Methods of forming ruthenium-containing films by atomic layer deposition and/or chemical vapor deposition are provided. The methods include a first step of forming a first film on a surface of the substrate and a second step of forming the ruthenium-containing film on at least a portion of the first film. The first step includes delivering a titanium precursor and a first nitrogen-containing co-reactant to the substrate and delivering a first ruthenium precursor and a second nitrogen-containing co-reactant to the substrate to form the first film. The second step includes delivering a second ruthenium precursor and a third co-reactant to the substrate. Ruthenium-containing films are also provided.

A controller includes an accumulation determiner configured to determine a first accumulation value that indicates an amount of accumulation of material on surfaces within a processing chamber and a pressure controller configured to obtain the first accumulation value, obtain at least one of a setpoint pressure an etching step and a duration of the etching step, and, to control the pressure within the processing chamber during the etching step, adjust a control parameter based on (i) the first accumulation value and (ii) the at least one of the setpoint pressure and the duration of the etching step.

A controller includes an accumulation determiner configured to determine a first accumulation value that indicates an amount of accumulation of material on surfaces within a processing chamber and a pressure controller configured to obtain the first accumulation value, obtain at least one of a setpoint pressure an etching step and a duration of the etching step, and, to control the pressure within the processing chamber during the etching step, adjust a control parameter based on (i) the first accumulation value and (ii) the at least one of the setpoint pressure and the duration of the etching step.

A method of depositing material over a sample in a deposition region of the sample with a charged particle beam column, the method comprising: positioning a sample within a vacuum chamber such that the deposition region is under a field of view of the charged particle beam column; cooling the deposition region by contacting the sample with a cyro-nanomanipulator tool in an area adjacent to the deposition region; injecting a deposition precursor gas into the vacuum chamber at a location adjacent to the deposition region; generating a charged particle beam with a charged particle beam column and focusing the charged particle beam on the sample; and scanning the focused electron beam across the localized region of the sample to activate molecules of the deposition gas that have adhered to the sample surface in the deposition region and deposit material on the sample within the deposition region

A method of depositing material over a sample in a deposition region of the sample with a charged particle beam column, the method comprising: positioning a sample within a vacuum chamber such that the deposition region is under a field of view of the charged particle beam column; cooling the deposition region by contacting the sample with a cyro-nanomanipulator tool in an area adjacent to the deposition region; injecting a deposition precursor gas into the vacuum chamber at a location adjacent to the deposition region; generating a charged particle beam with a charged particle beam column and focusing the charged particle beam on the sample; and scanning the focused electron beam across the localized region of the sample to activate molecules of the deposition gas that have adhered to the sample surface in the deposition region and deposit material on the sample within the deposition region

Methods of forming ruthenium-containing films by pulsed chemical vapor deposition are provided. The methods include at least one deposition cycle. The deposition cycle includes pulsing a zerovalent Ru precursor with a carrier gas in the absence of a co-reactant onto a surface of a substrate, and delivering a purge gas to the surface of the substrate.

Organometallic precursors and methods of depositing high purity metal films are discussed. Some embodiments utilize a method comprising exposing a substrate surface to an organometallic precursor comprising one or more of molybdenum (Mo), tungsten (W), osmium (Os), technetium (Tc), manganese (Mn), rhenium (Re) or ruthenium (Ru), and an iodine-containing reactant comprising a species having a formula RI.sub.x, where R is one or more of a C.sub.1-C.sub.10 alkyl, C.sub.3-C.sub.10 cycloalkyl, C.sub.2-C.sub.10 alkenyl, or C.sub.2-C.sub.10 alkynyl group, I is an iodine group and x is in a range of 1 to 4 to form a carbon-less iodine-containing metal film. Some embodiments advantageously provide methods of forming metal films having low carbon content (e.g., having greater than or equal to 95% metal species on an atomic basis), without using an oxidizing agent or a reductant.

Processes for forming Mo and W containing thin films, such as MoS.sub.2, WS.sub.2, MoSe.sub.2, and WSe.sub.2 thin films are provided. Methods are also provided for synthesizing Mo or W beta-diketonate precursors. Additionally, methods are provided for forming 2D materials containing Mo or W.

Processes for forming Mo and W containing thin films, such as MoS.sub.2, WS.sub.2, MoSe.sub.2, and WSe.sub.2 thin films are provided. Methods are also provided for synthesizing Mo or W beta-diketonate precursors. Additionally, methods are provided for forming 2D materials containing Mo or W.

A ruthenium film forming method includes: causing chlorine to be adsorbed to an upper portion of a recess at a higher density than to a lower portion of the recess by supplying a chlorine-containing gas to a substrate including an insulating film and having the recess; and forming a ruthenium film in the recess by supplying a Ru-containing precursor to the recess to which the chlorine is adsorbed.