Plasma-deposited polycrystalline Si films [or microcrystalline Si (pc-Si) films] produced by plasma enhanced chemical vapor deposition (PECVD) have attracted considerable attention as novel, low-cost and stable materials for the photovoltaic i-layer in p-i-n junction thin-film solar cells. The mu c-Si films prepared under various deposition conditions show widely various micro structures, from a crystalline-amorphous mixed state to an almost perfect crystalline state, with different crystallographic orientations. These structural changes directly influence the carrier transport properties that play a dominant role in determining photovoltaic performance. Furthermore, obtaining a uniform built-in electric field throughout the i-layer is a crucial issue for achieving excellent photovoltaic performance. To obtain a uniform electric field, the following terms should be required for the i-layer: 'truly' intrinsic characteristic (or not n-type characteristics) as well as structural uniformity in the growth direction without an incubation layer. Here, structural properties of pc-Si for achieving truly intrinsic characteristics are reviewed with an emphasis on collations with the crystalline volume function and the degree of (220) crystallographic preferential orientation in the crystalline phase. In addition, we reviewed a growth mechanism for the pc-Si film that is actually used in the photovoltaic i-layer in highly efficient solar cells: hybrid-phase growth consisting of conventional vapor-phase growth at the surface and the solid-phase crystallization that simultaneously occurs in the film. That growth is very effective in producing structural uniformity along the growth direction and for formation of crystallites directly on the underlying doped layer. (c) 2006 Elsevier Ltd. All rights reserved.