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Laboratorio de Materiales y Superficie (Unidad Asociada al CSIC), Departamentos de Fsica Aplicada &
Ingeniera Qumica, Universidad de Mlaga, E29071 Mlaga, Spain
b
Facultad de Ingeniera, Instituto de Fsica, 11000 Montevideo, Uruguay
Magnetite, goethite, and lepidocrocite thin films have been electrochemically grown on titanium substrates by the anodic oxidation
of ferrous ions in a 0.01 M FeSO4NH42SO46H2O + 0.04 M CH3COOK, pH 6.0, aqueous solution. It is demonstrated that the
deposition potential can be used as a tool to tune the obtainment of the different pure phases of the iron oxide-oxyhydroxides thin
films. Results of an exhaustive structural characterization, a morphological study, and X-ray photoelectron spectroscopy characterization are presented.
2007 The Electrochemical Society. DOI: 10.1149/1.2424416 All rights reserved.
Manuscript submitted March 31, 2006; revised manuscript received October 23, 2006. Available electronically January 17, 2007.
E-mail: dalchiel@fing.edu.uy
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Table I. Literature survey of iron oxide-oxyhydroxide thin films obtained by electrodeposition onto inert substrates. Here are reviewed only
those works in which the iron oxide thin films were obtained by one-step electrodeposition process.
Iron oxide/
oxyhydroxide
thin film
Fe3O4
Fe3O4
Fe3O4
-FeOOH
-FeOOH
Fe3O4
Fe3O4
a
b
Substrate
ITO
Observations
Ref.
29
30
31
Pot.-potentiostatic electrodeposition.
Galv.-galvanostatic electrodeposition.
Experimental
The diverse iron oxides were anodically deposited in a conventional three-electrode, single-compartment electrochemical cell
under potentiostatic conditions, from mildly stirred solutions.
Electrolytic bath was an aqueous solution of 0.01 M
FeSO4NH42SO46H2O and 0.04 M CH3COOK, pH 6.0 adjusted
with NaOH, was kept at a constant temperature of 90C. As the
bath temperature was near the boiling point of the solution, a condenser was used in order to avoid very high evaporation and then
concentration of the electrolytic solution. All solutions were prepared from analytical grade reagents and 18 M cm Millipore water. The electrolyte solutions were purged with nitrogen for 30 min
prior to each experimental series and then kept under flowing nitrogen during the experiments. The substrates were titanium plates
about 1 cm2 of geometric area, which before each experiment
were polished with emery paper, rinsed with deionized water, then
immersed for 10 s in 5% HF solution, and finally rinsed with water.
In both electrochemical growth and electrochemical measurements,
a platinum sheet was used as a counter electrode and a silver-silver
chloride saturated electrode Ag/AgCl, KCl satd; E = 0.197 V vs
NHE served as reference electrode. All potential values in this paper are reported vs this reference electrode.
The electrochemical measurements and electrodepositions were
carried out using a model 1286 Solartron electrochemical potentiostat. The total electrical charge passed was monitored to estimate
the film thickness assuming a faradaic efficiency of 100% using
the equation d = MQ/nAF; where d is the film thickness; M molecular weight; Q the total charge passed during deposition; A film
area; the density of the film; F the Faraday constant; and n the
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Based on the Nernst equation, the thermodynamic equilibrium electrode potential at 25C can be expressed as
E = 0.98 0.236pH 0.0886 logFe2+
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270 mV, new XRD peaks corresponding to goethite appear, indicating then the formation of a mixture of phases: magnetite goethite. Despite the presence of this new goethite phase, the diffraction
pattern corresponding to the magnetite has not changed, maintaining
the peaks relative intensity ratios. At this potential, the goethite
phase is polycrystalline, presenting a slight 111 preferred orientation. When the electrodeposition potential has been moved anodically to E = 180 mV, the magnetite phase disappears, and the film
is constituted exclusively by a single goethite phase. The corresponding diffractogram shows a decrease in the 110 peak intensity,
and a very important increase of 021 and 002 diffraction peaks.
Then, the electrodeposited goethite thin films have a polycrystalline
nature with a 002 crystallographic preferred orientation.
Further moving the growth potential toward more anodic values,
the corresponding typical XRD patterns for films deposited at
E = 130, 100, 75, and 0 mV are presented in Fig. 3. These
patterns are representatives of the structural behavior of films deposited in the 180 to 0 mV potential range. The films electrodeposited
at E = 130 and 100 mV are constituted by a single-phase goethite, having a polycrystalline structure. The film deposited at
100 mV shows a further increase in the 002 peak intensity, becoming the film with a very definite and strong 002 preferred
orientation. Moreover, the sharpness of the diffraction peaks indicates a very high crystallinity of these goethite thin films. When the
applied potential is 75 mV, the appearance of new diffraction
peaks that have been assigned to lepidocrocite has been observed,
with two phases coexisting: goethite and lepidocrocite. Continuing
this trend, it can be observed that at E = 0 mV the films present
lepidocrocite and goethite as main and secondary phases, respectively.
Figure 4 shows that from 200 to 1000 mV, -FeOOH is the only
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Figure 6. SEM images of electrodeposited iron oxide thin films, plane and
cross-sectional views, 1 and 2, respectively. a1, a2 magnetite; b1, b2
goethite; c1, c2 lepidocrocite.
Fig. 6b1 and b2. The goethite films which have been grown at potentials more cathodic than 100 mV present the same columnar
morphology, but with more rhomboidal columns and not as well
normal to the surface substrate as in the case of those obtained at
E = 100 mV.
Figure 6c1 and c2 shows the SEM images of the top and crosssectional views of an electrodeposited lepidocrocite thin film obtained at E = +600 mV, during 30 min with a charge transfer of
3.5 C/cm2. The crystals are lathlike, elongated in the c-direction,
with each individual lath grown normal to the substrate surface. This
is the same preferred orientation present in the lepidocrocite films
obtained by Antony et al.29 When comparing both works, an important improvement in particle crystallinity is observed here, probably
promoted by the higher bath temperature used in the present work,
90C, against 55C used by Antony et al. In the top view the lepidocrocite laths present a shape more planar than that presented by
the goethite laths above described. The film thickness obtained using
the bulk density of lepidocrocite = 3.97 g/cm3 was 8.2 m,
slightly smaller than the one observed in Fig. 6c2, which agrees with
the less compact morphology of the films, as can be appreciated in
Fig. 6c1 and c2. All the electrodeposited lepidocrocite films showed
similar morphological structures similar to the one described here
for the film deposited at E = 600 mV.
Further structural characterization by TEM was performed for
the same samples for which SEM images have been shown above.
Figure 7 shows typical TEM images and its SAED patterns. TEM
observations show crystals of different morphologies: cubes for
magnetite, and lathlike for goethite and lepidocrocite particles. The
spot diffraction patterns of the magnetite, goethite, and lepidocrocite
particles revealed that they are single-crystalline, which is in good
agreement with the XRD results.
XPS characterization. As an additional test to verify the presence of magnetite rather than maghemite -Fe2O3, which has an
almost identical XRD diffraction pattern, and to confirm the presence of the goethite and lepidocrocite phases, XPS was used to
examine and elucidate these points.
XPS Fe 2p, O 1s, and O 2p photoelectron and valence band
spectra of the Fe3O4, -FeOOH, and -FeOOH samples are shown
in Fig. 8. As can be seen from the XPS spectra, clear features permit
us to distinguish between Fe3O4 and the oxyhydroxide phases. Two
different contributions of photoelectrons are visible in the Fe 2p
spectrum of the Fe3O4 sample. They are seen in the Fe 2p3/2 peak at
binding energies of 710.8 eV as peak maximum and 708.3 eV as a
shoulder. These contributions can be assigned to Fe3+ and Fe2+
states of magnetite.37-39 Similarly, two contributions can be discerned in the Fe LMM Auger peak of the Fe3O4 sample at 700.6 and
703.3 eV of kinetic energy Auger spectra not shown. Distinct from
that, -FeOOH and -FeOOH samples show only one contribution
Fe3+ states, found at 711.3 eV in binding energy for the Fe 2p3/2
peak and around 700.6 eV in kinetic energy for Fe LMM not
shown. Furthermore, the absence of a satellite peak in the Fe 2p
spectrum of the Fe3O4 sample is characteristic for magnetite.40,41
Moreover, the lack of this satellite peak at ca. 719 eV, which is a
major characteristic of Fe3+ in -Fe2O3, clearly excluded the formation of maghemite in the electrodeposited magnetite films. This Fe
2p3/2 satellite peak is found in the - and -FeOOH samples at
719.3 eV, similar to other iron oxide samples of only Fe3+ states.42
We observe in the O 1s spectra of Fig. 8 two contributions in the
case of the oxyhydroxide samples, more clearly separated in the
-FeOOH sample. They are found at 530.0 eV corresponding to
FeO bonds and at 531.1 eV due to FeOH bonds.37,38 In the O 1s
spectrum of the Fe3O4 sample, the O 1s peak has its maximum at
530.0 eV due to FeO bonds. However, at higher binding energies a
broad shoulder can be seen. These are contributions due to CO
bonds, because this sample reveals an inherent higher carbon surface
contamination about 35 atom % compared to about 15 atom % for
-FeOOH and 10 atom % for -FeOOH samples. Due to that adventitious surface contamination of the samples, XPS atomic concentrations could not be used to confirm the stoichiometry of magnetite or iron oxyhydroxide phases. After recording the spectra
shown in Fig. 8, sample surface cleaning in the spectrometer by
4 keV Ar+ ion etching was carried out. Then, only Fe and O atoms
were detected, confirming the purity of the obtained iron oxides.
With regard to stoichiometry, Ar+ sputtering in the case of iron
oxides leads readily to ion beam induced chemical reduction, i.e.,
preferential sputtering of oxygen, thus altering the chemical states
and composition of the surface under analysis.39 The features observed in the O 1s spectra of the three samples in its original state,
before sputtering are also visible in the O 2p peak, which is shown
together with the valence band region in Fig. 8. The valence band
spectra as well clearly show the difference between iron oxyhydrox-
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Figure 8. XPS Fe 2p, O 1s, and O 2p photoelectron and valence band spectra of the Fe3O4, -FeOOH, and -FeOOH samples. Characteristic binding energies
for magnetite and Fe hydroxide are indicated. The arrow indicates the position of the Fermi level EF.
ide and magnetite phases. In the case of the Fe3O4 sample, the shape
of the XPS valence band spectrum is a typical fingerprint of
magnetite.43 Photoelectrons are detected up to energies of the Fermi
level. This shows the property of electrical conductance in magnetite, and further clearly differentiates this phase from the oxyhydroxide ones.
Conclusions
Reproducible, homogeneous, and well-adherent magnetite, goethite, and lepidocrocite thin films were electrodeposited onto titanium substrates. These different phases were obtained on the basis
of tuning the electrodeposition potential and employing the same
electrolytic bath. Three different electrodeposition potential windows for the obtainment of the iron oxide pure phases have been
identified. The very sharp and intense XRD diffraction peaks are an
indication of the very well crystallized layers. Polycrystalline magnetite thin films without a defined texture, and goethite and lepidocrocite thin films with a very strong 002 crystallographic preferred orientation have been obtained. The iron oxide thin films
present well-crystallized particles as exhibited by the SEM images:
magnetite films presenting well-faceted polyhedral crystallites randomly oriented; goethite layers showing an aggregation of rhomboidal columns with some little gaps between them, and lepidocrocite
films presenting lathlike crystallites. The magnetite phase has been
identified due to typical XPS features as two Fe 2p contributions
corresponding to Fe3+ and Fe2+ states, absence of Fe 2p satellite
peaks and a fingerprint valence band shape. The hydroxide phase
becomes evident by O 1s contributions due to FeOH bonds.
Acknowledgments
The authors are grateful to Universidad de Mlaga, Mlaga,
Spain, for the financial support received. E.A.D. also acknowledges
the financial support of PEDECIBA-Fsica, and especially to
C.S.I.C., Universidad de la Repblica, Montevideo, Uruguay. The
authors also thank A. Martnez Orellana Mlaga, Spain for the
TEM measurements.
Departamento de Fsica Aplicada assisted in meeting the publication
costs of this article.
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