Si nanowires (NWs) were doped with large amounts of Li+ ions by an electrochemical insertion method at room temperature. Si NWs with different doping levels were obtained by controlling the discharging/charging of Li/Si NWs cell. The microstructures of Si NWs with different doses of Li+ ions were investigated by high-resolution electron microscopy. The crystalline structure of the Si NWs was destroyed gradually with the increasing of Li+ ion dose. When the Li+ ions were extracted from the amorphous Li-doped Si NWs by the same electrochemical method, local ordering of atoms occurred and recrystallization was observed. The photoluminescence peak and intensity of Li+-doped Si NWs are closely related to the doping dose.
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