CN117806089A - All-solid-state electrochromic device and preparation method thereof - Google Patents

All-solid-state electrochromic device and preparation method thereof Download PDF

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CN117806089A
CN117806089A CN202311848512.9A CN202311848512A CN117806089A CN 117806089 A CN117806089 A CN 117806089A CN 202311848512 A CN202311848512 A CN 202311848512A CN 117806089 A CN117806089 A CN 117806089A
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oxide
color
dielectric film
solid
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赵俊亮
陶鑫杰
曹小虎
邹玉君
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Shanghai Centaur Enterprise Development Group Co ltd
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Shanghai Centaur Enterprise Development Group Co ltd
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Abstract

The invention relates to the technical field of electrochromic devices, in particular to an all-solid-state electrochromic device and a preparation method thereof. The invention provides an all-solid-state electrochromic device which comprises a transparent substrate, a fourth dielectric film layer, a first functional layer, a first color-changing layer, a first dielectric film layer, an ion providing and conducting layer, a second dielectric film layer, a second color-changing layer, a third dielectric film layer, a second functional layer and a protective layer which are sequentially stacked; the first color-changing layer is made of a mixture of nickel oxide and vanadium oxide and/or single-phase nickel-vanadium oxide, and the second color-changing layer is made of tungsten oxide. The all-solid-state electrochromic device has a short response time and high contrast.

Description

All-solid-state electrochromic device and preparation method thereof
Technical Field
The invention relates to the technical field of electrochromic devices, in particular to an all-solid-state electrochromic device and a preparation method thereof.
Background
Electrochromic devices can be classified into solution type, gel type, all solid type, etc. according to the morphology of electrochromic materials. Electrochromic devices in which the ion-providing conductive layer is contained in a solid state form and the thin film constitutes an all-solid state are referred to as all-solid state see-through electrochromic devices.
The typical structure of the existing all-solid-state electrochromic device comprises a substrate, a transparent conductor, a first color-changing layer, an ion conducting layer, a second color-changing layer and a transparent conductor, wherein the first color-changing layer (ion storage layer) is nickel oxide, and a nickel material is magnetic and has high sputtering difficulty. The existing all-solid-state electrochromic device has the defect that the response time of the device is long and is 4-6 minutes, and the quick response requirement of automobile users cannot be met.
Disclosure of Invention
The invention aims to provide an all-solid-state electrochromic device and a preparation method thereof. The all-solid-state electrochromic device has a short response time and high contrast.
In order to achieve the above object, the present invention provides the following technical solutions:
the invention provides an all-solid-state electrochromic device which comprises a transparent substrate, a fourth dielectric film layer, a first functional layer, a first color-changing layer, a first dielectric film layer, an ion providing and conducting layer, a second dielectric film layer, a second color-changing layer, a third dielectric film layer, a second functional layer and a protective layer which are sequentially stacked;
the first color-changing layer is made of a mixture of nickel oxide and vanadium oxide and/or single-phase nickel-vanadium oxide, and the second color-changing layer is made of tungsten oxide.
Preferably, the transparent substrate is a common glass substrate, a quartz glass substrate or a transparent plastic substrate.
Preferably, the first dielectric film layer, the second dielectric film layer, the third dielectric film layer and the fourth dielectric film layer are transparent insulating layers;
the thickness of the transparent insulating layer is 5-200 nm; the transparent insulating layer is made of one or more of silicon oxide, silicon nitride, zinc oxide, aluminum oxide, silicon aluminum oxide, indium tin oxide, tungsten oxide and azo compounds.
Preferably, the first functional layer and the second functional layer are transparent conductor layers;
the surface sheet resistance of the transparent conductor layer is less than or equal to 100 omega/≡and the thickness is 50-300 nm;
the transparent conductor layer is made of one or more of ITO, FTO, ATO and AZO.
Preferably, the mass percentage of the vanadium oxide in the mixture of the nickel oxide and the vanadium oxide is 1-50%;
the vanadium oxide is one or more of vanadium oxide, vanadium monoxide, vanadium trioxide, vanadium dioxide and vanadium pentoxide;
the nickel oxide in the mixture of the nickel oxide and the vanadium oxide is one or more of nickel oxide, nickel sesquioxide, nickel hydroxide oxide and nickel hydroxide;
The single-phase nickel-vanadium oxide is nickel vanadate and NiO 6 V 2 、Ni 3 V 2 O 8 And NiV 3 O 8 One or more of them.
Preferably, the surface sheet resistance of the first color-changing layer is more than or equal to 0.8Ω/≡and the thickness is 50-400 nm;
the material of the first color-changing layer is nano amorphous or crystalline.
Preferably, the surface sheet resistance of the second color-changing layer is more than or equal to 2Ω/≡, and the thickness is 100-900 nm;
the tungsten oxide is an amorphous nanoparticle.
Preferably, the ion providing and conducting layer is made of one or more of lithium salt, lithium oxide and lithium oxynitride;
the material of the ion providing and conducting layer is of an amorphous structure, and the thickness of the ion providing and conducting layer is 100-800 nm.
Preferably, the thickness of the protective layer is 20-500 nm;
the protective layer is a metal layer, an inorganic oxide layer or a high polymer film.
The invention also provides a preparation method of the all-solid-state electrochromic device, which comprises the following steps:
and sputtering a fourth dielectric film layer, a first functional layer, a first color-changing layer, a first dielectric film layer, an ion providing and conducting layer, a second dielectric film layer, a second color-changing layer, a third dielectric film layer, a second functional layer and a protective layer on the surface of the transparent substrate in sequence to obtain the all-solid-state electrochromic device.
The invention provides an all-solid-state electrochromic device which comprises a transparent substrate, a fourth dielectric film layer, a first functional layer, a first color-changing layer, a first dielectric film layer, an ion providing and conducting layer, a second dielectric film layer, a second color-changing layer, a third dielectric film layer, a second functional layer and a protective layer which are sequentially stacked; the first color-changing layer is made of a mixture of nickel oxide and vanadium oxide and/or single-phase nickel-vanadium oxide, and the second color-changing layer is made of tungsten oxide.
Compared with the prior art, the technical scheme provided by the invention has the following excellent effects:
1) The invention adopts the mixture of nickel oxide and vanadium oxide and/or single-phase nickel-vanadium oxide as the first color-changing layer, thereby overcoming the defect of magnetic materials and enabling the response time of the solid electrochromic device to be shorter and 3-8 s;
2) The first dielectric film layer, the second dielectric film layer, the third dielectric film layer and the fourth dielectric film layer can reduce the mutual conduction phenomenon among the film layers, improve the resistivity of the whole film layer in the vertical direction, enhance the relative contrast of the film layers and reduce the leakage current of the whole all-solid-state electrochromic device between two electric fields. Thus, the original state holding time of the all-solid-state electrochromic device is effectively prolonged after power failure.
Drawings
FIG. 1 is a schematic diagram of the structure of an all-solid-state electrochromic device according to the present invention;
FIG. 2 is a schematic diagram of the packaged structure of the all-solid-state electrochromic device according to example 1 and comparative examples 1 to 5;
FIG. 3 is a spectral diagram of the all-solid-state electrochromic device of example 1 in a transparent state and an absorption state;
FIG. 4 is a graph of the transmittance of an all-solid state electrochromic device according to example 1 by voltage regulation;
FIG. 5 is a schematic diagram of the structure of an all-solid-state electrochromic device according to comparative example 1;
FIG. 6 is a schematic diagram of the structure of an all-solid-state electrochromic device according to comparative example 2;
FIG. 7 is a schematic diagram of the structure of an all-solid-state electrochromic device according to comparative example 3;
FIG. 8 is a schematic diagram of the structure of an all-solid-state electrochromic device according to comparative example 4;
FIG. 9 is a schematic diagram of an all-solid-state electrochromic device according to comparative example 5;
FIG. 10 is a cross-sectional scanning electron microscope image of an all-solid-state electrochromic device according to example 1;
FIG. 11 is a cross-sectional scanning electron microscope image of an all solid state electrochromic device according to comparative example 1.
Detailed Description
The invention provides an all-solid-state electrochromic device which comprises a transparent substrate, a fourth dielectric film layer, a first functional layer, a first color-changing layer, a first dielectric film layer, an ion providing and conducting layer, a second dielectric film layer, a second color-changing layer, a third dielectric film layer, a second functional layer and a protective layer which are sequentially stacked;
The first color-changing layer is made of a mixture of nickel oxide and vanadium oxide and/or single-phase nickel-vanadium oxide, and the second color-changing layer is made of tungsten oxide.
In the present invention, the transparent substrate is preferably a common glass substrate, a quartz glass substrate, or a transparent plastic substrate; the material of the transparent plastic substrate is preferably PET. In the present invention, the thickness of the transparent substrate is preferably 0.1 to 10mm, more preferably 1 to 8mm, and most preferably 1 to 4mm.
In the invention, the first dielectric film layer, the second dielectric film layer, the third dielectric film layer and the fourth dielectric film layer are all preferably transparent insulating layers; the thickness of the transparent insulating layer is preferably 5 to 200nm, more preferably 20 to 160nm, and most preferably 50 to 120nm; the material of the transparent insulating layer is preferably one or more of silicon oxide, silicon nitride, zinc oxide, aluminum oxide, silicon aluminum oxide, indium tin oxide, tungsten oxide and azo compound, and when the material of the transparent insulating layer is two or more of the above specific choices, the proportion of the above specific substances is not particularly limited, and the transparent insulating layer is mixed according to any proportion.
In the invention, the first dielectric film layer, the second dielectric film layer, the third dielectric film layer and the fourth dielectric film layer are used for preventing the color-changing layer and the transparent conductive layer from diffusing mutually, ensuring the independence among the film layers and preventing ions from entering the transparent conductive layer. The dielectric film layer is used as a transition layer, so that the phenomenon that ions are diffused in the transparent conductor due to excessive electrification can be prevented.
In the present invention, the first functional layer and the second functional layer are each preferably a transparent conductor layer; the surface sheet resistance of the transparent conductor layer is preferably equal to or less than 100 Ω/≡s, more preferably equal to or less than 80 Ω/≡s, and most preferably equal to or less than 60 Ω/≡s; the thickness is preferably 50 to 300nm, more preferably 100 to 260nm, most preferably 150 to 200nm; the material of the transparent conductor layer is preferably one or more of ITO, FTO, ATO and AZO, and when the material of the transparent conductor layer is two or more of the above specific choices, the invention does not have any special limitation on the ratio of the above specific substances, and the materials can be mixed according to any ratio.
In the invention, the first functional layer and the second functional layer are transparent conductor layers, the transparent conductor layers are used as electric field introduction electrodes, the surfaces of the transparent conductor layers are flat and uniform, and the transparent conductor layers are well combined with the transparent substrate and the first color-changing layer.
In the invention, the material of the first color-changing layer is preferably a mixture of nickel oxide and vanadium oxide and/or single-phase nickel vanadiumOxygen. The mass percentage of the vanadium oxide in the mixture of nickel oxide and vanadium oxide is preferably 1 to 50%, more preferably 1 to 10%, 11 to 20%, 21 to 30%, 31 to 40% or 41 to 50%. In the present invention, the valence state of vanadium in the vanadium oxide is preferably one or more of 0, -1, +1, +2, +3, +4 and +5; the valence state of nickel in the nickel oxide is preferably one or more of-1, +1, +2, +3 and +4. The vanadium oxide is preferably one or more of vanadium oxide, vanadium monoxide, vanadium trioxide, vanadium dioxide and vanadium pentoxide, and when the vanadium oxide is two or more of the above specific choices, the ratio of the above specific substances is not particularly limited, and the mixture can be mixed according to any ratio. In the present invention, the nickel oxide in the mixture of nickel oxide and vanadium oxide is preferably one or more of nickel oxide, nickel sesquioxide, nickel hydroxide and nickel hydroxide, and when the nickel oxide is two or more of the above specific choices, the ratio of the above specific substances is not particularly limited, and the mixture may be mixed according to any ratio. In the invention, the single-phase nickel-vanadium oxide is preferably nickel vanadate or NiO 6 V 2 、Ni 3 V 2 O 8 And NiV 3 O 8 When the single-phase nickel-vanadium-oxygen is two or more of the above specific choices, the invention does not have any special limitation on the ratio of the above specific substances, and the mixture can be mixed according to any ratio.
In the invention, compared with the traditional nickel oxide color-changing layer, the material of the first color-changing layer can ensure that the magnetism of the metal nickel target disappears, thereby being beneficial to improving the sputtering rate and the electrochromic performance.
In the invention, the surface sheet resistance of the first color-changing layer is preferably more than or equal to 0.8kΩ/≡s, more preferably more than or equal to 1kΩ/≡s, and most preferably more than or equal to 2kΩ/≡s; the thickness is preferably 50 to 400nm, more preferably 50 to 100nm, 100 to 200nm, 200 to 300nm or 300 to 400nm; the material of the first color-changing layer is preferably nano amorphous or crystalline.
In the invention, the surface sheet resistance of the second color-changing layer is preferably more than or equal to 2kΩ/≡s, and more preferably is 20-50 kΩ/≡s; the thickness is preferably 100 to 900nm, more preferably 200 to 800nm, most preferably 400 to 600nm; the second color-changing layer is made of tungsten oxide, and the tungsten oxide is amorphous nano particles.
In the invention, when voltage is applied, ions are transferred between the first color-changing layer and the second color-changing layer, and the transmittance of the all-solid-state electrochromic device is changed; the first color-changing layer is in a transparent state during ion implantation, and the visible light transmittance is more than or equal to 75%; the ion is in a coloring state when being migrated, and the visible light transmittance is less than or equal to 10%; the second color-changing layer is in a coloring state when ion implantation, the visible light transmittance is less than or equal to 10%, and is in a transparent state when ion migration occurs, and the visible light transmittance is more than or equal to 80%.
In the present invention, the thickness of the ion-providing and conducting layer is preferably 100 to 800nm, more preferably 200 to 700nm, and most preferably 400 to 600nm; the material of the ion providing and conducting layer is preferably an amorphous structure, the material of the ion providing and conducting layer is preferably one or more of lithium salt, lithium oxide and lithium oxynitride, more preferably one or more of lithium tantalate, lithium niobate, lithium cobaltate, lithium phosphate, lithium iron phosphate, lithium silicate, lithium aluminate, lithium nitride and lithium oxide, and when the material of the ion providing and conducting layer is two or more of the above specific choices, the proportion of the above specific substances is not limited in any way, and the mixture can be mixed according to any proportion.
In the present invention, the ion-providing and conducting layer is capable of supplying lithium ions.
In the present invention, the thickness of the protective layer is preferably 20 to 500nm, more preferably 100 to 400nm, and most preferably 200 to 300nm. In the present invention, the protective layer is preferably a metal layer, an inorganic oxide layer, or a polymer film; the material of the metal layer is preferably one or more of silver, aluminum, copper, titanium, platinum and tungsten; the material of the inorganic oxide layer is preferably one or more of aluminum oxide, silicon oxide, zirconium oxide, silicon aluminum oxide, tungsten oxide, indium tin oxide, titanium oxide and silicon nitride, and when the material of the inorganic oxide layer is two or more of the above specific choices, the ratio of the above specific substances is not particularly limited, and the materials are mixed according to any ratio. The material of the polymer film is preferably PTFE.
In the present invention, the protective layer functions to prevent oxidation of the surface of the second functional layer.
In the invention, the maximum visible light transmittance adjustment range of the all-solid-state electrochromic device is 1-75%, and different transmittances can be obtained by controlling the time and voltage of the voltage applied to the electrode.
In the invention, the bonding between the layers in the all-solid-state electrochromic device is good, in particular, the single first color-changing layer, or the single ion-providing and conducting layer, or the single second color-changing layer is poor in electron conductivity and good in ion conductivity. Each layer is only contacted with the adjacent layer, and cross-layer communication is not generated. On the circuit connection, an external circuit is mainly connected with the transparent conductor layer, and the ion migration inside the device is controlled by applying voltage to the two layers; the working principle is as follows: when a voltage is applied, ions move from the ion-providing and conducting layer to the first color-changing layer, initiating a redox reaction, resulting in a color change of the first color-changing layer. Subsequently, the ions continue to migrate to the second color-changing layer, triggering a redox reaction, resulting in a color change of the second color-changing layer. The electron conductivity of each layer is poor, so that electrons cannot pass through the layer, and the independence of the color change of each layer is ensured. Through the design, the voltage is regulated through an external circuit, so that the color change of the whole device can be accurately controlled.
The invention also provides a preparation method of the all-solid-state electrochromic device, which comprises the following steps:
and sputtering a fourth dielectric film layer, a first functional layer, a first color-changing layer, a first dielectric film layer, an ion providing and conducting layer, a second dielectric film layer, a second color-changing layer, a third dielectric film layer, a second functional layer and a protective layer on the surface of the transparent substrate in sequence to obtain the all-solid-state electrochromic device.
Before sputtering, the transparent substrate is pretreated, preferably, the transparent substrate is heated by ultrapure water in a cleaning tank, then is added with cleaning liquid, is subjected to ultrasonic treatment and lifting by a grading rinsing tank, enters a slow-pull tank for final rinsing, enters a hot air drying box for drying, and finally is inspected to see whether the surface of the glass is clean and no visible hidden injury, scratch, water stain residue and the like exist, so that the surface of the transparent substrate is clean and free of any residues and scratches.
In the present invention, the first color-changing layer is preferably obtained by reactive sputtering of nickel-vanadium alloy, or by sputtering or electron beam evaporation of an oxide target. The sputtering or electron beam evaporation process is not particularly limited in the present invention, and may be performed by a process known to those skilled in the art.
In the present invention, the preparation method of the ion providing and conducting layer preferably includes a magnetron sputtering method or an electron beam evaporation method; the process of the magnetron sputtering method or the electron beam evaporation method is not particularly limited, and may be performed by a process well known to those skilled in the art.
In the present invention, the second color-changing layer is preferably obtained by a reactive magnetron sputtering method for metallic tungsten, or is obtained by sputtering a tungsten oxide target, or is obtained by electron beam evaporation; the sputtering and electron beam evaporation processes are not particularly limited in the present invention, and may be performed by processes well known to those skilled in the art.
In the present invention, the preparation methods of the fourth dielectric film layer, the first functional layer, the first dielectric film layer, the second dielectric film layer, the third dielectric film layer, the second functional layer and the protective layer are preferably magnetron sputtering, and the process of the magnetron sputtering is not limited in any way, and can be performed by adopting a process well known to those skilled in the art.
In the invention, when the first functional layer and the second functional layer are transparent conductor layers, reversible conversion between transmission and absorption states can be realized, namely the transmission type electrochromic device, and the all-solid electrochromic device can be applied to buildings, decoration glass, front and rear windshield glass, side window glass, roof glass, aircraft suspended windows, medium and large-sized mail wheels and all equipment facilities needing light modulation, and has the same functions of energy conservation, intelligence and concealment.
The present invention provides an all-solid electrochromic device and a method for manufacturing the same, which are described in detail below with reference to examples, but they should not be construed as limiting the scope of the present invention.
Example 1
As shown in fig. 1, the all-solid-state electrochromic device comprises a bright substrate (common glass substrate, thickness of 2 mm), a fourth dielectric film (silicon aluminum oxide, thickness of 70 nm), a first functional layer (ITO layer, thickness of 160 nm), a mixture of a first color-changing layer (nickel oxide) and vanadium oxide (vanadium oxide in particular), wherein the mass percentage of the vanadium oxide is 10%, the material is amorphous, the surface sheet resistance is not less than 2KΩ/, the thickness is 300 nm), the first dielectric film (tungsten oxide, thickness is 100nm, the surface sheet resistance is not less than 8KΩ/, the surface sheet resistance is increased in the vertical direction, the ion providing conductive layer (lithium tantalate, thickness is 200nm, the amorphous structure), the second dielectric film (tungsten oxide, thickness is 100nm, the surface sheet resistance is not less than 26KΩ/≡), the second color-changing layer (tungsten oxide, thickness is 400nm, the amorphous porous structure is not less than 40KΩ/≡), the surface sheet resistance is not less than 60nm, the surface sheet resistance is not less than 30 nm, the surface sheet resistance is not less than 50 nm, the surface sheet resistance is not less than 30 nm, and the surface sheet resistance is not more than 30 nm; the first functional layer and the second functional layer are connected with the electrode;
The preparation process comprises the following steps:
1) Heating a common glass substrate by using ultrapure water in a cleaning tank, adding cleaning liquid (specifically alcohol and acetone with volume ratio of 1:1), carrying out ultrasonic treatment and lifting by using a grading rinsing tank, then entering a slow-pulling tank for final rinsing, entering a hot air drying tank for drying, and finally checking whether the surface of the glass is clean and invisible hidden injuries, scratches, water stain residues and the like are not visible, so as to ensure that the surface of the common glass substrate is clean and free of any residues and scratches;
2) Preparing a fourth dielectric film layer on the surface of the common glass substrate by adopting a magnetron sputtering method: placing the common glass substrate treated in the step 1) into a magnetron sputtering cavity, wherein a silicon-aluminum target (purity is more than or equal to 99%) is adopted as a target material, a direct-current power supply is adopted as a sputtering power supply, and the power density is 3W/cm 2 The atmosphere adopts argon-oxygen mixture (the volume percentage of oxygen is 20%), the air pressure is 1Pa, and the sputtering time is 12min, so as to obtain a fourth dielectric film layer;
3) Preparing a first functional layer (transparent conductor layer) on the surface of the fourth dielectric film layer by using a magnetron sputtering method: placing the product obtained in the step 2) into a magnetron sputtering cavity, wherein the target material is an ITO target material, the sputtering power supply is a direct current power supply, and the power density is 2W/cm 2 Sputtering for 10min at room temperature (25 ℃) under the condition that the atmosphere is pure argon and the pressure is 0.5Pa to obtain a first functional layer, and paving a circuit capable of being connected with an electrode on an edge pin of the first functional layer;
4) Preparing a first color-changing layer on the surface of the first functional layer by adopting a magnetron sputtering method: putting the product obtained in the step 3) into a magnetron sputtering cavity, wherein a metal nickel vanadium alloy target (purity is more than or equal to 99%) is selected as a target, a direct current power supply is adopted as a sputtering power supply, and the power density is 3W/cm 2 The atmosphere is a mixed gas of argon and oxygen (the volume percentage of the oxygen is 10%), the air pressure is 1Pa, and the sputtering time is 30min, so that a first color-changing layer is obtained;
5) Preparing a first dielectric film layer on the surface of the first color-changing layer by adopting a magnetron sputtering method: placing the product obtained in the step 4) into a magnetron sputtering cavity, selecting a metal tungsten target (purity is more than or equal to 99%), wherein a sputtering power supply adopts a direct current power supply, and the power density is 3W/cm 2 The atmosphere is a mixed gas of argon and oxygen (the volume percentage of the oxygen is 80%), the air pressure is 1.5Pa, and the sputtering time is 20min, so that a first dielectric film layer is obtained;
6) Preparing ion providing and conducting layers on the surface of the first dielectric film layer by using a magnetron sputtering method: placing the product obtained in the step 5) Putting the powder into a magnetron sputtering cavity, adopting a lithium tantalate target (the purity is more than or equal to 99 percent), adopting a radio frequency power supply as a sputtering power supply, and enabling the power density to be 2W/cm 2 The atmosphere is pure argon, the air pressure is 1Pa, the sputtering time is 30min, and the ion providing and conducting layer is obtained;
7) Preparing a second dielectric film layer on the surface of the ion supply and conduction layer by using a magnetron sputtering method: placing the product obtained in the step 6) into a magnetron sputtering cavity, adopting a metal tungsten target (purity is more than or equal to 99%), and adopting a direct current power supply as a sputtering power supply, wherein the power density is 3W/cm 2 The atmosphere is a mixed gas of argon and oxygen (the volume percentage of the oxygen is 80%), the air pressure is 1.5Pa, and the sputtering time is 20min, so that a second medium layer is obtained;
8) Preparing a second color-changing layer on the surface of the second dielectric film layer by adopting a magnetron sputtering method: placing the product obtained in the step 7) into a magnetron sputtering cavity, adopting a metal tungsten target (purity is more than or equal to 99%), and adopting a direct current power supply as a sputtering power supply, wherein the power density is 3W/cm 2 The atmosphere is a mixed gas of argon and oxygen (the volume percentage of the oxygen is 6%), the air pressure is 2Pa, and the sputtering time is 30min, so that a second color-changing layer is obtained;
9) Preparing a third dielectric film layer on the surface of the second color-changing layer by adopting a magnetron sputtering method: placing the product obtained in the step 8) into a magnetron sputtering cavity, adopting a silicon-aluminum target material (purity is more than or equal to 99%), and adopting a direct-current power supply as a sputtering power supply, wherein the power density is 3W/cm 2 The atmosphere is a mixed gas of argon and oxygen (the volume percentage of the oxygen is 20%), the air pressure is 1Pa, and the sputtering time is 10min, so that a third medium film layer is obtained;
10 Preparing a second functional layer (transparent conductive layer) on the surface of the third dielectric film layer by using a magnetron sputtering method: placing the product obtained in the step 9) into a magnetron sputtering cavity, adopting an ITO target material, and adopting a direct current power supply as a sputtering power supply, wherein the power density is 2W/cm 2 The atmosphere is pure argon, the air pressure is 0.5Pa, and the sputtering time is 20min, so that a second functional layer is obtained; paving a circuit capable of being connected with the electrode on the edge pin of the second functional layer;
11 Using a magnetron sputtering method, in the secondPreparation of a protective layer on the functional surface: placing the product obtained in the step 10) into a magnetron sputtering cavity, adopting a silicon-aluminum target material (purity is more than or equal to 99%), and adopting a direct-current power supply as a sputtering power supply, wherein the power density is 3W/cm 2 The atmosphere is a mixed gas of argon and oxygen (the volume percentage of the oxygen is 20%), the air pressure is 1Pa, and the sputtering time is 30min, so that a protective layer is obtained;
packaging the obtained all-solid-state electrochromic device into a structure shown in fig. 2, wherein the first functional layer and the second functional layer are respectively connected with electrodes;
FIG. 3 is a spectral diagram of the all-solid-state electrochromic device in a transparent state and an absorbing state; as can be seen from fig. 3, the all-solid-state electrochromic device has a good infrared blocking function in the absorption state. The first color-changing layer is in a transparent state when ion implantation, the visible light transmittance is more than 75%, the first color-changing layer is in a coloring state when ion is migrated, and the visible light transmittance is less than 5%; the second color-changing layer is in a coloring state when ions are injected, and the visible light transmittance is below 5%; when the ions migrate out, the transparent state is shown, and the visible light transmittance is more than 75%; the electrochromic device with the structure can be used for buildings, decoration glass, front and rear windshields of automobiles, side window glass and roof glass, aircraft suspended windows, medium and large-sized mail wheels and all equipment and facilities needing light modulation, and has the same functions of energy conservation, intelligence and concealment;
fig. 4 is a graph showing the transmittance of the all-solid-state electrochromic device adjusted by voltage, and as can be seen from fig. 4, the all-solid-state electrochromic device can reach a transmittance ranging from 75% to 30% in 5s at a voltage of 1.5V, can reach a transmittance ranging from 75% to 18% in 5s at a voltage of 2V, and can reach a transmittance ranging from 75% to 5% in 5s at a voltage of 2.5V.
Comparative example 1
As shown in fig. 5, the all-solid-state electrochromic device comprises a transparent substrate (common glass substrate, thickness of 2 mm), a first functional layer (ITO layer, thickness of 160nm, surface sheet resistance of less than or equal to 30Ω/≡), a mixture of a first color-changing layer (nickel oxide in particular) and vanadium oxide (vanadium oxide in particular), wherein the mass percentage of the vanadium oxide is 10%, the material is amorphous, the surface sheet resistance is more than or equal to 800Ω/≡and the thickness is 300 nm), an ion providing and conducting layer (the material is lithium tantalate, the thickness is 200nm and has an amorphous structure), a second color-changing layer (the material is tungsten oxide, thickness is 400nm, amorphous porous loose structure, surface sheet resistance is more than or equal to 2kΩ/≡), a second functional layer (ITO layer, thickness is 300nm, surface sheet resistance is less than or equal to 300Ω/≡) and a protective layer (silicon oxide layer, thickness is 120 nm) which are sequentially stacked from bottom to top; the first functional layer and the second functional layer are connected with the electrode;
the preparation process comprises the following steps:
1) Heating a common glass substrate by using ultrapure water in a cleaning tank, adding cleaning liquid (specifically alcohol and acetone with volume ratio of 1:1), carrying out ultrasonic treatment and lifting by using a grading rinsing tank, then entering a slow-pulling tank for final rinsing, entering a hot air drying tank for drying, and finally checking whether the surface of the glass is clean and invisible hidden injuries, scratches, water stain residues and the like are not visible, so as to ensure that the surface of the common glass substrate is clean and free of any residues and scratches;
2) Preparing a first functional layer (transparent conductor layer) on the surface of the common glass substrate by using a magnetron sputtering method: placing the product obtained in the step 1) into a magnetron sputtering cavity, wherein the target material is an ITO target material, the sputtering power supply is a direct current power supply, and the power density is 2W/cm 2 Sputtering for 10min at room temperature (25 ℃) under the condition that the atmosphere is pure argon and the pressure is 0.5Pa to obtain a first functional layer, and paving a circuit capable of being connected with an electrode on an edge pin of the first functional layer;
3) Preparing a first color-changing layer on the surface of the first functional layer by adopting a magnetron sputtering method: putting the product obtained in the step 2) into a magnetron sputtering cavity, wherein a metal nickel vanadium alloy target (purity is more than or equal to 99%) is selected as a target, a direct current power supply is adopted as a sputtering power supply, and the power density is 3W/cm 2 The atmosphere is a mixed gas of argon and oxygen (the volume percentage of the oxygen is 10%), the air pressure is 1Pa, and the sputtering time is 30min, so that a first color-changing layer is obtained;
4) Preparing ion extraction on the surface of the first color-changing layer by using a magnetron sputtering methodAnd a supply and conduction layer: placing the product obtained in the step 4) into a magnetron sputtering cavity, adopting a lithium tantalate target material (purity is more than or equal to 99%), and adopting a radio frequency power supply as a sputtering power supply, wherein the power density is 2W/cm 2 The atmosphere is pure argon, the air pressure is 1Pa, the sputtering time is 30min, and the ion providing and conducting layer is obtained;
5) Preparing a second color-changing layer on the surface of the ion providing and conducting layer by using a magnetron sputtering method: placing the product obtained in the step 4) into a magnetron sputtering cavity, adopting a metal tungsten target (purity is more than or equal to 99%), and adopting a direct current power supply as a sputtering power supply, wherein the power density is 3W/cm 2 The atmosphere is a mixed gas of argon and oxygen (the volume percentage of the oxygen is 6%), the air pressure is 2Pa, and the sputtering time is 30min, so that a second color-changing layer is obtained;
6) Preparing a second functional layer (transparent conductive layer) on the surface of the second color-changing layer by using a magnetron sputtering method: placing the product obtained in the step 5) into a magnetron sputtering cavity, adopting an ITO target material, and adopting a direct current power supply as a sputtering power supply, wherein the power density is 2W/cm 2 The atmosphere is pure argon, the air pressure is 0.5Pa, and the sputtering time is 20min, so that a second functional layer is obtained; paving a circuit capable of being connected with the electrode on the edge pin of the second functional layer;
7) Preparing a protective layer on the surface of the second function by using a magnetron sputtering method: placing the product obtained in the step 10) into a magnetron sputtering cavity, adopting a silicon-aluminum target material (purity is more than or equal to 99%), and adopting a direct-current power supply as a sputtering power supply, wherein the power density is 1W/cm 2 The atmosphere is a mixed gas of argon and oxygen (the volume percentage of the oxygen is 20%), the air pressure is 0.5Pa, and the sputtering time is 60 minutes, so that the protective layer is obtained;
packaging the obtained all-solid-state electrochromic device into a structure shown in fig. 2, wherein the first functional layer and the second functional layer are respectively connected with electrodes;
the all-solid-state electrochromic device has a good infrared blocking function in an absorption state. The first color-changing layer is in a transparent state when ion implantation, the visible light transmittance is more than 60%, the first color-changing layer is in a coloring state when ion is migrated, and the visible light transmittance is less than 30%; the second color-changing layer is in a coloring state when ions are injected, and the visible light transmittance is below 27%; when the ions migrate out, the transparent state is shown, and the visible light transmittance is more than 75%; the electrochromic device with the structure can be used for buildings, decoration glass, front and rear windshields of automobiles, side window glass and roof glass, aircraft suspended windows, medium and large-sized mail wheels and all equipment and facilities needing light modulation, and has the same functions of energy conservation, intelligence and concealment;
the all-solid-state electrochromic device can achieve a transmittance ranging from 60% to 45% in 5s at a voltage of 1.5V, can achieve a transmittance ranging from 60% to 30% in 5s at a voltage of 2V, and can achieve a transmittance ranging from 60% to 28% in 5s at a voltage of 2.5V.
Comparative example 2
As shown in fig. 6, the all-solid-state electrochromic device comprises, from bottom to top, a bright substrate (common glass substrate, thickness of 2 mm), a first functional layer (ITO layer, thickness of 160nm, surface sheet resistance of no more than 30Ω/≡), a mixture of a first color-changing layer (nickel oxide in particular) and vanadium oxide (vanadium oxide in particular), wherein the mass percentage of vanadium oxide is 10%, the material is amorphous, surface sheet resistance is no less than 800 Ω/≡and thickness is 300 nm), a first dielectric film layer (tungsten oxide, thickness is 100nm, surface sheet resistance is no less than 6kΩ/≡and film layer vertical direction sheet resistance is increased), an ion providing and conducting layer (material is lithium tantalate, thickness is 200nm, amorphous structure), a second color-changing layer (material is tungsten oxide, thickness is 400nm, amorphous porous loose structure, surface sheet resistance is no less than 10kΩ/≡), a second functional layer (ITO layer, thickness is 300 nm), surface sheet resistance is no more than 220 Ω/≡and a protective layer (silicon-aluminum oxide layer, thickness is 200 nm); the first functional layer and the second functional layer are connected with the electrode;
the preparation process comprises the following steps:
1) Heating a common glass substrate by using ultrapure water in a cleaning tank, adding cleaning liquid (specifically alcohol and acetone with volume ratio of 1:1), carrying out ultrasonic treatment and lifting by using a grading rinsing tank, then entering a slow-pulling tank for final rinsing, entering a hot air drying tank for drying, and finally checking whether the surface of the glass is clean and invisible hidden injuries, scratches, water stain residues and the like are not visible, so as to ensure that the surface of the common glass substrate is clean and free of any residues and scratches;
2) Preparing a first functional layer (transparent conductor layer) on the surface of the common glass substrate by using a magnetron sputtering method: placing the product obtained in the step 1) into a magnetron sputtering cavity, wherein the target material is an ITO target material, the sputtering power supply is a direct current power supply, and the power density is 2W/cm 2 Sputtering for 10min at room temperature (25 ℃) under the condition that the atmosphere is pure argon and the pressure is 0.5Pa to obtain a first functional layer, and paving a circuit capable of being connected with an electrode on an edge pin of the first functional layer;
3) Preparing a first color-changing layer on the surface of the first functional layer by adopting a magnetron sputtering method: putting the product obtained in the step 2) into a magnetron sputtering cavity, wherein a metal nickel vanadium alloy target (purity is more than or equal to 99%) is selected as a target, a direct current power supply is adopted as a sputtering power supply, and the power density is 3W/cm 2 The atmosphere is a mixed gas of argon and oxygen (the volume percentage of the oxygen is 10%), the air pressure is 1Pa, and the sputtering time is 30min, so that a first color-changing layer is obtained;
4) Preparing a first dielectric film layer on the surface of the first color-changing layer by adopting a magnetron sputtering method: placing the product obtained in the step 3) into a magnetron sputtering cavity, selecting a metal tungsten target (purity is more than or equal to 99%), wherein a sputtering power supply adopts a direct current power supply, and the power density is 3W/cm 2 The atmosphere is a mixed gas of argon and oxygen (the volume percentage of the oxygen is 80%), the air pressure is 1.5Pa, and the sputtering time is 20min, so that a first dielectric film layer is obtained;
5) Preparing ion providing and conducting layers on the surface of the first dielectric film layer by using a magnetron sputtering method: placing the product obtained in the step 4) into a magnetron sputtering cavity, adopting a lithium tantalate target material (purity is more than or equal to 99%), and adopting a radio frequency power supply as a sputtering power supply, wherein the power density is 2W/cm 2 The atmosphere is pure argon, the air pressure is 1Pa, the sputtering time is 30min, and the ion providing and conducting layer is obtained;
6) Preparing a second color-changing layer on the surface of the ion providing and conducting layer by using a magnetron sputtering method: the step 5) is carried outThe product is put into a magnetron sputtering cavity, a metal tungsten target material (the purity is more than or equal to 99 percent) is adopted, a direct current power supply is adopted as a sputtering power supply, and the power density is 3W/cm 2 The atmosphere is a mixed gas of argon and oxygen (the volume percentage of the oxygen is 6%), the air pressure is 2Pa, and the sputtering time is 30min, so that a second color-changing layer is obtained;
7) Preparing a second functional layer (transparent conductive layer) on the surface of the second color-changing layer by using a magnetron sputtering method: placing the product obtained in the step 6) into a magnetron sputtering cavity, adopting an ITO target material, and adopting a direct current power supply as a sputtering power supply, wherein the power density is 2W/cm 2 The atmosphere is pure argon, the air pressure is 0.5Pa, and the sputtering time is 20min, so that a second functional layer is obtained; paving a circuit capable of being connected with the electrode on the edge pin of the second functional layer;
8) Preparing a protective layer on the surface of the second function by using a magnetron sputtering method: placing the product obtained in the step 7) into a magnetron sputtering cavity, adopting a silicon-aluminum target material (purity is more than or equal to 99%), and adopting a direct-current power supply as a sputtering power supply, wherein the power density is 1W/cm 2 The atmosphere is a mixed gas of argon and oxygen (the volume percentage of the oxygen is 20%), the air pressure is 0.5Pa, and the sputtering time is 60 minutes, so that the protective layer is obtained;
packaging the obtained all-solid-state electrochromic device into a structure shown in fig. 2, wherein the first functional layer and the second functional layer are respectively connected with electrodes;
the all-solid-state electrochromic device has a good infrared blocking function in an absorption state. The first color-changing layer is in a transparent state when ion implantation, the visible light transmittance is more than 65%, the first color-changing layer is in a coloring state when ion is migrated, and the visible light transmittance is less than 25%; the second color-changing layer is in a coloring state when ions are injected, and the visible light transmittance is below 26%; when the ions migrate out, the transparent state is shown, and the visible light transmittance is more than 75%; the electrochromic device with the structure can be used for buildings, decoration glass, front and rear windshields of automobiles, side window glass and roof glass, aircraft suspended windows, medium and large-sized mail wheels and all equipment and facilities needing light modulation, and has the same functions of energy conservation, intelligence and concealment;
The all-solid-state electrochromic device can achieve a transmittance ranging from 65% to 43% in 5s at a voltage of 1.5V, can achieve a transmittance ranging from 65% to 27% in 5s at a voltage of 2V, and can achieve a transmittance ranging from 65% to 25% in 5s at a voltage of 2.5V.
Comparative example 3
As shown in fig. 7, the all-solid-state electrochromic device comprises, from bottom to top, a bright substrate (common glass substrate, thickness of 2 mm), a first functional layer (ITO layer, thickness of 160nm, surface sheet resistance of no more than 30Ω/∈8), a mixture of a first color-changing layer (nickel oxide) and vanadium oxide (vanadium oxide), the mass percentage of vanadium oxide being 10%, the material being amorphous, surface sheet resistance of no less than 800Ω/∈8, thickness of 300 nm), an ion providing and conducting layer (lithium tantalate, thickness of 200nm, amorphous structure), a second dielectric film layer (tungsten oxide, thickness of 100nm, surface sheet resistance of no less than 7kΩ/∈8), a second color-changing layer (tungsten oxide, thickness of 400nm, amorphous porous structure, surface sheet resistance of no less than 1kΩ/∈8), a second functional layer (ITO layer, thickness of 300nm, surface sheet resistance of no more than 160Ω/∈8 nm), and a protective layer (oxide layer, thickness of 120 nm) which are laminated in this order; the first functional layer and the second functional layer are connected with the electrode;
The preparation process comprises the following steps:
1) Heating a common glass substrate by using ultrapure water in a cleaning tank, adding cleaning liquid (specifically alcohol and acetone with volume ratio of 1:1), carrying out ultrasonic treatment and lifting by using a grading rinsing tank, then entering a slow-pulling tank for final rinsing, entering a hot air drying tank for drying, and finally checking whether the surface of the glass is clean and invisible hidden injuries, scratches, water stain residues and the like are not visible, so as to ensure that the surface of the common glass substrate is clean and free of any residues and scratches;
2) Preparing a first functional layer (transparent conductor layer) on the surface of the common glass substrate by using a magnetron sputtering method: placing the product obtained in the step 1) into a magnetron sputtering cavity, wherein the target material is an ITO target material, the sputtering power supply is a direct current power supply, and the power density is 2W/cm 2 Sputtering for 10min at room temperature (25 ℃) under the condition that the atmosphere is pure argon and the pressure is 0.5Pa to obtain a first functional layer, and paving a circuit capable of being connected with an electrode on an edge pin of the first functional layer;
3) Preparing a first color-changing layer on the surface of the first functional layer by adopting a magnetron sputtering method: putting the product obtained in the step 2) into a magnetron sputtering cavity, wherein a metal nickel vanadium alloy target (purity is more than or equal to 99%) is selected as a target, a direct current power supply is adopted as a sputtering power supply, and the power density is 3W/cm 2 The atmosphere is a mixed gas of argon and oxygen (the volume percentage of the oxygen is 10%), the air pressure is 1Pa, and the sputtering time is 30min, so that a first color-changing layer is obtained;
4) Preparing an ion supply and conductive layer on the surface of the first color-changing layer by using a magnetron sputtering method: placing the product obtained in the step 3) into a magnetron sputtering cavity, adopting a lithium tantalate target material (purity is more than or equal to 99%), and adopting a radio frequency power supply as a sputtering power supply, wherein the power density is 2W/cm 2 The atmosphere is pure argon, the air pressure is 1Pa, the sputtering time is 30min, and the ion providing and conducting layer is obtained;
5) Preparing a second dielectric film layer on the surface of the ion supply and conduction layer by using a magnetron sputtering method: placing the product obtained in the step 4) into a magnetron sputtering cavity, adopting a metal tungsten target (purity is more than or equal to 99%), and adopting a direct current power supply as a sputtering power supply, wherein the power density is 3W/cm 2 The atmosphere is a mixed gas of argon and oxygen (the volume percentage of the oxygen is 80%), the air pressure is 1.5Pa, and the sputtering time is 20min, so that a second medium layer is obtained;
6) Preparing a second color-changing layer on the surface of the second dielectric film layer by adopting a magnetron sputtering method: placing the product obtained in the step 5) into a magnetron sputtering cavity, adopting a metal tungsten target (purity is more than or equal to 99%), and adopting a direct current power supply as a sputtering power supply, wherein the power density is 3W/cm 2 The atmosphere is a mixed gas of argon and oxygen (the volume percentage of the oxygen is 6%), the air pressure is 2Pa, and the sputtering time is 30min, so that a second color-changing layer is obtained;
7) Preparing a second functional layer (transparent conductive layer) on the surface of the second color-changing layer by using a magnetron sputtering method: putting the product obtained in the step 6) into a magnetIn the sputtering control cavity, an ITO target material is adopted, a direct current power supply is adopted as a sputtering power supply, and the power density is 2W/cm 2 The atmosphere is pure argon, the air pressure is 0.5Pa, and the sputtering time is 20min, so that a second functional layer is obtained; paving a circuit capable of being connected with the electrode on the edge pin of the second functional layer;
8) Preparing a protective layer on the surface of the second function by using a magnetron sputtering method: placing the product obtained in the step 10) into a magnetron sputtering cavity, adopting a silicon-aluminum target material (purity is more than or equal to 99%), and adopting a direct-current power supply as a sputtering power supply, wherein the power density is 3W/cm 2 The atmosphere is a mixed gas of argon and oxygen (the volume percentage of the oxygen is 20%), the air pressure is 1Pa, and the sputtering time is 30min, so that a protective layer is obtained;
packaging the obtained all-solid-state electrochromic device into a structure shown in fig. 2, wherein the first functional layer and the second functional layer are respectively connected with electrodes;
The all-solid-state electrochromic device has a good infrared blocking function in an absorption state. The first color-changing layer is in a transparent state when ion implantation, the visible light transmittance is more than 68%, the first color-changing layer is in a colored state when ion is migrated, and the visible light transmittance is less than 23%; the second color-changing layer is in a coloring state when ions are injected, and the visible light transmittance is below 24%; when the ions migrate out, the transparent state is shown, and the visible light transmittance is more than 75%; the electrochromic device with the structure can be used for buildings, decoration glass, front and rear windshields of automobiles, side window glass and roof glass, aircraft suspended windows, medium and large-sized mail wheels and all equipment and facilities needing light modulation, and has the same functions of energy conservation, intelligence and concealment;
the all-solid-state electrochromic device can achieve a transmittance ranging from 68% to 44% in 5s at a voltage of 1.5V, can achieve a transmittance ranging from 68% to 26% in 5s at a voltage of 2V, and can achieve a transmittance ranging from 68% to 24% in 5s at a voltage of 2.5V.
Comparative example 4
As shown in fig. 8, the all-solid-state electrochromic device comprises, from bottom to top, a bright substrate (common glass substrate, thickness of 2 mm), a first functional layer (ITO layer, thickness of 160nm, surface sheet resistance of no more than 30Ω/∈), a first color-changing layer (mixture of nickel oxide (nickel oxide in particular) and vanadium oxide (vanadium oxide in particular), wherein the mass percentage of vanadium oxide is 10%, the material is amorphous, surface sheet resistance is no less than 800Ω/∈and thickness is 300 nm), a first dielectric film layer (material is tungsten oxide, thickness is 100nm, surface sheet resistance is no less than 6kΩ/∈and thickness is increased in the vertical direction of the film layer), an ion providing and conducting layer (material is lithium tantalate, thickness is 200nm, amorphous structure), a second dielectric film layer (material is tungsten oxide, thickness is 100nm, surface sheet resistance is no less than 20kΩ/∈), a second color-changing layer (material is tungsten oxide, thickness is 400nm, no-porous loose structure is formed, surface sheet resistance is no less than 23kΩ/∈), a second functional layer (ITO thickness is no less than 300kΩ/∈) and thickness is no more than 120nm; the first functional layer and the second functional layer are connected with the electrode;
The preparation process comprises the following steps:
1) Heating a common glass substrate by using ultrapure water in a cleaning tank, adding cleaning liquid (specifically alcohol and acetone with volume ratio of 1:1), carrying out ultrasonic treatment and lifting by using a grading rinsing tank, then entering a slow-pulling tank for final rinsing, entering a hot air drying tank for drying, and finally checking whether the surface of the glass is clean and invisible hidden injuries, scratches, water stain residues and the like are not visible, so as to ensure that the surface of the common glass substrate is clean and free of any residues and scratches;
2) Preparing a first functional layer (transparent conductor layer) on the surface of the common glass substrate by using a magnetron sputtering method: placing the product obtained in the step 1) into a magnetron sputtering cavity, wherein the target material is an ITO target material, the sputtering power supply is a direct current power supply, and the power density is 2W/cm 2 Sputtering for 10min at room temperature (25 ℃) under the condition that the atmosphere is pure argon and the pressure is 0.5Pa to obtain a first functional layer, and paving a circuit capable of being connected with an electrode on an edge pin of the first functional layer;
3) Preparing a first color-changing layer on the surface of the first functional layer by adopting a magnetron sputtering method: putting the product obtained in the step 2) into a magnetIn the sputtering control cavity, the target material is a metal nickel-vanadium alloy target material (purity is more than or equal to 99 percent), the sputtering power supply is a direct current power supply, and the power density is 3W/cm 2 The atmosphere is a mixed gas of argon and oxygen (the volume percentage of the oxygen is 10%), the air pressure is 1Pa, and the sputtering time is 30min, so that a first color-changing layer is obtained;
4) Preparing a first dielectric film layer on the surface of the first color-changing layer by adopting a magnetron sputtering method: placing the product obtained in the step 3) into a magnetron sputtering cavity, selecting a metal tungsten target (purity is more than or equal to 99%), wherein a sputtering power supply adopts a direct current power supply, and the power density is 3W/cm 2 The atmosphere is a mixed gas of argon and oxygen (the volume percentage of the oxygen is 80%), the air pressure is 1.5Pa, and the sputtering time is 20min, so that a first dielectric film layer is obtained;
5) Preparing ion providing and conducting layers on the surface of the first dielectric film layer by using a magnetron sputtering method: placing the product obtained in the step 4) into a magnetron sputtering cavity, adopting a lithium tantalate target material (purity is more than or equal to 99%), and adopting a radio frequency power supply as a sputtering power supply, wherein the power density is 2W/cm 2 The atmosphere is pure argon, the air pressure is 1Pa, the sputtering time is 30min, and the ion providing and conducting layer is obtained;
6) Preparing a second dielectric film layer on the surface of the ion supply and conduction layer by using a magnetron sputtering method: placing the product obtained in the step 5) into a magnetron sputtering cavity, adopting a metal tungsten target (purity is more than or equal to 99%), and adopting a direct current power supply as a sputtering power supply, wherein the power density is 3W/cm 2 The atmosphere is a mixed gas of argon and oxygen (the volume percentage of the oxygen is 80%), the air pressure is 1.5Pa, and the sputtering time is 20min, so that a second medium layer is obtained;
7) Preparing a second color-changing layer on the surface of the second dielectric film layer by adopting a magnetron sputtering method: placing the product obtained in the step 6) into a magnetron sputtering cavity, adopting a metal tungsten target (purity is more than or equal to 99%), and adopting a direct current power supply as a sputtering power supply, wherein the power density is 3W/cm 2 The atmosphere is a mixed gas of argon and oxygen (the volume percentage of the oxygen is 6%), the air pressure is 2Pa, and the sputtering time is 30min, so that a second color-changing layer is obtained;
8) And a magnetron sputtering method is adopted to perform the second color changeSecond functional layer (transparent conductive layer) is prepared on the surface of the layer: placing the product obtained in the step 7) into a magnetron sputtering cavity, adopting an ITO target material, and adopting a direct current power supply as a sputtering power supply, wherein the power density is 2W/cm 2 The atmosphere is pure argon, the air pressure is 0.5Pa, and the sputtering time is 20min, so that a second functional layer is obtained; paving a circuit capable of being connected with the electrode on the edge pin of the second functional layer;
9) Preparing a protective layer on the surface of the second function by using a magnetron sputtering method: placing the product obtained in the step 8) into a magnetron sputtering cavity, adopting a silicon-aluminum target material (purity is more than or equal to 99%), and adopting a direct-current power supply as a sputtering power supply, wherein the power density is 3W/cm 2 The atmosphere is a mixed gas of argon and oxygen (the volume percentage of the oxygen is 20%), the air pressure is 1Pa, and the sputtering time is 30min, so that a protective layer is obtained;
packaging the obtained all-solid-state electrochromic device into a structure shown in fig. 2, wherein the first functional layer and the second functional layer are respectively connected with electrodes;
the all-solid-state electrochromic device has a good infrared blocking function in an absorption state. The first color-changing layer is in a transparent state when ion implantation, the visible light transmittance is more than 70%, the first color-changing layer is in a coloring state when ion is migrated, and the visible light transmittance is less than 20%; the second color-changing layer is in a coloring state when ions are injected, and the visible light transmittance is below 18%; when the ions migrate out, the transparent state is shown, and the visible light transmittance is more than 75%; the electrochromic device with the structure can be used for buildings, decoration glass, front and rear windshields of automobiles, side window glass and roof glass, aircraft suspended windows, medium and large-sized mail wheels and all equipment and facilities needing light modulation, and has the same functions of energy conservation, intelligence and concealment;
the all-solid-state electrochromic device can achieve a transmittance ranging from 70% to 45% in 5s at a voltage of 1.5V, can achieve a transmittance ranging from 70% to 27% in 5s at a voltage of 2V, and can achieve a transmittance ranging from 70% to 20% in 5s at a voltage of 2.5V.
Comparative example 5
As shown in fig. 9, the all-solid-state electrochromic device comprises, from bottom to top, a bright substrate (common glass substrate, thickness of 2 mm), a first functional layer (ITO layer, thickness of 160nm, surface sheet resistance of no more than 30Ω/≡), a first color-changing layer (mixture of nickel oxide (nickel oxide in particular) and vanadium oxide (vanadium oxide in particular), wherein the mass percentage of vanadium oxide is 10%, the material is amorphous, surface sheet resistance is no less than 800 Ω/≡and thickness of 300 nm), a first dielectric film layer (tungsten oxide, thickness of 100nm, surface sheet resistance is no less than 6kΩ/≡and thickness of film layer increases in the vertical direction), an ion providing and conducting layer (material is lithium tantalate, thickness of 200nm, amorphous structure), a second dielectric film layer (material is tungsten oxide, thickness of 100nm, surface sheet resistance is no less than 20kΩ/≡), a second color-changing layer (material is tungsten oxide, thickness of 400nm, non-porous loose structure, surface sheet resistance is no less than 23kΩ/≡), a third dielectric film layer (thickness of no less than 60kΩ/≡) and thickness of the surface sheet resistance is no less than 60Ω/≡0nm, surface sheet resistance is no less than 1200Ω/≡and thickness of the functional layer is no more than 20Ω/surface layer (ITO layer); the first functional layer and the second functional layer are connected with the electrode;
The preparation process comprises the following steps:
1) Heating a common glass substrate by using ultrapure water in a cleaning tank, adding cleaning liquid (specifically alcohol and acetone with volume ratio of 1:1), carrying out ultrasonic treatment and lifting by using a grading rinsing tank, then entering a slow-pulling tank for final rinsing, entering a hot air drying tank for drying, and finally checking whether the surface of the glass is clean and invisible hidden injuries, scratches, water stain residues and the like are not visible, so as to ensure that the surface of the common glass substrate is clean and free of any residues and scratches;
2) Preparing a first functional layer (transparent conductor layer) on the surface of the common glass substrate by using a magnetron sputtering method: placing the product obtained in the step 1) into a magnetron sputtering cavity, wherein the target material is an ITO target material, the sputtering power supply is a direct current power supply, and the power density is 2W/cm 2 Sputtering for 10min at room temperature (25deg.C) under pure argon at pressure of 0.5Pa to obtain a first functional layer, and laying edge pins of the first functional layer capable of connecting with electrodesA connected circuit;
3) Preparing a first color-changing layer on the surface of the first functional layer by adopting a magnetron sputtering method: putting the product obtained in the step 2) into a magnetron sputtering cavity, wherein a metal nickel vanadium alloy target (purity is more than or equal to 99%) is selected as a target, a direct current power supply is adopted as a sputtering power supply, and the power density is 3W/cm 2 The atmosphere is a mixed gas of argon and oxygen (the volume percentage of the oxygen is 80%), the air pressure is 1.5Pa, and the sputtering time is 20min, so that a first color-changing layer is obtained;
4) Preparing a first dielectric film layer on the surface of the first color-changing layer by adopting a magnetron sputtering method: placing the product obtained in the step 3) into a magnetron sputtering cavity, selecting a metal tungsten target (purity is more than or equal to 99%), wherein a sputtering power supply adopts a direct current power supply, and the power density is 3W/cm 2 The atmosphere is a mixed gas of argon and oxygen (the volume percentage of the oxygen is 80%), the air pressure is 1.5Pa, and the sputtering time is 20min, so that a first dielectric film layer is obtained;
5) Preparing ion providing and conducting layers on the surface of the first dielectric film layer by using a magnetron sputtering method: placing the product obtained in the step 4) into a magnetron sputtering cavity, adopting a lithium tantalate target material (purity is more than or equal to 99%), and adopting a radio frequency power supply as a sputtering power supply, wherein the power density is 2W/cm 2 The atmosphere is pure argon, the air pressure is 1Pa, the sputtering time is 30min, and the ion providing and conducting layer is obtained;
6) Preparing a second dielectric film layer on the surface of the ion supply and conduction layer by using a magnetron sputtering method: placing the product obtained in the step 5) into a magnetron sputtering cavity, adopting a metal tungsten target (purity is more than or equal to 99%), and adopting a direct current power supply as a sputtering power supply, wherein the power density is 3W/cm 2 The atmosphere is a mixed gas of argon and oxygen (the volume percentage of the oxygen is 80%), the air pressure is 1.5Pa, and the sputtering time is 20min, so that a second medium layer is obtained;
7) Preparing a second color-changing layer on the surface of the second dielectric film layer by adopting a magnetron sputtering method: placing the product obtained in the step 6) into a magnetron sputtering cavity, adopting a metal tungsten target (purity is more than or equal to 99%), and adopting a direct current power supply as a sputtering power supply, wherein the power density is 3W/cm 2 The atmosphere is a mixture of argon and oxygen (oxygen6% by volume, air pressure of 2Pa and sputtering time of 30min to obtain a second color-changing layer;
8) Preparing a third dielectric film layer on the surface of the second color-changing layer by adopting a magnetron sputtering method: placing the product obtained in the step 7) into a magnetron sputtering cavity, adopting a silicon-aluminum target material (purity is more than or equal to 99%), and adopting a direct-current power supply as a sputtering power supply, wherein the power density is 3W/cm 2 The atmosphere is a mixed gas of argon and oxygen (the volume percentage of the oxygen is 20%), the air pressure is 1Pa, and the sputtering time is 10min, so that a third medium film layer is obtained;
9) Preparing a second functional layer (transparent conductive layer) on the surface of the third dielectric film layer by using a magnetron sputtering method: placing the product obtained in the step 8) into a magnetron sputtering cavity, adopting an ITO target material, and adopting a direct current power supply as a sputtering power supply, wherein the power density is 2W/cm 2 The atmosphere is pure argon, the air pressure is 0.5Pa, and the sputtering time is 20min, so that a second functional layer is obtained; paving a circuit capable of being connected with the electrode on the edge pin of the second functional layer;
10 Using a magnetron sputtering method to prepare a protective layer on the surface of the second function: placing the product obtained in the step 10) into a magnetron sputtering cavity, adopting a silicon-aluminum target material (purity is more than or equal to 99%), and adopting a direct-current power supply as a sputtering power supply, wherein the power density is 3W/cm 2 The atmosphere is a mixed gas of argon and oxygen (the volume percentage of the oxygen is 20%), the air pressure is 1Pa, and the sputtering time is 30min, so that a protective layer is obtained;
packaging the obtained all-solid-state electrochromic device into a structure shown in fig. 2, wherein the first functional layer and the second functional layer are respectively connected with electrodes;
the all-solid-state electrochromic device has a good infrared blocking function in an absorption state. The first color-changing layer is in a transparent state when ion implantation, the visible light transmittance is more than 75%, the first color-changing layer is in a coloring state when ion is migrated, and the visible light transmittance is less than 12%; the second color-changing layer is in a coloring state when ions are injected, and the visible light transmittance is below 10%; when the ions migrate out, the transparent state is shown, and the visible light transmittance is more than 75%; the electrochromic device with the structure can be used for buildings, decoration glass, front and rear windshields of automobiles, side window glass and roof glass, aircraft suspended windows, medium and large-sized mail wheels and all equipment and facilities needing light modulation, and has the same functions of energy conservation, intelligence and concealment;
The all-solid-state electrochromic device can achieve a transmittance ranging from 75% to 40% in 5s at a voltage of 1.5V, can achieve a transmittance ranging from 75% to 24% in 5s at a voltage of 2V, and can achieve a transmittance ranging from 75% to 10% in 5s at a voltage of 2.5V.
Fig. 10 is a sectional scanning electron microscope view of the all-solid-state electrochromic device according to example 1, fig. 11 is a sectional scanning electron microscope view of the all-solid-state electrochromic device according to comparative example 1, and it is apparent from fig. 10 to 11 that different hierarchical structures can be clearly identified on the sectional views. The layers are clearly visible, and the layers are combined through interfaces, so that tight and seamless connection is ensured, and the occurrence of cracks or bubbles is avoided. In the first color-changing layer and the second color-changing layer, the particle and grain structure is remarkable, which may be closely related to oxidation-reduction reaction and color change. The surface flatness of each layer is good, and the uniformity and optical performance of the film are maintained.
In summary, adding a dielectric layer in the all-solid-state electrochromic device can effectively reduce the mutual conduction phenomenon between the film layers, improve the resistivity of the whole film layer in the vertical direction, enhance the relative contrast of the film layer, and reduce the leakage current of the whole all-solid-state electrochromic device between two electric fields, so that the original state retention time of the all-solid-state electrochromic device after power failure is effectively prolonged.
The foregoing is merely a preferred embodiment of the present invention and it should be noted that modifications and adaptations to those skilled in the art may be made without departing from the principles of the present invention, which are intended to be comprehended within the scope of the present invention.

Claims (10)

1. An all-solid-state electrochromic device is characterized by comprising a transparent substrate, a fourth dielectric film layer, a first functional layer, a first color-changing layer, a first dielectric film layer, an ion providing and conducting layer, a second dielectric film layer, a second color-changing layer, a third dielectric film layer, a second functional layer and a protective layer which are sequentially laminated;
the first color-changing layer is made of a mixture of nickel oxide and vanadium oxide and/or single-phase nickel-vanadium oxide, and the second color-changing layer is made of tungsten oxide.
2. The all-solid-state electrochromic device according to claim 1, wherein said transparent substrate is a plain glass substrate, a quartz glass substrate or a transparent plastic substrate.
3. The all-solid-state electrochromic device according to claim 1, wherein the first dielectric film layer, the second dielectric film layer, the third dielectric film layer and the fourth dielectric film layer are transparent insulating layers;
The thickness of the transparent insulating layer is 5-200 nm; the transparent insulating layer is made of one or more of silicon oxide, silicon nitride, zinc oxide, aluminum oxide, silicon aluminum oxide, indium tin oxide, tungsten oxide and azo compounds.
4. The all-solid-state electrochromic device according to claim 1, wherein the first and second functional layers are transparent conductor layers;
the surface sheet resistance of the transparent conductor layer is less than or equal to 100 omega/≡and the thickness is 50-300 nm;
the transparent conductor layer is made of one or more of ITO, FTO, ATO and AZO.
5. The all-solid-state electrochromic device according to claim 1, wherein the mass percentage of vanadium oxide in the mixture of nickel oxide and vanadium oxide is 1-50%;
the vanadium oxide is one or more of vanadium oxide, vanadium monoxide, vanadium trioxide, vanadium dioxide and vanadium pentoxide;
the nickel oxide in the mixture of the nickel oxide and the vanadium oxide is one or more of nickel oxide, nickel sesquioxide, nickel hydroxide oxide and nickel hydroxide;
the single-phase nickel-vanadium oxide is nickel vanadate and NiO 6 V 2 、Ni 3 V 2 O 8 And NiV 3 O 8 One or more of them.
6. The all-solid-state electrochromic device according to claim 1 or 5, wherein the surface sheet resistance of the first color-changing layer is not less than 0.8Ω/≡and the thickness is 50-400 nm;
the material of the first color-changing layer is nano amorphous or crystalline.
7. The all-solid-state electrochromic device according to claim 1, wherein the surface sheet resistance of the second color-changing layer is not less than 2 Ω/≡and the thickness is 100-900 nm;
the tungsten oxide is an amorphous nanoparticle.
8. The all-solid-state electrochromic device according to claim 1, wherein the material of the ion-providing and conducting layer is one or more of lithium salt, lithium oxide and lithium oxynitride;
the material of the ion providing and conducting layer is of an amorphous structure, and the thickness of the ion providing and conducting layer is 100-800 nm.
9. The all-solid-state electrochromic device according to claim 1, wherein the thickness of the protective layer is 20-500 nm;
the protective layer is a metal layer, an inorganic oxide layer or a high polymer film.
10. A method of manufacturing an all-solid-state electrochromic device according to any one of claims 1 to 9, comprising the steps of:
and sputtering a fourth dielectric film layer, a first functional layer, a first color-changing layer, a first dielectric film layer, an ion providing and conducting layer, a second dielectric film layer, a second color-changing layer, a third dielectric film layer, a second functional layer and a protective layer on the surface of the transparent substrate in sequence to obtain the all-solid-state electrochromic device.
CN202311848512.9A 2023-12-28 2023-12-28 All-solid-state electrochromic device and preparation method thereof Pending CN117806089A (en)

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