JP2003302659A - Electrochromic display - Google Patents

Electrochromic display

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Publication number
JP2003302659A
JP2003302659A JP2002109153A JP2002109153A JP2003302659A JP 2003302659 A JP2003302659 A JP 2003302659A JP 2002109153 A JP2002109153 A JP 2002109153A JP 2002109153 A JP2002109153 A JP 2002109153A JP 2003302659 A JP2003302659 A JP 2003302659A
Authority
JP
Japan
Prior art keywords
semiconductor
layer
ec
electrochromic display
electrolyte
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Pending
Application number
JP2002109153A
Other languages
Japanese (ja)
Inventor
Kiyoshi Fujimoto
潔 藤本
Original Assignee
Fuji Photo Film Co Ltd
富士写真フイルム株式会社
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Fuji Photo Film Co Ltd, 富士写真フイルム株式会社 filed Critical Fuji Photo Film Co Ltd
Priority to JP2002109153A priority Critical patent/JP2003302659A/en
Publication of JP2003302659A publication Critical patent/JP2003302659A/en
Application status is Pending legal-status Critical

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Abstract

<P>PROBLEM TO BE SOLVED: To provide an EC (electrochromic) display which facilitates full colorization, has excellent memory properties and is greatly improved in a response speed, color development efficiency, and repetitive durability. <P>SOLUTION: The EC display comprises holding an electrolyte layer between a pair of transparent electrodes formed with a semiconductor nano-porous layer on at least one surface and arranged to oppose the semiconductor nano- porous layer one another and has a structure of either a passive matrix panel structure and an active matrix panel structure. At least one EC dyestuffs which are reversely made to develop colors or to decolor by at least either of an electrochemical oxidation reaction and reduction reaction are incorporated into the electrolyte. <P>COPYRIGHT: (C)2004,JPO

Description

DETAILED DESCRIPTION OF THE INVENTION [0001] BACKGROUND OF THE INVENTION 1. Field of the Invention
In particular, it is easy to make full color
Yes, with excellent memory characteristics, response speed, coloring efficiency and repetition rate
Electrochromic disc with greatly improved return durability
Regarding spraying. [0002] [0002] Electrochromic (hereinafter referred to as “EC”)
(Abbreviated) devices, such as EC display devices, are not equipped with polarizing plates.
As it is essential, there is no viewing angle dependency and it is a light receiving type with excellent visibility.
Reversible color development or disappearance by electrochemical redox reaction
The electrolyte containing the EC material to be colored and a pair of electrodes are reduced.
If there is at least, it will be established, so the structure is simple and large size
Easy to obtain various colors by selecting the EC material
The electron transfer is blocked and the redox state is maintained.
The display state can be stopped by just turning it on.
However, no power is required to maintain the display state.
Since there are various advantages such as low power consumption,
It has been applied in the field. For example, on a glass substrate, a transparent electrode layer (invisible)
Electrode), tungsten trioxide thin film layer (EC layer), silicon dioxide
Insulating layer like silicon and electrode layer (anode)
All solid-state EC element is disclosed in Japanese Patent Publication No. 52-46098
It is disclosed. This EC element displays voltage (coloring voltage).
In addition, tungsten trioxide (WO3) The thin film layer is blue
Color it. After that, this EC element has a reverse polarity
When applying (erasing voltage), tungsten trioxide thin film layer
The blue color of disappears and returns to colorless. This coloring and decoloring mechanism
Although it has not been elucidated in detail, WO3Thin film layer and insulating layer
A small amount of water contained in the (ion conductive layer) is WO3Thin
It is understood that it dominates the coloring and decoloring of the membrane layer. Recently, for example, Japanese Patent Laid-Open No. 9-120088
Japanese Patent Laid-Open No. 7-152050, Japanese Patent Laid-Open No. 6-24
As shown in Japanese Patent No. 2474, etc.
The EC material is deposited on the electrode, and a supporting salt and a solvent are placed between the electrodes.
EC display device enclosed, EC material between a pair of electrodes
EC display device that encloses a salt, a supporting salt and a solvent.
EC display devices have been proposed. However, in these EC display devices,
Is accompanied by the movement of substances (ions) in color development / decoloration.
There is a serious problem that it is difficult to increase the response speed.
In the case of the latter EC display device, it is due to the diffusion of the coloring material.
Bleeding occurs and high-definition image display is difficult
There is a problem. For this reason, for example, JP-A-2000-2000
In the 19567 publication, the latter EC display device is used.
And it has been proposed to use solid polymer electrolytes
However, sufficient ionic conductivity cannot be obtained even when heated, etc.
There is a problem of inferiority. Therefore, it is easy to make full color,
Excellent memory performance, response speed, color development efficiency and repeated resistance
EC display with much improved durability is still available
The current situation is not. [0007] SUMMARY OF THE INVENTION The present invention is a conventional technique.
To solve the above problems and to solve the following problems
And That is, the present invention has a simple structure and is easy to manufacture.
It is easy to make full color, has excellent memory characteristics,
Significantly improved response speed, coloring efficiency and durability
An object is to provide an EC display. [0008] [Means for Solving the Problems] To solve the above problems
The means is as follows. That is, <1> A semiconductor nanoporous layer on at least one surface
A pair of formed transparent electrodes is formed between the semiconductor nanoporous layers.
Sandwich the electrolyte layer between the two so that they face each other.
Passive matrix panel structure and active mat
Electro having either structure of the Rix panel structure
A chromic display, in which the electrolyte
By at least one of aerochemical oxidation and reduction
At least one type of reversibly developing or decoloring
An electrochromic dye characterized by containing a rochromic dye.
It is a lectrochromic display. <2> Semiconductor nanoporous layer on at least one surface
A pair of formed transparent electrodes is formed between the semiconductor nanoporous layers.
Sandwich the electrolyte layer between the two so that they face each other.
Passive matrix panel structure and active mat
Electro having either structure of the Rix panel structure
A chromic display comprising the semiconductor nanoporous
In the material layer, at least electrochemical oxidation and reduction reactions
At least one kind that reversibly develops or decolors by either
Special electrochromic dye is supported.
This is an electrochromic display. <3> Electrochemical oxidation reaction and reduction reaction in the electrolyte layer
The color which is reversibly developed or decolored by at least one of the responses
Containing at least one lectrochromic dye
<2> The electrochromic display according to
The <4> Nanoporous semiconductor on both surfaces of a pair of transparent electrodes
Any one of <1> to <3> in which a porous layer is formed
This is an electrochromic display. <5> Further, a charge transfer agent is contained in the electrolyte layer.
The elect according to any one of <1> to <4>
It is a rochromic display. <6> Charge transfer agent supported on the semiconductor nanoporous layer
The electrochromic device according to <5>, wherein
It is a display. <7> Semiconductor fine particles contained in the semiconductor nanoporous layer
Single semiconductor, oxide semiconductor, compound semiconductor, organic semiconductor
Selected from conductors, complex oxide semiconductors and mixtures thereof
The elect according to any one of <1> to <6>
It is a rochromic display. <8> Composite oxide semiconductor is SnO2-ZnO, N
b2O5-SrTiO 3, Nb2O5-Ta2O5, N
b2O5-ZrO2, Nb2O5-TiO2Ti-S
nO2, Zr-SnO2In-SnO2And Bi-S
nO2The electrochroma according to <7>, selected from
Mick display. <9> The above-mentioned electrochromic dye is a semiconductor nano
<2>, wherein heat treatment is performed before supporting the porous layer.
To <8>.
It is a display. <10> The thickness of the semiconductor nanoporous layer is 100 μm or less
The electric device according to any one of <1> to <9>, wherein
It is a trochromic display. <11> Electrochromic dyes are organic compounds and
<1> to <10> selected from metal complexes
An electrochromic display
The <12> Area gradation method by mixing flat ground, by flat ground mixing
For density gradation method, area gradation method by lamination mixing and lamination mixing
Full color by any method selected from the density gradation method
Or any one of <1> to <11>
It is an electrochromic display. <13> Response until reaching ultimate transmittance or ultimate absorbance
The speed is 100 msec or less from <1> to <12
> Electrochromic display according to any one of
I. The EC display described in <1> is
A semiconductor nanoporous layer was formed on at least one surface
A pair of transparent electrodes, the semiconductor nanoporous layers face each other
The electrolyte layer is sandwiched between the
Trix panel structure and active matrix panel structure
In the electrolyte.
By at least one of aerochemical oxidation and reduction
At least one EC dye that reversibly develops or decolors
Is contained. In the EC display, transparent
The surface of the semiconductor nanoporous layer formed on the surface of the bright electrode
EC dye in the electrolyte layer is found throughout the micropores
Penetration efficiently, which greatly improves response speed
In addition, the electrode area can be expanded and the amount of dye on the electrode can be increased.
Color development efficiency (desired faster with lower applied voltage
To achieve a color density of 3). The EC display according to the above <2>
A semiconductor nanoporous layer was formed on at least one surface
A pair of transparent electrodes, the semiconductor nanoporous layers face each other
The electrolyte layer is sandwiched between the
Trix panel structure and active matrix panel structure
The semiconductor nanoporous structure having any structure of the structure
In the material layer, at least electrochemical oxidation and reduction reactions
At least one kind that reversibly develops or decolors by either
The EC dye is supported. In this EC display
Semiconductor nanoporous material formed on the surface of the transparent electrode
EC dye is supported on the surface and internal micropores of the layer and fixed
Since it is made into a material, the movement of substances (ions) for coloring and decoloring
The time for mass transfer due to diffusion is reduced.
Which can greatly improve response speed
In addition, the electrode area can be expanded and the amount of dye on the electrode can be increased.
As a result, the coloring efficiency is improved. The EC display according to the above <3>
In <2>, the electrochemical oxidation reaction in the electrolyte layer.
Reversibly develops color by at least one of reaction and reduction reaction
Contains at least one EC dye to be erased,
The semiconductor nanoporous layer formed on the surface of the transparent electrode
Combined with EC dye supported on surface and internal micropores
The response speed is greatly improved and the coloring efficiency is improved.
To do. The EC display according to the above <5>
In any one of the above items <1> to <4>, the charge transfer agent
Is contained in the electrolyte layer, so EC dye and charge transfer
By using the agent together, both colors develop on the electrode simultaneously
As the color density increases, the redox reaction becomes smoother.
The response speed is improved. The EC display according to the above <7>
In any one of the above items <1> to <6>, the semiconductor nano
As semiconductor fine particles contained in the porous layer, a single semiconductor,
Oxide semiconductor, compound semiconductor, organic semiconductor, complex oxidation
Surface by using physical semiconductors and their mixtures
And a semiconductor nanoporous layer having fine pores formed therein.
As a result, the adsorption amount of EC dye increases and the response speed and color development efficiency
Will improve. The EC display according to the above <9>
In any one of the above items <2> to <8>, the EC dye
Apply heat treatment before loading on the semiconductor nanoporous layer
Moisture adsorbed on the surface of the semiconductor nanoporous layer,
Activates the porous layer surface while removing other impurities
In addition, the EC dye can be efficiently adsorbed. EC display according to <10> above
Is a semiconductor according to any one of <1> to <9>.
The thickness of the nanoporous layer is 100 μm or less
Can be adsorbed without reducing transparency.
The amount of EC dye can be increased, improving the color development efficiency
obtain. EC display according to <12> above
Is any one of <1> to <12> above,
Area gradation method by mixing, density gradation method by mixing flat ground, product
Area gradation method by layer mixing and density gradation method by lamination mixing
By adopting one of the methods selected from
Can be easily achieved. [0017] DETAILED DESCRIPTION OF THE INVENTION The EC display of the present invention is a semi-
A conductor nanoporous layer formed on at least one surface
The semiconductor nanoporous layers face each other in a pair of transparent electrodes
The electrolyte layer is sandwiched between the
Submatrix panel structure and active matrix panel
(1) in the electrolyte layer
An EC display containing an EC dye in (2)
E in which an EC dye is supported on the semiconductor nanoporous layer
C display, preferably (3) EC dye is said semiconductor
The electrolyte layer is supported on the body nanoporous layer
EC display contained therein. In addition,
The EC display has a backlight inside the display.
Transmission type with a light source such as light, and external light such as sunlight as a light source
Reflective type to be used as a combination, or a combination of the former two
Any of a semi-transmissive type may be used. In addition, the EC
The display may be a single color or a multicolor display.
A full color type of color development may be used. FIG. 1 to FIG. 3 show monochromatic color passive matrices.
(A) is a perspective view, (B) is a schematic cross section
FIG. 1 (A) and 1 (B) show the semiconductor on the transparent electrode surface.
Conventional monochromatic coloring passi that do not have a nanoporous layer
Shows a submatrix panel, which is a pair of glass
On the substrates 12, 12, strip-shaped transparent plates arranged parallel to each other
It has bright electrodes 5 and 5 (for example, ITO electrodes) and is transparent
An electrolyte 9a containing an EC dye is disposed between the electrodes 5 and 5.
Is. 2 (A) and 2 (B) show the single color development of the present invention.
An example of a passive matrix panel, a pair of glass
On the substrates 12, 12, strip-shaped transparent plates arranged parallel to each other
It has bright electrodes 5 and 5 (for example, ITO electrodes) and is transparent
A pair of semiconductor nano-electrodes is interposed between the electrodes 5 and 5 via the electrolyte layer 9.
The porous layers 8, 8 are arranged so that they face each other
is there. 3 (A) and 3 (B) show the monochromatic coloring passi of the present invention.
An example of a submatrix panel is shown, and a pair of glass substrates 1
2 and 12, strip-shaped transparent electrodes arranged parallel to each other
5,5 (for example, ITO electrode), and the transparent electrodes 5,5
On top of this, semiconductor nanoporous membranes 8 and 8 are laminated.
Electrolyte layer with electrodes having semiconductor nanoporous membrane on the surface of the pair
9 is sandwiched. Either one of the transparent
You may create a semiconductor nanoporous membrane only on the bright electrode
Yes. In addition, even if EC dye is adsorbed on both poles,
Also, EC dye on one side and colorless redox on the other
Substances may be adsorbed. 4 to 6 show a full color type
The submatrix panel is shown, (A) is a perspective view, (B) is
It is a schematic sectional drawing. 4 (A) and 4 (B) are diagrams of the present invention.
An example of a rucolor type passive matrix panel
And strips arranged parallel to each other on the glass substrate 12
Transparent electrodes 5 and 5 (for example, ITO electrodes)
The semiconductor nanoporous film 8 is provided on the transparent electrode 5 of
Red (R) color developing EC dye, green (G) color developing EC dye and
Blue (B) color-developing EC dye is supported in order, and the other transparent
The electrolyte layer 9 is interposed between the bright electrode 5 and the light electrode 5.
5A and 5B show the full color type of the present invention.
An example of a sitive matrix panel is shown in FIG.
To increase the efficiency of the redox reaction on the counter electrode,
Is also provided with a semiconductor nanoporous film 8a, which is a colorless redox material
Is adsorbed. 6 (A) and (B)
One of the bright full color passive matrix panels
An example is given to develop color at both poles to improve coloring efficiency and response efficiency.
It is what was raised. That is, a semiconductor is formed on one transparent electrode 5
Body nanoporous membrane 8 is provided, and red (R) coloring EC dye, green
Color (G) coloring EC dye and blue (B) coloring EC dye in order
To the opposite electrode so as to be orthogonal to these
The semiconductor nanoporous film 8 is provided in a dot shape so that the colors match.
EC dye is adsorbed on the electrolyte layer 9 and the electrolyte layer 9 is interposed
Is. In the passive matrix panel
For example, a positive line composed of a plurality of positive electrodes and a plurality of positive electrodes
The negative electrode line consisting of negative electrodes intersects each other in a substantially perpendicular direction.
A circuit is formed. Red departures located at each intersection
Supports EC dyes for color, green and blue color development
The semiconductor nanoporous membrane that functions as a pixel
Correspondingly, there are a plurality of EC dyes. The passive mat
In the Rix panel, one of the positive electrodes in the positive line
And a constant current source for one of the negative electrodes in the negative line
When the current is applied by the
Current is applied to the EC dye, and the EC dye at that position develops color
To do. Easy to control the color development of this pixel unit
In addition, a full color image can be formed. FIG. 7 shows a monochromatic active matrix according to the present invention.
An example of a glass panel, the TFT substrate 20 is a glass substrate
Scan lines, data lines, and current supply lines are on the board.
Scan lines, etc. that are formed in a grid pattern and form a grid pattern
Connected to each other and driven by a TFT circuit placed on each grid.
Positive electrode 23 (for example, arranged in each grid)
For example, an ITO electrode). In this panel of FIG.
Does not adsorb EC dye on the TFT substrate side,
Semiconductor nanoporous so as to cover the whole on the glass substrate 12
A membrane 8 is provided, on which EC dye is adsorbed, and between the positive and negative electrodes
The electrolyte layer 9 is interposed. FIG. 8 illustrates the present invention.
An example of a single color active matrix panel is shown in FIG.
, Semiconductor nanoporous material on the positive electrode 23 of the TFT substrate
A membrane 8 is provided, on which EC dye is adsorbed, and between the positive and negative electrodes
The electrolyte layer 9 is interposed. FIG. 9 illustrates the present invention.
Example of full color type active matrix panel
The semiconductor nanoporous film on the positive electrode 23 of the TFT substrate
8 and a red (R) coloring EC dye, green for each pixel
(G) Colored EC dye and blue (B) Colored EC dye in order
On the glass substrate 12 on the negative electrode side.
The semiconductor nanoporous film 8a is provided so as to cover the
Adsorbed redox material with electrolyte layer 9 interposed
It is. FIG. 10 shows an actuator of the full color type of the present invention.
An example of an active matrix panel, the positive electrode of the TFT substrate
23 is provided with a semiconductor nanoporous film 8 and red for each pixel.
(R) Colored EC dye, green (G) Colored EC dye and blue
(B) The color developing EC dye is supported in order and the negative electrode side
Pattern semiconductor nanoporous membrane 8 in dots
However, the EC dye matches the color of the positive electrode for each dot (pixel).
It is adsorbed so that the electrolyte layer 9 is interposed.
The In the active matrix panel
Is, for example, a plurality of parallel scanning lines and a plurality of parallel scanning lines.
The data line and current supply line provided on the
A grid is formed at right angles to the grid.
A circuit in which the TFT for driving and the TFT for driving are connected
Is formed. When current is applied from the drive circuit,
Switching TFT and driving TFT are driven for each grid
It is possible. And each grid is for red coloring,
Each EC dye for green color development and blue color development functions as a pixel
In the active matrix panel
One of the scanning lines arranged in the vertical direction and the current arranged in the vertical direction
When current is applied from the drive circuit to the supply line,
At that time, the switching TFT located at the intersection is
And the driving TFT is driven accordingly, and the E at the position is driven.
C dye develops color. Control the color development of this pixel unit
Makes it easy to form full-color images.
The EC element constituting the EC display
Forms a semiconductor nanoporous layer on at least one surface
The paired transparent electrodes are paired with the semiconductor nanoporous layer.
The electrolyte layer is sandwiched between
EC dye is contained in the electrolyte layer, or the semiconductor
EC dye is supported on the body nanoporous layer. Below, each
The components will be described in detail. -Semiconductor nanoporous layer- The semiconductor nanoporous layer has at least a pair of transparent electrodes.
On the other hand, preferably formed on both surfaces to increase the surface area
EC dye on the surface and inside, if necessary
Correspondingly, it has micropores capable of supporting a charge transfer agent. Previous
The specific surface area of the semiconductor nanoporous layer is 1 to 5000 m.2
/ G is preferred, 10 to 2500 m2/ G is more preferred
Yes. Here, the specific surface area is B obtained from the adsorption amount of nitrogen gas.
ET specific surface area. If the specific surface area is too small, EC
This makes it possible to increase the amount of dye adsorbed.
May not be able to achieve the target. Semiconductor contained in the semiconductor nanoporous layer
The fine particles are not particularly limited and are appropriately selected according to the purpose.
For example, simplex semiconductors, oxide semiconductors
Body, compound semiconductor, organic semiconductor, complex oxide semiconductor,
Or mixtures thereof, which include dopants
Impurities may be included. The shape of the semiconductor
There is no particular limitation on the state, single crystal, polycrystal, amorphous or this
These mixed forms may also be used. As the single semiconductor, for example, silicon
(Si), germanium (Ge), tellurium (Te),
Etc. The oxide semiconductor is a metal oxide semiconductor.
For example, TiO2, Sn
O2, Fe2O3, SrTiO3, WO3, ZnO, Z
rO2, Ta2O5, Nb2O5, V2O5, In2O
3, CdO, MnO, CoO, TiSrO3, KTiO
3, Cu2O, sodium titanate, barium titanate
And potassium niobate. Examples of the compound semiconductor include CAD.
Sium 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-in
Examples thereof include sulfide of palladium. As the organic semiconductor, for example, poly
Offene, polypyrrole, polyacetylene, polypheny
Lembinylene, polyphenylene sulfide, etc.
It is. Examples of the composite oxide semiconductor include
SnO2-ZnO, Nb2O5-SrTiO3, N
b2O5-Ta2O5, Nb2O5-ZrO2, Nb2
O5-TiO2Ti-SnO2, Zr-SnO2, B
i-SnO2In-SnO2, Etc. Previous
SnO2-ZnO is a relatively large ZnO particle (particle size
SnO around the center of about 0.2μm)2Ultrafine particles (particle size
About 15nm), and the composite of both is quality
SnO in quantitative ratio2: ZnO = 70: 30 to 30:70
It is preferable that it is a surrounding. Nb2O5-SrTiO
3, Nb2O5-Ta2O5, Nb2O5-ZrO2,
And Nb2O5-TiO2Nb2O5The complex is
Nb2O5So that the mass ratio is 8: 2 to 2: 8.
Be merged. The shape of the semiconductor fine particles is not particularly limited.
Can be selected according to the purpose, spherical, nano
It can be any shape like a tube, rod, or whisker.
You can mix two or more kinds of fine particles with different shapes.
You can also. In the case of the spherical particles, the average particle size is
0.1 to 1000 nm is preferable, and 1 to 100 nm is preferable
More preferable. Two or more types of fine particles with different particle size distributions
You may mix children. In the case of the rod-like particles
Preferably has an aspect ratio of 2 to 50000,
5000 is more preferable. A method of forming the semiconductor nanoporous layer;
However, there is no particular limitation, and it is selected appropriately according to the type of semiconductor.
For example, metal anodic oxidation method, cathodic deposition
Method, screen printing method, sol-gel method, thermal oxidation method, vacuum steaming
Deposition, dc and rf sputtering, chemical vapor deposition, organic
Metal chemical vapor deposition, molecular beam deposition, laser ablation
Combination of the above methods
The semiconductor nanoporous layer can also be produced. -Method for forming oxide semiconductor nanoporous layer- Forming an oxide semiconductor (metal oxide) nanoporous layer 1
One method is to use a metal oxide precursor and a metal oxide precursor
A compound having at least one functional group that interacts with the precursor
In the solution containing the above, the metal oxide precursor is reacted to form a composite
A colloid that consists of metal oxide fine particles
A first step of obtaining a powdered sol, and applying the sol to a support;
This is dried or baked to produce a transparent conductive material on the transparent insulating substrate.
Forming a semiconductor nanoporous layer with micropores on an electroconductive membrane
Including a second step (hereinafter referred to as “composite game”).
It may be called "Legalization method"). In the first step, the diffusion controlled diffusion is obtained.
Since the formation reaction of metal oxide fine particles proceeds in the
Small granules with no formation of large grains or sedimentation
It is possible to obtain a colloidal dispersion sol solution in which the particles are uniformly dispersed
it can. In the so-called sol-gel method, the same metal oxide precursor is used.
For example, in the case of metal alkoxide, hydrolysis and dehydration
Gelation occurs by condensation reaction. In this case, -M
-OM- (where M is a metal element and O is an oxygen atom
It is prime. ) Chemically strong 3D bond network
Formed and cannot be solated again, once the gel
If it becomes, processing by means, such as application | coating, cannot be performed. Against this
The metal oxide precursor, and the phase of the metal oxide precursor
A metal oxide precursor in a solution containing the interacting compound;
In the method of obtaining a composite gel by reacting a metal oxide precursor,
Take advantage of the interaction nature of compounds that interact with the body
Can be made into sol again and has excellent workability
It becomes possible to make it. Here, as the metal oxide precursor,
Metal halides and metal complexes that are soluble in the solvent used
Compound, metal alkoxide, metal carboxylate or key
Examples include metal compounds such as rate compounds. concrete
Examples of the compound include TiCl.4(Titanium tetrachloride
), ZnCl2(Zinc chloride), WCl6(Tan hexachloride
Gusten), SnCl2(Stannous chloride), SrCl
6Metal halides such as (strontium chloride), Ti
(NO3)4(Titanium nitrate), Zn (NO3)2(nitric acid
Zinc), Sr (NO3)2(Strontium nitrate) etc.
Nitrate and 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 to be used. As the metal alkoxide, for example,
Zinc diethoxide, tungsten hexaethoxide, bar
Nazyl ethoxide, tin tetraisopropoxide, strike
Examples include rontium diisopropoxide. Specifically, a titanium oxide metal oxide layer is formed.
When formed, the metal alkoxide includes, for example,
Titanium tetraisopropoxide, titanium tetrano
Lumar propoxide, titanium tetraethoxide, titanium
Titanium tetranormal butoxide, titanium tetra
Isobutoxide, titanium tetratertiary buttoki
Sid etc. can be preferably used. Also, it interacts with the metal oxide precursor.
Examples of functional groups include carboxyl groups, amino groups, hydro
A xyl group etc. are mentioned. In addition, the metal oxide precursor and phase
Examples of functional groups that interact with each other include the amic acid structure as described above.
It may have one or more functional groups. The metal
Having at least one functional group that interacts with the oxide precursor
The compound is a carboxyl group, an amino group, a hydroxyl group,
A compound having one or more functional groups selected from amino acid structures
It is a compound. Particularly preferred are polymer compounds. this
Specific examples of such low molecular weight compounds include dicarboxylic acids,
Examples thereof include diamine, diol, and diamic acid. Further, specific examples of the polymer compound include
Ruboxyl group, amino group, hydroxyl group, amic acid structure
1 functional group selected from the structure on the main chain, side chain or cross-linked part
Examples thereof include polymer compounds having at least species. Polymerization
The main chain structure of the compound is not particularly limited
Are polyethylene-based structures, polystyrene-based structures,
Chrylate structure, polymethacrylate structure, polycarbonate
-Bonate structure, polyester structure, cellulose
Structure, silicone structure, vinyl polymer structure, polyamid
Structure, polyamideimide structure, polyurethane structure
Structure, polyurea structure, etc.
The thing which has arbitrary structures is mentioned. In addition, the carboxyl group, amino group,
Mainly functional groups selected from droxyl and amic acid structures
A polymer compound having at least one chain, side chain or cross-linked moiety;
Therefore, the form of interaction with the metal oxide precursor is appropriate.
From the viewpoint of polyacrylic acid having a carboxyl group in the side chain.
The use of formic acid is particularly preferred. Further, the metal oxide precursor
Polymer compounds having one or more functional groups that interact with the body
A polymer compound with a functional group that interacts with a carbo
Xyl group, amino group, hydroxyl group, amic acid structure
A polymer compound having a main chain structure similar to that described above
A copolymer may also be used. Mutual with the metal oxide precursor
Polymer compounds having one or more functional groups that act
Depending on the situation, two or more mixed systems, or carboxyl groups,
The above does not have a mino group, a hydroxyl group, or an amic acid structure
Use a mixed system with a polymer compound having the same main chain structure
May be. Functionality that interacts with the metal oxide precursor
The average degree of polymerization of the polymer compound having one or more groups is 10
About 0 to 10000000 is preferable, 5000 to 25
0000 is more preferable. Examples of the solvent include methanol,
Arco such as ethanol, isopropanol, butanol
Alcohol, formamide, dimethylformamide, geo
Dissolves metal oxide precursors such as xane and benzene, and
Use it if it does not react with the metal oxide precursor.
You can. In the following, metal alcohol is used as a metal oxide precursor.
As an example of the case of using oxide, the semiconductor nanoporous layer
The formation method will be described in detail. First, the metal alkoxide is added to the solvent.
(For example, an organic solvent such as alcohol). Further
In order to partially hydrolyze the metal alkoxide
Necessary water and catalyst such as hydrochloric acid, nitric acid, sulfuric acid or acetic acid
Add the acids. The amount of water and acids added here is
Depending on the degree of hydrolyzability of the metal alkoxide used
Can be selected as appropriate. Next, the resulting mixture
While stirring the solution, room temperature to 150 ° C. under a dry nitrogen stream
(Preferably room temperature to 100 ° C.)
The The metal used also for the reflux temperature and time
It can be selected appropriately according to the hydrolyzability of the oxide precursor
it can. As a result of the reflux, the metal alkoxide is partially
It is hydrolyzed. That is, the mixed solution
The amount of water contained is the amount of the metal alkoxide alcohol.
Small enough to not fully hydrolyze the xyl group
Therefore, the general formula M (OR)nThe metal alloy represented by
In lucoxide, all -OR groups are hydrolyzed.
Will result in a partially hydrolyzed state
The The metal alcohol in this partially hydrolyzed state
In xoxides, the polycondensation reaction does not proceed. others
Therefore, between the metal alkoxides,
Even if a chain is formed, the metal alkoxide is an oligo
Mer state. The metal alloy in this oligomer state
The refluxed mixed solution containing lucoxide is colorless and transparent.
There is almost no increase in viscosity. Next, the temperature of the mixed solution after reflux is set to room temperature.
To the mixed solution, carboxyl group, amino group, hydride
One or more functional groups selected from roxy groups and amino acid structures
A polymer compound (preferably polyacrylic acid)
Added. In this case, the organic solvent such as alcohol
Is difficult to dissolve, but this mixed solution contains
It dissolves easily and a transparent sol is obtained. This is the polymer
The carboxyl group of the compound and the metal alkoxide are salts
Bonded by a formation reaction to form a polymer complex compound
This is thought to be because of this. This transparent sol is usually
It is a colorless and transparent uniform solution. An excessive amount of water was further added to the transparent sol,
Room temperature to 150 ° C, preferably about room temperature to 100 ° C
And then continue the reaction for several minutes to an hour
The transparent sol gels at a degree, and the polymer compound and the gold
Formation of a composite gel with a cross-linked structure with a metal alkoxide
Is done. The resulting composite gel is further cooled to room temperature to 90 ° C. (through
(Normally about 80 ° C) and hold for 5 to 50 hours to continue the reaction.
Then, the composite gel is dissolved again and translucent metal oxide fine particles
A colloidal dispersion sol is obtained. This is the metal Al
When the polycondensation reaction proceeds by hydrolysis of coxide
Both the polymer compound and the metal alkoxide
Metal salt fine particles and carboxylic acid
This is due to the change to an ester or the like. The translucent metal oxide fine particles obtained as described above were obtained.
Particle colloidal dispersion sol was deposited on transparent insulating substrate
After applying to the transparent conductive film, by drying or baking,
A metal oxide film having fine holes is formed. The coating method is not particularly limited and is a known method.
Can be done, specifically, dip coating
Method, spin coating method, wire bar method, spray
A coating method is mentioned. Also, for drying, for example
Air drying, drying using a dryer such as an oven, vacuum
Freeze-drying is possible. Furthermore, the rotary evaporator
A method of evaporating the solvent using a device such as-may also be used. This
In this case, select the drying temperature and time appropriately according to the purpose.
Can be. Further, depending on the drying temperature, the metal oxide fine particles
Dry particle colloidal dispersion sol (liquid component containing the solvent)
The removal of the polymer compound or its reaction product
The product may not be removed. In such a case,
Firing is performed to remove these to form a pure metal oxide.
It is preferable. The firing is performed using, for example, a furnace.
The firing temperature is the same as the functional group used.
Depending on the type of polymer compound used,
The above temperature is generally employed. By the firing, crystals of metal oxide fine particles
And the sintering of metal oxide fine particles occurs simultaneously
Molecular components disappear due to thermal decomposition. In the formation of the semiconductor nanoporous layer
Of metal oxide particles in a composite gel with controlled diffusion
As the formation reaction proceeds, the formation of coarse particles and the precipitation of particles
Aggregation due to precipitation does not occur, and ultrafine particles with a small particle size are evenly distributed.
To obtain colloidal dispersion sol with finely dispersed metal oxide particles
be able to. Metal oxide fine particles of the semiconductor nanoporous layer
Child size, metal oxide fine particle aggregation structure period, metal acid
For the volume ratio between the fluoride fine particle agglomerated phase and the void phase,
For example, a metal oxide precursor with respect to the metal oxide precursor
Addition of compounds having one or more functional groups that interact with the body
The amount of the metal oxide precursor and the metal oxide precursor
A solid combined with a compound having one or more functional groups
The ratio of the amount of formation relative to the whole mixed solution to the desired degree
Can be controlled. That is, the metal oxide precursor and the functional group to be fired
Can be obtained by increasing the amount of the compound having one or more of
The volume ratio of the void phase in the semiconductor nanoporous layer is increased
The metal oxide precursor interacts with the metal oxide precursor
A solid component combined with a compound having one or more functional groups
If the ratio to the whole mixed solution is reduced, the resulting gold
The period of the metal oxide fine particle aggregation structure becomes smaller, and the void phase
Although the density increases, the size of the metal oxide particles themselves is large.
I'm angry. Metal oxidation for the metal oxide precursor
Compounds having one or more functional groups that interact with precursors
Is added to the whole mixed solution of the solid component
Depending on the proportion, it can be selected as appropriate and is generally mass
The ratio is preferably 0.1 to 1, more preferably 0.2 to 0.8.
Good. Metal oxide precursor versus metal oxide precursor
The amount of compound having one or more functional groups that interact with each other
Lower, dense semiconductor nanoporous layer with few macropores
When the mass ratio is less than 0.1,
A large three-dimensional network of -MOM
Therefore, the composite gel may not be redissolved. Ma
On the other hand, if the amount added is increased and exceeds 1,
It is easy to form a transparent semiconductor nanoporous layer with a gap. The solid component with respect to the whole mixed solution
As a ratio, the metal oxide precursor and the metal oxide precursor
Addition of compounds having one or more functional groups that interact with the body
Since it varies depending on the amount, it can be selected as appropriate.
1-10% by mass is preferable, and 2-5% by mass is more preferable.
Yes. When the ratio is less than 1% by mass, the composite gelation reaction
Metal oxidation in a transparent sol state with a slow response and high fluidity
Fine particles are formed, and coarse particles are formed.
On the other hand, if it exceeds 10% by mass, it is a composite gel from a transparent sol.
It may not be possible to obtain a uniform composite gel.
The In the following, tongues are used as metal alkoxides.
Take the case of using tenhexaethoxide as an example.
More detailed explanation of the method for forming the Ngüsten porous layer
To do. First, tungsten hexaethoxide is added.
Add to the alcohol to prepare a mixed solution. Arco
Water and acid as a catalyst are added to the
Water is 0.1 times that of tungsten hexaethoxide
Mol to equimolar amount, the acid is tungsten hexaethoxide.
About 0.05 times to 0.5 times mole
It is preferable to add them. The resulting mixed solution is at room temperature to
Reflux in a stream of dry nitrogen with stirring at 80 ° C. here
Reflux temperature and time at 80 ° C. for about 30 minutes to 3 hours
Is preferred. As a result of this reflux, a clear mixed solution is obtained.
The In this mixed solution, tungsten hexa
The ethoxide is in a partially hydrolyzed state.
In the oligomer state. Set the temperature of this mixed solution to room temperature.
And add polyacrylic acid. Originally alcohol
Polyacrylic acid, which is difficult to dissolve, is contained in this mixed solution.
A colorless transparent sol that dissolves easily is obtained. This is Polya
Crylic acid carboxylic acid and tungsten hexaethoxide
Are combined by a salt-forming reaction, and a polymer complex compound is formed.
This is because it is formed. More excess in this transparent sol
When water is added and kept at room temperature to 80 ° C. for several minutes to 1 hour
The transparent sol gelled in about a while, and polyacrylic acid and tan
Cross-linked structure containing at least gusten hexaethoxide
A complex gelation is formed. The composite gel was heated at about 80 ° C. for 5 to 50 hours.
When held, the composite gel dissolves again and a translucent sol is obtained.
It is done. This is because of the hydrolysis of tungsten hexaethoxide.
As the decomposition and polycondensation reactions proceed,
The salt structure of rilic acid and tungsten hexaethoxide
It turns into titanium oxide and carboxylic acid ester
Because. The obtained sol solution was dip coated.
Applied to a suitable substrate by a coating method, etc.
Heat to high temperature. With this heating, tungsten oxide fine particles
Crystallization of particles and sintering of tungsten oxide particles progress
At the same time, the polymer phase is thermally decomposed and tungsten oxide
Tungsten Oxide Fine Particles Aggregated in Phase Separation State
Will be formed. Poly (Tungsten hexaethoxide)
The amount of acrylic acid is 0.3 to 0.7 by mass ratio.
preferable. When the mass ratio is less than 0.3, -MO
-M- large 3D network is formed and the gel is dissolved
It may not be understood, and if it exceeds 0.7, it is relatively large
An air gap may be generated to form a transparent layer. In addition, tungsten hexaethoxide and poly
For the whole mixed solution of solid components with reacrylic acid
The ratio is preferably 1 to 10% by mass. The ratio is
If it is less than 1% by mass, the progress of the composite gelation reaction is slow,
Tungsten oxide particles are formed in a highly fluid sol state
And coarse tungsten oxide particles are formed.
There is. On the other hand, when it exceeds 10% by mass,
It is not possible to obtain a uniform composite gel that progresses quickly to a combined gel.
There is. -Method of forming compound semiconductor nanoporous layer- Examples of the method for forming the compound semiconductor nanoporous layer include:
For example, electrolytic deposition, chemical bath deposition, photochemical deposition, etc.
Yes, specifically as shown below. (Electrolytic Deposition Method) There are few electrolytic deposition methods.
In the electrolyte containing the ions of the elements to be deposited,
An electrode formed with a transparent conductive film on an edge substrate, and a pair of electrodes
Between the electrodes and electrochemically
Causes a redox reaction to make the compound semiconductor layer transparent conductive
It is formed on the electrode on which the film is formed (surface technology V
ol. 49, no. 1 3 pages 1998). The compound semiconductor produced in this process is an example.
For example, CuGaS2(Copper gallium sulfide), CuGaSe
2(Copper gallium selenide), CuGaTe2(Tellurization
Copper gallium), CuInS2(Copper indium sulfide), C
uInSe2(Copper indium selenide), CuInTe
2(Copper indium telluride), AgInS2(Silver sulfide
Nd), AgInSe2(Silver selenide Injiu
), AgInTe2(Indium telluride), Zn
Se (zinc selenide), ZnTe (zinc telluride), C
dTe (cadmium telluride), Cu2S (copper sulfide),
Cu2And Se (copper selenide). The electrolyte includes a raw material element in a solvent.
Use a mixture of solutes such as sulfur oxides and chlorides
Water (pure water, distilled water, etc.) is used as the electrolyte solvent.
I can. However, hydrogen is generated by electrolysis of water.
In the case of applying a voltage to the base, the solvent is effective as a non-aqueous solution.
Aircraft can be used. Organic solvents include aceto
Nitrile, dimethylformamide, propylene carbonate
Can be used. The non-aqueous solution
Is an inorganic non-aqueous solution such as liquid ammonia or liquid sulfur dioxide
Can be used as the solvent. The solute is an electrode such as sulfate or chloride.
Containing elements constituting compound semiconductors deposited on top
As long as it is soluble in the solvent. For example, sulfur
Acids include cuprous sulfate, indium sulfate, and gallium sulfate.
Um, silver sulfate, zinc sulfate, cadmium sulfate, etc.
The Also, as chlorides, cuprous chloride, indium chloride
Gallium chloride, silver chloride, zinc chloride, cadmium chloride
These compounds are used as reducing solutes.
The The solute is not limited to the above compound,
These may be used alone or in combination of two or more. Ma
As the solute, selenium oxide, selenium hydride, oxidation
Tellurium, tellurium hydride, sodium thiosulfate, thiourea
Etc. can be used as oxidized solutes. When the above oxidized solute is used, water
Contained in the oxidized solute by adjusting the concentration of elementary ions
The deposition of elemental ions can be promoted. The hydrogen ion
The concentration is adjusted with a regulator such as sulfuric acid or hydrochloric acid.
Can. Hydrogen ion adjusted by the adjusting agent
The on concentration is preferably pH 0.9 to 4.0, pH 1.5
-2.5 is more preferable. In addition to the above compounds as the electrolyte,
Involved in electrolytic reduction to obtain electrolyte conductivity during demolition
It is also possible to add a supporting electrolyte composed of no inert material
Yes. Examples of the supporting electrolyte include NaClO.4(salt
Sodium borate), LiClO4(Lithium chlorate) etc.
Is mentioned. The supporting electrolyte is 0.05-1 mol /
The content of 1 is preferable. When the deposition of the compound semiconductor proceeds
In order to increase the necessary adhesion, an additive is added to the electrolyte.
You can also put it in. Examples of the additive include amines and amines.
Lucaloid, sulfonic acid, mercaptan, sulfide, etc.
Is mentioned. Between the opposing electrodes arranged in the electrolyte
To apply a voltage to the third electrode as the voltage reference electrode.
A reference electrode can be used. Between the opposing electrodes
Use a reference electrode to control a constant voltage or current
You can also. The reference electrode is a standard hydrogen electrode, saturated
Calomel electrode, standard silver chloride electrode, standard mercury oxide electrode, etc.
Can be used. The porous semiconductor disposed in the electrolyte
As an electrode facing the body layer, voltage application in solution
A material that is difficult to dissolve, that is, a material with a low ionization tendency
Can be used. For example, platinum (Pt), gold (A
u), silver (Ag) and the like. Between opposed electrodes arranged in the electrolyte
The voltage applied to the electrolyte contained in the electrolyte
Elemental ions of compounds containing elements that constitute compound semiconductors
It is preferable that it is baser than the redox potential. The content of the compound contained in the electrolyte is 5
~ 400 mmol / l is preferable, reduced element ion stack
In the product, 5 to 20 mmol / l is more preferable.
100-400 mmol / l is good for deposition of elementary ions
More preferable. The temperature of the solution is preferably 20-100 ° C.
22 to 70 ° C. is more preferable. Voltage application time when forming the compound semiconductor layer
Is preferably 300-3600 seconds, 800-2400 seconds
Is more preferable. The compound semiconductor deposited in the step is baked.
And crystallize. The crystallization temperature is the compound semiconductor that is deposited
Although it depends on the type of body, 50 to 600 ° C. is preferable.
50-600 degreeC is more preferable. The crystallization time is 1 to
60 minutes is preferable and 15 to 30 minutes is more preferable. (Chemical bath deposition method) The chemical bath deposition method is a
In a solution containing at least one kind of deposited ions,
Place the electrode on which a transparent conductive film is formed on a bright insulating substrate,
Reduction reaction by adjusting the temperature and ion concentration of the solution
And the compound semiconductor layer is formed on the electrode
(Jonal of Applied Phys
ics, vol. 82, 2, 655, 1997). In this chemical bath deposition method, an oxidizing agent or a reducing agent is used.
To produce more elemental ions and stabilize them
Complexing agent, buffered to prevent fluctuations in hydrogen ion concentration
Addition of stabilizer, stabilizer to prevent natural decomposition in solution
The transparent conductive film is formed by these redox reactions.
The compound semiconductor can be deposited on the formed electrode.
The compound semiconductor produced in this process is particularly limited
ZnSe (zinc selenide), ZnTe (te
Zinc ruluide), CdTe (cadmium telluride), Cu
2S (copper sulfide), Cu2And Se (copper selenide)
It is. The solution is sulfated which becomes an ion in a solvent.
Use a mixture of solutes such as substances and chlorides. Said melting
As the medium, water (pure water, distilled water, etc.) or the like is used. Ma
Organic solvents can also be used, for example, acetonitrile
, Dimethylformamide, propylene carbonate, etc.
Can be used. Also liquid ammonia, liquid
An inorganic non-aqueous solution such as sulfur dioxide can also be used. The solute is the transparent material such as sulfate or chloride.
Compound semiconductor to be deposited on the electrode with conductive film
What is necessary is just to include the element to comprise. For example, sulfate
Examples include cuprous sulfate, indium sulfate, and gallium sulfate.
, Silver sulfate, zinc sulfate, cadmium sulfate, etc.
The Also, as chlorides, cuprous chloride, indium chloride
Gallium chloride, silver chloride, zinc chloride, cadmium chloride
Etc. Examples of the solute include selenium oxide, hydrogen
Selenium acid, tellurium oxide, tellurium hydride, sodium thiosulfate
Um, thiourea and the like can also be preferably used. When the above compound is used,
By adjusting the on-concentration, the elemental ion contained in the compound
Can promote the accumulation of ions. Adjust the hydrogen ion concentration
Examples of the adjusting agent for adjusting the concentration include sodium hydroxide
, Basic compounds such as ammonium hydroxide, inorganic acids, organic
Mechanical acid or the like can be used. In addition, the hydrogen ion concentration
The buffer used to control the variation in degree is
Sodium acetate sodium acetate, oxycarboxylic acid type
NO, inorganic acid such as boric acid or carbonic acid has a small dissociation constant
Or use alkali salts of organic and inorganic acids
Can do. As complexing agents, ammonium hydroxide,
Sodium citrate, sodium acetate, ethylene glyco
Or the like can be used. Lead chlorides, sulfides and nitrides as stabilizers
Etc. can be used. Of the compound semiconductor in the solution
The concentration of the compound containing the raw material element is 1.0 × 10-3
˜2 mol / l is preferred, 2.0 × 10-2~ 1mo
l / l is more preferred. The temperature of the solution is preferably 20 to 100 ° C.
22 to 70 ° C. is more preferable. In addition, the compound half
The formation time of the conductor layer is preferably 300 to 3600 seconds.
200-2400 seconds are more preferable. The compound semiconductor layer deposited in the step is
Firing and crystallization. The crystallization temperature is half of the compound
Depending on the type of conductor, 50 to 600 ° C. is preferable,
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) The photochemical deposition method is a
At least one sodium thiosulfate and one or more metal ions
A transparent conductive film was formed on the transparent insulating substrate in the solution containing
An electrode is placed, and a photoreaction occurs by irradiating the electrode with ultraviolet rays.
And the compound semiconductor layer is formed on the electrode.
(Japan Journal Applied Ph
ysics vol36, L1146 1997). This photochemical deposition method uses ions in solution.
Compound formation reaction by photoexcitation of (thiosulfate ion etc.)
Caused by the presence or absence of light irradiation and intensity change.
You can do it easily. The compound half produced in this process
The conductor is not particularly limited, but CuGaS2(Copper sulfide gas
Li), CuInS2(Copper indium sulfide), AgI
nS2(Silver indium sulfide), Cu2S (copper sulfide) etc.
Can be mentioned. The solution is sulfated which becomes an ion in a solvent.
Use a mixture of solutes such as substances and chlorides. Said melting
The quality of the compound such as sulfate or chloride that is desired to be deposited on the electrode.
Any element may be used as long as it contains an element constituting a physical semiconductor. example
Examples of sulfates include cuprous sulfate, indium sulfate, and sulfate.
Examples thereof include gallium acid and cadmium sulfate. Also salt
The compounds include cuprous chloride, indium chloride, and gallium chloride.
And cadmium chloride. The solute is limited to the above compound.
No, it may be used alone or in combination of two or more
Good. When using an oxidized compound as described above, hydrogen
Contained in the oxidized compound by adjusting the ion concentration
The deposition of elemental ions can be promoted. The hydrogen ion
The concentration can be adjusted with a regulator such as sulfuric acid.
it can. Hydrogen ion concentration adjusted by the adjusting agent
Is preferably pH 1.5 to 4.0, pH 2.5 to 3.5.
Is more preferable. The solution is preferably stirred,
It is preferable to stir at rpm or lower. Further, the light excitation
The light used to wake up is from a high-pressure mercury light source lamp, etc.
UV light is generated, condensed by a single convex lens, and the solution
Irradiation is performed on the electrode disposed therein. Single convex len
The glass is preferably made of quartz glass. Including the raw material elements of the compound semiconductor in the solution
The concentration of the compound is preferably 1.0 to 20 mmol / l.
More preferably, 2.0 to 10 mmol / l is more preferable. Previous
The temperature of the solution is preferably 20 to 40 ° C, and 22 to 35 ° C.
Is more preferable. In addition, the formation time of the compound semiconductor layer
Is preferably 2400-4800 seconds, 3000-360
0 seconds is more preferable. The deposited compound semiconductor is fired and sintered.
Crystallize. The crystallization temperature is the seed of the compound semiconductor to be deposited.
80 to 600 ° C. is preferable, depending on the
00 ° C. is more preferable. The crystallization time is 1 to 60 minutes.
Preferably, 15 to 30 minutes are more preferable. Especially sulfide type
80 to 400 ° C. for selenium, 300 to 550 for selenium
In the case of ° C and tellurium, 400 to 600 ° C is preferable. -Formation of composite oxide semiconductor nanoporous layer
Method-The composite oxide semiconductor nanoporous layer is
On the oxide semiconductor nanoporous layer formed by
An oxide semiconductor nanoporous layer is formed by the Lugel method,
A method of combining, or mixing two kinds of oxide semiconductor particles
A method of applying the paste on the electrode, etc.
The Specifically, an oxide semiconductor colloid aqueous solution
Acetic acid was added dropwise to the gel solution mixed well in the mortar.
A little oxide semiconductor powder, alcohol to be combined
Add one at a time and mix well. Add a surfactant.
This is mixed with a fluorine-doped tin oxide conductive film gas.
Hot plate (100-120)
)) By spray coating and firing, semiconductor fine particles
The crystallization of the child and the firing of the semiconductor fine particles proceed and the desired
Composite oxide semiconductor nanoporous layer with different porosity
To do. The semiconductor nanoporous layer is not limited to a single layer,
Multi-layer coating of semiconductor fine particle dispersions with different particle sizes,
Different types of semiconductor particles (or different binders, additives
The coating layer containing the additive) can also be applied in multiple layers.
Multi-layer coating is effective even when the film thickness is insufficient with a single coating.
is there. For the multilayer coating, an extrusion method or a scanning method is used.
The ride hopper method is suitable. Also apply multi-layer coating
In some cases, multiple layers may be applied at the same time.
Next, you may repaint. Furthermore, if you are overprinting sequentially,
A clean printing method can also be preferably used. The semiconductor nanoporous layer bears an EC dye.
Heat treatment (e.g. 10 to 100-550 ° C. before holding)
Minutes). As a result, many semiconductor nano
Can remove moisture and other impurities adsorbed on the surface of the porous layer
At the same time, the surface of the porous layer can be activated to absorb EC dyes.
Can be performed efficiently. The semiconductor nanoporous layer has a thickness of 100.
μm or less is preferable, 50 μm or less is more preferable, 2
More preferably 0 μm or less. The porous layer is too thin
The amount of EC dye that can be adsorbed
There is a case. On the other hand, if it is too thick, the transparency decreases, and E
In some cases, the loss of charge injected into the C element increases. -EC dye- The EC dye is formed on the surface and inside of the semiconductor nanoporous layer.
As well as the electrolyte as required.
It is preferable to be contained in a dissolved or dispersed state in the layer.
That's right. As the EC dye, an electrochemical oxidation reaction and
And color development or decoloration by at least one of the reduction reactions
There is no particular limitation as long as
For example, organic compounds and metal complexes are preferred.
Named appropriately. These may be used alone.
Two or more kinds may be used in combination. Examples of the metal complex include Prussia.
Blue, metal-bipyridyl complex, metal phenanthroli
Complex, metal-phthalocyanine complex, metaferricyani
And derivatives thereof. Examples of the organic material include (1) Pi.
Lysine compounds, (2) conductive polymers, (3) still
(4) Donor / acceptor type compounds,
(5) Other organic pigments are included. Examples of (1) pyridine compounds include
For example, viologen, heptyl viologen (dihepti
Ruviologen dibromide), methylenebispyridini
Um, phenanthroline, azobipyridinium, 2, 2
-Bipyridinium complexes, quinoline / isoquinoline, etc.
Is mentioned. Examples of (2) conductive polymers include
Polypyrrole, polythiophene, polyaniline, poly
Riphenylenediamine, polyaminophenol, polybi
Nylcarbazole, high molecular viologen polyioncon
Plex, TTF, and derivatives thereof
The Examples of (3) styryl compounds include
For example, 2- [2- [4- (dimethylamino) phenyl]
Ethenyl] -3,3-dimethylindolino [2,1-
b] oxazolidine, 2- [4- [4- (dimethylamino)
C) phenyl] -1,3-butadienyl] -3,3-di
Methylindolino [2,1-b] oxazolidine, 2-
[2- [4- (Dimethylamino) phenyl] ethenyl]
-3,3-dimethyl-5-methylsulfonylindolino
[2,1-b] oxazolidine, 2- [4- [4- (di
Methylamino) phenyl] -1,3-butadienyl]-
3,3-dimethyl-5-sulfonylindolino [2,1
-B] oxazolidine, 3,3-dimethyl-2- [2-
(9-Ethyl-3-carbazolyl) ethenyl] indori
[2,1-b] oxazolidine, 2- [2- [4-
(Acetylamino) phenyl] ethenyl] -3,3-di
Methylindolino [2,1-b] oxazolidine, etc.
Is mentioned. (4) Donor / Acceptor type compound
Examples include tetracyanoquinodimethane, teto, and the like.
Latiafulvalene, and the like. Examples of (5) other organic dyes include
For example, carbazole, methoxybiphenyl, anthrax
Non, quinone, diphenylamine, aminophenol,
Tris-aminophenylamine, phenylacetyle
, Cyclopentyl compounds, benzodithiolium compounds
, Squarium salt, cyanine, rare earth phthalocyanine
Complex, ruthenium diphthalocyanine, merocyanine,
Enanthroline complex, pyrazoline, redox indicator, p
H indicator, derivatives thereof, and the like. Among these, viologen, heptyl
Viologen (diheptyl viologen dibromide, etc.)
A viologen dye such as is preferred. In addition, the E
As the C dye, it shows a colorless or extremely light color in the oxidized state,
Reduced coloring type that develops color in reduced state, none in reduced state
Oxidation coloring type that shows color or ultra-light color and develops in oxidized state
Show color development in reduced or oxidized state, reduced or
A multicolored type that develops several colors depending on the degree of oxidation
Any of the above may be used, and it is appropriately selected according to the purpose.
be able to. A combination when two or more EC dyes are used in combination
There is no particular limitation on the combination, and it is appropriately selected according to the purpose.
For example, viologen and polyaniline
Combination with phosphorus, polypyrrole and polymethylthiophene
In combination with polyaniline and Prussian blue
And so on. On the surface and inside of the semiconductor nanoporous layer
There is no particular limitation on the method for supporting the EC dye,
Known techniques can be used. For example, a vacuum evaporation method
I-process, spin coating, etc., field deposition, electric
Boundary polymerization method, natural adsorption method, etc.
The method can be selected as appropriate. Above all, the natural adsorption method is
Reliably and evenly in the fine pores of the metal oxide layer
Does not require special equipment capable of supporting functional molecules
In many cases, it is about a monolayer, which is more than necessary.
Preferred method with many advantages, such as lack of quantity
It is. Specifically, it is well dried in an EC dye solution.
A transparent substrate having a doped semiconductor nanoporous layer
Or a method of applying a dye solution to a semiconductor nanoporous layer
Can be used. In the former case, immersion method, dip
The method, the roller method, the air knife method, etc. can be used. Immersion
In the case of the dipping method, the dye adsorption may be performed at room temperature,
Heating as described in Japanese Patent Application Laid-Open No. 7-249790
You may carry out by refluxing. Also, as the latter application method
The wire bar method, slide hopper method,
There are the fusion method, curtain method, spin method, spray method, etc.
The Examples of the solvent for dissolving the EC dye include
For example, water, alcohols (methanol, ethanol, t
-Butanol, benzyl alcohol, etc.), nitriles
(Acetonitrile, propionitrile, 3-methoxypropyl
Lopionitrile), nitromethane, halogenated hydrocarbons
Elementary (dichloromethane, dichloroethane, chloroform,
Chlorobenzene, etc.), ethers (diethyl ether,
Tetrahydrofuran, etc.), dimethyl sulfoxide, amino
(N, N-dimethylformamide, N, N-dimethyl)
Luacetamide, etc.), N-methylpyrrolidone, 1,3-di
Methyl imidazolidinone, 3-methyl oxazolidino
, Esters (ethyl acetate, butyl acetate, etc.), carbonate
Stealth (diethyl carbonate, ethylene carbonate, propylene carbonate)
Etc.), ketones (acetone, 2-butanone, cyclohexane)
Xanone), hydrocarbons (hexane, petroleum ether,
And mixed solvents thereof.
The The amount of adsorption of the EC dye is determined by the semiconductor nanoporous
Unit surface area (1m2) 0.01-100m
mol is preferred. In addition, it is compatible with EC dye semiconductor particles.
The adsorbed amount is 0.01 to 10 per 1 g of semiconductor fine particles.
A range of 0 mmol is preferred. EC dye
The concentration in the electrolyte is preferably 0.001 to 2 mol / l.
0.005 to 1 mol / l is more preferable. -Charge transfer agent- The charge transfer agent is a semiconductor nano-particle, similar to the EC dye.
Supported on the surface and internal micropores of the porous layer,
If necessary, in a state dissolved or dispersed in the electrolyte layer
It is preferable to contain. In addition, semiconductor of charge transfer agent
The nanoporous layer can be supported by the same method as EC dyes.
You can. Combined use of the charge transfer agent and an EC dye
And the additive color effect due to simultaneous color development of both
The redox reaction proceeds smoothly and the color development efficiency
Will be improved. The charge transfer agent is not particularly limited.
Can be selected according to the purpose.
Those exhibiting trochromic properties are suitable, for example
Drazone, phenothiazine, [β- (10-phenothia
Dil) -propoxy] phosphonic acid (phenothiazine derivative)
Body), etc., and one of these may be used alone or two of them
A combination of the above can be used. The amount of the charge transfer agent adsorbed is a large amount of semiconductor nano particles.
Unit surface area of porous layer (1m2) 0.01-100
mmol is preferred. Also, semiconductor particles of charge transfer agent
The adsorbed amount with respect to 1 g of semiconductor fine particles is 0.01 to
A range of 100 mmol is preferred. Also charge
The concentration of the transfer agent in the electrolyte is 0.001 to 2 mol / l.
Preferably, 0.005 to 1 mol / l is more preferable. -Electrolyte layer- The electrolyte layer is not particularly limited and is appropriately selected according to the purpose.
Contain EC dye and charge transfer agent
Preferably as EC dye and charge transfer agent
Can be used by appropriately selecting from the above.
However, EC dyes or electrical currents supported on the semiconductor nanoporous layer
The same as the load transfer agent is preferred. The form of the electrolyte layer and
Can be liquid, solid or gel.
Yes. (1) In the case of a liquid electrolyte layer When the electrolyte layer is liquid, I/ I3 , Br
/ Br3 Redox pairs such as quinone / hydroquinone pairs
(Redox couple) and can be transported between electrodes at a sufficient speed
It is necessary to use a charge transporting material such as an electrolyte dissolved in a solvent.
Are preferred. Examples of the electrolyte include iodine and odor.
Elementary, LiI, NaI, KI, CsI, CaI2, LiB
r, NaBr, KBr, CsBr, CaBr2Such as metal
Halide, tetraethylammonium iodide, iodine
Tetrapropylammonium iodide, tetrabutylammonium iodide
Ammonium, tetramethylammonium bromide, teto bromide
Raethylammonium, tetrabutylammonium bromide
Halogenated salts of ammonium compounds such as methylviolo
Alkynes such as gen chloride and hexyl viologen bromide
Ruviologen, hydroquinone, naphthohydroquinone
Such as polyhydroxybenzene, ferrocene, ferrocyan
By using at least one of iron complexes such as phosphate
However, the present invention is not limited to this. Also with iodine
Like a combination of lithium iodide, etc.
Used by mixing multiple electrolytes that produce (redox couple)
This improves the performance of the EC element, especially the current characteristics.
Is possible. Among these, iodine and ammonia
Preferred examples of such compounds include combinations of iodine compounds and iodine and metal iodides.
I can get lost. As a solvent for dissolving these electrolytes,
Ethylene carbonate, propylene carbonate, etc.
-Bonate compounds, dioxane, diethyl ether, ether
Ethers such as tylene glycol dialkyl ether,
Methanol, ethanol, isopropyl alcohol, ethanol
Tylene glycol, propylene glycol, polyethylene
Alcohols such as ethylene glycol, acetonitrile,
Nitriles such as zonitrile, dimethylformamide, di
Methyl sulfoxide, propylene carbonate, ethylene carbonate, etc.
Aprotic polar solvent, water, etc. can be used
However, it is not limited to these. Electrolyte concentration of the electrolyte in the solvent
Is preferably 0.001 to 2 mol / l,
005 to 1 mol / l is more preferable. Electrolyte concentration
If it is less than 0.001 mol, it is
Performance may not sufficiently work, and the characteristics may deteriorate.
The On the other hand, if it exceeds 2 mol / l, it will
The above effects do not appear and the viscosity of the electrolyte solution is high.
May lead to a decrease in current. (2) In the case of a solid electrolyte layer When the electrolyte layer is solid, it is ion conductive or electronic
Any substance exhibiting conductivity may be used, for example, A
gBr, AgI, CuCl, CuBr, CuI, Li
I, LiBr, LiCl, LiAlCl4LiAlF
4, Etc., AgSBr, C5H5NHAg
5I6, Rb4Cu16I7Cl13, Rb3Cu7C
l10Inorganic salt such as LiN, Li5NI2, Li6N
Br3Lithium nitride and its derivatives such as Li2S
O4, Li4SiO4, Li3PO4Lithium acid etc.
Borate, ZrO2, CaO, Gd2O3, HfO2, Y
2O3, Nb2O5, WO3, Bi2O3And these
Oxides such as solid solution of CaF, CaF2, PbF2, SrF2,
LaF3, TISn2F5, CeF3Fluoride such as C
u 2S, Ag2S, Cu2Se, AgCrSe2Etc.
Lucogenide, perfluorosulfur on vinyl fluoride polymer
Polymers containing phonic acid (eg Nafion), organic
Polythiophene, polyaniline,
Compounds such as polypyrrole, fragrances such as triphenylamine
Group amine compounds, carbazo such as polyvinylcarbazole
Silane compounds such as polyol compounds and polymethylphenylsilane
Can be used, but is not limited to this
Absent. (3) In the case of gel electrolyte layer In the case where the electrolyte layer is in the form of a gel, polymer addition, oil
Lugelling agent addition, polyfunctional monomers, the electrolyte and
It can be used by mixing with the solvent. The polymer
When gelating by addition, “Polymer E”
electrete Revie ews-1 and 2 "
(JR MacCallum and CA Vincen
Co-edition of t, ELSEVIER APPLIED SCI
ENCE) etc. can be used.
In particular, polyacrylonitrile, polyvinyl fluoride
Redene and the like are preferred. By adding the oil gelling agent
In the case of gelation, “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 "
The compounds described in etc. can be used
However, compounds having an amide structure in the molecular structure are particularly preferred.
Good. Further, the matrix material and the supporting electrolyte are mixed.
Using a solid electrolyte layer obtained by polymerizing the mixture to form a film
You can also. --Supporting electrolyte-- The supporting electrolyte is not particularly limited and depends on the purpose.
May be selected as appropriate, and may be an inorganic electrolyte.
Alternatively, it may be an organic electrolyte. These are one kind alone
May be used, two or more may be used in combination,
It may be a commercially available product or may be appropriately synthesized. Examples of the inorganic electrolyte include inorganic acids.
Anion-alkali metal salt, alkali metal salt, alkali
Earth metals, etc.
N-alkali metal salts are preferred, and inorganic acid lithium salts are preferred.
More preferable. The inorganic acid anion-alkali metal salt
For example, XAsF6, XPF 6, XBF4, XC
lO4(However, in these, X
Represents H, Li, K or Na. ), Specifically persalt
Preferable examples include lithium oxalate. Examples of the alkali metal salt include L
iI, KI, LiCF3SO3, LiPF6, LiCl
O4, LiBF4, LiSCN, LiAsF6, NaC
F3SO3, NaPF6, NaClO4, NaI, Na
BF4, NaAsF6, KCF6SO3, KPF6,
And so on. Examples of the organic electrolyte include organic acids.
Anion-alkali metal salt, quaternary ammonium salt, anion
On-active surfactants, imidazolium salts, etc.
Among these, organic acid anions-alkali metal salts are
Preferably, an organic acid lithium salt is more preferable. The organic acid anion-alkali metal salt
For example, XCF3SO3, XCnF2n + 1SO
3(N = 1-3), XN (CF3SO2)2, XC (C
F3SO2)3, XB (CH3)4, XB (C6H5)
4(In these, X is H,
Li, K or Na), specifically polymethacrylic
Preferable examples include lithium lurate. Examples of the quaternary ammonium salt include
[CH3(CH2)3]4N / Y, CnH2n + 1
N (CH3)3・ Y (n = 10-18), (CnH
2n + 1) 2N (CH3)2Y (n = 10-18),
(However, in these, Y is B
F4, PF6, ClO4, F, Cl, Br or OH
The ) Examples of the anionic surfactant include
CnH2n + 1COO.X (n = 10-18), C
nH2n + 1OCmH2mCOO.X (n = 10-1)
8, m = 10-18), C10H7COO ・ X 、 CnH
2n + 1C10H6COO.X (n = 10-18), C
nH2n + 1SO3-X (n = 10-18), CnH2
n + 1OCmH2mSO3X (n = 10-18, m =
10-18), C10H 7SO8・ X, CnH2n + 1
C10H6SO3-X (n = 10-18), CnH
2n + 1OSO3・ X (n = 10-18), etc.
Where X is H, Li, K or
Represents Na. ). As the supporting electrolyte, in particular, an inorganic acid lithium
It is preferable to contain an um salt and an organic acid lithium salt. --Matrix material-- The matrix material is not particularly limited,
Can be appropriately selected, for example, a heteroatom
And the like. A polymer compound having a hetero atom
For example, a polymer compound having an oxygen atom, nitrogen source
Polymer compound having a sulfur atom, polymer compound having a sulfur atom
Products, polymer compounds having halogen atoms, etc.
It is. As the polymer compound having an oxygen atom,
Is, for example, R1-(OCH2CH 2)nO-R2(N
Represents an integer and R1Are ethylene, styrene,
Lopylene 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 ketone
Ton group, acrylamide group, etc., R2H, CH
3Or R1Represents. The compound represented by
Specifically, polyethylene glycol, poly
Lopylene glycol, non-polyethers (eg poly
(3-hydroxypropionic acid), polyvinyl acetate),
Etc. are preferable. As the polymer compound having a nitrogen atom
Is, for example, R1-(NHCH2CH2)nNH-R2
(N represents an integer, R1Is ethylene group, styrene
Group, propylene group, butene group, butadiene group, vinyl chloride
Group, vinyl acetate group, acrylic acid group, methyl acrylate
Group, methacrylic acid group, methyl methacrylate group, methyl vinyl
Nylketone group, acrylamide group, etc., R2Is
H, CH3Or R1Represents. ) The compound represented by
Specific examples include polyethyleneimine, poly
Li-N-methylethyleneimine, polyacrylonitrile
Etc. As the polymer compound having a sulfur atom
Is, for example, R1-(SCH2CH 2)nS-R2(N
Represents an integer and R1Are ethylene, styrene,
Lopylene 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 ketone
Ton group, acrylamide group, etc., R2H, CH
3Or R1Represents. The compound represented by
Specifically, polyalkylene sulfides,
Etc. As the molecular weight of the matrix material,
There is no limit to the number, and it can be selected appropriately according to the purpose.
However, the lower one often has fluidity at room temperature,
From the viewpoint of film formability, a lower value is preferable.
The average molecular weight is preferably 1000 or less. In the electrolyte layer of the matrix material
The amount used is a molar ratio with the supporting electrolyte (matrix).
(Xox material: supporting electrolyte) is 70:30 to 5:95
Preferably 50:50 to 10:90
50:50 to 20:80 is particularly preferable.
Good. Note that the molar ratio is determined by the matrix material.
And the molar amount of ions of the supporting electrolyte
means. The molar amount of the matrix material is a polymer compound.
Means the molar amount converted to a single monomer unit
To do. The film-like solid electrolyte layer is formed of the matrix.
Benzoyl peroxide in a mixture of Lix material and supporting electrolyte
And a small amount of polymerization initiator such as azobisisobutyronitrile.
The added material is thinly stretched, and then heated to polymerize.
Or by adding a photopolymerization initiator such as Irgacure
It can be made by polymerizing by external irradiation.
it can. The thickness of the solid electrolyte film is usually 3
It is 0-500 micrometers, Preferably it is 50-200 micrometers. -Pair of transparent electrodes- The pair of transparent electrodes is transparent and conducts electricity.
There is no particular limitation as long as it is selected, depending on the purpose
For example, indium tin oxide (ITO), oxidation
Tin (NESA), tin oxide doped with fluorine (FT
O), indium oxide, zinc oxide, platinum, gold, silver, logistic
Um, copper, chromium, carbon and the like. Among these
Low surface resistance, good heat resistance, chemical stability
Fluorine dopin from the point that there is high light transmittance, etc.
Tin oxide (FTO), indium tin oxide (IT
O) is preferred. The surface resistance of the conductive substrate is as described above.
The lower one is preferable, and the specific surface resistance value and
100Ω / cm2The following is preferred, 10Ω / c
m2The following is more preferable. Further, the thickness of the transparent electrode and
There is no particular limitation, and it can be selected appropriately according to the purpose.
In the case of the transparent electrode, for example, 0.1 μm
m or more, particularly 0.1 to 20 μm
The -Support- The support is used as a base material on which the transparent electrode is provided.
The material, shape, structure, size, etc.
In particular, there is no particular limitation and it can be designed as appropriate. Previous
Examples of the support include glass plates and polymer films.
And the like. With polymer film materials
Tetraacetylcellulose (TAC), polyester
Tylene terephthalate (PET), polyethylene naphtha
Rate (PEN), syndiotactic polystyrene
(SPS), polyphenylene sulfide (PPS), poly
Recarbonate (PC), polyarylate (PAr),
Polysulfone (PSF), Polyester sulfone
(PES), polyetherimide (PEI), cyclic poly
Examples include olefins and brominated phenoxy. -Other members- The other members are not particularly limited, and EC
Can be selected as appropriate according to the application of the spray, etc.
For example, spacers, sealing members, lead wires, reflection means,
And so on. As an example of the EC element of the present invention, FIG.
As shown in 1 and 12, a semiconductor nanoparticle on which EC dye 2 is supported.
A transparent electrode 5 provided with a porous film 8 on its surface, and an EC color
Semiconductor nanoporous film 8 carrying element 2 is provided on the surface.
The electrolyte layer 9 is placed between the transparent electrode 5 and the semiconductor nanoporous material.
Sandwiched between the membrane 8 and the semiconductor nanoporous membrane 8
The ones that existed are listed. Transparent electrode 5 and transparent
The electrode 5 is connected by a lead wire 60 and connected to the power source 50.
It has been continued. The EC element includes a transparent electrode 5 and a transparent electrode.
5 is applied to the semiconductor nanoporous film 8 by applying a voltage between
The developed EC dye 2 is decolorized. The EC display of the present invention is particularly limited.
It is not, but the area gradation method by the flat ground mixing, by the flat ground mixing
For density gradation method, area gradation method by lamination mixing and lamination mixing
By one of the methods selected from the density gradation method
It is preferable to use it in color. [0145] The area gradation method by the mixing of the flat ground is a printed matter.
This is a method for expressing a color image based on the same principle as for halftone dots.
The For example, color develops in R (red), G (green), and B (blue)
Many minute pixels are provided in the plane, and the color density of each pixel
The color changes by ON / OFF at a constant density without gradation
A color image is expressed by the difference in area (example)
For example, the applied voltage and the applied time are constant). The density gradation method by the mixing of the flat ground is the same as that described above.
In the same way, color images are expressed using the same principle as the halftone dots of printed materials.
Is the method. However, each pixel has gradation in color density.
The cell can be controlled by controlling the applied voltage and time.
Color density can be controlled by controlling the amount of charge injected into
You can. The area gradation method based on the lamination mixing is the same as that described above.
In the same way, color images are expressed using the same principle as the halftone dots of printed materials.
It is a method, but three color cells are stacked vertically in the same pixel.
Therefore, the pixel density is lower than the area gray scale method using the above-mentioned flat ground mixing.
To be summed. The density gradation method by the lamination mixing is the same as the above-described flat gradation method.
It is a color development method similar to the density gradation method using ground mixing.
It is a full-color expression method similar to photographs. The EC display varies depending on the application.
However, in the case of a transmissive element, the response up to the ultimate transmittance is achieved.
The answer speed is preferably 100 msec or less, and 10 msec.
The following is more preferable. In the case of reflective elements
The response speed until the absorbance is reached is preferably 100 msec or less.
Preferably, 10 msec or less is more preferable. Note that images are displayed on the EC display.
There is no particular limitation on the voltage for forming the
Although it can select suitably according to, for example, 0.5-
About 10V is preferable and about 1-5V is more preferable. The EC display of the present invention is, for example, a co
Computer, in-vehicle display, outdoor display, household equipment,
Commercial equipment, home appliances, traffic indicators, clock displays
, Calendar display, luminescent screen, sound
Suitable for use in various fields including equipment
be able to. [0152] Examples of the present invention will be described below.
Is not limited to these examples. Example 1 Commercially available tin oxide powder (Wako
Made of pure medicine, surface area 60m2/ G; average primary particle size of 50 nm or less
Bottom) Water containing nonionic surfactant and acetylacetate
Concentration of about 1 quality in the mixed solution (volume mixing ratio = 20/1)
A slurry liquid was prepared by dispersing in an amount of%. Next, this
The rally solution was applied on an ITO glass substrate and dried.
The obtained dried product was calcined in air at 500 ° C. for 1 hour,
10 μm thick porous fired product film (transparent conductive)
Layer). Examining the microstructure of the film by SEM observation
As a result, a phase-separated aggregate structure is formed,
It had a quality structure. Specific surface area of the fired product film (transparent conductive film)
Is 100 g / cm2Met. The specific surface area is BE
T surface area measuring device (Mitsuwa Riken, Multisorb
12), and adsorb nitrogen gas at liquid nitrogen temperature
By the method. Next, the substrate is used as an EC dye,
0.02 mol / ml bis- (2-phosphonoethyl)
-4,4'-bipyridinium dibromide (viologen
Derivative) Immerse in an aqueous solution to perform dye adsorption treatment and dry at room temperature
A dried viologen-binding electrode was prepared. The obtained viologen-binding electrode substrate and T
Using an FT active matrix substrate, shown in FIG.
An EC display device was prepared. Through the spacer
Laminate both substrates and inject electrolyte into the gap between both substrates
Then, the periphery of the gap between the substrates was sealed with a curable resin. Both
The distance between the substrates was 0.5 mm. As electrolyte solution
Of tetra-n-butylammonium perchlorate
A 0.2M propylene carbonate solution was used. In addition,
The size of the display part of the produced EC display device is 2 cm × 2
cm. The obtained EC display device was measured at room temperature 3
When a voltage of V is applied, viologen is produced at the cathode.
The derivative is reduced to a radical cation,
It turned blue. The response speed until reaching the ultimate transmittance
The degree was 80 msec. Even if you stop applying voltage
Color development lasted over 600 seconds. Also, color development-decolorization is 1
Even if it is repeated 10,000 times, the color density at the time of coloring is also the transparency at the time of decoloring
Was almost unchanged. (Example 2) In Example 1, the electrolyte and
Then, using the following electrolyte solution,
Thickness using a spin coater on a viologen binding electrode
The film is coated to 800 μm and heated at 60 ° C. for 6 hours.
EC as in Example 1 except that an electrolyte layer was formed.
A display device was produced. -Electrolyte solution- Dissolve 67g lithium hydroxide in 27ml methanol
Into the solution, 7.68 g of methacrylic acid was added 12 m of methanol.
The solution dissolved in l was added dropwise with stirring. In addition, this
The mixed solution obtained here was dropped into 2 liters of acetone,
After the precipitate is collected by filtration, the precipitate is washed with acetone,
Lithium methacrylate white by air drying
2.38 g of powder was obtained. Next, 1M lithium methacrylate
50 ml of an aqueous solution of peroxydisulfuric acid
1% by mass of potassium added to lithium methacrylate
And maintained at 70 ° C. for 24 hours under a nitrogen atmosphere.
Polymerization of lithium crylate was carried out. After the polymerization reaction is completed
Then, reprecipitate using 500 ml of methanol
By collecting and drying the product,
1.73 g of white powder of um was synthesized. Next, the iodide
Tium: lithium perchlorate: the synthesized polymethacrylate
Lithium phosphate = 50:30:20 (molar ratio)
Polyethylene glycol as the matrix material
(Number average molecular weight = 600)
Ethylene oxide unit: lithium ion = 5
1:49 (molar ratio)), these were dissolved in water. Obtained viologen-binding electrode-electrolyte membrane
Bonding composite and TFT active matrix substrate
The periphery between both substrates is sealed with a curable resin, as shown in FIG.
An EC display device as described above was produced. This EC display device
When a voltage of 3 V was applied at room temperature,
The viologen derivative is reduced in the radical
The color changed from colorless to blue. It will be the ultimate transmittance
The response speed until was 100 msec. Apply voltage
Coloring lasted for more than 600 seconds even after stopping. Also,
Even if the coloring and decoloring is repeated 10,000 times, the color density at the time of coloring is
The transparency at the time of erasing was almost unchanged. Example 3 -Porous TiO2Electrode 6.41 g of titanium tetraisopropoxide
Diluted with 20 ml of water and stirred to a glass with a specific gravity of 1.38
0.514 g of acid and 0.2 ml of water were added. Mixing more
The operation was performed under a dry nitrogen atmosphere. This mixed solution is 80 ° C.
The temperature is raised to 2 hours and reduced for 2 hours under a dry nitrogen stream.
A sol solution was obtained. The sol solution is cooled to room temperature and then stirred.
While stirring, 0.1 g of polyacrylic acid with respect to 2 g of sol solution
Was dissolved. Add 2 ml of water to the obtained sol solution and add
A transparent and uniform sol solution was obtained. Use this sol solution in a glass container
And heated to 80 ° C. Sol solution is gel in about 5 minutes
Turned into an almost transparent and uniform gel. At 80 ° C
After 15 hours, the gel dissolves again and is whitish translucent
It became a sol solution. This sol solution was converted to TF by spin coating.
Apply on T active matrix substrate and raise to 400 ° C
It was heated and held for 20 minutes to fire. This coating and baking process
The process is repeated 20 times, and the porous TiO with a film thickness of 3.5 μm2
An electrode made of a film was formed. The crystal structure of the obtained film is X
As a result of investigation by line diffraction, anatase-type titanium oxide
It was confirmed that it was formed. SE of membrane microstructure
When examined by M observation, a phase-separated aggregate structure is formed.
It had been. Specific surface area of this fired product film (transparent conductive film)
Is 100 g / cm2Met. The specific surface area is BE
T surface area measuring device (Mitsuwa Riken, Multisorb
12), and adsorb nitrogen gas at liquid nitrogen temperature
By the method. Next, the substrate is used as an EC dye,
0.02 mol / ml bis- (2-phosphonoethyl)
-4,4'-bipyridinium dibromide (viologen
Derivative) Immerse in an aqueous solution to perform dye adsorption treatment and dry at room temperature
A dried viologen-binding electrode was prepared. The obtained viologen-binding electrode substrate and its substrate
Example 1 S as an electrode substrate (counter substrate) paired with this
nO2[Β- (10-phenothiazyl) propoxy on the electrode
Si] Adsorbed and supported phosphonic acid (phenothiazine derivative)
The EC display device as shown in FIG.
Made. In other words, both substrates are bonded via a spacer,
An electrolyte solution is injected into the gap between both substrates, and the circumference of the gap between the substrates is
The sides were sealed with a curable resin. The distance between both boards is 0.5
mm. As an electrolyte solution, tetra-n-butyl alcohol is used.
Nmonium perchlorate 0.2M propylene carbonate
Nate solution was used. In addition, table of produced EC display device
The size of the indicated part was 2 cm × 2 cm. For this EC display device, 3 V at room temperature.
When a voltage is applied, the viologen derivative appears at the cathode.
Reduced to radical cation, changing from colorless to blue
Wow. On the other hand, the phenothiazine derivative is oxidized at the anode.
Becomes a radical cation and turns from colorless to red
It was. As a result, as a whole, the wavelength 52
Blue-red with large absorption around 0nm and 600nm
The color changed. Note that the response speed until the ultimate transmittance is reached.
Was 60 msec. Even if you stop applying the voltage
The color lasted over 600 seconds. In addition, 10,000 colors can be developed and erased
Even when repeated, the color density at the time of coloring and the transparency at the time of decoloring
Almost unchanged. Example 4 In Example 3, the counter substrate
As the following ZnO / SnO2Mixed porous membrane electrode
Except for using notiazine derivative adsorbed and supported
An EC display device was assembled in the same manner as in Example 3. -ZnO / SnO2Mixed porous membrane electrode 15% SnO2Colloidal aqueous solution (particle size about 15 nm)
Add 5 ml of acetic acid dropwise to 5 ml and mix well in a mortar.
ZnO powder (particle size: about 0.2 μm) 0.3 in gel solution
g, add 20 ml of methanol little by little and mix well
It was. Add 0.2 ml of Triton X-100
Mix well and add 0.5 x 0.5 cm 2To mask
Two fluorine-doped tin oxide conductive film glasses (F
TO) electrode on hot plate (100-120 ° C)
Spray applied, fired at 550 ° C. and ZnO / SnO2mixture
A porous membrane electrode was formed. SEM observation of the fine structure of the film
From further investigation, ZnO and SnO2Particles agglomerate separately
Not around ZnO with a large particle diameter.
SnO to surround the enclosure2Fine particles were attached. This
The specific surface area of the fired product film (transparent conductive film) is 100 g / c.
m2Met. The specific surface area is the BET surface area measuring device.
Device (Mitsuwa Riken Co., Ltd., Multisorb 12)
Performed by adsorbing nitrogen gas at liquid nitrogen temperature
It was. With respect to the obtained EC display device, 2 at room temperature.
When a voltage of V is applied, viologen induction at the cathode
The body is reduced to a radical cation, colorless to blue
It changed to. On the other hand, the phenothiazine derivative is acid at the anode.
Into radical cations and turns from colorless to red
It was. As a result, the overall wavelength from transparent to 5
Blue with large absorption near 20nm and 600nm
It turned red. The response speed until reaching the ultimate transmittance
The degree was 60 msec. Even if you stop applying voltage
Color development lasted over 600 seconds. Also, color development-decolorization is 1
Even if it is repeated 10,000 times, the color density at the time of coloring is also the transparency at the time of decoloring
Was almost unchanged. Example 5 In Example 3, the counter substrate
The following TiO2SnO complexed with2Membrane electrode
Other than using an adsorbed and supported ethothiazine derivative
Was assembled in the same manner as in Example 3. -TiO2SnO complexed with2Membrane electrode SnO2Powder (ultrafine particles and grains having a particle size of 10 nm to 20 nm
(Mixed powder having a diameter of 200 nm) was dispersed in ethanol.
A dispersion was prepared. This dispersion and polyethylene for viscosity adjustment
SnO mixed with lenglycol2A paste was used. this
SnO2Two conductive sheets of paste by screen printing
It is applied on the functional glass and baked at 500 ° C. to make SnO2film
(Film thickness 8 μm) was obtained. Next, this SnO20.1 membrane
eta of mol / l titanium tetraisopropoxide
Immerse it in a sol solution and add SnO2The surface hydroxyl group of titani
Surface modification by hydrolyzing um tetraisopropoxide
did. Surface modified SnO2The film was baked at 500 ° C for 1 hour
TiO2SnO complexed with2A membrane was obtained. The obtained EC display device was measured at room temperature 2
When a voltage of V is applied, viologen induction at the cathode
The body is reduced to a radical cation, colorless to blue
It changed to. On the other hand, the phenothiazine derivative is acid at the anode.
Into radical cations and turns from colorless to red
It was. As a result, the overall wavelength from transparent to 5
Blue with large absorption around 20 nm and 600 nm
It turned red. The response speed until reaching the ultimate transmittance
The degree was 60 msec. Even if you stop applying voltage
Color development lasted over 600 seconds. Also, color development-decolorization is 1
Even if it is repeated 10,000 times, the color density at the time of coloring is also the transparency at the time of decoloring
Was almost unchanged. [0172] According to the present invention, the above-mentioned problems in the prior art.
The structure is simple and the manufacture is easy
It is easy to make full color, has excellent memory characteristics,
Significantly improved response speed, coloring efficiency and durability
An EC display can be provided.

BRIEF DESCRIPTION OF THE DRAWINGS FIG. 1 shows a conventional monochromatic color passive matrix panel, in which (A) is a perspective view and (B) is a schematic sectional view. 2A and 2B show an example of a monochromatic color passive matrix panel according to the present invention, in which FIG. 2A is a perspective view and FIG. 2B is a schematic cross-sectional view. FIGS. 3A and 3B show an example of a monochromatic color passive matrix panel according to the present invention, in which FIG. 3A is a perspective view and FIG. 3B is a schematic cross-sectional view. 4 shows an example of a passive matrix panel for full color development according to the present invention, (A) is a perspective view, and (B). FIG.
Is a schematic cross-sectional view. FIG. 5 shows an example of a passive matrix panel for full color development according to the present invention, where (A) is a perspective view and (B).
Is a schematic cross-sectional view. FIG. 6 shows an example of a passive matrix panel for full color development according to the present invention, (A) is a perspective view, and (B).
Is a schematic cross-sectional view. FIG. 7 is a perspective view showing an example of a single color active matrix device according to the present invention. FIG. 8 is a perspective view showing an example of a single color active matrix device according to the present invention. FIG. 9 is a perspective view illustrating an example of an active matrix panel for color development according to the present invention. FIG. 10 is a perspective view showing an example of a color-colored active matrix panel according to the present invention. FIG. 11 is a schematic cross-sectional view showing an example of an EC element. FIG. 12 is a partially enlarged view of a region X in FIG. 11; [Description of Symbols] 2 EC dye 5 Transparent electrode 8 Semiconductor nanoporous layer 9 Electrolyte layer 12 Glass substrate 20 TFT substrate 23 Positive electrode 50 Power supply 60 Lead wire

Claims (1)

  1. What is claimed is: 1. An electrolyte layer is formed between a pair of transparent electrodes formed with a semiconductor nanoporous layer on at least one surface so that the semiconductor nanoporous layers face each other. An electrochromic display that is sandwiched and has either a passive matrix panel structure or an active matrix panel structure, and reversibly develops color in the electrolyte by at least one of an electrochemical oxidation reaction and a reduction reaction Alternatively, an electrochromic display comprising at least one type of electrochromic dye that decolorizes. 2. A passive electrode comprising a pair of transparent electrodes, each having a semiconductor nanoporous layer formed on at least one surface, disposed so that the semiconductor nanoporous layers face each other. An electrochromic display having either a matrix panel structure or an active matrix panel structure, wherein the semiconductor nanoporous layer is reversibly colored or decolored by at least one of an electrochemical oxidation reaction and a reduction reaction An electrochromic display comprising at least one electrochromic dye supported thereon. 3. The electrochromic display according to claim 2, wherein the electrolyte layer contains at least one electrochromic dye that reversibly develops or decolors by at least one of an electrochemical oxidation reaction and a reduction reaction. 4. The electrochromic display according to claim 1, wherein a semiconductor nanoporous layer is formed on both surfaces of the pair of transparent electrodes. 5. The electrochromic display according to claim 1, wherein a charge transfer agent is further contained in the electrolyte layer. 6. The electrochromic display according to claim 5, wherein a charge transfer agent is supported on the semiconductor nanoporous layer. 7. The semiconductor fine particle according to claim 1, 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 composite oxide semiconductor, and a mixture thereof. The electrochromic display described in 1. 8. The composite oxide semiconductor is SnO 2 —Zn.
    O, 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 , T
    i-SnO 2, Zr-SnO 2, In-SnO 2 and B
    The electrochromic display according to claim 7 which is selected from i-SnO 2. 9. The electrochromic display according to claim 2, wherein the electrochromic dye is heat-treated before being supported on the semiconductor nanoporous layer. 10. A semiconductor nanoporous layer having a thickness of 100 μm
    The electrochromic display according to claim 1, wherein the electrochromic display is m or less. 11. The electrochromic display according to claim 1, wherein the electrochromic dye is selected from organic compounds and metal complexes. 12. Full colorization according to any one method selected from an area gradation method by flat ground mixing, a density gradation method by flat ground mixing, an area gradation method by stacking mixing, and a density gradation method by stacking mixing. The electrochromic display according to any one of 1 to 11. 13. The response speed until reaching the ultimate transmittance or the ultimate absorbance is 100 msec or less.
    The electrochromic display according to any one of 2 above.
JP2002109153A 2002-04-11 2002-04-11 Electrochromic display Pending JP2003302659A (en)

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Cited By (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2009048072A (en) * 2007-08-22 2009-03-05 Funai Electric Advanced Applied Technology Research Institute Inc Electrochromic display device
KR100979728B1 (en) 2008-05-02 2010-09-03 엘지이노텍 주식회사 Anisotropic conductive film having a optimum elastic restitution property and circuit board using the same
JP2011197033A (en) * 2010-03-17 2011-10-06 Konica Minolta Holdings Inc Electrochemical display element
JP2012037859A (en) * 2010-08-10 2012-02-23 J Touch Corp Electrochromic module and display device using the same
JP2012103659A (en) * 2010-11-12 2012-05-31 J Touch Corp Three-dimensional image display device and electrochromic module thereof
JP2012107195A (en) * 2010-10-29 2012-06-07 Chiba Univ Composition for electrochromic device, and electrochromic display device
JP2013214061A (en) * 2012-03-07 2013-10-17 Nec Corp Electrode and manufacture method thereof

Cited By (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2009048072A (en) * 2007-08-22 2009-03-05 Funai Electric Advanced Applied Technology Research Institute Inc Electrochromic display device
KR100979728B1 (en) 2008-05-02 2010-09-03 엘지이노텍 주식회사 Anisotropic conductive film having a optimum elastic restitution property and circuit board using the same
JP2011197033A (en) * 2010-03-17 2011-10-06 Konica Minolta Holdings Inc Electrochemical display element
JP2012037859A (en) * 2010-08-10 2012-02-23 J Touch Corp Electrochromic module and display device using the same
JP2012107195A (en) * 2010-10-29 2012-06-07 Chiba Univ Composition for electrochromic device, and electrochromic display device
JP2012103659A (en) * 2010-11-12 2012-05-31 J Touch Corp Three-dimensional image display device and electrochromic module thereof
JP2013214061A (en) * 2012-03-07 2013-10-17 Nec Corp Electrode and manufacture method thereof

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