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Materials Letters 62 (2008) 1521 1524

www.elsevier.com/locate/matlet

Nickel and cobalt nanoparticles produced by laser ablation

of solids in organic solution
Jin Zhang a,, Christopher Q. Lan b,
a

Department of Cellular and Molecular Medicine & Department of Physics, University of Ottawa, 504 Smyth Road, Ottawa, Canada ON K1H 8L6
b
Department of Chemical Engineering, University of Ottawa, 161 Louis Pasteur, Ottawa, Canada ON K1N 6N5
Received 24 May 2007; accepted 11 September 2007
Available online 26 September 2007

Abstract
Nanoparticles of nickel (Ni) and cobalt (Co) have been produced through laser ablation in organic solution. Pure Ni, Ni50Co50 alloy, and Co metal
plates as the targets, respectively, have been irradiated under 532 nm Nd:YAG laser in ethylene glycol (EG). The produced metal nanoparticles are
stabilized with poly (N-vinyl-2-pyrrollidone) (PVP) in EG. Under the same laser fluence and irradiation time, the average particle size of Ni nanoparticles
is 8 nm in diameter, smaller than 22 nm of Co nanoparticles. The laser-induced structural transition at interface of bulk metal and liquid has been
investigated. It has been found that laser-generated Co nanoparticles show fcc structure, while the target of laser ablation is hexagonal Co bulk. In
addition, the surface plasmon resonance (SPR) absorptions of Ni and Co nanoparticles stabled by PVP in EG are 355 nm and 510 nm, respectively. This
research demonstrates that laser ablation in liquid, a one-step, non-catalyst process, can produce stable Ni and Co nanoparticles.
2007 Elsevier B.V. All rights reserved.
Keywords: Laser ablation; Nanoparticles; X-ray diffraction; Surface plasomon resonance (SPR) absorption

1. Introduction
Nanoparticles of nickel (Ni) and cobalt (Co) with large
surface-volume ratio can be used in the conductive electrolytic
membranes of various fuel cells [1,2]. In addition, their enhanced
magnetic properties have been exploited in the field of data
storage devices and in ferrofluids [3,4]. However, the atmosphere
degradable makes the big challenge in their synthesis through wet
chemistry. Recently, formation of noble metal nanoparticles
under the laser ablation in aqueous has been developed. Since
there is no other specific catalyst used during the process,
generated nanoparticles keep their purity, which is frequently
suffered in the wet chemical method [5].
Mafun et al. have studied the mechanism of laser-induced
gold nanoparticles in aqueous [6]. The laser knocks off 10111012

Corresponding authors. Zhang is to be contacted at Tel.: +1 613 737

8899x72657; fax: +1 613 739 6070. Lan, Tel.: +1 613 562 5800x2050; fax: +1
613 562 5172.
E-mail addresses: Jin.Zhang@uottawa.ca (J. Zhang), clan@eng.uOttawa.ca
(C.Q. Lan).
0167-577X/$ - see front matter 2007 Elsevier B.V. All rights reserved.
doi:10.1016/j.matlet.2007.09.038

atoms of gold into a liquid solution with each shot. The atoms
within about 40 nm of each other rapidly congregate into a
particle. Surfactant, such as sodium dodecyl sulfate (SDS), will
coat the particles and compete with the gold, preventing the
particles from becoming large. Meanwhile, Tsuiji et al. studied
the dependence of particle size of silver on the laser wavelength,
and reported that particles decreased with the decreased
wavelength [7]. Later, AuAg alloy [8] at nanoscale has been
fabricated using laser ablation in aqueous. However, very few
efforts have been made to explore the method in transition metals,
e.g. Ni and Co. The possible reason is that their laser ejected d
electrons can easily react with H2O molecular to cause the
impurity. Our previous studies have shown that ethylene glycol
(EG) is used as reductive regent to produce metal nanoparticles in
polyol process [3]. Moreover, poly(N-vinyl-2-pyrrollidone)
(PVP) has been widely used as a stabilizer to work with EG for
the synthesis of various kinds of nanoparticles. Consequently, this
research therefore is exploiting the new method based on laser
ablation to produce Ni and Co nanoparticles in the present of
organic liquid. The structure transition at the interface of solid
liquid is discussed by studying the microstructures of the lasergenerated Ni and Co nanoparticles. The laser ablation in liquid

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J. Zhang, C.Q. Lan / Materials Letters 62 (2008) 15211524

used in TEM analysis; C K line came from the carbon coating on the grid.
In addition, no O K line was detected.
Previous studies demonstrate that the formation of nanoparticles
under laser irradiation of a metal (M) target immersed into a liquid
proceeds via local melting of the metal [9]. The process can be described
as below;
Mbulk

heating

e ejected by laser

cooling

Mfragment Matom Mnanoparticles

copping agent

The electronphonon coupling leads to a transfer of the electronic

excess energy into lattice heat. Subsequently to the thermal equilibration
Fig. 1. Illustration of laser ablation for generating metal nanoparticles in organic
solution.

media provides a novel non-catalyst technique for synthesizing

pure and stable Ni and Co nanoparticles.
2. Experimental
Metal targets, including Ni, Co, and Ni50Co50 plates, were put
on the bottom of the three-neck round bottom flask, respectively
(as shown in Fig. 1).
Nd:YAG laser at 532 nm with 50 mJ of total energy was used to
against the metal plate in 20 ml of EG. Produced nanoparticles can
be stabled in the presence of stabilizer agent, 0.003 mM PVP. The
pulse duration and repetition rate were 3 ns and 20 Hz,
respectively. The focus length was about 10 cm. The spot size
of the laser beam on the surface of the metal plate was around
1 mm in diameter. So, the laser fluence was estimated around
6.37 J/cm2. Moreover, the irradiation time (t) was 60 min. The
morphologies of laser-generated nanoparticles have been studied
by a Transmission Electron Microscope (TEM) (JEM-2100EX).
Electron Dispersed Energy X-ray Spectrum (EDS) was used
to detect if oxygen element came from nanoparticles. In addition,
X-ray Diffraction (XRD) (Philips) with Cu K radiation was
carried out to study the microstructure of laser-generated nanoparticles. The optical properties of nanoparticles in EG were
investigated through UVvis spectrometry.
3. Results and discussion
3.1. Morphologies and microstructures of metal nanoparticles
Laser-generated Ni and Co nanoparticles has been stabled in EG with
0.003 mM PVP. The corresponding TEM micrographs of Ni, bi-element
NiCo, and Co nanoparticles are displayed in Fig. 2.
The average particle size of Ni nanoparticles was only 8 nm in
diameter (d) with very narrow size distribution as shown in Fig. 2a. The
bi-element NiCo produced under the same laser fluence and t showed
bigger particle size, d = 15 nm, with broad size distribution (Fig. 2b).
While, the even bigger particle size was found in Fig. 2c, i.e. Co
nanoparticles with d = 22 nm. In addition, the EDS results indicated that
no oxygen element was traced for all of samples. The EDS acquired
from bi-element NiCo nanoparticles indicated that the atomic weight of
Co (at.%) was 40% larger than that of Ni (shown in Supplementary
materials). In the EDX spectrum, the Cu L line came from the Cu grid

Fig. 2. TEM micrographs of laser-generated Ni, bi-element NiCo, and Co

nanoparticles.

J. Zhang, C.Q. Lan / Materials Letters 62 (2008) 15211524

between electrons and lattice, the heat releasing to surround environment

finally lead the ejected fragments and atoms to form the particles with the
stabilizer/capping agents. Therefore, the bigger particle size for lasergenerated Co nanoparticles suggests that more Co fragments and atoms
have been ejected than Ni fragments under the same laser fluence and t.
In other words, higher concentration of PVP may be needed to compete
with the growth of Co nanoparticles in EG by comparing with
the formation of Ni nanoparticles under the laser ablation. The analysis
of X-ray Photonelectron Spectroscopy (XPS) also indicated the Co-rich
for bi-element of NiCo nanoparticles produced by laser against Ni50Co50
alloy.
To further understand the laser-induced structure transition at the
interface between metal and liquid, collected nanoparticles were dried in
vacuum oven and examined by XRD. The XRD profiles of Ni, NiCo and
Co nanoparticles are shown in Fig. 3.
Fcc Ni nanoparticles were found with broad peaks due to the
small crystallite size. For Co nanoparticles, two phases, hcp -Co and fcc
-Co, were detected, which is different with the hexagonal structure of
bulk cobalt. XRD pattern of bi-element NiCo indicated the single fcc
structure. It was reported that Ni (lattice parameter: 3.5238 ) and Co
(lattice parameter: 3.5447 ) are expected to form solid solutions [10].
While, most studies [11,12] have addressed that melting of the
nanoparticles may occur under high density of excitation energy, which
can cause the re-arrangement in the composition and structures of
nanoparticles. Thus, although XRD results show that the bi-elemental
nanoparticles have a single fcc phase, it is not possible to determine if
they are solid solutions or composites just through X-ray diffraction.
3.2. Optical spectroscopy studied on the interaction of laser-generated
nanoparticles and organic solution
The colloidals of Ni, bi-element NiCo, and Co nanoparticles show
colors from yellow to redbrown in EG with capping agent of PVP.
Noted the solution of EG/PVP without nanoparticles is colorless under
the same laser fluence and t. The color of metal nanoparticle colloid is
resulted from the coherent oscillation of the conduction band electrons
for metallic nanoparticles can be induced by the interacting electromagnetic field, which is named as surface Plasmon resonance (SPR) [13].

1523

Fig. 4. UVvis spectra of laser-generated Ni, NiCo, and Co nanoparticles

stabled by PVP in EG.

The SPR absorption of Ni nanoparticles in EG was 355 nm in the

UVvis spectrum as shown in Fig. 4, and the maximum SPR absorption
of Co nanoparticles was at 510 nm. Interestingly found, two weak
absorptions of bi-element NiCo nanoparticles in UVvis spectrum were
observed with centering at 335 nm, and 500 nm, respectively. The shift
could stem from the interaction between Ni and Co in the nanocomposites. It suggests that the laser-generated bi-element NiCo nanoparticles
from Ni50Co50 alloy could have a phase transition during the melting
process.
Based on Mie's theory, Creighton and Eadon [14] have reported the
calculated optical spectrum of various metal nanoparticles in water and in
vacuum where Ni nanoparticles exhibit surface plasmon resonance (SPR)
absorption between 300 nm and 400 nm, while Co nanoparticles show
the very weak absorption in the range of 250450 nm with a very broad
band. Concerning the organic molecules surrounding the laser-induced
nanoparticles, our calculation estimates that the SPR absorptions of Ni
and Co nanoparticles were around 360 nm and 495 nm, respectively.
Recently, Ganeev et al. reported that the SPR absorption of Co
nanoparticles-doped PVP in aqueous is about 520 nm [15], which is
quite close to the above result.

4. Conclusions

Fig. 3. X-ray diffraction patterns (powder scan) of Ni, bi-element NiCo and Co
nanoparticles.

Nanoparticles of pure Ni, bi-element NiCo, and pure Co have

been produced by laser ablation of metal plates in EG. PVP as
stabilizer agent was used to confine and stable the nanoparticles
in the organic solution. The results indicated that PVP was stable
under laser fluence at 6.37 J/cm2. The analysis of morphologies
of particles and EDS results suggested that more Co atoms and
fragments can be ejected in solution than that of Ni under the
same laser fluence and t. The fcc structure of Co nanoparticles
was different from the closed-packed hexagonal Co bulk because
of the local melting in liquid. The SPR absorptions for both of Ni
and Co nanoparticles stabled by PVP in EG were 360 nm and
510 nm, respectively. In summary, the laser ablation in organic
media is an alternative, efficient, and non-catalysis technique to
produce stable and pure Ni and Co nanoparticles.

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J. Zhang, C.Q. Lan / Materials Letters 62 (2008) 15211524

Acknowledgements
This work was supported by the University of Ottawa. We
thank Dr. Jinshen Pan from the Institute of Materials Research
Engineering at the National University of Singapore for the work
of XPS & TEM.
Appendix A. Supplementary data
Supplementary data associated with this article can be found,
in the online version, at doi:10.1016/j.matlet.2007.09.038.
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