Abstract: Provided are deposition processes including deposition of a thin, protective Mo layer using a molybdenum chloride (MoClx) precursor. This may be followed by Mo deposition to fill the feature using a molybdenum oxyhalide (MoOyXz) precursor. The protective Mo layer enables Mo fill using an MoOyXz precursor without oxidation of the underlying surfaces. Also provided are in-situ clean processes in which a MoClx precursor is used to remove oxidation from underlying surfaces prior to deposition. Subsequent deposition using the MoClx precursor may deposit an initial layer and/or fill a feature.

Abstract: Methods of filling features including metal and dielectric surfaces with conductive materials involve cleaning the metal surfaces with little or no damage to the dielectric surfaces. After cleaning, the feature may be exposed to one or more reactants to fill the feature with the conductive material in an atomic layer deposition (ALD) or chemical vapor deposition (CVD) process. Deposition may be selective or non-selective to the metal surface. In some embodiments, the filled feature is barrier-less, such that the conductive material directly contacts the metal and dielectric surfaces with no interposing barrier or adhesion layer.

Abstract: Provided are methods of filling patterned features with molybdenum (Mo). The methods involve selective deposition of Mo films on bottom metal-containing surfaces of a feature including dielectric sidewalls. The selective growth of Mo on the bottom surface allows bottom-up growth and high quality, void-free fill. Also provided are related apparatus.

Abstract: In some embodiments, deposition processes for ruthenium (Ru) feature fill include deposition of a thin, protective Ru film under reducing conditions, followed by a Ru fill step under oxidizing conditions. The presence of protective Ru films formed under oxygen-free conditions or with an oxygen-removing operation can enable Ru fill without oxidation of an underlying adhesion layer or metal feature.

Abstract: Provided herein are methods of forming conductive cobalt (Co) interconnects and Co features. The methods involve deposition of a thin manganese (Mn)-containing film on a dielectric followed by subsequent deposition of cobalt on the Mn-containing film. The Mn-containing film may be deposited on a silicon-containing dielectric, such as silicon dioxide, and annealed to form a manganese silicate.

Abstract: Provided are methods of forming diffusion barriers and adhesion layers for interconnects such as cobalt (Co) interconnects or ruthenium (Ru) interconnects. The methods involve selective deposition of tungsten carbon nitride (WCN) films on the oxide surfaces of a feature including a Co surface. The selective growth of WCN on oxide allows the contact resistance at an interface such as a Co—Co interface or a Co—Ru interface to be significantly reduced while maintaining good film coverage, adhesion, and/or barrier properties on the sidewall oxide surfaces.

Abstract: Provided herein are atomic layer deposition (ALD) methods of depositing cobalt in a feature. The methods involve two-step surface treatments during an ALD cycle, with one step involving the reaction of a co-reactant gas with an adsorbed cobalt precursor and the other step involving a growth-inhibiting reactant gas on the cobalt surface. The growth-inhibiting reactant gas significantly lowers cobalt growth rate, producing a highly conformal cobalt film. The described ALD processes enable improved controllability in film nucleation, step coverage, and morphology by the separate surface treatment and low process temperature. The methods are applicable to a variety of feature fill applications including the fabrication of metal gate/contact fill in front end of line (FEOL) processes as well as via/line fill in back end of line (BEOL) processes.

Abstract: A method for depositing a metal layer on a barrier layer includes a) arranging a substrate in a processing chamber. The substrate has been exposed to at least one of air and/or oxidizing chemistry and includes a barrier layer and one or more underlying layers, wherein the barrier layer includes a material selected from a group consisting of tantalum nitride, titanium nitride, tantalum and titanium. The method includes b) supplying a gas selected from a group consisting of hydrazine, a gas including fluorine species, a gas including chlorine species, derivatives of hydrazine, ammonia, carbon monoxide, a gas including amidinates, and/or a gas including metal organic ligands to the processing chamber for a predetermined period to remove oxidation from the barrier layer. The method includes c) depositing a metal layer on the barrier layer after b). The metal layer includes a metal selected from a group consisting of cobalt, copper, tungsten, ruthenium, rhodium, molybdenum, and nickel.

Abstract: Provided are deposition processes for ruthenium (Ru) feature fill. In some embodiments, the processes include deposition of a thin, protective Ru film under reducing conditions, followed by a Ru fill step under oxidizing conditions. The presence of protective Ru films formed under oxygen-free conditions or with an oxygen-removing operation can enable Ru fill without oxidation of an underlying adhesion layer or metal feature.

Abstract: Provided herein are atomic layer deposition (ALD) methods of depositing cobalt in a feature. The methods involve two-step surface treatments during an ALD cycle, with one step involving the reaction of a co-reactant gas with an adsorbed cobalt precursor and the other step involving a growth-inhibiting reactant gas on the cobalt surface. The growth-inhibiting reactant gas significantly lowers cobalt growth rate, producing a highly conformal cobalt film. The described ALD processes enable improved controllability in film nucleation, step coverage, and morphology by the separate surface treatment and low process temperature. The methods are applicable to a variety of feature fill applications including the fabrication of metal gate/contact fill in front end of line (FEOL) processes as well as via/line fill in back end of line (BEOL) processes.

Abstract: Provided are methods of forming diffusion barriers and adhesion layers for interconnects such as cobalt (Co) interconnects or ruthenium (Ru) interconnects. The methods involve selective deposition of tungsten carbon nitride (WCN) films on the oxide surfaces of a feature including a Co surface. The selective growth of WCN on oxide allows the contact resistance at an interface such as a Co—Co interface or a Co—Ru interface to be significantly reduced while maintaining good film coverage, adhesion, and/or barrier properties on the sidewall oxide surfaces.

Abstract: A method for depositing a metal layer on a barrier layer includes a) arranging a substrate in a processing chamber. The substrate has been exposed to at least one of air and/or oxidizing chemistry and includes a barrier layer and one or more underlying layers, wherein the barrier layer includes a material selected from a group consisting of tantalum nitride, titanium nitride, tantalum and titanium. The method includes b) supplying a gas selected from a group consisting of hydrazine, a gas including fluorine species, a gas including chlorine species, derivatives of hydrazine, ammonia, carbon monoxide, a gas including amidinates, and/or a gas including metal organic ligands to the processing chamber for a predetermined period to remove oxidation from the barrier layer. The method includes c) depositing a metal layer on the barrier layer after b). The metal layer includes a metal selected from a group consisting of cobalt, copper, tungsten, ruthenium, rhodium, molybdenum, and nickel.

Abstract: Provided herein are methods of forming conductive cobalt (Co) interconnects and Co features. The methods involve deposition of a thin manganese (Mn)-containing film on a dielectric followed by subsequent deposition of cobalt on the Mn-containing film. The Mn-containing film may be deposited on a silicon-containing dielectric, such as silicon dioxide, and annealed to form a manganese silicate.

Abstract: Provided herein are methods of depositing void-free cobalt into features with high aspect ratios. Methods involve (a) partially filling a feature with cobalt, (b) exposing the feature to a plasma generated from nitrogen-containing gas to selectively inhibit cobalt nucleation on surfaces near or at the top of the feature, optionally repeating (a) and (b), and depositing bulk cobalt into the feature by chemical vapor deposition. Methods may also involve exposing a feature including a barrier layer to a plasma generated from nitrogen-containing gas to selectively inhibit cobalt nucleation. The methods may be performed at low temperatures less than about 400° C. using cobalt-containing precursors. Methods may also involve using a remote plasma source to generate the nitrogen-based plasma. Methods also involve annealing the substrate.

Abstract: Provided herein are methods of depositing void-free cobalt into features with high aspect ratios. Methods involve (a) partially filling a feature with cobalt, (b) exposing the feature to a plasma generated from nitrogen-containing gas to selectively inhibit cobalt nucleation on surfaces near or at the top of the feature, optionally repeating (a) and (b), and depositing bulk cobalt into the feature by chemical vapor deposition. Methods may also involve exposing a feature including a barrier layer to a plasma generated from nitrogen-containing gas to selectively inhibit cobalt nucleation. The methods may be performed at low temperatures less than about 400° C. using cobalt-containing precursors.

Abstract: Provided herein are methods of depositing void-free cobalt into features with high aspect ratios. Methods involve (a) partially filling a feature with cobalt, (b) exposing the feature to a plasma generated from nitrogen-containing gas to selectively inhibit cobalt nucleation on surfaces near or at the top of the feature, optionally repeating (a) and (b), and depositing bulk cobalt into the feature by chemical vapor deposition. Methods may also involve exposing a feature including a barrier layer to a plasma generated from nitrogen-containing gas to selectively inhibit cobalt nucleation. The methods may be performed at low temperatures less than about 400° C. using cobalt-containing precursors. Methods may also involve using a remote plasma source to generate the nitrogen-based plasma. Methods also involve annealing the substrate.

Abstract: Provided herein are methods of depositing void-free cobalt into features with high aspect ratios. Methods involve (a) partially filling a feature with cobalt, (b) exposing the feature to a plasma generated from nitrogen-containing gas to selectively inhibit cobalt nucleation on surfaces near or at the top of the feature, optionally repeating (a) and (b), and depositing bulk cobalt into the feature by chemical vapor deposition. Methods may also involve exposing a feature including a barrier layer to a plasma generated from nitrogen-containing gas to selectively inhibit cobalt nucleation. The methods may be performed at low temperatures less than about 400° C. using cobalt-containing precursors.

Abstract: Systems and methods deposit a film on a substrate by introducing a precursor gas into a reaction volume of a processing chamber. A substrate is arranged in the reaction volume. After a predetermined soak period, the precursor gas is purged from the reaction volume. The substrate is exposed with plasma gas using a remote plasma source.

Abstract: Systems and methods deposit a film on a substrate by introducing a precursor gas into a reaction volume of a processing chamber. A substrate is arranged in the reaction volume. After a predetermined soak period, the precursor gas is purged from the reaction volume. The substrate is exposed with plasma gas using a remote plasma source.

Abstract: Systems, methods, and apparatus for depositing a tantalum layer on a wafer substrate are disclosed. In one aspect, a tantalum layer may be deposited on a surface of a wafer substrate using an ion-induced atomic layer deposition process with a tantalum precursor. A copper layer may be deposited on the tantalum layer.