Electrochromic film

Abstract

The utility model provides an electrochromic film. The electrochromic film comprises a first transparent conducting layer, a cathode electrochromic layer, an ion conduction layer, an anode electrochromic layer, a medium layer and a second transparent conducting layer which are sequentially arranged in a laminated mode in the outward direction of a glass substrate. According to the electrochromic thin film, the film layer structure of the electrochromic thin film is optimized, so that the optical modulation performance is improved, and larger modulation amplitude and shorter coloring time are further realized.

Description

Technical Field

[0001] This invention belongs to the field of electrochromic technology, and particularly relates to an electrochromic film. Background Technology

[0002] Electrochromism is a phenomenon in which the optical properties (reflectivity, transmittance, absorptivity, etc.) of a material undergo stable and reversible color changes under the influence of an applied electric field. This manifests as reversible changes in color and transparency. Materials exhibiting electrochromic properties are called electrochromic materials. Under the influence of an applied electric field, electrochromic materials undergo electrochemical oxidation-reduction reactions, gaining or losing electrons, thus changing their color.

[0003] Currently, the film structure of electrochromic modules mainly consists of a transparent conductive layer 1 (made of ITO), an anodic electrochromic layer (made of NiO), and an ion-conducting layer (mainly containing Li). + The film consists of six main layers: a gel, a cathode electrochromic layer (WO3), a transparent conductive layer 2 (ITO), and a protective layer (SiO2). + Ions are the functional particles that drive the electrochromic effect. Currently, preparation methods combine sol-gel and evaporation coating methods, and the resulting electrochromic components have the characteristic that their transmittance changes when an external voltage is applied.

[0004] However, existing electrochromic film structures have the following drawbacks: the film structure is simple, the color change time is long, and the color change range is narrow; the film materials mostly contain organic gel layers, resulting in a short film life, generally 3 to 5 years; the preparation methods mostly adopt evaporation coating and sol-gel methods, which limit the material life and film adhesion.

[0005] CN 101510038A discloses a method for fabricating an all-solid-state electrochromic device. The device comprises, sequentially, a first transparent conductive layer, an electrochromic thin film layer, an ion-conducting layer, an ion storage thin film layer, and a second transparent conductive layer. The fabrication method involves: depositing metallic tungsten on ITO glass using DC magnetron sputtering to obtain an ITO glass / electrochromic thin film layer; depositing an ion storage thin film layer on the ITO glass using chemical plating; injecting a gel electrolyte precursor between the two half-devices (the ITO glass / electrochromic thin film layer and the ITO glass / ion storage thin film layer); and obtaining the all-solid-state device after heat treatment. This fabrication method involves a sol-gel process, which limits the material's lifespan and film adhesion.

[0006] CN 113885265A discloses an all-solid-state inorganic electrochromic composite film smart glass component and its preparation method. The preparation method includes: (1) using two transparent conductive film glasses as substrates, the transparent conductive film glasses being ITO or FTO coated glasses, preparing a WO3-based thin film with a thickness of 100-500 nm on one of the conductive glasses as an electrochromic layer by magnetron sputtering, and preparing a NiO-based thin film with a thickness of 100-500 nm on the other conductive glass as an ion storage layer by magnetron sputtering; (2) preparing a Li-based film with a thickness of 100-500 nm on the prepared WO3-based and NiO-based thin films respectively by wet chemical sol-gel method. + (3) The two glass films were subjected to wet chemical treatment with Li + The doped AlPO4 thin film is bonded together as a dielectric and then heat-cured to form a wet chemical ion transport layer between the glass components. The preparation method described in this scheme involves a sol-gel process, which limits the material's lifespan and film adhesion.

[0007] In summary, there is a need to develop an electrochromic film that can not only improve the color-changing speed and shorten the color-changing time, but also promote a wider color-changing range. Utility Model Content

[0008] To address the shortcomings of existing technologies, the purpose of this invention is to provide an electrochromic film. This invention achieves a greater modulation amplitude and a shorter coloring time through optimized film structure, further improving the performance of electrochromic products.

[0009] To achieve this objective, the present invention adopts the following technical solution:

[0010] This invention provides an electrochromic thin film, which includes, in the direction from the glass substrate outward, a first transparent conductive layer, a cathode electrochromic layer, an ion-conducting layer, an anode electrochromic layer, a dielectric layer, and a second transparent conductive layer stacked sequentially.

[0011] This invention improves optical modulation performance by optimizing the stacking order of the electrochromic thin film layers, further achieving a larger modulation amplitude and a shorter coloring time. More specifically, placing the dielectric layer between the anode electrochromic layer and the second transparent conductive layer facilitates the penetration and filling of ions through the anode electrochromic layer into the ion-conducting layer and the cathode electrochromic layer, ensuring that each layer is fully filled with lithium ions and that the lithium ions are fully and uniformly distributed.

[0012] As a preferred technical solution of this utility model, the thickness of the glass substrate is 0.4 to 5 mm, for example, it can be 0.4 mm, 1 mm, 2 mm, 3 mm, 4 mm or 5 mm, etc., but is not limited to the listed values. Other unlisted values ​​within the range are also applicable.

[0013] Preferably, the roughness of the glass substrate on the side near the electrochromic film is 5 to 20 nm, for example, it can be 5 nm, 8 nm, 11 nm, 14 nm, 17 nm or 20 nm, but is not limited to the listed values. Other unlisted values ​​within the range are also applicable.

[0014] As a preferred technical solution of this utility model, the thickness of the first transparent conductive layer is 100-500nm, for example, it can be 100nm, 200nm, 300nm, 400nm or 500nm, etc., but is not limited to the listed values. Other unlisted values ​​within the range are also applicable.

[0015] Preferably, the first transparent conductive layer comprises an ITO film with a surface resistance of 5 to 15 Ω. The surface resistance of the ITO film is 5 to 15 Ω, for example, it can be 5 Ω, 7 Ω, 9 Ω, 11 Ω, 13 Ω or 15 Ω, but is not limited to the listed values. Other values ​​not listed within the range are also applicable.

[0016] As a preferred embodiment of this invention, the cathode electrochromic layer includes a tungsten oxide layer.

[0017] Preferably, the thickness of the cathode electrochromic layer is 200-500 nm, for example, it can be 200 nm, 250 nm, 300 nm, 400 nm or 500 nm, but is not limited to the listed values. Other unlisted values ​​within the range are also applicable.

[0018] As a preferred embodiment of this invention, the ion-conducting layer comprises a silicon oxide layer or a silicon-aluminum oxide layer.

[0019] Preferably, the thickness of the ion-conducting layer is 5 to 25 nm, for example, it can be 5 nm, 10 nm, 15 nm, 20 nm or 25 nm, but is not limited to the listed values. Other unlisted values ​​within the range are also applicable.

[0020] As a preferred embodiment of this invention, the anodic electrochromic layer comprises a tungsten nickel oxide layer.

[0021] Preferably, the thickness of the anodic electrochromic layer is 200–500 nm, for example, it can be 200 nm, 300 nm, 400 nm or 500 nm, but is not limited to the listed values. Other unlisted values ​​within the range are also applicable.

[0022] In this invention, the atomic ratio of tungsten to nickel in the tungsten-nickel oxide layer is 2-3:2-3, for example, it can be 2:2, 2:2.5, 2:3, 3:2, 3:2.5 or 3:2.8, etc., but is not limited to the listed values. Other unlisted values ​​within the range are also applicable.

[0023] In this invention, the anodic electrochromic layer and the cathode electrochromic layer have the same thickness, and the materials used for both have complementary color-changing effects. The superimposed color-changing effect can make the color-changing range larger.

[0024] In a preferred embodiment of this invention, the dielectric layer comprises a lithium layer.

[0025] Preferably, the thickness of the dielectric layer is 100-200 nm, for example, it can be 100 nm, 120 nm, 140 nm, 160 nm, 180 nm or 200 nm, etc., but is not limited to the listed values. Other unlisted values ​​within the range are also applicable.

[0026] In this invention, the function of the dielectric layer is to create dark and transparent states by moving lithium ions to different electrochromic layers; if the thickness is too large, the transparent state will not be transparent enough and the transmittance will be low, while if the thickness is too small, the dark state will not be deep enough and the transmittance will be high.

[0027] As a preferred embodiment of this invention, the thickness of the second transparent conductive layer is 300–900 nm, for example, it can be 300 nm, 400 nm, 500 nm, 600 nm, 700 nm, 800 nm, or 900 nm, but is not limited to the listed values. Other values ​​within the range not listed are also applicable.

[0028] Preferably, the second transparent conductive layer comprises an ITO film with a surface resistance of 5 to 15 Ω. The surface resistance of the ITO film is 5 to 15 Ω, for example, it can be 5 Ω, 7 Ω, 9 Ω, 11 Ω, 13 Ω or 15 Ω, but is not limited to the listed values. Other unlisted values ​​within the range are also applicable.

[0029] It is worth noting that when the first transparent conductive layer of the electrochromic film is connected to the negative electrode and the second transparent conductive layer is connected to the positive electrode, the electrochromic film exhibits a dark state; conversely, when the first transparent conductive layer is connected to the positive electrode and the second transparent conductive layer is connected to the negative electrode, the electrochromic film exhibits a transparent state.

[0030] The preparation method of the above-mentioned electrochromic thin film includes the following steps:

[0031] The electrochromic film is obtained by sequentially depositing a first transparent conductive layer, a cathode electrochromic layer, an ion-conducting layer, an anodic electrochromic layer, a dielectric layer, and a second transparent conductive layer on the glass substrate using a vacuum magnetron sputtering deposition method.

[0032] Preferably, the preparation method further includes quality inspection and surface cleaning of the glass substrate.

[0033] Preferably, the power density of the first transparent conductive layer during the magnetron sputtering process is 2 to 6 kW / m, for example, it can be 2 kW / m, 3 kW / m, 4 kW / m, 5 kW / m or 6 kW / m, but is not limited to the listed values. Other unlisted values ​​within the range are also applicable.

[0034] Preferably, the temperature of the first transparent conductive layer during the magnetron sputtering process is 230 to 350°C, for example, 230°C, 250°C, 290°C, 310°C or 350°C, but not limited to the listed values. Other unlisted values ​​within the range are also applicable.

[0035] Preferably, the pressure of the first transparent conductive layer during the magnetron sputtering process is 0.1 to 1.0 Pa, for example, it can be 0.1 Pa, 0.3 Pa, 0.5 Pa, 0.7 Pa or 1.0 Pa, but is not limited to the listed values. Other unlisted values ​​within the range are also applicable.

[0036] Preferably, the argon flow rate of the first transparent conductive layer during the magnetron sputtering process is 100 to 500 sccm, for example, it can be 100 sccm, 200 sccm, 300 sccm, 400 sccm or 500 sccm, but is not limited to the listed values. Other values ​​not listed within the range are also applicable.

[0037] Preferably, the oxygen concentration of the first transparent conductive layer during the magnetron sputtering process is 0.1% to 1%, for example, it can be 0.1%, 0.3%, 0.5%, 0.8% or 1%, etc., but is not limited to the listed values. Other unlisted values ​​within the range are also applicable.

[0038] Preferably, the velocity of the first transparent conductive layer during the magnetron sputtering process is 0.1 to 1.0 m / min, for example, it can be 0.1 m / min, 0.3 m / min, 0.5 m / min, 0.7 m / min or 1 m / min, but is not limited to the listed values. Other unlisted values ​​within the range are also applicable.

[0039] Preferably, the power density of the cathode electrochromic layer during the magnetron sputtering process is 10 to 20 kW / m, for example, it can be 10 kW / m, 12 kW / m, 15 kW / m, 18 kW / m or 20 kW / m, but is not limited to the listed values. Other unlisted values ​​within the range are also applicable.

[0040] Preferably, the temperature of the cathode electrochromic layer during the magnetron sputtering process is 250 to 400°C, for example, 250°C, 300°C, 350°C or 400°C, but not limited to the listed values. Other unlisted values ​​within the range are also applicable.

[0041] Preferably, the pressure of the cathode electrochromic layer during the magnetron sputtering process is 0.5 to 4.0 Pa, for example, it can be 0.5 Pa, 1 Pa, 2 Pa, 3 Pa or 4 Pa, but is not limited to the listed values. Other unlisted values ​​within the range are also applicable.

[0042] Preferably, the argon flow rate during the magnetron sputtering process of the cathode electrochromic layer is 200 to 1000 sccm, for example, it can be 200 sccm, 500 sccm, 800 sccm or 1000 sccm, but is not limited to the listed values. Other unlisted values ​​within the range are also applicable.

[0043] Preferably, the oxygen concentration of the cathode electrochromic layer during the magnetron sputtering process is 20% to 100%, for example, it can be 20%, 40%, 60%, 80% or 100%, but is not limited to the listed values. Other unlisted values ​​within the range are also applicable.

[0044] Preferably, the velocity of the cathode electrochromic layer during the magnetron sputtering process is 0.1 to 1.0 m / min, for example, it can be 0.1 m / min, 0.3 m / min, 0.5 m / min, 0.7 m / min or 1 m / min, but is not limited to the listed values. Other unlisted values ​​within the range are also applicable.

[0045] Preferably, the power density of the ion-conducting layer during the magnetron sputtering process is 5 to 12 kW / m, for example, it can be 5 kW / m, 7 kW / m, 9 kW / m or 12 kW / m, but it is not limited to the listed values. Other unlisted values ​​within the range are also applicable.

[0046] Preferably, the temperature of the ion-conducting layer during the magnetron sputtering process is 20 to 80°C, for example, 20°C, 40°C, 60°C or 80°C, but not limited to the listed values. Other unlisted values ​​within the range are also applicable.

[0047] Preferably, the pressure of the ion-conducting layer during the magnetron sputtering process is 0.1 to 1.0 Pa, for example, it can be 0.1 Pa, 0.3 Pa, 0.5 Pa, 0.7 Pa or 1.0 Pa, but is not limited to the listed values. Other unlisted values ​​within the range are also applicable.

[0048] Preferably, the argon flow rate of the ion-conducting layer during magnetron sputtering is 200 to 1000 sccm, for example, it can be 200 sccm, 400 sccm, 600 sccm, 800 sccm or 1000 sccm, but is not limited to the listed values. Other unlisted values ​​within the range are also applicable.

[0049] Preferably, the oxygen concentration of the ion-conducting layer during the magnetron sputtering process is 65% to 100%, for example, it can be 65%, 70%, 80%, 90% or 100%, but is not limited to the listed values. Other unlisted values ​​within the range are also applicable.

[0050] Preferably, the velocity of the ion-conducting layer during the magnetron sputtering process is 0.1 to 1.0 m / min, for example, it can be 0.1 m / min, 0.3 m / min, 0.5 m / min, 0.7 m / min or 1 m / min, but is not limited to the listed values. Other unlisted values ​​within the range are also applicable.

[0051] Preferably, the power density of the anodic electrochromic layer during the magnetron sputtering process is 10 to 20 kW / m, for example, it can be 10 kW / m, 12 kW / m, 14 kW / m, 16 kW / m, 18 kW / m or 20 kW / m, but is not limited to the listed values. Other unlisted values ​​within the range are also applicable.

[0052] Preferably, the temperature of the anodic electrochromic layer during the magnetron sputtering process is 20 to 80°C, for example, 20°C, 40°C, 60°C or 80°C, but not limited to the listed values. Other unlisted values ​​within the range are also applicable.

[0053] Preferably, the pressure of the anodic electrochromic layer during the magnetron sputtering process is 0.5–4.0 Pa, for example, 0.1 Pa, 0.3 Pa, 0.5 Pa, 0.7 Pa, or 1.0 Pa, but is not limited to the listed values; other unlisted values ​​within the range are also applicable.

[0054] Preferably, the argon flow rate during the magnetron sputtering process of the anodic electrochromic layer is 200 to 1000 sccm, for example, it can be 200 sccm, 400 sccm, 600 sccm, 800 sccm or 1000 sccm, but is not limited to the listed values. Other unlisted values ​​within the range are also applicable.

[0055] Preferably, the oxygen concentration of the anodic electrochromic layer during the magnetron sputtering process is 20% to 100%, for example, it can be 20%, 40%, 60%, 80% or 100%, but is not limited to the listed values. Other unlisted values ​​within the range are also applicable.

[0056] Preferably, the velocity of the anodic electrochromic layer during the magnetron sputtering process is 0.1 to 1.0 m / min, for example, it can be 0.1 m / min, 0.3 m / min, 0.5 m / min, 0.7 m / min or 1 m / min, but is not limited to the listed values. Other unlisted values ​​within the range are also applicable.

[0057] Preferably, the power density of the dielectric layer during the magnetron sputtering process is 2 to 10 kW / m, for example, it can be 2 kW / m, 4 kW / m, 6 kW / m, 8 kW / m or 10 kW / m, but is not limited to the listed values. Other unlisted values ​​within the range are also applicable.

[0058] Preferably, the temperature of the dielectric layer during the magnetron sputtering process is 20 to 80°C, for example, 20°C, 40°C, 60°C or 80°C, but not limited to the listed values. Other unlisted values ​​within the range are also applicable.

[0059] Preferably, the pressure of the dielectric layer during the magnetron sputtering process is 0.1 to 1.0 Pa, for example, it can be 0.1 Pa, 0.3 Pa, 0.5 Pa, 0.7 Pa or 1.0 Pa, but is not limited to the listed values. Other unlisted values ​​within the range are also applicable.

[0060] Preferably, the argon flow rate of the dielectric layer during the magnetron sputtering process is 100 to 1000 sccm, for example, it can be 100 sccm, 300 sccm, 500 sccm, 700 sccm or 1000 sccm, but is not limited to the listed values. Other unlisted values ​​within the range are also applicable.

[0061] Preferably, the velocity of the dielectric layer during the magnetron sputtering process is 0.1 to 1.0 m / min, for example, it can be 0.1 m / min, 0.3 m / min, 0.5 m / min, 0.7 m / min or 1 m / min, but is not limited to the listed values. Other unlisted values ​​within the range are also applicable.

[0062] Preferably, the power density of the second transparent conductive layer during the magnetron sputtering process is 2 to 6 kW / m, for example, it can be 2 kW / m, 3 kW / m, 4 kW / m, 5 kW / m or 6 kW / m, but is not limited to the listed values. Other values ​​not listed within the range are also applicable.

[0063] Preferably, the temperature of the second transparent conductive layer during the magnetron sputtering process is 20 to 80°C, for example, 20°C, 40°C, 60°C or 80°C, but not limited to the listed values. Other unlisted values ​​within the range are also applicable.

[0064] Preferably, the pressure of the second transparent conductive layer during the magnetron sputtering process is 0.1 to 1 Pa, for example, it can be 0.1 Pa, 0.3 Pa, 0.5 Pa, 0.7 Pa or 1.0 Pa, but is not limited to the listed values. Other unlisted values ​​within the range are also applicable.

[0065] Preferably, the argon flow rate of the second transparent conductive layer during the magnetron sputtering process is 100 to 500 sccm, for example, it can be 100 sccm, 200 sccm, 300 sccm, 400 sccm or 500 sccm, but is not limited to the listed values. Other unlisted values ​​within the range are also applicable.

[0066] Preferably, the oxygen concentration of the second transparent conductive layer during the magnetron sputtering process is 0.1% to 1%, for example, it can be 0.1%, 0.3%, 0.5%, 0.7% or 1%, etc., but is not limited to the listed values. Other unlisted values ​​within the range are also applicable.

[0067] Preferably, the velocity of the second transparent conductive layer during the magnetron sputtering process is 0.1 to 1.0 m / min, for example, it can be 0.1 m / min, 0.3 m / min, 0.5 m / min, 0.7 m / min or 1 m / min, but is not limited to the listed values. Other unlisted values ​​within the range are also applicable.

[0068] As a preferred embodiment of this invention, the method for preparing the electrochromic thin film of this invention includes the following steps:

[0069] The electrochromic film is obtained by sequentially depositing a first transparent conductive layer, a cathode electrochromic layer, an ion-conducting layer, an anode electrochromic layer, a dielectric layer, and a second transparent conductive layer on the glass substrate using a vacuum magnetron sputtering deposition method.

[0070] In the first transparent conductive layer, the power density during magnetron sputtering is 2-6 kW / m, the coating temperature is 230-350°C, the coating pressure is 0.1-1.0 Pa, the argon flow rate is 100-500 sccm, the oxygen concentration is 0.1-1%, and the velocity is 0.1-1 m / min.

[0071] The cathode electrochromic layer is subjected to a power density of 10–20 kW / m, a coating temperature of 250–400 °C, a coating pressure of 0.5–4 Pa, an argon flow rate of 200–1000 sccm, an oxygen concentration of 20–100%, and a velocity of 0.1–1 m / min during the magnetron sputtering process.

[0072] The ion-conducting layer has a power density of 5–12 kW / m, a coating temperature of 20–80 °C, a coating pressure of 0.1–1.0 Pa, an argon flow rate of 200–1000 sccm, an oxygen concentration of 65–100%, and a velocity of 0.1–1 m / min during the magnetron sputtering process.

[0073] The anodic electrochromic layer is subjected to a power density of 10–20 kW / m, a coating temperature of 20–80 °C, a coating pressure of 0.5–4 Pa, an argon flow rate of 200–1000 sccm, an oxygen concentration of 20–100%, and a velocity of 0.1–1 m / min during the magnetron sputtering process.

[0074] The dielectric layer has a power density of 2–10 kW / m during magnetron sputtering, a coating temperature of 20–80 °C, a coating pressure of 0.1–1.0 Pa, an argon flow rate of 100–1000 sccm, and a velocity of 0.1–1 m / min.

[0075] The second transparent conductive layer has a power density of 2-6 kW / m, a coating temperature of 20-80°C, a coating pressure of 0.1-1.0 Pa, an argon flow rate of 100-500 sccm, an oxygen concentration of 0.1-1%, and a velocity of 0.1-1 m / min during the magnetron sputtering process.

[0076] The numerical range described in this utility model includes not only the point values ​​listed above, but also any point values ​​within the numerical range not listed above. Due to space limitations and for the sake of brevity, this utility model will not exhaustively list the specific point values ​​included in the range.

[0077] The system refers to an equipment system, device system, or production device.

[0078] Compared with the prior art, the present invention has the following beneficial effects:

[0079] (1) The electrochromic film provided by this utility model has good optical modulation performance. In the spectral range of 380 to 780 nm, it has an optical modulation amplitude of up to 60%, which can increase the modulation amplitude of electrochromic products by about 10%.

[0080] (2) The electrochromic film provided by this utility model has a rapid coloring time. Under the adjustment voltage of 1 to 5V, the coloring speed of the electrochromic film can be increased by about 200s. Attached Figure Description

[0081] Figure 1 This is a schematic diagram of the structure of the electrochromic film provided in Embodiment 1 of this utility model;

[0082] Wherein: 1 is a glass substrate, 2 is a first transparent conductive layer, 3 is a cathode electrochromic layer, 4 is an ion-conducting layer, 5 is an anode electrochromic layer, 6 is a dielectric layer, and 7 is a second transparent conductive layer. Detailed Implementation

[0083] It should be understood that in the description of this utility model, the terms "center", "longitudinal", "lateral", "upper", "lower", "front", "rear", "left", "right", "vertical", "horizontal", "top", "bottom", "inner", and "outer" indicate the orientation or positional relationship based on the orientation or positional relationship shown in the accompanying drawings. They are only for the convenience of describing this utility model and simplifying the description, and do not indicate or imply that the device or element referred to must have a specific orientation, or be constructed and operated in a specific orientation. Therefore, they should not be construed as limitations on this utility model.

[0084] It should be noted that, in the description of this utility model, unless otherwise explicitly specified and limited, the terms "set," "connected," and "linked" should be interpreted broadly. For example, they can refer to a fixed connection, a detachable connection, or an integral connection; they can refer to a mechanical connection or an electrical connection; they can refer to a direct connection or an indirect connection through an intermediate medium; and they can refer to the internal connection of two components. Those skilled in the art can understand the specific meaning of the above terms in this utility model based on the specific circumstances.

[0085] The technical solution of this utility model will be further described below with reference to the accompanying drawings and specific embodiments.

[0086] Example 1

[0087] This embodiment provides an electrochromic thin film, such as Figure 1As shown, the electrochromic film includes, in the direction from the glass substrate 1 outward, a first transparent conductive layer 2, a cathode electrochromic layer 3, an ion-conducting layer 4, an anode electrochromic layer 5, a dielectric layer 6, and a second transparent conductive layer 7, which are stacked sequentially.

[0088] The glass substrate 1 has a thickness of 2.5 mm and a roughness of 5 nm on the side near the electrochromic film.

[0089] The first transparent conductive layer 2 is an ITO thin film with a thickness of 300 nm and a surface resistance of 10 Ω;

[0090] The cathode electrochromic layer 3 is a tungsten oxide layer with a thickness of 350 nm.

[0091] The ion-conducting layer 4 is a silicon oxide layer with a thickness of 15 nm;

[0092] The anodic electrochromic layer 5 is a tungsten-nickel oxide layer with a thickness of 350 nm;

[0093] The dielectric layer 6 is a lithium layer with a thickness of 150 nm;

[0094] The second transparent conductive layer 7 is an ITO thin film with a thickness of 600 nm and a surface resistance of 10 Ω.

[0095] The method for preparing the electrochromic thin film described in this embodiment includes the following steps:

[0096] The electrochromic film is obtained by sequentially depositing a first transparent conductive layer, a cathode electrochromic layer, an ion-conducting layer, an anode electrochromic layer, a dielectric layer, and a second transparent conductive layer on the glass substrate using a vacuum magnetron sputtering deposition method.

[0097] In this process, the power density of the first transparent conductive layer is 4 kW / m, the coating temperature is 300 °C, the coating pressure is 0.5 Pa, the argon flow rate is 300 sccm, the oxygen concentration is 0.5%, and the velocity is 0.5 m / min.

[0098] The cathode electrochromic layer was deposited at a power density of 15 kW / m, a coating temperature of 320 °C, a coating pressure of 2 Pa, an argon flow rate of 600 sccm, an oxygen concentration of 60%, and a velocity of 0.5 m / min during the magnetron sputtering process.

[0099] The ion-conducting layer is subjected to a power density of 8 kW / m, a coating temperature of 50°C, a coating pressure of 0.4 Pa, an argon flow rate of 400 ccm, an oxygen concentration of 80%, and a velocity of 0.1 m / min during the magnetron sputtering process.

[0100] The anodic electrochromic layer is subjected to a power density of 10-20 kW / m during magnetron sputtering, a coating temperature of 60°C, a coating pressure of 3.0 Pa, an argon flow rate of 400 sccm, an oxygen concentration of 40%, and a velocity of 1 m / min.

[0101] The dielectric layer was subjected to a power density of 2 kW / m², a coating temperature of 50 °C, a coating pressure of 0.2 Pa, an argon flow rate of 200 sccm, and a velocity of 0.5 m / min during the magnetron sputtering process.

[0102] The second transparent conductive layer was subjected to a power density of 3 kW / m, a coating temperature of 40 °C, a coating pressure of 0.6 Pa, an argon flow rate of 200 sccm, an oxygen concentration of 0.7%, and a velocity of 0.6 m / min during the magnetron sputtering process.

[0103] Example 2

[0104] This embodiment provides an electrochromic thin film, which includes a first transparent conductive layer 2, a cathode electrochromic layer 3, an ion-conducting layer 4, an anode electrochromic layer 5, a dielectric layer 6, and a second transparent conductive layer 7 stacked sequentially from the glass substrate 1 outward.

[0105] The glass substrate 1 has a thickness of 0.4 mm and a roughness of 20 nm on the side near the electrochromic film.

[0106] The first transparent conductive layer 2 is an ITO thin film with a thickness of 100nm and a surface resistance of 15Ω;

[0107] The cathode electrochromic layer 3 is a tungsten oxide layer with a thickness of 200 nm;

[0108] The ion-conducting layer 4 is a silicon oxide layer with a thickness of 5 nm;

[0109] The anodic electrochromic layer 5 is a tungsten-nickel oxide layer with a thickness of 200 nm.

[0110] The dielectric layer 6 is a lithium layer with a thickness of 100 nm;

[0111] The second transparent conductive layer 7 is an ITO thin film with a thickness of 300 nm and a surface resistance of 15 Ω.

[0112] Example 3

[0113] This embodiment provides an electrochromic thin film, which includes a first transparent conductive layer 2, a cathode electrochromic layer 3, an ion-conducting layer 4, an anode electrochromic layer 5, a dielectric layer 6, and a second transparent conductive layer 7 stacked sequentially from the glass substrate 1 outward.

[0114] The glass substrate 1 has a thickness of 5 mm and a roughness of 5 nm on the side near the electrochromic film.

[0115] The first transparent conductive layer 2 is an ITO thin film with a thickness of 500 nm and a surface resistance of 5 Ω;

[0116] The cathode electrochromic layer 3 is a tungsten oxide layer with a thickness of 500 nm;

[0117] The ion-conducting layer 4 is a silicon-aluminum oxide layer with a thickness of 25 nm;

[0118] The anodic electrochromic layer 5 is a tungsten nickel oxide layer with a thickness of 500 nm;

[0119] The dielectric layer 6 is a lithium layer with a thickness of 200 nm;

[0120] The second transparent conductive layer 7 is an ITO thin film with a thickness of 900 nm and a surface resistance of 5 Ω.

[0121] Example 4

[0122] This embodiment provides an electrochromic film, which differs from the electrochromic film of Embodiment 1 only in that:

[0123] In this embodiment, the thickness of the dielectric layer 6 is adjusted to 400 nm.

[0124] Example 5

[0125] This embodiment provides an electrochromic film, which differs from the electrochromic film of Embodiment 1 only in that:

[0126] In this embodiment, the thickness of the dielectric layer 6 is adjusted to 50 nm.

[0127] Example 6

[0128] This embodiment provides an electrochromic film, which differs from the electrochromic film of Embodiment 1 only in that:

[0129] In this embodiment, the thickness of the first transparent conductive layer 2 is adjusted to 600nm.

[0130] Example 7

[0131] This embodiment provides an electrochromic film, which differs from the electrochromic film of Embodiment 1 only in that:

[0132] In this embodiment, the thickness of the anodic electrochromic layer 5 is adjusted to 100 nm.

[0133] Example 8

[0134] This embodiment provides an electrochromic film, which differs from the electrochromic film of Embodiment 1 only in that:

[0135] In this embodiment, the thickness of the anodic electrochromic layer 5 is adjusted to 600 nm.

[0136] Comparative Example 1

[0137] This comparative example provides an electrochromic film, which differs from Example 1 only in that:

[0138] In this comparative example, the stacking order of the electrochromic thin film glass substrate in the outward direction is adjusted to be: a first transparent conductive layer, a cathode electrochromic layer, a dielectric layer, an ion-conducting layer, an anode electrochromic layer, and a second transparent conductive layer are disposed sequentially; that is, the dielectric layer is adjusted to be between the cathode electrochromic layer and the ion-conducting layer.

[0139] Comparative Example 2

[0140] This comparative example provides an electrochromic film, which differs from Example 1 only in that:

[0141] The dielectric layer is omitted in this comparative example.

[0142] Performance testing:

[0143] The optical modulation performance of the electrochromic films provided in the above embodiments and comparative examples was tested, and the results are shown in Table 1.

[0144] The optical modulation performance testing includes: using a spectrophotometer, under conditions of a conditioning voltage of 1-5V and a spectral range of 380-780nm, to detect the transmittance of the electrochromic film and the time required for the lowest transmittance (coloring time); and calculating the modulation amplitude based on the transmittance.

[0145] Table 1

[0146] Modulation amplitude / % Coloring time / s Example 1 63 430 Example 2 61 480 Example 3 65 400 Example 4 22 430 Example 5 15 300 Example 6 53 400 Example 7 17 350 Example 8 32 430 Comparative Example 1 50 680 Comparative Example 2 5 30

[0147] According to Table 1, the following points can be observed:

[0148] (1) Based on a comprehensive analysis of Examples 1-3, it can be seen that the electrochromic film provided by this utility model has good optical modulation performance, which can increase the modulation amplitude of the electrochromic product by about 10% and the coloring speed by about 200s (compared to Comparative Example 1).

[0149] (2) A comprehensive analysis of Examples 1, 4-5 and Comparative Example 2 shows that by adjusting the positive and negative poles of the connection voltage, the dielectric layer in the electrochromic film is used to enable lithium ions to move to different electrochromic layers, thereby achieving color change (a dark state in the cathode electrochromic layer and a transparent state in the anode electrochromic layer). If its thickness is too thick, the transmittance of the transparent state will be low, thus reducing the modulation amplitude; conversely, if its thickness is too thin, the transmittance of the dark state will be high, thus reducing the modulation amplitude.

[0150] Omitting the medium layer will result in virtually no color change and extremely small modulation amplitude.

[0151] (3) A comprehensive analysis of Examples 1 and 6-8 shows that the change in the film thickness of the electrochromic film will affect the optical modulation performance of the electrochromic film.

[0152] If the thickness of the first transparent conductive layer is too thick, it will lead to a decrease in the overall transmittance of the transparent film layer, which in turn will reduce the modulation amplitude.

[0153] If the thickness of the anodic electrochromic layer is too thick, the transmittance of the dark state will increase and the modulation amplitude will decrease; conversely, if its thickness is too thin, the dark state color will not be deep enough, the transmittance will increase and the modulation amplitude will decrease.

[0154] (4) A comprehensive analysis of Example 1 and Comparative Example 1 shows that the stacking order of the film layers in the electrochromic film will affect the optical modulation performance of the electrochromic film.

[0155] Adjusting the dielectric layer to be positioned between the cathode electrochromic layer and the ion-conducting layer will result in a decrease in modulation amplitude and a longer coloring time.

[0156] In summary, this invention provides an improved optical modulation performance by optimizing the film structure of the electrochromic film, thereby achieving a larger modulation amplitude and a shorter coloring time.

[0157] The applicant declares that the above description is only a specific embodiment of the present utility model, but the protection scope of the present utility model is not limited thereto. Those skilled in the art should understand that any changes or substitutions that can be easily conceived by those skilled in the art within the technical scope disclosed in the present utility model fall within the protection and disclosure scope of the present utility model.

Claims

1. An electrochromic thin film, characterized in that, The electrochromic film comprises, in the direction from the glass substrate outward, a first transparent conductive layer, a cathode electrochromic layer, an ion-conducting layer, an anode electrochromic layer, a dielectric layer, and a second transparent conductive layer, which are stacked sequentially.

2. The electrochromic thin film according to claim 1, characterized in that, The thickness of the glass substrate is 0.4–5 mm; The roughness of the glass substrate on the side near the electrochromic film is 5–20 nm.

3. The electrochromic thin film according to claim 1, characterized in that, The thickness of the first transparent conductive layer is 100–500 nm.

4. The electrochromic thin film according to claim 3, characterized in that, The first transparent conductive layer comprises an ITO thin film with a surface resistivity of 5 to 15 Ω.

5. The electrochromic thin film according to claim 1, characterized in that, The cathode electrochromic layer includes a tungsten oxide layer; The thickness of the cathode electrochromic layer is 200–500 nm.

6. The electrochromic thin film according to claim 1, characterized in that, The ion-conducting layer includes a silicon oxide layer or a silicon-aluminum oxide layer; The thickness of the ion-conducting layer is 5–25 nm.

7. The electrochromic thin film according to claim 1, characterized in that, The anodic electrochromic layer includes a tungsten nickel oxide layer; The thickness of the anodic electrochromic layer is 200–500 nm.

8. The electrochromic thin film according to claim 1, characterized in that, The dielectric layer includes a lithium layer; The thickness of the dielectric layer is 100–200 nm.

9. The electrochromic thin film according to claim 1, characterized in that, The thickness of the second transparent conductive layer is 300–900 nm.

10. The electrochromic thin film according to claim 9, characterized in that, The second transparent conductive layer comprises an ITO thin film with a surface resistivity of 5 to 15 Ω.

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