JP4512918B2 - Method for producing fine pattern with microring or microdot - Google Patents

Description

  The present invention relates to a method for producing a fine pattern having microrings or microdots. Specifically, the present invention relates to a microring or microdot-like fine pattern manufacturing method expected to be used for electronic circuits, photonic crystals, regenerative medical materials, and the like.

  Materials with a periodic structure on the nanometer to micrometer scale are used as electrical circuits such as transistor arrays, photonic materials such as diffraction gratings and photonic crystals, and regenerative medical materials that control cell differentiation and functions. It has attracted attention (Non-Patent Documents 1 to 4). In order to use it for these applications, it is required to produce the periodic structure with high quality and as low cost as possible using a material suitable for the application. As a manufacturing method therefor, photolithography technology is used (Non-patent Document 4), which requires extremely expensive equipment and highly skilled technology, and is one of the major factors that increase the cost of products. It was one.

  This is a film in which periodic shapes are regularly arranged by a process that is completely different from the above-described lithography process, as a result of earnest research by a number of research groups, including our research group. Was successfully created. More specifically, by developing a polymer solution on a substrate under high humidity, we succeeded in producing a honeycomb porous thin film having pores arranged in hexagonal using self-organization of water droplets, It was reported in an academic paper (Non-Patent Document 5). This research was further advanced, and honeycomb porous thin films were prepared from various materials, the control and application of the structure was examined, and patent applications were filed for the results (see Patent Documents 1 to 6), or various academic papers. (See Non-Patent Documents 6 to 10).

Gelinck, G.G. H. Geuns, T .; C. T.A. , De Leeuw, D. M.M. , Appl. Phys. Lett. 2000, 77 (10), 1487 Joannopoulos, J.A. D. Meade, R .; D. Winn, J .; N. Photonic Crystals? Molding the Flow of Light; Princeton University Press: New Jersey, 1995 Ostuni, E .; Chen, C .; S. Ingber, D .; E. Whitesides, G .; M.M. Langmuir 2001, 17 (9), 2828 Xia, Y .; Whitesides, G .; M.M. Annu. Rev. Mater. Sci. 1998, 28, 153 Karthaus, O. Maruyama, N .; Cieren, X .; Shimomura, M .; Hasegawa, H .; Hashimoto, T .; Langmuir 2000, 16 (15), 6071 Nishida, J. et al. Nishikawa, K .; Nishimura, S .; Wada, S .; Karino, T .; Nishikawa, T .; Ijiro, K .; Shimomura M .; Polym. J. et al. 2002, 34, 166-174 Kurono, N.A. Shimada, R .; Ishihara, T .; Shimomura M .; Mol. Cryst. Liq. Cryst. 2002, 377, 285-288 Karthaus, O. Cieren, X .; Maruyama, N .; Shimomura M .; Mater. Sci. Eng. 1999, C 10, 103-106 Nishikawa, T .; Nishida, J .; Okura, R .; Nishimura, S .; Wada, S .; Karino, T .; Shimomura M .; Mater. Sci. Eng. 1999, C 8-9, 485-500 H. Yabu, M .; Tanaka, K .; Ijiro, M.M. Shimomura, Langmuir, 19 (15), 6297-6300 (2003) JP 2003-149096 A JP 2003-128832 A JP 2003-080538 A JP 2002-347107 A JP 2002-335949 A JP 2001-157574 A

  However, the periodic structures described in these documents are in a state of presenting a honeycomb structure, and the periodic structure having other shapes is not mentioned, and microscale fine periodic structures other than the honeycomb structure are not mentioned. It was not possible to meet the demand for a structure having the same.

  The present invention is intended to meet such demands, and is a microring or microdot pattern having a microscale periodic structure made of a material having electronic, optical functionality and biocompatibility, or a structure having this pattern. Is intended to be provided by simple equipment and processes at low cost.

  Therefore, as a result of diligent research by the present inventors, a honeycomb membrane obtained on the basis of a technique for forming a honeycomb porous thin film using water droplets as a mold is heated on a substrate, and then the membrane is peeled off. The present inventors have succeeded in obtaining a structure having a periodic structure other than a ring-shaped or dot-shaped honeycomb by combining a so-called thermal transfer method in which a partial cross-sectional structure of a honeycomb is transferred onto a substrate. The present invention has been made based on the success and knowledge of this series of processes.

  That is, as a result of observing a film having a porous honeycomb structure that templated water droplets in the present inventors, the material developed around the water droplets has a difference in material and separation that are considered to be based on a kind of phase separation phenomenon. I found out. By heat-treating this on the substrate, a ring structure corresponding to the diameter of the pores of the honeycomb can be obtained by projecting this based on the difference in the phase-separated material, or if this treatment temperature is further increased, the honeycomb It was found that a structure in which the material was melted in the form of dots in the portion corresponding to the diameter of the hole was obtained. In summary, when pores and voids of a honeycomb structure using water droplets as a template are formed, it is considered that a kind of phase separation occurs in the material constituting the polymer at the interface near the pores. The reason for the phase separation is not clear, but in any case, it is presumed that separation based on the difference in material occurs. Therefore, if this is subjected to heat treatment, it is considered that a specific material portion is transferred, that is, a predetermined shape is obtained due to the difference in thermal behavior of the phase-separated material.

  Here, the process for obtaining the honeycomb porous thin film, which is the preceding process, is as described in the various documents introduced above, and can be easily obtained by referring to these documents in detail. The outline is as follows. First, a polymer solution is prepared, wet air is blown onto the solution surface, the solvent is evaporated, water droplets are condensed on the polymer surface, and the condensed water droplets are closely packed, so that the polymer has a space based on the water droplets and a polymer. A regular fine structure composed of regions is formed. That is, the condensed water droplets are arranged two-dimensionally on the surface of the polymer solution, that is, a pore mold is formed, and a structure having a uniform fine pore pattern is produced. Thus, a film having a honeycomb structure having a hole structure from which is removed is formed. In summary, it is manufactured by the above process.

  For the honeycomb film having the regularly arranged fine honeycomb holes obtained by the preceding process, in the present inventors, if only the trunk portion of the honeycomb is transferred to the substrate by some means, I thought that the thing different from a honeycomb could be obtained with periodicity. More specifically, as will be described later with reference to FIG. 7, if a phase separation phenomenon in the film forming process of a plurality of polymers constituting the honeycomb is utilized and one of the phase separated portions is thermally transferred to the substrate, a uniform microstructure can be obtained. I thought that could be realized.

  Specifically, the honeycomb porous film was subjected to heat treatment on an arbitrary substrate to peel the film from the substrate. This treatment succeeded in copying only the amphiphilic polymer onto the substrate due to the difference in Tg (glass transition temperature) between the amphiphilic polymer constituting the honeycomb film and the matrix material. That is, by the difference in Tg in the material constituting the honeycomb film and the heat treatment on the substrate, only the amphiphilic polymer distributed around the pores of the honeycomb film is copied on the substrate, and the ring shape is arranged in a hexagonal manner. It has succeeded in obtaining a structure. When the heating temperature is further increased, the both amphiphilic polymers are once dissolved and solidified in the voids, thereby succeeding in obtaining a dot structure similar to the pore diameter of the honeycomb.

The present invention has been made based on success and findings of this series of processes, the taken configurations are as described by below (1) to (7).

(1) After heat-treating on a substrate a honeycomb porous thin film made of an amphiphilic polymer having a glass transition point (Tg) of the amphiphilic polymer equal to or lower than the Tg of the matrix material and the matrix material , the substrate said honeycomb porous thin film is peeled off, or Utsushitoru only amphiphilic polymer distributed in the holes around the honeycomb porous thin film on the substrate, or, once dissolved only the amphiphilic polymer from The microrings or microdots presenting the microrings or microdots characterized by transferring the microrings or micropatterns presenting the microdots to the substrate by solidifying them in the voids of the honeycomb. A method for manufacturing a structure having a pattern.
(2) In the above (1), the honeycomb porous thin film uses a porous film formed by developing a solution of an amphiphilic polymer and a matrix material and evaporating the solvent under high humidity. A method for producing a fine pattern or a structure having the microring or microdot described above.
(3) structure pore diameter of the honeycomb porous thin film having a fine pattern or the pattern exhibited micro-ring or microdots according to (1) or (2), which is a 100nm~100μm Manufacturing method.
(4) A method for producing a microring or a fine structure having a microdot according to any one of (1) to (3) , or a structure having this pattern, wherein the amphiphilic polymer is biodegradable. A micro-pattern or a fine pattern having a micro-dot or a structure having this pattern, characterized by being a biocompatible material.
(5) A method for producing a microring or a fine structure having a microdot according to any one of (1) to (3) , or a structure having this pattern, wherein the amphiphilic polymer is an electronic function. A method for producing a microring or a fine structure having a microdot or a structure having this pattern, characterized by being a material or an optical functional material.
(6) A method for producing a microring or a fine structure having a microdot according to any one of (1) to (3) , or a structure having this pattern, comprising an amphiphilic polymer and biodegradation sex, biocompatible materials, electronic functional materials, optical functional materials ionic bond, covalent bond, or a fine pattern or the pattern exhibited micro-ring or microdots, characterized in that to further coupled for hydrophobic interaction A method for producing a structure having the same.
(7) A method for producing a microring or a fine structure having a microdot according to any one of (1) to (3) , or a structure having this pattern, comprising an amphiphilic polymer and a catalytic function method for manufacturing a structure material having an ionic bond, a fine pattern or the pattern exhibited micro-ring or microdots, characterized in that to further coupled for covalent or hydrophobic interactions.

  According to the present invention, a novel fine pattern structure exhibiting microrings or microdots and a method for manufacturing the same are provided. As a result, electrical circuits such as transistor arrays, photonics materials such as diffraction gratings and photonic crystals, anisotropic solid conductive materials and semiconductor materials, various recording media, cell culture substrates, DNA chips, and protein chips Then, useful carriers such as various biodiagnostic chips, battery diaphragm materials such as separators and ion exchange membranes, various catalysts, enzymes, antibodies and drugs are provided.

  Here, the matrix material used in the present invention includes general-purpose polymers such as polystyrene, polymethylhexadecylsiloxane, and polyvinylcarbazole, engineering plastics such as polysulfone, polymethyl methacrylate, polytetrahydrofurfuryl methacrylate, and polybutyl methacrylate. (Meth) acrylic polymer, styrene-butadiene elastomer, polyurethane polymer, polybutylene carbonate, aliphatic polycarbonate such as polyethylene carbonate, etc., polylactic acid, lactic acid-glycolic acid copolymer, polyhydroxybutyric acid, polycaprolactone, polyethylene adipate Biodegradable polymers such as polybutylene adipate are preferred from the viewpoint of solubility in organic solvents. These may be used alone or in combination of two or more.

  The amphiphilic polymer used in the present invention includes a polyethylene glycol / polypropylene glycol block copolymer and an acrylamide polymer as a main chain skeleton, and a parent having both a dodecyl group as a hydrophobic side chain and a lactose group or a carboxyl group as a hydrophilic side chain. Amphiphilic polymer or amphiphile with hydrophilic groups such as ion complexes of heparin, dextran sulfate, anionic polymers such as nucleic acids such as DNA and RNA and long chain alkyl ammonium salts, and water-soluble proteins such as gelatin, collagen and albumin It is desirable to use a functional polymer or the like, and functional materials such as biodegradability, biocompatibility, electronic functionality, and optical functionality and derivatives thereof can be used. It is also possible to bind a physiologically active material, a dye, a catalyst or the like to the patterned amphiphilic polymer via an ionic bond or a covalent bond.

  In producing a honeycomb porous thin film as a precursor of the microstructure of the present invention, it is essential to form fine water droplet particles on the polymer solution, so that the organic solvent to be used is water-insoluble. There must be something. Examples of these include halogen-based organic solvents such as chloroform, dichloromethane and dichloroethane, aromatic hydrocarbons such as benzene, toluene and xylene, esters such as ethyl acetate and butyl acetate, and water-insoluble ketones such as methyl isobutyl ketone. And carbon disulfide. These organic solvents can be used alone or as a mixed solvent in which these solvents are combined.

  The substrate used in the present invention is not particularly limited, but inorganic materials such as ITO, glass, metal, and silicon wafer, polymers excellent in organic solvent resistance such as polypropylene, polyethylene, polyetherketone, and fluororesin Can be used.

  The microring and dot structure film structure of the present invention and the manufacturing method thereof will be described below with reference to the drawings and examples. However, these are disclosed only as an aid for helping understanding of the present invention, and are not intended to limit the present invention.

Example 1;
(Honeycomb porous film production process):
Polymer 1 (chemical 1: dodecylacrylamide-ω-carboxyhexylacrylamide) and polybisphenol A carbonate (chemical 2) were mixed at 1: 9 as an amphiphilic polymer to prepare a chloroform solution. 5 mL of this solution was developed on a glass substrate, and chloroform as a solvent was evaporated while blowing high-humidity air (2 to 10 liters / min) to form a film. A scanning electron microscope image (SEM) of the produced honeycomb porous film is shown in FIG.

(Transfer process of phase separation structure on substrate);
The produced film was peeled off from the glass substrate, and the upper surface at the time of production was adhered to the ITO substrate. This sample was heated on a hot stage at a temperature of 120 ° C. to 200 ° C. for 5 minutes to 1 hour to transfer the structure onto the ITO substrate. After cooling to room temperature, the mold film was peeled off with an adhesive tape to obtain a transfer structure. The shape of the obtained structure was observed with an optical microscope (OM), a scanning electron microscope (SEM), and an atomic force microscope (AFM). Moreover, the chemical composition of the obtained structure was identified by FT-IR reflection absorption measurement (RAS). Furthermore, the thermal properties were identified by a scanning differential calorimeter (DSC).

Observation of the transferred structure;
Two types of structures were observed on the structure transferred onto the ITO substrate depending on the heating temperature. In the temperature range of 120 ° C. to 180 ° C., a ring-like structure (FIG. 2) arranged in hexagonal was formed. The diameter of the ring structure was almost the same as that of the honeycomb film used as a mold. It was found that when the hole diameter of the honeycomb film serving as a mold was changed, the ring diameter also changed (FIG. 3). However, the width and height of the ring were about 700 nm and about 200 nm.
When the temperature was 180 ° C. or higher, a dot-like structure arranged in hexagonal was observed (FIG. 4). The diameter was about the same as the hole diameter of the honeycomb film, and the diameter also increased when the hole diameter of the film serving as the mold changed. The height was around 500 nm.
FT-IR RAS measurement (Fourier transform infrared absorption spectrum; high-sensitivity reflection method using FT-IR; reflection-absorption spectroscopy method) shows the absorption of polybisphenol A carbonate (near 1790 cm ^-1 ) found in the honeycomb film by the ring and disappeared in dots, the absorption of C-H stretching (2800-2900cm ^-1) and amide (1710cm ^-1, 1650cm ^-1) is significantly appeared instead. Therefore, it became clear that the ring and dot structure consisted of the amphiphilic polymer 1 only (FIGS. 5.a and 5.b).
By DSC measurement, polymer 1 shows some lower transition points than polybisphenol A carbonate (FIG. 6). Furthermore, the thermal transition points of the honeycomb film are 116 ° C. and 183 ° C., which correspond to the temperatures at which rings and dots are formed, respectively.
From these results, it is considered that the ring and dot formation mechanism is as shown in FIG. Since the honeycomb film uses water droplets as a mold, the amphiphilic polymer 1 is concentrated at a high concentration around the water droplets serving as a mold. By heating this on the substrate, the film is softened at 116 ° C., but the honeycomb structure is maintained, and only the polymer 1 in contact with the substrate is transferred onto the substrate. On the other hand, when the temperature is raised and the temperature exceeds 180 ° C., the whole film is softened, the whole is crushed, and the pores of the honeycomb are simultaneously compressed. The polymer 1 originally concentrated in the space gathers to form a dot-like structure. In both cases, polybisphenol A carbonate having a high Tg is peeled off after cooling, and as a result, a ring structure and a dot structure are formed by polymer 1.
From the above formation mechanism, it is considered that the method can be applied to any material as long as it is an amphiphilic compound having a Tg lower than that of the matrix material.

  In the above transfer process, the honeycomb film was directly placed on the substrate material and heat treated to transfer the specific shape to the substrate, but the substrate was not affected by the heat treatment, and the material of the microring or microdot It is also possible to select a film made of a material that does not react with the substrate and easily peels from the substrate material, coats the film, and transfers the film through the coated film. In this case, after the transfer step is completed, the coating film is peeled off so that the microrings or microdots can be easily peeled off from the substrate and can be recovered as a film-like final product. The present invention includes such an embodiment. That is, in the present invention, the meaning of the structure is not particularly limited in shape and material, and includes various materials, various shapes, and structures as long as transfer is possible.

  The present invention provides a film in which microrings or microdots having a unique fine shape are regularly arranged, and has a periodic structure having a shape different from that of a so-called porous honeycomb structure film. In that respect, it provides a very specific film, and is expected to be used greatly in various technical fields such as electronic circuits, photonic crystals, and regenerative medical materials.

The figure which shows the SEM image of the honeycomb film produced in Example 1 The figure which shows the SEM image of the ring-shaped film transcribe | transferred on the ITO substrate. The figure which shows the SEM image which shows that the diameter of the ring transcribe | transferred on the ITO substrate differs The figure which shows the SEM image of the film of the dot structure transferred on the ITO substrate The figure which shows the identification and change of material by FT-RAS measurement The figure which shows the identification and change of material by FT-RAS measurement Diagram showing the transition point of the material used and the film produced Diagram showing the process by which microrings and microdots are formed

Claims (7)

After the glass transition point of the amphiphilic polymer (Tg) of the heat-treated honeycomb porous thin film made of amphiphilic polymer and the matrix material is less than it, or equal to the Tg of the matrix material on the substrate, the honeycomb from the substrate by peeling off the porous thin film, or Utsushitoru only the honeycomb porous amphiphilic polymer distributed in the pores near the thin film on the substrate, or, once dissolved only the amphipathic polymer, it by solidifying within the voids of the honeycomb, microring the substrate, or, with a fine pattern or the pattern exhibited micro-ring or microdots, characterized transferring a fine pattern exhibited microdots, that generate Manufacturing method of structure. Said honeycomb porous film expands the solution of the amphiphilic polymer and matrix material, micro-ring according to claim 1, characterized by using a porous thin film formed by evaporation of the solvent under high humidity Or a fine pattern exhibiting microdots or a method of manufacturing a structure having this pattern. 3. The method for manufacturing a microring or a fine pattern having a microdot or a structure having this pattern according to claim 1 or 2, wherein the honeycomb porous thin film has a pore diameter of 100 nm to 100 [mu] m. 4. A method of producing a micropattern or a structure having a microring having a microring or microdot according to any one of claims 1 to 3 , wherein the amphiphilic polymer is a biodegradable and biocompatible material. A method for producing a micropattern or a structure having this pattern, which is characterized by being a microring or microdot. A method for producing a micropattern or a structure having a microring having a microring or microdot according to any one of claims 1 to 3 , wherein the amphiphilic polymer is an electronic functional material or an optical functional material. A method for producing a micro-ring or a fine pattern having a micro-dot or a structure having this pattern, characterized in that the micro-ring or micro-dot is present. A method for producing a microring or a fine structure having a microdot according to any one of claims 1 to 3 , or a structure having this pattern, comprising an amphiphilic polymer and a biodegradable, biocompatible material , electronic functional materials, optical functional materials ionic bonding method for producing a structure having a fine pattern or the pattern exhibited micro-ring or microdots, characterized in that to further coupled for covalent or hydrophobic interactions . A method for producing a microring or a fine structure having a microdot according to any one of claims 1 to 3 , or a structure having this pattern, wherein the amphiphilic polymer and the catalytic functional material are ionically bonded and shared. bond or manufacturing method of a structure having a fine pattern or the pattern exhibited micro-ring or microdots, characterized in that to further coupled for hydrophobic interaction.

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