JP2003149401A - Particulate structure and its manufacturing method - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide particulate structures having respectively different periodical structures and formed on the same substrate and a method for manufacturing these particulate structures. SOLUTION: First and second particulate structures are formed on the same substrate, the 1st particulate structure has uniform particulate size and periodical structure of particulate arrangement positions and the 2nd particulate structure has uniform particulate size and periodical structure different from that of the 1st particulate structure. The 1st and 2nd particulate structures are respectively patterned as optional shapes. The particulate structure manufacturing method includes a process for applying and developing a dispersion solution of particulate having the uniform particulate size to the surface of the substrate having a recessed pattern on its surface and drying the developed solution to form a particulate film and a process for peeling the particulate film by using an adsorbing tool having a function capable of adsorbing fine particles and laminating respective particulate films to form the particulate structure.

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a fine particle structure (fine particle array film) in which fine particles are two-dimensionally and regularly arranged on a substrate, and fine particles are three-dimensionally arranged on a substrate (third order). Originally, the present invention relates to a fine particle structure and a manufacturing method thereof. Further, the fine particle structure of the present invention can be applied to all fields in which the effect of the structure in which the fine particles are periodically arranged is utilized, and for example, it is unique in that the structure in which the fine particles are periodically arranged is adopted. It can be used for optical parts, optical integrated circuits, etc. obtained by processing the structure into a desired shape by utilizing the optical characteristics. The structure in which the fine particles are periodically arranged as described herein also includes so-called photonic crystals.

[0002]

2. Description of the Related Art At present, a structure (fine particle array structure) manufactured by regularly arranging fine particles is used in various fields. For example, in the field of optical information recording media, a fine particle array structure is used as an information recording material. Also,
In the field of optical integrated circuits, optical fine particles are used to form a two-dimensional circuit pattern. Further, in the electronic integrated circuit, a small-scale electronic circuit arranges the fine particles formed on the surface and inside of the fine particles, thereby exhibiting a larger scale and a higher function. Further, a fine catalytic reactor formed by arranging fine particle catalysts two-dimensionally is also known.

The following is a conventional technique relating to the fine particle array structure. Patent No. 278348
No. 7: This is a method in which a solution of nanometer particles having a particle diameter of 200 nm or less is filled inside a millimeter-sized circular cell, and the solvent is evaporated under a controlled atmosphere such as air or oxygen to make the nanometer particles a solid surface. Above is a patent for a method of two-dimensional crystallization. Patent No. 282
No. 8374: This relates to a method of two-dimensionally aggregating fine particles by supplying a liquid dispersion medium of fine particles onto a flat surface substrate to form a liquid thin film and controlling the liquid thickness of the liquid dispersion medium by evaporation or the like. It is a patent.

Japanese Patent No. 2828375: This realizes a meniscus shape on the liquid surface from a cell structure 2 for accumulating a liquid dispersion medium of fine particles on a substrate, and covering the cell structure with a hermetically sealed container hood, This is a patent for a two-dimensional agglomeration forming apparatus for fine particles, which controls the liquid film thickness of a fine particle-dispersed liquid by controlling the evaporation amount of the liquid to form two-dimensional agglomeration of fine particles. Patent No. 2828384: This is a method in which a liquid film 2 is disposed on a supporting substrate, and then a particle dispersion liquid 1 is spread on the liquid film 2 without being mixed with the liquid film 2 to obtain a dispersion medium and a liquid film 2. It is a patent regarding a method for forming a particle thin film on the supporting substrate 3 by evaporating and.

Japanese Patent No. 2828386: This involves contacting a substrate with a dispersion suspension of fine particles, moving and sweeping the atmosphere, the meniscus tip at the three-phase contact line of the substrate and the suspension, and moving it. The present invention relates to a method for controlling the particle density and the number of particle layers of a particle thin film by using the moving speed (Vc) of the meniscus tip portion, the particle volume fraction, and the liquid evaporation rate (je) as parameters in manufacturing a particle film by the accumulation of particles. It is a patent. Patent No. 2834416
No .: This is a coefficient in which the volume fraction φ of the fine particles depends on the evaporation rate of the liquid medium, the viscosity coefficient of the liquid medium, etc., the average particle velocity divided by the average liquid molecular velocity, the fine particle film already formed. And the number of molecules per unit time that evaporate from the surface of the wetting film, the effective volume of the liquid medium, the film thickness of the wetting film, the viscosity of the mixed fluid, a method of making it larger than the value calculated by the effective density of the contact line, and This is a patent on a method of feedback controlling the pulling rate of a substrate.

Japanese Patent No. 2885587: This is a liquid containing fine particles or a liquid which forms fine particles by a reaction is once spread on the surface of a high density liquid to control the spread thickness of the liquid as a raw material for the fine particles. Is a patent for a method for forming a fine particle film by two-dimensionally aggregating fine particles and contacting and fixing the agglomerated two-dimensional particle thin film on the surface of a solid substrate. Patent No. 2912562: This is patterned by directly changing the solubility and the melting degree of particles according to a predetermined pattern by directly acting an energy ray on a single-particle film or a multi-particle film of submicron fine particles. This is a patent for a method for obtaining a single particle film or a multi-particle film.

Patent No. 2915812: This is a solid 2
A method of forming a fine particle film that forms a hydrophobic surface by activating or hydrophobizing the surface of the next substrate by irradiating with energy rays, or disposing a specific binding ligand film on the surface of the solid secondary substrate, Alternatively, a method of forming a fine particle film in which a denatured protein is generated by adsorbing a thiol group to transfer and attach the fine particle film, or a method of forming a fine particle film in which ultrafine particles are irradiated with energy rays to generate active radicals to transfer and adhere Is a patent on JP-A-8-22
No. 9474: In this publication, an LB film or an interface film made of a polymer is used as a binder layer to form a particle thin film in the formation of a single particle film or a multi-particle film of fine particles having a particle size of nanometer order by advection integration. The invention of a method of forming a particle film by controlling the formation and fixing it on a transfer substrate is described.

Japanese Laid-Open Patent Publication No. 9-92617: In this publication, the potential energy for charged particles in an electrolyte liquid film is secondarily minimized by controlling ionic strength to form a nanoscale secondary thin film, on which a nanoscale secondary thin film is formed. The invention of a method of confining and accumulating scale particles is described.
Japanese Unexamined Patent Publication No. 6-123886: In this publication, fine particles are selectively arranged in a plane by utilizing a trapping force of a laser beam, and then an in-plane pattern arrangement of the fine particles is frozen or an ultraviolet curable resin is used. The invention of a method for controlling the arrangement of fine particles to be fixed by means of is described.

Japanese Unexamined Patent Publication (Kokai) No. 6-212409: In this publication, a structure in which a fine particle is used as a raw material is to irradiate a position where a fine particle is to be grown with an electron beam and to charge the part to attract the fine particle from the surroundings. The invention of a method of making a body is described. The fine particles used as the raw material include
Assuming carbon particles. Japanese Unexamined Patent Publication No. 9-82939: This publication describes an invention of a fine structure element in which fine particles are arranged in concave portions of a substrate and a manufacturing method thereof. As a method of depositing fine particles, we describe a method of exciting the surface selectively by applying energy to a target position on the substrate surface with heat, light, ultrasonic waves, particle beams, microprobes, etc. to selectively deposit fine particles. ing. The problem to be solved by the present invention is to form an element having uniform characteristics in a finer region than that of a conventional fine processing technique, and regarding the combination of functions exhibited by the periodic structure of particles, , Neither described nor suggested.

Japanese Unexamined Patent Publication No. 10-102243: This publication describes an invention of an ultrafine structure in which ultrafine particles are arranged. Ultrafine particles are formed by irradiating a target with a high-energy beam. As can be seen from the manufacturing method, the present invention does not describe or suggest the effect of the fine particles having a periodic structure. Japanese Patent Laid-Open No. 10-173181: This publication describes an invention of an electronic device using a three-dimensional quantum dot array using fine particles. Specifically, a memory element is assumed as the electronic element. In the present invention, it can be said that the characteristics of the periodic structure of the fine particles are utilized in the three-dimensional quantum dot array, but no description or suggestion is made on the point of utilizing those having different periodic structures at the same time.

Japanese Unexamined Patent Publication No. 10-189601: This publication describes an invention of a method for producing a fine structure using fine particles as a mask. Although the present invention utilizes the feature of having a hexagonal close-packed structure when arranging the fine particles to be a mask, it does not positively utilize the characteristics due to the periodicity of the fine particles. Patent No. 285947
No. 7: This patent relates to a method of regularly arranging ultrafine particles, in which a quartz substrate is immersed in a bicarbonate buffer mixed with photoreactive biotin, and then light is selectively passed through the substrate through a photomask. Irradiation to form a biotin binding region on the light-irradiated portion of the substrate, and at the same time, prepare colloid avidin in which ultrafine particles are bound to avidin, and dip the substrate in a phosphate buffer containing this colloid avidin. By doing so, the ultrafine particles are bound to biotin via avidin to arrange the ultrafine particles. This invention also does not positively utilize the characteristics due to the periodicity of the fine particles.

Japanese Unexamined Patent Publication No. 2000-167387: This publication describes an invention of a method of precisely arranging minute particles one by one on a substrate.
A charged spot is formed by a focused ion beam or the like, and a minute object is attracted and attached to that position.
This invention also does not positively utilize the characteristics due to the periodicity of the fine particles. Patent No. 265342
No. 4: This patent relates to a method for manufacturing a micro component / micro structure by manipulating, bonding, and processing a metal micro object with a microprobe.

Japanese Patent No. 2967198: This patent relates to a three-dimensional precise arraying method of minute objects, in which minute objects are arrayed by facing electrodes, and protrusions are formed on the surface of one of the electrodes. The structure is such that the electric field is concentrated, and the space between the opposed electrodes is filled with a solution in which microscopic particles or fibrous substances are dispersed in a solvent, and an electric field is applied to the chain, which consists of microscopic particles on the protrusions. It is to grow the shape. This invention also does not positively utilize the characteristics due to the periodicity of the fine particles. Patent No. 3069579: This patent relates to a dipole electrode probe for handling microscopic objects.

Japanese Unexamined Patent Publication No. 6-279199: In this publication, a particle size of 2 is provided inside a millimeter-sized circular cell.
The invention describes that nanometer particles are two-dimensionally crystallized on a solid surface by filling a solution of nanometer particles of 00 nm or less and evaporating a solvent under a controlled atmosphere such as air or oxygen. JP-A-6-2775
No. 01 gazette: In this gazette, a liquid dispersion medium of fine particles is supplied onto a flat surface substrate to form a liquid thin film, and the liquid thickness of the liquid dispersion medium is controlled by evaporation or the like to agglomerate the fine particles two-dimensionally. The invention is described.

Japanese Unexamined Patent Publication No. 6-210158: In this publication, a meniscus shape of the liquid surface is realized by a cell structure for accumulating a liquid dispersion medium of fine particles on a substrate, and the cell structure is a hermetic container hood. The invention describes that the liquid film thickness of the fine particle-dispersed liquid is controlled by forming a two-dimensional agglomeration of fine particles by controlling the liquid evaporation amount of the liquid by controlling the liquid evaporation amount of the fine particles. Japanese Patent Laid-Open No. 6-339625: In this publication, a liquid film is provided on a supporting substrate, a particle dispersion liquid is developed on the liquid film without mixing with the liquid film, and then a dispersion medium is formed. An invention is described in which a liquid film is evaporated to form a particle thin film on a supporting substrate.

Japanese Patent Laid-Open No. 7-116502: In this publication, a substrate is brought into contact with a dispersion suspension of fine particles, and the tip of the meniscus at the three-phase contact line between the atmosphere and the substrate is swept developed. The invention has been described in which a fine particle film is produced by moving the particles and accumulating them. And at this time,
The particle density and the number of particle layers of the particle thin film are controlled by using the moving speed (Vc) of the tip portion of the meniscus, the volume fraction of the particles and the liquid evaporation rate (je) as parameters. Japanese Patent Laid-Open No. 8-155378: In this publication, the volume fraction φ of fine particles is a coefficient that depends on the evaporation rate of the liquid medium, the viscosity of the liquid medium, etc., and the average particle velocity divided by the average liquid molecular velocity. Calculated from the number of molecules per unit time that evaporates from the surface of the fine particle film and the wet film that have already been generated, the effective volume of the liquid medium, the film thickness of the wet film, the viscosity of the mixed fluid, and the effective density of the contact line. An invention is described in which the quality of the fine particle film is improved by increasing the value larger than the value. This publication also describes that the quality of the fine particle film is improved by feedback-controlling the pulling rate of the substrate.

Japanese Laid-Open Patent Publication No. 7-185311: In this publication, a liquid containing fine particles or a liquid forming fine particles by a reaction is once spread on the surface of a high density liquid, and a liquid as a raw material for the fine particles is spread. An invention is described in which a fine particle film is formed by two-dimensionally agglomerating fine particles while controlling the thickness, and bringing the agglomerated two-dimensional particle thin film into contact with the surface of a solid substrate to transfer and fix it. JP-A-8-234450
Publication: In this publication, by directly acting an energy ray on a single-particle film or a multi-particle film of submicron fine particles, the solubility and the melting degree of particles are locally changed according to a predetermined pattern, and patterned. The invention of forming a mono-particle film or a multi-particle film is described.

Japanese Unexamined Patent Publication No. 8-155379: This publication describes an invention of a method for forming a fine particle film in which the surface of a solid secondary substrate is activated or hydrophobized by irradiation with energy rays to form a hydrophobic surface. ing. In addition, a denatured protein is produced by disposing a specific binding ligand film on the surface of the solid secondary substrate or by adsorbing a thiol group,
The invention of a method for forming a fine particle film in which a fine particle film is transferred and attached or a method for forming a fine particle film in which ultrafine particles are irradiated with an energy ray to generate active radicals and transferred and adhered is described.

According to the conventional technique described above, it is possible to regularly agglomerate one particle layer made of particles having a spherical shape and a low specific gravity so as to be uniformly arranged. Further, even with respect to fine particles having a high specific gravity, which has been conventionally said to be difficult, the inventor of the present invention has made it possible to arrange the fine particles in a desired region by utilizing the unevenness of the substrate previously invented. However, although these conventional techniques can form a fine particle film in which fine particles are arranged on one surface or fine particles are arranged in a predetermined region, they cannot construct a flexible structure of fine particles. .

[0020]

Optical components such as photonic crystals are used in the ones utilizing the physical properties exhibited by the periodic repeating structure of fine particles or fine structures.
Alternatively, there is an optical integrated circuit in which it is integrated. Such a periodic structure is roughly classified and produced by the following two methods. (1) A method using a fine processing technique. (2) A method in which fine particles having a uniform shape are aggregated or arranged.

The features of each method will be briefly described. The method (1) utilizing the fine processing technique is basically two-dimensional processing, although it has an advantage of good integration with the device process. However, it is difficult to form a three-dimensional structure, and the period of the periodic structure needs to be about half of that of the light used. Therefore, there is a drawback that a very fine processing technique is required to manufacture a light for short wavelength light. However, due to the above advantages, application to optical integrated circuits and the like at present is limited to this method. On the other hand, the method (2) in which fine particles having a uniform morphology are aggregated or arranged allows a crystal body of fine particles to be produced, so that three-dimensionalization is easy and sophisticated fine processing technology is required. Although it has the advantage of not doing so, it takes a long time to manufacture, and problems such as patterning when making it into a device have not been solved,
There is no example applied to optical integrated circuits.

Looking at the optical recording drive, a combo drive in which a CD system and a DVD system are mounted on the same machine is beginning to appear on the market, and even here, light of different wavelengths is used by the same machine. Therefore, the advantage of being able to integrate the optical system is great. Further, even if optical interconnection and optical multiplexing techniques are advanced in the future, there is a great advantage that materials and devices in which optical components using different wavelengths are mounted on the same substrate can be used. Furthermore, even if only one type of light is used,
Considering the case where a waveguide and other optical components are integrated on the same substrate, a fine particle structure is selected depending on whether a periodic structure of fine particles is used as a waveguide or optical characteristics such as a super prism and a super lens are used. Since the required period is different, fine particle structures having different periodic structures are required on the same substrate.

The present invention has been made in view of the above problems of the prior art, and is a fine particle structure having a periodic structure composed of fine particles having a uniform particle diameter, a method for producing the same, and
It is intended to provide the applied article (optical component such as an optical integrated circuit). Further, another object of the present invention is to provide a fine particle structure having a periodic structure and a free shape, which utilizes a fine particle array film made of metal oxide fine particles having a uniform particle diameter.

[0024]

[Means for Solving the Problems] The above problems are solved in the following 1) to
It is solved by the invention of 16) (hereinafter referred to as the inventions 1 to 16). 1) A first fine particle structure and a second fine particle structure, which are composed of fine particles having a uniform particle diameter and have different periodic structures and are patterned in an arbitrary shape, are formed on the same substrate. A fine particle structure characterized by the above. 2) The fine particle structure according to 1), wherein the first and second fine particle structures are composed of spherical fine particles. 3) The fine particle structure according to 1) or 2), wherein the first and second fine particle structures are composed of fine particles having the same composition. 4) The fine particle structure according to 1) or 2), wherein the first and second fine particle structures are composed of fine particles having different compositions. 5) The first and second fine particle structures are composed of fine particles having different particle sizes from each other 1) to
The fine particle structure according to any one of 4). 6) The space between the fine particles forming the first and / or the second fine particle structure is filled with a substance made of a material different from the fine particles, according to any one of 1) to 5). Fine particle structure. 7) The fine particles constituting the first and second fine particle structures and the material of the substrate are both metal oxides, and the fine particle structure according to any one of claims 1 to 6. 8) An optical integrated circuit comprising the fine particle structure according to any one of claims 1 to 7, wherein an optical circuit is constructed by patterning the shapes of the first and second fine particle structures. 9) A fine particle film is formed on the concave pattern by applying and spreading a fine particle dispersion liquid in which fine particles having a uniform particle size are dispersed in a dispersion medium on a substrate having a concave pattern on the surface and drying. Fine particle film forming step, and fine particle structure forming step of forming a fine particle structure by stacking a plurality of fine particle films after peeling the fine particle film from the substrate using an adsorption device having a function of adsorbing a fine article A method for producing a fine particle structure, comprising: 10) The concave-shaped pattern formed on the substrate comprises a first concave-shaped pattern and a second concave-shaped pattern formed on the bottom of the inner surface of the first concave-shaped pattern. Is a first fine particle arranging step of arranging the first fine particles in the second concave pattern by applying and spreading a dispersion liquid of the first fine particles on the substrate and drying the dispersion liquid; A dispersion liquid of second fine particles having a particle diameter smaller than that of the first fine particles and the second fine particles, by coating and spreading the liquid on the substrate on which the dispersion liquid of the first fine particles is coated and spread, and drying. A mixed fine particle film forming step of forming a mixed fine particle film composed of the fine particles of
9. The method for producing a fine particle structure according to 9), which comprises: 11) The second concave-shaped pattern is composed of a set of concave-shaped portions formed at a constant period. 1
0) The method for producing a fine particle structure as described above. 12) A coating process of coating a coating layer that can be dissolved and removed on the substrate on which the concave-shaped pattern is formed; The method for producing a fine particle structure according to any one of 9) to 11), further comprising a coating layer removing step of dissolving and removing the layer. 13) Manufacturing of the fine particle structure according to any one of 9) to 12), which comprises a fine particle film electric pulse applying step of applying an electric pulse to the fine particle film formed on the concave pattern. Method. 14) A laminated fine particle film electric pulse applying step of applying an electric pulse to the fine particle films stacked in the fine particle structure forming step, 9) to 1)
3. The method for producing a fine particle structure according to any one of 3). 15) A fine particle film formed on the concave pattern,
15. The method for producing a fine particle structure according to any one of 9) to 14), comprising a hydrogen reduction step of exposing at least one of the fine particle films stacked in the fine particle structure forming step to a hydrogen reducing atmosphere. 16) The fine particles are metal oxide fine particles 9) to
15. The method for producing a fine particle structure according to any one of 15).

Hereinafter, the present invention will be described in detail. In the present invention, the fine particles forming the first and second fine particle structures must have uniform particle diameters. Here, the particle diameter being uniform means that the distribution of the particle diameter is within 5%, preferably within 2% from the average value. In other words, it means that the variation with respect to the standard particle diameter is within 5%, preferably within 2%. Examples of such fine particles include fine particles of metal oxides (metal oxide monodisperse particles) which have a particle size distribution that has been remarkably advanced in recent years. Further, the periodic structure in the present invention means a structure in which a large number of fine particles are arranged regularly and periodically. The periodic structure of such fine particles includes types such as "hexagonal close-packed structure" and "face-centered cubic structure" according to the properties of the space group, similar to the ordinary crystal system. The "different periodic structure" in the present invention includes two meanings that the crystal systems are different and that the crystal lattice lengths are different due to the different particle diameters. This is also shown in Examples described later.

In the method for producing a fine particle structure of the present invention, first, a fine particle (arrangement) film having a two-dimensional pattern (two-dimensional pattern) is formed using a substrate having a concave pattern on the surface. The formation of this fine particle film is performed by applying / spreading a dispersion liquid containing fine particles having a uniform particle diameter onto a substrate and drying. The two-dimensional pattern is formed to use the fine particle film as a part of the three-dimensional fine particle structure. That is, by repeating the work of peeling off the fine particle film from the substrate with microtweezers, moving it to another fine particle film that was peeled off earlier, and stacking it.
A three-dimensional fine particle structure is formed.

The above-mentioned method for producing a three-dimensional fine particle structure has the following advantages. (1) Since it is a method of stacking necessary fine parts, the material can be saved more than machining (cutting) performed by a micromachine or the like. (2) By adopting a method of stacking components, it is possible to easily form a shape that is difficult to perform by machining. For example, a shape of an overhang that protrudes upward from the substrate can be easily formed by the method of stacking components. (3) The conventional method for forming a fine particle film utilizing the cohesive force between fine particles can only obtain a fine particle structure having a close-packed structure. However, according to the method for producing a fine particle structure of the present invention, since the position of the fine particles can be controlled by the unevenness of the substrate,
It becomes possible to control various periodic structures.
This is a great advantage when the fine particle structure is used in the optical field. Further, since the position of the fine particles can be controlled by the unevenness, if fine particle films having different periodic structures are made as parts, it becomes possible to simultaneously make three-dimensional fine particle structures having different periodic structures.

Next, referring to the drawings, preferred embodiments 1 to 6 relating to the method for producing the fine particle structure will be described. <First Embodiment> First, a first embodiment will be described. FIG. 1 is a diagram for explaining the method of manufacturing the fine particle structure according to the first embodiment. In the first embodiment, TiO ₂
A glass substrate 101 having a concave pattern 101a on a surface of a dispersion liquid 102 in which fine particles 103 are dispersed in a dispersion medium.
Recessed pattern 101a is applied and spread on the surface and dried.
A TiO ₂ fine particle film 105 is formed on the TiO ₂ fine particle film 105, and then TiO ₂
The fine particle film 105 is peeled from the glass substrate 101 using the microtweezers 104, and then the TiO ₂ fine particle films 105 are stacked to form a three-dimensional fine particle structure 106.

That is, first, the concave pattern 101a is formed on the glass substrate 101 by using the photolithography technique. Then, the patterned glass substrate 10
A dispersion liquid (a water dispersion liquid) 102 of spherical TiO ₂ fine particles 103 having a particle diameter of about 800 nm is applied (dropped) and spread on the surface of No. 1 [FIG. 1 (a)]. At this time, the TiO ₂ fine particles 103, which are fine particles of metal oxide, have a large specific gravity, so after being dropped and spread, they settle on the surface of the glass substrate 101 at a relatively early stage. Here, by appropriately adjusting the liquidity of the dispersion liquid 102, the TiO ₂ fine particles 103 can continue the Brownian motion even on the surface of the glass substrate 101, and as a result, the TiO ₂ fine particles 103 have the concave pattern 101a. It falls into the concave surface [Fig. 1
(B)].

By drying the dispersion liquid 102 and the glass substrate 101 shown in FIG. 1B, a TiO ₂ fine particle film 105 is formed on the bottom surface of the concave pattern 101a.
In this case, using spherical TiO ₂ fine particles,
Since the bottom of the concave pattern 101a is flat, the TiO ₂ fine particle film 10 obtained by the concave pattern 101a is obtained.
No. 5 has a close-packed structure due to the agglomeration effect of fine particles when the dispersion is dried [FIG. 1 (c)].

Next, the TiO ₂ fine particle film 105 formed by the steps described above is attached to the microtweezers 104.
It is adsorbed by and is peeled off from the glass substrate 101 [Fig. 1
(D)]. TiO adsorbed by microtweezers 104
_{The 2} fine particle film 105 is moved and stacked on the TiO ₂ fine particle film 105 formed with another concave pattern 101a [FIG. 1 (e)]. The three-dimensional fine particle structure 106 is formed by repeating the step of stacking the TiO ₂ fine particle films 105. Micro tweezers 1
Although 04 refers to a microprobe used in an atomic force microscope, a tunnel microscope, or the like, for handling a minute substance, it is not the gist of the present invention, and a description thereof will be omitted. Although microtweezers are used in the description of the embodiments, as long as it is an adsorption device having a function of adsorbing a fine article such as the fine particle film of the present invention,
Others may be used.

2A to 2C are other diagrams for explaining the steps of the first embodiment. As shown in the figure, the glass substrate 101 has a plurality of types of concave-shaped patterns 101b, 101 for forming a component for forming a fine particle structure.
c, 101d. And the concave pattern 1
In 01b, 101c, and 101d, the TiO ₂ fine particle film 105 corresponding to each pattern shape is formed [FIG. 2 (a)]. Next, the TiO ₂ fine particle films 105 are respectively adsorbed by the microtweezers 104 [FIG.
(B)], The particles are stacked according to the three-dimensional shape of the fine particle structure [FIG. 2 (c)].

According to the first embodiment described above, TiO
_{Since the} fine particle structure is formed by stacking the _two fine particle films 105, the material can be saved more than the machining (cutting) performed by a normal micromachine or the like. Further, it is relatively easy to form a shape of an overhang that is difficult to perform by machining, for example, the shape of the overhang protruding as it goes up from the substrate.

<Second Embodiment> Next, a second embodiment of the present invention will be described. FIG. 3 is a diagram for explaining the method of manufacturing the fine particle structure according to the second embodiment. In addition, among the illustrated configurations, the same configurations as those of the first embodiment described above are denoted by the same reference numerals, and description thereof will be omitted.
In the second embodiment, the glass substrate 301 has a pattern including a first concave pattern 301a and a second concave pattern 301b formed on the bottom of the inner surface thereof.
This substrate 301, by applying and expanded drying a dispersion 102 obtained by dispersing TiO ₂ particles 103 in a dispersion medium, TiO ₂ fine particles to the second concave pattern 301b 1
Place 03. Next, a dispersion liquid 303 in which Al ₂ O ₃ fine particles 302 having a particle diameter smaller than that of the TiO ₂ fine particles 103 is dispersed in a dispersion medium is applied and spread on a substrate 301 on which the dispersion liquid 102 is applied and spread, and then dried. By doing so, a fine particle film 304 composed of the TiO ₂ fine particles 103 and the Al ₂ O ₃ fine particles 302 is formed.

That is, first, the first concave pattern 30 is formed on the glass substrate 301 by using the photolithography technique.
1a is formed, and then a second concave pattern 301b is formed on the inner bottom surface of the first concave pattern 301a by a photolithography technique. The first concave pattern 301a has a pattern shape suitable as a component shape of the final three-dimensional fine particle structure. Further, the second concave pattern 301b is a pattern composed of a set of concave portions formed at a constant cycle, and is for controlling the position where the TiO ₂ fine particles 103 are seated, so the diameter of the concave portion is The particle diameter is made substantially the same as that of the TiO ₂ particles 103 (about 800 nm in the second embodiment).

In the second embodiment, the TiO ₂ fine particles 1 are used.
The position where 03 is seated can be controlled by the shape of the recess of the second recessed pattern 301b. Therefore, by making the shape of the recesses have repeating periodicity, the arrangement of the TiO ₂ particles 103 can have periodicity other than the closest packing. In the second embodiment, in the same first concave pattern 301a, the repeating cycle of the concave shape is one type. This is the same first concave pattern 30.
This is to prevent the arrangement of particles from being disturbed due to the presence of concave shapes having a plurality of periods in 1a.

In the second embodiment, a dispersion liquid (which is an aqueous dispersion liquid) 102 of spherical TiO ₂ fine particles 103 having a particle diameter of about 800 nm is dropped and spread on the surface of a glass substrate 301 [FIG. 3 (a)]. . At this time, the TiO ₂ particles 103 can continue the Brownian motion even on the surface of the glass substrate 301 by appropriately adjusting the liquidity of the dispersion liquid 102. As a result, the TiO ₂ particles 103 are
The concave pattern 301b falls into the concave portion and is seated in the concave position [FIG. 3 (b)]. Then, the glass substrate 301 and the dispersion liquid 102 shown in FIG. 3B are dried to obtain a state in which the TiO ₂ fine particles 103 are seated in the concave portions of the second concave pattern 301b [FIG. )]. In this case, the recessed shape regulates the position where the TiO ₂ particles 103 are seated, so that the TiO ₂ particles 103 do not have a close-packed structure and do not form a self-supporting film (that is, the TiO ₂ particles 103). There is a gap between them).

Next, on the surface of the glass substrate 301, a dispersion liquid 3 of Al ₂ O ₃ fine particles 302 having a particle diameter of about 10 nm is prepared.
03 is dropped and developed [FIG. 3 (d)]. The Al ₂ O ₃ fine particles 302 in the dispersion liquid 303 settle and fill the gaps between the TiO ₂ fine particles 103 [FIG. 3 (e)]. When the substrate 301 and the dispersion liquid 303 shown in FIG. 3E are dried,
Since the Al ₂ O ₃ fine particles 302 are filled between the TiO ₂ fine particles 103, an aggregating effect between the fine particles is obtained, and T
A fine particle film 304 composed of iO ₂ fine particles 103 and Al ₂ O ₃ fine particles 302 is obtained [FIG. 3 (f)]. Figure 3
The state shown in (f) is enlarged and shown in FIG. The fine particle film 304 is adsorbed by the microtweezers 104 and peeled off from the glass substrate 301 [FIG. 3 (g)]. The fine particle film 304 adsorbed by the microtweezers 104 is moved and stacked on the fine particle film 304 formed in another concave portion [FIG. 3 (h)]. By repeating the process of stacking the fine particle films 304, the three-dimensional fine particle structure 305 is formed.

According to the second embodiment described above, of the fine particles used, the position of the fine particles having a larger particle diameter can be controlled by the second concave pattern. Therefore, in addition to the close-packed structure, it is possible to form a fine particle film in which fine particles are arranged in various cycles. This is a great advantage when the fine particle structure is used in the optical field. Furthermore, if fine particle films having different periodic structures are formed as parts, it becomes possible to simultaneously form three-dimensional fine particle structures having different periodic structures.

<Third Embodiment> Next, a third embodiment of the present invention will be described. FIG. 5 is a diagram for explaining the method of manufacturing the fine particle structure according to the third embodiment. In addition, among the illustrated configurations, the same configurations as those of the first and second embodiments described above are denoted by the same reference numerals, and description thereof will be omitted. In the third embodiment, after forming the concave pattern, the glass substrate is further coated with a coating layer capable of being dissolved and removed. In addition, the coating layer is dissolved and removed with a solvent as a pretreatment for peeling the fine particle film from the substrate. Therefore,
It will be described as an additional step of coating the coating layer and dissolving and removing the coating layer to the method for producing the fine particle structure of the second embodiment described above.

That is, first, the photolithography is performed on the glass substrate 301.
First concave pattern 301 using the technique of sography
a is formed, and then by the technique of photolithography
A second concave pattern is formed on the bottom of the inner surface of the first concave pattern 301a.
Form turn 301b. Then, the first concave putter
On the surface of the second concave pattern 301b.
The styrene layer 501 is coated. Next, the glass base
The surface of the plate 301 has a spherical shape with a particle diameter of approximately 800 nm.
TiO _TwoDispersion of fine particles 103 (which is an aqueous dispersion) 10
2 is dropped and spread [FIG. 5 (a)]. At this time, the dispersion
By adjusting the liquidity of 102, the glass substrate
Even on the surface of 301, TiO_TwoFine particles 103 are brown luck
The movement can be continued. As a result, TiO_TwoFine particles
103 falls in the concave portion of the second concave pattern 301b.
And then sit down in the concave position [Fig. 5 (b)].

By drying the glass substrate 301 and the dispersion liquid 102 shown in FIG. 5B, a state in which the TiO ₂ fine particles 103 are seated in the concave portions of the second concave pattern 301b is obtained [FIG. c)]. In this case, since the recessed shape regulates the position where the TiO ₂ fine particles 103 are seated, the TiO ₂ fine particles 103 do not have a close-packed structure, and do not form a self-supporting film (that is,
(There is a gap between the TiO ₂ particles 103). Next, on the surface of the glass substrate 301, Al having a particle diameter of about 10 nm was used.
A dispersion liquid 303 of ₂ O ₃ fine particles 302 is dropped and spread [FIG. 5 (d)]. Al ₂ O ₃ fine particles 3 in the dispersion liquid 303
02 sediments to fill the gaps between the TiO ₂ particles 103 [FIG. 5 (e)]. When the substrate 301 and the dispersion liquid 303 shown in FIG. 5E are dried, the TiO ₂ fine particles 103
Since the Al ₂ O ₃ fine particles 302 are filled between them, an aggregating effect between the fine particles is obtained, and a fine particle film 304 composed of the TiO ₂ fine particles 103 and the Al ₂ O ₃ fine particles 302 is obtained [FIG. )].

Next, in order to easily peel off the fine particle film 304 from the substrate, the polystyrene layer 501 on the surface of the glass substrate 301 is removed with toluene [FIG. 5 (g)]. After removing the polystyrene layer 501, the fine particle film 304 is adsorbed by the microtweezers 104 and peeled off from the glass substrate 301 [FIG. 5 (h)]. The fine particle film 304 adsorbed by the microtweezers 104 is moved and stacked on the fine particle film 304 formed in another concave portion [FIG.
(I)]. By repeating the process of stacking the fine particle films 304, the three-dimensional fine particle structure 305 is formed.

According to the third embodiment described above, the fine particle film can be easily peeled off from the substrate, and the fine particle film can be prevented from being damaged in the step of peeling from the substrate. As a result, the quality of the fine particle film can be improved. It is possible to improve the quality of the fine particle structure.

<Fourth Embodiment> Next, a fourth embodiment of the present invention will be described. FIG. 6 is a diagram for explaining the method of manufacturing the fine particle structure according to the fourth embodiment. Note that among the illustrated configurations, the same configurations as those of the first to third embodiments described above are denoted by the same reference numerals, and description thereof will be omitted. The fourth embodiment further includes a step of applying an electric pulse to the fine particle film formed on the concave pattern.

That is, first, the concave pattern 101a is formed on the glass substrate 101 by using the photolithography technique, and then the polystyrene layer 501 is coated on the surface. Next, a dispersion liquid (which is an aqueous dispersion liquid) 102 of spherical TiO ₂ fine particles 103 having a particle diameter of about 800 nm is dropped and spread thereon (FIG. 6A). TiO ₂
The fine particles 103 settle on the surface of the glass substrate 101, then continue the Brownian motion and fall into the concave portions of the concave pattern 101a [FIG. 6 (b)]. By drying the glass substrate 101 and the dispersion liquid 102 in the state shown in FIG. 6B, Ti in the concave portion of the concave-shaped pattern 101a is formed.
An O ₂ fine particle film 105 is formed [FIG. 6 (c)].

Next, an electric pulse is applied to the TiO ₂ fine particle film 105 using the probe of the microtweezers 104 [FIG. 6 (d)]. By applying an electric pulse, Ti
The binding force between the fine particles of the O ₂ fine particle film 105 is increased. Further, the TiO ₂ fine particle film 105 is formed on the glass substrate 101.
The polystyrene layer 501 on the surface of the substrate is removed with toluene to facilitate peeling from the substrate [FIG. 6 (e)]. Then, the TiO ₂ fine particle film 105 is attached to the microtweezers 10.
Adsorb at 4 and peel from the glass substrate 101 [Fig.
(F)]. The TiO ₂ fine particle film 105 is adsorbed, stacked and moved on to the concave pattern 101a TiO ₂ fine particle film 105 formed in the concave portion of [shown in FIG. 6 (g)]. The three-dimensional fine particle structure 106 is formed by repeating the step of stacking the TiO ₂ fine particle films 105.

According to the fourth embodiment described above, TiO
By applying electrical pulses to ₂ fine particle film 105 to increase the binding force between the TiO ₂ particles 103 constituting the TiO ₂ fine particle film 105, it is possible to improve the workability in the subsequent step.

<Fifth Embodiment> Next, a fifth embodiment of the present invention will be described. FIG. 7 is a diagram for explaining the method of manufacturing the fine particle structure according to the fifth embodiment. In addition, among the illustrated configurations, the same configurations as those of the first to fourth embodiments described above are denoted by the same reference numerals, and description thereof will be omitted. The fifth embodiment further includes the step of applying an electric pulse to the stacked fine particle films.

That is, first, the concave pattern 101a is formed on the glass substrate 101 by using the photolithography technique, and then the surface is coated with the polystyrene layer 501. Next, a dispersion liquid (which is an aqueous dispersion liquid) 102 of spherical TiO ₂ fine particles 103 having a particle diameter of about 800 nm is dropped and spread thereon (FIG. 7A). TiO ₂
The fine particles 103 settle on the surface of the glass substrate 101, continue the Brownian motion, and fall into the concave portions of the concave pattern 101a [FIG. 7 (b)]. By drying the glass substrate 101 and the dispersion liquid 102 in the state shown in FIG.
An iO ₂ fine particle film 105 is formed [FIG. 7 (c)].

Next, an electric pulse is applied to the TiO ₂ fine particle film 105 using the probe of the microtweezers 104 (FIG. 7D). In addition, the TiO ₂ fine particle film 105
In order to make it easy to peel off the glass substrate 101, the polystyrene layer 501 on the substrate surface is removed with toluene [FIG. 7 (e)]. Next, the TiO ₂ fine particle film 105 is adsorbed by the microtweezers 104 and peeled off from the glass substrate 101 [FIG. 7 (f)]. Adsorbed TiO ₂ particle film 10
5 is a T formed by the concave portion of the concave pattern 101a.
The particles are moved and stacked on the iO ₂ fine particle film 105. This T
By repeating the step of stacking the iO ₂ fine particle films 105, the three-dimensional fine particle structure 106 is formed.

Further, in the fifth embodiment, after stacking the TiO ₂ fine particle films 105, an electric pulse is applied to the fine particle structure 106 using the probe of the microtweezers 104 (FIG. 7 (g)). By applying an electric pulse, the binding force between the fine particle films is strengthened, and the fine particle structure 1
It can make 06 hard to break.

<Sixth Embodiment> Next, a sixth embodiment of the present invention will be described. FIG. 8 is a diagram for explaining the method of manufacturing the fine particle structure according to the sixth embodiment. In addition, among the illustrated configurations, the same configurations as those of the first to fifth embodiments described above are denoted by the same reference numerals, and description thereof will be omitted. The sixth embodiment further includes a hydrogen reduction step of exposing at least one of the fine particle film formed on the concave pattern and the stacked fine particle film to a hydrogen reducing atmosphere.

That is, α-F as metal oxide fine particles is formed on the concave pattern 801a formed on the glass substrate 801.
A three-dimensional fine particle structure 802 using e ₂ O ₃ fine particles is formed [FIG. 8 (a)]. The method for forming the fine particle structure 802 is the same as that of the fine particle structure 106 described in Embodiment Mode 1.
It is the same as the forming method. Next, the fine particle structure 802
Are placed in a chamber 803 equipped with a heating stage 804. The chamber 803 is filled with H to create a hydrogen reducing atmosphere.
₂ is introduced while being exhausted, and the fine particle structure 80
2 is exposed to a hydrogen reducing atmosphere while being heated to 400 ° C. by the heating stage 804 [FIG. 8 (b)]. By this treatment, the α-Fe ₂ O ₃ fine particles are reduced with hydrogen and converted into Fe ₃ O ₄ fine particles. Therefore, α-Fe ₂
The fine particle structure 802 composed of O ₃ fine particles is made of Fe ₃ O ₄
It becomes a fine particle structure 805 composed of fine particles [FIG.
(C)].

By the way, since the Fe ₃ O ₄ fine particles have spontaneous magnetization, it is difficult to directly arrange or arrange them. However, as described above, the state of the α-Fe ₂ O ₃ fine particles is as described above. After forming a three-dimensional fine particle structure with Fe ₃
If converted into O ₄ fine particles, it is possible to obtain a three-dimensional fine structure of Fe ₃ O ₄ fine particles easily. Further, the present invention is not limited to the configuration in which the α-Fe ₂ O ₃ fine particles in the state of the three-dimensional fine particle structure are hydrogen-reduced as in the sixth embodiment, and α in the state of a fine particle film is used. -Fe ₂
The O ₃ fine particles may be reduced with hydrogen. Furthermore, since metal fine particles generally have high activity and tend to aggregate,
The method for producing a three-dimensional fine particle structure of the sixth embodiment is also effective when forming a structure of metal fine particles.

The fine particles that can be used in the present invention are Ti particles described in the first to sixth embodiments.
It is not limited to O ₂ , Al ₂ O ₃ , α-Fe ₂ O _{3, and the} like. When using fine particles of a material different from these materials, a stable dispersion can be formed, and the liquidity may be adjusted so that the fine particles can move on the substrate surface. This is the principle of isoelectric point etc. Can be appropriately determined based on.

[0057]

EXAMPLES The present invention will be described in detail below with reference to examples, but the present invention is not limited to these examples.

Example 1 Spherical SiO ₂ fine particles were used as the first and second fine particles, and the particle size of the fine particles constituting the first fine particle structure was 2
90 nm, and the particle diameter of the fine particles forming the second fine particle structure was 300 nm (see FIG. 9). Both the first and second fine particle structures were produced so as to be the closest packed by utilizing the aggregation phenomenon of fine particles. The outline of the manufacturing method is as follows. That is, a fine particle dispersion liquid in which fine particles are dispersed in water is spread on a substrate and allowed to stand until a colloidal crystal in which the fine particles are regularly arranged is formed in the liquid. Next, hydrochloric acid is added to the liquid to lower the pH to strengthen the coagulation between the fine particles, and then the liquid is dried to obtain a fine particle structure. Since the method for producing the fine particle structure described here utilizes the agglomeration phenomenon of fine particles, both the first and second fine particle structures have a periodic structure of the fine particle structure that is different depending on the particle size of the fine particles used. It has been decided. The center of the photonic bandgap of the first fine particle structure is about 650 nm, and the center of the photonic bandgap of the second fine particle structure is about 700 nm. Therefore, using this fact, the same glass substrate is used. A waveguide structure made of the first fine particle structure and a supercollimator made of a photonic crystal made of the second fine particle structure were formed on the top (see FIG. 10).
In FIG. 10, a two-dimensional case is shown for ease of illustration, but it is also possible to integrate optical components in a three-dimensional manner by stacking the fine particle array films with the above-described microprobe. As described above, an optical integrated circuit for light having a wavelength of 650 nm having the waveguide structure and the supercollimator could be formed.

Example 2 The first fine particle structure was spherical SiO 2 having a particle size of 265 nm.
_Two fine particles were used, and the spaces between the fine particles were filled with TiO ₂ fine particles, and the periodic structure of the fine particles was a face-centered cubic structure with a lattice spacing of 290 nm. This first fine particle structure was produced by using the above-described fine processing on the substrate and macro tweezers. The second fine particle structure has a particle size of 265 nm.
Spherical TiO ₂ fine particles were used, and the periodic structure was made to be the most dense packing. Therefore, the periodic structure of the second fine particle structure is determined by the particle size of the fine particles used. The first and second fine particle structures were formed on the same silicon substrate with an oxide film (see FIG. 11). The center of the photonic bandgap of the first fine particle structure is about 650 nm, and the center of the photonic bandgap of the second fine particle structure is about 600 nm. , A superprism made of a photonic crystal composed of a first fine particle structure and a second fine particle structure was formed (see FIG. 12). In FIG. 12, a two-dimensional case is shown for ease of illustration, but a three-dimensional structure is also possible. As described above, the wavelength 650 having the waveguide structure and the super prism
An optical integrated circuit for nm light could be formed.

[0060]

EFFECTS OF THE INVENTION According to the present invention 1, it is possible to simultaneously utilize the phenomenon of the first fine particle structure and the phenomenon of the second fine particle structure on the same substrate. It is possible to realize device integration, multifunctionalization, and downsizing of integrated devices. According to the second aspect of the present invention, by using spherical fine particles, the dispersibility of the raw material liquid in which the fine particles are dispersed can be improved, and when the first or second fine particle structure is formed with a close-packed structure. It is possible to make a fine particle structure by utilizing the cohesive force of fine particles. According to the third aspect of the present invention, by forming the first and second fine particle structures with fine particles having the same composition, the dispersion of the raw material liquid in which the fine particles are dispersed is produced when the first and second fine particle structures are produced. The conditions can be made common, and the conditions for settling and fixing fine particles on the substrate can also be made common.

According to the fourth aspect of the present invention, the first and second fine particle structures are composed of fine particles having different compositions, so that when the fine particle structure is used as a photonic crystal, light is emitted in the band gap region. Elements that use non-transmissive properties (for example, waveguides and resonator mirrors) and elements that use special optical properties in the light wavelength region other than the bandgap region (for example, super prism, super collimator, super It is possible to use a material having a composition suitable for each of the lenses). Further, even when circuits for light of different wavelengths are formed on the same substrate, it becomes possible to use a composition having a composition suitable for each of different wavelength regions. According to the fifth aspect of the present invention, the first and second fine particle structures are formed of fine particles having different particle sizes, so that the first and second fine particle structures are closely packed by utilizing the aggregation phenomenon of the fine particles. When manufactured with a structure, it becomes possible to realize different periodic structures in the first fine particle structure and the second fine particle structure due to the difference in particle size of the fine particles.

According to the present invention 6, the fine particles constituting the first and / or the second fine particle structure are filled with a substance having a composition different from that of the fine particles, and the periodic structure of the fine particles in the fine particle structure. It is possible to increase the variety of phenomena that are caused by the substance between the fine particles. According to the present invention 7, since the substrate and the first and second fine particle structures are made of a metal oxide, when the fine particle structure is manufactured, the dispersibility of the raw material liquid in which the fine particles are dispersed and the dispersion of the fine particles can be improved. The pH of the raw material dispersion liquid can be used for aggregation and fixing to the substrate. According to the present invention 8, by the first and second fine particle structures,
Diffraction grating elements and photonic crystals having different periodic structures can be formed on the same substrate, and since the fine particle structures are patterned and integrated, a higher level of processing than conventional optical integrated circuits can be achieved.・ Calculation is possible, and circuits for multiple wavelength bands can be built on the same substrate.

According to the present invention 9, since fine particles having a uniform particle size are used, it is possible to obtain a high-quality fine particle film having regularity in the particle arrangement, and thus a fine particle structure composed of the fine particle film. The field of application can be expanded to fields such as optics. Further, by stacking fine particle films to be fine parts, the material for producing the three-dimensional fine particle structure can be saved, and the three-dimensional fine particle structure having a shape difficult to form by machining can be relatively easily produced. Further, by using the fine particle array film as a component, a fine particle structure having a free structure can be manufactured.

According to the tenth aspect of the present invention, the position where the fine particles are seated is controlled by the second concave pattern so that the second concave pattern has a repetitive periodicity, so that the periodicity other than the closest packing is obtained. Can be used as a part of the fine particle structure. Therefore, more diverse fine particle structures can be manufactured. According to the present invention 11, the first
The second concave-shaped pattern formed in the concave-shaped pattern is composed of a set of concave-shaped portions formed at a constant period, so that the quality of the periodicity of the particle film is improved and, by extension, the fine particle film is used. It is possible to improve the quality of the fine particle structure.

According to the twelfth aspect of the present invention, a step of peeling the fine particle film from the substrate by microtweezers (probes) by forming a coating layer on the surface of the substrate and dissolving and removing the coating layer before peeling the fine particle film. Can be facilitated. Therefore, it is possible to prevent the fine particle film from being damaged when the fine particle film is peeled off from the substrate, and to improve the quality of the fine particle structure composed of the fine particle film. According to the thirteenth aspect of the present invention, by applying an electric pulse to the fine particle film, the binding force between the fine particles in the fine particle film can be strengthened, which facilitates the subsequent handling of the fine particle film with the microtweezers (probe). It is possible to prevent damage to the fine particle film. Therefore, the quality of the fine particle structure formed by the fine particle film can be improved.

According to the fourteenth aspect of the present invention, by applying an electric pulse to the stacked fine particle films, the binding force between the particle films can be strengthened. Therefore, it is possible to strengthen the fine particle structure constituted by the fine particle film and improve the quality of the fine particle structure. According to the fifteenth aspect of the present invention, when fine particles made of a material having high activity and easy to aggregate, such as magnetic particles or metal particles, are used by exposing the fine particle film or the fine particle structure formed of the fine particle film to a hydrogen reducing atmosphere. In addition, the fine particle structure can be manufactured relatively easily. According to the sixteenth aspect of the present invention, it is possible to manufacture a fine particle structure utilizing the characteristics of the metal oxide.

[Brief description of drawings]

FIG. 1 is a diagram for explaining a method of manufacturing a fine particle structure according to a first embodiment. (A) A concave pattern 101a is formed on the glass substrate 101 using a photolithography technique, and then,
On its surface, a dispersion liquid 10 of spherical TiO ₂ fine particles 103
The process of applying (dropping) and developing 2 is shown. (B) The TiO ₂ fine particles 103 are the concave pattern 101
The state which fell in the concave surface of a is shown. (C) The concave pattern 10 is formed by drying the dispersion liquid 102 and the glass substrate 101 shown in FIG.
A process of forming the TiO ₂ fine particle film 105 on the bottom surface of 1a will be described. (D) A step of adsorbing the TiO ₂ fine particle film 105 with the microtweezers 104 and peeling it from the glass substrate 101 is shown. (E) TiO ₂ adsorbed by the microtweezers 104
A step of moving and stacking the fine particle film 105 on the TiO ₂ fine particle film 105 formed with another concave pattern 101a will be described.

FIG. 2 illustrates a method for manufacturing the fine particle structure shown in FIG.
It is another figure for. (A) The glass substrate 101 constitutes a fine particle structure.
Plural types of concave shape patterns 101 for creating parts for
b, 101c, 101d, and the concave pattern
In each case, TiO corresponding to each pattern shape_Two Fine particles
The state where the film 105 is formed is shown. (B) TiO_TwoThe fine particle film 105 is
The process of adsorbing with the tweezers 104 is shown. (C) Stacking according to the three-dimensional shape of the fine particle structure
The following shows the process.

FIG. 3 is a drawing for explaining the method of manufacturing the fine particle structure according to the second embodiment. (A) A step of dropping and spreading the dispersion liquid 102 of spherical TiO ₂ particles 103 on the surface of the glass substrate 301 is shown. (B) A step in which the TiO ₂ fine particles 103 fall into the concave portion of the second concave pattern 301b and are seated in the concave position. (C) Glass substrate 301 and dispersion 1 shown in (b)
By drying 02, the second concave pattern 30
The state where the TiO ₂ fine particles 103 are seated on the concave portion of 1b is shown. (D) A step of dropping and spreading the dispersion liquid 303 of Al ₂ O ₃ fine particles 302 on the surface of the glass substrate 301 is shown. (E) Al ₂ O ₃ fine particles 302 in the dispersion liquid 303
A step of settling and filling the gaps between the TiO ₂ fine particles 103 is shown. (F) The substrate 301 and the dispersion liquid 303 shown in (e) are dried to obtain TiO ₂ fine particles 103 and Al ₂ O ₃ fine particles 3.
A process of obtaining a fine particle film 304 composed of No. 02 is shown. (G) A step of adsorbing the fine particle film 304 to the microtweezers 104 and peeling it from the glass substrate 301 is shown. (H) A step of moving and stacking the fine particle film 304 adsorbed by the microtweezers 104 onto the fine particle film 304 formed in another concave portion is shown.

FIG. 4 is an enlarged view of FIG. 3 (f).

FIG. 5 is a drawing for explaining the method of manufacturing the fine particle structure according to the third embodiment. (A) After forming a first concave-shaped pattern 301a and a second concave-shaped pattern 301b on a glass substrate 301 using a photolithography technique, a polystyrene layer 501 is coated on the surface thereof, and then a spherical surface is formed on the surface. A step of dropping and developing the dispersion liquid 102 of TiO ₂ fine particles 103 will be described. (B) A step in which the TiO ₂ fine particles 103 fall into the concave portion of the second concave pattern 301b and are seated in the concave position. (C) Glass substrate 301 and dispersion 1 shown in (b)
By drying 02, the second concave pattern 30
The state where the TiO ₂ fine particles 103 are seated on the concave portion of 1b is shown. (D) A step of dropping and spreading the dispersion liquid 303 of Al ₂ O ₃ fine particles 302 on the surface of the glass substrate 301 is shown. (E) Al ₂ O ₃ fine particles 302 in the dispersion liquid 303
A step of settling and filling the gaps between the TiO ₂ fine particles 103 is shown. (F) The substrate 301 and the dispersion liquid 303 shown in (e) are dried to obtain TiO ₂ fine particles 103 and Al ₂ O ₃ fine particles 3.
A process of obtaining a fine particle film 304 composed of No. 02 is shown. (G) Polystyrene layer 501 on the surface of the glass substrate 301
The step of removing the is shown. (H) The fine particle film 304 is attached to the microtweezers 104.
A step of adsorbing the glass substrate and peeling it from the glass substrate 301 is shown. (I) The fine particle film 304 adsorbed by the microtweezers 104 is replaced by the fine particle film 30 formed in another concave portion.
4 shows the step of moving to and stacking on top of 4.

FIG. 6 is a drawing for explaining the method of manufacturing the fine particle structure according to the fourth embodiment. (A) After forming a concave pattern 101a on the glass substrate 101 using a photolithography technique, a polystyrene layer 501 is coated on the surface, and then a dispersion liquid 102 of spherical TiO ₂ fine particles 103 is dripped on it.・ Show the process of development. (B) A step in which the TiO ₂ fine particles 103 settle on the surface of the glass substrate 101 and then fall into the concave portions of the concave pattern 101a is shown. (C) A step of drying the glass substrate 101 and the dispersion liquid 102 in the state shown in (b) to form the TiO ₂ fine particle film 105 in the concave portions of the concave pattern 101a is shown. (D) A step of applying an electric pulse to the TiO ₂ fine particle film 105 using the probe of the microtweezers 104 is shown. (E) A step of removing the polystyrene layer 501 on the surface of the substrate is shown. (F) A step of adsorbing the TiO ₂ fine particle film 105 with the microtweezers 104 and peeling it from the glass substrate 101 is shown. (G) showing the step of stacking and moving the TiO ₂ fine particle film 105 adsorbed, on the TiO ₂ fine particle film 105 formed in the concave portion of the concave pattern 101a.

FIG. 7 is a drawing for explaining the method of manufacturing the fine particle structure according to the fifth embodiment. (A) After forming a concave pattern 101a on the glass substrate 101 using a photolithography technique, a polystyrene layer 501 is coated on the surface, and then a dispersion liquid 102 of spherical TiO ₂ fine particles 103 is dripped on it.・ Show the process of development. (B) A step in which the TiO ₂ fine particles 103 settle on the surface of the glass substrate 101 and then fall into the concave portions of the concave pattern 101a is shown. (C) A step of drying the glass substrate 101 and the dispersion liquid 102 in the state shown in (b) to form the TiO ₂ fine particle film 105 in the concave portions of the concave pattern 101a is shown. (D) A step of applying an electric pulse to the TiO ₂ fine particle film 105 using the probe of the microtweezers 104 is shown. (E) A step of removing the polystyrene layer 501 on the surface of the substrate is shown. (F) A step of adsorbing the TiO ₂ fine particle film 105 with the microtweezers 104 and peeling it from the glass substrate 101 is shown. The TiO ₂ fine particle film 105 which is (g) adsorption, after stacking moved onto the TiO ₂ fine particle film 105 formed in the concave portion of the concave pattern 101a, by using the probe of micro forceps 104, fine structure A process of applying an electric pulse to the body 106 is shown.

FIG. 8 is a drawing for explaining the method of manufacturing the fine particle structure according to the sixth embodiment. (A) A step of forming a three-dimensional fine particle structure 802 using α-Fe ₂ O ₃ fine particles on the concave pattern 801a formed on the glass substrate 801 is shown. (B) A step of placing the fine particle structure 802 in a chamber 803 equipped with a heating stage 804 and exposing it to a hydrogen reducing atmosphere is shown. (C) Fine particle structure 805 made of Fe ₃ O ₄ fine particles
Indicates.

FIG. 9 is an explanatory diagram of first and second fine particle structures according to the first embodiment.

FIG. 10 is an explanatory diagram of the optical integrated circuit according to the first embodiment.

FIG. 11 is an explanatory diagram of first and second fine particle structures according to the second embodiment.

FIG. 12 is an explanatory diagram of an optical integrated circuit according to a second embodiment.

[Explanation of symbols]

101 glass substrate 101a concave pattern 101b concave pattern 101c concave pattern 101d concave pattern 102 dispersion 103 TiO ₂ fine particles 104 microtweezers 105 TiO ₂ fine particle film 106 fine particle structure 301 glass substrate 301a first concave pattern 301b second Recessed pattern 302 Al ₂ O ₃ fine particles 303 Dispersion 304 Fine particle film (TiO ₂ + Al ₂ O ₃ ) 305 Fine particle structure 501 Polystyrene layer 801 Glass substrate 801a Recessed pattern 802 Fine particle structure 803 Chamber 804 Heating stage 805 Fine particle structure

Claims (16)

[Claims] 1. A first fine particle structure and a second fine particle structure, which are composed of fine particles having a uniform particle size, have periodic structures different from each other and are patterned in an arbitrary shape, are formed on the same substrate. A fine particle structure characterized by being provided. 2. The fine particle structure according to claim 1, wherein the first and second fine particle structures are composed of spherical fine particles. 3. The first and second fine particle structures are composed of fine particles having the same composition.
Or the fine particle structure described in 2. 4. The fine particle structure according to claim 1 or 2, wherein the first and second fine particle structures are composed of fine particles having different compositions. 5. The fine particle structure according to claim 1, wherein the first and second fine particle structures are constituted by fine particles having different particle sizes. 6. The material of the first and / or second fine particle structure is filled with a substance made of a material different from that of the fine particles, between the fine particles.
5. The fine particle structure according to any one of 1. 7. The fine particle structure according to any one of claims 1 to 6, wherein the material of the fine particles constituting the first and second fine particle structures and the substrate are both metal oxides. . 8. An optical integrated circuit comprising the fine particle structure according to claim 1 and an optical circuit constructed by patterning the shapes of the first and second fine particle structures. . 9. A fine particle film on the concave pattern by applying and spreading a fine particle dispersion liquid, in which fine particles having a uniform particle diameter are dispersed in a dispersion medium, on a substrate having a concave pattern on the surface thereof. And a fine particle structure for forming a fine particle structure by stacking a plurality of fine particle films after peeling the fine particle film from a substrate using an adsorption device having a function of adsorbing a fine article. A method of manufacturing a fine particle structure, comprising a body forming step. 10. The concave pattern formed on the substrate comprises a first concave pattern and a second concave pattern formed on a bottom portion of an inner surface of the first concave pattern, wherein the fine particles are formed. The film forming step includes a first fine particle arranging step of arranging the first fine particles in the second concave pattern by applying and developing a dispersion liquid of the first fine particles on the substrate and drying the dispersion liquid. The first fine particles are obtained by applying and spreading a dispersion liquid of second fine particles having a particle diameter smaller than that of the first fine particles on a substrate on which the dispersion liquid of the first fine particles is coated and spread, and drying. 10. The method for producing a fine particle structure according to claim 9, further comprising: a mixed fine particle film forming step of forming a mixed fine particle film composed of the second fine particles. 11. The method of manufacturing a fine particle structure according to claim 10, wherein the second concave-shaped pattern is composed of a set of concave-shaped portions formed at a constant period. 12. A coating step of coating a dissolution-removable coating layer on the substrate on which the concave pattern is formed, and a solvent as a pretreatment for peeling the fine particle film from the substrate in the fine particle structure forming step. A coating layer removing step of dissolving and removing the coating layer according to claim 9 to 11.
5. The method for producing a fine particle structure according to any one of 1. 13. The fine particle structure according to claim 9, further comprising a fine particle film electric pulse applying step of applying an electric pulse to the fine particle film formed on the concave pattern. Body manufacturing method. 14. The laminated fine particle film electric pulse applying step of applying an electric pulse to the fine particle films stacked in the fine particle structure forming step, according to claim 9. Method of manufacturing fine particle structure. 15. A hydrogen reduction step of exposing at least one of the fine particle film formed on the concave pattern and the fine particle film stacked in the fine particle structure forming step to a hydrogen reducing atmosphere. 15. The method for producing a fine particle structure according to any one of 9 to 14. 16. The method for producing a fine particle structure according to claim 9, wherein the fine particles are metal oxide fine particles.