JP3748541B2 - Method for producing mesostructured body - Google Patents

Description

[0001]
BACKGROUND OF THE INVENTION
The present invention relates to a method for producing a mesostructured body.
[0002]
[Prior art]
In the last 10 years or so, research on porous materials having mesochannels (2 to several tens of nanometer diameter channels) from which organic-inorganic mesostructures or organic substances have been removed has progressed greatly. Inorganic materials having a mesochannel structure synthesized by a sol-gel method using a surfactant aggregate as a template have attracted attention for applications such as reaction catalysts, separation, and low dielectric constant materials.
[0003]
However, most of these can be obtained in the form of a powder, and there are few known methods for forming a film by arbitrarily aligning the directions of the mesochannels, so that advanced use is limited.
[0004]
Method of aligning with strong magnetic field (Reference 1), micro contact printing method (Reference 2), or on rubbing polymer film (Reference 3) or orientation Langmuir-Blodgett film (Reference 4) In addition, there are known methods for orienting by preparing an organic-inorganic mesostructure, but these can be oriented over the entire film, but only the intended portion cannot be oriented in any direction.
[0005]
[Problems to be solved by the invention]
The present inventors have already applied polarized light onto an azobenzene monomolecular film on a substrate, produced an oriented polysilane film thereon, and succeeded in orientation and photopatterning of the target silica-based mesostructure. (Reference 5). However, since this method takes time, creation of a simple method is strongly desired.
[0006]
The present inventors have developed a technique for creating a relief structure on the surface of a polymer film by light (Japanese Patent Application No. 2001-282217) or orienting the main chain direction of a polymer film using polarized light. However, it is unclear whether the mesochannel tissue orientation can be easily controlled using these methods.
[0007]
If the organic-inorganic mesostructured thin film can be oriented by light, it is possible to prepare a locally oriented or patterned oriented film. It is desired to realize the patterning of the orientation and morphological structure of the mesoporous material excluding the organic-inorganic mesostructured film and the organic mold by light.
[0008]
This invention is made | formed in view of such a subject, and it aims at providing the novel manufacturing method of a mesostructure.
[0009]
[Means for Solving the Problems]
The method for producing a mesostructured body of the present invention comprises forming a polymer film on a substrate, irradiating the film with ultraviolet light, irradiating the film with visible light, and applying a mixed solution of a surfactant and a silane compound. In this method, a film is immersed in a mixed solution to form a deposit on the film. As a result, the mesostructure is deposited and grown at the same period as the relief structure under the influence of the relief structure formed on the film.
[0010]
The method for producing a mesostructured body of the present invention comprises forming a polymer film on a substrate, irradiating the film with ultraviolet light, and then irradiating the film with visible light through a photomask, and the surfactant and the silane compound. In this method, a mixed solution is prepared, and a film is immersed in the mixed solution to form a deposit on the film. Accordingly, as described above, the mesostructured body is deposited and grown at the same cycle as the relief structure under the influence of the relief structure formed on the film.
[0011]
The method for producing a mesostructured body of the present invention comprises forming a polysilane film on a substrate, irradiating the film with ultraviolet polarized light, preparing a mixed solution of a surfactant and a silane compound, and immersing the film in the mixed solution. This is a method for forming a deposit on the film. Accordingly, as described above, the mesostructured body is deposited and grown at the same cycle as the relief structure under the influence of the relief structure formed on the film.
[0012]
DETAILED DESCRIPTION OF THE INVENTION
Hereinafter, an embodiment of the invention according to a method for producing a mesostructure will be described.
In this Embodiment, the following three methods are used about the manufacturing method of a mesostructure.
[0013]
Initially, the 1st manufacturing method of a mesostructure is demonstrated.
A surface relief structure is easily produced with light, and the surface irregularities are utilized, and an inorganic material centering on silica is produced and deposited on the surface using a surfactant organic structure as a template, and is oriented by depositing it. Organic-inorganic mesostructures having mesochannels were prepared. The relief structure is made with the interfered argon ion laser light. After the production, the organic substance is removed by a photo-ozone treatment to obtain an oriented mesoporous material.
[0014]
The first method for producing a mesostructure is specifically described.
First, a polymer film is formed on a substrate.
[0015]
As the substrate, a substrate made of quartz can be used. However, the substrate is not limited to this quartz substrate. In addition, a substrate made of a general glass plate, a transparent crystal plate such as sodium fluoride, or a transparent polymer film such as polystyrene or polymethyl methacrylate can be employed.
[0016]
As a method of forming a polymer film on a substrate, for example, a method of forming a spin cast film, that is, a method of forming a thin film on a substrate by dropping a polymer organic solvent solution onto the substrate and rotating the substrate at a high speed Can be adopted. The method for forming the polymer film on the substrate is not limited to this method. In addition, it is possible to adopt a method such as thin film production by spraying and pulling up in a concentrated solution or spray coating.
[0017]
As the polymer, for example, poly {(ω-hydroxyoligo (ethylene oxide) -α-methacrylate-co-11- [4-[(4-hexylphenyl) azo] phenoxy] undecanoyl methacrylate)} can be used.
[0018]
However, the polymer is not limited to this. Other polymers include poly {(ω-hydroxyoligo (ethylene oxide))-α-methacrylate-co-11- [4-[(4-alkylphenyl) azo] phenoxy] alkanoyl methacrylate}, or poly {(ω- Adopt methacrylate-based or acrylate-based polymers such as hydroxy oligo (ethylene oxide))-α-acrylate-co-11- [4-[(4-alkylphenyl) azo] phenoxy] alkanoyl acrylate} or copolymers thereof Can do.
[0019]
The molecular weight of the polymer is preferably in the range of 10,000 to 1,000,000 in terms of weight average molecular weight. This is because when the weight average molecular weight is within this range, photorelief formation is effectively performed and sufficient form stability is provided.
[0020]
As a method of adjusting the thickness of the polymer film, for example, there is a method of changing the polymer concentration in the organic solvent at the time of producing the spin cast film. Other methods for adjusting the film thickness of the polymer include the number of revolutions during spin casting and a method of changing the evaporation rate by mixing a high boiling point solvent such as toluene with the solvent.
[0021]
The film thickness of the polymer is preferably in the range of 20 to 1,000 nm. This is because when the film thickness of the polymer is within this range, there is an advantage that a sufficiently large relief structure can be formed by light irradiation.
[0022]
After the spin cast film is formed on the substrate, the film is annealed.
It is preferable that the temperature of annealing exists in the range of 40-100 degreeC. This is because if the temperature is within this range, the solvent can be sufficiently evaporated.
[0023]
The annealing time is preferably in the range of 1 to 120 minutes. This is because if the time is within this range, the solvent can be sufficiently evaporated.
[0024]
Next, the polymer film formed on the substrate is irradiated with ultraviolet light.
The wavelength of the ultraviolet light is preferably in the range of 320 to 400 nm. This is because, when the wavelength is within this range, there is an advantage that azobenzene can be converted from the trans form to the cis form.
[0025]
The exposure amount of ultraviolet light is 0.05-10 Jcm ^-2 It is preferable that it exists in the range. This is because when the exposure dose is within this range, there is an advantage that photoisomerization from trans to cis can sufficiently proceed and photodegradation of azobenzene can be suppressed.
[0026]
Here, the reason for irradiating the polymer film formed on the substrate with ultraviolet light is that, when the relief structure is formed into a film by utilizing the optical mass transfer phenomenon, azobenzene is given in advance to give a flexible and fluid film. This is because it is necessary to keep the body and to be sensitive to the blue laser light, which is the next operation.
[0027]
Next, the polymer film irradiated with ultraviolet light is irradiated with blue laser light that has been interfered.
The wavelength of the laser light is preferably in the range of 400 to 550 nm. This is because when the wavelength is within this range, there is an advantage that cis-azobenzene is exposed to light.
[0028]
As a method for causing the laser beam to interfere, a method for causing the laser beam to interfere with the reflected light of the laser beam can be used. However, the method of causing the laser beam to interfere is not limited to this method. In addition, it is possible to employ a method of mixing the light into two beams after the beam is split by a beam splitter and causing interference.
[0029]
Laser light irradiation intensity is 5-100mWcm ^-2 It is preferable that it exists in the range. This is because when the irradiation light intensity is within this range, there is an advantage that a relief structure can be formed by inducing mass transfer.
[0030]
The exposure time of the laser light is preferably in the range of 0.5 to 60 seconds. This is because when the exposure time is within this range, there is an advantage that a relief structure is formed.
[0031]
By irradiating the interfered blue laser light to the polymer film irradiated with ultraviolet light, a relief structure can be produced on the polymer surface. This is because trans- and cis-patterns of azobenzene are formed in the film, and mass transfer starts from the imbalance.
[0032]
Next, a mixed solution of a surfactant and a silane compound is prepared.
For example, cetyltrimethylammonium chloride can be used as the surfactant. However, the surfactant is not limited to this. In addition, as the surfactant, an ammonium surfactant such as trimethylammonium halide having 12 to 20 carbon atoms can be employed.
[0033]
In addition, as the surfactant, nonionic surfactants such as alkylethylene oxides and block copolymers of ethylene oxide and propylene oxide can be employed.
[0034]
As the silane compound, for example, tetraethoxysilane can be used. However, the silane compound is not limited to this. As the silane compound, a silica-based glass condensation precursor such as tetraalkoxysilane having 1 to 4 carbon atoms can be used.
[0035]
Next, the film on which the relief is formed by irradiating the interfered blue laser light is immersed in the mixed solution to form a silica surfactant hybrid deposit on the film.
[0036]
The temperature immersed in the mixed solution is preferably in the range of 10 to 90 ° C. This is because when the temperature is within this range, there is an advantage that the sol-gel condensation reaction proceeds well at an appropriate rate.
[0037]
The time for immersion in the mixed solution is preferably in the range of 2 to 7 days. This is because when the time is within this range, there is an advantage that the film thickness of the deposit can be appropriately controlled.
[0038]
When the film irradiated with the blue laser light is immersed in the mixed solution, the substrate is preferably stationary on the spacer.
A method is used in which another substrate is provided facing the polymer film on the substrate on which the relief is formed at a distance of 0.1 to 1 mm. This is because the silica-based material is deposited on the relief in a controlled manner by suppressing the convection of the mixed solution. At this time, the distance between the substrates is controlled by sandwiching a polymer film or the like between both ends of the substrate as a spacer.
[0039]
Next, the deposit is irradiated with ultraviolet light in an oxygen-containing atmosphere (20 to 100%), and the deposit is subjected to photo-ozone treatment. Thereby, the organic substance can be removed.
[0040]
The wavelength of the ultraviolet light is preferably in the range of 180 to 260 nm. This is because when the wavelength is within this range, oxygen in the atmosphere is effectively converted into ozone, and organic substances can be decomposed.
[0041]
The irradiation time of ultraviolet light is preferably in the range of 0.5 to 20 hours. This is because when the irradiation time is within this range, there is an advantage that the surfactant used as a template can be almost completely removed.
[0042]
The method for removing the organic matter in the deposit is not limited to the above-described optical ozone treatment. In addition, a method of incineration at a temperature of 400 ° C. or higher can be employed.
[0043]
Next, a second method for producing a mesostructure is described.
A surface relief structure is easily produced with light, and the surface irregularities are utilized, and an inorganic material centering on silica is produced and deposited on the surface using a surfactant organic structure as a template, and is oriented by depositing it. Organic-inorganic mesostructures having mesochannels were prepared. The relief structure is manufactured using a photomask. After the production, the organic substance is removed by a photo-ozone treatment to obtain an oriented mesoporous material.
[0044]
The second method for producing a mesostructured body will be specifically described.
First, a polymer film is formed on a substrate.
Next, the film formed on the substrate is irradiated with ultraviolet light.
These two steps are the same as in the first manufacturing method described above.
[0045]
Next, visible light is irradiated to the film irradiated with ultraviolet light through a photomask. The wavelength of visible light is preferably in the range of 400 to 550 nm. This is because, when the wavelength is within this range, there is an advantage that cis-azobenzene is exposed to light and mass transfer is induced.
[0046]
It is preferable that the line and space intervals of the photomask are in the range of 2 to 8 μm when the same interval is used. This is because when the line and space spacing are within this range, there is an advantage that a well-organized relief structure can be obtained.
[0047]
However, the intervals between the lines and the spaces need not be the same. In addition, the line and space may be a combination of 2 μm to 8 μm of space for 2 μm of line, 4 μm to 8 μm of space for 4 μm of line, or conversely a combination of wide line and narrow space.
[0048]
Visible light exposure is 30-1000mJcm ^-2 It is preferable that it exists in the range. This is because when the exposure amount is within this range, there is an advantage that a relief structure is formed satisfactorily.
[0049]
Next, a mixed solution of a surfactant and a silane compound is prepared.
Next, the film irradiated with visible light through the photomask is immersed in the mixed solution to form a deposit on the film.
Next, the deposit is subjected to optical ozone treatment.
These three steps are the same as in the first manufacturing method described above.
[0050]
Next, a third method for producing a mesostructure is described.
When the spin cast film of polydihexylsilane is irradiated with polarized ultraviolet light, the main chain is cut in an orientation selective manner to form an oriented polymer film. Orientation can be achieved by producing a mesostructured body on this photo-alignment film by the same method.
[0051]
A third method for producing a mesostructure will be specifically described.
First, a polysilane film is formed on a substrate.
[0052]
As a method of forming a polysilane film on a substrate, for example, a method of forming a spin cast film, that is, a method of forming a thin film on a substrate by dripping an organic solvent solution of polysilane onto the substrate and rotating the substrate at a high speed. Can be used. The method for forming the polysilane film on the substrate is not limited to this method. In addition, it is possible to adopt a method such as thin film production by spraying up in a concentrated solution of a polysilane film or spray coating.
[0053]
As polysilane, for example, polydihexylsilane can be used. However, polysilane is not limited to this. In addition, polydibutylsilane, polydioctylsilane, polymethylphenylsilane, polymethylpropylsilane, and the like can be used as the polysilane.
[0054]
In addition to polysilane, σ-conjugated polymers such as polygermane and polystannane can be employed.
[0055]
The molecular weight of the polysilane is preferably in the range of 10,000 to 1,400,000 in terms of weight average molecular weight. This is because when the weight average molecular weight is within this range, there are advantages that the film-forming property is good and the orientation by photolysis is easy.
[0056]
As a method of adjusting the thickness of the polysilane film, for example, there is a method of changing the polysilane concentration in the organic solvent at the time of producing the spin cast film. Other methods for adjusting the film thickness of polysilane include the number of rotations during spin casting, and a method of changing the evaporation rate by mixing a high boiling point solvent such as toluene with the solvent.
[0057]
The film thickness of the polysilane is preferably in the range of 10 to 200 nm. This is because when the polysilane film thickness is within this range, there is an advantage that orientation by polarized light irradiation is easy.
[0058]
Next, ultraviolet polarized light is irradiated to the polysilane film formed on the substrate.
The wavelength of ultraviolet polarized light is preferably in the range of 300 to 380 nm. This is because when the wavelength is within this range, there is an advantage that main chain cleavage occurs easily.
[0059]
UV-polarized light exposure is 50-300mJcm ^-2 It is preferable that it exists in the range. This is because when the exposure amount is within this range, there is an advantage that effective orientation is possible.
[0060]
Here, the reason for irradiating the polysilane film with ultraviolet polarized light is to cut the main chain of polysilane anisotropically with polarized light.
[0061]
When the polysilane film is irradiated with ultraviolet polarized light, the main chain of the polymer is anisotropically cut, and at the same time, the main chain is strongly oriented in the vertical direction of polarized light by self-organization and recrystallization.
[0062]
After the polysilane film is irradiated with ultraviolet polarized light, the film is annealed to obtain a higher-quality alignment film.
The annealing temperature is preferably in the range of 40 to 120 ° C. This is because when the temperature is within this range, the polydihexylsilane is in a semi-molten state with its orientation maintained and there is an advantage that a highly oriented film can be prepared by recrystallization.
[0063]
The annealing time is preferably in the range of 5 to 120 minutes. This is because when the time is within this range, there is an advantage that a film in a semi-molten state can be obtained.
[0064]
Next, a mixed solution of a surfactant and a silane compound is prepared.
Next, the film irradiated with ultraviolet polarized light is immersed in the mixed solution to form a deposit on the film.
Next, the deposit is subjected to optical ozone treatment.
These three steps are the same as in the first manufacturing method described above.
[0065]
The film irradiated with ultraviolet polarized light is immersed in the mixed solution to form a deposit on the film, whereby the mesostructured body is oriented in a direction perpendicular to the ultraviolet polarized light irradiation surface. This is because, by irradiation with ultraviolet polarized light, the main chain is aligned in the direction perpendicular to the polarization direction, and when the surfactant aggregate adheres to the substrate surface, it is aligned in the main chain direction of the polysilane.
[0066]
As described above, the organic-inorganic mesostructured film, which has conventionally been able to align only a relatively large area, can be arbitrarily oriented in a microscopic region of the μm level. Mesoporous structures are regarded as promising as low dielectric constant (low k) materials essential for insulators in electronics, and new processes in the fabrication of electronic devices are possible by applying techniques that can pattern this material. Sex is born.
[0067]
This film scatters light when it is made to crack, but the light scattering direction depends on the orientation direction of the mesostructured body, and it can be used as an anisotropic light scattering material.
[0068]
If an oriented mesoporous material having high transparency can be obtained, a polarizing element and a polarizing light-emitting element can be manufactured by introducing a dye, a fluorescent dye, or the like into the mesochannel.
[0069]
If a metal or graphite can be introduced into the mesochannel, a conductive fine composite material with silica as a wall can be formed and its direction can be determined and patterned by light, so a new electric circuit fabrication method can be submitted.
[0070]
From the above, according to the present embodiment, a polymer film is formed on the substrate, the film is irradiated with ultraviolet light, and the blue laser light that is interfered with the film is irradiated. By creating a mixed solution and immersing the film in the mixed solution to form a deposit on the film, the mesostructures are deposited at the same period as the relief structure under the influence of the relief structure formed on the film. grow up. As a result, a novel method for producing a mesostructure can be provided.
[0071]
Form a polymer film on the substrate, irradiate the film with ultraviolet light, irradiate the film with visible polarized light, create a mixed solution of surfactant and silane compound, and immerse the film in the mixed solution By forming a deposit on the film, the mesostructured body is deposited and grown at the same cycle as the relief structure under the influence of the relief structure formed on the film, as described above. As a result, a novel method for producing a mesostructure can be provided.
[0072]
By forming a polysilane film on the substrate, irradiating the film with ultraviolet polarized light, preparing a mixed solution of a surfactant and a silane compound, and immersing the film in the mixed solution to form a deposit on the film Similar to the above, the mesostructured body is deposited and grown at the same period as the relief structure under the influence of the relief structure formed on the film. As a result, a novel method for producing a mesostructure can be provided.
[0073]
According to the present embodiment, by forming a mesochannel on an oriented polymer film, the direction of the channel can be arbitrarily determined and photopatterned.
[0074]
The present invention is not limited to the above-described embodiment, and various other configurations can be adopted without departing from the gist of the present invention.
[0075]
【Example】
Next, specific examples of the present invention will be described. However, it goes without saying that the present invention is not limited to these examples.
[0076]
Example 1
A 4 wt% tetrahydrofuran solution of poly {ω-hydroxyoligo (ethylene oxide) -α-methacrylate-co-11- [4-[(4-hexylphenyl) azo] phenoxy] undecanoyl methacrylate} shown in FIG. A spin cast film was produced on a quartz substrate under the conditions of 2000 rpm and 20 seconds.
[0077]
In the chemical formula of FIG. ₂ CH ₂ O) _4.5 Is (CH ₂ CH ₂ O) means a 1: 1 mixture of 4 and 5.
[0078]
In the formula, X represents a copolymerization ratio (0 <x <1) and is selected between 0.2 and 0.8.
[0079]
The spin cast film was annealed at 60 ° C. for 10 minutes. The film thickness was about 100 nm.
The following operations were performed on this film to produce a surface relief type diffraction grating-formed thin film.
As a pretreatment for improving the sensitivity of photosensitivity, ultraviolet light was pre-exposed. At this time, the light source is an emission line of 365 nm ultraviolet light (i-line) extracted from a 150 W mercury xenon lamp using an optical filter, and 1 J cm ^-2 Exposed slightly.
[0080]
By exposing the polymer thin film subjected to the pre-exposure (ultraviolet light irradiation) treatment as described above to the interfered blue laser light, the movement of the film material was induced to produce a surface relief diffraction grating pattern. The interference light was generated using direct light and light obtained by reflecting the direct light with a mirror. At this time, an argon ion laser of 488 nm is used as the light source. Irradiation light intensity is 5mWcm ^-2 The exposure time was 10 seconds.
[0081]
The distance (Λ) of the diffraction grating is given by Bragg's relational expression Λ = λ / 2 sinθ (where λ is the wavelength of the laser beam and θ is the angle between the incident surface and the substrate surface). A surface relief type diffraction grating exhibiting an arbitrary periodic structure can be produced. In this case, θ = 3.5 ° and Λ = 4 μm. The relief structure was confirmed using atomic force microscope observation. As shown in FIG. 2, when the surface morphology is observed with an atomic force microscope, it can be seen that irregularities of about 200 nm are observed.
[0082]
After forming the relief, chemical crosslinking between the hydroxyl groups at the end of the ethylene oxide proceeds and the relief structure is more firmly fixed by exposing it to formaldehyde vapor together with hydrogen chloride vapor in a sealed container at room temperature. Although it is better to perform this operation, it is possible to proceed to the next operation without performing this operation.
[0083]
Production of a silica-based mesopore structure material was deposited on the film having the relief structure thus produced in the following manner. As shown in FIG. 3, cetyltrimethylammonium chloride (surfactant as a template) was first dissolved in an aqueous hydrochloric acid solution, and then tetraethoxysilane was added and stirred for 2 to 3 minutes to prepare a precursor solution. A meso material was deposited on the substrate by immersing only the film having the relief structure of the produced substrate in this precursor solution at room temperature for 4 days (immersion time can be 2 to 7 days). The weight ratio of each substance in the mixed solution was hydrochloric acid (concentrated hydrochloric acid): water: cetyltrimethylammonium chloride: tetraethoxysilane = 0.57: 200: 0.03: 0.08.
[0084]
Moreover, in order to prevent the disorder of the orientation by a convection at the time of immersion, the 0.2 mm spacer was produced and the board | substrate was left still on the spacer.
The relief surface is made on a 1.5 x 3 cm substrate, and a 0.2 mm thick Teflon (registered trademark) plate is used as a spacer, through which the same size glass is faced. A plate was placed, allowed to stand on top of the mixed solution, and left for 4 days. The Teflon (registered trademark) plate spacer was installed using a place of about 5 mm from both ends of the substrate. The spacer is essential to prevent convection of the mixed solution and to deposit silica with a controlled mesostructure.
[0085]
When the form of the surface of the produced substrate was observed using an optical microscope, it was found that the silica mesostructured structure was uniaxially oriented under the influence of the relief structure as shown in FIG. 4B. Silica mesostructures were deposited and grown at the same period as the relief structure. On the other hand, in the case of a glass substrate not having a relief structure, the silica mesostructures are randomly oriented as shown in FIG.
[0086]
Further, even when the photo-ozone treatment using an ultraviolet lamp (185 nm and 245 nm) is performed at room temperature for 1 hour and the organic substance as a template is removed, the orientation of the silica mesostructure is maintained as shown in FIG. I found out.
[0087]
In addition, as shown in FIG. 6, the pore size is maintained at about 3 nm from XRD measurement, and there is no change in the diffraction profile after photo-ozone treatment, so that the pore structure is maintained. I understood.
[0088]
The peak of the profile in FIG. 6 shows the periodic structure of the tissue, and the diffraction angle of 3.3 ° corresponds to the periodic structure of the channel of about 3 nm from the Bragg equation.
[0089]
When a surfactant is used as a mold, a layered lamellar structure may be obtained. In this case, the layer spacing is greatly reduced when the mold is removed by ozone treatment. In this experiment, the periodic structure hardly changes even after the ozone treatment is evidence that a honeycomb structure of about 3 nm channel is formed and the mesostructure of silica is maintained even if the mold is removed.
[0090]
Example 2
A polymer spin cast film was prepared in the same manner as in Example 1. First, as a pretreatment for improving the sensitivity of photosensitivity, ultraviolet light (365 nm) was pre-exposed as in Example 1 using a mercury lamp. Then, visible light of 436 nm extracted from the 150 W mercury xenon lamp using an optical filter was transferred to 400 mJcm through a photomask. ^-2 Irradiated as described above. At this time, mass transfer occurred from the exposed part to the unexposed part, and a relief structure reflecting the shape of the mask was formed.
[0091]
A silica mesostructure was produced on the film having the relief structure thus produced in the same manner as in Example 1. As shown in FIG. 7, the silica mesostructure was selectively deposited only on the exposed portion. This was confirmed by optical microscope observation.
[0092]
It was also found that there is an appropriate film thickness for patterning. The deposition time was 2 to 7 days, and when deposited for 10 days or more, the film thickness of the silica mesostructure was increased, and deposition was performed regardless of the exposed and unexposed areas.
[0093]
In order to deposit a silica mesostructure having a controlled orientation, it was necessary to use a mask with lines and spaces at intervals of 2 μm (A in FIG. 7). When the line and space were 4 μm or more, the orientation at the deposited location was randomized, and orientation organization became difficult (BD in FIG. 7).
[0094]
Further, as shown in FIG. 8, it was found that not only a straight line but also a broken line portion can be patterned, and it was found that orientation patterning in an arbitrary direction is possible on the two-dimensional plane of the substrate.
[0095]
Example 3
The same operation as in Example 2 was performed using a photomask having an arbitrary shape instead of lines and spaces. It was found that when the deposition time of the mesostructured material was within 7 days, the mesostructured material was deposited only in the exposed portion and no mesostructured material was deposited in the unexposed portion, as shown in FIG.
In addition, although the orientation is not controlled in a pattern of 4 μm or more, patterning can be performed by separately forming a deposited portion and a non-deposited portion.
[0096]
Example 4
As shown in FIG. 10, a 1.0 wt% hexane solution of polydihexylsilane (PDHS) was prepared, and a spin cast film (film thickness 100 nm) was produced on a quartz substrate under the conditions of 2000 rpm and 20 seconds.
[0097]
This film was exposed to ultraviolet polarized light. As a light source, a 265 nm ultraviolet light (i-line) taken out using an optical filter using a mercury xenon lamp was used. 100mJcm through polarizing plate for exposure ^-2 Exposed slightly.
[0098]
From the measurement of polarized ultraviolet visible absorption spectrum, it was found that the main chain of PDHS was uniaxially oriented in the direction perpendicular to the polarization axis, as shown in FIG.
Polysilane absorbs light strongly in the direction in which the main chain extends. Of the two polarization spectra on the dotted line and the solid line, the one with the higher intensity is observed with polarized light perpendicular to the previously irradiated ultraviolet polarized light. That is, these spectral data indicate that the main chain is oriented perpendicular to the irradiation polarization axis.
[0099]
Furthermore, from observation of the surface form using an atomic force microscope, it was found that the fibrous structure developed in a direction parallel to the polarized light irradiation direction, as shown in FIG.
The brightly displayed part in the atomic microscope observation represents the high part. After annealing, a fibrous structure developed, and it was observed that the fibers were sticking in the vertical direction of the figure.
[0100]
The method for depositing the mesostructured material using this oriented polymer film substrate was performed in the same manner as in Example 1.
When the morphology of the substrate surface was observed with an optical microscope, it was found that the silica mesostructure was uniaxially oriented under the influence of the substrate surface, as shown in FIG. 13B. The orientation direction was found to be perpendicular to the polarized light irradiation surface, that is, the direction of main chain orientation. On the other hand, when the ultraviolet polarized light was not irradiated, the silica mesostructured body was randomly oriented as shown in FIG.
[0101]
Example 5
It was possible to change the film thickness by changing the concentration of the hexane solution during the production of the polydihexylsilane (PDHS) spin cast film. The film thickness capable of strongly orienting PDHS was in the range of 10 to 200 nm.
[0102]
A molecular weight of 10,000 to 1.4 million in terms of weight average molecular weight could be used.
In addition, the degree of orientation of PDHS is increased by increasing the amount of ultraviolet polarized light, which is about 500 mJcm. ^-2 1Jcm can be best aligned with the irradiation light quantity ^-2 As described above, the degree of orientation decreased.
[0103]
In addition, after annealing at 100 ° C. for 5 minutes, the degree of orientation was improved by crystallizing PDHS by storing at room temperature for 3 days (solid and dotted lines in FIG. 11 and FIG. 12). A and B).
[0104]
50-300mJcm ^-2 It was also found that the order parameter, which was small before the annealing treatment, increased with the annealing treatment in the PDHS film subjected to the irradiation light amount of.
[0105]
The degree of orientation (order parameter (S)) can be calculated from the intensity ratio of the polarization spectrum observed using polarized light in the vertical and horizontal directions. S = 0 when completely random, and S = 1 when completely aligned. 100mJcm ^-2 In FIG. 11 where irradiation was performed, when the order parameter was calculated, before annealing (dotted line), S = 0.09 greatly increased to S = 0.70 after annealing. 300mJcm ^-2 14 similarly, S = 0.44 before annealing was improved to S = 0.76 after annealing.
[0106]
100mJcm ^-2 Although the silica mesostructure deposited on the irradiated polysilane film has a relatively fine shape (FIG. 13B), it is 300 mJcm. ^-2 In the case of irradiation, a large structure spread more flatly was obtained (C in FIG. 13). It was found that the size of the entire alignment mesostructure can be changed by the amount of irradiation light.
[0107]
However, 500mJcm ^-2 It was found that the PDHS film to which the irradiation light quantity was applied decreased the degree of orientation by annealing treatment, and was not suitable as an orientation film for mesostructured materials.
[0108]
[References]
(1) About magnetic field orientation:
SH Tolbert, A. Firouzi, GD Stucky, BF Chmelka, Science278, 264 (1997)
(2) Orientation by microcontact printing:
M. Trau 1 et al., Nature390, 674 (1997).
(3) Orientation by rubbing film:
H. Miyata, K. Kuroda, 1 Chem. Mater. 11, 1609 (1999).
(4) Orientation by Langmuir-Blodgett film:
H. Miyata, K. Kuroda, 1Adv. Mater. 11, 1448 (1999).
(5) Orientation by azobenzene monomolecular film by the present inventors:
・ 79th Annual Meeting of the Chemical Society of Japan Yasuhiro Kawashima, Takahiro Seki, Kunihiro Ichimura “Orientation control of mesoporous silica using azobenzene monolayer”
・ The 50th Annual Meeting of the Society of Polymer Science Yasuhiro Kawashima, Takahiro Seki, Kunihiro Ichimura “Control of photo-alignment of mesoporous silica using azobenzene monolayer”
・ The 50th Polymer Symposium Yasuhiro Kawashima, Masaru Nakagawa, Takahiro Seki, Kunihiro Ichimura “Photoalignment of Mesoporous Silica and Introduction of Liquid Crystal / Dye Mixture into Pore”
・ 13th Japan MRS Academic Symposium Yasuhiro Kawashima, Masaru Nakagawa, Takahiro Seki, Kunihiro Ichimura “Control of photo-alignment of mesoporous silica using azobenzene polymer”
[0109]
【The invention's effect】
The present invention has the following effects.
Form a polymer film on the substrate, irradiate the film with ultraviolet light, irradiate the film with blue laser light, create a mixed solution of surfactant and silane compound, and immerse the film in the mixed solution By forming a deposit on the film, a novel method for producing a mesostructure can be provided.
[0110]
Form a polymer film on the substrate, irradiate the film with ultraviolet light, irradiate the film with visible polarized light, create a mixed solution of surfactant and silane compound, and immerse the film in the mixed solution By forming a deposit on the film, a novel method for producing a mesostructured body can be provided.
[0111]
By forming a polysilane film on the substrate, irradiating the film with ultraviolet polarized light, preparing a mixed solution of a surfactant and a silane compound, and immersing the film in the mixed solution to form a deposit on the film A novel method for producing a mesostructured body can be provided.
[Brief description of the drawings]
FIG. 1 is a diagram showing the chemical structure of a polymer used in the method for producing a mesostructured body of the present invention.
FIG. 2 is a diagram showing a cross section of a relief structure confirmed by atomic force microscope observation.
FIG. 3 is a diagram showing a production process of a mesoporous silica film.
FIG. 4 is a diagram of observation results showing that the relief structure affects the orientation of the mesostructured body.
FIG. 5 is a view showing a mesoporous structure after the photo-ozone treatment of the mesostructured body.
FIG. 6 is a diagram showing XRD spectra of a mesostructured body and a mesoporous structure.
FIG. 7 is a diagram observing the change in the deposition state by changing the interval between the line and the space.
FIG. 8 is a diagram observing a change in a deposition state when a line and a space are changed in a perpendicular direction.
FIG. 9 is a diagram showing a correspondence between a photomask pattern and a deposition state pattern;
FIG. 10 is a diagram showing a production process of mesoporous silica using a polysilane film irradiated with polarized light.
FIG. 11 shows polarized ultraviolet light (100 mJcm ^-2 It is a figure which shows a polarization ultraviolet-visible absorption spectrum at the time of irradiation.
FIG. 12 shows before and after the annealing treatment. It is a figure which shows the surface state observed using the atomic force microscope.
FIG. 13 is a diagram showing a state of a mesoporous tissue when the exposure amount of polarized ultraviolet light is changed.
FIG. 14 shows polarized ultraviolet light (300 mJcm ^-2 It is a figure which shows a polarization ultraviolet-visible absorption spectrum at the time of irradiation.
[Explanation of symbols]
DESCRIPTION OF SYMBOLS 1 ... SRG film, 2 ... Mixed solution, 3 ... Teflon (registered trademark) container, 4 ... Unexposed part, 5 ... Polarizing plate

Claims (3)

Form a polymer film on the substrate,
Irradiate the film with ultraviolet light,
Irradiate visible light that interferes with the film,
Make a mixed solution of surfactant and silane compound,
A method for producing a mesostructured body, comprising immersing the film in the mixed solution to form a deposit on the film. Form a polymer film on the substrate,
Irradiate the film with ultraviolet light,
The film is irradiated with visible light through a photomask,
Make a mixed solution of surfactant and silane compound,
A method for producing a mesostructured body, comprising immersing the film in the mixed solution to form a deposit on the film. Form a polysilane film on the substrate,
Irradiate the film with ultraviolet polarized light,
Make a mixed solution of surfactant and silane compound,
A method for producing a mesostructured body, comprising immersing the film in the mixed solution to form a deposit on the film.

Images