pubs.acs.

org/EF Article

Manifestation of the Enhanced Photovoltaic Performance in Eco-

Friendly AgBiS2 Solar Cells Using Titanium Oxynitride as the
Electron Transport Layer
Akhil S.,† Mithun Prakash Ravikumar,† Mohammed Jalalah, Mabkhoot Alsaiari, Farid A. Harraz,*
Sakar Mohan,* and R. Geetha Balakrishna*
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sı Supporting Information

ABSTRACT: In this study, titanium oxynitride with empirical composition of TiON is developed using a sol−gel and ammonia-
gas-assisted thermal nitridation process. The obtained TiON phase is employed as the photoanodic electron transport layer (ETL)
in a silver bismuth sulfide (AgBiS2) quantum-dot-sensitized solar cell (QDSSC) device and compared to a QDSSC consisting of
commercial TiO2 as the ETL. The obtained X-ray photoelectron spectroscopy spectra and Mott−Schottky plots of the samples
suggested that the valence and conduction bands of TiON are significantly shifted (EVB = 2.9 eV and ECB = −0.3 eV) with respect to
that of TiO2 (EVB = 1.88 eV and ECB = −0.51 eV), which eventually decreased its band gap energy to 2.46 eV compared to TiO2 (3.2
eV). A decrease in the charge transfer resistance (Rct = 38.2 Ω) and improvement in carrier lifetime (τ = 5.3 ms) are observed in the
developed TiON device. The work also endorses the use of eco-friendly green quantum dots of AgBiS2 as photoabsorbers in solar
cells. Although the photovoltaic performance is not found to be greater, the demonstration of the enhanced performance of the
TiON-based device with ∼50% enhancements, owing to its improved open circuit voltage and current density by 20 and 35%, is
achieved in this work. Titanium oxynitride can, hence, be considered a suitable alternative to existing commercial TiO2 in all
applications that involve solar energy conversion.

■ INTRODUCTION
Quantum dot solar cells (QDSCs) are potential candidates in
third-generation photovoltaics (PVs) and can successfully
compete with other PV technologies.1,2 Their ability to create
multiple excitons and enhance dynamic light absorption ranges
have enabled them to achieve power conversion efficiencies
nearing 14%.3 However, usage of heavy metals, such as Cd and
Pb, in the chalcogenide-based quantum dots in quantum-dot-
sensitized solar cells (QDSSCs) remains a major barrier for
their commercialization as a result of the toxicity involved. To
overcome this, researchers are working on less toxic, green
quantum dots as photosensitizing materials in QDSSCs. For
this, heavy-metal-free chalcogenide-based ternary green
quantum dots with an ABX2 structure (A = Ag and Cu; B =
Bi, Sb, and In; and X = S and Se) are better alternatives.4 Silver
bismuth sulfide (AgBiS2) QDs with an optimal band gap
energy of 1−1.5 eV and high absorption coefficient can be
favorable for solar cell applications.5,6 On the other hand, it
should be noted that the architecture of QDSSC generally
consists of the electron transport layer (ETL), photosensitizer
(i.e., QDs), hole transport layer (HTL), and counter electrode
(CE). The misalignments of energy levels of the ETL and
HTL across the interfaces lead to recombination losses in the
device and become a major factor for the poor performance of
the device. TiO2 is one of the well-recognized materials as the
Received: July 8, 2022
Revised: October 20, 2022
Published: November 14, 2022

© 2022 American Chemical Society https://doi.org/10.1021/acs.energyfuels.2c02287

14393 Energy Fuels 2022, 36, 14393−14402
Energy & Fuels
ETL. Even though it is a widely used material, the surface
oxygen defects in TiO2 can act as the primary trap states and
localize the electrons in the system. These defects delay the
photoelectronic transfers from the active layer (AgBiS2) to the
electrode. Additionally, these defect states in TiO2 will
significantly increase charge recombination at the AgBiS2−
TiO2 interface by blocking the injection of electrons to TiO2
from AgBiS27−11 and decrease the overall performance of the
device.12,13 Therefore, the quest for alternative material is a
potential interest of this field. The introduction of dopants
could facilitate additional charge carriers, enhance the carrier
lifetime, and reduce the recombination loss in the system.14
Anionic non-metals, such as boron, nitrogen, and fluorine, are
commonly utilized dopants that drastically reduce the
recombination loss by introducing the mid-band-gap states in
the system.15
In the conventional AgBiS2 device, deposited via the
successive ionic layer adsorption and reaction (SILAR)
method, mesoporous TiO2 is often used as the ETL, which
transfers the generated carriers from the photosensitizer (QDs)
to the conductive substrate.16 There are reports on the usage
of ZnO and SnO2 as ETLs for AgBiS2-based devices, which
offer appropriate band alignments in the system, enabling
efficient charge carrier dynamics across the interfaces. Also,
several modifications on these ETLs reflected in boosting the
device performance of AgBiS2.17,18 However, the performance
of these devices using TiO2 as an ETL is relatively low
compared to ZnO- and SnO2-based devices. Although
attempts have been made to enhance the charge extraction
properties of TiO2 by modifications,19 improper band
alignment resulted in reduced charge extraction and device
performance. Thus, the misalignment of energy band levels
between conventional TiO2 and AgBiS2 is one of the major
reasons for the reduced performance in these devices. In
addition to being eco-friendly, they are predicted to show a
power conversion efficiency (PCE) of ∼26%.1 Modification of
the ETL has a major role in enhancing the device performance
because it can address the mis-band alignment between the
photoabsorber and ETL. One can see several reports on ETL
modifications to enhance charge extraction from the photo-
absorber to ETL to improve the device performance.6,20,21
Creating an ETL with suitable band structures can lead to
energy level optimization and favorable alignment for optimal
charge extraction, reduced interfacial and surface recombina-
tion of charge carriers, and uninterrupted charge transport in
the device. However, the energy level alignment is highly
dependent upon the energy level positions of the adjacent
interface layers, where it enables a proper built-in potential and
favors a high charge transportation in solar cells.16
In this context, we have developed a titanium oxynitride
system using a simple sol−gel-assisted nitridation process and
employed it as the ETL for the first time in the AgBiS2-based
QDSSC and achieved an enhanced performance via appro-
priate band alignment of materials in the device. Structural,
optical, morphological, electrical, and PV properties of the
developed titanium-oxynitride-based device have been studied
in comparison to the device fabricated using conventional
TiO2.
■ EXPERIMENTAL SECTION
Materials and Methods. The following chemicals are used in this
study. Titanium tetrachloride (99.5%) and Triton X-100 (binder)
were acquired from Spectrochem. Fluorine-doped tin oxide (FTO)
pubs.acs.org/EF Article
glasses (surface resistivity of ∼7 Ω/sq and an optical transmission of
99.8%), titanium(IV) isopropoxide, TiO2 (99%), sodium sulfide
nonahydrate (Na2S·9H2O, 98%), and anhydrous citric acid were
purchased from Sigma-Aldrich. Silver nitrate (AgNO3, 99.9%) was
purchased from Fisher Scientific. Bismuth(III) nitrate pentahydrate
[Bi(NO3)3·5H2O] and sodium selenite (Na2SeO3, 98%) were
purchased from Avra and Loba Chemie, respectively. Ni(NO3)2·
6H2O were purchased from Merck. CuS nanoparticles were procured
from Sigma-Aldrich. Glacial acetic acid was procured from Avra. All of
the chemicals were used as-is with no further purifications.
Synthesis of Titanium Oxynitride. Titanium oxynitride, which
is used as the ETL, was synthesized as follows: A total of 1 mL of
titanium(IV) isopropoxide was taken in a beaker containing 5 mL of
glacial acetic acid and kept for stirring at room temperature for 1 h.
Subsequently, 100 mL of double-distilled water was added to the
above solution in a controlled manner and stirred for another 6 h.
After that, the solution was dried by placing it on a hot plate. The
resulting powder was ground using a mortar and pestle and calcined
in a tubular furnace for 3 h under optimized 100 standard cubic
centimeters per minute (SCCM) flow of NH3 at different temper-
atures, such as 450, 550, and 650 °C. Once the furnace reached room
temperature, the formed titanium oxynitride (TiOxNy) powder was
collected and stored at room temperature for further use. For
convenience, TiOxNy is called TiON throughout the paper and the
deduced elemental composition for the same is provided in the X-ray
photoelectron spectroscopy (XPS) section. For the comparison
studies, commercial anatase TiO2 was used.
Synthesis of NiO. NiO as the HTL was synthesized by the
chemical precipitation method, as reported by Chandrasekhar et al.22
Briefly, 3 g of Ni(NO3)2·6H2O was dissolved in 60 mL of deionized
water at room temperature until a clear green solution was obtained.
To this, NH4OH solution was added to adjust pH to 10 and stirred
for 15 min. The obtained green colloidal precipitate was centrifuged
at 10 000 rpm for 15 min to separate the product and washed thrice
with distilled water followed by ethanol. The resultant green adduct
was dried in a hot air oven overnight at 80 °C, ground, and calcined at
280 °C for 4 h, and finally the black-colored NiO powders were
obtained. Phase confirmation of synthesized NiO was performed
using X-ray diffraction (XRD) analysis and represented in Figure S1
of the Supporting Information.
Device Fabrication. The electrodes were fabricated on FTO
conductive substrates. The substrates were pre-cleaned using
surfactant, deionized water, acetone, and ethanol in an ultrasonicator
for 15 min to remove the impurities. TiCl4 was dip-coated onto FTO
by continuously dipping in 40 mM aqueous solution at 70 °C for 30
min, followed by rinsing the electrodes with deionized water and
ethanol. This helps with the formation of few nanometer thick
titanium hydroxide layers on FTO; this creates a blocking layer at this
interface to ensure that FTO is not exposed directly to the hole
conductor (redox electrolyte), hence aiding in the reduction of back
transfer recombination.23 Also, a proper contact with good adhesion
between the ETL and FTO is obtained by introducing a TiCl4
blocking layer.24,25 The TiON (or TiO2) paste was prepared by
grinding 0.5 g of powder by dispersing it in 0.5 mL of acetic acid and
0.5 mL of Triton X-100 until a homogeneous paste was formed. Then,
the paste was coated with FTO employing the doctor blade method
and sintered at 80 and 500 °C for 15 and 45 min, respectively.
The SILAR technique was employed for the deposition of AgBiS2
(edges were masked to avoid shorting). In this procedure, 0.07 g
(0.016 M) of AgNO3 dissolved in 25 mL of distilled water and 0.25 g
(0.025 M) of Bi(NO3)3 dissolved in 20 mL of distilled water (with 5
mL of acetic acid) were prepared to obtain the AgBiS2 QDs.
Utilization of acetic acid was to effectively dissolve Bi(NO3)3 in
distilled water. For the anionic source, 0.048 g (0.025 M) of Na2S was
dissolved in 25 mL of distilled water, where one cycle of SILAR
consisted of (i) immersion of the TiO2 (or TiON)-coated substrate
into Ag+ solution for 30 s and rinsing for 30 s in deionized water, (ii)
immersion of the Ag+-deposited electrode into the S2− source for 30 s
and then rinsing in deionized water for 30 s, (iii) immersion of Ag+
and S2− electrodes treated with the Bi3+ source for 30 s and then
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Energy Fuels 2022, 36, 14393−14402
Energy & Fuels pubs.acs.org/EF
rinsed in deionized water for 30 s, and (iv) immersion of the Ag+/
S2−/Bi+-deposited electrode into the S2− source for 30 s in distilled
water followed by rinsing in deionized water for 30 s. The synthesized
NiO powder (HTL) was dispersed in an aqueous solution (30 mg/
mL) and sonicated for 1 h. This well-dispersed NiO was then drop-
casted onto the photoanode (edges were masked to avoid shorting)
consisting of TiO2 (or TiON)/AgBiS2 and allowed for drying before
the measurements. Similarly, the CuS powder (counter electrode) was
dispersed in ethanol to obtain a thick paste, drop-casted on a separate
FTO, and vacuum-dried at 80 °C overnight (counter electrode). The
device follows an architecture of TiO2 (or TiON)/AgBiS2/NiO/
CuS), as shown in Figure 1. The device is further characterized by
sandwiching the properly masked photoanode and counter electrode.
Figure 1. Device architecture of the fabricated solar cell.
Characterizations. The crystal structure of the materials was
analyzed using powder XRD using Cu Kα radiation (1.5406 Å) by
Rigaku (scan rate of 3° min−1) at 40 kV and 30 mA. Surface
morphology of the sample was analyzed with field emission scanning
electron microscopy (FESEM) JSM 7100F JEOL deposited on
carbon tape, coated with 20 nm of gold. The sample pore distribution
and surface area were investigated using the Brunauer−Emmett−
Teller (BET) and Barrett−Joyner−Halenda (BJH) methods with
BELSORP Max, Japan. The optical properties of the materials were
investigated using ultraviolet−visible diffuse reflectance spectroscopy
(UV−vis DRS, Lambda 365, PerkinElmer) with integrating sphere
assembly. In addition to the optical studies. Elemental and chemical
state analyses were carried out using XPS with Al Kα (1486.6 eV) set
at 150 W and pass energy of 50 eV. The PV performance of the
QDSSC was measured over an area of 0.25 cm2 in triplicates (2 sets)
using the integrated I−V test station (PVIV-211V) with a Keithley
2420 source meter and 94023A Oriel Sol3A, class AAA solar
simulator (power output, 100 mW/cm2; lamp power, 450 W)
equipped with an AM 1.5 filter. The alternating current (AC)
impedance analysis was carried out using an electrochemical
workstation (CHI660D) in the frequency range from 1 MHz to 1
Hz with an AC amplitude of 10 V. The Tafel polarization study was
carried out in the same electrochemical workstation with a scan rate of
10 mV/s for symmetric cells.
Figure 2. (a) Full XRD pattern and (b and c) zoomed-in view of the XRD pattern of synthesized titanium oxynitride and commercial TiO2 (inset
of panel c shows the photographic images of the respective samples).
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■ RESULT AND DISCUSSION
Material Characterizations. As mentioned in the
Experimental Section, TiON particles were obtained at three
different temperatures (450, 550, and 650 °C). Among all,
TiON obtained at 550 °C showed a relatively enhanced PV
device performance compared to the other temperatures. The
device performances of all of the samples have been discussed
in the respective section below (Figure S4 and Table S1 of the
Supporting Information). However, only TiON obtained at
550 °C has been analyzed for its basic characteristics, as
discussed in the following sections.
The XRD patterns of synthesized titanium oxynitride
(TiON) and commercial titanium dioxide (TiO2) are
displayed in Figure 2a. The obtained XRD pattern reveals
that the major crystal phase is TiO2, corresponding to the Joint
Committee on Powder Diffraction Standards (JCPDS) data
89-4921. Similar to nitrogen-doped TiO2 that shows peak
broadening,26 a clear shift toward lower 2θ was observed for
TiON (Figure 2b), which indicates a decrease in the lattice
constant and that there could be a lattice occupancy of
nitrogen atoms in TiO2, leading to the formation of its
oxynitride (TiON) phase. It can be realized that the doping
essentially means the introduction of foreign elements in the
trace level, which hardly shows any changes in the
stoichiometric ratio of the material (i.e., in TiO2). In contrast,
the oxynitride phase consists of nitrogen atoms occupying the
lattices by replacing the lattice oxygen atoms, which leads to
the emergence of a crystal plane corresponding to the Ti−O−
N structure in the system. Accordingly, it is worth noticing that
the peak at 2θ of ∼43.05° that appeared in the XRD pattern of
TiON (Figure 2c) can be attributed to the formation of the
TiON phase, which matches with the cubic phase of titanium
oxynitride as reported in the literature.27,28 Further, the
observed shift in the XRD peaks of TiON with respect to
TiO2 can also be ascribed to the occupancy of nitrogen in the
lattices corresponding to the formation of the oxynitride phase
(Figure 2c) rather than a simple doping of nitrogen into the
system. Further, the presence of nitrogen in TiON resulted in
the change of its powder color to light gray, while bare TiO2 is
white in color (inset of Figure 2c).
The crystallite size of the sample was estimated using
Scherrer’s formula (D = Kλ/β cos θ), where D is the crystallite
size, λ is the wavelength of X-rays (1.514 Å for Cu Kα), K is
the crystallite shape constant (0.9), and β is the full width at
half maximum and found to be ∼23.3 and ∼14.4 nm for TiO2
https://doi.org/10.1021/acs.energyfuels.2c02287
Energy Fuels 2022, 36, 14393−14402
Energy & Fuels
Figure 3. FESEM images of (a and b) bare TiO2 and (c and d) TiON.
Figure 4. BET N2 adsorption−desorption isotherms of (a) bare TiO2 and (b) TiON. The insets in the respective panels show the BJH pore size
distribution in the samples.
and TiON, respectively. The observed reduction in the
crystallite size of TiON and decreased lattice parameters and
cell volume could be attributed to the larger ionic radius of
nitrogen atoms compared to the oxygen atoms in the lattices.
Interstitial doping would more likely happen if the dopant
atom is smaller, which tends to increase the cell volume of the
system. Accordingly, the hybridization of these elements (Ti−
O−N) results in the controlled growth of TiON crystallites
with reduced sizes. Hybridization and formation of this
oxynitride phase is further validated by XPS studies and
reported in the section ahead.
The FESEM images of TiO2 and TiON samples are
displayed in panels a−d of Figure 3. The particle size and
shape of both systems are found to be irregular and
homogeneously distributed with a size of around 50−80 nm.
The relatively well-ordered homogeneous distribution of
TiON particles can enable better diffusion of ions across the
pubs.acs.org/EF Article
channel.29 The elemental presence of Ti, O, and N in TiO2
and TiON, respectively, is confirmed by energy-dispersive X-
ray analysis (EDAX), as shown in panels a−d of Figures S2 and
S3 of the Supporting Information. The elemental mapping of
samples as displayed in panels b−d of Figure S3 of the
Supporting Information shows the homogeneous and uniform
distribution of the respective elements, more obvious in the
TiON sample (Ti, O, and N), which likely indicates that the
prepared system is very less agglomerated and also
stoichiometric in composition.
The surface area of bare TiO2 and TiON was determined
using BET analysis, and the obtained isotherms are displayed
in panels a and b of Figure 4, respectively. The obtained BET
curves showed typical type IV with type H3 hysteresis loops
according to the International Union of Pure and Applied
Chemistry (IUPAC) classification for both TiO2 and TiON
samples. This observed characteristic of the samples can be
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Figure 5. XPS spectra of the bare TiO2 and TiON systems: (a) Ti 2p, (b) O 1s, (c) N 1s, and (d) valence band XPS spectra.
attributed to the presence of interparticle porous structures
formed in both bare TiO2 and TiON.30,31 The obtained pore
size distribution curves (BJH) indicated the existence of a
narrow distribution of pores in the TiON system, with a mean
pore size of ∼9.7 nm (inset of Figure 4b), while the
distribution is relatively broader for bare TiO2, with a mean
decreased pore size of ∼7.2 nm (inset of Figure 4a). This
represents that TiON can possibly have a stable, homoge-
neous, and reactive surface, which is much more compatible
for the sensitizer deposition interaction.
The surface area of ∼84.15 and ∼99.85 m2/g was observed
for bare TiO2 and TiON, respectively, where the increased
surface area of TiON could be attributed to the relatively
increased pore size and less agglomerated reactive surface
compared to bare TiO2. It should be noted that the hysteresis
starts at a relative pressure of 5 p/p0 for bare TiO2, whereas it
starts at 7 p/p0 for TiON, which indicates that the TiON
surface is smooth and highly favorable for the effective sorption
process on the surface. Such surface properties of TiON
facilitate its effective interaction with environmental stimuli,
such as chemical reactions and physical interactions (optical,
electrical, etc.), on the surface as well as at the interfaces.32
The XPS spectra of bare TiO2 and TiON reveal the
chemical oxidation state and characteristic presence of N in the
TiON system. The obtained data are shown in panels a−d of
Figure 5. The C 1s spectrum was set at 284.6 eV to calibrate
the obtained XPS spectrum of the elements. Accordingly,
carbon correction and Shirley’s background corrections were
performed before the deconvolution of peaks.33 The Ti XPS
signal showed two peaks: weak Ti 2p1/2 and strong Ti 2p3/2
(Figure 5a). The Ti 2p1/2 and Ti 2p3/2 peaks are at 458.38 and
464.09 eV, respectively, for bare TiO2, while they are observed
at 458.08 and 463.8 eV, respectively, for TiON.34,35 Further,
the deconvolution of the TiON spectrum reveals a shoulder
peak with a lower binding energy at 463.4 eV that corresponds
to Ti3+, and both Ti4+ and Ti3+ are formed.14 The significant
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peak shift observed in the spectrum of TiON toward a low
binding energy with respect to TiO2 indicates the substitution
of a higher electronegative O atom by a less electronegative N
atom. The Ti−O environment is considerably affected as a
result of the nitridation process, which possibly corresponds to
the lattice occupancy by the N atom and formation of Ti−O−
N lattices. This observed shift in the Ti binding energy
represents that the chemical environment of Ti (i.e., Ti−O) is
considerably modified through the formation of the Ti−O−N
network.
The oxygen XPS spectrum of bare TiO2 and TiON is
displayed in Figure 5b, which shows the O 1s peak at 529.62
eV for bare TiO2 and 529.37 eV for TiON. The blue shift in
the binding energy of oxygen indicates that there could be
oxygen vacancies in TiON, which, in turn, is ascribed to the
lattice occupancy of nitrogen (N) atoms in the system through
the hybridization of O−N. In addition, the observed notable
peaks at 531.13 eV for TiO2 and 530.91 eV for TiON clearly
indicate that there could be a larger presence of adsorbed
oxygen corresponding to hydroxyl (OH) groups in the system.
However, this peak is drastically reduced for TiON, and it can
be attributed to the stability of the system. Further, the
deconvolution of TiON spectra reveals a weaker peak at 530.0
eV ascribed to Ti2O3, which formed as a result of Ti3+ and
vacancies in the system.36 The nitrogen XPS spectrum of
TiON is displayed in Figure 5c, which shows the N 1s peak at
399.7 eV, which confirms the lattice occupancy of chemisorbed
nitrogen in the TiON system37 and the peak at 398.6 eV
attributed to the bonding between titanium and nitrogen
corresponding to the presence of the oxynitride phase in the
formed system.38 On the basis of the area under the peaks
corresponding to oxygen and nitrogen, the elemental
composition of the obtained TiON phase is deduced to be
TiO1.98N0.02.
To validate and gain further insights into the lattice presence
of N in TiON and its effect on the electronic structure, the
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Figure 6. (a) UV−vis absorption spectra, (b) Tauc’s plot, and (c) band structure diagram of the bare TiO2 and TiON systems.
Figure 7. (a) Mott−Schottky plots of TiO2 and TiON, (b) I−V characteristics, (c) Nyquist plot (inset showing the equivalent circuit), and (d)
Bode plot of the solar cell device with TiO2 and TiON as the ETL.
valence band (VB) XPS spectra of TiO2 and TiON were
obtained and displayed in Figure 5d. In the obtained spectra,
the edge position of TiON is drastically red-shifted to 1.88 eV
compared to that of bare TiO2, which is 2.90 eV. This drastic
reduction in the binding energy indicates that the VB edge
position of TiON is considerably upshifted with respect to the
VB position of bare TiO2. Unlike N-doped TiO2 that creates a
new energy level above the existing VB,39 the nitridation
process makes the N 2p orbital be involved in the making of
the VB energy level through its hybridization with O 2p and Ti
3d orbitals, which also influences the conduction band (CB)
potential. This process drastically alters the band gap structure
by shifting the band edge potential and reduces the overall
band gap energy of the material, leading to more visible light
absorption with improved delocalization of the excited carriers
in the system.
The optical properties of bare TiO2 and TiON were
examined using UV−vis absorption, and the obtained results
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are displayed in panels a and b of Figure 6. The absorption
spectrum of TiO2 showed a sharp band edge fall in the UV
region (<400 nm), whereas this absorption band edge is
extended and tailing to the visible region in the case of TiON.
This indicates that the VB position of TiON can possibly be
dispersed as a result of the incorporation of nitrogen in the
oxygen lattices via the hybridization of O 2p and N 2p orbitals,
leads to the band gap reduction in the system, and shows the
manifestation of visible light-driven properties in TiON.
Accordingly, the band gap estimation using Tauc’s plot
indicated a band gap reduction from 3.2 eV (for TiO2) and
2.46 eV (for TiON), as displayed in Figure 6b. Further to
examine the VB maximum position of the synthesized
materials, VB spectral analysis was carried out. We determined
the VB position of TiO2 and TiON with the help of VB XPS,
as reported by Khan et al.40 and shown in Figure 6c. The
obtained band edge positions suggest an upshift in band energy
levels of TiON over TiO2, and this can enable an enhanced
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charge extraction from AgBiS2 to the ETL, thus reducing the
probability of back transfer recombination losses at the
photoanode (ETL/AgBiS2)−HTL interface, which is reflected
in the performance of the device.
Solar Cell Performance Studies. To understand the
origin of improved conductivity and mechanism of TiON, the
Mott−Schottky (MS) analysis was conducted to estimate the
flat-band potential values (Vfb), as shown in Figure 7a. The MS
curve is fitted using eq 1
1 2 ij KBT yz
= jjVapp Vfb zz
C2 0
2
A eNd k e {
where C denotes the differential capacitance of the space-
charge region, ε denotes the dielectric constant of the material,
ε0 denotes the permittivity of free space, A denotes the active
area, e denotes the charge of the electron, Nd denotes the
electron density, Vapp denotes the applied voltage, KB denotes
the Boltzmann constant, and T denotes the temperature. The
flat-band potential represents the potential that emerged as a
result of the charge accumulation or depletion in a semi-
conductor, and therefore, it will not lead to any band bending
at the interface region.41 The fitting parameters show a more
negative flat-band potential of −1.24 V for TiON than TiO2,
which is −1.1 V. Further, the positive slopes of tangent lines in
the linear part of the curves represent the n-type behavior of
the systems. The results (Figure 7a) evidently show that the
CB of TiON shifts negatively with respect to TiO2. This
enables an establishment of a higher Fermi level and enhances
the injection rate of electrons from AgBiS2 QDs (sensitizer) to
TiON (ETL). Theoretical and experimental studies reveal that
Voc is typically determined using the potential difference
between the redox potential of the electrolyte and flat-band
potential of the semiconductor photoanode.42 Thus, the
obtained flat-band energy values suggest that the recombina-
tion of the excited charge carriers at the interfaces of AgBiS2/
NiO and TiON/NiO can be drastically reduced in the
device.43
The developed TiON as an ETL was mounted on the device
with an architecture of FTO/TiON/AgBiS2/NiO/CuS, and
the corresponding photovoltage characteristics of the device
were investigated. The obtained results (Figure 7b) showed
that there is improvement in the PV performance of the TiON-
based (TiON-550) device, with a PCE of ∼2%, while it is
around ∼1% for the TiO2-based device (Table 1). The
Table 1. Photovoltaic Parameters of the Solar Cell Device
with Different ETLs (TiO2 and TiON) Measured at AM 1.5
G under 1 Sun Illumination (Average of Six Cells)
Voc Jsc cell Rshunt Rseries
ETL (V) (mA/cm2) FF efficiency (Ω) (Ω)
TiO2
TiON
0.25
0.30
11.9
16.1
48.4
49.7
1.0 ± 0.05
2.0 ± 0.03
21.7
49.7
79
58
obtained band energy levels suggest enhancement in the
electron injection rate from AgBiS2 (photosensitizer) to TiO2
(ETL), thus reducing recombination across the interfaces and
tweaking device performance. The I−V characteristics of the
samples nitrided at different temperatures and their perform-
ance parameters are provided in Figure S4 and Table S1 of the
Supporting Information. Also, the as-obtained device perform-
ance of TiON is compared to various ETLs used for AgBiS2
(given in Table S2 of the Supporting Information). It is
pubs.acs.org/EF Article
evident from the obtained band gap values and MS plots that
the position of CB of TiON is relatively more favorable (in
comparison to TiO2) and is effectively injected with excited
electrons from AgBiS2 in the device. The device using TiON as
the ETL exhibits more Voc (0.3 V) compared to the
conventional TiO2-based device (0.25 V). The upshift of the
Fermi level in the ETL accelerates the electron transfer and
reduces the recombination loss across the interfaces of QDs/
HTL and ETL/HTL, which eventually results in the
enhancement of Voc. Also, more negative flat-band potential
and higher concentration of charge carriers as realized from the
(1) MS plot account for the observed enhanced Voc and Jsc.44−46
The observed deviations in the diode curve for the devices are
attributed to the poor contacts at the HTL/CE interfaces,
causing the lowering of shunt resistance; this can be overcome
by engineering counter electrode materials.47,48 The external
quantum efficiencies (EQEs) of these devices were not
obtained as a result of lower shunt resistance.49,50 However,
it can be anticipated that this limitation can be further
overcome by engineering better deposition of hole transport
material (HTM) onto CE.
To understand the charge carrier dynamics across the
interface of the device, the electron impedance spectroscopy
(EIS) studies were carried out in the dark by applying bias
potential close to that of Voc. Table 2 shows the extracted
Table 2. EIS Parameters of the Solar Cell Device with
Different ETLs (TiO2 and TiON) Measured in the Dark
ETL Rs (Ω) Rct (Ω) Rrec (Ω) τ (ms)
TiO2 47.6 55.2 5220 4.6
TiON 27.5 38.2 8698 5.3
parameters from EIS analysis (Figure 7c). The larger semicircle
radius obtained for the device with TiON (with respect to
TiO2) indicates the enhanced charge collection and boosted
charge transport properties, owing to reduced recombination
losses in the device.51 This higher recombination resistance for
TiON with respect to TiO2 suggests that there is a reduced
recombination of electrons with holes. This can be readily
attributed to the observed enhanced Voc values obtained for
TiON. Also, the lower charge transfer resistance values indicate
the existence of a greater transfer of charges across the TiON/
AgBiS2 interface, which agrees well with the obtained band
edge energy values in this study. The frequency maximum
values were identified from the Bode plot (Figure 7d) and are
found to be 31.7 and 34.7 Hz for TiON and TiO2, respectively.
In addition, the recombination time of the excited charge
carriers were found to be ∼5.3 ms for TiON and ∼4.6 ms for
TiO2, indicating the higher lifetime of the charge carriers in the
TiON-based device compared to the TiO2-based device.
■ CONCLUSION
Titanium oxynitride with a chemical composition of
TiO1.98N0.02 was synthesized using the sol−gel-assisted
nitridation process under NH3 gas and employed as the ETL
in AgBiS2-based green QDSSCs. In comparison to the standard
TiO2, the solar cell using synthesized TiO1.98N0.02 as the ETL
performed better in the PV process. The observed enhance-
ment occurred via a rapid diffusion of electrons and ions in the
system, which effectively facilitated the injection of electrons to
the ETL from the sensitizer. Particularly, the introduction of
TiON as the ETL was favorable to align the energy bands of
14399 https://doi.org/10.1021/acs.energyfuels.2c02287
Energy Fuels 2022, 36, 14393−14402
Energy & Fuels
the materials in the device, which ultimately improved the
charge extraction from the photoanode and decreased the back
electron transfer recombination losses between the ETL/HTL
interface and QD/HTL interface. The device using TiON as
the ETL showed an efficiency of ∼2% compared to standard
TiO2, which showed around 1% efficiency. This result was
validated by the observed larger negative flat-band potential
and the measured electrical impedance in the device with
TiO1.98N0.02 as the ETL. According to the study, oxynitride
could be a potential ETL material to replace the metal oxides
in solar cells.
■
*
ASSOCIATED CONTENT
sı Supporting Information
The Supporting Information is available free of charge at
https://pubs.acs.org/doi/10.1021/acs.energyfuels.2c02287.
XRD analysis of NiO (Figure S1), energy-dispersive
spectrum and elemental mapping of TiO2 and TiON
(Figures S2 and S3), I−V characteristic curves for
different TiON samples (Figure S4), tabulation of the
PV performance of TiON synthesized at different
temperatures (Table S1), and comparative study on
the performance achieved by the AgBiS2 device using
various ETLs (Table S2) (PDF)
■ AUTHOR INFORMATION
Corresponding Authors
Farid A. Harraz − Promising Centre for Sensors and Electronic
Devices (PCSED), Advanced Materials and Nano-Research
Centre, Najran University, Najran 11001, Saudi Arabia;
Nanomaterials and Nanotechnology Department, Central
Metallurgical Research and Development Institute (CMRDI),
Cairo 11421, Egypt; orcid.org/0000-0001-7776-7099;
Email: faharraz@nu.edu.sa
Sakar Mohan − Centre for Nano and Material Sciences, Jain
University, Bangalore, Karnataka 562112, India;
orcid.org/0000-0001-9722-581X; Email: m.sakar@
jainuniversity.ac.in
R. Geetha Balakrishna − Centre for Nano and Material
Sciences, Jain University, Bangalore, Karnataka 562112,
India; orcid.org/0000-0002-7247-4921;
Email: br.geetha@jainuniversity.ac.in
Authors
Akhil S. − Centre for Nano and Material Sciences, Jain
University, Bangalore, Karnataka 562112, India
Mithun Prakash Ravikumar − Centre for Nano and Material
Sciences, Jain University, Bangalore, Karnataka 562112,
India
Mohammed Jalalah − Promising Centre for Sensors and
Electronic Devices (PCSED), Advanced Materials and Nano-
Research Centre and Department of Electrical Engineering,
Faculty of Engineering, Najran University, Najran 11001,
Saudi Arabia
Mabkhoot Alsaiari − Promising Centre for Sensors and
Electronic Devices (PCSED), Advanced Materials and Nano-
Research Centre and Department of Chemistry, Faculty of
Science and Arts at Sharurah, Najran University, Najran
11001, Saudi Arabia
Complete contact information is available at:
https://pubs.acs.org/10.1021/acs.energyfuels.2c02287
pubs.acs.org/EF Article
Author Contributions
†
Akhil S. and Mithun Prakash Ravikumar contributed equally
to the work.
Notes
The authors declare no competing financial interest.
■ ACKNOWLEDGMENTS
The authors would like to acknowledge the support of the
Deputyship for Research and Innovation - Ministry of
Education, Kingdom of Saudi Arabia for this research through
a grant (NU/IFC/INT/01/002) under the Institutional
Funding Committee at Najran University, Kingdom of Saudi
Arabia. Authors acknowledge DST-SERB, Govt. of India for
financial assistance (EMR Project Sanction No: (CRG/2018/
000942)). The authors also acknowledge the funding support
through the DST-INSPIRE Faculty Fellow Award (DST/
INSPIRE/04/2016/002227). The authors also acknowledge
the funding support from Jain University minor project grand.
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