To provide a film forming material and a film forming process for forming, at a lower temperature, a Ge-containing Co film including a desired amount of Ge. A film forming material for forming a Ge-containing Co film according to the invention is represented by either formula (1) or formula (2) below R.sup.1R.sup.2R.sup.3GeCo(CO).sub.4 (1) (where R.sup.1, R.sup.2 and R.sup.3 are each independently hydrogen, a nonaromatic hydrocarbon group, a halogeno group or a halogenated nonaromatic hydrocarbon group; however, the nonaromatic hydrocarbon group excludes a crosslinked nonaromatic hydrocarbon group, and the halogenated nonaromatic hydrocarbon group excludes a crosslinked halogenated nonaromatic hydrocarbon group) Co(CO).sub.4R.sup.4R.sup.5GeCo(CO).sub.4 (2) (where R.sup.4 and R.sup.5 are each independently hydrogen, a nonaromatic hydrocarbon group, a halogeno group or a halogenated nonaromatic hydrocarbon group; however, the nonaromatic hydrocarbon group excludes a crosslinked nonaromatic hydrocarbon group, and the halogenated nonaromatic hydrocarbon group excludes a crosslinked halogenated nonaromatic hydrocarbon group).

Methods and apparatus for depositing a cobalt layer in a feature, such as, a word line formed in a substrate, are provided herein. In some embodiments, method of processing a substrate includes: exposing a substrate at a first temperature to a cobalt containing precursor to deposit a cobalt layer within a word line feature formed in the substrate, wherein the word line feature is part of a 3D NAND device; and annealing the substrate to remove contaminants from the cobalt layer and to reflow the cobalt layer into the word line feature, wherein the substrate is at a second temperature greater than the first temperature during the annealing.

Methods and apparatus for depositing a cobalt layer in a feature, such as, a word line formed in a substrate, are provided herein. In some embodiments, method of processing a substrate includes: exposing a substrate at a first temperature to a cobalt containing precursor to deposit a cobalt layer within a word line feature formed in the substrate, wherein the word line feature is part of a 3D NAND device; and annealing the substrate to remove contaminants from the cobalt layer and to reflow the cobalt layer into the word line feature, wherein the substrate is at a second temperature greater than the first temperature during the annealing.

Disclosed are methods of depositing a transition metal such as tungsten on a semiconductor substrate. The method includes providing a gas mixture of diborane with a balance of hydrogen, where the hydrogen serves to stabilize the diborane in the gas mixture. The method further includes delivering the gas mixture to the semiconductor substrate to form a boron layer, where the boron layer serves as a reducing agent layer to convert a metal-containing precursor to metal, such as a tungsten-containing precursor to tungsten. In some implementations, the semiconductor substrate includes a vertical structure, such as a three-dimensional vertical NAND structure, with horizontal features or wordlines having openings in sidewalls of the vertical structure, where the boron layer may be conformally deposited in the horizontal features of the vertical structure.

Disclosed are methods of depositing a transition metal such as tungsten on a semiconductor substrate. The method includes providing a gas mixture of diborane with a balance of hydrogen, where the hydrogen serves to stabilize the diborane in the gas mixture. The method further includes delivering the gas mixture to the semiconductor substrate to form a boron layer, where the boron layer serves as a reducing agent layer to convert a metal-containing precursor to metal, such as a tungsten-containing precursor to tungsten. In some implementations, the semiconductor substrate includes a vertical structure, such as a three-dimensional vertical NAND structure, with horizontal features or wordlines having openings in sidewalls of the vertical structure, where the boron layer may be conformally deposited in the horizontal features of the vertical structure.

A film-forming apparatus includes a processing container having a vacuum atmosphere therein, a stage having a heater and disposed in the processing container to load a substrate thereon, a gas discharge mechanism provided at a position to face the stage, and an exhaust part configured to exhaust an inside of the processing container. The gas discharge mechanism includes a gas intake port configured to introduce a processing gas into the processing container, a first plate-shaped member having a first opening formed in a more radially outward position than the gas intake port and a shower plate disposed between the first plate-shaped member and the stage to supply the processing gas from the first opening to a process space through a plurality of gas holes.

A method of forming a RuSi film includes performing a process a plurality of times, the process including alternately repeating: supplying a Ru(DMBD)(CO).sub.3 gas into a processing container accommodating a substrate; and supplying a hydrogenated silicon gas into the processing container.

A method of forming a RuSi film includes performing a process a plurality of times, the process including alternately repeating: supplying a Ru(DMBD)(CO).sub.3 gas into a processing container accommodating a substrate; and supplying a hydrogenated silicon gas into the processing container.

A method is provided for void-free Ru metal filling of features in a substrate. The method includes providing a substrate containing features, depositing a Ru metal layer in the features, removing the Ru metal layer from a field area around an opening of the features, and depositing additional Ru metal in the features, where the additional Ru metal is deposited in the features at a higher rate than on the field area. According to one embodiment, the additional Ru metal is deposited until the features are fully filled with Ru metal.

A method is provided for void-free Ru metal filling of features in a substrate. The method includes providing a substrate containing features, depositing a Ru metal layer in the features, removing the Ru metal layer from a field area around an opening of the features, and depositing additional Ru metal in the features, where the additional Ru metal is deposited in the features at a higher rate than on the field area. According to one embodiment, the additional Ru metal is deposited until the features are fully filled with Ru metal.