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We present an ab initio molecular dynamics simulation of the aqueous liquid-vapor interface. Having successfully stabilized a region of bulk water in the center of a water slab, we were able to reproduce and further quantify the experimentally observed abundance of surface \"acceptor-only\" (19%) and \"single-donor\" (66%) moieties as well as substantial surface relaxation approaching the liquid-vapor interface. Examination of the orientational dynamics points to a faster relaxation in the interfacial region. Furthermore, the average value of the dipole decreases and the average value of the highest occupied molecular orbital for each water molecule increases approaching the liquid-vapor interface. Our results support the idea that the surface contains, on average, far more reactive states than the bulk.

Gas-phase synthesis characterizes a class of bottom-up methods for producing multifunctional nanoparticles (NPs) from individual atoms or molecules. This review aims to summarize recent achievements using this approach, and compare its potential to other physical or chemical NP fabrication techniques. More specifically, emphasis is given to magnetron-sputter gas-phase condensation, since it allows for flexible growth of complex, sophisticated NPs, owing to the fast kinetics and non-equilibrium processes it entails. Nanoparticle synthesis is decomposed into four stages, i.e. aggregation, shell-coating, mass-filtration, and deposition. We present the formation of NPs of various functionalities for different applications, such as magnetic, plasmonic, catalytic and, gas-sensing, emphasizing on the primary dependence of each type on a different stage of the fabrication process, and their resultant physical and chemical properties.

Ultrathin ferroelectric materials could potentially enable low-power logic and nonvolatile memories 1 , 2 . As ferroelectric materials are made thinner, however, the ferroelectricity is usually suppressed. Size effects in ferroelectrics have been thoroughly investigated in perovskite oxides—the archetypal ferroelectric system 3 . Perovskites, however, have so far proved unsuitable for thickness scaling and integration with modern semiconductor processes 4 . Here we report ferroelectricity in ultrathin doped hafnium oxide (HfO 2 ), a fluorite-structure oxide grown by atomic layer deposition on silicon. We demonstrate the persistence of inversion symmetry breaking and spontaneous, switchable polarization down to a thickness of one nanometre. Our results indicate not only the absence of a ferroelectric critical thickness but also enhanced polar distortions as film thickness is reduced, unlike in perovskite ferroelectrics. This approach to enhancing ferroelectricity in ultrathin layers could provide a route towards polarization-driven memories and ferroelectric-based advanced transistors. This work shifts the search for the fundamental limits of ferroelectricity to simpler transition-metal oxide systems—that is, from perovskite-derived complex oxides to fluorite-structure binary oxides—in which ‘reverse’ size effects counterintuitively stabilize polar symmetry in the ultrathin regime. Enhanced switchable ferroelectric polarization is achieved in doped hafnium oxide films grown directly onto silicon using low-temperature atomic layer deposition, even at thicknesses of just one nanometre.

The Jahn–Teller effect, in which electronic configurations with energetically degenerate orbitals induce lattice distortions to lift this degeneracy, has a key role in many symmetry-lowering crystal deformations 1 . Lattices of Jahn–Teller ions can induce a cooperative distortion, as exemplified by LaMnO 3 (refs. 2 , 3 ). Although many examples occur in octahedrally 4 or tetrahedrally 5 coordinated transition metal oxides due to their high orbital degeneracy, this effect has yet to be manifested for square-planar anion coordination, as found in infinite-layer copper 6 , 7 , nickel 8 , 9 , iron 10 , 11 and manganese oxides 12 . Here we synthesize single-crystal CaCoO 2 thin films by topotactic reduction of the brownmillerite CaCoO 2.5 phase. We observe a markedly distorted infinite-layer structure, with ångström-scale displacements of the cations from their high-symmetry positions. This can be understood to originate from the Jahn–Teller degeneracy of the d xz and d yz orbitals in the d 7 electronic configuration along with substantial ligand–transition metal mixing. A complex pattern of distortions arises in a 2 2 × 2 2 × 1 tetragonal supercell, reflecting the competition between an ordered Jahn–Teller effect on the CoO 2 sublattice and the geometric frustration of the associated displacements of the Ca sublattice, which are strongly coupled in the absence of apical oxygen. As a result of this competition, the CaCoO 2 structure forms an extended two-in–two-out type of Co distortion following ‘ice rules’ 13 . A distorted infinite-layer lattice of single-crystal CaCoO 2 originates from competition between an ordered Jahn–Teller effect and geometric frustration.

The electrochemical double layer plays a critical role in electrochemical processes. Whilst there have been many theoretical models predicting structural and electrical organization of the electrochemical double layer, the experimental verification of these models has been challenging due to the limitations of available experimental techniques. The induced potential drop in the electrolyte has never been directly observed and verified experimentally, to the best of our knowledge. In this study, we report the direct probing of the potential drop as well as the potential of zero charge by means of ambient pressure X-ray photoelectron spectroscopy performed under polarization conditions. By analyzing the spectra of the solvent (water) and a spectator neutral molecule with numerical simulations of the electric field, we discern the shape of the electrochemical double layer profile. In addition, we determine how the electrochemical double layer changes as a function of both the electrolyte concentration and applied potential. The electrochemical double layer is a key concept in chemistry, but its properties are hard to probe experimentally. Here, the authors use ambient pressure X-ray photoelectron spectroscopy to probe the electrochemical double layer potential profile at the solid/liquid interface, under polarization conditions.

Charge carrier diffusion coefficient and length are important physical parameters for semiconducting materials. Long-range carrier diffusion in perovskite thin films has led to remarkable solar cell efficiencies; however, spatial and temporal mechanisms of charge transport remain unclear. Here we present a direct measurement of carrier transport in space and in time by mapping carrier density with simultaneous ultrafast time resolution and ∼50-nm spatial precision in perovskite thin films using transient absorption microscopy. These results directly visualize long-range carrier transport of ∼220 nm in 2 ns for solution-processed polycrystalline CH 3 NH 3 PbI 3 thin films. Variations of the carrier diffusion coefficient at the μm length scale have been observed with values ranging between 0.05 and 0.08 cm 2  s −1 . The spatially and temporally resolved measurements reported here underscore the importance of the local morphology and establish an important first step towards discerning the underlying transport properties of perovskite materials. Determining the mechanism of charge carrier transport in solar cells is important for their development towards higher efficiencies. Here, the authors elucidate the spatial and temporal diffusion of charge carriers in hybrid perovskite thin films through ultrafast transient absorption microscopy.

Ferroelectricity in binary oxides including hafnia and zirconia has riveted the attention of the scientific community due to the highly unconventional physical mechanisms and the potential for the integration of these materials into semiconductor workflows. Over the last decade, it has been argued that behaviours such as wake-up phenomena and an extreme sensitivity to electrode and processing conditions suggest that ferroelectricity in these materials is strongly influenced by other factors, including electrochemical boundary conditions and strain. Here we argue that the properties of these materials emerge due to the interplay between the bulk competition between ferroelectric and structural instabilities, similar to that in classical antiferroelectrics, coupled with non-local screening mediated by the finite density of states at surfaces and internal interfaces. Via the decoupling of electrochemical and electrostatic controls, realized via environmental and ultra-high vacuum piezoresponse force microscopy, we show that these materials demonstrate a rich spectrum of ferroic behaviours including partial-pressure-induced and temperature-induced transitions between ferroelectric and antiferroelectric behaviours. These behaviours are consistent with an antiferroionic model and suggest strategies for hafnia-based device optimization.Ferroelectricity in hafnia-based systems seems to be correlated with oxygen vacancy dynamics, but the coupling of this and ferroelectric response is rarely studied. Here it is shown that Hf0.5Zr0.5O2 can be antiferroionic, with antiferroelectric behaviour coupled to surface electrochemistry.

The segregation of solute atoms at grain boundaries (GBs) can profoundly impact the structural properties of metallic alloys, and induce effects that range from strengthening to embrittlement. And, though known to be anisotropic, there is a limited understanding of the variation of solute segregation tendencies across the full, multidimensional GB space, which is critically important in polycrystals where much of that space is represented. Here we develop a machine learning framework that can accurately predict the segregation tendency—quantified by the segregation enthalpy spectrum—of solute atoms at GB sites in polycrystals, based solely on the undecorated (pre-segregation) local atomic environment of such sites. We proceed to use the learning framework to scan across the alloy space, and build an extensive database of segregation energy spectra for more than 250 metal-based binary alloys. The resulting machine learning models and segregation database are key to unlocking the full potential of GB segregation as an alloy design tool, and enable the design of microstructures that maximize the useful impacts of segregation. Predicting segregation energies of alloy systems can be challenging even for a single grain boundary. Here the authors propose a machine-learning framework, which maps the local environments on a distribution of segregation energies, to predict segregation energies of alloy elements in polycrystalline materials.

Superconductivity is among the most fascinating and well-studied quantum states of matter. Despite over 100 years of research, a detailed understanding of how features of the normal-state electronic structure determine superconducting properties has remained elusive. For instance, the ability to deterministically enhance the superconducting transition temperature by design, rather than by serendipity, has been a long sought-after goal in condensed matter physics and materials science, but achieving this objective may require new tools, techniques and approaches. Here, we report the transmutation of a normal metal into a superconductor through the application of epitaxial strain. We demonstrate that synthesizing RuO 2 thin films on (110)-oriented TiO 2 substrates enhances the density of states near the Fermi level, which stabilizes superconductivity under strain, and suggests that a promising strategy to create new transition-metal superconductors is to apply judiciously chosen anisotropic strains that redistribute carriers within the low-energy manifold of d orbitals. Epitaxial strain is a promising control knob to modulate Tc to enhance superconductivity. Here, the authors show that a metallic oxide RuO 2 can be turned superconducting through application of epitaxial strain in thin films grown on a (110)-oriented TiO 2 substrate.

A quantum anomalous Hall (QAH) state is a two-dimensional topological insulating state that has a quantized Hall resistance of h /( Ce 2 ) and vanishing longitudinal resistance under zero magnetic field (where h is the Planck constant, e is the elementary charge, and the Chern number C is an integer) 1 , 2 . The QAH effect has been realized in magnetic topological insulators 3 – 9 and magic-angle twisted bilayer graphene 10 , 11 . However, the QAH effect at zero magnetic field has so far been realized only for C  = 1. Here we realize a well quantized QAH effect with tunable Chern number (up to C  = 5) in multilayer structures consisting of alternating magnetic and undoped topological insulator layers, fabricated using molecular beam epitaxy. The Chern number of these QAH insulators is determined by the number of undoped topological insulator layers in the multilayer structure. Moreover, we demonstrate that the Chern number of a given multilayer structure can be tuned by varying either the magnetic doping concentration in the magnetic topological insulator layers or the thickness of the interior magnetic topological insulator layer. We develop a theoretical model to explain our experimental observations and establish phase diagrams for QAH insulators with high, tunable Chern number. The realization of such insulators facilitates the application of dissipationless chiral edge currents in energy-efficient electronic devices, and opens up opportunities for developing multi-channel quantum computing and higher-capacity chiral circuit interconnects. The number of edge channels in quantum anomalous Hall insulators is controlled by varying either the magnetic dopant concentration or the interior spacer layer thickness, yielding Chern numbers up to 5.