CN110658660A - Electrochromic device based on multilayer functional thin film and preparation method thereof - Google Patents

Electrochromic device based on multilayer functional thin film and preparation method thereof Download PDF

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CN110658660A
CN110658660A CN201910982712.0A CN201910982712A CN110658660A CN 110658660 A CN110658660 A CN 110658660A CN 201910982712 A CN201910982712 A CN 201910982712A CN 110658660 A CN110658660 A CN 110658660A
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functional layer
color
changing
cathode
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CN110658660B (en
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杨恢东
彭斯冉
邵海平
张婧妍
夏锦辉
宋香荣
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Guangdong Tisnawell New Material Technology Co ltd
Jinan university shaoguan institute
Jinan University
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Guangdong Tisnawell New Material Technology Co ltd
Jinan university shaoguan institute
Jinan University
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    • G02F1/01—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour 
    • G02F1/15—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour  based on an electrochromic effect
    • G02F1/1514—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour  based on an electrochromic effect characterised by the electrochromic material, e.g. by the electrodeposited material
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    • C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
    • C23C14/06—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the coating material
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    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
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    • C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
    • C23C14/06—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the coating material
    • C23C14/08—Oxides
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    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
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    • C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
    • C23C14/22—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the process of coating
    • C23C14/34—Sputtering
    • C23C14/35—Sputtering by application of a magnetic field, e.g. magnetron sputtering
    • C23C14/352—Sputtering by application of a magnetic field, e.g. magnetron sputtering using more than one target
    • G—PHYSICS
    • G02—OPTICS
    • G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
    • G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
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    • G02F1/15—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour  based on an electrochromic effect
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    • G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
    • G02F1/01—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour 
    • G02F1/15—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour  based on an electrochromic effect
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Abstract

The invention relates to an electrochromic device based on a multilayer functional film and a preparation method thereof, wherein the device comprises a first transparent electrode layer, a plurality of cathode color-changing functional layers, an electrolyte layer, an anode color-changing functional layer and a second transparent electrode layer which are sequentially connected, wherein the first transparent electrode layer is arranged on the opposite outer surface of the cathode color-changing functional layer, and the second transparent electrode layer is arranged on the opposite outer surface of the anode color-changing functional layer; the plurality of cathodic discoloration functional layers comprise MoO3MaterialThe color-changing functional layer comprises a main cathode color-changing functional layer and an auxiliary cathode color-changing functional layer coated on the outer surface of the main cathode color-changing functional layer, wherein the thickness of the main cathode color-changing functional layer is larger than that of the auxiliary cathode color-changing functional layer. The invention integrates the advantages of a plurality of color-changing functional layer materials, solves the problems of poor adhesion and poor stability of the electrochromic device of molybdenum oxide, improves the comprehensive properties of the manufactured device such as stability, electrochromic response speed, light modulation range and the like, and reduces the manufacturing cost of the device.

Description

Electrochromic device based on multilayer functional thin film and preparation method thereof
Technical Field
The invention relates to an electrochromic device technology, in particular to an electrochromic device based on a multilayer functional film and a preparation method thereof.
Background
Electrochromism is a phenomenon that the optical properties (reflectivity, transmittance, absorptivity and the like) of a material generate stable and reversible color change under the action of an external electric field, and the electrochromism is represented as reversible change of color and transparency in appearance. Materials having electrochromic properties are referred to as electrochromic materials, and devices made with electrochromic materials are referred to as electrochromic devices.
The electrochromic device has adjustability of light absorption and transmission under the action of an electric field, can selectively absorb or reflect external heat radiation and internal heat diffusion, and reduces a large amount of energy which is consumed for keeping office buildings and civil houses cool in summer and warm in winter; meanwhile, the purposes of improving the natural illumination degree and preventing peeping are achieved; the problem of urban light pollution which is continuously worsened in modern times is solved, and the method is a development direction of energy-saving building materials. Electrochromic devices have attracted attention in areas such as windows, rear view mirrors, and display screens. Meanwhile, all-solid-state electrochromic devices also have some problems, such as higher cost, unsatisfactory stability of the devices, and the like, and at present, deep research on all-solid-state electrochromic devices is still needed to help the performance improvement and industrialization realization of the electrochromic devices.
The complementary electrochromic device is an electrochromic device with better light modulation range and stability at present, and researchers have proposed the structure of 'electrode// anode color-changing functional layer// electrolyte layer// cathode color-changing functional layer// electrode'. The electrochromic functional layer is a core layer of the electrochromic device and is also a generation layer of a color change reaction. Tungsten oxide (WO)3) The active layer is often used as a cathode discoloration active layer, and has relatively good stability, so that the active layer is widely researched by a plurality of researchers and has more mature report results. There is still room for improvement in the structure of "electrode// anode discoloration functional layer// electrolyte layer// cathode discoloration functional layer// electrode" described above.
In contrast, molybdenum (Mo) is a group-homologous metal element of tungsten (W), an oxide of molybdenum (MoO)3) But the molybdenum oxide film has poor adhesion and poor stability when serving as an electrochromic functional layer, and shows that the film is easy to fall off, the electrochromic effect is obviously reduced after several times of electric field conversion, and few reports are made in academia on electrochromic devices based on molybdenum oxide. Corresponding to the disadvantages, the advantages of molybdenum oxide as an electrochromic functional layer are: 1) the lower driving voltage means that the electrochromic device of molybdenum oxide is more energy-saving and environment-friendly than the electrochromic device of tungsten oxide; 2) the global resource reserves of molybdenum are larger, about 1100 ten thousand tons, and tungsten is about 330 ten thousand tons, and the market price of molybdenum is lower than that of tungsten; 3) MoO3Has a flatter absorption spectrum curve in the visible region, thus showing a better appearance than WO3Softer neutral color, with better visual aesthetics. If the above MoO can be solved3Based on MoO3Electrochromic devices will either gain tremendous development. In addition, titanium oxide (TiO)2) Etc. also have electrochromic effects.
From the above, the electrochromic device based on oxides of molybdenum, tungsten, etc. still has major disadvantages, and efforts are still needed to improve the overall electrochromic performance of the device.
Disclosure of Invention
In order to solve the problems in the prior art, the invention provides an electrochromic device based on a multilayer functional film, which adopts an electrochromic device structure with a plurality of color-changing functional layers and integrates the advantages of materials of the plurality of color-changing functional layers so as to solve the problems of poor adhesion and poor stability of an electrochromic device of molybdenum oxide, and improves the comprehensive performance of the electrochromic device such as the stability, electrochromic response speed, light modulation range and the like of the manufactured device and reduces the manufacturing cost of the device by integrating the advantages of a plurality of functional films.
The electrochromic device based on the multilayer functional film comprises a first transparent electrode layer, a plurality of cathode color-changing functional layers, an electrolyte layer, an anode color-changing functional layer and a second transparent electrode layer which are sequentially connected, wherein the first transparent electrode layer is arranged on the opposite outer surface of the cathode color-changing functional layer, and the second transparent electrode layer is arranged on the opposite outer surface of the anode color-changing functional layer;
the plurality of cathodic discoloration functional layers comprise MoO3The color-changing functional layer comprises a main cathode color-changing functional layer made of the material and an auxiliary cathode color-changing functional layer coated on the opposite outer surface of the main cathode color-changing functional layer, wherein the thickness of the main cathode color-changing functional layer is larger than that of the auxiliary cathode color-changing functional layer.
Preferably, the thickness of the primary cathode color-changing functional layer is several times of that of the secondary cathode color-changing functional layer, and the secondary cathode color-changing functional layer can be formed by WO3And TiO2Etc. are made from one or more of the materials in layers.
Preferably, the auxiliary cathode color-changing functional layer comprises a first cathode color-changing functional layer, the first cathode color-changing functional layer is covered on the first transparent electrode layer, and the main cathode color-changing functional layer is a second cathode color-changing functional layer and is covered on the first cathode color-changing functional layer.
Preferably, the secondary cathode discoloration functional layer further comprises a third cathode discoloration functional layer disposed between the primary cathode discoloration functional layer and the electrolyte layer.
The invention relates to a preparation method of an electrochromic device based on a multilayer functional film, which comprises the following steps:
cutting a substrate layer into a proper size, removing dirt and scale, cleaning in an ultrasonic cleaning machine, washing with deionized water, drying with industrial nitrogen, placing into a magnetron sputtering chamber, and vacuumizing the magnetron sputtering chamber;
the first transparent electrode layer and the second transparent electrode layer are sputtered by taking indium tin oxide as a target under the argon environment and are respectively coated on the substrate layer and the anode discoloration function layer;
the first cathode discoloration functional layer is pure tungsten as a target material, the gas flow of oxygen and argon is adjusted, sputtering is carried out at normal temperature, and tungsten ions and oxygen ions are combined to form WO3Is covered on the first transparent electrode layer;
the second cathode color-changing functional layer takes pure molybdenum as a target material, adjusts the gas flow of oxygen and argon, performs sputtering at normal temperature, and combines molybdenum ions and oxygen ions to form MoO3Is covered on the first cathode color-changing functional layer;
the electrolyte layer takes lithium tantalate as a target material, regulates the gas flow of argon in an argon environment, sputters at normal temperature, and is coated on the second cathode discoloration functional layer;
the anode discoloration functional layer takes nickel as a target material, adjusts the gas flow of oxygen and argon, performs sputtering at normal temperature, and combines nickel ions and oxygen ions to form NiOx to be coated on the electrolyte layer.
By means of the explanation of the technical scheme, compared with the prior art, the invention has the following beneficial effects:
1. the device of the invention is due to the thinner WO3The oxide with better stability is used as other cathode discoloration functional layers to cover the thicker main cathode discoloration layer MoO3To the opposite outer surface ofThe novel structure of the plurality of color-changing functional layers of the electrode/anode color-changing functional layer/electrolyte layer/plurality of cathode color-changing functional layers/electrode integrates the advantages of the materials of the plurality of color-changing functional layers, so that the MoO is combined on the premise of keeping better electrochromic performance (indexes such as optical modulation range, response time and the like) of the device3Better isolate from the external water oxygen environment, namely play the role of similar buffer layer, improve the MoO3The stability of the layer; and because W and Mo are VIB group elements, the oxides of the two elements can be combined well, and MoO3The problem of poor adhesion is solved, the improvement of the comprehensive performance of devices such as stability, electrochromic response speed, light modulation range and the like is realized, and the manufacturing cost of the devices is reduced.
2. The device of the invention uses MoO3The main electrochromic functional layer has a plurality of beneficial effects, and has more friendly visual perception of human eyes due to a flatter absorption spectrum curve; the driving voltage of the second device is more than that of WO3The dominant electrochromic device is low, which means more energy saving and environmental protection; and thirdly, the using amount of W is greatly reduced, so that the cost of the whole device is reduced.
3. All structural film layers of the device are made of inorganic materials, so that the finished product has long service life, relatively low cost and high feasibility of industrialization.
Drawings
FIG. 1 is a schematic structural diagram of an electrochromic device based on a multi-layer functional thin film in example 1 of the present invention;
FIG. 2 is a schematic structural diagram of an electrochromic device based on a multi-layer functional thin film in example 2 of the present invention;
FIG. 3 is a graph showing the change of optical transmittance of a device manufactured in example 2 of the present invention during operation.
Detailed Description
The present invention will be described in detail below with reference to the accompanying drawings, but embodiments of the invention are not limited thereto.
The electrochromic device comprises a first transparent electrode layer, a plurality of cathode color-changing functional layers, an electrolyte layer and an anode color-changing function which are sequentially connectedA layer and a second transparent electrode layer. The first transparent electrode layer is arranged on the opposite outer surface of the cathode color-changing functional layer, the second transparent electrode layer is arranged on the opposite outer surface of the anode color-changing functional layer, the first transparent electrode layer and the second transparent electrode layer are made of Indium Tin Oxide (ITO) materials, and the surface resistance is 10-50 omega-cm2And the thickness is 150-200 nm.
A plurality of cathode discoloration functional layers are made of MoO3、WO3And TiO2The materials are combined in layers, wherein, MoO3The number of other cathode color-changing functional layers (namely, auxiliary cathode color-changing functional layers) can be increased or reduced for the necessary main cathode color-changing functional layer, and one or more layers of other cathode color-changing functional layers are often coated on the main color-changing functional layer MoO3An opposing outer surface of (a); a plurality of cathode color-changing functional layers are covered on the first transparent electrode layer; MoO contributing to the primary electrochromic Effect3The layer thickness is thicker, between 150nm and 400nm, and is generally several times thicker than other film layers.
The electrolyte layer adopts tantalum oxide Ta2O5Lithium borate LiBO2And lithium tantalate (LiTaO)3One of the materials is coated on the second cathode color-changing functional layer, and the film thickness is 150-300 nm. The anode color-changing functional layer adopts nickel oxide NiOx and iridium oxide IrO2Rhodium (Rh) oxide2O3One of these materials, preferably 100-150nm thick.
The following will explain the structure of the plurality of functional layers for cathodic discoloration by way of example.
Example 1
As shown in fig. 1, the multilayer functional thin film electrochromic device of the present embodiment sequentially includes: the color-changing cathode substrate comprises a substrate layer 1, a first transparent electrode layer 2 arranged on the substrate layer 1, a first cathode color-changing functional layer 3 arranged on the first transparent electrode layer 2, a second cathode color-changing functional layer 4 arranged on the first cathode color-changing functional layer 3, an electrolyte layer 5 arranged on the first cathode color-changing functional layer 4, an anode color-changing functional layer 6 arranged on the electrolyte layer 5 and a second transparent electrode layer 7 arranged on the anode color-changing functional layer 6. In addition, for the convenience of the device in the actual use process, an electrode wiring port 8 is arranged beside the first transparent electrode layer 2, and an electrode wiring port 9 is arranged beside the second transparent electrode layer 7.
The structural layers of the device can be coated by adopting one or more methods of chemical vapor deposition, sol-gel process, vacuum evaporation deposition, pulsed excimer laser valvetrain deposition, magnetron sputtering and the like. The magnetron sputtering method has a wide application range, and can be used for coating a thin film by magnetron sputtering as long as the target with a proper specification is made of a conductive or non-conductive substance. Meanwhile, the magnetron sputtering method has the advantages of low temperature required in the preparation process, simple process and high process repeatability, reduces the manufacturing cost of the device, and is adopted by each layer of structural film layer in the embodiment.
In this embodiment, the coating of each structural layer film is preferably performed by a magnetron sputtering method, and the adopted magnetron sputtering device has a vacuum system, so that the vacuum degree in the sputtering chamber reaches 3 × 10-3Pa, which is a necessary prerequisite for the subsequent sputtering of the film. When the sputtering target material is used for growing the film, the required film performance is obtained by controlling parameters such as temperature, pressure, gas flow, sputtering power and the like in the magnetron sputtering chamber. The characteristics and fabrication process of each structural layer will be described in detail below.
The substrate layer 1 functions as a device to which films of the functional structure layers are attached, and may be made of different materials such as window glass, a screen, a rearview mirror, and the like, depending on the actual application. Cutting the substrate layer 1 into proper size, removing dirt and removing dirt with detergent and alcohol, oscillating for 20 minutes in an ultrasonic cleaning machine to clean, washing clean with deionized water, blow-drying with industrial nitrogen, placing into a magnetron sputtering chamber, and preparing for sputtering coating after vacuumizing the chamber.
The first transparent electrode layer 2 and the second transparent electrode layer 7 are sputtered by taking Indium Tin Oxide (ITO) as a target under the argon environment at 100 ℃ and are respectively coated on the substrate layer and the anode discoloration functional layer; the sputtering pressure is controlled to be between 0.3 Pa and 5Pa, the sputtering power is controlled to be between 50 watts and 200 watts of direct current power, and the film thickness of the first transparent electrode layer 2 and the second transparent electrode layer 7 is controlled to be between 150nm and 200 nm. The transparent electrode layer is used to collect and guide current in a certain direction while ensuring that visible light can normally transmit through the material.
The first cathode discoloration functional layer 3 takes 99.99 percent of pure tungsten (W) as a target material, adjusts the gas flow of oxygen and argon, carries out sputtering at normal temperature, and combines tungsten ions and oxygen ions to form WO3Is covered on the first transparent electrode layer 2; the sputtering pressure is controlled to be between 1 and 4.5Pa, the sputtering power is controlled to be between 100 and 200 watts of direct current power, and the film thickness of the first cathode discoloration functional layer 3 is controlled to be between 50 and 150 nm. The role of the first functional cathodochromic layer 3 is to provide MoO in addition to partial electrochromic properties3Better isolate from the external water oxygen environment, namely play the role of similar buffer layer, improve the MoO3The stability of the layer; and W and Mo are VIB group elements, oxides of the two elements can be well combined, and the first cathode color-changing functional layer 3 provides good attachment points for the subsequent second cathode color-changing functional layer 4.
The second cathode color-changing functional layer 4 is used as a main cathode color-changing functional layer, 99.99 percent of pure molybdenum (Mo) is used as a target material, the gas flow of oxygen and argon is adjusted, normal-temperature sputtering is carried out, and molybdenum ions and oxygen ions are combined to form MoO3Is coated on the first functional cathode discolouring layer 3. The sputtering pressure is controlled to be between 1 Pa and 4.5Pa, the sputtering power is controlled to be between 100-200 watts of direct current power, and the film thickness of the second cathode color-changing functional layer 4 is controlled to be between 250-600 nm. The second cathodochromic functional layer 4 contributes to the main electrochromic properties, and brings better performance and lower cost to the whole device by virtue of material characteristics such as smaller driving voltage, large global earth crust resource storage and flat optical transmission curve.
The electrolyte layer 5 was made of 99.5% lithium tantalate (LiTaO)3) In the argon environment, the gas flow of argon is adjusted, normal temperature sputtering is carried out, the target material is coated on the second cathode discoloration functional layer 4, the sputtering pressure is controlled to be between 0.5 and 2Pa, the sputtering power is controlled to be between 100 and 200 watts of alternating current power, and the film thickness of the electrolyte layer 5 is controlled to be between 100 and 200 nm. The electrolyte layer 5 serves to provide a pathway for ion transport during device operation, discolouring the anodeThe electron transport between the functional layer 6 and the second cathodochromic functional layer 4 is isolated, namely: when the first cathode discoloration functional layer 3, the second cathode discoloration functional layer 4 and the anode discoloration functional layer 6 have electrochromic effect, extracted or injected ions are transmitted through the electrolyte layer 5, and electrons are isolated at two ends of the electrolyte layer 5 to the greatest extent possible.
The anode discoloration functional layer 6 takes 99.95% of nickel as a target material, adjusts the gas flow of oxygen and argon, performs sputtering at normal temperature, and combines nickel ions and oxygen ions to form NiOx which is coated on the electrolyte layer 5; the sputtering pressure is controlled to be between 1 and 5Pa, the sputtering power is controlled to be between 80 and 200 watts, and the film thickness of the anode discoloration functional layer 6 is controlled to be between 100 and 200 nm. The function of the anodic discolouration functional layer 6 is: the electrochromic device and each cathode color-changing functional layer form a complementary type electrochromic device which is respectively arranged on one side of a positive electrode and one side of a negative electrode, so that when the device works, the two color-changing layers can mutually form respective ion storage layers, the stability of the device is improved, and meanwhile, due to double electrochromic, the contrast of the device is higher.
After the magnetron sputtering chamber is coated with each functional layer, the device is taken out from the chamber, the electrode wiring port 8 is adhered to the side edge of the first transparent electrode layer 2, the electrode wiring port 9 is adhered to the side edge of the second transparent electrode layer 7, and the used materials can be common conductors such as copper wires, aluminum wires and conductive adhesive tapes. The width of the electrode tap 8 and the electrode tap 9 may be 3mm or less, and the thickness may be 1mm or less.
Example 2
As shown in FIG. 2, the structure of this embodiment is similar to that of example 1, except that a third functional cathode discoloration layer 10 is additionally added between the second functional cathode discoloration layer 4 and the electrolyte layer 5 for converting MoO of the second functional cathode discoloration layer 43Isolated from the electrolyte layer 5, and moderating MoO ion pairs from the electrolyte layer 53The impact of the layer, thus make the stability of the second cathodic discoloration functional layer 4 better, because the third cathodic discoloration functional layer 10 also adopts the tungsten material, the film adhesion of the second cathodic discoloration functional layer 4 can be further improved.
The preparation method of this example andexample 1 the same, except that a third functional cathode discolouring layer 10 is prepared on the second functional cathode discolouring layer 4 between the second functional cathode discolouring layer 4 and the electrolyte layer 5. The process adopted by the layer is still a magnetron sputtering method, 99.99 percent of pure tungsten (W) is taken as a target, the gas flow of oxygen and argon is adjusted, sputtering is carried out at normal temperature, and WO is formed3Is covered on the second cathode color-changing functional layer 4; the sputtering pressure is controlled to be between 1 Pa and 4.5Pa, the sputtering power is controlled to be between 100 and 200 watts of direct current power, and the film thickness of the third cathode discoloration functional layer 10 is controlled to be between 50nm and 120 nm.
The change curve of the optical transmittance of the device manufactured in this example in operation is shown in fig. 3. In order to show the state change of the coloring and the fading of the device for many times, a square wave signal with the potential of +/-1.8 volts is artificially applied to the manufactured device, and the pulse width is 60 seconds. As can be seen from FIG. 3, the device fabricated in this example has better stability, the optical transmittance curve is stable after a plurality of square wave signal cycles, and no large amplitude attenuation occurs, which also proves that MoO3The layer has no membrane shedding and has better adhesiveness; the optical transmittance of the manufactured device in a faded state is about 66%, the optical transmittance of the manufactured device in a colored state is about 12%, and the optical modulation range is 54%, so that the effect is ideal.
According to the above examples, the device was produced with a coloring driving voltage of-0.5 volt to-2 volts and a discoloring driving voltage of 0.5 volt to 2 volts. The optical transmittance of the prepared device in a colored state is between 5% and 20%, and the optical transmittance of the prepared device in a faded state is between 60% and 90%; the coloring reaction time of the prepared device is between 5 seconds and 40 seconds, and the fading response time is between 0.5 seconds and 5 seconds. MoO of the device made3The stability and adhesion of the layer are better and better electrochromic properties are obtained overall. The manufactured device has long service life, relatively low cost and high feasibility of industrialization.
The above embodiments are preferred embodiments of the present invention, but the present invention is not limited to the above embodiments, and any other changes, modifications, substitutions, combinations, and simplifications which do not depart from the spirit and principle of the present invention should be construed as equivalents thereof, and all such changes, modifications, substitutions, combinations, and simplifications are intended to be included in the scope of the present invention.

Claims (10)

1. The electrochromic device based on the multilayer functional film is characterized by comprising a first transparent electrode layer, a plurality of cathode color-changing functional layers, an electrolyte layer, an anode color-changing functional layer and a second transparent electrode layer which are sequentially connected, wherein the first transparent electrode layer is arranged on the outer surface opposite to the cathode color-changing functional layer, and the second transparent electrode layer is arranged on the outer surface opposite to the anode color-changing functional layer;
the plurality of cathodic discoloration functional layers comprise MoO3The color-changing functional layer comprises a main cathode color-changing functional layer made of the material and an auxiliary cathode color-changing functional layer coated on the opposite outer surface of the main cathode color-changing functional layer, wherein the thickness of the main cathode color-changing functional layer is larger than that of the auxiliary cathode color-changing functional layer.
2. The electrochromic device based on multi-layered functional thin film according to claim 1, wherein the thickness of the primary cathode color-changing functional layer is several times as thick as that of the secondary cathode color-changing functional layer, and the secondary cathode color-changing functional layer is formed by WO3And TiO2The material is made by layering.
3. The electrochromic device according to claim 1, wherein the first transparent electrode layer and the second transparent electrode layer are made of indium tin oxide material and have an area resistance of 10-50 Ω -cm2And the thickness is 150-200 nm.
4. The electrochromic device based on multi-layer functional film according to claim 1, wherein the auxiliary cathode color-changing functional layer comprises a first cathode color-changing functional layer, the first cathode color-changing functional layer is coated on the first transparent electrode layer, and the main cathode color-changing functional layer is a second cathode color-changing functional layer and is coated on the first cathode color-changing functional layer.
5. The electrochromic device based on multi-layer functional thin film as claimed in claim 4Element, characterized in that said first cathodic discolouring functional layer is WO3A layer having a thickness of between 50-150 nm; the thickness of the second cathode color-changing functional layer is between 250-600 nm.
6. The multilayer functional film-based electrochromic device according to claim 4, wherein the secondary cathodic discoloration functional layer further comprises a third cathodic discoloration functional layer disposed between the primary cathodic discoloration functional layer and the electrolyte layer.
7. The electrochromic device based on multi-layered functional film according to claim 6, wherein the third functional layer for cathode color change is WO3A layer with a thickness of between 50 and 120 nm.
8. The electrochromic device according to claim 4 or 6, further comprising a substrate layer, wherein the first transparent electrode layer is disposed on the substrate layer.
9. The method for preparing an electrochromic device based on a multi-layered functional thin film according to claim 8, comprising the steps of:
cutting a substrate layer into a proper size, removing dirt and scale, cleaning in an ultrasonic cleaning machine, washing with deionized water, drying with industrial nitrogen, placing into a magnetron sputtering chamber, and vacuumizing the magnetron sputtering chamber;
the first transparent electrode layer and the second transparent electrode layer are sputtered by taking indium tin oxide as a target under the argon environment and are respectively coated on the substrate layer and the anode discoloration function layer;
the first cathode discoloration functional layer is pure tungsten as a target material, the gas flow of oxygen and argon is adjusted, sputtering is carried out at normal temperature, and tungsten ions and oxygen ions are combined to form WO3Is covered on the first transparent electrode layer;
the second cathode color-changing functional layer takes pure molybdenum as a target material, adjusts the gas flow of oxygen and argon, and performs normal-temperature sputtering to obtain molybdenum ionsCombined with oxygen ions to form MoO3Is covered on the first cathode color-changing functional layer;
the electrolyte layer takes lithium tantalate as a target material, regulates the gas flow of argon in an argon environment, sputters at normal temperature, and is coated on the second cathode discoloration functional layer;
the anode discoloration functional layer takes nickel as a target material, adjusts the gas flow of oxygen and argon, performs sputtering at normal temperature, and combines nickel ions and oxygen ions to form NiOx to be coated on the electrolyte layer.
10. The method of claim 9, wherein the secondary cathodic discoloration functional layer further comprises a third cathodic discoloration functional layer disposed between the primary cathodic discoloration functional layer and the electrolyte layer;
the preparation method further comprises the following steps: preparing a third cathode color-changing functional layer, taking pure tungsten as a target, adjusting the gas flow of oxygen and argon, and sputtering at normal temperature to form WO3Is coated on the second cathode color-changing functional layer.
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