Tetragonal tungsten bronze (TTB) materials are one of the most promising classes of materials for ferroelectric and nonlinear optical devices, owing to their very unique noncentrosymmetric crystal structure. In this work, a new TTB phase of LiNb6Ba5Ti4O30 (LNBTO) has been discovered and studied. A small amount of a secondary phase, LiTiO2 (LTO), has been incorporated as nanopillars that are vertically embedded in the LNBTO matrix. The new multifunctional nanocomposite thin film presents exotic highly anisotropic microstructure and properties, e.g., strong ferroelectricity, high optical transparency, anisotropic dielectric function, and strong optical nonlinearity evidenced by the second harmonic generation results. An optical waveguide structure based on the stacks of α-Si on SiO2/LNBTO-LTO has been fabricated, exhibiting low optical dispersion with an optimized evanescent field staying in the LNBTO-LTO active layer. This work highlights the combination of new TTB material designs and vertically aligned nanocomposite structures for further enhanced anisotropic and nonlinear properties.
Light coupling with patterned subwavelength hole arrays induces enhanced transmission supported by the strong surface plasmon mode. In this work, a nanostructured plasmonic framework with vertically built-in nanohole arrays at deep-subwavelength scale (6 nm) is demonstrated using a two-step fabrication method. The nanohole arrays are formed first by the growth of a high-quality two-phase (i.e., Au–TiN) vertically aligned nanocomposite template, followed by selective wet-etching of the metal (Au). Such a plasmonic nanohole film owns high epitaxial quality with large surface coverage and the structure can be tailored as either fully etched or half-way etched nanoholes via careful control of the etching process. The chemically inert and plasmonic TiN plays a role in maintaining sharp hole boundary and preventing lattice distortion. Optical properties such as enhanced transmittance and anisotropic dielectric function in the visible regime are demonstrated. Numerical simulation suggests an extended surface plasmon mode and strong field enhancement at the hole edges. Two demonstrations, including the enhanced and modulated photoluminescence by surface coupling with 2D perovskite nanoplates and the refractive index sensing by infiltrating immersion liquids, suggest the great potential of such plasmonic nanohole array for reusable surface plasmon-enhanced sensing applications.
Three-dimensional (3D) strain induced in self-assembled vertically aligned nanocomposite (VAN) epitaxial films provides an unrivaled method to induce very large strains in thin films. Here, by growing VAN films of EuTiO3 (ETO)-Eu2O3 (EO) with different EO fractions, the vertical strain was systematically increased in ETO, up to 3.15%, and the Eu-Ti-Eu bond angle along ⟨111»decreased by up to 1°, leading to a weakening of the antiferromagnetic interactions and switching from antiferromagnetic to ferromagnetic behavior. Our work has shown for the first time that Eu-Ti-Eu superexchange interactions play a key role in determining the magnetic ground state of ETO. More broadly, our work serves as an exemplar to show that multifunctionalities in strong spin-lattice coupling perovskite oxides can be uniquely tuned at the atomic scale using simple VAN structures.
Ultrathin epitaxial films of ferromagnetic insulators (FMIs) with Curie temperatures near room temperature are critically needed for use in dissipationless quantum computation and spintronic devices. However, such materials are extremely rare. Here, a room-temperature FMI is achieved in ultrathin La0.9Ba0.1MnO3 films grown on SrTiO3 substrates via an interface proximity effect. Detailed scanning transmission electron microscopy images clearly demonstrate that MnO6 octahedral rotations in La0.9Ba0.1MnO3 close to the interface are strongly suppressed. As determined from in situ X-ray photoemission spectroscopy, O K-edge X-ray absorption spectroscopy, and density functional theory, the realization of the FMI state arises from a reduction of Mn eg bandwidth caused by the quenched MnO6 octahedral rotations. The emerging FMI state in La0.9Ba0.1MnO3 together with necessary coherent interface achieved with the perovskite substrate gives very high potential for future high performance electronic devices.
Intermetallic alloys possess exceptional soft magnetic properties, including high permeability, low coercivity, and high saturation induction, but exhibit poor mechanical properties that make them impractical to bulk process and use at ideal compositions. We used laser-based Additive Manufacturing to process traditionally brittle Fe–Co and Fe–Si alloys in bulk form without macroscopic defects and at near-ideal compositions for electromagnetic applications. The binary Fe–50Co, as a model material, demonstrated simultaneous high strength (600–700 MPa) and high ductility (35%) in tension, corresponding to a ∼300% increase in strength and an order-of-magnitude improvement in ductility relative to conventionally processed material. Atomic-scale toughening and strengthening mechanisms, based on engineered multiscale microstructures, are proposed to explain the unusual combination of mechanical properties. This work presents an instance in which metal Additive Manufacturing processes are enabling, rather than limiting, the development of higher-performance alloys.
Thin tellurium (Te) has been predicted as a potential two dimensional system exhibiting superior thermoelectric and electrical properties. Here, we report the synthesis of high quality ultrathin Te nanostructures and the study of their electrical properties at room temperature. High quality ultrathin Te nanostructures are obtained by high temperature vapor phase deposition on c-plane sapphire substrates. The obtained nanostructures are as thin as 3 nm and exhibit α-Te phase with trigonal crystal structure. Room temperature electrical measurements show significantly higher electrical conductivity compared to prior reports of Te in bulk form or in nanostructure form synthesized by low temperature vapor deposition or wet chemical methods. Additionally, these nanostructures exhibit high field effect hole mobility comparable to black-phosphorous measured previously under similar conditions.
Grain boundary (GB) solute segregation has been proposed as a new mechanism to stabilize nanocrystalline (NC) metals. In this study, we investigate the thermal stability and GB solute segregation in a noble metal alloy system (Pt–Au). Thermal stability of the Pt.90Au.10 alloy system was evaluated by annealing a thin film (∼20 nm in thickness) at 500 °C and 700 °C as well as a thick film (∼2 µm in thickness) at a temperature range from 200 °C to 700 °C. The remarkable stability of the Pt.90Au.10 alloy system was demonstrated by comparing its thermal stability to that of pure Pt films processed under identical conditions. Although presence of voids in the GBs may contribute to thermal stability, the enhanced thermal stability of the Pt.90Au.10 alloy is mainly attributed to preferential Au segregation to GBs in the alloy film, which is revealed by aberration-corrected scanning transmission electron microscopy. Our results show that Au segregation to GBs is heterogeneous, with variation in solute content between different GBs as well as non-uniformity along individual GBs. The heterogeneity is dependent on the annealing temperature and is less pronounced at a higher processing temperatures (e.g., 700 °C). By using the noble Pt–Au system, which avoids oxidation and impurities, this study validates the mechanism of GB solute segregation and provides further understanding of the thermodynamics and kinetics underlying NC stabilization.
Vertically aligned nanocomposite (VAN) films have self-assembled pillar-matrix nanostructures. Owing to their large area-to-volume ratios, interfaces in VAN films are expected to play key roles in inducing functional properties, but our understanding is hindered by limited knowledge about their structures. Motivated by the lack of definitive explanation for the experimentally found enhanced ionic conductivity in Sm-doped-CeO2/SrTiO3 VAN films, we determine the structure at vertical interfaces using random structure searching and explore how it can affect ionic conduction. Interatomic potentials are used to perform the initial searching, followed by first-principles calculations for refinement. Previously unknown structures are found, with lower energy than that of an optimized hand-built model. We find a strongly distorted oxygen sublattice which gives a complex landscape of vacancy energies. The cation lattice remains similar to the bulk phase, but has a localized strain field. The excess energy of the interface is similar to that of high angle grain boundaries in SrTiO3.
A long-term goal for superconductors is to increase the superconducting transition temperature, TC. In cuprates, TC depends strongly on the out-of-plane Cu-apical oxygen distance and the in-plane Cu-O distance, but there has been little attention paid to tuning them independently. Here, in simply grown, self-assembled, vertically aligned nanocomposite thin films of La2CuO4+δ + LaCuO3, by strongly increasing out-of-plane distances without reducing in-plane distances (three-dimensional strain engineering), we achieve superconductivity up to 50 K in the vertical interface regions, spaced ∼50 nm apart. No additional process to supply excess oxygen, e.g., by ozone or high-pressure oxygen annealing, was required, as is normally the case for plain La2CuO4+δ films. Our proof-of-concept work represents an entirely new approach to increasing TC in cuprates or other superconductors.
Tunable plasmonic structure at the nanometer scale presents enormous opportunities for various photonic devices. In this work, we present a hybrid plasmonic thin film platform: i.e., a vertically aligned Au nanopillar array grown inside a TiN matrix with controllable Au pillar density. Compared to single phase plasmonic materials, the presented tunable hybrid nanostructures attain optical flexibility including gradual tuning and anisotropic behavior of the complex dielectric function, resonant peak shifting and change of surface plasmon resonances (SPRs) in the UV-visible range, all confirmed by numerical simulations. The tailorable hybrid platform also demonstrates enhanced surface plasmon Raman response for Fourier-transform infrared spectroscopy (FTIR) and photoluminescence (PL) measurements, and presents great potentials as designable hybrid platforms for tunable optical-based chemical sensing applications.
We discuss chemical, structural, and ellipsometry characterization of low temperature epitaxial Si. While low temperature growth is not ideal, we are still able to prepare crystalline Si to cap functional atomic precision devices.
Nanocrystalline metals offer significant improvements in structural performance over conventional alloys. However, their performance is limited by grain boundary instability and limited ductility. Solute segregation has been proposed as a stabilization mechanism, however the solute atoms can embrittle grain boundaries and further degrade the toughness. In the present study, we confirm the embrittling effect of solute segregation in Pt–Au alloys. However, more importantly, we show that inhomogeneous chemical segregation to the grain boundary can lead to a new toughening mechanism termed compositional crack arrest. Energy dissipation is facilitated by the formation of nanocrack networks formed when cracks arrested at regions of the grain boundaries that were starved in the embrittling element. This mechanism, in concert with triple junction crack arrest, provides pathways to optimize both thermal stability and energy dissipation. A combination of in situ tensile deformation experiments and molecular dynamics simulations elucidate both the embrittling and toughening processes that can occur as a function of solute content.
Magnetic property enhancement of alnico, a rare-earth free permanent magnet, is highly dependent on both the initial microstructure and the evolution of the spinodal decomposition (SD) inside each grain during the heat treatment process. The size, shape and distribution of the magnetic FeCo-rich (α1) phase embedded in continuous non-magnetic AlNi-rich (α2) phase as well as a minor Cu-enriched phase residing in between are shown to be crucial in controlling coercivity. Phase and magnetic domain morphology in a commercial alnico 9 alloy was studied using a combination of structural characterization techniques, including scanning electron microscopy, electron backscatter diffraction, aberration-corrected scanning transmission electron microscopy and Lorentz microscopy. Our results showed that casting created structural nonuniformity and defects, such as porosity, TiS2 precipitates and grain misorientation, are heterogeneously distributed, with the center section having the best crystallographic orientation and minimal defects. The optimal spinodal is a “mosaic structure”, composed of rod-shape α1 phase with {110} or {100} planar faceting and diameter of ~30–45nm. There is also a Cu-enriched phase residing at the corners of two < 110 > facets of the α1 phase. Furthermore, it was observed that grain boundary phase reverse magnetization direction at lower external magnetic field compared to the SD region inside the grain. Improving grain orientation uniformity, reducing detrimental grain boundary phase volume fraction, and the branching of the α1 rods, as well as their diameter, are promising routes to improve energy product of alnico.
