CN102540607A - Electrochromic module of organic and inorganic materials and display device incorporating the same - Google Patents

Abstract

The display device is prepared by arranging the electrochromic module on the surface of an image display module, wherein the electrochromic module comprises a first transparent substrate and a second transparent substrate, a transparent conductive element and an electrochromic layer are arranged between the substrates, and the electrochromic layer is prepared by mixing organic and inorganic materials and dissolving the organic and inorganic materials in a solvent. The ionic valence number in the material is changed by the transfer and transmission of electrons between the organic and inorganic materials, and when the ionic valence number is reduced by the supply of electrons and the electrons disappear to generate oxidation, the color change is caused, so that the color change speed is faster and more uniform, and the material has the advantages of smaller driving voltage and the like.

Description

Electrochromic module of organic and inorganic materials and display device combining the module

technical field

This case belongs to the field of optoelectronic devices, and in particular refers to an electrochromic module combining organic and inorganic materials, and a display device using the electrochromic module.

Background technique

Electrochromism (EC for short) material means that under the action of current or electric field, the electrochromism material undergoes light absorption or light scattering, resulting in a reversible change in color. As shown in FIG. 1 , the known electrochromic module 3 is respectively provided with a first transparent conductive element 311 and a second transparent conductive element 321 between a first transparent substrate 31 and a second transparent substrate 32. An electrolyte layer 34 and an electrochromic layer 33 are disposed between the transparent substrate 31 and the second transparent substrate 32 . Or as shown in Figure 2, another electrochromic layer 33 is further provided, and the electrochromic layer 33 is located between the electrolytic layer and the second transparent conductive element, as an ion storage layer and an auxiliary color-changing layer, and the electrochromic layer 33 is located between the electrolytic layer and the second transparent conductive element. Color-changing materials can be divided into inorganic electrochromic materials and organic electrochromic materials according to material types. In practical applications, they must have the following characteristics: (1) good electrochemical redox reversibility, (2) fast color change response time, (3) The color change is reversible, (4) The color change sensitivity is high, (5) The cycle life is long, (6) There is a certain storage memory function and (7) Good chemical stability.

The materials of the known electrochromic module 3 are all made of transition element oxides or hydroxides or their derivatives into inorganic solid films or mixed with organic compounds/electrolyte materials to form composite materials, through which electrons and additional ion sources (such as Electrolyte or second electrochromic material) make ions into the crystal lattice to cause discoloration effect, such as WO ₃ , Ni(OH) ₂ , Prussian blue, etc. In addition to the above-mentioned electrochromic materials, the performance of inorganic electrochromic materials is stable, and its light absorption changes are caused by double injection and double extraction of ions and electrons. Organic electrochromic materials include polyaniline, viologen and Rare earth phthalocyanines, etc., have a variety of rich colors, and are also formed by the redox reaction of organic matter itself. Although the speed is faster than inorganic materials, it also has environmental protection and toxicity problems; and the above-mentioned known electrochromic mechanism and structure Patents such as: "Electrochromic Film" in Taiwan Publication No. I273131, "Electrochromic Display Device" in Publication No. I289236, etc.

The principle of general stereoscopic image display technology is to use binocular disparity (Binocular disparity) to receive different images through the left and right eyes respectively, and finally fuse them into a stereoscopic image in the brain. In naked-eye stereoscopic display technology, it can be roughly divided into two types according to its structure: lenticular and barrier. Electrochromic materials are used to achieve the barrier, and it has the ability to switch to display stereoscopic images or flat surfaces. Stereoscopic image display module for images, related patents such as:

China Taiwan Patent Gazette, Announcement No. M368088 "Integrated Electrochromic 2D/3D Display", Announcement No. M371902 "Display Device for Switching 2D Planar Image/3D Stereoscopic Image Display Screen", Announcement No. I296723 "Color Filters for Liquid Crystal Panels Capable of Stereoscopic Images and Manufacturing Method Thereof" and U.S. Patent Publication No. 2006087499 "Autostereoscopic 3D display device and fabrication method thereof", etc., the above patents all use electrochromism The material is used as a parallax barrier device for displaying stereoscopic images, but the common defect in the structure of M368088 and M371902 is that they lack the necessary electrolyte layer for the electrochromic device. Because of the lack of an electrolyte layer that can provide ions to the electrochromic layer, the electrochromic The color-changing device will not be able to produce reversible reactions of oxidation or reduction to complete the coloring or decolorization changes, so these patents should not be implemented in practice; in addition, the transparent electrode layer and the electrochromic material layer of the parallax barrier device are set in a fence pattern , the layered coating, sputtering or etching in the manufacturing process, so that each stack must be accurately aligned, the process is quite complicated, and all the stacks are set in a fence pattern, resulting in a hollow between each fence and the fence The area will affect the overall light penetration, refraction or reflection, even for general 2D display, it may also affect the image quality of the display, causing problems such as color difference or uneven brightness; and I296723 is embedded in the LCD and formed in the color filter The structure of the light sheet, and the electrochromic layers in all the above patents use known electrochromic materials and color-changing mechanisms, which require a large driving voltage, so it is easy to cause problems such as material defects and short service life.

Contents of the invention

In view of the above-mentioned needs, the present inventor has made careful research and accumulated many years of personal experience in this business, and finally designed a brand-new "electrochromic module of organic and inorganic materials and a display device combined with the module".

An object of the present invention is to provide an electrochromic module with reduced thickness and simplified manufacturing process.

An object of the present invention is to provide an electrochromic module that does not require an additional electrolyte.

An object of the present invention is to provide an electrochromic module with fast coloring/fading, high cycle life and low driving voltage.

One object of the present invention is to provide an electrochromic module which has the advantages of organic/inorganic electrochromic materials but has no disadvantages.

In order to achieve the above-mentioned purpose, the color-changing material of the electrochromic module of the present invention is prepared by mixing and dissolving organic materials and inorganic materials in a solvent. The organic materials include redox indicators, pH indicators or organic compounds, and the Inorganic materials contain transition elements (including scandium subgroup (IIIB), titanium subgroup (IVB), vanadium subgroup (VB), chromium subgroup (VIB), manganese subgroup (VIIB), iron series (VIII), copper subgroup Inorganic derivatives such as oxides, sulfides, chlorides, hydroxides of group (IB), zinc subgroup (IIB) or platinum group (VIII), etc.), and halogen group (VIIA), oxygen group (VIA), One of the inorganic derivatives of nitrogen group (VA), carbon group (IVA), boron group (IIIA), alkaline earth group (IIA), alkali metal group (IA) and other inorganic derivatives, and its discoloration mechanism is formed by organic and inorganic materials. System, in this system, the conductive element provides electrons to cause a reduction reaction of the organic material in the electrochromic material. After reduction, the potential energy of the free radical or ion state is different from the potential energy of the ion of the inorganic material, so the electrons naturally The transfer of organic ions to inorganic ions changes the valence of the material and changes its color. The valence of the material is reduced by electrons and oxidized by the disappearance of electrons. The electrochromic speed is fast and uniform, and the driving voltage is small and the life is long.

In order to achieve the above-mentioned purpose, the "electrochromic module of organic and inorganic materials" of the present invention includes a first transparent substrate, a second transparent substrate, and an electrochromic module arranged between the first transparent substrate and the second transparent substrate. layer, and at least one transparent conductive element, wherein the transparent conductive element can be set on the surface of the first transparent substrate, or can be set on the surface of the second substrate, or can be set on both the first transparent substrate and the second transparent substrate For the corresponding surface, the electrochromic layer is made by mixing organic materials and inorganic materials dissolved in a solvent. The electrochromic layer is provided by the electrons provided by the transparent conductive element, and the complementary mechanism of the electrochromic material itself leads to ions Changes in color due to valence changes.

Another object of the present invention is to provide a display device that uses the electrochromic module and can switch between display states of 2D images and 3D images.

Another object of the present invention is to provide a display device that increases the contact area between the electrochromic module and the electrodes, and increases the discoloration rate.

In order to achieve the above-mentioned purpose, the present invention combines the above-mentioned electrochromic module with an image display module to form the display device. When the display device is converted from a plane image to a three-dimensional image, the displayed image will be divided into left-eye image and right-eye image. The eye image, at this time, the transparent conductive element is electrically conductive, so that the color of the electrochromic layer changes from transparent to dark in the light-shielding area, and is generated in the electrochromic module according to the interval arrangement of the electrochromic module. Multiple light-shielding areas arranged at intervals, the images passing through these light-shielding areas are divided into three-dimensional images of left-eye images and right-eye images, and some overlapping image areas are eliminated through the light-shielding areas, so that no overlapping will occur after being accepted by the naked eye and form a three-dimensional image.

A display device comprising: an image display module for displaying a planar image and a three-dimensional image; an electrochromic module arranged on the surface of the image display module, the electrochromic module includes: a first transparent substrate , the surface of which is provided with at least one first transparent conductive element; a second transparent substrate; and a plurality of electrochromic layers arranged at intervals between the first transparent substrate and the second transparent substrate, the electrochromic The material of the layer is made by mixing organic materials and inorganic materials dissolved in a solvent.

In order to achieve the above purpose, when the electrochromic module is used as a mask for a stereoscopic image display, the electrochromic layer is arranged in a plurality of intervals in the module, and the electrochromic modules can be arranged in three ways, the first One way is to mix conductive polymers and arrange them in the form of screen printing, the second way is to use a barrier unit to divide the electrochromic layers into multiple strips, and the third way is to directly use transparent The conductive element is used as a blocking unit; the above three methods are used to make the electrochromic layers form light-shielding areas of the grid body to form a light barrier (Barrier).

Generally, when displaying stereoscopic images, two additional devices, lenticular or barrier, are added to the display. , when displaying a stereoscopic image, the display device can directly display a stereoscopic image that has been divided into a left-eye image and a right-eye image.

Description of drawings

Fig. 1 is a cross-sectional view of a known electrochromic module;

Fig. 2 is the second sectional view of the electrochromic module in the known technology;

3 is a three-dimensional exploded schematic view of the first preferred embodiment of the present invention;

FIG. 4 is a first structural schematic diagram of a transparent conductive element according to the first preferred embodiment of the present invention;

FIG. 5 is a second structural schematic diagram of a transparent conductive element in the first preferred embodiment of the present invention;

Fig. 6 is a structural schematic diagram III of a transparent conductive element in the first preferred embodiment of the present invention;

Fig. 7 is a three-dimensional exploded schematic diagram of a second preferred embodiment of the present invention;

FIG. 8 is a first structural schematic diagram of a transparent conductive element according to a second preferred embodiment of the present invention;

Fig. 9 is a second structural schematic diagram of a transparent conductive element according to the second preferred embodiment of the present invention;

FIG. 10 is a first structural schematic diagram of a transparent conductive element according to a third preferred embodiment of the present invention;

Fig. 11 is a second structural schematic diagram of a transparent conductive element according to the third preferred embodiment of the present invention;

Fig. 12 is a three-dimensional exploded schematic diagram of a fourth preferred embodiment of the present invention;

Fig. 13 is a cross-sectional view of a fourth preferred embodiment of the present invention;

Fig. 14 is a cross-sectional view of a fifth preferred embodiment of the present invention;

Fig. 15 is a schematic structural diagram of a transparent conductive element according to a fifth preferred embodiment of the present invention;

Fig. 16 is a cross-sectional view of a sixth preferred embodiment of the present invention;

Fig. 17 is a first structural top view of a transparent conductive element according to the sixth preferred embodiment of the present invention;

Fig. 18 is a first structural perspective view of a transparent conductive element according to the sixth preferred embodiment of the present invention;

Fig. 19 is the second perspective view of the structure of the transparent conductive element according to the sixth preferred embodiment of the present invention;

Fig. 20 is the second structural top view of the transparent conductive element according to the sixth preferred embodiment of the present invention;

Fig. 21 is a cross-sectional view of a seventh preferred embodiment of the present invention;

Fig. 22 is a structural top view of a transparent conductive element according to a seventh preferred embodiment of the present invention;

Fig. 23 is a structural perspective view of a transparent conductive element according to a seventh preferred embodiment of the present invention;

Fig. 24 is a cross-sectional view of an eighth preferred embodiment of the present invention;

Fig. 25 is a sectional view of a ninth preferred embodiment of the present invention;

Fig. 26 is a sectional view of a tenth preferred embodiment of the present invention;

Fig. 27 is a sectional view of an eleventh preferred embodiment of the present invention;

Fig. 28 is a sectional view of a twelfth preferred embodiment of the present invention;

Fig. 29 is a sectional view of a thirteenth preferred embodiment of the present invention.

Explanation of reference signs

Electrochromic module-1; first transparent substrate-11; first transparent conductive element-111; second transparent substrate-12; second transparent conductive element-121; electrochromic layer-13; barrier unit-14; image Display module-2; electrochromic module-3; first transparent substrate-31; first transparent conductive element-311; second transparent substrate-32; second transparent conductive element-321; electrochromic layer-33; electrolyte Layer - 34.

Detailed ways

In order to enable the examiner to clearly understand the content of the present invention, the following descriptions are provided together with the drawings, please refer to them.

Please refer to FIG. 3, which is a three-dimensional exploded schematic view of the first preferred embodiment of the present invention. As shown in the figure, the electrochromic module 1 of the present invention includes: a first transparent substrate 11, a second transparent substrate 12 with an electrochromic layer 13, wherein:

The upper surface of the first transparent substrate 11 is provided with a first transparent conductive element 111, and the material of the first transparent substrate 11 and the second transparent substrate 12 is plastic, polymer plastic, glass or a material selected from resin, polyethylene pair, etc. Phthalate (Polyethylene Terephthalate, PET), polycarbonate (Poly Carbonate, PC), polyethylene (polyethylene, PE), polyvinyl chloride (Poly Vinyl Chloride, PVC), polypropylene (Poly Propylene, PP), One of polystyrene (Poly Styrene, PS), polymethylmethacrylate (Polymethylmethacrylate, PMMA) or its mixture of plastic polymers; and the material of the first transparent conductive element 111 is selected from indium tin oxide (Indium tin oxide) Tin Oxide, ITO), indium zinc oxide (Indium Zinc Oxide, IZO), zinc aluminum oxide (Al-doped ZnO, AZO) or tin antimony oxide (Antimony Tin Oxide, ATO) composed of doped oxide (Impurity-Doped Oxides) group or one of them is a conductive polymer such as carbon nanotube (carbon nanotube) or poly-3,4-ethylenedioxythiophene (Poly-3,4-Ethylenedioxythiophene, PEDOT) or polyaniline material.

The electrochromic layer 13 is arranged between the first transparent substrate 11 and the second transparent substrate 12, and covers the surface of the first transparent conductive element 111, and the material of the electrochromic layer 13 is an organic material mixed in a solvent. It is made of inorganic materials, and its materials include at least one organic material and at least one inorganic material, but it can also be made of a variety of organic materials and a variety of inorganic materials mixed in a solvent. The electrochromic layer 13 is Using the complementary effect of organic materials and inorganic materials, it has the characteristics of oxidation and reduction reactions at the same time. The principle of color change is that electrons are provided by conductive elements, so that the transfer and transmission of electrons in electrochromic materials make the valence of ions Transformation and color change, the valence of which is provided by electrons to produce reduction and electron disappearance to produce oxidation. Compared with the known electrochromic mechanism of electrons and ions moving in and out to achieve color changing, the electrochromic speed of the present invention is fast and uniform. , and the driving voltage is small and the life is long.

The organic material includes a redox indicator (Redox Indicator), a pH indicator (acid-base indicator) or an organic compound.

Among them, the redox indicator (Redox Indicator) is an indicator used in redox titration, which can produce obvious color changes at a specific electrode potential, and is generally an organic reagent with redox properties itself. The reduced forms come in different colors and there are two common types of redox indicators: metal-organic complexes, organic redox systems, etc. Almost all redox indicators and organic redox systems involve protons (i.e. H ⁺ ) as participants in electrochemical reactions, so according to this characteristic, redox indicators can also be divided into two types: pH-dependent redox indicators reagents, and pH-independent redox indicators. pH-independent redox indicators include: 2,2'-bipyridyl ruthenium complex ion, 5-nitrophenanthrite complex ion, N-phenylanthranilic acid, 1,10-o-diazepine complex ion Ferrous complex ion, wool poppy red, paraquat, 2,2'-bipyridyl ferrous complex ion, 5,6-dimethyl-o-phenanthrin complex ion, 3,3'-dimethoxy Benzidine, sodium diphenylamine sulfonate, N,N'-diphenylbenzidine, diphenylamine, viologen, etc., but some indicators are toxic; and pH-dependent redox indicators include: dichlorophenol indophenol Sodium, sodium o-cresol indo, thionine, methylene blue, indigo tetrasulfonic acid, indigo trisulfonic acid, indigo carmine, indigo monosulfonic acid, phenol safranin, safranin T, neutral red, etc.

Among them, the pH indicator (acid-base indicator) is a chemical reagent used to test the pH value. It is a weak acid or weak base and contains a pigment. When it is dropped into the solution, the pigment will combine with hydrogen ions or hydroxide ions and convert into corresponding The acidic or basic formula, thus showing different colors, because the pH indicator can produce reversible color changes in solutions of different pH values, so in the neutralization analysis, it indicates the end of the reaction and can measure the pH value of the test solution , Commonly used pH indicators in the laboratory include: phenol red, Congo red, methyl orange, phenolphthalein, thymol blue, litmus, methyl violet, malachite green, methyl yellow, bromophenol blue, bromocresol Green, methyl red, bromocresol purple, bromothymol blue, thymolphthalein (Thymolphthalein), alizarin yellow R, etc.

A preferred embodiment of the electrochromic layer of the present invention is methylene blue (Methylene blue, C ₁₆ H ₁₈ ClN ₃ S 3H ₂ O), Dichlorophenolindophenol sodium (Dichlorophenolindophenolsodium, C ₁₂ H ₆ Cl ₂ NNaO ₂ ), N-phenylanthranilic acid (C ₁₃ H ₁₁ NO ₂ ), sodium diphenylamine sulfonate (C ₁₂ H ₁₀ NNaO ₃ S), N,N′-diphenylbenzidine (N, N'-Diphenylbenzidine, C20H20N2) or viologen (Viologen), and Variamine Blue B Diazonium salt B (Variamine Blue B Diazonium salt, C13H12ClN3O) as a pH indicator.

Wherein, the organic compound may be ferrocene (Ferrocene, Fe(C5H5)2), 7,7,8,8-tetracyanoquinodimethane (7,7,8,8-Tetracyanoquinodimetbane).

The material of the solvent can be dimethylsulfoxide [(CH3)2SO)], propylene carbonate (C4H6O3), water (H2O), γ-butyrolactone, acetonitrile, propionitrile, benzonitrile, glutaronitrile, formaldehyde Glutaronitrile, 3,3'-oxodipropionitrile, hydroxypropionitrile, dimethylformamide, N-methylpyrrolidone, sulfolane, 3-methylsulfolane or mixtures thereof.

The inorganic material is one of inorganic derivatives such as oxides, sulfides, chlorides, and hydroxides of transition metals; or it can be halogen (VIIA), oxygen (VIA), nitrogen (VA), carbon One of the inorganic derivatives of group (IVA), boron group (IIIA), alkaline earth group (IIA), and alkali metal group (IA).

Among them, the transition metal elements include: copper subgroup (IB), zinc subgroup (IIB), scandium subgroup (IIIB), titanium subgroup (IVB), vanadium subgroup (VB), chromium subgroup (VIB), Manganese subgroup (VIIB), iron series (VIIIB) and platinum series (fifth and sixth cycle VIIIB), etc.

Examples of the above-mentioned families are as follows:

Halogen (English VIIA):

Solid: I ₂ purple black; ICl dark red; IBr dark gray; IF ₃ yellow; ICl ₃ orange; I ₂ O ₅ white; I ₂ O ₄ yellow (ionic crystal); I ₄ O ₉ yellow (ionic crystal).

Oxygen group (English VIA):

Solid: S light yellow; Se gray, brown; Te colorless metallic luster; Na ₂ S, (NH ₄ ) ₂ S, K ₂ S, BaS white, soluble; ZnS white ↓; MnS meat red ↓; FeS black ↓ ; PbS black ↓; CdS yellow ↓; Sb ₂ S ₃ orange red ↓; SnS brown ↓; HgS black (precipitation), red (cinnabar); Ag ₂ S black ↓; CuS black ↓; Na ₂ S ₂ O ₃ white; Na ₂ S ₂ O ₄ white; SeO ₂ white, volatile; SeBr ₂ red; SeBr ₄ yellow; TeO ₂ white heated to yellow; H ₂ TeO ₃ white; TeBr ₂ brown; TeBr ₄ orange; TeI ₄ gray black; PoO ₂ Low-temperature yellow (face-centered cubic), high-temperature red (square); SO ₃ is colorless; SeO ₃ is colorless and deliquescent; TeO ₃ is orange; H ₆ TeO ₆ is colorless.

Nitrogen (English VA):

Solid: ammonium salt colorless crystal; metal nitride white; N ₂ O ₃ blue (low temperature); N ₂ O ₅ white; P white, red, black; P ₂ O ₃ white; P ₂ O ₅ white; PBr ₃ Yellow; PI ₃ red; PCl ₅ colorless; P ₄ Sx yellow; P ₂ S ₃ gray yellow; P ₂ S ₅ light yellow; H ₄ P ₂ O ₇ colorless glass; H ₃ PO ₂ white; As gray; As ₂ O ₃ white; As ₂ O ₅ white; AsI ₃ red; As ₄ S ₄ red (realgar); As ₄ S ₆ yellow (orpiment); As ₂ S ₅ light yellow; Sb silver white; Sb(OH) ₃ white ↓; Sb ₂ O ₃ white (antimony white, pigment); Sb ₂ O ₅ light yellow; SbX ₃ (X<>I) white; SbI ₃ red; Sb ₂ S ₃ orange red ↓; Sb ₂ S ₅ orange yellow; Bi silver white Slightly red; Bi ₂ O ₃ pale yellow; Bi ₂ O ₅ reddish brown; BiF ₃ off-white; BiCl ₃ white; BiBr ₃ yellow; BiI ₃ black↓; Bi ₂ S ₃ brown-black.

Carbon group (English IVA):

Solid: C (diamond) colorless and transparent; C (graphite) black metallic luster; Si gray-black metallic luster; Ge gray-white; Sn silver-white; Pb dark gray; SiO ₂ colorless and transparent; H ₂ SiO ₃ colorless and transparent gel↓ ; Na ₂ SiF ₆ white crystal; GeO black; GeO ₂ white; SnO black; SnO ₂ white; Sn(OH) ₂ white ↓; PbO yellow or yellow red; Pb ₂ O ₃ orange; Pb ₃ O ₄ red; PbO ₂ Brown; CBr ₄ light yellow; CI ₄ light red; GeI ₂ orange; GeBr ₂ yellow; GeF ₄ white; GeBr ₄ off-white _; GeI ₄ yellow; SnF 2 white; SnCl ₂ white; SnBr ₂ light yellow; SnI ₂ orange; SnF ₄ white; SnBr ₄ colorless; SnI ₄ red; PbF ₂ colorless ↓; PbCl ₂ white ↓; PbBr ₂ white; PbI ₂ golden; PbF ₄ colorless; GeS red; GeS ₂ white; SnS brown ↓; SnS ₂ golden (commonly known as "gold powder") ↓; PbS black ↓; PbS ₂ reddish brown; Pb(NO ₃ ) ₂ colorless; Pb(Ac) ₂ 3H ₂ O colorless crystal; PbSO ₄ white ↓; PbCO ₃ white ↓; Pb( OH) ₂ white ↓; Pb ₃ (CO ₃ ) ₂ (OH) ₂ lead white ↓; PbCrO ₄ bright yellow ↓.

Boron group (English IIIA):

Solid: B (amorphous) brown powder; B (crystal) black gray; Al silver white; Ga silver white (easy to liquefy); In silver gray; Tl silver gray; B ₂ O ₃ glassy; H ₃ BO ₃ colorless flakes; BN White; Na ₂ B ₄ O ₇ 10H ₂ O white crystal; Cu(BO ₂ ) ₂ blue ↓; Ni(BO ₂ ) ₂ green ↓; NaBO ₂ Co(BO ₂ ) ₂ blue ↓; NaBO ₂ 4H ₂ O colorless Crystal; anhydrous NaBO ₂ yellow crystal; Al ₂ O ₃ white crystal; AlF ₃ colorless; AlCl ₃ white; AlBr ₃ white; AlI ₃ brown; Al(OH) ₃ white ↓; Ga ₂ O ₃ white ↓Ga(OH ) ₃ white ↓; GaBr ₃ white; GaI ₃ yellow; In ₂ O ₃ yellow; InBr ₃ white; InI ₃ yellow; TlOH yellow; Tl ₂ O black; Tl ₂ O ₃ brown black; TlCl white ↓; TlI yellow ↓ (similar to silver); TlBr ₃ yellow; TlI ₃ black.

Alkaline earth (English IIA):

Simple substance: silver white

Flame color: Ca brick red; Sr magenta; Ba green.

Oxides: all white solids.

Hydroxide: white solid Be(OH) ₂ ↓, Mg(OH) ₂ ↓.

Salt: mostly colorless or white crystals; BeCl ₂ light yellow; BaCrO ₄ yellow ↓; CaF ₂ white ↓.

Alkali metal (English IA):

Simple substance: silver white

Flame color: Li red; Na yellow; K purple; Rb purple; Cs purple.

Oxides, peroxides, superoxides, ozonides: Li ₂ O white; Na ₂ O white; K ₂ O light yellow; Rb ₂ O bright yellow; Cs ₂ O orange red; Na ₂ O ₂ light yellow; KO ₂ Orange yellow; RbO ₂ dark brown; CsO ₂ dark yellow; KO ₃ orange.

Hydroxide: white, LiOH white ↓.

Salt: mostly colorless or white crystals and easily soluble in water.

Insoluble salt ↓ (those not specified are white crystals): LiF Li ₂ CO ₃ Li ₃ PO ₄ LiKFeIO ₆ Na【Sb(OH) ₆ 】NaZn(UO ₂ ) ₃ (Ac) ₉ 6H ₂ O yellow-green; M =K, Rb, Cs M ₃ 【Co(NO ₂ ) ₆ 】bright yellow; MBPh ₄ MClO ₄ M ₂ PtCl ₆ light yellow; CsAuCl ₄ .

Copper subgroup (English IB):

Elemental substance: Cu purple or dark red; Ag silver white; Au golden yellow.

Copper compounds: flame green; CuF red; CuCl white ↓; CuBr yellow ↓; CuI brown yellow ↓; CuCN white ↓; Cu ₂ O dark red; Cu ₂ S black; CuF ₂ white; CuCl ₂ brown yellow (solution yellow green ); CuBr ₂ brown; Cu(CN) ₂ brown yellow; CuO black ↓; CuS black ↓; CuSO ₄ colorless; CuSO ₄ 5H ₂ O blue; Cu(OH) ₂ light blue ↓; Cu(OH) ₂ CuCO ₃ Dark green; 【Cu(H ₂ O) ₄ 】 ²⁺ blue; 【Cu(OH) ₄ 】 ^2- blue-purple; 【Cu(NH ₃ ) ₄ 】 ²⁺ dark blue; 【CuCl ₄ 】 ^2- yellow; 【Cu( en) ₂ 】 ²⁺ deep blue-violet; Cu ₂ 【Fe(CN) ₆ 】brown red; copper alkyne red ↓.

Silver compounds: AgOH white (decomposed at room temperature); Ag ₂ O black; new AgOH brown yellow (mixed with Ag ₂ O); protein silver (AgNO ₃ drops on hand) black ↓; AgF white; AgCl white ↓; AgBr light yellow ↓ ; AgI yellow ↓ (colloid); Ag ₂ S black ↓; Ag ₄ [Fe(CN) ₆ ] white ↓; Ag ₃ [Fe(CN) ₆ ] white ↓; Ag ⁺ , [Ag(NH ₃ ) ₂ ] ⁺ , 【Ag(S ₂ O ₃ ) ₂ 】 ^3- , 【Ag(CN) ₂ 】 ^- colorless.

Gold compounds: HAuCl ₄ 3H ₂ O bright yellow crystals; KAuCl ₄ 1.5H ₂ O colorless flaky crystals; Au ₂ O ₃ black; H [Au(NO ₃ ) ₄ ] 3H ₂ O yellow crystals; AuBr grayish yellow↓; AuI lemon yellow ↓.

Zinc subgroup (I, IB):

Elemental substance: all are silvery white, and the precipitation of Hg in aqueous solution is black.

Zinc compound: ZnO white (zinc white pigment) ↓; ZnI ₂ colorless; ZnS white ↓; ZnCl ₂ white crystal (high solubility, acidic aqueous solution); K ₃ Zn ₃ 【Fe(CN) ₆ 】white; Zn ₃ 【 Fe(CN) ₆ 】 ₂ yellowish brown.

Cadmium compounds: CdO brown gray ↓; CdI ₂ yellow; CdS yellow (cadmium yellow pigment) ↓; HgCl ₂ (mercuric liter) white; HgNH ₂ Cl white ↓; Hg ₂ Cl ₂ (calomel) white ↓.

Mercury compounds: HgO red (large grain) or yellow (small grain) ↓; HgI ₂ red or yellow (slightly soluble); HgS black or red ↓; Hg ₂ NI H ₂ O red ↓; Hg ₂ (NO ₃ ) ₂ colorless crystals.

ZnS phosphor: Ag blue; Cu yellow-green; Mn orange.

Titanium subgroup (English IVB):

Titanium compound: Ti ³⁺ purple; [TiO(H ₂ O ₂ ) ₂ ] ²⁺ orange; H ₂ TiO ₃ white ↓; TiO ₂ white (titanium white pigment) or pink (rutile) ↓; (NH ₄ ) ₂ TiCl ₆ yellow crystals; [Ti(H ₂ O) ₆ ] Cl ₃ purple crystals; [Ti(H ₂ O) ₅ Cl] Cl ₂ H ₂ O green crystals; TiCl ₄ colorless fuming liquid.

Zirconium, hafnium: MO ₂ , MCl ₄ white.

Vanadium subgroup (English VB):

Vanadium compounds: V ²⁺ purple; V ³⁺ green; VO ²⁺ blue; V(OH) ^4- yellow; VO ₄ ^3- yellow; VO black; V ₂ O ₃ gray-black; V ₂ S ₃ brown-black; VO ₂ blue solid; VF ₄ green solid; VCl _{4 dark brown liquid; VBr 4 magenta} liquid; V ₂ O ₅ yellow or brick red; hydrated V 2 O ₅ brownish red; saturated _{V 2 O 5} solution (slightly soluble) pale Yellow; 【VO ₂ (O ₂ ) ₂ 】 ^3- yellow; 【V(O ₂ ) ₃ 】 ^3- red brown.

Condensation of vanadate: light yellow ^- dark red ^- light yellow as the ratio of vanadium oxygen atoms decreases.

Niobium and tantalum: slightly.

Chromium subgroup (English VIB):

Chromium compounds: Cr ²⁺ blue; Cr ³⁺ purple; Cr2O7 ^2- orange red; CrO4 ^2- yellow; Cr(OH) ^4- bright green; Cr(OH) ₃ gray blue; Cr ₂ O ₃ green; CrO ₃ dark red Acicular; [CrO(O ₂ ) ₂ ] OEt ₂ blue; CrO ₂ Cl ₂ dark red liquid; Na ₂ Cr ₂ O ₇ , K ₂ CrO ₇ orange red; Ag ₂ CrO ₄ brick red ↓; BaCrO ₄ yellow ↓; PbCrO ₄ yellow↓.

Purple Cr ₂ (SO ₄ ) ₃ 18H ₂ O——>Green Cr ₂ (SO ₄ ) ₃ 6H ₂ O——>Pink Cr ₂ (SO ₄ ) ₃

Dark green [Cr(H ₂ O) ₄ Cl ₂ ]Cl-cooled HCl->purple [Cr(H ₂ O) ₆ ]Cl ₃ -ether HCl->light green [Cr(H ₂ O) ₅ Cl]Cl ₂

【Cr(H ₂ O) ₆ 】 ³⁺ purple;【Cr(H ₂ O) ₄ (NH ₃ ) ₂ 】 ³⁺ purple red;【Cr(H ₂ O) ₃ (NH ₃ ) ₃ 】 ³⁺ light red; 【Cr(H ₂ O) ₂ (NH ₃ ) ₄ 】 ³⁺ orange red; 【Cr(NH ₃ ) ₅ H ₂ O】 ³⁺ orange yellow; 【Cr(NH ₃ ) ₆ 】 ³⁺ yellow.

Molybdenum, tungsten: MoO ₃ white; brown MoCl ₃ ; green MoCl ₅ ; MoS ₃ brown ↓; (NH ₄ ) ₃ [P(Mol ₂ O ₄ 0)] 6H ₂ O yellow crystal ↓; WO ₃ deep yellow; H ₂ WO ₄ xH ₂ O white colloid.

Manganese subgroup (English VIIB):

Manganese compounds: Mn ²⁺ meat red; Mn ³⁺ purple; MnO ₄ ^2- green; MnO ^4- purple; MnO ³⁺ bright green; Mn(OH) ₂ white ↓; MnO(OH) ₂ brown ↓; MnO ₂ black ↓; Anhydrous manganese salt (MnSO ₄ ) white crystal; Hexahydrate manganese salt (MnX ₂ 6H ₂ O, X=halogen, NO ₃ , ClO ₄ ) pink; MnS nH ₂ O meat red ↓; Anhydrous MnS dark green; MnCO ₃ white ↓; Mn ₃ (PO ₄ ) ₂ white ↓; KMnO ₄ purple red; K ₂ MnO ₄ green; K ₂ [MnF ₆ ] golden yellow crystal; Mn ₂ O ₇ brown oily liquid.

Technetium, rhenium: Omit.

Iron series (group VIII of the fourth cycle):

Iron compounds: Fe ²⁺ light green; [Fe(H ₂ O) ₆ ] ³⁺ light purple; [Fe(OH)(H ₂ O) ₅ ] ²⁺ yellow; FeO ₄ ^2- purple red; FeO black; Fe ₂ O ₃ dark red; Fe(OH) ₂ white ↓; Fe(OH) ₃ brown red ↓; FeCl ₃ or FeCl ₂ crystal brown red blue; anhydrous FeSO ₄ white; FeSO ₄ 7H ₂ O green; K ₄ [Fe( CN) ₆ 】(yellow blood salt) yellow crystal; K ₃ 【Fe(CN) ₆ 】(red blood salt) red crystal; Fe ₂ 【Fe(CN) ₆ 】Prussian blue↓; Fe【Fe(CN) ₆ 】 Black ↓; Fe(C ₅ H ₅ ) ₂ (ferrocene) orange-yellow crystal; M ₂ Fe ₆ (SO ₄ ) ₄ (OH) ₁₂ (jarosite, M=NH ₄ , Na, K) light yellow crystal ; Fe(CO) ₅ yellow liquid.

Cobalt compounds: Co ²⁺ pink; CoO gray green; Co ₃ O ₄ black; Co(OH) ₃ brown ↓; Co(OH) ₂ pink ↓; Co(CN) ₂ red; K ₄ [Co(CN) ₆ ] Purple crystals; Co ₂ (CO) ₈ yellow crystals; [Co(SCN) ₆ ] ^4- purple;

Cobalt chloride dehydration discoloration: pink CoCl ₂ 6H ₂ O-325K->purple red CoCl ₂ 2H ₂ O-313K->blue violet CoCl ₂ H ₂ O-393K->blue CoCl ₂ .

Nickel compounds: Ni ²⁺ bright green; 【Ni(NH ₃ ) ₆ 】 ²⁺ purple; Ni(OH) ₂ green ↓; Ni(OH) ₃ black ↓; anhydrous Ni(II) salt yellow; Na ₂ 【Ni (CN) ₄ 】yellow; K ₂ 【Ni(CN) ₄ 】orange; Ni(CO) ₄ colorless liquid.

Platinum group elements (group VIII of the fifth and sixth periods):

Os blue-gray volatile solid; Pd↓(aq) black; OsO ₄ colorless gas with special odor; H ₂ PtCl ₆ orange-red crystals; Na ₂ PtCl ₆ orange-yellow crystals; M ₂ PtCl ₆ (M=K, Rb, Cs, NH ₄ ) yellow ↓. Among the compounds listed above, the inorganic material of the present invention is preferably ferrous chloride (FeCl ₂ ), ferric chloride (FeCl ₃ ), titanium trichloride (TiCl ₃ ), One of titanium tetrachloride (TiCl ₄ ), bismuth chloride (BiCl ₃ ), copper chloride (CuCl ₂ ) or lithium bromide (LiBr).

The discoloration mechanism is, for example, dissolving ferric dichloride (FeCl ₂ ) and methylene blue in dimethyl sulfoxide (DMSO) to form an electrochromic solution of a complementary system, and the color of ferric dichloride crystal particles is blue (Fe ²⁺ is blue), surface oxidation will form reddish brown (Fe ³⁺ is light yellow), ferric dichloride is dissolved in the solvent, that is, because the oxidation changes from Fe ²⁺ to Fe ³⁺ , the solvent becomes light yellow, Electrons are provided by the first transparent conductive element 111. When the methylene blue molecules close to the first transparent conductive element 111 undergo a reduction reaction due to obtaining electrons, the methylene blue becomes a free radical, and when the external voltage is removed, the Fe The potential energy of ³⁺ is different from that of methylene blue free radicals, that is, the potential energy of methylene blue free radicals is lower than that of Fe ³⁺ , and electrons will spontaneously transfer from methylene blue free radicals to Fe ³⁺ , then light yellow Fe ³⁺ It is reduced to blue Fe ²⁺ , and then the entire electrochromic layer 13 changes from light yellow to blue due to the valence change due to reduction, achieving the effect of darkening the color, and it can be adjusted by adjusting the electrochromic solution. The color display effect of the electrochromic layer 13 is controlled by the concentration, the potential difference, the polarity of the solvent, the pH value, the distance between the electrodes and the difference in the dielectric constant.

The above-mentioned electrochromic layer 13 further contains at least one inert conductive salt, which can be lithium, sodium or tetraalkylamine salts, suitable anions for the above-mentioned conductive salts, especially as inert, non-reactive, redox in metal salts. The colored anions can be: tetrafluoroborate ion, tetraphenylborate ion, cyanotriphenylborate ion, tetramethoxyborate ion, perchlorate ion, chloride ion, nitrate ion, sulfate ion, phosphoric acid Radix ion, methanesulfonate ion, ethanesulfonate ion, tetradecanesulfonate ion, pentadecanesulfonate ion, trifluoromethanesulfonate ion, perfluorobutanesulfonate ion, perfluorooctanesulfonate ion , benzenesulfonate ion, chlorobenzenesulfonate ion, toluenesulfonate ion, butylbenzenesulfonate ion, tertiary butylsulfonate ion, dodecylbenzenesulfonate ion, trifluoromethylbenzenesulfonate ion, hexafluoro Phosphate ion, hexafluoroarsenate ion, hexafluorosilicate ion, etc.

In addition, the electrochromic layer 13 prepared above is mostly in a liquid state, and can also be mixed with conductive polymers to form an electrochromic ink, which can be used in conjunction with screen printing.

Please refer to Figures 4, 5, and 6, which are schematic diagrams 1-3 of the structure of the transparent conductive element in the first preferred embodiment of the present invention, which are the arrangement of the first transparent conductive element in the electrochromic module 1, when When there are a plurality of first transparent conductive elements on a first substrate (as shown in FIG. 4 ), preferably the first transparent conductive elements are arranged at intervals, and voltages of different potentials are given alternately, so that each There is a voltage difference between the electrodes so as to provide the electrons needed for the color change of an electrochromic layer 13. In addition, the first transparent conductive element 111 and the second transparent conductive element 111 and the second transparent conductive element 11 can also be provided on the first transparent substrate 11 and the second substrate 12 respectively. Conductive elements 121 are arranged in a manner of sandwiching the electrochromic layer 13 (as shown in FIG. 5 ), or the transparent conductive elements 111, 121 can be arranged in multiple intervals on the first transparent substrate 11 and the second transparent substrate 12 on (as shown in Figure 6).

The above-mentioned electrochromic module 1 can be applied to displays, e-books, 2D/3D display devices, rear-view mirrors and smart glass, etc. Please refer to FIG. 7, which is a three-dimensional decomposition of the second preferred embodiment of the present invention The schematic diagram is the application of the aforementioned electrochromic module to a flat/three-dimensional display device. As shown in the figure, the display device of the present invention combines an electrochromic module 1 with an image display module 2, wherein:

The image display module 2 is used to display a planar image and a stereoscopic image, and the displayed stereoscopic image can be generated by software, firmware or hardware technology, for example, the planar image is converted into a left-eye image and a right-eye image by software or firmware The image display module 2 can be a liquid crystal display (Liquid Crystal Display, LCD), a plasma display (Plasma Display Panel, PDP), a surface conduction electron emission display (Surface conduction Electron-emitter Display, SED), a field emission One of Field Emission Display (FED), Vacuum Fluorescent Display (VFD), Organic Light-Emitting Diode (OLED) or E-Paper.

The electrochromic module 1 is combined on the surface of the image display module 2, which includes a first transparent substrate 11, a second transparent substrate 12 and a plurality of electrochromic layers 13, wherein:

The upper surface of the first transparent substrate 11 is provided with a first transparent conductive element 111, and the lower surface of the second transparent substrate 12 is provided with a second transparent conductive element 121, and the electrochromic layers 13 are composed of the first transparent conductive element 111. and the electrical conduction of the second transparent conductive element 121 to produce a color change, but the illustration is only for illustration, and multiple transparent conductive elements (as shown in FIG. 12 ) can only be arranged on a single substrate, as long as each electrical The chromic layer 13 is in contact with transparent conductive elements with different potentials at the same time, so that electron energy can be injected and transmitted in the electrochromic layer when it changes color.

The materials of the first transparent substrate 11 and the second transparent substrate 12 and the material of the first transparent conductive element 111 are the same as those mentioned above, and will not be described here again.

The materials of the electrochromic layers 13 are made by dissolving organic materials and inorganic materials in a solvent. The organic materials can be redox indicator (Redox Indicator) and pH indicator (acid-base indicator), etc. The invention preferably uses methylene blue (Methylene blue, C ₁₆ H ₁₈ ClN ₃ S·3H ₂ O), dichlorophenol indophenol sodium (Dichlorophenolindophenol sodium, C ₁₂ H ₆ Cl ₂ NNaO ₂ ), N-phenyl o Aminobenzoic acid (C ₁₃ H ₁₁ NO ₂ ), sodium diphenylamine sulfonate (C ₁₂ H ₁₀ NNaO ₃ S), N,N′-diphenylbenzidine (C ₂₀ H ₂₀ N ₂ ), viologen (Viologen ) and Variamine Blue B Diazonium salt B (Variamine Blue B Diazonium salt, C ₁₃ H ₁₂ ClN ₃ O), etc., and the inorganic material can be selected from transition elements (including scandium subgroup (IIIB), titanium subgroup (IVB), Oxidation of vanadium subgroup (VB), chromium subgroup (VIB), manganese subgroup (VIIB), iron series (VIII), copper subgroup (IB), zinc subgroup (IIB) or platinum series (VIII), etc.) Compounds, sulfides, chlorides, hydroxides and other inorganic derivatives, or can be selected from halogen (VIIA), oxygen (VIA), nitrogen (VA), carbon (IVA), boron (IIIA), One of inorganic derivatives such as alkaline earth group (IIA) and alkali metal group (IA), the preferred embodiment of the present invention uses ferrous chloride (FeCl ₂ ), ferric chloride (FeCl ₃ ), titanium trichloride (TiCl ₃ ), titanium tetrachloride (TiCl ₄ ), bismuth chloride (BiCl ₃ ), copper chloride (CuCl ₂ ) or lithium bromide (LiBr); and the solvent can be dimethyl sulfoxide [ (CH ₃ ) ₂ SO)], propylene carbonate (C ₄ H ₆ O ₃ ), water (H ₂ O), γ-butyrolactone, acetonitrile, propionitrile, benzonitrile, glutaronitrile, methylglutadiene Nitrile, 3,3'-oxydipropionitrile, hydroxypropionitrile, dimethylformamide, N-methylpyrrolidone, sulfolane, 3-methylsulfolane or mixtures thereof, the present invention is different from general inorganic electrochromic Compared with the electrochromic layer, the inorganic electrochromic layer requires double loading of ions and electrons into the lattice, and requires a large driving voltage. Therefore, the solution causes defects in the material, and the service life is only about 10,000 to 20,000 times. The concept described in the present invention , only need to change the valence number of ions in the electrochromic material, not only the driving voltage is small, but also the material does not produce defects, and the service life can even reach more than 30,000 times, and the present invention is combined with an image display module as a 2D/3D Masks for image display, image display requires higher resolution and light transmittance, compared with the known electrochromic multilayer structure, the electrochromic layer of the present invention does not require junction Combined electrolyte or other auxiliary color-changing layers, so its thickness is greatly reduced and the light output rate is improved.

Please refer to Figures 8 and 9, which are schematic diagrams 1 and 2 of the structure of the transparent conductive element in the second preferred embodiment of the present invention. The first transparent conductive element 111 and the second transparent conductive element 121 can be integrally arranged on the On the surface of the first transparent substrate 11 and the second transparent substrate 12, the first transparent layer can also be arranged in a plurality of intervals according to the arrangement position and quantity of the electrochromic layers 13 arranged at intervals. The conductive element 111 and the second transparent conductive element 121 .

These electrochromic layers 13 can be mixed with conductive polymers to form electrochromic inks, and are arranged on the first transparent substrate 11 by screen printing, or as shown in FIGS. Schematic diagrams 1 and 2 of the structure of the transparent conductive element of the preferred embodiment, a plurality of barrier units 14 are arranged between the electrochromic layers 13 arranged at equal intervals, and the electrochromic layers 13 are separated into strips by the barrier units 14 , or use the blocking unit 14 to encapsulate the electrochromic layer 13 in the space region formed by the blocking unit 14, and the blocking unit can be a photoresist.

Please refer to Figures 12 and 13, which are perspective exploded schematic diagrams and cross-sectional views of the fourth preferred embodiment of the present invention. The first transparent conductive element 111 is to simplify the manufacturing process of the module; furthermore, between the electrochromic layers 13 arranged at intervals, a plurality of barrier units 14 are provided, as shown in FIG. 14 , to increase the structural strength and To separate the electrochromic layers 13, it should be noted that each electrochromic layer 13 needs to be in contact with two first transparent conductive elements 111 with different potentials at the same time. Schematic diagram of the structure of the transparent conductive element of the fourth preferred embodiment, each group of oppositely arranged first transparent conductive elements 111 is arranged corresponding to each electrochromic layer 13 arranged at intervals, so that each electrochromic layer 13 It is arranged on the first transparent conductive elements 111 with different potentials, but the illustration is only for illustration and not for limiting the present invention, and other corresponding changes and modifications should be included in the patent scope of the present invention.

Please refer to FIG. 16, which is a cross-sectional view of the sixth preferred embodiment of the present invention. Its structure directly uses the first transparent conductive elements 111 as barrier units, so as to achieve its function of separating the electrochromic layer 13 and also The contact area between the electrochromic layer 13 and the first transparent conductive element 111 can be increased. As shown in FIG. 17 , it is a top view of the structure of the first transparent conductive elements. There are two sets of first transparent conductive elements 111 arranged in a staggered interval, so that each adjacent first transparent conductive element 111 has a different potential to form a voltage difference. Please refer to Figures 18 and 19, which are transparent conductive elements The first and second perspective views of the structure, the first transparent conductive elements 111 can be formed in the form of partitions (as shown in Figure 18), or can form a plurality of accommodating grooves (as shown in Figure 19), and the electrochromic layer 13 is set In each accommodating groove, it should be noted that the first transparent conductive elements 111 with different potentials are not in contact with each other, and are arranged in a staggered interval.

In the above-mentioned structure of FIG. 17, in some cases, the electrochromic layer 13 will be at the positive end, such as the left side electrode in the figure. Due to the problem of the electric field effect, the discoloration effect close to the positive end will be stretched over time. will gradually become lighter, and form a color difference with the negative terminal. In order to solve the above problems, the first transparent conductive element 111 can be designed as shown in Figure 20. As shown in the figure, it is the first transparent conductive element. In the second top view of the structure, the first transparent conductive element 111 with negative voltage covers the first transparent conductive element 111 with positive voltage in an S-shaped manner.

Please refer to FIG. 21, which is a cross-sectional view of a seventh preferred embodiment of the present invention. The first transparent conductive element 111 and the second transparent conductive element 121 are arranged on the first transparent substrate 11 and the second transparent conductive element 121 in a plurality of intervals. The surface of the second transparent substrate 12, and a plurality of space regions are generated between the first transparent substrate 11 and the second transparent substrate 12, then the electrochromic layers 13 will be respectively arranged in the plurality of space regions, The purpose of the above setting is to use the first transparent conductive element 111 and the second transparent conductive element 121 as barrier units at the same time, as shown in Figures 22 and 23, which are the structural top view and structural perspective view of the conductive element of the seventh preferred embodiment , that is, the first transparent conductive elements 111 and the second transparent conductive elements 121 are alternately arranged at intervals, and the first transparent conductive elements 111 give a positive voltage, while the second transparent conductive elements 121 give a negative voltage , and vice versa, so that a voltage difference is formed between the first transparent conductive elements 111 and the second transparent conductive elements 112 arranged in strips, but this arrangement is only for illustration, and other corresponding modifications and changes are all Should be included in the patent scope of the present invention.

Please refer to Fig. 24 and shown in 25, which are cross-sectional views of the eighth and ninth preferred embodiments of the present invention. The discoloration state of the electrochromic layer 13 of the present invention will be affected by solution concentration, potential difference, solvent polarity, and pH value. , two-pole spacing and dielectric constant and other factors have different effects. As shown in the figure, the surface of the first transparent substrate 11 is provided with a plurality of first transparent conductive elements 111 arranged at intervals. These first transparent conductive elements 111 is to apply positive and negative voltages alternately, then the electrochromic layer 13 poured between the first transparent substrate 11 and the second transparent substrate 12 will cover the first transparent conductive elements 111 of the negative electrode and change color; As shown in Figure 24, in order to make the solution-type electrochromic layer 13 change color accurately on the surface or periphery of the first transparent conductive element 111 of the negative electrodes, a second transparent substrate 12 is added on the lower surface of the second transparent substrate 12. The transparent conductive element 121, and the second transparent conductive element 121 only provides a positive voltage, whereby the electrochromic layer 13 is limited to the range of discoloration on the negative first transparent conductive elements 111.

In addition, as shown in FIG. 26 , which are cross-sectional views of the tenth and eleventh preferred embodiments of the present invention, a plurality of first transparent conductive elements 111 arranged at intervals are arranged on the first transparent substrate 11. The first transparent conductive elements 111 The elements 111 provide positive and negative voltages alternately, and a plurality of barrier units 14 are laid on the surface of the first transparent conductive elements 111, so as to completely cover the surface of each first transparent conductive element 111, then the electro-induced After the power is supplied, the color-changing layer 13 will change color between the gaps of the first transparent conductive elements 111 of each positive and negative voltage, because the electrochromic layer 13 will change color by attaching to the walls of the first transparent conductive elements 111 , so the blocking unit 14 is to block the electrochromic layer 13 from attaching to the upper surface of the first transparent conductive element 111 to change color, and its material can be photoresist; as shown in Figure 26, it is another embodiment of the tenth embodiment. Variation type, in order to enable the electrochromic layer 13 to be pressed between the first transparent conductive elements 111 of positive and negative voltages when changing color, at least one second transparent conductive element is provided on the lower surface of the second transparent substrate 12. element 121 , and the second transparent conductive element 121 only provides positive voltage to limit the color changing range of the electrochromic layer 13 .

Please refer to Figures 27 and 28, which are cross-sectional views of the twelfth and thirteenth preferred embodiments of the present invention. Compared with the eighth preferred embodiment shown in Figure 23, the eighth preferred embodiment In order to lay on the surface of the substrate with a larger area, the eleventh preferred embodiment shown in FIG. There is a gap between the spacers and the second transparent substrate 12, so that the electrochromic layer 13 can circulate freely in the space encapsulated by the first transparent substrate 11 and the second transparent substrate 12, and its power supply method is also When the positive and negative voltages are given alternately, the electrochromic layer 13 will cover the periphery of the first transparent conductive element 111 of the negative electrode and change color; as shown in Figure 29, in order to make the electrochromic layer 13 of the solution When the surface or periphery of the first transparent conductive element 111 of the negative poles changes color, a second transparent conductive element 121 is added on the lower surface of the second transparent substrate 12, and the second transparent conductive element 121 only provides positive voltage. Therefore, the electrochromic layer 13 is limited to the range of discoloration on the first transparent conductive elements 111 of the negative electrodes.

In summary, in the display device of the present invention, the electrochromic module 1 is matched with the image display module 2, that is, the electrochromic module 1 is arranged on the image projection surface of the image display module 2, and the image display module 2. When displaying the processed multiple images (divided into left-eye image L and right-eye image R), through the light-shielding regions formed by the electrochromic layers 13 arranged at multiple intervals, it will not be visible after being received by the naked eye. Moirés are generated to form a three-dimensional image.

The above description of the present invention is illustrative rather than restrictive. Those skilled in the art understand that many modifications, changes or equivalents can be made to it within the spirit and scope of the claims, but they will all fall into within the protection scope of the present invention.

Claims (52)

1. the electrochromism module of organic and inorganic material is characterized in that, includes:

One first transparency carrier, its upper surface are provided with at least one first transparent conductive element;

One second transparency carrier; And

One electrochromic layer is located between this first transparency carrier and this second transparency carrier, and this electrochromic layer mixed organic material and inorganic material are dissolved in the solvent made.

2. the electrochromism module of organic and inorganic material as claimed in claim 1; It is characterized in that, the material of said transparency carrier be plastic cement, high molecular weight plastic, glass or for be selected from plastic polymer group that resin, polyethylene terephthalate, polycarbonate, tygon, PVC, polypropylene and polystyrene, polymethylmethacrylate form one of them.

3. the electrochromism module of organic and inorganic material as claimed in claim 1; It is characterized in that, the material of this first transparent conductive element be selected from that tin indium oxide, indium zinc oxide, zinc oxide aluminum and tin-antiomony oxide form mix one of them of oxide group.

4. the electrochromism module of organic and inorganic material as claimed in claim 1 is characterized in that the material of this first transparent conductive element is CNT, gathers-3,4-vinyl dioxy thiophene or polyaniline.

5. the electrochromism module of organic and inorganic material as claimed in claim 1 is characterized in that this organic material is redox indicator, pH indicator or organic compound.

6. the electrochromism module of organic and inorganic material as claimed in claim 5 is characterized in that this redox indicator is methylenum careuleum, dichlorophenol indophenol sodium, N-phenylanthranilic acid, diphenylamine sulfonic acid sodium salt, N, N '-diphenylbenzidine or purpurine.

7. the electrochromism module of organic and inorganic material as claimed in claim 5 is characterized in that, this pH indicator is the blue salt B in all Lamines.

8. the electrochromism module of organic and inorganic material as claimed in claim 5 is characterized in that this organic compound is ferrocene or 7,7,8,8-four cyano benzoquinone bismethane.

9. the electrochromism module of organic and inorganic material as claimed in claim 1 is characterized in that this inorganic material is an inorganic derivative.

10. the electrochromism module of organic and inorganic material as claimed in claim 9 is characterized in that this inorganic derivative is oxide, sulfide, chloride or the oxyhydroxide of transitional element.

11. the electrochromism module of organic and inorganic material as claimed in claim 10 is characterized in that, this transitional element is copper subgroup, zinc subgroup, scandium subgroup, titanium subgroup, vanadium subgroup, chromium subgroup, manganese subgroup, iron system and platinum group.

12. the electrochromism module of organic and inorganic material as claimed in claim 9 is characterized in that this inorganic derivative is halogen family, chalcogen, nitrogen family, carbon family, boron family, alkaline earth or alkali metal group.

13. the electrochromism module of organic and inorganic material as claimed in claim 1 is characterized in that this inorganic material is iron protochloride, ferric trichloride, titanium trichloride, titanium tetrachloride, bismuth chloride, cupric chloride or lithium bromide.

14. the electrochromism module of organic and inorganic material as claimed in claim 1; It is characterized in that; The material of this solvent is dimethyl sulfoxide (DMSO), carbonic allyl ester, water, gamma-butyrolacton, acetonitrile, propionitrile, benzene nitrile, glutaronitrile, methyl cellosolve acetate glutaronitrile, 3,3 '-oxydipropionitrile, hydroxypropionitrile, dimethyl formamide, N-methylpyrrole pyridine ketone, sulfolane, 3-methyl sulfolane or its potpourri.

15. the electrochromism module of organic and inorganic material as claimed in claim 1 is characterized in that this electrochromic layer further contains at least a inertia conducting salt.

16. combination as claimed in claim 15 is organic and the electrochromism module of inorganic material, it is characterized in that this inertia conducting salt is lithium, sodium or tetraalkyl amine salt.

17. the electrochromism module of organic and inorganic material as claimed in claim 1 is characterized in that, when this first transparent conductive element when being a plurality of, is located on this first transparency carrier with being distributed in distance.

18. the electrochromism module of organic and inorganic material as claimed in claim 1 is characterized in that this second transparency carrier surface further has one second transparent conductive element.

19. the electrochromism module of organic and inorganic material as claimed in claim 18 is characterized in that, when this first, second transparent conductive element when being a plurality of, is located on this first, second transparency carrier with being distributed in distance.

20. a display device is characterized in that, includes:

One image display module is in order to show a flat image and a stereopsis;

One electrochromism module is located at this image display module surface, includes:

One first transparency carrier, its surface are provided with at least one first transparent conductive element;

One second transparency carrier; And

A plurality of electrochromic layers are spaced and are located between this first transparency carrier and this second transparency carrier, and the material mixed organic material and the inorganic material of said electrochromic layer are dissolved in the solvent made.

21. display device as claimed in claim 20; It is characterized in that, the material of said transparency carrier be plastic cement, high molecular weight plastic, glass or by be selected from resin, polyethylene terephthalate, polycarbonate, tygon, PVC, polypropylene and polystyrene, polymethylmethacrylate one of them of composition plastic polymer group.

22. display device as claimed in claim 20 is characterized in that, the material of this first transparent conductive element be selected from that tin indium oxide, indium zinc oxide, zinc oxide aluminum and tin-antiomony oxide form mix one of them of oxide group.

23. display device as claimed in claim 20 is characterized in that, the material of this first transparent conductive element is CNT, gathers-3,4-vinyl dioxy thiophene or polyaniline.

24. display device as claimed in claim 20 is characterized in that, this organic material is redox indicator, pH indicator or organic compound.

25. display device as claimed in claim 24 is characterized in that, this redox indicator is methylenum careuleum, dichlorophenol indophenol sodium, N-phenylanthranilic acid, diphenylamine sulfonic acid sodium salt, N, N '-diphenylbenzidine or purpurine.

26. display device as claimed in claim 24 is characterized in that, this pH indicator is the blue salt B in all Lamines.

27. display device as claimed in claim 24 is characterized in that, this organic compound is ferrocene or 7,7,8,8-four cyano benzoquinone bismethane.

28. display device as claimed in claim 20 is characterized in that, this inorganic material is an inorganic derivative.

29. display device as claimed in claim 28 is characterized in that, this inorganic derivative is oxide, sulfide, chloride or the oxyhydroxide of transitional element.

30. display device as claimed in claim 29 is characterized in that, this transitional element is copper subgroup, zinc subgroup, scandium subgroup, titanium subgroup, vanadium subgroup, chromium subgroup, manganese subgroup, iron system and platinum group.

31. display device as claimed in claim 28 is characterized in that, this inorganic derivative is halogen family, chalcogen, nitrogen family, carbon family, boron family, alkaline earth or alkali metal group.

32. display device as claimed in claim 20 is characterized in that, this inorganic material is iron protochloride, ferric trichloride, titanium trichloride, titanium tetrachloride, bismuth chloride, cupric chloride or lithium bromide.

33. display device as claimed in claim 20; It is characterized in that; The material of this solvent is dimethyl sulfoxide (DMSO), carbonic allyl ester, water, gamma-butyrolacton, acetonitrile, propionitrile, benzene nitrile, glutaronitrile, methyl cellosolve acetate glutaronitrile, 3,3 '-oxydipropionitrile, hydroxypropionitrile, dimethyl formamide, N-methylpyrrole pyridine ketone, sulfolane, 3-methyl sulfolane or its potpourri.

34. display device as claimed in claim 20 is characterized in that, this electrochromic layer further contains at least a inertia conducting salt.

35. display device as claimed in claim 34 is characterized in that, this inertia conducting salt is lithium, sodium or tetraalkyl amine salt.

36. display device as claimed in claim 20 is characterized in that, said electrochromic layer further is mixed with conducting polymer to form electrochromism printing ink.

37. display device as claimed in claim 20 is characterized in that, when this first transparent conductive element when being a plurality of, is located on this first transparency carrier with being distributed in distance.

38. display device as claimed in claim 37 is characterized in that, said electrochromic layer is located between said first transparent conductive element, and separates said electrochromic layer with said first transparent conductive element.

39. display device as claimed in claim 37 is characterized in that, said first transparent conductive element more forms a plurality of storage tanks, and said electrochromic layer is located in the said storage tank.

40. display device as claimed in claim 37 is characterized in that, said first transparent conductive element is staggered gives positive and negative voltage.

41. display device as claimed in claim 37 is characterized in that, the said first transparent conductive element surface further is provided with blocker unit, to cover the upper surface of said first transparent conductive element.

42. display device as claimed in claim 41 is characterized in that, this blocker unit is a photoresistance.

43. display device as claimed in claim 20 is characterized in that, further is provided with a plurality of spaced blocker unit between said transparency carrier, said electrochromic layer is located between said blocker unit.

44. display device as claimed in claim 43 is characterized in that, said blocker unit is a photoresistance.

45. display device as claimed in claim 20 is characterized in that, the surface of this second transparency carrier further has at least one second transparent conductive element.

46. display device as claimed in claim 45; It is characterized in that; When this first, second transparent conductive element when being a plurality of; Be located at this corresponding surface of first, second transparency carrier, and each electrochromic layer produces change color according to each electrically conducting of first, second transparent conductive element of group with being distributed in distance.

47. display device as claimed in claim 45; It is characterized in that; When this first transparent conductive element and this second transparent conductive element are respectively a plurality of; Be located to series arrangement between said transparency carrier, said electrochromic layer is located between said first transparent conductive element and said second transparent conductive element.

48. display device as claimed in claim 45 is characterized in that, further is provided with a plurality of spaced blocker unit between said transparency carrier, said electrochromic layer is with being located at respectively between said blocker unit.

49. display device as claimed in claim 48 is characterized in that, this blocker unit is a photoresistance.

50. display device as claimed in claim 45 is characterized in that, when said first transparent conductive element when being a plurality of, its surface further is provided with a plurality of blocker unit, to cover the upper surface of said first transparent conductive element.

51. display device as claimed in claim 50 is characterized in that, this blocker unit is a photoresistance.

52. display device as claimed in claim 45; It is characterized in that, when this first transparent conductive element when being a plurality of, the upper surface of being located at this first transparency carrier that is distributed in distance; And staggered giving positive and negative voltage, this second transparent conductive element then gives positive voltage.

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