Silicon-containing film-forming composition, silicon-containing film, silicon-containing film-bearing substrate, and patterning method

• US 8,329,376 B2
• Filed: 04/10/2007
• Issued: 12/11/2012
• Est. Priority Date: 04/11/2006
• Status: Active Grant

• Current Assignee: Shin-Etsu Chemical Company Limited
• Original Assignee: Shin-Etsu Chemical Company Limited
• Inventors: Ogihara, Tsutomu, Ueda, Takafumi, Iwabuchi, Motoaki
• Primary Examiner(s): Huff, Mark F
• Assistant Examiner(s): Johnson, Connie P
• Application Number:
  US11/783,542
• Publication Number:
  US 20070238300A1
• Time in Patent Office: 2,072 Days
• Field of Search: 430/270.1, 528/14, 528/15, 528/16, 528/17, 528/18, 528/19, 528/20, 528/21, 528/22, 528/23, 528/10, 528/11, 528/12, 528/13, 528/24, 528/25, 528/26, 528/27, 528/28, 528/29, 528/30
• US Class Current: 430/270.1
• CPC Class Codes: C08G 77/08 characterised by the catalysts used
• CPC Class Codes: C08L 83/04 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 21/3122 layers comprising polysiloxane compounds

Abstract

A silicon-containing film is formed from a heat curable composition comprising (A) a silicon-containing compound obtained by effecting hydrolytic condensation of a hydrolyzable silicon compound in the presence of an acid catalyst, and substantially removing the acid catalyst from the reaction mixture, (B) a hydroxide or organic acid salt of lithium, sodium, potassium, rubidium or cesium, or a sulfonium, iodonium or ammonium compound, (C) an organic acid, and (D) an organic solvent. The silicon-containing film allows an overlying photoresist film to be patterned effectively. The composition is effective in minimizing the occurrence of pattern defects after lithography and is shelf stable.

Claims

1. A heat curable silicon-containing film-forming composition comprising

(A) a silicon-containing compound comprising a compound obtained by effecting hydrolytic condensation of a hydrolyzable silicon compound having the following general formula (3):

R¹_m1Si(OR)_(4-m1) 

 

(3)

wherein R is an alkyl group of 1 to 3 carbon atoms, R¹ is selected from the group consisting of methyl group, ethyl group, phenyl group and groups having the following formulae;

2. The silicon-containing film-forming composition of claim 1, wherein the counter ion is selected from the group consisting of hydroxyl, formate, acetate, propionate, malonate, maleate, fumarate, and citrate ions.

3. The silicon-containing film-forming composition of claim 1, further comprising a water-soluble organic solvent selected from the group consisting of methanol, ethanol, 1-propanol, 2-propanol, 1-butanol, 2-butanol, isobutyl alcohol, tert-butyl alcohol, 1,2-ethane diol, 1,2-propane diol, 1,3-propane diol, 1,4-butane diol, 2,3-butane diol, 1,5-pentane diol, glycerin, furfuryl alcohol, tetrahydrofurfuryl alcohol, diacetone alcohol, trifluoroethanol, methyl lactate, ethyl lactate, and acetonitrile.

4. The silicon-containing film-forming composition of claim 1, further comprising water.

5. The silicon-containing film-forming composition of claim 1, further comprising a photoacid generator.

6. A substrate having formed thereon, in sequence, an organic film, a silicon-containing film of the composition of claim 1, and a photoresist film.

7. A substrate having formed thereon, in sequence, an organic film, a silicon-containing film of the composition of claim 1, an antireflective coating, and a photoresist film.

8. The substrate of claim 7, wherein said organic film is a film having an aromatic framework.

9. A method for forming a pattern in a substrate, comprising the steps of:

providing the substrate of claim 7,

exposing a pattern circuit region of the photoresist film to radiation,

developing the photoresist film with a developer to form a resist pattern,

dry etching the silicon-containing film with the resist pattern made an etching mask,

etching the organic film with the patterned silicon-containing film made an etching mask, and

etching the substrate with the patterned organic film made an etching mask, for forming a pattern in the substrate.

10. A method for forming a pattern in a substrate, comprising the steps of:

providing the substrate of claim 8,

exposing a pattern circuit region of the photoresist film to radiation,

developing the photoresist film with a developer to form a resist pattern,

dry etching the antireflective coating and the silicon-containing film with the resist pattern made an etching mask,

etching the organic film with the patterned silicon-containing film made an etching mask, and

etching the substrate with the patterned organic film made an etching mask, for forming a pattern in the substrate.

11. The patterning method of claim 9, wherein said organic film is a film having an aromatic framework.

12. The patterning method of claim 9, wherein the exposing step is carried out by photolithography using radiation having a wavelength equal to or less than 300 nm.

13. A heat curable silicon-containing film-forming composition comprising

(A) a silicon-containing compound obtained by effecting hydrolytic condensation of a hydrolyzable silicon compound in the presence of an acid catalyst which is selected from mineral acids and sulfonic acid derivatives to form a reaction mixture containing the silicon-containing compound, and substantially removing the acid catalyst from the reaction mixture,

(B) a compound having the general formula (Q-1):

14. A method of forming a silicon-containing film comprising baking a coating of a heat curable silicon-containing film-forming composition at a temperature of 50 to 400°

C.,

said composition comprising

(A) a silicon-containing compound obtained by effecting hydrolytic condensation of a hydrolyzable silicon compound in the presence of an acid catalyst which is selected from mineral acids and sulfonic acid derivatives to form a reaction mixture containing the silicon-containing compound, and substantially removing the acid catalyst from the reaction mixture,

(B) a compound having the general formula (Q-1);