Metal patterning process and device based on capillary action and product

Abstract

The invention provides a metal patterning process and device based on capillary action and a product, and relates to the technical field of metal pattern processing, and the technical scheme is characterized in that the metal patterning process comprises the steps that a template with a corresponding pattern micro-columnar structure is prepared according to a needed pattern; preparing a substrate; preparing a medium solution; the template is placed below the substrate, and the distance between the template and the substrate is the distance capable of generating the capillary action; injecting the medium solution into a gap between the template and the substrate, and enabling the medium solution to flow along the corresponding pattern micro-columnar structure on the template; and connecting the template and the substrate to a closed circuit for electro-deposition. The metal patterning process, device and product based on the capillary action have the advantages of being low in cost, easy to operate, high in preparation efficiency and easy to control.

Description

Technical Field

[0001] The present application relates to the technical field of metal pattern processing, and in particular, to a metal patterning process, device and product based on capillary action. Background Art

[0002] Patterned metal micro-nano arrays have great potential applications in the fields of surface plasmon resonance sensors, surface enhanced Raman spectroscopy, surface enhanced fluorescence, solar cells, etc. At present, the main preparation methods for metal patterning include photolithography, electron beam etching, focused ion beam etching, transfer imprinting, polymer-assisted metal deposition, chemical vapor deposition, laser-assisted electrodeposition, etc. The traditional photolithography process is complex and is limited by the optical diffraction limit. Electron beam technology has problems such as high cost. Electrochemical deposition is often used to prepare metal films. Its advantages are low cost, simple operation, high preparation efficiency, and strong controllability. However, the traditional electrochemical deposition method is generally used to prepare metal film samples. It is difficult to achieve local metal deposition and it is impossible to perform specific metal patterning deposition at specific locations according to actual requirements.

[0003] In view of the above problems, the present application proposes a new technical solution. Summary of the invention

[0004] The purpose of the present application is to provide a metal patterning process based on capillary action, which has the advantages of low cost, simple operation, high preparation efficiency and easy control.

[0005] In the first aspect, the present application provides a metal patterning process based on capillary action, and the technical solution is as follows: include: According to the desired pattern, a template having a micro-columnar structure of a corresponding pattern is prepared; preparing a substrate; Prepare medium solution; placing the template below the substrate, and making the distance between the template and the substrate a distance capable of generating a capillary action; Injecting the medium solution into the gap between the template and the substrate, so that the medium solution flows along the corresponding pattern micro-columnar structure on the template; The template and the substrate are connected to a closed circuit for electrodeposition.

[0006] Further, in the present application, the step of preparing a template having a micro-columnar structure of a corresponding pattern according to a desired pattern includes: Polished on one side according to the required pattern <100> The non-etched portion of the N-type doped single crystal silicon exposed on the crystal surface is covered with photoresist; Etching the areas not protected by photoresist; The excess photoresist is removed to obtain the template having a micro-columnar structure with a corresponding pattern.

[0007] Furthermore, in the present application, the process also includes: Modifying the template having a corresponding pattern micro-columnar structure to obtain a modified template having asymmetric wettability, wherein the modified template is a template having a periodic microstructure of highly doped silicon columns and having asymmetric wettability; Using the modified template and the substrate to perform electrodeposition; The step of modifying the template having the corresponding pattern micro-columnar structure to obtain a modified template having asymmetric wettability comprises: Applying positive photoresist on top of the template having the corresponding pattern of micro-columnar structures; Adding silane as a modifying chemical to the template coated with positive photoresist; Vacuuming and drying; The excess positive photoresist is removed to obtain the modified template with asymmetric wettability.

[0008] Furthermore, in the present application, the silane used as the modifying chemical is perfluorooctyltrichlorosilane and / or octadecyltrimethoxysilane.

[0009] Furthermore, in the present application, the step of preparing the substrate comprises: The substrate was ultrasonically cleaned in ethanol, acetone, and isopropanol in sequence, dried using a nitrogen gun, and treated using a plasma cleaner.

[0010] Furthermore, in the present application, the medium solution includes at least a main salt and a conductive salt, and the main salt is a metal ion deposited during the electrodeposition process, including at least one of copper ions, silver ions, gold ions, and nickel ions.

[0011] Furthermore, in the present application, the step of preparing the medium solution comprises: Prepare a sulfate copper plating solution as the medium solution, or prepare a silver nitrate silver plating solution as the medium solution; When the sulfate copper plating solution is used as the medium solution, the components of the sulfate copper plating solution are: Copper sulfate 160-180 g / L; Sulfuric acid 60-70 g / L; Hydrochloric acid 1ml / L; When the silver nitrate plating solution is used as the medium solution, the components of the silver nitrate plating solution are: Silver nitrate 40-45 g / L; Sodium thiosulfate 230 g / L; Potassium metabisulfite 40 g / L; Ammonium acetate 25 g / L; Thiosemicarbazide 0.7 g / L.

[0012] Further, in the present application, the step of connecting the template and the substrate to a closed circuit for electrodeposition includes: The template and the substrate were connected to a closed circuit and 0.001A / dm 2 ~10A / dm 2 The constant current lasts from 1 minute to 600 minutes.

[0013] In a second aspect, the present application further proposes a metal patterning device based on capillary action, which is used to complete the above-mentioned metal patterning process based on capillary action, and at least includes: An XYZ three-axis driving platform is provided on the XYZ three-axis driving platform, wherein an upper mold fixing plate capable of moving in the Z-axis direction and a lower mold fixing plate capable of moving in the Z-axis and Y-axis directions are provided, the template is arranged on the lower mold fixing plate, the substrate is arranged on the upper mold fixing plate, a power supply for electrically connecting the template and the substrate and a microscope located above the substrate are also provided, the substrate is made of a transparent material, and under the drive of the XYZ three-axis driving platform, the substrate is controlled to be aligned with the template, and the distance between the substrate and the template is made to be 500 nanometers to 10 micrometers.

[0014] In a third aspect, the present application further proposes a product having a metal pattern, wherein the product is manufactured using the above-mentioned metal patterning process based on capillary action.

[0015] From the above, it can be seen that the metal patterning process, device and product based on capillary action provided in the present application realize precise metal patterning at the micro-nano scale by utilizing a method combining capillary action and electrodeposition, while reducing the preparation cost, simplifying the operation process, and improving the preparation efficiency and controllability. BRIEF DESCRIPTION OF THE DRAWINGS

[0016] Figure 1 A flow chart of a metal patterning process based on capillary action provided in this application.

[0017] Figure 2 A schematic diagram of the structure of a template with a corresponding pattern micro-columnar structure provided in this application.

[0018] Figure 3 Schematic diagram of the structure of the modified template with asymmetric wettability provided in this application.

[0019] Figure 4A schematic structural diagram of a metal patterning device based on capillary action provided in this application.

[0020] Figure 5 Schematic diagram of electrodeposition provided for this application.

[0021] Figure 6 A schematic diagram of a substrate after electrodeposition provided in one embodiment of the present application.

[0022] Figure 7 for Figure 6 EDS spectrum of the medium substrate.

[0023] Figure 8 A schematic diagram of a substrate after electrodeposition provided in one embodiment of the present application.

[0024] Fig. 9 for Figure 8 EDS spectrum of the substrate.

[0025] Fig.10 A schematic diagram of a substrate after electrodeposition provided in one embodiment of the present application.

[0026] Fig.11 for Fig.10 EDS spectrum of the medium substrate.

[0027] In the figure: 300, medium solution; 400, XYZ three-axis driving platform; 401, transfer stage Z direction adjustment knob; 402, microscope; 403, fixing knob; 404, upper transfer stage; 405, upper mold fixing plate; 406, substrate; 407, template; 408, transfer stage X direction adjustment knob; 409, transfer stage Y direction adjustment knob; 410, transfer stage horizontal rotation knob; 411, microscope Z direction adjustment knob; 412, power supply; 413, microscope X direction adjustment knob; 414, microscope Y direction adjustment knob; 415, lower transfer stage. DETAILED DESCRIPTION

[0028] The technical solutions in the present application will be clearly and completely described below in conjunction with the drawings in the present application. Obviously, the described embodiments are only a part of the embodiments of the present application, rather than all the embodiments. The components of the present application generally described and shown in the drawings here can be arranged and designed in various different configurations. Therefore, the following detailed description of the embodiments of the present application provided in the drawings is not intended to limit the scope of the present application for protection, but merely represents the selected embodiments of the present application. Based on the embodiments of the present application, all other embodiments obtained by those skilled in the art without making creative work belong to the scope of protection of the present application.

[0029] It should be noted that similar reference numerals and letters represent similar items in the following drawings, so once an item is defined in one drawing, it does not need to be further defined and explained in subsequent drawings. At the same time, in the description of this application, the terms "first", "second", etc. are only used to distinguish the description and cannot be understood as indicating or implying relative importance.

[0030] Patterned metal micro-nano arrays have great potential applications in the fields of surface plasmon resonance sensors, surface enhanced Raman spectroscopy, surface enhanced fluorescence, solar cells, etc. However, traditional metal patterning methods such as photolithography and electron beam etching have problems such as complex processes and high costs, making it difficult to achieve local metal deposition and metal patterning deposition at specific locations. Although electrochemical deposition is low-cost, simple to operate, and has high preparation efficiency, it is also difficult to achieve local metal deposition.

[0031] In order to overcome the above technical limitations, this application proposes a metal patterning process based on capillary action. This process prepares a template with a micro-columnar structure of a corresponding pattern, and uses the capillary action between the template and the substrate to guide the flow of the medium solution on the template, and finally realizes metal patterning through electrodeposition.

[0032] Specifically, refer to Figure 1 , the process steps include: S110, preparing a template having a micro-columnar structure with a corresponding pattern according to a desired pattern; S120, preparing a substrate; S130, preparing a medium solution; S140, placing the template below the substrate, and making the distance between the template and the substrate a distance that can produce a capillary action; S150, injecting the medium solution into the gap between the template and the substrate, so that the medium solution flows along the corresponding pattern micro-columnar structure on the template; S160, connecting the template and the substrate to a closed circuit for electrodeposition.

[0033] This process is used to solve the technical problem that traditional electrochemical deposition methods are difficult to achieve local selective deposition. Among them, the template has a structure with a corresponding pattern of micro-columnar structures, which can be prepared by single-crystal silicon through photolithography and etching processes. The substrate refers to the substrate used for metal deposition, which can be made of transparent conductive glass or silicon wafers. The dielectric solution refers to an electrolyte containing metal ions to be deposited.

[0034] The core innovation of this application is to use capillary action to achieve local selective deposition of metal. By precisely controlling the distance between the template and the substrate, the medium solution flows along the micro-columnar structure on the template, thereby achieving precise deposition of metal in a specific area.

[0035] In this process, the capillary action between the template and the substrate is key. By controlling the distance between the two, the dielectric solution can be distributed along the corresponding pattern micro-columnar structure on the template. The electrodeposition step deposits metal ions on the template and substrate by applying a constant current to form the desired metal pattern.

[0036] During the implementation process, different medium solutions can be selected according to different needs.

[0037] Compared with the prior art, the metal patterning process based on capillary action of the present application has significant advantages. First, the process guides the flow of the dielectric solution through capillary action, avoiding the complicated photolithography and etching steps in the traditional process. Secondly, metal patterning is achieved through electrodeposition, which is simple to operate and low in cost. In addition, the process also has high preparation efficiency and controllability, and can achieve local metal deposition and metal patterning at specific locations.

[0038] Through the above steps, the metal patterning process based on capillary action of the present application can effectively solve the limitations of the prior art and achieve efficient and accurate metal patterning. Specifically, a template with a micro-columnar structure of a corresponding pattern is prepared, and the flow of the medium solution is guided by the capillary action between the template and the substrate, and finally the preparation of the metal pattern is achieved by electrodeposition. This process is not only simple to operate and low in cost, but also has high preparation efficiency and controllability, and can meet the needs of various application fields.

[0039] Furthermore, the present application also proposes that the step of preparing a template having a micro-columnar structure with a corresponding pattern according to a desired pattern comprises: polishing on one side according to the desired pattern; <100> The non-etched part of the N-type doped single crystal silicon exposed on the crystal surface is covered with photoresist; the area without photoresist protection is etched; and the excess photoresist is removed to obtain a template with a micro-columnar structure of a corresponding pattern.

[0040] By polishing on one side <100> The desired micro-columnar structure template can be obtained by performing photolithography and etching on the N-type doped single crystal silicon with the crystal surface exposed. <100> The exposed N-type doped single crystal silicon is covered with photoresist to avoid damage to the non-etched parts. Then the area without photoresist protection is etched to form the required micro-columnar structure. Finally, the excess photoresist is removed to obtain a template with a micro-columnar structure of the corresponding pattern.

[0041] For example, by UV lithography, single-sided polishing <100> The non-etched parts of the exposed N-type doped single crystal silicon (about 4 inches in diameter and 525 microns in thickness) are covered with a layer of SUN-1150P positive photoresist. The parts not protected by the photoresist are etched by plasma etching. Compared with single crystal silicon, photoresist is more difficult to etch, so the exposed silicon is etched by plasma, while the parts covered by the photoresist are retained. The excess photoresist is removed by oxygen plasma to obtain a template with a micro-columnar structure with the corresponding pattern.

[0042] The advantage of this technical solution is that the shape and size of the micro-columnar structure can be precisely controlled through etching, the preparation process is simple and efficient, and it is suitable for large-scale production. In addition, this method can form a high-precision micro-columnar structure, which is beneficial to the subsequent metal patterning electrodeposition process and improves the accuracy and consistency of the metal pattern.

[0043] Furthermore, the present application also proposes to modify a template having a corresponding pattern micro-columnar structure to obtain a modified template having asymmetric wettability, wherein the modified template is a template having a periodic microstructure of highly doped silicon columns and having asymmetric wettability. Electrodeposition is performed using the modified template and a substrate.

[0044] A modified template with asymmetric wettability is obtained by coating a positive photoresist on the top of a template with a micro-columnar structure of a corresponding pattern, adding silane as a modifying chemical, evacuating and drying, and finally removing excess positive photoresist.

[0045] In some specific embodiments, a layer of RZJ-304 positive photoresist is coated on the top of the template, and then the template is placed in a vacuum dryer and 1 μL of fluorosilane is added, and after vacuuming for 30 minutes, it is moved into a 120° C. oven and heated for 3 hours. After the modification is completed, it is placed in a developing solution to remove the photoresist, thereby obtaining a template with asymmetric wettability.

[0046] This technical solution can effectively solve the problem that the traditional electrochemical deposition method is difficult to achieve local metal deposition, and achieve the goal of patterned deposition of specific metals at specific locations. Compared with the prior art, the technical solution of this application has the advantages of simple process, low cost, high preparation efficiency and strong controllability.

[0047] Furthermore, the present application also proposes that the silane used as the modifying chemical is perfluorooctyltrichlorosilane and / or octadecyltrimethoxysilane.

[0048] The present application relates to a metal patterning process based on capillary action, wherein a positive photoresist is applied on the top of a template, silane is added as a modifying agent, and after vacuuming and drying, the excess positive photoresist is removed to obtain a modified template with asymmetric wettability. Silane can be selected as a modifying agent such as perfluorooctyltrichlorosilane and / or octadecyltrimethoxysilane. This modification process makes the surface and side of the template have asymmetric wettability, further improving the fineness and uniformity of the metal pattern in the electrodeposition process.

[0049] Perfluorooctyltrichlorosilane and octadecyltrimethoxysilane are used as modifying agents to form a stable modification layer on the side of the template. Perfluorooctyltrichlorosilane has strong hydrophobicity and can effectively prevent excessive diffusion of the solution during electrodeposition; while octadecyltrimethoxysilane increases the hydrophobicity and chemical stability of the surface through its long-chain alkyl structure. By selecting different silane modifiers, the wettability of the template surface can be adjusted according to specific application requirements, thereby better controlling the formation of metal patterns.

[0050] In addition, a positive photoresist is coated on the top of the template to make the top of the template hydrophilic and the side of the template hydrophobic, so that when the dielectric solution is subsequently injected between the template and the substrate, the dielectric solution can be moved away from the hydrophobic area and close to the hydrophilic area, thereby enhancing the capillary action and improving the deposition effect of metal ions.

[0051] The present application significantly improves the wettability and pattern fineness of the template by coating the template surface with positive photoresist and modifying it with silane. Compared with the prior art, the technical solution of the present application not only simplifies the process flow, but also improves the accuracy and consistency of the metal pattern, and solves the problem that the traditional electrochemical deposition method is difficult to achieve local metal deposition. Therefore, the technical solution of the present application has significant advantages in achieving high-precision metal patterning.

[0052] Furthermore, the present application also proposes that the substrate is ultrasonically cleaned in ethanol, acetone, and isopropanol in sequence, blown dry with a nitrogen gun, and treated with a plasma cleaner.

[0053] This application ensures the cleanliness and activity of the substrate surface by fine cleaning and treatment of the substrate. Specifically, the substrate is first ultrasonically cleaned in ethanol to remove organic contaminants on the surface; then ultrasonically cleaned in acetone to further remove grease and impurities on the surface; and then ultrasonically cleaned in isopropanol to remove residual solvents and contaminants. After cleaning, a nitrogen gun is used to blow dry the surface of the substrate to avoid water stains and residual particles. Finally, the substrate is treated with a plasma cleaner to further activate the substrate surface and improve adhesion and uniformity in subsequent processes.

[0054] In actual operation, the time and power of ultrasonic cleaning can be adjusted according to the material and degree of contamination of the substrate. For example, for heavily contaminated substrates, the cleaning time can be appropriately extended or the ultrasonic power can be increased to ensure the cleaning effect. The processing time and power of the plasma cleaner can also be adjusted according to specific needs to achieve the best cleaning and activation effect.

[0055] Through the above steps, the present application provides an efficient and reliable method for substrate cleaning and processing, which significantly improves the cleanliness and activity of the substrate surface, ensures the smooth progress of subsequent processes and the quality stability of the final product.

[0056] Furthermore, the present application also proposes that the medium solution includes at least a main salt and a conductive salt. The main salt is a metal ion deposited during the electrodeposition process, including at least one of copper ions, silver ions, gold ions, and nickel ions. The metal ions in the medium solution can be determined according to actual needs. In addition, the medium solution also contains some related complexing agents and additives.

[0057] In some embodiments, the step of preparing the medium solution comprises: A sulfate copper plating solution is prepared as a medium solution, or a silver nitrate silver plating solution is prepared as a medium solution; When the sulfate copper plating solution is used as the medium solution, the components of the sulfate copper plating solution are: Copper sulfate 160-180 g / L; Sulfuric acid 60-70 g / L; Hydrochloric acid 1ml / L; When silver nitrate plating solution is used as the medium solution, the components of the silver nitrate plating solution are: Silver nitrate 40-45 g / L; Sodium thiosulfate 230 g / L; Potassium metabisulfite 40 g / L; Ammonium acetate 25 g / L; Thiosemicarbazide 0.7 g / L.

[0058] By preparing a sulfate copper plating solution or a silver nitrate silver plating solution with a specific composition, it is ensured that the required metal ions can be obtained during the electrodeposition process, thereby achieving precise deposition of the metal pattern.

[0059] Specifically, among the components of the sulfate copper plating solution, copper sulfate provides copper ions, sulfuric acid serves as an electrolyte, and hydrochloric acid is used to adjust the pH value and stability of the solution; while among the components of the silver nitrate silver plating solution, silver nitrate provides silver ions, and sodium thiosulfate, potassium pyrosulfite, ammonium acetate and thiosemicarbazide are used for complexation, stabilization and regulation of the deposition process, respectively.

[0060] Through the above method, the composition and concentration of the dielectric solution can be effectively controlled to ensure that the concentration and distribution of metal ions are uniform during the electrodeposition process, thereby improving the quality and consistency of the metal pattern.

[0061] Furthermore, the present application also proposes a step of connecting the template and the substrate to a closed circuit for electroplating, comprising connecting the template and the substrate to a closed circuit, applying 0.001A / dm 2 ~10A / dm 2 The constant current lasts from 1 minute to 600 minutes.

[0062] By connecting the template and substrate to a closed circuit and applying 0.001A / dm 2 ~10A / dm 2 The constant current can effectively carry out electrodeposition. The magnitude and duration of the current can be adjusted according to actual needs to achieve the best electrodeposition effect. This method can ensure that the metal ions are uniformly deposited on the micro-columnar structure of the template, thereby forming the desired metal pattern.

[0063] In the specific implementation process, different current densities and durations can be selected to meet different metal patterning requirements. For example, for a metal pattern with a larger area, a higher current density and a longer duration can be selected; while for a metal pattern with a smaller area, a lower current density and a shorter duration can be selected. In this way, the formation process of the metal pattern can be flexibly controlled.

[0064] This application effectively solves the problem that it is difficult to achieve local metal deposition in traditional electrochemical deposition methods by connecting the template and the substrate to a closed circuit and applying a constant current for electrodeposition. Compared with the prior art, the technical solution of this application has the advantages of simple operation, low cost, high preparation efficiency, etc. It can perform patterned deposition of specific metals at specific locations according to actual needs, thereby improving the flexibility and controllability of the process.

[0065] Specifically, refer to Figures 2 to 11 In some of the embodiments, the specific process of the scheme of the present application is as follows: Large-area copper arrays were prepared on ITO substrates using this method: 1) Preparation of template 407: Polishing on one side by UV lithography <100> The non-etched part of the N-type doped single crystal silicon (about 4 inches in diameter and 525 microns in thickness) with exposed crystal surface is covered with a layer of SUN-1150P positive photoresist. The part without photoresist protection is etched by plasma etching method, and the etching depth is 20 microns. The excess photoresist is removed by oxygen plasma to obtain the template 407 of the corresponding patterned micro-columnar structure, as shown in FIG. Figure 2 shown.

[0066] 2) Modification of template 407: A layer of RZJ-304 positive photoresist is applied on the top of template 407, and then template 407 is placed in a vacuum dryer and 1 μL of fluorosilane is added. After vacuuming for 30 minutes, it is moved into a 120°C oven and heated for 3 hours. After the modification is completed, it is placed in a developing solution to remove the photoresist, and a template 407 with asymmetric wettability is obtained (i.e., a modified template, referred to as template 407 below). Figure 3 The left side shows the contact angle test result of the top lyophilic area, with a contact angle of about 2°, and the right side shows the contact angle test result of the side lyophobic area, with a contact angle of about 90°.

[0067] 3) Prepare substrate 406: Place 2x2 cm 2 The substrate 406 (i.e., the ITO substrate, hereinafter referred to as substrate 406) is immersed in an ethanol solution for ultrasonic cleaning for 15 minutes, and then ultrasonically cleaned with acetone, isopropanol, and ethanol for 15 minutes each. After cleaning, it is blown dry with nitrogen and treated with a plasma cleaner for 10 minutes.

[0068] 4) Configuration of medium solution 300: The main components of the copper plating solution are copper sulfate and sulfuric acid. The components are 180 g / L copper sulfate, 60 g / L sulfuric acid, and 1 ml / L hydrochloric acid.

[0069] 5) Assembly of the device: The template 407 prepared in steps 1 and 2) is placed on the lower transfer platform 415 of the XYZ three-axis driving platform 400 and fixed by a vacuum adsorption device. The substrate 406 prepared in step 3) is placed on the upper transfer platform 404 of the XYZ three-axis driving platform 400 and mechanically fixed with screws. Then, the relative position between the template 407 and the substrate 406 is adjusted, as shown in FIG. Figure 4 Then, the distance between the template 407 and the substrate 406 is adjusted to 1 micron.

[0070] 6) Electrodeposition: Inject the medium solution 300 prepared in step 4) between the template 407 and the substrate 406 assembled in step 5). The medium solution 300 will be positioned spontaneously according to the pattern on the modified template 407 under the action of capillary force. Connect the negative pole of the power supply 412 to the substrate 406, and the positive pole of the power supply 412 to the template 407. Set the current to 0.01A / dm 2 , deposition time 300 seconds, clamping voltage 5V, start power supply 412 for electrodeposition, such as Figure 5 After completion, the template 407 is separated from the substrate 406 by the XYZ three-axis driving platform 400.

[0071] 7) Washing the substrate 406: Soak the electrodeposited substrate 406 in deionized water for 1 minute to remove excess medium solution 300 on the surface, thereby obtaining a substrate 406 having a specific micro-nano metal pattern on the surface, such as Figure 6 The corresponding EDS spectrum is shown as Figure 7 shown.

[0072] Specifically, in some other embodiments, the specific process of the solution of the present application is as follows: Large-area metallic silver arrays were prepared on ITO substrates by this method: 1) Preparation of deposition template 407: polishing on one side by UV lithography <100> The non-etched part of the N-type doped single crystal silicon (about 4 inches in diameter and 525 microns in thickness) with exposed crystal surface is covered with a layer of SUN-1150P positive photoresist. The part without photoresist protection is etched by plasma etching method, and the etching depth is 20 μm. The excess photoresist is removed by oxygen plasma to obtain the template 407 of the corresponding patterned micro-columnar structure.

[0073] 2) Modification of template 407: A layer of RZJ-304 positive photoresist is applied on the top of template 407, and then template 407 is placed in a vacuum dryer and 1 μL of fluorosilane is added. After vacuuming for 30 minutes, it is moved into a 120°C oven and heated for 3 hours. After the modification is completed, it is placed in a developing solution to remove the photoresist, and a template 407 with asymmetric wettability is obtained (i.e., a modified template, referred to as template 407 below).

[0074] 3) Prepare substrate 406: Place 2x2 cm 2 The substrate 406 (i.e., the ITO substrate, hereinafter referred to as substrate 406) is immersed in an ethanol solution for ultrasonic cleaning for 15 minutes, and then ultrasonically cleaned with acetone, isopropanol, and ethanol for 15 minutes each. After cleaning, it is blown dry with nitrogen and treated with a plasma cleaner for 10 minutes.

[0075] 4) Preparation of medium solution 300: The components of silver nitrate plating solution are silver nitrate 40-45 g / L, sodium thiosulfate 230 g / L, potassium pyrosulfite 40 g / L, ammonium acetate 25 g / L, and thiosemicarbazide 0.7 g / L.

[0076] 5) Assembly of the device: The template 407 prepared in steps 1 and 2) is placed on the lower transfer platform 415 of the XYZ three-axis driving platform 400 and fixed by a vacuum adsorption device. The substrate 406 prepared in step 3) is placed on the upper transfer platform 404 of the XYZ three-axis driving platform 400 and mechanically fixed with screws. Then, the relative position between the template 407 and the substrate 406 is adjusted, as shown in FIG. Figure 4 Then, the distance between the template 407 and the substrate 406 is adjusted to 1 micron.

[0077] 6) Electrodeposition: Inject the medium solution 300 prepared in step 4) between the template 407 and the substrate 406 assembled in step 5). The medium solution 300 will be positioned spontaneously according to the pattern on the template 407 under the action of capillary force. Connect the negative electrode of the power supply 412 to the ITO substrate 406, and the positive electrode of the power supply 412 to the template 407. Set the current to 0.01A / dm 2 , deposition time 300 seconds, clamping voltage 5V, start power supply 412 to perform electrodeposition. After completion, the template 407 is separated from the substrate 406 by the XYZ three-axis driving platform 400.

[0078] 7) Washing the substrate 406: Soak the electrodeposited substrate 406 in deionized water for 1 minute to remove excess medium solution 300 on the surface, thereby obtaining a substrate 406 having a specific micro-nano metal pattern on the surface, such as Figure 8 The corresponding EDS spectrum is shown as Fig. 9 shown.

[0079] Specifically, in some other embodiments, the specific process of the solution of the present application is as follows: Deposition of metallic copper array on highly doped silicon substrate: 1) Preparation of template 407: Polishing on one side by UV lithography <100> The non-etched part of the N-type doped single crystal silicon (about 4 inches in diameter and 525 microns in thickness) with exposed crystal surface is covered with a layer of SUN-1150P positive photoresist. The part without photoresist protection is etched by plasma etching method, and the etching depth is 20 microns. The excess photoresist is removed by oxygen plasma to obtain the template 407 of the corresponding patterned micro-columnar structure.

[0080] 2) Modification of template 407: A layer of RZJ-304 positive photoresist is applied on the top of template 407, and then template 407 is placed in a vacuum dryer and 1 μL of fluorosilane is added. After vacuuming for 30 minutes, it is moved into a 120°C oven and heated for 3 hours. After the modification is completed, it is placed in a developing solution to remove the photoresist, and a template 407 with asymmetric wettability is obtained (i.e., a modified template, referred to as template 407 below).

[0081] 3) Prepare substrate 406: Place 2x2 cm 2 The substrate 406 (i.e., the highly doped silicon substrate, hereinafter referred to as substrate 406) is immersed in an ethanol solution for ultrasonic cleaning for 15 minutes, and then ultrasonically cleaned with acetone, isopropanol, and ethanol for 15 minutes each. After cleaning, it is blown dry with nitrogen and treated with a plasma cleaner for 10 minutes.

[0082] 4) Configuration of medium solution 300: The main components of the copper plating solution are copper sulfate and sulfuric acid. The components are 180 g / L copper sulfate, 60 g / L sulfuric acid, and 1 ml / L hydrochloric acid.

[0083] 5) Assembly of the device: The template 407 prepared in steps 1 and 2) is placed on the lower transfer platform 415 of the XYZ three-axis driving platform 400 and fixed by a vacuum adsorption device. The substrate 406 prepared in step 3) is placed on the upper transfer platform 404 of the XYZ three-axis driving platform 400 and mechanically fixed with screws. Then, the relative position between the template 407 and the substrate 406 is adjusted, as shown in FIG. Figure 4 Then, the distance between the template 407 and the substrate 406 is adjusted to 1 micron.

[0084] 6) Electrodeposition: Inject the electroplating solution prepared in step 4) between the template 407 and the substrate 406 assembled in step 5). The medium solution 300 will be positioned spontaneously according to the pattern of the template 407 under the action of capillary force. Connect the negative pole of the power supply 412 to the substrate 406, and the positive pole of the power supply 412 to the template 407. Set the current to 0.01A / dm 2 , deposition time 300 seconds, clamping voltage 5V, start power supply 412 to perform electrodeposition. After completion, the template 407 is separated from the substrate 406 by the XYZ three-axis driving platform 400.

[0085] 7) Washing the substrate 406: Soak the electrodeposited substrate 406 in deionized water for 1 minute to remove excess medium solution 300 on the surface, thereby obtaining a substrate 406 having a specific micro-nano metal pattern on the surface, such as Fig.10 The corresponding EDS spectrum is shown as Fig.11 shown.

[0086] Second, refer to Figure 4 The present application also proposes a capillary action-based metal patterning device for completing the above-mentioned capillary action-based metal patterning process.

[0087] The device includes at least one XYZ three-axis driving platform 400, on which an upper mold fixing plate 405 capable of moving in the Z-axis direction and a lower mold fixing plate capable of moving in the Z-axis and Y-axis are provided. A template 407 is arranged on the lower mold fixing plate, and a substrate 406 is arranged on the upper mold fixing plate 405. In addition, the device also includes a power supply 412 for electrically connecting the template 407 and the substrate 406, and a microscope 402 located above the substrate 406. The substrate 406 is made of a transparent material. Under the drive of the XYZ three-axis driving platform 400, the substrate 406 and the template 407 are controlled to be aligned, and the distance between the substrate 406 and the template 407 is maintained between 500 nanometers and 10 micrometers.

[0088] The template 407 and the substrate 406 are precisely aligned by using the XYZ three-axis drive platform 400, and the effectiveness of the capillary action is ensured by adjusting the distance between the substrate 406 and the template 407. This design solves the shortcomings of the traditional electrochemical deposition method in local metal deposition, making it possible to deposit specific metal patterns at specific locations.

[0089] The design of the device realizes precise control and easy operation of the metal patterning process by combining the XYZ three-axis drive platform 400. Compared with the prior art, the device of the present application can better meet the refinement and customization requirements of metal patterning, and significantly improves the controllability and efficiency of the process.

[0090] Specifically, the XYZ three-axis driving platform 400 has a transfer table Z direction adjustment knob 401, a transfer table X direction adjustment knob 408, a transfer table Y direction adjustment knob 409, an upper transfer table 404, and a lower transfer table 415. The transfer table Z direction adjustment knob 401 is used to adjust the movement of the upper transfer table 404 in the Z-axis direction, the transfer table X direction adjustment knob 408 and the transfer table Y direction adjustment knob 409 are used to adjust the movement of the lower transfer table 415 in the horizontal direction. In addition, a transfer table horizontal rotation knob 410 can be provided to adjust the movement of the lower transfer table 415 in the horizontal direction. The upper mold fixing plate 405 is arranged on the upper transfer table 404 and is fixed by the fixing knob 403. The lower mold fixing plate is arranged on the lower transfer table 415. The template 407 is arranged on the lower mold fixing plate. 406 is arranged on the upper mold fixing plate 405, and the substrate 406 and the template 407 are aligned by the transfer stage X-direction adjustment knob 408 and the transfer stage Y-direction adjustment knob 409, and the distance between the substrate 406 and the template 407 is adjusted by the transfer stage Z-direction adjustment knob 401. After the two are adjusted to maintain a specified distance, the substrate 406 and the template 407 are connected to the power supply 412, and the working parameters are set. After the power supply 412 is started, a closed loop is formed for electrodeposition. After the electrodeposition is completed, the results are observed through the microscope 402 located above the substrate 406. The microscope 402 is respectively provided with a microscope X-direction adjustment knob 413, a microscope Y-direction adjustment knob 414 and a microscope Z-direction adjustment knob 411 to realize the three-axis direction adjustment of the microscope 402.

[0091] In a third aspect, the present application further proposes a product having a metal pattern, wherein the product is made using a metal patterning process based on capillary action.

[0092] The product controls the distance between the template 407 and the substrate 406 within a range capable of generating capillary action, so that the medium solution 300 flows along the patterned micro-columnar structure on the template 407 and forms a metal pattern on the substrate 406 by an electrodeposition method.

[0093] The product has the advantages of low preparation cost and high production efficiency.

[0094] The above description is only an embodiment of the present application and is not intended to limit the protection scope of the present application. For those skilled in the art, the present application may have various modifications and variations. Any modification, equivalent replacement, improvement, etc. made within the spirit and principle of the present application shall be included in the protection scope of the present application.

Claims

1. A metal patterning process based on capillary action, characterized in that: include: According to the desired pattern, a template having a micro-columnar structure of a corresponding pattern is prepared; preparing a substrate; Prepare medium solution; placing the template below the substrate, and making the distance between the template and the substrate a distance capable of generating a capillary action; Injecting the medium solution into the gap between the template and the substrate, so that the medium solution flows along the corresponding pattern micro-columnar structure on the template; The template and the substrate are connected to a closed circuit for electrodeposition.

2. The metal patterning process based on capillary action according to claim 1, characterized in that: The step of preparing a template having a micro-columnar structure with a corresponding pattern according to a desired pattern comprises: Polished on one side according to the required pattern <100> The non-etched portion of the N-type doped single crystal silicon exposed on the crystal surface is covered with photoresist; Etching the areas not protected by photoresist; The excess photoresist is removed to obtain the template having a micro-columnar structure with a corresponding pattern.

3. The metal patterning process based on capillary action according to claim 2, characterized in that: The process also includes: Modifying the template having a corresponding pattern micro-columnar structure to obtain a modified template having asymmetric wettability, wherein the modified template is a template having a periodic microstructure of highly doped silicon columns and having asymmetric wettability; Using the modified template and the substrate to perform electrodeposition; The step of modifying the template having the corresponding pattern micro-columnar structure to obtain a modified template having asymmetric wettability comprises: Applying positive photoresist on top of the template having the corresponding pattern of micro-columnar structures; Adding silane as a modifying chemical to the template coated with positive photoresist; Vacuuming and drying; The excess positive photoresist is removed to obtain the modified template with asymmetric wettability.

4. The metal patterning process based on capillary action according to claim 3, characterized in that: The silane used as the modifying chemical is perfluorooctyltrichlorosilane and / or octadecyltrimethoxysilane.

5. A metal patterning process based on capillary action according to any one of claims 1 to 3, characterized in that: The step of preparing the substrate comprises: The substrate was ultrasonically cleaned in ethanol, acetone, and isopropanol in sequence, dried using a nitrogen gun, and treated using a plasma cleaner.

6. A metal patterning process based on capillary action according to any one of claims 1 to 3, characterized in that: The medium solution at least includes a main salt and a conductive salt. The main salt is a metal ion deposited during the electrodeposition process, and includes at least one of copper ions, silver ions, gold ions, and nickel ions.

7. The metal patterning process based on capillary action according to claim 6, characterized in that: The step of preparing the medium solution comprises: Prepare a sulfate copper plating solution as the medium solution, or prepare a silver nitrate silver plating solution as the medium solution; When the sulfate copper plating solution is used as the medium solution, the components of the sulfate copper plating solution are: Copper sulfate 160-180 g / L; Sulfuric acid 60-70 g / L; Hydrochloric acid 1ml / L; When the silver nitrate plating solution is used as the medium solution, the components of the silver nitrate plating solution are: Silver nitrate 40-45 g / L; Sodium thiosulfate 230 g / L; Potassium metabisulfite 40 g / L; Ammonium acetate 25 g / L; Thiosemicarbazide 0.7 g / L.

8. The metal patterning process based on capillary action according to claim 1, characterized in that: The step of connecting the template and the substrate to a closed circuit for electrodeposition comprises: The template and the substrate were connected to a closed circuit and 0.001A / dm 2 ~10A / dm 2 The constant current lasts from 1 minute to 600 minutes.

9. A metal patterning device based on capillary action, used to complete a metal patterning process based on capillary action as claimed in any one of claims 1 to 8, characterized in that: At least: An XYZ three-axis driving platform is provided on the XYZ three-axis driving platform, wherein an upper mold fixing plate capable of moving in the Z-axis direction and a lower mold fixing plate capable of moving in the Z-axis and Y-axis directions are provided, the template is arranged on the lower mold fixing plate, the substrate is arranged on the upper mold fixing plate, a power supply for electrically connecting the template and the substrate and a microscope located above the substrate are also provided, the substrate is made of a transparent material, and under the drive of the XYZ three-axis driving platform, the substrate is controlled to be aligned with the template, and the distance between the substrate and the template is made to be 500 nanometers to 10 micrometers.

10. A product having a metal pattern, characterized in that: The product is made using a capillary action-based metal patterning process as described in any one of claims 1 to 8.

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