Abstract: The invention includes a method of promoting atomic layer etching (ALE) of a surface. In certain embodiments, the method comprises sequential reactions with a metal precursor and a halogen-containing gas. In other embodiments, the etching rate is increased by removing residual species bound to and/or adsorbed onto the surface.

Abstract: Generally, the present invention relates to patterning techniques for creating nanoscale features on a substrate. The invention offers an improved method over traditional e-beam or photolithographic techniques and uses atomic layer deposition (ALD) chemistries and a source of high-energy ions. These either as focused or a flood of ions facilitate ALD deposition by providing additional energy to the reaction or, more significantly, can form part of the final chemical structure of the ALD coating. Additional embodiments include using ion beam-assisted ALD to deposit a seed layer for subsequent thermal ALD processes, and ion beam-assisted molecular layer deposition chemistries (MLD) for direct patterning of organic and/or inorganic long-chain macromolecules (e.g., polymers, proteins, peptides and polysaccharides). A further embodiment combines both ALD and MLD methods to allow fabrication of unique hybrid metal, semiconductor or dielectric ALD and organic or inorganic MLD films.