JP2011093123A - Method of manufacturing structure with comb type structure, method of manufacturing mold for molding resin structure, and resin molding - Google Patents

Abstract

A method of manufacturing a structure having a large area and a fine comb shape on the surface, and a method of manufacturing a mold for resin molding produced by the structure.
SOLUTION: A step of forming a laminated structure 3 composed of at least two kinds of different resins 1 and 2 selected from thermoplastic resins, and cutting the laminated structure to obtain the two or more kinds of different thermoplastic resins 1. , 2 are arranged to form an exposed cut surface, and the cut surface is obtained by preferentially removing at least one of the thermoplastic resins constituting the laminated structure 3 from the cut surface. And a step of forming a comb-shaped concavo-convex structure thereon. The method of manufacturing the resin structure 5 having a comb-shaped structure.
[Selection] Figure 1

Description

  The present invention relates to a method for producing a resin structure having a fine comb-shaped concavo-convex structure used for a nanoimprint mold and its original mold and the like, and a resin molded body obtained thereby.

  In recent years, with the miniaturization and high performance of electronic devices, energy storage devices, sensors, and the like, devices having a structure with a size of less than 50 nm have been actively developed. In addition, new devices that make use of phenomena peculiar to nanometer-scale three-dimensional microstructures have been actively developed. Various applications such as anti-reflection nanostructures that reduce light reflection, photonic crystals that artificially control the direction of light propagation, and quarter-wave plates that can be built on the surface of other optical components are being studied. Has been.

  In general, a technique for drawing a fine pattern called lithography is used to manufacture such a microstructure device. The lithography technique includes at least the following steps. After the photosensitive resin layer is formed on the substrate to be processed, the radiation that the photosensitive resin layer is exposed to only a predetermined region on the photosensitive resin layer, such as ultraviolet rays, X-rays, electron beams, ion beams, etc. Is selectively irradiated, and if necessary, heat treatment is performed, thereby causing a chemical change in the irradiated region and forming a latent image. Thus, after forming a latent image, it is immersed in a developing solution. Due to the chemical change of the photosensitive resin in the irradiated area, a difference in dissolution rate between the irradiated area and the non-irradiated area in the developer occurs, and the area having a low dissolution rate remains as a pattern. Thereby, a mother die having a fine structure in which grooves are dug to a desired depth is obtained. A stamper is manufactured using this matrix as a prototype. Currently, an optical lithography method using short-wavelength light such as vacuum ultraviolet light, an electron beam lithography method using an electron beam, and the like are used.

  However, in the photolithographic method, it has become difficult in recent years to further reduce the wavelength of the light source in order to produce a finer structure, and enormous investment is required for development including peripheral technologies.

  On the other hand, the electron beam lithography method enables fine drawing of about 10 nm, but it is necessary to reduce the beam diameter to increase the resolution, and the drawing speed is slow and it takes time to increase the area. For example, even if a dot pattern with a pitch of 40 nm is drawn in a range of 1 mm × 1 mm, several hours are required. Moreover, the apparatus for generating an electron beam is large and requires enormous investment.

  Under such circumstances, a technique that applies a phenomenon in which substances naturally form a structure, that is, a so-called self-organization phenomenon, is attracting attention. In particular, the technique applying the self-organization phenomenon of the polymer block copolymer, the so-called micro phase separation phenomenon, can form a fine regular structure having various shapes of several tens to several hundreds of nanometers by a simple coating process. This is an excellent technique.

  Here, when different types of polymer segments constituting the polymer block copolymer are not mixed with each other, a micro structure having specific regularity is self-organized by microphase separation of these polymer segments. And, using such a self-organization phenomenon, a known technique is known in which a polymer block copolymer thin film is used as an etching mask and a structure such as a fine hole or a line and space is formed on a substrate. (For example, refer nonpatent literature 2 and nonpatent literature 3.).

  According to the microphase separation phenomenon of the polymer block copolymer, a polymer thin film having a structure in which spherical or columnar microdomains are regularly arranged in a continuous phase can be obtained. When such a microphase-separated structure is used as a pattern transfer body such as an etching mask, it is desirable that the columnar microdomains are regularly arranged in the continuous phase so as to stand upright on the substrate. This is because in the case of a structure in which columnar microdomains are aligned and aligned in a direction perpendicular to the substrate, the aspect ratio of the resulting structure is compared to a structure in which spherical microdomains are regularly aligned on the substrate surface. This is because the ratio can be adjusted freely.

  However, many of the columnar microdomain structures due to the microphase separation phenomenon of the polymer block copolymer show a structure oriented in a direction parallel to the film surface.

Examples of conventional methods for aligning columnar microdomains that are easily aligned in a direction parallel to the film surface in a direction perpendicular to the substrate include the following.
A first conventional method is a structure in which a columnar microdomain is oriented in the direction of an electric field by applying an extremely high electric field to a film of a polymer block copolymer in a direction penetrating the film surface to stand upright on the film surface. (See, for example, Non-Patent Document 4). However, in the first conventional method described above, in order to apply a high electric field to the polymer block copolymer film, it is necessary to apply an electrode to the film surface and apply a voltage to the film between very narrow gaps. Some special processes or equipment are required.

In the second conventional method, the substrate surface is chemically modified and processed so as to have equal affinity for each segment of the polymer block copolymer to obtain a structure in which the columnar microdomains stand upright on the substrate. It is a method (for example, refer nonpatent literature 5). However, it is generally not easy to treat the substrate surface to have equal affinity for each segment of the polymer block copolymer.
That is, in these conventional methods, there is a problem that it is not practical to align the columnar microdomains in an upright direction with respect to the film surface.

JP-A-4-278324 JP-A-2005-349881

SPIE Advanced Lithography, Feb. 2008. Science 276 (1997) 1401 Polymer 44 (2003) 6725 Macromolecules 24 (1991) 6546 Macromolecules 32 (1999) 5299

  However, in order to efficiently operate devices such as single-electron transistors and light-emitting elements that are expected as high-performance devices in the future, it is necessary to form nanostructures with a size of several nm at intervals of the nm order. . In addition, it is necessary to shorten the production time for improving productivity and to produce a large area. Formation of such a high resolution, high density and large area pattern is difficult to produce by a process using a top-down technique such as the existing lithography technique or a self-organization phenomenon.

  An object of the present invention is to solve the above-mentioned conventional problems by using a laminated structure produced by multilayer extrusion molding, and a method for producing a structure having a large area and a fine comb shape on the surface, and the structure It is in providing the manufacturing method of the metal mold | die for resin molding produced by.

  The present invention includes a step (1) of forming a laminated structure made of at least two or more different resins selected from thermoplastic resins, and cutting the laminated structure so that the two or more different thermoplastic resins are arranged. And forming the exposed cut surface (2), and preferentially removing at least one of the thermoplastic resins constituting the laminated structure from the cut surface on the cut surface. And a step (3) of forming a comb-shaped concavo-convex structure, and a method for producing a resin structure having a comb-shaped structure.

In the method for producing the resin structure,
The step (3) includes a step of preferentially removing at least one of the thermoplastic resins constituting the laminated structure from the cut surface of the laminated structure using a difference in removal speed. This is a method for producing a resin structure having a comb structure.

In the method for producing the resin structure,
Subsequent to the step (3), the method includes a step (4) of transferring the comb-shaped structure to the transferred body by bringing the transferred body into close contact with the cut surface of the laminated structure having a comb-shaped uneven structure. This is a method for producing a resin structure having a comb structure.

  Furthermore, the step (1) of forming a laminated structure made of at least two different resins selected from thermoplastic resins, and cutting the laminated structure, the two or more different thermoplastic resins are arranged. A step (5) of obtaining a laminate having two exposed cut surfaces facing each other, and a step of removing at least one of the thermoplastic resins constituting the laminate having the two cut surfaces facing each other ( 6) and a step (7) of forming a comb-shaped uneven structure on the surface of the molded body by etching the molded body using the other resin remaining in the step (6) as a mask. This is a method for manufacturing a structure having a comb structure.

  Moreover, it is a comb mold for resin molding manufactured using the process including the manufacturing method of the resin structure described above.

  Furthermore, it is a comb-shaped resin molded body manufactured by using a comb mold for resin molding manufactured using a process including a method for manufacturing a resin structure.

  Moreover, this invention is a resin molding which has the comb-shaped structure manufactured using the structure which has the comb-shaped structure manufactured using the process including the manufacturing method of the above-mentioned resin structure as a type | mold for resin molding.

  ADVANTAGE OF THE INVENTION According to this invention, the manufacturing method of the board | substrate which has a resin structure which has a large area and fine comb structure excellent in productivity can be provided. Moreover, the resin structure can be used as a mother mold, and a resin molding die, a method for producing the mold, and a resin molded body having a comb structure can be provided.

It is the schematic diagram which showed the process of the manufacturing method of the resin structure which has a comb-shaped structure which concerns on embodiment of this invention. It is a schematic diagram which shows the state which arranged the cut-out laminated structure on the board | substrate. It is the schematic diagram which showed the process of the manufacturing method of the resin structure which has the comb-shaped structure which concerns on embodiment of this invention, and the process drawing which showed the process of the manufacturing method of the resin mold. It is the schematic diagram which showed the process of the manufacturing method of the resin structure which has a comb-shaped structure which concerns on embodiment of this invention. 3 is a SEM photograph of the surface of a resin structure according to Example 1.

A method for producing a resin structure having a comb structure according to an embodiment of the present invention will be described with reference to FIG.
Using the conventional multilayer extrusion molding technique, a laminate structure 3 in which two different types of resins (resin 1 and resin 2) are alternately arranged is prepared, and the laminate structure 3 is obtained by cutting out the laminate structure 3. FIG. 1A shows a cross section of the laminated structure 3 in which different thermoplastic resins are arranged and exposed. The shape of the laminated structure 3 is not particularly limited, but it is preferable that the laminated direction is oriented perpendicular to the etching direction.

  The multilayer extrusion molding technique shown here indicates, for example, a co-extrusion technique as described in Patent Document 1 or Patent Document 2, and the multilayer structure 3 is produced by using this multilayer extrusion molding technique. Multi-layer extrusion techniques may involve passing various streams from various extruders to a multi-layer manifold die or multi-layer feedblock and a film die. The individual streams merge in the feed block and can enter the die as a stack to obtain a stack.

  The magnitude | size of the laminated structure 3 shown here can be changed with the use. Moreover, it is possible to produce a resin structure having a large area by arranging a plurality of laminated structures 3 so as to adhere to each other perpendicularly to the etching direction. The number of the laminated structures 3 arranged is not particularly limited, but is preferably one in the arrangement direction.

  Further, as shown in FIG. 2A, it is possible to take a form in which the cut-out laminated structure 3 is arranged on the substrate 4 so that the cross section stands perpendicular to the substrate direction.

  At this time, the substrate 4 can be selected according to its purpose, such as Si wafer, glass, ITO, resin, or the like.

  Next, the target resin 2 is selectively removed from the laminated structure 3 in FIG. 1A, and a comb-shaped structure in which the resins 1 as shown in FIG. Obtainable. Although not shown in the figure, it is also possible to selectively remove the target resin 1 from the laminated structure 3 and obtain a resin structure 5 having a comb structure in which the resins 2 are regularly arranged. As described above, the resin structure 5 having a comb structure in which the resins 1 or 2 are regularly arranged can be used as a substrate. In this step, a substrate including the resin structure 5 having a comb structure is manufactured. It will be done. Although not shown in the figure, this process can also be applied in the form as shown in FIG.

By the way, as the two kinds of resins used in the present invention, those capable of selectively removing the target resin are used. In this case, it is preferable to use the difference in removal rate with respect to other etching methods such as reactive ion etching (RIE) or wet etching. For example, when polystyrene and polybutadiene are used, development processing is possible so that only polystyrene is left by ozone treatment. When polystyrene and polymethyl methacrylate are used, polystyrene has higher etching resistance to RIE using oxygen or CF ₄ as an etchant than polymethyl methacrylate. For this reason, it is possible to selectively remove only polymethyl methacrylate by RIE.

  Here, an etching method will be described. As an etching method, physical dry etching by a sputtering phenomenon using an inert gas or reactive ion etching (RIE) using a reactive gas such as oxygen, chlorine-based gas, or fluorine-based gas can be used. . Plasma generation methods include plasma by electron cyclotron resonance (ECR) and plasma by inductive coupling (ICP).

As the etching _{gas, Ar, H 2, N 2} , O 2, CO, CO 2, CF 4, CHF 3, CH 2 F 2, C 2 F 6, C 3 F 6, C 4 F 8, NH Gases used for well-known dry etching, such as ₃ , Cl ₂ , BCl ₃ , and SF ₆ , can be used alone or in combination.

  On the other hand, when using wet etching with chemicals, for example, various organic solvents can be used for dissolving polystyrene, but it is preferable to use benzene, toluene, xylene, carbon tetrachloride, methyl ethyl ketone, cyclohexanone, or the like.

  The resin used in the present invention is flowable and can be applied to any curable material, but is not particularly limited. For example, acrylic resin, cycloolefin resin, styrene resin, acrylic / styrene resin Copolymers, polycarbonate resins, polyester resins such as polyethylene terephthalate, ethylene / vinyl alcohol copolymers, thermoplastic elastomers such as polyamide / olefin / styrene / urethane, soft vinyl chloride resin, fluorine resin, Thermosetting resins such as silicone resins such as polydimethylsiloxane, thermosetting resins such as epoxy resins, phenolic resins, urethane resins and unsaturated polyester resins, and photocurable resins such as polyfunctional acrylic resins Can be mentioned.

  These resins may be used as necessary, for example, liquids, lubricants, light stabilizers, flame retardants, anti-sticking agents, ultraviolet absorbers, antioxidants, foaming agents, photoinitiators, antifogging agents, pigments, antistatic agents. The organic or inorganic additives such as blocking agents can be used alone or in combination.

Next, another embodiment according to a method for manufacturing a substrate having a comb structure will be described with reference to FIG.
The steps from FIG. 3A to FIG. 3B are the same as the steps from FIG. 1A to FIG.
Then, as shown in FIG. 3C, a resin structure 5 having a comb structure is used as a matrix, and a conductive film 6 is deposited on the structure 5. Next, as shown in FIG. 3D, the electric pole layer 7 is deposited by electroforming to a desired thickness. Thereafter, as shown in FIG. 3E, the resin structure 5 is peeled off to obtain a substrate 8 having a comb structure. The substrate 8 having a comb structure can be used as a mold for molding a resin molded product having a comb structure. Further, the resin structure 5 having a comb structure obtained in the steps of FIGS. 2A to 2B can also be used as a mother mold of the mold.

  Here, a method for forming the conductive film is not particularly limited, but preferably, vacuum deposition or sputtering can be used. Examples of the conductive film include nickel, gold, silver, platinum, copper, and aluminum.

  Moreover, the metal deposited by electroforming is not particularly limited, but nickel, copper, gold, nickel-cobalt alloy can be mentioned, and nickel is preferably used from the viewpoint of economy and durability.

  A resin molded product can be formed using a molding die for a resin molded product having the comb structure. The molding method of the resin molded product is not particularly limited. For example, an imprint method such as thermal imprint or optical imprint, injection molding, press molding, monomer cast molding, solvent cast molding, hot emboss molding, roll transfer method by extrusion molding Etc.

Next, another embodiment according to a method for manufacturing a substrate having a comb structure will be described with reference to FIG.
Since the steps of FIGS. 4A and 4B are the same as the steps of FIG. 2A already described, description thereof will be omitted. The target resin 2 is selectively removed from the laminated structure 3 on the substrate 4 to obtain a resin structure 5 having a comb structure in which the resins 1 are regularly arranged as shown in FIG. .
Then, as shown in FIG. 4C, among the resin structures 5 having the comb-shaped structure, the molded body 9 is subjected to reactive ion etching (RIE) using the remaining resin array made of the resin 1 as a mask. Alternatively, by performing etching using another etching method, a structure 10 having a comb structure is formed on the molded body 9 as shown in FIG. When the resin 1 remaining on the surface of the structure 10 is removed by RIE or a solvent, a substrate 11 having a comb structure is obtained as shown in FIG.

  Here, the molded body 9 may be the same as or different from the substrate 4. The material of the molded body 9 is not limited to resin as long as it can be etched, and various materials can be used, and Si wafer, glass, resin, and the like can be selected according to the purpose.

  The substrate 11 having the comb structure can also be used as a matrix of the substrate 8 having a comb structure by electroforming instead of the resin structure 5 of FIG. 3B, and the obtained substrate 8 having the comb structure is obtained. Can be used as a mold for molding a resin molded product having a comb structure.

  A structure having a large aspect ratio and a large comb structure can be manufactured by the method for manufacturing a structure having a comb structure described above.

  Moreover, it is necessary to select between the pitch of two types of resin which comprises the said laminated structure 3, layer width, and the size of the laminated structure 3 according to the size of the target pattern. An object of the present invention is to form a large comb and a fine comb structure which is difficult to achieve by a conventional top-down method or a method using self-organization. The pitch and the layer width of the two types of resins constituting the laminated structure 3 can be easily controlled by adjusting the extrusion amount of the two types of resins at the time of producing the laminated structure 3 or by changing the number of laminated layers. can do.

  The substrate having a comb structure obtained by the manufacturing method of the present invention can be easily manufactured and can have a large area, and thus can be applied to various uses. For example, it can be applied to optical parts such as non-reflective plates, wavelength selection filters, polarization conversion elements, biodevices such as cell culture and muscle fiber analysis, semiconductor parts of solar cells, information recording media, magnetic recording media, etc. It is.

  Next, examples of the present invention will be described. However, the present invention is not limited to these examples.

<Example 1>
Polymethyl methacrylate (PMMA, manufactured by Kuraray Co., Ltd., Parapet G) was used as the resin A, and polystyrene (PS, manufactured by Toyo Styrene Co., Ltd., HRM-1) was prepared as the resin B. Resin A was dried overnight at 80 ° C., and then resins A and B were supplied to the extruder.

  Resins A and B were melted at a temperature of 240 ° C. using an extruder, and measured with a gear pump so that the discharge ratio would be resin A / resin B = 1/1. Thus, a structure in which 2049 layers of the resin A layer and the resin B layer were alternately laminated in the width direction in a resin structure having a width of 3 mm and a length of 30 mm was produced.

  A piece (width direction-thickness direction cross section) was cut out from the above structure so that the laminated structure appeared in a cross section using a precision low-speed cutting machine, and the surface of the cut piece was flattened using a microtome. .

  Next, the surface of the cut piece of the obtained laminate was subjected to oxygen plasma etching at an output of 500 W to remove the PMMA layer. The surface of the obtained structure was observed with a scanning electron microscope (SEM). In the SEM image shown in FIG. 5, the PMMA layer is decomposed and removed on the surface, and the PSt layer remains, so that the PMMA region formed by the PMMA layer and the PS region formed by the PS layer have a depth of 890 nm on the surface of the resin structure. A state in which fine comb-shaped shapes having a width of 1000 nm were arranged in the length direction of 30 mm was observed.

DESCRIPTION OF SYMBOLS 1, 2 Two types of different resin 3 Laminated structure 4 Substrate 5 Resin structure 6 which has a comb structure 6 Conductive film 7 Electroformed layer 8 Substrate having a comb structure 9 Molded object 10 Resin structure having a comb structure Body 11 Substrate having comb-shaped structure

Claims (7)

  Step (1) of forming a laminated structure made of at least two different resins selected from thermoplastic resins, and cutting the laminated structure so that the two or more different thermoplastic resins are arranged and exposed. Step (2) of forming a cut surface, and comb-shaped irregularities on the cut surface by preferentially removing at least one of the thermoplastic resins constituting the laminated structure from the cut surface A process for producing a resin structure having a comb structure, comprising the step (3) of forming a structure.   The step (3) includes a step of preferentially removing at least one of the thermoplastic resins constituting the laminated structure from the cut surface of the laminated structure using a difference in removal speed. The method for producing a resin structure having a comb structure according to claim 1.   Subsequent to the step (3), the method includes a step (4) of transferring the comb-shaped structure to the transferred body by bringing the transferred body into close contact with the cut surface of the laminated structure having a comb-shaped uneven structure. The method for producing a resin structure having a comb structure according to claim 1 or 2.   Step (1) of forming a laminated structure made of at least two different resins selected from thermoplastic resins, and cutting the laminated structure so that the two or more different thermoplastic resins are arranged and exposed. A step (5) of obtaining a laminate having two cut surfaces facing each other, and a step (6) of removing at least one of the thermoplastic resins constituting the laminate having the two cut surfaces facing each other. And a step (7) of forming a comb-shaped concavo-convex structure on the surface of the molded body by etching the molded body using the other resin remaining in the step (6) as a mask. A method for manufacturing a structure having a comb structure.   A method for producing a mold for molding a resin structure, comprising a step (8) of transferring the surface structure of the structure obtained by the method for producing a structure according to claim 1 or 4 by electroforming.   A resin molded body having a comb structure manufactured using a mold obtained by the method for manufacturing a mold for molding a resin structure according to claim 5.   A resin molded product having a comb structure obtained by using the structure obtained by the method for producing a structure having a comb-shaped uneven structure according to claim 1 or 4 as a molding die for resin molding.