Materials Science (cond-mat.mtrl-sci)

Abstract: We have successfully synthesized single crystals, solved the crystal structure, and studied the magnetic properties of a new family of copper halides (C$_4$H$_{14}$N$_2$)Cu$_2X_6$ ($X$= Cl, Br). These compounds crystallize in an orthorhombic crystal structure with space group $Pnma$. The crystal structure features Cu$^{2+}$ dimers arranged parallel to each other that makes a zig-zag two-leg ladder-like structure. Further, there exists a diagonal interaction between two adjacent dimers which generates inter-dimer frustration. Both the compounds manifest a singlet ground state with a large gap in the excitation spectrum. Magnetic susceptibility is analyzed in terms of both interacting spin-$1/2$ dimer and two-leg ladder models followed by exact diagonalization calculations. Our theoretical calculations in conjunction with the experimental magnetic susceptibility establish that the spin-lattice can be described well by a frustrated two-leg ladder model with strong rung coupling ($J_0/k_{\rm B} \simeq 116$ K and 300 K), weak leg coupling ($J^{\prime\prime}/k_{\rm B} \simeq 18.6$ K and 105 K), and equally weak diagonal coupling ($J^{\prime }/k_{\rm B} \simeq 23.2$ K and 90 K) for Cl and Br compounds, respectively. These exchange couplings set the critical fields very high, making them experimentally inaccessible. The correlation function decays exponentially as expected for a gapped spin system. The structural aspects of both the compounds are correlated with their magnetic properties. The calculation of entanglement witness divulges strong entanglement in both the compounds which persists upto high temperatures, even beyond 370~K for the Br compound.

Abstract: Now-a-days, the development of clean and green energy sources is the prior interest of research due to increasing global energy demand and extensive usage of fossil fuels that create pollutants. Hydrogen has the highest energy density by weight among all chemical fuels. For the commercial-scale production of hydrogen, water electrolysis is the best method which in turn requires an efficient, cost-effective and earth-abundant electrocatalyst. Recent studies have shown that the 2D Janus TMDs are highly effective in the electrocatalytic activity for HER. Herein we report a 2D monolayer WSeTe Janus TMD electrocatalyst for HER. We studied the electronic properties of 2D monolayer WSeTe Janus TMD using periodic DFT calculations, and the direct electronic band gap was obtained to be 2.39 eV. After the calculations of electronic properties, we explored the HER intermediates including various transition state structures (Volmer TS, Heyrovsky TS, and Tafel TS) using a molecular cluster model of WSeTe noted as W10Se9Te12. The present calculations revealed that the 2D monolayer WSeTe Janus TMD is a potential electrocatalyst for HER. It has the lowest energy barriers for all the TSs among other TMDs, such as MoS2, Mn-MoS2, MoSSe, etc. The calculated Heyrovsky energy barrier (= 8.72 kcal.mol-1) for the Volmer-Heyrovsky mechanism is larger than the Tafel energy barrier (=3.27 kcal.mol-1) in the Volmer-Tafel mechanism. Hence our present study suggests that the formation of H2 is energetically more favorable via the Vomer-Tafel mechanism. This work helps shed light on the rational design of effective HER catalysts.

Abstract: The large bandgap and strong covalent bonds of hexagonal boron nitride (hBN) had long been thought to be chemically inert. Due to its inertness with saturated robust covalent bonds, the pristine 2D monolayer hBN cannot be functionalized for applications of energy conversion. Therefore, it is necessary to make the 2D hBN chemically reactive for potential applications. Here, we have computationally designed a single nitrogen (N) and boron (B) di-vacancy of the 2D monolayer hBN, noted by VBN defective-BN (d-BN), to activate the chemical reactivity, which is an effective strategy to use the d-BN for potential applications. Single Pt atom absorbed on the defective area of the VBN d-BN acts as a single-atom catalyst which exhibits distinctive performances for O2 reduction reaction (ORR). First-principles based dispersion-corrected periodic hybrid Density Functional Theory (DFT-D) method has been employed to investigate the equilibrium structure and properties of the Pt-absorbed 2D defective boron nitride (Pt-d-BN). The present study shows the semiconducting character of Pt-d-BN with an electronic bandgap of 1.30 eV, which is an essential aspect of the ORR. The ORR mechanism on the surface of 2D monolayer Pt-d-BN follows a 4e-reduction route because of the low barriers to OOH formation and dissociation, H2O2 instability and water production at the Pt-d-BN surface. Here, both the dissociative and associative ORR mechanisms have been investigated, and it is found that results for both mechanisms with the ORR pathways are almost equally favorable. Therefore, it can be mentioned here that the 2D monolayer Pt-d-BN exhibits a high selectivity for the four-electron reduction pathway. According to the calculations of the relative adsorption energy of each step in ORR, the Pt-d-BN is anticipated to exhibit substantial catalytic activity.

Abstract: Interfacial thermal resistance arises challenges for the thermal management as the modern semiconductors are miniatured to nanoscale. Previous studies found that graded mass distribution in interface can maximumly enhance the interfacial thermal conductance of crystalline interface, however, whether this strategy is effective for amorphous interface is less explored. In this work, graded mass distribution in the amorphous interface between crystalline Si and crystalline Ge is optimized to increase the interfacial thermal conductance by the extended atomistic Greens function method.

Abstract: A non-iterative method is presented to calculate the closest Wannier functions (CWFs) to a given set of localized guiding functions, such as atomic orbitals, hybrid atomic orbitals, and molecular orbitals, based on minimization of a distance measure function. It is shown that the minimization is directly achieved by a polar decomposition of a projection matrix via singular value decomposition, making iterative calculations and complications arising from the choice of the gauge irrelevant. The disentanglement of bands is inherently addressed by introducing a smoothly varying window function and a greater number of Bloch functions, even for isolated bands. In addition to atomic and hybrid atomic orbitals, we introduce embedded molecular orbitals in molecules and bulks as the guiding functions, and demonstrate that the Wannier interpolated bands accurately reproduce the targeted conventional bands of a wide variety of systems including Si, Cu, the TTF-TCNQ molecular crystal, and a topological insulator of Bi$_2$Se$_3$. We further show the usefulness of the proposed method in calculating effective atomic charges. These numerical results not only establish our proposed method as an efficient alternative for calculating WFs, but also suggest that the concept of CWFs can serve as a foundation for developing novel methods to analyze electronic structures and calculate physical properties.

Abstract: Microscopy images are usually analyzed qualitatively or manually and there is a need for autonomous quantitative analysis of objects. In this paper, we present a physics-based computational model for accurate segmentation and geometrical analysis of one-dimensional irregular and deformable objects from microscopy images. This model, named Nano1D, has four steps of preprocessing, segmentation, separating overlapped objects and geometrical measurements. The model is tested on Ag nanowires, and successfully segments and analyzes their geometrical characteristics including length, width and distributions. The function of the algorithm is not undermined by the size, number, density, orientation and overlapping of objects in images. The main strength of the model is shown to be its ability to segment and analyze overlapping objects successfully with more than 99% accuracy, while current machine learning and computational models suffer from inaccuracy and inability to segment overlapping objects. Nano1D can analyze one-dimensional (1D) nanoparticles including nanowires, nanotubes, nanorods in addition to other 1D features of microstructures like microcracks, dislocations etc.

Abstract: Resistivity measurements are widely exploited to uncover electronic excitations and phase transitions in metallic solids. While single crystals are preferably studied to explore crystalline anisotropies, these usually cancel out in polycrystalline materials. Here we show that in polycrystalline Mn3Zn0.5Ge0.5N with non-collinear antiferromagnetic order, changes in the diagonal and, rather unexpected, off-diagonal components of the resistivity tensor occur at low temperatures indicating subtle transitions between magnetic phases of different symmetry. This is supported by neutron scattering and explained within a phenomenological model which suggests that the phase transitions in magnetic field are associated with field induced topological orbital momenta. The fact that we observe transitions between spin phases in a polycrystal, where effects of crystalline anisotropy are cancelled suggests that they are only controlled by exchange interactions. The observation of an off-diagonal resistivity extends the possibilities for realising antiferromagnetic spintronics with polycrystalline materials.

Abstract: Defects in the lattice are of primal importance to tune graphene chemical, thermal and electronic properties. Electron-beam irradiation is an easy method to induce defects in graphene following pre-designed patterns, but no systematic study of the time evolution of the resulting defects is available. In this paper, the change over time of defected sites created in graphene with low-energy ($\leq 20$ keV) electron irradiation is studied both experimentally via micro-Raman spectroscopy for a period of $6\times 10^3$ hours and through molecular dynamics simulations. During the first 10 h, the structural defects are stable at the highest density value. Subsequently, the crystal partially reconstructs, eventually reaching a stable, less defected condition after more than one month. The simulations allow the rationalization of the processes at the atomic level and confirm that the irradiation induces composite clusters of defects of different nature rather than well-defined nanoholes as in the case of high-energy electrons. The presented results identify the timescale of the defects stability, thus establishing the operability timespan of engineerable defect-rich graphene devices with applications in nanoelectronics. Moreover, long-lasting chemical reactivity of the defective graphene is pointed out. This property can be exploited to functionalize graphene for sensing and energy storage applications.

Abstract: Electron-photon temporal correlations in electron energy loss (EELS) and cathodoluminescence (CL) spectroscopies have recently been used to measure the relative quantum efficiency of materials. This combined spectroscopy, named Cathodoluminescence excitation spectroscopy (CLE), allows the identification of excitation and decay channels which are hidden in average measurements. Here, we demonstrate that CLE can also be used to measure excitation's decay time. In addition, the decay time as a function of the excitation energy is accessed, as the energy for each electron-photon pair is probed. We used two well-known insulating materials to characterize this technique, nanodiamonds with \textit{NV$^0$} defect emission and h-BN with a \textit{4.1 eV} defect emission. Both also exhibit marked transition radiations, whose extremely short decay times can be used to characterize the instrumental response function. It is found to be typically 2 ns, in agreement with the expected limit of the EELS detector temporal resolution. The measured lifetimes of \textit{NV$^0$} centers in diamond nanoparticles (20 to 40 ns) and \textit{4.1 eV} defect in h-BN flakes ($<$ 2 ns) matches those reported for those materials previously.

Abstract: Exploiting chemical short-range order (SRO) is a promising new avenue for manipulating the properties of alloys. However, existing modeling frameworks are not sufficient to understand and predict SRO in multicomponent (>3) alloys. In this work, we developed a hybrid computational thermodynamics framework by marrying unique advantages from CVM (Cluster Variation Method) and CALPHAD (CALculation of PHAse Diagram) method through incorporating chemical SRO into CALPHAD with a novel cluster-based solution model. The key is to use the Fowler-Yang-Li transform to decompose the cumbersome cluster chemical potentials in CVM into fewer site chemical potentials of the basis cluster, thereby considerably reducing the number of variables that must be minimized for multicomponent systems. The new framework puts more physics, primarily intrinsic SRO, into CALPHAD, while maintaining its practicality and efficiency. It leverages statistical mechanics to yield a more physical description of configurational entropy and opens the door to cluster-based CALPHAD database development. The application of this newly proposed model in the prototype FCC AB system demonstrated that this model can correctly capture the essential features of the phase diagram and thermodynamic properties. The hybrid CVM-CALPHAD framework represents a new methodology for thermodynamic modeling that enables atomic-scale order to be exploited as a dimension for materials design, which potentially leads to novel complex concentrated alloys. It achieves a balance between the accuracy and computational cost for modeling multicomponent alloys with the intrinsic SRO in the context of CALPHAD.

Abstract: The dielectric properties of Bi$_2$Te$_3$, a layered compound crystallizing in a rhombohedral structure, are investigated by means of first-principles calculations at the random phase approximation level. A special attention is devoted to the anisotropy in the dielectric function and to the local field effects that strongly renormalize the optical properties in the UV-visible range when the electric field is polarized along the stacking axis. Furthermore, both the Born effective charges for each atom and the zone center phonon frequencies and eigenvectors needed to describe the dielectric response in the infrared range are computed. Our theoretical near-normal incidence reflectivity spectras in both the UV-visible and infrared range are in fairly good agreement with the experimental spectras, provided that the free carriers Drude contribution arising from defects is included in the infrared response. The anisotropic plasmon frequencies entering the Drude model are computed within the rigid band approximation, suggesting that a measurement of the reflectivity in the infrared range for both polarizations might allow to infer not only the type of doping but also the level of doping.

Abstract: EPIq (Electron-Phonon wannier Interpolation over k and q-points) is an open-source software for the calculation of electron-phonon interaction related properties from first principles.Acting as a post-processing tool for a density-functional perturbation theory code ( Quantum ESPRESSO ) and wannier90, EPIq exploits the localization of the deformation potential in the Wannier function basis and the stationary properties of a force-constant functional with respect to the first-order perturbation of the electronic charge density to calculate many electron-phonon related properties with high accuracy and free from convergence issues related to Brillouin zone sampling. EPIq features includes: the adiabatic and non-adiabatic phonon dispersion, superconducting properties (including the superconducting band gap in the Migdal-Eliashberg formulation), double-resonant Raman spectra and lifetime of excited carriers. The possibility to customize most of its input makes EPIq a versatile and interoperable tool. Particularly relevant is the interaction with the Stochastic Self-Consistent Harmonic Approximation (SSCHA) allowing anharmonic effects to be included in the calculation of electron-properties. The scalability offered by the Wannier representation combined with a straightforward workflow and easy-to-read input and output files make EPIq accessible to the wide condensed matter and material science communities.

Abstract: Magnetic random access memory (MRAM) is a leading emergent memory technology that is poised to replace current non-volatile memory technologies such as eFlash. However, the scaling of MRAM technologies is heavily affected by device-to-device variability rooted in the stochastic nature of the MRAM writing process into nanoscale magnetic layers. Here, we introduce a non-contact metrology technique deploying Scanning NV Magnetometry (SNVM) to investigate MRAM performance at the individual bit level. We demonstrate magnetic reversal characterization in individual, < 60 nm sized bits, to extract key magnetic properties, thermal stability, and switching statistics, and thereby gauge bit-to-bit uniformity. We showcase the performance of our method by benchmarking two distinct bit etching processes immediately after pattern formation. Unlike previous methods, our approach unveils marked differences in switching behaviour of fully contacted MRAM devices stemming from these processes. Our findings highlight the potential of nanoscale quantum sensing of MRAM devices for early-stage screening in the processing line, paving the way for future incorporation of this nanoscale characterization tool in the semiconductor industry.

Abstract: We investigate optically induced magnetization in Floquet-Weyl semimetals generated by irradiation of a circularly-polarized continuous-wave laser from the group II-V narrow gap semiconductor Zn$_3$As$_2$ in a theoretical manner. Here, this trivial and nonmagnetic crystal is driven by the laser with a nearly resonant frequency with a band gap to generate two types of Floquet-Weyl semimetal phases composed of different spin states. These two phases host nontrivial two-dimensional surface states pinned to the respective pairs of the Weyl points. By numerically evaluating the laser-induced transient carrier-dynamics, it is found that both spins are distributed in an uneven manner on the corresponding surface states, respectively, due to significantly different excitation probabilities caused by the circularly-polarized laser with the nearly resonant frequency. It is likely that such spin-polarized surface states produce surface magnetization, and furthermore the inverse Faraday effect also contributes almost as much as the spin magnetization. To be more specific, excited carries with high density of the order of $10^{21}\: {\rm cm}^{-3}$ are generated by the laser with electric field strength of a few MV/cm to result in the surface magnetization that becomes asymptotically constant with respect to time, around 1 mT. The magnitude and the direction of it depend sharply on both of the intensity and frequency of the driving laser, which would be detected by virtue of the magneto-optic Kerr effect.

Abstract: SiGe heteroepitaxial growth yields pristine host material for quantum dot qubits, but residual interface disorder can lead to qubit-to-qubit variability that might pose an obstacle to reliable SiGe-based quantum computing. We demonstrate a technique to reconstruct 3D interfacial atomic structure spanning multiqubit areas by combining data from two verifiably atomic-resolution microscopy techniques. Utilizing scanning tunneling microscopy (STM) to track molecular beam epitaxy (MBE) growth, we image surface atomic structure following deposition of each heterostructure layer revealing nanosized SiGe undulations, disordered strained-Si atomic steps, and nonconformal uncorrelated roughness between interfaces. Since phenomena such as atomic intermixing during subsequent overgrowth inevitably modify interfaces, we measure post-growth structure via cross-sectional high-angle annular dark field scanning transmission electron microscopy (HAADF-STEM). Features such as nanosized roughness remain intact, but atomic step structure is indiscernible in $1.0\pm 0.4$~nm-wide intermixing at interfaces. Convolving STM and HAADF-STEM data yields 3D structures capturing interface roughness and intermixing. We utilize the structures in an atomistic multivalley effective mass theory to quantify qubit spectral variability. The results indicate (1) appreciable valley splitting (VS) variability of roughly $\pm$ $50\%$ owing to alloy disorder, and (2) roughness-induced double-dot detuning bias energy variability of order $1-10$ meV depending on well thickness. For measured intermixing, atomic steps have negligible influence on VS, and uncorrelated roughness causes spatially fluctuating energy biases in double-dot detunings potentially incorrectly attributed to charge disorder.

Abstract: Zinc dialkyldithiophosphates (ZDDPs) have been commonly used as anti-wear additives in the automotive industry for the past 80 years. The morphology, composition and structure of the ZDDPs phosphate-based tribofilm, which is essential for its lubricant functioning, have been widely studied experimentally. However, despite their widespread use, a general agreement on their primary functioning mechanism is still lacking. The morphology and composition of the ZDDPs phosphate-based tribofilm have been widely studied experimentally, but the formation process and the relevant driving forces are still largely debated. In particular, it is unclear whether the stress-induced molecular dissociation occurs in the bulk oil or on the substrate. In this work, we employ ab initio density-functional theory simulations to compare ZDDP fragmentation in vacuum and over a reactive substrate, considering the effects of surface oxidation on the dissociation path. Our results show that the molecular dissociation is highly endothermic in the absence of a supporting substrate, while in the presence of an iron substrate it becomes highly energetically favoured. Moreover, the presence of the substrate changes the reaction path. At the same time, surface oxidation reduces the molecule-substrate interaction. These findings provide valuable insights into the early stages of the formation of phosphate-based tribofilms.