Applied Surface Science 258 (2012) 8040–8045

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Applied Surface Science

journal homepage: www.elsevier.com/locate/apsusc

Controllability study on the preparation of pure phase BiFeO3 thin films by liquid
phase self-assembled method
Xuan Ru Ren a,∗ , Guo Qiang Tan b , Hong Yan Miao b , Zi Yu Li b
a
C/C Composites Research Center, State Key Laboratory of Solidification Processing, Northwestern Polytechnical University, Xi’an, Shaanxi 710072, PR China
b
College of Material Science and Engineering, Shaanxi University of Science and Technology, Xi’an, Shaanxi 710021, PR China

a r t i c l e i n f o a b s t r a c t

Article history: Pure phase BiFeO3 (BFO) thin films were prepared on the ITO/glass substrates covered with function-
Received 29 January 2012 alized OTS self-assembled monolayers (SAMs) by controllable liquid phase self-assembled method. The
Received in revised form 16 April 2012 hydrophobic surface of OTS-SAMs was changed into hydrophilic surface after UV irradiation, which is
Accepted 27 April 2012
helpful to make BFO precursor solutions fully wet the substrate surface. A dense film was formed only on
Available online 4 May 2012
the hydrophilic silnaol group regions, which shows the selectively deposition of BFO precursors. Chang-
ing the pH value of BFO precursor solutions will affect the phase purity. The pure phase BFO thin films
Keywords:
can be obtained under various pH values, which indicates that the liquid phase self-assembled method is
Liquid phase self-assembled method
OTS-SAMs
controllable. All pure phase BFO films are dense, smooth, well-grown polycrystalline films, but the size
Controllability study of grains increased gradually along with the increase of pH values. The micropattern of BiFeO3 film has
BiFeO3 clear edges. The possible growth mechanism of BFO thin films was discussed.
Thin films © 2012 Elsevier B.V. All rights reserved.
Hard-Soft-Acid-Base principle

1. Introduction growth mechanism of BFO thin films by liquid phase self-assembled

method will be discussed.
Recently, BiFeO3 (BFO) materials have attracted more attention
since it shows the coexistence of ferromagnetism and ferroelec-
2. Experimental procedures
tricity as a multiferroic material which can be used in multiferroic
devices such as the multiple-states magnetoelectric memories
The preparation of functionalized OTS-SAMs was shown else-
[1,2]. BFO thin films have been successfully fabricated via vari-
where [9]. The surface modification of OTS-SAMs was achieved by
ous techniques such as sol–gel method [3], pulsed laser deposition
the use of UV light, which was generated by a Photo Surface Pro-
[4], magnetron sputtering [5], and the liquid phase self-assembled
cessor (PL16-110, Sen Lights Corporation, Japan) with a Hg lamp of
method [6]. As we know, the liquid phase self-assembled method is
low pressure ( = 185 and 254 nm). The functionalized OTS-SAMs
a simple, cost-effective, energy efficient and environment-friendly
was obtained after 40 min UV irradiation. The starting materials
process for thin film preparation [7]. Octadecyl trichlorosilane self-
used were Bi(NO3 )3 ·5H2 O, Fe(NO3 )3 ·9H2 O and citrate acid. At first,
assembled monolayers (OTS-SAMs) is the key technique of this
0.01 mol/L Bi(NO3 )3 ·5H2 O, 0.026 mol/L Fe(NO3 )3 ·9H2 O, 0.02 mol/L
method, which can be used as a template to tailor the morphol-
citrate acid were mixed and dissolved in deionized water con-
ogy of thin films and control crystal nucleation. In addition, it can
taining a certain amount of ice acetic to form BiFeO3 precursor
be used to prepare micropatterns of functional ceramic films and
solutions. Followed the solutions were stirring for 50 min to form
small devices of required size and shape with prominent preci-
a transparent solution. BiFeO3 thin films were prepared under pre-
sion through a one-step process at lower temperature [8]. But
cursor solutions with various pH values (pH = 1.50, 1.55, 1.60, 1.65,
till now, there are seldom detailed controllability studies on the
respectively). The pH values were adjusted by adding dilute nitric
preparation of pure phase BFO thin films by liquid phase self-
acid and ammonia. In order to obtain pure phase BFO thin films
assembled method. In this work, the preparation of pure phase BFO
under various pH values, Fe3+ /Bi3+ molar ratios were adjusted.
thin films under various pH values, micropatterning as well as the
The contact angle of the OTS-SAMs was measured using con-
tact angle meter (SL200B, Solon Tech. Shanghai Inc., Ltd.). Atomic
Force Microscope (AFM, 400-SPI3800N) was used to characterize
∗ Corresponding author at: No. 541 Mail Box, Northwestern Polytechnical Uni- the surface of OTS-SAMs. Phase analysis of the films were per-
versity, 127 Youyi Xilu, Xi’an, Shaanxi 710072, PR China. Tel.: +86 13891980230. formed at room temperature by X-ray diffraction patterns recorded
E-mail address: renxuanru1986@163.com (X.R. Ren). on a (DMax 2000PC) with Cu K␣ radiation. The Fe ion oxidation

0169-4332/$ – see front matter © 2012 Elsevier B.V. All rights reserved.
http://dx.doi.org/10.1016/j.apsusc.2012.04.166
 X.R. Ren et al. / Applied Surface Science 258 (2012) 8040–8045 8041

Fig. 1. Illustration of functionalized OTS-SAMs formation and subsequent BFO films formation.

state was determined by an X-ray photoelectron spectroscopy (XPS, 3.2. Controllability study on pure phase BiFeO3 thin films
Axis Ultra, Kratos Ltd.). The surface and cross-sectional micrographs
of the BiFeO3 films were observed with Field Emission Scanning Fig. 3(a) shows the XRD patterns of BiFeO3 films on ITO/glass
Electron Microscopy (FE-SEM, JSM-6700F). A FT-IR spectrometer substrates prepared under various pH values. From which it can
(EQUINX55) was used to characterize the BFO precursors. be seen that when the pH value is 1.5, the BFO thin film is pure
phase, and the BFO peaks match well to the distorted rhombo-
hedral R3c structure. But with the increase of pH values, Bi2 O2.33
3. Experimental results and discussions impurity phase peaks with strong intensity were observed in the
BiFeO3 film, and the intensities of Bi2 O2.33 peaks get stronger and
3.1. Characterization of functionalized OTS-SAMs on the ITO/glass stronger, while that of BFO peaks get weaker and weaker, which
substrates indicates that Bi3+ has larger deposition rate and the Bi element in
the films is surplus. Therefore, changing the pH value of BFO precur-
Funtionalized OTS-SAMs is the key technique for the liquid sor solutions will affect the phase purity, and the Fe3+ /Bi3+ molar
phase self-assembled method, which is essential to the growth of ratios must be increased to obtain pure phase BFO thin films when
films since it can not only enhance heterogeneous nucleation but the pH values were adjusted to higher pH values. Fig. 3(b) shows the
also contribute to the formation of oriented crystals. Fig. 1 shows appropriate Fe3+ /Bi3+ molar ratios for BFO precursor solutions with
the illustration of functionalized OTS-SAMs formation and subse- various pH values to obtain pure phase BFO thin films. From which it
quent BFO films formation. From which it can be seen that at first can be seen that when the pH value is 1.5, the appropriate Fe3+ /Bi3+
the OTS hydrolyzed and liberated HCl; next, the OTS-SAMs com- molar ratio is 2.6, and the ratios increases along with the increase
posed of octadecyl groups was self-assembled onto the ITO/glass of pH values, which indicates that pure phase BFO thin films can be
substrate by the combination between the hydrolyzed OTS and the obtained in BFO precursor solutions with various pH values. There-
ITO/glass substrate, which formed a covalent siloxane (Si O Si) fore, the growth environment of pure phase BFO thin films is not the
bond; then, the OTS-SAMs was UV irradiated, thereby making
extremely reactive Si radical formed on the surface through the
cleavage at the Si C bond, which can immediately react with water
vapor in the air to form polar functional silanol (Si OH) groups;
finally, the BFO precursors were adsorbed onto the functional-
ized substrate which is very reactive to the reaction of chemical
adsorption of ceramic precursors from a solution, thus gradually
assembling the amorphous BFO films.
Fig. 2 shows the relationship between the OTS-SAMs’ contact
angles and the UV irradiation time.
From which it can be seen that with the increase of the UV irra-
diation time, the contact angles decrease monotonically. And we
can observe that the contact angle of OTS-SAMs before UV irra-
diation is 107.50◦ ; while that after 40 min UV irradiation is 4.50◦ ,
which indicates that the surface of OTS-SAMs was changed from
hydrophobic into hydrophilic and therefore the functionalized OTS-
SAMs is helpful to make BFO precursor solutions fully wet the Fig. 2. Relationship between the OTS-SAMs’ contact angles and the UV irradiation
substrate surface. time.
8042 X.R. Ren et al. / Applied Surface Science 258 (2012) 8040–8045
Fig. 3. (a) XRD patterns of BiFeO3 films prepared under various pH values and (b) appropriate Fe3+ /Bi3+ molar ratios for BFO precursor solutions with various pH values.
only, which indicates that the liquid phase self-assembled method
is controllable.
This is because that according to the Hard-Soft-Acid-Base princi-
ple, hard acids prefer to associate with hard bases, soft acids prefer
to associate with soft bases, thus forming a strong bond complexes;
while hard acids associate with soft bases or hard-medial-soft
bases, hard bases associate with soft acids or hard-medial-soft acids
would form a weak bond complexes. Since Fe3+ is hard acid, Bi3+
is hard-medial-soft acid, citric acid is hard base, H2 O prefers to
dissolve ferric citrate complex, thus making the solubility of fer-
ric citrate greater. Therefore, the bismuth citrate complex would
reach its supersaturation degree prior to ferric citrate complex,
thus making Bi3+ have larger deposition rate and the functional-
ized ITO/glass substrates preferentially adsorb the bismuth citrate
complex. Therefore, the Fe3+ /Bi3+ molar ratio needs to be increased
to an appropriate value to obtain pure phase BFO thin films.
For the liquid phase self-assembled method, the stability of the
BFO precursor solution deteriorates with the increase of pH values.
Therefore, more bismuth citrate complexes are generated with the
increase of pH values, thus leading to the appearance of Bi2 O2.33
peaks which get stronger and stronger. When the Fe3+ /Bi3+ molar
ratio is increased to an appropriate value, the surplus Bi3+ are con-
sumed to combine with Fe3+ , thus forming the pure phase BFO film.
Therefore, the appropriate Fe3+ /Bi3+ molar ratios increased along
with the increase of pH values to obtain pure phase BFO thin films,
Fig. 4 shows the wide range and Fe2p XPS spectrum of the pure
phase BFO thin film prepared when the pH is 1.5. From which it can
be seen that the Bi5d, Bi4f, Bi4p, Fe2p, O1s peaks all appears, which
are corresponding to BiFeO3 . In addition, the C1s peak appeared
in the spectrum may be due to the main contaminant, the Si2p,
Na1s, In3d, In3p and Sn3d are from the ITO/glass substrates. For
Fe3+ ion, it has been reported by many researchers that the value
of Fe 2p3/2 peak position between 710.6 and 711.2 eV which has
associated satellite peaks at around 718.6 eV and 724.2 eV; while
for Fe2+ ion, the 2p3/2 core level appears at 709.5 eV [10]. The 3/2
and 1/2 spin–orbit doublet components of the Fe2p photoemission
obtained from our study located at 710.8 eV and 723.6 eV respec-
tively, which indicates that the oxidation state of Fe ion should be
Fe3+ without detectable Fe2+ .
Fig. 5(a)–(e) shows the FE-SEM images of pure phase BFO films
on ITO/glass substrates prepared under different pH values. The
pH value is a very important factor for liquid phase self-assembled
technique, which can affect not only the deposition rate of BFO
precursors but also the morphology of BFO thin films. It can be seen
that all films are dense, smooth, well-grown polycrystalline films,
but the size of grains increased gradually along with the pH values
since the deposition rate of Fe3+ and Bi3+ increases along with the
increase of pH values, thus leading to the formation of precursors
with greater diameter by the aggregation among BFO precursors,
thereby making the size of grains increased. Fig. 5(f) shows the
cross-section image of pure phase BFO film prepared when pH is
1.50. From which it can be seen that the pure phase BFO film has
even thickness of about 500 nm.
3.3. Micropatterning control of BiFeO3 thin films
The patterning technique is an important application of liq-
uid phase self-assembled method, which can be used to prepare
micropatterns of BFO films. Since the OTS-SAMs show large con-
trast in physical and chemical properties before and after UV
irradiation, it can be used to prepare a patterned template to assem-
ble the micropatterns. The patterned OTS-SAMs can be formed by
the UV irradiation through a photomask, which will cause a pho-
tocleavage reaction on the exposed areas while unexposed areas
unchanged. Fig. 6(a) shows the illustration of patterned OTS-SAMs.
From which it can be seen that the patterned OTS-SAMs was com-
posed of hydrophobic octadecyl regions next to the hydrophilic
silnaol regions. Fig. 6(b) shows the SEM image of micropattern of
BiFeO3 film. It can be seen that the micropattern is composed of
white and black lines which have clear edges. Fig. 6(c) and (d) shows
the SEM images of white and black lines. It can be seen that there are
only a few grains formed on the black lines which is composed of
hydrophobic octadecyl groups; while a dense and uniform film was
formed on the white lines which is composed of hydrophilic silnaol
groups. The large contrast between the two parts shows different
nucleation and growth behaviors, it suggests successfully selective
deposition of BFO precursors on silnaol regions, which is consistent
with that the Gao [11] has been reported.
3.4. Growth mechanism of BiFeO3 thin films
Citric acid was used as chelating agent in our work, which
plays a great role in the preparation of BFO thin films by liq-
uid phase self-assembled method. Fig. 7 shows the FT-IR spectra
of BFO precursors. From which it can be seen that the band at
3400 cm−1 is attributed to the OH stretching mode. The bands
at 1550 cm−1 and 1385 cm−1 are attributed to the COO stretch-
ing mode, which indicates the combination between citric acid, Bi3+
 X.R. Ren et al. / Applied Surface Science 258 (2012) 8040–8045 8043

Fig. 4. (a) XPS analysis of the pure phase BFO thin films and (b) Fe2p spectrum.

Fig. 5. (a–e) FE-SEM images of pure phase BFO thin films prepared under various pH values: pH = 1.50, 1.55, 1.60, 1.65, 1.70, respectively; (f) cross-section image of pure
phase BFO film when pH is 1.50.
8044 X.R. Ren et al. / Applied Surface Science 258 (2012) 8040–8045

Fig. 6. (a) Illustration of patterned OTS-SAMs; (b) SEM image of micropattern of BiFeO3 film; SEM images of (c) white lines and (d) black lines.

and Fe3+ . The band at 1616 cm−1 is attributed to the COOH char-
acteristic stretching mode, which shifts towards low wave number
since the band for pure citric acid appears at around 1700 cm−1 .
Therefore, the COOH is the main complex group.
Fig. 8 shows the XRD patterns of BiFeO3 thin films annealed at
different temperatures. From which it can be seen that when the
annealing temperature is 300 ◦ C, no BFO diffraction peaks appeared,
which indicates that the film is still in the amorphous state. As the
annealed temperature increased to 450 ◦ C the BFO diffraction peaks
emerged out, which indicates the transformation of BFO thin films
from amorphous state to crystalline state; but Bi2 O2.33 and Fe2 O3
diffraction peaks can be observed, which indicates that the BFO
thin films have not fully crystallized. With the increase of annealing
temperature, the intensities of BFO diffraction peaks get stronger
and the peaks become sharp, which shows better crystallinity.
Finally, the pure phase and crystalline BFO thin film was obtained
when the annealing temperature is 550 ◦ C. It can be seen that the
pure phase BFO peaks match well to the distorted rhombohedral
R3c structure.
The possible growth mechanism of BFO thin films may be as
follows:
(1) first, the three ligand COOH of citric acid provide lone electron
pairs, which combined with the empty tracks provided by Bi3+
and Fe3+ , thus forming polydentate ligand bismuth citrate and
ferric citrate;
(2) then, complicated BFO precursors were generated through the
polycondensation reaction between bismuth citrate and ferric
citrate;
(3) next, BFO precursors would precipitate from the BFO precursor
solutions when they reach their supersaturation degree;

Fig. 7. FT-IR spectra of BFO precursors. Fig. 8. XRD patterns of BFO thin films annealed at different temperatures.
 X.R. Ren et al. / Applied Surface Science 258 (2012) 8040–8045
(4) afterwards, after UV irradiation, the functionalized OTS-SAMs
composed of hydrophilic silanol groups is conducive to the het-
erogeneous nucleation of BFO precursors, and it was used as
templates, thus making the BFO precursors deposited onto the
functionalized surface by the electrostatic attraction of OTS-
SAMs, thereby gradually assembling the amorphous BFO films;
(5) finally, the pure phase BFO films were changed from amorphous
state into crystalline state after the annealing process at the
temperature of 550 ◦ C.
4. Conclusion
In conclusion, BiFeO3 thin films were grown on the ITO/glass
substrates covered with functionalized OTS-SAMs by liquid phase
self-assembled method at an annealing temperature of 550 ◦ C.
Changing the pH value of BFO precursor solutions will affect
the phase purity. According to the Hard-Soft-Acid-Base principle,
Bi3+ has larger deposition rate and therefore the Fe3+ /Bi3+ molar
ratio need to be adjusted to a higher value. The pure phase BFO
thin films can be obtained under various pH values and the appro-
priate Fe3+ /Bi3+ molar ratio increased along with the increase of
pH values, which indicates that the liquid phase self-assembled
method is controllable and the growth environment of pure phase
BFO thin films is not the only. All pure phase BFO films are well-
grown polycrystalline films, which have thickness of about 500 nm.
The micropattern of BiFeO3 film has clear edges, and a dense film
was formed only on the hydrophilic silnaol group regions, which
shows the selectively deposition of BFO precursors. The citric acid
chelated Bi3+ and Fe3+ through the three ligand COOH to form
BFO precursors, which were subsequently assembled on the tem-
plate provided by the functionalized OTS-SAMs to form amorphous
BFO thin films. The pure phase BFO films were changed from amor-
phous state into crystalline state after the annealing process at the
temperature of 550 ◦ C.
8045
Acknowledgement
This work was supported by the Project of National Natural Sci-
ence Foundation of China (50872077).
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