Maskless electrochemical metal 3D printing device and method based on light-operated ion release
By introducing photocontrolled ion release technology into the electrodeposition technology, using projection equipment to project the ultraviolet light pattern and apply voltage, selective deposition of specific areas on the substrate is achieved, solving the problem of deposition non-selectivity in the prior art, and reducing the Cost and complexity, improving efficiency and utilization.
Patent Information
- Application Number
- CN202411597690.3
- Authority / Receiving Office
- CN · China
- Patent Type
- Applications(China)
- Current Assignee / Owner
- Filing Date
- 2024-11-11
- Publication Date
- 2025-02-11
AI Technical Summary
Existing electrodeposition techniques are difficult to achieve selective deposition of specific regions on the substrate, resulting in reduction of metal ions throughout the surface rather than only in local areas, increasing the complexity and cost of the manufacturing process.
Using a maskless electrochemical metal 3D printing device based on photocontrolled ion release, the ultraviolet light pattern is projected into the plating solution through projection equipment, destroying the metal complex structure, and applying voltage to realize local electrodeposition of metal ions, and preparing patterning metal microelectrode.
The preparation of patterned metal microelectrodes can be achieved without the need for physical masks or lithography, reducing manufacturing costs and process complexity, and improving printing efficiency and utilization.
Smart Images
Figure CN119411200A_ABST
Abstract
Description
Technical Field
[0001] The present invention relates to the technical field of electrochemical metal printing devices, and in particular to a maskless electrochemical metal 3D printing device and method based on light-controlled ion release. Background Art
[0002] Metal microelectrodes are electrodes with at least one micrometer or nanometer size. Due to their unique size effect, they exhibit excellent electrochemical properties such as high current density, fast response and high sensitivity. These properties make metal microelectrodes widely used in many fields, including electrochemical analysis, biomedical research, environmental monitoring, energy electrochemistry and materials science. In the biomedical field, they are used for the measurement of intracellular potential and in vivo analysis; in environmental monitoring, they are used to detect pollutants in water quality and air; in the energy field, they help to research and develop new batteries and capacitors.
[0003] Electrodeposition is a common method for preparing metal microelectrodes, which involves depositing a metal layer on a conductive substrate by electrolysis. In this process, metal ions migrate from the electrolyte solution to the surface of the working electrode and are reduced on the electrode to form solid metal. However, as a global process, the challenge of electrodeposition is that it is difficult to achieve selective deposition in specific areas on the substrate. Since the current is distributed over the entire surface of the substrate, the metal ions are reduced over the entire surface, not just in local areas. In order to achieve deposition in specific areas, additional techniques such as photolithography or the use of physical templates to define the deposition area are usually required. These techniques form a mask pattern or cover template on the substrate to limit the range of the current, thereby achieving local deposition. Nevertheless, these methods increase the complexity and cost of the manufacturing process and may be limited by resolution, especially when achieving fine patterning on flexible or irregularly shaped substrates. These challenges are particularly evident.
[0004] Photo-controlled digital electrodeposition is an advanced micro-nanoscale patterning technology that uses a photosensitive substrate material as the working electrode for electrodeposition. It combines optical control and electrodeposition principles to achieve on-demand deposition of thin films directly on semiconductor substrates. When the photosensitive substrate is irradiated by a specific pattern of light, its local conductivity will increase significantly due to the generation of photogenerated electron-hole pairs, thereby forming a local area of high conductivity in the illuminated area.
[0005] However, the above methods involve complex operations and high costs, which are not conducive to practical applications. First of all, the manufacture of cathode photoconductive substrates requires vacuum coating technology, which is relatively expensive during the preparation process. Vacuum coating technologies include cathode arc technology, magnetron sputtering technology, evaporation technology, gas ion etching and auxiliary deposition technology. Although these technologies can achieve the deposition of materials, they often require sophisticated equipment and control conditions, which greatly increases the time and technical costs; in addition, because the metal ions are directly deposited on the cathode photoconductive substrate during the experiment and form a dense coating, the photoconductive substrate can only be used once, and the utilization rate is low. Summary of the invention
[0006] In view of the problems existing in the prior art, the present invention provides a maskless electrochemical metal 3D printing device and method based on photocontrolled ion release, which can efficiently manufacture patterned metal microelectrodes.
[0007] The technical solution of the present invention is as follows: In a first aspect of the present invention, a maskless electrochemical metal 3D printing device based on photocontrolled ion release is provided, comprising a projection device, a plating tank, a support frame, a cathode ITO glass and a copper anode; a plating solution is placed in the plating tank, the plating tank is horizontally placed above the projection screen of the projection device, the cathode ITO glass is placed in the plating tank as a cathode and fixed at the bottom of the plating tank; the copper anode is mounted on the support frame and arranged parallel to the cathode ITO glass, the cathode ITO glass and the copper anode are respectively connected to the negative electrode and the positive electrode of a DC power supply; the ultraviolet light pattern generated on the projection screen of the projection device irradiates the plating solution on the surface of the cathode ITO glass, and a metal pattern is deposited on the surface of the cathode ITO glass by applying an external voltage. In some embodiments of the present invention, the middle part of the upper surface of the copper anode is fixedly connected to the support frame, the connection between the copper anode and the support frame is an insulating connection, the support frame is connected to the slider through a mounting plate, and the slider is slidably connected to the movable track.
[0008] In some embodiments of the present invention, the movable track is vertically arranged, and the slider moves on the movable track to drive the support frame and the copper anode to move in the Z-axis direction.
[0009] In some embodiments of the present invention, the projection device is connected to a computer. After receiving a digital signal from the computer, the projection device controls the DMD micromirror to flip quickly to reflect the light source. The light source emits ultraviolet light, which is reflected by the DMD micromirror to the projection screen to generate an ultraviolet light pattern.
[0010] In some embodiments of the present invention, the plating solution is a mixed plating solution of a metal complex Cu-EDTA and a photocatalyst titanium dioxide.
[0011] In some embodiments of the present invention, the plating tank is made of UV-transmitting glass, and the surface of the cathode ITO glass opposite to the copper anode is conductive.
[0012] In a second aspect of the present invention, a maskless electrochemical metal 3D printing method based on photo-controlled ion release is provided, comprising the following steps: The cathode ITO glass and the copper anode separated by a set distance are placed in a mixed plating solution of the metal complex Cu-EDTA and the photocatalyst titanium dioxide; The projected ultraviolet light pattern irradiates the mixed plating solution on the surface of the cathode ITO glass, causing the metal complex in the mixed plating solution to react and decomplex to release metal copper ions; Voltages were applied to the cathode ITO glass and the copper anode respectively, and a copper metal pattern was directionally electrodeposited on the side of the cathode ITO glass opposite to the copper anode to complete the preparation of the metal microelectrode. In some embodiments of the present invention, the preparation process of the mixed plating solution includes: Add disodium EDTA, copper sulfate pentahydrate and deionized water to a beaker, stir with a glass rod until all dissolved, and let stand for a while to allow for full complexation; Repeatedly diluting the metal complex solution to a set concentration, and then dissolving titanium dioxide powder in the prepared metal complex solution and stirring; After stirring, the solution was placed in an ultrasonic cleaning chamber for oscillation to allow the titanium dioxide particles to be fully dispersed throughout the solution. After the ultrasonic cleaning, the solution was placed in a dark environment for later use.
[0013] In some embodiments of the present invention, before the cathode ITO glass is placed in the mixed plating solution, the cathode ITO glass is cleaned and blown dry with nitrogen. Before the copper anode is placed in the mixed plating solution, the copper anode is leveled until it is parallel to the cathode ITO glass, and the electrode spacing is adjusted to a set distance.
[0014] In some embodiments of the present invention, after the metal microelectrode is printed, the DC power supply is turned off first and then the projection device is stopped, the cathode ITO glass is taken out, the residual liquid on the surface is cleaned, and the glass is stored in a dry environment for reuse.
[0015] One or more technical solutions of the present invention have the following beneficial effects: (1) The present invention utilizes a projection device to project a designed ultraviolet light pattern into a local plating solution, thereby destroying the metal complex structure inside the plating solution, and then realizing local electrodeposition of metal ions under the action of an external DC power supply, thereby rapidly preparing a patterned metal microelectrode.
[0016] (2) The present invention controls the electrodeposition process through photocatalytic technology, adopts a mixed plating solution of metal complex Cu-EDTA and photocatalyst titanium dioxide, and the cathode is a single-sided conductive ITO transparent conductive glass, the surface of which does not need to be modified by manufacturing a physical mask or photolithography technology. Through optical mode control, the preparation of maskless patterned metal microelectrodes is completed. The morphology and size of the deposited metal are controlled by the projection pattern, forming a new maskless electrochemical metal 3D printing technology.
[0017] (3) The present invention accurately controls the electrode spacing between the copper anode and the cathode ITO glass by moving the slide rail, thereby accelerating the reaction speed, shortening the metal ion deposition time, improving the deposition effect, and improving the printing efficiency; in addition, the cathode ITO glass can be cleaned and reused after the metal microelectrode is prepared, thereby improving the utilization rate and reducing the cost. BRIEF DESCRIPTION OF THE DRAWINGS
[0018] Figure 1 It is a schematic structural diagram of a maskless electrochemical metal 3D printing device based on light-controlled ion release of the present invention; Figure 2 This is a schematic diagram of the principle of the maskless electrochemical metal 3D printing device based on light-controlled ion release of the present invention.
[0019] In the figure: 1. projection equipment; 2. projection screen; 3. plating tank; 4. support frame; 5. mounting plate; 6. slider; 7. cathode ITO glass; 8. copper anode; 9. moving track; 10. DC power supply. DETAILED DESCRIPTION
[0020] The present invention will be further described below in conjunction with the accompanying drawings and embodiments.
[0021] Example 1 In a typical embodiment of the present invention, a maskless electrochemical metal 3D printing device based on photocontrolled ion release is proposed, comprising a projection device 1, a plating tank 3, a support frame 4, a cathode ITO glass 7 and a copper anode 8; a plating solution is placed in the plating tank 3, the plating tank 3 is horizontally placed above the projection screen 2 of the projection device 1, and the cathode ITO glass 7 is placed in the plating tank 3 as a cathode and fixed at the bottom of the plating tank 3; the copper anode 8 is mounted on the support frame 4 and arranged parallel to the cathode ITO glass 7, and the cathode ITO glass 7 and the copper anode 8 are respectively connected to the negative electrode and the positive electrode of a DC power supply 10; the ultraviolet light pattern generated on the projection screen 2 of the projection device 1 irradiates the plating solution on the surface of the cathode ITO glass 7, and a metal pattern is deposited on the surface of the cathode ITO glass 7 by applying an external voltage.
[0022] In this embodiment, the middle part of the upper surface of the copper anode 8 is fixedly connected to the support frame 4, and the connection between the copper anode 8 and the support frame 4 is an insulated connection. The support frame 4 is connected to the slider 6 through the mounting plate 5, and the slider 6 is slidably connected to the movable track 9. Further, the movable track 9 is vertically arranged, and the slider 6 moves on the movable track 9 to drive the support frame 4 and the copper anode 8 to move in the Z-axis direction. In a specific implementation of this embodiment, the movable track 9 and the slider 6 are threadedly matched, and the rotation of the movable track drives the slider to move up and down, thereby driving the support frame 4 and the copper anode 8 to move up and down in the Z-axis direction, so as to adjust the electrode spacing between the copper anode and the cathode ITO glass.
[0023] In this embodiment, the projection device 1 is connected to a computer. After receiving a digital signal from the computer, the projection device controls the DMD micromirror to quickly flip to reflect the light source. The light source emits ultraviolet light, which is reflected by each DMD micromirror to the projection screen to generate an ultraviolet light pattern. The projection device directly uses an existing DLP projector. Further, the parallel light passes through the plating tank 3 and irradiates the plating solution on the surface of the cathode ITO glass 7.
[0024] In this embodiment, the plating solution is a mixed plating solution of a metal complex Cu-EDTA and a photocatalyst titanium dioxide. The liquid level of the plating solution in the plating tank exceeds the upper surface of the copper anode. Figure 2 As shown, under ultraviolet light projection, highly active electrons and holes are formed inside the titanium dioxide in the plating solution on the cathode surface. They migrate to the titanium dioxide surface and react with oxygen and water molecules to generate free radicals such as hydroxyl groups with strong oxidizing properties. Under the oxidation of free radicals, the metal complex in the plating solution will undergo a dissociation reaction, decomplexing and releasing metal copper ions. At this time, an external voltage can be applied to directionally electrodeposit a copper metal pattern on the surface of the cathode ITO glass 7. Compared with the existing metal ion solution as a plating solution, by using a mixed plating solution of metal complex Cu-EDTA and photocatalyst titanium dioxide, it is possible to print a patterned metal microelectrode structure without treating the cathode surface.
[0025] In this embodiment, the plating tank 3 is made of UV-transmitting glass, which can transmit ultraviolet light of a certain wavelength while absorbing visible light to improve photosensitivity and deposit metal microelectrodes with the same shape as the projection pattern.
[0026] In this embodiment, the cathode ITO glass is conductive on one side, and the thickness of the cathode ITO glass is 0.4-0.8 mm, and the preferred thickness is 0.6 mm. The cathode ITO glass is conductive facing the upper surface of the copper anode, and the thickness of the cathode ITO glass will affect the transmittance of ultraviolet light. By limiting the thickness of the cathode ITO glass, it is helpful to increase the transmittance of ultraviolet light, improve the photosensitivity, and thus improve the accuracy of the printed pattern.
[0027] In this embodiment, the copper anode 8 and the cathode ITO glass 7 have the same size and are separated from the inner wall of the plating tank 3 by a set distance. In a specific implementation, the copper anode 8 and the cathode ITO glass 7 have a size of 5×5 cm and are 2 cm away from the inner wall of the plating tank.
[0028] The method for using the maskless electrochemical metal 3D printing based on light-controlled ion release provided in this embodiment is as follows: Step (1): First, wipe the dust on the surface of the cathode ITO glass 7 with deionized water, then use an acid-base cleaning agent to remove grease and pollution, rinse with deionized water several times to ensure that there is no residual cleaning liquid, and finally blow dry with nitrogen to complete the cleaning process.
[0029] Step (2): The plating tank 3 is placed horizontally on the projection screen 2, the cathode ITO glass 7 is fixed at the bottom of the plating tank 3, the copper anode 8 is fixed at the lower end of the support frame 4, and then it is leveled until it is parallel to the cathode ITO glass 7, and the movable slide rail 9 is adjusted to make the electrode spacing between the copper anode 8 and the cathode ITO glass 7 to a set distance, the upper part of the copper anode 8 is connected to the positive electrode of the DC power supply 10, and the cathode ITO glass 7 is connected to the negative electrode of the DC power supply 10.
[0030] Furthermore, the electrode spacing between the copper anode 8 and the cathode ITO glass 7 is adjusted to 1-2 cm, preferably 1 cm. The electrode spacing will affect the electric field distribution. Too large an electrode spacing will lead to uneven electric field distribution, affecting the quality of the deposited layer and being unfavorable for metal pattern deposition. Therefore, a smaller electrode spacing is the optimal solution.
[0031] Step (3): prepare a mixed plating solution of the metal complex Cu-EDTA and the photocatalyst titanium dioxide, stir it manually and place it in an ultrasonic cleaning machine, oscillate it for a period of time so that the titanium dioxide particles are fully dispersed in the entire solution, and place it in a dark environment for use after ultrasonication.
[0032] Step (4): Turn on the DLP projection device and connect it to the computer. After the PC adjusts the resolution, brightness and other parameters of the projection image, it outputs a digital signal to the DLP projection device, which is reflected by the DMD micromirror to the projection screen 2 to generate an ultraviolet light projection pattern. At this time, turn on the DC power supply 10, and the photocatalysis and electrodeposition synergistically deposit for a period of time to prepare the metal microelectrode.
[0033] Furthermore, the output voltage of the DC power supply is a constant voltage of 3V.
[0034] Step (5): After the preparation is completed, turn off the DC power supply 10, then stop the DLP projection device, take out the cathode ITO glass 7, clean the residual liquid on the surface, and store it in a dry environment.
[0035] The maskless electrochemical metal 3D printing device based on photocontrolled ion release provided in this embodiment uses a projection device to project a designed ultraviolet light pattern into a local plating solution to destroy the metal complex structure inside the plating solution, and then realizes local electrodeposition of metal ions under the action of an external DC power supply to quickly prepare patterned metal microelectrodes.
[0036] Example 2 In a typical embodiment of the present invention, a maskless electrochemical metal 3D printing method based on photo-controlled ion release is provided, comprising the following steps: The cathode ITO glass and the copper anode separated by a set distance are placed in a mixed plating solution of the metal complex Cu-EDTA and the photocatalyst titanium dioxide; The projected ultraviolet light pattern irradiates the mixed plating solution on the surface of the cathode ITO glass, causing the metal complex in the mixed plating solution to react and decomplex to release metal copper ions; Voltages were applied to the cathode ITO glass and the copper anode respectively, and a copper metal pattern was directionally electrodeposited on the side of the cathode ITO glass opposite to the copper anode to complete the preparation of the metal microelectrode.
[0037] Furthermore, the preparation process of the mixed plating solution includes: Add disodium EDTA, copper sulfate pentahydrate and deionized water to a beaker, stir until all dissolved, and let stand for a while to allow for full complexation; Repeatedly diluting the metal complex solution to a set concentration, and then dissolving titanium dioxide powder in the prepared metal complex solution and stirring; After stirring, the solution was placed in an ultrasonic cleaning chamber for oscillation to allow the titanium dioxide particles to be fully dispersed throughout the solution. After the ultrasonic cleaning, the solution was placed in a dark environment for later use.
[0038] Taking the preparation of 30mg / L Cu-EDTA-0.3g / L titanium dioxide mixed plating solution as an example, the specific preparation process is as follows: First, add 0.093g of disodium ethylenediaminetetraacetate, 0.0625g of copper sulfate pentahydrate and 50ml of deionized water into a beaker, stir with a glass rod until all dissolved, and let it stand for a while to allow it to fully complex; repeatedly dilute the metal complex solution to 200ml so that the concentration of Cu-EDTA is 30mg / L, dissolve 0.06g of titanium dioxide powder in the prepared metal complex solution, stir for 2min, then place it in an ultrasonic cleaning machine, oscillate for 20min to allow the titanium dioxide particles to be fully dispersed in the entire solution, and place it in a dark environment for use after ultrasonication.
[0039] During the preparation process, titanium dioxide and Cu-EDTA are fully mixed by utilizing the oscillation effect of a high-power, high-frequency ultrasonic cleaner. If the ultrasonic dispersion is insufficient, the mixed liquid will agglomerate, greatly affecting subsequent printing work.
[0040] Furthermore, before the cathode ITO glass is placed in the mixed plating solution, the cathode ITO glass is cleaned and dried with nitrogen. Before the copper anode is placed in the mixed plating solution, the copper anode is leveled until it is parallel to the cathode ITO glass, and the electrode spacing is adjusted to a set distance.
[0041] Furthermore, after the metal microelectrode is printed, the DC power supply is turned off first and then the projection equipment is stopped, the cathode ITO glass is taken out, the residual liquid on the surface is cleaned, and it is stored in a dry environment for reuse.
[0042] In this embodiment, the electrodeposition process is controlled by photocatalytic technology. The cathode is a single-sided conductive ITO transparent conductive glass, and its surface does not need to be modified by manufacturing a physical mask or photolithography technology. The preparation of maskless patterned metal microelectrodes is completed through optical mode control. The morphology and size of the deposited metal are controlled by the projection pattern, forming a new maskless electrochemical metal 3D printing technology.
[0043] Although the above describes the specific implementation mode of the present invention in conjunction with the accompanying drawings, it is not intended to limit the scope of protection of the present invention. Those skilled in the art should understand that various modifications or variations that can be made by those skilled in the art on the basis of the technical solution of the present invention without creative work are still within the scope of protection of the present invention.
Claims
1. A maskless electrochemical metal 3D printing device based on photo-controlled ion release, characterized in that: The invention comprises a projection device, a plating tank, a support frame, a cathode ITO glass and a copper anode; the plating solution is placed in the plating tank, the plating tank is horizontally placed above the projection screen of the projection device, the cathode ITO glass is placed in the plating tank and fixed at the bottom of the plating tank; the copper anode is installed on the support frame and arranged in parallel with the cathode ITO glass, the cathode ITO glass and the copper anode are respectively connected to the negative electrode and the positive electrode of a direct current power supply; the ultraviolet light pattern generated on the projection screen of the projection device irradiates the plating solution on the surface of the cathode ITO glass, and a metal pattern is deposited on the surface of the cathode ITO glass by applying an external voltage.
2. The maskless electrochemical metal 3D printing device based on light-controlled ion release according to claim 1, characterized in that: The middle part of the upper surface of the copper anode is fixedly connected to the support frame, the connection between the copper anode and the support frame is an insulating connection, the support frame is connected to the slider through a mounting plate, and the slider is slidably connected to the moving track.
3. The maskless electrochemical metal 3D printing device based on light-controlled ion release according to claim 2, characterized in that: The moving track is vertically arranged, and the sliding block moves on the moving track to drive the supporting frame and the copper anode to move in the Z-axis direction.
4. The maskless electrochemical metal 3D printing device based on light-controlled ion release according to claim 1, characterized in that: The projection device is connected to a computer. After receiving a digital signal from the computer, the projection device controls the DMD micromirror to quickly flip to reflect the light source. The light source emits ultraviolet light, which is reflected by the DMD micromirror to the projection screen to generate an ultraviolet light pattern.
5. The maskless electrochemical metal 3D printing device based on photo-controlled ion release according to claim 1, characterized in that: The plating solution is a mixed plating solution of metal complex Cu-EDTA and photocatalyst titanium dioxide.
6. The maskless electrochemical metal 3D printing device based on light-controlled ion release according to claim 1, characterized in that: The plating tank is made of ultraviolet transparent glass, and the surface of the cathode ITO glass opposite to the copper anode is conductive.
7. A maskless electrochemical metal 3D printing method based on photo-controlled ion release, implemented by the device according to any one of claims 1 to 6, characterized in that: The following steps are involved: The cathode ITO glass and the copper anode separated by a set distance are placed in a mixed plating solution of the metal complex Cu-EDTA and the photocatalyst titanium dioxide; The projected ultraviolet light pattern irradiates the mixed plating solution on the surface of the cathode ITO glass, causing the metal complex in the mixed plating solution to react and decomplex to release metal copper ions; Voltages were applied to the cathode ITO glass and the copper anode respectively, and a copper metal pattern was directionally electrodeposited on the side of the cathode ITO glass opposite to the copper anode to complete the preparation of the metal microelectrode.
8. The maskless electrochemical metal 3D printing method based on photo-controlled ion release according to claim 7, characterized in that: The preparation process of the mixed plating solution comprises: Add disodium EDTA, copper sulfate pentahydrate and deionized water to a beaker, stir until all dissolved, and let stand for a while to allow for full complexation; Repeatedly diluting the metal complex solution to a set concentration, and then dissolving titanium dioxide powder in the prepared metal complex solution and stirring; After stirring, the solution was placed in an ultrasonic cleaning machine for oscillation to allow the titanium dioxide particles to be fully dispersed throughout the solution. After ultrasonication, the solution was placed in a dark environment for later use.
9. The maskless electrochemical metal 3D printing method based on photo-controlled ion release according to claim 7, characterized in that: Before the cathode ITO glass is placed in the mixed plating solution, it is cleaned and dried with nitrogen. Before the copper anode is placed in the mixed plating solution, it is leveled until it is parallel to the cathode ITO glass, and the electrode spacing is adjusted to a set distance.
10. The maskless electrochemical metal 3D printing method based on photo-controlled ion release according to claim 7, characterized in that: After the metal microelectrode printing is completed, turn off the DC power supply first and then stop the projection equipment, take out the cathode ITO glass, clean the residual liquid on the surface, and store it in a dry environment for reuse.