Ceramics International 44 (2018) 9053–9057

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Ceramics International
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Structural, electrical and magnetic properties of (110)-oriented BF-BZT-ST T

Films
⁎
Caimin Menga,b,c, Bobo Tiand, Haoliang Wanga,b,c, Shuo Suna, Hong Shena, Tie Lina, , Jian Yue,
Jinglan Suna, Xiangjian Menga, Junhao Chua,b
a
State Key Laboratory of Infrared Physics, Shanghai Institute of Technical Physics, Chinese Academy of Sciences, 500 Yu Tian Road, Shanghai 200083, China
b
ShanghaiTech University, Shanghai 201210, China
c
University of Chinese Academy of Sciences, China
d
Key Laboratory of Polar Materials and Devices, Ministry of Education, East China Normal University, Shanghai 200241, China
e
Institute of Functional Materials, Donghua University, Shanghai 201620, China

A R T I C L E I N F O A B S T R A C T

Keywords: Highly (110)-oriented BiFeO3-Bi(Zn/Ti)O3-SrTiO3 thin films were prepared on conductive Nb doped SrTiO3
BiFeO3 substrates by pulsed laser deposition. The results demonstrate that the films show a pure perovskite phase with
Pulsed laser deposition R3c symmetry. The films have a low dielectric loss, and a typical multiferroics character, possessing both of
Multiferroics ferroelectric and ferromagnetic properties. The reduced dielectric loss is attributed to thermodynamic stabili-
zation and charge compensation mechanisms in the BiFeO3 system. The remnant polarization (Pr) and the
remnant magnetization (Mr) are ~ 46.2 μC/cm2 and ~ 4.6 emu/cm3 respectively.

1. Introduction phases in thermodynamic equilibrium over a wide temperature range,

i.e., perovskite BiFeO3, sillenite Bi25FeO39, and mullite Bi2Fe4O9 [3].
Multiferroics are materials that exhibit two or more primary ferroic The secondary phases of Bi25FeO39 and Bi2Fe4O9 often coexist with
order parameters simultaneously, which have provoked great scientific perovskite BiFeO3 during the solid-state reaction between Bi2O3 and
interests because of their potential applications in information storage, Fe2O3, or peritectic decomposition from perovskite BFO [3,4]. These
spintronics, and sensor devices [1,2]. In general, multiferroism often secondary phases are considered as the major causes of the high leakage
refers to any combination of ferroelectricity and magnetism (both fer- current and dielectric loss in BFO system. Besides the thermodynamic
romagnetism (FM) and anti-ferromagnetism (AFM)) in one particular stabilization, charge compensation mechanisms should also be taken
material. Among the numerous reported multiferroics, BiFeO3 (BFO) is into account to fabricate robust insulating phase-pured bismuth ferrite
the most investigated both in theories and experiments. BFO exhibits a compounds [3,5,6].
unique property, i.e., the coexistence of ferroelectrics (the Curie tem- Element-substitutions to Bi or Fe sites are frequently used to sup-
perature, TC is ~ 1103 K) and antimagnetism (the Néel Temperature, TN press the secondary phase and improve the thermodynamic stability of
~ 643 K), making it appealing for wide applications in high-density perovskite BFO. Recently we developed a ternary solid solution, Bi1-
memory devices, sensors, actuators, etc. [2] xLaxFe1-yTiyO3 ceramics, where both the Bi and Fe are partially sub-
Although substantial progresses have been achieved in the physics stituted by La and Ti respectively [3]. In our ceramics, the secondary
and material sciences of BFO system, some pending issues are still to be phases of Bi25FeO39 and Bi2Fe4O9 are effective suppressed and the
resolved in such material system, e.g., the larger dielectric loss and high ceramics shows a robust electrical insulative feature, which is essential
leakage current density, the weak magnetoelectric effect, which are the to the possess of ferroelectricity [7]. The spin configuration of BFO
major obstacles to explore the practical devices. To date, various me- exhibits G-type antiferromagnetism, wherein neighboring Fe spins
chanisms have been proposed to explain the high leakage current and couple ferromagnetically within pseudocubic (111) planes and anti-
high dielectric loss in BFO ceramics and thin films, such as off- ferro-magnetically between neighboring (111) planes [8,9]. The sym-
stoichiometry caused by the volatility of Bi2O3, presence of Bi25FeO39 metry of BFO allows for a small canting of the Fe spins between
and Bi2Fe4O9 secondary phases, coexistence of Fe2+ and Fe3+, etc. BFO neighboring (111) planes, giving rise to a net magnetization and a weak
can be regarded a binary system of Bi2O3 and Fe2O3. There are three ferromagnetic moment of the Dzyaloshinskii–Moriya type [10,11]. It is

⁎
Corresponding author.
E-mail address: [email protected] (T. Lin).

https://doi.org/10.1016/j.ceramint.2018.02.109
Received 29 January 2018; Received in revised form 11 February 2018; Accepted 12 February 2018
Available online 13 February 2018
0272-8842/ © 2018 Elsevier Ltd and Techna Group S.r.l. All rights reserved.
C. Meng et al. Ceramics International 44 (2018) 9053–9057

proposed that Ti4+(d0) substitution can destroy the incommensurate

cycloidal spin configuration of BFO into homogeneous AFM one, which
provides availability to release parasitic FM through spin canting, thus
enhancing the magnetism [12]. In addition, the substitution of Bi-site
may also influence both the lattice and magnetic properties of BFO
system. From the point view of crystal symmetry, it is necessary to keep
the BFO system with a trigonal lattice. We successfully prepared a
ternary-solid-solution ceramics with the component of 0.70(BiFeO3)-
0.04Bi(Zn1/2Ti1/2)O3-0.26SrTiO3, which shows a low dielectric loss (~
0.02), obvious ferroelectric feature and a high remanent magnetic
moment. Both ferroelectricity and ferromagneticity have been realized
in the 0.70(BiFeO3)-0.04Bi(Zn1/2Ti1/2)O3-0.26SrTiO3 ceramics as a
ternary solid solution [13].
As Chu et al. pointed out, BFO thin film was a playground for ex-
ploring multifunctionalities, where the multiferroics and magneto-
electric effect could be expected to be enhanced if the ceramics with a
ternary solid solution could be transferred into thin films [9]. Eeren-
stein et al. also pointed out that to reduce the dimensionality might
achieve large magnetoelectric effects at room temperature [14]. The
magnetoelectric effect in a single-phase crystal is governed by sym-
metry in accordance with Neumann Principle. For materials with no
symmetry center and time asymmetry, the linear magnetoelectric(ME)
coefficient aij can only be non-zero [9,14]. For R3c lattice which be-
longs to 3 m point group, magnetoelectric coefficient α12 is the only
non-zero coefficient of the ME rank tensor. To correspond the compo-
nent with the lattice, here we noted Cartesian coordinates with the z
axis aligned along the polar axis of BFO (pseudocubic direction [111])
as i = 3rd component, [110] as 2nd, and the axis perpendicular to those
Fig. 1. a) Hysteresis loops with 1000-ms preset delay and 1-ms hysteresis period. The two axis as 1st. In this case, (110)-oriented film will obtain the possible
electrode area is 0.04 mm2. b) Magnetic hysteresis loops of the < 110 > oriented epi-
linear magnetic effect in terms of symmetry. In the present work,
taxial films of BF-BZT-ST grown on STO.
modified BFO thin films with the component of 0.70(BiFeO3)-0.04Bi
(Zn1/2Ti1/2)O3-0.26SrTiO3 are prepared on the Nb doped (110) SrTiO3
(NSTO) substrates by pulse laser deposition (PLD) in order to obtain the
(110)-oriented films. The modified BFO thin films show a low dielectric

Fig. 2. a) XPS spectrum of the (110) oriented epitaxial film of BFO70-BZT4-STO26 grown on STO. b)–d) High-resolution XPS spectra of the Bi 4f, Fe 2p, and O 1s core level, respectively.

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Fig. 3. a) εr/tanδ-f curves from frequency ranging from 100 to 10E6 Hz, Dissipation curves between 1000 and 10,000 Hz shows that the relaxation was eliminated by the annealing
process and valid for films of different thicknesses. b) εr/tanδ-f − 1000/T curves at 100–10,000 Hz, from 160 K to 330 K.

target are 13 mm and 3 mm respectively. The films were prepared in an

oxygen ambient of 5.22 × 10−2 mbar using a KrF excimer laser (~
248 nm) with an averaged energy of ~ 58.1 mJ (~ 1.465 J/cm3) and a
frequency of 6 Hz. The substrate was heated by a Gauss-distributed
laser beam on the RA330 holder, and the temperature was detected by a
pyrometer on the holder with emission of 90. Silver glue was used to
stick the substrate with the holder. The temperature of the substrate is
620 °C. Sequentially, the as-grown films were heated to 750 °C with a
rate of 5 °C/min in an oxygen of 200 mbar, annealed for one hour, and
cooled down to room temperature with a rate of 5 °C/min. The average
thickness of our BiFeO3-Bi(Zn/Ti)O3-SrTiO3 films is about 200 nm for
23,999 pulses, which is verified by Scanning Electron Microscope
(SEM). The crystal structures were investigated by using X-ray dif-
Fig. 4. Arrhenius plot lnσ− 1000/T at 1 kHz. The original data is present in black bubble fraction (XRD) (Bruker D8 tools). X-ray photoelectric spectroscopy
and the fitted data in blue with a slope of − 0.1528. (For interpretation of the references (XPS) was applied to analyze the crystal phases and the oxidation states
to color in this figure legend, the reader is referred to the web version of this article.) of the elements of the films, and the XPS measurements are in the
analyzer mode of constant analyzer energy (CAE) with pass energy of
loss, good ferroelectric properties and clear ferromagneticity. 50.0 eV.
Ti/Au (~ 20/65 nm) was sputtered on the BiFeO3-Bi(Zn/Ti)O3-
SrTiO3 films with a mask to form the capacitor structure for electrical
2. Experimental measurements. The size of the top electrodes was ~ 400 µm2. The fre-
quency dependent dielectric constant and dielectric loss were obtained
Here the BiFeO3-Bi(Zn/Ti)O3-SrTiO3 films were deposited on NSTO by using Agilent E4980A with an ac driven voltage of 0.02 V.
substrates (Nb 0.07 wt%) by a PLD system (TSST Inc.). The target is a Polarization-Electric (P-E) hysteresis loop was obtained by Radiant
ternary solid solution ceramics with the component of 0.70(BiFeO3)- Precision LC. The field-dependent magnetic measurements (M-H
0.04Bi(Zn1/2Ti1/2)O3-0.26SrTiO3. The diameter and the thickness of the

Fig. 5. a) Hysteresis loops with 1000-ms preset delay and 1-ms hysteresis period. The electrode area is 0.04 mm2. b) Magnetic hysteresis loops of the < 110 > oriented epitaxial BF-BZT-
ST film grown on STO.

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hysteresis loops) were carried out by using PPMS-9 with vibrating drive voltage, which are up to 585 kV/cm and ~ 46.2 μC/cm2, re-
sample magnetometer (Quantum Design). All the measurements were spectively, as the drive voltage is 23 V. The Pr of our films is smaller
carried out at room temperature. than that of the other reported BFO thin films [20], which can be at-
tributed to the (110) orientation of our films while the spontaneous
3. Results and discussion ferroelectric polarization points along < 111 > directions in BFO
crystals. However, our films exhibit much better ferroelectricity than its
Fig. 1a shows XRD patterns of the BF70-BZT4-ST26 films. The counterpart in ceramics form. The enhancement of ferroelectricity in
patterns show a highly (110) orientation with only (110) BFO pseu- film form compared with ceramics can be caused by the constraints
docubic peaks apart from the NSTO substrate peaks. The only (110) resulted from the substrates. Note that the P-E loops show an asym-
oriented diffraction peaks indicate that the films have a pure phase, and metric feature, which is normally due to the pining effect by defect
demonstrate a thermodynamic equilibrium in our films as their coun- dipoles or defect clusters on domain walls. In our case, the different
terpart in bulk ceramics [4]. The result also show that the BF-BZT-ST materials for the top and bottom electrodes also have a contribution to
films belong to the combination of R3c space group compared to their the asymmetric P-E loops. Although the P-E loops obtained at high drive
bulk counterpart structure which only keeps (110) peaks around 32.4° voltages are close to saturated shape, there is still a slight rounded
[15]. Fig. 1b provides the SEM image of the film grown on NSTO. It feature near the maximum voltage in the loop, indicating the existence
could be concluded that the film was grown in islands with a thickness of weak leakage currents. In addition, a pinched part is demonstrated in
of around 200 nm. the second quadrant of the P-E loops. The weak leakage current and
Fig. 2(a–d) are the XPS spectrum of the films. It can be seen that the slightly distorted P-E loop are resulted from the potential residual
films are constituted of elements of Bi, Fe, O and Sr, which is constant to charged defects in the BF-BZT-ST films.
the main elements of the target. The two peaks positioned at 158 and The out-plane and in-plane magnetic moments depending on ex-
164 eV respectively are corresponding to Bi 4f7/2 and Bi 4f5/2, con- ternal magnetic field hysteresis (M-H hysteresis) are shown in Fig. 5b.
firming the trivalent oxidation state of Bi, i.e., Bi3+ in our BF-BZT-ST The coercive magnetic field (Mc) and the remanent magnetization (Mr)
films. The peaks located at 710.2 eV and 724.1 eV are ascribed to Fe3+. are ~ 330 Oe and ~ 4.6 emu/cm3, respectively. Although both the films
A weak peak is shown adjacent to the peak associated with O 1s at and ceramics have the same composition, the Mr of our films is much
528 eV, which may be resulted from the surface contamination of the higher that of the ceramics. On the one hand, this is consistent to the
samples. No other distinct peaks of any impurities are observed in the assumption of that the un-neutralized spin order perpendicular to the
XPS spectrum, confirming the high purity of our films. spin cycloid of < 111 > direction generates a parasitic ferromagnetism.
The frequency dependence of the dielectric permittivity of the films On the other hand, enhancement in ferromagnetism may be related to
is displayed in Fig. 3a. Compared with the as-grown films, the annealed the distortion in the crystal symmetry of BF-BZT-ST films.
films show a rather lower dielectric loss with less than 0.05, which is Although our (110)-oriented BF-BZT-ST films show both a high
slightly higher than that of the ceramics, but much lower than that of electric polarization and high remanent magnetization, no direct po-
the pure BFO thin films. The lower dielectric loss is due to the stable larization change is observed by applying external direct magnetic field
thermodynamic equilibrium suppression of the secondary phases, bias (up to 1 T) and alternative magnetic field (~ 1 Oe from 1 kHz to
which can stabilize the desired perovskite phase. In addition, no ob- 5 kHz). This is contradictory to our aforementioned theoretical ex-
vious change is observed in the dielectric loss for the films with dif- pectation in the introduction part. The discrepancy is assumed to be
ferent thicknesses (not shown here). The lower dielectric loss guaran- offset by the inconsistent domains in our films. Due to the unclear
tees the regular measurements of the P-E loops. Fig. 3b presents the mechanisms in the ME coupling, these inconsistent domains may gen-
results of dielectric permittivity and dielectric loss depends on 1000/T erate polarity offset by each other and exhibit zero output in total. In
from 100 to 10,000 Hz with the temperature ranging from 160 K to further investigation, the epitaxial BF-BZT-ST films with a single-do-
330 K. Both of the curves show a remarkably increase when the tem- main structure will be pursued to verify our assumptions.
perature goes higher than the room temperature. It can be contributed
to the substrate-induced strain commonly existing in films [16]. How-
ever, we didn’t obtain the dielectric loss peaks which are usually as- 4. Conclusions
signed to the loss of Bi2O3 through volatilization and reaction [17].
Though further experiments may be needed to investigate the dielectric We have prepared highly (110)-oriented BF-BZT-ST thin films on
properties, this result partially demonstrates the stability of our films. conductive NSTO substrates by PLD technique. The BFO films show a
Fig. 4 gives the Arrhenius plot ln(σ) at 1 kHz. The electrical con- pure perovskite phase with R3c symmetry. The films demonstrate a low
ductivity of semiconductor materials is usually thermally activated over dielectric loss, which is due to the suppression of the impurity phases.
a limited temperature and follows the Arrhenius law, Our investigations provide a way to enhance the multiferroic properties
both in ferroelectricity and magnetism by preparing BFO films with
Ea
σ = σ0exp (− ) (110) orientation. However, no obvious ME coupling is found in our
kB T
films. The ME coupling effect may be enhanced by optimize the crys-
where σ0 is a pre-exponential factor determined by the properties of the tallization and domain structure of the films.
material. Ea, kB, and T are the activation energy for conduction,
Boltzmann constant, and absolute temperature, respectively. Ea can be
calculated from the slope of the straight line given by least-mean-square Acknowledgements
analysis of ln(σ) vs. 1000/T [18]. In the low temperature region, the
plot fits the Arrhenius law with Ea ~ 0.0111 eV which is greatly lower We would like to thank Yuanyuan Zhang (East China Normal
than the generally oxygen-vacancy contributed electron hopping [19]. University) for the magnetism measurement and the insightful discus-
In the high temperature region from 290 K to 330 K, the slope turns to sions. This work was partially supported by the Major State Basic
positive and no longer corresponds to the Arrhenius law. It indicates Research Development Program (Grant nos. 2016YFB0400801 and
that the electron hopping is not thermally activated or the conduction is 2016YFB0400104), Key Research Project of Frontier Sciences of
not dominated by electrons. Chinese Academy of Sciences (QYZDY-SSW-JSC042), National Natural
Fig. 5a shows the P-E loops for the films measured with the fre- Science Foundation of China (Grant nos. 61474131, 61574152 and
quency of 1 kHz at room temperature. It can be seen that both the 61674157). Natural Science Foundation of Shanghai (Grant no.
coercive filed (Ec) and the remanent polarization (Pr) increase with the 16ZR1447600).

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