Crosslinkable graft polymer non-preferentially wetted by polystyrene and polyethylene oxide
First Claim
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1. A method of forming a self-assembled block copolymer structure, comprising:
- preparing an azido-functionalized random poly(styrene-r-ethylene oxide) graft copolymer by;
reacting a reaction mixture comprising p-chloromethylstyrene and styrene to form polymer chains comprising chloromethyl moieties and repeating units derived from p-chloromethylstyrene and styrene, wherein the reaction mixture comprises p-chloromethylstyrene in a molecular amount greater than a molecular amount of the styrene;
reacting the polymer chains with one or more oligomers or polymers of poly(ethylene oxide) to form a graft copolymer comprising chloromethyl moieties, wherein the poly(ethylene oxide) has only one nucleophilic end; and
reacting the graft copolymer comprising chloromethyl moieties with an azide compound to displace chlorine atoms of the chloromethyl moieties to form azidomethyl moieties on the graft copolymer;
forming the azido-functionalized random poly(styrene-r-ethylene oxide) graft copolymer over at least a portion of a floor of a trench in a substrate to provide a trench having at least one portion of the floor bearing azido-functionalized random poly(styrene-r-ethylene oxide) graft copolymer and at least one portion of the floor exposing the substrate;
forming a block copolymer material within the trench in the substrate; and
annealing the block copolymer material to self-assemble the block copolymer material into first and second self-assembled domains of a first polymer block of the block copolymer material in a matrix of a second polymer block, the first self-assembled domains over the at least a portion of the floor of the trench bearing a crosslinked material of the azido-functionalized random poly(styrene-r-ethylene oxide) graft copolymer, the first self-assembled domains oriented perpendicular to the at least a portion of the floor of the trench bearing the crosslinked material of the azido-functionalized random poly(styrene-r-ethylene oxide) graft copolymer and parallel to sidewalk of the trench, the second self-assembled domains over the at least a portion of the floor of the trench exposing the substrate, the second self-assembled domains oriented parallel to the floor and sidewalls of the trench.
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Abstract
Methods for fabricating a random graft PS-r-PEO copolymer and its use as a neutral wetting layer in the fabrication of sublithographic, nanoscale arrays of elements including openings and linear microchannels utilizing self-assembling block copolymers, and films and devices formed from these methods are provided. In some embodiments, the films can be used as a template or mask to etch openings in an underlying material layer.
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Citations
20 Claims
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1. A method of forming a self-assembled block copolymer structure, comprising:
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preparing an azido-functionalized random poly(styrene-r-ethylene oxide) graft copolymer by; reacting a reaction mixture comprising p-chloromethylstyrene and styrene to form polymer chains comprising chloromethyl moieties and repeating units derived from p-chloromethylstyrene and styrene, wherein the reaction mixture comprises p-chloromethylstyrene in a molecular amount greater than a molecular amount of the styrene; reacting the polymer chains with one or more oligomers or polymers of poly(ethylene oxide) to form a graft copolymer comprising chloromethyl moieties, wherein the poly(ethylene oxide) has only one nucleophilic end; and reacting the graft copolymer comprising chloromethyl moieties with an azide compound to displace chlorine atoms of the chloromethyl moieties to form azidomethyl moieties on the graft copolymer; forming the azido-functionalized random poly(styrene-r-ethylene oxide) graft copolymer over at least a portion of a floor of a trench in a substrate to provide a trench having at least one portion of the floor bearing azido-functionalized random poly(styrene-r-ethylene oxide) graft copolymer and at least one portion of the floor exposing the substrate; forming a block copolymer material within the trench in the substrate; and annealing the block copolymer material to self-assemble the block copolymer material into first and second self-assembled domains of a first polymer block of the block copolymer material in a matrix of a second polymer block, the first self-assembled domains over the at least a portion of the floor of the trench bearing a crosslinked material of the azido-functionalized random poly(styrene-r-ethylene oxide) graft copolymer, the first self-assembled domains oriented perpendicular to the at least a portion of the floor of the trench bearing the crosslinked material of the azido-functionalized random poly(styrene-r-ethylene oxide) graft copolymer and parallel to sidewalk of the trench, the second self-assembled domains over the at least a portion of the floor of the trench exposing the substrate, the second self-assembled domains oriented parallel to the floor and sidewalls of the trench. - View Dependent Claims (3, 4, 5, 6, 7, 8, 9, 10, 11, 12)
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2. A method of forming a self-assembled block copolymer structure, comprising:
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preparing an azido-functionalized random poly(styrene-r-ethylene oxide) graft copolymer by; reacting a reaction mixture comprising p-chloromethylstyrene to form a p-chloromethylstyrene homopolymer comprising chloromethyl moieties and repeating units derived from p-chloromethylstyrene; reacting the p-chloromethylstyrene homopolymer with one or more oligomers or polymers of poly(ethylene oxide) to form a graft copolymer comprising chloromethyl moieties, wherein the poly(ethylene oxide) has only one nucleophilic end; and reacting the graft copolymer comprising chloromethyl moieties with an azide compound to displace chlorine atoms of the chloromethyl moieties to form azidomethyl moieties on the graft copolymer; forming the azido-functionalized random poly(styrene-r-ethylene oxide) graft copolymer over at least a portion of a floor of a trench in a substrate to provide a trench having at least one portion of the floor bearing azido-functionalized random poly(styrene-r-ethylene oxide) graft copolymer and at least one portion of the floor exposing the substrate; forming a block copolymer material within the trench in the substrate; and annealing the block copolymer material to self-assemble the block copolymer material into first and second self-assembled domains of a first polymer block of the block copolymer material in a matrix of a second polymer block, the first self-assembled domains over the at least a portion of the floor of the trench bearing a crosslinked material of the azido-functionalized random poly(styrene-r-ethylene oxide) graft copolymer, the first self-assembled domains oriented perpendicular to the at least a portion of the floor of the trench bearing the crosslinked material of the azido-functionalized random poly(styrene-r-ethylene oxide) graft copolymer and parallel to sidewalls of the trench the second self-assembled domains over the at least a portion of the floor of the trench exposing the substrate, the second self-assembled domains oriented parallel to the floor and sidewalls of the trench.
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13. A self-assembled block copolymer structure within a trench in a substrate, the self-assembled block copolymer structure comprising:
first self-assembled domains of a block copolymer material over a crosslinked material of an azido-functionalized random poly(styrene-r-ethylene oxide) graft copolymer on at least a portion of a floor of the trench, the first self-assembled domains oriented perpendicular to the floor of the trench, the first self-assembled domains comprising a plurality of lamellar polymer domains at a pitch distance of about Lo of the block copolymer material and separated by linear openings exposing the floor of the trench. - View Dependent Claims (14, 19, 20)
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15. A self-assembled block copolymer structure within a trench in a substrate, the self-assembled block copolymer structure comprising:
first self-assembled domains of a block copolymer material over a crosslinked material of an azido-functionalized random poly(styrene-r-ethylene oxide) graft copolymer on at least a portion of a floor of the trench, the first self-assembled domains oriented perpendicular to the floor of the trench and comprising a plurality of cylinders in a hexagonal array at a pitch distance of about Lo of the block copolymer material, the floor of the trench exposed between the self-assembled domains. - View Dependent Claims (16)
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17. A self-assembled block copolymer structure within a trench in a substrate, the self-assembled block copolymer structure comprising:
first self-assembled domains of a block copolymer material over a crosslinked material of an azido-functionalized poly(styrene-r-ethylene oxide) graft copolymer on at least a portion of a floor of the trench, the first self-assembled domains oriented perpendicular to the floor of the trench and comprising a plurality of cylinders in a single array at a pitch distance of about Lo of the block copolymer material, the floor of the trench exposed between the self-assembled domains. - View Dependent Claims (18)
Specification