Compositions and methods using same for carbon doped silicon containing films
Described herein are compositions and methods using same for forming a silicon-containing film such as, without limitation, a carbon doped silicon oxide film, a carbon doped silicon nitride, a carbon doped silicon oxynitride film in a deposition process. In one aspect, the composition comprises at least cyclic carbosilane having at least one Si—C—Si linkage and at least one anchoring group selected from a halide atom, an amino group, and combinations thereof.
1. A composition comprising at least one precursor selected from the group consisting of:
a cyclic halocarbosilane selected from the group consisting of 1-chloro-1,3-disilacyclobutane, 1-bromo-1,3-disilacyclobutane, 1-iodo-1,3-disilacyclobutane, 1,3-dichloro-1,3-disilacyclobutane, 1,3-dibromo-1,3-disilacyclobutane, 1,3-diiodo-1,3-disilacyclobutane, 1,1-dichloro-1,3-disilacyclobutane, 1,1-dibromo-1,3-disilacyclobutane, 1,1-diiodo-1,3-disilacyclobutane, 1,1,3,3-tetrabromo-1,3-disilacyclobutane, 1,1,3,3-tetraiodo-1,3-disilacyclobutane, 1,3-dichloro-1,3-dimethyl-1,3-disilacyclobutane, 1,1,3,3,5,5-hexachloro-1,3,5-trisilacyclohexane, 1,1,3,3-tetrachloro-1,3,5-trisilacyclohexane, and 1,3,5-trichloro-1,3,5-trisilacyclohexane;
a cyclic haloaminocarbosilane selected from the group consisting of 1,3-bis(dimethylamino)-1,3-dichloro-1,3-disilacyclobutane, 1,3-bis(diethylamino)-1,3-dichloro-1,3-disilacyclobutane, and 1-(dimethylamino)-1,3,3-trichloro-1,3-disilacyclobutane; and
a cyclic aminocarbosilane selected from the group consisting of 1,1,3,3-tetrakis(methylamino)-1,3-disilacyclobutane, 1,1,3,3-tetrakis(dimethylamino)-1,3-disilacyclobutane, 1,3-bis(dimethylamino)-1,3-dimethyl-1,3-disilacyclobutane, 1,3-bis(methylamino)-1,3-dimethyl-1,3-disilacyclobutane, and 1,3-bis(iso-propylamino)-1,3-dimethyl-1,3-disilacyclobutane.
2. A method for depositing a carbon doped silicon containing film selected from a carbon doped silicon oxide film and a carbon doped silicon oxynitride film, the method comprising:
placing a substrate into a reactor;
heating the reactor to one or more temperatures ranging from about 100° C. to about 700° C.;
introducing at least one cyclic carbosilane precursor selected from the group consisting of a cyclic halocarbosilane, a cyclic haloaminocarbosilane, a cyclic aminocarbosilane and combinations thereof;
introducing a nitrogen source under conditions sufficient to react with the at least one cyclic carbosilane precursor and form a carbon doped silicon nitride film; and
optionally exposing the silicon carbonitride film to an oxygen source to convert the silicon carbonitride film to the film at one or more temperatures ranging from about 100° C. to 1000° C.
3. The method of claim 2 further comprising treating the silicon containing film with at least one selected from the group consisting of annealing, a plasma, ultraviolet light exposure, laser exposure, electron beam exposure, and combinations thereof.
4. The method of claim 2 wherein the cyclic carbosilane comprises the cyclic halocarbosilane selected from the group consisting of 1-chloro-1,3-disilacyclobutane, 1-bromo-1,3-disilacyclobutane, 1-iodo-1,3-disilacyclobutane, 1,3-dichloro-1,3-disilacyclobutane, 1,3-dibromo-1,3-disilacyclobutane, 1,3-diiodo-1,3-disilacyclobutane, 1,1-dichloro-1,3-disilacyclobutane, 1,1-dibromo-1,3-disilacyclobutane, 1, 1-diiodo-1,3-disilacyclobutane, 1,1,3,3-tetrachloro-1,3-disilacyclobutane, 1,1,3,3-tetrabromo-1,3-disilacyclobutane, 1,1,3,3-tetraiodo-1,3-disilacyclobutane, 1,3-dichloro-1,3-dimethyl-1,3-disilacyclobutane, 1,1,3,3,5,5-hexachloro-1,3,5-trisilacyclohexane, 1,1,3,3-tetrachloro-1,3,5-trisilacyclohexane, and 1,3,5-trichloro-1,3,5-trisilacyclohexane.
5. The method of claim 2 wherein the cyclic carbosilane comprises the cyclic haloaminocarbosilane selected from the group consisting of 1,3-bis(dimethylamino)-1,3-dichloro-1,3-disilacyclobutane, 1,3-bis(diethylamino)-1,3-dichloro-1,3-disilacyclobutane, and 1-(dimethylamino)-1,3,3-trichloro-1,3-disilacyclobutane.
6. The method of claim 2 wherein the cyclic carbosilane comprises the cyclic aminocarbosilane selected from the group consisting of 1,1,3,3-tetrakis(methylamino)-1,3-disilacyclobutane, 1,1,3,3-tetrakis(dimethylamino)-1,3-disilacyclobutane, 1,3-bis(dimethylamino)-1,3-dimethyl-1,3-disilacyclobutane, 1,3-bis(methylamino)-1,3-dimethyl-1,3-disilacyclobutane, and 1,3-bis(iso-propylamino)-1,3-dimethyl-1,3-disilacyclobutane.
7. The method of claim 2 wherein the film comprises a carbon content of about 10 atomic weight % or greater as measured by XPS.
8. The method of claim 2 wherein the film comprises a wet etch of about 0.15 Å/s or less as measured by dilute hydrofluoric acid.
9. A method for depositing a silicon containing film selected from a silicon carbide film and a carbon doped silicon nitride film, the method comprising:
placing a semi-conductor substrate into a reactor;
heating the reactor to one or more temperatures ranging from about 100° C. to about 700° C. and optionally maintaining the reactor at a pressure of 100 torr or less;
introducing at least one cyclic carbosilane selected from the group consisting of a cyclic halocarbosilane, a cyclic haloaminocarbosilane, and combinations thereof;
introducing into the reactor a nitrogen-containing plasma source under conditions sufficient to react with the carbosilane precursor and form the film.
10. The method of claim 9 wherein the nitrogen-containing plasma source is selected from the group consisting of nitrogen plasma, a plasma comprising nitrogen and helium, a plasma comprising nitrogen and argon, ammonia plasma, a plasma comprising ammonia and helium, a plasma comprising ammonia and argon, helium plasma, argon plasma, neon plasma, hydrogen plasma, a plasma comprising hydrogen and helium, a plasma comprising hydrogen and argon, an organic amine plasma, organic diamine plasma, and combinations thereof.
11. The method of claim 9 further comprising treating the silicon containing film with at least one selected from the group consisting of annealing, a plasma treatment, ultraviolet light exposure, laser exposure, electron beam exposure, and combinations thereof.
12. The method of claim 9 further comprising exposing the film to an oxygen source into the reactor to convert the silicon containing film into a silicon oxide or carbon doped silicon oxide films.
13. The method of claim 12 wherein the oxygen source is selected from the group consisting of water vapor, water plasma, oxygenated water, oxygenated water steam, oxygen, oxygen plasma, a plasma comprising oxygen and helium, a plasma comprising oxygen and argon plasma, a plasma comprising a nitrogen oxide, a plasma comprising carbon dioxide, hydrogen peroxide, organic peroxides, and combinations thereof.
14. The method of claim 12 wherein the cyclic carbosilane comprises the cyclic halocarbosilane selected from the group consisting of 1-chloro-1,3-disilacyclobutane, 1-bromo-1,3-disilacyclobutane, 1-iodo-1,3-disilacyclobutane, 1,3-dichloro-1,3-disilacyclobutane, 1,3-dibromo-1,3-disilacyclobutane, 1,3-diiodo-1,3-disilacyclobutane, 1,1-dichloro-1,3-disilacyclobutane, 1,1-dibromo-1,3-disilacyclobutane, 1, 1-diiodo-1,3-disilacyclobutane, 1,1,3,3-tetrachloro-1,3-disilacyclobutane, 1,1,3,3-tetrabromo-1,3-disilacyclobutane, 1,1,3,3-tetraiodo-1,3-disilacyclobutane, 1,3-dichloro-1,3-dimethyl-1,3-disilacyclobutane, 1,1,3,3,5,5-hexachloro-1,3,5-trisilacyclohexane, 1,1,3,3-tetrachloro-1,3,5-trisilacyclohexane, and 1,3,5-trichloro-1,3,5-trisilacyclohexane.
15. The method of claim 12 wherein the cyclic carbosilane comprises the cyclic haloaminocarbosilane selected from the group consisting of 1,3-bis(dimethylamino)-1,3-dichloro-1,3-disilacyclobutane, 1,3-bis(diethylamino)-1,3-dichloro-1,3-disilacyclobutane, and 1-(dimethylamino)-1,3,3-trichloro-1,3-disilacyclobutane.
16. A method for depositing a carbon doped silicon oxide film, the method comprising:
placing a substrate into a reactor;
introducing at least one cyclic carbosilane precursor having the following Formulae I and II:
wherein X 1 , X 5 , and X 6 are each independently chosen from a hydrogen atom; a halide atom selected from F, Cl, Br, and I; an amino group having the formula NR 1 R 2 wherein R 1 and R 2 are independently selected from the group consisting of a hydrogen atom, a C 1 to C 10 linear alkyl group; a C 3 to C 10 branched alkyl group; a C 3 to C 10 cyclic alkyl group; a C 3 to C 10 alkenyl group; a C 4 to C 10 aryl group; and a C 4 to C 10 heterocyclic group;
introducing a nitrogen source under conditions sufficient to react with the at least one cyclic carbosilane precursor and form a carbon doped silicon nitride film; and,
exposing the carbon doped silicon nitride film to an oxygen source under conditions sufficient to convert the carbon doped silicon nitride film to the carbon doped silicon oxide film.
17. The method of claim 16 wherein the precursor comprises Formulae I and X 1 , X 2 , X 3 and X 4 are Cl.
18. The method of claim 16 wherein the exposing comprises thermal annealing the carbon doped silicon nitride film in the presence of the oxygen source.
19. The method of claim 18 wherein the oxygen source comprises at least one of air and water.
20. The method of claim 16 further comprising treating the silicon doped silicon oxide film with a hydrogen containing plasma.