Curable composition and cured product thereof, method for producing cured product, method for manufacturing optical component, method for manufacturing circuit board, and method for manufacturing electronic component

Patent metadata

Field	Value
Publication number	US-10023673-B2
Application number	US-201515308823-A
Country	US
Kind code	B2
Filing date	Apr 28, 2015
Priority date	May 9, 2014
Publication date	Jul 17, 2018
Grant date	Jul 17, 2018

Abstract

To provide a curable composition for nanoimprinting that can form a cured product that has a sufficiently cured surface and is less prone to a pattern collapse defect even when the curable composition is cured by a photo-nanoimprint method at a low exposure dose. To provide a nanoimprint method for forming such a cured product. To provide a cured product that is less prone to a pattern collapse defect even when cured at a low exposure dose, a method for producing such a cured product, a method for manufacturing an optical component, a method for manufacturing a circuit board, and a method for manufacturing an electronic component.
A curable composition that satisfies the formula (1) in a cured state:

Er 1 /Er 2 ≥1.10  (1)
wherein Er 1 denotes the surface reduced modulus (GPa) of a cured product of the curable composition, and Er 2 denotes the internal reduced modulus (GPa) of the cured product.

First claim

The invention claimed is:

1. A curable composition that satisfies the following formula (1) in a cured state:
Er 1 /Er 2 ≥1.10  (1)

wherein Er 1 denotes a surface reduced modulus (GPa) of a cured product of the curable composition, and Er 2 denotes an internal reduced modulus (GPa) of the cured product.

2. The curable composition according to claim 1 , comprising:
a polymerizable compound component (A); and
a photopolymerization initiator component (B),
wherein the cured state is a cured product of the curable composition cured at an exposure dose of 200 mJ/cm 2 has an average film thickness of 3.2 μm:
wherein Er 1 denotes an average reduced modulus (GPa) in a depth range of 4 nm or less from a surface of the cured product, and Er 2 denotes a reduced modulus (GPa) at a depth of 200 nm from the surface of the cured product.

3. The curable composition according to claim 1 , wherein
Er 1 is an average surface reduced modulus (GPa) of the cured product measured with a nanoindenter and determined by a Hertz method, and
Er 2 is an internal reduced modulus (GPa) of the cured product measured with a nanoindenter and determined by an Oliver-Pharr method.

4. The curable composition according to claim 1 , further satisfying the following formula (3):
Er 1 ≥3.00  (3)

wherein Er 1 denotes a surface reduced modulus (GPa) of the cured product.

5. The curable composition according to claim 1 , wherein the component (A) is composed mainly of a monofunctional (meth)acrylic compound and/or a polyfunctional (meth)acrylic compound.

6. The curable composition according to claim 1 , wherein the component (A) contains at least one of isobornyl acrylate, benzyl acrylate, 2-naphthylmethyl acrylate, dicyclopentanyl acrylate, m-xylylene diacrylate, dimethyloltricyclodecane diacrylate, phenylethylene glycol diacrylate, 1,10-decanediol diacrylate, and neopentyl glycol diacrylate.

7. The curable composition according to claim 1 , wherein the component (A) is composed mainly of a (meth)acrylic compound, and 20% by weight or more of the component (A) is a polyfunctional (meth)acrylic compound.

8. The curable composition according to claim 1 , wherein the component (A) is composed mainly of a (meth)acrylic compound, and 30% by weight or more of the component (A) is a (meth)acrylic compound having a ring structure.

9. The curable composition according to claim 1 , wherein the component (A) is composed mainly of dicyclopentanyl acrylate and m-xylylene diacrylate, and the weight ratio of dicyclopentanyl acrylate to m-xylylene diacrylate ranges from 40:60 to 60:40.

10. The curable composition according to claim 1 , wherein the component (B) contains at least one of alkylphenone polymerization initiator[s] and acylphosphine oxide polymerization initiator[s].

11. The curable composition according to claim 1 , wherein the component (B) contains at least one of 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)-butanone-1 and 2,4,6-trimethylbenzoyldiphenylphosphine oxide.

12. The curable composition according to claim 1 , wherein the component (A) is composed mainly of dicyclopentanyl acrylate and m-xylylene diacrylate, the weight ratio of dicyclopentanyl acrylate to m-xylylene diacrylate ranges from 40:60 to 60:40, and the amount of component (B) ranges from 0.01% to 10% by weight of the total amount of the component (A).

13. The curable composition according to claim 1 , further comprising at least one of fluorosurfactants and hydrocarbon surfactants as an internal release agent.

14. The curable composition according to claim 1 , further comprising at least one sensitizer having a benzophenone structure.

15. The curable composition according to claim 1 , further comprising at least one hydrogen donor having a benzophenone structure.

16. The curable composition according to claim 1 , wherein the curable composition has a viscosity of 1 cP or more and 100 cP or less.

17. The curable composition according to claim 1 , wherein the curable composition is a composition for photo-nanoimprinting.

18. A cured product of the curable composition according to claim 1 .

19. A method for producing a patterned film, comprising:
a step [1] of placing the curable composition according to claim 1 on a substrate;
a step [2] of bringing the curable composition into contact with a mold having an original pattern to be transferred;
a step [3] of aligning the substrate with the mold;
a step [4] of forming a cured film by photoirradiation of the curable composition; and
a step [5] of separating the cured film from the mold.

20. The method for producing a patterned film according to claim 19 , wherein the mold in the step of bringing the curable composition into contact with a mold having an original pattern to be transferred has a pattern height of 4 nm or more and 200 nm or less and an aspect ratio of 1 or more and 10 or less.

21. The method for producing a patterned film according to claim 19 , wherein the exposure dose in the step of forming a cured film by photoirradiation of the curable composition is 90 mJ/cm 2 or less.

22. The method for producing a film according to claim 19 , wherein the mold contact step is performed in an atmosphere containing a condensable gas.

23. The method for producing a film according to claim 22 , wherein the condensable gas is 1,1,1,3,3-pentafluoropropane.

24. The method for producing a film according to claim 22 , wherein the atmosphere containing a condensable gas is a gas mixture of helium and the condensable gas.

25. A method for manufacturing an optical component, comprising a step of forming a patterned film by the method for producing a film according to claim 19 .

26. A method for manufacturing a circuit board, comprising: a step of forming a patterned film by the method for producing a film according to claim 19 ; and a step of subjecting the substrate to etching or ion implantation using the patterned film as a mask.

27. The method for manufacturing a circuit board according to claim 26 , wherein the circuit board is a semiconductor device.

28. A method for manufacturing an electronic component, comprising a step of forming a patterned film by the method for producing a film according to claim 19 .

29. A curable composition, comprising:
a polymerizable compound component (A); and
a photopolymerization initiator component (B),
wherein the curable composition satisfies the following formula (1) when a cured product of the curable composition cured at an exposure dose of 200 mJ/cm 2 has an average film thickness of 3.2 μm:
Er 1 /Er 2 ≥1.10  (1)

wherein Er 1 denotes an average reduced modulus (GPa) in a depth range of 4 nm or less from a surface of the cured product, and Er 2 denotes a reduced modulus (GPa) at a depth of 200 nm from the surface of the cured product.

30. The curable composition according to claim 1 , wherein the curable composition is adjusted such that a concentration distribution of the composition differs between an upper layer and an inner layer of a film in a case where the curable composition is made into the film.

31. The curable composition according to claim 1 , further comprising a surfactant containing a perfluoroalkyl group or a long-chain alkyl group, and polyalkylene oxide group having 2 to 4 carbon atoms.

Assignees

• Canon Kk

Inventors

• Kato Jun
• Kawasaki Youji
• Yonezawa Shiori
• Ito Toshiki

Classifications

• H10P76/4085

  characterised by the processes involved to create the masks · CPC title

• H10P76/405

  characterised by their composition, e.g. multilayer masks · CPC title

• H10P50/695

  characterised by the process involved to create the mask, e.g. lift-off masks or sidewalls or to modify the mask · CPC title

• H10P50/692

  characterised by their composition, e.g. multilayer masks or materials · CPC title

• H10P50/242

  of Group IV materials · CPC title