Materials Science (cond-mat.mtrl-sci)

Abstract: III-nitrides and related alloys are widely used for optoelectronics and as acoustic resonators. Ferroelectric wurtzite nitrides are of particular interest because of their potential for direct integration with Si and wide bandgap semiconductors, and unique polarization switching characteristics; such interest has taken off since the first report of ferroelectric Al$_{1-x}$Sc$_x$N alloys. However, the coercive fields needed to switch polarization are on the order of MV/cm, which is 1-2 orders of magnitude larger than oxide perovskite ferroelectrics. Atomic-scale point defects are known to impact the dielectric properties, including breakdown fields and leakage currents, as well as ferroelectric switching. However, very little is known about the native defects and impurities in Al$_{1-x}$Sc$_x$N, and their effect on the dielectric properties. In this study, we use first-principles calculations to determine the formation energetics of native defects and unintentional oxygen incorporation in Al$_{1-x}$Sc$_x$N. We find that nitrogen vacancies are the dominant native defects, and that they introduce multiple mid-gap states that can lead to premature dielectric breakdown in ferroelectrics and carrier recombination in optoelectronics. Growth under N-rich conditions will reduce the concentration of these deep defects. We also investigate unintentional oxygen incorporation on the nitrogen site and find that the substitutional defect is present in high concentrations, which can contribute to increased temperature-activated leakage currents. Our findings provide fundamental understanding of the defect physics in Al$_{1-x}$Sc$_x$N alloys, which is critical for future deployment of ferroelectric devices.

Abstract: Kagome magnets showing diverse topological quantum responses are crucial for next-generation topological engineering. Here we report the physical properties of a newly discovered titanium-based Kagome ferromagnet SmTi3Bi4, mainly focusing on its anisotropy and high-pressure tunability of magnetism. The crystal structure of SmTi3Bi4 belongs to the RETi3Bi4 (RE = Rare earth element) prototype, featuring a distorted Ti Kagome lattice in TiBi layer and Sm-atomic zig-zag chain along the c axis. By the temperature-dependent resistivity, heat capacity, and magnetic susceptibility measurements, a ferromagnetic (FM) ordering temperature Tc is determined to be 23.2 K, above which a T-linear resistivity and quite large density of states near Fermi level are hinted to exist. A large magnetic anisotropy was observed by rotating the in-plane magnetic field, showing the b axis is the easy magnetizations axis. The resistance under high pressure shows a suppression from 23.2 K to 8.5 K up to 23.5 GPa first and a following little enhancement up to 44.8 GPa. Considering the large in-plane magnetization between stacked Kagome lattices and tunability of FM order, possible topological phase transitions can be anticipated in SmTi3Bi4, which should be a new promising platform to explore the complex electronic and magnetic phases based on Kagome lattice.

Abstract: The potential for low-threshold optical nonlinearity has received significant attention in the fields of photonics and conceptual optical neuron networks. Excitons in two-dimensional (2D) semiconductors are particularly promising in this regard as reduced screening and dimensional confinement foster their pronounced many-body interactions towards nonlinearity. However, experimental determination of the interactions remains ambiguous, as optical pumping in general creates a mixture of excitons and unbound carriers, where the impacts of band gap renormalization and carrier screening on exciton energy counteract each other. Here by comparing the influences on exciton ground and excited states energies in the photoluminescence spectroscopy of monolayer MoSe$_2$, we are able to identify separately the screening of Coulomb binding by the neutral excitons and by charge carriers. The energy difference between exciton ground state (A-1s) and excited state (A-2s) red-shifts by 5.5 meV when the neutral exciton density increases from 0 to $4\times 10^{11}$ cm$^{-2}$, in contrast to the blue shifts with the increase of either electron or hole density. This energy difference change is attributed to the mutual screening of Coulomb binding of neutral excitons, from which we extract an exciton polarizability of $\alpha_{2D}^{\rm exciton} = 2.55\times 10^{-17}$ eV(m/V)$^2$. Our finding uncovers a new mechanism that dominates the repulsive part of many-body interaction between neutral excitons.

Abstract: Potassium tantalate (KTaO$_{3}$) is a promising material for dielectric applications at low temperature. However, dense and single-phase ceramics cannot be obtained by conventional sintering because of the evaporation of potassium that leads to secondary phases. Here, we demonstrate that spark plasma sintering is a suitable method to obtain dense and single-phase KTaO$_{3}$ ceramics, by optimizing three parameters: initial composition, temperature, and pressure. A 2 mol% K-excess in the precursors leads to a large grain growth and dense single-phase ceramics. Without K-excess, a small amount of secondary phase (K$_{6}$Ta$_{10.8}$O$_{30}$) is observed at the surface but can be removed by polishing. At 10 K, the dielectric permittivity is 4 times higher in the ceramic from the 2 mol% K-excess powder, because of the larger grain size. The thermal conductivity decreases with decreasing grain size and stays above the thermal conductivity of KNbO$_{3}$ ceramics.

Abstract: Two-dimensional (2D) materials tend to have the preferably formation of vacancies at the outer surface. Here, contrary to the normal notion, we reveal a type of vacancy that thermodynamically initiates from the interior part of the 2D backbone of germanium selenide ({\gamma}-GeSe). Interestingly, the Ge-vacancy (VGe) in the interior part of {\gamma}-GeSe possesses the lowest formation energy amongst the various types of defects considered. We also find a low diffusion barrier (1.04 eV) of VGe which is a half of those of sulfur vacancy in MoS2. The facile formation of mobile VGe is rooted in the antibonding coupling of the lone-pair Ge 4s and Se 4p states near the valence band maximum, which also exists in other gamma-phase MX (M=Sn, Ge; X=S, Te). The VGe is accompanied by a shallow acceptor level in the band gap and induces strong infrared light absorption and p-type conductivity. The VGe located in the middle cationic Ge sublattice is well protected by the surface Se layers-a feature that is absent in other atomically thin materials. Our work suggests that the unique well-buried inner VGe, with the potential of forming structurally protected ultrathin conducting filaments, may render the GeSe layer an ideal platform for quantum emitting, memristive, and neuromorphic applications.

Abstract: Hydrogen as the cleanest energy carrier is a promising alternative renewable resource to fossil fuels. There is an ever-increasing interest in exploring efficient and cost-effective approaches of hydrogen production. Recent experiments have shown that single platinum atom immobilized on the metal vacancies of MXenes allows a high-efficient hydrogen evolution reaction (HER). Here using ab initio calculations, we design a series of substitutional Pt-doped Tin+1CnTx (Tin+1CnTx-PtSA) with different thicknesses and terminations (n = 1, 2 and 3, Tx = O, F and OH), and investigate the quantum-confinement effect on the HER catalytic performance. Surprisingly, we reveal a strong thickness effect of the MXene layer on the HER performance. Amongst the various surface-terminated derivatives, Ti2CF2-PtSA and Ti2CH2O2-PtSA are found to be the best HER catalysts with the change of Gibbs free energy {\Delta}G*H ~ 0 eV, complying with the thermoneutral condition. The ab initio molecular dynamics simulations reveal that Ti2CF2-PtSA and Ti2CH2O2-PtSA possess a good thermodynamic stability. The present work shows that the HER catalytic activity of the MXene is not solely governed by the local environment of the surface such as Pt single atom. We point out the critical role of thickness control and surface decoration of substrate in achieving a high-performance HER catalytical activity.

Abstract: Nitrate reduction to ammonia has attracted much attention for nitrate (NO3-) removal and ammonia (NH3) production. Identifying promising catalyst for active nitrate electroreduction reaction (NO3RR) is critical to realize efficient upscaling synthesis of NH3 under low-temperature condition. For this purpose, by means of spin-polarized first-principles calculations, the NO3RR performance on a series of graphitic carbon nitride (g-CN) supported double-atom catalysts (denoted as M1M2@g-CN) are systematically investigated. The synergistic effect of heterogeneous dual-metal sites can bring out tunable activity and selectivity for NO3RR. Amongst 21 candidates examined, FeMo@g-CN and CrMo@g-CN possess a high performance with low limiting potentials of -0.34 and -0.39 V, respectively. The activities can be attributed to a synergistic effect of the M1M2 dimer d orbitals coupling with the anti-bonding orbital of NO3-. The dissociation of deposited FeMo and CrMo dimers into two separated monomers is proved to be difficult, ensuring the kinetic stability of M1M2@g-CN. Furthermore, the dual-metal decorated on g-CN significantly reduces the bandgap of g-CN and broadens the adsorption window of visible light, implying its great promise for photocatalysis. This work opens a new avenue for future theoretical and experimental design related to NO3RR photo-/electrocatalysts.

Abstract: Kagome materials have attracted a surge of research interest recently, especially for the ones combining with magnetism, and the ones with weak interlayer interactions which can fabricate thin devices. However, kagome materials combining both characters of magnetism and weak interlayer interactions are rare. Here we investigate a new family of titanium based kagome materials RETi3Bi4 (RE = Eu, Gd and Sm). The flakes of nanometer thickness of RETi3Bi4 can be obtained by exfoliation due to the weak interlayer interactions. According to magnetic measurements, out-of-plane ferromagnetism, out-of-plane anti-ferromagnetism, and in-plane ferromagnetism are formed for RE = Eu, Gd, and Sm respectively. The magnetic orders are simple and the saturation magnetizations can be relatively large since the rare earth elements solely provide the magnetic moments. Further by angle-resolved photoemission spectroscopy (ARPES) and first-principles calculations, the electronic structures of RETi3Bi4 are investigated. The ARPES results are consistent with the calculations, indicating the bands characteristic with kagome sublattice in RETi3Bi4. We expect these materials to be promising candidates for observation of the exotic magnetic topological phases and the related topological quantum transport studies.

Abstract: Natural minerals contain ions that become hydrated when they come into contact with water in vapor and liquid forms. Muscovite mica -- a common phyllosilicate with perfect cleavage planes -- is an ideal system to investigate the details of ion hydration. The cleaved mica surface is decorated by an array of K$^+$ ions that can be easily exchanged with other ions or protons when immersed in an aqueous solution. Despite the vast interest in the atomic-scale hydration processes of these K$^+$ ions, experimental data under controlled conditions have remained elusive. Here, atomically resolved non-contact atomic force microscopy (nc-AFM) is combined with X-ray photoelectron spectroscopy (XPS) to investigate the cation hydration upon dosing water vapor at 100 K in ultra-high vacuum (UHV). The cleaved surface is further exposed to ultra-clean liquid water at room temperature, which promotes ion mobility and partial ion-to-proton substitution. The results offer the first direct experimental views of the interaction of water with muscovite mica in UHV. The findings are in line with previous theoretical predictions.

Abstract: We show that the interplay between spin-orbit coupling and cubic symmetry breaking in SrTiO3 results in a highly anisotropic Zeeman effect, which can be measured via electrically-driven, electrically-detected spin resonance enabled by the momentum dependence of spin-orbit coupling effects that become particularly effective if the inversion symmetry is broken. The proposed effects are expected to provide a unique insight into the roles of spin-orbit interaction and symmetry breaking in SrTiO3 and its heterostructures.

Abstract: Owing to its atomically thin thickness, layer-dependent tunable band gap, flexibility, and CMOS compatibility, MoS$_2$ is a promising candidate for photodetection. However, mono-layer MoS2-based photodetectors typically show poor optoelectronic performances, mainly limited by their low optical absorption. In this work, we hybridized CVD-grown monolayer MoS$_2$ with a gold nanodisk (AuND) array to demonstrate a superior visible photodetector through a synergetic effect. It is evident from our experimental results that there is a strong light-matter interaction between AuNDs and monolayer MoS$_2$, which results in better photodetection due to a surface trap state passivation with a longer charge carrier lifetime compared to pristine MoS$_2$. In particular, the AuND/MoS$_2$ system demonstrated a photoresponsivity of $8.7 \times 10^{4}$ A/W, specific detectivity of $6.9 \times 10^{13}$ Jones, and gain $1.7 \times 10^{5}$ at $31.84 \mu W/cm^{2}$ illumination power density of 632 nm wavelength with an applied voltage of 4.0 V for an AuND/MoS$_2$-based photodetector. To our knowledge, these optoelectronic responses are one order higher than reported results for CVD MoS$_2$-based photodetector in the literature.