The present disclosure is directed to a method and system for the localized deposition of a metal layer on a surface. The method involves introducing at least two gaseous reactants to a substrate surface that is locally heated by a laser. The surface is heated to a temperature at which the gaseous reactants undergo a reaction that results in metal crystal growth on the substrate surface. The reaction is maintained for a desired period of time and under desired conditions to produce a localized deposit of a metal layer on the heated zone of the substrate. In some embodiments, the gas outlets and the laser may be moved in a controlled manner so that a metal layer may be deposited in a desired pattern on the substrate surface.

A raw material gas supply apparatus is configured to obtain a difference between a set value and a measured value of a vaporized raw material, add the difference as a correction value to the set value of the flow rate of the carrier gas to maintain an amount of the vaporized raw material at the set value, and subtract a difference from a set value of a flow rate of the dilution gas to maintain a total flow rate of the carrier gas and the dilution gas at a constant level. The amount of the vaporized raw material is calculated by subtracting an integration value of a measured value of the flow rate of the inert gas in the supply period of the raw material gas from an integration value of the flow rate of the raw material gas which is measured in the supply period.

A raw material gas supply apparatus is configured to obtain a difference between a set value and a measured value of a vaporized raw material, add the difference as a correction value to the set value of the flow rate of the carrier gas to maintain an amount of the vaporized raw material at the set value, and subtract a difference from a set value of a flow rate of the dilution gas to maintain a total flow rate of the carrier gas and the dilution gas at a constant level. The amount of the vaporized raw material is calculated by subtracting an integration value of a measured value of the flow rate of the inert gas in the supply period of the raw material gas from an integration value of the flow rate of the raw material gas which is measured in the supply period.

In a manufacturing method of a semiconductor device according to one embodiment, a first gas containing a first metal element is introduced into a chamber having a substrate housed therein. Next, the first gas is discharged from the chamber using a purge gas. Subsequently, a second gas reducing the first gas is introduced into the chamber. Next, the second gas is discharged from the chamber using the purge gas. Further, a third gas different from the first gas, the second gas, and the purge gas is introduced into the chamber at least either at a time of discharging the first gas or at a time of discharging the second gas.

In a manufacturing method of a semiconductor device according to one embodiment, a first gas containing a first metal element is introduced into a chamber having a substrate housed therein. Next, the first gas is discharged from the chamber using a purge gas. Subsequently, a second gas reducing the first gas is introduced into the chamber. Next, the second gas is discharged from the chamber using the purge gas. Further, a third gas different from the first gas, the second gas, and the purge gas is introduced into the chamber at least either at a time of discharging the first gas or at a time of discharging the second gas.

A substrate holder according to one embodiment of the present disclosure comprises a stage made of a dielectric material and configured to support a substrate; an attraction electrode provided in the stage and configured to electrostatically attract the substrate; and a heater configured to heat the stage. By applying a DC voltage to the attraction electrode, the substrate is electrostatically attached to a surface of the stage by a Johnsen-Rahbek force. The stage comprises an annular close contact area with which the substrate comes into close contact at a position corresponding to an outer periphery of the substrate on the surface of the stage; and a groove provided in an annular shape in a portion outside the close contact area, and a conductive deposition film formed by the raw material gas is accumulated in the groove.

Vapor deposition processes for forming thin films comprising molybdenum on a substrate are provide. In some embodiments the processes comprise a plurality of deposition cycles in which the substrate is separately contacted with a vapor phase molybdenum precursor comprising a molybdenum halide, a first reactant comprising CO, and a second reactant comprising H.sub.2. In some embodiments the thin film comprises MoC, Mo.sub.2C, or MoOC. In some embodiments the substrate is additionally contacted with a nitrogen reactant and a thin film comprising molybdenum, carbon and nitrogen is deposited, such as MoCN or MoOCN.

A method for forming a semiconductor device includes: a substrate is provided; a barrier layer is formed on an upper surface of the substrate, and a proportion of crystal orientation <111> in crystal orientations of the barrier layer is at least a preset value; and a metal material layer is formed on an upper surface of the barrier layer, crystal orientations of the metal material layer including a crystal orientation <111>.

Vapor deposition methods for depositing tungsten-containing thin films are provided. In some embodiments a substrate is contacted with a vapor phase first reactant comprising a tungsten precursor, such as a tungsten oxyhalide, a second reactant such as CO, and a third reactant such as H.sub.2. In some embodiments a substrate is contacted with a vapor phase first reactant comprising a tungsten precursor, such as a tungsten hexacarbonyl, a second reactant comprising a first oxidant, such as H.sub.2O, and a third reactant comprising a reducing agent, such as CO. In some embodiments the deposition process is an ALD process.

Methods of forming metallic tungsten films selectively on a conductive surface relative to a dielectric surface are described. A substrate is exposed to a first process condition to deposit a tungsten-containing film that is substrate free of tungsten metal. The tungsten-containing film is then converted to a metallic tungsten film by exposure to a second process condition.