We study the structure and optical properties of arrays of silicon nanowires (SiNWs) with a mean diameter of approximately 100 nm and length of about 1–25 μm formed on crystalline silicon (c-Si) substrates by using metal-assisted chemical etching in hydrofluoric acid solutions. In the middle infrared spectral region, the reflectance and transmittance of the formed SiNW arrays can be described in the framework of an effective medium with the effective refractive index of about 1.3 (porosity, approximately 75%), while a strong light scattering for wavelength of 0.3 ÷ 1 μm results in a decrease of the total reflectance of 1%-5%, which cannot be described in the effective medium approximation. The Raman scattering intensity under excitation at approximately 1 μm increases strongly in the sample with SiNWs in comparison with that in c-Si substrate. This effect is related to an increase of the light-matter interaction time due to the strong scattering of the excitation light in SiNW array. The prepared SiNWs are discussed as a kind of ‘black silicon’, which can be formed in a large scale and can be used for photonic applications as well as in molecular sensing.

Silicon nanowires (SiNWs) were fabricated by metal-assisted chemical etching (MACE) where hydrofluoric acid (HF), which is typically used in this method, was changed into ammonium fluoride (NH4F). The structure and optical properties of the obtained SiNWs were investigated in details. The length of the SiNW arrays is about 2 μm for 5 min of etching, and the mean diameter of the SiNWs is between 50 and 200 nm. The formed SiNWs demonstrate a strong decrease of the total reflectance near 5–15 % in the spectral region λ < 1 μm in comparison to crystalline silicon (c-Si) substrate. The interband photoluminescence (PL) and Raman scattering intensities increase strongly for SiNWs in comparison with the corresponding values of the c-Si substrate. These effects can be interpreted as an increase of the excitation intensity of SiNWs due to the strong light scattering and the partial light localization in an inhomogeneous optical medium. Along with the interband PL was also detected the PL of SiNWs in the spectral region of 500–1100 nm with a maximum at 750 nm, which can be explained by the radiative recombination of excitons in small Si nanocrystals at nanowire sidewalls in terms of a quantum confinement model. So SiNWs, which are fabricated by environment-friendly chemistry, have a great potential for use in photovoltaic and photonics applications.