Method of controlling block copolymer characteristics and articles manufactured therefrom

Patent metadata

Field	Value
Publication number	US-9738814-B2
Application number	US-201414580307-A
Country	US
Kind code	B2
Filing date	Dec 23, 2014
Priority date	Dec 31, 2013
Publication date	Aug 22, 2017
Grant date	Aug 22, 2017

Abstract

Disclosed herein is a composition comprising a brush polymer; where the brush polymer comprises a reactive moiety that is reacted to a substrate upon which it is disposed; and a block copolymer; where the block copolymer comprises a first block and a second block that are covalently bonded to each other; where the first block comprises a first polymer and a second block comprises a second polymer; where the first polymer comprises less than or equal to 10 atomic percent polysiloxane; where the second polymer comprises at least 15 atomic percent polysiloxane; where the brush polymer is chemically different from the first polymer and the second polymer; and where the first polymer is chemically different from the second polymer; and wherein the block copolymer is disposed upon the brush polymer.

First claim

What is claimed is:

1. An article comprising:
a brush polymer; where the brush polymer is reacted with a substrate upon which it is disposed; and
a block copolymer; where the block copolymer comprises a first block and a second block that are covalently bonded to each other; where the first block comprises a first polymer and a second block comprises a second polymer; where the first polymer comprises less than or equal to 10 atomic percent of silicon; where the second polymer comprises at least 15 atomic percent silicon; where the brush polymer is chemically different from the first polymer and the second polymer; and where the first polymer is chemically different from the second polymer;
and wherein the block copolymer is disposed upon the brush polymer; where the first block comprises a first polymer derived from o-methylstyrene, m-methylstyrene, o-ethylstyrene, m-ethylstyrene, p-ethylstyrene, α-methyl-p-methylstyrene, 2,4-dimethylstyrene, monochlorostyrene, 4-tert-butylstyrene, or a combination thereof.

2. The article of claim 1 , where the brush polymer has a surface energy that is lower than the surface energy of the block copolymer.

3. The article of claim 1 , where the brush polymer has a surface energy that is higher than the surface energy of the block copolymer.

4. The article of claim 1 , where the brush polymer has the structure of formulas (7A) or (7B):

where the reactive species X is a hydroxyl group, a thiol group, an amine group, a carboxyl group, a silane group or an alkoxy groups, R 1 , R 2 and R 3 are the same or different and is a hydrogen, a C 1-10 alkyl group, a C 1-10 alkyl ester group, a C 3-10 cycloalkyl ester group, a C 7-10 aralkyl ester group, a C 6 -C 14 aryl, a C 7 -C 13 alkylaryl or a C 7 -C 13 arylalkyl group.

5. The article of claim 1 , where the brush polymer is a polystyrene, a polysiloxane, a polymethylmethacrylate, a polyacrylate, a polyvinylacetate, a polydiene, a polyether, a polyester, a polysiloxane, a polyorganogermane, or a combination comprising at least one of the foregoing polymers.

6. The article of claim 1 , where the brush polymer is a copolymer; where the brush copolymer is poly(styrene-b-vinyl pyridine), poly(styrene-b-butadiene), poly(styrene-b-isoprene), poly(styrene-b-methyl methacrylate), poly(styrene-b-alkenyl aromatics), poly(isoprene-b-ethylene oxide), poly(styrene-b-(ethylene-propylene)), poly(ethylene oxide-b-caprolactone), poly(butadiene-b-ethylene oxide), poly(styrene-b-t-butyl (meth)acrylate), poly(methyl methacrylate-b-t-butyl methacrylate), poly(ethylene oxide-b-propylene oxide), poly(styrene-b-tetrahydrofuran), poly(styrene-b-isoprene-b-ethylene oxide), poly(styrene-b-dimethylsiloxane), poly(styrene-b-trimethylsilylmethyl methacrylate), poly(methyl methacrylate-b-dimethylsiloxane), poly(methyl methacrylate-b-trimethylsilylmethyl methacrylate), or a combination comprising at least one of the foregoing copolymers.

7. The article of claim 1 , where the brush polymer is a hydroxyl terminated polystyrene, hydroxyl terminated polydimethylsiloxane, hydroxyl terminated poly(methylmethacrylate-random-trifluoroethylmethacrylate), a hydroxyl terminated poly(methylmethacrylate-random-dodecafluoroheptylmethacrylate), or a combination comprising at least one of the foregoing polymers.

8. The article of claim 1 , where the brush polymer comprises an ethylenically unsaturated monomer that is represented by formula (1):

where R 1 is a hydrogen or an alkyl group having 1 to 10 carbon atoms, by the formula (2):

where R 1 is a hydrogen or an alkyl group having 1 to 10 carbon atoms and R 2 is a C 1-10 alkyl, a C 3-10 cycloalkyl, or a C 7-10 aralkyl group, or by the formula (3):

where R 1 is a hydrogen or an alkyl group having 1 to 10 carbon atoms and R 3 is a C 2-10 fluoroalkyl group.

9. The article of claim 1 , where the block copolymer comprises a polysiloxane has the structure of formula (4)

wherein each R is independently a C 1 -C 10 alkyl, a C 3 -C 10 cycloalkyl, a C 6 -C 14 aryl, a C 7 -C 13 alkylaryl or a C 7 -C 13 and where n in the formula (4) is 25 to 5,000.

10. The article of claim 1 , where the block copolymer is poly(t-butylstyrene)-b-poly(dimethylsiloxane).

11. A method comprising:
disposing a brush polymer upon a substrate; where the brush polymer comprises a reactive moiety that is reacted with the substrate; and
disposing upon the brush a block copolymer; where the block copolymer comprises a first block and a second block that are covalently bonded to each other; where the first block comprises a first polymer and a second block comprises a second polymer; where the first polymer comprises less than or equal to 10 atomic percent silicon; where the second polymer comprises at least 15 atomic percent silicon; where the brush polymer is chemically different from the first polymer and the second polymer; and where the first polymer is chemically different from the second polymer; where the first block comprises a first polymer derived from o-methylstyrene, m-methylstyrene, o-ethylstyrene, m-ethylstyrene, p-ethylstyrene, α-methyl-p-methylstyrene, 2,4-dimethylstyrene, monochlorostyrene, 4-tert-butylstyrene, or a combination thereof.

12. The method of claim 11 , further comprising annealing the substrate.

13. The method claim 11 , further comprising etching at least one block of the block copolymer.

Assignees

• Dow Global Technologies Llc
• Rohm & Haas Elect Mat

Inventors

• Chang Shih-Wei
• Park Jong Keun
• Kramer John W
• Vogel Erin B
• Hustad Phillip D
• Trefonas Iii Peter

Classifications

• C08G77/16

  to hydroxy groups · CPC title

• Y10T428/31663

  As siloxane, silicone or silane · CPC title

• C08G77/442

  containing vinyl polymer sequences · CPC title

• C09D183/10 Primary

  Block or graft copolymers containing polysiloxane sequences (obtained by polymerising a compound having a carbon-to-carbon double bond on to a polysiloxane C09D151/08, C09D153/00) · CPC title

• C08J2483/10

  Block- or graft-copolymers containing polysiloxane sequences · CPC title