Tyndall National Institute present the first computational study of thermal Atomic Layer Etch of metal oxides by exposure to HF

Modeling the Chemical Mechanism of the Thermal Atomic Layer Etch of Aluminum Oxide: A Density Functional Theory Study of Reactions during HF Exposure

Suresh Kondati Natarajan and Simon D. Elliott
Tyndall National Institute, University College Cork
Chem. Mater., Article ASAP
DOI: 10.1021/acs.chemmater.8b01930, Publication Date (Web): August 9, 2018

Reprinted with permission from (DOI: 10.1021/ACS.CHEMATER.8b01930). Copyright (2018) American Chemical Society.

Thermal atomic layer etch, the reverse of atomic layer deposition, uses a cyclic sequence of plasma-free and solvent-free gas surface reactions to remove ultrathin layers of material with a high degree of control. A theoretical investigation of the hydrogen fluoride pulse in the thermal atomic layer etch of monoclinic alumina has been performed using density functional theory calculations. From experiments, it has been suggested that the HF pulse forms a stable and nonvolatile layer of AlF₃ on an alumina surface. Consistent with this, the desorption of an AlF₃ molecule from an HF-saturated surface was computed to be energetically unfavorable. HF molecules adsorbed on the alumina surface by forming hydrogen bonds and either remained intact or dissociated to form Al–F and O–H species. At higher coverages, a mixture of molecularly and dissociatively adsorbed HF molecules in a hydrogen-bonded network was observed. Binding energies converged as the coverage of dissociated F became saturated, consistent with a self-limiting reaction. The formation of H₂O molecules in the HF pulse was found to be endoergic with an energy barrier of at least +0.9 eV, but their subsequent desorption was computed to cost as little as +0.2 eV. On the basis of a model of the saturated Al–F surface, the theoretical maximum of the etch rate was estimated to be −0.57 ± 0.02 Å/cycle (−20.0 ± 0.8 ng cm^–2 cycle^–1), which matches the range of maximum experimental values. The actual etch rate will, however, be dependent on the specific reagent used in the subsequent step of the atomic layer etch cycle. 

Big step forward by Suresh Kondati Natarajan in @Mick__geek group @tyndallinstitut - the first computational study of the ground-breaking @GeorgeGroupCU process for thermal Atomic Layer Etch #ALEt of oxides by exposure to HF @Schrodinger #ALDep @ChemMater https://t.co/oh8cT3qEJd

— Simon Elliott (@Simon_D_Elliott) August 24, 2018