Journal of Inorganic and Organometallic Polymers and Materials (2021) 31:1066–1078

https://doi.org/10.1007/s10904-020-01751-y

Impact of ­Zn2+ Doping on the Structural, Morphological

and Photodiode Properties of ­V2O5 Nanorods
N. Senthil Kumar1 · J. H. Chang2 · Mon‑Shu Ho3,4 · Babu Balraj3,4 · S. Chandrasekar3,4 · B. Mohanbabu5 ·
M. Gowtham6 · Donghui Guo5 · K. Mohanraj2

Received: 14 July 2020 / Accepted: 9 September 2020 / Published online: 19 September 2020
© Springer Science+Business Media, LLC, part of Springer Nature 2020

Abstract
In the present study, the effects of ­Zn2+ doping on the microstructural, morphological and photodiode response of the
­V2O5 nanorods have been studied. Pure and ­Zn2+ doped ­V2O5 nanorods were prepared by a simple and cost effective wet
chemical solution process. The XRD studies confirmed that the pure and ­Zn2+ doped samples exhibit crystalline nature with
mixed phases for Zn doping. From the morphology analysis, it is observed that substitution of ­Zn2+ into the ­V2O5 matrix is
found to gradually transform the morphology from hexagonal face rods to short rods mixed with the plate like structures.
The luminescence features of nanostructures are analyzed using photoluminescence studies. Moreover, the V2O5/p-Si and
­ZnV2O5/p-Si photodiodes parameters were studied under dark and light environments.

Keywords Phase change · Doping · Morphological · Junction diode · Nanorods

1 Introduction

As one of the excellent semiconductor materials, vana-

dium pentoxide (­ V2O5) is deliberated to be a vital n-type
semiconductor. Because it has exclusive electrical proper-
ties and thus has been used in the semiconductor indus-
* N. Senthil Kumar try. In the context, vanadium oxides are a superior variety
[email protected] of oxidation states, for instance, VO ­(V2+), ­V2O3 ­(V3+),
* B. Mohanbabu ­VO2 ­(V4+), and ­V2O5 ­(V5+). These oxide states are reliant
[email protected] on the atmospheric conditions. Consequently, the phase
* K. Mohanraj change can occur between their oxides by the atmosphere.
[email protected] Among the different oxide phases, the ­V2O5 oxide phase
1
PG and Research Department of Physics, Kongunadu Arts is considered for real time applications as it is regarded
and Science College, Coimbatore, Tamil Nadu 641029, India as the most oxidized state and, thus, stable oxide phase.
2
Department of Environmental Engineering and Management, Subsequently, it expands applications not limited to ­Li+
Chaoyang University of Technology, Taichung 41349, batteries, memory devices, solar cells, Sensors, electri-
Taiwan cal and optical switching devices [1–18], etc. The ­V2O5
3
Department of Physics, National Chung Hsing University, nanoparticles are to be synthesized by various methods
Taichung 40227, Taiwan such as precipitation [19], thermal decomposition [7], a
4
Innovation and Development Center of Sustainable solvothermal method [6], the hydrothermal method [5].
Agriculture (IDCSA), National Chung Hsing University, Though, the solution-based wet chemical method is a
Taichung 40227, Taiwan capable alternative method in the various available syn-
5
Department of Electronic Engineering, School thesis process because of the easy and cost-effective route
of Electronic Science and Technology, Xiamen University, for synthesizing ­V2O5 nanomaterials. This synthetization
Xiamen 361005, China
process is possible at low temperatures (< 90 °C) as well.
6
Department of Physics, Sri Ramakrishna College of Arts Additionally, this method helps to control the dopants,
and Science, Peelamedu, Tamil Nadu 641006, India

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Journal of Inorganic and Organometallic Polymers and Materials (2021) 31:1066–1078 1067

and thus facilitate to prepare one dimensional nanostruc- 2.2 Characterization Techniques

ture for various applications. Since the energy level can
be engineered by doping various metal atoms to suits the Various characterization techniques study the qual-
specific application, the ­V2O5 energy level has been tuned ity of the synthesized nanoparticles. A Bruker AXS D8
precisely for electrical application. As the refinement of advance discover X-ray diffractometer with CuKα radia-
optical, electrical and magnetic properties of nanocrys- tion (λ = 1.5406 Å) was used to analysis the structural
tals are vital in semiconductor electronics, the transition properties of the synthesized nanoparticles. The SEM
metal ions are, generally, promising doping agents in engi- and TEM morphology of the samples were investigated by
neering semiconductor properties according to particular JEOL-Model JSM-6390 LV and TECHNAI T20, respec-
needs. Numerous literature has been reported and studied tively. The EDS spectra for all samples are recorded by the
the ­V2O5 nanoparticles with various transition metal ions EDS Spectrum analyser (Oxford X-Max 50 ­mm2) detec-
[20–24]. In this context, already few authors have doped tor incorporated in the Zeiss Ultra Plus SEM system. The
Zn with the ­V2O5 and reported their structure. The ionic ultraviolet (UV) spectrum of the prepared samples was
radius of Z­ n2+ (0.074 nm) is lightly larger than the V­ 5+ recorded using a Perkin Elmer UV-Visible DRS spectrom-
(0.059) which makes the possible incorporation of Z ­ n2+ eter. The photoluminescence spectrum was also inspected
ions into the ­V2O5 lattice [25, 26]. In this work, the wet by the instrument model of Horiba Jobin Yuon Fluorolog
chemical method was used to produce pure and Zn-V2O5 with the range of 185–900 nm on the sample. The photore-
nanoparticles with various concentrations of Zn. sponse features of the fabricated diode were analyzed with
a Keithley 6517 B instrument.

2 Methods
3 Results and Discussion
2.1 Synthesis of Pure and ­Zn2+ Doped ­V2O5
Nanoparticles 3.1 Structural Analysis of ­Zn2+ Doped ­VO2 Samples
Annealed at 60 °C for 12 h
An ammonium metavanadate ­[NH4VO3] (Sigma-Aldrich,
ACS reagent, ≥ 99.0%) and hydrogen peroxide ­[H 2O 2] The XRD patterns of pure and ­Zn2+ doped ­VO2 (Zn = 5, 10
(Sigma-Aldrich, 30% (w/w) in H ­ 2O) and zinc nitrate hexahy- and 15 wt%) samples with different dopant concentrations
drate ­[ZnNO3)2.6H2O] (Sigma-Aldrich, reagent grade, 98%) were annealed at 60 °C for 12 h, as shown in Fig. 1a. The
were used as a starting material. A typical reaction process diffraction peaks at scattering angle 2θ values of 14.38o,
was used to synthesis ­Zn2+ doped ­V2O5 by involving the fol- 18.22 o, 20.927, 23.97 o and 29.79 o are associated with
lowing methods. Zinc nitrate of dopant materials at a differ- (110), (111), (200), (002) and (220) planes, respectively.
ent weight percentage and 4.2 g of ammonium metavanadate All the observed peaks can be assigned to the tetragonal
are mixed with 50 ml deionized water. The resultant solu- rutile structure of V­ O2 with lattice constants of a = 8.483
tion was continuously stirred for 20 min. Concurrently, the Å and c = 7.615 Å, which are confirmed by reference pat-
homogenous solution was prepared by adding 10 ml of H ­ 2O2 tern JCPDS card No: 82-1074. No characteristic peaks
dropwise. The yellow color solution’s pH value was adjusted of some impurities were observed in the diffractogram,
to 2.5 by adding a few drops of concentrated ­HNO3 (Sigma- which indicating the single phase formation. The struc-
Aldrich, ACS reagent, 70%). Later, the mixture solution was tural analysis of Z­ nVO2 samples reflects the segregation
vigorously stirred until color changes to a dull orange shade. of the secondary phase and their additional peaks at 2θ
Then, the chemical method was adapted by adding 0.05 g of 11.28o and 12.428o (marked by star *) are associated
polyvinylpyrrolidone(PVP) ((K30) BioChemica) in the solu- with α-ZnV3O8 (JCPDS card No: 24-1481). It should be
tion. The obtained mixture was put into continuous stirring noted that, even though no zinc clusters or other second-
at 45 °C for 24 h. Later, the settled pale yellow solid yields ary phases are detected by XRD analysis, the existence of
were filtered and washed several times with double distilled secondary phases cannot be excluded entirely due to the
water and ethanol to remove the organic impurities. The limitation of this characterization technique. However, all
obtained fine powder was dried at 60 °C for 12 h. Finally, doping levels, the limited number of dopant ions caused
the samples of ­Zn2+ doped ­V2O5 nanoparticles are collected the reaction to be incomplete. Hence, ­Zn2+ enters partially
after annealing the powder at 600 °C under the air atmos- into the host as interstitial ions and the un-substitution of
phere for 1 h. Besides, the same procedure was followed ­Zn2+ ions form individual ­V2+ sites and secondary phase.
without doping source material to prepare the undoped ­V2O5 The secondary phase intensity is increased due to the
nanoparticles for comparison.

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1068 Journal of Inorganic and Organometallic Polymers and Materials (2021) 31:1066–1078

Fig. 1  XRD pattern of a ­Zn2+ doped V ­ n2+ doped V

­ O2 (Zn = 0, 5, 10 and 15 wt%) samples at 60 °C for 12 h, b a shift position of Z ­ O2, c ­Zn2+
2+
doped ­V2O5 samples annealed at 600 °C for 1 h and d a shift position of Z
­ n doped ­V2O5

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Journal of Inorganic and Organometallic Polymers and Materials (2021) 31:1066–1078 1069

excess amount of ­Zn2+ readily reacts with the ­V2+ ions in to ­V2+ ions are replaced by Z­ n2+ ions because of the smaller
2+
the medium. From Fig. 1b, it is observed that the major radius of Z­ n (0.74 Å) than V ­ 2+ (0.93 Å). Therefore, the
diffraction peaks of ­Zn2+ doped V ­ O2 samples show that a change of lattice constant could be attributed to Zn incorpo-
small shift towards higher 2θ value when compared to that ration and it is indicative of defect evolution in the lattice.
of pure ­VO2. This shift is attributed to the substitution of a
smaller ionic radius of ­Zn2+ ­(rZn2+ = 0.74 Å) ions to ­V2+
3.1.1 Structural Analysis of ­ZnV2O5 Samples Annealed
­(rV2+ = 0.93 Å) larger ionic radius. The average crystallite
at 600 °C for 1 h
size of the studied samples have been estimated with the
help of the Debye Scherer’s Eq. (1),
The XRD patterns of ­Zn2+ doped V ­ 2O5 (where x = 5, 10
k𝜆 and 15%) samples annealed at 600 °C for 1 h, as shown
D= (1) in Fig. 1c. The position of diffraction peaks at 2θ values
𝛽cos𝜃
of 15.47o, 20.39o, 26.27o and 31.14o are assigned to miller
where D-is the crystallite size, k is a constant which depends indices (200), (001), (110) and (400), which shows a good
on the shape of the crystallite, Miller indices and Bragg agreement with the orthorhombic crystal structure of
demonstrated that its value is about 0.9, λ is the wavelength ­V2O5 (JCPDS card No.: 41-1426) and are lattice param-
of the incident radiation, β is the broadening of the diffrac- eters a = 11.51, b = 3.565 and c = 4.372 Å. However, the
tion line (FWHM) and θ the Bragg diffraction angle. The orthorhombic structure of undoped V ­ 2O5 is not alerted by
estimated crystallite size of pure and Zn doped V ­ O2 samples the doping of Z ­ n2+ ions. Notably, the Z ­ n2+ doped samples
are presented in Table 1 and it has been found that crystal- exhibit the secondary phase and the emergence of additional
lite size decreases from 27.16 to 12.52 nm as ­Zn2+ doping peaks at 2θ of 27.13o and 29.35o are associated with the
increasing from 5 to 15 wt%. This decrease may be due to monoclinic phase of ­Zn3(VO4)2 (JCPDS card No: 34-0378)
the suppression of nucleation and subsequent growth of ­VO2 [28]. As the doping concentration (x) increases, the peak
by ­Zn2+ doping. The lattice spacing (d), angle of diffraction positions in the XRD patterns were also shifted to higher 2θ
(2θ) and FWHM values are also presented in Table 1. From values (Fig. 1d), which is due to the occupancy of V ­ 5+ sites
the XRD results it is interesting to notice that the synthe- 2+
by ­Zn causing some kind of lattice distortion that induced
sized pure and Zn doped samples annealed at 60 °C exhib- due to tensile stress. This shift is related to the higher substi-
its the tetragonal phase of ­VO2 and transformed into the ­ n2+ (0.74 Å) with ­V5+ (0.54 Å) ions. The FWHM
tution of Z
orthorhombic phase of V ­ 2O5 when the samples annealed gradually increased with doping of Zn contents, which, in
at 600 °C. It is also reported earlier that a phase conversion turn, decreased the crystallite size for all doping levels.
occurred at 600 °C in the case of V ­ 2O5 materials [27]. The The average crystalline size has been estimated by Scherrer
lattice parameters of pure and Zn doped V ­ O2 samples for Eq. (2) using the FWHM of the major peaks and its values
tetragonal crystal structure were estimated using the follow- are listed in Table 2. As shown, the crystallite size is in
ing Eq. (2), the range between 25.05 and 13.16 nm and it decrease with
the increase of Zn contents, which reveals that the presence
1 h2 + k 2 l2
2
= 2
+ 2 (2) of Zn ions in ­V2O5 prevented the growth of crystal grains,
d a c
suggesting that the dopant influences the grain growth. This
where d-is the lattice spacing of the crystallographic plane decrease may be owing to the suppression of nucleation and
and hkl are the Miller indices of the reflection plane. The lat- subsequent growth of ­V2O5 by ­Zn2+ doping. In the case,
tice constant ‘c’ has been calculated from the (002) diffrac- more defects such as interstitials and vacancies in the lat-
tion peak and presented in Table 1. As seen in this table, the tice are usually created when doped by the foreign impurity.
lattice parameters decrease with the increase of Zn contents. The nucleation is suppressed by these defects on the grain
This decrease in the lattice parameters can be expected due surface/boundaries and prevents subsequent grain growth.

Table 1  Structural parameters of Z

­ nVO2 samples annealed at 60 °C for 12 h
ZnVO2 (Zn= 0, 5, 2θ (degree) D-spacing (nm) FWHM (degree) Grain Size (D) nm Lattice constant (Å)
10 and 15 wt%)
JCPDS Observed JCPDS Observed C-axis

00 23.3440 23.3389 3.8026 3.80837 0.31460 25.797 7.616740

05 23.3440 23.1827 3.8026 3.83367 0.29870 27.163 7.667340
10 23.3440 23.6798 3.8026 3.75431 0.33970 23.906 7.508620
15 23.3440 23.6070 3.8026 3.76572 0.64520 12.522 7.531440

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Table 2  Structural parameters of Z
­ nV2O5 samples annealed at 600 °C for 1 h
ZnV2O5 (Zn= 0, 5, 2θ (degree) Hkl D-spacing (nm) FWHM (degree) Grain size (D) nm Dislocation density Micro-strain (ε) Volume (Å3) Lattice constants (Å)
10 and 15 wt%) ­(1014 lines/m2) ­104 ­lin−2 ­m−4
a b c

00 15.4136 200 5.74406 0.31750 25.2620 0.001567 0.159152

20.3600 001 4.35865 0.33750 23.9268 0.001747 0.167283 177.85 11.48 3.555 4.358
26.2487 110 3.39242 0.29870 27.3226 0.001340 0.177739
51.3571 020 1.77766 0.27460 32.1134 0.000970 0.190126
05 15.1000 200 5.86264 0.32000 25.0554 0.001593 0.157962
20.6303 001 4.28951 0.37040 21.8109 0.002102 0.165156 178.90 11.72 3.559 4.289
26.5382 110 3.35606 0.39640 20.6006 0.002356 0.170761
51.3000 020 1.77951 0.25140 35.0686 0.000813 0.190956
10 15.7111 200 5.63595 0.56030 14.3200 0.004877 0.129223
20.8546 001 4.25609 0.49470 16.3364 0.003747 0.153182 169.74 11.27 3.539 4.256
26.7290 110 3.33254 0.42660 19.1498 0.002727 0.168760
51.6000 020 1.76986 0.44400 19.8814 0.002530 0.184064
15 15.8865 200 5.57412 0.60940 13.1690 0.005766 0.123873
20.6906 001 4.28945 0.53030 15.2357 0.004308 0.149398 168.37 11.14 3.524 4.289
26.5341 110 3.35657 0.50190 16.2702 0.003778 0.162947
51.8434 020 1.76213 0.49180 17.9675 0.003098 0.182433
Journal of Inorganic and Organometallic Polymers and Materials (2021) 31:1066–1078
Journal of Inorganic and Organometallic Polymers and Materials (2021) 31:1066–1078 1071

The added structural parameters, dislocation density (δ) and size of the particle is observed by increasing dopant per-
microstrain (ε) were resolved using the relation (3) and (4), centage of 5–15 wt%. Subsequently, a greater number of
nucleation sites were observed by adding Z ­ n2+ ions into the
1 5+
𝛿= (3) ­V solution. Accordingly denser nanorods were resulted by
D2
reduced grains. The small particles were agglomerated and
bound to the nanorods mix nano-box like particles due to the
𝛽cos𝜃 doping of Z ­ n2+. Numerous kinds of shapes of nanoparticles
𝜀= (4)
4 from large sheets, long rods, short rods, incomplete face rod
The estimated dislocation density (δ) and microstrain (ε) to small plates were attained for various concentrations of
values are listed in Table 2 and it is observed that the dislo- ­Zn2+ from 0 to 15%. Similarly, the accumulation of obtained
cation density is slightly increased with the increase of dop- nanoparticles is owed to the increment of the surface area
ing concentration. This may be due to the decrease in grain to volume ratio.
size and the presence of larger defect states. The orthorhom- The EDS spectra of the synthesized samples are depicted
bic crystal structure, the lattice parameters of ­V2O5 at dif- in Fig. 3a–d and the inset table shows the atomic percentage
ferent contents of Zn were determined using the relation (5) distribution of the individual elements. The EDS spectra
revealed that the synthesized samples are free from contami-
nations or impurities and showing the typical peaks for V,
√
1 h2 k 2 l2
= + 2+ 2 (5)
dhkl a 2 b c ­ n2+ atomic
Zn, and O elements. It is clearly shown that the Z
percentage increases with increasing the doping percentage
where a, b and c are the lattice constants; h, k and l are of the synthesized samples.
the miller indices of the plane, and ­dhkl is the interplanar
spacing. The interplanar d-spacing can be calculated from 3.3 TEM Analysis
Bragg’s law. The calculated lattice parameters are listed in
Table 2 and it is clearly indicated that a decrease in the lat- The TEM image, shown in Fig. 4a of undoped V ­ 2O5 and
tice parameters seems to be entirely justified as ionic radii their derived product, were composed of small tightly-
of ­Zn2+ is higher than that of V
­ 5+ [29]. The volume of the packed one-dimensional short nanorods. The HRTEM image
unit cell of the orthorhombic system can be estimated from of ­V2O5 nanorods in Fig. 4a shows that well-resolved lattice
the Eq. (6), spacing of 0.579 nm matching to d-spacing of orthorhom-
V=a∗b∗c (6) bic ­V2O5. The bright field TEM images in Fig. 4b–d shows
that zinc-doped V ­ 2O5 with different dopant concentrations.
where a, b and c are lattice parameters. The volume of Z ­ n2+ The particles were less agglomerated and nanorods with
doped ­V2O5 (Zn = 5 wt%) slightly increases and its micro- smooth sidewalls and uniformed diameters are observed.
strain decrease than that of pure ­V2O5 (Table 2), which may The concentration of Zn in the precursor decides the den-
be because the substitution impurity has been trapped in sity and diameters of nanorods. The diameter and length
non-equilibrium positions. But as the doping concentration of 5 wt% ­Zn2+ doped ­V2O5 are nearly the same as those of
increases, the impurity ions shifted to the equilibrium posi- the undoped ­V2O5 nanorods and significant some rods are
tions, which form the secondary phase [30]. Besides, the incomplete. From the TEM image in Fig. 4c, the average
volume seems to decrease from 10 to 15 wt% Z ­ n2+, which diameter and length of 10 wt% Z ­ n2+ doped ­V2O5 nanorods
may be due to the mismatch between ­Zn and ­V5+ radii.
2+
were measured as 0.85 and 1.8 μm, respectively, indicating
that a slight increment in nanorod dimensions and many of
3.2 SEM Analysis the nanorods showed a rippled surface. At higher concentra-
­ n2+ doped V
tion of Z ­ 2O5 (Fig. 4d) shows that the obtained
The introduction of Z ­ n2+ dopant in V­ 2+ lattice constructs single nanorods are relatively straight and uniform with
the microclusters entrench in a loose matrix. The photog- a diameter between 406 nm and length between 762 nm,
raphy of SEM images of synthesized samples annealed at respectively. The surfactant effect was observed with Zn ions
60 °C is shown in Fig. 2a–d. One can see that the studied to hinder the growth of vanadium species. Consequently,
samples appeared as microclusters with big particles and the overall growth rate in all dimensions was decreased
it’s an average diameter range of 2–5 μm. As exposed in with Zn doping. In Fig. 4b–d, the lattice d-spacing of Z ­ n2+
the figure, the representative overview of doped V ­ O2 archi- doped ­V2O5 nanorods calculated from the HRTEM images
tectures at certain magnifications, reveales that some micro is 0.518–0.548 nm and compared with the lattice parameter
rods with mixed particles and mostly irregular surface of of (200) plane of V ­ 2O5. The inset figure confirms the high
rods. Figure 2e–h shows the SEM photography of pure and
doped ­V2O5 samples annealed at 600 °C. The increasing

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­ n2+ doped ­VO2 samples annealed at 60 °C for 12 h and e–h pure and Z
Fig. 2  SEM images of a–d pure and Z ­ n2+ doped ­V2O5 samples annealed
at 600 °C for 1 h

degree of crystallinity of prepared nanoparticles via a wet ­V2O5 samples was confirmed by diffraction bright spots,
chemical method. The reduced crystallinity of Z­ n2+ doped which agree to the orthorhombic structure.

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Journal of Inorganic and Organometallic Polymers and Materials (2021) 31:1066–1078 1073

­ n2+ doped ­V2O5

Fig. 3  a–d EDS spectra of pure and Z

3.4 Optical Studies highest transparent and has an average reflectance of 50% in

the visible region obtained, as shown in Fig. 5b. Figure 5c,
Absorption spectroscopy is a powerful non-destructive the optical band gap was estimated from diffuse reflectance
technique used to explore the optical properties of semi- spectra by plotting the square of the Kubelka–Munk function
conducting nanoparticles. Absorption spectra show an F(R)2 given by the relation F(R) = (1 − R)2/2R [31], where
ultraviolet cut-off wavelength around 270–305 nm, which R is the magnitude of reflectance as a function of energy for
can be attributed to the photo-excitation of electrons from ­Zn2+ doped ­V2O5 samples and to obtain the optical gap the
the valence band to the conduction band. The absorption liner part of F(R)2 curve was extrapolated until it intersects
edge of different samples varies, as the concentration of Zn the energy axis at F(R)2 = 0. The optical band gap of the
in the ­V2O5 nanoparticles varies as shown in Fig. 5a. Fig- various compositions in ­Zn2+ doped ­V2O5 samples shows
ure 5b it is observed that with increasing Zn content, there that un-doped ­V2O5, the band gap comes out to be 2.527 eV
is a trend of decreasing reflectance in the visible region of and by the reported value [32]. The optical band gap values
the spectrum consistent with higher absorption by the Zn of ­Zn2+ doped ­V2O5 (Zn= 5, 10 and 15 wt%) samples are
ions due to the aforementioned transitions in tetrahedral 2.727, 2.852 and 2.913 eV, respectively, which are higher
symmetry. This decrement in reflectance may be due to the than the bulk ban gap value of V­ 2O5 (2.47). This increase in
increase in scattering centers and more grain boundaries the band gap may be due to the decrease in particle size with
formed after the Zn doping effect. The pure V ­ 2O5 is the an increase in Zn contents; the particle size lies within the

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1074 Journal of Inorganic and Organometallic Polymers and Materials (2021) 31:1066–1078

Fig. 4  TEM images of a ­V2O5 with SAED pattern and lattice fringes, and b–d ­Zn2+ doped ­V2O5 samples with SAED patterns and lattice fringes

range of (25–13 nm) a few nanometers. This increase was vacancies and interstitials of vanadium and oxygen atoms in
due to the Burnstein–Moss effect, which suggested that low the structure sources defects in the structure. These defects
energy transitions were blocked and the energy band gap also give rise to blue-green emission. Thus, the electrons
increased due to the Fermi level shifting close to the conduc- easily transferred from ionized oxygen vacancies to the val-
tion band caused by the increased carrier concentration. The ance band in the structure of the nanoparticles. The splitting
issue gets more striking with increasing Zinc concentration, of the band from Vanadium 3d to oxygen 2p valance band is
indicating an increase in the band gap of ­V2O5 caused by the confirmed with an emission peak at 550 nm [34]. Addition-
substitution of Z­ n2+ ions at V
­ 2+ site. This blue-shift may be ally, the observed peaks intensity decreases by increasing
attributed to strong quantum confinement effects. There is the substitution of Zn up to 5–10 wt%. So, the occurrence
no data available on the optical absorption of ­Zn2+ doped of nonradiative recombination in the structure may be the
­V2O5 nanoparticles for comparison. basis for the reduction in PL emission intensity [35]. Wang
et al., work also suggests the same kind of results observed
3.5 Photoluminescence Analysis in the nanoparticles [36]. However, the emission intensity
decreases by increasing the defects density, thus causes the
The Photoluminescence spectra of ­Zn2+ doped ­V2O5 nano- non-radiative recombination process [37].
particles were verified at room temperature and shown in
Fig. 6a. Three distinct emission peaks were detected in the 3.6 Fabrication of the Device
­V2O5 nanoparticles. The first two bands were observed in the
ultraviolet emission at 418 nm and blue emission at 440 nm. In our experiment, p-Si (100) substrate with an electrical
The third one is in broad visible emission at 549.2 nm. The resistivity of 0.008 Ω-cm was used as the growth substrate.
experimental spectrum of ­V2O5 nanoparticles is identified In the proclamation, the wafer was engrossed for 1–2 min
similar to earlier report work [33]. The wide band gap of into a buffered solution of HF (HF:H2O = 1:7) to eliminate
­V2O5 nanoparticles causes the near-band edge (NBE) exci- the native oxide layer on the surface of silicon [38]. Also, the
ton emission. Thus exciton recombination in grain bounda- substrate was ultrasonically cleaned with acetone, methanol
ries. Hence, a PL emission peak was observed at 418 nm and deionized water for 10 min. The methodically cleaned Si
because of interface traps in the nanoparticles. The self- substrate was used to fabricate the device by using a spray
trapped excitons recombination process raises the blue- technique. Herein, the precursor was prepared by dispersing
green emission peak at 453 nm due to charge transfer excited 100 mg of the synthesized nanopowders in 100 ml of 2-pro-
state of the nanoparticles. Correspondingly, the presence of panol and put in constant stirring for 24 h. The substrate was

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Journal of Inorganic and Organometallic Polymers and Materials (2021) 31:1066–1078 1075

Fig. 5  UV-Visible diffuse absorption spectra of a ­Zn2+ doped ­V2O5, b Reflectance spectra of Z
­ n2+ doped ­V2O5 and c band gap energy of ­Zn2+
doped ­V2O5 samples annealed at 600 °C for 1 h

placed on the sample holder of a spray setup. The aqueous particular applied voltage is below the current obtained with
solution was deposit via the nebulizer spray on a preheated the illumination of the diode. This is also perceived from the
Si (100) substrate at 150 °C. Additionally, the high purity of I-V characteristics. This behavior of the diode may be due to
Ag paste was used to make an ohmic contact in the prepared the photo-excitation of the charge carriers from the valance
device. band to the host state perturbed by defects. Additionally,
the electron–hole pairs were engendered in the depletion
3.7 Current–Voltage Characteristics of Ag/Zn2+ region because of high energy photons by the illumination
Doped ­V2O5/p‑Si/Ag Photodiodes of the diode. Thus, dark current in the diode leads the illu-
minated current leading to a high value of n, in reverse bias
Figure 7a–d depicts the current–voltage characteristic curve direction. As seen in Fig. 7e, the studied photodiodes exhib-
of the fabricated device by using synthesized nanoparticles. ited a rectifying behavior and decreased by increasing Zn-
The V–I characteristics of Z­ n2+ doped ­V2O5/p-Si photodi- dopant concentrations compared with undoped n-V2O5/p-Si
odes were measured under dark and illumination conditions diode under dark condition (Fig. 8a, b). The current changes
at room temperature. The Schottky junction photodiodes exponentially with applied voltage for 3kT/q < 0.5 V. Hence,
structure was obtained by nanoparticles on p-Si sandwiched the fabricated ­V2O5:Zn/p-Si photodiodes are evaluated as
between thin Ag layers. Typically, the reverse dark current at Schottky type diodes. Moreover, the considered diodes

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1076 Journal of Inorganic and Organometallic Polymers and Materials (2021) 31:1066–1078

current decreased. The calculated ideality factor values are

higher than unity in all fabricated diodes. This is due to the
formation of the interfacial thin native oxide layer at the Zn
and ­V2O5. The series resistance effect was also observed.
Henceforth, the surface states are high enough to alter the
barrier height in the device.

4 Conclusions

In summary, pure and Z ­ n2+ doped V ­ 2O5 nanoparticles with

various content of Zn, ranging from 5 to 15 wt%, were syn-
thesized through the wet chemical method. The tetragonal
and orthorhombic phases of synthesized nanoparticles were
by annealing at 60 °C calcinating at 600 °C, respectively.
Also, the preferential orientation direction with the (002)
Fig. 6  PL spectrum of a ­Zn2+ doped ­V2O5 (where x = 0, 5, 10, and plane was confirmed by structural analysis. SEM/TEM stud-
15%) samples
ies analysis revealed that the variation in size and shape of
the grains in the V­ 5+ lattice by Zn-doping concentration.
show a non-ideal behavior characteristic because of the The substitution of Zn-leads to reduce of PL intensity by
nanocrystalline nature of the ­V2O5 and the presence of an the increment of nonradiative recombination centers in
oxide layer. These surface states offer multiple current path- the surface. Further, pure and doped junction photodiodes
ways in the diode with additional energy states. The corre- were fabricated by using the nebulizer spray technique. The
sponding changes of ideality factor (n) with the Zn content electrical parameters of those photodiodes were calculated
in the structure are listed in Table 3. The high composi- with both dark and illumination environments. The photo-
tional fraction of zinc dopant in the nanostructure decreases electrical conductivity confirms the high photocurrent than
the electrical conductivity of the device and thus forward that of the dark current. Thus, it advocates the light sensitive

Fig. 7  I-V characteristics of a ­V2O5/p-Si, b–d ­Zn2+ doped ­V2O5/p-Si, e current density–voltage plots of Z
­ n2+ doped ­V2O5 and f F(V)–V plots for
pure and ­Zn2+ doped ­V2O5/p-Si diodes

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Journal of Inorganic and Organometallic Polymers and Materials (2021) 31:1066–1078 1077

Fig. 8  a A log–log plot of ­Zn2+ doped V ­ n2+ doped

­ 2O5/p-Si photodiodes diodes and b transient photocurrent measurements of pure and Z
­V2O5/p-Si photodiodes

Table 3  Optimized the diode parameters of pure and Z

­ nV2O5/p-Si samples
ZnV2O5/p-Si (Zn= 5, 10 Ideality factor (n) Barrier height Saturation current Rectification ratio Norde function
and 15 wt%) (ΦB) (eV) ­(Is) (μA) (RR) (±3 V)
ΦB Rs
(eV) (kΩ)

00 2.7945 0.3923 1.05 × 10−4 1.8209 × 10−10 0.4234 2.49E + 02

05 2.3942 0.3989 8.17 × 10−5 1.4715 × 10−10 0.4083 3.20E + 02
10 2.9073 0.4177 3.97 × 10−5 1.4692 × 10−10 0.4224 6.58E + 02
15 3.5142 0.4224 3.30 × 10−5 1.2971 × 10−10 0.4649 7.91E + 02

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