Previous Lecture: (And On Shape, Size, Neighbors)

CREOL, College of Optics & Photonics, University of Central Florida
www.creol.ucf.edu
Previous lecture
- Light interaction with spherical particles: described in quasi electrostatic limit - Particles << exhibit dipolar oscillation mode (Frhlich mode) - Resonance depends on - N: large free electron concentration concentration, high resonance frequency - : long scattering lifetimes sharp resonance - H: large host polarizability low resonance frequency (and on shape, size, neighbors) - Noble metals give sharp resonances at visible frequencies - Plasmon resonance leads to enhanced abs. (and heating), scattering, E-fields
Today: Shape effects, finite size effects, particle-particle interaction
Optical Properties of Nanostructured Materials Spring 2010 - Class 4
Resonances in ellipsoidal particles

In the previous lecture we found that the extinction cross-section of a single spherical scatterer was given by:
The plasmon resonance condition was apparent since the denominator vanishes for M = -2H Note: M=metal, H=host. Often: in, out, m (metal), d (dielectric), OR m (matrix) Note: here represents the dielectric function, NOT the permittivity (check units) At this resonance, do we have .. - relatively small / medium / large oscillating dipole moment? - relatively small / medium / large extinction? - 90 / ~0 / -90 phase delay of Ein compared to the driving field? Dipole moment of isotropic np (*) follows from polarizability : For sub- spherical particle, polarizability is
( ) = ( ) E ( )
= 4 0 R 3
m + 2 m
2
(*) in isotropic environment!
OSE6650 Spring 2010 - Class 4: SPs on anisotropic particles
www.creol.ucf.edu

For ellipsoidal particles under illumination with E along one of the principal axes, the polarizability can be written in a similar form as obtained for spheres In this case the solution to the polarizability can be written in the form
3 =4 3 0 R
m m + L( m )
= m 1
1 L
with L a geometry dependent factor between 0 and 1 (shape factor) From this equation, it follows that resonance occurs when (or more precisely, when
m + L( m ) reaches a minimum - discuss)
For spheres, the geometrical factor L has a value L=1/3 Check: resonance when
= m 1 = 2 m which is what we had before 3 1
The geometry factor L can be calculated analytically (next slide)

Optical Properties of Nanostructured Materials Spring 2010 - Class 4 3

The shape factor L3 for polarization along the c axis can be calculated using the following integral:
b c a
a, b, and c are the semi-axes of the ellipse Where f(q) (q) is g given by y
For the derivation, see Bohren and Huffman Chapter 5

www.creol.ucf.edu
Resonance frequency vs. aspect ratio

For each particle shape and orientation one can calculate L// and L can find relation between (particle) and m (medium) for resonance
Elongated particles: Resonance requires that is more negative Drude tells you that this corresponds to a lower resonance freq.
Note: this is for Ag NOT related to the similar looking curve on the left!!
E
B&H page 344 B&H page 344
Note: infinite flat particle: resonance when = 0 (plasma frequency)

Resonance frequency vs. aspect ratio

Exercise: what aspect ratio do we need to give a copper particle in Si3N4 (n=2) to obtain a dipolar plasmon resonance at ~850nm, based on the provided values values
E
B&H page 344
www.creol.ucf.edu
Resonance frequency vs. shape - intuitive picture

We found: elongated particles illuminated with E along length have low res Resonance is due to internal field that acts as restoring force Field strength for small particles (electrostatic limit) described by Coulomb forces Field given by total coulomb force due to surface charge
Spherical particle: integrate force due to charge on hemispherical shell Total force for a given charge displacement dz = spring constant
Elongated particle of same length: distances the same (force per charge unaltered) but total surface area less reduced field for same dz Reduced field per dz reduced res
7
Extinction spectrum
Ellipsoidal particles: resonance depends on particle orientation relative to field A collection of ellipsoidal particles can show multiple p resonances Example: calculated extinction of randomly oriented Al nanoparticles using the dielectric function shown below Dashed line: spheres, one resonance Solid peaks: single spectrum of ellipsoids with 3 different main axes Note: extinction shows superposition of resonance peaks, not intermediate resonance frequencies ! Why?
B&H page 346
www.creol.ucf.edu
Example: extinction measurement on array of Au nanoparticles

White light source
Polarization filter
S L
Array
Monochromator Detector
figure: M.L. Brongersma
Sample: dense array of metal nanoparticles on glass slide Polarization along long axis (L) resonantly enhanced extinction at low Polarization along short axis (S) resonantly enhanced extinction at high
Example: extinction measurement on array of Au nanoparticles

Electron-beam lithography (EBL) (also available at CREOL)
Felidj et al., Appl. Phys. Lett. 82, 3095 (2003)
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Example: Resonance tuning by index modulation

Anisotropic refractive index will also lead to discrete resonances Example: gold nanoparticles in liquid crystal
Muller et al., Appl. Phys. Lett. 81, 171 (2002)

The effect of damping on the resonance linewidth

We had where M represents the imaginary part of the dielectric function of the particle. This imaginary part is related to electron scattering through (in Drude model) :
2 r " ( ) = p
p / = 2 2 + 1 + 2 2
2
Note that for M = 0 the cross section would approach infinity: damping affects the scattering cross section and the local field strength Discuss: what would happen if we place nanoparticle in gain medium ( negative) Plasmon decay is caused by electron-electron collisions and re-radiation (dipole emission) The rate at which the plasmon oscillation energy decays is
[ see e.g. T. Klar et al, Phys. Rev. Lett. 80, 4249 (1998) ]
h hom ( J )
short decay times or large damping correspond to large linewidth

www.creol.ucf.edu
Relaxation processes
Plasmon relaxation occurs through radiative and nonradiative processes Described by energy decay time T1 (or ) and field decay time T2 (dephasing time) The dephasing time T2 is related to the resonance width :
[ see e.g. T. Klar et al, Phys. Rev. Lett. 80, 4249 (1998) ]
T2 =
2h = 2 hom ( J )
The initial fast energy decay due e-h pair generation and e-e interactions followed by a slower process of electron-phonon coupling leading to the conversion or electronic kinetic energy into thermal energy
Snnichsen et al. - Phys. Rev. Lett. 88, 077402 (2002)
13
Relaxation processes
Starting point: no plasmon, electrons in thermal equilibrium with surroundings
EF
Energy
a)
b)
c)
d)
EF
Energy
EF
Energy
EF
Energy
EF
Energy gy
a) optical excitation conduction electrons collectively have increased energy [alternatingly kinetic and potential energy. Open question: corresponding k?] b) rapid field oscillation due to plasmon excites e-h pairs (=non-thermal distribution) c) e-e scattering produces hot electrons in quasi equilibrium d) e-phonon scattering eventually results in thermal equilibrium
www.creol.ucf.edu
Absorption by small Au particles intermediate size

Absorption of 30.6 nm Au particles
4
Absorption Efficiency
0 15 1.5 20 2.0 25 2.5
calculated using measured extinction bulk values of

30 3.0 35 3.5 40 4.0
energy (eV)
For large (but < ) particles, optical properties nanoparticles near resonance well described by electrostatic formula with bulk dielectric functions.
15
Damping in very small particles

Very small particles (d<10nm): electrons start to interact significantly with the particle surface, leading to additional damping due to surface scattering Effect becomes significant if particle diameter << mean free path
7 6 5 4 3 2
= bulk + A
total damping
vF a
Im Epsilon
Particle Size: 30 6 nm 30.6 6.9 nm
surface component
Here described in terms of Fermi velocity vf, diameter a, and electron scattering coefficient A Value for gold: vf 1.4106 m/s
1.5 2.0 2.5 3.0 3.5 4.0 4.5 Diameter of 14 nm: vf/a= 1014 s-1 energy (eV) Frequency of red light: 51014 s-1 Dielectric function of the metal particle is size dependent for small diameter
See M. Quinten, Zeitschrift fr Physik B, 211 (1996)
Discuss dielectric function near surface

16
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Example 1: calculated Al resonance vs. diameter
B&H page 338
Small particles: quasi-electrostatic limit OK, bulk dielectric function no longer accurate significant surface scattering increases and damping, resulting in General broadening for decreasing size
= bulk + A
vF a
17
Why no peak shift for very small particles? - intuitive picture

Small particle limit: electrostatics can be used to calculate forces Force due to charge q given by Coulomb force E =
q 4 0 r 2
Small particle: 1. charges closer force per charge increases as 1/r2 2. smaller surface area number of charges for fixed dz down as r2 Effects cancel resonance frequency ~ size independent for small r
www.creol.ucf.edu
Fields around finite size particle - beyond quasi electrostatic limit

Irradiation of a small object results in polarization and resulting scattering as well as absorption. General solution quite complicated. Total field given by
E 2 = Ei + E s
Maxwell equations for time harmonic fields:
Vector wave equation:
E + k 2E = 0
2
H + k 2H = 0
2
where k 2 = 2
Boundary conditions at the particle surface:
=0 E2 ( x ) E1 ( x ) n =0 H 2 ( x ) H1 ( x ) n
From the solutions, we can find the total energy flow outside the particle:
* * * * 1 1 S = Si + S s + S ext = 1 2 Re {Ei H i } + 2 Re {E s H s } + 2 Re {Ei H s + E s H i }
This problem has been solved analytically for spherical objects by Gustav Mie
Extinction by a sphere - Mie Theory

Solution makes use of the fact that one can construct functions that satisfy the vector wave equation based on a function that satisfies the scalar wave equation
These vector harmonic solutions are constructed from according to : First: solve the scalar wave equation Next: construct solutions to vector wave equation Scalar solutions: where h
emn = cos ( m ) Pnm ( cos ) zn ( kr ) omn = sin ( m ) Pnm ( cos ) zn ( kr )
Pnm are Legendre L d polynomials l i l and d zn are Bessel functions (see e.g. B&H Ch. 4)
Obtained vector functions form a complete basis set We can solve the scattering problem by describing the incident field, the internal field, and the scattered field in terms of N and M, and satisfying the boundary conditions Even solutions e lead to allowed E N, odd Optical Properties of Nanostructured Materials Spring 2010 - Class 4 solutions o lead to allowed E M
20
10
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Electromagnetic Normal Modes of a Sphere

M and N represent a collection of allowed field distributions inside the particle
Electric dipole p Magnetic g dipole p
Electric quadrupole Magnetic quadrupole
an and bn are the corresponding scattering coefficients resulting from satisfying the boundary conditions under plane wave illumination
Note: lines correspond to field lines on the sphere surface (!), not the field lines inside the sphere volume. Hence the curvature in the dipolar mode
Any field in the particle can now be described in terms of a superposition of excited normal modes of the sphere
polarization of particles not simply dipolar, but superposition of multipolar modes as found by Mie
Mie Theory: Cross Sections

Total far-field scattering and extinction of a finite size spherical particle follows from cross sections that can be calculated with Mie theory: Scattering and extinction under plane-wave illumination is composed of the scattering coefficients for all possible vector spherical harmonics
22
11
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Mie Theory: Cross Sections

Size dependence of multipolar plasmon frequencies Example: sodium resonance in air, shown for zero damping and damping = 1eV (----)
localized SP condition
Eur. Phys. J. Special Topics 144, 9399 (2007)
Fixed radius: mode order up frequency up (shorter plasmon wavelength) Increasing size: longer circumference and internal field down frequency down
Example 1: calculated Al resonance vs. diameter

Large particles : electrostatic limit no longer a good approximation
B&H page 338
finite phase delay between front and back of particle leads to excitation of multipolar modes
General broadening and red-shift of resonance for larger size Small particles : electrostatic limit OK, bulk dielectric function no longer accurate
significant g surface scattering g increases and damping, resulting in

General broadening for decreasing size
24
12
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Example 2: absorption by Au vs. diameter
B&H page 370
25
Summary: metal nanoparticle plasmons

Metal nanoparticles support collective charge oscillations
Absorption and scattering of light by small particles, Bohren & Huffman
- Electron oscillation amplitude strong near the nanoparticle plasmon resonance - Absorption (electronic collisions) strong near resonance - Optical scattering (dipole radiation) strong near resonance - Sharpest resonance for high AC conductivity materials -Sharpest resonance for particles with d > ~5nm (prevents surface damping) and d << (prevents multipolar excitations) - Resonance frequency depends on shape and dielectric environment
13
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Inter-particle coupling
Individual particle : resonance determined by size, shape, dielectric, metal charge displacements leads to surface charge restoring force resonance
Excitation by plane wave, vertically polarized, moving into page
Multiple particles : neighboring particles introduce additional field components modified restoring force modified resonance
This situation: neighbor in-phase and laterally displaced increased restoring force for same dz increased resonance frequency
Inter-particle coupling collective modes, dipole picture blue-shifted resonance
Transverse oscillation
Longitudinal oscillation
red-shifted resonance
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14
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Inter-particle coupling collective modes, Coulomb force interpretation

Transverse oscillation Coulomb forces add: blue-shifted resonance Note, at center of particle, neighbor-induced forces perfectly vertical Forces stronger near particle edges (closer to neighbor), and field lines not exactly vertical (see also previous slide)
Longitudinal oscillation
Coulomb forces subtract: red-shifted resonance
Important realization: for large, closely spaced particles, neighbor fields not homogeneous over particle volume higher order modes can be excited
Metal nanoparticle arrays made by e-beam lithography

50 nm Au particles on ITO coated glass
1 m
300 nm
Dense array of particle lines, so large fraction of surface area covered
extinction measurements possible

Do polarization dependent extinction measurements, and look for resonantly enhanced extinction peaks
Optical Properties of Nanostructured Materialswith Spring 2010 - Class 4 and Paul Maker, Jet Propulsion Laboratory (JPL) 30 Structures fabricated in collaboration Richard Muller
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Experimental observation of collective modes

transverse polarization
Maier et al., Phys. Rev. B 65, 193408 (2003)
1.0
0.8
T L
Extinction (a.u.)
0.6
0.4
0.2
Extinction measurements show presence of frequencyshifted collective resonances
0.0
2.0
2.1
2.2
2.3
2.5
2.6
31
Energy (eV)
Next: propagating modes in nanoparticle arrays

Nanoparticle arrays: - individual particles have specific resonance frequency - closely spaced particles show coupled oscillation modes - light propagation through coupled resonators - optical waveguides with mode confinement << - propagation length up to ~um length scale
32
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CREOL, College of Optics & Photonics, University of Central Florida

Today: Shape effects, finite size effects, particle-particle interaction

Optical Properties of Nanostructured Materials Spring 2010 - Class 4

Resonances in ellipsoidal particles

(*) in isotropic environment!

OSE6650 Spring 2010 - Class 4: SPs on anisotropic particles

CREOL, College of Optics & Photonics, University of Central Florida

Resonances in ellipsoidal particles

m + L( m ) reaches a minimum - discuss)

= m 1 = 2 m which is what we had before 3 1

The geometry factor L can be calculated analytically (next slide)

Resonances in ellipsoidal particles

For the derivation, see Bohren and Huffman Chapter 5

OSE6650 Spring 2010 - Class 4: SPs on anisotropic particles

CREOL, College of Optics & Photonics, University of Central Florida

Resonance frequency vs. aspect ratio

Note: infinite flat particle: resonance when = 0 (plasma frequency)

Resonance frequency vs. aspect ratio

Optical Properties of Nanostructured Materials Spring 2010 - Class 4

OSE6650 Spring 2010 - Class 4: SPs on anisotropic particles

CREOL, College of Optics & Photonics, University of Central Florida

Resonance frequency vs. shape - intuitive picture

Optical Properties of Nanostructured Materials Spring 2010 - Class 4

B&H page 346

OSE6650 Spring 2010 - Class 4: SPs on anisotropic particles

CREOL, College of Optics & Photonics, University of Central Florida

Example: extinction measurement on array of Au nanoparticles

Example: extinction measurement on array of Au nanoparticles

Optical Properties of Nanostructured Materials Spring 2010 - Class 4

OSE6650 Spring 2010 - Class 4: SPs on anisotropic particles

CREOL, College of Optics & Photonics, University of Central Florida

Example: Resonance tuning by index modulation

Muller et al., Appl. Phys. Lett. 81, 171 (2002)

The effect of damping on the resonance linewidth

short decay times or large damping correspond to large linewidth

OSE6650 Spring 2010 - Class 4: SPs on anisotropic particles

CREOL, College of Optics & Photonics, University of Central Florida

Snnichsen et al. - Phys. Rev. Lett. 88, 077402 (2002)

Optical Properties of Nanostructured Materials Spring 2010 - Class 4

OSE6650 Spring 2010 - Class 4: SPs on anisotropic particles

CREOL, College of Optics & Photonics, University of Central Florida

Absorption by small Au particles intermediate size

0 15 1.5 20 2.0 25 2.5

calculated using measured extinction bulk values of

Optical Properties of Nanostructured Materials Spring 2010 - Class 4

Damping in very small particles

Particle Size: 30 6 nm 30.6 6.9 nm

Discuss dielectric function near surface

Optical Properties of Nanostructured Materials Spring 2010 - Class 4

OSE6650 Spring 2010 - Class 4: SPs on anisotropic particles

CREOL, College of Optics & Photonics, University of Central Florida

Example 1: calculated Al resonance vs. diameter

B&H page 338

Optical Properties of Nanostructured Materials Spring 2010 - Class 4

Why no peak shift for very small particles? - intuitive picture

OSE6650 Spring 2010 - Class 4: SPs on anisotropic particles

CREOL, College of Optics & Photonics, University of Central Florida

Fields around finite size particle - beyond quasi electrostatic limit

Maxwell equations for time harmonic fields:

Vector wave equation:

* * * * 1 1 S = Si + S s + S ext = 1 2 Re {Ei H i } + 2 Re {E s H s } + 2 Re {Ei H s + E s H i }

Extinction by a sphere - Mie Theory