• 专利附录
  • 专利说明
  • 权利要求
  • 类似技术
  • 同族专利
  • 引用文献
  • 法律状态
  • 优先权
    • 专利摘要:
    The invention relates to a nano-structured nano-structured block copolymer film at a predetermined temperature, obtained from an unstructured basic block copolymer at said predetermined temperature and at least one block comprising styrene and at least one block comprising at least one other block comprises methyl methacrylate. This block copolymer film is characterized in that it has the following modified chemical formula: (Aα (i) -co-Cγ) nb- (Bβ (k) -co-Dδ) n-1-b- (Aα (i + 1) -co-Eε) n-2-b- (Bβ (k + 1) -co-Fζ) n-3-b- b -...- (Bβ (k + x) - co-Wω) np (I) wherein: "n" represents the block number of the block copolymer, "A" represents styrene and "B" represents methyl methacrylate, or conversely, "C", "D" , "E", "F", ..., "W" respectively represent a comonomer, or a mixture of comonomers, introduced into each of the blocks of the block copolymer, the comonomer, or a mixture of co-monomers; -monomers, introduced into a styrene-based block being different from the comonomer, or mixture of comonomers, introduced into a block based on methyl methacrylate, the indices a 1 and βk represent the numbers of styrene monomer units or methyl methacrylate present in each block of the block copolymer, and are all inde endings of each other, the indices y, δ, ε, ζ ..., and ω represent the numbers of comonomer units in a given block, and are all independent of each other, the indices αi, βk , y, δ, ε, ζ ..., and ω being all greater than or equal to 1.
    公开号:FR3014877A1
    申请号:FR1362735
    申请日:2013-12-17
    公开日:2015-06-19
    发明作者:Christophe Navarro；Celia Nicolet；Xavier Chevalier
    申请人:Arkema France SA；
    IPC主号:
    专利说明:

    [0001] METHOD OF NANOSTRUCTURING BLOCK COPOLYMER FILM FROM NON - STRUCTURED BLOCK COPOLYMER BASED ON STYRENE AND METHYL METHACRYLATE, AND NANOSTRUCTURE BLOCK COPOLYMER FILM. FIELD OF THE INVENTION [0001] The present invention relates to the field of nano-structured block copolymers having nano-domains oriented in a particular direction. More particularly, the invention relates to a block copolymer film based on styrene and methyl methacrylate having a high phase segregation and nano-domains of small size, of the order of a nanometer to a few nanometers. The invention further relates to a method of nanostructuring a block copolymer film from an unstructured basic block copolymer at a predetermined temperature. [0003] The development of nanotechnologies has made it possible to constantly miniaturize the products of the field of microelectronics and mechanical microelectronic systems (MEMS) in particular. Today, conventional lithography techniques no longer meet these needs for miniaturization, because they do not allow to achieve structures with dimensions less than 60nm. It was therefore necessary to adapt the lithography techniques and create etching masks that can create smaller and smaller patterns with high resolution. With block copolymers it is possible to structure the arrangement of the constituent blocks of the copolymers, by phase segregation between the blocks thus forming nano-domains, at scales of less than 50 nm. Because of this ability to nanostructure, the use of block copolymers in the fields of electronics or optoelectronics is now well known. Among the masks studied to perform nano-lithography, block copolymer films, especially based on Polystyrene-b-Poly (methyl methacrylate), hereinafter noted PS-b-PMMA, appear as solutions very promising because they allow to create patterns with good resolution. In order to be able to use such a block copolymer film as an etching mask, a copolymer block Ref: 0396-ARK45 / AM3224 must be selectively removed to create a porous film of the residual block, the patterns of which can be subsequently transferred by etching to a underlying layer. With respect to the PS-b-PMMA film, PMMA (Poly (methyl methacrylate)) is usually selectively removed to create a residual PS (Polystyrene) mask. To create such masks, the nano-domains must be oriented perpendicularly to the surface of the underlying layer. Such a structuring of the domains requires particular conditions such as the preparation of the surface of the underlying layer, but also the composition of the block copolymer. The ratios between the blocks make it possible to control the shape of the nano-domains (arrangement in the form of lamellae, cylinders, spheres, etc.) and the molecular mass of each block makes it possible to control the size and the spacing of the blocks. that is, the period of the block copolymer. Another very important factor is the phase segregation factor, also called the Flory-Huggins interaction parameter and denoted "X". This parameter makes it possible to control the size of the nano domains. More particularly, it defines the tendency of blocks of the block copolymer to separate into nano-domains. Thus, the product XN, of the degree of polymerization N, and the Flory-Huggins parameter x, give an indication of the compatibility of two blocks and whether they can separate. For example, a diblock copolymer of strictly symmetrical composition separates into micro-domains if the product XN is greater than 10.49. If this product XN is less than 10.49, the blocks mix and the phase separation is not observed at the observation temperature. Due to the constant need for miniaturization, it is sought to increase this degree of phase separation, in order to produce nano-lithography masks making it possible to obtain very high resolutions, typically less than 20 nm, and preferably less than 20 nm. 10nm, while maintaining certain basic properties of the block copolymer, such as the high glass transition temperature Tg, the good temperature resistance of the block copolymer, or a depolymerization of PMMA under UV treatment when the block copolymer is a PS -b-PMMA, etc. [0009] In Macromolecules, 2008, 41, 9948, Y. Zhao et al. estimated the Flory-Huggins parameter for a PS-b-PMMA block copolymer. The parameter of Flory-Huggins x obeys the following relation: x = a + b / T, where the values a Ref: 0396-ARK45 / AM3224 and b are constant specific values depending on the nature of the blocks of the copolymer and T is the temperature of the heat treatment applied to the block copolymer to enable it to organize itself, ie to obtain a phase separation of the domains, an orientation of the domains and a reduction of the number of defects. More particularly, the values a and b respectively represent the entropic and enthalpic contributions. Thus, for a PS-bPMMA block copolymer, the phase segregation factor obeys the following relationship: x = 0.0282 + 4.46 / T. Therefore, even if this block copolymer makes it possible to generate domain sizes slightly smaller than 1 Onm, it does not make it possible to go much lower in terms of domain size, because of the low value of its interaction parameter. from Flory-Huggins x. This low value of the interaction parameter of Flory-Huggins therefore limits the interest of block copolymers based on PS and PMMA, for the realization of structures at very high resolutions. To circumvent this problem, Rodwogin MD et al, ACS Nano, 2010, 4, 725, demonstrated that one can change the chemical nature of the blocks of the block copolymer in order to greatly increase the parameter of Flory- Huggins x and obtain a desired morphology with a very high resolution, that is to say, whose size of the nano-domains is less than 10 nm. These results have been demonstrated in particular for a triblock copolymer of PLA-b-PDMS-b-PLA (poly (lactic acid) -blocpoly (dimethylsiloxane) -block-poly (lactic acid) H. Takahashi et al., Macromolecules , 2012, 45, 6253, studied the influence of the Flory-Huggins x interaction parameter on the copolymer's assembly kinetics and the reduction of defects in the copolymer, and demonstrated that when this parameter x becomes too much importantly, there is generally a significant slowdown in the assembly kinetics, kinetics of phase segregation also causing a slowing down of the kinetics of decrease of the defects at the time of the organization of the domains. [0013] Another problem, reported by S. Ji et al., ACS Nano, 2012, 6, 5440, also arises when one considers the kinetics of organization of block copolymers containing a plurality of blocks all chemically different from each other. Indeed, the diffusion kinetics of the polymer chains, and hence also the kinetics of organization and reduction of defects within the self-assembled structure Ref: 0396-ARK45 / AM3224, depend on the segregation parameters. x between each of the different blocks. In addition, these kinetics are also slowed down because of the multi-block nature of the copolymer, since the polymer chains then have lower degrees of freedom to organize with respect to a block copolymer having fewer blocks. US Pat. Nos. 8304493 and 8450418 describe a process for modifying base block copolymers whose interaction parameter x is high, as well as modified block copolymers. These block copolymers are modified to reduce the value of the Flory-Huggins x interaction parameter, such that the block copolymer can be structured in nano-domains of small sizes with slower kinetics. More particularly, these documents seek to reduce the Flory-Huggins x parameter of a PS-b-PDMS block copolymer (polystyrene -block-poly (dimethylsiloxane)) whose nano-domains are oriented parallel to the surface on which they are deposited. The assembly kinetics of the block copolymers described in these documents, however, remain very slow since they can last a few hours, typically up to 4 hours. Document WO 2013/019679 describes the possibility of modifying at least one of the blocks of a base block copolymer. Modification of at least one of the blocks of the block copolymer influences the surface and interfacial energies of the nanodomains and involves a modification of the morphology and orientation of the nanodomains in the block copolymer. This document remains silent as to the kinetics of organization of the modified bead copolymer and does not seek to modify the value of the interaction parameter x to allow nano-structuring of an unstructured block copolymer at a given temperature. Because PS-b-PMMA block copolymers already achieve dimensions close to 10nm, the plaintiff sought a solution to modify this type of block copolymer so that it nano-structure nano -domains of smaller size while maintaining its kinetics of organization very fast. More particularly, the Applicant has sought a solution for modifying such an unstructured block copolymer at a given temperature, by its value of XN less than 10, so as to increase the parameter of Flory- Ref: 0396-ARK45 / AM3224 Huggins x and to access a structuring of the nano-domains without penalizing the kinetics of organization of the blocks of the copolymer which must be fast, that is to say of the order of a few minutes. (TECHNICAL PROBLEM) [0018] The object of the invention is therefore to remedy at least one of the disadvantages of the prior art.The invention aims in particular at providing a nanostructuring process, in nano-domains of sizes of less than 10 nm, of a block copolymer film from an unstructured basic block copolymer at a predetermined temperature and at least one block of which comprises styrene and at least one other block comprises methyl methacrylate. The block copolymer is modified so that the product XN is greater than or equal to 7 and preferably greater than or equal to 10 to allow good phase segregation between the nano-domains and obtaining a resolution of The nanostructuring process must also allow a very fast organization of the block copolymer with organizational kinetics of the order of a few minutes. In the order of a few minutes, the product XN must also be less than or equal to 500, and preferably less than or equal to 200. The invention also aims at providing a nano-structured block copolymer film. in nano-domains of sizes less than 10 nm at a given temperature, obtained from an unstructured basic block copolymer at said determined temperature and at least one block of which comprises styrene and at least one other block comprises styrene methacrylate; methyl, said copolymer being modified to nano-structure in nano-domains with kinetics of fast block organization. (BRIEF DESCRIPTION OF THE INVENTION [0019] Surprisingly, it has been discovered that a nano-structured nano-structured block copolymer film at a determined temperature, obtained from a base block copolymer unstructured at said predetermined temperature and at least one block of which comprises styrene and at least one other block comprises methyl methacrylate, said block copolymer film being characterized in that it is in the following modified chemical form: Aaw-co-Cy) nb- (BE3 (k) -co-DE) n_i -b- (Aa0 + 1) -co-Ejn_2-b- (BE3 (k + i) -co-F () n_3-b in which: Ref: 0396-ARK45 / AM3224 "n" represents the number of blocks of the block copolymer, "A" represents styrene and "B" represents methyl methacrylate, or conversely, "C", "D", "E", "F", "W" represent respectively a comonomer, or a mixture of comonomers, introduced into each blocks of the block copolymer, the comonomer, or comonomer mixture, introduced into a styrene-based block being different from the comonomer, or mixture of comonomers, introduced into a block based on methyl methacrylate, the indices a 1 and 13k represent the number of units of styrene or methyl methacrylate monomers present in each block of the block copolymer, and are all independent of each other, the indices y, δ, c, ..., and w represent the numbers of comonomer units in a given block, and are all independent of each other, the indices ai, 13k, y, δ, c, and w being all greater than or equal to 1, 15 allows to obtain an XN value in the desired range and makes it possible to obtain nano-domains of small sizes, typically less than 10 nm, while retaining kinetics of organization and reduction of defects that are suitable and of the same order of magnitude that organizational kinetics ion of a base block copolymer, that is to say unmodified, PS-b-PMMA, typically of the order of a few minutes to a few tens of minutes. The invention also relates to a nano-structuring process in nano-domains, a block copolymer film from an unstructured basic block copolymer at a predetermined temperature and at least one block comprises styrene and at least one other block comprises methyl methacrylate, said process being characterized in that it comprises the following steps: - synthesizing said block copolymer by incorporating into each block of said block copolymer base, at least one comonomer, said block copolymer then corresponding to the following modified formula (I): (Aci (j) -CO-COn-b- (Bij (k) -CO-DE) nlb- (Aa (j + 1) -CO-E1-2-b- (B13 (k + 1) -CO-F () n-3-b- ... - b- (BE3 (k + x) -CO-V Wherein: "n" represents the number of blocks of the block copolymer, "A" represents styrene and "B" represents methyl methacrylate, or conversely, Ref: 0396-ARK45 / AM3224 "C "," D "," E "," F ", ...," W "" respectively represent comonomers, or mixtures of comonomers, introduced into each of the blocks of the block copolymer, the comonomer, or mixture of comonomers, introduced into a block based on styrene being different from the -monomer, or mixture of comonomers, introduced into a block based on methyl methacrylate, the indices a 1 and pk represent the numbers of monomeric units styrene or methyl methacrylate present in each block of the block copolymer, and are all independent of each other, the indices y, Ô, c, ..., and w represent the numbers of units of comonomers in a given block, and are all independent of each other, the indices ai, pk wherein y, Ô, c, and w are all greater than or equal to 1, applying a solution of said block copolymer in the form of a film to a surface, evaporation of the solvent from the solution and annealing at said determined temperature. The invention finally relates to a nano-lithography mask obtained from a film of said block copolymer described above, deposited on a surface to be etched according to the above method, said copolymer film comprising nano-domains oriented perpendicular to the surface to be engraved. Other features and advantages of the invention will appear on reading the description given by way of illustrative and non-limiting example, with reference to the appended figures, which represent: - Figure 1, a diagram of a An example of a polymerization plant that can be used is: FIG. 2, a photograph, taken under a scanning electron microscope, of a sample of a modified and nanostructured PS-b-PMMA block copolymer film according to FIG. invention. Detailed Description of the Invention [0023] The term "monomer" as used refers to a molecule that can undergo polymerization. The term "polymerization" as used refers to the process of converting a monomer or a mixture of monomers into a polymer. Ref: 0396-ARK45 / AM3224 [0025] The term "copolymer block" or "block" means a copolymer comprising several monomer units of several types. By "block copolymer" is meant a polymer comprising at least two copolymer blocks as defined above, the two copolymer blocks being different from one another and having a phase segregation parameter such that they are not miscible and separate into nano-domains. The term "miscibility" used above refers to the ability of two compounds to mix completely to form a homogeneous phase. The principle of the invention is to modify the chemical backbone of a PS-b-PMMA base block copolymer, while keeping styrene and methyl methacrylate units in each block, by introducing co-monomers when of the polymerization reaction of each block. This introduction of co-monomers into each of the blocks makes it possible to gradually modulate the Flory-Huggins x interaction parameter of a PS and PMMA block copolymer, depending on the extent of the skeletal modification. Thus, thanks to such a modification, it becomes possible to increase the product XN so that it becomes greater than 10, in order to allow nano-structuring of the nano-domain block copolymer, the size of which is less than 10 nm. and preferably from 1 to a few nanometers, while maintaining very fast organization kinetics, of the order of one to a few minutes. For this purpose, the block copolymer has the following chemical formula: (Aaw-co-Cy) nb- (BE3 (k) -co-DE) n_i -b- (Aa0 + 1) -co-Ejn_2- b- (BE3 (k + 1) -co-F () n3-b- -b- (Bf3 (k + x) -CO-Ww) np (I) in which: "n" represents the number of blocks of the block copolymer, "A" represents styrene and "B" represents methyl methacrylate, or conversely, "C", "D", "E", "F" W "are the respective comonomers introduced into each of the blocks of the block copolymer The comonomer, or mixture of comonomers, introduced into a styrene-based block is different from the comonomer, or mixture of comonomers, introduced into a block based on methyl methacrylate The indices a 1 and 13k represent the number of units of monomers styrene or methyl methacrylate present in each block of the copolymer Ref: 0396-ARK45 / AM3224 blocks, and are all independent of each other. the indices y, Ô, E, ..., and wr represent the numbers of comonomer units in a given block, and are also all independent of each other. Furthermore, all the indices of the formula (I), representing the number of units of each monomer in the blocks, must simultaneously satisfy the following relations: a (i) 1, a (i + 1) 1, , a (i + x) 1, [3 (k)> _ 1, [3 (k + 1)> 1,, 13 (k + x) 1, and c.o1. Having all these indices greater than or equal to 1 makes it possible to modulate as finely as possible the phase segregation parameter x of the block copolymer. Preferably, these indices are furthermore all less than or equal to 5000. [0032] The number n of blocks of the block copolymer is preferably less than or equal to 7 and, even more preferably 21-13. [0033] Given the problems generated when a polymer has an x parameter that is too high, notably leading to a slowing down of the kinetics of organization and of reduction of defects, the XN product of the modified block copolymer, obeying the formula (I Previous, must be large enough to obtain optimum phase segregation and nano-domains smaller than 10nm, but not too high not to cause problems of kinetics of organization and reduction of defects. In the product XN, N represents the total degree of polymerization of the block copolymer (N = Zai + El3k + y-FE, FE ++ ... + w). Thus, in order to obtain a fast organization of the block copolymer and a nano-domain size of less than 10 nm, the XN product should preferably be in the range of XN 500, and even more preferably XN 200. Due to the physical definition of the interaction parameter x = (a + b / T), where "a" 25 and "b" represent an entropy and enthalpic contribution respectively, and T the temperature (in degrees Kelvin), this amounts to to write that the block copolymer should preferentially satisfy the relation 10e1 (a + b / T) 200. T represents the organization temperature of the block copolymer, that is to say the annealing temperature at which a phase separation between the different blocks is obtained, an orientation of the nano-domains obtained and a reduction in the number of defaults. Preferably, this temperature T is within a temperature range of 293 ° K673 ° K. Ref: 0396-ARK45 / AM3224 [0034] In the present invention, even if we do not limit ourselves to the number of blocks of the block copolymer, we will mainly consider the synthesis of triblock or diblock copolymers, and preferably of diblock copolymers. In the case of a block copolymer comprising an odd number of blocks, the two blocks at the ends of the block copolymer may optionally comprise either styrene or methyl methacrylate. Such a block copolymer based on PS and PMMA, whose chemical skeleton is modified by the introduction of co-monomers in each of the blocks, makes it possible to generate patterns of small sizes, of the order of one nanometer at a few nanometers, to preserve the properties related to the chemistry of the base block copolymer, ie a high glass transition temperature Tg, a good temperature resistance and a depolymerization of the blocks containing PMMA under UV, etc. ... while being able to add new properties to the modified block copolymer, such as, for example, a better resistance of the mask obtained with respect to the transfer in the substrate, a better sensitivity of one or more blocks facing a given radiation, or properties of luminescence or electron transport / holes .... The block copolymer therefore comprises at least one block copolymer formed from a styrene monomer and one or more other comonomers other than styrene and at least one other copolymer block formed from a monomer of methyl methacrylate MMA and one or more other comonomers other than methyl methacrylate. The comonomers of each of the blocks may have a statistical or gradient type arrangement. The synthesis of block copolymers can be a sequential synthesis.
    [0002] In this case, whether in radical, cationic or anionic polymerization, a first block is first synthesized with a first monomer mixture, then, in a second step, the monomers of the other blocks are introduced. In the case of a radical polymerization, it is possible to obtain a block copolymer by introducing all of the monomers concomitantly, batchwise or continuously, provided that sufficiently high reactivity ratios are observed between each monomer. In the modified block copolymer corresponding to formula (I), the sequence of different copolymer blocks can adopt either a linear structure Ref: 0396-ARK45 / AM3224, via a synthesis carried out sequentially for example, or a star structure, when the synthesis is carried out from a multifunctional initiator for example. Obtaining this modified block copolymer can also be envisaged by grafting the various blocks pre-synthesized between them, via the reactive ends. The copolymerization reaction of each block can be carried out by the usual techniques, that is to say controlled radical polymerization, anionic polymerization or ring opening polymerization, etc. In addition, it is possible to consider the copolymerization of a given copolymer block by a given technique, while the copolymerization of another copolymer block is carried out by another technique. When the copolymer blocks are not polymerizable by the same polymerization technique, two cases are then possible. In a first case, a first functionalized block is synthesized which, under the action of an initiator, can initiate the polymerization of a second block.
    [0003] In a second case, each functionalized block is synthesized separately by the polymerization technique that suits it, their functions at the end of the chain then react with each other in order to attach the blocks together. The symbols "C", "D", "E", "F", ..., "W" may each represent either pure chemical entities, that is to say a single chemical compound co- polymerized by block, or represent a set of comonomers in a given block. In this case, the copolymer block (Aa (i) -co-Cy) n, for example, then defines either styrene or methyl methacrylate as "A", co-polymerized with "C", where "C" is either a single comonomer or a set of comonomers, the number of which is any. The comonomers can be chosen from a usual list of comonomers, so that the XN of the block copolymer obtained is included in the desired range. For this we can use abacuses to know the relationship between the composition and the XN, to change the composition and content of comonomer incorporated in each block. When the polymerization process is conducted by a controlled radical pathway, any controlled radical polymerization technique may be used, whether 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 ("lodine Transfer Polymerization"). Preferably, the polymerization process by a controlled radical route will be carried out by NMP. [0043] More particularly, the nitroxides derived from the alkoxyamines derived from the stable free radical (1) are preferred RL-C-N-O '(1) 10 in which the radical RL has a molar mass greater than 15.0342 g / mol The radical RL can be a halogen atom such as chlorine, bromine or iodine, a linear hydrocarbon group, branched or cyclic It may be saturated or unsaturated, such as an alkyl or phenyl radical, or a -COOR ester group or an alkoxy -OR group, or a phosphonate -PO (OR) 2 group, provided that it has a molar mass greater than 15.0342. The radical RL, monovalent, is said in position relative to the nitrogen atom of the nitroxide radical. The remaining valences of the carbon atom and the nitrogen atom in the formula (1) can be linked to various radicals such as a hydrogen atom, a hydrocarbon radical such as an alkyl, aryl or aryl radical. -alkyl, comprising from 1 to 10 carbon atoms. It is not excluded that the carbon atom and the nitrogen atom in the formula (1) are connected to one another via a divalent radical so as to form a ring. Preferably, however, the remaining valencies of the carbon atom and the nitrogen atom of the formula (1) are attached to monovalent radicals. Preferably, the radical RL has a molar mass greater than 30 g / mol. The radical RL can for example have a molar mass of between 40 and 450 g / mol. By way of example, the radical RL may be a radical comprising a phosphoryl group, said radical RL possibly being represented by the formula: ## STR2 ## in which R 3 and R 4, may be identical or different, may be selected from alkyl, cycloalkyl, alkoxyl, aryloxyl, aryl, aralkyloxyl, perfluoroalkyl, aralkyl, and may include from 1 to 20 carbon atoms. R3 and / or R4 may also be a halogen atom such as a chlorine or bromine or fluorine or iodine atom. The radical RL may also comprise at least one aromatic ring, such as for the phenyl radical or the naphthyl radical, the latter being able to be substituted, for example by an alkyl radical comprising from 1 to 4 carbon atoms. More particularly alkoxyamines derived from the following stable radicals are preferred: N-tert-butyl-1-phenyl-2-methyl-propyl-nitroxide, N-tert-butyl-1- (2-naphthyl) -2-methylpropyl-nitroxide, N-tert-butyl-1-diethylphosphono-2,2-dimethylpropyl nitroxide, N-tert-butyl-1-dibenzylphosphono-2,2-dimethylpropyl-nitroxide, 15-N-phenyl-1-diethylphosphono-2,2-dimethylpropyl nitroxide, N-phenyl-1-diethyl phosphono-1-methyl ethyl nitroxide, N- (1-phenyl-2-methylpropyl) -1-diethylphosphono-1-methylethyl nitroxide, -4-oxo-2,2, 6,6-tetramethyl-1-piperidinyloxy, -2,4,6-tri-tert-butylphenoxy. [0045] Preferably, the alkoxyamines derived from N-tert-butyl-1-diethylphosphono-2,2-dimethylpropyl nitroxide will be used. The co-monomer (s) incorporated in a styrene-based block is (are) advantageously different from the co-monomer (s) incorporated into another block based on methyl methacrylate. The constituent comonomers of each of the styrene and methyl methacrylate-based block copolymers will be chosen from the following monomers: vinyl, vinylidene, diene, olefinic, allylic, (meth) acrylic or cyclic monomer. These monomers are chosen more particularly from vinylaromatic monomers such as styrene or substituted styrenes, especially alpha-methylstyrene, acrylic monomers such as acrylic acid or its salts, alkyl acrylates, cycloalkyl acrylates or aryl such as methyl acrylate, ethyl acrylate, butyl acrylate, ethylhexyl acrylate or phenyl acrylate, hydroxyalkyl acrylates Ref. 0396-ARK45 / AM3224 such as 2-hydroxyethyl acrylate, alkyl ether acrylates such as 2-methoxyethyl acrylate, alkoxy- or aryloxy-polyalkyleneglycol acrylates such as methoxypolyethylene glycol acrylates, ethoxypolyethylene glycol acrylates, methoxypolypropyleneglycol acrylates, methoxy-polyethyleneglycol-polypropyleneglycol acrylates or mixtures thereof, aminoalkyl acrylates such as 2- (dimethylamino) ethyl acrylate (ADAME), fluorinated acrylates, silyl acrylates, phosphorus acrylates such as s that alkylene glycol phosphate acrylates, glycidyl acrylates, dicyclopentenyloxyethyl acrylates, methacrylic monomers such as methacrylic acid or its salts, alkyl, cycloalkyl, alkenyl or aryl methacrylates such as methacrylate; Methyl (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, methoxypolyethylene glycol-polypropylene glycol methacrylates or mixtures thereof, aminoalkyl methacrylates such as 2- (dimethylamino) ethyl methacrylate (MADAME), fluorine methacrylates such as 2,2,2-trifluoroethyl methacrylate, silylated methacrylates such as 3-methacryloylpropyltrimethylsilane, phosphorus methacrylates such as alkylene glycol phosphate methacrylates, hydroxyethylimidazolidone methacrylate, hydroxy methacrylate - ethylimidazolidinone, 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, alkyl maleates or hemimaleate or alkoxy- or aryloxy-polyalkyleneglycol, vinylpyridine, vinylpyrrolidinone, (alkoxy) poly (alkylene glycol) vinyl ether or divinyl ether, such as methox poly (ethylene glycol) vinyl ether, poly (ethylene glycol) divinyl ether, olefinic monomers, among which mention may be made of ethylene, butene, 1,4-diphenylethylene, hexene and 1-octene, dienic monomers including butadiene, isoprene and fluorinated olefinic monomers, and vinylidene monomers, among which mention may be made of vinylidene fluoride, or mixtures thereof, the cyclic monomers, of which mention lactones such as e5 caprolactone, lactides, glycolides, cyclic carbonates such as trimethylenecarbonate, siloxanes such as octamethylcyclotetrasiloxane, cyclic ethers such as trioxane, cyclic amides such as ε-caprolactam, cyclic acetals such as 1,3-dioxolane, phosphazenes such as hexachlorocyclotriphosphazene, N-carboxyanhydrides, cyclic phosphorus esters such as cyclophosphorinans, cyclophospholanes, oxazo lines, where appropriate protected to be compatible with polymerization processes. During the controlled radical polymerization, the residence time in the polymerization reactor influences the value of the Flory-Huggins parameter x of the final block copolymer. Indeed, because of the different reactivities of the monomers to be incorporated in the copolymer blocks, they do not all integrate at the same speed in the chain. Therefore, depending on the residence time, the relative proportions of the different comonomers in the copolymer blocks will be different and therefore the value of the x parameter of the final block copolymer also varies. In general, radical polymerization seeks to obtain conversion rates of the order of 50-70%. Therefore, a maximum residence time in the polymerization reactor corresponding to these conversion rates is set. Thus, to obtain a conversion of 50 to 70%, the starting ratio of the comonomers to be polymerized is modified. For this, we can use abacuses to know the relationship between the starting ratio of co-monomers to be polymerized and the degree of conversion on the one hand, and between the composition of the block copolymer and the XN d 'somewhere else. When the polymerization process is carried out by an anionic route, which is the preferred route used in the invention, any anionic polymerization mechanism, whether it is liganded anionic polymerization or anionic opening polymerization, may be considered. cycle. In the preferred context of the invention will be used an anionic polymerization process in an apolar solvent, and preferably toluene, as described in patent EP0749987, and involving a micro-mixer. From Ref: 0396-ARK45 / AM3224 generally, the comonomers incorporated in each copolymer block must have a pKa such that it must be close to that of the propagating species. More particularly, the difference in pKa between the propagating species and the incorporated comonomer must be less than or equal to 12, preferably less than or equal to 10, and even more preferably less than or equal to 5. [0051] constituent monomers of the styrene-based copolymer block will be chosen from the following monomers: vinyl, vinylidene, diene, olefinic, allylic, (meth) acrylic or cyclic monomers. These monomers are chosen more particularly from vinylaromatic monomers such as styrene or substituted styrenes, especially alpha-methylstyrene, silylated styrenes, acrylic monomers such as alkyl acrylates, cycloalkyl acrylates or aryl acrylates such as acrylate. of methyl, 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, methoxypolypropylene glycol acrylates, methoxy-polyethylene 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, alkyl, cycloalkyl, alkenyl or aryl methacrylates such as methyl methacrylate (MMA), lauryl, cyclohexyl, allyl, phenyl or naphthyl, ether alkyl methacrylates such as methacrylate 2-ethoxyethyl, alkoxy- or aryloxy-polyalkylene glycol methacrylates such as methoxypolyethylene glycol methacrylates, ethoxypolyethylene glycol methacrylates, methoxypolypropylene glycol methacrylates, methoxypolyethylene 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, phosphorus methacrylates such as phosphate methacrylates; alkylene glycol, hydroxyethylimidazolidone methacrylate, hydroxyethyl methacrylate hylim idazolidinone, 2- (2-oxo-1-imidazolidinyl) ethyl methacrylate, Ref: 0396-ARK45 / AM3224 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 hemimaleates alkyl or alkoxy- or aryloxy-polyalkylene glycol, vinylpyridine, vinylpyrrolidinone, (alkoxy) poly (alkylene glycol) vinyl ether or divinyl ether, such as methoxy poly (ethylene glycol) vinyl ether, poly (ethylene glycol) divinyl ether, the olefinic monomers, among which mention may be made of ethylene, butene, 1,1-diphenylethylene, hexene and 1-octene, dienic monomers including butadiene and isoprene; as well as fluorinated olefinic monomers, and vinylidene monomers, among which mention may be made of vinylidene fluoride, cyclic monomers among which may be mentioned lactones such as ε-caprolactone, lactides, glycolides, cyclic carbonates such as trimethylenecarbonate , siloxanes such as octamethylcyclotetrasiloxane, cyclic ethers such as trioxane, cyclic amides such as ε-caprolactam, cyclic acetals such as 1,3-dioxolane, phosphazenes such as hexachlorocyclotriphosphazene, N-carboxyanhydrides, esters. Phosphorus cyclics such as cyclophosphorinans, cyclophospholanes, oxazolines, the protected case to be compatible with polymerization processes, globular methacrylates such as isobornyl methacrylates, halogenated isobornyl, halogenated alkyl methacrylate, naphthyl methacrylate, alone or in a mixture of at least two monomers mentioned above. The constituent comonomers of the copolymer block based on methyl methacrylate will be chosen from the monomers previously mentioned for the styrene-based block, excluding the possibility of using the same comonomer for the block based on styrene and the block based on methyl methacrylate. The relative proportions, in monomeric units, of each comonomer or mixture of comonomers in each copolymer block based respectively on styrene and methyl methacrylate, are then between 1% and 99%, and of preferably between 5% and 49%, limits included, relative to the comonomer of each block, respectively styrene and methyl methacrylate. Ref: 0396-ARK45 / AM3224 [0054] In addition, the comonomers "C", "D", "E", "F" W "introduced into each block may all be chemically and / or structurally different. This means that an "E" comonomer, for example, introduced into a styrene-based copolymer block, may be chemically identical to an "F" comonomer introduced into another methyl methacrylate-based copolymer block, while by being structurally different, that is, presenting another arrangement in space. This may for example be a monomer in the form of an isomer in one block and in the form of another isomer in the other block. Thus, for example, the block copolymer may comprise cis-1,4-polybutadiene in the styrene-based copolymer block and trans-1,4-polybutadiene in the methyl methacrylate copolymer block. In another example, the monomer may be a chiral monomer and may be present in one copolymer block as an enantiomer and in another copolymer block as the other enantiomer. Finally, the monomer added in the various copolymer blocks can lead to obtaining a different tacticity in the different copolymer blocks. All the indices ai of the block copolymer are independent of each other, as well as for all pk. This means that each block may contain any number of styrene or methyl methacrylate monomers. Similarly, the indices y, δ, c, ..., and w represent the numbers of comonomer units, or set of comonomers, in a given block, and are also independent of each other. others. Therefore, for example for the copolymer block "(Aa (i) -co-Cy) n", the sum ai + y is therefore equal to the degree of polymerization of this block of the block copolymer. The greater the number of incorporated comonomer units in the blocks, the more significantly the x will be modified with respect to that of a PS-bPMMA whose blocks are pure, because it is closer to more and more x of a block copolymer consisting of only comonomers. The volume fraction of each copolymer block relative to the total volume of the block copolymer may individually vary preferably from 5 to 95%, and even more preferably from 15 to 85%. In addition, the molecular weight M of each copolymer block is preferably between 500 and 200,000, inclusive, and the dispersity index Ref: 0396-ARK45 / AM3224 3014 877 19 PDi is preferably less than or equal to 2, and even more preferably it is between 1.02 and 1.7 (inclusive). In anionic polymerization, the polarity and temperature are parameters that can influence the reactivity of the monomers. It is therefore necessary to master these parameters in order to achieve conversions of 100% of the monomers, to obtain the relative proportions of each monomer initially introduced and thus to control the value of the parameter X. The temperature and the polarity of the solvent will therefore be chosen and fixed. depending on the comonomers to be incorporated and the final value of x desired for the block copolymer. Such a block copolymer, the blocks of which have a chemical structure modified by the incorporation of co-monomers can be used in various application processes such as lithography, to produce lithography masks in particular, the manufacture of membranes, functionalization and coating of surfaces, the manufacture of inks and composites, the nano-structuring of surfaces, the manufacture of transistors, diodes, or organic memory points for example. The invention also relates to a nano-structuring process, in nano-domains of size less than 10 nm, of a block copolymer film from a base block copolymer based on PS-PMMA. unstructured at a given temperature. Such a method makes it possible to control the phase segregation (XN) between the copolymer blocks of this block copolymer whose chemical structure is modified. For this, following the synthesis of the block copolymer, it is applied in solution on a surface, to form a film. The solvent of the solution is then evaporated and the film is subjected to a heat treatment. This heat treatment, or annealing, allows the block copolymer to organize itself properly, that is to say to obtain in particular a phase separation between the nano-domains, an orientation of the domains and a reduction in the number of defaults. Preferably, the temperature T of this heat treatment is such that 293 ° K T 673 ° K. The resulting block copolymer film has an ordered structuring for a given total polymerization degree, while a chemically unmodified PS-b-PMMA film does not exhibit an ordered patterning for the same degree of polymerization. Advantageously, such a modified block copolymer with a value of XN greater than 10 makes it possible to nano-structure with kinetics Ref: 0396-ARK45 / AM3224 of organization of the same order of magnitude as that of the copolymer basic block (PS-b-PMMA), that is to say a kinetics of the order of a few minutes. Preferably, the kinetics of organization is less than or equal to 5 minutes, and even more preferably it is less than or equal to 2 minutes. The invention further relates to a nano-lithography mask obtained from the modified block copolymer, deposited on a surface to be etched according to the nano-structuring process. The film thus deposited on the surface comprises nano-domains oriented perpendicularly to the surface to be etched. In the case of lithography, the desired structure, for example the generation of nano-domains perpendicular to the surface, however, requires the preparation of the surface on which the copolymer solution is deposited in order to control the energy of the area. 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 that is 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. Among the preferred surfaces include surfaces made of 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. Once the prepared surface, a solution of the modified block copolymer according to the invention is deposited and 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. Subsequently, a heat treatment is carried out which allows the block copolymer to organize properly, that is to say to obtain in particular a phase separation between the nano-domains, an orientation of the domains, a reduction of the number of defects. Preferably, the temperature T of this heat treatment is such that 293 ° K T 673 ° K, and the kinetics of organization is less than or equal to 5 minutes, preferably less than or equal to 2 minutes. This annealing step, allowing nano-structuring of the block copolymer film, can be carried out Ref: 0396-ARK45 / AM3224 under a solvent atmosphere, or thermally, or by a combination of these two methods. A modified block copolymer, corresponding to formula (I) thus makes it possible to obtain an assembly of the blocks perpendicularly to the surface on which it is deposited, with a significant phase segregation, making it possible to obtain nano-domains. small sizes, of the order of a nanometer to a few nanometers, and this with fast organization kinetics. Such a block copolymer therefore allows better control of the lithography process whose resolution is high and compatible with the current requirements in terms of component dimensions. The following examples illustrate in a non-limiting way the scope of the invention: Example 1: synthesis of a diblock copolymer P (styrene-co-111-diphenyl ethylene) -bP (methyl methacrylate) co-2- (dimethylamino) ethyl methacrylate) (P (S-co-DPE) -bP (MMA-co-MADAME)): The installation of the polymerization used is shown schematically in FIG. 1. A solution of the macro-initiator system is prepared in a Cl capacity and a solution of the monomers in a C2 capacity. The flow of the capacitor C2 is sent to an exchanger E to be brought to the initial polymerization temperature. The two streams are then sent to a mixer M, which in this example is a statistical mixer, as described in patent applications EP0749987, EP0749987 and EP0524054 and then to the polymerization reactor R which is a conventional tubular reactor. The product is received in a C3 capacity which is then transferred to a C4 capacity to be precipitated. In the capacity C1, a solution is prepared at 27.5% by weight in toluene at 45 ° C. of the P block (s-co-DPE) so that the latter is a macroinitiator system allowing subsequent initiation. the second block P (MMA-co-MADAME). For this, a solution of toluene, 133 ml of 1.5M sbutyllithium in hexane, is added under an inert atmosphere of nitrous, to which 4 kg of a mixture of styrene / 1,1-diphenylethylene at 90/10 mass are added. After 2 hours of polymerization at 45 ° C., the temperature of the Cl capacity is lowered to -20 ° C. and a solution of lithium methoxyethanolate and 72.1 g of 1,1-diphenylethylene in toluene are added in order to obtain a ratio of 1/6 molar between poly (styrylco-1,1-diphenylethyl) CH 2 C (Ph) 2 Li and CH 3 OCH 2 CH 2 OLI. The toluene solution is Ref: 0396-ARK45 / AM3224 of 23.2% by weight. The macroporous [oly (styryl-co-1,1-diphenylethyl) CH 2 C (Ph) 2 Li] [CH 3 OCH 2 CH 2 OLi 16 system is then obtained. These syntheses are also described in patent applications EP0749987 and EP0524054. In the capacity C2, is stored at -15 ° C a solution composed of MMA / MADAME (70/30 mass) previously passed on molecular sieve of alumina, 6.2% by mass in toluene. The flow of the solution of the macroinitiator system is set at 60 kg / h. The flow of the MMA / MADAME solution of the C2 capacity is sent to an exchanger so that the temperature is lowered to -20 ° C and the flow of the MMA / MADAME solution is set to 56 kg / h. The two streams are then mixed in the statistical mixer and then recovered in a C3 capacity where the copolymer is deactivated by the addition of a methanol solution. The conversion determined by measurement of the solid content is greater than 99%. The content of the C3 capacity is then precipitated dropwise in a C4 capacity with stirring containing heptane. The volume ratio between the contents of the capacitor C3 and that of C4 is 1/7. At the end of the addition of the solution of the C3 capacity, the stirring is stopped and the copolymer sediments. It is then recovered by elimination of the supernatant and filtration. After drying, the characteristics of the copolymer are the following: Mn = 29.1 kg / mol Mw / Mn = 1.2 [0082] Mass ratio P (S-co-DPE) / P (MMA-co) MADAME) = 69.8 / 30.2 [0083] EXAMPLE 2 Nano-Structuring Process of a Modified Block Copolymer Film Based on PS-b-PMMA: [0085] A Silicon Substrate is Manually Cut into Pieces 3x3cm, then the pieces are cleaned by a conventional treatment (piranha solution, oxygen plasma ...). A random copolymer of PS-r-PMMA, previously dissolved in propylene glycol monomethyl ether acetate (PGMEA) at 2% by weight, is then deposited on the substrate to be functionalized by spincoating, or any other technique of deposit known to those skilled in the art, so as to form a polymer film of about 60 to 80nm thick. The substrate is then annealed at 230.degree. C. for 5 to 10 minutes so as to graft the polymer chains onto the surface. The substrate is subsequently rinsed abundantly in PGMEA so as to remove the excess ungrafted polymer chains, then the functionalized substrate is dried under a stream of nitrogen. The modified PS-b-PMMA block polymer, as synthesized and described above, is dissolved in PGMEA at a level of 1 to 2% by mass according to the target film thickness, and is deposited on the spin-coating surface to form a film of desired thickness. By way of example, a 1.5% by weight solution may give a block copolymer film approximately 45 to 50 nm thick, when it is deposited on the surface by the 2000 spin-coating technique. revolutions / minute. The film thus formed is then annealed at 160 ° C. for 5 minutes to allow nano-structuring of the nano-domain blocks. Note that in this example, a silicon substrate has been used. This method can of course be transposed without any major modification to any other substrate of interest for the electronics described in the patent application No. FR 2974094. [0089] The photograph represented in FIG. 2, obtained by scanning electron microscopy , illustrates a nano-structured block copolymer film according to the method which has just been described. This block copolymer film comprises cylindrical blocks having a period of 20 to 21 nm where the rolls are oriented perpendicular to the substrate. The period represents the minimum distance between two blocks based on styrene, or methyl methacrylate, separated by a block based on methyl methacrylate, or styrene, and vice versa. Therefore, the resulting block copolymer film rapidly nano-structures, for a duration of less than or equal to 5 minutes, into nano-domains of sizes less than 10 nm. Ref: 0396-ARK45 / AM3224
    权利要求:
    Claims (17)
    [0001]
    REVENDICATIONS1. Nano-structured nano-structured block copolymer film at a predetermined temperature, obtained from an unstructured base block copolymer at said determined temperature and at least one block of which comprises styrene and at least one other block comprises methyl methacrylate, said block copolymer film being characterized in that it is in the following modified chemical formula: (Aaw-co-Cy) nb- (BE3 (k) -co-D6) n_i-b- (Aa0 + 1) -co-Ejn_2-b- (BE3 (k + 1) -co-F () n3-b -...- b- (Bf3 (k + x) -CO-Ww) np (I ) in which: "n" represents the number of blocks of the block copolymer, "A" represents styrene and "B" represents methyl methacrylate, or conversely "C", "D", "E", "F" "W" represent respectively a comonomer, or a mixture of comonomers, introduced into each block of the block copolymer, the comonomer, or mixture of comonomers, introduced into a styrene-based block being different of the co-monomer, or mixture of comonomers, introduced into a block based on methyl methacrylate, the indices a 1 and Bk represent the number of units of monomers styrene or methyl methacrylate present in each block of the block copolymer , and are all independent of each other, the indices y, δ, c, ..., and w represent the numbers of comonomer units in a given block, and are all independent of one another, the indices ai, Bk, y, Ô, c, and w being all greater than or equal to 1.
    [0002]
    The block copolymer film according to claim 1, characterized in that said comonomers, or comonomer mixtures, incorporated in each of the blocks are all chemically and / or structurally different from each other.
    [0003]
    3. Block copolymer film according to one of claims 1 to 2, characterized in that the number n of blocks is preferably such that and even more preferably 21-13. 30
    [0004]
    4. Block copolymer film according to one of claims 1 to 3, characterized in that the indices ai, Bk, y, Ô, c, and w are also less than or equal to 5000.
    [0005]
    5. Block copolymer film according to one of claims 1 to 4, characterized in that the relative proportions, in units of monomers, of each co-monomer, Ref: 0396-ARK45 / AM3224 or mixture of co-monomers, incorporated in each block are between 1 and 99%, preferably between 5 and 49% with respect to the co-monomer with which it copolymerizes.
    [0006]
    6. Block copolymer film according to one of claims 1 to 5, characterized in that the molecular weights of each block are between 500 and 200000 with a dispersity index of less than or equal to 2, and preferably between 1.02 and 1.70.
    [0007]
    7. Block copolymer film according to one of claims 1 to 6, characterized in that the volume fraction of each block relative to the total volume of the block copolymer ranges from 5 to 95% and preferably from 15 to 85%. %.
    [0008]
    8. block copolymer film according to one of claims 1 to 7, characterized in that the comonomers of each of the copolymer blocks have a statistical type of arrangement or gradient.
    [0009]
    9. Process for nano-domain nanostructuring of a block copolymer film from an unstructured basic block copolymer at a predetermined temperature and at least one block comprising styrene and at least one other block comprising methyl methacrylate, said process being characterized in that it comprises the following steps: - synthesizing said block copolymer by incorporating, into each of the blocks 20 of said base block copolymer, at least one comonomer, said copolymer at block then responding to the following modified formula (I): (Aa (j) -CO-Cy) nb- (B13 (k) -CO-DEI) nb- (Aa (j + 1) -Co-EE) n -2-b- (B13 (k + 1) -CO-F () n-3-b- ... - b- (B13 (k + x) -CO-Ww) n -p (I) in which: n "represents the block number of the block copolymer," A "represents styrene and" B "represents methyl methacrylate, or conversely" C "," D "," E "," F "W" " represent respectively comonomers, or mixtures comonomers introduced into each block of the block copolymer, the comonomer or comonomer mixture introduced into a styrene-based block being different from the co-monomer, or mixture of co-monomers; , introduced in a block based on methyl methacrylate, Ref: 0396-ARK45 / AM3224indicates ai and pk represent the numbers of monomeric units styrene or methyl methacrylate present in each block of the block copolymer, and are all independent of each other, the indices y, Ô, c, ..., and w represent the numbers of units of comonomers in a given block, and are all independent of each other, the indices ai, pk, y, O, c, and w being all greater than or equal to 1, applying a solution of said block copolymer in the form of a film to a surface, evaporation of the solvent from the solution and annealing at said determined temperature.
    [0010]
    10. Process according to claim 9, characterized in that the synthesis is carried out by controlled radical polymerization.
    [0011]
    11. Process according to claim 9, characterized in that the synthesis is carried out by anionic polymerization.
    [0012]
    12. Process according to claim 11, characterized in that the difference of pKa between the propagating species of a copolymer block to be synthesized and the comonomer, or incorporated comonomer mixture, is less than or equal to 12 and of preferably less than or equal to 10.
    [0013]
    13. Method according to one of claims 9 to 12, characterized in that the annealing step allows nano-structuring of the block copolymer film deposited on said surface and is carried out at a temperature T between 293 ° K and 673 ° K.
    [0014]
    14. Method according to one of claims 9 to 13, characterized in that the annealing step for nano-structuring the block copolymer film is performed under a solvent or a thermal atmosphere, or a combination of these two methods. 25
    [0015]
    15. Method according to one of claims 9 to 14, characterized in that at the time of the annealing step, the copolymer blocks are organized in nano-domains with a kinetics less than or equal to 5 minutes, preferably less than or equal to 2 minutes.
    [0016]
    16. Method according to one of claims 9 to 15, characterized in that the co30 monomer or the mixture of comonomers incorporated in each of the blocks Ref: 0396-ARK45 / AM3224copolymers is incorporated with relative proportions, in monomeric units, between 1% and 99%, and preferably between 5% and 49% with respect to the comonomer with which it copolymerizes to form a copolymer block.
    [0017]
    17. Nano-lithography mask obtained from the block copolymer film according to one of claims 1 to 8, deposited on a surface to be etched according to the method according to one of claims 9 to 16, said copolymer film comprising nano-domains oriented perpendicular to the surface to be engraved. Ref: 0396-ARK45 / AM3224
    类似技术:
    公开号 | 公开日 | 专利标题
    FR3014877A1|2015-06-19|METHOD FOR NANOSTRUCTURING A BLOCK COPOLYMER FILM FROM A NON-STRUCTURED BLOCK COPOLYMER BASED ON STYRENE AND METHYL METHACRYLATE, AND NANOSTRUCTURE BLOCK COPOLYMER FILM
    WO2015087005A1|2015-06-18|Method allowing the creation of nanometric structures by self-assembly of block copolymers
    FR3008986A1|2015-01-30|METHOD OF CONTROLLING THE PERIOD CHARACTERIZING THE MORPHOLOGY OBTAINED FROM A MIXTURE OF BLOCK COPOLYMER AND | POLYMER FROM ONE OF THE BLOCKS
    FR3022249A1|2015-12-18|METHOD FOR CONTROLLING THE PERIOD OF A NANOSTRUCTUE BLOCK COPOLYMER FILM BASED ON STYRENE AND METHYL METHACRYLATE, AND NANOSTRUCTURE BLOCK COPOLYMER FILM
    WO2013083919A1|2013-06-13|Method for preparing surfaces
    FR3010413A1|2015-03-13|METHOD FOR CONTROLLING THE PERIOD OF A NANO-STRUCTURE ASSEMBLY COMPRISING A MIXTURE OF BLOCK COPOLYMERS
    FR3010414A1|2015-03-13|PROCESS FOR OBTAINING NANO-STRUCTURED THICK FILMS OBTAINED FROM A BLOCK COPOLYMER COMPOSITION
    WO2012140383A2|2012-10-18|Method for the preparing surfaces
    WO2016193581A1|2016-12-08|Method for reducing the defectivity of a block copolymer film
    EP3019915A1|2016-05-18|Method for the perpendicular orientation of nanodomains of block copolymers, using statistical or gradient copolymers, the monomers of which differ at least in part from those present in each of the blocks of the block copolymer
    EP3080217B1|2019-02-06|Method allowing the creation of nanometric structures by self-assembly of block copolymers
    FR3010411A1|2015-03-13|METHOD FOR CONTROLLING THE PERIOD OF A NANO-STRUCTURE ASSEMBLY COMPRISING A MIXTURE OF BLOCK COPOLYMERS
    EP3080198A1|2016-10-19|Method for producing a block copolymer film on a substrate
    WO2017068259A1|2017-04-27|Process for creating nanometric structures by self-assembly of diblock copolymers
    EP3105295B1|2019-03-27|Method for controlling the surface energy of a substrate
    FR3010412A1|2015-03-13|PROCESS FOR OBTAINING NANO-STRUCTURE THICK FILMS OBTAINED FROM BLOCK COPOLYMERS
    WO2021064329A1|2021-04-08|Neutral sub-layer for a block copolymer and polymer stack comprising such a sub-layer covered with a block copolymer film
    WO2021064328A1|2021-04-08|Neutral sub-layer for a block copolymer and polymer stack comprising such a sub-layer covered with a block copolymer film
    FR3045642A1|2017-06-23|METHOD FOR REDUCING THE STRUCTURING TIME OF ORDINATED BLOCK COPOLYMER FILMS
    FR3045644A1|2017-06-23|PROCESS FOR OBTAINING THICK ORDERED FILMS AND HIGH PERIODS COMPRISING A BLOCK COPOLYMER
    同族专利:
    公开号 | 公开日
    FR3014877B1|2017-03-31|
    CN105829239A|2016-08-03|
    TWI548657B|2016-09-11|
    EP3083488A1|2016-10-26|
    KR20160100351A|2016-08-23|
    SG11201604475WA|2016-07-28|
    US20170002127A1|2017-01-05|
    JP2019173019A|2019-10-10|
    JP2017501270A|2017-01-12|
    US10011675B2|2018-07-03|
    KR101840960B1|2018-03-21|
    TW201536825A|2015-10-01|
    WO2015092241A1|2015-06-25|
    引用文献:
    公开号 | 申请日 | 公开日 | 申请人 | 专利标题
    US20120046415A1|2010-08-20|2012-02-23|Micron Technology, Inc.|Methods of forming block copolymers, methods of forming a self-assembled block copolymer structure and related compositions|WO2017103082A1|2015-12-18|2017-06-22|Arkema France|Process for obtaining thick ordered films with increased periods comprising a block copolymer|
    WO2017103084A1|2015-12-18|2017-06-22|Arkema France|Process for reducing defects in an ordered film of block copolymers|
    WO2017103062A1|2015-12-18|2017-06-22|Arkema France|Process for reducing the structuring time of ordered films of block copolymer|
    WO2017103073A1|2015-12-18|2017-06-22|Arkema France|Process for improving the critical dimension uniformity of ordered films of block copolymer|FR2679237B1|1991-07-19|1994-07-22|Atochem|PRIMING SYSTEM FOR THE ANIONIC POLYMERIZATION OF ACRYLIC MONOMERS.|
    FR2735480B1|1995-06-15|1997-07-18|Atochem Elf Sa|CONTINUOUS ANIONIC POLYMERIZATION PROCESS OF AT LEAST ONE ACRYLIC MONOMER FOR THE OBTAINING OF POLYMERS WITH A HIGH SOLID RATE|
    US6835778B2|1995-08-29|2004-12-28|Chevron Phillips Chemical Company Lp|Conjugated diene/monovinylarene block copolymers blends|
    US7255920B2|2004-07-29|2007-08-14|3M Innovative Properties Company|acrylate block copolymer pressure sensitive adhesives|
    KR101007166B1|2006-05-16|2011-01-12|닛뽕소다 가부시키가이샤|Block copolymers|
    US7964107B2|2007-02-08|2011-06-21|Micron Technology, Inc.|Methods using block copolymer self-assembly for sub-lithographic patterning|
    US8425982B2|2008-03-21|2013-04-23|Micron Technology, Inc.|Methods of improving long range order in self-assembly of block copolymer films with ionic liquids|
    FR2974094A1|2011-04-15|2012-10-19|Arkema France|PROCESS FOR PREPARING SURFACES|
    KR101963924B1|2011-07-29|2019-03-29|위스콘신 얼럼나이리서어치 화운데이션|Block copolymer materials for directed assembly of thin films|FR3029921B1|2014-12-16|2018-06-29|Arkema France|METHOD FOR CONTROLLING THE SYNTHESIS OF A BLOCK COPOLYMER CONTAINING AT LEAST ONE APOLAR BLOCK AND AT LEAST ONE POLAR BLOCK AND USE OF SUCH A BLOCK COPOLYMER IN DIRECT SELF-ASSEMBLY NANO-LITHOGRAPHY APPLICATIONS|
    US11155666B2|2016-11-30|2021-10-26|Lg Chem, Ltd.|Block copolymer|
    法律状态:
    2015-11-10| PLFP| Fee payment|Year of fee payment: 3 |
    2016-11-11| PLFP| Fee payment|Year of fee payment: 4 |
    2017-11-13| PLFP| Fee payment|Year of fee payment: 5 |
    2019-11-14| PLFP| Fee payment|Year of fee payment: 7 |
    2020-11-12| PLFP| Fee payment|Year of fee payment: 8 |
    2021-11-09| PLFP| Fee payment|Year of fee payment: 9 |
    优先权:
    申请号 | 申请日 | 专利标题
    FR1362735A|FR3014877B1|2013-12-17|2013-12-17|METHOD FOR NANOSTRUCTURING A BLOCK COPOLYMER FILM FROM A NON-STRUCTURED BLOCK COPOLYMER BASED ON STYRENE AND METHYL METHACRYLATE, AND NANOSTRUCTURE BLOCK COPOLYMER FILM|FR1362735A| FR3014877B1|2013-12-17|2013-12-17|METHOD FOR NANOSTRUCTURING A BLOCK COPOLYMER FILM FROM A NON-STRUCTURED BLOCK COPOLYMER BASED ON STYRENE AND METHYL METHACRYLATE, AND NANOSTRUCTURE BLOCK COPOLYMER FILM|
    TW103143326A| TWI548657B|2013-12-17|2014-12-11|Process for the nanostructuring of a block copolymer film using a nonstructured block copolymer based on styrene and on methyl methacrylate, and nanostructured block copolymer film|
    EP14827509.2A| EP3083488A1|2013-12-17|2014-12-15|Process for the nanostructuring of a block copolymer film using a nonstructured block copolymer based on styrene and on methyl methacrylate, and nanostructured block copolymer film|
    SG11201604475WA| SG11201604475WA|2013-12-17|2014-12-15|Process for the nanostructuring of a block copolymer film using a nonstructured block copolymer based on styrene and on methyl methacrylate, and nanostructured block copolymer film|
    CN201480068975.6A| CN105829239A|2013-12-17|2014-12-15|Process for the nanostructuring of a block copolymer film using a nonstructured block copolymer based on styrene and on methyl methacrylate, and nanostructured block copolymer film|
    KR1020167019169A| KR101840960B1|2013-12-17|2014-12-15|Process for the nanostructuring of a block copolymer film using a nonstructured block copolymer based on styrene and on methyl methacrylate, and nanostructured block copolymer film|
    PCT/FR2014/053329| WO2015092241A1|2013-12-17|2014-12-15|Process for the nanostructuring of a block copolymer film using a nonstructured block copolymer based on styrene and on methyl methacrylate, and nanostructured block copolymer film|
    US15/105,245| US10011675B2|2013-12-17|2014-12-15|Process for the nanostructuring of a block copolymer film using a nonstructured block copolymer based on styrene and on methyl methacrylate, and nanostructured block copolymer film|
    JP2016539329A| JP2017501270A|2013-12-17|2014-12-15|Method for nanostructuring block copolymer films using unstructured block copolymers based on styrene and methyl methacrylate, and nanostructured block copolymer films|
    JP2019091140A| JP2019173019A|2013-12-17|2019-05-14|Method for making nanostructure of block copolymer film using non-structured block copolymer based on styrene and methyl methacrylate, and nanostructure block copolymer film|
    [返回顶部]