Light/matter interaction of low-dimensional silicon (Si) strongly correlated with its geometrical features, which resulted in being highly critical for the practical development of Si-based photovoltaic applications. Yet, orientation modulation together with apt control over the size and spacing of aligned Si nanowire (SiNW) arrays remained rather challenging. Here, we demonstrated that the transition of formed SiNWs with controlled diameters and spacing from the crystallographically preferred <100> to <110> orientation was realized through the facile adjustment of etchant compositions. The underlying mechanism was found to correlate with the competing reactions between the formation and removal of oxide at Ag/Si interfaces that could be readily tailored through the concentration ratio of HF to H2O2. By employing inclined SiNWs for the construction of hybrid solar cells, the improved cell performances compared with conventional vertical-SiNW-based hybrid cells were demonstrated, showing the conversion efficiency of 12.23%, approximately 1.12 times higher than that of vertical-SiNW-based hybrid solar cells. These were numerically and experimentally interpreted by the involvement of excellent light-trapping effects covering the wide-angle light illuminations of inclined SiNWs, which paved the potential design for next-generation optoelectronic devices.
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