See

discussions, stats, and author profiles for this publication at: https://www.researchgate.net/publication/224403106

Enhanced Ferroelectric Properties of Cr-Doped

BiFeO3 Thin Films Grown by Chemical Solution
Deposition

Article in Applied Physics Letters · April 2006

DOI: 10.1063/1.2189453 · Source: IEEE Xplore

CITATIONS READS

215 233

5 authors, including:

Jong Kuk Kim Sang Su Kim

Soongsil University Changwon National University
74 PUBLICATIONS 1,226 CITATIONS 101 PUBLICATIONS 1,246 CITATIONS

SEE PROFILE SEE PROFILE

Ruyan Guo
University of Texas at San Antonio
478 PUBLICATIONS 7,526 CITATIONS

SEE PROFILE

Some of the authors of this publication are also working on these related projects:

THE CREATION OF NON-LINEAR ELEMENTS FOR TRANSPARENT ELECTRONICS View project

Magnetic Control of THz Propogation View project

All content following this page was uploaded by Ruyan Guo on 27 June 2016.

The user has requested enhancement of the downloaded file.

 Enhanced ferroelectric properties of Cr-doped BiFeO3 thin films grown by
chemical solution deposition
Jong Kuk Kim, Sang Su Kim, Won-Jeong Kim, Amar S. Bhalla, and Ruyan Guo

Citation: Appl. Phys. Lett. 88, 132901 (2006); doi: 10.1063/1.2189453

View online: http://dx.doi.org/10.1063/1.2189453
View Table of Contents: http://apl.aip.org/resource/1/APPLAB/v88/i13
Published by the American Institute of Physics.

Additional information on Appl. Phys. Lett.

Journal Homepage: http://apl.aip.org/
Journal Information: http://apl.aip.org/about/about_the_journal
Top downloads: http://apl.aip.org/features/most_downloaded
Information for Authors: http://apl.aip.org/authors

Downloaded 12 Apr 2013 to 129.115.2.47. This article is copyrighted as indicated in the abstract. Reuse of AIP content is subject to the terms at: http://apl.aip.org/about/rights_and_permissions
 APPLIED PHYSICS LETTERS 88, 132901 共2006兲

Enhanced ferroelectric properties of Cr-doped BiFeO3 thin films

grown by chemical solution deposition
Jong Kuk Kim, Sang Su Kim,a兲 and Won-Jeong Kim
Department of Physics, Changwon National University, Changwon Kyungnam 641-773, Korea
Amar S. Bhalla and Ruyan Guo
187 Materials Research Laboratory, The Pennsylvania State University, University Park,
Pennsylvania 16802
共Received 22 September 2005; accepted 27 February 2006; published online 27 March 2006兲
Multiferroic Cr-doped BiFeO3 共BFO兲 thin films were prepared on Pt/ TiO2 / SiO2 / Si共100兲 substrates
by a chemical solution deposition method. From the x-ray photoelectron spectroscopy
measurements, it was observed that the valence number of Fe ion in undoped and Cr-doped BFO
thin films was found to be almost 3+. It was found that Cr-doped BFO thin films exhibited good
ferroelectric properties, such as improved leakage-current density and P-E hysteresis characteristics.
The 3 mol % Cr-doped BFO thin film showed a leakage-current density of 9.2⫻ 10−7 A / cm2 at
100 kV/ cm and a large remanent polarization 共Pr兲 of 61 ␮C / cm2 at room temperature. © 2006
American Institute of Physics. 关DOI: 10.1063/1.2189453兴

Multiferroic materials that exhibit long range electric as
well as magnetic orderings have been studied for a new type
of memory application using a combination of ferroelectric
and ferromagnetic properties.1,2 Among them, BiFeO3 共BFO兲
with a rhombohedrally distorted simple perovskite structure,
has been of much interest due to its antiferromagnetic behav-
ior with a relatively high Néel temperature 共TN ⬃ 380 ° C兲
and its ferroelectric behavior with a high Curie temperature
共TC ⬃ 810 ° C兲.3 The spontaneous polarization of bulk BFO
was expected to be ⬃91.5 ␮C / cm2 because of large atomic
displacements and a high Curie temperature.4 However, the
spontaneous polarizations reported in the literature were
much lower than the theoretical 共ideal兲 one.5–7 This can be
attributed to the high leakage current densities of BFO, since
the ferroelectric properties of BFO disappeared with the high
bias electric fields due to the high leakage current.
Recently it was reported that epitaxial and polycrystal-
line BFO thin films prepared by pulsed laser deposition
共PLD兲 in narrow ranges of oxygen partial pressure exhibited
well-saturated ferroelectric hysteresis loops, including large
remanent polarizations Pr 共50– 150 ␮C / cm2兲 and large coer-
cive fields Ec 共120– 200 kV/ cm兲.8–11 However, good ferro-
electric BFO thin films prepared by a chemical solution
deposition method, which has an advantage in the mass pro-
duction of thin films, have not been reported yet. Meanwhile,
it is well known that many physical properties of materials
may vary significantly with a small change of chemical com-
position through doping or substitution of impurities. For
example, partial substitution of Fe ion by 2 at. % Ti ion in
BFO films increased the dc resistivity by more than three
orders of magnitude, although Ti-doped BFO films did not
exhibit saturated polarization.6 In order to improve ferroelec-
tric properties of BFO thin films grown by chemical solution
deposition, Cr has been partially substituted for Fe.
a兲
Electronic mail: sskim@changwon.ac.kr; present address: Materials Re-
search Laboratory, The Pennsylvania State University, University Park, PA
16802; electronic mail: ssk11@psu.edu
In this letter, improved ferroelectric properties of Cr-
doped BFO thin films grown by chemical solution deposition
have been reported.
BFO thin films, with or without a Cr dopant, were grown
on the Pt/ TiO2 / SiO2 / Si共100兲 substrates by a chemical solu-
tion deposition method. For a typical preparation of Cr-
doped BFO thin films, bismuth nitrate 关Bi共NO3兲3 · 5H2O兴
共5 mol % excess兲 and iron nitrate 关Fe共NO3兲3 · 5H2O兴 were
dissolved in acetic acid at room temperature using a stirring
mixer. Then chromium nitrate 共as a dopant precursor with
concentrations ranging from 1 to 10 mol %兲 was dissolved
into the Bi-Fe stock solution. The Cr-doped BFO thin films
were coated by the spin-coating technique at 3000 rpm for
25 s with the precursor solution. The coated thin films were
crystallized at 550 ° C for 30 min in a N2 atmosphere. The
crystalline structures of the thin films were analyzed by x-ray
diffraction 共Philips APD system兲 analysis, and the valence
numbers of Fe ion in BFO thin films were obtained by the
x-ray photoelectron spectroscopy 共XPS, ESCALAB 250兲
measurements. In order to fabricate capacitors, gold elec-
trodes were deposited by an e-beam evaporation method
through a shadow mask. The hysteresis loops and leakage
current characteristics of the Cr-doped BFO thin film capaci-
tors were measured using a ferroelectric tester 共Radiant Pre-
cision LC兲 and an electrometer 共Keithley 6517A兲.
Figure 1 shows the x-ray diffraction patterns of Cr-doped
BFO thin films annealed in N2 atmosphere. The effect of Cr
doping on the structure of BFO thin films was analyzed in
the range of 0 – 10 mol %. BFO thin films with less than
3 mol % Cr dopant have been identified as polycrystalline
perovskite without secondary phases. Furthermore, the peak
positions corresponding to perovskite structure are not
changed appreciably by 3 mol % Cr doping. However, an
additional peak 共2␪ = 27.7° 兲 has been observed from the
x-ray diffraction pattern of the BFO thin films with more
than 5 mol % Cr dopant, which could be attributed to the
共310兲 reflection of the Bi25FeO40 phase. The 共310兲 peak in-
tensity of Bi25FeO40 phase increases with increased Cr dop-
ant, which may indicate that the limit of Cr substitution in
BiFeO3 is close to 3 mol %.

0003-6951/2006/88共13兲/132901/3/$23.00 88, 132901-1 © 2006 American Institute of Physics

Downloaded 12 Apr 2013 to 129.115.2.47. This article is copyrighted as indicated in the abstract. Reuse of AIP content is subject to the terms at: http://apl.aip.org/about/rights_and_permissions
132901-2 Kim et al.
FIG. 1. X-ray diffraction patterns of 550 ° C annealed Cr-doped
共0 – 10 mol % 兲 BFO thin films on Pt/ TiO2 / SiO2 / Si共100兲 substrates.
The room temperature P-E hysteresis loops of undoped
and 3 mol % Cr-doped BFO thin films annealed at 550 ° C
for 30 min in N2 atmosphere are shown in Fig. 2. The un-
doped BFO thin film exhibits a poor P-E hysteresis loop
关Fig. 2共a兲兴, which has been typically observed from conduc-
tive ferroelectrics. The undoped BFO thin film gave up the
ferroelectricity with increased bias electric field due to a
large leakage current. In contrast, the 3 mol % Cr-doped
BFO thin film shows well-saturated hysteresis characteristics
with a large remanent polarization 共Pr兲 of 61 ␮C / cm2 and a
coercive field 共Ec兲 of 290 kV/ cm at a maximum applied
electric field of 1000 kV/ cm. Although the measured Pr is
similar to that of epitaxial BFO thin films 共50– 60 ␮C / cm2兲
grown by a PLD method, the measured Ec is larger than
those of ⬃180 kV/ cm.8 It seems that the relatively large
coercive field is caused by the well-known resistance of the
Cr3+ ion to displacement from its centrosymmetric position
FIG. 2. P-E hysteresis loops of 共a兲 undoped and 共b兲 Cr-doped BFO thin
films as a function of electric field.
Downloaded 12 Apr 2013 to 129.115.2.47. This article is copyrighted as indicated in the abstract. Reuse of AIP content is subject to the terms at: http://apl.aip.org/about/rights_and_permissions
Appl. Phys. Lett. 88, 132901 共2006兲
FIG. 3. J-E characteristics of the undoped and Cr doped BFO thin films.
in an octahedral environment, which restricts reversing of the
polarization.12
Figure 3 illustrates the influence of Cr doping on the
leakage-current densities of BFO thin films. The data show
that the leakage-current density 共JL兲 of 3 mol % Cr-doped
BFO thin films is significantly decreased from that of un-
doped BFO thin films. The JL of 9.2⫻ 10−7 A / cm2 at a bias
electric field of 100 kV/ cm for the 3 mol % Cr-doped BFO
thin film is approximately four orders of magnitude lower
than that of 1.7⫻ 10−2 A / cm2 for the undoped BFO thin
film. This result demonstrates that the enhanced electrical
resistance of Cr modified BFO up to a higher field region
plays a critical role in sustaining a ferroelectric polarization
at room temperature. Qi et al.6 reported that the Ti4+-doped
BFO film was unable to reach a saturated polarization due to
the high JL at higher field region, although the JL of Ti-doped
BFO films decreased more than three orders of magnitude
from that of undoped BFO film at low electric field region.
Generally, it was assumed that the conduction mecha-
nism of BFO was related to the hopping of electrons from
Fe2+ to Fe3+ when oxygen vacancies are present in the lat-
tice, which act as a “bridge” between Fe2+ and Fe3+ and play
an important role in the electronic conduction.13
In order to identify the valence numbers of Fe ion for
undoped and 3 mol % Cr-doped BFO thin films, the BFO
thin films were investigated by the XPS. Figure 4 shows the
Fe 2p XPS spectra of the BFO thin films. It has been known
that the binding energies of Fe2+ and Fe3+ are slightly differ-
ent, which can be separated from the XPS spectra. However,
FIG. 4. Fe 2p XPS spectra of the undoped and Cr-doped BFO thin films
annealed at 550 ° C after being in situ etched by an Ar+ ion beam for 3 min.
132901-3 Kim et al. Appl. Phys. Lett. 88, 132901 共2006兲

the measured Fe 2p3/2 peaks were not able to deconvolute good ferroelectric BFO thin films. Furthermore, it was
into two peaks, corresponding to Fe2+ and Fe3+ states, which clearly demonstrated that the good multiferroic BFO thin
suggests that the concentration ratio between Fe2+ and Fe3+ films could be fabricated by a chemical solution deposition
is not compatible. The Fe 2p3/2 spectra have been fitted with method, which is advantageous for real device applications.
a single peak. The center of the peak was calculated to be
711.2 eV, which reflects that the valence number of Fe ion in This work was supported by the Korean Research Foun-
undoped and 3 mol % Cr-doped BFO thin films is close to dation 共Grant No. KRF-2000-005-Y00070兲.
trivalent 共Fe3+兲.14 Furthermore, XPS spectra of both BFO 1
N. Hur, S. Park, P. A. Sharma, J. S. Ahn, S. Guha, and S.-W. Cheong,
thin films are almost identical, which suggests that the dif- Science 429, 392 共2004兲.
ference of Fe valance states in both films are negligible 2
T. Kimura, S. Kawamoto, I. Yamade, M. Azuma, M. Takano, and Y.
within the instrument resolution. Eerenstein et al.15 reported Tokura, Phys. Rev. B 67, 180401 共2003兲.
3
an activation energy of 1.03± 0.05 eV, compatible with only C. Michel, K.-M. Moreau, G. D. Achenbach, R. Gerson, and W. J. James,
a small concentration of oxygen vacancies, by measuring Solid State Commun. 7, 701 共1969兲.
4
J. B. Neaton, C. Ederer, U. V. Waghmare, N. A. Spaldin, and K. M. Rabe,
high-temperature conductivity of BFO. Therefore, it was de- Phys. Rev. B 71, 014113 共2005兲.
duced that the high leakage current density in the undoped 5
V. R. Palkar, J. John, and R. Pinto, Appl. Phys. Lett. 80, 1628 共2002兲.
BFO thin film was originated from relatively low level Fe2+ 6
X. Qi, J. Dho, R. Tomov, M. G. Blamire, and J. L. MacManus-Driscoll,
ions, though the Fe2+ state was not observed in the XPS Appl. Phys. Lett. 86, 062903 共2005兲.
7
spectra. Only a small change in chemical composition by Cr S. Lakovlev, C.-H. Solterbeck, M. Kuhnke, and M. Es-Souni, J. Appl.
Phys. 97, 094901 共2005兲.
substitution, resistant to oxidation and reduction, with Fe in 8
J. Wang, J. B. Neaton, H. Zheng, V. Nagarajan, S. B. Ogale, B. Liu, D.
BFO thin film suppresses the formation of oxygen vacancy Viehland, V. Vaithyanathan, D. G. Schlom, U. V. Waghmare, N. A. Spal-
and subsequently lowers the conductivity. din, K. M. Rabe, M. Wuttig, and R. Ramesh, Science 299, 1719 共2003兲.
9
In conclusion, single phase BFO and Cr-doped BFO J. Wang, H. Zheng, Z. Ma, S. Prasertchoung, M. Wuttig, R. Droopad, J.
thin films were successfully deposited on the Yu, K. Eisenbeiser, and R. Ramesh, Appl. Phys. Lett. 85, 2574 共2004兲.
10
K. Y. Yun, M. Noda, and M. Okuyama, Appl. Phys. Lett. 83, 3981 共2003兲.
Pt/ TiO2 / SiO2 / Si共100兲 substrates by the chemical solution 11
K. Y. Yun, D. Ricinschi, T. Kanashima, M. Noda, and M. Okuyama, Jpn.
deposition method. The leakage-current density of a 3 mol % J. Appl. Phys., Part 2 43, L647 共2004兲.
12
Cr-doped BFO thin film was significantly decreased. The N. A. Hill, P. Bättig, and C. Daul, J. Phys. Chem. B 106, 3383 共2002兲.
13
3 mol % Cr-doped BFO thin film showed a leakage-current W. M. Zhu and Z.-G. Ye, Ceram. Int. 30, 1435 共2004兲.
14
Th. Schedel-Niedrig, W. Weiss, and R. Schlëgl, Phys. Rev. B 52, 17449
density of 9.2⫻ 10−7 A / cm2 at 100 kV/ cm and a large rem- 共1995兲.
anent polarization 共Pr兲 of 16 ␮C / cm2 at room temperature. 15
W. Eerenstein, F. D. Morrison, J. Dho, M. G. Blamire, J. F. Scott, and N.
These results indicate that Cr is an effective substituent for D. Mathur, Science 307, 1203a 共2005兲.

View publication stats

Downloaded 12 Apr 2013 to 129.115.2.47. This article is copyrighted as indicated in the abstract. Reuse of AIP content is subject to the terms at: http://apl.aip.org/about/rights_and_permissions