One step from nanofiber to functional hybrid structure: Pd doped ZnO/SnO2 heterojunction nanofibers with hexagonal ZnO columns for enhanced low-temperature hydrogen gas sensing

In this paper, a novel hybrid structure of Pd doped ZnO/SnO₂ heterojunction nanofibers with hexagonal ZnO columns was one step synthesized from electrospun precursor nanofibers. Due to the synergistic effect of hexagonal ZnO, SnO₂ and Pd, the structure exhibited excellent hydrogen (H₂) gas sensing properties. At low-temperature of 120 °C, the response (R_a/R_g) to 100 ppm H₂ gas exceeded 160, the response/recovery time was only 20 s and 6 s respectively and the limit of detection was only 0.5 ppm. Meanwhile, it also had good selectivity for H₂ gas and excellent linearity. In addition, the materials were characterized by XRD, FESEM, HRTEM, XPS, and the synthesis mechanism and gas sensing mechanism were proposed.     

Enhanced NO2 sensing properties of Zn2SnO4-core/ZnO-shell nanorod sensors

Zn₂SnO₄-core/ZnO-shell nanorods were synthesized using a two-step process: synthesis of Zn₂SnO₄ nanorods the thermal evaporation of a mixture of ZnO, SnO₂, and graphite powders, followed by atomic layer deposition (ALD) of ZnO. The nanorods were 50–250 nm in diameter and a few to a few tens of micrometers in length. The cores and shells of the nanorods were face-centered cubic-structured single crystal Zn₂SnO₄ and wurtzite-structured single crystal ZnO, respectively. The multiple networked Zn₂SnO₄-core/ZnO-shell nanorod sensors showed a response of 173–498% to NO₂ concentrations of 1–5 ppm at 300 °C. These response values are 2–5 times higher than those of the Zn₂SnO₄ nanorod sensor over the same NO₂ concentration range. The NO₂ sensing mechanism of the Zn₂SnO₄core/ZnO-shell nanorods is discussed.     

Preparation and characterization of heteroepitaxial Zn2SnO4 single crystalline films prepared on MgO (100) substrates

Zinc stannate (Zn₂SnO₄) films were deposited on MgO (100) substrates by pulsed laser deposition, and Zn₂SnO₄ monocrystalline films were obtained by postannealing process. The structures, surface morphologies, and optical properties of the Zn₂SnO₄ films annealed at different temperatures were investigated in detail. Crystal structure analyses showed that the film annealed at 800°C was single crystal Zn₂SnO₄ with an inverse-spinel structure. The heteroepitaxial mechanism was further clarified by a schematic diagram, and the epitaxial relationships between the film and substrate were Zn₂SnO₄ (400) || MgO (200) with Zn₂SnO₄ [001] || MgO [001]. The obtained Zn₂SnO₄ films exhibited excellent transparency. The optical band gap of the 800°C-annealed Zn₂SnO₄ film was about 3.97 eV. The extinction coefficients and refractive indexes of the Zn₂SnO₄ films annealed at different temperatures as a function of wavelength were analyzed in detail.     

Heterostructure nanoarchitectonics with ZnO/SnO2 for ultrafast and selective detection of CO gas at low ppm levels

Heterojunction-based gas sensors are very attractive as they substantially improve the sensing characteristics due to the effective potential barrier present at the interface. Taking the advantages of two excellent semiconducting gas sensing materials i.e., SnO₂ and ZnO, herein, we have constructed ZnO/SnO₂ heterojunction by the combination of vacuum evaporation and r.f. sputtering or atomic layer deposition techniques. The ZnO/SnO₂ heterostructure with optimized thickness of ZnO (～10 nm) shows a 6-fold enhancement in sensing response compared to bare SnO₂ films against CO gas. The sensing responses of 81 and 85 % have been obtained for ZnO/SnO₂ heterostructures with ZnO deposited by sputtering and atomic layer deposition (ALD) methods, respectively, against 91 ppm of CO gas with an estimated limit of detection of 1.67 and 0.37 ppm. The ALD ZnO/SnO₂ sample displays an extremely fast response time of 5 s. The heterostructure sensors are also highly selective towards CO gas in the presence of other interfering toxic agents. The enhanced sensing characteristics of ZnO/SnO₂ are assigned to the formation of n-n heterojunction as depicted by X-ray photoelectron spectroscopic band alignment study and the strong CO adsorption on ZnO surface as derived from density functional theory calculations.     

Multilayer porous Pd-doped SnO2 thin film: Preparation and H2 sensing performance

Porous pure and Pd-doped SnO₂ films are prepared using sol-gel synthesis with polystyrene (PS) microspheres as the template. Different characterizations are performed to analyze the microstructure and morphology of the films. The sensing performance of the films at various temperatures and hydrogen concentrations is investigated. Results show that high concentration of PS template significantly influences the continuity of films and the H₂ sensing performance. The porous SnO₂ film with 0.1 wt% PS microspheres exhibits the best performance. At 225 °C, the response magnitude of the porous 1 mol% Pd-doped SnO₂ thin film to 1000 ppm H₂ is 93.18, which is approximately 10.58 times of the pure sample.     

Electroless plated SnO2–Pd–Au composite thin film for room temperature H2 detection

Extremely thin SnO₂ nanosheets with high surface area were fabricated through a one-pot hydrothermal method. In this work, gas sensing property of the SnO₂ nanosheets was studied. SnO₂–Pd–Au mixed thin films were prepared by electroless deposition of Pd, Au, and nanostructured SnO₂ onto the surface of a high resistance alumina substrate. The whole fabrication process was carried out at room temperature without any thermal treatment required. The films deposited on the alumina substrate were characterized by SEM and EDS. The co-deposited Au improved the electric conductance of the sensing film. A relatively large amount of Pd (Pd/Sn ratio around 1:1) was obtained for the film instead of the usually low doping value of Pd (∼0.1% level) for SnO₂ hydrogen sensor. It has been found that the SnO₂–Pd–Au composite film sensor has fast response in the range of 134–1469 ppm toward hydrogen gas at room temperature. The sensor also shows good stability and repeatability. Effects of annealing condition of the sensing film on H₂ gas sensing performance was investigated as well. A possible machnism for SnO₂–Pd room temperature hydrogen sensing is proposed.     

Fabrication and thermo stability of the SnO2/Ag/SnO2 tri-layer transparent conductor deposited by magnetic sputtering

Using the magnetic sputtering technique, the SnO₂/Ag/SnO₂ tri-layer transparent films were fabricated on float glasses successfully. Compared with the commercial FTO (F-doped SnO₂) film, the SnO₂/Ag/SnO₂ tri-layer films have higher visible-light transmittance and better conductivity. The total thickness of the SnO₂/Ag/SnO₂ films is one third of the commercial FTO film leading to the high visible-light transmittance. The high carrier concentration of the SnO₂/Ag/SnO₂ films contributes to the tri-layer films’ low resistivity. In addition, to further improve the performance of the SnO₂/Ag/SnO₂ tri-layer films, samples were annealed under different temperatures. The results illustrate that the lowest sheet resistance (5.92 Ω/sq) and the highest visible-light transmittance (87.0%) were obtained after annealing at 200 °C. Furthermore, the thermal stability of the films could be enhanced by a multi-step annealing process due to the recrystallization effect.     

Preparation of ordered porous SnO2 films by dip-drawing method with PS colloid crystal templates

Ordered macroporous SnO₂ thin films were fabricated by using colloid crystal template of polystyrene (PS) spheres. Efficient dip-drawing method was used in both PS template assembly and the fabrication of porous structure. The PS templates were orderly assembled on clean glass substrates through colloid crystallization of monodisperse PS latex spheres, which were synthesized by an emulsion polymerization technique. The porous SnO₂ thin films were prepared through filling SnO₂ precursor sol into the spaces among the close-packed PS templates, and then annealing at 500 °C to remove the PS spheres and form SnO₂ crystal wall. The forming mechanism of PS templates through dip-drawing method was explained based on three driving forces existing in the assembly processes. The SnO₂ sol concentration and PS sphere size had important effects on formation of ordered porous structure The X-ray diffraction (XRD) spectra indicated the thin film was rutile structure and consisted of nanometer grains. The transmittance spectrum showed that optical transmittance kept above 80% beyond the wavelength of 440 nm. Optical band-gap of the porous SnO₂ film was 3.68 eV.     

Effect of rapid thermal annealing on the properties of zinc tin oxide films prepared by plasma-enhanced atomic layer deposition

The effect of rapid thermal annealing treatments on the microstructure, surface morphology, and optical characteristics of zinc tin oxide (ZTO) films produced by plasma-enhanced atomic layer deposition was investigated. The ZTO films were annealed in oxygen atmosphere for 2 min at four selected temperatures from 500 to 800 °C. The X-ray diffraction showed that the annealing temperature has a great influence on the crystalline characteristics of ZTO films. The film shows complete amorphous structure for as-deposited ZTO film. Meanwhile, the spinel zinc stannate Zn₂SnO₄ was obtained for the samples annealed from 500 to 800 °C, which shows polycrystalline nature. The X-ray photoelectron spectroscopy proved that the annealing process in oxygen gas can effectively can reduce the oxygen vacancy defects in the films. In addition, the photoluminescence spectroscopy manifests an ultraviolet emission with a broad peak range from 345 to 385 nm. Moreover, the ultraviolet luminescence intensity increases continuously with the increase of annealing temperature. Spectroscopic ellipsometry analyses demonstrate that the refractive index of annealed films increases as the increase of annealing temperature, while the extinction coefficient decreases gradually with the increase of annealing temperature in the visible light range.     

High-quality c-axis oriented non-vacuum Er doped ZnO thin films

Preparation, growth, structure and optical properties of high-quality c-axis oriented non-vacuum Er doped ZnO thin films were studied. Zn_1−xEr_xO (x=0.0, 0.01, 0.02, 0.04, and 0.05) precursor solutions were prepared by sol–gel synthesis using Zn, and Er based alkoxide which were dissolved into solvent and chelating agent. Zn_1−xEr_xO thin films with different Er doping concentration were grown on glass substrate using sol–gel dip coating. Thin films were annealed at 600 °C for 30 min, and tried to observe the effect of doping ratio on structural and optical properties. The particle size, crystal structure, surface morphologies and microstructure of all samples were characterized by X-Ray diffraction (XRD) and Scanning Electron Microscope (SEM). The UV–vis spectrometer measurements were carried out for the optical characterizations. The surface morphology of the Zn_1−xEr_xO films depend on substrate nature and sol–gel parameters such as withdrawal speed, drying, heat treatment, deep number (film thickness) and annealing condition. Surface morphologies of Er doped ZnO thin films were dense, without porosity, uniform, crack and pinhole free. XRD results showed that, all Er doped ZnO thin films have a hexagonal structure and (002) orientation. The optical transmittance of rare earth element (Er) doped ZnO thin films were increased. The Er doped ZnO thin films showed high transparency (>85) in the visible region (400–700 nm).     

ZnO–SnO2 nanocubes for fluorescence sensing and dye degradation applications

ZnO–SnO₂ nanocubes were used as promising material for efficient sensing of p-nitrophenol and faster photocatalytic degradations of dyes like methyl orange (MO), methylene Blue (MB) and acid orange 74 (AO74). ZnO–SnO₂ nanocubes were prepared by the facile solution process at 50 °C using Zn(NO₃)₂·6H₂O and SnCl₂·2H₂O as a precursor in the presence of ethylenediammine. The synthesized material was examined for its morphological, structural, crystalline, optical, vibrational, and compositional studies by using field emission scanning electron microscopy (FESEM), X-ray diffraction (XRD), Fourier Transform Infrared (FTIR) spectroscopy, X-ray photoelectron spectroscopy (XPS) and photoluminescence spectroscopy. FESEM studies revealed the formation of well-defined ZnO–SnO₂ nanocubes where the structural examinations revealed the formation of a crystalline tetragonal rutile phase for SnO₂ with some crystal sites doped with Zn. The as-synthesized nanocubes were explored for their photocatalytic activities towards three different dye viz. MO, MB, and AO74. Practically, complete degradation of AO74 was seen within 4 minutes of photo-irradiation in the presence of 0.05 g ZnO–SnO₂ nanocubes. However, 97.17% and 41.63% degradations were observed for MB and MO within 15 and 60 minutes, respectively. All the dye degradation processes followed the pseudo-first-order kinetic model. Moreover, the as-synthesized nanocubes were utilized to fabricate highly sensitive and selective fluorescent chemical sensor for the detection of p-nitrophenol (PNP). ZnO–SnO₂ nanocubes showed a very low detection limit of 4.09 μM for the detection of PNP as calculated according to the 3σ IUPAC criteria. Further, the as-synthesized ZnO–SnO₂ nanotubes were found to be highly selective for p-nitrophenol as compared to the other two isomers.     

Schottky barrier effect of ZnO modified methyl glycol thin films for detection of hydrogen sulfide gas

Highly nanocrystalline ZnO modified methyl glycol thin films have been deposited on a p-type silicon substrate via the sol–gel spin coating manner. The morphology of the as-deposited film was scrutinized using scanning electron microscopy. I–V characteristics of the as-prepared ZnO film under vacuum and in open air were monitored. The results showed that the ZnO films have a barrier height of 0.38 eV under vacuum and 0.62 eV in open air. The Schottky barrier height between ZnO grains was determined for different reducing gases. The ZnO film showed high sensitivity to H₂S gas compared with other reducing gases due to the reduction of barrier height between ZnO grains. The as-prepared ZnO film was annealed at four different temperatures. X-ray diffraction manifested that the wurtzite hexagonal structure of ZnO deviated from ideality at annealing temperature greater than 650 °C. The barrier height of ZnO film decreased due to the increase of annealing temperature up to 650 °C and then decreased. The results also confirmed that the change of barrier height strongly affected the sensitivity of ZnO film.     

Highly sensitive C2H2 gas sensor based on Ag modified ZnO nanorods

The sliver (Ag) modified zinc oxide (ZnO) nanorods were successfully obtained with a simplified and environmentally friendly solvothermal method. Materials characterization indicated that the metallic Ag was located on the outside of ZnO nanorods after annealing. In comparison with ZnO nanorods, Ag modified ZnO (Ag–ZnO) nanorods exhibited a considerably enhanced response to C₂H₂. The response of the 3 at% Ag–ZnO based sensor operating at 175 °C is 539 (R_a/R_g), which is the highest value among all the sensors in detecting 100 ppm C₂H₂. The Ag–ZnO based sensors exhibited fast response speed, lower operation temperature and higher selectivity.     

Sintering densification behavior of ZnO–SnO2 binary ceramic targets

In this work, high-performance ZnO–SnO₂ binary ceramic targets for magnetron sputtering of transparent conductive oxide (TCO) films were prepared by pressureless oxygen atmosphere sintering. The sintering behavior and densification mechanism of the ZnO–SnO₂ binary targets were analyzed by systematically studying the oxide powder state, formation process of the solid reaction phase, and evolution of the target microstructure. The data revealed that the ZnO–SnO₂ powder treatment improved the sintering activity and the powder dispersion; furthermore, it promoted a mutual reaction between the different components during sintering and the homogeneity of the target composition. The densification of the pure SnO₂ ceramic target was difficult to achieve, and the addition of ZnO led to a continuous interaction between the ZnO and SnO₂ components. The Zn₂SnO₄ phase started to form, and a temporary shrinkage of the target occurred above 800°C. After formation of the stable Zn₂SnO₄ and SnO₂ phases, the target shrunk rapidly with increasing temperature, densification occurred during growth, and the two phases started to interact. The sintering temperature provided the driving force for the target densification, with the densification activation energy of the ZnO–SnO₂ binary ceramic target estimated to be 580 kJ/mol based on the master sintering curve. A binary ceramic target with a high density (99.78% relative density), a fine grain size, and a homogeneous phase structure was achieved at a temperature of 1600°C. These findings are promising for the further improvement and performance enhancement of SnO₂-based materials.     

Improved photoluminescence emission and gas sensor properties of ZnO thin films

In this article, we report a comparative study of the influence of pressure-assisted (1.72 MPa) versus ambient pressure thermal annealing on both ZnO thin films treated at 330 °C for 32 h. The effects of pressure on the structural, morphological, optical, and gas sensor properties of these thin films were investigated. The results show that partial preferential orientation of the wurtzite-structure ZnO thin films in the [002] or [101] planes is induced based on the thermal annealing conditions used (i.e., pressure assisted or ambient pressure). UV–vis absorption measurements revealed a negligible variation in the optical -band gap values for the both ZnO thin films. Consequently, it is deduced that the ZnO thin films exhibit different distortions of the tetrahedral [ZnO₄] clusters, corresponding to different concentrations of deep and shallow level defects in both samples. This difference induced a variation of the interface/bulk-surface, which might be responsible for the enhanced optical and gas sensor properties of the pressure-assisted thermally annealed film. Additionally, pressure-assisted thermal annealing of the ZnO films improved the H₂ sensitivity by a factor of two.     

Sandwich-structured ZnO-MnO2-ZnO thin film varistors prepared via magnetron sputtering

ZnO varistors are widely used to protect electronic circuits form transient voltages. However, it is difficult to prepare varistors with voltage less than 10 V using ZnO ceramics. Here we prepared a ZnO-MnO₂-ZnO (ZMZ) sandwich thin film via magnetron sputtering and subsequent annealing at 200-500 °C. With the increase of annealing temperature, the manganese oxide sandwich layer reacts with the upper and lower ZnO layer and becomes thinner. After annealed at 500 °C, because of ZnO grain growth, the upper and lower ZnO layers joined together. The electrical properties of ZMZ films annealed at 400 °C show strong nonlinear I-V characteristics. A ZMZ low voltage thin film varistor with planar boundary potential barrier was obtained whose nonlinear coefficient α and varistor voltage V1 mA are about 30 and 6.0 V, respectively. The stable and excellent nonlinear characteristics make it a promising candidate for overvoltage protection in low operating voltage circuits.     

Structural, Electrical and Optical Properties of p-Type Transparent Conducting SnO2:Zn Film

Highly transparent, p-type conducting SnO₂:Zn films were deposited on quartz substrates by radio frequency (RF) magnetron sputtering using a 12 wt% ZnO doped with 88 wt% SnO₂ ceramic target followed by annealing at various temperatures. The effect of annealing temperature on the structural, electrical and optical performances of SnO₂:Zn films has been studied. XRD results show that all the SnO₂:Zn films possess tetragonal rutile structure with the preferred orientation of (101). Hall effect results indicate that at 873 K for 3 h was the optimum annealing parameters for p-type SnO₂:Zn films with relatively high hole concentration and low resistivity of 3.334 × 10¹⁹ cm⁻³ and 3.588 Ω cm, respectively. The average transmission of the p-type SnO₂:Zn films were above 80% in the visible light range. In addition, p-type conductivity was also confirmed by the non-linear characteristics of a p-type SnO₂:Zn/n-type SnO₂:Sb structure.     

Sputtering deposition of transparent conductive F-doped SnO2 (FTO) thin films in hydrogen-containing atmosphere

F-doped SnO₂ (FTO) thin films have been prepared by sputtering SnO₂-SnF₂ target in Ar+H₂ atmosphere. The effects of H₂/Ar flow ratio on the structural, electrical and optical properties of the films were investigated at two substrate temperatures of 150 and 300 °C and two base pressures of 3.5×10⁻³ and 1.5×10⁻² Pa. The results show that introducing H₂ into sputtering atmosphere can lead to the formation of a FTO film with a (101) preferred orientation and produce oxygen vacancy (V_O) at lower H₂/Ar flow ratios, but SnO phase at higher H₂/Ar flow ratios in the films. Accordingly, the resistivity of the films first decreases and then increases, but the transmittance decreases continuously with increasing H₂/Ar flow ratio. When H₂/Ar flow ratio is increased above a certain value, more amorphous SnO phase forms in the films, resulting in a big decrease in conductivity, transmittance, and band gap (E_g). Increasing substrate temperature can increase the Hall mobility due to the improvement of film crystallinity, but decrease the carrier concentration due to outward-diffusion of fluorine in the films. At a base pressure of 3.5×10⁻³ Pa, high substrate temperature (300 °C) can hinder the formation of SnO and thus improve the transparent conductive properties of the films. At a base pressure of 1.5×10⁻² Pa, the range of H₂/Ar flow ratio for forming the SnO₂ phase and hence for obtaining high transparent conductive FTO films is widened at both substrate temperatures of 150 and 300 °C.     

Low temperature processed SnO2 films using aqueous precursor solutions

We present a comparison study of the microstructure developments during aqueous solution deposition of SnO₂, particularly, through chemical bath deposition (CBD) and liquid phase deposition (LPD) at very low temperatures (40–75 °C). The effects of solution chemistry on the microstructural details and electrical properties of SnO₂ thin films are presented and discussed. Smooth, nanoparticulate SnO₂ films were obtained from supersaturated precursor solutions with lower precursor concentrations while more aggregated SnO₂ films were generated from higher precursor concentrations. Loosely-packed and porous structures were obtained from low supersaturation solutions with very low pHs. The deposition rates were also evaluated under various deposition conditions. XRD result shows that annealing process helps improve the degree of crystallinity of the as-deposited films that are composed of 3–10 nm nanocrystalline particles. One advantage of LPD of SnO₂ films is in-situ fluorine doping during deposition. The resulting electrical resistivity of F-doped SnO₂ films was about 18.7 Ω cm after the films were annealed at 450 °C.     

Preparation of hollow SnO2/ZnO cubes for the high-performance detection of VOCs

Detecting volatile organic compounds is essential to improving the environment and human health. This study prepared a novel composite of hollow SnO₂/ZnO cubes using a self-template hydrothermal method followed by a calcination process. The morphology and structure of the composites were characterized using a series of analysis techniques, and the formation mechanism of a hollow cube-like structure was explored. Compared to the hollow SnO₂ cube sensor, the hollow SnO₂/ZnO cube sensor exhibited a strong response (148–100 ppm formaldehyde), fast response/recovery time (15 s/25 s), good linearity (R² = 0.995), good repeatability, and excellent stability. The superior gas sensing property of the hollow SnO₂/ZnO cubes was attributed to the combined advantages of hollow structures and heterojunctions.