Search for: All records

As lithographic techniques advance in their capabilities of shrinking microelectronics devices, the need for improved resist materials, especially for extreme ultraviolet (EUV), has become increasingly pressing. In this work, we study the molecular layer deposition (MLD) of an Al-based hybrid thin film resist, known as “alucone,” extending our previous research that tested the Hf-based hybrid thin film “hafnicone” as an EUV resist. Alucone is grown at 100 ºC using the metal precursor trimethylaluminum and the organic precursor ethylene glycol. Like hafnicone, alucone behaves as a negative tone resist that can resolve 50-nm line widths, though preliminary data suggest that alucone’s line patterns are more sharply defined than those of hafnicone. Whereas hafnicone’s sensitivity is 400 μC/cm2 using 3 M HCl as the developer, alucone’s sensitivity is not yet as good (4800 μC/cm2 using 0.125 M HCl). Our study of alucone offers new insight into structural features of an MLD film that can lead to desired EUV-responsive behavior. This insight may accelerate the development of vapor-deposited inorganic resists for use in electron-beam and EUV lithography. 

Atomic layer deposition (ALD) is a technologically important method to grow thin films with high conformality and excellent thickness control from vapor phase precursors. The development of new thermal ALD processes can be limited by precursor reactivity and stability: reaction temperature and precursor design are among the few variables available to achieve higher reactivity, unlike in solution synthesis where the use of solvent and/or a catalyst can promote a desired reaction. To bridge this synthesis gap between vapor and solution, we demonstrate the use of an ultrathin coating layer of a vapor-phase compatible solvent—an ionic liquid (IL)— onto our growth substrate to perform ALD of SnO. Successful SnO deposition is achieved using tin acetylacetonate and water, a process that otherwise would require a stronger counter-reactant such as ozone. The layer of IL allows a solvent-mediated reaction mechanism to take place on the growth substrate. We report a growth per cycle of 0.67 Å/cycle at a deposition temperature of 100 °C in an IL comprised of 1-ethyl-3-methylimidazolium hydrogen sulfate. Characterization of the ALD films confirms the SnO film composition, and 1H and 13C NMR are used to probe the solvent-mediated ALD reaction, suggesting a solvent-mediated addition-elimination type mechanism forming acetone and acetate. Density functional theory calculations show that the ionic liquid solvent is beneficial to the proposed solvent-mediated mechanism by lowering the C-C bond cleavage energetics of acetylacetonate compared to the vapor phase. A general class of ligand-modification reactions for thermal ALD is thus introduced in this work.