30th ICPIG, August 28th September 2nd 2011, Belfast, Northern Ireland, UK

Fabrication of metal nanoparticle films using pulsed laser deposition

I. Mirza and J. G. Lunney
P

School of Physics, Trinity College Dublin, Dublin 2, Ireland.

Nanoparticle metal films were prepared using nanosecond and femtosecond pulsed laser
deposition in vacuum. The equivalent solid-density thickness of films was measured using a
quartz crystal deposition monitor. A Langmuir ion probe was used to record the ion time-of-flight
signal, from which the ion fluence and energy distribution were measured. Scanning transmission
electron microscopy showed that films contain nanoparticles with diameter in the range of 1- 40
nm. The optical absorption spectra of nanoparticle films showed the expected surface plasmon
resonance, which shifts to longer wavelength and increases in magnitude as the equivalent
thickness was increased.

1. Introduction
The term nanoparticle (NP) usually refers to
condensed phase particles with size in the range of 1
100 nm. In recent years there has been much
interest in the fabrication and characterization of
transition metal and noble metal NPs due to their
interesting optical, catalytic, electronic and magnetic
properties [1]. For many of these potential
applications the NPs need to be deposited on solid
substrate. A wide variety of techniques, such as
thermal evaporation, molecular beam epitaxy, ion
sputtering and pulsed laser deposition (PLD) have
been used for the preparation of nanostructured
films. PLD is relatively simple and flexible
technique for thin film deposition and
nanofabrication. Both nanosecond (ns) and
femtosecond (fs) pulsed lasers can be used for the
ablation process.
For NP growth with ns-PLD, there is much
evidence that the NP growth takes place by surface
diffusion of deposited material. Dolbec et al. [2]
have prepared Pt NPs on highly oriented pyrolithic
graphite by ns-PLD. By studying the morphology of
NPs at different equivalent thickness they found that
the NP size varies with equivalent solid-density
thickness. A similar trend has been observed in the
fabrication of nanocomposite films of Cu and
amorphous alumina by Afonso et al. [3] .
In fs ablation of Ni Amoruso et al. observed that
NPs are present in the ablation plume and can be
collected on a solid substrate [4]. By studying the
ablation plume dynamics using fast photography and
optical emission spectroscopy, they have found that
the ablation plume has two very distinct
components: a fast atomic plume moving at few
km-s-1 followed by a NP plume expanding with 10
times smaller velocity.
In present paper, we present results of an
experiment to compare nature of thin Ag NP films
deposited by ns- and fs-PLD in vacuum. We also

show a comparison of the plasma part of the fs and

ns laser plumes obtained using a planar Langmuir
ion probe.
2. Experimental setup
The laser ablation was performed in high vacuum
(210-5 mbar) using a KrF excimer laser (=248
nm, 25 ns, 10 Hz) and a Ti sapphire laser (=800
nm, 130 fs, 10 Hz). In both cases the laser fluence
was 0.8 J cm-2. The Ag target was continuously
rotated to extend the region of ablation and the angle
of incidence was 450. The substrate-to-target
distance was 6 cm for ns-PLD and 8 cm for fs-PLD.
A 0.09 cm2 planar Langmuir ion probe biased at -30
V was positioned directly in front of the target to
measure the ion flux, and hence determine the ion
energy distribution. The probe-to-target distance was
5.8 cm for ns-PLD and 4.8 cm for fs-PLD. A quartz
crystal deposition monitor (QCDM) was used to
measure equivalent solid-density thickness of the
deposited film. Both 5 mm 5 mm quartz substrates
and carbon coated TEM grids were used for
deposition. Before deposition the quartz substrates
were cleaned for 10 minutes in ultrasonic baths of
acetone and isopropanol. The morphology of
deposited films was examined using scanning
transmission electron microscopy (STEM) at 25 kV.
The optical absorption of the films on quartz
substrates was measured using Cary 50 single beam
UV/visible spectrophotometer.
3. Results and discussion
Figure 1 shows the Langmuir probe ion signals
for (a) ns and (c) fs ablation. The ion flux rises
rapidly as the front of the ablation plume arrives at
the probe and then decreases as the plume expands
beyond the probe position. Figure 1(b) and (d) show
the corresponding ion energy distributions (dN/dE),
which were obtained from the ion current signals
thus:

(a) ns

800

-2

Current density (mA cm )

30th ICPIG, August 28th September 2nd 2011, Belfast, Northern Ireland, UK

600

400

200

0
0

10

15

20

25

30

35

40

2.0x10

15

1.5x10

15

1.0x10

15

5.0x10

14

(b) ns

-1

-2

dN/dE (eV m )

Time (s)

0.0
0

50

100

150

200

250

300

Energy (eV)

(c) fs

-2

Current density (mA cm )

5
4

where I is the ion current, t is the ion time of flight,

A is the area of the probe, m is ion mass and d is the
target-probe distance.
ce. The average ion energy is 76
eV for ns ablation and 42 eV for fs ablation. In both
cases the plume ions are sufficiently energetic
energe
to
cause self-sputtering
sputtering of growing films. The ion
fluence and net deposition were compared for two
ablation regimes. The ion fluence was obtained by
integrating the ion TOF signal in Figure
Fig
1 while net
deposition, in atoms per cm2 per laser shot, was
derived from the deposition rates measured on the
QCDM.
13
For ns-PLD
PLD the ion fluence was 1.210
1.2
ions cm2
-3
and the net deposition rate was 2.610 nm per
12
laser shot, which corresponds to 9.410
9.4
atoms cm2
. The observation that the ion fluence is higher than
the net deposition indicates that the plume is
strongly ionised and that some self-sputtering
self
in
taking place.
For fs-PLD the ion fluence was 2.01010 ions cm2
. The net deposition was 2.21012 atoms cm-2, which
is 100
100 times larger than the ion fluence, showing
that in fs ablation near the ablation threshold only a
small fraction of the material is removed as plasma.
It is known from other studies that for fs ablation
most of the ablated material leaves
leave the target as NPs
[4].

(a)

3 nm

5 nm

1
0
0

10

15

20

25

30

35

40

50 nm

50 nm

Time ( s)

(b)

12

5.6x10

3 nm

5 nm

(d) fs

-1

-2

dN/dE (eV m )

12

4.2x10

12

2.8x10

Figure 2: STEM images of Ag thin films with equivalent

thickness of 3 and 5 nm prepared using (a) nsns and (b) fs-PLD
on TEM grids.

12

1.4x10

0.0
0

50

100

150

200

250

300

Energy (eV)

Figure 1: Ion flux signals and corresponding ion energy

distributions for (a) and (b) ns, and (b) and (c) fs ablation of Ag
at 0.8 J cm-2

Figure 2 shows STEM images of Ag thin films

prepared using (a) ns- and (b) fs-PLD
fs
with
equivalent thickness of 3 and 5 nm in each case. The
3 nm ns-PLD
PLD films show rather rounded and well
separated NPs. However as the equivalent thickness
is increased to 5 nm the NPs increase in size and
begin to coalesce.

30th ICPIG, August 28th September 2nd 2011, Belfast, Northern Ireland, UK

For fs-PLD (Fig. 2(b)) the 3 nm thick film is

comprised of uniformly distributed NPs with an
average diameter of 3 nm together with a small
number of large particulates with diameters of 50
nm. When the equivalent thickness is increased to 5
nm the NPs remain quite rounded but the average
diameter increases to 5.1 nm.

5. References

0.35

Absorbance

0.30

fraction while the fs ablation plume contains only a

small fraction of ionized material. From STEM it is
observed that in both cases NP size increases with
increasing equivalent thickness. Though in the ns
case, NP coalescence takes place for the thicker
films. The films produced by both methods show the
expected SPR in optical absorption.

(a) ns

1.
2.

5 nm
3 nm

0.25
0.20

3.

0.15
0.10
0.05
0.00
350 400 450 500 550 600 650

4.
700 750 800

Wavelength (nm)

5nm
3nm

0.18

Absorbance

0.15

(b) fs

0.12
0.09
0.06
0.03
0.00
350

400

450

500

550

600

650

700

Wavelength (nm)

Figure 3: Optical absorption spectra of films with equivalent

thickness of 3 and 5 nm prepared using (a) ns- and (b) fs-PLD
on TEM grids.

The optical properties of Ag NP films were

c) absorption spectrometry.
studied using UV/visible
d)
Figure 3 shows the optical absorption spectra of Ag
NP films prepared using (a) ns- and (b) fs-PLD. It
can be seen that absorption of the films in both cases
increases as equivalent thickness is increased. The
expected surface plasmon resonance (SPR) peak
increases in amplitude and shifts to the longer
wavelength as equivalent thickness increased. It can
also be observed that the width of SPR peak
absorption band is narrower for fs-PLD films as
compared to ns-PLD films.
4. Summary
Nanoparticle films of Ag have been prepared
using both ns- and fs-PLD. Comparison of Langmuir
probe ion flux and deposition rate measurements
have shown that the ns ablation plume has a high ion

5.

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S. Amoruso, R. Bruzzese, X Wang, N. N.
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