Selective Epitaxial Growth of Ca2NH and CaNH Thin Films by Reactive Magnetron Sputtering under Hydrogen Partial Pressure Control.

Calcium compounds with N and H are promising catalysts for NH3 conversion, and their epitaxial thin films provide a platform to quantitatively understand the catalytic activities. Here we report the selective epitaxial growth of Ca2NH and CaNH thin films by controlling the hydrogen partial pressure (PH2) during reactive magnetron sputtering. We find that the hydrogen charge states can be tuned by PH2: Ca2NH containing H- is formed at PH2 < 0.04 Pa, while CaNH containing H+ is formed at PH2 > 0.04 Pa. In situ plasma emission spectroscopy reveals that the intensity of the Ca atomic emission (∼422 nm) decreases as PH2 increases, suggesting that Ca reacts with H2 and N2 to form Ca2NH at lower PH2, whereas at higher PH2, CaHx is first formed on the target surface and then sputtered to produce CaNH. This study provides a novel route to control the hydrogen charge states in Ca-N-H epitaxial thin films.

Heteroepitaxial Growth of a Ta3N5 Thin Film with Clear Anisotropic Optical Properties.

Ta3N5 is a promising semiconductor photocatalyst which can generate H2 gas from water under visible light illumination. It is expected that Ta3N5 exhibits a strong anisotropy in its physical properties stemming from its highly anisotropic crystal structure. However, such anisotropic properties have not been verified experimentally due to the difficulty in synthesizing a large single crystal. Here, we report the synthesis of (010)-oriented Ta3N5 single-crystalline thin films by solid phase epitaxy on the (110) plane of perovskite LaAlO3 substrates. The obtained epitaxial thin films of Ta3N5 exhibited clear optical anisotropy (pleochroism) as predicted by previous first-principles calculations. The optical gap for E||[100] polarization (∼2.12 eV) was smaller than that for E||[100] polarization (∼2.27 eV).

High-Quality Heteroepitaxial Growth of Thin Films of the Perovskite Oxynitride CaTaO2N: Importance of Interfacial Symmetry Matching between Films and Substrates.

Perovskite oxynitrides have been studied with regard to their visible light-driven photocatalytic activity and novel electronic functionalities. The assessment of the intrinsic physical and/or electrochemical properties of oxynitrides requires the epitaxial growth of single-crystalline films. However, the heteroepitaxy of perovskite oxynitrides has not yet matured compared to the progress realized in work with perovskite oxides. Herein, we report the heteroepitaxial growth of CaTaO2N thin films with (100)pc, (110)pc, and (111)pc crystallographic surface orientations (where the subscript pc denotes a pseudocubic cell) on SrTiO3 substrates using reactive radio frequency magnetron sputtering, along with investigations of crystallinity and surface morphology. Irrespective of surface orientation, stoichiometric CaTaO2N epitaxial thin films were grown coherently on SrTiO3 substrates and showed clear step and terrace surfaces in the case of low values of film thickness of approximately 20 nm. A (110)pc-oriented film was also more highly crystalline than (100)pc- and (111)pc-oriented specimens. This relationship between crystallinity and surface orientation is ascribed to the number of inequivalent in-plane rotational domains, which stems from the symmetry mismatch between the orthorhombic CaTaO2N and cubic SrTiO3. A CaTaO2N thin film grown on a lattice- and symmetry-matched orthorhombic DyScO3 substrate exhibited a significant crystallinity and a clear step and terrace surface even though the film was thick (∼190 nm). These results are expected to assist in developing the heteroepitaxial growth of high-quality perovskite oxynitride thin films.

Strain-induced creation and switching of anion vacancy layers in perovskite oxynitrides.

Perovskite oxides can host various anion-vacancy orders, which greatly change their properties, but the order pattern is still difficult to manipulate. Separately, lattice strain between thin film oxides and a substrate induces improved functions and novel states of matter, while little attention has been paid to changes in chemical composition. Here we combine these two aspects to achieve strain-induced creation and switching of anion-vacancy patterns in perovskite films. Epitaxial SrVO3 films are topochemically converted to anion-deficient oxynitrides by ammonia treatment, where the direction or periodicity of defect planes is altered depending on the substrate employed, unlike the known change in crystal orientation. First-principles calculations verified its biaxial strain effect. Like oxide heterostructures, the oxynitride has a superlattice of insulating and metallic blocks. Given the abundance of perovskite families, this study provides new opportunities to design superlattices by chemically modifying simple perovskite oxides with tunable anion-vacancy patterns through epitaxial lattice strain.

Reversible Changes in Resistance of Perovskite Nickelate NdNiO3 Thin Films Induced by Fluorine Substitution.

Perovskite nickel oxides are of fundamental as well as technological interest because they show large resistance modulation associated with phase transition as a function of the temperature and chemical composition. Here, the effects of fluorine doping in perovskite nickelate NdNiO3 epitaxial thin films are investigated through a low-temperature reaction with polyvinylidene fluoride as the fluorine source. The fluorine content in the fluorinated NdNiO3-xFx films is controlled with precision by varying the reaction time. The fully fluorinated film (x ≈ 1) is highly insulating and has a bandgap of 2.1 eV, in contrast to NdNiO3, which exhibits metallic transport properties. Hard X-ray photoelectron and soft X-ray absorption spectroscopies reveal the suppression of the density of states at the Fermi level as well as the reduction of nickel ions (valence state changes from +3 to +2) after fluorination, suggesting that the strong Coulombic repulsion in the Ni 3d orbitals associated with the fluorine substitution drives the metal-to-insulator transition. In addition, the resistivity of the fluorinated films recovers to the original value for NdNiO3 after annealing in an oxygen atmosphere. By application of the reversible fluorination process to transition-metal oxides, the search for resistance-switching materials could be accelerated.

Effects of hydrogen in working gas on valence States of oxygen in sputter-deposited indium tin oxide thin films.

X-ray photoelectron spectroscopy (XPS) and Rutherford backscattering spectroscopy-elastic recoil detection analysis (RBS-ERDA) revealed that hydrogen in working gas for dc-plasma sputter deposition resided in indium tin oxide (ITO) films and generated the O(-) state seen as the suboxide-like O 1s peak in XPS. Growth of the suboxide-like O 1s peak was parallel with an increase of the resided hydrogen quantified by RBS-ERDA. The first-principles band structure calculation revealed that the electronic structure of In(2)O(3) crystal was realized typically for the most conductive as-deposited film grown in the gas containing hydrogen of 1%. The as-deposited film grown in the gas containing hydrogen of more than 1% exhibited rather high density but low mobility of carriers and showed the electronic structure above 4 eV originated from the O(-) state due to the resided hydrogen in addition to that of the most conducting one. Both well preserved In(2)O(3) band structure and proper concentration of the O(2-) vacancy are indispensable for achieving the highest conductivity; however, the O(-) state lowers efficiency of the carrier doping using the O(2-) vacancy in the lattice and increases density of the ionized scattering center for the carriers.

Direct observation of strain-induced change in surface electronic structure.

We have observed a novel modification of a surface state due to a local strain field induced by a nanopattern formation. N adsorption on the Cu(100) surface induces a nanoscale grid pattern, where the clean Cu regions remain periodically. The lattice is contracted on the clean region by adjacent c(2 x 2)N domains, which have a larger lattice constant. On this patterned surface, we have investigated the Tamm-type surface state at M by means of angle-resolved ultraviolet photoelectron spectroscopy. The binding energy of the Tamm state shifts toward the Fermi level continuously with increasing N coverage, i.e., the intensity of the strain field. This behavior due to the strain field is completely different from that caused by electron confinement observed on vicinal surfaces. The Brillouin zone extension corresponding to the lattice contraction was also detected.