High performance ceramic substrate, method of making and metallization via dry film exposure and etch protection

Abstract

The application discloses a high-performance ceramic substrate and a preparation method and a metalized hole groove dry film exposure corrosion protection method thereof, and relates to the technical field of electronic ceramic packaging materials. The high-performance ceramic substrate provided by the application realizes the synergistic improvement of density and mechanical properties by in-situ construction of a multi-element synergistic densification system of modified inorganic fillers and hyperbranched polyester dispersants during casting and sintering processes, effectively deals with the process pain points of abnormal grain growth and residual pores of the ceramic substrate in the sintering process, solves the technical problems of abnormal grain growth caused by uneven distribution of traditional sintering aid doping method and insufficient densification caused by weak interface bonding of the nano filler filling method, and meanwhile, the dry film exposure development process forms complete protection on the metalized hole groove in the wet spray etching process, and solves the technical pain points of high hole breakage rate caused by uneven coverage and insufficient mechanical strength of the traditional photoresist protection method.

Description

Technical Field

[0001] This application relates to the field of electronic ceramic packaging materials technology, and in particular to high-performance ceramic substrates and their preparation methods and metallized trench dry film exposure corrosion protection methods. Background Technology

[0002] High-performance ceramic substrates, as key foundational materials for power semiconductor devices, LED packaging, microwave RF devices, and high-density integrated modules, possess excellent thermal conductivity, insulation properties, mechanical strength, and chemical stability. They are widely used in high-end electronic packaging fields such as new energy vehicles, 5G communication base stations, aerospace electronics, and smart grids, serving as core functional materials to ensure efficient heat dissipation and long-term reliable operation of electronic devices. With the rapid development of power devices towards higher power density, higher integration, and miniaturization, and the large-scale application of third-generation semiconductor materials (SiC, GaN), the industry has placed more stringent requirements on the density, thermal conductivity, surface quality, and mechanical properties of ceramic substrates. High-quality, high-performance ceramic substrates must effectively balance high density and high bending strength while meeting high power heat dissipation requirements, and simultaneously ensure microstructure uniformity and batch consistency. These performance indicators directly determine their applicability in various application scenarios, such as power module packaging, microwave and millimeter-wave circuits, and high-temperature electronic devices. According to data from the electronic ceramics industry, the annual demand for ceramic substrates in the power semiconductor packaging field continues to rise. High-power density modules and high-frequency devices account for over 70% of the requirements for substrate density, grain uniformity, and mechanical properties, necessitating the simultaneous fulfillment of multiple technical demands such as high thermal conductivity, high insulation, high reliability, and processing consistency. However, existing ceramic substrate manufacturing technologies struggle to achieve a synergistic improvement in density and mechanical properties, leading to problems such as abnormal grain growth, high porosity, and insufficient strength in practical applications. This severely restricts their long-term application in high-end electronic packaging.

[0003] To address the technical challenge of synergistically improving the density and mechanical properties of ceramic substrates, the industry has successively developed technical approaches such as sintering aid doping and nanofiller filling. Among them, the sintering aid doping method adds sintering aids such as MgO, Y2O3, CaO, and SiO2 to the alumina matrix and promotes densification through liquid-phase sintering mechanism. It is cost-controllable and the process is mature. However, traditional sintering aids are introduced by direct physical mixing, which has problems such as uneven distribution and local enrichment. This leads to defects such as abnormal grain growth, high porosity, and insufficient strength in the ceramic substrate after sintering. The nanofiller filling method introduces nanofillers such as nano-SiO2 and nano-Al2O3 into the ceramic formula to fill the intergranular micropores and improve density. However, due to their large specific surface area and high surface energy, nanoparticles are prone to irreversible agglomeration in the slurry. This not only fails to exert the nano effect but also forms a local defect source. In addition, the interfacial bonding force between the nanoparticles modified by traditional small molecule silane coupling agents and the ceramic matrix is ​​limited. After the organic part of the coupling agent decomposes during sintering, it leaves interfacial pores, which limits the full realization of the densification effect. In addition, traditional linear dispersants have limited steric hindrance effect and their dispersion effect in high solid content slurry systems is not ideal, making it difficult to achieve uniform distribution of each component in the slurry, which further affects the uniformity of the microstructure of the ceramic substrate after sintering.

[0004] To address the aforementioned technical shortcomings, there is an urgent need to improve existing technologies. Summary of the Invention

[0005] In view of this, this application provides a high-performance ceramic substrate and its preparation method and a metallized via dry film exposure etching protection method. The high-performance ceramic substrate has multiple advantages such as high density, excellent mechanical properties and uniform microstructure. At the same time, it avoids the problems of uneven distribution of sintering aid leading to abnormal grain growth, agglomeration of nanofillers leading to interface defects, and failure of photoresist protection leading to via breakage in traditional technologies. It can meet the application requirements of high density, high bending strength and via conductivity integrity in the field of electronic packaging.

[0006] In the first aspect, this application provides a high-performance ceramic substrate, the technical solution of which is as follows: A high-performance ceramic substrate, comprising the following components: The composition includes 80-95 parts alumina, 0.5-3 parts magnesium oxide, 0.5-2 parts yttrium oxide, 0.5-3 parts calcium oxide, 0.5-3 parts silicon dioxide, 1-5 parts zirconium oxide, 3-12 parts modified inorganic filler, 8-18 parts polyvinyl butyral, 8-15 parts dibutyl phthalate, 0.5-3 parts hyperbranched polyester dispersant, 0.1-0.5 parts defoamer, and 40-80 parts organic solvent.

[0007] Optionally, the preparation method of the modified inorganic filler includes the following steps: Silicon carbide and anhydrous ethanol were mixed and subjected to ultrasonic treatment to obtain a silicon carbide suspension. The silicon carbide suspension and 3-isocyanate propyltriethoxysilane were mixed and stirred at 60-80°C to obtain pre-modified silicon carbide. The modified silicon carbide, glycidyl methacrylate, and azobisisobutyronitrile were mixed and then subjected to in-situ polymerization at 70-90°C to obtain the modified inorganic filler.

[0008] Optionally, the mass-to-volume ratio of silicon carbide to anhydrous ethanol is 1 g: (8~15) mL, and the average particle size of the silicon carbide is 30~100 nm.

[0009] Optionally, the ultrasonic treatment has a power of 200-500W, a duration of 30-60min, and a frequency of 20-40kHz.

[0010] Optionally, the mass-to-volume ratio of the silicon carbide suspension to 3-isocyanate propyltriethoxysilane is 1 g: (0.1~0.2) mL.

[0011] Optionally, the stirring reaction is carried out at a speed of 400-600 r / min for a duration of 4-8 h.

[0012] Optionally, the mass-to-volume ratio of the initially modified silicon carbide, glycidyl methacrylate, and azobisisobutyronitrile is 1 g: (0.25~0.5) mL: (0.003~0.008) g.

[0013] Optionally, the in-situ polymerization reaction is carried out under stirring conditions, wherein the stirring speed is 300~500 r / min and the time is 3~6 h.

[0014] Optionally, the preparation method of the hyperbranched polyester dispersant includes the following steps: Trimethylolpropane, 2,2-dimethylolpropionic acid and p-toluenesulfonic acid were mixed and subjected to polycondensation reaction at 140~160℃ to obtain hydroxyl-terminated hyperbranched polyester. The hyperbranched polyester with terminal hydroxyl groups and castor oil fatty acids are mixed and then subjected to esterification reaction at 180~200℃ to obtain the hyperbranched polyester dispersant.

[0015] Optionally, the mass-to-volume ratio of trimethylolpropane, 2,2-dimethylolpropionic acid and p-toluenesulfonic acid is 1:5~7:0.03~0.08.

[0016] Optionally, the polycondensation reaction is carried out under stirring conditions, wherein the stirring speed is 100~300 r / min and the time is 6~10 h.

[0017] Optionally, the mass-to-volume ratio of the terminal hydroxyl hyperbranched polyester to castor oil fatty acid is 1 g: (0.15~0.3) mL.

[0018] Optionally, the esterification reaction is carried out under stirring conditions, wherein the stirring speed is 150~350 r / min and the time is 3~5 h.

[0019] Optionally, the defoamer is selected from one or both of n-butanol or silicone defoamers.

[0020] Optionally, the organic solvent is selected from one or both of toluene and anhydrous ethanol.

[0021] Secondly, this application provides a method for preparing a high-performance ceramic substrate, comprising the following steps: Alumina, magnesium oxide, yttrium oxide, calcium oxide, silicon dioxide, zirconium oxide, organic solvent and hyperbranched polyester dispersant are mixed and then subjected to a first ball milling process to obtain a primary slurry; The primary slurry, polyvinyl butyral, dibutyl phthalate and defoamer are mixed and then subjected to a second ball milling process to obtain the secondary slurry. The secondary slurry and modified inorganic filler are mixed and stirred to obtain a casting slurry. The casting slurry is subjected to vacuum degassing treatment, and then cast molding treatment is performed to obtain a green tape; The green strip is debonded and then sintered to obtain a high-performance ceramic substrate.

[0022] Optionally, the first ball milling process uses alumina balls as the milling medium, the diameter of the milling medium is 5~15mm, the material-to-ball mass ratio is 1:2~4, and the first ball milling process is carried out under stirring conditions, the stirring speed is 200~400r / min, and the time is 12~48h.

[0023] Optionally, the ball milling media used in the second ball milling process are alumina balls with a diameter of 5-15 mm and a material-to-ball mass ratio of 1:2-4. The second ball milling process is carried out under stirring conditions, with a stirring speed of 200-400 r / min and a time of 12-36 h.

[0024] Optionally, the stirring speed is 200~500 r / min and the time is 1~4 h.

[0025] Optionally, the vacuum degree of the vacuum degassing treatment is -0.08 to -0.095 MPa, and the degassing time is 20 to 60 min.

[0026] Optionally, the casting process is carried out on a casting machine with a scraper gap of 0.3~1.5mm, a casting speed of 0.5~2.0m / min, a drying temperature of 60~100℃, and a green strip thickness of 0.2~1.0mm.

[0027] Optionally, the heating rate of the glue removal process is 0.5~2.0℃ / min, the glue removal temperature is 550~650℃, and the holding time is 2~6h.

[0028] Optionally, the heating rate of the sintering process is 3~10℃ / min, the temperature is 1550~1680℃, the time is 2~6h, and the sintering atmosphere is air or oxygen.

[0029] Thirdly, this application provides a method for dry film exposure etching protection treatment of metallized vias on high-performance ceramic substrates as described in the foregoing scheme, comprising the following steps: Hole and groove processing is performed on the high-performance ceramic substrate. After cleaning, a metal film layer is sputtered to obtain a coated ceramic substrate. The coated ceramic substrate is placed on a bakelite board and dry film is applied. After the film is applied, it is removed and rehydrated. The ceramic substrate with holes and grooves protected by a dry film is obtained by performing alignment exposure according to the exposure dosage and exposure drawing, followed by secondary rehydration after exposure, and spray development according to the developer solution. The ceramic substrate with the hole grooves protected by the dry film is subjected to patterned outer film etching treatment, and then the film is removed and cleaned to obtain a high-performance ceramic substrate with complete metallized hole grooves.

[0030] Optionally, the hole and groove are processed by laser drilling or mechanical drilling, with a hole diameter range of 50~300μm.

[0031] Optionally, the sputtered metal film is a magnetron sputtered TiW / Au film, wherein the thickness of the TiW layer is 0.08~0.15μm and the thickness of the Au layer is 0.2~0.5μm.

[0032] Optionally, the film application speed of the dry film application process is 10~20 mm / s, the upper roller temperature is 85~95℃, the lower roller temperature is 85~95℃, and the application pressure is 8~15 N / cm. 2 The thickness of the dry film used is 15~30μm.

[0033] Optionally, the rehydration time is 10-30 minutes.

[0034] Optionally, the secondary rehydration time is 10-30 minutes.

[0035] Optionally, the exposure dose for the alignment exposure treatment is 3000~5000mJ.

[0036] Optionally, the developing solution for the spray developing process is an aqueous solution of sodium carbonate, wherein the mass concentration of sodium carbonate in the developing solution is 14-20%, the developing temperature is 40-50℃, and the developing time is 2-5 min.

[0037] Optionally, the dry film is a fully water-soluble photosensitive dry film, comprising a protective film, a substrate film, and a photosensitive resist layer, wherein the photosensitive resist layer contains acrylate photopolymerizable monomers.

[0038] The high-performance ceramic substrate provided in this application achieves a synergistic improvement in density and mechanical properties, effectively addressing the process pain points of abnormal grain growth and residual pores encountered during the sintering of ceramic substrates. It also solves the technical problems of uneven distribution of traditional sintering aid doping methods and weak interfacial bonding in nanofiller filling methods. This application constructs a multi-element synergistic densification system in situ during tape casting and sintering by using modified inorganic fillers and hyperbranched polyester dispersants. The modified inorganic filler, with a core-shell structure of nano-silicon carbide as the core and epoxy-containing organic polymer as the shell, provides dual functions of interfacial chemical bonding and grain boundary pinning. The nano-silicon carbide core pins grain boundaries and inhibits abnormal grain growth during sintering, while the surface epoxy groups open rings and chemically bond with the hydroxyl groups on the surface of the ceramic powder in the early stage of sintering, forming an organic-inorganic covalent interface layer and promoting sintering densification. The hyperbranched polyester dispersant provides excellent steric stabilization through its three-dimensional spherical hyperbranched structure and multi-long-chain fatty acid ester end groups, ensuring uniform dispersion of each component in the slurry. Compared with existing technologies, this high-performance ceramic substrate has the characteristics of high volume density, uniform grain size, and excellent bending strength. Moreover, the preparation process is simple and controllable, which can meet the long-term application requirements of electronic packaging and has the potential for industrial application. Attached Figure Description

[0039] Figure 1 This is a schematic diagram of the alignment morphology of the circuit pattern and via array after exposure of the high-performance ceramic substrate in Embodiment 1 of the present invention.

[0040] Figure 2 This is a schematic diagram of the morphology of the dry film development and protection effect of the through-hole in the high-performance ceramic substrate array in Embodiment 1 of the present invention; Figure 3 This is a schematic diagram of the morphology of the dry film covering and bonding at the transition of the irregular hole groove of the high-performance ceramic substrate in Embodiment 1 of the present invention. Figure 4 This is a schematic diagram of the finished product microstructure of a single metallized through-hole in a high-performance ceramic substrate according to Embodiment 1 of the present invention. Figure 5 This is a schematic diagram of the finished appearance of the entire high-performance ceramic substrate after the metallization of the hole grooves has been completed in Embodiment 1 of the present invention. Detailed Implementation

[0041] The technical solutions in the embodiments of this application will be clearly and completely described below with reference to the embodiments of this application. 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 skilled in the art without creative effort are within the scope of protection of this application. In addition, it should be understood that the specific implementation methods described herein are only for illustration and explanation of this application and are not intended to limit this application.

[0042] In the description of this application, the term "comprising" means "including but not limited to". The terms first, second, third, etc. are used merely as illustrative purposes and do not impose numerical requirements or establish an order.

[0043] In this application, "and / or" describes the relationship between related objects, indicating that three relationships can exist. For example, A and / or B can represent: A existing alone, A and B existing simultaneously, or B existing alone. A and B can be singular or plural.

[0044] In this application, "at least one" means one or more, and "more than one" means two or more. "One or more", "at least one of the following", or similar expressions refer to any combination of these items, including any combination of single or multiple items. For example, "at least one of a, b, or c", or "at least one of a, b, and c", can both mean: a, b, c, ab (i.e., a and b), ac, bc, or abc, where a, b, and c can be single or multiple.

[0045] Various embodiments of this application may exist in the form of a range; it should be understood that the description in the form of a range is merely for convenience and brevity and should not be construed as a hard limitation on the scope of this application; therefore, it should be considered that the range description has specifically disclosed all possible sub-ranges and single numerical values ​​within that range. For example, it should be considered that the range description from 1 to 6 has specifically disclosed sub-ranges such as from 1 to 3, from 1 to 4, from 1 to 5, from 2 to 4, from 2 to 6, from 3 to 6, etc., and single numbers within the range, such as 1, 2, 3, 4, 5, and 6, regardless of the range. Furthermore, whenever a numerical range is referred to herein, it means including any referenced number (fraction or integer) within the referred range.

[0046] The present application will be specifically described below through specific embodiments. The following embodiments are only some embodiments of the present application and are not intended to limit the present application.

[0047] In the first aspect, this application provides a high-performance ceramic substrate, the technical solution of which is as follows: A high-performance ceramic substrate, comprising the following components: The composition includes 80-95 parts alumina, 0.5-3 parts magnesium oxide, 0.5-2 parts yttrium oxide, 0.5-3 parts calcium oxide, 0.5-3 parts silicon dioxide, 1-5 parts zirconium oxide, 3-12 parts modified inorganic filler, 8-18 parts polyvinyl butyral, 8-15 parts dibutyl phthalate, 0.5-3 parts hyperbranched polyester dispersant, 0.1-0.5 parts defoamer, and 40-80 parts organic solvent.

[0048] In some embodiments, the alumina has a purity ≥99.6% and an average particle size of 1.0~2.5μm. Alumina, as the main crystalline phase of the ceramic substrate, forms a corundum structure after sintering, providing the substrate with mechanical strength, thermal conductivity, and insulation properties. If the alumina content is less than 80 parts, the proportion of the main crystalline phase is insufficient, resulting in a higher proportion of glass phase in the substrate after sintering, leading to a decrease in mechanical strength and thermal conductivity, and a reduction in flexural strength exceeding 20%. If the content is greater than 95 parts, the total amount of sintering aids is correspondingly reduced, resulting in insufficient driving force for liquid-phase sintering, a decrease in densification, an increase in porosity to over 5%, and the formation of interconnected residual pores within the substrate, reducing insulation reliability.

[0049] In some embodiments, the purity of the magnesium oxide is ≥99.5%. Magnesium oxide acts as a grain growth inhibitor, segregating at the alumina grain boundaries during sintering. Through the solute dragging effect, it reduces the grain boundary migration rate, inhibits abnormal grain growth in alumina, and promotes grain homogenization. Simultaneously, magnesium oxide undergoes a solid-state reaction with alumina at high temperatures, forming a magnesium-aluminum spinel second phase at the grain boundaries, further pinning the grain boundaries. If the amount of magnesium oxide is less than 0.5 parts, the grain boundary solute concentration is insufficient, the dragging effect is weak, and the probability of abnormal grain growth increases significantly, resulting in an average grain size exceeding 5 μm and uneven distribution after sintering. If it is more than 3 parts, excessive magnesium oxide forms an excessively thick spinel layer at the grain boundaries, increasing the grain boundary glass phase. Although the grain size is small, the strength of the grain boundary phase is lower than the strength of the grain bulk, leading to a decrease in the bending strength of the substrate.

[0050] In some embodiments, the purity of the yttrium oxide is ≥99.9%. As a sintering aid, yttrium oxide undergoes a solid-state reaction with alumina at high temperatures, forming a yttrium aluminum garnet (YAG) phase at the grain boundaries. This YAG phase forms a localized liquid phase at the sintering temperature, promoting mass transport and densification through a dissolution-precipitation mechanism. If the amount of yttrium oxide is less than 0.5 parts, the amount of generated YAG liquid phase is insufficient, resulting in inadequate dissolution-precipitation mass transfer, slow densification rate, and a substrate density below 94% after sintering. If the amount is greater than 2 parts, excess YAG liquid phase accumulates at the grain boundaries, forming a coarse grain boundary glass phase upon cooling. This glass phase may experience creep and subcritical crack propagation during subsequent service, reducing the long-term reliability of the substrate.

[0051] In some embodiments, the purity of the calcium oxide is ≥98.0%. Calcium oxide, as a eutectic liquid phase sintering aid, forms a eutectic system with alumina and silica, generating a liquid phase at relatively low temperatures, promoting particle rearrangement and densification. If the amount of calcium oxide is less than 0.5 parts, the amount of eutectic liquid phase is insufficient, the driving force for particle rearrangement is weak, the sintering temperature window is narrow, and production efficiency is reduced; if it is more than 3 parts, the amount of eutectic liquid phase is excessive, and during sintering, the liquid phase overflows to the substrate surface, causing glass spots and compositional segregation on the substrate surface. Simultaneously, excessive Ca... 2+ Enrichment in the grain boundary glass phase reduces the chemical stability of the grain boundary phase, making it prone to hydrolysis in humid and hot environments, leading to blistering or pulverization on the substrate surface.

[0052] In some embodiments, the purity of the silicon dioxide is ≥99.0%. As a network forger, silicon dioxide forms a silicate liquid phase with alkaline earth metal oxides such as calcium oxide and magnesium oxide at high temperatures, filling intergranular pores and promoting densification. If the amount of silicon dioxide is less than 0.5 parts, the amount of silicate liquid phase is insufficient, the intergranular pores are not fully filled, and the residual porosity is high; if it is more than 3 parts, excess silicon dioxide forms a silicon-rich glass phase at the grain boundaries. The thermal conductivity of the glass phase is only 1 / 10 to 1 / 20 that of alumina grains, significantly increasing the grain boundary thermal resistance and reducing the overall thermal conductivity of the substrate by more than 15%. Furthermore, the silicon-rich glass phase may undergo ion migration under the action of a high-temperature electric field, reducing the electrical insulation reliability of the substrate.

[0053] In some embodiments, the purity of the zirconium oxide is ≥99.5%. Zirconia in an alumina matrix enhances the fracture toughness of the substrate through a dual mechanism of phase transformation toughening and microcrack toughening. During sintering and cooling, tetragonal zirconium oxide undergoes stress-induced phase transformation into a monoclinic phase, accompanied by a 3%–5% volume expansion, generating a compressive stress field at the crack tip, hindering crack propagation. If the zirconium oxide content is less than 1 part, the toughening effect is insufficient, with the improvement in substrate fracture toughness less than 10%; if it is more than 5 parts, the excess zirconium oxide is unevenly distributed in the matrix, and local agglomeration areas generate excessive volume expansion stress during the phase transformation, which may induce spontaneous microcracks. Once these microcracks connect, they can actually reduce the substrate strength and density.

[0054] In some embodiments, the method for preparing the modified inorganic filler includes the following steps: Silicon carbide and anhydrous ethanol were mixed and subjected to ultrasonic treatment to obtain a silicon carbide suspension. The silicon carbide suspension, 3-isocyanate propyltriethoxysilane and water were mixed and stirred at 60~80°C to obtain the initial modified silicon carbide. The modified silicon carbide, glycidyl methacrylate, and azobisisobutyronitrile were mixed and then subjected to in-situ polymerization at 70-90°C to obtain the modified inorganic filler.

[0055] It should be noted that this preparation method involves a two-step reaction of coupling anchoring and in-situ polymerization to prepare a coating layer on the surface of nano-silicon carbide, forming a modified inorganic filler with a core-shell structure. The nano-silicon carbide surface naturally oxidizes in air to form a thin SiO2 layer approximately 1-3 nm thick. This thin layer is rich in silanol groups, providing reaction sites for coupling anchoring. During the stirred reaction, the triethoxysilane group of 3-isocyanate propyltriethoxysilane hydrolyzes in an aqueous ethanol system to generate silanol groups. These silanol groups undergo a condensation reaction with the Si-OH groups on the surface of the nano-silicon carbide to form Si-O-Si covalent bonds, anchoring the 3-isocyanate propyltriethoxysilane molecule to the surface of the nano-silicon carbide. Simultaneously, the isocyanate group (-NCO) at the other end of the 3-isocyanate propyltriethoxysilane molecule is exposed, providing grafting sites for subsequent polymerization. In the in-situ polymerization reaction, glycidyl methacrylate monomers undergo free radical polymerization under the action of an initiator (azobisisobutyronitrile). Polymer segments are grafted onto the surface of nano-silicon carbide through copolymerization of the C=C double bonds in 3-isocyanate propyltriethoxysilane molecules, forming an organic polymer coating layer rich in epoxy groups. The advantages of this core-shell structure are: the organic polymer coating layer reduces van der Waals attraction between nano-silicon carbide particles through steric hindrance, effectively preventing agglomeration of nanoparticles in the slurry; the surface epoxy groups undergo thermal ring-opening reaction in the early stages of sintering (approximately 300-500°C), chemically bonding with hydroxyl groups on the ceramic powder surface to form an organic-inorganic covalent interface layer, rather than simple physical adsorption; as the sintering temperature further increases, the organic polymer coating layer thermally decomposes, and the residual carbon from its decomposition undergoes a localized carbothermal reduction reaction with oxides at the interface, generating trace oxygen vacancies in situ, promoting grain boundary diffusion and mass transfer, and accelerating the densification process. In some embodiments, the average particle size of the silicon carbide is 30-100 nm.

[0056] In some embodiments, the mass-to-volume ratio of silicon carbide to anhydrous ethanol is 1 g: 8-15 mL. If the mass-to-volume ratio is less than 1 g: 8 mL, the concentration of the silicon carbide suspension is too high, the viscosity is too large, the ultrasonic cavitation effect is severely attenuated, the nanoparticle aggregates cannot be effectively depolymerized, and the subsequent IPTS grafting is uneven. If the mass-to-volume ratio is greater than 1 g: 15 mL, the suspension concentration is too low. Although the dispersion effect is good, the hydrolysis and self-condensation side reactions of IPTS in dilute solutions are aggravated. The IPTS molecules undergo Si-OH condensation to form oligomeric siloxanes, which consumes effective coupling agent, reduces the grafting density on the silicon carbide surface, and the large amount of solvent increases the post-processing cost.

[0057] In some embodiments, the ultrasonic treatment has a power of 200-500W, a duration of 30-60 minutes, and a frequency of 20-40kHz. The ultrasonic treatment utilizes a localized high-temperature, high-pressure microjets generated by acoustic cavitation to break down nano-silicon carbide agglomerates into monodisperse particles or small-sized agglomerates.

[0058] In some embodiments, the mass-to-volume ratio of the silicon carbide suspension, 3-isocyanate propyltriethoxysilane, and water is 1 g : (0.1~0.2) mL : (0.02~0.05) mL.

[0059] In some embodiments, the stirring reaction is carried out at a speed of 400-600 r / min for a duration of 4-8 h. The stirring reaction ensures that IPTS is uniformly dispersed in the nano-silicon carbide suspension, while simultaneously promoting the condensation reaction between the silanol groups generated by the hydrolysis of IPTS and the Si-OH groups on the silicon carbide surface.

[0060] In some embodiments, the mass-to-volume ratio of the initially modified silicon carbide, glycidyl methacrylate, and azobisisobutyronitrile (AIOBR) is 1 g: (0.25~0.5) mL: (0.003~0.008) g. The amount of glycidyl methacrylate monomer determines the thickness of the organic polymer coating layer. If the mass-to-volume ratio is less than 1 g: 0.25 mL, the amount of glycidyl methacrylate monomer is insufficient, resulting in a coating layer that is too thin after polymerization. The organic coating layer cannot effectively shield the van der Waals attraction between the nano-silicon carbide particles, and the steric hindrance effect is insufficient, causing the particles to still tend to agglomerate in the slurry. If the mass-to-volume ratio is greater than 1 g: 0.5 mL, the amount of glycidyl methacrylate monomer is excessive, resulting in a coating layer that is too thick after polymerization. Although the dispersibility is good, the excessively thick organic layer decomposes and generates a large amount of gas during the sintering and debinding stage, forming large residual pores at the interface, which reduces the densification effect. Furthermore, the excessively thick coating layer increases the cost of using GMA monomer.

[0061] In some embodiments, the in-situ polymerization reaction is carried out under stirring conditions, with a stirring speed of 300-500 r / min and a stirring time of 3-6 h. In the in-situ polymerization reaction, glycidyl methacrylate monomers undergo free radical polymerization under the action of an initiator, and polymer segments are copolymerized and grafted onto the surface of nano-silicon carbide through the C=C double bonds of 3-isocyanate propyltriethoxysilane molecules. If the stirring speed is below 300 r / min, the glycidyl methacrylate monomers are unevenly distributed in the reaction system, and the excessively high local concentration of glycidyl methacrylate leads to intensified homopolymerization, forming free polyglycidyl methacrylate (PGMA) homopolymers and reducing grafting efficiency. If the stirring speed is above 500 r / min, shear force may break the growing polymer segments, reducing the degree of polymerization. If the reaction time is less than 3 hours, the conversion rate of glycidyl methacrylate monomer is low and the coating layer is incomplete. If the reaction time is more than 6 hours, the glycidyl methacrylate monomer has been basically completely converted, and continuing the reaction will not further increase the coating layer thickness. Moreover, prolonged heating may cause some epoxy groups to undergo thermal ring-opening side reactions, reducing the content of effective epoxy groups in the coating layer.

[0062] In some embodiments, the preparation method of the hyperbranched polyester dispersant includes the following steps: Trimethylolpropane, 2,2-dimethylolpropionic acid and p-toluenesulfonic acid were mixed and subjected to polycondensation reaction at 140~160℃ to obtain hydroxyl-terminated hyperbranched polyester. The hyperbranched polyester with terminal hydroxyl groups and castor oil fatty acids are mixed and then subjected to esterification reaction at 180~200℃ to obtain the hyperbranched polyester dispersant.

[0063] It should be noted that this preparation method constructs a hyperbranched polyester dispersant with a three-dimensional spherical structure and long-chain fatty acid ester end groups through a two-step reaction of melt polycondensation and end-group esterification modification. In the polycondensation reaction, trimethylolpropane acts as the core molecule, providing three reactive hydroxyl groups, and 2,2-dimethylolpropionic acid acts as the branching monomer. Under the catalysis of p-toluenesulfonic acid, the carboxyl group of 2,2-dimethylolpropionic acid undergoes esterification with the hydroxyl groups of trimethylolpropane or intermediate products. Simultaneously, the two hydroxyl groups of 2,2-dimethylolpropionic acid itself provide branching sites for the next reaction. After multiple iterations of polycondensation, a highly branched structure and a surface rich in hydroxyl groups are formed, resulting in a terminal hydroxyl hyperbranched polyester. In the second esterification reaction, some of the hydroxyl groups of the terminal hydroxyl hyperbranched polyester undergo esterification with the carboxyl groups of castor oil fatty acids, introducing long-chain fatty acid ester end groups. The main component of castor oil fatty acids is ricinoleic acid (12-hydroxy-9-octadecenoic acid), whose long-chain alkyl segments provide excellent steric hindrance and good compatibility with organic binder systems. The advantages of this hyperbranched polyester dispersant compared to traditional linear dispersants are as follows: the three-dimensional spherical hyperbranched structure forms a dense steric hindrance layer on the surface of powder particles, and the steric hindrance effect is significantly stronger than the single-point or double-point adsorption of linear molecules; multiple long-chain fatty acid ester end groups can be simultaneously anchored to the surface of multiple ceramic powder particles, forming multi-point adsorption with high adsorption strength and not easily desorbed under ball mill shear force; castor oil fatty acid segments have good compatibility with PVB resin and will not undergo phase separation or precipitation during slurry drying. If the amount of hyperbranched polyester dispersant is less than 0.5 parts, the coverage of dispersant molecules on the surface of ceramic powder is insufficient, some powder surfaces do not adsorb dispersant, and powder particles aggregate through van der Waals forces, increasing the viscosity of the slurry, making casting difficult, and resulting in uneven powder distribution in the substrate after sintering. If the amount is more than 3 parts, the excess dispersant forms free micelles in the slurry. The free micelles volatilize or decompose during the drying process, leaving pores and reducing the density of the green body. Furthermore, the organic residues of the excess dispersant decompose during the debinding process, which may lead to blistering or cracking of the green body.

[0064] In some embodiments, the mass ratio of trimethylolpropane, 2,2-dimethylolpropionic acid, and p-toluenesulfonic acid is 1:5~7:0.03~0.08. This ratio determines the degree of branching and molecular weight of the hyperbranched polyester. The molar ratio of 2,2-dimethylolpropionic acid to trimethylolpropane controls the branching generation. Theoretical calculations show that this ratio range corresponds to 3~5 generations of branched structures, and the number average molecular weight of the resulting hyperbranched polyester is 3000~8000. If the amount of 2,2-dimethylolpropionic acid is less than 500, the branching generation is insufficient, the molecular structure tends to be linear rather than spherical, the steric hindrance effect is weakened, and the dispersion efficiency decreases. If the amount of 2,2-dimethylolpropionic acid is more than 700, the branching is too high, the internal space of the molecule is crowded, some hydroxyl groups are embedded inside the molecule and cannot participate in subsequent esterification reactions, and the accessibility of end groups decreases. If the amount of p-toluenesulfonic acid is less than 3 parts, the catalytic activity is insufficient, the esterification reaction rate is slow, the polycondensation reaction time is long, and the production efficiency is low; if it is more than 8 parts, the catalyst residue is high, the residual p-toluenesulfonic acid may catalyze side reactions in the subsequent esterification reaction, and the acidic residue in the slurry system may affect the chemical stability of PVB resin.

[0065] In some embodiments, the polycondensation reaction is carried out under stirring conditions, with a stirring speed of 100-300 r / min and a time of 6-10 h. The polycondensation reaction is a melt bulk polymerization, and the viscosity of the system gradually increases as the reaction proceeds. If the stirring speed is below 100 r / min, insufficient stirring leads to uneven local temperature and reactant concentrations, resulting in a wide molecular weight distribution. If the stirring speed is above 300 r / min, the high shear force in the high-viscosity melt may cause mechanical breakage of the molecular chains. If the time is less than 6 h, the esterification reaction is incomplete, the molecular weight is low, and the steric hindrance effect of the dispersant is insufficient. If the time is longer than 10 h, the molecular weight is too high, the solubility of the dispersant in organic solvents decreases, making it difficult to completely dissolve during slurry preparation, thus reducing the dispersion effect.

[0066] In some embodiments, the mass-to-volume ratio of the hydroxyl-terminated hyperbranched polyester to castor oil fatty acid is 1 g: (0.15~0.3) mL. If the mass-to-volume ratio is less than 1 g: 0.15 mL, the amount of castor oil fatty acid is insufficient, the esterification rate of the hydroxyl-terminated molecules is low, and a large number of unmodified hydroxyl groups remain on the surface of the dispersant molecules. In the slurry system, intermolecular hydrogen bonds are formed between hydroxyl groups, leading to the self-aggregation of dispersant molecules and failure to effectively disperse ceramic powder. If the mass-to-volume ratio is greater than 1 g: 0.3 mL, the esterification rate is too high, and there are almost no residual hydroxyl groups on the surface of the dispersant molecules. Although it has good compatibility with PVB resin, it lacks the ability to form hydrogen bonds with the hydroxyl groups on the surface of ceramic powder, resulting in a decrease in the adsorption strength of the dispersant on the powder surface and easy desorption under the shear force of ball milling.

[0067] In some embodiments, the esterification reaction is carried out under stirring conditions, with a stirring speed of 150-350 r / min and a stirring time of 3-5 h. If the stirring speed is lower than 150 r / min, mass transfer in the high-viscosity reaction system is uneven, resulting in a slow and uneven esterification reaction rate. If the stirring speed is higher than 350 r / min, high shear force may cause oxidation or polymerization side reactions of the unsaturated double bonds in castor oil fatty acids. If the time is less than 3 h, the esterification reaction is incomplete, the esterification rate is low, and the compatibility and dispersion effect of the dispersant in the slurry are insufficient. If the time is longer than 5 h, prolonged high-temperature treatment may cause thermal oxidative crosslinking of the unsaturated bonds in castor oil fatty acids, resulting in a darker color of the dispersant and the possible formation of insoluble gel particles, affecting the slurry filtration and casting quality.

[0068] In some embodiments, the defoamer is selected from one or both of n-butanol and silicone defoamers. If the amount of defoamer is less than 0.1 parts, the defoaming effect is insufficient, and residual bubbles remain in the cast green belt, forming closed pores after sintering, reducing the substrate density and insulation strength; if it is more than 0.5 parts, the excess defoamer migrates to the surface of the green belt during the slurry drying process, forming a low surface tension region, which leads to a decrease in interlayer bonding during subsequent lamination, and interlayer cracking may occur after sintering.

[0069] In some embodiments, the organic solvent is selected from one or both of toluene and anhydrous ethanol. If the total amount of organic solvent is less than 40 parts, the solid content of the slurry is too high, the viscosity is too large, the ball milling efficiency is low, the slurry fluidity is insufficient during casting, and the thickness of the green belt is uneven; if it is more than 80 parts, the solid content of the slurry is too low, the solvent evaporation during casting drying is large, the energy consumption is increased, and the low solid content slurry is prone to powder sedimentation and stratification during storage, resulting in poor slurry stability.

[0070] Secondly, this application provides a method for preparing a high-performance ceramic substrate, comprising the following steps: Alumina, magnesium oxide, yttrium oxide, calcium oxide, silicon dioxide, zirconium oxide, organic solvent and hyperbranched polyester dispersant are mixed and then subjected to a first ball milling process to obtain a primary slurry; The primary slurry, polyvinyl butyral, dibutyl phthalate and defoamer are mixed and then subjected to a second ball milling process to obtain the secondary slurry. The secondary slurry and modified inorganic filler are mixed and stirred to obtain a casting slurry. The casting slurry is subjected to vacuum degassing treatment, and then cast molding treatment is performed to obtain a green tape; The green strip is debonded and then sintered to obtain a high-performance ceramic substrate.

[0071] It should be noted that the first ball milling process involves mixing and milling the ceramic matrix powder, hyperbranched polyester dispersant, and organic solvent. During this stage, the long-chain fatty acid ester end groups of the hyperbranched polyester dispersant anchor onto the surface of the ceramic powder particles, increasing steric hindrance and allowing the ceramic powder particles to be uniformly dispersed in the solvent, achieving initial particle refinement. The impact and shear force of the milling media break up powder agglomerates, and the hyperbranched polyester dispersant adsorbs onto the surface of the newly formed particles, preventing secondary agglomeration. The second ball milling process introduces polyvinyl butyral and dibutyl phthalate. Polyvinyl butyral dissolves in the organic solvent to form a polymer solution, which uniformly coats the surface of the dispersed ceramic powder particles, forming a continuous organic bonding network. Dibutyl phthalate inserts between the polyvinyl butyral molecular chains, reducing interchain forces and giving the green body good flexibility. The modified inorganic filler is added by stirring after ball milling, rather than ball milling it together with the ceramic powder. This is because the organic polymer coating layer of the modified inorganic filler may be damaged under the impact and shear force of prolonged high-energy ball milling, leading to damage to the core-shell structure, coating layer detachment, and loss of interface modification function. The shear force of stirring is much lower than that of ball milling, ensuring that the modified inorganic filler is uniformly dispersed in the secondary slurry without damaging its core-shell structure. Vacuum degassing removes residual air bubbles from the slurry. Casting process involves scraping the slurry onto the base film of the casting machine to form a uniformly thick wet film, which is then dried to evaporate the solvent, forming a green belt with good flexibility and strength. Debinding process involves slow heating in an air or oxygen atmosphere, causing the polyvinyl butyral, dibutyl phthalate, hyperbranched polyester dispersant, and the organic coating layer of the modified inorganic filler in the green belt to gradually oxidize and decompose, and be discharged as gaseous products. At the same time, initial neck connections are formed between powder particles. Sintering treatment at high temperatures densifies powder particles through solid-phase diffusion and liquid-phase sintering mechanisms, forming a dense corundum structure ceramic substrate.

[0072] In some embodiments, the first ball milling process uses alumina balls as the milling media, the diameter of which is 5-15 mm, and the material-to-ball mass ratio is 1:2-4. The first ball milling process is carried out under stirring conditions, the stirring speed is 200-400 r / min, and the time is 12-48 h. Using alumina balls as the milling media avoids the introduction of impurities incompatible with the matrix composition. If the material-to-ball mass ratio is less than 1:2, the amount of milling media is insufficient, resulting in low grinding efficiency, inadequate powder refinement and dispersion, and insufficient sintering activity. If the ratio is greater than 1:4, there is too much milling media, reducing the free space inside the milling jar, restricting media movement, and actually decreasing grinding efficiency. Furthermore, the wear of the milling media itself is accelerated, increasing the introduction of alumina abrasive particles and affecting the accuracy of the formulation. If the rotation speed is below 200 r / min, the ball mill media movement mode is cascading, and the grinding action is mainly friction, resulting in insufficient impact crushing force and low deagglomeration efficiency. If the rotation speed is above 400 r / min, the ball mill media movement mode is cascading or centrifugal, resulting in excessive impact force. The violent collision between the ball mill media leads to an accelerated crushing rate, and wear debris is incorporated into the slurry. Furthermore, the excessive energy input causes the slurry temperature to rise, which may lead to the volatilization of some organic solvents and changes in slurry viscosity.

[0073] In some embodiments, the ball milling media used in the second ball milling process are alumina balls with a diameter of 5-15 mm and a ball-to-material mass ratio of 1:2-4. The second ball milling process is carried out under stirring conditions, with a stirring speed of 200-400 r / min and a time of 12-36 h. The purpose of the second ball milling process is to completely dissolve polyvinyl butyral and uniformly coat it onto the surface of the ceramic powder particles, while simultaneously dispersing dibutyl phthalate uniformly between the polyvinyl butyral particles. If the time is less than 12 h, the polyvinyl butyral will not dissolve completely or coat unevenly, resulting in insufficient binder content in local areas of the green belt. These areas will have low strength and are prone to breakage during subsequent cutting and handling. If the time is longer than 36 h, the prolonged ball milling will cause the slurry temperature to rise slowly. Under the warm environment, polyvinyl butyral may undergo slight cross-linking or degradation, resulting in changes in molecular weight distribution and affecting the mechanical properties and binder removal behavior of the green belt.

[0074] In some embodiments, the stirring speed is 200-500 r / min, and the time is 1-4 h. The moderate shear force from the stirring ensures that the modified inorganic filler is uniformly dispersed in the secondary slurry. If the speed is below 200 r / min, the dispersion efficiency is low, the distribution of the modified inorganic filler in the slurry is uneven, and the filler content in local areas is too high or too low, resulting in uneven grain size and density in the corresponding areas of the substrate after sintering. If the speed is above 500 r / min, the shear force is too high, and prolonged stirring may cause the organic polymer coating layer of the modified inorganic filler to deform, elongate, or even partially peel off under shear force, losing the integrity of the core-shell structure. If the time is less than 1 h, the dispersion is insufficient; if the time is longer than 4 h, the dispersion is already uniform, and continued stirring is not beneficial and increases the risk of damage to the coating layer.

[0075] In some embodiments, the vacuum degree of the vacuum degassing process is -0.08 to -0.095 MPa, and the degassing time is 20 to 60 minutes. Under negative pressure, bubbles in the slurry expand and rise due to the internal and external pressure difference, eventually bursting and being removed from the surface. If the vacuum degree is lower than -0.08 MPa, the driving force for bubble expansion is insufficient, and small bubbles cannot be effectively removed, remaining in the slurry. If the vacuum degree is higher than -0.095 MPa, it is close to the saturated vapor pressure of the organic solvent, and the solvent evaporates in large quantities under low pressure. The evaporation of solvent on the slurry surface carries away heat, causing the surface temperature to drop. At the same time, a skin forms on the slurry surface due to the rapid evaporation of solvent. The skin hinders the escape of lower-layer bubbles, thus reducing the degassing efficiency. If the time is less than 20 minutes, the bubbles are not sufficiently removed; if the time is longer than 60 minutes, the continuous evaporation of solvent causes the slurry viscosity to increase, which is not conducive to subsequent casting molding.

[0076] In some embodiments, the casting process is performed on a casting machine with a doctor blade gap of 0.3~1.5mm, a casting speed of 0.5~2.0m / min, and a drying temperature of 60~100℃, resulting in a green strip thickness of 0.2~1.0mm. The doctor blade gap directly controls the wet film thickness, and the thickness of the green strip after drying is approximately 40%~70% of the wet film thickness. If the doctor blade gap is less than 0.3mm, the wet film is too thin, and the uniformity of the slurry spreading on the base film is significantly affected by the slurry viscosity and surface tension, easily leading to thickness fluctuations and streak defects. If the gap is greater than 1.5mm, the wet film is too thick, and during drying, the surface solvent evaporates first to form a dense skin, hindering the diffusion of the inner solvent outward, and the internal solvent accumulates to form bubbles or pinhole defects. If the casting speed is less than 0.5m / min, the production efficiency is low; if it is greater than 2.0m / min, the slurry spreading time on the base film is short, and the wet film surface does not have enough time to level before entering the drying stage, resulting in increased surface roughness. If the drying temperature is below 60℃, the solvent evaporation rate is slow, the drying is insufficient, and the residual solvent content in the green belt is high. During subsequent lamination, the residual solvent seeps out under pressure, resulting in poor interlayer adhesion. If the drying temperature is above 100℃, the solvent evaporation rate is too fast, the surface of the green belt forms a skin quickly, the internal solvent evaporation is hindered, and surface bubbles or internal pores are formed. In addition, dibutyl phthalate may partially evaporate at high temperatures, the flexibility of the green belt decreases, and it is easy to crack during cutting.

[0077] In some embodiments, the heating rate of the debinding process is 0.5~2.0℃ / min, the debinding temperature is 550~650℃, and the holding time is 2~6h. The debinding process is the step in the transformation of the green body into the ceramic body, during which organic matter gradually decomposes and is discharged in the form of gaseous products. If the heating rate is lower than 0.5℃ / min, the debinding cycle is too long, resulting in low production efficiency; if the heating rate is higher than 2.0℃ / min, the organic matter decomposes too quickly, and the decomposed gaseous products accumulate inside the body, forming high-pressure bubbles. When the pressure inside the bubbles exceeds the local strength of the body, they burst, forming cracks or interlayer delamination in the body. If the holding time is less than 2h, the organic matter decomposes incompletely, and the residual carbon undergoes a carbothermic reduction reaction with oxides in the subsequent sintering stage, forming CO / CO2 pores or oxygen vacancy defects inside the substrate; if the holding time is longer than 6h, the organic matter has completely decomposed, and continuing to hold the temperature is not beneficial and increases energy consumption.

[0078] In some embodiments, the heating rate of the sintering treatment is 3~10℃ / min, the sintering temperature is 1550~1680℃, the holding time is 2~6h, and the sintering atmosphere is air or oxygen. The sintering treatment densifies the porous green body after binder removal through mass transport. If the heating rate is below 3℃ / min, the sintering cycle is too long, and during the slow heating period, the grains may grow sufficiently before densification is complete, resulting in grain coarsening before densification and ultimately unsatisfactory density. If the heating rate is above 10℃ / min, the temperature difference between the inside and outside of the green body is too large, causing the surface to densify before the interior, forming a dense outer shell that seals the internal interconnected pores, preventing internal gas from escaping and ultimately forming closed pores, leading to a decrease in density. The sintering temperature of 1550~1680℃ is the liquid phase sintering temperature window for alumina-based ceramics. Within this temperature range, the amount of liquid phase formed by the sintering aid is moderate, providing sufficient dissolution and mass transfer channels without excessive grain growth or liquid phase overflow. If the sintering temperature is below 1550℃, the amount of liquid phase generated is insufficient, and sintering is mainly solid-phase diffusion, resulting in a slow densification rate and an inability to achieve high density within the holding time. If the temperature is above 1680℃, although the densification rate is fast, the excessive amount of liquid phase causes alumina grains to grow rapidly in the liquid phase, resulting in abnormal grain growth. Furthermore, the liquid phase viscosity near the melting point of alumina (approximately 2050℃) decreases significantly, and some liquid phase migrates to the bottom of the substrate under gravity, creating a compositional gradient and inconsistent properties between the upper and lower surfaces of the substrate. A holding time of 2–6 hours allows for sufficient removal of pores and moderate grain growth to reach an equilibrium state. If the holding time is less than 2 hours, pore removal is insufficient, resulting in a high residual porosity. If the holding time is longer than 6 hours, grains continue to grow in the liquid phase, leading to over-burning, with grain sizes exceeding 10 μm and a decrease in mechanical properties.

[0079] Thirdly, this application provides a method for dry film exposure etching protection treatment of metallized vias on high-performance ceramic substrates as described in the foregoing scheme, comprising the following steps: Hole and groove processing is performed on the high-performance ceramic substrate. After cleaning, a metal film layer is sputtered to obtain a coated ceramic substrate. The coated ceramic substrate is placed on a bakelite board and dry film is applied. After the film is applied, it is removed and rehydrated. The ceramic substrate with holes and grooves protected by a dry film is obtained by performing alignment exposure according to the exposure dosage and exposure drawing, followed by secondary rehydration after exposure, and spray development according to the developer solution. The ceramic substrate with the hole grooves protected by the dry film is subjected to patterned outer film etching treatment, and then the film is removed and cleaned to obtain a high-performance ceramic substrate with complete metallized hole grooves.

[0080] It should be noted that this protective treatment method uses a pre-formed, fully water-soluble photosensitive dry film instead of traditional liquid photoresist as a protective masking layer for the metallized vias during the spray etching process. The dry film lamination process uses heated rollers to press the photosensitive resist layer onto the surface of the coated ceramic substrate. Under temperature and pressure, the resist layer undergoes plastic flow, filling the microscopic unevenness and irregularities at the edges of the vias, forming a defect-free, complete coverage. The rehydration process allows the molecular chains of the photosensitive resist layer to reorient and reach equilibrium during the cooling process, releasing the internal stress generated during lamination and stabilizing the physical adsorption between the resist layer and the metal film. During the alignment exposure process, the photosensitive resist layer in the exposed area undergoes a free radical photopolymerization reaction. The acrylate photopolymer monomers crosslink and solidify under the action of a photoinitiator, forming a hardened protective layer insoluble in the developer, covering the metallized vias. The secondary rehydration process ensures the photopolymerization reaction is fully completed, the free radicals are completely consumed, and post-polymerization is avoided. During the spray development process, the alkaline environment of the sodium carbonate aqueous solution and the acidic groups (carboxyl groups) in the photoresist layer of the unexposed areas cause the unexposed dry film to dissolve and detach. Meanwhile, the exposed and hardened areas remain due to the dense cross-linked network, making it difficult for the sodium carbonate solution to penetrate, thus forming a robust protective layer that precisely covers the metallized vias. In the pattern outer film etching process, the etchant selectively dissolves the metal film layer not protected by the dry film and photoresist. The dry film protective layer, due to its excellent chemical corrosion resistance and mechanical strength, maintains its structural integrity under spray pressure and etchant impact, ensuring that the metal layer within the vias is not corroded. The film removal cleaning process removes the dry film and photoresist protective layer, exposing a complete and continuous metallized via structure.

[0081] In some embodiments, the hole and groove processing is carried out by laser drilling or mechanical drilling, and the hole diameter ranges from 50 to 300 μm.

[0082] In some embodiments, the sputtered metal film is a magnetron sputtered TiW / Au film, wherein the thickness of the TiW layer is 0.08~0.15μm and the thickness of the Au layer is 0.2~0.5μm.

[0083] In some embodiments, the film application speed of the dry film application process is 10~20 mm / s, the upper roller temperature is 85~95℃, the lower roller temperature is 85~95℃, and the film application pressure is 8~15 N / cm. 2 The thickness of the dry film used is 15~30μm.

[0084] In some embodiments, the rehydration time is 10-30 minutes.

[0085] In some embodiments, the secondary rehydration time is 10-30 minutes.

[0086] In some embodiments, the exposure dose of the alignment exposure process is 3000~5000mJ.

[0087] In some embodiments, the developing solution for the spray developing process is an aqueous sodium carbonate solution, wherein the mass concentration of sodium carbonate in the developing solution is 14-20%, the developing temperature is 40-50°C, and the developing time is 2-5 min.

[0088] In some embodiments, the dry film is a fully water-soluble photosensitive dry film, comprising a protective film, a substrate film, and a photosensitive resist layer, wherein the photosensitive resist layer contains acrylate photopolymerizable monomers.

[0089] The present application will be specifically described below through specific embodiments. The following embodiments are only some embodiments of the present application and are not intended to limit the present application.

[0090] Example 1 This embodiment provides a high-performance ceramic substrate, its preparation method, and a method for protecting the metallized trench dry film exposure etching, specifically including the following: The high-performance ceramic substrate comprises, by weight, the following components: 90 parts alumina, 1.5 parts magnesium oxide, 1.0 part yttrium oxide, 1.5 parts calcium oxide, 2.0 parts silicon dioxide, 3.0 parts zirconium oxide, 8 parts modified inorganic filler, 12 parts polyvinyl butyral, 10 parts dibutyl phthalate, 1.8 parts hyperbranched polyester dispersant, 0.3 parts defoamer, and 55 parts organic solvent; The alumina has a purity of 99.7% and an average particle size of 1.8 μm; the magnesium oxide has a purity of 99.6%; the yttrium oxide has a purity of 99.9%; the calcium oxide has a purity of 98.5%; the silicon dioxide has a purity of 99.2%; the zirconium oxide has a purity of 99.6%; the defoamer is n-butanol; and the organic solvent is toluene.

[0091] The preparation method of the modified inorganic filler includes the following steps: 10g of silicon carbide (average particle size 50nm) was mixed with 120mL of anhydrous ethanol and ultrasonically treated for 45min at a power of 300W and a frequency of 25kHz to obtain a silicon carbide suspension. The silicon carbide suspension was mixed with 1.5 mL of 3-isocyanate propyltriethoxysilane and stirred at 70 °C and 500 r / min for 6 h to obtain the initial modified silicon carbide. The modified silicon carbide was mixed with 3.5 mL of glycidyl methacrylate, and 0.05 g of azobisisobutyronitrile was added. The mixture was then subjected to in-situ polymerization at 80 °C and a stirring speed of 400 r / min for 5 h. After centrifugation (10000 r / min, 15 min), washing three times with anhydrous ethanol, and vacuum drying at 60 °C for 8 h, the modified inorganic filler was obtained.

[0092] The preparation method of the hyperbranched polyester dispersant includes the following steps: 10g of trimethylolpropane, 60g of 2,2-dimethylolpropionic acid and 0.5g of p-toluenesulfonic acid were mixed and subjected to polycondensation reaction at 150℃, stirring speed of 200r / min and nitrogen protection for 8h to obtain hydroxyl-terminated hyperbranched polyester. 50g of the terminal hydroxyl hyperbranched polyester and 10mL of castor oil fatty acid were mixed and then subjected to esterification reaction at 190℃, stirring speed of 250r / min and nitrogen protection for 4h to obtain the hyperbranched polyester dispersant.

[0093] The method for preparing the high-performance ceramic substrate includes the following steps: 900g of alumina, 15g of magnesium oxide, 10g of yttrium oxide, 15g of calcium oxide, 20g of silicon dioxide, 30g of zirconium oxide, 370mL of toluene and 18g of hyperbranched polyester dispersant were mixed and then ball-milled for 36 hours at a mass ratio of 1:3 using alumina balls (10mm in diameter) as the ball milling medium to obtain a primary slurry. The primary slurry, 120g of polyvinyl butyral, 100g of dibutyl phthalate and 3g of n-butanol were mixed and then subjected to a second ball milling treatment at 300r / min for 24h with alumina balls (10mm in diameter) as the ball milling medium and a material-to-ball mass ratio of 1:3, to obtain the secondary slurry. The secondary slurry and 80g of modified inorganic filler were mixed and stirred at 350r / min for 2h to obtain the casting slurry. The casting slurry was subjected to vacuum degassing treatment at a vacuum degree of -0.09MPa for 30 minutes, and then cast on a casting machine with a doctor blade gap of 0.8mm, a casting speed of 1.0m / min, and a drying temperature of 80℃ to obtain a green strip with a thickness of 0.5mm. The green strip is heated to 600°C at a heating rate of 1°C / min for debinding treatment and held at that temperature for 4 hours. Then, it is heated to 1620°C at a heating rate of 5°C / min for sintering treatment and held at that temperature for 4 hours. The sintering atmosphere is air, and the strip is cooled in the furnace to obtain the high-performance ceramic substrate.

[0094] The method for protecting metallized trench dry film through exposure etching includes the following steps: Through holes with a diameter of 100μm are processed on the high-performance ceramic substrate using ultraviolet laser drilling, with 100 holes per substrate, followed by ultrasonic cleaning and drying. A TiW (0.10 μm) / Au (0.30 μm) seed layer was deposited on both sides of the substrate and the inner wall of the hole using a magnetron sputtering device. The W content in TiW was 15 wt%. Then, Au was electroplated on the whole plate to thicken the coating to a thickness of 2.0 μm, thus obtaining a coated ceramic substrate. The coated ceramic substrate is placed on an insulating bakelite board and subjected to dry film lamination on a laminating machine. The lamination speed is 15 mm / s, the upper roller temperature is 90°C, the lower roller temperature is 90°C, and the lamination pressure is 10 N / cm. 2 The dry film used is a fully water-soluble photosensitive dry film (20μm thick, including a protective film, a substrate film and a photosensitive resist layer containing acrylate photopolymer monomers). After applying the film, remove it and rehydrate for 15 minutes. Alignment exposure was performed in a laser direct imaging exposure device at an exposure dose of 4000 mJ, followed by a second water rehydration for 15 min. The surface morphology of the exposed substrate was then photographed using a metallographic microscope. The alignment status of the circuit pattern and the via array is shown below. Figure 1 As shown; by Figure 1 It can be seen that the alignment accuracy between the protected pattern and the through-hole array after exposure processing is high, the edges of the pattern are neat and sharp, the hole positions and the preset protected area have good overlap, and there is no obvious misalignment or pattern distortion.

[0095] The top protective film of the dry film was removed, and the substrate was spray-developed at 45°C for 3 minutes using a developing solution (sodium carbonate concentration of 16.7%) to obtain a ceramic substrate with the vias protected by the dry film. The developed substrate was then photographed using a metallographic microscope, and the dry film protection effect in the array via area was shown as follows: Figure 2 As shown; by Figure 2 As can be seen, after development, all the array via openings were completely covered by the dry film, with clear and regular dry film boundaries. The protection status of the batch of vias was consistent, with no instances of missed development, over-development, or dry film peeling. Local magnified images of the transition area of ​​the irregularly shaped vias were taken using a metallurgical microscope, revealing the dry film adhesion status as follows: Figure 3 As shown; by Figure 3 It can be seen that the dry film can fully fill the micro-uneven structure at the edge of the pores and grooves, adhere tightly to the metal film layer, and has no curling edges, gaps or gaps. It has good adaptability to irregular pore and groove structures and can effectively prevent the penetration of subsequent corrosion liquid.

[0096] The ceramic substrate with the metallized vias protected by a dry film was subjected to patterned outer film etching. Excess unprotected gold layer was removed by spraying with a gold etching solution, followed by film removal and cleaning, yielding a high-performance ceramic substrate with complete metallized vias. The microstructure of individual metallized vias was imaged using a metallographic microscope, and the results are as follows: Figure 4 As shown; by Figure 4As can be seen, the metal layer inside the through-holes after etching and film removal is continuous, complete, and uniform in thickness, without any defects such as breakage, lateral corrosion, or missing parts. The hole shape has excellent roundness, verifying that the dry film exposure etching protection method can effectively reduce the hole breakage rate and ensure the conductivity integrity of the vias. A physical photograph of the entire ceramic substrate after all processing steps was taken, and the finished product appearance is as follows. Figure 5 As shown; by Figure 5 It can be seen that the final metallized pattern is well-arranged, with a smooth and flat surface, no obvious appearance defects, and good batch processing consistency, which can meet the needs of large-scale production of high-density electronic packaging.

[0097] Example 2 This embodiment provides a high-performance ceramic substrate, its preparation method, and a method for protecting the metallized trench dry film exposure etching, specifically including the following: The high-performance ceramic substrate comprises, by weight, the following components: 85 parts alumina, 1.0 part magnesium oxide, 1.5 parts yttrium oxide, 2.0 parts calcium oxide, 1.5 parts silicon dioxide, 4.0 parts zirconium oxide, 10 parts modified inorganic filler, 15 parts polyvinyl butyral, 12 parts dibutyl phthalate, 2.2 parts hyperbranched polyester dispersant, 0.4 parts defoamer, and 65 parts organic solvent; The alumina has a purity of 99.6% and an average particle size of 2.2 μm; the magnesium oxide has a purity of 99.5%; the yttrium oxide has a purity of 99.9%; the calcium oxide has a purity of 98.2%; the silicon dioxide has a purity of 99.1%; the zirconium oxide has a purity of 99.5%; the defoamer is an organosilicon defoamer; and the organic solvent is anhydrous ethanol.

[0098] The preparation method of the modified inorganic filler includes the following steps: 10g of silicon carbide (average particle size 80nm) was mixed with 100mL of anhydrous ethanol and ultrasonically treated for 35min at a power of 400W and a frequency of 30kHz to obtain a silicon carbide suspension. The silicon carbide suspension was mixed with 1.8 mL of 3-isocyanate propyltriethoxysilane and stirred at 65 °C and 450 r / min for 7 h to obtain the initial modified silicon carbide. The modified silicon carbide was mixed with 4.0 mL of glycidyl methacrylate, and 0.06 g of benzoyl peroxide was added. The mixture was then subjected to in-situ polymerization at 85 °C and a stirring speed of 350 r / min for 4 h. After centrifugation (9000 r / min, 20 min), washing three times with anhydrous ethanol, and vacuum drying at 55 °C for 10 h, the modified inorganic filler was obtained.

[0099] The preparation method of the hyperbranched polyester dispersant includes the following steps: 10g of trimethylolpropane, 65g of 2,2-dimethylolpropionic acid and 0.6g of p-toluenesulfonic acid were mixed and subjected to polycondensation reaction at 155℃, stirring speed of 250r / min and nitrogen protection for 9h to obtain hydroxyl-terminated hyperbranched polyester. 50g of the terminal hydroxyl hyperbranched polyester and 12mL of castor oil fatty acid were mixed and then subjected to esterification reaction at 185℃, stirring speed of 200r / min and nitrogen protection for 4.5h to obtain the hyperbranched polyester dispersant.

[0100] The method for preparing the high-performance ceramic substrate includes the following steps: 850g of alumina, 10g of magnesium oxide, 15g of yttrium oxide, 20g of calcium oxide, 15g of silicon dioxide, 40g of zirconium oxide, 650mL of anhydrous ethanol and 22g of hyperbranched polyester dispersant were mixed and then ball-milled for 30h at a mass ratio of 1:2.5 using alumina balls (12mm in diameter) as the ball milling medium to obtain a primary slurry. The primary slurry, 150g of polyvinyl butyral, 120g of dibutyl phthalate and 4g of silicone defoamer were mixed and then subjected to a second ball milling treatment at 350r / min for 20h using alumina balls (12mm in diameter) as the ball milling medium and a material-to-ball mass ratio of 1:2.5 to obtain the secondary slurry. The secondary slurry was mixed with 100g of modified inorganic filler and stirred at 400r / min for 2.5h to obtain the casting slurry. The casting slurry was subjected to vacuum degassing treatment at a vacuum degree of -0.085MPa for 40 minutes, and then cast on a casting machine with a doctor blade gap of 1.0mm, a casting speed of 0.8m / min, and a drying temperature of 90℃ to obtain a green strip with a thickness of 0.6mm. The green strip is heated to 580°C at a heating rate of 1.5°C / min for debinding and held at that temperature for 5 hours. Then, it is heated to 1580°C at a heating rate of 8°C / min for sintering and held at that temperature for 3 hours. The sintering atmosphere is air, and the strip is cooled in the furnace to obtain the high-performance ceramic substrate.

[0101] The method for protecting metallized trench dry film through exposure etching includes the following steps: Through holes with a diameter of 200μm were processed on the high-performance ceramic substrate using ultraviolet laser drilling, with 80 holes per substrate. The substrate was then ultrasonically cleaned and dried. A TiW (0.15μm) / Au (0.35μm) seed layer was deposited on both sides of the substrate and the inner wall of the hole using a magnetron sputtering device. Then, Au was electroplated on the whole plate to thicken the coating to a thickness of 3.0μm, resulting in a coated ceramic substrate. The coated ceramic substrate was placed on a bakelite board and dry film was applied on a laminating machine at a lamination speed of 12 mm / s, an upper roller temperature of 95°C, a lower roller temperature of 95°C, a lamination pressure of 12 N / cm², and a dry film thickness of 25 μm. After lamination, the substrate was removed and rehydrated for 20 minutes. The laser direct imaging exposure device was used for alignment exposure treatment at an exposure dose of 3500mJ, followed by a second water rehydration for 20 minutes after exposure. Remove the top protective film of the dry film, and spray develop it at 48°C for 4 minutes using a developing solution (sodium carbonate mass concentration of 14.3%) to obtain a ceramic substrate with the cavity protected by the dry film. The ceramic substrate with the hole grooves protected by the dry film is subjected to patterned outer film etching treatment, and then the film is removed and cleaned to obtain a high-performance ceramic substrate with complete metallized hole grooves.

[0102] Example 3 This embodiment provides a high-performance ceramic substrate, its preparation method, and a method for protecting the metallized trench dry film exposure etching, specifically including the following: The high-performance ceramic substrate comprises, by weight, the following components: 93 parts alumina, 2.5 parts magnesium oxide, 0.8 parts yttrium oxide, 1.0 part calcium oxide, 2.5 parts silicon dioxide, 2.0 parts zirconium oxide, 5 parts modified inorganic filler, 10 parts polyvinyl butyral, 9 parts dibutyl phthalate, 1.2 parts hyperbranched polyester dispersant, 0.2 parts defoamer, and 48 parts organic solvent; The alumina has a purity of 99.8% and an average particle size of 1.5 μm; the magnesium oxide has a purity of 99.7%; the yttrium oxide has a purity of 99.9%; the calcium oxide has a purity of 98.6%; the silicon dioxide has a purity of 99.3%; the zirconium oxide has a purity of 99.7%; the defoamer is n-butanol; and the organic solvent is a mixture of toluene and anhydrous ethanol in a volume ratio of 1:1.

[0103] The preparation method of the modified inorganic filler includes the following steps: 10g of silicon carbide (average particle size 35nm) was mixed with 140mL of anhydrous ethanol and ultrasonically treated for 55min at a power of 250W and a frequency of 20kHz to obtain a silicon carbide suspension. The silicon carbide suspension was mixed with 1.2 mL of 3-isocyanate propyltriethoxysilane and stirred at 75 °C and 550 r / min for 5 h to obtain the initial modified silicon carbide. The modified silicon carbide was mixed with 3.0 mL of glycidyl methacrylate, and then 0.04 g of azobisisobutyronitrile was added. The mixture was subjected to in-situ polymerization at 75 °C and a stirring speed of 450 r / min for 5.5 h. After centrifugation (11000 r / min, 12 min), washing three times with anhydrous ethanol, and vacuum drying at 65 °C for 7 h, the modified inorganic filler was obtained.

[0104] The preparation method of the hyperbranched polyester dispersant includes the following steps: 10g of trimethylolpropane, 55g of 2,2-dimethylolpropionic acid and 0.4g of p-toluenesulfonic acid were mixed and subjected to polycondensation reaction at 145℃, stirring speed of 180r / min and nitrogen protection for 7h to obtain hydroxyl-terminated hyperbranched polyester. 50g of the terminal hydroxyl hyperbranched polyester and 9mL of castor oil fatty acid were mixed and then subjected to esterification reaction at 195℃, stirring speed of 300r / min and nitrogen protection for 3.5h to obtain the hyperbranched polyester dispersant.

[0105] The method for preparing the high-performance ceramic substrate includes the following steps: 930g of alumina, 25g of magnesium oxide, 8g of yttrium oxide, 10g of calcium oxide, 25g of silicon dioxide, 20g of zirconium oxide, 480mL of toluene / anhydrous ethanol mixed solvent (volume ratio 1:1) and 12g of hyperbranched polyester dispersant were mixed and then ball-milled for 42h at a speed of 250r / min using alumina balls (diameter 8mm) as the ball milling medium and a ball-to-material mass ratio of 1:3.5 to obtain a primary slurry. The primary slurry, 100g of polyvinyl butyral, 90g of dibutyl phthalate and 2g of n-butanol were mixed and then subjected to a second ball milling treatment at 250r / min for 30h using alumina balls (8mm in diameter) as the ball milling medium and a material-to-ball mass ratio of 1:3.5 to obtain the secondary slurry. The secondary slurry was mixed with 50g of modified inorganic filler and stirred at 300r / min for 3h to obtain a casting slurry. The casting slurry was subjected to vacuum degassing treatment at a vacuum degree of -0.092MPa for 25 minutes, and then cast on a casting machine with a doctor blade gap of 0.5mm, a casting speed of 1.5m / min, and a drying temperature of 75℃ to obtain a green strip with a thickness of 0.3mm. The green strip is heated to 620°C at a heating rate of 0.8°C / min for debinding treatment and held at that temperature for 3 hours. Then, it is heated to 1650°C at a heating rate of 4°C / min for sintering treatment and held at that temperature for 5 hours. The sintering atmosphere is oxygen, and the strip is cooled in the furnace to obtain the high-performance ceramic substrate.

[0106] The method for protecting metallized trench dry film through exposure etching includes the following steps: Through holes with a diameter of 150μm are machined on the high-performance ceramic substrate using mechanical drilling, with 120 holes per substrate. The substrate is then ultrasonically cleaned and dried. A TiW (0.08 μm) / Au (0.25 μm) seed layer was deposited on both sides of the substrate and the inner wall of the hole using a magnetron sputtering device. Then, Au was electroplated on the whole plate to thicken the coating to a thickness of 1.8 μm, resulting in a coated ceramic substrate. The coated ceramic substrate was placed on a bakelite board and dry film was applied on a laminating machine at a lamination speed of 18 mm / s, an upper roller temperature of 88°C, a lower roller temperature of 88°C, a lamination pressure of 9 N / cm², and a dry film thickness of 20 μm. After lamination, the substrate was removed and rehydrated for 25 min. The laser direct imaging exposure equipment was used for alignment exposure treatment at an exposure dose of 4500mJ, followed by a second water rehydration for 25 minutes after exposure. Remove the top protective film of the dry film, and spray develop it at 42°C for 2.5 min using a developing solution (sodium carbonate concentration of 20%) to obtain a ceramic substrate with the cavity protected by the dry film. The ceramic substrate with the hole grooves protected by the dry film is subjected to patterned outer film etching treatment, and then the film is removed and cleaned to obtain a high-performance ceramic substrate with complete metallized hole grooves.

[0107] Comparative Example 1 This comparative example provides a high-performance ceramic substrate and its preparation method, specifically including the following: The high-performance ceramic substrate comprises, by weight, the following components: 93 parts aluminum oxide, 2.5 parts magnesium oxide, 0.8 parts yttrium oxide, 1.0 part calcium oxide, 2.5 parts silicon dioxide, 2.0 parts zirconium oxide, 5 parts nano silicon carbide, 10 parts polyvinyl butyral, 9 parts dibutyl phthalate, 1.2 parts fish oil, 0.2 parts defoamer, and 48 parts organic solvent; The nano-silicon carbide is unmodified silicon carbide with an average particle size of 35 nm; The fish oil mentioned is commercially available refined fish oil with a viscosity of approximately 50 mPa·s; The remaining components and preparation methods are the same as in Example 3; The preparation method of the high-performance ceramic substrate is the same as that in Example 3.

[0108] Comparative Example 2 This comparative example provides a high-performance ceramic substrate and its preparation method, specifically including the following: The high-performance ceramic substrate comprises, by weight, the following components: 93 parts alumina, 2.5 parts magnesium oxide, 0.8 parts yttrium oxide, 1.0 part calcium oxide, 2.5 parts silicon dioxide, 2.0 parts zirconium oxide, 5 parts modified inorganic filler, 10 parts polyvinyl butyral, 9 parts dibutyl phthalate, 1.2 parts hyperbranched polyester dispersant, 0.2 parts defoamer, and 48 parts organic solvent; The components are the same as those in Example 3; The method for preparing the high-performance ceramic substrate includes the following steps: 930g of alumina, 25g of magnesium oxide, 8g of yttrium oxide, 10g of calcium oxide, 25g of silicon dioxide, 20g of zirconium oxide, 50g of modified inorganic filler, 480mL of toluene / anhydrous ethanol mixed solvent and 12g of hyperbranched polyester dispersant were mixed and ball-milled at 250r / min for 42h using alumina balls as the ball milling medium to obtain a primary slurry. The primary slurry, 100g of polyvinyl butyral, 90g of dibutyl phthalate and 2g of n-butanol were mixed and then ball-milled at 250r / min for 30h to obtain a cast slurry. The subsequent vacuum degassing, casting, debinding, and sintering processes are the same as in Example 3.

[0109] The performance of the high-performance ceramic substrates prepared in Examples 1-3 and Comparative Examples 1-2 was tested, and the test results are shown in Table 1.

[0110] The volume density and compactness detection specifically includes the following steps: Samples with dimensions of 20mm × 20mm were cut from the high-performance ceramic substrates prepared in each embodiment and comparative example. The bulk density was determined using Archimedes' displacement method with deionized water as the test medium and at 23℃. The samples were first dried to constant weight in a 110℃ oven, and the dry weight was measured. Then, the samples were boiled in boiling water for 2 hours to fully absorb water. After cooling, the mass of the saturated sample in air and its buoyant weight in water were measured. The bulk density (g / cm³) was then determined according to the formula. 3 The bulk density is calculated as follows: (dry weight / (mass in saturated air - buoyant weight in water)). The density is then calculated according to the formula: "Bulk density (%) = (bulk density / theoretical density) × 100%". The theoretical density of alumina ceramics is taken as 3.99 g / cm³. 3 Each group of samples shall contain no fewer than 5 samples, and the arithmetic mean shall be taken.

[0111] The bending strength test specifically includes the following steps: Samples with dimensions of 3mm×4mm×40mm were cut from the high-performance ceramic substrates prepared in each embodiment and comparative example. The surface was ground and polished to Ra≤0.2μm, and the edges were chamfered to 0.1mm. Three-point bending tests were performed using a universal testing machine with a lower support span of 30mm and an upper indenter loading rate of 0.5mm / min. The maximum load at which the sample broke was recorded. The bending strength was calculated according to "bending strength (MPa) = 3FL / (2bh²)", where F is the breaking load (N), L is the span of 30mm, b is the sample width of 4mm, and h is the sample thickness of 3mm. There were no fewer than 10 samples in each group, and the arithmetic mean was taken.

[0112] The average grain size detection specifically includes the following steps: After grinding and polishing the cross-sections of the high-performance ceramic substrates prepared in each embodiment and comparative example, they were hot-etched for 30 minutes at a temperature 100°C lower than the sintering temperature. The microstructure was observed using a scanning electron microscope at 2000x magnification. Ten fields of view were randomly photographed, and the grain size was measured using the truncation method. At least 50 grains were counted in each field of view. The average grain size was calculated according to "average grain size = 1.56 × L", where L is the average intercept of the truncation line, and the arithmetic mean of all fields of view was taken.

[0113] The detection of the broken porosity of the metallized slots specifically includes the following steps: The high-performance ceramic substrates of each embodiment and comparative example, which have undergone metallization and etching treatment, were examined one by one using a metallographic microscope at 100x magnification. All metallized vias on each substrate were inspected. The number of vias with missing, broken, or laterally etched metal layers that prevented effective conduction was counted. The via breakage rate was calculated according to "breach rate (%) = number of breaches / total number of metallized vias × 100%". Each group of samples consisted of no less than 10 pieces, and the arithmetic mean was taken.

[0114] Table 1 Performance Test Results The technical solutions provided by the embodiments of this application have been described in detail above. Specific examples have been used to illustrate the principles and implementation methods of this application. The description of the above embodiments is only for the purpose of helping to understand the method and core ideas of this application. At the same time, for those skilled in the art, there will be changes in the specific implementation methods and application scope based on the ideas of this application. Therefore, the content of this specification should not be construed as a limitation of this application.

Claims

1. A high-performance ceramic substrate, characterized in that, The raw materials include the following parts by weight: The composition includes 80-95 parts alumina, 0.5-3 parts magnesium oxide, 0.5-2 parts yttrium oxide, 0.5-3 parts calcium oxide, 0.5-3 parts silicon dioxide, 1-5 parts zirconium oxide, 3-12 parts modified inorganic filler, 8-18 parts polyvinyl butyral, 8-15 parts dibutyl phthalate, 0.5-3 parts hyperbranched polyester dispersant, 0.1-0.5 parts defoamer, and 40-80 parts organic solvent.

2. The high-performance ceramic substrate according to claim 1, characterized in that, The preparation method of the modified inorganic filler includes the following steps: Silicon carbide and anhydrous ethanol were mixed and subjected to ultrasonic treatment to obtain a silicon carbide suspension. The silicon carbide suspension, 3-isocyanate propyltriethoxysilane and water were mixed and stirred at 60~80°C to obtain the initial modified silicon carbide. The modified silicon carbide, glycidyl methacrylate, and azobisisobutyronitrile were mixed and then subjected to in-situ polymerization at 70-90°C to obtain the modified inorganic filler.

3. The high-performance ceramic substrate according to claim 2, characterized in that, The mass-to-volume ratio of silicon carbide to anhydrous ethanol is 1 g:(8~15) mL, and the average particle size of the silicon carbide is 30~100 nm; and / or The ultrasonic treatment has a power of 200-500W, a duration of 30-60 minutes, and a frequency of 20-40kHz; and / or The mass-to-volume ratio of the silicon carbide suspension, 3-isocyanate propyltriethoxysilane, and water is 1 g : (0.1~0.2) mL : (0.02~0.05) mL; and / or The stirring reaction is carried out at a speed of 400-600 r / min for a duration of 4-8 h; and / or The mass-to-volume ratio of the initially modified silicon carbide, glycidyl methacrylate, and azobisisobutyronitrile is 1 g : (0.25~0.5) mL : (0.003~0.008) g; and / or The in-situ polymerization reaction is carried out under stirring conditions, with a stirring speed of 300~500 r / min and a stirring time of 3~6 h.

4. The high-performance ceramic substrate according to claim 1, characterized in that, The preparation method of the hyperbranched polyester dispersant includes the following steps: Trimethylolpropane, 2,2-dimethylolpropionic acid and p-toluenesulfonic acid were mixed and subjected to polycondensation reaction at 140~160℃ to obtain hydroxyl-terminated hyperbranched polyester. The hyperbranched polyester with terminal hydroxyl groups and castor oil fatty acids are mixed and then subjected to esterification reaction at 180~200℃ to obtain the hyperbranched polyester dispersant.

5. The high-performance ceramic substrate according to claim 4, characterized in that, The mass ratio of trimethylolpropane, 2,2-dimethylolpropionic acid, and p-toluenesulfonic acid is 1:5~7:0.03~0.08; and / or The polycondensation reaction is carried out under stirring conditions, wherein the stirring speed is 100~300 r / min and the time is 6~10 h; and / or The mass-to-volume ratio of the terminal hydroxyl hyperbranched polyester to castor oil fatty acids is 1 g : (0.15~0.3) mL; and / or The esterification reaction is carried out under stirring conditions, with a stirring speed of 150~350 r / min and a stirring time of 3~5 h.

6. The high-performance ceramic substrate according to claim 1, characterized in that, The defoamer is selected from one or both of n-butanol or silicone defoamers; and / or The organic solvent is selected from one or both of toluene and anhydrous ethanol.

7. The method for preparing the high-performance ceramic substrate according to any one of claims 1 to 6, characterized in that, Includes the following steps: Alumina, magnesium oxide, yttrium oxide, calcium oxide, silicon dioxide, zirconium oxide, organic solvent and hyperbranched polyester dispersant are mixed and then subjected to a first ball milling process to obtain a primary slurry; The primary slurry, polyvinyl butyral, dibutyl phthalate and defoamer are mixed and then subjected to a second ball milling process to obtain the secondary slurry. The secondary slurry and modified inorganic filler are mixed and stirred to obtain a casting slurry. The casting slurry is subjected to vacuum degassing treatment, and then cast molding treatment is performed to obtain a green tape; The green strip is debonded and then sintered to obtain a high-performance ceramic substrate.

8. The method for preparing a high-performance ceramic substrate according to claim 7, characterized in that, The first ball milling process uses alumina balls as the milling media, the diameter of which is 5-15 mm, and the material-to-ball mass ratio is 1:2-4. The first ball milling process is carried out under stirring conditions, the stirring speed being 200-400 r / min, and the time being 12-48 h; and / or The second ball milling process uses alumina balls as the milling media, the diameter of which is 5-15 mm, and the material-to-ball mass ratio is 1:2-4. The second ball milling process is carried out under stirring conditions, with a stirring speed of 200-400 r / min and a time of 12-36 h; and / or The stirring speed is 200~500 r / min, and the time is 1~4 h; and / or The vacuum degree of the vacuum degassing treatment is -0.08 to -0.095 MPa, and the degassing time is 20 to 60 min; and / or The casting process is performed on a casting machine with a doctor blade gap of 0.3~1.5mm, a casting speed of 0.5~2.0m / min, a drying temperature of 60~100℃, and a green strip thickness of 0.2~1.0mm; and / or The heating rate for the glue removal process is 0.5~2.0℃ / min, the glue removal temperature is 550~650℃, and the holding time is 2~6h; and / or The sintering process involves a heating rate of 3-10℃ / min, a temperature of 1550-1680℃, a time of 2-6 hours, and a sintering atmosphere of air or oxygen.

9. The method for dry film exposure etching protection treatment of metallized vias on high-performance ceramic substrates according to any one of claims 1 to 6, comprising the following steps: Hole and groove processing is performed on the high-performance ceramic substrate. After cleaning, a metal film layer is sputtered to obtain a coated ceramic substrate. The coated ceramic substrate is placed on a bakelite board and dry film is applied. After the film is applied, it is removed and rehydrated. The ceramic substrate with the holes and grooves protected by a dry film is obtained by performing alignment exposure according to the exposure dosage and exposure drawing, followed by secondary rehydration after exposure, and spray development according to the developer solution. The ceramic substrate with the hole grooves protected by the dry film is subjected to patterned outer film etching treatment, and then the film is removed and cleaned to obtain a high-performance ceramic substrate with complete metallized hole grooves.

10. The method for dry film exposure etching protection treatment of metallized trenches on high-performance ceramic substrates according to claim 9, characterized in that, The hole and groove are processed by laser drilling or mechanical drilling, with a hole diameter ranging from 50 to 300 μm; and / or The sputtered metal film is a magnetron sputtered TiW / Au film, wherein the TiW layer has a thickness of 0.08~0.15μm and the Au layer has a thickness of 0.2~0.5μm; and / or The dry film lamination process has a lamination speed of 10~20 mm / s, an upper roller temperature of 85~95℃, a lower roller temperature of 85~95℃, and a lamination pressure of 8~15 N / cm. 2 The dry film thickness used is 15~30μm; and / or The rehydration time is 10-30 minutes; and / or The secondary rehydration time is 10-30 minutes; and / or The exposure dose for the alignment exposure treatment is 3000~5000 mJ; and / or The developing solution for the spray developing process is an aqueous sodium carbonate solution, wherein the mass concentration of sodium carbonate in the developing solution is 14-20%, the developing temperature is 40-50℃, and the developing time is 2-5 min; and / or The dry film is a fully water-soluble photosensitive dry film, comprising a protective film, a substrate film, and a photosensitive resist layer, wherein the photosensitive resist layer contains acrylate photopolymerizable monomers.

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