A method for preparing a powered electrochromic film
By preparing multilayer thin films with modified indium oxide, tin oxide, and vanadium pentoxide, the stress problem of ITO electrochromic films during bending was solved, achieving rapid photoelectric response and stability, and improving the bending stability and photoelectric response speed of electrochromic films.
Patent Information
- Authority / Receiving Office
- CN · China
- Patent Type
- Patents(China)
- Current Assignee / Owner
- PLA AIR FORCE AVIATION UNIVERSITY
- Filing Date
- 2023-10-23
- Publication Date
- 2026-05-19
AI Technical Summary
Existing ITO electrochromic films are prone to stress during repeated bending, which affects the photoelectric response speed.
A multilayered thin film with modified indium oxide, tin oxide and vanadium pentoxide was deposited by magnetron sputtering and combined with vacuum annealing to prepare an electrically opaque photochromic film with a porous structure. The dispersibility and stability were improved by surface treatment of modified indium oxide.
It eliminates internal stress during bending, improves bending stability and response speed, and achieves rapid photoelectric response speed. The channel structure increases the contact of the electrode/electrolyte interface, improves charge transfer speed, and achieves rapid photoelectric response speed, thereby improving the stability and response speed of the technology, and at the same time improving the stability and photoelectric response of the product.
Abstract
Description
Technical Field
[0001] This invention relates to the field of electrochromic materials technology, specifically to a method for preparing an electrochromic thin film that is opaque when electrically conductive. Background Technology
[0002] Electrochromic materials refer to materials whose optical properties (reflectivity, transmittance, absorptivity, etc.) 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. Electrochromic devices mainly consist of a substrate, a transparent electrode, and an electrochromic thin film. Existing ITO electrochromic thin films are transparent and prone to stress during repeated bending, affecting the photoelectric response speed. Summary of the Invention
[0003] To address the shortcomings of existing technologies, the present invention aims to provide a method for preparing an electrically opaque photochromic thin film, thereby solving the problems mentioned in the background section.
[0004] The present invention solves the technical problem by adopting the following technical solution:
[0005] This invention provides a method for preparing an electrically opaque photochromic thin film, comprising the following steps:
[0006] S01. Before coating, the substrate is ultrasonically cleaned in a cleaning solution, dried with nitrogen, and then placed in a vacuum chamber with a pressure of 1×10⁻⁶. -3 Pa-5×10 -1 Pa, which makes the temperature of the substrate 150-250℃;
[0007] S02. Remove the substrate from the vacuum chamber and sequentially deposit the first oxide layer, the metal layer, and the second oxide layer using magnetron sputtering.
[0008] S03. Vacuum annealing is performed on the product after step S02 to obtain an electrochromic film.
[0009] The first oxide layer and the second oxide layer are made of the same material, which includes modified indium oxide, tin oxide and vanadium pentoxide in a mass ratio of 85-90:8-10:6.
[0010] Preferably, the method for preparing the modified indium oxide includes the following steps:
[0011] First, a porous carrier with a volume ratio of 1:10-12 is ultrasonically mixed with a 50% indium nitrate solution for 80-120 min. The precipitate is then pyrolyzed at 400-450℃ for 1-3 h. The pyrolyzed precipitate is then mixed with sodium hydroxide powder at a mass ratio of 1:1-2. The mixture is then reacted at 800-1200℃ under argon atmosphere for 30-80 min. After the reaction, a 20% carbonic acid solution is added at 50-60℃, with a volume ratio of 8-10:1 between the carbonic acid solution and the solid powder in the container. The mixture is then reacted for 1-2 h. After the reaction, the precipitate is collected to obtain porous indium oxide. The dried porous indium oxide is then subjected to a surface modification treatment to obtain modified indium oxide.
[0012] Preferably, the step of modifying the surface of the dried porous indium oxide includes:
[0013] The dried porous indium oxide and dispersant were added to the dispersion medium and ultrasonically mixed until homogeneous. After homogeneous mixing, the mixture was ball-milled for 5-10 hours and finally dried to obtain modified indium oxide.
[0014] Preferably, the porous carrier is prepared by mixing and contacting a treatment agent with carbon nanotubes at a mass ratio of 2.2-2.4:1 under the protection of argon at 800-1200℃, and then etching the carbon nanotubes to create pores for 30-80 minutes.
[0015] Preferably, the treatment agent is one of potassium hydroxide and sodium hydroxide.
[0016] Preferably, in step S01, before coating, the substrate is placed in a cleaning solution for ultrasonic cleaning, dried with nitrogen, and then placed in a vacuum chamber with a pressure of 1×10⁻⁶. -3 Pa-5×10 -1 Pa, which makes the temperature of the substrate 150-250℃;
[0017] S02. Remove the substrate from the vacuum chamber and sequentially deposit the first oxide layer, the metal layer, and the second oxide layer using magnetron sputtering. The working gas for magnetron sputtering is argon, and the purity of the argon is >99.9%. The sputtering temperature is 20-30℃.
[0018] The steps for magnetron sputtering deposition of the first oxide layer are as follows: a mixture of modified indium oxide, tin oxide and vanadium pentoxide in a mass ratio of 85-90:8-10:6 is uniformly mixed, and the first oxide layer is deposited by magnetron sputtering. During the sputtering deposition of the first oxide layer, the sputtering power of the RF target is 600-800 watts, the sputtering rate is 0.05-2 nm / s, and the thickness of the first oxide layer is 10-12 nm.
[0019] The steps for magnetron sputtering to deposit a metal layer are as follows: a metal layer is deposited by sputtering using a magnetron sputtering method. When sputtering the first oxide layer, the sputtering power of the DC target is 50-100 watts, the sputtering rate is 0.05-0.1 nm / s, and the thickness of the metal layer is 4-5 nm.
[0020] The steps for magnetron sputtering deposition of the second oxide layer are as follows: Modified indium oxide, tin oxide, and vanadium pentoxide are mixed uniformly in a mass ratio of 85-90:8-10:6, and the first oxide layer is deposited by magnetron sputtering. During the sputtering deposition of the first oxide layer, the sputtering power of the RF target is 600-800 watts, the sputtering rate is 0.05-2 nm / s, and the thickness of the second oxide layer is 6-8 nm.
[0021] Preferably, the vacuum annealing process in step S03 includes: placing the product from step S02 into a vacuum chamber and annealing it at 300-500°C for 20-30 minutes to obtain an electrochromic film.
[0022] Preferably, the metal in the metal layer is one or a mixture of Ag, Au and Cu.
[0023] Preferably, the metal in the metal layer is a mixture of Au and Cu with a mass ratio of 1-1.5:1.
[0024] Preferably, the cleaning solution in step S01 is one or a mixture of ethanol, acetone, and deionized water, and the ultrasonic cleaning time is 10-15 minutes.
[0025] Preferably, the dispersant is one of KH570 silane coupling agent and octadecyl alcohol.
[0026] Preferably, the dispersant is KH570 silane coupling agent.
[0027] Compared with the prior art, the present invention has the following beneficial effects:
[0028] This invention prepares porous indium oxide by using a porous carrier, indium nitrate solution, and sodium hydroxide in combination. The porous structure can eliminate internal stress during bending and improve bending stability. At the same time, the pore structure increases the contact between the electrode and electrolyte interface, improves the charge transfer ion transport rate, and improves the electrode reaction kinetics to achieve a rapid photoelectric response. Furthermore, the surface modification of the porous indium oxide with a dispersant can further prevent agglomeration and improve dispersibility, thereby further improving the stability and photoelectric response of the product. Detailed Implementation
[0029] The technical solutions of the embodiments of the present invention will be clearly and completely described below with reference to specific examples. Obviously, the described embodiments are only some embodiments of the present invention, and not all embodiments. Based on the embodiments of the present invention, all other embodiments obtained by those skilled in the art without creative effort are within the scope of protection of the present invention.
[0030] This embodiment of the invention provides a method for preparing an electrically opaque photochromic thin film, comprising the following steps:
[0031] S01. Before coating, the substrate is ultrasonically cleaned in a cleaning solution, dried with nitrogen, and then placed in a vacuum chamber with a pressure of 1×10⁻⁶. -3 Pa-5×10 -1 Pa, which makes the temperature of the substrate 150-250℃;
[0032] S02. Remove the substrate from the vacuum chamber and sequentially deposit the first oxide layer, the metal layer, and the second oxide layer using magnetron sputtering.
[0033] S03. Vacuum annealing is performed on the product after step S02 to obtain an electrochromic film.
[0034] The first oxide layer and the second oxide layer are made of the same material, which includes modified indium oxide, tin oxide and vanadium pentoxide in a mass ratio of 85-90:8-10:6.
[0035] The method for preparing the modified indium oxide described in this embodiment includes the following steps:
[0036] First, a porous carrier with a volume ratio of 1:10-12 is ultrasonically mixed with a 50% indium nitrate solution for 80-120 min. The precipitate is then pyrolyzed at 400-450℃ for 1-3 h. The pyrolyzed precipitate is then mixed with sodium hydroxide powder at a mass ratio of 1:1-2. The mixture is then reacted at 800-1200℃ under argon atmosphere for 30-80 min. After the reaction, a 20% carbonic acid solution is added at 50-60℃, with a volume ratio of 8-10:1 between the carbonic acid solution and the solid powder in the container. The mixture is then reacted for 1-2 h. After the reaction, the precipitate is collected to obtain porous indium oxide. The dried porous indium oxide is then subjected to a surface modification treatment to obtain modified indium oxide.
[0037] The steps of modifying the surface of the dried porous indium oxide in this embodiment include:
[0038] The dried porous indium oxide and dispersant were added to the dispersion medium and ultrasonically mixed until homogeneous. After homogeneous mixing, the mixture was ball-milled for 5-10 hours and finally dried to obtain modified indium oxide.
[0039] The porous carrier described in this embodiment is prepared by mixing carbon nanotubes with a treatment agent at a mass ratio of 2.2-2.4:1 under the protection of argon at 800-1200℃, and then etching the carbon nanotubes to create pores for 30-80 minutes.
[0040] The treatment agent described in this embodiment is one of potassium hydroxide and sodium hydroxide.
[0041] In this embodiment, S01, before coating, the substrate is placed in a cleaning solution for ultrasonic cleaning, dried with nitrogen, and then placed in a vacuum chamber with a pressure of 1×10⁻⁶. -3 Pa-5×10 -1 Pa, which makes the temperature of the substrate 150-250℃;
[0042] S02. Remove the substrate from the vacuum chamber and sequentially deposit the first oxide layer, the metal layer, and the second oxide layer using magnetron sputtering. The working gas for magnetron sputtering is argon, and the purity of the argon is >99.9%. The sputtering temperature is 20-30℃.
[0043] The steps for magnetron sputtering deposition of the first oxide layer are as follows: a mixture of modified indium oxide, tin oxide and vanadium pentoxide in a mass ratio of 85-90:8-10:6 is uniformly mixed, and the first oxide layer is deposited by magnetron sputtering. During the sputtering deposition of the first oxide layer, the sputtering power of the RF target is 600-800 watts, the sputtering rate is 0.05-2 nm / s, and the thickness of the first oxide layer is 10-12 nm.
[0044] The steps for magnetron sputtering to deposit a metal layer are as follows: a metal layer is deposited by sputtering using a magnetron sputtering method. When sputtering the first oxide layer, the sputtering power of the DC target is 50-100 watts, the sputtering rate is 0.05-0.1 nm / s, and the thickness of the metal layer is 4-5 nm.
[0045] The steps for magnetron sputtering deposition of the second oxide layer are as follows: Modified indium oxide, tin oxide, and vanadium pentoxide are mixed uniformly in a mass ratio of 85-90:8-10:6, and the first oxide layer is deposited by magnetron sputtering. During the sputtering deposition of the first oxide layer, the sputtering power of the RF target is 600-800 watts, the sputtering rate is 0.05-2 nm / s, and the thickness of the second oxide layer is 6-8 nm.
[0046] The vacuum annealing process in step S03 of this embodiment includes: placing the product from step S02 into a vacuum chamber and annealing it at 300-500°C for 20-30 minutes to obtain an electrochromic film.
[0047] The metal in the metal layer of this embodiment is one or a mixture of Ag, Au and Cu.
[0048] In this embodiment, the metal in the metal layer is a mixture of Au and Cu with a mass ratio of 1-1.5:1.
[0049] In this embodiment, the cleaning solution in step S01 is one or a mixture of ethanol, acetone, and deionized water, and the ultrasonic cleaning time is 10-15 minutes.
[0050] The dispersant in this embodiment is one of KH570 silane coupling agent and octadecyl alcohol.
[0051] The dispersant in this embodiment is KH570 silane coupling agent.
[0052] Example 1.
[0053] This embodiment of a method for preparing an electrically opaque photochromic thin film includes the following steps:
[0054] S01. Before coating, the substrate is ultrasonically cleaned in a cleaning solution, dried with nitrogen, and then placed in a vacuum chamber with a pressure of 1×10⁻⁶. -3 Pa, which makes the temperature of the substrate 150°C, wherein the substrate is a transparent conductive glass;
[0055] S02. Remove the substrate from the vacuum chamber and sequentially deposit a first oxide layer, a metal layer, and a second oxide layer using magnetron sputtering. The working gas for magnetron sputtering is argon, with a purity of >99.9%, and the sputtering temperature is 20°C.
[0056] The steps for magnetron sputtering deposition of the first oxide layer are as follows: the modified indium oxide, tin oxide and vanadium pentoxide are mixed uniformly in a mass ratio of 85:8:6, and the first oxide layer is deposited by magnetron sputtering. During the sputtering deposition of the first oxide layer, the sputtering power of the radio frequency target is 600 watts, the sputtering rate is 0.05 nm / second, and the thickness of the first oxide layer is 20 nm.
[0057] The steps for magnetron sputtering to deposit a metal layer are as follows: a metal layer is deposited by sputtering using a magnetron sputtering method. When sputtering the first oxide layer, the sputtering power of the DC target is 50 watts, the sputtering rate is 0.05 nm / second, and the thickness of the metal layer is 4 nm.
[0058] The steps for magnetron sputtering deposition of the second oxide layer are as follows: Modified indium oxide, tin oxide and vanadium pentoxide are mixed uniformly in a mass ratio of 85:8:6, and the first oxide layer is deposited by magnetron sputtering. During the sputtering deposition of the first oxide layer, the sputtering power of the RF target is 600 watts and the sputtering rate is 0.05 nm / second. The thickness of the second oxide layer is 6 nm.
[0059] S03. Vacuum annealing is performed on the product after step S02 to obtain an electrochromic film.
[0060] The method for preparing the modified indium oxide described in this embodiment includes the following steps:
[0061] First, a porous carrier with a volume ratio of 1:10 and a 50% indium nitrate solution were ultrasonically mixed for 80 minutes at a power of 200W. The precipitate was then removed and pyrolyzed at 400℃ for 1 hour. The pyrolyzed precipitate was then mixed with sodium hydroxide powder at a mass ratio of 1:1. The mixture was reacted at 800℃ under argon atmosphere for 30 minutes. After the reaction, a 20% carbonic acid solution was added at 50℃, with a volume ratio of 8:1 between the carbonic acid solution and the solid powder in the container. The mixture was reacted for 1 hour. After the reaction, the precipitate was collected to obtain porous indium oxide. The dried porous indium oxide was then subjected to a surface modification treatment to obtain modified indium oxide.
[0062] The steps of modifying the surface of the dried porous indium oxide in this embodiment include:
[0063] The dried porous indium oxide and dispersant were added to the dispersion medium and ultrasonically mixed until homogeneous. After homogeneous mixing, the mixture was ball-milled for 5 hours and finally dried to obtain modified indium oxide. The dispersant was KH570 silane coupling agent and the dispersion medium was ethylene glycol.
[0064] The porous carrier described in this embodiment is prepared by mixing carbon nanotubes with a treatment agent at a mass ratio of 2.2:1 under the protection of argon at 800°C, and then etching the carbon nanotubes to form pores for 30-80 minutes. The carbon nanotubes are multi-walled carbon nanotubes with a diameter of 0.4 nm and a length of 0.2 nm.
[0065] The treatment agent described in this embodiment is one of potassium hydroxide and sodium hydroxide.
[0066] In this embodiment, the cleaning solution in step S01 is deionized water, the ultrasonic cleaning time is 10 minutes, and the ultrasonic cleaning power is 180W.
[0067] The vacuum annealing process in step S03 of this embodiment includes: placing the product from step S02 into a vacuum chamber and annealing it at 300°C for 20 minutes to obtain an electrochromic film.
[0068] The metal in the metal layer of this embodiment is Ag.
[0069] Example 2.
[0070] This embodiment of the method for preparing an electrically opaque photochromic thin film includes the following steps:
[0071] S01. Before coating, the substrate is ultrasonically cleaned in a cleaning solution, dried with nitrogen, and then placed in a vacuum chamber with a pressure of 5 × 10⁻⁶. -1 Pa, which makes the temperature of the substrate 250°C, wherein the substrate is a transparent conductive glass;
[0072] S02. Remove the substrate from the vacuum chamber and sequentially deposit a first oxide layer, a metal layer, and a second oxide layer using magnetron sputtering. The working gas for magnetron sputtering is argon, with a purity of >99.9%, and the sputtering temperature is 30°C.
[0073] The steps for magnetron sputtering deposition of the first oxide layer are as follows: the modified indium oxide, tin oxide and vanadium pentoxide are mixed uniformly in a mass ratio of 90:10:6, and the first oxide layer is deposited by magnetron sputtering. During the sputtering deposition of the first oxide layer, the sputtering power of the radio frequency target is 800 watts, the sputtering rate is 2 nm / second, and the thickness of the first oxide layer is 30 nm.
[0074] The steps for magnetron sputtering to deposit a metal layer are as follows: a metal layer is deposited by sputtering using a magnetron sputtering method. When sputtering the first oxide layer, the sputtering power of the DC target is 100 watts, the sputtering rate is 0.1 nm / second, and the thickness of the metal layer is 5 nm.
[0075] The steps for magnetron sputtering deposition of the second oxide layer are as follows: Modified indium oxide, tin oxide and vanadium pentoxide are mixed uniformly in a mass ratio of 90:10:6, and the first oxide layer is deposited by magnetron sputtering. During the sputtering deposition of the first oxide layer, the sputtering power of the RF target is 800 watts, the sputtering rate is 2 nm / second, and the thickness of the second oxide layer is 10 nm.
[0076] S03. Vacuum annealing is performed on the product after step S02 to obtain an electrochromic film.
[0077] The method for preparing the modified indium oxide described in this embodiment includes the following steps:
[0078] First, a porous carrier with a volume ratio of 1:12 and a 50% indium nitrate solution were ultrasonically mixed for 120 min at a power of 200 W. The precipitate was then pyrolyzed at 450 °C for 3 h. The pyrolyzed precipitate was then mixed with sodium hydroxide powder at a mass ratio of 1:2. The mixture was reacted at 1200 °C under argon atmosphere for 80 min. After the reaction, a 20% carbonic acid solution was added at 60 °C at a volume ratio of 10:1 to the solid powder in the container. The mixture was reacted for 2 h. After the reaction, the precipitate was collected to obtain porous indium oxide. The dried porous indium oxide was then subjected to a surface modification treatment to obtain modified indium oxide.
[0079] The steps of modifying the surface of the dried porous indium oxide in this embodiment include:
[0080] The dried porous indium oxide and dispersant were added to the dispersion medium and ultrasonically mixed until homogeneous. After homogeneous mixing, the mixture was ball-milled for 10 hours and finally dried to obtain modified indium oxide. The dispersant was KH570 silane coupling agent and the dispersion medium was ethylene glycol.
[0081] The porous carrier described in this embodiment is prepared by mixing carbon nanotubes with a treatment agent at a mass ratio of 2.4:1 under the protection of argon at 1200°C, and then etching the carbon nanotubes to create pores for 80 minutes. The carbon nanotubes are multi-walled carbon nanotubes with a diameter of 0.4-1 nm and a length of 0.3 nm.
[0082] The treatment agent described in this embodiment is one of potassium hydroxide and sodium hydroxide.
[0083] In this embodiment, the cleaning solution in step S01 is deionized water, the ultrasonic cleaning time is 15 minutes, and the ultrasonic cleaning power is 180W.
[0084] The vacuum annealing process in step S03 of this embodiment includes: placing the product from step S02 into a vacuum chamber and annealing it at 500°C for 30 minutes to obtain an electrochromic film.
[0085] In this embodiment, the metal in the metal layer is a mixture of Au and Cu with a mass ratio of 1.5:1.
[0086] Example 3.
[0087] This embodiment of the method for preparing an electrically opaque photochromic thin film includes the following steps:
[0088] S01. Before coating, the substrate is ultrasonically cleaned in a cleaning solution, dried with nitrogen, and then placed in a vacuum chamber with a pressure of 3 × 10⁻⁶. -3Pa, which makes the temperature of the substrate 200°C, wherein the substrate is a transparent conductive glass;
[0089] S02. Remove the substrate from the vacuum chamber and sequentially deposit a first oxide layer, a metal layer, and a second oxide layer using magnetron sputtering. The working gas for magnetron sputtering is argon, with a purity of >99.9%, and the sputtering temperature is 25°C.
[0090] The steps for magnetron sputtering deposition of the first oxide layer are as follows: Modified indium oxide, tin oxide and vanadium pentoxide are mixed uniformly in a mass ratio of 88:9:6, and the first oxide layer is deposited by magnetron sputtering. During the sputtering deposition of the first oxide layer, the sputtering power of the RF target is 700 watts, the sputtering rate is 0.1 nm / second, and the thickness of the first oxide layer is 25 nm.
[0091] The steps for magnetron sputtering to deposit a metal layer are as follows: a metal layer is deposited by sputtering using a magnetron sputtering method. When sputtering the first oxide layer, the sputtering power of the DC target is 80 watts, the sputtering rate is 0.08 nm / second, and the thickness of the metal layer is 4 nm.
[0092] The steps for magnetron sputtering deposition of the second oxide layer are as follows: Modified indium oxide, tin oxide and vanadium pentoxide are mixed uniformly in a mass ratio of 88:9:6, and the first oxide layer is deposited by magnetron sputtering. During the sputtering deposition of the first oxide layer, the sputtering power of the RF target is 700 watts and the sputtering rate is 0.1 nm / second. The thickness of the second oxide layer is 8 nm.
[0093] S03. Vacuum annealing is performed on the product after step S02 to obtain an electrochromic film.
[0094] The method for preparing the modified indium oxide described in this embodiment includes the following steps:
[0095] First, a porous carrier with a volume ratio of 1:11 and a 50% indium nitrate solution were ultrasonically mixed for 100 min at a power of 200 W. The precipitate was then pyrolyzed at 420°C for 2 h. The pyrolyzed precipitate was then mixed with sodium hydroxide powder at a mass ratio of 1:1.5. The mixture was reacted at 1000°C under argon atmosphere for 60 min. After the reaction, a 20% carbonic acid solution was added at 55°C at a volume ratio of 9:1 to the solid powder in the container. The mixture was reacted for 1.5 h. After the reaction, the precipitate was collected to obtain porous indium oxide. The dried porous indium oxide was then subjected to a surface modification treatment to obtain modified indium oxide.
[0096] The steps of modifying the surface of the dried porous indium oxide in this embodiment include:
[0097] The dried porous indium oxide and dispersant were added to the dispersion medium and ultrasonically mixed until homogeneous. After homogeneous mixing, the mixture was ball-milled for 8 hours and finally dried to obtain modified indium oxide. The dispersant was KH570 silane coupling agent and the dispersion medium was ethylene glycol.
[0098] The porous carrier described in this embodiment is prepared by mixing carbon nanotubes with a treatment agent at a mass ratio of 2.3:1 under the protection of argon at 800-1200℃, and then etching the carbon nanotubes to form pores for 60 minutes. The carbon nanotubes are multi-walled carbon nanotubes with a diameter of 1 nm and a length of 0.2 nm.
[0099] The treatment agent described in this embodiment is one of potassium hydroxide and sodium hydroxide.
[0100] In this embodiment, the cleaning solution in step S01 is deionized water, the ultrasonic cleaning time is 15 minutes, and the ultrasonic cleaning power is 180W.
[0101] The vacuum annealing process in step S03 of this embodiment includes: placing the product from step S02 into a vacuum chamber and annealing it at 400°C for 25 minutes to obtain an electrochromic film.
[0102] In this embodiment, the metal in the metal layer is a mixture of Au and Cu in a mass ratio of 1:1.
[0103] Comparative Example 1.
[0104] Unlike Example 3, carbon nanotubes are directly used as the porous carrier.
[0105] Comparative Example 2.
[0106] Unlike Example 3, the dried porous indium oxide was not subjected to any surface modification treatment.
[0107] Comparative Example 3.
[0108] Unlike Example 3, indium oxide is used instead of indium oxide in the modified indium oxide.
[0109] Comparative Example 4.
[0110] Unlike Example 3, the KH570 silane coupling agent in the dispersant is replaced with octadecyl alcohol.
[0111] The products prepared in Examples 1-3 and Comparative Examples 1-4 were cut into 2×2cm samples with a bending radius of 2mm. The number of bends was measured and is shown in Table 1 below.
[0112] Table 1
[0113] Group Number of bends Example 1 3950 Example 2 4100 Example 3 4200 Comparative Example 1 3200 Comparative Example 2 3800 Comparative Example 3 2600 Comparative Example 4 3900
[0114] The experimental data from Examples 1-3 and Comparative Examples 1-4 show that the products prepared in Examples 1-3 of this invention can eliminate internal stress during bending and improve bending stability by utilizing a porous structure.
[0115] The performance test results of fading time and coloring time of the products prepared in Examples 1-3 and Comparative Examples 1-4 are shown in Table 2.
[0116] Table 2
[0117] Group Bleaching time (s) Coloring time (s) Example 1 1.9 2.1 Example 2 1.4 1.9 Example 3 1.0 1.6 Comparative Example 1 3.6 2.7 Comparative Example 2 2.5 2.3 Comparative Example 3 5.5 4.6 Comparative Example 4 2.3 2.2
[0118] As can be seen from the experimental data in Table 2, the coloring and fading times of the electrochromic films prepared in Examples 1-3 of this invention are relatively short, indicating that the products prepared by this invention have a fast response speed. By comparing with the data of Comparative Examples 1-4, it can be seen that pore-forming carbon nanotubes is beneficial to the preparation of porous indium oxide, so that the prepared products have a pore structure. This can eliminate bending internal stress and improve the photoelectric response speed through the pore structure. Furthermore, by modifying the surface of porous indium oxide, agglomeration can be further avoided and dispersion can be improved, thereby further improving the stability and photoelectric response of the products.
[0119] It will be apparent to those skilled in the art that the present invention is not limited to the details of the exemplary embodiments described above, and that the invention can be implemented in other specific forms without departing from the spirit or essential characteristics of the invention. Therefore, the embodiments should be considered in all respects as exemplary and non-limiting, and the scope of the invention is defined by the appended claims rather than the foregoing description. Thus, it is intended that all variations falling within the meaning and scope of equivalents of the claims be included within the present invention.
[0120] Furthermore, it should be understood that although this specification describes embodiments, not every embodiment contains only one independent technical solution. This narrative style is merely for clarity. Those skilled in the art should consider the specification as a whole, and the technical solutions in each embodiment can also be appropriately combined to form other embodiments that can be understood by those skilled in the art.
Claims
1. A method for preparing an electrically opaque photochromic thin film, characterized in that, Includes the following steps: S01. Before coating, the substrate is ultrasonically cleaned in a cleaning solution, dried with nitrogen, and then placed in a vacuum chamber with a pressure of 1×10⁻⁶. -3 Pa-5×10 -1 Pa, which makes the temperature of the substrate 150-250℃; S02. Remove the substrate from the vacuum chamber and sequentially deposit the first oxide layer, the metal layer, and the second oxide layer using magnetron sputtering. S03. Vacuum annealing is performed on the product after step S02 to obtain an electrochromic film. Wherein, the first oxide layer and the second oxide layer are made of the same material, and the first oxide layer and the second oxide layer are made of modified indium oxide, tin oxide and vanadium pentoxide in a mass ratio of 85-90:8-10:
6. The preparation method of the modified indium oxide includes the following steps: First, a porous carrier with a volume ratio of 1:10-12 is ultrasonically mixed with a 50% indium nitrate solution for 80-120 min. The precipitate is then pyrolyzed at 400-450℃ for 1-3 h. The pyrolyzed precipitate is then mixed with sodium hydroxide powder at a mass ratio of 1:1-2. The mixture is reacted at 800-1200℃ under argon atmosphere for 30-80 min. After the reaction, a 20% carbonic acid solution is added at 50-60℃, with a volume ratio of 8-10:1 between the carbonic acid solution and the solid powder in the container. The mixture is reacted for 1-2 h. After the reaction, the precipitate is collected to obtain porous indium oxide. The dried porous indium oxide is then subjected to a surface modification treatment to obtain modified indium oxide. The steps for modifying the surface of dried porous indium oxide include: The dried porous indium oxide and dispersant were added to a dispersion medium and ultrasonically mixed until homogeneous. After homogeneity, the mixture was ball-milled for 5-10 hours and finally dried to obtain modified indium oxide. The dispersant was KH570 silane coupling agent. The porous carrier is prepared by mixing carbon nanotubes with a treatment agent at a mass ratio of 2.2-2.4:1 under argon protection at 800-1200℃, and then etching the carbon nanotubes to create pores for 30-80 minutes.
2. The method for preparing an electrically opaque photochromic thin film according to claim 1, characterized in that, The treatment agent is either potassium hydroxide or sodium hydroxide.
3. The method for preparing an electrically opaque photochromic thin film according to claim 1, characterized in that, S02. Remove the substrate from the vacuum chamber and sequentially deposit the first oxide layer, the metal layer, and the second oxide layer using magnetron sputtering. The working gas for magnetron sputtering is argon, and the purity of the argon is >99.9%. The sputtering temperature is 20-30℃. The steps for magnetron sputtering deposition of the first oxide layer are as follows: a mixture of modified indium oxide, tin oxide and vanadium pentoxide in a mass ratio of 85-90:8-10:6 is uniformly mixed, and the first oxide layer is deposited by magnetron sputtering. During the sputtering deposition of the first oxide layer, the sputtering power of the RF target is 600-800 watts, the sputtering rate is 0.05-2 nm / s, and the thickness of the first oxide layer is 20-30 nm. The steps for magnetron sputtering to deposit a metal layer are as follows: a metal layer is deposited by sputtering using a magnetron sputtering method. When sputtering the first oxide layer, the sputtering power of the DC target is 50-100 watts, the sputtering rate is 0.05-0.1 nm / s, and the thickness of the metal layer is 4-5 nm. The steps for magnetron sputtering deposition of the second oxide layer are as follows: a mixture of modified indium oxide, tin oxide, and vanadium pentoxide in a mass ratio of 85-90:8-10:6 is homogeneous, and the first oxide layer is deposited by magnetron sputtering. During the sputtering deposition of the first oxide layer, the sputtering power of the RF target is 600-800 watts, the sputtering rate is 0.05-2 nm / s, and the thickness of the second oxide layer is 6-10 nm.
4. The method for preparing an electrically opaque photochromic thin film according to claim 1, characterized in that, The vacuum annealing process in step S03 includes: placing the product from step S02 into a vacuum chamber and annealing it at 300-500°C for 20-30 minutes to obtain an electrochromic film.
5. The method for preparing an electrically opaque photochromic thin film according to claim 1, characterized in that, The metal in the metal layer is one or a mixture of Ag, Au and Cu.
6. The method for preparing an electrically opaque photochromic thin film according to claim 5, characterized in that, The metal in the metal layer is a mixture of Au and Cu with a mass ratio of 1-1.5:
1.
7. The method for preparing an electrically opaque photochromic thin film according to claim 1, characterized in that, The cleaning solution in step S01 is one or a mixture of ethanol, acetone, and deionized water, and the ultrasonic cleaning time is 10-15 minutes.