Substrate pretreatment compositions for nanoimprint lithography

• US 10,317,793 B2
• Filed: 03/03/2017
• Issued: 06/11/2019
• Est. Priority Date: 03/03/2017
• Status: Active Grant

• Current Assignee: Canon Kabushiki Kaisha (Canon Inc.)
• Original Assignee: Canon Kabushiki Kaisha (Canon Inc.)
• Inventors: Stachowiak, Timothy Brian, Liu, Weijun, Wan, Fen
• Primary Examiner(s): Mazumder, Didarul A
• Application Number:
  US15/449,395
• Publication Number:
  US 20180252999A1
• Time in Patent Office: 830 Days
• Field of Search: 438763, 427282, 428172
• 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 7/027 Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds G03F7/075 takes precedence
• CPC Class Codes: G03F 7/16 Coating processes; Apparatus therefor applying coatings to base materials in general B05; applying photosensitive compositions to base for photographic purposes G03C1/74
• CPC Class Codes: H01L 21/0271 comprising organic layers

Abstract

A nanoimprint lithography method includes coating a surface of a nanoimprint lithography substrate with a pretreatment composition to yield a layer of the pretreatment composition on the surface of the substrate, disposing an imprint resist on the layer of the pretreatment composition to yield a composite layer on the surface of the substrate, contacting the composite layer with a nanoimprint lithography template, and forming a polymeric layer on the surface of the substrate by polymerizing the composite layer. The pretreatment composition includes a polymerizable component having a molecular mass between about 300 and about 750. The imprint resist is a polymerizable composition. The composite layer includes a mixture of the pretreatment composition and the imprint resist. An average spreading rate of the imprint resist to form the composite layer exceeds an average spreading rate of the imprint resist on the substrate under otherwise identical conditions.

Claims

1. A nanoimprint lithography method comprising:

coating a surface of a nanoimprint lithography substrate with a pretreatment composition to yield a layer of the pretreatment composition on the surface of the nanoimprint lithography substrate, wherein the pretreatment composition is a liquid comprising a polymerizable component having a molecular mass between about 300 and about 750;

disposing an imprint resist on the layer of the pretreatment composition to yield a composite layer on the surface of the nanoimprint lithography substrate, wherein the imprint resist is a polymerizable composition, the composite layer comprises a mixture of the pretreatment composition and the imprint resist, and an average spreading rate of the imprint resist on the pretreatment composition to form the composite layer exceeds an average spreading rate of the imprint resist disposed directly on the nanoimprint lithography substrate under otherwise identical conditions;

contacting the composite layer with a nanoimprint lithography template; and

forming a polymeric layer on the surface of the nanoimprint lithography substrate by polymerizing the composite layer, wherein polymerizing the composite layer comprises forming a covalent bond between the polymerizable component of the pretreatment composition and a component of the imprint resist.

2. The method of claim 1, wherein the pretreatment composition is substantially free of a polymerization initiator.

3. The method of claim 1, wherein the polymerizable component comprises a (meth)acrylate monomer.

4. The method of claim 3, wherein the (meth)acrylate monomer comprises at least one glycol unit.

5. The method of claim 4, wherein the at least one glycol unit is an ethylene glycol unit (EO or OCH₂CH₂O) or a propylene glycol unit (PO or —

OCHCH₃CH₂O—

).

6. The method of claim 1, wherein the polymerizable component comprises at least one of tripropylene glycol diacrylate, tetraethylene glycol diacrylate, poly(ethylene glycol) diacrylate, tricyclodecane dimethanol diacrylate, stearyl acrylate, iso-stearyl acrylate, alkoxylated 1,6-hexanediol diacrylate, phenol tetraethylene glycol acrylate, neopentylglycol dipropylene glycol diacrylate, 1,12-dodecanediol dimethacrylate, 1,3-bis((2-hydroxyethoxy)methyl)benzene diacrylate, 4-hexylresorcinol diacrylate, 1,4-bis((2-hydroxyethoxy)methyl)cyclohexane diacrylate, 1,3-bis((2-hydroxyethoxy)methyl)-cyclohexane diacrylate, 3-benzyloxy-1,2-propanediol (EO)_n diacrylate (n=1-6), 2-phenyl-1,3-propanediol (EO)₂ diacrylate, 4-benzyloxy-1,3-butanediol diacrylate, 4-benzyloxy-1,3-butanediol (EO)₂ diacrylate, trimethylolpropane trimethacrylate, caprolactone acrylate, pentaerythritol tetraacrylate, alkoxylated pentaerythritol tetraacrylate, alkoxylated nonyl phenol acrylate, methoxy polyethylene glycol monoacrylates, alkoxylated lauryl acrylate, propoxylated (3) glyceryl triacrylate, alkoxylated trimethylolpropane triacrylate, ethoxylated bisphenol A diacrylate, ditrimethylolpropane tetraacrylate, dipentaerythritol pentaacrylate, and dipentaerythritol hexaacrylate.

7. The method of claim 6, wherein the polymerizable component comprises at least one of monomers:

1,3-bis((2-hydroxyethoxy)methyl)benzene diacrylate;

4-hexylresorcinol diacrylate;

3-benzyloxy-1,2-propanediol (EO)₁ diacrylate;

2-phenyl-1,3-propanediol (EO)₂ diacrylate;

4-benzyloxy-1,3-butanediol diacrylate; and

4-benzyloxy-1,3-butanediol (EO)₂ diacrylate.

8. The method of claim 1, wherein an interfacial surface energy between the polymerizable component and air is at least 35 mN/m.

9. The method of claim 8, wherein the interfacial surface energy between the polymerizable component and air is 45 mN/m or less.

10. The method of claim 1, wherein the difference between an interfacial surface energy between the pretreatment composition and air and between the imprint resist and air is in a range of 0.5 mN/m to 25 mN/m.

11. The method of claim 10, wherein the interfacial surface energy between the imprint resist and air is in a range of 20 mN/m to 60 mN/m.

12. The method of claim 1, wherein a viscosity of the pretreatment composition in a range between 1 cP and 150 cP at 23°

C.

13. The method of claim 12, wherein the viscosity of the pretreatment composition is in a range between 1 cP and 100 cP at 23°

C.

14. A method for manufacturing an article, the method comprising:

coating a surface of a nanoimprint lithography substrate with a pretreatment composition to yield a layer of the pretreatment composition on the surface of the nanoimprint lithography substrate, wherein the pretreatment composition is a liquid comprising a polymerizable component having a molecular mass between about 300 and about 750;

disposing an imprint resist on the layer of the pretreatment composition to yield a composite layer on the surface of the nanoimprint lithography substrate, wherein the imprint resist is a polymerizable composition, the composite layer comprises a mixture of the pretreatment composition and the imprint resist, and an average spreading rate of the imprint resist on the pretreatment composition to form the composite layer exceeds an average spreading rate of the imprint resist disposed directly on the nanoimprint lithography substrate under otherwise identical conditions;

contacting the composite layer with a nanoimprint lithography template; and

forming a polymeric layer on the surface of the nanoimprint lithography substrate to yield the article, wherein forming the polymeric layer comprises polymerizing the composite layer, and polymerizing the composite layer comprises forming a covalent bond between the polymerizable component of the pretreatment composition and a component of the imprint resist.

15. The method of claim 14, wherein the article comprises a processed nanoimprint lithography substrate or an optical component.

16. The article of claim 15.

17. A kit comprising:

a pretreatment composition comprising a polymerizable component having a molecular mass between about 300 and about 750; and

an imprint resist,

wherein the imprint resist is a polymerizable composition, an average spreading rate of the imprint resist on the pretreatment composition to form a composite layer exceeds an average spreading rate of the imprint resist disposed directly on a nanoimprint lithography substrate under otherwise identical conditions, and polymerizing a liquid mixture of the pretreatment composition and the imprint resist forms a covalent bond between the polymerizable component of the pretreatment composition and a component of the imprint resist.

18. The kit of claim 17, wherein the polymerizable component comprises a (meth)acrylate monomer.

19. The kit of claim 18, wherein the polymerizable component comprises at least one of monomers:

1,3-bis((2-hydroxyethoxy)methyl)benzene diacrylate;

4-hexylresorcinol diacrylate;

3-benzyloxy-1,2-propanediol (EO)₁ diacrylate;

2-phenyl-1,3-propanediol (EO)₂ diacrylate;

4-benzyloxy-1,3-butanediol diacrylate; and

4-benzyloxy-1,3-butanediol (EO)₂ diacrylate.

20. A pretreatment composition for a nanoimprint lithography substrate, the pretreatment composition comprising at least one of monomers:

1,3-bis((2-hydroxyethoxy)methyl)benzene diacrylate;

4-hexylresorcinol diacrylate;

3-benzyloxy-1,2-propanediol (EO)₁ diacrylate;

2-phenyl-1,3-propanediol (EO)₂ diacrylate;

4-benzyloxy-1,3-butanediol diacrylate; and

4-benzyloxy-1,3-butanediol (EO)₂ diacrylate.