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A series of samples deposited by VHF-PECVD at different pressures were studied. The measurement results of photosensitivity (photo conductivity/dark conductivity) and activation energy indicated near the same rule with the change of the pressure. The results measured by Raman scattering spectra,X-ray diffraction and FTIR all proved the evident crystallization of the materials. Treating the p/i interface by hydrogen has a great improving effect on the performance of the microcrystalline silicon (μc-Si) p-i-n solar cells if the treatment time was appropriate. An efficiency of 4.24% for μc-Si p-i-n solar cells deposited by VHF-PECVD was firstly obtained.