ZnO as a buffer layer for growth of BiFeO 3 thin films

Jiagang Wu and John Wang

Citation: Journal of Applied Physics 108, 034102 (2010); doi: 10.1063/1.3460108

View online: http://dx.doi.org/10.1063/1.3460108
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 JOURNAL OF APPLIED PHYSICS 108, 034102 共2010兲

ZnO as a buffer layer for growth of BiFeO3 thin films

Jiagang Wua兲 and John Wangb兲
Department of Materials Science and Engineering, Faculty of Engineering, National University
of Singapore, Singapore 117574
共Received 30 March 2010; accepted 5 June 2010; published online 5 August 2010兲
Multiferroic BiFeO3 thin film was grown on the ZnO-buffered Pt/ TiO2 / SiO2 / Si共100兲 substrate by
off-axis radio frequency magnetron sputtering, where the ZnO buffer layer gave rise to a strong
共110兲 texture for the BiFeO3 thin film. The resulting BiFeO3 / ZnO thin film exhibits diode-like and
resistive hysteresis behavior, in which the resistive hysteresis and rectifying ratio are dependent on
the applied voltage and temperature. The resistive switching behavior of the BiFeO3 / ZnO thin film
is shown to relate to the trap-controlled space charge limited conduction and interface-limited
Fowler–Nordheim tunneling, while the polarization reversal takes place in the BiFeO3 layer of the
heterostructure. The BiFeO3 / ZnO thin film is also demonstrated with a higher remanent polarization
共2Pr ⬃ 153.6 ␮C / cm2兲, a much lower dielectric loss 共tan ␦ ⬃ 0.012兲, and a better fatigue endurance
as compared to those of the BiFeO3 thin film without a ZnO buffer layer, where the much reduced
leakage is largely responsible for the enhanced ferroelectric behavior. The ZnO as a buffer layer for
BiFeO3 significantly changes the dielectric relaxation and conduction mechanisms, when the
dielectric relaxation and electrical conduction are governed by the thermal excitation of carriers
from the second-ionization and short-range motion of oxygen vacancies, respectively, while the
relaxation process remains the same over the entire temperature range of 20 to 200 ° C investigated
in the present study. © 2010 American Institute of Physics. 关doi:10.1063/1.3460108兴

I. INTRODUCTION investigations into the current-voltage 共I-V兲 relationship and

Lead-free BiFeO3 共BFO兲, which exhibits a giant rema-
nent polarization, a room-temperature magnetization, and a
high Curie temperature 共Tc = 1103 K兲 in thin film form,1–6
promises as an excellent candidate material for high-density
ferroelectric random access memories and several other
technologically demanding applications.1–7 However, the
large leakage current observed at room temperature for
the BFO thin films hinder these potentially important
applications.1,3,4,6 Accordingly, several different attempts
have been made in order to reduce the leakage current of
BFO thin films, for example, by the employment of a single
crystal substrate,4,8,9 use of an appropriate buffer layer,4,6,10
construction of multilayer structures,11–15 and cation substi-
tutions for Bi and/or Fe in the BFO lattice.16–18 Indeed, sev-
eral types of buffer layers have also been shown effective in
promoting the growth of BFO and reducing the leakage
current.4,6,10,18–20
ZnO is an interesting semiconducting oxide that exhibits
a piezoelectric wurtzite-structure and thus an irreversible
spontaneous polarization, together with a wide spectral trans-
parency as well as the strongly excitonic, direct electronic
band to band transition.21 It would be, therefore, of consid-
erable interest to investigate the feasibility of using ZnO as a
buffer layer for the growth of the BFO thin film. Although
the combination of ferroelectric thin films and ZnO has been
demonstrated with interesting electrical behavior, the physi-
cal origin for the observed resistive hysteresis is still a sub-
ject of debate.22–24 Moreover, there have been few systematic
a兲
Electronic addresses: msewj@nus.edu.sg and wujiagang0208@163.com.
b兲
Electronic mail: msewangj@nus.edu.sg.
multiferroic behavior of the double layer structure consisting
of ZnO buffer layer and BFO thin films.24 The objectives of
the present work are to investigate the feasibility of con-
structing a double-layer structure consisting of multiferroic
BFO and semiconducting ZnO, and to study the resistive
hysteresis and electrical conduction behavior of such a bilay-
ered thin film, by conducting a systematic investigation into
the temperature and frequency dependences of the key pa-
rameters involved.
The BFO thin films with and without ZnO layer were
deposited by off-axis radio frequency 共rf兲 magnetron sputter-
ing on Pt共111兲 / TiO2 / SiO2 / Si共100兲 substrates, where the ef-
fects of the ZnO buffer layer on the film texture, ferroelec-
tric, leakage, and fatigue behavior of BFO thin films are
addressed. As detailed below, the ZnO buffer layer gives rise
to a strong 共110兲 film texture. A diode-like behavior and re-
sistive hysteresis loop are shown by the BFO/ZnO thin film,
while the ferroelectric and fatigue behavior are greatly im-
proved. The trap-controlled space charge limited conduction
and interface-limited Fowler–Nordheim 共FN兲 tunneling are
shown to be responsible for the resistive switching of BFO/
ZnO thin films, together with the polarization reversal in the
ferroelectric layer. The ZnO as a buffer layer for the growth
of the BFO thin film also significantly changes the dielectric
relaxation and conduction mechanisms, although the type of
relaxation process remains the same over the entire tempera-
ture range investigated in the present study.
II. EXPERIMENTAL
The BFO thin films with and without a ZnO buffer layer
were deposited by off-axis rf magnetron sputtering on

0021-8979/2010/108共3兲/034102/8/$30.00 108, 034102-1 © 2010 American Institute of Physics

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 034102-2 J. Wu and J. Wang
FIG. 1. 共Color online兲 共a兲 XRD patterns of BFO/ZnO and ZnO thin films, where the inset is the expanded XRD patterns of BFO/ZnO and ZnO thin films.
SEM micrographs showing 共b兲 cross section and 共c兲 surface morphologies of BFO/ZnO thin films. 共d兲 Dielectric behavior of BFO/ZnO and BFO thin films.
Pt共111兲 / TiO2 / SiO2 / Si共100兲 substrates. The preparation pro-
cedure for the Bi1.10FeO3 ceramic target has been described
elsewhere.12,15 The ZnO ceramic target was prepared by sin-
tering of ZnO powder. A buffer layer of ⬃80 nm ZnO in
thickness was grown in situ by off-axis rf magnetron sput-
tering on the Pt/ TiO2 / SiO2 / Si共100兲 substrate at the substrate
temperature of 620 ° C. The BFO thin film was then depos-
ited on the ZnO/ Pt/ TiO2 / SiO2 / Si共100兲 substrate at the sub-
strate temperature of 570 ° C. They were both deposited un-
der a rf power of 120 W, and at a base pressure of 5
⫻ 10−6 Torr and a deposition pressure of 10 mTorr with Ar
and O2 at a ratio of 4:1, giving rise to a growth rate of 3.0
nm/min and 2.5 nm/min for the BFO and ZnO layers, respec-
tively. The resultant thicknesses of BFO and ZnO layers
were measured to be ⬃300 nm and 80 nm, respectively.
Circular Au electrodes of 0.1 mm in diameter were sputtered
on the film surface by using a shadow mask in order to
investigate their electrical behavior.
The phases present in the BFO/ZnO thin film were ana-
lyzed by using x-ray diffraction 共XRD兲 共Bruker D8 Ad-
vanced XRD, Bruker AXS Inc., Madison, WI, Cu K␣兲. Field
emission scanning electron microscopy 共FE-SEM兲 共Philips,
XL30兲 was employed to study the cross section and surface
morphologies of thin films. Their ferroelectric and fatigue
behavior were studied by using the Radiant precise worksta-
tion 共Radiant Technologies, Medina, NY兲. An impedance
analyzer 共Solartron Grain Phase Analyzer兲 was used to char-
acterize the dielectric behavior of thin films. Their leakage
currents were measured by using a Keithley meter 共Keithley
6430, Cleveland, OH兲, where the voltage was swept as
−Vmax → +Vmax → −Vmax 共Vmax = 1, 2, 3, 4, and 5 V兲.
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J. Appl. Phys. 108, 034102 共2010兲
III. RESULTS AND DISCUSSION
Figure 1共a兲 shows the XRD patterns of the BFO/ZnO
thin film and ZnO buffer layer. The desired BFO and ZnO
phases were well retained in the BFO/ZnO thin film, as rep-
resented by the strong BFO 共110兲 and ZnO 共002兲 peaks 关inset
of Fig. 1共a兲兴, where no other secondary phases were detected.
The BFO thin film deposited on the Pt/ TiO2 / SiO2 / Si共100兲
substrate without a ZnO buffer layer exhibits a polycrystal-
line structure, often with one or more secondary phases.11,15
The bottom ZnO buffer layer had, therefore, improved the
phase purity of BFO and gave rise to a strong 共110兲 texture
for the BFO thin film deposited above. Figures 1共b兲 and 1共c兲
show the FE-SEM micrographs for the cross section and sur-
face morphology of the BFO/ZnO thin film. The BFO/ZnO
thin film appears to be dense and well adhered to Pt coated
silicon substrate. Figure 1共d兲 plots the dielectric behavior of
BFO/Pt and BFO/ZnO thin films in the frequency range of
101 Hz– 106 Hz. The dielectric loss of the BFO/ZnO thin
film is much lower than that of the BFO/Pt thin film, that is,
the dielectric loss measured for BFO/Pt and BFO/ZnO thin
films was 15.7% and 1.2% at 10 kHz, respectively. The
high dielectric loss measured for the BFO/Pt thin film
without a ZnO buffer layer is consistent with what has
been observed for the BFO thin film deposited on the
Pt/ TiO2 / SiO2 / Si共100兲 substrate.11,15 It is dramatically low-
ered when a ZnO layer buffer layer is inserted between the
substrate and BFO thin film, and the dense microstructure is
expected to contribute positively toward the dielectric behav-
ior.
Figure 2共a兲 shows the I-V relationship for the
BiFeO3 / ZnO thin film, which was measured at 300 K and
 034102-3 J. Wu and J. Wang
FIG. 2. 共Color online兲 共a兲 I-V curves of the BFO/ZnO thin film at varying
voltages. 共b兲 Rectifying ratio as a function of applied voltages. 共c兲 I-V
curves of the BFO/ZnO thin film with varying temperatures. 共d兲 Von of the
BFO/ZnO thin film with varying voltages and temperatures.
applied voltage range of 1–5 V. A diode-like behavior, char-
acterized by a strong asymmetry of I-V curve is demon-
strated. The leakage current asymmetry increases quickly
with the increase in applied voltages 关Fig. 2共b兲兴. The leakage
current increases by three orders of magnitude when the ap-
plied voltage is increased up to 5 V. It is well known that
charges carriers can be drained in the ZnO thin film under an
applied voltage. However, the overall electrical conductivity
of the BFO/ZnO thin film is not that high, attributed to the
highly resistive behavior of the BFO thin film. Electrons
move rather freely within the n-type ZnO layer in one direc-
tion and the electric potential drops quickly across the BFO
layer. In the other direction, however, electrons are drained
when crossing the ZnO layer, thereby building up a space-
charge region at the interface between BFO and ZnO. This is
also consistent with what is expected from the “work-
function” between the top 共Au兲 and bottom 共Pt兲 electrodes.25
A resistive hysteresis located at the positive direction is
clearly observed for the BFO/ZnO thin film and it becomes
more and more saturated with the increase in applied volt-
ages. The voltage at which the hysteresis occurs on the posi-
tive voltage side is defined as Von, the value of which de-
creases with the increase in applied voltages, as indicated in
Fig. 2共d兲. A resistive hysteresis under a dc applied field can
arise from the polarization reversal in the ferroelectric
layer.22,24,26,27 Indeed, a similar phenomenon has been ob-
served in ZnO/ BaTiO3.26 Fig. 2共c兲 shows the temperature
dependence of I-V curves for the BFO/ZnO thin film mea-
sured at 60 ° C, 110 ° C, and 150 ° C, respectively. The re-
sistive hysteresis located at the positive voltage side in the
I-V loop shows a strong temperature dependence, that is, the
resistive hysteresis becomes more and more saturated with
the increase in measurement temperature. Moreover, the Von
value decreases with the increase in measurement tempera-
ture, as shown in Fig. 2共d兲.
Although the diode-like behavior for the “ferroelectric-
semiconductor” heterostructure have been explained,22,26,27
their physical origins are still a subject of debate. In the past,
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J. Appl. Phys. 108, 034102 共2010兲
FIG. 3. 共Color online兲 I-V relationship of the Au/BFO/ZnO/Pt thin film
structure. Data fittings are used to identify the dominating leakage process:
共a兲 SCLC, 共b兲 Schottky barriers, 共c兲 PF emission, and 共d兲 FN tunneling.
the resistive hysteresis was accounted for by the polarization
reversal in the ferroelectric layer.22,24,25,27 Although the po-
larization reversal may well be involved in the BFO/ZnO
thin film, the resistive hysteresis is also closely associated
with the leakage, where one or more of the conduction pro-
cesses such as the space-charge-limited conduction 共SCLC兲,
interface-limited Schottky emission, bulk limited Poole–
Frenkel 共PF兲 emission, and interface-limited FN tunneling
may well be involved. These conduction processes can be
described by the following equations:28–31
9 ␮ ␧ 0␧ r 2
JSCLC = E , 共1兲
8d
쏗− 冑q3E/␲␧0K
JS = AT2e− , 共2兲
K BT
EI − 冑q3E/␲␧0K
JPF = BEe− , 共3兲
K BT
D冑␸3i
2
JFN = CE2e− , 共4兲
E
where ␧r is the relative dielectric constant, ␧0 is the permit-
tivity of free space, ␮ is the charge carrier mobility, d is the
film thickness, K is the optical dielectric permittivity, and A,
B, and C are constants; 쏗, EI, and ␸i are the height of
Schottky barrier, trap ionization energy, and potential barrier
height, respectively. In order to identify the actual dominat-
ing leakage process involved in the BFO/ZnO thin film, the
measured data can be fitted as a function of electric fields
according to Eqs. 共1兲–共4兲, where the 0 → Vmax is defined as
the positive direction and Vmax → 0 as the negative direction.
The leakage plotted as J versus E2 according to Eq. 共1兲 is
shown in Fig. 3共a兲, where a linear fitting would suggest
SCLC as the dominant leakage process. Indeed, a more or
less linear fit in both the positive and negative directions was
observed at the low electric fields, and thus, the SCLC is
largely responsible for the leakage behavior of the BFO/ZnO
thin film at low electric fields. To further determine whether
the Schottky barriers, PF emissions, or interface-limited FN
 034102-4 J. Wu and J. Wang
FIG. 4. 共Color online兲 I-V relationship of the Au/BFO/ZnO/Pt thin film in
the positive direction, in accordance with SCLC under varying voltages. 共a兲
1 V, 共b兲 2 V, 共c兲 3 V, 共d兲 4 V, and 共e兲 5 V; 共f兲 ln共J / E2兲 vs 共1 / E兲 in the positive
direction and voltages of 1–5 V.
tunneling are largely involved, similar analyses were con-
ducted according to of Eqs. 共2兲–共4兲. For a linear fitting of
Eqs. 共2兲 and 共3兲, an appropriate K value is necessary in order
to extract the optical dielectric permittivity of BFO from the
slopes of these plots. The refraction index for BFO is about
n ⬃ 2.5, and thus, an optical dielectric permittivity of K = n2
⬃ 6.25 can be reasonably assumed.32 From the Schottky and
PF plots in Figs. 3共b兲 and 3共c兲, the K value is greatly devi-
ated from K ⬃ 6.25 for BFO, indicating the very unlikely
involvement of Schottky barriers and PF emissions. Al-
though PF emission has been shown to dominate the leakage
for single layer BFO thin film,33,34 the conduction behavior
of the BFO/ZnO thin film is strongly dependent on the ZnO
buffer layer. As discussed above, the leakage at low electric
fields could be well described by Eqs. 共1兲–共3兲. However, at
high electric fields, it cannot be accounted for by any of the
SCLC, Schottky, and PF emission. On the other hand, the
interface-limited FN tunneling is known to make substantial
contribution toward the leakage current at high electric
fields.31 Figure 3共d兲 shows the plot of ln共J / E2兲 as a function
of 1 / E for the BFO/ZnO thin film in the positive and nega-
tive directions. It appears to be a straight line in the high
electric field region according to Eq. 共4兲, suggesting that the
interface-limited FN tunneling is a dominating process at
high electric fields.
To further understand the resistive switching behavior,
the conduction of the BFO/ZnO thin film was investigated as
a function of applied voltages 共1–5 V兲. Figures 4共a兲–4共e兲
show log共J兲 versus log共E兲 curves in the positive direction at
different voltages. They are of the similar gradients regard-
less of different voltages. The slope varies from ⬃1 to 2, and
then increases with further increasing electric fields. The
electrical current is linearly dependent on voltage, J⬁E
共Ohm’s law兲, and then on the square of voltage, J⬁E2
共Child’s law兲. The conduction behavior is thus consistent
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FIG. 5. 共Color online兲 I-V relationship of the Au/BFO/ZnO/Pt thin film in
the negative direction, in accordance with SCLC under varying voltages. 共a兲
1 V, 共b兲 2 V, 共c兲 3 V, 共d兲 4 V, and 共e兲 5 V; 共f兲 ln共J / E2兲 vs 共1 / E兲 in the
negative direction and the voltages of 1–5 V.
with SCLC at low electric fields. The fits for different volt-
ages were plotted in Fig. 4共f兲, in accordance with the
interface-limited FN tunneling of Eq. 共4兲, confirming that it
is largely responsible for the leakage behavior at high elec-
tric fields. Similar analyses were repeated for the BFO/ZnO
thin film in the negative direction, as shown in Figs.
5共a兲–5共f兲, which also confirmed the similar leakage behavior
as in the positive direction. These observations demonstrate
that the trap-controlled SCLC and interface-limited FN tun-
neling are involved in the resistive switching behavior of the
BFO/ZnO thin film.
The resistive hysteresis of the BFO/ZnO thin film shows
strong temperature dependence, as demonstrated in Fig. 2共c兲.
There however remains the question whether the leakage
process changes with temperature. To answer this question,
leakages in both positive and negative directions were inves-
tigated as a function of temperature, at the same applied
voltage of 3 V, as plotted in Figs. 6共a兲–6共d兲 and 7共a兲–7共d兲. In
the positive direction, it exhibits a SCLC behavior at low
electric fields, and an interface-limited FN tunneling at high
electric fields. Similar analyses were also conducted for the
BFO/ZnO thin film in the negative direction, again showing
the involvement of the same processes. The dominating leak-
age process is however unchanged over the temperature
range investigated.
Figure 8共a兲 shows the polarization behavior 共P-E兲 of the
BFO/ZnO thin film, which was measured at 2 kHz and 300
K. It exhibits much improved ferroelectric behavior than that
of the BFO/Pt thin film without a ZnO buffer layer,11,15
where the ZnO buffer layer dramatically reduces the involve-
ment of space charges. Indeed, the BFO/Pt thin film without
a ZnO buffer layer exhibits a roundish shape of the P-E
loop.11,15 The much enhanced polarization measured for the
BFO/ZnO thin film is attributed to strong 共110兲 film texture
 034102-5 J. Wu and J. Wang
FIG. 6. 共Color online兲 I-V relationship of the Au/BFO/ZnO/Pt thin film in
the positive direction, in accordance with SCLC under varying temperatures.
共a兲 60 ° C, 共b兲 110 ° C, 共c兲 150 ° C; 共d兲 ln共J / E2兲 vs 共1 / E兲 in the positive
direction and temperatures of 20, 60, 110, and 150 ° C.
and the much reduced leakage current.8 In order to accu-
rately measure the switchable polarization, which shall
largely exclude the contributions from leakage and space
charges, the pulsed polarization positive up negative down
共PUND兲 measurement was conducted at a pulse width of 0.5
ms. The remanent polarization value measured for PUND
关Fig. 8共b兲兴 is slightly lower as compared to that measured by
P-E hysteresis loop 关Fig. 8共a兲兴, suggesting that the leakage
and the space charge at the interface between BFO and ZnO
had made limited contribution toward the overall polariza-
tion. Magnetic behavior of BFO/ZnO and BFO/Pt thin films
measured at 300 K and room temperature is shown in Fig.
8共c兲, where a saturated magnetic hysteresis loop is achieved
with M s ⬃ 5.0 emu/ cm3 for the BFO/ZnO thin film. This
indicates that the spin structure of the top BFO layer was
largely unaffected by the bottom ZnO buffer layer in the
BFO/ZnO thin film. Figure 8共d兲 shows the fatigue behavior
as a function of switching cycles for the BFO/ZnO and
BFO/Pt thin films measured under a fixed electric field of
⬃350 kV/ cm and room temperature. The fatigue endurance
of the BFO/ZnO thin film is dependent on frequency, i.e., the
FIG. 7. 共Color online兲 I-V relationship of the Au/BFO/ZnO/Pt thin film in
the negative direction, in accordance with SCLC under varying tempera-
tures. 共a兲 60 ° C, 共b兲 110 ° C, 共c兲 150 ° C; 共d兲 ln共J / E2兲 vs 共1 / E兲 in the
negative direction and temperatures of 20, 60, 110, and 150 ° C.
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J. Appl. Phys. 108, 034102 共2010兲
FIG. 8. 共Color online兲 共a兲 P-E loops and 共b兲 PUND measurement of the
BFO/ZnO thin film. 共c兲 M-H curve of BFO/ZnO and BFO/Pt thin films. 共d兲
Fatigue endurance of bilayered BFO/ZnO and BFO/Pt thin films as a func-
tion of frequencies.
fatigue endurance is deteriorated when the frequency is de-
creased from high frequency 共1 MHz兲 to low frequency 共1
kHz兲. At high frequencies 共e.g., at 1.0 MHz兲, it is almost
fatigue-free upon 6 ⫻ 109 switching cycles, which is in
agreement with a previous report on the BFO multilayers
with SrRuO3 electrodes.12 However, a fatigue degradation
occurred at lower frequencies, i.e., there is an apparent de-
crease in fatigue endurance upon 5.5⫻ 107 switching cycles
at 50 kHz, while the polarization was lowered by about 50%
from the initial value at 1 kHz. At high frequencies of 1.0
MHz, oxygen vacancies and deep traps in the BFO thin film
respond slowly to the applied voltages, and the compensation
of polarization charges is made mainly with free carriers
from the top and bottom electrodes.35 As a result, the polar-
ization will not change too much during the fatigue test.
However, at low frequencies 共e.g., 1.0 kHz兲, oxygen vacan-
cies can easily migrate and the trapped charges respond
steadily to the applied voltage. The rearrangement of oxygen
vacancies hinders the switching of ferroelectric domain and
thus results in a decrease in the polarization.36 Metal elec-
trodes, such as Pt electrode, also affects the fatigue endur-
ance by forming a “dead layer,” where a “dead layer” be-
tween thin films and electrode dramatically degraded
ferroelectric properties of ferroelectric thin films.37 The top
and bottom electrode 共Pt兲 used in the present work may also
contribute to the measured fatigue endurance.
Although the fatigue endurance decreases with the de-
creasing frequencies, the fatigue endurance of the BFO/ZnO
thin film is much improved as compared to that of the
BFO/Pt thin film with a ZnO buffer layer. The improved
fatigue endurance of the BFO/ZnO thin film is attributed to
the improvement in the film texture arising from ZnO as
buffer layer, where the dead layer effect will be suppressed.37
The ZnO buffer layer can also effectively act as a barrier
layer blocking the migration of oxygen vacancies between
BFO and Pt, and thus, minimizing the charge injection from
the bottom electrode to BFO layer.38 A decrease in the in-
volvement of oxygen vacancies for the BFO thin film help
 034102-6 J. Wu and J. Wang
FIG. 9. 共Color online兲 ac conductivity plotted for 共a兲 BFO/Pt and 共b兲 BFO/
ZnO thin films as a function of frequencies at varying temperatures in the
range of 20– 200 ° C, where the insets in 共a兲 and 共b兲 are plots for permittiv-
ity vs frequency as a function of temperature of BFO and BFO/ZnO thin
films, respectively. Frequency dependence of imaginary part 共Z⬙ / Zmax ⬙ 兲 of
the impedance for 共c兲 BFO and 共d兲 BFO/ZnO thin films.
improve the fatigue endurance by limiting the defect migra-
tion and related domain wall pinning effects.36
To further understand the effect of ZnO buffer layer on
the electrical conduction and dielectric relaxation, the com-
plex impedance spectroscopy is employed to identify the dif-
ference in the conduction and relaxation behavior between
the BFO/ZnO and BFO/Pt thin film without a ZnO buffer
layer. Figures 9共a兲 and 9共b兲 show the ac conductivity plotted
as a function of frequencies at varying temperatures 共in the
range of 20 to 200 ° C兲 for the BFO/Pt and BFO/ZnO thin
films, respectively. The frequency dependence of conductiv-
ity can be described by the power-law relationship proposed
by Jonscher39
␴共␻兲 = ␴共0兲 + A␻s , 共5兲
where ␴共␻兲 is the total conductivity, ␴共0兲 is the frequency-
independent dc conductivity, ␻ is angular frequency, and co-
efficient A and exponent s are the temperature and material
dependent parameters 共0 ⬍ s ⬍ 1兲. The plots for both BFO/Pt
and BFO/ZnO thin films tend to become more flattened in
the low frequency region with rising temperature and the
flattened region becomes wider and is shifted toward higher
frequencies, indicating that ␴ac then becomes almost
frequency-independent. The frequency-independent plateau-
like region observed in the low frequency region is attributed
to the frequency-independent conductivity 关␴共0兲兴 in Eq. 共5兲.
With an increase in frequencies, a frequency-dependent con-
ductivity 关␴共␻兲 ⬃ A␻s兴 region is observed. It is of interest to
note that BFO/ZnO possesses a narrower dc conduction re-
gion and much lower conduction 共above three orders兲 as
compared to those of the BFO/Pt thin film without a ZnO
buffer layer at the same condition, indicating that ZnO buffer
layer greatly improves the resistance of BFO thin films. Ow-
ing to the enhanced mobility of oxygen vacancies and or
other structural defects, conductivities of both films increase
with the increase in temperature, and the flattened region
shifts upwards and dominates over a larger range of
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J. Appl. Phys. 108, 034102 共2010兲
FIG. 10. 共Color online兲 Inverse of the peak frequency 共relaxations time ␶兲 as
a function of temperature for 共a兲 BFO/Pt and 共b兲 BFO/ZnO thin films; dc
conductivity vs 1 / T plots at different frequencies for 共c兲 BFO/Pt and 共d兲
bilayered BFO/ZnO thin films.
frequencies.40 Moreover, the permittivities of BFO/Pt and
BFO/ZnO thin films increase with rising temperature, as
shown in the insets of Figs. 9共a兲 and 9共b兲. Figures 9共c兲 and
9共d兲 plot the frequency dependence of imaginary part
⬙ 兲 of the impedance for BFO/Pt without a ZnO
共Z⬙ / Zmax
buffer layer and BFO/ZnO as a function of frequencies at
different temperatures. Only a single Debye-like peak with
the characteristic frequency maxima 共f max兲 was observed for
both BFO/Pt and BFO/ZnO in the range of temperatures and
frequencies investigated. The peak position of relaxation fre-
quencies due to the grain effect is gradually shifted toward
higher frequencies with increasing temperature, indicating
the relaxation rate for this process increases with tempera-
ture. The grain boundary peaks are not observed in the fre-
quency window and temperature range studied for the
BFO/Pt and BFO/ZnO thin films.
Figures 10共a兲 and 10共b兲 plot the inverse of the peak fre-
quency 共relaxations time ␶兲 as a function of temperature for
the BFO/Pt without a ZnO buffer layer and bilayered BFO/
ZnO thin film, where the linear relationship confirms the
Debye-like behavior.41 The relaxation time is observed to
decrease with the increase in temperature. The activation en-
ergy for the dielectric relaxation can be calculated according
to the Arrhenius equation
␶ = ␶o exp共ER/kBT兲, 共6兲
where ␶o is the relaxation time at infinite temperature, ER is
the activation energy of dielectric relaxation, kB is the Bolt-
zmann constant, and T is the absolute temperature. The BFO
thin films have been demonstrated with different activation
energies, depending on temperature. In contrast, the activa-
tion energy for the BFO/ZnO thin film is almost unchanged
regardless of the change in temperature, indicating the in-
volvement of the same relaxation process at different tem-
peratures. Moreover, the activation energy value is distinctly
different between the BFO/Pt without a ZnO buffer layer and
BFO/ZnO thin film, where the activation energy for the di-
electric relaxation is 0.33 eV and 0.56 eV at low and high
temperatures, respectively, for BFO/Pt without a ZnO buffer
 034102-7 J. Wu and J. Wang J. Appl. Phys. 108, 034102 共2010兲

layer. An activation energy value of 0.98 eV is calculated for

the BFO/ZnO thin film regardless of temperature. In oxide-
based ferroelectric thin films, oxygen vacancies 共VO ••
兲 are the
very likely mobile charges, which often play an important
role in the dielectric relaxation.42 The above calculated val-
ues of activation energy suggest the involvement of oxygen
vacancies at high temperatures, where the first-ionization of
oxygen vacancies is responsible for the dielectric relaxation
of BFO/Pt without a ZnO buffer layer. In contrast, the acti-
vation energy value calculated for the dielectric relaxation in
BFO/ZnO is rather different, suggesting the involvement of
••
short-range motion of the VO , as shown in Fig. 10共b兲. There-
fore, the ZnO as buffer layer in the ZnO/BFO thin film had
significantly changed the dielectric relaxation process. Fig-
ures 10共c兲 and 10共d兲 plot the dc conductivity versus 1000/ T
at different frequencies. The temperature dependence of dc
conductivity can be described by the Arrhenius equation 关Eq.
共7兲兴
␴dc = ␴dco exp共− Ea/kBT兲, 共7兲

where ␴o and kB are constant and Ea is the electrical activa-
tion energy of conduction, which can be calculated over dif-
ferent frequencies from the linear slopes in Figs. 10共c兲 and
10共d兲. Different conduction processes are expected in the
two films at different temperatures. The calculated activation
energy for the BFO/Pt thin film at low and high temperatures
was 0.32 eV and 0.42 eV, respectively, indicating that the
first-ionization of oxygen vacancies is responsible for the
conduction. For the BFO/ZnO thin film, it can be fitted with
one single linear relationship over the entire temperature re-
gion investigated. Therefore, the conduction is dominated by
the same process, regardless of the variation in temperatures.
The activation energy of conduction calculated for the
BFO/Pt thin film is 0.78 eV, indicating that its electrical con-
duction is largely governed by the thermal excitation of car-
riers from the second-ionization of oxygen vacancies.42 The
calculated value of ER is close to Ea value for the BFO/Pt
thin film, confirming that the same type of charge carriers is
responsible for both dielectric relaxation and conduction. In
contrast, the BFO/ZnO thin film exhibits notably different ER
and Ea values. To further show the scaling behavior of the
two films with and without a ZnO buffer layer, the imaginary
part of impedance was scaled. Figures 11共a兲 and 11共b兲 plot
the scaling behavior of the imaginary part 共Z⬙兲 for the
BFO/Pt and BFO/ZnO thin films at different temperatures,
where Zmax⬙ and f max are employed as the scaling parameters
for Z⬙ and f, respectively.43 Although temperature affects the
activation energy value 共ER兲 of the BFO/Pt thin film, the
dielectric relaxation and electrical conduction appear to be
the same type of charge carriers, as shown in the scaling of
imaginary part 共Z⬙兲 in Fig. 11共a兲. The very similar spectra in
Fig. 11共b兲 shows that the relaxation dynamics, which vary
little with temperature, do not change much for BFO/ZnO. In
order to further identify the difference in relaxation between
two thin films, Figs. 11共c兲 and 11共d兲 show the frequency
dependence of normalized peaks 共Z⬙ / Zmax⬙ and M⬙ / Mmax ⬙ 兲 for
the BFO/Pt without a ZnO buffer layer and BFO/ZnO thin
films, respectively. The peak positions for Z⬙ / Zmax ⬙ and
⬙ of the BFO/Pt thin film are almost overlapped,
M⬙ / Mmax
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129.8.242.67 On: Sat, 11 Jul 2015 00:31:18
FIG. 11. 共Color online兲 Scaling behavior of the imaginary part for 共a兲
BFO/Pt and 共b兲 BFO/ZnO thin films, as a function of temperature. Fre-
⬙ and M⬙ / Mmax
quency dependence of the normalized peaks 共Z⬙ / Zmax ⬙ 兲 of 共c兲
BFO/Pt and 共d兲 BFO/ZnO thin films. 共e兲 Comparable scaling behavior of the
imaginary part for BFO/Pt and BFO/ZnO thin films at 160 ° C.
⬙
indicating a long range relaxation.44 In contrast, the Z⬙ / Zmax
⬙ peaks of the BFO/ZnO thin film do not over-
and M⬙ / Mmax
lap, suggesting a localized relaxation.44 Figure 11共e兲 shows
the scaling behavior of imaginary part 共Z⬙兲 for the BFO/Pt
without a ZnO buffer layer and BFO/ZnO thin films at a
fixed temperature of 160 ° C. Apparently, they possess rather
different spectra, confirming the different types of dielectric
relaxation.
IV. CONCLUSIONS
The ZnO as a buffer layer promoted the growth of 共110兲
film texture for the BiFeO3 thin film deposited on the
Pt/ TiO2 / SiO2 / Si共100兲 substrate by off-axis rf magnetron
sputtering. The BiFeO3 / ZnO thin film exhibits a much low-
ered dielectric loss 共tan ␦ ⬃ 0.012兲 than that of the film with-
out a ZnO buffer layer. Due to the much reduced leakage
current, the bilayered thin film demonstrates a well estab-
lished P-E hysteresis loop, characterized by 2Pr
⬃ 153.6 ␮C / cm2 and 2Ec ⬃ 857.2 kV/ cm. The fatigue en-
durance of the BFO/ZnO thin film is strongly dependent on
measurement frequencies. A diode-like behavior and resis-
tive hysteresis are observed for the BFO/ZnO thin film,
where the rectifying ratio increases with the increase in ap-
plied voltages. The voltage at which the hysteresis occurs on
the positive voltage side decreases with increasing voltage
and temperature. The resistive switching behavior of the be-
layed BFO/ZnO thin film is shown to closely associate with
the trap-controlled space charge limited current and
interface-limited FN tunneling. ZnO had significantly
changed the dielectric relaxation and electrical condition,
where the dielectric relaxation and electrical conduction are
 034102-8 J. Wu and J. Wang J. Appl. Phys. 108, 034102 共2010兲

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