TW201944150A - Improved electronic control full-solid intelligent dimming product and glass window thereof solving the problems of high difficulty, low productivity, low yield, high cost and slightly small product size - Google Patents

Abstract

This invention relates to an improved electronic control full-solid intelligent dimming product and a glass window thereof. By optimizing a film layer structure of an existing solid intelligent dimming product and simplifying a production process, the problems of high difficulty, low productivity, low yield, high cost and slightly small product size caused by producing the solid intelligent dimming product by using a large-area magnetron sputtering technology are solved; a transparent electrode produced by using a novel process can achieve a low resistance value under non-annealing preparation; and a dielectric composite strengthened layer increases the transmittance during full transmission of the product, and a dielectric composite protective layer enhances the later processing capacity of the product and can also enrich the display color of the product.

Description

   Improved electronically controlled all-solid-state intelligent dimming product and its glass window   

The invention relates to the technical field of energy saving, in particular to an improved electronically controlled all-solid-state intelligent dimming device and a preparation method thereof.

The existing conventional solid-state electrochromic system in the field of electrochromic technology consists of a so-called "six-layer" basic model structure including a transparent substrate: a transparent substrate; a lower transparent electrode layer; a lower electrochromic layer; an ion conductive layer ; An electrochromic layer; and a transparent electrode layer.

The electrochromic system in the above model includes two layers of materials that can be reversibly oxidized or reduced. One of the oxidation states is generally transparent and the other reduced state is generally transparent. The transparent conductive layer is connected to an external power source and is applied to Appropriate normal-phase DC voltage between the upper and lower transparent conductive electrodes, the ions of the ion storage layer are extracted, enter the electrochromic layer through the ion conductor, and realize power-free memory. When the reverse voltage is applied, the electrochromic layer The middle ions are extracted and then enter the storage layer, and the glass returns to transparent. By controlling different changes in the transmittance and color of the product, it can selectively absorb or reflect external thermal radiation and internal thermal diffusion. In some application fields, a combination of two substrates may be used, and each substrate may maintain a part of the electrochromic function, and the entire dimming and color changing system is a combination of two substrates.

Among basic electrochromic materials, the cathode color changing material amorphous tungsten oxide is most practical. The counter electrode generally uses another electrochromic material that is complementary to the electrochromic layer. Anode electrochromic material for electrodes. Under the action of an applied voltage, the cathode and anode will be colored and faded at the same time, so that the color in the colored state is deeper and the light transmittance in the faded state is higher. The typical combination of this complementary discoloration is WO-NiO, where WO is colored in the reduced state, and NiO is colored in the oxidized state, which can deepen the discoloration. Similarly, when WO is in an oxidized state, NiO is in a reduced state, so that a glass with high transmittance can be produced. In addition, solid ionic conductors have also received great attention from people. LiF, LiA ₁ F ₄ , LiN, LiA ₁ C ₁ plasma conductor films all have good comprehensive properties.

In order to solve the problems of high production cost of the original all solid-state intelligent dimming products, single color during full light transmission and discoloration, poor visual effect, small finished product size, low transmittance during full transmission, and high temperature preparation of conductive film. The present invention improves the visible light transmittance through the preferred film layer material, film layer structure, and process method, and particularly adds a dielectric composite reinforced layer and a dielectric composite protective layer, and also increases the range of color selection during total transmission and discoloration. .

The technical solution of the present invention is as follows: One object of the present invention is to provide an improved electronically controlled all-solid-state intelligent dimming device, which includes a transparent substrate, and at least one side of the transparent substrate is provided in order from bottom to top: A dielectric composite strengthening layer, a lower transparent electrode layer, a lower electrochromic layer, an ion conductive layer, an upper electrochromic layer, an upper transparent electrode layer, and a dielectric composite protective layer.

Another object of the present invention is a glass window with the aforementioned improved electronically controlled all-solid-state intelligent dimming device.

In order that the review committee can further understand and understand the purpose, technical features and effects of the present invention, the embodiments are described in detail with the drawings as follows:

     [Learning]     

None

     〔this invention〕     

1‧‧‧ transparent substrate

1A, 1B, 1C‧‧‧bearing substrate

2‧‧‧ Dielectric Composite Strengthening Layer

3‧‧‧ lower transparent electrode layer

4‧‧‧ Electrochromic layer

5‧‧‧ ion conducting layer

6‧‧‧ Electrochromic layer

7‧‧‧ on transparent electrode layer

8‧‧‧Dielectric composite protective layer

Fig. 1 is a schematic diagram of the basic structure of the improved electronically controlled all-solid-state intelligent dimming device of the present invention; Fig. 2 is a schematic diagram of the film layer manufacturing process of the improved electrically-controlled all-solid-state intelligent dimming device of the present invention; Fig. 3 FIG. 4 is a schematic diagram of another embodiment of the improved electronically controlled all-solid-state intelligent dimming product of the present invention; and FIG. 4 is a schematic diagram of still another embodiment of the improved electronically-controlled all-solid-state intelligent dimming product of the present invention.

The present invention is an improved electronically controlled all-solid-state intelligent dimming product and its glass window. As shown in FIG. 1, in one embodiment, at least one side of a transparent substrate 1 is in order from bottom to top. Follow-up film structure: a dielectric composite reinforcement layer 2, a lower transparent electrode layer 3, a lower electrochromic layer 4, an ion conductive layer 5, an upper electrochromic layer 6, an upper transparent electrode layer 7, and a dielectric The composite protective layer 8, and in other embodiments, the improved electronically controlled all-solid-state intelligent dimming product formed by the aforementioned structure can be made into the state of a glass window required by the industry.

The transparent substrate 1 can be various transparent substrates such as glass, PMMA, PC, and PET. Among them, the preferred glass substrates of the present invention include various functional glasses such as automotive-grade coated plates, solar ultra-whiteboards, and colored glass. The original plate.

The dielectric composite reinforced layer 2 can be conductive or insulated, and has the function of anti-reflection or reflection of visible light. The dielectric composite reinforced layer 2 is composed of SiO ₂ , TiO ₂ , Si ₃ N ₄ , SiN ₂ O, ZnSnO ₂ , Nb ₂ O. _5. ZnO, ZrO ₂ , NbZr, BiO ₂ , Al ₂ O ₃ , Cr ₂ N and other materials, and the dielectric composite reinforcement layer 2 has a thickness of 10-150 nm, preferably 40 -120 nm, more preferably 60-100 nm in thickness.

The lower transparent electrode layer 3 has high conductivity and low visible light absorption. When there is a need for reflection, a metallic material can be selected. The lower transparent electrode layer 3 is composed of FTO, ITO, ATO, AZO, Pt, Au, Ag, It is composed of doped oxide or metal or alloy materials in Cu, Al, and Cr. The thickness of the lower transparent electrode layer 3 is 10-600 nm, preferably 30-300 nm, and more preferably 50-150 nm.

The lower electrochromic layer 4 is for improving interface performance and durability, and can add non-chromic or / and electrolytic materials; the multilayer or material produced by the addition is not defined as an electrolyte because it does not participate in ion conduction, and the lower electrochromic Layer 4 is composed of one or more materials of WO ₃ , MoO ₃ , Nb ₂ O ₅ , Ir ₂ O ₃ , TiO ₂ , Ta ₂ O ₅ , V ₂ O ₅ or WO ₃ , MoO doped with oxide ₃ , Nb ₂ O ₅ , TiO ₂ , SnO ₂ , Ta ₂ O ₅ , V ₂ O ₅ composed of one or more materials, and the lower electrochromic layer 4 has a thickness of 100-800 nm, and preferably a thickness of 150- 600 nm, more preferably 200-400 nm.

The ion-conducting layer 5 having an electron insulating, ion-conducting function; visible absorbance is less than 6%; nitride state electrolyte can improve the life of the system, the difficulty of reducing the film deposition, and the ion-conducting layer 5 by the LiNbO _3, LiBO _2, LiF, Li ₃ N, LiTaO ₃ , LiA ₁ F ₄ , LiA ₁ C ₁ and other materials, which can be single or multiple layers, and the thickness of the ion conductive layer 5 is 10-2000nm, preferably 50 -300 nm, more preferably 100-200 nm in thickness.

The electrochromic layer 6 and the lower electrochromic layer 4 are interchangeable in position under different application requirements to achieve complementary colors and / or charge balance requirements, and the electrochromic layer 6 is composed of NiOx, Ir ₂ O ₃ , Rh ₂ O ₃ , CoO ₂ , InN or one or more materials or oxide-doped NiOx, Ir ₂ O ₃ , Rh ₂ O ₃ , CoO ₂ or more materials, and the above The electrochromic layer 6 has a thickness of 1 to 600 nm, more preferably a thickness of 50 to 500 nm, and preferably a thickness of 150 to 350 nm.

The upper transparent electrode layer 7 has high conductivity and low visible light absorption; when there is a need for reflection, a metal performance material can be selected. The resistance of the lower transparent electrode layer 3 and the upper transparent electrode layer 7 is less than 20Ω / □ (area resistance). ), And all are prepared by a vacuum high temperature annealing process, and the upper transparent electrode layer 7 is made of doped oxides or metals in Cr, Al, ITO, Pt, Ni, FTO, Au, ATO, Ag, Cu, AZO Alloy materials. When the system requires reflection, one or more conductive materials can be selected from metals. The thickness of the upper transparent electrode layer 7 is 10-600 nm, preferably 30-300 nm, and more preferably 50-250 nm. . In other embodiments, the upper transparent electrode layer 7 can be first disposed on a carrier substrate 1A, and can be disposed in the dimming product together.

The dielectric composite protective layer 8 can be conductive or insulated; and the dielectric composite protective layer 8 is composed of TiO ₂ , Cr ₂ N, ZnSnO ₂ , ZnO, ZrO ₂ , NbZr, Si ₃ N ₄ , SiO ₂ , SiN ₂ O, BiO _2. Several materials of Al ₂ O ₃ , Nb ₂ O ₅ , Cr, Al, and Pd. They can be single or multiple layers. In addition, the thickness of the dielectric composite protective layer 8 is 1-200 nm, preferably 20-180 nm. More preferably, the thickness is 50-150 nm. In other embodiments, the dielectric composite protective layer 8 can be firstly disposed on another supporting substrate 1B, and can be provided in the dimming product together, or the dielectric composite protective layer 8 and the upper transparent electrode layer 7 can be provided together. They are sequentially arranged on the same supporting substrate 1C, and are also arranged in the dimming product together. In addition, the dielectric composite protective layer 8 is different from a side of the transparent substrate 1 and can also be provided with a low-radiation functional film, a sun-protective functional film, a hydrophobic functional film, a hydrophilic functional film, an anti-reflection functional film, a One of the electromagnetic shielding functional film, a dust-resistant photocatalytic functional film, or a combination thereof.

In this embodiment, where x in NiOx is different from the stoichiometry of nickel oxide NiO, the specific value range of NiOx is 0 <x <1, preferably 0.2 <x <0.9, and more preferably 0.4 <x <0.8.

The following is the basic target structure and process parameters of the present invention:

In the field of electrochromic technology disclosure, the above-mentioned example is a reference scheme, and does not limit the present invention in any form. It should be understood that there are different modifications without exceeding the technical scheme described in the claims.

In order to explain in detail the technical content, structural features, achieved objectives, and effects of the present invention, the following will be described in detail with reference to the embodiments and the accompanying drawings.

The main optical properties of the solid-state smart dimming manufactured product developed by the above invention are as follows:

a. Use the present invention to make a 6mm EC + 12A + 6mm + 12A + 6mm (color-changing film layer on the inner surface of an outdoor sheet, filled with an inert gas) structure of hollow glass. The measurement data is as follows (glass is 6mm ordinary white glass) :

b. Use the present invention to make 6mm + 1.52SGP + 6mm EC + 12A + 6mm (color changing film layer on the inner surface of the outdoor sheet, filled with inert gas) structure of hollow glass, the measurement data is as follows (glass is 6mm ordinary white glass ):

c. Use the present invention to make 6mm + 1.52SGP + 6mm EC + 12A + 6mm (color-change film layer on the inner surface of the outdoor sheet, filled with inert gas) structure, the measured data are as follows:

d. Using the present invention to make 6mm + 1.52SGP + 6mm EC + 12A + 6mm (color-change film layer on the inner surface of the outdoor sheet, filled with inert gas) structure, the measured data are as follows:

Those skilled in the art should understand that various modifications and variations can be made to the present invention without departing from the spirit or scope of the invention. Accordingly, if any modification or variation falls within the protection scope of the appended claims and equivalents, the present invention is considered to cover these modifications and variations.

Claims (24)

    An improved electronically controlled all-solid-state intelligent dimming device includes a transparent substrate, and at least one side of the transparent substrate is sequentially provided from bottom to top: a dielectric composite reinforcement layer, a lower transparent electrode layer, and a lower electrochromic layer. , An ion conductive layer, an electrochromic layer, a transparent electrode layer, and a dielectric composite protective layer.     The improved electronically controlled all-solid-state intelligent dimming device according to claim 1, wherein the dielectric composite reinforced layer can be composed of SiO ₂ , TiO ₂ , Si ₃ N ₄ , Si ₂ N ₂ O, ZnSnO ₂ , Nb ₂ O _{5. One} or more of ZnO, ZrO ₂ , NbZr, BiO ₂ , Al ₂ O ₃ , and Cr ₂ N. The improved electronically controlled all-solid-state intelligent dimming device according to claim 2, wherein the dielectric composite protective layer can be composed of TiO ₂ , Cr ₂ N, ZnSnO ₂ , ZnO, ZrO ₂ , NbZr, Si ₃ N ₄ , SiO _{2. One} or more of Si ₂ N ₂ O, BiO ₂ , Al ₂ O ₃ , Nb ₂ O ₅ , Cr, Al, and Pd.     The improved electronically controlled all-solid-state intelligent dimming device according to claim 3, wherein the lower transparent electrode layer can be oxide-doped or metal-doped or undoped FTO, ATO, ITO, Ag, Au, It is composed of at least one of Cu, AZO, GZO, GXO, Al, Cr, and Pt.         The improved electronically controlled all-solid-state intelligent dimming device according to claim 4, wherein the upper transparent electrode layer can be doped with oxide, metal, or undoped Cr, Al, ITO, Ni, FTO, It is composed of at least one of Au, ATO, Ag, Cu, AZO, and Pt.     The improved electronically controlled all-solid-state intelligent dimming device according to claim 5, wherein the electrochromic layer can be composed of WO ₃ , Ta ₂ O ₅ , V ₂ O ₅ , MoO ₃ , Nb ₂ O ₅ , TiO _2. At least one of Ir ₂ O ₃ is constituted. The improved electrically controlled all-solid-state intelligent dimming device according to claim 5, wherein the lower electrochromic layer can be WO ₃ , Ta ₂ O ₅ , V ₂ O ₅ , MoO ₃ , Nb doped with oxides _{It is} composed of at least one of ₂ O ₅ , TiO ₂ , and SnO ₂ . The improved electronically controlled all-solid-state intelligent dimming device according to claim 1, wherein the ion-conducting layer can be composed of LiTaO ₃ , Li ₃ N, LiNbO ₃ , LiBO ₂ , LiF, LiA ₁ F ₄ , One of LiA ₁ C ₁ and LIPON or a combination thereof. The improved electronically controlled all-solid-state intelligent dimming device according to claim 1, wherein the electrochromic layer can be composed of at least one of NiOx, Ir ₂ O ₃ , Rh ₂ O ₃ , CoO ₂ , and InN . The improved electronically controlled all-solid-state intelligent dimming device according to claim 1, wherein the electrochromic layer can be one of NiOx, Ir ₂ O ₃ , Rh ₂ O ₃ , and CoO ₂ doped with oxides. Or several materials.     The improved electronically controlled all-solid-state intelligent dimming product according to claim 9 or 10, wherein x in NiOx is different from the stoichiometry of nickel oxide NiO, and the specific value range of NiOx is 0 <x <1.         The improved electronically controlled all-solid-state intelligent dimming device according to claim 11, wherein the specific value range of NiOx is preferably 0.2 <x <0.9.         The improved electronically controlled all-solid-state intelligent dimming device according to claim 12, wherein the specific value range of NiOx is more preferably 0.4 <x <0.8         The improved electronically controlled all-solid-state intelligent dimming device according to claim 1, wherein the thickness of the dielectric composite reinforcement layer is 60-100 nm, the thickness of the lower transparent electrode layer is 50-150 nm, and the thickness of the lower electrochromic layer is 200-400nm, the thickness of the ion conductive layer is 10-2000nm, the thickness of the upper electrochromic layer is 150-350nm, the thickness of the upper transparent electrode layer is 50-250nm, and the thickness of the dielectric composite protective layer is 50-150nm.         The improved electronically controlled all-solid-state intelligent dimming device as described in claim 14, wherein the resistances of the lower transparent electrode layer and the upper transparent electrode layer are less than 20Ω.         The improved electronically controlled all-solid-state intelligent dimming device according to claim 15, wherein the lower transparent electrode layer and the upper transparent electrode layer are both prepared by a vacuum high temperature annealing process.         The improved electronically controlled all-solid-state intelligent dimming device according to claim 16, wherein the transparent substrate is at least one of glass, PMMA, PC, and PET.         The improved electronically controlled all-solid-state intelligent dimming product according to claim 17, wherein the dielectric composite protective layer is different from a side of the transparent substrate, and can further be provided with a low-radiation functional film, a sun-protective functional film, a One of a hydrophobic functional film, a hydrophilic functional film, an antireflection functional film, an electromagnetic shielding functional film, an anti-dust photocatalytic functional film, or a combination thereof.         A glass window, wherein the glass window has the improved electronically controlled all-solid-state intelligent dimming device as described in claim 1-18.         The improved electronically controlled all-solid-state intelligent dimming device according to any one of claims 1 to 10 or 14 to 19, wherein the light-to-heat ratio of the improved electronically controlled all-solid-state intelligent dimming device is 4.0 to 7.8.         The improved electronically controlled all-solid-state intelligent dimming device according to claim 13, wherein the light-to-heat ratio of the improved electronically controlled all-solid-state intelligent dimming device is 4.0 to 7.8.         The improved electronically controlled all-solid-state intelligent dimming device according to any one of claims 1 to 10 or 14 to 19, wherein the dielectric composite strengthening layer, the lower transparent electrode layer, the lower electrochromic layer, the The ion conductive layer, the upper electrochromic layer, the upper transparent electrode layer, and the dielectric composite protective layer are all prepared by a vacuum magnetron sputtering process.         The improved electronically controlled all-solid-state intelligent dimming device according to claim 13, wherein the dielectric composite reinforcing layer, the lower transparent electrode layer, the lower electrochromic layer, the ion conductive layer, and the upper electrochromic layer The upper transparent electrode layer and the dielectric composite protective layer are all prepared by a vacuum magnetron sputtering process.         The improved electronically controlled all-solid-state intelligent dimming device according to claim 22, wherein the vacuum magnetron sputtering process uses a dual AC rotating cathode, a dual AC planar cathode, a dual DC planar cathode, a single DC planar cathode, and a single DC At least one of the rotating cathodes is deposited into a film in an argon-oxygen, argon-nitrogen, or argon-oxygen-nitrogen atmosphere. The controlled sputtering process uses at least one of a dual AC rotating cathode, a dual AC planar cathode, a dual DC planar cathode, a single DC planar cathode, and a single DC rotating cathode to be deposited and deposited in an argon-oxygen, argon-nitrogen, or argon-oxygen-nitrogen atmosphere.