Applied Surface Science 254 (2007) 160–163

www.elsevier.com/locate/apsusc

Crystalline orientation of BiMnO3 thin films grown by rf-sputtering

E.E. Kaul *, N. Haberkorn, J. Guimpel
Centro Atómico Bariloche and Instituto Balseiro, Comisión Nacional de Energı́a Atómica and
Universidad Nacional de Cuyo, S.C. de Bariloche, Argentina

Available online 10 July 2007

Abstract
BiMnO3 thin films were deposited by means of rf-sputtering onto [1 0 0] oriented SrTiO3 substrates. X-ray diffraction measurements revealed
epitaxial growth with [0 0 l]m orientation in the monoclinic structure representation, equivalent to the ½1 1 1pc direction of the pseudocubic cationic
lattice. This [0 0 l]m orientation was obtained in a wide deposition parameters range. Preliminary magnetization measurements suggest that these
films do not present ferromagnetism below the bulk Curie temperature, T C ¼ 105 K.
# 2007 Elsevier B.V. All rights reserved.

Keywords: Multiferroic materials; BiMnO3; Multiferroism; Thin films; Magnetoelectric; rf-sputtering

1. Introduction BiMnO3 structure is monoclinic (m), space group C2, with unit
cell parameters: a ¼ 9:5323 Å, b ¼ 5:6064 Å, c ¼ 9:8535 Å
Multiferroic [1,2] materials are scarce and combine at least and b ¼ 110:667 . A unit cell of the monoclinic structure
two of the properties of ferromagnetism, ferroelectricity and representation is shown in Fig. 1. It can be seen that there are
ferroelasticity. These materials are intensively studied at three inequivalent Mn atoms arranged in parallel layers in
present because they offer the possibility of realizing a whole the monoclinic [1 0 0]m and [0 1 0]m directions. The
range of new applications. Therefore big interest exists on its relation between these two possible ways of visualizing this
synthesis in thin film form which also would allow for its structure consists in ½2 0 2m ’ ½0 1 0pc ; ½0 4 0m ’ ½2 0 2pc ;
integration on micro- or nano-sized applications. ½1 1 1m ’ ½1 0 0pc ¼ ½0 0 1pc ; ½0 0 4m ’ ½1 1 1pc , etc.
Bulk BiMnO3 is an insulating multiferroic perovskite
material which in bulk form presents both ferroelectricity 2. Experimental details
below T E  550 K, and ferromagnetism below T C  105 K,
with an interaction between them [3]. Unfortunately it is The BiMnO3 films were deposited onto [1 0 0] SrTiO3
difficult to synthesize in bulk form because it requires high single-crystalline substrates by magnetron rf-sputtering in a
pressures (about 6 GPa) [4] and thus only recently single- 90% Ar/10% O2 atmosphere, starting from a Bi rich ceramic
crystalline samples have been obtained [5]. For this reason target of composition Bi1.1MnOx. The small Bi excess was
measurements performed using only either polycrystalline added intentionally in order to compensate for the high Bi
samples or thin films can be found in the literature. volatility, which tends to produce a Bi deficient film. The target
The BiMnO3 structure was initially identified [6,7], as being was sintered from a stoichiometric mixture of Bi2O3 and MnO2
a triclinically distorted pseudocubic (pc) perovskite lattice, of composition Bi1.2MnO3.8. This mixture was pre-reacted in
with the following cell parameters: a ¼ c ¼ 3:935 Å, atmospheric air at 700  C for 1 day. In order to obtain a denser
a ¼ g ¼ 918280 . However, recent detailed neutron and electron target, polyvinyl butyral (PVB) was added to the reacted
diffraction measurements at room temperature [8], as well as powder in a 2.26 wt%. The PVB was removed by a 5 h
high-temperature X-ray diffraction [9], determined that the annealing at 500  C in air. Finally, the pellet was sintered at
750  C, in a hermetic furnace with a static oxygen atmosphere
for 4 h. A small crucible containing Bi2O3 was placed inside
* Corresponding author. the furnace chamber in order to provide a high Bi partial
E-mail address: [email protected] (E.E. Kaul). pressure to avoid Bi loss during the sintering process. A
0169-4332/$ – see front matter # 2007 Elsevier B.V. All rights reserved.
doi:10.1016/j.apsusc.2007.07.012
 E.E. Kaul et al. / Applied Surface Science 254 (2007) 160–163 161

Fig. 2. X-ray diffraction pattern of our BiMnO3 thin films grown on

SrTiO3 [1 0 0] substrates. Only peaks corresponding to the [0 0 l] direction
of the BiMnO3 monoclinic lattice are observed.

in the following ranges: 450  C < T S < 750  C, 2.8 cm

< z < 5 cm, 25 mTorr < PT < 400 mTorr, 10 % <
PAr < 95 %, 5 % < PO < 90 %, 20 W < W rf < 25 W,
1 h < tdep < 4 h.
Fig. 1. A unit cell of BiMnO3 structure, viewed along the [0 1 0]m direction. Bi
Our main result is about the film epitaxy. For almost the
atoms are shown as white spheres while oxygen atoms are shown as small dark-
grey spheres. The octahedral coordination of Mn atoms is represented by light- whole range of explored deposition parameters we observe a
grey (Mn1), grey (Mn2) or dark-grey (Mn3) octahedra. textured growth along the [0 0 l] direction of the monoclinic
BiMnO3 lattice onto the [1 0 0] STO substrates, as can be seen
compact, dark-grey, pellet was obtained with a density of the in Fig. 2. This orientation corresponds to the [1 1 1] of the
order of 78% of the theoretical one. The EDS measurements pseudocubic lattice. Surprisingly, this result is different from
indicated a Bi:Mn ratio of 1.1 and a uniform composition along most previous works [11–13], which used PLD, where a growth
the target, within the accuracy of this technique. along the [0 0 1] direction of the pseudocubic lattice is
The deposition protocol consisted of heating up the substrate reported. We used the diffraction Bragg law: 2d sinu ¼ nl,
to the desired deposition temperature, between 600 and 800  C, where d is the distance within planes, u the incidence angle of
at the system base pressure (in the 107 Torr range); applying the X-ray beam and l is the X-ray wavelength (in our case
the deposition gas mixture; depositing the film in an off-axis lCu 1.54056 Å) and the 2u values of the measured [0 0 n]m
configuration [10] to avoid resputtering problems and finally peaks in order to get d. We used all the measured reflections (up
cooling down the substrate down to room temperature in the to n ¼ 7) collecting them in a sinðuÞ versus n plot. These data
deposition gas mixture. points were fitted by a line using a standard least-square
The crystalline structure was analyzed with X-ray diffrac- method, the slope of such line corresponding to l=2d. From this
tion while the composition was assessed by EDS experiments. procedure we got d ¼ 9:338  0.004 Å which yielded a value
Film thickness was measured with a contact profilometer and of 9.980  0.004 Å for the c lattice parameter of our film (after
the magnetic properties were measured in a SQUID magnet- taking into account the reported monoclinic angle
ometer. b = 110.667 ). This c value is slightly larger than the reported
bulk value of 9.8535 Å [8]. The difference of about 0.127 Å
3. Results amounts for an expansion of about 1.3%. This small c axis
increase might be due to a probable small contraction of the unit
Many reports on BiMnO3 thin film growth with pulsed laser cell in the ab plane owing to tensile strains induced by the
deposition, PLD, can be found in the literature [11–13]. On the substrate. Since we did not found neither peaks corresponding
other hand, we could not find previous works about the growth to other reflections of the BiMnO3 nor the typical bump of a
of BiMnO3 thin films by the sputtering technique. Thus, the glassy structure we concluded that these peaks correspond to
deposition parameter space for the sputtering method has not the structure of most (if not all) the deposited film. Rocking-
been explored, as is the case for other perovskite materials. curve measurements performed on the BiMnO3 peaks yield an
Therefore, we explored a rather wide range for some of the average value of about 0.5 for the half-width-at-half-
deposition parameters, in order to optimize the deposition maximum parameter.
conditions. We deposited films varying the deposition Regarding the dependence on deposition temperature, the
temperature, T S , the target to substrate distance, z, the [0 0 1]m oriented films were obtained between 425 and 600  C.
deposition gas mixture pressure, PT , the percentage oxygen Below 425  C, no peaks on the X-ray diffraction patterns
in the deposition gas mixture, PO , the sputtering gun power, corresponding to BiMnO3 were observed. Above 600  C peaks
W rf and the deposition time, i.e. the film thickness, tdep corresponding to BiMn2O5 were also detected. Above 625  C
162 E.E. Kaul et al. / Applied Surface Science 254 (2007) 160–163

and up to 700  C only BiMn2O5 peaks are observed. At

temperatures above 725  C, the EDS analysis showed a
complete lack of Bi, suggesting that at these temperatures the
high volatility of Bi prevents its incorporation in the film.
Another important parameter was determined to be the
target to substrate distance, relevant in connection to the
chemical composition of the films. A systematic variation of the
Bi:Mn ratio was observed, with a clear tendency to form Mn
richer films at larger distances and Bi richer films at shorter
distances. However, this behavior depended also on other
parameters, most notably T S and PT . Therefore, the optimum
distance yielding 1:1 Bi to Mn ratio has to be determined for
each particular set of T S and PT .
Concerning the effects of the total gas pressure in the
chamber, we qualitatively observed better adherence and
smoother films at rather low pressures (around 50 mTorr). The
film morphology and properties presented low dependance on
Fig. 3. View of the BiMnO3 structure perpendicular to the ab plane. The Mn–
the oxygen partial pressure. Mn distances are shown. Observation: these distances are kept in all the
Although the structural parameters were optimized, we have successive layers of inequivalent Mn ions.
not yet observed ferromagnetic behavior for the films down to
1.4 K. This peculiar behavior could be due to different reasons.
In our opinion, the most probable cause is that this unusual
epitaxy could be imposing substrate induced strains to the
lattice, preventing ferromagnetism. However, it is also possible
that there is substitutional disorder between Bi and Mn at the
cationic sites, or oxygen non-stoichiometry, or even the
existence of an incorrect Bi:Mn ratio not detected within the
resolution of the EDS analysis. At present we do not have
enough data to decide between these hypotheses and more
characterization work is under way.
In summary, we have optimized the growth of BiMnO3 film
with respect to structural parameters. The best results (Fig. 2),
consist of a [0 0 l]m textured film, for the following deposition
parameters: T S ¼ 500  C, PT ¼ 50 mTorr (90% Ar/10%
oxygen), z ¼ 3:5 cm in an off-axis configuration and an rf-
power of 25 W for our 1.5 in. diameter targets. After
deposition, the substrate was cooled down to room temperature
in the same deposition atmosphere. For a tdep of 1 h, a 3100 Å
thick film was grown. Fig. 4. Proposed epitaxial mechanism for matching the [1 0 0] oriented surface
of the SrTiO3 substrate (down lying dark-gray octahedra) and the [0 0 l]m
4. Conclusions (½1 1 1pc ) oriented BiMnO3 deposited film (overimposed light-grey octahedra).

In published works using the PLD technique, the usual cube- microscopy (HRTEM) experiments are under way in order to
over-cube epitaxial growth was obtained for [1 0 0] SrTiO3 confirm this hypothesis.
substrates. However, in this work a [0 0 1]m texture, correspond-
ing to a [1 1 1] orientation in the pseudocubic lattice, was found. Acknowledgements
In Fig. 3 we show a view of the BiMnO3 structure along the
monoclinic [0 0 l] direction. This atomic arrangement has to be Work partially supported by ANPCyT PICT2003-03-13289
matched to the square-like ion arrangement of SrTiO3 along the and Fundación Antorchas. EK, NH and JG also at CONICET,
cubic [1 0 0] direction. Since the two Mn–Mn distances (of Argentina.
about 5.529 and 5.606 Å) are quite larger than the SrTiO3 cell
parameter of 3.9046 Å but closer to its diagonal distance of about
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