COPOLYMER FORMULATION FOR DIRECTED SELF ASSEMBLY, METHODS OF MANUFACTURE THEREOF AND ARTICLES COMPRISING THE SAME

• US 20160186004A1
• Filed: 11/18/2015
• Published: 06/30/2016
• Est. Priority Date: 12/30/2014
• Status: Active Grant

• Current Assignee: Dow Global Technologies LLC (Dow, Inc.), Rohm and Haas Electronic Materials LLC (DuPont de Nemours, Inc.)
• Original Assignee: Dow Global Technologies LLC (Dow, Inc.), Rohm and Haas Electronic Materials LLC (DuPont de Nemours, Inc.)
• Inventors: Hustad, Phillip D., Trefonas, Peter III, Chang, Shih-Wei
• Granted Patent: US 11,021,630 B2
• Time in Patent Office: Days
• US Class Current: 1/1
• CPC Class Codes: C08L 25/04 Homopolymers or copolymers of styrene
• CPC Class Codes: C09D 153/00 Coating compositions based on block copolymers containing at least one sequence of a polymer obtained by reactions only involving carbon-to-carbon unsaturated bonds; Coating compositions based on derivatives of such polymers
• CPC Class Codes: G03F 7/0002 Lithographic processes using patterning methods other than those involving the exposure to radiation, e.g. by stamping

Abstract

Disclosed herein is a method comprising disposing upon a substrate a composition comprising a block copolymer; where the block copolymer comprises a first polymer and a second polymer; where the first polymer and the second polymer of the block copolymer are different from each other and the block copolymer forms a phase separated structure; an additive polymer; where the additive polymer comprises a reactive moiety that is operative to react with a substrate upon which it is disposed; and where the additive polymer comprises a homopolymer that is the chemically and structurally the same as one of the polymers in the block copolymer or where the additive polymer comprises a random copolymer that has a preferential interaction with one of the blocks of the block copolymers; and a solvent; and annealing the composition.

Claims

1. A method comprising:

disposing upon a substrate a composition comprising;

a block copolymer;

where the block copolymer comprises a first polymer and a second polymer;

where the first polymer and the second polymer of the block copolymer are different from each other and the block copolymer forms a phase separated structure;

an additive polymer;

where the additive polymer comprises a reactive moiety that is operative to react with a substrate upon which it is disposed; and

where the additive polymer comprises a homopolymer that is the chemically and structurally the same as one of the polymers in the block copolymer or where the additive polymer comprises a random copolymer that has a preferential interaction with one of the blocks of the block copolymers; and

a solvent; and

annealing the composition to facilitate bonding or complexation or coordination of the additive polymer to the substrate and domain separation between the first polymer and the second polymer of the block copolymer to form a morphology of periodic domains formed from the first polymer and the second polymer;

where a longitudinal axis of the periodic domains are parallel to the substrate or wherein the domains are spherical.

2. The method of claim 1, further comprising removing at least one domain of the block copolymer.

3. The method claim 1, where the additive polymer has the structure of formulas (7A) or (7B):

4. The method of claim 1, where the additive 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.

5. The method of claim 1, where the additive polymer is a copolymer;

where the 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.

6. The method of claim 1, where the additive polymer is a hydroxyl terminated polystyrene, a hydroxyl terminated polydimethylsiloxane, a hydroxyl terminated poly(methylmethacrylate-random-trifluoro ethylmethacrylate), a hydroxyl terminated poly(methylmethacrylate-random-dodecafluoroheptylmethacrylate), or a combination comprising at least one of the foregoing additive polymers.

7. The method of claim 1, where the first polymer or the second polymer of the block copolymer comprises a polymer derived from monomers of a vinyl aromatic monomer, an ethylenically unsaturated monomer, 1-butene, 1,3-butadiene, isoprene, vinyl acetate, dihydropyran, norbornene, maleic anhydride, siloxane, or a combination comprising at least one of the foregoing monomers.

8. The method of claim 7, where the vinyl aromatic monomer is styrene, o-methylstyrene, p-methylstyrene, m-methylstyrene, α

-methylstyrene, o-ethylstyrene, m-ethylstyrene, p-ethylstyrene, α

-methyl-p-methylstyrene, 2,4-dimethylstyrene, monochlorostyrene, p-tert-butylstyrene, 4-tert-butylstyrene, hydroxy styrene, acetoxy styrene, or a combination comprising at least one of the foregoing vinyl aromatic monomers.

9. The method of claim 7, where the ethylenically unsaturated monomer is represented by formula (2):

10. The method of claim 1, where the block copolymer is a poly(styrene)-block(b)-poly(alkylsiloxane), a poly(alkylstyrene)-b-poly(alkylsiloxane), or a combination thereof.