A process for area selective atomic layer deposition (ALD) at the near atomic scale (sub 10 nm) is disclosed. A substrate surface is cleaned and terminated with hydrogen and a pattern written in the hydrogen terminated surface by selectively depassivating the surface using scanning tunneling microscope lithography. The depassivated regions are subjected to a halogen flux with the thus passivated regions further subjected to a functionalization process creating functionalized regions. The role of hydrogen and halogen can be inverted to invert the tone of the pattern. The substrate is then subjected to the ALD process, with growth occurring only in the non-functionalized regions. The substrate may then optionally be subjected to selective etching to remove the functionalized regions and the portions of the substrate under the functionalized regions.

A method of processing a silicon surface includes using a first radical species to remove contamination from the surface and to roughen the surface; and using a second radical species to smooth the roughened surface. Reaction systems for performing such a method, and silicon surfaces prepared using such a method, also are provided.

Methods of selectively depositing a low-k dielectric film are described. In one or more embodiments, the methods include exposing a substrate to a blocking compound, the substrate including a first surface and a second surface, the first surface including hydrogen-terminated silicon, the blocking compound selectively depositing on the first surface to form a blocked first surface; and selectively depositing the low-k dielectric film on the second surface. Methods of forming an inner spacer layer are described. In one or more embodiments, the methods include pretreating a substrate to remove oxide from a hydrogen-terminated silicon (Si) channel of the substrate, the substrate including the hydrogen-terminated silicon channel and a silicon germanium (SiGe) surface; exposing the substrate to a blocking compound, the blocking compound selectively depositing on the hydrogen-terminated silicon (Si) channel to form a blocked silicon channel; and depositing the inner spacer layer selectively on the silicon germanium surface.

Methods for selective deposition are provided. Material is selectively deposited on a first surface of a substrate relative to a second surface of a different material composition. An inhibitor, such as a polyimide layer, is selectively formed from vapor phase reactants on the first surface relative to the second surface. A layer of interest is selectively deposited from vapor phase reactants on the second surface relative to the first surface. The first surface can be metallic while the second surface is dielectric. Accordingly, material, such as a dielectric transition metal oxides and nitrides, can be selectively deposited on metallic surfaces relative dielectric surfaces using techniques described herein.

There is provided a technique that includes: (a) supplying a film-forming agent to the substrate having a recess on a surface thereof, the recess having a bottom surface formed by a first base and a side surface formed by a second base, and forming a first film on the first base with a thickness greater than a thickness of a first film formed on the second base; and (b) supplying an etching agent to the substrate, and removing the first film formed on the second base while leaving at least a part of the first film formed on the first base.

There is provided a technique that includes: (a) supplying a silicon- and ligand-containing gas to a substrate having a surface on a first base and second base are exposed to adsorb silicon contained in the silicon- and ligand-containing gas on a surface of one of the first and second base; (b) supplying a fluorine-containing gas to the substrate after the silicon is absorbed, to cause the silicon to react with the fluorine-containing gas to modify the surface to be F-terminated; and (c) supplying a film-forming gas to the substrate after the surface is modified, to thereby form a film on a surface of the other of the first base and the second base, which is different from the one of the first base and the second base.

A method of processing a silicon surface includes using a first radical species to remove contamination from the surface and to roughen the surface; and using a second radical species to smooth the roughened surface. Reaction systems for performing such a method, and silicon surfaces prepared using such a method, also are provided.

A substrate processing method includes: preparing a substrate having a recess on a surface thereof; supplying chlorine gas to the substrate, thereby forming an adsorption-inhibiting layer in the recess; supplying a source gas to the substrate, thereby forming a molecular layer of the source gas in the recess; and supplying a nitriding gas to the substrate, thereby nitriding the molecular layer formed in the recess. The source gas is a gas that is inhibited by the adsorption-inhibiting layer from the formation of the molecular layer in the recess. The formation of the adsorption-inhibiting layer includes: retaining, in a retaining portion, the chlorine gas before being supplied to the substrate, and generating chlorine radicals from the chlorine gas by irradiating, with an ultraviolet ray, the chlorine gas inside the retaining portion.