Precursors for depositing group 4 metal-containing films
View Patent ↗Described herein are Group 4 metal-containing precursors, compositions comprising Group 4 metal-containing precursors, and deposition processes for fabricating conformal metal containing films on substrates. In one aspect, the Group 4 metal-containing precursors are represented by the following formula I: wherein M comprises a metal chosen from Ti, Zr, and Hf; R and R 1 are each independently selected from 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 chosen from hydrogen or an alkyl group comprising from 1 to 3 carbon atoms; R 4 is an alkyl group comprising from 1 to 6 carbon atoms and wherein R 2 and R 4 are different alkyl groups. Also described herein are methods for making Group 4 metal-containing precursors and methods for depositing films using the Group 4 metal-containing precursors.
1. A method for forming a metal-containing film on at least a surface of a substrate comprising:
forming via vapor deposition the metal-containing film on the surface from a composition comprising Group 4 metal-containing precursor having the following formula I:
wherein M is Ti; R and R 1 are each independently selected from 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 chosen from hydrogen or an alkyl group comprising from 1 to 3 carbon atoms; R 4 is an alkyl group comprising from 1 to 6 carbon atoms and wherein R 2 and R 4 are different alkyl groups; and
at least one solvent selected from the group consisting of: an aliphatic hydrocarbon, an aromatic hydrocarbon, an ether, an ester, a nitrite, an amine, an organic amide, an alcohol, an imine, a carbodiimide, a ketone, an aldehyde, an amidine, a guandadine, an isourea, a glyme solvent having from 1 to 6 oxygen atoms and mixtures thereof wherein the viscosity of the composition at a temperature of 25° C. is 50 centipoise or less,
wherein the vapor deposition is at least one selected from cyclic chemical vapor deposition, plasma enhanced chemical vapor deposition, or atomic layer deposition.
2. The method of claim 1 wherein R 2 comprises a tert-butyl group, R 4 comprises a methyl group, and R 3 comprises hydrogen.
3. The method of claim 2 wherein R and R 1 each comprise a tert-butyl group.
4. The method of claim 2 wherein R and R 1 each comprise an ethyl group.
5. The method of claim 2 wherein R and R 1 each comprise an iso-propyl group.
6. The method of claim 1 wherein R 2 comprises an iso-butyl group, R 4 comprises a methyl group, and R 3 comprises hydrogen.
7. The method of claim 6 wherein R and R 1 each comprise a tert-butyl group.
8. The method of claim 6 wherein R and R 1 each comprise an ethyl group.
9. The method of claim 6 wherein R and R 1 each comprise an iso-propyl group.
10. The method of claim 1 wherein the metal-containing precursor has a melting point of 60° C. or below.
11. A composition for forming a metal-containing film comprising:
at least 50 percent by weight or greater of at least one Group 4 metal-containing precursor having the following formula I
wherein M is Ti; R and R 1 are each independently selected from 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 chosen from hydrogen or an alkyl group comprising from 1 to 3 carbon atoms; R 4 is an alkyl group comprising from 1 to 6 carbon atoms and wherein R 2 and R 4 are different alkyl groups; and
at least one solvent selected from the group consisting of: an aliphatic hydrocarbon, an aromatic hydrocarbon, an ether, an ester, a nitrite, an amine, an organic amide, an alcohol, an imine, a carbodiimide, a ketone, an aldehyde, an amidine, a guandadine, an isourea, a glyme solvent having from 1 to 6 oxygen atoms and mixtures thereof wherein the viscosity of the composition at a temperature of 25° C. is 50 centipoise or less.
12. The composition of claim 11 wherein the at least one solvent is selected from the group consisting of: the ether selected from the group consisting of glyme solvents having from 1 to 6 oxygen atoms; the alcohol comprising C 2 -C 12 alkanols, the ether selected from the group consisting of dialkyl ethers comprising C 1 -C 6 alkyl moieties, C 4 -C 8 cyclic ethers; C 12 -C 60 crown O 4 -O 20 ethers wherein the prefixed Ci range is the number i of carbon atoms in the ether compound and the suffixed Oi range is the number i of oxygen atoms in the ether compound; the hydrocarbons comprising C 6 -C 12 aliphatic hydrocarbons; the hydrocarbons comprising C 6 -C 18 aromatic hydrocarbons; an organic amide of the form RCONR′R″ wherein R and R′ are alkyl groups comprising from 1 to 10 carbon atoms and can be can be connected to form a cyclic group (CH 2 ) n , wherein n is from 4 to 6, and R″ is selected from an alkyl group comprising from 1 to 4 carbon atoms and an cycloalkyl group.
13. The composition of claim 12 wherein the at least one solvent comprises at least one selected from the group consisting of octane, dodecane, toluene, and mesitylene.
14. The composition of claim 11 wherein the viscosity is 25 cP or less at 25° C.
15. The composition of claim 14 wherein the viscosity is 10 cP or less at 25° C.
16. A composition comprising:
a plurality of Group 4 metal-containing precursors wherein at least one of the Group 4 metal-containing precursors is a precursor having the following formula I:
wherein M comprises a metal chosen from Ti, Zr and Hf; R and R 1 are each independently selected from 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 chosen from hydrogen or an alkyl group comprising from 1 to 3 carbon atoms; R 4 is an alkyl group comprising from 1 to 6 carbon atoms and wherein R 2 and R 4 are different alkyl groups; and
wherein the at least one of the Group 4 metal-containing precursor having formula I is selected from the group consisting of bis(iso-propoxy)bis(2,2-dimethyl-3,5-hexanedionato)titanium, (iso-proxy)(n-butoxy)bis(2,2-dimethyl-3,5-hexanedionato)titanium, and bis(n-butoxy)bis(2,2-dimethyl-3,5-hexanedionato)titanium.
17. A composition comprising:
a plurality of Group 4 metal-containing precursors wherein at least one of the Group 4 metal-containing precursors is a precursor having the following formula I:
wherein M comprises a metal chosen from Ti, Zr and Hf; R and R 1 are each selected independently selected from 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 chosen from hydrogen or an alkyl group comprising from 1 to 3 carbon atoms; R 4 is an alkyl group comprising from 1 to 6 carbon atoms and wherein R 2 and R 4 are the same alkyl groups; and
wherein the at least one of the Group 4 metal-containing precursor having formula I is selected from the group consisting of bis(ethoxy)bis(2,2,6,6-tetramethyl-3,5-heptanedionato)titanium, (ethoxy)(isoproxy)bis(2,2,6,6-tetramethyl-3,5-heptanedionato)titanium, and bis(iso-propoxy)bis(2,2,6,6-tetramethyl-3,5-heptanedionato)titanium.
18. A method for forming a metal-containing film on at least a surface of a substrate comprising:
forming via vapor deposition the metal-containing film on the surface from a composition comprising Group 4 metal-containing precursor having the following formula I:
wherein M comprises a metal chosen from Ti, Zr and Hf; R and R 1 are each independently selected from 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 chosen from hydrogen or an alkyl group comprising from 1 to 3 carbon atoms; R 4 is an alkyl group comprising from 1 to 6 carbon atoms and wherein R 2 and R 4 are different alkyl groups; and
wherein the at least one of the Group 4 metal-containing precursor having formula I is selected from the group consisting of bis(iso-propoxy)bis(2,2-dimethyl-3,5-hexanedionato)titanium, (iso-proxy)(n-butoxy)bis(2,2-dimethyl-3,5-hexanedionato)titanium, and bis(n-butoxy)bis(2,2-dimethyl-3,5-hexanedionato)titanium.