Deposition of metal-containing films

A method of forming a molybdenum-containing layer on a substrate comprising:

• providing a substrate in a processing chamber;
• introducing a low valent molybdenum precursor and at least one reactant into the processing chamber,
• wherein the low valent molybdenum precursor comprises an oxidation state of zero, one, two or three,
• wherein the low valent molybdenum precursor comprises a structure of Formula (I), Formula (II), or Formula (III):
• and
• wherein:
• each L is independently a monodentate ligand, an ambidentate ligand, a bidentate ligand, or a tridentate ligand,
• L′ is a linking moiety,
• n is 2, 3, 4, 5 or 6;
• and
• m is 1, 2 or 3;
• and
• reacting the low valent molybdenum precursor and the at least one reactant to form a molybdenum-containing layer on the substrate.

A metal coordination complex comprising a structure of Formula (VI), Formula (IX), Formula (X), Formula (XI), or Formula (XV):

• wherein:
• R4, R6, R7 and R16 each independently comprises-CH3, —C2H5, —C3H7, —C4H9, —C5H11, —CF3, —C(F)—CF2, —C(F)═C(F)CF3, —CF2C(F)—CF2, —C4F9, —C5F11, —CH2CF3, —CH(CF3)2, —CH(CH3)(CF3), —C(CH3)2(CF3), —C(CF3)3, —Si(CH3)3, —Si(C2H5)3, —CH2Si(CH3)3, —CH(Si(CH3)3)2, —C(Si(CH3)3)3, —P(CH3)3, —CH2P(CH3)3, —P(O)OH, —P(O)(OCH3)2, —P(O)(OCH2CH3)2, —CH(Si(CH3)3)(P(CH3)3), —SO2CF3, —SO2C3N2H3, —C(O)C3F7, —CHCHSO2C6H5, —SO2OCH3 or —SO2C6H4CH3,
• G comprises ═O, ═NR, ═S or ═CR2,
• each R independently comprises an aliphatic, an aryl, a haloalkyl, or haloaryl group,
• each R8 independently comprises allyl, allenyl, ethenyl, mesitylenyl, tolyl, xylyl, benzyl, cyclopentadienyl, indenyl, anilinyl, N,N-dimethylanilinyl, tetrahydrofuranyl, piperidinyl, pyrrolyl, pyrrolidinyl, pyridinyl, imidazolyl, pyrimidinyl, —NO, —CO, —P(CH3)3, —P(CH2CH3)3 or —CNR9, and
• R9 comprises an aliphatic, an aryl, or a heterocyclyl group.

A method of depositing a film on a semiconductor substrate, the method comprising:

• providing a semiconductor substrate in a process chamber;
• forming an iodine bond-containing metal species in the process chamber;
• and
• exposing the iodine bond-containing metal species to a reducing agent, thereby forming a metal-containing film on the semiconductor substrate,
• wherein forming the iodine bond-containing metal species comprises (i) introducing a metal-containing precursor in the process chamber comprising the semiconductor substrate;
• and (ii) introducing an iodine-containing reagent to react with the metal-containing precursor, or wherein forming the iodine bond-containing metal species comprises (i) introducing an iodine-containing reagent to the process chamber comprising the semiconductor substrate;
• and (ii) introducing a metal-containing precursor to react with the iodine-containing reagent;
• wherein the metal-containing precursor comprises a low valent molybdenum precursor, the low valent molybdenum precursor comprises an oxidation state of zero, one, two or three,
• wherein the low valent molybdenum precursor comprises a structure of Formula (I), Formula (II), or Formula (III):
• and
• wherein:
• each L is independently a monodentate ligand, an ambidentate ligand, a bidentate ligand, or a tridentate ligand,
• L′ is a linking moiety,
• n is 2, 3, 4, 5 or 6;
• and
• m is 1, 2 or 3.