Use of silyl bridged alkyl compounds for dense OSG films

• US 10,249,489 B2
• Filed: 10/20/2017
• Issued: 04/02/2019
• Est. Priority Date: 11/02/2016
• Status: Active Grant

• Current Assignee: Versum Materials US Inc.
• Original Assignee: Versum Materials US Inc.
• Inventors: Vrtis, Raymond Nicholas, Ridgeway, Robert Gordon, Achtyl, Jennifer Lynn Anne, Entley, William Robert, Sinatore, Dino, Theodorou, Kathleen Esther, Adamczyk, Andrew J.
• Primary Examiner(s): Smoot, Stephen W
• Application Number:
  US15/789,790
• Publication Number:
  US 20180122632A1
• Time in Patent Office: 529 Days
• CPC Class Codes: C23C 16/401 containing silicon
• CPC Class Codes: C23C 16/46 characterised by the method used for heating the substrate C23C16/48, C23C16/50 take precedence
• CPC Class Codes: C23C 16/48 by irradiation, e.g. photolysis, radiolysis, particle radiation
• CPC Class Codes: C23C 16/50 using electric discharges generation and control of plasma in discharge tubes for surface treatment H01J37/32, H01J37/34
• CPC Class Codes: C23C 16/505 using radio frequency discharges
• 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 21/02137 the material comprising alkyl silsesquioxane, e.g. MSQ
• CPC Class Codes: H01L 21/02203 the layer being porous
• CPC Class Codes: H01L 21/02216 the compound being a molecule comprising at least one silicon-oxygen bond and the compound having hydrogen or an organic group attached to the silicon or oxygen, e.g. a siloxane
• CPC Class Codes: H01L 21/02271 deposition by decomposition or reaction of gaseous or vapour phase compounds, i.e. chemical vapour deposition H01L21/02266 takes precedence
• CPC Class Codes: H01L 21/02274 in the presence of a plasma [PECVD]
• CPC Class Codes: H01L 21/02348 treatment by exposure to UV light
• CPC Class Codes: H01L 21/0262 Reduction or decomposition of gaseous compounds, e.g. CVD

Abstract

Low dielectric organosilicon films are deposited by a process comprising the steps of: providing a substrate within a vacuum chamber; introducing into the vacuum chamber a gaseous silicon containing precursor composition comprising at least one organosilicon precursor selected from the group consisting of Formula (I) and Formula (II):

• • wherein, R₁, R₂, R₃, R₄, R₅, and R₆ are as defined herein, and applying energy to the gaseous structure forming composition in the vacuum chamber to induce reaction of the at least one organosilicon precursor to deposit a film on at least a portion of the substrate.

Claims

1. A chemical vapor deposition method for depositing an organosilicate film on at least a part of a substrate, the process comprising the steps of:

providing a substrate within a vacuum chamber;

introducing into the vacuum chamber a gaseous structure forming composition comprising at least one organosilicon precursor selected from the group consisting of Formula (I) and Formula (II);

2. The chemical vapor deposition method of claim 1 wherein the film has a dielectric constant between 2.8 and 3.5.

3. The method of claim 2 wherein the film has a Young'"'"'s modulus greater than 20 GPa and/or a nanoindentation hardness greater than 3.5 GPa.

4. The chemical vapor deposition method of claim 1 wherein the energy is plasma energy.

5. The chemical vapor deposition method of claim 1 further comprising the step of subjecting the film to a post treatment comprising UV radiation.

6. The chemical vapor deposition method of claim 5 wherein the film has a dielectric constant between 2.8 and 3.5.

7. The chemical vapor deposition method of claim 5 where the UV treatment is carried out at elevated temperatures preferably 200-500°

C.

8. The chemical vapor deposition method of claim 5 where the UV treatment is carried out in a reactive environment comprising at least one selected from the group consisting of O₂, H₂, and NH₃.

9. The method of claim 5 wherein the film has a Young'"'"'s modulus greater than 20 GPa and/or a nanoindentation hardness greater than 3.5 GPa.

10. The chemical vapor deposition method of claim 1 further comprising the step of subjecting the film to a post treatment comprising heat.

11. The chemical vapor deposition method of claim 1 wherein the at least one organosilicon precursor is a precursor of Formula (I).

12. The chemical vapor deposition method of claim 11 wherein the at least one organosilicon precursor is at least one precursor selected from the group consisting of 1,1,1,3,3-pentamethoxy-2-methyl-1,3-disilabutane (PMOM-DSB), 1,2-bis(methyldimethoxysilyl)ethane,1,2-bis(trimethoxysilyl)ethane, 1,2-bis(dimethoxysilyl)ethane, 1,1-bis(trimethoxysilyl)ethane, 1,1-bis(methyldimethoxysilyl)ethane, 1,1-bis(dimethoxysilyl)ethane, 1,1-dimethyl-1,1-bis(trimethoxysilyl)methane, 1,1-dimethyl-1,1-bis(methyldimethoxysilyl)methane, 1,1-dimethyl-1,1-bis(dimethoxysilyl)methane, 1,1,1,3,3-pentaethoxy-2-methyl-1,3-disilabutane, 1,2-bis(methyldiethoxysilyl)ethane, 1,2-bis(triethoxysilyl)ethane, 1,2-bis(diethoxysilyl)ethane, 1,1-bis(triethoxysilyl)ethane, 1,1-bis(methyldiethoxysilyl)ethane, 1,1-bis(diethoxysilyl)ethane, 1,1-dimethyl-1,1-bis(triethoxysilyl)methane, 1,1-dimethyl-1,1-bis(methyldiethoxysilyl)methane, and 1,1-dimethyl-1,1-bis(diethoxysilyl)methane.

13. The chemical vapor deposition method of claim 1 wherein the at least one organosilicon precursor is a precursor of Formula (II).

14. The chemical vapor deposition method of claim 13 wherein the at least one organosilicon precursor is at least one precursor selected from the group consisting of 1,1,3,3-tetramethoxy-1,3-disilacyclobutane, 1,3-dimethoxy-1,3-dimethyl-1,3-disilacyclobutane, 1,3-diemthoxy-1,3-disilacyclobutane, 1,3,3-trimethoxy-1-methyl-1,3-disilacyclobutane, 1,3-dimethoxy-1-methyl-disilacyclobutane, 1,1-dimethoxy-1,3-disilacyclobutane, 1,1,4,4-tetramethoxy-1,4-disilacyclohexane, 1,4-dimethoxy-1,4-dimethyl-1,4-disilacyclohexane, 1,4-diemthoxy-1,4-disilacyclohexane, 1,4,4-trimethoxy-1-methyl-1,4-disilacyclohexane, 1,4-dimethoxy-1-methyl-disilacyclohexane, 1,1-dimethoxy-1,4-disilacyclohexane,1,1,3,3-tetraethoxy-1,3-disilacyclobutane, 1,3-diethoxy-1,3-dimethyl-1,3-disilacyclobutane, 1,3-diemthoxy-1,3-disilacyclobutane, 1,3,3-triethoxy-1-methyl-1,3-disilacyclobutane, 1,3-diethoxy-1-methyl-disilacyclobutane, 1,1-diethoxy-1,3-disilacyclobutane,1,1,4,4-tetraethoxy-1,4-disilacyclohexane,1,4-diethoxy-1,4-dimethyl-1,4-disilacyclohexane, 1,4-diemthoxy-1,4-disilacyclohexane, 1,4,4-triethoxy-1-methyl-1,4-disilacyclohexane,1,4-diethoxy-1-methyl-disilacyclohexane, and 1,1-diethoxy-1,4-disilacyclohexane.

15. The chemical vapor deposition method of claim 1 wherein the at least one organosilicon precursor is free of halide ions, Al³⁺ ions, Fe²⁺ ions, Fe³⁺ ions, Ni²⁺ ions, and Cr³⁺ ions.

16. The chemical vapor deposition method of claim 15 wherein the halide ions include chlorides, fluorides, bromides, and iodides.

17. The chemical vapor deposition method of claim 1 wherein the method is a plasma enhanced chemical vapor deposition method.

18. The chemical vapor deposition method of claim 1 wherein the method is a thermal chemical vapor deposition method.

19. The chemical vapor deposition method of claim 1 wherein the substrate is a silicon wafer.

20. The chemical vapor deposition method of claim 1 wherein the film has one or more bond types selected from the group consisting of Si—

O—

C, Si—

O—

Si, Si—

C, Si—

F, Si—

H, C—

O, C—

H, and C—

F.

21. The chemical vapor deposition method of claim 1 wherein the one or more reactive substances are selected from the group consisting of a gaseous or liquid organic substance, ammonia, hydrogen, carbon dioxide, carbon monoxide, a fluorocarbon, and mixtures thereof.

22. A film formed by the method of claim 1.

23. The film of claim 22 wherein said film has a density of 1.8 g/cc or greater.

24. The film of claim 23 wherein said film has a density of 2.0 or greater.

25. The film of claim 24 wherein said film has a dielectric constant of 2.5 to 3.5 and a Young'"'"'s modulus greater than 20 GPa and/or a nanoindentation hardness greater than 3.5 GPa.