Materials Science (cond-mat.mtrl-sci)

Abstract: The freshly synthesized two-dimensional biphenylene carbon network composed of a hexagon, a square and an octagonal configuration is a fascinating structure that attracts attention. In this work, the first principles calculations have been used to explore the similar biphenylene network of boron-carbon-nitrogen. There are six possible phases of borocarbonitrides which are isoelectronic to biphenylene carbon networks with a stoichiometric ratio of 1:1:1 for borons, C, and N atoms. All possible isoelectronic structures of the BCN combination of biphenylene networks are found to be stable, according to first principles calculations. The relatively significant number of robust C-C, B-N bonds and strong partial ionic-covalent B-C and C-N bonds inside these bpn-BCN monolayers efficiently stabilize in terms of formation energies, phonon dispersion calculations, mechanical strength ( by elastic moduli) and ab initio molecular dynamics at finite temperature. The electronic properties reveal the metallic nature of all bpn-BCN phases. These conducting monolayers might be advantageous for electrochemical potential, catalytic activity, and hydrogen evolution processes.

Abstract: In recent years, coherent electrons driven by light fields have attracted significant interest in exploring novel material phases and functionalities. However, observing coherent light-field-driven electron dynamics in solids is challenging because the electrons are scattered within several ten femtoseconds in ordinary materials, and the coherence between light and electrons is disturbed. However, when we use Weyl semimetals, the electron scattering becomes relatively long (several hundred femtoseconds - several picoseconds), owing to the suppression of the back-scattering process. This study presents the light-field-driven dynamics by the THz pulse to Weyl semimetal Co3Sn2S2, where the intense THz pulse of a monocycle electric field nonlinearly generates direct current (DC) via coherent acceleration without scattering and non-adiabatic excitation (Landau-Zener Transition). In other words, the non-Ohmic current appears in the Weyl semimetal with a combination of the long relaxation time and an intense THz pulse. This nonlinear DC generation also demonstrates a Keldysh crossover from a photon picture to a light-field picture by increasing the electric field strength.

Abstract: A novel carbon allotrope, hexagonal C12, is proposed from crystal chemistry and quantum density functional theory DFT calculations of ground state and physical properties. The structure exhibits corner sharing distorted tetrahedra with the presence of C3 triangular cyclopropane-like moiety connecting planar carbon. C12 allotrope is found cohesive and stable both mechanically (elastic constants and their combinations) and dynamically -- phonons band structures -- and presents ultra-hardness with Vickers number of 70 GPa. The temperature dependence of the heat capacity CV shows close magnitudes to experimental results of diamond. The electronic band structure reveals closely insulating behavior with 2.5 eV band gap, half smaller than in diamond.

Abstract: Two-dimensional transition metal dichalcogenides are among the most promising materials for water-splitting catalysts. While a variety of methods have been applied to promote the hydrogen evolution reaction on the transition metal dichalcogenides, doping of transition metal heteroatoms have attracted much attention since it provides effective ways to optimize the hydrogen adsorption and H2 generation reactions. Herein, we provide in-depth and systematic analyses on the trends of the free energy of hydrogen adsorption ({\Delta}GH*), the most well-known descriptor for evaluating hydrogen evolution reaction performance, in the doped transition metal dichalcogenides. Using the total 150 doped transition metal dichalcogenides, we carried out the atom-level analysis on the origin of {\Delta}GH* changes upon the transition metal heteroatom doping, and suggest two key factors that govern the hydrogen adsorption process on the doped transition metal dichalcogenides: 1) the changes in the charge of chalcogen atoms where hydrogen atoms adsorbed for the early transition metal doped structures, and 2) the structural deformation energies accompanying in introduced dopants for the late transition metal doped structures. Based on our findings, we interpret from a new perspective how vacancies in the TM-doped TMDs can provide optimal {\Delta}GH* in HER. We suggest electrostatic control for early TM doped systems and structural control for late TM doped systems as the effective strategies for the thermoneutral {\Delta}GH* in TMD.

Abstract: In the fundamental understanding of magnetic interactions between atoms in solids, the crystal lattice is one of the key parameters. As the effective tool for controlling the lattice using tensile stress is limited, there are only few demonstrations of the control in magnetic properties with expanding the lattice structure. Here, we observe that the Curie temperature (Tc) of quasi two-dimensional Cr2Ge2Te6 with NiO overlayer doubles from ~60 K to ~120 K, describe a clear correlation of magnetic properties with lattice expansion, which is characterized by several probes and computational approaches, and address on the mechanisms leading to the increase in Tc via the change in exchange interactions.

Abstract: Surface roughness is a key factor when it comes to friction and wear, as well as to other physical properties. These phenomena are controlled by mechanisms acting at small scales, in which the topography of apparently-flat surfaces is revealed. Roughness in natural surfaces has been reported to conform to self-affine statistics in a wide variety of settings (ranging from earthquake physics to micro-electro-mechanical devices), meaning that the height profile can be described using a spectrum where the amplitude is proportional to its wavelength raised to a constant power, which is related to a statistical parameter named Hurst exponent. We analyze the roughness evolution in atomistic surfaces during molecular dynamics simulations of wear. Both pairs of initially-flat and initially-rough surfaces in contact are worn by a third body formed by particles trapped between them during relative sliding. During the first sliding stages, the particles trapped between the first bodies scratch the surfaces. Once the former become coated with atoms from the latter, the wear process slows down and becomes "adhesive-like". The initial particle sizes are consistent with the minimum size to be expected for the debris, but tend to grow by material removal from the surfaces and to agglomerate. We show that, for the particular configurations under consideration, the surface roughness seems to converge to a steady state characterized by Hurst exponent close to 0.8, independently of the initial conditions.

Abstract: The two-dimensional (2D) bulk photovoltaic effect (BPVE) is a cornerstone for future highly efficient 2D solar cells and optoelectronics. The ferromagnetic semiconductor 2H-FeCl2 is shown to realize a new type of BPVE in which spatial inversion (P), time reversal (T), and space-time reversal (PT) symmetries are broken (PT-broken). Using density functional theory and perturbation theory, we show that 2H-FeCl2 exhibits giant photocurrents, photo-spin-currents, and photo-orbital-currents under illumination by linearly polarized light. The injection-like and shift-like photocurrents coexist and propagate in different directions. The material also demonstrates substantial photoconductance, photo-spin-conductance, and photo-orbital-conductance, with magnitudes up to 4650 (nm{\cdot}{\mu}A/V2), 4620 (nm{\cdot}{\mu}A/V2 {\hbar}/2e), and 6450 (nm{\cdot}{\mu}A/V2 {\hbar}/e), respectively. Furthermore, the injection-currents, shift-spin-currents, and shift-orbital-currents can be readily switched via rotating the magnetizations of 2H-FeCl2. These results demonstrate the superior performance and intriguing control of a new type of BPVE in 2H-FeCl2.

Abstract: A long operational lifetime is required for the use of solar cells in real-life photovoltaic applications. The optimization of operational lifetimes is achieved through understanding the inherent degradation phenomena in solar cells. In this study, graphene/Si Schottky-junction solar cells were produced, utilizing liquid-phase-exfoliated graphene as an active surface. The operational and interface stability of these solar cells over a period of 5 years in ambient conditions (following ISOS-D protocols: dark storage/shelf life) was examined, and the origin of their degradation was reported. It was found that the dominant degradation mechanism could be attributed to the degradation of silver contacts. This was indicated by a decrease in shunt resistance, an increase in the ideality factor (due to a higher carrier recombination), and a constant defect density in graphene films for up to 4 years. Measurements across the solar cell's active area during the 5-year period revealed neither significant spatial inhomogeneity, nor shunt channel defects.

Abstract: We present a method, based on the classical Green-Kubo theory of linear response, to compute the heat conductivity of extended systems, leveraging energy-density, rather than energy-current, fluctuations, thus avoiding the need to devise an analytical expression for the macroscopic energy flux. The implementation of this method requires the evaluation of the long-wavelength and low-frequency limits of a suitably defined correlation function, which we perform using a combination of recently-introduced cepstral-analysis and Bayesian extrapolation techniques. Our methodology is demonstrated against standard current-based Green-Kubo results for liquid argon and water, and compared with a recently proposed similar technique, which utilizes mass-density, instead of energy-density, fluctuations.

Abstract: White light emitting diodes are gaining popularity and are set to become the most common light source in the US by 2025. Their performance is still limited by the lack of an efficient red-emitting component with narrow band emission. The red phosphor SrLiAl$_3$N$_4$:Eu$^{2+}$ is among the first promising phosphors with small bandwidth for the next-generation lighting but the microscopic origin of this narrow emission remains elusive. In the present work, density functional theory, the $\Delta$SCF-constrained occupation method, and a generalized Huang-Rhys theory are used to provide an accurate description of the vibronic processes occurring at the two Sr$^{2+}$ sites that the Eu$^{2+}$ activator can occupy. The emission bandshape of Eu(Sr1), with a zero-phonon line at 1.906 eV and high luminescence intensity, is shown to be controlled by the coupling between the 5d$_{z^2}$-4f electronic transition and the low-frequency phonon modes associated to Sr and Eu displacements along the Sr channel. The good agreement between our computations and experimental results allows us to provide a structural assignment of the observed total spectrum. By computing explicitly the effect of the thermal expansion on zero-phonon line energies, the agreement is extended to the temperature-dependent spectrum. These results provide insights into the electron-phonon coupling accompanying the 5d-4f transition in similar UCr$_4$C$_4$-type phosphors: they highlight the importance of the Sr channel in shaping the narrow emission of SrLiAl$_3$N$_4$:Eu$^{2+}$, and shed new light into the structure-property relations of such phosphors.

Abstract: We study the molecular beam epitaxy of AlN nanowires between 950 and 1215 {\deg}C, well above the usual growth temperatures, to identify optimal growth conditions. The nanowires are grown by self-assembly on TiN(111) films sputtered onto Al$_2$O$_3$. Above 1100 {\deg}C, the TiN film is seen to undergo grain growth and its surface exhibits {111} facets where AlN nucleation preferentially occurs. Modelling of the nanowire elongation rate measured at different temperatures shows that the Al adatom diffusion length is maximised at 1150 {\deg}C, which appears to be the optimum growth temperature. However, analysis of the nanowire luminescence shows a steep increase in the deep-level signal already above 1050 {\deg}C, associated with O incorporation from the Al$_2$O$_3$ substrate. Comparison with AlN nanowires grown on Si, MgO and SiC substrates suggests that heavy doping of Si and O by interdiffusion from the TiN/substrate interface increases the nanowire internal quantum efficiency, presumably due to the formation of a SiN$_x$ or AlO$_x$ passivation shell. The outdiffusion of Si and O would also cause the formation of the inversion domains observed in the nanowires. It follows that for optoelectronic and piezoelectric applications, optimal AlN nanowire ensembles should be prepared at 1150 {\deg}C on TiN/SiC substrates and will require an ex situ surface passivation.

Abstract: Sensors based on spin qubits in 2D crystals offer the prospect of nanoscale sensing volumes, where the close proximity of the sensor and source could provide access to otherwise inaccessible signals. For AC magnetometry, the sensitivity and frequency range is typically limited by the noise spectrum, which determines the qubit coherence time. This poses a problem for III-V materials, as the non-zero spin of the host nuclei introduces a considerable source of magnetic noise. Here, we overcome this with a sensing protocol based on phase modulated continuous concatenated dynamic decoupling, which extends the coherence time towards the $T_1$ limit at room temperature and enables tuneable narrowband AC magnetometry. We demonstrate the protocol with an ensemble of negatively charged boron vacancies in hexagonal boron nitride, detecting in-plane AC fields within $\pm 150~\mathrm{MHz}$ of the electron spin resonance, and out-of-plane fields in the range of $\sim10-150~\mathrm{MHz}$. We measure an AC magnetic field sensitivity of $\sim1~\mathrm{\mu T/\sqrt{Hz}}$ at $\sim2.5~\mathrm{GHz}$, for a sensor volume of $\sim0.1~\mathrm{\mu m^3}$, and demonstrate that the sensor can reconstruct the AC magnetic field from a wire loop antenna. This work establishes the viability of spin defects in 2D materials for high frequency magnetometry, demonstrating sensitivities that are comparable to nitrogen vacancy centres in diamond for microscopic sensing volumes, and with wide-ranging applications across science and technology.

Abstract: Nonreciprocal gyrotropic materials have attracted significant interest recently in material physics, nanophotonics, and topological physics. Most of the well-known nonreciprocal materials, however, only show nonreciprocity under a strong external magnetic field and within a small segment of the electromagnetic spectrum. Here, through first-principles density functional theory calculations, we show that due to strong spin-orbit coupling manganese-bismuth (MnBi) exhibits nonreciprocity without any external magnetic field and a large gyrotropy in a broadband long-wavelength infrared regime (LWIR). Further, we design a multi-layer structure based on MnBi to obtain a maximum degree of spin-polarized thermal emission at 7 $\mu$m. The connection established here between large gyrotropy and the spin-polarized thermal emission points to a potential use of MnBi to develop spin-controlled thermal photonics platforms.

Abstract: We have performed a comprehensive, first-principles high-throughput study of the magnetic properties of halide double perovskites, $Cs_2BB^\prime Cl_6$, with magnetic ions occupying one or both B and B$^\prime$ sites. Our findings indicate a general tendency for these materials to exhibit antiferromagnetic ordering with low N\'eel temperatures. At the same time, we reveal a few potential candidates that predicted to be ferromagnetic with relatively high Curie temperatures. Achieving ferromagnetic coupling might be feasible via simultaneously alloying at B and B$^\prime$ sites with magnetic 3d and non-magnetic 5d ions. With this approach, we discover that $Cs_2HgCrCl_6$, $Cs_2AgNiCl_6$ and $Cs_2AuNiCl_6$ have high Curie temperatures relative to their peers, with the latter two exhibiting half metallic behaviour. Further, this study illuminates the underpinning mechanism of magnetic exchange interactions in halide double perovskites, enabling a deeper understanding of their magnetic behaviour. Our findings, especially the discovery of the compounds with robust half-metallic properties and high Curie temperatures holds promise for potential applications in the field of spintronics.