JP7029750B2 - Organic microdisk array and its manufacturing method - Google Patents

Description

The present invention relates to an organic microdisk array and a method for manufacturing the same.

Structures made by integrating polymer particles on the nanometer to micrometer scale are attracting attention because they exhibit new electronic and optical functions. In particular, by integrating structures with a size close to the wavelength in the ultraviolet to visible range, it is expected that a photonic material exhibiting a new photoelectronic function will be realized.
As such a photonic material, for example, a pi-conjugated alternating copolymer having a tetramethyldithiophene structural element is known, and a method for producing the pi-conjugated alternating copolymer is also known (for example, non-patent documents). 1). Further, a method for forming fine particles and nanoparticles made of a pi-conjugated copolymer is also known (see, for example, Non-Patent Document 2).

By forming a spherical structure of such a photonic material and arranging the spherical structure on a silicon substrate to form an array, it can be applied to a light emitting device or the like.
As the structural element of the polymer for forming the spherical structure, the present inventors can easily form the spherical structure by the steam diffusion method in the pie-conjugated copolymer having tetramethylbithiophene as one component. (See, for example, Non-Patent Document 2). In addition, the present inventors disclose a polymer spherical array composed of spheres and hemispheres made of pi-conjugated polymers directly formed on one surface of a substrate, and a method for producing the same (for example, Patent Documents). 1).

Japanese Unexamined Patent Publication No. 2016-044273

Synthesis of pi-conjugated alternating copolymers with tetramethyldithiophene structural elements, Polym. Chem. 2013, 4, 947; doi: 10.1039 / c2py20917a Formation of fine particles and nanoparticles composed of pi-conjugated alternating copolymers, J. Mol. Am. Chem. Soc. 2013, 135,870; doi: 10.102 / ja3106626

However, conventionally, there has not been disclosed at all that an array composed of spheres or hemispheres made of pie-conjugated polymer is directly formed at equal intervals and at high density on one surface of a substrate. Further, no method has been disclosed for directly forming an array composed of spheres or hemispheres made of pie-conjugated polymers on one surface of a substrate at equal intervals and at high density.

The present invention has been made in view of the above circumstances, and an array composed of spheres or hemispheres composed of at least one of a pi-conjugated polymer and a photochromic molecule is formed at equal intervals and high density on one surface of a substrate. It is an object of the present invention to provide an organic microdisk array and a method for manufacturing the same.

[1] A substrate, a self-assembled monolayer having lyophilic regions and sparsely formed regions formed alternately on one surface of the substrate at equal intervals, and a solubilized region of the self-assembled monolayer. It comprises a plurality of spherical structures or hemispherical structures formed on one surface and made of at least a pie-conjugated polymer having low crystallinity, and the pie-conjugated polymer is composed of poly [(9,9-dioctylfluorenyl). -5-octylthiono [3,4-c] crystal-4,6-dione), Poly [2-methoxy-5- (3', 7'-dimethyloxyloxy) -1,4-phenylenevinylene] ..
[2] The organic microdisk array according to [1], wherein the plurality of spherical structures or hemispherical structures are composed of the pi-conjugated polymer having low crystallinity and a photochromic molecule.

[ 3 ] A substrate, a self-assembled monomolecular film having positivity regions and sparsely liquefied regions formed alternately on one surface of the substrate at equal intervals, and a solubilized region of the self-assembled monomolecular membrane. A method for manufacturing an organic microdisk array comprising a plurality of spherical structures or hemispherical structures formed on one surface and made of at least a pi-conjugated polymer having low crystallinity, which is formed on one surface of the substrate. , The step of forming the self-assembled monomolecular film and the self-assembled monomolecular film formed on one surface of the substrate are formed with the arsenic region and the sparsely liquor region at equal intervals and alternately. In the step, a solution containing at least the pi-conjugated polymer is applied to one surface of the self-assembled monomolecular film to form a coating film, and the coating film is dried to obtain at least the pi-conjugated polymer. By contacting the thin film with the vapor of a mixed solvent of chloroform and methanol, the self-assembled monomolecular film can be exposed to at least one surface of the liquor-friendly region from the pi-conjugated polymer. The pi-conjugated polymer has a step of forming a plurality of spherical structures or hemispherical structures, and the py-conjugated polymer is composed of poly [(9,9-dioctylfluorenyl-5-octylthieno [3,4-c] pyrrole-). 4,6-dione), Poly [2-methoxy-5 (3', 7'-dimethylocaltyloxy) -1,4-phenylenevinylene], a method for manufacturing an organic microdisk array.

[ 4 ] The method for producing an organic microdisk array according to [ 3 ], wherein the solution contains a photochromic molecule.

[ 5 ] The method for producing an organic microdisk array according to [ 3 ] or [ 4 ], wherein the blending ratio of chloroform and methanol in the mixed solvent is 1: 0.5 to 1: 1 in volume ratio.

[ 6 ] The production of the organic microdisk array according to any one of [ 3 ] to [ 5 ], wherein when the thin film is brought into contact with the vapor of the mixed solvent, the temperature of the vapor is 30 ° C. or higher and 40 ° C. or lower. Method.

[ 7 ] The method for manufacturing an organic microdisk array according to any one of [ 3 ] to [ 6 ], wherein the time for contacting the thin film with the vapor of the mixed solvent is 1.5 hours or more.

According to the present invention, an organic microdisk array in which arrays composed of spheres or hemispheres composed of at least one of a pi-conjugated polymer and a photochromic molecule are formed at equal intervals and high density on one surface of a substrate and a method for producing the same. Can be provided.

It is a perspective view which shows one Embodiment of the organic microdisk array of this invention. It is sectional drawing which follows the AA line of FIG. It is sectional drawing which shows 1st Embodiment and 2nd Embodiment of the manufacturing method of the organic microdisk array of this invention. It is sectional drawing which shows 1st Embodiment of the manufacturing method of the organic microdisk array of this invention. It is sectional drawing which shows the 2nd Embodiment of the manufacturing method of the organic microdisk array of this invention. It is an optical microscope image in Experimental Example 1. It is an optical microscope image in Experimental Example 2. It is a scanning electron microscope image in Experimental Example 2. It is an optical microscope image in Experimental Example 3. It is a scanning electron microscope image in Experimental Example 3. It is an optical microscope image in Experimental Example 4. It is a scanning electron microscope image in Experimental Example 5. It is an optical microscope image which shows the light emission of the hemispherical structure in Experimental Example 5. It is a figure which shows the result of having measured the emission spectrum of the hemispherical structure in Experimental Example 5. It is an optical microscope image in Experimental Example 6. It is a figure which shows the result of having measured the emission spectrum of the hemispherical structure in Experimental Example 6. It is an optical microscope image which shows the light emission of the hemispherical structure in Experimental Example 7. It is a figure which shows the result of having measured the emission spectrum of the hemispherical structure in Experimental Example 7. It is an optical microscope image in Experimental Example 8. It is a figure which shows the result of having measured the emission spectrum of the hemispherical structure in Experimental Example 8. It is an optical microscope image in Experimental Example 9. It is a fluorescence microscope image in Experimental Example 9. It is a scanning electron microscopic image in Experimental Example 9. It is a figure which shows the result of having measured the absorption spectrum and the emission spectrum of the hemispherical structure in Experimental Example 9. It is a fluorescence microscope image in Experimental Example 9. It is a fluorescence microscope image in Experimental Example 9.

An embodiment of the organic microdisk array of the present invention and a method for manufacturing the same will be described.
It should be noted that the present embodiment is specifically described in order to better understand the gist of the invention, and is not limited to the present invention unless otherwise specified.

[Organic microdisk array]
The organic microdisk array of the present embodiment has a substrate, a self-assembled monolayer having a solubilized region and a sparsely liquefied region formed on one surface of the substrate, and a parent liquid of the self-assembled monolayer. It comprises a plurality of spherical or hemispherical structures composed of at least one of a pi-conjugated polymer having low crystallinity and a photochromic molecule formed on one surface of a sex region at equal intervals and alternately.

Hereinafter, the organic microdisk array of the present embodiment will be described with reference to FIGS. 1 and 2.
FIG. 1 is a perspective view showing an example of an organic microdisk array of the present embodiment. FIG. 2 is a cross-sectional view taken along the line AA of FIG.
The organic microdisk array 10 of the present embodiment is a self-assembled monolayer having a substrate 20 and a conditioned liquid region 31 and a sparsely liquid region 32 formed alternately on one surface 20a of the substrate 20 at equal intervals. It consists of 30 and at least one of a pi-conjugated polymer having low crystallinity and a photochromic molecule formed on one surface 31a of the self-assembled monolayer 31 and more than the self-assembled monolayer 30. It is roughly composed of a plurality of hemispherical structures 40 projecting on the side opposite to one surface 20a of the substrate 20 (in the thickness direction of the substrate 20).

The self-assembled monolayer 30 is formed as follows.
When the substrate 20 is immersed in a solution containing an organic compound described later, the organic compound is chemically adsorbed on one surface 20a of the substrate 20. Then, in the process of chemisorption, the organic compound is further accumulated at a high density on one surface 20a of the substrate 20 due to the intramolecular interaction, and the orientation of the organic compound is aligned to form the self-assembled monolayer 30. Will be done.

When the self-assembled monolayer 30 is formed, the organic compound forming the self-assembled monolayer 30 is the end opposite to the one side 20a of the substrate 20 (the end not bonded to the one side 20a of the substrate 20). ) Is a molecule having a sparse (hydrophobic) functional group. Examples of the sparse (hydrophobic) functional group include an alkyl group, a phenyl group, and a fluorine group.

The wicking region 31 of the self-assembled monomolecular film 30 is not subjected to the liquefaction treatment described later by removing the sparse functional group of the organic compound by the liquefaction treatment described later (the liquefaction treatment described later). That is, it is a region that is relatively liquid-friendly (hydrophilic) with respect to the sparsely liquor region 32 (in which the sparsely liquid functional group of the organic compound is not removed). Such a lipophilic region 31 is excellent in wettability of a solution containing at least one of a pi-conjugated polymer and a photochromic molecule, which will be described later. Therefore, a hemispherical structure 40 composed of at least one of a pi-conjugated polymer and a photochromic molecule is formed on one surface 31a of the liquid-friendly region 31 by the method for manufacturing an organic microdisk array described later.

As shown in FIG. 1, the liquid-friendly region 31 and the leaching region 32 are formed on one surface 20a of the substrate 20 in the width direction of the substrate 20 (X direction shown in FIG. 1) and the length direction of the substrate 20 (the X direction shown in FIG. 1). It is formed at equal intervals and alternately along the Y direction shown in FIG. In other words, the lyophilized region 31 is a grid-like region formed at equal intervals in the membrane (self-assembled monolayer 30) composed of the hydrophobic region 32.
Therefore, as shown in FIG. 1, the plurality of hemispherical structures 40 are formed on one surface 31a of the positivity regions 31 formed at equal intervals, whereby the plurality of hemispherical structures 40 are formed in the width direction of the substrate 20 (X shown in FIG. 1). It is formed at equal intervals along the direction) and the length direction of the substrate 20 (Y direction shown in FIG. 1).

The width of the liquor region 31 (length in the X direction shown in FIG. 1) W ₁ and the width of the sparse region 32 (length in the X direction shown in FIG. 1) W ₂ are equal. The width W ₁ of the liquor region 31 and the width W ₂ of the sparse region 32 are not particularly limited and are appropriately adjusted according to the intended use of the organic microdisk array 10, but are formed in the liquor region 31. From the viewpoint of constructing a photonic crystal in the visible to near-infrared light region, the hemispherical structure 40 is preferably 1 μm or more and 10 μm or less, and more preferably 2 μm or more and 5 μm or less.

Further, the length L 1 of the lipophilic region 31 (the length in the Y direction shown in FIG. 1) L ₁ and the length L 2 of the sparse liquid region 32 (the length in the Y direction shown in FIG. 1) L ₂ are equal. .. The length L ₁ of the liquor region 31 and the length L ₂ of the sparse region 32 are not particularly limited and are appropriately adjusted according to the use of the organic microdisk array 10 and the like, but the liquor region 31 From the viewpoint of constructing a photonic crystal in the visible to near-infrared light region, the hemispherical structure 40 formed in is preferably 1 μm or more and 10 μm or less, and more preferably 2 μm or more and 5 μm or less.

Further, the width W ₁ of the oleophobic region 31, the width W ₂ of the leaching region 32, the length L ₁ of the wicking region 31 and the length L ₂ of the leaching region 32 are equal to each other. Is preferable. By making all of these lengths equal, the hemispherical structure 40 can be arranged at high density on one surface 20a of the substrate 20.

The diameter of the hemispherical structure 40, that is, the diameter of the circle formed by the interface between the hemispherical structure 40 and the arsenic region 31 (D in FIG. 2) is not particularly limited, and the use of the organic microdisk array 10 is not limited. However, from the viewpoint of constructing a photonic crystal in the visible to near-infrared light region, it is preferably 1 μm or more and 10 μm or less, and more preferably 2 μm or more and 5 μm or less. Since the hemispherical structure 40 is formed in the positivity region 31, the diameter D of the hemispherical structure 40 is the width W1 of the _positivity region 31 and the length L of the positivity region 31. It is ₁ or less.

The height of the hemispherical structure 40, that is, the height to the apex of the hemispherical structure 40 with respect to one surface 31a of the lyophilic region 31 (H in FIG. 2) is not particularly limited, and is an organic microdisk. It is appropriately adjusted according to the application of the array 10, but from the viewpoint of confining visible to near-infrared light, it is preferably 0.5 μm or more and 5 μm or less, and more preferably 1 μm or more and 3 μm or less.

Examples of the substrate 20 include a silicon substrate, a quartz substrate, a glass substrate, a sapphire substrate, a mica substrate, and the like.

The organic compound forming the self-assembled monomolecular film 30 is not particularly limited, but for example, when a quartz or glass substrate is used, a silane coupling agent (hexamethyldisilazane, arylalkylsilane, fluoroalkylsilane, etc.) is used. (Fluorophenylsilane, etc.) and oxides thereof are used, and when a metal substrate is used, an alkylthiol, an alkylphosphonic acid, or the like to which a thiol or phosphonic acid bond site and an alkyl group or the like are bonded is used. These organic compounds have sparse (hydrophobic) functional groups such as alkyl groups, phenyl groups and fluorine groups.

The hemispherical structure 40 is composed of at least one of a pi-conjugated polymer having low crystallinity and a photochromic molecule. That is, the hemispherical structure 40 may be composed of only a pi-conjugated polymer having low crystallinity or only a photochromic molecule, and may be composed of only a pi-conjugated polymer having low crystallinity and a photochromic molecule. It may be composed of. When the hemispherical structure 40 is composed of a pie-conjugated polymer having low crystallinity and a photochromic molecule, the hemispherical structure 40 is a compound in which a photochromic molecule is bound to a pie-conjugated polymer having low crystallinity, or a compound. It is composed of a mixture of pi-conjugated polymer and photochromic molecule with low crystallinity. When the hemispherical structure 40 is composed of a pi-conjugated polymer having low crystallinity and a photochromic molecule, the compounding ratio of each molecule is appropriately adjusted according to the desired characteristics.

In the present embodiment, the pi-conjugated polymer having low crystallinity is a pi-conjugated polymer that forms a spherical structure in a solvent. Since a highly crystalline polymer is anisotropic, crystals also grow heterotropically. Therefore, the highly crystalline polymer does not form a spherical structure. On the other hand, a polymer having low crystallinity is not anisotropic, so that the crystal grows isotropically. Therefore, a polymer having low crystallinity forms a spherical structure (isotropic structure).
As a method for confirming whether or not the pi-conjugated polymer forms a spherical structure in a solvent, the pi-conjugated polymer is dissolved in chloroform or the like, and methanol or the like, which is a highly polar poor solvent, is vapor-diffused. Examples thereof include a method of slowly adding the structure by the method and observing the precipitated structure with an electron microscope or an optical microscope.
Further, the pi-conjugated polymer having low crystallinity has a property of absorbing light in the ultraviolet to near-infrared region and emitting light having a longer wavelength than the absorbed light.

Examples of the pi-conjugated polymer having low crystallinity in the present embodiment include poly [(9,9-dioctylfluorenyl-2,7-dyyl) -alt- (3,3') represented by the following formula (1). , 4,4'-tetramethylbiophene-2,5'-diyl)] (F8TMT2), poly [(N- (2-ethylhexyl) phenothiazine-3,7-diyl) -alt- (3,3', 4,4'-tetramethylbiophene-2,5'-dyyl)] (PTTMT2), poly [(9,9-dioctylfluorenyl-5-octylthieno] expressed by the following formula (3) -C] pyrrole-4,6-dione) (F8TPD), Poly [2-methoxy-5- (3', 7'-dimethyloxyloxy) -1,4-phenylenevinylene] (MDMPPV) represented by the following formula (4). ), Poly [(N-octadecylcarbazol-2,7-diyl) -alt- (3,3', 4,4'-tetramethylbithiophene-2,5'-diyl)] (2) represented by the following formula (5). , 7-CTMT2), poly [(N-octadecylcarbazol-3,6-diyl) -alt- (3,3', 4,4'-tetramethylbiophene-2, 5'-diyl) represented by the following formula (6). )] (3,6-CTMT2), poly [(9,9-dioctylfluorenyl-2,7-dyyl) -alt- (3,4-ethylenedioxythiophene-2,5-dyl) represented by the following formula (7). ] (F8EDOT), poly [(N- (4-octylphenyl) iminoazobeneze-4,4'-diyl)] (AZOANI) represented by the following formula (8), poly [((9)) represented by the following formula (9). 1,4-dioctylphenyl-2,5-diyl) -alt- (3,3', 4,4'-(tetramethylbithiophene-2, 5'-diyl)) (DOPTMT2) and the like can be mentioned.

In the present embodiment, the photochromic molecule is a compound capable of reversibly producing two states having different colors by a photoreaction. For example, when a photochromic molecule is irradiated with light in a certain wavelength range A, the color changes to a color different from that before the light is irradiated, and when light in a wavelength range B different from the wavelength range A is irradiated, the light in the wavelength range A is emitted. It has the property of returning to the color before irradiation. Both states have the same molecular weight and are composed of the same atoms, but their bonding modes are different.

Examples of the photochromic molecule in the present embodiment include diarylethene (derivative group of 1,2-dithienylethene) represented by the following formula (10), azobenzene, spiropyran, hexaarylimidazole derivative and the like.

When the hemispherical structure 40 is composed of only a pi-conjugated polymer having low crystallinity, when the hemispherical structure 40 absorbs light in the ultraviolet to near-infrared region, it has a longer wavelength than the absorbed light. It emits light. Therefore, the organic microdisk array 10 of this embodiment can be used as a light emitting device, a display, or the like.

When the hemispherical structure 40 is composed of only photochromic molecules, when the hemispherical structure 40 is irradiated with light in a certain wavelength range (A), the hemispherical structure 40 is irradiated with light in the wavelength range (A). It changes to a different color than before. Further, when the hemispherical structure 40 is irradiated with light in a wavelength range (B) different from the wavelength range (A), the hemispherical structure 40 returns to the color before irradiation with the light in the wavelength range (A). Therefore, the organic microdisk array 10 of this embodiment can be used as an optical memory device, a display, or the like.

When the hemispherical structure 40 is composed of a pi-conjugated polymer having low crystallinity and a photochromic molecule, when the hemispherical structure 40 is irradiated with light in a certain wavelength range (C), the hemispherical structure 40 becomes It absorbs light in the wavelength range (D) (light in the ultraviolet to near-infrared region) different from that before irradiating the light in the wavelength range (C), and emits light having a longer wavelength than the absorbed light. Further, when the hemispherical structure 40 is irradiated with light in a wavelength range (E) different from the wavelength range (C), the hemispherical structure 40 has the same wavelength range as before the light in the wavelength range (C) is irradiated. It absorbs the light of F) (light in the ultraviolet to near-infrared region) and emits light having a longer wavelength than the absorbed light. Therefore, the organic microdisk array 10 of this embodiment can be used as a light emitting device, a display, an optical memory device, and the like.

According to the present embodiment, since the plurality of hemispherical structures 40 are formed on one surface 31a of the liquid-friendly regions 31 formed at equal intervals, the plurality of hemispherical structures 40 are formed in the width direction of the substrate 20. The organic microdisk array 10 is arranged at equal intervals and at high density along the (X direction shown in FIG. 1) and the length direction (Y direction shown in FIG. 1) of the substrate 20.

In the organic microdisk array 10 of the present embodiment, a plurality of hemispherical structures 40 composed of at least one of a pi-conjugated polymer having low crystallinity and a photonic molecule are arranged at equal intervals and at high density, so that the organic photo It is suitably used as a nick crystal, an optical memory device, a light emitting device, an ultra-high resolution display, and a retinal projection display.

In this embodiment, a case where a plurality of hemispherical structures 40 are formed on one surface 20a of the substrate 20 is illustrated, but the present embodiment is not limited to this. In the present embodiment, a plurality of spherical structures may be formed on one surface 20a of the substrate 20.

Further, in the present embodiment, a case where one hemispherical structure 40 is formed in the positivity region 31 of the self-assembled monolayer 30, but the present embodiment is not limited to this. In the present embodiment, a plurality of hemispherical structures 40 may be formed adjacent to each other in the positivity region 31 according to the size (area) of the positivity region 31.

[Manufacturing method of organic microdisk array]
(First Embodiment)
The method for manufacturing an organic microdisk array of the present embodiment includes a substrate, a self-assembled monomolecular film having a solubilized region and a leached region formed alternately at equal intervals on one surface of the substrate, and self-assembled. A method for producing an organic microdisk array comprising a plurality of spherical structures or hemispherical structures made of at least a pi-conjugated polymer having low crystallinity, which are formed on one surface of a solubilized region of a monomolecular film. Therefore, the step of forming a self-assembled monomolecular film on one surface of the substrate and the self-assembled monomolecular film formed on one surface of the substrate are alternately spaced with a liquor-friendly region and a sparsely liquefied region at equal intervals. The step of forming and one surface of the self-assembled monomolecular film are coated with a solution containing at least a pie-conjugated polymer to form a coating film, and the coating film is dried to consist of at least a pie-conjugated polymer. By contacting the thin film with the vapor of a mixed solvent of chloroform and methanol, a plurality of spheres composed of at least a pi-conjugated polymer are formed on one surface of the arsenic region of the self-assembled monomolecular film. It comprises the steps of forming a structure or a hemispherical structure.

Hereinafter, a method for manufacturing an organic microdisk array according to the present embodiment will be described with reference to FIGS. 3 and 4.
3 and 4 are cross-sectional views showing a method of manufacturing the organic microdisk array of the present embodiment.

The substrate 20 is immersed in a solution containing an organic compound forming the self-assembled monolayer 30 to form the self-assembled monolayer 30 on one surface 20a of the substrate 20 as shown in FIG. 3A. (Self-assembled monolayer formation step).

Examples of the solvent of the solution containing the above organic compound, that is, the solvent for dissolving the organic compound include chloroform, dichloromethane, tetrahydrofuran, toluene, chlorobenzene and the like.
The content (concentration) of the organic compound in the solution containing the organic compound is preferably 0.1 mg / mL or more and 10 mg / mL or less, and more preferably 1 mg / mL or more and 2 mg / mL or less.

As shown in FIG. 3B, the self-assembled monolayer 30 has a sparse functional group at the end opposite to the one side 20a of the substrate 20 (the end not bonded to the one side 20a of the substrate 20). (In FIG. 3 (b), it has a methyl group (CH ₃ )).

Next, as shown in FIGS. 3 (c) and 3 (d), the self-assembled monolayer 30 formed on one surface 20a of the substrate 20 is provided with the lyophilized region 31 and the sparsely liquefied region 32, and the like. It is formed at intervals and alternately (parent liquid / sparse liquid pattern forming step).

In the parent liquid / sparse liquid pattern forming step, as shown in FIG. 3C, the photomask 100 is arranged so as to face the self-assembled monolayer 30 formed on one surface 20a of the substrate 20. The self-assembled monolayer 30 is irradiated with ultraviolet rays α through the photomask 100 to expose the self-assembled monolayer 30.

As the photomask 100, a photomask 100 having a transmitting portion 100a that transmits light in the thickness direction of the photomask 100 is used. The transmission portions 100a are formed at equal intervals along the width direction of the photomask 100 and the length direction of the photomask 100. Further, the transmission portion 100a is opened by one surface 100b and the other surface 100c of the photomask 100. The width W ₃ of the permeation portion 100a is appropriately adjusted according to the width of the target liquid-friendly region 31. Here, in order to simplify the explanation, the width W ₃ of the transmission portion 100a is defined as a width along the width direction of the photomask 100 and a width along the length direction of the photomask 100. In that case, the width W ₃ of the transmissive portion 100a is the width W 1 of the positivity region 31 (the length in the X direction shown in FIG. 1) and the length W ₁ of the positivity region 31 (the Y direction shown in FIG. 1). Length) It is adjusted appropriately according to _L1 . That is, the area of the lyophilized region 31 and the sparsely liable region 32 and the interval at which the lyophilized region 31 and the sparsely liquefied region 32 are provided are not particularly limited, and the hemispherical structure formed in the wicked region 31 is not particularly limited. It is appropriately adjusted according to the size (diameter) and height required for the body 40, the interval at which the hemispherical structure 40 is provided, and the like.

As the ultraviolet ray α, ultraviolet rays having high directivity are used. As such ultraviolet rays, light having an emission intensity in a wavelength range of 150 nm or more and 240 nm or less is used. By using ultraviolet rays having such high directivity, when the self-assembled monolayer 30 formed on one surface 20a of the substrate 20 is irradiated with ultraviolet rays α via the photomask 100, FIG. 3C is shown. As shown in the above, the self-assembled monolayer 30 can be irradiated with ultraviolet rays α along the shape of the transmission portion 100a provided in the photomask 100. As a result, as shown in FIG. 3D, the sparse functional group in the region irradiated with ultraviolet α in the self-assembled monolayer 30 is eliminated, and the desired position of the self-assembled monolayer 30 is obtained. In addition, a lyophilized region 31 that is relatively lyophilic can be formed. Further, the region of the self-assembled monolayer 30 that has not been irradiated with ultraviolet rays α is a sparsely sparse region 32 that is relatively sparse because the sparse functional groups have not disappeared. In this way, the lipophilic region 31 and the sparsely liquid region 32 are formed alternately at equal intervals on the self-assembled monolayer 30 formed on one surface 20a of the substrate 20.

The time for irradiating the self-assembled monolayer 30 formed on one surface 20a of the substrate 20 via the photomask 100 with ultraviolet rays α is preferably 100 seconds or more and 150 seconds or less.

As a means for irradiating the self-assembled monolayer 30 formed on one surface 20a of the substrate 20 with ultraviolet rays having high directivity, for example, an excimer lamp or a vacuum ultraviolet lamp is used.

Next, as shown in FIG. 4A, a solution containing at least a pi-conjugated polymer is applied to one surface 31a of the liquor-friendly region 31 and one surface 32a of the sparsely liquefied region 32, and at least the pi-conjugated system is applied. A thin film 50 made of a polymer is formed (thin film forming step).

Examples of the solvent of the solution containing at least the pi-conjugated polymer, that is, the solvent for dissolving at least the pi-conjugated polymer include chloroform, dichloromethane, tetrahydrofuran, toluene, chlorobenzene and the like.
In this embodiment, the solution for forming the thin film 50 is a solution containing only a pi-conjugated polymer or a solution containing a pi-conjugated polymer and a photochromic molecule.

The content (concentration) of the pi-conjugated polymer or the like in the solution containing at least the pi-conjugated polymer is preferably 0.1 mg / mL or more and 10 mg / mL or less, and 1 mg / mL or more and 2 mg / mL or less. Is more preferable.

In the thin film forming step, first, a solution containing at least a pi-conjugated polymer is applied to one surface 31a of the lipophilic region 31 and one surface 32a of the leaching region 32 to form a coating film composed of this solution.
The method for forming a coating film composed of a solution containing at least a pi-conjugated polymer on one surface 31a of the liquor-friendly region 31 and one surface 32a of the sparsely liquefied region 32 is not particularly limited, but for example, the bar coat method. Ordinary wet coating methods such as a flow coating method, a dip coating method, a spin coating method, a roll coating method, a spray coating method, a meniscus coating method, and a brush coating method are used.

The thickness of the coating film is appropriately adjusted according to the height required for the hemispherical structure 40 or the spherical structure in the final application of the organic microdisk array 10.

In the thin film forming step, the coating film formed on one surface 31a of the liquor-friendly region 31 and the one-sided 32a of the liquefiable region 32 is then dried to form one surface 31a of the liquor-friendly region 31 and the sparse-liquidity region 32. A thin film 50 made of at least a pi-conjugated polymer is formed on one surface 32a.
The temperature at which the coating film is dried is not particularly limited and is appropriately adjusted depending on the type of solvent, but is preferably 30 ° C. or higher and 80 ° C. or lower, for example.
Further, in order to form the hemispherical structure 40 having a uniform size, it is preferable that the thickness of the thin film 50 is uniform.

Next, as shown in FIG. 4B, the thin film 50 formed on one surface 31a of the liquor-friendly region 31 and the one-sided surface 32a of the sparsely liquefied region 32 is brought into contact with the vapor 110 of a mixed solvent of chloroform and methanol. As a result, a hemispherical structure 40 made of at least a pi-conjugated polymer is formed in the lyophilic region 31 (structure formation step). As a result, the organic microdisk array 10 as shown in FIG. 4C is obtained.

In the structure forming step, a solvent vapor annealing (SVA) method is used as a method of contacting the thin film 50 with the vapor 110 of a mixed solvent of chloroform and methanol.
When the thin film 50 is brought into contact with the steam 110 by the SVA method, the thin film 50 is placed on one surface 31a of the liquor-friendly region 31 and one surface 32a of the leaching region 32 in a closed container such as a reagent bottle containing a mixed solvent. Places the substrate 20 on which the

The mixing ratio of chloroform and methanol in the mixed solvent of chloroform and methanol is preferably 1: 0.5 to 1: 1 in volume ratio, and more preferably 1: 1.
When the blending ratio of chloroform and methanol is less than 1: 0.5 by volume, an amorphous protruding structure made of at least a pi-conjugated polymer is formed, or the thin film 50 does not change at all. On the other hand, if the mixing ratio of chloroform and methanol exceeds 1: 1 by volume, the thin film 50 is dissolved in chloroform and the thin film 50 is destroyed.

After that, a closed container containing the substrate 20 on which the thin film 50 is formed is placed in a constant temperature bath, and the closed container is allowed to stand at a predetermined temperature for a predetermined time.
The temperature in the constant temperature bath, that is, the temperature of the steam 110 when the thin film 50 is brought into contact with the steam 110 is preferably 30 ° C. or higher and 40 ° C. or lower, and more preferably 30 ° C. or higher and 35 ° C. or lower.
If the temperature of the steam 110 is less than 30 ° C., the hemispherical structure 40 cannot be formed. On the other hand, there is no difference in the effect even if the temperature of the steam 110 exceeds 40 ° C.

The time for contacting the thin film 50 with the steam 110 is preferably 1.5 hours or more.
If the time for contacting the thin film 50 with the vapor 110 is less than 1.5 hours, the hemispherical structure 40 cannot be formed on one surface 30a of the liquid-friendly region 31.

When the thin film 50 is brought into contact with the steam 110 of a mixed solvent of chloroform and methanol by the SVA method, the pi-conjugated polymer forming the thin film 50 is gradually dissolved in chloroform constituting the mixed solvent, and in chloroform, The pi-conjugated polymers gather. Here, since the pi-conjugated polymer has high hydrophobicity, when highly polar (hydrophilic) methanol approaches the pi-conjugated polymer, the pi-conjugated polymer does not want to come into contact with methanol, so the surface area is increased. It is made smaller to form the hemispherical structure 40.
If the contact between the thin film 50 and the steam 110 is stopped, the above-mentioned action does not occur, so that the formation of the hemispherical structure 40 is also stopped.

According to the method for manufacturing an organic microdisk array of the present embodiment, a plurality of hemispherical structures 40 are arranged at equal intervals and at high density along the width direction of the substrate 20 and the length direction of the substrate 20. The disk array 10 is obtained.

(Second embodiment)
The method for manufacturing an organic microdisk array according to the present embodiment includes a substrate, a self-assembled monolayer having lyophilic regions and leached regions formed alternately at equal intervals on one surface of the substrate, and self-assembled monolayer. A method for manufacturing an organic microdisk array comprising a plurality of spherical structures or hemispherical structures composed of photochromic molecules formed on one surface of a self-assembled monolayer, wherein the organic microdisk array is formed on one surface of a substrate. A step of forming a self-assembled monolayer, a step of forming lyophilic regions and sparsely liquefied regions at equal intervals and alternately on the self-assembled monolayer formed on one surface of the substrate, and self-assembly. The process of applying a solution containing photochromic molecules to one surface of the monolayer to form a coating film consisting of the solution, and drying the coating film to apply photochromic to one surface of the self-assembled monolayer. It comprises a step of forming a plurality of spherical structures or hemispherical structures composed of molecules.

Hereinafter, a method for manufacturing an organic microdisk array according to the present embodiment will be described with reference to FIGS. 3 and 5.
3 and 5 are cross-sectional views showing a method of manufacturing the organic microdisk array of the present embodiment.

Similar to the first embodiment, as shown in FIGS. 3A and 3B, a self-assembled monolayer 30 is formed on one surface 20a of the substrate 20 (self-assembled monolayer formation). Process).

Next, in the same manner as in the first embodiment, as shown in FIGS. 3 (c) and 3 (d), the self-assembled monolayer 30 formed on one surface 20a of the substrate 20 is liable to be liquid-friendly. Regions 31 and sparsely liquor regions 32 are formed at equal intervals and alternately (parent liquid / sparse liquid pattern forming step).

Next, as shown in FIG. 5 (a), a solution containing a photochromic molecule is applied to one surface 31a of the lipophilic region 31 and one surface 32a of the sparsely liquefied region 32 to form a coating film 60 composed of the solutions. (Coating film forming step).

Examples of the solvent of the solution containing the photochromic molecule, that is, the solvent for dissolving the photochromic molecule include chloroform, dichloromethane, tetrahydrofuran, toluene, chlorobenzene and the like.

The content (concentration) of the photochromic molecule in the solution containing the photochromic molecule is preferably 0.1 mg / mL or more and 10 mg / mL or less, and preferably 1.0 mg / mL or more and 2.0 mg / mL or less. More preferred.

The method for forming the coating film 60 composed of a solution containing photochromic molecules on one surface 31a of the liquor-friendly region 31 and one surface 32a of the sparsely liquefied region 32 is not particularly limited, and is, for example, a bar coating method or a flow coating method. , Dip coat method, spin coat method, roll coat method, spray coat method, meniscus coat method, brush coating method, etc., ordinary wet coat methods are used.

The thickness of the coating film 60 is appropriately adjusted according to the height required for the hemispherical structure 40 or the spherical structure in the final application of the organic microdisk array 10.

Next, as shown in FIG. 5 (b), the self-assembled monolayer 30 is formed by drying the coating film 60 formed on one surface 31a of the lipophilic region 31 and one surface 32a of the sparsely liquefied region 32. A hemispherical structure 40 made of photochromic molecules is formed on one surface 31a of the liquor-friendly region 31 (structure forming step). As a result, the organic microdisk array 10 as shown in FIG. 5C is obtained.

In the structure forming step, the temperature at which the coating film 60 is dried is not particularly limited and is appropriately adjusted depending on the type of solvent, but is preferably 30 ° C. or higher and 80 ° C. or lower, for example. In the structure forming step, by drying the coating film 60, the solution containing the photochromic molecules forming the coating film 60 moves to one surface 31a of the lyophilized region 31, and finally the photochromic molecules become a hemispherical structure. Form 40.
Further, in order to form the hemispherical structure 40 having a uniform size, it is preferable that the thickness of the coating film 60 is uniform.

According to the method for manufacturing an organic microdisk array of the present embodiment, a plurality of hemispherical structures 40 are arranged at equal intervals and at high density along the width direction of the substrate 20 and the length direction of the substrate 20. The disk array 10 is obtained.

In the method for manufacturing an organic microdisk array of the present embodiment, the case where the hemispherical structure 40 is formed on one surface 31a of the liquid-friendly region 31 is exemplified, but the present invention is not limited thereto. In the method for producing an organic microdisk array of the present invention, the place where the photochromic molecules gather is determined by adjusting the type of solvent for dissolving the photochromic molecules, the concentration of the photochromic molecules in the solution containing the photochromic molecules, and the like. It can be controlled to control the position where the hemispherical structure is formed.

Hereinafter, the present invention will be described in more detail with reference to experimental examples, but the present invention is not limited to the following experimental examples.

[Experimental Example 1]
A silicon substrate having a thickness of 0.5 μm was cut into a size of 10 mm in length × 10 mm in width to obtain a test substrate.
The test substrate was washed for 10 minutes by UV ozone washing.
Then, the test substrate was allowed to stand at 50 ° C. for 30 minutes in a mixed solution of sulfuric acid (H ₂ SO ₄ ) and hydrogen peroxide (H ₂ O ₂ ). The mixing ratio of sulfuric acid and hydrogen peroxide in the mixture was set to 4: 1 by volume.
After that, the test substrate was washed with pure water, and the cleaning of the test substrate was completed.
F8TMT2, a pi-conjugated polymer, was dissolved in chloroform to prepare an F8TMT2 solution. The content (concentration) of F8TMT2 in this solution was set to 1 mg / mL.
Next, the test substrate was placed on the spin coater, and 10 μL to 50 μL of the F8TMT2 solution was dropped onto the test substrate while rotating the test substrate at 1500 rpm for 10 seconds and then at 3000 rpm for 40 seconds. A coating film consisting of this solution was formed.
Then, the coating film was dried at room temperature to form a thin film made of F8TMT2 on one surface of the test substrate.
Next, the test substrate on which the thin film was formed was cut out into a size of 5 mm in length × 5 mm in width.
The test substrate on which the thin film was formed was then placed in a 50 mL reagent bottle containing chloroform.
Next, a reagent bottle containing the test substrate on which the thin film was formed was placed in a constant temperature bath, and the reagent bottle was allowed to stand at 30 ° C. for 4 hours. As a result, the thin film formed on one surface of the test substrate was brought into contact with the vapor of chloroform.
The test substrate was then vacuum dried.
Then, the test substrate after vacuum drying was observed with an optical microscope. The optical microscope image is shown in FIG.
From the scanning electron microscope image of FIG. 6, it was confirmed that the hemispherical structure made of F8TMT2 was not formed on the test substrate.

[Experimental Example 2]
In the same manner as in Experimental Example 1, a thin film made of F8TMT2 was formed on one surface of the test substrate.
Next, the test substrate on which the thin film was formed was cut out into a size of 5 mm in length × 5 mm in width.
Next, the test substrate on which the thin film made of F8TMT2 was formed was placed in a 50 mL reagent bottle containing a mixed solvent of chloroform and methanol.
The mixing ratio of chloroform and methanol in the mixed solvent of chloroform and methanol was set to 1: 0.5 by volume.
Then, in the same manner as in Experimental Example 1, the thin film formed on one surface of the test substrate was brought into contact with the vapor of a mixed solvent of chloroform and methanol.
The test substrate was then vacuum dried.
The test substrate after vacuum drying was then observed with an optical microscope and a scanning electron microscope (SEM). The optical microscope is shown in FIG. Further, a scanning electron microscope image is shown in FIG.
From the optical microscope of FIG. 7 and the scanning electron microscope image of FIG. 8, it was confirmed that a hemispherical structure made of F8TMT2 was formed on the test substrate. Further, when viewed in a plan view, the hemispherical structure was a circle having a diameter of 2 μm or more and 6 μm or less.

[Experimental Example 3]
In the same manner as in Experimental Example 1, a thin film made of F8TMT2 was formed on one surface of the test substrate.
Next, the test substrate on which the thin film was formed was cut out into a size of 5 mm in length × 5 mm in width.
Next, the thin film formed on one surface of the test substrate was formed in the same manner as in Experimental Example 1 except that the mixing ratio of chloroform and methanol in the mixed solvent of chloroform and methanol was 1: 1. It was contacted with the vapor of a mixed solvent of chloroform and methanol.
The test substrate was then vacuum dried.
Then, the test substrate after vacuum drying was observed with an optical microscope and a scanning electron microscope. The optical microscope is shown in FIG. Further, a scanning electron microscope image is shown in FIG.
From the optical microscope of FIG. 9 and the scanning electron microscope image of FIG. 10, it was confirmed that a hemispherical structure made of F8TMT2 was formed on the test substrate. Further, when viewed in a plan view, the hemispherical structure was a circle having a diameter of 1 μm or more and 4 μm or less.

[Experimental Example 4]
In the same manner as in Experimental Example 1, a thin film made of F8TMT2 was formed on one surface of the test substrate.
Next, the test substrate on which the thin film was formed was cut out into a size of 5 mm in length × 5 mm in width.
Next, the thin film formed on one surface of the test substrate was formed in the same manner as in Experimental Example 1 except that the mixing ratio of chloroform and methanol in the mixed solvent of chloroform and methanol was 1: 2. It was contacted with the vapor of a mixed solvent of chloroform and methanol.
The test substrate was then vacuum dried.
Next, the test substrate after vacuum drying was observed with an optical microscope image. The optical microscope image is shown in FIG.
From the optical microscope image image of FIG. 11, it was confirmed that the hemispherical structure made of F8TMT2 was not formed on the test substrate.

[Experimental Example 5]
A silicon substrate having a thickness of 0.5 μm was cut into a size of 10 mm in length × 10 mm in width to obtain a test substrate.
The test substrate was washed for 10 minutes by UV ozone washing.
Then, the test substrate was allowed to stand at 50 ° C. for 30 minutes in a mixed solution of sulfuric acid (H ₂ SO ₄ ) and hydrogen peroxide (H ₂ O ₂ ). The mixing ratio of sulfuric acid and hydrogen peroxide in the mixture was set to 4: 1 by volume.
After that, the test substrate was washed with pure water, and the cleaning of the test substrate was completed.
Hexamethyldisilazane (HMDS) was dissolved in chloroform to prepare an HMDS solution. The content (concentration) of HMDS in this solution was set to 2 mg / mL.
Then, the washed test substrate was immersed in the HMDS solution for 24 hours to form a self-assembled monolayer on one surface of the test substrate.
Next, a photomask is placed so as to face the self-assembled monolayer formed on one surface of the test substrate, and the self-assembled monolayer is irradiated with ultraviolet rays via the photomask to self-assemble. The monolayer was exposed.
As the photomask, a photomask in which a plurality of transmissive portions were formed at equal intervals on the entire surface thereof was used. The width of the transmissive portion along the width direction of the photomask and the width along the length direction of the photomask were set to 2 μm. Further, the distance between the transmissive portions was set to 2 μm.
The ultraviolet rays irradiating the self-assembled monolayer had a peak emission wavelength of 200 nm and a half width of the peak emission wavelength of 10 nm.
Further, the time for irradiating the self-assembled monolayer with ultraviolet rays was set to 130 seconds, and the period for irradiating the self-assembled monolayer with ultraviolet rays was set to 151 Hz.
F8TMT2, a pi-conjugated polymer, was dissolved in chloroform to prepare an F8TMT2 solution. The content (concentration) of F8TMT2 in this solution was set to 1 mg / mL.
Next, the test substrate on which the self-assembled monolayer was formed was placed on the spin coater, and the test substrate was rotated at 1500 rpm for 10 seconds and then at 3000 rpm for 40 seconds on the test substrate. 10 μL to 50 μL of the F8TMT2 solution was added dropwise to form a coating film composed of this solution.
Then, the coating film was dried at room temperature to form a thin film made of F8TMT2 on the self-assembled monolayer formed on one surface of the test substrate.
Next, the test substrate on which the thin film was formed was cut out into a size of 5 mm in length × 5 mm in width.
The test substrate on which the thin film was formed was then placed in a 50 mL reagent bottle containing a mixed solvent of chloroform and methanol.
The mixing ratio of chloroform and methanol in the mixed solvent of chloroform and methanol was set to 1: 1 by volume.
Next, a reagent bottle containing the test substrate on which the thin film was formed was placed in a constant temperature bath, and the reagent bottle was allowed to stand at 30 ° C. for 4 hours. As a result, the thin film formed on one surface of the test substrate was brought into contact with the vapor of the mixed solvent of chloroform and methanol.
The test substrate was then vacuum dried.
Next, the test substrate after vacuum drying is observed with a scanning electron microscope, and the scanning electron microscope image is shown in FIG.
From the scanning electron microscope image of FIG. 12, a hemispherical structure made of F8TMT2 is formed on a region (parental liquid region) exposed to ultraviolet rays in a self-assembled monolayer formed on one surface of a test substrate. It was confirmed that it was formed.
Further, when the hemispherical structure made of F8TMT2 formed on the test substrate was irradiated with light having a wavelength of 400 nm, it was confirmed that the hemispherical structure emitted light (FIG. 13). The emission spectrum of the hemispherical structure was measured by exciting the hemispherical structure with a laser focused by a microscope lens of an optical microscope. The emission spectrum of the hemispherical structure is shown in FIG.
From the results of FIG. 14, it was confirmed that the hemispherical structure absorbs light having a wavelength of 400 nm and emits light having a wavelength of 470 nm, which is longer than the absorbed light.

[Experimental Example 6]
Similar to Experimental Example 5 except that PTTMT2 was used as the pi-conjugated polymer, the region exposed to ultraviolet rays in the self-assembled monolayer formed on one surface of the test substrate (parental liquid region). ), A thin film made of PTTMT2 was formed.
Then, in the same manner as in Experimental Example 5, the thin film formed on one surface of the test substrate was brought into contact with the vapor of a mixed solvent of chloroform and methanol.
The test substrate was then vacuum dried.
Next, the test substrate after vacuum drying is observed with an optical microscope, and the optical microscope image thereof is shown in FIG.
From the optical microscope image of FIG. 15, a hemispherical structure made of PTTMT2 is formed on a region (parental liquid region) exposed to ultraviolet rays in the self-assembled monolayer formed on one surface of the test substrate. It was confirmed that
Moreover, the emission spectrum of the hemispherical structure was measured in the same manner as in Experimental Example 5. The emission spectrum of the hemispherical structure is shown in FIG.
As a result, it was confirmed that the hemispherical structure absorbs light having a wavelength of 400 nm and emits light having a wavelength of 470 nm, which is longer than the absorbed light.

[Experimental Example 7]
Similar to Experimental Example 5 except that F8TPD was used as the pi-conjugated polymer, the region exposed to ultraviolet rays in the self-assembled monolayer formed on one surface of the test substrate (parental liquid region). ), A thin film made of F8TPD was formed.
Then, in the same manner as in Experimental Example 5, the thin film formed on one surface of the test substrate was brought into contact with the vapor of a mixed solvent of chloroform and methanol.
The test substrate was then vacuum dried.
Next, the test substrate after vacuum drying is observed with an optical microscope, and the optical microscope image thereof is shown in FIG.
From the optical microscope image of FIG. 17, a hemispherical structure made of F8TPD is formed on a region (parental liquid region) exposed to ultraviolet rays in the self-assembled monolayer formed on one surface of the test substrate. It was confirmed that
Moreover, the emission spectrum of the hemispherical structure was measured in the same manner as in Experimental Example 5. The emission spectrum of the hemispherical structure is shown in FIG.
As a result, it was confirmed that the hemispherical structure absorbs light having a wavelength of 400 nm and emits light having a wavelength of 530 nm, which is longer than the absorbed light.

[Experimental Example 8]
A thin film made of MDMOPPV was formed on the self-assembled monolayer formed on one surface of the test substrate in the same manner as in Experimental Example 5 except that MDMOPPV was used as the pi-conjugated polymer.
Then, in the same manner as in Experimental Example 5, the thin film formed on one surface of the test substrate was brought into contact with the vapor of a mixed solvent of chloroform and methanol.
The test substrate was then vacuum dried.
Next, the test substrate after vacuum drying is observed with an optical microscope, and the optical microscope image thereof is shown in FIG.
From the optical microscope image of FIG. 19, a hemispherical structure made of MDMOPPV is formed on a region (parental liquid region) exposed to ultraviolet rays in a self-assembled monolayer formed on one surface of a test substrate. It was confirmed that
Further, when the hemispherical structure made of MDMOPPV formed on the test substrate was irradiated with light having a wavelength of 400 nm, it was confirmed that the hemispherical structure emitted light.
Moreover, the emission spectrum of the hemispherical structure was measured in the same manner as in Experimental Example 5. The emission spectrum of the hemispherical structure is shown in FIG.
From the results of FIG. 20, it was confirmed that the hemispherical structure absorbs light having a wavelength of 400 nm and emits light having a wavelength of 600 nm longer than the absorbed light.

[Experimental Example 9]
In the same manner as in Experimental Example 5, a self-assembled monolayer was formed on one surface of the test substrate, and the self-assembled monolayer was exposed.
The photochromic molecule diarylethene was dissolved in chloroform to prepare a diarylethene solution. The content (concentration) of diarylethene in this solution was 1.5 mg / mL.
Then, 10 μL to 30 μL of the diarylethene solution was directly dropped onto the test substrate on which the self-assembled monolayer was formed, and the test substrate was vacuum-dried.
Next, the test substrate after vacuum drying is observed with an optical microscope, and the optical microscope is shown in FIG. Further, when a hemispherical structure made of diarylethene formed on a test substrate is irradiated with light having a wavelength of 450 nm to 490 nm, it is observed with a fluorescence microscope, and the fluorescence microscope image is shown in FIG. 22. Further, the test substrate after vacuum drying is observed with a scanning electron microscope, and the scanning electron microscope image is shown in FIG. 23.
From the optical microscope image of FIG. 21, the fluorescence microscope image of FIG. 22, and the scanning electron microscope image of FIG. 23, the region exposed to ultraviolet rays in the self-assembled monolayer formed on one surface of the test substrate (parent liquid). It was confirmed that a hemispherical structure composed of diarylethene was formed on the sex region).
Further, when the hemispherical structure made of diarylethene formed on the test substrate was irradiated with light having a wavelength of 450 nm to 490 nm for 60 minutes, the hemispherical structure gradually darkened, so that quenching was confirmed.
Further, in the same manner as in Experimental Example 5, when the hemispherical structure made of diarylethene formed on the test substrate is irradiated with light having a wavelength of 450 nm to 490 nm, the absorption spectrum and the emission spectrum of the hemispherical structure are obtained. The measurement results are shown in FIG. In FIG. 24, the alternate long and short dash line shows the absorption spectrum of the diarylethene in the open ring state, the broken line shows the absorption spectrum of the diarylethene in the closed ring state, and the solid line shows the emission spectrum of the diarylethene in the closed ring state.
From the results shown in FIG. 24, it was confirmed that the hemispherical structure absorbs light having a wavelength of 450 nm and emits light having a wavelength of 530 nm, which is longer than the absorbed light.
Further, when the blackened hemispherical structure was irradiated with light having a wavelength of 350 nm to 390 nm for 1 minute, it was confirmed that the hemispherical structure was emitting light.
FIG. 25 shows a fluorescence microscope image when the hemispherical structure is irradiated with light having a wavelength of 450 nm to 490 nm (FIG. 25 (a)), and a fluorescence microscope image of the blackened hemispherical structure (FIG. 25 (b)). The fluorescence microscope image (FIG. 25 (c)) when the hemispherical structure is irradiated with light having a wavelength of 350 nm to 390 nm is shown.
Further, as shown in FIG. 26, among the hemispherical structures made of diarylethene formed on the test substrate, when the hemispherical structure at a predetermined position is irradiated with light having a wavelength of 355 nm, the hemispherical structure irradiated with light is irradiated. Only the structure can emit light. After that, the light emitting hemispherical structure can be extinguished by irradiating it with light having a wavelength of 450 nm to 490 nm. 26 (a) is a fluorescence microscope image of the hemispherical structure before irradiation with light, and FIG. 26 (b) is a fluorescence microscope image of the hemispherical structure when light with a wavelength of 355 nm is irradiated, FIG. 26 (b). c) is a fluorescence microscope image of the hemispherical structure after irradiation with light having a wavelength of 450 nm to 490 nm.

The organic microdisk array of the present invention can be used as an organic photonic crystal because a plurality of hemispherical structures consisting of at least one of a pi-conjugated polymer having low crystallinity and a photochromic molecule are arranged at equal intervals and at high density. It can be applied to applications such as, as an optical memory device, as a light emitting device, as an ultra-high resolution display, as a retinal projection display, and the like.

10 ... Organic microdisk array, 20 ... Substrate, 30 ... Self-assembled monolayer, 31 ... Hydrophilic region, 32 ... Leaky region, 40 ... Hemispherical Structure, 50 ... thin film, 60 ... coating film, 100 ... photomask, 110 ... steam.

Claims (7)

On one surface of the substrate, a self-assembled monolayer having lyophilic regions and sparsely formed regions formed at equal intervals and alternately on one surface of the substrate, and on one surface of the self-assembled monolayer. A plurality of spherical or hemispherical structures made of at least a pie-conjugated polymer having low crystallinity formed .
The py-conjugated polymer is poly [(9,9-dioctylfluoreneyl-5-octylthiono [3,4-c] pyrrole-4,6-dione)), Poly [2-methoxy-5 (3', 7'). -Dimethyloctyloxy) -1,4-phenylene vinylene], which is an organic microdisk array. The organic microdisk array according to claim 1, wherein the plurality of spherical structures or hemispherical structures are composed of the pi-conjugated polymer having low crystallinity and a photochromic molecule. On one surface of the substrate, a self-assembled monolayer having lyophilic regions and sparsely formed regions formed at equal intervals and alternately on one surface of the substrate, and on one surface of the self-assembled monolayer. A method for producing an organic microdisk array comprising a plurality of spherical structures or hemispherical structures formed of at least a pie-conjugated polymer having low crystallinity.
A step of forming the self-assembled monolayer on one surface of the substrate,
A step of forming the wicking region and the leaching region alternately at equal intervals on the self-assembled monolayer formed on one surface of the substrate.
A solution containing at least the pi-conjugated polymer is applied to one surface of the self-assembled monolayer to form a coating film, and the coating film is dried to form a thin film composed of at least the pi-conjugated polymer. The process of forming and
By contacting the thin film with the vapor of a mixed solvent of chloroform and methanol, a plurality of spherical structures or hemispheres composed of at least the pi-conjugated polymer are placed on one surface of the arsenic region of the self-assembled monolayer. It has a step of forming a shaped structure and
The py-conjugated polymer is poly [(9,9-dioctylfluorenyl-5-octylthiono [3,4-c] pyrrole-4,6-dione)), Poly [2-methoxy-5 (3', 7'). -A method for manufacturing an organic microdisk array, characterized in that it is (dimethyloctyloxy) -1,4-phenylenevinylene] . The method for producing an organic microdisk array according to claim 3 , wherein the solution contains a photochromic molecule. The method for producing an organic microdisk array according to claim 3 or 4 , wherein the blending ratio of chloroform and methanol in the mixed solvent is 1: 0.5 to 1: 1 in volume ratio. The organic microdisk array according to any one of claims 3 to 5 , wherein when the thin film is brought into contact with the vapor of the mixed solvent, the temperature of the vapor is 30 ° C. or higher and 40 ° C. or lower. Manufacturing method. The method for manufacturing an organic microdisk array according to any one of claims 3 to 6 , wherein the time for contacting the thin film with the vapor of the mixed solvent is 1.5 hours or more .

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