Analysis of silicon surfaces etched in aqueous HF-(HBr)–Br2-mixtures

Abstract

Solutions containing hydrofluoric acid (HF), hydrobromic acid (HBr) and bromine (Br2) were investigated as novel acidic, NOx-free mixtures for wet-chemical etching of silicon wafers. HF–Br2-mixtures exhibit isotropic etching behaviour towards silicon, etch rates up to 4.0 ​μm ​min−1 were observed at room temperature, which are higher than the etch rates of commercially used alkaline solutions. HF–HBr–Br2-mixtures show anisotropic etching behaviour, texturing the surface of monocrystalline silicon wafers with random upright or random inverted pyramidal structures. Etch rates up to 2.4 ​μm ​min−1 were observed, the etch rate increases linearly with the concentration of Br2 in the etching solution. Silicon surfaces were investigated by scanning electron microscopy (SEM), X-ray photoelectron spectroscopy (XPS) and diffuse reflectance infrared Fourier transform spectroscopy (DRIFTS). The light trapping efficiency of wafers etched by HF–HBr–Br2 solutions was compared to commercially available textured wafers by UV/Vis-reflectivity measurements indicating lower reflectivities for the HF–HBr–Br2-treated samples. A reaction scheme for the anisotropic dissolution of silicon in bromine-containing aqueous HF-solutions is proposed, which involves bromine as oxidizing agent.

Keywords

• Silicon
• Etching
• Polishing
• Texturization
• Photovoltaic
• Semiconductor