pubs.acs.

org/acsaelm Article

Perovskite-Based Facile NiO/CH3NH3PbI3 Heterojunction Self-

Powered Broadband Photodetector
Vishesh Manjunath, Prashant Kumar Mishra, Rachit Dobhal, Santosh Bimli, Parasharam M. Shirage,
Somaditya Sen, Parvez A. Shaikh,* and Rupesh S. Devan*
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ABSTRACT: Perovskite light absorbers have drawn attention worldwide for optoelectronic devices due to their solution-
processable photovoltaic properties, high carrier mobility, broad spectral range, and integration with a wide range of substrates, etc. A
facile NiO/CH3NH3PbI3 heterojunction was fabricated in an ambient environment for self-powered and high-performance
photodetector (PD) application. The self-powered PD showed a high responsivity of 33.39 mA/W for UV light and 5.79 mA/W for
white light at zero bias, which further increases up to 28.6 A/W for UV light and 29.2 A/W for white light at +1 V. Subsequently, the
detectivity for an entire UV and visible spectrum was observed to be above 1010 Jones at zero bias. Interestingly, the stability study
for PDs in the air up to 38 days revealed the highest photoresponsivity of 40.56 mA/W at zero bias. This enhancement is attributed
to the intrinsic modification within metal halide perovskites that lead to optimized PbI2 content. Additionally, a systematic study of
X-ray diffraction patterns at an interval of days revealed the presence of PbI2 content. Further, the photodetection ability was
retained for up to 58 days with a decrease in light current without encapsulation. Our results indicate that a NiO/CH3NH3PbI3
heterojunction-based PD paves the way for ambient friendly, high-performance, self-powered, stable optoelectronic applications.
KEYWORDS: perovskite, photodetector, NiO/CH3NH3PbI3 heterojunction, self-powered, detectivity

■ INTRODUCTION
The field of optoelectronics has been transformed with the
invention of broadband PDs utilizing CH3NH3PbI3 (MAPI)
perovskites has triggered excitement due to its high photo-
advent of metal halide perovskites that possess unique current (Iphoto).11 Dou et al.12 demonstrated perovskite PDs
optoelectronic properties, namely, direct tunable bandgap, with solution-processed CH3NH3PbI3−xClx, after which
large charge diffusion length, high absorption coefficient, and various perovskite PDs are described in the literature.13−16
photon recycling, etc.,1 which can be further tuned by merely Generally, to enhance the performance of perovskite-based
varying the chemical composition of ABX3 (where A and B are photodetection, the three main strategies used are (i)
cations and X is a halide anion) metal halide perovskite engineering device structures,17 (ii) controlling the morphol-
structures.2 Therefore, these perovskite halides have shown ogy of perovskite films,18 and (iii) construction of hetero-
promise toward various optoelectronic applications in solar junctions.19−21 Among these strategies, the heterojunction
cells,3−6 microlasers,7 photodetectors (PDs),8 and light-
emitting diodes,9,10 etc. However, PDs, intelligent optoelec- Received: August 2, 2021
tronic devices that convert optical input signals to electrical Accepted: September 22, 2021
outputs, attract attention due to their advancement in sensing, Published: October 11, 2021
imaging, communication, and environmental monitoring.
Although several semiconducting materials were employed in
the PDs depending on the absorption range and bandgap, the

© 2021 American Chemical Society https://doi.org/10.1021/acsaelm.1c00679

4548 ACS Appl. Electron. Mater. 2021, 3, 4548−4557
ACS Applied Electronic Materials pubs.acs.org/acsaelm Article

facilitates exciton dissociation and carrier transport, resulting in responsivity of 33.39 mA/W for UV light, followed by 6.48,
broad spectral response and improved performance.8,13,22−25 2.57, 2.29, and 5.79 mA/W for blue, green, red, and white
Therefore, several organic and inorganic semiconductors along lights, respectively, at zero bias. Additionally, high detectivity in
with metal halide perovskites were used to fabricate the order of 1010 Jones was observed. Further, the stability of
heterojunction PDs.13,26−28 Among the inorganic semiconduc- the self-powered PD was studied for up to 58 days. Though the
tors, nickel oxide (NiO) with high chemical stability is of X-ray diffraction studies revealed that the degradation of MAPI
prime importance and is a promising candidate for films contributed to the reduction in current, the optimized
optoelectronic and energy/conversion applications.29−32 content of PbI2 in MAPI films enhanced the PD performance
Recently, self-powered perovskite-based PDs have attracted due to reduction of dark current. Overall, our findings suggest
intense attention due to their independence, less complicated that NiO and the MAPI heterojunction are promising to
circuitry, and self-sufficient potential for device operation. fabricate low-cost and high-performance self-powered PDs for
These PDs depend on photovoltaic behavior to produce light optoelectronic applications.

■
current at 0 V bias, which is achieved by forming Schottky
junctions with single perovskite crystals and p-i-n junc- EXPERIMENTAL DETAILS
tions.33−35 However, these materials are thermally unstable Chemicals and Reagents. Nickel (99.5%, Alfa Aesar), lead
and degrade in the ambient atmosphere.35,36 This becomes a iodide (99.9985%, Alfa Aesar), methylamine hydroiodide (TCI),
critical issue in inhibiting device performance for real-time N,N-dimethylformamide (DMF) (Sigma-Aldrich), dimethyl sulfoxide
applications such as optical communication, imaging, sensing, (DMSO) (Sigma-Aldrich), ethanol (SRL Chem), and isopropyl
etc.37−39 Therefore, a systematic study on degradation alcohol (SRL Chem) were used as received.
mechanisms and intrinsic modification within metal halide Device Fabrication. The device was fabricated in the piecemeal
perovskite in the presence of a foreign layer is highly desirable. processing of FTO, NiO, MAPI, and Au constituents. The schematic
of the device fabrication process is shown in Figure 2. FTO-coated
In this work, high-performance self-powered NiO and MAPI
glass substrates were ultrasonically cleaned sequentially with soap
heterojunction PDs are engineered in an ambient environment solution, DI water, acetone, and ethanol, which were further dried in
to observe a broad spectral response ranging from ultraviolet hot air. The as-cleaned substrates were coated with highly transparent
(UV) to visible spectra. The performance of self-powered PDs NiO thin films following the recipes reported in previous studies.6
is probed at five different wavelengths of 290 ± 5 nm (UV), Initially, high purity nickel metal (i.e., 99.5%) was thermally
450 ± 5 nm (blue), 540 ± 5 nm (green), 640 ± 5 nm (red), evaporated over FTO substrates and further oxidized for 3 h in
and white light which provides a thorough outline of the entire ambient at 580 °C to form NiO thin films. MAPI perovskite was
UV−vis spectra (Figure 1), which have been scarcely deposited in ambient with a two-step deposition process. Lead iodide
(1.2 M) dissolved in 19:1 (DMF:DMSO) was spin-coated on NiO
investigated in earlier reported studies. To account for the
films at 1500 rpm for 30 s and further dried at 75 °C for 60 s. It was
figures-of-merit of the PD, the responsivity (R), detectivity further dipped in methylamine hydroiodide and isopropyl alcohol
(D*), sensitivity (S), and on/off ratio were measured at each solution for 20 s (10 mg/mL) to obtain reddish-brown perovskite
probing wavelength. The self-powered PD delivered a films, which were rinsed in isopropyl alcohol to remove excess growth
of perovskite and immediately spun at 4500 rpm for 10 s to form
smooth and transparent films. Transparent thin films converted into
reddish-brown films upon heating at 100 °C for 30 min were allowed
to cool at room temperature. Further, Au was thermally evaporated
through a shadow mask to form a counter electrode. The active area
of the device was defined at 0.7 cm2.
Characterization. The surface morphology and thickness of each
layer deposited were analyzed from field emission scanning electron
microscopy (FESEM, JEOL, JSM-7610 F). Absorption spectra of NiO
and MAPI films were recorded using a UV−Vis spectrophotometer
(Shimadzu, UV-2600) to confirm the absorption range and bandgap.
The structural and chemical variations in the MAPI films were
recorded using an X-ray diffractometer (Bruker D2 Phaser) to
understand the effect of light exposure on the device’s performance.
I−V conductance was measured using a Keithley Source meter 2401.
Photosensing studies on the self-powered PDs were performed in
ambient utilizing a customized setup and placed inside a dark box to
ensure the absence of any external light. Steady LED light sources of
various wavelengths, i.e., 290, 450, 540, and 640 nm, and white light
with a constant power of 1.15 mW were used to perform the
photosensing studies. A minimum of 4 on/off cycles of photo-
illumination were studied with the sequential periodicity of 30 s light
on and off for each wavelength. ΔI was evaluated at the 90% change
in Ilight during light on and off as shown in eq 2.40 The sensitivity (S)
of the NiO/MAPI heterojunction at a different probing wavelength
was calculated with eq 3. The ratio of the on current to that of the off
current was calculated from eq 4. The ability to generate photocurrent
per incident power (Pin) per illumination area (A) given by
responsivity (R) is shown in eq 5. Conversely, detectivity (D*),
defined as the ability of the self-powered NiO/MAPI heterojunction
Figure 1. Schematic of the self-powered NiO and MAPI to detect a minimum optical signal above the noise, is shown in eq
heterojunction PD engineered to perform at different wavelengths 6.41,42 The rise time (Tr), the time taken by NiO/MAPI PD to switch
in the UV−vis region. from the off state to the on state, was defined as the time required for

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Figure 2. Schematic of the fabrication process of a NiO/MAPI heterojunction-based photodetector device at ambient atmospheric conditions.

the Idark to reach 90% of Ilight. Similarly, the fall time (Tf) was the time
required for NiO/MAPI PD to switch from 90% Ilight to Idark. The key
parameter to understand the performance of PD was calculated using
the following equations
Iphoto = Ilight − Idark (1)

ΔI = 90% of Ilight − Idark (2)

(90% of Ilight − Idark)

S=
Idark (3)

on Ilight
ratio =
off Idark (4)

Iphoto
R=
Pin (5)

R
D* =
2qJdark (6)

Intensity of PbI 2
content of PbI 2 = × 100
Intensity of PbI 2 + Intensity of MAPI Figure 3. (a) Schematics of the fabricated NiO/MAPI photodetector.
(7) (b) Cross-sectional FESEM image of the NiO/MAPI photodetector
where Pin is the incident light energy; Jdark is dark current density; and (as highlighted with dotted lines in (a)). Pale blue, green, and red
q is the electronic charge. colors highlight the FTO, NiO, and MAPI, respectively. (c)

■
Schematics of the corresponding band diagram.
RESULTS AND DISCUSSION
The self-powered PD was fabricated with FTO/NiO/MAPI/ MAPI progresses with time and tailors the energy level
Au device architecture. The schematic of the fabricated self- alignment, which is expected to alter the PD performance.
powered PD is shown in Figure 3(a). The corresponding cross- UV−vis spectroscopy was used to record the absorption
section FESEM image of NiO and the MAPI heterojunction spectra of the fabricated NiO/MAPI heterojunction. The UV−
formed over an FTO-coated glass substrate is shown in Figure vis absorption spectroscopy of NiO thin films synthesized over
3(b). The thin layer of NiO is stacked between FTO and FTO-coated glass substrates (Supporting Information, Figure
MAPI. Three distinct layers were observed in the cross- S1) showed minimum absorption in the visible range (400−
sectional FESEM image and highlighted with pale blue (for 800 nm), allowing maximum visible wavelength to irradiate
FTO), green (for NiO), and red (for MAPI) colors. The MAPI films. The NiO thin-film absorption onset was observed
estimated thickness of FTO, NiO, and MAPI films was ∼550− at ∼378 nm, and the corresponding bandgap of 3.28 eV was
575, ∼35−45, and ∼500−530 nm, respectively. The observed estimated by Tauc’s plot (inset of Figure S1(a)). Further, the
thickness of NiO film is akin to our previously reported data.6 absorption range and corresponding bandgaps of plain MAPI
The corresponding band diagram of the NiO/MAPI films and MAPI coated over NiO (i.e., NiO/MAPI) film are
heterojunction where PbI2 evolved with time (Figure 3(c)) shown in Figure 4(a) and (b), respectively. The pristine MAPI
is prepared utilizing the energy levels from the literature,6,43 coated over FTO (i.e., FTO/MAPI) and MAPI film over NiO
revealing that the well-aligned energy levels of NiO and the (i.e., FTO/NiO/MAPI) in the NiO/MAPI heterojunction
MAPI heterojunction can facilitate the collection of photo- showed an excellent absorption range in the visible spectrum.
generated charge carriers. However, the PbI2 formed from A slight extension of the absorption range over 750 nm may be
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Figure 4. (a) UV−vis absorption spectrum and corresponding (b) Tauc’s plot for estimating the bandgap of MAPI films coated over plain FTO
(i.e., CH3NH3PbI3/FTO) and NiO-coated FTO substrates (i.e., CH3NH3PbI3/NiO/FTO corresponds to NiO/MAPI).

possible due to sub-band states arising from pinholes in the

films. The bandgaps of 1.55 and 1.58 eV obtained for FTO/
MAPI and FTO/NiO/MAPI heterojunctions, respectively,
exhibited that insignificant variation is akin to the liter-
ature.44,45 Even though NiO absorbs UV and MAPI absorbs vis
spectra independently, the NiO/MAPI heterojunction alto-
gether absorbs both the UV and visible spectra. However, the
visible-range absorption of MAPI film over NiO in a
heterojunction was higher than the MAPI film over the FTO
substrate, indicating NiO as a template enhanced visible-range
absorption.
Figure 5 shows the FESEM micrographs of MAPI film
deposited over the plain FTO substrate (Figure 5(a)) and
NiO-loaded FTO substrate (Figure 5(b)). Uniform grain
growth of MAPI on the FTO substrates resulted in the
formation of plain MAPI film over a large area. The high-
magnification micrographs to the inset of Figure 5(a) revealed
no pinholes in the plain MAPI films. Figure 5(c) depicts the
schematics of uniform grains of MAPI films coated over the
FTO substrate. However, NiO over the FTO substrate has led
to the formation of nonuniform grains along with a few
secondary grains of MAPI. The high-magnification FESEM
image to the inset of Figure 5(b) revealed the large number of
pinholes of diameter between ∼50 and 300 nm in MAPI film
coated over NiO. Figure 5(d) represents the schematic of
many pinholes produced in the MAPI films coated over the
NiO, typically observed with a thermally evaporated metal
oxide underlayer,6,46 which can be tailored under controlled
thickness or roughness of NiO film. Overall, plain MAPI films
showed a larger area uniformity than MAPI films in the NiO/
MAPI heterojunction.
The NiO/MAPI heterojunction formed over the FTO-
coated glass substrate was subsequently tested for its
application as UV and visible-light PDs. I−V curves in Figure
6(a) highlight the clear difference in dark current and light
current under the illumination of different wavelengths.
Additionally, the I−V curves at the applied voltage of −1 to
Figure 5. Top-view FESEM images of the (a) plain MAPI films
1 V are shown in the inset of Figure 6(a). Further, Figure S2 coated over FTO and (b) MAPI films coated over NiO film. Inset:
(Supporting Information) highlights the distinct variation in their respective high-magnification images. Schematics of (c) plain
Idark and Ilight at 0 bias for different wavelengths. This illustrates MAPI films coated over FTO and (d) MAPI films with pinholes
that photogenerated carriers at NiO and perovskite films upon coated over NiO film.
illumination for UV and visible light produced higher current
for a fixed voltage than the dark. The built-in potential at the
NiO/MAPI heterojunction facilitates operation in a self-
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Figure 6. (a) I−V curves of the NiO/MAPI heterojunction photodetector in the dark and under illumination. (b) Variation of responsivity and
detectivity of the NiO/MAPI heterojunction under white light illumination at the applied bias of 0 to +1 V.

powered mode (i.e., at 0 V). The low shunt resistance in NiO/

MAPI resulting from pinholes in MAPI and NiO films might
have produced insignificant rectification. Consequently, the
conductance of the NiO/MAPI heterojunction was measured
at a minimum voltage of 10 mV. The variation in conductance
after illumination at different wavelengths is shown in the
Supporting Information (Figure S3). The least conductance of
0.020 Ω−1 observed in the dark has increased further after
illumination. UV illumination delivered the highest con-
ductance of 0.029 Ω−1, followed by white (i.e., 0.027 Ω−1),
blue (i.e., 0.026 Ω−1), red (i.e., 0.02586 Ω−1), and green (i.e.,
0.02546 Ω−1) light illumination. The variation in conductance
depending on the probing wavelength can be attributed to the
absorption intensity of the NiO/MAPI heterojunction at these
wavelengths. The key parameters such as responsivity and
detectivity were evaluated further to investigate the perform-
ance of the NiO/MAPI heterojunction PD. Figure 6(b) shows
a typical plot of applied bias (0 to +1 V) dependent variation
in the responsivity and detectivity under white light
illumination. The maximum photoresponsivity of 5.79 mA/
W and 29.2 A/W was observed for white light at zero bias and
+1 V, respectively. The variation in the photoresponsivity in
the applied voltage range of +1 V to −1 V is included in the
Supporting Information (Figure S4).
Furthermore, the photodetectivity is one of the important
figures of merit, which is calculated to be 2.3 × 1010 Jones at
zero bias and 2.2 × 1011 Jones at +1 V for visible light. The
values of responsivity and detectivity for NiO/MAPI
heterojunction PDs are analogous to the conventional
perovskite-based PDs consisting of multilayers of ETL−
perovskite−HTL, which include NiO as a front HTL contact
layer. 47,48 Further, the NiO/MAPI heterojunction was
subjected to 30 s illumination cycles with different probing
wavelengths under self-powering mode (i.e., zero bias). Figure
7 shows the light-sensing cycles of the as-fabricated devices
under illumination wavelength of different regions/colors. The
square wave-like sensing cycles were obtained for all the
measurements, which confirms reversible and reproducible
temporal photoresponse at zero bias. Six continuous cycles Figure 7. Probing wavelength-dependent photoresponse cycles of the
involving 60 s dark and light illuminations were performed to NiO/MAPI heterojunction (day 1).
examine the stable light current at zero bias. The highest light
current (i.e., Ilight) was obtained for UV illumination, followed
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Figure 8. Probing wavelength-dependent variation in the (a) difference between Ilight and Idark (i.e., ΔI), (b) sensitivity and on/off ratio, and (c)
responsivity and detectivity of NiO/MAPI heterojunction PDs.

Figure 9. Time-dependent variation in the (a) difference between Ilight and Idark (i.e., ΔI), (b) sensitivity, (c) on/off ratio, (d) responsivity, and (e)
detectivity for NiO/MAPI heterojunction PDs.

by blue-, green-, and red-light illumination, which is akin to the The difference between Ilight and Idark (i.e., ΔI), sensitivity,
absorption spectrum of NiO and MAPI thin films. Further, on/off ratio, responsivity, and detectivity of the NiO/MAPI
these transient measurements were used to evaluate the heterojunction PDs is thoroughly investigated from the
difference between Ilight and Idark (i.e., ΔI) (Supporting temporal response shown in Figure 7. Figure 8(a) shows the
Information, Figure S5) and rise (Tr) and fall (Tf) times at wavelength-dependent variation in the difference between Ilight
90% of Ilight (Supporting Information, Table S1) for each and Idark (i.e., ΔI). The self-powered NiO/MAPI hetero-
junction PD showed the highest ΔI of 38.4 μA for UV light at
illuminating wavelength. The evaluated response time of 300
zero bias. However, the increase in the probing wavelength has
to 400 ms is akin to that of thin-film-assembled perovskite- decreased ΔI. The probing wavelength of 450 ± 5 nm (i.e.,
based PDs.49,50 The low values of rise and fall time are not yet blue), 540 ± 5 nm (green), and 640 ± 5 nm (red) has resulted
well understood. Still, they are believed to arise from the in reduced ΔI of 7.46, 2.96, and 2.64 μA, respectively.
nonuniformity of NiO and MAPI (pinholes), which leads to Nevertheless, white light, a mixture of all wavelengths of visible
scattering of the incident illumination and a decrease in the lights, showed ΔI of 6.66 μA. The probing wavelength-
shunt resistance of the heterojunction. dependent variation in ΔI is in accordance with the measured
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conductance shown in the Supporting Information (Figure NiOx:PbI2-based perovskite PDs.47 Further, the sensitivity
S2). Figure 8(b) reveals the variation in sensitivity and on/off (Figure 9(b)) and on/off ratio (Figure 9(c)) variation
ratio of the self-powered NiO/MAPI heterojunction PDs. The observed for probing wavelength (i.e., UV and vis) on day 1
highest sensitivity and on/off ratio of 169 and 98, respectively, was continued until day 38. It is observed that both sensitivity
were observed for UV sensing. The probing wavelength and on/off ratio were increased for white light from day 1 to
relevant to blue, green, and red light has decreased the day 38. This increase might be attributed to a reduction in Idark,
sensitivity to 71, 40, and 15, respectively. Similarly, the on/off though the decrease in Ilight can be witnessed after the 14th
ratio has reduced from 98 to 14 after increasing the probing day.47 Furthermore, transient characteristics such as rise (Tr)
wavelength from UV to red. However, the sensitivity and on/ and fall (Tf) were investigated for different probing wave-
off ratios of 31 and 33 for white-light sensing of self-powered lengths between day 1 and day 38 and are listed in Supporting
NiO/MAPI PDs are in line with ΔI for different lights. Figure Information Table S2. The response time depends on the RC
8(c) shows the probing wavelength-dependent variation in time constant and carrier transit time at the depletion width,
responsivity and detectivity of self-powered NiO/MAPI and hence the response time has not changed significantly even
heterojunction PDs. The NiO/MAPI heterojunction delivered though the degradation occurred in perovskite during the 38th
a maximum responsivity of 33.39 mA/W at 0 bias for UV light, day.8,55 The slow response of the device might be because of
followed by 6.48, 2.57, 2.29, and 5.79 mA/W for blue, green, developed photodetectors are hole-only devices and the
red, and white lights, respectively. Hu et al.11 have reported depletion width present at both sides of the perovskite.
similar responsivity for UV light illumination, which decreased Moreover, the pinholes in MAPI and NiO films offer low shunt
with increasing wavelength. It is argued that incident light with resistance, which can be improved further by forming a
a smaller wavelength has higher energy to generate more uniform and compact NiO underlayer and processing perov-
electron−hole pairs under the same applied bias. However, in skite in a controlled environment. The improvement in the
our case, it is worth mentioning that the NiO front contact shunt resistance will drastically reduce the response time.
layer contribution in the photocurrent under UV light Time-dependent variation of responsivity and detectivity of
illumination at the NiO/MAPI interface cannot be denied, as self-powered NiO/MAPI heterojunction PDs is as shown in
in NiO heterojunctions with silicon51 and ZnO.52,53 Further, Figure 9(d) and Figure 9(e), respectively. The maximum
the detectivity in the order 1011 Jones was achieved for UV responsivity of 40.56 mA/W was observed on the 14th day for
light. Further increase in probing wavelength to the visible blue light, followed by UV, green, red, and white wavelengths.
region led to decreased detectivity (order of 1010 Jones). The This is in line with the variation of ΔI reaching a peak value at
high values of responsivity (above 1 mA/W) and detectivity the 14th day and suggests optimized PbI2 content was
(order of 1010 Jones) reveal the good functionality of our developed at the 14th day. Additionally, Figure 9(e) shows
device in the entire UV and visible spectrum. excellent detectivity in the order of 1010 Jones for the NiO/
The MAPI perovskite can lead to the deterioration in the MAPI heterojunction up to 38 days.
performance of the PD. The moisture-induced degradation of The moisture-induced degradation of MAPI films strongly
MAPI can result in the formation of PbI2 and aqueous influences the photoresponse of the self-powered NiO/MAPI
CH3NH3I, which fundamentally change the charge transport heterojunction PDs. Consequently, it is important to under-
characteristics in MAPI films.54 Therefore, to understand the stand the structural changes resulting from perovskite
temporal stability of ambient stored and self-powered NiO/ degradation with passing days in an ambient atmosphere.
MAPI heterojunction PD, the temporal cycles for each probing XRD patterns of MAPI films in NiO/MAPI heterojunctions
wavelength were measured at random intervals for 58 days. shown in Figure 10 were measured before each sensing cycle
The sensing performance of the NiO/MAPI self-powered on respective days. The XRD pattern of MAPI films in the
heterojunction measured at zero bias for different probing inset of Figure 10 reveals that the tetragonal phase is consistent
wavelengths during the 4th, 14th, 28th, 38th, and 58th day is with the JCPDS card no. 41-1445 and reported litera-
shown in the Supporting Information (Figure S6−S10, ture.44,56−58 The signature peak observed at 12.65° (identified
respectively). The cyclic temporal performance degraded as
the days progressed and disfigured on the 58th day
(Supporting Information Figure S10). Therefore, the photo-
detection parameters for each incident wavelength were
calculated up to 38 days (Figure 9). As the days progressed,
ΔI of self-powered NiO/MAPI heterojunction PD increased
up to 14 days and decreased after that until 58 days (Figure
9(a)). However, the 14th day rise in ΔI for the blue light might
be due to the wavelength proximity of the blue and UV region.
The optimal content of PbI2 resulting from degradation of
perovskite might be behind the maximum values of ΔI on the
14th day. Similarly, high values of light current and
responsivity were observed for a wide range of PbI2 content.
It was concluded that the higher conduction band edge and
lower valence band edge energy levels of PbI2 than that of
MAPI further suppress the electron injection from MAPI into
the NiO (Figure 3(c)). The MAPI degrades with time, and the
evolution of PbI2 in MAPI takes place, resulting in suppressed
dark current and increased responsivity. These observations are Figure 10. Illumination-day-dependent XRD pattern of MAPI films
akin to literature reporting the enhanced photocurrent in (inset shows XRD up to 35°).

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as *) represents the existence of PbI2.59 The intensity of the UV−vis absorption spectrum of NiO film; I−V and
peak at 12.65° was insignificant for as-prepared NiO/MAPI conductance curve of the NiO/MAPI heterojunction at
heterojunction thin films on day 1, indicating the negligible 0 bias; photoresponsivity, photocurrent at ON/OFF
existence of PbI2. However, a gradual increase in its intensity cycles and wavelength- and time-dependent photo-
reflects the formation of PbI2 as the days progressed. The response of the NiO/MAPI heterojunction; switching
distinguishable existence of PbI2 was observed on day 4. The time of self-powered NiO/MAPI; and comparative
highest intensity of the PbI2 peak was observed on the 58th studies of metal-oxide-based perovskite PDs (PDF)

■
day. The peak intensity ratio of PbI2 (i.e., IDx/ID1, where x = 4,
14, 28, 38, and 58) has increased from 11.46 to 35.58 from day AUTHOR INFORMATION
4 to day 58. The formation of the larger amount of PbI2 on day Corresponding Authors
58 might have disfigured the sensing cycle and drastically Rupesh S. Devan − Department of Metallurgy Engineering
degraded the PD performance. The presence of an optimal and Materials Science, Indian Institute of Technology Indore,
amount of PbI2 in MAPI films might have resulted in an Simrol 453552, India; orcid.org/0000-0001-9550-7506;
increase in ΔI up to 14 days. The content of PbI2 in MAPI Email: [email protected]
films on the 14th day was calculated with eq 7 and found to be Parvez A. Shaikh − Department of Metallurgy Engineering
61 ± 2%. However, after 14 days, the degradation has and Materials Science, Indian Institute of Technology Indore,
progressed further, and >62% PbI2 content was observed in Simrol 453552, India; Department of Physics, AKI’s Poona
MAPI. The larger PbI2 content has suppressed optoelectronic College of Arts, Science and Commerce, Pune, Maharashtra
properties of MAPI perovskite light absorber (i.e., reduced Idark 411001, India; orcid.org/0000-0002-4389-2286;
and Ilight) and gives rise to lower ΔI. These observations are Email: [email protected]
akin to literature reporting the enhanced photocurrent in
NiOx:PbI2-based perovskite PDs.47 In total, it is observed that Authors
high-performance PDs can be fabricated by tailoring the Vishesh Manjunath − Department of Metallurgy Engineering
concentration/formation of PbI2 in MAPI films. Further, the and Materials Science, Indian Institute of Technology Indore,
developed PDs use p−n junctions, unlike n-i-p or p-i-n Simrol 453552, India; orcid.org/0000-0003-4316-8180
junctions reported in the literature (Supporting Information, Prashant Kumar Mishra − Department of Physics, Indian
Table S3). Recently, Nguyen et al.60 demonstrated self- Institute of Technology Indore, Simrol 453552, India
powered perovskite-based PD delivering performance similar Rachit Dobhal − Department of Physics, Indian Institute of
to the present study, but the use of complex perovskite Technology Indore, Simrol 453552, India
composition and an expensive spiro-OMeTAD is not cost- Santosh Bimli − Department of Metallurgy Engineering and
effective. On the other hand, the present studies provide a Materials Science, Indian Institute of Technology Indore,
candid guide to understand the effect of intrinsic modifications Simrol 453552, India; orcid.org/0000-0003-2096-0458
on the optoelectronic properties of organic−inorganic perov- Parasharam M. Shirage − Department of Metallurgy
skites for application in self-powered PDs. Engineering and Materials Science, Indian Institute of

■ CONCLUSION
In conclusion, we have successfully fabricated a self-powered
Technology Indore, Simrol 453552, India; orcid.org/
0000-0003-2884-7548
Somaditya Sen − Department of Physics, Indian Institute of
NiO/MAPI heterojunction PD in ambient conditions. NiO Technology Indore, Simrol 453552, India; orcid.org/
thin films were synthesized by thermal evaporation followed by 0000-0002-6129-8344
oxidation, and the MAPI overlayer was coated with a two-step Complete contact information is available at:
deposition process in ambient. The multifunctional NiO film https://pubs.acs.org/10.1021/acsaelm.1c00679
provided PD with both built-in potentials and also acted as a
template to enhance the light absorption of the MAPI films. Author Contributions
Thus, self-powered NiO/MAPI heterojunction PD showed R.S.D. supervised the experiments. V.M. performed the
high detectivity in the order of 1010 Jones. Further, the experiments. V.M., P.A.S., and R.S.D. wrote the manuscript.
performance parameters of self-powered PD for each probing All authors analyzed data, discussed the results thoroughly, and
wavelength from UV to visible were studied for up to 58 days provided comments about the manuscript.
stored in ambient. The X-ray diffraction (XRD) was recorded Funding
for up to 58 days to analyze the degradation of MAPI. The The authors would like to thank TARE-DST India and UGC-
changes in performance parameters of self-powered PD were DAE CSR Indore for their financial support to this research
related to the degradation of MAPI films. These results not under grant nos. TAR/2019/000106 and CSR-IC-BL-65/
only explain the degradation of MAPI w.r.t. performance of CRS-182/2017-18/189, respectively.
PDs but also helps to understand the influence of intrinsic
modifications of hybrid perovskite on the photoresponse of Notes
The authors declare no competing financial interest.

■
such perovskite heterojunctions used in other optoelectronic
devices. This study will instigate researchers to modulate the
REFERENCES
optoelectronic properties of metal halide perovskite through
intrinsic modifications. (1) Leung, S.-F.; Ho, K.-T.; Kung, P.-K.; Hsiao, V. K. S.; Alshareef,

■
H. N.; Wang, Z. L.; He, J. H. A self-powered and flexible
organometallic halide perovskite photodetector with very high
ASSOCIATED CONTENT
detectivity. Adv. Mater. 2018, 30, 1704611.
*
sı Supporting Information
(2) Jena, A. K.; Kulkarni, A.; Miyasaka, T. Halide Perovskite
The Supporting Information is available free of charge at Photovoltaics: Background, Status, and Future Prospects. Chem. Rev.
https://pubs.acs.org/doi/10.1021/acsaelm.1c00679. 2019, 119, 3036−3103.

4555 https://doi.org/10.1021/acsaelm.1c00679
ACS Appl. Electron. Mater. 2021, 3, 4548−4557
ACS Applied Electronic Materials pubs.acs.org/acsaelm Article

(3) Gonzalez-Pedro, V.; Juarez-Perez, E. J.; Arsyad, W.-S.; Barea, E. Nanotubes Array for Broadband Response Photodetector. Adv.
M.; Fabregat-Santiago, F.; Mora-Sero, I.; Bisquert, J. General Working Funct. Mater. 2017, 27, 1703115.
Principles of CH3NH3PbX3 Perovskite Solar Cells. Nano Lett. 2014, (21) Gao, T.; Zhang, Q.; Chen, J.; Xiong, X.; Zhai, T. Performance-
14, 888−893. Enhancing Broadband and Flexible Photodetectors Based on
(4) Alsalloum, A. Y.; Turedi, B.; Almasabi, K.; Zheng, X.; Naphade, Perovskite/ZnO-Nanowire Hybrid Structures. Adv. Opt. Mater.
R.; Stranks, S. D.; Mohammed, O. F.; Bakr, O. M. 22.8%-Efficient 2017, 5, 1700206.
single-crystal mixed-cation inverted perovskite solar cells with a near- (22) Zhu, Y.; Song, Z.; Zhou, H.; Wu, D.; Lu, R.; Wang, R.; Wang,
optimal bandgap. Energy Environ. Sci. 2021, 14, 2263−2268. H. Self-powered, broadband perovskite photodetector based on ZnO
(5) Maniarasu, S.; Korukonda, T. B.; Manjunath, V.; Ramasamy, E.; microspheres as scaffold layer. Appl. Surf. Sci. 2018, 448, 23−29.
Ramesh, M.; Veerappan, G. Recent advancement in metal cathode (23) Zhou, H.; Song, Z.; Tao, P.; Lei, H.; Gui, P.; Mei, J.; Wang, H.;
and hole-conductor-free perovskite solar cells for low-cost and high Fang, G. Self-powered, ultraviolet-visible perovskite photodetector
stability: A route towards commercialization. Renewable Sustainable based on TiO2 nanorods. RSC Adv. 2016, 6, 6205−6208.
Energy Rev. 2018, 82, 845−857. (24) Yu, J.; Chen, X.; Wang, Y.; Zhou, H.; Xue, M.; Xu, Y.; Li, Z.;
(6) Manjunath, V.; Bimli, S.; Parmar, K. H.; Shirage, P. M.; Devan, Ye, C.; Zhang, J.; van Aken, P. A.; Lund, P. D.; Wang, H. A high-
R. S. Oxidized Nickel films as highly transparent HTLs for inverted performance self-powered broadband photodetector based on a
planar perovskite solar cells. Sol. Energy 2019, 193, 387−394. CH3NH3PbI3 perovskite/ZnO nanorod array heterostructure. J.
(7) Gu, Z.; Wang, K.; Sun, W.; Li, J.; Liu, S.; Song, Q.; Xiao, S. Two- Mater. Chem. C 2016, 4, 7302−7308.
Photon Pumped CH3NH3PbBr3 Perovskite Microwire Lasers. Adv. (25) Shen, L.; Fang, Y.; Wang, D.; Bai, Y.; Deng, Y.; Wang, M.; Lu,
Opt. Mater. 2016, 4, 472−479. Y.; Huang, J. A Self-Powered, Sub-nanosecond-Response Solution-
(8) Wang, H.-P.; Li, S.; Liu, X.; Shi, Z. F.; Fang, X. S.; He, J. H. Low- Processed Hybrid Perovskite Photodetector for Time-Resolved
dimensional metal halide perovskite photodetectors. Adv. Mater. Photoluminescence-Lifetime Detection. Adv. Mater. 2016, 28,
2021, 33, 2003309. 10794−10800.
(9) Tan, Z.-K.; Moghaddam, R. S.; Lai, M. L.; Docampo, P.; Higler, (26) Li, J.; Yuan, S.; Tang, G.; Li, G.; Liu, D.; Li, J.; Hu, X.; Liu, Y.;
R.; Deschler, F.; Price, M.; Sadhanala, A.; Pazos, L. M.; Credgington, Li, J.; Yang, Z.; Liu, S. F.; Liu, Z.; Gao, F.; Yan, F. High-Performance,
D.; Hanusch, F.; Bein, T.; Snaith, H. J.; Friend, R. H. Bright light- Self-Powered Photodetectors Based on Perovskite and Graphene.
emitting diodes based on organometal halide perovskite. Nat. ACS Appl. Mater. Interfaces 2017, 9, 42779−42787.
Nanotechnol. 2014, 9, 687−692. (27) Liu, Y.; Jia, R.; Wang, Y.; Hu, Z.; Zhang, Y.; Pang, T.; Zhu, Y.;
(10) Cho, H.; Jeong, S.-H.; Park, M.-H.; Kim, Y.-H.; Wolf, C.; Lee, Luan, S. Inhibition of Zero Drift in Perovskite-Based Photodetector
C.-L.; Heo, J. H.; Sadhanala, A.; Myoung, N.; Yoo, S.; Im, S. H.; Devices via [6,6]-Phenyl-C61-butyric Acid Methyl Ester Doping. ACS
Friend, R. H.; Lee, T.-W. Overcoming the electroluminescence Appl. Mater. Interfaces 2017, 9, 15638−15643.
efficiency limitations of perovskite light-emitting diodes. Science 2015, (28) Qin, L.; Wu, L.; Kattel, B.; Li, C.; Zhang, Y.; Hou, Y.; Wu, J.;
350, 1222−1225. Chan, W.-L. Using Bulk Heterojunctions and Selective Electron
(11) Hu, X.; Zhang, X.; Liang, L.; Bao, J.; Li, S.; Yang, W.; Xie, Y. Trapping to Enhance the Responsivity of Perovskite−Graphene
High-Performance Flexible Broadband Photodetector Based on Photodetectors. Adv. Funct. Mater. 2017, 27, 1704173.
Organolead Halide Perovskite. Adv. Funct. Mater. 2014, 24, 7373− (29) Patil, R. A.; Devan, R. S.; Lin, J.-H.; Ma, Y.-R.; Patil, P. S.; Liou,
7380. Y. Efficient electrochromic properties of high-density and large-area
(12) Dou, L.; Yang, Y.; You, J.; Hong, Z.; Chang, W.-H.; Li, G.; arrays of one-dimensional NiO nanorods. Sol. Energy Mater. Sol. Cells
Yang, Y. Solution-processed hybrid perovskite photodetectors with 2013, 112, 91−96.
high detectivity. Nat. Commun. 2014, 5, 5404. (30) Devan, R. S.; Patil, R. A.; Lin, J.-H.; Ma, Y.-R. One-Dimensional
(13) Sutherland, B. R.; Johnston, A. K.; Ip, A. H.; Xu, J.; Adinolfi, V.; Metal-Oxide Nanostructures: Recent Developments in Synthesis,
Kanjanaboos, P.; Sargent, E. H. Sensitive, Fast, and Stable Perovskite Characterization, and Applications. Adv. Funct. Mater. 2012, 22,
Photodetectors Exploiting Interface Engineering. ACS Photonics 2015, 3326−3370.
2, 1117−1123. (31) Dalavi, D. S.; Devan, R. S.; Patil, R. S.; Ma, Y.-R.; Patil, P. S.
(14) Dong, Y.; Gu, Y.; Zou, Y.; Song, J.; Xu, L.; Li, J.; Xue, J.; Li, X.; Electrochromic performance of sol-gel deposited NiO thin film.
Zeng, H. Improving All-Inorganic Perovskite Photodetectors by Mater. Lett. 2013, 90, 60−63.
Preferred Orientation and Plasmonic Effect. Small 2016, 12, 5622− (32) Dalavi, D. S.; Devan, R. S.; Patil, R. S.; Ma, Y.-R.; Kang, M.-G.;
5632. Kim, J.-H.; Patil, P. S. Electrochromic properties of dandelion flower
(15) Zhang, T.; Wu, J.; Zhang, P.; Ahmad, W.; Wang, Y.; Alqahtani, like nickel oxide thin films. J. Mater. Chem. A 2013, 1, 1035−1039.
M.; Chen, H.; Gao, C.; Chen, Z. D.; Wang, Z.; Li, S. High Speed and (33) Lu, H.; Tian, W.; Cao, F.; Ma, Y.; Gu, B.; Li, L. A Self-Powered
Stable Solution-Processed Triple Cation Perovskite Photodetectors. and Stable All-Perovskite Photodetector−Solar Cell Nanosystem. Adv.
Adv. Opt. Mater. 2018, 6, 1701341. Funct. Mater. 2016, 26, 1296−1302.
(16) Liu, B.; Gutha, R. R.; Kattel, B.; Alamri, M.; Gong, M.; Sadeghi, (34) Zhou, H.; Zeng, J.; Song, Z.; Grice, C. R.; Chen, C.; Song, Z.;
S. M.; Chan, W.-L.; Wu, J. Z. Using Silver Nanoparticles-Embedded Zhao, D.; Wang, H.; Yan, Y. Self-Powered All-Inorganic Perovskite
Silica Metafilms as Substrates to Enhance the Performance of Microcrystal Photodetectors with High Detectivity. J. Phys. Chem.
Perovskite Photodetectors. ACS Appl. Mater. Interfaces 2019, 11, Lett. 2018, 9, 2043−2048.
32301−32309. (35) Li, F.; Liu, M. Recent efficient strategies for improving the
(17) Li, F.; Ma, C.; Wang, H.; Hu, W.; Yu, W.; Sheikh, A. D.; Wu, T. moisture stability of perovskite solar cells. J. Mater. Chem. A 2017, 5,
Ambipolar solution-processed hybrid perovskite phototransistors. Nat. 15447−15459.
Commun. 2015, 6, 8238. (36) Divitini, G.; Cacovich, S.; Matteocci, F.; Cinà, L.; Di Carlo, A.;
(18) Saidaminov, M. I.; Adinolfi, V.; Comin, R.; Abdelhady, A. L.; Ducati, C. In situ observation of heat-induced degradation of
Peng, W.; Dursun, I.; Yuan, M.; Hoogland, S.; Sargent, E. H.; Bakr, O. perovskite solar cells. Nat. Energy 2016, 1, 15012.
M. Planar-integrated single-crystalline perovskite photodetectors. Nat. (37) Zhang, Z.; Suchan, K.; Li, J.; Hetherington, C.; Kiligaridis, A.;
Commun. 2015, 6, 8724. Unger, E.; Scheblykin, I. G.; Wallentin, J. Vertically Aligned CsPbBr3
(19) Alwadai, N.; Haque, M. A.; Mitra, S.; Flemban, T.; Pak, Y.; Wu, Nanowire Arrays with Template-Induced Crystal Phase Transition
T.; Roqan, I. High-Performance Ultraviolet-to-Infrared Broadband and Stability. J. Phys. Chem. C 2021, 125, 4860−4868.
Perovskite Photodetectors Achieved via Inter-/Intraband Transitions. (38) Gu, L.; Tavakoli, M. M.; Zhang, D.; Zhang, Q.; Waleed, A.;
ACS Appl. Mater. Interfaces 2017, 9, 37832−37838. Xiao, Y.; Tsui, K.-H.; Lin, Y.; Liao, L.; Wang, J.; Fan, Z. 3D Arrays of
(20) Zheng, Z.; Zhuge, F.; Wang, Y.; Zhang, J.; Gan, L.; Zhou, X.; 1024-Pixel Image Sensors based on Lead Halide Perovskite
Li, H.; Zhai, T. Decorating Perovskite Quantum Dots in TiO2 Nanowires. Adv. Mater. 2016, 28, 9713−9721.

4556 https://doi.org/10.1021/acsaelm.1c00679
ACS Appl. Electron. Mater. 2021, 3, 4548−4557
ACS Applied Electronic Materials pubs.acs.org/acsaelm Article

(39) Bao, C.; Yang, J.; Bai, S.; Xu, W.; Yan, Z.; Xu, Q.; Liu, J.; Zhang, (56) Jassim, S. M.; Bakr, N. A.; Mustafa, F. I. Synthesis and
W.; Gao, F. High Performance and Stable All-Inorganic Metal Halide characterization of MAPbI3 thin film and its application in C-Si/
Perovskite-Based Photodetectors for Optical Communication Appli- perovskite tandem solar cell. J. Mater. Sci.: Mater. Electron. 2020, 31,
cations. Adv. Mater. 2018, 30, 1803422. 16199−16207.
(40) Li, C.; Han, C.; Zhang, Y.; Zang, Z.; Wang, M.; Tang, X.; Du, J. (57) Tavakoli, M. M.; Gu, L.; Gao, Y.; Reckmeier, C.; He, J.;
Enhanced photoresponse of self-powered perovskite photodetector Rogach, A. L.; Yao, Y.; Fan, Z. Fabrication of efficient planar
based on ZnO nanoparticles decorated CsPbBr3 films. Sol. Energy perovskite solar cells using a one-step chemical vapor deposition
Mater. Sol. Cells 2017, 172, 341−346. method. Sci. Rep. 2015, 5, 14083.
(41) Qi, Z.; Fu, X.; Yang, T.; Li, D.; Fan, P.; Li, H.; Jiang, F.; Li, L.; (58) Peng, H.; Lan, C.; Chen, S.; Fan, P.; Liang, G.; Lan, H. N,N-
Luo, Z.; Zhuang, X.; Pan, A. Highly stable lead-free Cs3Bi2I9 dimethylformamide vapor effect on microstructural and optical
perovskite nanoplates for photodetection applications. Nano Res. properties of CH3NH3PbI3 film during solvent annealing. Surf. Coat.
2019, 12, 1894−1899. Technol. 2019, 359, 162−168.
(42) Hussain, A. A.; Rana, A. K.; Ranjan, M. Air-stable lead-free (59) Zhang, H.; Tao, M.; Gao, B.; Chen, W.; Li, Q.; Xu, Q.; Dong, S.
hybrid perovskite employing self-powered photodetection with an Preparation of CH3NH3PbI3 thin films with tens of micrometer scale
electron/hole-conductor-free device geometry. Nanoscale 2019, 11, at high temperature. Sci. Rep. 2017, 7, 8458.
1217−1227. (60) Nguyen, T. M. H.; Kim, S.; Bark, C. W. Solution-processed and
(43) Park, J. H.; Seo, J.; Park, S.; Shin, S. S.; Kim, Y. C.; Jeon, N. J.; self-powered photodetector in vertical architecture using mixed-halide
Shin, H.-W.; Ahn, T. K.; Noh, J. H.; Yoon, S. C.; Hwang, C. S.; Seok, perovskite for highly sensitive UVC detection. J. Mater. Chem. A 2021,
S. I. Efficient CH3NH3PbI3 Perovskite Solar Cells Employing 9, 1269−1276.
Nanostructured p-Type NiO Electrode Formed by a Pulsed Laser
Deposition. Adv. Mater. 2015, 27, 4013−4019.
(44) Song, J.; Zheng, E.; Bian, J.; Wang, X.-F.; Tian, W.; Sanehira,
Y.; Miyasaka, T. Low-temperature SnO2-based electron selective
contact for efficient and stable perovskite solar cells. J. Mater. Chem. A
2015, 3, 10837−10844.
(45) Shi, Y.; Xing, Y.; Li, Y.; Dong, Q.; Wang, K.; Du, Y.; Bai, X.;
Wang, S.; Chen, Z.; Ma, T. CH3NH3PbI3 and CH3NH3PbI3−xClx in
Planar or Mesoporous Perovskite Solar Cells: Comprehensive Insight
into the Dependence of Performance on Architecture. J. Phys. Chem.
C 2015, 119, 15868−15873.
(46) Wang, K.; Tian, Y.; Jiang, H.; Chen, M.; Xu, S. Surface
Treatment on Nickel Oxide to Enhance the Efficiency of Inverted
Perovskite Solar Cells. Int. J. Photoenergy 2019, 2019, 4360816.
(47) Zhu, H. L.; Cheng, J.; Zhang, D.; Liang, C.; Reckmeier, C. J.;
Huang, H.; Rogach, A. L.; Choy, W. C. H. Room-Temperature
Solution-Processed NiOx:PbI2 Nanocomposite Structures for Realiz-
ing High-Performance Perovskite Photodetectors. ACS Nano 2016,
10, 6808−6815.
(48) Afzal, A. M.; Bae, I.-G.; Aggarwal, Y.; Park, J.; Jeong, H.-R.;
Choi, E. H.; Park, B. Highly efficient self-powered perovskite
photodiode with an electron-blocking hole-transport NiOx layer. Sci.
Rep. 2021, 11, 169.
(49) Xia, H.-R.; Li, J.; Sun, W.-T.; Peng, L.-M. Organohalide lead
perovskite based photodetectors with much enhanced performance.
Chem. Commun. 2014, 50, 13695−13697.
(50) Deng, H.; Dong, D.; Qiao, K.; Bu, L.; Li, B.; Yang, D.; Wang,
H.-E.; Cheng, Y.; Zhao, Z.; Tang, J.; Song, H. Growth, patterning and
alignment of organolead iodide perovskite nanowires for optoelec-
tronic devices. Nanoscale 2015, 7, 4163−4170.
(51) Al-Hardan, N. H.; Ahmed, N. M.; Almessiere, M. A.; Aziz, A. A.
Low-Intensity UV light sensor based on p-NiO/n-Si heterojunction.
Mater. Res. Express 2019, 6, 126332.
(52) Zhang, Y.; Ji, T.; Zou, R.; Ha, E.; Hu, X.; Cui, Z.; Xu, C.; He, S.
a.; Xu, K.; Zhang, Y.; Hu, J. An efficiently enhanced UV-visible light
photodetector with a Zn:NiO/p-Si isotype heterojunction. J. Mater.
Chem. C 2020, 8, 3498−3508.
(53) Echresh, A.; Chey, C. O.; Zargar Shoushtari, M.; Khranovskyy,
V.; Nur, O.; Willander, M. UV photodetector based on p-NiO thin
film/n-ZnO nanorods heterojunction prepared by a simple process. J.
Alloys Compd. 2015, 632, 165−171.
(54) Toloueinia, P.; Khassaf, H.; Shirazi Amin, A.; Tobin, Z. M.;
Alpay, S. P.; Suib, S. L. Moisture-Induced Structural Degradation in
Methylammonium Lead Iodide Perovskite Thin Films. ACS Appl.
Energy Mater. 2020, 3, 8240−8248.
(55) Li, C.; Wang, H.; Wang, F.; Li, T.; Xu, M.; Wang, H.; Wang, Z.;
Zhan, X.; Hu, W.; Shen, L. Ultrafast and broadband photodetectors
based on a perovskite/organic bulk heterojunction for large-dynamic-
range imaging. Light: Sci. Appl. 2020, 9, 31.

4557 https://doi.org/10.1021/acsaelm.1c00679
ACS Appl. Electron. Mater. 2021, 3, 4548−4557