Halogenated organoaminosilane precursors and methods for depositing films comprising same

A method of forming a dielectric film via an atomic layer deposition (ALD) process, the method comprising the steps of:

• a. providing a substrate in an ALD reactor;
• b. providing in the ALD reactor an at least one halogenated organoaminosilane precursor having the following Formula I:
• XmR1nHpSi(NR2R3)4-m-n-p I
• wherein X is a halide selected from the group consisting of Cl, Br, I;
• R1 is independently selected from a linear or branched C1 to C10 alkyl group, a C2 to C12 alkenyl group, a C2 to C12 alkynyl group, a C4 to C10 cyclic alkyl, and a C6 to C10 aryl group;
• R2 is selected from a linear or branched C3to C10 alkyl group, a C3 to C12 alkenyl group, a C3 to C12 alkynyl group, a C4 to C10 cyclic alkyl group, and a C6 to C10 aryl group;
• R3 is selected from a branched C1 to C10 alkyl, a C3 to C12 alkenyl group, a C3 to C12 alkynyl group, a C4 to C10 cyclic alkyl group, and a C6 to C10 aryl group;
• m is 1 or 2;
• n is 0, 1, or 2;
• p is 0, 1 or 2;
• and the sum of (m+n+p) is less than 4 and wherein R2 and R3 are linked to form a ring or R2 and R3 are not linked to form a ring;
• c. purging the ALD reactor with an inert gas;
• d. providing a nitrogen-containing source in the ALD reactor;
• e. purging the ALD reactor with an inert gas;
• and
• repeating the steps b through e until a desired thickness of the dielectric film is obtained wherein the at least one halogenated organoaminosilane precursor is selected from the group consisting of 2,6 -dimethylpiperidinodichlorosilane, 2,6-dimethylpiperidinochlorosilane, cyclohexylmethylaminochlorosilane, cyclohexylethylaminochlorosilane, and cyclohexyl-iso-propylaminochlorosilane.

A method of forming a dielectric film onto at least a surface of a substrate using a plasma enhanced atomic layer deposition (PEALD) process, the method comprising:

• a. providing a substrate in an ALD reactor;
• b. providing in the ALD reactor an at least one halogenated organoaminosilane precursor having the following Formula I:
• XmR1nHpSi(NR2R3)4-m-n-p I
• wherein X is a halide selected from the group consisting of Cl, Br, I;
• R1 is independently selected from a linear or branched C1 to C10 alkyl group, a C2 to C12 alkenyl group, a C2 to C12 alkynyl group, a C4 to C10 cyclic alkyl, and a C6 to C10 aryl group;
• R2 is selected from a linear or branched C1 to C10 alkyl group, a C3 to C12 alkenyl group, a C3 to C12 alkynyl group, a C4 to C10 cyclic alkyl group, and a C6 to C10 aryl group;
• R3 is selected from a branched C3 to C10 alkyl group, a C3 to C12 alkenyl group, a C3 to C12 alkynyl group, a C4 to C10 cyclic alkyl group, and a C6 to C10 aryl group;
• m is 1 or 2;
• n is 0, 1, or 2;
• p is 0, 1 or 2;
• and the sum of (m+n+p) is less than 4 and wherein R2 and R3 are linked to form a ring or R2 and R3 are not linked to form a ring;
• c. purging the ALD reactor with an inert gas;
• d. providing a plasma nitrogen-containing source in the ALD reactor;
• e. purging the ALD reactor with an inert gas;
• and
• repeating the steps b through e until a desired thickness of the dielectric film is obtained wherein the at least one halogenated organoaminosilane precursor is selected from the group consisting of 2,6-dimethylpiperidinodichlorosilane, 2,6-dimethylpiperidinochlorosilane, cyclohexylmethylaminochlorosilane, cyclohexylethylaminochlorosilane, and cyclohexyl-iso-propylaminochlorosilane.

A method for forming a silicon oxide film on a substrate comprising:

• reacting an oxidizing agent with a precursor comprising a halogenated organoaminosilane represented by the following Formula I:
• XmR1nHpSi(NR2R3)4-m-n-p I
• wherein X is a halide selected from the group consisting of Cl, Br, I;
• R1 is independently selected from a linear or branched C1 to C10 alkyl group, a C2 to C12 alkenyl group, a C2 to C12 alkynyl group, a C4 to C10 cyclic alkyl, and a C6 to C10 aryl group;
• R2 is selected from a linear or branched C1 to C10 alkyl group, a C3 to C12 alkenyl group, a C3 to C12 alkynyl group, a C4 to C10 cyclic alkyl group, and a C6 to C10 aryl group;
• R3 is selected from a branched C3to C10 alkyl group, a C3 to C12 alkenyl group, a C3 to C12 alkynyl group, a C4 to C10 cyclic alkyl group, and a C6 to C10 aryl group;
• m is 1 or 2;
• n is 0, 1, or 2;
• p is 0, 1 or 2;
• and the sum of (m+n+p) is less than 4 and wherein R2 and R3 are linked to form a ring in a vapor deposition process to form the silicon oxide film on the substrate wherein the at least one halogenated organoaminosilane precursor is selected from the group consisting of 2,6-dimethylpiperidinodichlorosilane, 2,6-dimethylpiperidinochlorosilane, cyclohexylmethylaminochlorosilane, cyclohexylethylaminochlorosilane, and cyclohexyl-iso-propylaminochlorosilane.

A method for forming a silicon oxide film on a substrate comprising:

• forming via vapor deposition of the silicon oxide film on the substrate from a composition comprising at least one organoaminosilane precursor having the following Formula I:
• XmR1nHpSi(NR2R3)4-m-n-p I
• wherein X is a halide selected from the group consisting of Cl, Br, I;
• R1 is independently selected from a linear or branched C1 to C10 alkyl group, a C2 to C12 alkenyl group, a C2 to C12 alkynyl group, a C4 to C10 cyclic alkyl, and a C6 to C10 aryl group;
• R2 is selected from a linear or branched C1 to C10 alkyl group, a C3 to C12 alkenyl group, a C3 to C12 alkynyl group, a C4 to C10 cyclic alkyl group, and a C6 to C10 aryl group;
• R3 is selected from a branched C3 to C10 alkyl group, a C3 to C12 alkenyl group, a C3 to C12 alkynyl group, a C4 to C10 cyclic alkyl group, and a C6 to C10 aryl group;
• m is 1 or 2;
• n is 0, 1, or 2;
• p is 0, 1 or 2;
• and the sum of (m+n+p) is less than 4 and wherein R2 and R3 are linked to form a ring or R2 and R3 are not linked to form a ring and at least one oxidizing agent,
• wherein the vapor deposition is at least one selected from chemical vapor deposition, low pressure vapor deposition, plasma enhanced chemical vapor deposition, cyclic chemical vapor deposition, plasma enhanced cyclic chemical vapor deposition, atomic layer deposition, and plasma enhanced atomic layer deposition;
• and wherein the at least one halogenated organoaminosilane precursor is selected from the group consisting of 2,6-dimethylpiperidinodichlorosilane, 2,6-dimethylpiperidinochlorosilane, cyclohexylmethylaminochlorosilane, cyclohexylethylaminochlorosilane, and cyclohexyl-iso-propylaminochlorosilane.

A method for forming a silicon oxide film on a substrate comprising:

• introducing a halogenated organoaminosilane represented by the following Formula I:
• XmR1nHpSi(NR2R3)4-m-n-p I
• wherein X is a halide selected from the group consisting of Cl, Br, I;
• R1 is independently selected from a linear or branched C1 to C10 alkyl group, a C2 to C12 alkenyl group, a C2 to C12 alkynyl group, a C4 to C10 cyclic alkyl, and a C6 to C10 aryl group;
• R2 is selected from a linear or branched C1 to C10 alkyl, a C3 to C12 alkenyl group, a C3 to C12 alkynyl group, a C4 to C10 cyclic alkyl group, and a C6 to C10 aryl group;
• R3 is selected from a branched C3to C10 alkyl group, a C3 to C12 alkenyl group, a C3 to C12 alkynyl group, a C4 to C10 cyclic alkyl group, and a C6 to C10 aryl group;
• m is 1 or 2;
• n is 0, 1, or 2;
• p is 0, 1 or 2;
• and the sum of (m+n+p) is less than 4 and wherein R2 and R3 are linked to form a ring or R2 and R3 are not linked to form a ring into a reactor;
• introducing at least one oxidizing agent into the reactor wherein the at least one oxidizing agent reacts with the organoaminosilane to provide the silicon oxide film on the substrate wherein the halogenated organoaminosilane is selected from the group consisting of 2,6-dimethylpiperidinochlorosilane, 2,6-dimethylpiperidinodichlorosilane, dicyclohexylaminochlorosilane, cyclohexylmethylaminochlorosilane, cyclohexylethylaminochlorosilane, cyclohexyl-iso-propylaminochlorosilane, N -(chlorosilyl)perhydroguinoline, phenylallylaminochlorosilane, m-tolylmethylaminochlorosilane, N-(chlorosilyl)carbazole, N-(chlorosilyl)-tetrahydroguinoline, N-(chlorosilyl)indole, N-(chlorosilyl)-2-methylindole, N-(chlorosilyl)-3-methylindole, and N-(chlorosilyI)-1,2,3,4-Tetrahydro-2-methylguinoline.

A method for forming a silicon oxide film on a substrate wherein the film comprises a thickness, the method comprising:

• a. introducing an at least one halogenated organoaminosilane represented following Formula I:
• XmR1nHpSi(NR2R3)4-m-n-p I
• wherein X is a halide selected from the group consisting of Cl, Br, I;
• R1 is independently selected from a linear or branched C1 to C10 alkyl group, a C2 to C12 alkenyl group, a C2 to C12 alkynyl group, a C4 to C10 cyclic alkyl, and a C6 to C10 aryl group;
• R2 is selected from a linear or branched C1 to C10 alkyl, a C3 to C12 alkenyl group, a C3 to C12 alkynyl group, a C4 to C10 cyclic alkyl group, and a C6 to C10 aryl group;
• R3 is selected from a branched C3to C10 alkyl group, a C3 to C12 alkenyl group, a C3 to C12 alkynyl group, a C4 to C10 cyclic alkyl group, and a C6 to C10 aryl group;
• m is 1 or 2;
• n is 0, 1, or 2;
• p is 0, 1 or 2;
• and the sum of (m+n+p) is less than 4 and wherein R2 and R3 are linked to form a ring into a deposition chamber;
• b. chemisorbing the at least one halogenated organoaminosilane precursor onto the substrate;
• c. purging away the unreacted at least one halogenated organoaminosilane precursor using a purge gas;
• d. providing an oxygen source to the halogenated organoaminosilane precursor onto the heated substrate to react with the sorbed at least one halogenated organoaminosilaneprecursor;
• and
• e. optionally purging away any unreacted oxygen source;
• wherein the at least one organoaminosilane precursor is selected from the group consisting of 2,6-dimethylpiperidinodichlorosilane, 2,6-dimethylpiperidinochlorosilane, cyclohexylmethylaminochlorosilane, cyclohexylethylaminochlorosilane, and cyclohexyl-iso-propylaminochlorosilane.

A method for forming a silicon-containing film on at least one surface of a substrate by a deposition process chosen from a chemical vapor deposition process and an atomic layer deposition process, the method comprising:

• providing the at least one surface of the substrate in a reaction chamber;
• introducing at least one halogenated organoaminosilane precursor having the following formula:
• CIH2Si(NR2R3)
• wherein R2 is selected from a linear or branched C1 to C10 alkyl group, a C3 to C12 alkenyl group, a C3 to C12 alkynyl group, a C4 to C10 cyclic alkyl group, and a C6 to C10 aryl group;
• R3 is selected from a branched C3 to C10 alkyl group, a C3 to C12 alkenyl group, a C3 to 012 alkynyl group, a C4 to C10 cyclic alkyl group, and a C6 to C10 aryl group;
• and wherein R2 and R3 can form a cyclic or alkyl substituted cyclic ring into the reaction chamber wherein the at least one halogenated organoaminosilane reacts to provide the film on the at least one surface.