CN113189822A - Electrochromic device and preparation method thereof - Google Patents

Electrochromic device and preparation method thereof Download PDF

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Publication number
CN113189822A
CN113189822A CN202110446775.1A CN202110446775A CN113189822A CN 113189822 A CN113189822 A CN 113189822A CN 202110446775 A CN202110446775 A CN 202110446775A CN 113189822 A CN113189822 A CN 113189822A
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China
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layer
thickness
conducting layer
magnetron sputtering
diffusion
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Inventor
王红莉
唐春梅
石倩
王磊
许伟
汪唯
唐鹏
郭朝乾
苏一凡
黄淑琪
韦春贝
林松盛
代明江
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Institute of New Materials of Guangdong Academy of Sciences
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Institute of New Materials of Guangdong Academy of Sciences
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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
    • 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
    • G02F1/1506—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 caused by electrodeposition, e.g. electrolytic deposition of an inorganic material on or close to an electrode
    • G02F1/1508—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 caused by electrodeposition, e.g. electrolytic deposition of an inorganic material on or close to an electrode using a solid electrolyte
    • 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
    • G02F1/1514—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
    • 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
    • G02F1/155—Electrodes

Abstract

The invention provides an electrochromic device and a preparation method thereof, and belongs to the field of electrochromic devices. The electrochromic device is made of pure solid materials, and is high in safety and stability; a multilayer composite structure is adopted as a transparent conducting layer structure, wherein the metal layer can obviously improve the conductivity of the conducting layer, so that the response speed of the obtained device is improved; the bottom diffusion-resistant layer and the top diffusion-resistant layer are compounded, so that the diffusion and oxidation of the metal layer of the device in a high-temperature environment can be effectively prevented, and the service life and the cycle stability of the device are guaranteed; the anode discoloring layer is made of specific lithium ion doped nickel oxide, so that the adjusting range of the visible light transmittance of the obtained electrochromic device can be greatly improved, and the application range is wide. The invention also provides a preparation method of the product, each layer structure of the device is prepared by deposition through a magnetron sputtering method, the vacuum environment is not required to be broken or the segmented treatment is not required, the operation steps are simple and stable, and the industrialized large-scale production can be realized.

Description

Electrochromic device and preparation method thereof
Technical Field
The invention belongs to the technical field of color-changing devices, and particularly relates to an electrochromic device and a preparation method thereof.
Background
Electrochromic material is a material whose optical properties can be changed reversibly and durably firmly under an applied voltage. The electrochromic material has wide application prospect in the technical fields of building energy-saving glass, non-glare automobile rearview mirrors, airplane portholes and the like due to excellent optical performance, and has great market potential.
The electrochromic intelligent glass can selectively transmit, absorb or reflect external heat radiation and internal heat diffusion under the action of an electric field, so that a large amount of energy which is consumed for keeping office buildings and civil houses cool in summer and warm in winter is reduced, and the aims of improving the natural illumination degree and preventing peeping are fulfilled. The electrochromic material has bistable performance, only needs 2-5V voltage for driving when the optical transmittance is changed, and the maintenance of a stable state does not consume power, so that the aim of saving energy is fulfilled.
A typical electrochromic device consists of a transparent conductive layer, an electrochromic layer, an ion conductive layer and an ion storage layer in this order. The transparent conductive layer serves as an electrode for conducting electrons, and generally commercially produced Indium Tin Oxide (ITO) or fluorine-doped tin oxide (FTO) glass is used. The electrochromic layer plays a decisive role in the performance of the whole electrochromic device, and the optical characteristics of the film are reversibly changed along with the injection or extraction of lithium ions, hydrogen ions, aluminum ions and the like, and the film shows reversible change of color in a visible light range. Currently, the most common inorganic electrochromic layer material is tungsten oxide, which exhibits dark blue and transparent colors in colored and faded states, respectively. The function of the ion storage layer is to prevent deposition of ions on the electrodes, and to collect ions as they are extracted from the electrochromic layer. The most common inorganic ion storage layer is currently nickel oxide. The ion conducting layer, also called electrolyte, mainly provides the ion transport channels needed in the electrochromic process.
The existing electrochromic devices are classified into three types according to the different forms of ion conducting layers: liquid electrolyte electrochromic devices, organic solid electrolyte electrochromic devices, and inorganic solid electrolyte electrochromic devices. The potential safety hazard is large after the liquid electrolyte is leaked, the stability and the weather resistance of the organic solid electrolyte are poor, and the phenomena of nonuniform color change, reduced optical modulation performance, bubble generation and the like of the device are easy to occur along with the increase of the size of the device, so that the large-scale application of the device is severely limited. The inorganic all-solid-state electrochromic device adopts inorganic solid electrolyte, has good stability and high safety, can be used for large-area devices, and is more suitable for large-scale industrial production and application. However, the inorganic all-solid-state electrochromic device has the problems of low response speed, small optical modulation amplitude, poor cycle stability, short service life and the like, and the large-scale application of the inorganic all-solid-state electrochromic device is severely restricted.
Disclosure of Invention
Based on the defects in the prior art, the invention aims to provide an electrochromic device, which is used as an inorganic all-solid-state electrolyte device, and the transparent conducting layer hierarchical structure of a bottom conducting layer/a bottom diffusion-resistant layer/a metal layer/a top diffusion-resistant layer/a top conducting layer is adopted, so that the advantages of the inorganic solid-state electrolyte are maintained, the response speed and the cycle stability of the electrochromic device are obviously improved, the service life is prolonged, and the adjustment range of the visible light transmittance is enlarged.
In order to achieve the purpose, the invention adopts the technical scheme that:
an electrochromic device comprises a substrate, a first transparent conducting layer, a cathode color changing layer, an ion conducting layer, an anode color changing layer and a second transparent conducting layer from bottom to top in sequence; the first transparent conducting layer and the second transparent conducting layer are of a composite structure, and the transparent conducting layer comprises a bottom conducting layer, a bottom resistance diffusion layer, a metal layer, a top resistance diffusion layer and a top conducting layer from bottom to top; the anode discoloring layer is a lithium ion doped nickel oxide film.
The electrochromic device is made of pure solid materials, so that the problems of leakage of a liquid electrolyte device or aging of an organic solid electrolyte device do not exist, and the electrochromic device is high in safety and stability; the bottom conducting layer/bottom diffusion-resistant layer/metal layer/top diffusion-resistant layer/top conducting layer similar to the multilayer sandwich composite structure is adopted as a transparent conducting layer structure, wherein the metal layer can obviously improve the conductivity of the conducting layer, so that the response speed of the obtained device is improved; the bottom diffusion-resistant layer and the top diffusion-resistant layer are compounded, so that the diffusion and oxidation of the metal layer of the device in a high-temperature environment can be effectively prevented, and the service life and the cycle stability of the device are guaranteed; the anode discoloring layer is made of specific lithium ion doped nickel oxide, so that the adjusting range of the visible light transmittance of the obtained electrochromic device can be greatly improved, and the application range is wide.
Preferably, the substrate is a glass substrate, and the thickness of the glass substrate is 2-10 mm;
more preferably, the thickness of the glass substrate is 5 mm.
Preferably, the component of the cathode discoloration layer is metal oxide, the metal oxide is at least one of tungsten oxide, niobium oxide, molybdenum oxide and titanium oxide, and the thickness of the cathode discoloration layer is 100-800 nm;
more preferably, the cathode discoloration layer is tungsten oxide, and the thickness of the cathode discoloration layer is 200-350 nm.
The metal oxide selected for the cathode discoloring layer has stable property under a specific thickness, and can effectively realize the injection and extraction of ions and ensure the rapid implementation of ion transportation and conversion.
Preferably, the components of the ion conducting layer comprise at least one of lithium phosphorus oxynitride, lithium niobate, lithium carbonate and lithium vanadate, and the thickness of the ion conducting layer is 100-1000 nm;
more preferably, the components of the ion conducting layer comprise at least one of lithium phosphorus oxynitride, lithium niobate and lithium carbonate, and the thickness of the ion conducting layer is 200-500 nm;
more preferably, the composition of the ion-conducting layer is lithium phosphorus oxynitride, and the thickness of the ion-conducting layer is 300 nm.
The ion conducting layer mainly plays a role in a channel for storing and transmitting ions in the electrochromic layer, so that the coloring or the fading of a device is realized, and a stable lithium ion binding component is needed; the above-mentioned conductive layer, which consists of a preferred lithium salt and has a preferred thickness, ensures stable, fast conductive storage of the ions.
Preferably, in the first transparent conductive layer and the second transparent conductive layer, the bottom conductive layer and the top conductive layer comprise at least one of Indium Tin Oxide (ITO), aluminum-doped zinc oxide (AZO), and fluorine-doped tin oxide (FTO), the bottom conductive layer has a thickness of 30-100 nm, and the top conductive layer has a thickness of 30-100 nm;
more preferably, the thickness of the bottom conducting layer is 50-80 nm, and the thickness of the top conducting layer is 50-80 nm.
Preferably, in the first transparent conductive layer and the second transparent conductive layer, the metal layer comprises at least one of gold, silver, copper and aluminum, and the thickness of the metal layer is 5-30 nm;
more preferably, the thickness of the metal layer is 8-18 nm.
Preferably, in the first transparent conductive layer and the second transparent conductive layer, the bottom resistance diffusion layer and the top resistance diffusion layer comprise at least one of nickel and cobalt, the thickness of the bottom resistance diffusion layer is 3-8 nm, and the thickness of the top resistance diffusion layer is 3-8 nm;
more preferably, the bottom diffusion barrier layer has a thickness of 5nm, and the top diffusion barrier layer has a thickness of 5 nm.
According to the two-layer transparent conducting layer electrode, metal oxide with stable property and high conductivity is used as a conducting electrode component, metal with low resistivity is used as a metal layer, metal with diffusion resistance and diffusion resistance is used as a diffusion resistance layer, so that the conductivity of the whole conducting layer is effectively improved, the metal layer can be prevented from being diffused or oxidized due to external influence, and the performance influence of a device is avoided.
Preferably, in the anode discoloration layer, the mass content of lithium ions in the lithium ion-doped nickel oxide film is 3-20%; more preferably, the mass content of the lithium ions in the lithium ion doped nickel oxide film is 10%.
The lithium ion doped color-changing layer with the optimal content is adopted, the optical adjusting range of the product can be effectively improved to a certain extent, the adjusting range of the visible light transmittance of the product is enlarged, and the usable range is widened.
Preferably, the thickness of the anode discoloration layer is 120-350 nm; more preferably, the thickness of the anodically coloring layer is 150 nm.
Another object of the present invention is to provide a method for preparing the electrochromic device, the method comprising the steps of: and placing the substrate in a vacuum environment, and depositing a first transparent conducting layer, a cathode color changing layer, an ion conducting layer, an anode color changing layer and a second transparent conducting layer on the substrate in sequence by adopting a magnetron sputtering method to obtain the electrochromic device.
In the preparation method of the product, each layer structure of the device is prepared by deposition by a magnetron sputtering method, the vacuum environment is not required to be broken or the segmented treatment is not required, the operation steps are simple and stable, the production efficiency of the product can be effectively improved, and the industrial large-scale production can be realized.
Preferably, the vacuum degree of the vacuum environment is less than or equal to5×10-4Pa。
Preferably, the electrochromic device is kept rotating while being deposited and prepared by a magnetron sputtering method.
During magnetron sputtering deposition, the substrate and the deposited structure layer are kept rotating, and the deposition uniformity of each subsequent layer of film can be effectively guaranteed.
Preferably, the first transparent conductive layer and the second transparent conductive layer are deposited by a direct current magnetron sputtering method, and a bottom conductive layer, a bottom diffusion-resistant layer, a metal layer, a top diffusion-resistant layer and a top conductive layer are sequentially deposited.
Preferably, the cathode discoloration layer is deposited by a direct-current reactive magnetron sputtering method, a radio frequency magnetron sputtering method or a medium frequency magnetron sputtering method.
Preferably, the ion conducting layer is deposited by adopting a radio frequency magnetron sputtering method or a medium frequency magnetron sputtering method.
Preferably, the anodic color-changing layer is deposited by radio frequency magnetron sputtering or medium frequency magnetron sputtering.
The electrochromic device has the beneficial effects that the electrochromic device is made of pure solid materials, the problem of leakage of a liquid electrolyte device or aging of an organic solid electrolyte device is solved, and the electrochromic device is high in safety and stability; the bottom conducting layer/bottom diffusion-resistant layer/metal layer/top diffusion-resistant layer/top conducting layer similar to the multilayer sandwich composite structure is adopted as a transparent conducting layer structure, wherein the metal layer can obviously improve the conductivity of the conducting layer, so that the response speed of the obtained device is improved; the bottom diffusion-resistant layer and the top diffusion-resistant layer are compounded, so that the diffusion and oxidation of the metal layer of the device in a high-temperature environment can be effectively prevented, and the service life and the cycle stability of the device are guaranteed; the anode discoloring layer is made of specific lithium ion doped nickel oxide, so that the adjusting range of the visible light transmittance of the obtained electrochromic device can be greatly improved, and the application range is wide. The invention also provides a preparation method of the product, each layer structure of the device is prepared by deposition through a magnetron sputtering method, the vacuum environment is not required to be broken or the segmented treatment is not required, the operation steps are simple and stable, the production efficiency of the product can be effectively improved, and the industrial large-scale production can be realized.
Drawings
FIG. 1 is a schematic structural diagram of an electrochromic device according to the present invention (the diagram includes a substrate 10, a first transparent conductive layer 11, a cathode discoloration layer 12, an ion conductive layer 13, an anode discoloration layer 14, and a second transparent conductive layer 15, wherein the first transparent conductive layer includes a bottom conductive layer 111, a bottom diffusion-blocking layer 112, a metal layer 113, a top diffusion-blocking layer 114, and a top conductive layer 115; the second transparent conductive layer includes a bottom conductive layer 151, a bottom diffusion-blocking layer 152, a metal layer 153, a top diffusion-blocking layer 154, and a top conductive layer 155);
FIG. 2 is a graph of a chronoamperometric test of an electrochromic device according to example 1 of the present invention;
FIG. 3 is a graph showing the change in optical transmittance in the initial visible range of an electrochromic device according to example 1 of the present invention;
fig. 4 is a graph showing the change in optical transmittance in the visible light range after 5000 cycles of the electrochromic device according to example 1 of the present invention.
Detailed Description
In order to better illustrate the objects, technical solutions and advantages of the present invention, the present invention will be further described with reference to specific examples and comparative examples, which are intended to be understood in detail, but not intended to limit the invention. All other embodiments obtained by a person skilled in the art without making any inventive step are within the scope of protection of the present invention.
Example 1
The electrochromic device of the invention, as shown in fig. 1, comprises a substrate 10, a first transparent conducting layer 11, a cathode discoloration layer 12, an ion conducting layer 13, an anode discoloration layer 14 and a second transparent conducting layer 15 in sequence from bottom to top, wherein the first transparent conducting layer comprises a bottom conducting layer 111, a bottom diffusion-resistant layer 112, a metal layer 113, a top diffusion-resistant layer 114 and a top conducting layer 115; the second transparent conductive layer includes a bottom conductive layer 151, a bottom diffusion-preventing layer 152, a metal layer 153, a top diffusion-preventing layer 154, and a top conductive layer 155;
the preparation method of the product comprises the following steps:
(1) ultrasonically cleaning and drying 5mm of ultra-white glass by acetone, ethanol and deionized water, and then putting the ultra-white glass into a vacuum coating chamber; the vacuum degree of the vacuum coating chamber is less than or equal to 1 multiplied by 10-4Pa；
(2) Adopting a direct-current magnetron sputtering ITO target to prepare an ITO layer by deposition: setting the power to be 250W, introducing pure argon gas with the pressure of 0.5Pa, and depositing the film with the thickness of 60 nm;
(3) adopting direct current magnetron sputtering Ni target material, depositing and preparing a Ni layer: setting the power to be 80W, introducing pure argon gas with the pressure of 0.3Pa, and setting the thickness of a deposited film layer to be 5 nm;
(4) adopting a direct current magnetron sputtering Ag target to prepare an Ag layer by deposition: setting the power at 150W, introducing pure argon gas with the pressure of 0.3Pa, and depositing a film layer with the thickness of 10 nm;
(5) adopting direct current magnetron sputtering Ni target material, depositing and preparing a Ni layer: setting the power to be 80W, the pressure of pure argon to be 0.3Pa, and the thickness of a deposited film layer to be 5 nm;
(6) adopting a direct-current magnetron sputtering ITO target to prepare an ITO layer by deposition: setting the power to be 250W, the pressure of pure argon to be 0.5Pa, and the thickness of a deposited film layer to be 60 nm;
(7) preparing WO by deposition by adopting direct-current magnetron sputtering W target3Layer (b): setting the power at 250W, introducing argon: the oxygen ratio is 1:1, the air pressure is 2.5Pa, and the thickness of the deposited film layer is 300 nm;
(8) magnetron sputtering Li by radio frequency reaction3PO4Target, deposition preparation of LiPON layer: setting the power to be 180W, introducing pure nitrogen gas with the pressure of 3.0Pa, and depositing the film with the thickness of 250 nm;
(9) preparing Li-NiO by depositing and sputtering Li-NiO target by radio frequency magnetron sputteringx: setting the power at 150W, introducing argon: the oxygen ratio is 95:5, the air pressure is 1.0Pa, and the thickness of the deposited film layer is 150 nm;
(10) adopting a direct-current magnetron sputtering ITO target to prepare an ITO layer by deposition: setting the power to be 250W, introducing pure argon gas with the pressure of 0.5Pa, and depositing the film with the thickness of 60 nm;
(11) adopting direct current magnetron sputtering Ni target material, depositing and preparing a Ni layer: setting the power to be 80W, the pressure of pure argon to be 0.3Pa, and the thickness of a deposited film layer to be 5 nm;
(12) adopting a direct current magnetron sputtering Ag target to prepare an Ag layer by deposition: setting the power at 150W, the pressure of pure argon at 0.3Pa, and the thickness of a deposited film layer at 10 nm;
(13) adopting direct current magnetron sputtering Ni target material, depositing and preparing a Ni layer: setting the power to be 80W, the pressure of pure argon to be 0.3Pa, and the thickness of a deposited film layer to be 5 nm;
(14) adopting a direct-current magnetron sputtering ITO target to prepare an ITO layer by deposition: setting the power to be 250W, the pressure of pure argon to be 0.5Pa and the thickness of a deposited film layer to be 60nm, thus obtaining the electrochromic device.
The obtained device product was subjected to a power-on test by applying a negative voltage of-1.5V and a positive voltage of 1.5V for 30s, respectively, to cause coloring and discoloration of the device, and the results of the obtained timing current curve are shown in FIG. 2. As can be seen from the figure, the coloring time and the fading time of the device obtained in the embodiment are respectively 8s and 8.8s, the total response time is 16.8s, and the device is shorter than the existing product, so that the problem of slow response speed of the device of the existing product is effectively solved.
The obtained device was subjected to a visible light optical transmittance test, and the results are shown in fig. 3 and 4. As can be seen in fig. 3, the optical transmittance of the electrochromic device at 560nm in the faded state is about 80.3%; in contrast, the optical transmittance at 560nm or so in the colored state was about 1.6%, and the optical modulation width was about 78.7%. Therefore, the inorganic all-solid-state thin film electrochromic device prepared in the embodiment 1 has larger optical modulation amplitude in a visible light range; as can be seen from fig. 4, the device still maintains 59.3% of optical modulation amplitude after 5000 cycles, has less performance attenuation, and thus can be widely applied to the field of commodities such as architectural glass energy-saving windows and the like.
Example 2
The difference between this example and example 1 is only that the process for the preparation of the product comprises the following steps:
(1) ultrasonically cleaning and drying 10mm of ultra-white glass by acetone, ethanol and deionized water, and then putting the ultra-white glass into a vacuum coating chamber; the vacuum degree of the vacuum coating chamber is less than or equal to 1 multiplied by 10-4Pa；
(2) Adopting a direct-current magnetron sputtering ITO target to prepare an ITO layer by deposition: setting the power to be 250W, introducing pure argon gas with the pressure of 0.5Pa, and depositing the film with the thickness of 80 nm;
(3) adopting direct current magnetron sputtering Ni target material, depositing and preparing a Ni layer: setting the power to be 80W, introducing pure argon gas with the pressure of 0.3Pa, and depositing the film with the thickness of 3 nm;
(4) adopting a direct current magnetron sputtering Cu target to prepare a Cu layer by deposition: setting the power at 180W, introducing pure argon gas with the pressure of 0.3Pa, and depositing the film with the thickness of 20 nm;
(5) adopting direct current magnetron sputtering Ni target material, depositing and preparing a Ni layer: setting the power to be 80W, the pressure of pure argon to be 0.3Pa, and the thickness of a deposited film layer to be 3 nm;
(6) adopting a direct-current magnetron sputtering ITO target to prepare an ITO layer by deposition: setting the power to be 250W, the pressure of pure argon to be 0.5Pa, and the thickness of a deposited film layer to be 80 nm;
(7) preparing WO by deposition by adopting direct-current magnetron sputtering W target3Layer (b): setting the power at 250W, introducing argon: the oxygen ratio is 1:1, the air pressure is 2.5Pa, and the thickness of the deposited film layer is 200 nm;
(8) magnetron sputtering Li by radio frequency reaction3PO4Target, deposition preparation of LiPON layer: setting the power to be 180W, introducing pure nitrogen gas with the pressure of 3.0Pa, and setting the thickness of the deposited film layer to be 500 nm;
(9) preparing 10 wt% doped Li-NiO by depositing and sputtering Li-NiO target by radio frequency magnetron sputteringx: setting the power at 150W, introducing argon: the oxygen ratio is 95:5, the air pressure is 1.0Pa, and the thickness of the deposited film layer is 250 nm;
(10) adopting a direct-current magnetron sputtering ITO target to prepare an ITO layer by deposition: setting the power to be 250W, introducing pure argon gas with the pressure of 0.5Pa, and depositing the film with the thickness of 50 nm;
(11) adopting direct current magnetron sputtering Ni target material, depositing and preparing a Ni layer: setting the power to be 80W, the pressure of pure argon to be 0.3Pa, and the thickness of a deposited film layer to be 8 nm;
(12) adopting a direct current magnetron sputtering Cu target to prepare a Cu layer by deposition: setting the power to be 180W, the pressure of pure argon to be 0.3Pa, and the thickness of a deposited film layer to be 10 nm;
(13) adopting direct current magnetron sputtering Ni target material, depositing and preparing a Ni layer: setting the power to be 80W, the pressure of pure argon to be 0.3Pa, and the thickness of a deposited film layer to be 8 nm;
(14) adopting a direct-current magnetron sputtering ITO target to prepare an ITO layer by deposition: setting the power to be 250W, the pressure of pure argon to be 0.5Pa and the thickness of a deposited film layer to be 50nm, thus obtaining the electrochromic device.
Example 3
The difference between this example and example 1 is only that the process for the preparation of the product comprises the following steps:
(1) ultrasonically cleaning and drying 5mm of ultra-white glass by acetone, ethanol and deionized water, and then putting the ultra-white glass into a vacuum coating chamber; the vacuum degree of the vacuum coating chamber is less than or equal to 1 multiplied by 10-4Pa；
(2) Adopting a direct current magnetron sputtering ITO target to prepare an AZO layer by deposition: setting the power at 220W, introducing pure argon gas with the pressure of 0.5Pa, and depositing the film with the thickness of 60 nm;
(3) adopting direct current magnetron sputtering Co target material to prepare a Co layer by deposition: setting the power to be 100W, introducing pure argon gas with the pressure of 0.3Pa, and setting the thickness of a deposited film layer to be 5 nm;
(4) adopting a direct current magnetron sputtering Ag target to prepare an Ag layer by deposition: setting the power at 150W, introducing pure argon gas with the pressure of 0.3Pa, and depositing a film layer with the thickness of 10 nm;
(5) adopting direct current magnetron sputtering Co target material to prepare a Co layer by deposition: setting the power to be 100W, the pressure of pure argon to be 0.3Pa, and the thickness of a deposited film layer to be 5 nm;
(6) adopting a direct current magnetron sputtering ITO target to prepare an AZO layer by deposition: setting the power to be 250W, the pressure of pure argon to be 0.5Pa, and the thickness of a deposited film layer to be 60 nm;
(7) preparing WO by deposition by adopting direct-current magnetron sputtering W target3Layer (b): setting the power as 220W, introducing argon: the oxygen ratio is 1:1, the air pressure is 2.5Pa, and the thickness of the deposited film layer is 300 nm;
(8) magnetron sputtering Li by radio frequency reaction3PO4Target, deposition preparation of LiPON layer: setting the power to be 180W, introducing pure nitrogen gas with the pressure of 3.0Pa, and depositing the film with the thickness of 250 nm;
(9) preparing Li-NiO by depositing and sputtering Li-NiO target by radio frequency magnetron sputteringx: setting the power at 150W, introducing argon: oxygen ratio of 95:5, air pressure of 1.0Pa, deposition of film layerThe thickness is 150 nm;
(10) adopting a direct current magnetron sputtering AZO target to prepare an AZO layer by deposition: setting the power at 220W, introducing pure argon gas with the pressure of 0.5Pa, and depositing the film with the thickness of 60 nm;
(11) adopting direct current magnetron sputtering Co target material to prepare a Co layer by deposition: setting the power to be 100W, the pressure of pure argon to be 0.3Pa, and the thickness of a deposited film layer to be 5 nm;
(12) adopting a direct current magnetron sputtering Ag target to prepare an Ag layer by deposition: setting the power at 150W, the pressure of pure argon at 0.3Pa, and the thickness of a deposited film layer at 10 nm;
(13) adopting direct current magnetron sputtering Co target material to prepare a Co layer by deposition: setting the power to be 100W, the pressure of pure argon to be 0.3Pa, and the thickness of a deposited film layer to be 5 nm;
(14) adopting a direct current magnetron sputtering AZO target to prepare an AZO layer by deposition: setting the power to be 220W, the pressure of pure argon to be 0.5Pa and the thickness of a deposited film layer to be 60nm, thus obtaining the electrochromic device.
Finally, it should be noted that the above embodiments are only used for illustrating the technical solutions of the present invention and not for limiting the protection scope of the present invention, and although the present invention is described in detail with reference to the preferred embodiments, it should be understood by those skilled in the art that modifications or equivalent substitutions can be made on the technical solutions of the present invention without departing from the spirit and scope of the technical solutions of the present invention.

Claims (10)

1. An electrochromic device is characterized by comprising a substrate, a first transparent conducting layer, a cathode color changing layer, an ion conducting layer, an anode color changing layer and a second transparent conducting layer from bottom to top in sequence; the first transparent conducting layer and the second transparent conducting layer are of a composite structure, and the transparent conducting layer comprises a bottom conducting layer, a bottom resistance diffusion layer, a metal layer, a top resistance diffusion layer and a top conducting layer from bottom to top; the anode discoloring layer is a lithium ion doped nickel oxide film.
2. The electrochromic device according to claim 1, wherein said substrate is a glass substrate, said glass substrate having a thickness of 2 to 10 mm; preferably, the thickness of the glass substrate is 5 mm.
3. The electrochromic device according to claim 1, wherein the component of the cathodically coloring layer is a metal oxide, the metal oxide is at least one of tungsten oxide, niobium oxide, molybdenum oxide, and titanium oxide, and the thickness of the cathodically coloring layer is 100 to 800 nm; preferably, the cathode discoloring layer is tungsten oxide, and the thickness of the cathode discoloring layer is 200-350 nm.
4. The electrochromic device according to claim 1, wherein the composition of said ion-conducting layer comprises at least one of lithium phosphorus oxynitride, lithium niobate, lithium carbonate, and lithium vanadate, and the thickness of said ion-conducting layer is 100 to 1000 nm; preferably, the ion conducting layer comprises at least one of lithium phosphorus oxynitride, lithium niobate and lithium carbonate, and the thickness of the ion conducting layer is 200-500 nm.
5. The electrochromic device according to claim 1, wherein in the first transparent conductive layer and the second transparent conductive layer, the components of the bottom conductive layer and the top conductive layer comprise at least one of indium tin oxide, aluminum-doped zinc oxide and fluorine-doped tin oxide, the thickness of the bottom conductive layer is 30-100 nm, and the thickness of the top conductive layer is 30-100 nm; preferably, the thickness of the bottom conducting layer is 50-80 nm, and the thickness of the top conducting layer is 50-80 nm.
6. The electrochromic device according to claim 1, wherein in the first transparent conductive layer and the second transparent conductive layer, the composition of the metal layer comprises at least one of gold, silver, copper and aluminum, and the thickness of the metal layer is 5 to 30 nm; preferably, the thickness of the metal layer is 8-18 nm.
7. The electrochromic device according to claim 1, wherein in the first transparent conductive layer and the second transparent conductive layer, the bottom diffusion-resistant layer and the top diffusion-resistant layer comprise at least one of nickel and cobalt, the bottom diffusion-resistant layer has a thickness of 3 to 8nm, and the top diffusion-resistant layer has a thickness of 3 to 8 nm; preferably, the thickness of the bottom resistance diffusion layer is 5nm, and the thickness of the top resistance diffusion layer is 5 nm.
8. The electrochromic device according to claim 1, wherein in the anodically coloring layer, the mass content of lithium ions in the lithium ion doped nickel oxide thin film is 3-20%, and the thickness of the anodically coloring layer is 120-350 nm; preferably, the mass content of the lithium ions in the lithium ion doped nickel oxide film is 10%, and the thickness of the anode discoloration layer is 150 nm.
9. The method for producing an electrochromic device according to any one of claims 1 to 8, characterized by comprising the steps of: and placing the substrate in a vacuum environment, and depositing a first transparent conducting layer, a cathode color changing layer, an ion conducting layer, an anode color changing layer and a second transparent conducting layer on the substrate in sequence by adopting a magnetron sputtering method to obtain the electrochromic device.
10. The method of claim 9, wherein the vacuum is less than or equal to 5 x 10-4Pa; the first transparent conducting layer and the second transparent conducting layer are deposited by a direct-current magnetron sputtering method, and a bottom conducting layer, a bottom diffusion resistance layer, a metal layer, a top diffusion resistance layer and a top conducting layer are sequentially deposited; the cathode color changing layer is deposited by adopting a direct-current reactive magnetron sputtering method, a radio frequency magnetron sputtering method or a medium frequency magnetron sputtering method; the ion conducting layer is deposited by adopting a radio frequency magnetron sputtering method or a medium frequency magnetron sputtering method; and the anode color changing layer is deposited by adopting a radio frequency magnetron sputtering method or a medium frequency magnetron sputtering method.
CN202110446775.1A 2021-04-23 2021-04-23 Electrochromic device and preparation method thereof Pending CN113189822A (en)

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