Predictions of delafossite-hosted honeycomb and kagome phases.

Delafossites, typically denoted by the formula ABO2, are a class of layered materials that exhibit a wide range of electronic and optical properties. Recently, the idea of modifying these delafossites into ordered kagome or honeycomb phases via strategic doping has emerged as a potential way to tailor these properties. In this study, we use high-throughput density functional theory calculations to explore many possible candidate kagome and honeycomb phases by considering dopants selected from the parent compounds of known ternary delafossite oxides from the inorganic crystal structure database. Our results indicate that while A-site in existing delafossites can host a limited range of elemental specifies, and display a low propensity for mixing or ordering, the oxide sub-units in the BO2 much more readily admit guest species. Our study identifies four candidate B-site kagome and fifteen candidate B-site honeycombs with a formation energy more than 50 meV f.u.-1 below other competing phases. The ability to predict and control the formation of these unique structures offers exciting opportunities in materials design, where innovative properties can be engineered through the selection of specific dopants. A number of these constitute novel correlated metals, which may be of interest for subsequent efforts in synthesis. These novel correlated metals may have significant implications for quantum computing, spintronics, and high-temperature superconductivity, thus inspiring future experimental synthesis and characterization of these proposed materials.

More Than 30 000-fold Field Enhancement of Terahertz Nanoresonators Enabled by Rapid Inverse Design.

The rapid development of 6G communications using terahertz (THz) electromagnetic waves has created a demand for highly sensitive THz nanoresonators capable of detecting these waves. Among the potential candidates, THz nanogap loop arrays show promising characteristics but require significant computational resources for accurate simulation. This requirement arises because their unit cells are 10 times smaller than millimeter wavelengths, with nanogap regions that are 1 000 000 times smaller. To address this challenge, we propose a rapid inverse design method using physics-informed machine learning, employing double deep Q-learning with an analytical model of the THz nanogap loop array. In ∼39 h on a middle-level personal computer, our approach identifies the optimal structure through 200 000 iterations, achieving an experimental electric field enhancement of 32 000 at 0.2 THz, 300% stronger than prior results. Our analytical model-based approach significantly reduces the amount of computational resources required, offering a practical alternative to numerical simulation-based inverse design for THz nanodevices.

Quantum Phase Engineering of Two-Dimensional Post-Transition Metals by Substrates: Toward a Room-Temperature Quantum Anomalous Hall Insulator.

We propose a new strategy to engineer topological and magnetic properties of two-dimensional (2D) hexagonal lattices consisting of post-transition metals. Our first-principles calculations demonstrate that substrates serve as templates to form 2D lattices with high thermodynamic stability, where their topological properties as well as magnetic properties sensitively change as a function of lattice constants, i.e., the system undergoes a first-order phase transition from nonmagnetic to ferromagnetic state above a critical lattice constant. Consequently, substrates can be used to explore versatile magnetic, electronic, and quantum topological properties. We establish phase diagrams of versatile quantum phases in terms of exchange coupling and spin-orbit coupling effectively tuned by the lattice constants. We further reveal the first room-temperature quantum anomalous Hall (QAH) effect, i.e., Sn on 2√3 × 2√3 graphane is a QAH insulator with a large spin-orbit coupling gap of ∼0.2 eV and a Curie temperature of ∼380 K by using the 2D anisotropic Heisenberg model.

Crystal structures and rotational dynamics of a two-dimensional metal halide perovskite (OA)2PbI4.

The extended charge carrier lifetime in metal halide perovskites is responsible for their excellent optoelectronic properties. Recent studies indicate that the superb device performance in these materials is intimately related to the organic cation dynamics. Here, we focus on the investigation of the two-dimensional hybrid perovskite, (C8H17NH3)2PbI4 (henceforth, OA+ = C8H17NH3 +). Using elastic and quasielastic neutron scattering techniques and group theoretical analysis, we studied the structural phase transitions and rotational modes of the C8H17NH3 + cation in (OA)2PbI4. Our results show that, in the high-temperature orthorhombic (T > 310 K) phase, the OA+ cation exhibits a combination of a twofold rotation of the NH3-CH2 head group about the crystal c-axis with a characteristic relaxation time of ∼6.2 ps, threefold rotations (C3) of NH3 and CH3 terminal groups, and slow librations of the other atoms. Contrastingly, only the C3 rotation is present in the intermediate-temperature orthorhombic (238 K < T < 310 K) and low-temperature monoclinic (T < 238 K) phases.

Origin of long lifetime of band-edge charge carriers in organic-inorganic lead iodide perovskites.

Long carrier lifetime is what makes hybrid organic-inorganic perovskites high-performance photovoltaic materials. Several microscopic mechanisms behind the unusually long carrier lifetime have been proposed, such as formation of large polarons, Rashba effect, ferroelectric domains, and photon recycling. Here, we show that the screening of band-edge charge carriers by rotation of organic cation molecules can be a major contribution to the prolonged carrier lifetime. Our results reveal that the band-edge carrier lifetime increases when the system enters from a phase with lower rotational entropy to another phase with higher entropy. These results imply that the recombination of the photoexcited electrons and holes is suppressed by the screening, leading to the formation of polarons and thereby extending the lifetime. Thus, searching for organic-inorganic perovskites with high rotational entropy over a wide range of temperature may be a key to achieve superior solar cell performance.

First-Principles Prediction of New Electrides with Nontrivial Band Topology Based on One-Dimensional Building Blocks.

We introduce a new class of electrides with nontrivial band topology by coupling materials database searches and first-principles-calculations-based analysis. Cs_{3}O and Ba_{3}N are for the first time identified as a new class of electrides, consisting of one-dimensional (1D) nanorod building blocks. Their crystal structures mimic ß-TiCl_{3} with the position of anions and cations exchanged. Unlike the weakly coupled nanorods of ß-TiCl_{3}, Cs_{3}O and Ba_{3}N retain 1D anionic electrons along the hollow interrod sites; additionally, a strong interrod interaction in C_{3}O and Ba_{3}N induces band inversion in a 2D superatomic triangular lattice, resulting in Dirac-node lines. The new class of electrides can serve as a prototype for new electrides with a large cavity space that can be utilized for various applications such as gas storage, ion transport, and metal intercalation.

Surface Magnetism of Cobalt Nanoislands Controlled by Atomic Hydrogen.

Controlling the spin states of the surface and interface is key to spintronic applications of magnetic materials. Here, we report the evolution of surface magnetism of Co nanoislands on Cu(111) upon hydrogen adsorption and desorption with the hope of realizing reversible control of spin-dependent tunneling. Spin-polarized scanning tunneling microscopy reveals three types of hydrogen-induced surface superstructures, 1H-(2 × 2), 2H-(2 × 2), and 6H-(3 × 3), with increasing H coverage. The prominent magnetic surface states of Co, while being preserved at low H coverage, become suppressed as the H coverage level increases, which can then be recovered by H desorption. First-principles calculations reveal the origin of the observed magnetic surface states by capturing the asymmetry between the spin-polarized surface states and identify the role of hydrogen in controlling the magnetic states. Our study offers new insights into the chemical control of magnetism in low-dimensional systems.

Nonequilibrium Synthesis of TiO2 Nanoparticle "Building Blocks" for Crystal Growth by Sequential Attachment in Pulsed Laser Deposition.

Nonequilibrium growth pathways for crystalline nanostructures with metastable phases are demonstrated through the gas-phase formation, attachment, and crystallization of ultrasmall amorphous nanoparticles as building blocks in pulsed laser deposition (PLD). Temporally and spatially resolved gated-intensified charge couple device (ICCD) imaging and ion probe measurements are employed as in situ diagnostics to understand and control the plume expansion conditions for the synthesis of nearly pure fluxes of ultrasmall (∼3 nm) amorphous TiO2 nanoparticles in background gases and their selective delivery to substrates. These amorphous nanoparticles assemble into loose, mesoporous assemblies on substrates at room temperature but dynamically crystallize by sequential particle attachment at higher substrate temperatures to grow nanostructures with different phases and morphologies. Molecular dynamics calculations are used to simulate and understand the crystallization dynamics. This work demonstrates that nonequilibrium crystallization by particle attachment of metastable ultrasmall nanoscale "building blocks" provides a versatile approach for exploring and controlling the growth of nanoarchitectures with desirable crystalline phases and morphologies.

Formation of Ideal Rashba States on Layered Semiconductor Surfaces Steered by Strain Engineering.

Spin splitting of Rashba states in two-dimensional electron system provides a promising mechanism of spin manipulation for spintronics applications. However, Rashba states realized experimentally to date are often outnumbered by spin-degenerated substrate states at the same energy range, hindering their practical applications. Here, by density functional theory calculation, we show that Au one monolayer film deposition on a layered semiconductor surface ß-InSe(0001) can possess "ideal" Rashba states with large spin splitting, which are completely situated inside the large band gap of the substrate. The position of the Rashba bands can be tuned over a wide range with respect to the substrate band edges by experimentally accessible strain. Furthermore, our nonequilibrium Green's function transport calculation shows that this system may give rise to the long-sought strong current modulation when made into a device of Datta-Das transistor. Similar systems may be identified with other metal ultrathin films and layered semiconductor substrates to realize ideal Rashba states.

Tailoring Vacancies Far Beyond Intrinsic Levels Changes the Carrier Type and Optical Response in Monolayer MoSe2-x Crystals.

Defect engineering has been a critical step in controlling the transport characteristics of electronic devices, and the ability to create, tune, and annihilate defects is essential to enable the range of next-generation devices. Whereas defect formation has been well-demonstrated in three-dimensional semiconductors, similar exploration of the heterogeneity in atomically thin two-dimensional semiconductors and the link between their atomic structures, defects, and properties has not yet been extensively studied. Here, we demonstrate the growth of MoSe2-x single crystals with selenium (Se) vacancies far beyond intrinsic levels, up to ∼20%, that exhibit a remarkable transition in electrical transport properties from n- to p-type character with increasing Se vacancy concentration. A new defect-activated phonon band at ∼250 cm(-1) appears, and the A1g Raman characteristic mode at 240 cm(-1) softens toward ∼230 cm(-1) which serves as a fingerprint of vacancy concentration in the crystals. We show that post-selenization using pulsed laser evaporated Se atoms can repair Se-vacant sites to nearly recover the properties of the pristine crystals. First-principles calculations reveal the underlying mechanisms for the corresponding vacancy-induced electrical and optical transitions.

First-Principles Prediction of Thermodynamically Stable Two-Dimensional Electrides.

Two-dimensional (2D) electrides, emerging as a new type of layered material whose electrons are confined in interlayer spaces instead of at atomic proximities, are receiving interest for their high performance in various (opto)electronics and catalytic applications. Experimentally, however, 2D electrides have been only found in a couple of layered nitrides and carbides. Here, we report new thermodynamically stable alkaline-earth based 2D electrides by using a first-principles global structure optimization method, phonon spectrum analysis, and molecular dynamics simulation. The method was applied to binary compounds consisting of alkaline-earth elements as cations and group VA, VIA, or VIIA nonmetal elements as anions. We revealed that the stability of a layered 2D electride structure is closely related to the cation/anion size ratio; stable 2D electrides possess a sufficiently large cation/anion size ratio to minimize electrostatic energy among cations, anions, and anionic electrons. Our work demonstrates a new avenue to the discovery of thermodynamically stable 2D electrides beyond experimental material databases and provides new insight into the principles of electride design.

Nitrogen Doping Enables Covalent-Like π-π Bonding between Graphenes.

The neighboring layers in bilayer (and few-layer) graphenes of both AA and AB stacking motifs are known to be separated at a distance corresponding to van der Waals (vdW) interactions. In this Letter, we present for the first time a new aspect of graphene chemistry in terms of a special chemical bonding between the giant graphene "molecules". Through rigorous theoretical calculations, we demonstrate that the N-doped graphenes (NGPs) with various doping levels can form an unusual two-dimensional (2D) π-π bonding in bilayer NGPs bringing the neighboring NGPs to significantly reduced interlayer separations. The interlayer binding energies can be enhanced by up to 50% compared to the pristine graphene bilayers that are characterized by only vdW interactions. Such an unusual chemical bonding arises from the π-π overlap across the vdW gap while the individual layers maintain their in-plane π-conjugation and are accordingly planar. The existence of the resulting interlayer covalent-like bonding is corroborated by electronic structure calculations and crystal orbital overlap population (COOP) analyses. In NGP-based graphite with the optimal doping level, the NGP layers are uniformly stacked and the 3D bulk exhibits metallic characteristics both in the in-plane and along the stacking directions.

Growth of Metal Phthalocyanine on Deactivated Semiconducting Surfaces Steered by Selective Orbital Coupling.

Using scanning tunneling microscopy and density functional theory, we show that the molecular ordering and orientation of metal phthalocyanine molecules on the deactivated Si surface display a strong dependency on the central transition-metal ion, driven by the degree of orbital hybridization at the heterointerface via selective p-d orbital coupling. This Letter identifies a selective mechanism for modifying the molecule-substrate interaction which impacts the growth behavior of transition-metal-incorporated organic molecules on a technologically relevant substrate for silicon-based devices.

Alloy Engineering of Defect Properties in Semiconductors: Suppression of Deep Levels in Transition-Metal Dichalcogenides.

Developing practical approaches to effectively reduce the amount of deep defect levels in semiconductors is critical for their use in electronic and optoelectronic devices, but this still remains a very challenging task. In this Letter, we propose that specific alloying can provide an effective means to suppress the deep defect levels in semiconductors while maintaining their basic electronic properties. Specifically, we demonstrate that for transition-metal dichalcogenides, such as MoSe_{2} and WSe_{2}, where anion vacancies are the most abundant defects that can induce deep levels, the deep levels can be effectively suppressed in Mo_{1-x}W_{x}Se_{2} alloys at low W concentrations. This surprising phenomenon is associated with the fact that the band edge energies can be substantially tuned by the global alloy concentration, whereas the defect level is controlled locally by the preferred locations of Se vacancies around W atoms. Our findings illustrate a concept of alloy engineering and provide a promising approach to control the defect properties of semiconductors.

Electronic Properties of Bilayer Graphene Strongly Coupled to Interlayer Stacking and an External Electric Field.

Bilayer graphene (BLG) with a tunable band gap appears interesting as an alternative to graphene for practical applications; thus, its transport properties are being actively pursued. Using density functional theory and perturbation analysis, we investigated, under an external electric field, the electronic properties of BLG in various stackings relevant to recently observed complex structures. We established the first phase diagram summarizing the stacking-dependent gap openings of BLG for a given field. We further identified high-density midgap states, localized on grain boundaries, even under a strong field, which can considerably reduce the overall transport gap.

Revealing the preferred interlayer orientations and stackings of two-dimensional bilayer gallium selenide crystals.

Characterizing and controlling the interlayer orientations and stacking orders of two-dimensional (2D) bilayer crystals and van der Waals (vdW) heterostructures is crucial to optimize their electrical and optoelectronic properties. The four polymorphs of layered gallium selenide (GaSe) crystals that result from different layer stackings provide an ideal platform to study the stacking configurations in 2D bilayer crystals. Through a controllable vapor-phase deposition method, bilayer GaSe crystals were selectively grown and their two preferred 0° or 60° interlayer rotations were investigated. The commensurate stacking configurations (AA' and AB stacking) in as-grown bilayer GaSe crystals are clearly observed at the atomic scale, and the Ga-terminated edge structure was identified using scanning transmission electron microscopy. Theoretical analysis reveals that the energies of the interlayer coupling are responsible for the preferred orientations among the bilayer GaSe crystals.

Highly responsive ultrathin GaS nanosheet photodetectors on rigid and flexible substrates.

The first GaS nanosheet-based photodetectors are demonstrated on both mechanically rigid and flexible substrates. Highly crystalline, exfoliated GaS nanosheets are promising for optoelectronics due to strong absorption in the UV-visible wavelength region. Photocurrent measurements of GaS nanosheet photodetectors made on SiO2/Si substrates and flexible polyethylene terephthalate (PET) substrates exhibit a photoresponsivity at 254 nm up to 4.2 AW(-1) and 19.2 AW(-1), respectively, which exceeds that of graphene, MoS2, or other 2D material-based devices. Additionally, the linear dynamic range of the devices on SiO2/Si and PET substrates are 97.7 dB and 78.73 dB, respectively. Both surpass that of currently exploited InGaAs photodetectors (66 dB). Theoretical modeling of the electronic structures indicates that the reduction of the effective mass at the valence band maximum (VBM) with decreasing sheet thickness enhances the carrier mobility of the GaS nanosheets, contributing to the high photocurrents. Double-peak VBMs are theoretically predicted for ultrathin GaS nanosheets (thickness less than five monolayers), which is found to promote photon absorption. These theoretical and experimental results show that GaS nanosheets are promising materials for high-performance photodetectors on both conventional silicon and flexible substrates.

Distance-Dependent Evolution of Electronic States in Kagome-Honeycomb Lateral Heterostructures in FeSn.

In this work, we demonstrate the formation and electronic influence of lateral heterointerfaces in FeSn containing Kagome and honeycomb layers. Lateral heterostructures offer spatially resolved property control, enabling the integration of dissimilar materials and promoting phenomena not typically observed in vertical heterostructures. Using the molecular beam epitaxy technique, we achieve a controllable synthesis of lateral heterostructures in the Kagome metal FeSn. With scanning tunneling microscopy/spectroscopy in conjunction with first-principles calculations, we provide a comprehensive understanding of the bonding motif connecting the Fe3Sn-terminated Kagome and Sn2-terminated honeycomb surfaces. More importantly, we reveal a distance-dependent evolution of the electronic states in the vicinity of the heterointerfaces. This evolution is significantly influenced by the orbital character of the flat bands. Our findings suggest an approach to modulate the electronic properties of the Kagome lattice, which should be beneficial for the development of future quantum devices.

Role of Curvature in Stabilizing Boron-Doped Nanocorrugated Graphene.

Boron-doped carbon nanostructures have attracted great interest recently because of their remarkable electrocatalytic performance comparable to or better than that of conventional metal catalysts. In a previous work (Carbon 123, 605 (2017)), we reported that along with significant performance improvement, B doping enhances the oxidation resistance of few-layer graphene (FLG) that provides increased structural stability for intermediate-temperature fuel-cell electrodes. In general, detailed characterization of the atomic and electronic structure transformations that occur in B-doped carbon nanostructures during fuel-cell operation is lacking. In this work, we use aberration-corrected scanning transmission electron microscopy, nanobeam electron diffraction, and electron energy-loss spectroscopy (EELS) to characterize the atomic and electronic structures of B-doped FLG before and after fuel-cell operation. These data point to the nanoscale corrugation of B-doped FLGs as the key factor responsible for increased stability and high corrosion resistance. The similarity of the 1s to π* and σ* transition features in the B K-edge EELS to those in B-doped carbon nanotubes provides an estimate for the curvature of nanocorrugation in B-FLG.