Atomic Layer Etching of HfO2Using Sequential, Self-Limiting Thermal Reactions with Sn(acac)2and HF

The atomic layer etching (ALEt) of HfO 2 was performed using sequential, self-limiting thermal reactions with tin(II) acetylacetonate (Sn(acac) 2 ) and HF as the reactants. The HF source was a HF-pyridine solution. The etching of HfO 2 was linear with atomic level control versus number of Sn(acac) 2 and HF reaction cycles. The HfO 2 ALEt was measured at temperatures from 150–250°C. Quartz crystal microbalance (QCM) measurements determined that the mass change per cycle (MCPC) increased with temperature from −6.7 ng/(cm 2 cycle) at 150°C to −11.2 ng/(cm 2 cycle) at 250°C. These MCPC values correspond to etch rates from 0.070 Å/cycle at 150°C to 0.117 Å/cycle at 250°C. X-ray reflectivity analysis confirmed the linear removal of HfO 2 and measured an HfO 2 ALEt etch rate of 0.11 Å/cycle at 200°C. Fourier transform infrared (FTIR) spectroscopy measurements also observed HfO 2 ALEt using the infrared absorbance of the Hf-O stretching vibration. FTIR analysis also revealed absorbance features consistent with HfF 4 or HfF x surface species as a reaction intermediate. The HfO 2 etching is believed to follow the reaction: HfO 2 + 4Sn(acac) 2 + 4HF → Hf(acac) 4 + 4SnF(acac) + 2H 2 O. In the proposed reaction mechanism, Sn(acac) 2 donates acac to the substrate to produce Hf(acac) 4 . HF allows SnF(acac) and H 2 O to leave as reaction products. The thermal ALEt of many other metal oxides, as well as metal nitrides, phosphides, sulfides and arsenides, should be possible by a similar mechanism.