Research Article

Cite This: ACS Appl. Mater. Interfaces 2019, 11, 23372−23381 www.acsami.org

Manipulation of Oxygen Vacancy for High Photovoltaic Output in

Bismuth Ferrite Films
Tiantian Yang,† Jie Wei,*,† Yaxin Guo,† Zhibin Lv,† Zhuo Xu,† and Zhenxiang Cheng‡
†
Electronic Materials Research Laboratory, Key Laboratory of Ministry of Education & International Center for Dielectric Research,
School of Electronic and Information Engineering, Xi’an Jiaotong University, Xi’an 710049, P.R. China
‡
Institute for Superconducting and Electronic Materials (ISEM), University of Wollongong, Innovation Campus, Squires Way,
North Wollongong, NSW 2500, Australia
*
S Supporting Information
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ABSTRACT: Very recently, the ferroelectric photovoltaic property of

Downloaded via UNIV OF SOUTHERN INDIANA on July 18, 2019 at 22:15:49 (UTC).

bismuth ferrite (BiFeO3, BFO) has attracted much attention. However, the
physical mechanisms for its anomalous photovoltaic effect and switchable
photovoltaic effect are still largely unclear. Herein, a novel design was
proposed to realize a high photovoltaic output in BiFeO3 films by
manipulating its oxygen vacancy concentration through the alteration of
the Bi content. Subsequent results and analysis manifested that the highest
photovoltaic output was achieved in Bi1.05FeO3 films, differing 1000 times
from that of Bi0.95FeO3 films. Simultaneously, the origin of photovoltaic
effect in all BiFeO3 films was suggested as the bulk photovoltaic mechanism instead of the Schottky effect. Moreover, oxygen
vacancy migration should be the dominant factor determining the switchable photovoltaic effect rather than the ferroelectric
polarization. A switchable Schottky-to-Ohmic interfacial contact model was proposed to illustrate the observed switchable
photovoltaic or diodelike effect. Therefore, the present work may open a new way to realize the high power output and
controllable photovoltaic switching behavior for the photovoltaic applications of BiFeO3 compounds.
KEYWORDS: bismuth ferrite film, ferroelectric, photovoltaic, oxygen vacancy, diodelike effect

1. INTRODUCTION ferroelectric polarization. Yang et al.2 prepared a specific BFO

Bismuth ferrite (BiFeO3, BFO), as a prototype multiferroic
material, has attracted much attention because of its high
ferroelectric Curie temperature (TC ∼ 1100 K) and Neel
temperature (TN ∼ 650 K), making it have broad application
prospects in optoelectronic devices, spintronic devices, ferro-
electric memory, magnetic storage, and other fields.1−7 More
recently, the ferroelectric photovoltaic effect in BFO systems is
of particular interest mostly due to its large polarization (∼90
μC/cm2), relatively low band gap (Eg = 2.2−2.8 eV), and large
light absorption coefficient,1,2,6−10 which make it able to
absorb more photons in the visible range unlike the
conventional ferroelectric materials such as BaTiO3, LiNbO3,
or Pb(Zr, Ti)O3.11−15
Especially, an extremely large open-circuit voltage (VOC)
exceeding several times its band gap (anomalous photovoltaic
effect) and a unique polarization-dependent switchable
behavior of photocurrent (switchable photovoltaic effect)
have been successively reported in BFO films and crys-
tals,1,2,6−10,16,17 which make BFO attractive for application in
optoelectronic or photovoltaic devices. Thereafter, several
studies have shown that polarization,18−21 domain wall,2,22 and
oxygen vacancies20,22−24 were the main factors affecting the
ferroelectric photovoltaic effect. Yi et al.20 studied the
mechanism of photovoltaic effect generated in BFO films,
indicating that photovoltaic effect originates from ferroelectric
polarization, and the direction of photocurrent is opposite to
film with all domain walls parallelly aligned at 71°, whereas the
experiments showed that the open-circuit photovoltage (VOC)
in BFO is not determined by the width of band gap but is
related to the particular interface of domain walls. Gao et
al.24,25 changed the distribution of oxygen vacancies by
applying the pulse to the heterojunction to study the short-
circuit photocurrent under different oxygen vacancy distribu-
tions.
Although the ferroelectric photovoltaic effect or property of
BFO has been studied for years, the physical mechanisms for
the anomalous photovoltaic effect and switchable photovoltaic
effect in BFO are still largely unclear. For example, the origin
of the anomalous photovoltaic effect observed in BFO epitaxial
thin films was first attributed to domain walls, in which
electrons and holes could be efficiently separated by the
internal electric field.2,26 However, subsequent studies
suggested that the bulk photovoltaic effect (BPV) arising
from the noncentrosymmetric nature of ferroelectric materials
might be the actual mechanism for the anomalous photovoltaic
effect.27−30 Alexe et al.17 demonstrated via temperature
photovoltaic measurements that BPV should indeed be the
origin of the anomalous photovoltaic effect in BFO films. For
Received: April 17, 2019
Accepted: June 5, 2019
Published: June 5, 2019

© 2019 American Chemical Society 23372 DOI: 10.1021/acsami.9b06704

ACS Appl. Mater. Interfaces 2019, 11, 23372−23381
ACS Applied Materials & Interfaces
the BFO films with periodic ferroelectric stripe domain
patterns,26 high VOC values might be and could only be
observed in the specific geometry with the domain walls
running parallel to the collecting electrodes. On the contrary,
VOC value beyond the band gap could not be observed at the
polycrystalline BFO films at all, in which the ferroelectric
photovoltaic effect was generally attributed to the Schottky
barrier formed in the interface between the metal and the
semiconductor.31,32 On the other hand, Choi et al.1 observed
the switchable photovoltaic effect in a BFO single crystal,
displaying that the photocurrent could be reversibly switchable
by applying an external electric field. Later studies displayed
that BFO thin films exhibited or did not exhibit the switchable
photovoltaic behavior depending on the quality of the films or
even the synthesis process. Concerning the physical mecha-
nism for this switchable photovoltaic effect, there is also no
unified conclusion. Initially, ferroelectric polarization was
considered to be the dominant factor controlling the
switchable photovoltaic behavior.20 However, more and more
evidence revealed that the electromigration of chemical defects
such as oxygen vacancies might play a key role in the
switchable photovoltaic effect.23
Moreover, the photocurrent density (short-circuit current
density, JSC) of BFO observed in bulk crystals or thin films is
very small, usually several μA/cm2 below the magnitude of
mA/cm2 for general silicon-based solar cells.18,29,32 It makes
the power conversion efficiency of BFO-based photovoltaic
devices very poor, usually less than 1%, severely hampering
future applications in ferroelectric photovoltaics or photo-
electronics.14,33 Thanks to the fruitful investigations on the
physical properties of BFO compounds in the past, oxygen
vacancy is believed to play a key role on leakage and
ferroelectric properties of BFO, which in turn should have
great impacts on its photovoltaic properties.23,34,35
On the basis of the above analysis and discussion, we
proposed a novel design to realize high photovoltaic output in
bismuth ferrite films. In this framework, manipulation of
oxygen vacancy by adjusting the content of Bi in the BFO film
capacitor finally achieved more than 1000 times improvement
on its photovoltaic output (VOC × JSC). Meanwhile, in our
case, all Au/BixFeO3/FTO (x = 0.95, 1, and 1.05) film
capacitors have the same geometric electrode structure and
thereby almost the same Schottky barrier, whereas their
ferroelectric photovoltaic performances are quite different
because of the different oxygen vacancy concentration in these
films. It revealed that the origin of photovoltaic effect in all
BixFeO3 (x = 0.95, 1, and 1.05) films should be the bulk
photovoltaic effect. Similarly, oxygen vacancy concentration
worked on the switchable photovoltaic effect since this effect
could be observed in the Bi0.95FeO3 and BiFeO3 films and not
in the Bi1.05FeO3 film. Based on these observations, a
switchable Schottky-to-Ohmic interfacial contact model was
proposed to illustrate the switchable photovoltaic or diodelike
effect in our samples. In our case, oxygen vacancy migration
should be the dominant factor determining the switchable
photovoltaic effect, rather than the ferroelectric polarization.
2. EXPERIMENTAL SECTION
BixFeO3 (x = 0.95, 1, and 1.05, corresponding to Bi0.95FeO3, BiFeO3,
and Bi1.05FeO3) films were deposited on the F-doped SnO2 (FTO)/
glass substrate using a chemical solution deposition process. In a
typical run, bismuth nitrate (Bi(NO3)3·5H2O) and iron nitrate
(Fe(NO3)3·9H2O) were mixed and stirred in acetic acid for 30 min at
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Research Article
room temperature. Then, 2-methoxyethanol was added and stirred for
another 3 h to form the precursor solution. The depositions were
carried out by the spin-coating technique at 600 rpm for 9 s and then
at 4000 rpm for an additional 30 s. The wet film was preannealed at
200 °C for 2 min and then annealed at 550 °C for 5 min in air. The
above process was repeated several times to obtain the desired
thickness. Finally, the sample was annealed at 550 °C for 30 min to
obtain a denser film.
The phase purity and crystalline structure of the films were
investigated by X-ray diffraction (XRD, X’pert PRO) and laser Raman
spectroscopy (HR800). The surface morphologies of the films were
observed with a scanning electron microscope (SEM, Quanta F250).
Ion valences were determined by X-ray photoelectron spectroscopy
(XPS, Thermo Fisher ESCALAB Xi+). The surface element contents
of as-prepared films were also measured and analyzed by XPS after
cleaning and etching the films by a 3 keV Ar-ions gun (etch time: 1
min; etch current: 2.73 μA; spot size: 3.25 mm; source gun type: Al
Kα). The leakage current characteristics of the films (J−E) were
characterized by the Keithley 4200-SCS meter. The photovoltaic
effect was evaluated illuminating the film between the electrodes by a
405 nm laser (hv = 3.06 eV) with a maximum power density of 50
mW/cm2. Simultaneously, the current−voltage curves were recorded
by a precise source/measure unit (Keysight B2901a). The absorption
spectrum was investigated by UV−visible spectroscopy.
3. RESULTS AND DISCUSSION
3.1. Crystalline Structure. The phase purity and
crystalline structure of BixFeO3 (x = 0.95, 1, and 1.05) films
were measured by X-ray diffraction (XRD), as shown in Figure
1. XRD patterns show that all detectable diffraction peaks of
Figure 1. XRD patterns of BixFeO3 (x = 0.95, 1, and 1.05) films.
the films can be easily indexed into a rhombohedral distorted
perovskite structure with a space group of R3c (PDF#86-
1518), indicating a single phase structure without any
secondary phase. Meanwhile, the sharpness of the main
peaks indicates a highly crystallized quality of all films. It
notes that the change in Bi content did not alter the crystalline
structure of BiFeO3, simultaneously confirmed by the
observation from the Raman spectra as shown in Figure S1.
Surface morphology SEM images and cross-section structure of
BixFeO3 (x = 0.95, 1, and 1.05) films are shown in Figure S2,
and the thickness of the BiFeO3 film is about 500 nm. The
other films have almost the same thickness because of the
deposition in the same condition. Details on film growth,
morphology, and structure are given in Figures S1−S3 of the
Supporting Information.
3.2. Leakage Properties. Figure 2 shows the leakage
current density (J) as a function of electric field (E) of BixFeO3
(x = 0.95, 1, and 1.05) films measured at room temperature.
Leakage current densities of all of the films increase markedly
with the increase of electric field. The leakage current density
of the Bi0.95FeO3 film is 2 orders of magnitude higher than that
of the Bi1.05FeO3 film. Evidently, Bi content has a great impact
on the leakage properties of BFO films, which should be
DOI: 10.1021/acsami.9b06704
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ACS Applied Materials & Interfaces Research Article

and the semiconductor that charges must overcome. The

ÄÅ É
1/2 Ñ
ÅÅ ÑÑ
current density across the barrier is

Å i y
J = AT 2 exp −ÅÅÅÅ
j
jj zz ÑÑÑÑ
z
j z
ÅÅ kBT kBT jk 4πε0εrL z{ ÑÑÑÑ
3
Φ 1 q V

ÅÅÇ ÑÖ
−
(2)

where A is the Richardson constant and Φ is the height of the

Figure 2. Leakage current density of BixFeO3 (x = 0.95, 1, and 1.05)
films measured at a varied direct-current electric field from −200 to
200 kV/cm at room temperature.
Schottky barrier.
PF emission, being similar to Schottky emission, involves a
process of charge carrier transmission, in which charge carriers
trapped in defect centers emit into the conduction band under
an applied electric field and thereby contribute to the
conduction process. PF emission is hence called the “internal
Schottky emission”. The current density due to the bulk

ÅÄÅ ÑÉ
limited PF emission is given by36,38

ÅÅ −(φt − e eE /πεrε0 ) ÑÑÑ

primarily attributed to the change in the oxygen vacancy.23,36

As requirement of the charge balance in BFO, Bi vacancies lead
to an increase in the oxygen vacancy concentration, whereas
excessive Bi should be bound to a decrease in the oxygen
vacancy concentration. Combined with the SEM analysis (as
shown in Figure S2), one can deduce that excessive Bi leads to
a smoother surface, larger grain size, less grain boundaries, and
lower oxygen vacancy concentration, which should be the main
reason for the lower leakage current density at the high electric
field region in the Bi1.05FeO3 film.
It should be noted that the plots of leakage current density
vs electric field corresponding to BixFeO3 (x = 0.95, 1) in
Figure 2 show a slight offset with respect to the 0 point, instead
of x = 1.05. Such a slight offset may be relevant to the
measuring process. The measurement of leakage current was
obtained by applying the voltage from −10 to +10 V (or the
electric field from −200 to 200 kV/cm) to the samples. When
the negative bias was continuously applied to BFO, its internal
spontaneous polarization shifted into one direction. It would
form an internal electric field and affect oxygen vacancy
migration. Once the applied voltage was reversed, the internal
partial carriers were not fully inverted to the new direction,
eventually resulting in a slight offset. The offset did not
apparently present in the Bi1.05FeO3 film due to the lowest
oxygen vacancy concentration in this film.
To find why excessive Bi can improve the electrical
properties of the film, the leakage-conduction mechanisms
for the films were analyzed and discussed. Previously, many
reports proposed several leakage-conduction mechanisms for
BFO, including space charge-limited conductance (SCLC),
Poole−Frenkel emission (PF), Fowler−Nordheim tunneling
(FN), and Schottky barrier model (SE).37−39 Among them,
SCLC and PF belong to the bulk limited conduction emission
mechanism, whereas FN and SE belong to the interface limited
mechanism. The conduction mechanism of SCLC is formed by
the current impeding the formation of space charge when the
speed of charges injected from the electrodes into the films is
faster than they can penetrate the film, which can be expressed
as38
9 V2
J= μεrε0
8 L (1)
where μ is the charge carrier mobility, εr is the relative
dielectric constant, ε0 is permittivity of free space, V is voltage,
and L is the film thickness.
Schottky barrier results from the Fermi-level difference
between the metal electrode and the semiconductor film. The
energy difference creates a potential barrier between the metal
JPF = AE expÅÅ Å ÑÑ
ÑÑ
ÅÅ ÑÑÑ
ÅÇÅ Ö
k BT (3)
where A is a constant, φt is the trap ionization energy, and T is
the temperature.
Another type of leakage current conduction mechanism is
the FN leakage-conduction mechanism. The carrier at the
electrode passes through the electrode−film interface barrier,
entering the film through a tunneling pattern, and its
corresponding expression is36
ij −Cϕ 3/2 yz
J = BE2 expjjjj zz
z
j E zz
k {
i
(4)
where B and C are constants and φi is the potential barrier
height.
First, we could exclude the FN leakage-conduction
mechanism because the thickness of as-prepared films in this
case is about 500 nm, much larger than 50 nm for the possible
tunneling depth.40 Second, we can determine if it is the SCLC,
PF, or SE conduction mechanism by, respectively, plotting the
log E − log J, E1/2 − ln J/E, and E1/2 − ln J curves according to
expressions 1−3. After fitting the corresponding curves, we
observed the linear parts in log E − log J curves under the low
electric field regions, and their corresponding slopes are
around 1 for all films, whereas the linear fits in the high electric
field regions were found in E1/2 − ln J curves, as shown in
Figure 3. It clearly shows that the leakage mechanism for as-
prepared films is a typical Ohmic conduction behavior under
the low electric field regions and the SE mode in the high
electric field regions. Meanwhile, the PF mechanism can be
ruled out in all films since no linear behavior is found in the
E1/2 − ln J/E curves, as shown in Figure S4.
Figure 3. Leakage current behaviors presented as the (a) SCLC
model and (b) SE model for BixFeO3 (x = 0.95, 1, and 1.05) films.

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Figure 4. (a, e), (b, f), (c, g), and (d, h) corresponding out-of-plane PFM phase images of Bi1.05FeO3 films with 5, 10, 12, and 15 V tip bias on and
after the tip bias domain writing, respectively.

Figure 5. (a) Bi 4f, (b) Fe 2p, and (c) O 1s core-level XPS spectra for BixFeO3 (x = 0.95, 1, and 1.05) films.

Table 1. Binding Energy (eV) of Bi, Fe, and O Elements for Bi0.95FeO3, BiFeO3, and Bi1.05FeO3
elements Bi0.95FeO3 BiFeO3 Bi1.05FeO3
binding energy (eV) Bi Bi 4f7/2 158.5 ± 0.1 158.4 ± 0.2 158.2 ± 0.1
Bi 4f5/2 163.8 ± 0.1 163.7 ± 0.1 163.5 ± 0.2
Fe Fe 2p3/2 709.7 ± 0.2 709.0 ± 0.3 709.4 ± 0.2
satellite 717.9 ± 0.2 717.7 ± 0.2 717.6 ± 0.3
Fe 2p1/2 723.3 ± 0.2 724.1 ± 0.3 723.2 ± 0.2
O oxygen−metal bond 528.9 ± 0.1 529.0 ± 0.3 528.6 ± 0.1
dangling bond 530.9 ± 0.1 530.6 ± 0.1 530.7 ± 0.2
surface adsorbed oxygen 532.1 ± 0.3 531.7 ± 0.1 531.4 ± 0.1
RIR 1.57 ± 0.01 2.65 ± 0.02 3.03 ± 0.02

3.3. Piezo Force Microscopy (PFM). Although BFO has
been well known as a ferroelectric for a long time,41−43 the
saturated ferroelectric hysteresis loop is very difficult to achieve
in pure BFO polycrystalline samples (BFO polycrystalline films
or ceramics) mainly due to the problem of large leakage
currents.41,44−47 Doping or substitution by other metal ions in
A- or B-site of BFO is believed to be an effective method to
possibly observe the saturated ferroelectric hysteresis loop. In
our case, pure BFO polycrystalline films (BixFeO3 (x = 0.95, 1,
1.05)) prepared by the spin-coating process presented severe
leakage behaviors (as shown in Figure 2), and hence we could
not observe the saturated loops in these films. To confirm the
23375
ferroelectric nature of our samples, we investigated the
ferroelectricity of the Bi1.05FeO3 film by a supplementary
piezo force microscopy (PFM) measurement as shown in
Figure 4. Domain writing was performed by applying 5, 10, 12,
and 15 V direct current bias in the PFM mode. An obvious and
clear domain inversion can be seen in Figure 4h, corresponding
to an applied domain writing bias of 15 V, demonstrating the
ferroelectric nature of BixFeO3 films.
3.4. X-ray Photoelectron Spectroscopy (XPS) Anal-
ysis. XPS was employed to determine the chemical states of
Bi, Fe, and O elements in as-prepared films. Figure 5 shows Bi
4f, Fe 2p, and O 1s XPS spectra for BixFeO3 (x = 0.95, 1, and
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1.05) films. Figure 5a shows the high-resolution spectra of Bi 4f
for three BFO samples. The binding energies of Bi 4f7/2 and Bi
4f5/2 for all films are listed in Table 1. Compared with the XPS
data illustrative map, there is no remarkable difference in the
two peaks’ profile, implying that Bi elements in all films are in
the Bi3+ valence state.48 However, the two peaks in the Bi 4f
spectra of three samples inappreciably deviated from the
standard position, which may be attributed to the difference in
the chemical environment, electric charge effect, instrument
state, etc.
Figure 5b shows the high-resolution Fe 2p spectra of three
samples. The binding energies of Fe corresponding to Fe 2p3/2
and Fe 2p1/2 are shown in Table 1, which should be attributed
to the interaction of the spin−orbital effect. The satellite peak
around 717.7 eV (about 8.0 eV above the Fe 2p3/2 peak) was
found in all BFO samples, indicating that the valence state of
the Fe element is Fe3+.49,50 For BFO films with different Bi
contents, however, some peaks observed in the Bi and Fe
spectra transferred to a high binding energy. The displacement
of these XPS peaks could generally be ascribed to the
formation of oxygen vacancies, which increase the equilibrium
electron density and hence increase the binding energy.51
Figure 5c shows O 1s core-level XPS spectra of all samples.
The three peaks of O 1s XPS spectra corresponding to binding
energy from low to high are responsible for the oxygen−metal
bond, the dangling bond, and surface adsorbed oxygen.52 In
general, the emergence of these two peaks of the dangling
bond and adsorbed oxygen in the O 1s spectrum was
considered representative of the formation of oxygen vacancies
in perovskite oxides.53 Based on the relative peak’s intensity
ratio (RIR) between the oxygen−metal bond and the sum of
the dangling bond and adsorbed oxygen [RIR = IO−M /(IDL +
IADS), where IO−M is the relative peak’s intensity of the
oxygen−metal bond, IDL is the relative peak’s intensity of the
dangling bond, and IADS is the relative peak’s intensity of the
adsorbed oxygen], the content of oxygen vacancies can be
roughly estimated.52,54 In other words, the lower value of RIR
manifests the higher concentration of oxygen vacancies. The
calculated RIR values for Bi0.95FeO3, BiFeO3, and Bi1.05FeO3
are about 1.57, 2.65, and 3.03, respectively. It implies that the
lower the Bi content, the higher the oxygen vacancy
concentration in BFO films.
In the meanwhile, the surface element composition of BFO
films was also measured and analyzed by XPS after ion cleaning
the films by a 3 keV Ar-ion gun. As shown in Table 2, the
results displayed that the element composition or content of
BFO films is the same as what we expected to be prepared. For
example, the measured element ratio of Bi/Fe/O in the
Table 2. Surface Element Contents for Bi0.95FeO3, BiFeO3,
and Bi1.05FeO3
sample elements atomic content
Bi0.95FeO3 Bi 14.3(9)%
Fe 15.0(4)% Bi/Fe ∼ 0.95
O 55.8(6)% O/Fe ∼ 3.69
BiFeO3 Bi 9.9(2)%
Fe 9.9(9)% Bi/Fe ∼ 0.99
O 38.5(5)% O/Fe ∼ 3.85
Bi1.05FeO3 Bi 15.6(3)%
Fe 14.3(7)% Bi/Fe ∼ 1.08
O 55.8(9)% O/Fe ∼ 3.88
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Bi0.95FeO3 film is 0.95:1:3.69, which is almost the same as that
of its molecular formula. However, it is obvious that the
content of O element is slightly higher than the ratio set by the
precursor, which may be attributed to the small amount of
adsorbed oxygen residually attached to the surface of the film
although the films were etched by Ar ions. Furthermore, it
should be noted that the element ratio between the oxygen and
the metal in BFO films gradually increased accompanied with
the increased content of Bi, which clearly shows that the lower
the Bi content, the higher the oxygen vacancy concentration in
BFO films.
Therefore, XPS confirmed that the Bi1.05FeO3 film had the
least oxygen vacancy concentration; conversely, the highest
one was for the Bi0.95FeO3 film. In brief, more oxygen vacancies
in the Bi0.95FeO3 film due to the small content of Bi result in
smaller particles, more defects, and poor uniformity, which
directly affect the film’s electric and photovoltaic properties.
3.5. Photovoltaic Effect. To study the photovoltaic
properties of BixFeO3 (x = 0.95, 1, and 1.05) films, we
measured the photocurrent and photovoltage at zero bias by
controlling the light to be in the on or off condition, called
short-circuit current density (JSC) and open-circuit voltage
(VOC), respectively. JSC and VOC were measured under light
and dark conditions, in which the light source was alternately
turned on and off for 15 s, and repeated four times. As shown
in Figure 6, all films presented apparent optical response
Figure 6. (a) Photocurrent density (JSC) and (b) open-circuit voltage
(VOC) for BixFeO3 (x = 0.95, 1, and 1.05) films at zero bias by
controlling the light to be in on and off conditions.
behavior when the light was turned on. JSC of Bi1.05FeO3 is the
largest, and its value is 13 times higher than that of Bi0.95FeO3
and about 6 times higher than that of BiFeO3. Similarly, VOC of
Bi1.05FeO3 is also significantly higher than that of Bi0.95FeO3
and BiFeO3; detail values are shown in Table 3. Accordingly,
Table 3. Values of Photocurrent Density (JSC) and Open-
Circuit Voltage (VOC) for BFO Films under Zero Bias and
Light On Condition
JSC/VOC Bi0.95FeO3 BiFeO3 Bi1.05FeO3
JSC (μA/cm2) 5.31 ± 0.02 10.97 ± 0.01 66.42 ± 0.03
VOC (mV) 1.0 ± 0.1 22.8 ± 0.1 89.3 ± 0.2
the short-circuit current density and open-circuit voltage
increased with the increase of Bi content in films. That is,
the lesser the oxygen defects, the better are the photovoltaic
properties of the BiFeO3 film. In addition, if the photovoltaic
output could be simply estimated as the arithmetic product of
JSC and VOC (VOC × JSC), one can find that the photovoltaic
output of Bi1.05FeO3 increases more than 1000 times compared
with that of Bi0.95FeO3. It means that we can greatly tune or
improve the photovoltaic output of the BFO compound just by
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Figure 7. Time-dependent photocurrent densities for (a) Bi0.95FeO3, (b) BiFeO3, and (c) Bi1.05FeO3 films under different biases.
Figure 8. JSC−V curves for (a) Bi0.95FeO3, (b) BiFeO3, and (c) Bi1.05FeO3 films at rves were observed in the Bopposite bias voltages. Inset illustrates
the device structure under the measurement.
manipulating its oxygen vacancy concentration. Therefore, our
work may open a way to the design of photovoltaic devices
with high power output by simply manipulating oxygen
vacancies in the perovskites.
It should be mentioned that the open-circuit voltage (VOC)
values of our films are relatively low compared with those in
some other reports in the literature.2,7,17 Yang et al.2 observed
a high VOC of more than 15 V in high-quality epitaxial BFO
films with stripe 71° domains. Alexe et al.17 also reported a
high VOC of 13 V in the BFO single crystal. However, relatively
low VOC was generally observed in polycrystalline BFO
films.8−10,19,23,32,33 Especially, VOC of polycrystalline BFO
films prepared by the chemical solution deposition process is
usually less than 1 V. For example, Dong et al.19 reported a low
VOC of 0.63 V in polycrystalline BFO films. Even a very low
VOC of 0.08 V was also observed in polycrystalline BFO films
prepared by a sol−gel/spin-coating method.8 Therefore, it is
very difficult to obtain a high VOC in polycrystalline BFO films
prepared by the chemical solution deposition process. The
possible reason for low VOC in our films could be explained as
follows. Many defects or grain boundaries exist in polycrystal-
line BFO films, which act as recombination centers to trap the
photon-generated carriers. The photon-generated electrons
and holes cannot be efficiently separated and reach the
electrodes, which eventually lead to a relatively low VOC.
Based on the above results, a possible mechanism was
proposed to illuminate the effect of oxygen vacancies on the
photovoltaic properties and the origin of ferroelectric photo-
voltaic effect in BFO films. In this case, since all BixFeO3 films
exhibited the same crystalline structure as shown before, they
have almost the same band gap (shown in Figure S3; the
optical band gap of the film can be estimated by Tauc’s plot
from the UV−visible spectra), indicating that the number of
electron−hole pairs generated in the films under illumination is
almost the same. Therefore, all Au/BixFeO3/FTO film
capacitors are expected to exhibit similar photovoltaic
performance. In our case, however, quite different photovoltaic
properties were observed in Au/BixFeO3/FTO film capacitors,
which implies that oxygen vacancy has a great influence on the
electric and photovoltaic performances of the BixFeO3 films. As
mentioned above, Bi defects induced more oxygen vacancies in
the BixFeO3 films. In other words, more oxygen vacancies
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should be present in the Bi0.95FeO3 film and less in the
Bi1.05FeO3 film. Based on the above discussion, it is deduced
that the photocurrent reduced greatly in the Bi0.95FeO3 thin
film because many photogenerated electrons are trapped by
the positive oxygen vacancies and consequently result in severe
recombination with photogenerated holes. Therefore, the
minimum short-circuit current was obtained from the
Bi0.95FeO3 film compared with the others because the highest
oxygen vacancy concentration was found in this film, which
was also confirmed by XPS analysis.
Blom et al. believed that the origin of photovoltaic effect in
the metal-BFO polycrystalline film heterojunction was
generally attributed to the Schottky barrier formed in the
interface between the metal and the semiconductor.31,55 In our
case, all Au/BixFeO3/FTO film capacitors have the same
geometric electrode structure and thereby almost the same
Schottky barrier. Therefore, they should present similar
photovoltaic properties if the Schottky barrier was the origin
of photovoltaic effect in the BFO films. Apparently, it is not the
case in our samples. JSC and VOC of Bi1.05FeO3 are quite higher
than that of Bi0.95FeO3 as observed in Figure 6 and Table 3.
Therefore, the Schottky barrier induced the photovoltaic effect
is not dominant in our samples. As discussed and analyzed
above, since all BixFeO3 films have the same crystalline
structure and almost the same band gap, they should have
similar bulk photovoltaic effects. The difference in the
photocurrent and photovoltage of BixFeO3 films was indeed
affected by the existence and difference of oxygen vacancies
since oxygen vacancies as the trap centers greatly influenced
the recombination of photogenerated carriers. Therefore, the
origin of photovoltaic effect in all BixFeO3 films should be
attributed to the bulk photovoltaic effect, as observed in the
BFO single crystal.56
3.6. Switchable Photovoltaic Property. To investigate
the switchable photovoltaic property, we measured the time-
dependent photocurrent for the three films under different
biases, as shown in Figure 7. It can be seen that all three
samples presented an enhanced photovoltaic response after
applying a negative bias voltage, relative to their virgin states,
as shown in Figure 6 and Table 3. For example, photocurrent
for the Bi1.05FeO3 film increased from 66.4 up to 139.5 μA/cm2
after applying a bias voltage of −5 V. More interestingly, as
DOI: 10.1021/acsami.9b06704
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ACS Applied Materials & Interfaces
seen in Figure 7a,b, the apparent reversible switching
photovoltaic effect was found in both Bi0.95FeO3 and BiFeO3
films since the photocurrent was flipped at +3 and +5 V bias,
respectively. However, it was difficult to observe this effect for
Bi1.05FeO3 even at a bias higher than +5 V until it was broken
down, indicating that the direction of polarization is not
necessary for the reversal of photocurrent. Therefore, it is not
always possible to control the direction of photocurrent by
changing the polarization direction as reported previ-
ously.1,20,57
Figure 8 shows the J−V curves of the three films at opposite
bias voltages under the light on or off condition. By applying
the bias voltage onto the samples, it is expected to observe a
pronounced diodelike behavior in both Bi0.95FeO3 and BiFeO3
films since the asymmetric J−V curves were observed in these
two films. In this case, applying the positive and negative bias
voltages on the top electrode is depicted as downward and
upward poling, respectively. For example, it could be described
that the diode forward direction is from bottom to top when a
negative direct-current bias voltage was applied on the top
electrode of the Bi0.95FeO3 film (i.e., upward poling) (as shown
in the inset of Figure 8a). When positive bias voltage was
applied to the Bi0.95FeO3 film, the poling switched to the
downward direction, and the diode forward direction also
changed. In this condition (applying a positive bias voltage),
however, the diodelike behavior is not so distinct since the
currents along two directions (upward and downward) are not
quite different. This result is well in accordance with the
photocurrent switching behavior as shown in Figure 7, which
should be linked to the presence of a depletion layer of the
Schottky junction at the Au−BFO and BFO−FTO interfaces.
A similar one-side diode effect was also observed in the BiFeO3
film, in spite of the requirement of higher bias voltage.
In our case, however, the symmetric J−V curves were
observed in the Bi1.05FeO3 film even at bias voltage higher than
±5 V, although it could not completely exclude the diodelike
nature of the sample.32,58−60 It should be noted that the
oxygen vacancy concentration in these films is quite different,
as confirmed by XPS analysis. The difference in J−V curves
might be intensely related to the different oxygen vacancy
concentration in the three samples, which is also discussed
later.
Concerning the mechanism for this diodelike behavior or
photocurrent switchable character, either the ferroelectric
polarization or the electromigration of chemical defects was
considered as the dominating factor.23 In this case, the
photocurrents in Bi0.95FeO3 and BiFeO3 films were flipped at
±3 and ±5 V bias, respectively. This means that the maximum
value of the reversal electric field (E) for photocurrent is only
100 kV/cm, which is far lower than the coercive field of the
polycrystalline BFO film as EC ∼ 250 kV/cm.29,61 That is, the
reversal of ferroelectric polarization does not really occur at
this low bias voltage. In our case, therefore, ferroelectric
polarization is not the dominating factor controlling the
photocurrent switching in Bi0.95FeO3 and BiFeO3 films. In fact,
the most significant difference in BixFeO3 films is the
concentration of oxygen vacancy. As discussed above, the
oxygen vacancy intensely affected the leakage current,
photocurrent, and photovoltage in BixFeO3 films. In this
case, meanwhile, the electromigration of oxygen vacancies is
also considered to play a key role in this kind of switchable
photovoltaic effect. Based on the above analysis and discussion,
a switchable Schottky-to-Ohmic interfacial contact model was
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Research Article
proposed to illustrate the switchable photovoltaic or diodelike
effects in our samples, as shown in Figure 9. When a bias
Figure 9. Distribution diagram of oxygen vacancies and the
corresponding barrier height for three BFO films in the original
state (a−c) and the bias state (d−f).
electric field lower than its coercive field is applied onto the
sample, the positively charged oxygen vacancies migrate
toward the electrode interface. In the p-type BFO film, the
barrier height can be reduced by introducing a high-
concentration oxygen vacancy layer to the interface between
the BFO film and the electrodes. In this case, specifically, when
a positive bias is applied onto the BFO devicean electric
field along the FTO to BFO directionthe positive oxygen
vacancies will migrate to the FTO side, and then the barrier
height at the FTO−BFO interface will decrease. In this
condition, the heightened difference of the Schottky barrier
height between FTO/BFO and Au/BFO means that the
photocurrent along the electric field E direction is only
permitted and the reversed photocurrent is forbidden, namely,
generating a diodelike effect.23 The more the oxygen defects
exist, the more pronounced is this asymmetry in the barrier
height and the lower is the requirement of the bias voltage in
the diodelike effect. That is why photocurrent in the Bi0.95FeO3
film can reverse at only 3 V, whereas a higher value of 5 V is
necessary for the BiFeO3 film. Moreover, the photocurrent
reversal in Bi1.05FeO3 is impossible even at bias voltage higher
than 5 V until it was broken down since the concentration of
oxygen vacancies in this film is too low to generate enough
asymmetry in the barrier height. It can be used to explain why
the symmetric J−V curves were observed in the Bi1.05FeO3 film
even at bias voltage higher than ±5 V. Note that the
asymmetric electrodes of Au and FTO in our samples will also
bring about a Schottky barrier imbalance. In fact, we could
simply estimate the Schottky barrier height of BFO with
different metal electrodes on the basis of the metal-induced-
gap-state model just calculating the difference between the
work function of the metal and the electron affinity of BFO.
The work functions of Au and FTO (ΦAu, ΦFTO) are about 5.1
and 4.4 eV, respectively.62 The electron affinity of BFO (χBFO)
is estimated as 3.3 eV. The contacted energy band diagram of
metal electrodes and the p-type semiconductor BFO film is
shown in Figure S6. Schottky barrier height of the Au−BFO
interface can be estimated as ΦAu/BFO = Eg‑BFO−(ΦAu − χBFO),
and then the barrier height of the BFO−FTO interface can be
estimated similarly as ΦBFO/FTO = Eg‑BFO−(ΦFTO − χBFO). The
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ACS Applied Materials & Interfaces
imbalance of the Schottky barrier can be obtained by |ΦAu/BFO
− ΦBFO/FTO|. Obviously, |ΦAu/BFO − ΦBFO/FTO| = |ΦAu − ΦFTO|
∼ 0.7 eV, which is far lower than the required reversal voltages
of 3 V for the Bi0.95FeO3 film or 5 V for the BiFeO3 film.
Apparently, the effect of this Schottky barrier imbalance can be
ruled out in our samples. In our case, the electromigration of
oxygen vacancies should be the dominating factor to determine
the switchable photovoltaic effect or diodelike behavior, rather
than ferroelectric polarization or the inappreciable Schottky
barrier imbalance.63,64
4. CONCLUSIONS
We prepared bismuth ferrite films with different Bi contents on
FTO/glass substrates by a sol−gel spin-coating method. We
concluded by measuring the surface morphology and electric
and photovoltaic properties of the films that the lesser the Bi
content, the poorer is the morphology of the films, and the
more are the chemical defects (oxygen vacancies), resulting in
the larger leakage current and degraded photovoltaic perform-
ance. On the contrary, photocurrent reversal easily occurs in
BFO films with high oxygen vacancies under the application of
a small bias voltage.
Apparently, the effect of oxygen vacancies on the surface
morphology and electric and photovoltaic properties of BFO
films should not be underestimated. Better understanding of
the effect and inherent mechanism of oxygen vacancies on the
photovoltaic characteristics of BFO films will be helpful to
expand its application in the field of ferroelectric photovoltaics.
Furthermore, the present work may open a way to tune or
realize the high power output and controllable photovoltaic
switching behavior for photovoltaic applications of BFO
compounds.
■
ASSOCIATED CONTENT
*
S Supporting Information
The Supporting Information is available free of charge on the
ACS Publications website at DOI: 10.1021/acsami.9b06704.
Details on structure analysis, morphology, and optical
band-gap estimation (Figures S1−S3); E1/2 − ln J/E
curves of the PF mechanism (Figure S4); electronic
band structures for BFO films (Figure S5); band analysis
data of BixFeO3 (x = 0.95, 1, and 1.05) films (Table S1);
contacted energy band diagram of the metal electrode
and the BFO film (Figure S6) (PDF)
■ AUTHOR INFORMATION
Corresponding Author
*E-mail: weij2008@xjtu.edu.cn, jiewei2013wj@gmail.com.
ORCID
Jie Wei: 0000-0003-0612-8606
Author Contributions
T.Y. conceived and carried out the experiments. T.Y. and J.W.
analyzed the data and wrote the paper. All authors read and
approved the final manuscript.
Notes
The authors declare no competing financial interest.
Electronic Materials Research Laboratory, Key Laboratory of
Ministry of Education & International Center for Dielectric
Research, School of Electronic and Information Engineering,
Xi’an Jiaotong University, Xi’an 710049, P.R. China.
23379
Research Article
■ ACKNOWLEDGMENTS
Financial support by the National Natural Science Foundation
of China (Grant no. 51272204) is gratefully acknowledged.
Thanks largely to Jiamei Liu for the help of XPS measurement.
The authors also thank Dai and Ma for their help in using FE-
SEM at the International Center for Dielectric Research
(ICDR), Xi’an Jiaotong University, China.
■
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23381 DOI: 10.1021/acsami.9b06704

ACS Appl. Mater. Interfaces 2019, 11, 23372−23381