Method of making conformal lining layers for damascene metallization

A process for forming metal structures in an integrated circuit, comprising:

• forming a dual damascene trench and contact structure in a partially fabricated integrated circuit;
• supplying a first chemistry to surfaces of the trench and contact structure;
• removing the first chemistry from the trench and contact structure, wherein removing the first chemistry comprises removing a reactant containing the first chemistry from a reaction chamber containing the partially fabricated integrated circuit;
• exposing the trench and contact structure to a non-radical reducer;
• supplying a second chemistry to the trench and contact structure after removing the first chemistry;
• removing the second chemistry from the trench and contact structure, wherein removing the second chemistry comprises removing a reactant containing the second chemistry from the reaction chamber before introducing other reactants into the reaction chamber;
• and
• repeating supplying and removing the first chemistry and supplying and removing the second chemistry at least about 10 times.

A method of forming a metal nitride barrier layer in a dual damascene structure having a trench and a contact via formed through an insulating layer in an integrated circuit, comprising:

• forming no more than about one monolayer of a metal-containing species in a self-limited reaction;
• removing the metal-containing species from the trench and the contact via;
• reacting the monolayer with a non-radical reducer after removing the metal-containing species;
• reacting a nitrogen-containing species with the monolayer after reacting the monolayer;
• and
• removing the nitrogen-containing species from the trench and the contact via.

A metallization process, comprising:

• forming an opening in an insulating layer above a semiconductor substrate to expose at least part of an underlying conductive element;
• lining surfaces of the opening with no more than about one monolayer of a halide-terminated metal species in a first phase;
• removing halogen tails from the halide-terminated metal with a reducer including triethyl boron (TEB) in a second phase distinct from the first phase;
• adsorbing no more than about one monolayer of a reactive species upon the metal species in a third phase;
• and
• repeating the first, second and third phases in at least about 10 cycles, wherein the metal species is removed from a reaction chamber containing the substrate after the first phase, the reducer and the halogen tails are removed from the chamber after the second phase and before the third phase, and the reactive species is removed from the chamber after the third phase.

A method of forming a metal nitride liner in a damascene structure including a trench during metallization of an integrated circuit, the method comprising:

• chemisorbing no more than about one monolayer of a metal halide species upon surfaces of the trench;
• removing halogen atoms from the metal halide species with triethyl boron;
• reacting a nitrogen-containing species with the monolayer after removing halogen atoms;
• and
• repeatedly chemisorbing, removing and reacting until a thickness of metal nitride forms over surfaces of the trench sufficient to prevent copper diffusion therethrough.