CN113138506A - Color-changing glass and preparation method thereof - Google Patents
Color-changing glass and preparation method thereof Download PDFInfo
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- CN113138506A CN113138506A CN202010059413.2A CN202010059413A CN113138506A CN 113138506 A CN113138506 A CN 113138506A CN 202010059413 A CN202010059413 A CN 202010059413A CN 113138506 A CN113138506 A CN 113138506A
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- 239000011521 glass Substances 0.000 title claims abstract description 50
- 238000002360 preparation method Methods 0.000 title abstract description 13
- 239000010410 layer Substances 0.000 claims abstract description 323
- 239000010416 ion conductor Substances 0.000 claims abstract description 54
- 239000000758 substrate Substances 0.000 claims abstract description 19
- 239000011241 protective layer Substances 0.000 claims abstract description 11
- 239000000463 material Substances 0.000 claims description 65
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 28
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 26
- 239000010955 niobium Substances 0.000 claims description 25
- 239000010936 titanium Substances 0.000 claims description 25
- 229910052758 niobium Inorganic materials 0.000 claims description 24
- 229910052715 tantalum Inorganic materials 0.000 claims description 24
- 229910052719 titanium Inorganic materials 0.000 claims description 24
- 239000011572 manganese Substances 0.000 claims description 23
- 229910052741 iridium Inorganic materials 0.000 claims description 22
- 229910052748 manganese Inorganic materials 0.000 claims description 22
- 229910052750 molybdenum Inorganic materials 0.000 claims description 22
- 229910052759 nickel Inorganic materials 0.000 claims description 22
- 229910052721 tungsten Inorganic materials 0.000 claims description 22
- 229910052742 iron Inorganic materials 0.000 claims description 21
- 229910052720 vanadium Inorganic materials 0.000 claims description 21
- 238000000034 method Methods 0.000 claims description 11
- 238000002845 discoloration Methods 0.000 claims description 8
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 claims description 5
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 claims description 5
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 5
- 229910017052 cobalt Inorganic materials 0.000 claims description 5
- 239000010941 cobalt Substances 0.000 claims description 5
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims description 5
- GKOZUEZYRPOHIO-UHFFFAOYSA-N iridium atom Chemical compound [Ir] GKOZUEZYRPOHIO-UHFFFAOYSA-N 0.000 claims description 5
- 239000011733 molybdenum Substances 0.000 claims description 5
- GUCVJGMIXFAOAE-UHFFFAOYSA-N niobium atom Chemical compound [Nb] GUCVJGMIXFAOAE-UHFFFAOYSA-N 0.000 claims description 5
- GUVRBAGPIYLISA-UHFFFAOYSA-N tantalum atom Chemical compound [Ta] GUVRBAGPIYLISA-UHFFFAOYSA-N 0.000 claims description 5
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 claims description 5
- 239000010937 tungsten Substances 0.000 claims description 5
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 claims description 5
- 230000033228 biological regulation Effects 0.000 abstract description 10
- 239000003086 colorant Substances 0.000 abstract description 5
- 239000013077 target material Substances 0.000 description 33
- 238000004544 sputter deposition Methods 0.000 description 15
- 238000000151 deposition Methods 0.000 description 10
- JAONJTDQXUSBGG-UHFFFAOYSA-N dialuminum;dizinc;oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[O-2].[O-2].[Al+3].[Al+3].[Zn+2].[Zn+2] JAONJTDQXUSBGG-UHFFFAOYSA-N 0.000 description 7
- 239000007789 gas Substances 0.000 description 7
- 230000008569 process Effects 0.000 description 7
- 239000011734 sodium Substances 0.000 description 7
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 6
- 239000011777 magnesium Substances 0.000 description 6
- 238000004519 manufacturing process Methods 0.000 description 6
- 239000001301 oxygen Substances 0.000 description 6
- 229910052760 oxygen Inorganic materials 0.000 description 6
- 229910052708 sodium Inorganic materials 0.000 description 6
- 229910052744 lithium Inorganic materials 0.000 description 5
- 229910052749 magnesium Inorganic materials 0.000 description 5
- 229910052700 potassium Inorganic materials 0.000 description 5
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 4
- 238000004040 coloring Methods 0.000 description 4
- 229910052739 hydrogen Inorganic materials 0.000 description 4
- 238000010438 heat treatment Methods 0.000 description 3
- 230000001105 regulatory effect Effects 0.000 description 3
- GYHNNYVSQQEPJS-UHFFFAOYSA-N Gallium Chemical compound [Ga] GYHNNYVSQQEPJS-UHFFFAOYSA-N 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 229910052733 gallium Inorganic materials 0.000 description 2
- 239000002346 layers by function Substances 0.000 description 2
- 150000004767 nitrides Chemical class 0.000 description 2
- 229910052710 silicon Inorganic materials 0.000 description 2
- 238000001228 spectrum Methods 0.000 description 2
- 229910052718 tin Inorganic materials 0.000 description 2
- 239000011135 tin Substances 0.000 description 2
- 230000007704 transition Effects 0.000 description 2
- 229910052725 zinc Inorganic materials 0.000 description 2
- 239000011701 zinc Substances 0.000 description 2
- 239000011787 zinc oxide Substances 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- 229910052581 Si3N4 Inorganic materials 0.000 description 1
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 1
- GDMRBHLKSYSMLJ-UHFFFAOYSA-N [F].O=[Si] Chemical compound [F].O=[Si] GDMRBHLKSYSMLJ-UHFFFAOYSA-N 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 238000000137 annealing Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 230000005684 electric field Effects 0.000 description 1
- 238000004134 energy conservation Methods 0.000 description 1
- 230000005284 excitation Effects 0.000 description 1
- 239000005329 float glass Substances 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052738 indium Inorganic materials 0.000 description 1
- APFVFJFRJDLVQX-UHFFFAOYSA-N indium atom Chemical compound [In] APFVFJFRJDLVQX-UHFFFAOYSA-N 0.000 description 1
- AMGQUBHHOARCQH-UHFFFAOYSA-N indium;oxotin Chemical compound [In].[Sn]=O AMGQUBHHOARCQH-UHFFFAOYSA-N 0.000 description 1
- 230000014759 maintenance of location Effects 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- 238000005546 reactive sputtering Methods 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 239000004332 silver Substances 0.000 description 1
- 239000005315 stained glass Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
Images
Classifications
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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
-
- 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
-
- 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
- G02F2001/1536—Constructional details structural features not otherwise provided for additional, e.g. protective, layer inside the cell
Abstract
The embodiment of the invention discloses color-changing glass and a preparation method thereof. The color-changing glass comprises a substrate, and a first transparent conductive layer, a first auxiliary color-changing layer, a first ion conductor layer, a first main color-changing layer, a second transparent conductive layer, a second main color-changing layer, a second auxiliary color-changing layer, a second ion conductor layer, a third transparent conductive layer, a first mixed color-changing layer, a third ion conductor layer, a second mixed color-changing layer, a fourth transparent conductive layer and an outer protective layer which are sequentially formed on one side of the substrate. The color-changing glass provided by the embodiment of the invention enlarges the color regulation range of the glass, and realizes regulation and control of more colors.
Description
Technical Field
The invention relates to the technical field of glass, in particular to color-changing glass and a preparation method thereof.
Background
Due to the characteristics of low carbon, energy conservation, adjustable color and the like, the color-changing glass is gradually applied to various industries such as buildings and the like. The optical performance of the material of the color-changing glass can be continuously and reversibly changed under the action of an external electric field, so that the color and the transparency of the glass can be reversibly changed, and the regulation and the change of a plurality of colors can be realized. However, the color regulation and control range of the current color-changing glass is single, the uniformity of the color is poor, and the requirement of industry development is difficult to meet.
Disclosure of Invention
In view of at least part of the problems, the embodiment of the invention provides a color-changing glass and a preparation method thereof.
On one hand, the color-changing glass provided by the embodiment of the invention comprises a substrate, and a first transparent conductive layer, a first auxiliary color-changing layer, a first ion conductor layer, a first main color-changing layer, a second transparent conductive layer, a second main color-changing layer, a second auxiliary color-changing layer, a second ion conductor layer, a third transparent conductive layer, a first mixed color-changing layer, a third ion conductor layer, a second mixed color-changing layer, a fourth transparent conductive layer and an outer protection layer which are sequentially formed on one side of the substrate; wherein the materials of the first main color layer and the second main color layer are respectively selected from oxides of at least two combinations of tungsten, molybdenum, niobium, titanium and tantalum; the first auxiliary color-changing layer and the second auxiliary color-changing layer are made of oxides of at least two elements selected from nickel, vanadium, cobalt, iridium, iron and manganese; the first mixed color matching layer comprises a first color matching material and a second color matching material, the first color matching material is selected from oxides of at least two combinations of W, Mo, Nb, Ti and Ta, and the second color matching material is selected from oxides of at least two combinations of Ni, V, Co, Ir, Fe and Mn; the second mixed color matching layer comprises a third color matching material and a fourth color matching material, the third color matching material is selected from oxides of at least two combinations of W, Mo, Nb, Ti and Ta, and the fourth color matching material is selected from oxides of at least two combinations of Ni, V, Co, Ir, Fe and Mn.
In another aspect, the color-changing glass provided by the embodiment of the invention includes a substrate, and a first transparent conductive layer, a first auxiliary color-changing layer, a first ion conductor layer, a first main color-changing layer, a second transparent conductive layer, a second main color-changing layer, a second auxiliary color-changing layer, a second ion conductor layer, a third transparent conductive layer, a first mixed color-changing layer, a third ion conductor layer, a second mixed color-changing layer, a fourth transparent conductive layer, and an outer protection layer, which are sequentially formed on one side of the substrate.
In one embodiment of the present invention, the materials of the first primary color layer and the second primary color layer are respectively selected from oxides of at least two combinations of tungsten, molybdenum, niobium, titanium and tantalum.
In one embodiment of the present invention, the materials of the first primary chromic layer and the second primary chromic layer are the same.
In one embodiment of the present invention, the first and second primary dichroic layers have a thickness ranging from 30nm to 500nm, respectively.
In one embodiment of the present invention, the materials of the first auxiliary coloring layer and the second auxiliary coloring layer are respectively selected from oxides of at least two elements of nickel, vanadium, cobalt, iridium, iron and manganese.
In one embodiment of the present invention, the first auxiliary color-changing layer and the second auxiliary color-changing layer are made of the same material.
In one embodiment of the present invention, the first auxiliary coloring layer and the second auxiliary coloring layer have a thickness ranging from 20nm to 500nm, respectively.
In one embodiment of the present invention, the first mixed color tone layer comprises a first color tone material selected from oxides of at least two combinations of W, Mo, Nb, Ti, Ta, and a second color tone material selected from oxides of at least two combinations of Ni, V, Co, Ir, Fe, Mn; the second mixed color matching layer comprises a third color matching material and a fourth color matching material, the third color matching material is selected from oxides of at least two combinations of W, Mo, Nb, Ti and Ta, and the fourth color matching material is selected from oxides of at least two combinations of Ni, V, Co, Ir, Fe and Mn.
In one embodiment of the invention, the materials of the first and second mixed color modulation layers are the same.
On the other hand, the preparation method of the color-changing glass provided by the embodiment of the invention comprises the following steps: forming a first transparent conductive layer on a substrate; forming a first auxiliary color-changing layer on the first transparent conductive layer; forming a first ion conductor layer on the first auxiliary color-changing layer; forming a first main color changing layer on the first ion conductor layer; forming a second transparent conducting layer on the first main transformer color layer; forming a second main color changing layer on the second transparent conducting layer; forming a second auxiliary color changing layer on the second main color changing layer; forming a second ion conductor layer on the second auxiliary color-changing layer; forming a third transparent conductive layer on the second ion conductor layer; forming a first mixed color-changing layer on the third transparent conductive layer; forming a third ion conductor layer on the first mixed color-changing layer; forming a second hybrid discoloration layer on the third ion conductor layer; forming a fourth transparent conductive layer on the second mixed color-changing layer; and forming an outer protective layer on the fourth transparent conductive layer.
One or more of the above technical solutions may have the following advantages or beneficial effects: the color-changing glass provided by the embodiment of the invention adopts three different color-changing functional film layers which are respectively and independently regulated and controlled, namely a specific film layer structure which combines three different settings of an auxiliary color-changing layer and a main transformer layer interval, an adjacent main transformer layer and an auxiliary color-changing layer, and a double-mixed color-changing layer interval, thereby increasing the color regulation range of the color-changing glass, realizing regulation and control of more colors, and having wider color coordinate range of the color-changing glass. The preparation method of the color-changing glass provided by the embodiment of the invention simplifies the production process, reduces the production cost and improves the production efficiency.
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 a photochromic glass according to an embodiment of the present invention.
FIG. 2 is a schematic flow chart of a method for preparing a photochromic glass according to an embodiment of 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, one embodiment of the present invention provides a stained glass 200. The color-changing glass 200 includes a substrate 5, and a first transparent conductive layer 11, a first auxiliary color-changing layer 12, a first ion conductor layer 13, a first main color-changing layer 14, a second transparent conductive layer 21, a second main color-changing layer 22, a second auxiliary color-changing layer 23, a second ion conductor layer 24, a third transparent conductive layer 31, a first hybrid color-changing layer 32, a third ion conductor layer 33, a second hybrid color-changing layer 34, a fourth transparent conductive layer 50, and an outer protective layer 60, which are sequentially formed on one side of a base 10.
The color-changing glass provided by the embodiment of the invention adopts three color-changing functional film layers which are respectively and independently regulated and controlled and have different structures, namely, a specific film layer structure which combines three different settings of the interval between the auxiliary color-changing layer and the main transformer layer, the adjacent interval between the main transformer layer and the auxiliary color-changing layer and the interval between the double mixed color-changing layers, the color regulation range of the color-changing glass is enlarged, the regulation and control of more colors are realized, the color coordinate range of the color-changing glass is wider, and the uniformity of the color is improved.
Specifically, the substrate 5 may be, for example, a glass substrate or other similar substrates. Specifically, the glass substrate is, for example, float glass, ultra-white glass, or the like. The thickness of the substrate 5 may range, for example, from 0.05 to 20 mm.
The materials of the first transparent conductive layer 11, the second transparent conductive layer 21, the third transparent conductive layer 31 and the fourth transparent conductive layer 50 are inorganic color-changing materials, respectively. The inorganic color-changing material is selected from one or a combination of at least two of fluorine silicon oxide (FTO), Indium Tin Oxide (ITO), Indium Gallium Zinc Oxide (IGZO), Aluminum Zinc Oxide (AZO), Gallium Zinc Oxide (GZO) and silver (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. Preferably, at least two of the first transparent conductive layer 11, the second transparent conductive layer 21, the third transparent conductive layer 31, and the fourth transparent conductive layer 50 are made of the same material. The thickness ranges of the first transparent conductive layer 11, the second transparent conductive layer 21 and the third transparent conductive layer 31 are 1-1100nm respectively. The thickness of the fourth transparent conductive layer 50 ranges from 10 to 1000 nm. Preferably, the thicknesses of the first transparent conductive layer 11, the second transparent conductive layer 21, the third transparent conductive layer 31 and the fourth transparent conductive layer 50 are respectively 10-300 nm. Further preferably, the thicknesses of the first transparent conductive layer 11 and the second transparent conductive layer 21, and the thicknesses of the third transparent conductive layer 31 and the fourth transparent conductive layer 50 are equal to each other.
The first main color changing layer 14 and the second main color changing layer 22 are main spectrum adjusting functional layers. The materials of the first main color changing layer 14 and the second main color changing layer 22 are inorganic color changing materials respectively. The inorganic colour change material may for example be selected from oxides of combinations of at least two elements of tungsten (W), molybdenum (Mo), niobium (Nb), titanium (Ti), tantalum (Ta), for example oxides of any two combinations of W, Mo, Nb, Ti, Ta, such as WMoOx, wnbo x, or oxides of WMoOx, WNbTaOx, or even combinations of more of the three. Preferably, the materials of the first primary dichroic layer 14 and the second primary dichroic layer 22 are the same. The thickness ranges of the first main color changing layer 14 and the second main color changing layer 22 are 30-500nm respectively. Preferably, the thicknesses of the first primary dichroic layer 14 and the second primary dichroic layer 22 are equal.
The first auxiliary color changing layer 12 and the second auxiliary color changing layer 23 are spectrum auxiliary adjusting functional layers. The materials of the first auxiliary color-changing layer 12 and the second auxiliary color-changing layer 23 are respectively selected from oxides of at least two combinations of nickel (Ni), vanadium (V), cobalt (Co), iridium (Ir), iron (Fe), and manganese (Mn). Specifically, the materials of the first auxiliary coloration layer 12 and the second auxiliary coloration layer 23 may be, for example, oxides of a combination of two of Ni, V, Co, Ir, Fe, Mn, such as an oxide of NiVOx, NiCoOx, NiIrOx, NiFeOx, or a combination of three, or even an oxide of a combination of more. Preferably, the materials of the first auxiliary color-changing layer 12 and the second auxiliary color-changing layer 23 are the same. The thicknesses of the first auxiliary color changing layer 12 and the second auxiliary color changing layer 23 are respectively 20nm-500 nm. Preferably, the thicknesses of the first auxiliary color-changing layer 12 and the second auxiliary color-changing layer 23 are equal.
The material of the first mixed toning layer 32 includes, for example, a first toning material and a second toning material. Wherein the first toner material is selected from oxides of at least two combinations of W, Mo, Nb, Ti, Ta, e.g. oxides of any two combinations of W, Mo, Nb, Ti, Ta, such as WMoOx, wnbo x, or oxides of the three combinations WMoTiOx, WNbTaOx, or even more combinations. The second toner material is selected from oxides of a combination of at least two of Ni, V, Co, Ir, Fe, Mn, in particular may be oxides of a combination of two of Ni, V, Co, Ir, Fe, Mn such as NiVOx, NiCoOx, NiIrOx, NiFeOx, or oxides of a combination of three, or even oxides of a combination of more. The first mixed color modulation layer 32 has a thickness ranging from 30nm to 500 nm.
In view of the above, the material of the second mixed color modulation layer 34 comprises, for example, a third color modulation material and a fourth color modulation material, wherein the third color modulation material is selected from oxides of at least two combinations of W, Mo, Nb, Ti, Ta, for example, oxides of any two combinations of W, Mo, Nb, Ti, Ta, such as WMoOx, wnbo x, or oxides of the three combinations, such as WMoTiOx, WNbTaOx, or even oxides of more combinations; the fourth toner material is selected from oxides of a combination of at least two of Ni, V, Co, Ir, Fe, Mn, in particular may be oxides of a combination of two of Ni, V, Co, Ir, Fe, Mn such as NiVOx, NiCoOx, NiIrOx, NiFeOx, or oxides of a combination of three, or even oxides of a combination of more. The second mixed color modulation layer 34 has a thickness ranging from 20nm to 500 nm.
Preferably, the first mixed color modulation layer 32 and the second mixed color modulation layer 34 are the same material. The first mixed color modulation layer 32 and the second mixed color modulation layer 34 have the same thickness.
The materials of the first ion conductor layer 13, the second ion conductor layer 24, and the third ion conductor layer 33 are respectively selected from one or a combination of at least two of hydrogen (H), lithium (Li), sodium (Na), potassium (K), and magnesium (Mg), for example, a combination of two thereof such as Li and Na, a combination of three thereof such as Na, K, and Mg, and even more thereof. Preferably, the materials of the first ion conductor layer 13, the second ion conductor layer 24, and the third ion conductor layer 33 are the same. The thicknesses of the first ion conductor layer 13, the second ion conductor layer 24, and the third ion conductor layer 33 are in the range of 10nm to 100nm, respectively. Preferably, the thicknesses of the first ion conductor layer 13, the second ion conductor layer 24, and the third ion conductor layer 33 are equal.
The outer protective layer 60 may be well protected and is selected from materialsOxides or nitrides or oxynitrides of one of Si, Ti, Zn, Sn, Nb, Ta, e.g. Si3N4. The thickness of the outer protective layer ranges, for example, from 0.1 to 100 nm.
In addition, the embodiment of the invention also provides a preparation method of the color-changing glass, for example, the preparation method is used for preparing the color-changing glass 200. As shown in fig. 2, the method for preparing the color-changeable glass, for example, comprises the steps of:
s11: a substrate is provided.
S12: a first transparent conductive layer is formed on a substrate. Specifically, the substrate is heated to a preset temperature, wherein the preset temperature range is, for example, 280-300 ℃, one or a combination of at least two of FTO, ITO, IGZO, AZO, GZO, and Ag is used as a target material, and the first transparent conductive layer is deposited under a preset vacuum sputtering pressure. The preset vacuum sputtering pressure is, for example, 1.0E-3～9.0E-3mbar. Preferably, the first transparent conductive layer can also be a pre-prepared conductive film layer. This allows better index matching between the layers.
S13: and forming a first auxiliary color-changing layer on the first transparent conductive layer. Specifically, oxides of at least two combinations of Ni, V, Co, Ir, Fe and Mn are used as target materials, and the target materials are deposited under the condition of preset vacuum sputtering pressure to obtain the first auxiliary discoloring layer. The stoichiometric ratio of the oxide in the target material may be sufficient oxygen or less than the stoichiometric ratio of oxygen. Optionally, the first auxiliary color-changing layer can also be formed by adopting a plurality of target positions at the same time so as to obtain better bonding force between the film layers. The process gas ratios employed for the plurality of target sites may be non-uniform.
S14: and forming a first ion conductor layer on the first auxiliary color changing layer. One or a combination of at least two of H, Li, Na, K and Mg is used as a target material, and the target material is deposited under the condition of preset vacuum sputtering air pressure to obtain a first ion conductor layer. Preferably, the first ion conductor layer can also be formed by using a plurality of target sites at the same time, so as to obtain better bonding force between films. The process gas ratios employed for the plurality of target sites may be non-uniform.
S15: and forming a first main color changing layer on the first ion conductor layer. The oxide of at least two of W, Mo, Nb, Ti and Ta is used as the target material. The stoichiometric ratio of the oxide may be sufficient oxygen or less than the stoichiometric ratio of oxygen. And (3) depositing the target material under a preset vacuum sputtering pressure to obtain a first main variable color layer. Preferably, the first primary color changing layer can also be formed by simultaneously adopting a plurality of target positions, so that 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.
S16: and forming a second transparent conductive layer on the first main color changing layer. Specifically, one or a combination of at least two of FTO, ITO, IGZO, AZO, GZO and Ag is used as a target material, and the target material is deposited under the condition of preset vacuum sputtering air pressure to obtain the second transparent conductive layer. Preferably, the second transparent conductive layer can also be a pre-prepared conductive film layer. This allows better index matching between the layers.
S17: and forming a second main color changing layer on the second transparent conducting layer. The oxide of at least two of W, Mo, Nb, Ti and Ta is used as the target material. And (3) depositing the target material under a preset vacuum sputtering pressure to obtain a second main variable color layer. Preferably, the second primary color layer can also be formed by simultaneously adopting a plurality of target positions, so that 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.
S18: and forming a second auxiliary color changing layer on the second main color changing layer. Specifically, oxides of at least two combinations of Ni, V, Co, Ir, Fe and Mn are used as target materials, and the target materials are deposited under the condition of preset vacuum sputtering pressure to obtain the second auxiliary discoloring layer. The stoichiometric ratio of the oxide in the target material may be sufficient oxygen or less than the stoichiometric ratio of oxygen. Preferably, the second auxiliary color-changing layer can also be formed by using a plurality of target sites at the same time, so as to obtain better bonding force between the film layers. The process gas ratios employed for the plurality of target sites may be non-uniform.
S19: and forming a second ion conductor layer on the second auxiliary color changing layer. And taking one or the combination of at least two of H, Li, Na, K and Mg as a target material, and depositing the target material under the condition of preset vacuum sputtering air pressure to obtain a second ion conductor layer. Preferably, the second ion conductor layer can also be formed by using a plurality of target sites at the same time, so as to obtain better bonding force between films. The process gas ratios employed for the plurality of target sites may be non-uniform.
S20: and forming a third transparent conductive layer on the second ion conductor 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 preset vacuum sputtering pressure to obtain the third transparent conductive layer. Preferably, the third transparent conductive layer can also be a conductive film layer prepared in advance. This allows better index matching between the layers.
S21: and forming a first mixed color changing layer on the third transparent conductive layer. 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 depositing the first target material and the second target material under the condition of preset vacuum sputtering air pressure to obtain a first mixed color-adjusting layer. Preferably, the first mixed toner layer can also be formed simultaneously with multiple target sites to achieve better binding force between the film layers.
S22: and forming a third ion conductor layer on the first mixed color-changing layer. And taking one or the combination of at least two of H, Li, Na, K and Mg as a target material, and depositing the target material under the condition of preset vacuum sputtering air pressure to obtain a third ion conductor layer. Preferably, the third ion conductor layer can also be formed by using a plurality of target sites at the same time, so as to obtain better bonding force between films.
S23: and forming a second mixed color-changing layer on the third ion conductor layer. And 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 depositing the third target material and the fourth target material under a preset vacuum sputtering gas pressure to obtain a second mixed color-adjusting layer. Preferably, the second mixed toner layer can also be formed by using a plurality of target sites at the same time, so that better bonding force between the film layers can be obtained.
S24: and forming a fourth transparent conductive layer on the second mixed 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 preset vacuum sputtering pressure to obtain the fourth transparent conductive layer. Preferably, the fourth transparent conductive layer may also be a conductive film layer prepared in advance. This allows better index matching between the layers.
S25: and forming an outer protective layer on the fourth transparent conductive layer. Taking 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 preset vacuum sputtering pressure to obtain an outer protective layer. Preferably, the outer protective layer can also be formed simultaneously with multiple target sites to achieve better binding between the layers.
In addition, the preparation method of the color-changing glass provided by the embodiment of the invention can also comprise a heat treatment step. Specifically, a vacuum heat treatment and annealing process is performed, wherein the heat treatment temperature is, for example, 300-.
Furthermore, the preparation method of the color-changing glass provided by the embodiment of the invention can also comprise pre-vacuum transition and parallel connection of electrodes to finish the preparation of the color-changing glass. The pre-vacuum transition and the electrode connection can be completed by adopting the method in the prior art, and the details are not repeated here.
In summary, the color-changing glass provided by the embodiment of the invention adopts three different color-changing functional film layers which are respectively and independently regulated and controlled, namely, a specific film layer structure which combines three different arrangements of an auxiliary color-changing layer and a main color-changing layer interval, a main color-changing layer and an auxiliary color-changing layer adjacent to each other, and a double-mixed color-changing layer interval, so that the color regulation range of the color-changing glass is enlarged, regulation and control of more colors are realized, the color coordinate range of the color-changing glass is wider, the color is more stable, the color uniformity of a large area is better, the color retention time after one-time excitation color mixing is longer, and the color-changing glass can be widely applied to various occasions. In addition, the preparation method of the color-changing glass provided by the embodiment of the invention adopts a magnetron reactive sputtering deposition method to form each film layer, thereby avoiding multiple times of entering and exiting of coating equipment in the production process, simplifying the production process and improving the production efficiency.
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 will 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 (10)
1. The color-changing glass is characterized by comprising a substrate, and a first transparent conducting layer, a first auxiliary color-changing layer, a first ion conductor layer, a first main color layer, a second transparent conducting layer, a second main color layer, a second auxiliary color-changing layer, a second ion conductor layer, a third transparent conducting layer, a first mixed color-changing layer, a third ion conductor layer, a second mixed color-changing layer, a fourth transparent conducting layer and an outer protective layer which are sequentially formed on one side of the substrate; wherein the materials of the first main color layer and the second main color layer are respectively selected from oxides of at least two combinations of tungsten, molybdenum, niobium, titanium and tantalum; the first auxiliary color-changing layer and the second auxiliary color-changing layer are made of oxides of at least two elements selected from nickel, vanadium, cobalt, iridium, iron and manganese; the first mixed color matching layer comprises a first color matching material and a second color matching material, the first color matching material is selected from oxides of at least two combinations of W, Mo, Nb, Ti and Ta, and the second color matching material is selected from oxides of at least two combinations of Ni, V, Co, Ir, Fe and Mn; the second mixed color matching layer comprises a third color matching material and a fourth color matching material, the third color matching material is selected from oxides of at least two combinations of W, Mo, Nb, Ti and Ta, and the fourth color matching material is selected from oxides of at least two combinations of Ni, V, Co, Ir, Fe and Mn.
2. The utility model provides a color-changing glass, its characterized in that includes the base plate and the first transparent conducting layer, first supplementary discoloration layer, first ion conductor layer, first main discoloration layer, second transparent conducting layer, second main discoloration layer, the supplementary discoloration layer of second, second ion conductor layer, third transparent conducting layer, first mixed discoloration layer, third ion conductor layer, the mixed discoloration layer of second, fourth transparent conducting layer and the outer protective layer that form in proper order of base plate one side.
3. The color-changing glass according to claim 1, wherein the materials of the first primary color-changing layer and the second primary color-changing layer are respectively selected from oxides of at least two combinations of tungsten, molybdenum, niobium, titanium and tantalum.
4. The color-changing glass according to claim 2, wherein the materials of the first primary color-changing layer and the second primary color-changing layer are the same.
5. The color-changing glass according to claim 1, wherein the first primary color-changing layer and the second primary color-changing layer have a thickness ranging from 30nm to 500nm, respectively.
6. The photochromic glass of claim 1, wherein the materials of the first and second auxiliary photochromic layers are respectively selected from oxides of at least two elements selected from nickel, vanadium, cobalt, iridium, iron and manganese.
7. The photochromic glass of claim 5, wherein the first auxiliary color-changing layer and the second auxiliary color-changing layer are made of the same material; the thickness ranges of the first auxiliary color changing layer and the second auxiliary color changing layer are respectively 20nm-500 nm.
8. The color shifting glass of claim 1, wherein the first mixed color shifting layer comprises a first color shifting material selected from oxides of at least two combinations of W, Mo, Nb, Ti, Ta and a second color shifting material selected from oxides of at least two combinations of Ni, V, Co, Ir, Fe, Mn; the second mixed color matching layer comprises a third color matching material and a fourth color matching material, the third color matching material is selected from oxides of at least two combinations of W, Mo, Nb, Ti and Ta, and the fourth color matching material is selected from oxides of at least two combinations of Ni, V, Co, Ir, Fe and Mn.
9. Changing glass according to claim 1, characterised in that the material of the first and second mixed colour control layers is the same.
10. A method for preparing color-changing glass is characterized by comprising the following steps:
forming a first transparent conductive layer on a substrate;
forming a first auxiliary color-changing layer on the first transparent conductive layer;
forming a first ion conductor layer on the first auxiliary color-changing layer;
forming a first main color changing layer on the first ion conductor layer;
forming a second transparent conducting layer on the first main transformer color layer;
forming a second main color changing layer on the second transparent conducting layer;
forming a second auxiliary color changing layer on the second main color changing layer;
forming a second ion conductor layer on the second auxiliary color-changing layer;
forming a third transparent conductive layer on the second ion conductor layer;
forming a first mixed color-changing layer on the third transparent conductive layer;
forming a third ion conductor layer on the first mixed color-changing layer;
forming a second hybrid discoloration layer on the third ion conductor layer;
forming a fourth transparent conductive layer on the second mixed color-changing layer; and
and forming an outer protective layer on the fourth transparent conductive layer.
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