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    • 专利摘要:
    The invention relates to a method for controlling the surface energy at the upper interface of a block copolymer (BPC1), the lower interface of which is in contact with a previously neutralized surface of a substrate, to enable the obtaining an orientation of the nano-domains of said block copolymer (BPC1) perpendicular to the two lower and upper interfaces, said method consisting of covering the upper surface of said block copolymer (BPC1) with a surface neutralization top layer (TC) , and being characterized in that said surface neutralization top layer (TC) is constituted by a second block copolymer (BPC2).
    公开号:FR3037070A1
    申请号:FR1554982
    申请日:2015-06-02
    公开日:2016-12-09
    发明作者:Xavier Chevalier；Celia Nicolet；Christophe Navarro；Georges Hadziioannou
    申请人:Centre National de la Recherche Scientifique CNRS；Arkema France SA；Universite des Sciences et Tech (Bordeaux 1)；Institut Polytechnique de Bordeaux；
    IPC主号:
    专利说明:

    [0001] FIELD OF THE INVENTION [0001] The present invention relates to the field of controlling surface energy at each interface. a block copolymer film to control pattern generation and orientation at the time of nano-structuring said block copolymer.  More particularly, the invention relates to a method for controlling the surface energy of a block copolymer at its upper interface, in contact with a compound, or mixture of compounds, liquid, solid or gaseous.  The invention furthermore relates to a method for manufacturing a nano-lithography mask from a block copolymer, said method comprising the steps of the method of controlling the surface energy at the upper interface of said block copolymer.  Finally, the invention also relates to a surface neutralization top layer intended to cover the upper surface of the block copolymer.  PRIOR ART [0003] 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.  The block copolymers intended to form nano-lithography masks, however, must have nano-domains oriented perpendicularly to the surface of the substrate, in order to then be able to selectively remove one of the blocks of the copolymer to be used. blocks and create a porous film with the residual block (s).  The patterns thus created in the porous film can be subsequently transferred, by etching, to an underlying substrate.  [0006] Each of the blocks i, j of a block copolymer, denoted by BCP, has a surface energy denoted Nu. .  yi, which is its own and which is a function of its chemical constituents, that is to say of the chemical nature of the monomers or comonomers which compose it.  Each of the blocks i, j of the BCP block copolymer furthermore has a Flory-Huggins type interaction parameter, denoted: Xix, when it interacts with a given "x" material, which may be a gas or a liquid, a solid surface, or another polymer phase, for example, and an inter-facial energy denoted "Vix", with yix = Yi- (yx cos eix), where (Ten is the contact angle between materials i and x.  The interaction parameter between two blocks i and j of the block copolymer is therefore denoted xi.  Jia & al. , Journal of Macromolecular Science, B, 2011, 50, 1042, have shown that there is a relation binding the surface energy y; and the Hildebrand solubility parameter δ; of a given material i.  In fact, the FloryHuggins interaction parameter between two given materials i and x is indirectly related to the surface energies y; and yx specific to materials.  We therefore speak either in terms of surface energies or in terms of interaction parameter to describe the physical phenomenon of interaction appearing at the interface of the materials.  To obtain a structuring of the nano-domains constituting a block copolymer, perfectly perpendicular to the underlying substrate, it therefore appears necessary to precisely control the interactions of the block copolymer with the different interfaces with which it is physically in contact.  In general, the block copolymer is in contact with two interfaces: an interface called "lower" in the following description, in contact with the underlying substrate, and a so-called "upper" interface, in contact with another compound or mixture of compounds.  In general, the compound or mixture of compounds at the upper interface consists of ambient air or a controlled composition atmosphere.  However, it may more generally be composed of any compound, or mixture of compounds, constitution and surface energy defined, whether solid, gaseous or liquid that is to say non-volatile at the temperature of self-organization of nano-domains.  Ref: 0456-ARK62 3037070 3 [0009] When the surface energy of each interface is not controlled, there is generally a random orientation of the units of the block copolymer, and more particularly an orientation parallel to the substrate and this, whatever the morphology of the block copolymer.  This parallel orientation is mainly due to the fact that the substrate and / or compound (s) at the upper interface has a preferential affinity with one of the constituent blocks of the block copolymer at the self-heating temperature. arranging said block copolymer.  In other words, the Flory-Huggins type interaction parameter of a block i of the BCP block copolymer with the underlying substrate, denoted Xi-substrate, and / or the Flory type interaction parameter. -Huggins of a block i of the BCP block copolymer with the compound at the upper interface, for example air, noted Xi-air, is different from zero and equivalently, the inter-facial energy yi-substrate and / or yi-air is different from zero.  In particular, when one of the blocks of the block copolymer has a preferential affinity for the compound (s) of an interface, the nano-domains then tend to orient themselves parallel to this interface. .  The diagram of FIG. 1 illustrates the case where the surface energy at the upper interface, between a block copolymer referenced BCP and the ambient air in the example, is not controlled, whereas the lower interface between the underlying substrate and the BCP block copolymer is neutral with a Flory-Huggins parameter for each of the i blocks. . .  of the Xi-substrate and Xi-substrate block copolymer equal to zero or, more generally, equivalent for each of the blocks of the BCP block copolymer.  In this case, a layer of one of the blocks i or j of the block copolymer BCP, having the highest affinity with air, is organized in the upper part of the film of the BCP block copolymer, that is to say say at the interface with the air, and is paralleling this interface.  [0011] Consequently, the desired structuring, that is to say the generation of domains perpendicular to the surface of the substrate, whose patterns may be cylindrical, lamellar, helical or spherical, for example, requires a control of the energies of the substrate. surface not only at the lower interface, ie at the interface with the underlying substrate, but also at the upper interface.  Today, the control of the surface energy at the lower interface, that is to say at the interface between the block copolymer and the underlying substrate, is well known and controlled. .  Thus, Mansky et al.  in Science, vol. 275, pages 1458-1460 (March 7, 1997) have for example shown that a random copolymer of Ref: 0456-ARK62 Poly (methyl methacrylate-co-styrene) (PMMA-r-PS), functionalized by a hydroxyl function at the end of the chain, allows a good grafting of the copolymer on the surface of a silicon substrate having a native oxide layer (Si / SiO 2 native) and the obtaining of a non-surface energy preferential for blocks of the 5-block copolymer BCP nano-structurer.  In this case, we speak of "neutralization" of surface.  The key point of this approach lies in obtaining a grafted layer, to act as a barrier vis-à-vis the clean surface energy of the substrate.  The interfacial energy of this barrier with a given block of the BCP block copolymer is equivalent for each of the blocks of the BCP block copolymer, and is modulated by the ratio of comonomers present in the grafted random copolymer.  The grafting of a random copolymer thus makes it possible to eliminate the preferential affinity of one of the blocks of the block copolymer for the surface of the substrate, and thus to avoid obtaining a preferential orientation of the nano-domains parallel to the surface of the substrate.  To obtain a structuring of the nano-domains of a BCP block copolymer which is perfectly perpendicular with respect to the lower and upper interfaces, that is to say at the BCP-BCPair copolymer and substrate copolymer interfaces in the For example, the surface energy of the two interfaces must be equivalent to the blocks of the BCP block copolymer.  [0014] When the surface energy at the upper interface of the copolymer is poorly controlled, a significant defectivity appears due to the non-perfect perpendicularity of the nano-domains of the block copolymer once self-assembled.  [0015] If the lower interface between the BCP block copolymer and the underlying substrate is today controlled, for example by grafting a random copolymer, the upper interface between the block copolymer and a compound or a mixture of gaseous, solid or liquid compounds, such as the atmosphere for example, is much less so.  Different approaches, described below, however, exist to remedy this, the surface energy at the lower interface between the BPC block copolymer 30 and the underlying substrate being controlled in the three approaches below.  A first solution could be to anneal the BCP block copolymer in the presence of a gaseous mixture to meet the conditions of neutrality with respect to each block of the block copolymer Ref: 0456-ARK62 3037070 5 BPC.  However, the composition of such a gas mixture seems very complex to find.  A second solution, when the mixture of compounds at the upper interface consists of ambient air, consists in using a BCP block copolymer whose constituent blocks all have identical (or very close) surface energy. in relation to each other, at the temperature of self-organization.  In such a case, illustrated in the diagram of FIG. 2, the perpendicular organization of the nano-domains of the BCP block copolymer is obtained on the one hand, thanks to the BCP / substrate S copolymer interface neutralized by means of a for example, because the blocks ij of the BCP block copolymer naturally have a comparable affinity for the component at the upper interface, in this case air in the example.  We then have Xi-substrate Xj-substrate (= 0 preferably) and Yi-air Yj-air.  Nevertheless, there is only a limited number of block copolymers having this feature.  This is for example the case of the PS-b-PMMA block copolymer.  However, the interaction parameter of Flory Huggins for the PS-bPMMA copolymer is low, that is to say of the order of 0.039, at the temperature of 150 ° C. for self-organization of this copolymer, which limits the minimum size of the nano-domains generated.  In addition, the surface energy of a given material depends on the temperature.  However, if we increase the temperature of self-organization, for example when we want to organize a block copolymer of large mass or large period, then requiring a lot of energy to obtain a correct organization, it is possible that the The surface energy difference of the blocks then becomes too great for the affinity of each of the blocks of the block copolymer for the compound at the upper interface to still be considered equivalent.  In this case, the increase in the self-organization temperature can then cause the appearance of defects related to the non-perpendicularity of the assembly, due to the difference in surface energy between the blocks of the copolymer to blocks at 30 self-organization temperature.  A last considered solution, described by Bates et al in the publication entitled "Polarity-switching top coats enable orientation of sub-10nm block copolymer domains", Science 2012, Vol. 338, p. 775 - 779 and in the document Ref: 0456-ARK62 3 0 3 70 70 6 US2013 280497, consists in controlling the surface energy at the upper interface of a nano-structuring block copolymer, of poly (trimethylsilystyrene) type. -b-lactide) or poly (styrene-b-trimethylsilystyrene-b-styrene), by introducing an upper layer, also called "top coat" throughout the rest of the description, deposited on the surface of the copolymer to blocks.  In this document, the top coat, polar, is deposited by "spin coating" on the nano-structuring block copolymer film.  The top coat is soluble in an acidic or basic aqueous solution, which allows its application to the upper surface of the block copolymer, which is insoluble in water.  In the example described, the top coat is soluble in an aqueous solution of ammonium hydroxide.  The top coat is a random or alternating copolymer whose composition comprises maleic anhydride.  In solution, the ring opening of maleic anhydride allows the top coat to lose ammonia.  At the time of self-organization of the block copolymer at the annealing temperature, the maleic anhydride cycle of the top coat closes, the top coat undergoes a transformation in a less polar state and becomes neutral with respect to the copolymer. in blocks, thus allowing a perpendicular orientation of the nano-domains with respect to the two lower and upper interfaces.  The top coat is then removed by washing in an acidic or basic solution.  Likewise, the document US 2014238954A describes the same principle as that of document US2013 208497, but applied to a block copolymer containing a silsesquioxane type block.  This solution allows to replace the upper interface between the block copolymer to be organized and a compound or mixture of gaseous compounds, solid or liquid, such as air in the example, by a block copolymer interface - 25 top coat, noted "BCP-TC".  In this case, the top coat "TC" has an equivalent affinity for each of the blocks i. . .  of the BCP block copolymer at the assembly temperature considered (Xi-Tc = = Xj-TC (preferably -0)).  The difficulty of this solution lies in the deposit of the top coat itself.  On the one hand, it is necessary to find a solvent making it possible to solubilize the top coat, but not the block copolymer, with the risk of dissolving the layer of block copolymer previously deposited on the substrate itself neutralized and on the other hand, that the top coat may have equivalent surface energy for each of the different blocks of the PCB block copolymer to be nanostructured at the time of the heat treatment.  Ref: 0456-ARK62 3037070 7 The various approaches described above for controlling the surface energy at the upper interface of a block copolymer, previously deposited on a substrate whose surface is neutralized, generally remain too much tedious and complex to implement and do not significantly reduce the defect related to the non-perfect perpendicularity of the block copolymer patterns.  The solutions envisaged also seem to be too complex to be compatible with industrial applications.  (Technical problem) [0024] The object of the invention is therefore to remedy at least one of the disadvantages of the prior art.  The aim of the invention is in particular to propose a simple and industrially feasible alternative solution for controlling the surface energy at the upper interface of a block copolymer so as to allow, on the one hand, self-assembly of the blocks. block copolymer such that the generated patterns are oriented perpendicular to the substrate and the upper interface and on the other hand, a significant reduction in defectivity, related to the non-perpendicularity of the patterns.  (BRIEF DESCRIPTION OF THE INVENTION) To this end, the subject of the invention is a method for controlling the surface energy at the upper interface of a block copolymer, the lower interface of which is in contact with a previously neutralized surface of a substrate, to provide an orientation of the nano-domains of said block copolymer perpendicular to both the lower and upper interfaces, said method comprising covering the top surface of said block copolymer by a upper layer of surface neutralization, and being characterized in that said upper surface neutralization layer is constituted by a second block copolymer.  [0026] Thus, the blocks of the block copolymer may have a modulated surface energy with respect to one another so that at the self-organization temperature of the first block copolymer, at least one of the blocks of the second The block copolymer has a neutral surface energy with respect to all the blocks of the first block copolymer.  According to other optional characteristics of the surface energy control method: the first block copolymer and the second block copolymer are mixed in a common solvent and are deposited simultaneously, in a single step, on the previously neutralized surface of the substrate, - the two block copolymers are immiscible with each other, - the first nano-structuring block copolymer is deposited on the previously neutralized surface of said substrate, then the second copolymer The block copolymer is deposited on the first block copolymer (BCP1) to allow a neutralization of its upper surface. A step subsequent to the deposition of the two block copolymers consists in thermally treating the stack obtained, comprising the substrate, a layer of neutralization, the first block copolymer and the second block copolymer, so as to nano-structure at least one of the two block copolymers, the nano-structuring of the two block copolymers is carried out in a single heat treatment step at a single annealing temperature, - the time required for the organization of the second block copolymer is less than or equal to that of the first block copolymer, the nano-structuring of the two block copolymers is carried out in several successive stages of heat treatment, using different temperatures and / or annealing times, the second block copolymer being organized more rapidly or at a lower temperature than the first, the second block copolymer is unstructured at the organization temperature of the first block copolymer and the surface energy of a block, or set of blocks, of the second block copolymer is modulated by another block, or set of blocks of the second block copolymer so that all the blocks of the second copolymer The block type has equivalent surface energy for each block of the first block copolymer.  The invention further relates to a nano-lithography mask manufacturing process from a block copolymer, whose lower interface is in contact with a previously neutralized surface of an underlying substrate , said method comprising controlling the steps of the method of controlling the surface energy at the upper interface of said block copolymer as described above, and being characterized in that after the nanoparticles, The first block copolymer, the second block copolymer forming the top neutralization layer and at least one of the patterns generated in said first block copolymer are removed to form a film for use as a mask.  According to other optional features of the mask manufacturing process: the removal of the second block copolymer on the one hand and at least one of the first block copolymer's units is carried out in one or more successive steps; the removal step is carried out by dry etching or by rinsing the second block copolymer in a solvent or solvent mixture, in which the first block copolymer is at least partly insoluble, prior to the step of withdrawal, a stimulus is applied on all or part of the stack constituted by the substrate, the lower layer of neutralization, the first block copolymer and the second block copolymer, - the stimulus consists of an exposure of all or part of the stacking with UV-visible radiation, an electron beam, or with a liquid having acid-base or oxidation-reduction properties, - after the application of the stimulus, the second cop the block copolymer is removed by dissolution in a solvent or solvent mixture in which the first block copolymer is at least partly insoluble before and / or after exposure to the stimulus, at least one block of the first block copolymer is responsive to the stimulus applied, so that it can be removed simultaneously with the second block copolymer.  The invention finally relates to a surface neutralization upper layer intended to cover the upper surface of a block copolymer, the lower interface of which is in contact with a previously neutralized surface of a substrate, for allow to obtain an orientation of the nano-domains of said block copolymer perpendicularly to the lower and upper surfaces, said top surface neutralization layer being characterized in that it consists of a second copolymer to blocks.  According to other optional characteristics of the surface neutralization top layer: the block copolymer comprises at least two blocks, or sets of blocks, different, the block copolymer can be synthesized by any technique or combination of techniques known to those skilled in the art, each block of the block copolymer may consist of a set of co-monomers, copolymerized together under a block, gradient, random, random, alternating architecture, comb, the block copolymer comprises a first block, or set of blocks, whose surface energy is the lowest of all the constituent blocks of the two block copolymers, and a second block, or set of blocks, Having zero or equivalent affinity for each block of the first block copolymer, the block copolymer comprises m blocks, m being an integer 2 and 11, and preferably the morphology of the block copolymer. The block opolymer is preferably lamellar, without excluding the other possible morphologies; the volume fraction of each block of the block copolymer varies from 5 to 95% with respect to the volume of the block copolymer, the first block, or block set, whose energy is the lowest, has a volume fraction of between 50% and 70% relative to the volume of the second block copolymer, the second block copolymer has an annealing temperature less than or equal to that of the first block copolymer, the molecular weight of the block copolymer varies between 1000 and 500000 g / mol, each block of the block copolymer may comprise comonomers present in the backbone of the first block copolymer (BCP1). the first block, or group of blocks, whose energy is the weakest, is soluble in a solvent or a mixture of solvent, so that it promotes the solubilization of the block copolymer in said solvent / solvent mixture at the time of its removal, the upper neutralization layer is in contact with a compound, or mixture of compounds, of defined constitution and surface energy, which may be solid, gaseous or liquid at the organization temperature of the first and second block copolymers.  Other features and advantages of the invention will appear on reading the description given by way of illustrative and nonlimiting example, with reference to the appended figures which represent: FIG. 1, already described, a diagram of FIG. a block copolymer before and after the annealing step necessary for its self-assembly, when the surface energy at the upper interface is not controlled, FIG. 2, already described, a diagram of a copolymer with blocks before and after the annealing step necessary for its self-assembly, when all the blocks of the block copolymer have a comparable affinity with the compound at the upper interface, FIG. 3, a diagram of a copolymer with front blocks and after the annealing step necessary for its self-assembly, when the block copolymer is covered with a surface neutralization topcoat according to the invention, - Figure 4, a diagram of a front block copolymer and after removal of the surface neutralization top layer of Figure 3.  DETAILED DESCRIPTION OF THE INVENTION By "polymers" is meant either a copolymer (of statistical type, gradient, block, alternating), or a homopolymer.  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.  By "copolymer" is meant a polymer comprising several different monomer units.  By "random copolymer" is meant a copolymer in which the distribution of the monomer units along the chain follows a statistical law, by Ref: 0456-ARK62 10 - - 15 - 3037070 12 example of the Bernoullien type (order Markov zero) or Markovian first or second order.  When the repeat units are randomly distributed along the chain, the polymers were formed by a Bernouilli process and are called random copolymers.  The term random copolymer is often used, even when the statistical process which prevailed in the synthesis of the copolymer is not known.  The term "gradient copolymer" is understood to mean a copolymer in which the distribution of the monomer units varies progressively along the chains.  By "alternating copolymer" is meant a copolymer comprising at least two monomeric entities which are distributed alternately along the chains.  The term "block copolymer" is understood to mean a polymer comprising one or more uninterrupted sequences of each of the different polymeric species, the polymer blocks being chemically different from one another, or from the other (s), and being linked between they are chemically bonded (covalent, ionic, hydrogen bonding, or coordination).  These polymer blocks are still referred to as polymer blocks.  These blocks have a phase segregation parameter (Flory-Huggins interaction parameter) such that, if the degree of polymerization of each block is greater than a critical value, they are not miscible with each other and separate into nano -areas.  [0041] The term "miscibility" refers to the ability of two or more compounds to mix completely to form a homogeneous phase.  The miscibility of a mixture can be determined when the sum of the glass transition temperatures (Tg) of the mixture is less than the sum of the Tg of the compounds taken alone.  In the description, we speak as well of "self-assembly" as "self-organization" or "nano-structuring" to describe the well-known phenomenon of phase separation of block copolymers, an assembly temperature also called annealing temperature.  The term "lower interface" of a block copolymer to be nanostructured means the interface in contact with an underlying substrate on which a film of said block copolymer is deposited.  It will be noted that, throughout the rest of the description, this lower interface is neutralized by a technique known to the skilled person, such as the grafting of a random copolymer on the surface of the substrate beforehand. depositing the block copolymer film for example.  The term "upper interface" or "upper surface" of a nano-structured block copolymer means the interface in contact with a compound, or a mixture of compounds, of constitution and surface energy defined. whether it is solid, gaseous or liquid, that is to say non-volatile at the self-organization temperature of the nano-domains.  In the example described in the following description, this mixture of compounds is constituted by the ambient air, but the invention is not limited to this case.  Thus, when the compound at the upper interface is gaseous, it can also be a controlled atmosphere, when the compound is liquid, it can be a solvent or solvent mixture in which the block copolymer is insoluble, when the compound is solid, it may for example be another substrate such as a silicon substrate for example.  The principle of the invention consists in covering the upper surface of a nano-structured block copolymer, referenced BCP1 in the following, itself previously deposited on an underlying substrate S whose surface has been neutralized, by grafting a layer N of random copolymer for example, with a top layer, hereinafter called "top coat" and referenced TC, the composition of which allows a control of the surface energy at the upper interface of said BPC1 block copolymer.  Such a layer of TC top coat then makes it possible to orient the patterns generated during the nano-structuration of the BCP1 block copolymer, whether these are of cylindrical, lamellar, or other morphology. . .  perpendicular to the surface of the underlying substrate S and the upper surface.  For this, the top coat layer TC is advantageously constituted by a second block copolymer, referenced BCP2 thereafter.  Preferably, the second block copolymer BCP2 comprises at least two blocks, or sets of blocks, different.  Preferably, this second block copolymer BCP2 comprises, on the one hand, a block, or a set of blocks, referenced "s2", whose surface energy is the lowest of all the constituent blocks. of the two block copolymers BPC1, BPC2 and on the other hand, a block, or a set of blocks, referenced "r2", having zero affinity with all the blocks of the first block copolymer BPC1 to be nano-structured.  Ref: 0456-ARK62 3037070 [0048] "Block set" means blocks having the same or similar surface energy.  The underlying substrate S may be a solid of inorganic, organic or metallic nature.  As regards the nano-structuring block copolymer film, denoted BCP1, it comprises "n" blocks, n being an integer greater than or equal to 2 and preferably less than 11 and, more preferably , less than 4.  The BCP1 copolymer is more particularly defined by the following general formula: Al-b-B1-b-Cl-b-D1-b-. . . . -b-Z1 where A1, B1, ci, D1 ,. . . , L are all "i" blocks. . .  "Jl" representing either pure chemical entities, that is to say that each block is a set of monomers of identical chemical natures, polymerized together, or a set of co-monomers copolymerized together, in form, in whole or in part , block copolymer or statistical or random or gradient or alternating.  [0051] Each of the "i" blocks. . .  Thus, the "jl" of the BCP1 block copolymer to be nanostructured can potentially be written as: ## STR1 ## . . -co-z; ', with i' #. . .  #j ', in whole or in part.  The volume fraction of each garlic entity. . . zil can go from 1 to 100% in each of the blocks there. . .  of the BCP1 block copolymer.  [0053] The volume fraction of each of the blocks II. . .  can range from 5 to 95% of the BCP1 block copolymer.  The volume fraction is defined as the volume of an entity relative to that of a block, or the volume of a block relative to that of the block copolymer.  [0055] The volume fraction of each entity of a block of a copolymer, or block of a block copolymer, is measured as described hereinafter.  In a copolymer in which at least one of the entities, or one of the blocks in the case of a block copolymer, comprises several comonomers, it is possible to measure, by means of proton, the mole fraction of each monomer throughout the copolymer, then back to the mass fraction using the molar mass of each monomer unit.  In order to obtain the mass fractions of each entity of a block, or each block of a copolymer, it is then sufficient to add the mass fractions of the constituent comonomers of the entity or of the block.  The volume fraction of each entity or block can then be determined from the mass fraction of each entity or block and the density of the polymer forming the entity or block.  However, it is not always possible to obtain the density of the polymers whose monomers are co-polymerized.  In this case, the volume fraction of an entity or a block is determined from its mass fraction and the density of the bulk majority of the entity or block.  The molecular weight of the BCP1 block copolymer can range from 1000 to 500000 g. mo1-1.  The BCP1 block copolymer can have any type of architecture: linear, star (tri- or multi-arm), grafted, dendritic, comb.  As regards the second block copolymer, denoted BCP2, constituting the upper neutralization layer, also called top coat and referenced TC, it is more particularly defined by the following general formula: A2-b-B2- b-C2. . .  -b-Z2, wherein A2, B2, C2, D2 ,. . . , Z2, are all blocks "i2". . .  "J2" representing either pure chemical entities, i.e. each block is a set of monomers of identical chemical natures, polymerized together, either a set of co-monomers copolymerized together, in form, in all or part, block copolymer or statistical or random or gradient or alternating.  Each block "i2". .  "J2" of the BCP2 block copolymer may consist of any number of comonomers, of any chemical nature, optionally including comonomers present in the backbone of the first BCP1 block copolymer to be nano-structured, over any or part of the BCP2 block copolymer constituting the top coat.  Each block "i2". .  "J2" of the BCP2 block copolymer comprising comonomers, can be indifferently co-polymerized in the form of block copolymer or random or random or alternating or gradient on all or part of the blocks of the BCP2 block copolymer.  In the order of preference, it is co-polymerized in the form of a random copolymer, or a gradient or random or alternating copolymer.  Ref: 0456-ARK62 3037070 16 [0061] The blocks "i2". .  "J2" of the BCP2 block copolymer may be different from each other, either by the nature of the comonomers present in each block, or by their number, or the two by two as long as there are at least two blocks or different sets of blocks in the BCP2 block copolymer.  Advantageously, one of the blocks, or set of blocks, denoted "s2" of the block copolymer BPC2 constituting the top coat, has the lowest surface energy of all the blocks of the two block copolymers BPC1 and BPC2.  Thus, at the annealing temperature necessary for nano-structuring the second block copolymer BPC2, and if this annealing temperature is greater than the glass transition temperature of the first block copolymer BCP1, the block "s2" of the second block copolymer BPC2 blocks comes into contact with the compound at the upper interface and is then parallel to the upper surface of the layer stack consisting of the substrate S, the neutralization layer N, the block copolymer film BPC1 to nano -structuring and the BPC2 block copolymer forming the TC top coat.  In the example described, the compound at the upper interface is constituted by a gas, and more particularly by ambient air.  The gas can also be a controlled atmosphere for example.  The greater the surface energy difference of the block, or set of blocks, "s2" with the other blocks of the two block copolymers BPC1 and BPC2, the greater its interaction with the compound at the upper interface, in the same way. occurrence of air in the example, is favored, which also promotes the effectiveness of the TC top coat layer.  The difference in surface energy of this block "s2" with the other blocks of the two copolymers must therefore have a value sufficient to allow the block "s2" to be at the upper interface.  We then have Xs2-air 25-0. - - Xil-air> 0, Xj1-air> 0, Xi2-air> 0, Xj2-air> 0- [0063] In order to obtain a perpendicular orientation of the patterns generated by the nano-structuring of the first BCP1 block copolymer, It is preferable that the second BCP2 block copolymer is already assembled or that it can self-organize at the same annealing temperature, but with faster kinetics.  The annealing temperature at which the second block copolymer self-organizes is therefore preferably less than or equal to the annealing temperature of the first BPC1 block copolymer.  Ref: 0456-ARK62 3037070 [0064] Preferably, the block "s2" which has the lowest surface energy of all the blocks of the block copolymers BPC1, BPC2 is also the one which has the largest volume fraction of the copolymer to BPC2 blocks.  Preferably, its volume fraction can range from 50 to 70% based on the total volume of the BPC 2 block copolymer.  In addition to the first condition on the block "s2", another block, or set of blocks, denoted "r2", of the block copolymer BPC2 constituting the top coat, must also have a zero affinity for all the blocks of the first BPC1 block copolymer to be nanostructured.  Thus, the block "r2" is "neutral" with respect to all the blocks 10 of the first block copolymer BPC1.  We then have xi1-r2 =. . .  = -0 preferably) and> 0,, Xj1-j2> 0.  The block "r2" then makes it possible to neutralize and control the upper interface of the first block copolymer BPC1, and thus contributes, with the block "s2", to the orientation of the nano-domains of the copolymer BPC1 perpendicularly to the lower and upper surfaces. stacking.  The block "r2" can be defined according to any method known to those skilled in the art to obtain a "neutral" material for a given BPC1 block copolymer, such as for example a copolymerization in statistical form of the comonomers constituting the first copolymer BPC1 blocks according to a precise composition.  Thanks to the combined action of these two blocks, or sets of blocks, 20 "s2" and "r2" of the BPC2 block copolymer forming the top coat layer TC, it is possible to obtain a stack such that illustrated in the diagram of FIG. 3, leading to a perpendicular structuring of the patterns of the first BPC1 block copolymer with respect to its lower and upper surfaces.  In this FIG. 3, the BPC2 block copolymer constituting the top coat is self-assembled, and the "s2" block is oriented parallel to the interface with the ambient air and the "r2" block is oriented parallel to interfacing with the blocks of the BPC1 block copolymer film, thereby permitting perpendicular organization of the BPC1 block copolymer patterns.  Advantageously, the BCP2 block copolymer consists of 30 "m" blocks, m being an integer 2 and preferably less than or equal to 11 and, more preferably, less than or equal to 5.  The period of the self-organized patterns of BCP2, noted L02, may have any value.  Typically, it is located between 5 and 100nm.  The morphology Ref: 0456-ARK62 3037070 18 adopted by the BCP2 block copolymer can also be arbitrary, that is lamellar, cylindrical, spherical, or more exotic.  Preferably, it is lamellar.  The volume fraction of each block can vary from 5 to 95% relative to the volume of the BCP 2 block copolymer.  Preferably, but not limited to, at least one block will have a volume fraction ranging from 50 to 70% of the volume of the BCP2 block copolymer.  Preferably, this block representing the largest volume fraction of the copolymer is constituted by the block, or set of blocks, "s2".  The molecular weight of BCP 2 can range from 1000 to 500,000 g / mol.  Its molecular dispersity can be between 1.01 and 3.  The BPC2 block copolymer can be synthesized by any appropriate polymerization technique, or combination of polymerization techniques, known to those skilled in the art, such as, for example, anionic polymerization, cationic polymerization, controlled radical polymerization. or not, ring opening polymerization.  In this case, the one or more constituent comonomers of each block will be selected from the usual list of monomers corresponding to the chosen polymerization technique.  When the polymerization process is conducted by a controlled radical route, for example, 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 controlled radical polymerization method will be carried out by NMP.  More particularly, the nitroxides derived from alkoxyamines derived from the stable free radical (1) are preferred.  Wherein the RL radical 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, branched or cyclic hydrocarbon group, saturated or unsaturated such as an alkyl or phenyl radical, or a COOR ester group or a OR 5 alkoxy group, or a PO (OR) 2 phosphonate group, as soon as it has a molar mass greater than 15.0342.  The radical RL, monovalent, is said at position 13 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 radical, an aryl radical or a radical. aryl-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 valences 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 may be a radical comprising a phosphoryl group, said radical RL possibly being represented by the formula: ## STR1 ## in which R 3 and R 4, which may 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 capable of being 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: Ref: 0456-ARK62 3037070 20-N-tert-butyl-1-phenyl-2-methylpropyl-nitroxide, N-tert-butyl-1- (2-naphthyl) -2 methyl propyl nitroxide, N-tert-butyl-1-diethylphosphono-2,2-dimethylpropyl nitroxide, N-tert-butyl-1-dibenzylphosphono-2,2-dimethylpropyl nitroxide, 5-N-phenyl-1-diethylphosphonium 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.  [0076] Preferably, the alkoxyamines derived from N-tert-butyl-1-diethylphosphono-2,2-dimethylpropyl nitroxide will be used.  The constituent comonomers of the polymers synthesized by a radical route, for example, will be chosen from the following monomers: vinylic, vinylidene, diene, olefinic, allylic or (meth) acrylic or cyclic monomers.  These monomers are chosen more particularly from vinylaromatic monomers such as styrene or substituted styrenes, in particular alphamethylstyrene, acrylic monomers such as acrylic acid or its salts, alkyl, cycloalkyl or aryl acrylates such as methyl acrylate, ethyl acrylate, butyl acrylate, ethylhexyl acrylate or phenyl acrylate, hydroxyalkyl acrylates such as 2-hydroxyethyl acrylate, 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 acrylate, and the like. 2- (dimethylamino) ethyl (ADAME), fluorinated acrylates, silylated acrylates, phosphorus acrylates such as alkylene glycol phosphate, glycidyl acrylates, dicyclopentenyloxyethyl acrylates, methacrylic monomers such as methacrylic acid or its salts, alkyl, cycloalkyl, alkenyl or aryl methacrylates such as methyl methacrylate (MMA) lauryl, cyclohexyl, allyl, phenyl or naphthyl, hydroxyalkyl methacrylates such as 2-hydroxyethyl methacrylate or 2-hydroxypropyl methacrylate, ether alkyl methacrylates such as methacrylate of 2 ethoxyethyl, alkoxy- or aryloxy-polyalkylene glycol methacrylates such as methacrylates of Ref: 0456-ARK62 3037070 21 methoxypolyethylene glycol, methacrylates of ethoxypolyethylene glycol, methacrylates of methoxypolypropylene glycol, methacrylates of methoxypolyethylene glycol-polypropylene glycol or mixtures thereof, methacrylates aminoalkyl such as 2- (dimethylamino) ethyl methacrylate (MADAME), methacrylates fluorinated compounds such as 2,2,2-trifluoroethyl methacrylate, silylated methacrylates such as 3-methacryloylpropyltrimethylsilane, phosphorus methacrylates such as alkylene glycol phosphate methacrylates, hydroxyethylimidazolidone methacrylate, methacrylate and the like; hydroxyethylimidazolidinone, 2- (2-oxo-1-imidazolidinyl) ethyl methacrylate, acrylonitrile, acrylamide or substituted acrylamides, 4-acryloylmorpholine, N-methylolacrylamide, methacrylamide or substituted methacrylamides N-methylolmethacrylamide, methacrylamido-propyltrimethylammonium chloride (MAPTAC), glycidyl, dicyclopentenyloxyethyl methacrylates, itaconic acid, maleic acid or its salts, maleic anhydride, alkyl maleates or hemimaleates. or alkoxy- or aryloxy-polyalkyleneglycol, vinylpyridine, vinylpyrrolidinone, (alkoxy) poly (alkylene glycol) vinyl ether or divinyl ether, such methoxy poly (ethylene glycol) vinyl ether, poly (ethylene glycol) divinyl ether, olefinic monomers, among which mention may be made of ethylene, butene, 1,1-diphenylethylene, hexene and octene, diene monomers including butadiene, isoprene as well as fluorinated olefinic monomers, and vinylidene monomers, among which mention may be made of vinylidene fluoride, the protected case to be compatible with the polymerization processes.  When the polymerization process is conducted by an anionic route, any anionic polymerization mechanism, whether it is the liganded anionic polymerization or the anionic ring opening polymerization, may be considered.  Preferably, an anionic polymerization process in an apolar solvent, and preferably toluene, as described in Patent EP0749987, and involving a micro-mixer.  When the polymers are synthesized cationically, anionically or by ring opening, the constituent comonomer (s) of the polymers, for example, will be chosen from the following monomers: vinylic, vinylidene, diene, olefinic and allylic monomers , (meth) acrylic or cyclic.  These monomers are chosen more particularly from vinylaromatic monomers such as styrene or substituted styrenes, in particular alpha-methylstyrene, silylated styrenes and acrylic monomers, such as alkyl acrylates, cycloalkyl acrylates and the like. aryl such as methyl, ethyl, butyl, ethylhexyl or phenyl acrylate, alkyl ether acrylates such as 2-methoxyethyl acrylate, alkoxy- or aryloxy-polyalkylene glycol acrylates; such as methoxypolyethylene glycol acrylates, ethoxypolyethylene glycol acrylates, methoxypolypropylene glycol acrylates, methoxy-polyethylene glycol polypropylene glycol acrylates or mixtures thereof, aminoalkyl acrylates such as 2- (dimethylamino) ethyl acrylate (ADAME), fluorinated acrylates, silylated acrylates, phosphorus acrylates such as alkylene glycol phosphate acrylates, glycidyl acrylates, dicyclopentenyloxyethyl, alkyl, cycloalkyl, alkenyl or aryl methacrylates such as methyl methacrylate (MMA), lauryl, cyclohexyl, allyl, phenyl or naphthyl, methacrylates of alkyl ether 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, methacrylates Aminoalkyl such as 2- (dimethylamino) ethyl methacrylate (MADAME), fluorinated methacrylates such as 2,2,2-trifluoroethyl methacrylate, silylated methacrylates such as 3-methacryloylpropyltrimethylsilane, phosphorus methacrylates such as alkylene glycol phosphate methacrylates, hydroxyethylimidazol methacrylate idone, hydroxyethylimidazolidinone methacrylate, 2- (2-oxo-1-imidazolidinyl) ethyl methacrylate, acrylonitrile, acrylamide or substituted acrylamides, 4-acryloylmorpholine, N-methylolacrylamide, methacrylamide or substituted methacrylamides, N-methylolmethacrylamide, methacrylamido-propyltrimethyl ammonium chloride (MAPTAC), glycidyl, dicyclopentenyloxyethyl methacrylates, itaconic acid, maleic acid or its salts, maleic anhydride, maleates or alkyl or alkoxy- or aryloxy-polyalkylene glycol hemimaleate, vinylpyridine, vinylpyrrolidinone, (alkoxy) poly (alkylene glycol) vinyl ether or divinyl ether, such as methoxy poly (ethylene glycol) vinyl ether, poly (ethylene glycol) divinyl ether, Ref: 0456-ARK62 3037070 23 olefinic monomers, among which mention may be made of ethylene, butene, 1,1-diphenylethylene, hexene and 1-octene, the monomers dienics including butadiene, isoprene and fluorinated olefinic monomers, and vinylidene monomers, among which mention may be made of vinylidene fluoride, the cyclic monomers, among which mention may be made of 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, epoxides, cyclosiloxanes, cyclic phosphorus esters such as cyclophosphorinans, cyclophospholanes, oxazolines, the protected case to be compatible with polymerization processes, globular methacrylates such as methacrylates, isobornyl, halogenated isobornyl, halogenated alkyl methacrylate, methacrylate naphthyl, alone or as a mixture of at least two monomers mentioned above.  With regard to the surface energy control method at the upper interface of the first BCP1 block copolymer, the second BCP2 block copolymer forming the TC top coat layer can be deposited on the copolymer film. BCP1 block, itself previously deposited on an underlying substrate S 20 whose surface has been neutralized N by any means known to those skilled in the art, or it can be deposited simultaneously with the first BCP1 block copolymer.  That the two block copolymers BCP1 and BCP2 are deposited successively or simultaneously, they can be deposited on the surface of the substrate S previously neutralized N, according to techniques known to those skilled in the art, such as for example the so-called "Spin coating", "doctor blade" "knife system" or "slot die system".  According to a preferred embodiment, the two block copolymers BCP1 and BCP2 have a common solvent, so that they can be deposited on the underlying substrate S, the surface of which has been previously neutralized, in one one and the same step.  For this, the two copolymers are solubilized in the common solvent and form a mixture of any proportions.  The proportions may, for example, be chosen according to the desired thickness of the BCP1 block copolymer film intended to serve as a nano-lithography mask.  However, the two copolymers BCP1 and BCP2 must not be miscible with one another, or at least very little miscible, in order to prevent the second BCP2 copolymer from disturbing the morphology adopted by the first BCP1 block copolymer.  The mixture of BCP1 + BCP2 block copolymers can then be deposited on the surface of the substrate, according to techniques known to those skilled in the art, such as for example the technique known as "spin coating", "doctor blade" "knife" 10 system "or" slot die system ".  Following the deposition of the two block copolymers BCP1 and BCP2 successively or simultaneously, a stack of layers is thus obtained comprising the substrate S, a neutralization layer N, the first block copolymer BCP1 and the second block copolymer BCP2.  [0087] The BPC2 block copolymer forming the top coat layer TC exhibits the well-known phenomenon of phase separation block copolymers at an annealing temperature.  The stack obtained is then subjected to a heat treatment so as to nano-structure at least one of the two block copolymers.  [0089] Preferably, the second BCP2 block copolymer is nano-structured first so that its lower interface can exhibit neutrality with respect to the first BCP1 copolymer at the time of its self-organization.  For this, the annealing temperature of the second block copolymer BCP 2 is preferably less than or equal to the annealing temperature of the first block copolymer BCP 1 while being greater than the highest glass transition temperature of BCP 1.  In addition, when the annealing temperature is identical, that is to say when the two block copolymers can self-assemble in a single step at the same annealing temperature, the time required for the organization of the second BCP2 block copolymer is preferably less than or equal to that of the first block copolymer.  When the annealing temperature of the two block copolymers BCP1 and BCP2 is identical, the first block copolymer BPC1 self-organizes and generates patterns, while the second block copolymer BPC2 also structures Ref: 0456- ARK62 3037070 25 so as to have at least two distinct domains "s2" and "r2".  We therefore preferably have xs242. Nt> 10.5, where Nt is the total degree of polymerization of the "s2" and "r2" blocks for a strictly symmetric BPC2 block copolymer.  Such a copolymer is symmetrical when the volume fractions of each block constituting the copolymer BPC2 are equivalent, in the absence of particular interactions or specific frustration phenomena between different blocks of the BPC2 block copolymer, leading to a distortion of the block diagram. phase relating to the BPC2 copolymer.  More generally, it is appropriate that xs242. Nt is greater than a curve describing the phase separation limit, named "MST" (of the acronym 10 "Microphase Separation Transition") between an ordered system and a disordered system, dependent on the intrinsic composition of the BCP2 block copolymer .  This condition is for example described by L.  Leibler in the document entitled "Theory of Microphase Separation in Block Copolymers", Macromolecules, 1980, Vol. 13, p.  1602 - 1617.  However, it is possible that, in an alternative embodiment, the BPC2 block copolymer does not exhibit structuring at the assembly temperature of the first BPC1 block copolymer.  Then we have xs2_r2. nt <10.5 or xs242.Nt <MST curve. In this case, the surface energy of the block "r2" is modulated by the presence of the block "s2", and it must be readjusted so as to have an equivalent surface energy with respect to all the blocks of the first BCP1 block copolymer. According to this approach, the block "s2" serves in this case only solubilizing group for the block copolymer BPC2. It should be noted, however, that the surface energy of the blocks of the BCP2 block copolymer strongly depends on the temperature. [0092] Preferably, the time required for organizing the BCP2 block copolymer forming the top coat is less than or equal to that of the first BCP1 block copolymer. Therefore, it is the orientation parallel to the surface of the stack obtained, the patterns generated during the self-assembly of the second BCP2 block copolymer, which makes it possible to obtain the perpendicular orientation of the patterns of the first BCP1 block copolymer. Ref: 0456-ARK62 3037070 [0094] Optionally, the "s2" block of the BPC2 block copolymer constituting the top coat TC may be highly soluble in a solvent, or mixture of solvents, which is not a solvent or solvent mixture of the first BPC1 copolymer to be nano-structured to form a nano-lithography mask. Block "s2" can then act as an agent promoting the solubilization of the BPC2 block copolymer in this particular solvent or solvent mixture, denoted "MS2", which then allows the subsequent removal of the second BCP2 block copolymer. As regards the method for manufacturing a nano-lithography mask, when the BCP1 block copolymer film is nano-structured and its patterns are oriented perpendicularly to the surface of the stack, it is advisable to removing the top layer of top coat TC formed by the second block copolymer BCP2, in order to be able to use the nano-structured BCP1 block copolymer film as a mask in a nanolithography process, to transfer its patterns in the underlying substrate. For this, the removal of the block copolymer BPC2 may be carried out either by rinsing with a solvent, or solvent mixture MS2, non-solvent, at least in part, for the first BCP1 block copolymer, or by dry etching, such as plasma etching, for example, in which the gas chemistry (s) used is adapted according to the intrinsic constituents of the BCP2 block copolymer. After removal of the BCP2 block copolymer, a nano-structured BCP1 block copolymer film is obtained, whose nano-domains are oriented perpendicularly to the surface of the underlying substrate, as shown in FIG. Figure 4. This block copolymer film is then able to serve as a mask, after removal of at least one of its blocks to leave a porous film and thus be able to transfer its patterns in the underlying substrate by a method of nano-lithography. [0097] Optionally, prior to removal of the BCP2 block copolymer constituting the upper neutralization layer, a stimulus may also be applied to all or part of the stack obtained, consisting of the substrate 30 S, the layer N of surface neutralization of the substrate, the BCP1 block copolymer film and the BCP2 block copolymer top layer. Such a stimulus can for example be achieved by exposure to UV-visible radiation, an electron beam, or to a liquid having acid-base or oxidation-reduction properties, for example . The stimulus then makes it possible to induce a chemical modification on all or part of the block copolymer BCP2 of the upper layer, by cleavage of polymer chains, formation of ionic species, etc. Such a modification then facilitates the dissolution of the copolymer. BCP2 block in a solvent or mixture of solvents noted "MS3", wherein the first BCP1 copolymer at least in part, is not soluble before or after exposure to the stimulus. This MS3 solvent or solvent mixture may be the same as or different from the MS2 solvent, depending on the extent of the solubility change of the BPC2 block copolymer following exposure to the stimulus. It is also envisaged that the first block copolymer BCP1, at least in part, that is to say at least one block constituting it, may be sensitive to the stimulus applied, so that the block in question can to be modified following the stimulus, following the same principle as the modified BCP2 block copolymer with the stimulus. Thus, simultaneously with the removal of the constituent BPC2 block copolymer from the topcoat top layer, at least one block of the BPC1 block copolymer can also be removed so that a film for use as a mask is obtained. In one example, if the BCP1 copolymer for use as a mask is a block copolymer of PS-b-PMMA, a stimulus by exposing the stack to UV radiation will cleave the PMMA polymer chains. In this case, the PMMA units of the first block copolymer can be removed, simultaneously with the second block copolymer BCP2, by dissolving in a solvent or solvent mixture MS2, MS3. In a simple example where the BPC1 block copolymer intended to serve as a nano-lithography mask is of lamellar morphology and constituted by a diblock system of PS-b-PMMA type, then the BPC 2 block copolymer constituting the upper layer of top coat TC can be written in the form: s2-b-r2 = s2-bP (MMA-rS) where the group s2 can be a block obtained by polymerization of a monomer of the fluoroalkyl acrylate type, for example . [0100] To simplify the description, only the atmosphere has been described as the constituent compound of the upper interface. However, there are a large number of compounds, or mixtures of compounds, capable of constituting such an interface, whether they are liquid, solid or gaseous at the temperature of organization of the two block copolymers. Thus, for example, when the compound at the interface is constituted by a liquid fluoropolymer, at the annealing temperature of the block copolymers, then one of the constituent blocks of the second block copolymer BCP 2, forming the upper neutralization layer, will include a fluorinated copolymer. Ref: 0456-ARK62
    权利要求:
    Claims (29)
    [0001]
    REVENDICATIONS1. A method for controlling the surface energy at the upper interface of a block copolymer (BPC1), the lower interface of which is in contact with a previously neutralized surface of a substrate (S), for obtaining orienting the nano domains of said block copolymer (BPC1) perpendicular to both the lower and upper interfaces, said method comprising covering the upper surface of said block copolymer (BPC1) with a surface neutralization top layer (TC), and characterized in that said surface neutralization top layer (TC) is constituted by a second block copolymer (BPC2).
    [0002]
    2. Method according to claim 1, characterized in that the first block copolymer (BCP1) and the second block copolymer (BCP2) are mixed in a common solvent and are deposited simultaneously, in a single step, on the surface previously neutralized substrate.
    [0003]
    3. Method according to claim 2, characterized in that the two block copolymers (BCP1 and BCP2) are immiscible with each other.
    [0004]
    4. Method according to claim 1, characterized in that the first block copolymer (BCP1) to be nanostructured is deposited on the previously neutralized surface of said substrate, then the second block copolymer (BCP2) is deposited on the first copolymer to blocks (BCP1) to allow neutralization of its upper surface.
    [0005]
    5. Method according to one of claims 1 to 4, characterized in that a step subsequent to the deposition of the two block copolymers (BCP1 and BCP2) comprises heat-treating the resulting stack, comprising the substrate (S), a neutralization layer (N), the first block copolymer (BCP1) and the second block copolymer (BCP2), so as to nanostruct at least one of the two block copolymers.
    [0006]
    6. Process according to claim 5, characterized in that the nano-structuring of the two block copolymers (BCP1 and BCP2) is carried out in a single heat treatment step at a single annealing temperature. Ref: 0456-ARK62 3037070 30
    [0007]
    7. Method according to claim 6, characterized in that the time required for the organization of the second block copolymer (BCP2) is less than or equal to that of the first block copolymer (BCP1).
    [0008]
    8. Process according to claim 5, characterized in that the nano-structuring of the two block copolymers (BCP1 and BCP2) is carried out in several successive stages of heat treatment, using different temperatures and / or annealing times, the second block copolymer (BCP2) organizing more rapidly, or at a lower temperature, than the first (BCP1).
    [0009]
    9. Process according to claim 5, characterized in that the second block copolymer (BCP2) is unstructured at the organization temperature of the first block copolymer (BCP1) and in that the surface energy of a block, or set of blocks, "r2" of the second block copolymer is modulated by the presence of another block, or set of blocks, "s2", so that all the blocks of the second block copolymer (BCP2) has equivalent surface energy for each block of the first block copolymer (BCP1).
    [0010]
    10. A method for manufacturing a nano-lithography mask from a block copolymer (BCP1), the lower interface of which is in contact with a previously neutralized (N) surface of a substrate (S) under said method comprising the steps of the method of controlling the surface energy at the upper interface of said block copolymer (BCP1) according to one of claims 1 to 8, and being characterized in that after the nano -structuring the first block copolymer (BCP1), the second block copolymer (BCP2) forming the upper neutralization layer and at least one of the patterns generated in said first block copolymer (BCP1) are removed to create a film for to serve as a mask.
    [0011]
    11. Process according to claim 10, characterized in that the removal of the second block copolymer (BCP2) on the one hand and at least one of the units of the first block copolymer (BCP1) is carried out in one or more successive stages. .
    [0012]
    12. Method according to one of claims 10 to 11, characterized in that the removal step 30 is by dry etching or rinsing the second block copolymer (BCP2) in a solvent or solvent mixture (MS2), wherein the first block copolymer is at least partly insoluble. Ref: 0456-ARK62 3037070 31
    [0013]
    13. Method according to one of claims 10 to 12, characterized in that prior to the step of withdrawal, a stimulus is applied on all or part of the stack consisting of the substrate (S), the layer (N) lower neutralization, the first block copolymer (BCP1) and the second block copolymer (BCP2). 5
    [0014]
    14. The method of claim 13, characterized in that the stimulus consists of exposing all or part of the stack to UV-visible radiation, an electron beam, or a liquid with acid-base properties or redox.
    [0015]
    15. Method according to one of claims 13 to 14, characterized in that after application of the stimulus, the second block copolymer (BCP2) is removed by dissolving in a solvent or mixture of solvents (MS3) in which the first copolymer block (BCP1) is at least partially insoluble before and / or after exposure to the stimulus.
    [0016]
    16. Process according to one of Claims 13 to 15, characterized in that at least one block of the first block copolymer (BCP1) is sensitive to the stimulus applied, so that it can be withdrawn simultaneously with the second copolymer. to blocks (BCP2).
    [0017]
    17. A surface neutralization top layer for covering the upper surface of a block copolymer (BCP1), the lower interface of which is in contact with a previously neutralized (N) surface of a substrate (S), for allow to obtain an orientation of the nano-domains of said block copolymer (BPC1) perpendicularly to the lower and upper surfaces, said top surface neutralization layer being characterized in that it consists of a second block copolymer (BCP2) ). 25
    [0018]
    18. Surface neutralization top layer according to claim 17, characterized in that the block copolymer (BCP2) comprises at least two blocks, or sets of blocks, different.
    [0019]
    19. Upper surface neutralization layer according to one of claims 17 to 18, characterized in that each block of the block copolymer (BCP2) may consist of a set of co-monomers, copolymerized together under an architecture of block type, gradient, statistic, random, alternating, comb. Ref: 0456-ARK62 3037070 32
    [0020]
    20. Upper surface neutralization layer according to one of claims 17 to 19, characterized in that the block copolymer (BCP2) comprises a first block, or set of blocks, ("s2") whose surface energy is the lowest of all the building blocks of the two block copolymers (BCP1 and BCP2), and a second block, or set of blocks, ("r2") having zero or equivalent affinity for each of the blocks of the first block copolymer (BCP1).
    [0021]
    21. Upper surface neutralization layer according to one of claims 17 to 20, characterized in that the block copolymer (BCP2) comprises "m" blocks, m being an integer 2 and 11, and preferably 10
    [0022]
    22. Top surface neutralization layer according to one of claims 17 to 21, characterized in that the morphology of the block copolymer (BCP2) is preferably lamellar.
    [0023]
    23. Upper surface neutralization layer according to one of claims 17 to 22, characterized in that the volume fraction of each block of the block copolymer (BCP2) varies from 5 to 95% relative to the volume of the block copolymer. .
    [0024]
    Surface neutralization top layer according to one of claims 20 to 23, characterized in that the first block, or set of blocks, ("s2") whose energy is the weakest, has a volume fraction included between 50% and 70% relative to the volume of the second block copolymer (BCP2). 20
    [0025]
    25. Surface neutralization top layer according to one of claims 17 to 24, characterized in that the second block copolymer (BCP2) has an annealing temperature less than or equal to that of the first block copolymer (BCP1).
    [0026]
    26. Upper surface neutralization layer according to one of claims 17 to 25, characterized in that the molecular weight of the block copolymer (BCP2) varies between 1000 and 500000 g / mol.
    [0027]
    27. Top surface neutralization layer according to one of claims 17 to 26, characterized in that each block (i2 ... j2) of the block copolymer (BCP2) may comprise comonomers present in the skeleton of the first Block copolymer (BCP1). Ref: 0456-ARK62 3037070 33
    [0028]
    28. Surface neutralization top layer according to one of claims 20 to 27, characterized in that the first block, or set of blocks, ("s2") whose energy is the weakest, is soluble in a solvent or solvent mixture (MS2), so that it promotes the solubilization of the block copolymer (BCP2) in said solvent / solvent mixture (MS2) at the time of its removal.
    [0029]
    29. Upper surface neutralization layer according to one of claims 17 to 28, characterized in that it is in contact with a compound, or mixture of compounds, constitution and surface energy defined, which can be solid, gaseous or liquid at the organization temperature of the first and second block copolymers. Ref: 0456-ARK62
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    同族专利:
    公开号 | 公开日
    CN107735727A|2018-02-23|
    JP2018524154A|2018-08-30|
    KR20180005223A|2018-01-15|
    SG11201709937SA|2017-12-28|
    WO2016193582A1|2016-12-08|
    EP3304198A1|2018-04-11|
    TW201715296A|2017-05-01|
    FR3037070B1|2019-05-31|
    US20180173094A1|2018-06-21|
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    WO2013119832A1|2012-02-10|2013-08-15|Board Of Regents, The University Of Texas System|Anhydride copolymer top coats for orientation control of thin film block copolymers|
    WO2014035963A1|2012-08-31|2014-03-06|Wisconsin Alumni Research Foundation|Topcoat surfaces for directing the assembly of block copolymer films on chemically patterned surfaces|
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    优先权:
    申请号 | 申请日 | 专利标题
    FR1554982|2015-06-02|
    FR1554982A|FR3037070B1|2015-06-02|2015-06-02|METHOD FOR CONTROLLING SURFACE ENERGY AT THE INTERFACE BETWEEN A BLOCK COPOLYMER AND ANOTHER COMPOUND|FR1554982A| FR3037070B1|2015-06-02|2015-06-02|METHOD FOR CONTROLLING SURFACE ENERGY AT THE INTERFACE BETWEEN A BLOCK COPOLYMER AND ANOTHER COMPOUND|
    KR1020177035413A| KR20180005223A|2015-06-02|2016-05-26|Method for controlling the surface energy at the interface between a block copolymer and another compound|
    CN201680039637.9A| CN107735727A|2015-06-02|2016-05-26|For the method for the surface energy for controlling the interface between block copolymer and other compound|
    SG11201709937SA| SG11201709937SA|2015-06-02|2016-05-26|Method for controlling the surface energy at the interface between a block copolymer and another compound|
    JP2017562680A| JP2018524154A|2015-06-02|2016-05-26|Method for controlling the surface energy of an interface between a block copolymer and another compound|
    US15/579,063| US20180173094A1|2015-06-02|2016-05-26|Process for controlling the surface energy at the interface between a block copolymer and another compound|
    PCT/FR2016/051252| WO2016193582A1|2015-06-02|2016-05-26|Method for controlling the surface energy at the interface between a block copolymer and another compound|
    EP16730881.6A| EP3304198A1|2015-06-02|2016-05-26|Method for controlling the surface energy at the interface between a block copolymer and another compound|
    TW105116664A| TW201715296A|2015-06-02|2016-05-27|Process for controlling the surface energy at the interface between a block copolymer and another compound|
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