# US 8,785,559 B2 · Crosslinkable graft polymer non-preferentially wetted by polystyrene and polyethylene oxide > Agents: this data is available as JSON from the patentgrep API and MCP server — see https://patentgrep.com/llms.txt - Number: US 8,785,559 B2 - Document ID: US8785559B2 - Status: Granted - Kind: B2 - Application number: 13/934,676 - Filed: 2013-07-03 - Published: 2013-11-07 - Granted: 2014-07-22 - Earliest claimed: 2007-06-19 - Assignees: Micron Technology, Inc. - Applicants: Micron Technology, Inc. - Inventors: Dan B. Millward - Web page: https://patentgrep.com/patent/US8785559B2 ## CPC - G03F 7/40: Treatment after imagewise removal, e.g. baking - B32B 3/10: characterised by a discontinuous layer, i.e. formed of separate pieces of material - B81C 1/00031: {Regular or irregular arrays of nanoscale structures, e.g. etch mask layer (photomechanical, e.g. photolithographic, production of textured or patterned surfaces G03F7/00; lithographic processes for making patterned surfaces using printing and stamping G03F7/0002)} - B82Y 30/00: Nanotechnology for materials or surface science, e.g. nanocomposites - C08G 81/02: at least one of the polymers being obtained by reactions involving only carbon-to-carbon unsaturated bonds - G03F 7/12: Production of screen printing forms or similar printing forms, e.g. stencils - B81C 2201/0149: Forming nanoscale microstructures using auto-arranging or self-assembling material - B81C 2201/0198: for making a masking layer - Y10T 428/24174: including sheet or component perpendicular to plane of web or sheet - Y10T 428/24182: Inward from edge of web or sheet - Y10T 428/24521: with component conforming to contour of nonplanar surface - Y10T 428/24612: Composite web or sheet - G03F: PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR; (phototypographic composing devices B41B; photosensitive materials or processes for photographic purposes G03C; electrophotography, sensitive layers or processes therefor G03G) - B32B: LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM - B81C: PROCESSES OR APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OR TREATMENT OF MICROSTRUCTURAL DEVICES OR SYSTEMS (making microcapsules or microballoons B01J13/02; processes or apparatus specially adapted for the manufacture or treatment of piezoelectric, electrostrictive or magnetostrictive elements per se H10N30/01) - B82Y: SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES - C08G: MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS - Y10T: TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION ## 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. ## Claims ### Claim 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. ### Claim 2 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 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. ### Claim 3 (depends on 1) The method of claim 1, wherein annealing the block copolymer material to self-assemble the block copolymer material comprises: forming lamella domains over 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, the lamella 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 the sidewalls; and forming half-cylindrical domains over the at least a portion of the floor of the trench exposing the substrate, the half-cylindrical domains oriented parallel to the floor and sidewalls of the trench. ### Claim 4 (depends on 1) The method of claim 1, wherein annealing the block copolymer material to self-assemble the block copolymer material comprises: forming cylindrical domains over 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, the cylindrical 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 the sidewalls; and forming half-cylindrical domains over the at least a portion of the floor of the trench exposing the substrate, the half-cylindrical domains oriented parallel to the floor and sidewalls of the trench. ### Claim 5 (depends on 4) The method of claim 4, wherein forming cylindrical domains over 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 comprises forming cylindrical domains in a hexagonal array perpendicular to the floor of the trench and parallel to the sidewalls. ### Claim 6 (depends on 4) The method of claim 4, wherein forming cylindrical domains over 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 comprises forming cylindrical domains in a single array perpendicular to the floor of the trench and parallel to the sidewalls. ### Claim 7 (depends on 1) The method of claim 1, further comprising selectively removing the second polymer block of the block copolymer material to provide a self-assembled structure within the trench, the self-assembled structure comprising a plurality of linear openings exposing the substrate and separated by lamellar domains of the first polymer block, the lamellar domains of the first polymer block supported by 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. ### Claim 8 (depends on 1) The method of claim 1, further comprising selectively removing the first polymer block of the block copolymer material to provide a self-assembled structure within the trench, the self-assembled structure comprising a plurality of linear openings exposing the substrate and separated by lamellar domains of the second polymer block, the lamellar domains of the second polymer block supported by 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. ### Claim 9 (depends on 1) The method of claim 1, further comprising selectively removing the second polymer block of the block copolymer material to provide a self-assembled structure within the trench, the self-assembled structure comprising a plurality of cylinders of the first polymer block supported by 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, the plurality of cylinders arranged in a hexagonal array at a pitch distance of about Lo of the block copolymer material, the plurality of cylinders oriented perpendicular to the floor of the trench. ### Claim 10 (depends on 1) The method of claim 1, further comprising selectively removing the second polymer block of the block copolymer material to provide a self-assembled structure within the trench, the self-assembled structure comprising a plurality of cylinders of the first polymer block supported by 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, the plurality of cylinders arranged in a single array at a pitch distance of about Lo of the block copolymer material, the plurality of cylinders oriented perpendicular to the floor of the trench. ### Claim 11 (depends on 1) The method of claim 1, further comprising selectively removing the first polymer block of the block copolymer material to provide a self-assembled structure within the trench, the self-assembled structure comprising a plurality of cylindrical openings in a hexagonal array within the matrix of the second polymer block, the plurality of cylindrical openings exposing the floor of the trench and oriented perpendicular to the floor of the trench. ### Claim 12 (depends on 1) The method of claim 1, further comprising selectively removing the first polymer block of the block copolymer material to provide a self-assembled structure within the trench, the self-assembled structure comprising a plurality of cylindrical openings in a single array within the matrix of the second polymer block, the plurality of cylindrical openings exposing the floor of the trench and oriented perpendicular to the floor of the trench. ### Claim 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. ### Claim 14 (depends on 13) The self-assembled block copolymer structure of claim 13, further comprising: second self-assembled domains of the block copolymer material over at least a portion of the floor of the trench exposing the substrate, the second self-assembled domains comprising half-cylindrical domains oriented parallel to the sidewalls and the floor of the trench. ### Claim 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. ### Claim 16 (depends on 15) The self-assembled block copolymer structure of claim 15, further comprising: second self-assembled domains of the block copolymer material over at least a portion of the floor of the trench exposing the substrate, the second self-assembled domains comprising half-cylindrical domains oriented parallel to the substrate and the sidewalls. ### Claim 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. ### Claim 18 (depends on 17) The self-assembled block copolymer structure of claim 17, further comprising: second self-assembled domains of the block copolymer material over at least a portion of the floor of the trench exposing the substrate, the second self-assembled domains comprising half-cylindrical domains oriented parallel to the substrate and the sidewalls. ### Claim 19 (depends on 13) The self-assembled block copolymer structure of claim 13, wherein the block copolymer material comprises poly(styrene-b-ethylene oxide) block copolymer. ### Claim 20 (depends on 13) The self-assembled block copolymer structure of claim 13, wherein the linear openings are about 5 nm to 60 nm wide.