Patterned electrolysis device and preparation method for patterned conductive polymer thin film
Patent Information
- Application Number
- PCT/CN2025/097187
- Authority / Receiving Office
- WO · WO
- Patent Type
- Applications
- Current Assignee / Owner
- Priority Date
- 2025-03-11
- Filing Date
- 2025-05-26
- Publication Date
- 2026-09-17
Smart Images
Figure CN2025097187_17092026_PF_FP_ABST
Abstract
Description
Method for preparing patterned electrolysis apparatus and patterned conductive polymer thin film
[0001] Related applications
[0002] This application claims priority to Chinese Patent Application No. 202510286490.4, filed on March 11, 2025, entitled "Patterned Electrolysis Apparatus and Method for Preparing Patterned Conductive Polymer Thin Films". Technical Field
[0003] This invention relates to the field of electropolymerization and electrodeposition technology, specifically to a patterned electrolysis device and a method for preparing patterned conductive polymer films. Background Technology
[0004] Patterned conductive polymer films are conductive polymer films with specific patterns. These films have applications in many fields, such as electronic devices and wearable sensors. Although there are many existing methods for preparing patterned conductive polymer films, common methods include inkjet printing, printing, photopolymerization, photolithography, oxidant stencils, and self-assembly.
[0005] It is important to note that existing methods have certain limitations when fabricating complex patterns involving multiple materials. For example, inkjet printing and printing technologies require polymer inks with suitable viscosity; otherwise, insufficient pattern resolution or ink diffusion may occur. While configuring inks with appropriate viscosity, it is also crucial to ensure that the electrical properties of the polymer are not compromised. Photopolymerization and photolithography processes require consideration of the impact of subsequent processes on the cured material. Especially in the preparation of multiple materials, the solvent of the next material may damage the already cured conductive polymer layer, thus affecting the integrity and electrical properties of the pattern. The preparation of the photopolymerization and photocuring precursor solutions also needs to be considered. Oxidant templates and self-assembly methods require pre-fabrication of patterns on the substrate, which is complex for complex patterns. Furthermore, these methods typically require complex processes and expensive equipment when processing high-precision complex patterns, increasing manufacturing costs and time. Summary of the Invention
[0006] To address the aforementioned technical problems, this invention provides a patterned electrolysis device and a method for preparing patterned conductive polymer films. By fabricating a special patterned electrolysis device to control the contact area between the liquid and the electroplating substrate, patterned films with different patterns and compositions can be prepared in a single electropolymerization and electrodeposition process.
[0007] Therefore, the present invention provides the following technical solution:
[0008] In a first aspect, the present invention provides a patterned electrolysis apparatus in an optional embodiment, comprising a patterned electrolysis cell, a conductive electrode, and a conductive substrate;
[0009] The patterned electrolytic cell has several patterned channels on one side of its upper part. The opening of each patterned channel has a predetermined shape. The lower end of each patterned channel is connected to a corresponding liquid flow channel. Each liquid flow channel is isolated from each other and is used to deliver electrolyte to its respective patterned channel.
[0010] The conductive electrode is located at the bottom of the patterned electrolytic cell;
[0011] The conductive substrate is located at the top of the patterned electrolytic cell, and its lower surface is attached to the upper surface of the patterned channel. It is used to form a polymer film on the conductive area of the lower surface of the conductive substrate after the electrolyte is electropolymerized.
[0012] In this invention, by designing liquid flow channels, the electrolyte in the liquid flow channels directly contacts the conductive substrate at the channel opening of the patterned channel, and the pattern formed on the contact surface is the pattern required for electropolymerization. Furthermore, by designing mutually isolated liquid flow channels, the patterned electrolysis device can simultaneously accommodate different electrolytes, and different electrolytes can directly contact different positions on the conductive substrate.
[0013] Preferably, a liquid injection port is provided on the other side of the upper part of the patterned electrolytic cell, and the liquid injection port is connected to each liquid flow channel for conveying the electrolyte to each liquid flow channel; the height of the liquid injection port is higher than the height of the patterned channel.
[0014] In a second aspect, the present invention provides, in optional embodiments, a method for preparing a patterned conductive polymer film, comprising the following steps:
[0015] Fabrication of patterned electrolysis devices;
[0016] The upper surface of the patterned electrolytic cell and the lower surface of the conductive substrate are subjected to non-wetting treatment;
[0017] The inner wall of the patterned channel is impregnated.
[0018] For each channel opening of the patterned channel, the electrolyte corresponding to the polymer film to be formed at the channel opening is injected through the injection port of the patterned electrolytic cell into the liquid flow channel communicating with the channel opening, so that the electrolyte fills the liquid flow channel and the patterned channel communicating with the liquid flow channel, and the liquid level of the electrolyte in the patterned channel is attached to the lower surface of the conductive substrate; and the conductive electrode and the conductive substrate are respectively connected to the power source for electropolymerization, so that the electrolyte in the patterned channel electropolymerizes on the conductive area of the lower surface of the conductive substrate to form a patterned film.
[0019] In this invention, the power source is an electrochemical workstation. When a three-electrode system is required, a reference electrode can be inserted at the liquid inlet of the patterned electrolytic cell. This invention designs liquid flow channels that allow the electrolyte and conductive substrate to directly contact each other on one side of the cell. The pattern formed on the contact surface is the pattern required for electropolymerization. Different patterned channel openings can be designed at different locations on the contact surface, thereby forming polymer films with different patterns at different locations on the contact surface. Furthermore, by designing mutually isolated liquid flow channels, the electrolytic cell can simultaneously accommodate different electrolytes, and different electrolytes can directly contact different locations on the conductive substrate, enabling the formation of conductive polymer films of various materials.
[0020] In this invention, the upper surface of the patterned electrolytic cell and the lower surface of the conductive substrate need to be non-wetting treated. This is because if the upper surface of the patterned electrolytic cell and the lower surface of the conductive substrate are wetted, the electrolyte will spread in the gap between them, resulting in unclear / blurred boundaries of the final thin film pattern, or even the pattern connecting the entire surface. Additionally, the inner wall of the patterned channel needs to be wetted. This is because, due to the narrowness of the patterned channel, without wetting, the surface tension is too high, and the electrolyte will not reach the height of the upper surface of the patterned channel, making it difficult to contact the lower surface of the conductive substrate. Therefore, the patterned channel needs to be wetted to improve the affinity of the electrolyte for the inner wall of the patterned channel, increase the electrolyte level in the patterned channel, and allow the electrolyte to contact the lower surface of the conductive substrate.
[0021] Preferably, when the electrolyte is an aqueous solution, the upper surface of the patterned electrolytic cell and the lower surface of the conductive substrate are treated to be hydrophobic, and the inner wall of the patterned channel is treated to be hydrophilic; or, when the electrolyte is an oil-phase solution, the upper surface of the patterned electrolytic cell and the lower surface of the conductive substrate are treated to be hydrophilic, and the inner wall of the patterned channel is treated to be hydrophobic. The hydrophobic treatment of the upper surface of the patterned electrolytic cell and the lower surface of the conductive substrate is performed by coating the patterned electrolytic cell and the conductive substrate with a hydrophobic material; or, polishing the patterned electrolytic cell and the conductive substrate. The hydrophilic treatment of the upper surface of the patterned electrolytic cell and the lower surface of the conductive substrate is performed by coating the patterned electrolytic cell and the conductive substrate with a hydrophilic material; or, surface plasma cleaning of the patterned electrolytic cell and the conductive substrate. The hydrophobic treatment of the inner wall of the patterned channel is performed by coating the wall of the patterned channel with a hydrophobic material. The method for hydrophilic treatment of the inner wall of the patterned channel is to coat the wall of the patterned channel with a hydrophilic material.
[0022] Furthermore, the method for hydrophilic or hydrophobic treatment of the inner wall of the patterned channel is to fill the patterned channel with gel; the method of filling the gel includes: injecting gel material into the patterned channel for curing; or, filling the patterned channel with cured gel material.
[0023] Preferably, the gel material is selected from one or more of polyacrylamide, agarose, dextran sulfate, cellulose acetate, starch, siloxane, polystyrene-divinylbenzene, polyvinylpyrrolidone, polyethylene glycol, silica gel, xanthan gum, carrageenan, or paraffin; and / or, when filling the patterned channel with gel, space needs to be reserved at the bottom of the patterned electrolytic cell for electrolyte injection, or, the electrolyte is mixed into the gel material.
[0024] In this invention, hydrophilic or hydrophobic treatment of the inner wall of the patterned channel filler can further restrict the flow direction of the electrolyte and improve the patterning resolution and adhesion of the film.
[0025] "It can further restrict the flow direction of the electrolyte" can be understood as follows: if the electrolyte is an aqueous phase, and the electrolytic cell material itself is a hydrophobic material, the electrolyte cannot enter the through hole, causing the ITO glass to not contact the electrolyte surface. Therefore, a hydrophilic gel coating is set on the inner wall of the patterned channel to increase the electrolyte surface height.
[0026] Preferably, the preparation method further includes coating the top surface of the patterned electrolytic cell with a removable adhesive after the step of preparing the patterned electrolytic device.
[0027] In this invention, the electrolyte injection method is as follows: first, the electrolyte is vacuum-defoamed; then, a long needle is used to draw the electrolyte into an injection container; the electrolyte is injected from the injection port at the top of the patterned electrolytic cell using the injection container to ensure that the electrolyte fills the liquid flow channels within the patterned electrolytic cell. By coating the top surface of the patterned electrolytic cell with a removable adhesive, the adhesion between the conductive substrate and the patterned electrolytic cell is increased, further preventing electrolyte overflow, and ensuring that the conductive substrate can be easily removed after electropolymerization.
[0028] Preferably, the patterned electrolytic cell is fabricated using 3D printing technology, silicone molding technology, or computer numerical control processing technology. The conductive electrode material is selected from platinum sheets, graphite sheets, silver sheets, or conductive glass; and / or, the conductive substrate is selected from conductive glass, metal, or a flexible substrate coated with a conductive coating. The electrolyte is a conductive polymer monomer solution or a conductive polymer solution; the conductive polymer monomer solution includes polymer monomers, dopants, stabilizers, and solvents. The conductive polymer monomer is selected from one or more of aniline and its derivatives, thiophene and its derivatives, or pyrrole and its derivatives. There are no special requirements for the selection of the conductive polymer monomer, as long as it is an electropolymerizable monomer; and / or, when the electrolyte of the electrolyte is an aqueous phase electrolyte, the dopant is a substance that can simultaneously provide protons (hydrogen ions) and anions, and the specific type is not required, such as: polystyrene sulfonic acid, camphor sulfonic acid, hydrochloric acid, sulfuric acid, benzene sulfonic acid, etc. When the electrolyte of the electrolyte is an oil-phase electrolyte: the dopant is selected from one or more of organic acids, organic anionic salts, or ionic liquids. For example, the organic acid can be p-toluenesulfonic acid, octadecyl sulfonic acid, fluorosulfonic acid, or methanesulfonic acid; the organic anionic salt can be potassium tetrafluoroborate, lithium hexafluorophosphate, or lithium trifluoromethanesulfonate; and the ionic liquid can be 1-ethyl-3-methylimidazolium tetrafluoroborate, 1-butyl-3-methylimidazolium hexafluorophosphate, or 1-butyl-3-methylimidazolium trifluoromethanesulfonate, etc.; and / or, the stabilizer is selected from one or more of polyethylene glycol, polyacrylamide, polyvinyl alcohol, polymethyl methacrylate, or polyvinylpyrrolidone; and / or, the solvent is selected from water, organic solvents, or a mixture of water and organic solvents that are miscible with water.
[0029] In this invention, the mold for preparing the patterned electrolytic cell has a hollow structure. When using silicone molding technology or computer numerical control (CNC) processing technology, the mold needs to be designed in sections. The mold material is selected from one of photosensitive resin, nylon, engineering plastics, polytetrafluoroethylene, plexiglass, or silicone.
[0030] Preferably, the area of the conductive electrode covers the area of the channel opening of the patterned channel.
[0031] Preferably, the conductive region on the lower surface of the conductive substrate has a first shape, the shape region of the channel opening of the patterned channel has a second shape, and the shape formed by the patterned thin film on the conductive substrate is the intersection of the first shape and the second shape.
[0032] The conductive substrate can be conductive across the entire surface, conductive in a specific area, or have independently controlled conductivity in a specific zone.
[0033] The method for fabricating the partitioned independently conductive substrate includes etching the conductive layer of the conductive substrate or printing a partitioned conductive coating.
[0034] This invention further restricts the formed pattern by adjusting the actual conductive area and region of the conductive region on the lower surface of the conductive substrate. The formed pattern is the intersection of the actual conductive region and the shape region of the channel opening of the patterned channel. The conductive electrode is installed by bending the conductive electrode material into the bottom of the patterned electrolytic cell, or by directly and uniformly coating the bottom of the patterned electrolytic cell with a slurry of conductive electrode material.
[0035] Thirdly, in an optional embodiment, the present invention provides an application of the above-described method for preparing patterned conductive polymer films in the preparation of electrochromic lateral devices.
[0036] In this invention, the method for preparing an electrochromic lateral device includes the following steps:
[0037] A conductive layer is disposed on a substrate, and a patterned conductive polymer film is obtained by electroplating on the conductive layer using the method described above. A first conductive electrode and a second conductive electrode are disposed on both sides of the conductive layer, with a preset distance between the first and second conductive electrodes and the conductive layer. A baffle is disposed on the other two sides of the conductive layer, and the baffle is tightly connected to the first and second conductive electrodes to form a frame structure. Finally, a substrate is covered on top of the first conductive electrode, the electrolyte, the second conductive electrode, and the baffle. The electrolyte is injected between the first conductive electrode, the second conductive electrode, and the conductive layer, and the electrolyte covers the electrochromic layer to obtain an electrochromic lateral device.
[0038] Compared with the prior art, the present invention has one of the following beneficial effects:
[0039] 1. This invention designs liquid flow channels that allow the electrolyte in the liquid flow channels to directly contact the conductive substrate at the channel opening of the patterned channel, and the pattern formed on the contact surface is the pattern required for electropolymerization. Furthermore, by designing mutually isolated liquid flow channels, the patterned electrolysis device can simultaneously accommodate different electrolytes, and different electrolytes can directly contact different positions on the conductive substrate.
[0040] 2. The preparation method provided by this invention offers a novel patterning technique that exhibits better adhesion compared to printed and electroplated films. It does not require modification of existing electrochemical polymerization formulations and is compatible with all electrochemical polymerization and electrodeposition schemes in solution phases.
[0041] 3. This method is simple, has low production cost, and produces high-quality films. Compared with equally simple printing and printing, it does not have the coffee ring effect and does not require the preparation of high-viscosity inks. Attached Figure Description
[0042] To more clearly illustrate the technical solutions in the embodiments of the present invention, the accompanying drawings used in the embodiments will be briefly introduced below. Obviously, the drawings described below are only some embodiments of the present invention. For those skilled in the art, other drawings can be obtained based on these drawings without creative effort.
[0043] Figure 1 is a schematic diagram of the patterned electropolymerization technology of the present invention, a design diagram of the patterned electrolytic cell, and a physical image of the patterned electrolytic cell;
[0044] Figure 2 is a schematic diagram of the patterned electrolytic cell of the present invention;
[0045] Figure 3 shows a model diagram of the patterned electrolytic cell, a physical diagram of the patterned electrolytic device, and a physical diagram of the patterned thin film according to Embodiment 1 of the present invention.
[0046] Figure 4 shows a physical diagram of the patterned electrolysis device and the patterned thin film of Embodiment 2 of the present invention;
[0047] Figure 5 is a schematic diagram of the patterned electrolytic cell of Embodiment 3 of the present invention;
[0048] Figure 6 is a physical image of the patterned thin film of Embodiment 3 of the present invention;
[0049] Figure 7 is a diagram showing the relationship between the patterned electrolytic cell, the conductive substrate, and the solution wettability in Embodiment 1 of the present invention;
[0050] Figure 8 is a model diagram of the patterned electrolytic cell of Embodiment 4 and Comparative Example 1 of the present invention;
[0051] Figure 9 is a physical image of the patterned thin film prepared in Comparative Example 2 of the present invention;
[0052] Figure 10 shows a physical image of the electrochromic lateral device prepared according to an application embodiment of the present invention, and gradient spectra of three conductive polymer films on the electrochromic lateral device. 1-Patterned electrolytic cell, 2-Conductive electrode, 3-Conductive substrate, 4-Patterned channel, 5-Liquid flow channel, 6-Injection port. Detailed Implementation
[0053] To make the objectives, technical solutions, and advantages of this invention clearer, the invention will be further described in detail below with reference to specific embodiments. It should be understood that the specific embodiments described herein are merely illustrative of the invention and are not intended to limit the invention.
[0054] With the rapid development of 3D printing technology, the production of high-precision (below 0.1mm) three-dimensional hollow molds has become both simple and low-cost. 3D printing technology can not only quickly and accurately manufacture the required molds, but also offers a wide range of material choices, including not only traditional rigid plastics but also metals or flexible materials. Therefore, microchannel molds with complex geometries can be designed and fabricated to replace traditional electropolymerization electrolytic cells, thereby enabling the fabrication of complex multi-material conductive polymer patterns.
[0055] Figure 1a schematically illustrates the principle of preparing patterned thin films using electropolymerization according to the present invention. The conductive substrate 3 is ITO glass and is located at the top of the patterned electrolytic cell 1. The two liquid flow channels 5 of the patterned electrolytic cell 1 are respectively filled with solution a and solution b (solution a and solution b are different). The conductive electrode 2 is located at the bottom of the patterned electrolytic cell 1. The conductive substrate 3 and the conductive electrode 2 are respectively connected to a power source. Through electropolymerization, two rectangular patterned thin films are formed on the ITO glass.
[0056] Figure 1b schematically illustrates the structure of a patterned electrolytic cell 1. The upper part of the patterned electrolytic cell 1 has several patterned channels 4, each with a rectangular opening. The lower end of each patterned channel 4 is connected to a corresponding liquid flow channel 5. The liquid flow channels 5 are isolated from each other and are used to deliver electrolyte to their respective patterned channels 4. Four fluid flow channels 5 are schematically shown in the figure, each corresponding to three patterned channels 4. The electrolyte used in the three patterned channels 4 is the same, but the electrolytes in different liquid flow channels 5 can be different.
[0057] Figure 1c schematically shows the actual patterned electrolytic cell 1 mold made using stereolithography 3D printing technology and JS-UV-CBY-01 photosensitive resin. The upper part of the patterned electrolytic cell 1 has four different sized patterns, and the use of conductive copper foil as conductive electrodes 2 is further illustrated. For a detailed structural diagram, see Figure 2, where 1 is the patterned electrolytic cell, 4 is the patterned channel, and 6 is the liquid injection port, with the height of the liquid injection port 6 being higher than the height of the patterned channel 4.
[0058] In Examples 1-3, since the patterned electrolytic cell is made of polytetrafluoroethylene, which is hydrophobic, and the electrolyte used in Examples 1-3 is an aqueous electrolyte, no additional non-wetting treatment is required.
[0059] Example 1
[0060] This embodiment provides a method for preparing a patterned conductive polymer thin film, including the following steps:
[0061] (1) A patterned electrolytic cell made of polytetrafluoroethylene (PTFE) material is fabricated using CNC machining technology. A physical image of the patterned electrolytic cell is shown in Figure 3a. The upper part of the patterned electrolytic cell has three patterned channels, each with a rectangular opening. The lower ends of the three patterned channels are connected to corresponding liquid flow channels. The three liquid flow channels are isolated from each other and are used to deliver electrolyte to their respective patterned channels. In the accompanying drawings of this embodiment, the patterned channels and liquid flow channels are integrated, meaning that the shape and area of the channel openings, the area at the connection point between the patterned channels and the liquid flow channels, and the horizontal area of the liquid flow channels are the same. Carbon rods are used as conductive electrodes and placed at the bottom of the patterned electrolytic cell. ITO glass is used as a conductive substrate, with its conductive surface facing the patterned electrolytic cell, as shown in Figure 3b.
[0062] (2) In this embodiment, the relationship between the patterned electrolytic cell, the conductive substrate, and the solution wettability was further investigated. The results are shown in Figure 7. Figure 7a schematically illustrates the effects of plasma cleaning technology and siloxane hydrophobic technology on the hydrophilic and hydrophobic modification of ITO glass. It can be clearly seen that the contact between the electrolyte and the conductive substrate is greatly affected by wettability, which is also a key influencing step in the patterning process using the electrolytic cell. Figure 7b schematically illustrates the solvent connection state at the interface of the ITO glass after adding deionized water to the hydrophilic silicone electrolytic cell and immersing it in a hydrophobic reagent for hydrophobic treatment. The solvent fills the entire cavity and covers the ITO film, and it does not overflow along the cell. In addition, a removable adhesive is coated on the top surface of the patterned electrolytic cell (i.e., the top surface of the area used to separate different patterned channels and the outer area of the entire electrolytic cell).
[0063] (3) The inner wall of the patterned channel is wetted (i.e., the inner wall of the patterned channel is hydrophilic), specifically: a hydrophilic gel coating (the gel material is polyacrylamide) is applied to the inner wall of the patterned channel.
[0064] (4) The three electrolytes are poured into the three liquid flow channels respectively. The electrolytes fill the liquid flow channels and the liquid level rises continuously to the patterned channel connected to the liquid flow channel. Finally, the electrolytes are attached to the lower surface of the conductive substrate (ITO glass) at the horizontal plane of the patterned channel. Electrolyte a includes 0.1 mol / L aniline, 0.2 mol / L camphor sulfonic acid and 5 wt% polyethylene glycol with a molecular weight of 20,000. Electrolyte b includes 0.1 mol / L 3,4-ethylenedioxythiophene, 0.2 mol / L camphor sulfonic acid and 5 wt% polyethylene glycol with a molecular weight of 20,000. Electrolyte c includes 0.1 mol / L pyrrole, camphor sulfonic acid and 5 wt% polyethylene glycol with a molecular weight of 20,000.
[0065] (5) The conductive electrode is connected to the working electrode alligator clip of the electrochemical workstation through carbon conductive tape, and the conductive substrate is connected to the counter electrode alligator clip through copper foil. Ag / AgCl is used as the reference electrode, and constant voltage electropolymerization is performed. The electropolymerization time is 600s. The patterned film obtained is shown in Figure 3c.
[0066] Example 2
[0067] This embodiment provides a method for preparing a patterned conductive polymer thin film, including the following steps:
[0068] (1) A patterned electrolytic cell made of polytetrafluoroethylene (PTFE) material was fabricated using CNC machining technology. The upper part of the patterned electrolytic cell had two patterned channels (see Figure 4b). The openings of the two patterned channels were horizontally elongated rectangles. The lower ends of the two patterned channels were connected to the corresponding liquid flow channels. The two liquid flow channels were isolated from each other and were used to deliver electrolyte to their respective patterned channels. Carbon rods were used as conductive electrodes and placed at the bottom of the patterned electrolytic cell. ITO glass was used as a conductive substrate with its conductive surface facing the patterned electrolytic cell. The conductive area on the lower surface of the conductive substrate was a vertically elongated rectangle. The shape of the patterned film was the intersection of the horizontally elongated rectangles at the openings of the two patterned channels and the vertically elongated rectangles on the lower surface of the conductive substrate (see Figure 3a).
[0069] (2) Apply removable adhesive to the top surface of the patterned electrolytic cell.
[0070] (3) The inner wall of the patterned channel is wetted (i.e., the inner wall of the patterned channel is hydrophilic), specifically: a hydrophilic gel coating (the gel material is polyacrylamide) is applied to the inner wall of the patterned channel.
[0071] (4) Pour the electrolyte into the two liquid flow channels respectively. The electrolyte fills the liquid flow channels and the liquid level rises continuously to the patterned channel connected to the liquid flow channels. Finally, the electrolyte is attached to the lower surface of the conductive substrate (ITO glass) at the horizontal plane of the patterned channel. The electrolyte includes 0.1 mol / L aniline, 0.2 mol / L camphor sulfonic acid and 5 wt% polyethylene glycol with a molecular weight of 20,000.
[0072] (5) The conductive electrode is connected to the working electrode alligator clip of the electrochemical workstation through carbon conductive tape, and the conductive substrate is connected to the counter electrode alligator clip through copper foil. Ag / AgCl is used as the reference electrode, and constant voltage electropolymerization is performed. The electropolymerization time is 600s. The patterned film obtained is shown in Figure 4b.
[0073] Example 3
[0074] This embodiment provides a method for preparing a patterned conductive polymer thin film, including the following steps:
[0075] (1) A patterned electrolytic cell made of polytetrafluoroethylene (PTFE) material was fabricated using CNC machining technology. A schematic diagram of the patterned electrolytic cell is shown in Figure 5. The upper side of the patterned electrolytic cell has three patterned channels, each with a rectangular opening. The lower ends of the three patterned channels are connected to their respective liquid flow channels, which are isolated from each other. The other side of the upper part of the patterned electrolytic cell has a liquid injection port, which is connected to the three liquid flow channels. The height of the liquid injection port is higher than the height of the patterned channels, used to deliver the electrolyte to each liquid flow channel. Carbon rods were used as conductive electrodes and placed at the bottom of the patterned electrolytic cell. ITO glass was used as the conductive substrate, with its conductive surface facing the patterned electrolytic cell.
[0076] (2) Apply removable adhesive to the top surface of the patterned electrolytic cell.
[0077] (3) The inner wall of the patterned channel is wetted (i.e., the inner wall of the patterned channel is hydrophilic), specifically: a hydrophilic gel coating (the gel material is polyacrylamide) is applied to the inner wall of the patterned channel.
[0078] (4) The three electrolytes are poured into the three liquid flow channels from the injection port respectively. The electrolytes fill the liquid flow channels and the liquid level rises continuously to the patterned channel connected to the liquid flow channel. Finally, the electrolytes are attached to the lower surface of the conductive substrate (ITO glass) at the horizontal plane of the patterned channel. Electrolyte a includes 0.1 mol / L aniline, 0.2 mol / L camphor sulfonic acid and 5 wt% polyethylene glycol with a molecular weight of 20,000. Electrolyte b includes 0.1 mol / L 3,4-ethylenedioxythiophene, 0.2 mol / L camphor sulfonic acid and 5 wt% polyethylene glycol with a molecular weight of 20,000. Electrolyte c includes 0.1 mol / L pyrrole, camphor sulfonic acid and 5 wt% polyethylene glycol with a molecular weight of 20,000.
[0079] (5) Connect the conductive electrode to the working electrode alligator clip of the electrochemical workstation through carbon conductive tape, and connect the conductive substrate to the counter electrode alligator clip through copper foil. Use Ag / AgCl as the reference electrode (inserted into the liquid injection port of the patterned electrolytic cell) to perform constant voltage electropolymerization (polymerization voltage of electrolyte a is 0.8V, polymerization voltage of electrolyte b is 1.2V, and polymerization voltage of electrolyte c is 0.625V) for 600s. The resulting patterned film is shown in Figure 6.
[0080] Example 4
[0081] This embodiment provides a method for preparing a patterned conductive polymer thin film, including the following steps:
[0082] (1) A patterned electrolytic cell made of polytetrafluoroethylene (PTFE) material was fabricated using CNC machining technology. A physical image of the patterned electrolytic cell is shown in Figure 8b. One side of the upper part of the patterned electrolytic cell has a patterned channel with a rectangular opening. The lower end of the patterned channel is connected to the corresponding liquid flow channel. The other side of the upper part of the patterned electrolytic cell has a liquid injection port, which is connected to the liquid flow channel. The height of the liquid injection port is higher than the height of the patterned channel, used to deliver the electrolyte to each liquid flow channel. Carbon rods were used as conductive electrodes and placed at the bottom of the patterned electrolytic cell. ITO glass was used as the conductive substrate, with its conductive surface facing the patterned electrolytic cell.
[0083] (2) Apply removable adhesive to the top surface of the patterned electrolytic cell.
[0084] (3) Pour the electrolyte into the liquid flow channel from the injection port, so that the electrolyte fills the liquid flow channel and the liquid level rises continuously to the patterned channel connected to the liquid flow channel, so that the electrolyte is finally attached to the lower surface of the conductive substrate (ITO glass) at the horizontal plane of the patterned channel. The electrolyte includes 0.1 mol / L aniline, 0.2 mol / L camphor sulfonic acid and 5 wt% polyethylene glycol with a molecular weight of 20000.
[0085] (4) The conductive electrode is connected to the working electrode alligator clip of the electrochemical workstation through carbon conductive tape, and the conductive substrate is connected to the counter electrode alligator clip through copper foil. Ag / AgCl is used as the reference electrode, and constant voltage electropolymerization is performed. The electropolymerization time is 600s, and a rectangular patterned thin film is obtained by electropolymerization.
[0086] Comparative Example 1
[0087] This comparative example provides a method for preparing a patterned conductive polymer thin film, comprising the following steps:
[0088] (1) A patterned electrolytic cell made of polytetrafluoroethylene (PTFE) material is fabricated using CNC machining technology. A physical image of the patterned electrolytic cell is shown in Figure 8a. The upper part of the patterned electrolytic cell has a patterned channel with a rectangular opening. The lower end of the patterned channel is connected to a corresponding liquid flow channel for supplying electrolyte to the respective patterned channel. In the accompanying drawings of this embodiment, the patterned channel and the liquid flow channel are integrated, meaning that the shape and area of the channel opening, the area at the connection point between the patterned channel and the liquid flow channel, and the horizontal area of the liquid flow channel are the same. A carbon rod is used as a conductive electrode and placed at the bottom of the patterned electrolytic cell. ITO glass is used as a conductive substrate, with its conductive surface facing the patterned electrolytic cell.
[0089] (2) Apply removable adhesive to the top surface of the patterned electrolytic cell.
[0090] (3) The electrolyte is poured into the liquid flow channel. Since the height of the liquid flow channel at the pouring position is the same as the height of the liquid flow channel below the patterned channel, the electrolyte cannot rise into the patterned channel through the liquid flow channel below the patterned channel. As a result, the electrolyte in the liquid flow channel cannot contact the lower surface of the conductive substrate. The electrolyte includes 0.1 mol / L aniline, 0.2 mol / L camphor sulfonic acid and 5 wt% polyethylene glycol with a molecular weight of 20,000.
[0091] (4) The conductive electrode was connected to the working electrode alligator clip of the electrochemical workstation through carbon conductive tape, and the conductive substrate was connected to the counter electrode alligator clip through copper foil. Ag / AgCl was used as the reference electrode, and constant voltage electropolymerization was performed. The electropolymerization time was 600s. It was found that patterned thin films could not be electropolymerized.
[0092] Comparative Example 2
[0093] This comparative example provides a method for preparing a patterned conductive polymer thin film, comprising the following steps:
[0094] (1) A patterned electrolytic cell made of polytetrafluoroethylene (PTFE) material was fabricated using CNC machining technology. A physical image of the patterned electrolytic cell is shown in Figure 8b. One side of the upper part of the patterned electrolytic cell has a patterned channel with a rectangular opening. The lower end of the patterned channel is connected to the corresponding liquid flow channel. The other side of the upper part of the patterned electrolytic cell has a liquid injection port, which is connected to the liquid flow channel. The height of the liquid injection port is higher than the height of the patterned channel, used to deliver the electrolyte to each liquid flow channel. Carbon rods were used as conductive electrodes and placed at the bottom of the patterned electrolytic cell. ITO glass was used as the conductive substrate, with its conductive surface facing the patterned electrolytic cell.
[0095] (2) Pour the electrolyte into the liquid flow channel from the injection port, so that the electrolyte fills the liquid flow channel and the liquid level rises continuously to the patterned channel connected to the liquid flow channel, so that the electrolyte is finally attached to the lower surface of the conductive substrate (ITO glass) at the horizontal plane of the patterned channel. The electrolyte includes 0.1 mol / L aniline, 0.2 mol / L camphor sulfonic acid and 5 wt% polyethylene glycol with a molecular weight of 20000.
[0096] (3) The conductive electrode was connected to the working electrode alligator clip of the electrochemical workstation through carbon conductive tape, and the conductive substrate was connected to the counter electrode alligator clip through copper foil. Ag / AgCl was used as the reference electrode, and constant voltage electropolymerization was performed. The electropolymerization time was 600s. It was found that the top surface of the patterned electrolytic cell was not coated with removable adhesive, which caused the electrolyte to overflow. The actual electroplating area exceeded the part of the patterned channel, resulting in the inability to obtain the desired electroplating pattern. See Figure 9.
[0097] Application Examples
[0098] This embodiment provides a method for preparing an electrochromic lateral device using the method of Example 3, including the following steps:
[0099] An indium tin oxide (ITO) film is deposited on an insulating glass substrate. The substrate is then electroplated sequentially in a solution of aniline monomers (0.1 mol / L aniline, 0.025 mol / L sodium polystyrene sulfonate, 0.025 mol / L camphor sulfonic acid, 0.05 mol / L sulfuric acid, with water as the solvent), a solution of thiophene monomers (0.1 mol / L thiophene, 0.025 mol / L sodium polystyrene sulfonate, 0.025 mol / L camphor sulfonic acid, 0.05 mol / L sulfuric acid, with water as the solvent), and a solution of poly(3,4-ethylenedioxythiophene-2-methanol) monomers (0.1 mol / L 3,4-ethylenedioxythiophene-2-methanol, 0.025 mol / L sodium polystyrene sulfonate, 0.025 mol / L camphor sulfonic acid, 0.05 mol / L sulfuric acid, with water as the solvent). This process deposits three films—polyaniline, polypyrrole, and poly(3,4-ethylenedioxythiophene-2-methanol)—on top of the ITO film.
[0100] On insulating glass, a copper foil conductive tape is attached to both sides of an ITO film to serve as the first and second conductive electrodes. The first and second conductive electrodes are spaced at a predetermined distance from the conductive layer and the electrochromic layer. Then, encapsulating adhesive is applied to both sides of the first and second conductive electrodes on the insulating glass, and the encapsulating adhesive is tightly connected to the first and second conductive electrodes. Transparent glass is then placed over the first conductive electrode, the electrolyte, the second conductive electrode, and the barrier. Finally, 0.005 mol / L sulfuric acid electrolyte is injected between the first and second conductive electrodes and the conductive layer using a syringe, and the electrolyte covers the electrochromic layer, resulting in an electrochromic lateral device.
[0101] When the positive terminal of a constant voltage power supply is connected to the first conductive electrode and the negative terminal is connected to the second conductive electrode, and a voltage of 3V is applied, it is observed that the three films simultaneously exhibit a uniform gradient effect (as shown in Figure 10A). The gradient spectra of the three films are measured using a thin film transmission spectroscopy test device constructed with a tungsten lamp light source, an electric displacement stage, and a spectrometer, as shown in Figures 10B-10D.
[0102] Although the principles of the present invention have been described in detail above with reference to preferred embodiments, those skilled in the art should understand that the above embodiments are merely illustrative explanations of the implementation of the present invention and are not intended to limit the scope of the present invention. The details in the embodiments do not constitute a limitation on the scope of the present invention. Any obvious changes, such as equivalent transformations or simple substitutions, based on the technical solutions of the present invention without departing from the spirit and scope of the present invention fall within the protection scope of the present invention.
Claims
1. A patterned electrolysis apparatus, characterized in that, Includes patterned electrolytic cells, conductive electrodes, and conductive substrates; The patterned electrolytic cell has several patterned channels on one side of its upper part. The opening of each patterned channel has a predetermined shape. The lower end of each patterned channel is connected to a corresponding liquid flow channel. Each liquid flow channel is isolated from the others and is used to deliver electrolyte to its respective patterned channel. The conductive electrode is located at the bottom of the patterned electrolytic cell; The conductive substrate is located at the top of the patterned electrolytic cell, and its lower surface is attached to the upper surface of the patterned channel, so as to form a polymer film on the conductive area on the lower surface of the conductive substrate after the electrolyte is electropolymerized.
2. The patterned electrolysis apparatus according to claim 1, characterized in that, The patterned electrolytic cell has a liquid injection port on the other side of its upper part, and the liquid injection port is connected to each liquid flow channel for delivering the electrolyte to each liquid flow channel. The height of the injection port is higher than the height of the patterned channel.
3. A method for preparing a patterned conductive polymer thin film, characterized in that, Includes the following steps: Fabrication of patterned electrolysis devices; The upper surface of the patterned electrolytic cell and the lower surface of the conductive substrate are subjected to non-wetting treatment; The inner wall of the patterned channel is impregnated. For each channel opening of the patterned channel, the electrolyte corresponding to the polymer film to be formed at the channel opening is injected into the liquid flow channel communicating with the channel opening through the liquid injection port of the patterned electrolytic cell, so that the electrolyte fills the liquid flow channel and the patterned channel communicating with the liquid flow channel, and the liquid level of the electrolyte in the patterned channel is in contact with the lower surface of the conductive substrate. as well as The conductive electrode and the conductive substrate are respectively connected to a power source for electropolymerization, which causes the electrolyte in the patterned channel to electropolymerize on the conductive area on the lower surface of the conductive substrate to form a patterned thin film.
4. The method for preparing a patterned conductive polymer thin film according to claim 3, characterized in that, When the electrolyte is an aqueous solution, the upper surface of the patterned electrolytic cell and the lower surface of the conductive substrate are treated to be hydrophobic, and the inner wall of the patterned channel is treated to be hydrophilic; or, When the electrolyte is an oil-phase solution, the upper surface of the patterned electrolytic cell and the lower surface of the conductive substrate are treated to be hydrophilic, and the inner wall of the patterned channel is treated to be hydrophobic.
5. The method for preparing a patterned conductive polymer thin film according to claim 4, characterized in that, The method for hydrophobic treatment of the upper surface of the patterned electrolytic cell and the lower surface of the conductive substrate is as follows: The patterned electrolytic cell and the conductive substrate are coated with a hydrophobic material; or The patterned electrolytic cell and the conductive substrate are polished.
6. The method for preparing a patterned conductive polymer thin film according to claim 4, characterized in that, The method for hydrophilic treatment of the upper surface of the patterned electrolytic cell and the lower surface of the conductive substrate is as follows: The patterned electrolytic cell and the conductive substrate are coated with a hydrophilic material; or The patterned electrolytic cell and conductive substrate are cleaned using surface plasma cleaning.
7. The method for preparing a patterned conductive polymer thin film according to claim 4, characterized in that, The method for hydrophobic treatment of the inner wall of the patterned channel is as follows: coating the wall of the patterned channel with a hydrophobic material; and / or The method for hydrophilic treatment of the inner wall of the patterned channel is to coat the wall of the patterned channel with a hydrophilic material.
8. The method for preparing a patterned conductive polymer thin film according to claim 3, characterized in that, It also includes coating the top surface of the patterned electrolytic cell with a removable adhesive after the step of preparing the patterned electrolytic device; The area of the conductive electrode covers the area of the opening of the patterned channel.
9. The method for preparing a patterned conductive polymer thin film according to claim 3, characterized in that, The conductive region on the lower surface of the conductive substrate has a first shape, the shape region of the channel opening of the patterned channel has a second shape, and the shape formed by the patterned thin film on the conductive substrate is the intersection of the first shape and the second shape.
10. The application of the method for preparing the patterned conductive polymer film according to claim 3 in the preparation of electrochromic lateral devices.