Methods and apparatus for depositing a dielectric material include: providing a first gas mixture into a processing chamber having a substrate disposed therein; forming a first remote plasma comprising first radicals in a remote plasma source and delivering the first radicals to an interior processing region in the processing chamber to form a layer of dielectric material in an opening in a material layer disposed on the substrate in a presence of the first gas mixture and the first radicals; terminating the first remote plasma and applying a first RF bias power to the processing chamber to form a first bias plasma; contacting the layer of dielectric material with the first bias plasma to form a first treated layer of dielectric material; and subsequently forming a second remote plasma comprising second radicals in the remote plasma source and delivering the second radicals to the interior processing region in the processing chamber in a presence of a second gas mixture while applying a second RF bias power to the processing chamber to form a second bias plasma, wherein the second radicals and second bias plasma contact the first treated layer of dielectric material to increase a hydrophobicity or a viscosity of the first treated layer of dielectric material.

Examples of a method for manufacturing a semiconductor device include forming an initial film having a film thickness of 1 to 3 nm made of a metal or a metal nitride by applying plasma film formation with plasma power of 0.07 to 0.30 W/cm.sup.2 and an RF pulse width within a range of 0.1 to 1 sec, and forming, after forming the initial film, a bulk film made of a metal or metal nitride on the initial film by applying plasma film formation with plasma power higher than the plasma power when the initial film is formed.

Examples of a method for manufacturing a semiconductor device include forming an initial film having a film thickness of 1 to 3 nm made of a metal or a metal nitride by applying plasma film formation with plasma power of 0.07 to 0.30 W/cm.sup.2 and an RF pulse width within a range of 0.1 to 1 sec, and forming, after forming the initial film, a bulk film made of a metal or metal nitride on the initial film by applying plasma film formation with plasma power higher than the plasma power when the initial film is formed.

Embodiments include a method of processing a substrate. In an embodiment, the method comprises flowing one or more source gasses into a processing chamber, and inducing a plasma from the source gases with a plasma source that is operated in a first mode. In an embodiment, the method may further comprise biasing the substrate with a DC power source that is operated in a second mode. In an embodiment, the method may further comprise depositing a film on the substrate.

An article has a cavity defined by an inner surface, the cavity having a size such that a largest sphere placeable in the cavity has a diameter of less than 7 cm and a smallest sphere placeable in the cavity has a diameter of 0.5 mm; and a hard coating on the inner surface, the hard coating having a hardness between 18 to 100 GPa, the hard coating distributed on the inner surface such that a ratio of a coating thickness at a first region of the hard coating to that at a second region of the hard coating ranges from 0.75 to 1.33.

Embodiments include a method of processing a substrate. In an embodiment, the method comprises flowing one or more source gasses into a processing chamber, and inducing a plasma from the source gases with a plasma source that is operated in a first mode. In an embodiment, the method may further comprise biasing the substrate with a DC power source that is operated in a second mode. In an embodiment, the method may further comprise depositing a film on the substrate.

A method and composition for producing a porous low k dielectric film via chemical vapor deposition is provided. In one aspect, the method comprises the steps of: providing a substrate within a reaction chamber; introducing into the reaction chamber gaseous reagents including at least one structure-forming precursor comprising a alkoxysilacyclic or acyloxysilacyclic compound with or without a porogen; applying energy to the gaseous reagents in the reaction chamber to induce reaction of the gaseous reagents to deposit a preliminary film on the substrate, wherein the preliminary film contains the porogen, and the preliminary film is deposited; and removing from the preliminary film at least a portion of the porogen contained therein and provide the film with pores and a dielectric constant of 3.2 or less. In certain embodiments, the structure-forming precursor further comprises a hardening additive.

A method and composition for producing a porous low k dielectric film via chemical vapor deposition is provided. In one aspect, the method comprises the steps of: providing a substrate within a reaction chamber; introducing into the reaction chamber gaseous reagents including at least one structure-forming precursor comprising a alkoxysilacyclic or acyloxysilacyclic compound with or without a porogen; applying energy to the gaseous reagents in the reaction chamber to induce reaction of the gaseous reagents to deposit a preliminary film on the substrate, wherein the preliminary film contains the porogen, and the preliminary film is deposited; and removing from the preliminary film at least a portion of the porogen contained therein and provide the film with pores and a dielectric constant of 3.2 or less. In certain embodiments, the structure-forming precursor further comprises a hardening additive.

A method of forming crystallographically stabilized ferroelectric hafnium zirconium based films for semiconductor devices is described. The hafnium zirconium based films can be either doped or undoped. The method includes depositing a hafnium zirconium based film with a thickness greater than 5 nanometers on a substrate, depositing a cap layer on the hafnium zirconium based film, heat-treating the substrate to crystallize the hafnium zirconium based film in a non-centrosymmetric orthorhombic phase, a tetragonal phase, or a mixture thereof. The method further includes removing the cap layer from the substrate, thinning the heat-treated hafnium zirconium based film to a thickness of less than 5 nanometers, where the thinned heat-treated hafnium zirconium based film maintains the crystallized non-centrosymmetric orthorhombic phase, the tetragonal phase, or the mixture thereof.

An apparatus for depositing a coating on a substrate at atmospheric pressure comprises (a) a plasma torch comprising a microwave source coupled to an antenna disposed within a chamber having an open end, the chamber comprising a gas inlet for flow of a gas over the antenna to generate a plasma jet; (b) a substrate positioned outside the open end of the chamber a predetermined distance away from a tip of the antenna; and (c) a target material to be coated on the substrate disposed at the tip of the antenna.