Abstract: Provided herein are methods and apparatuses for reducing line bending when depositing a metal such as tungsten, molybdenum, ruthenium, or cobalt into features on substrates by periodically exposing the feature to nitrogen, oxygen, or ammonia during atomic layer deposition, chemical vapor deposition, or sequential chemical vapor deposition to reduce interactions between metal deposited onto sidewalls of a feature. Methods are suitable for deposition into V-shaped features.

Abstract: Methods of depositing fluorine-free tungsten by sequential CVD pulses, such as by alternately pulsing a fluorine-free tungsten precursor and hydrogen in cycles of temporally separated pulses, are provided. Some methods involve depositing fluorine-free tungsten by sequential CVD without depositing a tungsten nucleation layer. Methods also include depositing tungsten directly on a substrate surface using alternating pulses of a chlorine-containing tungsten precursor and hydrogen without treating the substrate surface. Methods also include depositing a tungsten layer using a reducing agent and fluorine-free tungsten-containing precursor and depositing bulk tungsten in sequential CVD cycles of alternating pulses of hydrogen and a tungsten-containing precursor.

Abstract: Provided herein are low resistance metallization stack structures for logic and memory applications and related methods of fabrication. In some implementations, the methods involve providing a tungsten (W)-containing layer on a substrate; and depositing a molybdenum (Mo)-containing layer on the W-containing layer. In some implementations, the methods involve depositing a Mo-containing layer directly on a dielectric or titanium nitride (TiN) substrate without an intervening W-containing layer.

Abstract: A method for depositing tungsten includes arranging a substrate including a titanium nitride layer in a substrate processing chamber and performing multi-stage atomic layer deposition of tungsten on the substrate using a precursor gas includes tungsten chloride (WCIx) gas, wherein x is an integer. The performing includes depositing the tungsten during a first ALD stage using a first dose intensity of the precursor gas, and depositing the tungsten during a second ALD stage using a second dose intensity of the precursor gas. The first dose intensity is based on a first dose concentration and a first dose period. The second dose intensity is based on a second dose concentration and a second dose period. The second dose intensity is 1.5 to 10 times the first dose intensity.

Abstract: A method for depositing tungsten includes arranging a substrate including a titanium nitride layer in a substrate processing chamber and performing multi-stage atomic layer deposition of tungsten on the substrate using a precursor gas includes tungsten chloride (WClx) gas, wherein x is an integer. The performing includes depositing the tungsten during a first ALD stage using a first dose intensity of the precursor gas, and depositing the tungsten during a second ALD stage using a second dose intensity of the precursor gas. The first dose intensity is based on a first dose concentration and a first dose period. The second dose intensity is based on a second dose concentration and a second dose period. The second dose intensity is 1.5 to 10 times the first dose intensity.

Abstract: Provided herein are low resistance metallization stack structures for logic and memory applications and related methods of fabrication. In some implementations, the methods involve providing a tungsten (W)-containing layer on a substrate; and depositing a molybdenum (Mo)-containing layer on the W-containing layer. In some implementations, the methods involve depositing a Mo-containing layer directly on a dielectric or titanium nitride (TiN) substrate without an intervening W-containing layer.

Abstract: A vaporizer system is provided that allows for rapid shifts in the flow rate of a vaporized reactant while maintaining a constant overall flow rate of vaporized reactant and carrier gas.

Abstract: Methods of depositing fluorine-free tungsten by sequential CVD pulses, such as by alternately pulsing a fluorine-free tungsten precursor and hydrogen in cycles of temporally separated pulses, are provided. Some methods involve depositing fluorine-free tungsten by sequential CVD without depositing a tungsten nucleation layer. Methods also include depositing tungsten directly on a substrate surface using alternating pulses of a chlorine-containing tungsten precursor and hydrogen without treating the substrate surface. Methods also include depositing a tungsten layer using a reducing agent and fluorine-free tungsten-containing precursor and depositing bulk tungsten in sequential CVD cycles of alternating pulses of hydrogen and a tungsten-containing precursor.

Abstract: Provided herein are methods of depositing fluorine-free tungsten by sequential CVD pulses, such as by alternately pulsing a chlorine-containing tungsten precursor and hydrogen in cycles of temporally separated pulses, without depositing a tungsten nucleation layer. Methods also include depositing tungsten directly on a substrate surface using alternating pulses of a chlorine-containing tungsten precursor and hydrogen without treating the substrate surface.

Abstract: Provided herein are methods and apparatuses for reducing line bending when depositing a metal such as tungsten, molybdenum, ruthenium, or cobalt into features on substrates by periodically exposing the feature to nitrogen, oxygen, or ammonia during atomic layer deposition, chemical vapor deposition, or sequential chemical vapor deposition to reduce interactions between metal deposited onto sidewalls of a feature. Methods are suitable for deposition into V-shaped features.

Abstract: A method for depositing tungsten includes arranging a substrate including a titanium nitride layer in a substrate processing chamber and performing multi-stage atomic layer deposition of tungsten on the substrate using a precursor gas includes tungsten chloride (WClx) gas, wherein x is an integer. The performing includes depositing the tungsten during a first ALD stage using a first dose intensity of the precursor gas, and depositing the tungsten during a second ALD stage using a second dose intensity of the precursor gas. The first dose intensity is based on a first dose concentration and a first dose period. The second dose intensity is based on a second dose concentration and a second dose period. The second dose intensity is 1.5 to 10 times the first dose intensity.

Abstract: Vapor accumulator reservoirs for semiconductor processing operations, such as atomic layer deposition operations, are provided. Such vapor accumulator reservoirs may include an optical beam port to allow an optical beam to transit through the vapor and allow measurement of the vapor concentration in the reservoir. In some implementations, the reservoir may be integrated with a vacuum pumping manifold and the reservoir and manifold may be heated by a common heating system to prevent condensation of the vapor.

Abstract: A vaporizer system is provided that allows for rapid shifts in the flow rate of a vaporized reactant while maintaining a constant overall flow rate of vaporized reactant and carrier gas.

Abstract: Methods for processing a substrate are described herein. Methods can include positioning a substrate with an exposed surface comprising a silicon oxide layer in a processing chamber, biasing the substrate, treating the substrate to roughen a portion of the silicon oxide layer, heating the substrate to a first temperature, exposing the exposed surface of the substrate to ammonium fluoride to form one or more volatile products while maintaining the first temperature, and heating the substrate to a second temperature, which is higher than the first temperature, to sublimate the volatile products.

Abstract: Provided herein are methods of depositing fluorine-free tungsten by sequential CVD pulses, such as by alternately pulsing a chlorine-containing tungsten precursor and hydrogen in cycles of temporally separated pulses, without depositing a tungsten nucleation layer. Methods also include depositing tungsten directly on a substrate surface using alternating pulses of a chlorine-containing tungsten precursor and hydrogen without treating the substrate surface.

Abstract: Methods for forming tungsten film using fluorine-free tungsten precursors such as tungsten chlorides are provided. Methods involve depositing a tungsten nucleation layer by exposing a substrate to a reducing agent such as diborane (B2H6) and exposing the substrate to a tungsten chloride, followed by depositing bulk tungsten by exposing the substrate to a tungsten chloride and a reducing agent. Methods also involve diluting the reducing agent and exposing the substrate to a fluorine-free precursor in pulses to deposit a tungsten nucleation layer. Deposited films exhibit good step coverage and plugfill.

Abstract: A tungsten nucleation film is formed on a surface of a semiconductor substrate by alternatively providing to that surface, reducing gases and tungsten-containing gases. Each cycle of the method provides for one or more monolayers of the tungsten film. The film is conformal and has improved step coverage, even for a high aspect ratio contact hole.

Abstract: Methods for processing a substrate are described herein. Methods can include positioning a substrate with an exposed surface comprising a silicon oxide layer in a processing chamber, biasing the substrate, treating the substrate to roughen a portion of the silicon oxide layer, heating the substrate to a first temperature, exposing the exposed surface of the substrate to ammonium fluoride to form one or more volatile products while maintaining the first temperature, and heating the substrate to a second temperature, which is higher than the first temperature, to sublimate the volatile products.

Abstract: Methods for plasma treatment of films to remove impurities are disclosed herein. Methods for removing impurities can include positioning a substrate with a barrier layer in a processing chamber, the barrier layer comprising a barrier metal and one or more impurities, maintaining the substrate at a bias, creating a plasma comprising a treatment gas, the treatment gas comprising an inert gas, delivering the treatment gas to the substrate to reduce the ratio of one or more impurities in the barrier layer, and reacting a deposition gas comprising a metal halide and hydrogen-containing gas to deposit a bulk metal layer on the barrier layer. The methods can further include the use of diborane to create selective nucleation in features over surface regions of the substrate.

Abstract: Methods for processing a substrate are described herein. Methods can include positioning a substrate with an exposed surface comprising a silicon oxide layer in a processing chamber, biasing the substrate, treating the substrate to roughen a portion of the silicon oxide layer, heating the substrate to a first temperature, exposing the exposed surface of the substrate to ammonium fluoride to form one or more volatile products while maintaining the first temperature, and heating the substrate to a second temperature, which is higher than the first temperature, to sublimate the volatile products.