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.

Methods are provided for selectively depositing a material on a first surface of a substrate relative to a second, different surface of the substrate. The selectively deposited material can be, for example, a metal, metal oxide, or dielectric material.

Methods are provided for selectively depositing a material on a first surface of a substrate relative to a second, different surface of the substrate. The selectively deposited material can be, for example, a metal, metal oxide, or dielectric material.

Provided herein are methods and related apparatus for purging processing chambers during an atomic layer deposition (ALD) process. The methods involve flowing purging gas from one or more accumulators to remove process gases from the processing chambers. Following the flowing of purging gas, additional reactants may be introduced into the processing chamber to continue an ALD cycle.

A treatment method according to the present invention includes bringing a metal oxyfluoride of the general formula: MO.sub.(6-x)/2F.sub.x (where 0<x<6; and M=W or Mo) into contact with a fluorine-containing gas at a reaction temperature higher than or equal to 0° C. and lower than 400° C., thereby converting the metal oxyfluoride to a metal hexafluoride of the general formula: MF.sub.6 (where M=W or Mo). This treatment method enables conversion of the metal oxyfluoride to the high vapor pressure compound without the use of a plasma generator and can be applied to cleaning of a metal fluoride production apparatus or cleaning of a film forming apparatus.

There is provided a film formation method. The method comprises: preparing a substrate having a first region on which an oxide formed by oxidization of a surface of a conductive material is exposed and a second region on which an insulating material is exposed; replacing a film of the oxide with a film of boron oxide by supplying a boron halide gas to the substrate; etching the boron oxide film in the first region and forming a self-assembled monolayer film in the second region by supplying a gas of a fluorine-containing silane compound to the substrate; and forming a conductive target film selectively in the first region, from the first region and the second region, using the self-assembled monolayer film formed in the second region, the first region having the conductive material exposed thereon.

Methods of depositing a tungsten nucleation layers that achieve very good step coverage are provided. The methods involve a sequence of alternating pulses of a tungsten-containing precursor and a boron-containing reducing agent, while co-flowing hydrogen (H2) with the boron-containing reducing agent. The H2 flow is stopped prior to the tungsten-containing precursor flow. By co-flowing H2 with the boron-containing reducing agent but not with the tungsten-containing precursor flow, a parasitic CVD component is reduced, resulting in a more self-limiting process. This in turn improves step coverage and conformality of the nucleation layer. Related apparatuses are also provided.

Provided herein are methods and apparatuses for reducing line bending when depositing a metal such as tungsten, molybdenum, ruthenium, or cobalt into features on substrates by periodically exposing the feature to nitrogen, oxygen, or ammonia during atomic layer deposition, chemical vapor deposition, or sequential chemical vapor deposition to reduce interactions between metal deposited onto sidewalls of a feature. Methods are suitable for deposition into V-shaped features.

The invention provides a facile process for preparing various Group VI precursor compounds useful in the vapor deposition of such Group VI metals onto solid substrates, especially microelectronic semiconductor device substrates. The process provides an effective means to obtain such volatile materials, which can then be sources of molybdenum, chromium, or tungsten-containing materials to be deposited on such substrates. Additionally, the invention provides a method for vapor deposition of such compounds onto microelectronic device substrates.

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.