Dual functionality of the BiN monolayer: unraveling its photocatalytic and piezocatalytic water splitting properties.

To achieve scalable and economically viable green hydrogen (H2) production, the photocatalytic and piezocatalytic processes are promising methods. The key to successful overall water splitting (OWS) for H2 production in these processes is using suitable semiconductor catalysts with appropriate band edge potentials, efficient optical absorption, higher mechanical flexibility, and piezoelectric coefficients. Thus, we explore the bismuth nitride (BiN) monolayer using density functional theory simulations, revealing intriguing catalytic properties. The BiN monolayer is a semiconductor with an indirect electronic bandgap (Eg) of 2.08 eV and displays excellent visible light absorption (approximately 105 cm-1). Detailed analyses show that the band edges satisfy the redox potential for photocatalytic OWS via biaxial strain engineering and pH variation. Notably, the solar to hydrogen conversion efficiency (ηSTH) for the BiN monolayer can reach 17.18%, which exceeds the 10% efficiency limit of photocatalysts for economical green H2 production. The obtained in-plane piezoelectric coefficient of e11 = 16.18 ŠC m-1 is superior to widely studied 2D materials. Moreover, the generated piezopotential under oscillatory strain stands at 28.34 V, which can initiate the water redox reaction via the piezocatalytic mechanism. This originates from the mechanical flexibility coupled with higher piezoelectric coefficients. The result highlights the BiN monolayer's potential application in photocatalytic, piezocatalytic, and photo-piezo-catalytic OWS.

Two-dimensional gallium nitride realized via graphene encapsulation.

The spectrum of two-dimensional (2D) and layered materials 'beyond graphene' offers a remarkable platform to study new phenomena in condensed matter physics. Among these materials, layered hexagonal boron nitride (hBN), with its wide bandgap energy (∼5.0-6.0 eV), has clearly established that 2D nitrides are key to advancing 2D devices. A gap, however, remains between the theoretical prediction of 2D nitrides 'beyond hBN' and experimental realization of such structures. Here we demonstrate the synthesis of 2D gallium nitride (GaN) via a migration-enhanced encapsulated growth (MEEG) technique utilizing epitaxial graphene. We theoretically predict and experimentally validate that the atomic structure of 2D GaN grown via MEEG is notably different from reported theory. Moreover, we establish that graphene plays a critical role in stabilizing the direct-bandgap (nearly 5.0 eV), 2D buckled structure. Our results provide a foundation for discovery and stabilization of 2D nitrides that are difficult to prepare via traditional synthesis.

Hubbard gap modulation in vanadium dioxide nanoscale tunnel junctions.

We locally investigate the electronic transport through individual tunnel junctions containing a 10 nm thin film of vanadium dioxide (VO2) across its thermally induced phase transition. The insulator-to-metal phase transition in the VO2 film collapses the Hubbard gap (experimentally determined to be 0.4 ± 0.07 V), leading to several orders of magnitude change in tunnel conductance. We quantitatively evaluate underlying transport mechanisms via theoretical quantum mechanical transport calculations which show excellent agreement with the experimental results.

Atomically thin heterostructures based on single-layer tungsten diselenide and graphene.

Heterogeneous engineering of two-dimensional layered materials, including metallic graphene and semiconducting transition metal dichalcogenides, presents an exciting opportunity to produce highly tunable electronic and optoelectronic systems. In order to engineer pristine layers and their interfaces, epitaxial growth of such heterostructures is required. We report the direct growth of crystalline, monolayer tungsten diselenide (WSe2) on epitaxial graphene (EG) grown from silicon carbide. Raman spectroscopy, photoluminescence, and scanning tunneling microscopy confirm high-quality WSe2 monolayers, whereas transmission electron microscopy shows an atomically sharp interface, and low energy electron diffraction confirms near perfect orientation between WSe2 and EG. Vertical transport measurements across the WSe2/EG heterostructure provides evidence that an additional barrier to carrier transport beyond the expected WSe2/EG band offset exists due to the interlayer gap, which is supported by theoretical local density of states (LDOS) calculations using self-consistent density functional theory (DFT) and nonequilibrium Green's function (NEGF).

A folded π-system with supramolecularly oriented dipoles: single-component piezoelectric relaxor with NLO activity.

Organic molecules with an active dipole moment have a natural propensity to align in an antiparallel fashion in the solid state, resulting in zero macroscopic polarization. This primary limitation makes the material unresponsive to switching with electric fields, mechanical forces, and to intense laser light. A single-component organic material that bestows macroscopic dipole-driven electro-mechanical and optical functions, e.g., piezoelectric, ferroelectric and nonlinear optical (NLO) activity, is unprecedented due to the design challenges imparted by crystal symmetry and dipole orientations. Herein we report a crystalline organic material that self-assembles with a polar order (P 1), and is endowed with a high piezoelectric coefficient (d 33-47 pm V-1), as well as ferroelectric and Debye-type relaxor properties. In addition, it shows second harmonic generation (SHG) activity, which is more than five times that of the benchmark potassium dihydrogen phosphate. Piezoelectric force microscopy (PFM) images validated electro-mechanical deformations. Piezoresponse force spectroscopy (PFS) studies confirmed a signature butterfly-like amplitude and a phase loop. To the best of our knowledge, this is the first report of a folded supramolecular π-system that manifests unidirectionally oriented dipoles and exhibits piezoelectricity, ferroelectricity, and has excellent ability to generate second harmonic light. These findings can herald new design possibilities based on folded architectures to explore opto-, electro- and mechano-responsive multifaceted functions.

Intrinsic ferroelectricity and large bulk photovoltaic effect in novel two-dimensional buckled honeycomb-like lattice of NbP: first-principles study.

Using first-principles calculations, we predict that the two-dimensional (2D) monolayers of NbP with the buckled honeycomb-like and puckered tetragonal structure can be obtained from the (110) and (001) orientations, respectively, of its bulk crystal structure. The electronic properties of these monolayers are spectacularly different as tetragonal lattice is metallic whereas the honeycomb-like lattice (h-NbP) is a semiconductor and exhibits intrinsic ferroelectricity originating from a raresd2-sp2hybridization. The shift current bulk photovoltaic effect (BPVE) is systematically investigated in the h-NbP monolayer (1.21 Å thickness) using the Wannier interpolation method. Strong absorption of visible light at ∼2 eV and a large 3D shift current of ∼180µA V-2is obtained which is attributed to the partial delocalization of Bloch states due tosd2-sp2hybridization. We compare the shift current response of h-NbP monolayer with that of some previously reported bulk ferroelectrics and 2D monolayers, suggesting that h-NbP monolayer can yield a large shift current at an ultimate thickness and is a promising 2D material for the BPVE application under the visible light. Strain effect is also investigated, revealing that the h-NbP monolayer is dynamically stable up to a strain limit of ±3%, and the shift current increases by ∼9% at a compressive strain of -3% as the Bloch states are more delocalized due to the strengthening ofsd2-sp2hybridization. The results presented in this study can pave the paths to fabricate the 2D monolayered structures of NbP, and realize the BPVE based next-generation solar cells of h-NbP monolayer.

Strain engineering of ferroelectric KNbO3 for bulk photovoltaic applications: an insight from density functional theory calculations.

A large ferroelectric (FE) polarization and low bandgap are essential to improving the bulk photovoltaic response which is the generation of photocurrent in the polar non-centrosymmetric materials such as FE perovskite oxides. Among various perovskite oxides, Potassium Niobate (KNbO3, KNO) is a promising FE material for bulk photovoltaic applications as its bandgap and polarization can be tuned effectively by strain, doping, or by applying an electric field. In this work, using the density functional theory calculations, we present an insight into the strain engineering of polarization, band structure, and optical properties of the cubic (C), tetragonal (T), and orthorhombic (O) structures of KNO. The tensile and compressive strain under the triaxial, biaxial, and uniaxial conditions are applied along the direction parallel and perpendicular to the polar axis of KNO structures. We find that the bandgap decreases along with a substantial increment of polarization on the application of tensile strain along the direction parallel to the polar axis. In T (O) phase at +2% strain, the polarization increases by 18 µC cm-2 (14 µC cm-2) in triaxial, 26 µC cm-2 (16 µC cm-2) in biaxial, and 29 µC cm-2 (29 µC cm-2) in uniaxial conditions with a considerable decreasing of bandgap with respect to zero strain condition. Therefore, wisely applying the tensile strain along the direction parallel to the polar axis, the photovoltaic efficiency of KNO can be improved.

Investigation of room temperature ferromagnetism in transition metal doped BiFeO3.

Spintronic functionality in ferromagnetic materials is a next-generation technique, to be used in data storage, high-frequency communications, and logic devices with minimum energy consumption. Ultra-low energy consumption in high-speed logic devices can be envisioned by inducing ferromagnetic behavior into room temperature multiferroic materials. However, there is a scarcity of room temperature multiferroic materials which have a definite spin degree of freedom. To fully exploit these technological challenges, we introduce the induced ferromagnetism in bismuth ferrite (BiFeO3, BFO) by doping transition metal (Cr, Ni, Co) elements. Our investigation initiates with the experimental study on chemically synthesized BiFe(1-x)M x O3 samples where x = 0.0625 (6.25%) and M = Cr, Ni and Co. Experimental findings are verified by theoretical simulation using density functional theory (DFT + U) and gauge including projector augmented wave (GIPAW) based calculation. All the experimental studies are done at room temperature while the theoretical verification using DFT is carried to understand the underlying mechanism behind the magnetic behavior of doped BiFeO3. It is done by optimizing the structural parameters comparable to the room temperature values. Microstructural and magnetic properties are studied using x-ray diffraction (XRD), transmission electron microscopy (TEM) and Vibrating sample magnetometer (VSM). All these experimental studies confirm the structural changes and induced ferromagnetism with doping. X-ray photoelectron spectroscopy (XPS) verified the reason behind this ferromagnetic property on the basis of oxygen vacancy content. Electron paramagnetic resonance (EPR) spectroscopy shows the tuning of Δg values due to enhanced magnetization. The density of states (DOS) calculations were performed on BFO (band-gap 1.89 eV) after structural optimization using DFT + U method, confirm our experimental findings. Magnetic moment values change drastically with doping elements (M), i.e. almost negligible for BFO (antiferromagnetic) to maximum (2.85 µ B/f.u.) for Ni-doped sample. We also compute the EPR g-tensor using GIPAW method to confirm the tuning of Δg values due to enhanced magnetization. These results can highlight the impact and importance of suitable transition element doping to induce the room temperature ferromagnetism in BiFeO3.

Stabilizing the commensurate charge-density wave in 1T-tantalum disulfide at higher temperatures via potassium intercalation.

The 1T phase of tantalum disulfide (1T-TaS2) possesses a variety of charge-density-wave (CDW) orders, and as a result, it attracts an increasing amount of academic and technological interest. Researchers have devoted tremendous efforts towards understanding the impacts of doping, alloying, intercalation or other triggering agents on its charge density wave orders. In this work, we demonstrate that incorporating potassium chloride (KCl) during chemical vapor deposition (CVD) of TaS2 can control the phase (1T, 2H or metal nanowires) via the intercalation of potassium ions (K+) between TaS2 layers. Finally, we demonstrate that K+ not only impacts the structure during synthesis but also strongly impacts the CDW phase transition as a function of temperature, increasing the nearly commensurate (NCCDW) to commensurate (CCDW) transition to just below room temperature.

Atomically thin resonant tunnel diodes built from synthetic van der Waals heterostructures.

Vertical integration of two-dimensional van der Waals materials is predicted to lead to novel electronic and optical properties not found in the constituent layers. Here, we present the direct synthesis of two unique, atomically thin, multi-junction heterostructures by combining graphene with the monolayer transition-metal dichalcogenides: molybdenum disulfide (MoS2), molybdenum diselenide (MoSe2) and tungsten diselenide (WSe2). The realization of MoS2-WSe2-graphene and WSe2-MoS2-graphene heterostructures leads to resonant tunnelling in an atomically thin stack with spectrally narrow, room temperature negative differential resistance characteristics.