Abstract: Methods of selectively inhibiting deposition of silicon-containing films deposited by atomic layer deposition are provided. Selective inhibition involves exposure of an adsorbed layer of a silicon-containing precursor to a hydrogen-containing inhibitor, and in some instances, prior to exposure of the adsorbed layer to a second reactant. Exposure to a hydrogen-containing inhibitor may be performed with a plasma, and methods are suitable for selective inhibition in thermal or plasma enhanced atomic layer deposition of silicon-containing films.

Abstract: Aluminum oxide films with a thickness of between about 10-50 ?, characterized by a dielectric constant (k) of less than about 7 (such as about 4-6) and having a density of at least about 2.5 g/cm3 (such as about 3.0-3.2 g/cm3) are deposited on partially fabricated semiconductor devices over a metal (e.g., cobalt or copper) such that the metal does not show signs of oxidation. In some embodiments, the films are etch stop films.

Abstract: Methods and apparatuses for selectively depositing silicon nitride on exposed surfaces of a substrate having hydroxyl end groups relative to exposed surfaces having S—H bonds are provided herein. Techniques involve providing a transition metal-containing reactant or a non-hydride aluminum-containing gas to the substrate to form a transition metal-containing or an aluminum-containing moiety on an exposed surface having hydroxyl end groups and selectively depositing silicon nitride on the surface using alternating pulses of an aminosilane and a hydrazine by thermal atomic layer deposition catalyzed by the transition metal-containing or aluminum-containing moiety on the exposed surface having hydroxyl end groups relative to an exposed surface having S—H bonds.

Abstract: Provided are methods for the selective deposition of material on a sidewall surface of a patterned feature. In some embodiments, the methods involve providing a substrate having a feature recessed from a surface of the substrate. The feature has a bottom and a sidewall which extends from the bottom. A conformal film is deposited on the feature using an atomic layer deposition (ALD) process. The conformal film deposited on the bottom is modified by exposing the substrate to directional plasma such that the conformal film on the bottom is less dense than the conformal film on the sidewall. The modified conformal film deposited on the bottom of the feature is preferentially etched. Also provided are methods for the selective deposition on a horizontal surface of a patterned feature.

Abstract: Aluminum oxide films with a thickness of between about 10-50 ?, characterized by a dielectric constant (k) of less than about 7 (such as about 4-6) and having a density of at least about 2.5 g/cm3 (such as about 3.0-3.2 g/cm3) are deposited on partially fabricated semiconductor devices over a metal (e.g., cobalt or copper) such that the metal does not show signs of oxidation. In some embodiments, the films are etch stop films.

Abstract: Methods and apparatuses for selectively growing metal-containing hard masks are provided herein. Methods include providing a substrate having a pattern of spaced apart features, each feature having a top horizontal surface, filling spaces between the spaced apart features with carbon-containing material to form a planar surface having the top horizontal surfaces of the features and carbon-containing material, selectively depositing a metal-containing hard mask on the top horizontal surfaces of the features relative to the carbon-containing material, and selectively removing the carbon-containing material relative to the metal-containing hard mask and features.

Abstract: Methods and apparatuses for selectively depositing oxide on an oxide surface relative to a nitride surface are described herein. Methods involve pre-treating a substrate surface using ammonia and/or nitrogen plasma and selectively depositing oxide on an oxide surface using alternating pulses of an aminosilane silicon precursor and an oxidizing agent in a thermal atomic layer deposition reaction without depositing oxide on an exposed nitride surface.

Abstract: Aluminum oxide films characterized by a dielectric constant (k) of less than about 7 (such as between about 4-6) and having a density of at least about 2.5 g/cm3 (such as about 3.0-3.2 g/cm3) are deposited on partially fabricated semiconductor devices over both metal and dielectric to serve as etch stop layers. The films are deposited using a deposition method that does not lead to oxidative damage of the metal. The deposition involves reacting an aluminum-containing precursor (e.g., a trialkylaluminum) with an alcohol and/or aluminum alkoxide. In one implementation the method involves flowing trimethylaluminum to the process chamber housing a substrate having an exposed metal and dielectric layers; purging and/or evacuating the process chamber; flowing t-butanol to the process chamber and allowing it to react with trimethylaluminum to form an aluminum oxide film and repeating the process steps until the film of desired thickness is formed.

Abstract: Methods are provided for integrating atomic layer etch and atomic layer deposition by performing both processes in the same chamber or reactor. Methods involve sequentially alternating between atomic layer etch and atomic layer deposition processes to prevent feature degradation during etch, improve selectivity, and encapsulate sensitive layers of a semiconductor substrate.

Abstract: Methods and apparatuses for selectively growing metal-containing hard masks are provided herein. Methods include providing a substrate having a pattern of spaced apart features, each feature having a top horizontal surface, filling spaces between the spaced apart features with carbon-containing material to form a planar surface having the top horizontal surfaces of the features and carbon-containing material, selectively depositing a metal-containing hard mask on the top horizontal surfaces of the features relative to the carbon-containing material, and selectively removing the carbon-containing material relative to the metal-containing hard mask and features.

Abstract: Methods and apparatuses for selectively depositing silicon oxide on a silicon oxide surface relative to a silicon nitride surface are described herein. Methods involve pre-treating a substrate surface using ammonia and/or nitrogen plasma and selectively depositing silicon oxide on a silicon oxide surface using alternating pulses of an aminosilane silicon precursor and an oxidizing agent in a thermal atomic layer deposition reaction without depositing silicon oxide on an exposed silicon nitride surface.

Abstract: Methods are provided for conducting a deposition on a semiconductor substrate by selectively depositing a material on the substrate. The substrate has a plurality of substrate materials, each with a different nucleation delay corresponding to the material deposited thereon. Specifically, the nucleation delay associated with a first substrate material on which deposition is intended is less than the nucleation delay associated with a second substrate material on which deposition is not intended according to a nucleation delay differential, which degrades as deposition proceeds. A portion of the deposited material is etched to reestablish the nucleation delay differential between the first and the second substrate materials. The material is further selectively deposited on the substrate.

Abstract: Vacuum-integrated photoresist-less methods and apparatuses for forming metal hardmasks can provide sub-30 nm patterning resolution. A metal-containing (e.g., metal salt or organometallic compound) film that is sensitive to a patterning agent is deposited on a semiconductor substrate. The metal-containing film is then patterned directly (i.e., without the use of a photoresist) by exposure to the patterning agent in a vacuum ambient to form the metal mask. For example, the metal-containing film is photosensitive and the patterning is conducted using sub-30 nm wavelength optical lithography, such as EUV lithography.

Abstract: Methods are provided for conducting a deposition on a semiconductor substrate by selectively depositing a material on the substrate. The substrate has a plurality of substrate materials, each with a different nucleation delay corresponding to the material deposited thereon. Specifically, the nucleation delay associated with a first substrate material on which deposition is intended is less than the nucleation delay associated with a second substrate material on which deposition is not intended according to a nucleation delay differential, which degrades as deposition proceeds. A portion of the deposited material is etched to reestablish the nucleation delay differential between the first and the second substrate materials. The material is further selectively deposited on the substrate.

Abstract: Methods and apparatuses for selectively depositing silicon oxide on surfaces relative to a metal-containing surface such as copper are provided. Methods involve exposing a substrate having hydroxyl-terminated or dielectric surfaces and copper surfaces to a copper-blocking reagent such as an alkyl thiol to selectively adsorb to the copper surface, exposing the substrate to a silicon-containing precursor for depositing silicon oxide, exposing the substrate to a weak oxidant gas and igniting a plasma, or water vapor without plasma, to convert the adsorb silicon-containing precursor to form silicon oxide. Some methods also involve exposing the substrate to a reducing agent to reduce any oxidized copper from exposure to the weak oxidant gas.

Abstract: Methods and apparatuses for selectively growing metal-containing hard masks are provided herein. Methods include providing a substrate having a pattern of spaced apart features, each feature having a top horizontal surface, filling spaces between the spaced apart features with carbon-containing material to form a planar surface having the top horizontal surfaces of the features and carbon-containing material, selectively depositing a metal-containing hard mask on the top horizontal surfaces of the features relative to the carbon-containing material, and selectively removing the carbon-containing material relative to the metal-containing hard mask and features.

Abstract: Vacuum-integrated photoresist-less methods and apparatuses for forming metal hardmasks can provide sub-30 nm patterning resolution. A metal-containing (e.g., metal salt or organometallic compound) film that is sensitive to a patterning agent is deposited on a semiconductor substrate. The metal-containing film is then patterned directly (i.e., without the use of a photoresist) by exposure to the patterning agent in a vacuum ambient to form the metal mask. For example, the metal-containing film is photosensitive and the patterning is conducted using sub-30 nm wavelength optical lithography, such as EUV lithography.

Abstract: Methods are provided for integrating atomic layer etch and atomic layer deposition by performing both processes in the same chamber or reactor. Methods involve sequentially alternating between atomic layer etch and atomic layer deposition processes to prevent feature degradation during etch, improve selectivity, and encapsulate sensitive layers of a semiconductor substrate.

Abstract: Methods and apparatuses for selectively depositing silicon nitride on silicon surfaces relative to silicon oxide surfaces and selectively depositing silicon nitride on silicon oxide surfaces relative to silicon surfaces are provided herein. Methods involve blocking one surface while leaving another surface unblocked and selectively depositing silicon nitride on the unblocked surface. The blocked surface may include an organic moiety having an Si—C bond. The method may include blocking one of an exposed hydroxyl-terminated silicon-containing surface and an exposed hydrogen-terminated silicon-containing surface of the substrate. Apparatuses include a process chamber having a pedestal, an outlet, and a controller for providing instructions for causing delivery of a semiconductor substrate to the pedestal, causing introduction of a silicon-containing precursor and causing introduction of a nitrogen-containing reactant without igniting a plasma.

Abstract: Methods and apparatuses for selectively depositing silicon oxide on dielectric surfaces relative to a metal-containing surface such as copper are provided. Methods involve exposing a substrate having dielectric and copper surfaces to a copper-blocking reagent such as an alkyl thiol to selectively adsorb to the copper surface, exposing the substrate to a silicon-containing precursor for depositing silicon oxide, exposing the substrate to a weak oxidant gas and igniting a plasma to convert the adsorb silicon-containing precursor to form silicon oxide, and exposing the substrate to a reducing agent to reduce any oxidized copper from exposure to the weak oxidant gas.