Direct Electroplating Ruthenium Precursor on the Surface Oxidized Nickel Foam for Efficient and Stable Bifunctional Alkaline Water Electrolysis.

Water electrolysis to produce hydrogen (H2) using renewable energy is one of the most promising candidates for realizing carbon neutrality, but its reaction kinetics is hindered by sluggish anodic oxygen evolution reaction (OER). Ruthenium (Ru) in its high-valence state (oxide) provides one of the most active OER sites and is less costly, but thermodynamically unstable. The strong interaction between Ru nanoparticles (NPs) and nickel hydroxide (Ni(OH)2) is leveraged to directly form Ru-Ni(OH)2 on the surface of a porous nickel foam (NF) electrode via spontaneous galvanic replacement reaction. The formation of Ru─O─Ni bonds at the interface of the Ru NPs and Ni(OH)2 (Ru-Ni(OH)2) on the surface oxidized NF significantly enhance stability of the Ru-Ni(OH)2/NF electrode. In addition to OER, the catalyst is active enough for the hydrogen evolution reaction (HER). As a result, it is able to deliver overpotentials of 228 and 15 mV to reach 10 mA cm-2 for OER and HER, respectively. An industry-scale evaluation using Ru-Ni(OH)2/NF as both OER and HER electrodes demonstrates a high current density of 1500 mA cm-2 (OER: 410 mV; HER: 240 mV), surpassing commercial RuO2 (OER: 600 mV) and Pt/C based performance (HER: 265 mV).

Suppressed terahertz dynamics of water confined in nanometer gaps.

Nanoconfined waters exhibit low static permittivity mainly due to interfacial effects that span about one nanometer. The characteristic length scale may be much longer in the terahertz (THz) regime where long-range collective dynamics occur; however, the THz dynamics have been largely unexplored because of the lack of a robust platform. Here, we use metallic loop nanogaps to sharply enhance light-matter interactions and precisely measure real and imaginary THz refractive indices of nanoconfined water at gap widths ranging from 2 to 20 nanometers, spanning mostly interfacial waters all the way to quasi-bulk waters. We find that, in addition to the well-known interfacial effect, the confinement effect also contributes substantially to the decrease in the complex refractive indices of the nanoconfined water by cutting off low-energy vibrational modes, even at gap widths as large as 10 nanometers. Our findings provide valuable insights into the collective dynamics of water molecules which is crucial to understanding water-mediated processes.

Optoelectronic Manifestation of Orbital Angular Momentum Driven by Chiral Hopping in Helical Se Chains.

Chiral materials have garnered significant attention in the field of condensed matter physics. Nevertheless, the magnetic moment induced by the chiral spatial motion of electrons in helical materials, such as elemental Te and Se, remains inadequately understood. In this work, we investigate the development of quantum angular momentum enforced by chirality by using static and time-dependent density functional theory calculations for an elemental Se chain. Our findings reveal the emergence of an unconventional orbital texture driven by the chiral geometry, giving rise to a nonvanishing current-induced orbital moment. By incorporating spin-orbit coupling, we demonstrate that current-induced spin accumulation arises in the chiral chain, which fundamentally differs from the conventional Edelstein effect. Furthermore, we demonstrate optoelectronic detection of the orbital angular momentum in the chiral Se chain, providing an alternative to the interband Berry curvature, which is ill-defined in low dimensions.

Unusual Spin Polarization in the Chirality-Induced Spin Selectivity.

Chirality-induced spin selectivity (CISS) refers to the fact that electrons get spin polarized after passing through chiral molecules in a nanoscale transport device or in photoemission experiments. In CISS, chiral molecules are commonly believed to be a spin filter through which one favored spin transmits and the opposite spin gets reflected; that is, transmitted and reflected electrons exhibit opposite spin polarization. In this work, we point out that such a spin filter scenario contradicts the principle that equilibrium spin current must vanish. Instead, we find that both transmitted and reflected electrons present the same type of spin polarization, which is actually ubiquitous for a two-terminal device. More accurately, chiral molecules play the role of a spin polarizer rather than a spin filter. The direction of spin polarization is determined by the molecule chirality and the electron incident direction. And the magnitude of spin polarization relies on local spin-orbit coupling in the device. Our work brings a deeper understanding on CISS and interprets recent experiments, for example, the CISS-driven anomalous Hall effect.

Giant bulk photovoltaic effect driven by the wall-to-wall charge shift in WS2 nanotubes.

The intrinsic light-matter characteristics of transition-metal dichalcogenides have not only been of great scientific interest but have also provided novel opportunities for the development of advanced optoelectronic devices. Among the family of transition-metal dichalcogenide structures, the one-dimensional nanotube is particularly attractive because it produces a spontaneous photocurrent that is prohibited in its higher-dimensional counterparts. Here, we show that WS2 nanotubes exhibit a giant shift current near the infrared region, amounting to four times the previously reported values in the higher frequency range. The wall-to-wall charge shift constitutes a key advantage of the one-dimensional nanotube geometry, and we consider a Janus-type heteroatomic configuration that can maximize this interwall effect. To assess the nonlinear effect of a strong field and the nonadiabatic effect of atomic motion, we carried out direct real-time integration of the photoinduced current using time-dependent density functional theory. Our findings provide a solid basis for a complete quantum mechanical understanding of the unique light-matter interaction hidden in the geometric characteristics of the reduced dimension.

Erratum: Identification of the Mott Insulating Charge Density Wave State in 1T-TaS_{2} [Phys. Rev. Lett. 126, 196406 (2021)].

This corrects the article DOI: 10.1103/PhysRevLett.126.196406.

Identification of the Mott Insulating Charge Density Wave State in 1T-TaS_{2}.

We investigate the low-temperature charge density wave (CDW) state of bulk TaS_{2} with a fully self-consistent density-functional theory with the Hubbard U potential, over which the controversy has remained unresolved regarding the out-of-plane metallic band. By examining the innate structure of the Hubbard U potential, we reveal that the conventional use of atomic-orbital basis could seriously misevaluate the electron correlation in the CDW state. By adopting a generalized basis, covering the whole David star, we successfully reproduce the Mott insulating nature with the layer-by-layer antiferromagnetic order. Similar consideration should be applied for description of the electron correlation in molecular solid.

First-principles identification of the charge-shifting mechanism and ferroelectricity in hybrid halide perovskites.

Hybrid halide perovskite solar cells have recently attracted substantial attention, mainly because of their high power conversion efficiency. Among diverse variants, (CH3NH3)PbI3 and HC(NH2)2PbI3 are particularly promising candidates because their bandgap well matches the energy range of visible light. Here, we demonstrate that the large nonlinear photocurrent in ß-(CH3NH3)PbI3 and α-HC(NH2)2PbI3 is mostly determined by the intrinsic electronic band properties near the Fermi level, rooted in the inorganic backbone, whereas the ferroelectric polarization of the hybrid halide perovskite is largely dominated by the ionic contribution of the molecular cation. The spatial charge shift upon excitation is attributed to the charge transfer from iodine to lead atoms in the backbone, which is independent of the presence of the cationic molecules. Our findings can serve as a guiding principle for the design of future materials for halide-perovskite solar cells with further enhanced photovoltaic performance.

Facile Ferroelectric Phase Transition Driven by Si Doping in HfO2.

The recently discovered ferroelectricity in thin-film orthorhombic HfO2, which can be directly integrated into complementary metal-oxide semiconductor technology, has become an important research target. However, the use of orthorhombic HfO2 in practical devices has been limited by undesirable mixing with the monoclinic phase, which is nonpolar and thus degrades the ferroelectric properties. Here, we demonstrate that a Si dopant significantly stabilizes the ferroelectric phase because of its unique bonding characteristics, particularly its intrinsic tendency to form strong covalent bonds with O, thereby weakening the phase boundary to stabilize the ferroelectric orthorhombic phase over the nonpolar monoclinic phase, relatively. On the basis of our theoretical predictions, we conducted transmission electron microscopy measurements and confirmed that Si substitution doping indeed induced monoclinic structural components into the orthorhombic phase, which is a strong indication of the weakened phase boundary and subsequent facilitation of the ferroelectric transition. This work thus provides an atomic-scale picture for understanding the unique role of Si in promoting the ferroelectric phase and the dopant dependence on the wake-up effect in HfO2, offering a substantial advancement toward integrating ferroelectrics into practical devices.

One-dimensional hexagonal boron nitride conducting channel.

Hexagonal boron nitride (hBN) is an insulating two-dimensional (2D) material with a large bandgap. Although known for its interfacing with other 2D materials and structural similarities to graphene, the potential use of hBN in 2D electronics is limited by its insulating nature. Here, we report atomically sharp twin boundaries at AA'/AB stacking boundaries in chemical vapor deposition-synthesized few-layer hBN. We find that the twin boundary is composed of a 6'6' configuration, showing conducting feature with a zero bandgap. Furthermore, the formation mechanism of the atomically sharp twin boundaries is suggested by an analogy with stacking combinations of AA'/AB based on the observations of extended Klein edges at the layer boundaries of AB-stacked hBN. The atomically sharp AA'/AB stacking boundary is promising as an ultimate 1D electron channel embedded in insulating pristine hBN. This study will provide insights into the fabrication of single-hBN electronic devices.

Ruthenium anchored on carbon nanotube electrocatalyst for hydrogen production with enhanced Faradaic efficiency.

Developing efficient and stable electrocatalysts is crucial for the electrochemical production of pure and clean hydrogen. For practical applications, an economical and facile method of producing catalysts for the hydrogen evolution reaction (HER) is essential. Here, we report ruthenium (Ru) nanoparticles uniformly deposited on multi-walled carbon nanotubes (MWCNTs) as an efficient HER catalyst. The catalyst exhibits the small overpotentials of 13 and 17 mV at a current density of 10 mA cm-2 in 0.5 M aq. H2SO4 and 1.0 M aq. KOH, respectively, surpassing the commercial Pt/C (16 mV and 33 mV). Moreover, the catalyst has excellent stability in both media, showing almost "zeroloss" during cycling. In a real device, the catalyst produces 15.4% more hydrogen per power consumed, and shows a higher Faradaic efficiency (92.28%) than the benchmark Pt/C (85.97%). Density functional theory calculations suggest that Ru-C bonding is the most plausible active site for the HER.

Exploitable Magnetic Anisotropy of the Two-Dimensional Magnet CrI3.

Magnetic anisotropy often plays a central role in various static and dynamic properties of magnetic materials. In particular, for two-dimensional (2D) van der Waals materials, as inferred from the Mermin-Wagner theorem, it is an essential prerequisite for stabilizing ferromagnetic order. In this work, we carry out first-principles calculations for a CrI3 monolayer and investigate how its magnetic anisotropy is interrelated to adjustable parameters governing the underlying electronic structure. We explore various routes for controlled manipulation of magnetic anisotropy: chemical adsorption, substitutional doping, optical excitation, and charge transfer through a heterostructure. In particular, the vertical stacking of CrI3 and graphene is noteworthy in regard to controlling magnetic anisotropy: the spin anisotropy axis is switchable between the out-of-plane and in-plane directions, which is accompanied by a variation in the anisotropy energy of up to 500%. Our results show the possibility that dynamic control of the anisotropy of the 2D magnet CrI3 may enable the development of an advanced spintronic device with enhanced energy efficiency and high operation speed.

Screening of suitable cationic dopants for solar absorber material CZTS/Se: A first principles study.

The earth abundant and non-toxic solar absorber material kesterite Cu2ZnSn(S/Se)4 has been studied to achieve high power conversion efficiency beyond various limitations, such as secondary phases, antisite defects, band gap adjustment and microstructure. To alleviate these hurdles, we employed screening based approach to find suitable cationic dopant that can promote the current density and the theoretical maximum upper limit of the energy conversion efficiency (P(%)) of CZTS/Se solar devices. For this task, the hybrid functional (Heyd, Scuseria and Ernzerhof, HSE06) were used to study the electronic and optical properties of cation (Al, Sb, Ga, Ba) doped CZTS/Se. Our in-depth investigation reveals that the Sb atom is suitable dopant of CZTS/CZTSe and also it has comparable bulk modulus as of pure material. The optical absorption coefficient of Sb doped CZTS/Se is considerably larger than the pure materials because of easy formation of visible range exciton due to the presence of defect state below the Fermi level, which leads to an increase in the current density and P(%). Our results demonstrate that the lower formation energy, preferable energy gap and excellent optical absorption of the Sb doped CZTS/Se make it potential component for relatively high efficient solar cells.

Prediction of ferroelectricity-driven Berry curvature enabling charge- and spin-controllable photocurrent in tin telluride monolayers.

In symmetry-broken crystalline solids, pole structures of Berry curvature (BC) can emerge, and they have been utilized as a versatile tool for controlling transport properties. For example, the monopole component of the BC is induced by the time-reversal symmetry breaking, and the BC dipole arises from a lack of inversion symmetry, leading to the anomalous Hall and nonlinear Hall effects, respectively. Based on first-principles calculations, we show that the ferroelectricity in a tin telluride monolayer produces a unique BC distribution, which offers charge- and spin-controllable photocurrents. Even with the sizable band gap, the ferroelectrically driven BC dipole is comparable to those of small-gap topological materials. By manipulating the photon handedness and the ferroelectric polarization, charge and spin circular photogalvanic currents are generated in a controllable manner. The ferroelectricity in group-IV monochalcogenide monolayers can be a useful tool to control the BC dipole and the nonlinear optoelectronic responses.

Scratch to sensitize: scratch-induced sensitivity enhancement in semiconductor thin-film sensors.

Semiconductor gas sensors are advantageous in miniaturization and can be used in a wide range of applications, yet consume large power due to high operating temperature. Here we demonstrated the ability of nanoscale scratches produced with mechanical abrasion to enhance the chemical sensitivity of thin-film-type semiconductor sensors. Well-aligned arrays of scratches parallel to the electrical current direction between the source and drain electrodes were made, using typical polishing machines with diamond suspensions, on semiconductor thin films produced with various deposition methods such as atomic layer deposition (ALD), sputtering, and the sol-gel technique. Processing with sharp diamond microparticles left nano-grooves on the surface, together with changes in chemical composition. For all of the tested metal oxide thin films, the introduction of scratches yielded increased quantities of oxygen vacancies and metallic components. Scratched ZnO devices exhibited superior performance even at room temperature, as predicted by a computational simulation that showed increased binding energy of gas molecules on defects. The scratch technique shown in the present study may be used to produce dense arrays of nanometer-scale, chemically functionalized line patterns on substrates larger than a few tens of centimeters with minimum cost, which in turn may be used in a variety of applications including massive arrays of sensors displaying high sensitivity.

Atomic-Level Customization of 4 in. Transition Metal Dichalcogenide Multilayer Alloys for Industrial Applications.

Despite many encouraging properties of transition metal dichalcogenides (TMDs), a central challenge in the realm of industrial applications based on TMD materials is to connect the large-scale synthesis and reproducible production of highly crystalline TMD materials. Here, the primary aim is to resolve simultaneously the two inversely related issues through the synthesis of MoS2(1- x ) Se2 x ternary alloys with customizable bichalcogen atomic (S and Se) ratio via atomic-level substitution combined with a solution-based large-area compatible approach. The relative concentration of bichalcogen atoms in the 2D alloy can be effectively modulated by altering the selenization temperature, resulting in 4 in. scale production of MoS1.62 Se0.38 , MoS1.37 Se0.63 , MoS1.15 Se0.85 , and MoS0.46 Se1.54 alloys, as well as MoS2 and MoSe2 . Comprehensive spectroscopic evaluations for vertical and lateral homogeneity in terms of heteroatom distribution in the large-scale 2D TMD alloys are implemented. Se-stimulated strain effects and a detailed mechanism for the Se substitution in the MoS2 crystal are further explored. Finally, the capability of the 2D alloy for industrial application in nanophotonic devices and hydrogen evolution reaction (HER) catalysts is validated. Substantial enhancements in the optoelectronic and HER performances of the 2D ternary alloy compared with those of its binary counterparts, including pure-phase MoS2 and MoSe2 , are unambiguously achieved.

Spin-Split Band Hybridization in Graphene Proximitized with α-RuCl3 Nanosheets.

Proximity effects induced in the two-dimensional Dirac material graphene potentially open access to novel and intriguing physical phenomena. Thus far, the coupling between graphene and ferromagnetic insulators has been experimentally established. However, only very little is known about graphene's interaction with antiferromagnetic insulators. Here, we report a low-temperature study of the electronic properties of high quality van der Waals heterostructures composed of a single graphene layer proximitized with α-RuCl3. The latter is known to become antiferromagnetically ordered below 10 K. Shubnikov-de Haas oscillations in the longitudinal resistance together with Hall resistance measurements provide clear evidence for a band realignment that is accompanied by a transfer of electrons originally occupying the graphene's spin degenerate Dirac cones into α-RuCl3 band states with in-plane spin polarization. Left behind are holes in two separate Fermi pockets, only the dispersion of one of which is distorted near the Fermi energy due to spin selective hybridization with these spin polarized α-RuCl3 band states. This interpretation is supported by our density functional theory calculations. An unexpected damping of the quantum oscillations as well as a zero-field resistance upturn close to the Néel temperature of α-RuCl3 suggest the onset of additional spin scattering due to spin fluctuations in the α-RuCl3.

Paramagnetic Carbon Nanosheets with Random Hole Defects and Oxygenated Functional Groups.

Ordered graphitic carbon nanosheets (GCNs) were, for the first time, synthesized by the direct condensation of multifunctional phenylacetyl building blocks (monomers) in the presence of phosphorous pentoxide. The GCNs had highly ordered structures with random hole defects and oxygenated functional groups, showing paramagnetism. The results of combined structural and magnetic analyses indicate that the hole defects and functional groups are associated with the appearance and stabilization of unpaired spins. DFT calculations further suggest that the emergence of stabilized spin moments near the edge groups necessitates the presence of functionalized carbon atoms around the hole defects. That is, both hole defects and oxygenated functional groups are essential ingredients for the generation and stabilization of spins in GCNs.

Unraveling materials Berry curvature and Chern numbers from real-time evolution of Bloch states.

Materials can be classified by the topological character of their electronic structure and, in this perspective, global attributes immune to local deformations have been discussed in terms of Berry curvature and Chern numbers. Except for instructional simple models, linear response theories have been ubiquitously used in calculations of topological properties of real materials. Here we propose a completely different and versatile approach to obtain the topological characteristics of materials by calculating physical observables from the real-time evolving Bloch states: The cell-averaged current density reveals the anomalous velocities that lead to the conductivity quantum. Results for prototypical cases are shown, including a spin-frozen valley Hall and a quantum anomalous Hall insulator. The advantage of this method is best illustrated by the example of a quantum spin Hall insulator: The quantized spin Hall conductivity is straightforwardly obtained irrespective of the non-Abelian nature in its Berry curvature. Moreover, the method can be extended to the description of real observables in nonequilibrium states of topological materials.