AZA-polysilane precursors and methods for depositing films comprising same
View Patent ↗Described herein are precursors and methods for forming silicon-containing films. In one aspect, there is provided an aza-polysilane precursor comprising at least two Si—N bonds, at least one Si—Si bond, and at least two SiH 2 groups represented by the following Formula IA, IB and IC: wherein R 1 and R 2 are independently selected from a linear or branched C 1 to C 10 alkyl group, a linear or branched C 3 to C 10 alkenyl group, a linear or branched C 3 to C 10 alkynyl group, C 3 to C 10 cyclic alkyl group, C 3 to C 10 hetero-cyclic alkyl group, a C 5 to C 10 aryl group, and a C 3 to C 10 hetero-aryl group, a C 2 to C 10 dialkylamino group, a C 3 to C 10 cyclic alkylamino group; R 3 and R 4 are independently selected from hydrogen, a linear or branched C 1 to C 10 alkyl group, a linear or branched C 2 to C 10 alkenyl group, a linear or branched C 2 to C 10 alkynyl group, C 3 to C 10 cyclic alkyl group, C 3 to C 10 hetero-cyclic alkyl group, a C 5 to C 10 aryl group, and a C 3 to C 10 hetero-aryl group, a C 2 to C 10 dialkylamino group, a C 3 to C 10 cyclic alkylamino group; wherein R 1 in Formula IA cannot both be methyl, R 1 and R 2 in Formula IB cannot both be iso-propyl, tert-butyl, and bezenyl and R 3 and R 4 cannot both be methyl and phenyl.
1. A method for forming a silicon and nitrogen containing film on at least one surface of a substrate by 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 aza-polysilane precursor comprising at least two Si—N bonds, at least one Si—Si bond, and at least two SiH 2 groups represented by the following Formulae IA, IB, and IC:
wherein R 1 and R 2 are independently selected from a linear or branched C 1 to C 10 alkyl group, a linear or branched C 3 to C 10 alkenyl group, a linear or branched C 3 to C 10 alkynyl group, C 3 to C 10 cyclic alkyl group, C 3 to C 10 hetero-cyclic alkyl group, a C 5 to C 10 aryl group, a C 3 to C 10 hetero-aryl group, a C 2 to C 10 dialkylamino group, and a C 3 to C 6 cyclic alkylamino group; R 3 and R 4 are independently selected from hydrogen, a linear or branched C 1 to C 10 alkyl group, a linear or branched C 2 to C 10 alkenyl group, a linear or branched C 2 to C 10 alkynyl group, C 3 to C 10 cyclic alkyl group, C 3 to C 10 hetero-cyclic alkyl group, a C 5 to C 10 aryl group, and a C 3 to C 10 hetero-aryl group, a C 2 to C 10 dialkylamino group, and a C 3 to C 10 cyclic alkylamino group wherein the aza-polysilane precursor is prepared by reacting at least one of a monochlorodisilane, monobromodisilane and dialkylaminodisilane with a primary amine; and
introducing a nitrogen-containing source into the reactor wherein the at least one aza-polysilane precursor and the nitrogen-containing source react at a temperature of less than 300 C under atomic layer deposition process conditions to form the film on the at least one surface; and
wherein when the at least one aza-polysilane precursor is represented by Formula 1B R 1 and R 2 in Formula IB cannot both be iso-propyl, tert-butyl, or benzyl.
2. The method of claim 1 wherein the precursor further comprises a solvent wherein the solvent has a boiling point and wherein the difference between the boiling point of the solvent and that of the at least one aza-polysilane is 40° C. or less.
3. The method of claim 2 wherein the solvent comprises at least one selected from the group consisting of ether, tertiary amine, alkyl hydrocarbon, aromatic hydrocarbon, tertiary aminoether.
4. The method of claim 1 wherein the at least one aza-polysilane precursor is selected from the group consisting of 3-iso-propyl-3-aza-pentasilane, 3-tert-butyl-3-aza-pentasilane, 3-tert-pentyl-3-aza-pentasilane, 3-cyclopentyl-3-aza-pentasilane, 3-cyclohexyl-3-aza-pentasilane, 3-(2,6-dimethylcyclohexyl-3-aza-pentasilane, 3-(tetrahydropyran-4-yl)-3-aza-pentasilane, 3-(1-methylpiperidin-4-yl)-3-aza-pentasilane, 3-phenyl-3-aza-pentasilane, 3-(2-methyl-tolyl)-3-aza-pentasilane, 3-(2,6-dimethyl-tolyl)-3-aza-pentasilane, 3-(pyridin-3-yl)-3-aza-pentasilane, 3-(4-methylpyridin-3-yl)-3-aza-pentasilane 1,4-bis(cyclopentyl)-1,4-diaza-2,3,5,6-tetrasilacyclohexane, 1,4-bis(cyclohexyl)-1,4-diaza-2,3,5,6-tetrasilacyclohexane, 1,4-bis(2,6-dimethylcyclohexyl)-1,4-Diaza-2,3,5,6-tetrasilacyclohexane, 1,4-bis(iso-propyl)-1,4-diaza-2,3,5,6-tetrasilacyclohexane, 1,4-bis(tert-butyl)-1,4-diaza-2,3,5,6-tetrasilacyclohexane, 1,4-bis(tert-pentyl)-1,4-diaza-2,3,5,6-tetrasilacyclohexane.
5. The method of claim 1 wherein the dialkylaminodisilane comprises di-iso-propylaminodisilane.
6. A method of forming a silicon-containing film via an atomic layer deposition (ALD) process, the method comprising the steps of:
a. providing a substrate in an ALD reactor wherein the substrate is heated to a temperature of less than about 300C;
b. providing in the ALD reactor at least one aza-polysilane precursor represented by the following Formula
wherein R 1 and R 2 are independently selected from a linear or branched C 1 to C 10 alkyl group, a linear or branched C 3 to C 10 alkenyl group, a linear or branched C 3 to C 10 alkynyl group, C 3 to C 10 cyclic alkyl group, C 3 to C 10 hetero-cyclic alkyl group, a C 5 to C 10 aryl group, a C 3 to C 10 hetero-aryl group, a C 2 to C 10 dialkylamino group, and a C 3 to C 10 cyclic alkylamino group;
c. purging the ALD reactor with an inert gas;
d. alternatively providing at least one of the aza-polysilane precursor, an oxygen-containing source and a nitrogen-containing source in the ALD reactor;
e. purging the ALD reactor with an inert gas; and wherein steps b through e are repeated under ALD process conditions until a desired thickness of the film is obtained
wherein the at least one aza-polysilane precursor comprises at least one member selected from the group consisting of 1,4-bis(cyclopentyl)-1,4-diaza-2,3,5,6-tetrasilacyclohexane, 1,4-bis(cyclohexyl)-1,4-diaza-2,3,5,6-tetrasilacyclohexane, 1,4-bis(2,6-dimethylcyclohexyl)-1,4-Diaza-2,3,5,6-tetrasilacyclohexane, 1,4-bis(iso-propyl)-1,4-diaza-2,3,5,6-tetrasilacyclohexane, 1,4-bis(tert-butyl)-1,4-diaza-2,3,5,6-tetrasilacyclohexane, and 1,4-bis(tert-pentyl)-1,4-diaza-2,3,5,6-tetrasilacyclohexane and wherein the aza-polysilane precursor is prepared by reacting at least one of a monochlorodisilane, monobromodisilane or dialkylaminodisilane with a primary amine.
7. The method of claim 6 wherein the reacting step is conducted at a temperature of 200° C. or less.
8. The method of claim 6 wherein the reacting step is conducted at a temperature of 100° C. or less.
9. The method of claim 6 wherein the reacting step is conducted at 50° C. or less.
10. The method of claim 6 wherein the method further comprises at least one post-deposition treatment.
11. A method of forming a silicon-containing film onto at least a surface of a substrate using a plasma enhanced atomic layer (PEALD) deposition process, the method comprising:
a. providing a substrate in an ALD reactor;
b. providing in the ALD reactor at least one aza-polysilane precursor comprising at least two Si—N bonds, at least one Si—Si bond, and at least two SiH 2 groups represented by the following Formulae:
wherein R 1 and R 2 are independently selected from a linear or branched C 1 to C 10 alkyl group, a linear or branched C 3 to C 10 alkenyl group, a linear or branched C 3 to C 10 alkynyl group, C 3 to C 10 cyclic alkyl group, C 3 to C 10 hetero-cyclic alkyl group, a C 5 to C 10 aryl group, a C 3 to C 10 hetero-aryl group, a C 2 to C 10 dialkylamino group, and a C 3 to C 10 cyclic alkylamino group wherein the aza-polysilane precursor is prepared by reacting at least one of a monochlorodisilane, monobromodisilane and dialkylaminodisilane with a primary amine;
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 wherein the steps b through e are repeated using the PEALD deposition process until a desired thickness of the silicon-containing film is obtained.
12. The method of claim 11 wherein the at least one aza-polysilane precursor is selected from the group consisting of 1,4-bis(cyclopentyl)-1,4-diaza-2,3,5,6-tetrasilacyclohexane, 1,4-bis(cyclohexyl)-1,4-diaza-2,3,5,6-tetrasilacyclohexane, 1,4-bis(2,6-dimethylcyclohexyl)-1,4-Diaza-2,3,5,6-tetrasilacyclohexane, 1,4-bis(iso-propyl)-1,4-diaza-2,3,5,6-tetrasilacyclohexane, 1,4-bis(tert-butyl)-1,4-diaza-2,3,5,6-tetrasilacyclohexane, 1,4-bis(tert-pentyl)-1,4-diaza-2,3,5,6-tetrasilacyclohexane.
13. A method of forming a silicon-containing 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 at least one aza-polysilane precursor represented by the following Formula IB:
wherein R 1 and R 2 are independently selected from a linear or branched C 1 to C 10 alkyl group, a linear or branched C 3 to C 10 alkenyl group, a linear or branched C 3 to C 10 alkynyl group, C 3 to C 10 cyclic alkyl group, C 3 to C 10 hetero-cyclic alkyl group, a C 5 to C 10 aryl group, a C 3 to C 10 hetero-aryl group, a C 2 to C 10 dialkylamino group, and a C 3 to C 10 cyclic alkylamino group and is prepared by reacting at least one of a monochlorodisilane, monobromodisilane or dialkylaminodisilane with a primary amine;
c. purging the ALD reactor with an inert gas;
d. alternatively providing the aza-polysilane precursor, an oxygen-containing source and a nitrogen-containing source in the ALD reactor;
e. purging the ALD reactor with an inert gas; and wherein steps b through e are repeated under ALD process conditions until a desired thickness of the film is obtained.
14. The method of claim 13 wherein the at least one aza-polysilane precursor is selected from the group consisting of 1,4-bis(cyclopentyl)-1,4-diaza-2,3,5,6-tetrasilacyclohexane, 1,4-bis(cyclohexyl)-1,4-diaza-2,3,5,6-tetrasilacyclohexane, 1,4-bis(2,6-dimethylcyclohexyl)-1,4-Diaza-2,3,5,6-tetrasilacyclohexane, 1,4-bis(iso-propyl)-1,4-diaza-2,3,5,6-tetrasilacyclohexane, 1,4-bis(tert-butyl)-1,4-diaza-2,3,5,6-tetrasilacyclohexane, and 1,4-bis(tert-pentyl)-1,4-diaza-2,3,5,6-tetrasilacyclohexane.
15. The method of claim 13 wherein the ALD process is a plasma enhanced atomic layer (PEALD) process.
16. The method of claim 13 wherein the method further comprises at least one post-deposition treatment.
17. The method of claim 13 wherein the silicon containing film comprises silicon oxide.
18. The method of claim 13 wherein the nitrogen-containing source is selected from the group consisting of ammonia, hydrazine, monoalkylhydrazine, dialkylhydrazine, nitrogen, nitrogen/hydrogen, ammonia plasma, nitrogen plasma, nitrogen/hydrogen plasma, nitrogen/helium plasma, nitrogen/argon plasma, helium plasma, argon plasma, hydrogen plasma, and mixtures thereof.
19. The method of claim 13 wherein the silicon-containing film is selected from the group consisting of silicon nitride and silicon carbonitride.
20. A method of forming a silicon-containing film via an atomic layer deposition (ALD) process, the method comprising the steps of:
a. providing a substrate in an ALD reactor wherein the substrate is heated to a temperature of less than about 300 C;
b. providing in the ALD reactor at least one aza-polysilane precursor represented by the following Formula
wherein R 1 and R 2 are independently selected from a linear or branched C 1 to C 10 alkyl group, a linear or branched C 3 to C 10 alkenyl group, a linear or branched C 3 to C 10 alkynyl group, C 3 to C 10 cyclic alkyl group, C 3 to C 10 hetero-cyclic alkyl group, a C 5 to C 10 aryl group, a C 3 to C 10 hetero-aryl group, a C 2 to C 10 dialkylamino group, and a C 3 to C 10 cyclic alkylamino group;
c. purging the ALD reactor with an inert gas;
d. alternatively providing at least one of the aza-polysilane precursor, an oxygen-containing source and a nitrogen-containing source in the ALD reactor;
e. purging the ALD reactor with an inert gas; and wherein steps b through e are repeated under ALD process conditions until a desired thickness of the film is obtained
wherein the at least one aza-polysilane precursor comprises at least one member selected from the group consisting of 1,4-bis(cyclopentyl)-1,4-diaza-2,3,5,6-tetrasilacyclohexane, 1,4-bis(cyclohexyl)-1,4-diaza-2,3,5,6-tetrasilacyclohexane, 1,4-bis(2,6-dimethylcyclohexyl)-1,4-Diaza-2,3,5,6-tetrasilacyclohexane, 1,4-bis(iso-propyl)-1,4-diaza-2,3,5,6-tetrasilacyclohexane, 1,4-bis(tert-butyl)-1,4-diaza-2,3,5,6-tetrasilacyclohexane, and 1,4-bis(tert-pentyl)-1,4-diaza-2,3,5,6-tetrasilacyclohexane; wherein the aza-polysilane precursor is prepared by reacting at least one of monochlorodisilane and monobromodisilane with a primary amine.
21. A method of forming a silicon-containing 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 at least one aza-polysilane precursor represented by the following Formula IB:
wherein R 1 and R 2 are independently selected from a linear or branched C 1 to C 10 alkyl group, a linear or branched C 3 to C 10 alkenyl group, a linear or branched C 3 to C 10 alkynyl group, C 3 to C 10 cyclic alkyl group, C 3 to C 10 hetero-cyclic alkyl group, a C 5 to C 10 aryl group, a C 3 to C 10 hetero-aryl group, a C 2 to C 10 dialkylamino group, and a C 3 to C 10 cyclic alkylamino group;
c. purging the ALD reactor with an inert gas;
d. alternatively providing the aza-polysilane precursor, an oxygen-containing source and a nitrogen-containing source in the ALD reactor;
e. purging the ALD reactor with an inert gas; and wherein steps b through e are repeated under ALD process conditions until a desired thickness of the film is obtained; and
wherein the aza-polysilane precursor is prepared by reacting at least one of monochlorodisilane and monobromodisilane with a primary amine.