WO2011114998A1 - Couche mince transparente d'oxyde de métal de transition ayant des nano-espaces de grand diamètre, son procédé de production et électrode de dispositif à colorant - Google Patents

Couche mince transparente d'oxyde de métal de transition ayant des nano-espaces de grand diamètre, son procédé de production et électrode de dispositif à colorant Download PDF

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WO2011114998A1
WO2011114998A1 PCT/JP2011/055705 JP2011055705W WO2011114998A1 WO 2011114998 A1 WO2011114998 A1 WO 2011114998A1 JP 2011055705 W JP2011055705 W JP 2011055705W WO 2011114998 A1 WO2011114998 A1 WO 2011114998A1
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thin film
nanospace
transparent thin
transition metal
large pore
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Japanese (ja)
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木村　辰雄
デブラージ チャンドラ
加藤　一実
大司　達樹
修司 曾根▲崎▼
允 戸次
雅子 中村
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独立行政法人産業技術総合研究所
Toto株式会社
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    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
    • C01G23/00—Compounds of titanium
    • C01G23/04—Oxides; Hydroxides
    • C01G23/047—Titanium dioxide
    • C01G23/053—Producing by wet processes, e.g. hydrolysing titanium salts
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
    • B01J20/0203—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising compounds of metals not provided for in B01J20/04
    • B01J20/0211—Compounds of Ti, Zr, Hf
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
    • B01J20/0203—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising compounds of metals not provided for in B01J20/04
    • B01J20/024—Compounds of Zn, Cd, Hg
    • B01J20/0244—Compounds of Zn
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
    • B01J20/0203—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising compounds of metals not provided for in B01J20/04
    • B01J20/0251—Compounds of Si, Ge, Sn, Pb
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
    • B01J20/06—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising oxides or hydroxides of metals not provided for in group B01J20/04
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/28—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties
    • B01J20/28054—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties characterised by their surface properties or porosity
    • B01J20/28078—Pore diameter
    • B01J20/2808—Pore diameter being less than 2 nm, i.e. micropores or nanopores
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/30—Processes for preparing, regenerating, or reactivating
    • B01J20/305—Addition of material, later completely removed, e.g. as result of heat treatment, leaching or washing, e.g. for forming pores
    • B01J20/3064—Addition of pore forming agents, e.g. pore inducing or porogenic agents
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B82—NANOTECHNOLOGY
    • B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
    • C01G19/00—Compounds of tin
    • C01G19/02—Oxides
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
    • C01G9/00—Compounds of zinc
    • C01G9/02—Oxides; Hydroxides
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2004/00—Particle morphology
    • C01P2004/60—Particles characterised by their size
    • C01P2004/62—Submicrometer sized, i.e. from 0.1-1 micrometer
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2004/00—Particle morphology
    • C01P2004/60—Particles characterised by their size
    • C01P2004/64—Nanometer sized, i.e. from 1-100 nanometer
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K30/00—Organic devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation
    • H10K30/80—Constructional details
    • H10K30/81—Electrodes
    • H10K30/82—Transparent electrodes, e.g. indium tin oxide [ITO] electrodes

Definitions

  • the present invention relates to a transparent thin film having a large amount of large pore nanospaces of titanium oxide, tin oxide and zinc oxide prepared in the presence of a surfactant, and a method for producing the same, and includes a transition metal oxide surface and biologically relevant molecules.
  • a transparent thin film of transition metal oxide having a pore size nanospace As an electrode material that enables high-sensitivity sensing of dye-sensitized devices that use biologically relevant molecules immobilized on the surface of transition metal oxides
  • the present invention relates to a transparent thin film of transition metal oxide having a pore size nanospace.
  • the mesoporous material synthesized by utilizing the property that the amphiphilic organic compound self-assembles in the solution is expected to develop various applications depending on the composition constituting the skeleton.
  • centering on silica-based materials while using organic modification etc. in parallel with research and development on pore size control, morphology control, introduction of foreign elements into the skeleton, functionalization in mesopores, etc.
  • Use in adsorption separation involving relatively large organic molecules such as pharmaceuticals, drug delivery systems (DDS), catalytic reactions, and the like has been studied.
  • the control range of the pore diameter of the mesoporous material by the silica-based material is not wide, and the present situation is not yet satisfactory with respect to the above utilization.
  • n PO m EO polyoxyethylene-polyoxypropylene-polyoxyethylene
  • n , n and m are the number of polymerization of each unit) synthesized using a triblock copolymer, and the control range of the pore diameter is not wide.
  • pore diameter is generally in the range of 10 nm or less, and therefore the size of protein or DNA is 10 nm. Therefore, it cannot be used for selectively handling biologically related molecules exceeding the above range, and therefore further increase in pore size is desired.
  • Non-Patent Document 1 a method of obtaining a macroporous body (reverse opal structure) having a large pore nanospace of an inorganic oxide by transferring a regular laminated structure (opal structure) of spherical particles such as polystyrene (hereinafter abbreviated as PS).
  • PS polystyrene
  • the rate of lamination (sedimentation) of small PS spherical particles is slower than the volatilization rate of the dispersion solvent, it is difficult to precisely laminate the PS spherical particles, and the spherical particles are laminated and the inorganic precursor solution is immersed.
  • Another disadvantage of this process is that it requires a multi-step synthesis process such as drying of the dispersion solvent. For example, when a thin film is formed, if the film is formed by spin coating, the volatilization rate of the solvent is high, so the thin film is formed before the spherical particles are stacked, and the spherical PS particles are introduced into the thin film in an isolated state. It may be done.
  • PS n -b-PEO m polystyrene-polyoxyethylene diblock copolymer
  • a feature of the synthesis using PS n -b-PEO m is that spherical mesopores are likely to be generated. Even if the diameter of the generated mesopores corresponds to the size of the bio-related molecule, Since the entire inside of the thin film cannot be used effectively unless the bio-related molecules can pass through the connecting holes between the mesopores, handling can be performed by simply relating the diameter of the generated mesopores directly to the size of the bio-related molecules. It doesn't matter.
  • spherical mesopores with a pore diameter of 10 nm are connected by pores of less than 1 nm and exist in an almost isolated state (non-patented) Reference 2).
  • mesoporous carbon synthesized using PS 230 -b-PEO 125 spherical mesopores are generated and the maximum pore diameter is 26 nm, but there are about 5 nm connecting pores.
  • Non-patent Document 4 The pore diameter of mesoporous platinum synthesized using PS 35 -b-PEO 109 is only 15 nm, and in this case, the pores are merely connected by small pores.
  • a crater-like space exists in the entire thin film, and it is not a porous thin film.
  • the diameter of the crater-like space that can be calculated from the description is not so large as about 30 nm (Non-Patent Document 5). Therefore, regarding the synthesis using PS n -b-PEO m , the synthesis of a thin film having a porous structure capable of diffusing biomolecules throughout the thin film has not been realized.
  • the present invention has been made in view of the circumstances as described above, and has a large pore diameter in the range of 30 to 150 nm so that biologically relevant molecules and the like can be handled selectively and in large quantities.
  • the present inventor used an extremely large polymerization number and synthesized an inorganic raw material optimally when synthesizing a semiconductor oxide thin film in the presence of PS n -b-PEO m. As a result, it was found that the intended purpose can be achieved, and the present invention has been completed.
  • a polyoxyethylene unit that plays a hydrophilic role (hereinafter abbreviated as a PEO unit) and a polystyrene unit that plays a hydrophobic role within a range of 300 to 4000 (hereinafter abbreviated as a PS unit) )
  • a transition metal oxide precursor made of one or more of a metal salt of titanium, tin or zinc and a metal alkoxide as a raw material A method for producing a transparent thin film of a transition metal oxide having a large pore nanospace, wherein the surfactant is removed.
  • the structure of the transparent thin film is regular or irregular defined by self-assembly of the surfactant. It is a set of spherical spaces.
  • the diameter of the large pore nanospace defined by the self-assembly of the surfactant is in the range of 30 to 150 nm. It is.
  • the large pore size nanospaces are connected by pores larger than 10 nm.
  • the main component of the transparent thin film is titanium oxide, tin oxide or zinc oxide, It has a crystalline structure, a crystal structure or an intermediate phase thereof.
  • the transparent thin film is crystallized in the process of removing the surfactant at a high temperature.
  • a transparent thin film produced by the above first to sixth methods characterized in that spherical large pore nanospaces defined by self-assembly of surfactants are regularly or irregularly assembled. It is the transparent thin film of the transition metal oxide which has large-pore-diameter nanospace.
  • the diameter of the spherical large pore nanospace defined by the self-assembly of the surfactant is 30 to 150 nm.
  • the spherical large pore nanospace defined by the self-assembly of the surfactant is a pore having a diameter larger than 10 nm. It is connected by.
  • the transparent thin film of transition metal oxide having a large pore nanospace is one or more selected from amorphous titanium oxide, tin oxide or zinc oxide It is composed of
  • a biologically related molecule adsorption / separation material comprising a transparent thin film of a transition metal oxide having a large pore nanospace according to any one of the seventh to tenth aspects.
  • Twelfth Dye sensitization characterized by immobilizing functional dye molecules in the large pore size nanospace of the transparent metal oxide transparent thin film having the large pore size nanospace according to any one of the seventh to tenth aspects Type device electrode.
  • the kind of the transition metal oxide in the presence of PS n -b-PEO m having a very large number of polymerizations which defines the number of polymerizations of the block copolymer of PS units. It is possible to form a transition metal oxide having a large pore nanospace whose diameter exceeds 100 nm by preparing a transparent precursor solution with a prescribed thickness, and to reduce the wall thickness around the large pore nanospace Thus, the connecting holes can be generated and increased.
  • a transparent thin film of transition metal oxide having a large pore nanospace can be realized by the methods of the first to sixth inventions.
  • the transition metal oxide transparent thin film having a large pore nanospace can immobilize a large amount of biologically relevant molecules, and thus can be used as an adsorptive separation material.
  • biologically relevant molecules labeled with dye molecules they can be used as electrode members for dye-sensitized solar cells and electrode members for high-sensitivity sensors for harmful chemical substances using the principle of dye sensitization.
  • FIG. 2 is a graph of powder X-ray diffraction (hereinafter abbreviated as XRD) of a powder sample obtained by drying a transparent precursor solution used when synthesizing a transparent thin film of titanium oxide having a large pore nanospace of Example 1.
  • FIG. is there. 4 is a SEM photograph of a tin oxide transparent thin film having a large pore nanospace of Example 2.
  • FIG. 3 is an XRD graph of a tin oxide transparent thin film having a large pore nanospace of Example 2.
  • (A) is a graph showing the adsorption behavior of cytochrome c on the surface of a transparent thin film of titanium oxide having a large pore nanospace, which was formed at a spin coating speed of 3000 rpm and fired at 400 ° C. in Example 4
  • (B) is a graph showing the desorption behavior.
  • 6 is a graph showing changes in the amount of cytochrome c adsorbed on the surface of a transparent thin film of titanium oxide having large pore nanospaces synthesized at different firing temperatures in Example 4.
  • FIG. 4 is a comparison of the amount of cytochrome c adsorbed on the surface of a porous thin film of various titanium oxides of Example 4.
  • FIG. 6 is a graph showing a comparison of the amount of Cy5-ssDNA adsorbed on the surface of a porous thin film of various titanium oxides of Example 5.
  • FIG. 7 is a graph showing a comparison between photocurrent generated when Cy5-ssDNA immobilized on the surface of a titanium oxide thin film having a large pore nanospace in Example 5 is excited with 120 mW light and various porous thin films of titanium oxide. is there.
  • FIG. 6 is a graph showing a comparison between photocurrent generated when Cy5-ssDNA immobilized on the surface of a titanium oxide thin film having a large pore nanospace of Example 5 is excited with 6 mW light and various porous thin films of titanium oxide. is there.
  • 6 is a graph showing the adsorption of Cy5-XG69 on the surface of a titanium oxide thin film having a large pore diameter nanospace baked at 400 ° C. in Example 6.
  • FIG. 6 is a graph showing a comparison between photocurrent generated when Cy5-XG69 immobilized on the surface of a titanium oxide thin film having a large pore nanospace in Example 6 is excited with 120 mW light and various porous thin films of titanium oxide. is there.
  • metal raw material of the transition metal oxide used in the present invention one or more selected from a metal salt of titanium, tin or zinc and a metal alkoxide can be used.
  • the metal raw material In order to make the metal raw material a transition metal oxide, it can be prepared by a method of adding a metal salt to an ethanol solution, or a method of hydrolyzing a metal alkoxide by adding hydrochloric acid.
  • the metal raw material for example, if hydrogen chloride is generated from chloride during the reaction or the solution is acidified by adding hydrochloric acid, the hydrophilic portion of the surfactant described later is protonated. , Interaction with dissolved inorganic species becomes stronger.
  • metal alkoxide when metal alkoxide is used, it is sufficient to prepare an acidic precursor solution by adding hydrochloric acid at the same time as the purpose of controlling the reaction. There is no problem even if a salt (nitrate, acetate, etc.) is used as a starting material. Even by mixing the chloride and the alkoxide, the formation of an oxide network is promoted, and at the same time, hydrogen chloride is generated to prepare an acidic precursor solution.
  • the surfactant used in the present invention is a block copolymer composed of a PEO unit that plays a hydrophilic role and a PS unit that plays a hydrophobic role.
  • the above surfactant is dissolved in a solvent to prepare a surfactant solution.
  • a solvent capable of completely dissolving PS n -b-PEO m is not easily selected because of its low solubility in various solvents.
  • THF tetrahydrofuran
  • a mixed solvent of THF and ethanol is preferable as the solvent, and a mixed solvent of THF and ethanol.
  • a polar solvent such as dioxane is also excellent in the ability to dissolve PS n -b-PEO m and can be suitably used.
  • PEO units can interact with dissolved inorganic species in solution by hydrogen bonding, and when used in acidic hydrochloric acid, protonated PEO units and dissolved inorganic species are more strongly and electrostatically Even in the process of interaction and surfactant self-assembly, inorganic species can exist stably in the vicinity of the hydrophilic part, and inorganic organic mesostructures can be generated through bond formation between inorganic species. This is preferable because it is possible.
  • the unit exhibiting hydrophobicity is a PS unit
  • the surfactant is used even when a block copolymer having a large molecular weight, that is, a high degree of polymerization is used.
  • a self-assembled structure is formed.
  • many synthesizing mesoporous materials using EO n PO m EO n have been reported from all over the world, but the maximum number of polymerizations per unit is about 100.
  • phase separation occurs, which makes it difficult to use the structure regularity at the nano level. Therefore, not a polyoxypropylene chain but a block copolymer containing a strongly hydrophobic PS unit is required as a structure-directing agent for a compound having a large pore nanospace.
  • a block copolymer composed of units having a large difference between hydrophilicity and hydrophobicity such as PS n -b-PEO m has a strong property of self-assembling spherically in a polar solvent. For this reason, the nanostructure of the transparent thin film of transition metal oxide having a large pore nanospace is assumed to be an aggregate of spherical large pore nanospaces defined by the self-assembly of the surfactant.
  • the size of the spherical aggregates varies due to the difference in the number of associations and molecular weights, and the assembly of nanopores may become irregular.
  • the number of polymerizations of PS n -b-PEO m is important.
  • the density of PS units is 1.06 gcm ⁇ 3 (refer to the density of 100 nm latex spheres), and PS 35 -b-PEO 109
  • a spherical PS portion having a diameter of 10 nm (10 nm for silica) (see Non-Patent Document 2) and PS 230 -b-PEO 125 having a diameter of 20 nm (31 nm for silica) (see Non-Patent Document 2) is generated.
  • the number of polymerization of the PS unit and the pore size are not in a simple proportional relationship, and when PS n -b-PEO m having a large polymerization number is used, it can be interpreted that several molecules are associated. .
  • a porous body having a pore size of about 30 nm is generated by synthesis using PS 230 -b-PEO 125 (see Non-Patent Document 3), at least about 4 PS 230 -b-PEO 125 molecules are present. It can be interpreted as meeting.
  • the PS unit in order to realize generation of the core part of a PS unit having a diameter of 30 nm in one molecule assembly, the PS unit must have a molecular weight of about 100,000 (the number of polymerization is about 960), and several molecules should be associated. If possible, it can be expected that a larger PS unit core will be generated.
  • the number of associations of a surfactant increases with an increase in molecular weight. Therefore, the molecular structure of the surfactant can be defined in consideration of both the number of polymerizations and the association ability, and the diameter actually exceeds 30 nm. In order to obtain a compound having a large pore nanospace, it is necessary to consider both the number of polymerizations and the number of associations of the PS unit at the same time.
  • the number of polymerized PS units is about 300, it is considered that a PS core portion of about 30 nm can be formed when three molecules are associated. Even if the number of polymerizations is increased to about 4000, it is possible to form a spherical aggregate of about 50 nm with one molecule. To form the core part of a 150 nm PS unit, the number of associations should be about 30 molecules.
  • the number of polymerization of PS n -b-PEO m is not so strict as long as the generated core portion can be surrounded.
  • the PEO unit corresponds to a shell portion, and if the amount of transition metal species that interact with the portion to form a skeleton is too large, the large holes that are generated at the corner are isolated. Even when a transparent thin film of a transition metal oxide having a large pore nanospace with a diameter of 30 to 150 nm can be obtained, the size of the linkage is sufficient to selectively handle a large amount of biologically relevant molecules exceeding 10 nm. The holes are not necessarily present.
  • the wall thickness around the large pore size nano space is largely determined by the amount of inorganic raw material supplied, it is related to the number of polymerizations of the PEO unit, so the connection hole is controlled by reducing the wall thickness by controlling that amount. be able to.
  • titanium tetrapropoxide (0.135 g) is added to a mixed solvent in which PS 960 -b-PEO 3400 (0.08 g) is dissolved in THF / ethanol (11.25 mL) at a volume ratio of 4: 1.
  • a precursor solution prepared by mixing hydrolyzed concentrated hydrochloric acid (0.296 mL), PS 960 -b-PEO 3400 (0.08 g) was added at a volume ratio of 4: 1.
  • hydrochloric acid Sex under include a precursor solution prepared from anhydrous zinc acetate (0.087 g) and the like.
  • the amount of inorganic species that can be present in the shell portion can be controlled by interaction, so the wall condition can be achieved by optimizing the synthesis conditions of the polymerization number and the addition amount of the inorganic raw material.
  • the connection hole can be controlled by controlling the thickness.
  • the structure of a transparent thin film of transition metal oxide having a large pore nanospace and the molecular structure of PS n -b-PEO m are largely related to PS n -b-PEO m.
  • various synthesis conditions such as the THF / ethanol ratio, the amount of solvent, the amount of hydrochloric acid, the reaction time, etc. are appropriately adjusted and desired It becomes possible to obtain a transparent thin film.
  • PS n -b-PEO m itself has a strong tendency to assemble into a spherical shape in a solvent, it is extremely important to prepare a transparent precursor solution.
  • the amount of transition metal species relative to PS n -b-PEO m is also important in order to introduce a large pore nanospace into the entire transparent thin film, and this greatly affects the connectivity of the spherical nanospace.
  • an acidic solution obtained by adding chloride to an ethanol solution or a solution obtained by hydrolyzing alkoxide with concentrated hydrochloric acid is separately prepared. Mix with solution.
  • the surfactant is removed to obtain a transparent thin film of transition metal oxide having a large pore nanospace.
  • the substrate is not particularly limited as long as it has a smooth surface and does not interfere with film formation.
  • a substrate such as glass, quartz, silicon, single crystal ITO, graphite, or Teflon (registered trademark) is preferable. Can be used.
  • a coating method for film formation it can be applied by a known method such as spin coating or dip coating. According to these methods, the film thickness can be controlled by appropriately adjusting coating conditions such as spin coating speed and dip coating pulling speed.
  • the surfactant from the formed thin film it can be removed by baking or UV ozone treatment.
  • the transition metal species As a condition for removing the surfactant by firing, for example, it is possible to remove the surfactant even at a low temperature of 250 ° C. In this case, the transition metal species remains in an amorphous structure and a large pore size nanospace is formed. A transparent thin film of a transition metal oxide can be obtained.
  • the crystallization temperature differs depending on the transition metal species, the structure of the large pore nanospace where the transition metal species is crystallized does not collapse even when processed at a higher temperature. A transparent thin film can be obtained.
  • the transition metal oxide thin film containing a large amount of spherical PS n -b-PEO m aggregates has high transparency, in addition to the removal of the surfactant by the above baking, the surfactant is also removed by UV ozone treatment by ultraviolet irradiation. It can be removed.
  • a transparent thin film of transition metal oxide having a large pore nanospace made of titanium oxide, tin oxide or zinc oxide having an amorphous skeleton structure Can be obtained.
  • the surfactant is removed by baking at a temperature higher than the crystallization temperature of each of titanium oxide, tin oxide, or zinc oxide, the crystallization of the skeleton structure proceeds gradually and includes microcrystals (amorphous structure and crystal It becomes possible to obtain a transparent thin film of a transition metal oxide having a large pore nanospace made of titanium oxide, tin oxide or zinc oxide having a unique crystal structure from the intermediate phase of the structure.
  • a large amount of large pore nanospace exists in the range of 30 to 150 nm in the transparent thin film of transition metal oxide, and exceeds 10 nm. Since it has a connecting hole of sufficient size to handle such biologically relevant molecules selectively and in large quantities, it is extremely selective in vivo in proteins and DNA, as represented by enzyme reactions and the like. It can be a specific reaction field for handling functional organic compounds that play an important role in various reactions efficiently.
  • the functional dye molecules can be adsorbed selectively and in large quantities by utilizing the interaction with the surface of the transition metal oxide that constructs the large pore nanospace, the functional dye molecules can be strongly immobilized Can also be separated from the mixture.
  • the transparent thin film of transition metal oxide having a large pore nanospace of the present invention can also be used as an electrode material.
  • Non-Patent Document 6 In research on Gratzel type dye-sensitized solar cells (see Non-Patent Document 6), various combinations of transition metal oxides such as titanium oxide, tin oxide, zinc oxide, and tungsten oxide with dyes have been studied. None has been found that shows conversion efficiency exceeding the combination of titanium and ruthenium complex. For example, it has been reported that a conversion efficiency of 10% is realized by a combination of titanium oxide nanocrystal particles and a ruthenium complex (see Non-Patent Documents 7 to 9). This describes that the titanium oxide electrode is designed with nanoparticles in order to increase the amount of dye molecules (ruthenium complex) adsorbed.
  • the transition metal oxide transparent thin film having a large pore nanospace according to the present invention is not only an extremely useful electrode material, but also can greatly increase the amount of dye molecules adsorbed, and also has a very high thin film transparency. An efficient conversion can be expected.
  • the transparent thin film of transition metal oxide having a large pore nanospace of the present invention can be effectively used as an electrode material for a dye-sensitized solar cell.
  • transition metal oxide transparent thin film having a large pore nanospace of the present invention can be used as an electrode material for the construction of a sensor system using the principle of dye sensitization.
  • a dye-sensitized device is constructed using a labeling dye in order to highly sensitively detect environmental hormones that are highly toxic even in very small amounts. It is extremely important for high sensitivity to adsorb chemical substances (dioxins, estradiol, bisphenol A, etc.) suspected as environmental hormones on the surface of the semiconductor electrode as much as possible and selectively.
  • a dye-sensitized solar cell sunlight can be used on the principle that energy is transferred from a photoexcited dye to a semiconductor electrode to generate a current.
  • fluorescence or electrons (photocurrent) generated from the photoexcited labeling dye are detected using a fluorescence spectrum measurement or an ammeter, respectively.
  • dioxins interact with DNA molecules very selectively. Since the labeling dye is denatured simultaneously with the adsorption, dioxins can be sensed with high sensitivity by detecting fluorescence or photocurrent from the denatured dye.
  • the DNA at this time is called a dioxin receptor. If the estradiol receptor is immobilized on the electrode surface, estradiol can be sensed with high sensitivity.
  • a large amount of DNA molecules can be immobilized even on a transparent electrode having a large pore nanospace such as titanium oxide, tin oxide and zinc oxide.
  • PS n -b-PEO m having a PS unit number average molecular weight of 100,000 (polymerization number of about 960) and a PEO unit number average molecular weight of 150,000 (polymerization number of about 3400) (PS 960 -b -PEO 3400 ) was used to synthesize a transparent thin film of titanium oxide having a large pore nanospace.
  • PS 960 -b-PEO 3400 (0.08 g) was completely dissolved in a mixed solvent of THF / ethanol (11.25 mL) at a volume ratio of 4: 1.
  • a concentrated solution (0.296 mL) is slowly added dropwise to titanium tetrapropoxide (0.135 g) to prepare a transparent hydrolyzed solution, which is then mixed with a surfactant solution to prepare a transparent precursor solution.
  • the thin film was obtained by spin-coating the obtained solution on a glass substrate. Immediately after the film formation, the thin film was cooled to ⁇ 20 ° C. to slow down the formation of the titanium oxide skeleton network, and proceeded to a drying operation at 50 ° C. before frost was formed inside the thin film by moisture in the air.
  • the surfactant was removed by baking at 400 ° C. to obtain a transparent thin film of titanium oxide having a large pore nanospace.
  • PS n -b-PEO m having a small number of polymerizations, it was possible to obtain a transparent thin film of titanium oxide having a nanospace with an arbitrarily smaller diameter.
  • the powder sample obtained by drying the transparent precursor solution in a tray was fired at 250 ° C. and 400 ° C., and the relationship between the crystallinity of the titanium oxide skeleton and the firing temperature was measured by XRD. The result is shown in FIG. The presence of diffraction peaks that can be attributed to the anatase phase of titanium oxide was confirmed in most cases when it was fired at 250 ° C., and when it was fired at 400 ° C.
  • the crystallinity of the skeleton of the transition metal oxide having a large pore nanospace can be controlled by the firing temperature. Further, when the thin film was shaved and observed with a transmission electron microscope at a high magnification, it was observed that a large amount of anatase crystals of about 5 to 10 nm were present inside the skeleton of the thin film fired at 400 ° C. As a result of film formation at a spin coating speed of 800 to 3000 rpm, the film thickness after baking at 250 ° C. or 400 ° C. was about 200 nm. As a result of evaluating the porosity of the thin film by krypton (Kr) gas adsorption measurement, the specific surface area was about 30 m 2 cm ⁇ 3 .
  • a transparent thin film of tin oxide having a large pore nanospace was synthesized using PS 960 -b-PEO 3400 .
  • PS 960 -b-PEO 3400 (0.08 g) was completely dissolved in a THF / ethanol (10 g) mixed solvent having a volume ratio of 4: 1.
  • pure water 0.2 mL was added to a solution obtained by hydrolyzing in advance by adding concentrated hydrochloric acid (0.296 mL) dropwise to anhydrous tin dichloride (0.06 g), and PS 960- b-PEO 3400
  • a clear precursor solution was prepared by mixing with the solution.
  • the thin film was obtained by spin-coating the obtained solution on a glass substrate. Immediately after the film formation, the thin film was cooled to ⁇ 20 ° C., dried at 50 ° C. and then fired at 450 ° C. to remove the surfactant.
  • the large pore nanospace of the obtained thin film exists in the entire thin film, the diameter of the nanospace can be estimated to be 10 to 150 nm, and the large pore nanospace is larger than 10 nm. It was confirmed that the holes were connected by holes. It was confirmed that the large pore nanospace was surrounded by the tin oxide nanocrystals, and as a result of direct XRD measurement of the transparent thin film, it was confirmed that the tin oxide skeleton was sufficiently crystallized. The result of the XRD measurement is shown in FIG.
  • a transparent thin film of zinc oxide having a large pore nanospace was synthesized using PS 960 -b-PEO 3400 .
  • PS 960 -b-PEO 3400 (0.08 g) was completely dissolved in a THF / ethanol (11.76 mL) mixed solvent having a volume ratio of 4: 1.
  • a transparent precursor solution was prepared by mixing a transparent solution prepared from anhydrous zinc acetate (0.087 g) with a surfactant solution under acidic conditions of hydrochloric acid.
  • a film was formed by spin-coating the obtained solution on a glass substrate, completely dried, and then baked at 400 ° C. to remove the surfactant and crystallize the zinc oxide skeleton.
  • Cy-c cytochrome c
  • UV-Vis ultraviolet-visible spectroscopy
  • FIG. 5 (a) shows the desorption behavior in FIG. 5 (b).
  • FIG. 6 shows changes in the amount of Cy-c adsorbed on the surface of a transparent thin film of titanium oxide having a large pore nanospace synthesized at different firing temperatures of 250 to 600 ° C. From this XRD measurement, it was confirmed that when the firing temperature was increased, an anatase phase was generated and the crystallinity was improved. Increasing the calcination temperature increased the amount of Cy-c adsorbed, although the specific surface area hardly changed. Therefore, it can be seen that the crystallinity of the titanium oxide skeleton also affects the amount of Cy-c adsorption.
  • the transparent thin film of titanium oxide having large pore nanospaces of the present invention which is composed of macropores and a large number of large connecting pores, has excellent adsorption characteristics for relatively large molecules such as Cy-c. It can be interpreted as shown.
  • a transparent thin film of transition metal oxide having a large pore nanospace by the transparent precursor solution prepared in Example 1 was formed on a fluorine-doped tin oxide (FTO) substrate, and a DNA adsorption experiment was performed.
  • FTO fluorine-doped tin oxide
  • One molecule of dye (cytochrome) was labeled with respect to one DNA molecule, and the amount of adsorbed DNA was calculated from intensity measurement of fluorescence emission from the labeled dye.
  • the molecule is expressed as Cy5-ssDNA (base sequence: GCGGCATGAACCTGAGGCCCCATCCT).
  • porphyrin ring structure with a metal center of iron (Fe), which functions as an electron transfer protein in vivo, but the porphyrin ring structure is used as a dye molecule for capturing light energy.
  • Fe metal center of iron
  • ssDNA dissolved in water was denatured by heating at 95 ° C. for 10 minutes, and 5 mL was spot-dropped on the thin film and held at 95 ° C. for 10 minutes.
  • the thin film was washed with 0.2% sodium dodecyl sulfate aqueous solution, rinsed with pure water, immersed in boiling water for 2 minutes, and then immersed in ethanol at 4 ° C. for 2 minutes to remove excess biomolecules.
  • Cy-c strongly interacts with the surface of titanium oxide and tin oxide from the behavior of adsorption from aqueous solution and desorption into water. Showed that.
  • Cy5-ssDNA was immobilized on the thin film surface, and then the substrate was thoroughly washed to remove excess biomolecules. Nevertheless, Cy5-ssDNA was immobilized on the thin film surface. Therefore, it was confirmed that it was extremely strongly immobilized.
  • Cy5-ssDNA was adsorbed on the surface of the tin oxide thin film having a large pore nanospace that was baked at 450 ° C. to crystallize the skeleton.
  • the amount of Cy5-ssDNA adsorbed was an order of magnitude less than that of a titanium oxide thin film having a large pore nanospace that was baked at 400 ° C. to crystallize the skeleton.
  • the current value was saturated.
  • 6 mW There was a good relationship between the photocurrent and the amount of dye adsorbed when the light source was very weak, 6 mW, indicating a larger current value than the titanium oxide thin film.
  • a transparent thin film of a transition metal oxide having a large pore nanospace with the transparent precursor solution prepared in Example 1 was formed on an FTO substrate, and proteins (Anti-AFP antibody NB0-13, AFP: alpha-feto-protein) , Japan Biotest) adsorption experiment.
  • a molecule in which one molecule of dye (Cy5) was labeled with respect to NB0-131 molecule was expressed as Cy5-NB0-13, and the amount of protein adsorbed was calculated from the measurement of the intensity of fluorescence emitted from the labeled dye. It was also confirmed whether photocurrent generated from adsorbed Cy5 was detected.
  • the protein was detected using the antigen-antibody reaction.
  • PSA Prostate Specific Antigen
  • XG-69 goat: Fitzgerald Industries International, Inc.
  • the secondary antibody was a protein (Anti-PSA monoclonal antibody: 5A6, neutral: 5A6-mouseGoneBoth )
  • 5A61 5A61 molecule
  • the photocurrent measurement result also shows a good correlation with the fluorescence value, and in the case of a tin oxide thin film, photocurrent detection using the principle of a dye-sensitized solar cell is possible. there were.

Abstract

L'invention porte sur un procédé pour la production d'une couche mince transparente d'un oxyde de métal de transition, des pores de grande taille, ayant un diamètre dans la plage de 30-150 nm qui peuvent traiter des molécules biologiquement appropriées sélectivement et en volumes importants, étant présents et les pores de raccordement pour ceux-ci ayant une taille telle que des molécules biologiquement appropriées peuvent y passer. Ce procédé est caractérisé en ce que, après mélange d'un agent tensioactif, qui est fabriqué par copolymérisation en séquence d'un motif polyoxyéthylène qui joue un rôle hydrophile et d'un motif polystyrène ayant un degré de polymérisation dans la plage de 300-4000 qui joue un rôle hydrophobe, un sel métallique de titane, d'étain ou de zinc et un oxyde de métal de transition précurseur ayant un ou plusieurs alcoolates métalliques comme matière de départ inorganique sont ajoutés et, après la croissance de la couche mince, l'agent tensioactif est éliminé. L'invention porte également sur la couche mince transparente.
PCT/JP2011/055705 2010-03-19 2011-03-10 Couche mince transparente d'oxyde de métal de transition ayant des nano-espaces de grand diamètre, son procédé de production et électrode de dispositif à colorant WO2011114998A1 (fr)

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JP6083635B2 (ja) * 2012-06-13 2017-02-22 国立研究開発法人産業技術総合研究所 球状マクロ孔を含む金属酸化物多孔質厚膜及びその製造方法

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