JP2003315840A - Electrochromic display - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide an electrochromic display which is easily made full-color, has an excellent memory performance and is drastically improved in response rate, coloring efficiency and repeating durability. <P>SOLUTION: The electrochromic display is made by holding an electrolyte layer containing an electrochromic dyestuff which reversibly is colored or decolored by at least one of electrochemical oxidation reaction and reduction reaction between semiconductor nono porous layers disposed opposite to each other and is made by laminating plural sheets of structural units having either structure of a passive matrix panel structure and an active matrix panel structure. <P>COPYRIGHT: (C)2004,JPO

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an electrochromic display, and more particularly to an electrochromic display which can be easily made into a full color image, has an excellent memory property, and has significantly improved response speed and repeated durability.

[0002]

2. Description of the Related Art Electrochromic (hereinafter abbreviated as "EC") devices, such as EC display devices, do not require a polarizing plate or the like, and therefore have no light-receiving type and are excellent in visibility and are electrochemically oxidized. The structure is simple and easy to increase in size because at least an electrolyte containing the EC material that reversibly develops or discolors by a reduction reaction and a pair of electrodes are provided. Color tone can be obtained, the display state can be stopped just by blocking the movement of electrons and maintaining the redox state, so that it has excellent memory properties, and it does not require power to maintain the display state, so power consumption is low, It has been applied in various fields because of its various advantages.

For example, an all-solid-state EC in which a transparent electrode layer (cathode), a tungsten trioxide thin film layer (EC layer), an insulating layer such as silicon dioxide, and an electrode layer (anode) are sequentially laminated on a glass substrate. A device is disclosed in Japanese Examined Patent Publication No. 52-46098. When a voltage (coloring voltage) is applied to this EC element, the tungsten trioxide (WO ₃ ) thin film layer is colored blue. After that, when a voltage (decoloring voltage) having a reverse polarity is applied to this EC element, the blue color of the tungsten trioxide thin film layer disappears and it returns to colorless. The mechanism of this color fading has not been clarified in detail, but it is said that a small amount of water contained in the WO ₃ thin film layer and the insulating layer (ion conductive layer) controls the color fading of the WO ₃ thin film layer. To be understood.

Recently, for example, JP-A-9-120088, JP-A-7-152050, and JP-A-6-24.
2474, etc., the EC material is vapor-deposited on a pair of electrodes, and a supporting salt and a solvent are enclosed between the electrodes, or an EC display device between the pair of electrodes. Various EC display devices such as an EC display device in which a supporting salt and a solvent are enclosed have been proposed.

However, in these EC display devices, there is a serious problem that it is difficult to increase the response speed because the movement of the substance (ion) is involved in coloring and decoloring. Especially, in the case of the latter EC display device. However, there is a problem that bleeding occurs due to the diffusion of the coloring substance, and it is difficult to display a high-definition image. Therefore, for example, Japanese Patent Laid-Open No. 2000-
In Japanese Patent Laid-Open No. 19567, it is proposed to use a polymer solid electrolyte in the latter EC display device, but there is a problem that sufficient ionic conductivity is not obtained even by heating and the like and the response is poor.

Therefore, it is easy to realize full color,
At present, there is no EC display that has excellent memory performance, and has significantly improved response speed, color development efficiency and repetition durability.

[0007]

SUMMARY OF THE INVENTION It is an object of the present invention to solve the above problems in the prior art and to solve the following problems. That is, it is an object of the present invention to provide an EC display which has a simple structure, is easy to manufacture, can be easily made into a full color image, has an excellent memory property, and has significantly improved response speed, color development efficiency, and repetitive durability. And

[0008]

Means for solving the problems Means for solving the above problems are as follows. That is, <1> electrochemical oxidation reaction and reduction reaction are performed while a pair of transparent electrodes having a semiconductor nanoporous layer formed on at least one surface thereof are arranged so that the semiconductor nanoporous layers face each other. Sandwiching an electrolyte layer containing an electrochromic dye capable of reversibly developing or erasing color by at least one of, and laminating a plurality of structural units having any one of a passive matrix panel structure and an active matrix panel structure. It is an electrochromic display characterized by <2> A pair of transparent electrodes having a semiconductor nanoporous layer carrying an electrochromic dye capable of reversibly developing or decoloring by at least one of an electrochemical oxidation reaction and a reduction reaction formed on at least one surface thereof, An electrolyte layer is sandwiched between the semiconductor nanoporous layers arranged so as to face each other, and a plurality of structural units each having a passive matrix panel structure or an active matrix panel structure are laminated. It is an electrochromic display characterized in that <3> The electrochromic display according to <1> or <2>, in which 2 to 4 structural units are laminated. <4> The electrochromic display according to <2> or <3>, in which a different electrochromic dye is carried for each structural unit. <5> The electrochromic display according to any one of <1> to <4>, wherein at least one of the semiconductor nanoporous layers has a multi-layer structure. <6> The electrochromic display according to <5>, wherein both semiconductor nanoporous layers have a multilayer structure. <7> The electrochromic display according to <5> or <6>, in which semiconductor nanoporous layers are laminated by low temperature firing at 150 to 200 ° C. <8> The electrochromic dye different for each layer of the semiconductor nanoporous layer having a multi-layered structure is <5.
The electrochromic display according to any one of <> to <7>. <9> The electrochromic display according to any one of <1> to <8>, further including a charge transfer agent in the electrolyte layer. <10> The electrochromic display according to any one of <2> to <9>, wherein the charge transfer agent is carried on the semiconductor nanoporous layer. <11> Any one of the above <1> to <10>, wherein the semiconductor fine particles contained in the semiconductor nanoporous layer are selected from a single semiconductor, an oxide semiconductor, a compound semiconductor, an organic semiconductor, a complex oxide semiconductor, and a mixture thereof. The electrochromic display according to claim 2. <12> the complex oxide _{semiconductor,} SnO 2 -ZnO,
_{Nb 2 O 5 -SrTiO 3, Nb} 2 O 5 -Ta 2 O 5,
_{Nb 2 O 5 -ZrO 2, Nb} 2 O 5 -TiO 2, Ti-
_{SnO 2, Zr-SnO 2,} In-SnO 2 and Bi-
The electrochromic display according to <11>, which is selected from SnO ₂ . <13> The above <2> which is obtained by performing heat treatment before supporting the electrochromic dye on the semiconductor nanoporous layer.
The electrochromic display according to any one of <> to <12>. <14> The electrochromic display according to any one of <1> to <13>, wherein the semiconductor nanoporous layer has a thickness of 100 μm or less. <15> The electrochromic dye is the electrochromic display according to any one of <1> to <14>, wherein the electrochromic dye is selected from organic compounds and metal complexes. <16> Full-colorized by any one method selected from an area gradation method by level ground mixing, a density gradation method by level ground mixing, an area gradation method by layer mixing and a density gradation method by layer mixing. To <15>. <17> From <1> to <16, wherein the response speed until reaching the ultimate transmittance or the ultimate absorbance is 100 msec or less.
> Is an electrochromic display.

The EC display according to <1> above,
While arranging a pair of transparent electrodes having a semiconductor nanoporous layer formed on at least one surface so that the semiconductor nanoporous layers face each other, reversible by at least one of electrochemical oxidation reaction and reduction reaction. A plurality of structural units each having a passive matrix panel structure or an active matrix panel structure are laminated by sandwiching an electrolyte layer containing an electrochromic dye that is colored or erased selectively. In the EC display, the EC dye in the electrolyte layer is efficiently permeated to the surface of the semiconductor nanoporous layer formed on the surface of the transparent electrode constituting each structural unit and to the inside and outside of the micropores, thereby responding. The speed is greatly improved, the electrode area can be expanded, and the coloring amount on the electrode is increased, so that the coloring efficiency (the desired coloring density can be reached faster with a lower applied voltage) is improved.

The EC display according to <2> above,
A pair of transparent electrodes having a semiconductor nanoporous layer carrying an electrochromic dye capable of reversibly developing or decoloring by at least one of an electrochemical oxidation reaction and a reduction reaction formed on at least one surface of the semiconductor nanoporous layer. An electrolyte layer is sandwiched between porous layers facing each other, and a plurality of structural units each having a passive matrix panel structure or an active matrix panel structure are laminated. In the EC display, since the EC dye is supported and immobilized on the surface and inside micropores of the semiconductor nanoporous layer formed on the surface of the transparent electrode constituting each structural unit, coloring and decoloring are performed. Since there is no movement of substances (ions), the time for substance movement due to diffusion can be eliminated, the response speed is greatly improved, the electrode area can be expanded, and the amount of dye on the electrode is increased. Coloring efficiency is improved.

The EC display according to <4> above,
In the above <2> or <3>, different EC dyes are carried for each structural unit, and by stacking them, it is possible to easily achieve black coloring or full colorization of the AE element.

The EC display according to <5> above,
In any one of the above items <1> to <4>, at least one of the semiconductor nanoporous layers is formed in a multi-layered structure, which can enhance the coloring intensity and allow each layer to carry a different electrochromic dye. Can easily achieve full color.

The EC display according to <7> above,
150 to 2 in any of the above <5> or <6>
By stacking semiconductor nano-porous layers at a low temperature of 00 ° C, it is possible to efficiently form multi-layer semiconductor nano-porous layers, enabling black color development of AE elements and full-color electronic paper and display devices. Becomes

The EC display according to <8> above,
In any one of the above items <5> to <7>, full-colorization can be easily achieved by supporting different EC dyes in each layer of the semiconductor nanoporous layer formed in the multilayer structure.

The EC display according to <9> above,
In any one of the above items <1> to <8>, by using the EC dye and the charge transfer agent together, both of them can develop color at the same time on the electrode, the color density is increased, and the redox reaction smoothly proceeds. As a result, the response speed is improved.

In the EC display described in <11>, in any one of the above <1> to <10>, the semiconductor fine particles contained in the semiconductor nanoporous layer are a single semiconductor, an oxide semiconductor, a compound semiconductor, an organic semiconductor. By using a semiconductor, a complex oxide semiconductor, or a mixture thereof, a semiconductor nanoporous layer having micropores on the surface and inside can be formed, and the EC dye adsorption amount is increased to improve the response speed and the coloring efficiency. To do.

The EC display according to the above <13> is the EC display according to any one of the above <2> to <12>.
By performing heat treatment before supporting the dye on the semiconductor nanoporous layer, water and other impurities adsorbed on the surface of the semiconductor nanoporous layer can be removed, and the surface of the porous layer can be activated, and the EC dye Adsorption can be performed efficiently.

In the EC display described in <14>, in any one of the above <1> to <13>, the semiconductor nanoporous layer has a thickness of 100 μm or less, so that transparency is not deteriorated. The amount of EC dye that can be adsorbed can be increased, and the coloring efficiency can be improved.

The EC display described in <16> is the same as any one of <1> to <15>, in which an area gradation method by level ground mixing, a density gradation method by level ground mixing, and an area gradation method by layer mixing are used. By adopting any one method selected from the density gradation method based on the above-mentioned mixing and lamination, full-colorization can be easily achieved.

[0020]

BEST MODE FOR CARRYING OUT THE INVENTION The EC display of the present invention is
(1) A pair of transparent electrodes, each having a semiconductor nanoporous layer formed on at least one surface thereof, are arranged such that the semiconductor nanoporous layers face each other, and an electrolyte layer containing an EC dye is sandwiched between the transparent electrodes. An EC display formed by stacking a plurality of structural units each having a passive matrix panel structure or an active matrix panel structure,
(2) A pair of transparent electrodes, each having a semiconductor nanoporous layer supporting an EC dye formed on at least one surface thereof, are arranged such that the semiconductor nanoporous layers face each other, and an electrolyte layer is sandwiched between the transparent electrodes. And an EC display in which a plurality of structural units each having a passive matrix panel structure or an active matrix panel structure are laminated. The EC display is either a transmissive type that has a light source such as a backlight inside the display, a reflective type that uses external light such as sunlight as a light source, or a semi-transmissive type that is a combination of the former two. I don't mind. Further, the EC display may be a monochromatic color type or a multicolor type full color type.

1 to 3 show a monochromatic passive matrix panel, in which (A) is a perspective view and (B) is a schematic sectional view. 1 (A) and 1 (B) show a conventional monochromatic color passive matrix panel in which a semiconductor nanoporous layer is not formed on the surface of a transparent electrode, which panels are parallel to each other on a pair of glass substrates 12 and 12. The strip-shaped transparent electrodes 5 and 5 (for example, ITO electrodes) arranged in the above are provided, and the electrolyte 9a containing the EC dye is arranged between the transparent electrodes 5 and 5. 2A and 2B show an example of a monochromatic color passive matrix panel of the present invention, in which strip-shaped transparent electrodes 5 and 5 (for example, (ITO electrode), and the pair of semiconductor nanoporous layers 8 and 8 are arranged between the transparent electrodes 5 and 5 with the electrolyte layer 9 interposed therebetween. 3 (A) and 3 (B) show an example of the monochromatic color passive matrix panel of the present invention.
2, 12 have strip-shaped transparent electrodes 5, 5 (for example, ITO electrodes) arranged in parallel with each other, and the transparent electrodes 5, 5
The semiconductor nanoporous membranes 8 and 8 are laminated on top of this, and the electrolyte layer 9 is sandwiched between the electrodes having the semiconductor nanoporous membrane on the pair of surfaces. The semiconductor nanoporous film may be formed only on one of the transparent electrodes. Further, the EC dye may be adsorbed on both electrodes or only one of them may be adsorbed, or the EC dye may be adsorbed on one side and the colorless redox substance may be adsorbed on the other side.

4 to 6 show a full-color type passive matrix panel, in which (A) is a perspective view and (B) is a schematic sectional view. 4 (A) and 4 (B) show an example of a full-color type passive matrix panel of the present invention, in which strip-shaped transparent electrodes 5 and 5 (for example, ITO electrodes) arranged in parallel to each other on a glass substrate 12. And a semiconductor nanoporous film 8 is provided on one transparent electrode 5 and sequentially supports a red (R) coloring EC dye, a green (G) coloring EC dye and a blue (B) coloring EC dye. Then, the electrolyte layer 9 is interposed between the other transparent electrode 5.
5A and 5B show an example of a full-color type passive matrix panel of the present invention, and in FIG.
In order to increase the efficiency of the redox reaction on the counter electrode, the semiconductor nanoporous film 8a is also provided on the counter electrode to adsorb a colorless redox substance. FIGS. 6A and 6B show an example of a full-color type passive matrix panel of the present invention, in which color is developed at both electrodes to improve the coloring efficiency and response efficiency. That is, the semiconductor nanoporous film 8 is provided on one transparent electrode 5, and the red (R) coloring EC dye, the green (G) coloring EC dye, and the blue (B) coloring EC dye are carried in order, and The semiconductor nanoporous film 8 is provided in a dot shape on the counter electrode so as to be orthogonal to each other, the EC dye is adsorbed so that the colors match, and the electrolyte layer 9 is interposed.

In the passive matrix panel, for example, a positive electrode line formed of a plurality of positive electrodes and a negative electrode line formed of a plurality of negative electrodes intersect each other in a substantially orthogonal direction to form a circuit. The semiconductor nanoporous film, which is located at each intersection and carries the EC dyes for red color, green color, and blue color, functions as a pixel, and there are a plurality of EC dyes corresponding to each pixel. . In the passive matrix panel, when a current is applied to one of the positive electrodes in the positive line and one of the negative lines in the negative line by the constant current source, the current is applied to the EC dye located at the intersection, The EC dye at the position develops color. By controlling the color development for each pixel, a full-color image can be easily formed.

FIG. 7 shows an example of a monochromatic active matrix panel of the present invention. The TFT substrate 20 has a glass substrate on which scanning lines, data lines and current supply lines are formed in a grid pattern. It has a positive electrode 23 (for example, an ITO electrode) that is connected to a scanning line that forms an eye shape, can be driven by a TFT circuit that is arranged in each grid, and is arranged in each grid. In the panel of FIG. 7, the EC dye is not adsorbed on the TFT substrate side, the semiconductor nanoporous film 8 is provided on the glass substrate 12 on the negative electrode side so as to cover the whole, and the EC dye is adsorbed on the film. The electrolyte layer 9 is interposed between the positive and negative electrodes. FIG. 8 shows an example of the monochromatic active matrix panel of the present invention.
In the above, the semiconductor nanoporous film 8 is provided on the positive electrode 23 of the TFT substrate, the EC dye is adsorbed on this, and the electrolyte layer 9 is interposed between the positive and negative electrodes. FIG. 9 shows an example of a full-color type active matrix panel of the present invention, in which a semiconductor nanoporous film 8 is provided on a positive electrode 23 of a TFT substrate, and a red (R) coloring EC dye and a green (G) coloring are provided for each pixel. An EC dye and a blue (B) coloring EC dye are carried in order, and a semiconductor nanoporous film 8a is provided on the glass substrate 12 on the negative electrode side so as to cover the whole, and a colorless redox substance is adsorbed to form an electrolyte. The layer 9 is interposed. FIG. 10 shows an example of a full-color type active matrix panel of the present invention, in which a semiconductor nanoporous film 8 is provided on a positive electrode 23 of a TFT substrate, and a red (R) coloring EC dye and a green (G) coloring are provided for each pixel. The EC dye and the blue (B) color-developing EC dye are carried in order, and the semiconductor nanoporous film 8 is patterned in a dot shape on the negative electrode side so that the EC dye and the positive electrode match in color for each dot (pixel). It is made to adsorb | suck to, and the electrolyte layer 9 is interposed.

In the active matrix panel, for example, a plurality of scanning lines provided in parallel and a plurality of data lines and current supply lines provided in parallel are orthogonal to each other to form a grid pattern. A circuit is formed by connecting the switching TFT and the driving TFT to the eyes. When a current is applied from the driving circuit, the switching TFT and the driving TFT can be driven for each grid. And each grid is for red coloring,
Each of the EC dyes for green color development and blue color development functions as a pixel, and in the active matrix panel, a driving circuit is provided for one of the scanning lines arranged in the horizontal direction and the current supply line arranged in the vertical direction. When current is applied from
At that time, the switching TFT located at the intersection is driven, and the driving TFT is driven accordingly, and the E
C dye develops color. By controlling the color development for each pixel, a full-color image can be easily formed.

In the EC element constituting the EC display, a pair of transparent electrodes each having a semiconductor nanoporous layer formed on at least one surface thereof are arranged so that the semiconductor nanoporous layers face each other, and Sandwiching the layers,
An EC dye is contained in the electrolyte layer, or an EC dye is carried on the semiconductor nanoporous layer. Hereinafter, each component will be described in detail.

A plurality of structural units constituting the EC display, preferably 2 to 4 are laminated, and the coloring intensity can be adjusted by carrying the same kind of EC dye for each structural unit, and the coloring intensity can be adjusted. Can be enhanced.
Further, full-colorization can be easily achieved by supporting EC dyes of different colors (for example, three primary colors of blue, green and red) for each structural unit.

-Semiconductor Nanoporous Layer- The semiconductor nanoporous layer is formed on the surface of at least one, preferably both, of the pair of transparent electrodes, and in order to increase the surface area, an EC dye, It has fine pores capable of supporting a charge transfer agent as needed.

The specific surface area of the semiconductor nanoporous layer is 1
~ 5000 m < ² > / g is preferable, and 10-2500 m < ² > /
g is more preferred. Here, the specific surface area means the BET specific surface area obtained from the adsorption amount of nitrogen gas. If the specific surface area is too small, the amount of EC dye adsorbed may be increased, and the object of the present invention may not be achieved.

In the semiconductor nanoporous layer, at least one of the pair of transparent electrodes, preferably both of them, is formed in a multilayer structure, for example, a 2 to 4 layer structure, and the semiconductor nanoporous layer of the multilayer structure is of the same kind. By supporting the EC dye, the coloring intensity can be adjusted and the coloring intensity can be enhanced. Further, full-colorization can be easily achieved by carrying EC dyes of different colors (for example, the three primary colors of blue, green, and red) on each layer of the semiconductor nanoporous layer having a multilayer structure.

In the EC device of the present invention, a plurality of structural units are laminated, so that the semiconductor nanoporous layer may be formed in a multi-layered structure if necessary, and the coloring intensity may be adjusted more efficiently. , Full color can be easily achieved.

The semiconductor fine particles contained in the semiconductor nanoporous layer are not particularly limited and can be appropriately selected according to the purpose. For example, a single semiconductor, an oxide semiconductor, a compound semiconductor, an organic semiconductor, a complex oxide semiconductor,
Alternatively, a mixture thereof may be used, and these may contain impurities as a dopant. There is no particular limitation on the form of the semiconductor, and it may be single crystal, polycrystal, amorphous, or a mixed form thereof.

Examples of the single semiconductor include silicon (Si), germanium (Ge), tellurium (Te),
And so on.

The oxide semiconductor is a metal oxide and has a semiconductor property, for example, TiO ₂ , Sn.
O ₂ , Fe ₂ O ₃ , SrTiO ₃ , WO ₃ , ZnO, Z
rO ₂ , Ta ₂ O ₅ , Nb ₂ O ₅ , V ₂ O ₅ , In ₂ O
₃ , CdO, MnO, CoO, TiSrO ₃ , KTiO
₃ , Cu ₂ O, sodium titanate, barium titanate, potassium niobate, and the like.

Examples of the compound semiconductor include cadmium sulfide, zinc sulfide, lead sulfide, silver sulfide, antimony sulfide, bismuth sulfide, cadmium selenide, lead selenide. , Cadmium telluride, zinc phosphide, gallium phosphide, indium phosphide, cadmium phosphide, gallium-arsenide selenide, copper-indium selenide, copper-indium sulfide, etc. To be

Examples of the organic semiconductor include polythiophene, polypyrrole, polyacetylene, polyphenylene vinylene, polyphenylene sulfide, and the like.

Examples of the complex oxide semiconductor include SnO ₂ —ZnO, Nb ₂ O ₅ —SrTiO ₃ and N.
_{b 2 O 5 -Ta 2 O 5} , Nb 2 O 5 -ZrO 2, Nb 2
_{O 5 -TiO 2, Ti-SnO} 2, Zr-SnO 2, B
_{i-SnO 2, In-SnO} 2, and the like. The SnO ₂ —ZnO is composed of relatively large ZnO particles (particle size: about 0.2 μm) and the surrounding is coated with SnO ₂ ultrafine particles (particle size: about 15 nm). SnO ₂ : ZnO = 70: 30 to 30:70 is preferable. The Nb ₂ O ₅ —SrTiO 3
_{3, Nb 2 O 5 -Ta 2} O 5, Nb 2 O 5 -ZrO 2,
And _Nb 2 _{O 5} complex, such as _{Nb 2 O} 5 -TiO 2, the
It is compounded so that the mass ratio with Nb ₂ O ₅ is 8: 2 to 2: 8.

The shape of the semiconductor fine particles is not particularly limited and may be appropriately selected according to the purpose. It may be spherical, nanotube-shaped, rod-shaped or whisker-shaped, and may have different shapes. It is also possible to mix more than one type of fine particles. In the case of the spherical particles, the average particle size is preferably 0.1 to 1000 nm, more preferably 1 to 100 nm. It should be noted that two or more kinds of fine particles having different particle size distributions may be mixed. In the case of the rod-shaped particles, the aspect ratio is preferably 2 to 50000, and 5 to 2
5000 is more preferable.

The method for forming the semiconductor nanoporous layer is not particularly limited and may be appropriately selected depending on the type of semiconductor. For example, metal anodization method, cathodic deposition method, screen printing method, sol-gel method. Method, thermal oxidation method, vacuum vapor deposition method, dc and rf sputtering method, chemical vapor deposition method, metalorganic chemical vapor deposition method, molecular beam deposition method, laser ablation method, etc., and a combination of the above methods. The semiconductor nanoporous layer can also be prepared.

-Method for forming oxide semiconductor nanoporous layer-Forming oxide semiconductor (metal oxide) nanoporous layer 1
One method is to react the metal oxide precursor in a solution containing a metal oxide precursor and a compound having one or more functional groups that interact with the metal oxide precursor to form a composite gel. Then, the first step of obtaining a colloidal dispersion sol composed of metal oxide fine particles, and applying the sol to a support,
A second step of drying or firing this to form a semiconductor nanoporous layer having fine pores on the transparent conductive film on the transparent insulating substrate (hereinafter referred to as “composite gelation method”). Sometimes.)

In the first step, the formation reaction of metal oxide fine particles proceeds in the gel whose diffusion is regulated, so that formation of coarse particles and sedimentation of particles do not occur, and fine particles having a small particle diameter become uniform. It is possible to obtain a dispersed colloidal dispersion sol solution. In the so-called sol-gel method, when the metal oxide precursors are, for example, metal alkoxides, they undergo gelation by hydrolysis or dehydration condensation reaction.
A network of chemically strong three-dimensional bonds of -OM- (where M is a metal element and O is an oxygen element) is formed, cannot be re-solified, and once gelled. Then, it cannot be processed by means such as coating. On the other hand, in the method of obtaining a composite gel by reacting the metal oxide precursor in a solution containing the metal oxide precursor and a compound that interacts with the metal oxide precursor, By utilizing the interaction property of the compound that interacts with the body, it can be made into a sol again, and excellent processability can be provided.

Here, as the metal oxide precursor,
Examples thereof include metal compounds such as metal halides, metal complex compounds, metal alkoxides, metal carboxylates or chelate compounds which are soluble in the solvent used. Specific compounds include, for example, TiCl ₄ (titanium tetrachloride), ZnCl ₂ (zinc chloride), WCl ₆ (tungsten hexachloride), SnCl ₂ (stannous chloride), SrCl.
Metal halides such as ₆ (strontium chloride), Ti
(NO ₃ ) ₄ (titanium nitrate), Zn (NO ₃ ) ₂ (zinc nitrate), Sr (NO ₃ ) ₂ (strontium nitrate) and other nitrates, and the general formula M (OR) _n (where M is a metal element). ,
R is an alkyl group, and n is the oxidation number of the metal element. ) And metal alkoxides.

Examples of the metal alkoxide include:
Examples thereof include zinc diethoxide, tungsten hexaethoxide, vanadyl ethoxide, tin tetraisopropoxide, and strontium diisop.

For example, when a metal oxide layer of titanium oxide is formed, examples of the metal alkoxide include titanium tetraisopropoxide, titanium tetranormal propoxide, titanium tetraethoxide, titanium tetranormal butoxide, titanium tetraisobutoxide. , Titanium tetratert-butoxide and the like can be preferably used.

Examples of the functional group that interacts with the metal oxide precursor include a carboxyl group, an amino group and a hydroxyl group. The functional group that interacts with the metal oxide precursor may be one having one or more of the above functional groups such as an amic acid structure. The compound having at least one functional group that interacts with the metal oxide precursor is a carboxyl group, an amino group, a hydroxyl group,
It is a compound having one or more functional groups selected from the amino acid structure. Particularly preferred are polymer compounds. Specific examples of such low molecular weight compounds include dicarboxylic acid,
Examples thereof include diamine, diol, diamic acid and the like.

Further, as a specific example of the polymer compound, a functional group selected from a carboxyl group, an amino group, a hydroxyl group and an amic acid structure is attached to the main chain, side chain or cross-linking portion.
Examples of the polymer compound include one or more species. The main chain structure of the polymer compound is not particularly limited, polyethylene structure, polystyrene structure, polyacrylate structure, polymethacrylate structure, polycarbonate structure, polyester structure, cellulose structure, Examples thereof include those having any structure such as a silicone structure, a vinyl polymer structure, a polyamide structure, a polyamideimide structure, a polyurethane structure, a polyurea structure, or a copolymer structure thereof.

Further, the polymer compound having at least one functional group selected from the above-mentioned carboxyl group, amino group, hydroxyl group and amic acid structure in the main chain, side chain or crosslinked portion is a metal oxide precursor. The use of polyacrylic acid having a carboxyl group in the side chain is particularly preferable from the viewpoint that the form of interaction is appropriate. Further, the polymer compound having at least one kind of functional group that interacts with the metal oxide precursor has a carboxyl group, an amino group, a hydroxyl group, and an amic acid structure with a polymer compound having a functional group that interacts. It may be a copolymer with a polymer compound having the same main chain structure as described above. The polymer compound having one or more kinds of functional groups that interact with the metal oxide precursor has a mixed system of two or more kinds, or has a carboxyl group, an amino group, a hydroxyl group, or an amic acid structure, depending on the purpose. Alternatively, a mixed system with a polymer compound having the same main chain structure as described above may be used. The average degree of polymerization of the polymer compound having at least one functional group that interacts with the metal oxide precursor is 10
0 to 10,000,000 is preferable, and 5000 to 25
0000 is more preferable.

As the solvent, alcohols such as methanol, ethanol, isopropanol and butanol, and metal oxide precursors such as formamide, dimethylformamide, dioxane and benzene are dissolved but do not react with the metal oxide precursor. Anything can be used.

The method for forming the semiconductor nanoporous layer will be described in detail below, taking the case of using a metal alkoxide as the metal oxide precursor as an example.

First, the metal alkoxide is added to the solvent (for example, an organic solvent such as alcohol). Further, water necessary for partially hydrolyzing the metal alkoxide and acids such as hydrochloric acid, nitric acid, sulfuric acid or acetic acid as a catalyst are added. The amount of water and acids added here is
It can be appropriately selected depending on the degree of hydrolysis of the metal alkoxide used. Next, the resulting mixed solution is stirred at room temperature to 150 ° C. under a stream of dry nitrogen.
(Preferably, room temperature to 100 ° C.) is heated (or refluxed). The reflux temperature and time can also be appropriately selected according to the hydrolyzability of the metal oxide precursor used. As a result of the reflux, the metal alkoxide is in a partially hydrolyzed state. That is, since the amount of the water contained in the mixed solution is so small as not to sufficiently hydrolyze the alkoxyl group of the metal alkoxide, the metal alkoxide represented by the general formula M (OR) _n is used. In, all of the -OR groups are not hydrolyzed, resulting in a partially hydrolyzed state. The polycondensation reaction does not proceed in the partially hydrolyzed metal alkoxide. Therefore, even if a chain of -MO-M- is formed between the metal alkoxides, the metal alkoxides are in an oligomer state. The mixed solution containing the metal alkoxide in the oligomer state after the reflux is colorless and transparent and has almost no increase in viscosity.

Next, the temperature of the mixed solution after the reflux is lowered to room temperature, and the mixed solution has at least one functional group selected from a carboxyl group, an amino group, a hydroxy group and an amino acid structure (preferably a polymer compound. Is polyacrylic acid). In this case, the polymer compound, which is originally difficult to dissolve in an organic solvent such as alcohol, is easily dissolved in this mixed solution to obtain a transparent sol. It is considered that this is because the carboxyl group of the polymer compound and the metal alkoxide are bonded by a salt forming reaction to form a polymer complex compound. This transparent sol is usually
It is a colorless and transparent homogeneous solution.

An excess amount of water was further added to this transparent sol,
By maintaining the temperature at room temperature to 150 ° C., preferably at room temperature to 100 ° C. and further continuing the reaction, the transparent sol gels in about several minutes to one hour, and a cross-linked structure of the polymer compound and the metal alkoxide. A composite gel with is formed.

When the obtained composite gel is further kept at room temperature to 90 ° C. (usually about 80 ° C.) for 5 to 50 hours to continue the reaction, the composite gel is dissolved again and the semitransparent metal oxide fine particle colloidal dispersion sol. Is obtained. This is because, as the polycondensation reaction proceeds due to the hydrolysis reaction of the metal alkoxide, the salt structure of the polymer compound and the metal alkoxide is decomposed and converted into metal oxide fine particles and carboxylic acid ester. It is due to.

The semi-transparent metal oxide fine particle colloidal dispersion sol obtained above is applied to a transparent conductive film deposited on a transparent insulating substrate, and then dried or baked,
A metal oxide film having fine pores is formed.

The coating method can be carried out by a known method without particular limitation. Specific examples thereof include a dip coating method, a spin coating method, a wire bar method and a spray coating method. For drying, for example, air drying, drying performed using a dryer such as an oven, or vacuum freeze drying can be performed. Alternatively, a method of evaporating the solvent using a device such as a rotary evaporator may be used. In this case, the drying temperature, time and the like can be appropriately selected according to the purpose.

Depending on the drying temperature, the polymer compound or its reaction product may not be removed only by drying the metal oxide fine particle colloidal dispersion sol (removing the liquid component containing the solvent). In such a case, it is preferable to perform calcination in order to further remove them to obtain a pure metal oxide. The firing can be performed using, for example, a furnace, and the firing temperature varies depending on the type of the polymer compound having the functional group used, but a low temperature is suitable for achieving a multilayer structure. , About 100 ℃ -700
C. is preferable, and 100.degree. C. to 400.degree. C. is more preferable.

The firing causes crystallization of the metal oxide fine particles and sintering of the metal oxide fine particles, and at the same time, the organic polymer component is thermally decomposed and disappears.

In the formation of the semiconductor nanoporous layer, the formation reaction of the metal oxide fine particles proceeds in the composite gel in which the diffusion is restricted, so that the formation of coarse particles and the aggregation due to the sedimentation of the particles do not occur. It is possible to obtain a metal oxide fine particle colloidal dispersion sol in which ultra fine particles having a small particle size are uniformly dispersed.

Regarding the size of the metal oxide fine particles in the semiconductor nanoporous layer, the period of the metal oxide fine particle agglomerate structure, the volume ratio of the metal oxide fine particle agglomerate phase to the void phase, and the like, for example, the metal oxide Addition amount of a compound having at least one functional group that interacts with the metal oxide precursor to the precursor, and a compound having at least one functional group that interacts with the metal oxide precursor and the metal oxide precursor The ratio can be controlled to a desired degree by the ratio of the solid components of the above and the total mixed solution.

That is, when the addition amount of the metal oxide precursor and the compound having at least one functional group to be baked is increased, the volume ratio of the void phase in the obtained semiconductor nanoporous layer is increased, and the metal oxide precursor is added. When the ratio of the solid component of the compound and the compound having at least one functional group that interacts with the metal oxide precursor is reduced with respect to the entire mixed solution, the period of the obtained metal oxide fine particle agglomerate structure becomes small, and voids are formed. Although the density of the phase increases, the size of the metal oxide fine particles themselves increases.

The addition amount of the compound having at least one functional group that interacts with the metal oxide precursor to the metal oxide precursor varies depending on the ratio of the solid component to the entire mixed solution and can be appropriately selected. In general, the mass ratio is preferably 0.1 to 1, and more preferably 0.2 to 0.8. If the addition amount of the compound having at least one functional group that interacts with the metal oxide precursor to the metal oxide precursor is reduced, a dense semiconductor nanoporous layer with few macropores is likely to be formed, and the above mass ratio Is less than 0.1,
The complex gel may not be redissolved because a large three-dimensional network of -MOM is formed. On the other hand, if the addition amount is increased to exceed 1, on the other hand, a relatively large void is generated and a transparent semiconductor nanoporous layer tends to be formed.

The ratio of the solid component to the entire mixed solution varies depending on the addition amount of the metal oxide precursor and the compound having at least one functional group that interacts with the metal oxide precursor, and is appropriately selected. It is possible, but generally 1 to 10 mass% is preferable, and 2 to 5 mass% is more preferable. When the ratio is less than 1% by mass, the progress of the complex gelation reaction is slow, and the metal oxide fine particles are formed in a transparent sol state having high fluidity, and coarse particles are formed. If it exceeds%, the progress from the transparent sol to the composite gel is rapid and a uniform composite gel may not be obtained.

The method for forming the tungsten oxide porous layer will be described in more detail below by taking the case of using tungsten hexaethoxide as the metal alkoxide as an example.

First, tungsten hexaethoxide is added to alcohol to prepare a mixed solution. At this time, water and an acid as a catalyst are added to the alcohol. The water is about 0.1 times to equimolar to the tungsten hexaethoxide, and the acid is converted to the tungsten hexaethoxide. It is preferable to add about 0.05 times to 0.5 times the mol of each. Room temperature ~
Reflux under a stream of dry nitrogen with stirring at 80 ° C. The reflux temperature and time here are preferably 80 ° C. and about 30 minutes to 3 hours. As a result of this reflux, a transparent mixed solution is obtained.

In this mixed solution, tungsten hexaethoxide is in a partially hydrolyzed state and in an oligomer state. The temperature of this mixed solution is lowered to room temperature, and polyacrylic acid is added. Polyacrylic acid, which is essentially insoluble in alcohol, is easily dissolved in this mixed solution to obtain a colorless transparent sol. This is because the carboxylic acid of polyacrylic acid and tungsten hexaethoxide are bound by a salt forming reaction to form a polymer complex compound. When an excess amount of water is further added to this transparent sol and the temperature is maintained at room temperature to 80 ° C., the transparent sol gels in several minutes to 1 hour, and a composite having a crosslinked structure containing at least polyacrylic acid and tungsten hexaethoxide. A gelling is formed.

When this composite gel is kept at about 80 ° C. for 5 to 50 hours, the composite gel is dissolved again and a translucent sol is obtained. This is because, as the hydrolysis reaction and polycondensation reaction of tungsten hexaethoxide proceed, the salt structure of polyacrylic acid and tungsten hexaethoxide decomposes and changes into titanium oxide and carboxylic acid ester. .

The obtained sol solution is applied to a suitable substrate by a dip coating method or the like, and the temperature is about 100 ° C to 60 ° C.
Heat to a high temperature of 0 ° C. By this heating, crystallization of the tungsten oxide fine particles and sintering of the tungsten oxide fine particles proceed at the same time, and at the same time, the polymer phase is thermally decomposed to form film-shaped tungsten oxide fine particles in which tungsten oxide is aggregated in a phase-separated state. Becomes

The mass ratio of polyacrylic acid to tungsten hexaethoxide is preferably 0.3 to 0.7. When the mass ratio is less than 0.3, -MO.
A three-dimensional network having a large -M- may be formed and the gel may not be dissolved. If the mass ratio exceeds 0.7, a relatively large void may be formed to form a transparent layer.

The ratio of solid components of tungsten hexaethoxide and polyacrylic acid to the total mixed solution is preferably 1 to 10% by mass. When the ratio is less than 1% by mass, the progress of the complex gelation reaction is slow,
Tungsten oxide fine particles may be formed in a sol state having high fluidity, and coarse tungsten oxide fine particles may be formed. On the other hand, if it exceeds 10% by mass, the progress from the transparent sol to the composite gel is rapid and a uniform composite gel may not be obtained.

-Method for forming compound semiconductor nanoporous layer-As a method for forming the compound semiconductor nanoporous layer, there are electrolytic deposition method, chemical bath deposition method, photochemical deposition method and the like. It is shown.

(Electrolytic deposition method) In the electrolytic deposition method, an electrode having a transparent conductive film formed on a transparent insulating substrate in an electrolyte containing at least ions of an element to be deposited, and an electrode facing the electrode. And an electrochemical oxidation-reduction reaction are caused between these electrodes to form the compound semiconductor layer on the electrode on which the transparent conductive film is formed (Surface Technology V
ol. 49, No. 13 pages 1998).

The compound semiconductor produced in this step is, for example, CuGaS ₂ (copper gallium sulfide) or CuGaSe.
₂ (copper gallium selenide), CuGaTe ₂ (copper gallium telluride), CuInS ₂ (copper indium sulfide), C
uInSe ₂ (copper indium selenide), CuInTe
₂ (copper indium telluride), AgInS ₂ (silver indium silver sulfide), AgInSe ₂ (silver indium selenide), AgInTe ₂ (silver indium telluride), Zn
Se (zinc selenide), ZnTe (zinc telluride), C
dTe (cadmium telluride), Cu ₂ S (copper sulfide),
Cu ₂ Se (selenium copper), and the like.

As the electrolyte, a mixture of solutes such as sulfates and chlorides as raw material elements in a solvent is used, and water (pure water, distilled water, etc.) is used as a solvent of the electrolyte. However, when a voltage that hydrogen is generated by electrolysis of water is applied to the base, the solvent may be an organic substance as a non-aqueous solution. As the organic solvent, acetonitrile, dimethylformamide, propylene carbonate or the like can be used. The non-aqueous solution may use an inorganic non-aqueous solution such as liquid ammonia or liquid sulfur dioxide as the solvent.

The solute may be one that contains an element such as a sulfate or chloride that constitutes a compound semiconductor to be deposited on the electrode, and is soluble in the solvent. Examples of the sulfate include cuprous sulfate, indium sulfate, gallium sulfate, silver sulfate, zinc sulfate, cadmium sulfate and the like. Examples of chlorides include compounds such as cuprous chloride, indium chloride, gallium chloride, silver chloride, zinc chloride, and cadmium chloride, which are used as reduced solutes. The solute is not limited to the above compounds,
They may be used alone or in combination of two or more. As the solute, selenium oxide, selenium hydrogen oxide, tellurium oxide, tellurium hydrogen oxide, sodium thiosulfate, thiourea and the like can be used as an oxidized solute.

When the above-mentioned oxidized solute is used, by adjusting the hydrogen ion concentration, the deposition of elemental ions contained in the oxidized solute can be promoted. The hydrogen ion concentration can be adjusted with a regulator such as sulfuric acid or hydrochloric acid. The hydrogen ion concentration adjusted by the adjusting agent is preferably pH 0.9 to 4.0 and pH 1.5.
~ 2.5 is more preferable.

As the electrolyte, in addition to the above compounds, a supporting electrolyte composed of an inert substance that does not participate in electrolytic reduction may be added to the electrolyte in order to obtain conductivity of the electrolyte. Examples of the supporting electrolyte include NaClO ₄ (sodium chlorate) and LiClO ₄ (lithium chlorate). The supporting electrolyte is 0.05 to 1 mol /
It is preferable to include 1 amount.

Additives may be added to the electrolyte in order to improve the adhesion required when the deposition of the compound semiconductor proceeds. Examples of the additives include amines, alkaloids, sulfonic acids, mercaptans and sulfides.

To apply a voltage between the opposing electrodes arranged in the electrolyte, a reference electrode can be used with the third electrode as a voltage reference electrode. A reference electrode can also be used to control a constant voltage or current between the opposing electrodes. As the reference electrode, a standard hydrogen electrode, a saturated calomel electrode, a standard silver-silver chloride electrode, a standard mercury oxide electrode or the like can be used.

As the electrode facing the porous semiconductor layer arranged in the electrolyte, a material which is hardly dissolved by applying a voltage in a solution, that is, a material having a small ionization tendency can be used. For example, platinum (Pt), gold (A
u), silver (Ag), and the like.

The voltage applied between the opposing electrodes arranged in the electrolyte may be lower than the redox potential of the element ion of the compound containing the element constituting the compound semiconductor to be deposited contained in the electrolyte. preferable.

The content of the compound contained in the electrolyte is 5
Is preferably 400 to 400 mmol / l, more preferably 5 to 20 mmol / l in the reduction type element ion deposition, and more preferably 100 to 400 mmol / l in the oxidation type element ion deposition. 20-100 degreeC is preferable and, as for the temperature of the said solution, 22-70 degreeC is more preferable.

The voltage application time for forming the compound semiconductor layer is preferably 300 to 3600 seconds, more preferably 800 to 2400 seconds.

The compound semiconductor deposited in the above step is baked and crystallized. The crystallization temperature depends on the kind of the compound semiconductor to be deposited, but is preferably 50 to 600 ° C.
50-600 degreeC is more preferable. The crystallization time is 1 to
60 minutes are preferable and 15 to 30 minutes are more preferable.

(Chemical bath deposition method) In the chemical bath deposition method, an electrode having a transparent conductive film formed on a transparent insulating substrate is placed in a solution containing at least one kind of ions to be deposited,
A compound semiconductor layer is formed on an electrode by causing a reduction reaction by adjusting the temperature of the solution and adjusting the ion concentration (Journal of Applied Phys).
ics, vol. 82, 2, 655, 1997).

In this chemical bath deposition method, elemental ions are generated by an oxidizing agent or a reducing agent, a complexing agent is used to stabilize the ions, a buffering agent is used to prevent fluctuations in hydrogen ion concentration, and By adding a stabilizer or the like for preventing spontaneous decomposition, the compound semiconductor can be deposited on the electrode on which the transparent conductive film is formed by the redox reaction thereof.
The compound semiconductor produced in this step is not particularly limited, but ZnSe (zinc selenide), ZnTe (zinc telluride), CdTe (cadmium telluride), Cu
₂ S (copper sulfide), _Cu 2 Se (selenium copper), and the like.

The solution used is a mixture of solutes such as sulfates and chlorides which become ions in a solvent. Water (pure water, distilled water, etc.) or the like is used as the solvent. An organic solvent can also be used, and for example, acetonitrile, dimethylformamide, propylene carbonate, etc. can be used. It is also possible to use an inorganic non-aqueous solution such as liquid ammonia or liquid sulfur dioxide.

The solute may be any so long as it contains an element such as a sulfate or a chloride that constitutes the compound semiconductor to be deposited on the electrode on which the transparent conductive film is formed. Examples of the sulfate include cuprous sulfate, indium sulfate, gallium sulfate, silver sulfate, zinc sulfate, cadmium sulfate and the like. Examples of chlorides include cuprous chloride, indium chloride, gallium chloride, silver chloride, zinc chloride and cadmium chloride. As the solute, selenium oxide, selenium hydrogen oxide, tellurium oxide, tellurium hydrogen oxide, sodium thiosulfate, thiourea and the like can also be preferably used.

When a compound as described above is used, adjusting the hydrogen ion concentration can promote the deposition of elemental ions contained in the compound. As the adjusting agent for adjusting the hydrogen ion concentration, for example, a basic compound such as sodium hydroxide or ammonium hydroxide, an inorganic acid, an organic acid or the like can be used. Further, the buffer used to suppress the fluctuation of the hydrogen ion concentration, sodium citrate sodium acetate, those of the oxycarboxylic acid type, those having a small dissociation constant of inorganic acids such as boric acid or carbonic acid, Alkali salts of organic and inorganic acids can be used. Further, as a complexing agent, ammonium hydroxide,
Sodium citrate, sodium acetate, ethylene glycol and the like can be used.

As the stabilizer, lead chloride, sulfide, or nitric acid can be used. The concentration of the compound containing the raw material element of the compound semiconductor in the solution is 1.0 × 10 ^−3.
~ ² mol / l is preferable, and 2.0 x 10 ^{-2 to 1} mo.
1 / l is more preferred.

The temperature of the solution is preferably 20 to 100 ° C, more preferably 22 to 70 ° C. The formation time of the compound semiconductor layer is preferably 300 to 3600 seconds, and 1
200 to 2400 seconds is more preferable.

The compound semiconductor layer deposited in the above step is baked and crystallized. The crystallization temperature depends on the kind of the compound semiconductor to be deposited, but is preferably 50 to 600 ° C.,
150-550 degreeC is more preferable. The crystallization time is 1
-60 minutes are preferable, and 15-30 minutes are more preferable.

(Photochemical Deposition Method) In the photochemical deposition method, an electrode having a transparent conductive film formed on a transparent insulating substrate is placed in a solution containing at least one kind of sodium thiosulfate and one or more metal ions, and the electrode is attached to the electrode. The compound semiconductor layer is formed on an electrode by irradiating ultraviolet rays to cause a photoreaction (Japan Journal Applied Ph).
ysics vol36, L1146 1997).

In this photochemical deposition method, a compound formation reaction is caused by photoexcitation of ions (thiosulfate ions, etc.) in a solution, and the film thickness can be easily controlled by the presence or absence of light irradiation and the intensity change. The compound semiconductor produced in this step is not particularly limited, but CuGaS ₂ (copper gallium sulfide), CuInS ₂ (copper indium sulfide), AgI
Examples include nS ₂ (silver indium sulfide) and Cu ₂ S (copper sulfide).

The solution used is a mixture of solutes such as sulfates and chlorides which become ions in a solvent. The solute may be any so long as it contains an element such as a sulfate or chloride that constitutes the compound semiconductor to be deposited on the electrode. Examples of the sulfate include cuprous sulfate, indium sulfate, gallium sulfate, cadmium sulfate and the like. Examples of chlorides include cuprous chloride, indium chloride, gallium chloride and cadmium chloride.

The solute is not limited to the above compounds and may be used alone or in combination of two or more. When the above-mentioned oxidation type compound is used, by adjusting the hydrogen ion concentration, it is possible to promote the deposition of the element ions contained in the oxidation type compound. The hydrogen ion concentration can be adjusted with a regulator such as sulfuric acid. The hydrogen ion concentration adjusted by the adjusting agent is preferably pH 1.5 to 4.0, and pH 2.5 to 3.5.
Is more preferable.

It is preferable to stir the solution, 60
It is preferable to stir at rpm or less. Further, the light used for the photoexcitation generates ultraviolet light by a high-pressure mercury light source lamp or the like, is condensed by a single convex lens, and is irradiated onto the electrode arranged in the solution. The single convex lens is preferably made of quartz glass.

The concentration of the compound containing the raw material element of the compound semiconductor in the solution is preferably 1.0 to 20 mmol / l, more preferably 2.0 to 10 mmol / l. The temperature of the solution is preferably 20 to 40 ° C, and 22 to 35 ° C.
Is more preferable. The formation time of the compound semiconductor layer is preferably 2400 to 4800 seconds, and 3000 to 360.
0 second is more preferable.

The deposited compound semiconductor is baked and crystallized. The crystallization temperature depends on the kind of the compound semiconductor to be deposited, but is preferably 80 to 600 ° C., and 80 to 5 ° C.
00 ° C is more preferable. The crystallization time is preferably 1 to 60 minutes, more preferably 15 to 30 minutes. Especially in the case of sulfide type, it is 80 ~ 400 ℃, and in the case of selenium type, it is 300
It is preferably 550 to 550 ° C, and 400 to 600 ° C in the case of tellurium.

—Method for Forming Complex Oxide Semiconductor Nanoporous Layer— The complex oxide semiconductor nanoporous layer is formed on the oxide semiconductor nanoporous layer formed by the above method, and further by the sol-gel method. Examples thereof include a method of forming a nanoporous layer and forming a composite, or a method of applying a paste in which two kinds of oxide semiconductor particles are mixed onto an electrode.

Specifically, acetic acid is added dropwise to the oxide semiconductor colloid aqueous solution, and the oxide semiconductor powder and alcohol to be composited are added little by little to the gelled solution that is well mixed in a mortar and mixed well. Further, a surfactant is added and mixed well, and this is mixed with a fluorine-doped tin oxide conductive film glass (FTO) electrode on a hot plate (100 to 120).
(° C.) by spray coating and firing, the crystallization of the semiconductor fine particles and the firing of the semiconductor fine particles proceed to form a complex oxide semiconductor nanoporous layer having a desired porosity.

The semiconductor nanoporous layer may be formed by applying a multi-layered dispersion of semiconductor fine particles having different particle sizes or a multi-layered coating layer containing different kinds of semiconductor fine particles (or different binders or additives). You can also Multi-layer coating is effective even when the film thickness is insufficient by one coating. An extrusion method or a slide hopper method is suitable for the multilayer coating. In the case of applying multiple layers, the multiple layers may be applied at the same time, or may be applied repeatedly several times to ten or more times. Furthermore, a screen printing method can also be preferably used if it is applied in sequence. In this case, it is preferable to perform a process of adsorbing and carrying an EC dye on each semiconductor nanoporous layer formed in a multi-layer structure. Different EC dyes may be adsorbed and carried on each layer, or the same EC dye may be adsorbed and carried on each layer. It doesn't matter.

The semiconductor nanoporous layer is heat-treated (for example, 10 to 100 ° C. to 550 ° C.) before supporting the EC dye.
It is preferable to do this for a minute. This makes it possible to remove moisture and other impurities adsorbed on the surface of the semiconductor nanoporous layer, activate the surface of the porous layer, and efficiently adsorb the EC dye.

The semiconductor nanoporous layer has a thickness of 100.
μm or less is preferable, 50 μm or less is more preferable, and 2
It is more preferably 0 μm or less. If the thickness of the porous layer is too thin, the amount of EC dye that can be adsorbed may decrease. On the other hand, if it is too thick, the transparency will decrease and E
In some cases, the charge injected into the C element may increase in loss.

—EC Dye— The EC dye is carried on the surface and inside the fine pores of the semiconductor nanoporous layer and, if necessary, is contained in a state of being dissolved or dispersed in the electrolyte layer. It is preferable. The EC dye is not particularly limited as long as it exhibits a function of developing or decoloring by at least one of an electrochemical oxidation reaction and a reduction reaction, and it can be appropriately selected according to the purpose. For example, an organic compound, a metal Suitable examples include complexes. These may be used alone or in combination of two or more.

Examples of the metal complex include Prussian blue, metal-bipyridyl complex, metal phenanthroline complex, metal-phthalocyanine complex, metaferricyanide, and derivatives thereof.

Examples of the organic material include (1) pyridine compounds, (2) conductive polymers, (3) styryl compounds, (4) donor / acceptor type compounds,
(5) Other organic dyes and the like.

Examples of the pyridine compounds (1) include viologen, heptylviologen (diheptylviologen dibromide, etc.), methylenebispyridinium, phenanthroline, azobipyridinium, 2,2.
-Bipyridinium complex, quinoline / isoquinoline, and the like.

Examples of the above-mentioned (2) conductive polymers include polypyrrole, polythiophene, polyaniline, polyphenylene diamine, polyaminophenol, polyvinylcarbazole, polymer viologen polyion complex, TTF, and derivatives thereof.

Examples of the above-mentioned (3) styryl compounds include 2- [2- [4- (dimethylamino) phenyl]
Ethenyl] -3,3-dimethylindolino [2,1-
b] oxazolidine, 2- [4- [4- (dimethylamino) phenyl] -1,3-butadienyl] -3,3-dimethylindolino [2,1-b] oxazolidine, 2-
[2- [4- (dimethylamino) phenyl] ethenyl]
-3,3-Dimethyl-5-methylsulfonylindolino [2,1-b] oxazolidine, 2- [4- [4- (dimethylamino) phenyl] -1,3-butadienyl]-
3,3-Dimethyl-5-sulfonylindolino [2,1
-B] oxazolidine, 3,3-dimethyl-2- [2-
(9-Ethyl-3-carbazolyl) ethenyl] indolino [2,1-b] oxazolidine, 2- [2- [4-
(Acetylamino) phenyl] ethenyl] -3,3-dimethylindolino [2,1-b] oxazolidine, and the like.

Examples of the (4) donor / acceptor type compounds include tetracyanoquinodimethane and tetrathiafulvalene.

Examples of the (5) other organic dyes include carbazole, methoxybiphenyl, anthraquinone, quinone, diphenylamine, aminophenol,
Tris-aminophenylamine, phenylacetylene,
Cyclopentyl compound, benzodithiolium compound, squarylium salt, cyanine, rare earth phthalocyanine complex,
Examples thereof include ruthenium diphthalocyanine, merocyanine, phenanthroline complex, pyrazoline, redox indicator, pH indicator, and derivatives thereof.

Among these, viologen, heptyl viologen (diheptyl viologen dibromide, etc.)
Viologen-based dyes such as are suitable. Also, the above E
As the C dye, it shows a colorless to ultra-light color in the oxidized state,
Reducing color type that develops color in the reduced state, colorless to ultra-light color in the reduced state, oxidative color type that develops in the oxidized state, coloration in both the reduced state and the oxidized state, and several types depending on the degree of reduction or oxidation. It may be of any of the multicolor-developing type that develops color, and can be appropriately selected according to the purpose.

The combination when two or more of the EC dyes are used in combination is not particularly limited and may be appropriately selected depending on the intended purpose. For example, a combination of viologen and polyaniline, polypyrrole and polymethylthiophene, and the like. And a combination of polyaniline and Prussian blue.

The method for supporting the EC dye on the surface and inside of the semiconductor nanoporous layer is not particularly limited,
Known techniques can be used. For example, a dry process such as a vacuum vapor deposition method, a coating method such as spin coating, an electric field deposition method, an electric field polymerization method, and a natural adsorption method of immersing in a solution of a compound to be supported can be appropriately selected. Among them, the natural adsorption method is
The functional molecules can be surely supported evenly throughout the fine pores of the metal oxide layer, no special equipment is required, and in many cases it is about a monomolecular layer and an excessive amount is needed. It is a preferable method because it has many advantages such as lack.

Specifically, a method of immersing a well-dried transparent substrate having a semiconductor nanoporous layer in an EC dye solution or applying a dye solution to the semiconductor nanoporous layer can be used. In the former case, a dipping method, a dipping method, a roller method, an air knife method or the like can be used. In the case of the dipping method, the dye may be adsorbed at room temperature, or may be heated under reflux as described in JP-A-7-249790. The latter coating method includes a wire bar method, a slide hopper method, an extrusion method, a curtain method, a spin method and a spray method.

As a solvent for dissolving the EC dye, for example, water, alcohols (methanol, ethanol, t
-Butanol, benzyl alcohol, etc.), nitriles (acetonitrile, propionitrile, 3-methoxypropionitrile, etc.), nitromethane, halogenated hydrocarbons (dichloromethane, dichloroethane, chloroform,
Chlorobenzene, etc., ethers (diethyl ether,
Tetrahydrofuran etc.), dimethyl sulfoxide, amides (N, N-dimethylformamide, N, N-dimethylacetamide etc.), N-methylpyrrolidone, 1,3-dimethylimidazolidinone, 3-methyloxazolidinone, esters ( Ethyl acetate, butyl acetate, etc.), carbonates (diethyl carbonate, ethylene carbonate, propylene carbonate, etc.), ketones (acetone, 2-butanone, cyclohexanone, etc.), hydrocarbons (hexane, petroleum ether, benzene, toluene, etc.) And mixed solvents of these.

The adsorbed amount of the EC dye is 0.01 to 100 m per unit surface area (1 m ² ) of the semiconductor nanoporous layer.
mol is preferred. The amount of the EC dye adsorbed on the semiconductor fine particles is 0.01 to 10 per 1 g of the semiconductor fine particles.
It is preferably in the range of 0 mmol. Further, the concentration of the EC dye in the electrolyte is preferably 0.001 to 2 mol / l, more preferably 0.005 to 1 mol / l.

—Charge Transfer Agent— Like the EC dye, the charge transfer agent is carried on the surface and inside the micropores of the semiconductor nanoporous layer, and
If necessary, it is preferably contained in a state of being dissolved or dispersed in the electrolyte layer. The charge transfer agent can be loaded on the semiconductor nanoporous layer by the same method as for the EC dye. When the charge transfer agent and the EC dye are used in combination, a coloring effect by simultaneous color development of the both and an interaction between the two can smoothly proceed the redox reaction to further improve the color development efficiency.

The charge transfer agent is not particularly limited and may be appropriately selected depending on the intended purpose, but those exhibiting electrochromic properties are preferable, and examples thereof include hydrazone, phenothiazine, [β- (10- Phenothiazyl) -propoxy] phosphonic acid (phenothiazine derivative), and the like, and one of these may be used alone or two or more thereof may be used in combination.

The charge transfer agent is adsorbed in an amount of 0.01 to 100 per unit surface area (1 m ² ) of the semiconductor nanoporous layer.
mmol is preferred. The amount of the charge transfer agent adsorbed on the semiconductor fine particles is 0.01 to 1 g of the semiconductor fine particles.
It is preferably in the range of 100 mmol. The concentration of the charge transfer agent in the electrolyte is preferably 0.001 to 2 mol / l, more preferably 0.005 to 1 mol / l.

-Electrolyte Layer- The electrolyte layer is not particularly limited and may be appropriately selected depending on the intended purpose, but preferably contains an EC dye and a charge transfer agent. As the EC dye and the charge transfer agent, Although it can be appropriately selected and used from the above-mentioned ones, the same one as the EC dye or the charge transfer agent supported on the semiconductor nanoporous layer is preferable. The form of the electrolyte layer may be liquid, solid, or gel.

(1) Liquid Electrolyte Layer When the electrolyte layer is a liquid, I ⁻ / I ₃ ⁻ , Br ⁻
It is preferable to use a charge-transporting substance such as an electrolyte, which contains a redox pair (oxidation-reduction pair) such as / Br ₃ ⁻ and a quinone / hydroquinone pair, and which can be transported between electrodes at a sufficient rate in a solvent.

Examples of the electrolyte include iodine, bromine, LiI, NaI, KI, CsI, CaI ₂ , and LiB.
Metal halides such as r, NaBr, KBr, CsBr, CaBr ₂ , tetraethylammonium iodide, tetrapropylammonium iodide, tetrabutylammonium iodide, tetramethylammonium bromide, tetraethylammonium bromide, tetrabutylammonium bromide, etc. At least one of halogenated salts of ammonium compounds, alkyl viologens such as methyl viologen chloride and hexyl viologen bromide, polyhydroxybenzenes such as hydroquinone and naphthohydroquinone, and iron complexes such as ferrocene and ferrocyanate can be used. However, the present invention is not limited to this. In addition, when a plurality of electrolytes that previously generate a redox pair (oxidation-reduction pair) are mixed and used, such as a combination of iodine and lithium iodide, it is possible to improve the performance of the EC element, particularly the current characteristics. Become. Among these, a combination of iodine and an ammonium compound, a combination of iodine and a metal iodide, and the like are preferable.

As a solvent for dissolving these electrolytes,
Carbonate compounds such as ethylene carbonate and propylene carbonate, ethers such as dioxane, diethyl ether and ethylene glycol dialkyl ether,
Alcohols such as methanol, ethanol, isopropyl alcohol, ethylene glycol, propylene glycol and polyethylene glycol, nitriles such as acetonitrile and benzonitrile, aprotic polar solvents such as dimethylformamide, dimethylsulfoxide, propylene carbonate and ethylene carbonate, water, etc. Can be used, but is not limited thereto.

The electrolyte concentration of the electrolyte in the solvent is preferably 0.001 to 2 mol / l,
More preferably, it is 005 to 1 mol / l. When the electrolyte concentration is less than 0.001 mol, the function as a carrier does not work sufficiently, and the characteristics may deteriorate. On the other hand, when it exceeds 2 mol / l, the above-mentioned effect corresponding to it does not appear, and the viscosity of the electrolyte solution becomes high, which may lead to a decrease in current.

(2) In case of solid electrolyte layer When the electrolyte layer is solid, ionic conductivity or electron
It may be any conductive material, for example, A
gBr, AgI, CuCl, CuBr, CuI, Li
I, LiBr, LiCl, LiAlCl_Four, LiAlF
_Four, Halides such as AgSBr, C₅H₅NHAg
₅I₆, Rb_FourCu₁₆I₇Cl_Thirteen, Rb_ThreeCu₇C
l₁₀Inorganic condensate, LiN, Li₅NI_Two, Li₆N
Br_ThreeSuch as lithium nitride and its derivatives, Li_TwoS
O_Four, Li_FourSiO_Four, Li_ThreePO_FourLithium acid etc
Phosphate, ZrO_Two, CaO, Gd_TwoO_Three, HfO_Two, Y
_TwoO_Three, Nb_TwoO₅, WO_Three, Bi_TwoO_Three, And these
Solid solution oxides, CaF_Two, PbF_Two, SrF_Two,
LaF_Three, TISn_TwoF₅, CeF_ThreeFluoride such as C
u _TwoS, Ag_TwoS, Cu_TwoSe, AgCrSe_TwoEtc.
Rucogenide, perfluorosulfur in vinyl fluoride polymer
Polymers containing phonic acid (eg Nafion), organic
As a cargo-transporting substance, polythiophene, polyaniline,
Compounds such as polypyrrole, fragrances such as triphenylamine
Carbazo such as group amine compounds and polyvinylcarbazole
Silane compound such as a polyol compound or polymethylphenylsilane
Can be used, but is not limited to
Absent.

(3) Gel Electrolyte Layer When the electrolyte layer is in a gel form, a polymer addition, an oil gelling agent addition, and polyfunctional monomers can be mixed with the electrolyte and the solvent and used. When gelation is performed by adding the polymer, “Polymer E
"lectrolyte Revews-1 and 2"
(J.R. MacCallum and CA Vincen
ELSEVIER APPLIED SCI
ENCE) and the like can be used, but polyacrylonitrile, polyvinylidene fluoride and the like are particularly preferable. When gelation is performed by adding the oil gelling agent, “J. Chem Soc.
pan, Ind. Chem. Sec. , 46,779
(1943) "," J. Am. Chem. Soc., 1 ".
11, 5542 (1989), "" J. Chem. So.
c. Chem. Commun. , 1993, 39
0 "," Angew. Chem. Int. Ed. Eng.
l. , 35, 1949 (1996) "," Chem. L.
ett. , 1996, 885 "," J. Chem. So.
c. Chem. Commun. , 1997, 545 "
Although the compounds described in, etc. can be used, a compound having an amide structure in the molecular structure is particularly preferable.

It is also possible to use a solid electrolyte layer formed into a film by polymerizing a mixed solution of a matrix material and a supporting electrolyte. —Supporting Electrolyte— The supporting electrolyte is appropriately selected depending on the intended purpose without any limitation, and it may be an inorganic electrolyte or an organic electrolyte. These may be used alone or in combination of two or more,
It may be a commercially available product or may be appropriately synthesized.

Examples of the inorganic electrolyte include inorganic acid anions-alkali metal salts, alkali metal salts, alkaline earth metals and the like. Among these, inorganic acid anions-alkali metal salts are preferable, and inorganic acid lithium Salts are more preferred.

As the inorganic acid anion-alkali metal salt
For example, XAsF₆, XPF ₆, XBF_Four, XC
10_Four, Etc. (However, in these, X
Represents H, Li, K or Na. ), Specifically oversalt
Preference is given to lithium oxalate and the like.

Examples of the alkali metal salt include L
iI, KI, LiCF ₃ SO ₃ , LiPF ₆ , LiCl
O ₄ , LiBF ₄ , LiSCN, LiAsF ₆ , NaC
_{F 3 SO 3, NaPF 6,} NaClO 4, NaI, Na
_{BF 4, NaAsF 6, KCF 6} SO 3, KPF 6, and the like.

Examples of the organic electrolyte include organic acid anions-alkali metal salts, quaternary ammonium salts, anionic surfactants, imidazolium salts, and the like. Among these, organic acid anions-alkali metals Salts are preferred, and organic acid lithium salts are more preferred.

Examples of the organic acid anion-alkali metal salt include XCF ₃ SO ₃ and XC _n F _{2n + 1} SO.
_{3 (n = 1~3), XN} (CF 3 SO 2) 2, XC (C
_{F 3 SO 2) 3, XB} (CH 3) 4, XB (C 6 H 5)
₄ , etc. (wherein X is H,
Li, K or Na), specifically, lithium polymethacrylate is suitable.

As the quaternary ammonium salt, for example,
For example, [CH_Three(CH_Two)_Three]_FourN ・ Y, C_nH_{2n + 1}
N (CH_Three)_Three・ Y (n = 10 to 18), (C_nH
_{2n + 1}) _TwoN (CH_Three)_Two・ Y (n = 10 to 18),
(However, in these, Y is B
F_Four, PF₆, ClO_Four, F, Cl, Br or OH
You )

Examples of the anionic surfactant include
For example, C_nH_{2n + 1}COO · X (n = 10-18), C
_nH_{2n + 1}OC_mH_2mCOO · X (n = 10 to 1
8, m = 10-18), C₁₀H₇COO / X, C_nH
_{2n + 1}C₁₀H₆COO · X (n = 10-18), C
_nH_{2n + 1}SO_Three・ X (n = 10 to 18), C_nH_{Two
n + 1}OC_mH_2mSO_Three・ X (n = 10 to 18, m =
10-18), C₁₀H ₇SO₈・ X, C_nH_{2n + 1}
C₁₀H₆SO_Three・ X (n = 10 to 18), C_nH
_{2n + 1}OSO_Three・ X (n = 10 to 18), etc.
(However, in these, X is H, Li, K or
Represents Na. ).

The supporting electrolyte preferably contains an inorganic acid lithium salt and an organic acid lithium salt.

—Matrix Material— The matrix material is appropriately selected depending on the intended purpose without any limitation, and examples thereof include a polymer compound having a hetero atom.

Examples of the polymer compound having a hetero atom include a polymer compound having an oxygen atom, a polymer compound having a nitrogen atom, a polymer compound having a sulfur atom, and a polymer compound having a halogen atom. Can be mentioned.

As the polymer compound having the oxygen atom
Is, for example, R¹-(OCH_TwoCH _Two)_nOR^Two(N
Represents an integer, R¹Is an ethylene group, styrene group,
Ropylene group, butene group, butadiene group, vinyl chloride group,
Vinyl acetate group, acrylic acid group, methyl acrylate group,
Tacrylic acid group, methyl methacrylate group, methyl vinyl chloride
R represents a ton group, an acrylamide group, etc.^TwoIs H, CH
_ThreeOr R¹Represents ) And the like are preferred.
Specifically, polyethylene glycol, polyp
Ropylene glycol, non-polyethers (eg poly
(3-hydroxypropionic acid), polyvinyl acetate),
And the like.

Examples of the polymer compound having a nitrogen atom include R ^1- (NHCH ₂ CH ₂ ) _n NH-R ²
(N represents an integer, R ¹ represents an ethylene group, a styrene group, a propylene group, a butene group, a butadiene group, a vinyl chloride group, a vinyl acetate group, an acrylic acid group, a methyl acrylate group, a methacrylic acid group, or methacrylic acid. Represents a methyl group, a methyl vinyl ketone group, an acrylamide group, etc., and R ² is
Represents H, CH ₃ or R ¹ . And the like. Specific examples thereof include polyethyleneimine, poly-N-methylethyleneimine, and polyacrylonitrile.

As the polymer compound having the sulfur atom
Is, for example, R¹-(SCH_TwoCH _Two)_nSR^Two(N
Represents an integer, R¹Is an ethylene group, styrene group,
Ropylene group, butene group, butadiene group, vinyl chloride group,
Vinyl acetate group, acrylic acid group, methyl acrylate group,
Tacrylic acid group, methyl methacrylate group, methyl vinyl chloride
R represents a ton group, an acrylamide group, etc.^TwoIs H, CH
_ThreeOr R¹Represents ) And the like are preferred.
Specifically, polyalkylene sulfides,
And so on.

The molecular weight of the matrix material is not particularly limited and may be appropriately selected depending on the intended purpose. However, the lower the molecular weight is, the more often it has fluidity at room temperature.
From the viewpoint of film formability, it is preferably low, and for example, the number average molecular weight is preferably 1,000 or less.

The amount of the matrix material used in the electrolyte layer is preferably 70:30 to 5:95, preferably 50:50 to 10, in a molar ratio with the supporting electrolyte (matrix material: supporting electrolyte). : 90 is more preferable, and 50:50 to 20:80 is particularly preferable.

The molar ratio means the ratio of the molar amount of the matrix material to the molar amount of the ions of the supporting electrolyte. The molar amount of the matrix material means a molar amount calculated by converting the monomer unit of the polymer compound into one molecule.

The film-like solid electrolyte layer is obtained by thinly extending a mixture of the matrix material and the supporting electrolyte to which a small amount of a polymerization initiator such as benzoyl peroxide or azobisisobutyronitrile is added, and then heating. It can be produced by carrying out polymerization or by adding a photopolymerization initiator such as Irgacure and polymerizing by irradiation with ultraviolet rays. The thickness of the solid electrolyte film is usually 3
It is 0 to 500 μm, preferably 50 to 200 μm.

—A Pair of Transparent Electrodes— The pair of transparent electrodes is not particularly limited as long as it is transparent and conducts electricity, and can be appropriately selected according to the purpose. For example, indium tin oxide (ITO). , Tin oxide (NESA), fluorine-doped tin oxide (FT
O), indium oxide, zinc oxide, platinum, gold, silver, rhodium, copper, chromium, carbon and the like. Among these, fluorine-doped tin oxide (FTO) and indium tin oxide (IT) have low surface resistance, good heat resistance, chemical stability, and high light transmittance.
O) is preferred.

The surface resistance of the conductive substrate is preferably lower as described above, and the specific surface resistance value is preferably 100 Ω / cm ² or less, and 10 Ω / c.
It is more preferably m ² or less. The thickness of the transparent electrode is not particularly limited and may be appropriately selected depending on the intended purpose. In the case of the transparent electrode, for example, 0.1 μm
It is generally m or more, particularly 0.1 to 20 μm.

—Support— The support can be used as a base material or the like on which the transparent electrode is provided, and its material, shape, structure, size, etc. are not particularly limited and can be appropriately designed. . Preferable examples of the support include a glass plate and a polymer film. Materials for the polymer film include tetraacetyl cellulose (TAC), polyethylene terephthalate (PET), polyethylene naphthalate (PEN), syndiotactic polystyrene (SPS), polyphenylene sulfide (PPS), polycarbonate (PC), polyarylate ( PAr),
Examples thereof include polysulfone (PSF), polyester sulfone (PES), polyetherimide (PEI), cyclic polyolefin, and brominated phenoxy.

-Other members-The other members are not particularly limited and may be appropriately selected depending on the application of the EC display. For example, spacers, sealing members, lead wires, reflecting means, etc. Is mentioned.

An example of the EC device of the present invention is shown in FIG.
As shown in Nos. 1 and 12, the transparent electrode 5 provided with the semiconductor nanoporous film 8 carrying the EC dye 2 on the surface and the semiconductor nanoporous film 8 carrying the EC dye 2 provided on the surface An example is one in which three semiconductor nanoporous films 8 and three structural units 45 are interposed so as to be sandwiched between the transparent electrode 5 and the semiconductor nanoporous film 8 and the semiconductor nanoporous film 8. The transparent electrode 5 and the transparent electrode 5 are connected by a lead wire 60 and are connected to a power source 50.

Further, as shown as an example in FIGS. 13 and 14, the transparent electrode 5 having the two-layered structure semiconductor nanoporous film 8, 8 on which the EC dye 2 is carried, and the EC dye 2 are carried. The electrolyte layer 9 is sandwiched between the semiconductor nanoporous film 8 and the transparent electrode 5 having the formed two-layer structure semiconductor nanoporous film 8 and 8 on its surface. An example is a stack of three structural units 45 thus interposed. The transparent electrode 5 and the transparent electrode 6 are connected by a lead wire 60 and connected to a power source 50.

The EC devices shown in FIGS. 11 to 14 are for applying a voltage between the transparent electrodes 5 to cause the EC dye 2 carried on the semiconductor nanoporous film 8 to develop and decolorize. is there.

The EC display of the present invention is not particularly limited, and any one selected from an area gradation method by flat ground mixing, a density gradation method by flat ground mixing, an area gradation method by layer mixing and a density gradation method by layer mixing. It is preferable to use a full color by the above method.

The area gradation method based on the plain mixture is a method of expressing a color image on the same principle as that of halftone dots on a printed matter. For example, a large number of minute pixels for coloring R (red), G (green), and B (blue) are provided in a plane, and the change in color density of each pixel does not have a gradation and color is generated by turning on / off a constant density. A color image is represented by a difference in area (for example, when the applied voltage and the applied time are constant).

The density gradation method based on the level ground mixing is a method of expressing a color image on the same principle as that of halftone dots on a printed matter as described above. However, since the color density of each pixel can have gradation, the color density can be controlled by controlling the applied voltage and the application time to control the amount of charge injected into the cell.

The area gradation method based on the layer mixture is a method of expressing a color image on the same principle as the halftone dot of the printed matter as described above, but since cells of three colors are vertically laminated in the same pixel, Pixel density is relaxed as compared with the area gradation method based on flatland mixing.

The density gradation method by the layered mixture is a coloring method similar to the density gradation method by the plain mixture, and is a full-color expression method similar to silver halide photography.

The EC display varies depending on the application, but in the case of a transmissive element, the response speed until reaching the ultimate transmittance is preferably 100 msec or less, and 10 msec.
The following is more preferable. Further, in the case of a reflective element, the response speed until reaching the ultimate absorbance is preferably 100 msec or less, more preferably 10 msec or less.

The voltage for forming an image on the EC display is not particularly limited and may be appropriately selected depending on the intended purpose.
About 10V is preferable, and about 1-5V is more preferable.

The EC display of the present invention is, for example, a computer, an in-vehicle display, an outdoor display, a household appliance,
It can be suitably used in various fields including commercial equipment, home appliances, traffic related indicators, clock indicators, calendar indicators, luminescent screens, audio equipment and the like.

[0161]

EXAMPLES Examples of the present invention will be described below, but the present invention is not limited to these examples.

(Example 1) Titanium oxide paste (Sol
Ti-Nanoxide HT manufactured by Aronix was applied on an ITO glass substrate using a doctor blade and dried. The obtained dried product was baked in air at 550 ° C. for 30 minutes to form a porous film having a thickness of 10 μm on a glass substrate.

Then, using the above substrate as an EC dye,
Dye adsorption treatment by immersing in 0.02M 2- {2- [4- (dimethylamino) phenyl] ethenyl} -3,3-dimethyl-5-phosphonoindolino [2,1-b] oxazoline in acetonitrile And dried at room temperature to prepare a magenta dye-bonded electrode.

A magenta color EC display device as shown in FIG. 7 was assembled using the obtained dye-bonded electrode and a TFT active matrix substrate as a counter substrate forming a pair therewith. Both substrates were bonded together via a spacer, an electrolyte solution was injected into the gap between both substrates, and the peripheral portion of the gap between the substrates was sealed with a curable resin. The distance between both substrates was 0.5 mm. As the electrolyte solution, a 0.2M propylene carbonate solution of tetra-n-butylammonium perchlorate was used. The size of the display portion of the manufactured magenta color EC display device was 2 cm × 2 cm.

Next, using 2- {2- [4- (dimethylamino) phenyl] -1,3-butadienyl} -3,3-dimethyl-5-carboxyindolino [2,1-b] oxazoline. The same operations as those for the magenta color EC display device were carried out to produce a cyan color EC display device.

Furthermore, using 2- {2- [4- (methoxy) phenyl] ethenyl} -3,3-dimethyl-5-phosphonoindolino [2,1-b] oxazoline, the above magenta coloring EC The same operation as that of the display device was performed to produce a yellow color EC display device.

Using the above-mentioned three kinds of EC display devices as structural units, three structural units were laminated and each was connected to produce an EC display device having a laminated structure.

In the EC display device having this laminated structure, when a voltage of 3 V was applied to the magenta color forming structural unit at room temperature, the styryl derivative was oxidized at the anode,
It changed from colorless to magenta. Next, when a voltage of 3 V was applied to the cyan color-forming structural unit at room temperature, the styryl derivative was oxidized at the anode and changed from colorless to cyan. In addition, 3V at room temperature with respect to the yellow coloring structural unit
When a voltage of 2 was applied, the styryl derivative was oxidized at the anode and changed from colorless to yellow.

Furthermore, when a voltage of 3 V was simultaneously applied to the magenta color-forming structural unit and the cyan color-forming structural unit at room temperature, the styryl derivative was oxidized at the anodes of the respective structural units to develop magenta and cyan colors, and as a whole. It changed from colorless to blue. Next, when a voltage of 3 V was applied simultaneously to the magenta color-forming structural unit and the yellow color-forming structural unit at room temperature, the styryl derivative was oxidized at the anode of each structural unit to develop magenta and yellow, and the overall colorless to colorless It turned red. When a voltage of 3 V was simultaneously applied to the cyan color forming structural unit and the yellow color forming structural unit at room temperature, the styryl derivative was oxidized at the anodes of the respective structural units to form cyan and yellow colors, and overall colorless to green. Changed to.

Furthermore, when a voltage of 3 V was simultaneously applied to the three color-forming structural units at room temperature, the styryl derivative was oxidized at the anodes of the respective structural units to develop magenta, cyan, and yellow, and the overall colorless to It turned black.

The response speed until reaching the ultimate transmittance was 80 msec in all cases. Even when the application of voltage was stopped, color development continued for 600 seconds or longer. Further, even when the color development-color erasing was repeated 10,000 times, the color strength during color development and the transparency during color erasure hardly changed.

(Example 2) In Example 1, the following electrolyte solution was used as an electrolyte, and this electrolyte solution was applied on one dye-bonding electrode with a spin coater to a thickness of 800.
The laminated EC was prepared in the same manner as in Example 1 except that the film-shaped electrolyte layer was formed by applying the coating solution to a thickness of 60 μm and heating at 60 ° C. for 6 hours.
A cover device was produced.

-Electrolyte Solution- In a solution of 67 g of lithium hydroxide dissolved in 27 ml of methanol, 7.68 g of methacrylic acid was added to 12 m of methanol.
The solution dissolved in 1 was added dropwise with stirring. Furthermore, the mixed solution obtained here was added dropwise to 2 liters of acetone,
The precipitate was collected by filtration, washed with acetone, and vacuum dried to obtain 2.38 g of white powder of lithium methacrylate. Next, 50 ml of a 1M aqueous solution of lithium methacrylate was prepared, and 1% by mass of potassium peroxodisulfate was added to this, and the mixture was kept at 70 ° C. for 24 hours in a nitrogen atmosphere to obtain lithium methacrylate. Was polymerized. After the completion of the polymerization reaction, reprecipitation was performed using 500 ml of methanol, and the precipitate was collected and dried to synthesize 1.73 g of white powder of lithium polymethacrylate. Next, lithium iodide: lithium perchlorate: the synthesized polylithium methacrylate = 50: 30: 20 (molar ratio) was used, and polyethylene glycol (number average molecular weight = 600) was used as the matrix material ( Ethylene oxide unit of polyethylene glycol: lithium ion = 5
1:49 (molar ratio)), these were dissolved in water.

In the obtained EC display device, when a voltage of 3 V was applied to the magenta color-forming structural unit at room temperature, the styryl derivative was oxidized at the anode and changed from colorless to magenta. Next, when a voltage of 3 V was applied to the cyan color-forming structural unit at room temperature, the styryl derivative was oxidized at the anode and changed from colorless to cyan.
When a voltage of 3 V was applied to the yellow color-forming structural unit at room temperature, the styryl derivative was oxidized at the anode and changed from colorless to yellow.

Furthermore, when a voltage of 3 V was simultaneously applied to the magenta color-forming structural unit and the cyan color-forming structural unit at room temperature, the styryl derivative was oxidized at the anodes of the respective structural units to develop magenta and cyan colors. It changed from colorless to blue. Next, when a voltage of 3 V was applied simultaneously to the magenta color-forming structural unit and the yellow color-forming structural unit at room temperature, the styryl derivative was oxidized at the anode of each structural unit to develop magenta and yellow, and the overall colorless to colorless It turned red. When a voltage of 3 V was simultaneously applied to the cyan color forming structural unit and the yellow color forming structural unit at room temperature, the styryl derivative was oxidized at the anodes of the respective structural units to form cyan and yellow colors, and overall colorless to green. Changed to.

Furthermore, when a voltage of 3 V was simultaneously applied to the three color-forming structural units at room temperature, the styryl derivative was oxidized at the anodes of the respective structural units to develop magenta, cyan, and yellow, and the overall color was colorless. It turned black.

The response speed to reach the ultimate transmittance was 100 msec in all cases. Even when the application of voltage was stopped, color development continued for 600 seconds or longer. Further, even when the color development-color erasing was repeated 10,000 times, the color strength during color development and the transparency during color erasure hardly changed.

(Example 3) -Porous TiO ₂ electrode-Titanium tetraisopropoxide (6.41 g) was diluted with 20 ml of ethanol, and 0.514 g of nitric acid having a specific gravity of 1.38 and 0.2 ml of water were added with stirring. It was The above mixing operation was performed in a dry nitrogen atmosphere. This mixture is at 80 ℃
The temperature was raised to 2, and reduction was performed for 2 hours under a stream of dry nitrogen to obtain a colorless and transparent sol liquid. After cooling the sol liquid to room temperature, 0.1 g of polyacrylic acid was added to 2 g of the sol liquid while stirring.
Was dissolved. 2 ml of water was further added to the obtained sol liquid to obtain a colorless, transparent and uniform sol liquid. The sol solution was sealed in a glass container and heated to 80 ° C. The sol liquid gelled in about 5 minutes and became a substantially transparent and uniform gel. When kept at 80 ° C. for a further 15 hours, the gel was dissolved again and became a whitish translucent sol liquid.

This sol solution was subjected to TF by spin coating.
It was coated on a T active matrix substrate, heated to 450 ° C., held for 20 minutes, and baked. This coating and baking process was repeated 20 times to obtain a porous TiO ₂ film having a thickness of 3.5 μm.
An electrode composed of a film was formed. The crystal structure of the obtained film is X.
As a result of examination by line diffraction, it was confirmed that anatase type titanium oxide was formed. SE for fine structure of film
When examined by M observation, a phase-separated aggregate structure was formed. The specific surface area of this fired product film (transparent conductive film) was 100 g / cm ² . The specific surface area is BE
The measurement was performed by a method of adsorbing nitrogen gas at a liquid nitrogen temperature using a T surface area measuring device (Multisorb 12 manufactured by Mitsuwa Rikagaku Kogyo).

Next, the above substrate was immersed in a 0.02 M methanol solution of 1,1′-ferrocene dicarboxylic acid as an oxidation-reduction substance, subjected to adsorption treatment, and dried at room temperature to prepare a ferrocene-bonded electrode.

A magenta coloring EC display device as shown in FIG. 9 was assembled by using the obtained ferrocene-bonded electrode and the dye-bonded electrode of Example 1 as a counter substrate forming a pair with the ferrocene-bonded electrode. Both substrates were bonded together via a spacer, an electrolyte solution was injected into the gap between both substrates, and the peripheral portion of the gap between the substrates was sealed with a curable resin. The distance between both substrates was 0.5 mm. As the electrolyte solution, a 0.2M propylene carbonate solution of tetra-n-butylammonium perchlorate was used. The size of the display portion of the manufactured magenta color EC display device was 2 cm × 2 cm. Also,
Similarly, a cyan color EC display device and a yellow color E display device
A C display device was manufactured.

Three of the above structural units were laminated, and each pair of electrodes was connected by a lead wire (a dye-bonding electrode for the anode and a ferrocene-bonding electrode for the cathode) to produce a laminated EC display device.

In this EC display device, when a voltage of 3 V was applied to the magenta coloring structural unit at room temperature,
The styryl derivative was oxidized at the anode and changed from colorless to magenta. Next, when a voltage of 3 V was applied to the cyan color-forming structural unit at room temperature, the styryl derivative was oxidized at the anode and changed from colorless to cyan. When a voltage of 3 V was applied to the yellow color-forming structural unit at room temperature, the styryl derivative was oxidized at the anode and changed from colorless to yellow. It should be noted that, in the above-mentioned color-developing household, the ferrocene derivative of the counter electrode also causes a redox reaction, but since the oxidant and the reductant are colorless, it does not affect the color observed as a whole.

Furthermore, when a voltage of 3 V was applied simultaneously to the magenta color-forming structural unit and the cyan color-forming structural unit at room temperature, the styryl derivative was oxidized at the anodes of the respective structural units to develop magenta and cyan colors, and as a whole. It changed from colorless to blue. Next, when a voltage of 3 V was applied simultaneously to the magenta color-forming structural unit and the yellow color-forming structural unit at room temperature, the styryl derivative was oxidized at the anode of each structural unit to develop magenta and yellow, and the overall colorless to colorless It turned red. When a voltage of 3 V was simultaneously applied to the cyan color forming structural unit and the yellow color forming structural unit at room temperature, the styryl derivative was oxidized at the anodes of the respective structural units to form cyan and yellow colors, and overall colorless to green. Changed to.

Furthermore, when a voltage of 3 V was simultaneously applied to the three color-forming structural units at room temperature, the styryl derivative was oxidized at the anode of each structural unit to develop magenta, cyan, and yellow, and the overall colorless to It turned black.

The response speed to reach the ultimate transmittance was 80 msec in all cases. Even when the application of voltage was stopped, color development continued for 600 seconds or longer. Further, even when the color development-color erasing was repeated 10,000 times, the color strength during color development and the transparency during color erasure hardly changed.

[0187]

According to the present invention, the above-mentioned problems in the prior art can be solved, full color can be easily realized, the memory property is excellent, and the response speed, the coloring efficiency and the repeating durability are greatly improved. Can be provided.

[Brief description of drawings]

1A and 1B show a conventional monochromatic color passive matrix panel, in which FIG. 1A is a perspective view and FIG. 1B is a schematic sectional view.

2A and 2B show an example of a monochromatic passive matrix panel of the present invention, FIG. 2A is a perspective view, and FIG. 2B is a schematic sectional view.

3A and 3B show an example of a monochromatic passive matrix panel of the present invention, FIG. 3A is a perspective view, and FIG. 3B is a schematic sectional view.

FIG. 4 shows an example of a passive matrix panel for full-color color development of the present invention, (A) is a perspective view and (B) is a perspective view.
Is a schematic cross-sectional view.

5A and 5B show an example of a full-color color passive matrix panel of the present invention, in which FIG. 5A is a perspective view and FIG.
Is a schematic cross-sectional view.

6A and 6B show an example of a full-color color passive matrix panel of the present invention, in which FIG. 6A is a perspective view and FIG.
Is a schematic cross-sectional view.

FIG. 7 is a perspective view showing an example of a monochromatic active matrix panel of the present invention.

FIG. 8 is a perspective view showing an example of a monochromatic color active matrix panel of the present invention.

FIG. 9 is a perspective view showing an example of a color-developing active matrix panel of the present invention.

FIG. 10 is a perspective view showing an example of a color-developing active matrix panel of the present invention.

FIG. 11 is a schematic explanatory view showing an example of an EC device.

FIG. 12 is a partially enlarged view of an X area in FIG. 11.

FIG. 13 is a schematic explanatory view showing an example of an EC device.

FIG. 14 is a partially enlarged view of an X area in FIG.

[Explanation of symbols]

2 EC dye 5 Transparent electrode 8 Semiconductor nanoporous layer 9 Electrolyte layer 12 glass substrates 14 Positive electrode 20 EC element 22 Negative electrode 24 EC element for red color development 26 EC element for green color development 28 EC element for blue color development 40 TFT circuit 45 structural units 50 power 60 lead wire

Claims (17)

[Claims] 1. An electrochemical oxidation reaction and reduction reaction while a pair of transparent electrodes having a semiconductor nanoporous layer formed on at least one surface are arranged so that the semiconductor nanoporous layers face each other. Sandwiching an electrolyte layer containing an electrochromic dye capable of reversibly developing or erasing color by at least one of, and laminating a plurality of structural units having any one of a passive matrix panel structure and an active matrix panel structure. An electrochromic display that is characterized by 2. A pair of transparent electrodes having, on at least one surface thereof, a semiconductor nanoporous layer carrying an electrochromic dye capable of reversibly developing or erasing color by at least one of electrochemical oxidation reaction and reduction reaction. By sandwiching an electrolyte layer between the semiconductor nanoporous layers so as to face each other, and laminating a plurality of structural units having either a passive matrix panel structure or an active matrix panel structure. An electrochromic display characterized by 3. The electrochromic display according to claim 1, wherein 2 to 4 of the structural units are laminated. 4. The electrochromic display according to claim 2, wherein a different electrochromic dye is carried for each structural unit. 5. The electrochromic display according to claim 1, wherein at least one of the semiconductor nanoporous layers has a multilayer structure. 6. The electrochromic display according to claim 5, wherein both semiconductor nanoporous layers have a multilayer structure. 7. The electrochromic display according to claim 5, wherein the semiconductor nanoporous layer is laminated by low temperature firing at 150 to 200 ° C. 8. The electrochromic display according to claim 5, wherein a different electrochromic dye is carried in each layer of the semiconductor nanoporous layer having a multilayer structure. 9. The electrochromic display according to claim 1, further comprising a charge transfer agent in the electrolyte layer. 10. The electrochromic display according to claim 2, wherein a charge transfer agent is supported on the semiconductor nanoporous layer. 11. The semiconductor fine particles contained in the semiconductor nanoporous layer are a single semiconductor, an oxide semiconductor, a compound semiconductor,
The electrochromic display according to claim 1, which is selected from an organic semiconductor, a complex oxide semiconductor, and a mixture thereof. 12. The composite oxide semiconductor is SnO._Two-Z
nO, Nb_TwoO₅-SrTiO_Three, Nb_TwoO₅-Ta_Two
O₅, Nb_TwoO₅-ZrO_Two, Nb_TwoO₅-TiO_Two,
Ti-SnO_Two, Zr-SnO_Two, In-SnO_Twoas well as
Bi-SnO _TwoThe elect according to claim 11, which is selected from
Trochromic display. 13. The electrochromic display according to claim 2, wherein a heat treatment is performed before the electrochromic dye is supported on the semiconductor nanoporous layer. 14. The semiconductor nanoporous layer has a thickness of 100 μm.
The electrochromic display according to any one of claims 1 to 13, which has a thickness of m or less. 15. The electrochromic display according to claim 1, wherein the electrochromic dye is selected from organic compounds and metal complexes. 16. A full color image is formed by any one of an area gradation method by level ground mixing, a density gradation method by level ground mixing, an area gradation method by layer mixing and a density gradation method by layer mixing. The electrochromic display according to any one of 1 to 15. 17. The response speed until reaching the ultimate transmittance or the ultimate absorbance is 100 msec or less.
6. The electrochromic display according to any one of 6.