Applied Surface Science 127–129 Ž1998.

398–402

The preparation of iron complex oxide nanoparticles by

pulsed-laser ablation
T. Sasaki ) , S. Terauchi, N. Koshizaki, H. Umehara
Department of Composite Materials, National Institute of Materials and Chemical Research, 1-1 Higashi, Tsukuba, Ibaraki 305, Japan

Abstract

Nanoparticles of a calcium–iron complex oxide were prepared by pulsed laser ablation on silicon wafer substrates placed
at off-axial positions against a target. An ArF excimer laser was used to irradiate a CaFe 2 O4 target in atmospheres of Ar and
O 2 at room temperature. The effects of ambient pressure and laser pulse energy on size and composition of nanoparticles
were investigated using atomic force microscopy and X-ray photoelectron spectroscopy. The nanoparticles obtained were
almost spherical and 2 to 26 nm in diameter. The size distributions of the nanoparticles were very narrow and agreed with
the log-normal distribution function. The nanoparticle size increased with ambient pressure and pulse energy. The CarFe
atomic ratios in the nanoparticles, however, decreased with increasing ambient pressure and were independent of pulse
energy. By this technique, the size and composition of nanoparticles can be easily controlled by laser fluence and pressure
during the laser ablation. q 1998 Elsevier Science B.V.

Keywords: Nanoparticles; Iron complex oxide; Laser ablation; Nanoparticle deposition

1. Introduction It is well known that complex oxides such as

perovskite type and spinel type oxides have various
Nanoparticles of various materials such as metal,
functionality originating from their stoichiometry and
semiconductor and oxide have been studied because
crystallinity. Some of these complex oxides such as
of their unique physical andror chemical properties,
calcium–iron complex oxide are very useful materi-
which are different from those of the bulk materials.
als for photoelectrodes, photocatalysts and gas sen-
For example, nanoparticles of Si have photolumines-
sors w4x. The complex oxide nanoparticles have more
cent properties w1x. Those of Au and Co oxide in
unique properties than simple component nanoparti-
SiO 2 have nonlinear optical properties for optical
cles such as metal and simple oxide nanoparticles.
devices w2x and cause optical transmittance change
However, it is very difficult to prepare complex
by ambient gases for gas-sensor w3x, respectively.
oxide nanoparticles by evaporation because of their
Their unique properties result from quantum size
multicomponents and high melting point.
effects, and interface andror surface effects.
Nanoparticles have been prepared by physical
vapor deposition techniques such as resistive evapo-
)
Corresponding author. Fax: q81-298-54-6252; e-mail: ration w5x and sputtering w6–9x. Since the develop-
tsasaki@nimc.go.jp. ment of laser induced chemical vapor deposition,

0169-4332r98r$19.00 q 1998 Elsevier Science B.V. All rights reserved.

PII S 0 1 6 9 - 4 3 3 2 Ž 9 7 . 0 0 6 6 3 - 6
 T. Sasaki et al.r Applied Surface Science 127–129 (1998) 398–402 399

some lasers such as CO 2 and Nd:YAG lasers have

been used for the preparation of particles of Si and
Si 3 N4 w10,11x and ultrafine particles from refractory
oxides w12x. Recently, the fabrication of nanoparti-
cles using laser ablation has also been reported.
Johnston et al. w13,14x investigated the generation of
AlN and Al 2 O 3 nanoparticles by XeCl excimer laser
ablation of Al in N2 and O 2 atmosphere. Si nanopar-
ticles have been prepared by ArF excimer laser
ablation of a Si wafer in inert gas of He w1,15x, and
glass nanoparticles have been prepared in air at
atmospheric pressure with KrF excimer and Nd:YAG
laser ablation w16x. These preparation methods using
laser ablation have the following advantages. Particle
contamination is suppressed and this technique can
be applied to many kinds of materials such as metals,
intermetallic compounds, simple oxides, complex ox- Fig. 1. Schematic diagram of the laser ablation.
ides and polymers. The ablation process can be
easily controlled by laser parameters such as fluence
and wavelength. posited on the substrates of silicon wafers Ž100. at
In this paper, the preparation and characterization room temperature. A substrate was placed at an off
of calcium–iron complex oxide nanoparticles using axial position against the target in the chamber as
ArF excimer laser ablation is demonstrated. shown in Fig. 1. The background gas pressure was
varied from 0.133 Pa to 133 Pa of oxygen and argon.
Morphological observations of nanoparticles were
2. Experimental performed using an atomic force microscope ŽAFM:
Digital Instruments Nanoscope w III. in tapping mode
The preparation system is shown schematically in using an Si tip. The size distributions of the nanopar-
Fig. 1. A Lambda Physik ArF excimer laser Žwave- ticles were determined from the AFM images by
lengths 193 nm: LPX110i. was used for the abla- manual measurement. The composition of the
tion. The repetition rate and pulse width of laser nanoparticles was investigated by X-ray photo-
were 10 Hz and 17 ns, respectively. The laser light
was focused onto the target through a lens for 50 s
and its pulse energy was varied from 50 to 200
mJrpulse. The laser focal spot size was 0.115 cm2 .
The target material for the excimer laser ablation
was CaFe 2 O4 pellets Ž20 mm diameter= 4 mm thick.
prepared by the usual ceramic technique. a-Fe 2 O 3
and CaCO 3 were used as starting materials for the
preparation of CaFe 2 O4 . These powders were stoi-
chiometrically mixed, followed by calcining at
11008C for 5 h in air and firing again under the same
conditions. Finally, the CaFe 2 O4 pellets were pre-
pared by pressing into a pellet under a pressure of
125 MPa and sintering at 11008C for 5 h. The target
was put on the rotating target holder in the ablation
chamber and was rotated at 45.0 rpm during the Fig. 2. Typical AFM image of the calcium iron oxide nanoparti-
irradiation by the ArF laser. Nanoparticles were de- cles deposited at 200 mJrpulse in 66.6 Pa of Ar.
400 T. Sasaki et al.r Applied Surface Science 127–129 (1998) 398–402
Fig. 3. Size distributions of nanoparticles prepared at 200 mJrpulse
in 66.6 Pa of Ar ŽA. and O 2 ŽB. atmospheres.
electron spectroscopy ŽXPS: PHI 5600 ci.. The X-ray
source was monochromated Al K a Ž14 kV, 100 W..
The atomic ratios of CarFe in the nanoparticles
were calculated from the Ca2p and Fe2p peak areas.
3. Results and discussion
Usually, a substrate for film deposition by laser
ablation is placed parallel to the target surface. As is
well known, in the case of film depositions of com-
plex oxides such as high-Tc superconductor by ex-
cimer laser ablation, a serious problem in film qual-
ity is droplet-like large particles, where particle size
ranges from several hundreds of nanometers to sev-
eral micrometers. The target temperature can be over
the boiling point immediately upon the laser irradia-
tion, resulting in explosive spouting of the molten
target which flies directly to the substrate. Thus,
droplet-like large particles are mainly emitted along
the surface normal direction of the target w17x. Actu-
ally, the calcium–iron complex oxide particles de-
posited on the substrate mounted parallel to the
Table 1
Normal and log–normal statistics of the size distributions for the nanoparticles deposited at 200 mJrpulse in 66.6 Pa of Ar and O 2
Ablation atmosphere Mean diameter Žnm. Standard deviation s Žnm.
in Ar 14.2 2.79
in O 2 11.2 3.98
target surface at a distance of 1 cm had a very wide
size distribution, where droplet-like large particles
were observed. Therefore, the substrate was oriented
parallel to target normal as shown in Fig. 1, in order
to avoid the large particle deposition of complex
oxides.
Typical AFM images of the calcium–iron oxide
nanoparticles which were deposited at 200 mJrpulse
in 66.6 Pa of Ar are shown in Fig. 2. Nanoparticles
were clearly observed and almost the same images
were obtained from different parts on the substrate.
The shape of these nanoparticles is almost spherical.
Juang et al. w16x reported that soda-lime glass micro-
spheres could be prepared by excimer laser ablation.
These results suggest that ‘spherical’ particles can
easily be prepared by laser ablation.
The size distributions of the nanoparticles pre-
pared at 200 mJrpulse in 66.6 Pa of Ar ŽA. and O 2
ŽB. are shown in Fig. 3. The size of these nanoparti-
cles was determined from AFM images. The
nanoparticle size range was from 2 to 26 nm and the
size distributions matched very well with the log-
normal distribution. The statistics of the size distribu-
tions Žnormal and log–normal. for nanoparticles de-
posited at 200 mJrpulse in 66.6 Pa of Ar and O 2 are
given in Table 1. The geometric mean diameter and
dispersion of the nanoparticles prepared in Ar were
14.0 nm and 0.19, respectively. As can be seen in
Table 1, the dispersion of the nanoparticles prepared
in O 2 was larger than that of the nanoparticles
prepared in Ar. This tendency was observed for
nanoparticles at all pressure ranges used in the exper-
iment. According to the XPS measurement, the
Fe2p 3r2 peak positions of the samples prepared in
O 2 Ž711.0 eV. are different in binding energy from
those of the samples prepared in Ar Ž710.5–710.7
eV.. These results suggest that ablated species can
react with O 2 gas in the atmosphere.
Nanoparticle size ŽA. and CarFe atomic ratios
ŽB. in the nanoparticles as functions of ambient
a s srdiameter Geometric mean diameter Žnm. ln sg s a
0.19 14.0 0.19
0.36 10.4 0.38
 T. Sasaki et al.r Applied Surface Science 127–129 (1998) 398–402
Fig. 4. Nanoparticle size ŽA. and CarFe atomic ratios ŽB. in the
nanoparticles as functions of ambient pressure of Ar and O 2 . The
nanoparticles were deposited at a constant pulse energy of 200
mJrpulse.
pressure of Ar and O 2 , and irradiated laser pulse
energy are shown in Figs. 4 and 5, respectively. The
nanoparticle size increased with ambient pressure
and pulse energy. The maximum and minimum mean
diameters of the nanoparticles prepared by laser abla-
tion were 16.5 nm and 8.5 nm, obtained with 200
mJrpulse in 133 Pa of Ar and 50 mJrpulse in 0.133
Pa of Ar, respectively. The nanoparticle size can be
more easily controlled in the smaller size range than
Fig. 5. Nanoparticle size ŽA. and CarFe atomic ratios ŽB. in the
nanoparticles as functions of irradiated laser pulse energy. The
nanoparticles were deposited under a constant pressure of 66.6 Pa
of Ar.
401
in the 20-nm range by ambient pressure and laser
pulse energy. The CarFe atomic ratios calculated
from XPS data were almost constant in different
analyzed parts of a substrate where the nanoparticles
were deposited. The CarFe atomic ratios are also
dependent on the ambient pressure as well as particle
size. The CarFe atomic ratios in the nanoparticles
decrease with increasing ambient pressure, indicating
that the composition of the nanoparticles can also be
controlled by pressure. The CarFe atomic ratios in
the nanoparticles were independent of the pulse en-
ergy as shown in Fig. 5B. Consequently, both the
size and composition of nanoparticles can be easily
controlled by laser fluence and pressure during the
pulsed laser ablation.
The dependence of nanoparticle size upon ambi-
ent pressure during ablation indicates that the
nanoparticles can be formed through a vapor conden-
sation process where the nucleation and growth of
the particles will proceed. It is ambiguous whether
the composition change of the nanoparticles arose
from differences in reactivity andror mean free path
among the ablated species. However, it is not yet
possible to determine the mechanism of the nanopar-
ticle formation process.
4. Conclusion
We have demonstrated a new method for prepar-
ing nanoparticles of calcium–iron complex oxide
with a diameter ranging from 2 to 26 nm using
pulsed laser ablation. From AFM observation it was
determined that the shape of the nanoparticles was
spherical. The size distribution of the nanoparticles
deposited on the substrates placed at off-axial posi-
tions against a target was very narrow and followed
a log–normal distribution. The size of the nanoparti-
cles was dependent on both the ambient pressure and
laser pulse energy. The CarFe atomic ratios in the
nanoparticles were dependent on the ambient pres-
sure but were independent of the pulse energy. By
this technique, the size and composition of nanopar-
ticles can be easily controlled by laser fluence and
pressure during the laser ablation. In addition, the
nanoparticles obtained were nearly monodisperse.
402 T. Sasaki et al.r Applied Surface Science 127–129 (1998) 398–402
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