Atomic layer deposition (ALD) of smooth and highly conformal films of hafnium and zirconium oxides was studied using six metal alkylamide precursors for hafnium and zirconium. Water was used as an oxygen source during these experiments. As deposited, these films exhibited a smooth surface with a measured roughness equivalent to that of the substrate on which they were deposited. These films also exhibited a very high degree of conformality:  100% step coverage on holes with aspect ratios greater than 35. The films were completely uniform in thickness and composition over the length of the deposition reactor. The films were free of detectable impurities and had the expected (2:1) oxygen-to-metal ratio. Films were deposited at substrate temperatures from 50 to 500 °C from precursors that were vaporized at temperatures from 40 to 140 °C. The precursors were found to be highly reactive with hydroxylated surfaces. Their vapor pressures were measured over a wide temperature range. Deposition reactor design and ALD cycle design using these precursors are discussed.

Highly conformal coatings can be deposited inside narrow features, such as holes, using complementary self-limiting reactions of two vapors with a surface. A simple theory is developed for the conditions needed to deposit coatings with uniform thickness in narrow holes of arbitrary cross section. Two conditions are found to be necessary: 1) certain minimum amounts of vapor must be supplied, and 2) a certain minimum product of vapor pressure and its exposure time at the entrance to the hole. The theory is in good agreement with data from the reaction of hafnium dimethylamide vapor and water vapor to form hafnium dioxide films that are completely conformal in holes with an aspect ratio of 43. The theory provides simple scaling laws to predict the conditions needed to coat holes with other aspect ratios.

Highly uniform and conformal coatings can be made by the alternating exposures of a surface to vapors of two reactants, in a process commonly called atomic layer deposition (ALD). The application of ALD has, however, been limited because of slow deposition rates, with a theoretical maximum of one monolayer per cycle. We show that alternating exposure of a surface to vapors of trimethylaluminum and tris(tert-butoxy)silanol deposits highly conformal layers of amorphous silicon dioxide and aluminum oxide nanolaminates at rates of 12 nanometers (more than 32 monolayers) per cycle. This process allows for the uniform lining or filling of long, narrow holes. We propose that these ALD layers grow by a previously unknown catalytic mechanism that also operates during the rapid ALD of many other metal silicates. This process should allow improved production of many devices, such as trench insulation between transistors in microelectronics, planar waveguides, microelectromechanical structures, multilayer optical filters, and protective layers against diffusion, oxidation, or corrosion.

Area-selective atomic layer deposition (AS-ALD) is a promising "bottom-up" alternative to current nanopatterning techniques. Self-assembled monolayers (SAM) have been successfully employed as deactivating agents to achieve AS-ALD. In this work, the formation of octadecylphosphonic acid (ODPA) SAMs is studied on four technologically important metal substrates: Cu, Co, W, and Ru. The SAM quality is shown to be dependent on temperature, solvent, and the nature of the substrate. The blocking ability of the ODPA-treated substrates is evaluated using ZnO and Al 2 O 3 model ALD processes. Spectroscopic analyses reveal that ODPA-assisted ALD blocking can be achieved to varying degrees of success on each metal. ODPAprotected W showed >90% selectivity after 32 nm ZnO and 8 nm Al 2 O 3 ALD, exhibiting the best blocking overall. For all substrates, ZnO ALD proved consistently easier to block than Al 2 O 3 , indicating the importance of precursor chemistry. Additionally, we show that the self-correcting process previously reported for Cu using an acetic acid etchant can be extended to Co. This process improves selective deposition of Al 2 O 3 on patterned Co/SiO 2 with feature sizes as small as 25 nm. Additional studies reveal that feature size and density affect the apparent selectivity in SAM-based AS-ALD, highlighting the importance of such considerations in future process developments.

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