Citation
Mr. A. V. Patila,* ,Dr S. B.Patilb,
Dr. P. V. Dalalc,*
a,*SSVPS late. Dr.P.R.Ghogrey Science College Deopur, Dhule- 424 002,
Maharashtra, India
bS. S. M. M. Arts, Science and Commerce College, Pachora- 424 201,
Maharashtra, India
c*Nanomaterials Research Laboratory,
Department of Physics, Shri. V. S. Naik, A.C.S. College, Raver,425508, India
Abstract:
ZnSnO3
is a promising ternary oxide semiconductor owing to its favorable structural,
electrical, and optoelectronic properties. In this work, ZnSnO3 samples were
synthesized using a simple and cost-effective technique and characterized
through thermoelectric power (TEP), electrical, and photosensing studies.
Thermoelectric power measurements revealed a positive Seebeck coefficient,
indicating p-type conductivity and dominant hole transport. Electrical studies
showed temperature-dependent conductivity, confirming the semiconducting
behavior of ZnSnO3. Photosensing measurements under ultraviolet (UV)
illumination demonstrated a significant enhancement in photocurrent compared to
dark current, along with stable and repeatable photoresponse. The observed
photosensingbehavior is attributed to efficient generation of charge carriers
and surface-related trapping mechanisms under light illumination. The combined
results highlight the potential of ZnSnO₃ for applications in photodetectors
and optoelectronic devices.
1.Introduction
Researchers are very
interested in ternary oxide semiconductors because they can change their
physical properties and can be used in many different ways in optoelectronics,
sensing, and energy devices. Zinc stannate (ZnSnO3) has become a promising
material because of its unique electrical and structural properties. ZnSnO3
usually crystallises in a structure linked to perovskite that is orthorhombic.
By changing the conditions under which it is made, you can change its phase
purity, crystallinity, and microstructure. Such structural characteristics
significantly affect its electrical and optical properties[1].
X-ray diffraction (XRD) is a typical way to study the structural properties of
ZnSnO3. It shows that the phases are forming and the crystals are of good
quality. XRD examinations of ZnSnO₃ nanoparticles frequently demonstrate an
orthorhombic perovskite phase, signifying distinct lattice configurations that
enhance effective charge transport. [1]Additionally, synthesis parameters like
pH, precipitation conditions, and calcination temperature have a big effect on
the size of the crystallites and the strain in the lattice, which in turn
affects the optoelectronic performance[2].
ZnSnO3 has a broad band gap in
the near-UV region, which makes it great for detecting ultraviolet light and
for use in clear electronic devices. Studies using UV-visible spectroscopy have
found that the band gap values for ZnSnO3 nanoparticles are between 3.5 and 3.7
eV, which is compatible with how wide-bandgap semiconductors work. This broad
band gap lets UV light be absorbed well while keeping the visible spectrum
clear, which is critical for optoelectronic devices like UV photodetectors and
clear conductors[3].
The optoelectronic characteristics of ZnSnO3 are intricately associated with
its charge carrier dynamics and photodetection abilities. Photogenerated
carriers improve electrical conductivity when exposed to UV light. This effect
is used in photodetectors and photoresponsive sensors. Recent investigations
show that ZnSnO3-based structures have a strong photoresponse, which is similar
to other wide band gap oxide semiconductors. This shows that ZnSnO3 could be
useful for high-performance photosensingapplications[4].
ZnSnO3 is still being studied for use in sophisticated optoelectronic and
sensing technologies because it has a stable structure, a large optical band
gap, and reacts to light. Nonetheless, comprehending the interaction among
crystal structure, defect densities, and carrier transport is essential for
enhancing device performance[6-11].
2.Experimental details
2.1. Preparation of ZnO-SnO2nanocomposites
and pervoskite ZnSnO3 thin films
Nanocomposite andperovskite thin films have been
synthesized on glass substrates by employing spray pyrolysis technique. To
create nanocomposite thin films of ZnO-SnO2 and perovskite ZnSnO3
on a glass substrate that has been preheated, zinc chloride (ZnCl2
from Merck, extra pure) and tin (II) chloride pentahydrate (SnCl2.5H2O
from Merck, extra pure) were utilized. Table 1 shows the results of mixing zinc
chloride with tin (II) chloride pentahydrate in various ratios, including
25:75, 50:50, and 75:25 (1:3, 1:1, and 3:1).
Table 1: Varying
amount of reactants and spraying solutions
|
Thin film Sample |
ZnCl2 (cm3) |
SnCl2.5H2O (cm3) |
Volume Ratio |
Reactants |
|
S1 |
25 |
75 |
1:3 |
ZnO-SnO2 |
|
S2 |
50 |
50 |
1:1 |
ZnO-SnO2 |
|
S3 |
75 |
25 |
3:1 |
ZnSnO3 |
Based on the composition, the prepared films were
label as S1 and S2 (both nanocomposites ZnO-SnO2), and S3
(perovskite based ZnSnO3 thin films). Depending on the size of the
droplets, the chemical reaction, droplet landing, and solvent evaporation all
play a critical role in the creation of the film. We optimized the synthesis
parameters are listed in Table 2. The carrier gas pressure, to and fro nozzle
movement and substrate temperature were kept constant during the process.
Notably, the point during which the droplet approaches the glass substrate
sufficiently for the solvent to completely evaporate is the optimal condition
for film creation.The synthesized nanocomposites ZnO-SnO2 and
perovskite ZnSnO3 thin films samples were annealed at 500 0C
for 1 h in the presence of air to enhance its electrical, morphological,
microstructure properties and gas sensing capabilities.
3. Characterization
of thin films:
3.1Electrical properties:
A) TEP measurement
Figure 1: Temperature dependence of
thermoelectric power measurement.
An Arrhenius plot of ZnO-SnO2
and ZnSnO3 thin films is shown in Fig. 2. Figure 3.5 shows temperature curves
and thermoelectric power for thin films of ZnO-SnO2 and ZnSnO3 with different
compositions (different amounts of Zn and Sn). Figure 2 clearly shows that the
thermoelectric power of all samples goes up as the temperature goes up. TEP is
negative for all samples in the temperature range of 320–424 K, indicating
n-type conductivity [15,16]. All of the samples act like semiconductors.
The difference in temperature in the thermoemf measurement makes a carrier
migrate from the hot end to the cold end. This generates an electric field that
calculates the thermal voltage. The difference in temperature across the
semiconductor is exactly equal to this voltage that is created by heat. The
thermoemf was positive at the hot end compared to the cold end, which showed
that ZnO-SnO2 and ZnSnO3 films are n-type conductors.
B) Electrical conductivity
The electrical conductivity of the
nanocrystalline thin films was measured using the DC two-probe method in the
temperature range of 298–423 K. The conductivity (σ) was evaluated using the
Arrhenius-type relation (1):
where σ0 is the pre-exponential factor, ΔE is the activation
energy, k is the Boltzmann constant, and T is the absolute temperature.
Figure2.Variation
of log (σ) with inverse of operating temperature (K)
Figure 3 shows the variation of log(σ) with the inverse of temperature
(1000/T). As the temperature increases, the conductivity of all samples
increases, which is a characteristic feature of semiconducting materials with a
negative temperature coefficient (NTC) of resistance. This confirms that the
nanocrystalline thin films exhibit semiconducting behaviour [13].
The conductivity studies reveal two distinct activation energy regions,
corresponding to low- and high-temperature ranges at 323-373 K and 373-423 K
respectively. The activation energy values, extracted from the slopes of the
ln(σ) versus 1/T plots, are summarized in Table 2. The presence of two
activation energies indicates two donor levels - one deep and one shallow -
located near the conduction band edge. At higher temperatures (423 K), the
activation energy decreases slightly, which can be attributed to oxygen
adsorption at the film surface. The adsorbed oxygen atoms capture free
electrons from the conduction band and form weak bonds with zinc atoms, thereby
affecting the conduction process through surface states.
|
Sample |
Thickness (nm) |
Activation
energy (∆E) |
|
|
323 K (Low temperature) |
423 K (High temperature) |
||
|
S1 |
810 |
0.23 eV |
0.19 eV |
|
S2 |
843 |
0.17 eV |
0.14 eV |
|
S3 |
839 |
0.19 eV |
0.17 eV |
Table 2:Measurement of thickness with activation
energy
It is evident from Table 2 that the activation energy decreases with
increasing film thickness (S1 to S2). This behavior is likely due to improved
crystallinity and grain growth with thickness, which reduces grain boundary
scattering and enhances carrier mobility. However, for sample S3, although the
thickness decreases slightly compared to S2, the activation energy increases.
This anomalous behavior may be associated with structural modifications,
possibly the formation of a perovskite-like phase, which alters the electronic
structure and increases the barrier for conduction [14].Thus, the combined
analysis of conductivity behavior and activation energy trends highlights the
role of microstructural features and surface states in governing the charge
transport mechanism in the nanocrystalline thin films.
3.3.Photosensing of ZnO-SnO2 and ZnSnO3 sample:
Figure3.Dark current (pA) vs DC
voltage (V) for three samples (S1, S2, S3).
Figure
demonstrates how the dark current changes when different DC voltages are
applied to samples S1, S2, and S3. For all samples, the dark current goes up
steadily as the voltage goes up. This shows that the electrical conduction is
stable and the electrode contact is good. S3 has the most dark current of the
three samples, whereas S1 has the least current across the whole measured
voltage range. The behaviour shown can be explained by differences in the
concentration of charge carriers and the density of defects in the samples. The
low dark current seen in sample S1 is very useful for photosensing applications
because it improves the signal-to-noise ratio when there is light[16].
Figure5.Illumination current (pA) Vs DC
voltage (V) for three samples (S1, S2, S3).
When light is shown on them,
all of the samples show a clear increase in current when the DC voltage goes
up, which shows that they are photosensitive. Sample S3 exhibits the largest
photocurrent, which is ascribed to an increased density of photogenerated
carriers and diminished grain boundary barriers. In contrast, sample S1 has a
relatively lower photocurrent but higher stability[17]. The clear difference
between the dark and lighted current shows that the samples being studied are
good at detecting light.
Conclusion:
The research shows that thin
films of ZnO-SnO2 and ZnSnO3 made by spray pyrolysis have good structural and
morphological properties. The size of the crystals gets smaller as the Zn-to-Sn
ratio changes. Dark and lit I–V measurements validate robust photosensing
characteristics in all samples. Sample S3 has the largest photocurrent and
photosensitivity because it makes more photocarriers, while S1 has a low dark
current that is good for low-noise detection.
Acknowledgement:
The authors thank Shri. V.S.
Naik, the Principal of the Art, Commerce, and Science College in Raver, for
giving them access to the lab for this work.
References:
1.
J Sol-Gel SciTechnol 112,
703–714 (2024). https://doi.org/10.1007/s10971-024-06550-2
2. https://doi.org/10.3390/engproc2025087004
3. https://doi.org/10.1016/j.jallcom.2024.174854
4. I. M. El Radaf Promising novel transparent conductive
F-doped ZnSnO3 thin films for optoelectronic
applications, J. Mater. Sci.: Mater. Electron., 2023,
5. https://doi.org/10.1039/D3RA05481K
6.
N. Lu, A selective methane gas sensor with printed
catalytic films as active filters Sens. Actuat. B Chem (2021)
7.
T. Hübert,
Hydrogen sensors – A review Sens Actuators B Chem, (2011)
8.
L.N. Acquaroli et al. Innovative design for optical
porous silicon gas sensor Sens Actuators B Chem (2010)
9.
Y. Triana, Application of boron doped diamond
electrodes to electrochemical gas sensor CurrOpinElectrochem,(2022)
10. SagarikaPanda,SavitaMehlawat,NeerajDhariwal,Ashwani
Kumar, Amit Sanger,Materials Science and Engineering: B Volume 308, (2024),
117616
11. Chenghong
Wei, ZiyiGuo, Heng Wang,
Shiqi Zhang, DandanHao and
Jia Huang, Recent progress of gas sensors based on perovskites, Material
Horizons,2(2025)
12. U.R.
Shwetha, M.S. Latha, C.R. Rajith Kumar, M.S. Kiran, V.S. Betageri, Facile
synthesis of zinc oxide nanoparticles using novel Areca catechu leaves extract
and their in vitro antidiabetic and anticancer studies, J. Inorg. Organomet.
Polym. Mater. 30 (12) (2020) 4876–4883.
13. U.R.
Shwetha, M.S. Latha, C.R. Rajith Kumar, M.S. Kiran, V.S. Betageri, Facile
synthesis of zinc oxide nanoparticles using novel Areca catechu leaves extract
and their in vitro antidiabetic and anticancer studies, J. Inorg. Organomet.
Polym. Mater. 30 (12) (2020) 4876–4883.
14. S.
Deepa, K. PrasannaKumari, B. Thomas, Contribution of oxygen-vacancy
defect-types in enhanced CO2 sensing of nanoparticulate Zn-doped SnO2 flms.
Ceram. Int. 43, 17128–17141 (2017). https://doi.org/10.1016/j.ceramint.
2017.09.134
15. J.
Wang, Z. Chen, Y. Liu, C.-H. Shek, C.M.L. Wu et al., Heterojunctions and
optical properties of ZnO/SnO2 nanocomposites adorned with quantum dots. Sol.
Energy Mater. Sol.Cells 128, 254–259 (2014).
https://doi.org/10.1016/j.solmat.2014.05.038
16. Author(s). (2024). High-performance
solar-blind photodetectors based on Ta-doped ZnSnO3 single crystal thin films,
Journal of Alloys and Compounds, 997, 174854.
https://doi.org/10.1016/j.jallcom.2024.174854 C. Hu,
L. Chen, Y. Hu, A. Chen, L. Chen et al., Light-motivated SnO2/TiO2
heterojunctions enabling the breakthrough in energy density for lithium-ion
batteries. Adv. Mater. 33, e2103558 (2021).
https://doi.org/10.1002/adma.202103558
17. Author(s). (2022). BifunctionalZnO
nanowire/ZnSnO₃ heterojunction thin films for photoelectrochemical water
splitting and photodetector applications, Materials Letters, 322,
132450. https://doi.org/10.1016/j.matlet.2022.132450


