Photo-curable nanoimprint composition, method for formatting pattern using the composition, and nanoimprint replica mold comprising cured product of the composition

• US 9,228,035 B2
• Filed: 10/19/2011
• Issued: 01/05/2016
• Est. Priority Date: 10/20/2010
• Status: Active Grant

• Current Assignee: SCIVAX Corporation
• Original Assignee: Tokuyama Corporation
• Inventors: Umekawa, Hideki, Kawabata, Yuichiro, Sasaki, Yuko
• Primary Examiner(s): Choi, Ling
• Assistant Examiner(s): Whiteley, Jessica E
• Application Number:
  US13/822,024
• Publication Number:
  US 20130214453A1
• Time in Patent Office: 1,539 Days
• Field of Search: 522/99, 522/148, 522/1, 520/1
• US Class Current: 1/1
• CPC Class Codes: B82Y 10/00 Nanotechnology for information processing, storage or transmission, e.g. quantum computing or single electron logic
• CPC Class Codes: B82Y 40/00 Manufacture or treatment of nanostructures
• CPC Class Codes: C08F 222/10 Esters
• CPC Class Codes: C08F 283/124 on to polysiloxanes having carbon-to-carbon double bonds
• CPC Class Codes: C08F 30/08 containing silicon
• CPC Class Codes: C08G 77/20 containing silicon bound to unsaturated aliphatic groups C08G77/045 takes precedence
• CPC Class Codes: C09D 183/06 containing silicon bound to oxygen-containing groups C09D183/12 takes precedence
• CPC Class Codes: G03F 7/0002 Lithographic processes using patterning methods other than those involving the exposure to radiation, e.g. by stamping
• CPC Class Codes: G03F 7/0046 with perfluoro compounds, e.g. for dry lithography G03F7/0048 takes precedence
• CPC Class Codes: G03F 7/027 Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds G03F7/075 takes precedence
• CPC Class Codes: G03F 7/0757 Macromolecular compounds containing Si-O, Si-C or Si-N bonds G03F7/0752 takes precedence

Abstract

Provided is a photo-curable nanoimprint composition that has excellent properties in terms of etching resistance, dispersibility, and productivity. In addition, the photo-curable nanoimprint composition enables easy transcription of patterns even when a mold is pressed with a relatively low pressure. The photo-curable nanoimprint composition includes: (A) partial hydrolysate obtained by hydrolyzing a mixture of an organic silicon compound and a silicon compound containing (meth)acrylic groups with water in the molar amount of not less than 0.1 times but less than 1.0 times with respect to the number of moles of all alkoxy groups present in the mixture; (B) polymerizable monomer containing (meth)aclyic groups; and (C) pothopolymerization initiator. In addition, the mixture of partial hydrolysate (A) may include further partial hydrolysate of fluorinated silicone compound and/or metal oxide.

Claims

1. A photo-curable nanoimprint composition, said composition comprising:

(A) partial hydrolysate,

(B) polymerizable monomer having (meth)acrylic group; and

(C) photoinitiator,

wherein said partial hydrolysate (A) is selected from a group consisting of

(A-1) mixture of partial hydrolysate of organic silicon compound having a general formula (1);

2. The photo-curable nanoimprint composition according to the claim 1, wherein the partial hydrolysate (A) comprises the (A-1) mixture of partial hydrolysates of organic silicon compound having the general formula (1) and partial hydrolysate of (meth)acrylic group-containing silicon compound having the general formula (2) and the partial hydrolysate of metal alkoxide having the general formula (5), said partial hydrolysate (A) being a product obtained by hydrolyzing a mixture of the organic silicon compound having the general formula (1), the (meth)acrylic group-containing silicon compound having the general formula (2) and the metal alkoxide having the general formula (5) with water in the molar amount of not less than 0.1 times but less than 1.0 times with respect to the number of moles of all alkoxy groups present in the mixture.

3. The photo-curable nanoimprint composition according to the claim 1, wherein the partial hydrolysate (A) comprises the (A-2) mixture of partial hydrolysate of fluorinated silane compound having the general formula (3) and partial hydrolysate of (meth)acrylic group-containing silicon compound having the general formula (2) and the partial hydrolysate of metal alkoxide having the general formula (5), said partial hydrolysate (A) being a product obtained by hydrolyzing a mixture of the fluorinated silane compound having the general formula (3), the (meth)acrylic group-containing silicon compound having the general formula (2) and the metal alkoxide having the general formula (5) with water in the molar amount of not less than 0.1 times but less than 1.0 times with respect to the number of moles of all alkoxy groups present in the mixture.

4. The photo-curable nanoimprint composition according to the claim 1, wherein the partial hydrolysate (A) comprises the (A-3) mixture of partial hydrolysate of organic silicon compound having the general formula (1), partial hydrolysate of (meth)acrylic group-containing silicon compound having the general formula (2) and partial hydrolysate of fluorinated silane compound having the general formula (3) and the partial hydrolysate of metal alkoxide having the general formula (5), said partial hydrolysate (A) being a product obtained by hydrolyzing a mixture of the organic silicon compound having the general formula (1), the (meth)acrylic group-containing silicon compound having the general formula (2), the fluorinated silane compound having the general formula (3) and the metal alkoxide having the general formula (5) with water in the molar amount of not less than 0.1 times but less than 1.0 times with respect to the number of moles of all alkoxy groups present in the mixture.

5. The photo-curable nanoimprint composition according to the claim 1, wherein the partial hydrolysate (A) comprises the (A-3) mixture of partial hydrolysate of organic silicon compound having the general formula (1), partial hydrolysate of (meth)acrylic group-containing silicon compound having the general formula (2) and partial hydrolysate of fluorinated silane compound having the general formula (3) and the partial hydrolysate of metal alkoxide having the general formula (5), said partial hydrolysate (A) being a product obtained by the steps of hydrolyzing a mixture of the (meth)acrylic group-containing silicon compound having the general formula (2) and the fluorinated silane compound having the general formula (3) with water in the molar amount of not less than 0.1 times but less than 1.0 times with respect to the number of moles of all alkoxy groups present in the mixture to prepare a mixture of the partial hydrolysate of (meth)acrylic group-containing silicon compound having the general formula (2) and the partial hydrolysate of fluorinated silane compound having the general formula (3),

adding the organic silicon compound having the general formula (1) and the metal alkoxide having the general formula (5) to the prepared mixture of the partial hydrolysates, and

hydrolyzing the resulting mixture with water in the molar amount of not less than 0.1 times but less than 1.0 times with respect to the number of moles of all alkoxy groups present in the mixture.

6. The photo-curable nanoimprint composition according to claim 1, wherein said composition comprises the (A-1) mixture of partial hydrolysates obtained by hydrolyzing a mixture of 10-250 part by mass of the organic silicon compound having the general formula (1) and 3-300 parts by mass of the (meth)acrylic group-containing silicon compound having the general formula (2) with water in the molar amount of not less than 0.1 times but less than 1.0 times with respect to the number of moles of all alkoxy group present in the mixture, and 1-10 parts by mass of the photoinitiator (C) with respect to 100 parts by mass of the polymerizable monomer having (meth)acrylic group (B).

7. The photo-curable nanoimprint composition according to claim 1, wherein said composition comprises the (A-2) mixture of partial hydrolysates, each of which is obtained by hydrolyzing 0.001-4 part by mass of the fluorinated organic silane compound or 3-300 parts by mass of the (meth)acrylic group-containing silicon compound, and 1-10 parts by mass of the photoinitiator (C) with respect to 100 parts by mass of the polymerizable monomer having (meth)acrylic group (B).

8. The photo-curable nanoimprint composition according to claim 1, wherein said composition comprises the (A-3) mixture of partial hydrolysates, each of which is obtained by hydrolyzing 0.001-4 part by mass of the fluorinated organic silane compound, 10-250 parts by mass of the organic silicon compound, or 3-300 parts by mass of the (meth)acrylic group-containing silicon compound, and 1-10 parts by mass of the photoinitiator (C) with respect to 100 parts by mass of the polymerizable monomer having (meth)acrylic group (B).

9. The photo-curable nanoimprint composition according to claim 1, wherein the partial hydrolysate (A) comprises 0.2-100 parts by mass of metal alkoxide with respect to 100 parts by mass in total of the organic silicon compound (1) and the (meth)acrylic group-containing silicon compound (2) in case of the mixture of partial hydrolysates (A-1), in the total of the fluorinated organic silane (3) and the (meth)acrylic group-containing silicon compound (2) in the case of the mixture of partial hydrolysates (A-2), or in the total of the organic silicon compound (1), the (meth)acrylic group-containing silicon compound (2) and the fluorinated silane compound (3) in case of the mixture of partial hydrolysates (A-3).

10. A method of forming a pattern on a substrate by nanoimprinting, said method comprises the steps of

applying the photo-curable nanoimprint composition according to claim 1 on said substrate to form a coating film of said composition;

contacting said coating film with a pattern-forming surface of a mold, on which a desirable pattern has been formed, and irradiating with light as remaining the situation to cure said coating film, and

releasing said mold from the cured coating film, whereby a pattern which corresponds to the pattern formed in said pattern-forming surface of mold is formed on said substrate.

11. A replica mold for nanoimprint, wherein said mold has the cured product of the photo-curable nanoimprint composition according to claim 1.

12. A replica mold for nanoimprint, wherein said mold has the cured product of the photo-curable nanoimprint composition according to claim 2.

13. A replica mold for nanoimprint, wherein said mold has the cured product of the photo-curable nanoimprint composition according to claim 3.

14. A replica mold for nanoimprint, wherein said mold has the cured product of the photo-curable nanoimprint composition according to claim 4.

15. A replica mold for nanoimprint, wherein said mold has the cured product of the photo-curable nanoimprint composition according to claim 5.

16. A replica mold for nanoimprint, wherein said mold has the cured film of the photo-curable nanoimprint composition according to claim 5.