# Metallic Nanoparticles Embedded in a Dielectric Matrix:

Authors: M. García del Muro; Z. Konstantinovic; M. Varela; X. Batlle; A. Labarta
Journal: Journal of Nanomaterials
 (2008)

---

## Abstract

We present a study of the preparation and structural characterization of granularAg-ZrO2, Co-ZrO2, and Au-ZrO2 thin films grown by pulsed laser deposition (PLD) in a wide range of volume fraction
x of metal  (0.08<xAg<0.28, 0.06<xCo<0.40, and 0.08<xAu<0.55). High-resolution transmission electron microscopy (HRTEM) showed regular distribution of spherical Au, Co, and Au nanoparticles having very sharp interfaces with the amorphous matrix. The structural results are compared aiming to stress the effect of the actual microstructure on the percolation threshold. Two different mechanisms of particle growing as a function of the metal content are evidenced: nucleation and particle coalescence, with their relative significance depending strongly on the type of metal, giving rise to very different values of the percolation threshold (xc(Ag)∼0.28, xc(Co)∼0.35, and xc(Au)∼0.55).


---

## Body

## 1. Introduction

The latest great
advances in fine particle systems field have been promoted by the development
of new measuring techniques and refinement of synthesis methods allowing the
preparation of particles at the nanometric scale with promising technological
applications in many different fields. In particular, granular films, in which
a distribution of ultrafine metallic particles is embedded in a dielectrix
matrix, comprise a very active research topic. From a
fundamental point of view, these composite systems show a variety of behaviors
related to percolation processes that the standard percolation theories have
not satisfactorily explained yet [1–3]. From technological aspect, spherical
particles of noble metals homogeneously dispersed in dielectric matrix exhibit
promising optical applications [4–6], associated with its large third-order nonlinear
susceptibility [7–9] and ultrafast response [10]
when approaching percolation. When the metal is magnetic, granular
magnetic solids are excellent materials to study basic properties, such as finite-size
interaction and surface effects, and enhanced and tailored properties [11]. From the technological point of view, their
magnetic and magnetotransport properties also suggest attractive applications,
including high coercive films for information storage [12, 13],
high-permeability high-resistivity films for shielding and bit writing at high
frequencies [14], and giant magnetoresistance for read
heads and magnetic sensors [15].In this paper, we present the preparation and structural
characterization by HRTEM of granular Ag-ZrO2, Co-ZrO2, and
Au-ZrO2 thin films grown by PLD from a single composite target
within a wide range of volume fraction x of metal, from the dielectric regime
until percolation (0.08 < xAg < 0.28,  0.06 < xCo < 0.40,
and 0.08 < xAu < 0.55). Statistical analysis of TEM images
provides us with the mean size and width of the size distribution as a function
of metal concentration. In particular, we observe that for the three prepared
metals, the mean size of the particles increases in a very different way with
the metal content. The role played by the two identified growing mechanisms
(coalescence and nucleation) is shown to be very different in these three
systems, and so leading to different percolation threshold.


## 2. Experimental

Ag-ZrO2, Co-ZrO2,
and Au-ZrO2 granular films were grown by KrF laser ablation
(wavelength of 248 nm, pulse duration of τ=34 ns). The samples were deposited at room
temperature in a vacuum chamber with rotating composite targets made of sectors
of ZrO2 and metal (silver, cobalt, or gold). Several surface ratios
of target components led to obtainning samples with different volume fractions
x of Ag/Co/Au, ranging from metallic to dielectric regimes. The distance
between target and substrate was fixed to 35 mm. The laser fluency typically used was
about 2 J/cm2. Zirconia was stabilized with 7 mol.% Y2O3,
which provides the matrix with very good properties, such as good oxidation
resistance, thermal expansion coefficient matching that of metal alloys, and
very high fracture toughness values. It has been observed that ZrO2 matrix gives rise to sharper interfaces between the amorphous matrix and
nanoparticles [16]. Besides, the high oxygen affinity of ZrO2  prevents oxidation of the metallic nanoparticles.Sample composition was
determined by microprobe analyses. The size distribution of metal nanoparticles
was determined from TEM.
The substrates for TEM experiments were membrane
windows of silicon nitride, which enabled direct observation of as-deposited
samples.


## 3. Results and Discusion

The analysis of TEM
images allowed us to obtain the particles size distribution for each metal
concentration. TEM images provide direct observation of the nanoparticles even
for very low metal contents. Typical TEM images are shown in Figure1 for
Ag-ZrO2, in Figure 2 for Co-ZrO2, and in Figure 3 for
Au-ZrO2. The dark regions correspond to the Ag, Co, and Au particles
and the light regions to the amorphous ZrO2 matrix. The particles
are seen to have clearly defined interfaces with the matrix.Bright field TEM images of Ag-ZrO2 films with
(a) x=0.08, (b) x=0.18, (c) x=0.23, (d) x=0.26, and (e) x=0.28. The scale length
is indicated in each image. The inset in Figure 1(e) shows lattice fringes
inside an Ag particle.
(a)(b)(c)(d)(e)Bright
field TEM images of Co-ZrO2 films with (a) x=0.06, (b) x=0.12, (c)
x=0.25, (d) x=0.30, and (e) x=0.35. The inset in Figure 2(e) shows lattice
fringes inside a Co particle.
(a)(b)(c)(d)(e)Bright field TEM images of Au-ZrO2 films
with (a) x=0.08, (b) x=0.23, (c) x=0.41, (d) x=0.51, and (e) x=0.55. The inset in Figure 3(e) shows lattice fringes
inside an Au particle.
(a)(b)(c)(d)(e)The lattice fringes
observed in the metal grains correspond to Ag/Co/Au atomic planes indicating
good crystallinity even for very low metal content (see insets to Figures1–3). Lattice
fringes are not present in the ZrO2 matrix, confirming its amorphous
nature.The particles have
spherical shape forxAg < 0.18, xCo < 0.25, and xAu < 0.41, (see Figures 1(a) and 1(b),
2(a)–2(c), and 3(a)
and 3(b)). For xAg > 0.18, xCo > 0.25, and xAu > 0.41, the neighboring particles start to coalesce, giving rise to
larger particles not always with spherical shape (see elongated particles in Figures
1(b)–1(d), 2(d), and
3(c) and 3(d)). Increasing the metal content, the particles form big aggregates
(see Figures 1(e), 2(e), and 3(e)), indicating rapid approaching to the
percolation threshold, above which metal forms a continuum.The distributions of
particle size are well described by a log-normal function:(1)f(D)=12πσDexp⁡[−ln⁡2(D/D0)2σ2],where the fitting
parameters D0 and σ
are the most probable particle size and the
width of the distribution, respectively, (see Table 1). At low Ag content, the particle
size distribution is centered between 1 and 2 nm (see Figure 1(a)). Increasing
the Ag content, the size distribution shifts towards larger sizes, due to
coalescence of smaller particles into the big ones, which
produces a net narrowing effect on the particle size distribution (σ goes from 0.4 to 0.2). About xAg=0.28,
the size distribution broadens abruptly (σ=0.5) because of massive coalescence of the
nanoparticles taking place at percolation.Table 1
Particle
size distribution parameters obtained from TEM data as a function of the metal
volume concentration (x): D0 (most
probable diameter), DM (average particle diameter, DM=D0exp(σ2/2)),
and σ (with of the distribution).
xAgD0 (nm)DMσ0.081.71.80.400.181111.20.200.231717.40.220.263939.90.210.28220249.30.50xCoD0 (nm)DMσ0.062.02.00.200.122.72.80.250.2577.40.350.3010.511.00.300.351415.50.45xAuD0 (nm)DMσ0.081.21.30.450.2322.20.400.4133.30.450.515.96.10.250.559.5100.32A quite different evolution
of the microstructure is observed for Au-ZrO2 as the Au content is
increased. At low Au content, the width of the particle size distribution is
similar to that observed for silver with xAg=0.08. Nevertheless, in
this case, a very smooth shift of the size distribution towards larger sizes is
observed even for Au contents as high as xAu=0.41 (see Table 1),
suggesting that in a wide range of concentrations Au particles tend to be
coated by the matrix, which minimizes particle coalescence and maintains the
width of the size distribution almost constant. The onset of coalescence
processes takes place about xAu > 0.41, giving rise to a similar
narrowing of the size distribution (from σ=0.45 to σ=0.25) as it is also observed in Ag-ZrO2,
but in this case occurring at metal contents very close to percolation.
Finally, at xAu⁢~0.55 massive coalescence of the nanoparticles
arising from percolative processes takes place, which produces a broadening of
the size distribution, as it is also observed for Ag-ZrO2. In the case
of the Co-ZrO2 system, the evolution of the microstructure is closer
to Au than to Ag. The coalescence is observed to start about xCo > 0.25 (see Figure 2(d)),
where the width of the size distribution becomes narrower (see Table 1), and a
final increase in σ
is observed for xCo=0.35, anouncing
percolation.Average particle size for
silver, cobalt, and gold increases with metal concentration, but following very
different behaviors. With increasing Au content, mean particle size slightly
increases, since in this case and below aboutxAu=0.04, particles
grow essentially by condensation of the gold atoms available in the
neighborhood of each nucleating seed, according to TEM images (see Figures 3(a) and
3(b)). However, for Ag-ZrO2, the mean particle size increases
abruptly with xAg because particle growth is arising from nucleation
and further coalescence of neighboring particles even at low metal contents. The
Co-ZrO2 is an intermediate case between the extreme behaviors of Au-ZrO2 and Ag-ZrO2.The role played by the
two different mechanisms of particle growing observed in Ag-ZrO2, Co-ZrO2, and Au-ZrO2 granular films gives rise to very different values
of the percolation threshold in these granular materials. The approach to percolation with the
metal content can be better evidenced by the abrupt increase of the standard
deviation of the size distribution, defined as λ=DM[exp⁡(σ2)−1]1/2 [17]. Figure 4 shows the variation of λ(x). The
metal contents, at which massive particle coalescence preceding percolation
takes place, correspond to the range of the λ(x) curves where a significant
departure from linear behavior is observed. For Ag-ZrO2, percolation threshold deduced from Figure
4 and according to TEM images (xc(Ag) ~ 0.28) is very close to the
theoretical prediction for the model of random percolation of hard spheres [18].
In contrast, particle coalescence in Co-ZrO2 and Au-ZrO2 is inhibited by the better efficiency of the matrix to coat the particles with
respect to silver ones, which retards the occurrence of percolating processes,
shifting the critical value of the metal content to xc(Co) ~ 0.35 and xc(Au) ~ 0.55.Figure 4
Standard deviation of the size distribution versus metal content.


## 4. Conclusions

We have shown that pulsed
laser deposition is an appropriate technique to prepare silver, cobalt, and
gold nanoparticles embedded in ZrO2 matrix, in a wide range of
volume concentration (0.08 < xAg < 0.28, 0.06 < xCo < 0.40,
and 0.08 < xAu < 0.55). Sharp interfaces between rounded
crystalline particles and amorphous matrix are observed in the as-prepared
samples, without needing ulterior thermal treatment. The mean nanoparticle
diameter increases with metal volume concentration, but through different mechanisms depending on the
metal element. Silver nanoparticles are obtained in a wider range of diameters
(1–200 nm) than that
corresponding to cobalt (2–15 nm) and gold
ones (1–10 nm) which were
observed obtained under the same preparation conditions. Distinct
microstructures are shown to be the consequence of the relative contribution of
the two particle-growing mechanisms: nucleation and particle coalescence.
Consequently, the percolation thresholds are very different in these three
systems, (xc(Ag) ~ 0.28, xc(Co) ~ 0.35,
and xc(Au) ~ 0.55).



---

*Source: 475168-2008-03-30.xml*