Bandgap modulation in the two-dimensional core-shell-structured monolayers of WS2.

Tungsten disulfide (WS2) has tunable bandgaps, which are required for diverse optoelectronic device applications. Here, we report the bandgap modulation in WS2 monolayers with two-dimensional core-shell structures formed by unique growth mode in chemical vapor deposition (CVD). The core-shell structures in our CVD-grown WS2 monolayers exhibit contrasts in optical images, Raman, and photoluminescence spectroscopy. The strain and doping effects in the WS2, introduced by two different growth processes, generate PL peaks at 1.83 eV (at the core domain) and 1.98 eV (at the shell domain), which is distinct from conventional WS2 with a primary PL peak at 2.02 eV. Our density functional theory (DFT) calculations explain the modulation of the optical bandgap in our core-shell-structured WS2 monolayers by the strain, accompanying a direct-to-indirect bandgap transition. Thus, the core-shell-structured WS2 monolayers provide a practical method to fabricate lateral heterostructures with different optical bandgaps, which are required for optoelectronic applications.

Orbital Gating Driven by Giant Stark Effect in Tunneling Phototransistors.

Conventional gating in transistors uses electric fields through external dielectrics that require complex fabrication processes. Various optoelectronic devices deploy photogating by electric fields from trapped charges in neighbor nanoparticles or dielectrics under light illumination. Orbital gating driven by giant Stark effect is demonstrated in tunneling phototransistors based on 2H-MoTe2 without using external gating bias or slow charge trapping dynamics in photogating. The original self-gating by light illumination modulates the interlayer potential gradient by switching on and off the giant Stark effect where the dz 2-orbitals of molybdenum atoms play the dominant role. The orbital gating shifts the electronic bands of the top atomic layer of the MoTe2 by up to 100 meV, which is equivalent to modulation of a carrier density of 7.3 × 1011 cm-2 by electrical gating. Suppressing conventional photoconductivity, the orbital gating in tunneling phototransistors achieves low dark current, practical photoresponsivity (3357 AW-1 ), and fast switching time (0.5 ms) simultaneously.

Mitrofanovite, Layered Platinum Telluride, for Active Hydrogen Evolution.

Two-dimensional (2D) layered catalysts have been considered as a class of ideal catalysts for hydrogen evolution reaction (HER) because of their abundant active sites with almost zero Gibbs energy change for hydrogen adsorption. Despite the promising performance, the design of stable and economic electrochemical catalyst based on 2D materials remains to be resolved for industrial-scale hydrogen production. Here, we report layered platinum tellurides, mitrofanovite Pt3Te4, which serves as an efficient and stable catalyst for HER with an overpotential of 39.6 mV and a Tafel slope of 32.7 mV/dec together with a high current density exceeding 7000 mA/cm2. Pt3Te4 was synthesized as nanocrystals on a metallic molybdenum ditelluride (MoTe2) template by a rapid electrochemical method. X-ray diffraction and high-resolution transmission microscopy revealed that the Pt3Te4 nanocrystals have a unique layered structure with repeated monolayer units of PtTe and PtTe2. Theoretical calculations exhibit that Pt3Te4 with numerous edges shows near-zero Gibbs free-energy change of hydrogen adsorption, which shows the excellent HER performance as well as the extremely large exchange current density for massive hydrogen production.

Nanoporous Silver Telluride for Active Hydrogen Evolution.

Silver-based nanomaterials have been versatile building blocks of various photoassisted energy applications; however, they have demonstrated poor electrochemical catalytic performance and stability, in particular, in acidic environments. Here we report a stable and high-performance electrochemical catalyst of silver telluride (AgTe) for the hydrogen evolution reaction (HER), which was synthesized with a nanoporous structure by an electrochemical synthesis method. X-ray spectroscopy techniques on the nanometer scale and high-resolution transmission electron microscopy revealed an orthorhombic structure of nanoporous AgTe with precise lattice constants. First-principles calculations show that the AgTe surface possesses highly active catalytic sites for the HER with an optimized Gibbs free energy change of hydrogen adsorption (-0.005 eV). Our nanoporous AgTe demonstrates exceptional stability and performance for the HER, an overpotential of 27 mV, and a Tafel slope of 33 mV/dec. As a stable catalyst for hydrogen production, AgTe is comparable to platinum-based catalysts and provides a breakthrough for high-performance electrochemical catalysts.

Polymorphic Spin, Charge, and Lattice Waves in Vanadium Ditelluride.

Lattice distortion, spin interaction, and dimensional crossover in transition metal dichalcogenides (TMDs) have led to intriguing quantum phases such as charge density waves (CDWs) and 2D magnetism. However, the combined effect of many factors in TMDs, such as spin-orbit, electron-phonon, and electron-electron interactions, stabilizes a single quantum phase at a given temperature and pressure, which restricts original device operations with various quantum phases. Here, nontrivial polymorphic quantum states, CDW phases, are reported in vanadium ditelluride (VTe2 ) at room temperature, which is unique among various CDW systems; the doping concentration determines the formation of either of the two CDW phases in VTe2 at ambient conditions. The two CDW polymorphs show different antiferromagnetic spin orderings in which the vanadium atoms create two different stripe-patterned spin waves. First-principles calculations demonstrate that the magnetic ordering is critically coupled with the corresponding CDW in VTe2 , which suggests a rich phase diagram with polymorphic spin, charge, and lattice waves all coexisting in a solid for new conceptual quantum state-switching device applications.