Precursors for Depositing Group 4 Metal-Containing Films

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 comprises a metal chosen from Ti, Zr, and Hf;
• R and R1 are each independently selected from an alkyl group comprising from 1 to 10 carbon atoms;
• R2 is an alkyl group comprising from 1 to 10 carbon atoms;
• R3 is chosen from hydrogen or an alkyl group comprising from 1 to 3 carbon atoms;
• R4 is an alkyl group comprising from 1 to 6 carbon atoms and wherein R2 and R4 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.

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 R1 are each selected independently selected from an alkyl group comprising from 1 to 10 carbon atoms;
• R2 is an alkyl group comprising from 1 to 10 carbon atoms;
• R3 is chosen from hydrogen or an alkyl group comprising from 1 to 3 carbon atoms;
• R4 is an alkyl group comprising from 1 to 6 carbon atoms and wherein R2 and R4 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(ethoxy)bis(2,2,6,6-tetramethyl-3,5-heptanedionato)titanium;
• (ethoxy)(isoproxy)bis(2,2,6,6-tetramethyl-3,5-heptanedionato)titanium;
• bis(iso-propoxy)bis(2,2,6,6-tetramethyl-3,5-heptanedionato)titanium;
• (ethoxy)(t-butoxy)bis(2,2,6,6-tetramethyl-3,5-heptanedionato)titanium;
• bis(t-butoxy)bis(2,2,6,6-tetramethyl-3,5-heptanedionato)titanium;
• bis(iso-propoxy)bis(2,2-dimethyl-3,5-hexanedionato)titanium, (iso-proxy)(n-butoxy)bis(2,2-dimethyl-3,5-hexanedionato)titanium, bis(n-butoxy)bis(2,2-dimethyl-3,5-hexanedionato)titanium, and combinations thereof.

A method for forming a metal-containing film on at least one surface of a substrate, the method comprising:

• providing the at least one surface of the substrate in a deposition chamber;
• and forming the metal-containing film on the at least one surface by a deposition process chosen from a cyclic chemical vapor deposition process and an atomic layer deposition process from an at least one Group 4 metal-containing precursor having the following formula I:
• wherein M comprises a metal chosen from Ti, Zr, and Hf;
• R and R1 are each independently selected from an alkyl group comprising from 1 to 10 carbon atoms;
• R2 is an alkyl group comprising from 1 to 10 carbon atoms;
• R3 is chosen from hydrogen or an alkyl group comprising from 1 to 3 carbon atoms;
• R4 is an alkyl group comprising from 1 to 6 carbon atoms and wherein R2 and R4 are different alkyl groups.

A method for forming a metal-containing film on a substrate, the method comprising the steps of:

• a. introducing a Group 4 metal-containing precursor having the following formula I into a deposition chamber and then chemisorbing the Group 4 metal onto at least a portion of the substrate which is heated;
• wherein M comprises a metal chosen from Ti, Zr, and Hf;
• R and R1 are each selected independently from an alkyl group comprising from 1 to 10 carbon atoms;
• R2 is an alkyl group comprising from 1 to 10 carbon atoms;
• R3 is chosen from hydrogen or an alkyl group comprising from 1 to 3 carbon atoms;
• R4 is an alkyl group comprising from 1 to 6 carbon atoms and wherein R2 and R4 are different alkyl groups
• b. purging away the unreacted Group 4 metal-containing precursor;
• c. introducing a oxidizing agent comprising at least one selected from group consisting of water, oxygen, oxygen plasma, ozone, and water plasma;
• d. introducing a polydentate β-ketoiminate selected from the group consisting of:
• wherein
• M is a group 2 metal selected from the group consisting of:
• magnesium, calcium, strontium, and barium;
• R1 is selected from the group consisting of:
• a C1 to C10 alkyl, a C1 to C10 alkoxyalkyl, a C1 to C10 alkoxy, a C1 to C10 fluoroalkyl, a C3 to C10 cycloaliphatic, and a C6 to C10 aryl;
• R2 is selected from the group consisting of:
• hydrogen, a C1 to C10 alkyl, a C1 to C10 alkoxyalkyl, a C1 to C10 alkoxy, a C3 to C10 cycloaliphatic, and a C6 to C10 aryl;
• R3 is selected from the group consisting of:
• a C1 to C10 alkyl, a C1 to C10 alkoxyalkyl, a C1 to C10 alkoxy, a C3 to C10 cycloaliphatic, and a C6 to C10 aryl;
• R4 is a C1 to C6 linear or branched alkyl bridge;
• and
• R5 is selected from the group consisting of:
• a C1 to C10 alkyl, a C1 to C10 fluoroalkyl, a C3 to C10 cycloaliphatic, and a C6 to C10 aryl, and;
• wherein
• M is a metal group having a valence of from 2 to 5;
• R1 is selected from the group consisting of alkyl, fluoroalkyl, cycloaliphatic, and aryl, having from 1 to 10 carbon atoms;
• R2 is selected from the group consisting of hydrogen, alkyl, alkoxy, cycloaliphatic, and aryl;
• R3 is selected from the group consisting of alkyl, fluoroalkyl, cycloaliphatic, and aryl;
• R4 is a linear or branched alkyl bridge;
• R5-6 are individually selected from the group consisting of alkyl, fluoroalkyl, cycloaliphatic, aryl, and heterocyclic containing either oxygen, or nitrogen atoms;
• and
• n is an integer equal to the valence of the metal M;
• and
• e. purging away the unreacted polydentate β-ketoiminate gas;
• f. introducing a oxidizing agent selected from group consisting of water, oxygen, oxygen plasma, ozone, and water plasma
• wherein steps a through f are repeated to deposit the metal-containing film.

A method for forming a metal-containing film on a substrate comprising:

• introducing a Group 4 metal-containing precursor represented by the formulas:
• wherein M comprises a metal chosen from Ti, Zr, and Hf;
• R and R1 are each independently selected from an alkyl group comprising from 1 to 10 carbon atoms;
• R2 is an alkyl group comprising from 1 to 10 carbon atoms;
• R3 is chosen from hydrogen or an alkyl group comprising from 1 to 3 carbon atoms;
• and R4 is an alkyl group comprising from 1 to 6 carbon atoms and wherein R2 and R4 are different alkyl groups;
• and
• introducing at least one oxidizing agent into the deposition chamber wherein the at least one oxidizing agent reacts with the Group 4 metal-containing precursor to provide the metal-containing film on the substrate.