Materials Letters 65 (2011) 35973600

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Materials Letters
j o u r n a l h o m e p a g e : w w w. e l s ev i e r. c o m / l o c a t e / m a t l e t

Using deep eutectic solvents to electrodeposit CoSm lms and nanowires

P. Cojocaru a, L. Magagnin a, E. Gomez b, E. Valls b,
a
b

Dipartimento di Chimica, Materiali e Ingegneria Chimica Giulio Natta, Politecnico di Milano, via Mancinelli 7, 20131 Milano, Italy
Departament de Quimica Fisica and Institut de Nanocincia I nanotecnologia (IN2UB), Universitat de Barcelona, Marti i Franques 1, E-08028 Barcelona, Spain

a r t i c l e

i n f o

Article history:
Received 11 July 2011
Accepted 2 August 2011
Available online 8 August 2011
Keywords:
Electrodeposition
Ionic liquids
Rare earth alloys
Nanostructured materials

a b s t r a c t
A Deep Eutectic Solvent of 1 chlorine chloride: 2 urea eutectic mixture at 70 C has been tested as useful to
electrodeposit both magnetic SmCo lms and nanowires. Galvanostatic deposition allows obtaining homogeneous
deposits over metallic substrate with variable composition as a function of the current density applied. The
deposits obtained at 0.51.5 mA cm 2 were uniform and they correspond to a cobalt hexagonal crystalline phase
with magnetic anisotropy and coercivity of 250 Oe. It has been possible to deposit SmCo nanowires from the DES
solvent using alumina templates. Uniform CoSm nanowires of 50 nm of diameter have been obtained; they
correspond also to hexagonal phase, but they present higher coercivity.
2011 Elsevier B.V. All rights reserved.

1. Introduction
The main limitation of aqueous electrolytes is their narrow
electrochemical window for the electrodeposition of metals with
very negative reduction standard potential. The use of ionic liquids,
showing a wider electrochemical window, opened the possibility of
obtaining metals and alloys of elements till now not obtained in
aqueous medium. The third generation of ionic liquids supposes the
use of eutectic mixtures of quaternary ammonium salts with amides.
Abbott [1] coined the name of Deep Eutectic Solvents (DES) to
describe these room-temperature eutectic mixtures; their use has a
low environmental impact given their biodegradability.
In a previous basic study over vitreous carbon substrate, the possibility
of electrodepositing Sm, Co and simultaneously Sm and Co using 1
chlorine chloride: 2 urea eutectic mixture at 70 C was tested [2]. From
these promising results, in this work the possibility of obtaining magnetic
CoSm alloys in the form of micrometric lms over metallic substrates or
CoSm nanowires from the DES mixture will be tested. The interest is the
preparation of homogeneous magnetic deposits of controlled composition
in this medium in which, moreover, hydrogen evolution reaction during
the electrodeposition is not favoured. Simultaneously, the use of DES
solvent, very viscous medium, to permit CoSm nanowires deposition will
be also tested.
In some conditions, the SmCo alloy can be a hard-magnetic alloy [35]
but their deposition in aqueous medium is ill-advised. Improved hardmagnetic alloys that could be incorporated as elements of micro-electromechanical-systems (MEMS) or in recording media systems are subject
of interest in recent studies [68]. In this line, in our group different

Corresponding author. Tel.: + 34 934039238; fax: + 34 934021231.

E-mail address: e.valles@ub.edu (E. Valls).
0167-577X/$ see front matter 2011 Elsevier B.V. All rights reserved.
doi:10.1016/j.matlet.2011.08.003

studies analysing the possibility of electrodeposit hard-magnetic

composites [9] or alloys has been performed [10] with the objective of
future implementation.

2. Experimental
A 1 choline chloride: 2 urea molar DES mixture was developed for
SmCo electrodeposition (0.039 M SmCl3 + 0.046 M CoCl2). Electrodeposits were prepared galvanostatically at 70 C using a EG&G
galvanostat/potentiostat. A cylindrical three electrode cell of 300 ml
was used. Plating solution was mechanically stirred (200 rpm). Films
preparation was performed over copper substrates cleaned in alcohol
and water. An Ag/AgCl/KCl and a Ti/Pt sheet were used as reference
and counter electrodes, respectively. After obtaining the deposits,
they were recovered with a gold layer (800 nm thick from gold sulte
electrolyte, c.d. 7 mA/cm 2, 50 C, pH 7.5) to minimize the possible
oxidation of the deposits.
Nanoporous alumina templates (50 nm diameter of porous) were
used to nanowires formation. Membranes were prepared by anodic
oxidation in 0.3 M oxalic solution with Ti as cathode in a dual step
process [11] from aluminum sheet of high purity (99.99). For the
posterior electrodeposition, a thin Au PVD coating of 30 nm on the
bottom membrane side was used to make it conductive. After
nanowires formation, a new layer of gold was deposited, as in layers
deposition, to protect the deposit.
Elemental analysis of the deposits was performed with a Fischerscope
X-ray XAN (XRF) and conrmed with a scanning electron microscope
(SEM) Zeiss EVO 50 equipped with microanalysis. The morphology of the
deposits was examined by SEM (Zeiss EVO 50). Phase analysis
measurement was done by X-ray diffraction using monochromatic
CoK rays (XRD, Siemens D 5000).

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Table 1
Composition of the lm deposits for different current densities applied.

Fig. 1. Voltammetric curve (50 mVs 1) of a) blank solution, b) deposition solution.

Initial potential: 0.4 V.

Magnetization vs. magnetic eld curves were recorded by applying

the magnetic eld parallel or perpendicular to the samples in a SQUID
magnetometer at room temperature in helium atmosphere.
3. Results and discussion
Voltametric study in quiescent conditions and scan rate of 50 mVs 1
was performed to establish the current/potential range at which
deposition occurs. Fig. 1 shows the voltammograms recorded from the
blank solution (curve a) and the selected deposition solution (curve b) on
copper substrate. Deposition process was observed from 0.85 V and the
contribution of the solvent reduction process to the total current is
negligible at potentials less negative than 1.4 V. Current densities
(between 0.5 and 2 mA cm 2) corresponding to potentials in this
range (0.85 to 1.4) were selected to test the alloy electrodeposition.
The same range of current densities was applied for deposition of both
lms and nanowires.
Galvanostatic curves of CoSm deposition over the metallic substrate
(Cu) shows (Fig. 2A) the stabilization of the potential in 850 to
1050 mV range; as it was expected, more negative potentials were
attained by applying more negative current densities. The prole of the
curves is similar to the obtained values for usual galvanostatic
electrodeposition processes in aqueous medium over metallic substrates.
The potentialtime curves varied signicantly when the deposition was
performed on the alumina template: although a stabilization potential
was observed at low current density (Fig. 1B, curve a), the potential
evolved to very negative values when current densities more negative
than 1 mA cm 2 were applied (Fig. 2B, curve b). It seems that in these
conditions the viscosity of the DES medium makes the entry of the
electroactive species into the porous difcult and very negative values of

j/mA cm 2

wt. % Co

wt. % Sm

0.5
1
1.5
2

54
50
43
21

46
50
57
79

potential were necessary to maintain the reduction current, probably

corresponding to simultaneous nanowires formation and solvent
reduction.
The reduction current led to deposit formation. CoSm lms, 34 m
thick, were obtained at the different current densities applied, showing
cracks at the major current density applied. The morphology of the
deposits was not analyzed due to the presence of the gold layer (800 nm
thick) over them. SmCo deposits were formed, with variable composition as a function of the current density applied (Table 1). The
percentage of Sm, the more hardly deposited element, can be increased
by decreasing the current density. The variation of the composition of
the deposits revealed that it is possible to regulate the deposit
composition in the DES solvent from a xed electrolytic bath by varying
the deposition conditions.
Micrometric nanowires (Fig. 3) were also obtained in the alumina
template from the DES solvent, despite the high viscosity of the
medium. Nanowires of homogeneous thickness were only obtained
by applying low current densities in according to the simultaneous
solvent reduction predicted by the galvanostatic response. Then,
current densities of 0.51 mA cm 2 were selected. Nanowires of
4650 wt.%Sm (around 22.5:1 Co:Sm ratio) were obtained in these
conditions. Similar composition of the SmCo deposits was obtained for
both lms and nanowires by applying low current densities.
The crystalline structure of the SmCo lms was analysed from XRD
using grazing incidence to minimize the signals of the copper substrate.
The deposits with higher proportion of cobalt (4754 wt.% Co) were
analysed to compare both lms and nanowires of similar compositions.
The magnetic response of both congurations was also compared.
In the lms deposits, next to the peaks corresponding to the
copper and gold layer, some peaks assigned to the deposit were
observed at 41.6, 75.9 and 84.0 2 (Fig. 4A). These peaks can be
assigned to a cobalt hexagonal phase oriented in 100. The higher
proportion of cobalt into the deposits can justify the hcp cobalt phase
detected. The peaks were slightly shifted to lower 2 values than those
of pure-cobalt due to the incorporation of Sm into the crystalline
lattice, revealing solid solution formation.
CoSm micrometric lms magnetized easily when the lm was placed
parallel to the magnetic eld (Fig. 4C). In this case the magnetization of
saturation was attained at 5000 Oe whereas it was necessary to apply

Fig. 2. Galvanostatic curves over: A) metallic electrode, B) alumina template.

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were detected (Fig. 4B). These peaks appeared at the same position of
those in CoSm lms due to the similar Sm percentage into the
deposits. The magnetic response was also similar to that of CoSm
lms. The nanowires magnetized easily when the membrane was
perpendicular to the magnetic eld (nanowires parallel to H)
(Fig. 4D). An increase of the coercivity up to 350 Oe was observed
in the parallel conguration of the nanowires of 50 nm diameter
respect to the micrometric lms.
4. Conclusions

Fig. 3. SEM images of the templates with the SmCo nanowires prepared at A) 0.5,
B) 1.5 mA cm 2.

15,000 Oe to attain the magnetization of saturation in the conguration

perpendicular to the eld. Magnetic anisotropy was, then, observed as a
consequence of both the 2D shape of the lms and the magnetic
anisotropy of the hexagonal structure. Coercivity of the lm was 250 Oe,
higher than pure hcp Cobalt deposits [12] probably as a consequence of
the distortion of the crystalline phase by incorporation of Sm into the
lattice.
Nanowires were not detached of the template from magnetic
characterization but they were isolated for XRD characterization by
dissolving the alumina template with NaOH 1 M. In the XRD prole of
the nanowires, the peaks at 41.6 and 75.9 2 of the hcp cobalt phase

Electrodeposition in DES solvent allows preparing CoSm alloys in

both lms and nanowires conguration. This opens the possibility of
obtaining alloys containing rare earth elements because the electrochemical window in enlarged respect to aqueous solvent. Nanowires
preparation is possible from DES solvent if the working temperature is
enough high to minimize medium viscosity, which permit the
entering of the electroactive species into the channel porous.
The selected bath used for the test allows obtaining deposits with
variable composition. For moderate current densities applied, deposits of
hexagonal crystalline structure and intermediate coercivities were
obtained. From these results, the possibility of preparing Sm-rich CoSm
alloys with potential hard-magnetic properties is open.
Acknowledgements
This paper was supported (CTQ2010-20726, BQU) by the Comisin
Interministerial de Ciencia y Tecnologa (CICYT). The authors thank the
Centres Cientcs I Tecnolgics (UB) for the use of their equipment.

Fig. 4. XRD (A) and M/Ms-H magnetic curves (B) of CoSm deposits obtained in the 0.5 to 1.5 mA cm 2 range. XRD (C) and M/Ms-H magnetic curve (D) of SmCo nanowires
obtained in the 0.5 to 1 mA cm 2 range.

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