Polylactide/silicon-containing block copolymers for nanolithography

Patent metadata

Field	Value
Publication number	US-9834700-B2
Application number	US-201514827876-A
Country	US
Kind code	B2
Filing date	Aug 17, 2015
Priority date	Feb 10, 2012
Publication date	Dec 5, 2017
Grant date	Dec 5, 2017

Abstract

The present invention includes a diblock copolymer system that self-assembles at very low molecular weights to form very small features. In one embodiment, one polymer in the block copolymer contains silicon, and the other polymer is a polylactide. In one embodiment, the block copolymer is synthesized by a combination of anionic and ring opening polymerization reactions. In one embodiment, the purpose of this block copolymer is to form nanoporous materials that can be used as etch masks in lithographic patterning.

First claim

The invention claimed is:

1. A method of synthesizing a silicon and lactide-containing block copolymer, comprising:
a) providing first and second monomers, said first monomer comprising a silicon atom and said second monomer being a lactide based monomer lacking silicon;
b) treating said second monomer under conditions such that reactive polymer of said second monomer is formed; and
c) reacting said first monomer with said reactive polymer of said second monomer under conditions such that said silicon-containing block copolymer is synthesized, wherein the glass transitions of both blocks are above room temperature, wherein one of the blocks is polytrimethylsilylstyrene.

2. The method of claim 1 , wherein at least one of said blocks is cross-linkable.

3. The method of claim 1 , wherein a third monomer is provided and said block copolymer is a triblock copolymer.

4. The method of claim 1 , wherein said block copolymers form nanostructured materials that can be used as etch masks in lithographic patterning processes.

5. The method of claim 1 , wherein the method further comprises the step d) coating a substrate with said block copolymer so as to create a block copolymer film.

6. The method of claim 5 , wherein said substrate comprises silicon.

7. The method of claim 5 , wherein said substrate is a silicon wafer.

8. The method of claim 5 , wherein said substrate is quartz.

9. The method of claim 5 , wherein said substrate is glass.

10. The method of claim 5 , wherein said substrate is plastic.

11. The method of claim 10 , wherein said plastic is polyethylene terephthalate.

12. The method of claim 10 , wherein said plastic is polytetrafluoroethylene.

13. The method of claim 5 , wherein said substrate is a transparent substrate.

14. The method of claim 5 , wherein said substrate is coated with a substrate surface energy neutralizing layer with surface energy in between that of two blocks.

15. The method of claim 14 , wherein said substrate surface energy neutralizing layer is selected from the group consisting of: (a) high Tg polymer, (b) a cross-linked polymer, (c) vapor deposited polymer such as parylene, (d) small molecule derivatives of silylating agents, and (e) polymer brush by end-attaching polymer to substrate.

16. A method of synthesizing a silicon and lactide-containing block copolymer, comprising:
a) providing first and second monomers, said first monomer comprising a silicon atom and said second monomer being a lactide based monomer lacking silicon;
b) treating said second monomer under conditions such that reactive polymer of said second monomer is formed; and
c) reacting said first monomer with said reactive polymer of said second monomer under conditions such that said silicon-containing block copolymer is synthesized, wherein the glass transitions of both blocks are above room temperature, wherein said block copolymer is endcapped.

17. The method of claim 16 , wherein said block copolymer is endcapped with a functional group.

18. The method of claim 16 , wherein said block copolymer is endcapped with a hydroxyl functionality by reacting with ethylene oxide.

19. A method of synthesizing a silicon and lactide-containing block copolymer, comprising:
a) providing first and second monomers, said first monomer comprising a silicon atom and said second monomer being a lactide based monomer lacking silicon;
b) treating said second monomer under conditions such that reactive polymer of said second monomer is formed; and
c) reacting said first monomer with said reactive polymer of said second monomer under conditions such that said silicon-containing block copolymer is synthesized, wherein the glass transitions of both blocks are above room temperature, wherein the method further comprises precipitating said silicon-containing block copolymer in methanol.

20. A method of synthesizing a silicon and lactide-containing block copolymer, comprising:
a) providing first and second monomers, said first monomer comprising a silicon atom and said second monomer being a lactide based monomer lacking silicon;
b) treating said second monomer under conditions such that reactive polymer of said second monomer is formed; and
c) reacting said first monomer with said reactive polymer of said second monomer under conditions such that said silicon-containing block copolymer is synthesized, wherein the glass transitions of both blocks are above room temperature, wherein said first monomer is trimethylsilylstyrene.

21. A method of synthesizing a silicon and lactide-containing block copolymer, comprising:
a) providing first and second monomers, said first monomer comprising a silicon atom and said second monomer being a lactide based monomer lacking silicon;
b) treating said second monomer under conditions such that reactive polymer of said second monomer is formed; and
c) reacting said first monomer with said reactive polymer of said second monomer under conditions such that said silicon-containing block copolymer is synthesized, wherein the glass transitions of both blocks are above room temperature, wherein said first monomer is a silicon-containing methacrylate.

22. The method of claim 21 , wherein said first monomer is methacryloxymethyltrimethylsilane (MTMSMA).

Assignees

• Univ Texas

Inventors

• Ellison Christopher J
• Willson Carlton Grant
• Cushen Julia
• Bates Christopher M

Classifications

• B05C21/005

  Masking devices (stencils B05C17/06; masking devices for which the means for applying liquids or other fluent material is spraying or is not important B05B12/20) · CPC title

• Y10T428/24851

  Intermediate layer is discontinuous or differential · CPC title

• C08F2810/40

  taking place solely at one end or both ends of the polymer backbone, i.e. not in the side or lateral chains · CPC title

• B05D1/005

  Spin coating · CPC title

• C08F112/14

  substituted by hetero atoms or groups containing heteroatoms · CPC title