Modified pai-based high-entropy ceramic coating, coating and ceramic substrate electronic circuit

Abstract

The present application relates to the technical field of electronic circuit preparation, in particular to a nano-modified PAI-based temperature-resistant high-entropy ceramic coating, a preparation method, a coating layer, a preparation method, a ceramic substrate electronic circuit and a preparation method.The present application uses high-entropy ceramic catalyst systems (CoCrFeMnZn)3O4 and (CoCrFeNiZn)3O4 with spinel structure as catalysts, and uses PAI as a binder for high-temperature-resistant ceramic coating, which can be obtained by spraying in a controllable thickness and can be processed on flat surfaces and curved surfaces.In addition, the ceramic characteristics after solidification and the effect of the binder have a good sealing effect on the surface pores of the sintered LTCC ceramic, thereby improving the air tightness and corrosion resistance of the ceramic device.

Description

Technical Field

[0001] This invention relates to the field of electronic circuit fabrication technology, specifically to a nano-modified PAI-based high-temperature resistant high-entropy ceramic coating, its preparation method, coating, preparation method, and ceramic substrate electronic circuit. Background Technology

[0002] In the future, with the development of high-performance AI chips and future applications such as cloud computing, big data, the Internet of Things, new energy vehicle charging modules, high-frequency optoelectronic communication modules, aerospace, and 5G radio frequency and base station modules, the demand for high-speed processing of large-capacity data will continue to increase. High-performance computing (HPC) clusters will be widely used as a solution for high-performance data processing. In high-performance computing cluster (HPC) devices, CPO (co-packaged optoelectronic modules), and other MCMs (Multi-Chip-Modules), in order to achieve high integration of multiple chips, it is necessary to simultaneously improve the ceramic materials and device size (material brittleness), high strength (thermal stress deformation), high-temperature hermeticity, high-temperature resistance (high-temperature dimensional stability), and multilayer substrate manufacturing technology. LTCC and HTCC are important manufacturing technologies for multilayer ceramic substrates.

[0003] The standard process for inner layer circuitry involves printing, drying, and drilling on a green ceramic tape, followed by isostatic pressing and co-firing. The sintered outer layer, consisting of fine pins and pads, is then metallized on the bare ceramic surface using TSV technology, a combination of DPC and PVD, and technologies such as AMB and DBC. Finally, photo-resistant coating, exposure, development, and etching are performed to obtain the fine circuitry. This traditional process is lengthy, costly, and can only achieve circuitry in quasi-planar structures within 2.5D.

[0004] The manufacturing technologies that can be used for the outer electronic circuitry of packaged LTCCs include: AMB, DBC, DPC, TFC, and TPC. However, these technologies have certain limitations for three-dimensional multilayer ceramic substrates. This is because their metal underlayers require copper plating through printing or lamination, and neither printing nor lamination currently possesses the capability for 3D structure manufacturing.

[0005] LTCC (Low-Temperature Ceramic Carbide) has attracted widespread interest due to its characteristics such as low sintering temperature, low power consumption at high frequencies, thermal expansion coefficient matching that of the mounted chip (Si or GaAs), low cost, multilayer interconnect, compatibility with various metal systems (especially Cu, Au, and Ag), and good hermeticity. Furthermore, the material's low dielectric constant can shorten signal delay time and increase the signal-to-noise ratio.

[0006] LTCCs (Low-Temperature Ceramic Tubes) can integrate passive components such as resistors, capacitors, and inductors, playing a crucial role in microelectronic packaging for satellite communications, mobile phones, and high-speed data transmission. Reducing power consumption in RF or DC circuits is of great significance to high-frequency and mobile communication fields. This reduction in power consumption is mainly reflected in two aspects: increasing signal amplitude (low dispersion) and reducing heat dissipation. To meet these requirements, the industry hopes to gain a comprehensive understanding of the microstructure of materials and their corresponding macroscopic properties, ultimately achieving the goal of material design and material tailoring for product series.

[0007] The manufacturing technology of packaged LTCC electronic circuits is divided into inner layer circuit manufacturing technology and outer layer circuit manufacturing technology. Many steps of the classic inner layer are based on existing thick-film processes. Using thick-film materials, according to a pre-designed structure, low-temperature sintered ceramic powder is made into a precisely thick and dense green ceramic tape, which is then used as the substrate material for the circuit. The required circuit patterns are created on the green ceramic tape using processes such as laser drilling, micro-orifice injection, and precision conductor paste printing. The inner and outer circuits use metals such as Ag, Cu, Au, and their alloys, respectively, and the circuit materials, substrate, and electronic devices are fired in one step at a temperature of approximately 900°C or below. Alternatively, a three-dimensional circuit substrate with built-in passive components can be made, and chips and active devices can be mounted on its surface to create passive and active integrated functional modules. Device embedding and co-firing processes reduce the number of production steps and passive components, which further reduces costs. To achieve high-frequency, high-density, and high-reliability packaging, LTCC materials need to meet the requirements of low coefficient of thermal expansion, low loss, high thermal conductivity, and high flexural strength.

[0008] In actual processing, besides meeting the material processing performance requirements, the formulation design also needs to incorporate a large number of additives to meet other performance indicators due to the differences in the final use requirements of the product. These additives include improving the dielectric properties of the material, enhancing its combustion performance, adding pigments to improve color requirements, and adding fibers to improve dimensional stability. This typically results in the inclusion of a large amount of inorganic fillers.

[0009] Conventional methods involve directly mixing and filling these materials without any pretreatment, which affects their performance. Therefore, existing technologies need further improvement and development. Summary of the Invention

[0010] To overcome the shortcomings of the aforementioned technologies, this invention proposes a nano-modified PAI-based high-entropy ceramic coating, its preparation method, coating, preparation method, and electronic circuit. This invention uses high-entropy ceramic catalyst systems (CoCrFeMnZn)3O4 and (CoCrFeNiZn)3O4 with spinel structures as catalysts, and PAI as a binder to create a high-temperature resistant ceramic coating. The coating can be applied by spraying to achieve controllable thickness and can be processed on both flat and curved surfaces. Furthermore, the superior ceramic properties after curing and the effect of the binder provide excellent sealing of surface pores in sintered LTCC ceramics, improving the airtightness and corrosion resistance of ceramic devices.

[0011] One objective of this invention is to provide a nano-modified PAI-based high-entropy ceramic coating, wherein the PAI-based ceramic coating comprises the following components: CaO 8-12%, SiO2 20-30%, Al2O3 10-15%, high-entropy ceramic catalyst 20-30%, nano-modified polyamide-imide resin liquid 15-25%, and dispersant 0.2-1%; further, the nano-modified polyamide-imide resin liquid is prepared by filtering with a 400-mesh stainless steel filter with a diameter of 0.028 mm and mechanically stirring for 24 hours to obtain a uniform and stable nano-modified polyamide-imide resin liquid; the solid content of the nano-modified polyamide-imide resin liquid is 38%.

[0012] The mesh diameter determines the minimum coating thickness, and the 400-mesh particle size determines the particle size of the additive. A higher mesh number requires a smaller additive particle size, which in turn leads to higher additive manufacturing costs. Therefore, a particle size range of 400 mesh is preferred.

[0013] Furthermore, the particle size of the CaO, SiO2, Al2O3, and high-entropy ceramic catalyst is between 300nm and 800nm; this facilitates dispersion and the generation of an "iceberg" effect after laser treatment. If the particles are too small, the iceberg effect is not obvious and the adhesion is poor; if the particles are too large, it will lead to coarse metal crystals.

[0014] Furthermore, the dispersant is trioleic acid glyceride;

[0015] Furthermore, the high-entropy ceramic catalyst is either (CoCrFeMnZn)3O4 or (CoCrFeNiZn)3O4.

[0016] The second objective of this invention is to provide a method for preparing the above-mentioned nano-modified PAI-based high-entropy ceramic coating, comprising the following steps: slowly adding CaO, SiO2, dispersant, and high-entropy ceramic catalyst to the nano-modified polyamide-imide resin liquid in proportion, mechanically stirring at 50-70 rpm for 10-12 hours at room temperature, and ultrasonically dispersing for 8-15 minutes to obtain the nano-modified PAI-based high-entropy ceramic coating.

[0017] The third objective of this invention is to provide a nano-modified PAI-based high-temperature-entropy ceramic coating, wherein the high-temperature-entropy ceramic coating is prepared from the above-mentioned nano-modified PAI-based high-temperature-entropy ceramic coating.

[0018] The fourth objective of this invention is to provide a method for preparing the above-mentioned nano-modified PAI-based high-entropy ceramic coating, comprising the following steps: using nano-modified PAI-based high-entropy ceramic coating as raw material, ceramic plate as carrier, uniformly spreading film using ordinary spraying equipment, then placing it in an oven, heating at 180-220℃ for 10-20 min to dry the solvent, and then raising the temperature to 250℃ and heating for 1 h; thus obtaining the nano-modified PAI-based high-entropy ceramic coating.

[0019] Furthermore, the coating thickness is 50-60 μm / coating, with 1-2 coatings applied, preferably airless spraying.

[0020] The fifth objective of this invention is to provide a nano-modified PAI-based high-temperature-entropy electronic circuit, the electronic circuit comprising a substrate layer, a nano-modified PAI-based high-temperature-entropy ceramic coating, and a metal plating layer, wherein the substrate layer is a ceramic plate, the nano-modified PAI-based high-temperature-entropy ceramic coating is the aforementioned nano-modified PAI-based high-temperature-entropy ceramic coating; the metal plating layer comprises a copper plating layer, a nickel plating layer, and a gold plating layer; the copper plating layer has a thickness of 6-10 μm, the nickel plating layer has a thickness of 4-8 μm, and the ENIG gold plating layer has a thickness of 0.05-0.15 μm.

[0021] The sixth objective of this invention is to provide a method for preparing a nano-modified PAI-based high-temperature-resistant, high-entropy electronic circuit, comprising the following steps:

[0022] Step 1: The nano-modified PAI-based high-entropy ceramic coating is directly patterned using a laser;

[0023] Step 2: Perform ultrasonic water washing on the high-entropy ceramic coating after laser treatment in Step 1;

[0024] Step 3: The high-entropy ceramic coating after ultrasonic treatment is subjected to two water washing processes.

[0025] Step 4: Perform impact copper treatment on the high-entropy ceramic coating after the water washing treatment in Step 3;

[0026] Step 5: The high-entropy ceramic coating after the impact copper treatment in Step 4 is subjected to two water washing processes.

[0027] Step 6: Perform a thick copper plating treatment on the high-entropy ceramic coating after the two water washing processes in Step 5.

[0028] Step 7: After the high-entropy ceramic coating in Step 6 has been chemically plated with thick copper, it is subjected to three pure water washes.

[0029] Step 8: Pre-immersion treatment of the high-entropy ceramic coating after the three pure water washes in Step 7 is performed using a transfer fixture.

[0030] Step 9: Perform nickel pre-activation treatment on the high-entropy ceramic coating after the pre-impregnation treatment in step 8;

[0031] Step 10: The high-entropy ceramic coating after the nickel pre-activation treatment in Step 9 is subjected to two pure water washes.

[0032] Step 11: Perform a post-immersion treatment on the high-entropy ceramic coating after the two pure water washes in Step 10;

[0033] Step 12: Perform three pure water washes on the high-entropy ceramic coating after the immersion treatment in step 11.

[0034] Step 13: Perform chemical nickel plating on the high-entropy ceramic coating after the three pure water washes in Step 12.

[0035] Step 14: Perform two pure water washes on the high-entropy ceramic coating after the electroless nickel plating treatment in Step 13.

[0036] Step 15: Perform nickel-gold protection treatment on the high-entropy ceramic coating after the two pure water washes in Step 14.

[0037] Step 16: Perform three pure water washes on the high-entropy ceramic coating after the nickel-gold protection treatment in Step 15.

[0038] Step 17: Perform a hot water wash on the high-entropy ceramic coating after the three pure water washes in Step 16.

[0039] Step 18: Dry the high-entropy ceramic coating after hot water treatment in step 17 to obtain the nano-modified PAI-based high-entropy electronic circuit.

[0040] Furthermore, the laser processing parameters in step 1 are as follows: fill spacing: <50 micrometers, scanning frequency: 40-100 kHz, scanning speed: 1000-2500 mm / s, power: 7-10 watts, laser wavelength: 1064 nm, 532 nm, 365 nm;

[0041] Furthermore, in step 2, the ultrasonic water washing treatment lasts for 5 to 15 minutes, with a dripping time of 20 to 30 seconds, and is carried out in an environment of 50 to 60°C.

[0042] Furthermore, in step 3, the water washing process lasts for 1 to 2 minutes, the dripping time is 15 to 30 seconds, and it is carried out at room temperature. The water washing process is carried out by air agitation.

[0043] Furthermore, in step 4, the treatment time is 10-30 minutes, the dripping time is 20-30 seconds, and the temperature is 54-62°C. The treatment process can be carried out by any one of the following methods: air stirring, mechanical circulation, or filtration.

[0044] Furthermore, in step 5, the water washing process lasts for 0.5 to 1 minute, with a dripping time of 20 to 30 seconds, and is carried out at room temperature. The water washing process is performed using air agitation.

[0045] Furthermore, in step 6, the treatment time is 60 to 180 minutes, the dripping time is 20 to 30 seconds, and the temperature is 50 to 56°C. The treatment process adopts any one of the following methods: air stirring, mechanical circulation, or filtration.

[0046] Furthermore, in step 7, the water washing process lasts for 30 minutes, with a dripping time of 20-30 seconds, and is carried out at room temperature. The water washing process is performed using air agitation.

[0047] Furthermore, in step 8, the treatment time is 3 to 5 minutes, the dripping time is 20 to 30 seconds, and it is carried out at room temperature. The pre-soaking process uses air agitation.

[0048] Furthermore, in step 9, the treatment time is 5 to 10 minutes, the dripping time is 20 to 30 seconds, and the process is carried out at a temperature of 32 to 38°C. The treatment process uses mechanical circulation.

[0049] Furthermore, in step 10, the water washing process lasts for 1 to 2 minutes, the dripping time is 20 to 30 seconds, and it is carried out at room temperature. The water washing process is carried out by air agitation.

[0050] Furthermore, the processing time in step 11 is 2 to 5 minutes, the dripping time is 20 to 30 seconds, and it is carried out at room temperature. The processing can be carried out by any one of the following methods: air stirring, mechanical circulation, or filtration.

[0051] Furthermore, in step 12, the processing time is 1 to 2 minutes, the dripping time is 20 to 30 seconds, and the process is carried out at room temperature, with air stirring used during the process;

[0052] Furthermore, in step 13, the processing time is 10 to 25 minutes, the dripping time is 20 to 30 seconds, and the process is carried out at 60 to 80°C. The process can be carried out by air agitation, mechanical circulation, or filtration.

[0053] Furthermore, in step 14, the processing time is 1 to 2 minutes, the dripping time is 20 to 30 seconds, and the process is carried out at room temperature, with air stirring used during the process;

[0054] Furthermore, in step 15, the processing time is 3 to 8 minutes, the dripping time is 20 to 30 seconds, and the process is carried out at 35 to 45°C. The process can be carried out by air agitation, mechanical circulation, or filtration.

[0055] Furthermore, in step 16, the processing time is 1 to 2 minutes, the dripping time is 20 to 30 seconds, and the process is carried out at room temperature, with air stirring used during the process;

[0056] Furthermore, in step 17, the processing time is 1 to 2 minutes, the dripping time is 20 to 30 seconds, and the process is carried out at 60 to 70°C, with air stirring used during the process;

[0057] Furthermore, the drying process in step 18 takes 25-30 minutes at a temperature of 60-70°C.

[0058] The chemical plating process of the present invention has the following advantages:

[0059] (1) The coating is uniform, the grains are fine and there are no inclusions. It has good corrosion resistance, low contact resistance and good conductivity.

[0060] (2) Chemical plating process equipment is simple and does not require power supply or electrodes.

[0061] (3) Chemical plating is not affected by the complexity of the substrate and does not require a shaped anode. It can be used for complex wiring substrates with independent pads on the functional surface and vias with AR>8:1, which simplifies the surface plating process and makes it the preferred solution for LTCC / HTCC (low temperature / high temperature co-fired ceramic) high-density wiring substrates and three-dimensional structure substrates.

[0062] (4) The coating obtained by ENIG process or Ni / Pd / Au process can meet the requirements of various packaging processes, such as surface mount technology, wire bonding, and flip chip bonding. Here, Ni-P electroless nickel plating with a phosphorus content of less than 7% is preferred.

[0063] The seventh objective of this invention is to provide an application of the above-mentioned nano-modified PAI-based high-entropy ceramic coating, the application of which includes, but is not limited to, circuit manufacturing on two-dimensional ceramic surfaces, and preferably, application in the manufacturing of electronic circuits on 3D ceramic surfaces. Beneficial effects

[0064] 1. The core of this invention is a high-temperature resistant ceramic coating using a high-entropy alloy as a catalyst and PAI as a binder. It can be applied by spraying to achieve controllable thickness and can be processed on both flat and curved surfaces. Furthermore, its superior ceramic properties after curing and the effect of the binder provide excellent sealing of surface pores in sintered LTCC ceramics, improving the airtightness and corrosion resistance of ceramic devices. This coating meets the requirements for surface sealing, temperature resistance, solderability, and reliability of ceramic substrates. Simultaneously, this high-entropy ceramic catalytic coating material can be induced by a 1086nm or 532nm laser to deposit metal circuits in the induced area, including but not limited to single-layer or composite metal layers such as Ni, Cu, Ag, Sn, and Au.

[0065] 2. The coating application method of this invention can meet the requirements for fabricating complex and 3D surface circuits. This breaks through the original limitation that LTCC / HTCC can only manufacture planar circuits, because with the PAI-based high-temperature sealed ceramic coating, the airtightness of the ceramic substrate or shell is naturally greatly improved, while simultaneously meeting the requirements for surface circuit fabrication.

[0066] 3. The polyamide-imide (PAI) of the present invention is a thermoplastic resin in which flexible amide groups and heat-resistant aromatic imide groups coexist in the molecule. It has the advantages of both polyimide and polyamide, and has excellent heat resistance, mechanical properties, dielectric properties, wear resistance, adhesion properties and chemical stability.

[0067] 4. This invention relates to a ceramic coating using PAI as a binder base material. The coating leverages the high-temperature resistance and adhesive properties of PAI. The main function of this coating is to provide a sealing effect on the ceramic surface after LTCC / HTCC casting and co-firing, significantly improving the hermeticity of the co-fired ceramic substrate. By optimizing the use of an MMO component with a high-entropy spinel structure, the coating surface is induced by laser light at a wavelength of 1064nm or 532nm, followed by laser trimming, enabling the fabrication of fine electronic circuits with linewidths of 50-100 micrometers with good adhesion on the bare ceramic substrate surface. Attached Figure Description

[0068] Figure 1 Metallization circuit effects under different laser parameters when the coating thickness is 50µm;

[0069] Figure 2 The effect of different laser activation parameters on metallization circuits when the coating thickness is 50 μm;

[0070] Figure 3 The image shows the effect of laser activation of the material under different laser processing angles when the coating thickness is 50 μm. Implementation

[0071] To enable those skilled in the art to better understand the technical solution of the present invention, the following detailed embodiments are provided. Figure 1-3 This invention will be described in detail below. Experimental methods in the following examples, unless otherwise specified, are generally performed under conventional conditions or as recommended by the manufacturer. Unless otherwise specified, all test materials used in the following examples were purchased from a regular biochemical reagent store. Percentages and parts are by weight unless otherwise stated. Unless otherwise defined, all technical and scientific terms used herein have the same meaning as commonly understood by one of skill in the art. Furthermore, any methods and materials similar to or equivalent to those described herein may be used in this invention. The preferred embodiments and materials described herein are for illustrative purposes only.

[0072] The endpoints and any values ​​of the ranges disclosed herein are not limited to the precise ranges or values, and these ranges or values ​​should be understood to include values ​​close to these ranges or values. For numerical ranges, the endpoint values ​​of the various ranges, the endpoint values ​​of the various ranges and individual point values, and individual point values ​​can be combined with each other to obtain one or more new numerical ranges, which should be considered as specifically disclosed herein. Example

[0073] A nano-modified PAI-based high-entropy ceramic coating is disclosed, comprising the following components: 11% CaO, 28% SiO2, 12% Al2O3, 27% high-entropy ceramic catalyst, 21.5% nano-modified polyamide-imide resin liquid, and 0.5% dispersant. Further, the nano-modified polyamide-imide resin liquid is prepared by filtering through a 400-mesh stainless steel filter with a diameter of 0.028 mm and mechanically stirring for 24 h to obtain a uniform and stable nano-modified polyamide-imide resin liquid; the solid content of the nano-modified polyamide-imide resin liquid is 38%.

[0074] The particle size of the CaO, SiO2, Al2O3, and high-entropy ceramic catalyst is 500 nm.

[0075] The dispersant is trioleic acid glyceride;

[0076] The high-entropy ceramic catalyst is (CoCrFeNiZn)3O4. Example

[0077] The above-mentioned method for preparing nano-modified PAI-based high-entropy ceramic coating includes the following steps: CaO, SiO2, dispersant, and high-entropy ceramic catalyst are slowly added to nano-modified polyamide-imide resin liquid in proportion, and mechanically stirred at 60 rpm for 11 hours at room temperature, followed by ultrasonic dispersion for 12 minutes to obtain nano-modified PAI-based high-entropy ceramic coating. Example

[0078] A nano-modified PAI-based high-entropy ceramic coating is prepared from the nano-modified PAI-based high-entropy ceramic coating in Example 2. Example

[0079] A method for preparing a nano-modified PAI-based high-entropy ceramic coating includes the following steps: using the nano-modified PAI-based high-entropy ceramic coating from Example 2 as raw material, and a ceramic plate as a carrier, a uniform film is laid using ordinary spraying equipment. Then, the coating is placed in an oven and heated at 200°C for 15 min to dry the solvent. The temperature is then increased to 250°C and heated for 1 h to obtain the nano-modified PAI-based high-entropy ceramic coating.

[0080] The coating thickness is 50 μm / coating, with one coat applied, preferably using airless spraying. Example

[0081] The only difference between Example 5 and Example 4 is that two coats of paint are used. Example

[0082] A nano-modified PAI-based high-temperature-resistant and high-entropy electronic circuit is disclosed. The electronic circuit includes a substrate layer, a nano-modified PAI-based high-temperature-resistant and high-entropy ceramic coating, and a metal plating layer. The substrate layer is a ceramic plate, and the nano-modified PAI-based high-temperature-resistant and high-entropy ceramic coating is the aforementioned nano-modified PAI-based high-temperature-resistant and high-entropy ceramic coating. The metal plating layer includes a copper plating layer, a nickel plating layer, and a gold plating layer. The copper plating layer has a thickness of 6 μm, the nickel plating layer has a thickness of 4 μm, and the gold plating layer has a thickness of 0.01 μm. Example

[0083] A method for preparing a nano-modified PAI-based high-entropy electronic circuit includes the following steps:

[0084] Step 1: The nano-modified PAI-based high-entropy ceramic coating is directly patterned using a laser;

[0085] Step 2: Perform ultrasonic water washing on the high-entropy ceramic coating after laser treatment in Step 1;

[0086] Step 3: The high-entropy ceramic coating after ultrasonic treatment is subjected to two water washing processes.

[0087] Step 4: Perform impact copper treatment on the high-entropy ceramic coating after the water washing treatment in Step 3;

[0088] Step 5: The high-entropy ceramic coating after the impact copper treatment in Step 4 is subjected to two water washing processes.

[0089] Step 6: Perform a thick copper plating treatment on the high-entropy ceramic coating after the two water washing processes in Step 5.

[0090] Step 7: After the high-entropy ceramic coating in Step 6 has been chemically plated with thick copper, it is subjected to three pure water washes.

[0091] Step 8: Pre-immersion treatment of the high-entropy ceramic coating after the three pure water washes in Step 7 is performed using a transfer fixture.

[0092] Step 9: Perform nickel pre-activation treatment on the high-entropy ceramic coating after the pre-impregnation treatment in step 8;

[0093] Step 10: The high-entropy ceramic coating after the nickel pre-activation treatment in Step 9 is subjected to two pure water washes.

[0094] Step 11: Perform a post-immersion treatment on the high-entropy ceramic coating after the two pure water washes in Step 10;

[0095] Step 12: Perform three pure water washes on the high-entropy ceramic coating after the immersion treatment in step 11.

[0096] Step 13: Perform chemical nickel plating on the high-entropy ceramic coating after the three pure water washes in Step 12.

[0097] Step 14: Perform two pure water washes on the high-entropy ceramic coating after the electroless nickel plating treatment in Step 13.

[0098] Step 15: Perform nickel-gold protection treatment on the high-entropy ceramic coating after the two pure water washes in Step 14.

[0099] Step 16: Perform three pure water washes on the high-entropy ceramic coating after the nickel-gold protection treatment in Step 15.

[0100] Step 17: Perform a hot water wash on the high-entropy ceramic coating after the three pure water washes in Step 16.

[0101] Step 18: Dry the high-entropy ceramic coating after hot water treatment in step 17 to obtain the nano-modified PAI-based high-entropy electronic circuit.

[0102] The laser processing parameters in step 1 are: fill gap: <50 micrometers, scanning frequency: 40 kHz, scanning speed: 2500 mm / s, power: 4.5 W, laser wavelength: 1064 nm;

[0103] In step 2, the ultrasonic water washing treatment lasts for 10 minutes, with a dripping time of 25 seconds, and is carried out in an environment of 55°C.

[0104] In step 3, the water washing process lasts for 1 minute, with a dripping time of 20 seconds, and is carried out at room temperature. The water washing process is performed using air agitation.

[0105] Step 4 involves a processing time of 20 minutes and a dripping time of 25 seconds, conducted at 55°C. The processing can be carried out using any one of the following methods: air agitation, mechanical circulation, or filtration.

[0106] In step 5, the water washing process lasts for 0.8 minutes, with a dripping time of 25 seconds, and is carried out at room temperature. The water washing process is performed using air agitation.

[0107] The treatment time in step 6 is 100 minutes, the drip time is 25 seconds, and it is carried out at 53°C. The treatment process uses any one of the following methods: air agitation, mechanical circulation, or filtration.

[0108] In step 7, the water washing process lasts for 30 minutes, with a dripping time of 25 seconds, and is carried out at room temperature. The water washing process is performed using air agitation.

[0109] Step 8 involves a 4-minute treatment time and a 25-second drip time, conducted at room temperature. The pre-soaking process utilizes air agitation.

[0110] Step 9 involves a treatment time of 8 minutes, with a dripping time of 25 seconds, conducted at a temperature of 35°C, and using mechanical circulation in the process.

[0111] In step 10, the water washing process lasts for 1 minute, with a dripping time of 25 seconds, and is carried out at room temperature. The water washing process is performed using air agitation.

[0112] The processing time in step 11 is 3 minutes, the dripping time is 25 seconds, and it is carried out at room temperature. The processing can be done by air agitation, mechanical circulation, or filtration.

[0113] The processing time in step 12 is 1 minute, the dripping time is 25 seconds, and it is carried out at room temperature. The process is carried out by air agitation.

[0114] The processing time in step 13 is 15 minutes, the dripping time is 25 seconds, and it is carried out at 70℃. The processing can be carried out by air agitation, mechanical circulation, or filtration.

[0115] The processing time in step 14 is 1 minute, the dripping time is 25 seconds, and it is carried out at room temperature. The process is carried out by air agitation.

[0116] The processing time in step 15 is 5 minutes, the dripping time is 25 seconds, and it is carried out at 40℃. The processing can be carried out by air agitation, mechanical circulation, or filtration.

[0117] The processing time in step 16 is 1 minute, the dripping time is 25 seconds, and it is carried out at room temperature. The process is carried out by air agitation.

[0118] In step 17, the processing time is 1 minute, the dripping time is 25 seconds, and the process is carried out at 65°C. Air agitation is used during the process.

[0119] The drying time in step 18 is 25 minutes, carried out at a temperature of 65°C.

[0120] Among them, the impact copper cylinder opening ratio (as in step 4 above)

[0121] Add the chemicals strictly in the above order and mix thoroughly to avoid concentration polarization. After the temperature reaches 54-62℃, add 1 piece of the tank plate and treat for 30 minutes. Analyze the concentration of each tank and adjust it to the appropriate level before starting work. Among them, Ms is the complexing agent (HOOC-CH2)2N-CH2-CH2-N(CH2-COOH)2; S is the stabilizer; CS is the alkalinity adjuster NaOH; A is the copper ion main salt; and H is the reducing agent formaldehyde.

[0122] a) Add 50% pure water to the prepared clean plating tank.

[0123] b) After stirring with air, add 180 ml / L of SPS 2000Ms solution.

[0124] c) Add 35 ml / L of SPS 2000A solution

[0125] d) Add 1.5 ml / L of SPS 2000S solution

[0126] e) Add 32 ml / L of SPS 2000CS solution

[0127] f) Add pure water to the prepared solution volume

[0128] g) Heat the plating bath to 54-62℃

[0129] h) Add 16 ml / L of SPS 2000H solution

[0130] i) After heating to the operating conditions, analyze the concentrations of copper ions, formaldehyde, sodium hydroxide, and complexing agent, and adjust them to be within the process range for trial production.

[0131] A fine, dense, and highly bonded bright red copper layer is obtained on the surface of the workpiece after laser activation treatment.

[0132] 1) SPS-2000 cylinder opening ratio

[0133] Copper start-up ratio

[0134] Add the chemicals strictly in the above order and mix thoroughly to avoid concentration polarization. Add agent H after the temperature reaches 50-56℃. Among them, Ms is the complexing agent (HOOC-CH2)2N-CH2-CH2-N(CH2-COOH)2; S is the stabilizer; CS is the alkalinity adjuster NaOH; A is the copper ion main salt; and H is the reducing agent formaldehyde.

[0135] 2) Solution preparation process

[0136] a) Add approximately 50% pure water to the prepared clean plating tank.

[0137] b) After stirring with air, add 150 ml / L of SPS 2000M solution.

[0138] c) Add 22 ml / L of SPS 2000A solution

[0139] d) Add 0.5 ml / L of SPS 2000S solution

[0140] e) Add 22 ml / L of SPS 2000C solution

[0141] f) Add pure water to the prepared solution volume

[0142] g) Heat the plating bath to 50-55℃

[0143] h) Add 10 ml / L of SPS 2000H solution

[0144] After heating to the operating conditions, the content of complexing agent, copper ions, formaldehyde, and sodium hydroxide was analyzed. After adjustments were made, the material was fed into the trial production.

[0145] 3) Thick copper content control

[0146] General operating procedure: Ultrasonic degreasing -> Dust removal -> Pre-copper (water washing) -> Thick copper -> Water washing (2 steps) -> Acid immersion -> Palladium activation -> Water washing (3 steps) -> Nickel plating -> Water washing (3 steps) -> Passivation -> Water washing (3 steps) / [Chemical gold plating -> Gold recovery -> Water washing (3 steps) -> Immersion in protective agent] -> Hot water washing (50℃) -> Water washing (25-40℃) -> Spin dry -> Drying (80℃).

[0147] In the process of electroless plating of high-entropy ceramic alloy coatings after laser-induced processing, electroless plating solutions are used, with a full plating time of less than 30 minutes and an initial plating time of 5-10 minutes. The deposition rate in the pre-plating stage is 3-5 micrometers / hour. The electroless plating results in a uniform metallization layer with fine crystals and good adhesion, enabling the creation of fine lines of 100 micrometers and below. Example

[0148] The only difference between Example 8 and Example 7 is the scanning frequency: 50 KHz and the power: 5W. Example

[0149] The only difference between Example 9 and Example 7 is the scanning frequency: 60 KHz and the power: 5.5W.

[0150] Micro-region structure characterization and performance testing

[0151] The thickness of coatings and plating layers was measured using a CAM 900 or FISCHER film thickness meter. Before testing different materials, the film thickness meter needed to be calibrated using a reference sheet. The dispersion state of nanoparticles and their microstructure in high-entropy ceramic materials were observed using a transmission electron microscope (JEM-2100). Characteristic absorption peaks of the composite material were analyzed using a Bruker 55 FT-IR spectrometer (Germany). The dielectric constant, dielectric loss, and conductivity of the composite material were measured at room temperature using a Novel Control broadband dielectric spectrometer (Germany). The thermal decomposition temperature of pure PAI and composite materials with different doping amounts was measured using a METTLER TOLEDO SDTA851 thermogravimetric analyzer.

[0152] The coating of Example 5 of the present invention meets the following test requirements:

[0153] The Cu / Ni / Au coating meets the following test requirements:

[0154] Figure 1 The image shows the metallization circuit effect under different laser parameters when the coating thickness is 50µm; for example... Figure 1 As shown, Figure 1 a, b, and c are metallization circuit diagrams showing the effect of a 50µm coating thickness under the following laser parameters: 40kHz, 4.5W, 2500mm / s; 50kHz, 5.0W, 2500mm / s; and 60kHz, 5.5W, 2500mm / s. Figure 1 As can be seen, the metallization circuit with the laser parameters of 60KHz, 5.5W, and 2500mm / s has the best effect, and the circuit has obvious metallic luster.

[0155] Figure 2 The effect of different laser activation parameters on the metallization circuit when the coating thickness is 50 μm; for example Figure 2 As shown, when the coating thickness is 50 μm, where Figure 2 a. Single laser head scanning is used, with laser parameters: 440KHz, 2000mm / s, 4W;

[0156] Figure 2 b uses dual laser head scanning, with laser parameters: 45KHz, 2500mm / s, 4W;

[0157] Figure 2 c uses dual laser heads for cross scanning, with laser parameters of 45KHz, 2500mm / s, and 5W.

[0158] Figure 2d employs dual laser heads for cross-scanning, with laser parameters of 45KHz, 2500mm / s, and 6W.

[0159] from Figure 2 It can be seen from this that Figure 2 c and Figure 2 The adhesion of coating d is significantly better than Figure 2 a and b;

[0160] Figure 3 Images showing the effect of laser activation on the material at different laser processing angles when the coating thickness is 50µm; for example... Figure 3 As shown in Figures 3a-c, when the coating thickness is 50 μm and a 1064 nm laser is used, the laser activation effect is observed at angles of 0° (perpendicular), 45°, and 60° between the coating and the laser. From Figures 3a-c, it can be seen that under the same laser parameters, different laser processing angles result in different degrees of material activation. The laser activation effect is best in the area perpendicular to the surface of the processed material (e.g., [image of laser activation effect]). Figure 3 a) The degree of activation changes with the angle.

[0161] The metallization and sealing functions of this invention differ from those of traditional LTCC / HTCC Mo-Mn thick-film metallization, low-temperature glass gelation, and chemical gelation methods. LTCC / HTCC co-fired ceramics have a natural porosity of 10-20%, but these pores are rarely directly conductive; instead, micro-blind pore structures account for over 90%. In harsh environments with high temperatures, high humidity, and high salinity, these microporous structures pose a risk of substrate corrosion and device damage. Under these conditions, the ceramic housings and circuitry used must meet more stringent requirements. This high-temperature, high-entropy ceramic coating is printed onto the ceramic surface and, upon curing, seals the micropores on the ceramic surface.

[0162] Finally, it should be noted that the above description is only a preferred embodiment of the present invention. Those skilled in the art, under the guidance of the present invention, can make various similar representations without departing from the spirit and claims of the present invention, and such modifications all fall within the protection scope of the present invention.

Claims

1. A nano-modified PAI-based high-entropy ceramic coating, characterized in that, The PAI-based ceramic coating is composed of the following components: CaO 8-12%, SiO2 20-30%, Al2O3 10-15%, high-entropy ceramic catalyst 20-30%, nano-modified polyamide-imide resin liquid 15-25%, and dispersant 0.2-1%. The nano-modified polyamide-imide resin solution is prepared by filtering with a 400-mesh stainless steel filter screen with a diameter of 0.028 mm and mechanically stirring for 24 h to obtain a uniform and stable nano-modified polyamide-imide resin solution; the solid content of the nano-modified polyamide-imide resin solution is 38%; the particle size of the CaO, SiO2, Al2O3, and high-entropy ceramic catalyst is 300nm-800nm; The dispersant is trioleic acid glyceride; The high-entropy ceramic catalyst is either (CoCrFeMnZn)3O4 or (CoCrFeNiZn)3O4.

2. The preparation method of the nano-modified PAI-based high-entropy ceramic coating as described in claim 1, characterized in that, The process includes the following steps: CaO, SiO2, dispersant, and high-entropy ceramic catalyst are slowly added to the nano-modified polyamide-imide resin solution in proportion. At room temperature, the mixture is mechanically stirred at 50-70 rpm for 10-12 hours and ultrasonically dispersed for 8-15 minutes to obtain a nano-modified PAI-based high-entropy ceramic coating.

3. A nano-modified PAI-based high-entropy ceramic coating, characterized in that, The high-entropy temperature resistant ceramic coating is prepared from the nano-modified PAI-based high-entropy temperature resistant ceramic coating of claim 1 or the nano-modified PAI-based high-entropy temperature resistant ceramic coating prepared by the method of claim 2.

4. The method for preparing a nano-modified PAI-based high-entropy ceramic coating as described in claim 3, characterized in that, Includes the following steps: Using nano-modified PAI-based high-entropy ceramic coating as raw material and ceramic plate as carrier, a uniform film is laid using ordinary spraying equipment. Then, the film is placed in an oven and heated at 180-220℃ for 10-20 min to dry the solvent. The temperature is then increased to 250℃ and heated for 1 h to obtain the nano-modified PAI-based high-entropy ceramic coating.

5. The method for preparing a nano-modified PAI-based high-entropy ceramic coating as described in claim 4, characterized in that, Coating thickness: 50-60um / coat, 1-2 coats.

6. An electronic circuit based on a nano-modified PAI-based high-entropy ceramic substrate, characterized in that: The electronic circuit includes a substrate layer, a nano-modified PAI-based high-temperature-resistant ceramic coating, and a metal plating layer. The substrate layer is a ceramic substrate, and the nano-modified PAI-based high-temperature-resistant ceramic coating is the nano-modified PAI-based high-temperature-resistant ceramic coating as described in claim 3. The metal plating layer includes a copper plating layer, a nickel plating layer, and a gold plating layer. The copper plating layer has a thickness of 6-10 μm, the nickel plating layer has a thickness of 4-8 μm, and the gold plating layer has a thickness of 0.05-0.15 μm.

7. The method for preparing electronic circuits on nano-modified PAI-based high-entropy ceramic substrates according to claim 6, characterized in that: Includes the following steps: Step 1: The nano-modified PAI-based high-entropy ceramic coating is directly patterned using a laser; Step 2: Perform ultrasonic water washing on the high-entropy ceramic coating after laser treatment in Step 1; Step 3: The high-entropy ceramic coating after ultrasonic treatment is subjected to two water washing processes. Step 4: Perform impact copper treatment on the high-entropy ceramic coating after the water washing treatment in Step 3; Step 5: The high-entropy ceramic coating after the impact copper treatment in Step 4 is subjected to two water washing processes. Step 6: Perform a thick copper plating treatment on the high-entropy ceramic coating after the two water washing processes in Step 5. Step 7: After the high-entropy ceramic coating in Step 6 has been chemically plated with thick copper, it is subjected to three pure water washes. Step 8: Pre-immersion treatment of the high-entropy ceramic coating after the three pure water washes in Step 7 is performed using a transfer fixture. Step 9: Perform nickel pre-activation treatment on the high-entropy ceramic coating after the pre-impregnation treatment in step 8; Step 10: The high-entropy ceramic coating after the nickel pre-activation treatment in Step 9 is subjected to two pure water washes. Step 11: Perform a post-immersion treatment on the high-entropy ceramic coating after the two pure water washes in Step 10; Step 12: Perform three pure water washes on the high-entropy ceramic coating after the immersion treatment in step 11. Step 13: Perform chemical nickel plating on the high-entropy ceramic coating after the three pure water washes in Step 12. Step 14: Perform two pure water washes on the high-entropy ceramic coating after the electroless nickel plating treatment in Step 13. Step 15: Perform nickel-gold protection treatment on the high-entropy ceramic coating after the two pure water washes in Step 14. Step 16: Perform three pure water washes on the high-entropy ceramic coating after the nickel-gold protection treatment in Step 15. Step 17: Perform a hot water wash on the high-entropy ceramic coating after the three pure water washes in Step 16. Step 18: Dry the high-entropy ceramic coating after hot water treatment in step 17 to obtain the nano-modified PAI-based high-entropy electronic circuit.

8. The method for preparing electronic circuits on nano-modified PAI-based high-entropy ceramic substrates according to claim 7, characterized in that: The laser processing parameters in step 1 are: fill gap: <50 micrometers, scanning frequency: 40-100 kHz, scanning speed: 1000-2500 mm / s, power: 7-10 watts, laser wavelength: 1064nm, 532nm, 365nm; In step 2, the ultrasonic water washing treatment lasts for 5 to 15 minutes, with a dripping time of 20 to 30 seconds, and is carried out in an environment of 50 to 60°C. In step 3, the water washing process lasts for 1 to 2 minutes, and the dripping time is 15 to 30 seconds. It is carried out at room temperature, and air agitation is used during the water washing process. In step 4, the treatment time is 10-30 minutes, the dripping time is 20-30 seconds, and the temperature is 54-62℃. The treatment process can be carried out by any one of the following methods: air agitation, mechanical circulation, or filtration. In step 5, the water washing process lasts for 0.5 to 1 minute, with a dripping time of 20 to 30 seconds, and is carried out at room temperature. The water washing process is performed using air agitation. The treatment time in step 6 is 60 to 180 minutes, the drip time is 20 to 30 seconds, and it is carried out at 50 to 56°C. The treatment process can be carried out by air agitation, mechanical circulation, or filtration. In step 7, the water washing process lasts for 30 minutes, with a dripping time of 20-30 seconds, and is carried out at room temperature. The water washing process is performed using air agitation. The treatment in step 8 lasts for 3 to 5 minutes, with a dripping time of 20 to 30 seconds, and is carried out at room temperature. Air agitation is used during the pre-soaking process. In step 9, the treatment time is 5 to 10 minutes, the dripping time is 20 to 30 seconds, and the process is carried out at a temperature of 32 to 38°C. The treatment process uses mechanical circulation. In step 10, the water washing process lasts for 1 to 2 minutes, with a dripping time of 20 to 30 seconds. The process is carried out at room temperature, and air agitation is used during the water washing process. The processing time in step 11 is 2 to 5 minutes, the dripping time is 20 to 30 seconds, and it is carried out at room temperature. The processing can be carried out by air agitation, mechanical circulation, or filtration. The processing time in step 12 is 1 to 2 minutes, the dripping time is 20 to 30 seconds, and it is carried out at room temperature. The process is carried out by air agitation. The treatment time in step 13 is 10 to 25 minutes, the dripping time is 20 to 30 seconds, and it is carried out in an environment of 60 to 80°C. The treatment process adopts any one of the following methods: air agitation, mechanical circulation, or filtration. The processing time in step 14 is 1 to 2 minutes, the dripping time is 20 to 30 seconds, and it is carried out at room temperature. The process is carried out by air agitation. The treatment time in step 15 is 3 to 8 minutes, the dripping time is 20 to 30 seconds, and it is carried out at 35 to 45°C. The treatment process can be carried out by air agitation, mechanical circulation, or filtration. The processing time in step 16 is 1 to 2 minutes, the dripping time is 20 to 30 seconds, and it is carried out at room temperature. The process is carried out by air agitation. In step 17, the treatment time is 1 to 2 minutes, the dripping time is 20 to 30 seconds, and the process is carried out at 60 to 70°C. Air agitation is used during the treatment process. The drying process in step 18 takes 25-30 minutes at a temperature of 60-70°C.

9. The application of the nano-modified PAI-based high-entropy ceramic coating as described in claim 1, characterized in that: The applications include, but are not limited to, the fabrication of circuits on two-dimensional ceramic surfaces.

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