Materials Science (cond-mat.mtrl-sci)

Abstract: The magnetic structure is crucial in determining the physical properties inherent in magnetic compounds. We present an adequate descriptor for magnetic structure with proper magnetic symmetry and high discrimination performance, which does not depend on artificial choices for coordinate origin, axis, and magnetic unit cell in crystal. We extend the formalism called ``smooth overlap of atomic positions'' (SOAP) providing a numerical representation of atomic configurations to that of magnetic moment configurations. We introduce the descriptor in terms of the vector spherical harmonics to describe a magnetic moment configuration and partial spectra from the expansion coefficients. We discuss that the lowest order partial spectrum is insufficient to discriminate the magnetic structures with different magnetic anisotropy, and a higher order partial spectrum is required in general to characterize detailed magnetic structures on the same atomic configuration. We then introduce the fourth-order partial spectrum and evaluate the discrimination performance for different magnetic structures, mainly focusing on the difference in magnetic symmetry. The modified partial spectra that are defined not to reflect the difference of magnetic anisotropy are also useful in evaluating magnetic structures obtained from first-principles calculations without spin-orbit coupling. We apply the present method to the symmetry-classified magnetic structures for the crystals of Mn$_3$Ir and Mn$_3$Sn, which are known to exhibit anomalous transport under the antiferromagnetic order, and examine the discrimination performance of the descriptor for different magnetic structures on the same crystal.

Abstract: We investigate the morphologies of the Ge(001) surface that are produced by bombardment with a normally incident, broad argon ion beam at sample temperatures above the recrystallization temperature. Two previously-observed kinds of topographies are seen, i.e., patterns consisting of upright and inverted rectangular pyramids, as well as patterns composed of shallow, isotropic basins. In addition, we observe the formation of an unexpected third type of pattern for intermediate values of the temperature, ion energy and ion flux. In this type of transitional morphology, isolated peaks with rectangular cross sections stand above a landscape of shallow, rounded basins. We also extend past theoretical work to include a second order correction term that comes from the curvature dependence of the sputter yield. For a range of parameter values, the resulting continuum model of the surface dynamics produces patterns that are remarkably similar to the transitional morphologies we observe in our experiments. The formation of the isolated peaks is the result of a term that is not ordinarily included in the equation of motion, a second order correction to the curvature dependence of the sputter yield.

Abstract: We have demonstrated a simple and accurate method for characterizing the capacitance of Graphene/n-Si Schottky junction solar cells (GSSCs) which embed the metal-oxide-semiconductor (MOS) capacitor. We measured two types of GSSCs, one with thermal annealing treatments (w-a) and one without (wo-a). It was found that the wo-a GSSC exhibits a two-step feature in the phase versus forward bias voltage relationship, which may be attributed to the presence of polymethyl methacrylate residues. By considering the capacitance of the MOS capacitor (Cmos) and its standard deviation, we successfully obtained the capacitance of the Schottky junction (CSch), and evaluated meaningful built-in potentials (Schottky barrier heights) which are 0.51V (0.78eV) and 0.47V (0.75eV) for the w-a and wo-a GSSCs, respectively, by the Mott-Schottky analysis. We also briefly discuss the relationship between CSch and the Nyquist and Bode plots, finding that the RC time constant decreases due to the subtraction of Cmos.

Abstract: Self-doping can not only suppress the photogenerated charge recombination of semiconducting quantum dots by self-introducing trapping states within the bandgap, but also provide high-density catalytic active sites as the consequence of abundant non-saturated bonds associated with the defects. Here, we successfully prepared semiconducting copper selenide (CuSe) confined quantum dots with abundant vacancies and systematically investigated their photoelectrochemical characteristics. Photoluminescence characterizations reveal that the presence of vacancies reduces the emission intensity dramatically, indicating a low recombination rate of photogenerated charge carriers due to the self-introduced trapping states within the bandgap. In addition, the ultra-low charge transfer resistance measured by electrochemical impedance spectroscopy implies the efficient charge transfer of CuSe semiconducting quantum dots-based photoelectrocatalysts, which is guaranteed by the high conductivity of their confined structure as revealed by room-temperature electrical transport measurements. Such high conductivity and low photogenerated charge carriers recombination rate, combined with high-density active sites and confined structure, guaranteeing the remarkable photoelectrocatalytic performance and stability as manifested by photoelectrocatalysis characterizations. This work promotes the development of semiconducting quantum dots-based photoelectrocatalysis and demonstrates CuSe semiconducting quantum confined catalysts as an advanced photoelectrocatalysts for oxygen evolution reaction.

Abstract: Diamond displays outstanding chemical, physical, and tribological properties, making it attractive for numerous applications ranging from biomedicine to tribology. However, the reaction of the materials with molecules present in the air, such as oxygen, hydrogen, and water, could significantly change the electronic and tribological properties of the films. In this study, we performed several density functional theory calculations to construct a database for the adsorption energies and dissociation barriers of these molecules on the most relevant diamond surfaces, including C(111), C(001), and C(110). The adsorption configurations, reaction paths, activation energies, and their influence on the structure of diamond surfaces are discussed. The results indicate that there is a strong correlation between adsorption energy and surface energy. Moreover, we found that the dissociation processes of oxygen molecules on these diamond surfaces can significantly alter the surface morphology and may affect the tribological properties of diamond films. These findings can help to advance the development and optimization of devices and antiwear coatings based on diamond.

Abstract: This work investigates the effect of copper substitution on the magnetic properties of SmCo$_{5}$ thin films synthesized by molecular beam epitaxy. A series of thin films with varying concentrations of Cu were grown under otherwise identical conditions to disentangle structural and compositional effects on the magnetic behavior. The combined experimental and theoretical studies show that Cu substitution at the Co$_{3g}$ sites not only stabilizes the formation of the SmCo$_{5}$ structure but enhances magnetic anisotropy and coercivity. Density functional theory calculations indicate that Sm(Co$_4$Cu$_{3g}$)$_5$ possesses a higher single-ion anisotropy as compared to pure SmCo$_{5}$. In addition, X-ray magnetic circular dichroism reveals that Cu substitution causes an increasing decoupling of the Sm 4\textit{f} and Co 3\textit{d} moments. Scanning transmission electron microscopy confirms predominantly SmCo$_{5}$ phase formation and reveals nanoscale inhomogeneities in the Cu and Co distribution. Our study based on thin film model systems and advanced characterization as well as modeling reveals novel aspects of the complex interplay of intrinsic and extrinsic contributions to magnetic hysteresis in rare earth-based magnets, \textit{i.e.} the combination of increased intrinsic anisotropy due to Cu substitution and the extrinsic effect of inhomogeneous elemental distribution of Cu and Co.

Abstract: Molybdenum dithiocarbamates (MoDTCs) are lubricant additives very efficient in reducing the friction of steel and they are employed in a number of industrial applications. The functionality of these additives is ruled by the chemical interactions occurring at the buried sliding interface, which are of key importance for the improvement of the lubrication performance. Yet, these tribochemical processes are very difficult to monitor in real time. Ab initio molecular dynamics simulations are the ideal tool to shed light into such a complicated reactivity. In this work we perform ab initio simulations, both in static and tribological conditions, to understand the effect of surface oxidation on the tribochemical reactivity of MoDTC and we find that when the surfaces are covered by oxygen, the first dissociative steps of the additives are significantly hindered. Our preliminary tribological tests on oxidized steel discs support these results. Bare metallic surfaces are necessary for a stable adsorption of the additives, their quick decomposition, and the formation of a durable MoS$_2$ tribolayer. This work demonstrates the importance of the catalytic role of the substrate and confirms the full capability of the computational protocol in the pursuit of materials and compounds more efficient in reducing friction.

Abstract: In the pursuit of sustainable lubricant materials, the conversion of common organic molecules into graphitic material has been recently shown to effectively reduce friction of metallic interfaces. Aromatic molecules are perfect candidates due to their inertness and possibility to form carbon-based tribofilms. Among many promising possibilities, we selected a group of common aromatic compounds and we investigated their capability to reduce the adhesion of iron interface. Ab initio molecular dynamic simulations of the sliding interface show that hypericin, a component of St. John's wort, effectively separates the mating iron surfaces better than graphene. This phenomenon is due to the size of the molecule, the reactivity of the moieties at its edges and the possibility to stack several of these structures that can easily slide on top of each other. The decomposition of the lateral groups of hypericin observed in the dynamic simulations suggests that the clustering of several molecules is possible, offering innovative paths to lubricate sliding contacts with compounds not typically employed in tribology.

Abstract: In the rapidly expanding field of two-dimensional materials, magnetic monolayers show great promise for the future applications in nanoelectronics, data storage, and sensing. The research in intrinsically magnetic two-dimensional materials mainly focuses on synthetic iodide and telluride based compounds, which inherently suffer from the lack of ambient stability. So far, naturally occurring layered magnetic materials have been vastly overlooked. These minerals offer a unique opportunity to explore air-stable complex layered systems with high concentration of local moment bearing ions. We demonstrate magnetic ordering in iron-rich two-dimensional phyllosilicates, focusing on mineral species of minnesotaite, annite, and biotite. These are naturally occurring van der Waals magnetic materials which integrate local moment baring ions of iron via magnesium/aluminium substitution in their octahedral sites. Due to self-inherent capping by silicate/aluminate tetrahedral groups, ultra-thin layers are air-stable. Chemical characterization, quantitative elemental analysis, and iron oxidation states were determined via Raman spectroscopy, wavelength disperse X-ray spectroscopy, X-ray absorption spectroscopy, and X-ray photoelectron spectroscopy. Superconducting quantum interference device magnetometry measurements were performed to examine the magnetic ordering. These layered materials exhibit paramagnetic or superparamagnetic characteristics at room temperature. At low temperature ferrimagnetic or antiferromagnetic ordering occurs, with the critical ordering temperature of 38.7 K for minnesotaite, 36.1 K for annite, and 4.9 K for biotite. In-field magnetic force microscopy on iron bearing phyllosilicates confirmed the paramagnetic response at room temperature, present down to monolayers.

Abstract: Diamond-based coatings are employed in several technological applications, for their outstanding mechanical properties, biocompatibility, and chemical stability. Of significant relevance is the interface with silicon oxide, where phenomena of adhesion, friction, and wear can affect drastically the performance of the coating. Here we monitor such phenomena in real-time by performing massive ab initio molecular dynamics simulations in tribological conditions. We take into account many relevant factors that can play a role, i.e. the diamond surface orientation and reconstruction, silanol density, as well as, the type and concentration of passivating species. The large systems size and the long simulations time, put our work at the frontier of what can be currently done with fully ab initio molecular dynamics. The results of our work point to full hydrogenation as an effective way to reduce both friction and wear for all diamond surfaces, while graphitization is competitive only on the (111) surface. Overall we expect that our observations will be useful to improve technological applications where the silica-diamond interface plays a key role. Moreover, we demonstrate that realistic and accurate in silico experiments are feasible nowadays exploiting HPC resources and HPC optimized software, paving the way to a more general understanding of the relationship between surface chemistry and nanoscale-tribology.

Abstract: We show that a lattice mode of arbitrary symmetry induces a well-defined macroscopic polarization at first order in the momentum and second order in the amplitude. We identify a symmetric flexoelectric-like contribution, which is sensitive to both the electrical and mechanical boundary conditions, and an antisymmetric Dzialoshinskii-Moriya-like term, which is unaffected by either. We develop the first-principles methodology to compute the relevant coupling tensors in an arbitrary crystal, which we illustrate with the example of the antiferrodistortive order parameter in SrTiO$_3$.

Abstract: Interfacial charge transfer in oxide heterostructures gives rise to a rich variety of electronic and magnetic phenomena. Designing heterostructures where one of the thin-film components exhibits a metal-insulator transition opens a promising avenue for controlling such phenomena both statically and dynamically. In this letter, we utilize a combination of depth-resolved soft X-ray standing-wave and hard X-ray photoelectron spectroscopies in conjunction with polarization-dependent X-ray absorption spectroscopy to investigate the effects of the metal-insulator transition in $LaNiO_{3}$ on the electronic and magnetic states at the $LaNiO_{3}/CaMnO_{3}$ interface. We report on a direct observation of the reduced effective valence state of the interfacial Mn cations in the metallic superlattice with an above-critical $LaNiO_{3}$ thickness (6 u.c.) due to the leakage of itinerant Ni 3d $e_{g}$ electrons into the interfacial $CaMnO_{3}$ layer. Conversely, in an insulating superlattice with a below-critical $LaNiO_{3}$ thickness of 2 u.c., a homogeneous effective valence state of Mn is observed throughout the $CaMnO_{3}$ layers due to the blockage of charge transfer across the interface. The ability to switch and tune interfacial charge transfer enables precise control of the emergent ferromagnetic state at the $LaNiO_{3}/CaMnO_{3}$ interface and, thus, has far-reaching consequences on the future strategies for the design of next-generation spintronic devices.