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Above-Band-Gap Voltage from Oriented Bismuth Ferrite Ceramic

Photovoltaic Cells
Kun Yao Liang, Ye Feng Wang, Zhou Yang, Shi Peng Zhang, Shi Yao Jia, and Jing Hui Zeng*

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ABSTRACT: An open-circuit voltage of 6.9 V was received on oriented ceramic

Downloaded via UNIV AUTONOMA DE MADRID on August 7, 2022 at 18:50:38 (UTC).

bismuth ferrite (BFO) thin-film solar cells working in an “out-of-plane” mode.

The above-band-gap voltage is strongly related to the crystallinity, orientation, and
thickness of the BFO film contributing to the bulk photovoltaic effects, which
have been further verified by powder X-ray diffraction, scanning electron
microscopy, and atomic force microscopy results. The current density−voltage
traces show the highest open-circuit voltage of 6.9 V on 600 nm thick cells heated
at 500 °C. Polings along the opposite directions would modify the current
density−voltage traces accordingly, which suggests the ferroelectric nature of the
solar cells.

KEYWORDS: ceramic photovoltaic cell, above-band-gap voltage, bulk photovoltaic effect, ferroelectric, “out-of-plane” mode

■ INTRODUCTION
An open-circuit voltage limited by the band gap is a general
gap open-circuit voltages.14 Nevertheless, the origin of the
anomalous high-voltage bulk photovoltaic effects based on
domain walls is still a subject of debate. Research studies show
efficiency limitation in solar cells due to the device working
that the generation and recombination of photogenerated
principle.1 Solar cells with an above-band-gap voltage are
carriers in BFO single crystals are primarily affected by the
attracting research interest these days for multiferroic
presence of shallow energy levels, and domain walls do not
materials.2−5 Since the research on the mechanism of high
play a major role in the corresponding photovoltaic effect.17
voltage above the band gap was initiated from 1946,6 lead
Apart from the debate on the mechanism of the above-band-
sulfide, cadmium telluride, and cadmium sulfide are very initial
gap voltage, most of the current reports are on single-crystal
reported materials to open-circuit voltages of 3, 7, and 17 V,
films in the “in-plane” mode.3,18 Devices working in the “out-
respectively, higher than their corresponding band gaps.7,8
of-plane” mode remain a challenge. Either a method to arrange
Subsequently, more and more materials with an open-circuit
domain walls in a vertically parallel mode or a new insight into
voltage higher than the band gap have been reported, such as
both the working principle and the device fabrication must be
the multiferroic material barium titania (BTO) and bismuth
proposed.
ferrite (BFO) with a relatively small band gap (2.2−2.7 Although there are reports on out-of-plane devices (Scheme
eV).3,9,10 1b), their working mechanism follows those of heterojunction
The above-band-gap voltages follow two major mechanisms, cells. A stacking of Ag/Spiro-OMeTAD/BFO/TiO2/FTO cell
domain walls and bulk photovoltaic effects (BPVs).11,12 records a short-circuit density of 62.6 μA·cm−2 and an open-
Accumulated high voltage of over 16 V from 10 mV on circuit voltage of 0.29 V.19 A detailed study suggests that the
successive BFO domain walls is reported (Scheme 1a).4 A aliovalent substitution (Ca2+ at Bi3+ site) is used to control the
BFO single-crystal film of around 100 nm thickness is lattice oxygen vacancies, while Ca and Ti co-substitution is
deposited on a single-crystal substrate of DyScO3, SrTiO3, or used to bring out only grain boundary oxygen vacancies. With
SrRuO3 substrate to ensure that it has the specific crystal plane
orientation as (001).4,13−16 The above-band-gap voltage is
strongly related to the orientation of the electrode. If the Received: August 11, 2021
electrodes are deposited parallel to the domain walls, no Accepted: October 17, 2021
photo-induced voltage is obtained.4 A detailed study detecting Published: November 2, 2021
terahertz radiation emanating by the photogenerated currents
enables a direct probe of the intrinsic charge separation and an
in-depth understanding of the mechanism of the above-band-

© 2021 American Chemical Society https://doi.org/10.1021/acsaem.1c02395

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Scheme 1. Schematic Diagram of the Above-Band-Gap Voltage Received from BFO Films: In-Plane Mode with Successively
Accumulated Domain Walls on an Epitaxial Single-Crystal Film (a); Out-of-Plane Mode on a Polycrystalline Thin Solid Film
(b); and This Work, Out-of-Plane Mode on an Oriented Ceramic Film (c)
Table 1. Summary of the Parameters of the Reported BFO Devices
structure Voc (V)
this work 6.90
FTO/BFO/Au20 0.3
Au/BFO/Pt23 1.28
FTO/BFO/Au24 0.41
FTO/BFO/ITO25 0.2
BTO/probe1 1.2
Pt/BTO/Pt26 0.7
STO/SRO/BFO/Au27 0.3
STO/LSMO/BFO/Pt28 0.56
ITO/BFO/Al-ITO29 0.24
Pt/TiO2/SiO2/Si/BFO/Au30 0.435
ITO/CdS/BFO/PbS/Ag31 0.13
delicate dopings, open-circuit voltages were claimed to be
tuned from 0.5−3 to 3−8 V. However, the reported data
support an average voltage of 6 V with a widely dispersed
voltage from 3 to 8 V, in which the highest voltage is claimed
as the top voltage in the literature. Remarkable efficiencies of
0.11−0.22% were recorded for FTO/Bi0.8Ca0.2FeO3−δ/Au cells
with open-circuit voltages from 0.1 to 0.3 V and current
densities of ∼2.6 to 3.2 mA·cm−2.20 Although the enhanced
ferroelectric properties account for the high voltage on doped
BFO samples, the varied current and voltage on a definite
component are vague, reflecting the uncertainty about the
nature of the reported above-band-gap voltages. Up to now,
the highest PCEs of 8.1 and ∼4.2% in out-of-plane devices
have been reported for Bi2FeCrO6 and BiMnO3−BiMn2O5
thin-film cells deposited on oriented conducting single-crystal
substrates by the pulse laser deposition technique with open-
circuit voltages of 0.84 and ∼1.48 V, respectively.21,22 Most of
the research works on BFO photovoltaics show below-band-
gap voltages on single-crystal and polycrystalline films. Cells
with above-band-gap voltages especially on ceramic BFO films
with the BPV mechanism are still theoretically and practically
desirable (Table 1).
In this work, BFO particles were synthesized hydrothermally
and spin-coated on an FTO substrate and subjected to thermal
treatment (Scheme 1c). Scanning electron microscopy (SEM)
and atomic force microscopy (AFM) survey illustrated a
preferred orientation of these BFO particles. Photovoltaic cells
were assembled by covering an Au-coated FTO glass onto the
BFO films. An above-band-gap voltage of 6.90 V was recorded
on these oriented BFO ceramic films with a short-circuit
current density of ∼6 μA·cm−2. Cells with an effective incident
light area of 28.26 mm2 generated 0.0180% power conversion
efficiency. In-depth research on the above-band-gap voltage
indicated that the internal electrical field caused by a dipole is
the main driving force for the carrier transport in the cells and
accounts for the high open-circuit voltage in the device.
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Jsc (μA·cm−2) area (mm2)
6.0 28.26
3 × 103 3.14
105 0.00785
0.3 0.785
3.6 0.0625
19.1 10−6
9 3.14 × 10−4 to 7.85 × 10−3
0.4
2.5 0.0004−0.01
0.17 4
2350
239.60 small metallic contact
■ EXPERIMENT SECTION
Synthesis of BFO Particle. Bi(NO3)3·5H2O (3.8 g) and
3.2 g of Fe(NO3)3·9H2O were dissolved successively in
deionized water and stirred for 30 min. Forty to sixty milliliters
of a 4M NaOH solution was added. After the slurry turned
reddish-brown, stirring was continued for another 4 h and the
mixture was then transferred into autoclaves and heated at 180
°C for 10 h. After cooling to room temperature naturally, the
reactant was centrifuged at 5000 rpm and then washed with
deionized water and ethanol to receive the products. The
products were dried at 60 °C for further applications.
Preparation of BFO Film and Device. BFO particles (0.5
g) were put into a mortar. Glacial acetic acid, deionized water,
and ethanol were added in sequence. The slurry was ground
thoroughly to make the BFO particles finer. The finely ground
BFO particles were dispersed in ethanol, stirred, and sonicated
to obtain a BFO paste.
The FTO is cleaned and pasted with 3M tape with 6 mm
holes. The BFO paste was spin-coated on the conductive glass
at a rotation speed of 3000 rpm. Then, the films were put into
a Muffle furnace and heated at 200−600 °C.
The counter electrode is ion-sputtering gold onto the FTO
substrate. The BFO films and the gold electrode were
assembled on the final photovoltaic cells.
Polings. A DC power supply (Maynuo DC M8811) was
used to apply a voltage of 6 V for 10 s to the BFO thin-film
device to conduct polings in different directions. In the present
work, a voltage bias applied from the top electrode (FTO side)
to the down electrode (Au side) is defined as a downward
poling. An inverse poling bias is defined as an upward poling.
Photovoltaic performances were recorded with the virgin cells
without poling and the cells with downward and upward
polings.
Characterizations. X-ray diffraction (XRD) patterns were
collected on a Rigaku Smart Lab(9) diffractometer using Cu
Kα radiation (voltage = 45 kV, current = 200 mA, λ = 1.5418
Å, sweeping rate = 5°/min). Field emission scanning electron
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microscopy (FESEM) images were recorded on Hitachi SU-
8020. Atomic force microscopy (AFM) was performed on
Bruker Dimension ICON to reveal the orientation of the
ceramic films. The current density−voltage curves were traced
on a CHI660E electrochemical workstation (CHI Instruments,
Shanghai Chenhua Inc.) under a standard sun simulator (100
mW·cm−2). The light was incident from the FTO side of the
cells.
■ RESULTS AND DISCUSSION
The phase purity of BFO particles synthesized hydrothermally
was confirmed by XRD (Figure 1). All of the diffraction peaks
Figure 1. XRD patterns of BFO particles and BFO films. Bottom, the
standard JCPDS (Card No. 20-0169) of bismuth ferrite.
could be well indexed to those of BiFeO3 (JCPDS Card No.
20-0169) with no detectable impurity peak. After being
deposited onto the FTO substrate, the BFO films reserve the
Figure 2. Typical SEM image, top-down (a), cross-sectional (b), and AFM stereogram (c) of the BFO film heated at 500 °C. AFM surface surveys
of the BFO films heated at 200 °C (d), 500 °C (e), and 600 °C (f).
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phase purity with an even stronger signal-to-noise ratio in the
diffraction peaks. Meanwhile, there are relative intensity
variations in the three strongest diffraction peaks, suggesting
a more regular morphology and preferred orientation in the
deposited BFO films.
Surface morphologies and orientations of the BFO ceramic
films are investigated with SEM and AFM. A typical SEM top-
down image of the film heated at 500 °C illustrates uniform
particle sizes and well-developed facets. Furthermore, the tips
of the enclosed facets tend to face upward, resulting in the
preferred orientation of BFO ceramics (Figure 2a), which is
crucial for the high voltage. The ceramic particles cover the
FTO substrate thoroughly and uniformly according to various
spin-coating cycles (Figure 2b), which are discussed later in
the paper. The decisive structure is further depicted by AFM.
In the representative stereogram of the BFO film, peaks
outstretch among the mountains of the BFO ceramic particles
(Figure 2c). The peaks under AFM are much more uniform
than those observed in the SEM image, suggesting the
ferroelectric nature of the faceted BFO ceramic particles
(Figure 2e). The orientation of BFO ceramics is proved to
show the critical effect on the above-band-gap voltage.
The sintering temperature is the crucial parameter in the
formation of the preferred orientation BFO films. When the
BFO films are treated at 200 °C, small particles with irregular
morphology dominate the sample (Figure 2d). There is also no
observable uniformity both in particle size and orientation of
the ceramics. A drastic transformation is found in the BFO
ceramic films heated at 500 °C. In the surface morphology
survey scanning of the AFM image, prisms are re-treated as
triangles with golden shadings indicating the upward-facing
tips of the prisms (Figure 2e). We can also find that the
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Figure 3. Representative J−V traces on FTO/BFO/Au ceramic photovoltaic cells using FTO (a) and Au (b) side as the positive electrode at heat
treatment temperatures from 200 to 600 °C. A digital camera image of the BFO film (inset in (a)).
uniformity of size and orientation of the prisms is optimized
but is deteriorated in BFO films treated at higher temperatures
(Figure 2f). Although the size of BFO particles treated at 600
°C remains mostly uniform, the orientation, especially the
tipping up of the BFO prisms, faded.
Ceramic particle coverage on the films is another important
factor of cell performance. The particle size of BFO is around
200 nm (Figure 2a); there is a lack of continuous coverage on
200 nm thick films. When the film thickness is increased, the
coverage is more uniform until the film thickness is 600 nm.
The coverage uniformity does not increase obviously with
enhanced film thickness. The BPV effects originate from the
bulk BFO with preferred orientations. Films with appropriate
film thickness and favorable particle orientation result in higher
voltage.
Uniform coverage of BFO particles with preferred
orientations treated at optimal temperatures is the fundamental
requirement for high voltage. The self-polarization owning to
the structure is the origin of the high voltage present with the
preferred orientation. The open-circuit voltages using virgin
cells and after poling in opposite voltage directions are
discussed below.
First, and the most interesting and important thing, the
above-band-gap voltage from around 2.7 to 6.9 V can be
recorded on virgin cells treated at different temperatures
(Figure 3a and Table 2). When FTO sides are used as an
anode, the lowest open-circuit voltage of 2.7 V is obtained on
the cells heated at 200 °C. From the results discussed above,
the size of irregular BFO particles is small, lacking orientation.
However, the open-circuit voltage of 2.7 V is still much higher
than that of regular cells below the theoretical band gap limited
photovoltages, which is generally lower than about 1 V in p−n
Table 2. Open-Circuit Voltage versus Treatment
Temperature on FTO/BFO/Au Ceramic Photovoltaic Cells
Using FTO or Au as a Positive Electrode
voltage (V)
temperature (°C) FTO Au
200 2.7 2.0
300 3.7 2.2
400 5.0 4.1
500 6.9 5.1
600 4.2 2.5
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junction cells.22,32 At higher treatment temperatures, the
particle size increases with quite regular orientations as
illustrated in SEM and AFM surveys. As a result, the highest
voltage of 6.9 V is recorded for the BFO ceramic photovoltaic
cells heated at 500 °C. The voltage decays on the sample
heated at 600 °C agree with the random orientations on the
samples heated at higher temperatures. Variations in the open-
circuit voltage fit very well with the uniformity of BFO
orientation.
The relationship of high voltage with preferred BFO
orientations is the only existing phenomenon. We suspect
that the self-polarization is the backstage driving force, which is
supported in the controlled experiments, including the
exchange of positive and negative electrodes and J−V traces
after downward and upward polings. When the positive and
negative electrodes are reversed, i.e., Au instead of FTO sides
is used as the positive electrode, lower open-circuit voltages are
recorded (Figure 3b and Table 2). However, even the lowest
voltage of 2.0 V in the reversed electrode circumstance is still
higher than the band gap voltage. It is reported that a
downward self-polarization is favored on BFO films grown on a
conductive substrate.33−35 As a result, the ceramic photovoltaic
cells record a higher voltage when the FTO side is used as the
positive electrode.
The voltage of ceramic photovoltaic cells varies with poling
directions. When the FTO side is used as the positive
electrode, a virgin cell gives a voltage of 6.9 V. An upward
poling compensates the self-polarization so as to reduce the
open-circuit voltage to 5.6 V (Figure 4). Due to the
Figure 4. Open-circuit voltage on virgin FTO/BFO/Au ceramic
photovoltaic cells can be tuned up and down along with upward and
downward polings, reflecting the ferroelectric nature of the cells.
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ACS Appl. Energy Mater. 2021, 4, 12703−12708
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ferroelectric nature of BFO ceramics, the polarization can be
enhanced with reverse poling.36−38 From the J−V curve, we
can notice that the open-circuit voltage is increased back to 6.4
V, very close to 6.9 V on the virgin cell, when a downward
poling is applied. We assume that the open-circuit voltage can
be further increased if an optimal poling is applied on ceramic
photovoltaic cells using Au as the positive electrode, which is
evidenced in the following experiments. An open-circuit
voltage of 5.1 V is recorded on 600 nm thick BFO virgin
cells heated at 500 °C. The lower voltage compared to that
when FTO is used as a positive electrode is basically due to
self-polarization, which is discussed above. The voltage
increases drastically to 6.3 V when an upward poling is
applied. The increased voltage can be tuned back to 5.2 V,
which is very close to 5.1 V on virgin cells with an opposite
poling.
■
CONCLUSIONS
Above-band-gap voltages are received on ceramic photovoltaic
cells with oriented bismuth ferrite particles. Both the sintering
temperature and the film thickness have obvious influences on
the orientation of BFO ceramics, which affect their photo-
voltaic performance. An open-circuit voltage of 6.9 V is
received on ceramic photovoltaic cells using a 600 nm thick
BFO ceramic film and FTO as the positive electrode. The
voltage can be tuned by polarization under 6 V with upward
and downward polings. Further study is required to understand
the detailed working mechanism of the cell so as to increase
the photocurrent and the overall efficiency. The present work
exhibits a high-voltage out-of-plane ceramic photovoltaic cell
with both theoretical and practical importance.
■
AUTHOR INFORMATION
Corresponding Author
Jing Hui Zeng − School of Materials Science and Engineering
and Shaanxi Key Laboratory for Macromolecules, Shaanxi
Normal University, Xi’an 710119, P. R. China; orcid.org/
0000-0003-3279-0652; Email: nanosci@snnu.edu.cn
Authors
Kun Yao Liang − School of Materials Science and Engineering,
Shaanxi Normal University, Xi’an 710119, P. R. China
Ye Feng Wang − School of Chemistry and Chemical
Engineering and Shaanxi Key Laboratory for
Macromolecules, Shaanxi Normal University, Xi’an 710119,
P. R. China; orcid.org/0000-0001-5194-0287
Zhou Yang − School of Materials Science and Engineering,
Shaanxi Normal University, Xi’an 710119, P. R. China;
orcid.org/0000-0001-5203-8199
Shi Peng Zhang − School of Materials Science and
Engineering, Shaanxi Normal University, Xi’an 710119, P. R.
China
Shi Yao Jia − School of Materials Science and Engineering,
Shaanxi Normal University, Xi’an 710119, P. R. China
Complete contact information is available at:
https://pubs.acs.org/10.1021/acsaem.1c02395
Notes
The authors declare no competing financial interest.
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ACKNOWLEDGMENTS
The work is supported by the Fundamental Research Project
by Central Government Universities (Grant No. 202101007)
and the Shaanxi Normal University Postgraduate Innovation
Team Project from the Graduate School of Shaanxi Normal
University (Grant No. TD2020047Y).
■
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