Broken Screw Rotational Symmetry in the Near-Surface Electronic Structure of AB-Stacked Crystals.

We investigate the electronic structure of 2H-NbS_{2} and h-BN by angle-resolved photoemission spectroscopy (ARPES) and photoemission intensity calculations. Although in bulk form, these materials are expected to exhibit band degeneracy in the k_{z}=π/c plane due to screw rotation and time-reversal symmetries, we observe gapped band dispersion near the surface. We extract from first-principles calculations the near-surface electronic structure probed by ARPES and find that the calculated photoemission spectra from the near-surface region reproduce the gapped ARPES spectra. Our results show that the near-surface electronic structure can be qualitatively different from the bulk electronic structure due to partially broken nonsymmorphic symmetries.

Semiconducting Electronic Structure of the Ferromagnetic Spinel HgCr_{2}Se_{4} Revealed by Soft-X-Ray Angle-Resolved Photoemission Spectroscopy.

We study the electronic structure of the ferromagnetic spinel HgCr_{2}Se_{4} by soft-x-ray angle-resolved photoemission spectroscopy (SX-ARPES) and first-principles calculations. While a theoretical study has predicted that this material is a magnetic Weyl semimetal, SX-ARPES measurements give direct evidence for a semiconducting state in the ferromagnetic phase. Band calculations based on the density functional theory with hybrid functionals reproduce the experimentally determined band gap value, and the calculated band dispersion matches well with ARPES experiments. We conclude that the theoretical prediction of a Weyl semimetal state in HgCr_{2}Se_{4} underestimates the band gap, and this material is a ferromagnetic semiconductor.

Observation and control of the weak topological insulator state in ZrTe5.

A quantum spin Hall (QSH) insulator hosts topological states at the one-dimensional (1D) edge, along which backscattering by nonmagnetic impurities is strictly prohibited. Its 3D analogue, a weak topological insulator (WTI), possesses similar quasi-1D topological states confined at side surfaces. The enhanced confinement could provide a route for dissipationless current and better advantages for applications relative to strong topological insulators (STIs). However, the topological side surface is usually not cleavable and is thus hard to observe. Here, we visualize the topological states of the WTI candidate ZrTe5 by spin and angle-resolved photoemission spectroscopy (ARPES): a quasi-1D band with spin-momentum locking was revealed on the side surface. We further demonstrate that the bulk band gap is controlled by external strain, realizing a more stable WTI state or an ideal Dirac semimetal (DS) state. The highly directional spin-current and the tunable band gap in ZrTe5 will provide an excellent platform for applications.

Sacrificial Water-Soluble BaO Layer for Fabricating Free-Standing Piezoelectric Membranes.

The use of a sacrificial water-soluble BaO layer was investigated for the purpose of fabricating free-standing single-crystalline BaTiO3 membranes for vibrational energy harvesting applications. An epitaxial BaTiO3/SrTiO3/BaO heterostructure was deposited on a SrTiO3(001) substrate by pulsed laser deposition. The sacrificial BaO layer was dissolved by immersing the heterostructure in water. A single-crystalline BaTiO3 membrane was thereby released from the SrTiO3(001) substrate and transferred onto a glass or polyethylene terephthalate (PET) substrate coated with a polydimethylsiloxane (PDMS) adhesion layer. A 200 nm-thick BaTiO3 membrane was sandwiched between two flexible PDMS/ITO/PET electrode layers, forming a vibrational energy harvester test device that could operate at an average electrical power output of over 1 µW. This membrane fabrication process is applicable to various flexible structures and materials in vibrational energy harvesting or dynamic strain-sensing applications.

Strain-induced spontaneous Hall effect in an epitaxial thin film of a Luttinger semimetal.

Pyrochlore iridates have provided a plethora of novel phenomena owing to the combination of topology and correlation. Among them, much attention has been paid to [Formula: see text], as it is known as a Luttinger semimetal characterized by quadratic band touching at the Brillouin zone center, suggesting that the topology of its electronic states can be tuned by a moderate lattice strain and external magnetic field. Here, we report that our epitaxial [Formula: see text] thin films grown by solid-state epitaxy exhibit a spontaneous Hall effect that persists up to 50 K without having spontaneous magnetization within our experimental accuracy. This indicates that the system breaks the time reversal symmetry at a temperature scale that is too high for the magnetism to be due to Pr 4f moments and must be related to magnetic order of the iridium 5d electrons. Moreover, our analysis finds that the chiral anomaly induces the negative contribution to the magnetoresistance only when a magnetic field and the electric current are parallel to each other. Our results indicate that the strained part of the thin film forms a magnetic Weyl semimetal state.

Noble Metal Nanocluster Formation in Epitaxial Perovskite Thin Films.

We studied the synthesis of nanocomposite materials consisting of noble metal clusters embedded in an oxide semiconductor matrix. The embedded nanostructures form in a simple self-organized single-step growth process. The primary interest is in developing materials for photo-electrochemical energy conversion where spatially inhomogeneous band structures can enhance photogenerated charge separation and carrier extraction from a semiconductor. We show that spontaneous segregation of metallic Ir occurs during the initial growth of an Ir:SrTiO3 thin film. Cross-sectional transmission electron microscopy suggests that the nanoscale Ir clusters are epitaxial with the host lattice, and their presence is not detectable by surface morphology measurements.

Dielectric anomalies and interactions in the three-dimensional quadratic band touching Luttinger semimetal Pr2Ir2O7.

Dirac and Weyl semimetals with linearly crossing bands are the focus of much recent interest in condensed matter physics. Although they host fascinating phenomena, their physics can be understood in terms of weakly interacting electrons. In contrast, more than 40 years ago, Abrikosov pointed out that quadratic band touchings are generically strongly interacting. We have performed terahertz spectroscopy on the films of the conducting pyrochlore Pr2Ir2O7, which has been shown to host a quadratic band touching. A dielectric constant as large as [Formula: see text] is observed at low temperatures. In such systems, the dielectric constant is a measure of the relative scale of interactions, which are therefore in our material almost two orders of magnitude larger than the kinetic energy. Despite this, the scattering rate exhibits a T 2 dependence, which shows that for finite doping a Fermi liquid state survives-however, with a scattering rate close to the maximal value allowed.

Combinatorial screening of halide perovskite thin films and solar cells by mask-defined IR laser molecular beam epitaxy.

As an extension of combinatorial molecular layer epitaxy via ablation of perovskite oxides by a pulsed excimer laser, we have developed a laser molecular beam epitaxy (MBE) system for parallel integration of nano-scaled thin films of organic-inorganic hybrid materials. A pulsed infrared (IR) semiconductor laser was adopted for thermal evaporation of organic halide (A-site: CH3NH3I) and inorganic halide (B-site: PbI2) powder targets to deposit repeated A/B bilayer films where the thickness of each layer was controlled on molecular layer scale by programming the evaporation IR laser pulse number, length, or power. The layer thickness was monitored with an in situ quartz crystal microbalance and calibrated against ex situ stylus profilometer measurements. A computer-controlled movable mask system enabled the deposition of combinatorial thin film libraries, where each library contains a vertically homogeneous film with spatially programmable A- and B-layer thicknesses. On the composition gradient film, a hole transport Spiro-OMeTAD layer was spin-coated and dried followed by the vacuum evaporation of Ag electrodes to form the solar cell. The preliminary cell performance was evaluated by measuring I-V characteristics at seven different positions on the 12.5 mm × 12.5 mm combinatorial library sample with seven 2 mm × 4 mm slits under a solar simulator irradiation. The combinatorial solar cell library clearly demonstrated that the energy conversion efficiency sharply changes from nearly zero to 10.2% as a function of the illumination area in the library. The exploration of deposition parameters for obtaining optimum performance could thus be greatly accelerated. Since the thickness ratio of PbI2 and CH3NH3I can be freely chosen along the shadow mask movement, these experiments show the potential of this system for high-throughput screening of optimum chemical composition in the binary film library and application to halide perovskite solar cell.

Thermally Stable Sr2RuO4 Electrode for Oxide Heterostructures.

The use of thermally stable Sr2RuO4 electrodes in high-temperature synthesis of oxide heterostructures was investigated. Atomically smooth Sr2RuO4 thin films were grown on SrTiO3(001) substrates by pulsed laser deposition and used as a bottom electrode for ferroelectric BaTiO3 capacitors grown at temperatures of up to 1000 °C. The thermal stability of Sr2RuO4 electrodes was verified by structural and electrical measurements of the ferroelectric BaTiO3 films. The best growth temperature for the BaTiO3 films was found to be 900 °C, exhibiting the largest spontaneous polarization, dielectric constant, and pyroelectric response. We conclude that Sr2RuO4 films are suitable for use as thermally stable electrodes in heterostructures synthesized at temperatures up to at least 1000 °C and oxygen pressures from 10-6 to 10-1 Torr. This range of growth film conditions is much wider than that for other common oxide electrode materials such as SrRuO3, widening the available process window for optimizing the performance of oxide electronic devices.

Photoelectrochemical water splitting enhanced by self-assembled metal nanopillars embedded in an oxide semiconductor photoelectrode.

Production of chemical fuels by direct solar energy conversion in a photoelectrochemical cell is of great practical interest for developing a sustainable energy system. Various nanoscale designs such as nanowires, nanotubes, heterostructures and nanocomposites have been explored to increase the energy conversion efficiency of photoelectrochemical water splitting. Here we demonstrate a self-organized nanocomposite material concept for enhancing the efficiency of photocarrier separation and electrochemical energy conversion. Mechanically robust photoelectrodes are formed by embedding self-assembled metal nanopillars in a semiconductor thin film, forming tubular Schottky junctions around each pillar. The photocarrier transport efficiency is strongly enhanced in the Schottky space charge regions while the pillars provide an efficient charge extraction path. Ir-doped SrTiO3 with embedded iridium metal nanopillars shows good operational stability in a water oxidation reaction and achieves over 80% utilization of photogenerated carriers under visible light in the 400- to 600-nm wavelength range.

Epitaxial Bi5Ti3FeO15-CoFe2O4 pillar-matrix multiferroic nanostructures.

Epitaxial self-assembled ferro(i)magnetic spinel (CoFe2O4 (CFO)) and ferroelectric bismuth layered perovskite (Bi5Ti3FeO15 (BTFO)) pillar-matrix nanostructures are demonstrated on (001) single-crystalline strontium titanate substrates. The CFO remains embedded in the BTFO matrix as vertical pillars (∼50 nm in diameter) up to a volume fraction of 50%. Piezoresponse force microscopy experiments evidence a weak out-of-plane and a strong in-plane ferroelectricity in the BTFO phase, despite previously reported paraelectricity along the c-axis in a pure BTFO film. Phenomenological Landau-Ginzburg-Devonshire-based thermodynamic computations show that the radial stress induced by the CFO nanopillars can influence these ferroelectric phases, thus signifying the importance of the nanopillars. The CFO pillars demonstrate robust ferromagnetic hysteresis loops with little degradation in the saturation magnetization (ca. 4 µB/f.u.). Thus BTFO-CFO nanocomposites show significant promise as a lead-free magnetoelectric materials system.

Development of a new laser heating system for thin film growth by chemical vapor deposition.

We have developed a new laser heating system for thin film growth by chemical vapor deposition (CVD). A collimated beam from a high-power continuous-wave 808 nm semiconductor laser was directly introduced into a CVD growth chamber without an optical fiber. The light path of the heating laser inside the chamber was isolated mechanically from the growth area by bellows to protect the optics from film coating. Three types of heat absorbers, (10 × 10 × 2 mm(3)) consisting of SiC, Ni/NiO(x), or pyrolytic graphite covered with pyrolytic BN (PG/PBN), located at the backside of the substrate, were tested for heating performance. It was confirmed that the substrate temperature could reach higher than 1500 °C in vacuum when a PG/PBN absorber was used. A wide-range temperature response between 400 °C and 1000 °C was achieved at high heating and cooling rates. Although the thermal energy loss increased in a H(2) gas ambient due to the higher thermal conductivity, temperatures up to 1000 °C were achieved even in 200 Torr H(2). We have demonstrated the capabilities of this laser heating system by growing ZnO films by metalorganic chemical vapor deposition. The growth mode of ZnO films was changed from columnar to lateral growth by repeated temperature modulation in this laser heating system, and consequently atomically smooth epitaxial ZnO films were successfully grown on an a-plane sapphire substrate.