Abstract
Keywords
Introduction
The development of effective and sensitive gas sensors has been a continuous endeavor by the scientific community. Regulation and precise detection of hazardous gases, including H2, NO2, SO2, CO, H2S, etc., are the major current challenges in front of the research community under the environmental protection policy. Many studies are being conducted to create particular gas sensors with effective response characteristics. However, limited work has been reported on the detection of SO2, which contributes to acid rain and whose repeated exposure can cause permanent pulmonary impairment. Therefore, there is an utmost requirement for developing an efficient sensor for SO2 gas. Amongst diverse gas sensors, gas sensors based on the conductometric principle with semiconducting metal oxides as sensing layers are most preferred for efficient and easy detection of several gases like H2, NO2, NH3, H2S, CO2, etc.
The most extensively used semiconducting metal oxides investigated as effective gas sensing materials are WO3, ZnO, TiO2, SnO2, In2O, NiO, and others because of their high sensitivity, cheap fabricating costs, the potential for miniaturization, and simplicity of related electronics.1,2 The most researched among these are tin oxide (SnO2) thin films and nanostructure-based gas sensors due to their quick reaction times, excellent chemical stability, and capacity to detect all types of gases (oxidizing as well as reducing) with great sensitivity, without being poisonous, and low cost.3–6 However, there hasn’t been much work done in the advancement of SO2 gas sensors using conductometric techniques. Shimizu et al. observed a maximum sensing response of the sensor of ~25 for SO2 gas (800 ppm) using an Ag-doped WO3 semiconductor gas sensor with a temperature operating at 400 °C. 7 Han et al. reported the detection of H2S via photoactivation and photothermal activation of MXene/PbS sensor. 8 Few reports are also available on SO2 gas detection using electrochemical techniques. Liang et al. combined NASICON with V2O5 doped TiO2 electrode and observed a sensitivity of ~170 EMF/mV towards 50 ppm of SO2. 9 Li et al. and Bukun et al. exploited an electrochemical technique for SO2 detection and recorded sensor response of 5.4 × 10−11 A/ppm at room temperature and 0.2 units for 200 °C as an operating temperature, respectively.10,11 Ni-doped MoS2 nanocomposite sensors synthesized via a hydrothermal method demonstrated enhanced SO2 detection at room temperature, supported by DFT-based insights into adsorption behavior. 12 Previous studies on SO2 gas sensors based on the conductometric detection principle using metal oxide semiconductors reveal either a poor detecting response or a high working temperature (⩾400 °C).7–11 Therefore, efforts are still being made to create an effective SO2 gas sensor throughout the world. The first condition is by fabricating an adequate sensing layer having the desired morphological characteristics or by incorporating a catalyst or going for a second condition, which is using dopants into the sensing layer to obtain enhanced sensing response. Furthermore, it is reported in the literature for other toxic gases that incorporating a semiconducting dopant into the sensing layer and making either p-n or n-n heterojunction modulates the depletion region after interaction with the target gas, which results in an enhanced sensing response.3,4 In this regard, NiO is a desirable (p-type) material well recognized for its chemical stability, along with its outstanding optical and electrical characteristics, and as an excellent gas sensing material. The interaction of SO2 gas with different nano-clustered catalyst/SnO2 thin film sensors was studied, and NiO was discovered to be the best catalyst when loaded over SnO2 in a dotted nanocluster form. for detection of SO2 gas. 13
Recent advancements in gas sensing technology have increasingly focused on heterostructure-based materials due to their superior sensing performance compared to single-component sensors. Alam et al. comprehensively reviewed the development of chemoresistive-based heterostructure gas sensor technology, highlighting their enhanced sensitivity, selectivity, and stability while identifying future opportunities and challenges in this rapidly evolving field. 14 The fundamental principles and applications of mixed-dimensional van der Waals heterostructures in gas sensing have been extensively explored by Goel et al., who demonstrated how these unique structures enable improved charge transfer mechanisms and enhanced sensing capabilities through engineered interfaces. 15 Complementing these findings, Liu et al. investigated 1D/2D heterostructures, emphasizing their synthesis methodologies and applications in both photodetectors and sensors, showcasing the versatility of dimensionally engineered materials. 16 Nosovitskiy et al. provided insights into the latest advances in semiconductor gas sensing materials and structures, particularly focusing on breath analysis applications and the development of sophisticated algorithms for enhanced detection capabilities. 17 Furthermore, Ma et al. reviewed recent progress in graphene-based humidity sensors with particular emphasis on structural design considerations, demonstrating the critical role of material architecture in sensor performance. 18 The practical implementation of these advanced sensing technologies has been demonstrated by Nguyen and Lee, who developed chemical sensor devices specifically for monitoring hazardous gases in semiconductor manufacturing processes, bridging the gap between fundamental research and industrial applications. 19 These collective studies underscore the importance of heterostructure engineering and dimensional control in developing next-generation gas sensors with enhanced performance characteristics.
However, the work presented earlier was limited to a specific thickness (10 nm) of NiO catalyst only. According to research in the literature, the catalyst layer’s thickness has a significant influence on the gas-detecting capabilities of the sensor. As a result, optimizing the catalyst thickness of layers is crucial for producing an improved sensing response to a certain target gas. Therefore, for the current study, the variation in gas sensing response has been investigated for the diverse catalyst NiO thickness scattered over the SnO2 sensing layer in dotted nanoclusters in shape. Different sensing mechanisms have been explored for the sensing response changes with catalyst thickness variation for NiO/SnO2 sensors.
Experimental
Thin films of SnO2 have been deposited with a metal tin target (99.99% purity) within a controlled ambiance of argon and oxygen gas by the RF sputtering technique. All the parameters used for SnO2 deposition have been tabulated in Table 1.
SnO2 and NiO film deposition parameters for the sensor.
SnO2 thin film deposition was done on the Pt/Ti inter-digital electrodes pattern silicon substrate (description of the fabrication of Pt/Ti is mentioned elsewhere 13 ) for sensing applications and silicon substrate for other characterizations. RF sputtering technique is used for the incorporation of NiO catalysts with varying thicknesses (6–14 nm) have been incorporated over the thin film surface of SnO2 using the shadow masking technique, having a pore size of 50 microns shadow mask. The deposition characteristics are compiled in Table 1, where the SnO2 thin film layer was maintained at 90 nm in thickness. SnO2 thin film thickness and deposition parameters for obtaining enhanced sensing response have been taken from the previous report. 13 Deposition parameters were obtained in depositing NiO catalyst using the RF sputtering technique. NiO/SnO2 samples have been coded as N1 (6 nm), N2 (8 nm), N3 (10 nm), N4 (12 nm), N5 (14 nm) for varying thickness of NiO catalyst above the SnO2 thin film surface. For comparison, under the ideal conditions, a bare SnO2 thin film sensor has also been created; the bare sample is coded as N0.
Veeco Dektak 150 surface profiler measures the gas sensor thickness of deposited thin films. The MIRAJ TESCAN scanning electron microscope was used to examine the crystallinity of SnO2 thin films. The optical characteristics of the sensors were investigated by a UV-visible spectrometer (Perkin Elmer, Lambda 35). SO2 gas sensing properties of the prepared sensors were tested in-house developed GSTC “Gas Sensing Test Chamber.” A flowchart detailing the material preparation and sensor fabrication steps provides a clearer and more intuitive representation of the process and is shown in Figure 1.

Flowchart representing the fabrication process.
Results and discussions
Structural analysis
The XRD patterns of NiO and SnO2 targets are shown in Figure 2. The diffraction peaks for NiO correspond to the (111), (200), (220), (311), and (222) planes, consistent with the cubic phase of NiO (JCPDS No. 47-1049). 20 For SnO2 sharp and well-defined peaks are observed at (110), (101), (200), (211), (220), (002), (310), (112), (301), (202), and (321) planes, which are indexed to the tetragonal rutile structure of SnO2 (JCPDS No. 41-1445). 21 The absence of impurity peaks indicates high purity.

XRD profiles of NiO and SnO2 target.
Microstructural analysis
The microstructural properties of the prepared thin films were depicted using SEM micrographs as shown in Figure 3. Figure 3(a) illustrates the formation of a porous nanostructure with minute cracks on the surface of the pristine SnO2 thin film. SEM images of annealed SnO2 thin films with NiO catalyst integration are displayed in Figure 3(b). The microstructure of SnO2 thin film integrated with NiO catalyst exhibits uniformity and homogenous distribution of grains. The targeted gases may reach a considerable surface area of the SnO2 thin film through these cracks, which helps achieve a good sensing response.

(a) SEM image of annealed SnO2 thin film, (b) annealed SnO2 thin film integrated with NiO catalyst.
Gas sensing analysis
Studies of the sensing response of bare-SnO2 (N0) and all heterostructures gas sensors (N1, N2, N3, N4, N5) were carried out by varying the temperature from 100 °C to 300 °C, and the obtained change in sensor response concerning 100 ppm SO2 gas is shown in Figure 4.

Temperature-dependent changes in the sensing response of NiO/SnO2 heterostructure sensors with different NiO cluster thicknesses when SO2 gas is exposed at 100 ppm.
Every sensor exhibits the typical sensing response, which rises with substrate temperature, achieves its highest value at the operating temperature (
Illustrates parametric optimization for the current gas sensor.
It can be seen that as NiO modifier thickness increases to 10 nm (N3 sample), the sensing response also increases to ~54. But on further increasing the thickness of NiO clusters (>10 nm) the sensing response decreases continuously. This might be explained by considering that the 10 nm thin NiO clusters (N3) sample exhibits the optimal roughness that leads to enhanced desorption and adsorption of target SO2 gas on sensing layer. It is reported that if the surface roughness is very low or very high the sensing response is poor. 22 With further increasing thickness of the catalyst thickness (>10 nm) for N4 and N5 samples, the surface roughness is seen to be increasing but the quick desorption of gas may be responsible for decreasing the sensing response for these sensors. However, no change in the operating temperature (180 °C) is observed for all NiO/SnO2 sensors.
In Figure 5, the resistance changes of the sensor N3, as a function of ambient air temperature (

Resistance (
Figure 6(a) and (b) show the side view of the resulting NiO and SnO2 hetero-junction that shows the depletion region, as well as the diagrammatic representation of the heterojunction formed at the meeting point of p-type NiO clusters and n-type SnO2 thin film. As a result of the formation of a depletion region at the interface across n-type SnO2 and p-type NiO, the concentration of electrons in the conduction band of the SnO2 thin film drastically decreases and the sensor resistance (

Schematic diagram of the prepared NiO/SnO2 heterojunction showing space charge region and effective channel thickness in SnO2 thin film (a) before and (b) after exposure to SO2 gas.
When the sensors were exposed to 100 ppm of SO2 gas, all NiO/SnO2 heterostructure sensors showed variations in sensor resistance (
On the surface of the exposed SnO2, at
Due to the interaction that exists between the surface layer of the exposed SnO2 sensor and the emitted molecules of SO2 gas, more stored electrons are released to participate in SnO2 layer conduction, lowering the
This results in an increase in the optimum thickness of the conducting channel and a decrease in the region of depletion in the SnO2 layer (at the NiO/SnO2 junction). Resistivity of the sensor decreased significantly from
During the time of recovery, the SO2 gas vents off from the gas sensing chamber, and fresh air is inserted. When fresh dry air interacts with the sensor surface, NiS gets converted back into NiO as given in equation (3) 28 :
Also, the oxygen gas molecules get absorbed from the atmosphere onto the SnO2 surface and become O− species depending on the ambient temperature (
Figure 7(a) and (b) display the response and recovery time at different operating temperatures of all developed gas sensors (N0, N1, N2, N3, N4, N5) towards SO2 gas (100 ppm). After adding the NiO modifier to the SnO2 thin film surface layer, an increase in the values of response and recovery time was seen (Figures 6(b) and 7(a)). 15 Due to the conversion of NiO into NiS upon contact with SO2 gas, the Fermi energy control mechanism predominates for NiO/SnO2 sensors. This is a protracted process, and hence, the response time for all NiO/SnO2 sensors is higher than for bare SnO2 sensors. As with the bare-SnO2 sensor, recovery time is likewise poor. All sensor structures’ response and recovery periods decrease as temperature increases because gas molecules adsorb and desorb more quickly at higher temperatures. The response and recovery time obtained for the other NiO/SnO2 gas sensor designs are determined to be much shorter than the response and recovery time obtained for sensor N3, which is found to give response and recovery times of 75 and 60 s. This might be a result of the high surface roughness produced by the sensor N3, which causes more gas molecules to be trapped on the rough surface and lengthens the reaction time.

(a) Variation in sensor response time. (b) Recovery time of all the fabricated sensors (N0, N1, N2, N3, N4, and N5).
Figure 8 demonstrates the gas sensor N3 structure’s transient response to temperature. It is observed that when exposed to SO2 gas at 100 ppm, the resistance values of the sensor fluctuate most when the operating temperature (

Transient response structure of (10 nm) NiO/SnO2 sensor obtained at various temperatures towards SO2 gas at 100 ppm.
In Figure 9, the selectivity transient of the N3 sensor structure towards other toxic and harmful gases like LPG, methane, acetone, and CO2 at 1000 ppm gas concentration, along with the SO2 at 100 ppm. Operating temperature of 180 °C, which has been optimized for the sensor, N3 displays the best sensing response towards 100 ppm SO2 gas and exhibits poor response towards other interfering gases (Figure 9). Equation (4) has been used to estimate the selectivity parameter (β) of the N3 sensor for other interfering gases:

Selectivity study of (10 nm) NiO/SnO2 sensor (N3) with various gasses that interfere at 1000 ppm at an operating temperature of 180 °C.
The sensing reaction to SO2 gas (100 ppm) is known as

Variation of the (10 nm) NiO/SnO2 sensor structure’s selectivity parameter for various interfering gases.
Comparison table for lower operating temperature, higher response, and competitive response/recovery times.
Conclusion
The sensing response properties of the NiO/SnO2 thin film-heterostructure sensor of all the developed structures have been investigated for detecting the SO2 gas (100 ppm). The optimal thickness of NiO nanoclusters in the NiO/SnO2 heterostructure sensor has been established to be 10 nm to obtain the increased sensing response (54) with a shorter reaction time (75 s) and rapid recovery time (60 s) at a lower operating temperature (180 °C). It is discovered that during the contact of SO2 gas with the NiO/SnO2 heterojunction structure (10 nm modifier), the maximum modulation of the space charge region took place at the interface of p-type modifiers with n-type SnO2 thin film. This alteration in the space charge area drastically changed the sensor resistance (from
