NEW METAL PRECURSORS CONTAINING BETA-DIKETIMINATO LIGANDS

• US 20090197411A1
• Filed: 02/02/2009
• Published: 08/06/2009
• Est. Priority Date: 02/01/2008
• Status: Active Grant

• Current Assignee: American Air Liquide Incorporated (L'Air Liquide SA)
• Original Assignee: American Air Liquide Incorporated (L'Air Liquide SA)
• Inventors: Feist, Benjamin J., Dussarrat, Christian
• Granted Patent: US 9,103,019 B2
• Time in Patent Office: Days
• US Class Current: 438/681
• CPC Class Codes: C07C 251/08 being acyclic
• CPC Class Codes: C23C 16/18 from metallo-organic compounds
• CPC Class Codes: C23C 16/406 of iron group metals
• CPC Class Codes: H01L 21/32051 Deposition of metallic or metal-silicide layers

Abstract

Methods and compositions for depositing a metal containing thin film on a substrate comprises introducing a vapor phase metal-organic precursor into a reaction chamber containing one or more substrates. The precursor has at least one β-diketiminato ligand, and has the general formula:

M(R¹C(NR⁴)CR²C(NR⁵)R³)₂L_n

wherein M is a metal selected from nickel, cobalt, ruthenium, iridium, palladium, platinum, silver and gold. Each of R^1-5 is an organic ligand independently selected from H; and a C₁-C₄ linear or branched, alky group, alkylsilyl group, alkylamide group, alkoxide group, or alkylsilylamide group. Each L is independently selected from: a hydrocarbon; an oxygen-containing hydrocarbon; an amine; a polyamine; a bipyridine; an oxygen containing heterocycle; a nitrogen containing heterocycle; and combinations thereof; and n is an integer ranging from 0 to 4, inclusive.

A metal containing film is deposited onto the substrate, while the substrate is maintained at a temperature between about 100° C. and about 500° C.

Claims

1. A method for depositing a metal containing thin film on a substrate;

comprising;

a) introducing a vapor phase metal-organic precursor into a reaction chamber containing one or more substrates, wherein the precursor comprises a compound with at least one β

-diketiminato ligand, and which has the general formula;

M(R¹C(NR⁴)CR²C(NR⁵)R³)₂L_n

wherein;

M is a metal selected from the group consisting of;

nickel, cobalt, ruthenium, iridium, palladium, platinum, silver and gold;

each of R^1-5 is an organic ligand independently selected from the group consisting of;

H; and

a C₁-C₄ linear or branched, alky group, alkylsilyl group, alkylamide group, alkoxide group, or alkylsilylamide group;

each L is independently selected from the group consisting of;

a hydrocarbon;

an oxygen-containing hydrocarbon;

an amine;

a polyamine;

a bipyridine;

an oxygen containing heterocycle;

a nitrogen containing heterocycle; and

combinations thereof; and

n is an integer ranging from 0 to 4, inclusive;

b) depositing a metal containing film onto the substrate, wherein the substrate is maintained at a temperature between about 100°

C. and about 500°

C.

2. The method of claim 1, further comprising introducing at least one reactant into the reaction chamber.

3. The method of claim 2, wherein the metal containing film comprises oxygen, and wherein the reactant comprises at least one member selected from the group consisting of:

oxygen;

oxygen radicals (e.g. O. or OH.);

ozone;

nitric oxide;

nitrous oxide;

nitrogen dioxide;

water vapor;

hydrogen peroxide; and

mixtures thereof.

4. The method of claim 2, wherein the metal containing film comprises nitrogen, and wherein the reactant comprises at least one member selected from the group consisting of:

nitrogen;

ammonia;

hydrazine;

alkyl derivatives;

nitrogen containing radicals (e.g. N., NH., or NH₂.);

nitric oxide;

nitrous oxide;

nitrogen dioxide;

amines; and

mixtures thereof.

5. The method of claim 2, wherein the metal containing film comprises carbon, and wherein the reactant comprises at least one member selected from the group consisting of:

methane;

ethane;

propane;

butane;

ethylene;

propylene;

tert-butylene;

isobutylene;

carbon tetrachloride; and

mixtures thereof.

6. The method of claim 2, wherein the metal containing film comprises silicon, and wherein the reactant comprises at least one member selected from the group consisting of:

SiH₄;

Si₂H₆;

Si₃H₈;

a Si(NR¹R²)₄ wherein R¹ and R² are independently selected from H or a linear, branched or cyclic C₁-C₆ alkyl group;

(SiH₃)₃N;

(SiH₃)₂O;

an alkoxysilane of the general formula SiH_x(OR¹)_4-x, where x is an integer ranging from 0 to 4 inclusive, and R¹ is independently selected from H or a linear, branched or cyclic C₁-C₆ alkyl group;

a silanol of the general formula Si(OH)_x(OR¹)_4-x, where x is an integer ranging from 0 to 4 inclusive, and R¹ is independently selected from H or a linear, branched or cyclic C₁-C₆ alkyl group;

an aminosilane of the general formula SiH_x(NR¹R²)_4-x where x is an integer ranging from 0 to 4 inclusive, and R¹ and R² are independently selected from H or a linear, branched or cyclic C₁-C₆ alkyl group; and

mixtures thereof.

7. The method of claim 6, wherein the reactant comprises at least one member selected from the group consisting of:

Si(OH)(OtBu)₃;

SiH(NMe₂)₃;

SiH₂(NHtBU)₂; and

SiH₂(NEt₂)₂.

8. The method of claim 2, wherein the metal containing film comprises germanium, and wherein the reactant comprises at least one member selected from the group consisting of:

GeH₄;

Ge₂H₆;

Ge₃H₈;

a Ge(NR¹R²)₄ wherein R¹ and R² are independently selected from H or a linear, branched or cyclic C₁-C₆ alkyl group;

(GeH₃)₃N;

(GeH₃)₂O;

an alkoxy germane of the general formula GeH_x(OR¹)_4-x, where x is an integer ranging from 0 to 4 inclusive, and R¹ is independently selected from H or a linear, branched or cyclic C₁-C₆ alkyl group;

a germanol of the general formula Ge(OH)_x(OR¹)_4-x, where x is an integer ranging from 0 to 4 inclusive, and R¹ is independently selected from H or a linear, branched or cyclic C₁-C₆ alkyl group;

an aminogermane of the general formula GeH_x(NR¹R²)_4-x, where x is an integer ranging from 0 to 4 inclusive, and R¹ and R² are independently selected from H or a linear, branched or cyclic C₁-C₆ alkyl group; and

mixtures thereof.

9. The method of claim 8, wherein the reactant comprises at least one member selected from the group consisting of:

Ge(OH)(OtBu)₃;

GeH(NMe₂)₃;

GeH₂(NHtBu)₂; and

GeH₂(NEt₂)₂.

10. The method of claim 2, further comprising introducing the precursor and the reactant into the reaction chamber simultaneously.

11. The method of claim 2, further comprising introducing the precursor and the reactant into the reaction chamber sequentially.

12. The method of claim 2, further comprising mixing the precursor and the reactant together, and introducing the precursor and the reactant into the reaction chamber as a mixture.

13. The method of claim 2, further comprising introducing the precursor and the reactant into the reaction chamber by pulsing them into the reaction chamber.

14. The method of claim 2, further comprising decomposing the reactant into its radical form prior to introducing the reactant to the reaction chamber by passing the reactant through a remotely located plasma system.

15. The method of claim 1, wherein the precursor has a melting point less than or equal to about 80°

C.

16. The method of claim 15, wherein the precursor has a melting point less than or equal to about 35°

C.

17. The method of claim 1, wherein the substrate is maintained at a temperature between about 150°

C. and about 350°

C.

18. The method of claim 1, wherein the precursor has a vapor pressure greater than about 0.1 torr at about 130°

C.

19. The method of claim 1, wherein the precursor comprises at least one member selected from the group consisting of:

Ni(pda)₂;

Ni(dmpda)₂;

Ni(depda)₂;

Ni(diPrpda)₂;

Co(pda)₂;

Co(dmpda)₂;

Co(depda)₂; and

Co(diPrpda)₂.

21. The precursor of claim 18, wherein M is nickel or cobalt.

22. The precursor of claim 18, wherein the metal-organic precursor has a melting point less than about 35°

C.

20. A precursor for depositing a metal containing thin film on a substrate, comprising an metal-organic precursor with at least one β

-diketiminato ligand and which has the general formula;

M(R¹C(NR⁴)CR²C(NR⁵)R³)₂L_n

wherein;

M is a metal selected from the group consisting of;

nickel, cobalt, ruthenium, iridium, palladium, platinum, silver and gold;

each of R^1-5 is an organic ligand independently selected from the group consisting of;

H; and

a C₁-C₄ linear or branched, alky group, alkylsilyl group, alkylamide group, alkoxide group, or alkylsilylamide group;

each L is independently selected from the group consisting of;

a hydrocarbon;

an oxygen-containing hydrocarbon;

an amine;

a polyamine;

a bipyridine;

an oxygen containing heterocycle;

a nitrogen containing heterocycle; and

combinations thereof; and

n is an integer ranging from 0 to 4, inclusive;