Compositions and methods using same for carbon doped silicon containing films

• US 10,145,008 B2
• Filed: 02/04/2016
• Issued: 12/04/2018
• Est. Priority Date: 02/06/2015
• Status: Active Grant

• Current Assignee: Versum Materials US, LLC (Merck & Co., Inc.)
• Original Assignee: Versum Materials US, LLC (Merck & Co., Inc.)
• Inventors: Chandra, Haripin, Cuthill, Kirk Scott, Mallikarjunan, Anupama, Lei, Xinjian, MacDonald, Matthew R., Xiao, Manchao, Rao, Madhukar Bhaskara, Li, Jianheng
• Primary Examiner(s): CLARK, JASMINE JHIHAN B
• Application Number:
  US15/548,884
• Publication Number:
  US 20180023192A1
• Time in Patent Office: 1,034 Days
• CPC Class Codes: C23C 14/0605 Carbon
• CPC Class Codes: C23C 16/345 Silicon nitride
• CPC Class Codes: C23C 16/36 Carbonitrides
• CPC Class Codes: C23C 16/401 containing silicon
• CPC Class Codes: C23C 16/402 Silicon dioxide
• CPC Class Codes: C23C 16/45536 Use of plasma, radiation or electromagnetic fields
• CPC Class Codes: C23C 16/56 After-treatment
• CPC Class Codes: H01L 21/02126 the material containing Si, O, and at least one of H, N, C, F, or other non-metal elements, e.g. SiOC, SiOC:H or SiONC
• CPC Class Codes: H01L 21/02211 the compound being a silane, e.g. disilane, methylsilane or chlorosilane
• CPC Class Codes: H01L 21/02219 the compound comprising silicon and nitrogen
• CPC Class Codes: H01L 21/02274 in the presence of a plasma [PECVD]
• CPC Class Codes: H01L 21/0228 deposition by cyclic CVD, e.g. ALD, ALE, pulsed CVD
• CPC Class Codes: H01L 21/02326 into a nitride layer, e.g. changing SiN to SiON
• CPC Class Codes: H01L 21/02337 treatment by exposure to a gas or vapour
• CPC Class Codes: H01L 21/0234 treatment by exposure to a plasma
• CPC Class Codes: H01L 21/02348 treatment by exposure to UV light
• CPC Class Codes: H01L 21/02351 treatment by exposure to corpuscular radiation, e.g. exposure to electrons, alpha-particles, protons or ions
• CPC Class Codes: H01L 21/02354 using a coherent radiation, e.g. a laser

Abstract

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.

Claims

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;

17. The method of claim 16 wherein the precursor comprises Formulae I and X¹, X², X³ and X⁴ 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.