CN110777400B - Micro electroforming method based on elastic conductive silicon rubber mold - Google Patents
Micro electroforming method based on elastic conductive silicon rubber mold Download PDFInfo
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- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D1/00—Electroforming
- C25D1/10—Moulds; Masks; Masterforms
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
- C23C18/16—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by reduction or substitution, e.g. electroless plating
- C23C18/18—Pretreatment of the material to be coated
- C23C18/20—Pretreatment of the material to be coated of organic surfaces, e.g. resins
- C23C18/2006—Pretreatment of the material to be coated of organic surfaces, e.g. resins by other methods than those of C23C18/22 - C23C18/30
- C23C18/2046—Pretreatment of the material to be coated of organic surfaces, e.g. resins by other methods than those of C23C18/22 - C23C18/30 by chemical pretreatment
- C23C18/2073—Multistep pretreatment
- C23C18/2086—Multistep pretreatment with use of organic or inorganic compounds other than metals, first
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
- C23C18/16—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by reduction or substitution, e.g. electroless plating
- C23C18/31—Coating with metals
- C23C18/42—Coating with noble metals
- C23C18/44—Coating with noble metals using reducing agents
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Abstract
The invention relates to a micro electroforming method based on an elastic conductive silicon rubber mold, which comprises the following steps: putting an aminated PDMS mold into a Tris-HCl buffer solution of dopamine to obtain a PDMS mold with a polydopamine layer deposited on the surface; immersing the mold into a mixed solution of silver nitrate-containing ethanol and ethylene glycol to obtain a PDMS mold with nano-silver particles generated on the surface; thirdly, sequentially dripping the silver ammonia solution and the glucose solution into the micro cavity of the mold, and obtaining the chemically silver-plated PDMS mold after the reaction is finished; the chemical silvering PDMS mold is used as a cathode and is immersed into metal or ceramic electroforming liquid for direct current deposition; soaking, ultrasonic cleaning and demoulding to obtain the metal or ceramic micro-part; finally, the metal or ceramic micro-part is soaked in ammonia water until the surface has no nano silver layer; and repairing the damaged nano silver layer on the surface of the PDMS mould by chemical silvering. The invention can realize the purposes of reducing cost and improving production efficiency.
Description
Technical Field
The invention relates to the field of micro-forming manufacturing, in particular to a micro-electroforming method based on an elastic conductive silicon rubber mold.
Background
The micro electroforming technology is one of the main methods for forming micro parts, and has the advantages of high replication precision, low cost, capability of forming a micro structure with a complex shape, capability of forming a nano-crystalline metal material, wide application range of materials and the like. According to the micro electroforming process sequence, micro electroforming can be divided into the steps of preparation of a mould, preparation of electroforming liquid, electrodeposition forming, subsequent treatment and the like, wherein the mould with good conductivity and high precision is a precondition for micro electroforming to form high-quality micro parts.
At present, a mold generally used in the micro electroforming technology is composed of a photoresist microstructure prepared by photoetching or ion etching technology and a conductive substrate, for example, the microstructure prepared by commonly using photoresist SU-8 photoetching is adhered to a metal substrate to be used as a micro electroforming mold. In the preparation process, large and expensive photoetching equipment and a complex preparation process are needed, the internal stress in the photo-etched SU-8 microstructure is large, a swelling phenomenon exists in electroforming solution, the forming precision of a micro-part can be influenced in the electrodeposition process, the formed SU-8 microstructure is difficult to remove in demoulding, and a mould can be used only once.
Disclosure of Invention
The technical problem to be solved by the invention is to provide a micro electroforming method based on an elastic conductive silicon rubber mold, which reduces the cost and improves the production efficiency.
In order to solve the problems, the invention provides a micro electroforming method based on an elastic conductive silicon rubber mold, which comprises the following steps:
putting an aminated PDMS mold into a Tris-HCl buffer solution containing 1-20 g/L dopamine, and stirring for 20-30 h under the condition that the pH value is 8.5 to obtain the PDMS mold with a polydopamine layer deposited on the surface;
ultrasonically cleaning a PDMS mold with a polydopamine layer deposited on the surface in deionized water, blow-drying the PDMS mold with nitrogen, and then soaking the PDMS mold into a mixed solution of ethanol and ethylene glycol containing 1-10 mmol/L of silver nitrate for 50 min to obtain the PDMS mold with nano-silver particles generated on the surface;
thirdly, dripping the newly prepared 5-40 g/L silver ammonia solution into the micro cavity of the PDMS mold with the surface generating the nano silver particles, dripping 5-40 g/L glucose solution serving as a reducing agent into the micro cavity, and obtaining the PDMS mold with the chemical silvering after the reaction is finished;
immersing the chemically silvered PDMS mold serving as a cathode into a metal or ceramic electroforming solution for direct current deposition; after a mold cavity is fully cast, soaking the mold in ammonia water with the mass concentration of 20-25% for 5-10 hours, then soaking the mold in deionized water for ultrasonic cleaning, and demolding to obtain a metal or ceramic micro part; finally, soaking the metal or ceramic micro-part in ammonia water with the mass concentration of 20-25% until the surface is free of the nano silver layer; and repairing the damaged nano silver layer on the surface of the PDMS mould through chemical silvering.
The aminated PDMS mold is characterized in that the PDMS mixed liquid without bubbles is poured on a silicon template prepared by etching, is solidified for 30 min at 100 ℃, and is peeled off after being cooled to room temperature, so that the PDMS mold is obtained; and ultrasonically cleaning the PDMS mold by using acetone, absolute ethyl alcohol and deionized water in sequence for 15min, then placing the PDMS mold into a mixed solution of ethyl alcohol and water containing 2% of triethoxysilane for grafting an amino functional group (3), drying the PDMS mold at 110 ℃ for 20 min after 20 min, and repeating the step for 3 times to obtain the PDMS mold.
The PDMS mixed liquid is obtained by mixing a polydimethylsiloxane prepolymer and a curing agent at room temperature according to a volume ratio of 10: 1.
The mixed solution of ethanol and water containing 2% of triethoxysilane is a solution obtained by adding 20-30 g of triethoxysilane to 1L of 60-70% ethanol water solution by volume concentration and mixing uniformly.
The step II is to add 1-10 mmol/L of silver nitrate into 1L of ethanol-ethylene glycol solution and uniformly mix the obtained solution, wherein the mixed solution of ethanol and ethylene glycol containing 1-10 mmol/L of silver nitrate is obtained.
The ethanol-ethylene glycol solution is prepared by mixing ethanol with the volume concentration of 99.0-99.7% and ethylene glycol according to the ratio of 3: 1, and uniformly mixing the obtained solution.
The condition of direct current deposition in the step four is that the current density is 2-10A/dm2。
The metal or ceramic electroforming solution in the step four is a water-based or alcohol-based electroforming solution.
Compared with the prior art, the invention has the following advantages:
1. the invention combines soft etching and chemical plating to prepare a novel elastic conductive silicon rubber mold, replaces the mold prepared by the traditional photoetching technology to carry out micro electroforming on metal and ceramic micro parts, can prepare the micro electroforming mold with short flow and low cost, and can repair the prepared mold through chemical plating to realize repeated use, thereby reducing the manufacturing cost of electroforming micro parts and improving the production efficiency.
2. The invention uses the soft etching technology to copy the microstructure of the transfer template, and uses the restorable elastic conductive silicon rubber mold as the mold for micro electroforming, can solve the defects of complex preparation process, high manufacturing cost, short service life and the like of the current micro electroforming mold, obviously reduces the production cost of micro electroforming metal and ceramic micro parts, improves the production efficiency and is suitable for batch forming.
3. The invention uses chemical silver plating to endow the elastic silicon rubber mold prepared by soft etching with conductivity, so that the elastic silicon rubber mold meets the requirements of micro electroforming.
4. The invention uses water-based and alcohol-based electroforming solution, and is generally suitable for forming metal and ceramic micro parts.
5. The invention can be used for precisely electroforming metal and ceramic micro parts with high depth-to-width ratio, and the elastic conductive silicon rubber mould has complete microstructure and no deformation after being used for 5 times.
6. By adopting the method, the nano silver layer adhered to the surface of the micro part after demoulding can be conveniently removed by soaking in ammonia water. Meanwhile, the PDMS mould can be repaired after being demoulded so as to realize the repeated use of the mould.
Drawings
The following describes embodiments of the present invention in further detail with reference to the accompanying drawings.
FIG. 1 is a schematic diagram of a soft etching process of the present invention.
FIG. 2 is a schematic view of the electroless silver plating process of the present invention.
FIG. 3 is a schematic diagram of a micro electroforming process of the present invention.
FIG. 4 is a schematic diagram of the demolding and electroless plating repair process of the present invention.
Fig. 5 shows the surface (left) and cross-sectional profile (right) of the metallic nickel microstructure prepared by the method of the present invention.
Fig. 6 shows the surface (left) and cross-sectional profile (right) of an alumina microstructure prepared by the method of the present invention.
Fig. 7 shows the surface (left) and cross-sectional profile (right) of the microstructure of the elastic conductive silicone rubber mold prepared by the method of the present invention after 5 times of use.
In the figure: 1-a silicon template; 2-PDMS mold; 3-amino functional group; 4-a polydopamine layer; 5-nano silver layer; 6-metal or ceramic micro-parts.
Detailed Description
A micro electroforming method based on an elastic conductive silicon rubber mold comprises the following steps:
firstly, putting an aminated PDMS mold into a Tris-HCl buffer solution containing 1-20 g/L dopamine, and stirring for 20-30 h under the condition that the pH value is 8.5 to obtain the PDMS mold 2 with a polydopamine layer 4 deposited on the surface.
Wherein: the aminated PDMS mold is prepared by pouring the bubble-removed PDMS mixed solution onto an etched silicon template 1, curing at 100 deg.C for 30 min, cooling to room temperature, and peeling to obtain PDMS mold 2 (see FIG. 1). And ultrasonically cleaning the PDMS mold 2 in an ultrasonic cleaning machine by using acetone, absolute ethyl alcohol and deionized water in sequence for 15min, then placing the cleaned PDMS mold 2 into a mixed solution of ethyl alcohol and water containing 2% of triethoxysilane for grafting amino functional groups 3, drying the PDMS mold 2 at 110 ℃ for 20 min after 20 min, and repeating the drying for 3 times to improve the grafting effect of the amino functional groups 3 to obtain the product.
The PDMS mixed solution is prepared by mixing Polydimethylsiloxane (PDMS) prepolymer and curing agent according to the proportion of 10 mL: the resulting mixture was mixed at room temperature in a volume ratio of 1 mL. The curing agent is Dow Corning 184. The PDMS mixture was placed in a vacuum chamber at room temperature to remove air bubbles.
The mixed solution of ethanol and water containing 2% of triethoxysilane is a solution obtained by adding 20-30 g of triethoxysilane to 1L of 60-70% ethanol water solution by volume concentration and mixing uniformly.
Secondly, the PDMS mold 2 with the polydopamine layer 4 deposited on the surface is ultrasonically cleaned in deionized water and dried by nitrogen, and then is immersed in silver nitrate (AgNO) containing 1-10 mmol/L3) In the mixed solution of ethanol and ethylene glycol, a PDMS mold 2 (see fig. 2) with nano silver particles generated on the surface is obtained after 50 min.
Wherein: containing 1 to 10 mmol/L silver nitrate (AgNO)3) The mixed solution of ethanol and glycol is a solution obtained by adding 1-10 mmol of silver nitrate into 1L of ethanol-glycol solution and uniformly mixing.
The ethanol-ethylene glycol solution is prepared by mixing ethanol with the volume concentration of 99.0-99.7% and ethylene glycol according to the ratio of 3: 1, and uniformly mixing the obtained solution.
Thirdly, newly prepared 5-40 g/L silver ammonia solution is dripped into the micro cavity of the PDMS mold 2, the surface of which generates the nano silver particles, 5-40 g/L glucose solution is dripped into the micro cavity as a reducing agent, the chemically silvered PDMS mold 2 is obtained after the reaction is finished, and the uniform and compact nano silver layer 5 is accurately prepared at the microstructure part of the mold through the reduction reaction of silver ions, so that the PDMS mold is endowed with conductivity.
Fourthly, immersing the chemically silvered PDMS mold 2 serving as a cathode into metal or ceramic electroforming liquid for direct current deposition, wherein the current density is 2-10A/dm2. After the mold cavity is fully cast, the mold is immersed into ammonia water with the mass concentration of 20-25% for soaking for 5-10 hours to dissolve part of the nano silver layer 5 between the mold and the micro part, and the dissolution of the silver layer is beneficial to subsequent complete demolding. And then, the mould is immersed into deionized water for ultrasonic cleaning, and demoulding is carried out to obtain the metal or ceramic micro-part 6 (see figure 3). In the demolding process, because strong interface adhesion exists between the mold and the micro part, the nano silver layer 5 on the surface of the mold can be peeled off and further adhered to the surface of the micro part during demolding, and finally the metal or ceramic micro part 6 is soaked in ammonia water with the mass concentration of 20-25% to be dissolved and removed to remove the nano silver layer 5 adhered to the surface of the micro part until no nano silver layer 5 exists. The damaged nano silver layer 5 on the surface of the PDMS mold 2 is repaired by electroless silver plating to realize reuse of the electroless silver plating mold (see fig. 4).
Wherein: the metal or ceramic electroforming solution refers to a water-based or alcohol-based electroforming solution.
Example 1 metallic nickel microstructures were electroformed based on this novel elastic conductive mold. The overall size of the micro-part is 6 multiplied by 0.7 mm, wherein the line width of the micro-structure is 60 μm, the depth is 135 μm, and the depth-to-width ratio is 2.25, the micro-structure is shown in figure 5, and the specific steps are as follows:
the method comprises the steps of preparing a silicon template 1 with the line width of 60 mu m by using a deep reactive ion etching technology, uniformly mixing 5 mL of PDMS prepolymer and 0.5 mL of curing agent, and placing the mixture in a vacuum drying oven to remove bubbles in the PDMS prepolymer;
soft etching and forming of the PDMS mold: the PDMS mixture was poured onto the silicon template 1. Then curing the film in an oven at 100 ℃ for 30 min, and peeling off the PDMS mold 2 after cooling to room temperature, so as to copy and transfer the microstructure with the line width of 60 μm to the PDMS mold 2, as shown in figure 1. And finally, ultrasonically cleaning the prepared PDMS mold 2 by using acetone, absolute ethyl alcohol and deionized water respectively for later use.
Surface amination of PDMS mold: 30g of absolute ethanol solution and 20 g of aqueous solution are mixed uniformly, and 1 g of APTES (triethoxysilane, NH) is added dropwise2(CH2)3Si(OC2H5) Preparing a mixed solution to perform amination treatment on the surface of the mold. And (3) immersing the PDMS mould 2 which is cleaned by ultrasonic into the mixed solution for 20 min for grafting the amino functional group 3, and drying the PDMS mould 2 in an oven at 110 ℃ for 20 min after grafting is finished, wherein the attached figure 2 shows. The above process was repeated 3 times to improve the grafting effect of the amino functional group 3.
Secondly, chemical silvering is carried out on the surface of the PDMS mould 2: uniformly mixing 15 g of absolute ethyl alcohol solution and 5 g of ethylene glycol solution, then dropwise adding 0.03 g of silver nitrate to prepare an organic silver solution, then placing the PDMS mold 2 with the polydopamine layer 4 deposited on the surface into the organic silver solution, soaking for 50 min for activation, and generating nano silver particles on the surface of the mold to catalyze the subsequent silver ion reduction.
Thirdly, respectively dripping the silver ammonia solution and the glucose into the cavity of the activated PDMS mold 2, and reacting at room temperature for 40 min to accurately prepare the nano silver layer 5 at the microstructure of the mold through the reduction reaction of silver ions, as shown in the attached drawing 2.
The preparation process of the silver ammonia solution comprises the following steps: and (3) dripping 0.1 g of silver nitrate into 10mL of deionized water, slowly dripping ammonia water with the mass concentration of 20-25% into the solution after the silver nitrate is completely dissolved until the solution becomes turbid from clear, and stopping dripping the ammonia water when the solution becomes colorless and transparent from turbid to obtain the silver nitrate.
The preparation process of the glucose solution comprises the following steps: 0.1 g of glucose is added into 10mL of deionized water dropwise to obtain the glucose-free glucose-reducing agent.
Fourth, micro electroforming and demolding: PDMS mold 2, made of electroless silver plating, was used as the cathode and a pure nickel plate (> 99% purity) was used as the anode immersed in the watt's solution. The formula of the watt liquid is 295-305 g/L of nickel sulfate, 55-60 g/L of nickel chloride, 35-40 g/L of boric acid, 0.1-0.4 g/L of sodium dodecyl sulfate and 4-6 g/L of saccharin, the pH value of the electroforming liquid is 3.9-4.2, and the temperature is 50-55 ℃. Performing direct current electrodeposition with an electrochemical workstation at a current density of 5A/dm2. After the cavity of the PDMS mold 2 is fully cast (see the attached drawing 3), the PDMS mold 2 is immersed into ammonia water with the mass concentration of 20-25% to dissolve part of the nano silver layer 5 between the mold and the metal nickel micro-part, then the PDMS mold 2 is subjected to ultrasonic treatment for 30 min by using deionized water, and finally the metal nickel micro-part is obtained after demolding.
Repairing the conductive layer: the nano silver layer 5 adhered to the surface of the metal nickel micro-part in the demolding process can be dissolved by soaking in ammonia water with the mass concentration of 20-25% until the nano silver layer 5 on the surface of the casting layer is completely removed. The damaged nano silver layer 5 on the surface of the mold can be repaired by chemical plating by dripping the silver ammonia solution and the glucose solution again so as to realize the repeated use of the mold, as shown in figure 4. Finally, the novel elastic conductive silicon rubber mold is used for precisely electroforming a metal nickel microstructure with the line width of 60 um, the depth of 135 microns and the depth-to-width ratio of 2.25, and as can be seen from the attached drawing 5, the electroformed metal nickel microstructure is complete and has no defect, and the elastic conductive silicon rubber mold is complete and has no deformation after being used for 5 times (see the attached drawing 7).
Example 2 an alumina microstructure was electroformed based on this novel elastic conductive mold. The micro-part size is 6 multiplied by 0.7 mm, wherein the micro-structure line width is 60 μm, the depth is 135 μm, and the depth-to-width ratio is 2.25, the alumina micro-structure is shown in figure 6, and the specific steps are as follows:
the steps are as in example 1.
Fourth, micro electroforming and demolding: PDMS mold 2 made of electroless silver plating was used as a cathode, a platinum electrode was used as an anode, and immersed in an alcohol-based ceramic electroforming solution having a solid content of 75 wt.%, and direct current deposition was performed at room temperature using an electrochemical workstation at a current density of 5A/dm2. And (3) demolding to obtain the aluminum oxide micro-part after the mold cavity is fully cast (see the attached figure 3). It can be seen from fig. 6 that the electroformed alumina microstructure is intact and defect free and that the microstructure is intact and non-deformed after 5 uses of the elastic conductive silicone rubber mold (see fig. 7).
Claims (8)
1. A micro electroforming method based on an elastic conductive silicon rubber mold comprises the following steps:
putting an aminated PDMS mold into a Tris-HCl buffer solution containing 1-20 g/L dopamine, and stirring for 20-30 h under the condition that the pH value is 8.5 to obtain a PDMS mold (2) with a polydopamine layer (4) deposited on the surface;
ultrasonically cleaning a PDMS mold (2) with a poly dopamine layer (4) deposited on the surface in deionized water, blow-drying the PDMS mold with nitrogen, immersing the PDMS mold into a mixed solution of ethanol and ethylene glycol containing 1-10 mmol/L of silver nitrate, and obtaining the PDMS mold (2) with nano-silver particles generated on the surface after 50 min;
thirdly, dripping newly prepared 5-40 g/L silver ammonia solution into the micro cavity of the PDMS mold (2) with the surface generating the nano silver particles, then dripping 5-40 g/L glucose solution serving as a reducing agent into the micro cavity, and obtaining the PDMS mold (2) with the chemical silvering after the reaction is finished;
fourthly, immersing the chemically silvered PDMS mold (2) serving as a cathode into a metal or ceramic electroforming solution for direct current deposition; after the mold cavity is fully cast, soaking the mold in ammonia water with the mass concentration of 20-25% for 5-10 h, then soaking the mold in deionized water for ultrasonic cleaning, and demolding to obtain the metal or ceramic micro part (6); finally, the metal or ceramic micro-part (6) is soaked in ammonia water with the mass concentration of 20-25% until no nano silver layer (5) exists on the surface; and repairing the damaged nano silver layer (5) on the surface of the PDMS mould (2) by chemical silvering.
2. The method of claim 1, wherein the method comprises the following steps: the method comprises the steps of pouring a PDMS mixed solution with bubbles removed onto a silicon template (1) prepared by etching, curing at 100 ℃ for 30 min, cooling to room temperature, and peeling to obtain a PDMS mold (2); and ultrasonically cleaning the PDMS mold (2) by using acetone, absolute ethyl alcohol and deionized water in sequence for 15min, then placing the cleaned PDMS mold into a mixed solution of ethyl alcohol and water containing 2% of triethoxysilane for grafting an amino functional group (3), drying the PDMS mold (2) at 110 ℃ for 20 min after 20 min, and repeating the step for 3 times to obtain the product.
3. The method of claim 2, wherein the method comprises the following steps: the PDMS mixed liquid is obtained by mixing a polydimethylsiloxane prepolymer and a curing agent at room temperature according to a volume ratio of 10: 1.
4. The method of claim 2, wherein the method comprises the following steps: the mixed solution of ethanol and water containing 2% of triethoxysilane is a solution obtained by adding 20-30 g of triethoxysilane to 1L of 60-70% ethanol water solution by volume concentration and mixing uniformly.
5. The method of claim 1, wherein the method comprises the following steps: the step II is to add 1-10 mmol/L of silver nitrate into 1L of ethanol-ethylene glycol solution and uniformly mix the obtained solution, wherein the mixed solution of ethanol and ethylene glycol containing 1-10 mmol/L of silver nitrate is obtained.
6. The method of claim 5, wherein the method comprises the following steps: the ethanol-ethylene glycol solution is prepared by mixing ethanol with the volume concentration of 99.0-99.7% and ethylene glycol according to the ratio of 3: 1, and uniformly mixing the obtained solution.
7. The method of claim 1, wherein the method comprises the following steps: the condition of direct current deposition in the step four is that the current density is 2-10A/dm2。
8. The method of claim 1, wherein the method comprises the following steps: the metal or ceramic electroforming solution in the step four is a water-based or alcohol-based electroforming solution.
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