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EVALUATION OF METALORGANIC PRECURSORS FOR PREPARING

BiFeO3 THIN FILMS BY LIQUID DELIVERY CHEMICAL VAPOR
DEPOSITION
Y. Tasakia; T. Kanokob; M. Kabeyab; N. Chifub; S. Yoshizawab
a
Toshima MFG Co., Ltd., Higashimatsuyama, Saitama, Japan b Meisei University 2-1-1 Hodokubo,
Tokyo, Hino, Japan

To cite this Article Tasaki, Y. , Kanoko, T. , Kabeya, M. , Chifu, N. and Yoshizawa, S.(2006) 'EVALUATION OF
METALORGANIC PRECURSORS FOR PREPARING BiFeO3 THIN FILMS BY LIQUID DELIVERY CHEMICAL VAPOR
DEPOSITION', Integrated Ferroelectrics, 81: 1, 281 — 288
To link to this Article: DOI: 10.1080/10584580600663706
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 Integrated Ferroelectrics, 81: 281–288, 2006
Copyright © Taylor & Francis Group, LLC
ISSN 1058-4587 print / 1607-8489 online
DOI: 10.1080/10584580600663706

Evaluation of Metalorganic Precursors

for Preparing BiFeO3 Thin Films by Liquid
Delivery Chemical Vapor Deposition

Y. Tasaki,1 T. Kanoko,2 M. Kabeya,2 N. Chifu,2 and S. Yoshizawa2,∗

Downloaded By: [Seoul National University 2011] At: 06:12 20 April 2011

1
Toshima MFG Co., Ltd., 1414 Shimonomoto, Higashimatsuyama,
Saitama 355-0036, Japan
2
Meisei University 2-1-1 Hodokubo, Hino, Tokyo 191-8506, Japan

ABSTRACT

The metalorganic precursors to fabricate multiferroic BiFeO3 thin films by liquid-

delivery metalorganic chemical vapor deposition were investigated. Among the eval-
uated compounds, the combinations of Bi(p-Tol)3 and iron β-diketonates were suitable
to control the metal composition in BiFeO3 films. The films obtained using the precursor
solution with the molar ratio of Bi:Fe=1:1 included excess bismuth. The films with only
BiFeO3 phase could be fabricated at the substrate temperatures of 500◦ C and 525◦ C by
using the precursor solution of Bi(p-Tol)3 and Fe(IBPM)3 with the molar ratio of 2:1.
Though the remnant polarization of the film obtained at 525◦ C was very small, it was
confirmed that the BiFeO3 film had ferroelectricity.

Keywords: Multiferroic material; liquid-delivery CVD; bismuth iron oxide; precursor

INTRODUCTION

BiFeO3 is known as a multiferroic material that has simultaneously ferroelec-

tricity and ferromagnetism. Recently, BiFeO3 has been researched as a suit-
able material for the capacitor of non-volatile memories because a crystallized
BiFeO3 thin film could be prepared at the substrate temperature below 500◦ C
and showed giant ferroelectric polarization [1].
In most of reports on preparation of BiFeO3 films, laser deposition [1, 2]
or spin-coating [3–5] was selected as a fabrication method. In order to fabricate
films with high quality, metalorganic chemical vapor deposition (MOCVD) can
be adopted as an appropriate method. Especially, liquid-delivery MOCVD is a

Received April 17, 2005; in final form January 23, 2006.

∗
Corresponding author. E-mail: yoshizaw@chem.meisei-u.ac.jp

[2421]/281
 282/[2422] Y. Tasaki et al.

suitable method to mass production due to its high reproducibility. However,

it has never been reported that preparation of BiFeO3 films by liquid-delivery
MOCVD.
When thin films are prepared by MOCVD, it is very important to select
appropriate metalorganic precursors because different properties of precursors
affect deposition rates, compositions, surface morphology, crystallinity, ori-
entation and required characters for applications. In this study, the appropri-
ate metalorganic precursors to prepare BiFeO3 thin films by liquid-delivery
MOCVD were investigated.
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EXPERIMENTAL

Tri-ortho-tolyl bismuth (Bi(o-Tol)3 ) and tri-para-tolyl bismuth (Bi(p-Tol)3 )

were evaluated as bismuth precursors. They have been used for preparing
bismuth titanate system films [6]. As iron precursors, both β-diketonates
and cyclopentadienydes were evaluated. tris[dipivaloylmethanato]iron
(Fe(DPM)3 ), tris[2,2,6,6-tetramethyl-3,5-octanedionato]iron (Fe(TMOD)3 ),
tris[diisobutyrylmethanato]iron (Fe(DIBM)3 ) and tris[isobutyrylpivaloyl-
methanato]iron (Fe(IBPM)3 ) were selected as iron β-diketonates and
bis[cyclopentadienyl] iron (Fe(Cp)2 ) and bis[methylcyclopentadienyl]iron
(Fe(MeCp)2 ) were selected as iron cyclopentadienydes. Fe(DPM)3
[7–10] and Fe(Cp)2 [11, 12] have been used as MOCVD precursors but
Fe(MeCp)2 , Fe(TMOD)3 , Fe(DIBM)3 and Fe(IBPM)3 have never been used
for fabricating thin films.
The precursor solutions were prepared by dissolving bismuth and iron
precursors into toluene selected as a solvent. The sum of bismuth and iron
precursors included in 1 kg of toluene was fixed at 0.01 mol. As shown in
Fig. 1, the liquid-delivery MOCVD apparatus by which fabrication of thin
films was carried out consists of a vaporizer (Lintec Co., Ltd., VU-510) and
hot-wall type quartz tube reactor. The vaporizer temperature was set at 170◦ C.
The flow rates of the precursor solution, argon carrier gas and oxygen were
fixed at 0.3 g/min, 200 cm3 /min and 100 cm3 /min, respectively. As a substrate,
Pt(200 nm)/Ti(50nm)/SiO2 (500 nm)/Si(100) was selected. It was placed in
the front region of homothermal zone in the reactor and heated at the range
of 450∼ 625◦ C. The reactor pressure was set at 10 torr. Identification of the
obtained films was carried out by X-ray diffraction (XRD) 2θ-scan (θ = 1◦ ).
The amounts of bismuth and iron in the solution made by dissolving the obtained
films with diluted nitric acid were measured by inductively coupled plasma
atomic emission spectrometry (ICP-AES) and the deposition rates of bismuth
and iron were calculated from the results. P-E hysteresis loops were measured by
a ferroelectric tester (Radiant Technologies Inc., Precision LC) after depositing
Pt top electrode by sputtering. The applied voltage and frequency were 1.5 V
and 100 Hz, respectively.
 Evaluation of Metalorganic Precursors for Preparing BiFeO3 [2423]/283
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Figure 1. Schematic diagram of liquid-delivery MOCVD apparatus.

RESULTS AND DISCUSSION

At the first experiment, an iron precursor was fixed at Fe(IBPM)3 and bis-
muth precursors were varied. The precursor solutions were prepared by mixing
bismuth and iron precursors with a molar ratio of 1:1 and dissolving them in
toluene.
The dependences of the deposition rates of bismuth and iron on substrate
temperatures were shown in Fig. 2. Regarding the deposition rate of iron, re-
markable dependence was not observed on the substrate temperatures and on
kinds of bismuth precursors. The deposition rate of bismuth from Bi(p-Tol)3
increased more gently than that from Bi(o-Tol)3 by raising substrate temper-
ature. This phenomenon was presumably caused by the difference of thermal
decomposition temperature of the precursors. It is difficult to control the metal
composition in films in the case of using the precursor which has steep increase
of deposition rate by raising substrate temperature. Therefore, a bismuth pre-
cursor was fixed at Bi(p-Tol)3 in the second experiment and iron precursors
were varied.
The dependences of the deposition rates of bismuth and iron on substrate
temperatures were shown in Figs. 3–5. In the case of using iron cyclopentadi-
enydes as iron precursors, iron was little deposited in films as shown in Fig. 3.
At the substrate temperature of more than 550◦ C, the deposition rate of iron
increased but that of bismuth transiently decreased at 575◦ C. It is presumed that
 284/[2424] Y. Tasaki et al.
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Figure 2. Dependence of the deposition rates of bismuth and iron on substrate temper-
atures in the case of using Bi(o-Tol)3 or Bi(p-Tol)3 as a bismuth precursor and fixing at
Fe(IBPM)3 as an iron precursor.

Figure 3. Dependence of the deposition rates of bismuth and iron on substrate tem-
peratures in the case of using Fe(Cp)2 or Fe(MeCp)2 as an iron precursor and fixing at
Bi(p-Tol)3 as a bismuth precursor.
 Evaluation of Metalorganic Precursors for Preparing BiFeO3 [2425]/285
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Figure 4. Dependence of the deposition rates of bismuth and iron on substrate temper-
atures in the case of using Fe(DPM)3 or Fe(DIBM)3 as an iron precursor and fixing at
Bi(p-Tol)3 as a bismuth precursor.

Figure 5. Dependence of the deposition rates of bismuth and iron on substrate temper-
atures in the case of using Fe(IBPM)3 or Fe(TMOD)3 as an iron precursor and fixing at
Bi(p-Tol)3 as a bismuth precursor.
 286/[2426] Y. Tasaki et al.

bismuth and iron were deposited on substrates after iron cyclopentadienydes

reacted to Bi(p-Tol)3 and changed into something intermediate. On the other
hand, when iron β-diketonates were used as iron precursors, the deposition rates
of iron were sufficient and relatively constant independent of the substrate tem-
peratures as shown in Figs. 4 and 5. From these results, it was found that iron
β-diketonates were more suitable as iron precursors for fabrication of BiFeO3
films than iron cyclopentadienydes. Especially, Fe(IBPM)3 shows the highest
deposition rate of iron among six iron compounds.
In order to prepare stoichiometric BiFeO3 thin films, Bi(p-Tol)3 and
Fe(IBPM)3 were selected as precursors. The mixing ratio in the precursor solu-
tion was changed into Bi(p-Tol)3 :Fe(DIBM)3 = 2:1 because the films obtained
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using the precursor solution with the molar ratio of Bi(p-Tol)3 :Fe(IBPM)3 =
1:1 included excess bismuth. Figure 6 shows the XRD patterns of the films
obtained at 500, 525 and 550◦ C by using the precursor solution. BiFeO3 phase
was observed in any film. Bi2 O3 phase was also observed at 550◦ C. It is thought
that increase of the deposition rate of bismuth by raising substrate temperature
generated this secondary phase. Figure 7 shows the P-E hysteresis loop of the
100nm-thick film fabricated at 525◦ C. Though the value of remnant polarization
was very small, it was confirmed that the BiFeO3 film had ferroelectricity.

Figure 6. XRD patterns of the films obtained at (a) 550◦ C; (b) 525◦ C and (c) 500◦ C by
using the precursor solution of Bi(p-Tol)3 and Fe(DIBM)3 with the molar ratio of 2:1.
 Evaluation of Metalorganic Precursors for Preparing BiFeO3 [2427]/287
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Figure 7. P-E hysteresis loop of the BiFeO3 film fabricated at 525◦ C by using the
precursor solution of Bi(p-Tol)3 and Fe(DIBM)3 with the molar ratio of 2:1.

CONCLUSIONS

The metalorganic precursors to fabricate BiFeO3 thin films by liquid-delivery

metalorganic chemical vapor deposition were investigated. The deposition rate
of bismuth from Bi(p-Tol)3 increased more gently than that from Bi(o-Tol)3 by
raising substrate temperature.
In the case of iron precursors, the deposition rates of iron from iron β-
diketonates were much higher than those from iron cyclopentadienydes and
were independent of substrate temperature and the kinds of bismuth precur-
sors. Therefore, the combinations of Bi(p-Tol)3 and iron β-diketonates can
be suggested as the appropriate precursors to fabricate BiFeO3 thin films by
MOCVD.

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