Use of nitrogen-containing ligands in atomic layer deposition methods

1. A method for atomic layer deposition of an elemental metal film comprising contacting a surface of a substrate with a vapor phase metal coordination complex comprising a transition metal cation or boron group cation M complexed with a ligand having a formula selected from the group consisting of:

a) R 1 R 2 N—(CR) x —N—(CR) y —NR 7 R 8 , wherein each R is independently hydrogen, C 1-6 alkyl, acyl, aldehyde, keto or C 2-4 alkenyl and x and y are independently 2-6;

b) R 1 R 2 N—Ar 1 —NH—Ar 2 -NR 3 R 4 , wherein each R is independently hydrogen, C 1-6 alkyl, acyl, aldehyde, keto or C 2-4 alkenyl, and Ar 1 and Ar 2 are aromatic hydrocarbon moieties which may be the same or different;

c) R 1 R 2 N—(CR 3 R 4 ) x —N Ar —(CR 5 R 6 ) y —NR 7 R 8 , wherein each R is independently hydrogen, C 1-6 alkyl, acyl, aldehyde, keto or C 2-4 alkenyl and N Ar is a heterocyclic aromatic moiety wherein the heteroatom is N, and;

d) N Ar1 —(CR 1 R 2 ) x —NR 5 —(CR 3 R 4 ) y —N Ar2 , wherein each R is independently hydrogen, C 1-6 alkyl, acyl, aldehyde, keto or C 2-4 alkenyl, and N Ar1 and N Ar2 are heterocyclic aromatic moieties wherein the heteroatom is an anionic nitrogen;

such that a layer is formed on the surface comprising the metal coordination complex bound to the surface by M;

contacting the bound metal complex with a reducing gas such that an exchange reaction occurs between the bound metal coordination complex and the reducing gas, thereby dissociating the bound metal complex and producing a layer of elemental M on the surface of the substrate.

2. The method of claim 1 wherein the ligand is selected from the group consisting of a ligand having a formula

a ligand having a formula

a ligand having a formula

a ligand having a formula

a ligand having a formula

and protonated forms of any of the foregoing.

3. The method of claim 2 , wherein R 1 , R 2 , R 7 and R 8 of formula I are each ethyl (Et) and each of R 3 -R 6 is independently hydrogen, C 1-6 alkyl, acyl, aldehyde, keto or C 2-4 alkenyl;

wherein each of R 1-4 of formula III is methyl; or

wherein each of R 1-4 of formula V is methyl.

4. The method of claim 1 , wherein the substrate is a semiconductor.

5. The method of claim 1 , wherein M is selected from the group consisting of aluminum, titanium, tungsten, zirconium, vanadium, niobium, tantalum, chromium, molybdenum, palladium, platinum, rhodium, iridium, silver, gold, hafnium, manganese, ruthenium and copper.

6. The method of claim 1 , further comprising purging excess unreacted vapor phase metal complex with an inert gas prior to addition of reducing gas.

7. The method of claim 1 , wherein the vapor phase metal complex is in a mixture with an inert gas.

8. The method of claim 1 , wherein the metal coordination complex has a formula

a formula

a formula

a formula

or a formula

wherein L is one or more neutral, anionic or mixed ligands.

9. The method of claim 8 , wherein L is an NNN ligand.

10. The method of claim 8 , wherein L is one or more of halogen, alkyl, amino and methylamino.

11. The method of claim 1 , further comprising contacting the layer of elemental M on the substrate surface with the vapor phase metal coordination complex such that an exchange reaction occurs between the metal complex and the elemental metal, thereby partially dissociating the metal complex and producing a second layer on the surface comprising the partially dissociated metal complex bound to the elemental metal layer by M, and;

contacting the bound metal complex of the second layer with a reducing gas such that an exchange reaction occurs between the bound metal complex and the reducing gas, thereby dissociating the bound metal complex and producing a second layer of elemental M on the surface of the substrate.

12. The method of claim 1 , wherein the reducing gas is hydrogen.