Journal of Power Sources 481 (2021) 228865

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Journal of Power Sources

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Transparent photovoltaic cells and self-powered photodetectors by TiO2/

NiO heterojunction
Thanh Tai Nguyen a, Malkeshkumar Patel a, Sangho Kim a, Rameez Ahmad Mir b, Junsin Yi c, ***,
Vinh-Ai Dao d, e, **, Joondong Kim a, *
a
Photoelectric and Energy Device Application Lab (PEDAL), Multidisciplinary Core Institute for Future Energies (MCIFE) and Department of Electrical Engineering,
Incheon National University, 119, Academy Road Yeonsu, Incheon, 22012, Republic of Korea
b
Functional Materials Lab, SPMS, Thapar Institute of Engineering and Technology, Patiala, Punjab, India
c
College of Information and Communication Engineering, Sungkyunkwan University, Suwon 16419, Republic of Korea
d
FM&D Lab., Institute of Fundamental and Applied Sciences, Duy Tan University, Ho Chi Minh City 700000, Viet Nam
e
Faculty of Electrical-Electronic Engineering, Duy Tan University, Da Nang 550000, Viet Nam

H I G H L I G H T S G R A P H I C A L A B S T R A C T

• All transparent photovoltaic cell (TPC)

was fabricated.
• Solid-state TPC was achieved by metal
oxide heterojunctions.
• Large-scale photovoltaic cells were
fabricated by sputtering method.
• Photovoltaic effect is realized for
Anatase- and Rutile-TiO2.
• Transparent photovoltaic cell moves a
motor (0.2 V, 10 mA).

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

Keywords: The transparent photovoltaic cell (TPC) is an invisible solar cell by passing the visible range light while absorbing
All-transparent harmful UV light to generate electric power. Different from the conventional opaque colors or shapes of solar
Solar cells cells, TPC is transparent to human eyes and which would serve as an invisible power source for the window
Metal-oxides
frames of mobile electronics, displays, and buildings. To fabricate the TPC, two different metal-oxide species are
Rutile/anatase TiO2
n-TiO2/p-NiO heterojunction
employed to make a transparent heterojunction. TiO2 is the n-type semiconductor and serves as the UV light
Self-powered photodetector absorber. Above TiO2 layer, p-type NiO is deposited for a high transmittance (>57%) for the visible light. The
TPC is very sensitive to UV signals and thus, TPC can be a high-performing photodetector by self-powered
operation due to the photovoltaic effect. The n-TiO2/p-NiO photodetector shows high responsivity (0.23 A
W− 1), detectivity (1.6 × 1010), and fast response time (4.1 ms). The power conversion efficiency of TPC is
reached to 2.1% with high open circuit voltage (>0.5 V). A practical demonstration is performed to move a

* Corresponding author. Photoelectric and Energy Device Application Lab (PEDAL), Multidisciplinary Core Institute for Future Energies (MCIFE) and Department
of Electrical Engineering, Incheon National University, 119, Academy Road Yeonsu, Incheon, 22012, Republic of Korea.
** Corresponding author. FM&D Lab., Institute of Fundamental and Applied Sciences, Duy Tan University, Ho Chi Minh City 700000, Viet Nam.
*** Corresponding author. College of Information and Communication Engineering, Sungkyunkwan University, Suwon 16419, Republic of Korea.
E-mail addresses: junsin@skku.edu (J. Yi), daovinhai@duytan.edu.vn (V.-A. Dao), joonkim@inu.ac.kr (J. Kim).

https://doi.org/10.1016/j.jpowsour.2020.228865
Received 21 April 2020; Received in revised form 3 August 2020; Accepted 26 August 2020
Available online 12 September 2020
0378-7753/© 2020 Elsevier B.V. All rights reserved.
T.T. Nguyen et al.
motor (0.2 V and 10 mA), powered by TPC. This clearly suggests the transparent solar cell as the invisible power
generator.
1. Introduction
The ever-growing technological advances significantly depend on
the energy sources. Most of the energy demand has been mostly fulfilled
by fossil fuels. The addiction on that not only causes environmental
hazards but also results into depletion of the fundamental resources of
the Earth. The feasible and valuable solution is the utilization of
renewable or green energy sources to overcome the rapidly growing
energy demand. In this context, solar energy sources emerge as the most
reliable, abundant, efficient, sustainable, inexhaustible and clean energy
source [1–4]. Solar energy is frequently used in our daily life including
photocatalysis, heating water and generating electricity [5]. The appli­
cation and development of photovoltaic devices and solar cells are the
most promising choices to convert solar power into electricity [6,7].
These devices can be used for wide range of applications including
medical purposes, military defences, self-powered electronics, and en­
ergy effective environment, such as clean energy vehicles or hydrogen
energy production [5–8].
The current focus of research community is to design and fabricate
cost effective and reliable photoelectric devices. The performance of
solar cell is governed by photo-generated electron-hole pairs in the
semiconductor material by absorbing photon energy [7,9]. The use of
opaque surface of conventional solar panels is a critical issue to hinder
the wide utilization in the human life. To overcome this problem, the
transparent photovoltaic cells (TPCs) are the promising approach,
because they ideally needs no extra space for installation as transparent
power generators [5,6,10]. Moreover, the transparent photovoltaic solar
cell is not the vision barrier to human eyes, and thus it can be the
invisible energy source to be applied as power windows in mobile
electronics, displays, vehicles, and buildings. The key requirement of the
semiconductor material for TPCs can pass the visible wavelength light to
be transparent to human eyes, while absorbing the invisible light of
ultraviolet or infrared range.
Till date various wide bandgap semiconductors, like metal-oxide and
chalcogenides have been developed and used for solar cells [11–14]. The
metal-oxide materials are potentially regarded as promising partners or
alternatives of conventional silicon based solar cells. Moreover, the
non-toxic metal-oxide entities may induce the friendly uses in human
electronics. Some metal-oxide materials such as, TiO2, ZnO, CuO, and
NiO have been applied for various types of photovoltaic cells [7,15–17].
Among all, TiO2 is one of the most desirable materials for photovoltaic
devices because it exhibits excellent optoelectronic properties, wide
bandgap, and eco-friendly in nature [18,19]. TiO2 has been widely
studied for various photovoltaic structure such as dye sensitized,
perovskite and polymer solar cells which clearly shows its vital role for
developing the third generation of solar cells [20,21]. Apparently, the
quest for rapid, large-scale, and reliable fabricating methods to obtain
high quality TiO2 plays a key step in realizing the practical application of
photovoltaic cell.
Developing heterostructure with TiO2 for photovoltaic cell has
gained huge research interest. Due to the stable formation of electric
field at the interface, photo-generated carriers can be collected more
efficiently, resulting in device performance improvement. Different
semiconductors can combine with TiO2 to establish a stable junction,
such as SnO2 [22], BiOCl [23], CdS [24], and MoS2 [25]. Among them,
p-type NiO has been recently considered for the good counterpart of
n-TiO2 to form the efficient metal-oxide p/n junction due to the high
mobility [26], optical transparency [27], natural availability properties.
The potential of NiO/TiO2 heterostructure was demonstrated in
various research subjects, including photo-detection, electrochromic
application and photocatalyst [18,26,28–30]. In the regard of
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Journal of Power Sources 481 (2021) 228865
photon-electric conversion application, K. Khun et al. first time utilized
NiO/TiO2 heterostructure for UV photodetector based on TiO2 nano­
rods, achieved by simple hydrothermal method [26]. The study pre­
sented the advantage of built-in electric field at NiO/TiO2
heterojunction for self-powered TiO2 based UV photodetector. Yanyan
Gao et al. further improved the UV detecting capability of NiO/TiO2
heterostructure through controlling growth of TiO2 nanorods which
resulted in enhancement of built-in electric field [18]. The aforemen­
tioned researches demonstrated the importance of NiO/TiO2 hetero­
junction for efficient UV utilizing device based TiO2. Nevertheless the
great potential, no or less researches have been reported on the NiO/­
TiO2 transparent photovoltaics.
Herein, the solid-state NiO/TiO2 heterojunction was fabricated for
transparent photovoltaic cells. The photovoltaic effect is demonstrated
for different polymorphs of TiO2 of Anatase and Rutile structures. Both
TiO2 structures were synthesised by rapid and large-scale methods.
Above n-TiO2 layer, p-type metal oxide of NiO is deposited to form the
transparent p/n heterojunction. The FTO and silver nanowires (AgNWs)
act as the bottom and the top electrodes, respectively. Devices possess
the excellent UV responses under the photovoltaic mode (0.23 A W− 1 for
Rutile-TiO2 and 0.19 A W− 1 for Anatase-TiO2) with high transparency in
visible light region (about 57%). Furthermore, the transparent photo­
voltaic NiO/TiO2 cells exhibit reasonable power conversion efficiency of
UV light (2.1% for Rutile-TiO2 device and 0.9% for Anatase-TiO2). This
work indicates the promising functional use of metal oxides NiO/TiO2
heterostructure for transparent solar photovoltaics.
2. Experimental section
2.1. Device fabrication
Prior to the depositing process, FTO/glass substrates (735,159
Aldrich, sheet resistance 7 Ω/□) were cleaned with a sequence of
acetone, methanol and deionized water under ultra-sonication for 10
min and then dried by flowing nitrogen gas. Rutile TiO2 layer was pre­
pared by two steps including DC sputtering of Ti metal and oxidation of
Ti layer by rapid thermal processing (RTP) method. Ti was deposited by
DC sputtering (SNTEK, Korea) using Ti target (iTASCO, purity 99.99%).
The Ar flow rate of 50 sccm, DC power of 300 W and working pressure of
5 mTorr were maintained during the deposition (10 min) of Ti. To form
Rutile TiO2, Ti/FTO/Glass was thermally oxidized in RTP system at
600 ◦ C for 15 min. Anatase TiO2 was deposited by reactive sputtering
(SNTEK, Korea) using Ti target (iTASCO, purity 99.99%) at a deposition
temperature of 500 ◦ C. The Ar/O2 flow rate of 50/2.5 sccm, DC power of
300 W and working pressure of 5 mTorr were set to grow TiO2 for 60
min. The NiO layer was fabricated by reactive sputtering method to form
heterostructure with both Rutile TiO2 and Anatase TiO2. The NiO film
was deposited using Ni target (iTASCO, purity 99.99%) with Ar/O2 flow
at a working pressure of 3 mTorr [15]. The base pressure of 5 × 10− 6
Torr was achieved prior to introducing the sputtering gas. Pre-sputtering
for 10 min was performed and substrate was rotated at 5 rpm to ensure
the film uniformity. Transparent device was achieved by AgNW layer
using spin coating. The AgNW ink purchased from nanopyrix, and used
as received (AgNW length of 25 μm and diameter of 32 nm). The
spin-coated films were dried at 100 ◦ C for 1 min using a hot plate. The
active areas of AgNW/NiO/Anatase-TiO2/FTO and AgNW/NiO/R­
utile-TiO2/FTO devices are ~1 cm2.
2.2. Material characterizations
The crystal structure and phase of different TiO2 types were
T.T. Nguyen et al.
confirmed by X-ray diffraction (XRD, Rigaku, SmartLab) with Cu Kα
radiation (λKα = 1.540598 Å) in Grazing mode with a scan speed of 4◦ /
min. The absorbance and transmittance spectra were recorded in the
wavelength (λ) range of 300–1200 nm with a UV–visible diffused
reflectance spectrophotometer (Shimadzu, UV-2600). The cur­
rent–voltage (I–V) characteristic of the device was measured using a
potentiostat/galvanostat (PGStat, ZIVE SP2, WonA Tech.). We applied
linear sweep voltammetry with scan range with positive scan direction
with a scan rate of 100 mV s− 1. Light source of 365 nm was used to
measure the device performances. UV power meter (Lutron, UV 340)
was used to calibrate the light source. The front AgNW and back FTO
transparent electrodes were connected to the positive and negative
terminals of the PGStat, respectively.
3. Result and discussions
Fig. 1a represents the schematic of TiO2-based transparent photo­
voltaic device. Two types of n-type TiO2 (Anatase or Rutile polymorphs)
structures were prepared and investigated as the light absorber. The
cross-section SEM image of both TiO2 devices are shown in Fig. S1
(Supporting Information). This result shows average thicknesses of TiO2
films (Anatase and Rutile) are ~350 nm. The p-type semiconductor NiO
serves as the heterojunction counterpart to n-type TiO2. The FTO and
silver nanowires (AgNWs) serve as the bottom and the top electrodes for
collecting photo-generated carriers, respectively. The image of fabri­
cated device (presented in Fig. 1b) shows high transparency and pro­
vides a clear vision of background feature by passing the visible range
light.
To confirm the transparency characteristic of transparent devices,
the optical studies were analysed by UV–Visible spectroscopy for
Anatase- TiO2 device (AgNWs/NiO/Anatase-TiO2/FTO) and Rutile-TiO2
device (AgNWs/NiO/Rutile-TiO2/FTO), as shown in Fig. 1c and d,
respectively. The UV–visible spectrum clearly indicates the transparency
of devices in visible light region which is attributed to the wide bandgap
properties of NiO (3.8 eV) and TiO2 (>3 eV). The transmittance pattern
of the light through Anatase and Rutile-TiO2 devices are nearly same
(Fig. 1c), with average visible light transparency around 57% which is
Fig. 1. (a) The schematic of AgNWs/NiO/TiO2/FTO device. (b) Image of the device to show high transparency. Optical profiles of AgNW/NiO/TiO2/FTO transparent
devices (Anatase- and Rutile-TiO2) for broad wavelength spectrum (250 nm–1200 nm). (c) Transmittance and (d) Absorbance.
3
Journal of Power Sources 481 (2021) 228865
much higher than the required 40% transparency for the practical ap­
plications of window-type TPCs. The absorption spectrum (Fig. 1d) is
found the maximum absorption edge at near 300 nm wavelengths and
rapidly decreased by around 390 nm or longer wavelengths. Both
(Anatase and Rutile) TiO2 TPCs exhibit strong absorption spectra for
short wavelength (λ < 390 nm), which is mainly attributed to strong
band-to-band electron transition in the TiO2 layer and the hetero­
junction of p-NiO/n-TiO2. This strongly demonstrates the high selec­
tivity of the incident light to pass of visible light for transparency or to
absorb UV photons for power generation.
The XRD profiles are presented for Rutile-TiO2 (Fig. 2a) and Anatase-
TiO2 (Fig. 2b), respectively. The peaks positions at 2θ > 50◦ , were
highlighted by shadow pattern, which are attributed to Si substrate. The
observed peaks in Fig. 2a at 2θ of 27.4, 36.3 and 41.4◦ , correspond to
(110), (101) and (111) planes. This obviously indicates Rutile phase of
TiO2 (Crystallography Open Database_COD-9007433). The Anatase-
TiO2 has XRD peaks (Fig. 2b) at 25.4, 38.5, and 48.2◦ , which are indexed
to planes (101), (112), and (200), respectively. This is in good agree­
ment with the standard Anatase phase of TiO2 (Crystallography Open
Database_COD-9008214). The XRD patterns confirmed the quality
crystalline structure and chemical purity of Anatase-TiO2 (fabricated by
reactive sputtering) and Rutile-TiO2 (formed by-RTP).
The current–voltage profiles (I–V) of AgNW/NiO/Rutile-TiO2/FTO
and AgNW/NiO/Anatase-TiO2/FTO devices were recorded under dark
and UV (λ = 365 nm) conditions to access the photon conversion
capability of TiO2. Fig. 3a presents the I–V characteristics of the devices
under semi-log-scale. Both types of TiO2 devices showed distinct per­
formances in I–V properties for the light illumination and the dark
condition. The ratios of photo-current to dark-current (Iph/Idark, at zero-
bias) are estimated to be 200 and 339 for Rutile-TiO2 device and
Anatase-TiO2 device, respectively. The high on/off value (Iph/Idark ratio)
clearly indicates the strong UV photon utilizing ability of the TiO2-based
transparent devices. UV sensitization of transparent NiO/TiO2 hetero­
structures was further demonstrated by measuring of the Responsivity
(R) and Detectivity (D). R and D are important parameters for evaluating
the photon sensing quality of a photodetector. Responsivity represents
photodetector output signal to incident optical signal, which can be
T.T. Nguyen et al. Journal of Power Sources 481 (2021) 228865

Fig. 2. XRD patterns of different TiO2 polymorphs, grown on Si. (a) Rutile-TiO2 and (b) Anatase-TiO2.

Fig. 3. (a) I–V profiles of AgNW/NiO/TiO2/FTO transparent devices under dark and UV illumination (λ = 365 nm) conditions. Photodetection performances of
Rutile-TiO2 and Anatase-TiO2 devices. (b) Responsivity, (c) Detectivity of devices and (d–e) Photoresponse times.

obtained by formula by R = Iph/P with Iph is photocurrent (mA cm− 2) and 10% of maximum photocurrent) of photocurrent signal by on and off.
P is the incident light intensity (mW cm− 2) [18,27]. The transparent Fig. 3d and e show the photocurrent responses of Rutile-TiO2 device and
NiO/TiO2 devices can have self-powered operation due to the photo­ Anatase-TiO2 device, respectively. Both devices clearly distinguish the
voltaic effect. At zero-bias, with the UV illumination (λ = 365 nm, 0.78 current outputs between on and off states of UV light by quick speed of
mW cm− 2), transparent AgNW/NiO/TiO2/FTO photodetector can ac­ photoresponse. Specifically, Rutile-TiO2 device responded to UV signal
quire high R values of 0.23 A W− 1 for Rutile-TiO2 and 0.19 A W− 1 for with τr of 4.1 ms and τf of 4.3 ms. For Anatase-TiO2 device, τr and τf are
Anatase-TiO2, respectively, as shown in Fig. 3b. Detectivity can be obtained to be 4.2 ms and 4.1 ms, respectively. Table 1 summarizes
R
estimated by the relation; D = √̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅ where q is elementary charge previous reports on solid-state of TiO2 UV photodetectors. The results
2×Idark ×q
clearly remark the fast response time of AgNW/NiO/TiO2/FTO devices
(Coulomb). The self-powered transparent NiO/TiO2 photodetector can
in millisecond unit, different from other reports. Generally, TiO2 based
detect by D values of 1.4 × 1010 Jones for Rutile-TiO2 and 1.6 × 1010
photoelectric devices usually have a TiO2 structure of nanowire, nano­
Jones for the Anatase-TiO2, as presented by Fig. 3c. The R and D have the
rods, and nanobelts. These structures have advantages of good sensi­
pattern to show the decreased trend by increasing UV intensity. This is
tivity and responsivity, attributed to a large number of surface trap
attributed to the recombination by the traps or defects [18,31] and
states. However, the slow response speed is observed for these struc­
shows the serious tendency at high excess carrier generation states ac­
tures, assigned to the adsorption and desorption process of oxygen at
cording to the intensive UV illumination condition. It is worth to
surface states [23,32]. Developing capping layers with bulk TiO2 based
mention that, higher R and D value can be achieved at extremely low UV
p-n discipline can reduce the effect of oxygen molecules at the surface.
light intensity from the AgNW/NiO/TiO2/FTO devices, indicating the
Additionally, p-n heterostructure based TiO2 can also efficiently sepa­
high sensitive performances.
rate the photogenerated charges by the internal electric field at junction
In addition, photoresponse speed is another critical figure of merit
interface, resulting in self-powered operation. Therefore, the response
for a photodetector, presenting how quick a photodetector reacts to light
speed of TiO2 based photoelectric devices can be improved under
signal. The rise time (τr) and fall time (τf) are defined by rising interval
non-biased condition. Moreover, it is worthy to mention that our devices
(from 10% to 90% of maximum photocurrent) and fall interval (90%–
are transparent and has self-operation mode.

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T.T. Nguyen et al. Journal of Power Sources 481 (2021) 228865

Table 1
Summarization of current research on solid state UV photodetector based photo-sensitized TiO2 performance with R, D, τr, τf are Responsivity, Detectivity, rise time and
fall time, respectively.
Device structure λ (nm), Bias (V) R (A W− 1) D (Jones) τr (s) τf (s) Year, Reference

Au/ZnO/TiO2/FTO/Glass 380, 6 150 – 0.18 6.63 2015 [19]

Ni/TiO2/MgF2 300, 5 4.85 – 43 10 2016 [47]
Au/NiO/TiO2/TiOx/FTO 365, 0 0.006 5.5 × 1011 <0.1 <0.1 2018 [18]
Pt/quasi-solid-state electrolyte/TiO2/SnO2/FTO 340, 0 0.15 – 0.14 0.06 2018 [48]
Ag/TiO2/FTO/Glass 380, − 1 3 0.3 0.5 2018 [49]
Ag/BiOCl/TiO2/Ti/Ag 350, − 5 41.94 1.4 × 1014 12.9 0.81 2018 [23]
Ag/TiO2/Ag/PET 365, 5 – – 25 50 2019 [50]
4
Au/TiO2/Au 365, 4 2 × 10− – 0.98 3.14 2019 [51]
Au/TiO2/Graphene oxide/Si 380, 3 0.048 2.3 × 1011 48 40 2019 [52]
AgNW/NiO/Rutile TiO2/FTO 365, 0 0.2 1.4 × 1010 0.0041 0.0043 This work
AgNW/NiO/AnataseTiO2/FTO 365, 0 0.19 1.6 × 1010 0.004 0.0042 This work

Beside the excellent UV photodetection performances, transparent
AgNW/NiO/TiO2/FTO device can generate electric power from the
light. The photovoltaic integrated device has diverse applications
ranging from low-power consumption products like sensors, mobile
electronics, and internet of things to high power generation for electric
vehicles and buildings by integrating transparent power sources in the
window [33–36]. Fig. 4a and b present the I–V characteristics of
AgNW/NiO/Rutile-TiO2/FTO under linear and semi-log-scale with
different UV light intensity. Similarly, Anatase-TiO2 device were also
recorded by varying UV illumination intensities, as shown in Fig. 4c and
d. Both Rutile-TiO2 and Anatase-TiO2 devices possess power generating
ability under UV illumination. The overall negative (− ) power product is
located in 4th quadrant due to positive (+) voltage values and negative
(− ) current values. And thus, solar cells can provide electric power to the
external circuit. Under photovoltaic condition, transparent AgNW/­
NiO/TiO2/FTO devices are able to generate 8 mAcm-2 of short circuit
current (ISC) and 0.5 V of open circuit voltage (VOC) for Rutile-TiO2
transparent solar cell (TSC) or 7 mAcm-2 of ISC and 0.3 V of VOC for
Anatase-TiO2 transparent solar cell.
Fig. 5a presents the modulation of ISC to the incident UV light in­
tensities. The upward trend of ISC is observed by increased UV intensities
both for Rutile-TiO2 and Anatase-TiO2 devices. For UV intensity ranging
from 0.78 mW cm− 2 to 45 mW cm− 2, the photocurrent of AgNW/NiO/
TiO2/FTO devices was increased from 0.18 mAcm-2 to 6.7 mAcm-2 for
Rutile-TiO2 device and from 0.15 mAcm-2 to 4.2 mAcm-2 for Anatase-
TiO2 device. The enhanced UV photon flux results in more photon ab­
sorption in TiO2, which leads to the higher photocurrent production. The
strong proportional relation between the photocurrent and light in­
tensities is clearly observed and demonstrates the excellent TiO2 capa­
bility of UV photon utilization. This proportional current-power relation
was further analysed by power law fitting, ISC = APα with A is a constant.
P is light intensity and α presents the recombination process or trapping
of electron-hole in semiconductor. The fitting curve is presented in
Fig. 5a with α value of 0.91 for Rutile-TiO2 related device and 0.72 for
Anatase-TiO2. Theoretically, the device with trap-free may have α value
close to 1 [37–39]. The α values in range of 0.5–1 indicate the existence
traps in the device [40,41]. The α value of Rutile-TiO2 (0.91 close to 1)
suggests the less trap states, compared to Anatase-TiO2 (α = 0.5). In

Fig. 4. I–V profiles of AgNW/NiO/TiO2/FTO device with different UV (λ = 365 nm) intensity. (a) Linear scale and (b) Semi-log-scale for Rutile-TiO2 transparent
photovoltaic cell and (c) Linear scale and (d) Semi-log-scale for Anatase-TiO2 transparent photovoltaic cell.

5
T.T. Nguyen et al.
Fig. 5. UV intensity-dependent transparent photovoltaic AgNW/NiO/TiO2/FTO device performances. (a) Short circuit current (ISC), (b) Open circuit voltage (VOC)
and (c) Power conversion efficiency. Upper and lower panel present Rutile-TiO2 and Anatase-TiO2, respectively.
addition to ISC, the open circuit voltage (VOC) value also exhibits the
rising trend according to the higher UV intensity, as shown in Fig. 5b.
With the same UV intensity range, VOC of AgNW/NiO/TiO2/FTO devices
increase from 0.03 V to 0.49 V for Rutile-TiO2 and from 0.06 V to 0.27 V
for Anatase-TiO2. The higher VOC values at high illuminating light in­
tensity suggest NiO/TiO2 heterostructure capability by efficient
photo-carrier collection from the incident photons due to the strong
electric field in the space charge region. AgNW/NiO/Anatase-TiO2/FTO
and AgNW/NiO/Rutile-TiO2/FTO can possibly achieve fill factor values
of around 30%, respectively, as shown in Fig. S2.
Fig. 5c presents the power conversion efficiency (PCE = output
power/input power) of AgNW/NiO/TiO2/FTO devices under illumina­
tion of UV light (λ = 365 nm). Both transparent photovoltaic cells
(Rutile-TiO2 and Anatase-TiO2 devices) show clear variation of PCE
values for different UV intensities. At low intensity UV of 0.78 mW cm− 2,
AgNW/NiO/Rutile-TiO2/FTO can have PEC of 0.15% while Anatase-
TiO2 device has improved PEC of 0.3%. By increasing UV intensity
(Fig. 5c), Rutile-TiO2 TSC can achieve PCE value up to 2.1% and
Anatase-TiO2 TSC can have 0.9% PEC. It is worth to notice that PCE of
Rutile-TiO2 device shows the upward trend with increasing incident
light intensities. Meanwhile, the Anatase-TiO2 device has lower PCE
values and readily saturated against the increase of intensity. At high
light intensity condition, the increase of trap states can turn into
recombination centers [37], which may reduce carrier collection,
retarding PCE improvement. In summary, Rutile-TiO2 device has less
trap-dependent behaviors under light illumination and induces more
effective performances. More or less, PCE varies by the light intensity;
however, the TiO2-based TSC can effectively convert the light to electric
power. This suggests the possibility of low-power electronics operation
under low-intensity indoor lights and high-power production from the
Sun by efficient TSC platforms. With high optical bandgap property (>3
eV), transparent NiO/TiO2 heterostructure can solely utilize ultraviolet
photon which accounts for 3.2% solar photon flux [42], resulting in
limitation of solar energy – electrical conversion as compared to the
conventional (typically dark) photovoltaic cells, absorbing the visible-IR
light region. The performance of AgNW/NiO/Anatase-TiO2/FTO and
AgNW/NiO/Rutile-TiO2/FTO under one Sun condition (AM 1.5G) are
presented by Fig. S3. Relatively high transparent thin film solar cells
have commonly investigated by dye, organic and perovskite solar cells
[43]. These wet-type solar cells may have a high potential in
throughput, however, which have serious barriers for practical appli­
cations due to the leakage problem and unstable performances mainly
due to the electrolyte [44–46]. Meanwhile, the solid-state metal-oxide
photovoltaic cell has strong benefit of the high stability in atmospheric
condition without any special capitulation. Moreover, metal-oxides are
earth-abundant and cost-effective materials and suitable for transparent
6
Journal of Power Sources 481 (2021) 228865
photovoltaic materials. The performance of solid-state of all metal-oxide
photovoltaic cell would be further improved by integration with low
band gap materials such as SnS [6], Cu2O [40] or Si thin films by keeping
the general transparency of the devices.
In order to understand the transparent photovoltaic effect of TSCs,
the working mechanism of AgNW/NiO/TiO2/FTO devices were inves­
tigated in the aspect of UV photon-responding carrier generation and
collection. Metal-oxide p-NiO/n-TiO2 photovoltaic cell is transparent
due to the wide energy bandgap. Semiconductor has an energy bandgap
which is defined by electron-occupied condition. Among the many
possible energy levels, the conduction band (EC) is defined by the lowest
energy level to be filled with electrons. Meanwhile, the valence band
(EV) is highest energy level filled with electrons. According to the po­
tential difference between EC and EV, semiconductor material has own a
certain amount of energy space to prevent the existence of electrons,
which is the energy forbidden gap or energy bandgap.
Photons have different energy by wavelength and the wavelength-
dependent photon energy (Ephoton) can be calculated by Ephoton (eV)
= 1240/λ (nm). From the relation, short wavelength light has strong
photon energy and can be absorbed in the light-absorbing materials. The
semiconductor has an energy bandgap and higher photons larger than
the energy bandgap can be absorbed in semiconducting materials. The
strong UV photons thus can be absorbed and the energy readily excites
the electron from the valence band to the conduction band. The metal-
oxide-based p-NiO/n-TiO2 solar cell is transparent. Due to the relatively
large energy bandgap of metal oxide materials (EG > 3 eV), the most
visible wavelength light (visible light wavelength: 380 nm–760 nm,
corresponding to photon energy 3.26 eV–1.63 eV) can be transmitted
without or less absorption in metal-oxide layers.
Fig. 6a and b show the energy band diagrams of NiO/Rutile-TiO2 and
NiO/Anatase-TiO2 transparent solar cell, respectively. Regarding to the
vacuum level (EVC), the difference of conduction band and valence band
positions between NiO and TiO2 results in the formation of type II het­
erojunction (staggered gap). The EC and EV values of NiO, Rutile-TiO2,
Anatase-TiO2 are found to be 1.44 eV and 5.24 eV [27], 4.3 eV and 7.3
eV [19] and 3.95 eV and 7.15 eV [28], respectively.
The built-in potential is induced by the difference of Fermi-level (EF)
between NiO and TiO2. Considering the similar location of Fermi-level,
the Rutile-TiO2 and Anatase-TiO2 have almost same amount of potential
difference or built-in potential. The light absorbed in the space charge
region can effectively collected by the same amount of electric field both
for Rutile-TiO2 TSC and Anatase-TiO2 TSC. Meanwhile, UV photons
absorbed in TiO2 bulk causes the difference of carrier generation. Rutile-
TiO2 has a relatively smaller energy bandgap (EG = 3 eV) than 3.2 eV of
Anatase-TiO2. And thus, more electrons can be generated in the con­
duction band of Rutile-TiO2, resulting in the enhanced photocurrent
T.T. Nguyen et al.
Fig. 6. Energy band diagram of transparent photovoltaic (AgNW/NiO/TiO2/FTO) devices. (a) Rutile-TiO2 and (b) Anatase-TiO2. (c) Demonstration. Transparent
solar cell produces power from UV light to move a fan (Supplementary information: Supporting video is available).
value from the Anatase-TiO2 TSC (as shown in Fig. 5a). This strongly
suggests the further improvement is possible for transparent photovol­
taics by optimizing optical and electrical aspects. Practically, the fabri­
cated transparent solar cell was demonstrated for operating a motor, as
shown in Fig. 6c. By UV illumination, the transparent solar cell gener­
ated power to move a motor (0.2 V and 10 mA). This clearly suggests the
transparent solar cell would serve as an invisible power generator.
4. Conclusions
The low cost and functional transparent photovoltaic devices have
been realized by p-NiO/n-TiO2 heterostructure with different poly­
morphs of Anatase and Rutile phase of TiO2. The transparent AgNW/
NiO/TiO2/FTO device can operate as a self-powered photodetector and
a power generator (solar cell), attributed to the established built-in
potential at the interface of NiO/TiO2 staggered gap heterojunction
and efficient photon-excited carrier collection. The transparent solar cell
(AgNW/NiO/Rutile-TiO2/FTO) was reached up to 2.1% and provides
power to operate a motor. Unique features of transparent photodetector
of transparent photovoltaic cell would open various applications in
many human electronics. Moreover, the transparent solar cell would be
an invisible power generator for the conventional window of electronics
and buildings. Human may get electric energy without losing the vision
in near future.
CRediT authorship contribution statement
Thanh Tai Nguyen: Methodology, Formal analysis, Data curation,
Writing - original draft. Malkeshkumar Patel: Data curation, Writing -
7
Journal of Power Sources 481 (2021) 228865
original draft. Sangho Kim: Formal analysis. Rameez Ahmad Mir:
Visualization. Junsin Yi: Supervision, Writing - original draft, Writing -
review & editing. Vinh-Ai Dao: Supervision, Writing - original draft,
Writing - review & editing. Joondong Kim: Supervision, Funding
acquisition, Writing - original draft, 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.
Acknowledgements
The authors acknowledge the financial support of High Risk, High
Return research program (2019) in Incheon National University and the
Korea Institute of Energy Technology Evaluation and Planning (KETEP-
20203030010310) of the Republic of Korea.
Appendix A. Supplementary data
Supplementary data to this article can be found online at https://doi.
org/10.1016/j.jpowsour.2020.228865.
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