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.

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