( ) 0

( ) =

0 1 ( i / )

For very low frequencies, ( ) << 1,

( ) ~ 0 : purely real and the electrons follow the electric field .

As the frequency of the applied field increases, the inertia of electrons introduces a phase lag in the electron response to the field , and ( ) is complex. For very high frequencies, ( ) >> 1,

( ) ~ i 0 / : purely imaginary, J i ( 0 / ) E = ei

( ) ( / ) E

and the electron oscillations are 90 out of phase with the applied field .

B. Drude model

Dielectric constant of free-electron plasma (Drude model)

2 2 p p = 1 2 +i r ( ) = 1 2 + 2 3 + 2 + i 2 p

N e2 = 0 c 0 = = m 0
2 p 2

N e2 0 = : static conductivity m

(1) For an optical frequency, visible >>

2 2 p p r ( ) 1 2 + i 3 / 2 2 p p = 1 2 + i 3

(2) Ideal case : metal as an undamped free-electron gas

no decay (infinite relaxation time) no interband transitions
2 p r ( ) r () = 1 2 0

B. Drude model

Note : What is the actual meaning of p

If the electrons in a plasma are displaced from a uniform background of ions, electric fields will be built up in such a direction as to restore the neutrality of the plasma by pulling the electrons back to their original positions. Because of their inertia, the electrons will overshoot and oscillate around their equilibrium positions with a characteristic frequency known as the plasma frequency.

E s = o / o = Ne ( x ) / o : electrostatic field by small charge separation x

x = xo exp( i p t ) : small-amplitude oscillation

d 2 ( x ) m = ( e ) E s 2 dt m 2 p = Ne 2

2 p

Ne 2 = m o

Note : plasma wavelength ,

p =

2 c

B. Drude model

Note : What happens in () when

2

p ?

2D E = ( E ) E = 0 2 (assume J = 0) t k (k E ) k E = (k , )
2

2
c
2

: E = E0 e j ( k r t )

(1) For transverse waves, (2) For longitudinal waves,

kE = 0
k (k E ) k 2 E = 0

k 2 = (k , )

c2 (k , ) = 0

Therefore, at the plasma frequency = p,

(k , = p ) = 0

D = 0 = 0E + P

E is a pure depolarization field (No transverse field strength in media). The quanta of these longitudinal charge oscillations are called plasmons (or, volume plasmons) Volume plasmons do not couple to transverse EM waves (can be only excited by particle impact)

B. Drude model

Note : What happens in () when

p ?
0

optical potential Incident energy

K inc = k02

(N. Garcia, et. Al, Zero permittivity materials, APL, 80, 1120 (2002))

If ( ) 0, K inc V

, the incident wave is completely reflected.

Wave propagation in this material can happen only with phase velocity being infinitely large satisfying the static-like equation
(A. Mario, et. Al, Epsilon-near-zero metamaterials and electromagnetic sources: Tailoring the radiation phase pattern, PR B, 75, 155410, 2007)

C. Drude-Sommerfeld model

C. b() in bound-electron region : Drude-Sommerfeld model

= Quasi-free-electron model

r ( ) = + i

( ) 0
2 p

[ = 1 + b ( ),

usually 1 10]

2 2 p p = 2 +i r ( ) = 2 2 3 + 2 + i +

gold

silver

Plasmons in metal nanostructures, Dissertation, University of Munich by Carsten Sonnichsen, 2001

C. Drude-Sommerfeld model

Measured data and modified Drude model for Ag:

2.48 eV
50

1.24 eV

0.62 eV

Drude model:

"
0

-d

2 2 p p ' = 1 2 , "= 3

-50

-100

Measured data: ' " ' Drude model: ' Bound SP mode : m < -d " Modified Drude model: '
200 400 600 800 1000 1200 1400 1600 1800

Modified Drude model:

2 2 p p '= 2 , "= 3

Contribution of bound electrons

-150

Wavelength (nm) Wavelength (nm)

500 nm 1000 nm 1500 nm

For Ag, = 3.7

p = 9.1 eV

For Ag, good matched bellow 2.5 eV

C. Drude-Sommerfeld model

Lets compare the modified Drude model with experimental measurement

2 2 p p r ( ) = 2 2 + i 3 + + 2

P. B. Johnson and R. W. Christy, Optical constants of the noble metals, Phys. Rev. B, 6, pp. 4370-4379 (1972).

Regions of interband transitions

Not good matched in interband regions!

Need something more.

C. Drude-Sommerfeld model
P. B. Johnson and R. W. Christy, Optical constants of the noble metals, Phys. Rev. B, 6, pp. 4370-4379 (1972).

D. Extended Drude model

D. bound-electron region : Extended Drude (Drude-Lorentz) model

Alexandre Vial, et.al, Improved analytical fit of gold dispersion: Application to the modeling of extinction spectra with a finite-difference time-domain method, Phys. Rev. B, 71, 085416 (2005).

The Drude-Lorentz model consists in addition of one Lorentz term to the modified Drude model. Since the Lorentz terms of insulators have a general form of
2 p For gold (Au), r ( ) = 2 + i

( ) =
j

f j 2 p

2 2 i j j

2 L 2 ( 2 ) + i L L

Excellent agreement within 500 nm ~ 1 m for gold (Au)

In summary :
Lorentz model for dielectric (insulator)

N ( ) = 1 + 1 N
j j j 1 3 j j
2 p

,
j

2 p / N j j = 2 , j 2 i

2 = j

Cj m

Drude model for metal in free-electron region

2 2 p p = 1 2 +i r ( ) = 1 2 + 2 3 + 2 + i

Modified Drude model for metal in bound-electron region

2 2 p p = 2 +i r ( ) = 2 2 3 + 2 + i + 2 p

Extended Drude (Drude-Lorentz) model

2 p r ( ) = 2 + i

2 L 2 ( 2 ) + i L L

Also, keep in mind..