The present disclosure relates to methods for depositing an elemental metal or semimetal-containing material on a substrate by a cyclic deposition process, to an elemental metal or semimetal-containing layer, to a semiconductor structure and a device, and to deposition assemblies for depositing elemental metal or semimetal-containing material on a substrate. A method according to the current disclosure comprises providing a substrate in a reaction chamber, providing a metal or a semimetal precursor to the reaction chamber in a vapor phase, and providing a reducing agent into the reaction chamber in a vapor phase to form elemental metal or semimetal-containing material on the substrate. The reducing agent according to the method comprises a cyclohexadiene compound selected from compounds comprising a germanium-containing substituent.

Molybdenum (Mo) metal-on-metal (MoM) deposition methods for providing true bottom-up fill in vias and/or other gap features in device structures. These device structures contain metal at the bottom surface and have dielectric sidewalls. The deposition process provides molybdenum growth only, in some cases, on the metal film/layer to provide a selective process that can be called a metal-on-metal (MoM) process. The Mo MoM deposition process described herein are not limited to thin films (e.g., films less than 50 Å) and can be used to deposit thicker films (e.g., greater than 50 Å in some cases and greater than 200 Å in other useful cases) on metal surfaces while no, or substantially no, deposition is found on dielectric surfaces.

Molybdenum (Mo) metal-on-metal (MoM) deposition methods for providing true bottom-up fill in vias and/or other gap features in device structures. These device structures contain metal at the bottom surface and have dielectric sidewalls. The deposition process provides molybdenum growth only, in some cases, on the metal film/layer to provide a selective process that can be called a metal-on-metal (MoM) process. The Mo MoM deposition process described herein are not limited to thin films (e.g., films less than 50 Å) and can be used to deposit thicker films (e.g., greater than 50 Å in some cases and greater than 200 Å in other useful cases) on metal surfaces while no, or substantially no, deposition is found on dielectric surfaces.

Molybdenum (Mo) metal-on-metal (MoM) deposition methods for providing true bottom-up fill in vias and/or other gap features in device structures. These device structures contain metal at the bottom surface and have dielectric sidewalls. The deposition process provides molybdenum growth only, in some cases, on the metal film/layer to provide a selective process that can be called a metal-on-metal (MoM) process. The Mo MoM deposition process described herein are not limited to thin films (e.g., films less than 50 Å) and can be used to deposit thicker films (e.g., greater than 50 Å in some cases and greater than 200 Å in other useful cases) on metal surfaces while no, or substantially no, deposition is found on dielectric surfaces.

A methodology for (a) the etching of films of Al.sub.2O.sub.3, HfO.sub.2, ZrO.sub.2, W, Mo, Co, Ru, SiN, or TiN, or (b) the deposition of tungsten onto the surface of a film chosen from Al.sub.2O.sub.3, HfO.sub.2, ZrO.sub.2, W, Mo, Co, Ru, Ir, SiN, TiN, TaN, WN, and SiO.sub.2, or (c) the selective deposition of tungsten onto metallic substrates, such as W, Mo, Co, Ru, Ir and Cu, but not metal nitrides or dielectric oxide films, which comprises exposing said films to WOCl.sub.4 in the presence of a reducing gas under process conditions.

Processing methods for forming iridium-containing films at low temperatures are described. The methods comprise exposing a substrate to iridium hexafluoride and a reactant to form iridium metal or iridium silicide films. Methods for enhancing selectivity and tuning the silicon content of some films are also described.

Processing methods for forming iridium-containing films at low temperatures are described. The methods comprise exposing a substrate to iridium hexafluoride and a reactant to form iridium metal or iridium silicide films. Methods for enhancing selectivity and tuning the silicon content of some films are also described.

Methods of forming molybdenum-containing films are provided. The methods include thermally depositing a first film on a surface of a substrate, for example, at a first temperature less than or equal to about 400° C., and thermally depositing the molybdenum-containing film (second film) on at least a portion of the first film, for example, at a second temperature of greater than about 400° C. The first film can include an elemental metal, for example, tungsten, molybdenum, ruthenium, or cobalt. The second film includes a reaction product of a molybdenum-containing precursor and a reducing agent.

A method for depositing tungsten includes arranging a substrate including a titanium nitride layer in a substrate processing chamber and performing multi-stage atomic layer deposition of tungsten on the substrate using a precursor gas includes tungsten chloride (WClx) gas, wherein x is an integer. The performing includes depositing the tungsten during a first ALD stage using a first dose intensity of the precursor gas, and depositing the tungsten during a second ALD stage using a second dose intensity of the precursor gas. The first dose intensity is based on a first dose concentration and a first dose period. The second dose intensity is based on a second dose concentration and a second dose period. The second dose intensity is 1.5 to 10 times the first dose intensity.

Methods and apparatus for selectively depositing a titanium material layer atop a substrate having a silicon surface and a dielectric surface are disclosed. In embodiments an apparatus is configured for forming a remote plasma reaction between titanium tetrachloride (TiCl.sub.4), hydrogen (H.sub.2) and argon (Ar) in a region between a lid heater and a showerhead of a process chamber at a first temperature of 200 to 800 degrees C.; and flowing reaction products into the process chamber to selectively form a titanium material layer upon the silicon surface of the substrate.