Classifications

• • 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
  • C09D183/00—Coating compositions based on macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon, with or without sulfur, nitrogen, oxygen, or carbon only; Coating compositions based on derivatives of such polymers
• • 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
  • B81C1/00388—Etch mask forming
  • B81C1/00428—Etch mask forming processes not provided for in groups B81C1/00396 - B81C1/0042
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
  • C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
• • 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
  • C09D153/00—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
• • 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
  • 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
• • 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

Definitions

• the invention relates to a method for the creation of nanometric structures by self - assembly of block copolymers, at least one of which blocks is crystallizable or has at least one liquid crystal phase.
• the invention also relates to the use of these materials in the fields of lithography (lithography masks), the storage of information but also the production of porous membranes or as a catalyst support.
• the invention also relates to the block copolymer masks obtained according to the method of the invention.
• Block copolymers it is possible to structure the arrangement of the constituent blocks of the copolymers, by phase segregation between the blocks thus forming nano-domains, at scales of less than 50 nm. Because of this ability to nano-structure, the use of Block copolymers in the fields of electronics or optoelectronics are now well known.
• block copolymer films in particular based on polystyrene-poly (methyl methacrylate), noted hereinafter PS-b-PMMA, appear as very promising solutions because they allow you to create patterns with high resolution.
• a block of the copolymer film In order to be able to use such a block copolymer film as an etching mask, a block of the copolymer must be selectively removed to create a porous film of the residual block, the patterns of which can be subsequently transferred by etching to an underlying layer.
• the minority block that is, PMMA (Poly (methyl methacrylate)
• PS Polystyrene
• the nano-domains must be oriented perpendicular to the surface of the underlying layer.
• Such structuring of the domains requires special conditions such as the preparation of the surface of the underlying layer, but also the composition of the block copolymer.
• the ratios between the blocks make it possible to control the shape of the nano-domains and the molecular mass of each block makes it possible to control the dimension of the blocks.
• Another very important factor is the phase segregation factor, also referred to as the Flory-Huggins interaction parameter and denoted "X".
• This parameter makes it possible to control the size of the nano domains. More particularly, it defines the tendency of blocks of the block copolymer to separate into nano-domains.
• the product ⁇ of the degree of polymerization, N, and the Flory-Huggins parameter ⁇ gives an indication of the compatibility of two blocks and if they can separate. For example, a di-block copolymer of symmetrical composition separates into micro-domains if the product ⁇ is greater than 10. If this product ⁇ is less than 10, the blocks mix and the phase separation is not observed.
• US Patents 8304493 and US 8450418 describe a process for modifying block copolymers as well as modified block copolymers. These modified block copolymers have a value of the modified Flory-Huggins interaction parameter, such that the block copolymer has nano-domains of small sizes.
• a block copolymer of which at least one of the blocks is crystallizable or having at least one liquid crystal phase, has the following advantages when it is deposited on a surface:
• a rapid self-assembly kinetics (between 1 and 20 minutes) for low molecular weights leading to domain sizes well below 10 nm, and at low temperatures (between 333 and 603 K and preferably between 373K and 603K).
• the invention relates to a nano - structured assembly process using a composition comprising a block copolymer of which at least one of the blocks is crystallizable or has at least one liquid crystal phase and comprising the following steps: - Solution of the block copolymer in a solvent. -Deposit of this solution on a surface.
• surface is meant a surface that can be flat or non-planar.
• annealing is meant a step of heating at a certain temperature for one evaporation of the solvent when it is present, and allowing the establishment of the nanostructuring searched in a given time ( ⁇ self assembly). Annealing also means the establishment of nano-structuring of the block copolymer film when said film is subjected to a controlled atmosphere of solvent vapors (s), these vapors giving the polymer chains sufficient mobility for s' arrange by themselves on the surface.
• solvent vapors solvent vapors
• Any block copolymer may be used in the context of the invention, be it diblock copolymer, linear or star triblock, linear multiblock, comb or as a star, provided that at least blocks of the block copolymer is crystallizable or has at least one liquid crystal phase.
• these are diblock or triblock copolymers, and more preferably diblock copolymers.
• copolymers may be synthesized by any techniques known to those skilled in the art among which polycondensation, ring-opening polymerization, anionic, cationic or radical polymerization may be mentioned, these techniques being able to be controlled or not.
• radical polymerization they may be controlled by any known technique such as NMP ("Nitroxide Mediated Polymerization"), RAFT ("Reversible Addition and Fragmentation Transfer”), ATRP ("Atom Transfer Radical Polymerization") , INIFERTER ("Initiator-Transfer-Termination”), RITP ("Reverse Iodine Transfer Polymerization"), ITP (“Iodine Transfer Polymerization”).
• crystallizable block or having at least one liquid crystal phase is meant a block having at least one measurable transition temperature by differential enthalpic analysis, whether it be a crystal-> smectic, smectic-> nematic, nematic-
• the block copolymer having a liquid crystal block may be a block copolymer having a lyotropic or thermotropic block.
• the block copolymer having a crystallizable block may be block copolymer having a crystalline or semi-crystalline block.
• the crystallizable blocks or having at least one liquid crystal phase may be of any type but preferably they will be chosen such that the Flory-Huggins parameter ⁇ of the block copolymer is between 0.01 and 100 and preferably between 0.04 and 25.
• the blocks which are not crystallizable or do not exhibit a liquid crystal phase consist of the following monomers: at least one vinyl, vinylidene, diene, olefinic, allylic or (meth) acrylic or cyclic monomer.
• These monomers are chosen more particularly from vinylaromatic monomers such as styrene or substituted styrenes, in particular alpha-methylstyrene, and acrylic monomers such as alkyl, cycloalkyl or aryl acrylates, such as methyl acrylate, dicyclohexyl acrylate and the like. ethyl, butyl, ethylhexyl or phenyl, ether alkyl acrylates such as 2-methoxyethyl acrylate, alkoxy- or aryloxypolyalkyleneglycol acrylates such as methoxypolyethylene glycol acrylates, ethoxypolyethylene glycol acrylates and the like.
• vinylaromatic monomers such as styrene or substituted styrenes, in particular alpha-methylstyrene
• acrylic monomers such as alkyl, cycloalkyl or aryl acrylates, such as methyl
• methoxypolypropylene glycol acrylates methoxypolyethylene glycol-polypropylene glycol acrylates or mixtures thereof, aminoalkyl acrylates such as 2- (dimethylamino) ethyl acrylate (ADAME), fluorinated acrylates, phosphorus acrylates such as alkylene glycol phosphate acrylates, glycidyl acrylates, dicyclopentenyloxyethyl acrylates, alkyl, cycloalkyl, alkenyl or aryl methacrylates such as methyl methacrylate (MMA), lauryl, cyclohexyl, allyl, phenyl or naphthyl, ether alkyl methacrylates such as 2-ethoxyethyl methacrylate, alkoxy- or aryloxy-polyalkylene glycol methacrylates such as methoxypolyethylene glycol methacrylates, ethoxypolyethylene glycol methacrylates
• acrylamide or substituted acrylamides 4-acryloylmorpholine, N-methylolacrylamide, methacrylamide or substituted methacrylamides, N-methylolmethacrylamide, methacrylamido-propyltrimethyl ammonium chloride (MAPTAC), glycidyl, dicyclopentenyloxyethyl methacrylates, anhydride maleic, alkyl or alkoxy- or aryloxy-polyalkylene glycol maleates or hemimaleate, vinylpyridine, vinylpyrrolidinone, (alkoxy) poly (alkylene glycol) vinyl ether or divinyl ether, such as methoxy poly (ethylene glycol) vinyl ether, poly (ethylene glycol) divinyl ether, olefinic monomers, among which mention may be made of ethylene, butene, hexene and 1-octene, diene monomers including butadiene, isoprene and fluorinated olefinic monomers
• the block copolymer is synthesized, it is dissolved in a suitable solvent and then deposited on a surface according to techniques known to those skilled in the art such as the so-called “spin coating” technique, “Doctor Blade””knifesystem”,”Slot die System” but any other technique can be used such as a dry deposit, that is to say without going through a prior dissolution.
• a surface include silicon, silicon having a native or thermal oxide layer, hydrogenated or halogenated silicon, germanium, hydrogenated or halogenated germanium, platinum and platinum oxide, tungsten and oxides, gold, titanium nitrides, graphenes.
• the surface is mineral and more preferably silicon. Even more preferably, the surface is silicon having a native or thermal oxide layer.
• the orientation of the block copolymer is defined by the thickness of the deposited block copolymer film. It is obtained in relatively short times, between 1 and 20 minutes inclusive and preferably between 1 and 5 minutes and at temperatures between 333 and 603 K and preferably between 373K and 603 K and still more preferably between 373 and 403 K.
• the method of the invention is advantageously applicable to the field of nano-lithography using block copolymer masks, or more generally in the field of nanostructuring of surfaces for electronics.
• the process of the invention also allows the manufacture of porous membranes or catalyst supports for which one of the domains of the block copolymer is degraded to obtain a porous structure.
• a first block is prepared according to a protocol described by Yamaoka et al., Macromolecules, 1995, 28, 7029-7031.
• the next block is constructed in the same way by sequentially adding the MMA, with a 1,1-diphenyl ethylene addition step to allow control of the reactivity of the active center.
• lithium chloride 85 mg
• 20 ml of THF 20 ml of heptane
• the solution is cooled to -50 ° C.
• 0.00025 moles of sec-BuLi are then introduced, followed by addition of 0.01 moles of 1,1-dimethylsilacyclobutane.
• the reaction mixture is stirred for 1 h and then 0.2 ml of 1,1-diphenyl ethylene is added.
• the molecular weights and dispersions corresponding to the ratio between weight-average molecular weight (Mw) and number-average molecular weight (Mn), are obtained by SEC (Size exclusion Chromatography), using 2 columns in series AGILENT 3ym ResiPore, in stabilized THF medium to BHT at a flow rate of 1 mL / min at 40 ° C with concentrated samples at 1 g / L, with prior calibration with calibrated polystyrene samples using a prepared Easical PS-2 pack.
• the films of Examples 1 and 2 were prepared by spin coating from 1.5% by weight solution in toluene and the thickness of the film was controlled by varying the spin-coating speed (1500 to 3000). rpm, typically less than 100 nm
• the promotion of the self-assembly inherent to the phase segregation between the blocks of the copolymer was obtained by short annealing (5 min) on a hot plate at 453 K. While the copolymer of Example 1 has a clearly visible phase transition by DSC ( Figure 1), the copolymer of Example 2 shows no transition, behaving amorphously ( Figure 2).
• the copolymer 1 shows a self assembly visible in Figure 3, while the copolymer 2 has no self ⁇ assembly (Figure 4).
• FIG. 1 is a DSC of the copolymer 1 during a heating-cooling-heating cycle under nitrogen at 10 ° C./min. The data presented represents cooling and the second heating.
• Figure 2 is a DSC of copolymer 2 during a heating-cooling-heating cycle under nitrogen at 10 ° C / min. The data presented represents cooling and the second heating.
• FIG. 3 is a photograph taken under AFM microscopy of a thin film self-assembly with a thickness less than 100 nm of the block copolymer of Example 1 having cylinders oriented perpendicularly to the substrate. Scale 100 nm.
• FIG. 4 is a photograph taken under AFM microscopy and shows the absence of self-assembly of the copolymer of

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• Health & Medical Sciences (AREA)
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• Polymers & Plastics (AREA)
• Graft Or Block Polymers (AREA)
• Exposure Of Semiconductors, Excluding Electron Or Ion Beam Exposure (AREA)
• Photosensitive Polymer And Photoresist Processing (AREA)
• Processes Of Treating Macromolecular Substances (AREA)
• Manufacture Of Porous Articles, And Recovery And Treatment Of Waste Products (AREA)
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• 2013
  • 2013-12-13 FR FR1362597A patent/FR3014888B1/fr not_active Expired - Fee Related
• 2014
  • 2014-12-11 TW TW103143324A patent/TWI547519B/zh not_active IP Right Cessation
  • 2014-12-11 CN CN201480068285.0A patent/CN105980494A/zh active Pending
  • 2014-12-11 EP EP14827499.6A patent/EP3080218A1/de not_active Withdrawn
  • 2014-12-11 WO PCT/FR2014/053279 patent/WO2015087005A1/fr active Application Filing
  • 2014-12-11 JP JP2016538584A patent/JP6404353B2/ja not_active Expired - Fee Related
  • 2014-12-11 KR KR1020167018199A patent/KR101990187B1/ko active IP Right Grant
  • 2014-12-11 US US15/103,740 patent/US20160333221A1/en not_active Abandoned
  • 2014-12-11 SG SG11201604777YA patent/SG11201604777YA/en unknown

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