Preparation,characterization of 1D ZnO nanorods and their gas sensing properties

The 1D ZnO nanorods (NR's) were grown with Zinc (Zn) ion precursor concentration variation on seed layer glass substrate by the low temperature hydrothermal method and utilized for nitrogen dioxide (NO₂) gas sensing application. Zn ion precursor concentration varied as 0.02, 0.03, 0.04, 0.05 and 0.06 M and thin films were characterized for structural, morphological, optical, electrical, surface defect study and gas sensing properties. All the film showed dominant orientation along the (002) direction, the intensity of the peak vary with the length of the nanorods. SEM cross images confirmed that nanorods had vertical alignment perpendicular to the plane of the substrate surface. The PL intensity of oxygen vacancy related defects for prepared samples was found to be linearly proportional to gas sensing phenomena. This result in good agreement with the theoretical postulation that, oxygen vacancies plays the important role for adsorption sites to NO₂ molecule. The gas sensing performance was studied as a function of operating temperature, Zn ion precursor concentration variation, and gas concentration. The maximum gas response is 113.32–100 ppm NO₂ gas at 150 °C for 0.05 M sample out of all prepared samples. Additionally, ZnO thin film sensor has potential to detect NO₂ as low as 5 ppm.     

Dispersant-assisted low frequency electrophoretically deposited TiO2 nanoparticles in non-aqueous suspensions for gas sensing applications

The effect of dispersant on deposition mechanism of TiO₂ nanoparticles at 1 Hz under non-uniform AC fields was investigated. It was found that by adding Dolapix to suspension, deposition pattern is drastically changed enabling particles to enter the gap leaving the electrodes intact. Using low frequency AC electrophoretic deposition technique in the presence of dispersant, we succeeded in fabricating gas sensor in less than 2 min. Gas sensing measurements were performed in the temperature range of 450–550 °C. The results explained that the sensor has good stability in time and repeatability performance toward high response. The maximum sensitivity of about 180 for the TiO₂ nanoparticles sensor is observed with 47 ppm NO₂ gas and the response and recovery times is about 60–150 s. The optimum temperature of the gas sensor was obtained in 450 °C where sensor showed a linear trend up to 50 ppm of NO₂ gas. This sensing behavior in un-doped TiO₂ as NO₂ sensor can be mainly ascribed to the porous structure of the sensing film and its good contacts to the substrate and electrode assembly.     

Characterization and gas sensing properties of bead-like ZnO using multi-walled carbon nanotube templates

We report bead-like ZnO nanostructures for gas sensing applications, synthesized using multi-walled carbon nanotube (MWCNT) templates. The ZnO nanostructures are grown following a two-step process: in the first, ZnO nanoparticles are synthesized on MWCNTs by thermal evaporation of a Zn powder; and in the second, the hybrid nanostructures are heat-treated at 800 °C. Scanning and transmission electron microscopy images indicate that the bead-like ZnO nanostructures have surface protuberances with nanoparticle sizes ranging from 20 to 60 nm, and a well-crystallized hexagonal structure. Gas sensors based on multiple-networked bead-like ZnO showed considerably enhanced electrical responses and better stability to both oxidizing (NO₂) and reducing (CO) gases compared with previously reported nanostructured gas sensors, even if the response to CO gas was slow to increase. Both the NO₂ and CO gas sensing properties increased dramatically when the working temperature was increased up to 300 °C. The response sensitivities measured were 2953%, 5079%, 9641%, 3568%, and 3777% to 20 ppm NO₂ at 200, 250, 300, 350 and 400 °C, respectively. For CO gas on the other hand, the response sensitivities were 107%, 110%, 114%, 118%, and 122% at 5, 10, 20, 50, and 100 ppm concentrations, respectively. For concentrations between 5 and 20 ppm, the recovery time of the oxidizing gas was much shorter than the response time. The origin of the NO₂/CO gas sensing mechanism of the bead-like ZnO nanostructures is discussed.     

Novel synthesis of CuO nanofiber balls and films and their UV–visible light filteration property

Self-assembled cupric oxide (CuO) nanofiber balls and films were synthesized via a facile solvothermal route directly from cupric acetate monohydrate (Cu(CH₃COO)₂·H₂O) in water and ethanol without any chemical additions or high temperature treatment. The CuO balls with size of 150 nm–1.5 µm had rough surfaces which consisted of lots of about 10 nm nanofibers in diameter. The sizes of CuO balls were controllable by changing reaction time and volume ratio of water to ethanol. CuO nanofiber films were prepared with the aid of the in situ hydrolysis of Cu(CH₃COO)₂·H₂O coating layer on a substrate at 60 °C. CuO films showed excellent UV–visible light filteration property and could be used as a potential candidate of UV–visible light filter. Compared with traditional method to fabricate CuO films, neither precursor nor Cu substrate was needed in this study. This technique could be used to produce CuO films without being confined to our template and to produce CuO powders in large scale with low cost.     

Studies on NO2 gas sensing properties of sprayed Co1−xMnxFe2O4 (0≤x≤0.5) spinel ferrite thin films

The Co_1−xMn_xFe₂O₄ (0≤x≤0.5) spinel ferrite thin films were deposited on quartz substrates by chemical spray pyrolysis technique. The effect of Mn substitution on to the structural, electrical, dielectric and NO₂ gas sensing properties of cobalt ferrite thin films was studied. The X-ray diffraction analysis reveals that deposited films exhibit spinel cubic crystal structure. The lattice constant increases with the increase in Mn²⁺ content. The decrease in resistivity with increase in temperature suggests that the films have a semiconducting nature. The room temperature dielectric properties such as dielectric constant (ε′), loss tangent (tanδ), dielectric loss (ε′′) and AC conductivity have been studied in the frequency range 20 Hz–1 MHz. The film shows the highest sensor response at moderately low (150 °C) operating temperature. The effect of operating temperature, gas concentration, film selectivity and substitution of Mn on to gas response is carefully studied. The manganese substituted cobalt ferrite films are extremely selective towards NO₂ with a 20 times gas response compared with other gases. The gas response achieved nearly 92% of its initial value after 150 days, indicating good stability of the films.     

Structural,optical and methanol sensing properties of sprayed In2O3 nanoparticle thin films

Indium oxide (In₂O₃) nanoparticle thin films were grown on cleaned glass substrates by the chemical spray pyrolysis technique using the precursor solution of indium nitrate (In (NO₃)₃). The XRD studies confirm that the films are polycrystalline In₂O₃, possessing cubic structure with lattice parameters, a = b = c = 10.17 Å. The optical studies show a direct optical band gap of 3.32 eV and an indirect band gap of 2.6 eV in the prepared films. The films exhibit high optical transparency >80% in the visible region, reaching a maximum of 85% at 684 nm wavelength. Further, the gas sensing properties of the films have been investigated for various concentrations of methanol in air at different operating temperatures. At 300 °C the film exhibits a very high response 99% to methanol vapor at a concentration of 40 ppm in air, which is ideal to be used as a methanol sensor. The film shows fast response and recovery to methanol vapor at higher operating temperatures. A possible methanol sensing mechanism has been proposed.     

Bias dependent NO2 sensitivity of SnO2 thin films at room temperature

Amorphous granular SnO₂ thin films were investigated from a standpoint of an NO₂ gas sensor working at room temperature. The films were deposited using pulsed laser deposition method with substrate at room temperature and ～90 nm thick SnO₂ films with amorphous structure were obtained as a result. SnO₂ films deposited on Pt electrode substrates formed a sensor structure that showed response I_air/I_gas to 4 ppm NO₂ up to ～8000. I–V characteristics of the sensor structure were described by the power law dependence, whereas the power indexes were different for measurements in pure air and in the presence of NO₂. As a result, the sensor response was highly dependent on bias voltage between the sensor electrodes. It was demonstrated that the nonlinear electrical characteristics and bias dependent gas sensitivity were the inherent properties of thin films and the contacts were ohmic.     

Hybrid diamond/graphite films: Morphological evolution,microstructure and tribological properties

Diamond films were deposited on silicon substrate by microwave plasma enhanced chemical vapor deposition (MPCVD) using H₂ and CH₄ gas mixture. The morphological evolution process was characterized systematically by means of field-emission scanning electron microscopy (SEM), X-ray diffraction (XRD) and Raman spectroscopy. Special attention has been paid to the influence of the methane concentrations on the microstructures of diamond films, which shows a gradual transition from nanocrystalline to microcrystalline films, and finally displays a hybrid diamond-graphite nanostructure with the length of a few micrometers. Finally, the friction behaviour of the hybrid films was studied. The value of the friction coefficient of the hybrid films is 0.10 and the corresponding wear resistance is below 1.9 × 10^− 7 mm³/N·m in diamond composites/Al₂O₃ sliding system in ambient atmosphere under dry sliding conditions. It is a convenient path to synthesize hybrid diamond/graphite nanostructures by MPCVD depending on higher methane concentrations in the absence of nitrogen or argon. The structure is appropriate for the potential applications as high efficient mechanical tools.     

Highly sensitive H2S gas sensors based on CuO-coated ZnSnO3 nanorods synthesized by thermal evaporation

ZnSnO₃ one-dimensional (1D) nanostrutures were synthesized by thermal evaporation. The morphology, crystal structure and sensing properties of the CuO-coated ZnSnO₃ nanostructures to H₂S gas at 100 °C were examined. Transmission electron microscopy and X-ray diffraction revealed both the ZnSnO₃ nanorods and CuO nanoparticles to be single crystals. The diameters of the CuO nanoparticles on the nanorods ranged from a few to a few tens of nanometers. The gas sensors fabricated from multiple networked CuO-coated ZnSnO₃ nanorods exhibited enhanced electrical responses to H₂S gas compared to the uncoated ZnSnO₃ nanorod sensors, showing 61.7-, 49.9-, and 31.3-fold improvement at H₂S concentrations of 25, 50, and 100 ppm, respectively. The response time of the nanorod sensor to H₂S gas was reduced by the CuO coating but the recovery time was similar. The mechanism for the enhanced H₂S gas sensing properties of ZnSnO₃ nanorods by the CuO coating is discussed.     

Ambipolar chemical sensors based on the self-assembled film of an amphiphilic (phthalocyaninato) (porphyrinato) europium complex

An amphiphilic mixed (phthalocyaninato) (porphyrinato) europium triple-decker complex Eu₂(Pc)₂(TPyP) has been synthesized and characterized. Introducing electron-withdrawing pyridyl substituents onto the meso-position of porphyrin ring in the triple-decker to ensure the sufficient hydrophilicity and suitable HOMO and LUMO energy levels and thus successfully realize amphiphilic ambipolar organic semiconductor. Importantly, high sensitive, reproducible p-type and n-type responses towards NH₃ and NO₂ respectively, based on the self-assembled film of the Eu₂(Pc)₂(TPyP) fabricated by a simple solution-based Quasi–Langmuir–Shäfer (QLS) method, have been first revealed. The good conductivity and crystallinity for the QLS film of Eu₂(Pc)₂(TPyP) render it excellent sensing property for both electron-donating gas NH₃ in 5–30 ppm range and electron-accepting gas NO₂ in 400–900 ppb range due to the optimized molecular packing in the uniform-sized nanoparticles depending on the effective intermolecular interaction between the triple-decker molecules, among the best results of phthalocyanine-based chemical sensors for room-temperature detection of NH₃ and NO₂, respectively. Furthermore, the responses of the QLS film are all linearly correlated to both NH₃ and NO₂ with excellent sensitivity of 0.04% ppm^− 1 and 31.9% ppm^− 1, respectively, indicating the great potential of semiconducting tetrapyrrole rare earth triple-decker compounds in the field of chemical sensors.     

Improving the dispersion of CeO2 on γ-Al2O3 to enhance the catalytic performances of CuO/CeO2/γ-Al2O3 catalysts for NO removal by CO

Acetic acid (HAc) aqueous was used as solvent in wetness impregnation to prepare CeO₂-modified γ-Al₂O₃ support. With the help of HAc, the dispersion of CeO₂ on γ-Al₂O₃ is significantly improved and the size of CeO₂ nanoparticles can be controlled through tuning the concentration of HAc aqueous. XPS analysis shows that the percentages of Ce^3 + in CeO₂ nanoparticles will vary with the size. Then we load CuO on the as-prepared CeO₂-modified γ-Al₂O₃ support and choose NO reduction with CO as a probe reaction to investigate the influences of impregnation solvent on the catalytic properties. The results demonstrate that the CuO/CeO₂/γ-Al₂O₃ prepared in the solvent with volume ratio of 20:1 (H₂O:HAc) has the highest activity in NO + CO reaction. Combing the structural characterizations and catalytic performances, we think that the size of the CeO₂ nanoparticles should be a key factor that affects the activities of CuO/CeO₂/γ-Al₂O₃. Furthermore, CuO dispersed on CeO₂ nanoparticles with an average size of ca. 5 nm should be the highest active sites for NO + CO reaction.     

Electronic and surface properties of H-terminated diamond surface affected by NO2 gas

Hydrogen-terminated diamond surface exhibits p-type conductivity during its exposure to air. To investigate this phenomenon, we examined the influence of different gases on the surface conductivity. Exposure to NO₂ gas resulted in the biggest increase in conductivity, while H₂O vapor decreased the surface conductivity. Moreover, even very low concentrations of NO₂ molecules in air increased the hole sheet concentration, and with increasing NO₂ concentration, the hole sheet concentration increased up to 2.3 × 10¹⁴ cm^? 2 (at 300 ppm NO₂). This increase of hole sheet concentration was observed during exposure to NO₂ gas and simultaneous adsorption of NO₂ molecules on the diamond surface, while it decreased when the exposure stopped and NO₂ molecules desorbed from the surface. X-ray photoelectron spectroscopy investigation showed upward band bending and partial oxidation of the hydrogen-terminated surface after exposure to air and NO₂. FETs exposed to NO₂ gas exhibited lower source and drain resistances, which led to a 1.8-fold increase of maximum drain current, transconductance increased 1.5-fold and maximum frequency of oscillation increased 1.6-fold.     

Rose-like CuO nanostructures for highly sensitive glucose chemical sensor application

This paper reports the synthesis, characterization and glucose chemical sensing applications of well-crystalline rose-like CuO nanostructures. The rose-like CuO nanostructures were synthesized by facile hydrothermal process at low-temperature and characterized in detail in terms of their morphological, compositional, structural, optical and sensing properties. The detailed characterizations revealed that the synthesized rose-like CuO nanostructures are nanocrystalline and possessing monoclinic structure. Further, the synthesized nanostructures were used as efficient electron mediator to fabricate non-enzymatic glucose sensor. The fabricated glucose chemical sensor shows a very high sensitivity of ~4.640 μA mM⁻¹ cm⁻² and an experimental detection limit of ~0.39 mM with correlation coefficient (R) of 0.9498. The observed linear dynamic range for the fabricated chemical sensor was from 0.78 mM to 100 mM. The presented work demonstrates that simply prepared CuO nanomaterials can efficiently be used to fabricate reliable and reproducible glucose chemical sensors.     

Thermal annealing induced mazy structure on MoO3 thin films and their high sensing performance to NO gas at room temperature

MoS₂ thin films were prepared by radio frequency (RF) magnetron sputtering and then annealed in air. X-ray diffraction (XRD), field-emission electron scanning microscopy (FESEM) and transmission electron microscopy (TEM) were adopted to characterize the phase structure and surface morphology. Interestingly, upon thermal annealing in air, MoS₂ thin films changed into α-MoO₃ with mazy morphology, and the thin films were covered by MoO₃ nano-sheets with a length of 30–50 nm and a width of 10 nm. α-MoO₃ thin films with mazy morphology showed excellent response to NO gas at room temperature. The response of 5% and 92% was obtained at 5 ppm and 200 ppm, respectively, and the response and recovery times were 30 s and 1500 s. Moreover, the mazy structure of MoO₃ exhibited good selectivity to NO gas with respect to SO₂, NH₃ and H₂ gases. The high surface-to-volume ratio was the dominant factor for high sensing performance.     

Preparation of hierarchical WO3 dendrites and their applications in NO2 sensing

Hierarchical WO₃ dendrites were synthesized via low-cost and environmental-friendly solvothermal strategy. Characterization results indicated that WO₃ dendrites were composed of several multi-directional dendritic nanosheets. To further understand the formation of WO₃ dendrites, time-dependent experiments were carried out and formation mechanism was investigated. Since such dendritic structures rarely occurred in the field of gas sensing, the synthesized WO₃ dendrites were subjected to detailed NO₂ sensing tests. Results demonstrated that WO₃ dendrites based sensors had low detection limit (200 ppb) and fast response and recovery (7 s, 12 s to 5 ppm NO₂). Moreover, the sensor was also highly sensitive, selective and stable at low optimal operating temperature of 140 °C.     

Aqueous chemical route deposition of nanocrystalline ZnO thin films as acetone sensor: Effect of molarity

Nanocrystalline ZnO thin films were deposited onto glass substrate using a simple and inexpensive aqueous chemical method at low temperature (90 °C). The concentration of precursor solution was varied in order to study its effect on structural, morphological, and gas response properties. Field-emission scanning electron microscopy (FESEM) images indicate the growth of ZnO with hexagonal shaped nanostructure. Further these films were used to explore gas response properties towards acetone, propanol and ethanol vapors. The sensor response was found to be decreased with increase in precursor concentration. The highest sensor response of 92% was observed towards acetone for the film deposited at 0.05 M at an operating temperature of 350 °C. The higher vapor response towards acetone is attributed to size and surface morphology of the film deposited at 0.05 M.     

H2 response characteristics for sol–gel-derived WO3-SnO2 dual-layer thin films

This paper describes the deposition of SnO₂ and WO₃ thin films and WO₃-SnO₂ dual-layer thin films using the sol-gel process. The microstructure and morphology of these three thin films were analyzed with FE-SEM and X-ray diffraction. The H₂ response characteristics, including response magnitude, time and transients of the three samples, were investigated at different operation temperatures and H₂ gas concentrations. Although the maximum response magnitude of 29.31 towards 1000 ppm H₂ gas appeared at 225 °C,the WO₃-SnO₂ dual-layer films still had a response magnitude of 24.23 at 175 °C, which is much higher than those of the SnO₂ (4.19) and WO₃ (6.73) thin films. The linear response magnitude profile of the WO₃-SnO₂ dual-layer thin films toward H₂ gas concentration was obtained. The mechanism of the enhanced gas response characteristics was explained by the band bending theory.     

Synthesis and ethanol sensing properties of CuO nanorods coated with In2O3

CuO/In₂O₃ core–shell nanorods were fabricated using thermal evaporation and radio frequency magnetron sputtering. X-ray diffraction and transmission electron microscopy showed that both the cores and shells were crystalline. The multiple networked CuO/In₂O₃ core–shell nanorod sensors showed responses of 382–804%, response times of 36–54 s and recovery times of 144–154 s at ethanol (C₂H₅OH) concentrations ranging from 50 to 250 ppm at 300 °C. These responses were 2.3–2.8 times higher than those of the pristine CuO nanorod sensor over the same C₂H₅OH concentration range. The origin of the enhanced ethanol sensing properties of the core–shell nanorod sensor is discussed.     

Low-temperature synthesis of copper oxide (CuO) nanostructures with temperature-controlled morphological variations

We demonstrate low-temperature formation of copper oxide (CuO) nanostructures as well as temperature-controlled variation of morphology by applying hydrothermal methods with copper(II) acetate Cu(CH₃COO)₂·H₂O and 2-piperidinemethanol (2PPM) as starting materials. Monoclinic CuO nanostructures produced at 25 °C were of dendritic morphology with short nanorod-like substructures and exhibited a consequently large surface area (179 m² g⁻¹). Cyclic voltammetry measurements confirmed pseudocapacitive behavior of these dendritic CuO nanostructures giving specific capacitance ca. 28.2 F g⁻¹ at a scan rate of 5 mV s⁻¹. Oxide nanomaterials prepared in this investigation were characterized using powder X-ray diffraction, scanning and transmission electron microscopies, and nitrogen adsorption/desorption techniques. It is expected that these materials exhibit improved sensing and catalytic properties due to the increased availability of surface adsorption sites.     

Thermal conversion synthesis of Cu2O photocathode and the promoting effects of carbon coating

Simplifying the synthesis of cuprous oxide (Cu₂O) photocathode has turned out to be critical for scalable application. Herein, we present a novel thermal conversion approach to synthesize a shell/core structured Cu₂O/Cu photocathode. In this method a shell comprising a mixture of CuO and Cu₂O is obtained by heating Cu mesh at 500 °C in air beforehand, and subsequent annealing in N₂ atmosphere converts the unwanted CuO into Cu₂O gradually, which results in the desired Cu₂O/Cu structure. A slightly viscous starch sol coats the Cu₂O shell as carbon source, after carbonizing under N₂ atmosphere, the Cu₂O/Cu is covered with compact carbon films, i.e. C/Cu₂O/Cu. Photoelectrochemical experiments reveal that the introduction of carbon layers on Cu₂O enhances the photocurrent density from − 1.5 to − 2.75 mA·cm^− 2 at 0 V vs. reversible hydrogen electrode (RHE). Moreover, the deposition of carbon films on Cu₂O in this work has little effect on improving the stability.