Thermal atomic layer etching of germanium-rich SiGe using an oxidation and “conversion-etch” mechanism

Abstract

The thermal atomic layer etching (ALE) of germanium-rich SiGe was demonstrated using an oxidation and “conversion-etch” mechanism with oxygen (O2) or ozone (O3), hydrofluoric acid (HF), and trimethylaluminum [TMA, Al(CH3)3] as the reactants. The crystalline germanium-rich SiGe film was prepared using physical vapor deposition and had a composition of Si0.15Ge0.85. In situ spectroscopic ellipsometry was employed to monitor the thickness of both the SiGe film and the surface oxide layer on the SiGe film during thermal ALE. Using a reactant sequence of O2-HF-TMA, the etch rate of the SiGe film increased progressively with temperatures from 225 to 290 °C. At 290 °C, the SiGe film thickness decreased linearly at a rate of 0.57 Å/cycle with a surface oxide thickness of 18–19 Å. This etch rate was obtained using reactant pressures of 25, 0.2, and 0.4 Torr and doses of 1.5, 1.0, and 1.0 s for O2, HF, and TMA, respectively. The TMA and HF reactions were self-limiting and the O2 reaction was reasonably self-limiting at 290 °C. Using an O3-HF-TMA reaction sequence, the SiGe ALE etch rate was 0.42 Å/cycle at 290 °C. This etch rate was obtained using reactant pressures of 15, 0.2, and 0.4 Torr and dose times of 0.5, 1.0, and 1.0 s for O3, HF, and TMA, respectively. The O3, TMA, and HF reactions were all self-limiting at 290 °C. Atomic force microscopy images revealed that thermal ALE with the O2-HF-TMA or O3-HF-TMA reaction sequences did not roughen the surface of the SiGe film. The SiGe film was etched selectively compared with Si or Si3N4 at 290 °C using an O2-HF-TMA reaction sequence. The etch rate for the SiGe film was >10 times faster than Si(100) or Si3N4 that was prepared using low-pressure chemical vapor deposition. This selectivity for the SiGe film will be useful to fabricate Si nanowires and nanosheets using SiGe as the sacrificial layer.