Surface of porous silicon under hydrophilization and hydrolytic degradation

Analysis of the IR absorption spectra is used to trace changes in the chemical composition of surface layers of mesoporous silicon crystals during the course of their hydrophilization via oxidation in hydrogen-peroxide solutions and as a result of indirect, by intermediate bromination, and direct nucleophilic substitution of bound hydrogen with a hydroxyl. The spontaneous process of atomic rearrangement with the transfer of oxygen atoms from adsorbed OH groups to lower-lying atomic layers of the crystalline skeleton, which yields Si–H bonds on its surface: –Si–Si–OH $\to$ –Si–O–Si–H, is revealed. The sequence of elementary processes that facilitate the hydrolytic degradation of porous silicon in weakly alkaline media is considered. The role played by the deformation of chemical bonds in a porous crystal in promoting the hydrolysis of silicon is noted. It is shown that the surface modification of porous silicon via bromination and subsequent treatment in water makes it possible to substantially increase the rate of its hydrolytic degradation in weakly alkaline solutions that are similar in pH values to biological fluids.