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Multiferroic BiFeO 3 thin films processed via chemical solution deposition: Structural

and electrical characterization


S. Iakovlev, C.-H. Solterbeck, M. Kuhnke, and M. Es-Souni

Citation: Journal of Applied Physics 97, 094901 (2005); doi: 10.1063/1.1881776


View online: http://dx.doi.org/10.1063/1.1881776
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JOURNAL OF APPLIED PHYSICS 97, 094901 2005

Multiferroic BiFeO3 thin films processed via chemical solution deposition:


Structural and electrical characterization
S. Iakovlev, C.-H. Solterbeck, M. Kuhnke, and M. Es-Sounia
Institute for Materials and Surface Technology, University of Applied Sciences of Kiel, Grenzstrasse 3,
D-24149 Kiel, Germany
Received 24 June 2004; accepted 3 February 2005; published online 14 April 2005
Polycrystalline BiFeO3 thin films were fabricated on 111Pt/Ti/SiO2/Si substrates via Bi-acetate-
and Fe-acetylacetonate-based chemical solution deposition and spin-coating techniques. The
processing parameters were optimized in order to obtain films with high resistivity. The optical
properties refractive indices and extinction coefficients were measured by means of ellipsometry
HeNe laser, = 632.8 . Microstructure characterization was made by means of atomic force
microscopy, grazing incidence x-ray diffractometry XRD, and texture analysis. Additionally,
powders prepared from a stoichiometric precursor were investigated by means of thermogravimetric
and differential thermal analyses and XRD. It is demonstrated that the formation of perovskite-type
BiFeO3 is accompanied by the appearance of bismuth oxide at low temperatures which then
transforms into Bi36Fe2O57. For the films it was found that annealing in oxygen leads to higher
indices of refraction, lower roughness, and smaller grain size. Complete crystallization of the films
was achieved at a substantially lower temperature compared to that of the powders. A 100
pseudocubic out-of-plane preferred orientation was revealed for specimens annealed in air and
oxygen. It is supposed that the crystal lattice of the thin film is close to cubic possibly due to stress
development at the substrate/film interface. The electrical properties of the films were measured at
room temperature by impedance analysis. The piezoelectric properties were determined using a laser
vibrometer. Room temperature resistances measured at 1 kHz for metal-film-metal configurations
for the specimens annealed in air and O2 were 14 and 1.35 k, respectively. This is explained in
terms of the high sensitivity of the oxidation state 2 or 3 of iron ions to oxygen stoichiometry
in the specimens. Further electrical characterization of the specimen annealed in O2 revealed very
low frequency dispersion of the dielectric constant. A dielectric loss of 1% or less was detected in
a wide range of frequency. The films annealed in oxygen showed piezoelectric activity with a value
of the piezoelectric coefficient d33 of 12 pm/V. A relatively weak ferroelectricity remnant
polarization 2Pr of approximately 1 C / cm2 was detected for the specimens annealed in
oxygen. 2005 American Institute of Physics. DOI: 10.1063/1.1881776

I. INTRODUCTION and films is, however, the high dc conductivity at room tem-
perature which is related to oxygen nonstoichiometry and
The structural and electrophysical properties of bismuth oxidation states of Fe which can be present as Fe2+ and Fe3+.
ferrite BiFeO3 have been investigated intensively during
In this respect the processing conditions have been reported
the last decade. The distinctive feature of BiFeO3 is the si-
to play a decisive role on the dc conductivity of BiFeO3.12,13
multaneous presence at room temperature of ferroelectricity
Analysis of the available literature revealed that the main
and antiferromagnetic order with weak ferromagnetism.13
efforts were directed towards pulsed-laser ablation technique
Bismuth ferrite belongs to the perovskite class of materials
for the BiFeO3 thin-film deposition.9,11,12 Chemical solution-
with a rhombohedrally distorted cell having the polar R3c
space group. Detailed structural investigations of BiFeO3 can deposited CSD thin films were investigated to a lesser ex-
be found elsewhere.4,5 Apart from the fact that the properties tent. Yun et al.10 prepared and characterized BiFeO3 thin
and magnetic structure of BiFeO3 are of great interest from films fabricated via CSD route and annealed in various at-
the fundamental point of view,6,7 the possibility to create new mospheres air, O2 and N2. They reported dramatic effects
electronic devices is also discussed.8 During the last few of annealing conditions on the conductivity of the films. The
years, special attention has been devoted to BiFeO3 thin microstructure and phase composition of the films were also
films912 since they allow direct integration of the material found to depend on the annealing conditions. A pure perov-
into the up-to-date semiconductor technology. Successful skite phase is reported for the specimens treated in N2 and
fabrication of epitaxial9 and polycrystalline1012 thin films air, while second phases, such as Bi2Fe4O9, were present in
processed via various techniques has been reported. The films annealed in O2 atmosphere. The highest conductivity is
most considerable drawback of BiFeO3 crystals, ceramics, reported for specimens annealed in air. Annealing in N2
caused a remarkable increase of resistivity. The results were
a
Author to whom correspondence should be addressed; electronic mail: explained10 in terms of the combined effects of the thin-film
me@fh-kiel.de microstructure and the oxidation state of Fe.

0021-8979/2005/979/094901/6/$22.50 97, 094901-1 2005 American Institute of Physics


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094901-2 Iakovlev et al. J. Appl. Phys. 97, 094901 2005

In view of the fact that chemical solution deposition and


related techniques are of great interest because they provide
versatile and cost-effective processing routes with controlled
stoichiometry and microstructure, it is surprising that CSD
BiFeO3 thin films are still inadequately explored. The present
work attempts to contribute to the understanding of BiFeO3
film formation and properties. A CSD processing method
was developed for the BiFeO3 thin-film deposition on plati-
nized silicon substrates using different annealing conditions.
Additionally, the crystallization of perovskite BiFeO3 is in-
vestigated on powders obtained from the precursor solution
used for thin-film deposition. The results are discussed, tak-
ing into account the effect of processing conditions on the
structural and electrophysical properties of the films and the
development of stress state due to thermal expansion mis- FIG. 1. TGA/DTA traces obtained simultaneously for the dried precursor
match between the film and the silicon substrate. 5 C/min in air.

trical characterization, Pt and Au were sputtered through a


II. EXPERIMENT
shadow mask one after another to get round electrodes of
Bi acetate Strem Chemicals, USA and Fe acetylaceto- 0.6-mm diameter. A post-top-electrode deposition annealing
nate Fluka, Germany were dissolved in de-ionized water was performed at 400450 C for 15 min in air. The
and acetic acid mixed in 1:2 volume ratio. The final concen- frequency-dependent conductivity and dielectric properties
tration of the precursor was 0.25 mol/l. Bi excess of 2 mol % of the films were measured at room temperature at an ac
was added to the solution used for thin-film deposition to driving signal amplitude of 25 mV using a computer-
compensate for bismuth loss during high-temperature an- controlled Agilent 4192A impedance analyzer. An interfero-
nealing. The powders for thermogravimentric and differential metric technique was utilized to investigate the piezoelectric
thermal analyses TGA/DTA and x-ray diffractometry response of the thin films. The experimental setup included a
XRD were prepared by evaporating the solvent. The TGA/ Polytec OFV 353 Germany sensor head laser source and
DTA analyses of the powders were conducted by heating optical system, a Polytec OFV 3001 interferometer control-
them up to 850 C in air with a temperature ramp of 5 C/ ler, a lock-in amplifier, and a function generator. A descrip-
min using a simultaneous thermal analyzer Netzsch STA tion of the method can be found elsewhere.15 The laser beam
409. A -2 XRD analysis Seifert PTS 3000 powder dif- was focused on the front electrode of interest. To excite the
fractometer equipped with a four-cycle goniometer, Cu K surface vibration due to inverse piezoelectric effect, an ac
monochromated radiation of = 1.5418 was performed on signal of various amplitudes was applied at a frequency of 1
powders annealed for 20 min at various temperatures in kHz to the corresponding pad using a computer-controlled
opened alumina crucible in air. The thin films were spin- function generator. The output signal surface velocity from
coated on commercial 111Pt/Ti/SiO2/Si substrates Inostek, the interferometer controller is measured with a lock-in am-
Seoul, Korea at 5000 rpm for 30 s. Each layer was dried on plifier and used for the calculation of the surface
a hot plate at 140150 C and, subsequently, at 210235 C displacement.15 The RT6000S ferroelectric testing system
for 5 min. The films were intermittently annealed in a pre- Radiant Technologies, Inc. was used to obtain room-
heated tube furnace in oxygen flow or in air at 650 C for 10 temperature PE polarization-field characteristics of the
min after each third-layer deposition. The total number of films.
coatings was nine. The films were finally annealed at 650 C
for 1 h in oxygen or in air. The film thickness was deter- III. RESULTS AND DISCUSSIONS
mined by means of ellipsometry HeNe laser, = 632.8 .
A. BiFeO3 powders
The ellipsometric film thickness and complex refractive in-
dex were obtained from a fit to the measured data, applying Figure 1 represents the results of the thermal DTA/
the Fresnel equation and a model for the layered system. The TGA analyses of the dried powder. A significant weight loss
data were obtained for various angles from 30 to 85. The accompanied by heat absorption endothermic peak on the
microstructures of the films were observed using Surface Im- DTA curve in the temperature range from 150 to 300 C is
aging System Germany atomic force microscope AFM in attributed to the decomposition of residual organic com-
noncontact mode. The grazing incidence GI XRD tech- pounds in the powder which is completed at approximately
nique was utilized for the phase analysis of the films. The 300 to 310 C. Further increase in temperature did not cause
grazing angle was kept at 2. Preferentially oriented states of any change in the sample weight. A small exothermic peak
the films were monitored via fiber texture FT plots obtained which appeared on the DTA trace at 823 C Fig. 1, inset is
by scanning the tilt angle of the goniometer with a step of attributed to the ferroelectric-to-paraelectric phase transition.
0.2. No corrections for defocusing and absorption were nec- It must be mentioned that there is no agreement on the values
essary since, for the thickness of the films studied, both ef- of the Curie point reported by various groups for bismuth
fects compensate each other in the range used.14 For elec- ferrite. Wang et al.16 cited TC = 830 C. Kubel and Schmid5,17
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094901-3 Iakovlev et al. J. Appl. Phys. 97, 094901 2005

FIG. 2. XRD pattern of the powder involved in TGA/DTA. All peaks belong
to the perovskite BiFeO3.

and Roginskaya et al.1 gave TC = 837 C and TC = 850 C,


respectively. It seems that the Curie transition temperature of
bismuth ferrite could vary slightly depending on the sample
processing conditions.
Figure 2 shows exemplary the XRD pattern of the pow-
der used in thermal analysis. It was found from the x-ray
analysis of the powders annealed at various temperatures that
the crystallization of BiFeO3 starts below 500 C and contin-
ues in a broad temperature range. However, second phases FIG. 4. Noncontact AFM pictures of BiFeO3 films annealed at 650 C for 1
are shown to be stable up to 750 C. The powder heated up h in air a and O2 b.
to 850 C with a temperature ramp of 5 C/min sample in-
volved in thermal analysis shows pure BiFeO3 Fig. 2. The
indices, N* = n jk j is the imaginary operator, to be ob-
detailed XRD spectra fragments corresponding to the
tained. The values for the films annealed in air are d
specimens annealed at 500, 600, and 700 C for 20 min are
= 220 2 nm and N* = 2.46 j0.041. Those of the films an-
shown in Fig. 3. The results illustrate the evolution of second
nealed in oxygen are d = 210 2 nm and N* = 2.5 j0.042.
phases with increasing temperature. It can be seen that at a
The refractive indices of BiFeO3 specimens are found to be
lower temperature the second phase is mainly bismuth oxide,
substantially lower compared to n = 2.73 recently reported for
which then subsequently transforms to cubic Bi36Fe2O57 at
sol-gel PbTiO3 thin films of similar thickness, using the same
higher temperatures. The presence of residual Bi36Fe2O57 in
frequency.18 The slightly lower film thickness and the sub-
BiFeO3 ceramics fabricated via conventional mixing-oxide
stantially higher real part of the refractive index n the imagi-
technique was reported by Wang et al.16 These second phases
nary part k remained practically unchanged found for the
can apparently be avoided using chemical solution routes for
films annealed in oxygen can be noticed. These results may
powder processing, as demonstrated in the present work.
be rationalized in terms of the formation of stoichiometric
B. BiFeO3 thin films thin films with better crystallinity and higher density. Similar
1. Optical properties effects of annealing conditions on n have been obtained on
Nb-substituted lead zirconate titanate PZT thin films.19
Optimization of ellipsometric data obtained at various
angles allows the thicknesses d and the complex refractive
2. Structural properties
The AFM micrographs of the films are illustrated in
Figs. 4a and 4b for the specimens annealed in air and
oxygen, respectively. The deposition conditions adopted lead
to uniform and crack-free films regardless of the atmosphere
chosen. At the same time, the films annealed in oxygen flow
are characterized by a smoother surface in comparison to
those annealed in air see vertical scale in Figs. 4a and
4b. The root-mean-square rms roughness values obtained
from the AFM data using the SCANNING PROBE IMAGING PRO-
CESSOR software SPIP, Image Metrology are 8.6 and 4.3
nm for the films annealed in air and oxygen, respectively.
The higher roughness of the films treated in air can be attrib-
uted to their porosity and larger grains. In contrast, annealing
FIG. 3. Selected XRD data of the powders annealed at 500, 600, and 700 C in oxygen flow promotes a rather dense structure with finer
for 20 min in air. crystallites. In this respect, the results agree with the ellipso-
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094901-4 Iakovlev et al. J. Appl. Phys. 97, 094901 2005

FIG. 5. GI XRD patterns of BiFeO3 films annealed at 650 C for 1 h in air


a and O2 b. FIG. 6. 100 FT plot normalized intensity of BiFeO3 films.

metric data and the stipulated better crystallinity of the films


powder analysis described above, at the early stages of film
annealed in oxygen.
crystallization. More investigations involving XRD and
Figure 5 shows the XRD spectra obtained in the grazing-
incidence geometry for films annealed in air a and oxygen high-resolution transmission electron microscopy HR TEM
b at 650 C for 20 min. The peaks are labeled assuming the are, however, necessary to elucidate fiber-texture formation.
pseudocubic lattice. The films consist solely of the perov- Another important result can be drawn from texture
skite phase, and no traces of Bi2O3 or Bi36Fe2O57 could be characterization. A close look at the data Fig. 6 reveals that
found. A pronounced 100 preferred orientation is prelimi- the 111 peak appears at approximately 54 which corre-
narily concluded for both specimens compare the ratio of sponds to the angle between 100 and 111 directions in the
peak intensities to the powder data in Fig. 2. The results cubic lattice for the rhombohedrally distorted lattice of
above differ substantially from those reported by Yun et al.10 BiFeO3 this angle is expected to be 59.4.5 This observation
for CSD BiFeO3 thin films. They reported considerable is in qualitative agreement with the results of Wang et al.,9
amounts of second phases in films annealed in O2, and, re- who report that the crystallography of epitaxial BiFeO3 thin
gardless of annealing conditions, no preferred orientation of films is strongly affected by stress states developed due to
the films was observed.10 The discrepancy between the re- lattice parameter mismatch.9 Unlike bulk materials which are
sults reported in the present work and those reported by Yun known to be rhombohedral see introduction and references
et al.10 may be attributed to the different processing condi- therein, epitaxial BiFeO3 thin films deposited on a SrRuO3/
tions adopted. Yun et al.10 used another precursor solution SrTiO3 substrate was found to be of tetragonal structure with
commercial, Toshima Mfg. Co., Ltd. concentration of 0.5 a small monoclinic distortion of about 0.5. Extremely high
mol/l and a lower annealing temperature 600 C. values of the spontaneous polarization 5060 C / cm2,
A detailed analysis of the texture includes the acquisition which are one order of magnitude higher than those mea-
of pole figures and/or fiber texture FT plots. The formation sured for bulk materials were explained by the high sensi-
of fiber uniaxial texture is usually found for the majority of tivity of polarization to changes in lattice parameters.9 It is
thin films deposited on polycrystalline substrates via sol-gel straightforward to suppose that stresses caused by thermal
or CSD techniques a uniform pole-density distribution with expansion mismatch between the films and the substrate ma-
respect to the azimuthal angle indicates the fiber or terials can also affect the structural properties of the films.
uniaxial character of the texture. Therefore emphasis will be We speculate that BiFeO3 thin films fabricated by CSD on
put on the analysis of the FT plots which are simply the platinized silicon substrate exhibit a near-cubic lattice struc-
cross sections of the corresponding pole figures = const ture which is supposed to be stabilized by tensile stresses. An
since the acquisition of a complete pole figure is rather a analogy to sol-gel lead-titanate thin films of close thick-
time-consuming experiment. Figure 6 shows normalized nesses fabricated on silicon substrates can be drawn. Lead-
100 pseudocubic lattice FT plots measured for BiFeO3 titanate films have been shown to be usually characterized by
annealed in air and oxygen. The results corroborate the for- reduced lattice tetragonality, i.e., their lattice structure is
mation of 100 preferred orientation in the films supposed closer to cubic in comparison to crystals or ceramics.20 It
before from the GI XRD data. A faint 111 component of the appears that the crystal structure of BiFeO3 thin films can be
fiber texture is present in the vicinity of = 54 but its inten- affected by stress and may take different variants depending
sity is negligibly small note that the results are plotted in on the substrate materials, processing routes, and processing
semilogarithmic coordinates. One of the possible reasons conditions. Unfortunately, published data on the interrelation
for the development of 100 preferred orientation could be between stress and the structural properties of BiFeO3 are
the formation of lattice-matched intermetallic phases com- still lacking, and further investigations involving detailed
posed of Fe, Pt, and Bi or other template layers, including XRD and selected area electron diffraction SAED analyses
Bi-oxide or Bi36Fe2O57 which might be inferred from the are required to corroborate this supposition.
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094901-5 Iakovlev et al. J. Appl. Phys. 97, 094901 2005

FIG. 8. Room temperature ferroelectric hysteresis loop of BiFeO3 thin film


annealed in oxygen flow.
FIG. 7. Dielectric properties real part of the dielectric constant and dielec-
tric loss of the specimen annealed in O2 at 650 C for 1 h.
must be pointed out additionally that the PE characteristic
of our film is a result of the superposition of the ferroelectric
3. Electrical and piezoelectric properties switching process note also the vertical shift of the hyster-
The annealing atmosphere was found to dramatically af- esis loop typical for ferroelectric materials rather than for
fect the electrical properties of BiFeO3 films. The room- leaky dielectrics and dc conductivity. That, in turn, can
temperature resistance of the films annealed in air and oxy- cause some overestimation of Pr.
gen determined at 1 kHz are 14 and 1.35 k, respectively. The piezoelectric response surface displacement ampli-
As reported previously see Introduction and references cited tude of the film annealed in O2 is illustrated in Fig. 9. The
therein, optimization of oxygen pressure is required to im- effective piezoelectric coefficient of 12 pm/V obtained from
prove oxygen stoichiometry in films and to stabilize the 3+ the slope of Fig. 9 was found to be constant in the entire
oxidation state of Fe and hence decrease the conductivity range of voltage amplitudes investigated. This value is com-
usually peculiar to BiFeO3. A somewhat lower conductivity parable to that estimated for 111 preferentially oriented
of films annealed in O2 compared to that for films annealed PZT 52/48 film of 500 nm thickness,15 but significantly
in air was also reported by Yun et al.10 At the same time, the lower than that determined for epitaxial BiFeO3 film 5060
highest resistance of CSD BiFeO3 films was reported by pm/V at zero dc bias, Ref. 9. The fact that the specimen did
these authors for the specimens annealed in N2. It is thought not show any voltage dependence of the piezoelectric coef-
that the conductivity in BiFeO3 is rather a complex phenom- ficient up to approximately 6 V higher bias led to break-
enon and is still to be addressed in more detail. Figure 7 down can be understood if we suppose that only the lattice
shows the frequency dependence of the dielectric properties intrinsic contribution to the piezoelectric response plays a
real part of the dielectric constant and loss tangent. role. Extrinsic contributions due to ferroelectric domain
While a very weak frequency dispersion of the dielectric switching might be active at bias voltages higher than the
constant is observed, the loss tangent varies considerably breakdown voltage.
with frequency Fig. 7, probably due to an increased contri-
IV. CONCLUSIONS
bution of dc conductivity at lower frequencies. Nevertheless,
the film shows good dielectric characteristics tan is an The chemical solution deposition and spin-coating routes
order of magnitude lower than that reported recently for were used to process crack-free BiFeO3 thin films on plati-
pulsed laser deposited PLD BiFeO3 thin films21 in a wide
frequency range. The experimentally determined frequency-
dependent dielectric constant could be well fitted to a loga-
rithmic law of the type Curievon Schweidler relation
m1, where is the angular frequency and m the disper-
sion exponent which is found to be very close to unity m
= 0.995. Such small dispersion is caused probably by a neg-
ligible contribution of film-electrode interfaces into the mea-
sured dielectric properties within the range of the frequencies
investigated.
The room-temperature ferroelectric hysteresis loop of
the specimen annealed in O2 is represented in Fig. 8. The
specimen shows poor ferroelectric properties with double
remnant polarization 2Pr of approximately 1 C / cm2, which
is substantially lower than that reported for pulsed-laser-
deposited films.21 It can be supposed that in the particular
case of CSD films, the coercive fields may exceed the break- FIG. 9. Piezoelectric properties of BiFeO3 thin film annealed in O2: surface
down fields preventing the effective switching of the films. It displacement vs amplitude of driving ac bias.
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094901-6 Iakovlev et al. J. Appl. Phys. 97, 094901 2005

nized silicon substrates. Additional thermal and XRD analy- Science Division, Argonne National Laboratory for useful
ses of powders obtained from the dried precursor were con- discussions. The financial support of this work by the Ger-
ducted in order to collect more data on phase transformation man Federal Ministry of Education and Research Grant No.
in this particular system. Based on the results described 17 006 02 is gratefully acknowledged.
above, the following conclusions may be inferred: i At the
early stages of the heat treatment lower temperatures the 1
Yu. E. Roginskaya, Yu. N. Venevtsev, S. A. Fedulov, and G. S. Zhdanov,
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1990.
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7
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characterization of the dielectric properties revealed a very 12
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electric properties 2Pr of approximately 1 C / cm2. 17
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ACKNOWLEDGMENTS 19
M. Es-Souni, A. Piorra, C.-H. Solterbeck, and M. Abed, Mater. Sci. Eng.,
The authors are grateful to Dr. W. F. Chu Chair for B 86, 237 2001.
20
S. Iakovlev, C.-H. Solterbeck, E. Skou, K. Rtzke, and M. Es-Souni, Appl.
Sensors and Solid State Ionics, Faculty of Engineering, Phys. A: Mater. Sci. Process. submitted.
ChristianAlbrechts University of Kiel for the thermal char- 21
K.-Y. Yun, M. Noda, M. Okuyama, H. Saeki, H. Tabata, K. Saito, J. Appl.
acterization of the powders, and to Dr. M. Avdeev Materials Phys. 96, 3399 2004.

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