Abstract: Processing methods comprising selectively orthogonally growing a first material through a mask to provide an expanded first material are described. The mask can be removed leaving the expanded first material extending orthogonally from the surface of the first material. Further processing can create a self-aligned via.

Abstract: Methods for deposition of elemental metal films on surfaces using metal coordination complexes comprising nitrogen-containing ligands are provided. Also provided are nitrogen-containing ligands useful in the methods of the invention and metal coordination complexes comprising these ligands.

Abstract: Methods are provided for deposition of films comprising manganese on surfaces using metal coordination complexes comprising an amidoimino-based ligand. Certain methods comprise exposing a substrate surface to a manganese precursor, and exposing the substrate surface to a co-reagent.

Abstract: Metal coordination complexes comprising a metal atom coordinated to at least one aza-allyl ligand having the structure represented by: where each R1-R4 are independently selected from the group consisting of H, branched or unbranched C1-C6 alkyl, branched or unbranched C1-C6 alkenyl, branched or unbranched C1-C6 alkynyl, cycloalkyl groups having in the range of 1 to 6 carbon atoms, silyl groups and halogens. Methods of depositing a film using the metal coordination complex and a suitable reactant are also described.

Abstract: Methods for deposition of elemental metal films on surfaces using metal coordination complexes comprising nitrogen-containing ligands are provided. Also provided are nitrogen-containing ligands useful in the methods of the invention and metal coordination complexes comprising these ligands.

Abstract: Provided are methods for etching films comprising transition metals. Certain methods involve activating a substrate surface comprising at least one transition metal, wherein activation of the substrate surface comprises exposing the substrate surface to heat, a plasma, an oxidizing environment, or a halide transfer agent to provide an activated substrate surface; and exposing the activated substrate surface to a reagent comprising a Lewis base or pi acid to provide a vapor phase coordination complex comprising one or more atoms of the transition metal coordinated to one or more ligands from the reagent. Certain other methods provide selective etching from a multi-layer substrate comprising two or more of a layer of Co, a layer of Cu and a layer of Ni.

Abstract: Methods for filling a substrate feature with a seamless ruthenium gap fill are described. The methods include depositing a ruthenium film, oxidizing the ruthenium film to form an oxidized ruthenium film, reducing the oxidized ruthenium film to a reduced ruthenium film and repeating the oxidation and reduction processes to form a seamless ruthenium gap fill.

Abstract: A process to selectively etch a substrate surface comprising multiple metal oxides comprising exposing the substrate surface to a halogenation agent, and then exposing the substrate surface to a ligand transfer agent. The etch rate of the metals in the multiple metal oxides is substantially uniform.

Abstract: Processing methods comprising exposing a substrate to an optional nucleation promoter followed by sequential exposure of a first reactive gas comprising a metal oxyhalide compound and a second reactive gas to form a metal film on the substrate.

Abstract: Provided are methods for etching films comprising transition metals which help to minimize higher etch rates at the grain boundaries of polycrystalline materials. Certain methods pertain to amorphization of the polycrystalline material, other pertain to plasma treatments, and yet other pertain to the use of small doses of halide transfer agents in the etch process.

Abstract: 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.

Abstract: Methods of depositing a film selectively onto a first substrate surface relative to a second substrate surface are described. The methods include exposing a substrate to a blocking molecule to selectively deposit a blocking layer on the first surface. A layer is selectively formed on the second surface and defects of the layer are formed on the blocking layer. The defects are removed from the blocking layer on the first surface.

Abstract: Methods for depositing a film comprising exposing a substrate surface to a bis-amidinate metal precursor and a co-reactant to form a metal containing film are described. The bis-amidinate metal precursor comprises a metal atom comprising one or more lanthanide.

Abstract: Processing methods comprising selectively orthogonally growing a first material through a mask to provide an expanded first material are described. The mask can be removed leaving the expanded first material extending orthogonally from the surface of the first material. Further processing can create a self-aligned via.

Abstract: Methods of forming a lanthanide-containing film comprising exposing a substrate surface to a lanthanide-containing precursor, a metal halide and a nitrogen precursor are described. The lanthanide-containing precursor has the general formula (CpRx)2Ln(N,N-dialkylamidinate) where Cp is a cyclopentadienyl or 6, 7 or 8 membered ring, R is H, C1-C4 alkyl, x=1 to number of C in Cp, alkyl is C1 to C4 alkyl. The metal halide deposits metal halide on the substrate surface and reacts with lanthanide-containing species to convert the lanthanide-containing species to a lanthanide halide. The nitrogen-containing precursor forms a lanthanide-metal-nitride film on the substrate surface.

Abstract: A process to selectively etch a substrate surface comprising multiple metal oxides comprising exposing the substrate surface to a halogenation agent, and then exposing the substrate surface to a ligand transfer agent. The etch rate of the metals in the multiple metal oxides is substantially uniform.

Abstract: Processing methods comprising exposing a substrate to an optional nucleation promoter followed by sequential exposure of a first reactive gas comprising a metal oxyhalide compound and a second reactive gas to form a metal film on the substrate.

Abstract: Embodiments include a method of processing a hardmask that includes forming an alloyed carbon hardmask over an underlying layer. In an embodiment, the alloyed carbon hardmask is alloyed with metallic-carbon fillers. The embodiment further includes patterning the alloyed carbon hardmask and transferring the pattern of the alloyed carbon hardmask into the underlying layer. According to an embodiment, the method may further include removing the metallic component of the metallic-carbon fillers from the alloyed carbon hardmask to form a porous carbon hardmask. Thereafter, the porous hardmask may be removed. In an embodiment, the metallic component of the metallic-carbon fillers may include flowing a processing gas into a chamber that volatizes the metallic component of the metallic-carbon fillers.

Abstract: Metal coordination complexes comprising at least one diazabutadiene based ligand having a structure represented by: where R1 and R4 are selected from the group consisting of C4-C10 alkyl groups; and R2 and R3 are each independently selected from the group consisting of H, C1-C6 alkyl, cycloalkyl, or aryl groups and the difference in the number of carbons in R2 and R3 is greater than or equal to 2. Processing methods using the metal coordination complexes are also described.

Abstract: Metal coordination complexes comprising at least one diazabutadiene based ligand having a structure represented by: where A1, A2, A3, and A4 are atoms in a 6-membered ring and are independently selected from C, N, O, S, and P; and where R1, R2, R3, R4, R5, and R6 are independently selected from the group consisting of H, amino groups, C1-C6 alkyl groups, or C4-10 cycloalkyl groups; and further provided that alkyl groups may optionally contain silicon; and where the metal coordination complex is capable of participating in a Diels-Alder type reaction with a dienophile. Processing methods using the metal coordination complexes are also described.