The {100}-oriented (CaxSr1-x)Si2 thin films have been prepared by co-sputtering method at various deposition temperatures. Constituent phase of the films primarily depends on the deposition temperature and the composition x. Although CaSi2 films consisted of layered structure regardless of deposition temperature, the phase was changed by the deposition temperature: the majority phases of the film deposited at 600°C, 650°C and 700°C were 1T layered structure, 1T layered structure + 2H layered structure and 1T layered structure + 6R layered structure, respectively. When the (CaxSr1-x)Si2 films deposited at 700°C, the α-SrSi2-type phase was mainly confirmed below x = 0.17, which is the most stable phase of SrSi2. However, the main phase of all CaxSr1-xSi2 films deposited at 600°C changed to be 1T-type layered structure. Substitution with Ca below x = 0.50 in the film deposited at 600°C led to the decrease in the electrical resistivity compared with that of pure SrSi2.

Metal Ir films were prepared by spray chemical vapor deposition (CVD) in air from an Ir precursor, (1,3-cyclohexadiene)(ethylcyclopentadienyl)iridium, Ir(EtCp)(CHD). Film deposition was ascertained at 270–430°C on a SiO2/Si substrate and the deposition rate increased with the deposition temperature but was saturated above 330°C. The obtained films consisted of Ir metal without any iridium oxide impurity irrespective of the deposition temperature. Films tended to orient to (111) with increasing deposition temperature. Resistivity of these Ir films decreased with increasing film thickness and reached to values on the order of 10-6 Ω・cm, which was the same order of the values for bulk Ir metal. Good step coverage was observed for the Ir metal films deposited at 270°C and 330°C. This shows that the simple spray CVD process in air is a good candidate for depositing Ir metal films with good conductivity and step coverage.

Ca-Mg-Si films were firstly prepared on (001)Al2O3 substrates by RF-magnetron sputtering method from Mg disc target together with Ca and Si chips. The composition of the deposited films was controlled by adjusting deposition temperature and Ca/Si area ratio of Ca and Si chips on Mg disk target. Ca0.32Mg0.33Si0.35 film deposited at 610 K consisted of a single phase of CaMgSi and this CaMgSi phase was stable after heat treated at 770 K under an atmospheric Ar with 5% -H2. As-deposited film shows the semiconductor behavior and have a power factor of 50 μW/(mK2) at 670 K, while annealed one showed the metallic behavior and its power factor down below 10 μW/(mK2) at 320-770 K. On the other hand, Ca0.27Mg0. 51Si0.2 film deposited at 590 K showed no obvious crystalline phase but became single phase of Ca7Mg7.25Si14 after heat treatment at 770 K under an atmospheric Ar with 5% -H2. As deposited film had a large power factor of 100 μW/(mK2) at 670 K. However, power factor decreased below 1 μW/(mK2) at 320-770K after the heat treatment at 770 K under an atmospheric Ar with 5% -H2.

A method for controlling the conduction-type in Mg2Si films without doping is investigated. Mg2Si films exhibit p-type conduction after a post-heat treatment up to 500 °C in atmospheric He. However, covering the films with Mg ribbon during a subsequent heat treatment at 500 °C converts the conduction to n-type, demonstrating that the heat treatment atmosphere can control the conduction type. Based on the reported first principles calculations suggesting that interstitial Mg and Mg vacancies in Mg2Si are the origins of n-type and p-type conduction, respectively, the post-heat treatment in He induces Mg vacancies due to the evaporation of Mg from the film, resulting in p-type conduction. The subsequent heat treatment when the film is covered with Mg ribbon fills the Mg vacancies and the additional interstitial Mg is incorporated, resulting in n-type conduction. These observations differ from the reported data for heat treatment of stable n-type conduction in non-doped Mg2Si-sintered bodies and may realize a novel control method for the conduction type in Mg2Si films.

Semiconducting iron disilicide (β-FeSi2) island grains of 50-100 nanometers in size were formed on the surface of Au-coated 3C-SiC powder by metal-organic chemical vapor deposition. On the surface of 3C-SiC powder, the Au-Si liquidus phase was obtained via a Au-Si eutectic reaction, which contributed to the formation of the β-FeSi2 island grains. This β-FeSi2/SiC composite powder could evolve hydrogen (H2) from methyl-alcohol aqueous solution under irradiation of visible light with wavelengths of 420-650 nm.

(KxNa1−x)NbO3 films were deposited on Nb-doped (100)SrTiO3 substrates at 240 °C for times between 1 and 6 h by a hydrothermal method. Over this time series, the measured (K + Na)/Nb ratio of the films was found to remain constant, but the bulk K/(K + Na) ratio, x, decreased from an initial value of 0.75–0.56. It was determined that film growth initially proceeded through crystallization of the K-rich phase (K0.75Na0.25)NbO3. For film growth times greater than 3 h, a second perovskite phase with a smaller unit cell volume was detected, with an estimated composition of (K0.36Na0.64)NbO3. As such, the measured bulk composition value x = 0.56 was determined to be the result of a combination of these two phases, as opposed to originating from a single phase. Cross-sectional transmission electron microscopy analyses of films prepared for 6 h revealed that they consist of two layers in the direction normal to the substrate; this bilayer-type structure, only observed for hydrothermal growth of this material, is considered to arise from the large solubility mismatch between the Nb precursor and KOH and NaOH in the growth solution.

We propose some chemical processing procedures for fabricating thin films in Hf-Zr-O system by a unique film deposition technique using supercritical carbon dioxide fluid (scCO2), i.e., supercritical fluid deposition (SCFD), which would be an prospective approach for fabricating metal-oxide films for integrated circuits because of its unique characteristics; e.g., extraction ability, transportation capability, and reaction equilibrium etc., are quite favorable for the film deposition from metal-complex precursors.

The SCFD was accomplished in a closed batch-type reaction apparatus, consisting of two steps; (a) material deposition and (b) subsequent post-treatment under scCO2 atmosphere. Thin films of amorphous Hf-Zr-O were deposited on platinized silicon [(111)Pt/TiO2/(100)Si] substrates by SCFD using metal-complex precursors M[OCH(CH3)]2(C9H11O2)2 (M = Hf or Zr) at reaction temperature of 100 – 300 °C, significantly lower than those for MOCVD. These films possessed dielectric permittivity’s of approximately 20 – 25, comparable to those from conventional processes, although they still included residue of organic species that prompt the dielectric degradation under lower-frequency bias application.

The Au-Si liquid phase was obtained by melting the Si surface via Au-Si eutectic reaction, which contributed to the formation of semiconducting iron disilicide (β-FeSi2), on Au-coated Si(100) substrates. By coating a substrate with an Au layer of 60 nm or more, the Au-Si liquid phase covered the entire Si substrate surface, and single-phase β-FeSi2 was grown on Si(100) substrates. A clear photoluminescence spectrum of β-FeSi2 indicated the formation of high-quality crystals with a low density of the non-radiative recombination center in the grains.

A RF magnetron sputtering method was used to prepare Mg2Si films at 300-400oC on (001) Al2O3 substrates from a Mg disc target with Si chips. Mg deposition was not detected at 400°C from a pure Mg disc target without Si chips due to the high vapor pressure of Mg. However, the amount of Mg deposition increased with the increase in Si/(Mg+Si) area ratio of the target surface together with the increase of the Si deposition. The obtained films had a stoichiometric composition of Si/(Mg+Si)=0.33 that consisted of the well crystalline Mg2Si single phase regardless of Si/(Mg+Si) area ratio of the target surface. This showed the existence of a “process window” against supply ratio of Si/(Mg+Si) for Mg2Si single phase films with a stoichiometric composition. This is considered to be due to the vaporization of the excess Mg prepared under the Mg excess condition as reported by Mahan et al. for Mg2Si films prepared at 200°C by ultra-high vacuum evaporation.

Changes in crystal structure and ferroelectric properties are investigated for (100)/(001)-oriented epitaxial PbTiO3 thin films grown on CaF2 substrates by metal organic chemical vapor deposition. In this work, PbTiO3 films, with thickness ranging from 60 to 2000 nm, presented volume fraction of (001)-oriented c-domain higher than 90%. Hence, the residual strain is smaller compared to films deposited on widely investigated SrTiO3 substrates. Additionally, more than 60 μC/cm2 remnant polarization is obtained for all film thickness ranges, and the estimated spontaneous polarization taking into account c-domain volume fraction is about 80 μC/cm2 regardless of film thickness, in good agreement with reported values for the single crystal.

Epitaxial rhombohedral Pb(Zr0.65Ti0.35)O3films with (100) and (110)/(10-1) and (111)/(11-1) orientations were grown on various kinds of singlecrystal substrates having different thermal expansion coefficient. Volume fractions of (110) and (111) orientations in respective (110)/(10-1) and (111)/(11-1)-oriented films were almost linearly increased with increasing thermal strain, εthermal, applied to the films that wasgenerated under the cooling process after the deposition from the growth temperature to the Curie temperature.Observed saturationpolarization (Psat)was changed linearly with the volume fractions of (110) and (111) orientations, in the same manner asthe volume fractions of (001) and (101) orientations in (001)/(100) and (101)/(110) oriented tetragonal Pb(Zr,Ti)O3 filmsreported previously. These results showed that the volume fraction of the non-180o domains Pb(Zr,Ti)O3films of both tetragonal and rhombohedral symmetriescan be manipulated by εthermal, which brings possibly to control the Psat value.

The growth mechanism of large-size domains in PbTiO3/SrTiO3 heteroepitaxial thin films was examined using annular bright field (ABF) – scanning transmission electron microscopy and geometric phase analysis (GPA). {101} domain walls surrounded 90° domains. The large 90° domain grows by the coalescence of the nano-size domains of less than 5 nm width. A strain map obtained from the GPA of ABF-STEM image showed that 90° domains interacted elastically and attractively with edge dislocations at PbTiO3/SrTiO3 interface through simple shear strain.

Crystal structure change with an applied electric field was investigated by Raman spectroscopy and X-ray diffraction (XRD) for the 1 μm-thick (100)/(001) one-axis oriented tetragonal Pb(Zr0.3Ti0.7)O3 films prepared on Pt-covered (100) Si substrates by chemical solution deposition technique. As-deposited films were under the strained condition in good agreement with the estimation from the thermal strain applied under the cooling process after the deposition from the Curie temperature to the room temperature. This strain was ascertained to be relaxed by an applied electric field in accompanying with the dramatic increase of the volume fraction of (001) orientation. These results demonstrate the importance of the crystal structure measurement not only as-deposited films, but also after applied electric field, such as after poling.

High-quality (010)-oriented epitaxial β-FeSi2 films were grown on Si(110) substrates by coating silver thin layer. The full width at half maximum of the rocking curve of β-FeSi2040 was 0.14o for the film deposited at 800°C on Si(110) substrates with 95 nm-thick silver layer. Moreover, this epitaxial β-FeSi2 film was constructed with single domain structure, and the lattice parameter of a-axis was extended by 0.7%. The photoluminescence spectrum from this epitaxial β-FeSi2 indicated that the band-gap was modulated by lattice strain of a-axis.

Films of piezoelectric and ferroelectric oxides have been widely investigated for various applications, including microelectromechanical systems (MEMS) for printing. Pb(Zr,Ti)O3 is of particular interest due to its excellent piezoelectric properties. Control of the density, crystalline orientation, and compositional uniformity is essential to obtain these properties. In this article, we review recent progress on the fabrication of epitaxial Pb(Zr,Ti)O3films, in which the aforementioned control can be achieved. We discuss the different approaches used for the deposition of the epitaxial piezoelectric layer as well as the achieved degrees of the epitaxy. Furthermore, the integration of these piezoelectric layers in MEMS and the corresponding performance are discussed.

Raman scattering spectra and ferroelectric properties of epitaxial tetragonal Pb(Zr, Ti)O3 were investigated for polar axis-oriented thin films with various Zr/(Zr + Ti) ratios and by changing the ratios from 0 to 0.50 at different measurement temperatures. The chosen films in the thickness range of 1–2 μm present the advantage of showing small residual strain. The E (TO) modes were successfully isolated using cross-polarization configurations, while A1 (TO) and B1 modes were activated using parallel polarization configurations. Systematic changes in Raman peak positions were observed with changes in the Zr/(Zr + Ti) ratios at different measurement temperatures. It was found in both cases that the tetragonal distortion (c/a-1) and the value of square of spontaneous polarization (Ps2) linearly increased with increasing ω2[A1(1TO)], where a and c are the lattice parameters of a and c-axes. This indicates that monitoring A1(1TO) mode is efficient as a characterization method of ferroelectricity. It can also be used as a novel nondestructive process check or reliability assessment technique during fabrication of microelectromechanical systems (MEMS) using piezoelectric materials.

A clear PL spectrum was observed from β-FeSi2 grains on gold (Au)-coated (100)Si substrates, and indicated the formation of crystal with the same high quality level as the β-FeSi2 on a copper (Cu)-coated Si substrate. Moreover, the temperature dependence of photoluminescence peak intensities showed lower density of the nonradiative recombination center in β-FeSi2 grains on Au-coated Si substrates than that of β-FeSi2 film on Cu-coated Si. Au was not detected in β-FeSi2 grains by STEM-EDX observation, while Cu was observed in the grains and grain boundaries of β-FeSi2 and rolled as non-radiative recombination center.