Journal of Physical Chemistry A, Vol.104, No.20, 4699-4703, 2000
Effect of hole trapping on the microscopic structure of oxygen vacancy sites in a-SiO2
To develop an improved fundamental understanding of the microscopic effects of hole trapping by oxygen vacancy sites (V-O) in amorphous a-SiO2, we have performed ab initio Hartree-Fock calculations of the structure and energy of model silicon dioxide clusters. Three different precursor clusters were employed in these calculations: (A) a 15-atom cluster without rings; (B) a 39-atom cluster containing four 6-atom (3-membered) rings; and (C) an 87-atom cluster with four 12-atom (6-membered) rings. For clusters A and B, a double-zeta plus polarization (DZP) basis set was used. For cluster C, a minimal (STO-3G) basis set was employed. Our results suggest that the energy of formation, Delta E-f of V-O in the neutral (V-O(0)) and positive (V-O(+1)) charge stares depends on the starting size and geometry of the precursor, Similarly, microscopic structural changes, primarily network relaxation, due to hole trapping by V-O(0) strongly depend on the initial local structure around the vacancy. A neutral vacancy, V-O(0), tends to form a Si-Si dimer bond regardless of the network structure. Similarly, hole trapping at V-O in a relatively rigid network containing 6-atom (3-membered) fused rings results in a small, but symmetric relaxation (i.e., elongation) of the Si-Si bond at the vacancy site. When the network contains more flexible structures, such as 12-atom (6-membered) rings adjacent to V-O and sufficient asymmetry, trapping of a hole causes an asymmetric relaxation of the two adjacent Si atoms, The asymmetric relaxation in our calculation proceeds without a barrier. The value of Delta E-f for V-O(0) and V-O(+1) decreases with the flexibility and asymmetry in the oxide network.