Next Article in Journal
Immobilization of Dextranase Obtained from the Marine Cellulosimicrobium sp. Y1 on Nanoparticles: Nano-TiO2 Improving Hydrolysate Properties and Enhancing Reuse
Next Article in Special Issue
Recent Progress in Spinel Ferrite (MFe2O4) Chemiresistive Based Gas Sensors
Previous Article in Journal
Emerging Trends in Nanotechnology: Aerogel-Based Materials for Biomedical Applications
Previous Article in Special Issue
Pd/Pt-Bimetallic-Nanoparticle-Doped In2O3 Hollow Microspheres for Rapid and Sensitive H2S Sensing at Low Temperature
 
 
Font Type:
Arial Georgia Verdana
Font Size:
Aa Aa Aa
Line Spacing:
Column Width:
Background:
Article

Investigation of High-Sensitivity NO2 Gas Sensors with Ga2O3 Nanorod Sensing Membrane Grown by Hydrothermal Synthesis Method

1
Department of Photonics, National Cheng Kung University, Tainan 701, Taiwan, Republic of China
2
Department of Electrical and Electronic Engineering, Chung Cheng Institute of Technology, National Defense University, Taoyuan 335, Taiwan, Republic of China
3
Department of Electrical Engineering, Yuan Ze University, Taoyuan 320, Taiwan, Republic of China
*
Author to whom correspondence should be addressed.
Nanomaterials 2023, 13(6), 1064; https://doi.org/10.3390/nano13061064
Submission received: 27 February 2023 / Revised: 13 March 2023 / Accepted: 13 March 2023 / Published: 15 March 2023
(This article belongs to the Special Issue Advanced Gas Sensors Developed by Nanocomposites)

Abstract

:
In this work, Ga2O3 nanorods were converted from GaOOH nanorods grown using the hydrothermal synthesis method as the sensing membranes of NO2 gas sensors. Since a sensing membrane with a high surface-to-volume ratio is a very important issue for gas sensors, the thickness of the seed layer and the concentrations of the hydrothermal precursor gallium nitrate nonahydrate (Ga(NO3)3·9H2O) and hexamethylenetetramine (HMT) were optimized to achieve a high surface-to-volume ratio in the GaOOH nanorods. The results showed that the largest surface-to-volume ratio of the GaOOH nanorods could be obtained using the 50-nm-thick SnO2 seed layer and the Ga(NO3)3·9H2O/HMT concentration of 12 mM/10 mM. In addition, the GaOOH nanorods were converted to Ga2O3 nanorods by thermal annealing in a pure N2 ambient atmosphere for 2 h at various temperatures of 300 °C, 400 °C, and 500 °C, respectively. Compared with the Ga2O3 nanorod sensing membranes annealed at 300 °C and 500 °C, the NO2 gas sensors using the 400 °C-annealed Ga2O3 nanorod sensing membrane exhibited optimal responsivity of 1184.6%, a response time of 63.6 s, and a recovery time of 135.7 s at a NO2 concentration of 10 ppm. The low NO2 concentration of 100 ppb could be detected by the Ga2O3 nanorod-structured NO2 gas sensors and the achieved responsivity was 34.2%.

1. Introduction

In recent years, due to the rapid development of industries in human society, environmental pollution has become increasingly serious, such as noise, air pollution, water pollution, and nuclear pollution, etc. Among them, the air pollution of nitrogen dioxide (NO2), causing harm to human health and the environment, is the most serious issue. Even a NO2 concentration of 3 ppm is enough to cause serious damage and human health problems, including throat irritation, respiratory illnesses, and even death [1,2]. Therefore, to avoid the harm caused by NO2 gas, it is very important to develop a gas sensor with high responsivity and high selectivity to detect NO2 gas.
Among several structures of gas sensors, a metal oxide semiconductor (MOS) gas sensor is the most attractive structure due to its inherent advantages of easy fabrication, simple operation, low prices, and a small size [3]. Many metal oxide semiconductor materials have played promising roles in resistive types of MOS-structured gas sensors, such as zinc oxide (ZnO) [4,5], stannic oxide (SnO2) [6,7], titanium dioxide (TiO2) [8,9], indium oxide (In2O3) [10,11], and gallium oxide (Ga2O3) [12,13]. Among the metal oxide semiconductor materials, in view of the advantages of non-toxicity, low prices, and good chemical stability [14,15], Ga2O3 has potential applications in high-temperature gas sensors [16,17]. Moreover, nanostructures have been designed to enhance the performance of gas sensors because of their high surface-to-volume ratio, high specific surface area, and more surface adsorption sites, recently [18,19,20,21]. In this work, the GaOOH nanorods were grown on the SnO2 seed layer by the hydrothermal synthesis method. The resulting GaOOH nanorods were then annealed to convert them into Ga2O3 nanorods. The surface morphology of the Ga2O3 nanorods was optimized for a high specific surface area, thereby achieving high responsivity and high selectivity in the NO2 gas sensors.

2. Materials and Methods

2.1. Materials

In this work, the SnO2 target (99.99%) with bonding on a 3 mm Cu plate was purchased from S.P. Alloys Co., Ltd., Keelung, Taiwan. Granules of gallium nitrate nonahydrate (Ga(NO3)3·9H2O, 99.9%) and hexamethylenetetramine (C6H12N4, HMT, 99.5%) were, respectively, purchased from Alfa Aesar (Heysham, UK)and Sigma-Aldrich (Darmstadt, Germany). A target-gas NO2 gas cylinder (1000 ppm) was purchased from Yun Shan Gas Co., Ltd., Tainan, Taiwan.

2.2. Material Characterization

X-ray diffraction (XRD, D8 DISCOVER with GADDS, Bruker AXS Gmbh, Karlsruhe, Germany) was used to characterize the seed layers of Ga2O3 nanorods. The morphological and structural analyses of the resulting Ga2O3 nanorods were performed with a field emission scanning electron microscope (FE-SEM, AURIGA, ZEISS, Oberkochen, Germany). The material characteristics of the annealing-treated GaOOH nanorods were measured using X-ray photoelectron spectroscopy (XPS, PHI 5000 VersaProbe III, ULVAC-PHI. Inc., Osaka, Japan). The current–voltage (I-V) characteristics were obtained with an Agilent 4156C (Santa Clara, CA, USA) semiconductor parameter analyzer.

2.3. Experimental Details

Figure 1 shows the schematic configuration of the Ga2O3 nanorod-structured NO2 gas sensors. A radio frequency (RF) magnetron sputtering system was used to deposit SnO2 films with various thicknesses of 50 nm, 100 nm, and 200 nm on quartz substrates as seed layers for GaOOH nanorods. The RF power, the Ar/O2 gas ratio, and the chamber pressure were maintained at 75 W, 48/2 sccm, and 5 mtorr, respectively. The growth rate of the SnO2 films was approximately 6.8 nm/min. After completing the various SnO2 seed layers, the GaOOH nanorods were grown on quartz substrates using the hydrothermal synthesis method with various concentration solutions consisting of Ga(NO3)3·9H2O and HMT at 180 °C for 4 h using a magnetic stirrer hotplate. The nanorods were then converted from GaOOH to Ga2O3 in a pure N2 ambient atmosphere using a furnace system for 2 h at 300 °C, 400 °C, and 500 °C, respectively. The hydrothermal synthesis processes and the material conversion during the thermal annealing processes are described in Equations (1–4), respectively [22].
C6H12N4 + 6H2O → 6HCNO + 4NH3
NH3 + H2O → NH4+ + OH
Ga3+ + 3OH → GaOOH + H2O
2GaOOH → Ga2O3 + H2O
The Ni/Au (20/100 nm) metals were deposited on the Ga2O3 nanorods as the electrodes of the gas sensors by an electron-beam evaporator.
Figure 2 shows the schematic configuration of the measurement system of the NO2 gas sensors. A target-gas NO2 gas cylinder and a mass flow controller (MFC) were installed with a closed chamber to provide a stable NO2 gas source, and an Agilent 4156C semiconductor parameter analyzer was equipped to measure the current–voltage (I-V) characteristics of the Ga2O3 nanorod-structured NO2 gas sensors. In addition, the closed chamber of the NO2 gas sensor measurements was equipped with a humidity controller to maintain a relative humidity of 30% during the testing process. When NO2 gas was introduced into the chamber, the NO2 molecules would react with the Ga2O3 sensing membrane, causing an increase in the resistance of the sensor. This reaction occurred as a result of the NO2 molecules extracting electrons from the Ga2O3 nanorod sensing membrane, which reacted with the O2(abs) in the sensing membrane. These reaction processes were as follows in Equations (5)–(8) [23].
O2(gas) → O2(abs)
O2(abs) + e → O2(abs)
NO2(gas) + e → NO2(abs)
NO2(gas) + O2(abs) + 2e→ NO2(abs) + 2O2(abs)
When the NO2 gas was removed from the chamber and purged by air, the electrons previously trapped by NO2 molecules were released back to the conductive band of the material, leading to a decrease in sensor resistance and a return to its initial state.

3. Results

Since the diameter of the resulting nanorods was dependent on the average grain size of the seed layer, which was increased with an increase in the film thickness [24,25,26], an amorphous seed layer with a small grain size has become a very important research target to obtain nanorods with a larger surface-to-volume ratio. In this work, to achieve a high surface-to-volume ratio, high specific surface area, and more surface adsorption sites, the surface morphology was optimized by changing the thickness of the SnO2 seed layer and the mixed solution concentration of the hydrothermal precursors.
Using the measurement of X-ray diffraction (XRD) with CuKα radiation, Figure 3 illustrates the crystalline characteristics of the SnO2 seed layers with various thicknesses of 50 nm, 100 nm, and 200 nm. As shown in Figure 3, the 50-nm-thick SnO2 film did not have any obvious peak in the XRD pattern. Furthermore, for the 100-nm-thick and 200-nm-thick SnO2 films, three diffraction peaks located at 26.5°, 34.0°, and 51.9°, corresponding to the SnO2 (110), (101), and (211) planes, respectively, were found [27]. It could be observed that the crystallinity of the SnO2 film was improved with an increase in the SnO2 thickness. Consequently, to enable the growth of GaOOH nanorods with a high surface-to-volume ratio morphology, the amorphous structure of a 50-nm-thick SnO2 film was required for the seed layer in this study.
Figure 4a–c illustrate the FE-SEM top-view and cross-section images of the GaOOH nanorods respectively synthesized on the various SnO2 seed layers by the hydrothermal synthesis method with Ga(NO3)3·9H2O and HMT concentrations of 12 mM and 10 mM. It was seen that the shape of the nanorods was approximately a rhombus and the dimension of the nanorods showed a uniform distribution. However, the size and number of the nanorods were obviously influenced by the thickness of the SnO2 seed layers. For the GaOOH nanorods grown on the SnO2 seed layers with various thicknesses of 50 nm, 100 nm, and 200 nm, the average short-side diagonal was approximately 52.0 nm, 60.2 nm, and 72.6 nm, respectively. The average short-side diagonal of the GaOOH nanorods was increased with an increase in the thickness of the SnO2 seed layers. The height of the resulting nanorods was almost kept at around 320 nm, with no significant difference. Consequently, it could be deduced that the morphology of the GaOOH nanorods was greatly influenced by the thickness of the seed layer. A larger surface-to-volume ratio of GaOOH nanorods was obtained in the thinner SnO2 seed layer due to the smaller grain size of the thinner seed layer.
In the hydrothermal synthesis processes, to obtain an optimized morphology of GaOOH nanorods by changing the concentration of Ga(NO3)3·9H2O and HMT precursors, the various Ga(NO3)3·9H2O/HMT precursor concentrations of 6 mM/5 mM, 12 mM/10 mM, and 18 mM/15 mM were utilized and investigated. The FE-SEM top-view and cross-section images of the various GaOOH nanorods grown on the 50-nm-thick SnO2 seed layer are shown in Figure 5a–c. The average short-side diagonal of the GaOOH nanorods grown using various Ga(NO3)3·9H2O/HMT precursor concentrations of 6 mM/5 mM, 12 mM/10 mM, and 18 mM/15 mM was 51.5 nm, 52.0 nm, and 70.7 nm, respectively. The corresponding height of the GaOOH nanorods was approximately 195 nm, 320 nm, and 352 nm, respectively. It was found that the average short-side diagonal of the GaOOH nanorods gradually increased with an increase in the concentration of the Ga(NO3)3·9H2O/HMT precursor. Although the smallest average short-side diagonal was obtained in the GaOOH nanorods grown using the precursor concentration of 6 mM/5 mM, the associated nanorods density and height were significantly lower than those grown with the other precursor concentrations. This phenomenon was attributed to the fact that the reactants using 6 mM/5 mM precursors were not sufficient in concentration to deposit at every site where the GaOOH nanorods could be formed. Consequently, the most suitable synthesis conditions for the GaOOH nanorods were the 50-nm-thickness SnO2 seed layer and the Ga(NO3)3·9H2O/HMT precursor concentration of 12 mM/10 mM, which exhibited the largest surface-to-volume ratio for the GaOOH nanorods.
To improve the gas sensitivity of the NO2 gas sensors, the GaOOH nanorods should be converted into Ga2O3 nanorods by annealing treatment. In addition, XPS was carried out to study the existence of oxygen vacancies (Ovacancy) and -OH bonds in the Ga2O3 nanorod sensing membranes with various annealing temperatures. Figure 6a–d show the O1s core level spectra of the GaOOH nanorods without and with annealing treatment for 2 h at 300 °C, 400 °C, and 500 °C, respectively. The O1s peak was composed of three bands located at the binding energy of 530.8 eV, 532.1 eV, and 533.0 eV, which were, respectively, assigned to the Ga3+, Ovacancy, and -OH bonds [28]. According to the XPS results, the peak intensity of the -OH bonds was significantly reduced when increasing the annealing temperature. This phenomenon indicated that the thermal energy in the annealing treatment process could cause the dehydroxylation reaction in the Ga2O3 nanorods [29]. Moreover, the peak ratio of the Ga3+ and Ovacancy bonds (Ga3+/Ovacancy) for the GaOOH nanorods without and with annealing treatment for 2 h at 300 °C, 400 °C, and 500 °C was 11.93, 8.43, 7.38, and 7.01, respectively. It is worth noting that the oxygen vacancies could be effectively increased on the surfaces of the Ga2O3 nanorods in the annealing treatment process, thereby increasing the active sites for the NO2 gas.
Figure 7 shows the temperature dependence of the resistance (RS(T)) for the NO2 gas sensors with Ga2O3 nanorod sensing membranes annealed at various temperatures. In general, the reaction rate and operating temperature were mainly affected by the activation energy (EA) in the gas sensors. The activation energy of the Ga2O3 nanorod-structured NO2 gas sensors was calculated using the following Arrhenius equation [30]:
R s T = R 0 e E A kT
ln R s T = ln R 0 + E A 1000 k 1000 T
where R0 is the pre-exponential factor, k is the Boltzmann constant, and T is the absolute temperature, respectively. The activation energy is determined by the slope of the Arrhenius plot. As shown in Figure 7, the activation energy of 248 meV, 214 meV, and 211 meV corresponded to the NO2 gas sensors with Ga2O3 nanorod sensing membranes annealed at 300 °C, 400 °C, and 500 °C, respectively. In general, the activation energy was inversely proportional to the carrier concentration [31,32], which was also increased with the amounts of oxygen vacancies in the Ga2O3 material [33]. According to the XPS results, the oxygen vacancies residing on the surfaces of Ga2O3 nanorods were effectively increased during the annealing treatment process. Consequently, it could be deduced that the activation energy was decreased with an increase in the annealing temperature.
In this study, the gas responsivity (R) was calculated using the following equation:
R % = R g R a R a × 100 %
where Rg and Ra are the resistances of the NO2 gas sensors in NO2 gas and air environments, respectively. Figure 8 shows the responsivity versus operating temperature characteristics of the NO2 gas sensors with Ga2O3 nanorod sensing membranes annealed at various temperatures. Under a bias voltage of 1 V and a NO2 gas concentration of 10 ppm, the optimal responsivity of the NO2 gas sensors with Ga2O3 nanorod sensing membranes annealed at 300 °C, 400 °C, and 500 °C was 225.8%, 1184.6%, and 824.9%, respectively. The corresponding operating temperatures of the optimal responsivity were 300 °C, 275 °C, and 250 °C. It could be found that the responsivity increased with an increase in the annealing temperature until 400 °C and then decreased when further increasing the annealing temperature to 500 °C. The reduction in operating temperature tendency was followed by the activation energy tendency of the annealing temperature of the Ga2O3 nanorod sensing membranes. The enhanced responsivity was attributed to the fact that the annealing thermal energy could effectively increase the oxygen vacancies, thereby providing more gas-reactive surface sites. However, the improvement responsivity of the NO2 gas sensors with 500 °C-annealed Ga2O3 nanorod sensing membranes was degraded. It could be deduced that the induced excessive carrier concentration present in the 500 °C-annealed Ga2O3 nanorod sensing membranes could reduce the resistance variation [34].
Figure 9a,b show the response time (τr) and recovery time (τd) of the NO2 gas sensors with Ga2O3 nanorod sensing membranes annealed at various temperatures under a bias voltage of 1 V and a NO2 gas concentration of 10 ppm at their associated individual optimal operating temperatures. In general, the response time and recovery time were calculated as the time from 0% to 90% of the maximum responsivity and from 100% to 10% of the maximum responsivity, respectively [35]. As shown in Figure 9a,b, under the individual optimal operating temperatures of 300 °C, 275 °C, and 250 °C, the response time of the NO2 gas sensors with Ga2O3 nanorod sensing membranes annealed at 300 °C, 400 °C, and 500 °C was 75.7, 63.6, and 61.5 s, respectively. The corresponding recovery time was 410.4, 135.7, and 125.9 s, respectively. These results indicated that both the response time and the recovery time of the resulting NO2 gas sensors decreased with an increase in the annealing temperature. This phenomenon was attributed to the fact that lower activation energy of the Ga2O3 nanorod-structured gas sensors could be achieved by annealing the sensing membranes at a higher temperature. The reduction in the response time and the recovery time of the resulting gas sensors could be induced by the lower activation energy [36,37].
Figure 10 presents the dynamic gas responsivity of the NO2 gas sensors with 400 °C annealed-Ga2O3 nanorod sensing membranes under various NO2 concentrations at an operating temperature of 275 °C. It could be found that the responsivity of the gas sensor increased with an increase in the NO2 concentration, reaching saturation at 50 ppm. The NO2 gas sensors with 400 °C annealed-Ga2O3 nanorod sensing membranes could be effectively detected even at a very low NO2 concentration of 100 ppb and the achieved responsivity was 34.2%.
To investigate the gas selectivity of the NO2 gas sensor with a Ga2O3 nanorod sensing membrane, alcohol (C2H5OH) and ammonia (NH3) were also used as the target gases in this study. Figure 11 shows the responsivity of the gas sensor with a 400 °C-annealed Ga2O3 nanorod sensing membrane under various target gases. Under a C2H5OH concentration of 100 ppm, a NH3 concentration of 100 ppm, and a NO2 concentration of 10 ppm, the responsivity of the NO2 gas sensors was 154.8%, 187.2%, and 1184.6%, respectively, at an operating temperature of 275 °C. This indicated that the gas sensor had certain sensing capability for C2H5OH and NH3 gases, but the responsivity was significantly lower than that of NO2 gas. Consequently, it could be concluded that the NO2 gas sensors using the 400 °C-annealed Ga2O3 nanorods as the sensing membranes had high selectivity for NO2 gas.
To further highlight the results of this work, the performance of the NO2 gas sensors using Ga2O3 nanorods as the sensing membranes were compared with other similar studied NO2 gas sensors reported previously, as listed in Table 1. The performance of the NO2 gas sensors with Ga2O3 nanorod sensing membranes exhibited excellent features.

4. Conclusions

In this study, various Ga2O3 nanorods were successfully grown on quartz substrates as sensing membranes of NO2 gas sensors using the hydrothermal synthesis method and annealing processes. To increase the surface-to-volume ratio of the GaOOH nanorods, the thickness of the SnO2 seed layer and the concentration of the hydrothermal precursor (Ga(NO3)3·9H2O/HMT) were optimized. The surface-to-volume ratio of the GaOOH nanorods decreased with an increase in the thickness of the SnO2 seed layer due to the reduction in the resulting grain size. Moreover, by decreasing the concentration of the hydrothermal precursor (Ga(NO3)3·9H2O/HMT), the surface-to-volume ratio of the resulting GaOOH nanorods gradually increased. Although the concentration of 6 mM/5 mM had the highest surface-to-volume ratio, its nanorod density was significantly lower than for the other concentrations. It was found that the surface-to-volume ratio of the GaOOH nanorods could be effectively optimized using the 50-nm-thick SnO2 seed layer and the Ga(NO3)3·9H2O/HMT concentration of 12 mM/10 mM. The dependence of oxygen vacancies on the annealing temperature of Ga2O3 nanorods was verified by the measurements of the XPS experimental results. When the Ga2O3 nanorods were annealed at various temperatures, the amounts of oxygen vacancies were increased and the number of -OH bonds was suppressed by the thermal treatment. Consequently, the associated activation energy of the NO2 gas sensors was decreased from 248 meV to 211 meV when increasing the annealing temperature of the Ga2O3 nanorod sensing membranes from 300 °C to 500 °C. The Ga2O3 nanorod sensing membrane annealed for 2 h at 400 °C achieved the maximum responsivity of 1184.6%. The response time and recovery time of the NO2 gas sensors with Ga2O3 nanorod sensing membranes were effectively improved by the annealing treatment, which was due to the activation energy tendency of the Ga2O3 nanorods. Furthermore, because the Ga2O3 nanorod-structured NO2 gas sensor revealed high sensitivity, it could even detect NO2 gas with a concentration as low as 100 ppb. Moreover, the gas sensor also exhibited high selectivity towards NO2 gas, and the responsivity of the gas sensors under the NO2 concentration of 10 ppm was larger than that under the C2H5OH and NH3 concentrations of 100 ppm. Consequently, it is verified that the low-cost hydrothermal synthesis method can grow GaOOH nanorods that can be converted into Ga2O3 nanorods using a thermal annealing process. The resulting Ga2O3 nanorods are promising candidates for NO2 gas sensors.

Author Contributions

Conceptualization, H.-Y.L. and C.-T.L.; data curation, S.-Y.C., M.-J.W. and T.-H.Y.; funding acquisition, H.-Y.L. and C.-T.L.; investigation, S.-Y.C., H.-Y.L. and C.-T.L.; writing—original draft, S.-Y.C. and T.-H.Y.; writing—review and editing, H.-Y.L. and C.-T.L. All authors have read and agreed to the published version of the manuscript.

Funding

This work was supported by the National Science and Technology Council (NSTC), Republic of China, under No. MOST-111-2221-E-006-045 and MOST-111-2221-E-006-229-MY3.

Institutional Review Board Statement

Not applicable.

Informed Consent Statement

Not applicable.

Data Availability Statement

The data presented in this study are available on request from the corresponding author.

Conflicts of Interest

The authors declare no conflict of interest.

References

  1. Shendage, S.S.; Patil, V.L.; Patil, S.P.; Vanalakar, S.A.; Bhosale, J.L.; Kim, J.H.; Patil, P.S. NO2 sensing properties of porous fibrous reticulated WO3 thin films. J. Anal. Appl. Pyrolysis 2017, 125, 9–16. [Google Scholar] [CrossRef]
  2. Kamble, D.L.; Harale, N.S.; Patil, V.L.; Patil, P.S.; Kadam, L.D. Characterization and NO2 gas sensing properties of spray pyrolyzed SnO2 thin films. J. Anal. Appl. Pyrolysis 2017, 127, 38–46. [Google Scholar] [CrossRef]
  3. Shankar, J.B.; Rayappan, B.B. Gas sensing mechanism of metal oxides: The role of ambient atmosphere, type of semiconductor and gases-a review. Sci. Lett. J. 2015, 4, 126. [Google Scholar]
  4. Nagarjuna, Y.; Lin, J.C.; Wang, S.C.; Hsiao, W.T.; Hsiao, Y.J. AZO-Based ZnO nanosheet MEMS sensor with different Al concentrations for enhanced H2S gas sensing. Nanomaterials 2021, 11, 3377. [Google Scholar] [CrossRef] [PubMed]
  5. Wang, M.S.; Zhu, Y.C.; Luo, Q.; Ge, C.X.; Liu, G.W.; Qiao, G.J.; Kim, E.J. Below-room-temperature solution-grown ZnO porous nanosheet arrays with ppb-level NO2 sensitivity under intermittent UV irradiation. Appl. Surf. Sci. 2021, 566, 150750. [Google Scholar] [CrossRef]
  6. Zhang, J.; Liu, X.H.; Neri, G.; Pinna, N. Nanostructured materials for room-temperature gas sensors. Adv. Mater. 2016, 28, 795–831. [Google Scholar] [CrossRef]
  7. Wu, H.; Ma, Z.; Lin, Z.X.; Song, H.Z.; Yan, S.C.; Shi, Y. High-sensitive ammonia sensors based on tin monoxide nanoshells. Nanomaterials 2019, 9, 388. [Google Scholar] [CrossRef] [Green Version]
  8. Cao, S.; Sui, N.; Zhang, P.; Zhou, T.T.; Tu, J.C.; Zhang, T. TiO2 nanostructures with different crystal phases for sensitive acetone gas sensors. J. Colloid Interface Sci. 2022, 607, 357–366. [Google Scholar] [CrossRef]
  9. Wang, W.H.; Zhang, L.; Kang, Y.L.; Yu, F. Light-excited Ag-doped TiO2-CoFe2O4 heterojunction applied to toluene gas detection. Nanomaterials 2021, 11, 3261. [Google Scholar] [CrossRef]
  10. Jian, L.Y.; Lee, C.T.; Lee, H.Y. Performance improvement of NO2 gas sensor using rod-patterned tantalum pentoxide-alloyed indium oxide sensing membranes. IEEE Sens. J. 2021, 21, 2134–2139. [Google Scholar] [CrossRef]
  11. Liang, X.; Zhang, J.; Du, L.Y.; Zhang, M.Z. Effect of resonant tunneling modulation on ZnO/In2O3 heterojunction nanocomposite in efficient detection of NO2 gas at room temperature. Sens. Actuators B Chem. 2021, 329, 129230. [Google Scholar] [CrossRef]
  12. Almaev, A.V.; Nikolaev, V.I.; Yakovlev, N.N.; Butenko, P.N.; Stepanov, S.I.; Pechnikov, A.I.; Scheglov, M.P.; Chernikov, E.V. Hydrogen sensors based on Pt/alpha-Ga2O3:Sn/Pt structures. Sens. Actuators B Chem. 2022, 364, 131904. [Google Scholar] [CrossRef]
  13. Fzal, A. Beta-Ga2O3 nanowires and thin films for metal oxide semiconductor gas sensors: Sensing mechanisms and performance enhancement strategies. J. Mater. 2019, 5, 542–557. [Google Scholar] [CrossRef]
  14. Pearton, S.J.; Yang, J.C.; Cary, P.H.; Ren, F.; Kim, J.; Tadjer, M.J.; Mastro, M.A. A review of Ga2O3 materials, processing, and devices. Appl. Phys. Rev. 2018, 5, 011301. [Google Scholar] [CrossRef] [Green Version]
  15. Zhang, J.H.; Jiao, S.J.; Wang, D.B.; Gao, S.Y.; Wang, J.Z.; Zhao, L.C. Nano tree-like branched structure with alpha-Ga2O3 covered by gamma-Al2O3 for highly efficient detection of solar-blind ultraviolet light using self-powered photoelectrochemical method. Appl. Surf. Sci. 2021, 541, 148380. [Google Scholar] [CrossRef]
  16. Vorobyeva, N.; Rumyantseva, M.; Platonov, V.; Filatova, D.; Chizhov, A.; Marikutsa, A.; Bozhev, I.; Gaskov, A. Ga2O3(Sn) oxides for high-temperature gas sensors. Nanomaterials 2021, 11, 2938. [Google Scholar] [CrossRef]
  17. Bagheri, M.; Khodadadi, A.A.; Mahjoub, A.R.; Mortazavi, Y. Strong effects of gallia on structure and selective responses of Ga2O3-In2O3 nanocomposite sensors to either ethanol, CO or CH4. Sens. Actuators B Chem. 2015, 220, 590–599. [Google Scholar] [CrossRef]
  18. Yao, Y.; Yin, M.L.; Yan, J.Q.; Liu, S.Z. P-type sub-tungsten-oxide based urchin-like nanostructure for superior room temperature alcohol sensor. Appl. Surf. Sci. 2018, 441, 277–284. [Google Scholar] [CrossRef]
  19. Nunes, D.; Pimentel, A.; Goncalves, A.; Pereira, S.; Branquinho, R.; Barquinha, P.; Fortunato, E.; Martins, R. Metal oxide nanostructures for sensor applications. Semicond. Sci. Technol. 2019, 34, 043001. [Google Scholar] [CrossRef] [Green Version]
  20. Wang, J.; Chen, R.S.; Xiang, L.; Komarneni, S. Synthesis, properties and applications of ZnO nanomaterials with oxygen vacancies: A review. Ceram. Int. 2018, 44, 7357–7377. [Google Scholar] [CrossRef]
  21. Liu, Y.P.; Zhu, L.Y.; Feng, P.; Dang, C.C.; Li, M.; Lu, H.L.; Gao, L.M. Bimetallic AuPt alloy nanoparticles decorated on ZnO nanowires towards efficient and selective H2S gas sensing. Sens. Actuators B Chem. 2022, 367, 132024. [Google Scholar] [CrossRef]
  22. Zhang, J.H.; Jiao, S.J.; Wang, D.B.; Ni, S.M.; Gao, S.Y.; Wang, J.Z. Solar-blind ultraviolet photodetection of an alpha-Ga2O3 nanorod array based on photoelectrochemical self-powered detectors with a simple, newly-designed structure. J. Mater. Chem. C 2019, 7, 6867–6871. [Google Scholar] [CrossRef]
  23. Wang, W.W.; Wang, D.Y.; Zhang, X.X.; Yang, C.Q.; Zhang, D.Z. Self-powered nitrogen dioxide sensor based on Pd-decorated ZnO/MoSe2 nanocomposite driven by triboelectric nanogenerator. Nanomaterials 2022, 12, 4274. [Google Scholar] [CrossRef] [PubMed]
  24. Pokai, S.; Limnonthakul, P.; Horprathum, M.; Eiamchai, P.; Pattantsetakul, V.; Limwichean, S.; Nuntawong, N.; Porntheeraphat, S.; Chitichotpanya, C. Influence of seed layer thickness on well-aligned ZnO nanorods via hydrothermal method. Mater. Today 2017, 4, 6336–6341. [Google Scholar] [CrossRef]
  25. Hou, S.W.; Li, C.Y. Aluminum-doped zinc oxide thin film as seeds layer effects on the alignment of zinc oxide nanorods synthesized in the chemical bath deposition. Thin Solid Films 2016, 605, 37–43. [Google Scholar] [CrossRef]
  26. Ghayour, H.; Rezaie, H.R.; Mirdamadi, S.; Nourbakhsh, A.A. The effect of seed layer thickness on alignment and morphology of ZnO nanorods. Vaccum 2011, 86, 101–105. [Google Scholar] [CrossRef]
  27. Benhaoua, B.; Abbas, S.; Rahal, A.; Benhaoua, A.; Aida, M.S. Effect of film thickness on the structural, optical and electrical properties of SnO2: F thin films prepared by spray ultrasonic for solar cells applications. Superlattices Microstruct. 2015, 83, 78–88. [Google Scholar] [CrossRef]
  28. Kim, W.G.; Tak, Y.J.; Ahn, B.D.; Jung, T.S.; Chung, K.B.; Kim, H.J. High-pressure gas activation for amorphous indium-gallium-zinc-oxide thin-film transistors at 100 °C. Sci. Rep. 2016, 6, 23039. [Google Scholar] [CrossRef] [Green Version]
  29. Pilliadugula, R.; Krishnan, N.G. Gas sensing performance of GaOOH and beta-Ga2O3 synthesized by hydrothermal method: A comparison. Mater. Res. Express 2019, 6, 025027. [Google Scholar] [CrossRef]
  30. Jian, L.Y.; Lee, H.Y.; Lee, C.T. Enhanced nitrogen dioxide gas-sensing performance using tantalum pentoxide-alloyed indium oxide sensing membrane. IEEE Sens. J. 2019, 19, 7829–7834. [Google Scholar] [CrossRef]
  31. Anand, V.; Sakthivelu, A.; Kumar, K.D.A.; Valanarasu, S.; Ganesh, V.; Shkir, M.; AlFaify, S.; Algarni, H. Rare earth Eu3+ co-doped AZO thin films prepared by nebulizer spray pyrolysis technique for optoelectronics. J. Sol-Gel Sci. Technol. 2018, 86, 293–304. [Google Scholar] [CrossRef]
  32. Kumar, M.; Bhat, T.N.; Roul, B.; Rajpalke, M.K.; Kalghatgi, A.; Krupanidhi, S. Carrier concentration dependence of donor activation energy in n-type GaN epilayers grown on Si (111) by plasma-assisted MBE. Mater. Res. Bull. 2012, 47, 1306–1309. [Google Scholar] [CrossRef]
  33. Chu, S.Y.; Yeh, T.H.; Lee, C.T.; Lee, H.Y. Mg-doped beta-Ga2O3 films deposited by plasma-enhanced atomic layer deposition system for metal-semiconductor-metal ultraviolet C photodetectors. Mater. Sci. Semicond. Process. 2022, 142, 106471. [Google Scholar] [CrossRef]
  34. Zhu, C.L.; Chen, Y.J.; Wang, R.X.; Wang, L.J.; Cao, M.S.; Shi, X.L. Synthesis and enhanced ethanol sensing properties of alpha-Fe2O3/ZnO heteronanostructures. Sens. Actuators B Chem. 2009, 140, 185–189. [Google Scholar] [CrossRef]
  35. Zhao, G.D.; Xuan, J.Y.; Liu, X.L.; Jia, F.C.; Sun, Y.P.; Sun, M.L.; Yin, G.C.; Liu, B. Low-cost and high-performance ZnO nanoclusters gas sensor based on new-type FTO electrode for the low-concentration H2S gas detection. Nanomaterials 2019, 9, 435. [Google Scholar] [CrossRef] [Green Version]
  36. Kumar, M.; Bhati, V.S.; Ranwa, S.; Singh, J.; Kumar, M. Pd/ZnO nanorods based sensor for highly selective detection of extremely low concentration hydrogen. Sci. Rep. 2017, 7, 236. [Google Scholar] [CrossRef]
  37. Zhang, P.S.; Pan, G.F.; Zhang, B.Q.; Zhen, J.L.; Sun, Y.C. High sensitivity ethanol gas sensor based on Sn-doped ZnO under visible light irradiation at low temperature. Mater. Res.-Ibero-Am. J. 2014, 17, 817–822. [Google Scholar] [CrossRef] [Green Version]
  38. Mohammadi, M.R.; Fray, D.J. Semiconductor TiO2-Ga2O3 thin film gas sensors derived from particulate sol-gel route. Acta Mater. 2007, 55, 4455–4466. [Google Scholar] [CrossRef]
  39. Wu, M.R.; Li, W.Z.; Tung, C.Y.; Huang, C.Y.; Chiang, Y.H.; Liu, P.L.; Horng, R.H. NO gas sensor based on ZnGa2O4 epilayer grown by metalorganic chemical vapor deposition. Sci. Rep. 2019, 9, 7459. [Google Scholar] [CrossRef] [Green Version]
  40. Shafiei, M.; Hoshyargar, F.; Motta, N.; O’Mullane, A.P. Utilizing p-type native oxide on liquid metal microdroplets for low temperature gas sensing. Mater. Des. 2017, 122, 288–295. [Google Scholar] [CrossRef] [Green Version]
  41. Mun, Y.; Park, S.; Ko, H.; Lee, C.; Lee, S. NO2 gas sensing properties of ZnO/ZnS core-shell nanowires. J. Korean Phys. Soc. 2013, 63, 1595–1600. [Google Scholar] [CrossRef]
  42. Li, C.; Yu, L.M.; Fan, X.H.; Yin, M.L.; Nan, N.; Cui, L.; Ma, S.; Li, Y.; Zhang, B. Nucleation density and pore size tunable growth of ZnO nanowalls by a facile solution approach: Growth mechanism and NO2 gas sensing properties. RSC Adv. 2020, 10, 3319–3328. [Google Scholar] [CrossRef] [PubMed] [Green Version]
  43. Kamble, V.S.; Zemase, R.K.; Gupta, R.H.; Aghav, B.D.; Shaikh, S.A.; Pawara, J.M.; Patil, S.K.; Salunkhe, S.T. Improved toxic NO2 gas sensing response of Cu-doped ZnO thin-film sensors derived by simple co-precipitation route. Opt. Mater. 2022, 131, 112706. [Google Scholar] [CrossRef]
Figure 1. Schematic configuration of NO2 gas sensors with Ga2O3 nanorod sensing membrane.
Figure 1. Schematic configuration of NO2 gas sensors with Ga2O3 nanorod sensing membrane.
Nanomaterials 13 01064 g001
Figure 2. Schematic configuration of measurement system of NO2 gas sensors.
Figure 2. Schematic configuration of measurement system of NO2 gas sensors.
Nanomaterials 13 01064 g002
Figure 3. XRD spectra of SnO2 seed layers with various thicknesses.
Figure 3. XRD spectra of SnO2 seed layers with various thicknesses.
Nanomaterials 13 01064 g003
Figure 4. FE-SEM top-view and cross-section images of GaOOH nanorods grown on SnO2 seed layers with a thickness of (a) 50 nm, (b) 100 nm, and (c) 200 nm.
Figure 4. FE-SEM top-view and cross-section images of GaOOH nanorods grown on SnO2 seed layers with a thickness of (a) 50 nm, (b) 100 nm, and (c) 200 nm.
Nanomaterials 13 01064 g004
Figure 5. FE-SEM top-view and cross-section images of GaOOH nanorods grown using various precursor concentrations of (a) 6 mM/5 mM, (b) 12 mM/10 mM, and (c) 18 mM/15 mM.
Figure 5. FE-SEM top-view and cross-section images of GaOOH nanorods grown using various precursor concentrations of (a) 6 mM/5 mM, (b) 12 mM/10 mM, and (c) 18 mM/15 mM.
Nanomaterials 13 01064 g005
Figure 6. XPS spectra of O1s core-level spectra of (a) as-grown GaOOH nanorods and annealed Ga2O3 nanorods treated at (b) 300 °C (c) 400 °C, and (d) 500 °C.
Figure 6. XPS spectra of O1s core-level spectra of (a) as-grown GaOOH nanorods and annealed Ga2O3 nanorods treated at (b) 300 °C (c) 400 °C, and (d) 500 °C.
Nanomaterials 13 01064 g006
Figure 7. Temperature dependence of resistance for NO2 gas sensors with Ga2O3 nanorod sensing membranes annealed at various temperatures.
Figure 7. Temperature dependence of resistance for NO2 gas sensors with Ga2O3 nanorod sensing membranes annealed at various temperatures.
Nanomaterials 13 01064 g007
Figure 8. Responsivity versus operating temperature of NO2 gas sensors with Ga2O3 nanorod sensing membranes annealed at various temperatures.
Figure 8. Responsivity versus operating temperature of NO2 gas sensors with Ga2O3 nanorod sensing membranes annealed at various temperatures.
Nanomaterials 13 01064 g008
Figure 9. (a) Response time and (b) recovery time of NO2 gas sensors with Ga2O3 nanorod sensing membranes annealed at various temperatures under 10 ppm NO2 gas concentration.
Figure 9. (a) Response time and (b) recovery time of NO2 gas sensors with Ga2O3 nanorod sensing membranes annealed at various temperatures under 10 ppm NO2 gas concentration.
Nanomaterials 13 01064 g009
Figure 10. Dynamic gas responsivity of NO2 gas sensor with 400 °C-annealed Ga2O3 nanorod sensing membrane under various NO2 concentrations at an operating temperature of 275 °C.
Figure 10. Dynamic gas responsivity of NO2 gas sensor with 400 °C-annealed Ga2O3 nanorod sensing membrane under various NO2 concentrations at an operating temperature of 275 °C.
Nanomaterials 13 01064 g010
Figure 11. Responsivity of gas sensor with 400 °C-annealed Ga2O3 nanorod sensing membrane under various target gases.
Figure 11. Responsivity of gas sensor with 400 °C-annealed Ga2O3 nanorod sensing membrane under various target gases.
Nanomaterials 13 01064 g011
Table 1. Performance comparison of various structured NO2 gas sensors.
Table 1. Performance comparison of various structured NO2 gas sensors.
Materials and StructureResponsivityOperating Temperature (°C)Minimum Concentration of NO2 (ppm)Ref.
TiO2-Ga2O3 thin film~2.42000.5[38]
ZGO thin film1.183000.5[39]
Oxidized galinstan~1.8%1001[40]
ZnO/ZnS core–shell nanowires293.29%3001[41]
ZnO nanowalls9.632205[42]
Cu-doped ZnO thin film26%2005[43]
Ga2O3 nanorods34.2%2750.1This work
Disclaimer/Publisher’s Note: The statements, opinions and data contained in all publications are solely those of the individual author(s) and contributor(s) and not of MDPI and/or the editor(s). MDPI and/or the editor(s) disclaim responsibility for any injury to people or property resulting from any ideas, methods, instructions or products referred to in the content.

Share and Cite

MDPI and ACS Style

Chu, S.-Y.; Wu, M.-J.; Yeh, T.-H.; Lee, C.-T.; Lee, H.-Y. Investigation of High-Sensitivity NO2 Gas Sensors with Ga2O3 Nanorod Sensing Membrane Grown by Hydrothermal Synthesis Method. Nanomaterials 2023, 13, 1064. https://doi.org/10.3390/nano13061064

AMA Style

Chu S-Y, Wu M-J, Yeh T-H, Lee C-T, Lee H-Y. Investigation of High-Sensitivity NO2 Gas Sensors with Ga2O3 Nanorod Sensing Membrane Grown by Hydrothermal Synthesis Method. Nanomaterials. 2023; 13(6):1064. https://doi.org/10.3390/nano13061064

Chicago/Turabian Style

Chu, Shao-Yu, Mu-Ju Wu, Tsung-Han Yeh, Ching-Ting Lee, and Hsin-Ying Lee. 2023. "Investigation of High-Sensitivity NO2 Gas Sensors with Ga2O3 Nanorod Sensing Membrane Grown by Hydrothermal Synthesis Method" Nanomaterials 13, no. 6: 1064. https://doi.org/10.3390/nano13061064

Note that from the first issue of 2016, this journal uses article numbers instead of page numbers. See further details here.

Article Metrics

Back to TopTop