Size controllable nanocrystalline silicon (nc‐Si) materials show novel electrical and optical characteristics of silicon quantum dots. Based on laser induced constrained crystallization principle, the one‐/two‐/three‐dimension (1D, 2D and 3D) ordered controllable nc‐Si array have been successfully obtained by using phase‐shifting grating mask combine with multilayer structures. The tunable photoluminescence (PL) and electro‐luminescence (EL) from this kind of nc‐Si films have been observed. The collective single‐electron resonant tunneling and charge storage in the uniform nc‐Si single layer have been studied by using I‐V and the C‐V measurement at room temperature. The double level charge storage in stacked nc‐Si layer based metal‐insulator‐semiconductor (MIS) structure has been demonstrated. (© 2009 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)