2. Nanowire-Based Nanomaterial Gas Sensors
Among different morphologies, nanowires (NWs) with aspect ratios greater than 20
[2][28] are highly popular for sensing applications, owing to their high surface area, straightforward preparation methods, ease of gas sensor fabrication, high and rapid response to the target gas, long-term stability, and high crystallinity
[3][4][29,30]. Accordingly, several studies have realized the enhanced gas-sensing capacity of NW-based gas sensors
[5][6][31,32]. In
[7][33], various methods to synthesize NWs are discussed in detail.
Among different MOSs with NW morphology, SnO
2 NWs are very popular for sensing purposes
[8][9][10][11][34,35,36,37]. SnO
2 has a band gap of 3–4 eV, depending on the synthesis method, size, surface states, and impurities
[12][38]. However, most studies have reported a band gap of 3.7 eV for this MOS
[13][39]. SnO
2 is the most stable n-type oxide, and is extensively used in the preparation of semiconductor gas sensors. Its high electron mobility (~160 cm
2/V·s) makes it a key choice for sensing applications
[14][15][19,40]. In addition, SnO
2 NWs exhibit good optical transparency and conductivity
[16][41]. Wang et al.
[17][42] performed one of the first studies on SnO
2 NWs for the detection of H
2 gas, and compared the results with those of SnO
2 nanorods (NRs). It was reported that owing to the higher surface area of NWs, size effects when the diameter of the NWs was less than the Debye length of SnO
2, and the small electrode gap of the SnO
2 NW gas sensor, a larger response was observed for the SnO
2 NWs at 300 °C than that for SnO
2 NRs. Notably, not only SnO
2 NWs, but also other MOS NWs, have been employed as gas sensors
[18][19][43,44]. The construction of n–n and p–n junctions is a commonly employed strategy for improving the sensitivity of NW-based gas sensors
[20][45]. Owing to the generation of these heterojunctions, the resistance of gas sensors is higher than that of the pure sensing material, and the subsequent modulation of resistance in the presence of target gases generates a high sensing signal for heterojunction gas sensors
[21][46].
Branched NWs (e.g., nanoforests or nanotrees) are a special type of NWs that have recently been used for sensing applications. Their 3D morphology and numerous homo- or heterojunctions make the branching NWs highly popular for sensing studies. With high surface area, branched NWs can detect extremely low amounts of gases. Branched NWs also offer an increased number of carrier paths and improved conduction between the NW branches and backbones
[22][23][24][47,48,49].
3. Nanofiber-Based Metal Oxide Semiconductor Gas Sensors
3. Nanofiber-Based MOS Gas Sensors
Nanofibers (NFs) are another type of 1D material used in MOS gas sensors. Similar to NWs, NFs have an aspect ratio of more than 20. However, their surfaces have many nanograins, which result in a further increase in the surface area
[25][78]. There are various methods to synthesize NFs; however, NFs are commonly produced using the electrospinning (ES) technique. The ES technique consists of a spinneret section, a high-voltage power supply, and a metal collector
[26][79]. During electrospinning, NFs are formed from a liquid jet and subsequently elongated under a high voltage. The NF formation process consists of the following: (i) onset of jetting and development of a rectilinear jet, (ii) bending deformation along with solvent evaporation to form solidified NFs, and (iii) NF collection
[27][80]. In a simplified view, a sol is initially prepared in this technique, and is subsequently poured into a syringe. Upon applying a high voltage to the sol with a defined viscosity, it is possible to collect extremely fine and long NFs on the collector placed at a fixed distance from the syringe. After calcination of the synthesized NFs at an appropriate temperature for sufficient time, the final diameter decreases due to evaporation of the solvent and organic materials
[26][79].
By optimization of the ES technique parameters—such as the applied voltage, distance between the needle tip and the collector, flow rate, and temperature—it is possible to tune the diameter of the resulting NFs
[28][29][81,82]. In particular, the viscosity of the solution can significantly affect the formation of long NFs
[30][83]. If the viscosity of the ES solution is not adjusted to the desired value, NFs with beads are formed
[30][83].
Furthermore, with a special type of ES technique, known as coaxial ES, it is possible to directly synthesize C–S NFs
[31][32][84,85]. Many MOSs have been successfully synthesized using the ES technique for gas-sensing studies
[33][86]. Similar to C–S NWs, the thickness of the shell layer should be adjusted to obtain the maximum response to the target gas. For example, Kim et al.
[34][87] reported that in SnO
2–Cu
2O C–S NF gas sensors with different shell thicknesses, the sensor with a shell thickness of 30 nm gave the highest response to CO gas—it showed a response to 5–10 ppm of CO gas at 300 °C.
4. Nanotube-Based Metal Oxide Semiconductor Gas Sensors
4. Nanotube-Based MOS Gas Sensors
Metal oxide nanotubes (NTs) have been studied less compared to their NW and NF counterparts
[35][95]. This may be due to the difficulty in the synthesis of MOS NTs. Various techniques can be used for synthesizing MOS NTs. However, the most common method is the use of a hard or soft sacrificial template. Hard templates have been prepared using silica, carbon, and polystyrene beads, while soft templates have been fabricated from bubbles, polymer vesicles, emulsion droplets, and surfactant micelles. The core can be removed by dissolving in a solvent or calcination to generate hollow structures
[36][96]. The main features of gas sensors based on hollow structures such as NTs are (i) wall permeability, (ii) wall thickness, and (iii) wall chemistry
[37][97]. Although thinner NTs are expected to provide greater surface area and more adsorption sites for gas molecules
[38][98], the presence of defects can sometimes alter the sensing properties. Hazra et al. investigated the effects of shell thickness on the sensing characteristics of TiO
2 NTs. Interestingly, the sensor with the thinnest wall and largest surface area did not show the highest response to the target gas, due to the lower amount of oxygen vacancies. The device with a thicker wall and sufficient oxygen vacancies exhibited the highest response
[39][99]. In conclusion, MOS-based NTs for gas-sensing studies offer a high surface area owing to the hollowness of their structure, which can provide many adsorption sites for gas molecules.
5. Nanorod-Based Metal Oxide Semiconductor Gas Sensors
5. Nanorod-Based MOS Gas Sensors
Nanorod-based gas sensors are another popular category of MOS materials for gas-sensing studies, owing to their unique electrical properties and high surface area provided by the NR morphology. The hydrothermal method provides a convenient, fast, versatile, and low-cost route for constructing well-ordered nanorod arrays
[40][41][42][43][100,101,102,103]. However, other methods—such as chemical bath deposition (CBD), which is economical, straightforward, and scalable—can also be used to prepare NRs from different materials
[44][104]. Chemical vapor deposition
[45][46][105,106], metal–organic chemical vapor deposition
[47][48][107,108], and pulsed laser deposition
[49][109] are other methods for obtaining NRs in MOSs. NR-based MOS materials are popular for sensing studies because of their ease of production, high surface area, and compositional versatility.
6. Nanosheet-Based Metal Oxide Semiconductor Gas Sensors
6. Nanosheet-Based MOS Gas Sensors
Two-dimensional MOS nanostructured materials with a sheet-like morphology are popular for gas-sensing studies due to their high surface area. Only a few 2D MOS (MoO
3, WO
3, and SnO
2) analogs of graphene are known. Two-dimensional (2D) layered MOSs have strong in-plane bonds and weak van der Waals forces between layers, and gas molecules can be adsorbed on these sites. Thus, 2D layered MOSs can be employed for the production of gas sensors
[50][110]. Apart from the naturally 2D layered MOSs, other MOSs can also be synthesized in a nanosheet-like morphology. For instance, Choi et al.
[51][111] synthesized porous ZnO nanosheets using a solvothermal technique for NO
2 detection. The sensor exhibited a high response to 74.68–10 ppm of NO
2 gas at 200 °C. The width of the EDL increased in the presence of NO
2 gas, contributing to the sensing signal. Moreover, homojunctions were formed, and changes in the height of the homojunctions led to resistance modulation in the presence of NO
2 gas. Furthermore, the highly porous morphology and high specific surface area (11.51 m
2/g) contributed to the increased availability of active sites for NO
2 gas molecules
[51][111].
7. Three-Dimensional Metal Oxide Semiconductor Gas Sensors
7. Three-Dimensional MOS Gas Sensors
Hierarchical nanostructures with three-dimensional (3D) morphology are composed of zero-, one-, two-, and three-dimensional morphologies, such as nanorods, nanotubes, or nanosheets
[52][22]. Hierarchical nanostructures with high surface area provide more adsorption sites for target gases. In addition, with pores or channels in their structure, the diffusion of gases is facilitated, resulting in better interaction of the target gas with deep parts of the sensing material
[53][113]. Vapor-phase growth and hydrothermal techniques are the two most-used methods to synthesize hierarchical nanostructures
[52][22]. Owing to these advantages, hierarchical morphologies of MOSs are widely used for sensing studies
[54][55][114,115].
For instance, Guo et al.
[56][116] used a 3D hierarchical hollow structure of CuO/WO
3 for p-xylene-sensing studies. The sensor showed a good response to 6.36–50 ppm of xylene gas at 260 °C. The sensing mechanism was related to the unique 3D hierarchical structure with a high surface area of 23.4962 m
2·g
−1, the formation of defects in the interfaces between CuO and WO
3, and the formation of p–n heterojunctions between CuO and WO
3. Recently, Yu et. al.
[57][117] reviewed MOSs with hierarchical structures for gas-sensing studies.
8. Noble-Metal-Decorated Metal Oxide Semiconductor Gas Sensors
8. Noble-Metal-Decorated MOS Gas Sensors
Gas-sensing properties can be improved by loading MOSs with small amounts of appropriately chosen noble metals. Noble metals such as Au, Pt, Pd, Ag, and Ru are widely used for the decoration or functionalization of the MOS surfaces to improve the overall performance of the resulting gas sensors.
It should be noted that the noble metals need to be dispersed as finely as possible on the surface of the MOSs. Agglomeration of noble metals on the surface of the sensing layer can lead to a poor response of the gas sensor. Generally, noble metals affect the gas-sensing performance via two well-known mechanisms: The chemical sensitization mechanism, which occurs via the spillover effect, is a commonly known phenomenon in catalytic chemistry. In this case, the noble metal activates the target gas to facilitate catalytic oxidation of gas. Noble metals increase the gas sensitivity as they increase the rate of chemical processes
[58][119]. In electronic sensitization, because noble metals generally have a larger work function than MOSs, electrons are transferred from the MOS to the noble metals, leading to the formation of Schottky barriers and contraction of the EDL or HAL inside the MOS. In the target gas atmosphere, the width of the EDL and the HAL changes, leading to significant modulation of the sensor resistance. Among noble metals, Pd is well known for H
2 gas detection
[59][120], owing to its excellent catalytic activation ability for hydrogen through the hydrogen spillover effect
[60][121]. When a sensor decorated with Pd NPs is placed in an atmosphere containing H
2 molecules, hydrogen can easily dissociate into hydrogen atoms on the Pd surface; in the spillover effect, hydrogen atoms move to the neighboring MOS surfaces, leading to additional reactions between atomic hydrogen and adsorbed oxygen
[61][122]. Other noble metals also exhibit good catalytic activities toward different gases. For example, Ag is often used for H
2S detection because of the generation of Ag
2S upon exposure to H
2S gas
[62][123]. Pt and Pd also have good catalytic activities toward C
7H
8 and C
6H
6 gases, respectively
[63][64][124,125].
9. Hybrid Metal Oxide Semiconductor Gas Sensors
9. Hybrid MOS Gas Sensors
A good strategy to enhance the gas-sensing characteristics of MOS-based gas sensors is using another material in combination with the MOS. Hybrid MOS nanocomposites are either (i) composites of MOS and carbon materials such as graphene, graphene oxide (GO), reduced graphene oxide (rGO), and carbon nanotubes, or (ii) composites of MOS and conductive polymers (CPs). Graphene, which comprises sp
2 carbon atoms, is utilized in gas sensors due to its high charge carrier mobility (200,000 cm
2 V
−1 s
−1) and large surface area (2630 m
2 g
−1)
[65][126]. The first ever graphene gas sensor was introduced in 2007
[66][127]. Owing to its single-layer or few-layer nature, graphene can even interact with a single molecule. Pristine graphene can easily agglomerate owing to the surface interactions. Furthermore, graphene has no band gap, hindering its gas-sensing usage
[67][128]. Thus, rGO, with its many functional groups—such as -OH and –O—as well as defects, is a better choice for gas-sensing studies. Although GO can be used for sensing applications, it has a very high resistance owing to the presence of oxygen-based functional groups, limiting its use in sensing studies
[68][129]. rGO can be synthesized from GO using chemical reduction, thermal reduction, and UV light reduction methods
[69][70][130,131]. Many papers on gas sensors with hybrids of MOSs and carbon allotropes have been reported. However, for sensing studies, rGO is the most effective allotrope of carbon in its hybrid form. This is because of its large surface area, presence of many defects, and high concentrations of charge carriers with high mobility—all of which are beneficial for sensing. Accordingly, several studies have been reported on hybrid MOS–rGO composites with the ability to operate at room temperature
[71][72][132,133].
CPs have tunable conductivity and high flexibility in synthesis and processing. However, because of the high affinity of CPs for moisture, they are unstable, and generally exhibit poor sensitivity and selectivity for different gases in their pristine form. The use of hybrid nanocomposites with CPs and MOSs could result in the development of room-temperature gas sensors
[73][134]. Accordingly, hybrids of CPs and MOSs have been used to enhance the sensitivity of nanostructured sensors at low or room temperature
[74][75][135,136]. One application of hybrids of MOSs and CPs is the development of flexible and wearable gas sensors. Flexible gas sensors are generally deposited on flexible substrates, and need to work at low temperatures, e.g., room temperature. Since composites of MOs and CPs can function at low temperatures, they are good candidates for such applications.
10. Comparison of Performance of Gas Sensors with Different Morphologies
Table 1 summarizes the performance of gas sensors with various morphologies. Different morphologies and compositions have been used for the detection of various gases at different temperatures. Moreover, pristine gas sensors show lower responses and higher sensing temperatures, while composite or decorated sensing materials show better performance at lower temperatures.
Table 1.
Gas-sensing properties of different sensors with various morphologies.