Materials Science in Semiconductor Processing 95 (2019) 7–19

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Materials Science in Semiconductor Processing

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Quantum efficient fast UV photodetectors based on nanocrystalline Zn1-xPxO T

(x = 0.00, 0.03, 0.07) thin films deposited by pulsed laser deposition
technique
⁎
Karmvir Singha, Ishpal Rawalb, , Neeru Sharmac, Prikshit Gautamb, Rakesh Dhara
a
Department of Physics, Guru Jambheshwar University of Science and Technology, Hisar, India
b
Department of Physics, Kirori Mal College, University of Delhi, Delhi, India
c
Department of Electronic and Communication, Jaypee University of Information Technology, Solan, India

A R T I C LE I N FO A B S T R A C T

Keywords: Here, we demonstrate the effect of phosphorous doping concentration on the structural, electrical and optical
ZnO thin films properties of ZnO thin films deposited by pulse laser deposition technique. X-ray diffraction studies performed
Pulse laser deposition on the deposited films reveal the polycrystalline nature of films and confirm the deposition of ZnO films in
UV photodetectors wurtzite phase. However, the incorporation of phosphorous does not lead to originate new peak in XRD patterns
External quantum efficiency
of the doped films, negating the formation of new phase or the formation of P2O5 phase of phosphorous. But this
doping influences the peak positions of pure ZnO film which suggests that phosphorous taking the interstitially
positions of Zn and compensates the incomplete bonds. The electrical conductivity of the deposited films is found
to significantly increases with phosphorous doping. The prepared photo-devices have shown exceptional UV-
photodetection ability under UVA light for fixed illumination intensity of 3.3 mW/cm2 and varying intensities of
~ 0.367 to 3.3 mW/cm2. All the prepared devices have fast response and high sensitivity towards UV light. The
response and recovery times for the deposited films are less than 200 ms, with sensitivity as high as ~ 85% at
3.3 mW/cm2 illumination intensity for the device with 7 wt% doping of phosphorous. The high responsivity and
detectivity as compared to reported literature, confirms the superior device performance and photo-character-
istic of the prepared devices.

1. Introduction
III-V Nitride materials are widely used in power saving devices like
LEDs, LCDs, and photo-detectors etc, but the major concern with GaN
and InGaN based devices is their efficiency droop [1,2]. In these de-
vices, initially with increase in current density, internal quantum effi-
ciency also increases up to a critical limit (80%) and beyond this limit,
for internal quantum efficiency a reverse trend starts. This declination
phenomenon of internal quantum efficiency at high current density is
referred as efficiency droop [1,2]. However, this problem can be
overcome up to certain limit by including some graded indium, polar-
ization doping and electron blocking layer, etc. but complete elimina-
tion is not possible. Therefore, material researchers are curious about
some other materials free from such discrepancies or limitations. Metal
oxide, in particular, zinc oxide is considered as one of the most fasci-
nating materials for optoelectronic devices including solar-blind UV-
photodetectors, light emitting diodes and laser diodes, etc. due to its
wide optical band gap, low cost and the most important easy to fabri-
cate in its pristine as well as doped form over the convention nitrite
materials (like GaN, BN) [1–10]. The visible blindness and the occur-
rence of deep trap states in the band gap region of ZnO make it a sui-
table material for UV-photodetectors [11,12]. The surface to volume
ratio (i.e high aspect ratio) and the presence of large number of deep
trap states in band gap region are the key parameters of superior op-
toelectronic devices. The presence of deep trap levels lengthen the
carrier life time, whereas, the reduced dimensionality significantly
shortens the carrier transit time. Thus, the prolong carrier life time with
reduced carrier transit time extensively improved the photoconduction
gain, which is defined as the ratio of the carrier life time to transit time
[1,11,12], resulting in an exceptional improvement in photocurrent.
Moreover, it is believed that the optoelectronic properties of ZnO
can be further improved via the incorporation of metallic elements of
X3+ type such as gallium (Ga), indium (In) and aluminum (Al) or the
elements of X5+ type like As, P and N, etc. However, these materials

⁎
Corresponding author.
E-mail addresses: rawalishpal@kmc.du.ac.in, rawalishpal@gmail.com (I. Rawal).

https://doi.org/10.1016/j.mssp.2019.02.004
Received 19 August 2018; Received in revised form 12 December 2018; Accepted 3 February 2019
Available online 10 February 2019
1369-8001/ © 2019 Elsevier Ltd. All rights reserved.
K. Singh et al. Materials Science in Semiconductor Processing 95 (2019) 7–19

have their own advantages and limitations. For example, Al is highly

reactive, resulting a fast oxidation during the growth and does not sa-
tisfy the expected requirements, while Ga is less reactive and more
stable against oxidation due to large electronegativity of Ga with
comparable covalent bond length to ZnO (i.e. covalent bond lengths
between Zn-O and Ga-O are 1.97 Å and 1.92 Å, respectively) and may
be advantageous for optoelectronic applications as compared to Al
[13,14]. Moreover, Phosphorous (P) is widely used as pentavalent im-
purity for silicon based technology for the growth of n-type silicon for
solar cells and white light photodetectors, etc. However, according to
the reported literature, P-doped ZnO thin films can have both n-type
and p-type characters [15–20]. Although, the structural, electrical and
magnetic properties of P-doped ZnO thin films are well studied [15–20]
but the effect of P-doping on the visibly blind optoelectronic (UV-
photodetection) characteristics is not well studied and still requires
serious attentions. P-doping in ZnO films may be good choice for im-
proved optical properties of ZnO for UV photodetectors [15–20].
Therefore, in the present study, we have made an attempt to grow
phosphorous doped ZnO thin films by pulsed laser deposition technique
with different phosphorous concentrations. The deposited films were
analyzed for structural and electrical conformations with phosphorous Fig. 1. Schematic representation of parallel surface electrodes (Ag/ZnO/Ag)
doping concentrations. The UV photodetection behavior of the de- geometry used for the measurements dark and photo-current under different
posited films was systematically analyzed at fixed illumination intensity illumination intensities.
as well as with varying intensities as a function of time and applied
potentials (I-V characteristics).
parallel electrode geometry (silver/ZnO/silver) as shown in Fig. 1. The
silver electrodes of thickness ~ 100 nm were deposited by thermal
2. Experimental details
evaporation technique under high vacuum of ~ 1.6 × 10−5 mbar
achieved by the combination of diffusion and rotary pumps. A UVA
2.1. Deposition of pristine and phosphorous doped ZnO thin films
tube of wavelength ~ 365 ± 10 nm was used as a UV light source and
the measurement set-up is well calibrated with distance from the
Undoped (ZnO) and phosphorous doped Zinc Oxide (Zn0.97P0.03O
sample holder for different intensities of UV light. The photoconduction
(with 3 wt% doping of phosphorous), Zn0.93P0.07O (with 7 wt% doping
characteristics of the deposited films were analyzed under UVA light
of phosphorous) thin films were deposited using KrF Excimer laser
(wavelength ~ 365 nm) of different intensities ranging from 0.367 m to
(λ = 248 nm) on p-type silicon wafers of dimension 1 cm × 1 cm. The
3.3 mW/cm2. The change in electric current at fixed voltage (0.01 V) as
silicon substrates were ultrasonically cleaned with acetone and me-
a function of time at fixed intensity (3.3 mW/cm2) and variable in-
thanol alternating for five minutes and dried with nitrogen gun before
tensities (0.367–3.3 mW/cm2) of UVA illumination, was recorded using
deposition. The targets for the deposition of these films were prepared
Keithley's 2410 source measure unit (SMU) connected with personal
by standard solid state reaction method in which the obtained bulk
computer through KUSB 488.2 in Labview environment. More details
precursor material (for example ZnO) was initially grinded for 7 h fol-
for these measurements and measurement set-up can be found else-
lowed by 12 h calcinations at 900 °C in ambient environment. The ob-
where [21]. The photodetection measurements were carried out in
tained material was further grinded for 2 h and mixed with PVA binder.
cycles of 30 s of OFF (dark current) and ON (under illumination) of
Finally, the mixture powder was converted into pellets of diameters
each, alternatively to avoid the contribution from heating effect and the
~ 20 mm and thickness of ~ 3 mm at a pressure of ~ 100 kN/cm2 fol-
data were recorded with time delay of 100 ms to ensure the response
lowed by sintering at 1100 °C. The base pressure was brought to
time. Furthermore, to check the effect of testing environment, the
1 × 10−6 Torr in the vacuum chamber using the turbo-molecular pump
measurements were also carried out in inert (nitrogen) atmosphere (N2
assisted with rotary pump. The laser fluence (energy density) of 1.5 J/
atmosphere) and under a vacuum of ~ 1.4 × 10−2 mbar achieved with
cm2 was used for all the depositions, while, the target was maintained
the help of a rotary pump, on the pristine ZnO and Zn0.93P0.07O thin
to rotate with a rate of 10 rpm. The other parameters like laser re-
films. I-V characteristics of photo-devices have also been recorded at
petition rate (10 Hz), oxygen partial pressure of (1 mtorr), target to
different illumination intensities of UVA light.
substrates distance (5 cm), and substrates temperature (450 °C) were
kept constant for all depositions of the thin films. The thickness for all
the deposited films was maintained to ~ 200 nm and measured by 3. Results and discussion
Dektak –150 (M/s Veeco USA) using stub process.
3.1. Structural and morphological properties
2.2. Structural and morphological characterizations of deposited ZnO thin
films Fig. 2(a-c) shows the XRD patterns of ZnO, Zn0.97P0.03O and
Zn0.93P0.07O thin films deposited on p-type silicon substrates by PLD
The structural analysis of the deposited films was done using X-ray technique. All the deposited films exhibit polycrystalline nature with
diffraction (XRD) carried out at X-ray diffractometer (D8 Discover, ASX- various peaks located at ~ 30.33, 33.8, 47.08, 69.32 and 70.02°, that
Bruker) using CuKα radiations (λ = 1.5406 Å), whereas, the surface are ascribed to the (hkl) planes (100), (002), (102), (201) and (004) of
morphological properties were studied using scanning electron micro- wurtzite phase of ZnO. One more reflection at 24.47° also observed in
scopy (SEM) (Leo Electron Microscope – model no. LEO 440) in the all patterns, which might be come from substrate structure. The XRD
secondary emission mode and atomic force microscopy at Digital patterns of deposited films are well matched with reported literature
Instrument Nanoscope III in contact mode (force constant = 0.58 N/m). and JCPDS data card no. 36–1451) of polycrystalline ZnO in wurtzite
Two terminal UV-photoconduction measurements were carried out in phase [17,21,22]. It is observed that all the films deposited with dif-
an indigenous developed UV photodetection measurement set-up in ferent concentrations of phosphorous (P) have a predominated peak

8
K. Singh et al. Materials Science in Semiconductor Processing 95 (2019) 7–19

Fig. 2. XRD patterns of (a) ZnO (b) Zn0.97P0.03O, (c) Zn0.93P0.07O and Magnified XRD patterns of the (002) plane in different thin films.

around 33.8° corresponding to preferential orientation of (002). The 0.9λ

∆=
dopant P may exist in two forms either in P2O5 or as a substituent for Zn β cosθ (1)
ion or O ion in ZnO matrix. However, No additional peak is observed in
XRD patterns due to phosphorous doping, which discarded the possi- Where, λ is the wavelength of the irradiation source (CuKα source,
bility of presence of independent phase of phosphorous via oxygen λ ≈ 1.5406 Å), β is the full width at half maximum corresponding to
bonding and thus, suggesting the possibility of the replacement of Zn or the peak located at an angle of θ. The observed values of the crystallite
O ion by P ion in ZnO crystal. The lattice defect induced by P5+ at the size are found to be 18, 19 and 14 nm for ZnO, Zn0.97P0.03O and
Zn2+ lattice sites may help in the compensation of oxygen vacancies in Zn0.93P0.07O films, respectively, and tabulated in Table 1. However, the
ZnO. It is observed that the films are preferably orientated with c-axis change in peak position, full width at half maximum and intensity
perpendicular to substrate axis and having a dominating phase of (002) confirms the doping of ZnO thin films by phosphorous and the change
whose intensity is strongly increased with P doping. This suggests the in electronic state of the deposited films. The shift in peak position can
formation of highly crystalline ZnO films with P doping, without af- be attributed to the lattice mismatching/disordering arise due to stress
fecting hexagonal wurtzite structure of ZnO. The peak position of (002) and change in lattice parameters (Table 1) [21,23]. The lattice para-
plane shifts towards higher angle (33.7–33.8°) with phosphorous meter (c) has also been calculated using the simplified Bragg's law for
doping (~ 3 wt%), along with increase in intensity as well as full width (002) plane [25] and found to change with change in doping type,
at half maximum (as shown in Fig. 2d). The shifting of peak position
Table 1
towards higher angle side with phosphorous doping may be due to
Lattice parameter ‘c’, grain size ‘Δ’, dislocation density ‘δ’, and stress ‘S’ strain
different atomic radii of phosphorous (0.034 Å) and zinc (0.074 Å)
‘ε’, for the pristine ZnO and P-doped ZnO thin films.
[13,17] and substitutional and interstitial effects. The increase in full
width at half maximum indicates the decrease in crystallite size with Sample name ZnO Zn0.97P0.03O Zn0.93P0.07O
phosphorous doping, while the change in the peak position suggest the
Lattice parameters ‘c’ (Å) 5.313 5.298 5.298
change in bond length via substitution of smaller size phosphorous Grain size ‘Δ’ (nm) 18 19 14
atom to zinc lattice site or the deformations arise due to the presence of Dislocation density ‘δ’ (lines/m3) 3.08 × 1015 2.76 × 1015 5.09 × 1015
phosphorous at interstitials sites. Strain ‘ε’ ×10−3 1.95 1.84 2.50
The crystallite size (Δ) in the present films was estimated using the Stress ‘S’ ×10−3 2.65 2.51 3.40
Inter-planer spacing (Å) 2.656 2.649 2.649
standard Scherrer's formula [23]

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K. Singh et al. Materials Science in Semiconductor Processing 95 (2019) 7–19

c=
λ the Zn0.93P0.07O thin film are found to be quite higher than the pristine
sinθ (2) ZnO film.
The change in lattice parameters and hence the lattice volume with Fig. 2(a) - (b) show the AFM images of Zn0.97P0.03O and Zn0.93P0.07O
P doping in ZnO can be determined by two factors: firstly by the size thin films, respectively. It is observed from Fig. 2(a) that there is a
uniform distribution of spherical shape grains/agglomerates of size
difference in ionic radii of Zn2+ (0.074Ǻ) and P5+ (0.034Ǻ) and sec-
~ 100 nm, while the size of the grains decrease significantly (below
ondly by the deformation of conduction band potential due to increase
50 nm) on increase the P-doping concentration, that might be due to
in the number of free carriers due to 5 + ionic nature of phosphorous.
catalytic effect of phosphorous on the deposition and alternation of
Similar type of effect has also been observed by Park et al. [24] with Ga
nucleation process. A more dense distribution of the grains is observed,
doping in ZnO.
that indicates the alteration of surface morphology due to catalytic
The dislocation density (δ) that defined as the length of dislocation
effect of phosphorous on deposition of ZnO. Moreover, the shape of the
line per unit volume has also been calculated for the pristine as well as
grains no longer remained the perfectly spherical but it becomes
P-doped ZnO thin films from the crystallite size (δ=1/Δ2). The ob-
somewhat random or oblate. The grain sizes observed for different films
tained data is summarized in Table 1. It is observed that the values of
from AFM studies are quite larger as compared to crystallite sizes ob-
dislocation density increase with increase in P-doping concentration as
served from XRD studies, which suggest that the surface agglomerates
compared to pristine ZnO film. The observed values for ZnO,
are contained more than one crystallite of different orientations. The
Zn0.97P0.03O and Zn0.93P0.07O are 3.08 × 1015, 2.76 × 1015 and
roughness of films also measured from AFM studies and the rms values
5.09 × 1015, respectively. Moreover, because of large difference in
of the roughness for ZnO, Zn0.97P0.03O and Zn0.93P0.07O are found to be
ionic radii of Zn2+ (0.74 Å) and P5+ (0.034 Å) ions, it is expected that
~ 2.34, 1.63 and 1.00 nm, respectively.
the crystal structure in deposited ZnO films have high the stress and
Fig. 3(c) and (d) show the SEM images of the pristine ZnO and
strain and therefore, the stress and strains have also been calculated for
phosphorous (~ 7 wt%) doped ZnO thin films, respectively. It has been
the present deposited films [26]
observed that there is a uniform distribution of smaller size nano-
λ β particles (< 100 nm) in both the films and not much difference in
S= −
∆sinθ tanθ (3) surface morphologies of thin films is observed from SEM studies. But a
and closer investigation of surface morphologies suggests that the phos-
phorous incorporation in ZnO film make it quite smoother, which may
βcosθ be caused by some catalytic effect. The deposited films seem to be
ε=
4 (4) denser and of good quality for device applications.
The observed values of stress and strain for the present deposited films
have been summarized on Table 1. The values of stress and strain for

Fig. 3. AFM micrographs of (a) Zn0.97P0.03O, and (b) Zn0.93P0.07O thin films, SEM images of (c) pristine ZnO and (d) Zn0.93P0.07O thin films.

10
K. Singh et al.
Fig. 4. (a) XPS general survey scans of pristine ZnO and Zn0.97P0.03O thin films (inset magnified region of general scans in the range of 120–150 eV), (b) XPS 2p core
level spectra of Zn in pristine ZnO, Zn0.97P0.03O and Zn0.93P0.07O thin films (c) 2p core level spectra of P in Zn0.97P0.03O and Zn0.93P0.07O thin films, and (d) O 1s core
level spectra of the deposited thin films.
3.2. X-ray photoelectron spectroscopy studies
For the elemental examination of the deposited films, XPS studies
are carried out on the pristine as well as P-doped ZnO thin films. Fig. 4a
shows the general survey scan of the pristine ZnO and Zn0.97P0.03O thin
films. It is observed from the figure that both the general scans con-
sisting of all the major bands of ZnO associated with the Zn 3d, 3p, 3s
and 2p states along with a sharp feature at ~ 530.88 eV corresponding
to oxygen 1 s (O 1 s), which confirms the deposition of ZnO thin films.
The inset of Fig. 4a shows the magnified view of Zn:3 s level in the
range of 120–150 eV. The presence of an addition peak at the lower
binding energy of 132.93 eV in the Zn0.97P0.03O thin film, associated
with the P:2p, confirms the replacement of Zn or O ions by P ions.
To investigate the relative chemical concentrations of the deposited
films, the core level spectra of Zn:2p, P:2p and O: 1s is separately re-
corded and plotted in Fig. 4(b-c). Fig. 4b elucidates the 2p level spectra
of Zn in pristine as well as P-doped ZnO thin films. It is observed that
due to strong spin-orbit coupling, the 2p level of Zn splits into two
levels located at ~ 1045.7 and 1022.6 eV, corresponding to 2p1/2 and
2p3/2, respectively. The energy difference between these components is
~ 23.1 eV, which is found to decrease to 23 eV with phosphorous
doping, as shown in Fig. 3b and the new positions for the 2p1/2 and 2p3/
2 components are found to ~ 1045.1 and 1022.1 eV, respectively for the
P-doped ZnO thin films i.e. the peak position of 2p3/2 shifts by 0.5 eV
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Materials Science in Semiconductor Processing 95 (2019) 7–19
and the peak position of 2p1/2 shifts by 0.6 eV with the incorporation of
P in ZnO matrix due to spin-orbit coupling. Fig. 4c shows the 2p1/3 level
spectra of phosphorous in the Zn0.97P0.03O and Zn0.93P0.07O thin films.
The peak positions of the 2p level of phosphorous in the Zn0.97P0.03O
and Zn0.93P0.07O thin films are found to 132.94 and 132.84 eV, re-
spectively. The observed peak positions are different from that gen-
erally observed for P2O5 (~ 135.5 eV), which negate the presence of
distinct phase of phosphorous (i.e. P2O5), that also confirmed from the
XRD measurements and suggest that P incorporated into the ZnO thin
film. It is also well reported that the peak positions for P: 2p3/2 in Zn3P2
and ZnP2 are found to be 128.3 and 129.8 eV, respectively, which is
quite lower (~ 3 eV) than the peak positions observed in the present
studies. Thus, the observed peak positions discard the possibility of the
formation of Zn-P bonds in the present films that means O does not
substituted by the P [27,28]. But the observed peak positions for P: 2p3/
2 is quite near to the P: 2p3/2 peaks located at ~ 133.3 and 133.8 eV in
P-O-P and P-O-Zn bonding states [27,29], which suggest that the P-
doping substitutes the Zn site and confirm the doping of ZnO thin films
by phosphorous. Fig. 4d demonstrates the core level (O 1s) spectra of
oxygen in all the deposited films. It is observed that the peak position of
the O 1s shifts toward the lower binding energy side by 0.18 eV (from
530.88 eV in pristine ZnO thin film to 530.70 eV in Zn0.93P0.07O thin
film), with the incorporation of P in ZnO matrix. Furthermore, the
change in the full width at half maximum (FWHM) and the intensity of
K. Singh et al.
Table 2
Sensitivity factors and percentage content of different elements in the deposited
films.
Sample name Sensitivity factor Content (at%)
ZnO Zn (p3/2) 5.3 46.08
O (1s) 0.63 53.92
Zn0.97P0.03O Zn (p3/2) 5.3 47.33
P (2p) 0.25 3.26
O (1s) 0.63 49.41
Zn0.93P0.07O Zn (p3/2) 5.3 41.77
P (2p) 0.25 7.19
O (1s) 0.63 51.04
curves have also been observed, which is accompanied with the change
in oxygen content in the deposited thin films. Now to check the relative
concentrations of the different elements such as Zn, P and O in the
deposited films, the area under the 2p3/2 curves for Zn and P, and the
area under the 1 s curve for O is estimated using the integration method
after base line correction for all the deposited films. The observed va-
lues of the area under the curves have been used to determine the
atomic percentage (at%) for various elements including Zn, P and O in
deposited films using the relation [30,31]
Ai / Si
at .% = x100
∑i Ai / Si (5)
Where, Ai is the area under the curve for a particular element such as
Zn, P or O and Si is sensitivity factor of the corresponding element for
different levels (2p3/2 or 1s core level, etc) and presented in Table 2.
The sensitivity values for Zn:2p3/2, P:2p and O:1s are 5.3, 0.25 and
0.63, respectively [30] and calculated values for the doping con-
centration of phosphorous in the Zn0.097P0.03O and Zn0.093P0.07O films
are found to be 3.26 and 7.19 at% (Table 2).
3.3. UV photodetection studies
The deposited films are further investigated for UV-photodetection
ability under UVA light (λ ≈ 365 nm) and the photoresponse of the
deposited films was characterized by measuring the current at a con-
stant voltage (0.01 V) as a function of time in periodic manner of ON
and OFF of UV light for 30 s each, at a step of 100 ms. Fig. 5(a-c) show
the change in electric current as a function of time at a fixed illumi-
nation intensity of ~ 3.3 mW/cm2 for the ZnO, Zn0.097P0.03O and
Zn0.093P0.07O films, respectively. It has been observed that all the films
have a stable dark current and once the UV light on, the current of the
films change vary rapidly to achieve a maximum value within 200 ms,
indicating a fast response of the films. It is observed that the electric
current of the ZnO films changes from ~5.3–8.5 μA, from ~ 42–70 μA
for Zn0.097P0.03O film, and from ~ 13.8–24.2 μA for Zn0.093P0.07O film,
which suggest a large change in electric current for phosphorous doped
films (Zn0.097P0.03O and Zn0.093P0.07O films) under UV light. Photo-
response of metal oxide sensors generally depends upon the adsorption-
desorption of oxygen molecules on the surface of metal oxides [22].
Under dark condition, oxygen molecules get adsorbed on the ZnO
surface and extract the electron from the conduction band of ZnO,
which results in a decrease in carrier concentration along with the
development of a potential barrier at the surface, grains, and grains
boundaries which limits the motion of charge carriers, resulting in a
decrease in electrical conductivity of ZnO films.
On exposing the ZnO films with UV light photon of energy greater
than band gap energy, electron-hole pairs [hν →e- + h+] are produced
and the photo-induced holes interact with adsorbed oxygen ions to
neutralize [h+ (hv) + O2- → O2 (ads.)] them and finally the desorption
of oxygen molecules take place from film surface [22,32,33]. Through
this process, electrons are returned back to conduction band as a result,
thickness of depletion layer decrease, charge carrier concentration at
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Materials Science in Semiconductor Processing 95 (2019) 7–19
the surface increase that causes in an increase in electrical conductivity
of films and recorded as a photoresponse of the films. When UV light
gets off, re-adsorption of oxygen molecules on the films surface takes
place, which results in the recapturing of electron and hence decreases
in electrical conductivity of the films leading to regain the original state
(recovery) of the sample. It has been observed that the photoresponse of
the phosphorous doped ZnO films is quite stable as compared to pure
ZnO film in UV light. The decrease in photo-induced current in ZnO
films may be due to higher recombination rate of electron-hole pair or
the presence of higher defect states. The photo-induced electrons are
neutralized by these defect states in ZnO films before reaching of
electrons at the electrodes, while in case of phosphorous doped ZnO
films these defects are compensated by the smaller size phosphorous
atoms. This reduces the recombination rate and hence a stable and very
high photoresponse of Zn0.097P0.03O and Zn0.093P0.07O films is ob-
served. Moreover, to ensure the repeatability of photodetection process
in these films, three cycles of photoresponse are recorded at the same
illumination intensity with 30 s ON/OFF pulses. The pulses of 30 s are
also considered to avoid the heating effect of the sample and observed
that all the films recovered within 200 ms to their original value which
negates any heating effect. The full response and recovery times for
pure ZnO films are found to be ~ 300 ms, while for phosphorous doped
films these times are observed to be ~ 200 ms. According to reported
literature [34–37] the photoresponse of the samples is generally varies
from several seconds to minutes, which suggests the excellent photo-
response of the present films. The slight decrease in electric current in
successive cycles as compared to the first cycle in pure ZnO film can be
attributed to the generation of internal heat caused by UV illumination,
which may slightly degrade carrier mobility in ZnO film. However, this
problem is solved in p-doped ZnO films and no heating effects are ob-
served at all. The observed change in electrical current as function of
time is converted in photoresponse using the relation [22,38].
Ip − Id
Response (%) = x100
Id (6)
Where, Ip is the current under UV illumination and Id is the dark cur-
rent.
The photoresponse of the deposited films has been shown in
Fig. 5(d-f) and found that the UV photoresponse of the deposited films
increase with phosphorous doping concentration. The photoresponse of
the pure ZnO found to be 50–65% while it is about 70% in Zn0.097P0.03O
and 82% in Zn0.093P0.07O films. The photoresponses of all the films are
repeatable and quite stable in phosphorous doped films. The deposited
films are found to be inactive for the white light which suggests their
blindness for visible region. The photoresponses of the deposited films
are also found to be strongly dependent on the type of substrates. The
photoresponse observed for the present pristine ZnO thin film deposited
on silicon substrate is quite higher (50–65%) than the pristine ZnO film
deposition on glass substrate (19.75%) with response and recovery
times of ~ 47 and 90 s, respectively [22]. Whereas, the response and
recovery times for the present pristine ZnO thin film deposited on si-
licon substrate is only about 200 ms. Such substrate effect on the UV
photodetection behavior of ZnO film may be due to conducting nature
of silicon substrate, which may provide some interfacing effect. More-
over, highly p-type character of silicon substrate and n-type nature of
ZnO thin film may lead to heterostructural formation resulting in im-
proved photoconductive behavior of the ZnO film.
The change in electric current has also been measured at different
illumination intensities of UVA light in the range 0.367–3.3 mW/cm2. It
is observed that the electrical current in all the films increases with
increase in illumination intensities. The increase in photo-induced
current can be attributed to increase in photo-generated electron-hole
pairs. Fig. 6(a-c) shows the variation in electric current in the ZnO,
Zn0.097P0.03O and Zn0.093P0.07O films, as a function of time and illu-
mination intensity. The electric current in all the films increase almost
linearly with illumination intensities and quite stable with time. All the
K. Singh et al. Materials Science in Semiconductor Processing 95 (2019) 7–19

Fig. 5. Variation of current in the (a) pristine ZnO, (b) Zn0.097P0.03O and (c) Zn0.093P0.07O as function of time, variation of photoresponse in the (d) pristine ZnO, (e)
Zn0.097P0.03O and (f) Zn0.093P0.07O thin films as function of time at fixed illumination intensity (3.3 mW/cm−2).

Fig. 6. Variation of current in the (a) pristine ZnO, (b) Zn0.097P0.03O and (c) Zn0.093P0.07O as function of time, variation of photoresponse in the (d) pristine ZnO, (e)
Zn0.097P0.03O and (f) Zn0.093P0.07O thin films as function of time at varying illumination intensity (0.367–3.3 mW/cm−2).

13
K. Singh et al. Materials Science in Semiconductor Processing 95 (2019) 7–19

Fig. 7. (a) Variation of photoresponse of pristine ZnO, Zn0.097P0.03O and Zn0.093P0.07O as function of illumination intensity, I-V characteristics of (b) pristine ZnO, (c)
Zn0.097P0.03O and (d) Zn0.093P0.07O thin films at varying illumination intensity (0.367–3.3 mW/cm−2).

Table 3 concentration is directly proportional to the absorbed photon flux, thus

Fitted parameters of power law for the ZnO, Zn0.97P0.03O and Zn0.93P0.07O an increase in photoresponse with illumination intensity is observed.
films. The dependence of photoresponse of the deposited films can be express
Sample name α β χ2 by power law of the form [39–41]

ZnO 15.03806 1.22752 0.99453 Response, R = α * Pdβ (7)

Zn0.97P0.03O 20.84539 1.06061
Zn0.93P0.07O 24.80512 1.02201
cycles of UV exposure and recovery are highly repeatable and samples
instantaneously reaches to their original values on switch off the UVA
light that negates the heating effect and fast recovery of the sample. The
change in electric current at different illumination intensities has also
been converted into photoresponse using the relation (2) and presented
in Fig. 6(d-f). The photoresponse of the pure ZnO films is found to
change from ~ 5.78 to 65%, while, it is changed from 5.98% to 82% in
the film deposited with 7 wt% doping of phosphorous in ZnO film. The
enhanced photoresponse of the deposited films doped with phos-
phorous can be attributed to the presence of deep trap states in band
gap region, which lengthen the carrier life time and enhance surface to
volume ratio (smaller size of surface structure), which shorten the
carrier transit time.i.e short channel length [1,4,22]. Thus, ultrahigh
photoresponse and fast response time suggests the defect induced
trapping and recombination at the surface.
Fig. 7(a) demonstrates the dependence of photoresponse of the de-
posited films on the illumination intensity in the range of
~ 0.367–3.3 mW/cm2. Since the photo-generated charge carrier
0.98524
0.9769
where, α is an constants, generally called photoresponse efficiency, Pd
is the illumination intensity, and the exponent ‘β’ is related with the
semiconducting processes like electron-hole pair generation, trapping
and recombination, etc. The value of parameter associated with pho-
toresponse efficiency is found to increase from 15.03806 to
20.84539–24.80512 with phosphorous doping concentrations 0.0 wt%
(pure ZnO film) to 3.0 wt% (Zn0.97P0.03O film) to 7.0 wt% (Zn0.93P0.07O
film). Whereas, the value of exponent ‘β’ found to decrease (from
1.22752 to1.06061 to 1.02201) with phosphorous doping concentra-
tion (Table 3) and approaches to unity, which indicates the change in
nonlinear to linear behavior of the photoresponse with phosphorous
doping, i.e. a direct dependence of photoresponse on illumination in-
tensity. The exactness of fitting can be illustrated from the χ2 values
and all the curves are found to be fitted better than 97.6%. A non-linear
dependence of photoresponse on the illumination intensity can be at-
tributed to the complex process like that of production of electron-hole
pairs, trapping, and recombination of charge carriers within the semi-
conductor [38]. The observed behavior of photoresponse of the de-
posited films is well matched with other published reports [39–41].
Boruah et al. [39] observed a value of 0.97 for β parameter for the
hydrogenated ZnO Nanoflakes.

14
K. Singh et al.
Fig. 7(b-c) shows the I-V characteristics of the pure ZnO,
Zn0.97P0.03O and Zn0.93P0.07O films recorded in dark as well as under
UV light of different illumination intensities from 0.0367 to 3.3 mW/
cm2. It has been observed that all the sample have a linear variation of
current with applied voltages in dark as well as under UV illumination,
which indicates the ohmic behavior of the electrodes and discards the
surface charge limiting current (SCLC) type of conduction. It is also
observed that the electric current in all the samples increases with il-
lumination intensity for all the applied voltages linearly and the change
in current is quite high in Zn0.93P0.07O film at all voltage as compared to
other samples. Moreover, the dark current is found to increase with
phosphorous doping concentration. i.e. Zn0.93P0.07O film has very high
electrical conductivity as compared to pure ZnO, which make it a sui-
table material for electronic and optoelectronic applications.
3.4. Parameters of device performance
Responsivity and detectivity are two key parameters used for the
evaluation of detection limit and device performance of photodetectors.
Responsivity (Rλ) is the measurement of sensitivity of a photodetector
towards the illumination intensity and generally defined as the amount
of current comes out from the device per incident photon of known
energy and mathematically represented as [39–47]
Jp ∆I
Rλ = = detectivity of all the deposited films is quite high and increases with
Pd Pd A
where, Jp is the photo-current density, Pd is the power density or
Fig. 8. (a) Variation of (a) responsivity (b) detectivity and (c) external quantum efficiency of pristine ZnO, Zn0.097P0.03O and Zn0.093P0.07O at a fixed illumination of
3.3 mW/cm−2.
Materials Science in Semiconductor Processing 95 (2019) 7–19
illumination intensity, A is the illuminated sample area, and ΔI˭Ip-Id is
the photo-current which is defined as the difference in current under
UV illumination (Ip) and dark current (Id). Fig. 8a illustrates the re-
sponsivity of deposited films at a fixed illumination intensity of
3.3 mW/cm2 and found that the responsivity of ZnO films increases
with phosphorous doping concentration. The film deposited with 7 wt%
phosphorous doping has a responsivity of ~ 0.18 A/W which is greater
than the reported values [39,48,49]. Boruah and Misra [39] observed a
responsivity value of ~ 2.65 mA/W for the ZnO nanoflakes prepared by
simple chemistry based chemical method, whereas, Zahedi et al. [49]
observed a responsivity values of 0.055 and 0.125 A/W for the ZnO/p-
Si and ZnO:N/p-Si heterojunction thin films. The observed value of the
responsivity is also found to be in the range of commercial UV photo-
detectors (~ 0.1–0.2 A/W) [50].
This suggests that the photoconductive behavior of prepared ma-
terial depends upon the structure as well as preparation technique.
Detectivity is another important parameter used to estimate the
device performance of a photodetector and defined as the ability of the
device to detect weak optical signal. It is the measurement of signal to
noise ratio (Fig. 8b) and mathematically can be expressed as [39–47]
Rλ
D=
2eJd (9)
where, e is the electronic charge and Jd is the dark current density. The
(8)
phosphorous-doping concentration. The detectivity of Zn0.93P0.07O film
is found to be ~ 2.6 × 1010 cm Hz1/2/W and well matched with the
15
K. Singh et al. Materials Science in Semiconductor Processing 95 (2019) 7–19

reported literature values [38,47,48,51] for ZnO films, which suggest
that the deposited films has superior device performance and photo-
characteristic with the ability to detect a much lower UV signal.
External quantum efficiency is an important parameter related with
the efficiency of the photodetectors to convert a photo-signal into a
useful electrical-signal and generally defined as the ratio of the number
of electrons collected per unit time to the number of photons of known
energy falls on the surface of the detector per unit time. The external
quantum efficiency or the photoconductive gain can be mathematically
expressed as [27,38–48,52]
Jp hc Rλ hc
EQE (%) = x100 = x 100
Pd eλ eλ
Where, λ (≈ 365 nm) is the wavelength of the incident radiation, h
is the Planck's constant, c is the velocity of UV light photon, and e is the
electronic charge. The EQE is strongly dependent on the carrier life-
time, transit time, and the density of the trap states in the band gap
region. The very high values of the external quantum efficiency
(~ 6.2 × 1010%) in the present samples (Fig. 8c), may be the resultant
of the exceedingly long carrier lifetime along with quite short carrier
transit time due to high quality of the films with reduced dimension-
ality of nanocrystals, such that each photon will participate in the
generation of electron-hole pair [34,39,53].
Linear dynamic range (LDR) is another crucial scientific figure-of-
merit of a photodetector, related with photocurrent to dark current and
signal to noise ratios. The linear dynamic range of a photodetector can
be estimated [34,39,53]
Ip
LDR = 20log (in dB )
Id
Where, symbols have their usual meanings. The variations of LDR de-
termined at various illumination intensities ranging from 0.367 m to
3.3 mW/cm2 is tabulated in Table 4. The reasonably high value of LDRs
for all the samples suggesting the effective conversion of UV light into
photocurrent at all the intensities. The significant value of LDR for these
samples indicating the reasonable absorption depth of UV light in ZnO
films and significant power conversion efficiency. The variation of LDR
with illumination intensity can be ascribed to the increase in photo-
induced electron-hole pairs with incident photon flux density [39].
The photocurrent enhancement factor (PEF) has also been calcu-
lated for the present metal oxide films using the relation [54–56]
Ipl d
PEF =
Izl d
where, IPℓd is the ratio of the photocurrent to dark current for the
phosphorous-doped ZnO thin films, and IZℓd is the ratio of photocurrent
Table 4
Parameters related to photoconductors performance such as LDR, Trap depth,
EEF, PEF.
Intensity Sample name LDR (dB) PEF Trap depth
(mW/cm2) (eV)
to dark current for the pristine ZnO thin film. The value of PEF is found
to vary from ~ 0.96 to 1.16 with illumination varying the intensity
from 0.367 to 1.467 mW/cm2 (Table 4). The observed value of photo-
enhancement factor (PEF ≈ 1) is comparable to value of observed by
Ahmad et al. [54] for their hybrid devices of vertical silicon nanowires
with ZnS nanoparticles and Huang et al. [55] for their silicon nano tips
and ZnS nanoparticles heterostructural devices.
The parameter associated with the amount of energy required to
eject the electron from trap state in the band gap region, so called trap
depth (E) has also been evaluated for the present films at different il-
lumination intensities using the expression [56–58] from the decay
curves
(10)
⎛
E = kT ⎜lnf − ln
( )
I
⎧ ln I0 ⎫ ⎞
⎟
⎜ ⎨ t ⎬⎟
⎝ ⎩ ⎭⎠ (13)
where, k is the Boltzmann constant, T is the temperature, and f (~ 109
Hz at room temperature) is the frequency factor, that can be defined as
the product of the number of attempts made by lattice vibration
(phonon) per second to release the electrons from the trap states and
the transition probability of the ejected electrons in the conduction
band [45,52,59]
The trap depth can be evaluated from the decay curve (i.e the curve
associated with the decrease in current after switch off the UV source),
where the transient decay current (I) at any instant of decay time can be
given by the relation [52,56,60]
I= I0 e−pt (14)
(11) where, I0 is the saturated value of the photocurrent or the current at
which the light is switched off and p is the probability of ejection of an
electron from the trap depth and the Eq. (14) is used for the determi-
nation of electron ejection probability (EEP). It is observed that the
value of the electron ejection probability lies in between the 0.3 and 2.8
at different illumination intensities and varies with doping concentra-
tions. The obtained values of ‘EEP’ are summarized in Table 4 and
further used to calculate trap depth (E) which is related with ‘EEP’ and
the temperature as [56,60]
p = fe−E / kT (15)
Thus, by using the frequency factor (f) and probability of electron
ejection (EEP) in the expression (15), which is another form of Eq. (13),
the trap depth (E) is determined for all the samples and provided in
(12) Table 4. The trap depth values evaluated at different illumination in-
tensities for the present samples are found to be in the range of
0.51–0.57 eV. The observed value of the trap depth for the present
samples is lesser than or comparable to the reported values 0.71 eV for
ZnS nanoparticles [57], and 0.67 eV for TiO2 nanoparticles [60], which
means a lesser energy value is required for the ejection of electron from
the trap states.
EEP 3.5. Mechanism of photoconduction

0.367 ZnO 0.64176 0.56198 0.36949 The photodetection behavior in the present ZnO thin films can be
Zn0.97P0.03O 0.37903 0.9702 0.5756 0.21822 governed by adsorption and desorption of oxygen molecules on the
Zn0.93P0.07O 0.68958 1.00552 0.56012 0.39703 surface of the film. In dark condition, when the deposited films are
0.528 ZnO 0.65664 0.56138 0.37806
exposed to the normal environment (air), oxygen molecules (red balls)
Zn0.97P0.03O 0.58263 0.99152 0.56448 0.33545
Zn0.93P0.07O 0.68958 1.0038 0.56012 0.39703 get absorbed on the films surface and transform into oxygen ion (green
0.825 ZnO 0.99938 0.55052 0.57539 balls) by pulling out the electron from the conduction band (Fig. 9a).
Zn0.97P0.03O 1.12701 1.0148 0.54741 0.64888 This mechanism can be understood by the following chemical processes
Zn0.93P0.07O 1.27957 1.03278 0.54412 0.73671 [22,32,61,62]
1.467 ZnO 1.62005 0.53802 0.93274
Zn0.97P0.03O 2.78639 1.14371 0.52398 1.60426 O2 (ads ) + e− ↔ O2− (ads) (16.i)
Zn0.93P0.07O 2.93874 1.16395 0.52261 1.69198
3.3 ZnO 4.47619 0.51172 2.57717 O2 (ads ) +2e−↔2O− (ads) (16.ii)
Zn0.97P0.03O 4.7542 1.03252 0.51016 2.73723
Zn0.93P0.07O 5.00053 1.06223 0.50885 2.87906 O− (ads ) +e− ↔ O 2 − (ads) (16.iii)

16
K. Singh et al.
The extraction of the electron from the conduction band or cap-
turing of electrons at the surface creates a space charge region (or de-
pletion region) which leads to an upward band bending (Fig. 9b) and
the thickness of depletion layer is generally represented by Debye
length and equal to the length of band bending region. This will leads to
decrease in carrier concentration and narrow down the conduction path
(Fig. 9c) for carriers [22,32,61,62]. As a result of this depletion layer,
the potential barrier at the grain boundaries increase, and related with
depletion width (WD), given by the relation
2 ∈ ϕB
WD =
Nd e 2 (17)
where, e is the electronic charge, Nd donor density, ε permittivity of
ZnO film. The height of potential barrier (ΦB = eVs) at the grain
boundaries equal to the upward band bending (eVs), and the electric
current (or electric resistance) in the film is given by [22,62]
⎛
−eVs
⎞ ⎛ −ϕB ⎞
⎜ ⎟
I = Io e⎝ kT ⎠ = Io e⎝ kT ⎠ (18)
Where, k is the Boltzmann's constant, T is the temperature and Vs is the
surface potential.
Fig. 9d illustrates the upward band bending of height equal to the
potential barrier (ΦB = eVs) at the surface and interfaces of the grain
boundaries. The double headed blue arrow indicates the depletion
width (WD) between the grains. Fig. 9e shows the electronic model of
the films, demonstrating the possible combinations of resistances con-
tributing in the total resistance of the film and participating in the
photoconduction. There can be four types of resistance contributing in
the present case (i) metal semiconductor contact resistances (electrode
resistance, Re) which are in series with other resistances (ii) outer space
charge layer resistance of the grains (Rs) and (iii) bulk resistance of the
grains (Rb), which are in parallel with each other and series with
electrode resistances, and (iv) grain-grain contact resistance (RGB) de-
pends on depletion width and in series with the individual grains
17
Materials Science in Semiconductor Processing 95 (2019) 7–19
Fig. 9. Schematic representation of (a) measurement of
dark current with the interaction of metal oxide thin film
surface with oxygen molecules, (b) upward band bending
due to adsorption of oxygen molecules, (c) formation of
depletion layer due to environmental exposure of metal
oxide thin films (d) variation of potential barrier height at
the grain boundaries in the absence of UV light, (e) elec-
trical equivalent circuit for the measurement of dark cur-
rent, (f) measurement of current under illumination with
conversion of oxygen ions (O2-) into oxygen molecules via
the combination of holes (h+) in the presence of UV light
(g) decrease in thickness of depletion layer under UV light
exposure (h) decrease in potential barrier height under UV
light (i) electrical equivalent circuit for the measurement
of current under illumination, (j) open neck grain-
boundary control mechanism for low resistance (k) open
neck neck-control mechanism for high resistance sample
(ℓ) open neck grain-control mechanism for high resistance
and (m) closed neck grain-control mechanism for high
resistance.
resistances (Rs//Rb). Thus if consider a model in which, there are total n
numbers of grains on the surface of the film in series, then on an
average, there are n number of parallel combination of grain resistances
(Rs//Rb) with n-1 numbers of grain- grain contact resistances (RGB),
along with two electrode resistances (Re), contributing in total surface
resistance of the film. Therefore, the photoresponse, which is governed
by the change in electrical resistance/current (ΔI/Io), can be given by
[22,61]
⎛ −e ∆ Vs ⎞ ⎛ −∆ ΦB ⎞
Response = e⎝ kT ⎠ = e⎝ kT ⎠ (19)
Where, ΔVs is the change in surface potential under UV illumination
leading to potential barrier height (ΔФB). Thus, the apparent change in
photoconduction in the present device can be attributed to the change
in potential barriers height. Apart from surface absorbed oxygen mo-
lecules, photoresponse can also be strongly influenced by the oxygen
vacancy defects on the surface, which lead to much more adsorption of
oxygen molecules on film surface, results in significantly increase in
space charge region. This will cause an upward band bending at the
grain-grain junctions.
On illumination with the light of suitable energy greater than band
gap (Eg), electron-hole pairs are generated [hν→ e- + h+], as demon-
strating in Fig. 9f. Out of these photo-generated electron-hole pairs,
holes (blue balls) migrate towards upper surface with varying potential
created by band bending and coupled with adsorbed oxygen ions (green
ball) to create oxygen molecules (red balls) (Fig. 9f). These photo-
generated oxygen molecules finally get desorbed from the film surface,
which can be understood via the chemical process of type [22,62–64]
h+ (hv ) + O2− → O2 (Des.) (20)
While, the photo-generated unpaired electrons are moved towards
the bulk i.e given back to conduction band, which results in a decrease
in the thickness of depletion layer (Fig. 9g) and depletion width. The
neutralize negative surface charges by the photo-generated holes (Eq.
K. Singh et al.
Fig. 10. Photoresponse of the (a) pristine ZnO film and (b) Zn0.93P0.07O thin films observed in air atmosphere, N2 atmosphere and vacuum.
(21)), causes in a decrease in surface band bending and hence corre-
spondingly potential barrier height at the grains or grain boundaries
along with the depletion width indicated by shortened double blue
arrow, in Fig. 9h [22,62–64]. Thus, these processes leads to a decrease
in all the resistances associated with the surface (Rs), bulk (Rb) and
grain boundaries (RGB), etc. between all the grains or between two
electrodes (Fig. 9i), however, all the resistances are still persisted. As a
result of this, concentration of charge charier received at the electrodes
significantly increases, which will responsible for a large and prompt
increase in electrical current/conductivity under UV illumination and
hence a quick response of the photodetector. The mechanism of pho-
toconduction discussed above is based on the grain boundary control
model having two adjacent particles/grains placed side by side (Figs. 9c
and 9g) and the resistance of the device is the barrier type of resistance
between two grains.
However, this model can be further improved for the samples de-
posited at high temperatures (~ 450 °C in the present case) or annealed
at relatively high temperature. The enhanced photoresponse of the
deposited films can be attributed to the multiple joint or neck con-
nectivity between the ZnO nanoparticles distributed throughout the
surface. Thus, the improved photoconductive behavior of the phos-
phorous-doped films can be further understood on the basis of grain size
(quantum size confinement) effect on the device performance in terms
of the neck width (i.e. size of the inter-connections shown by the double
headed vertical blue arrow) of two adjacent grains/particles (indicated
by the brown balls) formed due to high temperature growth process and
the width of space charge layer (shown by green colored region) gen-
erally represented by the Debye length for the electrons [64] as shown
in Figs. 9j to 9m. Since these grains are interconnected by the space
charge region, therefore, the Debye length can be treated equivalent to
the half of the depletion width (WD) shown by double headed red ar-
rows in Fig. 9k-m.
Figs. 9j to 9m represents various modes of inter-connections be-
tween two adjacent grains (i.e. relative values of neck width and Debye
length) responsible for sensitivity of the present samples. Fig. 9j re-
presents a grain-boundary type inter-connection between grains when
neck width is greater than the Debye length. This is an open neck type
of mode having very low contact resistance and the conductance of the
device depends upon the bulk of the grains for bigger size grains.
However, on the other hand if the size of the grains is very small and
the neck width is approximately equal to Debye length as shown in
Fig. 9k, then the resistance of the neck or inter-grain connection will
remain high and depends upon surface trap states. In such case, the
device performance can be understood through open neck control type
of model [64–66]. If the neck width further decrease as compared to
Debye length (Fig. 9ℓ), then the resistance of the sample/inter-
18
Materials Science in Semiconductor Processing 95 (2019) 7–19
connection become further high and the performance of the device is
governed by the grain-control type of model for open neck. The device
performance can also be governed by closed neck model when the size
of the crystals is large but the neck width is very small as compared to
the Debye length. The response of the device depends upon the surface
states and model is so called grain-control model (Fig. 9m). Since the
grains/particles observed on the film surfaces are sufficient larger size
(depletion layer) and the film surface are sufficiently dense to form
open neck grain-control type of structure. Thus, the photoresponse in
the present films can be understood through open neck grain-control
mechanism associated with change in depletion width on illumination
with UV light.
In order to confirm applicability of the above discussed mechanism
of adsorption-desorption of oxygen molecules for the photoconduction
behavior of the present deposited thin films, photoconductive mea-
surements are performed under three different conditions/environ-
ments (air atmosphere, N2 atmosphere and vacuum) on the pristine and
P-doped (7%) ZnO thin films and results are presented in Fig. 10. It is
observed for both the pristine as well as P-doped ZnO thin films that the
photoconductive response is quite higher in vacuum and N2 atmosphere
as compared to ambient air atmosphere. The highest photoresponse
under vacuum condition may be due to fast desorption of oxygen mo-
lecules from the films surface. However, the recovery of both the
samples is least under vacuum condition that can be attributed to the
unavailability of the oxygen molecules. The recovery of the samples is
also very slow in N2 atmosphere. However, as soon as the air is inserted
into the chamber, samples are recovered instantaneously. Moreover,
the recovery of the samples after inserting the air is somewhat slower,
when the measurements are carried out in N2 atmosphere which could
be due to slower replacement of N2 molecules by O2 molecules as
compared to vacuum condition. The observed behavior of the films
confirms that the present deposited films follow the mechanism of ad-
sorption-desorption of O2 molecules for conduction behavior.
4. Conclusions
Structural, morphological, electrical and optical properties of
phosphorous doped ZnO thin films deposited by pulsed laser deposition
technique are thoroughly investigated. A structural change in respect to
change in XRD peak positions has been observed with phosphorous
doping. However, the XRD studies negate the formation of P2O5 like
phase in phosphorous-doped ZnO films as no extra peaks were observed
due to such formation. Thus, the change in XRD peak position con-
firmed that phosphorous takes interstitial position of Zn or oxygen
vacancies, without affecting the wurtzite structure of ZnO film. The UV-
photodetection studies on the deposited films at fixed 3.3 mW/cm2 and
K. Singh et al. Materials Science in Semiconductor Processing 95 (2019) 7–19

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