Sensors & Actuators: A.

Physical 345 (2022) 113799

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Sensors and Actuators: A. Physical

journal homepage: www.journals.elsevier.com/sensors-and-actuators-a-physical

Performance evaluation of transparent self-powered n-ZnO/p-NiO

heterojunction ultraviolet photosensors
Parashurama Salunkhe , Prashant Bhat , Dhananjaya Kekuda *
Department of Physics, Manipal Institute of Technology, Manipal Academy of Higher Education, Manipal 576104, India

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

Keywords: We have constructed NiO/ZnO thin film heterojunction diodes by dc magnetron sputtering technique and
Self-powered evaluated their performance for ultraviolet sensor applications. The constructed device configuration, ITO/ZnO/
UV photodetector NiO/Ag exhibited excellent current-voltage rectifying characteristics in the order of 105 at room temperature.
N-ZnO/p-NiO heterojunction
The effect of rapid thermal annealing treatment on the fabricated ITO/ZnO/NiO thin film stack was evaluated for
Performance evaluation
their photodetector characteristics. The structural, optical, and spectroscopic properties were also investigated.
Further, the ITO/ZnO/NiO/Ag diodes were tested under 365 nm UV light illumination having a power density of
0.06 mW/cm2. Remarkably, a speed of response with rise/fall time of 197.29/537.10 ms has been recorded at
self-powered mode. Interestingly, the photodiode device has exhibited a spectral responsivity of 13.01 mA/W
and stable photo detectivity of 5.66 × 1011 Jones at room temperature. The n-ZnO/p-NiO heterojunction
photodetector has shown its ability to detect a faint UV light in a self-powered mode.

1. Introduction attracted numerous applications such as hole transport layer, an electron

blocking layer, buffer layer in organic solar cells, gas sensors, UV
UV detectors are critical for humanity’s survival and progress to- photodetector, Light-emitting diodes (LEDs), memory devices, thin film
wards a better livelihood since excessive exposure to UV radiation transistors, transparent solar cells, P-N junctions [9–16]. Among all
causes skin cancer, immune system damage, ageing process etc. [1–3]. oxide semiconductors, NiO is intrinsically solar blind and its physical
UV photodetectors are optoelectronic devices with a wide range of ap- properties show promising spectral responsivity in the UV region. It has
plications, including radiation detection, biological analysis, flame an optically wide direct band gap ranging from 3.2 to 3.6 eV with an
detection, UV imaging, pollution monitoring, and space communica- intrinsically p-type semiconductor behaviour and it has low electron
tions [4–6]. In recent years, a conventional silicon-based Ultra-Violet affinity ranging from 1.46 to 1.85 eV [17–19]. Moreover, NiO is avail-
(UV) detector has been used for many applications. It has an indirect able at a low cost since it is abundant in the earth’s crust, and it is a
band gap (Si ~ 1.1 eV) and the need for expensive filters for rejecting stable material even under harsh environmental conditions. Moreover, it
visible bands for UV photodetector applications are some of its draw- is environmentally friendly in which Nickel and Oxygen are less toxic
backs with poor performance, low efficiency, and increasing dark cur- compared to other transparent semiconductors. In UV photosensors, one
rent [5,7]. Hence exploring the wide band gap material’s physical of the different composites is responsible for photon absorption and the
properties and fabrication of UV photodetectors is necessary for the other enables the building of a junction. The construction of a hetero-
current scenario. structure, in which charges are kept separate, prevents photocarrier
Recently, transparent electronics has emerged as one of the most recombination and enhances detector sensitivity. To accomplish this,
sensational and promising fields of optoelectronics. By definition, op- lattice matched transparent metal oxide semiconductors (MOS) with
toelectronic devices, convert the light energy into an electrical signal superior electrical characteristics must be utilized. ZnO has been a
that can be utilized for sensitivity, selectivity, energy harvesting etc.[8]. well-known transparent n type semiconductor material among various
Most of the oxide semiconductors exhibit wide band gap nature, which available metal oxides due to its high optical band gap (3.40 eV), high
can be utilized as future candidates in the field of optoelectronics ap- exciton binding energy (60 meV) and is chemically stable hexagonal
plications. Vast material characteristics of oxide semiconductors crystal structure [18,20].

* Corresponding author.
E-mail address: [email protected] (D. Kekuda).

https://doi.org/10.1016/j.sna.2022.113799
Received 11 July 2022; Received in revised form 25 July 2022; Accepted 30 July 2022
Available online 3 August 2022
0924-4247/© 2022 Elsevier B.V. All rights reserved.
P. Salunkhe et al. Sensors and Actuators: A. Physical 345 (2022) 113799

The advantage of the ITO/ZnO/NiO/Ag Photodiode is the low and applied DC 50 W power. The deposition pressure was maintained at
complexity of the device structure with low contact resistance. NiO and 7.5mTorr throughout the sputtering process. Before the deposition, the
ZnO thin films can be utilised to fabricate the UV photodetector, by a DC magnetron sputtering chamber was pumped down to 5.25 × 10−6
simple and economically low-cost dc magnetron sputtering technique. Torr. All the samples were subjected to different rapid thermal annealing
The composition of the film depends on the operating conditions which procedures for about 15 min on a hot plate to get a better interface
can be easily controllable. In this case film purity was superior as between the ZnO and NiO films and to evaluate the device performance.
compared to the films grown by CVD methods and it is well suitable for Finally, top electrode silver of a thickness of 70 nm was thermally
the device applications. In the present work, a quality interface between evaporated at the rate of 5Å/s by using a shadow mask.
ZnO and NiO was formed with good adhesion because of their similar
lattice constants. It can open a new window for inexpensive deposition 2.2. Characterization and device measurements
of high crystal quality thin films. The previous literature reports address
on the morphology, doping concentration, crystallinity and varying the To investigate the crystal structure and structural properties of the
deposition parameters etc, to achieve a better photo sensor. Rapid ITO, ZnO, and NiO thin films, a Glancing angle x-ray diffraction (XRD,
thermal treatment is one of the simple and effective approaches to Rigaku smart lab, CuKα, λ = 1.540Å) was used. The optical properties
enhance the device performance by reducing grain boundaries, lowering were investigated by using SHIMADZU UV-1800 double beam spectro-
the material defects states, and increasing crystallinity. Even though photometer and the thickness of the films was measured by a Dektak
several attempts have been made on ZnO/NiO heterojunction UV- stylus profilometer. Field-Emission Scanning Electron Microscopy
Photodetectors and their figure of merits such as quantum efficiency (FESEM) was utilized for morphological examination of the individual
and linear dependence of responsivity (LDR) have not been explored layers and to view the device cross-section. The chemical composition
much under zero bias mode. In addition, a study on the effect of rapid and the oxidation state of the film were characterized by X-ray photo-
thermal annealing on ZnO/NiO heterojunction and their physical electron spectroscopy (XPS, Axis ultra DLD – Kratos analytical). The
properties is required to see their feasibility for photodetector applica- excitation source for XPS has contained monochromatic Al Kα X-rays
tions. In the present work, we have systematically carried out rapid (1486.69 eV). Dark mode current-voltage (IV) measurements were
thermal treatments for all the samples to modulate the charge transport performed by using Keithley 2636B dual source meter unit. The photo
mechanism at the ZnO/NiO interface. Finally, NiO/ZnO heterojunction response study of the detector was carried out by using a monochromatic
Photodiode was tested under the zero bias mode with the 365 nm UV 365 nm UV LED source lamp with a calibrated 0.06 mW/cm2 of optical
light illumination. power and 365 nm UV light was chopped by an optical chopper.

2. Experimental details 3. Results and discussions

2.1. Device fabrication The effect of thermal treatment on the structural, optical and spec-
troscopic properties of the ZnO/NiO layers have been studied system-
The UV photodetector with a design of ITO/ZnO/NiO/Ag hetero- atically. The Grazing angle X-ray diffraction (XRD) spectra of ZnO and
junction was constructed. The schematic representation of the photo- NiO thin film grown on ITO glass at room temperature is shown in Fig. 2
diode and their energy band diagram is illustrated in Fig. 1(a) and (b). (a). It was observed that NiO thin film XRD pattern has intense and
The chemically etched and patterned ITO coated glass substrates were sharp (200) preferred orientation followed by(111),(220), and(311)
used as a back contact. The ITO coated substrates were cleaned with Braggs peaks located at 43.04 , 37.04 , 62.84 74.72 , respectively
◦ ◦ ◦ ◦

deionized water, acetone and isopropyl alcohol using ultrasonication for [21]. It represents a FCC phase with cubic rock salt structure as per the
about 10 min. Further, all substrates were dried with Nitrogen gas standard JCPDS (data No. 03-065-2901) and there were no impurity
(purity-99.999 %). The ZnO and NiO thin films were deposited on phases observed. The ITO substrate Bragg reflection peak (400) is also
patterned ITO substrates by the DC magnetron sputtering technique. reflected in the XRD spectra and it is located at 34.40 [22]. For, the
◦

Firstly, a 2-inch circular Zn target (Hind High Vacuum, 99.99 % purity) stack of ITO/ZnO/NiO heterojunction, the XRD pattern of ZnO thin film
was used to deposit the ZnO film on patterned ITO substrates at 40 W of exhibited Bragg peak located at 2θ of 34.20 which is almost merged
◦

sputter power at room temperature under the ratio of 4:1 sccm of Ar/O2
with the ITO Bragg peak. In addition a small peak at 35.98 represent
◦

gas atmosphere. A Ni target (Hind High Vacuum, 99.99 % purity) was

(011) preferred orientation of ZnO having a wurtzite type of structure
used to deposit the NiO thin films at an Ar/O2 gas flow ratio of 6:1 sccm
with a space group of P63mc (COD: 9011662) [23,24]. The good

Fig. 1. (a) Schematic illustration of ZnO/NiO heterojuntion based Photodetector. (b) Energy band diagram of the ZnO/NiO haterojunction. EC, EV, EF represent the
conduction band edge,valence band edge and Fermi level, respectively.

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P. Salunkhe et al. Sensors and Actuators: A. Physical 345 (2022) 113799

Fig. 2.(. a) XRD spectrum of glass/NiO, ITO/NiO, ITO/ZnO/NiO thin films processed at room temperature. (b) Tauc plot of ZnO and NiO thin films and inset is a
transmittance curve of ZnO and NiO grown on ITO glass substrates. (c) transmittance spectra of ZnO/NiO bilayer.

interface between the NiO and ZnO layer confirms the better formation ZnO/NiO heterojunction field emission scanning electron microscopy
of crystallization as observed in the Bragg peaks. The quality of reactive (FESEM) images were recorded. Fig. 3 depicts columnar like structure
dc magnetron sputtering films primarily rely on the composition of the and uniformly distributed grains with good adhesion on the ITO surface.
Ar/O2 gas mixture condition and deposition sputter power. The grown Fig. 3(a), and (b) represents surface morphology and cross-sectional
NiO thin film crystallographic arrangement is a NaCl type of face view of ZnO thin film on glass substrates grown at room temperature
centered cubic (FCC) structure and its crystal structure strongly conditions. Uniformly covered grains without any pinholes are evident
depended on Ni2+, O2- ions [25]. The crystallite size of the individual and the cross-section view shows a homogeneously arranged nano rod-
layers was calculated by using Scherrer’s formula, D = βcosƟ0.9λ
where, λ like structure all over the film. Fig. 3(c), and (d) represents deposited
denotes the X-Ray wavelength (Cu Kα = 1.540 Å), β is Full-Width Half surface morphology and cross-sectional view of the NiO thin films on
Maximum (FWHM) and Ɵ is the Bragg angle of the diffraction peak. The ZnO/ITO structure at room temperature. Fig. 3(e), and (f) shows the
structural properties of the ZnO/NiO heterojunction are consolidated in surface morphology of samples and cross sectional view of ITO/ZnO/
Table 1. NiO thin films annealed at 250 ◦ C. The surface boundaries are densely
Fig. 2(b) represents the energy band gap plot of the ZnO, NiO thin packed and uniformly distributed all over the film without having pin
films with an inset graph depicting the individual transmittance pattern holes. Such kind of morphology is well suitable for optoelectronic device
of ZnO and NiO films grown on ITO substrates. Fig. 2(c) shows the fabrication.
transmittance spectra of ZnO/NiO heterojunction under rapid thermal The chemical composition and oxidation state of oxide thin films
treatment at different temperatures. It shows a visible blind character- were confirmed using X-ray photoelectron spectroscopy (XPS) studies.
istics and the absorption band edge strongly indicates the UV-A region in Fig. 4(a) and (d) shows an elemental mapping of NiO and ZnO thin film
the transmittance spectra of all the samples. The calculated energy band XPS broad spectra spanning a range of 0–1200 eV, with no impurity
gap (Eg) of the NiO and ZnO films by the Tauc plot, is illustrated in Fig. 2 peaks evident. NiO survey spectra include photoemission peaks such as
(b). A wide and direct allowed band transition was observed and the Ni3s, Ni3p, oxygen, carbon, and Ni2p, as well as Auger electron peaks Ni
estimated values of NiO, and ZnO films were 3.55 eV and 3.33 eV, LMM and the O KLL peak [27]. Similarly, ZnO film survey spectra
respectively. The optical band gap of NiO thin film was 3.55 eV, where include Zn3d, Zn3p, Zn3s, Zn LMM, and Zn2p peaks. Both the survey
light absorption takes place at 350 nm wavelength and the ZnO film spectra, core level Ni2p spectra, Zn2p spectra and their O1s spectrum
band gap was 3.33 eV, with light absorption happening at 373 nm. were set using the standard carbon adjustment to 284.8 eV before ana-
When the UV-Visible measurements were carried out on ITO/ZnO/NiO lysing them. All the XPS spectra were adopted with a Shirley-type
thin film heterojunction, the light absorption was prominent at wave- background and multiple peaks were detected using the Gaussian &
lengths below 370 nm and it reveals that the light is trapped at the Lorentzian mode deconvolution approach. In this scenario, deconvo-
interface of ITO/ZnO/NiO. The ZnO/NiO interface’s light trapping and luted Ni2p spectra shown in Fig. 4(b) consists of two binding energy
the interlayer light absorption between ZnO conduction band maximum peaks 853.77 eV and 871.12 eV which are associated with Ni2+ and
and NiO valence band maximum are both responsible for the p-n junc- represents Nickel-Oxygen bonding as well as face-centred cubic align-
tion’s increased light absorption in the UV region. In addition, the grown ment of the crystal structure. Following that, Ni3+ state has been iden-
NiO films consist of oxygen interstitials and due to the thermal treatment tified at 855.2 eV and 872.79 eV of binding energy and it is attributed to
Ni3+ states dominated the Ni2+ states. Moreover, 250 C annealed het-
◦
nickel vacancies [26,28]. Furthermore, a large satellite peak has been
erojunction transmittance has slightly reduced as compared to room detected, which depicts the shake-up process. Fig. 4(c) shows three
temperature processed samples [26]. Therefore, it suggested that the peaks of the O1s spectra, with the peak intensity at 529.30 eV revealing
chosen materials are suitable for applications involving optoelectronics a Ni-O interaction, confirming the octahedra void space with cubic
and transparent electronics. structure. The nickel vacancies and oxygen interstitials, or Ni3+ state,
To analyze the microstructure and cross-sectional feature of the ITO/ induced on the film’s surface is responsible for the peak at 531.14 eV.

Table 1
The structural properties of NiO thin film on ITO and ITO/ZnO thin films.
sample 2θ (degree) FWHM Crystallite size (nm) Dislocation density (1015 m−2) Lattice parameter (Å) D-Spacing (Å)
(degree)

Glass/NiO 43.40 0.46 18.49 2.92 4.16 2.08

ITO/NiO 43.11 0.45 18.84 2.81 4.19 2.09
ITO/ZnO/NiO 43.19 0.46 18.33 2.97 4.18 2.09

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P. Salunkhe et al. Sensors and Actuators: A. Physical 345 (2022) 113799

Fig. 3. FESEM images: (a) surface morphology of ZnO thin films (b) glass/ZnO cross section image. (c) surface morphology of NiO thin films (d) ITO/ZnO/NiO cross
section image of as deposited sample. (e) surface morphology of NiO thin films annealed at 250 ◦ C and (f) cross section image of ITO/ZnO/NiO bilayer processed
at 250℃.

Fig. 4. (a) XPS wide spectra of NiO thin films. (b) XPS spectra of the Ni 2p states of NiO thin films. (c) XPS O1s spectra of the NiO thin films. (d) XPS wide spectra of
ZnO thin films. (e) XPS spectra of the Zn 2p states of ZnO thin films. (f) XPS O1s spectra of the ZnO thin films.

Another two minor peaks at 532.42 eV and 533.37 eV, respectively, 531.03 eV represents the oxygen deficiency in the film. The detailed
depict the O-H group on the film’s surface and the absorbed oxygen chemical composition of XPS Ni2p, Zn2p and their O1s listed in Tables 2
element in the film [29]. Fig. 4(e), represents the Zn2p characteristic and 3 respectively.
core-level spectra and it has two spin-orbit couplings containing Zn2p3/2 Fig. 5(a) and 5(b) show the current-voltage characteristics of the
and Zn2p1/2, located at 1020.30 eV and 1043.41 eV respectively. The photodetector devices fabricated at room temperature under dark and
binding energy difference between the two spin-orbit couplings is UV 365 nm illumination. The following is the functionality of the p-
23.11 eV, which is in good agreement with the previously reported NiO/n-ZnO heterojunction photodiode. When two wide band gap ma-
values [30,31]. Fig. 4(f), shows the core level O1s spectra of Zn2p which terials such as n-ZnO and p-NiO are joined to form a junction, a sub-
is not symmetrical, and it can be de-convoluted into two peaks by stantial carrier concentration is generated at the interface. Furthermore,
applying Shirley type background. We have identified two peaks located positively charged donor ions in the n-type ZnO and negatively charged
at 529.24 eV and 531.03 eV in the O1s spectra. The binding energy peak acceptor ions in the p-type NiO cause a diffusion current flowing across
at 529.24 eV indicates the lattice oxygen interaction between Zn2+ and the heterojunction. The charge carriers continue to diffuse until the
O2- ion in the ZnO film. Another binding energy peak located at Fermi energy level becomes equivalent. Hence, the built-in electric field

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P. Salunkhe et al. Sensors and Actuators: A. Physical 345 (2022) 113799

Table 2 Where,
The XPS Ni2p and Zn2p thin film spectral peak positions and atomic
percentages. qΦB
Is = AA∗ T 2 exp( − )
Room Binding Energy FWHM Atomic Peak kT
Temperature (eV) (eV) (%) assignment Is is the reverse saturation current, T is the absolute temperature in
NiO 851.5 1.86 0.84 Ni0 kelvin, A is the junction area, A∗ is the effective Richardson constant, η is
853.77 1.14 13.27 Ni+2 the ideality factor, k is the Boltzmann constant, and ΦB is the barrier
855.46 2.81 41.08 Ni+3
height of the NiO/ZnO interface. It can be seen that at low voltages the
858.04 2.14 3.97 Intersite
860.75 3.22 28.76 Satellite, carriers exchange between ZnO and NiO layers in the thermal equilib-
shakeup rium mode. Therefore, optimized sputtering parameters such as thick-
863.41 2.2 5.71 Satellite, ness, sputter power, the ratio of argon/oxygen, and post-annealing
shakeup treatments can greatly impact the transport properties of the fabricated
865.9 3.5 6.37 Satellite,
devices.
shakeup
871.12 1.4 2.46 Ni+2 Fig. 6(a) shows UV Photodetector transient photocurrent response
872.79 3.03 11.39 Ni+3 with time for the devices treated at different rapid thermal annealing. A
878.84 7.76 24.54 Satellite, rapid rise and fall of UV response at 365 nm depicted in the current-time
shakeup
plot for different annealed samples are evident. We have performed
880.03 2.76 1.02 Satellite,
shakeup multiple time switches on and off using a standard chopper at different
ZnO 1020.3 1.64 69.2 Zn2p3/2 times. It can be observed that photocurrent rapidly rises when the UV-on
1043.41 1.68 30.8 Zn2p1/2 and falls as UV light goes off, which is indicating a UV response for the
photodetector. In the I-t plot, we have estimated the rise time as a
consideration of the 10–90 % and fall time as of 90–10 % on the period
is induced by a current flowing from ZnO to NiO across the junction.
of on-off mode. The photodetector’s ability to generate photocurrent at
Under dark conditions, electrons are injected from the cathode and holes
zero bias allows it to work in self-powered mode, employing the built-in
injected from the anode recombine at the depletion layer at the ZnO/
potential. The generated charge carriers react instantly to the built-in
NiO interface resulting in low current. A rectifying behaviour is due to
potential when exposed to UV light; the charge carriers are separated
the formation of a built-in electric field at the interface between the
and transferred along the built-in potential direction. As a result, at zero
ZnO/NiO heterojunction. Excitons are generated at the ZnO/NiO
bias, the transient photocurrent is enhanced, which is indicated by a
interface under the illumination of the 365 nm UV light, and they are
sudden increase in current. In addition, for ideal cases at 0 V bias dark
separated by the built-in electric field formed by the heterojunction. The
current must be zero ampere, but in this case, all self-powered devices
separated electrons are carried over ZnO to the ITO side, while the holes
exhibited some amount of dark current, which is of the order of 10−12 A,
can be gathered at the Ag through the NiO thin film, resulting in gen-
zero external bias. Fig. 6(b), and (c) classify the response speed as
eration of photocurrent in the external circuit. We observed the heter-
206.23 ms for the rise and 477.60 ms for the fall of the unannealed
ojunction dark current of 100 nA, and a photocurrent of 1 mA under
sample. Similarly, for 100℃ annealed sample a speed of response of
365 nm light illumination. All the devices have shown excellent recti-
197.29 ms for the rise and 537.10 ms for fall was observed. It confirms
fying behaviour in a dark mode, furthermore, as the rapid thermal
that the photodetector’s device properties have little effect on the
annealing increased from room temperature to 250 ◦ C, the dark current
thermal annealing treatment. However, as we increase thermal
has marginally raised, which could be due to reduced defects at the
annealing, response speed has marginally decreased. It could be due to
interface.
the formation of Ni3+ defects in the NiO thin films. The charge recom-
Under UV light illumination with a power of 0.006 mW/cm2, the
bination mechanisms in the heterojunction govern the decay time.
magnitude of the photo to dark rectification ratio has been reduced from
Regardless of the incident light intensity, the devices non-ideal series
the order 104 to 101 as a function of increasing rapid thermal annealing.
resistances could cause the excited carrier decay time. In the present
Consequently, by increasing the annealing treatment to 250◦ C effective
study, on analysing the I-t plot with different devices we found that all
barrier height reduced from 1 eV to 0.76 eV and the ideality factor has
devices have exhibited rise and decay times in milliseconds. Among all
been reduced from 2.59 to 1.17. Interestingly, increased rapid thermal
of them, 100℃ annealed devices have shown a better photo response
annealing treatment enhanced the heterojunction properties due to the
and other transport properties of photodetectors and the results are
reduction of the defects states in the interface and it is depicted in the
depicted in Fig. 6(a–e). The reported NiO/ZnO heterojunctions have
Fig. 5(c). The leakage current has notably increased, with increasing
response times in seconds that is listed in Table 4. In addition, to
post-annealing temperature, due to electrons-holes recombination at the
enhance the device response speed one need to work on the p-n junction
surface of ZnO and NiO. Utilizing the Thermionic Emission model (TE),
capacitance and potential barrier and appropriate band alignment are
we have extracted the heterojunction diode parameters such as satura-
playing the major role in the device performance.
tion current, ideality factor (η), and barrier height (ΦB) using the
Furthermore, Fig. 6(e) represents the plot of R and D* versus tem-
following equations.
[ ( ) ] perature. All self-powered devices responsivity systematically decreased
qV with increasing the rapid thermal annealing process, which strongly
I = Is exp −1
ηkT suggested that the electron-hole recombination process has been acti-
vated at the junction. Photo-responsivity (R) indicates the sensor’s

Table 3
The XPS Ni2p O1s and Zn2p O1s thin film spectral peak positions and atomic percentages.
NiO-O1s Spectral features ZnO-O1s Spectral features

Binding Energy (eV) FWHM (eV) Atomic (%) Peak assignment Binding Energy (eV) FWHM (eV) Atomic (%) Peak assignment

529.3 0.93 42.38 Ni2+ 529.24 1.23 68.36 lattice

531.14 1.39 47.89 Ni3+ 531.03 1.63 31.64 defects
532.42 0.99 6.35 O-H
533.37 1.21 3.38 Adsorbed Oxygen

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P. Salunkhe et al. Sensors and Actuators: A. Physical 345 (2022) 113799

Fig. 5. Current-Voltage characterstics of Photodiode. (a) under dark (b) under UV 365 nm (c) Barrier height and ideality factor versus annealing temperature, and
(d) Photograph of the fabricated ZnO/NiO Photodiode.

ability to respond to incident UV light and is given by where R denotes photo-responsivity, Id represents dark current, A is
/
Iilluminated − Idark the active area where incident light absorption occurs, and e denotes the
R= (A W) electronic charge. According to the above relation, high detectivity is
Pilluminated
expected if we suppress the background dark current. The detectivity of
The obtained current during UV illumination, current at dark mode, 5.66 × 1011 Jones at zero bias condition in un-annealed device was
and power of the light source falling on the device’s active area are achieved and it has marginally decreased to 2.74 × 1011 Jones with an
represented by Iilluminated , Idark , and Pilluminated , respectively. With increased increasing annealing temperature. It is essential to have a low dark
annealing temperature, we have found a decrement of R from current for improvement in the signal-to-noise ratio which ensures
13.01 mA/W to 6.52 mA/W due to the decrement in the depletion width reduced dark-noise effects. Fig. 6(f) shows a comparison of external
of the space charge region and the reduced diffusion capacitance in the quantum efficiency (EQE) and linear dynamic range (LDR) as a function
reverse bias mode. It is interesting to note that as the rapid thermal of post-annealing temperature. For any photodetector, EQE is one of the
annealing increases, the optical absorption edge has been reduced, important key parameters for performance evaluation and it can be
enabling charge carriers to easily move through the diffusion process expressed as the relationship of photocurrent to photon fluence falling
instead of the recombination process. The samples treated at 250 ◦ C had on the surface of the device. It can be evaluated using the relationship:
a modest photo response because it is noted that the dark to light current
rectification ratio has been recorded in the order of 101. This could be EQE (%) =
hc R
× 100
due to the photosensitizing centres of the ZnO/NiO interface. Moreover, q λ
when the bias is zero, the device’s on-off binary photo-response can be
improved by thermally annealed devices. The correlation drives the where h is Planck’s constant, c is the velocity of light in a vacuum, R is
Detectivity (D*), which is a vital attribute that represents the sensor’s the responsivity, q is the elementary charge of the electron and λ is the
ability to sense the faintest optical signal and it can be expressed as the wavelength of the incident photon. The EQE of the constructed PD de-
following relation: vice was 4.42 % for as deposited devices and it has reduced to 2.21 %
with increasing the post-annealing treatment to 250℃. The imple-
/
R A1/2 mentation of external bias may help to effectively separate and retrieve
D∗ = √̅̅̅̅̅̅̅̅̅ (Jones or cm Hz1 2W − 1)
2eId photogenerated carriers, leading to an increase in photocurrent and a
faster drift velocity could be leading to poor detectivity and EQE.

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P. Salunkhe et al. Sensors and Actuators: A. Physical 345 (2022) 113799

Fig. 6. (a) Self powered Photocurrent switch behaviour of the different post annealed devices under UV 365 nm light. (b) Rise time photo response at bias of 0 V (c)
Fall time photo response at bias of 0 V (self powered photodiode) (d) Photo current of ZnO/NiO photodetector as a function of post annealing temperature (e)
Responsivity and detectivity as a function of post annealing temperature (f) Signal to noise ratio and external quantum efficiency as a function of post annealing
temperature.

Table 4
Comparison of the performance of fabricated ZnO/NiO UV photodetector with recent articles (NR-not reported).
Device Wavelength of detection Condition (Self-biased) Responsivity Detectivity (D) (Jones) Rise and decay times Reference

NiO/ZnO 365 nm No 0.3 A/W NR NR [36]

ZnO/NiO 355 nm Yes 0.44 mA/W NR 0.23 s/0.21 s [37]
ZnO/NiO 350 nm No 10.2 A/W 4.6 × 1012 0.28 s/0.18 s [38]
ZnO/NiO 365 nm No NR NR 1.4 s/11.3 s [39]
NiO/ZnO 350 nm Yes 0.41 mA/W NR 7.5 s/4.8 s [40]
NiO/ZnO 365 nm No 0.19 A/W 3.8 × 1012 NR [41]
NiO/ZnO 365 nm No NR NR 6 s/22.5 s [42]
NiO/ZnO 365 nm No 2.23 mA/W NR 20/30 s [43]
NiO/ZnO 365 nm Yes 13.01 mA/W 5.66 £ 1011 206.23 ms/477.60 ms Present work
NiO/ZnO 365 nm Yes 12.51 mA/W 4.85 £ 1011 197.29 ms/537.10 ms Present work

However, responsivity is directly proportional to the external quantum quality of the interface, surface defects and crystalline nature of the films
efficiency of the UV sensors. Responsivity has decreased from can greatly influence the dark current, which can also tune the carrier
13.01 mA/W to 6.52 mA/W as thermal treatment increased from room recombination at the interface [32,33]. The better quality of the sput-
temperature to 250℃. Moreover, current-voltage characteristics plot of tered ZnO and NiO thin film’s physical properties and minimal surface
the dark to UV light has shown that the rectification ratio decreased defects could enhance the photocurrent of the device with zero bias
from 104 to 101 as we increased the thermal treatment to the interface. mode. In addition, the device’s performance was evaluated by the figure
In addition, Fig. 5(c) clearly shows that the barrier height of the p-n of merit parameters such as spectral photo-responsivity (R), transient
junction has decreased from 1 eV to 0.76 eV as a function of thermal photocurrent (speed of response), external quantum efficiencies, and
treatment. According to the relation between depletion width and built- detectivity (D*). Observing the results of prior studies consolidated in
in potential, narrow depletion width allows only a fraction of incident Table 4, it is clear that the vast majority of them focused on a small
UV light to be absorbed. Hence, EQE has decreased from 4.42–2.21 % as number of variables. Even though the majority of studies were effective
the thermal annealing temperature increases. In addition to the EQE, in improving the response time, there are some very unresolved issues
detectivity and LDR (linear dynamic range, typically denoted in dB) is with self-powered systems and the trade-off between other qualities
one of the important figures of merits for the UV detector and it can be such as responsivity, detectivity, external quantum efficiency etc. is
expressed as follows: needed. As a result, we have tried to explore these parameters in zero
bias mode. Room temperature processed device has shown a detectivity
Iilluminated
LDR = 20log (dB) of the NiO/ZnO heterojunction noticeably high as compared to values
Idark
obtained from the different post-annealed UV photosensors. This could
We have found LDR values from 53.55 dB to 46.93 dB as a function be due to the surface-induced traps and charge carrier transportation
of rapid thermal annealing. LDR is indirectly proportional to the dark arising at the Ag/NiO junction. At zero bias conditions, recombination
current so that better LDR can be obtained for smaller dark currents. The

7
P. Salunkhe et al. Sensors and Actuators: A. Physical 345 (2022) 113799

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CRediT authorship contribution statement Actuators A Phys. 338 (2022), 113479, https://doi.org/10.1016/j.
sna.2022.113479.
[16] O. Lupan, V. Postica, T. Pauporté, M. Hoppe, R. Adelung, UV nanophotodetectors:
Parashurama Salunkhe: Methodology, Investigation, Writing – a case study of individual Au-modified ZnO nanowires, Sens. Actuators A. Phys.
original draft, Validation. Prashant Bhat: Validation. Dhananjaya 296 (2019) 400–408, https://doi.org/10.1016/j.sna.2019.07.040.
Kekuda: Conceptualization, Supervision, Visualization. [17] M. Patel, H. Kim, J. Kim, All transparent metal oxide ultraviolet photodetector,
Adv. Electron. Mater. 1 (2015), 1500232, https://doi.org/10.1002/
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[18] R. Deng, B. Yao, Y.F. Li, Y.M. Zhao, B.H. Li, C.X. Shan, Z.Z. Zhang, D.X. Zhao, J.
Declaration of Competing Interest Y. Zhang, D.Z. Shen, X.W. Fan, X-ray photoelectron spectroscopy measurement of
n-ZnO/p-NiO heterostructure valence-band offset, Appl. Phys. Lett. 94 (2009),
The authors declare that they have no known competing financial 022108, https://doi.org/10.1063/1.3072367.
[19] M. Athira, S.P. Bharath, S. Angappane, SnO2 -NiO heterojunction based self-
interests or personal relationships that could have appeared to influence
powered UV photodetectors, Sens. Actuators A. Phys. 340 (2022), 113540, https://
the work reported in this paper. doi.org/10.1016/j.sna.2022.113540.
[20] W. Huang, S. Ding, Y. Chen, W. Hao, X. Lai, J. Peng, J. Tu, Y. Cao, X. Li, 3D NiO
hollow sphere/reduced graphene oxide composite for high-performance glucose
Data availability
biosensor, Sci. Rep. 7 (2017) 1–11, https://doi.org/10.1038/s41598-017-05528-1.
[21] P. Salunkhe, M.A.A. V, D. Kekuda, Investigation on tailoring physical properties of
Data will be made available on request. Nickel Oxide thin films grown by dc magnetron sputtering, Mater. Res. Express 7
(2020), 016427, https://doi.org/10.1088/2053-1591/ab69c5.
[22] O. Tuna, Y. Selamet, G. Aygun, L. Ozyuzer, High quality ITO thin films grown by dc
Acknowledgements and RF sputtering without oxygen, J. Phys. D Appl. Phys. 43 (2010), 055402,
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[23] D. Ban, M. Patel, T.T. Nguyen, J. Kim, All-transparent oxide photovoltaics: AZO
We would like to thank the Micro and Nano Characterization Facility
embedded ZnO/NiO/AgNW band selective high-speed electric power window,
(MNCF) at CeNSE, funded by the Ministry of Electronics and Information Adv. Electron. Mater. 5 (2019), 1900348, https://doi.org/10.1002/
Technology (MeitY), Government of India, Indian Institute of Science aelm.201900348.
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(IISc), Bengaluru for the XPS characterization.
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