Origin of Enhanced Thermal Atomic Layer Etching of Amorphous HfO2

HfO2 is a high-k material that is used in semiconductor devices. Atomic-level control of material processing is required for the fabrication of thin films of high-k materials at nanoscale device sizes. Thermal atomic layer etching (ALE) of metal oxides, in which up to one monolayer of material can be removed, can be achieved by sequential self-limiting (SL) fluorination and ligand-exchange reactions at elevated temperatures. First-principles based atomic-level simulations using density functional theory (DFT) can give deep insights into the precursor chemistry and the reactions that drive the etch of metal oxides. A previous study examined the hydrogen fluoride (HF) pulse in the first step in the thermal ALE process of crystalline HfO2 and ZrO2. This study examines the HF pulse on amorphous HfO2 using first-principles simulations. The Natarajan-Elliott analysis, a thermodynamic methodology is used to compare reaction models representing the self-limiting and spontaneous etch processes taking place during an ALE pulse. For the HF pulse on amorphous HfO2, we found that thermodynamic barriers impeding spontaneous etching are present at ALE relevant temperatures. HF adsorption calculations on the amorphous oxide surface is studied to understand the mechanistic details of the HF pulse. A HF molecule adsorbs dissociatively by forming Hf-F and O-H bonds. HF coverages ranging from 1.1 ± 0.3 to 18.0 ± 0.3 HF/nm2 are investigated and a mixture of molecularly and dissociatively adsorbed HF molecules is present at higher coverages. A theoretical etch rate of -0.82 ± 0.02 Å/cycle for amorphous HfO2 was calculated using a maximum coverage of 9.0 ± 0.3 Hf-F/nm2. This theoretical etch rate is greater than the theoretical etch rate for crystalline HfO2 that we previously calculated at -0.61 ± 0.02 Å/cycle. Undercoordinated atoms and void regions in amorphous HfO2 allows for more binding sites during fluorination whereas crystalline HfO2 has a limited number of adsorption sites.