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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. [ABSTRACT FROM AUTHOR]

Nanostructural modification of two-dimensional (2D) materials has attracted significant attention for enhancing hydrogen evolution reaction (HER) activity. In this study, the nanostructure of TaS2 films 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-TaS2 was analyzed by x-ray photoelectron spectroscopy, transmission electron microscopy, and atomic force microscopy, and the HER performance of the as-synthesized TaS2 fabricated 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-TaS2 was 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. [ABSTRACT FROM AUTHOR]

The influence of controlled phase shift between very high frequency (100 MHz) voltages applied to the powered electrodes on the plasma uniformity and etch rate was studied in a capacitive triode-type reactor. Radial profiles of plasma optical emission were measured as a function of the phase shift in process (C4F8/O2/Ar) plasma with the low frequency bias power both turned off and on. Radial profiles of KrF photoresist etch rate over a 300 mm wafer were obtained in the same conditions (with the bias power turned on). Besides, plasma density at the wafer center and edge was measured versus the phase shift in pure Ar plasma. It occurred that all measured characteristics strongly depend on the phase shift and correlate with each other. It has been shown that the phase-shift control can considerably improve both the plasma and etch-rate uniformity in very high-frequency capacitive reactors. [ABSTRACT FROM AUTHOR]

Atomic layer etching (ALE) is an alternative method for nanopatterning in which atomic layers of material are removed by sequential self-limiting surface reactions. In this study, the authors report a new cyclic process for atomic layer etching of Si3N4 films achieved by alternating exposure steps of CH3F gas adsorption and Ar+ bombardment. Self-limiting etching characteristics of the ALE process are demonstrated as a function of both CH3F etchant flow rate and CH3F exposure time. From comparative studies on the amount of Si3N4 etched using the ALE mode versus pure Ar+ ion sputtering, it is found that the ALE process operates with an ALE synergy factor of ∼67% and also removes Si3N4 with better uniformity due to cooperative interactions between the self-limited CH3F chemisorption and the Ar+ ion sputtering. Based on both the chemical bonding changes following the CH3F etchant exposure and reaction product analyses during the Ar+ plasma step, possible etch reaction steps for the ALE Si3N4 process are proposed. [ABSTRACT FROM AUTHOR]

The signals of positive ions and radicals formed in the fluorocarbon plasma of the capacitively coupled plasma reactor were measured using a quadrupole mass spectrometry and optical emission actinometry. The plasma was produced at 60 and 100 MHz frequencies for the same reactor configuration and gas mixtures. Experiments were performed at 25 mTorr with a SiO2 wafer on the grounded electrode. Mass spectra of ions were measured in C4F8/O2/Ar and C4F6/O2/Ar gas mixtures at 500–1500 W generator powers. For 60 and 100 MHz discharges production of fluorocarbon ions and radicals is discussed. It was found that the production of heavy species increases with frequency. The high mass signals such as C3F3+, C2F4+, C2F5+, C3F5+, C4F7+ decrease when CHF3 is added to the gas mixture. However, the signals of CFx+ (x=1,2,3) do not change significantly. These results are compared to the results of polymer film deposition on the wafer. It was suggested to control the polymerization film formation by adding small amount of CHF3 to the process mixture. [ABSTRACT FROM AUTHOR]