Method for Removal of Carbon From An Organosilicate Material

• US 20100151206A1
• Filed: 10/08/2009
• Published: 06/17/2010
• Est. Priority Date: 12/11/2008
• Status: Abandoned Application

• Current Assignee: Versum Materials US, LLC (Merck & Co., Inc.)
• Original Assignee: Air Products and Chemicals Incorporated (Linde Plc)
• Inventors: Braymer, Thomas Albert, Wu, Aiping, Weigel, Scott Jeffrey
• Application Number:
  US12/575,772
• Publication Number:
  US 20100151206A1
• Time in Patent Office: Days
• US Class Current: 428/158
• CPC Class Codes: B32B 5/18 characterised by features of a layer of foamed material
• CPC Class Codes: C23C 16/401 containing silicon
• 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 21/02203 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 21/02274 in the presence of a plasma [PECVD]
• CPC Class Codes: H01L 21/02282 liquid deposition, e.g. spin-coating, sol-gel techniques, spray coating
• CPC Class Codes: H01L 21/02334 in-situ cleaning after layer formation, e.g. removing process residues
• CPC Class Codes: H01L 21/02337 treatment by exposure to a gas or vapour
• CPC Class Codes: H01L 21/02345 treatment by exposure to radiation, e.g. visible light
• CPC Class Codes: H01L 21/3105 After-treatment
• CPC Class Codes: H01L 21/31604 Deposition from a gas or vapour H01L21/31691, H01L21/31695 take precedence
• CPC Class Codes: H01L 21/31695 Deposition of porous oxides or porous glassy oxides or oxide based porous glass
• CPC Class Codes: Y10T 428/24479 including variation in thickness
• CPC Class Codes: Y10T 428/24496 Foamed or cellular component

Abstract

Described herein is a method for removing at least a portion of the carbon-containing species within an organosilicate (OSG) film by treating the OSG film with a chemical, such as but not limited to an oxidizer, exposing the OSG film to an energy source comprising ultraviolet light, or treating the OSG film with a chemical and exposing the OSG film to an energy source.

Claims

1. A method for forming a porous organosilicate film comprising:

providing a composite organosilicate film wherein the composite organosilicate film is deposited from a composition comprising at least one silicon-containing precursor and at least one porogen-containing precursor and wherein the composite organosilicate film comprises carbon-containing species;

exposing the composite organosilicate film to an energy source comprising ultraviolet light; and

treating the composite organosilicate film to a chemical comprising at least one selected from an oxidizer, a fluorinating agent, a methylating agent, a reducing agent, and combinations thereof to remove at least a portion of the carbon-containing species contained therein and provide a porous organosilicate film.

2. The method of claim 1 further comprising exposing the porous organosilicate film to the energy source.

3. The method of claim 1 wherein the energy source further comprises at least one chosen from a thermal source, α

-particles, 6-particles, γ

-rays, x-rays, high energy electron, electron beam, visible light, infrared light, microwave, radio-frequency wavelengths, and combinations thereof.

4. The method of claim 1 wherein the chemical comprises an oxidizer.

5. The method of claim 4 wherein the oxidizer comprises at least one chosen from oxygen, ozone, ozonated water, SPM, oxygen atoms, radicals of O₂ or O₃, charged species of O₂ or O₃, and combinations thereof.

6. The method of claim 4 wherein the oxidizer comprises ozone.

7. The method of claim 4 wherein the oxidizer comprises ozonated water.

8. The method of claim 4 wherein the oxidizer comprises SPM.

9. The method of claim 1 wherein the chemical comprises a reducing agent.

10. The method of claim 9 wherein the reducing agent is at least one selected from hydrazine, a salt of hydrazine, a hydride, a carboxylic acid, a hydrocarbon, hydrogen, a stannous compound, a ferrous compound, carbon monoxide, and combinations thereof.

11. The method of claim 1 wherein the at least one silicon-containing precursor is chosen from diethoxymethylsilane, tetraethoxysilane, dimethyldiethoxysilane, dimethyldimethoxysilane, dimethylethoxysilane, triethoxysilane, trimethylphenoxysilane, phenoxysilane, hexamethyldisiloxane, 1,1,2,2-tetramethyldisiloxane, octamethyltrisiloxane, methyltriethoxysilane, methyltriacetoxysilane, tetraacetoxysilane, dimethylsilacyclobutane, octamethylcyclotetrasiloxane, 1,3,5,7-tetramethylcyclotetrasiloxane, methylsilane, dimethylsilane, trimethylsilane, tetramethylsilane, methylene bridged alkoxy silanes, and combinations thereof.

12. The method of claim 1 wherein the at least one porogen precursor is chosen from alpha-terpinene, limonene, cyclohexane, cyclooctane, bicyclohexadiene, gamma-terpinene, camphene, dimethylhexadiene, ethylbenzene, norbonadiene, cyclopentene oxide, 1,2,4-trimethylcyclohexane, 1,5-dimethyl-1,5-cyclooctadiene, camphene, adamantane, 1,3-butadiene, substituted dienes, decahydronaphthelene, toluene, and combinations thereof.

13. The method of claim 1 wherein the at least one porogen precursor comprises a gaseous hydrocarbon having from 1 to 13 carbon atoms.

14. The method of claim 1 wherein the treating step is conducted during at least a portion of the exposing step.

15. The method of claim 1 wherein the exposing step is conducted prior to the treating step.

16. The method of claim 1 wherein the treating step is conducted prior to the exposing step.

17. A method for forming a porous organosilicate film comprising:

forming via vapor deposition a composite organosilicate film from a composition comprising at least one silicon-containing precursor and at least one porogen-containing precursor wherein the composite organosilicate film comprises carbon-containing species;

treating the composite organosilicate film to a chemical to remove at least a portion of the carbon-containing species contained therein; and

exposing the composite organosilicate film to an energy source comprising ultraviolet light and optionally thermal energy to remove at least a portion of the carbon-containing species contained therein and provide the porous organosilicate film.

18. The method of claim 17 wherein the chemical in the treating step comprises an oxidizer.

19. The method of claim 18 wherein the oxidizer comprises at least one chosen from oxygen, ozone, ozonated water, SPM, oxygen atoms, radicals of O₂ or O₃, charged species of O₂ or O₃, and combinations thereof.

20. The method of claim 17 wherein the treating step is conducted during at least a portion of the exposing step.

21. The method of claim 17 wherein the exposing step is conducted prior to the treating step.

22. The method of claim 17 wherein the treating step is conducted prior to the exposing step.

23. A method for forming a porous organosilicate film comprising:

providing a composite organosilicate film wherein the composite organosilicate film comprises carbon-containing species, a first dielectric constant, and a first hardness;

treating the composite organosilicate film to a chemical comprising an oxidizer to remove at least a portion of the carbon-containing species therein; and

exposing the composite organosilicate film to an energy source comprising ultraviolet light to remove at least a portion of the carbon-containing species therein and provide the porous organosilicate film comprising a second dielectric constant and a second hardness wherein the second dielectric constant is substantially the same as or less than the first dielectric constant and wherein the second hardness is greater than the first hardness.

24. The method of claim 23 wherein the first dielectric constant, the second dielectric constant, or both the first and second dielectric constant is 2.7 or less.

25. A porous organosilicate film comprising:

a dielectric constant ranging from 1.2 to 2.5 and an extinction coefficient of the film measured at 240 nm by ellipsometer ranging from 0 to 0.03

26. The porous organosilicate film of claim 25 comprising pores wherein the average size of the pores is about 100 nanometers or less.

27. The porous organosilicate film of claim 25 wherein the extinction coefficient of the film measured at 240 nm ranges from 0 to 0.025.