Electrochemistry Communications 11 (2009) 22412244

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Electrochemistry Communications
journal homepage: www.elsevier.com/locate/elecom

Effects of well-dened magnetic eld gradients on the electrodeposition

of copper and bismuth
Kristina Tschulik *, Jakub Adam Koza, Margitta Uhlemann, Annett Gebert, Ludwig Schultz
Leibniz Institute for Solid State and Materials Research Dresden, P.O. Box 270116, D-01171 Dresden, Germany

a r t i c l e

i n f o

Article history:
Received 10 September 2009
Received in revised form 28 September
2009
Accepted 28 September 2009
Available online 1 October 2009
Keywords:
Magnetoelectrodeposition
Magnetic eld gradient
Deposit structuring
Field gradient force
Lorentz force

a b s t r a c t
Paramagnetic Cu2+-ions have been electrodeposited under application of magnetic eld gradients.
Obtained deposits show a direct correlation of the distribution of magnetic ux density B at the electrode
and the deposit thickness and morphology. In contrast to that no inuence on the deposit structure has
been observed for deposition of Bi from electrolytes containing diamagnetic Bi3+-ions. This indicates that
the structuring effect is mainly based on the action of the magnetic gradient force. A structuring-mechanism has been proposed that also discusses inuences of the Lorentz force.
2009 Elsevier B.V. All rights reserved.

1. Introduction
Electrodeposition is a well-established method for production
of thin metal layers and for surface nishing. In the past decades
the inuences of magnetic elds on electrochemical processes
have been studied widely [115]. Although remarkable changes
e.g. of the surface morphology of electrodeposits have been observed in non-homogenous magnetic elds, up to now no effort
has been made to structure deposits with intent by application of
magnetic eld gradients (rB-elds) [1518]. For the rst time
we report on the structuring of Cu deposits by means of tailored
moderate rB-elds generated by specically designed magnetic
eld templates in comparison to Bi deposits that remain unaffected
and we propose a structuring-mechanism.
2. Experimental
Electrochemical experiments have been performed at room
temperature in an optimized three electrode Teon cell coupled
to a potentiostat (Jaissle). A schematic of the cell geometry and
electrode arrangement used is given in [19]. As working electrodes
(WE) glass discs of 150 lm thickness evaporated with 200 nm of
Au(1 1 1) ( = 13 mm) have been used. To establish well-dened
rB-elds at the WE a magnetic eld template prepared from 21
* Corresponding author. Tel./fax: +49 (0) 351 4659 717x541.
E-mail address: K.Tschulik@ifw-dresden.de (K. Tschulik).
1388-2481/$ - see front matter 2009 Elsevier B.V. All rights reserved.
doi:10.1016/j.elecom.2009.09.041

pure Fe wires ( = 1 mm, l = 3 mm) embedded in PVC (Fig. 1a)

has been placed directly behind these discs. The wire axes have
been aligned perpendicularly to the horizontal, downward facing
WE and magnetized by a homogeneous magnetic eld Bex of
0.5 T (HV7, Walker Scientic). Bex has been superimposed during
electrodeposition in direction of the wire axes, i.e. perpendicularly
to the WE. Thus not only a given gradient of B has been used, but a
specic, well-dened rB-eld has been generated at the WE. The
B-distribution is easily adjustable by application of different magnetic eld templates.
For comparison deposition experiments without the template
in Bex = 0.5 T as well as without Bex have been performed. The
electrolyte for Cu deposition contained 0.01 M CuSO4 and
0.1 M Na2SO4 (as supporting electrolyte). Its pH value has been
adjusted to 3.0 with H2SO4. To achieve comparable limiting current densities (ilim) for Bi deposition a solution of 0.01 M
Bi(NO3)3 in 0.1 M HNO3 has been used. Based on cyclic voltammograms potentials of E = 160 mV for Cu deposition and
E = 140 mV vs. SHE for Bi deposition have been chosen for chronoamperometric depositions in the transport controlled regime.
No side-reactions have been observed at these potentials. Simulations of B-distributions have been performed using the
numerical 3D magnetostatic eld solver Amperes 6.0 (Enginia
Research Inc.). Sample topographies and reectivities have been
analysed with an optical prolometer (MikroProf, FRT), morphologies have been characterized by SEM micrographs (LEO
Gemini 1530, Zeiss).

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one order of magnitude when regions of low and high BrB are
compared. The remarkable inuence of rB-elds on the surface
morphology becomes obvious from SEM micrographs, as well.
The rough surfaces that are obtained in regions of high BrB are
characterized by columnar grain growth (Fig. 2e), whereas small
grains and smooth surfaces are observed elsewhere (Fig. 2f).
In contrast to the structuring effect described above no inuence of superimposed rB-elds could be observed for electrodeposition of equal amounts of bismuth. Homogenous Bi layers
have been obtained in all cases. Neither optical images of the
deposits (Fig. 1d) nor SEM micrographs of deposit morphologies
(not presented here) indicate any difference as regions of high
and low magnetic ux density are compared. Additionally no relevant inuence of homogenous or non-homogenous B on ilim has
been found.
4. Discussion

Fig. 1. Optical images of the used magnetic eld template (a), a homogenous Cu
layer deposited without the template (b), a structured Cu deposit (c) and a
homogenous Bi layer (d) observed with the template behind the WE. Displayed
deposits have been obtained by discharging 260 mC of Cu2+ or 400 mC of Bi3+ in
Bex = 0.5 T WE.

3. Results
As expected, electrochemical Cu depositions without Bex and in
a homogenous Bex = 0.5 T yield homogenous layers (Fig. 1b). Chronoamperometric measurements do not show signicant changes of
ilim. Yet, structured Cu deposits and a strong increase of ilim are obtained when the magnetized magnetic eld template is placed behind the WE during the deposition process. The optical image of
such a deposit is presented in Fig. 1c and displays, that the thickness distribution apparently correlates with the location of the Fe
wires and hence the rB caused by these wires. The distribution
of the magnetic ux density has been simulated and the product
BrB at the WE is visualized in Fig. 2a. Obviously maxima of BrB
are located near the Fe wire rims (indicated by black circles),
whereas BrB is lower above the wire centre and decreases dramatically with increasing distance from the wire rim. In the centre of
the WE the B-distribution above each wire is symmetric, whereas
it is strongly non-symmetric above wires at the outer part of the
template. This is a consequence of the interaction of the magnetic
ux densities generated by neighboring wires.
The lm thickness z exactly complies with this distribution. It is
more than ten times thinner in regions of low BrB (z < 100 nm)
than it is at the maxima of BrB (z  2 lm) as prolometric studies
of the Cu deposits reveal (Fig. 2bd). Especially it has to be emphasized that in the central region of the WE where the B-distribution
above one Fe wire is symmetric to its centre the same is valid for
the deposit thickness (Fig. 2c). On the other hand non-symmetric
deposit thicknesses result above Fe wires near the rim of the WE,
where the B-distribution above one wire is strongly non-homogenous (Fig. 2d).
Additionally the roughness of the surface that can be visualized
by reectivity measurements (Fig. 2b) correlates to the B-distribution at the WE. In fact the deposit roughness is increased by at least

The experimental data demonstrate that structuring of Cu electrodeposits is possible when rB-elds are superimposed during
the deposition process. Maxima of deposit thickness correlate with
maxima of BrB, so evidently rB-elds can alter the current distribution at the WE. As the depositions have been performed in the
mass-controlled regime this observation indicates enhanced
mass-transport of Cu2+-ions to these regions, leading to locally increased deposition rates. This assumption is reinforced by the
columnar grain growth in regions of high BrB, as it is typically observed at relatively high deposition rates [20]. Two different magnetic forces are known to be capable for such an effect: the Lorentz
Force FL and the magnetic eld gradient force FrB [9,11]. Mostly,
inuences of B-elds on electrodeposition are attributed to a FL induced convection, known as magnetohydrodynamic (MHD)-effect
[1]. FL results as cross-product of current density i and applied
magnetic eld B:

FL i  B

Hence, it should be negligible in our optimized experimental

setup [21], since Bex is parallel to i. The fact that without the Fe
wire template no inuence of Bex on ilim has been detected and that
homogenous layers have been deposited (Fig. 1b) conrms this
expectation. On the contrary FrB is only prominent in rB-elds
and signicant effects in moderate elds will result for processes
involving paramagnetic species, especially. This becomes obvious
as it is a function of the magnetic ux density B and its gradient
rB applied at an electrochemical system containing species with
molar magnetic susceptibility vm in a concentration c (l0 is the
magnetic constant):

F rB l1
0  c  B  rB

FrB attracts paramagnetic ions to regions of high BrB,

whereas it only slightly repels diamagnetic ions, as their vm is
essentially smaller [9,17]. Anyhow, if FL were the main driving
force for this structuring effect, it should only be affected by i
and B, but not by vm of the ions. This cannot be the case here,
as although these parameters have been kept constant a structuring effect was observed for Cu but not for Bi depositions. Thus the
structuring effect has to be attributed to FrB and vm of the deposited ions has to be taken into account. As mentioned above absolute values of vm are at least one order of magnitude smaller for
diamagnetic ions like Bi3+ (vm  0.5  109 m3/mol [22]) than
for paramagnetic ions like Cu2+ (vm  16  109 m3/mol [16]).
Hence FrB attracts Cu2+-ions to regions to of high BrB which results in an enhanced mass-transport to these regions, whereas
FrB is not strong enough to alter the ux of Bi3+-ions to the
electrode, signicantly. However, once FrB changed the ux of

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Fig. 2. Studies of deposit thickness and morphology in comparison to the magnetic ux density distribution at the WE. Calculated BrB-values at the WE (a) generated by a
magnetic eld template (Fig. 1a) in Bex = 0.5 T WE and measured reectivities (b) of a structured Cu deposit (Fig. 1c) show analog distribution. Additionally a strong
correlation of the BrB-distribution (a) and the deposit thickness above a central (c) and peripheral (d) Fe wire becomes obvious from prolometric analyses. SEM
micrographs reveal that rough deposits are obtained in regions of high BrB (e) whereas smooth deposits result in regions of low BrB (f).

Cu2+-ions in the solution the latter is not completely perpendicular to the WE anymore but contains some parallel fraction which
crosses the magnetic eld lines. Consequently FL will be induced
and the mass-transport will be further increased due to the MHDeffect. As the ion deection caused by FrB is only locally prominent (in regions of high BrB) the same is valid for FL which is induced by this deection. Therefore, the structuring effect will be
further amplied by interaction of FrB and FL and the resulting
deposit structure can be adjusted by the design of the magnetic
eld template.
The a priori design of such a template and consequently the
generated rB-elds requires comprehensive understanding of
the FrB and FL induced electrolyte convection that determines
the mass-transport to the WE. Yet up to now it is difcult to distinguish whether the inuence of FrB or FL prevails, as both forces are
expected to be of similar magnitude in the presented case of Cu
deposition. According to eqn.(2) the maximum values of FrB are

equal to about 102 N/m3, with vm(Cu2+) = 16  109 m3/mol,

l0 = 4p  107 V  s/(A  m), B  1.3 T and
c = 10 mol/m3,
rB  5  103 T/m. If only diamagnetic species such as Bi3+-ions
are involved in the deposition process the absolute value of FrB
will be decreased by one order of magnitude at least. With increasing distance from the WE BrB decreases across the whole crosssection and so FrB is maximal at the WE and paramagnetic species
are further accelerated in direction of the WE.
An estimation of FL is more difcult, as knowledge of the local
current distribution would be necessary for this, which is not
accessible experimentally. Yet, a rough valuation based on the
measured (average) i and the local thickness of the structured Cu
deposit is possible. As the layer is more than 10 times thicker at
positions of maximum BrB than afar from it, the maximum local
current density might be equal to 10ilim  100 A/m2. If this current
is assumed to be oriented perpendicularly to B  1.3 T with eqn. (1)
a Lorentz force of FL  102 N/m3 results.

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K. Tschulik et al. / Electrochemistry Communications 11 (2009) 22412244

Due to the similar magnitude of FrB and FL detailed experimental and computational studies of the convection of the electrolyte
are in progress to clarify the structuring-mechanism of magnetoelectrodeposition in rB-elds as a superposition of several complex convective effects has to be expected.
5. Conclusions
It has been demonstrated that structuring of Cu electrodeposits
is possible when rB-elds are superimposed during the deposition
process. To the authors knowledge this has not been accomplished
before. Considerations regarding the structuring mechanism
pointed out that a sufcient inuence of FrB is essential and that
FrB will be overlapped subsequently by FL inducing a local MHDconvection. Consequently signicant structuring can be achieved
only for depositions of paramagnetic ions such as Cu2+ or Fe2+
and Co2+. For these cases thicker and rougher or thinner and
smoother deposits result in regions of higher or lower BrB, respectively. Hence desired surface structures and morphologies are
accessible utilizing tailored magnetic eld templates. As not only
the local thickness, but also the local deposit morphology and
hence its local reactivity can be adjusted by this method it could
be of much interest for researches engaged in adsorption processes
or catalyses when paramagnetic species are involved.
Acknowledgements
The German National Academic Foundation (Studienstiftung)
and the German Research Foundation (DFG) in the framework of

the Collaborative Research Centre 609 are gratefully acknowledged

for the support of this work.
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