Recent industrialization has led to a high demand for the use of fossil fuels. Therefore, the need for producing hydrogen and its utilization is essential for a sustainable society. For an eco-friendly future technology, photoelectrochemical water splitting using solar energy has proven promising amongst many other candidates. With this technique, semiconductors can be used as photocatalysts to generate electrons by light absorption, resulting in the reduction of hydrogen ions. The photocatalysts must be chemically stable, economically inexpensive and be able to utilize a wide range of light. From this perspective, cuprous oxide(Cu2O) is a promising p-type semiconductor because of its appropriate band gap. However, a major hindrance to the use of Cu2O is its instability at the potential in which hydrogen ion is reduced. In this study, gold is used as a bottom electrode during electrodeposition to obtain a preferential growth along the (111) plane of Cu2O while imperfections of the Cu2O thin films are removed. This study investigates the photoelectrochemical properties of Cu2O. However, severe photo-induced corrosion impedes the use of Cu2O as a photoelectrode. Two candidates, TiO2 and SnO2, are selected for the passivation layer on Cu2O by by considering the Pourbaix-diagram. TiO2 and SnO2 passivation layers are deposited by atomic layer deposition(ALD) and a sputtering process, respectively. The investigation of the photoelectrochemical properties confirmed that SnO2 is a good passivation layer for Cu2O.

Nickel oxide(NiO) thin films, nanorods, and carbon nanotube(CNT)/NiO core-shell nanorod structures are fabricated by sputtering Nickel at different deposition time on alumina substrates or single wall carbon nanotube templates followed by oxidation treatments at different temperatures, 400 and 700 oC. Structural analyses are carried out by scanning electron microscopy and x-ray diffraction. NiO thinfilm, nanorod and CNT/NiO core-shell nanorod structurals of the gas sensor structures are tested for detection of H2S gas. The NiO structures exhibit the highest response at 200 oC and high selectivity to H2S among other gases of NO, NH3, H2, CO, etc. The nanorod structures have a higher sensing performance than the thin films and carbon nanotube/NiO core-shell structures. The gold catalyst deposited on NiO nanorods further improve the sensing performance, particularly the recovery kinetics.

Lithium-ion batteries have been considered the most important devices to power mobile or small-sized devices due to their high energy density. LixCoO2 has been studied as a cathode material for the Li-ion battery. However, the limitation of its capacity impedes the development of high capacity cathode materials with Ni, Mn, etc. in them. The substitution of Mn and Ni for Co leads to the formation of solid solution phase LiNixMnyCo1-x-yO2 (NMC, both x and y < 1), which shows better battery performance than unsubstituted LiCoO2. However, despite a high discharge capacity in the Ni-rich compound (Ni > 0.8 in the metal site), poor cycle retention capability still remains to be overcome. In this study, aiming to improve the stability of the physical and chemical bonding, we investigate the stabilization effect of Ca in the Ni-rich layered compound Li(Ni0.83Co0.12Mn0.05)O2, and then Ca is added to the modified secondary particles to lower the degree of cationic mixing of the final particles. For the optimization of the final grains added with Ca, the Ca content (x = 0, 2.5, 5.0, 10.0 at.%) versus Li is analyzed.

Hydrothermal synthesis of highly crystalline TiO2 nanorods is a well-developed technique and the nanorods have been widely used as the template for growth of various core-shell nanorod structures. Magneli/CdS core-shell nanorod structures are fabricated for the photoelectrochemical cell (PEC) electrode to achieve enhanced carrier transport along the metallic magneli phase nanorod template. However, the long and thin TiO2 nanorods may form a high resistance path to the electrons transferred from the CdS layer. TiO2 nanorods synthesized are reduced to magneli phases, TixO2x-1, by heat treatment in a hydrogen environment. Two types of magneli phase nanorods of Ti4O7 and Ti3O5 are synthesized. Structural morphology and X-ray diffraction analyses are carried out. CdS nano-films are deposited on the magneli nanorods for the main light absorption layer to form a photoanode, and the PEC performance is measured under simulated sunlight irradiation and compared with the conventional TiO2/CdS core-shell nanorod electrode. A higher photocurrent is observed from the stand-alone Ti3O5/CdS coreshell nanorod structure in which the nanorods are grown on both sides of the seed layer.

We report on the fabrication and photoelectrochemical(PEC) properties of a Cu2O thin film/ZnO nanorod array oxide p-n heterojunction structure with ZnO nanorods embedded in Cu2O thin film as an efficient photoelectrode for solardriven water splitting. A vertically oriented n-type ZnO nanorod array was first prepared on an indium-tin-oxide-coated glass substrate via a seed-mediated hydrothermal synthesis method and then a p-type Cu2O thin film was directly electrodeposited onto the vertically oriented ZnO nanorods array to form an oxide semiconductor heterostructure. The crystalline phases and morphologies of the heterojunction materials were characterized using X-ray diffraction and scanning electron microscopy as well as Raman scattering. The PEC properties of the fabricated Cu2O/ZnO p-n heterojunction photoelectrode were evaluated by photocurrent conversion efficiency measurements under white light illumination. From the observed PEC current density versus voltage (J-V) behavior, the Cu2O/ZnO photoelectrode was found to exhibit a negligible dark current and high photocurrent density, e.g., 0.77 mA/cm2 at 0.5 V vs Hg/HgCl2 in a 1 mM Na2SO4 electrolyte, revealing an effective operation of the oxide heterostructure. In particular, a significant PEC performance was observed even at an applied bias of 0 V vs Hg/ HgCl2, which made the device self-powered. The observed PEC performance was attributed to some synergistic effect of the p-n bilayer heterostructure on the formation of a built-in potential, including the light absorption and separation processes of photoinduced charge carriers.

We report on the efficient detection of NO gas by an all-oxide semiconductor p-n heterojunction diode structure comprised of n-type zinc oxide (ZnO) nanorods embedded in p-type copper oxide (CuO) thin film. The CuO thin film/ZnO nanorod heterostructure was fabricated by directly sputtering CuO thin film onto a vertically aligned ZnO nanorod array synthesized via a hydrothemal method. The transport behavior and NO gas sensing properties of the fabricated CuO thin film/ ZnO nanorod heterostructure were charcterized and revealed that the oxide semiconductor heterojunction exhibited a definite rectifying diode-like behavior at various temperatures ranging from room temperature to 250 oC. The NO gas sensing experiment indicated that the CuO thin film/ZnO nanorod heterostructure had a good sensing performance for the efficient detection of NO gas in the range of 2-14 ppm under the conditions of an applied bias of 2 V and a comparatively low operating temperature of 150 oC. The NO gas sensing process in the CuO/ZnO p-n heterostructure is discussed in terms of the electronic band structure.

In this study, (3,4-epoxycyclohexane)methyl 3,4-epoxycyclohexylcarboxylate acrylate was synthesized by reacting (3,4-epoxycyclohexane)methyl 3,4-epoxycyclohexylcarboxylate with acrylic acid to minimize hardening shrinkage and to improve heat resistance, which are known as disadvantages of photopolymers for 3D printing application. Urethane acrylate was synthesized by reacting 1,3,5-triazine-2,4,6-triamino alcohol, 2-hexylethyl acrylate, and isophorone diisocyanate in order to improve the mechanical properties without deteriorating the heat resistance. The physical properties before and after the synthesis of the acrylate and the mechanical properties when the urethane acrylate was applied were investigated. The reaction progress of the composite was examined by FTIR and 13C NMR. The heat deflection temperature, flexural strength, and surface hardness of the molding were measured. The curing behavior by Photo-DSC ultraviolet irradiation was also examined.

We report on the fabrication and characterization of a novel Cu2O/CuO heterojunction structure with CuO nanorods embedded in Cu2O thin film as an efficient photocathode for photoelectrochemical (PEC) solar water splitting. A CuO nanorod array was first prepared on an indium-tin-oxide-coated glass substrate via a seed-mediated hydrothermal synthesis method; then, a Cu2O thin film was electrodeposited onto the CuO nanorod array to form an oxide semiconductor heterostructure. The crystalline phases and morphologies of the heterojunction materials were examined using X-ray diffraction and scanning electron microscopy, as well as Raman scattering. The PEC properties of the fabricated Cu2O/CuO heterojunction photocathode were evaluated by photocurrent conversion efficiency measurements under white light illumination. From the observed PEC current density versus voltage (J-V) behavior, the Cu2O/CuO photocathode was found to exhibit negligible dark current and high photocurrent density, e.g. −1.05 mA/cm2 at −0.6 V vs. Hg/HgCl2 in 1 mM Na2SO4 electrolyte, revealing the effective operation of the oxide heterostructure. The photocurrent conversion efficiency of the Cu2O/CuO photocathode was estimated to be 1.27% at −0.6 V vs. Hg/HgCl2. Moreover, the PEC current density versus time (J-T) profile measured at −0.5 V vs. Hg/HgCl2 on the Cu2O/CuO photocathode indicated a 3-fold increase in the photocurrent density compared to that of a simple Cu2O thin film photocathode. The improved PEC performance was attributed to a certain synergistic effect of the bilayer heterostructure on the light absorption and electron-hole recombination processes.

Fabrication of iron oxide/carbon nanotube composite structures for detection of ammonia gas at room temperature is reported. The iron oxide/carbon nanotube composite structures are fabricated by in situ co-arc-discharge method using a graphite source with varying numbers of iron wires inserted. The composite structures reveal higher response signals at room temperature than at high temperatures. As the number of iron wires inserted increased, the volume of carbon nanotubes and iron nanoparticles produced increased. The oxidation condition of the composite structures varied the carbon nanotube/iron oxide ratio in the structure and, consequently, the resistance of the structures and, finally, the ammonia gas sensing performance. The highest sensor performance was realized with 500 oC/2 h oxidation heat-treatment condition, in which most of the carbon nanotubes were removed from the composite and iron oxide played the main role of ammonia sensing. The response signal level was 62% at room temperature. We also found that UV irradiation enhances the sensing response with reduced recovery time.

H2S is a flammable toxic gas that can be produced in plants, mines, and industries and is especially fatal to humanbody. In this study, CuO nanowire structure with high porosity was fabricated by deposition of copper on highly porous single-wall carbon nanotube (SWCNT) template followed by oxidation. The SWCNT template was formed on alumina substrates bythe arc-discharge method. The oxidation temperatures for Cu nanowires were varied from 400 to 800oC. The morphology andsensing properties of the CuO nanowire sensor were characterized by FESEM, Raman spectroscopy, XPS, XRD, and current-voltage examination. The H2S gas sensing properties were carried out at different operating temperatures using dry air as thecarrier gas. The CuO nanowire structure oxidized at 800oC showed the highest response at the lowest operating temperatureof150oC. The optimum operating temperature was shifted to higher temperature to 300oC as the oxidation temperature waslowered. The results were discussed based on the mechanisms of the reaction with ionosorbed oxygen and the CuS formationreaction on the surface.

We present the detection characteristics of nitrogen monoxide(NO) gas using p-type copper oxide(CuO) thin film gas sensors. The CuO thin films were fabricated on glass substrates by a sol-gel spin coating method using copper acetate hydrate and diethanolamine as precursors. Structural characterizations revealed that we prepared the pure CuO thin films having a monoclinic crystalline structure without any obvious formation of secondary phase. It was found from the NO gas sensin measurements that the p-type CuO thin film gas sensors exhibited a maximum sensitivity to NO gas in dry air at an operating temperature as low as 100 oC. Additionally, these CuO thin film gas sensors were found to show reversible and reliable electrical response to NO gas in a range of operating temperatures from 60 oC to 200 oC. It is supposed from these results that the ptype oxide semiconductor CuO thin film could have significant potential for use in future gas sensors and other oxide electronics applications using oxide p-n heterojunction structures.

We report the nitrogen monoxide (NO) gas sensing properties of p-type CuO-nanorod-based gas sensors. We synthesized the p-type CuO nanorods with breadth of about 30 nm and length of about 330 nm by a hydrothermal method using an as-deposited CuO seed layer prepared on a Si/SiO2 substrate by the sputtering method. We fabricated polycrystalline CuO nanorod arrays at 80˚C under the hydrothermal condition of 1:1 morality ratio between copper nitrate trihydrate [Cu(NO2)2·3H2O] and hexamethylenetetramine (C6H12N4). Structural characterizations revealed that we prepared the pure CuO nanorod array of a monoclinic crystalline structure without any obvious formation of secondary phase. It was found from the gas sensing measurements that the p-type CuO nanorod gas sensors exhibited a maximum sensitivity to NO gas in dry air at an operating temperature as low as 200˚C. We also found that these CuO nanorod gas sensors showed reversible and reliable electrical response to NO gas at a range of operating temperatures. These results would indicate some potential applications of the p-type semiconductor CuO nanorods as promising sensing materials for gas sensors, including various types of p-n junction gas sensors.

Photoelectrochemical cells have been used in photolysis of water to generate hydrogen as a clean energy source. A high efficiency electrode for photoelectrochemical cell systems was realized using a ZnO hierarchical nanostructure. A ZnO nanofiber mat structure was fabricated by electrospinning of Zn solution on the substrate, followed by oxidation; on this substrate, hydrothermal synthesis of ZnO nanorods on the ZnO nanofibers was carried out to form a ZnO hierarchical structure. The thickness of the nanofiber mat and the thermal annealing temperature were determined as the parameters for optimization. The morphology of the structures was examined by field-emission scanning electron microscopy, transmission electron microscopy, and X-ray diffraction. The performance of the ZnO nanofiber mat and the potential of the ZnO hierarchical structures as photoelectrochemical cell electrodes were evaluated by measurement of the photoelectron conversion efficiencies under UV light. The highest photoconversion efficiency observed was 63 % with a ZnO hierarchical structure annealed at 400˚C in air. The morphology and the crystalline quality of the electrode materials greatly influenced the electrode performance. Therefore, the combination of the two fabrication methods, electrospinning and hydrothermal synthesis, was successfully applied to fabricate a high performance photoelectrochemical cell electrode.

We investigated the detection properties of nitrogen monoxide (NO) gas using transparent p-type CuAlO2 thin film gas sensors. The CuAlO2 film was fabricated on an indium tin oxide (ITO)/glass substrate by pulsed laser deposition (PLD), and then the transparent p-type CuAlO2 active layer was formed by annealing. Structural and optical characterizations revealed that the transparent p-type CuAlO2 layer with a thickness of around 200 nm had a non-crystalline structure, showing a quite flat surface and a high transparency above 65 % in the range of visible light. From the NO gas sensing measurements, it was found that the transparent p-type CuAlO2 thin film gas sensors exhibited the maximum sensitivity to NO gas in dry air at an operating temperature of 180˚C. We also found that these CuAlO2 thin film gas sensors showed reversible and reliable electrical resistance-response to NO gas in the operating temperature range. These results indicate that the transparent p-type semiconductor CuAlO2 thin films are very promising for application as sensing materials for gas sensors, in particular, various types of transparent p-n junction gas sensors. Also, these transparent p-type semiconductor CuAlO2 thin films could be combined with an n-type oxide semiconductor to fabricate p-n heterojunction oxide semiconductor gas sensors.

A simple thermal oxidation of Cu thin films deposited on planar substrates established a growth of vertically aligned copper oxide (CuO) nanorods. DC sputter-deposited Cu thin films with various thicknesses were oxidized in environments of various oxygen partial pressures to control the kinetics of oxidation. This is a method to synthesize vertically aligned CuO nanorods in a relatively shorter time and at a lower cost than those of other methods such as the popular hydrothermal synthesis. Also, this is a method that does not require a catalyst to synthesize CuO nanorods. The grown CuO nanorods had diameters of ~100 nm and lengths of 1~25μm. We examined the morphology of the synthesized CuO nanorods as a function of the thickness of the Cu films, the gas environment, the oxidation time, the oxidation temperature, the oxygen gas flow rate, etc. The parameters all influence the kinetics of the oxidation, and consequently, the volume expansion in the films. Patterned growth was also carried out to confirm the hypothesis of the CuO nanorod protrusion and growth mechanism. It was found that the compressive stress built up in the Cu film while oxygen molecules incorporated into the film drove CuO nanorods out of the film.

We report on the NO gas sensing properties of non-directional ZnO nanofibers synthesized using a typical electrospinning technique. These non-directional ZnO nanofibers were electrospun on an SiO2/Si substrate from a solution containing poly vinyl alcohol (PVA) and zinc nitrate hexahydrate dissolved in distilled water. Calcination processing of the ZnO/PVA composite nanofibers resulted in a random network of polycrystalline ZnO nanofibers of 50 nm to 100 nm in diameter. The diameter of the nanofibers was found to depend primarily on the solution viscosity; a proper viscosity was maintained by adding PVA to fabricate uniform ZnO nanofibers. Microstructural measurements using scanning electron microscopy revealed that our synthesized ZnO nanofibers after calcination had coarser surface morphology than those before calcination, indicating that the calcination processing was sufficient to remove organic contents. From the gas sensing response measurements for various NO gas concentrations in dry air at several working temperatures, it was found that gas sensors based on electrospun ZnO nanofibers showed quite good responses, exhibiting a maximum sensitivity to NO gas in dry air at an operating temperature of 200˚C. In particular, the non-directional electrospun ZnO nanofiber gas sensors were found to have a good NO gas detection limit of sub-ppm levels in dry air. These results illustrate that non-directional electrospun ZnO nanofibers are promising for use in low-cost, high-performance practical NO gas sensors.

We report on the NO gas sensing properties of Al-doped zinc oxide-carbon nanotube (ZnO-CNT) wire-like layered composites fabricated by coaxially coating Al-doped ZnO thin films on randomly oriented single-walled carbon nanotubes. We were able to wrap thin ZnO layers around the CNTs using the pulsed laser deposition method, forming wire-like nanostructures of ZnO-CNT. Microstructural observations revealed an ultrathin wire-like structure with a diameter of several tens of nm. Gas sensors based on ZnO-CNT wire-like layered composites were found to exhibit a novel sensing capability that originated from the genuine characteristics of the composites. Specifically, it was observed by measured gas sensing characteristics that the gas sensors based on ZnO-CNT layered composites showed a very high sensitivity of above 1,500% for NO gas in dry air at an optimal operating temperature of 200˚C; the sensors also showed a low NO gas detection limit at a sub-ppm level in dry air. The enhanced gas sensing properties of the ZnO-CNT wire-like layered composites are ascribed to a catalytic effect of Al elements on the surface reaction and an increase in the effective surface reaction area of the active ZnO layer due to the coating of CNT templates with a higher surface-to-volume ratio structure. These results suggest that ZnO-CNT composites made of ultrathin Al-doped ZnO layers uniformly coated around carbon nanotubes can be promising materials for use in practical high-performance NO gas sensors.

Semiconducting metal oxides have been frequently used as gas sensing materials. While zinc oxide is a popular material for such applications, structures such as nanowires, nanorods and nanotubes, due to their large surface area, are natural candidates for use as gas sensors of higher sensitivity. The compound ZnO has been studied, due to its chemical and thermal stability, for use as an n-type semiconducting gas sensor. ZnO has a large exciton binding energy and a large bandgap energy at room temperature. Also, ZnO is sensitive to toxic and combustible gases. The NO gas properties of zinc oxide-single wall carbon nanotube (ZnO-SWCNT) composites were investigated. Fabrication includes the deposition of porous SWCNTs on thermally oxidized SiO2 substrates followed by sputter deposition of Zn and thermal oxidation at 400˚C in oxygen. The Zn films were controlled to 50 nm thicknesses. The effects of microstructure and gas sensing properties were studied for process optimization through comparison of ZnO-SWCNT composites with ZnO film. The basic sensor response behavior to 10 ppm NO gas were checked at different operation temperatures in the range of 150-300˚C. The highest sensor responses were observed at 300˚C in ZnO film and 250˚C in ZnO-SWCNT composites. The ZnO-SWCNT composite sensor showed a sensor response (~1300%) five times higher than that of pure ZnO thin film sensors at an operation temperature of 250˚C.

A cobalt oxide - tin oxide nanocomposite based gas sensor on an SiO2 substrate was fabricated. Granular thin film of tin oxide was formed by a rheotaxial growth and thermal oxidation method using dc magnetron sputtering of Sn. Nano particles of cobalt oxide were spin-coated on the tin oxide. The cobalt oxide nanoparticles were synthesized by polymer-assisted deposition method, which is a simple cost-effective versatile synthesis method for various metal oxides. The thickness of the film can be controlled over a wide range of thicknesses. The composite structures thus formed were characterized in terms of morphology and gas sensing properties for reduction gas of H2. The composites showed a highest response of 240% at 250˚C upon exposure to 4% H2. This response is higher than those observed in pure SnO2 (90%) and Co3O4 (70%) thin films. The improved response with the composite structure may be related to the additional formation of electrically active defects at the interfaces. The composite sensor shows a very fast response and good reproducibility.

We investigated the carbon monoxide (CO) gas-sensing properties of nanostructured Al-doped zinc oxide thin films deposited on self-assembled Au nanodots (ZnO/Au thin films). The Al-doped ZnO thin film was deposited onto the structure by rf sputtering, resulting in a gas-sensing element comprising a ZnO-based active layer with an embedded Pt/Ti electrode covered by the self-assembled Au nanodots. Prior to the growth of the active ZnO layer, the Au nanodots were formed via annealing a thin Au layer with a thickness of 2 nm at a moderate temperature of 500˚C. It was found that the ZnO/Au nanostructured thin film gas sensors showed a high maximum sensitivity to CO gas at 250˚C and a low CO detection limit of 5 ppm in dry air. Furthermore, the ZnO/Au thin film CO gas sensors exhibited fast response and recovery behaviors. The observed excellent CO gas-sensing properties of the nanostructured ZnO/Au thin films can be ascribed to the Au nanodots, acting as both a nucleation layer for the formation of the ZnO nanostructure and a catalyst in the CO surface reaction. These results suggest that the ZnO thin films deposited on self-assembled Au nanodots are promising for practical high-performance CO gas sensors.