Method for the formation of silica film, silica film, insulating film, and semiconductor device

• US 20030008155A1
• Filed: 06/10/2002
• Published: 01/09/2003
• Est. Priority Date: 06/11/2001
• Status: Active Grant

• Current Assignee: JSR Corporation
• Original Assignee: JSR Corporation
• Inventors: Yamada, Kinji, Shiota, Atsushi, Hayashi, Eiji, Nishikawa, Michinori
• Granted Patent: US 6,787,193 B2
• Time in Patent Office: Days
• US Class Current: 428/447
• CPC Class Codes: C09D 183/04 Polysiloxanes
• 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 21/02216 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 21/02282 liquid deposition, e.g. spin-coating, sol-gel techniques, spray coating
• CPC Class Codes: H01L 21/02343 treatment by exposure to a liquid
• CPC Class Codes: H01L 21/31133 by chemical means
• CPC Class Codes: H01L 21/31138 by dry-etching
• CPC Class Codes: H01L 21/3122 layers comprising polysiloxane compounds
• CPC Class Codes: H01L 21/31695 Deposition of porous oxides or porous glassy oxides or oxide based porous glass
• CPC Class Codes: Y02P 20/54 using solvents, e.g. supercritical solvents or ionic liquids
• CPC Class Codes: Y10T 428/31663 As siloxane, silicone or silane

Abstract

A method for the formation of a silica film which comprises treating a film in a supercritical medium, the film comprising (A) a siloxane compound and (B) at least one member selected from the group consisting of (B-1) a compound compatible with or dispersible in ingredient (A) and having a boiling or decomposition temperature of from 150 to 500° C. and (B-2) a surfactant. The silica film has excellent mechanical strength showing a dielectric constant of generally 2.2 or lower, and hence is useful as a dielectric film in semiconductor devices and the like.

Claims

1. A method for the formation of a silica film which comprises treating a film in a supercritical medium, the film comprising (A) a siloxane compound and (B) at least one member selected from the group consisting of (B-1) a compound compatible with or dispersible in ingredient (A) and having a boiling or decomposition temperature of from 150 to 500°

C. and (B-2) a surfactant.

2. The method as claimed in claim 1, wherein the siloxane compound (A) is at least either of a hydrolyzate and condensate of at least one compound selected from the group consisting of compounds represented by the following formula (1):

R¹_aSi(OR²)_4-a 

 

(1)

wherein R¹ represents a hydrogen atom, a fluorine atom or a monovalent organic group;

R² represents a monovalent organic group; and

a is an integer of 0 to 3, and compounds represented by the following formula (2);

R³_b(R⁴O)_3-bSi—

(R⁷)_d—

Si(OR⁵)_3-cR⁶_c 

 

(2)

wherein R³, R⁴, R⁵ and R⁶ may be the same or different and each represent a monovalent organic group;

b and c may be the same or different and each are a number of 0 to 2;

R⁷ represents an oxygen atom or a group represented by —

(CH₂)_n—

, wherein n is 1 to 6; and

d is 0 or 1.

3. The method as claimed in claim 1, wherein the ingredient (B-1) comprises at least one member selected from the group consisting of compounds having an alkylene oxide structure, (meth)acrylic polymers, polyesters, polycarbonates and polyanhydrides.

4. The method as claimed in claim 1, wherein the ingredient (B-1) is contained in an amount of from 20 to 300 parts by weight per 100 parts by weight of the ingredient (A) (in terms of the product of complete hydrolysis and condensation).

5. The method as claimed in claim 1, wherein the ingredient (B-2) comprises at least one member selected from the group consisting of nonionic surfactants and cationic surfactants.

6. The method as claimed in claim 1, wherein the ingredient (B-2) is contained in an amount of from 5 to 300 parts by weight per 100 parts by weight of ingredient (A) (in terms of the product of complete hydrolysis and condensation).

7. The method as claimed in claim 1, wherein the supercritical medium comprises carbon dioxide.

8. The method as claimed in claim 1, wherein the treatment in the supercritical medium is conducted under the conditions of a temperature of from 0 to 200°

C. and a pressure of from 10 to 200 atm.

9. A silica film obtained by the method as claimed in claim 1.

10. A method for the formation of a silica film which comprises subjecting the film obtained by the method as claimed in claim 1 to heat treatment at 200 to 500°

C.

11. A silica film obtained by the method as claimed in claim 10.

12. A low-dielectric film comprising the silica film as claimed in claim 9 or 11.

13. A semiconductor device having the low-dielectric film as claimed in claim 12.