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In this work, first principles calculations combined with advanced surface diagnostics are used to unravel the mechanisms of plasma oxygen interaction with organic films of interest for advanced patterning in semiconductor device manufacturing. Results from a combination of x-ray photoelectron spectroscopy (XPS) diagnosed oxygen plasma exposed polystyrene films and first principles modeling of organic films (polystyrene, polyethylene, and derivatives) provide insights into how organic films are oxidized by oxygen atoms. XPS measurements show the rapid formation of C-O structures and their saturation after oxygen exposure on both pristine and argon bombarded polystyrene samples. Quantum mechanics calculations confirm that C-OH formation can be immediate without recourse to previously formed dangling bonds. Multiple oxygen impacts are required for scission of pristine ethylene carbon strands. Therefore, ethylene films can be converted to polyols that are stable, whereas more likely strands are broken before polyol formation through the formation of water and C=O. On the contrary, intermediate compounds with adjacent C=O bonds are not likely to form stable structures. The combination of XPS measurements and modeling implies that the oxidation of polystyrene and polyethylene is self-limiting on both hydrogen saturated and dehydrogenated (after argon ion plasma bombardment) surfaces. [ABSTRACT FROM AUTHOR]

Lithium-sulfur batteries show remarkable potential for energy storage applications due to their high-specific capacity and the low cost of active materials, especially sulfur. However, whereas there is a consensus about the use of lithium metal as the negative electrode, there is not a clear and widely accepted architectural design for the positive electrode of sulfur batteries. The difficulties arise when trying to find a balance between high-surface-area architectures and practical utilization of the sulfur content. Intensive understanding of the interfacial mechanisms becomes then crucial to design optimized carbon-hosted sulfur architectures with enhanced electrochemical performance. In this work, we use density functional theory (DFT)-based first principles calculations to describe and characterize the growing mechanisms of Li2S active material on graphene, taken as an example of a nonencapsulated carbon host for the positive electrode of Li-S batteries. We first unravel the two growing mechanisms of Li2S supported nanostructures, which explain recent experimental findings on real-time monitoring of interfacial deposition of lithium sulfides during discharge, obtained by means of in situ atomic force microscopy. Then, using a combination of mathematical tools and DFT calculations, we obtain the first cycle voltage plot, explaining the three different regions observed that ultimately lead to the formation of high-order polysulfides upon charge. Finally, we show how the different Li2S supported nanostructures can be characterized in X-ray photoelectron spectroscopy measurements. Altogether, this work provides useful insights for the rational design of new carbon-hosted sulfur architectures with optimized characteristics for the positive electrode of lithium-sulfur batteries. [ABSTRACT FROM AUTHOR]

In this work, surface oxidation of monolayer MoS2 (one of the representative semiconductors in transition-metal dichalcogenides) has been investigated using density functional theory method. Oxygen interaction with MoS2 shows that, thermodynamically, the surface tends to be oxidized. However, the dissociative absorption of molecular oxygen on the MoS2 surface is kinetically limited due to the large energy barrier at low temperature. This finding elucidates the air stability of MoS2 surface in the atmosphere. Furthermore, the presence of defects significantly alters the surface stability and adsorption mechanisms. The electronic properties of the oxidized surface have been examined as a function of oxygen adsorption and coverage as well as substitutional impurities. Our results on energetics and kinetics of oxygen interaction with the MoS2 monolayer are useful for the understanding of surface oxidation, air stability, and electronic properties of transition-metal dichalcogenides at the atomic scale. [ABSTRACT FROM AUTHOR]

Using ab-initio methods, atomic structures and electronic properties of InP (001)/HfO2 (001) interface are studied within the framework of density functional theory. We examine the InP/HfO2 model interface electronic structures under varying oxidation conditions. The effects of indium and phosphorous concentrations on interfacial bonding, defect states, band offsets, and the thermodynamic stability at the interface are also investigated. The origin of interfacial gap states in InP (001)/HfO2 (001) interface are proposed, mainly from the P-rich oxides, which is validated by our experimental work. This highlights the importance of surface passivation prior to high-κ deposition based on the in situ spectroscopic results of atomic layer deposition of HfO2 on InP. [ABSTRACT FROM AUTHOR]

A theoretical study of the oxidation of InP(001)-(2 × 4) surface is performed using density functional theory methods. Our results on surface oxidation show that the oxygen adsorption does not produce any gap states in the bulk InP band gap, due to the saturation of surface In dangling bonds, whereas substitutional oxygen atoms produce gap states. This study also shows that the surface stability increases with the oxygen content, indicating a strong tendency for surface oxidation. Our results help to clarify the origin of surface gap states upon surface oxidation and provide an insight at the atomic level the mechanism of surface oxidation, which will assist in the understanding of the degradation of III-V devices upon oxygen exposure or interfacial oxidation with high dielectric constant oxides. [ABSTRACT FROM AUTHOR]

Atomic substitution and doping are two of the most adopted strategies to improve the electrochemical performance of layered cathode materials for Li-ion batteries (LIBs). In this work, we report a comprehensive study on the effects of seven dopants (Al, Ga, Mg, Si, Ti, V, and Zr) on the well-known drawbacks of Ni-rich LiNi1−2yCoyMnyO2 (NCM) (y≤ 0.1), one of the most promising next-generation cathode materials for LIBs, including phase instability, Li–Ni exchange, Ni segregation, lattice distortion, and oxygen evolution. Our results show that there is not a single dopant that can solve all the problems at the same time and, moreover, while they often improve certain properties, they may have no effect or even worsen others. By comparing different doping sites, we found a strong site preference due to the tradeoff between Mn and Co concentrations. This site preference indicates that a multicomponent-doping strategy should be adopted at both Mn and Co sites. Finally, a rationale for the optimization of the overall electrochemical performance of Ni-rich NCM is proposed, which will ultimately provide practical guidance (Ti or Zr at the Co site and Al at the Mn site) for the design of new Ni-rich layered cathode materials for LIBs. [ABSTRACT FROM AUTHOR]