A metal nanofilm and its preparation method
By covering the SnF cladding layer on the copper nanowire film to form a three-layer composite film, the problem of insufficient stability after electroplating of the copper nanowire film is solved, and the combination of high stability and high light transmittance is achieved.
Patent Information
- Application Number
- CN202311327071.8
- Authority / Receiving Office
- CN · China
- Patent Type
- Patents(China)
- Current Assignee / Owner
- Filing Date
- 2023-10-13
- Publication Date
- 2025-08-29
- Estimated Expiration
- 2043-10-13
AI Technical Summary
In the prior art, the copper nanowire film has insufficient stability after electroplating and cannot achieve ideal results.
By preparing a copper nanowire solution, spraying it on a PET substrate and electroplating, the SnF cladding layer is then coated on the electroplating copper nanowire transparent conductive film material to form a three-layer composite film, including a base layer, a spray coating layer, an electroplating layer and a cladding layer.
The stability of the copper nanowire film is improved while maintaining a low resistivity and high light transmittance. The performance of the three-layer composite film is better than that of the untreated copper nanowire film.
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Abstract
Description
Technical Field
[0001] The present invention belongs to the technical field of transparent electronic information material preparation, and relates to a metal nano film with high stability, high optical transmittance and electrical conductivity and a preparation method thereof. Background Art
[0002] With the development of information technology, transparent conductive films, due to their excellent optical and electrical properties, are widely used in electronic technologies such as touch screens and liquid crystal displays. As a key component of transparent electronic components, their research and development has always attracted widespread attention. Transmittance and resistance, as important factors in transparent electronic components, are important subjects for studying their optoelectronic properties. In recent years, the research of transparent conductive film materials with high transmittance (transmittance > 80%) and low square resistance (square resistance < 50Ω / sq.) has become a research hotspot in the field of information functional materials.
[0003] It has been found that after the CuNWs film (copper nanowire film) obtained by spraying is treated with glacial acetic acid, it can obtain lower resistivity and higher transmittance, but the uniformity and stability of the material are still insufficient. By applying electroplating and adding a protective layer to optimize the copper nanowire film, the uniformity and stability of the film can be improved, and a transparent conductive film material with good performance can be obtained. At this stage, the CuNWs film can be coated on the Cu 2+ Electroplating is performed in an electroplating solution to reduce the resistivity of CuNWs. However, the stability of the metal nanowires after electroplating is not high, and the ideal effect cannot be achieved. Summary of the Invention
[0004] The purpose of the present invention is to provide a metal nanofilm and a preparation method thereof, which can solve the problem of insufficient stability of copper nanowire films after electroplating in the prior art.
[0005] The purpose of the present invention is achieved through the following technical solutions:
[0006] In a first aspect, the present invention provides a method for preparing a metal nanofilm, comprising the following steps:
[0007] preparing a copper nanowire solution;
[0008] The copper nanowire solution is evenly sprayed on a PET substrate and naturally evaporated at room temperature to form a copper nanowire transparent conductive film material;
[0009] The copper nanowire transparent conductive film material was placed in the prepared 400 mL electroplating solution and electroplated for 20 seconds;
[0010] The coating liquid was coated on the electroplated copper nanowire transparent conductive film material for 1 hour. After the coating was completed, the surface was washed with deionized water and evaporated and dried at room temperature to obtain a metal nanofilm.
[0011] Furthermore, the step of preparing the copper nanowire solution includes:
[0012] Step S1: using an electronic balance to measure the molar ratio of CuCl2:C6H 12 O6:ODA=1:(1~3):(4~8) was prepared and dissolved in 60mL deionized water;
[0013] Step S2: placing the mixed solution obtained in step S1 in a magnetic stirrer and stirring at 300 rpm for 5 to 10 hours at room temperature to form a blue solution;
[0014] Step S3, transferring the uniformly stirred blue solution to a hydrothermal reactor, reacting at 110-130° C. for 24-30 hours, and naturally cooling to room temperature after the reaction to obtain a copper nanowire solution;
[0015] Step S4: cleaning the copper nanowire solution.
[0016] Furthermore, the step of cleaning the copper nanowire solution includes:
[0017] The copper nanowire solution was evenly distributed into an even number of centrifuge tubes;
[0018] Centrifuge and wash with deionized water: Add 20-30 mL of deionized water to each centrifuge tube, centrifuge at 2000 r / min for 5 min, then centrifuge at 12000 r / min for 5 min, and discard the supernatant.
[0019] Then, the product was centrifugally washed with n-hexane and isopropanol in the same manner as with deionized water. After completion, the product was dispersed in isopropanol for later use.
[0020] Furthermore, the step of uniformly spraying the copper nanowire solution on the PET substrate includes: diluting the copper nanowire solution and adding it to a spray bottle, rotating the spray bottle at a speed of 500 r / min and spraying the copper nanowire solution on the PET substrate.
[0021] Furthermore, the preparation process of the electroplating solution includes: 25g of HEDP, 4g of Cu 2+ and 16 g of K2CO3 were dissolved in 400 mL of deionized water, and the pH value was adjusted to between 9 and 10 with KOH.
[0022] Furthermore, the electroplating temperature is room temperature, and the electroplating voltage is 0.1V to 2V.
[0023] Preferably, the electroplating voltage is 0.7V.
[0024] Furthermore, the components and proportions of the coating solution are: SnF: isopropyl alcohol: deionized water = 0.04:25:17.
[0025] In a second aspect, the present invention provides a metal nanofilm prepared by the above-mentioned preparation method, which includes, from the inside out, a base layer, a spray layer, an electroplating side and a coating layer.
[0026] The metal nanofilm and its preparation method of the present invention utilize SnF (single SiO2 nanofibers) for surface modification of metal nanowires. By coating the electroplated metal nanowires with SnF to form a coating, the stability of the CuNWs film is significantly improved while maintaining low resistivity and high transmittance. The three-layer composite film exhibits far superior performance to untreated copper nanowire films. By adjusting the coating time, an optimal copper nanowire-based transparent conductive film can be obtained. DETAILED DESCRIPTION
[0027] The following is a detailed description of the embodiments of the present disclosure.
[0028] The following describes the embodiments of the present disclosure through specific examples, and those skilled in the art can easily understand other advantages and effects of the present disclosure from the contents disclosed in this specification. Obviously, the described embodiments are only a part of the embodiments of the present disclosure, rather than all of the embodiments. The present disclosure can also be implemented or applied through other different specific embodiments, and the details in this specification can also be modified or changed in various ways based on different viewpoints and applications without departing from the spirit of the present disclosure. It should be noted that, in the absence of conflict, the following embodiments and features in the embodiments can be combined with each other. Based on the embodiments in the present disclosure, all other embodiments obtained by ordinary technicians in this field without making creative work are within the scope of protection of the present disclosure.
[0029] Example 1
[0030] A method for preparing a metal nanofilm according to this embodiment includes the following steps:
[0031] Step S1: using an electronic balance to measure the molar ratio of CuCl2:C6H 12 O6:ODA (octadecylamine)=1:3:8 was prepared and dissolved in 60 mL of deionized water.
[0032] Step S2: Place the mixed solution obtained in step S1 in a magnetic stirrer and stir at 300 rpm for 10 h at room temperature to form a blue solution.
[0033] Step S3: Transfer the stirred and evenly mixed blue solution to a 1000 mL hydrothermal reactor and react at 130° C. for 30 h. After the reaction is completed, naturally cool to room temperature to obtain a brick-red liquid, i.e., a copper nanowire solution.
[0034] Step S4: washing the copper nanowire solution obtained in step S3.
[0035] Furthermore, the step of cleaning the copper nanowire solution in step S4 includes:
[0036] Use a dropper to add the copper nanowire solution to six centrifuge tubes, adding about 10 mL of the copper nanowire solution to each centrifuge tube;
[0037] Centrifuge and wash with deionized water: Add 20-30 mL of deionized water to each centrifuge tube, centrifuge at 2000 r / min for 5 min, then centrifuge at 12000 r / min for 5 min, and discard the supernatant.
[0038] Then, the product was washed with deionized water in the same manner, and centrifuged with n-hexane and isopropanol respectively. After completion, the product was dispersed in isopropanol for later use.
[0039] The number of centrifuge tubes can be an even number, and the copper nanowire solution can be evenly distributed among them. For ease of illustration, six centrifuge tubes are used in this example. An even number of centrifuge tubes is chosen because they should be placed opposite each other to maintain rotational balance during centrifugal rotation.
[0040] Step S5: evenly spray the cleaned copper nanowires onto a clean PET substrate and allow them to evaporate naturally at room temperature to form a copper nanowire transparent conductive film material.
[0041] Furthermore, the uniform spraying method includes: diluting the cleaned copper nanowire solution and adding it to a spray bottle, rotating the spray bottle at a speed of 500 r / min and spraying the copper nanowire solution on the PET substrate.
[0042] Step S6: Place the copper nanowire film material prepared in step S5 in 400 mL of the prepared electroplating solution for electroplating for 20 seconds.
[0043] The further preparation process of the electroplating solution includes: 25g of HEDP (hydroxyethyl diphosphonic acid), 4g of Cu 2+ and 16 g of K2CO3 were dissolved in 400 mL of deionized water, and the pH value was adjusted to between 9 and 10 with KOH (potassium hydroxide).
[0044] Furthermore, the electroplating temperature is room temperature, and the electroplating voltage is 0.1V to 2V, preferably 0.7V.
[0045] Step S7: coating the electroplated copper nanowire transparent conductive film material with a coating liquid for 1 hour. After coating, the surface is washed with deionized water and evaporated and dried at room temperature to obtain a metal nanofilm.
[0046] The components and proportions of the coating solution are: SnF:isopropyl alcohol:deionized water=0.04:25:17.
[0047] The copper nanowire transparent conductive film prepared according to Example 1 had a square resistance of 20.8Ω / sq and a light transmittance of 84.0%. After 12 hours in an environment with a humidity of 85% and a temperature of 85°C, the copper nanowire transparent conductive film became non-conductive.
[0048] The metal nanofilm prepared by the method of this embodiment includes, from the inside out, a base layer, a spray layer, an electroplating side, and a coating layer.
[0049] Example 2
[0050] A method for preparing a metal nanofilm according to this embodiment includes the following steps:
[0051] Step S1: using an electronic balance to measure the molar ratio of CuCl2:C6H 12 O6:ODA (octadecylamine)=1:1:6 was prepared and dissolved in 60 mL of deionized water.
[0052] Step S2: Place the mixed solution obtained in step S1 in a magnetic stirrer and stir at 300 rpm for 5 h at room temperature to form a blue solution.
[0053] Step S3: Transfer the stirred and evenly mixed blue solution to a 100 mL hydrothermal reactor and react at 110° C. for 24 h. After the reaction is completed, naturally cool to room temperature to obtain a brick-red liquid, i.e., a copper nanowire solution.
[0054] Step S4: washing the copper nanowire solution obtained in step S3.
[0055] The cleaning steps are the same as those in Example 1 and are not described here in detail.
[0056] Step S5: evenly spray the cleaned copper nanowires onto a clean PET substrate and volatilize naturally at room temperature to form a copper nanowire transparent conductive film material.
[0057] The method of uniform spraying is the same as that in Example 1 and will not be described in detail here.
[0058] Step S6: Place the copper nanowire transparent conductive film material prepared in step S5 in 400 mL of the prepared electroplating solution for electroplating for 20 seconds.
[0059] The preparation process of the electroplating solution, the electroplating temperature and the electroplating voltage are the same as those in Example 1 and will not be described in detail here.
[0060] Step S7: coating the electroplated copper nanowire transparent conductive film material with a coating liquid for 2 hours. After coating, the surface is washed with deionized water and evaporated and dried at room temperature to obtain a metal nanofilm.
[0061] The coating liquid is the same as that in Example 1 and will not be described again here.
[0062] The copper nanowire transparent conductive film prepared according to Example 2 had a square resistance of 21.5Ω / sq and a light transmittance of 84.0%. After 12 hours in an environment with a humidity of 85% and a temperature of 85°C, the copper nanowire transparent conductive film was no longer conductive.
[0063] Example 3
[0064] Step S1: using an electronic balance to measure the molar ratio of CuCl2:C6H 12 O6:ODA (octadecylamine)=1:3:10 was prepared and dissolved in 60 mL of deionized water.
[0065] Step S2: Place the mixed solution obtained in step S1 in a magnetic stirrer and stir at 300 rpm for 10 h at room temperature to form a blue solution.
[0066] Step S3: Transfer the stirred and evenly mixed blue solution to a 1000 mL hydrothermal reactor and react at 110° C. for 30 h. After the reaction is completed, naturally cool to room temperature to obtain a brick-red liquid, i.e., a copper nanowire solution.
[0067] Step S4: washing the copper nanowire solution obtained in step S3.
[0068] The cleaning steps are the same as those in Example 1 and are not described here in detail.
[0069] Step S5: evenly spray the cleaned copper nanowires onto a clean PET substrate and volatilize naturally at room temperature to form a copper nanowire transparent conductive film material.
[0070] The method of uniform spraying is the same as that in Example 1 and will not be described in detail here.
[0071] Step S6: Place the copper nanowire transparent conductive film material prepared in step S5 in 400 mL of the prepared electroplating solution for electroplating for 20 seconds.
[0072] The preparation process of the electroplating solution, the electroplating temperature and the electroplating voltage are the same as those in Example 1 and will not be described in detail here.
[0073] Step S7: coating the electroplated copper nanowire transparent conductive film material with a coating liquid for 2.5 hours. After coating, the surface is washed with deionized water and evaporated and dried at room temperature to obtain a metal nanofilm.
[0074] The coating liquid is the same as that in Example 1 and will not be described again here.
[0075] The copper nanowire transparent conductive film prepared according to Example 3 had a square resistance of 24.8Ω / sq and a transmittance of 83.8%. After 12 hours in an environment with a humidity of 85% and a temperature of 85°C, the square resistance of the copper nanowire transparent conductive film was 46.6Ω / sq.
[0076] Example 4
[0077] A method for preparing a metal nanofilm according to this embodiment includes the following steps:
[0078] Step S1: using an electronic balance to measure the molar ratio of CuCl2:C6H 12 O6:ODA (octadecylamine)=1:1:4 was prepared and dissolved in 60 mL of deionized water.
[0079] Step S2: Place the mixed solution obtained in step S1 in a magnetic stirrer and stir at 300 rpm for 5 h at room temperature to form a blue solution.
[0080] Step S3: Transfer the stirred and evenly mixed blue solution to a 60 mL hydrothermal reactor and react at 130° C. for 24 h. After the reaction is completed, naturally cool to room temperature to obtain a brick-red liquid, i.e., a copper nanowire solution.
[0081] Step S4: washing the copper nanowire solution obtained in step S3.
[0082] The cleaning steps are the same as those in Example 1 and are not described here in detail.
[0083] Step S5: evenly spray the cleaned copper nanowires onto a clean PET substrate and allow them to evaporate naturally at room temperature to form a copper nanowire transparent conductive film material.
[0084] The method of uniform spraying is the same as that in Example 1 and will not be described in detail here.
[0085] Step S6: Place the copper nanowire transparent conductive film material prepared in step S5 in 400 mL of the prepared electroplating solution for electroplating for 20 seconds.
[0086] The preparation process of the electroplating solution, the electroplating temperature and the electroplating voltage are the same as those in Example 1 and will not be described in detail here.
[0087] Step S7: coating the electroplated copper nanowire transparent conductive film material with a coating liquid for 3 hours. After coating, the surface is washed with deionized water and evaporated and dried at room temperature to obtain a metal nanofilm.
[0088] The coating liquid is the same as that in Example 1 and will not be described again here.
[0089] The copper nanowire transparent conductive film prepared according to Example 4 had a square resistance of 33.1Ω / sq and a light transmittance of 83.4%. After 12 hours in an environment with a humidity of 85% and a temperature of 85°C, the square resistance of the copper nanowire transparent conductive film was 256.7Ω / sq.
[0090] Example 5
[0091] A method for preparing a metal nanofilm according to this embodiment includes the following steps:
[0092] Step S1: using an electronic balance to measure the molar ratio of CuCl2:C6H 12 O6:ODA (octadecylamine)=1:3:10 was prepared and dissolved in 60 mL of deionized water.
[0093] Step S2: Place the mixed solution obtained in step S1 in a magnetic stirrer and stir at 300 rpm for 5 h at room temperature to form a blue solution.
[0094] Step S3: Transfer the stirred and evenly mixed blue solution to a 500 mL hydrothermal reactor and react at 130° C. for 24 h. After the reaction is completed, naturally cool to room temperature to obtain a brick-red liquid, i.e., a copper nanowire solution.
[0095] Step S4: washing the copper nanowire solution obtained in step S3.
[0096] The cleaning steps are the same as those in Example 1 and are not described here in detail.
[0097] Step S5: evenly spray the cleaned copper nanowires onto a clean PET substrate and volatilize naturally at room temperature to form a copper nanowire transparent conductive film material.
[0098] The method of uniform spraying is the same as that in Example 1 and will not be described in detail here.
[0099] Step S6: Place the copper nanowire transparent conductive film material prepared in step S5 in 400 mL of the prepared electroplating solution for electroplating for 20 seconds.
[0100] The preparation process of the electroplating solution, the electroplating temperature and the electroplating voltage are the same as those in Example 1 and will not be described in detail here.
[0101] Step S7: coating the electroplated copper nanowire transparent conductive film material with a coating liquid for 4 hours. After coating, the surface is washed with deionized water and evaporated and dried at room temperature to obtain a metal nanofilm.
[0102] The coating liquid is the same as that in Example 1 and will not be described again here.
[0103] The copper nanowire transparent conductive film prepared according to Example 5 had a square resistance of 49.6Ω / sq and a light transmittance of 83.7%. After 12 hours in an environment with a humidity of 85% and a temperature of 85°C, the square resistance of the copper nanowire transparent conductive film was 188.2Ω / sq.
[0104] The optical and electrical properties of the conductive films of Examples 1 to 5 at different coating times are shown in Table 1.
[0105] The experimental parameters of each embodiment of the present invention are as follows:
[0106]
[0107]
[0108] Table 1
[0109] The above is only for explaining the embodiments of the present invention and is not intended to limit the present invention. For those skilled in the art, any modification, equivalent replacement, improvement, etc. made within the spirit and principles of the present invention without creative work should be included in the scope of protection of the present invention.
Claims
1. A method for preparing a metal nanofilm, characterized in that: The following steps are involved: preparing a copper nanowire solution; The copper nanowire solution is evenly sprayed on a PET substrate and naturally evaporated at room temperature to form a copper nanowire transparent conductive film material; The copper nanowire transparent conductive film material was placed in the prepared 400 mL electroplating solution and electroplated for 20 seconds; The preparation process of the electroplating solution includes: 25g of HEDP, 4g of Cu 2+ and 16 g of K2CO3 dissolved in 400 mL of deionized water, and adjusted the pH to between 9 and 10 with KOH; A coating liquid is coated on the electroplated copper nanowire transparent conductive film material. The components and proportions of the coating liquid are: SnF: isopropyl alcohol: deionized water = 0.04:25:
17. The coating time is 1 hour. After the coating is completed, the surface is washed with deionized water and evaporated and dried at room temperature to obtain a metal nanofilm.
2. The method for preparing a metal nanofilm according to claim 1, wherein: The steps of preparing the copper nanowire solution include: Step S1: using an electronic balance to measure the molar ratio of CuCl2:C6H 12 Prepare O6:ODA=1:(1-3):(4-8) and dissolve in 60 mL of deionized water; Step S2: placing the mixed solution obtained in step S1 in a magnetic stirrer and stirring at 300 rpm for 5 to 10 hours at room temperature to form a blue solution; Step S3, transferring the uniformly stirred blue solution to a hydrothermal reactor, reacting at 110-130° C. for 24-30 h, and naturally cooling to room temperature after the reaction to obtain a copper nanowire solution; Step S4: cleaning the copper nanowire solution.
3. The method for preparing a metal nanofilm according to claim 2, wherein: The step of cleaning the copper nanowire solution comprises: The copper nanowire solution was evenly distributed into an even number of centrifuge tubes; Centrifuge and wash with deionized water: Add 20-30 mL of deionized water to each centrifuge tube, centrifuge at 2000 r / min for 5 min, then centrifuge at 12000 r / min for 5 min, and discard the supernatant. Then, the product was centrifugally washed with n-hexane and isopropanol in the same manner as with deionized water. After completion, the product was dispersed in isopropanol for later use.
4. The method for preparing a metal nanofilm according to claim 1, wherein: The step of uniformly spraying the copper nanowire solution on the PET substrate includes: diluting the copper nanowire solution and adding it to a spray bottle, rotating the spray bottle at a speed of 500 r / min and spraying the copper nanowire solution on the PET substrate.
5. The method for preparing a metal nanofilm according to claim 1, wherein: The electroplating temperature is room temperature, and the electroplating voltage is 0.1V~2V.
6. The method for preparing a metal nanofilm according to claim 5, wherein: The plating voltage was 0.7V.
7. A metal nanofilm, characterized in that: The metal nanofilm is prepared by the method for preparing the metal nanofilm according to any one of claims 1 to 6, and comprises, from the inside to the outside, a base layer, a spray layer, an electroplating side and a coating layer.