• 专利附录
  • 专利说明
  • 权利要求
  • 类似技术
  • 同族专利
  • 引用文献
  • 法律状态
  • 优先权
    • 专利摘要:
    The invention relates to a method for reducing the defectivity of a block copolymer film (BPC1), the lower surface of which is in contact with a previously neutralized surface (N) of a substrate (S) and whose upper surface is covered by a surface neutralization topcoat (TC), to obtain an orientation of the nano-domains of said block copolymer (BPC1) perpendicular to the two lower and upper interfaces, said method being characterized in that said surface-neutralizing top layer (TC) used to cover the upper surface of the block copolymer film (BCP1) is constituted by a second block copolymer (BPC2).
    公开号:FR3037071A1
    申请号:FR1554983
    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 The present invention relates to the field of reducing the defectivity of a block copolymer film, and more particularly to the field of reducing the defectivity of a block copolymer film. reduction of perpendicularity defects or defects related to a low mobility of the polymer chains within the patterns of said block copolymer film.] [0002] The development of nanotechnologies has made it possible to constantly miniaturize the products of the Microelectronics and mechanical microelectromechanical systems (MEMS) in particular Today, conventional lithography techniques no longer meet these constant needs for miniaturization, because they do not make it possible to produce structures with dimensions of less than 60 nm. 0003] It was therefore necessary to adapt the lithography techniques and create engraving masks that allow the creation of moti fs more and more small with great 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, so that they can then selectively remove one of the blocks of the block copolymer and create a porous film with the residual block (or blocks). The patterns thus created in the porous film can be subsequently transferred, by etching, to an underlying substrate. Each of the blocks i, j of a block copolymer, denoted BCP, has a surface energy denoted Nu..yi, which is specific to it and which is a function of its chemical constituents, that is to say the chemical nature of the monomers or comonomers that compose it. Each of the blocks i, j of the BCP block copolymer furthermore has a Flory-Huggins type interaction parameter, denoted: Xix, Ref: 0456B-ARK63-3037071 2 when it interacts with a given "x" material, which can be a gas, a liquid, a solid surface, or another polymer phase for example, and an inter-facial energy denoted "Yix", with Yix = Yi- (yx cos eix), where (Ten is the angle The interaction parameter between two blocks i and j of the block copolymer is therefore denoted xi [0006] Jia et al., Journal of Macromolecular Science, B, 2011, 50, 1042, have shown that there is a relationship between the surface energy y and the Hildebrand solubility parameter δ of a given material I. In fact, the interaction parameter of FloryHuggins between two given materials i and x is indirectly related to the energies of y surfaces and Y x specific to the materials, so we speak either in terms of surface energies or in terms of interaction parameter erms to describe the physical phenomenon of interaction appearing at the interface of the materials. [0007] 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 various interfaces with which he 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 an atmosphere of controlled composition. 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. When the surface energy of each interface is not controlled, there is generally a random orientation of the block copolymer units, and more particularly an orientation parallel to the substrate, regardless of the morphology of the copolymer. to blocks. This parallel orientation is mainly due to the fact that the substrate and / or the 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 Ref: 0456B-ARK63-3037071 3 with the underlying substrate, denoted Xi-substrate, and / or the Flory-Huggins type interaction parameter of a block i of the BCP block copolymer with the compound at the upper interface, for example air, denoted Xi-air, is nonzero 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 interface lower between the underlying substrate and the BCP block copolymer is neutral with a Flory-Huggins parameter for each of the blocks of the Xi-substrate and Xi-substrate block copolymer equal to zero or, more generally, equivalent for each block of the BCP block copolymer. In this case, a layer of one or more blocks of the BCP block copolymer having the highest air affinity is organized in the upper portion of the BCP block copolymer film; to say at the interface with the air, and is paralleling this interface. 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 poly (methylmethacrylate-co-styrene) (PMMA-r-PS), functionalized by a hydroxyl function in end of chain, allows a good grafting of the copolymer on the surface of a silicon substrate having a native oxide layer (Si / SiO2 native) and obtaining a non-preferential surface energy for the blocks of the copolymer 30 blocks to nano-structure BCP. 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 copolymer at Ref: 0456B-ARK63- 3037071 4 BCP blocks is equivalent for each of the blocks i ... j of the BCP block copolymer, and is modulated by the ratio of the monomers 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 in parallel with 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-substrate and BCP-air copolymer copolymer interfaces in For example, the surface energy of the two interfaces must be equivalent to the blocks of the BCP block copolymer. In addition, when the surface energy at the upper interface of the copolymer is poorly controlled, a significant amount of defects appear, such as, for example, defects in perpendicularity or defects related to too low mobility. polymer chains, within the nano-domains of the block copolymer once self-assembled. A low mobility of the polymer chains of a block copolymer can indeed lead to the occurrence of a high density of dislocation and / or disclination defects. These different types of defects can appear in nano-domains of different morphologies. Thus, for example, R. Hammond et al, in the article entitled "Adjustment of block copolymer nanodomains sizes at lattice defect sites", Macromolecules, 2003, 36, p.8712-8716, describe dislocation defects and / or disclination occurring in cylindrical or spherical nano-domains perpendicular to the surface of the substrate. X. Zhang et al, in Article 25 entitled "Fast assembly of ordered block copolymer nanostructures through microwave annealing", acsnano, 2010, Vol.4, No. 11, p.7021-7029, describe defects in nano-domains. lamellar or cylindrical morphologies lying down, ie parallel to the surface of the underlying substrate. [0015] If the lower interface between the BCP block copolymer and the underlying substrate is today controlled, via the grafting of a random copolymer, for example, 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. Various approaches, described below, however, exist to remedy this, the surface energy at the lower interface between the BPC block copolymer 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 that makes it possible to satisfy the conditions of neutrality with respect to each of the blocks of the BPC block copolymer. 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 neutralized BCP / S substrate copolymer interface by means of a random copolymer N grafted to the surface of the substrate for example, and secondly, thanks to the fact that the blocks ij of the BCP block copolymer naturally have a comparable affinity for the component at the upper interface, in this case the air in the example. We then have Xi-substrate Xj-substrate (= 0 preferably) and Yi-air Yj-air.
    [0002] 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 generated nano-domains. In addition, the surface energy of a given material depends on the temperature. However, if the temperature of self-organization is increased, for example when it is desired 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 difference in surface energy of the blocks then becomes too great for the affinity of each block of the block copolymer for the compound at the upper interface can still be considered equivalent. In this case, the increase of the self-organization temperature can then cause the appearance of perpendicularity defects or dislocation or disclination defects related to the mobility of the chains. polymers. By way of example, the appearance of perpendicular cylinders of ovoid rather than circular shape can be seen because of the difference in surface energy between blocks of the block copolymer at the 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 US2013 280497, consists in controlling the surface energy at the upper interface of a nano-structuring block copolymer of poly (trimethylsilystyrene-b-lactide) or poly (styrene-b-trimethylsilystyrene-b-styrene type). ), by the introduction of an upper layer, also called "top coat" throughout the remainder of the description, deposited on the surface of the block copolymer. In this document, the top coat, polar, is deposited by "spin coating" on the nano-structuring block copolymer film.
    [0003] The top coat is soluble in an acidic or basic aqueous solution, which allows it to be applied 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 cycle of the maleic anhydride of the top coat closes, the top coat undergoes a transformation in a less polar state and becomes neutral with respect to the copolymer. blocks, thereby permitting 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.  Similarly, the document US 2014238954A describes the same principle as that of US2013 208497, but applied to a block copolymer containing a silsesquioxane type block.  This solution makes it possible 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, with a top block copolymer interface. coat, denoted "BCP-TC".  In this case, the top coat "TC" has an equivalent affinity Ref: 0456B-ARK63- 303 70 71 7 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. 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.  In addition, it is not easy to find a top coat whose composition makes it possible to control the defectivity of the block copolymer and in particular to reduce the defects of perpendicularity, dislocation and / or disclination.  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 tedious and complex to implement. and do not significantly reduce the defectivity within the patterns of the block copolymer.  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 drawbacks of the prior art.  The invention aims in particular to provide a simple and industrially feasible solution, to be able to significantly reduce the defectivity of a block copolymer film.  BRIEF DESCRIPTION OF THE INVENTION [0025] To this end, the subject of the invention is a process for reducing the defectivity of a block copolymer film, the lower surface of which is in contact with a previously neutralized surface. of a substrate and whose upper surface is covered by a surface neutralization upper layer, to allow to obtain an orientation of the nano-domains of said block copolymer perpendicularly to the two lower and upper interfaces, said method being characterized in that said upper surface neutralization layer set to cover the upper surface of the block copolymer film is constituted by a second block copolymer.  Thus, the blocks of the second block copolymer may have a modulated surface energy with respect to each other so that at the self-organization temperature of the first block copolymer, at least one of the blocks of the second block copolymer has a neutral surface energy with respect to all the blocks of the first block copolymer film.  The composition of the second block copolymer can furthermore be easily adjusted and optimized so as to obtain a minimum of perpendicularity defects and / or dislocation and / or disclination defects at the time of assembly of the first film. of block copolymer.  According to other optional characteristics of the process for reducing the defectivity of a block copolymer film: the second block copolymer comprises a first block, or set of 15 blocks, whose surface energy is the lower 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 of the blocks of the first block copolymer, the second block copolymer comprises m blocks, m being an integer 2 and 11, and preferably - the volume fraction of each block of the second block copolymer varies from 5 to 95% with respect to the volume of the second block copolymer, - the first block, or set of blocks, whose energy is the weakest, has a volume fraction of between 50% and 70% relative to the volume of the second block copolymer, each block of the second block copolymer may comprise monomers present in the backbone of the first block copolymer (BCP1), the second block copolymer has an annealing temperature lower than or equal to that of the first block copolymer, the molecular weight of the second block copolymer varies between 1000 and 500,000 g / mol, Ref: 0456B-ARK63- 3037071 9 - each block of the second block copolymer may consist of a set of comonomers, copolymerized together under a block, gradient, random, random, alternating architecture, comb, - the morphology of the second block copolymer is preferably lamellar, without excluding the other possible morphologies, - the second block copolymer can be synthesized by any technique or combination of techniques known to man of the job.  Other features and advantages of the invention will become apparent upon 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 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, - Figure 2, already described, a diagram of a block copolymer 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, - Figure 3, a diagram of a block copolymer before 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; - FIG. a copolymer to blocks before 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 mixture of monomers into a polymer.  By "copolymer" is meant a polymer comprising several different monomer units.  Ref: 0456B-ARK63- 3037071 [0033] "Statistical copolymer" is understood to mean a copolymer in which the distribution of monomer units along the chain follows a statistical law, for example of the Bernoullian type (Markov zero order) or Markovian of the first or second order.  When the repeat units are randomly distributed along the chain, the polymers have been formed by a Bernoulli process and are referred to as random copolymers.  The term random copolymer is often used, even when the statistical process that prevailed during the synthesis of the copolymer is not known.  By "gradient copolymer" is meant a copolymer in which the distribution of the monomer units varies progressively along the chains.  The term "alternating copolymer", a copolymer comprising at least two monomer 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 polymer species, the polymer blocks being chemically different from one another, or from one another, 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 exhibit 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.  [0037] 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 strictly less than the sum of the Tg of the compounds taken alone.  In the description, it is referred to as "self-assembly" as well as "self-organization" or "nano-structuring" to describe the well-known phenomenon of phase separation of block copolymers. at an assembly temperature also called annealing temperature.  The term "lower interface" of a block copolymer to nanostructure, the interface in contact with an underlying substrate on which a film of said Ref: 0456B-ARK63-3037071 11 block copolymer is deposited .  It will be noted that, throughout the remainder of the description, this lower interface is neutralized by a technique known to those skilled in the art, such as the grafting of a random copolymer on the surface of the substrate prior to the deposition of the copolymer film at blocks for example.  The term "upper interface" or "upper surface" of a nano-structuring block copolymer means the interface in contact with a compound, or 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 mixture of solvents in which the block copolymer is insoluble, when the compound is solid it may for example be another substrate 15 such as a silicon substrate for example.  By "defects" within the nano-domains of a block copolymer is meant defects of perpendicularity but also dislocation defects and / or disclination related to too low mobility of the copolymer chains.  As regards the nano-structuring block copolymer film, referenced BCP1, it comprises "n" blocks, n being an integer greater than or equal to 2 and preferably less than 11, and even 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 Al, B1, Cl, D1,, Zl, are all blocks "i". . .  "Jl" representing either pure chemical entities, i.e. 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.  Each of the blocks "he". . .  Of the BCP1 block copolymer to be nanostructured, "j1" can therefore potentially be written as: ## STR1 ## . . -co-z; ', with i' #. . .  #j ', in whole or in part.  Ref: 0456B-ARK63- 3037071 12 [0044] 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.  The volume fraction of each of the blocks there. . .  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.  The volume fraction of each entity of a block of a copolymer, or of each block of a block copolymer, is measured in the manner described hereinafter.  Within a copolymer in which at least one of the entities, or one of the blocks in the case of a block copolymer, comprises more than one comonomer, it is possible to measure by NMR of the proton, the mole fraction of each monomer throughout the copolymer, then to go back to the mass fraction using the molar mass of each monomer unit.  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 comonomers constituting the entity or 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.  The principle of the invention consists in covering the upper surface of the nano-structuring block copolymer, referenced BCP1, itself previously deposited on an underlying substrate S whose surface has been neutralized, by grafting 30 d a layer N of random copolymer for example, by a top layer, hereinafter referred to as "top coat" and referenced TC, the composition of which not only allows a control of the surface energy at the upper interface of said Ref: 0456B BPC1 block copolymer but also a significant reduction of the perpendicularity defects, and / or defects of disclinations and / or dislocations, of said block copolymer.  Such a layer of TC top coat then makes it possible to orient the patterns generated during the nano-structuring of the BCP1 block copolymer, whether these be of cylindrical, lamellar, or other morphology. . .  perpendicular to the surface of the underlying substrate S and the upper surface, with a significantly reduced defectivity.  For this, the top coat layer TC is advantageously constituted by a second block copolymer, referenced BCP2 thereafter.  Preferably, the second BCP2 block copolymer comprises at least two different blocks, or sets of blocks.  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 two block copolymers BPC1, BPC2 and secondly, a block, or a set of blocks, referenced "r2", having a zero affinity with all the blocks of the first block copolymer BPC1 to nano-structure.  The term "set of blocks" blocks having the same or similar surface energy.  The underlying substrate S may be a solid of inorganic, organic or metallic nature.  The second block copolymer 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, 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.  Each block "i2". .  "J2" of the BCP2 block copolymer may consist of any number of co-monomers, of any chemical nature, optionally including co-monomers present in the backbone of the first BCP1 block copolymer Ref: 0456B-ARK63-3037071 nano-structuring, on all 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.  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 sets of blocks, different in the BCP2 block copolymer.  Advantageously, one of the blocks, or set of blocks, denoted "s2" of the BPC2 block copolymer constituting the top coat, has the lowest surface energy of all the blocks of the two BPC1 block copolymers. 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 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 with nano- structure 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 may 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 this case the 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 0,. . .  Xil-air> 0,, Xj1-air> 0, Xi2-air> 0,, Xj2-air> 0- Ref: 0456B-ARK63- 3037071 To obtain a perpendicular orientation of the patterns generated by the nano-structuration 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.  [0061] Preferably, the block "s2" which has the lowest surface energy of all the blocks of block copolymers BPC1, BPC2 is also the one with the largest volume fraction of the BPC2 block copolymer.  Preferably, its volume fraction can range from 50 to 70% relative to the total volume of the BPC2 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 in addition have a zero affinity for all the blocks. of the first BPC1 block copolymer to be nanostructured.  Thus, the block "r2" is "neutral" vis-à-vis all the blocks of the first block copolymer BPC1.  We then = -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 surfaces and top of the stack.  Block "r2" may be defined by 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 random copolymerization of co-monomers constituting the first copolymer BPC1 blocks according to a precise composition.  Thanks to the combined action of these two blocks, or sets of blocks, "s2" and "r2" of the BPC2 block copolymer forming the top coat layer TC, it is possible to obtain a stack such as illustrated in the diagram of FIG. 3, leading to 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 block "s2" finds itself oriented parallel to the interface with the ambient air, and the block "r2" is found oriented parallel to the The block copolymer film blocks BPC1, Ref: 0456B-ARK63- 3037071 16 are thus interfaced to permit a perpendicular organization of the BPC1 block copolymer units.  The particular composition of each of the blocks of the second BCP2 block copolymer makes it possible to control the defectivity.  In particular, abacuses can be used to find the best composition of the second block copolymer in order to minimize the defects that may appear in the first BCP1 block copolymer film.  Advantageously, the BCP2 block copolymer consists of "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, denoted L02, can have any value.  Typically, it is located between 5 and 100nm.  The morphology adopted by the BCP2 block copolymer may 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 BCP2 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 may vary 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 constituent comonomer (s) 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 Ref: 0456B-ARK63- 3037071 17 ("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 an alkoxyl group 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 in position [3 with respect to the nitrogen atom of the nitroxide radical.  The remaining valencies 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-alkyl, comprising from 1 to 10 carbon atoms.  It is not excluded that the carbon atom and the nitrogen atom in formula (1) are connected to one another via a divalent radical so as to form a ring.  Preferably, however, the remaining valencies of the carbon atom and the nitrogen atom of the formula (1) are attached to monovalent radicals.  Preferably, the radical RL has a molar mass greater than 30 g / mol.  The 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 being able to be represented by the formula: ## STR2 ## in which R3 and R4, which may be the same or different, may be chosen from alkyl, cycloalkyl, alkoxyl, aryloxyl, aryl, aralkyloxyl, perfluoroalkyl and aralkyl radicals, and may comprise 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-methyl-propyl-nitroxide, N-tert-butyl-1- (2-naphthyl) -2-methylpropyl-nitroxide, N-tert-butyl-1-diethylphosphono-2,2-dimethylpropyl nitroxide, 20-N-tertbutyl-1-dibenzylphosphono-2,2-dimethylpropyl-nitroxide, N-phenyl-1-diethylphosphono-2,2-dimethylpropyl nitroxide, N-phenyl-1-diethyl phosphono-1-methyl ethyl nitroxide, N- (1-phenyl-2-methylpropyl) -1-diethylphosphono-1-methylethyl nitroxide, -4-oxo-2,2, 6,6-tetramethyl-1-piperidinyloxy, 25-2,4,6-tri-tert-butylphenoxy.  [0074] 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: vinyl, 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 acrylates, cycloalkyl or aryl 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-polyalkyleneglycol acrylates such as methoxypolyethylene glycol acrylates, ethoxypolyethylene glycol acrylates, methoxypolypropyleneglycol acrylates, methoxy-polyethyleneglycolpolypropyleneglycol acrylates or mixtures thereof, aminoalkyl such as 2- (dimethylamino) ethyl acrylate (ADAME), fluorinated acrylates, silyl acrylates, phosphorus acrylates te such as alkylene glycol phosphate acrylates, glycidyl acrylates, dicyclopentenyloxyethyl acrylates, methacrylic monomers such as methacrylic acid or its salts, alkyl, cycloalkyl, alkenyl or aryl methacrylates such as methyl methacrylate (MMA), lauryl, cyclohexyl, allyl, phenyl or naphthyl, hydroxyalkyl methacrylates such as 2-hydroxyethyl methacrylate or 2-hydroxypropyl methacrylate, alkyl ether methacrylates 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 of aminoalkyl such as 2- (dimethylamino) ethyl methacrylate (MADAME), methacrylates fluorinated ates 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 of alkoxy- or aryloxy-polyalkylene glycol, vinylpyridine, vinylpyrrolidinone, (alkoxy) poly (alkylene glycol) vinyl ether or divinyl ether, such as methoxy poly (ethylene glycol) vinyl ether, poly (ethylene glycol) divinyl ether, Ref: 0456B-ARK63- 3037071 the olefinic monomers, among which mention may be made of ethylene, butene and 1,1-diphenylethylene hexene and 1-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 case being protected to be compatible with the polymerization processes.  When the polymerization process is conducted by an anionic route, any anionic polymerization mechanism may be considered, whether it is liganded anionic polymerization or anionic ring opening polymerization.  Preferably, an anionic polymerization process in an apolar solvent, and preferably toluene, as described in patent EP0749987, and involving a micro-mixer, will be used.  When the polymers are synthesized cationically, anionically or by ring opening, the constituent comonomer (s) of the polymers will, for example, 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, especially alpha-methylstyrene, silylated styrenes, acrylic monomers such as alkyl acrylates, cycloalkyl acrylates or aryl acrylates such as methyl acrylate, ethyl acrylate, butyl acrylate, ethylhexyl acrylate or phenyl 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 2- (dimethylamino) ethyl acrylate (ADAME), fluorinated acrylates, silyl acrylates, phosphorus acrylates such as alkylene glycol phosphate acrylates, glycidyl acrylates, dicyclopentenyloxyeth alkyl, cycloalkyl, alkenyl or aryl methacrylates such as methyl methacrylate (MMA), lauryl, cyclohexyl, allyl, phenyl or naphthyl, alkyl ether methacrylates such as 2-ethoxyethyl methacrylate, alkoxy- or aryloxy-polyalkylene glycol methacrylates such as methoxypolyethylene glycol methacrylates, ethoxypolyethylene glycol methacrylates, methoxypolypropylene glycol methacrylates, metoxypolyethylene glycol methacrylates, methacrylates of methoxypolyethylene glycol, and methoxypolyethylene glycol methacrylates. polypropylene glycol or mixtures thereof, aminoalkyl methacrylates such as 2- (dimethylamino) ethyl methacrylate (MADAME), fluorinated methacrylates such as 2,2,2-trifluoroethyl methacrylate, silylated methacrylates such as 3- methacryloylpropyltrimethylsilane, phosphorus methacrylates such as alkylene glycol phosphate methacrylates, hydroxyethylimidyl methacrylate azolidone, 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, alkyl or alkoxy- or aryloxy-polyalkylene glycol maleates or hemimaleates, vinylpyridine, vinylpyrrolidinone, (alkoxy) poly (alkylene glycol) vinyl ether or divinyl ether, such as methoxy poly (ethylene glycol) vinyl ether poly (ethylene glycol) divinyl ether, olefinic monomers, among which mention may be made of ethylene, butene, 1,1-diphenylethylene, hexene and 1-octene, the dienic monomers of which butadiene, isoprene as well as fluorinated olefinic monomers, and vinylidene monomers, among which mention may be made of vinylidene fluoride, and cyclic monomers, among which mention may be made of lactones such as ε-caprolactone, lactides and 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, phosphorus cyclic esters such as cyclophosphorinans, cyclophospholanes, oxazolines, the protected case to be compatible with polymerization processes, globular methacrylates such as isobornyl methacrylates, halogenated isobornyl, halogenated alkyl methacrylate, naphthyl methacrylate, only 1s or in a mixture of at least two monomers mentioned above.  The second BCP2 block copolymer forming the top coat layer TC may be deposited on the BCP1 block copolymer film, itself previously Ref: 0456B-ARK63- 3037071 22 deposited on an underlying substrate S whose The 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.  [0080] That the two block copolymers BCP1 and BCP2 are deposited successively or simultaneously, they can be deposited on the surface of the previously neutralized substrate S N, according to techniques known to those skilled in the art, such as for example the technique known as "Spin coating", "doctor blade" "knife system" or "slot die system".  According to a preferred embodiment, the two block copolymers BCP1 10 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.  Both BCP1 and BCP2 copolymers must not be miscible with each other, or at least very little miscible, to prevent the second BCP2 copolymer interferes with the morphology adopted by the first BCP1 block copolymer.  The mixture of block copolymers BCP1 + BCP2 can then be deposited on the surface of the substrate, according to techniques known to those skilled in the art, for example the so-called "spin coating" technique, "Doctor Blade" " knife system "or" slot die system ".  After the two block copolymers BCP1 and BCP2 have been deposited successively or simultaneously, a stack of layers comprising the substrate S, a neutralization layer N, the first block copolymer BCP1 and the second BCP2 blocks.  [0085] The BPC2 block copolymer forming the TC top coat layer exhibits the well known phenomenon of phase separation block copolymers at an annealing temperature.  Ref: 0456B-ARK63- 3037071 23 [0086] The stack obtained is then subjected to a heat treatment so as to nano-structure at least one of the two block copolymers.  Preferably, the second BCP2 block copolymer is nano-structured first so that its lower interface may have a 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 BCP2 is preferably less than or equal to the annealing temperature of the first block copolymer BCP1 while being greater than the highest glass transition temperature of BCP1.  In addition, when the annealing temperature is the same, 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 is also structured 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 BPC2 copolymer 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 boundary, termed "MST" (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 _, - 2. nt <10.5 or again xs2, -2.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 vis-à-vis all the blocks of the first BCP1 block copolymer.
    [0004] 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. [0090] Preferably, the time required for the organization of 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. The particular composition of each block of the second block copolymer makes it possible to control the defectivity. In particular, it will be possible to use abacuses to find the best composition of the second block copolymer in order to minimize the defects of perpendicularity, and / or the defects of dislocation and / or disclination, which may appear in the film of the first copolymer to BCP1 blocks. [0093] Optionally, the "s2" block of the BPC2 block copolymer constituting the TC top coat may be highly soluble in a solvent, or solvent mixture, which is not a solvent or solvent mixture of the first copolymer. BPC1 intended to be nano-structured to form a nano-lithography mask. The "s2" block 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. Once the nano-structured BCP1 block copolymer film, with an orientation of its patterns perpendicular to the surface of the stack, it is advisable to proceed with the removal of the top layer of TC top coat formed by the Ref. The second block copolymer BCP2 is used to utilize the nano-structured BCP1 block copolymer film as a mask in a nanolithography process to transfer its patterns to the underlying substrate. For this, the removal of the block copolymer BPC2 can 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, the nano-domains of which are oriented perpendicularly to the surface of the underlying substrate, as shown in the FIG. FIG. 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 process of FIG. nano-lithography. Optionally, prior to the removal of the BCP2 block copolymer of constitution of the upper neutralization layer, a stimulus may also be applied to all or part of the stack obtained, consisting of the substrate S, the N layer. 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 a liquid with acid-base properties or oxidation-reduction, 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 or different from the MS2 solvent, depending on the extent of the solubility change of the BPC2 block copolymer following exposure to the stimulus. Ref: 0456B-ARK63- 3037071 [0097] 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 applied stimulus, such that the block in question can be modified following the stimulus, following the same principle as the modified BCP2 block copolymer by 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 mask copolymer is a PS-b-PMMA block copolymer, 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 the 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 . 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: 0456B-ARK63-
    权利要求:
    Claims (10)
    [0001]
    REVENDICATIONS1. Process for reducing the defectivity of a block copolymer film (BPC1), the lower surface of which is in contact with a previously neutralized (N) surface of a substrate (S) and whose upper surface is covered by a layer surface neutralizing surface (TC), for obtaining an orientation of the nano-domains of said block copolymer (BPC1) perpendicular to the two lower and upper interfaces, said method being characterized in that said top layer (TC) of surface neutralization implemented to cover the upper surface of the block copolymer film (BCP1) is constituted by a second block copolymer (BPC2).
    [0002]
    2. Method according to claim 1, characterized in that the second block copolymer (BCP2) comprises a first block, or set of blocks, ("s2") whose surface energy is the lowest of all the constituent 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 block of the first block copolymer (BCP1).
    [0003]
    3. Method according to one of claims 1 to 2, characterized in that the second block copolymer (BCP2) comprises "m" blocks, m being an integer 2 and 11, and preferably
    [0004]
    4. Method according to one of claims 1 to 3, characterized in that the volume fraction of each block of the second block copolymer (BCP2) ranges from 5 to 95% relative to the volume of said second block copolymer.
    [0005]
    5. Method according to one of claims 2 to 4, characterized in that the first block, or set of blocks, ("s2") whose energy is the lowest, has a volume fraction of between 50% and 70% based on the volume of the second block copolymer (BCP2).
    [0006]
    6. Method according to one of claims 1 to 5, characterized in that each block (i2 ... j2) of the second block copolymer (BCP2) may comprise comonomers present in the backbone of the first block copolymer (BCP1). . Ref: 0456B-ARK63- 3037071 28
    [0007]
    7. Method according to one of claims 1 to 6, characterized in that the second block copolymer (BCP2) has an annealing temperature less than or equal to that of the first block copolymer (BCP1).
    [0008]
    8. Method according to one of claims 1 to 7, characterized in that the molecular weight of the second block copolymer (BCP2) varies between 1000 and 500000 g / mol.
    [0009]
    9. Method according to one of claims 1 to 8, characterized in that each block of the block copolymer (BCP2) may consist of a set of comonomers, copolymerized together under a block, gradient, statistical architecture, random, alternated, comb.
    [0010]
    10. Method according to one of claims 1 to 9, characterized in that the morphology of the second block copolymer (BCP2) is preferably lamellar. Ref: 0456B-ARK63-
    类似技术:
    公开号 | 公开日 | 专利标题
    FR3037071B1|2019-06-21|METHOD FOR REDUCING THE DEFECTIVITY OF A BLOCK COPOLYMER FILM
    EP2696993B1|2019-03-20|Method for the preparing surfaces
    FR3010413A1|2015-03-13|METHOD FOR CONTROLLING THE PERIOD OF A NANO-STRUCTURE ASSEMBLY COMPRISING A MIXTURE OF BLOCK COPOLYMERS
    FR3014877A1|2015-06-19|METHOD FOR NANOSTRUCTURING A BLOCK COPOLYMER FILM FROM A NON-STRUCTURED BLOCK COPOLYMER BASED ON STYRENE AND METHYL METHACRYLATE, AND NANOSTRUCTURE BLOCK COPOLYMER FILM
    EP3304198A1|2018-04-11|Method for controlling the surface energy at the interface between a block copolymer and another compound
    WO2015004392A1|2015-01-15|Method for the perpendicular orientation of nanodomains of block copolymers, using statistical or gradient copolymers, the monomers of which differ at least in part from those present in each of the blocks of the block copolymer
    FR3010411A1|2015-03-13|METHOD FOR CONTROLLING THE PERIOD OF A NANO-STRUCTURE ASSEMBLY COMPRISING A MIXTURE OF BLOCK COPOLYMERS
    FR3014876A1|2015-06-19|METHOD FOR PRODUCING A BLOCK COPOLYMER FILM ON A SUBSTRATE
    WO2021064328A1|2021-04-08|Neutral sub-layer for a block copolymer and polymer stack comprising such a sub-layer covered with a block copolymer film
    WO2021064329A1|2021-04-08|Neutral sub-layer for a block copolymer and polymer stack comprising such a sub-layer covered with a block copolymer film
    WO2015121568A1|2015-08-20|Method for controlling the surface energy of a substrate
    WO2019016487A1|2019-01-24|Method for controlling the orientation of nanodomains of a block copolymer
    FR3045645B1|2019-07-05|METHOD OF REDUCING DEFECTS IN ORDINATED BLOCK COPOLYMER FILM
    FR3105755A1|2021-07-02|Method of manufacturing an etching stop layer for nanolithography by directed self-assembly
    WO2019016488A1|2019-01-24|Method for controlling the orientation of nanodomains of a block copolymer
    FR3010412A1|2015-03-13|PROCESS FOR OBTAINING NANO-STRUCTURE THICK FILMS OBTAINED FROM BLOCK COPOLYMERS
    FR3045642A1|2017-06-23|METHOD FOR REDUCING THE STRUCTURING TIME OF ORDINATED BLOCK COPOLYMER FILMS
    FR3045644A1|2017-06-23|PROCESS FOR OBTAINING THICK ORDERED FILMS AND HIGH PERIODS COMPRISING A BLOCK COPOLYMER
    同族专利:
    公开号 | 公开日
    US20180171134A1|2018-06-21|
    KR20180005224A|2018-01-15|
    JP2018516301A|2018-06-21|
    EP3304200A1|2018-04-11|
    TW201702077A|2017-01-16|
    FR3037071B1|2019-06-21|
    SG11201709707TA|2017-12-28|
    CN107850836A|2018-03-27|
    WO2016193581A1|2016-12-08|
    引用文献:
    公开号 | 申请日 | 公开日 | 申请人 | 专利标题
    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|
    US20140069325A1|2012-09-07|2014-03-13|Kabushiki Kaisha Toshiba|Pattern forming method|
    WO2014169102A1|2013-04-10|2014-10-16|Kla-Tencor Corporation|Direct self assembly in target design and production|
    US20140370718A1|2013-06-14|2014-12-18|Tokyo Electron Limited|Etch process for reducing directed self assembly pattern defectivity using direct current positioning|
    US20140377518A1|2013-06-24|2014-12-25|Dow Global Technologies Llc|Orientation control layer polymers, methods of manufacture thereof and articles comprising the same|
    FR2735480B1|1995-06-15|1997-07-18|Atochem Elf Sa|CONTINUOUS ANIONIC POLYMERIZATION PROCESS OF AT LEAST ONE ACRYLIC MONOMER FOR THE OBTAINING OF POLYMERS WITH A HIGH SOLID RATE|
    US20130208497A1|2010-04-05|2013-08-15|University Of Utah Research Foundation|Infusion line identification lighting system|
    CN101837950B|2010-05-24|2012-09-05|山东大学|Device and method for assembling nanostructure directly by using two-block copolymer|
    KR101963924B1|2011-07-29|2019-03-29|위스콘신 얼럼나이리서어치 화운데이션|Block copolymer materials for directed assembly of thin films|
    US9718250B2|2011-09-15|2017-08-01|Wisconsin Alumni Research Foundation|Directed assembly of block copolymer films between a chemically patterned surface and a second surface|
    JP6027912B2|2013-02-22|2016-11-16|東京応化工業株式会社|Method of manufacturing structure including phase separation structure, pattern forming method, and topcoat material|
    US9382444B2|2013-06-24|2016-07-05|Dow Global Technologies Llc|Neutral layer polymers, methods of manufacture thereof and articles comprising the same|
    CN104370274B|2014-11-10|2016-09-28|中国科学院长春应用化学研究所|The guiding assemble method of nanostructured|FR3069339B1|2017-07-21|2021-05-14|Arkema France|METHOD OF CHECKING THE ORIENTATION OF THE NANO-DOMAINS OF A BLOCK COPOLYMER|
    FR3074179B1|2017-11-24|2021-01-01|Arkema France|METHOD OF CHECKING THE FLATNESS OF A POLYMERIC STACK|
    FR3074180B1|2017-11-24|2021-01-01|Arkema France|METHOD OF CHECKING THE FLATNESS OF A POLYMERIC STACK|
    FR3096281A1|2019-05-20|2020-11-27|Université De Bordeaux|process for preparing a block copolymer film for creating a nanolithography mask|
    法律状态:
    2016-05-16| PLFP| Fee payment|Year of fee payment: 2 |
    2016-12-09| PLSC| Search report ready|Effective date: 20161209 |
    2017-05-11| PLFP| Fee payment|Year of fee payment: 3 |
    2018-05-14| PLFP| Fee payment|Year of fee payment: 4 |
    2019-05-10| PLFP| Fee payment|Year of fee payment: 5 |
    2021-03-12| ST| Notification of lapse|Effective date: 20210205 |
    优先权:
    申请号 | 申请日 | 专利标题
    FR1554983|2015-06-02|
    FR1554983A|FR3037071B1|2015-06-02|2015-06-02|METHOD FOR REDUCING THE DEFECTIVITY OF A BLOCK COPOLYMER FILM|FR1554983A| FR3037071B1|2015-06-02|2015-06-02|METHOD FOR REDUCING THE DEFECTIVITY OF A BLOCK COPOLYMER FILM|
    PCT/FR2016/051251| WO2016193581A1|2015-06-02|2016-05-26|Method for reducing the defectivity of a block copolymer film|
    US15/579,112| US20180171134A1|2015-06-02|2016-05-26|Process for reducing the defectivity of a block copolymer film|
    JP2017562689A| JP2018516301A|2015-06-02|2016-05-26|Method for reducing defects in block copolymer films|
    SG11201709707TA| SG11201709707TA|2015-06-02|2016-05-26|Method for reducing the defectivity of a block copolymer film|
    CN201680044441.9A| CN107850836A|2015-06-02|2016-05-26|The defects of for reducing block copolymer film rate method|
    EP16732319.5A| EP3304200A1|2015-06-02|2016-05-26|Method for reducing the defectivity of a block copolymer film|
    KR1020177035414A| KR20180005224A|2015-06-02|2016-05-26|Method for reducing the defectivity of a block copolymer film|
    TW105116665A| TW201702077A|2015-06-02|2016-05-27|Process for reducing the defectivity of a block copolymer film|
    [返回顶部]