Abstract: Methods of filling gaps with tungsten are described. The methods include a tungsten dep-etch-dep sequence to enhance gapfilling yet avoid difficulty in restarting deposition after the intervening etch. The first tungsten deposition may have a nucleation layer or seeding layer to assist growth of the first tungsten deposition. Restarting deposition with a less-than-conductive nucleation layer would impact function of an integrated circuit, and therefore avoiding tungsten “poisoning” during the etch is desirable. The etching step may be performed using a plasma to excite a halogen-containing precursor while the substrate at relatively low temperature (near room temperature or less). The plasma may be local or remote. Another method may be used in combination or separately and involves the introduction of a source of oxygen into the plasma in combination with the halogen-containing precursor.

Abstract: Embodiments of the invention provide an improved process for depositing tungsten-containing materials. In one embodiment, the method for forming a tungsten-containing material on a substrate includes forming an adhesion layer containing titanium nitride on a dielectric layer disposed on a substrate, forming a tungsten nitride intermediate layer on the adhesion layer, wherein the tungsten nitride intermediate layer contains tungsten nitride and carbon. The method further includes forming a tungsten barrier layer (e.g., tungsten or tungsten-carbon material) from the tungsten nitride intermediate layer by thermal decomposition during a thermal annealing process (e.g., temperature from about 700° C. to less than 1,000° C.).

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 a plasma comprising 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: Embodiments of the invention provide an improved process for depositing tungsten-containing materials. In one embodiment, the method for forming a tungsten-containing material on a substrate includes forming an adhesion layer containing titanium nitride on a dielectric layer disposed on a substrate, forming a tungsten nitride intermediate layer on the adhesion layer, wherein the tungsten nitride intermediate layer contains tungsten nitride and carbon. The method further includes forming a tungsten barrier layer (e.g., tungsten or tungsten-carbon material) from the tungsten nitride intermediate layer by thermal decomposition during a thermal annealing process (e.g., temperature from about 700° C. to less than 1,000° C.).

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: A method for selectively controlling deposition rate of a catalytic material during a catalytic bulk CVD deposition is disclosed herein. The method can include positioning a substrate in a processing chamber including both surface regions and gap regions, depositing a first nucleation layer comprising tungsten conformally over an exposed surface of the substrate, treating at least a portion of the first nucleation layer with activated nitrogen, wherein the activated nitrogen is deposited preferentially on the surface regions, reacting a first deposition gas comprising tungsten halide and hydrogen-containing gas to deposit a tungsten fill layer preferentially in gap regions of the substrate, reacting a nucleation gas comprising a tungsten halide to form a second nucleation layer, and reacting a second deposition gas comprising tungsten halide and a hydrogen-containing gas to deposit a tungsten field layer.

Abstract: Methods for processing a substrate are described herein. Methods can include positioning a substrate comprising silicon in a processing chamber, delivering a plasma to the surface of the substrate while biasing the substrate, exposing the surface of the substrate to ammonium fluoride (NH4F), and annealing the substrate to a first temperature to sublimate one or more volatile byproducts.

Abstract: Embodiments of the invention provide an improved process for depositing tungsten-containing materials. In one embodiment, the method for forming a tungsten-containing material on a substrate includes forming an adhesion layer containing titanium nitride on a dielectric layer disposed on a substrate, forming a tungsten nitride intermediate layer on the adhesion layer, wherein the tungsten nitride intermediate layer contains tungsten nitride and carbon. The method further includes forming a tungsten barrier layer (e.g., tungsten or tungsten-carbon material) from the tungsten nitride intermediate layer by thermal decomposition during a thermal annealing process (e.g., temperature from about 700° C. to less than 1,000° C.).

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: Embodiments of the invention provide an improved process for depositing tungsten-containing materials. In one embodiment, the method for forming a tungsten-containing material on a substrate includes forming an adhesion layer containing titanium nitride on a dielectric layer disposed on a substrate, forming a tungsten nitride intermediate layer on the adhesion layer, wherein the tungsten nitride intermediate layer contains tungsten nitride and carbon. The method further includes forming a tungsten barrier layer (e.g., tungsten or tungsten-carbon material) from the tungsten nitride intermediate layer by thermal decomposition during a thermal annealing process (e.g., temperature from about 700° C. to less than 1,000° C.).

Abstract: The present invention addresses this need by providing methods for depositing low resistivity tungsten films in small features and features having high aspect ratios. The methods involve depositing very thin tungsten nucleation layers by pulsed nucleation layer (PNL) processes and then using chemical vapor deposition (CVD) to deposit a tungsten layer to fill the feature. Depositing the tungsten nucleation layer involves exposing the substrate to alternating pulses of a boron-containing reducing agent and a tungsten-containing precursor without using any hydrogen gas, e.g., as a carrier or background gas. Using this process, a conformal tungsten nucleation layer can be deposited to a thickness as small as about 10 Angstroms. The feature may then be wholly or partially filled with tungsten by a hydrogen reduction chemical vapor deposition process. Resistivities of about 14 ??-cm for a 500 Angstrom film may be obtained.

Abstract: Improved methods for depositing low resistivity tungsten films are provided. The methods involve depositing a tungsten nucleation layer on a substrate and then depositing a tungsten bulk layer over the tungsten nucleation layer to form the tungsten film. The methods provide precise control of the nucleation layer thickness and improved step coverage. According to various embodiments, the methods involve controlling thickness and/or improving step coverage by exposing the substrate to pulse nucleation layer (PNL) cycles at low temperature. Also in some embodiments, the methods may improve resistivity by using a high temperature PNL cycle of a boron-containing species and a tungsten-containing precursor to finish forming the tungsten nucleation layer.

Abstract: Methods for accurate and conformal removal of atomic layers of materials make use of the self-limiting nature of adsorption of at least one reactant on the substrate surface. In certain embodiments, a first reactant is introduced to the substrate in step (a) and is adsorbed on the substrate surface until the surface is partially or fully saturated. A second reactant is then added in step (b), reacting with the adsorbed layer of the first reactant to form an etchant. The amount of an etchant, and, consequently, the amount of etched material is limited by the amount of adsorbed first reactant. By repeating steps (a) and (b), controlled atomic-scale etching of material is achieved. These methods may be used in interconnect pre-clean applications, gate dielectric processing, manufacturing of memory devices, or any other applications where removal of one or multiple atomic layers of material is desired.

Abstract: The present invention addresses this need by providing methods for depositing low resistivity tungsten films in small features and features having high aspect ratios. The methods involve depositing very thin tungsten nucleation layers by pulsed nucleation layer (PNL) processes and then using chemical vapor deposition (CVD) to deposit a tungsten layer to fill the feature. Depositing the tungsten nucleation layer involves exposing the substrate to alternating pulses of a boron-containing reducing agent and a tungsten-containing precursor without using any hydrogen gas, e.g., as a carrier or background gas. Using this process, a conformal tungsten nucleation layer can be deposited to a thickness as small as about 10 Angstroms. The feature may then be wholly or partially filled with tungsten by a hydrogen reduction chemical vapor deposition process. Resistivities of about 14 ??-cm for a 500 Angstrom film may be obtained.

Abstract: The present invention addresses this need by providing methods for depositing low resistivity tungsten films in small features and features having high aspect ratios. The methods involve depositing very thin tungsten nucleation layers by pulsed nucleation layer (PNL) processes and then using chemical vapor deposition (CVD) to deposit a tungsten layer to fill the feature. Depositing the tungsten nucleation layer involves exposing the substrate to alternating pulses of a boron-containing reducing agent and a tungsten-containing precursor without using any hydrogen gas, e.g., as a carrier or background gas. Using this process, a conformal tungsten nucleation layer can be deposited to a thickness as small as about 10 Angstroms. The feature may then be wholly or partially filled with tungsten by a hydrogen reduction chemical vapor deposition process. Resistivities of about 14 ??-cm for a 500 Angstrom film may be obtained.

Abstract: The present invention provides improved methods of depositing tungsten-containing films on substrates, particularly on silicon substrates. The methods involve depositing an interfacial or “flash” layer of tungsten on the silicon prior to deposition of tungsten nitride. The tungsten flash layer is typically deposited by a CVD reaction of a tungsten precursor and a reducing agent. According to various embodiments, the tungsten flash layer may be deposited with a high reducing agent to tungsten-precursor ratio and/or at low temperature to reduce attack by the tungsten precursor. In many cases, the substrate is a semiconductor wafer or a partially fabricated semiconductor wafer. Applications include depositing tungsten nitride as (or as part of) a diffusion barrier and/or adhesion layer for tungsten contacts.

Abstract: Methods for depositing a tungsten nitride layer are described. The methods form a tungsten nitride layer using a carefully controlled deposition technique such as pulsed nucleation layer (PNL). Initially, a tungsten layer is formed on a substrate surface. The tungsten layer is then exposed to a nitriding agent to form a tungsten nitride layer. Methods of forming relatively thick layers of involve repeated cycles of contact with reducing agent, tungsten precursor and nitriding agent. In some cases, the cycle may also include contact with a dopant precursor such as phosphine or arsine.

Abstract: Improved methods for depositing low resistivity tungsten films are provided. The methods involve depositing a tungsten nucleation layer on a substrate and then depositing a tungsten bulk layer over the tungsten nucleation layer to form the tungsten film. The methods provide precise control of the nucleation layer thickness and improved step coverage. According to various embodiments, the methods involve controlling thickness and/or improving step coverage by exposing the substrate to pulse nucleation layer (PNL) cycles at low temperature. Also in some embodiments, the methods may improve resistivity by using a high temperature PNL cycle of a boron-containing species and a tungsten-containing precursor to finish forming the tungsten nucleation layer.

Abstract: Improved methods for depositing low resistivity tungsten films are provided. The methods involve depositing a tungsten nucleation layer on a substrate and then depositing a tungsten bulk layer over the tungsten nucleation layer to form the tungsten film. The methods provide precise control of the nucleation layer thickness and improved step coverage. According to various embodiments, the methods involve controlling thickness and/or improving step coverage by exposing the substrate to pulse nucleation layer (PNL) cycles at low temperature. Also in some embodiments, the methods may improve resistivity by using a high temperature PNL cycle of a boron-containing species and a tungsten-containing precursor to finish forming the tungsten nucleation layer.

Abstract: The present invention addresses this need by providing methods for depositing low resistivity tungsten films in small features and features having high aspect ratios. The methods involve depositing very thin tungsten nucleation layers by pulsed nucleation layer (PNL) processes and then using chemical vapor deposition (CVD) to deposit a tungsten layer to fill the feature. Depositing the tungsten nucleation layer involves exposing the substrate to alternating pulses of a boron-containing reducing agent and a tungsten-containing precursor without using any hydrogen gas, e.g., as a carrier or background gas. Using this process, a conformal tungsten nucleation layer can be deposited to a thickness as small as about 10 Angstroms. The feature may then be wholly or partially filled with tungsten by a hydrogen reduction chemical vapor deposition process. Resistivities of about 14 ??-cm for a 500 Angstrom film may be obtained.