JP2013129836A - Method of producing polymer thin film having microstructure and pattern substrate - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a method for producing a polymer thin film having a pattern with coexisted regions each consisting of regular patterns having different periods on a substrate surface or a pattern having a distribution in periods of regular patterns, which is formed by a micro-phase separation of a polymer block copolymer.SOLUTION: A method of producing a polymer thin film includes a step of arranging a polymer layer containing a polymer block copolymer composition on the surface of a substrate, and separating the micro-phase of the polymer layer. The substrate surface has patterns formed on a surface 1 and a surface 2 with different chemical characteristics. Moreover, a polymer mutually soluble into a first polymer chain or a second polymer chain, or a second polymer block copolymer is mixed in specific proportions with a polymer block copolymer in which the polymer block copolymer composition consists of a first polymer block chain and a second polymer block chain.

Description

  The present invention relates to a polymer thin film having a microstructure formed by phase separation of a polymer block copolymer on a substrate surface and a method for producing the same. The present invention also relates to a method of manufacturing a patterned substrate having a regular pattern of this microphase separation structure on the surface.

  In recent years, with the miniaturization and high performance of electronic devices, energy storage devices, sensors, etc., there is an increasing need to form a fine regular array pattern having a size of several nanometers to several hundred nanometers on a substrate. Therefore, establishment of a process capable of manufacturing such a fine pattern structure with high accuracy and low cost is required.

  As a processing method of such a fine pattern, a top-down method represented by lithography, that is, a method of giving a shape by finely carving a bulk material is generally used. For example, photolithography used for semiconductor microfabrication such as LSI manufacturing is a typical example.

  However, as the fineness of the fine pattern increases, the application of such a top-down method increases the difficulty in both the apparatus and the process. In particular, when the processing dimension of a fine pattern becomes as fine as several tens of nanometers, it is necessary to use an electron beam or deep ultraviolet light for patterning, and enormous investment is required for the apparatus. Further, when it becomes difficult to form a fine pattern using a mask, the direct drawing method must be applied, and thus the problem that the processing throughput is significantly reduced cannot be avoided.

  Under such circumstances, a process that applies a phenomenon in which a substance naturally forms a structure, that is, a so-called self-organization phenomenon, has attracted attention. In particular, the process applying the self-organization phenomenon of the polymer block copolymer, so-called microphase separation, can form a fine ordered structure having various shapes of several tens to several hundreds of nanometers by a simple coating process. In terms, it is an excellent process.

  Here, when different types of polymer segments forming the polymer block copolymer are not mixed with each other (incompatible), specific regularity is obtained by phase separation (microphase separation) of these polymer segments. The fine structure is self-organized.

  As an example of forming a fine regular structure using such a self-organization phenomenon, a polymer block copolymer thin film made of a combination of polystyrene and polybutadiene, polystyrene and polyisoprene, polystyrene and polymethyl methacrylate, etc. Is used as an etching mask, and a known technique in which a structure such as a hole or a line and space is formed on a substrate is known.

  According to the microphase separation phenomenon of this polymer block copolymer, a polymer having a structure in which fine spherical, columnar and plate-like (lamellar) microdomains are regularly arranged, which is difficult to achieve by a top-down method. A thin film can be obtained. However, in general, the self-organization phenomenon including the microphase separation phenomenon has the following problems when applied to patterning.

  That is, self-organization is excellent in short-range regularity but has long-range order and defects, and it is difficult to form an arbitrary pattern. In particular, since self-organization uses a structure formed by nature, that is, a structure having the smallest energy, it is generally difficult to obtain a structure other than a regular structure having a period specific to the material. Therefore, there is a drawback that the application range is limited. The following two methods have been devised so far to overcome these drawbacks.

  First, as a first conventional method, a groove is formed on the surface of a substrate, and a polymer block copolymer is formed inside the groove to develop microphase separation. According to this method, the fine structure developed by the microphase separation is arranged along the wall surface of the groove, so that the reportability of the regular structure can be controlled in one direction and the long-range order is improved. Moreover, since the regular structure is filled along the wall surface, the occurrence of defects is also suppressed. This effect is known as the graphoepitaxy effect, but this effect occurs as the groove width increases, and when the groove width becomes approximately 10 times the period of the regular structure, the effect becomes a regular structure at the center. Disturbance occurs. Moreover, since it is necessary to process a groove on the substrate surface, it cannot be used for applications that require a flat surface. Furthermore, in this method, it is possible to orient the regular structure in the direction along the groove, but the pattern cannot be arbitrarily controlled any more.

  As a second conventional technique, there is a method of controlling the structure expressed by microphase separation by chemically patterning the substrate surface by chemical interaction between the substrate surface and the polymer block copolymer. (Patent Documents 1 and 2).

  In this method, as shown in FIG. 1, a substrate having a surface patterned by a top-down method in a region having a different affinity for each block chain constituting the polymer block copolymer in advance is used. A polymer block copolymer is formed to develop microphase separation.

  For example, when a polymer diblock copolymer made of polystyrene and polymethyl methacrylate is used, the substrate surface is chemically patterned into a region having good affinity with polystyrene and a region having good affinity with polymethyl methacrylate. At this time, if the shape of the chemical pattern is equivalent to the microphase separation structure of polystyrene / polymethylmethacrylate diblock copolymer, a microdomain made of polystyrene is formed on a region having good affinity with polystyrene at the time of microphase separation. However, a structure in which microdomains made of polymethyl methacrylate are arranged on a region having good affinity with polymethyl methacrylate is obtained.

  That is, in this method, it is possible to arrange the microphase separation structure along the mark chemically placed on the substrate surface. Since the chemical pattern is formed by a top-down method, the long-range order of the obtained pattern is ensured by the top-down method, and a pattern having excellent regularity over a wide range and few defects can be obtained. This method is hereinafter referred to as a microdomain chemical registration method.

  In this method, the arbitraryness of the pattern to be formed is higher than in other methods. First, the arrangement direction of the regular structure pattern formed by microphase separation is in line with the direction of the chemical pattern formed on the substrate in advance. Therefore, the directionality of the microphase separation structure of the polymer block copolymer formed on the surface can be controlled by setting the direction of the regular arrangement of the chemical pattern to a desired direction. Furthermore, instead of a single polymer block copolymer, a polymer composition in which a plurality of polymer block copolymers are blended or a polymer composition in which a polymer block copolymer and a homopolymer are blended is used. There are also efforts to further improve the arbitraryness of the obtained pattern (Patent Document 3).

  According to this method, it is generally reported that a lamellar structure arranged in a straight line can be bent at a desired angle, or a columnar structure that is most stable to be arranged in hexagonal can be arranged in cubic. Yes.

USP 6,746,825, B2 USP 6,926,953, B2 US 2006/0134556

  As described above, a polymer composition in which a plurality of polymer block copolymers are blended or a polymer composition in which a polymer block copolymer and a homopolymer are blended is formed on a chemically patterned substrate surface. The method of forming a pattern by microphase separation is an excellent method that can form a fine structure with a certain degree of arbitraryness.

  However, when a polymer blend composition is formed on a substrate surface to exhibit microphase separation, it is often macroscopically phase-separated and difficult to control. When macroscopic phase separation occurs, not only the structure along the chemical pattern of the substrate surface does not appear, but also problems such as distribution of film thickness occur, making it difficult to apply to precise fine pattern formation. It is. Even when macroscopic phase separation does not occur, the size of the pattern to be obtained often varies or a defect is generated, which is difficult to apply to pattern formation.

  Furthermore, the period of the pattern obtained by the conventional method needs to be basically the same as the inherent period of the polymer blend composition. For this reason, it has been difficult to coexist regions composed of regular patterns having different periods or to provide distributions in the period of regular structure patterns.

  The present invention has been made for the purpose of improving the pattern optionality, which is a problem in producing a polymer thin film having a fine structure by applying a pattern formation process utilizing microphase separation of a polymer block copolymer. Is. In particular, there is a problem in a chemical registration method, that is, a method of obtaining an arbitrary pattern by self-organizing a polymer blend composition mainly composed of a polymer block copolymer on a chemically patterned substrate surface. Therefore, the present invention provides a method for producing a polymer thin film having a fine structure in which macroscopic phase separation is suppressed and variation in pattern size and defects are reduced. Furthermore, the present invention provides a method for producing a polymer thin film in which regions composed of regular patterns having different periods coexist or the distribution of regular structure pattern periods is distributed. Furthermore, the present invention provides a method for producing a patterned substrate based on the polymer thin film having a fine structure formed by the above method.

  In order to solve the above problems, the method for producing a polymer thin film having a microstructure according to the present invention is characterized by the following method.

  First, the first method for producing a polymer thin film having a fine structure according to the present invention includes a first stage in which a polymer layer containing a polymer block copolymer composition is disposed on a substrate surface; A second stage of phase separation to form a polymer phase.

  Here, the first polymer block copolymer composition of the present invention comprises at least a polymer block chain A1 having a molecular weight Mn (A1) and a polymer block chain A2 having a molecular weight Mn (A2). A is a polymer H1 having a molecular weight Mn (H1) compatible with the polymer phase 1 mainly composed of the polymer block chain A1, and a polymer phase 2 mainly composed of the polymer block chain A2. Mn (A1), Mn (A2), Mn (H1), and Mn (H2) have the following relationship when at least one polymer H2 having a molecular weight Mn (H2) to be dissolved is blended.

Mn (H1) <Mn (A1) ÷ 3, Mn (H2) <Mn (A2) ÷ 3
Further, the substrate surface has a first surface in which an interfacial tension with the first polymer phase is smaller than an interfacial tension with the second polymer phase, and an interfacial tension with the second polymer phase is first. The second surface is smaller than the interfacial tension with one polymer phase and is discretely arranged.

  Here, it is desirable that the polymer block chain A1 and the polymer H1 have the same chemical structure, and that the polymer block chain A2 and the polymer H2 have the same chemical structure.

  Moreover, the manufacturing method of the polymer thin film having the second microstructure of the present invention is replaced with the polymer block copolymer composition of the first polymer thin film manufacturing method, and the second polymer block described below is used. It is characterized by using a copolymer composition.

  That is, the polymer block copolymer composition is composed mainly of a polymer block copolymer A composed of a polymer block chain A1 having a molecular weight Mn (A1) and a polymer block chain A2 having a molecular weight Mn (A2). Polymer block chain B1 of molecular weight Mn (B1) compatible with polymer phase 1 mainly composed of molecular block chain A1 and molecular weight Mn compatible with polymer phase 2 mainly composed of polymer block chain A2 The polymer block copolymer B consisting of the polymer block chain B2 of (B2) is blended as a subcomponent, and Mn (A1, Mn (A2), Mn (B1), Mn (B2) It is characterized by having.

Mn (A2)> Mn (A1) and Mn (B2)> Mn (A2)
Here, the polymer block chain A1 and the polymer block chain B1 have the same chemical structure, and the polymer block chain A2 and the polymer block chain B2 have the same chemical structure. desirable.

  In the first and second polymer thin film production methods, the weight fraction of the polymer block copolymer A as the main component is 75% or more and 95% of the polymer block copolymer composition. The following is desirable. Moreover, it is desirable that one of the first polymer block chain and the second polymer block chain is polystyrene and the other is polymethyl methacrylate.

Further, in the first and second polymer thin film manufacturing methods, the fine structure has a region in which a columnar polymer phase is regularly arranged in a matrix polymer phase, or a plate-like polymer phase. It is characterized in that a regularly arranged region or both regions coexist. Here, the period d of the regular arrangement in the region and the natural period d ₀ of the microstructure formed by the microphase separation in the bulk state in the polymer block copolymer composition are:
0.9 × d ₀ <d <1.3 × d ₀
It is desirable to have this relationship. Furthermore, the present invention includes a case where there are at least two kinds of the regular array period d in the region.

  In the substrate of the present invention, the arrangement of the surface 1 or the surface 2 is regular, and the average period ds is equal to the period d of the regular arrangement in the region or is a natural number multiple of the period d. Features. Here, the surface 1 is made of a polymer having the same chemical composition as that of the first polymer block chain, or the surface 2 is made of a polymer having the same chemical composition as that of the second polymer block chain. It is desirable to consist of.

  Furthermore, the manufacturing method of the patterned substrate of the present invention uses the following method as its means.

  That is, a pattern substrate is manufactured by adding a step of selectively removing one of the polymer phases formed by microphase separation from the polymer thin film manufactured by the method for manufacturing a polymer thin film. Further, the substrate is processed via the remaining other polymer phase to transfer the microphase separation pattern to the surface of the substrate, or the remaining other polymer phase is transferred to the pattern substrate. Manufacturing. Furthermore, a pattern substrate is manufactured by doping one of the polymer phases manufactured by the method for manufacturing a polymer thin film or the pattern substrate.

  By applying the present invention, it is possible to improve the arbitraryness of the pattern when producing a polymer thin film having a fine structure by utilizing the microphase separation of the polymer block copolymer. In addition, it is possible to manufacture a polymer thin film having a fine structure in which macroscopic phase separation is suppressed and variation in pattern size and defects are reduced. In addition, it is possible to manufacture polymer thin films that have regular patterns with different periods, or to produce polymer thin films that have a distribution in the pattern period of regular structures, and it is possible to manufacture pattern substrates based on the obtained patterns. It becomes.

It is the schematic diagram which showed the concept of chemical registration. It is the schematic diagram which showed the process of this invention. It is a schematic diagram which shows the example of the structure in the polymer block copolymer microphase-separated on the substrate surface. It is a schematic diagram which shows an example of the chemical patterning process of a board | substrate. It is a schematic diagram which shows the example of the cross section of the board | substrate chemically patterned. It is a schematic diagram which shows the example of chemical registration. It is a schematic diagram which shows an example of embodiment of this invention. It is a schematic diagram which shows an example of embodiment of this invention. It is a schematic diagram which shows an example of the process which produces a pattern board | substrate by this invention. It is a figure which shows the pattern arrangement | positioning of the board | substrate in the Example of this invention. It is an atomic force microscope observation image of the pattern which a polymer block copolymer composition forms, and its two-dimensional Fourier-transform image. It is a scanning electron microscope image of the pattern which the polymer block copolymer composition forms on the chemically patterned substrate surface.

  Embodiments of the present invention will be described below with reference to the drawings.

  An outline of a manufacturing process (chemical registration process) of a polymer thin film having a microstructure according to the present invention will be described with reference to FIG. 2, and then each process step will be described in detail.

  First, as shown in FIG. 2A, a substrate 10 that serves as a base of a polymer thin film having a fine structure is prepared. Next, as shown in FIG. 2B, the substrate surface is patterned into a surface 1 and a surface 2 having different chemical properties. As shown in FIG.2 (c), the polymer resin composition 11 which has a polymer block copolymer as a main component is formed into a film on this substrate surface. As shown in FIG. 2D, the polymer resin composition 11 is microphase-separated to form a microstructure composed of the polymer phase 1 and the polymer phase 2 in the polymer composition layer. At this time, the polymer phase 1 has better wettability than the polymer phase 2 with respect to the surface 1 prepared in the stage shown in FIG. 2B, and the polymer phase 2 has a polymer phase with respect to the surface 2. When the chemical state of the surface 1 and the surface 2 and the chemical composition of the polymer composition are designed so that the wettability is better than 1, the polymer phase 1 and the polymer phase 2 as shown in FIG. Are disposed on surface 1 and surface 2. Finally, as shown in FIG. 2 (e), a polymer thin film having a fine structure can be formed by removing the polymer phase on one side.

  Hereinafter, materials used in the manufacturing process of the polymer thin film having the microstructure of the present invention will be described in detail.

(Polymer block copolymer composition)
The first polymer block copolymer composition used in the present invention is obtained by mixing (blending) homopolymer H as a minor component with polymer block copolymer A as a main component, and forming a film on the substrate surface. In this state, a desired fine structure is expressed by microphase separation. The second polymer block copolymer composition used in the present invention is obtained by mixing (blending) the second polymer block copolymer B as a subcomponent with the polymer block copolymer A as a main component. In order to express a desired fine structure by microphase separation in a state where a film is formed on the surface of the substrate.

  First, the polymer block copolymer A commonly used as the main component of the first and second polymer block copolymer compositions is composed of the first block chain A1 made of the polymer of the first monomer and the second monomer. It consists of a second block chain A2 made of a polymer. Here, the first block chain A1 and the second block chain A2 may be a combination that undergoes phase separation, but more desirably, the block chain A1 is a main component in the process step shown in FIG. It is even more desirable if the combination can selectively remove the microdomain that is or the microdomain whose main component is the block chain A2.

  Examples of the polymer block copolymer A that satisfies the above conditions include polybutadiene-polydimethylsiloxane, polybutadiene-4-vinylpyridine, polybutadiene-methyl methacrylate, polybutadiene-poly-t-butyl methacrylate, and polybutadiene-t. -Butyl acrylate, poly-t-butyl methacrylate-poly-4-vinyl pyridine, polyethylene-polymethyl methacrylate, poly-t-butyl methacrylate-poly-2-vinyl pyridine, polyethylene-poly-2-vinyl pyridine, polyethylene-poly -4-vinylpyridine, polyisoprene-poly-2-vinylpyridine, polymethyl methacrylate-polystyrene, poly-t-butyl methacrylate-polystyrene, polymethyl acrylate-polystyrene Polybutadiene-polystyrene, polyisoprene-polystyrene, polystyrene-poly-2-vinylpyridine, polystyrene-poly-4-vinylpyridine, polystyrene-polydimethylsiloxane, polystyrene-poly-N, N-dimethylacrylamide, polybutadiene-polyacryl Examples thereof include sodium acid, polybutadiene-polyethylene oxide, poly-t-butyl methacrylate-polyethylene oxide, polystyrene-polyacrylic acid, and polystyrene-polymethacrylic acid. In addition, this invention is not necessarily limited to these polymer block copolymers, If it is a combination which expresses micro phase separation, it can be used widely.

  The first polymer block copolymer composition in the present invention is obtained by blending the polymer block copolymer A as a main component with homopolymer H1, homopolymer H2 or both as subcomponents. Here, the homopolymer H1 is a polymer so as to be compatible with the block chain A1 of the polymer block copolymer A as the main component, and the homopolymer H2 is a block chain A2 of the polymer block copolymer A as the main component. It is a polymer that is compatible with. By adopting such a combination, the polymer block copolymer composition was phase-separated to develop microdomain 1 mainly composed of block chain A1 and microdomain 2 mainly composed of block chain A2. In this case, the homopolymer H1 is selectively compatible with the microdomain 1 and the homopolymer H2 is selectively compatible with the microdomain 2.

  Specifically, as the polymer block copolymer A, a polymer that can be applied as a homopolymer 1 and a homopolymer 2 is exemplified by a case of a polystyrene-block-polymethyl methacrylate copolymer (PS-b-PMMA). Is illustrated.

  First, polystyrene can be applied to the homopolymer H1, and polyphenylene ether, polymethyl vinyl ether, poly α-methyl styrene, nitrocellulose, etc., which are polymers compatible with polystyrene, can be applied.

  In addition, polymethyl methacrylate can be applied to the homopolymer H2, and styrene-acrylonitrile copolymer, acrylonitrile-butadiene copolymer, vinylidene fluoride-trifluoroethylene, which are polymers compatible with polymethyl methacrylate, can be used. Copolymer, vinylidene fluoride-tetrafluoroethylene copolymer, vinylidene fluoride-hexafluoroacetone copolymer, vinylphenol-styrene copolymer, vinylidene chloride-acrylonitrile copolymer, vinylidene fluoride homopolymer, etc. are applied can do.

  Even the above polymers may be incompatible with each other depending on the molecular weight and concentration, and in the case of a copolymer, depending on the composition. Moreover, it may become incompatible with temperature, and it is desirable that it is in a compatible state even at the temperature during heat treatment.

  Next, the relationship among the molecular weights of the polymer block copolymer A, homopolymer 1 and homopolymer 2 applied to the present invention will be described. First, the molecular weight of the block chain 1 constituting the polymer block copolymer A is Mn (A1), the molecular weight of the block chain 2 is Mn (A2), the molecular weight of the homopolymer 1 is Mn (H1), and the molecular weight of the homopolymer 2 is Mn. Assuming (H2), each molecular weight needs to satisfy the following formula.

Mn (H1) <Mn (A1) ÷ 3
Mn (H2) <Mn (A2) ÷ 3
By combining the molecular weights to satisfy this relationship, the macroscopic phase separation, which is a problem in pattern formation by the chemical registration method, is suppressed, and the microstructure with reduced pattern size variation and defects is reduced. It is possible to produce a polymer thin film having the same. Furthermore, it is possible to manufacture a polymer thin film having a regular pattern with a different period and coexisting with a pattern of a regular structure pattern, and a pattern substrate can be manufactured based on the obtained pattern. It becomes possible.

  Next, the second polymer block copolymer composition in the present invention comprises the polymer block copolymer A as the main component and the second polymer block copolymer B as a subcomponent. . Here, the polymer block copolymer B includes a third polymer block chain B1 that is compatible with the first polymer block chain and a fourth polymer block chain that is compatible with the second polymer block chain. It consists of B2. By adopting such a combination, the polymer block copolymer composition was phase-separated to develop microdomain 1 mainly composed of block chain A1 and microdomain 2 mainly composed of block chain A2. In this case, the block chain B1 is selectively compatible with the microdomain 1 and the block chain B2 is selectively compatible with the microdomain 2.

  Specifically, the polymer block copolymer A is exemplified by PS-b-PMMA, and examples of the polymer that can be applied as the block chain B1 and the block chain B2.

  First, polystyrene can be applied to the block chain B1, and polyphenylene ether, polymethyl vinyl ether, poly α-methyl styrene, nitrocellulose, etc., which are polymers compatible with polystyrene, can be applied.

  In addition, polymethyl methacrylate can be applied to the block chain B2, and styrene-acrylonitrile copolymer, acrylonitrile-butadiene copolymer, vinylidene fluoride-trifluoro, which are polymers compatible with polymethyl methacrylate. Ethylene copolymer, vinylidene fluoride-tetrafluoroethylene copolymer, vinylidene fluoride-hexafluoroacetone copolymer, vinylphenol-styrene copolymer, vinylidene chloride-acrylonitrile copolymer, vinylidene fluoride homopolymer, etc. Can be applied.

  Even the above polymers may be incompatible with each other depending on the molecular weight and concentration, and in the case of a copolymer, depending on the composition. Moreover, it may become incompatible with temperature, and it is desirable that it is in a compatible state even at the temperature during heat treatment.

  Next, the relationship between the molecular weights of the polymer block copolymer A and the polymer block copolymer B applied to the present invention will be described. First, when the molecular weight of the block chain B1 constituting the polymer block copolymer B is Mn (B1) and the molecular weight of the block chain B2 is Mn (B2), each molecular weight needs to satisfy the following formula.

Mn (A2)> Mn (A1) and Mn (B2)> Mn (A2)
By combining the molecular weights to satisfy this relationship, the macroscopic phase separation, which is a problem in pattern formation by the chemical registration method, is suppressed, and the microstructure with reduced pattern size variation and defects is reduced. It is possible to produce a polymer thin film having the same. Furthermore, it is possible to manufacture a polymer thin film having a regular pattern with a different period and coexisting with a pattern of a regular structure pattern, and a pattern substrate can be manufactured based on the obtained pattern. It becomes possible.

  In addition, in any case, the first polymer block copolymer composition and the second polymer block copolymer composition, the weight fraction of the polymer block copolymer A as the main component occupying the whole. Is preferably 75% to 95%. If the weight fraction deviates from this range, macro block copolymer A may macroscopically separate from macro block copolymer B or homopolymers H1 and H2, which are subcomponents, during microphase separation. Becomes higher.

  After satisfying the above conditions, the polymer block copolymer composition has a molecular weight and composition ratio of polymer chains constituting the polymer block copolymer composition according to the shape and size of the target pattern. Just choose.

  That is, the polymer block copolymer composition is polymer phase 1 mainly composed of block chain A1 by microphase separation (phase forming microdomain 1) and polymer phase 2 mainly composed of block chain A1 ( When the phase separation into the phase forming the microdomain 2), as the proportion of the polymer phase 1 in the total volume increases from 0% to 50%, the structure of the microphase separation is that the spherical microdomain 1 is a polymer. From a structure regularly arranged in a matrix composed of phase 2, a structure in which cylinder (pillar) -like microdomains 1 are regularly arranged in a matrix composed of polymer phase 2, and a plate (lamellar) -like microdomain It changes into a structure in which domain 1 and microdomain 2 are alternately arranged. Further, when the ratio of the polymer phase 1 to the total volume is increased, on the contrary, from the structure in which the plate (lamellar) microdomains 1 and microdomains 2 are alternately arranged, the cylinder (column) microdomain 2 Are regularly arranged in a matrix composed of the polymer phase 1, and further, the spherical microdomains 2 are changed into a structure regularly arranged in the matrix composed of the polymer phase 1.

  The size of the pattern is mainly defined by the total molecular weight of the polymer block copolymer A. As the molecular weight increases, the size of the structure increases.

  In the above description, the polymer block copolymer A is described as an example of a polymer diblock copolymer formed by bonding two types of block chains. However, the polymer block copolymer used in the present invention is not limited to such a form, and other ABA polymer triblock copolymers and ABC polymer comprising three or more polymer segments. It may be a linear polymer block copolymer such as a block copolymer, or a star-type polymer block copolymer.

  In addition, the polymer block copolymer and homopolymer may be synthesized by an appropriate method, but in order to improve the regularity of the microphase-separated structure, a synthesis method that reduces the molecular weight distribution as much as possible, for example, a living polymerization method It is appropriate to use

Now, the polymer block copolymer composition of the present invention exhibits a fine spherical, cylindrical, lamellar or other structure by microphase separation. As described above, the structure and size are determined according to the composition of the polymer block copolymer composition. That is, the structure and size that the polymer block copolymer composition develops are unique depending on the molecular weight and composition of the polymer that constitutes the polymer block copolymer composition. Here, the period of the regular structure that appears by microphase separation is defined as the natural period d ₀ . When the microphase separation structure is cylindrical, the cylinders are regularly arranged by packing into hexagonal as shown in FIG. In this case, the natural period d ₀ is defined by the lattice spacing of the hexagonal array. In addition, as shown in FIG. 3B, when the microphase separation structure is lamellar, the lamella has a alternately laminated structure. In this case, the natural period d ₀ is defined by the interval between lamellae. Further, when the microphase separation structure is spherical, the spheres are arranged in a body-centered lattice (BCC) shape. In this case, the natural period d ₀ is defined by the interval of the BCC lattice. The natural period d ₀ is the period of the fine structure when the polymer block copolymer is microphase-separated on the substrate surface not subjected to the chemical pattern.

(substrate)
In the chemical registration method, as shown in FIG. 2 (b), the surface of the substrate is patterned into surfaces 1 and 2 having different chemical properties, and a polymer block copolymer composition is formed on each surface. By arranging the domain 1 and the micro domain 2, the micro phase separation structure is controlled. Here, a method of patterning the substrate surface into surfaces A and B having different chemical properties will be described.

  First, the material of the substrate shown in FIG. 2A is not particularly limited. For example, a substrate made of an inorganic material such as glass or titania, a semiconductor such as silicon or GaAs, a metal such as copper, tantalum, or titanium, or an organic material such as epoxy resin or polyimide may be selected according to the purpose.

  An example of a method for patterning the substrate surface into chemically different surfaces 1 and 2 will be described with reference to FIG. In this example, the polymer block copolymer which is a main component constituting the polymer block copolymer composition is PS-b-PMMA. Therefore, polystyrene (PS) is the main component by microphase separation. This is based on the premise that microdomains and microdomains mainly composed of polymethyl methacrylate (PMMA) are expressed.

  First, as shown in FIG. 4A, the surface of the substrate 10 is chemically modified in order to make the entire surface of the substrate 10 more easily wettable by PS compared to PMMA. For chemical modification, it is preferable to use a method such as monomolecular film formation by silane coupling or polymer grafting. In order to make the surface of the substrate have a good affinity with PS, for example, in the case of monomolecular film formation, introduction of a phenethyl group by coupling reaction of phenethyltrimethoxysilane, or in the case of polymer modification, PS A polymer that is compatible with the substrate may be introduced onto the substrate surface by grafting.

  For polymer grafting, a chemical group that is the starting point of polymerization is first introduced into the substrate surface by a coupling method or the like, and the polymer is polymerized from the polymerization starting point or chemically coupled to the substrate surface. There is a method of synthesizing a polymer having a functional group in the terminal or main chain and then coupling it to the substrate surface. In particular, the latter method is simple and recommended.

  Here, specifically, a technique for grafting polystyrene onto the silicon surface in order to make the surface of the silicon substrate preferred by PS will be described. First, polystyrene having a hydroxyl group at the terminal is synthesized by a predetermined living polymerization. Next, the density of hydroxyl groups on the surface of the natural oxide film on the surface of the substrate is improved by exposing the silicon substrate to oxygen plasma or immersing it in a piranha solution. Polystyrene having a hydroxyl group at the terminal is dissolved in a solvent such as toluene, and a film is formed on a silicon substrate by a technique such as spin coating. Thereafter, the obtained substrate is heated in a vacuum atmosphere at a temperature of about 170 for about 72 hours using a vacuum oven or the like. By this treatment, the hydroxyl group on the substrate surface and the hydroxyl group at the end of the polystyrene are dehydrated and condensed, and polystyrene near the substrate surface is bonded to the substrate. Finally, the substrate is washed with a solvent such as toluene to remove the unbound polystyrene from the substrate surface, thereby obtaining a silicon substrate on which polystyrene is grafted.

  When the polymer is grafted on the substrate surface, the molecular weight of the polymer to be grafted is not particularly limited, but if the molecular weight is about 1,000 to 10,000, the film thickness on the substrate surface is increased by using the grafting method. It is possible to form a polymer ultrathin film of several nm.

  Next, the chemically modified layer provided on the substrate surface is patterned. As a patterning method, a known patterning technique such as photolithography or an electron beam direct drawing method may be applied according to a desired pattern size. That is, as shown in FIG. 4, first, a chemically modified layer 12 is formed on the surface of the substrate 10 (FIG. 4A) (FIG. 4B), and a resist film 13 is formed on the surface (FIG. 4). (C)), the resist film is patterned by exposure (FIG. 4 (d)), developed (FIG. 4 (e)), the resist is patterned, and then chemically modified by a technique such as oxygen plasma treatment. What is necessary is just to pattern by etching a layer (FIG.4 (f) (g)). Finally, by removing the resist film on the remaining chemically modified layer, a patterned chemically modified layer is obtained (FIG. 4H). This process is an example, and other means may be used as long as the chemically modified layer provided on the substrate surface can be patterned. 4 describes the method of discretely disposing the chemically modified layer on the surface of the substrate, the cross section of the obtained substrate is as shown schematically in FIG. This is a structure in which thin films having different chemical properties are formed. However, in the present invention, as schematically shown in FIG. 5B, a substrate in which regions whose surface states are chemically different from the substrate are embedded in a discrete manner inside the substrate, or FIG. As schematically shown in Fig. 5, a substrate or the like in which two types of chemically different thin films are arranged on the surface of the substrate may be applied.

  According to the method shown in FIG. 4, a substrate having a polystyrene modified layer patterned on the silicon substrate surface is obtained. That is, the surface of the substrate is patterned into a surface 1 where the silicon substrate is exposed and a surface 2 made of a polystyrene-modified layer, but the silicon surface has a property of favoring polymethyl methacrylate over polystyrene, and as a result, PS-b- A surface having selectivity with respect to each of the microdomain mainly composed of polystyrene and the microdomain mainly composed of polymethyl methacrylate expressed by the polymer block copolymer mixture mainly composed of PMMA is obtained.

  As mentioned above, the patterning method of the substrate surface has been described in detail for the polymer block copolymer mixture mainly composed of PS-b-PMMA, but the same applies to other polymer block copolymer mixtures. The substrate surface may be chemically patterned by a method.

(Chemical registration)
The chemical registration method was developed for the purpose of improving the long-range order of the microphase-separated structure formed by self-organization of the polymer block copolymer by a chemical mark provided on the substrate surface. The short-range order, that is, the pattern of the microscopic structure and the periodic structure thereof must be designed to be equivalent to the unique pattern of the polymer block copolymer.
For example, when using a polymer block copolymer having a microphase separation structure in which cylindrical microdomains are regularly arranged in a hexagonal manner with a lattice spacing d ₀ , the shape and size of the chemical pattern is as shown in FIG. It was necessary to pattern a circular pattern corresponding to the diameter of the cylindrical microdomain with a natural number multiple of the period d ₀ . In other words, in the conventional chemical registration method, it is possible to regularly form the unique pattern of the polymer block copolymer to be used over a long distance with the natural period d _0. Could not be formed with different shapes and different periods.

  As in the present invention, as a method for improving the optionality of a pattern formed by chemical registration, a high polymer mixed with a homopolymer or a second polymer block copolymer is used instead of a single polymer block copolymer. A method using a molecular block copolymer mixed system has been known. In this method, a homopolymer or a second polymer block copolymer is blended with the polymer block copolymer to give a degree of freedom to the microphase separation structure formed by the polymer block copolymer mixture system. This is based on the concept that it is possible to cope with a chemical pattern of a substrate having a shape whose arrangement or period is shifted from the inherent pattern of the polymer block copolymer mixture system.

  However, in the conventional method using a polymer block copolymer mixture system, depending on the pattern, the polymer block copolymer mixture system may perform macroscopic phase separation, pattern size variation or defects may occur. There was a problem. The present invention has been made to solve such a problem by using the first and second polymer block copolymer compositions as described above.

Typical examples of patterns that can be stably and accurately formed by applying the chemical registration method according to the present invention are shown below. A pattern that has become possible when the intrinsic pattern of the polymer block copolymer mixture system is cylindrical and the intrinsic period is d ₀ will be described with reference to FIG. FIG. 7 is a cross-sectional view of a pattern in a direction parallel to the substrate.

FIG. 7A shows a pattern in which cylindrical microdomains are arranged on the entire surface of the substrate with a period d ₀ in a state where the cylindrical microdomains stand upright on the substrate. This pattern can also be handled by a conventional method in which a single polymer block copolymer is formed on the surface of a chemically patterned substrate having the same shape as that shown in FIG.

Next, FIG. 7B shows a pattern in which the cylindrical microdomains are arranged on the entire surface of the substrate with a period d in a state where the cylindrical microdomains stand upright on the substrate. In the case of this pattern, unlike FIG. 7A, the period d is not the same as the natural period d ₀ . When a polymer block copolymer mixture having the composition of the present invention is used, if d is in the range of 0.9 × d ₀ <d <1.3 × d ₀ , it is stable even in the case of d ≠ d _0. Chemical registration can be realized with high accuracy.

FIGS. 7 (c-1) to 7 (c-3) show a case where the cylindrical microdomains are arranged in a hexagonal state upright on the substrate, and the period d is not uniform. As shown in FIG. 7 (c-1), when d changes in the uniaxial direction, or when the lattice size increases as a whole as shown in FIG. 7 (c-2), FIG. As shown, even in a pattern in which a plurality of regions having different d coexist, a chemical resist can be stably and accurately provided that d is in the range of 0.9 × d ₀ <d <1.3 × d _0. Is realized.

FIG. 7D shows a case where the cylindrical microdomains are arranged in a hexagonal state in an upright state on the substrate, but the lattice is distorted in an arc shape. In such a structure, not only the value of d is different between the upper part and the lower part of the lattice distorted on the arc, but the orientation of the first adjacent lattice adjacent to the lattice point deviates from the hexagonal lattice, but the lattice spacing d is 0. If it is in the range of 9 × d ₀ <d <1.3 × d ₀ , chemical registration can be realized stably and accurately.

  As described above, the cylindrical microdomain has been described as an example. However, in the case of a pattern in which the lamellar microdomains are arranged in an upright state with respect to the substrate, the chemical registration for the spacing between the lamellas and the bending of the lamella is similarly performed. The degree of freedom is increased by applying the polymer block copolymer composition having the first and second compositions of the present invention. In FIG. 7, the features of the present invention have been described focusing on the period of the pattern. However, the domain size can be reduced by applying the polymer block copolymer composition having the first and second compositions of the present invention. However, the degree of freedom increases, and it is possible to create a pattern having a distribution not only for the pattern period but also for the size and shape of the pattern. That is, when the case of the cylindrical microdomain is applied, it is possible to provide a distribution in the diameter of the cylinder or change the cross section of the cylinder from a circle to an ellipse.

  Furthermore, according to the present invention, by applying the polymer block copolymer composition having the first and second compositions, as shown in FIG. 8, a pattern in which the cylinder and the lamella coexist is also created by the chemical registration method. can do.

(Film formation and phase separation of polymer block copolymer composition)
A polymer block copolymer composition is formed on a chemically patterned substrate prepared by the above-described method to develop microphase separation. The method is described below.

First, the polymer block copolymer composition is dissolved in a solvent to obtain a dilute polymer block copolymer composition solution. Next, a polymer block copolymer composition solution is formed on the chemically patterned substrate surface as shown in FIG. The film forming method is not particularly limited, and a method such as spin coating or dip coating may be used. When spin coating is used, the polymer block copolymer composition thin film having a film thickness of several tens of nm is stable when the weight concentration of the solution is generally several percent and the spin coating rotation speed is 1000 to 5000 rotations. Can be obtained. Further, the film thickness of the polymer block copolymer composition is not particularly limited, but in order to maximize the effect of chemical registration, the intrinsic period d ₀ of the polymer block copolymer composition is set. It is desirable to be about 5 times or less.

  The structure of the polymer block copolymer composition formed on the chemically patterned substrate surface is generally not an equilibrium structure, although it depends on the film forming method. That is, with the rapid vaporization of the solvent during film formation, the polymer block copolymer composition does not sufficiently undergo microphase separation, and the structure is frozen in a non-equilibrium state or in a completely disordered state. In many cases, it is in a state where Therefore, the substrate is annealed in order to sufficiently advance the microphase separation process of the polymer block copolymer composition and obtain an equilibrium structure. Annealing is performed by thermal annealing that is left in a state where the polymer block copolymer composition is heated above the glass transition temperature, solvent annealing that is left in a state where the polymer block copolymer composition is exposed to a good solvent vapor, or the like. be able to. In the case of a polymer block copolymer composition mainly composed of PS-b-PMMA, thermal annealing is simple, and annealing treatment is performed by heating in a vacuum atmosphere at a temperature of 170 to 200 ° C. for several hours to several days. Complete.

(About pattern substrates)
Next, with reference to FIG. 9, various methods for producing a pattern substrate using the microphase separation structure of the polymer block copolymer composition will be described. In FIG. 9, surfaces having different chemical properties existing in a patterned state on the substrate surface are omitted. Here, the pattern substrate refers to a substrate on which a concavo-convex surface corresponding to a regular arrangement pattern of a microphase separation structure is formed on the substrate surface. In addition, for the sake of simplicity, the following description assumes a cylindrical structure as a microphase separation pattern. However, in the case of a lamella structure or a structure in which a lamella and a cylinder coexist, a pattern substrate is used in a similar manner. Can be obtained.

  First, the polymer phase B on one side is selectively removed from the microphase separation structure composed of the polymer phase A (continuous phase) and the polymer phase B (columnar phase) shown in FIG. As shown in FIG. 9B, a porous thin film D in which a plurality of fine holes H form a regular arrangement pattern is obtained.

  Although not shown, a polymer thin film in which a plurality of columnar structures (columnar phases B) form a regular array pattern can be obtained by selectively removing the polymer phase of the continuous phase A. Thus, the porous thin film D in which the plurality of fine holes H or the columnar structures form a regular arrangement pattern is formed on the substrate 20 to manufacture the pattern substrate.

  Although not described in detail, in FIG. 9B, the other remaining polymer phase (in FIG. 9B, the porous thin film D composed of the continuous phase A) is peeled off from the surface of the substrate 20 to obtain a single porous thin film D. Can be manufactured as a pattern substrate.

  By the way, as shown in FIG. 9B, as a method for selectively removing either the continuous phase A or the columnar phase B constituting the polymer thin film C, reactive ion etching (RIE) is used. ) Or other etching methods that use the difference in etching rate between the polymer phases. Here, it is also possible to improve the selectivity of etching by doping a metal atom or the like into either the continuous phase A or the columnar phase B. For example, in the case of a polymer block copolymer of polystyrene and polybutadiene, the polymer phase made of polybutadiene is more easily doped with osmium than the polymer phase made of polystyrene. Using this effect, it is possible to improve the etching resistance of the domain made of polybutadiene.

  Next, with reference to FIGS. 9C and 9D, another example of the method for manufacturing the pattern substrate will be described.

  The substrate is etched by RIE or plasma etching using the remaining polymer phase (porous thin film D) as in the continuous phase A shown in FIG. 9B as a mask. Then, as shown in FIG. 9 (c), the surface portion of the substrate corresponding to the portion of the polymer phase selectively removed through the fine holes H is processed, and the regular arrangement pattern of the micro separation structure becomes the surface of the substrate. Will be transferred to. Then, when the porous thin film remaining on the surface of the pattern substrate is removed with RIE or a solvent, fine holes H having a regular arrangement pattern corresponding to the columnar phase B are formed on the surface as shown in FIG. A patterned substrate can be obtained.

  Next, with reference to FIGS. 9E and 9F, another embodiment relating to a method of manufacturing a pattern substrate will be described.

  The other polymer phase (porous thin film D) remaining like the continuous phase A shown in FIG. 9B is brought into close contact with the transfer target 30 as shown in FIG. The regular array pattern is transferred to the surface of the transfer target 30. Thereafter, as shown in FIG. 9 (f), the transferred object is peeled from the pattern substrate 21 to obtain a replica (pattern substrate 31) to which the regular array pattern of the porous thin film D is transferred.

  Here, the material of the object to be transferred may be selected according to the application, such as nickel, platinum, gold or the like if it is a metal, or glass or titania if it is an inorganic material. When the transfer object is made of metal, the transfer object can be brought into close contact with the uneven surface of the pattern substrate by sputtering, vapor deposition, plating, or a combination thereof.

  Further, when the transfer target is an inorganic substance, it can be adhered by using, for example, a sol-gel method in addition to sputtering or CVD. Here, the plating or sol-gel method is a preferable method because it can accurately transfer a fine regular array pattern of several tens of nanometers in a microphase separation structure, and can reduce the cost by a non-vacuum process. .

  The patterned substrate obtained by the above-described manufacturing method is applied to various uses because the irregular surface of the regularly arranged pattern formed on the surface thereof is fine and the aspect ratio is large.

  For example, by repeatedly bringing the surface of the manufactured pattern substrate into close contact with the transfer object by the nanoimprint method or the like, it can be used for the purpose of manufacturing a large number of replicas of the pattern substrate having the same regular array pattern on the surface. .

  Hereinafter, a method for transferring a fine regular array pattern on the concavo-convex surface of the pattern substrate to the transfer object by the nanoimprint method will be described.

  The first method is a method in which a regular pattern is transferred by directly imprinting a produced pattern substrate onto a transfer target (not shown) (this method is called a thermal imprint method). This method is suitable when the material to be transferred is a material that can be directly imprinted. For example, when a thermoplastic resin typified by polystyrene is used as the material to be transferred, it is heated to a temperature higher than the glass transition temperature of the thermoplastic resin. After that, when the pattern substrate is released from the surface of the transfer object, a replica can be obtained.

  Further, as a second method, when the pattern substrate is made of a light transmissive material such as glass, a photocurable resin is applied as a transfer target (not shown) (this method is called a photoimprint method). ). When light is irradiated after the photocurable resin is closely attached to the pattern substrate, the photocurable resin is cured. Therefore, the pattern substrate is released and the photocurable resin (transfer object) after curing is removed. It can be used as a replica.

  Further, in such a photoimprint method, when a substrate such as glass is used as a transfer target (not shown), a photocurable resin is brought into close contact with a gap between the pattern substrate and the transfer target substrate. Irradiate light. Then, after curing the photocurable resin, the pattern substrate is released, and the cured photocurable resin having irregularities on the surface is used as a mask, and etching is performed with plasma, ion beam, or the like. There is also a method of transferring a regular arrangement pattern on the top.

(Regarding patterned media for magnetic recording)
As an example of a device realized in the present invention, a magnetic recording medium will be mentioned. Magnetic recording media are always required to improve data recording density. For this reason, the dots on the magnetic recording medium, which is a basic unit for engraving data, are also miniaturized and the interval between adjacent dots is narrowed to increase the density.

  Incidentally, in order to construct a recording medium having a recording density of 1 terabit / square inch, it is said that the period of the dot arrangement pattern needs to be about 25 nanometers. Thus, as the density of dots increases, there is a concern that the magnetism applied to turn on / off one dot affects adjacent dots.

  Therefore, in order to eliminate the influence of magnetism leaking from the adjacent dots, a pattern medium in which the dot area on the magnetic recording medium is physically divided has been studied.

  The present invention can be applied to the production of this patterned medium or a master for producing the patterned medium. In particular, in a patterned medium, it is necessary to arrange minute irregularities regularly and on an arc without a defect. As shown in FIG. 7D, such a pattern can be realized by the present invention. In addition, as the pattern of the magnetic recording pattern medium, it has a dot pattern serving as a recording layer and a servo pattern for performing a recording / reproducing operation, and the dot pattern and the servo pattern are provided with different periods and shapes, It is effective to apply the present invention that can improve pattern arbitraryness.

  In this example, the method for producing a polymer thin film having the first microstructure of the present invention was carried out using polystyrene-block-polymethyl methacrylate copolymer (PS-b-PMMA) as the polymer block copolymer. The results of these studies will be explained with reference to comparative examples as appropriate.

(Preparation of chemically patterned substrate)
The substrate is a Si wafer with a natural oxide film, and after polystyrene is grafted on the entire surface, the polystyrene graft layer is patterned by electron beam (EB) lithography to achieve different wettability with respect to polystyrene and polymethyl methacrylate. A substrate having a patterned surface with The procedure will be described in detail below.

  The polystyrene graft substrate was prepared by the following method. First, a Si wafer (4 inches) having a natural oxide film was washed with a piranha solution. Since the piranha treatment has an oxidizing action, in addition to removing organic substances on the substrate surface, the Si wafer surface can be oxidized to increase the surface hydroxyl group density. Next, polystyrene (PS-OH) (concentration: 1.0 wt%) having a terminal end doped with a hydroxyl group dissolved in toluene is applied to the surface of the Si wafer using a spin coater (1H-360S manufactured by Mikasa Co., Ltd.). The film was formed under the condition of 1,000,000 rpm. Here, the molecular weight of PS-OH was 3700. The film thickness of the obtained PS-OH was about 50 nm. Next, the substrate coated with PS-OH was put into a vacuum oven and heated at 140 ° C. for 48 hours. By this treatment, the hydroxyl group at the PS-OH end is chemically bonded to the hydroxyl group on the substrate surface by a dehydration reaction. Finally, unreacted PS-OH was removed by immersing the substrate in toluene and sonicating to obtain a substrate having a PS graft layer.

  In order to evaluate the surface state of the PS graft substrate, the thickness of the PS graft layer, the amount of carbon on the substrate surface, and the contact angle of PS with the substrate surface were measured. Spectral ellipsometry was used to measure the thickness of the PS graft layer, and X-ray photoelectron spectroscopy (XPS method) was used to determine the amount of surface carbon.

  The contact angle of PS with respect to the substrate surface was measured by the following method. First, a thin film of homopolystyrene hPS having a molecular weight of 4000 was spin-coated on the surface of the substrate so as to have a thickness of about 80 nm. Next, the substrate on which hPS was formed was annealed at a temperature of 170 ° C. for 24 hours in a vacuum atmosphere. By this treatment, the hPS thin film was dewetting on the substrate surface to form fine droplets. After the heat treatment, the substrate was taken out of the heating furnace, immersed in liquid nitrogen, and rapidly cooled to freeze the shape of the droplet. The cross-sectional shape of the obtained droplet was measured with an atomic force microscope, and the contact angle of hPS with respect to the substrate at the heating temperature was determined by measuring the angle of the interface between the substrate and the droplet. At this time, the angle was measured for 6 points, and the average value was taken as the contact angle.

  As a result of measurement, the thickness of the graft layer on the surface of the substrate grafted with polystyrene was 5.1 nm. When the amount of carbon on the substrate surface before and after the polystyrene grafting was identified by XPS, the integrated intensity of the peak derived from C1S was 4,500 cps and 27,000 cps. The contact angle of hPS was 9 degrees, which was smaller than the contact angle of 35 degrees with respect to the Si wafer before grafting. From this, it was confirmed that a polystyrene graft film could be formed on the silicon wafer surface.

  The PS graft layer on the surface of the PS graft substrate was patterned by the EB lithography method to form a chemical pattern substrate in which circular regions of radius r where the Si wafer was exposed on the surface of the PS graft layer were arranged in a hexagonal manner with a lattice spacing d. The pattern arrangement on the prepared substrate is shown in FIG. On one substrate, regions (50 μm square) having hexagonal patterns having a lattice interval d different from 2 nm to 26 nm from 26 nm to 48 nm are continuously arranged. The radius r was about 25% to 30% of the lattice spacing d.

With reference to FIG. 4, the manufacturing process of a chemical pattern board | substrate is typically shown. First, a substrate obtained by dicing the 4 inch PS graft substrate prepared by the above method into a size of 2 cm square was prepared (FIG. 4B). Next, a PMMA resist was spin-coated on the surface so as to have a thickness of 85 nm (FIG. 4C). Next, the PMMA resist was exposed at an acceleration voltage of 100 kV using an EB drawing measure (FIG. 4D), and thereafter the PMMA resist was developed (FIG. 4E). Here, the radius r of the pattern was adjusted by the exposure amount of the electron beam at each lattice point. Next, using the patterned PMMA resist as a mask, the PS graft layer was etched by reactive dry etching (RIE) using oxygen gas (FIGS. 4F and 4G). The RIE process was performed using an ICP dry etch apparatus. The RIE conditions were an output of 40 W, an oxygen gas pressure of 4 Pa, a gas flow rate of 30 cm ³ / min, and an etching time of 5 to 10 seconds. Finally, the PMMA resist remaining on the substrate surface was removed with toluene to obtain a substrate having a PS graft layer patterned on the surface (FIG. 4H).

(Preparation of polymer block copolymer mixing system)
In this example, a polymer block copolymer mixture system obtained by blending PS-b-PMMA with homopolystyrene hPS having various molecular weights at various mixing ratios was used. Here, as PS-b-PMMA, PS having a number average molecular weight Mn of 46,100, PMMA having a number average molecular weight Mn of 21,000 and a molecular weight distribution (Mw / Mn) of 1.09 was used. This PS-b-PMMA expresses a structure in which cylinders made of PMMA are regularly arranged in a continuous phase made of PS by self-assembly. Table 1 shows the composition of the prepared confusion system.

(Measurement of natural period)
The natural period d ₀ of each polymer block copolymer mixture system (PS-b-PMMA / hPS) was determined by the following method. First, a PS-b-PMMA / hPS mixed system sample blended at a predetermined mixing ratio was dissolved in semiconductor grade toluene to obtain a PS-b-PMMA solution having a predetermined concentration of 1.0 wt%. Next, a PS-b-PMMA solution was applied to the surface of the silicon substrate to a thickness of 45 nm using a spin coater. Next, the substrate was annealed at 170 ° C. for 24 hours using a vacuum oven, and the microphase separation process was advanced to develop an equilibrium self-organized structure.

  The microphase separation structure in the PS-b-PMMA thin film formed on the substrate surface was observed using an atomic force microscope (AFM) and a scanning electron microscope (SEM).

AFM observation was performed after the sample surface was irradiated with UV light for 6 minutes in a nitrogen atmosphere. For UV light irradiation, a UV etching apparatus UV-1 manufactured by Samco Corporation having a 1 kVA high-pressure mercury lamp was used. Although the sample surface is etched by about 10 nm by this treatment, since the etching rate of the PMMA phase is larger than the etching rate of the PS phase, unevenness of several nanometers in depth reflecting the microphase separation structure near the surface is formed on the sample surface. It is formed. For AFM measurement, Nanoscope IIIa manufactured by Veeco Instruments was used, and height images and phase images were observed in tapping mode.
At this time, Olympus OMCL-AC160TS-W2 (cantilever length: 11 μm, spring constant: 42 N / m, resonance frequency: 300 kHz) was used for the probe.

A typical AFM observation image is shown in FIG. PS-b-PMMA / hPS on the surface of the substrate is often arranged in hexagonal locally with the cylinder standing upright with respect to the substrate. From the AFM observation image of such a structure (FIG. 11 (a)), The natural period d ₀ was determined. The determination of d ₀ was performed by two-dimensional Fourier transform of the AFM observation image using general-purpose image processing software. That is, as shown in FIG. 11B, the two-dimensional Fourier transform image of the cylinders arranged on the surface of the silicon substrate gives a halo pattern in which a large number of spots are gathered. Therefore, d ₀ is determined from the first halo radius. did.

Table 1 shows the d ₀ determined for each PS-b-PMMA / hPS.

(Chemical registration)
PS-b-PMMA / hPS was formed on the chemically patterned substrate surface to develop a microphase separation structure. The method is the same as that described above. The pattern shape in the obtained PS-b-PMMA / hPS thin film was observed with a scanning electron microscope.

SEM observation was carried out under the condition of an acceleration voltage of 0.7 kV using Hitachi S4800. A sample for SEM observation was prepared by the following method. First, the PMMA microdomain existing in the PS-b-PMMA thin film was decomposed and removed by an oxygen RIE method to obtain a polymer thin film having a nanoscale uneven shape derived from the microphase separation structure. RIE-10NP manufactured by Samco Corporation was used for RIE, and etching was performed for 10 seconds at an oxygen gas pressure of 1.0 Pa, a gas flow rate of 10 cm ³ / min, and a power of 10 W. In order to accurately measure the fine structure, the necessary contrast was obtained by adjusting the acceleration voltage without performing deposition of Pt or the like on the surface of the sample, which is usually performed for the prevention of charging in SEM observation.

A representative result is shown in FIG. First, FIG. 12A shows an SEM when the self-organization of PS-b-PMMA / hPS can be controlled by chemical registration. The position of the PMMA cylinder formed by PS-b-PMMA / hPS is constrained by selective wetting to the exposed Si wafer on the surface of the chemically patterned substrate, and the PS continuous phase formed by PS-b-PMMA / hPS. It can be seen that the regular structure formed by PS-b-PMMA / hPS is periodically arranged for a long distance without defects by selectively wetting the polystyrene graft surface of the patterned substrate surface. In contrast, FIGS. 12B and 12C show typical patterns when the self-organization control by chemical registration is incomplete. The SEM image shown in FIG. 12B is a structure often observed when the chemical pattern period d of the substrate and the natural period d _{0 of the} polymer are slightly deviated, and as a whole, the cylinder is in a fixed direction. However, a large number of regions and point defects in which the cylinder lies on the substrate are recognized. FIG. 12C shows an example in which the cylinders are randomly arranged without being substantially affected by the substrate.

  Table 1 summarizes the results of experiments conducted on PS-b-PMMA / hPS mixed systems having various compositions using substrates having hexagonal patterns having various periods d. In this table, “◎” indicates a state in which a pattern similar to FIG. 12A is obtained, and “◯” indicates a result in which a pattern similar to FIG. 12B is obtained. On the other hand, “x” indicates a state in which the influence of the chemical pattern substrate on the arrangement of the cylinders was not recognized as in FIG. In particular, when the molecular weight of hPS is large and the mixing amount of hPS is large, after the PS-b-PMMA / hPS is annealed, the macross is divided into a region containing PS-b-PMMA as a main component and a region containing hPS as a main component. Copic phase separation was observed. In this case, in the region mainly composed of PS-b-PMMA, it was observed that the cylinder array was oriented in one direction by the chemically patterned substrate, but there was no pattern of hPS on the substrate. It was observed that the region was distributed like islands in a region mainly composed of PS-b-PMMA. The pattern obtained when such a situation appears is not suitable for practical use. In Table 1, when such a situation occurs, “macro phase separation” is indicated.

From the results of Table 1, it can be seen that in the case of the PS-b-PMMA single system, the natural period d ₀ and the substrate pattern period d need to substantially coincide with each other in order to realize good chemical registration.

In contrast, in a system in which hPS having a molecular weight of 4,000 is mixed, the mixing amount of hPS is 5% by weight or more and 25% by weight or less, and the period d of the substrate pattern with respect to the natural period d ₀ of the polymer mixed system is It has been found that good chemical registration can be realized within the range of 0.9 to 1.3.

  As a result of conducting the same experiment with the molecular weight of hPS increased, it was found that when hPS had a molecular weight of 12,000, chemical registration could be realized in a condition range substantially equivalent to that of the molecular weight of 4,000. However, when the mixing amount of hPS was 30% by weight, the mixed system phase-separated macroscopically.

When the molecular weight of hPS was further increased to 36,000, the range in which good chemical registration could be realized became extremely small. That is, when the mixing amount of hPS was 15% by weight or more, the mixed system phase-separated macroscopically. Macroscopic phase separation was not observed when the mixing amount was 10% by weight or less, but good chemical registration was realized only when the period d of the substrate pattern was substantially the same as the natural period d ₀ . there were.

  In this experiment, a region having a hexagonal pattern with a different period d was formed on a single substrate. As described above, by using PS-b-PMMA / hPS having the composition defined in the present invention, the period d It was shown that different patterns can be formed at once. This result not only eliminates the need to adjust the concentration and composition of the polymer block copolymer mixture system used for each pattern size, but also supports patterns in which patterns of different sizes are mixedly mixed on the substrate surface. This result suggests that is possible.

  In this example, the method for producing a polymer thin film having the second microstructure of the present invention was carried out using a system in which two types of PS-b-PMMA having different molecular weights were mixed as a polymer block copolymer. The results of the study will be described with reference to comparative examples as appropriate.

  The four types of PS-b-PMMA used in the experiment are described in detail below. First, as the main component, the first PS-b-PMMA having a PS segment number average molecular weight Mn of 35,500 and a PMMA segment number average molecular weight Mn of 12,200 was used. The molecular weight distribution Mw / Mn as a whole of PS-b-PMMA was 1.04. The following three types of PS-b-PMMA were mixed and used as subcomponents at a weight fraction of 0 to 30% in this main component.

  Second PS-b-PMMA used as subcomponent: Number average molecular weight Mn of PS segment: 52,000, Number average molecular weight Mn of PMMA segment: 52,000, Molecular weight distribution: 1.10.

  Third PS-b-PMMA used as an accessory component: number average molecular weight Mn of PS segment: 46,100, number average molecular weight Mn of PMMA segment: 21,000, molecular weight distribution: 1.09.

  Fourth PS-b-PMMA used as subcomponent: number average molecular weight Mn of PS segment: 12,800, number average molecular weight Mn of PMMA segment: 12,900, molecular weight distribution: 1.05.

Here, the first PS-b-PMMA has a molecular weight of 35,000 for the PS segment and a molecular weight of 12,000 for the PMMA segment, so that the cylinders made of PMMA are arranged in a continuous phase made of PS. A phase separation structure is formed. In the first PS-b-PMMA, the molecular weight of the PS segment is larger in the PMMA segment. Therefore, Mw (A2)> Mw (A1) and Mw (B2)> Mw (A2), which are the prescribed ranges of the composition of the second polymer block copolymer composition in the present invention.
In order to satisfy this relationship, the molecular weight of the PS segment as a subcomponent must be greater than 35,000. The second and third PS-b-PMMA satisfy this condition, but the fourth PS-b-PMMA does not satisfy this condition.

Using these PS-b-PMMA mixed systems, experiments were performed in the same manner as in Example 1.
Here, the film thickness of the PS-b-PMMA mixed system was set to 35 nm. Further, the period d of the chemical pattern substrate was changed at a pitch of 2 nm in the range of 24 nm to 46 nm. The results obtained are summarized in Table 2. In this table, “◎” indicates a state in which a pattern similar to FIG. 12A is obtained, and “◯” indicates a result in which a pattern similar to FIG. 14B is obtained. On the other hand, “x” indicates a state in which the influence of the chemical pattern substrate on the arrangement of the cylinders was not recognized as in FIG.

From the results shown in Table 2, it was found that in the case of the PS-b-PMMA single system, the natural period d ₀ and the substrate pattern period d need to substantially coincide with each other in order to realize good chemical registration. .

  On the other hand, when the third PS-b-PMMA is mixed as an auxiliary component, the sample whose mixing ratio is 10 wt% and 20 wt% has a pattern period d of 0.9 to 1.3. It was found that good chemical registration can be realized within the range.

  In addition, when the second PS-b-PMMA was mixed as a subcomponent, it was tested only when the mixing ratio was 10% by weight. However, the pattern period d should be in the range of 0.9 to 1.3. It was found that good chemical registration can be realized.

On the other hand, when the fourth PS-b-PMMA is mixed, even when the mixing ratio is 10% by weight, a good chemical registration is obtained only when the pattern period d is substantially equal to the natural period d ₀ . It turns out that it can be realized.

  In this experiment, a region composed of hexagonal patterns having different periods d was formed on one substrate. As described above, by using a PS-b-PMMA mixed system having the composition defined in the present invention, the period d It was shown that different patterns can be formed at once. This result not only eliminates the need to adjust the concentration and composition of the polymer block copolymer mixture system used for each pattern size, but also supports patterns in which patterns of different sizes are mixedly mixed on the substrate surface. This result suggests that is possible.

  Next, the Example which manufactured the pattern board | substrate is shown. First, an example in which the columnar phase in the polymer thin film C is decomposed and removed to form a porous thin film on the surface of the substrate in accordance with the steps shown in FIGS.

According to the procedure of Example 1, a polymer thin film having a structure in which the columnar phase B made of PMMA was upright with respect to the film surface (oriented in the penetration direction of the film) was formed on the substrate surface. Here, the arrangement shown in FIG. 10 was applied to the pattern arrangement as in the first embodiment. Moreover, as a polymer block copolymer composition, the number average molecular weight Mn of PS is 46,100 and the number average molecular weight Mn of PMMA is 21,5 as PS-b-PMMA as the main component, as in Example 1. 000 and a molecular weight distribution (Mw / Mn) of 1.09 were used. Further, hPS having a Mn of 4000 was used.
PS-b-PMMA / hPS was mixed so that hPS was 15% by weight.

  By applying PS-b-PMMA / hPS to a chemical pattern substrate to a film thickness of 45 nm and subjecting it to thermal annealing, microphase separation is manifested, and the cylinder made of PMMA is regular in the continuous phase made of PS. The structure arranged in is obtained. Next, an operation of removing the PMMA phase by RIE was performed to obtain a porous thin film D. Here, the gas pressure of oxygen was 1 Pa, and the output was 20 W. The etching processing time was 90 seconds.

  The surface shape of the produced porous thin film D was observed using a scanning electron microscope.

  As a result, it was confirmed that columnar fine holes H were formed in the porous thin film D over the entire surface and oriented in the penetration direction of the film. Here, the diameter of the micropore H was about 18 nm. Furthermore, as a result of detailed analysis of the arrangement state of the micropores H in the obtained porous thin film D, the micropores H are not defective in the region where the surface is chemically patterned in the range of the period d = 30 to 36 nm. It can be seen that they are arranged in a hexagonal state in a state oriented in the direction. On the other hand, although the micropores H are microscopically arranged in a region that is not chemically patterned or in a region where the chemical pattern period d is 26 nm or less, or 42 nm or more, it is macroscopic. In particular, it was found that the hexagonal region formed grains, and there were many lattice defects in the grain interface region.

  Here, a part of the thickness of the porous thin film D was peeled off from the surface of the substrate 20 with a sharp blade, and the level difference between the surface of the substrate 20 and the surface of the porous thin film D was measured by AFM observation. Met.

  The aspect ratio of the obtained micropore H is 2.6, and a large value that cannot be obtained with a spherical microdomain structure is realized. The reason why the film thickness of the polymer thin film C was 45 nm before the RIE was reduced to 40 nm is considered that the PS continuous phase A was slightly etched together with the PMMA phase by the RIE.

Next, the porous thin film D was transferred to the substrate by etching the silicon substrate 20 using the porous thin film D as a mask. Here, the etching was performed by dry etching with CF ₄ gas. As a result, the shape and arrangement of the fine holes H in the porous thin film D were successfully transferred to the silicon substrate.

10, 20 Substrate 11 Polymer resin composition 12 Chemically modified layer 13 Resist film 21, 31 Pattern substrate 30 Transferred object 32 Columnar body

Claims (6)

A first step of disposing a polymer layer comprising a polymer block copolymer composition on a substrate surface;
A second step of microphase separation of the polymer layer, and a method for producing a polymer thin film having a microstructure,
The polymer block copolymer composition is:
The main component is a polymer block copolymer A composed of at least a polymer block chain A1 having a molecular weight Mn (A1) and a polymer block chain A2 having a molecular weight Mn (A2).
A polymer block chain B1 having a molecular weight Mn (B1) that is compatible with the first polymer phase mainly composed of the polymer block chain A1, and a second polymer mainly composed of the polymer block chain A2. A polymer block copolymer B composed of a polymer block chain B2 having a molecular weight Mn (B2) compatible with the phase is blended as a subcomponent,
Mn (A1), Mn (A2), Mn (B2) have the following relationship:
Mn (A2)> Mn (A1) and Mn (B2)> Mn (A2)
The substrate surface has a first surface in which an interfacial tension with the first polymer phase is smaller than an interfacial tension with the second polymer phase, and an interfacial tension with the second polymer phase is The second surface, which is smaller than the interfacial tension with the first polymer phase, is discretely arranged, and there are at least two types of the period ds of the second surface,
The microstructure includes a region in which microdomains mainly composed of the polymer block chain A1 are regularly arranged in a matrix polymer phase mainly composed of the polymer block chain A2.
There are at least two kinds of regular arrangement periods d in the region, and the period d and the natural period d ₀ of the polymer block copolymer composition are 0.9 × d ₀ <d <1.3. A method for producing a polymer thin film, characterized by having a relationship of × d ₀ .   The polymer block chain A1 and the polymer block chain B1 have the same chemical structure, and the polymer block chain A2 and the polymer block chain B2 have the same chemical structure. Item 2. A method for producing a polymer thin film according to Item 1.   The method for producing a polymer thin film according to claim 1, wherein the microstructure includes a region in which columnar polymer phases are regularly arranged in a matrix polymer phase.   The method for producing a polymer thin film according to claim 1, wherein the microstructure includes a region in which plate-like polymer phases are regularly arranged.   2. The microstructure includes a region in which columnar polymer phases are regularly arranged in a matrix polymer phase and a region in which plate-like polymer phases are regularly arranged. A method for producing the polymer thin film according to 1.   2. The production of the polymer thin film according to claim 1, wherein a weight fraction occupied by the polymer block copolymer A is 75% or more and 95% or less with respect to the polymer block copolymer composition. Method.

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