Commercial WO₃ powder was obtained from Merck and used without further purification. MWCNTs were grown by the thermal chemical vapor deposition (CVD) process. The catalyst layer of aluminium oxide (10 nm) and stainless steel (5 nm) was deposited on the silicon (100) substrates (Semiconductor Wafer Inc.) using reactive sputtering apparatus. The synthesis of MWCNTs was performed under a flow of acetylene/hydrogen at a ratio of 3.6:1 at 700 °C for 3 min. To obtain high-purity MWCNTs, the water-assisted selective etching technique [28] was applied after each CNT’s growth stage. Water vapor (300 ppm) was introduced into the system by bubbling argon gas through liquid water at room temperature for 3 min. The sequence of acetylene/hydrogen and water vapor flows was repeated for five cycles. Based on the scanning electron microscopic (SEM) image, as shown in Figure 1, the diameter and length of the MWCNTs are ∼35 nm and ∼26 μm, respectively. The electrical conductivity of MWCNTs was ∼75 S/cm, as measured by a four-point probe method at room temperature. In addition, high-resolution transmission electron microscopic (HR-TEM) imaging, as shown in Figure 2, confirms that CNTs are multi-walled, with the width and number of walls being ∼4.6 nm and 14, respectively. Thus, the spacing between two graphitic layers is ∼0.33 nm, which is in good agreement with theoretical and experimental values.

MWCNT-doped WO₃ thin film was fabricated by the E-beam evaporation technique onto Cr/Au interdigitated electrodes on an alumina substrate [29]. The target was prepared by mixing 99 wt% of WO₃ powder with 1 wt% of MWCNT powder using a grinder in a mortar for 30 min and then pelletizing with a hydraulic compressor. Deposition was performed at a pressure of 5 × 10⁻⁶ Torr in the evaporation chamber. The substrate was rotated and kept at 130 °C during the deposition in order to obtain a homogeneous thin film. The deposition rate was 2 Å/sec and the final film thickness was 150 nm, as controlled by a quartz crystal monitor. After E-beam evaporation, the film was annealed at 500 °C for 3 h in air to stabilize the crystalline structure. In addition, an undoped WO₃ thin film was also fabricated using the same conditions for comparison.

To evaluate the gas sensing properties of the thus prepared thin films, MWCNT-doped WO₃ and undoped WO₃ gas sensors were placed inside a stainless steel chamber and the resistance measured using a 8846A Fluke multimeter with 6.5 digit resolution. The gas sensing measurements were made within a dynamic flow system with control of sensor operating temperatures (200–400 °C) under variable gas concentrations (100–50,000 ppm). Hydrogen (H₂), ethanol (C₂H₅OH), methane (CH₄), acetylene (C₂H₂), and ethylene (C₂H₄) were used to test the sensing properties and selectivity of the thin films. The sample gas flow time and the clean air reference flow time were fixed at 5 min and 15 min, respectively. It should be noted that these switching interval was selected so that the resistance change is at least 90% of the saturated value. The sensor resistances were sampled and recorded every second using LabVIEW with a USB DAQ device for subsequent analyses.

Surface morphology, particle size and crystalline structure of the films were characterized by SEM and TEM. Figure 3 shows the SEM surface morphology of MWCNT-doped WO₃ thin film deposited on an alumina substrate. It was seen that the film coated on the rough alumina substrate has approximate grain sizes ranging from 40 to 80 nm.

The nanometer grain size together with the roughness of the alumina substrate can enhance the gas sensitivity of thin films [30,31] because more gas adsorption sites are available due to the increased surface area and porosity. With the SEM resolution, CNT structure cannot be observed on the thin film surface. Therefore, TEM characterization was used to confirm CNT inclusion into the WO₃ film. It should be noted that copper TEM grid samples were loaded inside the evaporation chamber for sample deposition at the same time as coating on the Cr/Au interdigitated electrodes. TEM observation clearly shows CNT inclusion into the nanocrystalline WO₃, while the electron diffraction pattern exhibits polycrystalline phase in the film, as shown in Figure 4a,b, respectively.

The film morphology obtained in our study is in accordance with observations on nanocrystalline WO₃ films grown by other methods [32,33]. Doping of CNT does not change the phase or surface morphology of the film, but it may help form nanochannels in WO₃ films, leading to the enhancement of the sensitivity and reduction of the operating temperature.

The sensor response (S) of the thin films is defined as the percentage of resistance change: (1) S ( % ) = ( R 0 − R R 0 ) × 100where R₀ and R are the resistance of the thin films in pure air and test gas, respectively. Figure 5 shows the response of the undoped WO₃ and MWCNT-doped WO₃ thin films to 1,000 ppm H₂ at varying operating temperatures. It can be seen that the response of the films increases as the operating temperature increases up to 350 °C, and then decreases. The gas-sensing response increases with temperature in the 200–350 °C range because thermal energy helps the reactions involved overcome their respective activation energy barriers [34,35]. However, if the operating temperature becomes too high (i.e., >350 °C), the adsorbed oxygen species at the sensing sites on the film surface will be diminished and less available to react with H₂ molecules [36], thereby limiting the film’s response.

At any operating temperature, the sensor response of the MWCNT-doped WO₃ thin film is higher than that of the undoped WO₃ thin film. Specifically, at the optimum operating temperature (350 °C), MWCNT-doped WO₃ thin film yields a 26.9 % higher response than the undoped one. The doped sensor prepared in this work also shows higher response than the WO₃ films prepared by the sol–gel process [25].

One major advantage of MWCNT-doped WO₃ thin film is that the sensor can be operated at a lower operating temperature (250 °C), especially if this sensor is used to measure the H₂ gas at higher concentrations (5,000–50,000 ppm). As shown in Figure 6, at such a concentration range, there are sufficient numbers of H₂ molecules available to react with the surface oxygen adsorption sites. It is also well-known that MWCNTs contribute to the reduction of sensor resistance of metal oxides [37] and the activation energy between the WO₃ surface and H₂ gas. The details of the sensing mechanisms of MWCNT-doped WO₃ thin films will be discussed in the next section.

To demonstrate the selectivity of the MWCNT-doped WO₃ thin film, its sensing response (at the operating temperature of 350 °C) to various gas vapors, namely H₂, C₂H₅OH, CH₄, and C₂H₂, was measured and plotted (Figure 7). It can be seen that MWCNT-doped WO₃ thin film exhibits a strong response to H₂, and much weaker responses to C₂H₅OH, CH₄, and C₂H₂. In particular, this thin film was found to be insensitive to C₂H₄ at the optimum operating temperature of 350 °C. It is therefore concluded that the MWCNT-doped WO₃ thin film exhibits high selectivity to H₂.

It is well known that WO₃ is an n-type semiconductor while CNT is a p-type semiconductor. MWCNT-doped WO₃ thin film can be either p-type or n-type semiconductors depending on the quantity of MWCNTs and the operating temperature [38]. In this work, the produced MWCNTs-doped WO₃ thin film behaves as an n-type semiconductor since the electrical conductivity of the film increases when reducing gases, i.e., H₂, are absorbed by its surface. Doping of MWCNTs into the WO₃ matrix can introduce nanochannels and form p-n heterojunctions in the thin film. These nanochannels play an important role for gas diffusion. The gas molecules can easily transport into the gas-sensing layers leading to increasing sensitivity [39,40]. In addition, MWCNT-doped WO₃ thin film p-n heterojunctions could be formed at the interface between WO₃ and the MWCNTs [38,41]. When H₂ gas is exposed to MWCNT-doped WO₃ thin film, the widths of the depletion layers at the p-n heterojunctions can be modulated. The potential barriers at the interfaces or inside the WO₃ may be changed. This change of the depletion layer in the p–n heterojunctions of MWCNT-doped WO₃ thin film may explain the enhanced response of the film at low operating temperatures. Various oxygen species chemisorbed at the thin film surface such as O²⁻, O₂⁻, and O⁻ are available for catalytic reactions with H₂, thus depending on the temperature at the metal oxide surface [42]. At the operating temperature range of 200–400 °C, O⁻ is commonly chemisorbed. Consequently, the chemical reaction underlying the H₂ gas sensing in this study is given by [43]: (2) H 2 + O ads − → H 2 O + e −

The adsorbed O⁻ on the thin film surface reacts with the H₂ gas yielding H₂O and releasing electrons which contribute to the current increase through the thin film that causes the electrical conductivity to increase.