Materials Letters 210 (2018) 218–222

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Materials Letters
journal homepage: www.elsevier.com/locate/mlblue

BaBiO3: A potential absorber for all-oxide photovoltaics

Arun Singh Chouhan a,⇑, Eashwer Athresh b, Rajeev Ranjan c, Srinivasan Raghavan a, Sushobhan Avasthi a
a
Centre for Nanoscience and Engineering, Indian Institute of Science, Bangalore, Karnataka 560012, India
b
Interdisciplinary Centre for Energy Research, Indian Institute of Science, Bangalore, Karnataka 560012, India
c
Department of Materials Engineering, Indian Institute of Science, Bangalore, Karnataka 560012, India

a r t i c l e i n f o a b s t r a c t

Article history: BaBiO3 is presented as a potential absorber for all-oxide solar cells. Thin-films of BaBiO3 were deposited
Received 12 July 2017 by pulsed laser deposition. As-deposited thin-films were amorphous, but a rapid thermal anneal at
Received in revised form 15 August 2017 600 °C for 10 min yields polycrystalline thin-films. X-ray photoelectron spectroscopy measurements
Accepted 9 September 2017
show that deposited films have Barium in Ba+2 state and bismuth in both Bi+3 and Bi+5 state. UV–Vis
Available online 11 September 2017
spectrophotometer (UV–Vis) shows that BaBiO3 films have direct and indirect bandgap (Eg) of
2.25 eV and 2.02 eV respectively, while ultraviolet photoelectron spectroscopy (UPS) shows that
Keywords:
valence band maxima (EV), conduction band minima (EC) and work-function (/) of BaBiO3 is at
Thin-film
Oxide photovoltaics
5.82 eV, 3.8 eV and 4.22 eV respectively. BaBiO3 thin-film devices with a FTO/c-TiO2/BaBiO3/Au struc-
XPS ture show rectifying current–voltage characteristics in dark. Under illumination, a photo response with
Energy-band offset a Jlight/Jdark ratio of 1.75 is observed.
Ó 2017 Elsevier B.V. All rights reserved.

1. Introduction 2.2. Film deposition and device fabrication

Metal-oxide (MO) semiconductors are widely used in photo-
voltaic devices as transparent conducting oxides (TCO) [1] and car-
rier transport layers [2,3] but seldom as primary light absorbers
[4,5]. In this report we present BaBiO3 (BBO) a potential solar
absorber for all-oxides thin-film solar cells. BBO is a well-known
material used for high Tc superconductors like BaK1
xBixO3 [6].
Theoretically BBO is predicted to be a metal, however experimen-
tally BBO has been shown to be a semiconductor [7] with reported
band-gap of 2.05 eV [8].
The substrate was commercially sourced FTO-coated glass sub-
strate (Techinstro; 7 ohm/sq.). On the FTO layer, a 40 nm thick
compact-TiO2 (c-TiO2) was deposited by reactive sputtering using
a Ti target. Thin-films of BBO were deposited by pulsed laser depo-
sition (PLD) using a 248 nm Excimer laser in a custom-designed
system (Supplementary Information). PLD deposition parameters
are as given in Table 1. Diodes with FTO/c-TiO2/BBO/Au structure
were fabricated by depositing 100 nm of gold on top of BBO thin-
film using e-beam evaporation (Fig. 3(c)).

3. Results and discussion

2. Experimental section
2.1. Synthesis of BaBiO3
BBO was synthesized by solid state synthesis using BaCO3 and
Bi2O3. The precursors were grinded in a ball mill for 12 h followed
by calcination at 850 °C for 4 hours in a tube furnace. Resulting
BBO powder was pressed into a pellet of 5 mm diameter and sin-
tered at 900 °C for 2 h.
⇑ Corresponding author.
E-mail address: arunc@iisc.ac.in (A.S. Chouhan).
X-Ray diffraction (XRD) pattern of the BBO pellet was compared
with JCPDF card #07-070-0652 (Fig. 1(a)). All peaks are accounted
for, which confirms that the synthesized material is BBO. XRD
pattern of as-deposited BBO thin-films show low-intensity peaks
corresponding to the underlying FTO/TiO2 substrate (SnO2 and
TiO2) but no clear peaks of BBO, probably because as-deposited
BBO films are amorphous. For devices, more crystalline films are
desirable, so the as-deposited films were annealed for 10 min at
600 °C in O2. M.S.M-Gonzalez et al have previously reported that
high temperature anneals under an oxygen ambient lead to more
crystalline BBO thin-films [9]. XRD pattern of annealed films shows

http://dx.doi.org/10.1016/j.matlet.2017.09.038
0167-577X/Ó 2017 Elsevier B.V. All rights reserved.
 A.S. Chouhan et al. / Materials Letters 210 (2018) 218–222 219

Table 1 in the XPS chamber using an Ar-ion gun for 100 s. XPS spectra
Deposition parameters for BaBiO3 thin-films depos- show peaks at 780.3 eV and 795.5 eV, corresponding to Ba+2 3d
ited using PLD.
core levels (Fig. 2(a)). More crucially, peaks at 159.5 eV and
Deposition Temperature (°C) 500 161.4 eV, corresponding to Bi+3 4f and Bi+5 4f, respectively, are
Base Pressure (mBar) 2  10
5 observed. The separation between Bi+3 and Bi+5 peak is 2 eV,
Deposition Pressure (mBar) 0.1
Target-Substrate Distance (cm) 4
which is larger than the 1 eV separation typically observed
Laser Pulse Frequency (Hz) 5 between Bi+3 4f and Bi+4 4f or Bi+4 4f and Bi+5 4f core levels. Similar
Oxygen Flow (sccm) 0.55 observations have been reported for BBO films by Zalecki et al. [11]
Laser Energy (mJ) 100 Overall, we can confidently state that the deposited films do not
Laser spot area (mm2) 3
have Bi+4 impurities and are composed completely of as
Ba2Bi+3Bi+5O6.
UV–Visible spectrophotometer was used to measure optical
peaks corresponding to (1,1,0), (
1,1,2), (2,2,0) and (1,1,4) (Fig. 1 properties of 1 mm thick BBO films. The Tauc plot shows that BBO
(b)). Scanning electron microscope (SEM) images (Fig. 1(c and d)) has both a direct and an indirect optical bandgap of 2.25 eV and
confirm that annealing increases the grain-size of the BBO films: 2.02 eV respectively (Fig. 2(b)), in line with previous reports [8].
from 150 nm in the as-deposited film to 400 nm for annealed Ultra-violet photoelectron spectroscopy was used to characterize
films. Energy-dispersive X-ray spectroscopy (EDS) shows that the band energy levels in BBO films. The UPS signal roll-over at the
BBO films are stoichiometric, (Fig. 1(e)). higher binding energy corresponds to the photoemission cut-off
Reported first-principle band-calculations predict that BBO from which the work function (/) of films can be extracted. UPS
is metallic [10] but experiments have found BBO to be a onset at the lower binding energy corresponds to electrons
semi-conductor [7]. To explain this discrepancy, charge dispropor- photo-emitted from the top of the filled states, from which the dif-
tion in bismuth atoms is generally considered. ference between Fermi level and valence band (EF
EV) can be
þ4 þ3 þ5 extracted. For BBO thin-film the work-function and EF
EV were
2Bi ¼ Bi þ Bi ð1Þ 4.22 eV and 1.6 eV, respectively (Fig. 2(c)). Given the indirect opti-
Due to the twin oxidation state, BBO is better represented as cal bandgap of 2.02 eV, the absolute position of the valence-band
Ba2Bi+3Bi+5O6 [7]. X-ray Photoelectron spectroscopy (XPS) was maxima (EV) and conduction-band minima (EC) in BBO films is
used to investigate the oxidation states of barium and bismuth in found to be at 5.82 eV and 3.8 eV, respectively, below the vacuum
films. To remove surface contamination, BBO films were etched level.

Fig. 1. (a) XRD pattern of phase pure BBO pellet. (b) XRD pattern of BBO thin-film deposited by PLD on TiO2/FTO Stack, before and after annealing (c) SEM image of as-
deposited thin-film (d) SEM image of annealed BBO thin-film (e) EDS spectra for annealed BBO thin-film, showing the expected stoichiometry.
220 A.S. Chouhan et al. / Materials Letters 210 (2018) 218–222
Fig. 2. (a) XPS spectra of Ba 3d and Bi 4f (b) The Tauc plot showing indirect and direct bandgap of BBO film. (c) UPS spectra for BBO showing photoemission cutoff and onset
(d) Band-diagram for BBO/TiO2 heterojunction.
TiO2 films have conduction and valence band edges at 4.1 eV
and 7.3 eV, respectively, below vacuum level [12]. Based on the
band-alignment between BBO and TiO2, TiO2 is expected to be an
effective electron transport layer for BBO. To help visualize, the
complete band-energy diagram of BBO/TiO2 heterojunction is
given in Fig. 2(d). The large valence band offset (1.48 eV) at
TiO2/BBO heterojunction is expected to block transport of holes
from BBO to TiO2, while the small conduction band offset is
expected to allow transport of electrons from BBO to TiO2. On
the other hand Au, with a work-function of 5.1 eV, is expected to
make a hole-conducting Ohmic contact with BBO. Overall, the
FTO/TiO2/BBO/Au heterojunction should function like a diode with
rectifying J–V characteristics. The band-diagram of the proposed
devices is shown in Fig. 3(a). J–V characteristics in dark show con-
firm the diode-like behavior (Fig. 3(c)). The FTO/TiO2/BBO/Au diode
has a rectification ratio (If/Ir) between 2 and 15, depending on the
applied voltage (Fig. 3(b)).
The device was illuminated from the bottom with simulated
AM 1.5 light, through the FTO/TiO2 layers. FTO and TiO2 are trans-
parent to visible light, so most of the photons are absorbed in BBO.
Ideally, the absorbed photons will lead to excess holes and elec-
trons which will drift towards one of the electrodes – holes
towards Au electrode and electrons towards FTO electrode – giving
rise to a photocurrent. Under AM1.5 light, the TiO2/BBO show a
1.75 increase in forward bias current at a forward bias of 1.5 V
(Fig. 3(c)). However, a clear photovoltaic response with short-
circuit current (Jsc) and open-circuit voltage (Voc) is not measured,
probably due to recombination losses at defects. The defects can be
localized at the TiO2/BBO interface and/or in the bulk of the poly-
crystalline BBO film. A more in-depth study of these defects is cur-
rently underway but outside the scope of this report.
4. Conclusion
BaBiO3 (BBO) is a promising low-bandgap absorber for all-
oxide thin-film solar cells. Polycrystalline BBO thin-films were
deposited using PLD. BBO has an indirect and direct bandgap of
2.02 eV and 2.25 eV respectively, so BBO films are expected to
absorb solar radiation with wavelength below 600 nm. The
valence-band and conduction-band edges of BBO are at 3.8 eV
and 5.82 eV, respectively, below vacuum level. Based on the posi-
tion of the band-edges, TiO2 is expected to be good electron-
transport layer for BBO and Au is expected to a hole-conducting
Ohmic contact. FTO/TiO2/BBO/Au heterojunction diode show rec-
tifying characteristics with a rectification ration of 10 at 1.6 V
 A.S. Chouhan et al. / Materials Letters 210 (2018) 218–222
Fig. 3. (a) Band diagram for the FTO/TiO2/BBO/Au heterojunction diode, (b) Diode rectification ratio as a function of bias voltage (c) J–V characteristics of the diodes in dark
and under AM 1.5 illumination.
bias. Under AM1.5 illumination, BBO films photo-generated
excess carriers which lead to significant 1.75 increase in current
at 1.5 V forward bias.
Acknowledgements
This work is supported in part under the U.S.
India Partnership
to Advance Clean Energy-Research (PACE-R) for the Solar Energy
Research Institute for India and the United States (SERIIUS), funded
jointly by the U.S. Department of Energy (Office of Science, Office of
Basic Energy Sciences, and Energy Efficiency and Renewable
Energy, Solar Energy Technology Program, under Subcontract DE-
AC36-08GO28308 to the National Renewable Energy Laboratory,
Golden, Colorado) and the Government of India, through the
Department of Science and Technology under Subcontract
IUSSTF/JCERDC-SERIIUS/2012 dated 22nd Nov. 2012. This work is
also supported by Department of Science and Technology under
grant number SR/S3/ME/045/2007. The authors would also like to
acknowledge the support from Young Faculty Research Fellowship
and PhD Fellowship under the Visvesvaraya PhD Scheme for Elec-
221
tronics and IT by Ministry of Electronics & Information Technology
(MeitY), Government of India.
Appendix A. Supplementary data
Supplementary data associated with this article can be found, in
the online version, at http://dx.doi.org/10.1016/j.matlet.2017.09.
038.
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