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Article

Fabrication of Nanosized Island-Like CdO Crystallites-Decorated TiO2 Rod Nanocomposites via a Combinational Methodology and Their Low-Concentration NO2 Gas-Sensing Behavior

by
Yuan-Chang Liang
1,*,
Nian-Cih Xu
1,
Chein-Chung Wang
1 and
Da-Hua Wei
2,*
1
Institute of Materials Engineering, National Taiwan Ocean University, Keelung 20224, Taiwan
2
Graduate Institute of Manufacturing Technology and Department of Mechanical Engineering, National Taipei University of Technology, Taipei 10608, Taiwan
*
Authors to whom correspondence should be addressed.
Materials 2017, 10(7), 778; https://doi.org/10.3390/ma10070778
Submission received: 13 June 2017 / Revised: 5 July 2017 / Accepted: 6 July 2017 / Published: 10 July 2017
(This article belongs to the Special Issue Improving Performance of Nanocomposite Materials)
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Abstract

:
TiO2–CdO composite rods were synthesized through a hydrothermal method and sputtering thin-film deposition. The hydrothermally derived TiO2 rods exhibited a rectangular cross-sectional crystal feature with a smooth surface, and the as-synthesized CdO thin film exhibited a rounded granular surface feature. Structural analyses revealed that the CdO thin film sputtered onto the surfaces of the TiO2 rods formed a discontinuous shell layer comprising many island-like CdO crystallites. The TiO2–CdO composite rods were highly crystalline, and their surfaces were rugged. A comparison of the NO2 gas-sensing properties of the CdO thin film, TiO2 rods, and TiO2–CdO composite rods revealed that the composite rods exhibited superior gas-sensing responses to NO2 gas than did the CdO thin film and TiO2 rods, which can be attributed to the microstructural differences and the formation of heterojunctions between the TiO2 core and CdO crystallites.

1. Introduction

Gas sensors based on oxide semiconductors, such as TiO2, have the potential to detect harmful and toxic gases with high sensitivity [1,2,3,4]. TiO2 nanostructures have a large surface-to-volume ratio because of their one-dimensional structure, which is advantageous in providing high surface effects between the oxide surface and the detected gases. Several studies have investigated methods to fabricate TiO2-based one-dimensional structures with various morphologies for application as gas-sensing devices. For example, the high acetone gas-sensing response of electrospinning-synthesized TiO2 nanorods was investigated at 500 °C [5]. TiO2 nanotubes synthesized through anodization of Ti foil at room temperature were used to detect H2 gas [6]. TiO2 nanowires were synthesized by subjecting sol–gel derived solid thin films to a photolithographic process for application in visible ethanol vapor sensing [7]. TiO2 nanofibers are formed via the reaction of dense polycrystalline TiO2 in a H2/N2 environment at an elevated temperature and are investigated as gas sensing materials [8]. Moreover, gas sensors made from nano-heterostructures are shown to be a promising approach to enhance the gas-sensing response of the oxide semiconductors [9]. To further improve the gas-sensing performance of sensors composed of pure TiO2 nanostructures, TiO2 nanostructures on the surfaces of these sensors can be modified by using binary oxides such as ZnO, SnO2, and In2O3. Many core–shell structures of TiO2-based nanomaterials have been synthesized, and their applications in gas sensing have been investigated. ZnO sheet-decorated TiO2 fibers, synthesized through a combination of the electrospinning technique and the hydrothermal growth method, exhibited a response of 15.7 to 100 ppm ethanol at 280 °C, which is much higher than that of pure TiO2 and ZnO [10]. Heterostructures comprising SnO2 nanoparticles deposited on TiO2 nanobelts through a hydrothermal method exhibited high gas-sensing sensitivity for acetone vapor because of their large surface area [11]. Porous In2O3/TiO2 composite nanofibers synthesized through a facile electrospinning-based synthesis method, followed by appropriate thermal treatment under ambient conditions, exhibited higher gas-sensing responses to NOx gas than those of pure TiO2 nanofibers [12].
Few studies have used CdO—another promising gas-sensing binary oxide semiconductor—to decorate the surfaces of TiO2 for improving its gas-sensing performance toward various toxic gases. CdO has a bandgap in the visible-light region, and its native oxygen vacancies make it an n-type semiconductor with low resistance [13]. CdO thin films and nanostructures have been synthesized and examined through various physical and chemical techniques [14,15,16]. For example, the gas-sensing properties of chemical bath-deposited CdO thin films were studied for sensing liquefied petroleum gas at an operating temperature of 300 °C [17]. Highly crystalline CdO nanostructures prepared through microwave-assisted growth were investigated as the sensing layer in resistive sensors and tested for NO2 sensing [18]. Recently, gas sensors fabricated using composite materials incorporating CdO have been shown to exhibit superior gas-sensing performance than do the constituent individual oxides. For example, two-phase mixed CdO–MnO2 thin films enhanced the performance of the constituent individual oxide films when sensing reduced gases [19]. Moreover, the formation of CdO–ZnO heterostructures improved the applicability of CdO in gas sensors [20]. Incorporating CdO into one-dimensional TiO2 structures is promising for improving the gas-sensing response of one-dimensional TiO2-based sensors. However, limited studies have investigated the gas-sensing properties of one-dimensional TiO2–CdO composites. Therefore, in this study, island-like CdO crystallites were decorated onto TiO2 rods to form a core–shell structure, and the correlation between the microstructure and the gas-sensing performance of TiO2–CdO composite rods for sensing low-concentration NO2 gas was investigated.

2. Materials and Methods

In this study, TiO2 rods sputtering deposited a 100-nm-thick CdO thin film and were used as samples for investigating the structure-dependent NO2 gas-sensing response of the novel TiO2–CdO composite rods. The TiO2 rods were grown on glass substrates using a hydrothermal method in this study. An amount of 7.4 mL of DI water was mixed with 12.6 mL of concentrated HCl (35%) in a Teflon-lined digestion autoclave. The mixture was stirred at ambient conditions for 5 min and after that, 0.25 mL of TiCl4 was added into the mixed solution for preparation of the TiO2 rods. The hydrothermal synthesis was conducted at 180 °C for 3 h. After the synthesis reaction, the autoclave was cooled down to room temperature. Then the samples were removed, washed with DI water, and air dried. TiO2–CdO composite rods were fabricated by sputtering CdO thin films onto the surfaces of the hydrothermally derived TiO2 rod templates. The CdO thin films were fabricated through RF magnetron sputtering using a CdO target in mixed Ar/O2 ambient with a ratio of 20/5 at 350 °C. The working pressure during thin-film deposition was fixed at 2.67 Pa, and the RF sputtering power was fixed at 60 W.
Crystal structures of the as-synthesized samples were investigated by X-ray diffraction (XRD; D2 PHASER, Bruker, Karlsruhe, Germany) using Cu Kα radiation. The surface morphologies of the samples were characterized by scanning electron microscopy (SEM; S-4800, Hitachi, Tokyo, Japan). High-resolution transmission electron microscopy (HRTEM; Tecnai F20 G2, Philips, Amsterdam, The Netherlands) was used to investigate the detailed microstructures of the TiO2–CdO composite rods. The attached energy dispersive X-ray spectroscopy (EDS) was used to investigate the composition of the TiO2 and TiO2–CdO rod samples. The analyses of the transmittance and reflectance spectra of various samples were conducted by using a UV-Vis spectrophotometer (V750, Jasco, Tokyo, Japan). An X-ray photoelectron spectroscopy (XPS; ULVAC-PHI XPS, ULVAC, Chigasaki, Japan) analysis was used to determine the chemical binding status of the constituent elements of the samples. The gas sensing system used in this study consists of a gas flow system consisting of two lines. One is for a cylinder containing the background gas N2; the other one was connected to a cylinder containing diluted NO2 gas. The NO2 concentration for the gas-sensing tests was varied from 1.0 ppm to 5.0 ppm by controlling the relative flow rates of background gas and target gas through mass flow controllers. Before conducting the gas-sensing tests, the test chamber was pumped to a vacuum environment. Subsequently, highly pure nitrogen gas at a consistent flow rate of 1000 sccm was introduced into the test chamber for 10 min; thereafter, the sample holder was heated to the desired temperatures using a direct heating approach. After the electric resistance of the sensors was stabilized, NO2 gas at concentrations of 1.0, 2.5, and 5.0 ppm were introduced into the test chamber to investigate the NO2 gas-sensing performance of the samples. The gas-sensing response of the sensors made from the CdO film, TiO2 rods and TiO2–CdO rods to NO2 gas is defined as the Rg/Ra. Ra is the sensor electrical resistance in the absence of a target gas, and Rg is that in the target gas. The measurements of a gas-sensing response were conducted with various concentrations of NO2 gas. The 100 ppm CO, H2, and NH3 gases were used for a gas-sensing selectivity test. The gas-sensing responses for these reducing gases are defined as Ra/Rg.

3. Result and Discussion

Figure 1a shows the surface topography of a CdO film. The surface was rough and comprised many rounded, surface granular crystallites with a diameter of 20–45 nm. Figure 1b,c depict the morphologies of the TiO2 and TiO2–CdO composite rods. The TiO2 rods were dense and homogeneously distributed over the substrate. The pure TiO2 rods exhibited a smooth surface (inset, Figure 1b). The diameter of the TiO2 rods ranged from 100 to 140 nm, and the tip of the TiO2 rods exhibited a rectangular feature. By contrast, the TiO2 rods coated with CdO shell layers exhibited a rugged surface feature and high surface roughness (Figure 1c). High-magnification SEM revealed that the surfaces of the TiO2–CdO composite rods were comprised of many small, irregular-shaped, and clustered crystallites (inset, Figure 1c).
Figure 2a shows the XRD pattern of a 100-nm-thick CdO thin film. The three distinct Bragg reflections centered at approximately 33.02°, 38.3°, and 55.3° can be ascribed to the (111), (200), and (220) planes of cubic-phase CdO (JCPDS 005-0640). The multiple Bragg reflections in the XRD pattern revealed that the as-synthesized CdO thin film has a polycrystalline feature. Notably, the intense Bragg reflection of (111) revealed that most CdO grains in the film were highly oriented (111). The XRD patterns of the as-synthesized TiO2 rods (Figure 2b) revealed several marked Bragg reflections centered at approximately 27.5°, 36.0°, 39.3°, 41.1°, 44.1°, 54.2°, and 56.7°, which can be ascribed to the crystallographic plane of rutile TiO2 (JCPDS 001-1292); this result indicated that the as-synthesized TiO2 rods are polycrystalline. Figure 2c presents the XRD pattern of the TiO2 rods decorated with CdO crystallites through sputtering deposition, in which the Bragg reflection centered at approximately 33.02° can be ascribed to cubic CdO(111); the appearance of this reflection was consistent with the XRD findings for the CdO thin film, which indicated that the sputtering-deposited CdO thin film had a highly (111)-oriented crystallographic feature.
Figure 3a is a low-magnification TEM image of a single TiO2–CdO composite rod. As shown in the figure, the surface morphology of the shell layer indicated that this layer was comprised of many discontinuous island-like crystallites, and TiO2–CdO exhibited a rugged surface feature. The thickness distribution of the island-like CdO shell layer over the CdO crystallites was inhomogeneous and ranged from 15 to 30 nm. Notably, the thickness of the CdO shell layer on the TiO2 rod surface was less than the original two-dimensional 100-nm-thick CdO film; this was because the deposition of the two-dimensional continuous CdO film onto the three-dimensional free-standing TiO2 rods engendered a large surface dispersion effect and decreased the coverage thickness of the CdO on the TiO2 surface [21]. Figure 3b–e show the high-resolution TEM images of the various outer regions of the composite rod. Several boundaries in the CdS crystallites were visible in these images. The clear and ordered lattice fringes with an interval of approximately 0.27 nm in the CdO crystal corresponded to the {111} lattice plane. The crystalline CdO phase was sputtered onto the surface of the TiO2 rod. EDS spectroscopy revealed that Ti, Cd, and O are the main constituent elements of the composite rod (Figure 3f).
Figure 4a shows the optical transmittance spectrum of the CdO film. The transmittance of the film substantially decreased in the wavelength range of 500–600 nm, indicating that the CdO film has a bandgap in the visible-light region. The optical bandgap of the CdO film was evaluated using the Tauc model [22]. The inset in Figure 4a illustrates the plot of (ahv)2 vs. hv, where a is the absorption coefficient and hv is the photon energy. The bandgap of the CdO film, calculated by extrapolating the linear portion of the curve until it intercepted the horizontal axis (photon energy), was approximately 2.36 eV. Furthermore, the diffuse reflectance spectra of the TiO2 and TiO2–CdO rods were recorded and converted into absorption coefficient spectra by applying the Kubelka–Munk function [23] (Figure 4b). The optical absorbance edge of the TiO2 rods was located in the UV region at a wavelength of approximately 400 nm. The optical bandgap of the TiO2 rods was 3.02 eV (the inset in Figure 4b), which is similar to that reported for rutile TiO2 [24]. Notably, the optical absorbance edge of the TiO2–CdO rods broadened and extended to the visible-light region. This clear red-shift of the optical absorbance edge of the TiO2–CdO rods demonstrated the successful decoration of the CdO crystallites, which has a narrower bandgap, onto the surfaces of the TiO2 rods through sputtering.
Figure 5a presents the narrow-scan Cd 3d XPS spectrum for the CdO film. The Cd 3d XPS spectrum contained the main 3d5/2 and 3d3/2 spin-orbit components with the binding energies of approximately 404.56 and 411.36 eV, respectively. These binding energies are ascribed to the Cd2+ bonding state in the CdO phase [25]. Figure 5b shows the O1s spectrum of the CdO film. The asymmetricity of the spectrum revealed that the as-synthesized CdO film contained oxygen in multiple valence states. The low-binding-energy peak can be attributed to the Cd–O bonds, the medium-binding-energy peak results from the oxygen vacancy in the oxide lattice, and the relatively high-binding-energy peak is associated with the chemisorbed oxygen species on the film surface [26]. Figure 5c depicts the Ti 2p core spectra of the TiO2 rods. The 2p3/2 and 2p1/2 peaks were deconvoluted into four subpeaks. The subpeaks located in the higher-binding-energy regions of the 2p3/2 and 2p1/2 peaks can be assigned to the Ti4+ valence state, whereas those located in the lower-binding-energy regions can be assigned to the Ti3+ valance state. The presence of the mixed Ti4+/Ti3+ valance state indicated the presence of oxygen vacancies in the surfaces of the as-synthesized TiO2 rods [27]. The O1s spectrum of the TiO2 rods exhibited a marked asymmetric curve feature (Figure 5d). The O1s peak was deconvoluted into three subpeaks. The low-binding-energy component can be attributed to the Ti–O bonds, the medium-binding-energy component results from the oxygen vacancy in the oxide lattice, and the high-binding-energy component can be ascribed to the oxygen species chemisorbed from the ambient air [28]. The integrated area ratio of chemisorbed oxygen and the oxygen vacancy was 4.3% and approximately 43.8%, respectively. Figure 5e shows the XPS spectral signal of Cd 3d associated with the island-like CdO crystallites decorated onto the surfaces of the TiO2 rods. Figure 5f shows the Ti 2p core spectra of the surfaces of the TiO2 rods in the TiO2–CdO core–shell composites, which clearly demonstrates the mixed Ti4+/Ti3+ valance state in the TiO2 rods. No substantial differences were observed in the Ti4+/Ti3+ valance state of TiO2 rods with and without decoration with the island-like CdO crystallites. By contrast, the O1s spectral intensity substantially increased in the relatively high-binding-energy region of the TiO2 rods after decoration, revealing an increase in the number of crystal defects and chemisorbed oxygen species on the surfaces of the composite rods [2]. In addition, when the TiO2 rods were decorated with the island-like CdO crystallites, the integrated area ratio of chemisorbed oxygen and oxygen vacancy increased to 8.4% and 45.5%, respectively (Figure 5g). The increased oxygen vacancy in the composite rods can be attributed to the intrinsic crystal defects in the CdO crystallites, and the increase in the number of chemisorbed oxygen species can be attributed to the increase in the surface area of the composite rods due to its rugged surface morphology.
Figure 6 presents the gas-sensing responses of the CdO thin film, TiO2 rods, and TiO2–CdO composite rods as a function of the operating temperature on exposure to 1.0 ppm NO2 gas. To prevent microstructural changes in the deposited CdO thin film, the operating temperature was not increased beyond the CdO thin-film growth temperature of 350 °C. The CdO thin film exhibited its maximum gas-sensing response at a high operating temperature of 325 °C. By contrast, the gas-sensing response of the TiO2 rods and the TiO2–CdO rods peaked at 275 °C. The optimal operating temperature of the oxide sensors is highly associated with the balance between the chemical reactions and the gas diffusion rate [1,29]. Therefore, the differences in the specific surface area of the samples might crucially affect the optimal operating temperatures of the investigated samples. For example, because of its relatively low specific surface area, the CdO thin film required a relatively higher operating temperature to achieve effective chemisorption between the film surface and the reaction gas. By contrast, in one-dimensional TiO2 rods—which have a higher specific surface area than do the two-dimensional CdO thin films—equilibrium between the surface reaction with NO2 gas and the diffusion of NO2 gas to the surface of the TiO2 rods was achieved at a relatively low sensor operating temperature of 275 °C. The optimal operating temperature of the TiO2–CdO rods was similar to that of the TiO2 rods, revealing that the decoration of the TiO2 rods with island-like CdO crystallites did not markedly alter the temperature at which the aforementioned equilibrium was achieved.
Figure 7a–c show the gas-sensing response curves of the CdO film, TiO2 rods, and TiO2–CdO rods on exposure to various NO2 gas concentrations, respectively. The sensor operating temperature for the CdO film is 325 °C and those for the TiO2 and TiO2–CdO rods are 275 °C. TiO2 and CdO are n-type semiconductors; therefore, the resistance of the fabricated sensors increased upon their exposure to NO2 gas. This is because the adsorption of NO2 gas molecules onto the surfaces of the CdO film, TiO2 rods, and TiO2–CdO rods engendered the extraction of surface electrons, resulting in an increase in sensor resistance [30]. The reactions between the NO2 gas molecules and the surface electrons of the CdO film, TiO2 rods, and TiO2–CdO rods are as follows [30]:
NO2(g) + e− → NO2−(ads)
NO2(g)+ e− → NO(g) + O−(ads)
The CdO film, TiO2 rods, and TiO2–CdO rods exhibited evident NO2 gas-sensing behavior on exposure to various NO2 gas concentrations (Figure 7a–c); their gas-sensing responses are summarized in Figure 7d. The responses of the CdO film to 1.0, 2.5, and 5.0 ppm NO2 were approximately 1.78, 2.01, and 2.21, respectively. Those of the TiO2 rods were approximately 3.21, 4.26, and 4.73, respectively, and those of the TiO2 rods decorated with CdO crystallites were higher, at 4.44, 6.21, and 7.41, respectively. The gas-sensing responses of the TiO2−CdO rods were higher than those of the TiO2 rods and CdO film at all investigated NO2 gas concentrations, whereas the CdO film exhibited the lowest responses. In general, the gas-sensing responses of the CdO film, TiO2 rods, and TiO2–CdO rods increased with the NO2 concentration because of the increase in the number of NO2 gas molecules interacting with the surfaces of the samples in the NO2-rich test environment. However, the gas-sensing responses of the CdO film increased by only approximately 24% as the NO2 gas concentration increased from 1.0 to 5.0 ppm, whereas the corresponding change for the TiO2 rods and TiO2–CdO rods was 48% and 67%, respectively. Clearly, the one-dimensional TiO2 rods with a relative large specific surface area are more sensitive to NO2 gas at various gas concentrations than is the CdO film, whereas the sensitivity of TiO2–CdO rods to NO2 gas is even higher than that of the TiO2 rods. This result can be attributed to the differences in the rod surface morphology and the formation of heterojunctions between the TiO2 core and the CdO shell. The rugged and discontinuous island-like CdO crystallites on the surfaces of the TiO2 rods provided more sites for NO2 gas adsorption, as has been reported for one-dimensional semiconductors [31,32]. In addition, crystalline defects, such as surface oxygen vacancies and numerous boundaries in the island-like CdO crystallites, are favorable sites for NO2 absorption, and the presence of more such defects on the surfaces of the TiO2–CdO rods than on the surfaces of the TiO2 rods improved the adsorption efficiency of the TiO2 rods decorated with island-like CdO crystallites. In particular, an increase in oxygen vacancy defects in oxides is highly correlated with an increase in their gas-sensing performance [33]. A similar enhancement in gas-adsorption efficiency has been achieved for TiO2 nanobelts and ZnO nanorods through surface decoration of SnO2 and TiO2 nanoparticles, respectively [11,34]. The formation of TiO2–CdO core–shell heterostructures is expected to bend the energy bands at the TiO2/CdO interface. The interface potential barrier might be another factor to dominate the superior NO2 gas-sensing sensitivity of the TiO2–CdO rods than that of the pure TiO2 rods. Notably, the gas-sensing sensitivity of the TiO2–CdO rods on exposure to 0.25 ppm NO2 gas was still visible and reached to 3.91 in Figure 7e; however, no reliable sensing response curve was obtained for the pure TiO2 rods in this work. Furthermore, the gas-sensing selectivity of the TiO2–CdO rods was investigated on exposure to various target gases in Figure 7f. Comparatively, the TiO2–CdO rods are more sensitive to detect low-concentration NO2 gas in this work. The response times of the TiO2–CdO rods are approximately 41–53 s on exposure to 1.0–5.0 ppm NO2 gas, respectively. The recovery times are in the range of 305–341 s when the TiO2-CdO rods were exposed to 1.0–5.0 ppm NO2 gas, respectively. Table 1 summarized NO2 gas-sensing performance of other one-dimensional TiO2-based heterostructures prepared by various methods [35,36,37,38]. Comparatively, the TiO2–CdO rods have potential in gas sensor applications in detecting low-concentration NO2 gas.
By contrast, a formation of the heterojunction between the TiO2 and CdO is also an important factor that affects the NO2 gas-sensing response of the composite rods. Figure 8 depicts the energy diagram for the TiO2 and CdO phases [39,40]. As evident from the figure, many discontinuous electron-depleted regions were formed at the TiO2 core side when the island-like CdO crystallites discontinuously covered the surfaces of the TiO2 rods. Figure 9 illustrates the effect of interfacial potential barriers on the NO2 gas-sensing response of the TiO2 rods decorated with CdO crystallites. Many discontinuous depletion regions were initially formed over the surface of the TiO2 rods after they were coated with the CdO crystallites. Upon exposure to NO2 gas, the adsorption of the NO2 gas molecules onto the surface of the TiO2 rods resulted in the extraction of the surface electrons. This further induced the formation of a layer-like surface-depletion region on the TiO2 rod surface. The presence of this surface-depletion region markedly decreased the channel size for carrier transportation, increasing the resistance of the sensor made from the TiO2 rods. By contrast, when the TiO2–CdO rod was exposed to the NO2 gas, the inhomogeneous coverage of the island-like CdO crystallites absorbed more NO2 gas molecules onto the surface of the TiO2–CdO rod than did the pure TiO2 rod; this is because of the defective crystalline feature of the CdO and the increased surface area of the composite rod. The relatively large fluctuation in the charge density, caused by the adsorption of NO2 gas molecules onto the surfaces of the TiO2–CdO rods, further affected the size variation of the depletion region [31]. Consequently, the thickness distribution of the depletion regions over the TiO2 rod surface became more inhomogeneous, substantially decreasing the carrier transportation efficiency in the TiO2 rods. Therefore, the variation in sensor resistance on exposure to NO2 gas would be substantially larger for the TiO2–CdO rods than for the pure TiO2 rods. On the basis of the microstructural differences between the TiO2 and TiO2–CdO rods and the formation of numerous interfacial depletion regions in the TiO2–CdO rod, it can be concluded that the TiO2–CdO rods exhibit the highest NO2 gas detection ability among the samples investigated in this study.

4. Conclusions

In summary, TiO2–CdO core–shell composite rods were initially synthesized through a combination of hydrothermal and sputtering methods. Electron microscopy analyses revealed that the surfaces of the as-synthesized TiO2 rods were smooth. Moreover, the decoration of CdO thin film onto the surfaces of the TiO2 rods engendered the formation of a discontinuous shell layer, which comprised many island-like CdO crystallites of varying size. Structural analyses revealed that the as-synthesized TiO2–CdO composite rods were highly crystalline, and the XPS spectra provided evidence that oxygen vacancies exist in the surfaces of the TiO2 rods and CdO crystallites. The superior NO2 gas-sensing response of the TiO2–CdO composite rods relative to that of pure TiO2 rods and the CdO thin film in this study can be attributed to the increased surface area and surface defect density and the formation of the TiO2/CdO heterojunctions.

Acknowledgments

This work is supported by the Ministry of Science and Technology of Taiwan (Grant No. MOST 105-2628-E-019-001-MY3) and the University System of Taipei Joint Research Program (Grant No. USTP-NTUT-NTOU-105-01).

Author Contributions

Yuan-Chang Liang drafted the manuscript. Yuan-Chang Liang and Da-Hua Wei designed the experiments and contributed to data interpretation. Nian-Cih Xu and Chein-Chung Wang carried out the sample preparations, material analyses, and characterization tests. All authors read and approved the final manuscript.

Conflicts of Interest

The authors declare no conflict of interest.

References

  1. Liang, Y.C.; Lee, C.M. Cosputtering crystal growth of zinc oxide-based composite films: From the effects of doping to phase on photoactivity and gas sensing properties. J. Appl. Phys. 2016, 120, 135306–135309. [Google Scholar] [CrossRef]
  2. Liang, Y.C.; Liao, W.K.; Deng, X.S. Synthesis and substantially enhanced gas sensing sensitivity of homogeneously nanoscale Pd- and Au-particle decorated ZnO nanostructures. J. Alloys Compd. 2014, 599, 87–92. [Google Scholar] [CrossRef]
  3. Guillén, M.G.; Gámez, F.; Suárez, B.; Queirós, C.; Silva, A.M.G.; Barranco, Á.; Sánchez-Valencia, J.R.; Pedrosa, J.M.; Lopes-Costa, T. Preparation and Optimization of Fluorescent Thin Films of Rosamine-SiO2/TiO2 Composites for NO2 Sensing. Materials 2017, 10, 124. [Google Scholar] [CrossRef]
  4. Arafat, M.M.; Dinan, B.; Akbar, S.A.; Haseeb, A.S.M.A. Gas Sensors Based on One Dimensional Nanostructured Metal-Oxides: A Review. Sensors 2012, 12, 7207–7258. [Google Scholar] [CrossRef] [PubMed]
  5. Bian, H.; Ma, S.; Sun, A.; Xu, X.; Yang, G.; Gao, J.; Zhang, Z.; Zhu, H. Characterization and acetone gas sensing properties of electrospun TiO2 nanorods. Superlattices Microstruct. 2015, 81, 107–113. [Google Scholar] [CrossRef]
  6. Kılınç, N.; Şennik, E.; Işık, M.; Ahsen, A.Ş.; Öztürk, O.; Öztürk, Z.Z. Fabrication and gas sensing properties of C-doped and un-doped TiO2 nanotubes. Ceram. Int. 2014, 40, 109–115. [Google Scholar] [CrossRef]
  7. Francioso, L.; Taurino, A.M.; Forleo, A.; Siciliano, P. TiO2 nanowires array fabrication and gas sensing properties. Sens. Actuators B 2008, 130, 70–76. [Google Scholar] [CrossRef]
  8. Yoo, S.; Akbar, S.A.; Sandhage, K.H. Nanocarving of titania (TiO2): A novel approach for fabricating chemical sensing platform. Ceram. Int. 2004, 30, 1121–1126. [Google Scholar] [CrossRef]
  9. Miller, D.R.; Akbar, S.A.; Morris, P.A. Nanoscale metal oxide-based heterojunctions for gas sensing: A review. Sens. Actuators B 2014, 204, 250–272. [Google Scholar] [CrossRef]
  10. Lou, Z.; Deng, J.; Wang, L.; Wang, R.; Fei, T.; Zhang, T. A class of hierarchical nanostructures: ZnO surfacefunctionalized TiO2 with enhanced sensing properties. RSC Adv. 2013, 3, 3131–3136. [Google Scholar] [CrossRef]
  11. Wang, X.; Sang, Y.; Wang, D.; Ji, S.; Liu, H. Enhanced gas sensing property of SnO2 nanoparticles by constructing the SnO2–TiO2 nanobelt heterostructure. J. Alloys Compd. 2015, 639, 571–576. [Google Scholar] [CrossRef]
  12. Wu, H.; Kan, K.; Wang, L.; Zhang, G.; Yang, Y.; Li, H.; Jing, L.; Shen, P.; Li, L.; Shi, K. Electrospinning of mesoporous p-type In2O3/TiO2 composite nanofibers for enhancing NOx gas sensing properties at room temperature. Cryst. Eng. Commun. 2014, 16, 9116–9124. [Google Scholar] [CrossRef]
  13. Chandiramouli, R.; Jeyaprakash, B.G. Review of CdO thin films. Solid State Sci. 2013, 16, 102–110. [Google Scholar] [CrossRef]
  14. Yakuphanoglu, F. Nanocluster n-CdO thin film by sol–gel for solar cell applications. Appl. Surf. Sci. 2010, 257, 1413–1419. [Google Scholar] [CrossRef]
  15. Velusamy, P.; Babu, R.R.; Ramamurthi, K.; Elangovan, E.; Viegas, J.; Dahlem, M.S.; Arivanandhan, M. Characterization of spray pyrolytically deposited high mobility praseodymium doped CdO thin films. Ceram. Int. 2016, 42, 12675–12685. [Google Scholar] [CrossRef]
  16. Ueda, N.; Maeda, H.; Hosono, H.; Kawazoe, H. Band-gap widening of CdO thin films. J. Appl. Phys. 1998, 84, 6174–6177. [Google Scholar] [CrossRef]
  17. Bulakhe, R.N.; Lokhande, C.D. Chemically deposited cubic structured CdO thin films: Use in liquefied petroleum gas sensor. Sens. Actuators B 2014, 200, 245–250. [Google Scholar] [CrossRef]
  18. Rajesh, N.; Kannan, J.C.; Leonardi, S.G.; Neri, G.; Krishnakumar, T. Investigation of CdO nanostructures synthesized by microwave assisted irradiation technique for NO2 gas detection. J. Alloys Compd. 2014, 607, 54–60. [Google Scholar] [CrossRef]
  19. Chandiramoulia, R.; Jeyaprakash, B.G. Operating temperature dependent ethanol and formaldehyde detection of spray deposited mixed CdO and MnO2 thin films. RSC Adv. 2015, 5, 43930–43940. [Google Scholar] [CrossRef]
  20. Ban, S.G.; Liu, X.H.; Ling, T.; Dong, C.K.; Yang, J.; Du, X.W. CdO nanoflake arrays on ZnO nanorod arrays for efficient detection of diethyl ether. RSC Adv. 2016, 6, 2500–2503. [Google Scholar] [CrossRef]
  21. Gao, H.; Staruch, M.; Jain, M.; Gao, P.X.; Shimpi, P.; Guo, Y.; Cai, W.; Lin, H.J. Structure and magnetic properties of three-dimensional (La, Sr)MnO3 nanofilms on ZnO nanorod arrays. Appl. Phys. Lett. 2011, 98, 123105. [Google Scholar] [CrossRef]
  22. Baba, K.; Lazzaroni, C.; Nikravech, M. ZnO and Al doped ZnO thin films deposited by Spray Plasma: Effect of the growth time and Al doping on microstructural, optical and electrical properties. Thin Solid Films 2015, 595, 129–135. [Google Scholar] [CrossRef]
  23. Liang, Y.C.; Lung, T.W. Growth of Hydrothermally Derived CdS-Based Nanostructures with Various Crystal Features and Photoactivated Properties. Nanoscale Res. Lett. 2016, 11, 264. [Google Scholar] [CrossRef] [PubMed]
  24. Peia, Z.; Weng, S.; Liu, P. Enhanced photocatalytic activity by bulk trapping and spatial separation of charge carriers: A case study of defect and facet mediated TiO2. Appl. Catal. B 2016, 180, 463–470. [Google Scholar] [CrossRef]
  25. Golestani-Fard, F.; Hashemi, T.; Mackenzie, K.J.D.; Hogarth, C.A. Formation of cadmium stannates studied by electron spectroscopy. J. Mater. Sci. 1983, 18, 3679–3685. [Google Scholar] [CrossRef]
  26. Moholkar, A.V.; Agawane, G.L.; Sim, K.U.; Kwon, Y.B.; Choi, D.S.; Rajpure, K.Y.; Kim, J.H. Temperature dependent structural, luminescent and XPS studies of CdO:Ga thin films deposited by spray pyrolysis. J. Alloys Compd. 2010, 506, 794–799. [Google Scholar] [CrossRef]
  27. Tshabalala, Z.P.; Shingange, K.; Dhonge, B.P.; Ntwaeaborwa, O.M.; Mhlongo, G.H.; Motaung, D.E. Fabrication of ultra-high sensitive and selective CH4 room temperature gas sensing of TiO2 nanorods: Detailed study on the annealing temperature. Sens. Actuator B 2017, 238, 402–419. [Google Scholar] [CrossRef]
  28. Devi, L.G.; Nithya, P.M.; Abraham, C.; Kavitha, R. Influence of surface metallic silver deposit and surface fluorination on the photocatalytic activity of rutile TiO2 for the degradation of crystal violet a cationic dye under UV light irradiation. Mater. Today Commun. 2017, 10, 1–13. [Google Scholar] [CrossRef]
  29. Liang, Y.C.; Lee, C.M.; Lo, Y.J. Reducing gas-sensing performance of Ce-doped SnO2 thin films through a cosputtering method. RSC Adv. 2017, 7, 4724–4734. [Google Scholar] [CrossRef]
  30. Liang, Y.C.; Cheng, Y.R. Combinational physical synthesis methodology and crystal features correlated with oxidizing gas detection ability of one-dimensional ZnO–VOx crystalline hybrids. CrystEngCommun 2015, 17, 5801–5807. [Google Scholar] [CrossRef]
  31. Liang, Y.C.; Lina, T.Y.; Lee, C.M. Crystal growth and shell layer crystal feature-dependent sensing and photoactivity performance of zinc oxide–indium oxide core–shell nanorod heterostructures. CrystEngCommun 2015, 17, 7948–7955. [Google Scholar] [CrossRef]
  32. Liang, Y.C.; Liu, S.L.; Hsia, H.Y. Physical synthesis methodology and enhanced gas sensing and photoelectrochemical performance of 1D serrated zinc oxide-zinc ferrite nanocomposites. Nanoscale Res. Lett. 2015, 10, 350–356. [Google Scholar] [CrossRef] [PubMed]
  33. Yu, L.; Guo, F.; Liu, S.; Yang, B.; Jiang, Y.; Qi, L.; Fan, X. Both oxygen vacancies defects and porosity facilitated NO2 gas sensing response in 2D ZnO nanowalls at room temperature. J. Alloys Compd. 2016, 682, 352–356. [Google Scholar] [CrossRef]
  34. Zou, C.W.; Wang, J.; Xie, W. Synthesis and enhanced NO2 gas sensing properties of ZnO nanorods/TiO2 nanoparticles heterojunction composites. J. Colloid Interface Sci. 2016, 478, 22–28. [Google Scholar] [CrossRef] [PubMed]
  35. Wang, L.; Gao, J.; Wu, B.; Kan, K.; Xu, S.; Xie, Y.; Li, L.; Shim, K. Designed Synthesis of In2O3 Beads@TiO2–In2O3 Composite Nanofibers for High Performance NO2 Sensor at Room Temperature. ACS Appl. Mater. Interfaces 2015, 7, 27152–27159. [Google Scholar] [CrossRef] [PubMed]
  36. Epifani, M.; Comini, E.; Díaz, R.; Force, C.; Siciliano, P.; Fagli, G. TiO2 colloidal nanocrystals surface modification by V2O5 species: Investigation by Ti MAS-NMR and H2, CO and NO2 sensing properties. Appl. Surf. Sci. 2015, 351, 1169–1173. [Google Scholar] [CrossRef]
  37. Zhao, P.X.; Tang, Y.; Mao, J.; Chen, Y.X.; Song, H.; Wang, J.W.; Song, Y.; Liang, Y.Q.; Zhang, X.M. One-Dimensional MoS2-Decorated TiO2 nanotube gas sensors for efficient alcohol sensing. J. Alloys Compd. 2016, 674, 252–258. [Google Scholar] [CrossRef]
  38. Arafat, M.M.; Haseeb, A.S.M.A.; Akbar, S.A.; Quadir, M.Z. In-situ fabricated gas sensors based on one dimensional core-shell TiO2-Al2O3 nanostructures. Sens. Actuator B 2017, 238, 972–984. [Google Scholar] [CrossRef]
  39. Yang, Z.; Wang, B.; Zhang, J.; Cui, H.; Pan, Y.; An, H.; Zhai, J. Factors influencing the photocatalytic activity of rutile TiO2 nanorods with different aspect ratios for dye degradation and Cr(VI) photoreduction. Phys. Chem. Chem. Phys. 2015, 17, 18670–18676. [Google Scholar] [CrossRef] [PubMed]
  40. Saravanan, R.; Shankar, H.; Prakash, T.; Narayanan, V.; Stephen, A. ZnO/CdO composite nanorods for photocatalytic degradation of methylene blueunder visible light. Mater. Chem. Phys. 2011, 125, 277–280. [Google Scholar] [CrossRef]
Materials 10 00778 g001 550
Figure 1. (a) SEM image of the CdO film. (b) SEM image of the TiO2 rods. (c) SEM image of the TiO2–CdO rods.
Figure 1. (a) SEM image of the CdO film. (b) SEM image of the TiO2 rods. (c) SEM image of the TiO2–CdO rods.
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Materials 10 00778 g002 550
Figure 2. (a) XRD pattern of the CdO film. (b) XRD pattern of the TiO2 rods. (c) XRD pattern of the TiO2–CdO rods.
Figure 2. (a) XRD pattern of the CdO film. (b) XRD pattern of the TiO2 rods. (c) XRD pattern of the TiO2–CdO rods.
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Materials 10 00778 g003 550
Figure 3. TEM analyses of the TiO2–CdO composite rod: (a) Low-magnification TEM image of the TiO2–CdO rod; (b–e) HRTEM images taken from the local regions of the rod; (f) EDS spectra of Ti, Cd, and O elements taken from the rod.
Figure 3. TEM analyses of the TiO2–CdO composite rod: (a) Low-magnification TEM image of the TiO2–CdO rod; (b–e) HRTEM images taken from the local regions of the rod; (f) EDS spectra of Ti, Cd, and O elements taken from the rod.
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Figure 4. (a) Transmittance spectrum of the CdO film. The inset in (a) shows the Tauc plot of the CdO film. (b) Absorbance spectra of the TiO2 and TiO2–CdO rods. The inset in (b) shows the bandgap of the TiO2 rods is approximately 3.02 eV.
Figure 4. (a) Transmittance spectrum of the CdO film. The inset in (a) shows the Tauc plot of the CdO film. (b) Absorbance spectra of the TiO2 and TiO2–CdO rods. The inset in (b) shows the bandgap of the TiO2 rods is approximately 3.02 eV.
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Figure 5. XPS narrow scan analyses for the CdO thin film, TiO2 rods, and TiO2–CdO composite rods: (a) Cd 3d core-level doublet peaks of the CdO thin film; (b) O1s core-level spectrum of the CdO thin film; (c) Ti 2p core-level spectra of the TiO2 rods; (d) O1s core-level spectrum of the TiO2 rods; (e) Cd 3d core-level doublet peaks of the TiO2–CdO composite rods; (f) Ti 2p core-level spectra of the TiO2–CdO composite rods; (g) O1s core-level spectrum of the TiO2–CdO composite rods.
Figure 5. XPS narrow scan analyses for the CdO thin film, TiO2 rods, and TiO2–CdO composite rods: (a) Cd 3d core-level doublet peaks of the CdO thin film; (b) O1s core-level spectrum of the CdO thin film; (c) Ti 2p core-level spectra of the TiO2 rods; (d) O1s core-level spectrum of the TiO2 rods; (e) Cd 3d core-level doublet peaks of the TiO2–CdO composite rods; (f) Ti 2p core-level spectra of the TiO2–CdO composite rods; (g) O1s core-level spectrum of the TiO2–CdO composite rods.
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Figure 6. Gas sensing response value vs. operating temperature of the CdO film, TiO2 rods, and TiO2–CdO rods.
Figure 6. Gas sensing response value vs. operating temperature of the CdO film, TiO2 rods, and TiO2–CdO rods.
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Figure 7. Gas sensing response curves of various samples on exposure to various concentrations of NO2 gas (1.0, 2.5, and 5.0 ppm) at various temperatures: (a) CdO film at 325 °C; (b) TiO2 rods at 275 °C; (c) TiO2–CdO rods at 275 °C; (d) Gas sensing response values vs. NO2 gas concentration for various samples; (e) Gas sensing response curve of the TiO2–CdO rods on exposure to 0.25 ppm NO2 gas; (f) Gas sensing selectivity histogram of the TiO2–CdO rods tested to 5 ppm NO2 and 100 ppm of CO, H2, and NH3.
Figure 7. Gas sensing response curves of various samples on exposure to various concentrations of NO2 gas (1.0, 2.5, and 5.0 ppm) at various temperatures: (a) CdO film at 325 °C; (b) TiO2 rods at 275 °C; (c) TiO2–CdO rods at 275 °C; (d) Gas sensing response values vs. NO2 gas concentration for various samples; (e) Gas sensing response curve of the TiO2–CdO rods on exposure to 0.25 ppm NO2 gas; (f) Gas sensing selectivity histogram of the TiO2–CdO rods tested to 5 ppm NO2 and 100 ppm of CO, H2, and NH3.
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Figure 8. Energy diagram of the TiO2 and CdO phases.
Figure 8. Energy diagram of the TiO2 and CdO phases.
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Figure 9. A schematic of gas sensing mechanisms for the TiO2 and TiO2–CdO rods on exposure to NO2 gas. The size of arrows represented the current degree in the TiO2.
Figure 9. A schematic of gas sensing mechanisms for the TiO2 and TiO2–CdO rods on exposure to NO2 gas. The size of arrows represented the current degree in the TiO2.
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Table
Table 1. Comparisons of NO2 gas-sensing performance of various low-dimensional, TiO2–based composites.
Table 1. Comparisons of NO2 gas-sensing performance of various low-dimensional, TiO2–based composites.
MaterialsSynthesis MethodNO2 Sensing ConditionResponseResponse Time/Recovery TimeResponse DefinitionRef.
TiO2−In2O3Electrospinning2.9 ppm/RT3.58 s/56 s(Rg–Ra)/Ra
(N-type behavior)		[35]
TiO2–V2O5Sol–gel and solvothermal methods2 ppm/200 °C0.8N/A(Rg–Ra)/Ra
(N-type behavior)		[36]
TiO2–MoS2Anodization and hydrothermal methods100 ppm/150 °C1.1N/ARa/Rg
(P-type behavior)		[37]
TiO2–Al2O3Thermal oxidation1000 ppm/650 °C1.9180 s/180 sRg/Ra
(N-type behavior)		[38]
TiO2–CdOHydrothermal and sputtering methods5 ppm/275 °C7.4153 s/341 sRg/Ra
(N-type behavior)		Present work

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MDPI and ACS Style

Liang, Y.-C.; Xu, N.-C.; Wang, C.-C.; Wei, D.-H. Fabrication of Nanosized Island-Like CdO Crystallites-Decorated TiO2 Rod Nanocomposites via a Combinational Methodology and Their Low-Concentration NO2 Gas-Sensing Behavior. Materials 2017, 10, 778. https://doi.org/10.3390/ma10070778

AMA Style

Liang Y-C, Xu N-C, Wang C-C, Wei D-H. Fabrication of Nanosized Island-Like CdO Crystallites-Decorated TiO2 Rod Nanocomposites via a Combinational Methodology and Their Low-Concentration NO2 Gas-Sensing Behavior. Materials. 2017; 10(7):778. https://doi.org/10.3390/ma10070778

Chicago/Turabian Style

Liang, Yuan-Chang, Nian-Cih Xu, Chein-Chung Wang, and Da-Hua Wei. 2017. "Fabrication of Nanosized Island-Like CdO Crystallites-Decorated TiO2 Rod Nanocomposites via a Combinational Methodology and Their Low-Concentration NO2 Gas-Sensing Behavior" Materials 10, no. 7: 778. https://doi.org/10.3390/ma10070778

APA Style

Liang, Y. -C., Xu, N. -C., Wang, C. -C., & Wei, D. -H. (2017). Fabrication of Nanosized Island-Like CdO Crystallites-Decorated TiO2 Rod Nanocomposites via a Combinational Methodology and Their Low-Concentration NO2 Gas-Sensing Behavior. Materials, 10(7), 778. https://doi.org/10.3390/ma10070778

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