JP4423996B2 - Method for producing two-dimensional array structure - Google Patents

Description

  The present invention relates to a method for producing a two-dimensional array structure. More specifically, the present invention is a simple process utilizing a photoresponsive material that can cause optical deformation and exhibits a fixing ability when light is irradiated to a minute object arranged on the surface. Thus, the present invention relates to a method for producing a two-dimensional array structure capable of immobilizing micro objects in a two-dimensional specific arrangement form accurately and regularly.

  The present invention includes, for example, a photonic crystal in which silica particles and the like are two-dimensionally arranged and immobilized on a structure substrate, a protein chip in which proteins or DNA and the like are two-dimensionally arranged and immobilized on a structure substrate, It can be preferably applied to production of a bioreactor or a biosensor.

  2. Description of the Related Art Conventionally, there are roughly two techniques for producing an array structure in a state where a large number of minute objects are arrayed in a fixed arrangement on a fixed substrate. The first technique is a so-called top-down method using a semiconductor microfabrication technique. In this technique, light, an electron beam, an ion beam, or the like is used, or processing is performed by lithography or post-processing, etching or deposition. The following “Patent Document 1” discloses such a technical example. The second technique is a technique of arranging a large number of minute objects in a self-organized manner (self-assembly) by a so-called bottom-up method, and as a result, producing an array structure. The following “Patent Document 2” discloses such a technical example.

Kiyoshi Asakawa, Yoshimasa Sugimoto “2D Photonic Crystal Slab Waveguide and Optical Integrated Circuit” O plus E, Vol. 25, No. 2 Miyao Inoue, Masaaki Haga "2D and 3D arraying of colloidal particles and its applications" Colored materials, 76 [1], 24-33 (2003)

  However, although the above-described first conventional technique can produce a fine and accurate array structure, it requires a complicated process as is well known, and the production cost is increased accordingly. On the other hand, since the second prior art described above is expected for self-organized collection / arrangement of minute objects, it is difficult to arrange the minute objects accurately and regularly in a fixed arrangement. Further, it is not suitable for manufacturing an array structure over a wide area.

  In addition, in photonic crystals and protein chips, which are typical examples of the above-described arrangement structure, fine particles such as target inorganic particles and proteins are arranged in two dimensions (in one layer). There is a strong demand for fixed objects. In addition, there is a particularly strong demand for an immobilization region in which minute objects are arranged / immobilized and a non-immobilization region in which minute objects are not arranged / immobilized are arranged adjacent to each other in an arbitrary pattern.

  Accordingly, the present invention provides a two-dimensional array structure in which a large number of minute objects are arranged and fixed two-dimensionally and regularly in a fixed arrangement on the substrate, and further, such a minute object is fixed. It is a technical problem to be solved to provide a method capable of producing a two-dimensional array structure in which regions and non-immobilized regions are set in an arbitrary pattern at a low cost by a simple process.

(Configuration of the first invention)
The structure of the first invention of the present application for solving the above-described problem is that at least a photoresponsive material capable of causing optical deformation and exhibiting an immobilizing ability when irradiated with light on a minute object arranged on the surface is provided. A template forming step of forming a concavo-convex structure in which irregularities are regularly arranged in an arbitrary arrangement form by an arbitrary concavo-convex structure forming means on the surface of the structure base in the surface layer portion;
An alignment step of arranging and adsorbing a large number of micro objects having a size corresponding to the concave portion of the concave-convex structure in the concave portion;
An immobilization step of immobilizing the microscopic objects adsorbed on the array by irradiating the surface of the structure base with light;
Is a method for producing a two-dimensional array structure.

(Configuration of the second invention)
The structure of the second invention of the present application for solving the above-described problem is that a fine object fixing region and a minute object are formed on the surface of the structure base by using a mask pattern at the time of light irradiation in the fixing process according to the first invention. This is a method for producing a two-dimensional array structure in which an object non-immobilized region is set in an arbitrary pattern.

(Configuration of the third invention)
The structure of the third invention of the present application for solving the above problem is a method for producing a two-dimensional array structure in which the concavo-convex structure forming means used in the template forming step according to the first invention or the second invention is an optical means. is there.

(Configuration of the fourth invention)
The configuration of the fourth invention of the present application for solving the above problem is a method for producing a two-dimensional array structure, in which the optical means according to the third invention is irradiation of interference light onto the surface of the structure substrate.

(Structure of the fifth invention)
In order to solve the above-described problem, the fifth invention of the present application is such that the irradiation interference light according to the fourth invention is formed by two light fluxes, and the template forming step is performed by repeating irradiation with the incident angle and in-plane rotation controlled. This is a method for producing a two-dimensional array structure.

(Structure of the sixth invention)
The structure of the sixth invention of the present application for solving the above-described problem is a method for producing a two-dimensional array structure, in which the irradiation interference light according to the fourth invention is three or more luminous fluxes, and the template forming step is performed by one irradiation. It is.

(Structure of the seventh invention)
The structure of the seventh invention of the present application for solving the above problem is a two-dimensional array structure in which the optical means according to the third invention is an application of lithography (mask pattern exposure transfer) technology to the surface of the structure base. This is a manufacturing method.

(Configuration of the eighth invention)
The structure of the eighth invention of the present application for solving the above problem is a process of removing non-immobilized minute objects existing on the structure substrate after the immobilizing process according to any of the first to seventh inventions. Is a method for producing a two-dimensional array structure.

(Structure of the ninth invention)
The structure of the ninth invention of the present application for solving the above problem is that the concave portion of the concavo-convex structure formed in the template forming step according to any of the first to eighth inventions has a width in the range of 1 nm to 5 μm. This is a method for manufacturing a two-dimensional array structure that is densely arranged in size and via extremely minute protrusions.

(Configuration of the tenth invention)
The structure of the tenth invention of the present application for solving the above problem is a two-dimensional array structure in which the photoresponsive material according to any one of the first to ninth inventions is a material including a dye structure having an azo group. This is a method for producing a body.

(Structure of 11th invention)
The structure of the eleventh invention of the present application for solving the above problem is that the dye structure having an azo group according to the tenth invention comprises an intramolecular charge transfer structure having an electron-withdrawing substituent and an electron-donating substituent. This is a method for producing a two-dimensional array structure.

(Configuration of the twelfth invention)
The structure of the twelfth invention of the present application for solving the above problems is a two-dimensional array in which the micro object according to any of the first to eleventh inventions is made of any of the following materials (1) to (3). This is a method for manufacturing a structure.
(1) A polymer material, a ceramic material, a metal material, or a hybrid material of two or more of these materials.
(2) Protein. This category includes at least antigens, antibodies, enzymes and glycoproteins.
(3) A microsphere made of an arbitrary material and having a surface to which at least one protein of the above (2) or a nucleic acid molecule is attached or bound.

(Structure of the thirteenth invention)
The structure of the thirteenth invention of the present application for solving the above problem is a method for producing a two-dimensional array structure in which the two-dimensional array structure according to any one of the first to twelfth inventions is a photonic crystal structure. It is.

(Structure of the 14th invention)
The structure of the fourteenth invention of the present application for solving the above problem is a method for producing a two-dimensional array structure in which the photonic crystal structure according to the thirteenth invention is a two-dimensional slab type optical device.

(Structure of the fifteenth invention)
The structure of the fifteenth aspect of the present invention for solving the above-described problem is that a two-dimensional slab type optical device according to the fourteenth aspect of the present invention is an optical waveguide, an optical amplifier, or an optical modulator. It is.

(Effect of the first invention)
In the method for producing a two-dimensional array structure according to the first aspect of the present invention, a concavo-convex structure in which irregularities are regularly arranged in an arbitrary arrangement form is formed on a photoresponsive material having a predetermined function. A large number of minute objects are arranged and adsorbed in the recesses and fixed. Therefore, as long as the concavo-convex structure is accurately formed, a two-dimensional array structure in which a large number of minute objects are arranged and fixed accurately and regularly in a fixed arrangement can be produced. And since there are some concavo-convex structure forming means that can accurately form the concavo-convex structure in a predetermined manner in the known art, these means may be appropriately selected.

  In the arraying process, there may be a part where micro objects are stacked in two or more layers (three-dimensionally) on the structure base, but the immobilization action of the photoresponsive material in the immobilization process Acts only on the minute objects arranged in the recesses of the concavo-convex structure, and as a result, the minute objects are arranged and fixed two-dimensionally (in one layer) on the substrate.

  The manufacturing method of the two-dimensional array structure of the first invention includes the template forming step, the arraying step, and the immobilizing step, which are not particularly complicated processes, and are particularly expensive processing apparatuses or the like. Therefore, the production cost of the two-dimensional array structure does not increase.

  In terms of the function of the light-responsive material, even if a large number of micro objects are placed on the surface of the structure substrate without performing a template forming process and an immobilization process by light irradiation is performed, An object can be fixed. However, in this case, since the micro objects are arranged in a self-organized manner on the surface of the structure base, the accuracy and regularity of the arrangement are insufficient as described above with respect to the prior art.

(Effect of the second invention)
In the method for producing a two-dimensional array structure, as in the second invention, a mask pattern can be used at the time of light irradiation in the immobilization process, and as a result, a photoresponsive material is formed on the surface of the structure base. It is possible to set a portion where the immobilizing action is expressed and a portion where it is not expressed. As a result, the minute object immobilization region and the minute object non-immobilization region can be set in an arbitrary pattern.

(Effect of the third invention)
As the concavo-convex structure forming means used in the template forming step, an optical means is particularly preferable. The optical means as the concavo-convex structure forming means is advantageous in that the characteristics of the photoresponsive material can be used. In general, the concavo-convex structure has simpleness and low cost as a means, and has a very fine concavo-convex structure. It is also advantageous in that it can be formed regularly and accurately.

(Effect of the fourth invention)
Of the optical means as the concavo-convex structure forming means, a particularly preferable means is irradiation of interference light onto the surface of the structure base as in the fourth invention. Roughness suitable as a template for the arrangement and immobilization of micro objects by reflecting regular repetition of light intensity specific to interference light as regular repetition of the amount of light deformation of the photoresponsive material A structure can be formed.

(Effect of the fifth invention)
In the irradiation of the interference light on the surface of the structure body, one preferred embodiment is that the irradiation interference light is formed by two light beams, and the template forming process is performed by repeating irradiation with the incident angle and in-plane rotation controlled. is there.

  Of course, irradiating the interference light formed by the two light beams only once is also an aspect of an effective concavo-convex structure forming means, in which case a corrugated concavo-convex structure is formed on the surface of the structure base. The And, by irradiating the surface of the structure base on which such a corrugated plate-like concavo-convex structure is formed with the same interference light by controlling the incident angle and the in-plane rotation, the lattice shape in an arbitrary arrangement form A concavo-convex structure in which concavo-convex portions are arranged in a square lattice, a rectangular lattice, a hexagonal lattice, or the like can be formed.

(Effect of the sixth invention)
In the irradiation of the interference light on the surface of the structure base, another preferred embodiment is that the irradiation interference light has three or more luminous fluxes, and the template forming step is performed by one irradiation. In this case, it is possible to form a concavo-convex structure in which concavo-convex portions are arranged in a lattice shape having an arbitrary arrangement by one irradiation of interference light.

(Effect of the seventh invention)
Lithography (mask pattern exposure transfer) on the structure substrate surface as in the seventh invention, as another optical means as the concavo-convex structure forming means, which is complicated or expensive compared to the irradiation of the interference light described above. Application of the technology can be preferably exemplified.

(Effect of the eighth invention)
As described above with respect to the first invention, even if there is a portion in which the minute objects are laminated in two or more layers (three-dimensionally) on the structure base in the arranging step, the light responsiveness in the fixing step is present. The immobilization action of the material acts only on the minute objects arranged in the recesses of the concavo-convex structure. In the second invention, the immobilization action of the photoresponsive material acts only on the minute object in the minute object immobilization region.

  However, as a matter of fact, the minute objects that are layered and arranged in the second layer or more, and the minute objects that existed in the non-immobilized area of the minute object are partly fixed. May remain on the surface of the structure substrate in a state of simple adhesion or the like, and may adversely affect the completed two-dimensional array structure. Therefore, as in the eighth invention, it is more preferable to add a step of removing non-immobilized minute objects existing on the structure base after the fixing step.

(Effect of the ninth invention)
The concave and convex portions of the concavo-convex structure are set corresponding to the size of the minute object to be arranged and fixed, but the width is in the range of 1 nm to 5 μm and is densely arranged through extremely minute convex portions. It is preferable.

  In addition to acting as a partition between the concave portions, the convex portion of the concave-convex structure has a convex portion by setting the width of the convex portion slightly larger when it is desired to set a space between the individual minute objects arranged and fixed. The part can also act as a spacer.

(Effect of the tenth invention)
As the photoresponsive material, a material showing a corresponding function can be arbitrarily selected and used, but a material including a dye structure having an azo group is particularly preferable.

  This material undergoes isomerization from trans to cis or from cis to trans by light irradiation. Therefore, there is an effect of facilitating deformation and immobilization (of a minute object) due to a change in free volume inside the polymer and an increase in internal stress in the state where isomerization has occurred. This is due to a change in the arrangement of molecules, and is highly effective in terms of deformation and fixation under relatively gradual conditions.

(Effect of the 11th invention)
The dye structure having an azo group is particularly preferably an intramolecular charge transfer structure having an electron-withdrawing substituent and an electron-donating substituent.

  Those having such a structure cause isomerization from trans to cis by light irradiation, but the cis state is thermally unstable and often has a property of quickly returning to the trans state. For this reason, the trans-cis-trans cycle is repeated during light irradiation, and this property has the effect of dramatically increasing the efficiency of light deformation and light immobilization.

(Effect of the twelfth invention)
In the two-dimensional array structure, the type of micro object to be arranged and fixed is not limited. For example, a micro object made of any one of the materials (1) to (3) of the twelfth invention can be preferably exemplified. .

(Effect of the thirteenth invention)
The two-dimensional array structure can be a structure having various functions depending on the kind of micro objects to be arrayed and immobilized, but a typical example is a photonic crystal structure.

(Effect of the 14th invention)
As the photonic crystal structure, a two-dimensional slab type optical device can be preferably exemplified.

(Effect of the fifteenth invention)
As the two-dimensional slab type optical device, an optical waveguide, an optical amplifier, or an optical modulator can be preferably exemplified.

  Next, modes for carrying out the first to fifteenth inventions of the present application will be described including the best mode. In the following, the term “present invention” refers to each invention of the present application collectively.

[Method for producing two-dimensional array structure]
The method for producing a two-dimensional array structure according to the present invention includes a template formation step, an alignment step, and an immobilization step. After the immobilization step, a step of removing non-immobilized minute objects existing on the structure base can be added. Also, any necessary or beneficial steps can be added before, during or after each of these steps.

[Micro objects and two-dimensional array structure]
There are various categories of two-dimensional array structures depending on the types of micro objects to be arrayed and immobilized. The type of the minute object is not limited, but a representative example is one made of any of the following materials (1) to (3). The thing of (4) can also be illustrated preferably.

  (1) Metal particles, metal oxide particles, semiconductor particles, ceramic particles, plastic particles, or particles made of two or more materials (hybrid material) among them. By fixing these, for example, a field effect transistor or a two-dimensional photonic crystal can be formed. Further, by arranging and fixing them according to a fixed area distribution pattern, an electrical or optical integrated circuit chip or the like can be configured. Silica particles or plastic particles have the effect of confining light, and by introducing fluorescent molecules inside, laser oscillation by a resonator structure becomes possible, and an integrated device can be manufactured by fixing to an optical waveguide.

  (2) Proteins such as enzymes, antigens, antibodies, cell membrane receptor proteins, or various protein groups expressed in biological cells. These can be once fixed on microbeads made of plastic or the like, and the microbeads can be arranged and fixed on the structure substrate. Bioreactors and biosensors can be constructed by arranging and immobilizing enzymes, and integrated enzyme transistors can be constructed by arranging and immobilizing enzymes according to a fixed immobilization region distribution pattern. Sequences of various proteins expressed in biological cells, such as test chips for immunoassay by arrangement or immobilization of antigens or antibodies, and analysis means such as functions and signal transduction mechanisms of cells by arrangement and immobilization of cell membrane receptor proteins・ Proteome analysis test chips by immobilization, arrangement of a group of proteins that are expressed tissue-specific, pathologically specific or developmental / differentiation stage specific ・ Function of proteins by immobilization in relation to expression specificity Each means that can be analyzed can be configured.

  (3) Single-stranded or double-stranded nucleic acid, ie, polynucleotide. More specifically, a DNA fragment containing a single nucleotide polymorphic part, a restriction enzyme fragment or a DNA fragment containing a microsatellite part can be exemplified. Since these DNA fragments can be used as genetic markers, a DNA chip or a DNA microarray capable of analyzing an individual's SNP and genotype can be constructed by arrangement and immobilization thereof. And it can contribute to realization of forensic appraisal and tailor-made medicine. Examples include mRNA and fragments thereof, cDNA and fragments thereof, and genomic DNA fragments. These are also effective for gene analysis. When arranging and immobilizing a single-stranded polynucleotide, in order to facilitate hybridization, fine particles are bound in advance to the end of the polynucleotide, and the fine particles are arranged and immobilized on the structure base. As a result, the end of the polynucleotide is sequenced and immobilized on the structure base, and it is particularly preferable.

  (4) Cells or microorganisms. Particularly preferably cells or microorganisms in the living state. By arranging and immobilizing these, in addition to these morphological studies, a powerful means for in vitro analysis of the functions of biomolecules such as DNA and proteins using cells or microorganisms is provided. The

[Photo-responsive material]
The photo-responsive material refers to a material that can cause light deformation and exhibits an immobilization ability when irradiated with light on a minute object arranged on the surface.

  As a preferred example, a component (photoreactive component) that causes ablation, photochromism, photoinduced orientation of molecules, etc. by photoirradiation is included in the photoresponsive material, resulting in the volume, density, and free volume of the photoresponsive material. An organic or inorganic material in which photodeformation is generated by changing the above can be exemplified. In addition, inorganic materials such as those generally called chalcogenite glass including a structure in which any one of sulfur, selenium, and tellurium and any of germanium, arsenic, and antimony are combined can be exemplified.

  Although the kind of photoreactive component is not limited, For example, the photoisomerization component and photopolymerizable component which are components which can raise | generate anisotropic photoreaction accompanying the shape change of material can be illustrated preferably. When the micro object is a biological substance whose activity is impaired by a chemical reaction with the carrier material, a photoisomerization component is preferable as the photoreactive component.

  As the photoisomerization component, for example, a component causing trans-cis photoisomerization, particularly typically a dye structure having an azo group (—N═N—), particularly a component having a chemical structure of azobenzene or a derivative thereof. Can be preferably exemplified. When the photoresponsive material is a material including a dye structure having an azo group, the dye structure has one or more electron-withdrawing functional groups (electron-withdrawing substituents) and / or one or more. It is particularly preferable to have an electron donating functional group (electron donating substituent). As an electron-withdrawing functional group, a functional group having a positive value of the substituent constant σ in Hammett's rule, and as an electron-donating functional group, a functional group having a negative value of the substituent constant σ in Hammett's rule, respectively. Preferably exemplified.

  In the matrix of the photoresponsive material, the photoreactive component may be simply dispersed, but the distribution density of the photoreactive component in the matrix can be controlled, the heat resistance of the material or the stability over time, etc. It is particularly preferable that the photoreactive component is chemically bonded to the constituent molecules of the matrix. As the matrix material, an organic material such as a normal polymer material or an inorganic material such as glass can be used. In consideration of the uniform dispersibility or binding property of the photoreactive component to the matrix, an organic material, particularly a polymer material is preferable.

  The type of the polymer material is not limited, but the polymer repeating unit containing a urethane group, urea group, or amide group, and a ring structure such as a phenylene group in the polymer main chain It is preferable in terms of heat resistance. As long as the polymer material can be molded into a necessary shape, the molecular weight, the polymerization degree, and the polymerization form (linear, branched, ladder-like, etc.) are not limited. For the stability of light deformation over time (maintaining fixing force with respect to minute objects), it is preferable that the polymer material has a glass transition temperature as high as 100 ° C. or higher. Can be used at room temperature or lower.

  Specific examples of particularly preferable polymer materials containing a photoreactive component include those shown in the following “Chemical Formula 1” to “Chemical Formula 4” in addition to those described in the Examples. In these examples, -X represents a nitro group, a cyano group, a trifluoromethyl group, an aldehyde group, or a carboxyl group, -Y- represents -N = N-, -CH = N-, or -CH = CH-, R- represents a phenylene group, an oligomethylene group, a polymethylene group or a cyclohexane group, respectively. In “Chemical Formula 2”, the numerical ratio of m and n is arbitrary, and R ′ represents an alkyl group or a phenyl group.

構造体基盤の表層部を構成する光応答性材料の厚さは限定されないが、微小物体の固定化に必要な変形量を確保できる厚さは要求される。表層部を構成する光応答性材料は、一般的には５０ｎｍ以上、より好ましくは５００ｎｍ以上の厚さを有する。

The thickness of the photoresponsive material constituting the surface layer portion of the structure base is not limited, but a thickness that can secure the amount of deformation necessary for fixing the minute object is required. The photoresponsive material constituting the surface layer portion generally has a thickness of 50 nm or more, more preferably 500 nm or more.

[Irradiated light]
As irradiation light used in the template formation step and the immobilization step, any irradiation light such as propagating light, near-field light, or evanescent light can be used as long as there is no mismatch in combination with the photoresponsive material. Natural light, laser light, or the like can be used as the propagating light. The polarization characteristics can be used as propagating light, near-field light, or evanescent light. The wavelength of the irradiation light and the light source are not limited, but the wavelength is preferably a wavelength with high absorption efficiency of the photoresponsive material. When there is a possibility that a minute object is affected by inactivation, deterioration, or the like due to, for example, ultraviolet light (wavelength 300 to 400 nm), it is preferable to use visible light (wavelength 400 to 600 nm) as irradiation light. What is necessary is just to set the irradiation time of irradiation light arbitrarily as needed.

  In order to regularly form a large number of irregularities in the template forming step, it is preferable to use the light intensity distribution in the interference light.

  When setting a fixed area and a non-fixed area of a minute object on the structure base in the fixing process, it is possible to irradiate a narrow focused beam according to a specific pattern. A mask can be used. Although the usage method of a photomask is not limited, For example, a proximity exposure method and a projection exposure method can be illustrated. Furthermore, the light intensity distribution in the interference light can be used.

[Template formation process]
In the template formation process, the surface of the structure base that can cause light deformation and has at least a surface of a photoresponsive material that exhibits a fixing ability when light is irradiated to a minute object disposed on the surface. In addition, the concavo-convex structure in which the concavo-convex is regularly arranged in an arbitrary arrangement is formed by an arbitrary concavo-convex structure forming means.

  As a form of the structure base, there are a case where the substrate is made of only a photoresponsive material and a case where a substrate made of an appropriate material such as a glass substrate or a metal substrate is coated with the photoresponsive material.

  The type or content of the concavo-convex structure forming means is not limited, but it is preferable to use optical means, and as this optical means, application of lithography (mask pattern exposure transfer) technique to the surface of the structure substrate is also preferable. However, irradiation of interference light on the surface of the structure base is particularly preferable.

  In the irradiation of the interference light, it is preferable to perform the template forming step by repeating the irradiation in which the interference light is formed by two light beams and the incident angle and in-plane rotation are controlled. The incident angle of the interference light is a means for substantially defining the pitch of the concavo-convex structure as will be described later in the embodiment. The in-plane rotation refers to changing the crossing angle of the two-beam interference light with respect to the stripe pattern by rotating the structure base in the plane.

  In the interference light irradiation, it is also preferable that the interference light has three or more light beams, and the template forming step is performed by one irradiation. In this case, a lattice-shaped uneven structure can be formed by one irradiation of interference light. Examples of the lattice form include a two-dimensional periodic structure, and examples include various lattice forms such as a hexagonal lattice, a tetragonal lattice, a rectangular lattice, an orthorhombic lattice, and the like.

  The lithography (mask pattern exposure and transfer) technique described above is a mask that places an arbitrary mask pattern on the top of the photoresponsive material and irradiates light from above to induce photodeformation of the photoresponsive material. This is a technique for transferring a pattern shape to an uneven shape.

  For template formation, optical means are not necessarily used. For example, a template can be formed by transferring a mold plate having a desired concavo-convex structure formed on the surface thereof against the photoresponsive material layer on the surface of the structure substrate.

[Sequence process]
In the arranging step, a large number of minute objects having a size corresponding to the concave portions of the concave-convex structure are arranged and adsorbed on the concave portions. In addition, since the concave portions of the concavo-convex structure define the size and arrangement mode of minute objects, the width thereof is in the range of 1 nm to 5 μm, and the array is densely formed through extremely minute convex portions. It is preferable that

[Immobilization process]
In the immobilization step, the minute objects arranged and adsorbed in the concave portions of the concavo-convex structure are fixed by irradiating the surface of the structure base with light. By using a mask pattern at the time of light irradiation in the immobilization process, the minute object immobilization region and the minute object non-immobilization region can be set in an arbitrary pattern on the surface of the structure base.

  In addition, it is also preferable to add the process of removing the non-immobilized minute object existing on the structure base after the fixing process. This step can be performed, for example, by ultrasonic cleaning as in the examples described later.

(Example 1: Base preparation process)
As the photoresponsive material, a urethane-urea copolymer azo polymer represented by the following “Chemical Formula 5” was used. Then, this polymer was dissolved in pyridine at a certain concentration, and coated on a glass substrate with a spin coater at a predetermined number of revolutions to form a film having a thickness of about 1 μm. Next, the substrate of the structure used in the following examples was produced by subjecting it to drying and heat treatment at 150 ° C. overnight under vacuum.

  In addition to this, by using the urethane copolymer azo polymer shown in the following “Chemical Formula 6”, a structure base was prepared in the same manner as above (except that drying and heat treatment were performed at 130 ° C.). The same results are obtained by performing the same examples as those described above, but details thereof are omitted.

上記のガラス基板としては、後の固定化工程後の水洗浄時にコーティングフィルムがガラス基板から剥離しないように、表面が高密度アミノ基で覆われた剥離防止用ＭＡＳコートスライドグラス（松波ガラス社製）を用いた。因みに、通常のガラス基板を用いて同上の要領でポリマーのコーティングフィルムを作製した場合には、水洗浄時にコーティングフィルムが剥離する恐れがある。。

As the glass substrate, an MAS-coated slide glass for preventing peeling whose surface is covered with a high-density amino group so that the coating film does not peel from the glass substrate at the time of washing with water after the subsequent fixing step (manufactured by Matsunami Glass Co., Ltd.) ) Was used. Incidentally, when a polymer coating film is produced in the same manner as described above using a normal glass substrate, the coating film may be peeled off during washing with water. .

(Example 2: Template forming step 1)
Next, a concavo-convex structure in which irregularities were regularly arranged on the surface of the structure base (photoresponsive material film) was formed on the structure base by exposure with two-beam interference light. That is, after the first exposure of the two-beam interference light, the surface relief grating (SRG) having the corrugated uneven structure as shown in FIG. 1 (1) is formed by utilizing the optical deformation of the photoresponsive material. Then, after the structure substrate is rotated by 90 ° in the plane, the second two-beam interference light exposure is performed, and the irregularities as shown in (2) of FIG. 1 are regularly arranged in a square lattice pattern. (Uneven structure) was formed.

In both the first and second exposures described above, a water-cooled CW argon laser (manufactured by LEXEL) was used as the interference light source, and laser light with a wavelength of 488 nm was irradiated. The laser beam was divided into two by a non-polarizing beam splitter, and interference exposure was performed on the structure substrate at a predetermined incident angle. The incident angle was determined by the following calculation formula so that the unevenness occurred at the intended pitch. In this calculation formula, Λ _GR is the pitch of interference fringes, λ is the wavelength of incident light, and θ is the incident angle. When the laser beam was irradiated as it was, the irradiation power was irradiated at a maximum of 150 mw on one side.

Λ _GR = λ / (2 · sinθ)
After the template formation process is completed, the surface of the structure substrate is observed for deformation with a contact mode atomic force microscope (Digital Instruments: Nano Scope E), and the depth of recess deformation is also evaluated. did. In the following FIGS. 2A to 2C and FIGS. 3A to 3C, the depth of the recess deformation is shown in the end face portion of the figure. The whole image was also observed with an optical microscope.

  In order to increase the irradiation area of the interference light, the surface of the photoresponsive material film can be deformed by expanding the beam with a beam expander.

(Example 3: Template forming step 2)
FIG. 2A shows an atomic force microscope image of the SRG by the first interference light exposure when the incident angle θ of the interference light is 77.4 °, and the pitch of the corrugated deformation is 250 nm. there were. The atomic force microscope image of the SRG by the first interference light exposure when the incident angle θ of the interference light is 29.2 ° is shown in FIG. 2B, and the pitch of the corrugated deformation is 500 nm. . The atomic force microscope image of the SRG by the first interference light exposure when the incident angle θ of the interference light is 14.1 ° is shown in FIG. 2B, and the pitch of the corrugated deformation is 1000 nm. .

  When laser light with a wavelength of 488 nm is irradiated as described above, the diffraction limit (corresponding to an incident angle of 90 °) is about 244 nm, which is a half of the wavelength, and a concavo-convex structure is formed at a pitch that is almost close to the diffraction limit. It turns out that it is possible.

(Example 4: Template forming step 3)
Next, in performing the first interference light exposure, the in-plane rotation of the structure base, and the second interference light exposure, the incident angle of the first and second interference light and the degree of in-plane rotation are varied. I changed it. As can be seen from the following examples, in principle, any two-dimensional crystal structure can be produced by controlling the in-plane rotation angle of the structure base and the incident angle of the interference light.

  The first example is an example in which the corrugated plate-like deformation is formed at a pitch of 1000 nm in Example 3 above, and the structure base is rotated in the plane by 90 °, and then the interference light having the same incident angle as the first time is used. In this case, the second interference light exposure is performed. An atomic force microscope image of the resulting concavo-convex structure is shown in FIG. 3A. The concavo-convex structure is formed in a square lattice (a = b, α = 90 °) shape having a lattice length of 1000 nm. I understand that.

  The following example is an example in which the corrugated plate-like deformation is formed at a pitch of 500 nm in Example 3 above, and the structure base is rotated in the plane by 120 °, and then the interference light having the same incident angle as the first time. In this case, the second interference light exposure is performed. The resulting atomic force microscope image of the concavo-convex structure is shown in FIG. 3B. The concavo-convex structure is produced in a hexagonal lattice (a = b, α = 60 °) shape having a lattice length of 580 nm. I understand that.

  Another example is that, in contrast to the example in which the corrugated plate-like deformation is formed at a pitch of 1000 nm in Example 3 above, the structure base is rotated in the plane by 90 °, and the pitch of 1500 mm is different from the first time. In this case, the incident angle is changed so that the second interference light exposure is performed. An atomic force microscope image of the resulting concavo-convex structure is shown in FIG. 3C. The concavo-convex structure is in the form of a rectangular lattice having a lattice length of 1000 nm and 1500 mm (a and b are different, α = 90 °). It can be seen that is produced.

(Example 5: Arrangement process)
A doughnut-shaped disk is set on the surface of the structure substrate on which a square lattice-like concavo-convex structure is formed on the surface at a pitch of 1000 nm, as shown in FIG. Water in which Moritex Corporation) was suspended was dropped into the inside of the disk. Subsequently, as shown in FIG. 1 (4), water was pipetted several times with a micropipette, and the suspended water was sucked up from the vicinity of the inner peripheral wall of the disk. Next, after the moisture was dried, the disk was removed. And the arrangement | sequence state of the polystyrene microsphere was observed with the scanning laser confocal microscope (the Olympus company make: OLS1100). The microscope image is shown in FIG.

(Comparative example of Example 5 and comparison evaluation with Example 5)
FIG. 5 shows an image obtained by observing the arrangement state of the polystyrene microspheres with the above-mentioned microscope by performing the same operation as that of Example 5 on the above-described structure base that has not undergone the template formation step. In this case, as shown in FIG. 5, the polystyrene microspheres are basically arranged in a hexagonal lattice. That is, since the interaction between microspheres is strong, it is considered that the most stable hexagonal structure array was taken in terms of energy. At the same time, as is apparent from FIG. 5, it can be seen that such a hexagonal structure has a domain structure, and the boundary between domains is defective. This can be considered as a result of collision of crystal growth in the formation of a colloidal two-dimensional crystal.

  On the other hand, in the microscopic image of FIG. 4 which is the result of Example 5, a portion in which microspheres are arranged in a square lattice shape is recognized, and the arrangement portion is arranged in a single layer structure (two-dimensional). The reason for this is that, as is clear from the comparison with FIG. 5 described above, the concavo-convex structure on the surface of the structure base (the depth of the concave portion is about 100 nm) worked as an effective template, and as a result, arranged as described above. Can think.

  Further, in FIG. 4, a portion where polystyrene microspheres overlap each other and the polystyrene microspheres on the surface layer (uppermost layer) are arranged in a hexagonal lattice shape is widely observed. In this part, in summary, the polystyrene microspheres in the surface layer are not affected by the uneven structure on the surface of the structure base, and are arranged in a stable hexagonal lattice pattern by the interaction between the microspheres as in the case of FIG. Conceivable. In other words, even in such a portion, it is estimated that the microspheres are accurately arranged in a square lattice pattern in the lowest layer of the multi-layered overlap due to the template effect of the uneven structure on the surface of the structure base.

(Example 6: Immobilization step 1)
Next, interference exposure is performed on the surface of the structure substrate after the arrangement process of Example 5, and the same laser light as above is directly applied to the portion where the polystyrene microspheres are arranged as shown in FIG. Irradiation was performed from 100 to 300 mw from the surface side of the structure base for 5 to 15 minutes. Subsequently, the structure base was gently washed with distilled water in a beaker to the extent that the contents were shaken several times, and then ultrasonically cleaned for about 10 seconds with an ultrasonic cleaner. And after making it dry, the arrangement | sequence state of the polystyrene microsphere was observed with the said scanning laser confocal microscope. The observation image is shown in FIG.

  According to FIG. 6, only the polystyrene microspheres arranged by the template effect of the uneven structure on the surface of the structure base, even though only a part of them are dropped out, a single layer (two-dimensional) arranged accurately in a hexagonal lattice shape. In the part where the polystyrene microspheres overlap in multiple layers, the parts other than the lowermost polystyrene microspheres are excluded by ultrasonic cleaning. This means that only the polystyrene microspheres arranged by the template effect have been fixed with the strength to withstand ultrasonic cleaning by the irradiation of the laser beam in the fixing step.

  It should be noted that an example of an unprocessed structure base (that is, a structure base in which microspheres are arranged in a concavo-convex structure as in Example 5 and has not undergone the immobilization process according to Example 6) When ultrasonic cleaning was performed in the same manner as in No. 6, polystyrene microspheres fell off from the surface of the structure base.

(Example 7: Immobilization step 2)
As a modified example of the above-described Example 6, the structure substrate in which the corrugated plate-like deformation is formed at a pitch of 1000 nm in the above Example 3 is used as it is. An immobilization step similar to that in Example 6 was performed. The scanning laser confocal microscope image obtained as a result is shown in FIG.

  As is clear from FIG. 7, in the case of Example 7, the polystyrene microspheres are accurately arranged in the vertical direction (direction along the corrugated plate), but regularity is particularly seen in the horizontal arrangement. I can't. That is, the overall arrangement is neither a square lattice nor a hexagonal lattice. This indicates that the polystyrene microspheres are arrayed and fixed in accordance with the corrugated plate-like uneven structure as a template.

(Example 8: Production of two-dimensional slab type optical device)
As shown in FIG. 8A, in the case where polystyrene microspheres are arranged in a square lattice-like uneven structure on the surface of the structure base by the arrangement step of Example 5, Example 6 was performed using a photomask. The laser beam was irradiated in the immobilization step, followed by ultrasonic cleaning.

  As a result, when the surface of the structure base was observed with the scanning laser confocal microscope, the microscope itself was not presented, but as shown in FIG. 8B, areas where polystyrene microspheres were arranged and immobilized And regions not arranged and fixed were formed according to the pattern of the photomask. That is, these are two-dimensional slab type micro optical devices. The left side of FIG. 8B is a so-called “T-branch”, and the right side of FIG. 8B is a so-called “optical amplification resonator”. I have.

  In the present invention, various minute objects such as fine inorganic particles and proteins can be regularly arranged two-dimensionally on the structure base, and in that case, the immobilization region and the non-immobilization region of the minute object in an arbitrary pattern. Can be used, for example, for the production of protein chips and photonic crystals.

It is a figure which simplifies and shows the whole process of an Example.

It is a figure which shows the atomic force microscope image which concerns on an Example.

It is a figure which shows the atomic force microscope image which concerns on an Example.

It is a figure which shows the scanning laser confocal microscope image which concerns on an Example.

It is a figure which shows the scanning laser confocal microscope image which concerns on an Example.

It is a figure which shows the scanning laser confocal microscope image which concerns on an Example.

It is a figure which shows the scanning laser confocal microscope image which concerns on an Example.

It is a figure which simplifies and shows the preparation process of a two-dimensional slab type optical device.

Claims (13)

At least a surface responsive material capable of causing optical deformation and including a dye structure having an azo group and exhibiting an immobilizing ability upon light irradiation with respect to a minute object disposed on the surface. on the surface of the structure base with the, by optical means, the template forming step of forming an uneven structure that irregularities are regularly arranged and formed in any sequence form,
An alignment step of arranging and adsorbing a large number of micro objects having a size corresponding to the concave portion of the concave-convex structure in the concave portion;
An immobilization step of immobilizing the microscopic objects adsorbed on the array by irradiating the surface of the structure base with light;
A method for producing a two-dimensional array structure, comprising: The minute object immobilization region and the minute object non-immobilization region are set in an arbitrary pattern on the surface of the structure base by using a mask pattern at the time of light irradiation in the immobilization step. 2. A method for producing the two-dimensional array structure according to 1. The method for producing a two-dimensional array structure according to claim 1 or 2 , wherein the optical means is irradiation of interference light on the surface of the structure base. The method for producing a two-dimensional array structure according to claim 3 , wherein the irradiation interference light is formed by two light beams, and the template forming step is performed by repeating irradiation with controlled incident angle and in-plane rotation. The method for producing a two-dimensional array structure according to claim 3 , wherein the irradiation interference light has three or more light beams, and the template forming step is performed by one irradiation. 3. The method for producing a two-dimensional array structure according to claim 1, wherein the optical means is an application of lithography (mask pattern exposure transfer) technique to the surface of the structure base. The two-dimensional array structure according to any one of claims 1 to 6 , further comprising a step of removing non-immobilized minute objects existing on the structure base after the immobilization step. Manufacturing method. The concave portions of the concavo-convex structure formed in the template forming step are arranged in a dense array with extremely small convex portions having a width within a range of 1 nm to 5 μm. The method for producing a two-dimensional array structure according to claim 7 . Dye structure having the azo group, as claimed in any one of claims 1 to 8, characterized in that the intramolecular charge transfer structure provided with the an electron withdrawing substituent and electron donating substituent A method for producing a two-dimensional array structure. The method for producing a two-dimensional array structure according to any one of claims 1 to 9 , wherein the minute object is made of any one of the following materials (1) to (3).
(1) A polymer material, a ceramic material, a metal material, or a hybrid material of two or more of these materials.
(2) Protein. This category includes at least antigens, antibodies, enzymes and glycoproteins.
(3) A microsphere made of an arbitrary material and having at least one kind of the protein (2) or a nucleic acid molecule attached or bound on the surface. The method for producing a two-dimensional array structure according to any one of claims 1 to 10 , wherein the two-dimensional array structure is a photonic crystal structure. The method for producing a two-dimensional array structure according to claim 11 , wherein the photonic crystal structure is a two-dimensional slab type optical device. The method for producing a two-dimensional array structure according to claim 12 , wherein the two-dimensional slab type optical device is an optical waveguide, an optical amplifier, or an optical modulator.

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