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This study reports the preparation of Si nanowires (SiNWs) by selective electroless etching and fabrication of photovoltaic (PV) cells. It was found that the SiNWs with 3 μm average length and 100 nm average diameter were formed only in the areas not covered by the Cr electrodes. It was also found that average reflectance in the 400-1000 nm wavelength range reduced from 35% to around 2% with the SiNWs. Furthermore, it was found that we could enhance the short-circuit current density of the PV cells from 11.5 to 21.8 mA/cm2 and enhance conversion efficiency of the PV cells from 4.62% to 8.15% using the selective electroless etching.