Materials Science (cond-mat.mtrl-sci)

Abstract: Topological insulators and semimetals have been shown to possess intriguing thermoelectric properties promising for energy harvesting and cooling applications. However, thermoelectric transport associated with the Fermi arc topological surface states on topological Dirac semimetals remains less explored. In this work, we systematically examine thermoelectric transport in a series of topological Dirac semimetal Cd3As2 thin films grown by molecular beam epitaxy. Surprisingly, we find significantly enhanced Seebeck effect and anomalous Nernst effect at cryogenic temperatures when the Cd3As2 layer is thin. Combining angle-dependent quantum oscillation analysis, magnetothermoelectric measurement, transport modelling and first-principles simulation, we isolate the contributions from bulk and surface conducting channels and attribute the unusual thermoeletric properties to the topological surface states. Our analysis showcases the rich thermoelectric transport physics in quantum-confined topological Dirac semimetal thin films and suggests new routes to achieving high thermoelectric performance at cryogenic temperatures.

Abstract: The properties of semiconductors and functional dielectrics are defined by their response in electric fields, which may be perturbed by defects and the strain they generate. In this work, we demonstrate how diffraction-based X-ray microscopy techniques may be utilized to image the electric field in insulating crystalline materials. By analysing a prototypical ferro- and piezoelectric material, BaTiO$_{3}$, we identify trends that can guide experimental design towards imaging the electric field using any diffraction-based X-ray microscopy technique. We explain these trends in the context of dark-field X-ray microscopy, but the framework is also valid for Bragg scanning probe X-ray microscopy, Bragg coherent diffraction imaging and Bragg X-ray ptychography. The ability to quantify electric field distributions alongside the defects and strain already accessible via these techniques offers a more comprehensive picture of the often complex structure-property relationships that exist in many insulating and semiconducting materials.

Abstract: The ferroelectric semiconductor $\alpha$-SnTe has been regarded as a topological crystalline insulator and the dispersion of its surface states has been intensively measured with angle-resolved photoemission spectroscopy (ARPES) over the last decade. However, much less attention has been given to the impact of the ferroelectric transition on its electronic structure, and in particular on its bulk states. Here, we investigate the low-energy electronic structure of $\alpha$-SnTe with ARPES and follow the evolution of the bulk-state Rashba splitting as a function of temperature, across its ferroelectric critical temperature of about $T_c\sim 110$ K. Unexpectedly, we observe a persistent band splitting up to room temperature, which is consistent with an order-disorder contribution to the phase transition that requires the presence of fluctuating local dipoles above $T_c$. We conclude that no topological surface state can occur at the (111) surface of SnTe, at odds with recent literature.

Abstract: The oxygen evolution reaction (OER) is a key enabler of sustainable chemical energy storage. Here, the author assesses the current status of protocols for benchmarking the OER in materials- and device-centered investigations and makes suggestions for more comparable data.

Abstract: Organic molecular crystals encompass a vast range of materials from pharmaceuticals to organic optoelectronics and proteins to waxes in biological and industrial settings. Crystal defects from grain boundaries to dislocations are known to play key roles in mechanisms of growth and also in the functional properties of molecular crystals. In contrast to the precise analysis of individual defects in metals, ceramics, and inorganic semiconductors enabled by electron microscopy, significantly greater ambiguity remains in the experimental determination of individual dislocation character and slip systems in molecular materials. In large part, nanoscale dislocation analysis in molecular crystals has been hindered by the severely constrained electron exposures required to avoid irreversibly degrading these crystals. Here, we present a low-dose, single-exposure approach enabling nanometre-resolved analysis of individual extended dislocations in molecular crystals. We demonstrate the approach for a range of crystal types to reveal dislocation character and operative slip systems unambiguously.

Abstract: Obtaining in-depth understanding of the relationships between the additive manufacturing (AM) process, microstructure and mechanical properties is crucial to overcome barriers in AM. In this study, database of metal AM was created thanks to many literature studies. Subsequently meta-analyses on the data was undertaken to provide insights into whether such relationships are well reflected in the literature data. The analyses help reveal the bias and what the data tells us, and to what extent machine learning (ML) can learn from the data. The first major bias is associated with common practices in identifying the process based on optimizing the consolidation. Most reports were for consolidation while data on microstructure and mechanical properties was significantly less. In addition, only high consolidation values was provided, so ML was not able to learn the full spectrum of the process - consolidation relationship. The common identification of process maps based on only consolidation also poses another bias as mechanical properties that ultimately govern the quality of an AM build are controlled not only by the consolidation, but also microstructure. Meta-analysis of the literature data also shows weak correlation between process with consolidation and mechanical properties. This weak correlation is attributed to the stated biases and the non-monotonic and non-linear relationships between the process and quality variables. Fortunately, trained ML models capture well the influence and interactions between process parameters and quality variables, and predicts accurately the yield stress, suggesting that the correlation between process, microstructure and yield strength is well reflected in the data. Lastly, due to the current limitation in the process map identification, we propose to identify the process map based on not only the consolidation, but also mechanical properties.

Abstract: To reach a long term viable green hydrogen economy, rational design of active oxygen evolution reaction (OER) catalysts is critical. An important hurdle in this reaction originates from the fact that the reactants are singlet molecules, whereas the oxygen molecule has a triplet ground state with parallel spin alignment, implying that magnetic order in the catalyst is essential. Accordingly, multiple experimentalists reported a positive effect of external magnetic fields on OER activity of ferromagnetic catalysts. However, it remains a challenge to investigate the influence of the intrinsic magnetic order on catalytic activity. Here, we tuned the intrinsic magnetic order of epitaxial La$_{0.67}$Sr$_{0.33}$MnO$_{3}$ thin film model catalysts from ferro- to paramagnetic by changing the temperature in-situ during water electrolysis. Using this strategy, we show that ferromagnetic ordering below the Curie temperature enhances OER activity. Moreover, we show a slight current density enhancement upon application of an external magnetic field and find that the dependence of magnetic field direction correlates with the magnetic anisotropy in the catalyst film. Our work thus suggests that both the intrinsic magnetic order in La$_{0.67}$Sr$_{0.33}$MnO$_{3}$ films and magnetic domain alignment increase their catalytic activity. We observe no long-range magnetic order at the catalytic surface, implying that the OER enhancement is connected to the magnetic order of the bulk catalyst. Combining the effects found with existing literature, we propose a unifying picture for the spin-polarized enhancement in magnetic oxide catalysts.

Abstract: Altermagnets are compensated magnets with unconvetional $d$, $g$ and $i$-wave spin-channel order in reciprocal space. So far the search for new altermagnetic candidates has been focused on materials in which the magnetic unit cell is identical to the non-magnetic one, i.e. magnetic structures with zero propagation vector. Here, we substantially broaden the family of altermagnetic candidates by predicting supercell altermagnets. Their magnetic unit cell is constructed by enlarging the paramagnetic primitive unit cell, resulting in a non-zero propagation vector for the magnetic structure. This connection of the magnetic configuration to the ordering of sublattices gives an extra degree of freedom to supercell altermagnets, which can allow for the control over the order parameter spatial orientation. We identify realistic candidates MnSe$_2$ with a $d$-wave order, and RbCoBr$_3$, CsCoCr$_3$, and BaMnO$_3$ with $g$-wave order. We demonstrate the reorientation of the order parameter in MnSe$_2$, which has two different magnetic configurations, whose energy difference is only 5 meV, opening the possibility of controlling the orientation of the altermagnetic order parameter by external perturbations.

Abstract: Organic/inorganic interfaces formed by monolayer substrates and conjugated molecular adsorbates are attractive material platforms leveraging the modularity of organic compounds together with the long-range phenomena typical of condensed matter. New quantum states are known to be generated by electronic interactions in these systems as well as by their coupling with light. However, little is still known about hybrid vibrational modes. In this work, we discover from first principles the existence of an infrared-active chiral phonon mode in a pyrene-decorated MoSe$_{2}$ monolayer given by the combination of a frustrated rotation of the molecule around its central axis and an optical mode in the substrate. Our results suggest the possibility to enable phonon chirality in molecular superlattices.

Abstract: By expanding the gauge $\lambda_n(k)$ for magnon band $n$ in harmonics of momentum ${\bf k} =(k,\phi )$, we demonstrate that the only observable component of the magnon orbital angular momentum $O_n({\bf k})$ is its angular average over all angles $\phi$, denoted by $F_n(k)$. For both the FM honeycomb and zig-zag lattices, we show that $F_n(k)$ is nonzero in the presence of a Dzyalloshinzkii-Moriya (DM) interaction. The FM zig-zag lattice model with exchange interactions $0<J_1< J_2$ provides a new system where the effects of orbital angular momentum are observable. For the zig-zag model with equal exchange interactions $J_{1x}$ and $J_{1y}$ along the $x$ and $y$ axis, the magnon bands are degenerate along the boundaries of the Brillouin zone with $k_x-k_y =\pm \pi/a$ and the Chern numbers $C_n$ are not well defined. However, a revised model with $J_{1y}\ne J_{1x}$ lifts those degeneracy and produces well-defined Chern numbers of $C_n=\pm 1$ for the two magnon bands. When $J_{1y}=J_{1x}$, the thermal conductivity $\kappa^{xy}(T)$ of the FM zig-zag lattice is largest for $J_2/J_1>6$ but is still about four times smaller than that of the FM honeycomb lattice at high temperatures. Due to the removal of band degeneracies, $\kappa^{xy}(T)$ is slightly enhanced when $J_{1y}\ne J_{1x}$.

Abstract: While colossal magnetoresistance (CMR) in Eu-based compounds is often associated with strong spin-carrier interactions, the underlying reconstruction of the electronic bands is much less understood from spectroscopic experiments. Here using angle-resolved photoemission, we directly observe an electronic band reconstruction across the insulator-metal (and magnetic) transition in the recently discovered CMR compound EuCd2P2. This transition is manifested by a large magnetic band splitting associated with the magnetic order, as well as unusual energy shifts of the valence bands: both the large ordered moment of Eu and carrier localization in the paramagnetic phase are crucial. Our results provide spectroscopic evidence for an electronic structure reconstruction underlying the enormous CMR observed in EuCd2P2, which could be important for understanding Eu-based CMR materials, as well as designing CMR materials based on large-moment rare-earth magnets.

Abstract: The structure of amorphous silicon is widely thought of as a fourfold-connected random network, and yet it is defective atoms, with fewer or more than four bonds, that make it particularly interesting. Despite many attempts to explain such "dangling-bond" and "floating-bond" defects, respectively, a unified understanding is still missing. Here, we show that atomistic machine-learning methods can reveal the complex structural and energetic landscape of defects in amorphous silicon. We study an ultra-large-scale, quantum-accurate structural model containing a million atoms, and more than ten thousand defects, allowing reliable defect-related statistics to be obtained. We combine structural descriptors and machine-learned local atomic energies to develop a universal classification of the different types of defects in amorphous silicon. The results suggest a revision of the established floating-bond model by showing that fivefold-coordinated atoms in amorphous silicon exhibit a wide range of local environments, and it is shown that fivefold (but not threefold) coordination defects tend to cluster together. Our study provides new insights into one of the most widely studied amorphous solids, and has general implications for modelling and understanding defects in disordered materials beyond silicon alone.