VOLUME 85, NUMBER 4 PHYSICAL REVIEW LETTERS 24 JULY 2000

Observation of Hot-Electron Pressure in the Vibration Dynamics of Metal Nanoparticles

M. Perner, S. Gresillon, J. März, G. von Plessen, and J. Feldmann
Lehrstuhl f ür Photonik und Optoelektronik, Sektion Physik and CeNS, Ludwig-Maximilians-Universität München,
Amalienstrasse 54, D-80799 München, Germany

J. Porstendorfer, K.-J. Berg, and G. Berg

Fachbereich Physik, Martin-Luther-Universität Halle-Wittenberg, Friedemann-Bach-Platz 6, D-06108 Halle, Germany
(Received 3 May 1999)
We investigate the vibration dynamics of ellipsoidal silver nanoparticles, using time-resolved optical
pump-probe spectroscopy. When excited with femtosecond laser pulses, the particles execute anisotropic
shape oscillations. We show that these vibrations are triggered by the thermal expansion of the optically
heated particles. The time dependence of the vibrations indicates that this expansion is caused by two
mechanisms: The lattice anharmonicity and the extremely large pressure of the hot conduction electrons.

PACS numbers: 62.30. + d, 65.70. + y, 78.47. + p

The thermal expansion of metals has two fundamental on spherical particles for comparison. Upon deformation
causes: the anharmonicity of the ion-ion interaction, and into ellipsoidal shape, the surface-plasmon (SP) resonance
the thermal pressure of the free electron gas. The electron of the spherical particles at 2.82 eV (not shown here) splits
pressure gives a dominant contribution to the thermal ex- up into two spectrally separate surface-plasmon resonances
pansion at temperatures on the order of a few kelvins [1]. that can be excited with light polarized parallel to the short
At elevated temperatures, however, it is negligible com- and long axes, respectively, as shown by the extinction
pared to the ionic contribution. spectra in Fig. 1 [7,8]. The short-axis SP resonance (SAP)
Recently, fast heating of metals via absorption of ultra- peaks at an energy of 3.06 eV, while the long-axis SP
short laser pulses has attracted much interest. The thermal (LAP) peaks at 1.88 eV. Time-resolved optical pump and
expansion caused by such heating is time dependent and probe experiments are performed with 150 fs laser pulses
results in dynamic phenomena such as stress wave gen- generated by a regenerative amplifier and subsequent fre-
eration at metal surfaces [2]; it has also been suggested quency doubling or white-light continuum generation. The
to be the origin of acoustic vibrations in metal nanopar- SAP is pumped at 3.1 eV with frequency-doubled pulses
ticles [3–5]. When the metal is heated by femtosecond (pulse fluence: 1 mJ兾cm2 ) and the response of both SP’s
laser pulses, the electrons can momentarily reach tempera- is probed with polarized pulses at various wavelengths re-
tures much higher than that of the lattice [2]. One should alized by selecting part of the white-light spectrum with
then expect that the contribution of the electron pressure
to the thermal expansion is significantly modified com-
pared to room temperature. Indeed, it has been predicted
theoretically that this contribution should be dramatically
enhanced at high electron temperatures, and could even be-
come larger than the lattice contribution [6]. This effect, if
confirmed experimentally, could have very important con-
sequences for the time dependence and size of dynamical
thermal expansion phenomena in metals.
Here we show that the thermal pressure of the hot con-
duction electrons makes an extremely large contribution
to the thermal expansion of ellipsoidal silver nanopar-
ticles heated by femtosecond laser pulses. This contribu-
tion shows itself in the time dependence of acoustic particle
vibrations triggered by the thermal expansion.
The silver nanoparticles studied here were grown via
Ag1 兾Na1 ion exchange in a glass matrix, resulting in
spherical particles with a mean diameter of 60 nm. Ellip-
soidal particles were made by subjecting spherical particles FIG. 1. Optical extinction spectra taken on ellipsoidal silver
to tensile deformation [7]; they have mean axis lengths of nanoparticles with light polarizations as indicated by the
arrows. LAP and SAP denote the long-axis and short-axis
a 苷 b 艐 40 nm and c 艐 100 nm, respectively, and a uni- surface-plasmon resonances, respectively. Inset: transmission
form orientation. In this Letter, we will mainly focus on the electron micrograph of an ellipsoidal silver nanoparticle em-
ellipsoidal particles, but will also present some data taken bedded in glass.

792 0031-9007兾00兾85(4)兾792(4)$15.00 © 2000 The American Physical Society

VOLUME 85, NUMBER 4 PHYSICAL REVIEW LETTERS
interference filters. The differential transmission DT 兾T ,
i.e., the relative change in probe transmission induced by
the pump pulse, is recorded as a function of the time delay
between the pump and probe pulses, t.
Figure 2 shows two DT 兾T transients taken with the
probe pulses centered at the low-energy sides of the SAP
(2.25 eV) and LAP (1.77 eV), and polarized along the
short and long particle axes, respectively. In addition,
also a transient from a sample with spherical particles is
shown, where pumping and probing were done at 3.1 and
2.25 eV, respectively. In all cases, an initial rapid increase
of the signal is observed during the first picosecond after
excitation, followed by a two-step decay with decay times
of several picoseconds and several hundred picoseconds,
respectively. In addition, the signals exhibit periodic
modulations during the second decay step. Additional
measurements at different probe photon energies (not
shown here) demonstrate that these signals are caused
mainly by pump-induced redshifts of the respective SP’s.
The initial increase and the two-step decay of these
redshifts can be understood on the basis of earlier work on
metal nanoparticles excited by short laser pulses [9–12].
The initial increase of the SP redshift is caused by the
change of the dielectric properties of Ag brought about by
the laser-induced electron heating [12]. The time taken
by the redshift to reach its maximum (i.e., 艐1 ps) is the
thermalization time of the nonequilibrium electron-hole
distribution resulting from the decay of the SAP excited by
the pump pulse [10,11]. During the subsequent 5–10 ps,
the hot electrons cool down via phonon emission, thereby
heating up the lattice rapidly [9]; this electron cooling
results in a reduction of the redshift. In the second decay
step, the nanoparticle slowly cools to room temperature
via heat transfer to the surrounding glass matrix, resulting
FIG. 2. Differential transmission transients (upper curves: el-
lipsoidal particles; lowest curve: spherical particles; the tran-
sients are vertically offset for clarity). The light polarizations
and photon energies of the pump and probe pulses are indicated.
Solid lines: fits to the data as explained in part (iv) of the text.
24 JULY 2000
in the final return of the SP energies to their room-
temperature values.
An important observation is that the redshift in the
second signal-decay step exhibits periodic modulations
(Fig. 2). Similar modulations have been observed in
pump-probe experiments on spherical metal nanopar-
ticles, and explained as the signature of acoustic particle
vibrations [3–5]. A remarkable difference is that in our
ellipsoidal nanoparticles the time period of the modulation
depends on the particle axis probed. A time period of
艐22 ps is observed when probing the SAP (central trace
in Fig. 2), while a period of 艐52 ps is observed at the
LAP (upmost trace). The modulation periods are found to
be independent of pump intensity. In the following three
paragraphs (i)–(iii), we will show that these modulations
are caused by anisotropic acoustic vibrations of the ellip-
soidal particles, and that these vibrations are triggered by
the optically induced thermal expansion of the particles.
Subsequently, and most importantly, we will show in
part (iv) that the contribution of the electron pressure to
this expansion is extremely large.
(i) First, we will estimate the time periods of the vibra-
tions and show that they agree with the measured modu-
lation periods. In contrast to spherical particles, where
the frequency spectrum, and, hence, the vibration periods
can be calculated analytically using elasticity theory [13],
no such analytical treatment is known for ellipsoids.
Instead, we approximate here the vibrational normal
modes as standing one-dimensional acoustic waves with
free boundary conditions (the influence of the embedding
matrix will be treated later). Using the known longitudinal
sound velocity in Ag, yL 苷 3650 m兾s, the time periods
of the lowest longitudinal eigenmodes are calculated to
be 23 and 56 ps for vibrations along the short and long
particle axes, respectively, in very good agreement with
the observed modulation periods.
(ii) We will now discuss the mechanism triggering the
particle vibrations. The heating by the pump pulse is ex-
pected to result in a thermal expansion of the particle. Dur-
ing this expansion, the inertia of the ions will make them
overshoot their new (high-temperature) equilibrium posi-
tions. This overshoot will be followed by a reversal of the
expansion, due to the elasticity of the metal. The particle
thus begins to oscillate between a mechanically “overex-
panded” and a “compressed” state with respect to the high-
temperature equilibrium size. These length oscillations
occur at the vibrational eigenfrequencies estimated above;
we will calculate their amplitudes in part (iv).
(iii) We will now discuss the physical mechanism by
which the vibrations show themselves as periodic modula-
tions of the SP redshift. According to Ref. [4], the periodic
changes in electron density associated with the particle-
length oscillations are expected to change the dielectric
function of the metal, resulting in a periodic SP redshift.
In the present case of ellipsoidal nanoparticles, this mecha-
nism would imply that a change in electron density due to
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VOLUME 85, NUMBER 4 PHYSICAL REVIEW LETTERS 24 JULY 2000

a length change along one axis should be visible also along tures by using the standard two-temperature model with
the other axis. In contrast, we observe different modulation CL and Ce of silver as given in Ref. [12] and taking into
periods along the long and short axes; thus the explanation account the energy absorbed by each particle per pulse.
suggested in Ref. [4] cannot apply here. Instead, we sug- The thermalization of the electron system is modeled by
gest that the SP redshift is caused by an electromagnetic heating the cold Fermi sea with a time constant of 1.2 ps,
retardation effect known to shift the SP resonance towards as observed experimentally. The calculated time evolu-
low energies with increasing particle length [8]. In our ex- tions of the electron and lattice temperatures, Te and TL ,
periment, the particle-length oscillations, whose amplitude respectively, are plotted in Fig. 3(a). Using the stresses
we will calculate in part (iv), are expected to induce elec- sL and se calculated from TL and Te via Eq. (2), we now
tromagnetic SP shifts resulting in a DT 兾T of ⬃1%. The solve Eq. (1) to determine the particle elongation. In doing
effect suggested here is thus large enough to explain the so, we assume v0 苷 2p兾50 ps and r 苷 2p兾200 ps for
signal modulation amplitude observed experimentally. the lowest long-axis vibration (the ratio of v0 : r 苷 4 : 1
(iv) Having discussed the basic effects involved in the is typical for embedded particles). Here, as in Eq. (1), we
periodic modulation of the pump-probe signal, we will, neglect higher vibrational modes since a careful analysis
in the following, present a more quantitative evaluation, [15] shows that, under the present optical excitation con-
which will, in particular, clarify the role played by the ditions, s does not vary rapidly enough as to give great
electron pressure in the thermal expansion of the particles. spectral weight to higher vibration modes. The solution
In a first step, we will give expressions for the time of Eq. (1) is shown in Fig. 3(b); the dotted line shows the
dependence of the particle lengths. In an elastic continuum contribution to the particle elongation that results from
model of the particle, any force elongating the particle the lattice anharmonicity, DxL , and the dashed line shows
along one of the principal axes (such as the forces leading the contribution from the thermal pressure of the free
to the thermal expansion of the particle) can be described electrons, Dxe . Both contributions exhibit oscillations due
in terms of a stress s being exerted on the particle surface
along the same direction. The particle elongation Dx, i.e.,
the deviation from the equilibrium length of the particle,
is then described by the differential equation,
d2 d
2
Dx 1 2r Dx 1 v02 Dx 苷 As兾m , (1)
dt dt
where r describes the damping due to mechanical cou-
pling to the embedding matrix, A and m are the surface
area and mass of the particle, respectively, and v0 is the vi-
brational eigenfrequency along the respective particle axis
(for simplicity, we consider here only the lowest vibra-
tional eigenmode, which is expected to have a consider-
ably larger vibration amplitude than the higher modes, for
reasons to be discussed later). Equation (1) is the equa-
tion of motion of a dampled driven oscillator, and can be
solved if the time dependence of s is known. This time
dependence is found by the following considerations: The
total stress involved in the thermal expansion of the particle
consists of a lattice contribution and an electronic contri-
bution, s 苷 sL 1 se . These two contributions originate
from the lattice anharmonicity and the thermal pressure of
the free electrons, respectively, and are given by [14]
Z TL,e
sL,e 苷 2gL,e CL,e dTL,e . (2)
TR

Here, TL and Te are the temperatures of the lattice and

the electron system, respectively, CL and Ce 苷 Ce 共Te 兲
are their heat capacities, and gL 艐 2.4 and ge 艐 1.2 [1]
are their respective Grüneisen constants. TR denotes room
temperature.
Equations (1) and (2) enable us to calculate the time
dependence of Dx if those of TL and Te are known. For
this purpose, we calculate the lattice and electron tempera-
FIG. 3. (a) Calculated time dependence of the electron and
lattice temperatures, Te and TL . (b) Calculated time dependence
of the electronic 共Dxe 兲 and lattice 共DxL 兲 contributions to the
elongation of the long particle axis, Dx. (c) Circles: differential
transmission data (same as in the upmost curve in Fig. 2). Solid
line: fit to the data; dashed line: dielectric contribution to the
fit; dash-dotted line: elongation-induced contribution.

794
VOLUME 85, NUMBER 4 PHYSICAL REVIEW LETTERS
to the excitation of particle vibrations by the respective
temperature-induced stresses, sL and se . The phase shift
between the two contributions is due to the different time
dependencies of the stresses; while sL is controlled by TL
and, hence, essentially has a steplike time dependence, se
is controlled by Te and has a d-like time dependence. The
dash-dotted line in Fig. 3(b) shows the total particle elon-
gation, Dx 苷 Dxe 1 DxL . For late times, the oscillations
of Dx disappear due to the damping of the vibrations,
and Dx converges towards 0.3 nm, which is identical
with the estimated thermal expansion that would have
been obtained under adiabatic heating. We note that this
equilibrium value of the thermal expansion comes almost
entirely from DxL , thus illustrating the fact that the
electron-pressure contribution to the thermal expansion is
negligible under thermal equilibrium conditions.
We will, in the following, use the results for TL , Te ,
and Dx to fit the experimental signal. An exact calcula-
tion of the differential transmission DT 兾T (e.g., along the
lines described in Ref. [16]) is difficult since its precise
quantitative value depends on details of the Ag dielectric
function, which is not experimentally known for situations
where Te fi TL , and on the exact spectral distribution
of the inhomogeneous broadening. Therefore we use here
a simplified approach for the fit. We decompose DT 兾T
into two contributions, one of which originates from the
temperature-induced changes of the dielectric properties
of the metal [12], while the other one is caused by the axis
elongation. The first contribution is approximately linear
in the temperature rises DTe and DTL ; we choose the pro-
portionality factors such that the experimental DT 兾T trace
is reproduced during the first picosecond after the pump
pulse, when Dx is still small [dashed line in Fig. 3(c)]. The
elongation-induced contribution to DT 兾T is approximately
linear in Dx; we scale this contribution (dash-dotted line)
so that DT 兾T is reproduced at t 苷 100 ps by the sum of
the dielectric and elongation-induced contributions. The
solid curve in Fig. 3(c) shows the result, which reproduces
the measured signal modulations perfectly. Likewise, we
find very good agreement between calculation and experi-
ment for the short-axis vibration (center curve in Fig. 2),
and reasonably good agreement for the spherical particles
(lowest curve in Fig. 2). In particular, in all cases the cal-
culated oscillations are almost exactly in phase with the
measured ones. Conversely, if Dxe was zero, the calculated
oscillation would lag behind the measured one by a phase
shift of approximately 30±; this is shown by a comparison
of the phase of DxL [Fig. 3(b)] with that of the modu-
lation in Fig. 3(c). The good agreement achieved in the
24 JULY 2000
fit therefore demonstrates that the electron pressure makes
an essential contribution to the thermal expansion. At the
maximum of Te 共艐3000 K兲, the electron-pressure induced
stress is, according to Eq. (2), a factor of 艐800 greater
than at the temperature at which the electrons and lattice
equilibrate (450 K). This brings the electron-pressure con-
tribution to the thermal expansion into a range where it
becomes comparable to the contribution from the lattice
anharmonicity. Our results thus emphasize the necessity
of including the electron pressure in any treatment of the
structural dynamics of metals where very high electron
temperatures are involved.
In conclusion, we have observed anisotropic particle
vibrations of ellipsoidal silver nanoparticles. These vibra-
tions are triggered by the thermal expansion of the optically
heated particles. Their temporal phase shows that the pres-
sure of the hot conduction electrons makes an extremely
large contribution to the thermal expansion.
We acknowledge financial support from the European
Union (through the TMR network “Ultrafast Quantum Op-
toelectronics”) and the Deutsche Forschungsgemeinschaft.
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