Composites Science and Technology 63 (2003) 1203–1208

www.elsevier.com/locate/compscitech

Fast nonlinear refractive index of pure and alloy metallic

nanoclusters in silica glass
E. Cattaruzzaa,*, G. Battaglina, P. Calvellia, F. Gonellaa, G. Matteib, C. Mauriziob,
P. Mazzoldib, S. Padovanib, R. Pollonia, C. Sadab, B.F. Scremina, F. D’Acapitoc
a
INFM, Dipartimento di Chimica Fisica, Università di Venezia, Dorsoduro 2137, I-30123 Venezia, Italy
b
INFM, Dipartimento di Fisica, Università di Padova, via Marzolo 8, I-35131 Padova, Italy
c
INFM, GILDA-CRG, ESRF, B.P.220, F-38043 Grenoble, France

Abstract
Fast nonlinear refractive index and nonlinear absorption coefficient were measured at 527 nm of wavelength for composites
formed by either copper or gold-silver alloy nanoparticles embedded in silica by the Z-scan technique. A single 6 ps long pulse from
a Nd:glass laser was used in the Z-scan measurement, allowing to determine the fast (i.e., non-thermal) component of the nonlinear
response. Both the composites exhibit relatively large (and negative for the Au–Ag alloy) nonlinear index. Transmission electron
microscopy, optical absorption and extended X-ray absorption fine structure spectroscopies were also used to characterize the
samples. Some figures of merit for the two samples were evaluated, as well as the third-order optical susceptibilities.
# 2003 Elsevier Science Ltd. All rights reserved.
Keywords: A. Metal–matrix composites (MMCs); A. Nanostructures; B. Non-linear behaviour; E. Ion implantation

1. Introduction index of refraction n can be expressed as n=n(I)=n0

In recent years, several research groups have studied the
synthesis of nanometer-sized metal particles embedded in
dielectric matrices [1], for the increasing interest on com-
posite materials for all-optical devices as well as for their
magnetic and catalytic properties. Single and sequential
ion implantation are useful tools for preparing metal
nanocluster composite glasses (MNCGs) [2,3]. The thick-
ness of the composite films obtainable by ion implantation
is usually limited to a few hundreds nanometers: an alter-
native MNCG synthesis technique is the radiofrequency
magnetron sputtering deposition, that can easily produce
composite films up to several microns thick [4]. After the
ion implantation or the sputtering deposition, thermal
treatments in controlled atmosphere may tune the prop-
erties of the MNCG, by modifying both the structure and
the composition of the embedded nanoclusters [3,5,6].
The most attractive optical property of MNCGs is the
+n2I, where n0 is the linear refractive index, n2 is the
nonlinear refractive index, and I is the light intensity. If
we assume that the metal nanoparticles are spherical in
shape, with diameter D much smaller than the optical
wavelength l, uniformly and randomly dispersed inside
a dielectric matrix, and with a filling factor (i.e., a
volume ratio) p much smaller than 1, than the effective
dielectric constant "* of the material is [7]:
"  "0
"
¼ "0 þ 3p"0 ð1Þ
" þ 2"0
where "0 is the dielectric constant of the host matrix
(assumed to be a scalar and real quantity), and " ¼ "ð!Þ ¼
"1 þ i"2 is the frequency-dependent dielectric constant of
the embedded clusters. The effective dielectric constant "*
exhibits an enhancement close to a frequency !s such that
"1 ð!s Þ þ 2"0 ¼ 0, called surface plasmon resonance (SPR).
The linear absorption coefficient 0 can be written as:
Kerr nonlinearity, i.e. the refractive index dependence  
on the light intensity. For an optical Kerr material, the !  3"0 2 !  2
0 ¼ p   "2 ¼ p fe "2
n0 c " þ 2"0 n0 c
ð2Þ
* Corresponding author. Tel.: +39-041-234-8595; fax: +39-041- ! "3=2
0 "2
234-8594. ¼ 9p :
c ð"1 þ 2"0 Þ2 þ"22
E-mail address: cattaruz@unive.it (E. Cattaruzza).

0266-3538/03/$ - see front matter # 2003 Elsevier Science Ltd. All rights reserved.
doi:10.1016/S0266-3538(03)00079-4
1204 E. Cattaruzza et al. / Composites Science and Technology 63 (2003) 1203–1208
Factor fe is the local-field enhancement of the polar-
ization: the electric field that actually polarizes the clus-
ter can be much larger than the external applied electric
field. This effect is knows as dielectric confinement.
Depending on the cluster size and composition, at fre-
quencies close to !s the optical absorption spectra of
MNCGs exhibit a surface plasmon resonance band. For
embedded nanoclusters with diameter D < 50 nm and
for low metal volume fraction, the third-order optical
susceptibility, (3), of a MNCG can be written as [1,7]:
of the nonlinear optical properties of a material, Z-scan
allows to determine both sign and magnitude of n2 and
. The technique, originally proposed by Sheik-Bahae et
al. [15] was since then implemented and applied to the
study of several nonlinear composite glasses [12,15–17].
Z-scan technique is very sensitive to detect small non-
linear refraction, but it is however difficult to dis-
criminate between electronic and thermal effects [12,18].
In particular, the use of high repetition-rate lasers for
the Z-scan experiments [19,20] may trigger important
 2 heating of the composite glasses, giving rise to thermo-
ð3Þ ¼ p fe  ð fe Þ2 ðcl3Þ
where w(3)
cl is the third-order optical susceptibility of the
nanoclusters. MNCGs exhibit a third-order optical
nonlinearity that can be enhanced by operating at
wavelengths near the SPR band. For materials without
a preferred symmetry axis, as the MNCGs are, and for
low linear optical absorption, the nonlinear refractive
index n2 and the nonlinear absorption coefficient  are
simply proportional to the real and imaginary part of
(3), respectively, as follows [8]:



n2 m2 =W ¼ 120 2 =cn20 Reð3Þ ðe:s:u:Þ; ð4Þ

mbar, by using two different radiofrequency sources
ðm=WÞ ¼ 480 3 =lcn20 Imð3Þ ðe:s:u:Þ:
For an optical Kerr medium, the intensity-dependent
absorption coefficient can be written as =(I)=0 + I.
Due to the fast response time of the embedded metal
nanoclusters, typically of a few ps [9,10], MNCGs are
attractive for all-optical application up to the THz
range of frequency. However, the actual processing rate
of a device is determined not only by the response time
of the physical process (the optical nonlinearity), but
also by the recovery time of the whole composite system
of which the device is made. In a lot of literature, sur-
prisingly large values of the third-order optical suscept-
ibility, (3), as well as of the nonlinear refractive index,
n2, are usually reported: indeed, in most of the cases
they were measured by using experimental setups invol-
ving high repetition rate laser sources, or with pulse
duration larger than a few ps. The repetition rate and/or
the pulse duration cause important thermal loading
effects of the whole composite, thus inducing thermo-
optical nonlinearities, characterised by recovery times
much larger than few ps [11,12]. The performances of the
device materials are easily assessable by the evaluation of
some figure of merits, FOMs [12–14]. Depending on the
main absorption mechanism of a given material, i.e. lin-
ear or nonlinear, two conditions must be satisfied:
jn2 jImax l
W¼ > 1; T¼ < 1;
0 l j n2 j
where Imax is the damage threshold intensity value for
the material. Among the techniques for the measurement
ð3Þ optical nonlinearities (due to cumulative heating of the
sample) that can obscure all fast relaxation processes
[11,12,18]: as a consequence, the use of both very low
repetition-rate and pulse duration less than few ps is
recommended for the determination of fast nonlinearities.
2. Experimental
The copper MNCG sample (hereafter indicated as
‘‘45-H’’) was synthesized by radiofrequency magnetron
multitarget co-sputtering deposition of silica and cop-
per, in pure Ar atmosphere at a pressure of 30104
ð5Þ (for silica and copper, respectively). After deposition of
a 2.7 mm composite film on a silica substrate, a thermal
treatment on the sample was performed at 900 C, for 4
h, in N2 +H2 (4%) reducing atmosphere, to promote
the growth of copper metal nanoparticles. The Au+Ag
alloy MNCG sample (hereafter indicated as
‘‘Au3Ag6A’’) was synthesized by sequential ion
implantations on a silica substrate (Herasil, Heraeus) at
current densities lower than 2 mA/cm2. Implantations
were performed at INFN-INFM Ion Implantation
Laboratory (INFN—Legnaro National Laboratories,
Italy). The first irradiation was Au (190 keV) at a flu-
ence of 31016 ions/cm2, the second one was Ag (130
keV) at a fluence of 61016 ions/cm2. The implantation
energies were chosen to get the same projected range of
about 70 nm, i.e. a good overlapping of the different
atomic species. A subsequent thermal annealing in air at
800 C, for 1 h, was performed on the sample.
Rutherford backscattering spectrometry (RBS) mea-
surements were performed at INFN—Legnaro National
Laboratories, Italy, with a 4He+ beam at the energy of
2.2 MeV.
Transmission electron microscopy (TEM) and selec-
ted area electron diffraction (SAED) measurements
were performed at CNR-LAMEL Institute (Bologna,
Italy) with a Philips CM30T microscope, operated at
300 kV and equipped with an energy dispersive X-ray
ð6Þ spectrometer (EDS).
X-ray absorption fine structure (EXAFS) spectro-
scopy at the Ag K-edge (E0 =25414 eV) and the Au LIII-
edge (E0 =11919 eV), at liquid nitrogen temperature in
 E. Cattaruzza et al. / Composites Science and Technology 63 (2003) 1203–1208 1205

fluorescence mode, was performed on the GILDA

beamline at the European synchrotron radiation facility
(ESRF) in Grenoble, France.
Optical absorption spectra were determined in the
350–750 nm wavelength range by using a Cary UV–vis-
NIR dual-beam spectrophotometer.
Z-scan measurements were performed using a ring-
cavity, mode-locked Nd:phosphate glass laser as a
source. The laser supplies single shots at a very low
repetition rate (about 1 Hz), each one being a train of
about 100 pulses of nearly equal intensity, 5 ns spaced in
time. By means of a pulse-slicer, we used only a single 6
ps pulse for any shot, for evidencing the fast nonlinear
processes. The laser was operated in the TEM00 mode at
fixed power output; peak power was about 140 MW.
The beam waist w0 at the focal point of the apparatus
was about 20 mm. Using filters of different optical den-
sity, the peak intensity at the focal point was varied.
Each point in the Z-scan curve is the average of 20
Fig. 1. Optical absorption spectra of the copper MNCG before and
shots. The second harmonic (l=527 nm) of the laser after the thermal treatment. Arrow indicates the wavelength used
was used for the measurements, and CS2 was used as a during the Z-scan experiment.
reference sample (n2 =31014 cm2/W).

3. Results and discussion

RBS measurements on the 45-H sample show that

this composite is quite homogeneous in composition,
with 7% atomic fraction of copper embedded in a stoi-
chiometric silica matrix. In the Au3Ag6A sample, the
metal atomic fraction is 11%. RBS evidences that the
actual fluences of gold and silver are almost balanced,
while they were measured in the ratio 1:2 before the
thermal treatment: this is due to out-diffusion of a cer-
tain amount of silver atoms during the annealing in air.
Optical absorption analysis gives the first indication on
the actual metal nanoparticle formation. The absorp-
tion spectra of the Cu:SiO2 co-sputtered sample (Fig. 1)
exhibit a structured band only after the thermal treat-
ments: the SPR band is much more visible after anneal-
ing in reducing atmosphere (sample 45-H) and it is
centered around 560 nm of wavelength, the typical value
Fig. 2. Optical absorption spectrum of the Au3Ag6A sample, with the
for metallic copper nanoclusters embedded in silica SPR wavelength position for pure silver (410 nm) and gold (530 nm)
matrix [21]. The arrow indicates the wavelength used for nanoclusters in silica. The third arrow indicates the wavelength used
the Z-scan measurements. Due to the thickness of the during the Z-scan experiment.
sample, after the copper cluster formation the optical
absorbance is very high at low wavelengths. In Fig. 2
the absorption spectrum of the Au3Ag6A sample is metallic systems were present the optical density would
shown, together with the SPR wavelength position for exhibit two distinct peak, due to the SPR signals of sin-
pure silver (410 nm) and gold (530 nm) nanoclusters in gle metal nanoclusters [21]. A shift of the single SPR
silica. The third arrow indicates the wavelength used for band position or the disappearance of any absorption
the Z-scan measurements. The position of the SPR is at bands [22] are usually related to the alloy particle pre-
480 nm of wavelength, i.e. in between those of pure sil- sence. Thus, in the Au3Ag6A sample the SPR band
ver and pure gold. Being the optical properties of position suggests that an intermetallic gold-silver alloy
MNCGs strongly related to the composition and size of is formed. SAED analysis shows a single fcc Debye–
the embedded nanoclusters [Eq. (2)], if two separate Scherrer pattern of randomly oriented nanoparticles,
1206 E. Cattaruzza et al. / Composites Science and Technology 63 (2003) 1203–1208
Fig. 3. Far field Z-scan curve for the 45-H sample, together with the
curve fit (l=527 nm, single pulse 6 ps long, 1 Hz repetition rate,
I=10.7 GW/cm2).
with diameter 14.3
7.9 nm [6]. The detection of a intensity was 10.7 GW/cm2, slightly less than the
possible alloy formation is quite a critical task, because
the lattice parameter of fcc gold and silver bulk phases
0.2)1011 cm2/W, in
are very close (aAu =0.40786 nm, aAg =0.40862 nm):
therefore, the measured lattice parameter a=0.04079
0.1
0.00012 nm does not allow to unambiguously
demonstrate the alloy formation. However, by focusing
a nanometric electron probe on single clusters, the
0.2)107 cm/W.
resulting EDS spectrum indicates the presence of both
gold and silver atoms in the same nanoparticles, thus
assessing alloy formation [6]. EXAFS spectroscopy
confirms this conclusion. By collecting the X-ray
3)1011 cm2/W. The linear absorption coef-
absorption spectrum at Ag K-edge and Au LIII-edge,
the local order around the two species is separately
investigated: the first shell of atoms around the two
0.3)105 cm/W. The damage threshold inten-
dopants is composed by both gold and silver, indicating
that fcc gold-silver nanoparticles in solid solution are
formed [23,24]. From the coordination numbers that
result from the fitting procedures, it can be estimated
that the alloy composition is almost balanced (about
1:1), maybe slightly richer in silver [23]. No oxide phases
are detected.
In Fig. 3, the far field Z-scan curve recorded at l=527
nm with one pulse is shown for the 45-H sample, toge-
ther with the curve fit obtained following the Sheik-
Bahae frame [15]. During measurements, the peak
Table 1
Linear and nonlinear optical parameters of the two analyzed MNCGs (527 nm of wavelength, 6 ps pulse length, 1 Hz repetition rate). Figures of
merit W and T are also reported
Fig. 4. Far field Z-scan curve for the Au3Ag6A sample, together with
the curve fit (l=527 nm, single pulse 6 ps long, 1 Hz repetition rate,
I=1.6 GW/cm2).
damage threshold intensity (around 15 GW/cm2). The
calculated value of n2 is (1.1
agreement with previous results for copper MNCG
[8,12,18]. The linear absorption coefficient 0 is 2.6
mm1. The near field configuration data evidence also
nonlinear absorption effects: the calculated nonlinear
absorption coefficient  is (2.0
Fig. 4 shows the Z-scan curve for the Au3Ag6A sample,
recorded with a peak intensity of 1.6 GW/cm2: the sign
of n2 is negative, estimated for this sample as n2
=(16
ficient is 0 =15.3 mm1. Also the Au3Ag6A sample
exhibits nonlinear absorption: the calculated value for 
is (1.3
sity of this sample is around 5 GW/cm2. For both sam-
ples, an increase in the number of pulses on the same
laser shot did not give rise to detectable variation of the
n2 values: this evidence agrees with the determination of
the contribution to n2 of thermal loading of the MNCG,
that for our Z-scan system is few 1013 cm2/W for any
pulse of the single laser shot [12,18]. Starting from the
experimental values of the n2, 0, and , we are able to
estimate the FOM values for the analysed MNCGs.
Table 1 summarizes the values of n2, 0, , the modulus
and phase of (3), and the calculated FOMs. The values
 ð3Þ 
Sample n2 (cm2/W) 0 (mm1)  (cm/W)  ðesuÞ Phase of (3) W T

45-H (1.1
0.2)1011 2.6
0.1 (2.0
0.2)107 (5.9
1.0)1010 (4
1) 0.12 1
Au3Ag6A (16
3)1011 15.3
0.1 (1.3
0.3)105 (9.2
1.5)109 (160
10) 0.03 4.3
 E. Cattaruzza et al. / Composites Science and Technology 63 (2003) 1203–1208
for the 45-H sample are not so different from those
found for silica containing copper clusters by Tanahashi
et al. [8] at the SPR wavelength: we find a n2 value three
times larger (anyway, of the same magnitude order),
probably due to the low pulse duration they used (150 fs).
About the absorption parameters, Tanahashi et al.
detected a (negative) value for  four times larger, while
the reported linear absorption coefficient is about two
order of magnitude larger than ours. These two findings
are probably due to the different wavelength used dur-
ing Z-scan characterization: we used l=527 nm (SPR at
560 nm), while they worked exactly at the SPR of their
composite (l=580 nm), therefore enhancing the linear
and nonlinear absorptions of the material. The main
peculiarity of the nonlinear optical properties of the
Au3Ag6A sample is the very large (negative in sign)
value of n2. Recently, Ganeev et al. [25] studied the
optical nonlinearities of different metal colloidal solu-
tions by Z-scan, finding at l=532 nm negative n2 values
for the gold and copper cases at the initial stages of
aggregation. For silver, they evidenced a n2 sign change
from positive to negative upon clusters growth. They
correlated these peculiarities to the different aggregation
rate of the clusters (i.e., to their size inside the solution).
In our opinion, a careful study of magnitude and sign of
the local-field enhancement factor fe (strongly depen-
dent on the particle size and composition, as well as on
the wavelength used) could be the first step for giving
some useful insight on the understanding of the descri-
bed features [21].
4. Conclusion
Two MNCGs were synthesized by different synthesis
techniques, i.e. by radiofrequency magnetron sputtering
co-deposition of copper and silica, and by sequential ion
implantation of gold and silver in silica. The samples
were subsequently annealed in controlled atmosphere
and then their nanostructure was characterized by
means of TEM and EXAFS. The nonlinear optical
properties were investigated by the Z-scan technique.
The 45-H sample, formed by copper nanoparticles in
silica, exhibits the best figures of merit for technologi-
cal application. The Au3Ag6A sample, formed by
AuAg alloy nanoparticles in silica, shows the peculiar-
ity of a very large and negative in sign nonlinear
refractive index. The optical properties of the 45-H
sample are better if compared to a similar copper
MNCG [12,18], but yet insufficient for the application
of MNCG materials in all-optical switching technol-
ogy. In our opinion, the improvement of the figures of
merit could be attempted by synthesizing MNCGs with
very small nanoclusters (i.e., not larger than 1 nm in
size), and/or exploring very high values of the cluster
volume ratio [12].
1207
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