Controllable hierarchy of highly regular, single-crystalline nanorod, nanopencil and nanocone arrays with tunable geometry and etch anisotropy has been achieved over large areas (>1.5 cm × 1.5 cm) by using an [AgNO3 + HF + HNO3/H2O2] etching system. The etching mechanism has been elucidated to originate from the site-selective deposition of Ag nanoclusters. Different etch anisotropies and aspect ratios can be accomplished by modulating the relative concentration in the [AgNO3 + HF + HNO3/H2O2] etching system. Minimized optical reflectance is also demonstrated with the fabricated nano-arrays. Overall, this work highlights the technological potency of utilizing a simple wet-chemistry-only fabrication scheme, instead of reactive dry etching, to attain three-dimensional Si nanostructures with different geometrical morphologies for applications requiring large-scale, low-cost and efficient photon trapping (e.g. photovoltaics).
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