Substrate pretreatment and etch uniformity in nanoimprint lithography

• US 10,488,753 B2
• Filed: 09/08/2016
• Issued: 11/26/2019
• Est. Priority Date: 09/08/2015
• Status: Active Grant

• Current Assignee: Canon Kabushiki Kaisha (Canon Inc.)
• Original Assignee: Canon Kabushiki Kaisha (Canon Inc.)
• Inventors: Stachowiak, Timothy, Liu, Weijun, Wan, Fen, Doyle, Gary, Khusnatdinov, Niyaz
• Primary Examiner(s): Alanko, Anita K
• Application Number:
  US15/260,073
• Publication Number:
  US 20170068161A1
• Time in Patent Office: 1,174 Days
• CPC Class Codes: B29C 2059/023 Microembossing
• CPC Class Codes: B29C 59/02 by mechanical means, e.g. pressing B29C59/007 takes precedence; embossing expanded porous articles B29C44/5627
• CPC Class Codes: B29C 59/026 of layered or coated substantially flat surfaces
• CPC Class Codes: C09K 13/00 Etching, surface-brightening or pickling compositions for glass C03C15/00, C03C25/66; for mortars, concrete, artificial or natural stone or ceramics C04B41/5338 ; for metallic material C23F, C23G1/00, C25F1/00; for semi-conductors H01L
• CPC Class Codes: G03F 7/0002 Lithographic processes using patterning methods other than those involving the exposure to radiation, e.g. by stamping

Abstract

A nanoimprint lithography method includes contacting a composite polymerizable coating formed from a pretreatment composition and an imprint resist with a nanoimprint lithography template defining recesses. The composite polymerizable coating is polymerized to yield a composite polymeric layer defining a pre-etch plurality of protrusions corresponding to the recesses of the nanoimprint lithography template. The nanoimprint lithography template is separated from the composite polymeric layer. At least one of the pre-etch plurality of protrusions corresponds to a boundary between two of the discrete portions of the imprint resist, and the pre-etch plurality of protrusions have a variation in pre-etch height of ±10% of a pre-etch average height. The pre-etch plurality of protrusions is etched to yield a post-etch plurality of protrusions having a variation in post-etch height of ±10% of a post-etch average height, and the pre-etch average height exceeds the post-etch average height.

Claims

1. An imprint lithography method comprising:

disposing a pretreatment composition on a substrate to yield a liquid pretreatment coating on the substrate, wherein the pretreatment composition comprises a polymerizable component;

disposing discrete portions of an imprint resist on the pretreatment coating, wherein the imprint resist is a polymerizable composition;

forming a composite polymerizable coating on the substrate as each discrete portion of the imprint resist spreads on the liquid pretreatment coating;

after forming the composite polymerizable coating, contacting the composite polymerizable coating with an imprint lithography template defining recesses;

polymerizing the composite polymerizable coating to yield a composite polymeric layer defining a pre-etch plurality of protrusions corresponding to the recesses of the imprint lithography template, wherein at least one of the pre-etch plurality of protrusions corresponds to a boundary between two of the discrete portions of the imprint resist, and the pre-etch plurality of protrusions have a variation in pre-etch height of ±

10% of a pre-etch average height;

separating the imprint lithography template from the composite polymeric layer; and

etching the pre-etch plurality of protrusions to yield a post-etch plurality of protrusions, wherein the post-etch plurality of protrusions have a variation in post-etch height of ±

10% of a post-etch average height, and the pre-etch average height exceeds the post-etch average height.

2. The imprint lithography method of claim 1, wherein the pre-etch average height is up to 1 μ

m, up to 500 nm, or up to 200 nm.

3. The imprint lithography method of claim 1, wherein the variation in post-etch height is ±

5% of the post-etch average height.

4. The imprint lithography method of claim 1, wherein at least two of the pre-etch plurality of protrusions correspond to boundaries between two of the discrete portions of the imprint resist.

5. The imprint lithography method of claim 1, wherein each protrusion in the pre-etch plurality of protrusions has a width in a range of 5 nm to 100 μ

m along a dimension of the substrate.

6. The imprint lithography method of claim 1, wherein the pre-etch plurality of protrusions corresponds to a linear dimension of up to 50 mm along a dimension of the substrate.

7. The imprint lithography method of claim 1, wherein etching the pre-etch plurality of protrusions comprises exposing the plurality of protrusions to an oxygen- or halogen-containing plasma.

8. The imprint lithography method of claim 1, wherein the boundary between the two of the discrete portions of the imprint resist is formed from an inhomogeneous mixture of the imprint resist and the pretreatment composition.

9. The imprint lithography method of claim 1, wherein the pre-etch average height exceeds the post-etch average height by at least 1 nm.

10. The imprint lithography method of claim 1, wherein the pre-etch height and the post-etch height are assessed at intervals in a range of 1 μ

m to 50 μ

m along a dimension of the substrate.

11. The imprint lithography method of claim 1, wherein the pre-etch height and the post-etch height are assessed by atomic force microscopy, reflectometry, ellipsometry, or profilometry.

12. The imprint lithography method of claim 1, wherein the interfacial surface energy between the pretreatment composition and air exceeds the interfacial surface energy between the imprint resist and air or between at least a component of the imprint resist and air.

13. The imprint lithography method of claim 1, wherein the difference between the interfacial surface energy between the pretreatment composition and air and the interfacial surface energy between the imprint resist and air is in a range of 0.5 mN/m to 25 mN/m, 0.5 mN/m to 15 mN/m, or 0.5 mN/m to 7 mN/m;

the interfacial surface energy between the imprint resist and air is in a range of 20 mN/m to 60 mN/m, 28 mN/m to 40 mN/m, or 32 mN/m to 35 mN/m; and

the interfacial surface energy between the pretreatment composition and air is in a range of 30 mN/m to 45 mN/m.

14. The imprint lithography method of claim 1, wherein the viscosity of the pretreatment composition is in a range of 1 cP to 200 cP, 1 cP to 100 cP, or 1 cP to 50 cP at 23°

C.; and

the viscosity of the imprint resist is in a range of 1 cP to 50 cP, 1 cP to 25 cP, or 5 cP to 15 cP at 23°

C.

15. A method for manufacturing a device, the method comprising the imprint lithography method of claim 1.

16. An imprint lithography method comprising:

disposing a pretreatment composition on a substrate to yield a liquid pretreatment coating on the substrate, wherein the pretreatment composition comprises a polymerizable component;

disposing discrete portions of an imprint resist on the liquid pretreatment coating, wherein the imprint resist is a polymerizable composition;

forming a composite polymerizable coating on the substrate as each discrete portion of the imprint resist spreads on the liquid pretreatment coating;

after forming the composite polymerizable coating, contacting the composite polymerizable coating with an imprint lithography template; and

polymerizing the composite polymerizable coating to yield a composite polymeric layer on the substrate,

wherein the interfacial surface energy between the pretreatment composition and air exceeds the interfacial surface energy between the imprint resist and air.

17. The imprint lithography method of claim 16, wherein:

the difference between the 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,

the interfacial surface energy between the imprint resist and air is in a range of 20 mN/m to 60 mN/m, and

the interfacial surface energy between the pretreatment composition and air is in a range of 30 N/m to 45 mN/m.

18. The imprint lithography method of claim 16, wherein each discrete portion of the imprint resist is separated from at least one other discrete portion of the imprint resist by the pretreatment composition when the composite polymerizable coating is contacted with the imprint lithography template.

19. A method for manufacturing a processed substrate, the method comprising the imprint lithography method of claim 16.

20. A method for manufacturing an optical component, the method comprising the imprint lithography method of claim 16.

21. A method for manufacturing a mold replica, the method comprising the imprint lithography method of claim 16.

22. An imprint lithography method comprising:

disposing a pretreatment composition on a substrate to yield a liquid pretreatment coating on the substrate, wherein the pretreatment composition comprises a polymerizable component;

disposing discrete portions of imprint resist on the liquid pretreatment coating, each discrete portion of the imprint resist covering a target area of the substrate;

forming a composite polymerizable coating on the substrate as each discrete portion of the imprint resist spreads beyond its target area, wherein the composite polymerizable coating comprises a liquid mixture of the pretreatment composition and the imprint resist;

after forming the composite polymerizable coating, contacting the composite polymerizable coating with an imprint lithography template; and

polymerizing the composite polymerizable coating to yield a composite polymeric layer on the substrate,

wherein the interfacial surface energy between the pretreatment composition and air exceeds the interfacial surface energy between at least a component of the imprint resist and air.

23. A method for pretreating a substrate, the method comprising:

coating the substrate with a pretreatment composition, wherein the pretreatment composition comprises a polymerizable component;

disposing discrete portions of an imprint resist on the pretreatment composition; and

after disposing the discrete portions of the imprint resist on the pretreatment composition, contacting the imprint resist with an imprint lithography template,

wherein the imprint resist disposed in discrete portions on the pretreatment composition spreads more rapidly than the same imprint resist disposed on the same substrate in the absence of the pretreatment composition.

24. The method for pretreating a substrate of claim 23, wherein the pretreatment composition is free of a polymerization initiator.

25. The method for pretreating a substrate of claim 23, wherein a defined length of time has elapsed between the disposing of the discrete portions of the imprint resist on the pretreatment composition and the contacting of the imprint resist with the imprint lithography template.

26. An imprint method comprising:

disposing a discrete portion of an imprint resist on a liquid pretreatment coating on a substrate such that the discrete portion of the imprint resist spreads on the liquid pretreatment coating to yield a spread imprint resist, wherein the liquid pretreatment coating comprises a polymerizable component and the imprint resist is a polymerizable composition;

contacting the spread imprint resist with a template; and

polymerizing the spread imprint resist and the pretreatment coating to yield a polymeric layer on the substrate;

wherein a surface tension of the liquid pretreatment coating exceeds a surface tension of the imprint resist.

27. The imprint method according to claim 26, wherein the pretreatment coating is free of a polymerization initiator.

28. The imprint method according to claim 26, wherein the spread imprint resist and the liquid pretreatment coating form a composite polymerizable coating before the contacting the spread imprint resist with the template.

29. The imprint method according to claim 26, further comprising separating the template from the polymeric layer.

30. The imprint method according to claim 26, wherein a thickness of the liquid pretreatment coating on the substrate is between 1 nm and 15 nm.

31. The imprint method according to claim 26, wherein the surface tension of the liquid pretreatment coating exceeds the surface tension of the imprint resist by 0.5 mN/m to 25 mN/m.

32. A method for manufacturing a semiconductor device, the method comprising:

providing a liquid pretreatment coating on a substrate, wherein the liquid pretreatment coating comprises a polymerizable component;

disposing a discrete portion of an imprint resist on the liquid pretreatment coating such that the discrete portion of the imprint resist spreads on the liquid pretreatment coating to yield a spread imprint resist, wherein the imprint resist is a polymerizable composition, and a surface tension of the pretreatment coating exceeds a surface tension of the imprint resist;

contacting the spread imprint resist with a template;

polymerizing the spread imprint resist and the pretreatment coating to yield a polymeric layer on the substrate;

separating the template from the polymeric layer; and

etching the substrate via the polymeric layer.

33. The method according to claim 32, wherein:

providing the liquid pretreatment coating comprises coating the substrate using spin-coating, dip coating, chemical vapor deposition (CVD), or physical vapor deposition (PVD), and

further comprising;

processing the substrate to yield the polymeric layer on the substrate using an imprint lithography system; and

etching the substrate using reactive ion etching or high density etching.