Microstructures of epitaxial Ca0.33CoO2 thin films, which were grown on m plane and c(0001) plane of α–Al2O3 by the reactive solid-phase epitaxy (R-SPE) method and the subsequent ion-exchange treatment, were investigated in detail by using selected-area electron diffraction, high-resolution transmission electron microcopy, spherical-aberration-corrected high-angle annular dark-field scanning transmission electron microscopy (Cs-corrected HAADF-STEM), and electron energy-loss spectroscopy (EELS). Detailed electron diffraction analyses reveal that the orientation relationships between Ca0.33CoO2 thin film and substrate are and , having an angle of about 43° with for the film deposited on m plane, and and for the film deposited on c(0001) plane though a Ca–Al–O amorphous layer formed between them. CoO seed layer near the interface and residual Co3O4 phase inside the films were observed and identified by HAADF-STEM and EELS in both samples. Such microstructural configuration indicates that the processes of film growth during R-SPE are (i) oxidation of CoO into Co3O4 with residual CoO layer near the interface and (ii) intercalation of Na+ layer into Co3O4 to achieve the layered NaxCoO2 film while forming Na–Al–O amorphous layer at the interface.

Very recently, we have found that the high density 2DEG (ne ∼1021 cm−3), which is confined within a unit cell layer thickness of SrTiO3, exhibits unusually large Seebeck coefficient (S2DEG/Sbulk ∼5)[1]. In the optimum, extremely high ZT2DEG of ∼2.4 can be obtained at room temperature, while the effective ZTeff. was only ∼0.24 because 9 unit cells of electrically insulating SrTiO3 layers were used to fabricate the 2DEG structure. Thus, high ZTeff can be realized if the insulating layer thickness is reduced significantly. We selected BaTiO3∼SrTiO3:Nb superlattice to reduce insulating layer thickness because dielectric constant of BaTiO3 is one order of magnitude large (∼3,000) as compared to that of SrTiO3 (∼300). We expected that the conduction electrons can be confined much strongly in the SrTiO3:Nb layer by sandwiching between highly dielectric BaTiO3 layers. As a result, we clarified that the critical BaTiO3 layer thickness is 1.2 nm, significantly small as compared to SrTiO3 layer (4 nm). The BaTiO3/SrTiO3:Nb superlattice films were fabricated by a pulsed laser deposition (PLD) method on (001)-face of LaAlO3 single crystal substrate at 900°C. During the film growth, we monitored RHEED intensity oscillation to control layer thickness precisely. Out-of-plane high-resolution X-ray diffraction measurements and cross sectional HAADF-STEM observations revealed that the resultant films were high quality BaTiO3/SrTiO3:Nb superlattice. Hall mobility of the SrTiO3:Nb layer was 0.4 cm2·V−1·s−1, while that of superlattice decreased gradually with increasing BaTiO3 layer thickness most likely due to that intra layer diffusion of Ba2+ ion occurred between BaTiO3 and SrTiO3:Nb layers[2], which was clearly observed by the EELS mapping. Seebeck coefficient |S|300K of SrTiO3:Nb layer was 57 μV·K−1, which corresponds carrier concentration ne of 5×1021 cm−3. The |S|300K value became large with decreasing the SrTiO3:Nb layer thickness (dSrTiO3:Nb) and it reached 305 μV·K−1, which is approximately 5 times larger than that of SrTiO3:Nb bulk. The slope of log |S|- log dSrTiO3:Nb plots was 1/2, suggesting that quantum size effect occurred. Critical BaTiO3 layer thickness for the quantum confinement of the electrons was 1.2 nm (3 unit cells of BaTiO3), which is significantly small as compared to SrTiO3 (4 nm). Thus, BaTiO3/SrTiO3:Nb superlattice would be a promising candidate to realize high ZTeff.

Recently, we have found that high-density two-dimensional electron gas (2DEG) confined within a unit cell layer thickness in SrTiO3 exhibits extremely large Seebeck coefficient (|S|2D) [REF], approximately five times larger than |S|3D. Here we clarify the origin of giant |S|2D using [(SrTiO3)x/(SrTi0.8Nb0.2O3)y]20 (x = 1∼60, y = 1∼20) superlattices. The |S|2D value increased proportionally to y{0.5, indicating that the density of states of the conduction band increases with decreasing y (quantum size effect). Superlattices of [(SrTiO3)x/(SrTi0.8Nb0.2O3)y]z (x = 0∼60, y = 1∼20, z = 20) were fabricated on the (001)-face of LaAlO3 substrate by PLD using RHEED to count the number of SrTiO3 or SrTi0.8Nb0.2O3 layers. HR-XRD and HAADF-STEM studies revealed that high-quality [(SrTiO3)17/(SrTi0.8Nb0.2O3)y]z superlattices were successfully fabricated. A dramatic increase of |S|2D is seen with decreasing y-value of the [(SrTiO3)x/(SrTi0.8Nb0.2O3)y]z superlattices. The slope for the plots of log |S|2D - log y is -0.5, and reached 290 μVK−1 (y = 1), which is ∼5 times larger than that of the SrTi0.8Nb0.2O3 bulk (|S|3D = 61 μVK−1). Further, the |S|2D value monotonically increases with x-value and is saturated when x-value > 16 (6.25 nm). We clarified that the critical barrier thickness for electron tunneling in [(SrTiO3)x/(SrTi0.8Nb0.2O3)y]z superlattice is 6.25 nm (16 unit cell layers of SrTiO3). The present results give very important information to utilize the [(SrTiO3)x/(SrTi0.8Nb0.2O3)y]z superlattices for practical application.

We propose herein that amorphous oxide semiconductor (AOS) superlattices, which can be deposited on various substrate including glasses or plastics without any substrate heating, are appropriate for the realization of superlattice thermoelectric devices. As an example, thermoelectric properties of AOS superlattices composed of a-In-Zn-O (well) and a-In-Ga-Zn-O (barrier) layers, fabricated on SiO2 glass substrate by pulsed laser deposition at room temperature, were measured to clarify whether enhancement of Seebeck coefficient |S| occurs or not. The |S|2D value increases drastically with decreasing a-In-Zn-O thickness (dIZO) when the dIZO is < ∼5 nm, and reached 73 μV·K-1 (dIZO = 0.3 nm), which is ∼4 times larger than that of bulk |S|3D (19 μV·K-1), while it kept high electrical conductivity, clearly demonstrating that the quantum size effect can be utilized in AOS superlattices.

Objectives: We have compared mortality and risk factors for late deaths in patients with tetralogy of Fallot undergoing surgical repair in 1972 and 1982 in a Japanese multicentric study, examining in particular the impact of time of repair. Background: There is limited information on the effect that time of repair, and our constantly changing approach to it, has on late outcome in repaired tetralogy of Fallot. Methods: We analysed the Japanese registry of deaths occurring after surgical repair of tetralogy of Fallot. We studied two postoperative 1-year cohorts of survivors of surgery performed in 12 centers. Of the patients, 122, aged 29 ± 12 years, had undergone repair in 1972, their age at repair being 9.6 years. An additional 186 patients, aged 23 ± 8.7 years, had been repaired in 1982 at the age of 7.7 years. Results: Annual mortality, as judged per 100,000 population of patients with tetralogy of Fallot, declined from 0.387 in 1972 to 0.196 in 1982. Significant differences were deaths following surgery (27% vs. 13%, p < 0.001), patching of the subpulmonary outflow tract (48% vs. 89%, p < 0.001), and transjunctional patching (13% vs. 63%, p < 0.001). Late death was observed in 6 vs. 3 patients (9/308, 2.9%). The actuarial rate of survival calculated over 14 years was 97% vs. 98%. Reoperation was performed in 5 vs. 9 patients (14/308, 4.5%). Risk factors for late death were age at repair (p = 0.01), and history of reoperation (p < 0.001). Transjunctional patching (p = 0.01) proved to be associated with late mortality only in patients repaired in 1972. Conclusions: Late survival was excellent, with a low incidence of reoperations in both groups of patients. The era of repair has a big influence on total and operative mortality, but has only a small impact on late mortality. Ongoing analysis of follow-up will possibly reveal subsequent changes with time.

Processes and preparation conditions for growing epitaxial thin films of Cu-based, layered oxychalcogenides LnCuOCh (Ln = La, Ce, Pr or Nd; Ch = S1-xSex or Se1-yTey) are reported. Epitaxial thin films on MgO (001) substrates were prepared by a reactive solid-phase epitaxy method. Four-axes high-resolution x-ray diffraction measurements revealed that the crystallographic orientation is (001)[110] LnCuOCh || (001)[110] MgO and the internal stress of the crystalline lattices in the films are relaxed during thermal-annealing process of the reactive solid-phase epitaxy. Furthermore, except for CeCuOS, systematic variations in the lattice constant by chalcogen or lanthanide ion substitutions were observed. These results demonstrated that the reactive solid-phase epitaxy is an efficient technique for fabricating LnCuOCh epitaxial films.

Electronic structures of layered oxychalcogenides, LaCuOCh (Ch=S, Se, Te) and La2CdO2Se2, were studied using ab-initio band calculations in relation to their optical and electronic properties. It was found that the dispersions of the top valence bands are much smaller in Γ-Z direction than in Γ-X direction, indicating that the electronic structure is highly two-dimensional, and that holes are confined in the CuCh or CdSe layers. The two-dimensional electronic structure is supported experimentally by staircase-like structure observed in optical absorption spectra at 10 K associated with two excitonic absorption peaks split by spin-orbit interaction of Ch ions. La2CdO2Se2has the largest bandgap due to the two-dimensional network structure of CdSe tetrahedra.

Carrier transport properties and electronic structure of an n-type transparent oxide semiconductor, InGaO3(ZnO)5, were investigated using single-crystalline thin films. Room-temperature Hall mobility strongly depends on carrier concentration, and rapidly increased from ∼ 2 cm2(Vs)-1 to > 10 cm2(Vs)-1 around the carrier concentration (Nth ∼3 × 1018 cm−3. This change is associatedwith insulator-metal transition. These results are explained by a model similar to Anderson localization, in which shallow semi-localized states are formed originating from random distribution of Ga3+ and Zn2+ ions in the intrinsic crystal structure of InGaO3(ZnO)5. The present conclusion suggests that electron densities larger than Nth are necessary to attain high performances in drift carrier devices fabricated using InGaO3(ZnO)5. It was demonstrated that transparent filed-effect transistors exhibited good performances such as a “normally-offcharacteristics”, an on/off current ratios as large as 105 and a field-effect mobility ∼80 cm2(Vs)-1when high-k material, amorphous HfOx, was used as a gate insulator.

An amorphous p-type conductive oxide semiconductor was created based on a mother crystalline material, a p-type conductive ZnRh2O4 spinel. The amorphous film of ZnRh2O4 was deposited by an rf sputtering method. Seebeck coefficient was positive, +78 μVK-1, indicating that major carrier is a positive hole. A moderate electrical conductivity (2 S cm-1 at room temperature) for a p-type semiconductor was observed. Optical band gap was estimated to be 2.1 eV. P-n junction diodes with a structure of Au / a-ZnRh2O4 / a-InGaZnO4 / ITO fabricated on glass substrates, operated with a good rectifying characteristics, a rectification current ratio at ± 5V of ∼103. The threshold voltage was 2.1 eV, which corresponds to the band gap energy of the amorphous ZnRh2O4. This is the first discovery of a p-type amorphous oxide and the demonstration of p-n junction all composed of amorphous oxide semiconductors.

Epitaxial films of LaCuOS, a wide gap p-type semiconductor, were grown on yittria- stabi-lized-zirconia (YSZ) (001) or MgO (001) substrates by a reactive solid phase epitaxy (R-SPE) method. Crystal quality, electrical and optical properties on the epitaxial films on each substrate are examined in this paper. Achievement of the heteroepitaxial growth of LaCuOS on the MgO (001) substrate improves optical properties of LaCuOS such as spectral bandwidths and emission intensity, suggesting that the MgO (001) substrate is more preferable than the YSZ (001) for epitaxial growth substrate for LaCuOS.

Several Cu(I)-containing layered oxysulfides were selected as candidates for wide-gap p-type semiconductors by extending a concept of a materials design for transparent p-type conducting oxides. The electrical and optical properties of the selected oxysulfides were investigated, and their electronic structures were analyzed by energy band calculations. LaCuOS, Sr2Cu2ZnO2S2 and Sr2CuGaO3S were found to be wide-gap p-type semiconductors, and LaCuOS showed the largest energy gap (Eg=3.1eV) among these layered oxysulfides. It was also found that LaCuOS shows band edge emission under uv excitation at room temperature, which is consistent with the results of the energy band calculations that LaCuOS has a direct-allowed-type energy gap at Γ point. In further materials research, analogous layered oxychalcogenides such as LaCuOSe and LnCuOS (Ln=Pr, Nd) were found to show similar optical and electrical properties to those of LaCuOS. Therefore, it is considered that the layered crystal structure and the electronic structure are responsible for the wide-gap p-type conductive properties in these materials.

Indium-tin-oxide films were grown hetero-epitaxially on YSZ surface at a substrate temperature of 900 °C, and their surface microstructures were observed by using atomic force microscopy. ITO films grown on (111) surface of YSZ exhibited very high crystal quality; full width at half maximum of out-of-plane rocking curve was 54 second. The ITO was grown spirally, with flat terraces and steps corresponding to (222) plane spacing of 0.29 nm. Oxygen pressure during film growth is another key factor to obtain atomically flat surfaced ITO thin film.

A transparent oxide semiconductor with delafossite structure, CuInO2, was found to exhibit both p-type and n-type conduction by doping of an appropriate impurity and tuning of proper film-deposition conditions. Thin films of Ca-doped or Sn-doped CuInO2 were prepared on -Al2O3 (001) single crystal substrates by pulsed laser deposition method. The films were deposited at 723 K in O2 atmosphere of 1.0 Pa for the Ca-doped films or 1.5 Pa for the Sn-doped films. The positive sign of the Seebeck coefficient demonstrated p-type conduction in the Ca-doped films, while the Seebeck coefficient of the Sn-doped films was negative indicating n-type conductivity. The electrical conductivities of Ca-doped and Sn-doped CuInO2 thin films were 2.8×10−3 S·cm−1 and 3.8×10−3 S·cm−1, respectively, at 300 K. The optical band gap of each film was estimated to be ∼3.9 eV. Since CuInO2 exhibited bipolarity in electrical conduction, transparent p-n homojunctions based on CuInO2 were fabricated on (111) surface of yttria-stabilized zirconia single-crystal substrates. The structure of the diode was In2O3:Sn / n-CuInO2:Sn / p-CuInO2:Ca / In2O3:Sn electrode on the substrate. The contact between the n-and p-type CuInO2 semiconducting oxides was found to be rectifying. The turn-on voltage was ∼1.8 V.

Deep ultraviolet transparent and electrical conductive β-Ga2O3 film was prepared on SiO2 glass substrate. The film had electric conductivity of 1 Scm−1, carrier density of 1.4 × 1019cm−3 and mobility of 0.44 cm2V−1s−1. Internal transmittance at wavelength of 248 nm exceeded 50 %. Conductivity was enhanced at an oxygen pressure less than 10−4 Pa, and transparency appeared at a substrate temperature over 800 °C.

High quality ITO thin films were grown hetero-epitaxially on extremely flat substrate of (001) YSZ by a pulsed laser deposition technique at a substrate temperature of 600°C. The crystal orientation relationship between the film and YSZ were confirmed as ITO (001) // YSZ (001) and ITO (010) // YSZ (010), respectively, by HR-XRD and HR-TEM. The carrier densities of the films were almost equal to Sn02 concentration in the films. That is, almost all the doped Sn4+ ions were activated to release electrons to the conduction band. The carrier densities of the films were enhanced up to 1.9×1021cm−3, while the Hall mobility showed a slight, almost linear, decrease from 55 to 40cm2V−1s−1 with increasing SnO2 concentration. The low resistivity is due to larger electron mobility, which most likely resulted from good crystal quality of the films. The optical transmissivity of the film exceeded 85% at wavelengths from 340 to 780nm.

Room temperature operation of UV LED is realized for the first time using a hetero p-n junction composed of transparent conductive oxides, p-SrCu2O2 and n-ZnO. Ni/SrCu2O2/ZnO/ITO multi-layered film was epitaxially grown on an extremely flat YSZ (111) surface by a PLD. The grown films were processed by a conventional photolithography, followed by reactive ion etching to fabricate p-n junction diode. The resultant device exhibited rectifying I-V characteristics inherent to p-n junction whose turn-on voltage was about 1.5V. A relatively sharp electro-luminescence band centered at 382nm was generated when applying the forward bias voltage larger than the turn-on voltage of 3V. The red shift in the EL peak was noticed from that of photo-luminescence (377nm), which was most likely due to the difference in the excited state density between the emission processes. The EL band is attributed to transition in ZnO, probably to that associated with electron-hole plasma. The photo-voltage was also generated when the p-n junction was irradiated with UV light of which energy coincided with both exciton and band-to-band transitions in ZnO.

Heteroepitaxial ZnO films were grown on (111) surface of yttria stabilized zirconia (YSZ) and (0001) surface of sapphire by PLD method, using KrF eximer laser (248nm) in an ultra-high-vacuum chamber. ZnO grown on YSZ (111) at the substrate temperature of 800°C had an epitaxial relationship at the ZnO/YSZ interface of ZnO [1120]//YSZ [110]. Hexagonalshaped grains were observed whose surfaces were atomically flat. The grain size of ZnO increased and the Hall mobility rose toward 1400nm and 75cm2/Vs. respectively as film thickness increased from 10 nm to 800 nm.