Development of the ReaxFF Reactive Force Field for Inherent Point Defects in the Si/Silica System

We redeveloped the ReaxFF force field parameters for Si/O/H interactions that enable molecular dynamics (MD) simulations of Si/SiO2 interfaces and O diffusion in bulk Si at high temperatures, in particular with respect to point defect stability and migration. Our calculations show that the new force field framework (ReaxFFpresent), which was guided by the extensive quantum mechanical-based training set, describes correctly the underlying mechanism of the O-migration in Si network, namely, the diffusion of O in bulk Si occurs by jumping between the neighboring bond-centered sites along a path in the (110) plane, and during the jumping, O goes through the asymmetric transition state at a saddle point. Additionally, the ReaxFFpresent predicts the diffusion barrier of O-interstitial in the bulk Si of 64.8 kcal/mol, showing a good agreement with the experimental and density functional theory values in the literature. The new force field description was further applied to MD simulations addressing O diffusion in bulk Si at different target temperatures ranging between 800 and 2400 K. According to our results, O diffusion initiates at the temperatures over 1400 K, and the atom diffuses only between the bond-centered sites even at high temperatures. In addition, the diffusion coefficient of O in Si matrix as a function of temperature is in overall good agreement with experimental results. As a further step of the force field validation, we also prepared amorphous SiO2 (a-SiO2) with a mass density of 2.21 gr/cm3, which excellently agrees with the experimental value of 2.20 gr/cm3, to model a-SiO2/Si system. After annealing the a-SiO2/Si system at high temperatures until below the computed melting point of bulk Si, the results show that ReaxFFpresent successfully reproduces the experimentally and theoretically defined diffusion mechanism in the system and succeeded in overcoming the diffusion problem observed with ReaxFFSiOH(2010), which results in O diffusion in the Si substrate even at the low temperature such as 300 K