Remote-Controllable Interfacial Electron Tunneling at Heterogeneous Molecular Junctions via Tip-Induced Optoelectrical Engineering.

Molecular electronics enables functional electronic behavior via single molecules or molecular self-assembled monolayers, providing versatile opportunities for hybrid molecular-scale electronic devices. Although various molecular junction structures are constructed to investigate charge transfer dynamics, significant challenges remain in terms of interfacial charging effects and far-field background signals, which dominantly block the optoelectrical observation of interfacial charge transfer dynamics. Here, tip-induced optoelectrical engineering is presented that synergistically correlates photo-induced force microscopy and Kelvin probe force microscopy to remotely control and probe the interfacial charge transfer dynamics with sub-10 nm spatial resolution. Based on this approach, the optoelectrical origin of metal-molecule interfaces is clearly revealed by the nanoscale heterogeneity of the tip-sample interaction and optoelectrical reactivity, which theoretically aligned with density functional theory calculations. For a practical device-scale demonstration of tip-induced optoelectrical engineering, interfacial tunneling is remotely controlled at a 4-inch wafer-scale metal-insulator-metal capacitor, facilitating a 5.211-fold current amplification with the tip-induced electrical field. In conclusion, tip-induced optoelectrical engineering provides a novel strategy to comprehensively understand interfacial charge transfer dynamics and a non-destructive tunneling control platform that enables real-time and real-space investigation of ultrathin hybrid molecular systems.

Activation of nitrogen species mixed with Ar and H2S plasma for directly N-doped TMD films synthesis.

Among the transition metal dichalcogenides (TMD), tungsten disulfide (WS2) and molybdenum disulfide (MoS2) are promising sulfides for replacing noble metals in the hydrogen evolution reaction (HER) owing to their abundance and good catalytic activity. However, the catalytic activity is derived from the edge sites of WS2 and MoS2, while their basal planes are inert. We propose a novel process for N-doped TMD synthesis for advanced HER using N2 + Ar + H2S plasma. The high ionization energy of Ar gas enabled nitrogen species activation results in efficient N-doping of TMD (named In situ-MoS2 and In situ-WS2). In situ-MoS2 and WS2 were characterized by various techniques (Raman spectroscopy, XPS, HR-TEM, TOF-SIMS, and OES), confirming nanocrystalline and N-doping. The N-doped TMD were used as electrocatalysts for the HER, with overpotentials of 294 mV (In situ-MoS2) and 298 mV (In situ-WS2) at a current density of 10 mA cm-2, which are lower than those of pristine MoS2 and WS2, respectively. Density functional theory (DFT) calculations were conducted for the hydrogen Gibbs energy (∆GH) to investigate the effect of N doping on the HER activity. Mixed gas plasma proposes a facile and novel fabrication process for direct N doping on TMD as a suitable HER electrocatalyst.

Photo-oxidative degradation of polyacids derived ceria nanoparticle modulation for chemical mechanical polishing.

The effects of photo-oxidative degradation of polyacids at various concentrations and with different durations of ultraviolet (UV) irradiation on the photo-reduction of ceria nanoparticles were investigated. The effect of UV-treated ceria on the performance of chemical mechanical polishing (CMP) for the dielectric layer was also evaluated. When the polyacids were exposed to UV light, they underwent photo-oxidation with consumption of the dissolved oxygen in slurry. UV-treated ceria particles formed oxygen vacancies by absorbing photon energy, resulting in increased Ce3+ ions concentration on the surface, and when the oxygen level of the solution was lowered by the photo-oxidation of polymers, the formation of Ce3+ ions was promoted from 14.2 to 36.5%. Furthermore, chain scissions of polymers occurred during the oxidation process, and polyacids with lower molecular weights were found to be effective in ceria particle dispersion in terms of the decrease in the mean diameter and size distribution maintaining under 0.1 of polydispersity index. With increasing polyacid concentration and UV irradiation time, the Ce3+ concentration and the dispersity of ceria both increased due to the photo-oxidative degradation of the polymer; this enhanced the CMP performance in terms of 87% improved material removal rate and 48% lowered wafer surface roughness.

Energy-Band Engineering by Remote Doping of Self-Assembled Monolayers Leads to High-Performance IGZO/p-Si Heterostructure Photodetectors.

Metal oxide semiconductors are of great interest for enabling advanced photodetectors. However, operational instability and the absence of an appropriate doping technique hinder practical development and commercialization. Here, a strategy is proposed to dramatically increase the conventional photodetection performance, having superior stability in operational and environmental atmospheres. By performing energy-band engineering through an octadecylphosphonic acid (ODPA) self-assembled-monolayer-based doping treatment, the proposed indium-gallium-zinc oxide (IGZO)/p-Si heterointerface devices exhibit greatly enhance the photoresponsive characteristics, including a photoswitching current ratio with a 100-fold increase, and photoresponsivity and detectivity with a 15-fold increase each. The observed ODPA doping effects are investigated through comprehensive analysis with X-ray photoelectron spectroscopy (XPS), atomic force microscopy (AFM), and Kelvin probe force microscopy (KPFM). Furthermore, the proposed photodetectors, fabricated at a 4 in. wafer scale, demonstrate its excellent operation robustness with consistent performance over 237 days and 20 000 testing cycles.

Synthesis of vertically aligned wafer-scale tantalum disulfide using high-Ar/H2S ratio plasma.

Nanostructural modification of two-dimensional (2D) materials has attracted significant attention for enhancing hydrogen evolution reaction (HER) activity. In this study, the nanostructure of TaS2films was controlled by controlling the Ar/H2S gas ratio used in plasma-enhanced chemical vapor deposition (PECVD). At a high Ar/H2S gas ratio, vertically aligned TaS2(V-TaS2) films were formed over a large-area (4 in) at a temperature of 250 °C, which, to the best of our knowledge, is the lowest temperature reported for PECVD. Furthermore, the plasma species formed in the injected gas at various Ar/H2S gas ratios were analyzed using optical emission spectroscopy to determine the synthesis mechanism. In addition, the 4 in wafer-scale V-TaS2was analyzed by x-ray photoelectron spectroscopy, transmission electron microscopy, and atomic force microscopy, and the HER performance of the as-synthesized TaS2fabricated with various Ar/H2S ratios was measured. The results revealed that, depending on the film structure of TaS2, the HER performance can be enhanced owing to its structural advantage. Furthermore, the excellent stability and robustness of V-TaS2was confirmed by conducting 1000 HER cycles and post-HER material characterization. This study provides important insights into the plasma-assisted nanostructural modification of 2D materials for application as enhanced electrocatalysts.

High-Temperature Skin Softening Materials Overcoming the Trade-Off between Thermal Conductivity and Thermal Contact Resistance.

The trade-off between thermal conductivity (κ) and thermal contact resistance (Rc ) is regarded as a hurdle to develop superior interface materials for thermal management. Here a high-temperature skin softening material to overcome the trade-off relationship, realizing a record-high total thermal conductance (254.92 mW mm-2 K-1 ) for isotropic pad-type interface materials is introduced. A highly conductive hard core is constructed by incorporating Ag flakes and silver nanoparticle-decorated multiwalled carbon nanotubes in thermosetting epoxy (EP). The thin soft skin is composed of filler-embedded thermoplastic poly(ethylene-co-vinyl acetate) (PEVA). The κ (82.8 W m-1 K-1 ) of the PEVA-EP-PEVA interface material is only slightly compromised, compared with that (106.5 W m-1 K-1 ) of the EP core (386 µm). However, the elastic modulus (E = 2.10 GPa) at the skin is significantly smaller than the EP (26.28 GPa), enhancing conformality and decreasing Rc from 108.41 to 78.73 mm2 K W-1 . The thermoplastic skin is further softened at an elevated temperature (100 °C), dramatically decreasing E (0.19 GPa) and Rc (0.17 mm2 K W-1 ) with little change in κ, overcoming the trade-off relationship and enhancing the total thermal conductance by 2030%. The successful heat dissipation and applicability to the continuous manufacturing process demonstrate excellent feasibility as future thermal management materials.

Deletion analysis of LSm, FDF, and YjeF domains of Candida albicans Edc3 in hyphal growth and oxidative-stress response.

Candida albicans is an opportunistic fungal pathogen whose responses to environmental changes are associated with the virulence attributes. Edc3 is known to be an enhancer of the mRNA decapping reactions and a scaffold protein of cytoplasmic processing bodies (P-bodies). Recent studies of C. albicans Edc3 suggested its critical roles in filamentous growth and stress-induced apoptotic cell death. The edc3/edc3 deletion mutant strain showed increased cell survival and less ROS accumulation upon treatment with hydrogen peroxide. To investigate the diverse involvement of Edc3 in the cellular processes, deletion mutations of LSm, FDF, or YjeF domain of Edc3 were constructed. The edc3-LSmΔ or edc3-YjeFΔ mutation showed the filamentation defect, resistance to oxidative stress, and decreased ROS accumulation. In contrast, the edc3-FDFΔ mutation exhibited a wild-type level of filamentous growth and a mild defect in ROS accumulation. These results suggest that Lsm and YjeF domains of Edc3 are critical in hyphal growth and oxidative stress response.