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Coercivity Modulation in Fe–Cu Pseudo-Ordered Porous

Thin Films Controlled by an Applied Voltage: A Sustainable,
Energy-Efficient Approach to Magnetoelectrically Driven
Materials
Evangelia Dislaki,* Shauna Robbennolt, Mariano Campoy-Quiles, Josep Nogués,
Eva Pellicer, and Jordi Sort*

screening length of metals, which was

Fe–Cu films with pseudo-ordered, hierarchical porosity are prepared by a simple, previously thought to be a limiting factor
two-step procedure that combines colloidal templating (using sub-micrometer- for the electric field effect,[2] the magnetic
sized polystyrene spheres) with electrodeposition. The porosity degree of properties of ferromagnetic films, such
these films, estimated by ellipsometry measurements, is as high as 65%. as saturation magnetization, coercivity,
magnetoresistance, and magnetic ani-
The resulting magnetic properties can be controlled at room temperature
sotropy have been successfully manipu-
using an applied electric field generated through an electric double layer in an lated using electrical methods including
anhydrous electrolyte. This material shows a remarkable 25% voltage-driven voltage control.[3–12] In particular, the
coercivity reduction upon application of negative voltages, with excellent reduction of coercivity using electric fields
reversibility when a positive voltage is applied, and a short recovery time. is an appealing approach for minimizing
power dissipation during magnetic actua-
The pronounced reduction of coercivity is mainly ascribed to electrostatic
tion. More specifically, in order to switch
charge accumulation at the surface of the porous alloy, which occurs over a the magnetization, a magnetic field larger
large fraction of the electrodeposited material due to its high surface-area-to- than the coercivity needs to be externally
volume ratio. The emergence of a hierarchical porosity is found to be crucial applied. Electric currents are needed to
because it promotes the infiltration of the electrolyte into the structure of the generate such magnetic fields (or to switch
film. The observed effects make this material a promising candidate to boost magnetization by spin-torque effect).
Since flowing electric currents are asso-
energy efficiency in magnetoelectrically actuated devices.
ciated with Joule heating power dissipa-
tion, a reduction of the coercivity with DC
voltages can drastically boost the energy
1. Introduction efficiency in magnetically actuated devices. Voltage control of
magnetism can be achieved through several mechanisms. These
The potential toward voltage manipulation of magnetism is can be divided in five categories: (i) carrier accumulation, (ii)
currently a research topic of tremendous interest due to its strain, (iii) exchange coupling, (iv) orbital reconstruction, and
numerous prospective applications in areas such as magnetic (v) electrochemical effect.[1] The possible coupling between dif-
data storage or spin-based electronics.[1] Despite the short ferent magnetoelectric effects when the film thickness is in the

E. Dislaki, Dr. S. Robbennolt, Dr. E. Pellicer Prof. J. Nogués

Departament de Física Catalan Institute of Nanoscience and Nanotechnology (ICN2)
Universitat Autònoma de Barcelona (UAB) CSIC and the BIST
E-08193 Bellaterra, Spain Campus UAB, E-08193 Bellaterra, Spain
E-mail: evangelia.dislaki@uab.cat Prof. J. Nogués
Dr. M. Campoy-Quiles Institució Catalana de Recerca i Estudis Avançats (ICREA)
Institut de Ciència de Materials de Barcelona (ICMAB-CSIC) Passeig Lluís Companys 23, E-08010 Barcelona, Spain
Campus UAB, E-08193 Bellaterra, Spain Prof. J. Sort
The ORCID identification number(s) for the author(s) of this article Departament de Física
can be found under https://doi.org/10.1002/advs.201800499. Universitat Autònoma de Barcelona (UAB)
E-08193 Bellaterra, Spain
© 2018 The Authors. Published by WILEY-VCH Verlag GmbH & Co. KGaA,
E-mail: jordi.sort@uab.cat
Weinheim. This is an open access article under the terms of the Creative
Commons Attribution License, which permits use, distribution and Prof. J. Sort
reproduction in any medium, provided the original work is properly cited. Institució Catalana de Recerca i Estudis Avançats (ICREA)
Passeig Lluís Companys 23, E-08010 Barcelona, Spain
DOI: 10.1002/advs.201800499

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range of several nanometers and the determination of the dom- onto metallized substrates. Three macropore sizes (in the
inant factor are crucial issues requiring further investigation.[1] 200–500 nm range) were achieved through the selection of
In the case of ferromagnetic metals, carrier accumulation distinct colloidal sphere diameters. The close packing of the
and relaxation is often driving the change in magnetism.[13,14] spheres, which was achieved by electrophoretic deposition, ena-
In bulk metals, the strong screening effect prevents penetra- bled the formation of ultrathin pore walls, which were found to
tion of the electric field throughout the entire metal. However, exhibit an additional inherent nanoporosity according to ellip-
in the case of ultrathin metallic films with a high surface-to- sometry measurements, thereby rendering a truly hierarchically
volume ratio, a large electric field can be used to control car- porous alloy structure. The macropores are dispersed forming
rier density, and thus magnetism. The use of liquid electrolytes ordered or pseudo-ordered areas of ≈1 µm2. Importantly, the
has been shown to promote a large electric field owing to the dual porosity leads to a high surface-to-volume ratio, which
very small thickness of the electric double layer (EDL) (typically combined with the ultrathin pore walls, yields an excellent
<1 nm), which enables adjustment of the magnetic properties to material for carrier density modulation[2] despite an overall film
a considerable extent.[2] However, the need to use ultrathin mag- thickness of hundreds of nanometers. In fact, reversible coer-
netic layers is hampering the development of practical devices civity (Hc) reduction in the range of 21.6–25.3% was observed
based on these effects. Previously, with respect to thicker films, in all cases. Morphological, chemical, and structural analyses
this phenomenon had only been achieved when mediated by were carried out to correlate the structure–morphology with the
ion migration (magnetoionics)[11] or by producing nanoporous underlying mechanisms of the voltage control of magnetism.
alloys through highly sensitive and complex means such as
micelle-assisted electrodeposition in order to bypass the require-
ment of an ultrathin film.[3] For this reason, a high surface area 2. Results and Discussion
obtained by porosity was deemed a critical factor in attaining the
desired magnetoelectric effect in films with a thickness of hun- 2.1. Sample Morphology and Porosity Assessment
dreds of nanometers. Porous metallic materials have been pre-
pared in literature through the use of hydrogen bubble dynamic Schematic drawings of the colloidal templating process are given
template,[15,16] block copolymers,[17–19] surfactant micelles,[20] in Figure 1a,b. Representative field emission scanning electron
and hard templates.[21,22] Among these, colloidal templating is microscope (FESEM) images of the porous Fe–Cu films obtained
a particularly advantageous method since it entails a swift and after removal of the polystyrene (PS) spheres are shown in
straightforward approach which, in conjunction with the elec- Figure 1c,d. In this case, a monolayer assembly of PS spheres
trodeposition technique, allows for the creation of a multilay- was targeted. It can be clearly observed that the pore walls are
ered 3D architecture with controllable pore size. Moreover, the extremely narrow and, in some locations, they are even below
close packing of the colloidal spheres is conducive to the devel- 10 nm. In addition, transmission electron microscopy (TEM)
opment of exceptionally thin pore walls. imaging performed on a multilayer sample reveals that the
In this work, hierarchically porous thin Fe–Cu films have pore walls are, in turn, porous (as shown in Figure 2). We can,
been prepared by electrodeposition through colloidal templates therefore, consider that the pore walls are equivalent to ultrathin

Figure 1.  Schematic drawings of a) the assembly of PS spheres onto the metallized Si substrate and b) the electrodeposited Fe–Cu film after removal
of the nanospheres. FESEM images of resulting Fe–Cu films of c) 500 and d) 200 nm pore size.

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films for the purpose of assessing eventual voltage-driven mag- To evaluate the average degree of porosity inherent in the
netoelectric effects. Also, it should be noted that, while the films material, we first carried out spectroscopic ellipsometry on
were electroplated under the same conditions, the composition the reference electroplated (continuous, i.e., unpatterned and
for the 500 and 350 nm pore dimensions was ≈85 at% Fe while multilayer samples of three macropore sizes) and sputtered
for the smallest sphere size of 200 nm the atomic percentage of samples of similar composition. The optical properties for the
Fe fell to 75 at%. This is on account of the formation of expect- sputtered sample are shown in Figure 3a. The refractive index
edly narrower interstices during packing of the smallest 200 nm
diameter PS spheres. Since deposition of Cu is mass trans-
port controlled,[23] Cu cations can probably infiltrate the spaces
between the spheres in a more facile manner, thus resulting in
compositions slightly more depleted in Fe. Another reason could
be that the potential inside the spaces was positively shifting from
the overpotential for Fe reduction as the cavity size decreased.

Figure 3.  Results from ellipsometry measurements related to a) optical

Figure 2. Transmission electron microscopy (TEM) images of a cross properties derived from sputtered sample (compact reference), b) volume
section of a porous Fe–Cu electrodeposited film (obtained using colloidal of air contained in electroplated continuous film compared to porous
templating with spheres of 350 nm), revealing that the walls of the pores samples when modeling the films as two sublayers with different void
are not fully dense. content, and (c) reflectivity of porous deposits at an incident angle of 30°.

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of this sample was then used as a reference to model the data

for the electroplated samples and infer the average air content
by taking the effective medium approximation of the optical
properties via the Bruggeman model.[24] For the electroplated
samples, two clear observations could be made. First, all elec-
troplated samples, including the continuous case, exhibit a
lower density compared to the sputtered sample, as the models
contain large amounts of air (i.e., voids). Since the crystal-
line structure is the same, the lower density is here ascribed
mainly to some degree of nanoscale porosity. The electroplated
continuous film contained about a 33% volume fraction of air
compared to the sputtered reference sample. This result from
ellipsometry can be further supported by high magnification
FESEM images (not shown) which reveal the existence of dis-
perse nanopores. In comparison, the use of colloidal templating
increased the porosity value to around 65%. This is compatible
with a hierarchical distribution of pores.
The second observation is that the air distribution is not
homogeneous throughout the depth of the films, as the outer
surface appears to be much more porous than the inner layers.
Approximated depth profiles of air within the films are shown
in Figure 3b for a simple description of the layer as two sub-
layers with different void fractions (see the Experimental
Section for details). In this graph, the zero in the X-axis cor-
responds to the substrate, and the curves extend through the
depth of the film until the total thickness is reached (where
each horizontal line finishes abruptly), thus marking the sur-
face with air. This dual porosity results in a gradual variation of
the index of refraction, akin to an antireflective coating, which
results in a very low reflectivity in these materials (Figure 3c).
The reflectivity becomes lower with increasing pore size, as the
refractive index decreases (reducing index contrast with air)
and scattering increases due to pore dimensions which become
comparable to the wavelength of light.

2.2. Magnetoelectric Measurements and Coercivity Reduction

The magnetoelectric measurements were performed with sam-

ples obtained using each distinct colloidal sphere size (with a
monolayer thickness, i.e., resulting from plating between the
interstices of a single layer of PS spheres, to reduce the lack
of reflectivity issues), as well as with the sputtered and elec-
troplated continuous Fe85Cu15 samples. The formation of an
electrical double layer at the pore walls/electrolyte interface
(as depicted in Figure 4a) caused the existence of large electric
fields upon application of external voltages.
The protocol followed was to initially record a hysteresis
loop at 0 V, then gradually increase the applied voltage in
a stepwise manner up to +13 V and record the loops at each
value of applied voltage. It was first observed that application of Figure 4.  a) Schematic drawing to illustrate the formation of the electrical
positive values of voltage does not lead to a substantial change double layer at pore walls/electrolyte interface. b) Hysteresis loops cap-
in coercivity (Figure 4c). The coercivity remained the same tured for different values of applied voltage and c) voltage dependence
even when applying voltages as high as +25 V. Subsequently, a of coercivity in the range of +13 to –25 V for the 500 nm pore sample.
waiting time of 20 min was introduced after which the sample
was again measured at 0 V (with no appreciable changes with ≈21.6, ≈23.3, and ≈25.3% decrease for the 200, 350, and 500 nm
respect to the pristine as-deposited sample). Next, the voltage samples, respectively. These changes are considerably more pro-
was decreased in steps until reaching –25 V. A clear coercivity nounced than those observed in the seminal work by Weisheit
reduction was observed for the three porous samples, with et al. in ultrathin (nonporous) FePt and FePd films (where the

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maximum decrease in Hc was only 4.5%).[2] The most pro- 2.3. Investigation of Crystalline Structure and Surface Elemental
nounced Hc modulation from 0 to −25 V found for the 500 nm Composition during Voltage Actuation
pore sample is illustrated in Figure 4b,c. Figure 5 shows the
dependence of Hc on applied voltage for the 350 and 200 nm Upon verification of the feasibility of the voltage control of mag-
sphere diameters. Importantly, the Kerr amplitude (which is netism for the hierarchically porous Fe–Cu deposits, further
proportional to the saturation magnetization in a first approxi- examination of their structural characteristics and surface com-
mation) does not show variations for different voltage values. position was carried out with a special emphasis on identifying
As expected, for the sputtered, virtually pore-free film, no Hc and tracking any eventual changes resulting from the application
changes were observed with variation of the applied voltage. of voltage, which could contribute to the observed magnetoelec-
Finally, the electrodeposited continuous film showed only tric effects, besides the inherent electric charge accumulation.
small fluctuations with an average coercivity value of ≈117 The grazing incidence X-ray diffraction (GIXRD) patterns of a
which indicates that the electrolyte is interacting mainly with representative multilayer sample of 350 nm macropore size in
the surface but could not easily get infiltrated into the film. the as-prepared state (i.e., before any voltage manipulation) as
Moreover, it is apparent that the inherent nanoporosity of the well as after subjecting it to DC voltages of +13 V for 20 min and
material is not sufficient to induce any sizable magnetoelec- –15 V for 20 min, are shown in Figure 6. As can be readily dis-
tric effects in the absence of the well-defined, ultrathin pore cerned, there are no detectable shifts in the diffraction peaks for
walls. Therefore, the results confirm that the porous structure the large negative and positive voltage values (i.e., no changes
created by colloidal templating is indeed essential for the mag- in the cell parameter). In addition, no other peaks (e.g., stem-
netoelectric effect as it allows for the diffusion of the electrolyte ming from oxidation or a phase transition) were visible either.
throughout the entire porous network and leads to extremely It should be noted that all the porous films present the same
thin pore walls which are, in a sense, equivalent to ultrathin peaks corresponding to body-centered cubic (bcc) Fe and are,
films. therefore, single phase. Typically, phase separation into bcc and
face-centered cubic (fcc) phases can occur in this range of com-
positions for electrodeposited Fe–Cu films with a thickness of
several micrometers.[25] However, it was confirmed that this was
not the case for continuous films of 250–300 nm thickness as
in our case (only peaks from bcc Fe were observed, not shown).
Additionally, in the multilayer porous films, the formation of a
single phase is promoted by the forced growth in the narrow
interstices between the PS spheres. It has been previously
shown that confining electrodeposition in narrow cavities close
to or comparable to crystallite size can suppress phase separa-
tion.[23] Thus, the GIXRD results clearly indicate that the films
remain unaltered during the voltage application.
Subsequently, the chemical composition of the uppermost
surface layer was examined using X-ray photoelectron spectros-
copy (XPS). This revealed the presence of mainly Fe and Cu
oxides at the surface (i.e., a thin oxide passivation layer), which
were not detectable by XRD as they are below the threshold

Figure 5. Dependence of the coercivity on the applied voltage for the Figure 6. X-ray diffractograms of a representative sample taken in as-
electrodeposited Fe–Cu films grown using colloidal templated substrates, prepared condition and following negative and positive values of voltage
with spheres of a) 350 and b) 200 nm. applied.

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Table 1. Summary of results from cyclability measurements using the

500 nm pore sample.

Wait time [min] Hc at an applied Hc at an applied

voltage of +21 V voltage of –21 V
0 – 68
2 74 72
4 74 65
6 72 69

Fermi level due to the narrow 3d band. These electrons function

as the free charge carriers of the surface which govern the mag-
netic properties. The application of a high voltage alters the sur-
face charge and can thereby modify the magnetic behavior, as has
been demonstrated by ab initio calculations.[26] The fluctuation in
the number of 3d electrons has a direct influence on the magne-
tocrystalline anisotropy,[10,27] and thus on coercivity.
Finally, 5 min after removal of the voltage, a final hysteresis loop
was recorded showing good recovery of the system (Figure 4c).
The samples also showed good cyclability with alternating posi-
tive and negative voltage application. The corresponding Hc
values during successive alternation between +21 and –21 V of
applied voltage are summarized in Table 1. The wait time refers
to both the time between positive and negative applied voltages
as well as before starting the next pair of measurements.

3. Conclusions
Porous, pseudo-ordered thin metallic films consisting of non-
toxic, abundant elements and prepared using a simple, easily
Figure 7.  XPS detail spectra of a) Fe 2p and b) Cu 2p peaks of a chosen reproducible and environmentally friendly process have been
sample taken at as-prepared conditions and after voltage modulation. fabricated. The magnetic properties can be controlled by voltage
application in a facile manner at ambient conditions leading to a
detection limit. As seen in Figure 7a for the sample of 350 nm reversible coercivity reduction of around 25%. According to the
pore size, there is no appreciable change in the oxidation state of analysis of the film properties in the as-fabricated state as well as
Fe which presents mainly as a mixture of Fe2+ and Fe3+ oxidation after voltage application the phenomenon can be mainly ascribed
states. Contrarily, as shown in Figure 7b there is a clear shift in to carrier accumulation/dissipation. In view of these properties,
the Cu oxidation states, where for +13 V there is an enhancement the films are good candidates for voltage control magnetic appli-
of the Cu2+ peak. When the negative voltage of –15 V is applied, cations aimed at minimization of power consumption.
the Cu2+ peak and corresponding satellites are diminished and
the Cu0/1+ peak emerges strongly due to reduction. These struc-
tural changes seem to be mainly limited to the uppermost surface 4. Experimental Section
and, remarkably, the Fe peaks remain virtually unaltered. Addi- Sample Preparation, Hard-Templating Procedure, and Electrodeposition
tionally, it should be emphasized that a Cu enrichment of the Fe– of Porous Fe–Cu Films: Silicon/silicon dioxide (Si/SiO2) substrates with
Cu solid solution would have resulted in a reduction in saturation a 10 nm Ti adhesion layer and a 90 nm Au seed layer and cut into
magnetization, and in eventual shifts in the XRD peaks, which 1 × 1.5 cm2 dimensions were used with a working area of 1 ± 0.1 cm2.
Prior to use, the substrates were cleaned consecutively with acetone,
is shown not to be the case. Finally, it was previously established
isopropanol, and Milli-Q water. As a preparation for electrophoretic
that a higher Cu content in the electrodeposited Fe–Cu films actu- deposition, they were treated with a 10 × 10−3 m solution of 3-mercapto-
ally causes an increase in Hc rather than the reduction observed 1-propanesulfonic acid sodium salt (MPS) in ethanol at 50 °C for 1 h to
here for negative voltages.[25] Therefore, the structural changes increase the wettability of the surface.[28] Finally, they were alternatingly
induced by the electric field observed in this system mainly influ- rinsed in Milli-Q water and ethanol to remove excessive MPS layers.
ence the Cu species at the surface, whereas the Fe species con- Electrophoretic deposition was implemented using a Keysight B2902A
Precision Source/Measure Unit as a voltage source and a custom 3D-printed
trolling the magnetic behavior remain unaltered. Consequently,
cell consisting of a 1 cm × 1 cm × 0.6 cm poly(methyl methacrylate)
redox effects cannot be advocated to explain the voltage-induced (PMMA) chamber attached to a platinized titanium sheet serving as a
coercivity changes, which should then be mainly attributed to counter electrode. Monodisperse polystyrene (PS) sub-micrometer spheres
the carrier accumulation magnetoelectric effect. Indeed, iron has with three different diameters (200, 350, and 500 nm) in a 2.5% w/v solid–
four unpaired 3d electrons with a high density of states near the aqueous suspension were purchased from Polysciences, Inc.

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The final solution was prepared by mixing of the PS sphere with different void content, thus strongly indicating the existence of a
suspension (0.05 mL) in ethanol (0.45 mL) and was added to the custom gradient of composition through the depth of the film, in agreement with
cell covering a 1 cm2 area of the substrate which was secured by slots at SEM cross sections. More elaborate models, including concentration
the back of the chamber at a 0.5 cm distance from the counter electrode. profiles or a larger number of sublayers, were also employed to analyze
A constant potential of 40 V cm–1 in the case of the two smaller the data but reliable fit improvements could not be obtained due to the
sphere sizes and of 60 V cm–1 for the largest spheres was applied with relatively large experimental uncertainty related to the large pore size.
deposition times of 1 and 5 min, respectively.[28] The deposition time Magnetoelectric Measurements: In-plane hysteresis loops were
was tuned to allow for either monolayer or multilayer assemblies while recorded using a magneto-optical Kerr effect (MOKE) setup from
preserving quality regarding stability and number of defects. Following Durham Magneto-Optics while applying different values of DC voltage
the electrophoretic deposition, the samples were promptly placed on a at ambient conditions using the Keysight B2902A unit as a source. The
hot plate and heated at 50 °C for 15 min to evaporate the ethanol and sample was mounted vertically on a custom 3D-printed PMMA base
stabilize the assembled PS sphere layers.[28] and placed in a quartz SUPRASIL cell filled with anhydrous propylene
Electrodeposition was carried out using a three-electrode cell carbonate containing Na+ ions.[3] The sodium cations served a dual
connected to a Metrohm/Eco Chemie Autolab PGSTAT302N function of reacting with any water entering the system to form NaOH as
potentiostat/galvanostat. A Pt wire served as the counter electrode and a well as to enhance the electrical double layer owing to the presence of the
double junction Ag|AgCl (E = +0.210 V/SHE) as the reference electrode. dissolved Na+ and OH– ions.[3] The anhydrous nature of the electrolyte
The electrolyte (100 mL) was prepared with Millipore Milli-Q water minimized oxidation of the Fe–Cu during the measurements. After each
and ACS Reagent grade chemicals purchased from Sigma-Aldrich and change of the value of applied voltage, a waiting period of 300 s was
contained (NH4)2Fe(SO4)2·6H2O (58.8 g L−1), CuSO4·5H2O (1.25 g L−1), introduced before recording the hysteresis loop to allow the electrolyte to
C6H11NaO7 (22.9 g L−1), NaC12H25SO4 (0.2 g L−1), and C7H5NO3S enter the pore network and the electrical double layer to form.[3]
(0.46 g L−1). The samples were deposited from the as-prepared solution
with a pH of 4.1 at a temperature of 35 °C. The optimized electrolyte
composition and plating conditions were established previously with
unpatterned substrates.[25] Current densities of –25 mA cm–2 and Acknowledgements
deposition times between 15 and 50 s depending on the diameter of the This work was supported by the SELECTA (No. 642642) H2020-
previously deposited spheres and the desired thickness were applied. MSCA-ITN-2014 project. Partial financial support by the Spanish
Finally, the PS spheres were removed by immersing the samples in Ministry of Economy, Industry and Competitiveness (MINECO)
chloroform for 3 h followed by a final rinsing in acetone, ethanol, and (Project Nos. MAT2017-86357-C3-1-R, MAT2015-70850-P and
MQ-water. Unpatterned, continuous Fe–Cu films of 250–300 nm in associated FEDER), the Generalitat de Catalunya (2017-SGR-292), and
thickness were prepared whenever needed and used as control samples. the European Research Council (SPIN-PORICS and FOREMAT, with
Characterization Techniques: The sample morphology was imaged Agreement Nos. 648454 and 648901, respectively) is acknowledged.
by scanning electron microscopy using a Zeiss MERLIN FESEM. E.P. is grateful to MINECO for the “Ramon y Cajal” contract (RYC-2012-10839).
The elemental composition was determined by energy dispersive The ICN2 is funded by the CERCA programme/Generalitat de Catalunya.
X-ray spectroscopy (EDXS) at an acceleration voltage of 15 kV. The The ICN2 is supported by the Severo Ochoa programme of MINECO, grant
crystallographic structure of the deposits was studied by GIXRD using no. SEV-2013-0295. The authors thank Alberto Quintana and Eloy Isarain-
a Bruker-AXS, model A25 D8 Discover equipped with a LinxEye XE-T Chávez for providing the custom cell for magnetoelectric measurements, as
detector using CuKα radiation and a grazing incidence angle of 1°. well as Dr. Agustín Mihi (ICMAB-CSIC) for additional FTIR measurements
For the surface elemental composition and oxidation state detection, and useful discussion regarding the photonic properties of these systems.
XPS analyses were carried out on a PHI 5500 Multitechnique System
spectrometer from Physical Electronics with a monochromatic X-ray
source placed perpendicular to the analyzer axis and calibrated using
the 3d5/2 line of Ag. TEM analyses were performed with a Jeol-JEM 2011 Conflict of Interest
system with a field emission gun operating at 200 kV.
The authors declare no conflict of interest.
Ellipsometry Measurements and Data Analysis: In order to
quantitatively account for the porosity degree of the electrodeposited
Fe–Cu films, these were characterized by ellipsometry. A virtually
fully dense, sputter-deposited, Fe–Cu film of ≈100 nm thickness was Keywords
prepared by co-sputtering using an AJA International, Inc. magnetron
sputtering system and was taken as a reference. Fe was sputtered at coercivity, colloidal templating, electrodeposition, hierarchical porosity,
200 W (direct current, DC) and the Cu at 20 W (radio frequency, RF) for magnetoelectric effects, voltage-driven effects
20 min. Variable angle spectroscopic ellipsometry and reflectivity were
measured using a Sopralab GES5E rotating polarizer ellipsometer with a Received: April 2, 2018
focused spot size of ≈250 µm and CCD detection. At least three angles Revised: May 17, 2018
of incidence were measured for each sample. The angles were adjusted Published online: June 20, 2018
to be around the Brewster angle for each sample, which decreased with
pore size as one would expect for a lower refractive index. The data were
analyzed using the WinElli II software. For the sputtered sample, a two
[1] C. Song, B. Cui, F. Li, X. Zhou, F. Pan, Prog. Mater. Sci. 2017, 87, 33.
semi-infinite media approximation was applied for the direct inversion
[2] M. Weisheit, S. Fähler, A. Marty, Y. Souche, C. Poinsignon,
of the ellipsometric angles. The data for the electroplated samples
were analyzed within the effective medium approximation, mixing the D. Givord, Science 2007, 315, 349.
reference optical properties (those deduced for the sputtered sample) [3] A. Quintana, J. Zhang, E. Isarain-Chávez, E. Menéndez,
and void. Note that as the pore diameter increases, this approximation R. Cuadrado, R. Robles, M. D. Baró, M. Guerrero, S. Pané,
loses its validity. This was indeed observed in a worsening of the fit B. J. Nelson, C. M. Müller, P. Ordejón, J. Nogués, E. Pellicer, J. Sort,
quality with increasing pore diameter, particularly for the data of the Adv. Funct. Mater. 2017, 27, 1701904.
500 nm pore sample. It was found that fits that assumed a homogeneous [4] C. A. Vaz, J. Phys. Condens. Matter. 2012, 24, 333201.
volume fraction throughout the film did not result in acceptable fits of [5] C. Bi, Y. Liu, T. Newhouse-Illige, M. Xu, M. Rosales, J. W. Freeland,
the experimental data. The standard deviation of the fit was improved by O. Mryasov, S. Zhang, S. G. E. Te Velthuis, W. G. Wang, Phys. Rev.
a factor of about 5 by modeling the sample as containing two sublayers Lett. 2014, 113, 267202.

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Adv. Sci. 2018, 5, 1800499 1800499  (8 of 8) © 2018 The Authors. Published by WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim