Linear and Nonlinear Optics with

a Single Metal Nanoparticle

Natalia Del Fatti

FemtoNanoOptics Group
LASIM, Lyon - France
 Outlook

I. Introduction: optical response of metal nanoparticles

- Properties of spherical nanoparticles: Mie theory

- Size, shape and environment effects

II. Linear Optics: detection and spectroscopy of a single metal nanoparticle

- Far-field detection of a single nano-object

- “SMS” : Spatial Modulation Spectroscopy
- Optical characterization of a single nano-object

III. Nonlinear Optics: ultrafast dynamics of a single metal nanoparticle

- Femtosecond time resolved pump-probe technique

- Electronic and Vibrational response (acoustic oscillations)
Metal Nanoparticles... and colors

Metallic particles in glasses:

stained glass windows

Chartres cathedral - France

(red color: gold nanoparticles in glass)
 from IV ... to XXI century

Metallic particles in glasses: Ag Au

jewelry, ornament

Ancient cup (Central Europe)

Lycurgus Cup: a Roman Nanotechnology

Roman Era (4th Century A.D).
It appears green in reflected light
...and red in transmitted light.
 Metal Nanostructures

Metallic nanostructured materials :

- Physical and chemical synthesis,

different shapes, different matrices
(solid, liquid, deposited, ...)

- Intermediates between bulk / molecular systems

D = 40 nm : ~ 2 million atoms
D = 20 nm : ~ 250 000 atoms
D = 4 nm : ~ 4000 atoms
D = 2 nm : ~ 250 atoms
100 nm D = 3 nm : same number of atoms at the surface / core

- Specific properties, « Small is different »

Confinement effects (dielectric and quantum)

- Applications in optics, chemistry, biology,...

 Part I

Introduction: optical response of metal nanoparticles

- Spherical nanoparticles: Mie theory

- Dielectric constant of a metal
- Size, shape and environment effects

Linear Optics: detection and spectroscopy of a single metal nanoparticle

Nonlinear Optics: ultrafast dynamics of a single metal nanoparticle

 Optical response of metal nanoparticles

• Experimental studies: characteristic length → optical wavelength λ

small objects (<< λ): M. Faraday (Philos. Trans. R. Soc. 147, 145 (1857))
• Theoretical model:
- Absorption/Scattering by a nano-sphere
→ Mie theory (Am. Phys. (Leipzig) 25, 377 (1908))

- Small nano-spheres: quasi-static approximation

→ generalization: - nano-ellipsoids
- core-shell particles
- Numerical calculations

F. Bohren & D. R. Huffman, Absorption and Scattering of Light by Small Particles, John Wiley (1998)

U. Kreibig & M. Vollmer, Optical Properties of Metal Clusters, Springer Verlag, Berlin (1995)
 Optical response of a nano-object

ES

ε(ω) Spherical dielectric inclusion in a

Ee R εm dielectric matrix: optical response?

Ei Constituting materials:
dielectric constants

- Nano-sphere with radius R = D/2 and dielectric constant: ε = ε1 + iε2

in a non absorbing homogeneous dielectric environment: εm (real)
- Incident e.m. field: Ee (He) → scattered field: ES (?)
→ internal field: Ei (?)

- Cross sections (?) : scattering σs (scattered power PS = σS Ie)

absorption σa (absorbed power Pa = σa Ie)
extinction σe = σs + σa
 The nano-sphere: Mie theory
Electromagnetic problem:
- Maxwell’s equations
- Boundary conditions: continuity of E et H parallel to the surface
(and D et B orthogonal)
E ∧ n =cste ; H ∧ n =cste n
Ee + Es
- Incident field: linearly polarized plane wave Ei

E e = xˆ Ae e i ( kz −ωt ) + cc εm ε(ω)

But: mathematically complex:

- nanosphere: spherical symmetry → boundary conditions: spherical coordinates
- e.m. field: plane wave, Cartesian coordinates
Solution: development of the fields in spherical harmonics
→ internal and scattered electromagnetic field
⇒ σa et σs (and σe) expressed in terms of spherical Bessel functions
⇒ power series expansion in D / λ → numerical calculations
 Small size D << λ: dipolar approximation

Small size: D < λ/10 (~ 30 nm) Ei = x̂Aiei(kz − ωt) + cc

→ lowest order development

∆Φ = 0
of Mie theory (dipolar) z
⇔ quasi-static approximation Φi = −Aix

E e = xˆ Ae e i ( kz −ωt ) + cc with kz-ω t constant over the sphere

→ incident e.m. field constant over the nanosphere (at each time)

Electrostatic problem: much simpler → scalar potential

Poisson’s equation: ∆Φ = 0
∂ (Φ e + Φ s ) ∂Φ i
surface continuity: Φe + Φ s = Φ i ; εm =ε
∂r ∂r
- incident: Φ e = − Ae x
3ε m 3ε m
- internal: Φ i = − Ae x → internal electric field E i = E = f (ω ) E e
ε + 2ε m ε + 2ε m e

Proportionality factor f : local field factor (or dielectric confinement factor)

 Small size: quasi-static approximation

p.r ⎡ ε − εm ⎤
- scattered: Φs = with p = 3ε mε 0Vnp ⎢ ⎥ Ee
4πεmε0r3 ⎣ ε + 2ε m ⎦

→ scattered field: induced dipole p at the sphere center

x
Simple interpretation
Ee z
k p
Ee

electrons y

Displacement of electrons (-) / (+) lattice ions (fixed)

→ two displaced charged spheres ⇔ dipole (outside field)
→ oscillating dipole (dipolar approximation), electron oscillation at ω
+ restoring force (→ resonance)

→ large size: retardation effect (non uniform field over the sphere)
 Optical response of a nano-sphere: cross-sections
2
24π3Vnp
2
ε − εm
- Scattering cross-section: σs = ε 2m
λ4 ε + 2ε m

2
→ proportional to the square of the nano-sphere volume Vnp
- Absorption cross-section: 18πVnp ε2
σa = ε3m/ 2
λ ε + 2ε m
2

→ proportional to Vnp
• for small nano-spheres, absorption dominates:
σe ≈ σa >> σs (σs / σa ∝ (D/λ)3)
2
• both cross-sections depend on ε + 2ε m

→ ε2 weakly dispersed:
Resonance for ε1 + 2εm = 0 ⇒ ε1 < 0 → metals
→ Surface plasmon resonance
Dielectric confinement effect (resonant collective oscillation)
 Dielectric constant of bulk (noble) metals

Ag Parabolic conduction band:

h 2k 2
EF E (k ) =
2me

⇓
E
B.C.

EF

k
bandes d
Métal Structure a (Å) ne (x 1022 cm-3) me/m0 EF (eV)
Ag [Kr] 4d10 5s1 4.08 5.86 1 5.49
Au [Xe] 4f14 5d10 6s1 4.07 5.90 1 5.53
Cu [Ar] 3d10 4s1 3.61 8.47 1.5 4.67
 Dielectric constant of bulk (noble) metals
• Optical absorption : occupied to unoccupied states
- interband transitions:
C.b.
d electron state → conduction band state (E > EF)
EF
⇒ threshold hω > hΩib intraband
interband transitions
Métal Ag Au Cu
transitions
hΩ ib (eV) 3.9 2.4 2.1
d-bands
UV - VIS
- intraband transitions: Drude model ε2
⇒ ε2 ∝ 1/τ collision assisted (phonon) 0

Ag
• Dielectric constant of a noble metal

ε2
ε1
ε(ω) = εb(ω) − ωp2 ω(ω + i τ ) -20 6 ib
ε1
ε1 ; 4

2 ib
ε2
bound electrons free electrons 0
(interband) -40
(intraband) 2 4 6

( with ω 2p = ne e 2 / ε 0me ) 1 2 3
h ω ( eV )
4 5 6
 Dielectric constant of nanoparticles: confinement effects
Metal nanoparticle (D> 2nm ~ 250 atoms): “Small solid” Cond.band

Dielectric function of the confined metal: EF intraband

interband transitions
- Intraband contribution: transitions

• classical model: d-bands

electron mean free path: l ≈ vFτ ≈ 30 nm (vF ≈ 1.4 106 m/s, τ ≈ 10-20 fs)
l comparable to D → electrons-surface interaction time: ∝ D/vF

ε (ω ) = ε b (ω ) − ω 2p ω (ω + i τ nano )

with 1/τnano = 1/τ + 2g vF/D (g ≈ 1)

• quantum mechanics: → transition between confined states

(k is no more a good quantum number)
- Interband contribution:
non modified down to D > 2nm (experimental)
 Surface plasmon resonance: noble metals
ε1 + 2εm = 0 → Surface plasmon resonance: bound electrons
Frequency: ΩR = ω p ε 1b (Ω R ) + 2ε m environment
increase with size decrease (surface: g)
1 Ω 3R overlap with interband transitions:
Width: Γ= + ε 2ib ( Ω R )
τ nano ω 2p broadening
Wavelength (nm) Wavelength (nm)
700 500 300 800 700 600 500 400
10 10
ε2 ε2
0 0

-2 ε m -2 ε m
-10 -10
ε

hΩ R ε1 + 2εm = 0 hΩ R
-20 -20
ε1 ε1

3 0.10
Ag Au
αL (OD)

D = 13 nm D = 10 nm
2 h Ω ib
Extinction

0.05 ____ experimental

1 h Ω ib - - - - computed

0 0.00
2 3 4 1.5 2.0 2.5 3.0
h ω (eV) hω (eV)
 Surface plasmon resonance: noble metals
24π 3Vnp
2
2 ε − εm
2 18πVnp 3 / 2 ε2
Scattering: σs = εm << absorption: σe = εm
λ 4 ε + 2ε m λ ε + 2ε m 2
400
Ag in glass Au in glass
3000 D = 20 nm D = 20 nm
300
absorption
(nm )

absorption

(nm )
2

2
2000 scattering scattering
200

σa ; σs
σa ; σs

x100
1000 x10 100

0 0
350 400 450 500 500 600 700 800
Wavelength (nm) Wavelength (nm)
Ag Au
 Deviation from the dipolar (quasi-static) approximation

Ee Ei = x̂Aiei(kz − ωt) + cc

k large size: retardation effect

∆Φ = 0
non uniform field over the particle
Φi = −Aix

+
+ + - +
+ + ...
- - + -
-
electrons dipole quadrupole

Displacement of electrons / lattice ions

→ Multipolar expansion of the nanoparticle response

 Surface plasmon resonance: size effect
Wavelength (nm) hω (eV)
3.5 3 2.5 2
400 350 300
0.2
Na - Vacuum
D=40nm Ag - Vacuum 4
(nm )

D = 40 nm
-1

D=20nm g=1
D = 80 nm

σa (10 nm )
D=10nm 3

2
D = 120 nm
D=5nm

4
D = 160 nm
3

2
; σe / D

0.1 D = 200 nm

1
3
σs /D

20
0.0
3.0 3.5 4.0

σe (10 nm )
2
hω (eV)

4
• Dipolar approximation (few nm - few 10 nm): 10
- ΩR size independent
- width size (electrons-surface interaction)
• Mie theory (D ≥ 30-50 nm): 0
400 500 600 700
- red shift
- broadening (radiative damping) Wavelength (nm)
- multipolar resonances
 Surface plasmon resonance: environment effect

Nanoparticles in vacuum (εm = 1), water (1.77), silica (2.15) or alumina (3.1)

ΩR ≈ ω p ε 1b (Ω R ) + 2ε m

Wavelength (nm) Wavelength (nm)

600 500 400 300 800 700 600 500 400

1.0 Ag - D = 26 nm Au - D = 20 nm

εm=1
α (normalized)

εm=1,77
εm=2,15
0.5 εm=3,1

0.0
2 3 4 2.0 2.5 3.0
hω (eV) hω (eV)
 Surface plasmon resonance: environment effect

Gold colloidal solution (different solvents)

S. Underwood and P. Mulvanay, Langmuir 1994
Au, D ~ 16nm

Single nanoparticle (scattering)

Ag deposited on SiO2 + oil oil removed

dark blue: spheres 50-90 nm
light blue: hexagon nanoparticles J. J. Mock, D. R. Smith and S. Schultz
red: triangles Nano Letters 2003
Environment sensitivity → local nanosensors (bio-sensors)
 Surface plasmon resonance: shape effect
Small ellipsoids
z

c a x
π
quasi-static
8 3 2 2
V ε ε
approximation
np m − ε
2
(Mie-Gans),
σ si = m b
3λ4
for light polarized ε + (1 −the
Lialong εm i :
Li )axes y

2πVnpε m
3/ 2
ε2
σ ei = → Resonances ε 1 ( Ω iR ) + (1 / Li − 1)ε m = 0
λ Li ε + (1 − Li )ε m
2

Wavelength (nm)
Li : geometrical factors 700 500 300
depending on the aspect ratio
1.0
Ag - Prolate
- Sphere: Li = 1/3 (∑ Li = 1)
i

Ensemble of randomly
X Y,Z
σe
oriented ellipsoids (density N): 0.5

N
σ e,s = ∑
3 i
σ ei , s
0.0
2 3 4
→ Tuning the SPR spectral position hω (eV)
 Surface plasmon resonance: other shapes
Numerical approaches:

• Discrete Dipole Approximation (DDA), Goodman, Draine & Flatau, Opt. Lett. 1991
→ breaking up particle into small volumes, each of which carry dipole moment
• Finite Element Method (FEM), ex. COMSOL Multiphysics software
→ numerical solution of differential equations
• ...
external E-field enhancement contours
at 770nm → tip effect
Ag prisms

Ag prisms, thickness 16 nm. DDA calculations with a 2 nm K. L. Kelly et al,

cubic grid (for snip = 0: 68 704 dipoles are used) J. Phys. Chem. B 2003
 Practical Work...

Licurgus Cup

Question 1: Why does it appear

green or red depending on the
illumination conditions ?

Question 2: What is the size of

the nanoparticles ??

Gold nanospheres in glass

1.0 1.0

Scattering Absorption

σa (arb. units.)
σs (arb. units.)

0.5 0.5
Hint ...

0.0 0.0

400 500 600 700 800 400 500 600 700 800

Wavelength (nm) Wavelength (nm)

 Part II

Introduction: optical response of metal nanoparticles

Linear Optics: detection and spectroscopy of a single metal nanoparticle

- Far-field experimental techniques

- Optical signature: Gold nanospheres
- Shape effect: Gold nanorods

Nonlinear Optics: ultrafast dynamics of a single metal nanoparticle

 Optical study of a single metal nanoparticle

Ensemble measurement: 104 to 106 particles

⇒ Size and shape fluctuations ⇒ Single nano-object study

Non luminescent object: → Detection of light scattering or absorption

♦ Near field: local environment perturbation
T. Klar et al., Phys. Rev. Lett. 1998

♦ Far field: focused beam 300 - 500 nm → diluted sample ( < 1 particle / µm2 )
- Scattering (∝ V2 ; size ≥ 20 nm): → Dark field microscopy
C. Sönnichsen et al., Appl. Phys. Lett. 2000, New J. of Phys. 2002
(Heterodyne detection) K. Lindfords et al. Phys. Rev. Lett. 2004

- Absorption (∝ V ; small particle): Gold nanosphere D = 20 nm - 5 nm

absorption of ∆P/P ~ σext / Slaser ~ 10-3 - 10-5 of the incident light
→ Photothermal technique
D. Boyer et al., Science 2002, S. Berciaud et al. Phys. Rev. Lett. 2004
→ Spatial modulation technique (quantitative)
A. Arbouet et al., Phys. Rev. Lett. 93, 127401 (2004)
O. Muskens et al., Appl. Phys. Lett. 2006
 Dark Field Microscopy

Blocking the direct incoming light: collection of scattered light

blue: Ag sphere
green: Au sphere scattering
orange: Au rods
spectrum

scattered light

8π3Vnp
2
2 2
σs = ε − ε m f (ω)
3λ4

Single particle detection (D ≥ 20 nm)

condenser
 Size dependent dark-field scattering spectra

Single particle detection (D ≥ 20 nm)

• Dipolar approximation (few nm - few 10 nm):

- ΩR size independent
- width > size < (electrons-surface interaction)
• Multipolar Mie theory (D ≥ 30 - 50 nm):
- red shift
- broadening (radiative damping)
- multipolar resonances

Normalized scattering spectra

Au: experimental + Mie theory
(radiation damping,
quadrupolar effects)
C. Sönnichsen et al., New J. of Phys. 4 (2002)
 Spatial Modulation Spectroscopy (SMS)
Modulation of the nanoparticle position ⇔ Modulation of the transmitted light
objective f A. Arbouet et al., Phys. Rev. Lett. 2004
f , 2f
100x
lock-in amplifier
Gold nanoparticles
<D> ~ 16 nm
diluted on glass
piezo Transmitted
f power P

XY scanner

∆T/T
λ = 532 nm

X (µm)
X (µm)

Y (µm) Y (µm)
f 2f
 Metal Nanoparticles ?
400

Metal nanoparticle ⇒ 532 nm

Surface Plasmon Resonance 300

σext (nm )
2
200
Au - D = 20 nm :
633 nm
σext (532 nm) ≈ 10 σext (633 nm) 100
Au - 20nm

0
400 500 600 700

Wavelength (nm)

∆T
λ = 532 nm T λ = 633 nm

X (µm) X (µm)

Y (µm) Y (µm)
 Spatial Modulation : model

Nanoparticle at position (x0, y0) ⇒

I(x0,y0)
Transmitted power : Pt =Pi−σext I(x0,y0) δy
I : intensity profile at the focal spot
y0 y
Modulation of the position at f : y0 → y0 + δysin(2πft)

∂I σext ∂2I
Pt ≈ Pi − σext I (x0, y0 ) − σext δ y sin(2πft) − δ2y sin2 (2πft)
∂y y 2 ∂y2
0 y0

detection at f detection at 2f

δy << spot size

y y
 Absorption cross-section of a single nanoparticle

Au nanoparticle
f 2f
<D> = 10 nm

λ = 532 nm
dFWHM = 0.34 µm
δy = 0.27 µm

4
(d)
2
2
4
4

∆P / P x 10
∆P / P x 10

1 Absorption
0 cross-section
0
-2 σabs = (53 ± 2) nm2
@ λ = 532 nm
-1
-4
-0.50 -0.25 0.00 0.25 0.50 -0.50 -0.25 0.00 0.25 0.50

y - y0 (µm) y - y0 (µm)
 Absorption spectroscopy of a single nanoparticle

Ti- sapphire
femtosecond oscillator grating
100 mW - 780 nm - 20fs

Non-linear
Supercontinuum
photonic crystal fiber
λ > 450 nm

SMS microscope

Optical absorption signature

Quasi-spherical gold nanoparticles
 Single particle: Size effect

400 19.5 nm N anoscope < D > = 1 6.6 n m

15
300
White light
σabs (nm )
2

Counts
10
200

Spectroscopy 5
100
18 nm

0 0
450 500 550 600 12 13 14 15 16 <
TEM 17D >18= 119
6 .2 20
n m21
60 D iam eter (nm )
Wavelength (nm)
50
• Surface Plasmon Resonance (SPR) spectrum 40

Counts
30
Unpolarized light: Small sphere model
20
ε2
σabs = V 18π ε3m/ 2 10
λ ε + 2εm
2
0
12 13 14 15 16 17 18 19 20 21
D iam eter (nm )
• Absolute value of the extinction (absorption) cross-section:
→ Mie theory: optical determination of the particle size D
→ good agreement with TEM (mean diameter and size dispersion)
 Single particle: Anisotropy
Linearly polarized light → two "extreme" directions Aspect ratio statistics
N anoscope
400 120
90
60
12 < η > = 0 .9
350 150 30

Counts
180 0
300
(nm )

210 330
2

250
240 300 4
270
200 Polarization
Angle polarisation
σabs

angle 0
150 0 .5 0 .6 0 .7 0 .8 0 .9 1 .0
60 TEM
Au A sp e ct ratio c /a
100 < η > = 0 .9

50 40

Counts
0
450 500 550 600 650
20
Wavelength
Longueur d'onde (nm)
(nm)
Nanoellipsoids: SPR splitting ⇒ Aspect ratio: c/a = 0.92 0
0 .5 0 .6 0 .7 0 .8 0 .9 1 .0
2πVε3m/ 2 ε2
a
i A sp e ct ra tio c /a
σ abs =
λL2i 1 − Li
2
O.Muskens et al.,
ε+ ε c
Li m Appl. Phys. Lett. 2006

Optical identification of a nanoobject: size, anisotropy and orientation

→ studies of surface effects ; local environment effects ; …
Shape effect: gold nanorods

100 nm
 Shape effect: Gold nanorods (in PVOH)
10 Single nanorod M.P. Pileni - LM2N, Paris
A. Brioude, G. Bachelier - Lyon
8

40 - 60 nm
Ensemble
m)
2

6
-15
σext (x 10

90 nm
4
35 nm

15 - 20 nm
2

0
450 475 500 525 550 575 600 625 650 675 700
Wavelength (nm)
510 nm 630 nm
90
90
4 120 60
120 60
20
150 30 - Longitudinal SPR
2 150 30
10
- Transverse SPR
0 180 0
0 180 0

- Interband absorption
2 10
210 330
210 330

20
4 240 300
240 300
270
270
 Gold nanorods
Finite element model / DDA L
for fixed: - shape (cylinder with hemisphere caps)
- environment refractive index D
→ aspect ratio L/D = 2
→ Length (volume): L ≈ 50 nm
Transverse Longitudinal
10 90
120 60 1.0 ext
Extinction (norm.)

Extinction (norm.)
x9 abs
8 150 30
0.8 scatt
nm )
2

180 0
6 0.6
-15

210 330
σext (x 10

0.4
4 240
270
300
0.2
2 0.0
450 500 550 600 650 700 750
0 λ (nm)
450 500 550 600 650 700 Dominated by absorption
λ (nm)
New information ( / scattering experiments): O.Muskens et al., J. Phys. Chem. C 2008
- Volume
- Longitudinal / Transverse SPR amplitude (better agreement for sharper tips)
 One-by-one correlation with TEM:
nanoparticles on silica grids
P. Billaud et al., JPCC 2008
Optical TEM

1 µm

5
0° 90°
4 Ag@Si02
σext(λ) (10 nm )
2

3
4

Au D = 102 nm
2
Agreement with
1 Mie theory

0
400 500 600 700 800
Wavelength (nm)
Environment effect: “local” refractive index
 Single nanoparticles: local environment

500 Au - 16nm
Local environment: fixed size (D = 16 nm)
in PVOH
ε2
σabs = V 18π ε3m/ 2
400
λ ε + 2εm
2
(nm )
2

300
Effect on amplitude and SPR frequency
200
σabs

→ nm = 1.5
100 → nm = 1.4
→ nm = 1.25
0
450 500 550 600
Wavelength (nm)

→ Probe of its nano-environment: local refractive index

 Single nanoparticles: local environment statistics
Statistics: fluctuations of the “local” environment

Au/air

glass

PVOH

glass

PVOH added after /

before spin coating

Mean refractive index:

- on glass: 1.34
- embedded in polymer (PVOH): 1.45

→ “Local” refractive index of the nano-environment

O.Muskens et al., Phys. Rev. B 2008
 Surface plasmon resonance: environment effect

Environment sensitivity: scale ? SiO2

∆λmax
R = λR − λwater
R
→ Core-shell nanoparticle 1.0
(quasi-static approximation σe, σs)
0.8

max
∆λR / ∆λR
SiO2
0.6
Surface plasmon resonance shift as
a function of shell thickness 0.4 Au

0.2 water
Almost complete shift for
0.0
shell thickness ≡ core radius 0 1 2 3
Shell thickness / Core radius

Sensitivity to the environment over

a nanoscale (about its size)
⇔ extension of the local field
 Optical response: field (Ag)
f(ω) = |f(ω)|eiφ
Absorption:
10 |f(ω)|
Ag ϕ
ε 2
α = 1 p f(ω) αB σe

|f(ω)|
εm 5

3ε m
Local field factor: f (ω ) =
ε (ω ) + 2ε m 0

ϕ
2 3 4
hω (eV)
Enhancement of the internal field Internal/external field
3ε m hω=hΩR
Ei = E e = f (ω ) E e hω=hΩR+0,2 eV
ε + 2ε m 10 hω=hΩR-0,2 eV

|Ei, e+s / Ee|

z
and of the external field, 5
x

on a scale of about the radius R Ei

0
0 1 2 3
z/R
 Surface plasmon resonance: nanoparticles as sensors

Environment sensitivity → local nanosensors (bio-sensors)

G. Raschke et al., Nano Letters 3, 935 (2003)

Improved sensitivity: shape (nanorods, triangle, ...), structure (core-shell)

Confinement effect: SPR width and quality factor
 Single particle: width of the SPR
Electron scattering impact on absorption spectra: width of the SPR
σabs 18π 3 ε2 Ω3R Ω3R ib 1 2 gvF
= n Width: Γ(Ω R ) ≈ ε 2 (Ω R ) ≈ ε 2 (Ω R ) + +
V λ m 2 2 ω2p ω2p τ0 D
ε + 2nm

1 1 2 gvF Electron scattering rate

ε ( ω ) = ε b ( ω ) − ω 2p ω (ω + i τ ) with = +
τ τ0 D (τ0: e-phonons, g: e-surface)
→ g-surface scattering coefficient: fundamental problem
quantum mechanical predictions (Kubo, 1966) in air on glass
g=0
embedded in PVOH
... but hard to study: with PVOH after spin-coating 1
- Ensembles: inhomogeneous effects 2
(shape and environment distribution)
- Single: Exp. : non-controlled environment
(chemical damping)
Th. : g extracted by Mie theory fits
(dependence on ε tabulated values)
→ Large width fluctuations:
Single Au colloids:
g surface factor : 0.2 ≤ g ≤ 2 More precise studies: Ag@Si02
 Surface plasmon resonance damping: size dependence
Controlled environment: Ag@SiO2 nanoparticles
Luis Liz-Marzán, Universidad Vigo, Spain

e = 15 nm
SiO 2
Silver sphere mean diameter:
<D> = 12 nm
Ag <D> = 25 nm
<D> = 50 nm

Ag: surface plasmon resonance away from

<D> (nm)
1.0
the interband absorption: εib
50 30 20 10

2 (Ω R ) ≈ 0
0.8

(eV)
Extinction (norm.)
0.6

ens
ΓR
0.4

→ SPR width: size dependence 0.2

0.5 0.03 0.06 0.09
Ω3R 1 2 gvF 1 / <D> (nm )
-1

Γ (Ω R ) ≈ ε 2 (Ω R ) ≈ +
ω2p τ0 D

0.0
→ no surface effects visible on ensemble spectra 300 350 400 450 500 550 600
Wavelength (nm)
 Single nanoparticles: e-surface scattering in Ag
Polarization dependent spectra by SMS → aspect ratio η , equivalent diameter Deq

80°
• Big particles : radiative damping

σext (nm )
2
1000 400
2 gv F 1
170° • Small particles: ΓR ≈ +
800 η = 0.97 200 τ 0 Deq
σext (nm )
2

600
0
350 400 450 500 Diameter (nm)
400 λ (nm)
6050
5040 30 20 10
Deq = 13.2 nm 0.3
200 (14.2 nm) 0.5

ΓR (eV)
0.2
0
375 400 425 450 475 500 525 0.4 0.1

(eV)
0.04 0.06 0.08 0.10
Wavelength (nm) -1
1/Deq (nm )
0.3
g = 0.7

ΓR
→ g coefficient measured from exp. slope 0.2
1
g = 0.7 ≈ quantum-box Kubo model τ0
g’ = 0.45 including size-dependent 1/τ0
0.1 1/τ0(D)
⇒ more realistic quantum calculations : g’ ~ 0.4 0.02 0.04 0.06 0.08
-1
0.10
1 / Deq (nm )
→ Quantitative analysis of surface scattering at the single particle level
H. Baida et al., Nano Letters 2009
 Part III

Introduction: optical response of metal nanoparticles

Linear Optics: detection and spectroscopy of a single metal nanoparticle

Nonlinear Optics: ultrafast dynamics of a single metal nanoparticle

- Femtosecond time resolved pump-probe technique

- Electron-lattice coupling: Silver nanosphere
- Acoustic vibrations of a single nano-object
 The femtosecond laser

There are as many femtoseconds in one second …

1 fs = 10-15 s
than seconds in 30 million years !!

Ultrashort pulse laser:

Titanium - Sapphire

→ pulse duration ~ 20 fs
→ repetition rate ~ 100 MHz
→ infrared central wavelength
tunable λ : 680 → 1080 nm
→ average power 1 W
(peak power 500 kW, focused
peak intensity 1015 W/m2 )

See Prof. Chang Hee Nam’s lesson, Monday 30 November

 Non-linear optics
Nonlinear response of a material under strong em fields:

⇒ Polarization: P = PL + PNL
P = ε 0 χE + ε 0 χ ( 2 ) E⋅E + ...
χ(2) = 2nd order non-linear susceptibility

Second Harmonic Generation ω

ω + ω → 2ω ω Non linear
E(t) = A cos(ωt) crystal
→ PNL ∝ E . E ∝ cos(2ωt) 2ω

From IR fs pulses → blue / green fs pulses

1.0 1.0
(un. arb.)

Corrélation croisée
0.8 0.8

0.6 16nm 0.6 25 fs

Intensité

0.4 0.4

0.2 0.2

0.0 0.0
420 430 440 450 -100 -50 0 50 100

Longueur d'onde ( nm ) Temps ( fs )

→ generation of fs pulses at different wavelengths

 Time resolved pump-probe spectroscopy

Probe Sample

∆T/T

Pump

“ Pump pulse: ultrafast perturbation of the

system : modification of the medium
electronic and optical properties

“ Delayed Probe pulse: probe the system and

∆T/T
its relaxation to equilibrium.
The transmission change, ∆T/T,
induced by the pump
is measured as a function of the tunable 0 5 10 15 20 25
Pump - probe delay (ps)
30

pump-probe delay, tD
 Pump-probe: high sensitivity Lock-in detection scheme
Probe Sample
Pompe
Pump
Pump
∆T/T
Pump Sonde
Probe
Pump intensity modulated at frequency ω (chopper).
For a fixed pump-probe delay tD:
Chopper Pump- Probe
( ω) Retard
Sample Transmission: T (t D ) = T0 + ∆T pump (t D ) variable
Delay
( ω)
Photodiode: IT = T0 × I i + ∆T pump × Ii
Echantillon
Lock-in amplifier: ω modulated part Sample

→ sensitivity down to ∆T/T ~ 10-6 or better Signal Réfèrence

+ LOCK-IN
∆T/T

0 5 10 15 20 25 30
Pump - probe delay (ps)
 Fs experimental set-up in Lyon

• Home-made 18 fs oscillator, 76 MHz

• Coherent Chamaleon 680 - 1080 nm
• Coherent MIRA 100 fs oscillator
• Coherent REGA amplifier, 250kHz
• Coherent OPA system

• Non-linear SHG, THG

• Supercontinuum generation
• High sensitivity pump-probe setup
• SMS single nanoparticle setup
 Femtosecond investigation of metal nanoparticles

Probe hν
Sample

∆T/T Matrix e↔e Lattice Matrix

Pump τp-m τth τp-m
τe-ph

f0 f(0) f(t)
Te = T0 hωPp Te > T0
hωpr hωPp +hωPp

EF EF EF

t<0 t=0 t>0

• Femtosecond Pump: selective electron excitation (temperature increase ~ few 100 K)
• Investigation of the nonequilibrium electron kinetics (fs – ps time scale):
→ Intrinsic electron interaction processes (electrons-electrons / electrons-lattice)
→ Confined vibrational modes
→ Nanoparticle - environment coupling
 Ultrafast dynamics in metal nanoparticles
Electron Lattice
*First hundreds fs :
→ Internal thermalisation of
dynamics dynamics
the electron gaz at Te >To 1.0

∆T / T (norm.)
τth = 350 fs (Ag-bulk)

* First ps :
0.5
→ Energy transfer from
the electrons to the lattice

τ e-ph = 850 fs (Ag-bulk) 0.0

0 2 4 6 8 10 12
* Longer time scale : Retard sonde (ps)
→ Energy transfer to the matrix
Internal Thermalization Acoustic vibrations
→ Acoustic vibrations
of the electron gaz of the particles

Many studies in ensembles Energy transfer Energy transfer

(J. Phys. Chem. B 105, 2264 (2001)) to the lattice to the matrix
→ Single nanoparticle
 Femtosecond spectroscopy of a single nanoparticle

Pump femtosecond pump - probe:

∆T/T
IS T x IS probe around the SPR wavelength
Probe
∆T ∆σext
Sample =−
T 1nanoparticle S probe

Linear absorption: probe beam Nonlinear femtosecond response

detection and optical characterisation pump (2ω) & probe (ω)

First measurements: single silver nanospheres 20 - 30 nm

O.Muskens, N. Del Fatti and F. Vallee, Nano Letters 6, 552 (2006)
Electron-lattice energy exchanges: single Ag nanosphere
 Femtosecond spectroscopy of a single Ag nanosphere
Optical characterisation of a single nanoparticle (linear absorption spectrum)

Microscope
& femtosecond pump - probe study :
Objective
100x Transmitted
Power ∆T ⎛ ∆σ ext ⎞ σ
= −⎜⎜ ⎟⎟ ⋅ ext
T 1 nanoparticle ⎝ σ ext ⎠ pump S probe

IR excitation / SPR probing (425 nm)

∆T/Tmax (x 10 )
-4
1.0
10 1.2
Ag - D = 30 nm
0.5

∆T/T (x 10 )
-4
σext (x 10 m )
2

0.8 0.0
0 200 400
-15

PP (µW)
5
0.4
D = 21 nm

0.0
0
350 400 450 500 550 0 1 2 3
Longueur d'onde (nm) Probe delay (ps)
 Electron-phonon energy exchange in single Ag nanospheres

• ∆T/T ∝ electron excess energy

⇒ Decay: electron-lattice energy exchange → τe-ph

1.5

Strong excitation regime

1.2
excitation dependent decay: τe(Te)
(ps)
τe-ph

0.9 τ e−
0
ph
Weak excitation regime
∆T decay with τ0e-ph = c0 T0 / G
0.6
0.0 0.2 0.4
Pump power (mW)

Thermal distributions: Two temperature model ⎧ dTe

⎪⎪ e e dt = −G (Te − TL )
C (T )
Te ; TL ; G = e-lattice coupling constant ⎨
Ce(Te) = c0 Te ; CL : heat capacities ⎪C dTL = G (T − T )
⎪⎩ L dt e L
 Electron-phonon coupling in single Ag nanospheres

1.5

Known nanoparticle ⇒ known excitation Temax - T0

1.2
(ps)

→ comparison with the two-temperature model

τe-ph

0.9

2.0
pum
0.6 p po ∆Temax : 110 - 430 K (30nm)
0.0 0.2 0.4 wer
Pump power (mW) ∆Temax : 220 - 380 K (21nm)
⇒T max
e
1.5

τe-ph / τe-ph
0
Comparison wih two temperature model:
→ Same electron-phonon coupling
as in ensemble measurements (in glass) 1.0
→ No environment dependence
(large excitation) 0.1 1
max
→ No e-ph coupling dependence (T e
-T0) / T0
on excitation regime
O. Muskens, N. Del Fatti and F. Vallee, Nano Letters 2006
Non-linear SPR response: single Au nanorod
 Ultrafast nonlinear response of a gold nanorod
i) Detection and optical characterizaion 60 nm
Linear absorption spectroscopy
15 nm
8 nano-batonnet unique
ensemble

Absorption (arb. units)

Shape, size, orientation
6

4 ii) Ultrafast nonlinear response

2 pump & probe

0
500 600 700 800
W avelength (nm)

9 780 nm
800 nm
1.5 Simulations
830 nm
6

∆T/T (normalized)
1.0
Optical nonlinearity
(x 10 )
-5

of a single nanorod: 3 0.5

Quantitative interpretation 0 0.0

∆T/T

(no size, shape or orientation

-3 -0.5
averaging)
-6 -1.0

0.0 0.5 1.0 1.5 2.0 0.0 0.5 1.0 1.5 2.0
Probe delay (ps) Probe delay (ps)
Acoustic vibrations of a nano-object
 Optical Excitation and Detection of acoustic vibrations
• Ultrafast Pump pulse :
→ launches the vibration

• Delayed Probe pulse :

→ Volume-dependent signal
→ sensitive to vibrations
Vibrational acoustic modes:
- Frequency: size and shape dependent → Single nanoparticle
- Damping: environment, size-shape distribution
 Breathing nanoparticles...

T0

Acoustic breathing mode of a Ag nanoparticle with R = 12 nm :

Vibration period ~ 7 ps
Single Ag@SiO2 nanoparticle: pump-probe and TEM study
L. Liz-Marzan, Univ. Vigo, Spain
Pump / Probe
830 / 415 nm SiO2
e ~ 15nm
Ag

2.5

Extinction σext (x 10 nm )
2
1.5 2.0

4
1.5

∆T / T (x 10 )
-3
1.0 1.0
Single particle oscillation (Ag@Si02): 0.5
Size ~ 40 nm
spherical model ω = ξ vL/D 0.5 0.0
400 420 440 460 480
λ (nm)
→ Deq ~ 45 nm
0.0
From TEM : a = 38 nm / b = 47 nm.
0 10 20 30 40
Time Delay (ps)
Acoustic vibrations of a nano-prism
 Gold nanoprisms: detection
M. El-Sayed
SEM image Georgia Inst. Tech., Atlanta

Nanosphere lithography:
Organized nanoprisms: size 120 nm
thickness 30 nm

Optical image (at 410 nm)

AFM image

⇒ Optical observation 5 x 5 µm2

of prism pairs
 Gold nano-prisms:
Gold nanoprisms: acoustic
acoustic vibrations
vibrations
Time resolved spectroscopy of a single nanoprism pair
T1
0.2
0.8 pump

OD
(x10 )
-3

0.1
0.6 probe
T2
0.4 0.0 FFT
400 600 800
∆T/T

λ (nm)
0.2 electronic response
acoustic vibrations
0.0

0 50 100 150 200

Probe delay (ps)
Thickness breathing mode: T3 = 14 ps (film - 30 nm : 2e/vL → 18 ps)

Two main modes: period: T1 = 64 ps ; T2 = 49 ps

damping: τ1 = 120 ps ; τ2 = 45 ps
 Gold nanoprisms: acoustic vibrations
60
0.2

Main mode periods:

(x10 )
-3

0.1 T1 and T2 55

T2 (ps)
∆T/T

0.0
50
0 50 100 150
Probe delay (ps)

45
60 65 70 75
T1 (ps)
600 • Period fluctuations:
→ mean values: <T1> = 68 ps ; <T2> = 51 ps
→ agreement with ensemble measurements
τ1 (ps)

400
→ Correlated fluctuations → shape/size effect
• Damping: Energy transfer to the substrate
200
- 100 ps ≤ τ1 ≤ 600 ps → <τ1> ≈ 360 ps
- ensemble measurement: τ1 ≈ 70 ps
0
(inhomogeneous damping)
60 65 70 75 - No τ1 - T1 correlation
T1 (ps) → fluctuation of the prism-substrate contact
 Gold nanoprisms: acoustic vibrations

• M.A.El Sayed et al.,

125 J. Phys. Chem. B 109, 18881 (2005) Finite Element Method (FEM) simulations
Period T1 (ps)

100

75

50

Truncated
25
pyramid
Free prism: fundamental mode
0
50 100 150 200 250
Prism size (nm)

→ Weak substrate influence: free nanoprisms

→ Shape effect: truncated pyramid
J. Burgin et al., J. Phys. Chem. C 2008
 Conclusion

• Single metal nanoparticle detection

→ Spatial Modulation Technique: direct absorption measurement
→ absorption cross section down to a few nm2
→ far-field technique ⇒ dilute sample (< 1 particle per µm2)
→ spectroscopy: optical identification of a single nanoobject
→ combined optical response and electron microscopy

• Femtosecond time-resolved spectroscopy

→ electron-phonon coupling in a single metal nano-object
→ acoustic vibration: acoustic properties at a nanoscale
→ nonlinear optics with a single nanoobject
→ combination with electron microscopy
 Acknowledgements

FemtoNanoOptics group 
Lyon, France
H. Baida (PhD student)
V. Juvé (PhD student)
D. Mongin (PhD student)
Dr. Paolo Maioli
Dr. Aurélien Crut
Prof. Fabrice Vallée
Prof. Natalia Del Fatti

Université Bordeaux -France- Université Lyon Universidad Vigo - Spain

Prof. L. Liz-Marzan
Dr. D. Christofilos Prof. M. Broyer
Dr. O. Muskens Prof. M. Pellarin Université Paris VI - France
Dr. A. Arbouet Prof. J. Lermé Prof. M.P. Pileni
Dr. J. Burgin Dr. E. Cottancin
Dr. P. Langot Dr. G. Bachelier Georgia Institute of Technology - USA
Dr. A. Brioude Prof. M. El-Sayed