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EP3248064A1 - Method for reducing the assembly time of ordered films made of block copolymer - Google Patents

Method for reducing the assembly time of ordered films made of block copolymer

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Publication number
EP3248064A1
EP3248064A1 EP16703593.0A EP16703593A EP3248064A1 EP 3248064 A1 EP3248064 A1 EP 3248064A1 EP 16703593 A EP16703593 A EP 16703593A EP 3248064 A1 EP3248064 A1 EP 3248064A1
Authority
EP
European Patent Office
Prior art keywords
todt
block copolymer
block
mixture
copolymer
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Withdrawn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
EP16703593.0A
Other languages
German (de)
French (fr)
Inventor
Xavier CHEVALIER
Raber INOUBLI
Christophe Navarro
Celia NICOLET
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.)
Arkema France SA
Original Assignee
Arkema France SA
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 Arkema France SA filed Critical Arkema France SA
Publication of EP3248064A1 publication Critical patent/EP3248064A1/en
Withdrawn legal-status Critical Current

Links

Classifications

    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • 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
    • G03F7/004—Photosensitive materials
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C41/00—Shaping by coating a mould, core or other substrate, i.e. by depositing material and stripping-off the shaped article; Apparatus therefor
    • B29C41/003—Shaping by coating a mould, core or other substrate, i.e. by depositing material and stripping-off the shaped article; Apparatus therefor characterised by the choice of material
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C41/00—Shaping by coating a mould, core or other substrate, i.e. by depositing material and stripping-off the shaped article; Apparatus therefor
    • B29C41/34—Component parts, details or accessories; Auxiliary operations
    • B29C41/46—Heating or cooling
    • 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
    • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
    • C08J5/18—Manufacture of films or sheets
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L53/00—Compositions of block copolymers containing at least one sequence of a polymer obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of 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
    • G03F1/00—Originals for photomechanical production of textured or patterned surfaces, e.g., masks, photo-masks, reticles; Mask blanks or pellicles therefor; Containers specially adapted therefor; Preparation thereof
    • G03F1/50—Mask blanks not covered by G03F1/20 - G03F1/34; Preparation thereof
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/0002—Lithographic processes using patterning methods other than those involving the exposure to radiation, e.g. by stamping
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29K—INDEXING SCHEME ASSOCIATED WITH SUBCLASSES B29B, B29C OR B29D, RELATING TO MOULDING MATERIALS OR TO MATERIALS FOR MOULDS, REINFORCEMENTS, FILLERS OR PREFORMED PARTS, e.g. INSERTS
    • B29K2105/00—Condition, form or state of moulded material or of the material to be shaped
    • B29K2105/0085—Copolymers
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29L—INDEXING SCHEME ASSOCIATED WITH SUBCLASS B29C, RELATING TO PARTICULAR ARTICLES
    • B29L2011/00—Optical elements, e.g. lenses, prisms
    • 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
    • C08J2353/00—Characterised by the use of block copolymers containing at least one sequence of a polymer obtained by reactions only involving carbon-to-carbon unsaturated bonds; Derivatives of such polymers
    • 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
    • C08J2453/00—Characterised by the use of block copolymers containing at least one sequence of a polymer obtained by reactions only involving carbon-to-carbon unsaturated bonds; Derivatives of such polymers

Definitions

  • the present invention relates to a method for reducing the assembly time of an ordered film comprising a block copolymer (BCP).
  • BCP block copolymer
  • the invention also relates to the compositions used to obtain these ordered films and the ordered films thus obtained which can be used in particular as masks in the field of lithography.
  • the method which is the subject of the invention is particularly useful when it comes to obtaining large-area ordered films in times compatible with industrial production without this being to the detriment of the defectivity.
  • the nanostructuration of a block copolymer of a surface treated by the process of the invention can take the forms such as cylindrical (hexagonal symmetry (symmetry of hexagonal network primitive "6mm") according to the notation of Hermann-Mauguin, or tetragonal / quadratic ("4mm” tetragonal lattice symmetry),, spherical (hexagonal symmetry ("6mm” or “6 / mmm” primitive hexagonal lattice symmetry), or tetragonal / quadratic (“4mm” tetragonal lattice symmetry) , or cubic (network symmetry "”)), Lamellar, or gyroid.
  • the preferred form of nanostructuring is of the hexagonal cylindrical type.
  • the method for self-assembly of block copolymers on a treated surface according to the invention is governed by thermodynamic laws.
  • each cylinder is surrounded by 6 equidistant neighboring cylinders if there is no defect.
  • Several types of defects can thus be identified. The first type is based on the evaluation of the number of neighbors around a cylinder constituted by the arrangement of the block copolymer, also called coordination defects. If five or seven cylinders surround the cylinder considered, it will be considered that there is a lack of coordination.
  • the second type of defect considers the average distance between the cylinders surrounding the cylinder considered.
  • the firing required for the self-assembly of a block copolymer can take times ranging from several minutes to several hours. .
  • the method of the invention makes it possible to obtain nanostructured assemblies in the form of ordered films with a reduction in the time required for correct assembly compared to what is observed when only one block copolymer is used.
  • the invention relates to a method for reducing the assembly time of an ordered film of block copolymer, said ordered film comprising a mixture of at least one block copolymer having an order - disorder transition temperature (TODT) and at least one Tg with at least one compound having no TODT, this mixture having a TODT lower than the TODT of the block copolymer alone, the process comprising the following steps:
  • any block copolymer, whatever its associated morphology, may be used in the context of the invention, whether it concerns of diblock copolymer, linear or star triblock, linear multiblock, comb or star.
  • these are diblock or triblock copolymers, and more preferably diblock copolymers.
  • the order-disorder transition temperature TODT which corresponds to a phase separation of the constituent blocks of the block copolymer can be measured in different ways, such as DSC (differential scanning calorimetry, differential thermal analysis), SAXS (small angle X ray scattering, small angle X-ray scattering), static birefringence, dynamic mechanical analysis, DMA or any other method to visualize the temperature at which a phase separation occurs (corresponding to the disorder order transition). A combination of these techniques can also be used.
  • n m-block copolymers n being an integer between 1 and 10 inclusive.
  • n is between 1 and 5, inclusive, and preferably n is between 1 and 2 inclusive, and even more preferably n is 1, where m is an integer between 1 and 10, terminals included.
  • m is between 1 and 5, inclusive, and preferably, m is between 1 and 4, including terminals, and more preferably m is equal to 1.
  • block copolymers may be synthesized by any techniques known to those skilled in the art, among which mention may be made of polycondensation, ring-opening polymerization, anionic, cationic or radical polymerization, these techniques being controllable or not, and combined between they or not.
  • radical polymerization they may be controlled by any known technique such as NMP ("Nitroxide Mediated Polymerization"), RAFT ("Reversible Addition and Fragmentation Transfer”), ATRP (“Atom Transfer Radical Polymerization") , INIFERTER ("Initiator-Transfer-Termination"), RITP ("Reverse Iodine Transfer Polymerization"), ITP (“Iodine Transfer Polymerization”).
  • the block copolymers are prepared by controlled radical polymerization, more particularly by controlled polymerization with nitroxides, in particular N-tert-butyl-1-diethylphosphono-2,2-dimethylpropyl nitroxide. .
  • the block copolymers are prepared by anionic polymerization.
  • the constituent monomers of the block copolymers will be chosen from the following monomers: at least one monomer vinylic, vinylidene, diene, olefinic, allylic or (meth) acrylic.
  • This monomer is chosen more particularly from vinylaromatic monomers such as styrene or substituted styrenes, in particular alpha-methylstyrene, silylated styrenes, acrylic monomers such as acrylic acid or its salts, alkyl acrylates and cycloalkyl acrylates.
  • aryl such as methyl acrylate, ethyl acrylate, butyl acrylate, ethylhexyl acrylate or phenyl acrylate, hydroxyalkyl acrylates such as 2-hydroxyethyl acrylate, alkyl ether acrylates such as 2-methoxyethyl acrylate, alkoxy- or aryloxy-polyalkylene glycol acrylates such as methoxypolyethylene glycol acrylates, ethoxypolyethylene glycol acrylates, methoxypolypropylene glycol acrylates, methoxypolyethylene glycol-polypropylene glycol acrylates or mixtures thereof, acrylates of aminoalkyl such as 2- (dimethylamino) ethyl acrylate (ADAME), fluorinated acrylates, silyl acrylates, phosphor acrylates such as alkylene glycol phosphate acrylates, glycidyl, dicyclopentenyl
  • the monomers will be chosen, without limitation, from the following monomers: At least one vinyl, vinylidene, diene, olefinic, allylic or (meth) acrylic monomer. These monomers are chosen more particularly from vinylaromatic monomers such as styrene or substituted styrenes, in particular alpha-methylstyrene, and acrylic monomers such as alkyl, cycloalkyl or aryl acrylates, such as methyl acrylate, dicyclohexyl acrylate and the like.
  • vinylaromatic monomers such as styrene or substituted styrenes, in particular alpha-methylstyrene
  • acrylic monomers such as alkyl, cycloalkyl or aryl acrylates, such as methyl acrylate, dicyclohexyl acrylate and the like.
  • ether alkyl acrylates such as 2-methoxyethyl acrylate, alkoxy- or aryloxy-polyalkylene glycol acrylates such as methoxypolyethylene glycol acrylates, ethoxypolyethylene glycol acrylates and the like.
  • methoxypolypropylene glycol acrylates methoxypolyethylene glycol-polypropylene glycol acrylates or mixtures thereof, aminoalkyl acrylates such as 2- (dimethylamino) ethyl acrylate (ADAME), fluorinated acrylates, silyl acrylates, phosphorus acrylates such as alkylene glycol phosphate acrylates, glycidyl acrylates, dicyclopentenyloxyethyl acrylates, methylene glycol alkyl, cycloalkyl, alkenyl or aryl acrylates such as methyl methacrylate (MMA), lauryl, cyclohexyl, allyl, phenyl or naphthyl, methacrylates of ether alkyl such as methacrylate 2-ethoxyethyl, alkoxy- or aryloxy-polyalkylene glycol methacrylates such as methoxypolyethylene glycol methacrylates,
  • the block copolymers having an order-disorder transition temperature consist of block copolymer one of which blocks comprises a styrene monomer and the other block comprises a methacrylic monomer; more preferably, the block copolymers consist of block copolymer one of which blocks comprises styrene and the other block comprises methyl methacrylate.
  • the compounds which do not have an order-disorder transition temperature will be chosen from block copolymers, as defined above, but also random copolymers, homopolymers and gradient copolymers. According to a preferred variant, the compounds are homopolymers or random copolymers and have a monomer composition identical to that of one of the block copolymer blocks having a TOD.
  • the homopolymers or random copolymers comprise styrene or methacrylic monomers.
  • random homopolymers or copolymers include styrene or methyl methacrylate.
  • the compounds that do not have an order-disorder transition temperature will also be chosen from plasticizers, among which non-limiting examples are branched or linear phthalates such as di-n-octyl, dibutyl, -2-ethylhexyl phatalate, di-ethylhexyl, diisononyl, di-isodecyl, benzylbutyl, diethyl, di-cyclohexyl, dimethyl, linear di-undecyl, di-tridecyl linear, chlorinated paraffins, trimellitates, branched or linear, in particular di-trimellitate; ethyl hexyl, aliphatic esters or polymeric esters, epoxides, adipates, citrates, benzoates.
  • plasticizers among which non-limiting examples are branched or linear phthalates such as di-n-octyl, dibutyl, -2-ethy
  • the compounds that do not have an order-disorder transition temperature will also be chosen from fillers among which may be mentioned mineral fillers such as carbon black, nanotubes, of carbon or not, fibers, ground or not, stabilizing agents. (light, in particular UV, and heat), dyes, inorganic or organic photosensitive pigments such as porphyrins, photoinitiators, that is to say compounds capable of generating radicals under irradiation.
  • mineral fillers such as carbon black, nanotubes, of carbon or not, fibers, ground or not, stabilizing agents. (light, in particular UV, and heat), dyes, inorganic or organic photosensitive pigments such as porphyrins, photoinitiators, that is to say compounds capable of generating radicals under irradiation.
  • Compounds that do not have an order-disorder transition temperature will also be chosen from ionic compounds, polymeric or non-polymeric.
  • a combination of the compounds mentioned may also be used in the context of the invention, such as a block copolymer having no TODT and a statistical copolymer or homopolymer having no TODT.
  • a block copolymer having a TODT, a block copolymer which does not have TODT and a charge, a homopolymer or a random copolymer, for example having no TODT may be mixed.
  • the invention therefore also relates to compositions comprising at least one block copolymer having a TODT and at least one compound, this or these compounds having no TODT.
  • the TODT of the mixture which is the subject of the invention should be less than the TODT of the block copolymer organized alone, but should be greater than the glass transition temperature, measured by DSC (differential enthalpy analysis, Tg) of the block presenting the highest Tg. .
  • DSC differential enthalpy analysis
  • the composition comprising a block copolymer having an order-disorder transition temperature and at least one compound having no order-disorder transition temperature will exhibit a self-assembly at a lower temperature than that of the block-only copolymer.
  • the ordered films obtained according to the invention have an assembly kinetics of less than 10 minutes, preferably less than 3 minutes and more preferably less than 1 minute.
  • the baking temperatures allowing the self-assembly will be between the glass transition temperature, measured by DSC (differential enthalpy analysis, Tg) of the block having the highest Tg and the TODT of the mixture, preferably between 1 and 50 ° C. below the TODT of the mixture, preferably between 10 and 30 ° C below the TODT of the mixture, and more preferably between 10 and 20 ° C below the TODT of the mixture.
  • DSC differential enthalpy analysis
  • the product of the assembly temperature and the assembly time of the mixture comprising at least one BCP exhibiting at least one Tg and one TODT and at least one compound having no TODT is less than produces the assembly temperature and the time of assembly of a single block copolymer having a TODT, the temperatures being expressed in ° C and the assembly times being expressed in minutes.
  • the method of the invention allows the deposition of ordered film on a surface such as silicon, silicon having a native or thermal oxide layer, germanium, platinum, tungsten, gold, titanium nitrides, graphenes, BARC (bottom anti-reflective coating) or any other anti-reflective layer used in lithography. Sometimes it may be necessary to prepare the surface. Among the known possibilities, there is deposited on the surface a random copolymer whose monomers may be identical in whole or in part to those used in the block copolymer composition and / or the compound to be deposited. In a pioneering article Mansky et al. (Science, vol 275 pages 1458-1460, 1997) describes this technology well, now well known to those skilled in the art.
  • the surfaces may be said to be “free” (planar and homogeneous surface both from a topographic and chemical point of view) or to have structures for guiding the block copolymer "pattern", whether this guidance is chemical guidance type (called “chemistry-epitaxy guidance”) or physical / topographical guidance (called “graphoepitaxy guidance”).
  • a solution of the block copolymer composition is deposited on the surface and then the solvent is evaporated according to techniques known to those skilled in the art such as the so-called “spin coating” technique, “Doctor Blade” “Knife system”, “slot die System” but any other technique can be used such as a dry deposit, that is to say without going through a prior dissolution.
  • a heat treatment or solvent vapor is carried out, a combination of the two treatments, or any other treatment known to those skilled in the art, which allows the block copolymer composition to organize itself properly by nanostructuring itself, and so to establish the ordered film.
  • the firing is carried out thermally at a temperature below the TODT of the mixture of copolymers with a compound.
  • the nanostructuring of a block copolymer mixture having a TODT and a compound deposited on a surface processed by the process of the invention can take the forms such as cylindrical (hexagonal symmetry (symmetry of hexagonal network primitive "6mm") according to the Hermann-mauguin notation, or tetragonal / quadratic (symmetry of the original tetragonal network "4mm”) ), spherical (hexagonal symmetry ("6mm” or “6 / mmm” hexagonal lattice symmetry), or tetragonal / quadratic (“4mm” tetragonal lattice symmetry), or cubic (“mH” lattice symmetry)) , lamellar, or gyroid.
  • the preferred form of nanostructuring is of the hexagonal cylindrical type.
  • Example 1 T odt measurement by dynamic mechanical analysis. Two different molecular weight PS- ⁇ -PAM copolymers are synthesized by anionic polymerization, but commercially available products can also be used. The characterizations of these products are summarized in Table No. 1.
  • the AMD makes it possible to measure the conservation modulus G 'and the loss module G' 'of the material and to determine the damping factor tanA defined as the ratio G' '/ G'.
  • the measurements are made on an ARES type viscoelastic meter, on which the PLANS 25mm geometry is installed.
  • the Air gap adjustment is performed at the initial temperature of 100 ° C.
  • the sample pellet is placed between the planes inside the oven heated to 100 ° C, a slight normal force is applied to ensure the sample-to-plane contact and thus avoid slip problems that could distort the measurement. torque and therefore modules.
  • the temperature sweep is performed at the frequency of 1Hz.
  • the initial strain applied to the sample is 0.1%, then it is automatically adjusted to stay above the sensor sensitivity limit of 0.2 cm. boy Wut.
  • the temperature varies from 100 to 260 ° C in the bearing mode with one measurement every two degrees and a temperature equilibrium time of 30 seconds before the measurement.
  • the lower molecular weight block copolymer After the rubber tray, the lower molecular weight block copolymer has a G 'lower than G''thus reflecting the destructuring of the copolymer, hence the order-disorder transition.
  • the T odt is thus defined as being the first intersection between G 'and G''.
  • T odt is not observed in the case of the copolymer of higher molar mass, where at any time G 'remains greater than G ". This block copolymer do not present T odt below its degradation temperature.
  • Table 2 The results of AMD analysis are summarized in Table 2 and the associated graphs are in Figure No. 1.
  • Example 2 Films resulting from the self-assembly of block copolymers.
  • the silicon substrates are cleaved into 2.5x2.5cm pieces, then the residual particles are removed under a stream of nitrogen.
  • the substrates can be cleaned with either an oxygen plasma or a piranha solution (H 2 SO 4 / H 2 O 2 mixture in a proportion of 2: 1 by volume) for a few minutes and rinsed with distilled water.
  • a solution of PS-r-PMMA as described in WO2013083919 typically 2% by weight in PGMEA (propylene glycol ether-methyl acetate)
  • S / MMA composition is then deposited on the clean substrate by spin coating (or any another suitable technique known to those skilled in the art to make this deposit) so as to obtain a film ⁇ 70nm thick.
  • the substrate is annealed at 220 ° C for 10 minutes (or any other suitable temperature / time pair) so as to perform the covalent grafting of a monolayer of molecules on the substrate; the excess of non-grafted molecules is removed by rinsing with PGMEA.
  • the PS-j-PMMA block copolymer ("BCP") or block copolymer blend solution (typically 1% by mass in PGMEA) is dispensed onto the functionalized substrate by spin coating (or another technique) in order to obtain a dry film of desired thickness.
  • the film is then annealed according to the chosen technique, for example a thermal annealing at 230 ° C.
  • the substrate can be immersed for a few minutes in acetic acid and then rinsed with distilled water, or the film can undergo a very mild oxygen plasma, or a combination of these two techniques, in order to to increase the contrast between the different phases of the block copolymer film in order to facilitate imaging of the nanostructures by the chosen technique (SEM, AFM ).
  • the block copolymer (or mixing) solution When the block copolymer (or mixing) solution is dispensed onto the functionalized substrate, the final BCP film thickness is set at 50 nm, and the annealing for self-organization of the nanostructures is carried out at 230.degree. a variable time ranging from 5 to 20 minutes, as illustrated in FIG.
  • the block copolymer mixture produced is a mixture between the reference BCPs No. 2 and No. 3, at a level of 6: 4 (60% of No. 2 mixed with 40% of No. 3). It is noted that the mixture can be made either in the solid state (for example by mixing the BCPs in powder form) or in the liquid state (for example by mixing solutions of pure BCPs of the same concentrations; concentrations of the solutions are different, mixing will be done in order to respect the fixed ratio).
  • PCO "Reference # 1" serves as a reference system for the study.
  • the imaging is performed on a scanning electron microscope "CD - SEM H9300" from Hitachi. Images are taken at a constant magnification of 100,000, to facilitate comparison between different systems; each image measures 1349nm * 1349nm.
  • FIG. 2 the assembly obtained for different assembly times is visualized with the block-only and mixed copolymer compositions.
  • Mixed copolymer compositions exhibit less defect for the same assembly times. For a given defect rate it means that the mixed copolymer compositions will assemble more quickly.

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  • General Physics & Mathematics (AREA)
  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
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  • Manufacturing & Machinery (AREA)
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  • Compositions Of Macromolecular Compounds (AREA)
  • Laminated Bodies (AREA)
  • Manufacture Of Macromolecular Shaped Articles (AREA)
  • Exposure Of Semiconductors, Excluding Electron Or Ion Beam Exposure (AREA)
  • Preparing Plates And Mask In Photomechanical Process (AREA)
  • Processes Of Treating Macromolecular Substances (AREA)

Abstract

The invention relates to a method for reducing the assembly time comprising a block copolymer (BCP). The invention also relates to the compositions used to produce said ordered films, and to the ordered films thus produced which can be used in particular as masks in the field of lithography.

Description

Procédé de réduction du temps d'assemblage des films ordonnés de copolymère à blocs  Process for reducing the assembly time of ordered films of block copolymer

La présente invention concerne un procédé de réduction du temps d'assemblage d'un film ordonné comprenant un copolymère à blocs (BCP) . L' invention concerne également les compositions utilisées pour obtenir ces films ordonnés et les films ordonnés ainsi obtenus pouvant être utilisés en particulier comme masques dans le domaine de la lithographie. The present invention relates to a method for reducing the assembly time of an ordered film comprising a block copolymer (BCP). The invention also relates to the compositions used to obtain these ordered films and the ordered films thus obtained which can be used in particular as masks in the field of lithography.

Le procédé objet de l'invention est particulièrement utile lorsqu'il s'agit d'obtenir des films ordonnés de grande surface dans des temps compatibles avec des fabrications industrielles sans que cela soit au détriment de la défectivité. The method which is the subject of the invention is particularly useful when it comes to obtaining large-area ordered films in times compatible with industrial production without this being to the detriment of the defectivity.

L'utilisation des copolymères à blocs pour générer des masques de lithographie est maintenant bien connue. Si cette technologie est prometteuse, il subsiste des difficultés pour générer rapidement des surfaces de masques pouvant être exploitées industriellement tout en conservant les autres caractéristiques qui qualifient correctement un assemblage de copolymères à blocs en particulier le nombre de défauts. La nanostructuration d'un copolymère à bloc d'une surface traité par le procédé de l'invention peut prendre les formes telles que cylindriques (symétrie hexagonale (symétrie de réseau hexagonal primitif « 6mm ») selon la notation de Hermann-Mauguin, ou tétragonale/quadratique (symétrie de réseau tétragonal primitif « 4mm ») ) , , sphérique (symétrie hexagonale (symétrie de réseau hexagonal primitif « 6mm » ou « 6/mmm ») , ou tétragonale/quadratique (symétrie de réseau tétragonal primitif « 4mm ») , ou cubique (symétrie de réseau « ») ) , lamellaires, ou gyroïde. De préférence, la forme préférée que prends la nanostructuration est du type cylindrique hexagonal. The use of block copolymers to generate lithography masks is now well known. If this technology is promising, there are still difficulties in rapidly generating mask surfaces that can be exploited industrially while retaining the other characteristics that correctly qualify a block copolymer assembly, particularly the number of defects. The nanostructuration of a block copolymer of a surface treated by the process of the invention can take the forms such as cylindrical (hexagonal symmetry (symmetry of hexagonal network primitive "6mm") according to the notation of Hermann-Mauguin, or tetragonal / quadratic ("4mm" tetragonal lattice symmetry),, spherical (hexagonal symmetry ("6mm" or "6 / mmm" primitive hexagonal lattice symmetry), or tetragonal / quadratic ("4mm" tetragonal lattice symmetry) , or cubic (network symmetry "")), Lamellar, or gyroid. Preferably, the preferred form of nanostructuring is of the hexagonal cylindrical type.

Le procédé d'auto-assemblage des copolymères à bloc sur une surface traitée selon l'invention est gouverné par des lois thermodynamiques. Lorsque l'auto-assemblage conduit à une morphologie de type cylindrique, chaque cylindre est entouré de 6 cylindres voisins équidistants s'il n'y a pas de défaut. Plusieurs types de défauts peuvent ainsi être identifiés. Le premier type est basé sur l'évaluation du nombre de voisins autour d'un cylindre que constitue l'arrangement du copolymère à bloc, aussi appelés défauts de coordinance. Si cinq ou sept cylindres entourent le cylindre considéré, on considérera qu'il y a un défaut de coordinance. Le deuxième type de défaut considère la distance moyenne entre les cylindres entourant le cylindre considéré. [W.Li, F.Qiu, Y.Yang, and A.C.Shi, Macromolecules 43, 2644 (2010) ; K. Aissou, T. Baron, M. Kogelschatz, and A. Pascale, Macromol. 40, 5054 (2007) ; R. A. Segalman, H. Yokoyama, and E. J. Kramer, Adv. Matter. 13, 1152 (2003); R. A. Segalman, H. Yokoyama, and E. J. Kramer, Adv. Matter. 13, 1152 (2003)]. Lorsque cette distance entre deux voisins est supérieure à deux % de la distance moyenne entre deux voisins, on considérera qu'il y a un défaut. Pour déterminer ces deux types de défauts, on utilise classiquement les constructions de Voronoï et les triangulations de Delaunay associées. Après binarisation de l'image, le centre de chaque cylindre est identifié. La triangulation de Delaunay permet ensuite d'identifier le nombre de voisins de premier ordre et de calculer la distance moyenne entre deux voisins. On peut ainsi déterminer le nombre de défauts. Cette méthode de comptage est décrite dans l'article de Tiron et al. (J. Vac. Sci . Technol. B 29(6), 1071-1023, 2011) . Un dernier type de défaut concerne l'angle de cylindres du copolymère à bloc déposé sur la surface. Lorsque le copolymère à bloc est non plus perpendiculaire à la surface mais couché parallèlement à celle-ci on considérera qu'un défaut d'orientation apparaît. The method for self-assembly of block copolymers on a treated surface according to the invention is governed by thermodynamic laws. When the self-assembly leads to a morphology of cylindrical type, each cylinder is surrounded by 6 equidistant neighboring cylinders if there is no defect. Several types of defects can thus be identified. The first type is based on the evaluation of the number of neighbors around a cylinder constituted by the arrangement of the block copolymer, also called coordination defects. If five or seven cylinders surround the cylinder considered, it will be considered that there is a lack of coordination. The second type of defect considers the average distance between the cylinders surrounding the cylinder considered. [W.Li, F.Qiu, Y.Yang, and ACShi, Macromolecules 43, 2644 (2010); K. Aissou, T. Baron, M. Kogelschatz, and A. Pascale, Macromol. 40, 5054 (2007); RA Segalman, H. Yokoyama, and EJ Kramer, Adv. Matter. 13, 1152 (2003); RA Segalman, H. Yokoyama, and EJ Kramer, Adv. Matter. 13, 1152 (2003)]. When this distance between two neighbors is greater than two percent of the average distance between two neighbors, it will be considered that there is a fault. To determine these two types of defects, Voronoi constructions and associated Delaunay triangulations are conventionally used. After binarization of the image, the center of each cylinder is identified. The Delaunay triangulation then makes it possible to identify the number of first-order neighbors and to calculate the average distance between two neighbors. It is thus possible to determine the number of defects. This counting method is described in the article by Tiron et al. (J. Vac Sci Technol B 29 (6), 1071-1023, 2011). A last type of defect concerns the angle of cylinders of the block copolymer deposited on the surface. When the block copolymer is no longer perpendicular to the surface but lying parallel to it, it will be considered that a defect of orientation appears.

Lorsqu'il s'agit d'obtenir un film ordonné présentant les meilleurs caractéristiques, en particulier un minimum de défaut, la cuisson nécessaire à l'auto-assemblage d'un copolymère à blocs peut prendre des temps allant de plusieurs minutes à plusieurs heures. When it comes to obtaining an ordered film having the best characteristics, in particular a minimum of defect, the firing required for the self-assembly of a block copolymer can take times ranging from several minutes to several hours. .

Le procédé de l'invention permet d'obtenir des assemblages nanostructurés sous forme de films ordonnés avec une réduction du temps nécessaire à un assemblage correct par rapport à ce qui est observé lorsqu'un seul copolymère à blocs est utilisé. The method of the invention makes it possible to obtain nanostructured assemblies in the form of ordered films with a reduction in the time required for correct assembly compared to what is observed when only one block copolymer is used.

Les BCPs purs s' organisant en films ordonnés avec peu de défauts sont très difficiles à obtenir dans des temps compatibles avec des cycles industriels, c'est-à-dire quelques minutes voir quelques secondes. Dans ce dernier cas on peut parler de « trempe ». Les mélanges comprenant au moins un BCP sont une solution à ce problème, et on montre dans la présente invention que les mélanges comprenant au moins un BCP présentant une température ordre-désordre (TODT) , associé à au moins un composé ne présentant pas de TODT sont une solution, lorsque que la température de transition ordre-désordre (TODT) du mélange est inférieure à la TODT du BCP seul. On note une cinétique d'assemblage plus rapide sur les films ordonnés obtenus à l'aide de ces mélanges par rapport aux films ordonnés obtenus avec un copolymère à blocs seul. Pure BCPs organized into ordered films with few defects are very difficult to obtain in times compatible with industrial cycles, that is to say a few minutes or even seconds. In the latter case we can speak of "quenching". Mixtures comprising at least one BCP are a solution to this problem, and it is shown in the present invention that mixtures comprising at least one BCP having an order-disorder temperature (TODT), associated with at least one compound having no TODT are a solution, when the order-disorder transition temperature (TODT) of the mixture is lower at the PCO TODT alone. Faster assembly kinetics are noted on the ordered films obtained with the aid of these mixtures compared to the ordered films obtained with a block-only copolymer.

Résumé de l'invention : Summary of the invention

L' invention concerne un procédé de réduction du temps d'assemblage d'un film ordonné de copolymère à blocs, le dit film ordonné comprenant un mélange d'au moins un copolymère à blocs présentant une température de transition ordre- désordre (TODT) et au moins une Tg avec au moins un composé ne présentant pas de TODT, ce mélange présentant une TODT inférieure à la TODT du copolymère à blocs seul, le procédé comprenant les étapes suivantes : The invention relates to a method for reducing the assembly time of an ordered film of block copolymer, said ordered film comprising a mixture of at least one block copolymer having an order - disorder transition temperature (TODT) and at least one Tg with at least one compound having no TODT, this mixture having a TODT lower than the TODT of the block copolymer alone, the process comprising the following steps:

-Mélanger au moins un copolymère à blocs présentant une TODT et au moins un composé ne présentant pas de TODT dans un solvant, -Mixing at least one block copolymer having a TODT and at least one compound having no TODT in a solvent,

-Déposer ce mélange sur une surface, -Dest this mixture on a surface,

-Cuire le mélange déposé sur la surface à une température comprise entre la Tg la plus haute du copolymère à blocs et la TODT du mélange. -Bake the mixture deposited on the surface at a temperature between the highest Tg of the block copolymer and the TODT of the mixture.

Description détaillée : S' agissant du ou des copolymères à blocs présentant une température de transition ordre-désordre, tout copolymère à blocs, quelle que soit sa morphologie associée, pourra être utilisé dans le cadre de l'invention, qu'il s'agisse de copolymère di-blocs, tri-blocs linéaire ou en étoile, multi- blocs linéaires, en peigne ou en étoile. De préférence, il s'agit de copolymères di-blocs ou tri-blocs, et de façon encore préférée de copolymères di-blocs. DETAILED DESCRIPTION: With regard to the block copolymer or copolymers having an order-disorder transition temperature, any block copolymer, whatever its associated morphology, may be used in the context of the invention, whether it concerns of diblock copolymer, linear or star triblock, linear multiblock, comb or star. Preferably, these are diblock or triblock copolymers, and more preferably diblock copolymers.

La température de transition ordre-désordre TODT, qui correspond à une séparation de phase des blocs constitutifs du copolymère à blocs peut être mesurée de différente manière, telle que la DSC (differential scanning calorimetry, analyse thermique différentielle) , la SAXS (small angle X ray scattering, diffusion des rayons X aux petits angles), la biréfringence statique, l'analyse mécanique dynamique, DMA ou tout autre méthode permettant de visualiser la température à laquelle une séparation de phase apparaît (correspondant à la transition ordre désordre) . Une combinaison de ces techniques peut également être utilisée. The order-disorder transition temperature TODT, which corresponds to a phase separation of the constituent blocks of the block copolymer can be measured in different ways, such as DSC (differential scanning calorimetry, differential thermal analysis), SAXS (small angle X ray scattering, small angle X-ray scattering), static birefringence, dynamic mechanical analysis, DMA or any other method to visualize the temperature at which a phase separation occurs (corresponding to the disorder order transition). A combination of these techniques can also be used.

On peut citer de façon non limitative les références suivantes faisant état de la mesure de la TODT : The following references mentioning the measurement of the TODT may be cited in a nonlimiting manner:

-N.P. Balsara et al, Macromolecules 1992, 25, 3896-3901-N.P. Balsara et al, Macromolecules 1992, 25, 3896-3901

-N.Sakamoto et al, Macromolecules 1997, 30, 5321-5330 et Macromolecule 1997, 30, 1621-1632 -N.Sakamoto et al., Macromolecules 1997, 30, 5321-5330 and Macromolecule 1997, 30, 1621-1632

-J.K.kim et al, Macromolecules 1998, 31, 4045-4048 La méthode préférée utilisée dans la présente invention est la DMA.  KJ.Kim et al, Macromolecules 1998, 31, 4045-4048. The preferred method used in the present invention is DMA.

On pourra dans le cadre de l'invention mélanger n copolymères à blocs à m composés, n étant un nombre entier compris entre 1 et 10, bornes comprises. De façon préférée, n est compris entre 1 et 5, bornes comprises, et de façon préférée, n est compris entre 1 et 2, bornes comprises, et de façon encore préférée n est égal à 1, m étant un nombre entier compris entre 1 et 10, bornes comprises. De façon préférée, m est compris entre 1 et 5, bornes comprises, et de façon préférée, m est compris entre 1 et 4, bornes comprises, et de façon encore préférée m est égal à 1. In the context of the invention, it will be possible to mix n m-block copolymers, n being an integer between 1 and 10 inclusive. Preferably, n is between 1 and 5, inclusive, and preferably n is between 1 and 2 inclusive, and even more preferably n is 1, where m is an integer between 1 and 10, terminals included. Preferably, m is between 1 and 5, inclusive, and preferably, m is between 1 and 4, including terminals, and more preferably m is equal to 1.

Ces copolymères à blocs pourront être synthétisés par toutes techniques connue de l'homme du métier parmi lesquelles on peut citer la polycondensation, la polymérisation par ouverture de cycle, la polymérisation anionique, cationique ou radicalaire ces techniques pouvant être contrôlées ou non, et combinées entre elles ou non. Lorsque les copolymères sont préparés par polymérisation radicalaire, celles-ci pourront être contrôlées 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 Iodine Transfer Polymerization") , ITP ("Iodine Transfer Polymerization) . These block copolymers may be synthesized by any techniques known to those skilled in the art, among which mention may be made of polycondensation, ring-opening polymerization, anionic, cationic or radical polymerization, these techniques being controllable or not, and combined between they or not. When the copolymers are prepared by radical polymerization, they may be controlled by any known technique such as NMP ("Nitroxide Mediated Polymerization"), RAFT ("Reversible Addition and Fragmentation Transfer"), ATRP ("Atom Transfer Radical Polymerization") , INIFERTER ("Initiator-Transfer-Termination"), RITP ("Reverse Iodine Transfer Polymerization"), ITP ("Iodine Transfer Polymerization").

Selon une forme préférée de l'invention, les copolymères à blocs sont préparés par polymérisation radicalaire contrôlée, encore plus particulièrement par polymérisation contrôlée par les nitroxydes, en particulier le nitroxyde de N-tertiobutyl-l-diéthylphosphono-2 , 2-diméthyl-propyle . According to a preferred form of the invention, the block copolymers are prepared by controlled radical polymerization, more particularly by controlled polymerization with nitroxides, in particular N-tert-butyl-1-diethylphosphono-2,2-dimethylpropyl nitroxide. .

Selon une seconde forme préférée de l'invention, les copolymères à blocs sont préparés par polymérisation anionique . According to a second preferred form of the invention, the block copolymers are prepared by anionic polymerization.

Lorsque la polymérisation est conduite de façon radicalaire, les monomères constitutifs des copolymères à blocs seront choisis parmi les monomères suivants : au moins un monomère vinylique, vinylidénique, diénique, oléfinique, allylique ou (méth) acrylique . Ce monomère est choisi plus particulièrement parmi les monomères vinylaromatiques tels que le styrène ou les styrènes substitués notamment l'alpha- méthylstyrène, les styrènes silylés, 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' alkylèneglycol , les 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-l- imidazolidinyl) éthyle, 1 ' 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, seuls ou en mélange d'au moins deux monomères précités. When the polymerization is carried out in a radical manner, the constituent monomers of the block copolymers will be chosen from the following monomers: at least one monomer vinylic, vinylidene, diene, olefinic, allylic or (meth) acrylic. This monomer is chosen more particularly from vinylaromatic monomers such as styrene or substituted styrenes, in particular alpha-methylstyrene, silylated styrenes, acrylic monomers such as acrylic acid or its salts, alkyl acrylates and cycloalkyl acrylates. or aryl such as methyl acrylate, ethyl acrylate, butyl acrylate, ethylhexyl acrylate or phenyl acrylate, hydroxyalkyl acrylates such as 2-hydroxyethyl acrylate, alkyl ether acrylates such as 2-methoxyethyl acrylate, alkoxy- or aryloxy-polyalkylene glycol acrylates such as methoxypolyethylene glycol acrylates, ethoxypolyethylene glycol acrylates, methoxypolypropylene glycol acrylates, methoxypolyethylene glycol-polypropylene glycol acrylates or mixtures thereof, acrylates of aminoalkyl such as 2- (dimethylamino) ethyl acrylate (ADAME), fluorinated acrylates, silyl acrylates, phosphor acrylates such as alkylene glycol phosphate acrylates, glycidyl, dicyclopentenyloxyethyl acrylates, 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, methacrylates of ether alkyl such as 2-ethoxyethyl methacrylate, alkoxy- or aryloxy-polyalkylene glycol methacrylates such as methoxypolyethylene glycol methacrylates, ethoxypolyethylene glycol methacrylates, methoxypolypropylene glycol methacrylates, methoxy methacrylates and the like; polyethylene glycol-polypropylene glycol or mixtures thereof, aminoalkyl methacrylates such as 2- (dimethylamino) ethyl methacrylate (MADAME), fluorinated methacrylates such as 2,2,2-trifluoroethyl methacrylate, silylated methacrylates such as 3 methacryloylpropyltrimethylsilane, phosphorus methacrylates such as alkylene glycol phosphate methacrylates, hydroxyethylimidazolidone methacrylate, hydroxyethylimidazolidinone methacrylate, 2- (2-oxo-1-imidazolidinyl) ethyl methacrylate, acrylonitrile, acrylamide or substituted acrylamides, 4-acryloylmorpholine, N-methylolacrylamide, methacrylamide or substituted methacrylamides, N-methylolmethacrylamide, methacrylamido-propyltrimethyl ammonium chloride (MAPTAC), glycidyl, dicyclopentenyloxyethyl methacrylates , itaconic acid, maleic acid or its salts, maleic anhydride, maleates or alkyl or alkoxy- or aryloxy-polyalkylene glycol hemimaleate, vinylpyridine, vinylpyrrolidinone, (alkoxy) poly (alkylene glycol) vinyl ether or divinyl ether, such as methoxy poly (ethylene glycol) vinyl ether, poly (ethylene glycol) divinyl ether, olefinic monomers, among which mention may be made of ethylene, butene, hexene and 1-octene, diene monomers including butadiene, isoprene and fluorinated olefinic monomers, and vinylidene monomers, among which mention may be made of vinylidene fluoride, alone or as a mixture of at least two aforementioned monomers.

Lorsque la polymérisation est conduite par voie anionique les monomères seront choisis, de façon non limitative parmi les monomères suivants : Au moins un monomère 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 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' 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' alkylèneglycol , les acrylates de glycidyle, de dicyclopentenyloxyethyle, 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' 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-l- imidazolidinyl) éthyle, 1 ' 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'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, seuls ou en mélange d'au moins deux monomères précités. When the polymerization is carried out anionically, the monomers will be chosen, without limitation, from the following monomers: At least one vinyl, vinylidene, diene, olefinic, allylic or (meth) acrylic monomer. These monomers are chosen more particularly from vinylaromatic monomers such as styrene or substituted styrenes, in particular alpha-methylstyrene, and acrylic monomers such as alkyl, cycloalkyl or aryl acrylates, such as methyl acrylate, dicyclohexyl acrylate and the like. ethyl, butyl, ethylhexyl or phenyl, ether alkyl acrylates such as 2-methoxyethyl acrylate, alkoxy- or aryloxy-polyalkylene glycol acrylates such as methoxypolyethylene glycol acrylates, ethoxypolyethylene glycol acrylates and the like. methoxypolypropylene glycol acrylates, methoxypolyethylene glycol-polypropylene glycol acrylates or mixtures thereof, aminoalkyl acrylates such as 2- (dimethylamino) ethyl acrylate (ADAME), fluorinated acrylates, silyl acrylates, phosphorus acrylates such as alkylene glycol phosphate acrylates, glycidyl acrylates, dicyclopentenyloxyethyl acrylates, methylene glycol alkyl, cycloalkyl, alkenyl or aryl acrylates such as methyl methacrylate (MMA), lauryl, cyclohexyl, allyl, phenyl or naphthyl, methacrylates of ether alkyl such as methacrylate 2-ethoxyethyl, alkoxy- or aryloxy-polyalkylene glycol methacrylates 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 such as 3-methacryloylpropyltrimethylsilane, methacrylates phosphorus compounds such as alkylene glycol phosphate methacrylates, hydroxyethylimidazolidone methacrylate, hydroxyethylimidazolidinone methacrylate, 2- (2-oxo-1-imidazolidinyl) ethyl methacrylate, acrylonitrile, acrylamide or substituted acrylamides, substituted 4-acryloylmorpholine, N-methylolacrylamide, methacrylamide or methacrylamides, N-methylolmethacrylamide, methacrylamido-propyltrimethyl ammonium chloride (MAPTAC), glycidyl, dicyclopentenyloxyethyl methacrylates, maleic anhydride alkyl or alkoxy- or aryloxy-polyalkylene glycol maleates or hemimaleate, vinylpyridine, vinylpyrrolidinone, (alkoxy) poly (alkylene glycol) vinyl ether or divinyl ether, such as methoxy poly (ethylene glycol) vinyl ether poly (ethylene glycol) divinyl ether, olefinic monomers, among which mention may be made of ethylene, butene, hexene and 1-octene dienes, including butadiene, isoprene and fluorinated olefinic monomers, and vinylidene monomers, among which mention may be made of vinylidene fluoride, alone or as a mixture of at least two aforementioned monomers.

De préférence les copolymères à blocs présentant une température de transition ordre-désordre sont constitués de copolymère à blocs dont un des blocs comprend un monomère styrènique et l'autre bloc comprend un monomère méthacrylique ; de façon encore préférée, les copolymères à blocs sont constitués de copolymère à blocs dont un des blocs comprend du styrène et l'autre bloc comprend du méthacrylate de méthyle. Les composés ne présentant pas de température de transition ordre-désordre seront choisis parmi les copolymères à blocs, tels que définis ci-dessus mais également les copolymères statistiques, les homopolymères , les copolymères à gradients. Selon une variante préférée, les composés sont des homopolymères ou des copolymères statistiques et présentent une composition en monomère identique à celle de l'un des blocs du copolymère à blocs présentant une TOD . Selon une forme encore préférée, les homopolymères ou copolymères statistiques comprennent des monomères styrèniques ou méthacryliques . Selon encore une forme préférée, les homopolymères ou copolymères statistiques comprennent du styrène ou du méthacrylate de méthyle. Les composés ne présentant pas de température de transition ordre-désordre seront également choisis les plastifiants, parmi lesquels on peut citer de façon non limitative les phtalates branchés ou linéaires tels que les phatalate de di-n-octyle, dibutyle, -2-éthylhexyle, di-ethyl-hexyle, di- isononyle, di-isodécyle, benzylbutyle, diéthyle, di- cyclohexyle, diméthyle, di-undecyl linéaire, di tridecyl linéaire, les paraffines chlorées, les trimellitates , branchés ou linéaires , en particulier le trimellitate de di-ethyl hexyle, les esters aliphatiques ou les esters polymériques , les époxydes, les adipates, les citrates, les benzoates . Preferably, the block copolymers having an order-disorder transition temperature consist of block copolymer one of which blocks comprises a styrene monomer and the other block comprises a methacrylic monomer; more preferably, the block copolymers consist of block copolymer one of which blocks comprises styrene and the other block comprises methyl methacrylate. The compounds which do not have an order-disorder transition temperature will be chosen from block copolymers, as defined above, but also random copolymers, homopolymers and gradient copolymers. According to a preferred variant, the compounds are homopolymers or random copolymers and have a monomer composition identical to that of one of the block copolymer blocks having a TOD. In a still preferred form, the homopolymers or random copolymers comprise styrene or methacrylic monomers. In still another preferred form, random homopolymers or copolymers include styrene or methyl methacrylate. The compounds that do not have an order-disorder transition temperature will also be chosen from plasticizers, among which non-limiting examples are branched or linear phthalates such as di-n-octyl, dibutyl, -2-ethylhexyl phatalate, di-ethylhexyl, diisononyl, di-isodecyl, benzylbutyl, diethyl, di-cyclohexyl, dimethyl, linear di-undecyl, di-tridecyl linear, chlorinated paraffins, trimellitates, branched or linear, in particular di-trimellitate; ethyl hexyl, aliphatic esters or polymeric esters, epoxides, adipates, citrates, benzoates.

Les composés ne présentant pas de température de transition ordre-désordre seront également choisis parmi les charges parmi lesquelles on peut citer charges minérales telles que le noir de carbone, des nanotubes, de carbone ou non, des fibres, broyées ou non, des agents stabilisants (lumière, en particulier UV, et chaleur) , colorants, pigments minéraux ou organiques photosensibles comme par exemple les porphyrines, les photo-amorceurs , c'est-à-dire des composés susceptibles de générer des radicaux sous irradiation. The compounds that do not have an order-disorder transition temperature will also be chosen from fillers among which may be mentioned mineral fillers such as carbon black, nanotubes, of carbon or not, fibers, ground or not, stabilizing agents. (light, in particular UV, and heat), dyes, inorganic or organic photosensitive pigments such as porphyrins, photoinitiators, that is to say compounds capable of generating radicals under irradiation.

Les composés ne présentant pas de température de transition ordre-désordre seront également choisis parmi les composés ioniques, polymères ou non. Compounds that do not have an order-disorder transition temperature will also be chosen from ionic compounds, polymeric or non-polymeric.

Une combinaison des composés cités pourra également être utilisée dans le cadre de l'invention, telle qu'un copolymère à blocs ne présentant pas de TODT et un copolymère statistique ou homopolymère ne présentant pas de TODT. On pourra par exemple mélanger un copolymère à blocs présentant une TODT, un copolymère à blocs ne présentant pas de TODT et une charge, un homopolymère ou un copolymère statistique par exemple ne présentant pas de TODT.  A combination of the compounds mentioned may also be used in the context of the invention, such as a block copolymer having no TODT and a statistical copolymer or homopolymer having no TODT. For example, a block copolymer having a TODT, a block copolymer which does not have TODT and a charge, a homopolymer or a random copolymer, for example having no TODT, may be mixed.

L' invention concerne donc également les compositions comprenant au moins un copolymère à blocs présentant une TODT et au moins un composé, ce ou ces composés ne présentant pas de TODT. The invention therefore also relates to compositions comprising at least one block copolymer having a TODT and at least one compound, this or these compounds having no TODT.

La TODT du mélange objet de l'invention devra être inférieure à la TODT du copolymère à blocs organisé seul, mais devra être supérieure à la température de transition vitreuse, mesurée par DSC (analyse enthalpique différentielle, Tg) du bloc présentant la plus haute Tg. The TODT of the mixture which is the subject of the invention should be less than the TODT of the block copolymer organized alone, but should be greater than the glass transition temperature, measured by DSC (differential enthalpy analysis, Tg) of the block presenting the highest Tg. .

En termes de comportement morphologique du mélange lors de l'auto-assemblage, cela signifie que la composition comprenant un copolymère à blocs présentant une température de transition ordre-désordre et au moins un composé ne présentant pas de température de transition ordre-désordre présentera un auto-assemblage à plus basse température que celle du copolymère à bloc seul. Les films ordonnés obtenus conformément à l'invention présentent une cinétique d'assemblage inférieure à 10 min, de préférence inférieure à 3 min et de façon encore préférée inférieure à 1 min. In terms of the morphological behavior of the mixture during the self-assembly, this means that the composition comprising a block copolymer having an order-disorder transition temperature and at least one compound having no order-disorder transition temperature will exhibit a self-assembly at a lower temperature than that of the block-only copolymer. The ordered films obtained according to the invention have an assembly kinetics of less than 10 minutes, preferably less than 3 minutes and more preferably less than 1 minute.

Les températures de cuisson permettant l'auto-assemblage seront comprises entre la température de transition vitreuse, mesurée par DSC (analyse enthalpique différentielle, Tg) du bloc présentant la plus haute Tg et la TODT du mélange, de préférence entre 1 et 50°C en dessous de la TODT du mélange, de façon préférée entre 10 et 30°C en dessous la TODT du mélange, et de façon encore préférée entre 10 et 20°C en dessous la TODT du mélange. Dans le cadre de la présente invention, le produit de la température d'assemblage et du temps d'assemblage du mélange comprenant au moins un BCP présentant au moins une Tg et une TODT et au moins un composé ne présentant pas de TODT est inférieur au produit de la température d'assemblage et du temps d'assemblage d'un copolymère à blocs seul présentant une TODT, les températures étant exprimées en °C et les temps d'assemblages étant exprimés en minutes. The baking temperatures allowing the self-assembly will be between the glass transition temperature, measured by DSC (differential enthalpy analysis, Tg) of the block having the highest Tg and the TODT of the mixture, preferably between 1 and 50 ° C. below the TODT of the mixture, preferably between 10 and 30 ° C below the TODT of the mixture, and more preferably between 10 and 20 ° C below the TODT of the mixture. In the context of the present invention, the product of the assembly temperature and the assembly time of the mixture comprising at least one BCP exhibiting at least one Tg and one TODT and at least one compound having no TODT is less than produces the assembly temperature and the time of assembly of a single block copolymer having a TODT, the temperatures being expressed in ° C and the assembly times being expressed in minutes.

Le procédé de l'invention autorise le dépôt de film ordonné sur une surface telle que le silicium, le silicium présentant une couche d'oxyde natif ou thermique, le germanium, le platine, le tungstène, l'or, les nitrures de titane, les graphènes, le BARC (bottom anti reflecting coating) ou toute autre couche anti-réflective utilisée en lithographie. Parfois il peut être nécessaire de préparer la surface. Parmi les possibilités connues, on dépose sur la surface un copolymère statistique dont les monomères peuvent être identiques en tout ou partie à ceux utilisés dans la composition de copolymère à blocs et/ou du composé que l'on veut déposer. Dans un article pionnier Mansky et al. (Science, vol 275 pages 1458-1460, 1997) décrit bien cette technologie, maintenant bien connue de l'homme du métier. The method of the invention allows the deposition of ordered film on a surface such as silicon, silicon having a native or thermal oxide layer, germanium, platinum, tungsten, gold, titanium nitrides, graphenes, BARC (bottom anti-reflective coating) or any other anti-reflective layer used in lithography. Sometimes it may be necessary to prepare the surface. Among the known possibilities, there is deposited on the surface a random copolymer whose monomers may be identical in whole or in part to those used in the block copolymer composition and / or the compound to be deposited. In a pioneering article Mansky et al. (Science, vol 275 pages 1458-1460, 1997) describes this technology well, now well known to those skilled in the art.

Selon une variante de l'invention, Les surfaces peuvent être dites « libres » (surface plane et homogène tant d'un point de vue topographique que chimique) ou présenter des structures de guidage du copolymère à bloc « pattern », que ce guidage soit du type guidage chimique (appelé « guidage par chimie-épitaxie ») ou guidage physique/topographique (appelé « guidage par graphoépitaxie ». According to a variant of the invention, the surfaces may be said to be "free" (planar and homogeneous surface both from a topographic and chemical point of view) or to have structures for guiding the block copolymer "pattern", whether this guidance is chemical guidance type (called "chemistry-epitaxy guidance") or physical / topographical guidance (called "graphoepitaxy guidance").

Pour fabriquer le film ordonné, une solution de la composition de copolymère à blocs est déposée sur la surface puis le solvant est évaporé selon des techniques connues de l'homme de métier comme par exemple la technique dite « spin coating », « docteur Blade » « knife System », « slot die System » mais tout autre technique peut être utilisée telle qu'un dépôt à sec, c'est-à-dire sans passer par une dissolution préalable. To produce the ordered film, a solution of the block copolymer composition is deposited on the surface and then the solvent is evaporated according to techniques known to those skilled in the art such as the so-called "spin coating" technique, "Doctor Blade" "Knife system", "slot die System" but any other technique can be used such as a dry deposit, that is to say without going through a prior dissolution.

On effectue par la suite un traitement thermique ou par vapeur de solvant, une combinaison des deux traitements, ou tout autre traitement connu de l'homme du métier, qui permet à la composition de copolymère à blocs de s'organiser correctement en se nanostructurant , et ainsi d'établir le film ordonné. Dans le cadre préféré de l'invention, la cuisson s'effectue de façon thermique à une température inférieure à la TODT du mélange de copolymères avec un composé . Subsequently, a heat treatment or solvent vapor is carried out, a combination of the two treatments, or any other treatment known to those skilled in the art, which allows the block copolymer composition to organize itself properly by nanostructuring itself, and so to establish the ordered film. In the preferred context of the invention, the firing is carried out thermally at a temperature below the TODT of the mixture of copolymers with a compound.

La nanostructuration d'un mélange de copolymère à blocs présentant une TODT et d'un composé déposé sur une surface traitée par le procédé de l'invention peut prendre les formes telles que cylindriques (symétrie hexagonale (symétrie de réseau hexagonal primitif « 6mm ») selon la notation de Hermann-mauguin, ou tétragonale/quadratique (symétrie de réseau tétragonal primitif « 4mm ») ) , , sphérique (symétrie hexagonale (symétrie de réseau hexagonal primitif « 6mm » ou « 6/mmm ») , ou tétragonale/quadratique (symétrie de réseau tétragonal primitif « 4mm ») , ou cubique (symétrie de réseau « mH ») ) , lamellaires, ou gyroïde. De préférence, la forme préférée que prend la nanostructuration est du type cylindrique hexagonal . The nanostructuring of a block copolymer mixture having a TODT and a compound deposited on a surface processed by the process of the invention can take the forms such as cylindrical (hexagonal symmetry (symmetry of hexagonal network primitive "6mm") according to the Hermann-mauguin notation, or tetragonal / quadratic (symmetry of the original tetragonal network "4mm") ), spherical (hexagonal symmetry ("6mm" or "6 / mmm" hexagonal lattice symmetry), or tetragonal / quadratic ("4mm" tetragonal lattice symmetry), or cubic ("mH" lattice symmetry)) , lamellar, or gyroid. Preferably, the preferred form of nanostructuring is of the hexagonal cylindrical type.

Exemple 1 : mesure de Todt par analyse mécanique dynamique. Deux copolymères à blocs PS-j -PMMA de masse molaire différente sont synthétisés par polymérisation anionique, mais des produits commerciaux disponibles peuvent aussi être utilisés . Les caractérisations de ces produits sont résumées dans le Tableau n°l. Example 1: T odt measurement by dynamic mechanical analysis. Two different molecular weight PS-β-PAM copolymers are synthesized by anionic polymerization, but commercially available products can also be used. The characterizations of these products are summarized in Table No. 1.

Tableau n°l : Caractérisations des copolymères PS-j -PMMA Table No. 1: Characterizations of PS-J-PMMA Copolymers

Ces polymères sont analysés dans les mêmes conditions par analyse mécanique dynamique (AMD) . L'AMD permet de mesurer le module de conservation G' et le module de perte G' ' du matériau et de déterminer le facteur d'amortissement tanA défini comme le rapport G' '/G'.  These polymers are analyzed under the same conditions by dynamic mechanical analysis (DMA). The AMD makes it possible to measure the conservation modulus G 'and the loss module G' 'of the material and to determine the damping factor tanA defined as the ratio G' '/ G'.

Les mesures sont réalisées sur un viscoélasticimètre type ARES, sur lequel est installée la géométrie PLANS 25mm. Le réglage entrefer est réalisé à la température initiale de 100°C. La pastille d'échantillon est placée entre les plans à l'intérieur du four chauffé à 100°C, on applique une légère force normale afin de s'assurer du contact échantillon - plans et éviter ainsi les problèmes de glissement qui pourraient fausser la mesure du couple et donc des modules. Le balayage en température est réalisé à la fréquence de 1Hz. La déformation initiale appliquée à l'échantillon est de 0.1%, elle est ensuite automatiquement ajustée afin de rester au-dessus de la limite de sensibilité du capteur qui est de 0.2 cm. g. The measurements are made on an ARES type viscoelastic meter, on which the PLANS 25mm geometry is installed. The Air gap adjustment is performed at the initial temperature of 100 ° C. The sample pellet is placed between the planes inside the oven heated to 100 ° C, a slight normal force is applied to ensure the sample-to-plane contact and thus avoid slip problems that could distort the measurement. torque and therefore modules. The temperature sweep is performed at the frequency of 1Hz. The initial strain applied to the sample is 0.1%, then it is automatically adjusted to stay above the sensor sensitivity limit of 0.2 cm. boy Wut.

La température varie de 100 à 260°C en mode palier avec une mesure tous les deux degrés et un temps d'équilibre en température de 30 secondes avant la mesure.  The temperature varies from 100 to 260 ° C in the bearing mode with one measurement every two degrees and a temperature equilibrium time of 30 seconds before the measurement.

Dans le cas des deux copolymères, certaines transitions sont bien observées : après passage de la transition vitreuse (Tg) caractérisée par l'atteinte d'un premier maximum pour tanA, le polymère atteint le plateau caoutchoutique où G' est supérieur à G' ' . Dans le cas d'un copolymère à blocs présentant un assemblage, le copolymère à blocs est structuré sur le plateau caoutchoutique. In the case of the two copolymers, certain transitions are well observed: after passage of the glass transition (Tg) characterized by the achievement of a first maximum for tanA, the polymer reaches the rubbery plateau where G 'is greater than G " . In the case of a block copolymer having an assembly, the block copolymer is structured on the rubber tray.

Après le plateau caoutchoutique, le copolymère à blocs de plus petite masse molaire présente un G' inférieur à G' ' traduisant ainsi de la déstructuration du copolymère, donc de la transition ordre-désordre. La Todt est donc définie comme étant la première intersection entre G' et G' ' . After the rubber tray, the lower molecular weight block copolymer has a G 'lower than G''thus reflecting the destructuring of the copolymer, hence the order-disorder transition. The T odt is thus defined as being the first intersection between G 'and G''.

La Todt n'est pas observée dans le cas du copolymère de masse molaire plus élevée, où à tout moment G' reste supérieur à G' ' . Ce copolymère à blocs ne présente donc pas de Todt inférieure à sa température de dégradation. Les résultats de l'analyse AMD sont résumés dans le Tableau n°2 et les graphiques associés sont dans la Figure n°l. T odt is not observed in the case of the copolymer of higher molar mass, where at any time G 'remains greater than G ". This block copolymer do not present T odt below its degradation temperature. The results of AMD analysis are summarized in Table 2 and the associated graphs are in Figure No. 1.

Tableau n°2 : Todt des différents copolymères à blocs PS-£>- PMMA Table n ° 2: T odt of the various block copolymers PS- £> - PMMA

En figure 1 on trouvera l'évolution des modules G' et G'' en fonction de la température pour les différents copolymères à blocs PS-fc-PMMA. In FIG. 1, the evolution of the modules G 'and G "as a function of the temperature for the various PS-fc-PMMA block copolymers will be found.

Exemple 2 : films résultants de 1 ' autoassemblage des copolymères à blocs. Example 2: Films resulting from the self-assembly of block copolymers.

Les substrats de silicium sont clivés en pièces de 2.5x2.5cm, puis les particules résiduelles sont éliminées sous un flux d'azote. Optionnellement , les substrats peuvent être nettoyés soit avec un plasma d'oxygène, soit via une solution piranha (mélange H2SO4 / H2O2 en proportion de 2:1 en volume) durant quelques minutes et rincés à l'eau distillée. Une solution de PS-r-PMMA comme décrit dans WO2013083919 (typiquement à 2% massique dans le PGMEA (acétate d' éthermonométhylique de propylène glycol) ) de composition S/MMA appropriée est alors déposée sur le substrat propre par spin coating (ou tout autre technique appropriée connue de l'homme du métier pour réaliser ce dépôt) de façon à obtenir un film de ~70nm d'épaisseur. Puis le substrat est recuit durant 220°C durant 10 minutes (ou tout autre couple approprié température/temps) de façon à réaliser le greffage covalent d'une monocouche de molécules sur le substrat ; l'excès de molécules non-greffées est éliminé par un rinçage avec du PGMEA. Par la suite, la solution de copolymère à bloc (« BCP ») PS-j -PMMA ou de mélange de copolymère à bloc (typiquement 1% massique dans le PGMEA) est dispensée sur le substrat fonctionnalisé par spin coating (ou une autre technique) de façon à obtenir un film sec d'épaisseur souhaitée. Le film est alors recuit selon la technique choisie, par exemple un recuit thermique à 230°C durant 5 minutes, afin de procéder à l'auto- organisation du copolymère à bloc. Enfin, optionnellement le substrat peut être immergé durant quelques minutes dans l'acide acétique puis rincé à l'eau distillée, ou bien le film peut subir un plasma d'oxygène très doux, ou encore une combinaison de ces deux techniques, afin d'augmenter le contraste entre les différentes phase du film de copolymère à bloc pour faciliter d' imagerie des nano-structures par la technique choisie (MEB, AFM...) . The silicon substrates are cleaved into 2.5x2.5cm pieces, then the residual particles are removed under a stream of nitrogen. Optionally, the substrates can be cleaned with either an oxygen plasma or a piranha solution (H 2 SO 4 / H 2 O 2 mixture in a proportion of 2: 1 by volume) for a few minutes and rinsed with distilled water. A solution of PS-r-PMMA as described in WO2013083919 (typically 2% by weight in PGMEA (propylene glycol ether-methyl acetate)) of appropriate S / MMA composition is then deposited on the clean substrate by spin coating (or any another suitable technique known to those skilled in the art to make this deposit) so as to obtain a film ~ 70nm thick. Then the substrate is annealed at 220 ° C for 10 minutes (or any other suitable temperature / time pair) so as to perform the covalent grafting of a monolayer of molecules on the substrate; the excess of non-grafted molecules is removed by rinsing with PGMEA. Subsequently, the PS-j-PMMA block copolymer ("BCP") or block copolymer blend solution (typically 1% by mass in PGMEA) is dispensed onto the functionalized substrate by spin coating (or another technique) in order to obtain a dry film of desired thickness. The film is then annealed according to the chosen technique, for example a thermal annealing at 230 ° C. for 5 minutes, in order to proceed with the self-organization of the block copolymer. Finally, optionally the substrate can be immersed for a few minutes in acetic acid and then rinsed with distilled water, or the film can undergo a very mild oxygen plasma, or a combination of these two techniques, in order to to increase the contrast between the different phases of the block copolymer film in order to facilitate imaging of the nanostructures by the chosen technique (SEM, AFM ...).

Lorsque la solution de copolymère à blocs (ou de mélange) est dispensée sur le substrat fonctionnalisé, l'épaisseur de film de BCP finale est fixée à 50nm, et le recuit permettant l'auto-organisation des nanostructures est effectué à 230°C durant un temps variable allant de 5 à 20 minutes, comme illustré en figure 2.  When the block copolymer (or mixing) solution is dispensed onto the functionalized substrate, the final BCP film thickness is set at 50 nm, and the annealing for self-organization of the nanostructures is carried out at 230.degree. a variable time ranging from 5 to 20 minutes, as illustrated in FIG.

Trois coplymères à blocs synthétisés par polymérisation anionique ou disponibles commercialement sont utilisés. Leurs caractéristiques sont données au tableau 3 :  Three block copolymers synthesized by anionic polymerization or commercially available are used. Their characteristics are given in Table 3:

a) Déterminée par SEC (chromatographie d'exclusion de taille)  a) Determined by SEC (size exclusion chromatography)

b) Déterminée par RMN 1E b) Determined by NMR 1 E

c) Déterminée par DMA (analyse dynamique mécanique, inexistante sur les copolymères 3 et 4.  c) Determined by DMA (mechanical dynamic analysis, nonexistent on copolymers 3 and 4.

d) Non-déterminée Pour la suite, le mélange de copolymère à bloc réalisé est un mélange entre les BCP de référence n°2 et n°3 , à hauteur de 6:4 (60% de n°2 mélangé avec 40% de n°3) . On note que le mélange peut être réalisé indifféremment soit à l'état solide (par exemple en mélangeant les BCPs sous forme de poudre) , soit à l'état liquide (par exemple en mélangeant des solutions des BCPs pur de mêmes concentrations ; si les concentrations des solutions sont différentes, le mélange sera effectué de façon à respecter le ratio fixé) . Le BCP « référence n°l » sert de système de référence pour l'étude. d) Not determined For the following, the block copolymer mixture produced is a mixture between the reference BCPs No. 2 and No. 3, at a level of 6: 4 (60% of No. 2 mixed with 40% of No. 3). It is noted that the mixture can be made either in the solid state (for example by mixing the BCPs in powder form) or in the liquid state (for example by mixing solutions of pure BCPs of the same concentrations; concentrations of the solutions are different, mixing will be done in order to respect the fixed ratio). PCO "Reference # 1" serves as a reference system for the study.

Comparaisons des caractéristiques des films réalisés : Comparisons of characteristics of realized films:

L' imagerie est réalisée sur un microscope électronique à balayage « CD-SEM H9300 » de chez Hitachi. Les images sont prises à un grossissement constant de 100 000, afin de faciliter la comparaison entre les différents systèmes ; chaque image mesure 1349nm*1349nm. The imaging is performed on a scanning electron microscope "CD - SEM H9300" from Hitachi. Images are taken at a constant magnification of 100,000, to facilitate comparison between different systems; each image measures 1349nm * 1349nm.

Pour l'étude comparative, on a réalisé des films d'épaisseurs équivalentes pour chaque système ; le recuit d' auto- organisation varie de 5 à 20 minutes, à 230°C. La comparaison est réalisée pour chaque temps de recuit identique.  For the comparative study, films of equivalent thicknesses were produced for each system; the annealing of self-organization varies from 5 to 20 minutes, at 230 ° C. The comparison is made for each identical annealing time.

Pour les différents temps de recuit d'auto-organisation à 230 °C de chaque système (le mélange réalisé ou le copolymère à blocs pur) , les résultats des mesures de défectivité sont regroupés dans le tableau suivant : For the different self-organization annealing times at 230 ° C. of each system (the mixture produced or the pure block copolymer), the results of the defectivity measurements are grouped together in the following table:

Taux de défauts de Defect rate

Temps d'auto- Taux de défauts de Période du Période du coordinance du  Auto-Time Period Defects Period of the Coordinating Period

organisation à coordinance du mélange copolymère à copolymère à bloc pur  coordinating organization of the pure block copolymer copolymer blend

230°C (minutes) mélange (%) (nm) bloc pur (nm)  230 ° C (minutes) mixing (%) (nm) pure block (nm)

(%)  (%)

5 32,8 65,6 52,9 53,9 5 32.8 65.6 52.9 53.9

10 32,0 64,9 52,5 54,310 32.0 64.9 52.5 54.3

15 24,4 61,6 53,9 53,515 24.4 61.6 53.9 53.5

20 21,0 57,8 53,7 54,4 20 21.0 57.8 53.7 54.4

En figure 2 on visualise l'assemblage obtenu pour différent temps d'assemblage avec les compositions de copolymère à bloc seul et en mélange. Les compositions de copolymères mélangés présentent moins de défaut pour les même temps d'assemblage. Pour un taux de défaut donné cela signifie que les compositions de copolymères mélangés s'assembleront plus rapidement . In FIG. 2, the assembly obtained for different assembly times is visualized with the block-only and mixed copolymer compositions. Mixed copolymer compositions exhibit less defect for the same assembly times. For a given defect rate it means that the mixed copolymer compositions will assemble more quickly.

Claims

Revendications claims Procédé de réduction du temps d'assemblage d'un film ordonné de copolymère à blocs, le dit film ordonné comprenant un mélange d'au moins un copolymère à blocs présentant une température de transition ordre-désordre (TODT)et au moins une Tg avec au moins un composé ne présentant pas de TODT, le ou les dit composés étant choisi parmi les copolymères à blocs, les stabilisants lumière ou chaleur, les photo- amorceurs les composés ioniques de type polymère ou non les homopolymères ou les copolymères statistiques, ce mélange présentant une TODT inférieure à la TODT du copolymère à blocs seul, le procédé comprenant les étapes suivantes : A method of reducing the assembly time of an ordered block copolymer film, said ordered film comprising a mixture of at least one block copolymer having an order-disorder transition temperature (TODT) and at least one Tg with at least one compound having no TODT, the said compound (s) being chosen from block copolymers, light or heat stabilizers, photoinitiators, ionic compounds of the polymer type or non homopolymers or random copolymers, this mixture having a TODT lower than the TODT of the block copolymer alone, the process comprising the following steps: -Mélanger au moins un copolymère à blocs présentant une TODT et au moins un composé ne présentant pas de TODT dans un solvant, -Mixing at least one block copolymer having a TODT and at least one compound having no TODT in a solvent, -Déposer ce mélange sur une surface, -Dest this mixture on a surface, -Cuire le mélange déposé sur la surface à une température comprise entre la Tg la plus haute du copolymère à blocs et la TODT du mélange. -Bake the mixture deposited on the surface at a temperature between the highest Tg of the block copolymer and the TODT of the mixture. Procédé selon revendication 1 dans lequel le copolymère à blocs présentant une TODT est un copolymère di-blocs. The process of claim 1 wherein the block copolymer having a TODT is a di-block copolymer. Procédé selon la revendication 2 selon laquelle un des blocs du copolymère di-bloc comprend un monomère styrènique et l'autre bloc comprend un monomère méthacrylique . The process of claim 2 wherein one of the blocks of the diblock copolymer comprises a monomer styrene and the other block comprises a methacrylic monomer. Procédé selon la revendication 3 selon laquelle un des blocs du copolymère di-bloc comprend du styrène et l'autre bloc comprend du méthacrylate de méthyle. Procédé selon la revendication 1 dans lequel le copolymère à blocs ne présentant pas de TODT est un copolymère di-blocs.  The process of claim 3 wherein one block of the di-block copolymer comprises styrene and the other block comprises methyl methacrylate. The process of claim 1 wherein the block copolymer lacking TODT is a diblock copolymer. Procédé selon la revendication 5 selon laquelle un des blocs du copolymère di-blocs comprend un monomère styrènique et l'autre bloc comprend un monomère méthacrylique .  The method of claim 5 wherein one of the blocks of the diblock copolymer comprises a styrene monomer and the other block comprises a methacrylic monomer. Procédé selon la revendication 6 selon laquelle un des blocs du copolymère di-blocs comprend du styrène et l'autre bloc comprend du méthacrylate de méthyle. Procédé selon la revendication 1 dans lequel la surface est libre.  The method of claim 6 wherein one of the blocks of the diblock copolymer comprises styrene and the other block comprises methyl methacrylate. The method of claim 1 wherein the surface is free. Procédé selon la revendication 1 dans lequel la surface est guidée.  The method of claim 1 wherein the surface is guided. Procédé selon l'une quelquonque des revendications précédentes dans lequel le produit de la température d'assemblage et du temps d'assemblage du mélange comprenant au moins un BCP présentant au moins une Tg et une TODT et au moins un composé est inférieur au produit de la température d'assemblage et du temps d'assemblage d'un copolymère à blocs seul présentant une TODT.  A process according to any one of the preceding claims wherein the product of the assembly temperature and the assembly time of the mixture comprising at least one PCO having at least one Tg and one TODT and at least one compound is less than the product of assembly temperature and assembly time of a single block copolymer with TODT. Composition comprenant au moins un copolymère à blocs présentant une TODT et au moins un composé, ce ou ces composés ne présentant pas de TODT.  Composition comprising at least one block copolymer having a TODT and at least one compound, this or these compounds having no TODT. Utilisation du procédé selon l'une des revendications 1 à 10 pour générer des masques de lithographie ou des films ordonnés. Masque de lithographie ou film ordonné obtenu selon la revendication 12. Use of the method according to one of claims 1 to 10 for generating lithographic masks or ordered films. Mask lithography or ordered film obtained according to claim 12.
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