Liquid composition containing aminoether for deposition of metal-containing films

1. A formulation, comprising:

a) at least one metal-ligand complex, wherein one or more ligands are selected from the group consisting of, β-diketonate, β-ketoiminate, β-ketoesterate, β-diiminate, alkyl, carbonyl, alkyl carbonyl, cyclopentadienyl, pyrrolyl, alkoxide, amidinate, imidazolyl, and mixtures thereof; and the metal is selected from Group 2 to 16 elements of the Periodic Table of the Elements; and,

b) at least one aminoether solvent selected from the group consisting of R 1 R 2 NR 3 OR 4 NR 5 R 6 , R 1 OR 4 NR 5 R 6 , O(CH 2 C 2 ) 2 NR 1 , R 1 R 2 NR 3 N(CH 2 CH 2 ) 2 O, R 1 R 2 NR 3 OR 4 N(CH 2 CH 2 ) 2 O, O(CH 2 CH 2 ) 2 NR 3 OR 4 N(CH 2 CH 2 ) 2 O, and mixtures thereof, wherein R 1-2 and R 5-6 are independently selected from group consisting of C 1-10 linear alkyl, C 1-10 branched alkyl, C 1-10 cyclic alkyl, C 6 -C 10 aromatic, C 1-10 alkylamine, C 1-10 alkylaminoalkyl, C 1-10 ether, C 4 -C 10 cyclic ether, C 4 -C 10 cyclic aminoether, and mixture thereof; and R 3-4 are independently selected from group consisting of C 1-10 linear alkylene, C 1-10 branched alkylene, C 1-10 cyclic alkylene, C 6 -C 10 aromatic, C 1-10 alkylamine, C 1-10 alkylaminoalkyl, C 1-10 ether, C 4 -C 10 cyclic ether, C 4 -C 10 cyclic aminoether, and mixture thereof.

2. The formulation of claim 1 wherein the one or more ligands of the metal-ligand complex are monodentate, bidentate, multidentate and mixtures thereof.

3. The formulation of claim 1 wherein the formulation comprises aminoethers with a general formula of: R 1 R 2 NR 3 OR 4 NR 5 R 6 , wherein R 1-2 and R 5-6 are independently selected from group consisting of C 1-10 linear alkyl, C 1-10 branched alkyl, C 1-10 cyclic alkyl, C 6 -C 10 aromatic; and R 3-4 are independently selected from group consisting of C 1-10 linear alkylene, C 1-10 branched alkylene, C 1-10 cyclic alkylene, C 6 -C 10 aromatic, C 1-10 alkylamine, C 1-10 alkylaminoalkyl, C 1-10 ether, C 4 -C 10 cyclic ether, C 4 -C 10 cyclic aminoether, and mixture thereof.

4. The formulation of claim 1 wherein the aminoether is selected from the group consisting of:

and mixtures thereof.

5. The formulation of claim 3 wherein the metal-ligand complex is selected from the group consisting of:

(a) metal β-diketonates having the formula:

wherein M is selected from Group 2 to 16 metals, R 1-3 are individually selected from the group consisting of hydrogen, C 1-10 linear or branched alkyl, C 1-10 linear or branched alkoxy, C 4-10 cycloaliphatic, C 6-10 aryl, and C 1-10 fluorinated alkyl; and x=2, 3, or 4;

(b) metal β-ketoiminates having the formula:

wherein M is selected from Group 2 to 16 metals, R 1-4 are individually selected from the group consisting of hydrogen, C 1-10 linear or branched alkyl, C 1-10 linear or branched alkoxy, C 4-10 cycloaliphatic, C 6-10 aryl, and C 1-10 linear or branched fluorinated alkyl; and x=2, 3, 4;

(c) metal β-diiminates having the formula:

wherein M is selected from Group 2 to 16 metal, R 1-5 are individually selected from the group consisting of hydrogen, C 1-10 linear or branched alkyl, C 1-10 linear or branched alkoxy, C 4-10 cycloaliphatic, C 6-10 aryl, and C 1-10 linear or branched fluorinated alkyl; and x=2, 3, 4;

(d) metal β-ketoiminates having the formula:

wherein M is selected from Group 2 to 16 metal; R 1-6 and R 5-6 are individually selected from the group consisting of hydrogen, C 1-10 linear or branched alkyl, C 1-10 linear or branched alkoxy, C 4-10 cycloaliphatic, C 6-10 aryl, and C 1-10 linear or branched fluorinated alkyl; R 4 is selected from group consisting of hydrogen, C 1-10 linear or branched alkylene, C 1-10 linear or branched alkoxy, C 4-10 cycloaliphatic, C 6-10 aryl, and C 1-10 linear or branched fluorinated alkylene; and x=2,3;

(e) metal β-ketoiminates having the formula:

wherein M is an alkaline earth metal selected from Group 2; R 1 is a branched alkyl group containing 4 to 10 carbon atoms; R 2 is selected from the group consisting of hydrogen, C 1-10 linear or branched alkyl, C 1-10 linear or branched alkoxy, C 4-10 cycloaliphatic, C 6-10 aryl, and C 1-10 linear or branched fluorinated alkyl; R 3 is selected from the group consisting of C 1-10 linear or branched alkyl, C 1-10 linear or branched alkoxy, C 4-10 cycloaliphatic, C 6-10 aryl, and C 1-10 linear or branched fluorinated alkyl; R 4-5 are individually selected from the group consisting of C 1-10 linear or branched alkylene, C 1-10 linear or branched alkoxy, C 4-10 cycloaliphatic, C 6-10 aryl, and C 1-10 linear or branched fluorinated alkylene; R 6-7 are individually selected from the group consisting of C 1-10 linear or branched alkyl, C 1-10 linear or branched alkoxy, C 4-10 cycloaliphatic, C 6-10 aryl, and C 1-10 linear or branched fluorinated alkyl and a ring containing carbon, oxygen, or nitrogen atoms;

(f) metal β-ketoiminates having the formula:

wherein M is a metal ion selected from Group 4 metals; wherein R 1 is a branched alkyl group containing 4 to 10 carbon atoms; R 2 can be individually selected from the group consisting of hydrogen, C 1-10 linear or branched alkyl, C 1-10 linear or branched alkoxy, C 4-10 cycloaliphatic, C 6-10 aryl, and C 1-10 linear or branched fluorinated alkyl; R 3 is selected from the group consisting of C 1-10 linear or branched alkyl, C 1-10 linear or branched alkoxy, C 4-10 cycloaliphatic, C 6-10 aryl, and C 1-10 linear or branched fluorinated alkyl; R 4 is selected from group consisting of C 1-10 linear or branched alkylene, C 1-10 linear or branched alkoxy, C 4-10 cycloaliphatic, C 6-10 aryl, and C 1-10 linear or branched fluorinated alkylene; R 5-6 are individually selected from the group consisting of C 1-10 linear or branched alkyl, C 1-10 linear or branched alkoxy, C 4-10 cycloaliphatic, C 6-10 aryl, and C 1-10 linear or branched fluorinated alkyl; and a ring containing carbon, oxygen, or nitrogen atoms; R 7 is selected from the group consisting of C 1-10 linear or branched alkyl, C 1-10 linear or branched alkoxy, C 4-10 cycloaliphatic, C 6-10 aryl, and C 1-10 linear or branched fluorinated alkyl; and n=1,2,3;

(g) metal β-ketoiminates having the formula:

wherein M is a metal ion selected from Group 11; R 1 is a branched alkyl group containing 1 to 10 carbon atoms; R 2 is selected from the group consisting of hydrogen, C 1-10 linear or branched alkyl, C 1-10 linear or branched alkoxy, C 4-10 cycloaliphatic, C 6-10 aryl, and C 1-10 linear or branched fluorinated alkyl; R 3 is selected from the group consisting of C 1-10 linear or branched alkyl, C 1-10 linear or branched alkoxy, C 4-10 cycloaliphatic, C 6-10 aryl, and C 1-10 linear or branched fluorinated alkyl; R 4 is selected from groups consisting of C 1-10 linear or branched alkylene, C 1-10 linear or branched alkoxy, C 4-10 cycloaliphatic, C 6-10 aryl, and C 1-10 linear or branched fluorinated alkylene; R 5-6 are individually selected from the group consisting of C 1-10 linear or branched alkyl, C 1-10 linear or branched alkoxy, C 4-10 cycloaliphatic, C 6-10 aryl, and C 1-10 linear or branched fluorinated alkyl, and a ring containing carbon, oxygen, or nitrogen atoms; X is carbon or silicon; 7

(h) metal complex having the formula:

L n M R) X

wherein M is selected from Group 2 to 16 metals, wherein R is selected from the group consisting of hydrogen, C 1-10 linear, branched, saturated or unsaturated alkyl, C 1-10 linear or branched alkoxy, C 4-10 cycloaliphatic, C 6-10 aryl, and C 1-10 linear or branched fluorinated alkyl, cyclopentadienyl, alkyl substituted cyclopentadienyl, pyrollyl, alkyl substituted pyrollyl, imidazolyl, alkyl substituted imidazolyl and their derivatives; wherein x=2, 3, 4; L is a neutral or mono anion donor ligand containing oxygen or nitrogen atoms; and n=0, 1, 2, 3, 4;

(i) alkyl metal carbonyls having the formula:

(CO) y M R) X

wherein M is selected from Group 2 to 16 metals; R is selected from the group consisting of hydrogen, C 1-10 linear or branched alkyl, C 1-10 linear or branched alkoxy, C 4-10 cycloaliphatic, C 6-10 aryl, and C 1-10 linear or branched fluorinated alkyl, cyclopendienyl and their derivatives; x=2, 3, 4; and y=1, 2, 3, or 4;

(j) metal carbonyls having the formula:

M x (CO) y

wherein M is selected from Group 8 to 10 metal; x=1, 2, 3; and y=4 to 12;

(k) metal alkoxides having the formula:

M(OR)n

wherein M is selected from Group 2 to 16 metal; R is selected from the group consisting of C 1-10 alkyl, C 1-10 alkenyl, C 1-10 alkynyl, C 5 -C 10 cycloaliphatic, C 6-12 aryl, and fluorinated C 1-10 alkyl; and n is 2, 3, 4 or 5;

(l) metal amides having the formula:

M(NR 1 R 2 )n

wherein M is selected from Group 2 to 16 metal; R 1-2 are independently selected from the group consisting of C 1-10 linear or branched alkyl, C 1-10 linear or branched alkenyl, C 1-10 linear or branched alkynyl, C 3-10 linear or branched alkylsilyl, C 5 -C 10 cycloaliphatic, C 6-12 aryl, and linear or branched fluorinated C 1-10 alkyl; and n is 2, 3, 4, or 5;

(m) metal alkoxy β-diketonates having the formula:

wherein M comprises a metal selected from the group consisting of Ti, Zr, and Hf; R 1 is an alkyl group comprising from 1 to 10 carbon atoms; R 2 is an alkyl group comprising from 1 to 10 carbon atoms; R 3 is selected from the group consisting of hydrogen and an alkyl group comprising from 1 to 3 carbon atoms; and R 4 is an alkyl group comprising from 1 to 6 carbon atoms;

(n) metal amidinates having the formula:

wherein M is selected from Group 2 to 16 metals, wherein R 1-3 are individually selected from the group consisting of hydrogen, C 1-10 linear or branched alkyl, C 1-10 linear or branched alkoxy, C 4-10 cycloaliphatic, C 6-10 aryl, and C 1-10 linear or branched fluorinated alkyl; wherein x=2, 3, 4; and mixtures thereof.

6. The formulation of claim 1 wherein the aminoether is selected from the group consisting of 2,2′-oxybis(N,N-dimethylethanamine), 4-[2-(dimethylamino)ethyl]morpholine, and mixtures thereof.

7. The formulation of claim 6 wherein the aminoether is 2,2′-oxybis(N,N-dimethylethanamine) having less than 20 ppm of water.

8. The formulation of claim 6 wherein the aminoether is 2,2′-oxybis(N,N-dimethylethanamine) having less than 100 ppm of additional compounds containing hydroxyl or amine functionality.

9. A liquid formulation useful for deposition of metal-containing thin films in making semiconductor devices, comprising;

a) at least one metal-ligand complex selected from the group consisting of bis(2,2-dimethyl-5-(dimethylaminoethyl-imino)-3-hexanonato-N,O,N′)strontium, bis(2,2-dimethyl-5-(1-dimethylamino-2-propylimino)-3-hexanonato-N,O,N′)strontium, bis(2,2-dimethyl-5-(dimethylaminoethyl-imino)-3-hexanonato-N,O,N′)bis(tertbutoxy)titanium, tetrakis(2,2,6,6-tetramethyl-3,5-heptanedionato)cerium (IV), tris(2,2,6,6tetramethyl-3,5-heptanedionato)lanthanum, Sr( t Bu 3 Cp) 2 , Ba( t Bu 3 Cp) 2 , Sr( i Pr) 3 Cp) 2 ,Ba( i Pr 3 Cp) 2 , LaCp 3 , La(MeCp) 3 , La(EtCp) 3 , La( i PrCp) 3 , zirconium tert butoxide, bis(2-tert-butyl-4,5-di-tert-amylimidazolyl)strontium, bis(2-tert-butyl-4,5-di-tert amylimidazolyl)barium, bis(2,5-di-tert-butyl-pyrrolyl)strontium, bis(2,5-di-tert-butyl-pyrrolyl)barium, Ru(EtCp) 2 , Ru(EtCp)(DMPD) and mixtures thereof; and,

b) at least one aminoether selected from the group consisting of 2,2′-oxybis(N,N-dimethylethanamine), 4-[2-(dimethylamino)ethyl]morpholine, and mixtures thereof.

10. The formulation of claim 1 comprising bis(2,2-dimethyl-5-(dimethylaminoethyl-imino)-3-hexanonato-N,O,N′)strontium and 2,2′-oxybis(N,N-dimethylethanamine).

11. A process for depositing a metal-containing film by chemical vapor deposition or atomic layer deposition comprising contacting a substrate under conditions to deposit a metal-containing film from a formulation of claim 1 and depositing such metal-containing film.

12. A process for depositing a metal-containing film by chemical vapor deposition or atomic layer deposition comprising contacting a substrate under conditions to deposit a metal-containing film from a formulation of claim 4 and depositing such metal-containing film.

13. A process for depositing a metal-containing film by chemical vapor deposition or atomic layer deposition comprising contacting a substrate under conditions to deposit a metal-containing film from a formulation of claim 5 and depositing such metal-containing film.

14. The process of claim 11 wherein the formulation is delivered by direct liquid injection through a vaporizer.