Embodiments of methods of filling features with molybdenum (Mo) include depositing a first layer of Mo in a feature including an opening and an interior and non-conformally treating the first layer such that regions near the opening preferentially treated over regions in the interior. In some embodiments, a second Mo layer is deposited on the treated first layer. Embodiments of methods of filling features with Mo include controlling Mo precursor flux to transition between conformal and non-conformal fill.

A semiconductor device includes a gate structure on a semiconductor fin, a dielectric layer on the gate structure, and a gate contact extending through the dielectric layer to the gate structure. The gate contact includes a first conductive material on the gate structure, a top surface of the first conductive material extending between sidewalls of the dielectric layer, and a second conductive material on the top surface of the first conductive material.

Methods of depositing a metal film are discussed. A metal film is formed on the bottom of feature having a metal bottom and dielectric sidewalls. Formation of the metal film comprises exposure to a metal precursor and an alkyl halide catalyst while the substrate is maintained at a deposition temperature. The metal precursor has a decomposition temperature above the deposition temperature. The alkyl halide comprises carbon and halogen, and the halogen comprises bromine or iodine.

A method of preparing a self-aligned via on a semiconductor workpiece includes using an integrated sequence of processing steps executed on a common manufacturing platform hosting a plurality of processing modules including one or more film-forming modules, one or more etching modules, and one or more transfer modules. The integrated sequence of processing steps include receiving the workpiece into the common manufacturing platform, the workpiece having a pattern of metal features in a dielectric layer wherein exposed surfaces of the metal features and exposed surfaces of the dielectric layer together define an upper planar surface; selectively etching the metal features to form a recess pattern by recessing the exposed surfaces of the metal features beneath the exposed surfaces of the dielectric layer using one of the one or more etching modules; and depositing an etch stop layer over the recess pattern using one of the one or more film-forming modules.

A method includes providing a substrate having a conductive column, a dielectric layer over the conductive column, and a plurality of sacrificial blocks over the dielectric layer, the plurality of sacrificial blocks surrounding the conductive column from a top view; depositing a sacrificial layer covering the plurality of sacrificial blocks, the sacrificial layer having a dip directly above the conductive column; depositing a hard mask layer over the sacrificial layer; removing a portion of the hard mask layer from a bottom of the dip; etching the bottom of the dip using the hard mask layer as an etching mask, thereby exposing a top surface of the conductive column; and forming a conductive material inside the dip, the conductive material being in physical contact with the top surface of the conductive column.

Described herein are methods of filling features with tungsten and related apparatus. The methods described herein involve deposition of a tungsten nucleation layer prior to deposition of a bulk layer. The methods involve multiple atomic layer deposition (ALD) cycles. According to various embodiments, both a boron-containing reducing agent and silicon-reducing agent may be pulses during a single cycle to react with a tungsten-containing precursor and form a tungsten film.

The present disclosure describes a method for forming a nitrogen-rich protective layer within a low-k layer of a metallization layer to prevent damage to the low-k layer from subsequent processing operations. The method includes forming, on a substrate, a metallization layer having conductive structures in a low-k dielectric. The method further includes forming a capping layer on the conductive structures, where forming the capping layer includes exposing the metallization layer to a first plasma process to form a nitrogen-rich protective layer below a top surface of the low-k dielectric, releasing a precursor on the metallization layer to cover top surfaces of the conductive structures with precursor molecules, and treating the precursor molecules with a second plasma process to dissociate the precursor molecules and form the capping layer. Additionally, the method includes forming an etch stop layer to cover the capping layer and top surfaces of the low-k dielectric.

A method includes forming an insulating layer over a conductive feature; etching the insulating layer to expose a first surface of the conductive feature; covering the first surface of the conductive feature with a sacrificial material, wherein the sidewalls of the insulating layer are free of the sacrificial material; covering the sidewalls of the insulating layer with a barrier material, wherein the first surface of the conductive feature is free of the barrier material, wherein the barrier material includes tantalum nitride (TaN) doped with a transition metal; removing the sacrificial material; and covering the barrier material and the first surface of the conductive feature with a conductive material.

Described are methods for controlling the doping of metal nitride films such as TaN, TiN and MnN. The temperature during deposition of the metal nitride film may be controlled to provide a film density that permits a desired amount of doping. Dopants may include Ru, Cu, Co, Mn, Mo, Al, Mg, Cr, Nb, Ta, Ti and V. The metal nitride film may optionally be exposed to plasma treatment after doping.

Metal nitride diffusion barriers may be included between cobalt-based structures and ruthenium-based structures to reduce, minimize, and/or prevent intermixing of cobalt into ruthenium. A metal nitride diffusion barrier layer may include a cobalt nitride (CoN.sub.x), a ruthenium nitride (RuN.sub.x), or another metal nitride that has a bond dissociation energy greater than the bond dissociation energy of cobalt to cobalt (Co—Co), and may therefore function as a strong barrier to cobalt migration and diffusion into ruthenium. Moreover, cobalt nitride and ruthenium nitride have lower resistivity relative to other materials such as titanium nitride (TiN), tungsten nitride (WN), and tantalum nitride (TaN). In this way, the metal nitride diffusion barriers are capable of minimizing cobalt diffusion and intermixing into ruthenium-based interconnect structures while maintaining a low contact resistance for the interconnect structures. This may increase semiconductor device performance, may increase semiconductor device yield, and may enable further reductions in interconnect structure size.