WO2005009891A1

WO2005009891A1 - Structure and method for producing structure

Info

Publication number: WO2005009891A1
Application number: PCT/JP2004/010037
Authority: WO
Inventors: Xuan-Ming Duan; Hong-Bo Sun; Satoshi Kawata
Original assignee: Japan Science And Technology Agency
Priority date: 2003-07-15
Filing date: 2004-07-14
Publication date: 2005-02-03
Also published as: JPWO2005009891A1

Abstract

Disclosed are a structure composed of a resin and nanoparticles dispersed in the resin and a method for producing such a structure. A substance as the precursor of the nanoparticles is mixed into a monomer and/or oligomer as the raw material of the resin, and the monomer and/or oligomer is polymerized into the resin by two-photon photopolymerization. Then nanoparticles are formed by a chemical reaction such as oxidation, reduction, hydroxylation, dehydration, sulfuration, or oxidation-reduction, using the above-mentioned substance as a reactant.

Description

Specification

Structure and method of manufacturing structure

Technical field

The present invention relates to a structure and a method for manufacturing the structure, and more particularly, to a structure including a resin and nanoparticles dispersed in the resin, and a method for manufacturing the same. Background art

[0002] Polymer micro 'nano three-dimensional structures including nano-functional materials such as metal nanoparticles are available in MENS (Micro Electro Mechanical Systems) and NEMS (Nano Electro Mechanical Systems). Various types of microphones · New characteristics are given to nanodevices. For this reason, the above-mentioned three-dimensional structure of polymer micro'nano is expected to be applied to various uses.

[0003] A method for producing a structure including particles in a polymer is described in, for example, Non-Patent Document 1 and Patent Document 1. Non-Patent Document 1 discloses, as a prior art, a method of manufacturing a structure containing titanium dioxide in a photocurable resin. This method uses a solution containing titanium (IV) ethoxide, methacrylic acid as a photocurable resin, ethylene glycol dimethacrylate, and 2,2-dimethoxy-12-phenylacetophenone as a polymerization initiator. Is cured by ultraviolet light (wavelength: 355 nm).

[0004] Patent Document 1 discloses a method for producing a structure containing a fluorescent dye in a photocurable resin. In this method, a fluorescent dye is mixed with a photocurable resin, and the photocurable resin is photopolymerized and cured by two-photon absorption. Further, a method for manufacturing a micro'nano device using two-photon absorption is disclosed in Non-Patent Document 23, for example.

[Non-Patent Document 1] Atsushi Shishido, Ivan B. Diviliansky, I. C. Khoo, Theresa S.

Mayer, Suzushi Nishimura, Gina L. Egan, and Thomas E. Mallouk, APPLIED

PHYSICS LETTERS Vol. 79, No. 20, issued on November 12, 2001

(Non-patent literature 2) Satoshi Kawata, Hong-Bo Sun, Tomokazu Tanaka, Kenji Takada, Nature, Vol. 412, No. 6848, pp. 697-698 (Published August 16, 2001)

[Non-Patent Document 3] EUROPEAN MATERIALS RESEARCH SOCIETY 2003 SPRING MEETING (June 10-13, 2003 Proceedings)

[Patent Document 1] Japanese Patent Application Laid-Open No. 2003-1599 (Publication date: January 8, 2003) [Problems to be solved by the invention]

However, in the method of Non-Patent Document 1, it is difficult to mix titanium (IV) ethoxide with a photocurable resin, and furthermore, the titanium dioxide contained in the photocurable resin aggregates. Problem. Further, according to this method, the particle diameter of titanium dioxide contained in the photocurable resin can be reduced to only about 1 zm. In addition, the titanium (IV) ethoxide used in this method readily reacts with water vapor in the air. For this reason, the method disclosed in Non-Patent Document 1 has a problem that it must be performed in an atmosphere of an inert gas such as nitrogen or argon.

[0006] Further, the method described in Patent Document 1 is a method in which a fluorescent dye itself is mixed with a photocurable resin, so that the function of the fluorescent dye is affected by the relationship with the ultraviolet light that polymerizes the photocurable resin. There is a problem that S is restricted. In addition, Non-Patent Document 2 discloses a method of including particles in a photocurable resin, and discloses any method.

[0007] The present invention has been made in view of the above-described conventional problems, and has as its object to disperse fine particles in a resin without restricting the function of the fine particles, and to manufacture the resin by this method. Another object of the present invention is to provide a structure made of a resin containing nanoparticles, and a micro / nano device using the structure. Disclosure of the invention

[0008] In order to solve the above-mentioned problems, a method for producing a structure of the present invention is a method for producing a structure comprising a resin and nanoparticles dispersed in the resin, comprising: The precursors of the nanoparticles are mixed with the monomer and Z or oligomer, and the monomers and / or oligomers are cured by a two-photon photopolymerization method. It is characterized by producing nanoparticles.

[0009] Further, in the method for producing a structure of the present invention, the substance may include an ion or the ion. It is characterized by using a compound.

[0010] In the present invention, "nanoparticles" are fine particles produced by the method of the present invention. According to the method of the present invention, nanoparticles having an average particle diameter of less than 1 zm are easily produced. For example, those having an average particle diameter of 500 nm or less, 300 nm or less, and 100 nm or less can be easily produced. Further, the term “substance that is a precursor of nanoparticles” refers to a substance capable of producing nanoparticles, such as an ion and a compound containing the ion. The “two-photon photopolymerization method” means photopolymerization in which polymerization is initiated by two-photon absorption. Note that two-photon absorption is a kind of third-order nonlinear optical effect, and is a process in which molecules that simultaneously absorb two photons are excited. In two-photon absorption, two photons are excited, so the energy per photon is half that of normal one-photon absorption.

That is, in two-photon absorption, the frequency is half of one-photon absorption, and the wavelength is twice that of one-photon absorption. The probability of one-photon absorption is usually proportional to the intensity of incident light, while that of two-photon absorption is proportional to the square of the intensity of incident light. Therefore, according to two-photon absorption, molecules in a spatially minute region can be excited.

[0012] Further, in the two-photon absorption, the wavelength used is twice that of the one-photon absorption, and the molecules are excited at a long wavelength. Therefore, (1) the light transmittance to the substance is improved, and It has the advantage that molecules at deep positions can be excited. (2) The molecules excited and polymerized by photons are less susceptible to light scattering and refraction in the sample.

[0013] Accordingly, according to the configuration described above, a fine structure made of a resin can be obtained by curing a monomer and / or an oligomer as a raw material of the resin by a two-photon photopolymerization method. Further, according to this, the substance serving as the precursor of the nanoparticle can be held in the fine structure made of the resin. By using the substance held in the fine structure of the resin as a reactant and performing a chemical reaction to generate nanoparticles, a nanoparticle with an extremely small particle size is generated in the fine structure of the resin. Can be done.

[0014] Further, according to this, by adjusting the irradiation time, energy, irradiation direction, and the like of light when performing the two-photon photopolymerization method, the substance to be a precursor of the nanoparticle, which is held by the resin, is controlled. The distribution can be manipulated freely in two and / or three dimensions. That is, before Since the precursor can be arranged at a desired position in the resin, the precursor material of the nanoparticle has a structure in which the substance is regularly arranged in a plane and a structure in which the substance is regularly arranged in a three-dimensional manner. Alternatively, a structure in which a two-dimensional arrangement and a three-dimensional arrangement are combined can be easily manufactured.

[0015] Further, according to the above configuration, the monomer and Z or the oligomer as the raw material of the resin are mixed with the substance as the precursor of the nanoparticle rather than mixing the nanoparticle itself, and the two-photon light is obtained. Nanoparticles are generated after the resin is formed by polymerizing the raw materials by the polymerization method. For this reason, according to the production method of the present invention, the function of the nanoparticles is not limited by the condition that they are mixed with the monomer and / or the oligomer. In addition, since what is mixed into the monomer and / or oligomer used as the resin raw material is not the nanoparticle itself but the substance that serves as the precursor of the nanoparticle, it is included in the raw material that is related to the viscosity of the resin to be manufactured. Can be mixed evenly.

Therefore, according to the production method of the present invention, nanoparticles can be dispersed in the fine structure of the resin. Therefore, it is possible to manufacture a resin structure in which nanoparticles having a very small particle diameter are dispersed. In addition, in such a structure, the function provided by the nanoparticles is sufficiently exhibited. The ability to efficiently disperse nanoparticles in a resin with high viscosity can be achieved.

[0017] In order to solve the above problems, in the method for manufacturing a structure of the present invention, the chemical reaction includes an oxidation reaction, a reduction reaction, a hydroxylation reaction, a dehydration reaction, a sulfidation reaction, and a redox reaction. It is characterized by being at least one kind of chemical reaction selected from:

According to the above configuration, nanoparticles can be generated by a simple operation.

[0019] Further, in order to solve the above problems, the structure of the present invention is characterized by comprising a resin and nanoparticles dispersed in the resin and having an average particle diameter of 300 nm or less.

According to the above configuration, it is possible to provide a structure whose optical properties are controlled.

That is, the optical properties of the resin in which the nanoparticles are dispersed can be arbitrarily adjusted by controlling the distribution of the nanoparticles having an average particle diameter of 300 nm or less dispersed in the resin. Therefore, it is possible to provide a structure having suitable optical properties according to the purpose and application. [0021] In the structure of the present invention, in order to solve the above problems, it is preferable that the resin is a photocurable resin.

According to the above configuration, the mechanical properties of the structure can be improved. That is, according to the photocurable resin, a high-strength structure can be formed by curing the resin by irradiating light. Therefore, the mechanical properties of the structure can be improved by using the photocurable resin. Can be.

[0023] In the structure of the present invention, in order to solve the above-mentioned problems, it is preferable that the nanoparticles are made of at least one selected from metals, semiconductors, and oxides.

[0024] According to the above configuration, various functions can be imparted to the structure of the present invention. In other words, nanoparticles of metals, semiconductors, and oxides have various functions, such as conductivity and luminescent properties, and have various functions by dispersing them in resin. It can be a structure.

[0025] The structure of the present invention has a distance force of 10 / m or less between two furthest points on the outer shape of a cross section cut in a direction perpendicular to the direction of extension of the fine particle-containing portion including the nanoparticle. Configuration.

According to the above configuration, a photonic crystal can be formed from the structure according to the present invention.

[0027] The photonic crystal of the present invention comprises the above-described structure, and is characterized in that the lattice constant is 20 µm or less.

[0028] A micro'nano device according to the present invention includes an optical waveguide, an optical switch, or an optical integrated circuit constituted by the above structure.

According to the above configuration, by utilizing the optical properties of the structure of the present invention, it is possible to provide a micro / nano device having a conventional structure, a new structure, and a function. .

[0030] The structure and the photonic crystal manufactured by the manufacturing method of the present invention can be used as a micro'nano device having a new function. Micro-nano devices are manufactured by “nano processing” that combines “micro-machining”, a micro-processing technology, and “nano-machining”, which forms an ultra-fine structure at the atomic and molecular level. Can the manufacturing method produce new structures and photonic crystals? By using these, micro-nano devices with new functions can be realized.

[0031] Still other objects, features, and advantages of the present invention will be more fully understood from the following description. Also, the advantages of the present invention will become apparent in the following description with reference to the accompanying drawings.

Brief Description of Drawings

[FIG. 1 (a)] FIG. 1 (a) is a view schematically showing a structure that is effective in the present embodiment, and a hatched portion is a fine particle containing portion containing nanoparticles.

FIG. 1 (b) is a view schematically showing a structure acting on the present embodiment, which is a cross-sectional view taken along an arrow when cut in a direction perpendicular to a direction in which a resin portion containing fine particles extends. Is shown.

FIG. 2 is an absorbance curve showing the absorbance of titanium (IV) atalylate when the mixing ratio of titanium (IV) ethoxide and acrylic acid is changed.

FIG. 3 is an absorbance curve showing the absorbance of a titanium (IV) -containing resin when the ratio of titanium (IV) atalylate in the titanium (IV) -containing resin is changed.

FIG. 4 is a view showing a relationship between laser irradiation time and resin size by two-photon photopolymerization in Examples.

FIG. 5 is a view showing a relationship between laser irradiation time and resin size in Examples.

FIG. 6 is a view showing the state of a hydrated titanium (IV) -containing resin before and after heat treatment, observed with an electron microscope in Examples.

FIG. 7 (a) is a view showing the structure of the resin of FIG. 6 observed with an electron microscope.

FIG. 7 (b) is a view showing a state of a hydrated titanium (IV) -containing resin before heat treatment observed by the electron microscope of FIG.

FIG. 7 (c) is a view showing a state of the hydrated titanium (IV) -containing resin (structure of the example) after the heat treatment, observed with the electron microscope of FIG.

FIG. 8 is a graph showing the light transmittance of the monomer of the urethane acrylate-based photocurable resin SCR500, the resin containing titanium (IV) hydrate, and the structure of this example in the example of the present invention. is there. BEST MODE FOR CARRYING OUT THE INVENTION

[Embodiment]

The following will describe one embodiment of the present invention.

The structure according to the present embodiment has a configuration including a resin and nanoparticles dispersed in the resin. First, a method for manufacturing a structure according to the present invention will be described below.

[0035] In the manufacturing method according to the present embodiment, first, a substance serving as a precursor of nanoparticle is mixed with a monomer and / or oligomer (hereinafter, appropriately referred to as "monomer") serving as a raw material of a resin.

[0036] Here, the substance that is a precursor of the nanoparticle is, as described above, a substance that can generate a nanoparticle such as an ion or a compound containing the ion. If the nanoparticle to be used is titanium oxide (Ti〇), the precursor substance should be titanium

2

Ion (Ti ³⁺ (IV)).

[0037] In the present embodiment, when ions are used as a substance that is a precursor of the nanoparticles, the type of the ions is not particularly limited, and depends on the type of the nanoparticles dispersed in the resin. May be set appropriately. Further, one kind of the above-mentioned ions may be used, or two or more kinds may be used as needed.

[0038] In the present embodiment, ions themselves or compounds containing the ions can be used as the precursor of the nanoparticle, but these can be mixed with monomers and the like. is there. Specific examples of the compound include a metal complex such as titanium ethoxide (Ti (OCHCH)); a metal salt such as chloroauric acid; or cadmium oxide (CdO

2 3 4

) And the like, and these are compounds that are soluble in the above monomers and the like.

[0039] In addition, the above-mentioned monomer and the like are not particularly limited as long as they are a raw material of a resin and start photopolymerization by two-photon absorption. The degree of polymerization of the above oligomer is not particularly limited as long as it is about 2-20.

[0040] In the present embodiment, it is preferable to use, as the monomer or the like, one that becomes a photocurable resin by being cured by irradiation with ultraviolet light. Thermosetting resin cures monomer etc. Since the volumetric shrinkage and the mechanical strength at the time of the formation are small, the mechanical properties of the structure can be improved.

Therefore, in the present embodiment, acrylic acid (CH 2 = CHCOOH), methacrylic acid (C

2

H C (CH) COOH), acrylate (MMA, etc.), acrylic monomers, urethane

twenty three

It is preferable to use monomers such as phthalate, styrene and epoxy monomers and z or their oligomers. In the present embodiment, one type of these monomers and the like may be used, or two or more types may be used as necessary.

[0042] The mixing ratio of the substance serving as the precursor of the nanoparticle to the monomer (the substance serving as the precursor / monomer) is preferably in the range of 0.1% by weight to 60% by weight. More preferably, it is in the range of 1% by weight to 20% by weight. By setting the mixing ratio between the precursor substance and the monomer or the like to be equal to or more than the lower limit of the preferable range, the amount of the nanoparticles dispersed in the resin becomes too small, and the properties of the nanoparticles are utilized. It can be prevented from becoming a structure. Further, by setting the mixing ratio of the precursor substance and the monomer or the like to the upper limit of the above-mentioned preferable range or less, the amount of the nano-particles contained in the resin is too large, and thus the nano-particles are used. It is possible to control that the optical properties of the structure cannot be controlled.

When titanium ion (Ti ³⁺ (IV)) is used as the precursor substance, the ratio of titanium ion to monomer (titanium ion / monomer, etc.) is 1% by weight or more and 15% by weight or less. It is more preferable to be within the range of 2% by weight or more and 10% by weight or less.

When gold ion (Au ³⁺ ) is used as the precursor material, the mixing ratio (gold ion / monomer, etc.) of the gold ion and the above-mentioned monomer or the like is 1% by weight or more. It is more preferable to be within the range of 5% by weight or less, more preferably within the range of 5% by weight or more and 20% by weight or less.

[0045] Further, as a substance of the precursor, the case of using cadmium ion (Cd ^2+), the force Domiu Ion and mixing ratio of the monomers (cadmium ions / monomers) are 1 weight ^_0/0 or more It is more preferable that the content be in the range of 10% by weight or less, and it is further preferable that the content be 0.5% by weight or more and 5% by weight or less. Next, the monomer and the like are cured by a two-photon photopolymerization method. In this embodiment mode, the monomer or the like is irradiated with laser light to cause the monomer or the like to perform two-photon absorption. Then, two-photon photopolymerization is initiated using a polymerization initiator. The type of the polymerization initiator is not particularly limited, and may be appropriately set as needed.

[0047] At this time, the output of the laser beam (energy of the laser beam) may be in the range of 0.1 lmW or more and 10 OmW or less. In the present embodiment, the output is preferably in the range of lmW to 200 mW, more preferably in the range of 3 mW to 50 mW. When the output of the laser beam is equal to or more than the lower limit of the above preferable range, photopolymerization can be suitably performed. In addition, when the output of the laser beam is set to be equal to or less than the upper limit of the preferable range, the monomer and the like can be prevented from being denatured by the heat of the laser beam. Upon irradiation with the laser light, the monomer or the like that has absorbed two photons undergoes photopolymerization to become a resin.

[0048] In the production method of the present embodiment, since a monomer or the like is cured by a two-photon photopolymerization method, a fine structural resin can be obtained. As a result, the precursor of the nanoparticle is held in the fine resin. In addition, by adjusting the irradiation time, energy, irradiation direction, etc. of the laser beam when performing the two-photon photopolymerization method, the distribution of the precursor substance held in the resin can be two-dimensionally and / or three-dimensionally. It can be operated freely. In other words, by adjusting the conditions of two-photon polymerization, an arbitrary structure made of a resin can be produced in two-dimensional and / or three-dimensional directions, so that the distribution of the precursor substance contained in the resin can be freely determined. Can be operated.

[0049] Then, after preparing a resin having a fine structure holding a substance serving as a precursor of the nanoparticle, a chemical reaction using the substance as a reactant is performed to generate the nanoparticle in the resin. The above-mentioned chemical reaction is not particularly limited as long as it is a reaction for generating nanoparticles from a substance that is a precursor of the nanoparticles, and examples thereof include an oxidation reaction; a photoreduction reaction, a chemical reduction reaction, and the like. Reduction reaction; hydroxylation reaction; dehydration reaction by heating or the like; sulfidation reaction, and oxidation-reduction reaction. By generating nanoparticles by at least one kind of chemical reaction selected from these reactions, it is possible to generate nanoparticles by a simple operation. It should be noted that a plurality of the above reactions are combined to produce nanoparticles. May be.

If the substance serving as the precursor is cadmium ion (Cd ²⁺ ), nanoparticles can be generated by, for example, a sulfidation reaction. Here, the sulfurization reaction when the precursor material is Cd ²⁺ is shown by the following formula (1).

Cd ²⁺ + S ² — → CdS (1)

Alternatively, nanoparticles may be generated from cadmium ions by an oxidation-reduction reaction represented by the following formula (2).

Cd ²⁺ + Se ² — → CdSe (2)

As described above, according to the present embodiment, different types of nanoparticles can be generated from a substance that is a precursor of the same type of nanoparticles by performing different chemical reactions.

If the precursor substance is a titanium ion (Ti ³⁺ (IV)), the precursor substance, that is, the resin holding the titanium ion, is subjected to the two-photon photopolymerization method. Simply by leaving it in the air, the titanium ions react with the water vapor (H の) in the air,

2

Nanoparticles composed of titanium dioxide (TiO 2) are produced.

2

[0052] According to the present embodiment, a substance that is a precursor of the nanoparticle is not mixed with a monomer or the like that is a material of the resin, but is mixed with a monomer or the like that is a material of the resin. Since the nanoparticles are formed after the resin is formed by the two-photon photopolymerization method, the function of the nanoparticles is not limited. Therefore, it is possible to manufacture a structure in which the function of the nanoparticles is sufficiently exhibited. In addition, according to the manufacturing method of the present embodiment, since the substance serving as the precursor of the nanoparticle can be uniformly mixed in the monomer or the like, the precursor that is related to the viscosity of the resin produced by polymerization of the monomer or the like can be used. The body can be evenly dispersed. Therefore, it is possible to efficiently disperse the nanoparticles in a resin with high viscosity.

The structure obtained by the method according to the present embodiment is a structure in which nanoparticles are dispersed in a fine resin. According to the above-described method, by appropriately adjusting the chemical reaction for producing the nanoparticles, the average particle diameter of the nanoparticles can be reduced to 300 nm or less. In the present embodiment, the average particle diameter of the nanoparticles is set to 100 nm or less. It is more preferable that the thickness be 50 nm or less. As the average particle diameter of the nanoparticles becomes smaller, the optical properties of the structure can be more suitably controlled using the nanoparticles.

[0054] Although not particularly limited, a precursor of the nanoparticle is formed by the above-described chemical reaction such that the resin contains a substance such as a metal, a semiconductor, an oxide, or a pigment. It is preferred to select the type of substance. If the structure contains one or more types of substances composed of metals, semiconductors, oxides, and pigments as nanoparticles, the structure having various functions can be created by utilizing the properties of the nanoparticles. Can be provided. For example, a nanoparticle made of cadmium sulfide (CdS) can provide a structure having light emission characteristics.

Here, in the structure according to the present embodiment, the space region including the nanoparticles is referred to as a “particle-containing portion”. 1 (a) and 1 (b) schematically show a structure according to the present invention. In FIG. 1A, a hatched portion is a fine particle-containing portion. Fig. 1 (b) is a cross-sectional view taken along the arrow (A-A 'direction) perpendicular to the direction of elongation of the fine particle-containing portion (the direction indicated by arrow D in Fig. 1 (a)). FIG.

The structure according to the present embodiment has a distance between the two furthest points on the outer shape of the cross section cut in a direction perpendicular to the direction of extension of the fine particle-containing portion, that is, the point shown in FIG. The distance between B and B 'can be less than 500nm. In addition, the distance between B and B 'can be set to 200 nm or less, or 10 μΐη or less.

The “distance between the two furthest points on the outer shape” is, for example, the diameter of a circle if the cross section is circular, or the major axis of an ellipse if the cross section is elliptical.

Further, according to the present embodiment, the period of the nanoparticles contained in the particle-containing portion can be set to about the wavelength of light. Photonic crystals with a lattice constant of 20 xm or less and 750 nm or less can be constructed. Further, for example, if the structure having point defects or line defects is formed by controlling the distribution of the nanoparticles dispersed in the resin two-dimensionally or Z- or three-dimensionally, the structure according to the present invention can be obtained. , An optical waveguide, an optical switch, an optical integrated circuit, a light emitting element, a microlaser, a microlaser array, a surface emitting laser, and the like. That is, the present invention Utilizing the optical properties of the powerful structure, it is possible to construct micro / nano devices with new functions that have never existed before.

[0058] The present invention is not limited to the above-described embodiments, and various changes can be made within the scope of the claims, and are obtained by appropriately combining the technical means disclosed in the embodiments. Are also included in the technical scope of the present invention.

[Example]

Hereinafter, an embodiment of a method of manufacturing a structure according to the present invention will be described with reference to FIGS. 2 and 8, but the present invention is not limited thereto.

[(A) Synthesis of Titanium (IV) Atarilate]

Structural formula (1) as a raw material for resin

[Chemical 1]

To no

Acrylic acid represented by and titanium (IV) ethoxide (hereinafter referred to as “TE”) and a precursor of nanoparticle

Structural formula (2)

[Formula 2]

…)

, Mixed with titanium (IV) ethoxide (hereinafter referred to as "TE")

Structural formula (3)

Ti (OCH CH) m (OOCCH-CH) n (Where m and n each represent an integer, and m + n = 4)

Thus, titanium (IV) acrylate was obtained.

[0061] Fig. 2 shows the absorbance of titanium (IV) atalylate when the mixing ratio of TE and acrylic acid was changed. Note that the horizontal axis in FIG. 2; I indicates the wavelength of light incident on the titanium (IV) acrylate.

In FIG. 2, as a mixing ratio of TE and acrylic acid, the absorbance when TE: acrylic acid = 1: 1 is shown by a solid line, and the sphere height when TE: acrylic acid = 1: 2 is shown by a broken line. TE: Acrylic acid = 1

: The absorbance in the case of 4 is indicated by a dashed line.

[0062] From the absorbance curve of Fig. 2, as the ratio of acrylic acid is increased, in other words, T

It is shown that the absorbance decreases as the proportion of E decreases.

[(B) Synthesis of Titanium (IV) -Containing Resin by Two-Photon Photopolymerization Method]

The structural formula (4)

[Formula 3]

0

H ₂ C, ヽ (4)

Sun

H

(Wherein, R represents a hydrocarbon group)

After mixing the monomer of the urethane acrylate-based photocurable resin SCR500 (Nippon Synthetic Rubber Co., Ltd.) and the polymerization initiator represented by the formula, the polymer is irradiated with laser light and subjected to two-photon photopolymerization.

Structural formula (5)

[Formula 4]

And a titanium (IV) -containing resin represented by the following formula:

FIG. 3 shows an absorbance curve showing the absorbance of the titanium (IV) -containing resin when the ratio of the titanium (IV) atalylate in the titanium (IV) -containing resin was changed. In Figure 3, the proportion of titanium (IV) acrylate in the titanium (IV) -containing resin is 32.86% by weight (titanium (IV) acrylate: photocurable resin SCR500 monomer = 1: 2). the results in solid lines, 3 0.79 wt ^_0/0 (titanium (IV) Atari rate: photocurable resin SCR500 = 1: 3) by a dashed line the results of those, 28.65 wt% (titanium (IV) Atari rate : The result of the photocurable resin SCR500 = 1: 4) is shown by the dashed line.

[(C) Resolution of titanium (IV) -containing resin synthesized by two-photon photopolymerization method]

After mixing the above-mentioned titanium (IV) acrylate and the urethane acrylate-based photocurable resin SCR500 monomer and polymerization initiator, laser irradiation is performed when the two-photon photopolymerization method is performed by irradiating laser light. FIG. 4 shows the result of examining the relationship between the time (1 / second (s)) and the size of the resin obtained by the laser irradiation time. From the figure, it can be seen that the longer the laser irradiation time, the larger the size of the obtained resin.

[0066] Fig. 5 shows the laser irradiation time (1 / sec (s)) and the size of the resin cured by the irradiation when the laser light output was set to 300mW, 400mW, and 500mW (this is referred to as " Point size ”). The figure shows that the longer the laser irradiation time, the larger the size of the resin obtained by the irradiation.

[Manufacture of (D) Structure]

By leaving the titanium (IV) -containing resin in the air and reacting titanium (IV) ions contained in the titanium (IV) -containing resin with water vapor (HO) in the air, the general formula (6)

2

[Formula 5]

(Where n represents an integer)

A hydrated titanium (IV) -containing resin represented by the following formula was obtained.

Further, by heating the hydrated titanium (IV) -containing resin at 250 ° C. for 2 hours in the air, the structural formula (7)

[Formula 6]

Was obtained. FIG. 6 shows the state of the hydrated titanium (IV) -containing resin before the heat treatment (left side in the figure) and after the heat treatment (right side in the figure) observed by an electron microscope.

FIG. 7 (a) shows the resin of FIG. 6 observed with an electron microscope. As shown in the figure, the <100> plane of the structure had an 8 × 8 × 2 structure, and the lattice constant at that time was 2.5 μ μη.

[0070] Fig. 7 (b) shows the state of the hydrated titanium (IV) -containing resin before the above-mentioned heat treatment observed by an electron microscope, and Fig. 7 (c) shows the hydrated titanium hydrate after the above heat treatment. (IV) Containing resin (that is, one example of the structure of the present invention) is shown. The hydrated titanium (IV) -containing resin before the heat treatment has a sphere structure with a diameter of 580 nm as shown by the circle in Fig. 7 (b) and a length between the spheres in the stretching direction. Is a 500nm rod (indicated by a square in the figure) Two three-dimensional structures were formed.

[(E) Photonic band gap measurement]

FIG. 8 shows the results of examining the light transmittance of the urethane acrylate-based photocurable resin SCR500 monomer, the hydrated titanium (IV) -containing resin, and the structure of this example. In the figure, the `` base line '' is the background, the `` resin '' is the transmittance of the urethane acrylate-based photocurable resin SCR500 monomer, and the `` resin + Ti ⁴⁺ + before heat treatment '' is titanium (IV) hydrate. The transmittance of the contained resin, “resin + Ti ⁴ ++ after heat treatment” indicates the transmittance of the structure. From the results shown in FIG. 8, it was found that the band gap of the structure obtained in this example transits to a higher wavenumber region as compared with the hydrated titanium (IV) -containing resin before the heat treatment. Industrial potential

As described above, the structure and the method of manufacturing the same according to the present invention control the dispersion of the nanoparticle in the resin and the resin. Useful as

Claims

The scope of the claims

[1] A method for producing a structure comprising a resin and nanoparticles dispersed in the resin,

After mixing a substance that is a precursor of the nanoparticle with a monomer or the like that is a raw material of the resin and curing the monomer or the like by a two-photon photopolymerization method, the above-mentioned substance is reacted by a chemical reaction using the substance as a reactant. A method for producing a structure characterized by producing nanoparticles.

[2] The method for producing a structure according to claim 1, wherein an ion or a compound containing the ion is used as the substance.

[3] The chemical reaction is characterized by being at least one kind of chemical reaction selected from the group consisting of an oxidation reaction, a reduction reaction, a hydroxylation reaction, a dehydration reaction, a sulfidation reaction, and a redox reaction. A method for manufacturing the structure according to claim 1.

[4] A structure comprising a resin and nanoparticles dispersed in the resin and having an average particle diameter of 300 nm or less.

[5] The structure according to claim 4, wherein the resin is a photocurable resin.

6. The structure according to claim 4, wherein the nanoparticles are at least one selected from a metal, a semiconductor, and an oxide.

[7] The distance between the two furthest points on the outer shape of the cross section cut in a direction perpendicular to the elongation direction of the fine particle-containing portion containing the nanoparticle is 10 μm or less. The structure according to 4.

[8] A photonic crystal comprising the structure according to claim 7, having a lattice constant of 20 µm or less.

[9] A micro / nano device comprising an optical waveguide, an optical switch, or an optical integrated circuit, comprising the structure according to claim 3.