Sol-gel cobalt oxide-silica nanocomposite thin films for gas sensing applications

Various metal oxide-silica nanocomposite films have been recently proposed as gas-sensitive materials. This paper presents results on cobalt oxide-SiO₂ mesoporous nanocomposite thin films templated by a cationic surfactant. The films were deposited on glass substrate by dip-coating process, using [Co(CH₃COO)₂]·4H₂O and tetraethoxysilane (TEOS) as starting materials. The effect of withdrawal speed, number of layers and thermal treatment on the crystalline structure, morphology, Co-doping states, optical, electrical and gas sensing properties of the thin films has been investigated using X-ray diffraction, atomic force microscopy, X-ray photoelectron spectroscopy, optical transmittance and room temperature photoreduction-oxidation data.     

Effect of Si substrate on ethanol gas sensing properties of ZnO films

We prepared ZnO/n-Si heterojunctions by depositing ZnO films on n-Si substrates with different resistivities by radio-frequency magnetron sputtering. The microstructure of ZnO film was analyzed by X-ray diffraction and scanning electron microscopy. The current-voltage characteristics and ethanol gas sensing properties of the junctions were investigated at room temperature. It is found that optimization of n-Si substrate resistivity is critical to enhance the ethanol gas sensitivity of ZnO/n-Si heterojunction. The ZnO/n-Si heterojunction with n-Si substrate of 2-3 Ω cm exhibits the best ethanol gas sensing property. The junction shows the sensitivity of 29.41% to 0.24 g/L ethanol gas under + 0.52 V forward bias voltage.     

Influence of crystallinity on CO gas sensing for TiO2 films

In the present research, carbon monoxide (CO) gas sensing response was studied for TiO₂ thick films calcined and sintered between 700 and 900 °C. Crystalline phase, crystallite size, surface area, particle size, and amorphous content were measured for the calcined powder. Crystallinity of the powder was found to affect sensing response significantly towards CO. Anatase phase of TiO₂ thick film was stable up to 900 °C however, as calcination temperature increased from 700 to 900 °C, surface area and amorphous phase content decreased. Films calcined and sintered at 700 °C showed a lower response towards CO than those calcined at 800 °C. Upon increasing the calcination temperature further, particle growth and reduced surface area hindered the sensing response. A calcination temperature of 800 °C was necessary to achieve sufficient order in the crystal structure leading to more efficient adsorption and desorption of oxygen ions on the surface of TiO₂.     

Hybrid nanocomposite based on NbWO6 nanosheets and polyaniline

Synthesis and characterization of the hybrid nanocomposite based on polyaniline and NbWO₆ nanosheets is reported here. Formation of the nanocomposite is reflected by the increase of interlayer distance of NbWO₆ nanosheets and the XRD pattern depicts the formation of NbWO₆/polyaniline nanostructure with interlayer separations of 1.6 nm and 0.9 nm which is consistent with a bilayer and a monolayer of polyaniline molecules within the gallery of nanosheets. Transmission electron micrographs, infrared spectra and thermograms support the formation of the hybrid nanocomposite. Electrochemical investigations on the nanocomposite reveal the presence of polyaniline and the data is compared also with those of polyaniline and host.     

不同形貌纳米炭/聚苯胺复合材料对超级电容器电化学性能的影响

通过原位化学聚合制备了不同形貌的纳米炭材料(炭黑,碳纳米管及石墨烯纳米片)/聚苯胺复合电极材料.分析表明:石墨烯/聚苯胺复合材料相比于炭黑/聚苯胺、碳纳米管/聚苯胺复合物及纯聚苯胺,具有产率和比容量高,内阻低及明显提高的循环稳定性和倍率性能.石墨烯/聚苯胺复合材料更好的电化学性能归因于:(a)二维平面结构石墨烯有利于大量聚苯胺在其表面均匀沉积及更多的活性位使聚苯胺和电解液离子接触,从而有利于聚苯胺得失电子促使氧化还原反应的顺利进行;(b)石墨烯间的面接触有利于构建电子的快速传输网络使电极材料具有更低的电阻;(c)石墨烯及聚苯胺层层堆叠结构具有柔性包覆限制作用,可有效防止聚苯胺在充放电过程中因膨胀和收缩而从石墨烯表面脱离.     

Characterization of metal-modified and vertically-aligned carbon nanotube films for functionally enhanced gas sensor applications

Carbon nanotube (CNT) networked films have been grown by radiofrequency plasma enhanced chemical vapour deposition (RF-PECVD) technology onto low-cost alumina substrates, coated by nanosized Fe-catalyst for growing CNTs, to perform chemical detection of hazardous gases, at an operating sensor temperature in the range 25-150 °C. The morphology and structure of the CNT networks have been characterized by scanning electron microscopy (SEM), transmission electron microscopy (TEM) and Raman spectroscopy. The carbon nanotubes were “forest-like” with ropes vertically-aligned to the substrate surface. A dense network of bundles of multiple tubes consisting of multi-walled carbon nanostructures appears with a maximum length of 7-10 μm and single-tube diameter varying in the range of 5-35 nm. Surface functionalizations of the vertically-aligned CNT networks with nominally 5 nm thick Pt-, Ru- and Ag-nanoclusters, prepared by magnetron sputtering, provide higher sensitivity for significantly enhanced gas detection of NO₂, H₂, ethanol and toluene up to a low limit of sub-ppm level. The measured electrical conductance of the functionalized CNTs upon exposures of a given oxidizing and reducing gas is modulated by a charge transfer model with p-type semiconducting characteristics. Functionalized CNT gas sensors exhibited better performances compared to unmodified CNTs, making them highly promising candidates for environmental air monitoring applications, at ppb-level of toxic gas detection.     

Theoretical study of the gas sensitivity and response time of metal oxide thin films

In this paper, based on the gas sensitive mechanism of metal oxide semiconductor thin film, the law of gas diffusion, first order aerodynamics and the relative assumption, we present a simple model for the simulation of the steady state gas sensitivity of metal oxide thin film. Our model provides a general mathematical relationship between the steady state sensitivity and the film thickness. The metal oxide semiconductor thin film is supposed to be formed with a finite number of independent layers. Each layer consists of ideally spherical grains with close-packed structure. The target gas is assumed to affect the inner layers either by penetrating through the grain boundaries or by direct interacting with each layer surface. Besides we propose a model to analyze the thickness dependence of the response time for metal oxide gas-sensing film.     

Dissolution of Cu nanoparticles and antibacterial behaviors of TaN-Cu nanocomposite thin films

Previous study shows that TaN-Cu nanocomposite thin films can have both anti-wear and antibacterial properties. Both properties are dependent on the size and density of the surfaced Cu particles. The present study made an attempt to correlate the annealing conditions to the dissolving rate of Cu particles surfaced on TaN, which eventually decides the films' antibacterial performance. Cu powders with different particle sizes were first used to study the size effect on the Cu powders' dissolving behavior. The results were then used to understand the antibacterial performance of TaN-Cu nanocomposite thin films prepared under various conditions. It is found that the films with nano-sized Cu particles could respond faster in terms of antibacterial performance. When in contact with the TaN film, these Cu particles can have an even higher dissolving rate caused by galvanic effect. This implies that the annealed TaN-Cu nanocomposite thin films may have a different antibacterial function due to the difference in the particle size and density of surfaced Cu. Overall, the results imply that both short and long term antibacterial functions of these films can be controlled, provided that the emerged particle size and density of Cu are controlled.     

Carbon nanotubes/ceria composite layers deposited on surface acoustic wave devices for gas detection at room temperature

Surface acoustic wave (SAW) sensor on ATquartz piezoelectric substrate has been designed and fabricated. Test devices were based on asynchronous single-port resonators operating near the 434-MHz-centered industrial, scientific, and medical band. Multi-Walled Carbon Nanotubes/Ceria (MWNTs/CeO₂) nanocomposites were used as sensitive layers. The MWNTs were synthesized by catalytic chemical vapor deposition method and coated with nanosized ceria oxide. The composites were deposited on SAW quartz resonator using air-brush technique. MWNTs/CeO₂ nanocomposites were characterized using X-ray diffraction, transmission electron and atomic force microscopy. The sensor responses were tested under acetone (C₃H₅OH) and ethanol (C₂H₅OH) gases. The output signal was done by S₁₁ parameter of the SAW device and was monitored using a network analyzer. Frequency changes were observed under acetone and ethanol vapors. These changes depended on the surface conductivity of the nanocomposites deposited on the sensor. The single-port SAW gas sensor coated with the MWNTs/CeO₂ presented the highest sensitivity in the case of acetone vapor interacting with these layers, with a frequency shift of 200 kHz at room temperature.     

气体配比对硼掺杂碳纳米管生长特性的影响

采用电子回旋共振微波等离子体化学气相沉积技术（ECR-CVD）,以Fe3O4纳米粒子为催化剂,CH4 、B2H6和H2为气源,在多孔硅基底上制备出了掺硼碳纳米管.研究了不同B2H6/CH4气体配比对碳纳米管生长特性的影响.使用扫描电子显微镜（SEM）、透射电子显微镜（TEM）和X射线光电子谱（XPS）对样品的形貌、结构及组分进行表征.结果表明：B2H6对纳米管的生长具有较大影响.气源中含有少量的B2H6就会破坏纳米管的定向生长,使纳米管变得弯曲;随着气源中B2H6比例的增加,纳米管结构从中空结构转变为类竹节结构,多壁管外径由60 nm～90 nm增大至200 nm～250 nm,管壁由10 nm～20 nm增厚至70 nm～100 nm,表面变得粗糙,同时纳米管的生长速度降低;纳米管中的B/C原子比随着B2H6比例的增大而增大,当B2H6/CH4体积配比为2：1时B/C原子比增至28：72.     

Determination of the dopant weight fraction in polyaniline films using a quartz-crystal microbalance

The electrical conductivity of polyaniline depends on factors such as degree of oxidation, type of protonation, and dopant weight fraction. The last of these factors is connected with the loss of mass during the deprotonation of polyaniline, and can thus conveniently be determined in situ by the use of a quartz microbalance. This is illustrated in the present paper which concerns the determination of the weight fraction of acid in thin polyaniline films prepared by the chemical oxidation of aniline in the aqueous solutions of sulfuric and phosphoric acids. It is illustrated that the deprotonation-reprotonation processes are fast, complete, and reversible. Polyaniline has sulfate counter-ions in 0.1 M sulfuric acid while, in 0.5-1 M sulfuric acid, hydrogen sulfate counter-ions are present. The quartz microbalance involving polyaniline films can be used in the sensing of the acidity.     

Preparation and tribological properties of novel carbon nanotube self-assembled composite films

Carbon nanotube (CNT) composite thin films were prepared on a single-crystal silicon substrate by a self-assembling process from a specially formulated solution. Rare earth solution (RES) surface modification and appropriate acid-treatment methods were used to functionalise carbon nanotubes (CNTs). Silane coupling regent (3-mercaptopropyl trimethoxysilane (MPTS)) was prepared first. The terminal thiol groups (–SH) in the film was oxidised to sulphonic acid groups (–SO₃H) in situ to enhance the film with good chemisorption ability. Treated Caron nanotubes were deposited on the oxidised MPTS–SAM by means of chemisorption with the SO₃H group. The surface energy, chemical composition, phase transformation and surface morphology of the films were analysed using contact angle measurements, X-ray photoelectron spectroscopy (XPS), scanning electron microscope (SEM) and atomic force microscopy. As a result, a conclusion could be made that some lanthanum elements react with –SO₃H groups on the surface of the substrate by a chemical bond, which will improve the bonding strength between the films and the CNTs. Since the CNT thin films were well adhered to the silicon substrate, it might find promising application in the surface-modification of single-crystal Si and SiC in microelectromechanical systems (MEMS).     

多孔SnO2薄膜的导电和气敏特性

用RGTO方法制备多孔、颗粒状SnO2薄膜；根据SEM观察结果建立简单导电模型，并验证其导电机制主要是晶界导电；研究纯SnO2薄膜及掺杂SnO2薄膜对CO，乙醇等气体的气敏特性。掺Pt的薄膜对CO有很好的气敏响应；选择合适工作温度，可提高灵敏度改善选择性，用此种方法制得的薄膜具有良好的长期稳定性、非常短的响应和恢复时间等特点。     

Temperature enhanced gas sensing properties of diamond films

Nanocrystalline diamond (NCD) film was used as a functional part of gas sensor. The gas sensing properties of H-terminated nanocrystalline diamond films were examined to oxidizing gases (i.e., COCl₂ and humid air). Pronounced increase in the surface conductivity (3 orders of magnitude) was found after sensor exposure to phosgene gas and was explained by the surface transfer doping effect. We also present a possible way how to achieve sensor selectivity, i.e. how to distinguish between phosgene and humid air (the mostly present background gas in a common environment).     

Experimental investigations on barium titanate nanocomposite thin films as an opto-electronic humidity sensor

This article reports the synthesis and characterisation of Barium titanate (BaTiO₃) nanocomposite and its application as opto-electronic humidity sensor. Titanium tetrachloride and barium hydroxide were mixed in molar ratio 1?:?1 in deionised water under continuous stirring at room temperature. Later, sodium hydroxide solution was added to above solution with continuous stirring. Finally, BaTiO₃ gel was obtained. The synthesised nano-composite material was characterised using a scanning electron microscope, X-ray diffraction (XRD) and UV-Visible spectrophotometer. SEM image of the composite film shows that the film is porous having uniform grains. From XRD the minimum crystallite size of BaTiO₃ was found to be 8?nm using Debye–Scherer formula. UV-Visible absorption spectroscopy was used for optical characterisation of the film. It was found that the optical band gap of the composite material was 3.50?eV. Barium titanate thin film was deposited on the base of an equilateral prism using sol–gel spin coating process at 4000?rpm. The humidity sensing properties of the film was investigated at different angles of incidence. It was observed that the intensity of reflected light increased with an increase in relative humidity (%RH) in the range 5–95% at a particular angle of incidence. Sensing element has maximum sensitivity ～6?µW/%RH, which is quite significant for sensor fabrication purposes.     

Nanocomposite por-Si/SnOx layers formation for gas microsensors

Hetero-phase nanocomposite layers based on porous silicon and nonstoichiometric tin oxide (por-Si/SnO_x) were obtained by the chemical vapor deposition (CVD), magnetron sputtering, and molecular layer deposition methods. The structure, and the atomic and phase compositions of the nanocomposites were studied by means of transmission electron microscopy, energy-dispersive X-ray analysis (EDX), scanning electron microscopy, Raman spectroscopy, Auger spectroscopy, and X-ray photoelectron spectroscopy. The obtained data were indicative of the formation of por-Si/SnO_x nanocomposite layers up to 2 μm thick with x = 1.0-2.0. According to EDX data, in magnetron sputtering process the formation of por-Si/SnO_x nanocomposite layers proceeds on the externally exposed surface of polycrystalline por-Si skeleton elements with subsequent diffusion of tin atoms into the pores along the por-Si walls. The other two methods lead to formation of large SnO_x islands covering pores in the por-Si structure. Enhanced diffusion of tin atoms into porous matrix with D_eff ≈ 1 × 10⁻¹⁴ cm²/s was observed in samples annealed at 500 °C. Sensor heterostructures based on magnetron sputtered por-Si/SnO_x nanocomposite layers show high sensitivity to NO₂ environmental molecules and remarkable stability, thus offering promise in gas sensing applications.     

Ordered mesoporous ZnO for gas sensing

We report on the synthesis and the gas-sensing properties (CO and NO₂ detection) of mesoporous zinc oxide. A two-step structure replication method for the synthesis is employed. In the first step mesoporous SBA-15 silica is prepared by the utilization of self-organization of amphiphilic organic agents. This mesoporous silica is used as the structure matrix for synthesizing mesoporous carbon CMK-3, which, in turn, is employed for yet another replication step, using zinc nitrate as the precursor. The resulting material is characterized by X-ray diffraction and nitrogen physisorption and its gas-sensing properties are compared with a non-porous ZnO sample.     

Photocatalytic and antibacterial properties of TaON-Ag nanocomposite thin films

TaON-Ag nanocomposite thin films with Ag nano-particles embedded in TaON were prepared by reactive co-sputtering of Ta and Ag in the plasma of (O₂ + N₂)/Ar. The deposition temperature was either at room temperature or 300 °C. These films were characterized mainly by UV-Vis photometry and scanning electron microscopy. It is found that Ag doping into the TaON films leads to several beneficial changes on film properties. It would reduce the optical band gap and, therefore, enhance the films' photocatalytic behavior. It is also found that Ag nano-particles may emerge on the surface of TaON with or without RTA. This could be much meaningful since Ag particles' appearance is closely related to the antibacterial property of TaON-Ag films. The results show that TaON-Ag films deposited at 300 °C have an outstanding antibacterial behavior with the illumination of visible light due to the synergistic effects of Ag and photocatalytic behavior of TaON.     

Preparation and photochromism of nanocomposite thin film based on polyoxometalate and polyethyleneglycol

A photochromic nanocomposite based on Keggin structure phosphomolybdic acid (PMoA) well dispersed in polyethyleneglycol (PEG) was fabricated. TEM image showed that PMoA nanoparticles with narrow size distribution were finely dispersed in polymer matrix. FT-IR results showed that the Keggin geometry of polyoxometalates was still preserved inside the composites and strong coulombic interaction was built between PMoA and polymer matrix. Under UV irradiation, the film was reduced photochemically to yield a blue species, which was in accordance with a charge-transfer mechanism.     

Surface and mechanical characterization of TaN-Ag nanocomposite thin films

TaN-Ag nanocomposite thin films with Ag nano-particles dispersed in TaN matrix and surface were prepared by reactive co-sputtering of Ta and Ag in the plasma of N₂ and Ar. After deposition, the films were annealed using RTA (Rapid Thermal Annealing) at 350 °C for 2, 4, 8 min respectively to induce the nucleation and growth of Ag particles. C-AFM (Conductive-atomic Force Microscopy) and SSPM (Surface Scanning Potential Microscopy) were applied to characterize the emergence of Ag nano-particles on the surface of TaN-Ag thin films in this study. It is seen that Ag nano-particles may emerge in the matrix and on the surface of TaN and, possibly, grow. The results are compared with that obtained by FE-SEM (field-emission scanning electron microscopy). After comparison, C-AFM and SSPM are seen to be useful in characterizing the emergence and distribution of Ag particles. The results also show that the films' hardness and Young's modulus values would increase or decrease with the increase of annealing time, depending on Ag content and annealing time. This behavior is similar to that of TaN-Cu nanocomposite film. In addition, the increase of wear resistance of these coatings is proved.