EP3080198A1 - Method for producing a block copolymer film on a substrate - Google Patents

Method for producing a block copolymer film on a substrate

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Publication number
EP3080198A1
EP3080198A1 EP14827490.5A EP14827490A EP3080198A1 EP 3080198 A1 EP3080198 A1 EP 3080198A1 EP 14827490 A EP14827490 A EP 14827490A EP 3080198 A1 EP3080198 A1 EP 3080198A1
Authority
EP
European Patent Office
Prior art keywords
copolymer
block copolymer
block
random
copolymers
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Withdrawn
Application number
EP14827490.5A
Other languages
German (de)
French (fr)
Inventor
Guillaume FLEURY
Christophe Navarro
Georges Hadziioannou
Celia NICOLET
Xavier CHEVALIER
Chrystilla REBOUL
Véronica CASTILLO
Gilles PECASTAINGS
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Centre National de la Recherche Scientifique CNRS
Arkema France SA
Universite de Bordeaux
Institut Polytechnique de Bordeaux
Original Assignee
Centre National de la Recherche Scientifique CNRS
Arkema France SA
Universite de Bordeaux
Institut Polytechnique de Bordeaux
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Centre National de la Recherche Scientifique CNRS, Arkema France SA, Universite de Bordeaux, Institut Polytechnique de Bordeaux filed Critical Centre National de la Recherche Scientifique CNRS
Publication of EP3080198A1 publication Critical patent/EP3080198A1/en
Withdrawn legal-status Critical Current

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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
    • C09D187/00—Coating compositions based on unspecified macromolecular compounds, obtained otherwise than by polymerisation reactions only involving unsaturated carbon-to-carbon bonds
    • C09D187/005—Block or graft polymers not provided for in groups C09D101/00 - C09D185/04
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
    • C08J9/26—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof by elimination of a solid phase from a macromolecular composition or article, e.g. leaching out
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
    • B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
    • B01J31/06—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides containing polymers
    • 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
    • B05D3/00—Pretreatment of surfaces to which liquids or other fluent materials are to be applied; After-treatment of applied coatings, e.g. intermediate treating of an applied coating preparatory to subsequent applications of liquids or other fluent materials
    • B05D3/06—Pretreatment of surfaces to which liquids or other fluent materials are to be applied; After-treatment of applied coatings, e.g. intermediate treating of an applied coating preparatory to subsequent applications of liquids or other fluent materials by exposure to radiation
    • 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
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F293/00—Macromolecular compounds obtained by polymerisation on to a macromolecule having groups capable of inducing the formation of new polymer chains bound exclusively at one or both ends of the starting macromolecule
    • C08F293/005—Macromolecular compounds obtained by polymerisation on to a macromolecule having groups capable of inducing the formation of new polymer chains bound exclusively at one or both ends of the starting macromolecule using free radical "living" or "controlled" polymerisation, e.g. using a complexing agent
    • 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
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
    • H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
    • H01L21/027—Making masks on semiconductor bodies for further photolithographic processing not provided for in group H01L21/18 or H01L21/34
    • H01L21/0271—Making masks on semiconductor bodies for further photolithographic processing not provided for in group H01L21/18 or H01L21/34 comprising organic layers
    • 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
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F2438/00—Living radical polymerisation
    • C08F2438/02—Stable Free Radical Polymerisation [SFRP]; Nitroxide Mediated Polymerisation [NMP] for, e.g. using 2,2,6,6-tetramethylpiperidine-1-oxyl [TEMPO]

Definitions

  • the present invention relates to a process for producing a self-assembled block copolymer film on a substrate for neutralizing the interfacial energies between said block copolymer film and the substrate comprising the formation of a random copolymer layer capable of neutralizing said interfacial energies between the block copolymer film and the substrate in a thin film configuration.
  • the method applies to the field of lithography in which the block copolymer films constitute lithography masks, the storage of information in which the block copolymer films can locate magnetic particles.
  • the method is also applicable to 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.
  • the method advantageously applies to the field of nanolithography using block copolymer masks.
  • copolymers can form well separated domains similar to those of PS-b-PMMA, but, contrary to them, the oxidation of the inorganic blocks during the etching treatments forms an oxide layer which is much more resistant to etching. which makes it possible to keep intact the pattern of the polymer constituting the lithography mask.
  • ⁇ is equal to 0.04 for the PS / PMMA pair, to 393K, while for PS / PDMS (poly (dimethylsiloxane)) it is 0.191, for PS / P2VP (poly (2 vinyl pyridine)) it is 0.178, for PS / PEO (polyethylene oxide) it is 0.077 and for PDMS / PLA (poly (lactic acid)) it is 1 .1.
  • This parameter associated with the strong contrast during the etching between PLA and PDMS, allows a better definition of the domains and thus to go to sizes of domains lower than 22 nm.
  • Also known from WO 2010/1 15243 is a method for producing a polymer structure having a surface having a plurality of functionalized surface domains.
  • the method comprises producing a composition comprising at least one surface polymer, at least one block copolymer and at least one common solvent in which the block copolymers are in the general formula ABC wherein A is a polymer of the same type as the polymer of the surface polymer and miscible with the surface polymer, B being a polymer immiscible with the polymer A and C is an end group which is a reactive molecule or an oligomer.
  • PDMS PDMS
  • Tg glass transition temperatures
  • the silicon atoms of the PDMS give it good resistance to Reactive Ion Etching (RIE), thus allowing the pattern formed by the domains to be correctly transferred to the substrate layer.
  • RIE Reactive Ion Etching
  • PLA Another block of interest that can be advantageously associated with the PDMS is PLA.
  • Poly lactic acid is distinguished by its degradability which allows to easily degrade by chemical or plasma during the step of creating the copolymer mask (it is twice as sensitive to etching as the PS, which means that it can be degraded much more easily). It is easier to synthesize and inexpensive.
  • the grafting of a random copolymer brush requires thermal annealing of the high temperature statistical copolymer films. Indeed, thermal annealing can last up to 48 hours in a vacuum oven at a temperature above the glass transition temperature of the random copolymer. This step is expensive in energy and time.
  • the Applicant has sought to obtain a process for producing a self-assembled block copolymer film on a substrate for neutralizing the interfacial energies between said block copolymer film and the substrate which is less expensive in time and cost. energy than the known methods.
  • the proposed method advantageously makes it possible to control the orientation of the mesostructure formed by the self-assembly of the block copolymer and in particular for a mesostructure of rolls oriented perpendicularly to the substrate or lamellae oriented perpendicularly to the substrate.
  • the homopolymer migrates to the substrate and behaves similarly to a homopolymer grafted brush.
  • the PS-OH homopolymer is then of the same chemical nature as one of the constituents of the block copolymer. This solution does not include a thermal annealing step necessary for the grafting of a bump as described above, but does not address the problem of controlling the orientation of the block copolymer domains.
  • one of the constituents of the random copolymer is chemically identical to one of the constituents of the block copolymer.
  • the synthesis of random copolymers from the respective monomers, to apply the approach described above, is not feasible in the state of the current art.
  • This document describes a process for producing a self-assembled block copolymer film consisting of the poly (isoprene-b-methyl methacrylate) block copolymer and the poly (styrene-acrylonitrile) random copolymer.
  • the two copolymers are of different chemical nature and immiscible under certain conditions such as the ratio between the number-average molecular weight of poly (styrene-acrylonitrile) and the number-average molecular mass of poly-methyl methacrylate; or the mass ratio between poly-methyl methacrylate and poly (styrene-acrylonitrile).
  • the method described in this document does not include depositing on a substrate a solution containing a mixture of block copolymer and random or gradient copolymer.
  • the solutions obtained after mixing the block copolymer and the random copolymer are placed in Teflon cells to allow the evaporation of the solvent, THF, and thus to obtain dry films (page 806, first paragraph).
  • Teflon does not therefore serve as a substrate but simply as a constituent material of evaporation cells.
  • this document is a scientific publication aimed at studying the miscibility and morphology of a mixture comprising a block copolymer and a random copolymer and no application (use) of such a mixture is described in this document.
  • This document also describes such a support, obtained from a porous film comprising a polystyrene network, said film being obtained by treating a copolymer comprising blocks of poly (methyl methacrylate) and polystyrene blocks by ultraviolet radiation. and plasma.
  • a copolymer comprising blocks of poly (methyl methacrylate) and polystyrene blocks by ultraviolet radiation. and plasma.
  • the process described in this document does not indicate that the block copolymer and the random copolymer are of different chemical nature and immiscible.
  • the random copolymer is a poly (styrene-methyl methacrylate) whose ends are hydroxylated.
  • the diblock copolymer being a poly (styrene-block-methyl methacrylate), makes it possible to affirm that the two copolymers are of the same chemical nature and miscible. In addition, no application other than that of an electrodeposition support is described in the document.
  • the invention therefore aims to overcome the drawbacks of the prior art, by providing a method of producing a self-assembled block copolymer film and controlled orientation on a substrate, said method consisting in performing a simultaneous deposition of block copolymer and random copolymer using a solution containing a mixture, block copolymer and random copolymer of different chemical nature, and then performing an annealing heat treatment to promote the segregation of phases inherent to self-assembly of block copolymers.
  • the block copolymer and the random copolymer forming the mixture are advantageously immiscible.
  • the invention more particularly relates to a method for producing a self-assembled block copolymer film on a substrate, characterized in that it comprises the following steps:
  • the use of random or gradient copolymers whose monomers are different from those present respectively in each block of the block copolymer in the deposited solution effectively solves the problem described above and in particular to control the orientation of the mesostructure formed by the self-assembly of a block copolymer by a random copolymer not chemically related to the block copolymer.
  • the invention also relates to a film obtained by the process described above, said film constituting a mask for lithography applications or a support for the location of magnetic particles for storing information or guides for the formation of inorganic structures,
  • the invention also relates to a film obtained by the method described above, said film constituting a porous membrane or a catalyst support after removal of one of the domains formed during the self-assembly of the copolymer. to blocks.
  • the block copolymer is of the general formula A-b-B or A-b-B-b-A and the random copolymer is of the general formula C-s-D; the monomers of the random copolymer being different from those respectively present in each block of the block copolymer, - the block copolymer and the random copolymer are immiscible,
  • the annealing treatment is obtained by heat treatment or solvent vapor or microwave treatment
  • the random or gradient copolymer is prepared by radical radical polymerization
  • - The random or gradient copolymer is prepared by controlled radical polymerization
  • the random or gradient copolymer is prepared by radical polymerization controlled by nitroxides,
  • Nitroxide is N-tert-butyl-1-diethylphosphono-2,2-dimethylpropyl nitroxide
  • the block copolymer is chosen from diblock copolymers or linear or star-shaped triblock copolymers,
  • the block copolymer comprises at least one PLA block and at least one PDMS block;
  • the random or gradient copolymer comprises methyl methacrylate and styrene;
  • the annealing treatment is obtained by heat treatment or by solvent vapor or microwave treatment.
  • the invention also relates to the use of a film obtained by the method described above for mask use for lithography applications, support for the storage of discretized information or guides for the creation of inorganic structures .
  • the invention also relates to the use of a film obtained by the method described above for use of porous membrane or catalyst support.
  • FIG. 1 represents four images (a), (b), (c), and (d) obtained according to the imaging technique called Atomic Force Microscopy (AFM),
  • AFM Atomic Force Microscopy
  • FIG. 2a shows Auger electron emission spectra for a film obtained by the method for depositing a random copolymer brush according to the prior art
  • FIG. 2b shows Auger electron emission spectra for a film obtained by the process according to the invention.
  • the random or gradient copolymers used in the invention are of the general formula C-s-D, their constituent monomers are different from those respectively present in each block of the block copolymer used.
  • the random copolymers can be obtained by any route including polycondensation, ring-opening polymerization, anionic, cationic or radical polymerization, the latter being controllable or not.
  • radical polymerization or telomerization this can 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 lodine Transfer Polymerization"), ITP (“lodine Transfer Polymerization”).
  • the polymers are preferably prepared by radical polymerization, and more particularly by controlled radical polymerization, more particularly by controlled nitroxide polymerization.
  • nitroxides derived from alkoxyamines derived from the stable free radical (1) are preferred.
  • _ has a molar mass greater than 15.0342 g / mol.
  • the radical R 1 may be a halogen atom such as chlorine, bromine or iodine, a linear, branched or cyclic hydrocarbon group, saturated or unsaturated, such as an alkyl or phenyl radical, or an ester group. COOR or an alkoxyl-OR group, or a phosphonate group
  • the radical RL monovalent, is said in position ⁇ with respect to the nitrogen atom of the nitroxide radical.
  • the remaining valences of the carbon atom and the nitrogen atom in the formula (1) can be linked to various radicals such as a hydrogen atom, a hydrocarbon radical such as an alkyl, aryl or aryl radical. -alkyl, comprising from 1 to 10 carbon atoms. It is not excluded that the carbon atom and the nitrogen atom in formula (1) are connected to each other via a divalent radical, so as to form a ring.
  • the remaining valencies of the carbon atom and the nitrogen atom of the formula (1) are attached to monovalent radicals.
  • the R 1 radical has a molar mass greater than 30 g / mol.
  • _ may for example have a molar mass of between 40 and
  • radical R 1 may be a radical comprising a phosphoryl group, said radical R 1 may be represented by the formula:
  • R 3 and R 4 which may be the same or different, may be selected from alkyl, cycloalkyl, alkoxyl, aryloxyl, aryl, aralkyloxy, perfluoroalkyl, aralkyl, and may include from 1 to 20 carbon atoms.
  • R3 and / or R 4 may also be a halogen atom such as a chlorine or bromine atom or fluorine or iodine.
  • the radical R 1 may also comprise at least one aromatic ring, such as for the phenyl radical or the naphthyl radical, the latter may be substituted, for example by an alkyl radical comprising from 1 to 4 carbon atoms.
  • alkoxyamines derived from the following stable radicals are preferred:
  • N-tert-butyl-1-phenyl-2-methylpropyl nitroxide N-tert-butyl-1- (2-naphthyl) -2-methylpropyl nitroxide
  • N-phenyl-1-diethyl phosphono-1-methyl ethyl nitroxide N- (1-phenyl-2-methylpropyl) -1-diethylphosphono-1-methyl ethyl nitroxide,
  • the alkoxyamines used in controlled radical polymerization must allow good control of the sequence of monomers. Thus they do not all allow good control of certain monomers.
  • the alkoxyamines derived from TEMPO only make it possible to control a limited number of monomers, the same goes for the alkoxyamines derived from 2,2,5-tri-methyl-4-phenyl-3-azahexane-3-nitroxide. (TIPNO).
  • TIPNO 2,2,5-tri-methyl-4-phenyl-3-azahexane-3-nitroxide.
  • other alkoxyamines derived from nitroxides corresponding to formula (1) particularly those derived from nitroxides corresponding to formula (2) and even more particularly those derived from N-tertiobutyl-1-diethylphosphono-2,2-dimethylpropyl. nitroxide allow to expand to a large number of monomer controlled radical polymerization of these monomers.
  • alkoxyamines also influences the economic factor. The use of low temperatures will be preferred to minimize industrial difficulties.
  • TIPNO 2,2,5-tri-methyl-4-phenyl-3-azahexane-3-nitroxide
  • the constituent monomers random copolymers and block copolymers (the number of at least two) will be selected from vinyl, vinylidene, diene, olefinic, allylic or (meth) acrylic monomers.
  • These monomers are chosen more particularly from vinylaromatic monomers such as styrene or substituted styrenes, especially alpha-methylstyrene, acrylic monomers such as acrylic acid or its salts, alkyl, cycloalkyl or aryl acrylates, such as methyl acrylate, ethylene, butyl, ethylhexyl or phenyl, hydroxyalkyl acrylates such as 2-hydroxyethyl acrylate, alkyl ether acrylates such as 2-methoxyethyl acrylate, alkoxy acrylates and the like.
  • aryloxy-polyalkylene glycol such as methoxypolyethylene glycol acrylates, ethoxypolyethylene glycol acrylates, methoxypolypropylene glycol acrylates, methoxy-polyethylene glycol-polypropylene glycol acrylates or mixtures thereof, aminoalkyl acrylates such as 2- (dimethylamino) acrylate ethyl (ADAME), fluorinated acrylates, silylated acrylates, phosphorus acrylates such as alkylene glycol phosphate acrylates, glycidyl acrylates, dicyclo pentenyloxyethyl, methacrylic monomers such as methacrylic acid or its salts, alkyl, cycloalkyl, alkenyl or aryl methacrylates such as methyl methacrylate (MMA), lauryl, cyclohexyl, allyl, phenyl or naphthyl, hydroxyalkyl methacryl
  • the constituent monomers of the random copolymers will preferably be chosen from styrene or (meth) acrylic monomers, and more particularly styrene and methyl methacrylate.
  • the number-average molecular weight of the random copolymers used in the invention may be between 500 g / mol and 100 000 g / mol and preferably between 1000 g / mol and 20 000 g / mol, and even more particularly between 2000 g / mol and 10,000 g / mol with a dispersity index of 1 to 10 and preferably of from 1 to 5 to 3 and in particular of from 1 to 5 to 2.
  • the block copolymers used in the invention may be of any type (diblock, triblock, multiblock, gradient, star) provided that their constituent monomers are of a different chemical nature from those present in the random copolymers used in the invention.
  • Block copolymers By “block copolymer” is meant a polymer comprising at least two copolymer blocks as defined below, the two copolymer blocks being different from one another and having a phase segregation parameter such that they are not miscible and separate into nano-domains.
  • the block copolymers used in the invention are in the general formula AbB or AbBbA and may be prepared by any route of synthesis such as anionic polymerization, polycondensation of oligomers, ring opening polymerization, or controlled radical polymerization.
  • the building blocks may be selected from the following blocks: PLA, PDMS, polytrimethyl carbonate (PTMC), polycaprolactone (PCL).
  • PLA polytrimethyl carbonate
  • PCL polycaprolactone
  • block copolymers used in the invention will be chosen from the following:
  • PLA-PDMS PLA-PDMS-PLA, PTMC-PDMS-PTMC, PCL-PDMS-PCL, PTMC-PCL, PTMC-PCL-PTMC, PCL-PTMC-PCL. And more particularly PLA-PDMS-PLA, PTMC-PDMS-PTMC.
  • block copolymers in which one block contains either styrene or styrene and at least one X comonomer, the other block containing either methyl methacrylate, either methyl methacrylate and at least one comonomer Y, X being chosen from the following entities: hydrogenated or partially hydrogenated styrene, cyclohexadiene, cyclohexene, cyclohexane, styrene substituted with one or more fluorinated alkyl groups, or their mixtures in a mass proportion of X ranging from 1 to 99% and preferably from 10 to 80% with respect to the styrene-containing block; Y being selected from the following: fluorinated alkyl (meth) acrylate, especially trifluoroethyl methacrylate, dimethyl aminoethyl (meth) acrylate, globular (meth) acrylates such as
  • the number-average molecular weight of the block copolymers used in the invention measured by SEC with polystyrene standards, it may be between 2000g / mol and 80,000g / mol and preferably between 4000g / mol and 20,000g / mol, and even more particularly between 6000 g / mol and 15000 g / mol with a dispersity index of 1 .00 to 2 and preferably 1 .05 and 1 .4.
  • the ratios between the constituent blocks will be chosen as follows:
  • the different mesostructures of the block copolymers depend on the volume fractions of the blocks.
  • a mesostructure showing a hexagonal-type stack compact can be obtained with volume fractions of -70% for one block and -30% for the other block.
  • Flory-Huggins parameter will have a strong phase separation of the blocks. Indeed, this parameter is relative to the interactions between the strings of each of the blocks.
  • a high value of ⁇ means that the blocks move as far apart as possible, which will result in a good resolution of the blocks, and therefore a low line roughness.
  • Flory-Huggins parameter that is to say greater than 0.1 to 298 K
  • the treatments adapted to promote the self-assembly of block copolymers linked to the segregation behavior of can be thermal annealing, typically above the glass transition temperature (Tg) of the blocks, ranging from 10 to 250 ° C above the highest Tg, exposure to solvent vapors, or a combination of both, or microwave treatment.
  • Tg glass transition temperature
  • it is a heat treatment whose temperature will be a function of the chosen blocks and the order-disorder temperature of the mesostructure. If appropriate, for example when the blocks are judiciously chosen, a simple evaporation of the solvent will suffice, at room temperature, to promote the self-assembly of the block copolymer.
  • the substrates The process of the invention is applicable to the following substrates: silicon, silicon having a native or thermal oxide layer, hydrogenated or halogenated silicon, germanium, hydrogenated or halogenated germanium, platinum and oxides platinum, tungsten and tungsten oxides, gold, titanium nitrides, graphenes, resins used by those skilled in the art in optical lithography.
  • the surface is mineral and more preferably silicon. Even more preferably, the surface is silicon having a native or thermal oxide layer.
  • the process for producing a self-assembled block copolymer film on a substrate according to the invention comprises:
  • a step of depositing a solution containing a mixture of block copolymer and random or gradient copolymers according to techniques known to those skilled in the art, for example the so-called “spin coating” technique, “doctor blade” “knife” System “,” slot die System “or their combinations.
  • the solution containing the mixture of block copolymer and random copolymers or gradients is subjected to a heat treatment allowing the segregation of the phases inherent in the self-assembly of block copolymers and the hierarchization of the block copolymer system / random copolymer, i.e. the migration of the random copolymer between the block copolymer layer and the substrate.
  • the method of the invention aims to form a layer containing the mixture of block copolymer and random copolymers or gradients typically less than 300 nm and preferably less than 100 nm.
  • the block copolymers used for the mixture deposited on the surfaces treated by the process of the invention are preferably di-block copolymers or linear or star-shaped triblock copolymers. .
  • the surfaces treated by the process of the invention are advantageously used in lithography, membrane preparation, porous or catalysis media applications for which one of domains formed during self-assembly of the block copolymer is degraded to obtain a porous structure.
  • reaction mixture is heated at reflux (80 ° C) for 4 h and the isopropanol is evaporated under vacuum. 297 g of hydroxy-functionalized alkoxyamine are obtained in the form of a very viscous yellow oil.
  • toluene In a stainless steel reactor equipped with a mechanical stirrer and a jacket, are introduced toluene, as well as monomers such as styrene (S), methyl methacrylate (MMA), and the hydroxy functionalized alkoxyamine.
  • S styrene
  • MMA methyl methacrylate
  • Table 1 The mass ratios between the various styrene (S) and methyl methacrylate (MMA) monomers are described in Table 1 below.
  • the mass load of toluene is set at 30% relative to the reaction medium.
  • the reaction mixture is stirred and degassed by bubbling nitrogen at room temperature for 30 minutes.
  • the temperature of the reaction medium is then brought to 1 15 ° C.
  • the temperature is maintained at 115 ° C throughout the polymerization until reaching a monomer conversion of about 70%. Samples are taken at intervals to determine the kinetics of gravimetric polymerization (measurement of solids).
  • the reaction medium When the conversion of 70% is reached, the reaction medium is cooled to 60 ° C and the solvent and residual monomers are evaporated under vacuum. After evaporation, the methyl ethyl ketone is added to the reaction medium in an amount such that a polymer solution of the order of 25% by mass is produced.
  • This polymer solution is then introduced dropwise into a beaker containing a non-solvent (heptane), so as to precipitate the polymer.
  • a non-solvent heptane
  • the mass ratio between solvent and non-solvent is of the order of 1/10.
  • the precipitated polymer is recovered as a white powder after filtration and drying.
  • Example 3 Synthesis of the Triblock Copolymer PLA-PDMS-PLA
  • the products used for this synthesis are an initiator and HO-PDMS-OH homopolymer marketed by Sigma-Aldrich, a racemic lactic acid, in order to avoid any problem related to crystallization, an organic catalyst to avoid contamination problems. metals, triazabicyclodecene (TBD) and toluene.
  • TBD triazabicyclodecene
  • the volume fractions of the blocks were determined to obtain PLA cylinders in a PDMS matrix, that is to say about 70% of P DM S and 30% of PLA.
  • EXAMPLE 4 Self-assembly of a PLA-b-PDMS-b-PLA Triblock Copolymer
  • the block copolymer described in this study was chosen according to the needs of the lithography, that is to say the cylinders in a matrix, used as masks for creating cylindrical holes in a substrate after etching and degradation.
  • the desired morphology is therefore PLA cylinders in a PDMS matrix. 1st step :
  • the substrate on which the solution was deposited according to step 1 is placed on a heating plate at 180 ° C. for 1 h 30 at a temperature close to the order-disorder transition temperature of the block copolymer in order to neutralize the interfering energies.
  • the described example demonstrates the formation of an orthogonal cylindrical hexagonal PLA network in a PDMS matrix from a mixture of PLA-b-PDMS-b-PLA block copolymer, containing a fraction PDMS volume equal to 72.7%, with the PS-s-PMMA random copolymer containing 57.8% PS.
  • FIG. 1 which illustrates four AFM images obtained using the Atomic Force Microscopy (AFM) imaging technique.
  • the AFM images (a) and (b) respectively correspond to a PLA-b-PDMS-b-PLA film deposited on a PS-s-PMMA brush, and a mixture of 75% by weight of PLA-b-PDMS- b-PLA and 25% by mass of PS-s-PMMA, without heat treatment.
  • the images (c) and (d) correspond to (a) and (b) respectively after a heat treatment of 1 h 30 at 180 ° C.
  • Figure 2a shows Auger electron emission spectra for a thermally annealed film at 180 ° C for 1 h 30 composed of PLA-b-PDMS-b-PLA deposited on a brush previously grafted PS-s-PMMA
  • Figure 2b represents Auger electron emission spectra for a film composed of a mixture of 75/25% by mass of PLA-b -PDMS-b-PLA and PS-s-PMMA respectively.
  • DSC (acronym of Differential scanning colorimetry) and SAXS (acronym for Small-angle X-ray scattering) confirms, on the one hand, that the mixtures are not miscible, and on the other hand, that the structures in bulk are identical to that of the block copolymer alone, namely cylindrical hexagonal structures.
  • the atomic force microscopy images and for example the image (d) of FIG. 1 show a hexagonal array of PLA cylinders oriented perpendicularly to the surface in a PDMS matrix. Moreover, these results are similar to those observed during the grafting of the PS-stat-PMMA brush illustrated in the image (c) of FIG.
  • Auger electron emission analyzes illustrated by FIGS.
  • a random copolymer layer is formed between the PLA-b-PDMS-b-PLA block copolymer film and the substrate, neutralizing the interfacial energies.
  • the PDMS and PLA domains no longer have preferential interactions with the substrate, and a PLA cylinder structure oriented perpendicular to the surface in a PDMS matrix is obtained during the annealing step.

Abstract

The invention concerns a method for producing a self-assembled block copolymer film on a substrate, said method consisting of simultaneously depositing block copolymer and statistical copolymer by means of a solution containing a mixture of block copolymer and statistical copolymer having different chemical natures and being immiscible, then of carrying out an annealing treatment so as to promote the segregation of phases inherent to the self-assembling of the block copolymers.

Description

PROCEDE DE REALISATION D'UN FILM DE COPOLYMERE A BLOCS SUR UN  METHOD FOR PRODUCING A BLOCK COPOLYMER FILM ON A
SUBSTRAT  SUBSTRATE
[Domaine de l'invention! [0001 ] La présente invention concerne un procédé de réalisation d'un film de copolymère à blocs auto assemblés sur un substrat permettant de neutraliser les énergies interfaciales entre ledit film de copolymère à blocs et le substrat comprenant la formation d'une couche de copolymère statistique apte à neutraliser lesdites énergies interfaciales entre le film de copolymère à blocs et le substrat dans une configuration de films minces.  [Field of the invention! The present invention relates to a process for producing a self-assembled block copolymer film on a substrate for neutralizing the interfacial energies between said block copolymer film and the substrate comprising the formation of a random copolymer layer capable of neutralizing said interfacial energies between the block copolymer film and the substrate in a thin film configuration.
[0002] Le procédé s'applique au domaine de la lithographie dans lesquels les films de copolymères à blocs constituent des masques de lithographie, du stockage de l'information dans lesquels les films de copolymères à blocs permettent de localiser des particules magnétiques. Le procédé s'applique également à la fabrication de membranes poreuses ou de supports de catalyse pour lesquels un des domaines du copolymère à blocs est dégradé afin d'obtenir une structure poreuse. Le procédé s'applique avantageusement au domaine de la nanolithographie utilisant des masques de copolymères à blocs. The method applies to the field of lithography in which the block copolymer films constitute lithography masks, the storage of information in which the block copolymer films can locate magnetic particles. The method is also applicable to 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. The method advantageously applies to the field of nanolithography using block copolymer masks.
[Art antérieur] [0003] Beaucoup de procédés de lithographie avancée basés sur l'auto- assemblage des copolymères à blocs (BC) font intervenir des masques de PS- b-PMMA ((polystyrène- bloc-poly(méthacrylate de méthyle)). Cependant, le PS est un mauvais masque pour la gravure, car il a une faible résistance aux plasmas inhérents à l'étape de gravure. Par conséquent ce système ne permet pas un transfert optimal des motifs au substrat. De plus, la séparation de phases limitée entre le PS et le PMMA due au faible paramètre de Flory Huggins χ de ce système ne permet pas d'obtenir des tailles de domaines inférieures à la vingtaine de nanomètres limitant de par ce fait la résolution finale du masque. Pour palier à ces défauts, dans « Polylactide-Poly(dimethylsiloxane)-Polylactide Triblock Copolymers as Multifunctional Materials for Nanolithographie Applications». ACS Nano. 4(2): p. 725-732 , Rodwogin, M.D., et al. décrivent des groupes contenant des atomes de Si ou de Fe, tels que le PDMS (Poly(diméthylsiloxane)), le polyhedral oligomeric silesquioxane (POSS), ou encore le poly(ferrocenylsilane) (PFS) introduits dans les copolymères à blocs servant de masques. Ces copolymères peuvent former des domaines bien séparés similaires à ceux des PS-b-PMMA, mais contrairement à eux, l'oxydation des blocs inorganiques lors des traitements de gravure forme une couche d'oxyde qui est bien plus résistante à la gravure, ce qui permet de garder intact le motif du polymère constituant le masque de lithographie. BACKGROUND [0003] Many advanced lithography processes based on self-assembly of block copolymers (BC) involve masks of PS-b-PMMA ((polystyrene-block-poly (methyl methacrylate)) However, the PS is a bad mask for etching because it has a low resistance to plasmas inherent to the etching step, therefore this system does not allow an optimal transfer of the patterns to the substrate. limited phase between the PS and the PMMA due to the low Flory Huggins parameter χ of this system does not make it possible to obtain domain sizes lower than the twenty or so nanometers, thereby limiting the final resolution of the mask. defects, in "Polylactide-Poly (dimethylsiloxane) -Polylactide Triblock Copolymers as Multifunctional Materials for Nanolithography Applications." ACS Nano., 4 (2): 725-732, Rodwogin, MD, et al. groups containing Si or Fe atoms, such as PDMS (Poly (dimethylsiloxane)), polyhedral oligomeric silesquioxane (POSS), or alternatively poly (ferrocenylsilane) (PFS) introduced into block copolymers serving as masks. These copolymers can form well separated domains similar to those of PS-b-PMMA, but, contrary to them, the oxidation of the inorganic blocks during the etching treatments forms an oxide layer which is much more resistant to etching. which makes it possible to keep intact the pattern of the polymer constituting the lithography mask.
[0004] Dans l'article "Orientation-Controlled Self-Assembled Nanolithography Using a Polystyrene-Polydimethylsiloxane Block Copolymer". Nano Letters, 2007. 7(7): p. 2046-2050, Jung et Ross suggèrent que le masque idéal de copolymère à blocs doit avoir une forte valeur de χ, et qu'un des blocs doit être fortement résistant à la gravure. Une forte valeur de χ entre les blocs favorise la formation des domaines purs et bien définis sur tout le substrat comme cela est expliqué par Bang, J. et al., dans « Defect-Free Nanoporous Thin Films from ABC Triblock Copolymers ». J. Am. Chem. Soc, 2006. 128: p. 7622, c'est-à-dire une diminution de la rugosité de ligne, χ est égal à 0.04 pour le couple PS/PMMA, à 393K, tandis que pour PS/PDMS (poly(diméthyl siloxane)) il est de 0.191 , pour PS/P2VP (poly (2 vinyle pyridine)) il est de 0.178, pour PS/PEO (poly(oxyde d'éthylène)) il est de 0.077 et pour PDMS/PLA (poly(acide lactique)) il est de 1 .1 . Ce paramètre, associé au fort contraste lors de la gravure entre PLA et PDMS, permettent une meilleure définition des domaines et donc d'aller vers des tailles de domaines inférieures à 22 nm. Tous ces systèmes ont montré une bonne organisation avec des domaines ayant une taille limite inférieure à 10nm, selon certaines conditions. Cependant, beaucoup de systèmes ayant une forte valeur de χ sont organisés grâce à un recuit par vapeur de solvant, car de trop hautes températures seraient requises pour un recuit thermique, et l'intégrité chimique des blocs ne serait pas obligatoirement conservée. [0004] In the article "Orientation-Controlled Self-Assembled Nanolithography Using a Polystyrene-Polydimethylsiloxane Block Copolymer". Nano Letters, 2007. 7 (7): p. 2046-2050, Jung and Ross suggest that the ideal block copolymer mask must have a high value of χ, and that one of the blocks must be highly resistant to etching. A high value of χ between the blocks promotes the formation of pure and well-defined domains on the entire substrate as explained by Bang, J. et al., In Defect-Free Nanoporous Thin Films from ABC Triblock Copolymers. J. Am. Chem. Soc., 2006. 128: p. 7622, ie a decrease of the line roughness, χ is equal to 0.04 for the PS / PMMA pair, to 393K, while for PS / PDMS (poly (dimethylsiloxane)) it is 0.191, for PS / P2VP (poly (2 vinyl pyridine)) it is 0.178, for PS / PEO (polyethylene oxide) it is 0.077 and for PDMS / PLA (poly (lactic acid)) it is 1 .1. This parameter, associated with the strong contrast during the etching between PLA and PDMS, allows a better definition of the domains and thus to go to sizes of domains lower than 22 nm. All these systems have shown a good organization with domains having a size limit of less than 10nm, according to certain conditions. However, many systems with a high value of χ are organized by solvent vapor annealing because too high temperatures would be required for thermal annealing, and the chemical integrity of the blocks would not necessarily be retained.
[0005] On connaît aussi du document WO 2010/1 15243 un procédé pour réaliser une structure polymère ayant une surface ayant une pluralité de domaines de surfaces fonctionnalisés. La méthode comprend la réalisation d'une composition comprenant au moins un polymère de surface , au moins un copolymère à blocs et au moins un solvant commun dans laquelle les copolymères à blocs se présentent sous la formule générale A-B-C dans la quelle, A est un polymère de même type que le polymère du polymère de surface et miscible avec le polymère de surface, B étant un polymère non miscible avec le polymère A et C est un groupe terminal qui est une molécule réactive ou un oligomère. Also known from WO 2010/1 15243 is a method for producing a polymer structure having a surface having a plurality of functionalized surface domains. The method comprises producing a composition comprising at least one surface polymer, at least one block copolymer and at least one common solvent in which the block copolymers are in the general formula ABC wherein A is a polymer of the same type as the polymer of the surface polymer and miscible with the surface polymer, B being a polymer immiscible with the polymer A and C is an end group which is a reactive molecule or an oligomer.
[0006] Parmi les blocs constitutifs des copolymères à blocs qui présentent un intérêt, on peut citer le PDMS car il a déjà été utilisé en lithographie douce, c'est-à-dire non basée sur des interactions avec la lumière, plus précisément en tant que moule ou tampon encreur. Le PDMS possède une des plus faibles températures de transition vitreuse Tg des matériaux polymères. Il a une grande stabilité thermique, une faible absorption aux rayons UV et des chaînes hautement flexibles. De plus, les atomes de Silicium du PDMS lui confèrent une bonne résistance à la gravure ionique réactive (RIE : Reactive Ion Etching), permettant ainsi de correctement transférer le motif formé par les domaines à la couche de substrat. Among the constituent blocks of block copolymers which are of interest, mention may be made of the PDMS because it has already been used in soft lithography, that is to say not based on interactions with light, more specifically in as a mold or ink pad. PDMS has one of the lowest glass transition temperatures Tg of polymeric materials. It has high thermal stability, low UV absorption and highly flexible chains. In addition, the silicon atoms of the PDMS give it good resistance to Reactive Ion Etching (RIE), thus allowing the pattern formed by the domains to be correctly transferred to the substrate layer.
[0007] Un autre bloc présentant un intérêt que l'on peut avantageusement associer au PDMS est PLA. Another block of interest that can be advantageously associated with the PDMS is PLA.
[0008] Le poly acide lactique (PLA) se distingue par sa dégradabilité ce qui permet de facilement le dégrader par voie chimique ou plasma lors de l'étape de création du masque de copolymère (il est deux fois plus sensible à la gravure que le PS, ce qui signifie qu'il peut être dégradé bien plus facilement). Il est de plus facile à synthétiser et peu onéreux. Poly lactic acid (PLA) is distinguished by its degradability which allows to easily degrade by chemical or plasma during the step of creating the copolymer mask (it is twice as sensitive to etching as the PS, which means that it can be degraded much more easily). It is easier to synthesize and inexpensive.
[0009] Il a été démontré à plusieurs reprises que le greffage d'une brosse de copolymère statistique à savoir, l'utilisation d'une brosse de copolymère statistique de PS-s-PMMA permettait de contrôler l'énergie de surface du substrat comme on peut le lire chez les auteurs suivants: Mansky, P., et al., « Controlling polymer-surface interactions with random copolymer brushes ». Science, 1997. 275: p. 1458-1460, Han, E., et al., "Effect of Composition of Substrate-Modifying Random Copolymers on the Orientation of Symmetric and Asymmetric Diblock Copolymer Domains". Macromolecules, 2008. 41 (23): p. 9090-9097, Ryu, D.Y., et al., "Cylindrical Microdomain Orientation of PS-b- PMMA on the Balanced Interfacial Interactions: Composition Effect of Block Copolymers. Macromolecules, 2009". 42(13): p. 4902-4906, In, I., et al., "Side- Chain-Grafted Random Copolymer Brushes as Neutral Surfaces for Controlling the Orientation of Block Copolymer Microdomains in Thin Films". Langmuir, 2006. 22(18): p. 7855-7860, Han, E., et al., "Perpendicular Orientation of Domains in Cylinder-Forming Block Copolymer Thick Films by Controlled Interfacial Interactions. Macromolecules, 2009". 42(13): p. 4896-4901 ; afin d'obtenir des morphologies normalement instables, telles que des cylindres perpendiculaires au substrat dans une configuration de film mince pour un copolymère à blocs de PS-b-PMMA. L'énergie de surface du substrat modifié est contrôlée en faisant varier les fractions volumiques en unités de répétition du copolymère statistique. Cette technique est utilisée car elle est simple, rapide et permet de faire varier facilement les énergies de surface afin d'équilibrer les interactions préférentielles entre les domaines du copolymère à blocs et le substrat greffé par le copolymère statistique. It has been repeatedly demonstrated that the grafting of a random copolymer brush namely, the use of a random copolymer brush PS-s-PMMA allowed to control the surface energy of the substrate as it can be read in the following authors: Mansky, P., et al., "Controlling Polymer-Surface Interactions with Random Copolymer Brushes". Science, 1997. 275: p. 1458-1460, Han, E., et al., "Effect of Composition of Substrate-Modifying Random Copolymers on the Orientation of Symmetric and Asymmetric Diblock Copolymer Domains". Macromolecules, 2008. 41 (23): p. 9090-9097, Ryu, DY, et al., "Cylindrical Microdomain Orientation of PS-b-PMMA on the Balanced Interfacial Interactions: Composition Effect of Block Copolymers, Macromolecules, 2009". 42 (13): p. 4902-4906, In, I., et al., "Side-Chain-Grafted Random Copolymer Brushes as Neutral Surfaces for Controlling the Orientation of Block Copolymer Microdomains in Thin Films". Langmuir, 2006. 22 (18): p. 7855-7860, Han, E., et al., "Perpendicular Orientation of Domains in Cylinder-Forming Block Copolymer Thick Films by Controlled Interfacial Interactions, Macromolecules, 2009". 42 (13): p. 4896-4901; to obtain normally unstable morphologies, such as cylinders perpendicular to the substrate in a thin film configuration for a PS-b-PMMA block copolymer. The surface energy of the modified substrate is controlled by varying the volume fractions in repeating units of the random copolymer. This technique is used because it is simple, fast and makes it possible to easily vary the surface energies in order to balance the preferential interactions between the domains of the block copolymer and the substrate grafted by the random copolymer.
[0010] La plupart des travaux où une brosse de copolymère statistique est utilisée afin de minimiser les énergies de surface, montrent l'utilisation d'une brosse de PS-s-PMMA (copolymère statistique PS/PMMA) pour le contrôle de l'organisation d'un PS-b-PMMA. Ji et al. dans "Generalization of the Use of Random Copolymers To Control the Wetting Behavior of Block Copolymer Films. Macromolecules, 2008". 41 (23): p. 9098-9103. ont démontré l'utilisation d'un copolymère statistique de PS-S-P2VP afin de contrôler l'orientation d'un PS-b-P2VP, méthodologie semblable à celle utilisée dans le cas du système PS/PMMA. Most work where a statistical copolymer brush is used to minimize surface energies, show the use of a PS-s-PMMA brush (statistical copolymer PS / PMMA) for the control of the organization of a PS-b-PMMA. Ji et al. in "Generalization of the Use of Random Copolymers To Control the Wetting Behavior of Block Copolymer Films." Macromolecules, 2008 ". 41 (23): p. 9098-9103. demonstrated the use of a PS-S-P2VP random copolymer to control the orientation of a PS-b-P2VP, a methodology similar to that used for the PS / PMMA system.
[001 1 ] Toutefois, le greffage d'une brosse de copolymère statistique nécessite un recuit thermique des films des copolymères statistiques à haute température. En effet, le recuit thermique peut durer jusqu'à 48h dans un four sous vide à une température supérieure à la température de transition vitreuse du copolymère statistique. Cette étape est coûteuse en énergie et en temps. [0012] La demanderesse a cherché à obtenir un procédé de réalisation d'un film de copolymères à blocs auto assemblés sur un substrat permettant de neutraliser les énergies interfaciales entre ledit film de copolymère à blocs et le substrat qui soit moins onéreux en temps et en énergie que les procédés connus. Le procédé proposé permet avantageusement de contrôler l'orientation de la mésostructure formée par l'auto assemblage du copolymère à blocs et notamment pour une mésostructure de cylindres orientés perpendiculairement au substrat ou des lamelles orientés perpendiculairement au substrat. [001 1] However, the grafting of a random copolymer brush requires thermal annealing of the high temperature statistical copolymer films. Indeed, thermal annealing can last up to 48 hours in a vacuum oven at a temperature above the glass transition temperature of the random copolymer. This step is expensive in energy and time. The Applicant has sought to obtain a process for producing a self-assembled block copolymer film on a substrate for neutralizing the interfacial energies between said block copolymer film and the substrate which is less expensive in time and cost. energy than the known methods. The proposed method advantageously makes it possible to control the orientation of the mesostructure formed by the self-assembly of the block copolymer and in particular for a mesostructure of rolls oriented perpendicularly to the substrate or lamellae oriented perpendicularly to the substrate.
[0013] Dans l'article de Kim et al. intitulé « Controlling Orientation and Order in Block Copolymer Thin Films. » Advanced Materials, 20(24): 4851 -4856, une autre solution alternative est proposée afin de contrôler l'orientation d'une mésostructure obtenue à partir de l'auto-assemblagede copolymère à blocs. L'étude menée consiste à rajouter de l'homopolymère PS-OH dans la solution contenant le copolymère dibloc PS-b-PEO. Il est démontré par mesure de réflectivité de neutrons que les chaînes de PS-OH forment une fine couche à l'interface film de copolymère à blocs/substrat. Par conséquent, lors d'un recuit permettant de promouvoir l'auto-assemblage du copolymère PS-b-PEO, l'homopolymère migre vers le substrat et se comporte pareillement à une brosse greffée d'homopolymère. L'homopolymère PS-OH est alors de même nature chimique qu'un des constituants du copolymère à blocs. Cette solution ne comporte pas d'étape de recuit thermique nécessaire au greffage d'une bosse comme décrit précédemment, mais n'aborde pas le problème du contrôle de l'orientation des domaines de copolymères à blocs. In the article by Kim et al. "Controlling Orientation and Order in Block Copolymer Thin Films. Advanced Materials, 20 (24): 4851-4856, another alternative solution is proposed to control the orientation of a mesostructure obtained from the block copolymer self-assembly. The study carried out consists of adding homopolymer PS-OH in the solution containing the diblock copolymer PS-b-PEO. It is demonstrated by neutron reflectivity measurement that the PS-OH chains form a thin layer at the block copolymer / substrate film interface. Therefore, during annealing to promote the self-assembly of the PS-b-PEO copolymer, the homopolymer migrates to the substrate and behaves similarly to a homopolymer grafted brush. The PS-OH homopolymer is then of the same chemical nature as one of the constituents of the block copolymer. This solution does not include a thermal annealing step necessary for the grafting of a bump as described above, but does not address the problem of controlling the orientation of the block copolymer domains.
[0014] Peu de travaux font état du contrôle de l'orientation des domaines par l'utilisation de copolymères statistiques ou à gradient dont les monomères constitutifs sont différents au moins en partie de ceux présents dans le copolymère à blocs y compris dans le cas de systèmes autres que le PS-b- PMMA. Few studies report the control of the orientation of domains by the use of random or gradient copolymers whose constituent monomers are different at least in part from those present in the block copolymer including in the case of systems other than PS-b-PMMA.
[0015] Keen et al. dans "Control of the Orientation of Symmetric Poly(styrene)- block-poly(d,l-lactide) Block Copolymers Using Statistical Copolymers of Dissimilar Composition. Langmuir, 2012", ont démontré l'utilisation d'un copolymère statistique de PS-s-PMMA pour contrôler l'orientation d'un PS-b- PLA. Cependant il est important de noter qu'ici un des constituants du copolymère statistique est identique chimiquement à un des constituants du copolymère à blocs. [0016] Cependant, pour certains systèmes tels que le PDMS/PLA, la synthèse de copolymères statistiques à partir des monomères respectifs, permettant d'appliquer l'approche décrite ci-dessus, n'est pas réalisable dans l'état de l'art actuel. Keen et al. in "Control of the Orientation of Symmetric Poly (styrene) -block-poly (d, l-lactide) Block Copolymers Using Statistical Copolymers of Dissimilar Composition, Langmuir, 2012", demonstrated the use of a random copolymer of PS-s-PMMA to control the orientation of a PS-b-PLA. However, it is important to note that here one of the constituents of the random copolymer is chemically identical to one of the constituents of the block copolymer. However, for some systems such as PDMS / PLA, the synthesis of random copolymers from the respective monomers, to apply the approach described above, is not feasible in the state of the current art.
[0017] La demanderesse s'est également intéressée à contourner ce problème en réalisant le contrôle des énergies de surfaces entre le substrat et le copolymère à blocs par un matériau de nature chimique différente mais apportant la même finalité en termes de fonctionnalité à savoir l'obtention d'une couche de polymère statistique entre le polymère à blocs et le substrat neutralisant les énergies interfaciales sans étape de greffage. [0018] On pourra en outre se reporter à l'état de la technique constitué par les publications suivantes : The Applicant has also been interested in circumventing this problem by realizing the control of the surface energies between the substrate and the block copolymer by a material of different chemical nature but having the same purpose in terms of functionality namely the obtaining a random polymer layer between the block polymer and the substrate neutralizing the interfacial energies without grafting step. [0018] Reference may also be made to the state of the art constituted by the following publications:
- le document de Ming Jiang et al. Intitulé « Miscibility and Morphologie of AB/C-type blends composed of block copolymères and homopolymer or random copolymer, 2A ). Oblends with random copolymer effect », Macromolecular chemistry and Physics, Wiley-VCH VERLAG, WEINHEIM, DE, vol.196, n ° 3, 1 er Mars 1995 (1995-03-01 ), Pages 803-814, XP000496316,, ISSN :1022-1352, D0I :10.1002/MACP.1995.021960310-pages 805, alinéa 3-page 806, alinéa 2, page 806, tableau 2, page 807, alinéa 2-page 810, alinéa 1 . Ce document décrit un procédé de réalisation d'un film de copolymère à blocs auto-assemblés constitué du copolymère à blocs poly(isoprène-b-méthacrylate de méthyle) et du copolymère statistique poly(styrène-acrylonitrile). Les deux copolymères sont de nature chimique différente et non miscibles sous certaines conditions telles que le ratio entre la masse moléculaire en nombre du poly(styrène-acrylonitrile) et la masse moléculaire en nombre du poly-méthacrylate de méthyle ; ou encore le ratio massique entre le poly-méthacrylate de méthyle et le Poly(styrène- acrylonitrile). Cependant le procédé décrit dans ce document ne comprend pas le dépôt sur un substrat d'une solution contenant un mélange de copolymère à blocs et de copolymère statistique ou à gradient. Les solutions obtenues après mélange du copolymère à blocs et du copolymère statistique sont placées dans des cellules en Téflon pour permettre l'évaporation du solvant, le THF, et ainsi obtenir des films secs (page 806, premier paragraphe). Le Téflon ne sert donc pas de substrat mais simplement de matériau constitutif des cellules d'évaporation .En outre, ce document est une publication scientifique visant à étudier la miscibilité et la morphologie d'un mélange comportant un copolymère à blocs et un copolymère statistique et aucune application (utilisation) d'un tel mélange n'est décrite dans ce document. - Ming Jiang et al. Entitled "Miscibility and Morphology of AB / C-type blends composed of block copolymers and homopolymer or random copolymer, 2A). With a random copolymer effect, Macromolecular Chemistry and Physics, Wiley-VCH VERLAG, WEINHEIM, DE, vol.196, No. 3, March 1, 1995 (1995-03-01), pp. 803-814, XP000496316, ISSN : 1022-1352, D0I: 10.1002 / MACP.1995.021960310-pages 805, paragraph 3-page 806, paragraph 2, page 806, table 2, page 807, paragraph 2-page 810, paragraph 1. This document describes a process for producing a self-assembled block copolymer film consisting of the poly (isoprene-b-methyl methacrylate) block copolymer and the poly (styrene-acrylonitrile) random copolymer. The two copolymers are of different chemical nature and immiscible under certain conditions such as the ratio between the number-average molecular weight of poly (styrene-acrylonitrile) and the number-average molecular mass of poly-methyl methacrylate; or the mass ratio between poly-methyl methacrylate and poly (styrene-acrylonitrile). However, the method described in this document does not include depositing on a substrate a solution containing a mixture of block copolymer and random or gradient copolymer. The solutions obtained after mixing the block copolymer and the random copolymer are placed in Teflon cells to allow the evaporation of the solvent, THF, and thus to obtain dry films (page 806, first paragraph). Teflon does not therefore serve as a substrate but simply as a constituent material of evaporation cells. In addition, this document is a scientific publication aimed at studying the miscibility and morphology of a mixture comprising a block copolymer and a random copolymer and no application (use) of such a mixture is described in this document.
- le document de Qingling Zhang et al. Intitulé « Controlled Placement of CdSe Nanoparticules in Diblock Copolymer Templates by Electrophoretic Déposition », NANO LETTERS, AMERICAN CHEMICAL SOCIETY, US, vol.5 n °2, 1 février 2005 (2005-02-01 ), pages 357-361 , XP009132829, ISSN: 1530- 6984, D0I : 10.1021 /NL048103T [strait le 2005-01 -06] page 358, colonne de gauche, alinéa 2]. Ce document décrit un procédé d'électrodéposition de nanoparticules CdSe au sein des nanopores d'un support. Ce document décrit également un tel support, obtenu à partir d'un film poreux comprenant un réseau de polystyrène, ledit film étant obtenu en traitant un copolymère comprenant des blocs de poly(méthacrylate de méthyle) et des blocs de polystyrène par rayonnement ultra-violet et plasma. Cependant, le procédé décrit dans ce document n'indique pas que le copolymère à blocs et le copolymère statistique sont de nature chimique différente et non miscibles. Au contraire, dans la partie expérimentale page 360 colonne 2, il est indiqué que le copolymère statistique est un poly(styrène-méthacrylate de méthyle) dont les extrémités sont hydroxylées. Le copolymère dibloc étant un poly(styrène-bloc-méthacrylate de méthyle), permet d'affirmer que les deux copolymères sont de même nature chimique et miscibles. En outre, aucune application autre que celle d'un support d'électrodéposition n'est décrite dans le document. [0019] L'invention a donc pour but de remédier aux inconvénients de l'art antérieur, en proposant un procédé de réalisation d'un film de copolymères à blocs auto-assemblés et d'orientation contrôlée sur un substrat, ledit procédé consistant à effectuer un dépôt simultané de copolymère à blocs et de copolymère statistique au moyen d'une solution contenant un mélange, de copolymère à blocs et de copolymère statistique de nature chimique différente, puis à effectuer un traitement thermique de recuit permettant la promotion de la ségrégation de phases inhérente à l'auto-assemblage des copolymères à blocs. Le copolymère à blocs et le copolymère statistique formant le mélange sont avantageusement, non miscibles. - Qingling Zhang et al. Entitled "Controlled Placement of CdSe Nanoparticles in Diblock Copolymer Templates by Electrophoretic Deposition", NANO LETTERS, AMERICAN CHEMICAL SOCIETY, US Vol.5 No. 2, February 1, 2005 (2005-02-01), pages 357-361, XP009132829, ISSN: 1530-6984, D0I: 10.1021 / NL048103T [strait 2005-01 -06] page 358, left column, paragraph 2]. This document describes a process for electroplating CdSe nanoparticles within the nanopores of a support. This document also describes such a support, obtained from a porous film comprising a polystyrene network, said film being obtained by treating a copolymer comprising blocks of poly (methyl methacrylate) and polystyrene blocks by ultraviolet radiation. and plasma. However, the process described in this document does not indicate that the block copolymer and the random copolymer are of different chemical nature and immiscible. On the contrary, in the experimental part page 360 column 2, it is stated that the random copolymer is a poly (styrene-methyl methacrylate) whose ends are hydroxylated. The diblock copolymer being a poly (styrene-block-methyl methacrylate), makes it possible to affirm that the two copolymers are of the same chemical nature and miscible. In addition, no application other than that of an electrodeposition support is described in the document. The invention therefore aims to overcome the drawbacks of the prior art, by providing a method of producing a self-assembled block copolymer film and controlled orientation on a substrate, said method consisting in performing a simultaneous deposition of block copolymer and random copolymer using a solution containing a mixture, block copolymer and random copolymer of different chemical nature, and then performing an annealing heat treatment to promote the segregation of phases inherent to self-assembly of block copolymers. The block copolymer and the random copolymer forming the mixture are advantageously immiscible.
[0020] L'invention a plus particulièrement pour objet un procédé de réalisation d'un film de copolymères à blocs auto assemblés sur un substrat, principalement caractérisé en ce qu'il comprend étapes suivantes : The invention more particularly relates to a method for producing a self-assembled block copolymer film on a substrate, characterized in that it comprises the following steps:
-Dépôt sur un substrat d'une solution contenant un mélange de copolymère à blocs et de copolymère statistique ou à gradient de nature chimique différente et non miscibles, Deposition on a substrate of a solution containing a mixture of block copolymer and random or gradient copolymer of different chemical nature and immiscible,
-Traitement de recuit permettant la promotion de la ségrégation de phases inhérente à l'auto-assemblage des copolymères à blocs. - Annealing treatment to promote the phase segregation inherent in the self-assembly of block copolymers.
[0021 ] Avantageusement, l'utilisation de copolymères statistiques ou à gradient dont les monomères sont différents de ceux présents respectivement dans chacun des blocs du copolymère à blocs dans la solution déposée, permet de résoudre efficacement le problème exposé ci-dessus et notamment de contrôler l'orientation de la mésostructure formée par l'auto-assemblage d'un copolymère à blocs par un copolymère statistique ne présentant pas de parenté chimique avec le copolymère à blocs. Advantageously, the use of random or gradient copolymers whose monomers are different from those present respectively in each block of the block copolymer in the deposited solution, effectively solves the problem described above and in particular to control the orientation of the mesostructure formed by the self-assembly of a block copolymer by a random copolymer not chemically related to the block copolymer.
[0022] L'invention a également pour objet, un film obtenu par le procédé décrit précédemment, ledit film constituant un masque pour les applications de lithographie ou un support pour la localisation de particules magnétiques pour du stockage de l'information ou de guides pour la formation de structures inorganiques, [0023] L'invention a aussi pour objet, un film obtenu par le procédé décrit ci- dessus, ledit film constituant une membrane poreuse ou un support de catalyseurs après élimination d'un des domaines formés lors de l'auto- assembalge du copolymère à blocs. [0024] Selon d'autres caractéristiques de l'invention : The invention also relates to a film obtained by the process described above, said film constituting a mask for lithography applications or a support for the location of magnetic particles for storing information or guides for the formation of inorganic structures, The invention also relates to a film obtained by the method described above, said film constituting a porous membrane or a catalyst support after removal of one of the domains formed during the self-assembly of the copolymer. to blocks. According to other features of the invention:
- Le copolymère à blocs est de formule générale A-b-B ou A-b-B-b-A et le copolymère statistique est de formule générale C-s-D; les monomères du copolymère statistique étant différents de ceux présents respectivement dans chacun des blocs du copolymère à blocs, - Le copolymère à blocs et le copolymère statistique sont non miscibles, The block copolymer is of the general formula A-b-B or A-b-B-b-A and the random copolymer is of the general formula C-s-D; the monomers of the random copolymer being different from those respectively present in each block of the block copolymer, - the block copolymer and the random copolymer are immiscible,
- Avantageusement, le traitement de recuit est obtenu par traitement thermique ou vapeur de solvant ou traitement par micro-onde, - Advantageously, the annealing treatment is obtained by heat treatment or solvent vapor or microwave treatment,
- Le copolymère statistique ou à gradient est préparé par polymérisation radical aire, - Le copolymère statistique ou à gradient est préparé par polymérisation radicalaire contrôlée, - The random or gradient copolymer is prepared by radical radical polymerization, - The random or gradient copolymer is prepared by controlled radical polymerization,
- Le copolymère statistique ou à gradient est préparé par polymérisation radicalaire contrôlée par les nitroxides, The random or gradient copolymer is prepared by radical polymerization controlled by nitroxides,
- Le nitroxide est le nitroxide de N-tertiobutyl-1 -diéthylphosphono-2,2- diméthyl propyl, Nitroxide is N-tert-butyl-1-diethylphosphono-2,2-dimethylpropyl nitroxide,
- Le copolymère à bloc est choisi parmi les copolymères di-blocs ou les copolymères tri-blocs linéaires ou en étoile, The block copolymer is chosen from diblock copolymers or linear or star-shaped triblock copolymers,
- Le copolymère à bloc comprend au moins un bloc PLA et au moins un bloc PDMS, - Le copolymère statistique ou à gradient comprend du méthacrylate de méthyle et du styrène, The block copolymer comprises at least one PLA block and at least one PDMS block; the random or gradient copolymer comprises methyl methacrylate and styrene;
- Le traitement de recuit est obtenu par traitement thermique ou par vapeur de solvant ou traitement par micro-onde. [0025] L'invention concerne également l'utilisation d'un film obtenu par le procédé décrit précédemment à usage de masque pour les applications de lithographie, de support pour le stockage de l'information discrétisé ou de guides pour la création de structures inorganiques. [0026] L'invention concerne aussi l'utilisation d'un film obtenu par le procédé décrit précédemment à usage de membrane poreuse ou de support de catalyseurs. - The annealing treatment is obtained by heat treatment or by solvent vapor or microwave treatment. The invention also relates to the use of a film obtained by the method described above for mask use for lithography applications, support for the storage of discretized information or guides for the creation of inorganic structures . The invention also relates to the use of a film obtained by the method described above for use of porous membrane or catalyst support.
[0027] D'autres particularités et avantages de l'invention apparaîtront à la lecture de la description faite à titre d'exemple illustratif et non limitatif, en référence aux figures sur lesquelles : Other features and advantages of the invention will appear on reading the description given by way of illustrative and nonlimiting example, with reference to the figures in which:
- la Figure 1 représente quatre images (a), (b), (c), et (d) obtenues selon la technique d'imagerie dénommée microscopie à force atomique (AFM), FIG. 1 represents four images (a), (b), (c), and (d) obtained according to the imaging technique called Atomic Force Microscopy (AFM),
- la Figure 2a représente des spectres d'émission d'électron Auger pour un film obtenu par le procédé de dépôt d'une brosse de copolymères statistiques selon l'art antérieur,  FIG. 2a shows Auger electron emission spectra for a film obtained by the method for depositing a random copolymer brush according to the prior art,
- la figure 2b représente des spectres d'émission d'électron Auger pour un film obtenu par le procédé selon l'invention.  FIG. 2b shows Auger electron emission spectra for a film obtained by the process according to the invention.
[Description détaillée] Les copolymères statistiques ou à gradient : [Detailed description] Statistical or gradient copolymers:
[0028] On entend par copolymères statistiques ou à gradient dans la présente invention des macromolécules dans lesquelles la distribution des unités monomères obéit à des lois statistiques. By statistical or gradient copolymers in the present invention are meant macromolecules in which the distribution of the monomer units obeys statistical laws.
[0029] Les copolymères statistiques ou à gradient utilisés dans l'invention sont de formule générale C-s-D, leurs monomères constitutifs sont différents de ceux présents respectivement dans chacun des blocs du copolymère à bloc utilisé. The random or gradient copolymers used in the invention are of the general formula C-s-D, their constituent monomers are different from those respectively present in each block of the block copolymer used.
[0030] Les copolymères statistiques peuvent être obtenu par n'importe quelle voie parmi lesquelles on peut citer la polycondensation, la polymérisation par ouverture de cycle, la polymérisation anionique, cationique ou radicalaire cette dernière pouvant être contrôlée ou non. Lorsque les polymères sont préparés par polymérisation ou télomérisation radicalaire, celle-ci peut être contrôlée par toute technique connue telle que NMP ("Nitroxide Mediated Polymerization"), RAFT ("Réversible Addition and Fragmentation Transfer"), ATRP ("Atom Transfer Radical Polymerization"), INIFERTER ("Initiator-Transfer-Termination"), RITP ("Reverse lodine Transfer Polymerization"), ITP ("lodine Transfer Polymerization). The random copolymers can be obtained by any route including polycondensation, ring-opening polymerization, anionic, cationic or radical polymerization, the latter being controllable or not. When polymers are prepared by radical polymerization or telomerization, this can 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 lodine Transfer Polymerization"), ITP ("lodine Transfer Polymerization").
[0031 ] On privilégiera les procédés de polymérisation ne faisant pas intervenir de métaux. De préférence les polymères sont préparés par polymérisation radicalaire, et plus particulièrement par polymérisation radicalaire contrôlée, encore plus particulièrement par polymérisation contrôlée par les nitroxydes. It will be preferred polymerization processes not involving metals. The polymers are preferably prepared by radical polymerization, and more particularly by controlled radical polymerization, more particularly by controlled nitroxide polymerization.
[0032] Plus particulièrement les nitroxides issus des alcoxyamines dérivées du radical libre stable (1 ) sont préférées. More particularly, the nitroxides derived from alkoxyamines derived from the stable free radical (1) are preferred.
Ri Ri
— C— N— O (1 ) - C-N-O (1)
[0033] Dans laquelle le radical R|_ présente une masse molaire supérieure à 15,0342 g/mole. Le radical R|_ peut être un atome d'halogène tel que le chlore, le brome ou l'iode, un groupement hydrocarboné linéaire, ramifié ou cyclique, saturé ou insaturé tel qu'un radical alkyle ou phényle, ou un groupement ester — COOR ou un groupement alcoxyle— OR, ou un groupement phosphonate— In which the radical R | _ has a molar mass greater than 15.0342 g / mol. The radical R 1 may be a halogen atom such as chlorine, bromine or iodine, a linear, branched or cyclic hydrocarbon group, saturated or unsaturated, such as an alkyl or phenyl radical, or an ester group. COOR or an alkoxyl-OR group, or a phosphonate group
PO(OR)2, dès lors qu'il présente une masse molaire supérieure à 15,0342. Le radical RL, monovalent, est dit en position β par rapport à l'atome d'azote du radical nitroxyde. Les valences restantes de l'atome de carbone et de l'atome d'azote dans la formule (1 ) peuvent être liées à des radicaux divers tels qu'un atome d'hydrogène, un radical hydrocarboné comme un radical alkyle, aryle ou aryle-alkyle, comprenant de 1 à 10 atomes de carbone. Il n'est pas exclu que l'atome de carbone et l'atome d'azote dans la formule (1 ) soient reliés entre eux par l'intermédiaire d'un radical bivalent, de façon à former un cycle. De préférence cependant, les valences restantes de l'atome de carbone et de l'atome d'azote de la formule (1 ) sont liées à des radicaux monovalents. De préférence, le radical R|_ présente une masse molaire supérieure à 30 g/mole. Le radical R|_ peut par exemple avoir une masse molaire comprise entre 40 etPO (OR) 2, since it has a molar mass greater than 15.0342. The radical RL, monovalent, is said in position β with respect to the nitrogen atom of the nitroxide radical. The remaining valences of the carbon atom and the nitrogen atom in the formula (1) can be linked to various radicals such as a hydrogen atom, a hydrocarbon radical such as an alkyl, aryl or aryl radical. -alkyl, comprising from 1 to 10 carbon atoms. It is not excluded that the carbon atom and the nitrogen atom in formula (1) are connected to each other via a divalent radical, so as to form a ring. Preferably, however, the remaining valencies of the carbon atom and the nitrogen atom of the formula (1) are attached to monovalent radicals. Preferably, the R 1 radical has a molar mass greater than 30 g / mol. The radical R | _ may for example have a molar mass of between 40 and
450 g/mole. A titre d'exemple, le radical R|_ peut être un radical comprenant un groupement phosphoryle, ledit radical R|_ pouvant être représenté par la formule : 450 g / mole. By way of example, the radical R 1 may be a radical comprising a phosphoryl group, said radical R 1 may be represented by the formula:
I  I
- P - R4 (2) - P - R 4 (2)
II  II
o  o
dans laquelle R3 et R4, pouvant être identiques ou différents, peuvent être choisis parmi les radicaux alkyle, cycloalkyle, alkoxyle, aryloxyle, aryle, aralkyloxyle, perfluoroalkyle, aralkyle, et peuvent comprendre de 1 à 20 atomes de carbone. R3 et/ou R4, peuvent également être un atome d'halogène comme un atome de chlore ou de brome ou de fluor ou d'iode. Le radical R|_ peut également comprendre au moins un cycle aromatique comme pour le radical phényle ou le radical naphtyle, ce dernier pouvant être substitué, par exemple par un radical alkyle comprenant de 1 à 4 atomes de carbone. wherein R 3 and R 4 , which may be the same or different, may be selected from alkyl, cycloalkyl, alkoxyl, aryloxyl, aryl, aralkyloxy, perfluoroalkyl, aralkyl, and may include from 1 to 20 carbon atoms. R3 and / or R 4 may also be a halogen atom such as a chlorine or bromine atom or fluorine or iodine. The radical R 1 may also comprise at least one aromatic ring, such as for the phenyl radical or the naphthyl radical, the latter may be substituted, for example by an alkyl radical comprising from 1 to 4 carbon atoms.
[0034] Plus particulièrement les alcoxyamines dérivées des radicaux stables suivants sont préférées : More particularly alkoxyamines derived from the following stable radicals are preferred:
- N-tertiobutyl-1 -phényl-2 méthyl propyl nitroxyde, - N-tertiobutyl-1 -(2-naphtyl)-2-méthyl propyl nitroxyde, N-tert-butyl-1-phenyl-2-methylpropyl nitroxide, N-tert-butyl-1- (2-naphthyl) -2-methylpropyl nitroxide,
- N-tertiobutyl-1 -diéthylphosphono-2,2-diméthyl propyl nitroxyde, N-tert-butyl-1-diethylphosphono-2,2-dimethylpropyl nitroxide,
- N-tertiobutyl-1 -dibenzylphosphono-2,2-diméthyl propyl nitroxyde, N-tert-butyl-1-dibenzylphosphono-2,2-dimethylpropyl nitroxide,
- N-phényl-1 -diéthyl phosphono-2,2-diméthyl propyl nitroxyde, N-phenyl-1-diethyl phosphono-2,2-dimethylpropyl nitroxide,
- N-phényl-1 -diéthyl phosphono-1 -méthyl éthyl nitroxyde, - N-(1 -phényl 2-méthyl propyl)-1 -diéthylphosphono-1 -méthyl éthyl nitroxyde, N-phenyl-1-diethyl phosphono-1-methyl ethyl nitroxide, N- (1-phenyl-2-methylpropyl) -1-diethylphosphono-1-methyl ethyl nitroxide,
- 4-oxo-2,2,6,6-tétraméthyl-1 -piperidinyloxy, 4-oxo-2,2,6,6-tetramethyl-1-piperidinyloxy,
- 2,4,6-tri-tert-butylphenoxy. 2,4,6-tri-tert-butylphenoxy.
[0035] Les alkoxyamines utilisées en polymérisation radicalaire contrôlée doivent permettre un bon contrôle de l'enchaînement des monomères. Ainsi elles ne permettent pas toutes un bon contrôle de certains monomères. Par exemples les alcoxyamines dérivées du TEMPO ne permettent de contrôler qu'un nombre limité de monomères, il en va de même pour les alcoxyamines dérivées du 2,2,5-tri-methyl-4-phenyl-3-azahexane-3-nitroxyde (TIPNO). En revanche d'autres alcoxyamines dérivées des nitroxydes répondant à la formule (1 ), particulièrement celles dérivées des nitroxydes répondant à la formule (2) et encore plus particulièrement celles dérivées du N-tertiobutyl-1 - diéthylphosphono-2,2-diméthyl propyl nitroxyde permettent d'élargir à un grand nombre de monomère la polymérisation radicalaire contrôlée de ces monomères. The alkoxyamines used in controlled radical polymerization must allow good control of the sequence of monomers. Thus they do not all allow good control of certain monomers. For example, the alkoxyamines derived from TEMPO only make it possible to control a limited number of monomers, the same goes for the alkoxyamines derived from 2,2,5-tri-methyl-4-phenyl-3-azahexane-3-nitroxide. (TIPNO). On the other hand, other alkoxyamines derived from nitroxides corresponding to formula (1), particularly those derived from nitroxides corresponding to formula (2) and even more particularly those derived from N-tertiobutyl-1-diethylphosphono-2,2-dimethylpropyl. nitroxide allow to expand to a large number of monomer controlled radical polymerization of these monomers.
[0036] En outre la température d'ouverture des alcoxyamines influe également sur le facteur économique. L'utilisation de basses températures sera préférée pour minimiser les difficultés industrielles. On préférera donc les alkoxyamines dérivées des nitroxydes répondant à la formule (1 ), particulièrement celles dérivées des nitroxydes répondant à la formule (2) et encore plus particulièrement celles dérivées du N-tertiobutyl-1 -diéthylphosphono-2,2- diméthyl propyl nitroxyde à celles dérivées du TEMPO ou 2,2,5-tri-methyl-4- phenyl-3-azahexane-3-nitroxyde (TIPNO). Les monomères constitutifs des copolymères statistiques et des copolymères à blocs : In addition, the opening temperature of alkoxyamines also influences the economic factor. The use of low temperatures will be preferred to minimize industrial difficulties. Alkoxyamines derived from nitroxides corresponding to formula (1), particularly those derived from nitroxides corresponding to formula (2) and even more particularly those derived from N-tert-butyl-1-diethylphosphono-2,2-dimethylpropyl nitroxide, will thus be preferred. those derived from TEMPO or 2,2,5-tri-methyl-4-phenyl-3-azahexane-3-nitroxide (TIPNO). The constituent monomers of random copolymers and block copolymers:
[0037] Les monomères constitutifs des copolymères statistiques et des copolymères à blocs (au nombre de deux au minimum) seront choisis parmi les monomères vinylique, vinylidénique, diénique, oléfinique, allylique ou (méth)acrylique. Ces monomères sont choisis plus particulièrement parmi les monomères vinylaromatiques tels que le styrène ou les styrènes substitués notamment l'alpha-méthylstyrène, les monomères acryliques tels que l'acide acrylique ou ses sels, les acrylates d'alkyle, de cycloalkyle ou d'aryle tels que l'acrylate de méthyle, d'éthyle, de butyle, d'éthylhexyle ou de phényle, les acrylates d'hydroxyalkyle tels que l'acrylate de 2-hydroxyéthyle, les acrylates d'étheralkyle tels que l'acrylate de 2-méthoxyéthyle, les acrylates d'alcoxy- ou aryloxy-polyalkylèneglycol tels que les acrylates de méthoxypolyéthylèneglycol, les acrylates d'éthoxypolyéthylèneglycol, les acrylates de méthoxypolypropylèneglycol, les acrylates de méthoxy-polyéthylèneglycol- polypropylèneglycol ou leurs mélanges, les acrylates d'aminoalkyle tels que l'acrylate de 2-(diméthylamino)éthyle (ADAME), les acrylates fluorés, les acrylates silylés, les acrylates phosphorés tels que les acrylates de phosphate d'alkylèneglycoljes acrylates de glycidyle, de dicyclopentenyloxyethyle, les monomères méthacryliques comme l'acide méthacrylique ou ses sels, les méthacrylates d'alkyle, de cycloalkyle, d'alcényle ou d'aryle tels que le méthacrylate de méthyle (MAM), de lauryle, de cyclohexyle, d'allyle, de phényle ou de naphtyle, les méthacrylates d'hydroxyalkyle tels que le méthacrylate de 2- hydroxyéthyle ou le méthacrylate de 2-hydroxypropyle, les méthacrylates d'étheralkyle tels que le méthacrylate de 2-éthoxyéthyle, les méthacrylates d'alcoxy- ou aryloxy-polyalkylèneglycol tels que les méthacrylates de méthoxypolyéthylèneglycol, les méthacrylates d'éthoxypolyéthylèneglycol, les méthacrylates de méthoxypolypropylèneglycol, les méthacrylates de méthoxy- polyéthylèneglycol-polypropylèneglycol ou leurs mélanges, les méthacrylates d'aminoalkyle tels que le méthacrylate de 2-(diméthylamino)éthyle (MADAME), les méthacrylates fluorés tels que le méthacrylate de 2,2,2-trifluoroéthyle, les méthacrylates silylés tels que le 3-méthacryloylpropyltriméthylsilane, les méthacrylates phosphorés tels que les méthacrylates de phosphate d'alkylèneglycol, le méthacrylate d'hydroxy-éthylimidazolidone, le méthacrylate d'hydroxy-éthylimidazolidinone, le méthacrylate de 2-(2-oxo-1 - imidazolidinyl)éthyle, l'acrylonitrile, l'acrylamide ou les acrylamides substitués, la 4-acryloylmorpholine, le N-méthylolacrylamide, le méthacrylamide ou les méthacrylamides substitués, le N-méthylolméthacrylamide, le chlorure de méthacrylamido-propyltriméthyle ammonium (MAPTAC), les méthacrylates de glycidyle, de dicyclopentenyloxyethyle, l'acide itaconique, l'acide maléique ou ses sels, l'anhydride maléique, les maléates ou hémimaléates d'alkyle ou d'alcoxy- ou aryloxy-polyalkylèneglycol, la vinylpyridine, la vinylpyrrolidinone, les (alcoxy) poly(alkylène glycol) vinyl éther ou divinyl éther, tels que le méthoxy poly(éthylène glycol) vinyl éther, le poly(éthylène glycol) divinyl éther, les monomères oléfiniques, parmi lesquels on peut citer l'éthylène, le butène, l'hexène et le 1 -octène, les monomères dièniques dont le butadiène, l'isoprène ainsi que les monomères oléfiniques fluorés, et les monomères vinylidénique, parmi lesquels on peut citer le fluorure de vinylidène. The constituent monomers random copolymers and block copolymers (the number of at least two) will be selected from vinyl, vinylidene, diene, olefinic, allylic or (meth) acrylic monomers. These monomers are chosen more particularly from vinylaromatic monomers such as styrene or substituted styrenes, especially alpha-methylstyrene, acrylic monomers such as acrylic acid or its salts, alkyl, cycloalkyl or aryl acrylates, such as methyl acrylate, ethylene, butyl, ethylhexyl or phenyl, hydroxyalkyl acrylates such as 2-hydroxyethyl acrylate, alkyl ether acrylates such as 2-methoxyethyl acrylate, alkoxy acrylates and the like. or aryloxy-polyalkylene glycol such as methoxypolyethylene glycol acrylates, ethoxypolyethylene glycol acrylates, methoxypolypropylene glycol acrylates, methoxy-polyethylene glycol-polypropylene glycol acrylates or mixtures thereof, aminoalkyl acrylates such as 2- (dimethylamino) acrylate ethyl (ADAME), fluorinated acrylates, silylated acrylates, phosphorus acrylates such as alkylene glycol phosphate acrylates, glycidyl acrylates, dicyclo pentenyloxyethyl, methacrylic monomers such as methacrylic acid or its salts, alkyl, cycloalkyl, alkenyl or aryl methacrylates such as methyl methacrylate (MMA), lauryl, cyclohexyl, allyl, phenyl or naphthyl, hydroxyalkyl methacrylates such as 2-hydroxyethyl methacrylate or 2-hydroxypropyl methacrylate, ether alkyl methacrylates such as 2-ethoxyethyl methacrylate, alkoxy or aryloxy methacrylates; polyalkylene glycol such as methoxypolyethylene glycol methacrylates, ethoxypolyethylene glycol methacrylates, methoxypolypropylene glycol methacrylates, methoxy-polyethylene glycol-polypropylene glycol methacrylates or mixtures thereof, aminoalkyl methacrylates such as 2- (dimethylamino) ethyl methacrylate (MADAME) fluorinated methacrylates such as 2,2,2-trifluoroethyl methacrylate, silylated methacrylates, and such as 3-methacryloylpropyltrimethylsilane, phosphorus methacrylates such as alkylene glycol phosphate methacrylates, hydroxyethylimidazolidone methacrylate, hydroxyethylimidazolidinone methacrylate, 2- (2-oxo-1-imidazolidinyl) methacrylate ethyl acrylate, acrylonitrile, acrylamide or substituted acrylamides, 4-acryloylmorpholine, N-methylolacrylamide, methacrylamide or substituted methacrylamides, N-methylolmethacrylamide, methacrylamido-propyltrimethylammonium (MAPTAC), glycidyl, dicyclopentenyloxyethyl methacrylates, itaconic acid, maleic acid or its salts, maleic anhydride, alkyl or alkoxy- or aryloxy-polyalkyleneglycol 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, of which mention may be made of ethylene, butene, hexene and 1-octene, diene monomers including butadiene, isoprene and fluorinated olefinic monomers, and vinylidene monomers, among which mention may be made of vinylidene fluoride.
[0038] De préférence les monomères constitutifs des copolymères statistiques seront choisis parmi les monomères styrèniques ou (meth)acryliques, et plus particulièrement , le styrène et le méthacrylate de méthyle. The constituent monomers of the random copolymers will preferably be chosen from styrene or (meth) acrylic monomers, and more particularly styrene and methyl methacrylate.
[0039] Concernant la masse moléculaire en nombre des copolymères statistiques utilisés dans l'invention, elle peut être comprise entre 500g/mol et 100 OOOg/mol et de préférence entre 1000g/mol et 20 OOOg/mol, et encore plus particulièrement entre de 2000g/mol et 10000g/mol avec un indice de dispersité de 1 .00 à 10 et de préférence de 1 .05 à 3 en en plus particulièrement entre 1 .05 et 2. [0040] Les copolymères à blocs utilisés dans l'invention peuvent être de tout type (di-blocs, tri-blocs, multi-blocs, à gradient, en étoile) à condition que leurs monomères constitutifs soient de nature chimique différente de ceux présents dans les copolymères statistiques utilisés dans l'invention. Regarding the number-average molecular weight of the random copolymers used in the invention, it may be between 500 g / mol and 100 000 g / mol and preferably between 1000 g / mol and 20 000 g / mol, and even more particularly between 2000 g / mol and 10,000 g / mol with a dispersity index of 1 to 10 and preferably of from 1 to 5 to 3 and in particular of from 1 to 5 to 2. The block copolymers used in the invention may be of any type (diblock, triblock, multiblock, gradient, star) provided that their constituent monomers are of a different chemical nature from those present in the random copolymers used in the invention.
Les copolymères à blocs. [0041 ] On entend par « copolymère à blocs », un polymère comprenant au moins deux blocs copolymères tels que définis ci-dessous, les deux blocs copolymères étant différents l'un de l'autre et présentant un paramètre de ségrégation de phase tel qu'ils ne sont pas miscibles et se séparent en nano- domaines. [0042] Les copolymères à blocs utilisés dans l'invention sont sous la formule générale A-b-B ou A-b-B-b-A et peuvent être préparés par toute voie de synthèse telle que la polymérisation anionique, la polycondensation d'oligomères, la polymérisation par ouverture de cycle, ou encore la polymérisation radicalaire contrôlée. Block copolymers. By "block copolymer" is meant a polymer comprising at least two copolymer blocks as defined below, the two copolymer blocks being different from one another and having a phase segregation parameter such that they are not miscible and separate into nano-domains. The block copolymers used in the invention are in the general formula AbB or AbBbA and may be prepared by any route of synthesis such as anionic polymerization, polycondensation of oligomers, ring opening polymerization, or controlled radical polymerization.
[0043] Les blocs constitutifs pourront être choisis parmi les blocs suivants: PLA, PDMS, polytriméthyle carbonate (PTMC), polycaprolactone (PCL). The building blocks may be selected from the following blocks: PLA, PDMS, polytrimethyl carbonate (PTMC), polycaprolactone (PCL).
[0044] Selon une variante de l'invention, les copolymères à blocs utilisés dans l'invention seront choisis parmi les suivants : According to a variant of the invention, the block copolymers used in the invention will be chosen from the following:
PLA-PDMS, PLA-PDMS-PLA, PTMC-PDMS-PTMC, PCL-PDMS-PCL, PTMC-PCL, PTMC-PCL-PTMC, PCL-PTMC-PCL. Et plus particulièrement PLA-PDMS-PLA, PTMC-PDMS-PTMC. PLA-PDMS, PLA-PDMS-PLA, PTMC-PDMS-PTMC, PCL-PDMS-PCL, PTMC-PCL, PTMC-PCL-PTMC, PCL-PTMC-PCL. And more particularly PLA-PDMS-PLA, PTMC-PDMS-PTMC.
[0045] Selon une autre variante de l'invention, on pourra également considérer des copolymères à blocs dont un des blocs contient soit du styrène, soit du styrène et au moins un comonomère X, l'autre bloc contenant soit du méthacrylate de méthyle, soit du méthacrylate de méthyle et au moins un comonomère Y, X étant choisi parmi les entités suivantes : styrène hydrogéné ou partiellement hydrogéné, cyclohexadiène, cyclohexène, cyclohexane, styrène substitué par un ou plusieurs groupements akyle fluoré, ou leur mélanges dans des proportion massique de X allant de 1 à 99 % et de préférence de 10 à 80 % par rapport au bloc contenant du styrène; Y étant choisi parmi les entités suivantes :(méth)acrylate d'alkyle fluoré, particulièrement le méthacrylate de trifluoro éthyle, (méth) acrylate de diméthyle amino éthyle, les (meth)acrylates globulaires tels que les (méth)acrylates d'isoborrnyle, isobornyle halogénés, (méth)acrylate d'alkyle halogénés, (méth)acrylate de naphtyle, (meth)acrylate de silsesquioxane oligomérique polyhédral pouvant contenir un groupement fluoré, ou leur mélanges, dans des proportions massiques de Y allant de 1 à 99 % et de préférence de 10 à 80 % par rapport au bloc contenant du méthacrylate de méthyle. According to another variant of the invention, it is also possible to consider block copolymers in which one block contains either styrene or styrene and at least one X comonomer, the other block containing either methyl methacrylate, either methyl methacrylate and at least one comonomer Y, X being chosen from the following entities: hydrogenated or partially hydrogenated styrene, cyclohexadiene, cyclohexene, cyclohexane, styrene substituted with one or more fluorinated alkyl groups, or their mixtures in a mass proportion of X ranging from 1 to 99% and preferably from 10 to 80% with respect to the styrene-containing block; Y being selected from the following: fluorinated alkyl (meth) acrylate, especially trifluoroethyl methacrylate, dimethyl aminoethyl (meth) acrylate, globular (meth) acrylates such as isobornyl (meth) acrylates, halogenated isobornyl, halogenated (meth) acrylate, naphthyl (meth) acrylate, polyhedral oligomeric silsesquioxane (meth) acrylate which may contain a fluorinated group, or mixtures thereof, in mass proportions of Y ranging from 1 to 99% and preferably from 10 to 80% relative to the block containing methyl methacrylate.
[0046] Selon une autre variante de l'invention, on pourra également considérer des copolymères à blocs dont un des blocs est un carbosilane, l'autre bloc contenant soit du styrène, soit du styrène et au moins un comonomère X, soit du méthacrylate de méthyle, soit du méthacrylate de méthyle et au moins un comonomère Y, X étant choisi parmi les entités suivantes : styrène hydrogéné ou partiellement hydrogéné, cyclohexadiène, cyclohexène, cyclohexane, styrène substitué par un ou plusieurs groupements akyle fluoré, ou leur mélanges dans des proportion massique de X allant de 1 à 99 % et de préférence de 10 à 80 % par rapport au bloc contenant du styrène; Y étant choisi parmi les entités suivantes :(méth)acrylate d'alkyle fluoré, particulièrement le méthacrylate de trifluoro éthyle, (méth) acrylate de diméthyle amino éthyle, les (meth)acrylates globulaires tels que les (méth)acrylates d'isoborrnyle, isobornyle halogénés, (méth)acrylate d'alkyle halogénés, (méth)acrylate de naphtyle, (meth)acrylate de silsesquioxane oligomérique polyhédral pouvant contenir un groupement fluoré, ou leur mélanges, dans des proportions massiques de Y allant de 1 à 99 % et de préférence de 10 à 80 % par rapport au bloc contenant du méthacrylate de méthyle. According to another variant of the invention, one can also consider block copolymers of which one block is a carbosilane, the other block containing either styrene, styrene and at least one X comonomer or methacrylate methyl or methyl methacrylate and at least one comonomer Y, X being chosen from the following entities: hydrogenated or partially hydrogenated styrene, cyclohexadiene, cyclohexene, cyclohexane, styrene substituted with one or more fluorinated alkyl groups, or mixtures thereof in a mass proportion of X ranging from 1 to 99% and from preferably from 10 to 80% with respect to the styrene-containing block; Y being selected from the following: fluorinated alkyl (meth) acrylate, especially trifluoroethyl methacrylate, dimethyl aminoethyl (meth) acrylate, globular (meth) acrylates such as isobornyl (meth) acrylates, halogenated isobornyl, halogenated (meth) acrylate, naphthyl (meth) acrylate, polyhedral oligomeric silsesquioxane (meth) acrylate which may contain a fluorinated group, or mixtures thereof, in mass proportions of Y ranging from 1 to 99% and preferably from 10 to 80% relative to the block containing methyl methacrylate.
[0047] Concernant la masse moléculaire en nombre des copolymères à blocs utilisés dans l'invention, mesurée par SEC avec des étalons polystyrène, elle peut être comprise entre 2000g/mol et 80 OOOg/mol et de préférence entre 4000g/mol et 20 000g/mol, et encore plus particulièrement entre 6000g/mol et 15000g/mol avec un indice de dispersité de 1 .00 à 2 et de préférence 1 .05 et 1 .4. [0048] Les ratios entre les blocs constitutifs seront choisis de la manière suivante : Regarding the number-average molecular weight of the block copolymers used in the invention, measured by SEC with polystyrene standards, it may be between 2000g / mol and 80,000g / mol and preferably between 4000g / mol and 20,000g / mol, and even more particularly between 6000 g / mol and 15000 g / mol with a dispersity index of 1 .00 to 2 and preferably 1 .05 and 1 .4. The ratios between the constituent blocks will be chosen as follows:
[0049] Les différentes mésostructures des copolymères à blocs dépendent des fractions volumiques des blocs. Des études théoriques menées par Masten et al. dans « Equilibrium behavior of symmetric ABA triblock copolymers melts. The Journal of chemical physics, 1999 ». 1 1 1 (15) : 7139-7146., montrent qu'en faisant varier les fractions volumiques des blocs, les mésostructures peuvent être sphérique, cylindrique, lamellaire, gyroide etc .. Par exemple, une mésostructure montrant un empilement de type hexagonal-compact pourra être obtenue avec des fractions volumiques de -70% pour un bloc et -30% pour l'autre bloc. [0050] Ainsi, pour obtenir des lignes, nous utiliserons un copolymère à blocs linéaire ou non de type AB, ABA, ABC présentant une mesostructure lamellaire. Pour obtenir des plots nous pourrons utiliser le même type de copolymères à blocs mais présentant des mésostructures sphériques ou cylindriques et en dégradant le domaine matrice. Pour obtenir des trous nous pourrons utiliser le même type de copolymères à blocs présentant des mésostructures sphériques ou cylindriques et en dégradant les cylindres ou les sphères de la phase minoritaire. The different mesostructures of the block copolymers depend on the volume fractions of the blocks. Theoretical studies conducted by Masten et al. in "Equilibrium behavior of symmetric ABA triblock copolymers melts. The Journal of Chemical Physics, 1999 ". 1 1 1 (15): 7139-7146. Show that by varying the volume fractions of the blocks, the mesostructures can be spherical, cylindrical, lamellar, gyroid etc. For example, a mesostructure showing a hexagonal-type stack compact can be obtained with volume fractions of -70% for one block and -30% for the other block. Thus, to obtain lines, we will use a linear block copolymer or not of type AB, ABA, ABC having a lamellar mesostructure. To obtain pads we can use the same type of block copolymers but with spherical or cylindrical mesostructures and degrading the matrix domain. To obtain holes we can use the same type of block copolymers with spherical or cylindrical mesostructures and by degrading the cylinders or spheres of the minority phase.
[0051 ] De plus, les copolymères à blocs ayant des fortes valeurs de χ, paramètre de Flory-Huggins, auront une forte séparation de phase des blocs. En effet, ce paramètre est relatif aux interactions entre les chaînes de chacun des blocs. Une forte valeur de χ signifie que les blocs s'éloignent le plus possible les uns des autres, ce qui aura pour conséquence une bonne résolution des blocs, et donc une faible rugosité de ligne. [0052] On privilégiera ainsi des systèmes de copolymères à blocs à paramètre de Flory-Huggins élevé (c'est-à-dire supérieur à 0,1 à 298 K) et plus particulièrement des blocs polymériques contenant des hétéroatomes (atomes autres que C et H), et encore plus particulièrement des atomes de Si. In addition, block copolymers having high values of χ, Flory-Huggins parameter, will have a strong phase separation of the blocks. Indeed, this parameter is relative to the interactions between the strings of each of the blocks. A high value of χ means that the blocks move as far apart as possible, which will result in a good resolution of the blocks, and therefore a low line roughness. This will favor high block copolymer systems Flory-Huggins parameter (that is to say greater than 0.1 to 298 K) and more particularly polymer blocks containing hetero atoms (non-C atoms). and H), and even more particularly Si atoms.
Ségrégation de phases: [0053] Les traitements adaptés à la promotion de l'auto-assemblage de copolymères à blocs liée au comportement de ségrégation de peuvent être un recuit thermique, typiquement au-dessus des températures de transition vitreuse (Tg) des blocs, pouvant varier de 10 à 250 °C au-dessus de la Tg la plus haute, une exposition à des vapeurs de solvant, ou encore une combinaison de ces deux traitements ou bien un traitement aux microondes. De façon préférée il s'agit d'un traitement thermique dont la température sera fonction des blocs choisis et de la température d'ordre-désordre de la mésostructure. Le cas échéant, par exemple lorsque les blocs seront judicieusement choisis, une simple évaporation du solvant suffira, à température ambiante, à promouvoir l'auto-assemblage du copolymère à bloc. Segregation of phases: The treatments adapted to promote the self-assembly of block copolymers linked to the segregation behavior of can be thermal annealing, typically above the glass transition temperature (Tg) of the blocks, ranging from 10 to 250 ° C above the highest Tg, exposure to solvent vapors, or a combination of both, or microwave treatment. Preferably, it is a heat treatment whose temperature will be a function of the chosen blocks and the order-disorder temperature of the mesostructure. If appropriate, for example when the blocks are judiciously chosen, a simple evaporation of the solvent will suffice, at room temperature, to promote the self-assembly of the block copolymer.
Les substrats : [0054] Le procédé de l'invention est applicable sur les substrats suivants : le silicium, le silicium présentant une couche d'oxyde natif ou thermique, le silicium hydrogéné ou halogéné, le germanium, le germanium hydrogéné ou halogéné, le platine et oxydes de platine, le tungstène et oxydes de tungstène, l'or, les nitrures de titane, les graphènes, les résines utilisées par l'homme de l'art en lithographie optique. De préférence la surface est minérale et plus préférentiellement du silicium. De manière encore plus préférentielle, la surface est du silicium présentant une couche d'oxyde natif ou thermique. The substrates: The process of the invention is applicable to the following substrates: silicon, silicon having a native or thermal oxide layer, hydrogenated or halogenated silicon, germanium, hydrogenated or halogenated germanium, platinum and oxides platinum, tungsten and tungsten oxides, gold, titanium nitrides, graphenes, resins used by those skilled in the art in optical lithography. Preferably the surface is mineral and more preferably silicon. Even more preferably, the surface is silicon having a native or thermal oxide layer.
[0055] Le procédé de réalisation d'un film de copolymère à blocs auto assemblés sur un substrat selon l'invention comprend : The process for producing a self-assembled block copolymer film on a substrate according to the invention comprises:
- une étape de dépôt d'une solution contenant un mélange de copolymère à blocs et de copolymères statistiques ou à gradients selon des techniques connues de l'homme de métier comme par exemple la technique dite « spin coating », « docteur Blade » « knife System », « slot die System » ou leurs combinaisons. a step of depositing a solution containing a mixture of block copolymer and random or gradient copolymers according to techniques known to those skilled in the art, for example the so-called "spin coating" technique, "doctor blade" "knife" System "," slot die System "or their combinations.
- puis, la solution contenant le mélange de copolymère à blocs et de copolymères statistiques ou à gradients est soumise à un traitement thermique permettant la ségrégation des phases inhérente à l'auto-assemblage des copolymères à blocs ainsi que la hiérarchisation du système copolymère à blocs / copolymère statistique, c'est-à-dire la migration du copolymère statistique entre la couche de copolymère à blocs et le substrat. - Then, the solution containing the mixture of block copolymer and random copolymers or gradients is subjected to a heat treatment allowing the segregation of the phases inherent in the self-assembly of block copolymers and the hierarchization of the block copolymer system / random copolymer, i.e. the migration of the random copolymer between the block copolymer layer and the substrate.
[0056] Le procédé de l'invention vise à former une couche contenant le mélange de copolymère à blocs et de copolymères statistiques ou à gradients typiquement inférieure à 300 nm et de préférence inférieure à 100 nm. [0057] Selon une forme préférée de l'invention, les copolymères à blocs utilisés pour le mélange déposé sur les surfaces traitées par le procédé de l'invention sont de préférence des copolymères di-blocs ou des copolymères tri-blocs linéaires ou en étoile. The method of the invention aims to form a layer containing the mixture of block copolymer and random copolymers or gradients typically less than 300 nm and preferably less than 100 nm. According to a preferred form of the invention, the block copolymers used for the mixture deposited on the surfaces treated by the process of the invention are preferably di-block copolymers or linear or star-shaped triblock copolymers. .
[0058] Les surfaces traitées par le procédé de l'invention sont avantageusement utilisées dans les applications de lithographie, de préparation de membranes, poreuses ou de supports de catalyse pour lesquels un des domaines formés lors de l'auto-assemblage du copolymère à blocs est dégradé afin d'obtenir une structure poreuse. The surfaces treated by the process of the invention are advantageously used in lithography, membrane preparation, porous or catalysis media applications for which one of domains formed during self-assembly of the block copolymer is degraded to obtain a porous structure.
[0059] Exemples : a) Préparation d'un copolymère statistique par polymérisation radiculaire. Exemple 1 : préparation d'une alcoxyamine fonctionnalisée hydroxy à partir de l'alcoxyamine commerciale BlocBuilder®MA : Examples: a) Preparation of a random copolymer by radicular polymerization. EXAMPLE 1 Preparation of a Hydroxy-functionalized Alkoxyamine from the BlockBuilder®MA Commercial Alkoxyamine
[0060] Dans un ballon de 1 L purgé à l'azote, on introduit : In a 1 L flask purged with nitrogen, the following are introduced:
- 226,17 g de BlocBuilder®MA (1 équivalent) - 226.17 g of BlocBuilder®MA (1 equivalent)
- 68,9 g d'acrylate de 2-hydroxyethyle (1 équivalent) - 548 g d'isopropanol 68.9 g of 2-hydroxyethyl acrylate (1 equivalent) - 548 g of isopropanol
[0061 ] Le mélange réactionnel est chauffé à reflux (80 ° C) pendant 4h puis l'isopropanol est évaporé sous vide. On obtient 297 g d'alcoxyamine fonctionnalisée hydroxy sous la forme d'une huile jaune très visqueuse. The reaction mixture is heated at reflux (80 ° C) for 4 h and the isopropanol is evaporated under vacuum. 297 g of hydroxy-functionalized alkoxyamine are obtained in the form of a very viscous yellow oil.
Exemple 2 : [0062] Protocole expérimental de préparation de polymères Polystyrène / Polyméthacrylate de méthyle (PS/PMMA), à partir de l'alcoxyamine fonctionnalisée hydroxy préparée selon l'exemple 1 . EXAMPLE 2 Experimental Protocol for the Preparation of Polystyrene / Polymethylmethacrylate Polymers (PS / PMMA) from the Hydroxy-functionalized Alkoxyamine Prepared According to Example 1
[0063] Dans un réacteur en acier inoxydable équipé d'un agitateur mécanique et d'une double enveloppe, sont introduits le toluène, ainsi que les monomères tels que le styrène (S), le méthacrylate de méthyle (MMA), et l'alcoxyamine fonctionnalisée hydroxy. Les ratios massiques entre les différents monomères styrène (S) et méthacrylate de méthyle (MMA), sont décrits dans le tableau 1 ci - après. La charge massique de toluène est fixée à 30% par rapport au milieu réactionnel. Le mélange réactionnel est agité et dégazé par un bullage d'azote à température ambiante pendant 30 minutes. In a stainless steel reactor equipped with a mechanical stirrer and a jacket, are introduced toluene, as well as monomers such as styrene (S), methyl methacrylate (MMA), and the hydroxy functionalized alkoxyamine. The mass ratios between the various styrene (S) and methyl methacrylate (MMA) monomers are described in Table 1 below. The mass load of toluene is set at 30% relative to the reaction medium. The reaction mixture is stirred and degassed by bubbling nitrogen at room temperature for 30 minutes.
[0064] La température du milieu réactionnel est alors portée à 1 15°C. Le temps t=0 est déclenché à température ambiante. La température est maintenue à 1 15°C tout le long de la polymérisation jusqu'à atteindre une conversion des monomères de l'ordre de 70%. Des prélèvements sont réalisés à intervalles réguliers afin de déterminer la cinétique de polymérisation par gravimétrie (mesure d'extrait sec). The temperature of the reaction medium is then brought to 1 15 ° C. The time t = 0 is triggered at room temperature. The temperature is maintained at 115 ° C throughout the polymerization until reaching a monomer conversion of about 70%. Samples are taken at intervals to determine the kinetics of gravimetric polymerization (measurement of solids).
[0065] Lorsque la conversion de 70% est atteinte, le milieu réactionnel est refroidi à 60° C et le solvant et monomères résiduels sont évaporés sous vide. Après évaporation, la méthyléthylcétone est additionnée au milieu réactionnel en quantité telle que l'on réalise une solution de polymère de l'ordre de 25% massique. When the conversion of 70% is reached, the reaction medium is cooled to 60 ° C and the solvent and residual monomers are evaporated under vacuum. After evaporation, the methyl ethyl ketone is added to the reaction medium in an amount such that a polymer solution of the order of 25% by mass is produced.
[0066] Cette solution de polymère est alors introduite goutte à goutte dans un bêcher contenant un non-solvant (l'heptane), de manière à faire précipiter le polymère. Le ratio massique entre solvant et non-solvant (méthyléthylcétone/heptane) est de l'ordre de 1 /10. Le polymère précipité est récupéré sous la forme d'une poudre blanche après filtration et séchage. This polymer solution is then introduced dropwise into a beaker containing a non-solvent (heptane), so as to precipitate the polymer. The mass ratio between solvent and non-solvent (methyl ethyl ketone / heptane) is of the order of 1/10. The precipitated polymer is recovered as a white powder after filtration and drying.
[0067] Tableau 1 Table 1
[0068] (a) Déterminés par chromatographie d'exclusion stérique. Les polymères sont solubilisés à 1 g/l dans du THF stabilisé au BHT. L'étalonnage est effectué grâce à des étalons de polystyrène mono-disperses. La double détection par indice de réfraction et UV à 254nm permet de déterminer le pourcentage de polystyrène dans le polymère. b) Synthèse du copolymère à blocs : [0068] (a) Determined by size exclusion chromatography. The polymers are solubilized at 1 g / l in THF stabilized with BHT. Calibration is performed using mono-dispersed polystyrene standards. Double detection by refractive index and UV at 254 nm makes it possible to determine the percentage of polystyrene in the polymer. b) Synthesis of the block copolymer:
Exemple 3 : Synthèse du copolymère triblocs PLA-PDMS-PLA : [0069] Les produits utilisés pour cette synthèse sont un amorceur et homopolymère HO-PDMS-OH commercialisé par Sigma-AIdrich, un acide lactique racémique, afin d'éviter tout problème lié à la cristallisation, un catalyseur organique pour éviter les problèmes de contamination des métaux, le triazabicyclodécène (TBD) et du toluène. Example 3 Synthesis of the Triblock Copolymer PLA-PDMS-PLA The products used for this synthesis are an initiator and HO-PDMS-OH homopolymer marketed by Sigma-Aldrich, a racemic lactic acid, in order to avoid any problem related to crystallization, an organic catalyst to avoid contamination problems. metals, triazabicyclodecene (TBD) and toluene.
[0070] Les fractions volumiques des blocs ont été déterminés pour obtenir des cylindres de PLA dans une matrice de PDMS, c'est-à-dire environ 70% de P DM S et 30% de PLA. The volume fractions of the blocks were determined to obtain PLA cylinders in a PDMS matrix, that is to say about 70% of P DM S and 30% of PLA.
Exemple 4 : Auto-assemblage d'un copolymère tribloc PLA-b-PDMS-b-PLA [0071 ] Le copolymère à blocs décrit dans cette étude a été choisi en fonction des besoins de la lithographie, c'est-à-dire des cylindres dans une matrice, utilisés en tant que masques pour la création de trous cylindriques dans un substrat après gravure et dégradation. La morphologie souhaitée est donc des cylindres de PLA dans une matrice de PDMS. 1 ère étape : EXAMPLE 4 Self-assembly of a PLA-b-PDMS-b-PLA Triblock Copolymer The block copolymer described in this study was chosen according to the needs of the lithography, that is to say the cylinders in a matrix, used as masks for creating cylindrical holes in a substrate after etching and degradation. The desired morphology is therefore PLA cylinders in a PDMS matrix. 1st step :
[0072] - Préparation d'un mélange d'une solution contenant soit 5, soit 10 mg de copolymère statistique PS/PMMA obtenu selon l'exemple 2, et 15 mg de copolymère à blocs PLA/PDMS obtenu selon l'exemple 3, - on complète la solution avec un solvant adéquat, le PGMEA (Propylène Glycol Monométhyl Éther Acétate) jusqu'à 1 g de solution. Ensuite, 100 μί. de cette solution sont déposés sur un substrat de silicium d'une surface de 1 ,4x1 ,4 cm2 par spin- coating durant 30s, - Preparation of a mixture of a solution containing either 5 or 10 mg of statistical copolymer PS / PMMA obtained according to Example 2, and 15 mg of PLA / PDMS block copolymer obtained according to Example 3, - The solution is supplemented with a suitable solvent, PGMEA (Propylene Glycol Monomethyl Ether Acetate) up to 1 g of solution. Then 100 μί. of this solution are deposited on a silicon substrate with a surface of 1, 4x1, 4 cm 2 by spin-coating for 30s,
2 ème étape 2nd step
[0073] - On réalise un recuit : traitement thermique permettant la promotion de la ségrégation de phases. Le substrat sur lequel a été déposée la solution selon l'étape 1 est placé sur une plaque chauffante à 180°C durant 1 h30, à une température proche de la température de transition ordre-désordre du copolymère à blocs afin de neutraliser les énergies inter faciales film de polymère/substrat. [0074] L'exemple décrit, met en évidence la formation d'un réseau hexagonal cylindrique orthogonal de PLA dans une matrice de PDMS à partir d'un mélange de copolymère à blocs PLA-b-PDMS-b-PLA, contenant une fraction volumique de PDMS égale à 72,7%, avec le copolymère statistique PS-s-PMMA contenant 57,8% de PS. - Annealing is carried out: heat treatment for promoting segregation of phases. The substrate on which the solution was deposited according to step 1 is placed on a heating plate at 180 ° C. for 1 h 30 at a temperature close to the order-disorder transition temperature of the block copolymer in order to neutralize the interfering energies. Facial polymer film / substrate. The described example demonstrates the formation of an orthogonal cylindrical hexagonal PLA network in a PDMS matrix from a mixture of PLA-b-PDMS-b-PLA block copolymer, containing a fraction PDMS volume equal to 72.7%, with the PS-s-PMMA random copolymer containing 57.8% PS.
[0075] On pourra se reporter à la figure 1 qui illustre quatre images AFM obtenues selon la technique d'imagerie de microscopie à force atomique (AFM). Les images AFM (a) et (b) correspondent respectivement à un film de PLA-b- PDMS-b-PLA déposé sur une brosse de PS-s-PMMA, et un mélange de 75% massique de PLA-b-PDMS-b-PLA et 25% massique de PS-s-PMMA, sans traitement thermique. Les images (c) et (d) correspondent à (a) et (b) respectivement après un traitement thermique de 1 h30 à 180 ° C. FIG. 1, which illustrates four AFM images obtained using the Atomic Force Microscopy (AFM) imaging technique. The AFM images (a) and (b) respectively correspond to a PLA-b-PDMS-b-PLA film deposited on a PS-s-PMMA brush, and a mixture of 75% by weight of PLA-b-PDMS- b-PLA and 25% by mass of PS-s-PMMA, without heat treatment. The images (c) and (d) correspond to (a) and (b) respectively after a heat treatment of 1 h 30 at 180 ° C.
[0076] On pourra se reporter également à la Figure 2a qui représente des spectres d'émission d'électron Auger pour un film recuit thermiquement à 180° C durant 1 h30 composé de PLA-b-PDMS-b-PLA déposé sur une brosse greffé au préalable de PS-s-PMMA, et à titre de comparaison à la figure la figure 2b qui représente des spectres d'émission d'électron Auger pour un film composé d'un mélange de 75/25 % massique de PLA-b-PDMS-b-PLA et PS-s-PMMA respectivement. [0077] Des analyses de DSC (acronique de Differential scanning colorimetry) et de SAXS (acronyme de Small-angleX- ray scattering) confirment d'une part, que les mélanges ne sont pas miscibles, et d'autre part, que les structures en masse sont identiques à celle du copolymère à blocs seul, à savoir des structures hexagonales cylindriques. [0078] Les images de microscopie à force atomique et par exemple l'image (d) de la Figure 1 , montrent un réseau hexagonal de cylindres de PLA orientés perpendiculairement à la surface dans une matrice de PDMS. Par ailleurs, ces résultats sont similaires à ceux observés lors du greffage de la brosse de PS- stat-PMMA illustré sur l'image (c) de la Figure 1 . [0079] De plus, des analyses d'émission d'électrons Auger, illustrées par les Figure 2a et 2b, démontrent que les comportements des films sont identiques entre un film de copolymère à blocs déposé sur une brosse de copolymère statistique illustré par la figure 2a (image (a)), et un mélange de 75/25% massique de copolymère à blocs et de copolymère statistique respectivement illustré par la figure 2b (image (b). [0080] Par conséquent, lors du recuit thermique les chaînes du copolymère statistique PS-s-PMMA migrent vers le substrat et jouent le rôle de couche de neutralisation de la surface vis-à-vis du copolymère à blocs. We can also refer to Figure 2a which shows Auger electron emission spectra for a thermally annealed film at 180 ° C for 1 h 30 composed of PLA-b-PDMS-b-PLA deposited on a brush previously grafted PS-s-PMMA, and for comparison with Figure 2b which represents Auger electron emission spectra for a film composed of a mixture of 75/25% by mass of PLA-b -PDMS-b-PLA and PS-s-PMMA respectively. DSC (acronym of Differential scanning colorimetry) and SAXS (acronym for Small-angle X-ray scattering) confirms, on the one hand, that the mixtures are not miscible, and on the other hand, that the structures in bulk are identical to that of the block copolymer alone, namely cylindrical hexagonal structures. The atomic force microscopy images and for example the image (d) of FIG. 1 show a hexagonal array of PLA cylinders oriented perpendicularly to the surface in a PDMS matrix. Moreover, these results are similar to those observed during the grafting of the PS-stat-PMMA brush illustrated in the image (c) of FIG. In addition, Auger electron emission analyzes, illustrated by FIGS. 2a and 2b, demonstrate that the behaviors of the films are identical. between a block copolymer film deposited on a random copolymer brush illustrated in FIG. 2a (image (a)), and a mixture of 75/25% by weight of block copolymer and of random copolymer respectively illustrated by FIG. 2b ( image (b) [0080] Consequently, during thermal annealing, the chains of the PS-s-PMMA random copolymer migrate towards the substrate and act as surface neutralization layer with respect to the block copolymer.
[0081 ] Ainsi, une couche de copolymère statistique est formée entre le film de copolymère à blocs PLA-b-PDMS-b-PLA et le substrat, neutralisant les énergies interfaciales. En conséquence, les domaines de PDMS et de PLA n'ont plus d'interactions préférentielles avec le substrat, et une structure de cylindres de PLA orientés perpendiculairement à la surface dans une matrice de PDMS est obtenue lors de l'étape de recuit. [0081] Thus, a random copolymer layer is formed between the PLA-b-PDMS-b-PLA block copolymer film and the substrate, neutralizing the interfacial energies. As a result, the PDMS and PLA domains no longer have preferential interactions with the substrate, and a PLA cylinder structure oriented perpendicular to the surface in a PDMS matrix is obtained during the annealing step.

Claims

REVENDICATIONS. CLAIMS.
1 . Procédé de réalisation d'un film de copolymère à blocs auto assemblés sur un substrat, principalement caractérisé en ce qu'il comprend étapes suivantes : 1. Process for producing a self-assembled block copolymer film on a substrate, characterized in that it comprises the following steps:
-Dépôt sur un substrat d'une solution contenant un mélange de copolymère à blocs et de copolymère statistique ou à gradient de nature chimique différente et non miscibles, Deposition on a substrate of a solution containing a mixture of block copolymer and random or gradient copolymer of different chemical nature and immiscible,
-Traitement de recuit permettant la promotion de la ségrégation de phases inhérente à l'auto-assemblage des copolymères à blocs. - Annealing treatment to promote the phase segregation inherent in the self-assembly of block copolymers.
2. Procédé selon la revendication 1 , caractérisé en ce que le copolymère à blocs est de formule générale A-b-B ou A-b-B-b-A et le copolymère statistique est de formule générale C-s-D; les monomères du copolymère statistique étant différents de ceux présents respectivement dans chacun des blocs du copolymère à blocs. 2. Process according to claim 1, characterized in that the block copolymer is of the general formula A-b-B or A-b-B-b-A and the random copolymer is of the general formula C-s-D; the monomers of the random copolymer being different from those respectively present in each block of the block copolymer.
3. Procédé selon l'une quelconque des revendications précédentes, caractérisé en ce que le copolymère statistique ou à gradient est préparé par polymérisation radicalaire. 3. Method according to any one of the preceding claims, characterized in that the random or gradient copolymer is prepared by radical polymerization.
4. Procédé selon l'une quelconque des revendications précédentes, caractérisé en ce que le copolymère statistique ou à gradient est préparé par polymérisation radicalaire contrôlée. 4. Method according to any one of the preceding claims, characterized in that the random or gradient copolymer is prepared by controlled radical polymerization.
5. Procédé selon l'une quelconque des revendications précédentes, caractérisé en ce que le copolymère statistique ou à gradient est préparé par polymérisation radicalaire contrôlée par les nitroxides. 5. Method according to any one of the preceding claims, characterized in that the random or gradient copolymer is prepared by radical polymerization controlled by nitroxides.
6. Procédé selon la revendication 5, caractérisé en ce que le nitroxide est le nitroxide de N-tertiobutyl-1 -diéthylphosphono-2,2-diméthyl propyl. 6. Process according to claim 5, characterized in that the nitroxide is N-tert-butyl-1-diethylphosphono-2,2-dimethylpropyl nitroxide.
7. Procédé selon l'une quelconque des revendications précédentes, caractérisé en ce que le copolymère à bloc est choisi parmi les copolymères di-blocs ou les copolymères tri-blocs linéaires ou en étoile. 7. Process according to any one of the preceding claims, characterized in that the block copolymer is chosen from diblock copolymers or linear or star-shaped triblock copolymers.
8. Procédé selon l'une quelconque des revendications précédentes, caractérisé en ce que le copolymère à bloc comprend au moins un bloc PLA et au moins un bloc PDMS. 8. Method according to any one of the preceding claims, characterized in that the block copolymer comprises at least one PLA block and at least one PDMS block.
9. Procédé selon la revendication 5, caractérisé en ce que le copolymère statistique ou à gradient comprend du méthacrylate de méthyle et du styrène. 9. Process according to claim 5, characterized in that the random or gradient copolymer comprises methyl methacrylate and styrene.
10. Procédé selon l'une quelconque des revendications précédentes, caractérisé en ce que le traitement de recuit est obtenu par traitement thermique ou vapeur de solvant ou traitement par micro-onde. 10. Method according to any one of the preceding claims, characterized in that the annealing treatment is obtained by heat treatment or solvent vapor or microwave treatment.
1 1 . Utilisation d'un film obtenu par le procédé selon les revendications 1 à 10, comme masque pour les applications de lithographie ou un support pour la localisation de particules magnétiques pour du stockage de l'information ou de guides pour la formation de structures inorganiques. 1 1. Use of a film obtained by the process according to claims 1 to 10 as a mask for lithographic applications or as a support for the location of magnetic particles for information storage or as guides for the formation of inorganic structures.
12. Utilisation d'un film obtenu par le procédé selon les revendications 1 à 10, comme membrane poreuse ou un support de catalyseurs après élimination d'un des domaines du copolymère à blocs. 12. Use of a film obtained by the process according to claims 1 to 10, as a porous membrane or a catalyst support after removal of one of the domains of the block copolymer.
13. 13.
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