10.

Optics of metals - plasmons

Drude theory at higher frequencies
The Drude scattering time corresponds to
the frictional damping rate
The ultraviolet transparency of metals
Interface waves - surface plasmons
Plasmon excitations of metal
nanoparticles
Our guess from the last lecture
2 2 2
0
2 2 2 2
0
1 c c c
=
c c c
E E P
z t t
c

Recall the inhomogeneous wave equation:
As a guess, we replaced dP/dt with the current density
J (t) = o
0
E(t):
2 2
0 0 0
2 2 2
0
1 c c c c
= =
c c c c
E E J E
z t t t
c
o
4
0 0
0 0
1 = + ~

j
n j e
t
o o
c e c e
from which we found the complex refractive index:
large ~ = n k
When is this guess likely to be wrong?
Because o
0
is REAL, our guess, J (t) = o
0
E(t), implies
that the current is always in phase with the incident
electromagnetic wave!
Recall: in the Drude model, the electrons are free to
move - they are not bound to atoms by springs.
So, for low or moderate frequencies, this guess is ok.
But at a high enough frequency, it MUST fail.
2 2 2
0
2 2 2 2
0
1 c c c
=
c c c
E E P
z t t
c

So, we are back to the inhomogeneous wave equation.
what goes here?
The polarization when there is current
Lets go back to our forced oscillator model.
Newtons law F=ma gave us:
( )
( )
( )
2
2
0
0
2
2 e

= + I +
e e j t
e
e
d x t dx t
eE
x t
dt dt m
e
e
force due to the
incident light field
For a Drude metal, there is no spring
holding the electrons, so we take e
0
= 0.
( )
2
2 2
0
/
( )
2
(
=
(
I

e
Ne m
P t E t
j e e e
From this, we found
the polarization:
resonant frequency
of the spring
2
0
=
e
k
m
e
The plasma frequency
( )
2
2
/
( )
2
(
~
(
+ I

e
Ne m
P t E t
j e e
We nowuse this as a new and improved
guess: plug this in for the polarization term in
the wave equation.
Define a new constant, the plasma frequencye
P
:
2
2
0
=
P
e
Ne
m
e
c
( )
2
0
2
( )
2
~
+ I
P
P t E t
j
e
c
e e
Thus
Back to the wave equation
2
2 2 2 2
0 0 0
2 2 2 2 2 2
0
1
2
c c c c
= =
c c c + I c
P
E E P E
z t t j t
c
e
c
e e
But this is the same as a problem we solved earlier:
2
2 2
2 2 2 2
0
1
1 0
2
| |
c c
=
|
c + I c
\ .
P
E E
z j t
c
e
e e
This is the wave equation for a wave propagating in
a uniform medium, if we define the refractive index
of the medium as:
( )
( )
2
2
2
0
1
2
= =
+ I
P
n
j
c e
e
e
c e e
How does this compare to our earlier result?
For this new result, consider the low-frequency limit, e << I :
( )
2 2
0 0
2
1 1
2 2
| | | |
= ~ +
| |
+ I I
\ . \ .
P P
j
j
e e
c e c c
e e e
But in our last lecture, we found the Drude result:
( )
0 0
0
0 0
1 1
| |
= + = +
|
\ .
n j j
o o
c e c
c e c e
In the Drude model, we have , so thus:
2
0
=
e
Ne
m
t
o
2
0
0 0
=
e
Ne
m
o
t
c e c e
With our earlier definition of , we find:
2
2
0
=
P
e
Ne
m
e
c
2
2
0
1
2 2
=
I I
P
e
Ne
m
e
e c e
The two results are consistent at low frequency!
High frequency dielectric of metals
How does this dielectric function behave at higher frequencies?
( )
2
0
2
1
| |
~
|
\ .
P
e
c e c
e
For high frequencies, e >> I, we find:
The dielectric function becomes purely a real number.
And, it is negative below the plasma frequency and
positive above the plasma frequency.
Some numbers:
Recall from Drude theory, that t ~ 10
-14
sec, so I ~1/t ~ 10
14
Hz.
For a typical metal, e
P
will be 100 or even 1000 times larger.
(corresponding to the frequency of infrared light)
(corresponding to the frequency of ultraviolet light)
A plot of Re(c) and Im(c) for typical values:
imaginary part gets very small for high frequencies
real part has a zero crossing at the plasma frequency
real and imaginary parts are equal in magnitude at e = I
Dielectric function of metals
0 2000 4000 6000 8000 10000
0
-1
-2
-3
-4
-5
1
2
3
4
5
Frequency (cm
-1
)
c
(
e
)
/
c
0
Re(c)
Im(c)
linear scale
e
P
= 4000 cm
-1
I = 20 cm
-1
e
P
10
-3
10
-1
10
1
10
3
10
5
c
(
e
)
/
c
0
10
0
10
1
10
2
10
3
10
4
Frequency (cm
-1
)
log scale
e
P
Re(c)
Re(c)
Im(c)
I
10
5
10
-5
High frequency optical properties
( )
2
2
1 =
P
n
e
e
e
In the regime where e >> I, we find:
For frequencies below the plasma frequency, n is complex, so the
wave is attenuated and does not propagate very far into the metal.
For high frequencies above the plasma
frequency, n is real. The metal
becomes transparent! It behaves like a
non-absorbing dielectric medium.
reflectivity drops abruptly
at the plasma frequency
This is why x-rays can
pass through metal objects.
Another example: the ionosphere
the uppermost part of the
atmosphere, where many of
the atoms are ionized. There
are a lot of free electrons
floating around here
2
0
2 9 MHz = =
P
e
Ne
m
e t
c
For N ~ 10
12
m
-3
, the
plasma frequency is:
Radiation above 9 MHz is transmitted, while radiation at lower
frequencies is reflected back to earth.
Thats why AM radio broadcasts can be heard very far away.
Waves trapped at an interface
Consider a wave at the
interface between two
semi-infinite media.
Is there a solution to Maxwells equations describing a
wave that propagates along the surface?
c
1
c
2
z
x
z=0
We can guess a solution of the form:
( )
( )
( )
( )
1
1
1 1 1
1 1
,0,
0, ,0


=
=

z j kx t
x z
z j kx t
y
E E E e e
B B e e
k e
k e
(and similar for
medium #2)
subscript 1refers
to medium #1
This propagates along the interface, and
decays exponentially into both media.
(Note: this is not
a transverse
wavebut
thats ok)
Interface waves
In order to exist, the wave must satisfy Maxwells equations:
1 1 1 1 2 2 2 2
0 0
= =
y x y x
j B E j B E
c c
e e
k c k c
and also the continuity boundary conditions at z=0:
0 0 0 0
1 2 1 2
= = = =
= =
z z z z
y y x x
B B E E
It is easy to show that these conditions can only be satisfied if:
1 2
1 2
0 + =
c c
k k
Since k
1
and k
2
are always positive, this shows that
interface waves only exist if c
1
and c
2
have opposite signs.
We just showed: in a metal, c < 0 for frequencies less than e
P
.
Surface plasmon polaritons
surface plasmon polariton (SPP) - a surface wave moving
along the interface between a metal and a dielectric (e.g., air)
The electrons in the metal oscillate in conjunction with the
surface wave, at the same frequency. In fact, an SPP is
both an electromagnetic wave and a collective oscillation
of the electrons.
Surface plasmon sensors
Surface plasmons
are very sensitive
to molecules on
the metal surface.
Surface plasmons on small objects
Instead of considering a semi-infinite piece
of metal, what if the metal object is small?
e.g., a metal nanosphere
We can still excite a plasmon, but in this case it does not
propagate! The electrons just collectively slosh back and forth.
excess negative charge
excess positive charge
There is a restoring force on the
electron cloud! Once again, we
encounter something like a mass
on a spring, with a resonance
Surface plasmon resonance
2.8 nm copper
nanoparticles
Pedersen et al., J Phys ChemC (2007)
The sloshing electrons interact with light most strongly at the
resonant frequency of their oscillation.
gold nanoparticles give rise
to the red colors in stained
glass windows
Controlling the surface plasmon resonance
gold nano-shells
The frequency of the plasmon resonance can be tuned
by changing the geometry of the metal nano-object.
Halas group, Rice U.