Process for selectively depositing copper thin films on substrates with copper and ruthenium areas via vapor deposition

1. A process for preparing a multi-layered substrate comprising a first layer and a second layer, the process comprising:

providing the first layer comprising a ruthenium area and a copper area; and

depositing the second layer comprising copper onto the first layer using at least one precursor having any one of the formula (Ib) to provide the

wherein M is copper;

wherein X is selected from oxygen and NR 5 ;

wherein R 1 , R 2 , R 3 , and R 5 are each independently selected from a hydrogen atom; an alkyl having a formula C n H 2n+1 wherein n is a number ranging from 1 to 20; a fluoroalkyl having the formula C n H x F y wherein the product of the (x+y) equals the product of (2n+1) and n is a number ranging from 1 to 20,

wherein R 4 is selected from an alkyl having a formula C n H 2n+1 wherein n is a number ranging from 1 to 20; an alkoxy comprising from 1 to 20 carbon atoms; and wherein R 4 associates with L by having a hydrogen, an atom, or a group removed,

wherein L is a ligand selected from an alkylnitrile comprising from 2 to 20 carbon atoms; a silylnitrile having the formula (R 8 ) 3 SiCN wherein R 8 is each independently an alkyl, an alkoxy, or an amide comprising from 1 to 20 carbon atoms; an alkyne comprising from 1 to 20 carbon atoms; a silylalkyne having a formula (R 8 ) 3 SiCCR 10 wherein R 9 is each independently an alkyl, and R 10 is hydrogen or an alkyl comprising from 1 to 20 carbon atoms; a silylalkyne having a formula (R 11 ) 3 SiCCSi(R 11 ) 3 wherein R 11 is each independently an alkyl comprising from 1 to 20 carbon atoms; an alkene, diene, or triene comprising from 1 to 20 carbon atoms; a silylalkene having a formula (R 12 ) 3 SiCR 13 C(R 13 ) 2 wherein R 12 is each independently an alkyl, an alkoxy, an aryl, a vinyl, or an amide comprising from 1 to 20 carbon atoms and R 13 is each independently a hydrogen, an alkyl comprising from 1 to 20 carbon atoms, a bis(silyl)alkene having the formula (R 14 ) 3 SiCR 13 CR 13 Si(R 14 ) 3 wherein R 14 is each independently an alkyl comprising from 1 to 20 carbon atoms and R 13 is each independently a hydrogen atom or an alkyl comprising from 1 to 20 carbon atoms; and an allene comprising from 3 to 20 carbons and wherein L associates with R 4 by having a hydrogen, an atom, or a group removed;

wherein an organometallic bond between M and L is selected from 2 single bonds and 1 single bond; and

wherein the depositing provides the second layer comprising:

a first thickness ranging from about 20 Angstroms to about 2,000 Angstroms onto the ruthenium area and

a second thickness onto the copper area that is at least 90% less than the first thickness,

and wherein at least a portion of the depositing step is conducted in the presence of a reducing agent.

2. The process of claim 1 wherein any one of X, R 1 , R 2 , R 3 and R 4 are connected to form a cyclic structure.

3. The process of claim 1 wherein X and R 1 and connected to form a cyclic structure.

4. The process of claim 1 wherein the reducing agent is at least one chosen from an alcohol, a carboxylic acid, hydrogen gas, hydrogen plasma, remote hydrogen plasma, a silane, a borane, an alane, a germane, a hydrazine, ammonia, and mixtures thereof.

5. The process of claim 1 wherein the thickness of the second layer is substantially 0.

6. The process of claim 1 wherein the precursor having formula (Ib) is Cu((CH 2 ) 3 NCCHC(NCH 2 CH 2 OSiMe 2 C 2 H 3 )Me).

7. The process of claim 1 wherein the precursor having formula (Ib) is Cu(CF 3 C(O)CHC(NCH 2 CH 2 OSiMe 2 C 2 H 3 )CF 3 ).