Classifications

• • G—PHYSICS
  • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
  • 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
  • G03F1/00—Originals for photomechanical production of textured or patterned surfaces, e.g., masks, photo-masks, reticles; Mask blanks or pellicles therefor; Containers specially adapted therefor; Preparation thereof
  • G03F1/50—Mask blanks not covered by G03F1/20 - G03F1/34; Preparation thereof
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
  • B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
  • B05D1/00—Processes for applying liquids or other fluent materials
  • B05D1/002—Processes for applying liquids or other fluent materials the substrate being rotated
  • B05D1/005—Spin coating
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
  • B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
  • B05D5/00—Processes for applying liquids or other fluent materials to surfaces to obtain special surface effects, finishes or structures
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
  • B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
  • B05D7/00—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials
  • B05D7/50—Multilayers
  • B05D7/52—Two layers
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
  • B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
  • B05D7/00—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials
  • B05D7/50—Multilayers
  • B05D7/56—Three layers or more
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B81—MICROSTRUCTURAL TECHNOLOGY
  • B81C—PROCESSES OR APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OR TREATMENT OF MICROSTRUCTURAL DEVICES OR SYSTEMS
  • B81C1/00—Manufacture or treatment of devices or systems in or on a substrate
  • B81C1/00015—Manufacture or treatment of devices or systems in or on a substrate for manufacturing microsystems
  • B81C1/00023—Manufacture or treatment of devices or systems in or on a substrate for manufacturing microsystems without movable or flexible elements
  • B81C1/00031—Regular or irregular arrays of nanoscale structures, e.g. etch mask layer
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B82—NANOTECHNOLOGY
  • B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
  • B82Y10/00—Nanotechnology for information processing, storage or transmission, e.g. quantum computing or single electron logic
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B82—NANOTECHNOLOGY
  • B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
  • B82Y40/00—Manufacture or treatment of nanostructures
• • C—CHEMISTRY; METALLURGY
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
  • C09D137/00—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a heterocyclic ring containing oxygen; Coating compositions based on derivatives of such polymers
• • C—CHEMISTRY; METALLURGY
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
  • C09D167/00—Coating compositions based on polyesters obtained by reactions forming a carboxylic ester link in the main chain; Coating compositions based on derivatives of such polymers
• • G—PHYSICS
  • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
  • 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
  • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
  • G03F7/0002—Lithographic processes using patterning methods other than those involving the exposure to radiation, e.g. by stamping
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
  • B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
  • B05D2252/00—Sheets
  • B05D2252/02—Sheets of indefinite length
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B81—MICROSTRUCTURAL TECHNOLOGY
  • B81C—PROCESSES OR APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OR TREATMENT OF MICROSTRUCTURAL DEVICES OR SYSTEMS
  • B81C2201/00—Manufacture or treatment of microstructural devices or systems
  • B81C2201/01—Manufacture or treatment of microstructural devices or systems in or on a substrate
  • B81C2201/0101—Shaping material; Structuring the bulk substrate or layers on the substrate; Film patterning
  • B81C2201/0147—Film patterning
  • B81C2201/0149—Forming nanoscale microstructures using auto-arranging or self-assembling material
• • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
  • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
  • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
  • Y10T428/00—Stock material or miscellaneous articles
  • Y10T428/24—Structurally defined web or sheet [e.g., overall dimension, etc.]
  • Y10T428/24802—Discontinuous or differential coating, impregnation or bond [e.g., artwork, printing, retouched photograph, etc.]
• • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
  • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
  • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
  • Y10T428/00—Stock material or miscellaneous articles
  • Y10T428/31504—Composite [nonstructural laminate]
  • Y10T428/31652—Of asbestos
  • Y10T428/31663—As siloxane, silicone or silane
• • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
  • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
  • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
  • Y10T428/00—Stock material or miscellaneous articles
  • Y10T428/31504—Composite [nonstructural laminate]
  • Y10T428/31855—Of addition polymer from unsaturated monomers

Definitions

• the present invention involves the use of copolymer top coats that can be spin coated onto block copolymer thin fihns and used to control the interfacial energy of the top coat-block copolymer interface.
• the top coats are soluble in aqueous weak base and can change surface energy once they are deposited onto the block copolymer thin film.
• the use of self-assembled block copolymers to produce advanced lithographic patterns relies on their orientation control in thin films. Top coats potentially allow for the facile orientation control of block copolymers which would otherwise be quite challenging.
• the invention relates to a method of applying a top coat to a block copolymer film to create a layered structure, comprising: a) providing a surface, a surface energy neutralization layer copolymer, a block copolymer, and a top coat composition comprising maleic anhydride; b) treating said surface with said surface energy neutralization layer copolymer under conditions such that a first layer on said surface is created, said layer comprising a crosslinked polymer; c) coating said first layer with block copolymer under conditions such that a second layer on said surface is created comprising a block copolymer film; and d) coating said second layer with said top coat composition so as to create a third layer on said surface, said third layer comprising a top coat on said block copolymer film surface, said first, second and third layers comprising a layered structure.
• the invention further comprises: e) treating said layered structure under conditions such that nanostructures form.
• said treating comprises annealing.
• said annealing comprises heating.
• the method further comprises: f) etching said layered structure under conditions such that the top coat and part of the block copolymer is removed revealing said nanostructures.
• said etching comprises oxygen etching.
• said surface is on a silicon wafer.
• the invention relates to the nanostructures made according to the process described above.
• said surface energy neutralization layer polymer is composed of a plurality of polymer components one of which is maleic anhydride.
• the invention relates to a layered structure comprising first, second and third layers on a surface, wherein said first layer comprises a crosslinked polymer, wherein said second layer comprises a block copolymer film, and wherein said third layer comprises maleic anhydride.
• said surface comprises silicon.
• the invention relates to a layered structure comprising first, second and third layers on a surface, wherein said first layer comprises a maleic anhydride based substrate neutralization layer, wherein said second layer comprises a block copolymer film, and wherein said third layer comprises maleic anhydride.
• said surface comprises silicon.
• the invention relates to a method to achieve block copolymer domain orientation by: a) coating block copolymer film on a substrate, b) applying a top coat on top of the block copolymer by spin coating a polymer maleic anhydride based composition dissolved in an aqueous weak base, and c) annealing.
• said annealing is by exposure to solvent vapors.
• said annealing is by heating.
• said substrate comprises silicon.
• said substrate is a silicon wafer.
• said substrate is quartz.
• said substrate is glass.
• said substrate is plastic.
• said substrate is a transparent substrate.
• said treating comprises annealing. In one embodiment, said annealing comprises heating. In one embodiment, the invention further comprises: e) etching said layered structure under conditions such that the topcoat and part of the block copolymer is removed revealing said nanostructures. In one embodiment, said block copolymers form nano structured materials that can be used as etch masks in lithographic patterning processes. In one embodiment, a third monomer is provided and said block copolymer is a triblock copolymer. In one embodiment, the invention is related to the etched nanostructures made according to the process described above. In one embodiment, said etching comprises oxygen etching.
• said nanostructures are selected from the group consisting of: lamellae, cylinders, vertically aligned cylinders, horizontally alligned cylinders, spheres, gyroids, network structures, and hierarchical nanostructures.
• said nanostructures comprise cylindrical structures, said cylindrical structures being substantially vertically aligned with respect to the plane of the surface.
• the proportions of the components can be varied such that the surface energy of the layer is varied.
• the surface energy switches as the treatment composition is thermally annealed.
• applying the surface energy neutralizing layer comprises: dissolving said surface energy neutralizing layer polymer in a solvent; spin coating the surface energy neutralizing layer polymer upon the surface; cross-linking by exposure to 250 °C for 5 minutes; and subsequently washing with solvent.
• said solvent is toluene.
• the invention relates to a method of applying a top coat to a block copolymer film to create a layered structure, comprising: a) providing a surface, a surface energy neutralization layer polymer, a block copolymer, and a top coat composition comprising maleic anhydride; b) treating said surface with said surface energy neutralization layer polymer under conditions such that a first layer on said surface is created, said layer comprising a crosslinked polymer; c) coating said first layer with block copolymer under conditions such that a second layer on said surface is created comprising a block copolymer film; and d) coating said second layer with said top coat composition so as to create a third layer on said surface, said third layer comprising a top coat on said block copolymer film surface, said first, second and third layers comprising a layered structure.
• said top coat composition is dissolved in an aqueous weak base prior to step d) to create a casting solvent.
• said weak base is aqueous ammonium hydroxide and wherein the maleic anhydride opens and forms the ammonium salt of the corresponding maleic acid.
• said block-co-polymer is not soluble in the casting solvent.
• the method further comprises e) treating said layered structure under conditions such that nanostructures form.
• the method further comprises e) treating said layered structure under conditions such that nanostructures form.
• said treating comprises annealing.
• said annealing comprises heating.
• the method further comprises f) etching said layered structure under conditions such that the top coat and part of the block copolymer is removed revealing said nanostructures.
• said etching comprises oxygen etching.
• said a surface energy neutralization layer polymer comprises maleic anhydride.
• said surface energy neutralization layer polymer is dissolved in an aqueous weak base prior to step b) to create a casting solvent.
• said base is aqueous ammonium hydroxide and wherein the maleic anhydride opens and forms the ammonium salt of the corresponding maleic acid.
• said surface energy neutralization layer polymer is composed of various polymer components one of which is maleic anhydride.
• said surface energy neutralization layer polymer components must be soluble in aqeous base. In one embodiment, the proportions of the components can be varied such that the surface energy of the surface energy neutralization layer polymer layer is varied. In one embodiment, the surface energy switches as the surface energy neutralization layer polymer is baked. In one embodiment, said top coat composition is composed of various polymer components one of which is maleic anhydride. In one embodiment, said top coat components must be soluble in aqeous base. In one embodiment, the proportions of the components can be varied such that the surface energy of the top coat layer is varied. In one embodiment, the surface energy switches as the top coat is baked. In one embodiment, said surface is on a silicon wafer.
• the invention relates to the nano structures made according to the process above.
• said surface is treated under conditions such that said surface energy neutralization layer polymer is cross-linked to said surface comprises: i) dissolving said surface energy neutralization layer polymer in a solvent; ii) spin coating the surface energy neutralization layer upon the surface; iii) cross-linking by exposure to 250 °C for 5 minutes; and iv) subsequently washing with solvent.
• said solvent is toluene.
• said nanostructures comprise cylindrical structures, said cylindrical structures being substantially vertically aligned with respect to the plane of the surface.
• said a surface energy neutralization layer polymer comprises maleic anhydride.
• said surface energy neutralization layer polymer is dissolved in an aqueous weak base prior to step b) to create a casting solvent.
• said base is aqueous ammonium hydroxide and wherein the maleic anhydride opens and forms the ammonium salt of the corresponding maleic acid.
• the invention relates to a method of applying a top coat to a block copolymer film to create a layered structure, comprising 1) a surface energy neutralization layer polymer is dissolved in toluene and spin coated, 2) the surface energy neutralization layer polymer is cross-linked at 250 °C for 5 min, 3) Washed with toluene 2 times, 4) Block copolymer is dissolved in toluene and spin coated, 5) Post apply bake at 110 °C for 1 minute, 6) Top coat polymer is dissolved in 30 wt% H 4 OH and spin-coated, 7) Post apply bake at 150 °C for 5 minutes; 8) Anneal the thin films at 170 °C for 18 hours.
• the invention relates to a method of producing a domain orientation controlled block copolymer film, comprising: a) providing a surface, a surface energy neutralization layer, block copolymer, and a random copolymer top coat comprising at least one maleic anhydride unit; b) treating said surface under conditions such that said surface energy neutralization layer is cross-linked on said surface; c) coating said surface with surface energy neutralization layer with block copolymer under such conditions so as to create a block copolymer film; d)aqueous spin coat deposition of said random copolymer top coat onto said coated block copolymer film surface; and e) treating said film under conditions such that nanostructures form.
• said nanostructures comprise cylindrical structures, said cylindrical structures being substantially vertically aligned with respect to the plane of the surface.
• said surface is on a silicon wafer.
• the invention is the film made according to the process described above.
• said surface is treated under conditions such that said surface energy neutralization layer is cross-linked to said surface comprises: i) dissolving said surface energy neutralization layer polymer in a solvent; ii) spin coating the surface energy neutralization layer polymer upon the surface; iii) cross-linking by exposure to 250 °C for 5 minutes; and iv) subsequently washing with solvent.
• said solvent is toluene.
• said surface energy neutralization layer polymer is a surface energy neutralizing agent.
• said surface energy neutralizing agent include but are not limited to cross-linkable random copolymers comprised of polystyrene and poly(methyl methacrylate) and substituted derivatives : .
• substrate surface energy neutralization layer layers can be crosslinked random copolymers, they could also be comprised of other moleculas like substituted silanes which actually react with the surface chemistry or in a special case there may be not substrate surface energy neutralization layer required
• said surface energy neutralization layer polymer is selected from the group comprising:
• said conditions to create a block copolymer film comprise: i) dissolving said block copolymer in a solvent; ii) spin coating the block copolymer upon the surface cross-linked with surface energy neutralization layer polymer; and iii)subsequently baking for 110 °C for 1 minutes.
• said solvent is toluene.
• the method further comprises step e) comprises heating the thin film at 170 °C for 18 hours.
• the invention comprises the etched nanostnictures made according to the process of described above.
• the invention comprises a layered structure comprising first, second and third layers on a surface, wherein said first layer comprises a crosslinked polymer, wherein said second layer comprises a block copolymer film, and wherein said third layer comprises a surface energy neutralization layer polymer has been deposited by spin coat treatment.
• said surface comprises silicon, i one embodiment, the invention relates to the etched nanostructures made according to the process of described above.
• said surface is on a silicon wafer.
• said silicon wafer has a surface energy neutralization layer polymer.
• said surface energy neutralization layer polymer has been deposited by spin coat treatment upon the surface of said silicon wafer.
• the block copolymers form nano structured materials that can be used as etch masks in lithographic patterning processes.
• one of the blocks is polytrimethylsilylstyrene.
• said first monomer is trimethyl-(2-methylene-but-3-enyl)silane.
• said first monomer is a silicon-containing methacrylate.
• said first monomer is methacryloxymethyltrimethylsilane (MTMSMA).
• MTMSMA methacryloxymethyltrimethylsilane
• a third monomer is provided and said block copolymer is a triblock copolymer.
• the invention relates to the etched nanostructures made according to the process described above.
• Figure 1 shows the ring opening and closing of polymeric maleic anhydride and polymeric maleic acid.
• Figure 2 shows non-limiting structures of illustrative silicon-containing monomers and polymers.
• Figure 4 shows the basic concept of the top coat spincoated containing maelic anhydride as a key component.
• Figure 6 shows an example of random copolymer top coat polymers.
• Figure 7 shows some examples of polymer components that could be used in combination with other components along with maleic acid components for formulating top coat polymers layers or surface energy neutralization layer.
• Figure 8 shows fluorinated components that could be used in combination with other components along with maleic acid components for formulating top coat polymers layers or surface energy neutralization layer.
• Figure 9 shows a number of top coat polymer combinations already produced, component ratios are indicated in some cases.
• Figure 10 shows that water contact angle and surface energy change as a function of amiealing a thin film, because maleic anhydride ring opens and closes. Longer annealing times correspond to the ring closed form (higher contact angle because it is less polar, dislikes water). Ring opened anionic form is aqueous weak base soluble, ring closes to lower the surface energy once it is applied to the thin film and annealed.
• Figure 11 further explains proof of ring opening and closing in the applied coat.
• Figure 12 shows the processing of the layered structures into etched thin copolymer films who's block copolymer domain orientation is determined by applying the top coat and annealing before oxygen etching.
• Figure 13 shows a diagram of the construction process for the creation of the layers to be subsequently processed for orientation.
• 1) Surface energy neutralization layer polymer is dissolved in toluene and spin coated, 2) Cross-linked at 250 °C for 5 min, 3) Washed with toluene 2 times, 4) Block copolymer is dissolved in toluene and spin coated, 5) Post apply bake at 110 °C for 1 minute, 6) Top coat is dissolved in 30 wt% i 4 OH and spin-coated, and 7) Post apply bake at 150 °C for 5 minutes.
• Figure 14 shows a diagram of the annealing of the thin film to produce the desired block copoloymer orientation and subsequent oxygen plasma etching of the block copoloymer under the described conditions.
• 8) Anneal the thin films at 170 °C for 18 hours.
• 9) Strip the top coat by spinning the wafer at 3000 rpm and applying 10 drops of 30 wt% NH 4 OH aqueous solution dropwise.
• Figure 15 shows transmission electron microscope image of an etched thin film with the desired orientation.
• BCP Thickness before anneal 65.6 nm
• after stripping the top coat 66.9 nm
• film has been etched with 0 2 plasma, and demonstrates perpendicular lamellar features.
• Figure 16 shows transmission electron microscope image of an etched thin film with the desired orientation.
• BCP Thickness before anneal 34 nm, film has been etched with 0 2 plasma, and demonstrates perpendicular lamellar features.
• Figure 17 shows transmission electron microscope image of an etched thin film with the desired orientation.
• BCP Thickness 29.4 nm film has been etched with 0 2 plasma, and demonstrates perpendicular lamellar features.
• Figure 18 shows transmission electron microscope image of an etched thin film with the desired orientation.
• the film has been etched with 0 2 plasma, and demonstrates perpendicular lamellar features.
• Figure 19 shows a diagram of the construction process for the creation of the layers to be subsequently processed for orientation.
• l)Top coat is dissolved in 30 wt% ⁇ 40 ⁇ and spin coated, 2)Post apply bake at 150 °C for 5 minutes, 3) Block copolymer is dissolved in toluene and spin coated, 4) Post apply bake at 110 °C for 1 minute, 5) Top coat polymer is dissolved in 30 wt% NH 4 OH and spin-coated, 6) Post apply bake at 150 °C for 5 minutes;
• Figure 20 shows a diagram of an alternative annealing of the thin film to produce the desired block copoloymer orientation and subsequent oxygen plasma etching of the block copoloymer under the described conditions.
• atoms making up the compounds of the present invention are intended to include all isotopic forms of such atoms.
• Isotopes include those atoms having the same atomic number but different mass numbers.
• isotopes of hydrogen include tritium and deuterium
• isotopes of carbon include 13 C and 14 C.
• one or more carbon atom(s) of a compound of the present invention may be replaced by a silicon atom(s).
• one or more oxygen atom(s) of a compound of the present invention may be replaced by a sulfur or selenium atom(s).
• weak base refers to a chemical base that does not ionize fully in an aqueous solution.
• surface energy neutralization layer is the same as the “substrate energy neutralization layer.”
• the volume fraction of one of the blocks is 40-60, more preferably 50-50 and the degree of polymerization (N) and Flory-Huggins interaction parameter of the block copolymer is preferably greater than 10.5 and is more preferably greater than 25.
• the block copolymer or blend thereof can be cross-linked by any convenient method.
• the block copolymer or blend thereof is deposited as a film or coating and then cross-linked using UV light or ionizing radiation.
• free radical initiators or prorads may be added to the block copolymer or blend thereof in order to assist the cross-linking reaction.
• the block copolymer or blend thereof comprises a cross-linking agent, especially when the block copolymer or blend thereof is used in a film-forming or coating composition.
• the cross-linking agent and concentration of cross-linking agent are chosen such that the rate constant of the cross-linking reaction is relatively slow, thereby giving a relatively long pot life for the film-forming or coating composition.
• the rate constant of the cross-linking reaction is such that the speed of cross-linking is slower than the speed of self-assembly of the block copolymer or blend thereof.
• the block copolymer or blend thereof can be cross-linked by any convenient method.
• the block copolymer or blend thereof is deposited as a film or coating and then cross-linked using UV light or ionizing radiation.
• free radical initiators or prorads may be added to the block copolymer or blend thereof in order to assist the cross-linking reaction.
• the block copolymer or blend thereof comprises a cross-linking agent, especially when the block copolymer lor blend thereof is used in a film-forming or coating composition.
• the cross-linking agent and concentration of cross-linking agent are chosen such that the rate constant of the cross-linking reaction is relatively slow, thereby giving a relatively long pot life for the film- forming or coating composition. This is particularly important when the film-forming composition or coating composition is to be used as a printing ink or deposited using ink jet printing technology.
• the rate constant of the cross-linking reaction is such that the speed of cross-linking is slower than the speed of self-assembly of the block copolymer or blend thereof.
• Glass transition temperature is represented by the abbreviation T g
• Vitrification occurs when the glass transition temperature, T g , rises to the isothermal temperature of cure, as described in Gillham, J. K. (1986) [10].
• silylating agents also known as silanes or self-assembled monolayers
• organosilicon compounds with methoxy, ethoxy, or halide functionalities.
• Some non-limiting examples include methyldichlorosilane, methyldiethoxysilane, allyl(chloro)dimethylsilane, and (3-amniopropyl) triethoxysilane.
• brush polymers are a class of polymers that are adhered to a solid surface [11].
• the polymer that is adhered to the solid substrate must be dense enough so that there is crowding among the polymers which then, forces the polymers to stretch away from the surface to avoid overlapping. [12]
• Roll-to-roll processing also known as web processing, reel-to-reel processing or R2R
• R2R reel-to-reel processing
• a thin- film solar cell also called a thin-film photovoltaic cell (TFPV)
• TFSC thin-film photovoltaic cell
• Possible roll-to-roll substrates include, but are not limited to metalized polyethylene terphthalate, metal film (steel), glass films (e.g. Corning Gorilla Glass), graphene coated films, polyethylene naphthalate (Dupont Teonex), and Kapton film., polymer films, metalized polymer films, glass or silicon, carbonized polymer films, glass or silicon. Possible polymer films include polyethylene terephthalate, kapton, mylar, etc.
• a block copolymer consists of two or more polymeric chains (blocks), which are chemically different and covalently attached to each other.
• Block copolymers are being suggested for many applications based primarily on their ability to form nanometer scale patterns. These self-assembled patterns are being considered as nanohthographic masks as well as templates for the further synthesis of inorganic or organic structures. Such applications are made possible by taking advantage of contrasts in chemical or physical properties that lead to differential etch rates or attractions to new materials. New applications in, for example, fuel cells, batteries, data storage and optoelectronic devices generally rely on the inherent properties of the blocks. All of these uses depend on the regular self-assembly of block copolymers over macroscopic distances.
• Trimethyl(4-vinylphenyl)silane is another example of a styrene derivative and is
• Tert-butyldimethyl(4-vinylphenoxy)silane is another example of a styrene derivative
• Tert-butyldimethyl(oxiran-2-ylmethoxy)silane is an example of a silicon containing compound and is represented by the following structure:
• TMSS-Sty is represented by the following structure:
• the polymer X is represented by the following structure:
• the present invention also contemplates styrene "derivatives" where the basic styrene structure is modified, e.g. by adding substituents to the ring.
• Derivatives of any of the compounds shown in Figure 2 or Figure 3 can also be used.
• Derivatives can be, for example, hydroxy-derivatives or halo-derivatives.
• the block copolymer be used to create "nano structures" on a surface, or "physical features" with controlled orientation.
• These physical features have shapes and thicknesses.
• various structures can be formed by components of a block copolymer, such as vertical lamellae, in-plane cylinders, and vertical cylinders, and may depend on film thickness, surface energy neutralization layer, and the chemical properties of the blocks.
• said cylindrical structures being substantially vertically aligned with respect to the plane of the first film.
• Orientation of structures in regions or domains at the nanometer level i.e. "microdomains" or “nanodomains”
• domain spacing of the nano structures is approximately 50 nm or less.
• the methods described herein can generate structures with the desired size, shape, orientation, and periodicity. Thereafter, in one embodiment, these structures may be etched or otherwise further treated.
• the present invention involves the use of copolymer top coats that can be spin coated onto block copolymer thin films and used to control the interfacial energy of the top coat-block copolymer interface or as shown in Figure 19 & Figure 20, can be used to control block copolymer substrate interfacial energy.
• the top coats are soluble in aqueous weak base and can change surface energy once they are deposited onto the block copolymer thin film.
• the use of self-assembled block copolymers to produce advanced lithographic patterns relies on their orientation control in thin films. Top coats potentially allow for the facile orientation control of block copolymers which would otherwise be quite challenging.
• monomers that have lower surface energies than maleic anhydride can be used to decrease the overall surface energy of the top coat or surface energy neutralization layer as shown in Figure 8.
• the copolymer top coat is composed of maleic anyhydride and other monomers which can can be combined in various ratios to achieve a desired overall surface energy.
• the copolymer top coat is composed of three components M-N-L, of which M must be maleic acid or a maleic acid derivative.
• the variation of the amounts of the M-N-L components allows for fine tuning for the surface energy and its interaction with a block copolymer layer.
• the copolymer top coat monomers can be soluble in aqueous weak base to enable spin coat application.
• the copolymer top coat can be combined in ratios, provided at least one of the monomers is a maleic acid or maleic anyhydride deriviative.
• the copolymer top coat is removed by spinning the surface an applying a solution of an aqueous weak base, such as ammonium hydroxide (NH 4 OH).
• the maleic acid Upon annealing, the maleic acid reforms the anhydride (see Figure 1), which results in the loss of water and ammonia and changes the surface energy of the top coat to be closer to that of the block copolymer domains.
• Figure 1 This is compared with present technologies that use water-soluble polymers to allow for top coats to be spin-coated on top of block copolymer thin films, but the top coats do not change surface energy after they are deposited.
• the adjustable nature of the ratios of the top coat co-polymer monomers enables one to fine tune the surface energy of the deposited top which may enable improved orientation control of the block copolymers underneath.
• the top coat would have a surface energy intermittent to that of all the blocks contained in block copolymer, such that the interaction energy between each block and the top coat is the same, creating no preference for a specific block to exclusively be in contact with the top coat.
• multiple blocks can interact with the top coat and produce perpendicular features.
• the copolymer surface energy neutralization layer is composed of maleic anyhydride and other monomers which can include, but are not limited to functionalized methacrylates, acrylates, norbornenes, styrenes, butadienes, isoprenes, lactides, and ethylene oxides some examples of which are found in Figure 7.
• monomers that have lower surface energies than maleic anhydride such as fluorinated monomers of the type aforementioned, can be used to decrease the overall surface energy of the surface energy neutralization layer as shown in Figure 8.
• the copolymer top coat is composed of maleic anyhydride and other monomers which can be combined in various ratios to achieve a desired overall surface energy.
• both the top coat and the surface energy neutralization layer are both polymers that contain a maleic acid or maleic anyhydride deriviative. In one embodiment, both the top coat and the surface energy neutralization layer are both polymers that contain a maleic acid or maleic anyhydride deriviative, but have different mixtures of M-N-L components.
• the present invention provides advantages over current technologies.
• Current technologies have started to discuss the use of water soluble polymers as top coats, because they can be spin coated onto hydrophobic block copolymers without destroying the block copolymer thin film.
• water soluble polymers are polar, which inherently means they have high surface energies and are thus likely to have a surface energy which is too high and does not fall in the range required to produce perpendicular block copolymer features.
• the present invention overcomes these problems by having a reversible ring-opening and ring-close maleic anhydride component in the top coat random copolymer.
• the polymer In the ring-opened form the polymer is soluble in aqueous weak base, which allows the top coat to be spin coated onto the block copolymer (see Figure 1).
• the ring-closed maleic anhydride reforms during a post-apply bake, which reduces the polarity of the top coat significantly and brings the surface energy of the top coat closer to that of the block copolymer domains, promoting block copolymer orientation control.
• the block copolymer be used to create "nanostructures" on a surface, or "physical features" with controlled orientation.
• These physical features have shapes and thicknesses.
• various structures can be formed by components of a block copolymer, such as vertical lamellae, in-plane cylinders, and vertical cylinders, and may depend on film thickness, surface energy neutralization layer, and the chemical properties of the blocks.
• said cylindrical structures being substantially vertically aligned with respect to the plane of the first film. Orientation of structures in regions or domains at the nanometer level (i.e. "microdomains" or “nanodomains”) may be controlled to be approximately uniform, and the spatial arrangement of these structures may also be controlled.
• Block copolymers used in nanoscale lithographic patterning typically self-assemble to produce structures with characteristic sizes from 10-lOOnm.
• the invention includes the block together with a silicon containing synthetic block, the combination of which provides very high etch selectivity.
• the invention is a potential solution to overcoming the feature-size limitations of conventional lithography techniques involves using self-assembled block copolymers to pattern nanoscale features.
• Block copolymer lithography circumvents physical and cost limitations present in conventional lithography techniques. Polymers with high segregation strength can form features much smaller than those achievable by photolithography and can do so using a less time-intensive process than electron beam lithography. This can be overcome by incorporating crosslinking functional groups within the polymer structure.
• the top coat layer is composed of various polymer components.
• maleic anhydride is a constant component.
• the topcoat components must be soluble in aqeous base.
• the proportions of the components can be varied such that the surface energy of the top coat layer is varied.
• the surface energy switching is the result of maleic anhydride ring closing. Examples of top coat components are shown in Figure 9.
• the invention comprises a layered structure comprising first, second and third layers on a surface, wherein said first layer comprises a crosslinked polymer, wherein said second layer comprises a block copolymer film, and wherein said third layer comprises maleic acid.
• the layered structure, wherein said surface comprises silicon.
• a layered structure comprising first, second and third layers on a surface, wherein said first layer comprises a maleic acid based substrate neutralization layer, wherein said second layer comprises a block copolymer film, and wherein said third layer comprises maleic acid.
• the layered structure, wherein said surface comprises silicon.
• the method of applying spincoated copolymer surface energy neutralization layer to block-copolymers to provide a neutralizing interface to allow the formation of nanostructures could be used to allign liquid crystals.
• said aligned liquid crystals are useful for displays.
• Top coat is dissolved in 30 wt% NH40H and spin coated, 2)Post apply bake at 150 °C for 5 minutes for a substrate neutralization layer, 3) Block copolymer is dissolved in toluene and spin coated, 4) Post apply bake at 110 °C for 1 minute, 5) Top coat polymer is dissolved in 30 wt% NH 4 OH and spin-coated, 6) Post apply bake at 150 °C for 5 minutes; 7) Anneal the thin films at 170 °C for 18 hours. 8) Strip the top coat by spinning the wafer at 3000 rpm and applying 10 drops of 30 wt% NH 4 OH aqueous solution dropwise.
• Block Copolymer Lithography Periodic Arrays of -1011 Holes in 1 Square Centimeter, Science 276(5317), 1401-1404.

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