JP4334972B2 - Manufacturing method of three-dimensional periodic structure - Google Patents

Description

  The present invention relates to a method for manufacturing a three-dimensional periodic structure.

  Conventionally, Non-Patent Document 1 discloses a method of forming a periodic structure of thin skin particles. This method uses the periodic structure formed by the fine particles as a mold first, and after filling the polymer between the particles, the first particles are removed to form an inverted form of the periodic structure by the first particles. A thin skin particle periodic structure (Hollow structure) is formed in which a thin skin is formed on the inner wall of the reverse mold by a sol-gel reaction (liquid phase reaction) using the reverse mold and then the reverse mold is removed.

  Further, in Non-Patent Document 2, a periodic structure formed by silica particles is first formed, and this is used as a mold, and the surface of the silica particles is formed into a thin film by chemical vapor deposition (CVD). A method of making a thin skin particle periodic structure in which silica particles are removed after film formation is shown.

  Non-Patent Document 3 describes a method for forming a fine particle assembly using a template substrate.

  Patent Document 1 relates to a photonic crystal using fine particles and a method for manufacturing the photonic crystal. After introducing nanoparticles into a template of fine opal crystals to form a structure composed of nanoparticles, the first fine particle opal is disclosed. A so-called inverse structure formed by removing a crystalline template is shown.

  Patent Document 2 relates to a photonic crystal using the crystal structure of fine particles and a method for producing the photonic crystal, and shows that at least three or more layers of inorganic oxide particles arranged in layers are stacked.

  Patent Document 3 relates to a method for forming a photonic crystal that is compressed after arranging fine particles in a polymer medium.

  Patent Document 4 relates to a manufacturing method for forming a photonic crystal using fine particles, and a close-packed structure is formed by dropping a suspension of spherical fine particles on a substrate having a receiving portion and applying a load. It has been shown to obtain a photonic crystal.

  Patent Document 5 relates to a photonic crystal whose photonic band gap can be changed by an external force and a method for manufacturing the photonic crystal. In the photonic crystal, a plurality of bubbles are regularly arranged in a gel-like substance. It is constituted by.

  Patent Document 6 relates to a photonic crystal using fine particles and a method for producing the photonic crystal, and by modifying the surface of the particle with a functional group, a strong three-dimensional structure with a chemical bonding force stronger than electrostatic attraction is obtained. It has been shown to obtain a photonic crystal having.

  Patent Document 7 relates to an opal-like diffractive coloring film having a close-packed structure of fine particles and a method for producing the same.

  Further, Patent Document 8 discloses that a substrate is immersed in a raw material solution containing fine particles and nanoparticles that are erased during post-process firing so as to be aligned or tilted on the substrate, and then fired. The present invention relates to a method for forming a periodic porous structure by eliminating fine particles.

Patent Document 9 and Patent Document 10 relate to a method of forming a photonic crystal by using an original template to create a shape that is an inverted original template.
Vicki L. Colvin et al. “A Lost-Wax Approach to Monodisperse Colloids and Ther Crystals” (SCIENCE VOL291 19 January 2001, 453-457). Yurii A. Vlasov et al., “On-chip natural assembly of silicon photonic bandgap crystals”, “Nature”, November 15, 2001, Vol. 414, p. 289-293 S. M.M. Yang et al., “Opal Circuits of Light-Planarized Microphotonic Crystal Chips”, “Advanced Functional Materials”, June 2002, Vol. 6 + 7, p. 425-431 JP 2000-233999 A JP 2001-42144 A JP 2001-249234 A JP 2001-305359 A JP 2002-098848 A JP 2002-341161 A Japanese Patent No. 2905712 (Japanese Patent Laid-Open No. 8-234007) JP 2003-2687 A JP 2001-72414 A Japanese Patent No. 3376411 (Japanese Patent Laid-Open No. 2001-91777)

  A photonic crystal is a material having a periodic structure in which two or more materials having different refractive indexes (one may be air) have spatial symmetry and regularity. Since the photonic crystal has this regular structure / periodic structure, the photonic crystal exhibits characteristics that cannot be obtained by conventional optical materials. The most characteristic one is the expression of photonic band gap (PBG). In the photonic crystal, light having a wavelength corresponding to PBG is not completely transmitted, but light having other wavelengths is transmitted (see FIG. 1).

  A photonic crystal has a complete photonic band gap when the photonic crystal has a characteristic that does not allow light to pass through at a certain wavelength from any direction (see FIG. 2). A photonic crystal having a complete photonic band gap is highly anticipated in terms of application because a complete optical confinement effect can be obtained. However, it is very difficult to actually obtain a photonic crystal having a complete photonic band gap. In many crystals, even if it has a wavelength that does not transmit light from one direction, it cannot be obtained from another direction. Most crystals transmit light at that wavelength (see FIG. 3).

  In order to make the photonic band gap into a complete band gap, it is necessary to select a crystal structure that has a large refractive index modulation (difference in refractive index) of the periodic structure and is advantageous for forming a complete band gap. Here, it will be described how the photonic crystal having a complete photonic band gap is developed from a periodic structure obtained by utilizing the self-assembly phenomenon of fine particles.

  The periodic structure obtained by the self-assembly phenomenon of spherical fine particles is an aggregate of fine particles having a face-centered cubic structure. Usually, such a fine particle aggregate does not have a complete photonic band gap. The reason for this is that in order to form a high-quality periodic structure such as a photonic crystal, it is necessary to use spherical fine particles with a very good particle size distribution. This is because it is obtained only with a limited material such as polystyrene, and such fine particles are not necessarily high in refractive index. Furthermore, due to problems in the crystal structure, in order to form a complete photonic band gap with a face-centered cubic structure arrangement of fine particles, a very large refractive index modulation is required. Thus, a complete photonic band gap cannot be obtained with a face-centered cubic structure array of fine particles. For this reason, as in Patent Document 1, after filling the void portion of the first fine particle aggregate with a material having a large refractive index, the fine particles are removed and the inverted structure of the fine particle structure (inverse structure, see FIG. 4). ) To obtain a photonic crystal having a complete photonic band gap. The inverse structure is predicted by simulation that a complete photonic band gap is formed by using a material having a refractive index of 3 or more. However, the width of the complete photonic band gap is very narrow, It is very difficult to obtain a photonic crystal that is sensitive to imperfections and actually has a complete photonic band gap in various light wavelength ranges. In addition, the requirement for a refractive index of 3 or more may not be readily available depending on the wavelength range. For example, titanium oxide, which is known as a material having a high refractive index in the visible range, has a refractive index in the visible range of about 2.7 to 2.8, and the inverse structure cannot obtain a complete photonic band gap. . Therefore, in order to solve this problem, an aggregate of a thin skin structure as described above (Hollow structure, see FIG. 5) has been proposed.

  The process of the thin skin particle structure is as follows.

  That is, in the method disclosed in Non-Patent Document 2, first, a spherical silica particle having a uniform particle diameter is immersed in a raw material liquid dispersed in ethanol in a state where the substrate is erected, and a thin film of silica particles is formed on the substrate surface. A regular structure aggregate is obtained (see FIG. 6). Next, after a silicon thin film is formed on the surface of the silica particles by chemical vapor deposition (CVD), the silica particles are removed to form a thin particle structure (see FIG. 5). ). In this method, a thin skin particle structure can be formed directly from a thin-film regular structure assembly of silica particles by using chemical vapor deposition (CVD). With this method, the thin skin particle structure and the substrate can be integrated in the chemical vapor deposition method (CVD method). However, since it is difficult to apply a wide band gap metal oxide material such as titanium oxide on the surface of the particle by chemical vapor deposition, a photonic crystal having PBG in the visible range is used. It is difficult to form.

  On the other hand, in the method shown in Non-Patent Document 1, as in the above technique, first, the substrate is immersed in a raw material liquid in which spherical silica particles having a uniform particle diameter are dispersed in ethanol, A thin-film regular structure assembly of silica particles is obtained on the surface (FIG. 7A). Next, after the monomers are filled between the particles and polymerized (FIG. 7B), the first particles are removed to form an inverse structure of the polymer, thereby forming the inverse of the particle aggregate (FIG. 7). (C)). When forming the reverse mold, polystyrene is used as the reverse mold material. The reverse type void is filled with titanium alkoxide and turned to titanium oxide to form thin skin-like titanium oxide on the reverse type inner wall (FIG. 7D). Thereafter, the polystyrene is removed to obtain a thin skin particle structure of titanium oxide (FIG. 7 (e)). By the way, as a variation of this method, after that, using poly (methyl methacrylate) (PMMA) as the reverse type of the polymer, and in the same way as above, filling the reverse type void with titanium alkoxide and turning to titanium oxide A particle aggregate structure of titanium oxide can be obtained due to the difference in surface properties between polystyrene and PMMA.

  In this method, since a liquid phase reaction is used in the process of forming the thin skin particles, a sol-gel reaction or the like can be used to form a thin skin particle structure of a wide band gap metal oxide material. A photonic crystal having a PBG in the region can be formed. However, in this forming method, the mold is removed after the mold is filled with other materials, and the periodic structure and the substrate are peeled off at that time (see FIG. 7E). . Therefore, in order to pattern the periodic structure for device formation, after forming the periodic structure on the entire surface, the periodic structure is attached to the substrate, and then unnecessary regions are removed by etching or the like. However, it is generally difficult to pattern metal oxides such as titanium oxide by etching. For this reason, a technique capable of patterning a thin skin particle structure of a wide band gap material such as a metal oxide on a substrate has been desired.

  An object of the present invention is to provide a method for producing a three-dimensional periodic structure capable of integrally forming a thin skin particle structure of a wide band gap material such as a metal oxide on a substrate.

  Another object of the present invention is to provide a method for producing a three-dimensional periodic structure capable of patterning by integrating a thin skin particle structure of a wide band gap material such as a metal oxide on a substrate.

  In order to achieve the above object, according to the first aspect of the present invention, there is provided a method for producing a three-dimensional periodic structure having a three-dimensional periodic structure. Forming a body on the first substrate, and sandwiching the thin-film regular structure assembly formed on the first substrate between the second substrate, the first substrate and the second substrate, and the thin film Filling the precursor liquid of the second material between the particles of the regular ordered structure aggregate, solidifying and turning to the second material; removing the first material particles in the thin regular structure aggregate; The step of forming the thin film-like periodic structure of the second material on the second substrate by peeling from the first substrate, the thin film-like periodic structure of the second material on the second substrate, and the third The substrate is disposed in parallel at a minute distance, and the thin film-like periodic structure of the second material on the second substrate and the third substrate The third material of the precursor liquid filling, the steps to turn in the third material solidifies after this, is characterized by performing the removal of the second material and a release of the second substrate.

  According to a second aspect of the present invention, in the method for manufacturing a three-dimensional periodic structure according to the first aspect, the thin film-like periodic structure of the second material on the second substrate and the third substrate are made minute. The step of arranging in parallel at a distance is characterized in that an inter-substrate distance defining member is sandwiched between the thin film-like periodic structure of the second material on the second substrate and the third substrate.

  According to a third aspect of the present invention, in the method for manufacturing a three-dimensional periodic structure according to the second aspect, monodisperse particles are used as the inter-substrate distance defining material.

  According to a fourth aspect of the present invention, in the method for manufacturing a three-dimensional periodic structure according to the first aspect, a thin-film regular structure aggregate of spherical monodisperse particles made of the first material is formed on the first substrate. In this step, a thin-film regular structure aggregate of spherical monodisperse particles made of the first material is formed on the first substrate in an arbitrary pattern shape.

  The invention according to claim 5 is the method for producing a three-dimensional periodic structure according to claim 1, wherein the surface of the second material is hydrophilic and the surface of the third substrate is hydrophilic. It is characterized by that.

  According to a sixth aspect of the present invention, in the method for manufacturing a three-dimensional periodic structure according to the first aspect, the step of filling the third material precursor liquid, solidifying it and turning to the third material is the third step. This is characterized in that it is a step of filling an aqueous solution in which nanoparticles of the above material are dispersed and depositing the nanoparticles on the inner surface of the thin-film periodic structure and the surface of the third substrate.

  The invention described in claim 7 is the method for producing a three-dimensional periodic structure according to claim 1, wherein the step of filling the solid material precursor liquid, solidifying it and turning to the third material is a sol solution. After the filling, the third material is deposited on the inner surface of the thin-film periodic structure and the surface of the third substrate by firing.

According to the first to seventh aspects of the invention, the thin skin particle structure of a wide band gap material such as a metal oxide can be integrally formed on the substrate. Further, a thin skin particle structure of a wide band gap material such as a metal oxide can be integrated and patterned on a substrate.

  Hereinafter, the best mode for carrying out the present invention will be described.

(First form)
According to a first aspect of the present invention, in a method for producing a three-dimensional periodic structure having a three-dimensional periodic structure, a thin-film regular structure aggregate of spherical monodisperse particles made of a first material is formed on a first substrate. And the thin film-like ordered structure aggregate formed on the first substrate is sandwiched between the first substrate and the second substrate, and particles of the thin-film ordered structure aggregate. A step of filling a precursor liquid of the second material in between, solidifying and turning to the second material, removing particles of the first material in the thin-film regular structure assembly, and peeling from the first substrate The step of forming the thin film-like periodic structure of the second material on the second substrate and the thin film-like periodic structure of the second material on the second substrate and the third substrate at a minute distance The precursor liquid of the third material is placed between the thin film-like periodic structure of the second material on the second substrate and the third substrate. It Hama, the steps to turn in the third material solidifies after this, is characterized by performing the removal of the second material and a release of the second substrate.

  FIG. 8 is a diagram for explaining a manufacturing method of the three-dimensional periodic structure according to the first embodiment.

  Referring to FIG. 8, first, a thin-film regular structure assembly of spherical monodisperse particles made of a first material is formed on a first substrate (FIG. 8A), and then formed on the first substrate. The thin film-like ordered structure assembly is sandwiched between the second substrates, and the precursor liquid of the second material is filled between the first substrate and the second substrate and between the particles of the thin-film ordered structure integration, and solidified. Then, it turns to the second material (FIG. 8B). Thereafter, the particles of the first material in the thin-film regular structure assembly are removed, and peeling from the first substrate is performed to form a thin-film periodic structure of the second material on the second substrate ( FIG. 8 (c)). Next, the thin film-like periodic structure of the second material on the second substrate and the third substrate are arranged in parallel at a minute distance, and the thin film-like period of the second material on the second substrate is arranged. A precursor liquid of the third material is filled between the structure and the third substrate, and then solidified and turned into the second material (FIG. 8D). Finally, by removing the second material and peeling the second substrate, a thin-particle structure of the third material fixed on the third substrate can be obtained (FIG. 8 (e)). )).

  Thus, in the first embodiment, the reverse type of the thin-film regular structure aggregate of spherical monodisperse particles formed on the first substrate is intermediately transferred to the second substrate, and this reverse type is used. Then, when forming the thin skin particle structure, the thin film-like periodic structure of the second material on the second substrate and the third substrate are arranged in parallel at a minute distance, and the third material By filling and solidifying the precursor liquid, the third material is also filled in the gap between the third substrate and the three-dimensional periodic structure (thin skin particle structure) fixed on the third substrate. Body).

(Second form)
According to a second aspect of the present invention, in the method for manufacturing a three-dimensional periodic structure according to the first aspect, the thin film-like periodic structure of the second material on the second substrate is separated from the third substrate by a minute distance. In the step of arranging in parallel, the inter-substrate distance defining member is sandwiched between the thin film-like periodic structure of the second material on the second substrate and the third substrate.

  In the second embodiment, in the step of arranging the thin film-like periodic structure of the second material on the second substrate and the third substrate in parallel at a minute distance, the second material on the second substrate. By interposing the inter-substrate distance defining material between the thin-film periodic structure of the material and the third substrate, the second substrate and the third substrate can be arranged in parallel at a minute distance. It becomes.

(Third form)
According to a third aspect of the present invention, in the method for producing a three-dimensional periodic structure according to the second aspect, monodisperse particles are used as the inter-substrate distance defining material.

  In the third embodiment, since monodisperse particles are used for the inter-substrate distance defining material, the distance between the second substrate and the third substrate is minute, and a parallel arrangement can be easily realized. Become.

(4th form)
According to a fourth aspect of the present invention, in the method for manufacturing a three-dimensional periodic structure according to the first aspect, a thin-film regular structure aggregate of spherical monodisperse particles made of the first material is formed on a first substrate. The process is characterized in that a thin-film regular structure aggregate of spherical monodisperse particles made of the first material is formed in an arbitrary pattern shape on the first substrate.

  That is, in the fourth embodiment, the liquid phase process is used to form the third material, and the intermediate transfer process is used to fix the three-dimensional periodic structure on the substrate. It is possible to obtain a three-dimensional periodic structure (thin skin particle structure) fixed in the above and formed in an arbitrary pattern shape.

(5th form)
According to a fifth aspect of the present invention, in the method for manufacturing a three-dimensional periodic structure according to the first aspect, the surface of the second material is hydrophilic and the surface of the third substrate is hydrophilic. It is characterized by.

  In the fifth embodiment, a liquid phase process is performed by selecting, as the second material, a material in which the solidified surface of the second material is hydrophilic and the surface of the third substrate is hydrophilic. Using this, it is possible to obtain a thin skin particle structure fixed on the third substrate.

(Sixth form)
According to a sixth aspect of the present invention, in the method for manufacturing the three-dimensional periodic structure according to the first aspect, the step of filling the solid precursor liquid of the third material and solidifying it into the third material is the third step. It is characterized in that it is a step of filling an aqueous solution in which nanoparticles of material are dispersed and depositing the nanoparticles on the inner surface of the thin-film periodic structure and the surface of the third substrate.

  In the sixth embodiment, the step of filling the precursor liquid of the third material, solidifying and turning to the third material is filled with the aqueous solution in which the nanoparticles of the third material are dispersed, Since it is a step of depositing on the inner surface of the structure and the surface of the third substrate, the choice of materials used for the third material can be expanded.

(7th form)
According to a seventh aspect of the present invention, in the method of manufacturing the three-dimensional periodic structure according to the first aspect, the step of filling the third material precursor liquid, solidifying it, and turning to the third material, After filling, firing is performed to deposit a third material on the inner surface of the thin-film periodic structure and the surface of the third substrate.

  In the seventh embodiment, the step of filling the third material precursor liquid, solidifying and turning to the third material is performed by filling the sol solution and then baking the third material to form a thin film cycle. Since it is a step of depositing on the inner surface of the structure and the surface of the third substrate, the choice of materials used for the third material can be expanded.

  Example 1 is an example corresponding to the first, second, third, fifth, and seventh modes. FIG. 9 is a diagram for explaining the method of manufacturing the three-dimensional periodic structure according to the first embodiment.

  In Example 1, first, a well-cleaned glass substrate (first film) was prepared in a raw material liquid in which spherical monodispersed silica particles (particles of the first material) having a particle size of 300 nm were dispersed in ethanol dispersion medium at 4 wt%. As shown in FIG. 6, the substrate is dipped in the upright state. The container filled with the raw material liquid is placed on a hot plate set at 40 ° C. in order to promote the evaporation of ethanol and prevent the silica particles in the raw material liquid from precipitating. By placing in this state for 4 days, a thin-film regular structure assembly of silica particles is obtained on the surface of the glass substrate (FIG. 9A).

  Next, the silica particle thin-film regular structure assembly formed on the surface of the glass substrate is sandwiched between a hydrofluoric acid-treated silicon substrate (second substrate), styrene and a polymerization initiator (2, 2- A mixed solution of dimethyl-2-phenylacetophenone) is injected between the glass substrate and the silicon substrate. The injected mixed solution is favorably penetrated between the particles of the ordered structure of silica particle thin film by capillary action. Then, UV light is irradiated for 5 hours, and a liquid mixture turns into a polystyrene (polystyrene, 2nd material) (FIG.9 (b)).

  Thereafter, the composition formed in the above steps is immersed in a hydrofluoric acid solution for 5 hours to remove silica particles, and the structure is peeled from the glass substrate. As a result of this step, a polystyrene thin-film periodic structure is obtained on the silicon substrate (FIG. 9C).

  Next, a polystyrene thin-film periodic structure on a silicon substrate and a glass substrate (third substrate) are arranged in parallel at a distance of 2 μm. In order to satisfactorily perform this, particles having a particle diameter of 2 μm are adhered in advance to the surface and peripheral portions of the glass substrate as spacers for determining the distance.

  Then, titanium alkoxide is injected between the polystyrene thin film periodic structure on the silicon substrate and the glass substrate. The injected titanium alkoxide enters the pores in the polystyrene thin-film periodic structure satisfactorily by capillary action. Thereafter, pre-baking is performed at 120 ° C. for 1 hour. Titanium alkoxide is injected and pre-baked five times in total (FIG. 9 (d)). After the above steps, firing is performed at 500 degrees for 3 hours. By this process, polystyrene is almost disappeared, but finally, by rinsing with THF, the polystyrene residue is removed to obtain a thin skin particle structure of titanium oxide fixed on the glass substrate. (FIG. 9 (e)).

  Example 2 is an example corresponding to the first, second, third, fourth, fifth and seventh modes. FIG. 10 is a diagram for explaining the method of manufacturing the three-dimensional periodic structure according to the second embodiment.

  As the raw material liquid used in Example 2, the same liquid as in Example 1 is used.

  In Example 2, a substrate obtained by patterning a polymer on a glass substrate is used. About the method of forming this substrate, it is formed by a method generally described in Non-Patent Document 3, called MIMIC (Micromolding inside Microcapillaries).

  Similar to FIG. 6, the substrate is immersed in a container filled with the raw material liquid in a state where the substrate is erected. This container is placed on a hot plate set at 40 ° C. in order to promote the evaporation of ethanol and prevent the silica particles in the raw material liquid from precipitating. By placing in this state for 4 days, a thin-film regular structure assembly of silica particles is obtained in the region of the groove formed by patterning on the glass substrate (FIG. 10A). Next, the thin film-like ordered structure aggregate of silica particles formed on this substrate is sandwiched with a silicon substrate (second substrate) treated with hydrofluoric acid, and styrene and a polymerization initiator (2,2-dimoxy- 2-phenylacetophenone) is injected between the glass substrate and the silicon substrate. The injected mixed solution is favorably penetrated between the particles of the ordered structure of silica particle thin film by capillary action. Then, UV light is irradiated for 5 hours, and a liquid mixture turns into a polystyrene (polystyrene, 2nd material) (FIG.10 (b)).

  Thereafter, the composition formed in the above steps is immersed in a hydrofluoric acid solution for 5 hours to remove silica particles, and the structure is peeled from the glass substrate. As a result of this step, a polystyrene thin-film periodic structure is obtained on the silicon substrate (FIG. 10C).

  Next, a polystyrene thin-film periodic structure on a silicon substrate and a glass substrate (third substrate) are arranged in parallel at a distance of 2 μm. In order to satisfactorily perform this, particles having a particle diameter of 2 μm are adhered in advance to the surface and peripheral portions of the glass substrate as spacers for determining the distance.

  Then, titanium alkoxide is injected between the polystyrene thin film periodic structure on the silicon substrate and the glass substrate. The injected titanium alkoxide enters the pores in the polystyrene thin-film periodic structure satisfactorily by capillary action. Thereafter, pre-baking is performed at 120 ° C. for 1 hour. Titanium alkoxide is injected and temporarily fired five times (FIG. 10D). After the above steps, firing is performed at 500 degrees for 3 hours. This process almost eliminates the mold polystyrene and the polymer that was originally used for patterning, but finally, it is rinsed with THF so that the residue is removed and patterned on the glass substrate. Further, a thin skin particle structure of titanium oxide can be obtained (FIG. 10 (e)).

  As is clear from the above description, the fixation of the thin skin particle structure of titanium oxide on the substrate is the factor that enabled the patterning of the thin skin particle structure.

  Example 3 is an example corresponding to the first, second, third, fifth and sixth modes. FIG. 11 is a diagram for explaining the method of manufacturing the three-dimensional periodic structure according to the third embodiment.

  The raw material liquid and the first substrate used in Example 3 are the same as those in Example 1. Further, a titanium oxide nanoparticle solution in which titanium oxide nanoparticles having a particle diameter of 5 nm or less are dispersed in ethanol is prepared.

  In Example 3, first, a thin-film regular structure assembly of silica particles is obtained on a glass substrate (first substrate) by the same method as in Example 1 (FIG. 11A). Next, in the same manner as in Example 1, the silica particle thin-film regular structure assembly on the glass substrate was sandwiched between the hydrofluoric acid-treated silicon substrate (second substrate), styrene and the polymerization initiator ( 2,2-Dimethyl-2-phenylacetophenone) is injected between a glass substrate and a silicon substrate, and irradiated with UV light, whereby the mixture is converted into polystyrene (polystyrene, second material). It turns (FIG. 11 (b)). Thereafter, the silica particles are removed by the same method as in Example 1, and the structure is peeled from the glass substrate to obtain a polystyrene thin-film periodic structure on the silicon substrate (FIG. 11 (c). )). Next, in the same manner as in Example 1, using polystyrene particles having a particle diameter of 2 μm, a polystyrene thin-film periodic structure on a silicon substrate and a glass substrate (third substrate) are arranged in parallel at a distance of 2 μm. Then, a titanium oxide nanoparticle solution is injected between the polystyrene thin film periodic structure on the silicon substrate and the glass substrate, and ethanol is evaporated by treatment at 90 ° C. for 1 hour. The injection of the titanium oxide nanoparticle solution and the heat treatment are performed three times in total (FIG. 11 (d)). After the above steps, firing is performed at 500 degrees for 3 hours. By this process, polystyrene is almost disappeared, but finally, by rinsing with THF, the polystyrene residue is removed to obtain a thin skin particle structure of titanium oxide fixed on the glass substrate. (FIG. 11 (e)).

  In the above embodiment, the first material is silica, the second material is polystyrene, the third material is titanium oxide, the first substrate is a glass substrate, the second substrate is a silicon substrate, and the third substrate. Although a glass substrate is used for the present invention, the present invention is not limited to this material. The points required for each material are as follows.

  First, the points required for the first material are that monodisperse particles can be obtained and that they can be removed in a later step.

  The point required for the second material is that the precursor state before solidification is liquid, and the surface after solidification is hydrophilic.

  Further, the point required for the third material is that the precursor state before solidification is liquid, and a material capable of forming a uniform thin film upon solidification. In general, metal oxides and nanoparticles that can be formed from alkoxides as shown in the examples are applicable.

  In addition, the point required for the first substrate is that the particles are accumulated on this, so that good wettability is desired for the dispersion medium of the raw material liquid in which the first material is dispersed. .

  In addition, since the second substrate is required to be an intermediate transfer substrate, the second substrate is a material that does not cause substrate peeling in the first material removing step.

  The third substrate is required to be hydrophilic and to be a material that does not peel or disappear in the second material removal step.

The present invention is applicable to a field where a photonic crystal using a three-dimensional periodic structure can be used, such as an optical component and an optical integrated circuit.

It is a figure which shows the light transmission spectrum of a photonic crystal. It is a figure which shows the light transmission spectrum (when a complete photonic band gap is formed) of a photonic crystal. It is a figure which shows the light transmission spectrum (when a complete photonic band gap is not formed) of a photonic crystal. It is a figure which shows an inverse structure. It is a figure which shows a thin skin particle structure (Hollow structure). It is a figure for demonstrating the formation method of the thin film-like regular structure integration body of a silica particle. It is a figure which shows the formation process (issue which this invention is going to solve) of the thin-skin particle structure using a liquid phase process. It is a figure for demonstrating the manufacturing method of the three-dimensional periodic structure of this invention. FIG. 3 is a diagram for explaining Example 1; FIG. 6 is a diagram for explaining a second embodiment. FIG. 10 is a diagram for explaining Example 3;

Claims (7)

In the method for producing a three-dimensional periodic structure having a three-dimensional periodic structure, a step of forming a thin-film regular structure aggregate of spherical monodisperse particles made of a first material on a first substrate; The thin film-like ordered structure assembly formed on the substrate is sandwiched between the second substrates, and the precursor liquid of the second material is interposed between the first substrate and the second substrate and between the particles of the thin-film ordered structure assembly. And solidifying and turning to the second material, removing the particles of the first material in the thin-film regular structure assembly, and removing the first material from the first substrate, thereby removing the second material on the second substrate. The thin film-like periodic structure of the second material, the thin-film periodic structure of the second material on the second substrate, and the third substrate are arranged in parallel at a minute distance, and the second A precursor liquid of the third material is filled between the thin film-like periodic structure of the second material on the substrate and the third substrate, and solidified by third solidification. A step to turn on the quality, then this method of manufacturing a three-dimensional periodic structure and performs the removal of the second material and a release of the second substrate. The method of manufacturing a three-dimensional periodic structure according to claim 1, wherein the second material thin film-like periodic structure on the second substrate and the third substrate are arranged in parallel at a minute distance. A method for producing a three-dimensional periodic structure, characterized in that an inter-substrate distance defining material is sandwiched between a thin film-like periodic structure of a second material on a second substrate and a third substrate. 3. The method for manufacturing a three-dimensional periodic structure according to claim 2, wherein monodisperse particles are used as the inter-substrate distance defining material. 2. The method for producing a three-dimensional periodic structure according to claim 1, wherein in the step of forming a thin-film regular structure aggregate of spherical monodisperse particles made of the first material on the first substrate, the first material is used. A method for producing a three-dimensional periodic structure, comprising: forming a thin-film regular structure assembly of spherical monodisperse particles in an arbitrary pattern shape on a first substrate. 2. The three-dimensional periodic structure according to claim 1, wherein the surface of the second material is hydrophilic and the surface of the third substrate is hydrophilic. Manufacturing method. The method for manufacturing a three-dimensional periodic structure according to claim 1, wherein the step of filling the precursor liquid of the third material, solidifying and turning to the third material includes an aqueous solution in which nanoparticles of the third material are dispersed. A method for producing a three-dimensional periodic structure, comprising filling and depositing nanoparticles on the inner surface of the thin-film periodic structure and the surface of the third substrate. The method for manufacturing a three-dimensional periodic structure according to claim 1, wherein the step of filling the precursor liquid of the third material, solidifying and turning to the third material is performed by filling the sol solution and then baking. A method for producing a three-dimensional periodic structure, comprising the step of depositing a third material on the inner surface of the thin-film periodic structure and the surface of the third substrate.

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