Photocurable composition including a reactive polymer

Patent metadata

Field	Value
Publication number	US-12247133-B2
Application number	US-202217651544-A
Country	US
Kind code	B2
Filing date	Feb 17, 2022
Priority date	Feb 17, 2022
Publication date	Mar 11, 2025
Grant date	Mar 11, 2025

Abstract

A photocurable composition can comprise a polymerizable material, and a photoinitiator, wherein the polymerizable material can comprise at least one polymerizable monomer and at least one reactive polymer. The reactive polymer can have a carbon content of at least 75% based on the total weight of the reactive polymer; a molecular weight of the at least one reactive polymer can be at least 400 g/mol and not greater than 50,000 g/mol; an amount of the reactive polymer may be at least 5 wt %; and a viscosity of the photocurable composition may be not greater than 100 mPa s. The photocurable composition may have a low linear shrinkage after curing, a high carbon content and high etch resistance and being suitable for AIP or NIL processing.

First claim

What is claimed is:

1. A photocurable composition comprising a polymerizable material and a photoinitiator, wherein
the polymerizable material comprises at least one polymerizable monomer and at least one reactive polymer;
the reactive polymer comprises a carbon content of at least 75% based on the total weight of the reactive polymer;
a molecular weight of the at least one reactive polymer is at least 400 g/mol and not greater than 50,000 g/mol;
an amount of the reactive polymer is at least 5 wt % based on the total weight of the polymerizable material; and
a viscosity of the photocurable composition is not greater than 100 mPa·s, wherein
an amount of the polymerizable material is at least 50 wt % based on the total weight of the photocurable composition;
the polymerizable monomer comprises a multi-functional acrylate monomer in an amount of at least 50 wt % based on the total weight of the polymerizable material and further at least one mono-functional acrylate monomer; and
a total carbon content of the photocurable composition after curing is at least 69%.

2. The photocurable composition of claim 1 , wherein the reactive polymer comprises a structure of formula (1): R 1 —X n —R 2 (1), with X being repeating monomer units of a same type or different types, n being 3 to 300, R1 and R2 including independently or both a vinyl group, an acrylate group, a methacrylate group, or a vinylbenzene group.

3. The photocurable composition of claim 2 , wherein X is —O—Ar—, or —Ar—C═O, or —CH 2 —CHR 3 —CH 2 —, with R 3 being benzene, naphthene, anthracene, cyclohexane, isobornyl, or adamantane, and Ar being substituted or unsubstituted benzene, naphthalene, or anthracene.

4. The photocurable composition of claim 1 , wherein the reactive polymer comprises a structure of formula (2): R 1 —X n —Y—X m —R 2 (2), with X being repeating monomer units of same type or different types, n being 3 to 150, m being 3-150, Y being a linking unit, R1 and R2 including independently or both a vinyl group, an acrylate group, a methacrylate group, or a vinylbenzene group.

5. The photocurable composition of claim 4 , wherein X is —O—Ar—, or —Ar—C═O, with Ar being substituted or unsubstituted benzene, naphthalene, or anthracene.

6. The photocurable composition of claim 1 , wherein the reactive polymer comprises functional groups attached to repeating monomer units of the reactive polymer, and a number ratio of the functional groups to the repeating monomer units ranges from 1:3 to 1:100.

7. The photocurable composition of claim 1 , wherein the photocurable composition is adapted that a linear shrinkage of the photocurable composition after photo-curing is not greater than 6 percent.

8. The photocurable composition of claim 1 , wherein the viscosity of the photocurable composition is not greater than 35 mPa·s.

9. The photocurable composition of claim 1 , wherein the molecular weight of the reactive polymer is at least 800 g/mol and not greater than 10,000 g/mol.

10. The photocurable composition of claim 1 , wherein the amount of the reactive polymer is at least 5 wt % and not greater than 30 wt % based on the total weight of the polymerizable material.

11. The photocurable composition of claim 1 , wherein an amount of the polymerizable material is at least 80 wt % based on the total weight of the photocurable composition.

12. The photocurable composition of claim 1 , wherein the at least one multi-functional monomer has a boiling point of at least 250° C., and an amount of the multi-functional monomer is at least 80 wt % based on the total weight of the polymerizable material.

13. The photocurable composition of claim 1 , wherein a weight percent ratio of the at least one mono-functional acrylate monomer to the at least one multi-functional acrylate monomer ranges from 1:3 to 1:5.

14. The photocurable composition of claim 1 , wherein the photocurable composition is adapted for nanoimprint lithography (NIL) or inkjet adaptive planarization (IAP) processing.

15. The photocurable composition of claim 1 , wherein a thermal degradation temperature of the photocurable composition after photo-curing is at least 300° C.

16. A method of forming a photo-cured layer on a substrate, comprising:
applying a layer of a photocurable composition on the substrate, wherein the photocurable composition comprises a polymerizable material and a photoinitiator, wherein the polymerizable material comprises at least one polymerizable monomer and at least one reactive polymer; the reactive polymer comprises a carbon content of at least 75% based on the total weight of the reactive polymer; a molecular weight of the at least one reactive polymer is at least 400 g/mol and not greater than 50,000 g/mol; an amount of the reactive polymer is at least 5 wt % based on the total weight of the photocurable composition; a viscosity of the photocurable composition is not greater than 100 mPa·s; an amount of the polymerizable material is at least 50 wt % based on the total weight of the photocurable composition; and the polymerizable monomer comprises a multi-functional acrylate monomer in an amount of at least 50 wt % based on the total weight of the polymerizable material and further at least one mono-functional acrylate monomer, and a total carbon content of the photocurable composition after curing is at least 69%;
bringing the photocurable composition into contact with a template or a superstrate;
irradiating the photocurable composition with light to form a photo-cured layer; and
removing the template or the superstrate from the photo-cured layer.

17. The method of claim 16 , wherein a linear thermal shrinkage of the layer of the photocurable composition after forming the photo-cured layer is not greater than 6 percent.

18. A method of manufacturing an article, comprising:
applying a layer of a photocurable composition on the substrate, wherein the photocurable composition comprises a polymerizable material and a photoinitiator, wherein the polymerizable material comprises at least one polymerizable monomer and at least one reactive polymer; the reactive polymer comprises a carbon content of at least 75% based on the total weight of the reactive polymer; a molecular weight of the at least one reactive polymer is at least 400 g/mol and not greater than 50,000 g/mol; an amount of the reactive polymer is at least 5 wt % based on the total weight of the photocurable composition; a viscosity of the photocurable composition is not greater than 100 mPa·s; an amount of the polymerizable material is at least 50 wt % based on the total weight of the photocurable composition; and the polymerizable monomer comprises a multi-functional acrylate monomer in an amount of at least 50 wt % based on the total weight of the polymerizable material and further at least one mono-functional acrylate monomer, and a total carbon content of the photocurable composition after curing is at least 69%;
bringing the photocurable composition into contact with a template or a superstrate;
irradiating the photocurable composition with light to form a photo-cured layer;
removing the template or the superstrate from the photo-cured layer;
forming a pattern on the substrate;
processing the substrate on which the pattern has been formed in the forming; and

manufacturing an article from the substrate processed in the processing.

Assignees

• Canon Kk

Inventors

• Wan Fen
• Stachowiak Timothy Brian
• Liu Weijun

Classifications

• C09D11/00

  Inks · CPC title

• G03F7/2004

  characterised by the use of a particular light source, e.g. fluorescent lamps or deep UV light · CPC title

• G03F7/0045

  with organic non-macromolecular light-sensitive compounds not otherwise provided for, e.g. dissolution inhibitors · CPC title

• C09D11/101

  Inks specially adapted for printing processes involving curing by wave energy or particle radiation, e.g. with UV-curing following the printing · CPC title

• G03F7/0002

  Lithographic processes using patterning methods other than those involving the exposure to radiation, e.g. by stamping · CPC title