Combining Molecular Dynamics and Monte Carlo Simulations to Model Chemical Vapor Deposition: Application to Diamond

Gas-surface reactions of the type that contribute to growth during the chemical vapor deposition (CVD) of diamond films are generally completed in picoseconds, well within timescales accessible by molecular dynamics (MD) simulations. For low-pressure deposition, however, the time between collisions for a surface site can be microseconds, which makes direct modeling of CVD crystal growth impossible using standard MD methods. To effectively bridge this discrepancy in timescales, the gas-surface reactions can be modeled using MD trajectories, and then this data can be used to define probabilities in a Monte Carlo algorithm where each step represents a gas-surface collision. We illustrate this approach using the reaction of atomic hydrogen with a diamond (111) surface as an example, where we use abstraction and sticking probabilities generated using classical trajectories in a simple Monte Carlo algorithm to determine the number of open sites as a function of temperature. We also include models for the thermal desorption of hydrogen that predict that growth temperatures are not restricted by the thermal loss of chemisorbed hydrogen.