Method of controlling block copolymer characteristics and articles manufactured therefrom
View Patent ↗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.
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.