JP2006255878A - Method for producing fine structure and use thereof - Google Patents

Abstract

PROBLEM TO BE SOLVED: To form a fine structure having a period of 1 micron or less, more preferably having a period of 100 nm or less, and controlling the orientation of the fine structure irrespective of the presence or absence of crystallinity of a target substance. It is also possible to provide a fine structure manufacturing technique capable of increasing the degree of freedom of a fine structure formation target (substrate or the like).
For example, polytetrafluoroethylene is rubbed onto a smooth formation surface of a substrate to form an alignment film (alignment film forming step), and a target substance that becomes the fine structure is formed on the alignment film as a solvent. A liquid film of the target substance solution dissolved in the liquid film is formed (liquid film formation process), and convection is induced while the solvent is evaporated from the liquid film (convection induction process). Thereby, a fine structure having a lattice-like fine pattern with a period of several tens of nanometers can be manufactured more easily, at low cost, and with controllable orientation.
[Selection figure] None

Description

  The present invention relates to a method for producing a fine (micro) structure of a material having spatial regularity using a self-organization (self-assembly) phenomenon, a fine structure obtained thereby, and a typical use thereof. In particular, the present invention relates to a microstructure that can be suitably used for various optical materials and electronic materials, a manufacturing method thereof, and use thereof.

  In recent years, various electronic and optical devices manufactured using optical materials and electronic materials are increasingly required to have high performance. Specifically, for example, semiconductor devices and the like are required to further improve the degree of integration, and in devices that handle various types of information, further increase in the amount of information, especially image information if the device handles images. There is a demand for further higher definition.

  As one of methods for meeting such a demand, a technique using a quantum size effect has been proposed. That is, a substance used for an optical material or an electronic material, for example, a crystal of various metals or a semiconductor is controlled to a size of 1 to 100 nm (for convenience of explanation, the size of this range is referred to as “several tens of nm level”). For example, since the quantum size effect appears, it has been proposed to use the quantum size effect for manufacturing a high-performance device.

  Regardless of the fine structure of several tens of nanometers above, in general, in order to form a fine structure, it is necessary to control the size and form of the target substance to be processed. Examples of such a technique include a vapor deposition method using a mask, a photolithographic technique using a photochemical reaction and a polymerization reaction, a laser ablation technique, and the like.

  Recently, self-organization technology in the nanotechnology field is attracting attention as a new technology trend for forming fine structures. If self-organization technology is used for the formation of the fine structure, the productivity of the fine structure having such a fine structure can be improved, the manufacturing cost can be reduced, and the economy can be improved. Options for the object for forming the microstructure are expanded. Therefore, there exists an advantage that it is excellent in the freedom degree as a manufacturing technique.

  In many cases, a technique for forming a microstructure of several tens of nanometers by self-organization uses crystal growth. Specifically, for example, a technique for manufacturing semiconductor rods (rod-like structures), wires (string-like structures) made of a specific crystalline substance, and a lattice-like structure in which these are assembled is known. Yes.

  Furthermore, various techniques have been proposed for self-organization of non-crystalline substances. Specifically, the technique currently disclosed by the nonpatent literatures 1-4, the technique currently disclosed by patent document 1, etc. are mentioned, for example. According to the techniques disclosed in Non-Patent Documents 1 to 4, it is possible to form a fine structure in which honeycomb-shaped holes are repeated at a constant period. Further, according to the technique disclosed in Patent Document 1, it is possible to form a fine structure in which a parallel grid pattern in which straight lines are arranged is repeated. In this technique, it is also possible to form a film surface on the surface of a three-dimensional object.

In addition, a technique has been proposed that enables the orientation of the microstructure to be controlled when the microstructure is formed of a crystalline substance. For example, in Non-Patent Document 5, the orientation of the fine structure is controlled by utilizing the orientation growth of crystals.
JP 2003-151766 A (published May 23, 2003) Chemistry Letters p. 821-822 (1996) Thin Solid Films Vol. 327-329, p829-832 (1998) Thin Solid Films Vol. 327-329, p854-856 (1998) Chaos Vol. 9, p308-314 (1999) Nature Vol 352, p414-417 (1991)

  However, in the above conventional technique, the crystallinity of the target substance greatly affects the formation of the microstructure, the types of the microstructure that can be formed are limited, and the orientation of the microstructure can be controlled well. It has become difficult. Therefore, there is a problem that it is inferior in practicality when viewed as a manufacturing technique of a fine structure.

  Specifically, first, in the techniques disclosed in Non-Patent Documents 1 to 4, it has been confirmed that a periodic pattern of honeycomb-shaped holes is formed as a fine structure. It has not been confirmed to produce structures such as rod-like structures. In addition, in these techniques, only a structure having a pattern period in the range of 0.1 μm to several μm has been reported, and in particular, it is practically impossible to form the fine structure of the above-mentioned tens of nm level. Technically, further miniaturization is an issue.

  Further, in the technique disclosed in Patent Document 1, it is possible to form a lattice-like periodic pattern as a fine structure, but it is also the same as the technique disclosed in Non-Patent Documents 1 to 4 described above. In addition, the reported fine structure is a structure having a pattern period in a range of 0.1 μm to several μm. Therefore, further miniaturization is an issue in this technology.

  Furthermore, when the fine structure is used for a wide range of purposes, the fine structure included in the fine structure is a structure having a periodic lattice pattern (lattice structure), or a rod-like structure or a string-like structure. Thus, it is preferable that the lattice structure be formed by gathering. In addition, in manufacturing the microstructure, it is even more preferable that the orientation of the periodic structure can be controlled.

  However, the techniques disclosed in Non-Patent Documents 1 to 4 cannot form a lattice structure, a rod structure, or a string structure. On the other hand, in the technique disclosed in Patent Document 1, it is possible to form a lattice-like pattern and to control the orientation thereof. However, there is no disclosure of forming a fine structure having a pattern period of several tens of nanometers.

  In addition, the technique disclosed in Non-Patent Document 5 utilizes crystal orientation growth as described above. Therefore, the scope of application of this technique is limited to the production of a fine structure using a crystalline substance. Also, with this technique, the crystal orientation cannot be controlled even if the crystal orientation can be controlled, so that a rod-like structure, a string-like structure, or a lattice-like structure in which these are assembled cannot be formed. .

  As described above, when a microstructure having a shape controlled by self-organization is manufactured, in order to control the orientation of the periodic structure to be 100 nm or less and the orientation thereof is not crystalline, Don't be.

  Furthermore, when producing a microstructure by crystallizing such a crystalline substance, the crystalline substance has a property of growing along a specific crystallographic direction so as to exhibit a desired property. Must. Since such crystalline materials are limited, the materials that can be used for the production of microstructures are limited.

  In general, when a fine structure is formed on the surface of a substrate by self-organization using a solution of the target substance, it is necessary to appropriately combine wettability between the substance to be the substrate and the solution. For this reason, combinations of target substances, solvents, and substrates that can be used are severely restricted. Furthermore, in the case of an amorphous material, it has not yet been realized to sufficiently reduce the size of the periodic fine structure.

  The present invention has been made in view of the above problems, and its purpose is to form a microstructure having a period of 1 micron or less, more preferably a period of 100 nm or less, regardless of the presence or absence of crystallinity of the target substance. Provided is a fine structure manufacturing technique that can be formed and the orientation of the fine structure can be controlled, and further, the degree of freedom of a fine structure formation target (substrate, etc.) can be increased. There is.

  As a result of intensive studies in view of the above problems, the inventors of the present invention formed a coating film (liquid film) of the target substance on the substrate surface on which the alignment film made of the polymer material was formed, and evaporated the solvent from the liquid film. However, by inducing convection, it is possible to form a periodic fine structure on the order of several tens of nanometers, and it is possible to control the orientation of the substrate and to find that a wide range of substrates can be used. The present invention has been completed.

  That is, the fine structure manufacturing method according to the present invention has a structure in which a fine pattern is repeated at a constant period in order to solve the above-described problem, and the periodic interval of the fine pattern is at least 1 μm or less. A method for producing a microstructure, comprising: an alignment film forming step of forming an alignment film made of at least a polymer material on a smooth formation surface; and an object of forming the microstructure on the alignment film It includes a liquid film forming step for forming a liquid film of a target substance solution in which a substance is dissolved in a solvent, and a convection induction step for inducing convection while evaporating the solvent from the liquid film.

  In the production method, a fluororesin is preferably used as the polymer material, and the fluororesin is more preferably polytetrafluoroethylene.

  In the manufacturing method, in the alignment film forming step, it is preferable to form an alignment film by rubbing a polymer material on the forming surface, and the alignment film forming step includes a substrate having a smooth forming surface. It is preferable to be applied to.

  Further, in the manufacturing method, in the liquid film forming step, a liquid film may be formed by immersing the formation surface in a target substance solution, or applying, spraying, or dropping the target substance solution on the formation surface. Preferably, the liquid film forming step and the convection induction step are more preferably performed simultaneously.

  The fine structure obtained by the production method has a rod shape, a string shape, or a lattice shape in which these are assembled. Therefore, the present invention includes a fine structure produced by the production method. The body is also included. In addition, as a typical application technique of the present invention, an electronic and / or optical device using a fine structure can be cited.

  As described above, the present invention forms an alignment film by rubbing a polymer material such as fluororesin on a smooth substrate such as glass, and forms a liquid film by casting a solution of the target substance on the alignment film. Then, the solvent is evaporated from the liquid film so as to induce convection. Thereby, a fine structure in which rod-like structures or lattice-like fine patterns are periodically arranged at intervals of several tens to several hundreds of nanometers can be formed. In addition, the fine structure can be formed regardless of the crystallinity of the target substance, and the orientation of the fine structure can be controlled.

  In particular, the thickness of the rod-like structure that forms the lattice-like fine pattern can be 50 nm or less, and it is possible to form a fine structure using either a crystalline material or an amorphous material. Therefore, a fine structure having a quantum size effect can be manufactured using an appropriate material according to the purpose.

  In addition, using a self-organization phenomenon caused by a solution without using a resist or vapor deposition method, a periodic lattice structure having spatial regularity in a desired direction and a rod-like structure constituting the structure are formed. Can do. Therefore, a periodic fine structure of nanometer order can be formed with a simple process, low cost, resource saving, and energy saving.

  As described above, the present invention is a novel technique using a newly discovered type of self-structure formation phenomenon, and the manufactured microstructure is effectively used as a bottom-up substrate technique in nanotechnology. There is an effect that it can be.

  An embodiment of the present invention will be described below with reference to FIG. 6, but the present invention is not limited to this.

(I) Manufacturing method of microstructure according to the present invention A manufacturing method of a microstructure according to the present invention includes an alignment film forming step of forming an alignment film made of at least a polymer material on a smooth forming surface, and the alignment A liquid film forming step of forming a liquid film of a target substance solution in which the target substance to be the microstructure is dissolved in a solvent on the film; and a convection inducing step of inducing convection while evaporating the solvent from the liquid film; Is included. The obtained fine structure has a structure in which a fine pattern is repeated at a constant period (periodic fine structure). However, in the present invention, a lattice pattern or a rod shape constituting the fine pattern is used as the fine pattern. The structure can be formed, and the periodic interval of the fine pattern is at least 1 μm or less, preferably in the range of several tens to several hundreds of nm, more preferably 100 nm or less.

[Target substance and its solution]
In the present invention, the target substance for forming the fine structure is not particularly limited, and a suitable substance can be selected and used according to the use or type of the fine structure to be produced. In particular, in the present invention, since a fine structure can be produced regardless of the crystallinity of the target substance, a wider range of substances can be used as compared with conventional techniques.

  Typical examples of the target substance include crystalline polymers such as polyethylene, polypropylene, and polyvinyl chloride; amorphous polymers such as polystyrene and polymethyl methacrylate; 1,6-di (N-carbazolyl) ) Low molecular organic compounds such as -2,4-hexadiyne, porphyrin, phthalocyanine; metal salts such as calcium hydroxide and sodium stearate; metal colloidal particles such as gold and silver; polymer latex; nanostructures such as carbon nanotubes Body; and the like.

  The target substance is prepared as a solution or a dispersion, and formed as a liquid film on the alignment film by a liquid film forming step. The solvent (or dispersion medium) used to prepare the solution or dispersion is not particularly limited, and the target substance can be sufficiently dissolved or dispersed and evaporated to induce convection in the convection induction step. Anything is possible. However, materials that dissolve or corrode the substrate or penetrate the substrate are not suitable, and therefore the material of the substrate needs to be taken into consideration when selecting. In the following description, the solvent and the dispersion medium are simply referred to as “solvent” unless otherwise specified.

  Specific examples of the solvent include aromatic solvents such as benzene, toluene, and xylene; ketone solvents such as acetone and methyl ethyl ketone; alcohol solvents such as methanol, ethanol, butanol, and isopropanol; ether solvents such as diethyl ether. Other organic solvents; water; and the like. These solvents can be used alone or as a mixture of two or more.

  The wettability between the substrate and the solvent is not particularly limited. As described above, wettability between the substrate and the solvent is important in the formation of a fine structure by self-organization using a solution, but in the present invention, it is not necessary to consider wettability, so that it is used more than before. The degree of freedom of the solvent can be increased.

  In the present invention, the target substance may be a solution or a dispersion, but when used as a dispersion, the target substance particles are preferably at least 100 nm or less. Thereby, the size of the fine structure obtained can be further reduced. In the case of a dispersion, a known surfactant or emulsifier may be added so that the particles can be stably dispersed in a solvent. The amount of these additives is not particularly limited as long as the particles of the target substance can be effectively dispersed and do not adversely affect the liquid film formation step and the convection induction step.

In the present invention, the method for preparing the solution or dispersion is not particularly limited. In the case of a solution, depending on the combination of the target substance and the solvent, a known method can be used in consideration of the solubility of the target substance. What is necessary is just to prepare as a solution. Similarly, in the case of a dispersion, the dispersion may be prepared by a known method in consideration of the dispersibility of the target substance in a solvent. Further, the concentration of the target substance solution or dispersion is not particularly limited, but it is usually preferably in the range of 1.0 × 10 ^{−10 to} 1.0% by weight, and 1.0 × 10 More preferably, it is in the range of ^{-4 to} 0.1% by weight. If the target substance solution (or dispersion liquid) is not such a dilute solution (or dispersion liquid), a fine structure cannot be formed effectively in the convection induction process.

  Note that, for convenience of explanation, in this specification, a part where only “solution” is described can be rephrased as “dispersion liquid” depending on the combination of the target substance and the solvent. That is, the term “solution” used in the present invention includes a form of “dispersion” in which a target substance is dispersed in a solution (dispersion medium). In addition, the production method according to the present invention may include a step of preparing a target substance solution, if necessary.

〔substrate〕
In the present invention, the fine structure is preferably manufactured using a substrate having a smooth surface. That is, the smooth surface of the substrate is used as the formation surface of the fine structure. Here, it is not limited to a specific material of the substrate, can form a smooth surface, is stable with respect to the solvent used, such as an alignment film formation process, a liquid film formation process, a convection induction process, etc. What is necessary is just to have durability in each process.

  In particular, in the present invention, as described later, when polytetrafluoroethylene is preferably used as the material of the alignment film, the temperature of the substrate needs to be approximately 180 ° C. or higher. Therefore, it is preferable that the material withstands heating at least 180 ° C. or higher. More specifically, it preferably has sufficient hardness, strength, and rigidity at a temperature of 180 ° C.

  Specific examples of such substances include glass-based materials such as soda lime glass and alkali-free glass; silica-based materials such as cleaved surfaces of mica and silicon wafers; various metals; ) Polymer materials; other inorganic materials such as indium tin oxide (ITO) and tin oxide; and the like.

  The shape of the substrate may be a flat plate shape, and the size is not particularly limited, and a substrate having an appropriate size may be used according to the type of microstructure, manufacturing equipment, or the like. In the present invention, the surface on which the fine structure is formed needs only to be smooth, so the shape does not necessarily have to be a flat shape. It may be a surface having a three-dimensional structure (three-dimensional object) instead of a two-dimensional structure such as a substrate.

[Alignment film formation process]
The alignment film forming step is a step of forming an alignment film made of at least a polymer material on the formation surface of the microstructure. Here, as the polymer material that is the material of the alignment film, it can be effectively formed as an alignment film on the formation surface of the substrate, and exists stably in the subsequent liquid film formation process and convection induction process, and forms a fine structure. Although it will not specifically limit if it does not have a bad influence on this, Preferably a fluororesin is used. Among these, polytetrafluoroethylene can be particularly preferably used.

  The thickness of the alignment film is not particularly limited, and the thickness may be any thickness as long as the alignment film has unevenness at the molecular level. In the case of the alignment film of polytetrafluoroethylene, the film thickness may be 0.5 nm or more. In addition, the alignment film does not need to completely cover the surface of the substrate, and the surface of the substrate may be partially exposed as shown in Example 1 described later.

  Although the specific formation method of the said alignment film is not specifically limited, The method of forming an alignment film by rubbing a polymeric material on the said formation surface can be used suitably. The shape of the polymer material to be rubbed at this time is not particularly limited, and a material having a preferable shape may be used depending on the shape of the formation surface, the shape of the substrate, and the like. In the examples described later, rod-shaped polytetrafluoroethylene is used.

  By the way, an alignment film having unevenness at the molecular level is formed on a smooth substrate by rubbing polytetrafluoroethylene in advance, and various crystalline substances are formed on the alignment film by a technique such as solution, melt, or vapor deposition. It is known that orientation growth can be achieved (see Non-Patent Document 5). For example, the alignment film of polytetrafluoroethylene formed in Examples described later is the same as the technique disclosed in Non-Patent Document 5, but the operation of the alignment film is completely different.

  That is, in the technique disclosed in Non-Patent Document 5, the alignment film of polytetrafluoroethylene has an action of arranging a specific crystallographic direction in the crystalline material in parallel with the alignment direction of the alignment film. ing. On the other hand, the alignment film in the present invention does not require crystallinity in the material forming the lattice-like fine pattern, and is fine due to convection when the solvent evaporates from the liquid film formed on the alignment film. A pattern occurs.

  Hereinafter, the alignment film forming step will be described in more detail by taking as an example the case of forming an alignment film of polytetrafluoroethylene. In the alignment film of polytetrafluoroethylene, the temperature of the substrate is controlled within a range of 180 ° C. to 360 ° C., preferably within a range of 250 ° C. to 340 ° C., and polytetrafluoroethylene is formed on the surface (formation surface) of the substrate. It is formed by sliding while pressing the lump. When the substrate temperature is less than 180 ° C., a polytetrafluoroethylene thin film cannot be formed. Moreover, since it is higher than melting | fusing point of polytetrafluoroethylene when it exceeds 360 degreeC, problems, such as alignment being impaired and surface shape becoming rough, arise.

  Before forming the alignment film, it is preferable to clean the formation surface by an appropriate technique. Thereby, the alignment film can be stably formed on the formation surface. In the examples described later, the alignment film of polytetrafluoroethylene is formed after cleaning the surface of the glass substrate with an alkali cleaning solution, but is not limited to this, and is appropriate depending on the material of the formation surface, etc. The cleaning method and cleaning conditions should be selected.

  The conditions for rubbing polytetrafluoroethylene on the formation surface are not particularly limited, and appropriate conditions for forming the alignment film can be set according to the type of the formation surface (that is, the type of the substrate). That's fine. For example, in the embodiments described later, the alignment film is formed by moving a polytetrafluoroethylene rod while pressing it at a predetermined pressure and speed.

  A method for forming an alignment film of polytetrafluoroethylene on a flat substrate will be described more specifically with reference to FIG. In FIG. 6, the substrate 2 is heated to a predetermined temperature by the heating means 6. The type of the heating means 6 is not particularly limited, and a known heating device can be used according to the type of the substrate 2 (in the examples described later, a hot plate is used). The polytetrafluoroethylene solid (in this case, a rod-like shape) 5 is initially in the left position in the figure, but is slid rightward in the figure while being pressed against the substrate 2 by the compression moving device 7. As a result, a polytetrafluoroethylene thin film (alignment film) 1 is formed on the substrate 2.

  In the above example, as long as the alignment film can be formed by rubbing a mass of polytetrafluoroethylene in a heated state, the formation surface may have an arbitrary curved surface shape or the like. In addition, the shape of the formation surface is particularly limited as long as the liquid film can be formed and maintained in the subsequent liquid film forming process and the solvent can be evaporated from the liquid film so as to cause convection in the convection induction process. is not. Therefore, the target for forming the fine structure is not necessarily limited to the flat substrate.

  Whether or not the formed polytetrafluoroethylene thin film is an alignment film can be confirmed by observing the surface of the thin film with a differential interference optical microscope. In the case of the alignment film, streaky irregularities can be observed on the surface thereof.

[Liquid film formation process]
In the liquid film forming step, the liquid film is formed by immersing the forming surface in the target substance solution, or coating, spraying, or dropping the target substance solution on the forming surface. The liquid film here refers to a coating layer (or coating film) of the target substance solution formed on the alignment film. The method for forming the liquid film on the alignment film is not particularly limited. As described above, the substrate on which the alignment film is formed is immersed in the target substance solution and the substrate is pulled up (so-called dip coating method). Or a dipping method); a coating method using various coating means such as a bar coater, a roll coater, and a brush; a spraying method using an air brush or an atomizer; Usually, a dipping method and a spray method can be used more preferably.

  When forming the liquid film, it is not necessary to form the liquid film so that the entire substrate and the alignment film are uniformly covered with the liquid film, but in order to control the size and period of the fine pattern of the fine structure. The film thickness of the liquid film and other formation conditions are preferably controlled appropriately. In general, the film thickness of the liquid film is preferably in the range of 0.01 to 100 μm, and more preferably in the range of 0.1 to 10 μm. However, since the preferred range varies widely depending on various conditions such as the concentration of the solution and the temperature of the convection induction process, the film thickness of the liquid film used in the present invention is not limited to the above range.

  The temperature of the target substance solution in the liquid film forming step is not particularly limited as long as it is a temperature at which the target substance is dissolved (or dispersed) in a solvent. Moreover, the formed liquid film does not need to be held so as to be horizontal, and may be inclined. In the present invention, Marangoni convection due to the difference in chemical potential in the target substance solution is important when the solvent evaporates from the liquid film in the convection induction process described later. It can be used in any orientation.

[Convection induction process]
In the convection inducing step, convection, specifically Marangoni convection (possibly Benard convection) is induced by evaporating the solvent from the liquid film formed on the alignment film in the previous liquid film formation step. Thus, a periodic fine structure of at least 1 μm or less is formed. Marangoni convection is a flow of fluid near the surface caused by a difference in interface (liquid-liquid or liquid-gas) tension caused by a temperature gradient or concentration gradient. In the present invention, the solvent is evaporated from the liquid film. Thus, it is considered that Marangoni convection is generated, and thereby a lattice-like fine pattern can be periodically formed. Benard convection is convection caused by a descending fluid that has been cooled and increased in density on the upper surface, and is considered when the influence of gravity cannot be ignored.

  In this step, the method for evaporating the solvent from the liquid film is not particularly limited, and known methods such as heating, decompression, and combinations thereof can be used. For example, in the embodiments described later, a method of heating by a heating means such as a hot plate is used. In the examples described later, the liquid film is formed while heating the substrate on which the alignment film is formed. That is, the liquid film formation step and the convection induction step are performed simultaneously. Thus, depending on the type of target substance and the type of microstructure to be manufactured, the liquid film forming step and the convection inducing step may be performed simultaneously, or may be performed clearly as separate steps. Good.

  In this step, the uniformity of the fine pattern, the size of the formation cycle, and the like can be adjusted by adjusting the rate at which the solvent is evaporated when forming the fine structure. For this purpose, various conditions such as the temperature of the substrate, the solution, the atmosphere, the ambient pressure, and the vapor pressure of the solvent in the atmosphere may be appropriately controlled. By controlling various conditions in this way, it is possible to manufacture a fine structure in which the interval between fine patterns and the size of the period are variously changed.

  By controlling various conditions in this way, it is possible to manufacture a fine structure in which the period of the fine pattern and the thickness of the rod-like or string-like structure forming the fine pattern are variously changed. It is also possible to manufacture a fine structure in which the period of the fine pattern and the thickness of the rod-like structure change continuously according to the position. In particular, in the present invention, a repetitive structure of a lattice-like fine pattern can be formed as the fine structure, but the period of the lattice is at least in the range of 10 to 500 nm, and the thickness of the rod-like structure forming the lattice is 1 nm to It can be controlled to change within a range of 200 nm.

  In the present invention, a fine streak structure having a height of several nm to several hundred nm formed on the surface of the alignment film affects the evaporation of the solvent from the liquid film in the convection induction process. That is, the outline of the target substance solution in the evaporation process is fixed for a certain time along the streak structure. In the meantime, flow from the inside of the target substance solution to the contour occurs, and coupled with the convection accompanying evaporation, the target substance dissolved in the target substance solution is deposited on the substrate surface in a rod shape along the streak structure. Therefore, it becomes possible to form a lattice-like fine pattern having periodicity.

(II) Fine structure according to the present invention The fine structure according to the present invention is manufactured by the above-described manufacturing method, and specifically, a periodic rod-shaped structure, a string-shaped structure, or an assembly of these. It has a lattice structure.

  As described above, the fine structure manufactured according to the present invention is formed with a fine structure (grid-like structure) in which a lattice-like fine pattern is periodically repeated or a rod-like structure forming the fine structure. The formation period is at least 1 μm or less, preferably in the range of several tens to several hundreds of nanometers, more preferably several tens of nanometers.

  Further, even if the target substance is crystalline, the microstructure produced according to the present invention is non-crystalline or very low in crystallinity immediately after production.

  As described above, when a fine structure is used for a wide range of purposes, the fine structure included in the fine structure is a structure having a periodic lattice pattern (lattice structure), a rod-like structure, A structure that can form a lattice-like structure by gathering, such as a string-like structure, is preferable. In the present invention, not only can a microstructure having such a periodic lattice structure be manufactured simply, at low cost and with energy saving, but also the orientation of the lattice structure can be controlled. The degree of freedom of the target substance used is also wider than before. Therefore, the field of application of the present invention is very broad compared to the prior art.

  Conventionally, in order to form a pattern with a similar scale, a large-scale apparatus using radiation with a short wavelength (ie, high energy) such as an X-ray or an electron beam is required, and many work steps are required. I was trying. Therefore, there is a problem in terms of cost, and it has been used only for manufacturing high value-added products such as CPUs. On the other hand, in the present invention, a radiation generating device is unnecessary, and the manufacturing process is merely to rub a polymer against a substrate to form an alignment film, and then cast and evaporate the solution on the alignment film. It has become simple. Therefore, since the present invention can form a fine pattern very easily and inexpensively, it can be used for cost-intensive applications.

  Further, as a technique for forming a periodic fine pattern by self-organization using evaporation of a solvent, the technique disclosed in Patent Document 1 is known. Since the solvent is evaporated while being shifted, there is a restriction on the shape of the workable surface. Although the principle of the technique disclosed in Patent Document 1 is not so clear, the publication discloses that a fine structure can be formed in a wide range of 0.1 nm to 100 mm. Since only examples are given, it is unknown whether a fine pattern can be formed at a level of several tens of nm.

  On an order of magnitude larger than that of the present invention, finger-like pattern formation caused by Marangoni convection (convection caused by a difference in surface tension, which occurs even under weightlessness) is known. The size is several hundred μm, and the size is two to three orders of magnitude larger than a fine pattern of several tens nm level that can be formed by the present invention. Although the principle of the present invention is assumed to be related to Marangoni convection, the operation is different from that of the conventional fine pattern forming technology.

(III) Use of the present invention The method for producing the microstructure according to the present invention and the field of use of the microstructure obtained thereby are not particularly limited, and are widely used in fields where the quantum size effect can be utilized. Can do. As a typical example, an electronic and / or optical device using the microstructure can be given.

  More specifically, a quantum thin film, a quantum wire, an optical element, a surface adsorption protein inspection apparatus, a data recording material, a microelectronic circuit, a template used for producing them, a mask for nanolithography, and the like can be mentioned. .

  Alternatively, for example, by using the present invention and patterning with a conductive polymer material, it is possible to manufacture a small-sized conductive wire from the conductive polymer material. In addition, by using an electrochromic material, it is possible to create a display device or the like using a change in a pattern corresponding to a current.

  Furthermore, since the microstructure formed using the metal nanoparticles has optical anisotropy (Example 7 described later), it is also possible to create a display device using this characteristic for display operation. .

  Further, the optical device using the present invention can be used as a diffraction grating (grating material) or an interference filter in the wavelength region of visible light, ultraviolet light, and X-rays. If a fluorescent material or a phosphorescent material is used, it can be used as a filter for exposure materials having a regular pattern and display materials. By controlling the regular fine pattern, the same effect as that of the photonic crystal can be realized using an organic material.

  In addition, recording materials are manufactured by assigning addresses to predetermined fine patterns by using materials that can cause state changes and chemical changes by applying physical energy such as light, heat, electricity, and magnetism. Is also possible.

  Furthermore, the lattice structure is formed with a hole transport material and filled with an electron transport material, or conversely, the lattice structure is formed with an electron transport material and filled with a hole transport material. A photovoltaic device can be constructed by introducing a dye that is photoexcited into the light.

  As described above, the present invention is used to manufacture various microstructures on a substrate or a three-dimensional object and to display the microstructure on a display device, an optical device, an electronic device, a light emitting device, a photovoltaic device (collectively an electronic device and / or It can be used as an optical device). When manufacturing these electronic devices and optical devices, it is not necessary to form the structure directly used for the device according to the present invention with a target substance. For example, a fine structure is formed from the target substance, and then the target substance is changed by physical means such as irradiation of radiation or heating, or chemical means such as reaction of the target substance with another substance. A microstructure formed of the substance used can be obtained. In addition, a fine structure made of another substance can be manufactured using a fine structure constituted of a target substance as a template.

  Hereinafter, an example of a light-emitting device using the present invention will be specifically described.

  A light-emitting device using the present invention is an element having a light-emitting layer or an organic layer including a light-emitting layer between a pair of electrodes of an anode and a cathode, and in addition to the light-emitting layer, a hole injection layer, a hole transport layer, and an electron injection layer , An electron transport layer, a protective layer, etc., and each of these layers may have other functions. Various materials can be used for manufacturing each layer.

  In the light-emitting device using the present invention, the manufactured microstructure is preferably used as the organic layer of the light-emitting device, and the manufactured microstructure is more preferably used as the light-emitting layer of the light-emitting device.

  The anode supplies holes to a hole injection layer, a hole transport layer, a light emitting layer, and the like, and a metal, an alloy, a metal oxide, an electrically conductive compound, or a mixture thereof can be used. Is a material having a work function of 4 eV or more. Specifically, for example, conductive metal oxides such as tin oxide, zinc oxide, indium oxide and ITO; metals such as gold, silver, chromium and nickel; and a mixture of these metals and conductive metal oxides or Laminates; inorganic conductive materials such as copper iodide and copper sulfide; organic conductive materials such as polyaniline, polythiophene and polypyrrole; and laminates of these with ITO; Among these, conductive metal oxides are preferable, and ITO is particularly preferable from the viewpoints of productivity, high conductivity, transparency, and the like.

  The film thickness of the anode can be appropriately selected depending on the material, but is usually preferably in the range of 10 nm to 5 μm, more preferably in the range of 50 nm to 1 μm, and still more preferably in the range of 100 nm to 500 nm.

  The anode is usually formed as a layer on soda-lime glass, non-alkali glass, a transparent resin substrate or the like. When glass is used as the substrate, alkali-free glass is preferably used as the material in order to reduce ions eluted from the glass. Moreover, when using soda-lime glass, it is preferable to use what gave barrier coatings, such as a silica. The thickness of the substrate is not particularly limited as long as it is sufficient to maintain the mechanical strength, but when glass is used, it is usually 0.2 mm or more, preferably 0.7 mm or more. preferable.

  The anode can be produced by a known method depending on the material, and is not particularly limited. For example, in the case of ITO, an electron beam method, a sputtering method, a resistance heating vapor deposition method, a chemical reaction method (sol-gel method, etc.) A film is produced by a method such as application of a dispersion of indium tin oxide. The anode can be subjected to cleaning or other treatments to lower the drive voltage of the element or increase the light emission efficiency. For example, in the case of ITO, UV-ozone treatment, plasma treatment, etc. are effective.

  The cathode supplies electrons to the electron injection layer, the electron transport layer, the light emitting layer, etc., and the adhesion, ionization potential, stability, etc., between the negative electrode and the adjacent layer such as the electron injection layer, electron transport layer, light emitting layer, etc. Can be selected.

  As a material for the cathode, a metal, an alloy, a metal halide, a metal oxide, an electrically conductive compound, or a mixture thereof can be used. Specifically, for example, an alkali metal such as Li, Na, K, or Cs And its fluorides; alkaline earth metals such as Mg and Ca and their fluorides; gold, silver, lead, aluminum, sodium-potassium alloys or mixed metals thereof; lithium-aluminum alloys or mixed metals thereof; magnesium-silver Alloys or mixed metals thereof; rare earth metals such as indium and ytterbium; Among these, a material having a work function of 4 eV or less is preferable, and aluminum, a lithium-aluminum alloy or a mixed metal thereof, a magnesium-silver alloy, or a mixed metal thereof is more preferable.

  The cathode can take not only a single layer structure of the compound and the mixture but also a laminated structure including the compound and the mixture. The film thickness of the cathode can be appropriately selected depending on the material and is not particularly limited, but is usually preferably in the range of 10 nm to 5 μm, more preferably in the range of 50 nm to 1 μm, and 100 nm. More preferably, it is in the range of ˜1 μm.

  For the production of the cathode, methods such as an electron beam method, a sputtering method, a resistance heating vapor deposition method, and a coating method can be used. A metal can be vapor-deposited alone or two or more components can be vapor-deposited simultaneously. Furthermore, it is possible to produce an alloy electrode by simultaneously depositing a plurality of metals, or an alloy prepared in advance may be deposited. The sheet resistance of the anode and the cathode is preferably low.

  The material of the light emitting layer is a function that can inject holes from the anode or hole injection layer, hole transport layer and cathode or electron injection layer, electron transport layer when an electric field is applied, The layer is not particularly limited as long as it can manufacture a layer having a function of moving the injected charge and a function of emitting light by providing a recombination field of holes and electrons. Specifically, for example, amine compounds, benzoxazole derivatives, benzimidazole derivatives, benzothiazole derivatives, styrylbenzene derivatives, polyphenyl derivatives, diphenylbutadiene derivatives, tetraphenylbutadiene derivatives, naphthalimide derivatives, coumarin derivatives, perylene derivatives, perinones. Derivatives, oxadiazole derivatives, aldazine derivatives, pyralidine derivatives, cyclopentadiene derivatives, bisstyrylanthracene derivatives, quinacridone derivatives, pyrrolopyridine derivatives, thiadiazolopyridine derivatives, cyclopentadiene derivatives, styrylamine derivatives, aromatic dimethylidin compounds, 8- Various metal complexes represented by metal complexes and rare earth complexes of quinolinol derivatives, polythiophene, polyphenylene, polyphenylene Polymeric compounds such as vinylene and the like.

  The thickness of the light emitting layer is not particularly limited, but is usually preferably in the range of 1 nm to 5 μm, more preferably in the range of 5 nm to 1 μm, and still more preferably in the range of 10 nm to 500 nm. .

  The light-emitting material contained in the light-emitting layer (a substance that contributes to the light emission of the light-emitting element) is any light-emitting material such as one that emits light from singlet excitons, one that emits light from triplet excitons, or one that emits light from both. Can be used. In particular, the combination with a light-emitting material including light emission from triplet excited superons is preferable because the effect is more effectively exhibited.

  The manufacturing method of the light emitting layer is not particularly limited when the microstructure obtained by the present invention is not applied to the light emitting layer, but resistance heating vapor deposition, electron beam, sputtering, molecular lamination method, coating method (spin (Coating method, casting method, dip coating method, etc.), LB method, ink jet method and the like are used, preferably resistance heating vapor deposition and coating method are used.

  The material of the hole injection layer and the hole transport layer may be any one having a function of injecting holes from the anode, a function of transporting holes, or a function of blocking electrons injected from the cathode. Good. Specifically, for example, carbazole derivative, triazole derivative, oxazole derivative, oxadiazole derivative, imidazole derivative, polyarylalkane derivative, pyrazoline derivative, pyrazolone derivative, phenylenediamine derivative, arylamine derivative, amino-substituted chalcone derivative, styrylanthracene Derivatives, fluorenone derivatives, hydrazone derivatives, stilbene derivatives, silazane derivatives, aromatic tertiary amine compounds, styrylamine compounds, aromatic dimethylidin compounds, porphyrin compounds, polysilane compounds, poly (N-vinylcarbazole) derivatives, anilines Examples thereof include conductive polymer oligomers such as copolymer, thiophene oligomer, and polythiophene.

  The thicknesses of the hole injection layer and the hole transport layer are not particularly limited, but are usually preferably in the range of 1 nm to 5 μm, more preferably in the range of 5 nm to 1 μm, and 10 nm to More preferably, it is in the range of 500 nm. The hole injection layer and the hole transport layer may have a single-layer structure composed of one or more of the materials described above, or may have a multilayer structure composed of a plurality of layers having the same composition or different compositions.

  As a manufacturing method of the hole injection layer and the hole transport layer, when the fine structure obtained by the present invention is not applicable to each layer, a vacuum deposition method, an LB method, an ink jet method, and the hole injection transport agent as a solvent. A method of coating by dissolving or dispersing (a spin coating method, a casting method, a dip coating method, or the like) can be preferably used. In the case of the coating method, it can be dissolved or dispersed together with the resin component. Specific examples of the resin component include polyvinyl chloride, polycarbonate, polystyrene, polymethyl methacrylate, polybutyl methacrylate, polyester, polysulfone, and polyphenylene oxide. , Polybutadiene, poly (N-vinylcarbazole), ketone resin, phenoxy resin, polyamide, ethyl cellulose, vinyl acetate, ABS resin, polyurethane, unsaturated polyester resin, alkyd resin, epoxy resin, silicone resin, and the like.

  The material for the electron injection layer and the electron transport layer may be any material having any one of a function of injecting electrons from the cathode, a function of transporting electrons, and a function of blocking holes injected from the anode. Specifically, for example, triazole derivatives, oxazole derivatives, oxadiazole derivatives, fluorenone derivatives, anthraquinodimethane derivatives, anthrone derivatives, diphenylquinone derivatives, thiopyrandioxide derivatives, carbidiimide derivatives, fluorenylidenemethane derivatives, Various metals represented by metal complexes of distyrylpyrazine derivatives, heterocyclic tetracarboxylic anhydrides such as naphthaleneperylene, phthalocyanine derivatives, 8-quinolinol derivatives, metal phthalocyanines, benzoxazole and benzothiazole ligands A rust body etc. can be mentioned.

  The film thicknesses of the electron injection layer and the electron transport layer are not particularly limited, but are usually preferably in the range of 1 nm to 5 μm, more preferably in the range of 5 nm to 1 μm, and more preferably in the range of 10 nm to 500 nm. More preferably, it is within the range. The electron injection layer and the electron transport layer may have a single layer structure composed of one or more of the above-described materials, or may have a multilayer structure composed of a plurality of layers having the same composition or different compositions.

  As a manufacturing method of an electron injection layer and an electron transport layer, when the microstructure obtained by the present invention is not applied to each layer, a vacuum steamer method, an LB method, an ink jet method, or the electron injection transport agent is dissolved in a solvent or A method of coating by dispersing (spin coating method, casting method, dip coating method, etc.) can be used. In the case of the coating method, it can be dissolved or dispersed together with the resin component, and as the resin component, for example, those exemplified in the case of the hole injection transport layer can be used continuously.

As a material for the protective layer, any material may be used as long as it has a function of suppressing the entry of elements that promote element deterioration such as moisture and oxygen into the element. Specifically, for example, In, Sn, Pb, Au , Cu, Ag, Al, Ti, a metal such as _{Ni; MgO, SiO, SiO 2,} Al 2 O 3, GeO, NiO, CaO, BaO, Fe 2 Metal oxides such as O ₃ , Y ₂ O and TiO ₂ ; Metal fluorides such as MgF ₂ , LiF, AlF ₃ and CaF 2; Polymers such as polyethylene, polypropylene, polymethyl methacrylate, polyimide and polyurea; Polytetrafluoroethylene , Polychlorotrifluoroethylene, polydichlorodifluoroethylene, a copolymer of chlorotrifluoroethylene and dichlorodifluoroethylene, and a copolymer obtained by copolymerizing a monomer mixture containing tetrafluoroethylene and at least one comonomer , Halogen-based polymers such as fluorine-containing copolymers having a cyclic structure in the copolymer main chain Water absorption more than 1% of the water-absorbing material; water absorption of 0.1% or less proof materials; and the like.

  The method for producing the protective layer is not particularly limited, and specifically, for example, a vacuum steamer method, a sputtering method, a reactive sputtering method, a molecular beam epitaxy method, a cluster ion beam method, an ion plating method, A plasma polymerization method (high frequency excitation super ion plating method), a plasma CVD method, a laser CVD method, a thermal CVD method, a gas source CVD method, a coating method, and an ink jet method can be suitably used.

  The present invention will be described more specifically based on Examples and Comparative Examples, and FIGS. 1 to 5 and FIGS. 7A and 7B to 12, but the present invention is not limited thereto. . Those skilled in the art can make various changes, modifications, and alterations without departing from the scope of the present invention.

[Example 1]
A 1% by weight solution of potassium hydroxide as an alkaline detergent was prepared using a mixed solution of water and ethanol (weight mixing ratio 1:10) as a solvent. The slide glass (substrate) for an optical microscope was immersed in the alkaline detergent for 1 hour or more and then taken out, and the alkaline detergent was washed away with distilled water. The slide glass was air-dried and then placed on a hot plate heated to 300 ° C., and a polytetrafluoroethylene rod was moved from above by pressing it at a pressure of 0.8 MPa and a speed of 2.6 cm / sec. By these operations, an alignment film of polytetrafluoroethylene was formed on the slide glass. The differential interference optical microscope confirmed the stripe-like unevenness | corrugation by the said alignment thin film (alignment film formation process). In this case, the alignment film did not completely cover the substrate surface, and part of the substrate surface was exposed.

Next, para-xylene (manufactured by Wako Pure Chemicals, special grade) is used as a solvent, and this is heated and boiled to dissolve linear polyethylene (manufactured by Fluka, standard sample for GPC calibration, Mw = 36,500). A 3 × 10 ⁻⁴ wt% solution (target substance solution) was prepared. The polytetrafluoroethylene alignment film on the glass substrate is heated to a predetermined temperature (80 ° C. to 110 ° C.) on a hot plate, and the polyethylene solution heated to about 140 ° C. is sprayed thereon (liquid film formation) Process / convection induction process).

  Gold and carbon were vacuum-deposited on the microstructure thus obtained, the sample was peeled off from the glass substrate by a replica method, and observed with a transmission electron microscope. As a result, periodic formation of a lattice-like fine pattern as shown in FIG. 1 was confirmed.

  Further, when the relationship between the conditions of each process was examined when forming such a lattice-like structure, as shown in FIG. 2, between the average thickness of the lattice-like structure of the rod-like structure and the temperature of the hot plate. Correlation was seen. The correlation of FIG. 2 shows that the thickness of the rod-like structure can be controlled by the temperature at which the solvent is evaporated when the periodic lattice-like structure according to the present invention is formed. From the lattice-like fine pattern shown in FIG. 1, in the limited-field electron diffraction, no crystalline diffraction peak was detected in addition to the diffraction peak due to the polytetrafluoroethylene crystal. This indicates that the polyethylene is in an amorphous state.

[Comparative Example 1]
Except for forming a polyethylene lattice structure at a hot plate temperature of 80 ° C., and then heating and dissolving at 150 ° C. for 1 minute while attached to the slide glass, and then cooling to room temperature, the same as in Example 1 above. A microstructure was manufactured, gold and carbon were deposited, and observed with a transmission electron microscope.

  As a result, a lattice-like fine pattern was not observed, and a massive structure formed because polyethylene was dissolved was observed. In the limited-field electron diffraction, a diffraction peak due to the polyethylene crystal was confirmed from this massive structure. This indicates that the polyethylene molecules forming the lattice-like structure observed in Example 1 did not change and had sufficient crystallinity.

[Comparative Example 2]
The alignment film of polytetrafluoroethylene on the slide glass was heated to 80 ° C. on a hot plate, and paraxylene (only a solvent not containing polyethylene) heated to about 140 ° C. was sprayed thereon. Thereafter, as in Example 1, gold and carbon were deposited on the surface of the substrate and observed with a transmission electron microscope.

  As a result, a lattice-like fine pattern was not observed, and only an oriented polytetrafluoroethylene streaky structure was observed as shown in FIG. This confirms that the material forming the lattice structure observed in Example 1 was polyethylene.

[Example 2]
Methyl ethyl ketone (manufactured by Wako Pure Chemical Industries, Ltd.) was used as a solvent, and polystyrene (Scientific Polymer Products Inc., Mw = 45,000) was dissolved in this, and a 4.2 × 10 ⁻³ wt% solution (target substance solution) was dissolved. Prepared. In the same manner as in Example 1, a polytetrafluoroethylene alignment film is formed on a slide glass (substrate), and this is heated to a predetermined temperature (80 ° C. to 110 ° C.) at room temperature or on a hot plate. A polystyrene solution was sprayed. Thereafter, gold and carbon were deposited in the same manner as in Example 1 and observed with a transmission electron microscope. As a result, formation of a lattice-like fine pattern as shown in FIG. 4 was confirmed at any hot plate temperature.

Example 3
A polystyrene solution prepared in the same manner as in Example 2 was dropped at room temperature onto an alignment film of polytetrafluoroethylene on a slide glass prepared in the same manner as in Example 1, and the evaporation process was observed with a differential interference optical microscope. . As a result, the fluctuation of density formed by convection as shown in FIG. 5 was confirmed in the contour portion of the liquid film of the polystyrene solution. The lower part of FIG. 5 shows a state of a cross section cut in the horizontal direction in a part of the micrograph shown in FIG. In the figure, a liquid film of polystyrene methyl ethyl ketone solution 3 is further formed on a polytetrafluoroethylene alignment film 1 formed on a substrate (slide glass) 2, and a convection 4 of the solution is formed in the liquid film. It shows that it is formed.

Example 4
Polyvinyl alcohol (manufactured by Aldrich) was dissolved while boiling distilled water to prepare a 3.8 × 10 ⁻³ wt% solution (target substance solution). A polytetrafluoroethylene alignment film on a slide glass produced in the same manner as in Example 1 was heated to 80 ° C. on a hot plate, and the polyvinyl alcohol solution was dropped thereon to evaporate water. Thereafter, gold and carbon were vapor-deposited in the same manner as in Examples, and observed with a transmission electron microscope. As a result, formation of a lattice-like fine pattern similar to FIG. 4 was confirmed. In the limited field electron diffraction, the diffraction peak of the polyvinyl alcohol crystal was not observed from this lattice structure. This indicates that the polyvinyl alcohol is in an amorphous state.

Example 5
1,6-di (N-carbazolyl) -2,4-hexadiyne (1,6-di (N-carbazolyl) -2,4-hexadiyne, DCHD) is dissolved in acetone (manufactured by Wako Pure Chemical Industries). A 25 wt% solution was prepared. An alignment film of polytetrafluoroethylene on a slide glass produced in the same manner as in Example 1 was immersed in this DCHD solution, taken out, and then air-dried. Thereafter, gold and carbon were deposited in the same manner as in Example 1 and observed with a transmission electron microscope. As a result, formation of a lattice-like fine pattern similar to that in FIG. 1 was confirmed. In the limited field electron diffraction, no diffraction peak of the DCHD crystal was observed from this lattice structure. This indicates that DCHD is in an amorphous state.

Example 6
In the same manner as in Example 1, an alignment film of polytetrafluoroethylene was formed on a slide glass. The alignment film on the glass substrate is heated to 70 ° C. with a hot plate, and a gold colloid dispersion liquid having an average particle diameter of 5 nm, 15 nm, or 50 nm (manufactured by British BioCell International, Ltd., model numbers are EMGC5, EMGC15, EMGC50) was added dropwise to evaporate the water of the dispersion medium. Thereafter, carbon was vacuum-deposited in the same manner as in Example 1, the sample was peeled off from the glass substrate by the replica method, and observed with a transmission electron microscope. As a result, gold colloidal array structures with average particle sizes of 5 nm, 15 nm, and 50 nm were confirmed. FIGS. 7A and 7B show an arrangement structure of colloidal gold of 15 nm as an example. FIG. 7B is a partially enlarged view of FIG.

Example 7
The gold colloid dispersion liquid having an average particle diameter of 5 nm, 15 nm, and 50 nm used in Example 6 was dropped at room temperature onto the alignment film of polytetrafluoroethylene on the slide glass prepared in the same manner as in Example 1, and dispersed. The medium water was evaporated. And the glass substrate was observed with the differential interference microscope as it was. As a result, an array structure was confirmed for gold colloids having an average particle diameter of 5 nm, 15 nm, and 50 nm. An example is shown in FIGS. FIG. 8A shows an arrangement structure of gold colloids having an average particle diameter of 5 nm, and FIG. 8B shows an arrangement structure of gold colloids having an average particle diameter of 50 nm. In addition, the arrow in a figure shows the orientation direction of an alignment film.

  Moreover, carbon was vacuum-deposited on the glass substrate of each sample in the same manner as in Example 1, the sample was peeled off from the glass substrate by the replica method, and observed with a transmission electron microscope. FIGS. 9A and 9B show an arrangement structure of gold colloids having an average particle diameter of 50 nm as an example. FIG. 9 (b) is a partially enlarged view of FIG. 9 (a). 9A and 9B also confirmed the arrangement structure of the colloidal gold.

  Furthermore, when the sample for the transmission electron microscope was observed with a polarizing microscope, when the fine structure was oriented in the direction of 45 degrees with respect to the optical axis of the orthogonal polarizing plate, the transmitted light intensity became maximum, and the polarization When the optical axis of the plate and the orientation of the fine structure are parallel (or vertical), a phenomenon that the transmitted light intensity is minimized is observed. FIGS. 10A and 10B and FIGS. 11A and 11B show this phenomenon. FIGS. 10A and 10B are microscopic images obtained by observing the arrangement structure of colloidal gold particles having an average particle diameter of 50 nm using a polarizing microscope, and the arrows in the figure indicate the alignment direction of the alignment film. 10A is an image in a state where the optical axis of the polarizing plate is sandwiched between polarizing plates (orthogonal polarizing plates) in the horizontal direction of the paper and the vertical direction of the paper, respectively. FIG. It is an image in a state of being sandwiched between polarizing plates (parallel polarizing plates) in which the optical axes of the polarizing plates are both in the vertical direction of the paper. FIGS. 11A and 11B are microscopic images observed in a state where the respective fields of view of FIGS. 10A and 10B are rotated by 45 degrees. Comparing FIG. 10 (a) and FIG. 11 (a), it is shown that the transmitted light intensity of the fine structure (array structure) in FIG. 11 (a) is lower than that in FIG. 10 (a). It was.

Example 8
A slide prepared in the same manner as in Example 1 with a diluted solution obtained by adding distilled water to acrylonitrile-butadiene copolymer latex (manufactured by Zeon Corporation, Nipol1562, average particle size 50 nm, solid content 41%) and diluting 10,000 times It dropped at room temperature on the alignment film of the polytetrafluoroethylene on glass, and the water of the dispersion medium was evaporated. Thereafter, platinum palladium and carbon were vacuum-deposited, the sample was peeled off from the glass substrate by a replica method, and observed with a transmission electron microscope. The observation results are shown in FIG. As a result, as shown in FIG. 12, it was shown that an array structure was obtained with acrylonitrile-butadiene copolymer latex having an average particle diameter of 50 nm. The arrows in FIG. 12 indicate the alignment direction of the alignment film.

  Note that the present invention is not limited to the configurations described above, and various modifications are possible within the scope of the claims, and technical means disclosed in different embodiments and examples respectively. Embodiments and examples obtained by appropriately combining them are also included in the technical scope of the present invention.

  As described above, in the present invention, after the liquid film is formed on the alignment film, the solvent is evaporated so as to cause convection. Therefore, the orientation can be controlled regardless of the presence or absence of the crystallinity of the target substance, and a periodic fine structure can be formed easily and at low cost. Therefore, the present invention can be applied not only to various nanotechnology but also to a wide range of application fields, specifically, fields related to various electronic / optical devices and parts thereof for which higher performance is required. Is possible. Furthermore, among the microstructures obtained by the present invention, the microstructure formed using metal nanoparticles has optical anisotropy, and therefore the present invention can be widely applied to various display devices. is there.

BRIEF DESCRIPTION OF THE DRAWINGS It is a figure which shows the periodic lattice-like structure formed of polyethylene which is one Example of this invention (Example 1), the arrow shows the orientation direction of polytetrafluoroethylene, and a scale bar shows 200 nm. It is a graph which shows the relationship between the thickness of the rod-shaped structure which comprises the periodic lattice-shaped structure formed of the polyethylene shown in FIG. 1, and the substrate temperature at the time of forming the said lattice-shaped structure. In Comparative Example 2, it is a figure which shows the polytetrafluoroethylene orientation film | membrane processed only with the solvent, the arrow shows the orientation direction of a polytetrafluoroethylene, and a scale bar shows 200 nm. It is a figure which shows the periodic lattice-like structure formed of the polystyrene which is another Example of this invention (Example 2), the arrow shows the orientation direction of a polytetrafluoroethylene, and a scale bar shows 1 micrometer. . It is a figure which shows the mode of the convection which arises in the process of forming a lattice-like structure with a polystyrene solution, which is still another embodiment of the present invention. It is a schematic diagram which shows the mode of the cross section, and a scale bar shows 50 micrometers. In one Embodiment of this invention, it is a schematic diagram which shows the state which forms the alignment film of a polytetrafluoroethylene in the surface (formation surface) of a board | substrate. (A) * (b) is a figure which shows the arrangement | sequence structure (micro structure) formed with the gold colloid which is further another Example of this invention, The arrow shows the orientation direction of polytetrafluoroethylene, The scale bar in (a) indicates 500 nm, and the scale bar in (b) indicates 50 nm. (A) * (b) is a figure which shows the arrangement | sequence structure (micro structure) formed with the gold colloid which is further another Example of this invention, The arrow shows the orientation direction of polytetrafluoroethylene, The scale bar indicates 10 μm. (A) * (b) is a figure which shows the arrangement | sequence structure (micro structure) formed with the gold colloid which is further another Example of this invention, The arrow shows the orientation direction of polytetrafluoroethylene, The scale bar in (a) indicates 1 μm, and the scale bar in (b) indicates 50 nm. (A) * (b) is a figure which shows the arrangement | sequence structure (micro structure) formed with the gold colloid which is further another Example of this invention, (a) is the said arrangement | sequence structure between orthogonal polarizing plates. It is the figure which showed the state clamped, (b) is the figure which showed the state which clamped the said arrangement | sequence structure between parallel polarizing plates, the arrow shows the orientation direction of polytetrafluoroethylene, and a scale bar shows 10 micrometers. . (A) * (b) is the figure observed in the state which rotated each visual field of Drawing 10 (a) and (b) 45 degrees, and an arrow shows the orientation direction of polytetrafluoroethylene. (A) * (b) is a figure which shows the arrangement | sequence structure (micro structure) formed with the acrylonitrile butadiene copolymer latex which is further another Example of this invention, and an arrow is polytetrafluoroethylene. The orientation direction is indicated, and the scale bar indicates 10 μm.

Explanation of symbols

DESCRIPTION OF SYMBOLS 1 Polytetrafluoroethylene orientation film 2 Substrate 3 Polystyrene methyl ethyl ketone solution 4 Solution convection 5 Solid polytetrafluoroethylene 6 Heating device 7 Pressure transfer device

Claims (10)

It has a structure in which a fine pattern is repeated at a constant period, and a method for manufacturing a fine structure in which a period interval of the fine pattern is at least 1 μm or less,
An alignment film forming step of forming an alignment film made of at least a polymer material on a smooth forming surface;
On the alignment film, a liquid film forming step of forming a liquid film of a target substance solution in which the target substance to be the microstructure is dissolved in a solvent;
And a convection induction step of inducing convection while evaporating the solvent from the liquid film.   The method for producing a microstructure according to claim 1, wherein a fluororesin is used as the polymer material.   The method for producing a microstructure according to claim 2, wherein the fluororesin is polytetrafluoroethylene.   4. The method for producing a microstructure according to claim 1, wherein in the alignment film forming step, the alignment film is formed by rubbing a polymer material on the formation surface.   5. The method for manufacturing a microstructure according to claim 1, wherein the alignment film forming step is performed on a substrate having a smooth forming surface. 6.   6. The liquid film forming step of forming a liquid film by immersing a forming surface in a target substance solution or coating, spraying or dropping a target substance solution on the forming surface. The manufacturing method of the microstructure according to any one of the above.   The method for manufacturing a microstructure according to any one of claims 1 to 6, wherein the liquid film forming step and the convection inducing step are performed simultaneously.   The method for manufacturing a fine structure according to any one of claims 1 to 7, wherein the fine structure has a bar shape, a string shape, or a lattice shape in which these are aggregated. .   A microstructure manufactured by the method according to any one of claims 1 to 8.   An electronic and / or optical device using the microstructure according to claim 9.