JP2009053613A - Electrochromic display element and its manufacturing method - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a low cost electrochromic display element whose productivity is high and which has high response speed and reflection efficiency. <P>SOLUTION: The electrochromic display element is provided with a first electrode 102, a dielectric layer 104 formed on the first electrode 102, a second electrode 103 formed on the dielectric layer 104, a cavity 120 penetrating at least the dielectric layer 104 and the second electrode 103, an electrochromic layer 106 formed in the cavity 120 and electrically connected to the first electrode 102, and an electrolyte layer 105 formed on the electrochromic layer 106 and electrically connected to the second electrode 103. <P>COPYRIGHT: (C)2009,JPO&INPIT

Description

  The present invention relates to a method for manufacturing an electrochromic display element, and more particularly to a method for manufacturing an electrochromic display element having a cavity.

  In recent years, with the spread of computers, the role of paper used for storing and transmitting documents has decreased, but when browsing digital information, the tendency to print and read on paper is still strong. For this reason, the amount of paper discarded only for temporary use tends to increase. Considering books, magazines, and newspapers, the amount of paper consumed every day is a very serious problem from the viewpoint of resources and the environment.

  On the other hand, considering human information recognition methods and thinking methods, the superiority of paper over displays typified by cathode ray tubes (CRTs) and transmissive liquid crystals cannot be ignored. Therefore, as an electronic medium that replaces paper, electronic paper having both the advantages of paper and the advantages of a display is expected. The characteristics required for electronic paper include a reflective display element, a high white reflectance and a high contrast ratio, a high-definition display, a memory effect in display, and a low voltage. It can be driven, it is thin and light, and it is inexpensive.

  Electronic paper display methods include a reflective liquid crystal method, an electrophoretic method, a two-color ball method, and an electrochromic method. In the reflective liquid crystal system, a liquid crystal having optical rotation and a polarizing plate having birefringence are used, so that the display is dark. In addition, due to the nature of the metal reflector, the white display is a glaring reflected light, so that long-time use has the disadvantage of placing a burden on the eyes.

  In the electrophoresis method, a white pigment, black toner, or the like is laminated on an electrode by the action of an electric field. The two-color ball display system is composed of spheres that are separately painted in two colors, such as white in half and black in half, and utilizes rotation by the action of an electric field. Both methods require a gap for the granular material to enter and cannot be packed most closely, making it difficult to obtain high contrast.

The electrochromic system utilizes the fact that a reversible oxidation-reduction reaction occurs when an electric field is applied, and color development / decoloration associated therewith occurs. Since it is a reflective display element that repeats color development / decolorization electrically with respect to other display methods, it is advantageous in terms of the burden on the eyes and the contrast (see Patent Documents 1 to 3).
JP 2002-287173 A JP 2006-208862 A JP 2006-058617 A

  In a conventional electrochromic display element, at least one electrode needs to be transparent. However, since the conductivity of transparent conductive materials such as indium tin oxide (ITO) and zinc oxide (ZnO) is on the order of lower than that of ordinary metals, there is a problem that the response speed is inferior. In addition, ITO has a problem that it lacks chemical stability with respect to a specific electrochromic material. Further, in a layer structure such as a conventional electrochromic display element, ITO becomes a reflective material of the internal element, and the reflection efficiency taken out to the outside is lowered.

  In the conventional element structure, a spacer is required to fill the electrochromic material and the electrolyte between the display electrode and the counter electrode. This increases costs.

  The present invention has been made in view of the above problems, and an object thereof is to provide an electrochromic display element which is excellent in productivity and excellent in response speed, chemical stability with respect to electrochromic materials, and reflection efficiency. And

  The electrochromic display element according to the present invention includes a first electrode, a dielectric layer formed on the first electrode, a second electrode formed on the dielectric layer, and at least the dielectric A cavity penetrating the layer and the second electrode, an electrochromic layer formed in the cavity and electrically connected to the first electrode, and formed on the electrochromic layer, the second electrode And an electrolyte layer electrically connected to each other.

  Here, it is preferable that the electrochromic layer is formed on the first electrode. The first electrode is preferably formed on an insulating substrate made of a flexible transparent polymer material.

  The electrochromic layer preferably contains a conjugated polymer selected from the group consisting of polyparaphenylene, polythiophene, polyphenylene vinylene, polypyrrole, polyaniline, arylamine-substituted polyarylene vinylene, and polyfluorene polymer.

  Further, it is preferable that a layer made of a material that increases electron or hole injection is further provided between the first electrode and the electrochromic layer. Furthermore, it is preferable that both the first electrode and the second electrode are made of a metal material.

  The method for manufacturing an electrochromic display device according to the present invention includes forming a dielectric layer on a first electrode and a second electrode on the dielectric layer, and penetrating at least the dielectric layer and the second electrode. Forming a cavity, an electrochromic layer electrically connected to the first electrode in the cavity, and an electrolyte layer electrically connected to the second electrode on the electrochromic layer And a step of forming.

  The step of forming the cavity includes a step of forming a resist layer on the second electrode and patterning the resist layer on a region for forming the cavity, and the patterned resist. And etching the region not covered with the layer. Alternatively, the step of forming the cavity includes a step of forming a resist layer on the first electrode, and patterning the resist layer on a region where the cavity is to be formed, and the first electrode. And forming the dielectric layer and the second electrode on the patterned resist layer, and then removing the patterned resist layer.

  According to the present invention, it is possible to provide an electrochromic display element which is excellent in productivity, excellent in response speed and reflection efficiency.

  Embodiments of the present invention will be described below. However, the present invention is not limited to the following embodiment. In addition, for clarity of explanation, the following description and drawings are simplified as appropriate.

  Hereinafter, embodiments of the present invention will be described in detail with reference to the drawings. FIG. 1 is a cross-sectional view schematically showing a part of an electrochromic display element manufactured by using a manufacturing method according to an embodiment of the present invention. As shown in FIG. 1, the electrochromic display element according to the present invention includes a substrate 101, a first electrode 102, a second electrode 103, a dielectric layer 104, an electrolyte layer 105, and an electrochromic layer 106.

  In the electrochromic display element according to this embodiment, ions are doped into the electrochromic layer 106 through the electrolyte layer 105 by applying a forward voltage / reverse voltage between the first electrode 102 and the second electrode 103. -Dedoped. Thereby, the two states of color development and color erasure are repeated. Since the electrochromic material has a memory property, the coloring / decoloring state does not change even when the voltage is turned off.

  Since the substrate 101 does not need to be transparent, various insulating substrates can be used. For example, a glass substrate such as a quartz glass substrate and a white glass substrate, a ceramic substrate, a paper substrate, and a wood substrate can be used. However, the present invention is not limited thereto, and examples of the polymer material substrate include polyethylene naphthalate and polyethylene terephthalate. Polyesters, polyamides, polycarbonates, cellulose esters such as cellulose acetate, polyvinylidene fluoride, fluoropolymers such as poly (tetrafluoroethylene-co-hexafluoropropylene), polyethers such as polyoxymethylene, polyacetals, polystyrene, polyethylene, polypropylene , Polyolefins such as methylpentene polymer, and polyimides such as polyimide-amide and polyetherimide. When these polymer materials are used as a substrate, a rigid substrate that does not bend easily can be used, but a film-like structure having flexibility and transparency can also be used. In the case where the first electrode 102 has sufficient rigidity, the substrate 101 is not necessarily provided.

  Since neither the first electrode 102 nor the second electrode 103 needs to be transparent, a metal material can be used. For example, lithium, beryllium, magnesium, calcium, strontium, barium, boron, aluminum, gallium, indium, silver, gold, copper, nickel, palladium, platinum, chromium, molybdenum, tungsten, manganese, nickel, cobalt and the main components thereof Although the alloy etc. to be mentioned are mentioned, It is not limited to these. In particular, gold, silver, and copper are more preferable because they have high conductivity and are chemically inert. In addition, a highly reflective material may be stacked over the second electrode 103 in order to improve visibility. The thicknesses of the first electrode 102 and the second electrode 103 must be at least 20 nm or more in order to ensure film formation. Therefore, it is preferable to set it as 20-1000 nm and also 40-200 nm. In addition, since a forward voltage and a reverse voltage are applied to both electrodes to develop and erase the color, a work function is provided that facilitates electron transfer between the electrochromic material and the electrode at any voltage. It is preferable to use a material.

The dielectric layer 104 has a function of maintaining a distance between the electrodes and preventing a short circuit. Therefore, the dielectric layer 104 is substantially free of pinholes and is made of a high resistance material or insulator having an electric resistance of about 10 ⁸ Ωcm or more, preferably about 10 ¹² Ωcm or more. Examples of suitable high resistance materials include, but are not limited to, silicon nitride, boron nitride, aluminum nitride, silicon oxide, aluminum oxide, polyimide, polyvinylidene fluoride, and parylene. In addition, by reducing the thickness of the dielectric layer 104, the thickness of the entire electrochromic display element can be reduced, and the electrochromic efficiency and power saving can be improved. That is, the voltage required for electrochromic can be reduced by reducing the distance between the electrodes. On the other hand, since dielectric breakdown is likely to occur, the dielectric layer 104 is required to have sufficient dielectric strength according to the operating voltage.

The electrolyte layer 105 is formed on the electrochromic layer 106 in contact with the inside of the cavity 120 that penetrates the second electrode 103 and the dielectric layer 104 and reaches the first electrode 102. The form is not particularly limited. For example, in the case of a solution, since the ionic conductivity is large, the response speed, the driving voltage / current can be reduced. Moreover, if it is a gel form and a solid form, a highly reliable element which does not leak can be provided. As a solution electrolyte, it is common to use a solution in which a lithium salt such as LiClO ₄ , LiAsF ₆ , LiPF ₆ , LiBF ₄ or the like is dissolved in an organic solvent such as acetonitrile, butyrolactone, or propylene carbonate. Some use ionic liquids for the purpose of improving efficiency and safety, and examples include compounds having tetrafluoroborate, trifluoromethylsulfonylimide, pentafluoroethylsulfonylimide, and the like as anions. As cations, there are imidazolium cations such as ethylmethylimidazolium and methylbutylimidazolium, pyrrolidinium cations such as butylmethylpyrrolidinium and butylpyridinium, ammonium cations such as butyltrimethylammonium and diethylmethoxyethylmethylammonium, etc. Compounds. As the ionic liquid, any combination of these anions and cations can be used.

As the solid electrolyte, a solid electrolyte such as Ta ₂ O ₅ or MgF ₂ is used. As the polymer solid electrolyte, a supporting electrolyte is dispersed in a matrix polymer material. As the matrix polymer, the main chain units are-(C-C-O) _n -and-(C-C, respectively. _{-N) n -, - (C} -C-S) n - polyethylene oxide represented by, polyethyleneimine, polyethylene sulfide. These may be branched with the main chain structure. Polymethyl methacrylate, polyvinylidene fluoride, polycarbonate and the like are also preferable. When forming the solid electrolyte, it is preferable to add a required plasticizer to the matrix polymer. As the preferred plasticizer, when the matrix polymer is hydrophilic, water, ethyl alcohol, isopropyl alcohol and a mixture thereof are preferable. When the matrix polymer is hydrophobic, propylene carbonate, dimethyl carbonate, ethylene carbonate, γ-butyrolactone is preferable. Acetonitrile, sulfolane, dimethoxyethane, ethyl alcohol, isopropyl alcohol, dimethylformaldehyde, dimethyl sulfoxide, dimethylacetamide, n-methylpyrrolidone and mixtures thereof are preferred. The solid polymer electrolyte is formed by dispersing a supporting electrolyte in the matrix polymer. Examples of the electrolyte include LiCl, LiBr, LiI, LiBF ₄ , LiClO ₄ , LiPF ₆ , and LiCF ₃ SO ₃ . Lithium salts such as potassium salts such as KCl, KI and KBr, sodium salts such as NaCl, NaI and NaBr, or tetraethylammonium borofluoride, tetraethylammonium perchlorate, tetrabutylammonium borofluoride, tetrabutyl perchlorate Examples thereof include tetraalkylammonium salts such as ammonium and tetrabutylammonium halide. The alkyl chain length of the quaternary ammonium salt may be uneven.

The electrochromic layer 106 is formed on the first electrode 102 inside the cavity 120 that penetrates the second electrode 103 and the dielectric layer 104 and reaches the first electrode 102. It also has electroactivity and changes color due to electrochemical oxidation / reduction. The electrochromic material constituting the electrochromic layer 106 is not particularly limited as long as it is a material exhibiting electrochromic. For example, inorganic or _{non-polymeric, IrOx, NiOx, WO 3,} MoO 3, etc. TiO ₂ and the like. Further, in order to realize a discoloration with good display quality, a π-conjugated conductive polymer is suitable, for example, polyacetylene, polypyrrole, polyparaphenylene, polythiophene, poly-3-methylthiophene, polyisothianaphthene, poly Examples include, but are not limited to, paraphenylene sulfide, polyparaphenylene oxide, polyaniline, polyparaphenylene vinylene, polythiophene vinylene, polyperiphthalene, and nickel phthalocyanine. The electrochromic layer 106 can contain a surfactant. In addition, a buffer layer may be formed between the display electrode 102 and the electrochromic layer 106 by injecting a solution or dispersion of a material that increases electron or hole injection. The material for increasing the electron or hole injection forming the buffer layer is not particularly limited, but examples thereof include organic compounds doped with carbonates such as cesium carbonate and lithium carbonate, Alq3, LiF, triphenyldiamine derivatives, Although an oxadiazole derivative, a polyphylyl derivative, a stilbene derivative, etc. can be used, it is not restricted to this.

  Next, a method for manufacturing an electrochromic display element according to the present invention will be described. In the manufacturing process, the dielectric layer 104 and the second electrode 103 are formed on the first electrode 102, and the cavity 120 penetrating at least the dielectric layer 104 and the second electrode 103 is formed. Step (A), an electrochromic layer 106 electrically connected to the first electrode 102 inside the cavity 120, and an electrolyte layer 105 electrically connected to the second electrode 103 thereon (B) which forms. This will be described in order below.

  (A) A first electrode layer 102 is formed on a substrate 101, a dielectric layer 104 is formed on the first electrode 102, and a second electrode 103 is formed on the dielectric layer 104 to form a layer structure. To do. The order of the layer structure may be reversed, and the second electrode 103 may be formed on the substrate 101, the dielectric layer 104 may be formed thereon, and the first electrode 102 may be further formed thereon.

  Various techniques are used for forming the layer structure, and examples thereof include, but are not limited to, evaporation, sputtering, chemical vapor deposition, electroplating, spin coating, and semiconductor manufacturing techniques. In order to achieve the preferred thickness of each layer, vacuum deposition techniques are generally preferred. Such vacuum processes include techniques such as cathode arc physical vapor deposition, electron beam evaporation enhanced arc physical vapor deposition, chemical vapor deposition, magnetron sputtering, molecular beam epitaxy and the like, and combinations thereof. It is not limited.

  Next, a method for forming the cavity 120 penetrating the second electrode 103 and the dielectric layer 104 by photolithography technology and etching technology will be described with reference to FIGS. First, as illustrated in FIG. 2A, a resist layer 107 is formed on the second electrode 103.

  Next, as shown in FIG. 2B, the resist layer 107 is patterned so that the resist layer 107 in the region where the cavity 120 is formed is removed. By patterning the resist layer 107, an opening 110 is formed in a region where the cavity 120 is formed.

  Next, as shown in FIG. 2C, the opening 110 not covered with the resist layer 107 is etched. Specifically, etching is sequentially performed using an etchant that selectively etches only the second electrode 103 and only the dielectric layer 104. Thereby, a cavity 120 that penetrates through the second electrode 103 and the dielectric layer 104 and reaches the first electrode 102 is formed in the opening 110.

  In FIG. 2C, the cavity 120 having a cylindrical shape is formed, but the cavity 120 having other shapes can be formed by appropriately selecting an isotropic etching agent or an anisotropic etching agent. The etchant may be a gas, liquid, solid or a combination thereof and may require an energy source such as electromagnetic radiation or electrons. That is, dry etching or wet etching is performed.

  As shown in FIG. 2D, the resist layer 107 is removed before the electrochromic material is applied to the surface inside the cavity 120. The patterning process and etching process described above can be performed using known lithography techniques. Further, after the resist layer 107 is removed and before the electrochromic layer 106 is formed, the surface inside the cavity 120 may be subjected to surface treatment in order to remove an oxide film or remove contamination. Examples of surface treatments include, but are not limited to, dry cleaning (eg, exposure to plasma), wet etching, and solvent cleaning. Thereby, the adhesiveness between the first electrode 102 and the electrochromic layer 106 can be improved. Further, a layer made of a material that increases electron injection or hole injection may be formed between the first electrode 102 and the electrochromic layer 106.

  Next, another cavity forming method by the lift-off method will be described with reference to FIG. First, as shown in FIG. 3A, a resist layer 108 thicker than the stacked structure of the dielectric layer 104 and the second electrode 103 formed in a later process is formed on the first electrode 102.

  Next, as shown in FIG. 3B, the resist layer 108 is patterned so that the resist layer 108 remains in a region where the cavity 120 is formed. Here, the cross-sectional shape of the patterned resist layer 108 is a trapezoidal shape, and it is preferable that the lower bottom in close contact with the first electrode 102 is shorter than the upper bottom so that lift-off is easy in a later process.

  Next, as illustrated in FIG. 3C, the dielectric layer 104 and the second electrode 103 are formed on the first electrode 102 and the resist layer 108.

  Then, as shown in FIG. 3D, by removing the resist layer 108, a cavity 120 that penetrates the second electrode 103 and the dielectric layer 104 and reaches the first electrode 102 is formed.

  When the lift-off method is used, it is not necessary to surface-treat the surface inside the cavity 120 before the electrochromic layer 106 is formed.

  As described above, the cavity 120 can be formed by a known lithography technique or etching technique, but laser cutting or punching may be used. In addition, another layer may be formed between the respective layers in order to improve the adhesion between the respective layers or to improve the electrical characteristics.

  (B) An electrochromic layer 106 made of an electrochromic material is formed on the surface of the first electrode 102 inside the cavity 120. There are various electrochromic materials, but a conductive polymer film is preferable because it is relatively strong and excellent in durability. Examples of the film forming method include an electrolytic polymerization method and a wet coating method.

  In wet coating, the conductive polymer is dispersed or dissolved in a solvent, applied to a predetermined film thickness, and then dried. Here, water, acetone, toluene, tetrahydrofuran, chloroform, or the like can be used as the solvent. Moreover, sodium hydroxide, sodium carbonate, sulfuric acid, hydrochloric acid, etc. can be added as a PH adjuster for dispersion stability. It adjusts so that 1-20 mass% of conductive polymers may be contained in these solvents. This mixed solution is made into a uniform solution by a disperser or a stirrer. As the disperser, a colloid mill, a ball mill, a sand mill, or the like can be used. As the stirrer, a batch mixer, an in-line mixer, or the like can be used. Examples of the method for applying the coating solution thus adjusted include a spin coating method, a bar coating method, and an ink jet method.

  In the spin coating method, the substrate 101 is fixed to a device called a spinner by vacuum suction, a coating liquid is dropped on the substrate 101, and then rotated at a high speed for a predetermined time to obtain a predetermined film thickness. The rotation speed of the spinner is preferably 100 to 5000 rpm although it depends on the concentration of the coating solution. In addition, the rotation speed is rotated at 100 to 500 rpm for the first 5 to 60 seconds, then increased to 1000 to 5000 in 5 to 30 seconds, and further rotated at the rotation speed for 5 to 60 seconds. A more uniform film thickness can be obtained by performing rotation at a two-stage speed for switching to high speed.

  In the bar coating method, a bar with a constant distance from the substrate 101 is slid on the coating solution dropped on the substrate 101, or a round bar wound with a wire of a predetermined thickness is in contact with the bar coating method. Slide to a uniform film thickness.

  There are two types of ink jet methods: a thermal ink jet method in which bubbles are generated by a heating element, and ink is ejected by the pressure, and a piezoelectric method in which ink is extruded using a piezoelectric element that is deformed by a voltage load. In either case, ink is ejected from the head nozzle onto the substrate 101 to form a coating film. In this embodiment mode, a coating film made of an electrochromic material is formed over the first electrode 102 inside the cavity 120 using a piezo ink jet.

  This coating film is put into a drying apparatus and dried, or dried by heating on a hot plate. The drying device is not particularly limited, and a general hot air drying device or a vacuum drying device can be used. At this time, drying may be performed at a temperature of 40 to 140 ° C. for a time of 10 to 240 minutes. In particular, when the drying temperature is less than 40 ° C., the residual solvent increases, and bubbles may be generated in the film by the oxidation-reduction reaction. If it exceeds 140 ° C, the polymer film may be deteriorated. As drying temperature, 80-120 degreeC is more preferable. Further, the drying time is more preferably 30 minutes or longer because the residual solvent increases when the drying time is less than 10 minutes and film deterioration is likely to occur.

  The coating thickness is 10 to 2000 nm, preferably 50 to 300 nm after drying. If it is too thin, a sufficient color change cannot be obtained, and if it is too thick, the response speed deteriorates. Further, the film thickness needs to be thinner than that of the dielectric layer 104, and if it is thicker than this, the electrochromic layer 106 is directly connected to both electrodes 102 and 103, and no color change occurs.

  Next, an electrolyte is injected into the cavity 120 to form the electrolyte layer 105. A solution-like material is more preferable because it can be injected into the cavity 120 by a method equivalent to the electrochromic material wet coating method.

  Next, although the preferable Example of this invention is described with a comparative example, it is not limited to these Examples.

[Example 1]
A silver layer having a thickness of 150 nm for the first electrode 102 was formed on a 4-inch quartz wafer by sputtering. Next, after applying a photoresist on the silver layer, a resist pattern was formed. The first electrode 102 was formed by etching the silver layer not covered with the resist. After removing the resist pattern, a resist layer 108 for forming a cavity was formed on the first electrode 102 and patterned so that the resist layer 108 in the cavity forming region remained. Next, a silicon nitride layer having a thickness of 5000 nm is formed as the dielectric layer 104 on the first electrode 102 and the resist layer 108 by vacuum deposition, and further, a second electrode 103 having a thickness of 150 nm is formed thereon by sputtering. A silver layer was formed. Thereafter, the resist layer 108 was removed by a lift-off method to form a cavity 120 having a depth of about 5.2 μm and a diameter of 100 μm. A polyaniline dispersion liquid (polyaniline sulfonic acid 20 mass%, pure water 80 mass% dispersion: Aqua-PASS manufactured by Mitsubishi Rayon Co., Ltd.) is injected into the cavity 120 by an ink jet method, and then dried at 80 ° C. by a dryer. Then, the electrochromic layer 106 having a thickness of 200 nm was formed. Furthermore, an electrolytic solution (BMIM-BF ₄ , manufactured by Wako Pure Chemical Industries, Ltd.) composed of BF ₄ -and butylmethylimidazolium cations was filled by an inkjet method to form an electrolytic layer 105. Then, another quartz wafer was stacked on the cavity 120, and the periphery thereof was sealed with an epoxy resin so that the electrolyte solution did not leak, thereby producing an electrochromic display element.

  In the produced electrochromic display element, when the forward voltage / reverse voltage was inverted, the polyaniline film exhibited electrochromic properties and a color change from purple to yellow to green. When the reflectance was evaluated from the total light reflectance measurement in purple, it was 75%.

[Comparative Example 1]
An ITO layer having a thickness of 150 nm for the first electrode 102 was formed on a 4-inch quartz wafer by sputtering. Next, after applying a photoresist layer on the ITO layer, a resist pattern was formed. The first electrode 102 was formed by etching the ITO layer not covered with the resist. On the first electrode 102, the same polyaniline dispersion as in Example 1 was applied by spin coating, and dried at 80 ° C. for 30 minutes by a dryer to form an electrochromic layer 106 having a thickness of 200 nm. On the other hand, a 150 nm silver layer was formed as the second electrode 103 by sputtering on another 4-inch quartz wafer. Both the quartz wafers were opposed to each other through a 5 μm spacer (Micropearl, manufactured by Sekisui Chemical Co., Ltd.), and the same electrolytic solution as in Example 1 was filled therebetween. Then, the periphery was sealed with an epoxy resin so that the electrolyte did not leak, and an electrochromic display element was produced.

  In the produced electrochromic display element, when the forward voltage / reverse voltage was inverted, the polyaniline film exhibited electrochromic properties and a color change from purple to yellow to green. When the reflectance was evaluated from the total light reflectance measurement in purple, it was 25%.

  In this invention, since it is not necessary to provide the spacer for hold | maintaining an electrochromic material and electrolyte between electrodes, it is excellent in productivity. In addition, since the electrochromic material that is the reflective layer is not shielded by the electrodes, an electrochromic display element with high reflectivity and high contrast can be obtained.

It is typical sectional drawing which shows a part of electrochromic display element which concerns on embodiment. It is typical sectional drawing which shows the manufacturing method of the electrochromic display element which concerns on embodiment. It is typical sectional drawing which shows the other manufacturing method of the electrochromic display element which concerns on embodiment.

Explanation of symbols

101 Substrate 102 First electrode 103 Second electrode 104 Dielectric layer 105 Electrolyte layer 106 Electrochromic layers 107 and 108 Resist layer 110 Opening 120 Cavity

Claims (9)

A first electrode;
A dielectric layer formed on the first electrode;
A second electrode formed on the dielectric layer;
A cavity penetrating at least the dielectric layer and the second electrode;
An electrochromic layer formed inside the cavity and electrically connected to the first electrode;
An electrochromic display element comprising: an electrolyte layer formed on the electrochromic layer and electrically connected to the second electrode.   The electrochromic display element according to claim 1, wherein the electrochromic layer is formed on the first electrode.   The electrochromic display element according to claim 1, wherein the first electrode is formed on an insulating substrate made of a flexible transparent polymer material.   The electrochromic layer contains a conjugated polymer selected from the group consisting of polyparaphenylene, polythiophene, polyphenylene vinylene, polypyrrole, polyaniline, arylamine-substituted polyarylene vinylene, and polyfluorene polymer. The electrochromic display element according to any one of 3.   The electrochromic according to any one of claims 1 to 4, further comprising a layer made of a material that increases electron or hole injection between the first electrode and the electrochromic layer. Display element.   The electrochromic display element according to claim 1, wherein both the first electrode and the second electrode are made of a metal material. Forming a dielectric layer on the first electrode and a second electrode on the dielectric layer, and forming a cavity penetrating at least the dielectric layer and the second electrode;
Forming an electrochromic layer electrically connected to the first electrode and an electrolyte layer electrically connected to the second electrode on the electrochromic layer in the cavity; and A method for manufacturing an electrochromic display element. Forming the cavity comprises:
Forming a resist layer on the second electrode and then patterning the resist layer on a region where the cavity is formed;
The method for manufacturing an electrochromic display element according to claim 7, further comprising: etching a region not covered with the patterned resist layer. Forming the cavity comprises:
Forming a resist layer on the first electrode, and then patterning the resist layer on a region for forming the cavity,
And a step of removing the patterned resist layer after forming the dielectric layer and the second electrode on the first electrode and the patterned resist layer. Item 8. A method for producing an electrochromic display element according to Item 7.

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