Highly Dispersed Pt Clusters on F-Doped Tin(IV) Oxide Aerogel Matrix: An Ultra-Robust Hybrid Catalyst for Enhanced Hydrogen Evolution.

Dispersing the minuscule mass loading without hampering the high catalytic activity and long-term stability of a noble metal catalyst results in its ultimate efficacy for the electrochemical hydrogen evolution reaction (HER). Despite being the most efficient HER catalyst, the use of Pt is curtailed due to its scarcity and tendency to leach out in the harsh electrochemical reaction environment. In this study, we combined F-doped tin(IV) oxide (F-SnO2) aerogel with Pt catalyst to prevent metallic corrosion and to achieve abundant Pt active sites (approximately 5 nm clusters) with large specific surface area (321 cm2·g-1). With nanoscopic Pt loading inside the SnO2 aerogel matrix, the as-synthesized hybrid F-SnO2@Pt possesses a large specific surface area and high porosity and, thus, exhibits efficient experimental and intrinsic HER activity (a low overpotential of 42 mV at 10 mA·cm-2 in 0.5 M sulfuric acid), a 22-times larger turnover frequency (11.2 H2·s-1) than that of Pt/C at 50 mV, and excellent robustness over 10,000 cyclic voltammetry cycles. The existing metal support interaction and strong intermolecular forces between Pt and F-SnO2 account for the catalytic superiority and persistence against corrosion of F-SnO2@Pt compared to commercially used Pt/C. Density functional theory analysis suggests that hybridization between the Pt and F-SnO2 orbitals enhances intermediate hydrogen atom (H*) adsorption at their interface, which improves the reaction kinetics.

Density functional theory study of the mechanical behavior of silicene and development of a Tersoff interatomic potential model tailored for elastic behavior.

Silicene, a graphene-like 2D material made from Si atoms, has been fabricated and studied for its promising applications in micro/nanoelectronics. For the reliable function of silicene devices, it is important to investigate silicene's mechanical properties. In this study, the authors conducted density functional theory (DFT) simulations of mechanical tests of silicene and investigated the elastic modulus and mechanical response such as structural transformation. In addition, the authors optimized the Tersoff potential parameters using a gradient-based minimization with a grid search method in hyperdimensional parameter space, to match the DFT calculation results in the elastic regime. With the new parameter set, the elastic moduli of silicene in the zigzag (ZZ) and armchair (AC) directions were computed with molecular statics (MS) simulations and compared with those of other Si interatomic potential models and DFT results. In addition, uniaxial tensile tests along the ZZ and AC directions were performed to examine how far the Tersoff model is transferable with our new parameter set to describe the nonlinear mechanical behavior of silicene. The results of uniaxial tensile tests suggest that the angle penalty function in the Tersoff model needs to be modified and that the stress-strain curve predicted with this modification shows improvement compared to the original function.

High-energy proton irradiation damage on two-dimensional hexagonal boron nitride.

The dielectric layer, which is an essential building block in electronic device circuitry, is subject to intrinsic or induced defects that limit its performance. Nano-layers of hexagonal boron nitride (h-BN) represent a promising dielectric layer in nano-electronics owing to its excellent electronic and thermal properties. In order to further analyze this technology, two-dimensional (2D) h-BN dielectric layers were exposed to high-energy proton irradiation at various proton energies and doses to intentionally introduce defective sites. A pristine h-BN capacitor showed typical degradation stages with a hard breakdown field of 10.3 MV cm-1, while h-BN capacitors irradiated at proton energies of 5 and 10 MeV at a dose of 1 × 1013 cm-2 showed lower hard breakdown fields of 1.6 and 8.3 MV cm-1, respectively. Higher leakage currents were observed under higher proton doses at 5 × 1013 cm-2, resulting in lower breakdown fields. The degradation stages of proton-irradiated h-BN are similar to those of defective silicon dioxide. The degradation of the h-BN dielectric after proton irradiation is attributed to Frenkel defects created by the high-energy protons, as indicated by the molecular dynamics simulation. Understanding the defect-induced degradation mechanism of h-BN nano-layers can improve their reliability, paving the way to the implementation of 2D h-BN in advanced micro- and nano-electronics.

Carrier Transport Properties of MoS2 Asymmetric Gas Sensor Under Charge Transfer-Based Barrier Modulation.

Over the past few years, two-dimensional materials have gained immense attention for next-generation electric sensing devices because of their unique properties. Here, we report the carrier transport properties of MoS2 Schottky diodes under ambient as well as gas exposure conditions. MoS2 field-effect transistors (FETs) were fabricated using Pt and Al electrodes. The work function of Pt is higher than that of MoS2, while that of Al is lower than that of MoS2. The MoS2 device with Al contacts showed much higher current than that with Pt contacts because of its lower Schottky barrier height (SBH). The electrical characteristics and gas responses of the MoS2 Schottky diodes with Al and Pt contacts were measured electrically and were simulated by density functional theory calculations. The theoretically calculated SBH of the diode (under gas absorption) showed that NOx molecules had strong interaction with the diode and induced a negative charge transfer. However, an opposite trend was observed in the case of NH3 molecules. We also investigated the effect of metal contacts on the gas sensing performance of MoS2 FETs both experimentally and theoretically.

Carrier scattering in quasi-free standing graphene on hexagonal boron nitride.

Graphene, a two-dimensional material with a honeycomb lattice, has been promoted as a next generation material because of its ultrafast charge carriers and superior electrical properties. Hexagonal boron nitride (h-BN) is an insulator explored as an ideal substrate for graphene with lattice-matching. Using raido-frequency (RF) transmission measurement which provides specific characteristics of carrier scattering in a device, we profoundly investigated the electrical properties of quasi-free standing graphene on h-BN. RF devices with graphene supported and encapsulated with h-BN were fabricated to analyze the RF signal at low temperatures from 100 to 300 K. We demonstrated the carrier behavior in graphene with thermally excited carriers and acoustic photon scattering according to heat energy. Both h-BN supported and encapsulated graphene showed a significant enhancement in RF transmission, which is close to a gold interconnector. Our device with graphene on h-BN exhibited concealed nonlinear characteristics at a specific temperature of 180 K due to the internal effects of acoustic phonon scattering, while a usual device with graphene on SiO2/Si provided a linear variation. To anticipate the potential for electronic applications, the electrical circuit properties such as impedance, resistance, and inductance were extracted from the results of RF measurement.

Contact Effect of ReS2/Metal Interface.

Rhenium disulfide (ReS2) has attracted immense interest as a promising two-dimensional material for optoelectronic devices owing to its outstanding photonic response based on its energy band gap's insensitivity to the layer thickness. Here, we theoretically calculated the electrical band structure of mono-, bi-, and trilayer ReS2 and experimentally found the work function to be 4.8 eV, which was shown to be independent of the layer thickness. We also evaluated the contact resistance of a ReS2 field-effect transistor using a Y-function method with various metal electrodes, including graphene. The ReS2 channel is a strong n-type semiconductor, thus a lower work function than that of metals tends to lead to a lower contact resistance. Moreover, the graphene electrodes, which were not chemically or physically bonded to ReS2, showed the lowest contact resistance, regardless of the work function, suggesting a significant Fermi-level pinning effect at the ReS2/metal interface. In addition, an asymmetric Schottky diode device was demonstrated using Ti or graphene for ohmic contacts and Pt or Pd for Schottky contacts. The ReS2-based transistor used in this study on the work function of ReS2 achieved the possibility of designing the next-generation nanologic devices.