Frontier of transparent oxide semiconductors

Recent advancements of transparent oxide semiconductors (TOS) toward new frontiers of “oxide electronics” are reviewed based on our efforts, categorized as “novel functional materials”, “heteroepitaxial growth techniques”, and “device fabrications”. Topics focused in this paper are: (1) highly conductive ITO thin film with atomically flat surface, (2) p-type TOS material ZnRh₂O₄, (3) deep-ultraviolet (DUV) transparent conductive oxide β-Ga₂O₃ thin film, (4) electrochromic oxyfuolide NbO₂F, (5) single-crystalline films of InGaO₃(ZnO)_m grown by reactive solid-phase epitaxy, (6) p-type semiconductor LaCuOS/Se epitaxial films capable of emitting UV- and purple-light, (7) p–n homojunction based on bipolar CuInO₂, (8) transparent FET based on single-crystalline InGaO₃(ZnO)₅ films, and (9) UV-light emitting diode based on p–n heterojunction.     

Effects of electrode materials on freezing of supercooled water in electric freeze control

In order to clarify effects of electric charge on freezing of supercooled water, experiments were carried out with various kinds of electrodes in supercooled water. Water sample was kept in a test tube and cooled down at a constant cooling rate. When the water sample was maintained under a supercooling state, an electric charge was applied to the water sample with a small electric current. The degree of supercooling was measured continuously. Then the degree of supercooling at freezing was determined. Six kinds of materials were used for electrodes. Those materials were Aluminum, Copper, Argentum, Aurum, Platinum and Carbon. It was found that the effects of electric charge were distinct according to the material used for electrodes. The degree of supercooling at freezing was the lowest in the case of Aluminum. On the other hand, the highest value of the degree of supercooling at freezing was obtained in the case of carbon. The reason for the difference in the degree of supercooling at freezing by six materials was discussed.     

Thin film fabrication of nano-porous 12CaO·7Al2O3 crystal and its conversion into transparent conductive films by light illumination

Thin film fabrication of crystalline 12CaO·7Al₂O₃ (C12A7) with zeolitic structure was examined, and their electrical and optical properties were measured. Polycrystalline thin films were prepared by post-annealing of amorphous films in oxygen atmosphere at temperatures above 800 °C. Choice of substrates was crucial for obtaining single-phase thin films. Although various oxide substrates (single crystals of Al₂O₃, Y-stabilized ZrO₂, MgO and silica glass) were examined, single-phase films were obtained only for MgO substrates and the other substrates reacted with the CaO component in the films during post-annealing. The optical band gap of C12A7 was evaluated to be 5.9 eV. Hydride ions were incorporated into the film by a thermal treatment in a hydrogen atmosphere at 1200 °C. The resulting transparent thin films were converted into transparent persistent electronic conductors exhibiting an electrical conductivity 6.2×10⁻¹ S cm⁻¹ at 300 K by ultraviolet light illumination. This is the first example of transparent conductive thin film in which conductive areas can be patterned directly by light.     

ESR of Cu2+and Tl2+ in thallium borate glasses

The electron spin resonance (ESR) and optical absorption spectra of Cu²⁺ were measured in thallium borate glasses in order to investigate the effects of glass transition temperature,T _g, upon the responses of cupric ion in alkali borate glasses. The ESR of Tl²⁺ induced by-ray irradiation was also obtained. An abrupt increase in the covalency of in-plane Cu²⁺-O-bonding was observed in the Tl₂O system as well as in the Na₂O system in a similar B₂O₃ composition range althoughT _g for the Tl₂O glasses has little dependency on the composition compared with the Na₂O glasses. The trend in the variation of the S-character of the Tl²⁺ unpaired electron with composition agreed with that of the covalency of in-plane Cu²⁺-O-bonding. The structure of the anion group present in Tl₂O glasses was also examined by laser reman spectroscopy.     

Photochemical reaction in azobenzene-containing rigid poly(amide acid) networks

Photochemical reaction of azobenzenes embedded into rigid poly(amide acid) (PAA) networks, which undergo reversible photomechanical response upon alternating irradiation of 405 nm and 532 nm lights, was explored. Azobenzene functionalities are incorporated into the PAA backbone that is end-linked with tri- and tetra-armed crosslinkers, 1,3,5-tris(4-aminophenyl)benzene (TAPB) and tetra(4-aminophenyl)methane (TAPM), respectively, to give photoresponsive polymer networks. It was discovered that the trans-to-cis photoisomerization rate of azobenzene moiety is highly dependent on the network architecture. Before crosslinking, the photoisomerization rate is considerably low and totally independent on molecular weights of the backbone whereas, after crosslinking, the rate is dramatically enhanced and highly dependent on the molecular weights. A crosslinker effect on the photomechanical response is also disclosed. These results are attributed to an inter-chain aggregation of PAA backbones. The bulky structure and superior connectivity of TAPM make the network structure spatially extended with less defects, which not only prevents the aggregation but also contributes to the nano-to-macroscopic propagation of molecular deformation of azobenzene.     

Fine characterization of plasma‐polymerized films from a methane/air mixture

The plasma polymerization of methane/air mixtures was performed to produce a hydrophilic film on a substrate, and the obtained films were characterized with ellipsometry, elemental analysis, Fourier transform infrared spectroscopy, X‐ray photoelectron spectroscopy, atomic force microscopy, and contact‐angle measurements. Fourier transform infrared revealed that the structure of the plasma‐polymerized films changed with increasing film thickness; that is, an increase in the film thickness led to an increase in the absorbance ratio of the carbonyl band at 1664 cm^?1 to the methyl band at 1385 cm^?1. Although the contents of nitrogen and oxygen measured by elemental analysis changed with the film thickness, the contact angle and X‐ray photoelectron spectroscopy atomic ratio of the films were independent of it. Nitrogen and oxygen were contained in the bulk more than on the surface of the films. Nitrogen and oxygen were copolymerized with methane, and the properties of the obtained films were similar to those of an amide compound. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 101: 3408–3414, 2006     

Thermoelectric Power in Nonstoichiometric Orthorhombic Titanium Oxides

Nonstoichiometric orthorhombic titanium oxides (TiO _x ; x =1.86–1.94) prepared by reducing the anatase titanium oxide in H₂ at 950°C are found to show large thermoelectric power. Their Seebeck coefficients are in the range −0.060 to −0.518 mV/K, and theoretical discussions are made based on the assumption that the electronic spin entropy dominating the entropy current is a main factor of the thermoelectric power. The figure of merit for TiO_1.94 at 70°C is estimated at 0.195. The nonstoichiometric orthorhombic titanium oxides, containing no hazardous elements, are promising materials for thermoelectric power generation.     

Evolution model of δ³⁴S and δ¹⁸O in dissolved sulfate in volcanic fan aquifers from recharge to coastal zone and through the Jakarta urban area, Indonesia

The sources of sulfate in an aquifer system, and its formation/degradation via biogeochemical reactions, were investigated by determining sulfate isotope ratios (δ³⁴S_SO4 and δ¹⁸O_SO4) in dissolved sulfate in groundwater from the Jakarta Basin. The groundwater flow paths, water ages, and geochemical features are well known from previous studies, providing a framework for the groundwater chemical and isotopic data, which is supplemented with data for spring water, river water, hot spring water, seawater, detergents, and fertilizers within the basin. The sulfate isotope composition of groundwater samples varied widely from − 2.9‰ to + 33.4‰ for δ³⁴S_SO4 and + 4.9‰ to + 17.8‰ for δ¹⁸O_SO4 and changed systematically along its flow direction from the mountains north to the coastal area. The groundwater samples were classified into three groups showing (1) relatively low and narrow δ³⁴S_SO4 (+ 2.3‰ to + 7.6‰) with low and varied δ¹⁸O_SO4 (+ 4.9‰ to + 12.9‰) compositions, (2) high and varied δ³⁴S_SO4 (+ 10.2‰ to + 33.4‰) with high δ¹⁸O_SO4 (+ 12.4‰ to + 17.3‰) compositions, and (3) low δ³⁴S_SO4 (<+6.1‰) with high δ¹⁸O_SO4 (up to + 17.8‰) compositions. These three types of groundwater were observed in the terrestrial unconfined aquifer, the coastal unconfined and confined aquifers, and the terrestrial confined aquifer, respectively. A combination of field measurements, concentrations, and previously determined δ¹⁵N_NO3 data, showed that the observed isotopic heterogeneity was mainly the result of contributions of pollutants from domestic sewage in the rural area, mixing of seawater sulfate that had experienced previous bacterial sulfate reduction in the coastal area, and isotopic fractionation during the formation of sulfate through bacterial disproportionation of elemental sulfur. Our results clearly support the hypothesis that human impacts are important factors in understanding the sulfur cycle in present-day subsurface environments. A general model of sulfate isotopic evolution along with groundwater flow has rarely been proposed, due to the complicated hydrogeological research setting that causes varied isotope ratios, although its understanding has recently received great attention. This pioneer study on a simple volcanic fan aquifer system with a well-understood groundwater flow mechanism provides a useful model for future studies.