Composition for metal electroplating comprising leveling agent

A method of depositing copper on a semiconductor substrate comprising features having an aperture size of 1 to 30 nm, the method comprising contacting the semiconductor substrate with a leveling agent comprising at least one polyaminoamide comprising a polymer fragment of formula I

• or derivatives thereof obtainable by complete or partial protonation,
• wherein
• D1 is selected from a chemical bond or a divalent group selected from C1-C20-alkanediyl which may optionally be interrupted by a double bond, an imino group or is optionally, completely or partially, a constituent of one or more saturated or unsaturated carbocyclic 5- to 8-membered rings,
• D2, D3 are (a) independently selected from linear or branched C1-C12 alkanediyl, which may optionally be interrupted by O, S and NR10, or (b) both, together with the two N atoms, part of a 5 or 6-membered aromatic ring system,
• D4 is selected from a linear or branched C1-C12 alkanediyl, which may optionally be interrupted by O or S,
• R1 is, for each repeating unit 1 to p and r independently, selected from H, —O—(CR11R12—O)q—H, C1-C12-alkyl, and C1 to C15 arylalkyl, which alkyl may optionally be substituted by hydroxy or C1 to C10 alkoxy,
• R10 is selected from H and C1-C12 alkyl, which may optionally be substituted by hydroxy and C1 to C10 alkoxy,
• R11, R12 are each independently selected from H, C1-C10 alkyl and —CH2—O—R15,
• R15 is selected from H and C1-C10 alkyl,
• p, r are independently integers from 0 to 10, and p or r is an integer from 1 to 6, and
• q is, if R1 is —O—(CR11R12—O)q—H, an integer selected so that an average degree of alkoxylation is from 0.01 to 5.

A process for depositing a metal layer on a substrate comprising nanometer-sized recessed features, the process comprising:

• a) contacting a composition comprising at least one polyaminoamide comprising a polymer fragment of formula I
• or derivatives thereof obtainable by complete or partial protonation with the substrate, and
• b) applying a current density to the substrate for a time sufficient to deposit a metal layer onto the substrate,
• wherein the substrate comprises nanometer-sized recessed features and the deposition is performed to fill micrometer- or nanometer-sized features,
• wherein the substrate comprises recessed features having an aperture size of from 1 to 30 nm, and
• wherein
• D1 is selected from a chemical bond or a divalent group selected from C1-C20-alkanediyl which may optionally be interrupted by a double bond, an imino group or is optionally, completely or partially, a constituent of one or more saturated, unsaturated or aromatic carbocyclic or heterocyclic 5- to 8-membered rings,
• D2, D3 are (a) independently selected from linear or branched C1-C12 alkanediyl, which may optionally be interrupted by O, S and NR10, or (b) both, together with the two N atoms, part of a 5 or 6-membered heteroaromatic ring system,
• D4 is selected from a linear or branched C1-C12 alkanediyl, which may optionally be interrupted by O or S,
• R1 is, for each repeating unit 1 to p and r independently, selected from H, —O—(cR11R12—O)q—H, C1-C12-alkyl, and C1 to C15 arylalkyl, which alkyl may optionally be substituted by hydroxy or C1 to C10 alkoxy,
• R10 is selected from H and C1-C12 alkyl, which may optionally be substituted by hydroxy and C1 to C10 alkoxy,
• R11, R12 are each independently selected from H, C1-C10 alkyl and —CH2—O—R15,
• R15 is selected from H and C1-C10 alkyl,
• p, r are independently integers from 0 to 10, and p or r is an integer from 1 to 6, and
• q is, if R1 is —O—(CR11R12—O)q—H, an integer selected so that an average degree of alkoxylation is from 0.01 to 5.