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    • 专利摘要:
    The invention relates to a nano-structured nano-structured block copolymer film obtained from a base block copolymer having a molecular weight greater than 50 kg / mol and preferably greater than 100 kg / mol and less than 100 kg / mol. 250kg / mol, and at least one block comprises styrene and at least one other block comprises methyl methacrylate. This film is characterized in that the styrene-based block is formed by a copolymer of styrene and ethylene diphenyl (DPE).
    公开号:FR3022249A1
    申请号:FR1455294
    申请日:2014-06-11
    公开日:2015-12-18
    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 FOR CONTROLLING THE PERIOD OF A NANOSTRUCTURE BLOCK COPOLYMER FILM BASED ON STYRENE, AND METHYL METHACRYLATE, AND A NANOSTRUCTURE BLOCK COPOLYMER FILM. FIELD OF THE INVENTION [0001] The present invention relates to the field of nanostructured block copolymers having nano-domains oriented in a particular direction. [0002] More particularly, the invention relates to a block copolymer film. based on styrene and methyl methacrylate having a high phase segregation and a high period, preferably greater than 30 nm and even more preferably greater than 50 nm and less than 100 nm. method for controlling the period of a nanostructured block copolymer film from a base block copolymer comprising styrene and methyl methacrylate. means the minimum distance separating two neighboring domains of the same chemical composition, separated by a field of different chemical composition. The development of nanotechnologies has made it possible to constantly miniaturize products in the field of microelectronics and microelectromechanical 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. Ref: 0414-ARK50-AM3282 Among the masks studied to carry out nano-lithography, block copolymer films, in particular based on polystyrene-b-poly (methyl methacrylate), noted hereinafter b-PS -PMMA, appear as very promising solutions because they allow to create patterns with a good resolution. In order to use such a block copolymer film as an etch mask, a block of the copolymer must be selectively removed to create a porous film of the residual block, the patterns of which can be subsequently transferred by etching to an underlying layer. 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. [0008] An 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 nana-domains. Thus, the product xN, 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. [0009] Due to the constant need for miniaturization, it is sought to increase this degree of phase separation, in order to produce nanoscale lithography masks which make it possible to obtain very high resolutions, typically less than 20 nm, and preferably lower. at 10 nm, while maintaining certain basic properties of the block copolymer, such as the high glass transition temperature Tg, the good temperature stability of the block copolymer, or a depolymerization of the PMMA under UV treatment when the block copolymer is PS-b-PMMA, etc. [0010] In Macromolecules, 2008, 41, 9948, Y. Zhao et al. estimated the Flory-Huggins parameter for a PS-b-PMMA block copolymer. The parameter of Ref: 0414-ARK50 / AM3282 Flory-Huggins x obeys the following relation: x = a + b / T, where the values a 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-b-PMMA block copolymer, the phase segregation factor obeys the following relationship: x = 0.0282 + 4.46 / T. This low value of the Flory-Huggins interaction parameter thus limits the interest of block copolymers based on PS and PMMA, for producing structures with very high resolutions. To circumvent this problem, Rodwogin MD et al, ACS Nano, 2010, 4, 725, have 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 the size of the nano-domains is less than 10nm. These results have been demonstrated in particular for a triblock copolymer of PLA-b-PDMS-b-PLA (poly (lactic acid) -b / ocpoly (dimethylsiloxane) -b / oc-poly (lactic acid). [0013] H. Takahashi et al., Macromolecules, 2012, 45, 6253, have studied the influence of the Flory-Huggins x interaction parameter on the copolymer assembly kinetics and the reduction of defects in the copolymer. this parameter x becomes too important, there is generally a significant slowdown in the kinetics of assembly, the 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. US Pat. Nos. 8304493 and 8450418 disclose a process for modifying base block copolymers having high interaction parameter x, as well as modified block copolymers. s to reduce the value of the interaction parameter Flory-Huggins x, such that the block copolymer 30 can be structured in nano-domains of small size with a less slow kinetics. More particularly, these documents seek to reduce the Flory-Huggins x parameter of a block copolymer of PS-b-PDMS (polystyrene -block-poly (dimethylsiloxane)) whose nano-domains are oriented Ref: 0414-ARK50 / AM3282 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. The impact of the modification of at least one block of a PS-b-PMMA base block copolymer on the parameter x and on the structuring kinetics of the nano-domain block copolymer has been demonstrated. However, two other parameters are also important. These are on the one hand the ratios between the blocks which make it possible to control the shape of the nano-domains (arrangement in the form of lamellae, cylinders, spheres, etc.) and on the other hand the molecular mass of each block which makes it possible to control the size and spacing of the blocks, that is, the period of the block copolymer, denoted Lo. However, when it is desired to control the period of the block copolymer, so that it is high and greater than a threshold value of 30 nm for example, large polymer chains having a high degree of polymerization N, are necessary to form large blocks and therefore 15 important periods. Therefore, when it is desired to control the period of a block copolymer film, it is necessary to control the length of the polymer chains constituting each of the blocks. By way of example, to be able to produce a PS-b-PMMA block copolymer film having a large period Lo, for example greater than 30 nm, and even more preferably greater than 50 nm and less than 100 nm, the molecular masses each of the blocks must be greater than 15kg / mol. However, such a block copolymer, whose blocks are formed by large polymers then has a very high product xN and nano-structuring requires a lot of energy. Indeed, the annealing necessary for the organization of the blocks must be carried out at very high temperatures greater than or equal to 230 ° C., generally of the order of 250 ° C. for a relatively long time, generally from 2 to 4 hours, which then promotes the degradation of the polymer and the appearance of defects in the final block copolymer. Therefore, to control the period Lo of a nano structured block copolymer so that it is high, typically greater than 30nm and even more preferably greater than 50nm and less than 100nm, it is necessary to control the modulation of the product xN. It is indeed necessary that the parameter of Flory-Huggins x is Ref: 0414-ARK50 / AM3282 sufficient to allow optimal phase segregation between the blocks while having a high degree of polymerization N to allow to obtain a high period preferably greater than 30 nm. [0019] 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 attempt to increase the period of the nano-structured block copolymer. Because PS-b-PMMA block copolymers make nano-lithography masks with good resolution, the applicant sought a solution to modify this type of block copolymer in order to control its period, and in particular to obtain a period which is greater than a threshold value of 30 nm, and even more preferably greater than 50 nm and less than 100 nm, with fast nano-structuring kinetics and a significantly reduced defectivity. More particularly, the Applicant has sought a solution for modifying such a PS-b-PMMA type block copolymer, so as to be able to increase its Lo period, without the appearance of defects due to a nano-structuring temperature. high and / or slow nano-structuring kinetics. 'Technical problem.' The invention therefore aims to remedy at least one of the disadvantages of the prior art. The object of the invention is in particular to propose a method for controlling the period of nano-structuring in nano-domains of a block copolymer film from a base block copolymer having a molecular mass greater than 50 kg / mol , and preferably greater than 100kg / mol and less than 250kg / mol, and at least one block contains polystyrene, and at least one block contains methyl methacrylate. For this, 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 the obtaining a high Lo period Ref: 0414-ARK50 / AM3282, preferably greater than 30nm and even more preferably greater than 50nm and less than 100nm. The nano-structuring process must also allow a very fast organization of the block copolymer with organizational kinetics of the order of 1 to a few minutes and, at a so-called annealing temperature, lower than the degradation temperature. of the polymer. The invention also aims at providing a nano-structured nanostructured block copolymer film, obtained from a base block copolymer, having a molecular mass greater than 50 kg / mol, and preferably greater than 100 kg. / mol and less than 250kg / mol, and at least one block of which comprises styrene and at least one block comprises methyl methacrylate, said copolymer being modified in order to nanostructure with a high period, with a kinetics of organization fast blocks and / or at a temperature below the degradation temperature of the copolymer. BRIEF DESCRIPTION OF THE INVENTION Surprisingly, it has been discovered that a nano-structured nano-structured block copolymer film obtained from a base block copolymer having a molecular weight greater than 50 kg / mol, and preferably greater than 100 kg / mol and less than 250 kg / mol, and at least one block comprises styrene and at least one other block comprises methyl methacrylate, said block copolymer film being characterized in that the styrene-based block is formed by a copolymer of styrene and diphenyl ethylene (DPE), makes it possible to obtain an xN value in the desired range and makes it possible to obtain nanodomains with a high, typically higher, Lo period. at 30 nm, while allowing organization at a lower temperature than that required to organize the blocks of the base block copolymer, that is to say unmodified PS-bPMMA, and maintaining kinetics of fast organization with reduced defectivity compared to that obtained with said PS-bPMMA base block copolymer. [0026] The invention furthermore relates to a method for controlling the nano-domain nano-structuring period of a block copolymer film from a base block copolymer having a molecular weight. greater than 50kg / mol, and preferably greater than 100kg / mol and less than 250kg / mol, and of which Ref: 0414-ARK50 / AM3282 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: -synthesis of said block copolymer by incorporating into the block of said styrene-containing base block copolymer one or more diphenylethylene comonomer (DPE), 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 nanodomains oriented perpendicular to the surface to be etched and having a Lo period greater than 30 nm, and even more preferably greater than 50 nm and less than 100 nm. 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 example of polymerization plant that can be used, - Figure 2, photos, taken under a scanning electron microscope, different samples of nano-structured block copolymer, different composition and modified or not, Figure 3, photos , taken under a scanning electron microscope, of several samples of the same modified block copolymer having 2 different thicknesses and having undergone 2 different heat treatments, - Figure 4, photos, taken under a scanning electron microscope, of two samples of the same modified block copolymer having undergone a heat treatment for 2 different durations. Detailed Description of the Invention [0029] The term "monomer" as used refers to a molecule that can undergo polymerization. Ref: 0414-ARK50 / AM3282 The term "polymerization" as used refers to the process of converting a monomer or mixture of monomers into a polymer. By "block copolymer" or "block" is meant a polymer comprising several monomer units of several types, or of the same type. By "block copolymer" is meant a polymer comprising at least two blocks as defined above, the two blocks being different from one another and having a phase segregation parameter such that they are not miscible and separate into nano-domains. [0033] The term "miscibility" used above refers to the ability of two compounds to mix completely to form a homogeneous phase. In the description, when speaking of the molecular weight of the block copolymer, it is molecular weight peak Mp, measured by steric exclusion chromatography (SEC). [0035] The principle of the invention consists in modifying the chemical structure of a PS-b-PMMA base block copolymer, while keeping styrene and methyl methacrylate units in each block, by introducing diphenylethylene, also subsequently noted as DPE, during the polymerization reaction of the polystyrene-based block. This introduction of diphenylethylene into the polystyrene-based block induces a change in the mobility of the resulting P (S-co-DPE) -b-PMMA block copolymer structure. With this incorporation of DPE in the block based on Styrene, it was observed that identical chain length and therefore identical degree of polymerization N, the annealing time and the annealing temperature of the block copolymer P (S-co-DPE) -b-PMMA according to the invention are less than the time and annealing temperature of the unmodified, initial block copolymer of PS-b-PMMA. Until now, it was not possible, at identical chain length, to quickly nanostruct an unmodified PS-b-PMMA block copolymer having a high period, for example greater than 30 nm, without occurrence of defect, or even without destruction, while this becomes possible with the copolymer modified by the introduction of DPE into the PS block. The chain length of the obtained block copolymer P (S-co-DPE) -b-PMMA will be chosen according to the period Lo nano-structuring desired. The incorporation of DPE into the PS block allows the product value xN to be modulated gradually for Ref: 0414-ARK50 / AM3282 the nanostructured block copolymer film. To determine the rate of DPE to be incorporated in the PS block, we can use abacuses to know the relationship between the DPE content in the block copolymer and the product xN on the one hand, and between the degree of polymerization N and the period Lo on the other hand. This modification of the structure of the block copolymer according to the invention makes it possible to modulate the product xN around a high value, typically greater than 10, in order to allow nano-structuring of the nanodomain block copolymer, with a LO period greater than 30nm and even more preferably greater than 50nm and less than 100nm, while allowing a fast organization of the blocks (from 1 to a few minutes) at a reduced annealing temperature compared to an unmodified polymer PS- b-PMMA of identical chain length. The reduction of the annealing times and temperature is therefore particularly advantageous for making nano-structured block copolymers with a high period and without defects. The number n of blocks of the block copolymer is preferably less than or equal to 7 and even more preferably 2n53. In the present invention, even if it is not limited to the number of blocks of the block copolymer, the synthesis of triblock or diblock copolymers, and preferably of diblock copolymers, will be considered above all. In the case of a block copolymer comprising an odd number of blocks, the two blocks at the ends of the block copolymer may be either the styrene diphenyl ethylene copolymer P (S-co-DPE) or the polymethyl methacrylate PMMA. Given the problems generated when a polymer has a parameter x too high, resulting in particular a slowing of the kinetics of organization and reduction of defects, the xN product of the modified block copolymer must be large enough to obtain segregation phase optimum, but not too high not to cause problems of kinetics of organization and reduction of defects. To obtain a fast organization of the block copolymer and a nano-structuring period greater than 30 nm, the product xN should preferably be in the range of: xN 5500, and even more preferably xN 5200. Because of the physical definition of the interaction parameter x = (a + b / T), where "a" and "b" represent an entropy and enthalpic contribution respectively, and T the temperature (in degrees Kelvin), Ref: 0414-ARK50 / AM3282 this amounts to writing that the block copolymer should preferentially satisfy the relationship 105N (a + b / T) 5200. 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 defects . By introducing DPE into the PS block of the block copolymer, the entropic and enthalpy contributions of the block copolymer are modified. This modification of the contributions influences the temperature and the kinetics of annealing allowing the organization of the blocks. Due to this modification, the temperature T can then be lowered relative to the annealing temperature of a base copolymer, that is unmodified PS-bPMMA. It is preferably less than or equal to 230 ° C, and even more preferably, it is less than or equal to 210 ° C. Such an annealing temperature is lower than the degradation temperature of the block copolymer and therefore avoids the appearance of a very high concentration of defects in the modified block copolymer, when it is organized in nana-domains, and which can sometimes lead to destruction of the polymer. Advantageously, the backbone modification of the block copolymer does not disturb the properties related to the chemistry of the base block copolymer, that is to say unmodified PS-b-PMMA. Thus, the modified block copolymer retains a high glass transition temperature Tg, a good temperature resistance and a depolymerization of the blocks containing the PMMA under UV, etc. The block copolymer therefore comprises at least one copolymer block. formed from styrene monomers and diphenyl ethylene DPE comonomers and at least one other copolymer block formed from monomers of methyl methacrylate MMA. The comonomers of styrene S and diphenyl ethylene DPE of the copolymer block of P (S-co-DPE) may have a statistical or gradient type arrangement. The synthesis of the block copolymer can be a sequential synthesis. In this case, whether in radical, cationic or anionic polymerization, the first block of P (S-co-DPE) is first synthesized with a first mixture of styrene and DPE monomers, and then, in a second step, the MMA monomers of the other block are introduced. In the case of radical polymerization, it is possible to obtain a block copolymer by introducing all of the monomers concomitantly, batchwise or continuously, provided that the ratios of the block copolymer are respected. sufficiently high reactivity between each monomer. In the modified block copolymer the sequence of different copolymer blocks can adopt either a linear structure, via a synthesis carried out sequentially for example, or a star structure, when the synthesis is carried out from an initiator multi-functional 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 the P (S-co-DPE) block and the PMMA block can be carried out by the usual techniques, that is to say controlled radical polymerization, anionic polymerization or ring opening polymerization. [0047] When the polymerization process is conducted by a controlled radical route, 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 lodine Transfer Polymerization "), ITP (" lodine Transfer Polymerization "), preferably the polymerization process. by a controlled radical route will be carried out by the NMP More particularly the nitroxides from alkoxyamines derived from the stable free radical (1) are preferred RL 1 - C - N - 0. (1) 1 1 wherein the radical RL has a molar mass greater than 15.0342 g / mol.
    [0002] The radical RL can be a halogen atom such as chlorine, bromine or iodine, a linear, branched or cyclic hydrocarbon group, saturated or unsaturated such as an alkyl or phenyl radical, or a -COOR ester group or an alkoxyl group Ref: 0414-ARK50 / AM3282 -OR, or a phosphonate group -PO (OR) 2, provided that it has a molar mass greater than 15.0342. The radical RL, monovalent, is said at position i3 with respect to the nitrogen atom of the nitroxide radical. The remaining valences of the carbon atom and the nitrogen atom in the formula (1) can be linked to various radicals such as a hydrogen atom, a hydrocarbon radical such as an alkyl, aryl or aryl radical. -alkyl, comprising from 1 to 10 carbon atoms. It is not excluded that the carbon atom and the nitrogen atom in the formula (1) are connected to each other via a divalent radical, so as to form a ring. Preferably, however, the remaining valencies of the carbon atom and the nitrogen atom of the formula (1) are attached to monovalent radicals. Preferably, the radical RL has a molar mass greater than 30 g / mol. The RL radical may for example have a molar mass of between 40 and 450 g / mol. By way of example, the radical RL can be a radical comprising a phosphoryl group, said radical RL being able to be represented by the formula: R3 1 -P-R4 (2) O in which R3 and R4 can be identical or different, may be selected from alkyl, cycloalkyl, alkoxyl, aryloxyl, aryl, aralkyloxy, perfluoroalkyl, aralkyl, and may include from 1 to 20 carbon atoms. R3 and / or R4 may also be a halogen atom such as a chlorine or bromine atom or a 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-methylpropyl-nitroxide, N-tert-butyl-1- (2-naphthyl) -2-methylpropyl-nitroxide, N 1-tributyl-1-diethylphosphono-2,2-dimethylpropyl nitroxide, Ref: 0414-ARK50 / AM3282-N-tert-butyl-1-dibenzylphosphono-2,2-dimethylpropyl nitroxide, N-phenyl-1-diethylphosphono-2 2-dimethylpropyl nitroxide, N-phenyl-1-diethylphosphono-1-methylethyl 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. Preferably, the alkoxyamines derived from N-tert-butyl diethylphosphono-2, 2-dimethylpropyl nitroxide will be used. 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 comonomers to be incorporated in the copolymer block of P (S-co-DPE), 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, in radical polymerization, one 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 comonomers to polymerize and the degree of conversion on the one hand, and between the molecular weight of the block copolymer and the other xN go. 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 the liganded anionic polymerization or the anionic opening polymerization, may be considered. cycle. In the preferred context of the invention, use will be made of an anionic polymerization process in an apolar solvent, and preferably toluene, as described in patent EP0749987, and involving a micro-mixer. The relative proportions, in monomeric units, of DPE co-monomer in the styrene-based copolymer block are then between 1% to 25%, and of Ref: 0414-ARK50 / AIV13282 preferably of between 1%. and 10%, limits included, with respect to the styrene comonomer with which it copolymerizes. Within the limits of these proportions, the greater the number of incorporated DPE comonomer units in the styrene-based block, the more substantially the xN will be modified with respect to that of a PS- b-PMMA whose blocks are pure, and then it will be possible to nano-structure the copolymer with a high period. In addition, the molecular weight M of each copolymer block is preferably between 15 and 100 kg / mol, and even more preferably between 30 and 100 kg / mol, inclusive, and the dispersancy index PDi is preferably less than or equal to 2, and even more preferably it is between 1.02 and 1.7 (inclusive). Such a block copolymer, one block of which has a chemical structure modified by the incorporation of DPE co-monomers, may be used in various application methods such as lithography, for making lithographic masks in particular, or else the manufacture of membranes, functionalization and coating of surfaces, manufacture of inks and composites, nanostructuring of surfaces, fabrication of transistors, diodes, or organic memory points for example. The invention also relates to a method for controlling the nana-structuring period of a block copolymer film from a base block copolymer of PS-PMMA. Such a method makes it possible to control the nanostructuration period by modulating the phase segregation (xN) between the blocks of this block copolymer whose chemical structure is modified. For this, following the synthesis of the modified 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 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 defects. Preferably, the temperature T of this heat treatment is 5. 230 ° C, and even more preferably 210 ° C. The block copolymer film obtained has an ordered structuring for a Ref: 0414-ARK50 / AM3282 molecular weight greater than 50kg / mol, and preferably greater than 100kg / mol and less than 250kg / mol, while a PS film non-chemically modified b-PMMA can not be orderedly structured for the same molecular weight because such structuring requires temperatures and annealing times such that too many defects occur and prevents the nana-structured structuring of the copolymer to be realized. Advantageously, the annealing of such a modified block copolymer, whose molecular weight is high and greater than 50 kg / mol, and preferably greater than 100 kg / mol and less than 250 kg / mol and whose value of xN is greater than 10 allows nano-structuring with organizational kinetics of the order of 1 to 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, and between 1 and 2 minutes. In the case of lithography, the desired structure, for example the generation of nano-domains perpendicular to the surface, however, requires the prior preparation of the surface on which the copolymer solution is deposited in order to control the energy. of surface. Among the known possibilities, is deposited on the surface a random copolymer forming a neutralization layer, the 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 surface prepared, 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. Ref: 0414-ARK50 / AM3282 Thereafter the 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 , a domain orientation while obtaining a significantly reduced defectivity compared to that obtained with unmodified block copolymers of identical chain lengths. This annealing step, allowing nano-structuring of the block copolymer film, can be carried out under a solvent atmosphere, or thermally, or by a combination of these two methods. The method for controlling the period of nano-structuring of block copolymers according to the invention therefore makes it possible, in particular in the case of base copolymers with a high degree of polymerization, to obtain nanostructured copolymer films with a significantly reduced defectivity compared to the unmodified copolymer. Furthermore, the Applicant has furthermore found that the introduction of DPE into the PS block, with a content preferably of between 1% and 25% and preferably of between 1% and 10%, advantageously allows to obtain nanostructuring without defects for larger film thicknesses than those obtained using the unmodified block copolymer. These thicknesses may be greater than or equal to 30 nm and even greater than 40 nm without appearance of defects. With unmodified block copolymer, it is not possible to achieve such flawless thicknesses. A high thickness allows better control of the lithography process, because the transfer of the nano-structured patterns in the substrate by etching (dry or wet) is strongly dependent on the thickness of the films used as masks: films of which Thickness is less than 40 nm will not allow efficient transfer into the substrate, while thicker films will lead to larger form factors. A PS-b-PMMA block copolymer of high molecular weight, typically greater than 50 kg / mol, and preferably greater than 100 kg / mol and less than 250 kg / mol, and modified by introducing DPE into the block. styrene base, thus makes it possible to obtain an assembly of the blocks perpendicularly to the surface on which it is deposited, with a large phase segregation and a high Lo period, typically greater than 30 nm, and preferably greater than 50 nm and less than 50 nm. 100 nm, and this with a temperature lower than that Ref: 0414-ARK50 / AM3282 necessary to nano-structure the base block copolymer, that is to say unmodified, and with fast organization kinetics. The modified block copolymer has a reduced defectivity compared to the same unmodified block copolymer, even at very large thicknesses. Such a block copolymer therefore allows better control of the lithography process. The invention further relates to a nano-lithography mask obtained from the modified block copolymer, deposited on a surface to be etched in accordance with the nanostructuring process. The film thus deposited on the surface comprises nano-domains oriented perpendicular to the surface to be etched and has a period greater than or equal to 30 nm, and preferably greater than 50 nm and less than 100 nm. The following examples illustrate in a nonlimiting manner the scope of the invention: EXAMPLE 1 Synthesis of a diblock copolymer of P (styrene-co-diphenyl ethylene) -bP (methyl methacrylate) (P ( S-co-DPE) -b-PMMA) 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 capacity d2 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 Cl capacity, a 27.5% by weight solution in toluene at 45 ° C. of the P block (S-co-DPE) is prepared so that the latter is a macroinitiator system which can be primed by the following the second PMMA block. For this purpose, a solution of toluene, 133 ml of 1.5M s-butyllithium in hexane, is added under an inert atmosphere of nitrogen to which 4 kg of a 90/10 styrene / 1,1-diphenylethylene mixture are added. mass. 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 also 72.19 of 1,1-diphenylethylene in Ref: 0414-ARK50 / AM3282 toluene are added. to obtain a molar ratio of 1/6 between the poly (styrylco-1,1-diphenylethyl) CH2C (Ph) 2Li and the CH3OCH2CH2OLi. The toluene solution is 23.2% by weight. The macroporous system [oly (styryl-co-1,1-diphenylethyl) CH2C (Ph) 2LiKCH3OCH2CH2OLi.] 6 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 previously passed on molecular sieve 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 solution of the capacity C2 is sent to an exchanger so that the temperature is lowered to -20 ° C and the flow of the MMA solution is adjusted 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 as follows: Mp copolymer = 55.4 kg / mol Dispersibility: 1.09 Weight ratio P (S-co-DPE) / PMMA = 69.8 / 30.2 Various copolymers with base blocks, that is, unmodified PS - bPMMA blocks, were synthesized according to this method with different compositions (ie with different PS and PMMA contents) and different modified block copolymers of PS - bPMMA. P (S-co-DPE) -b-PMMA were also synthesized according to this method with different compositions in order to be able to make comparisons illustrated below in Comparative Examples A to C of Example 4. [0077] various compositions of the various synthesized block copolymers are collated in Table I presented below. Ref: 0414-ARK50 / AM3282 Table I Reference MpPS block copolymer (kg / mol) MpPMMA (kg / mol) Mpcopolymer (kg / mol) Dispersibility PS block PSb block, PMMA% m% mDPEb% mPMMAb C35 V1 38.6 17.6 56.2 1.06 68.7 0 31.3 C35 V3 38.1 15.9 54 1.06 70.6 0 29.4 C35 1DPE 40.8 21.6 62.4 1.10 64 , 8 0.6 34.6 C35 10DPE 38.7 18.7 55.4 1.09 65.2 4.6 30.2 C50 V2 74 29.2 103.2 1.15 71.7 0 29.3 C50 10DPE 91.2 36 127.2 1.12 67.4 4.6 28.0 a) Determined by size exclusion chromatography. The polymers are solubilized at 1 g / l in THF stabilized with BHT. Calibration is performed using monodisperse polystyrene standards. Double detection by refractive index and UV at 254 nm makes it possible to determine the percentage of polystyrene in the copolymer. b) Determined by 1 H NMR * Determined by calculation from the mass Mp PS determined by steric exclusion chromatography SEC and the composition determined by 1 H NMR.
    [0003] EXAMPLE 2 Synthesis of a PS-stat-PMMA Neutralization Layer [0078] 1st step: Preparation of a Hydroxy-functionalized Alkoxyamine from the BlockBuilder® Commercial Alkoxyamine (ARKEMA): In an IL-purged flask Nitrogen: 226.17 g of BlocBuilder® (1 equivalent) 68.9 g of 2-hydroxyethyl acrylate (1 equivalent) 548 g of isopropanol Ref: 0414-ARK 50 / AM3282 [0079] The mixture The reaction is refluxed (80 ° C.) for 4 h and then the isopropanol is evaporated under vacuum. 297 g of hydroxy functionalized alkoxyamine are obtained in the form of a very viscous yellow oil. [0080] 2nd step: Experimental protocol for the preparation of PS / PMMA random copolymer starting from the alkoxyamine of step 1. In a stainless steel reactor equipped with a mechanical stirrer and a double jacket toluene, as well as monomers such as styrene (S), methyl methacrylate (MMA), and the functionalized alkoxyamine of step 1 are introduced. The mass ratios between the various styrene monomers (S) and the Methyl methacrylate (MMA) are described in Table 2 below. The mass load of toluene is set at 30% relative to the reaction medium. The reaction mixture is stirred and degassed by bubbling nitrogen at room temperature for 30 minutes. The temperature of the reaction medium is then raised to 115 ° C. The time t = 0 is triggered at room temperature. The temperature is maintained at 115 ° C. throughout the polymerization until reaching a monomer conversion of about 70%. Samples are taken at regular intervals to determine the kinetics of gravimetric polymerization (measurement of dry extract). When the 70% conversion is reached, the reaction medium is cooled to 60 ° C. and the solvent and residual monomers are evaporated under vacuum. After evaporation, the methyl ethyl ketone is added to the reaction medium in an amount such that a copolymer solution of the order of 25% by weight is produced. This copolymer solution is then introduced dropwise into a beaker containing a non-solvent (heptane), so as to precipitate the copolymer. The mass ratio between solvent and non-solvent (methyl ethyl ketone / heptane) is of the order of 1/10. The precipitated copolymer is recovered as a white powder after filtration and drying. Ref: 0414-ARK50 / AM3282 Initial state of reaction% PS (a) Characteristics Mn (a) of the copolymer ip (a) Initial mass composition of the monomers Ratio mp (a) g / mol MW (a) g / mol S / Mass MMA g / mole g / mole alkoxyamine relative to monomers S, MMA 66/34 0.03 65% 15 480 11 930 15 900 1.3 Reference neutralization layer MGCLO4 a) Determined by size exclusion chromatography. The polymers are solubilized at 1 g / l in THF stabilized with BHT. Calibration is performed using monodisperse polystyrene standards. Double detection by refractive index and UV at 254 nm makes it possible to determine the percentage of polystyrene in the copolymer. Example 3 Nano-Structuring Process of a PS-b-PMMA Modified Block Copolymer Film A silicon substrate is cut manually into 3 × 3 cm pieces, then the pieces are cleaned by conventional treatment ( piranha solution, oxygen plasma ...). A statistical copolymer of PS-stat-PMMA, as prepared according to Example 2, previously dissolved in propylene glycol monomethyl ether acetate (PGMEA) at a level of 2% by weight, is then deposited on the substrate. to functionalize by spin-coating, or any other deposition technique known to those skilled in the art, so as to form a polymer film of about 60 to 80 nm thick. This random copolymer film then forms a neutralization layer. The substrate is then heated to a temperature of about 230 ° C for 2 to 5 minutes so as to graft the polymer chains on 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 in Example 1, is dissolved in PGMEA at 1 to 2% by weight Ref: 0414-ARK50 / AM3282 following the desired film thickness, and is deposited on the surface by spin-coating so as 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 between 210 and 230 ° C (as the case may be) for 2 minutes to allow the nanostructuring of the blocks into nanodomains. 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. EXAMPLE 4 Comparative Examples A) Influence of the Composition of the Modified Block Copolymer [0089] In FIG. 2, photographs taken by scanning electron microscope of various samples of modified or unmodified block copolymers whose compositions are collected are represented in FIG. in Table I above with respect to Example 1, and nano-structured according to the invention. In FIG. 2, the annealing temperatures and times of each block copolymer as well as the period and the thickness of each of the samples are also indicated. It can be seen that for comparable copolymer molar masses, that is to say at a comparable degree of polymerization N, the unmodified C35 block copolymer, which is annealed at 220 ° C. for a duration of 2 minutes, has a high defectivity for a period of the order of 30 nm and a thickness of 19 nm, while the modified copolymers C35 1DPE and C35 10DPE, which are annealed at temperatures of 220 and 210 ° C. respectively for a duration of 2 minutes have a higher Lo period, respectively 36 nm and greater than 40 nm nm and a significantly reduced defectivity to a comparable thickness of 20 nm and even a high thickness of 44 nm. [0091] Similarly, for polymers whose degree of polymerization N is even higher, that is to say the C50 and C50 10DPE copolymers, whose molecular mass is respectively 103.2 and 127.2 kg / mol, it is found that Ref: 0414-ARK50 / AM3282 the incorporation of DPE makes it possible to lower the annealing temperature and / or the annealing time and to obtain block copolymers whose period is high (greater than 50 nm) , without appearance of defects. It therefore follows from this FIG. 2 that the incorporation of DPE into the styrene block of the starting PS-b-PMMA block copolymer having a high molecular mass, greater than 50 kg / mol and preferably greater than 100 kg / mol. and less than 250 kg / mol, makes it possible to reduce the time and / or the annealing temperature in order to organize the blocks of the copolymer so that it is nano-structured with a high period, typically greater than 30 nm, without defects.
    [0004] B) Influence of annealing temperature on defectivity as a function of thickness FIG. 3 represents photographs A to D taken under the scanning electron microscope of copolymer C35 10DPE, the composition of which is described in Table 1 below. above, deposited on a neutralization layer whose synthesis is described above with respect to Example 2, at different thicknesses and after different annealing conditions. More particularly, four samples of the P (S-co-DPE) -b-PMMA block copolymer containing 4.6% of DPE in the PS block were subjected to thicknesses of 19. and 24nm, a 5-minute anneal at a temperature of 200 ° C (photos C and D) and a temperature of 180 ° C (photos A and B) [0095] It follows from these comparisons that, whatever the thickness of the sample, a lowering of the annealing temperature makes it possible to obtain a substantially reduced defectivity.
    [0005] C) Influence of the annealing time on the defectivity [0096] FIG. 4 represents the photos, taken under a scanning electron microscope, of two samples E and F of C35 10DPE copolymer containing 4.6% DPE in the PS block, and of which the thickness is equal to 19 nm, the samples having been annealed at 180 ° C. for a duration of 5 and 2 minutes, respectively. As a result of this comparison, a decrease in annealing time significantly reduces the defectivity of the nano-structured block copolymer film. The addition of DPE in initial copolymers of PS-b-PMMA, of high molecular mass, therefore allows to organize the blocks at a temperature below Ref: 0414-ARK50 / AM3282 that used to organize the blocks of initial copolymers and with very fast kinetics, and this with a significantly reduced defectivity. An additional advantage lies in the fact that the defectivity is reduced even for large thicknesses, typically greater than 40 nm, as can be seen in Figure 2. Ref: 0414-ARK50 / AM3282
    权利要求:
    Claims (13)
    [0001]
    REVENDICATIONS1. Nano-structured nano-structured block copolymer film, obtained from a base block copolymer having a molecular weight greater than 50kg / mol, and preferably greater than 100kg / mol and less than 250kg / mol, and at least one block comprises styrene and at least one other block comprises methyl methacrylate, said block copolymer film being characterized in that the styrene-based block is formed by a copolymer of styrene and diphenyl ethylene (DPE) ).
    [0002]
    2. Block copolymer film according to claim 1, characterized in that the relative proportions, in monomer units, of diphenyl ethylene (DPE), incorporated in the styrene-based block, are between 1 and 25%, preferably between 1 and 10% with respect to the styrene comonomer with which it copolymerizes.
    [0003]
    3. Block copolymer film according to one of claims 1 to 2, characterized in that the molecular weights of each block are between 15kg / mol and 100kg / mol, preferably between 30kg / mol and 100kg / mol, with a dispersity index of less than or equal to 2, and preferably between 1.02 and 1.70.
    [0004]
    4. Block copolymer film according to one of claims 1 to 3, characterized in that the number n of blocks is preferably such that r-17, and even more preferably 2r13.
    [0005]
    5. Block copolymer film according to one of claims 1 to 4, characterized in that the comonomers of the styrene-based copolymer block (P (S-co-DPE)) have a statistical or gradient type arrangement. .
    [0006]
    6. A process for controlling the nano-domain nanostructuring period of a block copolymer film from a base block copolymer having a molecular weight greater than 50kg / mol, and preferably greater than 100kg / mol and less than 250kg / mol, and at least one block of which comprises styrene and at least one other block comprises methyl methacrylate, said process being characterized in that it comprises the following steps: Ref: 0414-ARK50 / PRO1202synthesis of said block copolymer by incorporating, into the block of said styrene-containing block-base copolymer, one or more ethylene diphenyl comonomers (DPE), applying a solution of said film-shaped block copolymer onto a surface, evaporation of the solvent from the solution and annealing at said determined temperature.
    [0007]
    7. Process according to claim 6, characterized in that the synthesis is carried out by controlled radical polymerization.
    [0008]
    8. Process according to claim 6, characterized in that the synthesis is carried out by anionic polymerization.
    [0009]
    9. Method according to one of claims 6 to 8, 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 less than 230 ° C, preferably below 210 ° C.
    [0010]
    10. Method according to one of claims 6 to 9, 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.
    [0011]
    11. Method according to one of claims 6 to 10, 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 and between 1 and 2 minutes.
    [0012]
    12. Process according to one of Claims 6 to 11, characterized in that the ethylene diphenyl comonomer (s) incorporated in the styrene-based copolymer block is (are) incorporated with relative proportions. in monomer units of between 1% and 25% and preferably between 1% and 10% with respect to the styrene comonomer with which it co-polymerises to form a copolymer block. Ref: 0414-ARK50 / AM3282
    [0013]
    13. Nano-lithography mask obtained from the block copolymer film according to one of claims 1 to 5, deposited on a surface to be etched according to the method according to one of claims 6 to 12, said copolymer film comprising nano-domains oriented perpendicular to the surface to be etched and having a Lo period greater than or equal to 30 nm, preferably greater than 50 nm and less than 100 nm. Ref: 0414-ARK50 / PRO1202
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    同族专利:
    公开号 | 公开日
    KR20170016482A|2017-02-13|
    US20170145250A1|2017-05-25|
    TW201609936A|2016-03-16|
    TWI567127B|2017-01-21|
    SG11201610321UA|2017-01-27|
    KR101922353B1|2018-11-26|
    US9976053B2|2018-05-22|
    FR3022249B1|2018-01-19|
    JP2017524760A|2017-08-31|
    CN106661171A|2017-05-10|
    WO2015189495A1|2015-12-17|
    JP6449342B2|2019-01-09|
    EP3155028A1|2017-04-19|
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    优先权:
    申请号 | 申请日 | 专利标题
    FR1455294A|FR3022249B1|2014-06-11|2014-06-11|METHOD FOR CONTROLLING THE PERIOD OF A NANOSTRUCTUE BLOCK COPOLYMER FILM BASED ON STYRENE AND METHYL METHACRYLATE, AND NANOSTRUCTURE BLOCK COPOLYMER FILM|
    FR1455294|2014-06-11|FR1455294A| FR3022249B1|2014-06-11|2014-06-11|METHOD FOR CONTROLLING THE PERIOD OF A NANOSTRUCTUE BLOCK COPOLYMER FILM BASED ON STYRENE AND METHYL METHACRYLATE, AND NANOSTRUCTURE BLOCK COPOLYMER FILM|
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    SG11201610321UA| SG11201610321UA|2014-06-11|2015-06-01|Method for controlling the period of a nanostructured block copolymer film made of styrene and methyl methacrylate, and nanostructured block copolymer film|
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