An electric heating glass micro-nano additive-subtractive composite manufacturing method

Abstract

The application provides an electric heating glass micro-nano additive-subtractive composite manufacturing method, which comprises the following steps: pretreating the surface of a glass substrate, depositing a copper film on the pretreated glass substrate to prepare a copper-clad glass substrate; printing a designed electrode pattern on the copper-clad glass substrate by taking photoresist as a mask pattern forming material; performing solidification treatment after printing; etching the copper film by taking the solidified photoresist pattern as a mask to obtain a designed mask electrode pattern; removing the photoresist, cleaning and drying the copper-clad glass substrate; taking the etched copper conductive pattern as a seed layer to plate a metal layer on the seed layer; performing post-treatment on the formed transparent electric heating glass after plating the metal layer; and coating a protective layer on the surface of the post-treated transparent electric heating glass. The application can realize low-cost, high-efficiency and batch manufacturing of large-size and high-performance metal mesh transparent electric heating glass.

Description

Technical Field

[0001] This invention belongs to the field of transparent electrically heated glass technology, specifically relating to a method for manufacturing electrically heated glass micro-nano additive-subtractive composite materials. Background Technology

[0002] The statements in this section are merely background information related to the present invention and do not necessarily constitute prior art.

[0003] Transparent electrically heated glass, a special type of glass with electric heating function, can achieve functions such as de-icing, defogging, and defrosting. It has been widely used in many fields such as automotive windshields, optical windows, optoelectronic instruments, aircraft, and national defense. It is unaffected by external temperature differences and always maintains its light transmission without icing, fogging, or frost.

[0004] Traditional transparent electric heating glass typically uses indium tin oxide (ITO) coated glass. However, ITO's high cost and high sheet resistance prevent it from achieving high efficiency and low cost. In recent years, ITO alternatives, such as transparent conductive polymer films, carbon-based materials (graphene, carbon nanotubes, etc.), and metal nanowires (gold, silver, copper nanowires), have been developed and applied to the manufacture of transparent electric heating glass. Although these materials can all be used to manufacture transparent electric heating glass, they also face the challenge of achieving high light transmittance and low sheet resistance. In particular, using traditional coating processes, while increasing the thickness of the conductive material coating (reducing sheet resistance and improving conductivity), also reduces light transmittance. Furthermore, the manufacturing process cycle and production cost are further increased, limiting its widespread application in large-size (especially ultra-large size on the meter scale) and high-performance transparent electric heating fields.

[0005] Metal mesh, as an emerging transparent electrode material, can resolve the contradiction between simultaneously improving light transmittance and conductivity by adjusting linewidth, spacing, mesh shape, and arrangement. In particular, it enables the fabrication of large-area metal mesh across macro and micro scales. Currently, manufacturing technologies for transparent electrically heated glass based on metal mesh mainly include photolithography, laser direct writing, screen printing, nanoimprinting, inkjet printing, and electro-jet printing. Photolithography is one of the most commonly used techniques for high-performance transparent metal mesh electrodes; however, when the substrate size reaches the meter scale, it is difficult to achieve large-area photolithography and suffers from drawbacks such as the need for masks and high manufacturing costs. Laser direct writing can achieve the fabrication of large-area, high-transmittance metal mesh, but it suffers from high production costs, low material utilization, and requires the use of vacuum coating technologies, resulting in long production cycles. Large-size screen printing suffers from low precision in forming the metal mesh and requires high substrate flatness, failing to meet the requirements of high-performance metal mesh electrically heated glass. Nanoimprinting presents difficulties in manufacturing large-area, seamless molds, with high mold manufacturing costs, complex production processes, and long cycles. Inkjet printing suffers from limitations in its printing materials (typically with a viscosity less than 30 mPa·s), low resolution (difficult to achieve linewidths below 20 micrometers), and poor electrical properties and weak bonding strength with the substrate. Manufacturing large-size transparent metal mesh electrodes using electro-inkjet printing or other methods is prone to nozzle clogging during prolonged printing processes (especially since the nano-silver paste used for electric heating is prone to agglomeration and solidification, easily leading to nozzle blockage). Printing large-size substrates is particularly time-consuming, making long-term stable printing impossible and resulting in low yields. Therefore, there is an urgent need to develop a new manufacturing process for the low-cost, efficient, and mass production of high-performance transparent electrically heated metal mesh glass. Summary of the Invention

[0006] To address the aforementioned problems, this invention proposes a method for manufacturing electrically heated glass using micro / nano additive-subtractive composite materials. This invention enables low-cost, efficient, and mass production of large-size, high-performance metal mesh transparent electrically heated glass.

[0007] According to some embodiments, the present invention adopts the following technical solution:

[0008] A method for manufacturing electrically heated glass micro / nano additive-subtractive composites includes the following steps:

[0009] The surface of the glass substrate is pretreated, and a copper thin film is deposited on the pretreated glass substrate to prepare a copper-clad glass substrate.

[0010] Using photoresist as a molding material for mask patterns, the designed electrode patterns are printed on a copper-clad glass substrate. After printing, a curing process is performed.

[0011] Using the cured photoresist pattern as a mask, a wet etching process is used to etch the copper film to obtain conductive patterns with different electrode structures.

[0012] Remove the photoresist, clean and dry the copper-clad glass substrate;

[0013] Using the etched copper conductive pattern as a seed layer, a metal layer is plated on the seed layer;

[0014] After the metal layer is plated, the resulting transparent electrically heated glass undergoes post-processing.

[0015] A protective layer is applied to the surface of the post-processed transparent electrically heated glass.

[0016] Compared with the prior art, the beneficial effects of the present invention are as follows:

[0017] (1) The present invention can use an array of multi-nozzle electric field to drive micro-nano 3D printing photoresist materials to achieve efficient printing of large area and ultra-large size mask patterns. In particular, the use of precision electroplating enables efficient and high-precision bulk forming, which can realize efficient and low-cost manufacturing of large area flexible transparent electrically heated glass, and can realize efficient printing of large-size substrates. Precision electroplating is bulk forming, with high production efficiency, high precision, and good consistency.

[0018] (2) The present invention has high production stability and avoids nozzle clogging in large-area printing. Since photoresist is used as the printing material, it avoids the problem of nozzle clogging when printing conductive ink, which would prevent stable printing on large-size substrates. In addition, compared with conductive inks such as nano silver paste, photoresist has the outstanding advantage of low material cost. Therefore, the proposed method has high production stability and good consistency, and can meet the requirements of efficient and low-cost mass production of large-size high-performance electrically heated glass.

[0019] (3) The present invention has excellent performance in various aspects, including very good electrical, optical and electric heating properties. On the one hand, by using a seed layer of copper, and especially by continuing to deposit metal layers (conductive metals such as copper, nickel and silver), the electrical properties of the electric heating glass are greatly improved without sacrificing optical properties.

[0020] (4) The production cost of the present invention is low, avoiding the use of expensive equipment such as photolithography and laser processing, and overcoming the need for harsh production environments such as cleanrooms.

[0021] (5) The present invention has high production efficiency and makes full use of the advantages of micro-nano additive manufacturing (micro-nano 3D printing, metal deposition) and subtractive manufacturing (etching), especially the combination of array nozzles and deposited metal body forming: greatly improves production efficiency and meets the requirements of large-scale production.

[0022] (6) It has good compatibility with existing processes. The present invention uses copper as a seed layer, which overcomes the problems of high production costs caused by directly using nano-silver as a metal mesh in existing processes. It meets the requirements of low-cost green manufacturing.

[0023] To make the above-mentioned objects, features and advantages of the present invention more apparent and understandable, preferred embodiments are described below in detail with reference to the accompanying drawings. Attached Figure Description

[0024] The accompanying drawings, which form part of this invention, are used to provide a further understanding of the invention. The illustrative embodiments of the invention and their descriptions are used to explain the invention and do not constitute an improper limitation of the invention.

[0025] Figure 1 A physical image of a large-size transparent electrically heated glass provided in an embodiment of the present invention;

[0026] Figure 2 A manufacturing process flow diagram provided for an embodiment of the present invention;

[0027] Figure 3 This is a schematic diagram of a specific process provided for an embodiment of the present invention;

[0028] Figure 4 Scanning electron microscope (SEM) images and elemental analysis results of the deposited metal layers in this embodiment of the invention: (a) and (b) are Cu, Ni SEM images; (c) and (d) are Cu, Ni EDS images; (e) and (f) are Cu, Ni XPS images;

[0029] Figure 5 Temperature distribution images of transparent electrically heated glass under different voltages provided in this embodiment of the invention. Detailed implementation method:

[0030] The present invention will be further described below with reference to the accompanying drawings and embodiments.

[0031] It should be noted that the following detailed description is illustrative and intended to provide further explanation of the invention. Unless otherwise specified, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention pertains.

[0032] It should be noted that the terminology used herein is for the purpose of describing particular embodiments only and is not intended to limit the scope of exemplary embodiments according to the invention. As used herein, the singular form is intended to include the plural form as well, unless the context clearly indicates otherwise. Furthermore, it should be understood that when the terms "comprising" and / or "including" are used in this specification, they indicate the presence of features, steps, operations, devices, components, and / or combinations thereof.

[0033] Example 1

[0034] A method for mass production of transparent electrically heated glass based on electric field-driven micro / nano 3D printing, such as... Figure 2 As shown, the main steps include:

[0035] Step 1: Preparation of copper-clad glass substrate

[0036] Using glass as the substrate, the surface of the glass substrate is first cleaned and degreased. Then, a copper thin film is deposited on the cleaned glass substrate using processes such as magnetron sputtering, physical vapor deposition, or chemical vapor deposition to prepare a copper-clad glass substrate. Figure 1 As shown.

[0037] Step 2: Printing the photoresist mask pattern

[0038] Using photoresist as the mask material, micro / nano 3D printing technology driven by an array of multi-nozzle electric fields efficiently prints the designed electrode patterns (electrically heated conductive lines) on a copper-clad glass substrate, achieving preliminary pre-curing. By adjusting the printing parameters, patterns of different line types (straight lines, serpentine curves, circles, spirals, discontinuous lines, etc.) and sizes (linewidth, period, etc.) can be printed. After all printing is completed, post-curing treatment is performed to achieve complete curing of the photoresist.

[0039] Step 3: Etching of copper-clad glass substrate

[0040] Using the photoresist pattern printed and cured in step 2 as a mask, a copper thin film is etched using a wet etching process to obtain the designed mask electrode pattern.

[0041] Step 4: Remove photoresist

[0042] Remove the printed photoresist mask. Dissolve the photoresist using N-methylpyrrolidone (NMP) solution or developer; then rinse with deionized water and dry the etched copper-clad glass substrate.

[0043] Step 5: Deposit a metal layer

[0044] Using the etched copper conductive pattern as the seed layer, such as Figure 3 As shown, other metallic materials, including copper, silver, nickel, or gold, are deposited on top of the copper seed layer using chemical plating or precision micro-electroplating processes.

[0045] Step 6: Post-processing

[0046] After chemical plating or precision micro-plating is completed, ultrasonic cleaning with deionized water is used to remove residual plating solution and excess impurities, and then the solution is dried with nitrogen.

[0047] Step 7: Apply a protective layer.

[0048] Coating the surface of the transparent electrically heated glass in step 6 with a protective layer material can effectively improve the environmental stability of the transparent metal grid and enhance the bonding strength between the conductive pattern and the glass substrate.

[0049] In this embodiment, preferably, the glass-copper clad laminate selected in step 1 includes physical vapor deposition magnetron sputtering, chemical plating, electroplating, etc., and the thickness of the deposited copper seed layer is 10nm-10μm.

[0050] In this embodiment, preferably, the type of photoresist used for printing in step 2 includes, but is not limited to, SU-8 or ma-N400.

[0051] In this embodiment, preferably, the printing program for the electrode structure in step 2 can be designed with different path codes and imported into the machine to achieve printing of different geometric patterns, line widths, heights, and cycles through optimized printing process parameters. Specifically, this includes:

[0052] The required mesh size and period are designed according to the needs, and the corresponding processing code is generated using data processing software and input into the electric field driven jet deposition micro-nano 3D printing device.

[0053] Place the printing material into the barrel of the printing device; connect the nitrogen cylinder to the barrel via a pressure valve; connect the DC power supply to the flat electrode of the printing device via a wire;

[0054] Place the coated substrate onto the printing platform of the printing device. Turn on the micro-nano 3D printing device, and print the entire metal mesh according to the designed and optimized parameters such as mesh type (square, rhombus, triangle, hexagon, etc.), size (line width, period, height, etc.), and geometric arrangement, combined with optimized 3D printing process parameters.

[0055] In this embodiment, the printhead used has an inner diameter of 1μm-100μm, the distance between the printhead and the printing substrate is 20μm-200μm, the air pressure of the printing device is 50kpa-200kpa, the power supply voltage of the printing device is 100V-1500V, and the printing speed of the printing device is 1mm / s-180mm / s.

[0056] Preferably, the linewidth of the photoresist printing pattern in step 2 is 1 μm to 100 μm, and the period is 20 μm to 2000 μm.

[0057] In this embodiment, the photoresist mask pattern is cured in step 3 by ultraviolet light curing or thermal curing.

[0058] Preferably, the etching process described in step 3 requires precise time control, with an etching time ranging from 1 second to 120 seconds.

[0059] Preferably, the wet etching process described in step 3 includes direct immersion and vertical spray etching, with the specific etching process selected according to the copper film thickness.

[0060] Preferably, the speed of the wet etching process described in step 3 can be controlled by adjusting the temperature and the etchant concentration. The etchant temperature ranges from 20°C to 60°C, and the etchant concentration can be selected according to the type of etchant. The etchant concentration can be adjusted to reduce or increase the etching speed.

[0061] Preferably, the conductive pattern after removing the photoresist in step 4 is subjected to ultrasonic cleaning and drying.

[0062] In this embodiment, the deposited metal layer described in step 5 can be deposited using either electroplating or electroless plating processes. The deposited metal includes, but is not limited to, copper, silver, nickel, gold, etc. Figure 4 As shown.

[0063] In this embodiment, the protective layer material applied in step 7 includes, but is not limited to, varnish, polyimide solution, acrylic resin, etc.

[0064] Example 2

[0065] A method for manufacturing electrically heated glass micro / nano additive-subtractive composites includes the following steps:

[0066] Step 1: Preparation of copper-clad glass substrate

[0067] Ordinary float glass was selected as the substrate, and a copper metal film of uniform thickness was deposited on the surface of the substrate by magnetron sputtering. The glass size was 100mm×100mm, the glass thickness was 2mm, and the thickness of the sputtered copper film was 100nm.

[0068] Step 2: Printing the photoresist mask pattern

[0069] SU-8 photoresist was selected as the printing material, and micro / nano 3D printing driven by a multi-nozzle array electric field was used to achieve efficient fabrication of conductive mask patterns. In this embodiment, the printed pattern is a wire grid structure with an area of ​​90×90mm and a period of 0.5mm. The printing parameters are: DC voltage of 800-1200V, printing pressure of 10-20KPa, printing height of 0.15mm, and printing speed of 40-60mm / s. The resulting mask pattern has a linewidth of approximately 5μm. After printing, the mask was placed in a vacuum drying oven at 135℃ and cured for at least 10 minutes. Once the photoresist has cured, the conductive mask pattern is complete.

[0070] Step 3: Wet etching of copper-clad glass substrate

[0071] The photoresist mask pattern printed in step 2 is subjected to wet etching. A preferred specific process is as follows: a reusable basic copper chloride solution is used and heated to a constant temperature of 50°C. The glass copper-clad laminate is then immersed in the solution for etching. After the copper film not covered by the photoresist mask pattern is completely dissolved, deionized water is quickly sprayed, followed by nitrogen blowing and drying in a vacuum drying oven at 135°C. The copper foil not covered by the photoresist is completely etched away, leaving a conductive pattern with precise linewidth and shape.

[0072] Step 4: Remove photoresist

[0073] The photoresist mask pattern in step 3 is removed by immersing it in NMP photoresist remover solution until the photoresist mask is fully dissolved. Then, it is cleaned with deionized water and dried.

[0074] Step 5: Deposit a metal layer

[0075] Using the etched copper conductive pattern as a seed layer, a layer of silver is deposited on the seed layer using an electroplating process to form a copper-silver composite electrode structure. The specific operation process is as follows: the copper metal grid obtained in step 4 is connected to the electroplating equipment as the cathode, and a stainless steel metal plate on the other side is used as the anode, placed in the electroplating solution. An anode activator is added to the electroplating solution to improve the solubility of the anode, increase the conductivity, and improve the dispersion ability of the solution; an anti-pinhole agent is added to reduce the surface tension of the solution, making it difficult for hydrogen bubbles to remain on the cathode surface, thereby preventing the formation of pinholes.

[0076] When starting the electroplating equipment, to reduce surface roughness, a flow rate of 0.1 A / dm is preferred. 2 ~1A / dm 2 The current density is controlled by a constant temperature system to keep the temperature of the electroplating solution within the range of 23-25℃; a circulating pump is used to flush the solution, which agitates the solution at a speed of 1m / s to 2m / s; and an ultrasonic generator is used to quickly remove air bubbles adhering to the electrode surface during processing, thereby reducing concentration polarization and improving flow field characteristics.

[0077] Step 6: Post-processing

[0078] The part from step 5 was cleaned with deionized water to remove the residue generated during the deposition process. Then the part was dried to obtain a transparent electrically heated glass with a copper-silver composite electrode structure. The sheet resistance was measured to be around 1 Ω / sq and the light transmittance was over 90%.

[0079] Step 7: Apply a protective layer

[0080] A layer of UV varnish is sprayed on as a protective layer, and the sample is completed after curing. By coating the surface of the part with a protective layer, the environmental stability of the transparent metal wire mesh and its adhesion to the substrate can be effectively improved.

[0081] Example 3

[0082] A method for manufacturing electrically heated glass micro / nano additive-subtractive composites includes the following steps:

[0083] Step 1: Preparation of copper-clad glass substrate

[0084] Ordinary float glass was selected as the substrate, and a thin and uniform copper metal film was deposited on the surface of the flexible substrate by magnetron sputtering. The glass was 400mm×400mm in size and 10mm thick, and the deposited copper film was 150nm thick.

[0085] Step 2: Printing the photoresist mask pattern

[0086] SU-8 photoresist was selected as the mask printing material. Combined with a multi-nozzle array electric field-driven micro / nano 3D printing of mask electrode structure patterns, the printed pattern in this embodiment is a grid structure with an area of ​​350mm × 350mm and a period of 250μm. The printing process parameters are: DC voltage of 800-1200V, air pressure of 10-20KPa, printing height of 0.15-0.20mm, and printing speed of 40-60mm / s. The linewidth of the printed mask pattern is approximately 10μm. After printing, the sample was placed in a vacuum drying oven and heated to 135℃ for at least 10 minutes for curing. Once the photoresist has cured, the mask pattern preparation is complete.

[0087] Step 3: Wet etching of copper-clad glass substrate

[0088] The photoresist mask pattern printed in step 2 is then subjected to wet etching. A typical process involves using a reusable basic copper chloride solution, heating it to a constant temperature of 50°C, immersing the copper-clad glass substrate in the solution for 15 seconds, followed by a rapid 10-second deionized water spray. The substrate is then dried using nitrogen and placed in a vacuum drying oven at 135°C. Any copper foil not covered by the photoresist is completely etched away, leaving a conductive pattern with precise linewidth and shape.

[0089] Step 4: Remove photoresist

[0090] Remove the cured photoresist from step 3 by immersing it in a preferred NMP photoresist remover for 3-5 minutes to fully dissolve the photoresist, followed by cleaning and drying with deionized water.

[0091] Step 5: Deposit a metal layer

[0092] Using the etched copper conductive pattern as a seed layer, a layer of silver is deposited on the seed layer using an electroplating process to form a copper-silver composite electrode structure. The specific operation process is as follows: the copper metal grid obtained in step 4 is connected to the cathode of the precision micro electroplating equipment, and a stainless steel metal plate is used as the anode and placed in the electroplating solution; an anode activator is added to the electroplating solution to improve the solubility of the anode, increase the conductivity, and improve the dispersion ability of the solution; an anti-pinhole agent is added to reduce the surface tension of the solution, making it difficult for hydrogen bubbles to stay on the cathode surface, thereby preventing the formation of pinholes.

[0093] When starting the electroplating equipment, to reduce surface roughness, a pressure of 0.1 A / m is preferred. 2 ~2A / m 2 The current density is controlled by a constant temperature system to keep the temperature of the electroplating solution within the range of 45-55℃; a circulating pump is used to flush the solution, which agitates the solution at a speed of 1-2 m / s; and an ultrasonic generator is used to quickly remove air bubbles adhering to the electrode surface during processing, thereby reducing concentration polarization and improving flow field characteristics.

[0094] Step 6: Post-processing

[0095] The micro-electroplated or electroless plated samples were cleaned to remove residues generated during the deposition process. Then, the samples were repeatedly dried to prepare a large-area transparent copper-nickel composite metal mesh transparent electric heating glass. The sheet resistance was measured to be 3-5 Ω / sq and the light transmittance was over 80%.

[0096] Step 7: Apply a protective layer

[0097] In this embodiment, a layer of UV varnish is sprayed as a protective layer, and the sample preparation is completed after curing. By coating a protective layer on the sample surface, the environmental stability of the transparent metal wire grid and its adhesion to the substrate can be effectively improved.

[0098] The above embodiments use photoresist as the printing material and employ electric field-driven jet deposition micro / nano 3D printing technology with a multi-nozzle array to print the required electrode pattern structure (designed conductive pattern) on a copper-clad glass substrate. Then, a wet etching process is used to precisely etch the copper layer under the mask of different patterned electrode structures. Subsequently, the photoresist is removed. Finally, electroplating or chemical plating processes are used to manufacture highly conductive copper-silver metal mesh electrodes, or efficient copper-silver-nickel composite metal mesh electrodes. Combining efficient multi-nozzle printing and deposited metal layer forming, the electrical performance is greatly improved without sacrificing optical properties. This fully utilizes the advantages of micro / nano additive manufacturing (micro / nano 3D printing, precision electroplating) and subtractive manufacturing (etching), overcoming the shortcomings and limitations of existing manufacturing technologies and achieving efficient, low-cost mass production of large-size, high-performance transparent electrically heated glass.

[0099] The above embodiments are merely examples. In other embodiments, the parameters described above may be adjusted or changed according to specific circumstances.

[0100] The above description is merely a preferred embodiment of the present invention and is not intended to limit the invention. Various modifications and variations can be made to the present invention by those skilled in the art. Any modifications, equivalent substitutions, improvements, etc., that can be made by those skilled in the art without creative effort within the spirit and principles of the present invention should be included within the scope of protection of the present invention.

Claims

1. A method for manufacturing electrically heated glass micro / nano additive-subtractive composites, characterized in that, Includes the following steps: The surface of the glass substrate is pretreated, and a copper film is deposited on the pretreated glass substrate to prepare a copper-clad glass substrate. Using photoresist as a molding material for mask patterns, the designed electrode patterns are printed on a copper-clad glass substrate. After printing, a curing process is performed. Using the cured photoresist pattern as a mask, a wet etching process is used to etch the copper film, thereby obtaining the designed mask electrode pattern; Remove the photoresist, clean and dry the copper-clad glass substrate; Using the etched copper conductive pattern as a seed layer, a metal layer is plated on the seed layer; After the metal layer is plated, the resulting transparent electrically heated glass undergoes post-processing. A protective layer is applied to the surface of the post-processed transparent electrically heated glass.

2. The method for manufacturing electrically heated glass micro / nano additive-subtractive composite materials as described in claim 1, characterized in that, The pretreatment process for the glass substrate includes cleaning and degreasing the surface of the glass substrate, and depositing a copper film with a thickness of 10nm-10μm on the cleaned glass substrate by magnetron sputtering, physical vapor deposition or chemical vapor deposition.

3. The method for manufacturing electrically heated glass micro / nano additive-subtractive composite materials as described in claim 1, characterized in that, An array-type multi-nozzle electric field driven micro-nano 3D printing device was used to print the designed electrode pattern on a copper-clad glass substrate. By adjusting the printing parameters of the array-type multi-nozzle electric field driven micro-nano 3D printing device, patterns of different line types and sizes were printed.

4. The method for manufacturing electrically heated glass micro / nano additive-subtractive composite materials as described in claim 3, characterized in that, The required mesh size and cycle are designed according to the needs, the corresponding processing code is generated, and it is input into the array-type multi-nozzle electric field driven micro-nano 3D printing device; The printing material is placed into the barrel of the array-type multi-nozzle electric field driven micro-nano 3D printing device. The nitrogen cylinder is connected to the barrel through the pressure valve. The DC power supply is connected to the flat electrode of the array-type multi-nozzle electric field driven micro-nano 3D printing device through the wire. The coated substrate is placed on the printing platform of the printing device, and the array-type multi-nozzle electric field-driven micro-nano 3D printing device is turned on. Based on the designed and optimized grid type, size and geometric arrangement parameters, combined with the 3D printing process parameters, the entire metal grid is printed.

5. The method for manufacturing electrically heated glass micro / nano additive-subtractive composite materials as described in claim 3, characterized in that, The printing nozzles of the array-type multi-nozzle electric field driven micro-nano 3D printing device have an inner diameter of 1μm-100μm. The distance between the printing nozzle and the printing substrate is 20μm-200μm. The air pressure of the electric field driven micro-nano 3D printing device is 50kpa-200kpa, the power supply voltage is 100V-1500V, and the printing speed is 1mm / s-180mm / s. Or / and, the linewidth of the photoresist printed pattern is 1μm to 100μm, and the period is 20μm to 2000μm.

6. The method for manufacturing electrically heated glass micro / nano additive-subtractive composite materials as described in claim 1, characterized in that, The photoresist mask pattern is cured by ultraviolet light or by heat.

7. The method for manufacturing electrically heated glass micro / nano additive-subtractive composite materials as described in claim 1, characterized in that, Wet etching processes include direct immersion and vertical spraying, with the process method selected based on the thickness of the copper film. Or / and, the wet etching time is 1s to 120s; Or / and, the etching temperature ranges from 20°C to 60°C, and the etching concentration is adjusted according to the type of etching agent.

8. The method for manufacturing electrically heated glass micro / nano additive-subtractive composite materials as described in claim 1, characterized in that, A metal layer is deposited on the seed layer using electroplating or chemical plating processes. The metals include, but are not limited to, copper, silver, nickel, and gold.

9. The method for manufacturing electrically heated glass micro / nano additive-subtractive composite materials as described in claim 1, characterized in that, The post-treatment includes ultrasonic cleaning with deionized water to remove residual plating solution and excess impurities, followed by drying with nitrogen gas.

10. The method for manufacturing electrically heated glass micro / nano additive-subtractive composite materials as described in claim 1, characterized in that, Protective layer materials include, but are not limited to, varnish, polyimide solution, and acrylic resin.

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