Abstract: A dry etch method, apparatus, and system for etching a high-k material comprises sequentially contacting the high-k material with a vapor phase reducing agent, and a volatilizing etchant in a cyclical process. In some preferred embodiments, the reducing agent and/or volatilizing etchant is plasma activated. Control over etch rate and/or selectivity are improved by the pulsed process, where, in some embodiments, each step in the cyclical process has a self-limited extent of etching. Embodiments of the method are useful in the fabrication of integrated devices, as well as for cleaning process chambers.

Abstract: Method and structures are provided for conformal lining of dual damascene structures in integrated circuits. Trenches and contact vias are formed in insulating layers. The trenches and vias are exposed to alternating chemistries to form monolayers of a desired lining material. Exemplary process flows include alternately pulsed metal halide and ammonia gases injected into a constant carrier flow. Self-terminated metal layers are thus reacted with nitrogen. Near perfect step coverage allows minimal thickness for a diffusion barrier function, thereby maximizing the volume of a subsequent filling metal for any given trench and via dimensions.

Abstract: In one aspect, non-conformal layers are formed by variations of plasma enhanced atomic layer deposition, where one or more of pulse duration, separation, RF power on-time, reactant concentration, pressure and electrode spacing are varied from true self-saturating reactions to operate in a depletion-effect mode. Deposition thus takes place close to the substrate surface but is controlled to terminate after reaching a specified distance into openings (e.g., deep DRAM trenches, pores, etc.). Reactor configurations that are suited to such modulation include showerhead, in situ plasma reactors, particularly with adjustable electrode spacing.

Abstract: Methods of forming metal carbide thin films are provided. According to preferred embodiments, metal carbide thin films are formed in an atomic layer deposition (ALD) process by alternately and sequentially contacting a substrate in a reaction space with spatially and temporally separated vapor phase pulses of a metal source chemical, a reducing agent and a carbon source chemical. The reducing agent is preferably selected from the group consisting of excited species of hydrogen and silicon-containing compounds.

Abstract: In one aspect, non-conformal layers are formed by variations of plasma enhanced atomic layer deposition, where one or more of pulse duration, separation, RF power on-time, reactant concentration, pressure and electrode spacing are varied from true self-saturating reactions to operate in a depletion-effect mode. Deposition thus takes place close to the substrate surface but is controlled to terminate after reaching a specified distance into openings (e.g., deep DRAM trenches, pores, etc.). Reactor configurations that are suited to such modulation include showerhead, in situ plasma reactors, particularly with adjustable electrode spacing.

Abstract: Methods of controllably producing conductive tantalum nitride films are provided. The methods comprise contacting a substrate in a reaction space with alternating and sequential pulses of a tantalum source material, plasma-excited species of hydrogen and nitrogen source material. The plasma-excited species of hydrogen reduce the oxidation state of tantalum, thereby forming a substantially conductive tantalum nitride film over the substrate. In some embodiments, the plasma-excited species of hydrogen react with and removes halide residues in a deposited metallic film.

Abstract: Methods for forming passivated stoichiometric metal nitride films are provided along with structures incorporating such films. The preferred methods include contacting a substrate with alternating and sequential pulses of a metal source chemical, one or more plasma-excited species of hydrogen and a nitrogen source chemical to form a stoichiometric metal nitride film, followed by exposure of the stoichiometric metal nitride film to a source chemical of a passivating species to form a passivation layer over the stoichiometric metal nitride film.

Abstract: A method for forming a conductive thin film includes depositing a metal oxide thin film on a substrate by an atomic layer deposition (ALD) process. The method further includes at least partially reducing the metal oxide thin film by exposing the metal oxide thin film to a reducing agent, thereby forming a seed layer. In one arrangement, the reducing agent comprises one or more organic compounds that contain at least one functional group selected from the group consisting of —OH, —CHO, and —COOH. In another arrangement, the reducing agent comprises an electric current.

Abstract: The present invention relates generally to depositing elemental thin films. In particular, the invention concerns a method of growing elemental metal thin films by Atomic Layer Deposition (ALD) using a boron compound as a reducing agent. In a preferred embodiment the method comprises introducing vapor phase pulses of at least one metal source compound and at least one boron source compound into a reaction space that contains a substrate on which the metal thin film is to be deposited. Preferably the boron compound is capable of reducing the adsorbed portion of the metal source compound into its elemental electrical state.

Abstract: A method is proposed for improving the adhesion between a diffusion barrier film and a metal film. Both the diffusion barrier film and the metal film can be deposited in either sequence onto a semiconductor substrate. A substrate comprising a first film, which is one of a diffusion barrier film or a metal film, with the first film being exposed at least at part of the surface area of the substrate, is exposed to an oxygen-containing reactant to create a surface termination of about one monolayer of oxygen-containing groups or oxygen atoms on the exposed parts of the first film. Then the second film, which is the other one of a diffusion barrier film and a metal film, is deposited onto the substrate. Furthermore, an oxygen bridge structure is proposed, the structure comprising a diffusion barrier film and a metal film having an interface with the diffusion barrier film, wherein the interface comprises a monolayer of oxygen atoms.

Abstract: Methods for forming passivated stoichiometric metal nitride films are provided along with structures incorporating such films. The preferred methods include contacting a substrate with alternating and sequential pulses of a metal source chemical, one or more plasma-excited species of hydrogen and a nitrogen source chemical to form a stoichiometric metal nitride film, followed by exposure of the stoichiometric metal nitride film to a source chemical of a passivating species to form a passivation layer over the stoichiometric metal nitride film.

Abstract: Methods of controllably producing conductive tantalum nitride films are provided. The methods comprise contacting a substrate in a reaction space with alternating and sequential pulses of a tantalum source material, plasma-excited species of hydrogen and nitrogen source material. The plasma-excited species of hydrogen reduce the oxidation state of tantalum, thereby forming a substantially conductive tantalum nitride film over the substrate. In some embodiments, the plasma-excited species of hydrogen react with and removes halide residues in a deposited metallic film.

Abstract: A method for forming a conductive thin film includes depositing a metal oxide thin film on a substrate by an atomic layer deposition (ALD) process. The method further includes at least partially reducing the metal oxide thin film by exposing the metal oxide thin film to a reducing agent, thereby forming a seed layer. In one arrangement, the reducing agent comprises one or more organic compounds that contain at least one functional group selected from the group consisting of —OH, —CHO, and —COOH. In another arrangement, the reducing agent comprises an electric current.

Abstract: Methods of forming a metal carbide film are provided. In some embodiments, methods for forming a metal carbide film in an atomic layer deposition (ALD) type process comprise alternately and sequentially contacting a substrate in a reaction space with vapor phase pulses of a metal compound and one or more plasma-excited species of a carbon-containing compound. In other embodiments, methods of forming a metal carbide film in a chemical vapor deposition (CVD) type process comprise simultaneously contacting a substrate in a reaction space with a metal compound and one or more plasma-excited species of a carbon-containing compound. The substrate is further exposed to a reducing agent.

Abstract: Metallic-compound films are formed by plasma-enhanced atomic layer deposition (PEALD). According to preferred methods, film or thin film composition is controlled by selecting plasma parameters to tune the oxidation state of a metal (or plurality of metals) in the film. In some embodiments, plasma parameters are selected to achieve metal-rich metallic-compound films. The metallic-compound films can be components of gate stacks, such as gate electrodes. Plasma parameters can be selected to achieve a gate stack with a predetermined work function.

Abstract: Methods of forming metal carbide thin films are provided. According to preferred embodiments, metal carbide thin films are formed in an atomic layer deposition (ALD) process by alternately and sequentially contacting a substrate in a reaction space with spatially and temporally separated vapor phase pulses of a metal source chemical, a reducing agent and a carbon source chemical. The reducing agent is preferably selected from the group consisting of excited species of hydrogen and silicon-containing compounds.

Abstract: The present method provides tools for growing conformal metal nitride, metal carbide and metal thin films, and nanolaminate structures incorporating these films, from aggressive chemicals. The amount of corrosive chemical compounds, such as hydrogen halides, is reduced during the deposition of transition metal, transition metal carbide and transition metal nitride thin films on various surfaces, such as metals and oxides. Getter compounds protect surfaces sensitive to hydrogen halides and ammonium halides, such as aluminum, copper, silicon oxide and the layers being deposited, against corrosion. Nanolaminate structures (20) incorporating metal nitrides, such as titanium nitride (30) and tungsten nitride (40), and metal carbides, and methods for forming the same, are also disclosed.

Abstract: The present invention relates generally to depositing elemental thin films. In particular, the invention concerns a method of growing elemental metal thin films by Atomic Layer Deposition (ALD) using a boron compound as a reducing agent. In a preferred embodiment the method comprises introducing vapor phase pulses of at least one metal source compound and at least one boron source compound into a reaction space that contains a substrate on which the metal thin film is to be deposited. Preferably the boron compound is capable of reducing the adsorbed portion of the metal source compound into its elemental electrical state.

Abstract: This invention concerns a process for producing integrated circuits containing at least one layer of elemental metal which during the processing of the integrated circuit is at least partly in the form of metal oxide, and the use of an organic compound containing certain functional groups for the reduction of a metal oxide layer formed during the production of an integrated circuit. According to the present process the metal oxide layer is at least partly reduced to elemental metal with a reducing agent selected from organic compounds containing one or more of the following functional groups: alcohol (—OH), aldehyde (—CHO), and carboxylic acid (—COOH).

Abstract: Methods of producing metal-containing thin films with low impurity contents on a substrate by atomic layer deposition (ALD) are provided. The methods preferably comprise contacting a substrate with alternating and sequential pulses of a metal source chemical, a second source chemical and a deposition enhancing agent. The deposition enhancing agent is preferably selected from the group consisting of hydrocarbons, hydrogen, hydrogen plasma, hydrogen radicals, silanes, germanium compounds, nitrogen compounds, and boron compounds. In some embodiments, the deposition-enhancing agent reacts with halide contaminants in the growing thin film, improving film properties.