Emerging Leaders 2021

We investigate the spin-nonconserving relaxation channel of excitons by their couplings with phonons in two-dimensional transition metal dichalcogenides using ab initio approaches. Combining GW-Bethe–Salpeter equation method and density functional perturbation theory, we calculate the electron–phonon and exciton–phonon coupling matrix elements for the spin-flip scattering in monolayer WSe₂, and further analyze the microscopic mechanisms influencing these scattering strengths. We find that phonons could produce effective in-plane magnetic fields which flip spin of excitons, giving rise to relaxation channels complimentary to the spin-conserving relaxation. Finally, we calculate temperature-dependent spin-flip exciton–phonon relaxation times. Our method and analysis can be generalized to study other two-dimensional materials and would stimulate experimental measurements of spin-flip exciton relaxation dynamics.

The structure of the electrical double layer (EDL) formed near graphene in aqueous environments strongly impacts its performance for a plethora of applications, including capacitive deionization. In particular, adsorption and organization of multivalent counterions near the graphene interface can promote nonclassical behaviors of EDL including overcharging followed by co-ion adsorption. In this paper, we characterize the EDL formed near an electrified graphene interface in dilute aqueous YCl₃ solution using in situ high resolution x-ray reflectivity (also known as crystal truncation rod) and resonant anomalous x-ray reflectivity (RAXR). These interface-specific techniques reveal the electron density profiles with molecular-scale resolution. We find that yttrium ions (Y³⁺) readily adsorb to the negatively charged graphene surface to form an extended ion profile. This ion distribution resembles a classical diffuse layer but with a significantly high ion coverage, i.e., 1 Y³⁺ per 11.4 ± 1.6 Ų, compared to the value calculated from the capacitance measured by cyclic voltammetry (1 Y³⁺ per ∼240 Ų). Such overcharging can be explained by co-adsorption of chloride that effectively screens the excess positive charge. The adsorbed Y³⁺ profile also shows a molecular-scale gap (⩾5 Å) from the top graphene surfaces, which is attributed to the presence of intervening water molecules between the adsorbents and adsorbates as well as the lack of inner-sphere surface complexation on chemically inert graphene. We also demonstrate controlled adsorption by varying the applied potential and reveal consistent Y³⁺ ion position with respect to the surface and increasing cation coverage with increasing the magnitude of the negative potential. This is the first experimental description of a model graphene-aqueous system with controlled potential and provides important insights into the application of graphene-based systems for enhanced and selective ion separations.

We combine density functional theory simulations and active learning (AL) of element-embedding neural networks (NNs) to explore the sample efficiency for the prediction of vacancy layer formation energies and lattice parameters in ABX_n infinite-layer (n = 2) versus perovskite (n = 3) nitrides, oxides, and fluorides in the spirit of transfer learning. Following a comprehensive data analysis from different thermodynamic, structural, and statistical perspectives, we show that NNs model these observables with high precision, using merely $\sim 30\%$ of the data for training and exclusively the A-, B-, and X-site element names as minimal input devoid of any physical a priori information. Element embedding autonomously arranges the chemical elements with a characteristic recurrent topology, such that their relations are consistent with human knowledge. We compare two different embedding strategies and show that these techniques render additional input such as atomic properties negligible. Simultaneously, we demonstrate that AL is largely independent of the initial training set, and exemplify its superiority over randomly composed training sets. Despite their highly distinct chemistry, the present approach successfully identifies fundamental quantum-mechanical universalities between nitrides, oxides, and fluorides that enhance the combined prediction accuracy by up to 16% with respect to three specialized NNs at equivalent numerical effort. This quantification of synergistic effects provides an impression of the transfer learning improvements one may expect for similarly complex materials. Finally, by embedding the tensor product of the B and X sites and subsequent quantitative cluster analysis, we establish from an unbiased artificial-intelligence perspective that oxides and nitrides exhibit significant parallels, whereas fluorides constitute a rather distinct materials class.

The square-root descendants of higher-order topological insulators were proposed recently, whose topological property is inherited from the squared Hamiltonian. Here we present a three-dimensional (3D) square-root-like sonic crystal by stacking the 2D square-root lattice in the normal (z) direction. With the nontrivial intralayer couplings, the opened degeneracy at the K–H direction induces the emergence of multiple acoustic localized modes, i.e., the extended 2D surface states and 1D hinge states, which originate from the square-root nature of the system. The square-root-like higher order topological states can be tunable and designed by optionally removing the cavities at the boundaries. We further propose a third-order topological corner state in the 3D sonic crystal by introducing the staggered interlayer couplings on each square-root layer, which leads to a nontrivial bulk polarization in the z direction. Our work sheds light on the high-dimensional square-root topological materials, and have the potentials in designing advanced functional devices with sound trapping and acoustic sensing.

We present an in-depth study of metal–insulator interfaces within granular metal (GM) films and correlate their interfacial interactions with structural and electrical transport properties. Nominally 100 nm thick GM films of Co and Mo dispersed within yttria-stabilized zirconia (YSZ), with volumetric metal fractions (φ) from 0.2–0.8, were grown by radio frequency co-sputtering from individual metal and YSZ targets. Scanning transmission electron microscopy and DC transport measurements find that the resulting metal islands are well-defined with 1.7–2.6 nm average diameters and percolation thresholds between φ = 0.4–0.5. The room temperature conductivities for the φ = 0.2 samples are several orders of magnitude larger than previously-reported for GMs. X-ray photoemission spectroscopy indicates both oxygen vacancy formation within the YSZ and band-bending at metal–insulator interfaces. The higher-than-predicted conductivity is largely attributed to these interface interactions. In agreement with recent theory, interactions that reduce the change in conductivity across the metal–insulator interface are seen to prevent sharp conductivity drops when the metal concentration decreases below the percolation threshold. These interface interactions help interpret the broad range of conductivities reported throughout the literature and can be used to tune the conductivities of future GMs.

The magnetic ground states of R₂Ru₂O₇ and A₂Ru₂O₇ with R = Pr, Gd, Ho, and Er, as well as A = Ca, Cd are predicted devising a combination of the cluster-multipole (CMP) theory and spin-density-functional theory (SDFT). The strong electronic correlation effects are estimated by the constrained-random-phase approximation (cRPA) and taken into account within the dynamical-mean-field theory (DMFT). The target compounds feature d-orbital magnetism on Ru⁴⁺ and Ru⁵⁺ ions for R and A, respectively, as well as f-orbital magnetism on the R site, which leads to an intriguing interplay of magnetic interactions in a strongly correlated system. We find CMP + SDFT is capable of describing the magnetic ground states in these compounds. The cRPA captures a difference in the screening strength between R₂Ru₂O₇ and A₂Ru₂O₇ compounds, which leads to a qualitative and quantitative understanding of the electronic properties within DMFT.

Generalized Langevin equations (GLEs) can be systematically derived via dimensional reduction from high-dimensional microscopic systems. For linear models the derivation can either be based on projection operator techniques such as the Mori–Zwanzig (MZ) formalism or by 'integrating out' the bath degrees of freedom. Based on exact analytical results we show that both routes can lead to fundamentally different GLEs and that the origin of these differences is based inherently on the non-equilibrium nature of the microscopic stochastic model. The most important conceptional difference between the two routes is that the MZ result intrinsically fulfills the generalized second fluctuation–dissipation theorem while the integration result can lead to its violation. We supplement our theoretical findings with numerical and simulation results for two popular non-equilibrium systems: time-delayed feedback control and the active Ornstein–Uhlenbeck process.

Most transition-metal trihalides are dimorphic. The representative chromium-based triad, CrCl₃, CrBr₃, CrI₃, is characterized by the low-temperature (LT) phase adopting the trigonal BiI₃-type while the structure of the high-temperature (HT) phase is monoclinic of AlCl₃ type (C2/m). The structural transition between the two crystallographic phases is of the first-order type with large thermal hysteresis in CrCl₃ and CrI₃. We studied crystal structures and structural phase transitions of vanadium-based counterparts VCl₃, VBr₃, and VI₃ by measuring specific heat, magnetization, and x-ray diffraction as functions of temperature and observed an inverse situation. In these cases, the HT phase has a higher symmetry while the LT structure reveals a lower symmetry. The structural phase transition between them shows no measurable hysteresis in contrast to CrX₃. Possible relations of the evolution of the ratio c/a of the unit cell parameters, types of crystal structures, and nature of the structural transitions in V and Cr trihalides are discussed.

We revisit the concept of nonunitary superconductivity and generalize it to address complex quantum materials. Starting with a brief review of the notion of nonunitary superconductivity, we discuss its spectral signatures in simple models with only the spin as an internal degree of freedom. In complex materials with multiple internal degrees of freedom, there are many more possibilities for the development of nonunitary order parameters. We provide examples focusing on d-electron systems with two orbitals, applicable to a variety of materials. We discuss the consequences for the superconducting spectra, highlighting that gap openings of band crossings at finite energies can be attributed to a nonunitary order parameter if this is associated with a finite superconducting fitness matrix. We speculate that nonunitary superconductivity in complex quantum materials is in fact very common and can be associated with multiple cases of recently reported time-reversal symmetry breaking superconductors.

Surface-bound reactions have become a viable method to develop nanoarchitectures through bottom-up assembly with near atomic precision. However, the bottom-up fabrication of nanostructures on surfaces requires careful consideration of the intrinsic properties of the precursors and substrate as well as the complex interplay of any interactions that arise in the heterogeneous two-dimensional (2D) system. Therefore, it becomes necessary to consider these systems with characterization methods sensitive to such properties with suitable spatial resolution. Here, low temperature ultrahigh vacuum scanning tunneling microscopy (STM) and tip-enhanced Raman spectroscopy (TERS) were used to investigate the formation of 2D covalent networks via coupling reactions of tetra(4-bromophenyl)porphyrin (Br₄TPP) molecules on a Ag(100) substrate. Through the combination of STM topographic imaging and TERS vibrational fingerprints, the conformation of molecular precursors on the substrate was understood. Following the thermally activated coupling reaction, STM and TERS imaging confirm the covalent nature of the 2D networks and suggest that the apparent disorder arises from molecular flexibility.

Warm dense matter (WDM) describes an intermediate phase, between condensed matter and classical plasmas, found in natural and man-made systems. In a laboratory setting, WDM is often created dynamically. It is typically laser or pulse-power generated and can be difficult to characterize experimentally. Measuring the energy loss of high energy ions, caused by a WDM target, is both a promising diagnostic and of fundamental importance to inertial confinement fusion research. However, electron coupling, degeneracy, and quantum effects limit the accuracy of easily calculable kinetic models for stopping power, while high temperatures make the traditional tools of condensed matter, e.g. time-dependent density functional theory (TD-DFT), often intractable. We have developed a mixed stochastic-deterministic approach to TD-DFT which provides more efficient computation while maintaining the required precision for model discrimination. Recently, this approach showed significant improvement compared to models when compared to experimental energy loss measurements in WDM carbon. Here, we describe this approach and demonstrate its application to warm dense carbon stopping across a range of projectile velocities. We compare direct stopping-power calculation to approaches based on combining homogeneous electron gas response with bound electrons, with parameters extracted from our TD-DFT calculations.

The interfacial perpendicular magnetic anisotropy (PMA) plays a key role in spintronic applications such as memory recording and computational devices. Despite robust PMA being reported at the Fe/MgO interface, there are still inconsistencies in the disorder effects on the interfacial magnetic anisotropy. Here we reported a comprehensive study of the influence of the interfacial disorder, including the underoxidization, overoxidization, and oxygen migration, on the PMA of the Fe/MgO interface using first-principles calculations. Compared to the pristine Fe/MgO interface, the underoxidation at the Fe/MgO interface keeps the interfacial PMA but reduces the interfacial anisotropy constant (K_i). The overoxidization and oxygen migration at the interface both reduce the K_i and even switch the easy magnetization axis from the out-of-plane to in-plane direction at high oxygen percentage. In all the cases, the K_i was found strongly correlated to the difference of the orbital magnetic moment along the in-plane and out-of-plane direction. Calculated layer-resolved and orbital-resolved K_i revealed that the orbital coupling between the d_xy and ${d}_{{x}^{2}-{y}^{2}}$ states of the interfacial Fe layer plays a key role in determining the interfacial magnetic anisotropy. This work provides deep insights into the oxidation effects on the interfacial magnetic anisotropy of Fe/MgO system and a possible avenue to tune the K_i via interfacial engineering.

Using swarm-intelligence-based structure prediction methods, we predict a novel direct bandgap silicon allotrope with open channels at ambient conditions. This silicon phase, termed Si₃₂, can be produced by removing Sr atoms from a new Cmcm-SrSi₈ clathrate-like compound, which is calculated to be thermodynamically stable under epitaxial strain at high pressures. Si₃₂ is predicted to have a direct bandgap of ∼1.15 eV and exceptional optical properties. The prediction of novel silicon clathrate-like structure paves the way for the exploration of novel silicon phases with extensive application possibilities.

Chalcogen vacancies in transition metal dichalcogenides are widely acknowledged as both donor dopants and as a source of disorder. The electronic structure of sulphur vacancies in MoS₂ however is still controversial, with discrepancies in the literature pertaining to the origin of the in-gap features observed via scanning tunneling spectroscopy (STS) on single sulphur vacancies. Here we use a combination of scanning tunnelling microscopy and STS to study embedded sulphur vacancies in bulk MoS₂ crystals. We observe spectroscopic features dispersing in real space and in energy, which we interpret as tip position- and bias-dependent ionization of the sulphur vacancy donor due to tip induced band bending. The observations indicate that care must be taken in interpreting defect spectra as reflecting in-gap density of states, and may explain discrepancies in the literature.

We use video microscopy to study the full capture process for colloidal particles transported through microfluidic channels by a pressure-driven flow. In particular, we obtain trajectories for particles as they move from the bulk into confinement, using these to map in detail the spatial velocity and concentration fields for a range of different flow velocities. Importantly, by changing the height profiles of our microfluidic devices, we consider systems for which flow profiles in the channel are the same, but flow fields in the reservoir differ with respect to the quasi-2D monolayer of particles. We find that velocity fields and profiles show qualitative agreement with numerical computations of pressure-driven fluid flow through the systems in the absence of particles, implying that in the regimes studied here particle-particle interactions do not strongly perturb the flow. Analysis of the particle flux through the channel indicates that changing the reservoir geometry leads to a change between long-range attraction of the particles to the pore and diffusion-to-capture-like behaviour, with concentration fields that show qualitative changes based on device geometry. Our results not only provide insight into design considerations for microfluidic devices, but also a foundation for experimental elucidation of the concept of a capture radius. This long standing problem plays a key role in transport models for biological channels and nanopore sensors.

We investigate the spin-nonconserving relaxation channel of excitons by their couplings with phonons in two-dimensional transition metal dichalcogenides using ab initio approaches. Combining GW-Bethe–Salpeter equation method and density functional perturbation theory, we calculate the electron–phonon and exciton–phonon coupling matrix elements for the spin-flip scattering in monolayer WSe₂, and further analyze the microscopic mechanisms influencing these scattering strengths. We find that phonons could produce effective in-plane magnetic fields which flip spin of excitons, giving rise to relaxation channels complimentary to the spin-conserving relaxation. Finally, we calculate temperature-dependent spin-flip exciton–phonon relaxation times. Our method and analysis can be generalized to study other two-dimensional materials and would stimulate experimental measurements of spin-flip exciton relaxation dynamics.

Spatial models where growth is limited to the population edge have been instrumental to understanding the population dynamics and the clone size distribution in growing cellular populations, such as microbial colonies and avascular tumours. A complete characterization of the coalescence process generated by spatial growth is still lacking, limiting our ability to apply classic population genetics inference to spatially growing populations. Here, we start filling this gap by investigating the statistical properties of the cell lineages generated by the two dimensional Eden model, leveraging their physical analogy with directed polymers. Our analysis provides quantitative estimates for population measurements that can easily be assessed via sequencing, such as the average number of segregating sites and the clone size distribution of a subsample of the population. Our results not only reveal remarkable features of the genealogies generated during growth, but also highlight new properties that can be misinterpreted as signs of selection if non-spatial models are inappropriately applied.

We revisit the concept of nonunitary superconductivity and generalize it to address complex quantum materials. Starting with a brief review of the notion of nonunitary superconductivity, we discuss its spectral signatures in simple models with only the spin as an internal degree of freedom. In complex materials with multiple internal degrees of freedom, there are many more possibilities for the development of nonunitary order parameters. We provide examples focusing on d-electron systems with two orbitals, applicable to a variety of materials. We discuss the consequences for the superconducting spectra, highlighting that gap openings of band crossings at finite energies can be attributed to a nonunitary order parameter if this is associated with a finite superconducting fitness matrix. We speculate that nonunitary superconductivity in complex quantum materials is in fact very common and can be associated with multiple cases of recently reported time-reversal symmetry breaking superconductors.