Group V and VI transition metal precursors for thin film deposition

Patent metadata

Field	Value
Publication number	US-12410202-B2
Application number	US-202017616470-A
Country	US
Kind code	B2
Filing date	May 28, 2020
Priority date	Jun 5, 2019
Publication date	Sep 9, 2025
Grant date	Sep 9, 2025

Abstract

Described herein are Group V and VI compounds used as precursors for depositing Group V and VI-containing films. Ligands with alkyl, amide, imide, amidinate groups and/or cyclopentadienyl (Cp) ligands are used to form Group V and VI complexes used as precursors. Examples of Group V and VI precursor compounds include, but are not limited to, Cp amide imide alkyl vanadium compounds, Cp amide imide alkylamide vanadium compounds, Cp amide imide alkoxide vanadium compounds, Cp amide imide amidinate vanadium compounds, and alkylimide vanadium trichloride compounds. The Group V and VI precursors are used for deposition on substrate surfaces with superior film properties such as uniformity, continuity, and low resistance. Examples of substrate surfaces for deposition of metal-containing films include, but are not limited to metals, metal oxides, and metal nitrides.

First claim

The invention claimed is:

1. A precursor having a chemical structure selected from the group consisting of:

wherein:
M 1 is selected from the group consisting of vanadium, tantalum, niobium, chromium, molybdenum and tungsten;
X is a halide selected from chloride (Cl), bromide (Br) and iodide (I);
R 1 is a linear or branched C 1 -C10 alkyl, an amino group or an ether group for A and B, and is a linear or branched C 1 -C 10 alkyl, an amino group or an ether group but not tert-butyl for C and G;
R 2 is a linear or branched C 2 -C 10 alkylene;
R 3 , R 4 and R 6 are independently selected from the group consisting of a linear or branched C 1 -C 10 alkyl, an amino group and an ether group;
R 5 is selected from the group consisting of hydrogen and a linear or branched C 1 -C 10 alkyl;
L is selected from the group consisting of R 1 , OR 1 and NR 1 R 3 ;
L 1 is a substituted or unsubstituted cyclopentadienyl ligand;
L 2 is NR 1 R 3 ;
m has a value of 0, 1 or 2, and
n has a value of 1, 2, 3 or 4.

2. The precursor of claim 1 , wherein the precursor has the structure B; wherein M 1 is vanadium; R 2 is a linear C 2 alkylene; R 1 and R 3 are methyl; R 5 is hydrogen and R 4 and R 6 are selected from the same linear C 1 to C 2 alkyl.

3. The precursor of claim 1 , wherein the precursor has the structure C; wherein: M 1 is vanadium; and R 1 is selected from the group consisting of sec-butyl (Bu 5 ) and tert-amyl (Amyl t ).

4. The precursor of claim 1 , wherein the precursor has structure C and is selected from the group consisting of:

5. The precursor of claim 1 , wherein the precursor has the structure D; wherein: M 1 is vanadium; R 2 is a linear or branched C 2 to C 3 alkylene and R 3 is a linear C 1 to C 2 alkyl.

6. The precursor of claim 1 , wherein the precursor has the structure E; wherein: M 1 is vanadium; and R 1 and R 3 are selected from the same linear or branched chin C 1 to C 3 alkyl.

7. The precursor of claim 1 , wherein the precursor has the structure F; wherein m has a value of zero, n has a value of 3 and R 1 and R 3 are independently selected from the group consisting of methyl and ethyl groups.

8. The precursor of claim 1 , wherein the precursor has the structure F; wherein m has a value of 1, n has a value of 2 and R 1 and R 3 are independently selected from the group consisting of methyl and ethyl groups.

9. The precursor of claim 1 , wherein the precursor has the structure G and is selected from the group consisting of:

10. The precursor of claim 1 , wherein the precursor is selected from the group consisting of trichloro(tert-amylimino)vanadium; trichloro(sec-buty 1 imino)vanadium; and tert-amylimino-tris(dimethylamino)vanadium.

11. The precursor of claim 1 , wherein at least one cyclopentadienyl ligand is bound to a transition metal in η 5 -coordination by π bonding.

12. The precursor of claim 1 , wherein the precursor is substantially free of halide ions, metal impurities, or both of halide ions and metal impurities.

13. The precursor of claim 1 , wherein the precursor has a melting point of 120 degrees Celsius or less, 70 degrees Celsius or less, 60 degrees Celsius or less, 50 degrees Celsius or less, 40 degrees Celsius or less, or 30 degrees Celsius or less.

14. The precursor of claim 1 , wherein the precursor is in a liquid form at ambient temperature.

15. The precursor of claim 1 , wherein the precursor has chemical structure selected from the group consisting of B, C, D, E, F, and G.

16. A composition comprising the precursor of claim 1 and a solvent therefor.

17. The composition of claim 16 , wherein the solvent is a hydrocarbon solvent selected from the group consisting of an ether, a tertiary amine, an alkyl hydrocarbon, an aromatic hydrocarbon, a siloxane, a tertiary aminoether, and combinations thereof.

18. The composition of claim 16 , wherein the organometallic compound and the hydrocarbon solvent each comprise a boiling point, wherein a difference between the boiling point of the organometallic compound and the boiling point of the solvent is less than 40 degrees Celsius; 30 degrees Celsius; 20 degrees Celsius; or 10 degrees Celsius.

19. The composition of claim 16 , wherein the composition has a melting point of 120 degrees Celsius or less, 70 degrees Celsius or less, 60 degrees Celsius or less, 50 degrees Celsius or less, 40 degrees Celsius or less, or 30 degrees Celsius or less.

20. The composition of claim 16 , wherein the composition is in a liquid form at ambient temperature.

21. The composition of claim 16 , further comprising a melting point depression additive comprising a low volatility inert substance selected from the group consisting of a long chain, branched or cyclic saturated hydrocarbon C n H n+2 , wherein n has a value of 10 to about 20; a substituted arene; an organoamine; an aminoether; an ether; and combinations thereof.

22. A method for forming a transition metal-containing film on at least one surface of a substrate comprising:
a. providing the at least one surface of the substrate in a reaction chamber;
b. forming a transition metal-containing film on the at least one surface by a deposition process chosen from a chemical vapor deposition process and an atomic layer deposition process using the precursor of claim 1 or the composition of claim 16 as a metal source compound for the deposition process.

23. The method of claim 22 , wherein the precursor of claim 1 or the precursor of the composition of claim 16 in step b is selected from the group consisting of

24. The method of claim 22 , wherein the precursor of claim 1 or the precursor in the composition of claim 16 is in a liquid form at ambient temperature; and has a melting point of 120 degrees Celsius or less, 70 degrees Celsius or less, 60 degrees Celsius or less, 50 degrees Celsius or less, 40 degrees Celsius or less, or 30 degrees Celsius or less.

25. The method of claim 22 , wherein the precursor of claim 1 or the precursor in the composition of claim 16 in step b is selected from the group consisting of trichloro(tert-amylimino)Vanadium, trichloro(sec-butylimino)vanadium, and tert-amylimino-tris(dimethylamino)vanadium; and the transition metal-containing film is vanadium-containing film.

26. The method of claim 22 , further comprising introducing into the reaction chamber at least one oxygen-containing source selected from the group consisting of water, diatomic oxygen, hydrogen peroxide, oxygen plasma, ozone, NO, N 2 O, NO 2 , carbon monoxide, carbon dioxide and combinations thereof.

27. The method of claim 22 , further comprising introducing into the reaction chamber at least one nitrogen-containing source selected from the group consisting of ammonia, hydrazine, monoalkylhydrazine, dialkylhydrazine, nitrogen, nitrogen/hydrogen, ammonia plasma, nitrogen plasma, nitrogen/hydrogen plasma, and combinations thereof

Assignees

• Versum Mat Us Llc

Inventors

• Li Guocan
• Ivanov Sergei V
• Lei Xinjian
• Li Hongbo

Classifications

• C23C16/45553 Primary

  characterized by the use of precursors specially adapted for ALD · CPC title

• C23C16/45536

  Use of plasma, radiation or electromagnetic fields · CPC title

• C23C16/34

  Nitrides {(C23C16/303 takes precedence)} · CPC title

• C01B21/0617

  with vanadium, niobium or tantalum · CPC title

• C07F9/00

  Compounds containing elements of Groups 5 or 15 of the Periodic Table · CPC title