Bigot

Optics and Spin Photonics of Metallic Nanostructures Jean-Yves Bigot
Institut de Physique et Chimie des Matriaux de Strasbourg
Universit de Strasbourg - CNRS -
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Seoul - 2009 - Jean-Yves Bigot - Winter_school_IPCMS-QMMRC
1. The static optical and magneto-optical properties of metallic nanoparticles

1.1 The response function of metals to an optical excitation : intraband and interband transitions, transverse dielectric function of metals. Scattering of light by small metallic particles : theory of Mie, the effective medium response, surface plasmons. 1.2 General motivations, Magneto-optics of metals : Kerr and Faraday magneto-optical responses; Superparamagnetism of nanoparticles : Nel and Brown models
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Lycurgus Cup (Roman period : 4th century) exhibited at the British Museum.
Reflection
Transmission
Glass containing Au and Ag nanoparticles

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Gold and silver salts were used in medieval times to color glass used in church windows. For example, silver particles were used to stain glass yellow, while gold particles were used to stain glass red.
Rose window from Strasbourg Cathedral (15 m diameter)
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Au nanoparticles as agent for high contrast imaging

planar X-ray imaging: Kidneys in live mouse 60 minutes after intravenous injection
Au nanoparticles Iodine contrast medium
Ureter : 100 nm
70 mm
Courtesy : www.nanoprobes.com
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Nanoparticles as catalysts for controlling reactions

Optimizing chemical reactions over an energy barrier Energy
Without catalyst
Au
Reactants
with catalyst
Products
Au nanoparticle on oxide substrate. CO and CO2 molecules react on the surface of the nanoparticle
Generalized reaction coordinate
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Self organization of nanoparticles

What is the effect of 2D and 3D self-organization on optical and magneto-optical properties ?
Electron microscopy image : mono-layer of self organized cobalt nanoparticules Fourier transform : hexagonal order
3D supra crystals of Cobalt nano-particules
Collaboration : LM2N - Universit Pierre et Marie Curie Paris ; (I. Lisiecki, C. Petit, M.-P. Pilni)
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A historical note about Nanosciences
Faraday was the first to report what later came to be called metallic nanoparticles. In 1847 he discovered that the optical properties of gold colloids differed from those of the corresponding bulk metal. This was probably the first reported observation of the effects of size, and might be considered to be the birth of nanoscience
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Intuitive approach to the response function of metallic nanoparticles

Consider N nanoparticles in an external electric field E, with a dielectric function . It is an effective medium with dielectric function eff
-P
Then the polarization Pind, induced in the medium and the local field Eloc are:
ind,
Eloc
+ + + +
Pind = ( eff 0 ) E ; E loc
( 0 ) E Pind = 3N 0 ( + 2 0 ) loc
Pind = 0E + 3 0
The effective dielectric function eff is given by :
( 0 ) eff = 0 + 3N 0 ( + 2 0 )
y s n e d l a i t p O c
Resonance if :
e ( ) = 2 0
IP
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When does the condition for resonance occur ? and what is its effect on the optical properties ?
e ( ) = 2 0
For metals : () and Re() < 0 . Example Drude model of electrons:

Consider n electrons of mass m in an external field Ecos(t)
d x dx m 2 + m = eE dt dt
P = nex
(polarization)
D( ) P( ) metal ( ) = = 1 + 4 E ( ) E ( )
2 p
4ne 2 1 metal ( ) = 1 = 1 m ( + i ) ( + i )
2 p
4ne 2 = m
p : Volume
Plasmon resonance
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for metals (1/) = ~10-14 s, so typically for h ~ 2 eV (wavelength ~ 600 nm) : 22 >> 1
2 p e ( ) 1 2
2 2 p p m ( ) 3 = 3
10
Absorption of nanoparticles
absorption (a.u.)
5 0
2 1
0 2 4 6 8
1.0
surface plasmon resonance
0.5
- 20 -5
-10
= p
10 12
0.0
h (eV)
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e [ ( )] = 2 0
h (eV)
Absorption spectra of assemblies of Silver, Gold and Copper metallic nanoparticles
1.0 Absorption (normalized) 0.8 0.6 0.4 0.2 0.0 300
Au Ag Cu
Ag : 6.5 nm Au : 25 nm Cu : 10 nm
400
500
600
700
Wavelength (nm)
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Au - Ag bimetallic alloys of nanoparticles
from : Materials Chemistry and Physics 113 (2009) 276282 Au mole fraction max (nm) Particle size (nm) Zeta-potential (mV) Conductance (S) Emission peak
0.1 0.2 0.4 0.5 0.6 1
414 428 466 475 486 525
29 27 32 26 26 44
12 2 7 13 17 28
2098 1583 2156 2249 1989 1997
482 502 554 584 600 600
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What are the important parameters for the surface plasmon peak position and width of the resonance :? () is more complicated than just Drude theory Even with Drude theory, what is the meaning of damping ? What is the role of the size and shape of the particles ? What does self - organization do ?
Needs for comprehensive understanding of metallic nano-objects
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Classical model of conduction electrons : DRUDE model of non-interacting electrons Based on kinetic equation for n electrons (e, m) in a field E (Ecost).
p 4ne 2 1 = 1 D ( ) = 1 m ( + i ) ( + i )
2
2 p
4 ne 2 = m
p : Plasmon frequency (~10 eV) : damping !!!
100
100 10
e |D| m (D) -m (1/D)
50
1
0
0.1
0.0 0.5 1.0
-50
/ p
1.5
0.01
0.0
0.5
1.0 / 1.5
p
e (D) = 0 for = p
- for 0 1 for
m (D) ~ 0 for = p
for 0 0 for
-m (1/D) max for = p Excitation spectrum
Optical absorption
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What is missing in the Drude model ?
Dispersion : (q) Temperature of electrons: (, q, kbT) Interband transitions
Calculation of dielectric function for excitation by electromagnetic field
ih
= [H , ] ; H = H 0 + H int (r, t) t e H int (r, t) = p(r ).A (r ) Coulomb Gauge (.A = 0) 2mc
H o kl = Ekl kl and o kl = f o ( Ekl ) kl k: wave vector, l : band kl eigenstates Ekl E F k BT f o ( Ekl ) = 1 / 1 + e EF : Fermi energy
< kl = 1/ 2u kl (r)e ikr Bloch functions with lattice periodicity

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In first order perturbation one gets :
ih
kl 1 k + q, l ' t
= ( Ekl Ek + q ,l ' ) kl 1 k + q, l ' + [ f o ( Ek + q ,l ' ) f o ( Ekl )] kl H int (r, t ) k + q, l '
e with : kl H int (r, t ) k + q, l ' = kl p.A(q, t )eiqr k + q, l ' mc

For an adiabatic field excitation : A(q,t) is harmonic : A(q,t) = A(q) exp(-i+)t then the matrix elements are :
Note the damping parameter , which assures that A 0 when t -
kl 1 k + q, l ' =
S
[ f o ( Ek + q ,l ' ) f o ( Ekl )]
e kl p.A(q)eiqr k + q, l ' mc ih h Ek + q ,l ' + Ekl
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Current density operator J(q) :
e 1 e 0 J (q ) = Tr exp(iqr ) A(q) Tr exp(iqr ) p mc m

Diamagnetic response Paramagnetic response
Using the response theory : Ohms law
J ( q, ) =
i ( - 1) : conductivity ( q, ) A ( q ) ; = c 4i
One finally obtains the Transverse dielectric function:
4e 2 0 4e 2 lim ( q, ) = 1 { 2 2 2 m 0 m
k ,l ,l '
kl p k + q, l '
f o ( Ek + q ,l ' ) f o ( Ekl ) Ek + q ,l ' Ekl h + ih
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Advantages of the theory : 1) Dispersion is included ( depends on and q) 2) Two contributions : intraband (l = l) and interband l l 3) Temperature can be included via Fermi-Dirac f(Ekl, kbT) instead of f0(Ekl) * However the theory is not complete : in principle one should consider the Liouville equation to higher order perturbation theory ! * The theory is OK for multi-level systems but it does not solve the problem of the many-body electron gaz. Still one can grasp some physics !
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l = p band Fermi level EF
E intraband transition !
interband transition
kl p k + q, l '
2
l = d band
For photons q ~ 0 (as compared to Brillouin Zone)
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Excitation spectrum of quasi-particles (l=l)
( q, ) 1 +
4i
h =
( q, )
h 2 (q + 2qk F ) 2m
2 3vF 2 h P ( q ) = h P ( 1 + q ) 2 10 P
Re() = 0
Landau damping : decay of plasmons into quasiparticles
From longitudinal dielectric function
h =
Re() = 0
h 2 (q 2qk F ) 2m
2kF
Fermi surfaces of radius kF kF+q
Momentum space accessible for quasiparticles excitations

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Interband transitions
e 2h 2 int er ( ) = 2 2 m
E kl' h2k 2 = Eg + 2m
2hl 'l [(h ) 2 (hl 'l ) 2 (h ) 2 2ihh ] ' dk (h ) 2 [ f o ( Ekl ) f o ( Ekl ' )] [(h ) 2 (h ) 2 (h ) 2 ]2 + 4(h ) 2 (h ) 2 l ,l l 'l l 'l
3
Pll '
m: effective mass of electrons in corresponding band
In general Pll is assumed independant of k For parabolic p band and flat d band :
( ) = K dx
Eg
hx E g x
2 x 2 2 2i 2 (1 f o ( x )) 2 ( x 2 2 ) 2 + 4 2 2
Interband effects are most spectacular in noble metals They are are responsible for the colors of copper, gold and silver
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Reason for the different absorption of the transition metal nanoparticles
Copper
interband
Silver
Ag
Dielectric function e ()
experimental (Ehrenreich)
Dielectric function e ()
-5
Drude
-10 2 4 6 8 10
energy (eV)
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In real life one has to take into account the complexity of the bands in the Brillouin Zone
For silver
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Inhomogeneous systems and Dielectric confinement

Dielectric confinement results from the optical index matching at the surface of a nano-structure (boundary conditions for the EM field) Unlike the refraction at a dielectric surface, the light scattering from such nanostructure can display a complex mode structure. Simple case : metallic spheres. Plane wave has to be projected in spherical coordinates
Fourier transform of Maxwell equations

E + ( q0 )2 E = 0 H + ( q0 )2 H = 0
Helmoltz equations :
: dielectric function inside or outside the sphere
q0 =
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Mie scattering theory (exact solution for a sphere): Write equation in spherical coordinates r, ,
1 2(r ) 1 1 2 2 + 2 (sin )+ 2 2 + q0 2 = 0 r r 2 r sin r sin 2
Search solutions like : =R(r)()() Transmitted waves: 1 e r t = 2 cl l (kr)Pl( 1 )( cos ) cos k l =1
(a) (b)
r tm
2 = 2 0 2 k ( 2 )
d l l (kr)Pl( 1 )( cos ) sin

l =1
Scattered waves: 1 e r d = 2 al l(k d r)Pl ( 1 )( cos ) cos k d l =1
(a) (b)
2 r = 2 0 2 k d ( 2)
m d
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bl l(k d r)Pl ( 1 )( cos ) sin

l =1
Using the flux of energy per unit time :

S = c Re E H 8
W=
sphere
S ds
One obtains the cross sections of extinction and scattering

2 Wa + Wscat Qext = = 02 2nd Si
Qscat
Re[(i)
l =1
l +1
l +1
l (l + 1)(al + bl )
2 Wscat = = 02 2nd Si
(1)
l =1
l 2 (l + 1) 2 2 2 [ al + bl ] 2l + 1
2 2 n d l +1 x 2l +1 n 2 nd l a l i 2 l [1.3.5...( 2l 1 )]2 n 2 l + 1 n 2 d l 2 n d l +3 x 2l +3 l 2 (n 2 n d ) bl i l(l + 1 )( 2l + 1 )( 2l + 3 )[1.3.5...( 2l 1 )]2
To first order in l :
a1 = i d d
d 3 x + 2 d
p0 = a 3 d
for small spheres (d << ), the scattered light is the same as the one of a dipole centered on the sphere p=p0exp(it) and :
d + 2 d
Mie scattering of Metallic nanoparticles

(u.a)
0.6
d=50nm,lmax=1 d=50nm,lmax=5 d=50nm,lmax=7
0.4
Silver
0.4 0.2 0.2
0.0
2 3 nergie (eV)
d=50nm,lmax=1 d=50nm,lmax=5
0.0
nergie (eV)
(u.a)
Rule of thumb: First order is OK up to diameter ~/10
2 2 1 1 0
Copper
-1
2.0 2.5 nergie (eV)
3.0
2.0
nergie (eV)
2.5
3.0
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In chapter 2 we will discuss the damping parameter
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Performances in Spintronics devices

Tunnel Magneto Resistance
R
MRT = R
R
R

Perpendicular recording MRAM from TOSHIBA
writing
35,7 Mb/s on a theoretical bus of 1 data bit ~10 / 1 MB compare to ~10 / 1GB for RAM or flash memories (USB)
Explore new approaches : Spin Photonics ?

S
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Modify and study magnetization dynamics with light pulses Technology and fundamental physical processes
1 Terabits/inch2; 10 GHz 10 THz

Relevant physical scales : 100-10 nm; 100 ps 100 fs
Associate Ultrafast Optics with Magnetism

-20 10 0 20
50
M (u.a)
-50x10
-6
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-10
How fast and how short ?
Basic principles of magneto-optics
In 1845 Michael Faraday discovered that the polarization of light propagating through a magnetized substance is rotated. This magneto-optical (M.O.) effect, first observed in a sample of glass placed in an intense magnetic field and later in the reflectivity of metals by John Kerr, is now a widely used physical method to explore the properties of magnetic materials. The magneto-optical Kerr and Faraday effects are due to an asymmetric absorption and refraction for the left and right helicities of circularly polarized light due to the spin-orbit interaction.
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In the linear response theory these M.O. effects are well described by the off-diagonal complex dielectric tensor element xy For example, the Kerr rotation K and ellipticity K acquired by a linearly polarized light reflected from a ferromagnet is given, in the polar geometry, by :
n+ n n+ n K = m n n - 1 ; K = e n n - 1 + - + -
with n = = xx ixy
2
Refractive index for (+) and (-) circularly polarized light Simple case :
xx xy 0
H E E = 0 ; H = 0 t t D = 0 ( M , ) E
xy xx
0
0 0 zz
Onsager relation
2 D+ = 0 n+ ( E x + iE y ) 2 D = 0 n ( E x iE y )
ij (M, ) = ji (M, )
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Illustration of Faraday rotation and ellipticity
if M = 0 : e n+= e nm n+= m n-
if M = 0 : e n+ e nm n+= m n-
if M = 0 : e n+= e nm n+ m n-
Linearly polarized light
Linearly rotated Kerr magneto-optical configurations

(j,k) : sample plane
elliptic non-rotated
k j
b ent ncid I eam
M
Re
fle cte d
(i,j) : plane of incidence

Polar : M // i ; Longitudinal : M // j ; Transverse : M // k
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An easy way to understand Magneto-optics !
B v
f = e(E + v B )
Lorentz force
Working out the extended Drude model with a Lorentz force gives :
xy () = yx () =
2 p
2
+ i
2 2
with : p2 = Ne2/m0 and = eB0 /m

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Generalized magneto-optical response

Magnetic material with magnetization M, Polarization P excited by a monochromatic wave E(r,) with frequency
2 4ci x M (r, ) xx E(r, ) = - 2 E(r, ) + 4P(r, ) + c

P (r, ) = P L (r, ) + P NL (r, ) M (r, ) = M L (r, ) + M NL (r, )
Linear :
(1) Pi(1) () = ij () E j () j
Non magnetic response Magneto-optical response
(1)MO M i(1) () = ij () E j () j
Nonlinear (third order) :

jkl
Coupling with field H
(3) Pi(3) () = ijkl (; 1 , 2 , 3 ) E j (1 )E k ( 2 )E l ( 3 ) with = 1 + 2 + 3
(3)MO M i(3) () = ijkl (; 1 , 2 , 3 ) E j (1 )E k (2 )E l (3 ) ; = 1 + 2 + 3 jkl
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A less easy way to understand Magneto-optics !

J.-Y. Bigot, C. R. Acad. Sci. Ser. IV (Paris) 2, 1483-1504 (2001).
So far in our approach to the optical response of metals we Have neglected the spins. But we need to introduce them and in addition a coupling with the polarization. For this, we introduce the spin-orbit interaction : Since we dont know how to handle properly the Coulomb correlations in full, let us consider a sum of one body hamiltonians H0n , where the Coulomb interaction e 2/r nm between the electrons is replaced by an effective one body operator Veff (rn):
H 0n
Pn2 h Pn = + V(rn ) + s V(rn ) + Veff (rn ) 2 2 n 2m n 4m n c

Pn : General momentum of electron n. Amag(rn) : vector potential of the applied magnetic field
e Pn = p n + A mag (rn ) c
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The light matter interaction is treated semi-classically
H Rn =
e n A light (rn ) 2 mnc
Amag(rn) : vector potential of the applied light field
n = Pn + s n V(rn )
s n V(rn )
Spin orbit coupling sn : Pauli spin operator
Careful ! this is a pure 1/c2 relativistic interaction term !
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Total absorbed energy :
N P = e * E * E i = N h W ij j 2 ij
, : energy levels of the electronic system
W per unit time at energy h between the states |> and | > separated by the energy h. The Fermi golden rule gives :
2 EE * e 2 = 2 2 h 4m
[(h - h) + (h + h)]
( = x, y or = +, -) are the components of the generalized momentum. By definition :
= ( x y )
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Real and imaginary parts of the conductivity tensor : (allow to calculate the Kerr and Faraday rotation and ellipticity)
2 2 N e + e xy = - 2 2 2 2 hm ( ) ( 2 )
2
Ne 2 m xy = ( ) 2 2hm
- +
Transition probability elements
They include the spin-orbit coupling and the level separation which depends on the Zeeman splitting for uncorrelated systems and on the exchange interaction in ferromagnetic systems For ferromagnets it is admitted that the spin-orbit coupling is the most important contribution !!!
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Super-paramagnetism
Thermal fluctuations of magnetization
Nanoparticle with volume V
E = KV sin 2 H cos
Anisotropy K dipolar
E
KV
+H H
Louis Nel 1949 :
2 KV
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KV (1 H / H K ) 2 k BT
with : H K =
Fluctuations : (V, T, K)
K
0.5
Example:
d = 2 nm = 0 ~ 10-10 s d = 8 nm ~ 1017 s !
E / KV
Gyroscopic behavior : 0
M
0.5
E / KV
0 (P) W.F. Brown 1959 Langevin model

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P : Damping of the precession (frequency p)
Langevin approach to magnetization dynamics: Brown 1963

dM dM V + h(t ) = 0M dt dt M
usual damping : Gilbert Fluctuating field : Stationnary Gaussian stochastic process
hi (t ) = 0 ;
hi t )h j (t + ) = ij (t )
The magnetic moment for a single particle is distributed on a sphere with a density of probabilty W(,,t) which obeys a Fokker-Planck equation
with : H c 2K 0 M S
2M S H c 2 (M S ) 2 + 0
0 VM S H c 2 k BT
Coherent term
IP CM S
Incoherent term
Cobalt nanoparticles : ion implantation in dielectric matrices (Si02 and Al203)

C. DOrlans, C. Estourns
Spherical monodomain particles

Si02
Si wafer
SiO2, diameter ~8 nm (ferromagnetic at 295K) Al2O3, diameter ~4 nm (superparamagnetic at 295 K)
S
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Concentration profile
2x10 2x10
22
Co in Sapphire
22
16 14 12
At / cm
1x10 8x10
22
10 8 6 4 2
-5
21
4x10
21
Blocking temperature Tb ~ 80 K
Co (~4 nm) / Sapphire
50
100
150
200
250
2.0x10 1.5x10
Depth (nm)
-5
FC
2 M (emu.cm )
1.0x10 5.0x10
-5
-6
ZFC
0.0 0
100b T
200
300
400
T (K)
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2. Ultrafast laser optics of metals

2.1 A rapid overview of femtosecond laser optics. 2.2 The dynamics of the electron gas : Landau damping, electronelectron interaction and the Fermi liquid approximation, two temperatures model, non-thermal electron dynamics. 2.3 Time resolved studies of metallic films and nanoparticles. .
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The detection of primary events in the time evolution of many physical, chemical or biological systems require a femtosecond temporal resolution
Example : chloration of methane
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Estimates of the typical timescales associated with the energies involved in molecular systems
M1
r0
eM2
Electronic energy : Ee = p2/2me ~ h2/me r02 in SI units : me ~ 10-30 ; h ~ 10-34; r0 ~ 3x10-10 : Ee ~ 10-19 J ~ 1 eV The corresponding timescale is : T ~ h/E 1eV 10-15 s = 1 femtosecond Energy of vibration stretch : The force binding the two nuclei is comparable to the one of the electron bound to the molecule. Considering classical oscillators :
E vib = k/M ; E e = k/m e ; E vib = E e m e /M with : 1 1 1 = + M M1 M 2
Evib ~ 10-2 eV Tvib ~ 100 fs
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Probing transition states : The case of NaI (A. Zewail et al.)
A. Zewail, 1999 Nobel price in chemistry for his studies of the transition states of chemical reactions using femtosecond spectroscopy
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Wave-packet dynamics associated to C=C vibrations of Polydiacetylene

C=C
23 fs C=C stretch
CC
6 5 0 -4 0 0 6 0 0 4 0
Time (f s)
Chem. Phys. Lett., 259, 469-474 (1996)
S
8 0
5 5 0 1 2 0
gth len e av W
m) (n
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Quantum Beats between excitons

Appl. Phys. Lett., 87, 192104 (2005)
E1
Piezoelectric CdTe QW
HH1 HH2
e1h1 and e1h2 excitons sharing a common conduction band level
2.5
2.0
retard (ps)
1.5
1.0
0.5
2.5 2.0 1.5 1.0 0.5
0.0
rd ta re
0.0 790
780 785
775
770
765
790 785 780 775 770 765
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s) (p
) (nm
(nm)
Femtosecond isomerization in retinal proteins

Structure of rod rhodopsin Okada et al., JMB 2004
11-cis
all-trans
Retinal increases dipole moment when distorted (<200 fs) Electrostatic interaction with protein drives isomerization. Schenkl et al., Science 2005
All-trans form shows up as increased absorption at > 570 nm Isomerization occurs in 200 fs Wang et al., Science 1994
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* A sound wave propagating over a distance x = 100 in a metal : v ~104 m/s T = x/v ~ 10-12 s (acoustic waves : 1 picosecond) * Optical phonons in dielectric and semiconductors : ~100 fs) * Light interferometry : = 1 m ; c = 3 108 m/s T = /c ~ 3 femtoseconds * Electron-hole pair breaking in a semiconductor : Binding energy of excitons Eb ~ 10 meV (T~ 100 fs) Ultrafast spectroscopy performed with femtosecond pulses allows studying the dynamics of chemical and biological molecules as well as a variety of materials in condensed matter physics
But there is more than just temporal considerations !

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Time versus frequency domains
1 (t) = 2
e - i t d
An ideal -function pulse contains an infinite spectrum ! Typically : 2 C (if equality : Fourier transform pulse)
Pulse duration
12 fs pulse
Spectrum
exp[4 ln 2(t / ) 2 ] C = 0.441 1/[1 + (2t / ) 2 ] C = 0.221 1/[cosh (1.76t / )]2 C = 0.315
-80 -40
Time ( fs )
40
80
550
600
650
700
Wavelength ( nm )
time dependent spectroscopy is accessible in a very large bandwidth of the optical spectrum
A coherent white light source !

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Density of electromagnetic field

Typical energy of a low power CW laser (beam pointer): 1 mW The same energy in 10 fs : 1011 Watt (still only 1 mJ / pulse) Power density focused on a spot of 10 m diameter : 1017 Watt/cm2 Actual high power laser facilities : 1-10 J / pulse 1020 1021 Watt/cm2
109-1012 W/cm2 : Conventional Nonlinear Optics + Time resolved spectroscopy Material processing (electron plasma) + medical applications New laser design : self phase modulation, self focusing
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One photon excitation : h
Two-photon excitation : 2x(h/2)
fluorescence
fluorescence
h/2
S
Application to bio-imaging : Maybe one of the largest success of femtosecond Titanium Sapphire laser !
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Ablation of matter by lattice heating versus electron plasma
Nanosecond
Femtosecond
Laser fabrication of 100 m hole made in steel with nanosecond and femtosecond pulses
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Self phase modulation : generation of white light continuum
Kerr nonlinear index Phase of propagating laser pulse Instantaneous frequency
n = n 0 + n 2 I(t) + ... z (t) = n 2 I(t) c z dI(t) d(t) (t) = = n2 dt c dt
If n2 > 0 : when I increases (leading part of pulse) decreases red colors are generated when I decreases (falling part of pulse) increases blue colors generated
I(t)
Kerr medium
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1012-1016 W/cm2 : High intensity Nonlinear Optics High harmonic generation Xrays sources Attosecond lasers ?
1016-1020 W/cm2 : Relativistic plasma physics
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4e 2 0 4e 2 lim ( q, ) = 1 { 2 2 2 m 0 m
k ,l ,l '
kl p k + q, l '
* Temperature can be obtained from f0 : Fermi-Dirac distribution at finite temperature * Spins can be included (with temperature) Stoner model at finite temperature
What is missing ?
* Time is absent : theory of linear response function in the frequency domain. * We do not have a good description of damping: is simply there for causality.
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Screened Coulomb Interaction between quasi-particles
i
W( r,r; Ei Ef )
f E Fermi
Conduction electrons
1 dq 1 =2 Vq m (2) 3 (q, )
Vq : Fourier transform of Coulomb interaction

requires a model for (q, )
Random Phase Approximation (RPA) or (q, ) = RPA(q, ) G(q, )(RPA(q, ) -1) (G : local field factor)
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Alternatively: 1. Fermi liquid approach

For a Fermi liquid with temperature e quasiparticles near the Fermi level scatter according to (Pines & Nozires) :
( k Be ) 2 + (E - E F ) 2 E - EF 1 + exp( ) k Be 1
Good for interband processes specially if interested in the electron dynamics at the threshold of interband transitions 2. Density functional theory
* TDLDA: Time dependent local density approximation * TDLSDA: with spins (both can be performed at finite temperature : even if rigorously exact only for the ground state)
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Schematic of relaxation in a metal excited with (t) pulse

(E)
simple metal : Fermi-Dirac ( E,Te )
athermal Distribution
Electronic dephasing : t < 20 fs plasma oscillations

EF
(E)
Fermi-Dirac Hot : T ~ 1000 K

3
Thermalization of electrons: t < 200 fs diffusion between quasi-particles (Coulomb interaction)
(E)
Cooling of electrons and Heating of lattice : t < 5 ps (electrons-phonons interaction)

* lattice vibrations (coherent) : t < 100 ps * Relaxation of lattice Exchange with environment : t > 1 ns
Fermi-Dirac T > 300 K
EF
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Electron-lattice relaxation: two-temperatures model

Tl 10 - 3 Kfs 1 t Te 10 Kfs 1 t
C e (T e ) Cl dT l dt
dT e = G el (T l (t) T e (t) ) + P(t) dt r r = G el (T e (t) T l (t) ) l T l (t,
r r r e T e (t, r ) r r)
1200
Temperature (K)
Laser pulse
1000 800 600 400 200
Telectrons TLattice
0 5 10 (ps) 15
IP
CM
Time
Phenomenological account for non-thermal effects

dN = N N + P(t) dt r r r dT e C e (T e ) = G el (T l (t) T e (t) ) e T e (t, r ) + N dt r r r dT l Cl = G el (T e (t) T l (t) ) l T l (t, r ) + N dt
temperature (K)
N : Volume density of non-thermal electrons = 1/th : coupling between the non thermalized and thermalized electrons 650 : coupling to phonons.
600 550 500 450 400 350 -2 0
(electrons)
(lattice)
laser
n(t)
0.0 0.5 1.0 time (ps)
10
time (ps)
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Phenomenological approach to time dependent processes in metals 1)
(r,t) [r,Te(t)]
2) Suppose that we are in the adiabatic regime (the temperature changes slowly enough so that the medium respond instantaneous OK for electrons) D(r,t)=E(r,t) and B(r,t)=M(r,t) P(r,t)=eE(r,t) and M(r,t)=mH(r,t)
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Linear absorption spectrum of Cu nanoparticles
Optical density
0.8
Cu : 10 nm
0.4
0 1.8
Edp
2.2 2.6 (eV)
Edp : interband transition; quasi-particle/plasmon coupling
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Pump-probe dynamics of Cu Nanoparticles

0
Delay (picoseconds)
1.2 0.8 0.4 0

1.8 2.0 2.2 2
Energy (eV)
J.-Y. Bigot, J.-C. Merle, O. Crgut, A. Daunois
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Phys. Rev. Lett., 75, 4702-4705 (1995).
Thermalization of electrons in metallic nanoparticles

F. Valle - Bordeaux
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Surface plasmon dynamics

T/T (normalized)
1 ,0
Cu: 10 nm
2.255 eV 2.18 2.139
0 ,5
0 ,0 -1 0 1 2 3
Time delay (ps) Damping in nanoparticles : Kubos assumption
eff
= +
or + F g ( ) R
Origin of temperature dependent relaxation ?

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Screened Coulomb potential in a metallic sphere

V (r , r ') = Vbulk e2 + a 1 4 r r ' 1 lm ( , )lm ( ' , ') 2l + 1 a a l ( ) ( ) l ,m
l l
Many body calculation of damping associated to the Coulomb screening leads to :

h (E d , e ) =
A 1 f o (E c ) Im 2 (E E ) 3 a [E c E d ] d s c
A d hole can decay by emitting a plasmon : Excitation with photons of energy h leads to a resonant scattering of the holes created by the probe. This effect increases with the electron temperature (via f0(Ec)) and when the particle size decreases (via 1/a3).
h f o (E c ) Im
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s ( ) 1
Femtosecond dynamics of Silver nanoparticles
Effect of the surface scattering on the linear response
Dynamical shift of the surface plasmon resonance
J.-Y. Bigot, V. Halt, J.-C. Merle, A. Daunois - Chem. Phys., 251, 181-203 (2000).
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Dynamics of silver nanoparticles

t = 2 ps
1.00 1.00 0.75 0.50 0.25 0.00 -0.25 2.4 2.8 3.2 3.6
0.20 0.15 0.10 0.05 0.00 -0.05 2.4 2.8 3.2
T / T normalized
0.75 0.50 0.25 0.00 -0.25
Te = 600 K 0.20 Te = 1200 K

0.15 0.10 0.05 0.00 -0.05 3.6
T / T
(eV)
(eV)
Experiments
Phys. Rev. B, 60, 11738-11746 (1999). Chem. Phys., 251, 181-203 (2000).
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Theory (TDLDA)
Eur. Phys. J. D 24, 185 (2003) Phys. Rev. Lett., 92, 177402 (2004).
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3. The dynamics of magnetic metallic systems from femtomagnetism to the nanoscale

3.1 Ultrafast Magnetization Dynamics of thin ferromagnetic films
3.2 Ultrafast magnetization dynamics of nanostructures
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Laser field Photons (E, V; A, ) Electrons Charges, plasmons Electrons Spins, magnons
Photons : TeraHertz emission (spins) ; Brillouin scattering Micro-magnetic interactions : Internal Vibrational Relaxat Heat propagation (internal & to environment : substrate ) Precession and damping; Spin torque; Nucleation propagation & pinning of domain walls Fluctuations : Superparamagnetic fluctuations Domain fluctuations
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Photons : High Harmonics & Xrays TeraHertz emission (charges); Raman scattering Luminescence
Lattice Molecular vibrations, Phonons
1.0
M
0.5
C T Tc
Pierre Weiss
0.0
300
600
900
1200
Temperature (K)
TC
Time resolved spin thermometer

700 500 300 700 500 300
E(r,t)
probing Tspins with femtosecond temporal resolution

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Time resolved ellipsometry

Kerr configuration: , reflection
Analyzers Faraday configuration:

, transmission
Pump pulse
t
Probe pulse: linear polarization
sample with magnetization M
The rotation (K, F) and ellipticity (K, F) of the probe polarization are proportional to the Magnetization M
and are measured for each pump-probe delay t M(t)

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h
M
h
M
Ni thin films (M//) Phys. Rev. Lett. 76, 4250 (1996)
CoPt3 thin film (M) PRB, 58, 12134 (1998)

CoPt3 Kerr Signal (a.u.)
No pump
t =500 fs
-4
-2
0 2 H (kOe)
time
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About light pulses interacting with spins
H S E(r,t)
e, p, V(r)
Dirac relatisvistic
ih
(r, t ) = c (p - eA(r, t )) + mc 2 + eV(r) (r, t ) t

Development in 1/c2
(central potential)
Spin orbit coupling
eh 2 1 dV l.s 2 2 2m c r dr
p4 eh eh 2 (p eA ) 2 H= .E p 2 2 divE + eV(r ) 2 2 2 2 2m 8m c 4m c 8m c eh i 2 2 .xE Dont forget me ! 8m c

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Magnetization trajectory and Time domain Ferromagnetic Resonance

Heff
Co/Al2O3
M H0
Gilbert damping:
Pump :P(t)
Probe r dM dt r r r + M (t) Heff ( t ) = -P(t) M (t) r dM dt

damp
Femtosecond optical pulses
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Ferromagnetic resonance induced with femtosecond optical pulses
600
Field ( Gauss )
16 nm Co/Al203 MBE grown
500 400 0.00 -0.02 -0.04 -0.06 -0.08 -0.10 0 200 400 600 800 300 200 100
Time Delay ( ps ) 200 150 100 1 2 3 4
Period ( ps )
Applied field (kOe)

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Heff, M are vector quantities comprehensive description of dynamics involves the modulus and orientation of M(t)
Static polar, longitudinal, transverse (p-pol):
z
M- M- M H
External static field
Ox : Pol = [S() S()] Oy : Long = [S() S()] Oz : Trans = [R() R()]
and time resolved: T/T = [T(t) T0]/T0 R/R = [R(t) R0]/R0 Pol/Pol = [Pol(t) Pol]/Pol Long/Long = [Long(t) Long]/Long Trans/Trans = [Trans(t) Trans]/Trans
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Precession dynamics in 3D
Phys. Rev. Lett. 94, 237601 (2005)
Pol (10 )
-2
16 nm Co/Al203
Polar
0 -4 3 0 -3 2
0 -4
Long (10 )
3 0 -3 2 0
longitudinal
-2
Trans (10 )
transverse
-2
0 0 5 10 15 -2 20 0.0 0.2 0.4 0.6 0.8 1.0
Delay (ps)
Delay (ns)
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Ultrafast Magnetization Dynamics visualized in 3D
16 nm Co/Al203
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Precession dynamics in Co: perpendicular and parallel anisotropies
Co/Al2O3 HAnis sample

Pol/Pol x 10-2
0 -5 -10 -15
0 200 400 600
Co/MgO HAnis // sample

Pol/Pol x 10-2
4 0 -4
100
200
300
Delay (ps)
Delay (ps)
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Model of time dependent magnetization dynamics with anisotropy

* Electron/spin and lattice dynamics: two temperatures model
r dTe = G el (Tl (t) Te (t))+ P(t) e 2 Te (t, r) r dt r2 dT r C l l = G el (Te (t) Tl (t)) l Tl (t, r ) dt C e (Te )
Temperature
electrons lattice 0 time 20 ps
* Bloch equation or LL ( without assuming conservation of |M(t)| )

r r dM r r r dM = M H eff Te (t), Tl (t), M(t) dt dt relax
r r ~ r r H eff (t) = H 0 - N M(t) + H a (t)
* Temperature dependent magnetization modules

r r 2 M(Te (t)) = M s 1 - (Te /Tc ) for Te Tc and M = 0 for Te > Tc
* Temperature dependent magneto-crystalline anisotropie r M(T )

10 l K a (Tl ) = K a (0) MS
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In plane anisotropy
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Beating of spin waves

Co/MgO : excitation of 0 and 1st order standing spin waves
50 nm pol/Pol x 10-2
5 0 -5 -10 0.0 0.1 0.2
Ipump = 0.97 mJ/cm-2 Ipump = 1.84 mJ/cm-2
0 order SW
Delay (ns)
Fourier Transform (a.u.) 1
T1 = 29.5 ps T0 = 35.9 ps T1 = 33.5 ps T0 = 45.6 ps

0 50 100
1st order SW
Frequency (GHz)
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3. The dynamics of magnetic metallic systems from femtomagnetism to the nanoscale

3.1 Ultrafast Magnetization Dynamics of thin ferromagnetic films
3.2 Ultrafast magnetization dynamics of nanostructures
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Dots with perpendicular magnetization Multi-domains structure

MFM imaging of CoPt3 dots
(d=1 m) (d=250 nm)
Some are mono-domains

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Many are mono-domains
amplified Ti:S
(800 nm)
(400 nm)
Resolutions: spatial 300 nm, temporal 150 fs

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Femtosecond magneto-optical confocal microscope

Magnet ( 0.4T)
H
PM F Analyzer F PM Scanning piezo
y x
Sample Focal plane Objective lens:
/2
Pinhole (20 m)
N.A = 0.65 (x 40)
.
R= 5x10- 4 R//
(400 nm) Polarization bridge
Dichroic Beam splitter
Polarizer
Probe (400 nm) Pump (800 nm)
5kHz amplified Ti:S Pulse duration ~120 fs
Optics letters 32, 936-398 (2007)

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Individual 500 nm CoPt3 dot
Optics letters 32, 936-398 (2007)
Gauss250nm Crenel500nm
Gauss300nm Gauss900nm
Photo-induced dot on 15 nm film of CoPt3/Al2O3

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Magnetization dynamics of single CoPt3 dot (1 m)

Differential Magnetization :
M (t ) M (t ) ( I + H ( t ) I H ( t )) = M stat stat ( I + H I H ) stat
0 M / M
e (spin)-l
6 4 2 2 4 6 8
-0.1 -0.2 -0.3 0 e-l = 2.27 ps P1aser= 3.8 mJcm-2 5 10 Delay (ps) 15 20
Pump fluence ( mJ cm-2 )
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Dynamical imaging of a CoPt3 dot (1 m)
M PC
Laser induced writing-reading-erasing

-20 10 0 20
50
M (u.a)
-50x10
-6
Axe des X (m) 20 10 20 30 40 10
-10
Axe des X (m) 20 30 10
Axe des X (m) 20 30
15
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Axe des Y (m) 10 15
Axe des Y (m)
Axe des Y (m)
10
15
10
Reading contrast with the MOPPI: CoPt3/Al2O3
Pump-probe delays
t = 300 fs t = 2 ps t = 10 fs
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Writing a 150 nm single domain without external field CoPt/glass
Laser intensities : 4 mJcm-2 Pump 600 nm Kerr Images
8 mJcm-2
MFM Images
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Magnetization dynamics of a single Permalloy dot (5 x 5 m2 on glass substrate)
0 P= 8 mJ cm-2 -0.5
Precession period = 230 ps
damping = 946 ps
M/M
-0.5
10 Delay (ps)
20
0.5 Delay (ns)
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Dynamics of super-paramagnetic nanoparticles

E = KV sin H cos
2
(a)
0.5
E / KV
Anisotropy K
dipolar
E
(b)
0.5
0 01
12 1
E / KV
00
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KV (1 H / H K ) 2 k BT
HK =
2 KV
if d = 2 nm : = 0 ~ 10-10 s ; if d = 8 nm : ~ 1017 s !
I
Cobalt Nanoparticles Implanted in dielectric Matrices (glass, Al2O3)
D = 4 nm Co in Al2O3
0.0 0.0
t=0 t=1 ns
Pol/Pol (x10)
Long/Long
Pol/Pol
-0.5
-0.1
6 ps
-1.0
400 fs
-0.2 0 50 100 -1.5 -2 -1 0
Delay (ps)
1/p = 50 ps P = 90 ps
Long/Long (x10)
Phys. Rev. Lett. 97, 127401 (2006).

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Langevin approach : Brown 1963

dM dM V + h(t ) = 0M dt dt M
Gilbert damping Fluctuating field : Stationnary Gaussian Stochastic process
hi (t ) = 0 ;
hi t )h j (t + ) = ij (t )
The magnetic moment of one particle is distributed on a sphere with a density of probability W(,,t) which obeys a Fokker-Planck equation
avec : H c 2K 0 M S
2M S H c 2 (M S ) 2 + 0
0 VM SH c 2 k BT
incoherent term
coherent term
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For cobalt nanoparticles with diameter 4 nm in Al2O3:

coherent term : 4.8 x 1010 s-1 with = 90ps incoherent term : 0.38
0 = 55 ps !
2.5 nm = 3
The Gilbert damping varies with the size : = 2/MS0
film = 0.02
10 nm = 0.43
4 nm = 0.46
Magnetization precession The Gilbert damping increases when the size decreases The characteristic times of the Nel-Brown model are close : 1/P = 50ps ; P = 90 ps ; 0 = 55ps
The process of magnetization reversal is probably not fully coherent
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Personal references on electrons and spins dynamics in metallic films and nanostructures A. Ultrafast dynamics of magnetic metals.
* A. Laraoui, M. Albrecht, J.-Y. Bigot Optics. Letters 32, 936-398 (2007). * L.H.F. Andrade, A. Laraoui, M. Vomir, D. Muller, J.-P. Stoquert, C. Estourns, E. Beaurepaire, and J.Y. Bigot Phys. Rev. Lett. 97, 127401 (2006). * M. Vomir, L. H.F. Andrade, L. Guidoni, E. Beaurepaire, J.-Y. Bigot Phys. Rev. Lett. 94, 237601 (2005) * J.-Y. Bigot, M. Vomir, L.H.F. Andrade, E. Beaurepaire Chem. Phys. 318, 137 (2005). * J.-Y. Bigot, L. Guidoni, E. Beaurepaire, P. N. Saeta Phys. Rev. Lett. 93, 077401 (2004). * L. Guidoni, E. Beaurepaire, J.-Y. Bigot Phys. Rev. Lett., 89, 17401-17404 (2002). * J.-Y. Bigot, C. R. Acad. Sci. Ser. IV (Paris) 2, 1483-1504 (2001). * J. S. Dodge, A. B. Schumacher, J.-Y. Bigot, D. S. Chemla, N. Ingle, M. R. Beasley Phys. Rev. Lett., 83, 4650-4653 (1999). * D. S. Chemla, J.-Y. Bigot Chem. Phys., 210, 135-154 (1996). * E. Beaurepaire, J.-C. Merle, A. Daunois, J.-Y. Bigot Phys. Rev. Lett., 76, 4250-4253 (1996). B. Ultrafast electron dynamics in metallic nanoparticles and nanostructured films. * I. Lisiecki, V. Halt, C. Petit, M.-P. Pileni and J.-Y. Bigot, Adv. Mat. 20,1-4, (2008) * V. Halt, A. Benabbas and J.-Y. Bigot Optics Express, 16, 11611 (2008). * V. Halt, A. Benabbas, J.-Y. Bigot Opt. Express 14, 2909-2920 (2006). * A. Benabbas, V. Halt, J.-Y. Bigot Opt. Express 13, 8730 (2005). * P.-A. Hervieux, J.-Y. Bigot Phys. Rev. Lett., 92, 177402-177406 (2004). * J.-Y. Bigot, V. Halt, J.-C. Merle, A. Daunois Chem. Phys., 251, 181-203 (2000). * T. V. Shahbazyan, I. E. Perakis, J.-Y. Bigot Phys. Rev. Lett., 81, 3120-3123 (1998). * J.-Y. Bigot, J.-C. Merle, O. Crgut, A. Daunois Phys. Rev. Lett., 75, 4702-4705 (1995).
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Optics and Spin Photonics of Metallic Nanostructures Jean-Yves Bigot

Institut de Physique et Chimie des Matriaux de Strasbourg

Universit de Strasbourg - CNRS -

Seoul - 2009 - Jean-Yves Bigot - Winter_school_IPCMS-QMMRC

1. The static optical and magneto-optical properties of metallic nanoparticles

Seoul - 2009 - Jean-Yves Bigot - Winter_school_IPCMS-QMMRC

Glass containing Au and Ag nanoparticles

Rose window from Strasbourg Cathedral (15 m diameter)

Seoul - 2009 - Jean-Yves Bigot - Winter_school_IPCMS-QMMRC

Au nanoparticles as agent for high contrast imaging

Seoul - 2009 - Jean-Yves Bigot - Winter_school_IPCMS-QMMRC

Nanoparticles as catalysts for controlling reactions

Generalized reaction coordinate

Seoul - 2009 - Jean-Yves Bigot - Winter_school_IPCMS-QMMRC

Self organization of nanoparticles

3D supra crystals of Cobalt nano-particules

Seoul - 2009 - Jean-Yves Bigot - Winter_school_IPCMS-QMMRC

A historical note about Nanosciences

Seoul - 2009 - Jean-Yves Bigot - Winter_school_IPCMS-QMMRC

1. The static optical and magneto-optical properties of metallic nanoparticles

Seoul - 2009 - Jean-Yves Bigot - Winter_school_IPCMS-QMMRC

Intuitive approach to the response function of metallic nanoparticles

Pind = ( eff 0 ) E ; E loc

The effective dielectric function eff is given by :

Seoul - 2009 - Jean-Yves Bigot - Winter_school_IPCMS-QMMRC

For metals : () and Re() < 0 . Example Drude model of electrons:

Seoul - 2009 - Jean-Yves Bigot - Winter_school_IPCMS-QMMRC

surface plasmon resonance

Seoul - 2009 - Jean-Yves Bigot - Winter_school_IPCMS-QMMRC

Absorption spectra of assemblies of Silver, Gold and Copper metallic nanoparticles

1.0 Absorption (normalized) 0.8 0.6 0.4 0.2 0.0 300

Seoul - 2009 - Jean-Yves Bigot - Winter_school_IPCMS-QMMRC

Au - Ag bimetallic alloys of nanoparticles

0.1 0.2 0.4 0.5 0.6 1

414 428 466 475 486 525

2098 1583 2156 2249 1989 1997

482 502 554 584 600 600

Seoul - 2009 - Jean-Yves Bigot - Winter_school_IPCMS-QMMRC

Needs for comprehensive understanding of metallic nano-objects

Seoul - 2009 - Jean-Yves Bigot - Winter_school_IPCMS-QMMRC

p : Plasmon frequency (~10 eV) : damping !!!

-m (1/D) max for = p Excitation spectrum

Seoul - 2009 - Jean-Yves Bigot - Winter_school_IPCMS-QMMRC

What is missing in the Drude model ?

Dispersion : (q) Temperature of electrons: (, q, kbT) Interband transitions

Calculation of dielectric function for excitation by electromagnetic field

< kl = 1/ 2u kl (r)e ikr Bloch functions with lattice periodicity

Seoul - 2009 - Jean-Yves Bigot - Winter_school_IPCMS-QMMRC

In first order perturbation one gets :

= ( Ekl Ek + q ,l ' ) kl 1 k + q, l ' + [ f o ( Ek + q ,l ' ) f o ( Ekl )] kl H int (r, t ) k + q, l '

e with : kl H int (r, t ) k + q, l ' = kl p.A(q, t )eiqr k + q, l ' mc

e kl p.A(q)eiqr k + q, l ' mc ih h Ek + q ,l ' + Ekl

Seoul - 2009 - Jean-Yves Bigot - Winter_school_IPCMS-QMMRC

Current density operator J(q) :

e 1 e 0 J (q ) = Tr exp(iqr ) A(q) Tr exp(iqr ) p mc m

Using the response theory : Ohms law

One finally obtains the Transverse dielectric function:

f o ( Ek + q ,l ' ) f o ( Ekl ) Ek + q ,l ' Ekl h + ih

Seoul - 2009 - Jean-Yves Bigot - Winter_school_IPCMS-QMMRC

Seoul - 2009 - Jean-Yves Bigot - Winter_school_IPCMS-QMMRC

l = p band Fermi level EF

f o ( Ek + q ,l ' ) f o ( Ekl ) Ek + q ,l ' Ekl h + ih

For photons q ~ 0 (as compared to Brillouin Zone)