CN111410440A - Ultraviolet irradiation assisted electrochromic device low-temperature annealing process, device and glass - Google Patents
Ultraviolet irradiation assisted electrochromic device low-temperature annealing process, device and glass Download PDFInfo
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- 150000002500 ions Chemical class 0.000 description 7
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- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C23/00—Other surface treatment of glass not in the form of fibres or filaments
- C03C23/0005—Other surface treatment of glass not in the form of fibres or filaments by irradiation
- C03C23/002—Other surface treatment of glass not in the form of fibres or filaments by irradiation by ultraviolet light
-
- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03B—MANUFACTURE, SHAPING, OR SUPPLEMENTARY PROCESSES
- C03B25/00—Annealing glass products
-
- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C17/00—Surface treatment of glass, not in the form of fibres or filaments, by coating
- C03C17/34—Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions
- C03C17/36—Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions at least one coating being a metal
- C03C17/3602—Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions at least one coating being a metal the metal being present as a layer
- C03C17/3642—Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions at least one coating being a metal the metal being present as a layer the multilayer coating containing a metal layer
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- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C17/00—Surface treatment of glass, not in the form of fibres or filaments, by coating
- C03C17/34—Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions
- C03C17/36—Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions at least one coating being a metal
- C03C17/3602—Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions at least one coating being a metal the metal being present as a layer
- C03C17/3649—Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions at least one coating being a metal the metal being present as a layer made of metals other than silver
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- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C17/00—Surface treatment of glass, not in the form of fibres or filaments, by coating
- C03C17/34—Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions
- C03C17/36—Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions at least one coating being a metal
- C03C17/3602—Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions at least one coating being a metal the metal being present as a layer
- C03C17/3657—Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions at least one coating being a metal the metal being present as a layer the multilayer coating having optical properties
- C03C17/366—Low-emissivity or solar control coatings
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- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C17/00—Surface treatment of glass, not in the form of fibres or filaments, by coating
- C03C17/34—Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions
- C03C17/36—Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions at least one coating being a metal
- C03C17/3602—Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions at least one coating being a metal the metal being present as a layer
- C03C17/3668—Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions at least one coating being a metal the metal being present as a layer the multilayer coating having electrical properties
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- C03C2218/00—Methods for coating glass
- C03C2218/10—Deposition methods
- C03C2218/15—Deposition methods from the vapour phase
- C03C2218/154—Deposition methods from the vapour phase by sputtering
- C03C2218/156—Deposition methods from the vapour phase by sputtering by magnetron sputtering
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- C03—GLASS; MINERAL OR SLAG WOOL
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- C03C2218/00—Methods for coating glass
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Abstract
The invention provides an ultraviolet radiation assisted electrochromic device low-temperature annealing process, a device and glass, which comprise the following steps: coating an electrochromic film on a substrate to form an electrochromic device; and the electrochromic device is subjected to low-temperature annealing treatment under the irradiation of an ultraviolet light source. When the electrochromic device is subjected to low-temperature annealing treatment, the ultraviolet light source is added for irradiation, and the ultraviolet irradiation is utilized for assisting in annealing, so that the annealing temperature of the electrochromic device can be effectively reduced, the annealing temperature requirement of the polymer transparent flexible substrate is reduced, and the application of the electrochromic film in wearable and other electronic devices is greatly expanded.
Description
Technical Field
The invention relates to the technical field of Electrochromic (EC) glass, in particular to an ultraviolet irradiation assisted electrochromic device low-temperature annealing process, an electrochromic device and glass.
Background
The electrochromic glass can intelligently adjust the radiation of sunlight, selectively absorb or reflect external heat radiation, reduce the energy consumption of buildings or vehicles, and solve the problems of light pollution and dazzling which are gradually serious. Therefore, the electrochromic glass has huge market prospect and energy-saving significance. Due to the obvious advantages of reliability and service life in outdoor use scenes, the all-solid-state inorganic electrochromic film technology becomes the mainstream industrialized technology of intelligent windows and intelligent curtain walls.
The all-solid-state inorganic electrochromic film mainly comprises five layers of nano film layers, namely two transparent conducting layers (TCO), one electrochromic layer (such as tungsten trioxide), one ion conducting layer (IC) and one reverse electrochromic layer (EC such as nickel oxide).
And a small direct current voltage is used for driving L i ions in the film layer, so that the L i ions move in WO3 and NiO and generate reversible redox reaction, the reversible change of color, passing rate reflectivity and the like is realized, and the light and color regulation and control are finally realized.
The current all-solid-state inorganic electrochromic film uses continuous magnetron sputtering coating, and a key step is carried out after the coating is finished, and the annealing temperature is generally over 290 ℃. Such high temperatures have led to the use of only high glass transition temperature glasses as substrates. And polymer transparent flexible substrates such as Polyimide (PI) and polyethylene terephthalate (PET) cannot bear the high-temperature annealing treatment process after the coating of the color-changing film, so that the polymer transparent flexible substrates cannot be used as substrates of electrochromic all-solid-state films at present, which severely limits the application of the electrochromic films in wearable and other electronic devices. Therefore, the annealing temperature of the all-solid-state electrochromic thin film is higher than the glass transition temperature of the current flexible substrate, which is the most fundamental reason for the failure of producing flexible all-solid-state electrochromic devices.
Disclosure of Invention
The invention provides an ultraviolet irradiation assisted low-temperature annealing process for an electrochromic device, and provides a feasible solution for the production of a flexible all-solid-state electrochromic device.
In order to solve the technical problems, the invention adopts the following technical scheme:
an ultraviolet radiation assisted electrochromic device low-temperature annealing process comprises the following steps:
coating an electrochromic film on a substrate to form an electrochromic device;
and the electrochromic device is subjected to low-temperature annealing treatment under the irradiation of an ultraviolet light source.
Further, the irradiation region of the ultraviolet light source is the substrate side and/or the electrochromic film side.
Further, the temperature range of the low-temperature annealing treatment is 150-250 ℃.
An electrochromic device is prepared by the process.
An electrochromic glass comprises the electrochromic device.
According to the technical scheme, when the electrochromic device is subjected to low-temperature annealing treatment, the ultraviolet light source is added for irradiation, and the ultraviolet irradiation is used for assisting in annealing, so that the annealing temperature can be effectively reduced, the annealing temperature requirement of the electrochromic composite film layer is reduced, the annealing temperature is reduced to be lower than the upper limit of the tolerance temperature range of the transparent flexible substrate, and the application of the electrochromic film in wearable and other electronic devices is greatly expanded.
Drawings
FIG. 1 is a flow diagram of the process of the present invention;
FIG. 2 is a transmittance test before the flame-out of the examples;
FIG. 3 is a bright state transmittance test of an example;
FIG. 4 is a transmittance test in a colored state of the examples;
FIG. 5 is a transmittance test of one hour of deelectrification after coloration for the examples.
Detailed Description
A preferred embodiment of the present invention will be described in detail below with reference to the accompanying drawings.
The high-temperature annealing process of the electrochromic device mainly has the following two functions:
1. and (3) recrystallization: the metal oxide generated by sputtering in the film, such as WOx, NiOx and the like, is subjected to chemical bond deconstruction and reconstruction and oxygen vacancy redistribution. The film obtained by sputtering is converted from an amorphous state to a polycrystalline crystalline state through an annealing process, the size of crystalline particles is increased, and the optical bandwidth is reduced.
2. L i is dispersed in the form of atoms in the metal oxide before annealing, high-temperature annealing can enable L i atoms to react with the metal oxide to form corresponding lithium salts L iWOx and L iNiOx, and the L i ions can move freely under the driving of voltage, namely high-temperature annealing can realize the ionization of L i atoms in the film layer to form L i ions which can move freely.
Under the current process conditions, if the EC film formed by sputtering is not subjected to annealing treatment at a sufficient temperature, the electrochromic performance of the film is seriously affected, and the electrochromic performance is specifically represented that the transparent state cannot be faded to a high transmittance, and the colored state cannot be a low transmittance.
While high temperature annealing limits the use of all-solid-state electrochromic films on flexible films, the present invention attempts to use uv assisted annealing in order to lower the annealing temperature. The principle of uv assisted annealing is as follows:
ultraviolet light and blue light have shorter wavelength and higher energy, and in the related research of metal oxide nano particles, because the energy of the ultraviolet light is larger than the energy band gap of a ZnO nano material, researchers can increase and recast a nano ZnO crystal structure by using the blue light and ultraviolet laser irradiation, reduce the energy band bandwidth and further reduce the annealing temperature.
In addition, ultraviolet radiation (UV 185nm and UV285nm) is also widely studied to reduce the activation energy of ingazno (igzo) thin film transistors, and its introduction can reduce the thermal annealing activation temperature from 300 ℃ to 150 ℃, while increasing the electrical properties and stability of the film layer. The ultraviolet combined with low-temperature heat treatment can generate active oxygen radicals and degrade and recombine metal oxide chemical bonds in the IGZO film, thereby effectively increasing the metal-oxide bonds and reducing oxygen vacancies caused by defects. Ultraviolet radiation can decompose weaker chemical bonds and recombine into relatively more stable chemical bonds, and at the same time it can decompose oxygen molecules in the environment into active oxygen atoms, which react with metal elements in the film to reduce oxygen vacancies.
The ultraviolet radiation also has application in lithium salt containing oxometallate, lithium battery anode material metal oxide L iMn2O4Very similar to the lithiated electrochromic material system. Ultraviolet-blue light irradiation is used to initiate Mn4+ hole-electron pairs and further oxidize Mn3+ in the material to Mn4+ while more is simultaneously usedL i + is released, thereby enabling faster charging and discharging.
On the basis of theory, experiments prove that the invention provides the process for annealing the all-solid-state electrochromic film by using ultraviolet radiation assistance, and the annealing effect of the all-solid-state electrochromic film can be realized at a lower temperature
As shown in fig. 1, the ultraviolet radiation assisted low temperature annealing process for electrochromic device includes:
s1, coating the electrochromic film on the substrate to form an electrochromic device;
and S2, carrying out low-temperature annealing treatment on the electrochromic device under the irradiation of an ultraviolet light source.
Wherein the irradiation area of the ultraviolet light source is the substrate side and/or the electrochromic film side.
The ultraviolet light source is an ultraviolet light-emitting diode, a halogen lamp, a xenon lamp or a high-pressure mercury lamp.
The wavelength range of the ultraviolet radiation is 1-440 nm, and the more preferable range is 185-285 nm.
The electrochromic film coating comprises a first transparent conductive oxide layer, an anode electrochromic layer, an ion conducting layer, a cathode electrochromic layer, lithium sputtering and a second transparent conductive oxide layer which are sequentially superposed, and a protective layer, an antireflection layer and the like can be arranged on the second transparent conductive oxide layer.
The temperature range of the low-temperature annealing treatment of the invention is 150-250 ℃, which is lower than 300 ℃ of the common annealing treatment.
The invention also provides an electrochromic device which is prepared by the process.
The invention also provides electrochromic glass comprising the electrochromic device. The electrochromic glass is all-solid-state inorganic electrochromic glass. The all-solid-state electrochromic film is also a metal oxide film in nature, and the ultraviolet radiation assisted annealing can effectively reduce the annealing temperature.
All electrochromic devices are prepared by a magnetron sputtering method, and then annealing treatment is carried out by using different annealing temperatures and ultraviolet irradiation conditions. The initial sample size was 10cm x 10cm, the substrate was glass, the film structure was 50nm sio ox (insulating layer)/200 nm FTO (first transparent conductive oxide layer)/200 nm tungsten trioxide (cathodically coloring layer)/100 nm tantalum oxide (ion conductive layer)/320 nm lithiated nickel oxide (anodically coloring layer)/200 nm ito (second transparent conductive oxide layer), randomly divided into A, B, C, D, E, F groups, each containing 6 samples.
The group A samples are not subjected to any annealing treatment, the group B samples are subjected to low-temperature annealing (180 ℃, the gas atmosphere is air, the atmosphere of the group C-F is also air), the group C samples are subjected to high-temperature annealing at the temperature of 300 ℃, the group D-F samples are subjected to ultraviolet irradiation and low-temperature annealing simultaneously, the annealing temperature of the group D is 150 ℃, the annealing temperature of the group E is 180 ℃, the annealing temperature of the group F is 250 ℃, and the annealing temperature of each group of samples is 55 minutes.
The D-F group is provided with ultraviolet lamps at the upper and lower sides of the device respectively. After the annealing, all samples are assembled into an electrochromic device by the same process, and a lead is led out. Core performance indicators, such as fade state transmittance, stain state transmittance, and memory effect, were then tested for each set of samples.
The device film is formed by K.J, L esker PVD75 multi-target magnetron sputtering system, the annealing furnace is a Boliman-B L MT-1600 high-temperature annealing furnace, the ultraviolet irradiation light source is an ultraviolet lamp with the wavelength of 254nm, the power is 100W, all samples are driven by Keithley 24002V direct-current voltage (driven by colored state 2V and driven by faded state-2V), the transmittance is tested by a L S182 transmittance tester of the brand in forest, and the specific test data are as follows:
the transmittance of the six groups of samples A-F (without any voltage drive) is measured by using the same coating equipment and the same coating process before annealing after coating is completed in the same time period, and the transmittance of each group is shown in figure 2 (the labels of box line graphs are the transmission mean values of the reorganization, and the labels in subsequent pictures are the transmission mean values of the reorganization). It can be seen that the transmittance of the six groups of samples is between 37.2% and 37.7%, which indicates that the samples in each group converge randomly, i.e. the initial states of the groups can be regarded as equal, and the sample difference has no statistically significant difference or influence on the subsequent test.
Subsequently, the transmittance in the transparent state after the annealing (-2V voltage driven maintenance) of each of the samples of groups a to F was also measured (group a was used as a reference group, and no annealing treatment was performed), and the results are shown in fig. 3. The transmittance of the transparent state after the annealing can be used for evaluating the annealing effect, and the better the annealing effect is, the higher the transmittance of the transparent state is theoretically. As can be seen from fig. 3, when the group B samples are subjected to low-temperature annealing only, the transparent state transmittance is only slightly improved, which indicates that the annealing effect is not significant; the transparency of the C group is improved to about 57%, and the low-temperature and ultraviolet treated D-F group is improved to about 58%, which shows that the four C-F groups are sufficient in annealing condition, and compared with high-temperature annealing, the low-temperature and ultraviolet irradiation has even slightly better effect because the ultraviolet irradiation can decompose oxygen molecules in the environment to form active oxygen atoms, thereby accelerating the reaction of the oxygen atoms with metal elements in the film and further reducing oxygen vacancies.
The colored state transmission (-2V voltage driven hold) of each set of samples after de-ignition is tested as shown in fig. 4. It can be seen from the figure that the coloring degrees of the group a and the group B are very low, wherein the group a is colored only to about 27%, and the group B is also colored only to about 19%, which verifies again the analysis result of fig. 3, that is, the low temperature annealing cannot realize the complete annealing function, resulting in that the electrochromic film cannot normally change color. In contrast, the C-F group has a large transmittance drop under 2V driving, wherein the C group transmittance is about 2%, and the D-F group has a depth close to 1%, because the high temperature annealing can reduce the oxygen vacancies in the electrochromic film layer to form more coloring factors (i.e., W is the product of the reduction of the oxygen vacancies in the electrochromic film layer)3+W4+By oxidation to W5+And W6+) While the addition of uv radiation can further oxidize the electrochromic electrode, adding more L i+Is released moreL i of+Can participate in electrochromic reaction, further color and reduce transmittance. The overall oxidation process can be described by the following equation (in W)4+For example):
W4+by oxidation to W6+:O2+2Li2WO3→2WO3+4Li++4e-
W4+By oxidation to W5+:O2+4Li2WO3→2W2O5+4Li++4e-
Fig. 5 shows the transmittance of each group of samples after maintaining the color with 2V voltage and then removing the power supply, and it can be seen that the C-F group of samples all have good memory effect, and the transmittance is maintained below 4%, therefore, the memory effect of the electrochromic device is not affected by using ultraviolet radiation.
The above-mentioned embodiments are merely illustrative of the preferred embodiments of the present invention, and do not limit the scope of the present invention, and various modifications and improvements made to the technical solution of the present invention by those skilled in the art without departing from the spirit of the present invention should fall within the protection scope defined by the claims of the present invention.
Claims (10)
1. An ultraviolet radiation assisted electrochromic device low-temperature annealing process is characterized by comprising the following steps:
coating an electrochromic film on a substrate to form an electrochromic device;
and the electrochromic device is subjected to low-temperature annealing treatment under the irradiation of an ultraviolet light source.
2. The electrochromic device low-temperature annealing process according to claim 1, wherein the irradiation region of the ultraviolet light source is a substrate side and/or an electrochromic film side.
3. The electrochromic device low-temperature annealing process according to claim 1, wherein the ultraviolet light source is an ultraviolet light emitting diode, a halogen lamp, a xenon lamp or a high-pressure mercury lamp.
4. The electrochromic device low-temperature annealing process according to claim 1, wherein the ultraviolet radiation wavelength range is 1-440 nm.
5. The electrochromic device low-temperature annealing process according to claim 4, wherein the ultraviolet radiation wavelength range is 185nm-285 nm.
6. The electrochromic device low-temperature annealing process according to claim 1, wherein the electrochromic thin film coating film comprises a first transparent conductive oxide layer, an anode electrochromic layer, an ion conducting layer, a cathode electrochromic layer, lithium sputtering and a second transparent conductive oxide layer which are sequentially stacked.
7. The electrochromic device low-temperature annealing process according to claim 1, wherein the temperature of the low-temperature annealing treatment is in the range of 150 ℃ to 250 ℃.
8. An electrochromic device, characterized in that it is produced by a process according to any one of claims 1-7.
9. An electrochromic glazing comprising an electrochromic device according to claim 8.
10. The electrochromic glass according to claim 9, characterized in that it is an all-solid-state inorganic electrochromic glass.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202010374096.3A CN111410440A (en) | 2020-05-06 | 2020-05-06 | Ultraviolet irradiation assisted electrochromic device low-temperature annealing process, device and glass |
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| CN115786863A (en) * | 2022-11-30 | 2023-03-14 | 山东省科学院新材料研究所 | Electro-optical element with potassium tantalate-niobate crystal and electrode in ohmic contact and preparation method thereof |
| CN117263526A (en) * | 2023-10-25 | 2023-12-22 | 苏州光昛智能科技有限公司 | Post-treatment method for improving electrochromic film performance |
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