CN112745038B - Preparation method of electrically-controlled color-changing glass - Google Patents
Preparation method of electrically-controlled color-changing glass Download PDFInfo
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- CN112745038B CN112745038B CN201911044196.3A CN201911044196A CN112745038B CN 112745038 B CN112745038 B CN 112745038B CN 201911044196 A CN201911044196 A CN 201911044196A CN 112745038 B CN112745038 B CN 112745038B
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- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C17/00—Surface treatment of glass, not in the form of fibres or filaments, by coating
- C03C17/34—Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions
- C03C17/36—Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions at least one coating being a metal
- C03C17/3602—Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions at least one coating being a metal the metal being present as a layer
- C03C17/3649—Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions at least one coating being a metal the metal being present as a layer made of metals other than silver
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- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C17/00—Surface treatment of glass, not in the form of fibres or filaments, by coating
- C03C17/34—Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions
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- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C17/00—Surface treatment of glass, not in the form of fibres or filaments, by coating
- C03C17/34—Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions
- C03C17/3411—Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions with at least two coatings of inorganic materials
- C03C17/3429—Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions with at least two coatings of inorganic materials at least one of the coatings being a non-oxide coating
- C03C17/3435—Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions with at least two coatings of inorganic materials at least one of the coatings being a non-oxide coating comprising a nitride, oxynitride, boronitride or carbonitride
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- G—PHYSICS
- G02—OPTICS
- G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
- G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
- G02F1/01—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour
- G02F1/15—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour based on an electrochromic effect
- G02F1/1514—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour based on an electrochromic effect characterised by the electrochromic material, e.g. by the electrodeposited material
- G02F1/1523—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour based on an electrochromic effect characterised by the electrochromic material, e.g. by the electrodeposited material comprising inorganic material
- G02F1/1524—Transition metal compounds
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- G—PHYSICS
- G02—OPTICS
- G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
- G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
- G02F1/01—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour
- G02F1/15—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour based on an electrochromic effect
- G02F1/153—Constructional details
- G02F1/1533—Constructional details structural features not otherwise provided for
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- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C2218/00—Methods for coating glass
- C03C2218/10—Deposition methods
- C03C2218/15—Deposition methods from the vapour phase
- C03C2218/154—Deposition methods from the vapour phase by sputtering
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- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C2218/00—Methods for coating glass
- C03C2218/10—Deposition methods
- C03C2218/15—Deposition methods from the vapour phase
- C03C2218/154—Deposition methods from the vapour phase by sputtering
- C03C2218/156—Deposition methods from the vapour phase by sputtering by magnetron sputtering
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- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C2218/00—Methods for coating glass
- C03C2218/30—Aspects of methods for coating glass not covered above
- C03C2218/32—After-treatment
Abstract
The embodiment of the invention discloses a preparation method of electrically-controlled color-changing glass, which comprises the following steps: providing a glass substrate; forming a first conductive layer on the glass substrate; forming a first composite color changing layer on the first conductive layer; forming an ion conductor layer on the first composite color-changing layer; forming a second composite color changing layer on the ion conductor layer; forming a second conductive layer on the second composite color-changing layer; and forming a dielectric protection layer on the second conductive layer. The electrically-controlled color-changing glass prepared by the preparation method can improve the color-changing uniformity of the electrically-controlled color-changing glass in large-area product devices.
Description
Technical Field
The invention relates to the technical field of glass preparation, in particular to a preparation method of electrically-controlled color-changing glass.
Background
In the current industrialization process of the electric control color-changing glass, the electric control color-changing glass has a plurality of defects on the color-changing uniformity and the color-changing cycle life of large-area product devices, and the color-changing material is mainly WO 3 A material. WO 3 The material is a well-known high-efficiency cathode color-changing material, and WO is controlled through chemical oxidation and reduction reactions 3 The valence state change of the medium W can realize the absorption regulation and control effect on the spectrum. However, due to the large-area non-uniform color change, short cycle life and the like, the color change function near the electrode is seriously attenuated or even does not change color after the electrode is cycled for a certain number of times, so that the application of the electrode in engineering is greatly influenced.
Disclosure of Invention
In order to solve the above problems, embodiments of the present invention provide a method for preparing electrically controlled color-changing glass, so as to improve the color-changing uniformity of the electrically controlled color-changing glass in large-area product devices.
Specifically, the preparation method of the electrically-controlled color-changing glass provided by the embodiment of the invention comprises the following steps: providing a glass substrate, and heating the glass substrate to 280-300 ℃; one or the combination of at least two of FTO, ITO, IGZO, AZO, GZO and Ag is used as a target material, and the vacuum sputtering pressure is 1.0E -3 ～9.0E -3 Depositing a first conductive layer on the glass substrate under the mbar condition; the oxide of at least two of W, mo, nb, ti and Ta is used as the first target material, the oxide of at least two of Ni, V, co, ir, fe and Mn is used as the second target material, and the vacuum sputtering pressure is 1.0E -3 ～9.0E -3 Depositing a first composite color changing layer on the first conductive layer under the mbar condition; one or the combination of at least two of H, li, na, K and Mg is used as a target material, and the vacuum sputtering pressure is 1.0E -3 ～9.0E -3 Depositing an ion conductor layer on the first composite color changing layer under the mbar condition; taking oxides of at least two combinations of W, mo, nb, ti and Ta as a third target material, taking oxides of at least two combinations of Ni, V, co, ir, fe and Mn as a fourth target material, and sputtering under vacuum at a pressure of 1.0E -3 ～9.0E - 3 Depositing a second composite color changing layer on the ion conductor layer under the mbar condition; one or the combination of at least two of FTO, ITO, IGZO, AZO, GZO and Ag is used as a target material, and the vacuum sputtering pressure is 1.0E -3 ～9.0E -3 Depositing a second conductive layer on the second composite color-changing layer under the mbar condition; and using oxide or nitride or oxynitride of one of Si, ti, zn, sn, nb and Ta as target material, and sputtering in vacuum at 1.0E -3 ～9.0E -3 And depositing an outer protective layer on the second conductive layer under the mbar condition.
In an embodiment of the invention, the first target material is the same as the third target material and/or the second target material is the same as the fourth target material.
On the other hand, the preparation method of the electrically-controlled color-changing glass provided by the embodiment of the invention comprises the following steps: providing a glass substrate; forming a first conductive layer on the glass substrate; forming a first composite color changing layer on the first conductive layer; forming an ion conductor layer on the first composite color-changing layer; forming a second composite color changing layer on the ion conductor layer; forming a second conductive layer on the second composite color-changing layer; and forming a dielectric protection layer on the second conductive layer.
In one embodiment of the present invention, the forming of the first conductive layer on the glass substrate is: and depositing the first conductive layer on the glass substrate under a first preset vacuum sputtering air pressure condition by taking one or a combination of at least two of FTO, ITO, IGZO, AZO, GZO and Ag as a target material.
In one embodiment of the present invention, the first preset vacuum sputtering pressure is in the range of 1.0E -3 ～9.0E - 3 mbar。
In an embodiment of the present invention, the forming of the first composite color-changing layer on the first conductive layer is specifically: and depositing the first composite discoloring layer on the first conducting layer under a second preset vacuum sputtering air pressure condition by taking at least two combined oxides of W, mo, nb, ti and Ta as a first target material and at least two combined oxides of Ni, V, co, ir, fe and Mn as a second target material.
In an embodiment of the present invention, the forming of the ion conductor layer on the first composite color-changing layer is specifically: and depositing the ion conductor layer on the first composite color changing layer under a third preset vacuum sputtering air pressure condition by taking one or a combination of at least two of H, li, na, K and Mg as a target material.
In an embodiment of the present invention, the forming of the second composite color-changing layer on the ion conductor layer specifically includes: and depositing the second composite discoloring layer on the ion conductor layer under the fourth preset vacuum sputtering air pressure condition by taking the oxide of at least two combinations of W, mo, nb, ti and Ta as a third target material and the oxide of at least two combinations of Ni, V, co, ir, fe and Mn as a fourth target material.
In an embodiment of the present invention, the forming of the second conductive layer on the second composite color-changing layer is specifically: and depositing the second conducting layer on the second composite discoloring layer under the fifth preset vacuum sputtering air pressure condition by taking one or the combination of at least two of FTO, ITO, IGZO, AZO, GZO and Ag as a target material.
In an embodiment of the present invention, the forming of the dielectric protection layer on the second conductive layer specifically includes: and depositing the outer protective layer on the second conductive layer under a sixth preset vacuum sputtering air pressure condition by taking an oxide or a nitride or an oxynitride of one of Si, ti, zn, sn, nb and Ta as a target material.
The technical scheme has the following advantages: the preparation method of the electrochromic glass provided by the embodiment of the invention adopts a specific preparation process, so that the prepared electrochromic glass can actively adjust energy-saving parameters according to environmental changes, improve the color-changing uniformity of the electrically-controlled electrochromic glass in large-area product devices, and can be used for replacing building glass, automobile glass, aviation glass, decorative glass and the like.
Drawings
In order to more clearly illustrate the technical solutions of the embodiments of the present invention, the drawings needed to be used in the description of the embodiments are briefly introduced below, and it is obvious that the drawings in the following description are only some embodiments of the present invention, and it is obvious for those skilled in the art to obtain other drawings based on these drawings without creative efforts.
Fig. 1 is a schematic structural diagram of an electrochromic glass according to an embodiment of the present invention.
Fig. 2 is a schematic flow chart of a method for preparing electrochromic glass according to an embodiment of the present invention.
FIG. 3a is a graph showing the visible light transmittance spectra of the test sample 5 of the present invention at different color-changing positions.
Fig. 3b is a schematic diagram of the performance variation of the test sample 5 in different color-changing gears according to the present invention.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the drawings in the embodiments of the present invention, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the scope of the present invention.
As shown in fig. 1, an embodiment of the present invention provides an all-inorganic vacuum-coated electrically-controlled color-changing glass 900. The electrically controlled color-changing glass 900 comprises a glass substrate 10, and a first conductive layer 11, a first composite color-changing layer 12, an ion conductor layer 13, a second composite color-changing layer 14, a second conductive layer 20 and a medium protection layer 30 which are sequentially arranged on the glass substrate 10. The electric control color-changing glass provided by the embodiment of the invention adopts a specific film structure with double composite color-changing layers, can actively adjust energy-saving parameters according to environmental changes, and improves the color-changing uniformity of the electric control color-changing glass in large-area product devices.
The glass substrate 10 may be float glass, ultra-white glass, PET (Polyethylene terephthalate) film, or the like. The thickness of the glass substrate 10 may be, for example, 0.02 to 25mm.
The material of the first conductive layer 11 is selected from one or a combination of at least two of FTO (fluorinated silicone oxide), ITO (indium tin oxide), IGZO (indium gallium zinc oxide), AZO (aluminum zinc oxide), GZO (gallium zinc oxide), and Ag. The combination of at least two herein may be, for example, a combination of two such as AZO and GZO, or a combination of three such as FTO, ITO, GZO, even more, and the like. The thickness of the first conductive layer 11 is 1-1100nm. Preferably, the thickness of the first conductive layer is greater than 10nm and equal to or less than 300nm. Preferably, the thickness of the first conductive layer is greater than 10nm and equal to or less than 300nm.
The first composite color-changing layer 12 is made of an inorganic color-changing material. Specifically, the material of the first composite discoloration layer 12 includes, for example, a first discoloration material and a second discoloration material, wherein the first discoloration material is selected from oxides of at least two combinations of W, mo, nb, ti, and Ta, for example, oxides of any two combinations of W, mo, nb, ti, and Ta, such as WMoOx, wnbo ox, or oxides of WMoTiOx, wnbo taox, or even combinations of more thereof; the second color changing material is selected from oxides of at least two combinations of Ni, V, co, ir, fe, mn, in particular may be oxides of combinations of two of Ni, V, co, ir, fe, mn such as NiVOx, niCoOx, niIrOx, niFeOx, or oxides of combinations of three, or even oxides of combinations of more. The stoichiometric ratio of the oxide may be sufficient oxygen or less than the stoichiometric ratio of oxygen. The thickness of the first composite discoloration layer 12 is greater than 30nm and less than or equal to 500nm.
The ion conductor layer 13 is made of one or a combination of at least two of H, li, na, K, and Mg. H. The combination of elements in Li, na, K, mg includes, for example, a combination of two elements such as Li and Na, a combination of three elements such as Na, K, mg, and even more. The thickness of the ion conductor layer 13 is greater than 10nm and equal to or less than 100nm.
The material of the second composite discoloration layer 14 includes, for example, a third discoloration material and a fourth discoloration material, wherein the third discoloration material is selected from oxides of at least two combinations of W, mo, nb, ti, and Ta, for example, oxides of any two combinations of W, mo, nb, ti, and Ta, such as WMoOx, wnbo x, or oxides of WMoTiOx, WNbTaOx, or combinations of three thereof, or even combinations of more thereof; the fourth color change material is selected from oxides of at least two combinations of Ni, V, co, ir, fe, mn, and specifically may be oxides of two combinations of Ni, V, co, ir, fe, mn such as NiVOx, niCoOx, niIrOx, niFeOx, or oxides of three combinations, and even oxides of more combinations. The stoichiometric ratio of the oxides may be sufficient oxygen or insufficient oxygen. The thickness of the second composite color changing layer is more than 20nm and less than or equal to 500nm.
Further, the third color-changing material is the same as the first color-changing material, and/or the fourth color-changing material is the same as the second color-changing material.
The material of the second conductive layer 20 is an inorganic color-changing material. The inorganic color-changing material is selected from one or any combination of at least two of FTO (fluorine silicon oxide), ITO (indium tin oxide), IGZO (indium gallium zinc oxide), AZO (aluminum zinc oxide), GZO (gallium zinc oxide) and Ag. The thickness of the second transparent conductive layer 20 is 10-1000nm. Preferably, the thickness of the second conductive layer is greater than 10nm and equal to or less than 300nm.
The material of the dielectric protection layer 30 is selected from an oxide, nitride or oxynitride of one of Si, ti, zn, sn, nb, and Ta. The thickness of the outer protective layer is 0.2-100nm. Preferably, the material of the dielectric protection layer 30 is Si 3 N 4 。Si 3 N 4 The high-temperature ceramic material has the advantages of high hardness, high melting point, stable chemical property, strong corrosion resistance, mechanical scratch resistance and high-temperature oxidation resistance, and can well play a role in protection when being used as an outer protection layer.
In addition, the embodiment of the invention also provides a preparation method of the electrically controlled color-changing glass, for example, the method is used for preparing the electrically controlled color-changing glass 900. The preparation method of the electrically controlled color-changing glass comprises the following steps:
s11: a glass substrate is provided. And cleaning and drying the glass substrate.
S12: plating a first conductive layer on the glass substrate. Specifically, the glass substrate is heated to a preset temperature, for example, 280 to 300 ℃, and one or a combination of at least two of FTO, ITO, IGZO, AZO, GZO, and Ag is used as a target material to deposit the first conductive layer under a first preset vacuum sputtering pressure. A first predetermined vacuum sputtering pressure of, for example, 1.0E -3 ～9.0E -3 mbar. Preferably, the first conductive layer may also be a pre-prepared conductive film layer. This allows better index matching between the layers.
S13: plating a first composite color changing layer on the first conductive layer. The oxide of at least two of W, mo, nb, ti and Ta is used as a first target material, and the oxide of at least two of Ni, V, co, ir, fe and Mn is used as a second target material. The stoichiometric ratio of the oxides may be sufficient oxygen or insufficient oxygen. And depositing the first target material and the second target material under a second preset vacuum sputtering pressure to obtain the first composite color-changing layer. A second predetermined vacuum sputtering pressure of, for example, 1.0E -3 ～9.0E -3 mbar. The first composite color changing layer can also be plated by a plurality of target positions at the same time, so that better binding force between the film layers can be obtained. The process gases employed by the plurality of target sites may or may not be uniform.
S14: and plating an ion conductor layer on the first composite color-changing layer. One or the combination of at least two of H, li, na, K and Mg elements is used as a target material, and the target material is placed under the condition of third preset vacuum sputtering air pressureAnd depositing to obtain the ion conductor layer. Third predetermined vacuum sputtering pressure, e.g., 1.0E -3 ～9.0E -3 mbar. Also, preferably, the ion conductor layer can be plated with multiple target sites simultaneously to achieve better bonding force between the films. The process gas ratios employed for the plurality of target sites may be non-uniform.
S15: plating a second composite color-changing layer on the ion conductor layer. Specifically, an oxide of at least two combinations of W, mo, nb, ti and Ta is used as a third target material, and an oxide of at least two combinations of Ni, V, co, ir, fe and Mn is used as a fourth target material. The stoichiometric ratio of the oxide may be sufficient oxygen or less than the stoichiometric ratio of oxygen. And depositing the third target material and the fourth target material under a fourth preset vacuum sputtering pressure to obtain a second composite color-changing layer. Fourth predetermined vacuum sputtering pressure of, for example, 1.0E -3 ～9.0E -3 mbar. Thus, better bonding force between the film layers can be obtained. The process gases employed by the plurality of target sites may or may not be uniform. Furthermore, the first target material is the same as the third target material, and/or the second target material is the same as the fourth target material, so that the types of materials can be reduced and the cost can be saved under the condition of ensuring the performance of the glass.
S16: and plating a second conductive layer on the second composite color changing layer. And taking one or a combination of at least two of FTO, ITO, IGZO, AZO, GZO and Ag as a target material, and depositing the target material under a fifth preset vacuum sputtering pressure to obtain a second conducting layer. Fifth predetermined vacuum sputtering pressure of, for example, 1.0E -3 ～9.0E -3 mbar. Preferably, the second conductive layer may also be a pre-prepared conductive film layer. This allows better index matching between the layers.
S17: and plating a dielectric protection layer on the second conductive layer. And taking an oxide or nitride or oxynitride of one of Si, ti, zn, sn, nb and Ta as a target material, and depositing the target material under a sixth preset vacuum sputtering pressure to obtain the dielectric protective layer. Sixth predetermined vacuum sputtering pressure of, for example, 1.0E -3 ～9.0E -3 mbar. Preferably, media protectionThe layers can also be plated with multiple target sites simultaneously to achieve better bonding force between the layers. The process gas ratios employed for the plurality of target sites may be non-uniform.
In addition, the preparation method of the electrically controlled color-changing glass also comprises a heat treatment step, specifically, a vacuum heat treatment and annealing process is carried out, the heat treatment temperature is 300-600 ℃, and the heat treatment time is 5-120min.
Furthermore, the preparation method of the electrically-controlled color-changing glass also comprises pre-vacuum transition and parallel connection of electrodes. This step can be accomplished by methods known in the art and will not be described further herein.
The electronic control color-changing glass with more neutral color matching can be applied to the fields of building glass outer walls, interior decoration, automobile skylight glass, automobile side window glass, automobile rear windshield glass, automobile front windshield glass, automobile rearview mirrors, high-speed rail windows, airplane suspension windows, sunlight rooms, sunglasses, ski goggles and the like which need to adjust the light. The electric control color-changing glass provided by the embodiment of the invention adopts a specific film structure with double composite color-changing layers, can actively adjust energy-saving parameters according to environmental changes, and improves the color-changing uniformity of the electric control color-changing glass in large-area product devices. Moreover, because each layer can be formed by adopting a magnetron reactive sputtering deposition method during the production of the electric control color-changing glass, the multiple entering and exiting of coating equipment in the production process can be avoided, the production process is simplified, the production cost can be reduced, and the production efficiency can be improved.
The following describes the preparation process of the electrically controlled photochromic glass in detail by a specific example.
DETAILED DESCRIPTION OF EMBODIMENT (S) OF INVENTION
The electric control color-changing glass has a film layer structure which comprises the following components in sequence from a glass substrate to the outside: glass substrate/ITO (150 nm)/WNbOx + NiVOx (200 nm)/Li (40 nm)/WMoOx + NiCoOx (80 nm)/ITO (120 nm)/Si 3 N 4 (20nm)。
The process for preparing the electrically-controlled color-changing glass sequentially comprises the following steps:
(1) Cleaning and drying the glass substrate, scribing a line by laser, cleaning and drying again, and placing in a vacuum sputtering area;
(2) Depositing an ITO layer on a glass substrate in a magnetron sputtering mode, wherein the target material is an ITO rotating target, the power supply is direct current or a medium-frequency power supply with the frequency of 2000-40000Hz, the power is 1-30 KW, the process gas is argon, and the ITO layer is deposited at the temperature of 290 ℃;
(3) Depositing a WNbOx + NiVOx layer on the ITO layer in a magnetron sputtering mode, wherein a first target material is a metal WMo planar target, a second target material is a metal NiV planar target, a power supply is a direct-current power supply, the power is 1-30 KW, process gas is mixed gas of pure argon and oxygen, and the temperature is raised to 550 ℃ after deposition to enter a next coating area;
(4) Depositing a Li layer on the WNbOx + NiVOx layer by adopting a magnetron sputtering mode, wherein the used target material is a Li rotating target, the power supply is a medium-frequency or direct-current power supply, the power is 1-30 KW, the process gas is argon, and the deposition is carried out at the temperature of 550 ℃;
(5) Depositing a WMoOx + NiCoOx layer on the Li layer by adopting a magnetron sputtering mode, wherein a first target material is a metal WMo planar target, a second target material is a metal NiCo planar target, a power supply is a direct-current power supply, the power is 1-30 KW, a process gas is a mixed gas of pure argon and oxygen, and the temperature is raised to 550 ℃ after deposition at a corresponding temperature so as to enter a next coating area;
(6) Depositing an ITO layer on the WMoOx + NiCoOx layer in a magnetron sputtering mode, wherein the target material is an ITO rotating target, the power supply is a direct current or intermediate frequency power supply, the power is 1-30 KW, the process gas is argon, and the ITO layer is deposited at the temperature of 290 ℃;
(7) Depositing Si on the ITO layer by adopting a magnetron sputtering mode 3 N 4 The layer is deposited at room temperature by using SiAl rotary target as target material, medium frequency power supply as power supply, 1-10 KW power supply and mixed gas of argon and nitrogen as process gas.
(8) Annealing process, laser scribing process, electrode layout and wiring, testing and laminating process.
In addition, the performance of 6 electrochromic glasses is tested in the embodiment of the invention. The parameters of 12 test specimens of 6 electrochromic glazing units are shown in Table 1. Wherein, the 1 st is 2 test samples of the electrochromic glass in the prior art, and the other 5 test samples are 10 test samples of the electrochromic glass provided by the invention, and the materials of the first color-changing layer and the first auxiliary color-changing layer are different. The comparative data of the performance of the test samples under the same test conditions in different states are shown in table 2. Further, in this embodiment, the test sample 5 is tested at different color-changing positions, and the obtained performance parameters are shown in table 3 and fig. 3a and 3b.
TABLE 1 parameter Table of 6 test samples
Table 2 table 6 table of performance parameters of the test samples in different states
TABLE 3 Performance parameter Table for test sample 5 at different color-changing gears
| Transparent to colored | T | a*t | b*t | a*g | b*g | a*f | b*f |
| Test sample 5 |
59.75 | -7.86 | -5.50 | 12.85 | 10.15 | 8.51 | 22.10 |
| Test sample 5 |
42.84 | -5.39 | -10.98 | 10.49 | 8.49 | 3.64 | 25.98 |
| Test sample 5 transparent 3 grade | 31.11 | -3.67 | -14.12 | 9.53 | 8.73 | 1.05 | 26.95 |
| Test sample 5 transparent 4 grade | 22.72 | -2.51 | -15.61 | 7.66 | 6.35 | -0.27 | 26.96 |
| Test sample 5 transparent 5 grade | 16.60 | -1.75 | -15.95 | 5.69 | 5.32 | -0.90 | 26.85 |
| Test sample 5 transparent 6 grade | 12.11 | -1.28 | -15.50 | 4.17 | 3.39 | -1.16 | 26.90 |
| Test sample 5 transparent 7 grade | 8.80 | -0.98 | -14.56 | 3.17 | 1.77 | -1.23 | 27.16 |
| Test sample 5 transparent 8 grade | 6.37 | -0.79 | -13.35 | 2.63 | -0.29 | -1.20 | 27.56 |
| Test sample 5 transparent 9 grades | 4.59 | -0.64 | -12.03 | 1.47 | -1.68 | -1.12 | 28.05 |
| Test sample 5 transparent 10 grade | 3.30 | -0.51 | -10.73 | 0.62 | -3.69 | -1.01 | 28.53 |
As can be seen from table 2 and fig. 3a and 3b, the color appearance of the electrically controlled color-changing glass of the embodiment of the present invention is better than the color of the electrically controlled color-changing glass in the prior art, the visible light transmittance T of the electrically controlled color-changing glass in the prior art is in the range of 51.43% to 5.6%, and the visible light transmittance of the embodiment of the present invention is in the range of 59% to 2.0%. In addition, the visible light transmission color a x t, b x t of the electrically controlled color changing glass provided by the embodiment of the invention surrounds the vicinity of neutral color, and is nearly colorless, while the product of the electrically controlled color changing glass in the prior art is yellow before transmitting color change, transmits b x t and reaches 7.83, and displays blue b x t and reaches-30.54 after color change. The outdoor colors a x g and b x g of the electrically controlled color-changing glass are neutral, the color of the indoor surface is mainly seen as a transmission color due to the problem of the observation angle of an observer, and the color of the film surface is relatively secondary. Obviously, the electrically-controlled color-changing glass provided by the invention has more stable color and better large-area color uniformity in the preparation process and the subsequent color-changing use process.
In addition, it should be understood that the foregoing embodiments are merely exemplary illustrations of the present invention, and the technical solutions of the embodiments can be arbitrarily combined and collocated without conflict between technical features and structural contradictions, which do not violate the purpose of the present invention.
Finally, it should be noted that: the above examples are only intended to illustrate the technical solution of the present invention, but not to limit it; although the present invention has been described in detail with reference to the foregoing embodiments, it should be understood by those of ordinary skill in the art that: the technical solutions described in the foregoing embodiments may still be modified, or some technical features may be equivalently replaced; and such modifications or substitutions do not depart from the spirit and scope of the corresponding technical solutions of the embodiments of the present invention.
Claims (2)
1. The preparation method of the electrically-controlled color-changing glass is characterized by comprising the following steps:
providing a glass substrate, and heating the glass substrate to 280-300 ℃;
one or the combination of at least two of FTO, ITO, IGZO, AZO, GZO and Ag is used as a target material, and the vacuum sputtering pressure is 1.0E -3 ～9.0E -3 Depositing a first conductive layer on the glass substrate under the mbar condition;
taking oxides of at least two combinations of W, mo, nb, ti and Ta as a first target material, taking oxides of at least two combinations of Ni, V, co, ir, fe and Mn as a second target material, and sputtering under vacuum at the air pressure of 1.0E -3 ～9.0E -3 Depositing a first composite color changing layer on the first conductive layer under the mbar condition;
one or the combination of at least two of H, li, na, K and Mg is used as a target material, and the vacuum sputtering pressure is 1.0E -3 ～9.0E -3 Depositing an ion conductor layer on the first composite color changing layer under the mbar condition, wherein the thickness of the ion conductor layer is more than 10nm and less than or equal to 100nm;
w, mo,Oxide of at least two combinations of Nb, ti and Ta is taken as a third target material, oxide of at least two combinations of Ni, V, co, ir, fe and Mn is taken as a fourth target material, and the vacuum sputtering pressure is 1.0E -3 ～9.0E -3 Depositing a second composite color changing layer on the ion conductor layer under the mbar condition;
one or the combination of at least two of FTO, ITO, IGZO, AZO, GZO and Ag is used as a target material, and the vacuum sputtering pressure is 1.0E -3 ～9.0E -3 Depositing a second conductive layer on the second composite color-changing layer under the mbar condition; and
using oxide or nitride or oxynitride of one of Si, ti, zn, sn, nb and Ta as target material, and sputtering under vacuum at 1.0E -3 ～9.0E -3 And depositing an outer protective layer on the second conductive layer under the mbar condition.
2. The method for preparing electrically controlled color-changing glass according to claim 1, wherein the first target material is the same as the third target material, and/or the second target material is the same as the fourth target material.
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| CN104364707A (en) * | 2012-05-02 | 2015-02-18 | 唯景公司 | Electrochromic devices |
| CN104898344A (en) * | 2015-05-08 | 2015-09-09 | 上方能源技术(杭州)有限公司 | All-solid state electrochromic device preparation method and prepared electrochromic glass |
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| US7372610B2 (en) * | 2005-02-23 | 2008-05-13 | Sage Electrochromics, Inc. | Electrochromic devices and methods |
| US9261751B2 (en) * | 2010-04-30 | 2016-02-16 | View, Inc. | Electrochromic devices |
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| CN103771724A (en) * | 2012-10-19 | 2014-05-07 | 中国南玻集团股份有限公司 | All-solid-state film electrochromic glass and preparation method thereof |
| CN104898344A (en) * | 2015-05-08 | 2015-09-09 | 上方能源技术(杭州)有限公司 | All-solid state electrochromic device preparation method and prepared electrochromic glass |
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