Low-cost mass production method of large-size high-performance electric heating glass

Abstract

The application provides a large-size high-performance electric heating glass low-cost batch manufacturing method, which comprises the following steps: depositing a titanium film on a glass substrate, then depositing a copper film on the titanium film to prepare a copper-clad glass substrate; printing a designed electrode pattern on the titanium-clad copper glass substrate by taking polycaprolactone (PCL) as a mask pattern forming material; etching the copper film and the titanium film by taking the PCL pattern as a mask and adopting a wet etching process to transfer and copy the PCL conductive pattern to the copper film and the titanium film; removing the PCL, and cleaning and drying the titanium-clad copper glass substrate; taking the etched copper-titanium conductive pattern as a seed layer, and plating a metal layer on the seed layer; after the metal layer is plated, post-treating the formed transparent electric heating glass; and coating a protective layer on the surface of the post-treated transparent electric heating glass. The application can realize low-cost, efficient and batch manufacturing of large-size, high-performance metal mesh transparent electric heating glass.

Description

Technical Field

[0001] This invention belongs to the field of transparent electric heating glass technology, and in particular relates to a method for low-cost mass production of large-size, high-performance electric heating glass by combining micro-nano additive and subtractive material manufacturing. Background Technology

[0002] Transparent electrically heated glass is a special type of glass that appears transparent to the eye and has an electric heating function. It has high light transmittance and low resistance, and can achieve functions such as de-icing, defogging, and defrosting.

[0003] ●

[0004] Transparent electrically heated glass is widely used in automotive windshields, outdoor displays, smart windows, aircraft, national defense and military applications, thermal sensors, and heat sources for microchips, ensuring that the glass remains transparent and does not freeze, fog, or frost.

[0005] Transparent electric heating glass is made from materials with high electrical conductivity and high visible light transmittance. Traditional transparent electric heating glass generally uses indium tin oxide (ITO) coated glass, but ITO does not have the advantages of high efficiency and low cost, and has the disadvantages of being brittle, fragile, and slightly toxic, which limits its application in transparent heaters.

[0006] Recent studies have proposed several new-generation conductive materials that can replace ITO for transparent heaters.

[0007] ●

[0008] The materials mainly include carbon-based materials (carbon nanotubes, graphene, etc.), metal nanowires or metal nanofibers (gold, silver, copper), etc., but there are also problems that it is difficult to achieve both high transmittance and low resistance at the same time. In particular, when using traditional coating processes, while increasing its transmittance (reducing the thickness of the coating material), it also increases its resistance. In addition, the high manufacturing cost and long preparation process cycle limit its application in the field of large-area (especially ultra-large size on the meter scale) and high-performance transparent electric heating.

[0009] Metal mesh is a promising new conductive material and structure that can better balance the advantages and disadvantages of low resistance and high light transmittance by adjusting the spacing, line width and arrangement of the wires. In particular, it can also realize the manufacturing of large-area metal mesh across macro and micro scales.

[0010] Currently, the main manufacturing technologies for transparent electrically heated glass based on metal mesh grids include screen printing, photolithography, laser direct writing, nanoimprinting, and electro-inking. Large-size screen printing suffers from low printing precision and requires high flatness of the substrate, making it unsuitable for manufacturing large-area, high-performance transparent electrically heated glass with metal mesh grids. Photolithography, while one of the most commonly used techniques for high-performance metal mesh transparent electrodes, struggles to achieve large-area photolithography at the nanoscale and suffers from high costs due to the need for mask fabrication and expensive equipment. Laser direct writing can produce large-area, high-transmittance metal mesh grids, but it suffers from low material utilization, high cost, and requires vacuum coating, resulting in long production cycles. Large-area nanoimprinting is slow, difficult to detach from the imprint, and requires numerous steps to produce large-area imprint films, leading to high costs. Electro-inking is limited by the availability of printing materials (material viscosity typically less than 30 mPa·s), has low printing resolution (difficult to achieve linewidths below 20 micrometers), and exhibits weak adhesion to the substrate. During long-term printing, metal pastes are prone to clogging (for example, nano silver paste is prone to agglomeration and solidification, which can easily lead to nozzle clogging), making it difficult to achieve stable printing over a long period of time and resulting in a low printing yield.

[0011] Therefore, in order to overcome the problems of the above-mentioned technologies, there is an urgent need for a low-cost mass production method for large-size, high-performance electrically heated glass.

[0012] The statements in this section are merely background information related to the present invention and do not necessarily constitute prior art. Summary of the Invention

[0013] To address the limitations of existing technologies in achieving green, low-cost, high-efficiency, and mass production of large-size, high-performance products.

[0014] ●

[0015] Addressing the shortcomings and limitations of transparent electrically heated glass, this invention proposes a low-cost, mass production method for large-size, high-performance electrically heated glass. This method combines micro-nano additive manufacturing, such as multi-nozzle electric field-driven molten jet deposition high-resolution micro-nano 3D printing and precision electroplating. The multi-nozzle electric field-driven molten jet deposition high-resolution micro-nano 3D printing technology enables high-resolution, efficient printing of large-size substrates, and precision electroplating...

[0016] ●

[0017] The plating process is highly efficient, precise, and consistent. This application utilizes micro-nano subtractive manufacturing and employs wet etching to rapidly form a seed layer for precision electroplating, enabling efficient and low-cost mass production of large-area, high-performance transparent electrically heated glass.

[0018] In some embodiments of this application, a low-cost mass production method for large-size, high-performance electrically heated glass is proposed, comprising the following steps:

[0019] First, using polycaprolactone (PCL) as the printing material, a high-resolution micro-nano 3D printing technology with electric field driven melt jet deposition of a multi-nozzle array was used to print the designed grid pattern structure on titanium-coated and copper-coated glass substrates.

[0020] Then, a wet etching process is used to precisely etch the copper and titanium layers that are not covered by the mask; subsequently, the polycaprolactone mask is removed.

[0021] Finally, electroplating or chemical plating processes are used to manufacture highly conductive titanium-copper metal mesh electrodes, or to efficiently manufacture titanium-copper-silver or titanium-copper-nickel composite metal mesh electrodes.

[0022] In some embodiments of this application, a low-cost mass production method for large-size, high-performance electrically heated glass mainly includes the following steps:

[0023] Step 1: Preparation of titanium-coated copper-coated glass substrate

[0024] A titanium-coated copper-coated glass substrate is prepared by depositing a titanium thin film on the glass substrate and then depositing a copper thin film on the titanium thin film.

[0025] Step 2: Printing the molten polycaprolactone (PCL) mask pattern

[0026] Using molten PCL as the mask material, conductive patterns are printed on titanium-coated and copper-coated glass substrates using multi-nozzle electric field driven molten jet deposition micro-nano 3D printing technology. The nozzles are kept heated during printing, and different line types and sizes of conductive patterns can be printed by adjusting the printing parameters.

[0027] Step 3: Etching of titanium-coated and copper-coated glass substrates

[0028] Using the molten PCL pattern printed in step 2 as a mask, a wet etching process is used to etch copper and titanium films, transferring and replicating the PCL conductive pattern onto copper and titanium films.

[0029] Step 4: Remove PCL

[0030] Remove the printed PCL mask to obtain a titanium-copper composite conductive pattern;

[0031] Step 5: Deposit a metal layer

[0032] Using a titanium-copper composite conductive pattern as a seed layer, metallic materials are deposited on top of the titanium-copper seed layer.

[0033] ●

[0034] Step 6: Post-processing

[0035] After the metal material deposition is completed, the product from step 5 is cleaned and dried to obtain a transparent electroplated material.

[0036] ●

[0037] Hot glass;

[0038] Step 7: Apply a protective layer;

[0039] A protective layer material is coated onto the surface of the transparent electrically heated glass in step 6 to improve the environmental stability of the transparent metal grid and the bonding strength between the conductive pattern and the glass substrate.

[0040] In some embodiments of this application, a low-cost mass production method for large-size, high-performance electrically heated glass is characterized by comprising the following steps:

[0041] Step 1: Preparation of titanium-coated copper-coated glass substrate

[0042] Float glass is selected as the substrate. A titanium metal film of uniform thickness is first deposited on the surface of the substrate by magnetron sputtering, and then a copper metal film of uniform thickness is deposited. Preferably, the glass size is 400mm×400mm, the glass thickness is 10mm, the thickness of the sputtered titanium film is 100nm, and the thickness of the copper film is 900nm.

[0043] Step 2: Printing the PCL mask pattern

[0044] Using molten PCL as the printing material, combined with multi-nozzle array electric field-driven molten jet deposition high-resolution micro-nano 3D printing, efficient fabrication of conductive mask patterns is achieved; after printing, the conductive mask pattern is prepared.

[0045] Step 3: Etching of titanium-coated and copper-coated glass substrates

[0046] The PCL mask pattern printed in step 2 is subjected to wet etching. A reusable acidic ferric chloride solution is preferred. The solution is heated to a constant temperature of 50°C and the glass titanium-coated copper-clad laminate is immersed in the etching solution for 15 seconds. Then, deionized water is sprayed for 10 seconds, followed by nitrogen drying. The copper foil not covered by PCL is completely etched away, leaving a copper conductive pattern with precise line width and shape and an unetched titanium layer. A titanium stripping solution is used to immerse and etch the titanium layer at room temperature for 5 seconds. Then, deionized water is sprayed for 10 seconds, followed by nitrogen drying and drying in a vacuum drying oven at 135°C. The titanium foil not covered by PCL and copper is completely etched away, leaving a copper-titanium conductive pattern with precise line width and shape.

[0047] Step 4: Remove the PCL mask

[0048] ●

[0049] To remove the PCL mask pattern from step 3, soak the mask in anhydrous ethanol for 3-5 minutes to remove the PCL mask. Then, wash with deionized water to remove any remaining PCL and dry the mask.

[0050] Step 5: Deposit a metal layer

[0051] Using the etched titanium-copper conductive pattern as a seed layer, a layer of nickel is deposited on the seed layer using an electroplating process to form a copper-nickel composite electrode structure. The specific operation process is as follows: the titanium-copper metal grid structure obtained in step 4 is connected to the cathode of a precision micro electroplating device, and a nickel 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.

[0052] 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; the temperature of the electroplating solution is always controlled within the range of 45-55℃ by a constant temperature system; a circulating pump is used to...

[0053] ●

[0054] The rinsing process stirs the plating solution at a speed of 1m / s-2m / s. An ultrasonic generator is used to quickly remove air bubbles adhering to the electrode surface during processing, which also reduces concentration polarization and improves flow field characteristics.

[0055] Step 6: Post-processing

[0056] The micro-electroplated or electroless plated sample is cleaned to remove the residue generated during the deposition process. Then the sample is repeatedly dried to prepare a large-area transparent copper-nickel composite metal mesh transparent electric heating glass.

[0057] Step 7: Apply a protective layer

[0058] A protective layer is applied to the electrically heated glass from step 6, and the sample preparation is completed after curing. By coating a protective layer on the sample surface, the environmental stability of the transparent metal grid and its adhesion to the substrate are improved.

[0059] In some embodiments of this application, in step 2, the printed conductive pattern is a wire grid structure with an area of ​​390×390mm and a period of 0.25mm. The printing parameters are: DC voltage of 1500-2500V, printing air pressure of 1-20kpa, printing height of 0.2-0.4mm, printing speed of 40-60mm / s, heating temperature of the barrel of 90-100℃, heating temperature of the nozzle of 100-120℃, and the line width of the printed mask pattern is about 5μm.

[0060] Compared with existing technologies and processes, the beneficial effects of this invention are as follows:

[0061] (1) High-resolution micro / nano 3D printing of PCL material is achieved by using an array-type multi-nozzle electric field-driven molten jet deposition, eliminating the need for additional curing treatment. This enables efficient printing of large-area and ultra-large-size mask patterns. In particular, precision electroplating is used, which is a bulk forming process with high production efficiency and precision, and can achieve large-area printing.

[0062] ●

[0063] Transparent electrically heated glass can be manufactured efficiently and at low cost.

[0064] (2) High production stability and avoidance of nozzle clogging in large-area printing; because molten PCL is used as the printing material, the nozzle is always heated during printing, avoiding nozzle clogging when printing conductive inks, which would otherwise prevent stable printing on large-size substrates; in addition, compared with conductive inks such as nano silver paste, PCL has the significant 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.

[0065] (3) High printing accuracy. Compared with other materials printed at room temperature (such as silver paste, carbon nanotubes, etc.), hot-melt materials have a larger diameter reduction ratio during printing, resulting in higher printing accuracy.

[0066] (4) Excellent performance in various aspects. It has very good electrical, optical and electric heating properties. By using a seed layer of titanium-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;

[0067] ●

[0068] (5) Excellent bonding. Using a titanium layer as a transition layer between the seed copper layer and the glass substrate greatly improves the bonding between the seed copper layer and the glass substrate.

[0069] (6) Low production cost. It avoids the use of expensive equipment such as photolithography and laser processing, and overcomes the need for harsh production environments such as cleanrooms.

[0070] (7) High production efficiency, making 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 improving production efficiency and meeting the requirements of large-scale production.

[0071] (8) It has good compatibility with existing processes. It uses copper as a seed layer, which overcomes the problems of high production costs caused by directly using nano-silver as a metal grid in existing processes. It meets the requirements of low cost, green manufacturing and large-scale industrial production.

[0072] (9) Good consistency of metal grids. Metal grids made by wet etching have better edge consistency and lower surface roughness. Electroplating is a bulk process that can compensate for the defects in the line shape after wet etching, and can further improve the edge consistency of metal grids and reduce surface roughness.

[0073] (10) Strong resistance to harsh environments. Due to the presence of the titanium layer, the adhesion between the metal grid and the glass substrate is stronger. After the protective layer is applied, the adhesion can be further improved. The metal grid after magnetron sputtering and electroplating has better density and stronger scratch resistance.

[0074] (11) By combining efficient high-resolution multi-nozzle printing and deposited metal layer forming, the electrical performance is greatly improved without sacrificing optical properties. This method fully utilizes the advantages of micro-nano additive manufacturing (micro-nano 3D printing, precision electroplating) and subtractive manufacturing (wet etching), overcoming the shortcomings and limitations of existing manufacturing technologies, and realizing the green, efficient, and low-cost large-scale production of large-size, high-performance transparent electrically heated glass.

[0075] ●

[0076] Production. Attached Figure Description

[0077] 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.

[0078] Figure 1 A process flow diagram of the manufacturing method provided in an embodiment of the present invention.

[0079] Figure 2 A schematic diagram illustrating the principle of multi-nozzle electric field driven molten jet deposition micro / nano 3D printing.

[0080] Figure 3 The diagram illustrates a specific process according to an embodiment of the present invention.

[0081] Figure 4 The temperature distribution images of transparent electrically heated glass after applying different voltages are provided in the embodiments of the present invention.

[0082] Figure 5 This is a temperature characterization diagram of the electrically heated glass as a function of voltage, according to an embodiment of the present invention. Detailed Implementation

[0083] The present invention will be further described below with reference to the accompanying drawings and embodiments.

[0084] It should be noted that the following detailed description is illustrative and intended to provide further explanation of the invention.

[0085] ●

[0086] 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.

[0087] The technical solutions of the embodiments of this application will be clearly and completely described below with reference to the accompanying drawings. Obviously, the described embodiments are only some embodiments of this application, and not all embodiments. Based on the embodiments of this application, all other embodiments obtained by those of ordinary skill in the art without creative effort are within the scope of protection of this application.

[0088] In the description of this application, it should be understood that the terms "upper," "lower," "left," "right," "front," "rear," "inner," and "outer," etc., indicate the orientation or positional relationship based on the orientation or relative positional relationship shown in the accompanying drawings. They are used only for the convenience of describing this application and for simplification, and do not indicate or imply that the device or element referred to must have a specific orientation, or be constructed and operated in a specific orientation. Therefore, they should not be construed as limitations on this application. Unless otherwise specified, the above-mentioned orientational descriptions can be flexibly set in practical applications, provided that the relative positional relationships shown in the accompanying drawings are satisfied.

[0089] The terms "first" and "second" are used for descriptive purposes only and should not be construed as indicating or implying relative importance or implicitly specifying the number of technical features indicated. Therefore, a feature defined as "first" or "second" may explicitly or implicitly include one or more of that feature. In the description of this application, unless otherwise stated, "a plurality of" means two or more.

[0090] ●

[0091] In the description of this application, it should be noted that, unless otherwise expressly specified and limited, the terms "installation," "connection," "linking," and "communication" should be interpreted broadly, such as fixed connection, detachable connection, or integral connection. Connections can be direct or indirect through an intermediate medium; they can be internal connections between two components or electrical connections between two components. Those skilled in the art can understand the specific meaning of the above terms in this application based on the specific circumstances.

[0092] It should be noted that in practical applications, due to limitations in equipment precision or installation errors, achieving absolute parallelism or perpendicularity is difficult. The descriptions of perpendicularity, parallelism, or unidirectional orientation in this application are not absolute limitations, but rather indicate that perpendicular or parallel structural settings can be achieved within a preset error range (e.g., a vertical deviation of 5°) to achieve the corresponding preset effects. This maximizes the technical effect of the defined features and makes the corresponding technical solution easy to implement, demonstrating high feasibility.

[0093] In this application embodiment, the terms "comprising," "including," or any other variations thereof are intended to cover non-exclusive inclusion, such that a process, article, or apparatus that comprises a list of elements includes not only those elements but also other elements not expressly listed, or elements that constitute such a process, article, or apparatus.

[0094] The inherent elements of the apparatus. Without further limitations, an element defined by the phrase "including one..." does not exclude the presence of other identical elements in the process, article, or apparatus that includes that element.

[0095] In the embodiments of this application, the words "exemplary" or "for example" are used to indicate examples, illustrations, or descriptions. Any embodiment or design that is described as "exemplary" or "for example" in the embodiments of this application should not be construed as being more preferred or advantageous than other embodiments or designs. Rather, the use of the words "exemplary" or "for example" is intended to present the relevant concepts in a specific manner.

[0096] ●

[0097] In some embodiments of this application, a low-cost mass production method for large-size, high-performance electrically heated glass is proposed, comprising the following steps:

[0098] First, using polycaprolactone (PCL) as the printing material, a high-resolution micro-nano 3D printing technology with electric field driven melt jet deposition of a multi-nozzle array was used to print the designed grid pattern structure on titanium-coated and copper-coated glass substrates.

[0099] Then, a wet etching process is used to precisely etch the copper and titanium layers that are not covered by the mask; subsequently, the polycaprolactone mask is removed.

[0100] Finally, electroplating or electroless plating processes are used to manufacture highly conductive titanium-copper metal mesh electrodes.

[0101] ●

[0102] Alternatively, efficient manufacturing of titanium-copper-silver and titanium-copper-nickel composite metal mesh electrodes.

[0103] The following is combined Figure 1-3 Some embodiments of this application will be described below:

[0104] In some embodiments of this application, a low-cost mass production method for large-size, high-performance electrically heated glass mainly includes the following steps:

[0105] Step 1: Preparation of titanium-coated copper-coated glass substrate

[0106] A titanium-coated copper-coated glass substrate is prepared by depositing a titanium thin film on the glass substrate and then depositing a copper thin film on the titanium thin film.

[0107] Step 2: Printing the molten polycaprolactone (PCL) mask pattern

[0108] Using molten PCL as the mask material, conductive patterns are printed on titanium-coated and copper-coated glass substrates using multi-nozzle electric field driven molten jet deposition micro-nano 3D printing technology. The nozzles are kept heated during printing, and different line types and sizes of conductive patterns can be printed by adjusting the printing parameters.

[0109] Step 3: Etching of titanium-coated and copper-coated glass substrates

[0110] Using the molten PCL pattern printed in step 2 as a mask, a wet etching process is used to etch copper and titanium films, transferring and replicating the PCL conductive pattern onto copper and titanium films.

[0111] Step 4: Remove PCL

[0112] Remove the printed PCL mask to obtain a titanium-copper composite conductive pattern;

[0113] Step 5: Deposit a metal layer

[0114] Using a titanium-copper composite conductive pattern as a seed layer, metallic materials are deposited on top of the titanium-copper seed layer.

[0115] Step 6: Post-processing

[0116] After the metal material is deposited, the product from step 5 is cleaned and dried to obtain transparent electrically heated glass.

[0117] Step 7: Apply a protective layer;

[0118] A protective layer material is coated onto the surface of the transparent electrically heated glass in step 6 to improve the environmental stability of the transparent metal grid and the bonding strength between the conductive pattern and the glass substrate.

[0119] In some embodiments of this application, in step 2, an array of multi-nozzle electric field-driven melt jet deposition is used to print high-resolution micro / nano 3D PCL.

[0120] In some embodiments of this application, the metallic material includes, but is not limited to, highly conductive metallic materials such as copper, silver, nickel, and gold.

[0121] ●

[0122] In some embodiments of this application, before depositing titanium and copper thin films, the glass substrate is first subjected to a pre-treatment process.

[0123] The surface is pretreated; then titanium and copper films are deposited on the pretreated substrate surface.

[0124] In some embodiments of this application, the process for depositing the titanium thin film in step 1 is selected from one of physical vapor deposition, magnetron sputtering, electroless plating, electroplating, etc., and the process for depositing the copper thin film in step 1 is selected from one of physical vapor deposition, magnetron sputtering, electroless plating, electroplating, etc.

[0125] In some embodiments of this application, the thickness of the deposited titanium film is 10nm-100nm, and the thickness of the copper film is 100nm-10μm.

[0126] In some embodiments of this application, the titanium thin film deposited in step 1 serves to improve the bonding force between the glass substrate and the copper seed layer.

[0127] In some embodiments of this application, the molecular weight of the PCL used for printing in step 2 is 10,000-80,000.

[0128] In some embodiments of this application, the conductive pattern printing program in step 2 can be designed with different path codes and imported into the printing device to achieve printing of different conductive patterns, line widths, heights, periods, etc., through different printing process parameters. Specifically, it includes:

[0129] The size and period of the grid used to print conductive patterns are designed according to the requirements. The corresponding processing code is generated by data processing software and input into the multi-nozzle electric field driven melt jet deposition micro-nano 3D printing device.

[0130] Place the printing material into the barrel of the printing device; connect the nitrogen cylinder to the barrel via a pressure valve; connect the high-voltage DC power supply to the flat electrode of the printing device via a wire;

[0131] The titanium-coated and copper-coated glass substrate is placed on the printing platform of the printing device; the micro-nano 3D printing device is turned on, and the entire conductive pattern is printed according to the designed and optimized wire grid type and size (such as line width, period, height, etc.) and the optimized 3D printing process parameters.

[0132] In some embodiments of this application, the printhead used is a Musashi printhead with an inner diameter of 10-500μm, the distance between the printhead and the printing substrate is 10-400μm, the air pressure of the printing device is 1-20kpa, the power supply voltage of the printing device is 300-3500V, the printing speed of the printing device is 1-200mm / s, the heating temperature of the barrel is 50-120℃, and the heating temperature of the printhead is 50-120℃.

[0133] In some embodiments of this application, the array-type multi-nozzle electric field driven molten jet deposition micro / nano 3D printing device includes a heating module, a temperature control module, a printing nozzle module, a printing platform, a single-plate electrode, a high-voltage power supply, a feeding module, a back pressure control module, and an XYZ three-axis precision motion platform. Compared with existing multi-nozzle electric field driven molten jet deposition micro / nano 3D printing, it adds at least a heating module and a temperature control module.

[0134] ●

[0135] The heating module is used to heat the barrel and nozzle during printing, and the temperature control module is used for precise temperature control.

[0136] ●

[0137] Adjust the heating temperature of the printing cylinder and nozzle during the printing process.

[0138] Reference Figure 2 In some embodiments of this application, the heating module includes a material cylinder heating jacket and a nozzle heating jacket, which heats and melts the printing material for printing without clogging the nozzle.

[0139] In some embodiments of this application, the printing material is subjected to surface tension, electric field force, viscous force, viscous drag force, etc. in the printing nozzle, which generate mutual forces with the charge on the surface of the substrate, thereby printing the desired pattern on the printing material substrate. The electric field force can be divided into normal electric field force, tangential electric field force and polarized electric field force.

[0140] In some embodiments of this application, the PCL conductive pattern linewidth in step 2 is 1-100 μm, and the period is 20-2000 μm.

[0141] In some embodiments of this application, the etching time in step 3 is from 1 s to 120 s.

[0142] In some embodiments of this application, step 4 involves immersing the substrate in anhydrous ethanol to remove the PCL; subsequently, the etched titanium-coated copper-clad glass substrate is cleaned with deionized water and dried.

[0143] In some embodiments of this application, 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 and titanium films of different areas and thicknesses.

[0144] In some embodiments of this application, the wet etching process described in step 3 controls the speed by adjusting the temperature and etchant concentration. The etchant temperature is selected as 20-60°C, and the etchant concentration is determined according to the type of etchant. The etchant is selected by adjusting the etching speed.

[0145] In some embodiments of this application, the conductive pattern after PCL removal in step 4 is subjected to ultrasonic cleaning and drying.

[0146] In some embodiments of this application, the deposited metal layer described in step 5 is processed using precision electroplating or electroless plating, and the deposited metal includes, but is not limited to, copper, silver, nickel, gold, etc.

[0147] In some embodiments of this application, step 6 involves ultrasonic cleaning with deionized water to remove residual plating solution and excess impurities, followed by drying with nitrogen gas.

[0148] In some embodiments of this application, the protective layer material applied in step 7 includes, but is not limited to, varnish, polyimide, acrylic resin, etc.

[0149] Reference Figure 1 and 3 In some embodiments of this application, a low-cost mass production method for large-size high-performance electrically heated glass involves coating a substrate with titanium, then with copper, and then printing a mask on the copper film; subsequently, wet etching is used to etch away the unwanted titanium and copper films, and then the mask is removed, followed by electroplating to deposit a protective layer material.

[0150] ●

[0151] In some embodiments of this application, PCL is selected as the mask material.

[0152] In some embodiments of this application, a low-cost mass production method for large-size, high-performance electrically heated glass includes the following steps:

[0153] Step 1: Preparation of titanium-coated copper-coated glass substrate

[0154] Float glass was selected as the substrate, and a uniform thickness layer was first deposited on the substrate surface using magnetron sputtering.

[0155] ●

[0156] A uniform titanium metal thin film is deposited, followed by a copper metal thin film of uniform thickness. The glass size is 400mm×400mm, the glass thickness is 10mm, the sputtered titanium film thickness is 100nm, and the copper film thickness is 900nm.

[0157] Step 2: Printing the PCL mask pattern

[0158] Using PCL with a molecular weight of 80,000 as the printing material, and combining it with high-resolution micro / nano 3D printing driven by an electric field of a multi-nozzle array, conductive mask patterns were efficiently manufactured. In this embodiment, the printed conductive pattern is a wire grid structure with an area of ​​390×390mm and a period of 0.25mm. The printing parameters are: DC voltage of 1500-2500V, printing air pressure of 1-20kPa, printing height of 0.2-0.4mm, printing speed of 40-60mm / s, barrel heating temperature of 90-100℃, and nozzle heating temperature of 100-120℃. The linewidth of the printed mask pattern is approximately 5μm. After printing, the conductive mask pattern is complete.

[0159] Step 3: Etching of titanium-coated and copper-coated glass substrates

[0160] The PCL mask pattern printed in step 2 is subjected to wet etching. A reusable acidic ferric chloride solution is selected and heated to a constant temperature of 50°C. The glass-coated titanium-coated copper plate is immersed in the etching solution for 15 seconds, followed by a rapid 10-second deionized water spray, and then dried with nitrogen. The copper foil not covered by PCL is completely etched away, leaving a copper conductive pattern with precise linewidth and shape, and an unetched titanium layer. A commercially available titanium stripping solution is used to immerse and etch the titanium layer at room temperature for 5 seconds, followed by a rapid 10-second deionized water spray, and then dried with nitrogen and placed in a vacuum drying oven at 135°C. The titanium foil not covered by PCL and copper is completely etched away, leaving a copper-titanium conductive pattern with precise linewidth and shape.

[0161] Step 4: Remove the PCL mask

[0162] To remove the PCL mask pattern from step 3, soak the mask in anhydrous ethanol for 3-5 minutes to allow it to detach. Then, wash with deionized water to remove any remaining PCL and dry the mask.

[0163] Step 5: Deposit a metal layer

[0164] Using the etched titanium-copper conductive pattern as a seed layer, an electroplating process is used to deposit a layer of nickel on the seed layer.

[0165] ●

[0166] The copper-nickel composite electrode structure is formed by connecting the titanium-copper metal wire grid structure obtained in step 4 to the cathode of the precision micro electroplating equipment, using a nickel metal plate as the anode and placing it in the electroplating solution; adding an anode activator to the electroplating solution to improve the solubility of the anode, increase conductivity, and improve the dispersion ability of the solution; adding an anti-pinhole agent 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.

[0167] ●

[0168] 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 1m / s-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.

[0169] Step 6: Post-processing

[0170] The micro-electroplated or electroless plated samples were cleaned to remove residues generated during the deposition process. The samples were then repeatedly dried to prepare a large-area transparent copper-nickel composite metal mesh transparent electric heating glass. The measured line resistance was 0.42Ω / mm and the light transmittance was over 85%.

[0171] Step 7: Apply a protective layer

[0172] A layer of UV varnish is preferably sprayed as a protective layer, and the sample preparation is complete after curing. Applying a protective layer to the sample surface effectively improves the environmental stability of the transparent metal wire mesh and its adhesion to the substrate. (Refer to...) Figure 4 and Figure 5 Temperature distribution images of transparent electrically heated glass after applying different voltages show that its temperature changes are stable under different voltages, exhibiting excellent thermal properties.

[0173] Finally, it should be noted that the above description is merely a preferred embodiment of this application and is not intended to limit this application. Although this application has been described in detail with reference to the foregoing embodiments, those skilled in the art can still modify the technical solutions described in the foregoing embodiments or make equivalent substitutions for some of them. Any modifications, equivalent substitutions, improvements, etc., made within the spirit and principles of this application should be included within the protection scope of this application. Although the specific implementation methods of this application have been described above, they are not intended to limit the protection scope of this application. Those skilled in the art should understand that various modifications or variations that can be made by those skilled in the art without creative effort based on the technical solutions of this application are still within the protection scope of this application.

Claims

1. A low-cost mass production method for large-size, high-performance electrically heated glass, characterized in that, The main steps include: Step 1: Preparation of titanium-coated copper-coated glass substrate. Glass is used as the substrate. A titanium thin film is deposited on the glass substrate, and then a copper thin film is deposited on the titanium thin film to prepare a titanium-coated copper-coated glass substrate. Step 2: Molten Polycaprolactone (PCL) Mask Pattern Printing. Using molten PCL as the mask pattern forming material, conductive patterns are printed on a titanium-coated copper-coated glass substrate using 3D printing technology. The nozzle is kept heated during printing. By adjusting the printing parameters, conductive patterns of different line types and sizes can be printed. Step 3: Etching of the titanium-coated copper-coated glass substrate. Using the molten PCL pattern printed in Step 2 as a mask, a wet etching process is used to etch the copper and titanium films, transferring and replicating the PCL conductive pattern onto the copper and titanium films. Step 4: Remove the printed PCL mask to obtain the titanium-copper composite conductive pattern; Step 5: Deposit a metal layer. Using a titanium-copper composite conductive pattern as a seed layer, continue depositing metal material on top of the titanium-copper seed layer; Step 6: After the post-processing of the deposited metal material is completed, the product from Step 5 is cleaned and dried to obtain transparent electrically heated glass; Step 7: Apply a protective layer; A protective layer material is coated onto the surface of the transparent electrically heated glass in step 6 to improve the environmental stability of the transparent metal grid and the bonding strength between the conductive pattern and the glass substrate.

2. The method for low-cost mass production of large-size, high-performance electrically heated glass according to claim 1, characterized in that, The 3D printing technology mentioned in step 2 is to use an array of multi-nozzle electric field driven melt jet deposition to print high-resolution micro-nano 3D PCL.

3. The method for low-cost mass production of large-size, high-performance electrically heated glass according to claim 1, characterized in that, Before depositing titanium and copper films, the surface of the glass substrate is first pretreated; then titanium and copper films are deposited on the pretreated substrate surface.

4. The method for low-cost mass production of large-size, high-performance electrically heated glass according to claim 1, characterized in that, In step 1, the process for depositing the titanium thin film is selected from one of physical vapor deposition, magnetron sputtering, electroless plating, and electroplating. In step 1, the process for depositing the copper thin film is selected from one of physical vapor deposition, magnetron sputtering, electroless plating, and electroplating.

5. A method for low-cost mass production of large-size, high-performance electrically heated glass according to claim 2, characterized in that, The conductive pattern printing program in step 2 can be designed with different path codes and imported into the printing equipment to achieve printing of different conductive patterns, line widths, heights, and cycles using different printing process parameters. Specifically, this includes: The size and period of the grid used to print conductive patterns are designed according to the requirements. The corresponding processing code is generated by data processing software and input into the array-type multi-nozzle electric field driven melt jet deposition micro-nano 3D printing device. Place the printing material into the barrel of the printing device; connect the nitrogen cylinder to the barrel via the pressure valve; A high-voltage DC power supply is connected to the flat electrode of the printing device via wires; The titanium-coated and copper-coated glass substrate is placed on the printing platform of the printing device; the 3D printing device is turned on, and the entire conductive pattern is printed according to the designed and optimized wire grid type and size, combined with the optimized 3D printing process parameters.

6. A method for low-cost mass production of large-size, high-performance electrically heated glass according to claim 5, characterized in that, The printhead used is a Musashi printhead with an inner diameter of 10-500μm. The distance between the printhead and the printing substrate is 10-400μm. The air pressure of the printing device is 1-20kpa. The power supply voltage of the printing device is 300-3500V. The printing speed of the printing device is 1-200mm / s. The heating temperature of the barrel is 50-120℃. The heating temperature of the printhead is 50-120℃.

7. A method for low-cost mass production of large-size, high-performance electrically heated glass according to claim 1, characterized in that, The wet etching process described in step 3 includes direct immersion and vertical spray etching; in step 4, anhydrous ethanol is used to immerse the PCL to remove it; then, deionized water is used to clean and dry the etched titanium-coated copper glass substrate.

8. A method for low-cost mass production of large-size, high-performance electrically heated glass according to claim 1, characterized in that, The deposited metal layer described in step 5 is prepared using either precision electroplating or chemical plating processes, and the deposited metal includes copper, silver, nickel, and gold.

9. A method for low-cost mass production of large-size, high-performance electrically heated glass according to claim 1, characterized in that, The thickness of the deposited titanium film is 10nm-100nm, and the thickness of the copper film is 100nm-10μm.

10. A method for low-cost mass production of large-size, high-performance electrically heated glass according to claim 1, characterized in that, The PCL conductive pattern in step 2 has a linewidth of 1-100 μm and a period of 20-2000 μm.

11. A method for low-cost mass production of large-size, high-performance electrically heated glass according to claim 1, characterized in that, In step 3, the etching time is 1 to 120 seconds; the etching agent temperature is selected as 20-60℃.

12. A low-cost mass production method for large-size, high-performance electrically heated glass, characterized in that, Includes the following steps: Step 1: Preparation of Titanium-Clad and Copper-Clad Glass Substrate. Float glass is selected as the substrate. A titanium metal thin film of uniform thickness is first deposited on the surface of the substrate by magnetron sputtering. Then, a copper metal thin film of uniform thickness is deposited. The glass size is 400mm×400mm, the glass thickness is 10mm, the thickness of the sputtered titanium film is 100nm, and the thickness of the copper film is 900nm. Step 2: PCL mask pattern printing uses molten PCL as the printing material, combined with array-type multi-nozzle electric field driven molten jet deposition high-resolution micro-nano 3D printing, to achieve efficient manufacturing of conductive mask patterns; after printing, the conductive mask pattern preparation is complete; Step 3: Etching of the titanium-coated copper-clad glass substrate. The PCL mask pattern printed in Step 2 is wet etched. A reusable acidic ferric chloride solution is selected and heated to a constant temperature of 50°C. The titanium-coated copper-clad glass substrate is immersed in the etching solution for 15 seconds. Then, deionized water is sprayed for 10 seconds and then dried with nitrogen. The copper foil not covered by PCL is completely etched away, leaving a copper conductive pattern with precise line width and shape and an unetched titanium layer. A titanium removal solution is used to immerse and etch the titanium layer at room temperature for 5 seconds. Then, deionized water is quickly sprayed for 10 seconds. After that, nitrogen gas is blown dry and the titanium layer is dried in a vacuum drying oven at 135°C. The titanium foil not covered by PCL and copper is completely etched away, leaving a copper-titanium conductive pattern with precise line width and shape. Step 4: Remove the PCL mask. Remove the PCL mask pattern from Step 3 by soaking in anhydrous ethanol for 3-5 minutes to remove the PCL mask. Then, wash with deionized water to remove the residual PCL and dry. Step 5: Depositing a Metal Layer. Using the etched titanium-copper conductive pattern as a seed layer, a layer of nickel is deposited on the seed layer using an electroplating process to form a copper-nickel composite electrode structure. The specific operation process is as follows: The titanium-copper metal grid structure obtained in Step 4 is connected to the cathode of the precision micro-electroplating equipment, and a nickel 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. Turn on the electroplating equipment. To reduce surface roughness, use 0.1 A / m. 2 -2A / m 2 The current density; The temperature of the electroplating solution is always controlled within the range of 45-55℃ by a constant temperature system; the solution is flushed using a circulating pump to agitate it, and the flushing speed is 1m / s-2m / s. An ultrasonic generator is used to quickly remove air bubbles adhering to the electrode surface during processing, which also reduces concentration polarization and improves flow field characteristics. Step 6: Post-processing. Clean the micro-electroplated or chemically plated sample to remove residues generated during the deposition process. Then, repeatedly dry the sample to prepare a large-area transparent copper-nickel composite metal mesh transparent electric heating glass. Step 7: Apply a protective layer to the electrically heated glass from Step 6. After curing, the sample preparation is complete. By coating a protective layer on the sample surface, the environmental stability of the transparent metal grid and its adhesion to the substrate are improved.

13. A method for low-cost mass production of large-size, high-performance electrically heated glass according to claim 12, characterized in that, The printed conductive pattern is a wire grid structure with an area of ​​390×390mm and a period of 0.25mm. The printing parameters are: DC voltage of 1500-2500V, printing air pressure of 1-20kpa, printing height of 0.2-0.4mm, printing speed of 40-60mm / s, heating temperature of the barrel of 90-100℃, heating temperature of the nozzle of 100-120℃, and the line width of the printed mask pattern is 5μm.

Images