抄録
Pyrolysis of polysilanes with different molecular weights, solid states and substituents has been studied by quadrupole mass spectroscopy. The analysis of kinetics on the gas evolution spectra of a unit of the polysilanes gives their activation energies having Gaussian distributions. The number reduction of the weak Si-Si bonds with the decrease of the chain length of polysilanes results in the increase of activation energy of decomposition. The activation energy is also affected by the kind of solid states of polysilane. Because of the stronger interaction among the molecules, polysilane film has higher activation energies than powder. Due to the photodegradation and oxidation of polysilanes, photooxidized film has higher activation energies of decomposition and a broader distribution of activation energies than the unoxidized film. Furthermore, substituents give intense effects on the activation energies and the order of the decomposition reactions. It is found that the decomposition reactions occur at the low temperature if the substituents are easy to be disconnected from Si.
