Hydrogen-induced crystallization of amorphous Si thin films. II. Mechanisms and energetics of hydrogen insertion into Si-Si bonds

We report a detailed study of the mechanisms and energetics of hydrogen (H) insertion into strained Si-Si bonds during H-induced crystallization of hydrogenated amorphous Si (a-Si:H) thin films. Our analysis is based on molecular-dynamics (MD) simulations of exposure of a-Si:H films to H atoms from a H ₂ plasma through repeated impingement of H atoms. Hydrogen atoms insert into Si-Si bonds as they diffuse through the a-Si:H film. Detailed analyses of the evolution of Si-Si and Si-H bond lengths from the MD trajectories show that diffusing H atoms bond to one of the Si atoms of the strained Si-Si bond prior to insertion; upon insertion, a bridging configuration is formed with the H atom bonded to both Si atoms, which remain bonded to each other. After the H atom leaves the bridging configuration, the Si-Si bond is either further strained, or broken, or relaxed, restoring the Si-Si bond length closer to the equilibrium bond length in crystalline Si. In some cases, during its diffusion in the a-Si:H film, the H atom occupies a bond-center position between two Si atoms that are not bonded to each other; after the H diffuses away from this bond-center position, a Si-Si bond is formed between these previously nonbonded Si atoms. The activation energy barrier for the H insertion reaction depends linearly on both the initial strain in the corresponding Si-Si bond and a strain factor that takes into account the additional stretching of the Si-Si bond in the transition-state configuration. The role of the H insertion reactions in the structural relaxation of the a-Si:H network that results in disorder-to-order transitions is discussed.