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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
Ei Constituting materials:
dielectric constants
E e = xˆ Ae e i ( kz −ωt ) + cc εm ε(ω)
p.r ⎡ ε − εm ⎤
- scattered: Φs = with p = 3ε mε 0Vnp ⎢ ⎥ Ee
4πεmε0r3 ⎣ ε + 2ε m ⎦
x
Simple interpretation
Ee z
k p
Ee
electrons y
→ 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
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
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 )
-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 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
+
+ + - +
+ + ...
- - + -
-
electrons dipole quadrupole
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
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
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
Licurgus Cup
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
♦ 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
blue: Ag sphere
green: Au sphere scattering
orange: Au rods
spectrum
scattered light
8π3Vnp
2
2 2
σs = ε − ε m f (ω)
3λ4
XY scanner
∆T/T
λ = 532 nm
X (µm)
X (µm)
Y (µm) Y (µm)
f 2f
Metal Nanoparticles ?
400
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
∂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
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
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
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)
Au/air
glass
PVOH
glass
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
|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
0
0 1 2 3
z/R
Surface plasmon resonance: nanoparticles as sensors
e = 15 nm
SiO 2
Silver sphere mean diameter:
<D> = 12 nm
Ag <D> = 25 nm
<D> = 50 nm
2 (Ω R ) ≈ 0
0.8
(eV)
Extinction (norm.)
0.6
ens
ΓR
0.4
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
→ 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 )
⇒ Polarization: P = PL + PNL
P = ε 0 χE + ε 0 χ ( 2 ) E⋅E + ...
χ(2) = 2nd order non-linear susceptibility
Corrélation croisée
0.8 0.8
0.4 0.4
0.2 0.2
0.0 0.0
420 430 440 450 -100 -50 0 50 100
Probe Sample
∆T/T
Pump
∆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
+ LOCK-IN
∆T/T
0 5 10 15 20 25 30
Pump - probe delay (ps)
Fs experimental set-up in Lyon
Probe hν
Sample
f0 f(0) f(t)
Te = T0 hωPp Te > T0
hωpr hωPp +hωPp
EF EF EF
∆T / T (norm.)
τth = 350 fs (Ag-bulk)
* First ps :
0.5
→ Energy transfer from
the electrons to the lattice
Microscope
& femtosecond pump - probe study :
Objective
100x Transmitted
Power ∆T ⎛ ∆σ ext ⎞ σ
= −⎜⎜ ⎟⎟ ⋅ ext
T 1 nanoparticle ⎝ σ ext ⎠ pump S probe
∆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
1.5
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)
1.5
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
9 780 nm
800 nm
1.5 Simulations
830 nm
6
∆T/T (normalized)
1.0
Optical nonlinearity
(x 10 )
-5
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
T0
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
AFM image
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
0.1 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
100
75
50
Truncated
25
pyramid
Free prism: fundamental mode
0
50 100 150 200 250
Prism size (nm)
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