Prediction of glassy silica etching with hydrogen fluoride gas by kinetic Monte Carlo simulations.

Understanding the surface properties of glass during the hydrogen fluoride (HF)-based vapor etching process is essential to optimize treatment processes in semiconductor and glass industries. In this work, we investigate an etching process of fused glassy silica by HF gas with kinetic Monte Carlo (KMC) simulations. Detailed pathways of surface reactions between gas molecules and the silica surface with activation energy sets are explicitly implemented in the KMC algorithm for both dry and humid conditions. The KMC model successfully describes the etching of the silica surface with the evolution of surface morphology up to the micron regime. The simulation results show that the calculated etch rate and surface roughness are in good agreement with the experimental results, and the effect of humidity on the etch rate is also confirmed. Development of roughness is theoretically analyzed in terms of surface roughening phenomena, and it is predicted that the values of growth and roughening exponents are 0.19 and 0.33, respectively, suggesting that our model belongs to the Kardar-Parisi-Zhang universality class. Furthermore, the temporal evolution of surface chemistry, specifically surface hydroxyls and fluorine groups, is monitored. The surface density of fluorine moieties is 2.5 times higher than that of the hydroxyl groups, implying that the surface is well fluorinated during vapor etching.

Passivation of Mid-Gap Electronic States at Calcium Aluminosilicate Glass Surfaces upon Water Exposure: An Ab Initio Study.

When a clean glass surface is exposed to humid air, a thin water layer forms on the hydrophilic surface. Using ab initio molecular dynamics, we simulate the changes in the electronic structure of a CaO-Al2O3-SiO2 glass model upon vacuum fracture and subsequent exposure to H2O. When the glass is fractured, dangling bonds form, which lower the band gap of the surface by ∼1.8 eV compared to the bulk value due to mid-gap surface states. When H2O adsorbs onto the vacuum-fractured surface, the band gap increases to a value closer to that of the bulk band gap. Using two different hydroxylation methods, we find that the calculated band gap of the glass surface depends on the hydroxylation state. Surfaces with ∼4.5 OH/nm2 have smaller band gaps due to unfilled surface states, and surfaces with ∼2.5 OH/nm2 have larger band gaps with no apparent unfilled surface states. The resulting changes in the electronic structure, quantified by electron affinity and work function values, are hypothesized to play an important role in the electrostatic charge transfer based on the principles of surface state theory, which posit that the density of electronic surface states determines the amount of electronic charge transfer to or from material surfaces.

Review on Interfacial Bonding Mechanism of Functional Polymer Coating on Glass in Atomistic Modeling Perspective.

Atomistic modeling methods are successfully applied to understand interfacial interaction in nanoscale size and analyze adhesion mechanism in the organic-inorganic interface. In this paper, we review recent representative atomistic simulation works, focusing on the interfacial bonding, adhesion strength, and failure behavior between polymer film and silicate glass. The simulation works are described under two categories, namely non-bonded and bonded interaction. In the works for non-bonded interaction, three main interactions, namely van der Waals interaction, polar interaction, and hydrogen bonds, are investigated, and the contributions to interfacial adhesion energy are analyzed. It is revealed that the most dominant interaction for adhesion is hydrogen bonding, but flexibility of the polymer film and modes of adhesion measurement test do affect adhesion and failure behavior. In the case of bonded interactions, the mechanism of covalent silane bond formation through condensation and hydrolysis process is reviewed, and surface reactivity, molecular density, and adhesion properties are calculated with an example of silane functionalized polymer. Besides interfacial interactions, effects of external conditions, such as surface morphology of the glass substrate and relative humidity on the adhesion and failure behavior, are presented, and modeling techniques developed for building interfacial system and calculating adhesion strengths are briefly introduced.

Computational approaches for investigating interfacial adhesion phenomena of polyimide on silica glass.

This manuscript provides a comprehensive study of adhesion behavior and its governing mechanisms when polyimide undergoes various modes of detachment from silica glass. Within the framework of steered molecular dynamics, we develop three different adhesion measurement techniques: pulling, peeling, and sliding. Such computational methodologies can be applied to investigate heterogeneous materials with differing interfacial adhesion modes. Here, a novel hybrid potential involving a combination of the INTERFACE force field in conjunction with ReaxFF and including Coulombic and Lennard-Jones interactions is employed to study such interfaces. The studies indicate that the pulling test requires the largest force and the shortest distance to detachment as the interfacial area is separated instantaneously, while the peeling test is observed to exhibit the largest distance for detachment because it separates via line-by-line adhesion. Two kinds of polyimides, aromatic and aliphatic type, are considered to demonstrate the rigidity dependent adhesion properties. The aromatic polyimide, which is more rigid due to the stronger charge transfer complex between chains, requires a greater force but a smaller distance at detachment than the aliphatic polyimide for all of the three methodologies.

Surface criticality at a dynamic phase transition.

In order to elucidate the role of surfaces at nonequilibrium phase transitions, we consider kinetic Ising models with surfaces subjected to a periodic oscillating magnetic field. Whereas, the corresponding bulk system undergoes a continuous nonequilibrium phase transition characterized by the exponents of the equilibrium Ising model, we find that the nonequilibrium surface exponents do not coincide with those of the equilibrium critical surface. In addition, in three space dimensions, the surface phase diagram of the nonequilibrium system differs markedly from that of the equilibrium system.