Electrochromic assembly, preparation method thereof and electronic device

Abstract

The invention provides an electrochromic component, a preparation method thereof and an electronic device. The electrochromic component comprises a substrate, a titanium oxide layer, an electrochromic functional layer and a top conductive layer which are sequentially stacked, wherein the surface roughness Ra of the titanium oxide layer is less than or equal to 0.5 nm, and the surface defect rate of the electrochromic functional layer is less than or equal to 1.5%. The defects of the electrochromic assembly can be reduced, the quality of the electrochromic film is improved, and the application prospect is wide.

Description

Technical Field

[0001] This invention relates to the field of electronic device technology, and in particular to an electrochromic component, its preparation method, and an electronic device thereof. Background Technology

[0002] Electrochromic thin films typically consist of a multilayer structure (such as WO3 / electrolyte layer / NiWO3). x The performance of thin films is significantly affected by interface quality. In traditional magnetron sputtering or evaporation processes, thin films often suffer from defects such as pinholes and cracks due to uneven substrate surfaces, particulate contamination, or interfacial stress, which affect device response speed and cycle life.

[0003] In the existing technology, TiO x It can not only act as a barrier layer to prevent Na from entering the substrate. + When impurities diffuse into the functional layer, it also serves as a commonly used buffer layer material, improving ion transport efficiency, enhancing interlayer bonding, regulating interfacial stress, and reducing cracks.

[0004] However, currently TiO x Even if subsequent coatings are applied directly after the electrochromic layer deposition, the problem of poor performance of the electrochromic layer still exists. Summary of the Invention

[0005] To address the shortcomings of existing technologies, the present invention aims to provide an electrochromic component, its preparation method, and electronic device, which can improve the interlayer interface quality, thereby reducing defects such as thin film pinholes and cracks, and improving device performance.

[0006] To achieve this objective, the present invention adopts the following technical solution:

[0007] In a first aspect, the present invention provides an electrochromic component, the electrochromic component comprising a substrate, a titanium oxide layer, an electrochromic functional layer, and a top conductive layer stacked sequentially. The surface roughness Ra of the titanium oxide layer is ≤0.5 nm, and the surface defect rate of the electrochromic functional layer is ≤1.5%.

[0008] The surface roughness of titanium oxide in the electrochromic component provided by this invention is reduced to Ra≤0.5nm, and the surface defect rate of the final electrochromic functional layer is ≤1.5%. The device performance of the electrochromic component is significantly improved, and the modulation amplitude of the sample is significantly enhanced.

[0009] Specifically, the surface roughness Ra of the titanium oxide layer is ≤0.5nm, for example, it can be 0.5nm, 0.45nm, 0.4nm, 0.38nm, 0.35nm, 0.3nm, 0.28nm, 0.25nm, 0.2nm, 0.15nm or 0.1nm, etc.

[0010] The surface defect rate of the electrochromic functional layer is ≤1.5%, for example, it can be 1.5%, 1.3%, 1.2%, 1.0%, 0.9%, 0.8%, 0.5%, 0.1% or 0%, etc.

[0011] Preferably, the interface defect rate between the electrochromic layer and the titanium oxide layer is ≤5%, for example, it can be 5%, 4.8%, 4.5%, 4.2%, 4%, 3.8%, 3.5%, 3.2%, 3%, 2.8%, 2.5%, 2.2%, 2.0%, 1.8%, 1.5%, 1.2%, 1%, 0.8%, 0.5%, 0.2%, or 0.1%, etc.

[0012] This invention not only has a low defect rate in the electrochromic layer itself, but also a low interface defect rate between the electrochromic layer and the titanium oxide, resulting in products of excellent quality.

[0013] Preferably, the substrate comprises a transparent conductive substrate.

[0014] Preferably, the transparent conductive substrate comprises an ITO layer and / or an FTO layer.

[0015] Preferably, the thickness of the substrate is 300~800nm, for example, it can be 300nm, 350nm, 410nm, 460nm, 520nm, 570nm, 630nm, 680nm, 745nm or 800nm, but is not limited to the listed values. Other unlisted values ​​within this range are also applicable.

[0016] Preferably, the thickness of the titanium oxide layer is 5~100 nm, for example, it can be 5 nm, 5.5 nm, 6 nm, 6.5 nm, 7 nm, 7.5 nm, 8 nm, 8.5 nm, 9 nm, 9.5 nm, 10 nm, 20 nm, 30 nm, 40 nm, 50 nm, 60 nm, 70 nm, 80 nm, 90 nm or 100 nm, etc., but is not limited to the listed values, and other unlisted values ​​within this range are also applicable.

[0017] Preferably, the surface of the titanium oxide layer does not have titanium oxide dispersed particles.

[0018] Preferably, the thickness of the electrochromic layer is 300~900nm, for example, it can be 300nm, 350nm, 400nm, 500nm, 600nm, 700nm, 750nm, 800nm, 850nm or 900nm, but is not limited to the listed values. Other unlisted values ​​within this range are also applicable.

[0019] Preferably, the electrochromic layer is made of tungsten oxide and nickel tungsten oxide.

[0020] Preferably, the top conductive layer is made of ITO. In a second aspect, the present invention provides a method for preparing the electrochromic component described in the first aspect, the method comprising the following steps:

[0021] A titanium oxide layer is deposited on the surface of a substrate using magnetron sputtering to obtain a first component with the titanium oxide layer. The first component is then subjected to brush cleaning and ultrasonic cleaning sequentially to obtain a cleaned second component. An electrochromic functional layer and a top conductive layer are then sequentially deposited on the surface of the titanium oxide layer in the second component to obtain an electrochromic component.

[0022] The preparation method provided in the second aspect of the present invention preferably adopts the above method. Through the ultrasonic cleaning step, surface contaminants of the titanium oxide layer in the first component can be effectively removed, the interlayer interface quality can be improved, thereby reducing defects such as pinholes and cracks in the electrochromic functional layer, and ultimately improving the device performance.

[0023] Preferably, the magnetron sputtering power in the deposited titanium oxide layer is 1000~3000W, for example, it can be 1000W, 1200W, 1500W, 1800W, 2000W, 2200W, 2500W, 2800W, 2900W or 3000W, but is not limited to the listed values. Other unlisted values ​​within this range are also applicable.

[0024] Preferably, the magnetron sputtering temperature in the deposited titanium oxide layer is 200~300℃, for example, it can be 200℃, 210℃, 220℃, 230℃, 240℃, 250℃, 260℃, 270℃, 280℃, 290℃ or 300℃, but is not limited to the listed values. Other unlisted values ​​within this range are also applicable.

[0025] Preferably, the solvent for ultrasonic cleaning is water.

[0026] Preferably, the power of the ultrasonic cleaning is 200~500kW, for example, it can be 200kW, 230kW, 260kW, 300kW, 330kW, 360kW, 400kW, 430kW, 460kW or 500kW, but is not limited to the listed values. Other unlisted values ​​within this range are also applicable.

[0027] Preferably, the ultrasonic cleaning time is 2 to 5 minutes, for example, it can be 2 minutes, 2.4 minutes, 2.7 minutes, 3 minutes, 3.4 minutes, 3.7 minutes, 4 minutes, 4.4 minutes, 4.7 minutes or 5 minutes, but is not limited to the listed values. Other unlisted values ​​within this range are also applicable.

[0028] Preferably, the electrochromic functional layer is deposited using a magnetron sputtering process.

[0029] Preferably, the deposition of the electrochromic functional layer includes a pre-sputtering process followed by thickening deposition.

[0030] The present invention preferably employs a pre-sputtering treatment followed by a thickening deposition. The magnetron sputtering power of the pre-sputtering treatment is lower than that of the magnetron sputtering power of the thickening deposition. The temperature of the pre-sputtering treatment is lower than that of the thickening deposition. By using a lower sputtering power and temperature for pre-sputtering, a thinner electrochromic functional layer is first deposited tightly on the surface of the titanium oxide, followed by thickening deposition. This significantly improves the interfacial performance between the electrochromic functional layer and the titanium oxide layer, and has broad application prospects.

[0031] Preferably, the magnetron sputtering power of the pre-sputtering treatment is 1000~2000W, for example, it can be 1000W, 1100W, 1200W, 1300W, 1400W, 1500W, 1600W, 1700W, 1800W, 1900W or 2000W, but is not limited to the listed values. Other unlisted values ​​within this range are also applicable.

[0032] Preferably, the temperature of the pre-sputtering treatment is 200~300℃, for example, it can be 200℃, 210℃, 220℃, 230℃, 240℃, 250℃, 260℃, 270℃, 280℃, 290℃ or 300℃, but is not limited to the listed values. Other unlisted values ​​within this range are also applicable.

[0033] Preferably, the duration of the pre-sputtering treatment is 0.5 to 2 hours, for example, it can be 0.5 hours, 0.7 hours, 0.9 hours, 1 hour, 1.2 hours, 1.4 hours, 1.5 hours, 1.7 hours, 1.9 hours or 2 hours, but is not limited to the listed values. Other unlisted values ​​within this range are also applicable.

[0034] The present invention preferably controls the temperature, power and duration of the pre-sputtering treatment within the above-mentioned range, which can better improve the interface performance between the electrochromic functional layer and the titanium oxide layer, while increasing the density of the electrochromic functional layer and reducing the defect rate.

[0035] Preferably, the magnetron sputtering power for the thickening deposition is 1000~3000W, for example, it can be 1000W, 1100W, 1200W, 1500W, 1800W, 1900W, 2000W, 2100W, 2200W, 2500W, 2800W or 3000W, but is not limited to the listed values. Other unlisted values ​​within this range are also applicable.

[0036] Preferably, the temperature for thickening deposition is 200~300℃, for example, it can be 200℃, 210℃, 220℃, 230℃, 240℃, 250℃, 260℃, 270℃, 280℃, 290℃ or 300℃, but is not limited to the listed values. Other unlisted values ​​within this range are also applicable.

[0037] As a preferred technical solution of the present invention, the preparation method includes the following steps:

[0038] A titanium oxide layer was deposited on the surface of the substrate using a magnetron sputtering method with a power of 1000~3000W and a temperature of 200~300℃ to obtain a first component with a titanium oxide layer.

[0039] The first component is placed in water for ultrasonic cleaning. The ultrasonic cleaning power is 200~500kW and the time is 2~5min, resulting in the cleaned second component.

[0040] In the second component, the surface of the titanium oxide layer is first pre-sputtered at a temperature of 200-300°C, a power of 1000-2000W, and a time of 0.5-2h. Then, a thickening deposition is performed, with a magnetron sputtering power of 1000-3000W and a temperature of 200-300°C, to obtain the electrochromic component.

[0041] Thirdly, the present invention provides an electronic device comprising the electrochromic component described in the first aspect, and / or an electrochromic component obtained by the method for preparing the electrochromic component described in the second aspect.

[0042] Compared with the prior art, the present invention has at least the following beneficial effects:

[0043] (1) The electrochromic component provided by the present invention has a low defect rate, wherein TiO2 x The surface roughness (Ra) was reduced to below 0.5 nm, and the defect rate of the subsequent electrochromic functional layer was significantly reduced; moreover, the modulation amplitude of the sample was increased by more than 60%, indicating broad application prospects.

[0044] (2) The method for preparing the electrochromic component provided by the present invention is based on TiO2. x Adding a specific cleaning process after layer deposition, followed by subsequent electrochromic functional layer coating, can reduce defects such as pinholes and cracks in the electrochromic functional layer and improve device performance. Attached Figure Description

[0045] Figure 1 This is a schematic diagram of the electrochromic component provided by the present invention.

[0046] Figure 2This is a sample image of the titanium oxide layer in the electrochromic component provided in Embodiment 1 of the present invention before cleaning.

[0047] Figure 3 This is a sample image of the titanium oxide layer in the electrochromic component provided in Embodiment 1 of the present invention after cleaning.

[0048] In the figure: 1. Substrate; 2. Titanium oxide layer; 3. Electrochromic functional layer; 4. ITO conductive layer. Detailed Implementation

[0049] To facilitate understanding of the present invention, the following embodiments are provided. Those skilled in the art should understand that these embodiments are merely illustrative and should not be construed as limiting the scope of the invention.

[0050] It should be understood that in the description of this invention, the terms "center," "longitudinal," "lateral," "upper," "lower," "front," "rear," "left," "right," "vertical," "horizontal," "top," "bottom," "inner," and "outer," etc., indicate the orientation or positional relationship based on the orientation or positional relationship shown in the accompanying drawings. These terms are used only for the convenience of describing the invention and for 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 the invention. Furthermore, the terms "first," "second," etc., are used for descriptive purposes only and should not be construed as indicating or implying relative importance or implicitly specifying the number of indicated technical features. Thus, a feature defined with "first," "second," etc., may explicitly or implicitly include one or more of that feature. In the description of this invention, unless otherwise stated, "a plurality of" means two or more.

[0051] It should be noted that, in the description of this invention, 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 invention based on the specific circumstances.

[0052] TiO x It can not only act as a barrier layer to prevent Na from entering the substrate. + When impurities diffuse into the functional layer, TiO2 also serves as a commonly used buffer layer material, improving ion transport efficiency, enhancing interlayer bonding, regulating interfacial stress, and reducing cracking. However, in actual deposition processes, TiO2... xThe deposition layer is susceptible to problems such as surface contamination, particle residue, or non-uniform crystallization. Its surface state after deposition directly affects the nucleation and growth of subsequent electrochromic layers (such as WO3 and NiWOx), leading to defects such as pinholes, cracks, or interface peeling in subsequent functional layers, reducing device lifespan and optical contrast.

[0053] TiO x Directly performing subsequent coatings after layer deposition does not adequately address the following issues:

[0054] 1. TiO x Surface-adsorbed impurities (such as sputtered residual gases and unreacted organic precursors);

[0055] 2. Excessive surface roughness leads to stress concentration in subsequent thin films;

[0056] 3. Mismatch in interfacial chemical states leads to blockage of ion migration channels.

[0057] To address this issue, the present invention provides an electrochromic component that can improve the poor performance of the electrochromic functional layer after titanium oxide coating.

[0058] The following detailed description uses specific embodiments.

[0059] Example 1

[0060] This embodiment provides an electrochromic component, such as Figure 1 As shown, the electrochromic component includes a substrate 1, a titanium oxide layer 2, an electrochromic functional layer 3, and a top conductive layer 4 stacked sequentially.

[0061] The substrate 1 includes a transparent conductive substrate; the transparent conductive substrate includes an ITO layer; the thickness of the substrate 1 is 500 nm; the thickness of the titanium oxide layer 2 is 8 nm; the thickness of the electrochromic layer 3 is 600 nm; the electrochromic layer 3 is made of tungsten oxide; and the top conductive layer 4 is made of ITO.

[0062] This embodiment also provides a method for preparing the above-mentioned electrochromic component, the method comprising the following steps:

[0063] A titanium oxide layer (using a titanium target) was deposited on the surface of a substrate using magnetron sputtering at a power of 1200 W and a temperature of 230 °C to obtain a first component with a titanium oxide layer. A sample image of the titanium oxide layer is shown below. Figure 2 As shown;

[0064] The first component was placed in water and subjected to brush cleaning and ultrasonic cleaning sequentially. The ultrasonic cleaning power was 300kW and the time was 3 minutes. The second component was obtained after cleaning. The sample image of the titanium oxide layer after cleaning is shown in the figure. Figure 3As shown, from Figure 3 It can be seen that after ultrasonic cleaning, the surface of the titanium oxide layer no longer has titanium oxide particles and contaminants;

[0065] In the second component, the surface of the titanium oxide layer is first pre-sputtered (using a tungsten target) at a temperature of 220°C, a power of 1000W, and a time of 60 minutes. Then, a thickening deposition is performed using magnetron sputtering at a power of 1800W and a temperature of 240°C to deposit an electrochromic functional layer. Finally, a top conductive layer is deposited on the surface of the electrochromic functional layer to obtain the electrochromic component.

[0066] Example 2

[0067] This embodiment provides an electrochromic component, which includes a substrate, a titanium oxide layer, an electrochromic functional layer, and a top conductive layer stacked sequentially.

[0068] The substrate includes a transparent conductive substrate; the transparent conductive substrate includes an FTO layer; the thickness of the substrate is 300 nm; the thickness of the titanium oxide layer is 5 nm; the thickness of the electrochromic layer is 300 nm; the electrochromic layer is made of tungsten oxide, and the top conductive layer 4 is made of ITO.

[0069] This embodiment also provides a method for preparing the above-mentioned electrochromic component, the method comprising the following steps:

[0070] A titanium oxide layer (using a titanium target) was deposited on the surface of a substrate using magnetron sputtering at a power of 1000W and a temperature of 300℃ to obtain a first component with a titanium oxide layer.

[0071] The first component was placed in water and subjected to brush cleaning and ultrasonic cleaning in sequence. The ultrasonic cleaning power was 200kW and the time was 5min, resulting in the second component after cleaning.

[0072] In the second component, the surface of the titanium oxide layer is first pre-sputtered (using a tungsten target) at a temperature of 200°C, a power of 2000W, and a time of 2 hours. Then, a thickening deposition is performed using magnetron sputtering at a power of 3000W and a temperature of 200°C to deposit an electrochromic functional layer. Finally, a top conductive layer is deposited on the surface of the electrochromic functional layer to obtain the electrochromic component.

[0073] Example 3

[0074] This embodiment provides an electrochromic component, which includes a substrate, a titanium oxide layer, an electrochromic functional layer, and a top conductive layer stacked sequentially.

[0075] The substrate includes a transparent conductive substrate; the transparent conductive substrate includes an ITO layer; the thickness of the substrate is 800 nm; the thickness of the titanium oxide layer is 10 nm; the thickness of the electrochromic layer is 900 nm; the electrochromic layer is made of tungsten oxide, and the top conductive layer 4 is made of ITO.

[0076] This embodiment also provides a method for preparing the above-mentioned electrochromic component, the method comprising the following steps:

[0077] A titanium oxide layer (using a titanium target) was deposited on the surface of a substrate using magnetron sputtering at a power of 3000W and a temperature of 200℃ to obtain a first component with a titanium oxide layer.

[0078] The first component was placed in water and subjected to brush cleaning and ultrasonic cleaning in sequence. The ultrasonic cleaning power was 500kW and the time was 2min, resulting in the second component after cleaning.

[0079] In the second component, the surface of the titanium oxide layer is first pre-sputtered (using a tungsten target) at a temperature of 280°C, a power of 1000W, and a time of 0.5h. Then, a thickening deposition is performed using magnetron sputtering at a power of 1500W and a temperature of 300°C to deposit an electrochromic functional layer. Finally, a top conductive layer is deposited on the surface of the electrochromic functional layer to obtain the electrochromic component.

[0080] Example 4

[0081] This embodiment provides an electrochromic component. Except for the ultrasonic cleaning power of 150kW, the electrochromic component is the same as that in Embodiment 1, and will not be described again here.

[0082] Example 5

[0083] This embodiment provides an electrochromic component. Except for the ultrasonic cleaning power of 600kW, the electrochromic component is the same as that in Embodiment 1, and will not be described again here.

[0084] Example 6

[0085] This embodiment provides an electrochromic component, which is the same as that in Embodiment 1 except that it does not undergo pre-sputtering treatment, and will not be described again here.

[0086] Example 7

[0087] This embodiment provides an electrochromic component. Except for the pre-sputtering power of 800W, the electrochromic component is the same as that in Embodiment 1, and will not be described again here.

[0088] Example 8

[0089] This embodiment provides an electrochromic component. Except for the pre-sputtering temperature of 180°C, the electrochromic component is the same as that in Embodiment 1, and will not be described again here.

[0090] Comparative Example 1

[0091] This comparative example provides an electrochromic component, which is the same as that in Example 1 except that it does not undergo ultrasonic cleaning, and will not be described again here.

[0092] Test method: Defect rate of electrochromic functional layer: The electrochromic component is placed in a surface quality inspection system (micro-vision charge-coupled device CCD) to scan its surface. Then, the light signal is converted into an electrical signal and sent to a computer. The defect area of ​​the finished product is counted and recorded as the defect rate by dividing the defect area by the total surface area.

[0093] Roughness: The surface of the titanium oxide layer was tested using a roughness tester.

[0094] Interface defect rate between the electrochromic layer and the titanium oxide layer: The electrochromic component is cut in the thickness direction at 5 different locations. The interface between the electrochromic layer and the titanium oxide layer is scanned using a micro-vision charge-coupled device (CCD). The light signal is then converted into an electrical signal and transmitted to a computer. The defect length at the interface is statistically analyzed. The average defect length of the 5 cross sections is divided by the total length of the interface to obtain the interface defect rate.

[0095] The test results of the above embodiments and comparative examples are shown in Table 1.

[0096] Table 1

[0097]

[0098] As can be seen from Table 1, based on Examples 1-3, the surface roughness Ra of the titanium oxide in the electrochromic component provided by the present invention is ≤0.5nm, and the surface defect rate of the electrochromic functional layer is ≤1.5%. The present invention can reduce the defects of the electrochromic component, improve the quality of the electrochromic film, and has broad application prospects.

[0099] The present invention has been illustrated with the above embodiments to illustrate its detailed features, but the present invention is not limited to the above detailed features, that is, it does not mean that the present invention must rely on the above detailed features to be implemented. Those skilled in the art should understand that any improvements to the present invention, equivalent substitutions for the selected technical features, additions of auxiliary technical features, and selection of specific methods, etc., all fall within the protection scope and disclosure scope of the present invention.

Claims

1. An electrochromic component, characterized in that, The electrochromic component includes a substrate, a titanium oxide layer, an electrochromic functional layer, and a top conductive layer stacked sequentially. The surface roughness Ra of the titanium oxide layer is ≤0.5nm, and the surface defect rate of the electrochromic functional layer is ≤1.5%.

2. The electrochromic component according to claim 1, characterized in that, The interface defect rate between the electrochromic layer and the titanium oxide layer is ≤5%.

3. The electrochromic component according to claim 1 or 2, characterized in that, The substrate includes a transparent conductive substrate; Preferably, the transparent conductive substrate comprises an ITO layer and / or an FTO layer; Preferably, the thickness of the substrate is 300~800 nm; Preferably, the thickness of the titanium oxide layer is 5~100 nm; Preferably, the thickness of the electrochromic layer is 300~900 nm; Preferably, the electrochromic layer is made of tungsten oxide and nickel tungsten oxide; Preferably, the top conductive layer is made of ITO.

4. A method for preparing an electrochromic component according to any one of claims 1 to 3, characterized in that, The preparation method includes the following steps: A titanium oxide layer is deposited on the surface of a substrate using a magnetron sputtering method to obtain a first component with a titanium oxide layer; The first component is sequentially subjected to brush cleaning and ultrasonic cleaning to obtain the cleaned second component. An electrochromic functional layer and a top conductive layer are sequentially deposited on the surface of the titanium oxide layer in the second component to obtain an electrochromic component.

5. The preparation method according to claim 4, characterized in that, The magnetron sputtering power in the deposited titanium oxide layer is 1000~3000W; Preferably, the magnetron sputtering temperature in the deposited titanium oxide layer is 200~300℃.

6. The preparation method according to claim 4 or 5, characterized in that, The solvent used for ultrasonic cleaning is water.

7. The preparation method according to any one of claims 4 to 6, characterized in that, The power of the ultrasonic cleaning is 200~500kW; Preferably, the ultrasonic cleaning time is 2-5 minutes.

8. The preparation method according to any one of claims 4 to 7, characterized in that, The electrochromic functional layer was deposited using a magnetron sputtering process. Preferably, the deposition of the electrochromic functional layer includes a pre-sputtering process followed by thickening deposition.

9. The preparation method according to claim 8, characterized in that, The magnetron sputtering power of the pre-sputtering treatment is 1000~2000W; Preferably, the temperature of the pre-sputtering treatment is 200~300℃; Preferably, the pre-sputtering treatment lasts for 0.5 to 2 hours; Preferably, the magnetron sputtering power for the thickening deposition is 1000~3000W; Preferably, the temperature for the thickening deposition is 200~300℃.

10. An electronic device, characterized in that, The electronic device includes the electrochromic component according to any one of claims 1 to 3, and / or the electrochromic component obtained by the method for preparing the electrochromic component according to any one of claims 4 to 9.

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