METHOD FOR CONTROLLING THE PLANEITY OF A POLYMERIC STACK

专利摘要:
The invention relates to a method for controlling the flatness of a polymeric stack, said stack comprising at least a first and a second (co-) polymer layer (20, 30) stacked one on the other, the first an underlying (co) polymeric layer (20) which has not undergone any prior treatment allowing its crosslinking, at least one of the (co-) polymer layers being initially in a liquid or viscous state, said process being characterized in that the top layer (30), said top coat (TC) is deposited on the first layer (20) in the form of a pre-polymer composition (pre-TC), comprising at least one monomer (s) and / or dimer (s) and / or oligomer (s) and / or polymer (s) in solution, and in that it is then subjected to a stimulus able to cause a crosslinking / polymerization reaction of the molecular chains within said layer (30, TC).
公开号:FR3074180A1
申请号:FR1761179
申请日:2017-11-24
公开日:2019-05-31
发明作者:Xavier Chevalier；Ilias Iliopoulos
申请人:Arkema France SA；
IPC主号:

专利说明:

PROCESS FOR CONTROLLING THE PLANEITY OF A POLYMERIC STACK [Field of the Invention [0001] The present invention relates to the field of polymeric stacks.
More particularly, the invention relates to a method for controlling the flatness of such stacks. The invention also relates to a process for manufacturing a nano-lithography mask from such a stack, the flatness of which is controlled, and a polymeric stack obtained by said flatness control process.
Polymer stacks are used in a multitude of industrial applications among which we can cite, by way of non-exhaustive example, the production of coatings for the aerospace or aeronautics or automotive or wind power industries. , inks, paints, membranes, biocompatible implants, packaging materials, or even optical components, such as optical filters for example, or microelectronic, optoelectronic or microfluidic components. The invention is addressed to all applications whatever they are, since the stack comprises at least two polymeric materials stacked one on the other.
Among the various possible industrial applications, the invention is also concerned, and in a non-exhaustive manner, with applications dedicated to the field of organic electronics, and more particularly with applications of nano-lithography by directed self-assembly. , also called DSA (from the acronym "Directed Self-Assembly"), for which other requirements must be met concomitantly.
The prior art and stability of thin polymer films on a solid substrate or on an underlying layer, itself solid or liquid, are technologically important in certain industrial applications such as, for example, the surface protection for aerospace or aeronautics or automotive or wind power, paints, inks, membrane manufacturing, or even microelectronic, optoelectronic or microfluidic components.
Ref: 0559-ARK88 [0006] Polymer-based materials have so-called low surface energy interfaces, where molecular chains therefore have relatively low cohesion energy, compared with other solid interfaces such as surfaces 'oxides or metals having a significantly higher surface energy, therefore less likely to be deformable under the effect of any force.
[0007] In particular, the phenomenon of dewetting a polymer film deposited in the liquid or viscous state on the surface of an underlying layer, itself in the solid or liquid state, has been known for a long time. The term “liquid or viscous polymer” is understood to mean a polymer having, at a temperature above the glass transition temperature, due to its rubbery state, an increased capacity for deformation due to the possibility given to its molecular chains to move freely. . The hydrodynamic phenomena at the origin of dewetting appear as long as the material is not in a solid state, that is to say undeformable due to the negligible mobility of its molecular chains. This dewetting phenomenon is characterized by the spontaneous withdrawal of the polymer film applied to the surface of the underlying layer, when the initial stacking system is left free to evolve over time. There is then a loss of continuity of the initial film and a variation in thickness. The film does not spread and forms one or more spherical caps / droplets revealing a non-zero contact angle with the underlying surface. This phenomenon is illustrated in Figures 1A to 1C. FIG. 1A represents more particularly a solid substrate 10, on which is deposited a layer of polymer 20 in the liquid or viscous state. In this first case, the stacking system is in a "liquid / solid" configuration. After the deposition of such a polymer layer 20, the dewetting phenomenon appears and the polymer 20 no longer spreads correctly on the surface of the substrate 10, forming spherical caps and resulting in a stack whose surface is not flat. . FIG. 1B represents a solid substrate 10, on which a first layer of polymer 20 is deposited, this first layer being solidified at the time of deposition of a second upper polymer layer 30. In this case, the second polymer layer 30 to the upper surface is deposited in a liquid or viscous state on the solid surface of the first layer of polymer 20. It is said that the interface between the two layers of polymer is in a
Ref: 0559-ARK88 "liquid / solid" configuration. In this case too, after a certain time, a dewetting phenomenon occurs and the polymer 30 does not spread correctly on the surface of the first polymer layer 20, forming spherical caps and resulting in a stack whose surface n is not flat. Finally, FIG. 1C represents a solid substrate 10, on which is deposited a first layer of polymer 20 in the liquid or viscous state, itself covered with a second layer of polymer superior 30 in the liquid or viscous state. In this case, the interface between the two layers of polymer is in a "liquid / liquid" configuration. In this case also, the second upper layer 30 of polymer does not spread correctly on the surface of the first polymer layer 20 and it can also, optionally, dissolve in part in the first polymer layer 20, causing a phenomenon of inter-diffusion at the interface between the two layers. This layer 30 then deforms, inter alia under the combined effect of gravity, of its own density, of its surface energy, of the viscosity ratio between the materials of the polymer layers 30 and 20 in presence, as well as under the effect of Van der Waals interactions leading to the amplification of the capillary waves of the system. This deformation leads to the production of a discontinuous film 30, further comprising spherical caps, and also deforming the first underlying polymer layer 20. This therefore results in a stack whose surface is not flat and whose interface between the two layers of polymer is not clear.
The spreading coefficient of a liquid or viscous layer, noted S, is given by Young's equation below:
S = yc - (Ycl + Yl), in which y _c represents the surface energy of the underlying layer, solid or liquid, y _L represents the surface energy of the upper layer of liquid polymer and y _C L represents the energy at the interface between the two layers. Surface energy (denoted y _x ) of a given material “x” is understood to mean the excess energy at the surface of the material compared to that of the material taken as a mass. When the material is in liquid form, its surface energy is equivalent to its surface tension. When the spreading coefficient S is positive, then the wetting is total and the liquid film spreads completely over the surface of the underlying layer. When the spreading coefficient S is negative, then the wetting is partial, that is to say that the film does not spread completely over the surface of the underlying layer and
Ref: 0559-ARK88 we witness the phenomenon of dewetting if the initial stacking system is left free to evolve.
In these stacking systems of layer (s) of polymer materials, in which the configurations can for example be “liquid / solid” or “liquid / liquid”, the surface energies of the different layers can be very different, thus making the entire system metastable or even unstable due to the mathematical formulation of the spreading parameter S.
When a stacking system, deposited on any substrate, comprises different layers of polymeric material in the liquid / viscous state, stacked on each other, the stability of the entire system is governed by the stability of each layer at the interface with different materials.
For this kind of metastable or even unstable liquid / liquid system, dewetting phenomena were observed during the relaxation of the initial stresses, independently of the nature of the materials involved (small molecules, oligomers, polymers) . Different studies (F. Brochart-Wyart & al., Langmuir, 1993, 9, 3682-3690; C. Wang & al., Langmuir, 2001, 17, 6269-6274; M. Geoghegan & al., Prog. Polym. Sci. , 2003, 28, 261-302) have demonstrated and explained theoretically and experimentally the behavior as well as the origin of the dewetting observed. Whatever the mechanisms (spinodal decomposition or nucleation / growth), this type of liquid / liquid system tends to be particularly unstable and leads to the introduction of severe defects in the form of discontinuity of the film of interest, c that is to say in the example of FIG. 1C the first polymer layer 20, the initial flatness of which is disturbed, with the appearance, in the best of cases, of holes in the film or the double layer of polymer films thus rendering it unusable for the intended applications.
Dewetting is a thermodynamically favorable phenomenon, materials spontaneously seeking to minimize the contact surface with each other as much as possible. However, for all the applications referred to above, it is precisely sought to avoid such a phenomenon, in order to have perfectly flat surfaces. We also seek to avoid the phenomena of inter-diffusion between the layers in order to obtain clear interfaces.
A first problem that the applicant has sought to solve therefore consists in avoiding the appearance of dewetting phenomena in the
Ref: 0559-ARK88 polymer stack systems, at least one of the polymers of which is in a liquid / viscous state, whatever the polymers in the system and whatever the intended applications.
A second problem that the applicant has sought to solve consists in avoiding the phenomena of inter-diffusion at the interfaces, in order to obtain clear interfaces.
In the particular context of applications in the field of nanolithography by directed self-assembly, or DSA, block copolymers, capable of nanostructuring at an assembly temperature, are used as nano masks -lithography. For this, stacking systems of liquid / viscous materials are also used. These stacks comprise a solid substrate, on which is deposited at least one block copolymer film, denoted BCP below. This BCP block copolymer film, intended to form a nanolithography mask, is necessarily in a liquid / viscous state at the assembly temperature, so that it can self-organize into nano-domains, from made of phase segregation between blocks. The block copolymer film thus deposited on the surface of the substrate is therefore subject to dewetting phenomena when it is brought to its assembly temperature.
In addition, for the intended application, such a block copolymer must also preferably have nano-domains oriented perpendicular to the lower and upper interfaces of the block copolymer, in order to then be able to selectively remove one of the blocks from the copolymer with blocks, create a porous film with the residual block (s) and transfer, by etching, the patterns thus created to the underlying substrate.
However, this condition of perpendicularity of the patterns is fulfilled only if each of the lower (substrate / block copolymer) and upper (block copolymer / ambient atmosphere) interfaces is “neutral” with respect to each of the blocks of said BCP copolymer, that is to say that there is no preponderant affinity of the interface considered for at least one of the blocks constituting the BCP block copolymer.
With this in mind, the possibilities for controlling the affinity of the so-called "lower" interface, located between the substrate and the block copolymer, are well known and mastered today. There are two main techniques for
Ref: 0559-ARK88 to control and guide the orientation of the blocks of a block copolymer on a substrate: graphoepitaxy and / or chemistry-epitaxy. Graphoepitaxy uses a topological constraint to force the block copolymer to organize itself in a predefined and commensurable space with the periodicity of the block copolymer. For this, graphoepitaxy consists of forming primary patterns, called guides, on the surface of the substrate. These guides, of any chemical affinity for the blocks of the block copolymer, delimit zones within which a layer of block copolymer is deposited. The guides are used to control the organization of the blocks of the block copolymer to form secondary patterns of higher resolution, within these zones. Classically, the guides are formed by photolithography. By way of example, among the possible solutions, if the intrinsic chemistry of the monomers constituting the block copolymer allows it, a random copolymer comprising a judiciously chosen ratio of the same monomers as those of the BCP block copolymer can be grafted onto the substrate, thus making it possible to balance the initial affinity of the substrate for the BCP block copolymer. This is for example the conventional method of choice used for a system comprising a block copolymer such as PS-b-PMMA and described in the article by Mansky et al, Science, 1997, 275,1458). Chemistry-epitaxy uses a contrast in chemical affinities between a pre-drawn pattern on the substrate and the different blocks of the block copolymer. Thus, a pattern having a strong affinity for only one of the blocks of the block copolymer is pre-drawn on the surface of the underlying substrate, in order to allow the perpendicular orientation of the blocks of the block copolymer, while the rest of the surface has no particular affinity for the blocks of the block copolymer. For this, a layer is deposited on the surface of the substrate comprising on the one hand, neutral zones (consisting for example of grafted random copolymer), having no particular affinity with the blocks of the block copolymer to be deposited and of on the other hand, affine zones (consisting for example of grafted homopolymer of one of the blocks of the block copolymer to be deposited and serving as an anchoring point for this block of the block copolymer). The homopolymer serving as an anchor point can be made with a width slightly greater than that of the block with which it has a preferential affinity and allows, in this case, a “pseudo-equitable” distribution of the blocks of the block copolymer at the substrate surface. Such a layer is called "pseudo-neutral" because it
Ref: 0559-ARK88 allows a fair or "pseudo-fair" distribution of the blocks of the block copolymer on the surface of the substrate, so that the layer does not, as a whole, have preferential affinity with one of the blocks block copolymer. Consequently, such a chemistry-epitaxial layer on the surface of the substrate is considered to be neutral with respect to the block copolymer.
On the other hand, control of the so-called "upper" interface of the system, that is to say the interface between the block copolymer and the surrounding atmosphere, remains today much less well controlled. Among the different approaches described in the prior art, a first promising solution, described by Bâtes 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 document US2013 280497, consists in controlling the surface energy at the upper interface of a nano-structured block copolymer, of poly (trimethylsilystyrene-b-lactide) type, denoted PTMSS-b -PLA, or poly (styrene-b-trimethylsilystyrene-b-styrene), denoted PS-bPTMSS-b-PS, by the introduction of an upper layer, also called “top coat” and denoted TC thereafter, deposited on the surface of the block copolymer. In this document, the polar top coat is deposited by spinning (or “spin coating” in English terminology) on the block copolymer film to be nanostructured. The top coat is soluble in an acidic or basic aqueous solution, which allows its application on 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, the composition of which comprises maleic anhydride. In solution, the opening of the maleic anhydride cycle allows the top coat to lose ammonia. At the time of the 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 compared to the copolymer at blocks, thus allowing a perpendicular orientation of the nanodomains with respect to the two lower and upper interfaces. The top coat is then removed by washing in an acidic or basic solution.
In such systems, based on stacks noted TC / BCP / substrate, the TC top coat, applied by spin coating, has a liquid / viscous state. The BCP block copolymer is furthermore necessarily in its liquid / viscous state,
Ref: 0559-ARK88 in order to be able to self-organize at assembly temperature and create the desired patterns. However, in the same way as for any polymeric stack, the application of such a top coat layer TC, in the liquid or viscous state, on a layer of BCP block copolymer itself in the liquid state or viscous, causes the appearance, at the upper block copolymer / top coat (BCP / TC) interface, of the same dewetting phenomenon as that described above with reference to FIG. 1C. Indeed, because of hydrodynamic phenomena leading to the amplification of capillary waves of the TC top coat layer and of its interaction with the underlying layer of BCP block copolymer, this type of stacking tends to be particularly unstable and leads to the introduction of severe defects in the form of discontinuity of the BCP block copolymer film, thus making it unsuitable for use, for example, as a nano-lithography mask for electronics. In addition, the finer the deposited polymer film, that is to say at least once the radius of gyration of a molecular chain of the polymer considered, the more it will tend to be unstable or metastable, all the more when the surface energy of the underlying layer is different from that of said polymer and the system is left free to evolve. Finally, the instability of the polymer film deposited on the underlying layer is in general all the more important the higher the "annealing temperature / annealing time" couple.
Regarding the first solution described by Bâtes et al, just after the step of depositing the TC top coat layer by spin-coating, there remains solvent trapped in the polymer chains, as well as an "open" form maleate ", less rigid, of the monomer. These two parameters imply, in fact, a plasticization of the material and therefore a significant decrease in the glass transition temperature (Tg) of the material before thermal annealing allowing the return of said material to the anhydride form. In addition, the difference between the assembly temperature of the BCP block copolymer (which is 210 ° C for the PS-b-PTMSS-b-PS block copolymer and 170 ° C for the PTMSS block copolymer -b-PLA) with respect to the glass transition temperature of the TC top coat layer (which is respectively 214 ° C. for the TC-PS top coat deposited on the block copolymer of PS-b-PTMSS-b- PS and 180 ° C for the TC-PLA top coat deposited on the PTMSS-b-PLA block copolymer) is too low to be able to guarantee the absence of dewetting phenomenon. Finally, the assembly temperature also does not guarantee kinetics
Ref: 0559-ARK88 of correct assembly for the formation of patterns in the context of the targeted DSA application.
In addition, still concerning the solution described by Bâtes & al., To avoid the problem of inter-diffusion or solubilization of the TC top coat layer in the underlying BCP block copolymer, the transition temperature glassy Tg of the TC top coat layer must be high and higher than the assembly temperature of the block copolymer. For this, the constituent molecules of the top coat layer TC, are chosen so as to have a high molecular weight.
The molecules constituting the TC top coat must therefore have a high glass transition temperature Tg, as well as long molecular chains, in order to limit the solubilization of the TC top coat layer in the BCP block copolymer. and avoid the appearance of a dewetting phenomenon. These two parameters are particularly restrictive in terms of synthesis. Indeed, the top coat layer TC must have a sufficient degree of polymerization so that its glass transition temperature Tg is much higher than the assembly temperature of the underlying block copolymer. In addition, the possible choice of co-monomers, making it possible to vary the intrinsic surface energy of the TC top coat layer so that the latter has a neutral surface energy with respect to the sub-block copolymer. jacent, is limited. Finally, in their publication, Bâtes et al describe the introduction of co-monomers to stiffen the chains. These added co-monomers are rather carbon-based monomers, norbornene type, which do not promote correct solubilization in polar / protic solvents.
On the other hand, for the proper functioning of such stacked polymer systems intended for applications in the field of nano-lithography by directed self-assembly, not only the phenomena of dewetting and interdiffusion must be avoided in order to satisfy the conditions of surface flatness and clear interface, but in addition, additional requirements must be satisfied in order to allow in particular the obtaining of a perfect perpendicularity of the nano-domains of the block copolymer after assembly.
Among these additional requirements to be satisfied, the TC top coat layer must be soluble in a solvent, or solvent system, in which the BCP block copolymer itself is not soluble, under penalty of re-dissolving the
Ref: 0559-ARK88 ίο block copolymer at the time of the top coat layer deposition, the deposition of such a layer is generally carried out by the well-known spin coating technique. Such a solvent is also known as “solvent orthogonal to the block copolymer”. It is also necessary that the top coat can be easily removed, for example by rinsing in an appropriate solvent, preferably itself compatible with standard electronic equipment. In the publication by Bâtes et al cited above, the authors circumvent this point by using, as the main base of the polymer chain constituting the TC top coat, a monomer (maleic anhydride) whose polarity changes once in basic aqueous solution ( with the introduction of charges into the chain by acid-base reaction), then returns to its initial uncharged form once the material has been deposited and then annealed at high temperature.
A second requirement lies in the fact that the TC top coat layer must preferably be neutral with respect to the blocks of the BCP block copolymer, that is to say that it must have an equivalent interfacial tension for each of the different blocks of the block copolymer to be nano-structured, at the time of the heat treatment allowing the structuring of the BCP block copolymer, in order to guarantee the perpendicularity of the patterns with respect to the interfaces of the block copolymer film. Given all the aforementioned difficulties, the chemical synthesis of the top-coat material can prove to be a challenge in itself. Despite the difficulties in synthesizing such a top coat layer and the dewetting and interdiffusion phenomena to be avoided, the use of such a layer appears to be a priori essential for orienting the nano-domains of a copolymer with blocks perpendicular to the interfaces.
In a second solution described in the document by J. Zhang & al., Nano Lett., 2016, 16, 728-735, as well as in documents WO16193581 and WO16193582, a second block copolymer, BCP n ° 2, is used as a top coat layer, “embedded” with the first BCP block copolymer in solution. The BCP No. 2 block copolymer comprises a block having a different solubility, for example a fluorinated block, as well as a low surface energy, thus naturally allowing the segregation of the second BCPn ° 2 block copolymer on the surface of the first copolymer. after blocking and rinsing in an appropriate solvent, for example a fluorinated solvent. At least one
Ref: 0559-ARK88 of the blocks of the second block copolymer has, at the organization temperature, a neutral surface energy with respect to all the blocks of the first film of block copolymer to be organized perpendicularly. Like the first solution, this solution is also conducive to the appearance of dewetting phenomena.
In a third solution, described by HS Suh & al., Nature Nanotech., 2017, 12, 575-581, the authors deposit the TC top coat layer by the iCVD method (from the acronym "initiated Chemical Vapor Déposition ”), which allows them to overcome the problem of the solvent of the TC top coat at the time of deposition which must be“ orthogonal ”to the BCP block copolymer, that is to say non-solvent for the block copolymer PCO. However, in this case, the surfaces to be covered require special equipment (an iCVD chamber), and therefore involve a longer process time than with a simple spin-coating deposition. In addition, the ratios of different monomers to be reacted can vary from one iCVD chamber to another, so that it appears necessary to constantly make adjustments / corrections as well as quality control tests, in order to be able to use a such a process in the field of electronics.
The different solutions described above for producing a stack of polymer layers having a flat surface, with clear interfaces between the layers are not entirely satisfactory. In addition, when such a stack is intended for DSA applications, and comprise a film of block copolymer to be nano-structured with nano-domains which must be oriented perfectly perpendicular to the interfaces, the existing solutions generally remain too tedious and complex. to be implemented and do not make it possible to significantly reduce the defectiveness associated with dewetting and the non-perfect perpendicularity of the patterns of the block copolymer. The solutions considered also seem too complex to be compatible with industrial applications.
Therefore, in the context of the use of stacks comprising BCP block copolymers in the form of thin films, intended to be used as nanolithography masks, for applications in organic electronics, it is imperative to ability to check not only that the BCP block copolymer film covers the entire previously neutralized surface of the
Ref: 0559-ARK88 substrate considered without dewetting thereof, and that the top coat layer covers well the entire surface of the block copolymer without dewetting, but also that the top coat layer deposited at the upper interface does not have any preponderant affinity with any one of the blocks of the block copolymer, in order to guarantee the perpendicularity of the patterns with respect to the interfaces.
[Technical problem] The invention therefore aims to remedy at least one of the drawbacks of the prior art. The invention aims in particular to propose a method for controlling the flatness of a polymer stacking system, said method making it possible to avoid the appearance of dewetting phenomena of the stacked polymer layers, while at least one of the lower layers of the stack keeps the possibility of being in a liquid-viscous state depending on the temperature, as well as of phenomena of solubilization between the different layers and of inter-diffusion at the interfaces, so as to obtain stacks of which the layers are perfectly flat and whose interfaces between two layers are clear. The process must also be simple to implement and allow industrial execution.
The invention also aims to remedy other problems specific to applications dedicated to nano-lithography by directed self-assembly (DSA). In particular, it aims to allow the deposition of a top coat layer on the surface of a block copolymer, which avoids the appearance of the above-mentioned dewetting and interdiffusion phenomena and which also has an energy of neutral surface with respect to the blocks of the underlying block copolymer, so that the nano-domains of the block copolymer can orient themselves perpendicularly to the interfaces, at the assembly temperature of said block copolymer. It also aims to allow the deposition of such a top coat layer with a solvent which is orthogonal to the underlying block copolymer, that is to say not capable of attacking, even partially solvating or dissolving this -latest.
[Brief description of the invention] To this end, the invention relates to a method for controlling the flatness of a polymeric stack, said stack comprising at least a first and a second layer of (co-) polymer stacked on top of each other, the first underlying (co-) polymer layer having not undergone any prior treatment
Ref: 0559-ARK88 allowing its crosslinking, at least one of the (co-) polymer layers being initially in a liquid or viscous state, said process being characterized in that the upper layer, called top coat, is deposited on the first polymer layer in the form of a pre-polymer composition, comprising one or more monomer (s) and / or dimer (s) and / or oligomer (s) and / or polymer (s) in solution, and in that it is then subjected to a stimulus capable of causing a reaction of crosslinking or polymerization of the molecular chains within said layer. Thus, the top coat layer polymerizes / crosslinks quickly to form a rigid network, so that it has neither the time nor the physical possibility of wetting. The upper layer thus crosslinked / polymerized makes it possible to solve several different technical problems described above. Firstly, this crosslinking / polymerization makes it possible to eliminate the dewetting inherent in the top coat layer, since the molecular movements of the top coat layer are very restricted once it is fully crosslinked / polymerized. Secondly, this crosslinking / polymerization of the upper layer also makes it possible to eliminate the typical dewetting possibilities known as “liquid-liquid” from the system, the top coat layer being able to be considered as a solid, possibly deformable, and no longer as a viscous fluid after crosslinking / polymerization and once the system has been brought to a temperature of use, higher than the glass transition temperature of the underlying polymer layer. Third, the crosslinked / polymerized top coat layer also helps stabilize the underlying polymer layer so that it does not wilt from its substrate. Another remarkable and non-negligible point is that the step of chemical synthesis of the material of the top coat layer is facilitated because it makes it possible to overcome the problems linked to the need to synthesize a material of high molecular mass, thus offering a better control over the final architecture of the material (composition, mass, etc.) as well as significantly less drastic synthesis operating conditions (permissible impurity rate, solvent, etc.) than in the case of materials with large molecular weights . Finally, the use of small molecular weights for the upper layer makes it possible to widen the range of possible orthogonal solvents for this material. It is indeed well known that polymers of small masses are easier to solubilize than polymers of the same chemical composition having large masses.
Ref: 0559-ARK88 [0036] According to other optional characteristics of the method for controlling the flatness of a polymeric stack:
- the stimulus applied to initiate the crosslinking / polymerization reaction is chosen from plasma, ion bombardment, electrochemical process, chemical species (nucleophile, electrophile, etc.), light radiation;
- the stimulus applied to initiate the crosslinking / polymerization reaction is an electrochemical process applied via an electron beam;
- the stimulus for causing the crosslinking reaction within the pre-polymer layer is light radiation in wavelength ranges from ultraviolet to infra-red, between 10nm and 1500nm, and preferably between 100nm and 500nm;
the photo-crosslinking / photo-polymerization step of the layer of pre-polymer composition is carried out at an energy dose less than or equal to 200 mJ / cm ² , preferably less than or equal to 100 mJ / cm ² and so more preferred, less than or equal to 50 m J / cm ² ;
- The crosslinking / polymerization reaction propagates within the upper layer, bringing the stack to a temperature below 150 ° C and preferably below 110 ° C, for a period of less than 5 minutes, and preferably less 2 minutes;
- The pre-polymer composition is a composition formulated in a solvent, or used without solvent, and which comprises at least: a monomer, dimer, oligomer or polymer chemical entity, or any mixture of these different entities, of a chemical nature in all or identical part, and each comprising at least one chemical function capable of ensuring the crosslinking / polymerization reaction under the effect of a stimulus; and one or more chemical entities capable of initiating the crosslinking / polymerization reaction under the effect of the stimulus, such as a radical generator, an acid and / or a base;
- at least one of the chemical entities of the prepolymer composition has at least one fluorine and / or silicon and / or germanium atom, and / or an aliphatic carbon chain of at least two carbon atoms in its chemical formula ;
Ref: 0559-ARK88
said prepolymer composition also comprises in its formulation: a chemical entity chosen from an antioxidant, a base or a weak acid, capable of trapping said chemical entity capable of initiating the crosslinking / polymerization reaction, and / or one or more additives making it possible to improve wetting and / or adhesion, and / or the uniformity of the top layer of top coat deposited on the underlying layer, and / or one or more additives making it possible to absorb a or several ranges of light radiations of different wavelength, or to modify the electrical conductivity properties of the prepolymer;
- The pre-polymer composition comprises a cross-linking / polymerization photoinitiator and it is cross-linked / polymerized by radical polymerization;
- when the polymerization is radical, the monomer (s) and / or dimer (s) and / or oligomer (s) and / or polymer (s) constituting the pre-polymer layer, are chosen from the non-exhaustive list of acrylate or di- or tri-acrylate or multi-acrylate, methacrylate, or multi-methacrylate, or polyglycidyl or vinyl derivatives, fluoroacrylates or fluoromethacrylates, vinyl fluorides or fluorostyrene, acrylate or methacrylate alkyl, hydroxyalkyl acrylate or methacrylate, alkylsilyl acrylate or methacrylate, unsaturated esters / acids such as fumaric or maleic acids, vinyl carbamates and carbonates, allyl ethers, and thiol-ene systems;
- when the polymerization is radical, the photoinitiator is chosen from acetophenone, benzophenone, peroxide, phosphine, xanthone, hydroxyketone or diazonaphthoquinone, thioxanthone, α-amino ketone, benzile derivatives , benzoin;
- The prepolymer composition comprises an initiator and it is crosslinked / polymerized by cationic polymerization;
- when the polymerization is cationic, the monomer (s) and / or dimer (s) and / or oligomer (s) and / or polymer (s) constituting the pre-polymer layer, are derivatives comprising chemical functions of the epoxy / oxirane type, or vinyl ethers, cyclic ethers, thiirane, trioxane, vinyls, lactones, lactams, carbonates, thiocarbonates, maleic anhydride;
Ref: 0559-ARK88
- when the polymerization is cationic, the initiator is an acid photo-generated from a salt chosen from onium salts, such as the iodonium, sulfonium, pyrridinium, alkoxypyrridinium, phosphonium salts , oxonium, or diazonium;
- the photo-generated acid can optionally be coupled to a photosensitizing compound chosen from acetophenone, benzophenone, peroxide, phosphine, xanthone, hydroxycetone or diazonaphthoquinone, thioxanthone, α-aminoketone derivatives , benzile, benzoin, as long as said photo-sensitizer absorbs at the desired wavelength;
- The prepolymer composition comprises an initiator and it is crosslinked / polymerized by anionic polymerization reaction;
- when the polymerization is anionic, the monomer (s) and / or dimer (s) and / or oligomer (s) and / or polymer (s) constituting the pre-polymer layer, are derivatives alkyl cyanoacrylates, epoxides / oxiranes, acrylates, or derivatives of isocyanates or polyisocynanates;
- when the polymerization is anionic, the initiator is a photogenerated base from derivatives chosen from carbamates, acyloximes, ammonium salts, sulfonamides, formamides, amineimides, aminoketones, amidines;
- The first polymer layer is in a solid state when the stack is brought to a temperature below its glass transition temperature or in a liquid-viscous state when the stack is brought to a temperature above its glass transition temperature , or at its highest glass transition temperature;
the first polymer layer is a block copolymer capable of nanostructuring at an assembly temperature, said block copolymer being deposited on an underlying layer whose surface is previously neutralized, said assembly temperature being less than a temperature at which the top coat material behaves like a viscoelastic fluid, said temperature being higher than the glass transition temperature of said top coat material and preferably said
Ref: 0559-ARK88 assembly temperature is lower than the glass transition temperature of the top coat layer in its crosslinked / polymerized form;
- The underlying layer may or may not have patterns, said patterns being predrawn by a step or a sequence of lithography steps of any kind prior to the step of depositing the first layer of block copolymer, said patterns being intended guiding the organization of said block copolymer by a technique called chemistry-epitaxy or graphoepitaxy, or a combination of these two techniques, in order to obtain a neutralized or pseudo-neutralized surface;
- the block copolymer comprises silicon in one of its blocks;
- The first layer of block copolymer is deposited on a thickness at least equal to 1.5 times the minimum thickness of the block copolymer;
the solvent for the pre-polymer layer is chosen from solvents or mixtures of solvents whose Hansen solubility parameters are such that δ _ρ > 10 MPa ^1/2 and / or ôh> 10 MPa ^1/2 and with ôd <25 MPa ^1/2 ;
- The solvent for the prepolymer layer is chosen from alcohols such as methanol, ethanol, isopropanol, 1-methoxy-2-propanol, ethyl lactate; diols such as ethylene glycol or propylene glycol; or from dimethylsulfoxide (DMSO), dimethylformamide, dimethylacetamide, acetonitrile, gammabutyrolactone, water or a mixture thereof;
- The composition of the prepolymer layer comprises a multicomponent mixture of monomers and / or dimers and / or oligomers and / or polymers each carrying functions ensuring crosslinking / polymerization, as well as different monomer units whose surface energies vary d 'one monomer unit to another;
- the composition of the pre-polymer layer also comprises plasticizers and / or wetting agents, added as additives;
- The composition of the pre-polymer layer further comprises rigid comonomers chosen from derivatives comprising either one / more aromatic ring (s) in their structure, or mono or multicyclic aliphatic structures, and having one / more functions (s) chemical (s) suitable for the crosslinking / polymerization reaction targeted; and more particularly
Ref: 0559-ARK88 norbornene derivatives, isobornyl acrylate or methacrylate, styrenic, anthracene derivatives, adamantyl acrylate or methacrylate.
The invention further relates to a process for manufacturing a nano-lithography mask by directed assembly of block copolymers, from a polymeric stack obtained in accordance with the process which has just been described above, characterized in that once the cross-linked / polymerized top coat layer, the stack is subjected to annealing, preferably thermal, for a determined period, at the assembly temperature of the block copolymer so that it becomes nanostructure.
According to other optional characteristics of this process:
- after the nano-structuring step of the block copolymer, the top coat layer is removed in order to leave a film of nanostructured block copolymer of minimum thickness, then at least one of the blocks of said block copolymer, oriented perpendicular to the interfaces , is removed in order to form a porous film capable of serving as a mask for nano-lithography;
- When the block copolymer is deposited on a thickness greater than the minimum thickness, an additional thickness of said block copolymer is removed simultaneously or successively with the removal of the top coat layer, in order to leave a film of nano-structured block copolymer d minimum thickness, then at least one of the blocks of said block copolymer, oriented perpendicular to the interfaces, is removed in order to form a porous film capable of serving as a mask for nano-lithography;
the top coat layer and / or the excess thickness of the block copolymer and / or the block (s) of the block copolymer is / are removed by dry etching;
- The etching steps of the top coat layer and / or of the extra thickness of the block copolymer and of one or more blocks of the block copolymer, are carried out successively in the same etching frame, by plasma etching;
- at the time of the crosslinking / polymerization step of the top coat layer, the stack is subjected to light radiation and / or an electron beam located on certain areas of the top coat layer, in order to create crosslinked areas / polymerized top coat and non-crosslinked areas / polymerized;
Ref: 0559-ARK88
- in the context of the manufacture of a nano-lithography mask by directed assembly, the crosslinked / polymerized areas of top coat have a neutral affinity with respect to the underlying block copolymer, while the affinity of non-crosslinked / polymerized top coat areas vis-à-vis the blocks of the underlying block copolymer is not neutral;
- after the localized photo-crosslinking of the top coat layer, the stack is rinsed with the solvent which has allowed the deposition of the pre-polymer layer in order to remove the non-irradiated areas;
- another pre-polymer material, not neutral vis-à-vis the underlying block copolymer, is deposited in the previously non-irradiated areas and lacking a top coat layer, then said non-neutral pre-polymer material is exposed to a stimulus in order to crosslink / polymerize it at predefined locations;
- at the time of the annealing step of the stack at the assembly temperature of the block copolymer, nano-domains are formed perpendicular to the interfaces in zones located opposite the zones of the crosslinked neutral top coat layer / polymerized, and nano-domains parallel to the interfaces in areas of the block copolymer located opposite the areas lacking a crosslinked / polymerized neutral top coat layer.
The invention finally relates to a polymeric stack deposited on a substrate and comprising at least two layers of (co) polymer stacked one on the other, characterized in that the upper layer, called top coat, deposited on the first (co) polymer layer is obtained by crosslinking / polymerization in situ in accordance with the method described above, said stack being intended to be used in applications chosen from surface protection for aerospace or aeronautics or the automotive or wind power, paints, inks, membrane manufacturing, microelectronic, optoelectronic or microfluidic components.
More particularly, this stack is intended for applications in the field of nano-lithography by directed self-assembly, the first (co) polymer layer is a block copolymer and the surfaces of the layer on which the copolymer blocks is deposited and the top coat layer preferably have a neutral surface energy with respect to the blocks of the block copolymer.
Ref: 0559-ARK88 [0041] Other particularities 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:
• Figures 1A to 1 C, already described, diagrams seen in section of different stacks of polymers and their evolution over time, • Figure 2, already described, a diagram seen in section of a stack of polymers according to l invention, not undergoing any dewetting phenomenon or inter-diffusion, • Figure 3, a diagram seen in section of a stack according to the invention dedicated to an application in nano-lithography by directed self-assembly (DSA) for the production of a nano-lithography mask, • Figure 4, a diagram seen in section of another stack according to the invention dedicated to an application in nano-lithography by directed self-assembly (DSA), for the creation of different patterns in a substrate.
[Detailed description of the invention] By "polymers" means either a copolymer (of statistical type, gradient, block, alternating), or a homopolymer.
The term "monomer" as used relates to a molecule which can undergo polymerization.
The term "polymerization" as used relates to the process for transforming a monomer or a mixture of monomers into a polymer of predefined architecture (block, gradient, statistics, etc.).
The term “copolymer” means a polymer grouping together several different monomer units.
The term “statistical copolymer” is understood to mean a copolymer in which the distribution of the monomer units along the chain follows a statistical law, for example of the Bernoullien type (zero Markov order) or Markovian of the first or second order. When the repeating 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 that prevailed during the synthesis of the copolymer is not known.
Ref: 0559-ARK88 By "gradient copolymer" is meant a copolymer in which the distribution of the monomer units varies gradually along the chains.
The term "alternating copolymer" means a copolymer comprising at least two monomeric entities which are distributed alternately along the chains.
The term "block copolymer" means a polymer comprising one or more uninterrupted blocks of each of the distinct polymer species, the polymer blocks being chemically different from one or more, and being linked together by a chemical bond (covalent, ionic, hydrogen bond, or coordination). These polymer blocks are also called 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 in nanoparticles. areas.
The term "miscibility" above means the ability of two or more compounds to mix completely to form a homogeneous or "pseudo-homogeneous" phase, that is to say without crystal symmetry or almost - apparent crystal at short or long distance. The miscibility of a mixture can be determined when the sum of the glass transition temperatures (Tg) of the mixture is strictly lower than the sum of the Tg of the compounds taken in isolation.
In the description, we speak of both "self-assembly" as "self-organization" or "nanostructuring" to describe the well-known phenomenon of phase separation of block copolymers, an assembly temperature also called annealing temperature.
The term “minimum thickness” of a block copolymer is understood to mean the thickness of a block copolymer film serving as a nanolithography mask, below which it is no longer possible to transfer the patterns. block copolymer film in the underlying substrate with a satisfactory final form factor. In general, for block copolymers with a high phase segregation parameter χ, this minimum thickness "e" is at least equal to half of the period L _o of the block copolymer.
The term "porous film" denotes a block copolymer film in which one or more nano-domains have been removed, leaving holes whose
Ref: 0559-ARK88 shapes correspond to the shapes of the nano-domains having been removed and which can be spherical, cylindrical, lamellar or helical.
By "neutral" or "pseudo-neutral" surface is meant a surface which, as a whole, does not have preferential affinity with one of the blocks of a block copolymer. It thus allows a fair or "pseudo-equitable" distribution of the blocks of the block copolymer on the surface.
The neutralization of the surface of a substrate makes it possible to obtain such a "neutral" or "pseudo-neutral" surface.
The surface energy (denoted yx) of a given material "x" is defined as being the excess energy at the surface of the material compared to that of the material taken as a mass. When the material is in liquid form, its surface energy is equivalent to its surface tension.
When talking about surface energies or more precisely the interfacial tensions of a material and of a block of a given block copolymer, these are compared to a given temperature, and more particularly to a temperature allowing the self-organization of the block copolymer.
The term "lower interface" of a (co) polymer means the interface in contact with an underlying layer or substrate on which / which said (co) polymer is deposited. It will be noted that, throughout the rest of the description, when the polymer in question is a block copolymer to be nano-structured, intended to serve as a nanolithography mask, this lower interface is neutralized by a conventional technique, that is to say say that, as a whole, it does not have preferential affinity with one of the blocks of the block copolymer.
The term "upper interface" or "upper surface" of a (co) polymer means the interface in contact with an upper layer, called top coat and denoted TC, applied to the surface of the (co) polymer. It will be noted that, throughout the rest of the description, when the polymer in question is a block copolymer to be nanostructured, intended to serve as a nanolithography mask, the upper layer of top coat TC, like the underlying layer, does not preferably has no preferential affinity with one of the blocks of the block copolymer so that the nanodomains of the block copolymer can be oriented perpendicular to the interfaces at the time of assembly annealing.
Ref: 0559-ARK88 By “solvent orthogonal to a (co) polymer” is meant a solvent which is not capable of attacking or dissolving said (co) polymer.
The term "liquid polymer" or "viscous polymer" means a polymer having, at a temperature above the glass transition temperature, due to its rubbery state, increased deformation capacity due to the possibility given to its molecular chains to move freely. The hydrodynamic phenomena at the origin of dewetting appear as long as the material is not in a solid state, that is to say undeformable due to the negligible mobility of its molecular chains.
In the context of this invention, we consider any polymeric stacking system, that is to say a system comprising at least two layers of (co-) polymers stacked on top of each other. This stack can be deposited on a solid substrate of any kind (oxide, metal, semiconductor, polymer, etc.) depending on the applications for which it is intended. The different interfaces of such a system can have a "liquid / solid" or "liquid / liquid" configuration. Thus, an upper (co) polymer layer, having a liquid or viscous state, is deposited on an underlying (co) polymer layer which may be in a solid or liquid or viscous state, depending on the intended applications. More particularly, the underlying (co) polymer layer may be solid or liquid or viscous depending on the working temperature, relative to its glass transition temperature Tg, during the flatness control process. stack according to the invention.
Figure 2 illustrates such a polymeric stack. This stack is for example deposited on a substrate 10 and comprises for example two layers of polymer 20 and 30 stacked one on the other. Depending on the intended applications, the first layer 20 may be without a solid or liquid / viscous state at the time of the deposition of the second upper layer 30, called the TC top coat. More particularly, the first layer 20 is in a solid state when the stack is brought to a temperature below its glass transition temperature or in a viscous liquid state when the stack is brought to a temperature above its glass transition temperature. The TC top coat layer 30 is applied to the surface of the underlying layer 20, by a conventional deposition technique, by
Ref: 0559-ARK88 example by spinning or "spin coating", and is in a liquid / viscous state.
The term "flatness of a polymeric stack" within the meaning of the invention is addressed to all the interfaces of the stack. The method according to the invention makes it possible to control the flatness of the interface between the substrate 10 and the first layer 20, and / or the flatness of the interface between the first layer 20 and the top coat layer 30, and / or the flatness of the interface between the top coat layer 30 and the air.
To avoid the appearance of a phenomenon of dewetting the layer 30 of the TC top coat just after its deposition on the underlying layer 20, and to avoid an inter-diffusion phenomenon at the interface, in particular in in the case of a liquid / liquid configuration of the interface, corresponding to the case represented in FIG. 1C, the invention advantageously consists in depositing the upper layer 30 in the form of a pre-polymer composition, denoted pre-TC, comprising one or more monomer (s) and / or a dimer (s) and / or an oligomer (s) and / or a polymer (s) in solution. For the sake of simplification, these compounds are also called "molecules" or "entities" in the following description. Thanks to the application of a stimulus, a crosslinking / polymerization reaction takes place in situ, within the pre-TC pre-polymer layer deposited, and generates the creation of a TC polymer of high molecular mass. by means of the crosslinking reaction of the polymer chains constituting the deposited prepolymer layer. During this reaction, the initial chain size increases as the reaction propagates in the layer, thus greatly limiting the solubilization of the top coat layer TC crosslinked in the underlying polymer layer 20 when the latter is in a liquid or viscous state, and further delaying the appearance of a dewetting phenomenon.
Preferably, the prepolymer composition is formulated in a solvent orthogonal to the first layer 20 of polymer already present on the substrate, and comprises at least:
- a monomer, dimer, oligomer or polymer chemical entity, or any mixture of these different entities, of chemical nature in whole or in part identical, and each comprising at least one chemical function capable of ensuring the propagation of the crosslinking reaction / polymerization under the effect of a stimulus; and
Ref: 0559-ARK88
- one or more chemical entities capable of initiating the crosslinking / polymerization reaction under the effect of the stimulus, such as a radical generator, an acid and / or a base.
The prepolymer composition can, in an alternative embodiment, be used without solvent.
Preferably, in the context of the invention, at least one of the chemical entities of the prepolymer composition has at least one fluorine and / or silicon and / or germanium atom, and / or a chain aliphatic carbon of at least two carbon atoms in its chemical formula. Such entities make it possible to improve the solubility of the prepolymer composition in a solvent orthogonal to the underlying polymer layer 20 and / or to effectively modulate the surface energy of the TC top coat layer if necessary, in particular for DSA applications, and / or to facilitate the wetting of the pre-polymer composition on the underlying (co-) polymer layer 20, and / or to reinforce the resistance of the TC top coat layer with respect to screw of a subsequent plasma etching step.
Optionally, this pre-polymer composition can also comprise, in its formulation:
- a chemical entity chosen from an antioxidant, a base or a weak acid, capable of trapping said chemical entity capable of initiating the crosslinking / polymerization reaction, and / or
one or more additives making it possible to improve the wetting and / or the adhesion, and / or the uniformity of the top layer of top coat, and / or
- one or more additives making it possible to absorb one or more ranges of light radiation of different wavelength, or to modify the electrical conductivity properties of the prepolymer.
Crosslinking can be carried out by any known means such as chemical crosslinking / polymerization, by means of a nucleophilic or electrophilic chemical species or the like, by an electrochemical process (redox or by cleavage of monomers via a beam electrons), by plasma, by ion bombardment or by exposure to light radiation. Preferably, the stimulus is electrochemical in nature and applied via an electron beam or light radiation, and even more preferably, it is light radiation.
Ref: 0559-ARK88 In a particularly advantageous embodiment, the crosslinking reaction of the components of the pre-TC pre-polymer layer is activated by the exposure of the layer to light radiation, such as a radiation in wavelength ranges from ultraviolet to infrared. Preferably, the illumination wavelength is between 10 and 1500nm and more preferably, it is between 100nm and 500nm. In a particular embodiment, the light source making it possible to expose the layer to light radiation can be a laser device. In such a case, the wavelength of the laser will preferably be centered on one of the following wavelengths: 436nm, 405nm, 365nm, 248nm, 193nm, 172nm, 157nm or 126nm. Such a crosslinking / polymerization reaction has the advantage of operating at ambient or moderate temperature, preferably less than or equal to 150 ° C. and more preferably, less than or equal to 110 ° C. It is also very fast, on the order of a few seconds to a few minutes, preferably less than 2 minutes. Preferably, the constituent compounds of the prepolymer layer, before crosslinking, are stable in solution as long as they are protected from exposure to the light source. They are therefore stored in opaque containers. When such a prepolymer layer is deposited on the underlying polymer layer 20, the constituents, stable in solution, are subjected to light radiation allowing the crosslinking of the layer in a very rapid period (typically less than 2 minutes) . So the top coat does not have time to get wet. In addition, as the reaction propagates, the size of the chains increases which limits the problems of solubilization and inter-diffusion at the interface when the latter is in a "liquid / liquid" configuration.
Regarding this photo-induced crosslinking / polymerization, two main classes of compounds are distinguished for the composition of the pre-TC prepolymer layer.
A first class relates to the compounds which react via a species of radical type. It is therefore a free radical photo-polymerization, a possible reaction mechanism of which is illustrated by reaction (I) below.
Ref: 0559-ARK88
In this example reaction, the photoinitiator, denoted PI, is a photo-cleavable aromatic ketone and the telechelic / di-functional oligomer is a diacrylate with R being able to be chosen from polyesters, polyethers, polyurethanes or polysiloxanes for example .
More generally, the monomer (s) and / or dimer (s) and / or oligomer (s) and / or polymer (s) constituting the prepolymer composition is ( are) chosen from derivatives of acrylates or di- or tri-acrylates or multiacrylates, methacrylate, or multi-methacrylates, or polyglycidyl or vinyl, fluoroacrylates or fluoromethacrylates, vinyl fluorides or fluorostyrene, acrylate or alkyl methacrylate, hydroxyalkyl acrylate or methacrylate, alkylsilyl acrylate or methacrylate, unsaturated esters / acids such as fumaric or maleic acids, vinyl carbamates and carbonates, allyl ethers, and thiol-ene systems.
Preferably, but without limitation for the invention, the constituents of the pre-polymer layer are multifunctional and have at least two chemical functions on the same molecule capable of ensuring the polymerization reaction.
The composition also comprises a photo-initiator carefully chosen as a function of the illumination wavelength selected. There are very many radical photoinitiators on the market with various chemistries such as acetophenone, benzophenone, peroxide, phosphine, xanthone, hydroxycetone or diazonaphthoquinone, thioxanthone, α- aminoketones, benzile, benzoin for example.
Ref: 0559-ARK88 A second class of compounds which can enter into the composition of the pre-polymer layer, relates to the compounds which react by a cationic polymerization. This is for example the case of derivatives comprising chemical functions of the epoxy / oxirane type, or vinyl ethers, cyclic ethers, thiirane, trioxane, vinyls, lactones, lactams, carbonates, thiocarbonates, maleic anhydride which then crosslink / polymerize by means of a photo-generated acid, noted PAG. A mechanism for such a cationic photopolymerization reaction of an epoxy is illustrated by reaction (II) below.
(H)
... <] - 'Again, many structures of PAG photo-generated acid precursors are available on the market, thus giving access to a wide choice of possible light wavelengths for generating the acid. , HMtX _n , catalyst for the crosslinking reaction. Such a precursor may for example be chosen from onium salts, such as the iodonium, sulfonium, pyrridinium, alkoxypyrridinium, phosphonium, oxonium or diazonium salts. Onium salts form strong acids, HMtX _n , under irradiation. The acid thus formed then gives a proton to the polymerizable / crosslinkable chemical function (s) of the monomer. If the monomer is poorly basic / reactive, the acid must be strong enough to shift the equilibrium significantly towards the propagation of the crosslinking reaction and the growth of the chains, as shown in reaction (II) above.
Alternatively, it is also possible to couple the photo-generated acid PAG to a photo-sensitizer if the chosen illumination wavelength does not quite correspond to a correct absorbance of the acid PAG. Such a photosensitizer can for example be chosen from acetophenone, benzophenone, peroxide, phosphine, xanthone, hydroxy ketone or
Ref: 0559-ARK88 diazonaphthoquinone, thioxanthones, α-aminoketones, benzile, benzoin, as long as said photosensitizer absorbs at the desired wavelength.
Other ionic polymerizations with other types of derivatives are also possible. Thus, reactions for example by anionic polymerization / crosslinking can also be envisaged. In this reaction class, the reactive species is a photo-generated organic base (denoted PBG), which reacts on one / more polymerizable / crosslinkable function (s) carried by the ) monomer (s) of the composition of the pre-polymer layer.
In this case, the photo-generated organic base PBG can be chosen from compounds such as carbamates, acyloximes, ammonium salts, sulfonamides, formamides, amineimides, α-aminoketones, amidines .
As for the monomers, dimers, oligomers and / or polymers of the composition, they can be chosen from derivatives such as alkyl cyanoacrylates, epoxides / oxiranes, acrylates, or also isocyanate or polyisocynanate derivatives. In this case, the photo-generated organic base PBG can be inserted within the molecular structure of the chains constituting the polymer during the polymerization / crosslinking reaction.
The solvent for the prepolymer layer is chosen so as to be entirely "orthogonal" to the polymer system of the underlying layer in order to avoid a possible re-dissolution of this polymer in the solvent for the prepolymer layer during the deposition step (by spin-coating for example). The solvents of each respective layer will therefore be very dependent on the chemical nature of the polymer material already deposited on the substrate. Thus, if the polymer already deposited is not very polar / protic, its solvent being selected from solvents that are not very polar and / or not very protic, the pre-polymer layer can therefore be dissolved and deposited on the first polymer layer from solvents that are rather polar. and / or protics. Conversely, if the polymer already deposited is rather polar / protic, the solvents of the pre-polymer layer may be chosen from solvents that are not very polar and / or not very protic. According to a preferred embodiment of the invention, but without this being restrictive in view of what has been explained above, the pre-polymer layer is deposited from solvents / mixtures of polar and / or protic solvents. More precisely, the polarity / proticity properties of
Ref: 0559-ARK88 different solvents are described according to the nomenclature of Hansen solubility parameters (Hansen, Charles M. (2007) Hansen solubility parameters: a user's handbook, CRC Press, ISBN 0-8493-7248-8), where l 'ô _d ' represents the dispersion forces between solvent / solute molecules, 'δ _ρ ' represents the energy of the dipole forces between molecules, and 'ô _h ' represents the energy of the possible hydrogen bonding forces between molecules, including the values are tabulated at 25 ° C. In the context of the invention, by “polar and / or protic” is defined a solvent / molecule or mixture of solvents having a polarity parameter such as δ _ρ > 10 MPa ^1/2 and / or a hydrogen bonding parameter such than eh ^ 10 MPa ^1/2 . In the same way, a solvent / molecule or mixture of solvents is defined by “slightly polar and / or protic” when the Hansen solubility parameters are such that δρ <10 MPa ^1/2 and / or bh <10 MPa ^{1 / 2} , and preferably δρ <8 MPa ^1/2 and / or a hydrogen bonding parameter such as bh ^ 9 MPa ^1/2 .
According to a preferred but not restrictive embodiment of the invention, the solvent for the prepolymer layer is chosen from compounds having a hydroxy function, for example alcohols, such as methanol, ethanol, isopropanol , 1-methoxy-2-propanol, ethyl lactate; or diols such as ethylene glycol or propylene glycol; or among dimethylsulfoxide (DMSO), dimethylformamide, dimethylacetamide, acetonitrile, gammabutyrolactone, water or a mixture of these.
More generally, in the context of one of the preferred but not exhaustive embodiments of the invention, the various constituents of the pre-polymer layer are soluble and stable in solvents including the solubility parameters of Hansen are such that δ _ρ > 10 MPa ^1/2 and / or δ ^ 10 MPa ^1/2 as defined above, and with the dispersion parameter b _d <25 MPa ^1/2 .
The crosslinking / polymerization reaction, by irradiation of the prepolymer layer, can be carried out at a moderate temperature, much lower than the glass transition temperature of the underlying polymer layer, in order to promote the diffusion of the reactive species. and thus increase the rigidity of the crosslinked network. Typically, the activation of the photoinitiator or of the photo-generated acid PAG or of the photo-generated base, can be initiated at a temperature below 50 ° C. and preferably below 30 ° C., over a period of time. typically less than 5 minutes and preferably less than 1 minute. Then, in a second step, the reaction of
Ref: 0559-ARK88 crosslinking / polymerization can be propagated by bringing the stack to a temperature preferably lower than 150 ° C, and more preferably lower than 110 ° C, so as to favor the diffusion of the reactive species (protons, radicals) within the pre-polymer layer, for a period of less than 5 minutes, and preferably less than 2 minutes.
According to a variant of the invention, the light irradiation of the prepolymer layer is carried out directly on a stack brought to the desired temperature, preferably below 110 ° C, to optimize the total reaction time.
Before the crosslinking / polymerization reaction, the TC top coat layer may be in the form of a block or random, gradient, alternating or alternating block copolymer, which may have a linear or star structure when the one of the co-monomers is multifunctional for example.
The invention as described above can be applied to any type of polymeric stack. Among the various and varied applications of such stacks, the applicant has also been interested in nano-lithography by directed self-assembly, or DSA. However, the invention is not limited to this example which is given by way of illustration and is in no way limiting. In fact, in the context of such an application, the top coat TC top layer must also meet other additional requirements, in particular in order to allow the nanodomains of the underlying block copolymer to orient themselves perpendicularly to the interfaces.
Figure 3 illustrates such a polymeric stack dedicated to an application in the field of organic electronics. This stack is deposited on the surface of a substrate 10. The surface of the substrate is previously neutralized, or pseudo-neutralized, by a conventional technique. For this, the substrate 10 may or may not have patterns, said patterns being pre-drawn by a step or a sequence of lithography steps of any kind prior to the step of depositing the first layer (20) of block copolymer. (BCP), said patterns being intended to guide the organization of said block copolymer (BCP) by a technique called chemistry-epitaxy or graphoepitaxy, or a combination of these two techniques, to obtain a neutralized surface. A particular example consists in grafting a layer 11 of a random copolymer comprising a judiciously chosen ratio of the same monomers as those of the BCP block copolymer
Ref: 0559-ARK88 deposited over the top. Layer 11 of the random copolymer makes it possible to balance the initial affinity of the substrate for the BCP 20 block copolymer. The grafting reaction can be obtained by any thermal, photochemical or even redox method, for example. Then, a TC 30 top coat layer is deposited on the layer of BCP block copolymer 20. This TC layer 30 must have no preferential affinity with respect to the blocks of the block copolymer 20 so that the nano-domains 21, 22 which are created during annealing at the assembly temperature Tass, are oriented perpendicular to the interfaces, as illustrated in FIG. 3. The block copolymer is necessarily liquid / viscous at the assembly temperature, in order to to be able to nano-structure. The top coat layer TC 30 is deposited on the block copolymer 20 in a liquid / viscous state. The interface between the two polymer layers is therefore in a liquid / liquid configuration suitable for the phenomena of inter-diffusion and dewetting.
Preferably, the assembly temperature Tass of the block copolymer 20 is lower than the glass transition temperature Tg of the top coat layer TC in its crosslinked / polymerized form or at least below a temperature at which the TC top coat material behaves like a viscoelastic fluid. This temperature is then in a temperature zone, corresponding to this viscoelastic behavior, situated above the glass transition temperature Tg of the top coat material TC.
As regards the layer 20 of nano-structured block copolymer, also denoted BCP, it comprises “n” blocks, n being any integer greater than or equal to 2. The BCP block copolymer is more particularly defined by the following general formula:
AbBbCbDb -....- bZ where A, B, C, D, ..., Z, are as many blocks "i" ... "j" representing either pure chemical entities, that is to say that each block is a set of monomers of identical chemical nature, polymerized together, that is to say a set of comonomers copolymerized together, in the form, in whole or in part, of block copolymer or statistical or random or gradient or alternated.
Ref: 0559-ARK88 Each of the blocks "i" ... "j" of the BCP block copolymer to be nanostructured can therefore potentially be written in the form: i = aj-co-bi-co -... -co-Zj, with i # ... / j, in whole or in part.
The volume fraction of each entity aj ... z, can range from 1 to 99%, in units of monomer, in each of the blocks i ... j of the BCP block copolymer.
The volume fraction of each of the blocks i ... j can range from 5 to 95% of the BCP 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 as described below. Within a copolymer in which at least one of the entities, or one of the blocks if it is a block copolymer, comprises several co-monomers, it is possible to measure, by NMR of the proton, the molar fraction of each monomer in the entire copolymer, then go back to the mass fraction using the molar mass of each monomer unit. To obtain the mass fractions of each entity in a block, or each block of a copolymer, it suffices to add the mass fractions of the co-monomers constituting 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 polymers whose monomers are co-polymerized. In this case, the volume fraction of an entity or block is determined from its mass fraction and the density of the majority compound by mass of the entity or block.
The molecular weight of the BCP block copolymer can range from 1000 to 500,000 g.mol ' ¹ .
The BCP block copolymer can have any type of architecture: linear, star (tri- or multi-arm), grafted, dendritic, comb.
Each of the blocks i, ... j of a block copolymer has a surface energy denoted γ, ... yj, which is specific to it and which is a function of its chemical constituents, that is to say -display the chemical nature of the monomers or co-monomers which
Ref: 0559-ARR88 compose it. Likewise, each of the materials making up a substrate have their own surface energy value.
Each of the blocks i, ... j of the block copolymer also has an interaction parameter of the Flory-Huggins type, noted: χ _ίχ , when it interacts with a given material "x", which can be a gas, a liquid, a solid surface, or another polymer phase for example, and an inter-facial energy denoted “γ, _χ ”, with Yix = Yi- (YxCos 0 _ix ), where 0 _ix is the angle of contact between materials i and x. The interaction parameter between two blocks i and j of the block copolymer is therefore noted χ ^.
There is a relation linking γ, and the Hildebrand solubility parameter δ, of a given material i, as described in the document Jia & al., Journal of Macromolecular Science, B, 2011, 50, 1042. In fact, the Flory Huggins interaction parameter between two given materials i and x is indirectly linked to the surface energies γ, and γ _χ specific to materials, we can therefore either speak in terms of surface energies, or in interaction parameter terms to describe the physical phenomenon appearing at the interface of materials.
When we talk about surface energies of a material and those of a given BCP block copolymer, we mean that we compare the surface energies at a given temperature, and this temperature is the one (or at least part of the temperature range) allowing the self-organization of the BCP.
In the same manner as described above for any stack of polymers, the upper layer 30, which is deposited on layer 20 of BCP block copolymer, is in the form of a prepolymer composition, denoted pre-TC , and comprises one or more monomer (s) and / or dimer (s) and / or oligomer (s) and / or polymer (s) in solution. Thanks to the application of a stimulus, in this case light radiation whose wavelength ranges from ultraviolet to infrared, between 10nm to 1500nm, and preferably between 100nm and 500nm, a crosslinking or polymerization reaction of the molecular chains constituting the pre-polymer layer takes place in situ, within the pre-TC pre-polymer layer deposited, and generates the creation of a TC polymer of high molecular weight. This creates a single polymer chain which is extremely immiscible with the underlying BCP block copolymer, thus greatly limiting the solubilization of the TC top coat layer 30 in the underlying BCP block copolymer layer 20 and retarding all the more the appearance
Ref: 0559-ARK88 of a dewetting phenomenon. Thus, the photo-crosslinking / photo-polymerization of the TC top coat layer 30 avoids not only the problems of interdiffusion and dewetting of the TC top coat layer 30 on the underlying BCP 20 block copolymer. , but also to stabilize the block copolymer layer 20 so that it does not dewetting from its substrate 10. The crosslinking / polymerization of the top coat layer TC 30 therefore makes it possible to obtain a stack, the surface of which is perfectly flat. , with perfectly clear substrate / block copolymer (substrate / BCP) and block / top coat copolymer (BCP / TC) interfaces.
Such a TC top coat layer thus crosslinked / polymerized has surface energy, at the temperature allowing the self-assembly of the underlying BCP 20 block copolymer, of between 10 and 50 mN / m, preferably between 20 and 45 mN / m and more preferably between 25 and 40 mN / m.
However, this crosslinking reaction involves chemical species, such as carbanions, carbocations or radicals, which are more reactive than a simple non-crosslinkable top coat layer. It is therefore possible, in certain cases, that these chemical species can diffuse and possibly degrade the BCP 20 block copolymer. Such diffusion is a function of the propagation temperature of the reaction and the nature of the chemical species involved. It is however very limited, over a thickness of a few nanometers at most and in all cases less than 10 nm, due to the immiscible nature of the TC 30 top coat layers and of BCP 20 block copolymer. such diffusion, the effective thickness of the block copolymer layer can then be reduced. To compensate for this possible diffusion, the BCP 20 block copolymer can be deposited on a greater thickness (e + E), for example at least 1.5 times the minimum thickness e of the block copolymer. In this case, after nanostructuring and when removing the top coat layer TC, the excess thickness E of block copolymer is also removed in order to keep only the lower part, of minimum thickness e, of the block copolymer .
Anyway, if it takes place, the diffusion being limited over a thickness of a few nanometers at most, it forms an intermediate layer comprising an intimate mixture of the constituents of the block copolymer BCP 20 and the top layer TC 30 coat. This intermediate layer then has an intermediate surface energy, between that of the pure TC 30 top coat and that of the
Ref: 0559-ARK88 average surface energies of the blocks of the BCP 20 block copolymer, so that it has no particular affinity with one of the blocks of the BCP block copolymer and therefore makes it possible to orient the nano -domains of the underlying BCP 20 block copolymer perpendicular to the interfaces.
Advantageously, the deposition of a layer of prepolymer followed by its crosslinking / polymerization, makes it possible to overcome the problems associated with the need to synthesize a top coat material of high molecular weight. It suffices in fact to synthesize monomers, dimers, oligomers or polymers, the molecular weights of which are much more reasonable, typically of the order of one order of magnitude less, thus limiting the difficulties and the operating conditions specific to the stage of chemical synthesis. The crosslinking / polymerization of the prepolymer composition then makes it possible to generate these high molecular weights in situ.
The fact of depositing a pre-polymer composition, comprising monomers, dimers, oligomers or polymers of much lower molecular weight than a non-crosslinked top coat material, also makes it possible to widen the possible range of solvents for the TC top coat material, these solvents having to be orthogonal to the BCP block copolymer.
Advantageously, the pre-TC pre-polymer composition can comprise monomers, dimers, oligomers or fluorinated polymers, soluble in alcoholic solvents, such as for example methanol, ethanol or isopropanol, 1 -methoxy-2-propanol, ethyl lactate; in diols such as ethylene glycol or propylene glycol or in dimethylsulfoxide (DMSO), dimethylformamide, dimethylacetamide, acetonitrile, gammabutyrolactone, water or a mixture thereof in which the copolymers have blocks are generally not soluble.
In the same manner as described above, two main classes of compounds are distinguished for the composition of the pre-TC pre-polymer layer. A first class concerns the compounds which react via a species of radical type. It is a free radical photo-polymerization. The monomer (s) and / or dimer (s) and / or oligomer (s) and / or polymer (s) constituting the prepolymer composition is (are) chosen from derivatives of acrylates or di- or triacrylates or multi-acrylates, methacrylate or multi-methacrylates, or vinyl,
Ref: 0559-ARK88 fluoroacrylates or fluoromethacrylates, vinyl fluorides or fluorostyrene, alkyl acrylate or methacrylate, hydroxyalkyl acrylate or methacrylate, alkylsilyl acrylate or methacrylate, unsaturated esters / acids such as fumaric or maleic acids, vinyl carbamates and carbonates, allyl ethers, and thiol-ene systems. The composition also comprises a photoinitiator carefully chosen, as a function of the selected wavelength of illumination, from derivatives of acetophenone, benzophenone, peroxide, phosphines, xanthones, or hydroxycetone, thioxanthones, α-aminoketones, benzile, benzoin for example.
In another embodiment, the compounds of the prepolymer composition react with a cationic polymerization and are chosen from derivatives comprising chemical functions of epoxy / oxirane type, or vinyl ethers, cyclic ethers, thiirane, trioxane, vinyl , lactones, lactams, carbonates, thiocarbonates, maleic anhydride which then crosslink by means of a photogenerated acid PAG. In this case, the prepolymer composition further comprises a photo-generated acid precursor PAG, making it possible to generate the catalyst acid for the crosslinking reaction under illumination, which can be chosen from onium salts, such as iodinium, sulfonium or pyrridinium or alkoxypyrridinium, phosphonium, oxonium, diazonium salts.
In order to further limit a possible phenomenon of dewetting of the TC top coat layer 30, the rigidity (measured for example by estimating the Young's modulus of the TC top coat once crosslinked or polymerized) and the glass transition temperature of the top coat layer can be reinforced by the introduction, into the pre-TC pre-polymer composition, of rigid co-monomers chosen from derivatives comprising either an aromatic ring (s) (s) in their structure, either mono or multi-cyclic aliphatic structures, and having a chemical function (s) adapted to the crosslinking / polymerization reaction targeted. More particularly, these rigid co-monomers are chosen from norbornene derivatives, isobornyl acrylate or methacrylate, styrenic, anthracene derivatives, adamantyl acrylate or methacrylate. The rigidity and the glass transition temperature of the top coat layer can also be reinforced by multiplying the possible crosslinking points of the components, with oligomer chains or multifunctional monomeric derivatives, such as for example
Ref: 0559-ARK88 polyglycidyl derivatives or di or tri-acrylate or multi-acrylate derivatives, derivatives having unsaturation (s), such as “sp2” or “sp” hybridized carbon atoms in their chemical formula.
In all cases, care must be taken to ensure that the light wavelength used for the crosslinking of the top coat layer TC 30 does not or very little interfere with the components of the block copolymer BCP 20 under -jacent, in order to avoid a possible photo-induced degradation of the latter. The choice of photoinitiator, photo-generated acid or photo-generated base must therefore be made so that the light radiation does not come to degrade the block copolymer. However, in general, photo-crosslinking is particularly effective, with a significant quantum yield, even with a low dose of energy (typically ranging from a few milliJoules per square centimeter (mJ / cm ² ) to a few tens of mJ / cm ² , for example for doses equivalent to the lithography processes commonly used for exposure of photo-sensitive resins at 193 nm), unlike the degradation of the block copolymer at the same wavelength which generally requires a larger dose (typically, for example from 200 mJ / cm ² to 1000 mJ / cm ² at 193 nm for polymethyl methacrylate PMMA). Consequently, even with a covering with a TC top coat layer photocrosslinked at a degradation wavelength of the underlying block copolymer, the energy dose remains low enough not to deteriorate the BCP block copolymer. Preferably, the energy dose during the photo-crosslinking / photopolymerization is less than or equal to 200 mJ / cm ² , more preferably it is less than or equal to 100 mJ / cm ² and even more preferably, it is less or equal to 50 mJ / cm ² In order to obtain a layer 30 of crosslinked TC top coat which is neutral with respect to the underlying block copolymer, that is to say which does not have any particular affinity for each of the blocks of the block copolymer, the pre-TC pre-polymer composition preferably comprises a multi-component mixture of derivatives all carrying functions ensuring crosslinking / polymerization, but chemical groups different. Thus, for example, the composition could comprise a component with fluorinated groups, another with oxygenated groups, etc., this in order to be able to finely modulate the surface energy specific to the top coat layer TC once photo-crosslinked. So among the
Ref: 0559-ARK88 molecules reacting by cationic photo-polymerization with PAG photogenerated acids to form a crosslinked TC layer, there may be mentioned, for example, oligomers formed from a monomer of low surface energy, such as a fluorinated acrylate for example , a medium monomer with high surface energy, such as a hydroxylated acrylate for example, and a crosslinkable group, via an acid reaction thanks to the use of a photo-generated acid, such as an epoxy. In this case, the ratio of low surface energy monomer / high surface energy monomer, weighted by the proportion of crosslinkable monomer, conditions the neutrality of the crosslinked TC top coat layer with respect to the underlying BCP block copolymer. The rate of crosslinkable / polymerizable groups relative to the nature of the molecules of the pre-polymer composition, conditions the final rigidity of the crosslinked TC top coat layer. Finally, the physico-chemical structure of the photogenerated acid PAG conditions its activation wavelength and its solubility.
However, in the context of nano-lithography applications by directed self-assembly, it is necessary to ensure that the TC top coat once formed, does not correspond to a porous or multiphase network, in order to avoid possible problems of non-uniformity / demixing of the TC top coat for the underlying BCP block copolymer. To this end, the pre-TC pre-polymer composition may consist of a binary mixture of pre-polymer / photoinitiator and of any plasticizers or wetting agents as additives if necessary. In the context of other applications, such as the manufacture of biocompatible membranes or implants for example, it may on the contrary be advantageous for the TC top coat, once formed, to correspond to such a porous or multiphasic network.
In order to be able to manufacture a nano-lithography mask, for example, once the TC top coat layer is crosslinked, the stack obtained, having a clear BCP / TC interface and a perfectly flat surface, is subjected to annealing, preferably thermal, at an assembly temperature Tass, for a determined period, preferably less than 60 minutes and more preferably less than 5 minutes, in order to cause the nanostructuring of the block copolymer. The nano-domains 21, 22 which form are then oriented perpendicular to the neutralized interfaces of the BCP block copolymer.
Then, once the block copolymer has been organized, the TC top coat layer can be removed.
Ref: 0559-ARK88 [0120] One way to remove the crosslinked TC top coat layer is to use dry etching, such as plasma for example with appropriate gas chemistry, such as a majority oxygen base in a mixture with a rather inert gas such as He, Ar, N ₂ for example. Such dry etching is all the more advantageous and easy to carry out if the underlying BCP 20 block copolymer contains, for example, silicon in one of its blocks, then acting as an etching stop layer.
Such dry etching can also be advantageous in the case where the underlying BCP block copolymer has been deposited with an extra thickness E and where not only the top coat layer TC has to be removed but also the extra thickness E of copolymer with blocks. In this case, the chemistry of the gases making up the plasma must be adjusted as a function of the materials to be removed so as not to have a specific selectivity for a block of the BCP block copolymer. The top coat layer TC and the extra thickness E of the BCP block copolymer can then be removed simultaneously or successively, in the same etching frame, by plasma etching by adjusting the gas chemistry according to the constituents of each of the layers to be removed. .
In the same way, at least one of the blocks 21, 22 of the BCP block copolymer 20, is removed so as to form a porous film capable of serving as a mask for nano-lithography. This removal of the block (s) can also be carried out in the same dry etching frame, successively with the removal of the top coat layer TC and of the possible additional thickness E of block copolymer.
It is also possible to create stacks comprising a succession of these two alternating layers of BCP block copolymer and TC top coat. An example of such a stack is illustrated in the diagram of FIG. 4 which represents the first stack already described comprising a substrate 10 whose surface 11 is previously neutralized, a first layer of BCP1 block copolymer, then a first layer of top coat TC1. Then, once the TC1 top coat layer has been crosslinked, a second BCP2 block copolymer is deposited on the first top coat layer. This second BCP2 block copolymer may be identical or different in nature from the first and makes it possible to create patterns, at its assembly temperature, different from those of the first BCP1 block copolymer.
In this case, it is also necessary for the first top coat layer TC1 to be neutral with respect to the blocks of the second BCP2 block copolymer. If this
Ref: 0559-ARK88 is not the case, its surface should be neutralized, by grafting a random copolymer for example. Then, a second layer of pre-TC2 prepolymer is deposited on the second block copolymer BCP2 and illuminated in order to cause a crosslinking reaction and to stiffen it. This second cross-linked TC2 top coat layer must also be neutral with respect to the second BCP2 block copolymer. The assembly temperatures of the two block copolymers BCP1 and BCP2 can be the same or different. If they are identical, a single annealing is sufficient to cause the structuring of the two block copolymers simultaneously. If they are not identical, two anneals are necessary to structure them in turn. And so on, several alternating layers of block copolymers and top coat can thus be deposited on top of each other. Such stacks of polymers can be used in microelectronics or optoelectronics applications such as Bragg mirrors for example, or even to create specific anti-reflective layers. Thereafter, optionally, several successive etching steps make it possible to transfer the different patterns of the different block copolymers into the underlying substrate. These etching steps are then preferably carried out by plasma by adjusting the gas chemistry at each layer as a function of the constituents of the layer.
A very large additional advantage of the present invention lies in the possibilities of selectivity of the process by means of photogenerated species. Thus, if a local light source, of the laser type for example, is used to carry out the irradiation of the pre-TC pre-polymer layer, then it becomes possible to define zones on the stack, where the pre -pre-TC polymer can be crosslinked, by photo-irradiation, and other areas where the pre-TC prepolymer layer will remain in the molecular state because not irradiated. Such localized irradiation on the surface of the TC top coat can also be carried out by means of a lithography mask for example and overall irradiation of the surface covered with said mask.
In an alternative embodiment, such selectivity allowing the creation of crosslinked / polymerized zones and of noncrosslinked / unpolymerized zones can also be obtained by means of an electron beam.
Ref: 0559-ARK88 [0127] In the context of the application of the method according to the invention to nanolithography by directed self-assembly, the crosslinked / polymerized areas of top coat have a neutral affinity with respect to the copolymer underlying blocks, while the non-irradiated top coat areas may have a preferential affinity with at least one of the blocks of the underlying block copolymer. It then becomes possible to define areas of interest on the same stack, where the patterns of the underlying BCP block copolymer will be perpendicular to the interfaces, in areas located opposite the areas of the irradiated top coat and neutral towards screws of the blocks of the block copolymer, and of other zones, situated opposite the nonirradiated zones, where the patterns of the block copolymer will on the contrary be oriented parallel to the interfaces, the latter therefore not being able to be transferred into the substrate jacent during subsequent etching steps.
To do this, the following method can simply be carried out. The pre-TC pre-polymer layer is deposited, then areas of interest of this layer are irradiated, for example through a lithography mask. The layer obtained is then rinsed in the solvent used for its deposition, for example, the solvent being itself orthogonal to the block copolymer. This rinsing removes the non-irradiated areas. Optionally, another pre-polymer material, non-neutral vis-à-vis the underlying block copolymer, can be deposited in the areas not previously irradiated and having been rinsed, therefore devoid of top coat layer, then said material non-neutral prepolymer is exposed to a stimulus, which can be light radiation or another stimulus chosen from an electrochemical process, plasma, ion bombardment or a chemical species, in order to crosslink / polymerize it at predefined locations. The stack is then annealed at assembly temperature so that the block copolymer is structured. In this case, the nano-domains located opposite the irradiated and cross-linked zones of the TC top coat layer, and neutral with respect to the block copolymer, are oriented perpendicular to the interfaces, while the nano-domains opposite the areas without a crosslinked and neutral top coat are oriented parallel to the interfaces.

权利要求:
Claims (41)
[1" id="c-fr-0001]
1. Method for controlling the flatness of a polymeric stack, said stack comprising at least a first and a second layer of (co-) polymer (20, 30) stacked one on the other, the first layer (co -) underlying polymer (20) which has not undergone any prior treatment allowing its crosslinking, at least one of the (co-) polymer layers being initially in a liquid or viscous state, said process being characterized in that the layer upper (30), called top coat (TC) is deposited on the first layer (20) in the form of a pre-polymer composition (pre-TC), comprising at least one monomer (s) and / or dimer (s) ) and / or oligomer (s) and / or polymer (s) in solution, and in that it is then subjected to a stimulus capable of causing a reaction of crosslinking / polymerization of the molecular chains within said layer (30, TC).
[2" id="c-fr-0002]
2. Method according to claim 1, characterized in that the stimulus applied to initiate the crosslinking / polymerization reaction is chosen from plasma, ion bombardment, electrochemical process, chemical species, light radiation.
[3" id="c-fr-0003]
3. Method according to claims 1 and 2, characterized in that the stimulus applied to initiate the crosslinking / polymerization reaction is an electrochemical process applied via an electron beam.
[4" id="c-fr-0004]
4. Method according to one of claims 1 to 2, characterized in that the stimulus for causing the crosslinking reaction within the pre-polymer layer is light radiation in wavelength ranges from infrared ultraviolet, between 10nm and 1500nm, and preferably between 100nm and 500nm.
[5" id="c-fr-0005]
5. Method according to claim 4, characterized in that the photocrosslinking / photopolymerization step of the layer of prepolymer composition is carried out at an energy dose less than or equal to 200 mJ / cm ² , preferably less or equal to 100 mJ / cm ² and more preferably, less than or equal to 50 mJ / cm ²
[6" id="c-fr-0006]
6. Method according to one of claims 4 to 5, characterized in that the crosslinking / polymerization reaction propagates within the upper layer (30) by bringing the stack (20, 30) to a temperature below 150 ° C and preferably
Ref: 0559-ARK88 below 110 ° C, for a period of less than 5 minutes, and preferably less than 2 minutes.
[7" id="c-fr-0007]
7. Method according to one of claims 1 to 6, characterized in that the pre-polymer composition (pre-TC) is a composition formulated in a solvent, or used without solvent, and which comprises at least:
- a monomer, dimer, oligomer or polymer chemical entity, or any mixture of these different entities, of chemical nature in whole or in part identical, and each comprising at least one chemical function capable of ensuring the crosslinking / polymerization reaction under l effect of a stimulus,
- one or more chemical entities capable of initiating the crosslinking / polymerization reaction under the effect of the stimulus, such as a radical generator, an acid and / or a base.
[8" id="c-fr-0008]
8. Method according to one of claims 1 to 7, characterized in that at least one of the chemical entities of the pre-polymer composition has at least one fluorine and / or silicon and / or germanium atom, and / or an aliphatic carbon chain of at least two carbon atoms in its chemical formula.
[9" id="c-fr-0009]
9. Method according to claim 7 or 8, characterized in that said pre-polymer composition (pre-TC) further comprises in its formulation:
- a chemical entity chosen from an antioxidant, a base or a weak acid, capable of trapping said chemical entity capable of initiating the crosslinking / polymerization reaction, and / or
one or more additives making it possible to improve the wetting and / or the adhesion, and / or the uniformity of the upper layer (30) of top coat (TC) deposited on the underlying layer (20), and / or
- one or more additives making it possible to absorb one or more ranges of light radiation of different wavelength, or to modify the electrical conductivity properties of the pre-polymer (pre-TC).
[10" id="c-fr-0010]
10. Method according to one of claims 1 to 9, characterized in that the pre-polymer composition (pre-TC) comprises a cross-linking / polymerization photoinitiator and it is cross-linked / polymerized by radical polymerization.
[11" id="c-fr-0011]
11. Method according to claim 10, characterized in that the monomer (s) and / or dimer (s) and / or oligomer (s) and / or polymer (s) constituting the pre layer
Ref: 0559-ARK88 polymer (pre-TC), are derivatives of acrylates or di- or tri-acrylates or multiacrylates, methacrylate, or multi-methacrylates, or polyglycidyl or vinyl, fluoroacrylates or fluoromethacrylates, fluorides of vinyl or fluorostyrene, alkyl acrylate or methacrylate, hydroxyalkyl acrylate or methacrylate, alkylsilyl acrylate or methacrylate, unsaturated esters / acids such as fumaric or maleic acids, vinyl carbamates and carbonates, allyl ethers, and thiol-ene systems.
[12" id="c-fr-0012]
12. Method according to claims 9 and 11, characterized in that the photoinitiator is chosen from acetophenone, benzophenone, peroxide, phosphine, xanthone, hydroxycetone or diazonaphthoquinone, thioxanthone, α derivatives -aminoketones, benzile, benzoin.
[13" id="c-fr-0013]
13. Method according to one of claims 1 to 8, characterized in that the pre-polymer composition (pre-TC) comprises an initiator and it is crosslinked / polymerized by cationic polymerization.
[14" id="c-fr-0014]
14. Method according to claim 13, characterized in that the monomer (s) and / or dimer (s) and / or oligomer (s) and / or polymer (s) constituting the prepolymer layer ( pre-TC), are derivatives comprising chemical functions of the epoxy / oxirane type, or vinyl ethers, cyclic ethers, thiirane, trioxane, vinyls, lactones, lactams, carbonates, thiocarbonates, maleic anhydride.
[15" id="c-fr-0015]
15. Method according to claims 13 and 14, characterized in that the initiator is a photo-generated acid (PAG) from a salt chosen from onium salts, such as iodonium and sulfonium salts , pyrridinium, alkoxypyrridinium, phosphonium, oxonium, or diazonium.
[16" id="c-fr-0016]
16. The method of claim 15, characterized in that the photo-generated acid (PAG) is coupled to a photo-sensitizing compound chosen from acetophenone, benzophenone, peroxide, phosphine, xanthone, d hydroxycetone or diazonaphthoquinone, thioxanthones, α-aminoketones, benzile, benzoin, as long as said photosensitizer absorbs at the desired wavelength.
[17" id="c-fr-0017]
17. Method according to one of claims 1 to 8, characterized in that the pre-polymer composition (pre-TC) comprises an initiator and it is crosslinked / polymerized by anionic polymerization reaction.
Ref: 0559-ARK88
[18" id="c-fr-0018]
18. Method according to claim 17, characterized in that the monomer (s) and / or dimer (s) and / or oligomer (s) and / or polymer (s) constituting the prepolymer layer ( pre-TC), are derivatives of alkyl cyanoacrylates, epoxides / oxiranes, acrylates, or derivatives of isocyanates or polyisocynanates.
[19" id="c-fr-0019]
19. Method according to claims 17 and 18, characterized in that the initiator is a photo-generated base (PBG) from derivatives chosen from carbamates, acyloximes, ammonium salts, sulfonamides, formamides, amineimides, α-aminoketones, amidines.
[20" id="c-fr-0020]
20. Method according to one of claims 1 to 19, characterized in that the first polymer layer (20) is in a solid state when the stack is brought to a temperature below its glass transition temperature or in a state liquid-viscous when the stack is brought to a temperature higher than its glass transition temperature.
[21" id="c-fr-0021]
21. The method of claim 20, characterized in that the first polymer layer (20) is a block copolymer (BCP) capable of nanostructuring at an assembly temperature, said block copolymer being deposited on a layer underlying (10) whose surface is previously neutralized, said assembly temperature being lower than a temperature at which the top coat material (TC) behaves like a viscoelastic fluid, said temperature being higher than the glass transition temperature of said top coat material and preferably, said assembly temperature is lower than the glass transition temperature of the layer (30) of top coat (TC) in its crosslinked / polymerized form.
[22" id="c-fr-0022]
22. Method according to claim 21, characterized in that the underlying layer (10) may or may not have patterns, said patterns being pre-drawn by a step or a sequence of lithography steps of any kind prior to the step of deposition of the first layer (20) of block copolymer (BCP), said patterns being intended to guide the organization of said block copolymer (BCP) by a technique called chemistry-epitaxy or graphoepitaxy, or a combination of these two techniques, to obtain a neutralized or pseudo-neutralized surface.
Ref: 0559-ARK88
[23" id="c-fr-0023]
23. Method according to one of claims 21 to 22, characterized in that the block copolymer comprises silicon in one of its blocks.
[24" id="c-fr-0024]
24. Method according to one of claims 21 to 23, characterized in that the first layer (20) of block copolymer (BCP) is deposited on a thickness (e + E) at least equal to 1.5 times the minimum thickness of the block copolymer.
[25" id="c-fr-0025]
25. Method according to one of claims 1 to 24, characterized in that the solvent of the pre-polymer layer (pre-TC) is chosen from solvents or mixtures of solvents whose Hansen solubility parameters are such that δ _ρ > 10 MPa ^1/2 and / or ôh ^ 10 MPa ^1/2 , and with 5d <25 MPa ^1/2 .
[26" id="c-fr-0026]
26. The method of claim 25, characterized in that the solvent of the pre-polymer layer (pre-TC) is chosen from alcohols such as methanol, ethanol, isopropanol, 1-methoxy-2 -propanol, ethyl lactate, diols such as ethylene glycol or propylene glycol, or among dimethylsulfoxide (DMSO), dimethylformamide, dimethylacetamide, acetonitrile, gammabutyrolactone, water or a mixture of them.
[27" id="c-fr-0027]
27. The method of claim 21, characterized in that the composition of the pre-polymer layer (pre-TC) comprises a multi-component mixture of monomers and / or dimers and / or oligomers and / or polymers each carrying functions ensuring crosslinking / polymerization, as well as different monomer units whose surface energies vary from one monomer unit to another.
[28" id="c-fr-0028]
28. Method according to one of claims 21 to 27, characterized in that the composition of the pre-polymer layer (pre-TC) further comprises plasticizers and / or wetting agents, added as additives.
[29" id="c-fr-0029]
29. Method according to one of claims 1 to 28, characterized in that the composition of the pre-polymer layer (pre-TC) further comprises rigid comonomers chosen from derivatives comprising either one / more aromatic ring (s) (s) in their structure, either mono or multicyclic aliphatic structures, and having a chemical function (s) adapted to the crosslinking / polymerization reaction targeted; and more particularly norbornene derivatives, isobornyl acrylate or methacrylate, styrenic, anthracene derivatives, adamantyl acrylate or methacrylate.
Ref: 0559-ARK88
[30" id="c-fr-0030]
30. A method of manufacturing a nano-lithography mask by directed assembly of block copolymers, from a polymeric stack obtained in accordance with the method according to one of claims 21 to 29, characterized in that once the cross-linked / polymerized top coat layer (30, TC), the stack is subjected to annealing, preferably thermal, for a determined period, at the assembly temperature of the block copolymer (BCP) so that it becomes nanostructure.
[31" id="c-fr-0031]
31. Method according to claim 30, characterized in that after the nanostructuring step of the block copolymer (BCP) the top coat layer (TC) is removed in order to leave a film of nanostructured block copolymer of minimum thickness ( e), then at least one of the blocks (21, 22) of said block copolymer, oriented perpendicular to the interfaces, is removed in order to form a porous film capable of serving as a mask for nano-lithography.
[32" id="c-fr-0032]
32. Method according to claims 24 and 31, characterized in that when the block copolymer is deposited on a thickness greater than the minimum thickness (e), an excess thickness (E) of said block copolymer is removed simultaneously or successively with the removal of the top coat layer (30, TC), in order to leave a film of nano-structured block copolymer of minimum thickness (e), then at least one of the blocks of said block copolymer, oriented perpendicular to the interfaces, is removed in order to form a porous film capable of serving as a mask for nano-lithography.
[33" id="c-fr-0033]
33. Method according to one of claims 31 to 32, characterized in that the top coat layer (30, TC) and / or the excess thickness (E) of the block copolymer and / or the block (s) (21, 22 ) of the block copolymer is / are removed by dry etching.
[34" id="c-fr-0034]
34. Method according to claim 33, characterized in that the steps of etching the top coat layer (30, TC) and / or the excess thickness (E) of the block copolymer (20, BCP) and of one or more blocks (21, 22) of the block copolymer are produced successively in the same etching frame, by plasma etching.
[35" id="c-fr-0035]
35. Method according to one of claims 3 to 34, characterized in that at the time of the crosslinking / polymerization step of the top coat layer (30, TC), the stack is subjected to light radiation and / or an electron beam located on certain areas of the top coat layer, in order to create cross-linked / polymerized areas of top coat (TC) and non-cross-linked / polymerized areas (pre-TC).
Ref: 0559-ARK88
[36" id="c-fr-0036]
36. Method according to claim 35, characterized in that in the context of the manufacture of a nano-lithography mask by directed assembly, the crosslinked / polymerized areas of top coat have a neutral affinity with respect to the copolymer underlying blocks, while the affinity of the crosslinked / polymerized top coat zones with respect to the blocks of the underlying block copolymer is not neutral.
[37" id="c-fr-0037]
37. Method according to one of claims 35 or 36, characterized in that after the localized photo crosslinking of the top coat layer (30, TC), the stack is rinsed with the solvent which has allowed the deposition of the pre layer -polymer (pre-TC) to remove non-irradiated areas.
[38" id="c-fr-0038]
38. Method according to claims 36 and 37, characterized in that another pre-polymer material, not neutral vis-à-vis the underlying block copolymer, is deposited in the areas previously non-irradiated and devoid of layer top coat, then said non-neutral pre-polymer material is exposed to a stimulus in order to crosslink / polymerize it at predefined locations.
[39" id="c-fr-0039]
39. Method according to claims 21 and 36 to 38, characterized in that at the time of the annealing step of the stack at the assembly temperature (Tass) of the block copolymer (BCP), nano-domains (20, 21; 41, 42) perpendicular to the interfaces in areas located opposite the areas of the crosslinked / polymerized neutral top coat layer (TC), and nano-domains parallel to the interfaces in areas of the copolymer to blocks located opposite areas without a crosslinked / polymerized neutral top coat.
[40" id="c-fr-0040]
40. Polymeric stack comprising at least two layers of (co) polymer (20, 30) stacked one on the other, characterized in that the upper layer (30), called top coat (TC), deposited on the first (co) polymer layer (20) is obtained by crosslinking / polymerization in situ according to the method according to one of claims 1 to 39, said stack being intended to be used in applications chosen from surface protection for aerospace or aeronautics or automotive or wind power, paints, inks, manufacturing of membranes, production of microelectronic, optoelectronic or microfluidic components.
[41" id="c-fr-0041]
41. A stack according to claim 40, characterized in that it is intended for applications in the field of nano-lithography by directed self-assembly, in
Ref: 0559-ARK88 that the first (co) polymer layer (20) is a block copolymer (BCP) and that the surfaces of the layer (10) on which the block copolymer is deposited and of the top layer coat (TC) crosslinked / polymerized, have a neutral surface energy with respect to the blocks of the block copolymer.

类似技术:

---

公开号 | 公开日 | 专利标题

---

FR3074180A1|2019-05-31|METHOD FOR CONTROLLING THE PLANEITY OF A POLYMERIC STACK

---

FR3074179A1|2019-05-31|METHOD FOR CONTROLLING THE PLANEITY OF A POLYMERIC STACK

---

KR102115280B1|2020-05-26|Substrate pretreatment for reducing fill time in nanoimprint lithography

---

US9169421B2|2015-10-27|Method of producing structure containing phase-separated structure, method of forming pattern, and top coat material

---

EP2199854A1|2010-06-23|Process and method for modifying polymer film surface interaction

---

FR2798202A1|2001-03-09|Alkali-developable negative resist for production of electronic devices contains film-forming polymer with alkali-soluble and alcohol groups which react together under the action of acid from a light-sensitive acid generator

---

EP2856258B1|2021-01-06|Process of production of a nanopatterned article using nanoimprint lithography, nanopatterned article and uses thereof

---

FR3037071A1|2016-12-09|METHOD FOR REDUCING THE DEFECTIVITY OF A BLOCK COPOLYMER FILM

---

WO2020234549A1|2020-11-26|Process for preparing a block copolymer film intended for creating a nanolithography mask

---

WO2021136793A1|2021-07-08|Prepolymer composition intended to form a contrast layer and method for structuring an interface material

---

WO2014096662A1|2014-06-26|Process for fabricating nanolithography masks

---

WO2021074540A1|2021-04-22|Method for directed self-assembly lithography

---

TW202146482A|2021-12-16|Prepolymer composition for forming a contrast layer and method for structuring an interface material

---

FR3105755A1|2021-07-02|Method of manufacturing an etching stop layer for nanolithography by directed self-assembly

---

WO2021136794A1|2021-07-08|Method for nanostructuring a substrate

---

TW202141178A|2021-11-01|Method for nanostructuring a substrate

---

FR3101355A1|2021-04-02|Neutral underlayer for block copolymer and polymer stack comprising such an underlayer covered with a film of block copolymer

---

FR3069340A1|2019-01-25|METHOD FOR CONTROLLING THE ORIENTATION OF THE NANO-DOMAINS OF A BLOCK COPOLYMER

---

FR3101354A1|2021-04-02|Neutral underlayer for block copolymer and polymer stack comprising such an underlayer covered with a film of block copolymer

---

FR3069339A1|2019-01-25|METHOD FOR CONTROLLING THE ORIENTATION OF THE NANO-DOMAINS OF A BLOCK COPOLYMER

---

Correia2019|Directed self-assembly strategies for orientation-controlled block copolymers for advanced lithography.

---

WO2015121568A1|2015-08-20|Method for controlling the surface energy of a substrate

---

FR2878854A1|2006-06-09|New high antireflection-coating polymers useful for forming samples for semiconductor devices and in immersion lithography

同族专利:

---

公开号 | 公开日

---

CN111615665A|2020-09-01|

---

FR3074180B1|2021-01-01|

---

EP3714327A1|2020-09-30|

---

TW202004335A|2020-01-16|

---

SG11202004855YA|2020-06-29|

---

WO2019102158A1|2019-05-31|

---

JP2021504114A|2021-02-15|

---

KR20200088881A|2020-07-23|

---

US20200371437A1|2020-11-26|

引用文献:

---

公开号 | 申请日 | 公开日 | 申请人 | 专利标题

---

US20030059552A1|2001-04-13|2003-03-27|Fuji Photo Film Co., Ltd.|Lower layer resist composition for silicon-containing two-layer resist|

---

US20060165912A1|2003-02-13|2006-07-27|Koberstein Jeffrey T|Micropatterning of molecular surfaces via selective irradiation|

---

EP2216683A2|2009-02-08|2010-08-11|Rohm and Haas Electronic Materials, L.L.C.|Coating compositions suitable for use with an overcoated photoresist|

---

US20150205207A1|2014-01-23|2015-07-23|Tokyo Ohka Kogyo Co., Ltd.|Method of producing structure containing phase-separated structure, method of forming pattern and method of forming fine pattern|

---

US20150261090A1|2014-03-15|2015-09-17|Board Of Regents, The University Of Texas System|Ordering Block Copolymers|

---

US20160131973A1|2014-11-12|2016-05-12|Macdermid Printing Solutions, Llc|Flexographic Printing Plate with Improved Cure Efficiency|FR3105755A1|2019-12-31|2021-07-02|Arkema France|Method of manufacturing an etching stop layer for nanolithography by directed self-assembly|

---

FR3105793A1|2019-12-31|2021-07-02|Arkema France|PREPOLYMERIC COMPOSITION INTENDED TO FORM A CONTRAST LAYER AND PROCESS FOR STRUCTURING AN INTERFACE MATERIAL|

---

FR3105786A1|2019-12-31|2021-07-02|Arkema France|Process for nanostructuring a substrate|

---

EP3913433A1|2020-05-19|2021-11-24|Commissariat à l'énergie atomique et aux énergies alternatives|Method for manufacturing moulds for nanoimprint lithography|SG11201404414SA|2012-02-10|2014-08-28|Univ Texas|Anhydride copolymer top coats for orientation control of thin film block copolymers|

---

FR3037071B1|2015-06-02|2019-06-21|Arkema France|METHOD FOR REDUCING THE DEFECTIVITY OF A BLOCK COPOLYMER FILM|

---

FR3037070B1|2015-06-02|2019-05-31|Arkema France|METHOD FOR CONTROLLING SURFACE ENERGY AT THE INTERFACE BETWEEN A BLOCK COPOLYMER AND ANOTHER COMPOUND|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:
2019-05-31| PLSC| Publication of the preliminary search report|Effective date: 20190531 |

---

2019-10-14| PLFP| Fee payment|Year of fee payment: 3 |

---

2020-10-13| PLFP| Fee payment|Year of fee payment: 4 |

---

2021-11-09| PLFP| Fee payment|Year of fee payment: 5 |

优先权:

---

申请号 | 申请日 | 专利标题

---

FR1761179|2017-11-24|

---

FR1761179A|FR3074180B1|2017-11-24|2017-11-24|METHOD OF CHECKING THE FLATNESS OF A POLYMERIC STACK|FR1761179A| FR3074180B1|2017-11-24|2017-11-24|METHOD OF CHECKING THE FLATNESS OF A POLYMERIC STACK|

---

TW107138305A| TW202004335A|2017-11-24|2018-10-30|Process for manufacturing a planar polymeric stack|

---

US16/766,490| US20200371437A1|2017-11-24|2018-11-23|Method for producing a planar polymer stack|

---

EP18826414.7A| EP3714327A1|2017-11-24|2018-11-23|Method for producing a planar polymer stack|

---

CN201880086963.4A| CN111615665A|2017-11-24|2018-11-23|Method for producing a planar polymer stack|

---

JP2020528380A| JP2021504114A|2017-11-24|2018-11-23|Methods for Producing Flat Polymer Stacks|

---

KR1020207018082A| KR20200088881A|2017-11-24|2018-11-23|How to make a planner polymer stack|

---

SG11202004855YA| SG11202004855YA|2017-11-24|2018-11-23|Method for producing a planar polymer stack|

---

PCT/FR2018/052962| WO2019102158A1|2017-11-24|2018-11-23|Method for producing a planar polymer stack|