Low-energy argon ion bombardment-induced decomposition of physisorbed hydrofluorocarbons on silicon nitride surfaces: A computational mechanistic study.

Using a combination of tight binding molecular dynamics and ab initio molecular dynamics simulations, we study the mechanisms of bombardment-induced decomposition of hydrofluorocarbons (HFCs) physisorbed on silicon nitride for ion energies of ≤35 eV. We propose three key mechanisms by which bombardment-driven HFC decomposition can occur, focusing on the two pathways observed at these low ion energies: "direct decomposition" and "collision assisted surface reactions (CASRs)." Our simulation results clearly demonstrate the importance of the presence of favorable reaction coordinates for enabling CASR, which dominates at lower energies (≈11 eV). At higher energies, direct decomposition becomes more favored. Our work also predicts that the primary decomposition pathways for CH3F and CF4 are CH3F → CH3 + F and CF4 → CF2 + 2F, respectively. The fundamental details of these decomposition pathways and the decomposition products formed under ion bombardment have implications for plasma-enhanced atomic layer etching process design that will be discussed.

Synthetic Control of Intrinsic Defect Formation in Metal Oxide Nanocrystals Using Dissociated Spectator Metal Salts.

Crystallographic defects are essential to the functional properties of semiconductors, controlling everything from conductivity to optical properties and catalytic activity. In nanocrystals, too, defect engineering with extrinsic dopants has been fruitful. Although intrinsic defects like vacancies can be equally useful, synthetic strategies for controlling their generation are comparatively underdeveloped. Here, we show that intrinsic defect concentration can be tuned during the synthesis of colloidal metal oxide nanocrystals by the addition of metal salts. Although not incorporated in the nanocrystals, the metal salts dissociate at high temperatures, promoting the dissociation of carboxylate ligands from metal precursors, leading to the introduction of oxygen vacancies. For example, the concentration of oxygen vacancies can be controlled up to 9% in indium oxide nanocrystals. This method is broadly applicable as we demonstrate by generating intrinsic defects in metal oxide nanocrystals of various morphologies and compositions.

First-principles prediction on antimony-doping effects on the cyclic stability of tin anodes for lithium-ion batteries.

Tin-based materials are considered as promising anode materials for advanced Li-ion batteries (LIBs) due to their relatively high capacity and suitable working voltage, but they suffer from poor structural stability during electrochemical cycling. Herein, we present the possibility that the cyclic stability of the Sn LIB anode can be enhanced by adding a small amount of antimony (Sb), based on first-principles investigation of lithiation behavior of amorphous Sn doped with 3 at% Sb. At low Li contents (x < 1.5 in a-LixSn0.97Sb0.03), our simulations show that the preferential reaction of Li with Sb over Sn tends to lead to the formation of small lithiated Sb clusters. However, the aggregated Sb, if any, become fully separated upon further lithiation, implying that they may remain well dispersed in the lithiation/delithiation process if the Sb-doping concentration is sufficiently low. The weak aggregation and preferential lithiation tendency of Sb in the Sb-doped Sn anode can be expected to contribute to enhancing its structural stability during cycling, in comparison with pure Sn and SnSb alloy cases. We also compare lithiation-induced changes in the electrochemical, transport and mechanical properties between the Sb-doped and pure Sn systems. Our study highlights the importance of low concentration and uniform distribution of Sb in order to obtain desired properties of Sb-doped Sn as an anode for LIBs. This finding also provides some hints for the further development of Sn-based anodes via fine-tuning of doping.

On the mechanism of predominant urea formation from thermal degradation of CO2-loaded aqueous ethylenediamine.

This study attempts to explain the well-known experimental observation that 1,3-bis(2-aminoethyl)urea (urea) is preferentially formed over the other major product, 2-imidazolidone (IZD), from thermal degradation of aqueous ethylenediamine (EDA) during the CO2 capture process. This is in direct contrast to the case of monoethanolamine (MEA), preferentially forming oxazolidinone (OZD), rather than urea, which undergoes further reactions leading to more stable products. Given their similar molecular structures, the different preferred degradation pathways of EDA and MEA impose an intriguing question regarding the underlying mechanism responsible for the distinct difference. Thermal degradation of both EDA and MEA tends to proceed mainly via formation of an isocyanate intermediate that may further undergo either cyclization to IZD (or OZD) or a reaction with EDA (or MEA) forming urea. For the EDA case, our first-principles simulations clearly demonstrate that the urea formation reaction is kinetically more, but thermodynamically less, favorable than the cyclization reaction; the opposite is true for the MEA case. Our further analysis shows that EDA-isocyanate is less prone to cyclization than MEA-isocyanate, which in turn allows for more facile urea formation. The reconfiguration dynamics of isocyanate is found to be governed by the dynamic nature of the interaction between its terminal group and surrounding solvent molecules. Our work highlights the importance of kinetic effects associated with the local structure and dynamics of solvent molecules around the intermediates that may significantly alter the degradation process of amine solvents.

First-principles description of electrocatalytic characteristics of graphene-like materials.

Graphene-like materials (GLMs) have received much attention as a potential alternative to precious metal-based electrocatalysts. However, the description of their electrocatalytic characteristics may still need to be improved, especially under constant chemical potential. Unlike the case of conventional metal electrodes, the potential drop across the electrical double layer (ϕD) at the electrode-electrolyte interface can deviate substantially from the applied voltage (ϕapp) due to a shift of the Dirac point (eϕG) with charging. This may in turn significantly alter the interfacial capacitance (CT) and the relationship between ϕapp and free-energy change (ΔF). Hence, accurate evaluation of the electrode contribution is necessary to better understand and optimize the electrocatalytic properties of GLMs. In this work, we revisit and compare first-principles methods available to describe the ϕapp-∆F relation. Grand-canonical density functional theory is used to determine ΔF as a function of ϕapp or electrode potential (ϕq), from which the relative contribution of eϕG is estimated. In parallel, eϕG is directly extracted from a density functional theory analysis of the electronic structure of uncharged GLMs. The results of both methods are found to be in close agreement for pristine graphene, but their predictions deviate noticeably in the presence of adsorbates; the origin of the discrepancy is analyzed and explained. We then evaluate the application of the first-principle methods to prediction of the electrocatalytic processes, taking the reduction (hydrogenation) and oxidation (hydroxylation) reactions on pristine graphene as examples. Our work highlights the vital role of the modification of the electrode electronic structure in determining the electrocatalytic performance of GLMs.

Partial oxidation of methane to methanol by isolated Pt catalyst supported on a CeO2 nanoparticle.

Catalytic transformation of methane (CH4) into methanol in a single step is a challenging issue for the utilization of CH4. We present a direct method for converting CH4 into methanol with high selectivity over a Pt/CeO2 catalyst which contains ionic Pt2+ species supported on a CeO2 nanoparticle. The Pt/CeO2 catalyst reproducibly yielded 6.27 mmol/g of Pt with a selectivity of over 95% at 300 °C when CH4 and CO are used as reactants, while the catalyst had a lower activity when using only CH4 without CO. Active lattice oxygen created on the Pt and CeO2 interface provides selective reaction pathways for the conversion of CH4 to methanol. Based on high-angle annular dark-field scanning transmission electron microscopy, x-ray photoelectron spectroscopy, x-ray absorption near-edge structure, extended x-ray absorption fine structure, catalytic studies, and density functional theory calculations, we propose a mechanistic pathway involving CH4 activation at the active site in the vicinity of Pt2+ species.

Molecular dynamics investigation of reduced ethylene carbonate aggregation at the onset of solid electrolyte interphase formation.

Formation of the solid electrolyte interphase (SEI) at the anode surface during the initial charge cycles is critical to lithium ion battery operability. Reduction of electrolyte components must ultimately result in the formation of this ionically conducting and electronically insulating layer to compensate for the limited electrochemical stability window of conventional liquid electrolytes. One important reaction in SEI formation is the bimolecular combination of radical anions to form more stable products. Molecular dynamics simulations illustrate the nature and dynamics of the intermolecular interactions between the reactive intermediates produced from one-electron reduction in ethylene carbonate-based electrolytes. A clear concentration dependence is shown for this interaction, and its ramifications for SEI formation are discussed.

Molecular mechanisms for thermal degradation of CO2-loaded aqueous monoethanolamine solution: a first-principles study.

Thermal degradation of aqueous monoethanolamine (MEA), a benchmark solvent, in CO2 capture processes still remains a challenge. Here, we present molecular mechanisms underlying thermal degradation of MEA based on ab initio molecular dynamics simulations coupled with metadynamics sampling. Isocyanate formation via dehydration of carbamic acid (MEACOOH) is predicted to be highly probable and more kinetically favorable than the competing cyclization-dehydration reaction to 2-oxazolidinone (OZD), albeit not substantially. Isocyanate may undergo cyclization to form OZD, which is found to be more facile in aqueous MEA solution than reaction with MEA to form urea, although the latter is thermodynamically more favorable than the former. Our simulations also clearly demonstrate that OZD is a long-lived intermediate that plays a key role in MEA thermal degradation to experimentally observed products. Overall, this work highlights the importance of entropic contributions associated with the local structure and dynamics of solvent molecules around the intermediates, which cannot be solely explained by thermodynamics, in predicting the mechanism and kinetics of thermal degradation of CO2-loaded aqueous amine solutions.

Theoretical evaluation of thermal decomposition of dichlorosilane for plasma-enhanced atomic layer deposition of silicon nitride: the important role of surface hydrogen.

Silicon nitride (SiN) thin films have been widely employed for various applications including microelectronics, but their deposition presents a challenge especially when highly conformal layers are necessary on nanoscale features with high aspect ratios. Plasma-enhanced atomic layer deposition (PEALD) has been demonstrated to be a promising technique for controlled growth of SiN thin films at relatively low temperatures (<400 °C), in which thermal decomposition of Si-containing precursors on a N-rich surface is a critical step. Based on periodic density functional theory calculations, we present potential underlying mechanisms leading to facile thermal decomposition of dichlorosilane (DCS, SiH2Cl2) on the N-rich ß-Si3N4(0001) surface. Our study highlights the importance of high hydrogen content on the N-rich surface, rendering primary and secondary amine groups. When the N-rich ß-Si3N4(0001) surface is fully hydrogenated, the molecular adsorption of DCS is predicted to be exothermic by 0.6 eV. In this case, DCS decomposition appears to be initiated by nucleophilic attack by an amine lone-pair on the electrophilic Si, leading to the formation of a DCS-amine adduct intermediate followed by release of a Cl- anion and a proton. The predicted activation barrier for the DCS decomposition reaction is only 0.3 eV or less, depending on its adsorption configuration. We also discuss the formation and desorption of HCl, the subsequent formation and nature of Si-N bonds, and the interaction between adsorbed DCS molecules. While clearly demonstrating the advantageous features of DCS as a Si precursor, this work suggests that the thermal decomposition of Si precursors, and in turn the ALD kinetics and resulting film quality, can be strongly influenced by surface functional groups, in addition to product accumulation and precursor coverage.

Controlling Plasmon-Enhanced Fluorescence via Intersystem Crossing in Photoswitchable Molecules.

By harnessing photoswitchable intersystem crossing (ISC) in spiropyran (SP) molecules, active control of plasmon-enhanced fluorescence in the hybrid systems of SP molecules and plasmonic nanostructures is achieved. Specifically, SP-derived merocyanine (MC) molecules formed by photochemical ring-opening reaction display efficient ISC due to their zwitterionic character. In contrast, ISC in quinoidal MC molecules formed by thermal ring-opening reaction is negligible. The high ISC rate can improve fluorescence quantum yield of the plasmon-modified spontaneous emission, only when the plasmonic electromagnetic field enhancement is sufficiently high. Along this line, extensive photomodulation of fluorescence is demonstrated by switching the ISC in MC molecules at Au nanoparticle aggregates, where strongly enhanced plasmonic hot spots exist. The ISC-mediated plasmon-enhanced fluorescence represents a new approach toward controlling the spontaneous emission of fluorophores near plasmonic nanostructures, which expands the applications of active molecular plasmonics in information processing, biosensing, and bioimaging.

Molecular insights into the enhanced rate of CO2 absorption to produce bicarbonate in aqueous 2-amino-2-methyl-1-propanol.

2-Amino-2-methyl-1-propanol (AMP), a sterically hindered amine, exhibits a much higher CO2 absorption rate relative to tertiary amine diethylethanolamine (DEEA), while both yield bicarbonate as a major product in aqueous solution, despite their similar basicity. We present molecular mechanisms underlying the significant difference of CO2 absorption rate based on ab initio molecular dynamics simulations combined with metadynamics. Our calculations predict the free energy barrier for base-catalyzed CO2 hydration to be lower in aqueous AMP compared to DEEA. Further molecular analysis suggests that the difference in free energy barrier is largely attributed to entropic effects associated with reorganization of H2O molecules adjacent to the basic N site. Stronger hydrogen bonding of H2O with N of DEEA than AMP, in addition to the presence of bulky ethyl groups, suppresses the thermal rearrangement of adjacent H2O molecules, thereby leading to lower stability of the transition state involving OH- creation and CO2 polarization. Moreover, the hindered reorganization of adjacent H2O molecules is found to facilitate migration of OH- (created via proton abstraction by DEEA) away from the N site while suppressing CO2 approach. This leads us to speculate that catalyzed CO2 hydration in aqueous DEEA may involve OH- migration through multiple hydrogen-bonded H2O molecules prior to reaction with CO2, whereas in aqueous AMP it seems to preferentially follow the one H2O-mediated mechanism. This study highlights the importance of entropic effects in determining both mechanisms and rates of CO2 absorption into aqueous sterically hindered amines.

Understanding CO2 capture mechanisms in aqueous hydrazine via combined NMR and first-principles studies.

Aqueous amines are currently the most promising solution for large-scale CO2 capture from industrial sources. However, molecular design and optimization of amine-based solvents have proceeded slowly due to a lack of understanding of the underlying reaction mechanisms. Unique and unexpected reaction mechanisms involved in CO2 absorption into aqueous hydrazine are identified using 1H, 13C, and 15N NMR spectroscopy combined with first-principles quantum-mechanical simulations. We find production of both hydrazine mono-carbamate (NH2-NH-COO-) and hydrazine di-carbamate (-OOC-NH-NH-COO-), with the latter becoming more populated with increasing CO2 loading. Exchange NMR spectroscopy also demonstrates that the reaction products are in dynamic equilibrium under ambient conditions due to CO2 exchange between mono-carbamate and di-carbamate as well as fast proton transfer between un-protonated free hydrazine and mono-carbamate. The exchange rate rises steeply at high CO2 loadings, enhancing CO2 release, which appears to be a unique property of hydrazine in aqueous solution. The underlying mechanisms of these processes are further evaluated using quantum mechanical calculations. We also analyze and discuss reversible precipitation of carbamate and conversion of bicarbonate to carbamates. The comprehensive mechanistic study provides useful guidance for optimal design of amine-based solvents and processes to reduce the cost of carbon capture. Moreover, this work demonstrates the value of a combined experimental and computational approach for exploring the complex reaction dynamics of CO2 in aqueous amines.

The Bright Future for Electrode Materials of Energy Devices: Highly Conductive Porous Na-Embedded Carbon.

High electrical conductivity and large accessible surface area, which are required for ideal electrode materials of energy conversion and storage devices, are opposed to each other in current materials. It is a long-term goal to solve this issue. Herein, we report highly conductive porous Na-embedded carbon (Na@C) nanowalls with large surface areas, which have been synthesized by an invented reaction of CO with liquid Na. Their electrical conductivities are 2 orders of magnitude larger than highly conductive 3D graphene. Furthermore, almost all their surface areas are accessible for electrolyte ions. These unique properties make them ideal electrode materials for energy devices, which significantly surpass expensive Pt. Consequently, the dye-sensitized solar cells (DSSCs) with the Na@C counter electrode has reached a high power conversion efficiency of 11.03%. The Na@C also exhibited excellent performance for supercapacitors, leading to high capacitance of 145 F g-1 at current density of 1 A g-1.

What is the thermal conductivity limit of silicon germanium alloys?

The lowest possible thermal conductivity of silicon-germanium (SiGe) bulk alloys achievable through alloy scattering, or the so-called alloy limit, is important to identify for thermoelectric applications. However, this limit remains a subject of contention as both experimentally-reported and theoretically-predicted values tend to be widely scattered and inconclusive. In this work, we present a possible explanation for these discrepancies by demonstrating that the thermal conductivity can vary significantly depending on the degree of randomness in the spatial arrangement of the constituent atoms. Our study suggests that the available experimental data, obtained from alloy samples synthesized using ball-milling techniques, and previous first-principles calculations, restricted by small supercell sizes, may not have accessed the alloy limit. We find that low-frequency anharmonic phonon modes can persist unless the spatial distribution of Si and Ge atoms is completely random at the atomic scale, in which case the lowest possible thermal conductivity may be achieved. Our theoretical analysis predicts that the alloy limit of SiGe could be around 1-2 W m(-1) K(-1) with an optimal composition around 25 at% Ge, which is substantially lower than previously reported values from experiments and first-principles calculations.

First-principles assessment of CO2 capture mechanisms in aqueous piperazine solution.

Piperazine (PZ) and its blends have emerged as attractive solvents for CO2 capture, but the underlying reaction mechanisms still remain uncertain. Our study particularly focuses on assessing the relative roles of PZCOO- and PZH+ produced from the PZ + CO2 reaction. PZCOO- is found to directly react with CO2 forming COO-PZCOO-, whereas PZH+ will not. However, COO-PZCOO- appears very unlikely to be produced in thermodynamic equilibrium with monocarbamates, suggesting that its existence would predominantly originate from the surface reaction that likely occurs. We also find production of H+PZCOO- to be more probable with increasing CO2 loading, due partly to the thermodynamic favorability of the PZH+ + PZCOO- → H+PZCOO- + PZ reaction; the facile PZ liberation may contribute to its relatively high CO2 absorption rate. This study highlights an accurate description of surface reaction and the solvent composition effect is critical in thermodynamic and kinetic models for predicting the CO2 capture processes.

Structure and Li+ ion transport in a mixed carbonate/LiPF6 electrolyte near graphite electrode surfaces: a molecular dynamics study.

Electrolyte and electrode materials used in lithium-ion batteries have been studied separately to a great extent, however the structural and dynamical properties of the electrolyte-electrode interface still remain largely unexplored despite its critical role in governing battery performance. Using molecular dynamics simulations, we examine the structural reorganization of solvent molecules (cyclic ethylene carbonate : linear dimethyl carbonate 1 : 1 molar ratio doped with 1 M LiPF6) in the vicinity of graphite electrodes with varying surface charge densities (σ). The interfacial structure is found to be sensitive to the molecular geometry and polarity of each solvent molecule as well as the surface structure and charge distribution of the negative electrode. We also evaluated the potential difference across the electrolyte-electrode interface, which exhibits a nearly linear variation with respect to σ up until the onset of Li+ ion accumulation onto the graphite edges from the electrolyte. In addition, well-tempered metadynamics simulations are employed to predict the free-energy barriers to Li+ ion transport through the relatively dense interfacial layer, along with analysis of the Li+ solvation sheath structure. Quantitative analysis of the molecular arrangements at the electrolyte-electrode interface will help better understand and describe electrolyte decomposition, especially in the early stages of solid-electrolyte-interphase (SEI) formation. Moreover, the computational framework presented in this work offers a means to explore the effects of solvent composition, electrode surface modification, and operating temperature on the interfacial structure and properties, which may further assist in efforts to engineer the electrolyte-electrode interface leading to a SEI layer that optimizes battery performance.

Thickness-Dependent Dielectric Constant of Few-Layer In2Se3 Nanoflakes.

The dielectric constant or relative permittivity (ε(r)) of a dielectric material, which describes how the net electric field in the medium is reduced with respect to the external field, is a parameter of critical importance for charging and screening in electronic devices. Such a fundamental material property is intimately related to not only the polarizability of individual atoms but also the specific atomic arrangement in the crystal lattice. In this Letter, we present both experimental and theoretical investigations on the dielectric constant of few-layer In2Se3 nanoflakes grown on mica substrates by van der Waals epitaxy. A nondestructive microwave impedance microscope is employed to simultaneously quantify the number of layers and local electrical properties. The measured ε(r) increases monotonically as a function of the thickness and saturates to the bulk value at around 6-8 quintuple layers. The same trend of layer-dependent dielectric constant is also revealed by first-principles calculations. Our results of the dielectric response, being ubiquitously applicable to layered 2D semiconductors, are expected to be significant for this vibrant research field.

On the origin of preferred bicarbonate production from carbon dioxide (CO2) capture in aqueous 2-amino-2-methyl-1-propanol (AMP).

AMP and its blends are an attractive solvent for CO2 capture, but the underlying reaction mechanisms still remain uncertain. We attempt to elucidate the factors enhancing bicarbonate production in aqueous AMP as compared to MEA which, like most other primary amines, preferentially forms carbamate. According to our predicted reaction energies, AMP and MEA exhibit similar thermodynamic favorability for bicarbonate versus carbamate formation; moreover, the conversion of carbamate to bicarbonate also does not appear more favorable kinetically in aqueous AMP compared to MEA. Ab initio molecular dynamics simulations, however, demonstrate that bicarbonate formation tends to be kinetically more probable in aqueous AMP while carbamate is more likely to form in aqueous MEA. Analysis of the solvation structure and dynamics shows that the enhanced interaction between N and H2O may hinder CO2 accessibility while facilitating the AMP + H2O → AMPH(+) + OH(-) reaction, relative to the MEA case. This study highlights the importance of not only thermodynamic but also kinetic factors in describing CO2 capture by aqueous amines.

Reaction mechanisms of aqueous monoethanolamine with carbon dioxide: a combined quantum chemical and molecular dynamics study.

Aqueous monoethanolamine (MEA) has been extensively studied as a solvent for CO2 capture, yet the underlying reaction mechanisms are still not fully understood. Combined ab initio and classical molecular dynamics simulations were performed to revisit and identify key elementary reactions and intermediates in 25-30 wt% aqueous MEA with CO2, by explicitly taking into account the structural and dynamic effects. Using static quantum chemical calculations, we also analyzed in more detail the fundamental interactions involved in the MEA-CO2 reaction. We find that both the CO2 capture by MEA and solvent regeneration follow a zwitterion-mediated two-step mechanism; from the zwitterionic intermediate, the relative probability between deprotonation (carbamate formation) and CO2 removal (MEA regeneration) tends to be determined largely by the interaction between the zwitterion and neighboring H2O molecules. In addition, our calculations clearly demonstrate that proton transfer in the MEA-CO2-H2O solution primarily occurs through H-bonded water bridges, and thus the availability and arrangement of H2O molecules also directly impacts the protonation and/or deprotonation of MEA and its derivatives. This improved understanding should contribute to developing more comprehensive kinetic models for use in modeling and optimizing the CO2 capture process. Moreover, this work highlights the importance of a detailed atomic-level description of the solution structure and dynamics in order to better understand molecular mechanisms underlying the reaction of CO2 with aqueous amines.

Electron small polarons and their transport in bismuth vanadate: a first principles study.

Relatively low electron mobility has been thought to be a key factor that limits the overall photocatalytic performance of BiVO4, but the behavior of electrons has not been fully elucidated. We examine electron localization and transport in BiVO4 using hybrid density functional theory calculations. An excess electron is found to remain largely localized on one V atom. The predicted hopping barrier for the small polaron is 0.35 eV (with inclusion of 15% Hartree-Fock exchange), and tends to increase almost linearly with lattice constant associated with pressure and/or temperature changes. We also examine the interaction between polarons, and discuss the possible concentration-dependence of electron mobility in BiVO4.