JP2010056256A - Polymer thin film with microstructure, and method of manufacturing pattern substrate - Google Patents

Polymer thin film with microstructure, and method of manufacturing pattern substrate Download PDF

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JP2010056256A
JP2010056256A JP2008218958A JP2008218958A JP2010056256A JP 2010056256 A JP2010056256 A JP 2010056256A JP 2008218958 A JP2008218958 A JP 2008218958A JP 2008218958 A JP2008218958 A JP 2008218958A JP 2010056256 A JP2010056256 A JP 2010056256A
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substrate
segment
pattern
microdomain
block copolymer
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JP4654279B2 (en
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Yasuhiko Tada
Hiroshi Yoshida
博史 吉田
靖彦 多田
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Hitachi Ltd
株式会社日立製作所
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Abstract

<P>PROBLEM TO BE SOLVED: To provide a method of manufacturing a microstructure in which microdomain structures can be formed by a chemical registration method in an arbitrary pattern arrangement or at intervals different from a characteristic period do of microdomains of a high molecular block copolymer. <P>SOLUTION: In the method of manufacturing the microstructure including a first step of arranging a high molecular polymer layer containing a high molecular block copolymer composition having a first segment and a second segment on a substrate surface, and a second step of subjecting the polymer layer to micro-phase separation and developing a structure including a columnar microdomain consisting principally of the first segment and a continuous phase consisting principally of the second segment, the substrate surface is chemically patterned, and a film thickness t of the polymer thin film arranged in the first step and the characteristic period do of microdomains that the high molecular block polymer forms have a relation of (m+0.8)×do<t<(m+1.2)×do, where m is an integer not less than 0. <P>COPYRIGHT: (C)2010,JPO&INPIT

Description

  The present invention relates to a method for producing a microstructure having a microstructure in which a polymer block copolymer is microphase-separated on a substrate surface. The present invention also relates to a method for manufacturing a patterned substrate having the microdomain regular pattern on its surface.

  In recent years, with the miniaturization and high performance of electronic devices, energy storage devices, sensors, and the like, 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. In addition, when it becomes difficult to form a fine pattern using a mask, the direct drawing method must be applied. However, even when the direct drawing method is used, when a dot pattern having a diameter of 10 nm or less is drawn, the diameter and shape vary.

  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 the different polymer segments constituting the polymer block copolymer do not mix with each other (incompatible), the polymer segments have specific regularity due to phase separation (microphase separation). The microstructure 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.

  As described above, according to the microphase separation phenomenon of the polymer block copolymer, a structure in which fine spherical, columnar or plate-like (lamellar) microdomains that are difficult to achieve with a top-down method are regularly arranged. 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, the self-assembly by the polymer block copolymer is that it is difficult to control the microdomain structure at an arbitrary arrangement and interval. 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 three methods have been devised so far to overcome these drawbacks.

  First, as a first conventional technique, the molecular weight of any polymer segment of the polymer block copolymer is increased. According to this method, the interval between the columnar microdomains can be further increased. However, in the first conventional method, increasing the molecular weight of only one polymer segment changes the volume ratio with the other polymer segment, so the shape of the microdomain changes, and an arbitrary pattern shape is obtained. It cannot be formed at arbitrary intervals. Further, if a pattern is formed at an arbitrary pattern interval while keeping the volume ratio constant, the size of the microdomain is different from the desired size.

  As a second conventional technique, there is a technique of adjusting a pattern interval by mixing polymers having the same composition as one polymer segment in the microdomain structure formed by the polymer block copolymer. . According to this method, the pattern interval can be adjusted without changing the pattern size of the microdomain. On the other hand, in the second conventional method, it becomes difficult to obtain a desired microdomain structure when the mixing ratio of the polymer increases.

  Furthermore, in the first and second methods, it is difficult to form a microdomain structure with an arbitrary arrangement.

  As a third conventional technique, there is a method of chemically patterning the substrate surface and controlling the structure developed by microphase separation by chemical interaction between the substrate surface and the polymer block copolymer (for example, 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 deposited to develop microdomains.

  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 microdomain of the polystyrene-polymethylmethacrylate diblock copolymer, the microdomain made of polystyrene is formed on the region having good affinity with polystyrene at the time of microphase separation. 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 becomes possible to arrange the microdomains along marks that are 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 the chemical registration method, a chemical pattern is formed on the substrate, so that columnar microdomain structures can be placed on the chemical pattern, and the arrangement of the microdomain structures and the spacing between the domain structures are controlled. Is possible.

USP 6,746,825, B2 USP 6,926,953, B2

  However, when the chemical pattern is arranged, if the pattern interval is larger than the natural period of the microdomain structure formed by the polymer block copolymer, the columnar microdomains on the substrate other than the part where the chemical pattern is formed are also present. In some cases. Therefore, it is difficult to form a pattern with an arbitrary arrangement and interval.

  The present invention can form a micro domain structure with an arbitrary pattern arrangement or interval different from the natural period do of the micro domain of the polymer block copolymer in the manufacturing method of the fine structure using the chemical registration method. It aims at providing the manufacturing method of a fine structure. In particular, the present invention provides a method of arranging columnar microdomain structures having a desired diameter on a substrate at arbitrary pattern intervals. Furthermore, the present invention provides a method for producing a patterned substrate using a polymer thin film having a microstructure formed by this method.

  In order to solve the above-described problems, the present invention provides a first stage in which a polymer layer including a polymer block copolymer composition having at least a first segment and a second segment is disposed on a substrate surface; In a method of manufacturing a microstructure having phase separation and a second stage in which a structure formed from a columnar microdomain having the first segment as a main component and a continuous phase having the second segment as a main component is expressed. The substrate surface has an interfacial tension with the first segment larger than or substantially equal to an interfacial tension with the second segment, the first pattern member discretely disposed on the substrate surface, and the first segment; A second pattern member having an interface tension smaller than the interface tension with the second segment, and the film thickness t of the polymer thin film disposed in the first stage, Characterized in that the natural period do microdomains molecular block copolymer is formed with the following relationships.

(M + 0.8) × do <t <(m + 1.2) × dom is an integer greater than or equal to 0 Further, the method for manufacturing a 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 through the remaining polymer phase and the microphase separation pattern is transferred to the surface of the substrate, or the other polymer layer remaining is transferred to the pattern substrate. Manufacturing. Furthermore, a patterned substrate is manufactured by doping one of the polymer layers manufactured by the manufacturing method of the polymer thin film or the patterned substrate.

  Note that the microstructure in the present invention refers to a structure in which a polymer thin film having microdomains is formed on a substrate surface. In addition, the pattern substrate in the present invention is a microdomain regular pattern of such a fine structure, which is transferred on the surface in a concavo-convex shape, whether it is an original or a copy thereof. Absent.

  According to the present invention, columnar microdomains having a desired diameter formed by microphase separation of a polymer block copolymer can be oriented in a direction perpendicular to the substrate at any arrangement or interval.

  Moreover, the manufacturing method of the pattern board | substrate which has this pattern on the surface can be provided. Furthermore, it is possible to provide a pattern transfer body such as an etching mask that can obtain a fine regular arrangement pattern with a large aspect ratio on the surface of an object (transfer body).

  Embodiments of the present invention will be described below with reference to the drawings. In addition, although the following description mainly describes columnar micro domain, it can implement also about a lamellar micro domain by the same method.

  FIG. 2 shows a manufacturing process (chemical registration process) of a polymer thin film having a structure in which columnar microdomains according to the present invention stand upright on a substrate. Each process will be described in detail later.

  FIG. 2A shows a substrate for forming a polymer thin film having a structure in which columnar microdomains stand upright on the substrate 201. Next, as shown in FIG. 2B, this substrate is patterned into a surface 1 (202) (first pattern member) and a surface 2 (203) (second pattern member) having different chemical properties. . As shown in FIG. 2C, a polymer block copolymer is formed on the substrate surface so as to have a predetermined film thickness. As shown in FIG. 2D, the polymer block copolymer is microphase-separated to form a fine structure composed of a first segment and a second segment. Finally, as shown in FIG. 2E, a polymer thin film having a fine structure can be formed by removing the polymer block chain on one side.

  At this time, the first material constituting the first segment has better wettability than the second material constituting the second segment with respect to the surface 1 prepared in the stage shown in FIG. Design the chemical state of surface 1 and surface 2 so that the second material constituting the second segment has better wettability than the second material constituting the first segment, and control the film thickness within a predetermined range. Then, the first segment and the second segment are arranged on the surface 1 and the surface 2 as shown in FIG. Further, when the wettability is expressed by the interfacial tension, the interfacial tension between the surface 1 and the first segment is greater than or substantially equal to the interfacial tension with the first segment, and the interfacial tension between the first segment and the second segment. The surface 2 may be smaller than the tension. The relationship between the wettability or interfacial tension of the first surface, the second surface, the first segment of the polymer block copolymer, and the second segment of the substrate 201 is related to the phase separation of the polymer block copolymer. It is only necessary to satisfy the above-described relationship in the temperature at which the expression is performed. By setting it as such a relationship, it can be set as the structure where the 1st segment on the 1st surface and the 2nd segment were regularly arranged on the 2nd surface.

Further, in the process of FIG. 2C, the relationship between the film thickness t of the polymer thin film and the natural period do of the fine structure formed by the microphase separation of the polymer block copolymer in the bulk state,
(M + 0.8) × do <t <(m + 1.2) × dom is preferably an integer of 0 or more. By setting it as the said relationship, it can suppress that a columnar micro domain orientates in the orthogonal | vertical direction with respect to a board | substrate in the area | region where the surface 1 is not formed. Thus, by controlling the arrangement of the surface 1, columnar microdomains having a desired diameter can be formed at an arbitrary arrangement or interval.

  Note that the microdomains formed in the polymer thin film in FIGS. 1 and 2 exemplify columnar microdomains oriented in the penetration direction of the film. However, as described above, the microdomain of the microstructure in the present invention is not limited to such a columnar form. That is, it can be considered that all microdomains expressed by the polymer block copolymer are included, for example, have a lamellar lamellar form.

  Similarly, in FIG. 1 and FIG. 2, the continuous phase formed in the polymer thin film is exemplified such that regular patterns of columnar microdomains oriented in the penetration direction of the film are uniformly dispersed. However, the continuous phase of the microstructure in the present invention is not limited to such a form. In other words, as long as it is formed in a region sharing a boundary with microdomains that can take various forms as described above, it is defined as a continuous phase.

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

(High molecular block copolymer)
When the columnar microdomain structure is used, it is desirable that the polymerization degree of the first segment in the polymer block copolymer is smaller than the polymerization degree of the second segment, and that the molecular weight distribution of the polymer block copolymer is narrow. By adjusting the degree of polymerization, the boundary between the first segment and the second segment becomes easy to take a cylindrical shape, and the continuous phase region composed of the second segment and the columnar micro consisting mainly of the first segment. Domain regions are formed. When applying a lamellar microdomain structure, the polymerization degree of the second segment in the polymer block copolymer and the polymerization degree of the first segment may be adjusted to be equal.

  Examples of the polymer block copolymer that satisfies the above conditions include polystyrene-block-polymethyl methacrylate copolymer (PS-b-PMMA) and polystyrene-block-polydimethylsiloxane (PS-b-PDMS). However, the present invention is not limited to these polymer block copolymers, and can be widely used as long as the combination exhibits microphase separation.

  The polymer block copolymer may be synthesized by an appropriate method, but in order to improve the regularity of the microdomain, a synthesis method having a molecular weight distribution as narrow as possible is preferable. Examples of applicable synthesis methods include living polymerization methods.

  Further, as the polymer block copolymer in the present embodiment, an AB type polymer diblock copolymer formed by bonding the ends of the first segment and the second segment is exemplified. However, the polymer block copolymer used in this embodiment is not limited to such a form, and is an ABA polymer triblock copolymer, an 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.

  Now, the polymer block copolymer composition of the present invention exhibits a structure of columnar microdomains by microphase separation. As described above, the size is determined according to the molecular weight of the polymer block copolymer. That is, the size at which the polymer block copolymer is expressed is unique depending on the molecular weight of the polymer constituting the polymer block copolymer. Here, a period of a regular structure that appears by microphase separation is defined as a natural period do301. When the microdomains are columnar, the columnar microdomains are regularly arranged by packing into hexagonal as shown in FIG. In this case, the natural period do is defined by the lattice spacing of a hexagonal array. When the microdomain is lamellar, the lamella 302 is packed in parallel and regularly arranged as shown in FIG. In this case, the natural period do is defined by the interval between lamellae. The natural period do 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 present invention, as shown in FIG. 2 (b), the surface of the substrate is patterned into surfaces 1 and 2 having different chemical properties, and the first segment formed by the polymer block copolymer is formed on each surface. The microdomain is controlled by arranging the microdomain composed of the domain and the second segment. Here, a method for patterning the substrate surface into the surface 1 and the surface 2 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 the main component constituting the polymer block copolymer, is PS-b-PMMA, and by microphase separation, a microdomain having polystyrene (PS) as a main component, This is based on the premise that a microdomain mainly composed of polymethyl methacrylate (PMMA) is developed.

  First, as shown in FIG. 4A, the substrate surface is chemically modified in order to make the entire surface of the substrate easier to wet with PS than with PMMA. For chemical modification, a method such as monomolecular film formation by silane coupling or polymer grafting may be used. In order to make the surface of the substrate more easily wettable by PS, for example, in the case of monomolecular film formation, introduction of a phenethyl group by a coupling reaction of phenethyltrimethoxysilane, or in the case of polymer modification, PS and A compatible polymer may be introduced onto the substrate surface by grafting. The term “easy to get wet” here means that the interfacial tension is larger.

  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 ° C. 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. However, when 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 401 provided on the substrate surface is patterned with a desired pattern arrangement and interval. 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 401 is formed on the surface of the substrate (FIG. 4A) (FIG. 4B), and a resist film 402 is formed on the surface (FIG. 4C). ), Patterning the resist film by exposure 403 (FIG. 4D), and developing process 404 (FIG. 4E), patterning the resist, and then chemically modifying the layer by a technique such as oxygen plasma treatment May be patterned by etching (FIG. 4F). Finally, if the resist film on the remaining chemically modified layer is removed, a patterned chemically modified layer is obtained (FIG. 4G). 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. Therefore, as a result, polystyrene-based microdomains and polymethylmethacrylate-based microdomains expressed by the polymer block copolymer mixture based on PS-b-PMMA are selected. A characteristic surface 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.

(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 weight concentration of the solution is generally set to several percent so that the thickness of the coating film 204 shown in FIG. 2C is a predetermined value, and the rotation speed of the spin coating is 1000 to 5000 rotations. Then, a polymer block copolymer composition thin film having a film thickness of several tens of nm can be stably obtained.

  Next, the solvent is volatilized from the solution of the polymer block copolymer composition to fix the coating film 204 on the surface of the substrate 200. By the way, the thickness t of the coating film may be arbitrarily adjusted, but in order to align the columnar microdomains perpendicularly to the substrate at a desired position, (m + 0.8) × d <t <(m + 1.2). ) × d (m is an integer greater than or equal to 0). The integer of m is not particularly limited as to the upper limit. In order to maintain the columnar microdomains upright perpendicular to the substrate and maintain the desired pattern shape, the natural period of the polymer block copolymer composition is not limited. It is desirable to be an integer of about 5 times or less of do, that is, an integer between 0 and 5.

  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. This annealing treatment is preferably performed in a vacuum, nitrogen or argon atmosphere in order to prevent oxidation of the polymer block copolymer. 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.

  By the above method, a polymer thin film having a pattern in which a columnar microdomain structure is formed at a desired position by the microdomain as shown in FIG. 2E is formed on the substrate 201, and the microstructure 207 is manufactured. That's right.

  The continuous phase 206 as shown in FIG. 2 (d) is composed of a polymer block copolymer, and the columnar microdomains are parallel to the substrate, or oriented on the surface 1 perpendicular to the substrate. And a structure surrounding the columnar microdomain, or a structure in which the polymer segment constituting the columnar microdomain is inverted. However, the structure in the continuous phase 206 is not limited to these, and the surface 2 and the second segment may be in contact with each other.

(Chemical registration)
Representative examples in which the columnar microdomain spacing is adjusted according to the present invention are shown below. The pattern that has become possible when the natural period of the columnar microdomain formed by the polymer block copolymer is do will be described with reference to FIG.

  FIG. 6A shows a pattern in which the columnar microdomains are arranged on the entire surface of the substrate with a period do in a state where the columnar microdomains stand upright on the substrate. Since this pattern has the same period do as the natural period do of the polymer block copolymer, the conventional chemical registration method can be used.

  FIG. 6B shows a pattern in which the columnar microdomains are aligned perpendicularly to the substrate and arranged hexagonally across the front surface of the substrate at 1.3 times the natural period of the polymer block copolymer. This pattern could be dealt with by a conventional chemical registration method.

  FIG. 6C shows a pattern in which the columnar microdomains are aligned in the hexagonal state over the entire surface of the substrate at twice the natural period of the polymer block copolymer with the columnar microdomains oriented perpendicularly to the substrate. This pattern is realized by forming a chemical pattern in advance at the position where the columnar microdomains in FIG. 6C are oriented perpendicular to the substrate and controlling the film thickness of the polymer block copolymer. The

  FIG. 6 (d) shows a pattern in which the columnar microdomains are aligned on the front surface of the substrate with hexagonal three times the natural period of the polymer block copolymer with the columnar microdomains oriented perpendicular to the substrate. This pattern is realized by forming a chemical pattern in advance at the position where the columnar microdomains in FIG. 6D are oriented perpendicular to the substrate and controlling the film thickness of the polymer block copolymer. The

  Although not shown, the regularity of the chemical pattern is not particularly limited, and a plurality of pattern intervals may be mixed on the same substrate.

Further, the distance d between the chemical patterns is not particularly defined,
d = do × (n ± 0.3) It is desirable that n satisfies a natural number relationship.

(About pattern substrates)
Next, with reference to FIG. 7, various methods for producing a patterned substrate using the microdomains of the polymer block copolymer composition will be described. In FIG. 7, 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 an uneven surface corresponding to a regular arrangement pattern of microdomains is formed.

  First, in the microdomain shown in FIG. 7 (a), a porous polymer in which a polymer phase on one side is selectively removed and a plurality of micropores H form a regular arrangement pattern as shown in FIG. 7 (b). A thin film D 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. 7B, the other remaining polymer phase (in the figure, the porous thin film D composed of the continuous phase A) is peeled off from the surface of the substrate 200, and the single porous thin film D is separated. Can be manufactured as a pattern substrate.

  By the way, as shown in FIG. 7B, as a method for selectively removing one of the continuous phase A and 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.

  Thus, as a polymer block copolymer capable of forming a polymer thin film capable of selectively removing only one of the polymer phases, for example, polybutadiene-polydimethylsiloxane, polybutadiene-4-vinylpyridine, polybutadiene- Methyl methacrylate, polybutadiene-poly-t-butyl methacrylate, polybutadiene-t-butyl acrylate, poly-t-butyl methacrylate-poly-4-vinylpyridine, polyethylene-polymethyl methacrylate, poly-t-butyl methacrylate-poly-2- Vinylpyridine, polyethylene-poly-2-vinylpyridine, polyethylene-poly-4-vinylpyridine, polyisoprene-poly-2-vinylpyridine, polymethyl methacrylate-polystyrene, poly-t-butyl methacrylate -Polystyrene, polymethylacrylate-polystyrene, polybutadiene-polystyrene, polyisoprene-polystyrene, polystyrene poly-2-vinylpyridine, polystyrene poly-4-vinylpyridine, polystyrene polydimethylsiloxane, polystyrene poly-N, N-dimethylacrylamide, polybutadiene -Sodium polyacrylate, polybutadiene-polyethylene oxide, poly-t-butyl methacrylate-polyethylene oxide, polystyrene polyacrylic acid, polystyrene polymethacrylic acid, etc.

  It is also possible to improve etching selectivity by doping metal atoms or the like into one of the polymer phases of the continuous phase 10 or the columnar microdomain 20. 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. 7C and 7D, another example of the method for manufacturing a patterned 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. 7B as a mask. Then, as shown in FIG. 7C, 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 is changed to 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 by 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. 7 (e) and 7 (f), another embodiment relating to a method for manufacturing a patterned substrate will be described.

  The other polymer phase (porous thin film D) remaining like the continuous phase A shown in FIG. 7 (b) is brought into close contact with the transfer medium as shown in FIG. Is transferred to the surface of the transfer target. Thereafter, as shown in FIG. 7 (f), the transferred body is peeled from the pattern substrate to obtain a replica (pattern substrate) 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 the micro domain, 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.

  As described above, the embodiment of the present invention has been described focusing on the columnar microdomain structure. However, as described above, the present invention can also be applied to a lamellar microdomain structure.

  In this example, regarding the method for producing a polymer thin film having the first microstructure according to the present invention, the results of studies conducted using PS-b-PMMA forming a columnar microdomain structure as a polymer block copolymer are shown. The explanation will be made with reference to the comparative examples as appropriate.

(Preparation of chemically patterned substrate)
The substrate is a Si wafer with a natural oxide film. After grafting polystyrene on the entire surface, the polystyrene graft layer is patterned by electron beam (EB) lithography to achieve different wettability to polystyrene and polymethylmethacrylate. 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, on the surface of the Si wafer, polystyrene (PS-OH) (concentration: 1.0 wt%) terminated with a hydroxyl group dissolved in toluene was spin-coated using a spin coater (1H-360S manufactured by Mikasa Corporation). The film was formed under the condition of 3,000 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 homopolystyrene (hPS) thin film 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. A region (100 μm square) having a hexagonal pattern with a lattice interval d is continuously arranged on one substrate. The radius r was about 25% to 30% of the value obtained by multiplying the natural period do of the polymer block copolymer by 2 / √3.

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 with an acceleration voltage of 100 kV using an EB lithography measure (FIG. 4D), and then the PMMA resist was developed (FIG. 4E). Here, the diameter 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 (FIG. 4F). 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. 4G). Note that the resist used for EB lithography is not limited to a PMMA resist, and is not particularly limited as long as a good resolution can be obtained. Further, the solvent for removing the PMMA resist is not limited to toluene, and may be any good solvent for the PMMA resist, and is not particularly limited.

(Measurement of natural period)
The natural period do of the polymer block copolymer (PS-b-PMMA) was determined by the following method. As the polymer block copolymer PS-b-PMMA used, PS (46k) -b-PMMA (12k) having a PS chain number average molecular weight (Mn) of 46,100 and a PMMA chain Mn of 21,000 is used. Using. First, a PS-b-PMMA solution having a predetermined concentration of 1.0 wt% was obtained by dissolving a PS-b-PMMA sample in semiconductor grade toluene. Next, the 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.

  Microdomains in the PS-b-PMMA thin film formed on the substrate surface were observed using a scanning electron microscope (SEM).

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, a PMMA microdomain present in the PS-b-PMMA thin film was decomposed and removed by an oxygen RIE method, thereby obtaining a polymer thin film having a nanoscale uneven shape derived from the microdomain. RIE-10NP manufactured by Samco Corporation was used for RIE, and etching was performed for 30 seconds at an oxygen gas pressure of 1.0 Pa, a gas flow rate of 10 cm 3 / min, and a power of 20 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 typical SEM observation image is shown in FIG. PS-b-PMMA on the substrate surface has columnar microdomains standing upright with respect to the substrate and is often locally arranged in a hexagonal manner. From an SEM observation image of such a structure (FIG. 9A), The natural period do was determined. The determination of do was performed by two-dimensional Fourier transform of the SEM observation image using general-purpose image processing software. That is, as shown in FIG. 9B, the two-dimensional Fourier transform image of the columnar microdomain arranged on the surface of the silicon substrate gives a halo pattern in which a large number of spots are gathered. Therefore, do is calculated from the first halo radius. Upon determination, it was found that do = 32 nm.

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

  A typical result is shown in FIG. On a substrate chemically patterned with a period d = 32 nm and 61 nm, PS (46k) -b-PMMA (21k) is applied with a film thickness of 32 nm for a period of 32 nm and with a film thickness of 32 nm and 45 nm for a period of 61 nm. FIG. 10 shows an SEM observation result in which the self-organization is performed and the columnar microdomains are oriented perpendicularly to the substrate at a desired pattern interval. FIG. 10A shows that the position of the PMMA columnar microdomain formed by PS-b-PMMA is constrained by selective wetting of the exposed portion of the Si wafer on the surface of the chemically patterned substrate. The PS continuous phase to be formed wets selectively to the polystyrene graft surface of the patterned substrate surface. Furthermore, when patterning is performed at a period of 61 nm, which is about twice the natural period do, and self-organization is performed at a film thickness of 32 nm, the portion patterned from the contrast ratio in FIG. It was confirmed that a domain was formed and a continuous layer made of PS was formed between the patterns on the substrate surface. Further, when patterning is performed with a period 61 nm which is about twice the natural period do and self-organization is performed with a film thickness of 45 nm, the polymer block copolymer has a natural period of 32 nm on the substrate as shown in FIG. Columnar microdomains were formed and the desired pattern was not obtained.

(Comparative Example 1)
When patterns are arranged at intervals equal to or greater than the natural period do of PS-b-PMMA as in Example 1, a self-assembled film is formed after adjusting the film thickness on a chemically patterned substrate. In this case, as shown in FIG. 10B, it was recognized that the columnar microdomains were oriented perpendicular to the substrate at a desired pattern interval. Therefore, the following experiment was performed in order to confirm the influence of the film thickness of PS-b-PMMA.

  The substrate of PS (46k) -b-PMMA (21k) with various film thicknesses is obtained by the same method as the self-organization of PS (46k) -b-PMMA (21k) on the chemically patterned substrate. A microdomain was developed by forming a film on the surface of 200 and performing heat treatment. By decomposing and removing the PMMA microdomains present in the obtained PS-b-PMMA thin film by the oxygen RIE method, a polymer thin film having a nanoscale uneven shape derived from the microdomains was obtained. The obtained polymer thin film was observed by SEM.

  Table 1 shows the formation results of patterns with various film thicknesses on chemical patterns of PS (46k) -b-PMMA (21k) with periods of 32 nm and 61 nm. In this table, “◯” indicates a state where a pattern similar to FIG. 10A is obtained, “「 ”indicates a state where a pattern similar to FIG. 10B is obtained, and“ × ”indicates a state where FIG. The state where the same pattern as c) was obtained is shown.

  From the results in Table 1, in the case of a period of 61 nm, pattern formation at a desired pattern interval was recognized in the range of film thickness t of 0.8 × do <t <1.2 × do.

  From the above results, in order to form a pattern in which columnar microdomains made of PMMA are vertically oriented at an arbitrary pattern interval on the substrate, chemical patterning is performed on the substrate at a desired pattern interval, and the film thickness is increased. It has been demonstrated that the adjustment may be made so as to satisfy the relationship of (0.8 + m) × do <t <(1.2 + m) × do (m is an integer of 0 or more).

  Experiments were performed according to the steps described in Example 1 except that the polymer block copolymer was changed to that described below.

  As the polymer block copolymer, PS-b-PMMA having a PS number average molecular weight Mn of 35,500 and a PMMA Mn of 12,200 was used. The natural period do was obtained in the same manner as in Example 1 and found to be 24 nm. According to this value, a hexagonal pattern with d = 24 nm, 48 nm, and 72 nm was chemically patterned on the substrate, and the polymer block co-polymerized with a film thickness of 25 nm. The coalescence was applied and heat treatment was performed to develop microdomains. By decomposing and removing the PMMA microdomains present in the obtained PS-b-PMMA thin film by the oxygen RIE method, a polymer thin film having a nanoscale uneven shape derived from the microdomains was obtained. The obtained polymer thin film was observed by SEM. As a result, it was confirmed that a columnar microdomain structure was formed at a chemically patterned position, and it was recognized that patterning was possible at a desired position.

  In this example, the results of studies conducted using PS-b-polydimethylsiloxane (PDMS) as a polymer block copolymer for the method for producing a polymer thin film having the first microstructure of the present invention will be described. . Experiments were performed according to the steps described in Example 1 except that the polymer block copolymer was changed to PS-b-PDMS.

As the polymer block copolymer, PS-b-PMMA having a number average molecular weight Mn of PS of 8,500 and a Mn of PDMS of 4,500 was used. The natural period do was found to be 14 nm as in Example 1, and a hexagonal pattern with d = 14 nm, 28 nm, and 42 nm was chemically patterned on the substrate according to this value, and the polymer block co-polymerized with a film thickness of 14 nm. The coalescence was applied and heat treatment was performed to develop microdomains. The PS microdomain present in the obtained PS-b-PDMS thin film was decomposed and removed by RIE, thereby obtaining a polymer thin film having a nanoscale uneven shape derived from the microdomain. RIE-10NP manufactured by Samco Corporation was used for RIE. After etching for 5 seconds at a CF4 gas pressure of 1.0 Pa, a gas flow rate of 10 cm 3 / min and a power of 50 W, an oxygen gas pressure of 1.0 Pa and a gas flow rate of 10 cm 3 / For 20 minutes at a power of 100 W. The obtained polymer thin film was observed by SEM. As a result, it was confirmed that a columnar microdomain structure was formed at a chemically patterned position, and it was recognized that patterning was possible at a desired position.

  In this example, as a result of the investigation conducted using PS-b-PMMA that forms a lamellar microdomain structure as a polymer block copolymer, the method for producing a polymer thin film having the first microstructure of the present invention. Will be described with reference to comparative examples as appropriate.

(Preparation of chemically patterned substrate)
In the same manner as in Example 1, the PS graft layer on the surface of the PS graft substrate was patterned by the EB lithography method, and stripe regions having a width r in which the Si wafer was exposed on the surface of the PS graft layer were arranged in parallel at the lattice spacing d. A chemical pattern substrate was prepared. The pattern arrangement on the prepared substrate is shown in FIG. On one substrate, regions (100 μm square) having a stripe pattern with a lattice spacing d of 40, 80, and 120 nm are continuously arranged. The width r is about 25% to 30% of the lattice spacing d.

(Chemical registration)
A PS-b-PMMA film was formed on the chemically patterned substrate surface to develop microdomains. As PS-b-PMMA, PS (52k) -b-PMMA (52k) having a number average molecular weight (Mn) of PS chain of 52,000 and an Mn of PMMA chain of 52,000 is formed with various film thicknesses. Filmed. The pattern shape in the obtained PS-b-PMMA thin film was observed with a scanning electron microscope. Separately, when the natural period do was determined in the same manner as in Example 1, do = 40 nm.

  Table 2 summarizes the results of experiments conducted using PS (52k) -b-PMMA (52k) using a substrate having a striped pattern having various chemical pattern periods d and film thicknesses. In this table, “○” indicates a state where a pattern is obtained at a desired position, “△” indicates a state where a pattern is recognized only partially at a desired position, and “×” indicates a state where a defect is present. It shows a state in which no pattern was recognized. From the results of Table 3, when the natural period do coincides with the pattern period d of the substrate, a pattern is recognized at a desired position at any film thickness, and the regular structure formed by PS-b-PMMA has no defects. They are arranged periodically over long distances. On the other hand, when the pattern period d of the substrate is twice or three times the natural period do, the film thickness t is 0.8 × do <t <1.2 × do and 1.8 × do <t <2.2. Only in the case of xdo, it was recognized that patterning was possible at a desired position.

  In this experiment, the period d of the substrate of the chemical pattern was twice or three times the natural period do of PS-b-PMMA, but as described above, the film thickness of PS-b-PMMA defined in the present invention. It was shown that the lamella can be arranged at a desired position by self-organization.

  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 pattern arrangement shown in FIG. 9 was applied in the same manner as in the first embodiment. Further, as the polymer block copolymer composition, the number average molecular weight Mn of PS is 46,000, 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 1.04 were used.

  By applying PS-b-PMMA to a thickness of 32 nm on a chemically patterned substrate with a period twice the natural period do of PS (46k) -b-PMMA (21k) and subjecting it to thermal annealing. Microphase separation was developed to obtain a structure in which columnar microdomains composed of PMMA were regularly arranged in a continuous phase composed of PS. 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 15 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 were oriented in one direction without defects in the region where the surface was chemically patterned with a period d = 64 nm. You can see the hexagonal arrangement in the state. On the other hand, in the region that is not chemically patterned, the micropores H are microscopically arranged in a hexagonal manner, but macroscopically, the region that is arranged in a hexagonal manner forms grains. In addition, it has been found that there are many lattice defects particularly 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. It was 28 nm.

  The aspect ratio of the obtained micropore H is 2.0, 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 32 nm before the RIE was reduced to 28 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.

  In this example, a biodevice manufactured using the present invention will be described. FIG. 12 is a plan view of the cell culture sheet.

  As shown in FIG. 12, a cell culture sheet 601 is composed of a thin film (sheet) 601 mainly composed of PMMA having a thickness of 0.5 μm, and a plurality of columnar microprojections mainly composed of PMMA standing on the thin film 601. 603. The columnar fine protrusions 603 have a height of 50 nm and are arranged with a period (pitch) of 100 nm. The columnar fine protrusion 603 has a columnar shape and a diameter of 20 nm. Such a structure having a plurality of columnar fine protrusions 603 on a thin film 601 is a polymer block that forms columnar microdomains with a period of 50 nm and a diameter of 20 nm on a chemically patterned substrate at a pitch of 100 nm. Using a mask prepared by forming a copolymer with a film thickness of 50 nm and forming microdomains, a pattern substrate is prepared using the technique described in Example 2, and a nanoimprint method or the like is used. The pattern substrate can be pressed against a resin layer made of PMMA. In addition, a gap 604 was formed in a cross shape in a part of the columnar fine protrusion 603 by using the method according to the present invention.

  The cell culture sheet 601 is placed in a container such as a glass petri dish, and the culture is immersed in the container for culturing. FIG. 13 referred to here is a schematic diagram showing a state of culture using the cell culture sheet 601. As shown in FIG. 13, the culture is performed by placing a culture solution 605 such as cells (tissues) such as skin, bone, blood, etc., a medium, nutrients, etc. on the columnar fine protrusions 603 of the cell culture sheet 601.

  Since the cell culture sheet 601 is provided with a certain gap 604 (see FIG. 12), the culture solution 605 can easily flow and nutrients can be efficiently supplied to the cells to be cultured. . Moreover, the waste product of the cell at the time of culture | cultivation is discharged | emitted efficiently.

  By using such a cell culture sheet 601, it is possible to significantly reduce damage to the cells due to peeling from the petri dish that has occurred when using a normal glass petri dish, and fixing when the cells are transplanted The rate can be increased. In addition, as shown in FIG. 13, the culture medium 605 can easily flow through the entire cell through the gap 604 (see FIG. 12) formed in the lower part of the sheet-like epidermal cells formed by the columnar fine protrusions 603 on the cell culture sheet 40. . As a result, it is possible to efficiently supply nutrients to the cells and discharge the waste products of the cells, and to suppress the killing of the cells in the culture that has occurred conventionally.

Next, the cell culture sheet 601 was put in a glass petri dish with the culture solution immersed therein, and normal human epidermal keratinocytes were cultured on the cell culture sheet 601. For this culture, HuMedia-KB2 manufactured by Kurabo Industries Co., Ltd. was used as the medium, the culture temperature was 37 ° C., and the flow was performed under a flow of 5% CO 2 . As a result, on the cell culture sheet 601, epidermal keratinocytes adhered normally and proliferated into a sheet shape. The sheet-shaped epidermal keratinocytes with less damage were obtained by peeling the sheet-shaped cells 14 days after the start of the culture.

  Further, the columnar fine protrusion 603 may be a polymer material that has been subjected to a hydrophilic treatment by plasma treatment or the like. Further, the polymer material is not particularly limited, but it is preferable to select a material having little influence on the cells (tissue) to be cultured, and polystyrene, PMMA, and polylactic acid are particularly preferable.

  Examples of biodevices include those that have been micro-processed on the surface, which are generally referred to as μTAS as medical / diagnostic tools, and those that are used for detection / synthesis in the medical / chemical field.

  In this embodiment, a method for manufacturing a multilayer wiring board to which the present invention is applied will be described. FIGS. 14A to 14L are process explanatory views of a method for manufacturing a multilayer wiring board.

  As shown in FIG. 14A, after the chemical patterning is performed on the surface of the multilayer wiring board 61 composed of the silicon oxide film 62 and the copper wiring 63, the micro domain 52 is formed by the polymer block copolymer. Is done.

Next, when the exposed region 53 of the multilayer wiring substrate 61 is dry-etched with CF 4 / H 2 gas, the exposed region 53 on the surface of the multilayer wiring substrate 61 is processed into a groove shape as shown in FIG. Is done. Next, the resist 52 is resist-etched by RIE. Then, when the resist etching is performed until the resist in the low step portion is removed, the exposed region 53 of the multilayer wiring board 61 is enlarged around the resist 52 as shown in FIG. From this state, by further performing dry etching of the exposed region 53, the depth of the previously formed groove reaches the copper wiring 63 as shown in FIG.

  Next, by removing the resist 52, as shown in FIG. 14E, a multilayer wiring board 61 having a groove shape on the surface is obtained. Then, after a metal film (not shown) is formed on the surface of the multilayer wiring board 61, electrolytic plating is performed to form a metal plating film 64 as shown in FIG. 14 (f). Thereafter, the metal plating film 64 is polished until the silicon oxide film 62 of the multilayer wiring board 61 is exposed. As a result, as shown in FIG. 14G, a multilayer wiring board 61 having a metal wiring made of the metal plating film 64 on the surface is obtained.

  Here, another process for manufacturing the multilayer wiring board 61 will be described.

  When dry etching of the exposed region 53 is performed from the state shown in FIG. 14A, the etching is performed until the copper wiring 63 inside the multilayer wiring board 61 is reached, as shown in FIG. Next, the resist 52 is etched by RIE, and the resist 52 portion having a low step is removed as shown in FIG. Then, as shown in FIG. 14J, a metal film 65 is formed on the surface of the multilayer wiring board 61 by sputtering. Next, the resist 52 is removed by lift-off, thereby obtaining a structure in which the metal film 65 is partially left on the surface of the multilayer wiring board 61 as shown in FIG. Next, the remaining metal film 65 is subjected to electroless plating, whereby a multilayer wiring board 61 having a metal wiring made of the metal film 65 on the surface thereof is formed on the multilayer wiring board 61 as shown in FIG. can get. Thus, by applying the present invention to the production of the multilayer wiring board 61, metal wiring having high dimensional accuracy can be formed.

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 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. It is a figure which shows the pattern arrangement | positioning of the board | substrate in the Example of this invention. It is a top view of a cell culture sheet. It is a schematic diagram which shows the mode of culture | cultivation using the cell culture sheet. (A) to (l) are process explanatory views of a method for manufacturing a multilayer wiring board.

Explanation of symbols

101 First segment 102 Second segment 103 Polymer block copolymer 104 Columnar microdomain-like microdomain 105,406 Chemically patterned substrate 201 Substrate 202 Surface 1
203 Surface 2
204 Coating 205 Columnar Microdomain 206 Continuous Phase 207 Microstructure 208 Micropore 209 Polymer Thin Film 301 Natural Period do
401 Chemical modification layer 402 Resist film 403 Exposure 404 Development processing 405 Etching 407 Resist removal 501 Chemical modification layer 1
502 Chemical modification layer 2

Claims (11)

  1. A first step of disposing a polymer layer comprising a polymer block copolymer having at least a first segment and a second segment on a substrate surface;
    A second stage in which the polymer layer is phase-separated to develop a structure formed of a microdomain mainly composed of the first segment and a microdomain mainly composed of the second segment;
    In the manufacturing method of the fine structure having
    The substrate surface has a first pattern member discretely disposed on the substrate surface, wherein the first segment has an interfacial tension with the first segment greater than or substantially equal to an interfacial tension with the second segment, and the first segment. A second pattern member having an interface tension smaller than that of the second segment,
    The relationship between the thickness t of the polymer thin film disposed in the first stage and the natural period do of the microdomain formed by the polymer block copolymer is as follows:
    (M + 0.8) × do <t <(m + 1.2) × do
    And m is an integer greater than or equal to 0, The manufacturing method of the microstructure characterized by the above-mentioned.
  2.   2. The method for manufacturing a microstructure according to claim 1, wherein the interval between the first pattern members has a region larger than a natural period do of a microdomain formed by the polymer block copolymer.
  3.   2. The microstructure according to claim 1, wherein an interval between the microdomains formed in the second stage has a region larger than a natural period do of the microdomains formed by the polymer block copolymer. Manufacturing method.
  4. The first pattern member has regions arranged at intervals larger than the natural period do formed by the microdomain of the polymer block copolymer,
    2. The method for manufacturing a microstructure according to claim 1, wherein in the second stage, the microdomains are formed along an interval between the first pattern members. 3.
  5.   The method of manufacturing a microstructure according to claim 1, wherein the microdomain structure forms a columnar microdomain structure.
  6.   The method for producing a microstructure according to claim 1, wherein the structure of the microdomain forms a lamellar structure.
  7.   The manufacturing method of a microstructure including the process of selectively removing either one of the said continuous phase and the said micro domain of the microstructure manufactured by the manufacturing method of the microstructure of Claim 1.
  8. A first step of disposing a polymer layer comprising a polymer block copolymer having at least a first segment and a second segment on a substrate surface;
    A second stage in which the polymer layer is phase-separated to develop a structure formed of a microdomain mainly composed of the first segment and a continuous phase mainly composed of the second segment;
    A third step of selectively removing either the columnar microdomain or the continuous phase;
    Etching the substrate using the remaining columnar microdomain or continuous phase as a mask, and a fourth step of transferring the concavo-convex structure of the columnar microdomain or continuous phase to the substrate surface,
    The substrate surface has a first pattern member discretely disposed on the substrate surface, wherein the first segment has an interfacial tension with the first segment greater than or substantially equal to an interfacial tension with the second segment, and the first segment. A second pattern member having an interface tension smaller than that of the second segment,
    The relationship between the thickness t of the polymer thin film disposed in the first stage and the natural period do of the microdomain formed by the polymer block copolymer is as follows:
    (M + 0.8) × do <t <(m + 1.2) × do
    And m is an integer greater than or equal to 0, The manufacturing method of the pattern board | substrate characterized by the above-mentioned.
  9.   9. The method for manufacturing a patterned substrate according to claim 8, wherein an interval between the first pattern members has a region larger than a natural period do of a microdomain formed by the polymer block copolymer.
  10.   The pattern substrate according to claim 8, wherein the interval between the columnar microdomains formed in the second stage has a region larger than the natural period do of the microdomains formed by the polymer block copolymer. Manufacturing method.
  11. The first pattern member has regions arranged at intervals larger than the natural period do formed by the microdomain of the polymer block copolymer,
    9. The method of manufacturing a pattern substrate according to claim 8, wherein the columnar microdomains are formed in the second step along the interval between the first pattern members.
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JP2010115832A (en) * 2008-11-12 2010-05-27 Panasonic Corp Method for promoting self-formation of block copolymer and method for forming self-formation pattern of block copolymer using the method for promoting self-formation
JP2011243655A (en) * 2010-05-14 2011-12-01 Hitachi Ltd High polymer thin film, pattern media and their manufacturing methods, and surface modifying material
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WO2013161454A1 (en) 2012-04-26 2013-10-31 Jx日鉱日石エネルギー株式会社 Method for producing mold for transferring fine pattern, method for producing substrate having uneven structure using same, and method for producing organic el element having said substrate having uneven structure
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