Solar Energy 257 (2023) 34–44

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Solar Energy
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Impact of charge-compensated Fe and Nb co-substitution on BaTiO3:

Bandgap and grain size reduction and enhanced bulk photovoltaic power of
Al/BFNT/Ag solar cell
L. Venkidu a, N. Raja a, b, B. Sundarakannan a, *
a
Department of Physics, Manonmaniam Sundaranar University, Abishekapatti, Tirunelveli 627012, Tamil Nadu, India
b
The Institute of Mathematical Sciences, C.I.T. Campus, Taramani, Chennai 600113, India

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

Keywords: The generation of above bandgap photovoltage using bulk ferroelectric materials has become a subject of great
Bandgap interest, however, their photocurrent density is limited by a broad bandgap and poor conductivity. To overcome
Photocurrent this limitation, we replaced aliovalent metal ions (Fe3+ and Nb5+) at the B-site of robust ferroelectric BaTiO3 and
Open circuit voltage
fabricated an Al/BaTi1-2xFexNbxO3/Ag photovoltaic device. Both the experimental and the theoretical studies
Ferroelectric photovoltaic
showed that bandgap was lowered to ~2.55 eV and hence absorption of wide energy range of the solar spectrum
was attained. An apt top electrode, reduced bandgap and domain size resulted in greater photocurrent density of
1.46 μA/cm2 and photovoltage of 8.31 V for Al/0.075BFNT/Ag solar cell in unpoled condition. This research
suggest that reduced band gap, mixed structural phases and nano-sized domains suffices greatest PV power
output while the large polarization and poling are not necessary prerequisites.

1. Introduction ferroelectric ceramics is their low power conversation efficiency (PCE)

Photovoltaic solar energy is obtained by converting sunlight into
electricity using a p-n junction based on the semiconductors (Artur­
oMorales-Acevedo, 2009). Photovoltaic (PV) technology is playing a
significant role in modern industry to alleviate the energy crisis.
Traditional junction-based solar cell technology is widely used, though
the raw material of silicon (Si) is relatively high price and the fabrication
process requires so sophisticated technology. The output voltage in
semiconductor based material is limited by their bandgap and the power
conversion efficiency (PCE) depends on the complicated interfaces of PV
devices. Conversely, non-centrosymmetric bulk ferroelectric materials
proficiently separate electron-hole pairs through their internal electric
field originating from the spontaneous polarization represented as the
bulk photovoltaic effect (BPV) (Kola et al., 2019; Fridkin, 2001). BPV
devices are not limited by the bandgap and therefore produce a larger
photovoltage (anomalous photovoltaic effect) than traditional junction-
based PV devices (Kola et al., 2019; Fridkin, 2001; Swain et al., 2019). In
recent times, bulk ferroelectric polycrystalline photovoltaics have
attracted special attention because of their low cost, good stability, facile
fabrication of the device, and high photovoltage (Kola et al., 2019;
Fridkin, 2001; Swain et al., 2019; He et al., 2019). The main drawback of
mainly due to their low photocurrent density under light which is
related to their low conductivity (Kola et al., 2019; Fridkin, 2001; He
et al., 2019). Therefore, how to simultaneously enhance the photocur­
rent and photovoltage of bulk ferroelectric ceramics and thereby power
conversion efficiency becomes an important issue to pushing forward
the practically realizable application of the ferroelectric photovoltaic
device. Recent research focused on the BPV effect in various ferroelectric
systems such as ferroelectric ceramics (Kola et al., 2019; Fridkin, 2001;
Swain et al., 2019; He et al., 2019), single crystals (Noguchi and Matsuo,
2021; Liu et al., 2022) thin films (Zenkevich et al., 2014; Fridkin, 2015;
Fan et al., 2014), polymers (Liu et al., 2013), organic and inorganic
ferroelectric composites (Fan et al., 2015). Recent research has proposed
explanations for the BPV with various models such as domain wall
theory (Matsuo et al., 2016), ballistic model (Kola et al., 2019), shift-
current model (Pal et al., 2018), interface effect (Schottky- junction ef­
fect) (Zhang et al., 2012) electrode and depolarization field effect (Gaoa
et al., 2016). Considering the above models, ferroelectric materials with
relatively small bandgaps and large polarizations are promising candi­
dates for photovoltaic applications because the materials can absorb
large amounts of the solar spectrum while simultaneously separating
charge carriers.

* Corresponding author.
E-mail address: sundarakannan@msuniv.ac.in (B. Sundarakannan).

https://doi.org/10.1016/j.solener.2023.03.058
Received 30 December 2022; Received in revised form 10 March 2023; Accepted 31 March 2023
0038-092X/© 2023 International Solar Energy Society. Published by Elsevier Ltd. All rights reserved.
L. Venkidu et al.
In this regard, BaTiO3 (BT) is considered one of the promising eco-
friendly ferroelectric perovskite materials with off-center distortions
from its centrosymmetric position and large spontaneous polarization
arising from the strong hybridization among the lowest unoccupied
Ti4+-d0 state and O-2p state at room temperature (Pal et al., 2021; Kola
et al., 2019). However, pristine ferroelectric BT can only be able to
absorb the ultraviolet (UV) region of the solar spectrum due to its wide
bandgap (3.2 eV) (Pal et al., 2018; Pal et al., 2021; Baiju et al., 2021).
Only 3.5 % of solar radiation is encompassed by UV light (wavelength
200–390 nm) yet visible light accounts for 40 % of solar energy
(wavelength 390–700 nm) (He et al., 2019). Therefore, constructing a
ferroelectric BPV device with a narrow bandgap (Eg) is an essential
factor for absorbing abundant light and maintaining ferroelectricity.
Recent studies have focused on substituting ions at A-site and/or
partially occupied non-d0 ions at the B-site of BT, as a way to reduce its
bandgap as well as to control ferroelectric properties. In this regard, a
large short-circuit current density of Jsc = 7.51 μA/cm2 was obtained
with A-site Sr-doped BT, but it didn’t induce anomalous photovoltage
(Voc < 1.5 V i.e. Eg = 3.04 eV) (Bai et al., 2021). However, the maximum
Voc of about 16 V was attained by BT co-doping with Bi and Li ions at the
A-site, but the determined photocurrent was within the range of nano
ampere (Pal et al., 2018). Kola et al. achieved a large Voc of 16 V with a
single substitution on B-site as Ag/BaTi1-xSnxO3/Ag PV device based on
the shift current model, but the current density was very low around ~
2nA/cm2 range (Kola et al., 2019). However, there have been only a few
reports on the effect of co-substitution on the B-site of bulk ferroelectric
photovoltaic materials up to now. For example, L.Wu et al. reported that
Ni2+ and Nb5+ co-doped (0.9)BaTiO3-(0.1)Ba(Ni1/2Nb1/2)O2.75 pro­
vided a decreased bandgap of ~ 1.5 eV and maintained remnant po­
larization ~ 5 μC/cm2 with obtained steady-state current of 8nA/cm2
(Wu et al., 2019). In contrast to other transition metal pair substitutions
(such as Mg3+-Nb-5+, Co3+-Nb5+, and Sc3+-Nb5+), the Fe3+-Nb5+ pair at
the B-site of BT has little effect on the bandgap reduction, and the sig­
nificant suppression in ferroelectricity is be expected to reduce the
photovoltaic properties of BT and decrease the device performance (Hao
et al., 2022; Das et al., 2018). However, there is a lack of experimental
evidence.
Also, it has been noted that in conventional electrode/ferroelectric/
electrode architecture, the net build-in electric field (Ebi) of the top and
bottom metal electrodes can form two back-to-back Schottky barriers
that deplete the electrode-ferroelectric interface (Zhang et al., 2012;
Zhang et al., 2013). From the prior reports, lowering the height of the
Schottky barrier with a low-work function metal electrode can induce a
large photovoltaic effect of the device (Zhang et al., 2012; Zhang et al.,
2013). Therefore, by choosing a suitable configuration of electrodes in
contact with ferroelectric materials, the photocurrents and photo-
generated voltage of the device may also be enhanced. In this regard,
aluminium (Al) and silver (Ag) electrodes have been selected as the top
and bottom electrodes respectively, for our PV device. Considering that
as a scope, we used a ferroelectric material such as BaTiO3 to provide the
bandgap reduction, enhance photocurrent, photovoltage and main­
taining ferroelectricity through charge-neutral chemical co-substitution
of aliovalent Fe3+ and Nb5+ at B-site with an asymmetrical electrode
architecture. Both Nb5+ and Fe3+ perform a typical charge compensator
and bandgap reducers respectively, with strong photo response, high
electron mobility, reduced recombination loss, easy crystallization,
controlled oxygen vacancies and good candidates in the ferroelectric
photovoltaic system. In particular, the reduction of the bandgap from
3.2 eV to 2.55 eV and enhanced photocurrent density of 1.46 µA/cm2
have been achieved with Al/0.075BFNT/Ag device, which is larger than
that of the Ag/BBLT/Ag (Pal et al., 2021) and Ag/BST/Ag photovoltaic
cells (Kola et al., 2019). We perform theoretical computations to further
envisage our experimental results and to find the reason for the bandgap
reduction.
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Solar Energy 257 (2023) 34–44
2. Experimental procedure
The bulk ceramics powder with the composition Ba(Ti1-2xFexNbx)O3
(BFNT) (x = 0.0 0.025, 0.05, 0.075) was fabricated by solid-state reac­
tion method (SSR) and represented as BT, 0.025BFNT, 0.05BFNT and
0.075BFNT. The starting materials of BaCO3 (99.9 %), TiO2 (99 %),
Fe2O3 (99.9 %), and Nb2O5 (99.99 %) were weighted according to the
stoichiometry of each composition. The mixed powder was ground using
a mortar and pestle for 30 min. The mixture was calcined at 950 ◦ C/5 hr
in the air atmosphere for all compositions. The calcined powder was
mixed with a binder of PVA, (polyvinyl alcohol) by manual granulation
in a mortar. The uniaxially compressed pellets are 13 mm in diameter
and 1 mm thick under 7-ton weight. The pellets were sintered at 300 ◦ C/
1hr to remove the PVA and then sintered at 1300 ◦ C/2hr in a furnace.
Room temperature X-ray diffraction measurements were carried out
using λ = 0.9654 Å the angle-dispersive X-ray diffraction (ADXRD) at
the beamline-12 installed in Indus-2 synchrotron source RRCAT Indore,
India. The FT-Raman spectrometer (Bruker, RFS 27) was used to probe
the structural phases of the samples. The instrument is equipped with a
Nd:YAG laser (1064 nm) as a source and an InGaAs detector (1024 ×
256). It has a resolution of 2 cm− 1. The measured data was fitted with
Lorentz function using Origin software (version:8.5) and fitting pa­
rameters such as peak position and line width were added in supporting
information. To determine the bandgap of the samples, a diffuse
reflectance spectrophotometer (DRS) (UV-2400 Schimadzu) was used.
The silver paste was applied on both sides of the polished pellets for
measuring the room temperature polarization–electric field (P-E loop)
hysteresis loops using a Precision ferroelectric tester system (Radian
technologies P-E loop tracer). The PHI - VERSAPROBE III is an advanced
instrument that was used to obtain X-ray photoelectronic spectra. It
features a multichannel detector and monochromatic Al-Kα source with
energy of 1486.6 eV, providing excellent resolution ranging from 0.1 to
40 eV for sample analysis and characterization. The peaks background
were subtracted for more accuracy in peak fitting, then the Gaussian
function was used to fit each elemental XPS peaks with Origin software
(version: 8.5) and the parameters were included in supporting infor­
mation. The Energy Dispersive X-ray Spectrometer Quantax 200 with X
Flash® 6130 was used for EDX and mapping studies. The photovoltaic
measurements were done using Sol3A Class AAA solar simulator with
Keithley electrometer (2400) measuring setup.
2.1. Device fabrication
The PV studies were conducted on the cell configuration of Al/
BFNT/Ag, where Al and Ag are the top and bottom electrodes, respec­
tively. BFNT pellets were mirror polished and thickness of 0.5 mm,
diameter of 11 mm and area of pellets of ~ 0.95 cm2. For photovoltaic
measurements, Aluminium (Al) electrode was coated on the top surface
of the sample (0.1-mm thickness of shadow mask) and bottom surface
was covered with silver (Ag) electrode using a thermal evaporation
technique with heating the samples at 400 ◦ C/30 min. Ag paste was used
to connect the electrodes and copper wire for the photovoltaic
experiment.
2.2. Computational details
Density functional theory (DFT) simulations were performed to un­
derstand the substantial decrease in the measured bandgap value of
BFNT samples. Calculations were carried out on a 3 × 3 × 3 supercell of
135 atoms using the projector augmented wave (PAW) (Hammer et al.,
1999) method as implemented in the Vienna Ab Initio Simulation
Package (VASP) (Kresse and Joubert, 1999). The generalized gradient
approximation (GGA) (Perdew et al., 1996) was used to depict the ex­
change and correlations of electrons. A Monkhorst pack scheme (Mon­
khorst and Pack, 1976) k-points mesh was set to 2 × 2 × 2, and a plane
wave energy cut-off of 520 eV was chosen. To account for any possible
L. Venkidu et al.
strong correlation GGA + U approach was employed, with U = 4 eV for
the 3d-orbitals of the Fe-ions (Chandra et al., 2013). Since GGA func­
tionals tend to underestimate the bandgap values for most materials,
HSE hybrid functional is used on optimized structures to compute the
density of states (DOS) (Das et al., 2018; Wahl et al., 2008). DOS was
sampled with 3 × 3 × 3 k-mesh and Gaussian smearing of 0.1 eV.
3. Results and discussion
3.1. Synchrotron angle dispersive X-ray diffraction (ADXRD)
The synchrotron X-ray diffraction patterns of BT, 0.025BFNT,
0.05BFNT and 0.075BFNT samples were measured at room temperature
(RT) and are shown in Fig. 1(a). No impurity phase was observed in all
samples. Peak indexed for ceramics samples agrees with recently re­
ported BFNT (Wang, 2011; Venkidu et al., 2018), which has a perovskite
cubic phase with space group Pm 3 m because of an increase in co-
substitution. The gradual decrement in the (2 0 0)pc peak splitting is
evidence as seen in the enlarged view in Fig. 1(b). The two-phase model
was confirmed for BT samples from synchrotron ADXRD is consistent
with laboratory X-ray diffraction described in our prior study (Venkidu
et al., 2018; Rubavathi et al., 2019), the two-phases of the BT sample are
tetragonal (P4mm) and orthorhombic (Amm2).
The Rietveld analysis program Jana2006 package (Petricek et al.,
2014) was used for crystal structure refinement. Rietveld refinement
parameters for specified space groups are the lattice parameters, atomic
coordinates, atomic occupancies, scale factor, 2θ zero shift, 36-degree
Legendre polynomials for background and pseudo-Voigt line shape
with asymmetry. As per the nominal composition of the perovskite ABO3
structure, the A site atomic occupancy is Ba, and the B site atomic
Fig. 1. (a) ADXRD patterns of BT and BFNT samples at RT. (b) Enlarged (0 0 2), (2 0 0) reflections from BT and BFNT samples. Rietveld refinement of pure BT refined
with (c) P4mm (d) P4mm + Amm2 space groups (e-g) Rietveld refinement ADXRD patterns of 0.025BFNT, 0.05BFNT and 0.075BFNT ceramics.
36
Solar Energy 257 (2023) 34–44
occupancy is Ti/(Fe & Nb). Fig. 1 (c) and 1 (d) show the Rietveld
refinement fit of the synchrotron ADXRD pattern of pure BT using a
single-phase model, tetragonal (P4mm) and two-phase model tetragonal
(P4mm) + orthorhombic (Amm2) respectively. The goodness of fit (χ2)
parameters for the P4mm and P4mm + Amm2 models are χ2 = 5.71 and
4.71, respectively. The poor fit or misfits (Bragg position, peak shape,
intensities) could not be improved satisfactorily, as shown in the insets
of Fig. 1(c) [indicated by circle]. In contrast, P4mm and Amm2 two-
phase models could well account for the Bragg profiles, peak position,
and intensities. Fig. 1(d) illustrates the excellent fit in an enlarged view
of (1 1 1)pc and (2 0 0)pc for the two-phase model. Synchrotron ADXRD
patterns of co-substituted BT, depicted in Fig. 1(e)-(g), were refined with
P4mm (T) and Pm 3 m (C) structural models which conform with earlier
reports (Wang, 2011; Venkidu et al., 2018). Rietveld refined structural
parameters such as lattice parameter, volume, c/a, atomic position, R-
factor (wRp), phase fraction (%wt), and goodness of fit (χ2) of BFNT (x =
0.0, 0.025, 0.05, and 0.75) samples are listed in Table S1. The ratios of
phase percentage of P4mm and Pm 3 m crystal structure are 85.3:14.7,
76.7:23.3 and 41.5:58.5 for x = 0.025, 0.05, and 0.075 respectively. The
mixed phase structures of BT and BFNT samples were then verified by
Raman spectroscopy as shown in Fig. S1(a–d), and a detailed description
is given in the Supporting Information.
According to Vegard’s law (Vegard, 1921), the lattice constant of the
cubic unit cell increases with the concentration of substitution ions, as
shown in Table S1. Also, the volume of the cubic lattice increases with x
due to larger ionic radii (r3+ 5+
Fe =64.5 pm and rNb = 64 pm) in weight
compared to the host radius Ti (r4+ Ti = 60.5 pm). The c/a ratio of the
tetragonal unit cell constantly drops with increasing x, which can be
attributed to the aliovalent replacement ions such as Fe3+ and Nb5+ at
the Ti4+ site that induces an internal stress field in BT ceramics. The
L. Venkidu et al.
structural phase transition originated from this internal stress field by
the broken Ti-O hybridization. The change in lattice parameters and the
volume of the unit cell is associated with oxygen-octahedral tilting and
distortion of octahedra. The change in lattice parameters and the volume
of the unit cell is associated with the oxygen-octahedral tilting and
distortion of octahedra. The oxygen-octahedral tilt can be determined by
the equation given below (Alonso, 2000; Venkidu et al., 2022):
180 − θ
θtilt = (1)
2
where θ is the angle between two Ti4+ ions in adjacent unit cells bonded
with a face-centered oxygen ion (Ti4+–O2--Ti4+). The octahedral tilting
of BT compared with 0.075BFNT is illustrated in Fig. 2(a) and (b). Also,
the octahedral distortion can be estimated by the following relation
(Alonso, 2000):
1∑6 [δn − < δ >]2
Δoct = (2)
6 n=1 < δ >
where δn and < δ > denote the individual and average interatomic
metal–oxygen bond length. With increasing substitution at the B-site,
the structure of BFNT ceramics is closer to pseudo-cubic with reducing
octahedral tilting and distortion from Table S2. The decreasing octa­
hedra tilt could affect the bandgap of the samples.
3.2. X-ray photoelectron spectroscopy
To investigate the electronic states of each element in BaTi1-
2xFexNbxO3, the X-ray photoelectronic spectra were recorded. The
detailed survey and core-level spectra of Ba and Ti for BT, 0.025BFNT
and 0.075BFNT are discussed in the supporting information (Fig. S2).
Fig. 3(a) denotes that the binding energy of the Ti-2p spectrum shifted
into a lower energy level with increasing substitution. This can be
attributed to the local electric field. This local electric field induced to
decrease in the bandgap of the ferroelectric material (Luo et al., 2018).
As a result, the lowering bandgap influenced the intermediate charge
transfer, thus can suppress the resistivity of the material.
Fig. 3(b) illustrates the asymmetric nature of core-level Fe-3d spectra
of 0.025BFNT and 0.075BFNT and it can be split into Fe-2p3/2 and
Fe2p1/2 spin states. For 0.025BFNT, the XPS spectra can be deconvo­
luted into the characteristic peaks of Fe2+ and Fe3+ assigned to ~ 708.8
eV, ~713.7 eV and ~ 710.8 eV, 722.06 eV, respectively. The absence of
Fe2+ peaks in 0.075BFNT indicates the suppression of the oxygen va­
cancies. Additionally, the satellite peaks around ~ 718.12 eV and 720.1
eV were also found in Fig. 3(b). These results are matched with previous
literature (Luo et al., 2018; Srisombat et al., 2013). The absence of
doublet peaks around 719.9 eV and 706.7 eV indicates that the
substituted iron (Fe) is ionized and not metallic (Xie et al., 2012). The
photoelectronic spectra around ~ 204.3 eV and ~ 208.3 eV represent
Fig. 2. Enlarged view of two nearby linked TiO6 octahedra with octahedral tilting of (a) BT and (b) 0.075BFNT samples.
37
Solar Energy 257 (2023) 34–44
the Nb-3d5/2 and Nb-3d3/2 states respectively, were seen in Fig. 3(c) for
0.025BFNT and 0.075BFNT samples. The oxidized state of Nb is 5 + for
these peaks.
The core-level spectra of O-1 s of BT, 0.025BFNT and 0.075BFNT are
shown in Fig. 3(d). The O(I), O(II), and O(III) spectra represent the
lattice oxygen bonding with Ti/Fe/Nb, oxygen vacancies, and adsorbed
oxygen is assigned at ~ 529 eV, ~531 eV, and ~ 533 eV respectively.
The binding energy and area under the fitting curve of O(I), O(II), and O
(III) are listed in Table 1, where the area of the oxygen vacancy tends to
decrease with increasing substitution. This results from the simulta­
neous doping of donor (Nb5+) and acceptor (Fe3+) at the B-site can
neutralize the charge carriers and avoid the oxygen vacancies (Ismail,
2019). The reaction can be written using Kroger-Vink notation as
follows;
Fe2 O3 + Nb2 O3 →2Fe’Ti + 2Nb⋅Ti + 6Oo (3)
Hence, the samples are obeying the following condition of charge
neutrality (Heywang et al., 2008)
∑
n ∑
n
xAi nAi + xBi nBi = 6 (4)
i=1 k=1
where, xAi , xBi (for x = 0.0, 0.025, 0.05 and 0.075) are the fractions of
ions and nAi , nBi are the valances of ions (Ba-2+, Ti-4+, Fe-3+, Nb-5 + )
at the A & B sites, respectively.
3.3. Hysteresis loop
To find the impact on ferroelectricity under B-site substitution of BT
ceramics, the Polarization-Electric field (P-E) hysteresis loop was
measured at room temperature with a 30 kV/cm applied field, as shown
in Fig. 4. The shape of the P-E hysteresis loop tends to be unsaturated
with increasing metal substitution. The parameters such as remnant
polarization (Pr), spontaneous polarization (Ps), and coercive field (Ec)
were decreased with increasing x as in Fig. 4. It was suggested in the
literature that the reduction of ferroelectricity upon metal doping due to
the formation of oxygen vacancies leads to an increase in the leakage
current in ferroelectric samples (Rubavathi et al., 2019). However, in
the current study, the production of oxygen vacancies is strongly
restricted by the charge compensator Nb5+ which is further validated by
the XPS results of the Fe-2p and O-1s spectra. Therefore, the ferroelec­
tricity in BT ceramics was suppressed by the following features. The
origin of local polarization in BaTiO3 ceramics can be attributed to the
off-center displacement of d0 Ti-ion about the oxygen octahedral cage.
The inclusion of bigger-size ions helps reduce the octahedral distortion
and leads to suppressing the Ti-O off-center displacement of BT ce­
ramics. According to modern ferroelectric theories, the partially occu­
pied transition metal d-ion replaced at Ti-site supports centrosymmetric
L. Venkidu et al. Solar Energy 257 (2023) 34–44

Fig. 3. (a) XPS binding energy spectra of Ti-peak shifting and high-resolution core-level spectra of (b) Fe-2p, (c) Nb-3d and (d) O-1 s elements.

3.4. Bandgap
Table 1
Deconvolution of O-1s peak parameters for BT and BFNT samples obtained from
The DRS was used to investigate the optical characteristics of BT and
XPS measurement.
metal-substituted BT in the wavelength region of 200–900 nm as shown
Sample O(I) O(II) (%) O(III)(%) in Fig. 5 (a). Fig. 5 (a) illustrates the absorbance spectra of the samples;
Binding Peak Binding Peak Binding Peak in which all the substituted samples exhibit a shoulder around ~
energy area energy area energy area 400–500 nm (encircled region) and its absorbance increases along with
(eV) (%) (eV) (%) (eV) (%)
x and it broadens toward lower energy ranges. The bandgap energy of
BT 528.17 28.27 533.59 67.52 537.83 4.21 BT and BFNT samples can be estimated using the Tauc plot as shown in
0.025BFNT 527.48 26.59 531.41 70.15 534.06 3.24 Fig. 5(b) and listed in Table 2. The optical bandgap of pure BT (3.25 eV)
0.075BFNT 527.64 33.79 530.43 55.73 532.17 10.46
decreases with increasing metal substitution at the B-site. According to
previous studies, the valence band (VB) is assigned to the O-2p orbital
and therefore simultaneously reduces the off-center distortion needed and that of the conduction band (CB) to the Ti-3d0 orbital in pure BaTiO3
for ferroelectricity (Hill, 2000; Pal et al., 2020). The following theoret­ (Phuyal et al., 2019), which generates a bandgap energy of 3.25 eV.
ical calculations demonstrate the proof that the non-d0 Fe3+ state per­ Meanwhile, non-d0 metals like Fe3+ replaced on the B-site might affect
turbs both the valence and conduction band of BFNT materials. the electronic band structure due to the anisotropic crystal fields of the
Therefore, the ferroelectricity of BT was destabilized by the alterations octahedron created by the metal–oxygen interactions (Alkathy et al.,
in the hybridization of Ti-3d to O-2p orbital. These results are consistent 2021). In this context, the Fe/Ti/Nb could be treated as a point charge,
with the structural discussions and indicate that the ferroelectricity was and their spatial arrangement affects the energy of the d-orbital of the
suppressed by co-substitution. central metal atom. According to crystal field theory, a partially occu­
pied 3d orbital in an octahedral crystal field is divided into two eg

38
L. Venkidu et al. Solar Energy 257 (2023) 34–44

a larger bandgap in perovskite materials (Alkathy et al., 2021; Wang

et al., 2014). Here, the electronegativity difference of Nb-O (1.84) and
Fe-O (1.61) is much less than that of Ti-O (1.9), therefore the reduced
bandgap of BFNT largely depends on Fe3+ metal ion.
The d-orbital metal ions and the p-orbital of oxygen ions can be
defined using the linear combination of atomic orbitals model (LCAO). If
the density of the state is deemed constant, the following equations show
that the probability of an average d-orbital mixing (rd) in the valence
band can be calculated based on the bandgap (Eg) and bandwidth (EB)
(Ismail, 2019; Wolfram and Ellialtioglu, 2006);
1 η
rd = + ln(η) × 100 (5)
2 2(1 − η)

where η means the covalent mixing and it lies between 0 and 1. The
value of η can be determined by the following equation:
Eg
η= (6)
2EB
From Table 2 η values tend to be small with increasing metal
Fig. 4. Polarization- Electric field (P-E) hysteresis loop of BT and BFNT samples
at RT.
Table 2
Bandgap (Eg), Bandwidth (EB), η, and probability of d-orbital mixing obtained
orbitals and three t2g orbitals (Kola et al., 2019). This field causes eg to
for BT and BNFT samples.
evolve into one high energy state (d2x -d2y) and one low energy state (d2z ),
whereas t2g evolves into one high energy state (dxy) and two low energy Sample Eg (eV) EB (eV) η rd (%)

levels (dzy and dzx) (Alkathy et al., 2021b,a). As a result, the existence of BT 3.25 3.26 0.49816 15
the 3d state between CB and VB with Fe3+ ions is indicated by the inter- 0.025BFNT 2.68 3.14 0.42814 18
0.05BFNT 2.64 3.12 0.42290 18.5
band transition from d2z to dx2-dy2. Previous reports suggested that the
0.075BFNT 2.55 3.10 0.37958 19
large electronegativity difference between metal and oxygen can induce

Fig. 5. Absorption spectra of BT and BFNT samples as a function of (a) wavelength, and (b) Tauc’s plot. The total density of states (TDOS) and projected density of
states (PDOS) for the structures (c) tetragonal BT and (d) cubic 0.075BFNT. (In both graphs, the Fermi level is set to zero.).

39
L. Venkidu et al.
substitution indicating the strong covalent mixing.
The value of EB is found from the equation below:
√̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅
( )2
Eg
EB = +8(pdπ)2 (7)
2 circuit voltage (Voc) curve were measured under both dark and light
For perovskite samples, the value of pdπ = 1 eV (Alkathy et al., 2021)
and the calculated EB ; η and rd are listed in Table 2. The results obtained
here are evidence that the mixing of d-orbitals into valence bands is a
function of bandgap (Eg ). The decreasing bandgap suggests an increased
probability of d-orbitals mixing into the valence band, which is verified
by the DFT calculations as shown below.
3.5. Density functional theory
A 3 × 3 × 3 supercell was constructed using the experimental lattice
parameters of cubic BFNT. Four Ti ions in the supercell were replaced by
two Fe and two Nb ions to match the experimental doping concentration
(x = 0.075). Based on the dopant-dopant distance, eight distinct con­
figurations were identified as illustrated in fig.S3 and the ground state
energy calculations were performed to understand the effect of the
substitution ion interaction over the ground state energy. It is observed
that the calculated ground state energies differ relatively, as tabulated in
Table S5 and the optimized structure of the minimum energy
configuration-2 is used to calculate DOS.
Fig. 5 (c, d) shows the computed electronic density of states corre­
sponding to the tetragonal-BT and cubic-0.075BFNT structures in their
minimal energy configuration. The calculated bandgap values for pure
BT and 0.075BFNT were 3.26 and 2.49 eV, respectively. These values
are in line with the experimental results of 3.2 and 2.55 eV. The valence
band of pure BT is mostly occupied by the O-2p state, whereas the
conduction band consists primarily of the Ti-3d state, as seen in Fig. 5(c).
The estimated valence bandwidth is − 4.75 eV, which is consistent with
the DFT results from previous papers (Dahbi et al., 2021; Pinto and
Stashans, 2002).
It is remarkable to notice from Fig. 5(d) that on metal substitution at
B-site, the Ti-3d and O-2p orbital still dominate the CB minimum and VB
maximum of the BFNT respectively. With increasing substitution level to
x = 0.075, the formation of new 3d states of Fe and Nb was observed at
both the valence and conduction bands as shown in Fig. 5(d). The PDOS
in Fig. 5(d) shows the hybridization of Fe ion 3d-states with BT host
electronic states, close to the valence band maximum. The incorporation
of Fe-3d states localized in VB has resulted in stronger hybridization
with the O-2p state near the valance band edge than that observed for
Ti–O hybridization. HSE calculations clearly show the formation of new
states at the top of the valence band edge with predominant Fe 3d
character, which primarily decreases bandgap. Additionally, strong d–d
interaction between Ti–3d and Fe/Nb – d state at top of VB has led to the
accumulation of carriers near bottom CB as well as top VB edges. Also,
the contribution of lower Fe-3d (~-7.2 to − 6.7 eV) state increases the
width of VB from ~ -4.75 eV (i.e. BT) to ~ -8 eV as shown in fig. S4. Such
enhancement is beneficial for the mobility of the photogenerated charge
carriers within the material system as from an earlier report (Hsuan-
Chung et al., 2012). On the other hand, Fig. 5(d), the substitution of Fe
and Nb in BFNT results in the hybridization of Nb–O and Fe-O at the
conduction band, which effectively separates the photogenerated
electron-hole pair (Wang et al., 2018). Furthermore, this hybridization
between Fe-3d and Nb-3d with O-2p pushes the CB minimum towards
lower energy levels resulting in the significant reduction of the con­
duction band edge from 3.26 to 2.49 eV, as shown in Fig. 5(d) is the
reason for minimizing the photoexcitation energy of charge carriers. The
red shift of CBM combined with an increase in mobility of photo­
generated charge carriers along VB due to Fe–O & Nb–O in BFNT leads
to the expectation of improvement in photocurrent density.
40
Solar Energy 257 (2023) 34–44
3.6. Photovoltaic characteristics
To evaluate the photovoltaic (PV) response of BT ceramics with Fe
and Nb substitution, the short-circuit current density (Jsc) vs open-
irradiation of 100 mW/cm2 and the results are illustrated in Fig. 6(a).
Surprisingly, all the BT samples exhibit bulk photovoltaic characteristics
with Jsc in microampere and large Voc as listed in Table 3. It was noted
that the open-circuit voltage and short-circuit current density increased
under increasing the substitution and achieved 8.31 V and 1.46 µA/cm2
respectively, for 0.075BFNT. The large Voc (i.eVoc > Eg) justifies that it is
an anomalous photovoltaic effect. Further, the following relation can be
used to calculate the photoresponsivity (R) and specific detectivity (D)
of the device (Ma and Yang, 2019):
R=
Jsc
(8)
I
[ ]
D=
R
(9)
(2qJdark )1/2
where I means the light intensity (100 mW/cm2), q refers the elec­
tron charge (1.6 × 10-19C) and Jsc, Jdark stands for the short-circuit
current density and dark current density of the device, respectively.
According to Table 3 the maximum R and D values of 1.46 × 10-2 mA/W
and 3.57 × 108 Jones were obtained for Al/0.075BFNT/Ag device,
respectively, which is remarkably larger than prior reports (Ma et al.,
2017; Ma and Yang, 2019).
The time dependent photocurrent density curve for all samples was
measured under 100 mW/cm2 light irradiation with an ON/OFF
switching time of 60 s and a bias of 10 V, as shown in Fig. 6(b). It was
found that the photocurrent density of all ceramic samples increased
when the light was turned on, then decayed and returned to its original
state once the light source was turned off. This clearly shows that all of
the devices have a good ON/OFF switching response. Fig. 6(c) displayed
the performance of time resolved photocurrent density of BT and
0.075BFNT device. The photocurrent of both devices increased quickly
when the light source was turned on, followed by a modest improvement
in Jsc, until achieving saturation. After the light source is switched off,
the photocurrent was rapidly falls for both the devices, then slowly de­
cays until returning to the initial condition of Jsc (dark current). Such
rise and decay responses of both devices were detected using exponen­
tial fitting of the experimental data using the relation below;
[ ( )] [ ( )]
− t − t
I = I0 + Cexp + Dexp (10)
τ1 τ2
where I0 represents the steady state photocurrent, C and D are con­
stants, t is time and τ1 and τ2 are the relaxation time constants (Jin et al.,
2014). The excellent fitted photo response curves of BT and 0.075BFNT
samples as presented in Fig. 6 (c) where τr and τd are time constants for
rising and decay edges, respectively. The estimated time constants of BT
are: τr1 = 7.5 s, τr2 = 17.3 s, τd1 = 10.1 s, τd2 = 12.3 s and 0.075BFNT are:
τr1 = 7.0 s, τr2 = 8.6 s, τd1 = 10.6 s, τd2 = 13 s. The rising constants are
associated with the carrier creation process, whereas the decay con­
stants are associated with the carrier recombination process. As a result,
BT has a longer duration for carrier generation than 0.075BFNT, yet the
decay constants of both devices are comparable.
The PV properties of bulk BT ceramics depend on various factors
such as material thickness (Lu et al., 2019), the work function of the
electrode material (Zhang et al., 2013), light intensity (Pal et al., 2018),
applied poling field (Pal et al., 2021), electrical conduction and behavior
of domain walls (Matsuo et al., 2016), ferroelectric polarization (Pal
et al., 2021) and electrode/ferroelectric/electrode interface (Zhang
et al., 2012; Zhang et al., 2013). However, the bulk photovoltaic effect is
largely dependent on the interface of the top electrode/ferroelectric
material/bottom electrode architecture. According to Fan et al. the
L. Venkidu et al. Solar Energy 257 (2023) 34–44

Fig. 6. (a) J-V characteristics of BT and BFNT samples. (b) Time-dependent photocurrent density (J-t) curve. (c) Time-resolved photocurrent density rise and decay
curves of BT and 0.075BFNT device (d) Graph comparing Voc, Jsc and PV power of BFNT with other BT-based ferroelectric photovoltaics.

0.325 eV (if Al is a top electrode) and φB = 0.68 eV (if Ag is a top

Table 3
electrode). Comparatively, the barrier height is much smaller when Al
Photovoltaic parameters determined for BT and BFNT samples.
works as the top electrode of the device than Ag. In addition, the
Sample Jsc (μA/ Voc FF η R D enhancement of the PV response in pure BT can originate from the
cm2) (Volts) (%) (mA/ (× 108
coexistence of the tetragonal and orthorhombic phases. According to the
W) Jones)
shift current theory, the enhancement of PV properties in KNbO3 is
BT 0.69 3.40 0.290 0.0006 0.0069 1.688
achieved in excess in mixed of orthorhombic and rhombohedral phases
0.025BFNT 0.22 5.14 0.297 0.0003 0.0022 0.538
0.05BFNT 0.97 7.68 0.307 0.0022 0.0097 2.373 compared to that of the tetragonal phase (Wang and Rappe, 2015).
0.075BFNT 1.46 8.31 0.332 0.0041 0.0146 3.572 Moreover, Kola et al. reported that maximum Voc was attained in B-site
doped BT at a larger orthorhombic phase than that of the tetragonal
single phase (Kola et al., 2019). Therefore, the greater bulk PV response
comparative study of the bulk photovoltaic effect on Ti/BTO/SRO and in pure BT in this study than in Pal et al. (2018) result is based on the
Pt/BTO/SRO combinations revealed a short-circuit current (Isc) of about structural symmetry and low work function metal electrode.
1.2 nA and 0.3 nA, respectively (Fan et al., 2017). This result suggested The greatest variation in PV outcomes from metal substitution de­
that the suppression of photocurrent in Pt/BTO/SRO interface was due pends on the bandgap, grain size, domain size, and dielectric and
to the large work function of the Pt electrode (φPt = 5.5 eV) than Ti ferroelectric characteristics (Matsuo et al., 2016). The existence of an
electrode (φTi = 4.33 eV). A similar PV study was conducted for Mg/ aliovalent Fe3+-Nb5+ pair in BaTiO3 greatly alters the properties of both
PLZT/ITO, Pt/PLZT/ITO, and Ag/PLZT/ITO cell configurations, where the valence and conduction bands, according to theoretical DFT calcu­
the open-circuit voltage and short circuit current density increased in lation. The bandgap of the ferroelectric material decreased considerably
the order of large work function metal electrodes to less work function from 3.25 eV to 2.55 eV when B-site replacement increased. This
metal electrodes (Bai et al., 2021). Moreover, Subhajit Pal et al. reported reduction in bandgap potentially absorbs the maximum visible region of
that the pure BT ceramics with a cell configuration of Ag/BT/Ag provide the light source as shows in Fig. 5(a). Bandgap reduction is an important
a Voc of 2 V and Jsc of 3 nA/cm2 under the illumination of 160 mW/ cm2 component covering a wide area of the light source and is beneficial to
with the device thickness of about 0.5 mm (Pal et al., 2018). Although in increase the current density of the device. Additionally, the XPS findings
our case, Al/BT/Ag provides Jsc of 0.65 μA/cm2 and Voc of 3.4 V even of Fig. 3(b) demonstrated that the formation of minor oxygen vacancies
under 100 mW/cm2 illumination with a similar thickness as pure BT. was obtained in 0.025BFNT, however in the 0.075BFNT sample, the
Here, the height of the Schottky barrier (φB) can be determined by the oxygen vacancies were substantially controlled by the lack of Fe2+ state.
difference between the work function of the metal electrode (φM) and The oxygen vacancy suppression in 0.075BFNT increases the Jsc of the
the electron affinity (χ) of FE material (Neamen, 2012). Considering that device more sharply than that in 0.025BFNT by reducing the recombi­
the work functions of Al and Ag are 4.125 eV and 4.48 eV respectively nation between oxygen vacancies and hopping electrons.
and the electron affinity of BT is 3.8 eV (Wang et al., 2015), then φB = Meanwhile, the open-circuit voltage of the device can be expressed

41
L. Venkidu et al.
as (Pérez-Tomás et al., 2018)
Voc = Epv .d (11)
where Epv denotes the photovoltaic field and d is the distance be­
tween the metal electrodes. This equation suggests an anomalous
photovoltaic effect, in which the open-circuit voltage of the device is
substantially higher than the bandgap of the material and is not con­
strained by the bandgap of bulk ferroelectrics. For instance, A. M. Glass
et al. in Fe-doped LiNbO3 (Glass et al., 1974) attained the anomalous
photovoltage of around 1,000 V. Generally, the PV response of bulk
ferroelectrics depends on the grain size and domain size effect. In an
earlier study, we described the microstructure of Fe and Nb-modified
BaTiO3. Currently, the microstructure of 0.075BFNT was analyzed and
the results are shown in Fig. S5. Additionally, elemental analysis of all
samples was conducted using EDX mapping & spectra as depicted in
Fig. S6; further details regarding microstructure analysis can be found in
Supporting Information. According to Frank et al. it has been proposed
that the generated high photovoltage in ceramics is proportional to the
number of grains, i.e., high photovoltage is generated from the sum­
mation of individual photo-emf across the grains (Brody and Crowne,
1975). Consistent with this result, the number of grains in smaller grain
sizes is greater than in larger ones, resulting in higher output photo­
voltage with increasing metal substitution. In addition, the grain size of
BaTiO3 is co-related with the domain size by the simple relationship as
follows (Lv et al., 2020)
d∝g1/2 (12)
where g and d denote the grain and domain size of the ceramics,
respectively. The domain size will also be affected by changes in grain
size. Earlier reports stated that the open-circuit voltage of ferroelectrics
was induced by the addition of an electrostatic potential difference be­
tween the domain walls (Matsuo et al., 2016). Here the grain size of
BaTiO3 ceramics was decreased upon metal substitution in the order of
3.6 μm, 0.68 μm and 0.51 μm for x = 0.0, 0.025, and 0.05 respectively,
from our previous findings (Venkidu et al., 2018) and fig. S5 reveals the
grain size of x = 0.075 was 0.14 μm. Thus, the smaller grain size results
in smaller domain size and the smaller size of domains have a larger
number of domain walls and achieve a higher open-circuit voltage of the
device. As a result, the reduced grain size increased the photovoltage of
the Al/BFNT/Ag device.
The aforementioned findings demonstrated an inventive strategy to
enhance both the photocurrent and photovoltage of BFNT ceramics.
Numerous investigations have indicated that the large ferroelectric po­
larization is a crucial component for the anomalous photovoltaic effect,
in which the photovoltage of the ferroelectric material increases sub­
stantially above the bandgap of the material meanwhile the generated
photocurrent values are very low in the range of nano to pico ampere
(Hammer et al., 1999; Kresse and Joubert, 1999; P. Pal et al., 2021; S.
Pal et al., 2021; Pan et al., 2021; Su et al., 2019; Xiang et al., 2019). Even
for the pure BT sample, the anomalous photovoltage of around 3.4 V was
attained due to the larger polarization and non-centrosymmetry ortho­
rhombic + tetragonal phase structure, as confirmed by P-E loop and
ADXRD analysis respectively. However, the large anti-bonding property
between Ti-3d and O-2p results in a wide bandgap (Eg = 3.25 eV), hence
the generated photocurrent was quite low (Jsc = 0.65 μA/cm2). Ac­
cording to the first-principle calculations based on the shift current
mechanism, maximum polarization is not a necessary condition for the
BPV response, although inversion symmetry must be broken (Pal et al.,
2018, 2021). According to the above mechanism, the non-
centrosymmetric ferroelectric tetragonal phase coexists with the para­
electric cubic phase in metal-substituted BT, as proven by ADXRD and
Raman investigations, where the remnant polarization was reduced
compared to pure BT, but the photovoltaic parameters and PV power
(Voc × Jsc) of the 0.075BFNT device were remarkably improved and
comparable with recent studies, as shown in Fig. 6(d) and Table S7.
42
Solar Energy 257 (2023) 34–44
Therefore, we concluded from the overall experimental results and
theoretical DFT calculations that the high photoresponsivity, large
detectivity of solar spectrum with concurrent enhancement of both
photocurrent and photovoltage in bulk ferroelectric BT is possible
through appropriate co-substitution of aliovalent Fe3+-Nb5+ pair, which
is successfully tuning the bandgap to absorb abundant regions of the
solar spectrum, controlling oxygen vacancies to reduce the e-h recom­
bination rate, minimizing the grain size and using a low work function
top electrode.
4. Conclusion
In summary, the structural, optical, electrical and photovoltaic
properties of BaTi1-2xFexNbxO3 (x = 0.0, 0.025, 0.05 and 0.075) were
discussed. The synchrotron ADXRD data combined with Raman spectra
confirmed that the pure BT possesses the mixed phase of tetragonal +
orthorhombic at RT. Increasing the Fe3+ and Nb5+ substitution at B-site
modifies the structure to tetragonal + cubic symmetry, reducing octa­
hedral tilt, and distortion along with increasing internal stress field
contributed to tuning the bandgap into a lower energy state of 2.55 eV
and thus can efficiently absorb the larger area of the solar spectrum
(~500 nm). To comprehend the drastic decrement in the bandgap of
BFNT samples from pristine BT, DFT studies were carried out. It was
found that the band gap value decreases drastically from 3.28 eV to 2.49
eV because of the aliovalent Fe3+-Nb5+ ions contributions to the valance
and conduction band. The tuned bandgap develops the metal–oxygen
covalent character and enhances the charge carrier mobility of the de­
vice. Further, XPS analysis depicted a clear picture about suppression of
oxygen vacancies in 0.075BFNT through Fe-2p and O-1 s spectra.
Meanwhile, the grain size reduction is responsible for the continuous
growth of Voc. From time resolved J-t fitted curves, the slow response
rise time constant was improved for 0.075BFNT than BT device. Here,
the simultaneous enhancement of Jsc and Voc does not follow the
maximum polarization concept. Finally, an apt top electrode, reduced
bandgap, small grain size and suppression of oxygen vacancies are
contributed to enhance the PV power of Al/0.075BFNT/Ag device to ~
12 μW/cm2.
CRediT authorship contribution statement
L. Venkidu: Conceptualization, Methodology, Software, Writing –
original draft. N. Raja: Investigation, Software. B. Sundarakannan:
Conceptualization, Methodology, Validation, Investigation, Writing –
review & editing.
Declaration of Competing Interest
The authors declare that they have no known competing financial
interests or personal relationships that could have appeared to influence
the work reported in this paper.
Acknowledgments
This study was financially funded by the University Grant
Commission-Basic Science Research Fellowship scheme (F.No:25-1/
2014-15(BSR)/7-305/2010/(BSR), and L. Venkidu is thankful to the
government of India for funding this study. The author also thanks Dr. A.
K Sinhan, Dr. Archana Sagdeo, and Mr. Mandvendra Narayanan Singh,
Raja Ramanna Centre for Advanced Technology, Indore, India, for their
help in Angle Dispersive X-ray Diffraction (ADXRD) beamline-12 (BL-
12) at Indus-2 synchrotron radian source. The fabrication of the mask
(Al/BFNT/Ag) was carried out at the Center for Nano Science and En­
gineering (CeNSE), Indian Insitute of Science, Bangaluru, under the
INUP program funded by the Ministry of Education (MoE), Ministry of
Electronics and Information Technology (MeitY), and Nanomission,
Department of Science and Technology (DST), Government of India. The
L. Venkidu et al. Solar Energy 257 (2023) 34–44

author L.Venkidu sincerely thanks Ms. Adithi for their help during the Heywang, W., Lubitz, K. and Wersing, W. eds., 2008. Piezoelectricity: evolution and
future of a technology (Vol. 114). Springer Science & Business Media.
mask fabrication. SERB grant (CRG/2019/006990) is also acknowl­
Hill, N.A., 2000. Why Are There so Few Magnetic Ferroelectrics? J. Phys. Chem. B 104,
edged for the P-E loop tester. N. Raja gratefully acknowledges C. Kamal, 6694–6709. https://doi.org/10.1021/jp000114x.
Raja Ramanna Centre for Advanced Technology, Indore, India for the Hsuan-Chung, W.u., Li, S.-H., Lin, S.-W., 2012. Effect of Fe Concentration on Fe-Doped
fruitful discussions and help in calculations. N. Raja also acknowledges Anatase TiO2 from GGA + U Calculations. Int. J. Photoenergy 2012, 823498.
https://doi.org/10.1155/2012/823498.
Rajesh Ravindran and The Institute of Mathematical Sciences, Chennai, Ismail, M.M., 2019. Ferroelectric characteristics of Fe/Nb co-doped BaTiO3. Modern
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