We briefly review principles and main features of an electric double layer transistor (EDLT) as well as electric field induced superconductivity in SrTiO3. EDLT is a field-effect transistor that employs an electrolyte as a gate dielectric. An electric double layer between a semiconductor and the electrolyte attains much higher breakdown field than the maximum of a solid gate dielectric, resulting in high density charge accumulation up to 1014cm-2. That density is sufficient for inducing new physical phases, such as superconductivity and ferromagnetism, on various oxide systems. We employed a surface of a SrTiO3 single crystal as a semiconductor channel. We have demonstrated insulator-tosuperconductor transition by electric field-effect without chemical doping. Charge carrier density was linearly increased from zero to 1014 cm-2 with increasing gate bias to 3.5 V. Superconducting critical parameters, such as critical temperature Tc, critical magnetic field Hc, and critical current density Jc were examined as a function of carrier density by varying gate bias. Tc was almost constant as a function of the carrier density, contrasting to bell-shaped dependence of
Hc and Jc. Temperature dependence of I-V curve shows the BKT-type transition, which indicates two-dimensional superconductivity in the electric field induced superconductivity.
We present a fabrication procedure for ZnO channel waveguides intended for nonlinear optical applications. Ar ion
milling was used to etch the single crystal thin film samples, and the effects of bias power, chamber pressure and Ar flow
rate were investigated, finding optimal parameters for waveguide fabrication. The effect of sidewall roughness was
estimated by comparing the results of cut-back measurements and an analytical model. We show an easy and effective
method for the fabrication of ZnO channel waveguides.
Thin films of ZnO and MgxZn1-xO were epitaxially grown on Zn-polar ZnO substrates by plasma assisted
molecular beam epitaxy. The miscut of c-plane ZnO substrates toward the [1-100] axis direction leads to a flat substrate
surface with straight step edges. The growth mode of epitaxial ZnO films significantly depended on the growth
temperature, and a substrate temperature over 800°C was needed for flat film surfaces with monolayer-height steps.
Photoluminescence (PL) peak originating from the n = 2 state of A-free excitons was observed at 12 K for the ZnO films
grown under stoichiometric and O-rich growth conditions. MgxZn1-xO films were also fabricated under Zn-rich
conditions. The film surface exhibited a step-and-terrace structure. The effective PL lifetime of Mg0.08Zn0.92O film was as
long as 1.9 ns, which is the highest value ever reported, presumably due to a high purity level of the film.
We have used molecular beam epitaxy (MBE) to deposit gallium (Ga) doped ZnO (ZnO:Ga) films. The as-deposited ZnO:Ga films have worked as ohmic contacts for the p-type GaN layers without any kinds of post annealing process. The as-deposited ZnO:Ga films on a-plane sapphire substrates have resistivities of 2-4×10-4 Ωcm, and over 80 % transparency in the near-UV and visible wavelength regions. The brightness of InGaN light-emitting diodes (LEDs) with ZnO:Ga p-contacts has doubled compared to LEDs with conventional Ni/Au semi-transparent p-contacts when measuring the brightness from right above the device surfaces. In addition, using MBE, we have grown homoepitaxial polar ZnO films on (000+1)-plane (+c-plane) ZnO substrates, and also grown non-polar ZnO films on (1-100)-plane (m-plane) and (11-20)-plane (a-plane) ZnO substrates. Growth temperatures have not affected nitrogen-doping levels for +c-axis oriented (Zn-polar) nitrogen doped ZnO (ZnO:N) films. The phenomena were quite different from that for (000-1)-axis (-c-axis) oriented (oxygen-polar) growth, where nitrogen concentrations in ZnO decrease with increasing growth temperatures. We have observed c-axis direction growth for both of m-axis and a-axis oriented films. Oxygen-rich growth conditions flatten surfaces for both m-axis and a-axis oriented films, and the surfaces of m-axis oriented ZnO films flatten with increasing growth temperatures. Nitrogen concentrations in m-axis oriented ZnO:N films have been independent on growth temperatures.
We have grown a variety of oxide nanostructures, including nanodots, nanowires, and nanorings. The growth of these structures relies on precise growth mode control and requires a special pulsed laser deposition system which can work at temperatures above 1000C and at high background oxygen pressures. The dynamics of nanostructure growth have been studied in detail. In particular, we have determined the temperatures and deposition rates necessary for growing dot or wire structures on atomically flat surfaces. The nanostructures have been successfully included in fractional-layer superlattices for easier characterization.
High quality ZnO/Zn1MgO multi-quantum wells (MQWs) have been prepared on lattice-matched ScAIMgO4 substrates by laser-MBE method. Nine pixels of MQWs having different well widths were integrated in the same substrate by means of combinatorial masking techniques, which provided excellent specimens to systematically study the dependence of physical properties of MQWs on well widths. Optically pumped stimulated emission spectra were measured in these ZnO/Zn1MgO multi-quantum wells by using a tunable pulsed dye laser as excitation source. We investigated the pump-intensity dependence of the stimulated emission spectra from 5 to 300 K. At low temperatures, only one peak in the stimulated emission was observed, which could be assigned to the emission induced by exciton-exciton inelastic scattering (P-band). When the temperature increases above 160 K, there appears an additional peak at the lower energy side of the P-band, which was assigned to electronhole plasma emission. However, the emission due to the exciton-exciton scattering still remains up to room temperature. The gain spectrum for a multi-quantum well sample has been obtained by variable stripe method at room temperature. At an excitation intensity of about 2 MW/cm2, the peak gains for the P-band and electron-hole plasma emission are 239 cm1 and 380 cm1, respectively. The exciton binding energy was deduced from the energy difference between the P-band and free exciton band. The exciton binding energies of these samples having different well widths were found to increase with decreasing the well widths due to the quantum confinement effect. This enhancement of exciton binding energy should be favorable for the stability of exciton states at higher temperatures.
We have developed a laser molecular beam epitaxy system capable of the temperature-gradient and/or composition-spread integration of thin films in a substrate. The latter is achieved by using a moving mask system synchronizing with target exchange and laser pulse. The former employs a substrate holder having a controlled asymmetric thermal conduction heated by a focused Nd:YAG continuous wave laser beam. A concurrent x-ray diffractometer can immediately characterize the dependences of the lattice constant and crystalline quality on the film growth temperature and composition. The temperature-gradient method is very useful for revealing an optimum substrate temperature for epitaxial thin film growth. Several other characterization techniques such as magnetic field microscope and parallel transport measurement system developed for characterizing composition-spread thin films are presented.
Excitonic properties of high-quality ZnO/Zno,88Mgo.120 multiple quantum wells grown by laser molecular-beam epitaxy were investigated by excitonic absorption spectra taken at temperatures of 5—300 K. Strength of excitonphonon coupling was deduced from temperature dependence of linewidth of the fundamental excitonic absorption band. Significant reduction of the exciton-phonon coupling with decreasing the well width was observed, which is consistent with the confinement-induced enhancement of the exciton binding energy. The thermal shift of the lowest excitonic energy is independent of well width, suggesting the negligible strain effect characteristically inherent in this material. Growth temperature dependence of third-harmonic generation efficiency in (BaxSri1-x)2CuO3 alloyed epilayers is reported. It was found that, within the temperature range adopted in this work, the harmonic generation efficiency of the epilayer grown at higher temperature is larger than that grown at low temperature.
Combinatorial chemistry has been developed as an experimental method where it is possible to synthesize hundreds of samples all at once and examine their properties. Recently, we introduced the concept of combinatorial approach to computational chemistry for material design and proposed a new method called `a combinatorial computational chemistry'. In this approach, the effects of large number of dopants, substrates, and buffer layers on the structures, electronic states, and properties of metal oxide electronics material is estimated systematically using computer simulations techniques, in order to predict the best dopant, substrate, and buffer layer for each metal oxide electronics materials.
We report high-throughput optimizations for various material parameters of Mg,Zn1-xO and Zn1-xCdxO alloy films, Al-doped ZnO films, MgxZn1-xO/ZnO single quantum wells and superlattice structures with using combinatorial laser MBE. Combinatorial chips including nine thin film pixels were grown on lattice-matched ScAlMgO4 (0001) substrates by switching the mask patterns and targets during pulsed laser deposition.
TiO2 thin films doped with various transition metals were systematically fabricated by combinatorial laser MBE technique. Alternating KrF excimer laser ((lambda) equals 248 nm) ablation of TiO2 and Ti1-x MxO2 (M equals transition metal) was employed to deposit combinatorial library of 18 samples for each dopant with different concentrations. Anatase films with c-axis orientation were grown epitaxially on SrTiO3(001) substrate while the rutile phase films with a-axis orientation were on Al2O3(0001) substrate. Solid solubility of transition metals in both the phases was determined by X-ray diffraction. The anatase phase was found to dissolve the transition metals in higher concentrations than rutile phase. The parallel evaluation of the photocatalytic activity of the doped TiO2 in combinatorial libraries was performed with respect to photo-decomposition of water in presence of a small amount of oxidizing or reducing agent which induced pH changes on the pixels. The high throughput evaluation of combinatorially deposited photocatalytic thin films was realized by adopting a potentiometric pH field effect transistor for sensing such pH changes.
For the rapid structural characterization of combinatorial epitaxial thin films, we developed an X-ray diffraction system. A convergent X-ray beam from a curved crystal monochromator is focused on sample surface about 0.1 mm X 10 mm in size. Diffraction patterns of this area are simultaneously observed on the 2D detector within a few degree. Thus, rocking curve profiles of combinatorial epitaxial thin films for one-column pixels can be measured rapidly with Bragg peak of substrate; the measurement time depends on the film thickness, but the most cases are within one minute.
We have developed the simultaneous optical measurement method by using the optic fiber bundles specialized for combinatorial samples combined with the arrayed charge coupled devices. This also can be used for experiments done at cryogenic temperatures. The smoother dependence upon various growth parameters could be obtained by virtue of the combinatorial fabrication method. Our present study revealed that the use of lattice-matched ScAlMgO4 substrates greatly improved the optical (excitonic) properties of epitaxial ZnO layers as well as ZnO-based quantum wells. The improved points by virtue of lattice-matching are as follows: (1) reduction of the nonradiative decay rate of excitons, (2) settlement of the undesired criterion of well- width, the limit to which the relevant quantum confinement can be achieved, (3) bright excitonic photoluminescence at room temperature as the result of increased quantum efficiency.
Due to the non-steady state nature of film growth by laser MBE, as well as by the conventional pulsed laser deposition (PLD), we could find an advantage of the method for controlling the film growth. The independent optimization of nucleation and growth processes is possible by pulse sequence and laser energy density. Another critical factor for controlling the growth mode was revealed to exist in the surface state of the substrate as the stating point of film growth. We have developed a wet etching method for automatically finishing SrTiO3 substrate surface to facilitate the layer by layer growth of high Tc and other oxide thin films. The sequential deposition of SrO and BaO monolayers on the treated SrTiO3 substrate greatly reduced the nucleation of precipitates in the YBa2Cu3O7 (YBCO) thin films. Thus, PLD growth of YBCO thin film could be controlled on an atomic scale. Temperature gradient deposition achieved the orientational control of YBCO thin films on (100) and (110) SrTiO3 substrates. Laser MBE successfully produced high quality epitaxial oxide films by 2-dimensional layer by layer manner as well as by step-flow mode, as verified by the sharp RHEED intensity oscillation. This dimension control epitaxy enabled us to fabricate oxide superlattices and quantum wires. With the substrate treatment and buffer layer techniques, together with suitable choice of insulating layer material, we have verified the fabrication of superconducting-insulating-superconducting trilayer which is the prototype for tunneling junctions. A possibility of using (110) oriented YBCO thin films for Josephson THz laser is also discussed.
In relation to our research for the fabrication of high-Tc Josephson tunnel junction composed of YBCO(S)/oxide insulator(I)/YBCO layers, two crystal engineering issues are presented and discussed on pulsed laser processing of oxide thin films. One is the epitaxial growth of highly crystalline and orientation-controlled YBCO films and the other is the molecular layer epitaxy of perovskite and rock salt oxides films. Quantitative results are presented on the crystal quality, surface atomic layers and morphology, and electronic properties of the films and junctions. Discussion will be made on such problems as the thermodynamics versus kinetics in the film growth, identification and control of the topmost atomic layers of substrates and growing films, and electronic state of high-Tc films based on the scanning tunneling and photoelectron yield spectra.
We have designed and constructed a cryogenic photoelectron yield spectroscopy (PYS) and demonstrated a high energy resolution of 10 meV and a wide dynamic range of 7 orders of magnitude. This system enabled us to measure the absolute value of work function and analyze the electronic structure around the Fermi level (EF) for a Bi2Sr2CaCu2Ox(BSCCO) single crystal and YBa2Cu3O7-(delta ) (YBCO) epitaxial films. When the photoelectron was collected along <001> axis, semiconductive spectrum having a broad tail was observed for both materials. When the measurement was performed from the edge of CuO2 plane, we observed metallic spectra with sharp threshold, of which slope depended on temperature in a way consistent with the Fermi-Dirac distribution function. For BSCCO, a metallic spectrum superimposed a dip structure at 10 K in the vicinity of EF. The data could be well fitted with a curve numerically simulated from the BCS function with a superconducting gap value ((Delta) ) of 20 meV.
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