WO2020237979A1

WO2020237979A1 - Composite ceramic substrate and preparation method therefor

Info

Publication number: WO2020237979A1
Application number: PCT/CN2019/111951
Authority: WO
Inventors: 伍尚华; 聂光临; 黎业华
Original assignee: 广东工业大学
Priority date: 2019-05-24
Filing date: 2019-10-18
Publication date: 2020-12-03
Also published as: CN110092645A; CN110092645B

Abstract

Disclosed are a composite ceramic substrate and a preparation method therefor. The composite ceramic substrate comprises: an inner core layer and equal-thickness surface layers composited on two sides of the inner core layer, wherein the difference between thermal expansion coefficients of the inner core layer and the surface layer is Δα; the thickness of the inner core layer is H; the thickness of the surface layer is h; Δα needs to satisfy a first constraint condition, and the first constraint condition is: Δα is less than a first preconfigured value, Δα is less than a second preconfigured value and Δα is greater than a third preconfigured value; and h/H needs to satisfy a second constraint condition, and the second constraint condition is: h/H is greater than or equal to a fourth preconfigured value and is less than or equal to a fifth preconfigured value. By means of the composite ceramic substrate, the technical defect of existing ceramic substrates of mechanical strength being relatively low and the safety and reliability of an encapsulation component thereof being poor can be overcome.

Description

一种复合陶瓷基板及其制备方法Composite ceramic substrate and preparation method thereof

技术领域Technical field

本申请属于电子信息材料技术领域，尤其涉及一种复合陶瓷基板及其制备方法。This application belongs to the technical field of electronic information materials, and in particular relates to a composite ceramic substrate and a preparation method thereof.

背景技术Background technique

随着电子信息技术的不断发展，电路集成化程度越来越高，导致了电子设备的热流密度逐渐增大；且电子产品逐渐向小型化、便携化、大功率化、高频化方向快速发展，***结构越来越紧凑，这就使得电子设备的散热要求越来越高。此外，散热基板在使用过程中会承受的冷热冲击(Si芯片工作结温150～175℃)所产生的热应力作用，特别是对于高功率器件(例如：绝缘栅双极型晶体管IGBT、大功率LED等)的散热模块，这种热应力的作用更强。With the continuous development of electronic information technology, the degree of circuit integration is getting higher and higher, resulting in the gradual increase of the heat flow density of electronic equipment; and electronic products are gradually developing in the direction of miniaturization, portability, high power, and high frequency. , The system structure is becoming more and more compact, which makes the heat dissipation requirements of electronic equipment higher and higher. In addition, the heat dissipation substrate will withstand the thermal stress caused by the thermal shock (Si chip operating junction temperature 150～175℃) during use, especially for high-power devices (such as insulated gate bipolar transistor IGBT, large Power LED, etc.) heat dissipation module, this kind of thermal stress has a stronger effect.

目前使用较多的陶瓷基板主要是氧化铝、氮化铝和氮化硅陶瓷基板。由于陶瓷基板是典型的脆性材料，其在热应力疲劳作用下的破坏主要表现为突发性的开裂破坏，从而导致电子元器件的破坏与失效，继而易引发灾难性事故。其中氧化铝陶瓷力学、热、电学性能优良，且价格低廉，原料丰富，是目前电子行业中综合性能较好、应用最成熟的陶瓷材料，占陶瓷封装基板总量的90％以上。但是，由于电子设备的冷热冲击所产生的热应力作用，热应力值超过氧化铝陶瓷基板自身的本征抗拉强度时，陶瓷基板会开裂破坏。而由于氧化铝陶瓷强度较低(300～380MPa)，其使用寿命通常较短，例如氧化铝陶瓷基板在-55～150℃的冷热循环试验中，当循环次数>65次时，氧化铝基板即出现开裂破坏。因此，提高氧化铝陶瓷基板的强度可大幅度提高其使用寿命，对保障电子封装构件服役安全性与可靠性具有重要意义。此外，由于电子设备具有较高的散热要求，而氧化铝陶瓷基板的热导率一般为20～30W/(mK)，需要进一步提升氧化铝陶瓷基板的热导率以满足电子信息行业日益增长的散热需求。因此，提升陶瓷基板的力学强度对于确保其封装构件的服役安全性与可靠性至关重要。The ceramic substrates that are currently used more are mainly alumina, aluminum nitride and silicon nitride ceramic substrates. Since the ceramic substrate is a typical brittle material, its damage under the action of thermal stress fatigue is mainly manifested as sudden cracking damage, which leads to the damage and failure of electronic components, and then easily leads to catastrophic accidents. Among them, alumina ceramics have excellent mechanical, thermal and electrical properties, are low in price, and are rich in raw materials. They are currently the most comprehensive and mature ceramic materials in the electronics industry, accounting for more than 90% of the total ceramic packaging substrates. However, due to the thermal stress caused by the thermal shock of the electronic equipment, when the thermal stress exceeds the intrinsic tensile strength of the alumina ceramic substrate itself, the ceramic substrate will be cracked and destroyed. However, due to the low strength of alumina ceramics (300-380MPa), its service life is usually short. For example, in the cold and hot cycle test of -55～150℃ for alumina ceramic substrate, when the number of cycles is >65, the alumina substrate Cracking and destruction occurred. Therefore, increasing the strength of the alumina ceramic substrate can greatly increase its service life, which is of great significance for ensuring the service safety and reliability of electronic packaging components. In addition, because electronic equipment has high heat dissipation requirements, and the thermal conductivity of alumina ceramic substrates is generally 20-30W/(mK), it is necessary to further improve the thermal conductivity of alumina ceramic substrates to meet the growing demand in the electronic information industry. Heat dissipation requirements. Therefore, improving the mechanical strength of the ceramic substrate is very important to ensure the service safety and reliability of its packaging components.

申请内容Application content

本申请提供了一种高强度高导热的复合陶瓷基板，在确保陶瓷基板较高热导率的前提下，可通过层状复合设计提高陶瓷基板的力学强度，有利于提升陶瓷基板封装构件的服役寿命与安全可靠性。The present application provides a composite ceramic substrate with high strength and high thermal conductivity. Under the premise of ensuring high thermal conductivity of the ceramic substrate, the mechanical strength of the ceramic substrate can be improved through a layered composite design, which is beneficial to improve the service life of the ceramic substrate packaging component And safety and reliability.

有鉴于此，本申请提供了一种复合陶瓷基板，包括：In view of this, the present application provides a composite ceramic substrate, including:

内芯层和复合于所述内芯层的两侧的表面层；An inner core layer and surface layers compounded on both sides of the inner core layer;

其中，所述内芯层与所述表面层的热膨胀系数之差为Δα，所述内芯层的厚度为H，所述表面层的厚度为h；Wherein, the difference between the thermal expansion coefficient of the inner core layer and the surface layer is Δα, the thickness of the inner core layer is H, and the thickness of the surface layer is h;

所述Δα同时符合第一约束条件：The Δα also meets the first constraint condition:

所述第一约束条件为：Δα<第一预置数值，且Δα<第二预置数值，且Δα>第三预置数值；The first constraint condition is: Δα<first preset value, and Δα<second preset value, and Δα>third preset value;

所述

符合第二约束条件： Said

Meet the second constraint:

所述第二约束条件为：第四预置数值≤

≤第五预置数值。 The second constraint condition is: the fourth preset value ≤

≤The fifth preset value.

作为优选，所述于第一预置数值为

σ _内芯层为内芯层的弯曲强度；E ₂为内芯层的弹性模量；ΔT为所述复合陶瓷基板的软化温度与室温之差，所述复合陶瓷基板的软化温度为所述复合陶瓷基板的弹性模量开始出现急剧降低的温度点； Preferably, the first preset value is

σ _{inner core layer} is the bending strength of the inner core layer; E ₂ is the elastic modulus of the inner core layer; ΔT is the difference between the softening temperature of the composite ceramic substrate and room temperature, and the softening temperature of the composite ceramic substrate is the composite The elastic modulus of the ceramic substrate begins to show a sharp decrease in temperature;

所述第二预置数值为

σ _表面层为表面层的弯曲强度，σ _内芯层为内芯层的弯曲强度，E ₁为表面层的弹性模量；E ₂为内芯层的弹性模量；ΔT为所述复合陶瓷基板的软化温度与室温之差，所述复合陶瓷基板的软化温度为所述复合陶瓷基板的弹性模量开始出现急剧降低的温度点； The second preset value is

σ _{surface layer} is the bending strength of the surface layer, σ _{inner core layer} is the bending strength of the inner core layer, E ₁ is the elastic modulus of the surface layer; E ₂ is the elastic modulus of the inner core layer; ΔT is the composite ceramic substrate The difference between the softening temperature of the composite ceramic substrate and the room temperature, the softening temperature of the composite ceramic substrate is the temperature point at which the elastic modulus of the composite ceramic substrate begins to decrease sharply;

所述第三预置数值为

σ表面层为表面层的弯曲强度，σ内芯层为内芯层的弯曲强度，E ₁为表面层的弹性模量；E ₂为内芯层的弹性模量；ΔT为所述复合陶瓷基板的软化温度与室温之差，所述复合陶瓷基板的软化温度为所述复合陶瓷基板的弹性模量开始出现急剧降低的温度点。 The third preset value is

σ surface layer is the bending strength of the surface layer, σ inner core layer is the bending strength of the inner core layer, E ₁ is the elastic modulus of the surface layer; E ₂ is the elastic modulus of the inner core layer; ΔT is the composite ceramic substrate The difference between the softening temperature of the composite ceramic substrate and the room temperature, the softening temperature of the composite ceramic substrate is the temperature point at which the elastic modulus of the composite ceramic substrate begins to decrease sharply.

需要说明的是，本申请的内芯层和表面层的材料不受约束，只需要符合以上第一约束条件和第二约束条件即可，本申请的内芯层和表面层的材料可以是现有的材料或者日后发现的新物质。It should be noted that the materials of the inner core layer and the surface layer of the present application are not restricted, and only need to meet the above first and second constraint conditions. The materials of the inner core layer and the surface layer of the present application can be existing Some materials or new substances discovered in the future.

作为优选，所述第四预置数值为

所述第五预置数值为

其中， Preferably, the fourth preset value is

The fifth preset value is

among them,

κ ₁＝4β(E ₁σ _内芯层-E ₁E ₂ΔTΔα)； κ ₁ =4β (E ₁ σ _{inner core layer-} E ₁ E ₂ ΔTΔα);

κ ₂＝2(βE ₁σ _内芯层-βE ₁E ₂ΔTΔα+βE ₂σ _内芯层-E ₁σ _表面层)； κ ₂ = 2 (βE ₁ σ _{inner core layer-} βE ₁ E ₂ ΔTΔα + βE ₂ σ _{inner core layer-} E ₁ σ _{surface layer} );

κ ₃＝βE ₂σ _内芯层-E ₁E ₂ΔTΔα-E ₂σ _表面层； κ ₃ = βE ₂ σ _{inner core layer-} E ₁ E ₂ ΔTΔα-E ₂ σ _{surface layer} ;

其中，σ表面层为表面层的弯曲强度，σ内芯层为内芯层的弯曲强度，E ₁为表面层的弹性模量；E ₂为内芯层的弹性模量；ΔT为所述复合陶瓷基板的软化温度与室温之差，所述复合陶瓷基板的软化温度为所述复合陶瓷基板的弹性模量开始出现急剧降低的温度点；Δα为所述内芯层与所述表面层的热膨胀系数之差；β为所述表面层与所述内芯层的弹性模量之比，β＝E ₁/E ₂；x为表征理论计算与实际实验之间区别的经验参数，其中0<x<0.1。 Wherein, σ surface layer is the bending strength of the surface layer, σ inner core layer is the bending strength of the inner core layer, E ₁ is the elastic modulus of the surface layer; E ₂ is the elastic modulus of the inner core layer; ΔT is the composite The difference between the softening temperature of the ceramic substrate and the room temperature, the softening temperature of the composite ceramic substrate is the temperature point at which the elastic modulus of the composite ceramic substrate begins to decrease sharply; Δα is the thermal expansion of the inner core layer and the surface layer Coefficient difference; β is the ratio of the elastic modulus of the surface layer to the inner core layer, β=E ₁ /E ₂ ; x is an empirical parameter that characterizes the difference between theoretical calculations and actual experiments, where 0<x <0.1.

具体的，x为表征理论计算获得的最优层厚比

与实际实验获得的最优层厚比

之间区别的经验参数。 Specifically, x is the optimal layer thickness ratio obtained by characterizing theoretical calculations

Compared with the best layer thickness obtained by actual experiment

Empirical parameters for the difference between.

需要说明的是，第一预置数值

与第二预置数值

的大小根据内芯层和表面层的材料决定，因此，会存在第一预置数值>第二预置数值，以及第一预置数值<第二预置数值的情况。 It should be noted that the first preset value

And the second preset value

The size of is determined by the materials of the inner core layer and the surface layer. Therefore, there may be situations where the first preset value> the second preset value, and the first preset value <the second preset value.

需要说明的是，所述内芯层可以是多层结构组合的内芯层，也可以是单层结构的内芯层，所述表面层可以是多层结构组合的表面层，也可以是单层结构的表面层，本申请对于内芯层和表面层的层数结构不做具体限定。但内芯层与表面层的热膨胀系数之差与厚度之比必须满足第一约束条件和第二约束条件。It should be noted that the inner core layer may be an inner core layer of a combination of multiple layers, or an inner core layer of a single layer structure, and the surface layer may be a surface layer of a combination of multiple layers, or a single layer. For the surface layer of the layer structure, this application does not specifically limit the layer structure of the inner core layer and the surface layer. However, the ratio of the thermal expansion coefficient difference between the inner core layer and the surface layer to the thickness must satisfy the first constraint condition and the second constraint condition.

作为优选，所述内芯层的两侧的表面层的厚度相等。Preferably, the thicknesses of the surface layers on both sides of the inner core layer are equal.

作为优选，所述的表面层材料为内芯层材料与低膨胀组元混合而制备得到的复合陶瓷。Preferably, the surface layer material is a composite ceramic prepared by mixing an inner core layer material and a low expansion component.

具体的，内芯层材料为陶瓷材料。弯曲强度、弹性模量和软化温度等为陶瓷材料的参数。Specifically, the inner core layer material is a ceramic material. Bending strength, elastic modulus and softening temperature are parameters of ceramic materials.

需要说明的是，低膨胀组元可以是较内芯层主相材料热膨胀系数低的耐高温材料，也可以是耐高温的负膨胀系数材料或零膨胀系数材料。值得注意的是内芯层材料与低膨胀组元应高温环境下不发生化学反应(或生成新物相)，以确保低膨胀组元的掺加可以降低表面层材料的热膨胀系数。It should be noted that the low expansion component can be a high temperature resistant material with a lower thermal expansion coefficient than the main phase material of the inner core layer, or a high temperature resistant negative expansion coefficient material or a zero expansion coefficient material. It is worth noting that the inner core layer material and the low-expansion component should not undergo chemical reactions (or new phases) under high temperature environments to ensure that the addition of the low-expansion component can reduce the thermal expansion coefficient of the surface layer material.

需要说明的是，表面层中低膨胀组元的掺加是为了降低表面层材料的热膨胀系数，从而在烧结完成后于复合陶瓷基板表面引入残余压应力，继而达到预应力增强的目的。且表面层材料中是以内芯层材料为主相，由此可确保表面层与内芯层间的良好界面结合。其中，针对氧化铝、氮化铝、氮化硅陶瓷而言，所述的低膨胀组元分别为氮化铝、氮化硅和金刚石。It should be noted that the addition of low-expansion components in the surface layer is to reduce the thermal expansion coefficient of the surface layer material, so as to introduce residual compressive stress on the surface of the composite ceramic substrate after the sintering is completed, thereby achieving the purpose of pre-stress enhancement. And the inner core layer material is the main phase in the surface layer material, which can ensure a good interface combination between the surface layer and the inner core layer. Among them, for alumina, aluminum nitride, and silicon nitride ceramics, the low-expansion components are aluminum nitride, silicon nitride, and diamond, respectively.

需要说明的是，复合陶瓷基板的内芯层也可以是其他陶瓷基板材料，例如堇青石陶瓷，内芯层的材料可以为堇青石陶瓷混合物，表面层的材料可以为堇青石和石英的复合陶瓷混合物，也可以为堇青石和锂辉石的复合陶瓷混合物，通过现有常规的制备方法制得复合陶瓷基板，可通过在内芯层堇青石陶瓷外侧引入堇青石/石英复相陶瓷或堇青石/锂辉石复相陶瓷，但内芯层与表面层的热膨胀系数之差与厚度之比必须满足第一约束条件和第二约束条件，这可提升堇青石陶瓷的力学强度。It should be noted that the inner core layer of the composite ceramic substrate can also be other ceramic substrate materials, such as cordierite ceramics, the material of the inner core layer can be a cordierite ceramic mixture, and the material of the surface layer can be a composite ceramic of cordierite and quartz The mixture can also be a composite ceramic mixture of cordierite and spodumene. The composite ceramic substrate is prepared by the existing conventional preparation method, and the cordierite/quartz composite ceramic or cordierite can be introduced outside the cordierite ceramic of the inner core layer / Spodumene composite ceramics, but the ratio of the thermal expansion coefficient difference between the inner core layer and the surface layer to the thickness must meet the first and second constraints, which can improve the mechanical strength of cordierite ceramics.

作为优选，所述内芯层的材料选自氧化铝、氮化铝、氮化硅陶瓷中的一种；所述表面层材料分别为氧化铝/氮化铝复合陶瓷、氮化铝/氮化硅复合陶瓷、氮化硅/金刚石复合陶瓷。Preferably, the material of the inner core layer is selected from one of alumina, aluminum nitride, and silicon nitride ceramic; the material of the surface layer is alumina/aluminum nitride composite ceramic, aluminum nitride/nitride Silicon composite ceramics, silicon nitride/diamond composite ceramics.

需要说明的是，所述内芯层的材料为氧化铝陶瓷，所述表面层的材料选自氮化铝和氧化铝的复合陶瓷，氧化铝陶瓷的表面引入热膨胀系数较小的氮化铝/氧化铝复合陶瓷，从而在烧结完成后的降温过程中于复合陶瓷基板的表面引入残余压应力，从而可以大幅度提高复合陶瓷基板的弯曲强度。此外，在氧化铝陶瓷中掺加热导率较高的氮化铝，也可以有效提高复合陶瓷基板的热导率。It should be noted that the material of the inner core layer is alumina ceramic, the material of the surface layer is selected from composite ceramics of aluminum nitride and alumina, and the surface of the alumina ceramic introduces aluminum nitride with a smaller thermal expansion coefficient. Alumina composite ceramics can introduce residual compressive stress on the surface of the composite ceramic substrate during the cooling process after sintering, thereby greatly improving the bending strength of the composite ceramic substrate. In addition, adding aluminum nitride with higher heating conductivity to the alumina ceramic can also effectively improve the thermal conductivity of the composite ceramic substrate.

本申请还提供了一种复合陶瓷基板的制备方法，包括以下步骤：This application also provides a method for preparing a composite ceramic substrate, including the following steps:

步骤1、按照所述的第一约束条件和所述第二约束条件，将氧化铝、烧结助剂A、光敏树脂、分散剂和光引发剂混合，得到的内芯层的氧化铝陶瓷浆料； Step 1. Mix alumina, sintering aid A, photosensitive resin, dispersant, and photoinitiator according to the first constraint condition and the second constraint condition to obtain the alumina ceramic slurry of the inner core layer;

以及，按照所述的第一约束条件和所述第二约束条件，将氮化铝、氧化铝、烧结助剂B、光敏树脂、分散剂和光引发剂混合，得到表面层的氮化铝和氧化铝的复合陶瓷浆料，And, according to the first constraint condition and the second constraint condition, aluminum nitride, aluminum oxide, sintering aid B, photosensitive resin, dispersant, and photoinitiator are mixed to obtain aluminum nitride and oxide on the surface layer. Composite ceramic slurry of aluminum,

步骤2、按照所述的第一约束条件和所述第二约束条件，基于光固化3D打印的制备方法，将所述内芯层的氧化铝陶瓷浆料和所述表面层的氮化铝和氧化铝的复合陶瓷浆料制得复合陶瓷基板的层状坯体，然后经固化、脱脂后进行无压烧结或流动热压烧结，得到复合陶瓷基板。 Step 2. According to the first constraint condition and the second constraint condition, based on the preparation method of photocuring 3D printing, combine the alumina ceramic slurry of the inner core layer and the aluminum nitride of the surface layer with The composite ceramic slurry of alumina is used to prepare the laminated body of the composite ceramic substrate, which is then solidified and degreased and then subjected to pressureless sintering or flow hot pressing sintering to obtain the composite ceramic substrate.

作为优选，所述烧结助剂A选自MgO和稀土氧化物中的一种或多种，所述MgO的掺量为0～0.5wt％，所述烧结助剂A的稀土氧化物的掺量为0～3wt％；Preferably, the sintering aid A is selected from one or more of MgO and rare earth oxides, the content of MgO is 0-0.5wt%, and the content of rare earth oxides of the sintering aid A 0～3wt%;

作为优选，所述的烧结助剂B选自稀土氧化物或稀土氟化物中的一种或多种，所述烧结助剂B的掺量为1～6wt％。Preferably, the sintering aid B is selected from one or more of rare earth oxides or rare earth fluorides, and the content of the sintering aid B is 1 to 6 wt%.

更为优选，所述烧结助剂A的稀土氧化物为Y ₂O ₃。 More preferably, the rare earth oxide of the sintering aid A is Y ₂ O ₃ .

更为优选，所述烧结助剂B的稀土氧化物为Y ₂O ₃，稀土氟化物为YF ₃。 More preferably, the rare earth oxide of the sintering aid B is Y ₂ O ₃ , and the rare earth fluoride is YF ₃ .

具体的，本申请提供的复合陶瓷基板的制备方法为光固化3D打印的制备方法，基于光固化3D打印的制备方法可以制备得到厚度<1mm的复合陶瓷基板，也可以制备得到厚度>1mm的复合陶瓷基板，其制备方法包括以下步骤：Specifically, the preparation method of the composite ceramic substrate provided by the present application is a preparation method of light-curing 3D printing. The preparation method based on light-curing 3D printing can prepare composite ceramic substrates with a thickness of <1mm, or composite ceramic substrates with a thickness of >1mm. The preparation method of the ceramic substrate includes the following steps:

L1：将氧化铝粉与MgO、Y ₂O ₃在乙醇介质中球磨4～24h，然后干燥、研磨、过50～150目筛，造粒制得内芯层Al ₂O ₃粉体，然后，与光敏树脂混合，同时掺加占粉体质量1.5～2.0％的分散剂，球磨混合4～12h之后加入0.1～3％(占光敏树脂质量的百分数)的光引发剂，再次球磨3～10min，制得内芯层的氧化铝陶瓷浆料； L1: Ball mill alumina powder, MgO and Y ₂ O ₃ in ethanol medium for 4-24 hours, then dry, grind, pass through a 50-150 mesh sieve, and granulate to obtain the inner core layer Al ₂ O ₃ powder, then, Mix with photosensitive resin, and at the same time add a dispersant that accounts for 1.5 to 2.0% of the powder mass. After ball milling for 4-12 hours, add 0.1 to 3% (percentage of photosensitive resin mass) of photoinitiator, and ball mill again for 3 to 10 minutes. The alumina ceramic slurry of the inner core layer is prepared;

将氮化铝粉和氧化铝粉和Y ₂O ₃或YF ₃在乙醇介质中球磨4～24h，然后干燥、研磨、过50～150目筛，造粒制得表层Al ₂O ₃/AlN复合粉体，然后，与光敏树脂混合，同时掺加占粉体质量1.5～2.0％的分散剂，球磨混合4～12h之后加入0.1～3％(占光敏树脂质量的百分数)的光引发剂，再次球磨3～10min，制得表面层的氮化铝和氧化铝的复合陶瓷浆料； Ball mill aluminum nitride powder, aluminum oxide powder and Y ₂ O ₃ or YF ₃ in ethanol medium for 4-24 hours, then dry, grind, pass through a 50-150 mesh sieve, and granulate to obtain a surface layer Al ₂ O ₃ /AlN composite The powder is then mixed with the photosensitive resin, and 1.5-2.0% of the powder mass is added at the same time. After ball milling for 4-12 hours, 0.1-3% (percentage of the photosensitive resin) of the photoinitiator is added. Ball mill for 3-10 minutes to prepare a composite ceramic slurry of aluminum nitride and aluminum oxide on the surface layer;

L2：基于紫外光固化面成型技术，利用多物料3D打印机制备层状生坯，紫外光曝光量为4～100mJ/cm ²，打印层厚为10～20μm，单层固化时间为3～15s； L2: based on surface UV-curable molding technique, using a multi-layered material prepared green 3D printer, exposure to UV light in an amount of 4 ~ 100mJ / cm ^2, thickness of the print is 10 ~ 20μm, single curing time is 3 ~ 15s;

L3：将层状生坯置于紫外光灯辐照条件下进行进一步固化，固化时间为4～24h；然后依次进行真空脱脂、空气脱脂，制得层状坯体；L3: Place the layered green body under ultraviolet light irradiation conditions for further curing, and the curing time is 4-24h; then vacuum degreasing and air degreasing are carried out in sequence to obtain the layered green body;

L4：将制得的层状坯体置于石墨模具内，且层状坯体的几何尺寸较石墨模具模腔尺寸小，然后将石墨模具置于热压炉内进行流动热压烧结，烧结完成后即可获得氧化铝基复合陶瓷基板(结构为表面层等厚复合在内芯层的两侧)。L4: Put the prepared layered body in a graphite mold, and the geometric size of the layered body is smaller than that of the graphite mold cavity, and then place the graphite mold in a hot pressing furnace for flow hot pressing sintering, and the sintering is completed Then, the alumina-based composite ceramic substrate (the structure is the surface layer is compounded on both sides of the inner core layer with the same thickness).

对于3D打印制得的氧化铝基复合陶瓷坯体，也可采用无压烧结，即将坯体试样置于石墨模具或氮化硼模具内，置于气氛炉内，在流动氮气气氛下进行高温烧结，可制得氧化铝基复合陶瓷基板。For the alumina-based composite ceramic body produced by 3D printing, pressureless sintering can also be used, that is, the blank sample is placed in a graphite mold or a boron nitride mold, placed in an atmosphere furnace, and subjected to high temperature in a flowing nitrogen atmosphere. Sintering, an alumina-based composite ceramic substrate can be obtained.

更为优选，所述光敏树脂为环氧丙烯酸酯、丙烯酸正丁酯、丙烯酸异辛酯、甲基丙烯酸羟乙酯、甲基丙烯酸羟丙酯、醋酸乙烯酯、乙烯基吡咯烷酮、己二醇二丙烯酸酯、季戊四醇四丙烯酸酯、聚氨酯丙烯酸酯、新戊二醇二丙烯酸酯、二季戊四醇六丙烯酸酯中的一种或几种。More preferably, the photosensitive resin is epoxy acrylate, n-butyl acrylate, isooctyl acrylate, hydroxyethyl methacrylate, hydroxypropyl methacrylate, vinyl acetate, vinylpyrrolidone, hexanediol two One or more of acrylate, pentaerythritol tetraacrylate, urethane acrylate, neopentyl glycol diacrylate, and dipentaerythritol hexaacrylate.

更为优选，所述分散剂为BYK AT204、BYK 9076、BYK 9077、BYK P104S、BYK 110、BYK W9010、SOLSPERSE 8000、SOLSPERSE 17000、SOLSPERSE 24000中的任一种或多种。More preferably, the dispersant is any one or more of BYK AT204, BYK 9076, BYK 9077, BYK P104S, BYK 110, BYK W9010, SOLSPERSE 8000, SOLSPERSE 17000, and SOLSPERSE 24000.

更为优选，所述光引发剂为Darocur 1173、TPO、Irgacure 819、Irgacure 184、Irgacure 127、Irgacure 369、Irgacure 907中的任一种或多种，且光引发剂的吸收波长为250～460nm。More preferably, the photoinitiator is any one or more of Darocur 1173, TPO, Irgacure 819, Irgacure 184, Irgacure 127, Irgacure 369, and Irgacure 907, and the absorption wavelength of the photoinitiator is 250-460 nm.

更为优选，所述内芯层的氧化铝陶瓷浆料与表面层的氮化铝和氧化铝的复合陶瓷浆料的固含量均大于40vol％。More preferably, the solid content of the alumina ceramic slurry of the inner core layer and the composite ceramic slurry of aluminum nitride and alumina on the surface layer are both greater than 40 vol%.

更为优选，所述真空脱脂是将固化完全后的生坯置于真空炉内，以0.5～3℃/min的加热速率升温至400～600℃，其中每间隔100℃保温0.5～2h；真空脱脂完成后，将坯体置于马弗炉内，在空气气氛下进行进一步脱脂除碳，以0.5～3℃/min的加热速率升温至400～500℃，其中每间隔100℃保温0.5～2h。More preferably, the vacuum degreasing is to place the solidified green body in a vacuum furnace, and heat it to 400-600°C at a heating rate of 0.5-3°C/min, and hold the vacuum for 0.5-2h every 100°C; After the degreasing is completed, the green body is placed in a muffle furnace for further degreasing and decarbonization in an air atmosphere. The temperature is raised to 400-500°C at a heating rate of 0.5-3°C/min, and the temperature is kept at every 100°C for 0.5-2h .

更为优选，所述流动热压烧结是将石墨模具(其内放置3D打印制得的层状坯体)置于热压炉内，在氮气气氛下以5～10℃/min升温至1300～1450℃后，开始施加轴向压力，轴向压力为10～50MPa，然后以5～10℃/min升温至1500～1650℃，保温1～4h，进行烧结。More preferably, the flow hot-pressing sintering is to place a graphite mold (with a layered body produced by 3D printing inside) in a hot-pressing furnace, and heat up to 1300-1300°C at 5-10°C/min in a nitrogen atmosphere. After 1450°C, start to apply axial pressure, the axial pressure is 10-50MPa, and then the temperature is raised to 1500-1650°C at 5-10°C/min, and the temperature is kept for 1 to 4 hours for sintering.

更为优选，所述的无压烧结是在气氛炉内进行，在流动氮气气氛下，以5～10℃/min升温至1500～1650℃，保温1～4h，然后随炉冷却，完成烧结。More preferably, the pressureless sintering is carried out in an atmosphere furnace, in a flowing nitrogen atmosphere, the temperature is raised to 1500-1650°C at 5-10°C/min, the temperature is maintained for 1 to 4 hours, and then the furnace is cooled to complete the sintering.

本申请还提供了一种所述复合陶瓷基板的制备方法，所述复合陶瓷基板的厚度>1mm，采用分层铺粉与预压制的方法制备复合陶瓷基板，所述分层铺粉与预压制的方法包括以下步骤：This application also provides a method for preparing the composite ceramic substrate. The thickness of the composite ceramic substrate is greater than 1 mm. The composite ceramic substrate is prepared by a method of layered powder spreading and pre-pressing. The method includes the following steps:

步骤一、按照所述第一约束条件和所述第二约束条件，将氧化铝和烧结助剂C混合，造粒得到的内芯层粉体；Step 1: According to the first constraint condition and the second constraint condition, the inner core layer powder obtained by mixing alumina and sintering aid C to granulate;

以及，按照所述第一约束条件和所述第二约束条件，将氮化铝、氧化铝和烧结助剂D混合，造粒得到表面层粉体，And, according to the first constraint condition and the second constraint condition, aluminum nitride, aluminum oxide, and sintering aid D are mixed and granulated to obtain a surface layer powder,

步骤二、按照所述第一约束条件和所述第二约束条件，基于分层铺粉与预压制的制备方法，将所述内芯层粉体和所述表面层粉体制得复合陶瓷基板的层状坯体，然后烧结可制得复合陶瓷基板。 Step 2. According to the first constraint condition and the second constraint condition, based on the preparation method of layered powder spreading and pre-pressing, the inner core layer powder and the surface layer powder are formed into a composite ceramic substrate. The layered body is then sintered to obtain a composite ceramic substrate.

作为优选，所述烧结助剂C选自MgO和稀土氧化物中的一种或多种，所述MgO的掺量为0～0.5wt％，所述烧结助剂C的稀土氧化物的掺量为0～3wt％；Preferably, the sintering aid C is selected from one or more of MgO and rare earth oxides, the content of MgO is 0-0.5 wt%, and the content of rare earth oxides of the sintering aid C 0～3wt%;

所述烧结助剂D选自稀土氧化物和稀土氟化物中的一种或多种，所述烧结助剂D的掺量为1～6wt％。The sintering aid D is selected from one or more of rare earth oxides and rare earth fluorides, and the content of the sintering aid D is 1 to 6 wt%.

所述的烧结为无压烧结、热压烧结、流动热压烧结中的一种。The sintering is one of pressureless sintering, hot pressing sintering, and flow hot pressing sintering.

具体的，本申请提供的复合陶瓷基板的制备方法为采用分层铺粉与预压制的制备方法，基于分层铺粉与预压制的制备方法可以制备得到厚度>1mm的复合陶瓷基板，其制备方法包括以下步骤：Specifically, the preparation method of the composite ceramic substrate provided in the present application adopts the preparation method of layered powder spreading and pre-pressing. Based on the preparation method of layered powder spreading and pre-pressing, a composite ceramic substrate with a thickness of >1 mm can be prepared. The method includes the following steps:

S1：将氧化铝粉与MgO、Y ₂O ₃在乙醇介质中球磨4～24h，然后干燥、研磨、过50～150目筛，造粒制得内芯层Al ₂O ₃粉体； S1: Ball milling alumina powder, MgO and Y ₂ O ₃ in ethanol medium for 4-24 hours, then drying, grinding, passing through a 50-150 mesh sieve, and granulating to obtain inner core layer Al ₂ O ₃ powder;

S2：将氮化铝粉和氧化铝粉和Y ₂O ₃或YF ₃在乙醇介质中球磨4～24h，然后干燥、研磨、过50～150目筛，造粒制得表面层Al ₂O ₃/AlN复合粉体； S2: Ball milling aluminum nitride powder and aluminum oxide powder and Y ₂ O ₃ or YF ₃ in ethanol medium for 4-24 hours, then drying, grinding, passing through a 50-150 mesh sieve, and granulating to obtain the surface layer Al ₂ O ₃ /AlN composite powder;

S3：称取一定量(质量由表面层与内芯层的厚度比、模具的几何尺寸确定)表面层Al ₂O ₃/AlN复合粉体铺设于石墨模具中，振实均匀后进行预压，预压压力为5～20MPa； S3: Weigh a certain amount (the quality is determined by the thickness ratio of the surface layer to the inner core layer, and the geometric size of the mold). The surface layer Al ₂ O ₃ /AlN composite powder is laid in the graphite mold and pre-compressed after it is evenly vibrated. The preload pressure is 5-20MPa;

S4：称取一定量(质量由表层与内芯层的厚度比、模具的几何尺寸确定)的内芯层Al ₂O ₃粉体铺设于石墨模具中的Al ₂O ₃/AlN预压坯体表面，振实均匀后进行预压，预压压力为5～20MPa； S4: Weigh a certain amount (the quality is determined by the thickness ratio of the surface layer to the inner core layer, and the geometry of the mold) of the inner core layer Al ₂ O ₃ powder and pave the Al ₂ O ₃ /AlN pre-compact body in the graphite mold The surface is pre-compressed after it is evenly vibrated, and the pre-compression pressure is 5-20MPa;

S5：称取与S3相同质量的表面层Al ₂O ₃/AlN复合粉体铺设于石墨模具中Al ₂O ₃预压坯体表面，振实均匀后进行预压，预压压力为5～20MPa； S5: Weigh the surface layer Al ₂ O ₃ /AlN composite powder with the same quality as S3 and lay it on the surface of the Al ₂ O ₃ pre-compacted body in the graphite mold, and pre-compress after it is evenly vibrated. The pre-compression pressure is 5-20 MPa ；

S6：将石墨模具与层状预压坯体置于气氛炉或热压炉内，在氮气气氛下进行烧结。对于无压烧结，在流动氮气下，以5～10℃/min升温至1500～1650℃，保温1～4h，然后随炉冷却，完成烧结；对于热压烧结或流动热压烧结，施加轴向压力为10～50MPa，烧结温度为1500～1650℃，保温时间为1～4h，烧结完成后即可获得氧化铝基复合陶瓷基板(结构为表面层等厚复合在内芯层的两侧)。S6: Place the graphite mold and the layered pre-compacted body in an atmosphere furnace or a hot pressing furnace, and sinter in a nitrogen atmosphere. For pressureless sintering, heat up to 1500-1650°C at 5-10°C/min under flowing nitrogen, keep it for 1 to 4 hours, and then cool with the furnace to complete the sintering; for hot-press sintering or flow hot-press sintering, apply axial The pressure is 10-50MPa, the sintering temperature is 1500-1650°C, and the holding time is 1-4h. After sintering, an alumina-based composite ceramic substrate can be obtained (the structure is that the surface layer is compounded on both sides of the inner core layer with equal thickness).

本申请还提供了一种所述复合陶瓷基板的制备方法，包括以下步骤：The application also provides a method for preparing the composite ceramic substrate, including the following steps:

步骤1、按照所述的第一约束条件和所述第二约束条件，将氮化铝、烧结助剂E、光敏树脂、分散剂和光引发剂混合，得到所述氮化铝陶瓷混合物； Step 1. According to the first constraint condition and the second constraint condition, mix aluminum nitride, sintering aid E, photosensitive resin, dispersant and photoinitiator to obtain the aluminum nitride ceramic mixture;

以及，按照所述的第一约束条件和所述第二约束条件，将氮化铝、氮化硅、烧结助剂F、光敏树脂、分散剂和光引发剂混合，得到所述氮化铝和氮化硅的复合陶瓷混合物；And, according to the first constraint condition and the second constraint condition, aluminum nitride, silicon nitride, sintering aid F, photosensitive resin, dispersant, and photoinitiator are mixed to obtain the aluminum nitride and nitrogen Composite ceramic mixture of silicon dioxide;

步骤2、按照所述的第一约束条件和所述第二约束条件，基于光固化3D打印的制备方法，将所述氮化铝陶瓷混合物和所述氮化铝和氮化硅的复合陶瓷混合物制得复合陶瓷基板的层状坯体，然后经固化、脱脂后进行流动热压烧结，得到复合陶瓷基板。 Step 2. According to the first constraint condition and the second constraint condition, the aluminum nitride ceramic mixture and the composite ceramic mixture of aluminum nitride and silicon nitride are combined based on the preparation method of light curing 3D printing The layered body of the composite ceramic substrate is prepared, and then solidified and degreased and then subjected to flow hot pressing sintering to obtain the composite ceramic substrate.

作为优选，所述烧结助剂E选自稀土氧化物和稀土氟化物中的一种或多种，所述烧结助剂E的掺量为3～6wt％。Preferably, the sintering aid E is selected from one or more of rare earth oxides and rare earth fluorides, and the content of the sintering aid E is 3-6 wt%.

作为优选，所述烧结助剂F选自稀土氧化物和稀土氟化物的一种或多种，所述烧结助剂F的掺量为3～8wt％。Preferably, the sintering aid F is selected from one or more of rare earth oxides and rare earth fluorides, and the content of the sintering aid F is 3-8wt%.

步骤一、按照所述的第一约束条件和所述第二约束条件，将氮化铝和烧结助剂G混合，造粒得到的所述氮化铝陶瓷混合物；Step 1: According to the first constraint condition and the second constraint condition, the aluminum nitride and the sintering aid G are mixed to granulate the aluminum nitride ceramic mixture;

以及，按照所述的第一约束条件和所述第二约束条件，将氮化铝、氮化硅和烧结助剂H混合，造粒得到所述氮化铝和氮化硅的复合陶瓷混合物；And, according to the first constraint condition and the second constraint condition, mixing aluminum nitride, silicon nitride, and a sintering aid H, and granulating to obtain the composite ceramic mixture of aluminum nitride and silicon nitride;

步骤二、按照所述的第一约束条件和所述第二约束条件，基于利用分层铺粉与预压制的制备方法，将氮化铝陶瓷混合物和所述氮化铝和氮化硅的复合陶瓷混合物铺粉干压制得复合陶瓷基板的层状坯体，然后进行热压烧结或流动热压烧结，即可制得复合陶瓷基板。 Step 2. According to the first and second constraints, based on the preparation method of layered powder spreading and pre-pressing, the aluminum nitride ceramic mixture and the aluminum nitride and silicon nitride composite The ceramic mixture is powdered and dry pressed to obtain a layered body of the composite ceramic substrate, and then hot-press sintering or flow hot-press sintering is performed to obtain the composite ceramic substrate.

作为优选，所述烧结助剂G选自稀土氧化物和稀土氟化物中的一种或多种，所述烧结助剂G的掺量为3～6wt％。Preferably, the sintering aid G is selected from one or more of rare earth oxides and rare earth fluorides, and the content of the sintering aid G is 3-6 wt%.

作为优选，所述烧结助剂H选自稀土氧化物、稀土氟化物的一种或多种，所述烧结助剂H的掺量为3～8wt％。Preferably, the sintering aid H is selected from one or more of rare earth oxides and rare earth fluorides, and the content of the sintering aid H is 3-8wt%.

步骤1、按照所述的第一约束条件和所述第二约束条件，将氮化硅、烧结助剂J、光敏树脂、分散剂和光引发剂混合，得到所述氮化硅陶瓷混合物； Step 1. According to the first constraint condition and the second constraint condition, mixing silicon nitride, sintering aid J, photosensitive resin, dispersant and photoinitiator to obtain the silicon nitride ceramic mixture;

以及，按照所述的第一约束条件和所述第二约束条件，将氮化硅、金刚石微粉、烧结助剂K、光敏树脂、分散剂和光引发剂混合，得到所述氮化硅和金刚石的复合陶瓷混合物；And, according to the first constraint condition and the second constraint condition, silicon nitride, diamond powder, sintering aid K, photosensitive resin, dispersant, and photoinitiator are mixed to obtain the silicon nitride and diamond Composite ceramic mixture;

步骤2、按照所述的第一约束条件和所述第二约束条件，基于光固化3D打印的制备方法，将所述氮化硅陶瓷混合物和所述氮化硅和金刚石的复合陶瓷混合物制得复合陶瓷基板的层状坯体，然后经固化、脱脂后进行流动热压烧结，得到复合陶瓷基板。 Step 2. According to the first constraint condition and the second constraint condition, the silicon nitride ceramic mixture and the silicon nitride and diamond composite ceramic mixture are prepared based on the preparation method of light-curing 3D printing The layered body of the composite ceramic substrate is then solidified and degreased and then subjected to flow hot pressing sintering to obtain the composite ceramic substrate.

作为优选，所述烧结助剂J为氧化铝、氧化镁和稀土氧化物组成的复合助剂，所述氧化铝的掺量为0～3wt％，所述氧化镁的掺量为0～3wt％，所述烧结助剂J的稀土氧化物的掺量为3～8wt％。Preferably, the sintering aid J is a composite aid composed of aluminum oxide, magnesium oxide and rare earth oxides, the content of the aluminum oxide is 0-3wt%, and the content of the magnesium oxide is 0-3wt% The content of the rare earth oxide of the sintering aid J is 3-8wt%.

作为优选，所述烧结助剂K为氧化铝、氧化镁、稀土氧化物组成的复合助剂，所述氧化铝的掺量为1～3wt％，所述氧化镁的掺量为0.5～3wt％，所述烧结助剂K的稀土氧化物的掺量为2～6wt％。Preferably, the sintering aid K is a composite aid composed of alumina, magnesia, and rare earth oxides, the content of the alumina is 1 to 3 wt%, and the content of the magnesium oxide is 0.5 to 3 wt% The content of the rare earth oxide of the sintering aid K is 2-6wt%.

步骤一、按照所述的第一约束条件和所述第二约束条件，将氮化硅和烧结助剂M混合，造粒得到所述氮化硅陶瓷混合物；Step 1: According to the first restriction condition and the second restriction condition, mixing silicon nitride and a sintering aid M, and granulating to obtain the silicon nitride ceramic mixture;

以及，按照所述的第一约束条件和所述第二约束条件，将氮化硅、金刚石微粉和烧结助剂N混合，造粒得到所述氮化硅和金刚石的复合陶瓷混合物；And, according to the first constraint condition and the second constraint condition, mixing silicon nitride, diamond fine powder and sintering aid N to granulate to obtain the composite ceramic mixture of silicon nitride and diamond;

步骤二、按照所述的第一约束条件和所述第二约束条件，利用分层铺粉与预压制的制备方法，将所述氮化硅陶瓷混合物和所述氮化硅和金刚石的复合陶瓷混合物铺粉干压制得复合陶瓷基板的层状坯体，然后利用热压烧结或流动热压烧结可制得复合陶瓷基板。Step two, according to the first constraint condition and the second constraint condition, the silicon nitride ceramic mixture and the silicon nitride and diamond composite ceramic are combined by the preparation method of layered powder spreading and pre-pressing The mixture is spread powder and dry pressed to obtain a layered body of the composite ceramic substrate, and then the composite ceramic substrate can be obtained by hot pressing sintering or flow hot pressing sintering.

作为优选，所述烧结助剂M为氧化铝、氧化镁、稀土氧化物组成的复合助剂，所述氧化铝的掺量为0～3wt％，所述氧化镁的掺量为0～3wt％，所述烧结助剂M的稀土氧化物的掺量为3～8wt％。Preferably, the sintering aid M is a composite aid composed of alumina, magnesia and rare earth oxides, the content of the alumina is 0-3wt%, and the content of the magnesium oxide is 0-3wt% The content of the rare earth oxide of the sintering aid M is 3-8wt%.

作为优选，所述烧结助剂N为氧化铝、氧化镁、稀土氧化物组成的复合助剂，所述氧化铝的掺量为1～3wt％，所述氧化镁的掺量为0.5～3wt％，所述烧结助剂N的稀土氧化物的掺量为2～6wt％。Preferably, the sintering aid N is a composite aid composed of alumina, magnesia, and rare earth oxides, the content of the alumina is 1 to 3 wt%, and the content of the magnesium oxide is 0.5 to 3 wt% The content of the rare earth oxide of the sintering aid N is 2-6wt%.

需要说明的是，本申请的复合陶瓷基板的制备方法可以采用流延成型的制备方法(先进行多次流延，再叠片、模切，经干燥、脱脂后才可进行烧结)，也可以采用3D打印制备方法(直接制得层状生坯，经干燥固化、脱脂后即可进行烧结)，这极大地简化了工艺流程；且多层复合陶瓷基板的层厚比设计灵活，易于实现产品的多样化需求，流延成型的制备方法会和3D打印制备方法可以制备任意厚度的复合陶瓷基板，对于厚度>1mm的复合陶瓷基板，还能使用分层铺粉与预压制的制备方法。本申请的复合陶瓷基板的制备方法也可使用未来的新研发的制备方法，只需要内芯层和表面层符合第一约束条件和第二约束条件即可。It should be noted that the preparation method of the composite ceramic substrate of the present application can adopt the preparation method of casting molding (first casting multiple times, then lamination, die cutting, drying and degreasing before sintering), or The 3D printing preparation method is adopted (the layered green body is directly produced, which can be sintered after drying, curing and degreasing), which greatly simplifies the process; and the layer thickness of the multilayer composite ceramic substrate is flexible in design and easy to realize the product For diversified needs, the tape-casting preparation method and 3D printing preparation method can prepare composite ceramic substrates of any thickness. For composite ceramic substrates with a thickness of >1mm, layered powder and pre-pressing preparation methods can also be used. The preparation method of the composite ceramic substrate of the present application can also use a newly developed preparation method in the future, as long as the inner core layer and the surface layer meet the first constraint condition and the second constraint condition.

本申请公开的复合陶瓷基板广泛应用于微电子、功率电子、混合微电子、功率模块等领域。The composite ceramic substrate disclosed in this application is widely used in the fields of microelectronics, power electronics, hybrid microelectronics, power modules and the like.

从以上技术方案可以看出，本申请实施例具有以下优点：It can be seen from the above technical solutions that the embodiments of the present application have the following advantages:

本申请实施例中，提供了一种复合陶瓷基板，本申请的复合陶瓷基板为复相设计，基于预应力强化技术，通过层状复合设计以及计算可知，内芯层和表面层的热膨胀系数之差需要同时符合第一约束条件，且内芯层和表面层的厚度需要符合第二约束条件的复合陶瓷基板具备高强度，由于表面层的热膨胀系数较小，从而在烧结完成后的降温过程中于复合陶瓷基板的表面引入残余压应力，从而可以大幅度提高复合陶瓷基板的弯曲强度；本申请的内芯层和表面层的材料不受约束限制，只要内芯层与表面层的热膨胀系数之差符合第一约束条件，内芯层与表面层的厚度符合第二约束条件，可满足复合陶瓷基板的高强度制备需要，此外，本技术方案可以使用目前主流的流延成型技术制备，也可以使用3D打印技术制备，也可以使用分层铺粉与预压制的方法，也可以使用未来的新的制备方法制备，因此，本申请的复合陶瓷基板的制备可选择性大。In the embodiments of the application, a composite ceramic substrate is provided. The composite ceramic substrate of the application is a composite design. Based on the prestress strengthening technology, through the layered composite design and calculation, it can be known that the thermal expansion coefficient of the inner core layer and the surface layer The difference needs to meet the first constraint condition at the same time, and the thickness of the inner core layer and the surface layer need to meet the second constraint condition. The composite ceramic substrate has high strength. Due to the small thermal expansion coefficient of the surface layer, it will be in the cooling process after sintering. Introducing residual compressive stress on the surface of the composite ceramic substrate can greatly increase the bending strength of the composite ceramic substrate; the materials of the inner core layer and the surface layer of the present application are not restricted, as long as the thermal expansion coefficients of the inner core layer and the surface layer are less than The difference meets the first constraint condition, and the thickness of the inner core layer and the surface layer meets the second constraint condition, which can meet the high-strength preparation requirements of the composite ceramic substrate. In addition, this technical solution can be prepared by the current mainstream tape casting technology, or 3D printing technology is used for preparation, layered powder spreading and pre-pressing methods can also be used, and future new preparation methods can also be used for preparation. Therefore, the preparation of the composite ceramic substrate of the present application can be highly selective.

附图说明Description of the drawings

为了更清楚地说明本申请实施例或现有技术中的技术方案，下面将对实施例或现有技术描述中所需要使用的附图作简单地介绍。In order to more clearly illustrate the technical solutions in the embodiments of the present application or the prior art, the following will briefly introduce the drawings that need to be used in the description of the embodiments or the prior art.

图1为本申请实施例提供的复合陶瓷基板的横截面示意图，其中，1为复合陶瓷基板的表面层，2为复合陶瓷基板的内芯层；其中，复合在所述内芯层2两侧的表面层1的材料相同、厚度相等。Figure 1 is a schematic cross-sectional view of a composite ceramic substrate provided by an embodiment of the application, in which 1 is the surface layer of the composite ceramic substrate, and 2 is the inner core layer of the composite ceramic substrate; wherein the composite is on both sides of the inner core layer 2 The surface layer 1 has the same material and the same thickness.

具体实施方式Detailed ways

本申请提供了一种复合陶瓷基板及其制备方法，在确保陶瓷基板较高热导率的前提下，主要用于解决现有的陶瓷基板存在的力学强度低及其封装构件服役安全性和可靠性差的技术缺陷。The present application provides a composite ceramic substrate and a preparation method thereof. Under the premise of ensuring the high thermal conductivity of the ceramic substrate, it is mainly used to solve the low mechanical strength of the existing ceramic substrate and the poor service safety and reliability of its packaging components. Technical defects.

下面将对本申请实施例中的技术方案进行清楚、完整地描述，显然，所描述的实施例仅仅是本申请一部分实施例，而不是全部的实施例。基于本申请中的实施例，本领域普通技术人员在没有做出创造性劳动前提下所获得的所有其他实施例，都属于本申请保护的范围。The following will clearly and completely describe the technical solutions in the embodiments of the present application. Obviously, the described embodiments are only a part of the embodiments of the present application, rather than all of the embodiments. Based on the embodiments in this application, all other embodiments obtained by those of ordinary skill in the art without creative work fall within the protection scope of this application.

其中，以下实施例所用原料均为市售或自制，以下实施例的单相氧化铝陶瓷为以单一氧化铝为材料按照现有常规的光固化3D打印的制备方法或分层铺粉与预压制的制备方法制备得到的单相氧化铝陶瓷。Among them, the raw materials used in the following examples are all commercially available or self-made. The single-phase alumina ceramics in the following examples use a single alumina as a material according to the existing conventional light-curing 3D printing preparation method or layered powder coating and pre-pressing Single-phase alumina ceramic prepared by the preparation method.

实施例1Example 1

本申请实施例提供第一种复合陶瓷基板，其具体步骤如下：The embodiment of the present application provides the first composite ceramic substrate, and the specific steps are as follows:

a1：内芯层材料制备(Al ₂O ₃造粒)，将96.5重量份的氧化铝、0.5重量份的氧化镁与3重量份的氧化钇加入无水乙醇中，搅拌均匀后超声分散10min，然后置于球磨罐中球磨24h；然后将球磨后的浆料放入旋转蒸发仪，加热温度为60℃，干燥后过150目筛，造粒制得Al ₂O ₃粉体； a1: Preparation of inner core layer material (Al ₂ O ₃ granulation), add 96.5 parts by weight of alumina, 0.5 parts by weight of magnesium oxide and 3 parts by weight of yttrium oxide into absolute ethanol, stir well and ultrasonically disperse for 10 minutes, Then place the ball milled in a ball milling tank for 24 hours; then place the ball milled slurry in a rotary evaporator at a heating temperature of 60°C, and pass through a 150-mesh sieve after drying to obtain Al ₂ O ₃ powder;

a2：表面层材料制备(Al ₂O ₃/AlN造粒)，将81重量份的氧化铝、13重量份的氮化铝与6重量份的氟化钇加入无水乙醇中，搅拌均匀后超声分散10min，然后置于球磨罐中球磨24h；然后将球磨后的浆料放入旋转蒸发仪，加热温度为60℃，干燥后过150目筛，造粒制得Al ₂O ₃/AlN粉体； a2: Preparation of surface layer material (Al ₂ O ₃ /AlN granulation). Add 81 parts by weight of alumina, 13 parts by weight of aluminum nitride and 6 parts by weight of yttrium fluoride into absolute ethanol, stir well and then ultrasonic Disperse for 10 minutes, then place it in a ball milling tank and ball mill for 24 hours; then put the ball milled slurry into a rotary evaporator at a heating temperature of 60°C, and pass through a 150-mesh sieve after drying to obtain Al ₂ O ₃ /AlN powder. ；

a3：确定表层与内芯层层厚比，在流动的氮气气氛下Al ₂O ₃与Al ₂O ₃/AlN对进行烧结，轴向压力为50MPa，烧结温度为1500℃，保温时间为4h，然后降至室温，即可得Al ₂O ₃陶瓷与Al ₂O ₃/AlN陶瓷。分别利用三点弯曲试验与热膨胀仪测试二者的弹性模量、弯曲强度与热膨胀系数(室温～1200℃)。将测试值代入第一约束条件可得内芯层与表面层的热膨胀系数差值Δα需满足0<Δα<0.90×10 ^-6K ^-1，Al ₂O ₃陶瓷热膨胀系数8.5×10 ^-6K ^-1与Al ₂O ₃/AlN陶瓷热膨胀系数8.0×10 ^-6K ^-1之差满足上述要求，即说明Al ₂O ₃/AlN粉体中AlN的掺量是适宜的，将其设置为氧化铝陶瓷的表层材料可以起到增强效果。进一步利用第二约束条件可得最佳层厚比的范围为0.27<h/H<0.47，在此范围内进行上、下表层与内芯层铺粉量的设计。 a3: Determine the thickness ratio of the surface layer to the inner core layer, and sinter the pair of Al ₂ O ₃ and Al ₂ O ₃ /AlN in a flowing nitrogen atmosphere, the axial pressure is 50 MPa, the sintering temperature is 1500 ℃, and the holding time is 4 hours. Then it is lowered to room temperature to obtain Al ₂ O ₃ ceramics and Al ₂ O ₃ /AlN ceramics. The elastic modulus, flexural strength and thermal expansion coefficient of the two were tested by three-point bending test and thermal dilatometer (room temperature ~ 1200℃). Substituting the test value into the first constraint condition, the difference Δα between the thermal expansion coefficient of the inner core layer and the surface layer needs to satisfy 0<Δα<0.90×10 ^-6 K ^-1 , and the thermal expansion coefficient of Al ₂ O ₃ ceramics is 8.5×10 ^-6 K ^{The difference between -1} and Al ₂ O ₃ /AlN ceramic thermal expansion coefficient 8.0×10 ^-6 K ^-1 meets the above requirements, which means that the content of AlN in Al ₂ O ₃ /AlN powder is appropriate, and it is set to oxidation The surface material of aluminum ceramics can play a reinforcing effect. Further using the second constraint condition, the range of the optimal layer thickness ratio can be obtained as 0.27<h/H<0.47, within this range, the design of the powder spreading amount of the upper and lower layers and the inner core layer is carried out.

a4：下表面层铺粉预压，称取4.85g Al ₂O ₃/AlN粉体，并铺设于直径50mm的石墨模具中，振实均匀后进行预压，预压压力为20MPa； a4: Pre-press the lower surface layer with powder, weigh 4.85g Al ₂ O ₃ /AlN powder, and lay it in a graphite mold with a diameter of 50 mm, pre-press after it is evenly tapped, and the pre-compression pressure is 20 MPa;

a5：内芯层铺粉预压，称取13.43g Al ₂O ₃粉体，并铺设于石墨模具中下表层Al ₂O ₃/AlN预压坯体表面，振实均匀后进行预压，预压压力为20MPa； a5: Pour powder for the inner core layer, weigh out 13.43g Al ₂ O ₃ powder, and lay it on the surface of the lower Al ₂ O ₃ /AlN pre-compacted body in the graphite mold, and pre-compact after it is evenly vibrated. The pressure is 20MPa;

a6：上表面层铺粉预压，称取4.85g Al ₂O ₃/AlN粉体，并铺设于石墨模具中内芯层Al ₂O ₃预压坯体表面，振实均匀后进行预压，预压压力为20MPa，预压完成后即制得层状预压坯体； a6: Pour powder on the upper surface layer for pre-compression, weigh 4.85g Al ₂ O ₃ /AlN powder, and lay it on the surface of the inner core Al ₂ O ₃ pre-compressed body in the graphite mold, and pre-compress after it is evenly vibrated. The pre-compression pressure is 20 MPa, and the layered pre-compression body is obtained after the pre-compression is completed;

a7：热压烧结，将上述制得的层状预压坯体与石墨模具置于热压炉内，在流动的氮气气氛下进行烧结，轴向压力为50MPa，烧结温度为1500℃，保温时间为4h，然后降至室温即可制得厚度约为3mm的复合陶瓷基板(结构如图1所示)，即为氧化铝基复合陶瓷基板。a7: Hot-press sintering, the layered pre-compacted body and graphite mold prepared above are placed in a hot-pressing furnace, and sintered in a flowing nitrogen atmosphere, the axial pressure is 50MPa, the sintering temperature is 1500℃, and the holding time For 4 hours, and then lower to room temperature, a composite ceramic substrate with a thickness of about 3 mm can be prepared (the structure is shown in Figure 1), which is an alumina-based composite ceramic substrate.

a8：性能测试。利用光学显微镜测得氧化铝基复合陶瓷基板的上、下表面层厚度均为0.64mm，内芯层厚度约为1.72mm，即表层与内芯层层厚比为0.37；利用三点弯曲试验测得氧化铝基复合陶瓷基板的弯曲强度为505MPa，较单相氧化铝陶瓷的弯曲强度380MPa提高了约32.9％；利用闪光法测得氧化铝基复合陶瓷基板的热导率为33.7W/(m·K)，较氧化铝陶瓷的热导率30W/(m·K)提高了约12.3％。a8: Performance test. The thickness of the upper and lower surface layers of the alumina-based composite ceramic substrate are both 0.64mm measured by an optical microscope, and the thickness of the inner core layer is about 1.72mm, that is, the thickness ratio of the surface layer to the inner core layer is 0.37; measured by a three-point bending test The bending strength of the alumina-based composite ceramic substrate is 505MPa, which is about 32.9% higher than the bending strength of the single-phase alumina ceramic of 380MPa; the thermal conductivity of the alumina-based composite ceramic substrate is 33.7W/(m ·K), which is about 12.3% higher than the thermal conductivity of alumina ceramics of 30W/(m·K).

实施例2Example 2

本申请实施例提供第二种复合陶瓷基板，其具体步骤如下：The embodiment of the present application provides a second composite ceramic substrate, and the specific steps are as follows:

b1：内芯层材料制备(Al ₂O ₃造粒)，将100重量份的氧化铝加入无水乙醇中，搅拌均匀后超声分散10min，然后置于球磨罐中球磨4h；然后将球磨后的浆料放入旋转蒸发仪，加热温度为60℃，干燥后过50目筛，造粒制得Al ₂O ₃粉体； b1: Preparation of the inner core layer material (Al ₂ O ₃ granulation), add 100 parts by weight of alumina to absolute ethanol, stir evenly and ultrasonically disperse for 10 minutes, then place it in a ball milling tank and ball mill for 4 hours; then, the ball milled The slurry is put into a rotary evaporator at a heating temperature of 60°C, dried and passed through a 50-mesh sieve, and granulated to obtain Al ₂ O ₃ powder;

b2：表面层材料制备(Al ₂O ₃/AlN造粒)，将90.6重量份的氧化铝、8.4重量份的氮化铝与1重量份的氧化钇加入无水乙醇中，搅拌均匀后超声分散10min，然后置于球磨罐中球磨4h；然后将球磨后的浆料放入旋转蒸发仪，加热温度为60℃，干燥后过50目筛，造粒制得Al ₂O ₃/AlN粉体； b2: Preparation of surface layer material (Al ₂ O ₃ /AlN granulation), add 90.6 parts by weight of alumina, 8.4 parts by weight of aluminum nitride and 1 part by weight of yttrium oxide into absolute ethanol, stir well and then ultrasonically disperse 10min, then ball milled in a ball mill tank for 4 hours; then put the ball milled slurry into a rotary evaporator, heated at 60℃, dried, passed through a 50-mesh sieve, and granulated to obtain Al ₂ O ₃ /AlN powder;

b3：确定表层与内芯层层厚比，在流动的氮气气氛下Al ₂O ₃与Al ₂O ₃/AlN对进行烧结，轴向压力为10MPa，烧结温度为1650℃，保温时间为1h，然后降至室温，即可得Al ₂O ₃陶瓷与Al ₂O ₃/AlN陶瓷。分别利用三点弯曲试验与热膨胀仪测试二者的弹性模量、弯曲强度与热膨胀系数(室温～1200℃)。将测试值代入第一约束条件可得内芯层与表面层热膨胀系数差值Δα需满足0<Δα<0.86×10 ^-6K ^-1，Al ₂O ₃陶瓷热膨胀系数8.5×10 ^-6K ^-1与Al ₂O ₃/AlN陶瓷热膨胀系数8.2×10 ^-6K ^-1之差满足上述要求，即说明Al ₂O ₃/AlN粉体中AlN的掺量是适宜的，将其设置为氧化铝陶瓷的表面层材料可以起到增强效果。进一步利用第二约束条件可得最佳层厚比的范围为0.12<h/H<0.32，在此范围内进行上、下表面层与内芯层铺粉量的设计。 b3: Determine the thickness ratio of the surface layer to the inner core layer, and sinter the pair of Al ₂ O ₃ and Al ₂ O ₃ /AlN in a flowing nitrogen atmosphere, the axial pressure is 10 MPa, the sintering temperature is 1650 ℃, and the holding time is 1 h. Then it is lowered to room temperature to obtain Al ₂ O ₃ ceramics and Al ₂ O ₃ /AlN ceramics. The elastic modulus, flexural strength and thermal expansion coefficient of the two were tested by three-point bending test and thermal dilatometer (room temperature ~ 1200℃). The test values are substituted into the first constraint can be obtained with the inner core Delta] [alpha coefficients of thermal expansion of the surface layer must satisfy ^{0 <Δα <0.86 × 10 -6} K -1, Al 2 O 3 ceramic thermal expansion coefficient of 8.5 × 10 ^-6 K ^{- 1 The} difference between the thermal expansion coefficient of 8.2×10 ^-6 K ^-1 and Al ₂ O ₃ /AlN ceramic meets the above requirements, which means that the content of AlN in Al ₂ O ₃ /AlN powder is appropriate. Set it to alumina The surface layer material of ceramics can have a reinforcing effect. Further using the second constraint condition, the optimal layer thickness ratio can be obtained in the range of 0.12<h/H<0.32, and the powder spreading amount of the upper and lower surface layers and the inner core layer is designed within this range.

b4：下表面层铺粉预压，称取3.53g Al ₂O ₃/AlN粉体，并铺设于直径50mm的石墨模具中，振实均匀后进行预压，预压压力为5MPa； b4: Pre-press the lower surface layer with powder, weigh 3.53g Al ₂ O ₃ /AlN powder, and place it in a graphite mold with a diameter of 50 mm, and pre-press after it is evenly vibrated. The pre-compression pressure is 5 MPa;

b5：内芯层铺粉预压，称取16.25g Al ₂O ₃粉体，并铺设于石墨模具中下表层Al ₂O ₃/AlN预压坯体表面，振实均匀后进行预压，预压压力为5MPa； b5: Pre-pressing the inner core layer with powder, weighing 16.25g Al ₂ O ₃ powder, and laying it on the surface of the lower Al ₂ O ₃ /AlN pre-compacted body in the graphite mold. The pressure is 5MPa;

b6：上表面层铺粉预压，称取3.53g Al ₂O ₃/AlN粉体，并铺设于石墨模具中内芯层Al ₂O ₃预压坯体表面，振实均匀后进行预压，预压压力为5MPa，预压完成后即制得层状预压坯体； b6: Pre-pressing with powder on the upper surface layer, weighing 3.53g Al ₂ O ₃ /AlN powder, and laying it on the surface of the inner core Al ₂ O ₃ pre-compacted body in the graphite mold, and pre-compacting after being evenly vibrated. The pre-compression pressure is 5 MPa, and the layered pre-compression body is obtained after the pre-compression is completed;

b7：热压烧结，将上述制得的层状预压坯体与石墨模具置于热压炉内，在流动的氮气气氛下进行烧结，轴向压力为10MPa，烧结温度为1650℃，保温时间为1h，然后降至室温即可制得厚度约为3mm的复合陶瓷基板(结构如图1所示)，即为氧化铝基复合陶瓷基板。b7: Hot-press sintering, the layered pre-compacted body and graphite mold prepared above are placed in a hot-pressing furnace, and sintered in a flowing nitrogen atmosphere, the axial pressure is 10MPa, the sintering temperature is 1650°C, and the holding time For 1 hour, and then lower to room temperature, a composite ceramic substrate with a thickness of about 3 mm can be prepared (the structure is shown in Figure 1), which is an alumina-based composite ceramic substrate.

b8：性能测试，利用光学显微镜测得氧化铝基复合陶瓷基板的上、下表面层厚度约为0.46mm，内芯层厚度约为2.08mm，即表面层与内芯层层厚比为0.22；利用三点弯曲试验测得氧化铝基复合陶瓷基板的弯曲强度为487MPa，较单相氧化铝陶瓷的弯曲强度380MPa提高了约28.1％；利用闪光法测得氧化铝基复合陶瓷基板的热导率为31.6W/(m·K)，较单相氧化铝陶瓷的热导率30W/(m·K)提高了约5.3％。b8: Performance test, using an optical microscope to measure the thickness of the upper and lower surface layers of the alumina-based composite ceramic substrate is about 0.46mm, and the thickness of the inner core layer is about 2.08mm, that is, the thickness ratio of the surface layer to the inner core layer is 0.22; The bending strength of the alumina-based composite ceramic substrate measured by the three-point bending test is 487MPa, which is about 28.1% higher than the bending strength of the single-phase alumina ceramic of 380MPa; the thermal conductivity of the alumina-based composite ceramic substrate is measured by the flash method It is 31.6W/(m·K), which is about 5.3% higher than the thermal conductivity of single-phase alumina ceramics of 30W/(m·K).

实施例3Example 3

本申请实施例提供第三种复合陶瓷基板，其具体步骤如下：The embodiment of the present application provides a third composite ceramic substrate, and the specific steps are as follows:

c1：内芯层材料制备(Al ₂O ₃造粒)，将96.5重量份的氧化铝、0.5重量份的氧化镁与3重量份的氧化钇加入无水乙醇中，搅拌均匀后超声分散10min，然后置于球磨罐中球磨24h；然后将球磨后的浆料放入旋转蒸发仪，加热温度为60℃，干燥后过150目筛，造粒制得Al ₂O ₃粉体； c1: Preparation of inner core layer material (Al ₂ O ₃ granulation), add 96.5 parts by weight of alumina, 0.5 parts by weight of magnesium oxide and 3 parts by weight of yttrium oxide to absolute ethanol, stir well and ultrasonically disperse for 10 minutes, Then place the ball milled in a ball milling tank for 24 hours; then place the ball milled slurry in a rotary evaporator at a heating temperature of 60°C, and pass through a 150-mesh sieve after drying to obtain Al ₂ O ₃ powder;

c2：表面层材料制备(Al ₂O ₃/AlN造粒)，将83重量份的氧化铝、11重量份的氮化铝与6重量份的氟化钇加入无水乙醇中，搅拌均匀后超声分散10min，然后置于球磨罐中球磨24h；然后将球磨后的浆料放入旋转蒸发仪，加热温度为60℃，干燥后过150目筛，造粒制得Al ₂O ₃/AlN粉体； c2: Preparation of surface layer material (Al ₂ O ₃ /AlN granulation). Add 83 parts by weight of alumina, 11 parts by weight of aluminum nitride and 6 parts by weight of yttrium fluoride to absolute ethanol, stir well and then ultrasonic Disperse for 10 minutes, then place it in a ball milling tank and ball mill for 24 hours; then put the ball milled slurry into a rotary evaporator at a heating temperature of 60°C, and pass through a 150-mesh sieve after drying to obtain Al ₂ O ₃ /AlN powder. ；

c3：陶瓷浆料制备，将上述制得的75重量份的Al ₂O ₃粉体或Al ₂O ₃/AlN粉体加入25重量份的己二醇二丙烯酸酯，同时加入1.125重量份的BYK AT204后，球磨12h，然后加入0.025重量份的Darocur 1173，再次球磨10min，即可制得Al ₂O ₃浆料与Al ₂O ₃/AlN浆料。所制得的Al ₂O ₃陶瓷浆料的固含量约为42.9vol％，Al ₂O ₃/AlN陶瓷浆料固含量约为43.6vol％。 c3: Preparation of ceramic slurry, adding 75 parts by weight of Al ₂ O ₃ powder or Al ₂ O ₃ /AlN powder prepared above into 25 parts by weight of hexanediol diacrylate, while adding 1.125 parts by weight of BYK After AT204, ball mill for 12 hours, then add 0.025 parts by weight of Darocur 1173, and ball mill again for 10 minutes to prepare Al ₂ O ₃ slurry and Al ₂ O ₃ /AlN slurry. The prepared Al ₂ O ₃ ceramic slurry has a solid content of about 42.9 vol%, and the Al ₂ O ₃ /AlN ceramic slurry has a solid content of about 43.6 vol%.

c4：3D打印成型层状生坯，将上述制得的Al ₂O ₃浆料与Al ₂O ₃/AlN浆料置于多物料3D打印机中，按照预先设计的模型进行光固化打印成型。紫外光光源波长为460nm，曝光量为4mJ/cm ²，打印层厚为10μm，单层固化时间为15s。将打印制得的层状生坯置于紫外光辐照条件下进行进一步固化，辐照时间为4h。 c4: 3D printing and forming a layered green body, placing the Al ₂ O ₃ slurry and Al ₂ O ₃ /AlN slurry prepared above in a multi-material 3D printer, and performing light curing printing and forming according to the pre-designed model. The wavelength of the ultraviolet light source is 460nm, the exposure is 4mJ/cm ² , the printing layer thickness is 10μm, and the single layer curing time is 15s. The printed layered green body is placed under ultraviolet light irradiation conditions for further curing, and the irradiation time is 4h.

c5：真空脱脂，将固化完全后的层状生坯置于真空炉内，以3℃/min升至600℃，其中分别在100℃、200℃、300℃、400℃、500℃、600℃温度下保温0.5h，再以3℃/min降至室温即可完成真空脱脂。c5: Vacuum degreasing, place the cured layered green body in a vacuum furnace and raise it to 600°C at 3°C/min, which are respectively at 100°C, 200°C, 300°C, 400°C, 500°C, and 600°C Keep it at the temperature for 0.5h, then reduce to room temperature at 3℃/min to complete the vacuum degreasing.

c6：空气脱脂，真空脱脂完成后，将坯体置于马弗炉内，在空气气氛下以3℃/min升至500℃，其中分别在100℃、200℃、300℃、400℃、500℃温度下保温0.5h，再以3℃/min降至室温即可完成空气脱脂，制得层状坯体。c6: Air degreasing. After the vacuum degreasing is completed, place the green body in a muffle furnace and raise it to 500°C at 3°C/min in an air atmosphere, which are respectively at 100°C, 200°C, 300°C, 400°C, and 500°C Keep the temperature at ℃ for 0.5h, and then reduce to room temperature at 3℃/min to complete air degreasing to obtain a layered body.

c7：确定表面层与内芯层层厚比，按照GB/T 10700-2006、GB/T 6569-2006、GB/T 16535-2008的试样尺寸要求打印制备Al ₂O ₃与Al ₂O ₃/AlN陶瓷坯体。然后将制得的陶瓷坯体置于石墨模具内，再将石墨模具置于热压炉内，在流动的氮气气氛下，以5℃/min升温至1450℃后，开始施加轴向压力，轴向压力为50MPa，然后再以5℃/min升温至1650℃，保温1h后随炉冷却至室温即可得Al ₂O ₃陶瓷与Al ₂O ₃/AlN陶瓷。分别利用三点弯曲试验与热膨胀仪测试二者的弹性模量、弯曲强度与热膨胀系数(室温～1300℃)。将测试值代入第一约束条件可得内芯层与表层热膨胀系数差值Δα需满足0.04×10 ^-6K ^-1<Δα<0.87×10 ^-6K ^-1，Al ₂O ₃陶瓷热膨胀系数8.4×10 ^-6K ^-1与Al ₂O ₃/AlN陶瓷热膨胀系数8.0×10 ^-6K ^-1之差满足上述要求，即说明Al ₂O ₃/AlN粉体中AlN的掺量是适宜的，将其设置为氧化铝陶瓷的表层材料可以起到增强效果。进一步利用第二约束条件可得最佳层厚比的范围为0.16<h/H<0.36，在此范围内进行上、下表面层与内芯层打印层数的设计。本实施例中设计上、下表面层Al ₂O ₃/AlN的打印层数设置为18层，内芯层Al ₂O ₃的打印层数设置为74层。 c7: Determine the thickness ratio of the surface layer to the inner core layer, and print and prepare Al ₂ O ₃ and Al ₂ O ₃ according to the sample size requirements of GB/T 10700-2006, GB/T 6569-2006, and GB/T 16535-2008 /AlN ceramic body. Then put the prepared ceramic body in a graphite mold, and then place the graphite mold in a hot-pressing furnace. After heating up to 1450°C at 5°C/min under a flowing nitrogen atmosphere, start to apply axial pressure. The pressure is 50MPa, and then the temperature is increased to 1650°C at 5°C/min, and the furnace is cooled to room temperature after holding for 1 hour to obtain Al ₂ O ₃ ceramics and Al ₂ O ₃ /AlN ceramics. The elastic modulus, flexural strength and thermal expansion coefficient (room temperature ~ 1300°C) of the two were tested by a three-point bending test and a thermal expansion meter. Substituting the test value into the first constraint condition, the difference Δα between the thermal expansion coefficient of the inner core layer and the surface layer needs to be 0.04×10 ^-6 K ^-1 <Δα<0.87×10 ^-6 K ^-1 , and the thermal expansion coefficient of Al ₂ O ₃ ceramics is 8.4 The difference between ×10 ^-6 K ^-1 and Al ₂ O ₃ /AlN ceramic thermal expansion coefficient of 8.0 × 10 ^-6 K ^-1 meets the above requirements, which means that the AlN content in Al ₂ O ₃ /AlN powder is appropriate. Setting it as the surface layer material of alumina ceramic can have a reinforcing effect. Further using the second constraint condition, the range of the optimal layer thickness ratio can be obtained as 0.16<h/H<0.36, and the number of printing layers of the upper and lower surface layers and the inner core layer is designed within this range. In this embodiment, the number of printed layers of the upper and lower surface layers Al ₂ O ₃ /AlN is set to 18, and the number of printed layers of the inner core layer Al ₂ O ₃ is set to 74.

c8：流动热压烧结，将制得的层状坯体置于石墨模具内，且坯体的几何尺寸(45mm×5mm或25mm×25mm)较石墨模具模腔尺寸(Φ50mm)小。然后将石墨模具置于热压炉内，在流动的氮气气氛下，以5℃/min升温至1450℃后，开始施加轴向压力，轴向压力为50MPa，然后再以5℃/min升温至1650℃，保温1h后随炉冷却至室温即可制得厚度约为0.8mm的复合陶瓷基板，(结构如图1所示)，即为氧化铝基复合陶瓷基板。c8: Flow hot pressing sintering, the prepared layered body is placed in a graphite mold, and the geometric size of the body (45mm×5mm or 25mm×25mm) is smaller than that of the graphite mold cavity (Φ50mm). Then the graphite mold is placed in the hot pressing furnace, and the temperature is raised to 1450°C at 5°C/min under a flowing nitrogen atmosphere, and then the axial pressure is applied. The axial pressure is 50MPa, and then the temperature is raised to 5°C/min. A composite ceramic substrate with a thickness of about 0.8mm can be obtained by keeping the temperature at 1650°C for 1 hour and then cooling to room temperature in the furnace (the structure is shown in Figure 1), which is an alumina-based composite ceramic substrate.

c9：性能测试，利用光学显微镜测得氧化铝基复合陶瓷基板的上、下表面层厚度约为0.15mm，内芯层厚度约为0.59mm，即表面层与内芯层层厚比为0.26；利用三点弯曲试验结合拟涂层法(参考文献：高秀敏,聂光临,包亦望.拟涂层法评价薄陶瓷基片的弯曲强度及弹性模量[J].陶瓷学报,2018,39(04):463-467)测得氧化铝基复合陶瓷基板的弯曲强度为443MPa，较单相氧化铝陶瓷的弯曲强度355MPa提高了约24.8％；利用闪光法测得氧化铝基复合陶瓷基板的热导率为30.2W/(m·K)，较单相氧化铝陶瓷的热导率28W/(m·K)提高了约7.8％。c9: Performance test, using an optical microscope to measure the thickness of the upper and lower surface layers of the alumina-based composite ceramic substrate is about 0.15mm, and the thickness of the inner core layer is about 0.59mm, that is, the thickness ratio of the surface layer to the inner core layer is 0.26; Using the three-point bending test combined with the pseudo-coating method (Reference: Gao Xiumin, Nie Ling, Bao Yiwang. The pseudo-coating method is used to evaluate the bending strength and elastic modulus of thin ceramic substrates[J].Acta Ceramica Sinica,2018,39( 04):463-467) The measured bending strength of the alumina-based composite ceramic substrate is 443MPa, which is about 24.8% higher than the bending strength of the single-phase alumina ceramic of 355MPa; the thermal of the alumina-based composite ceramic substrate is measured by the flash method. The conductivity is 30.2W/(m·K), which is about 7.8% higher than the thermal conductivity of single-phase alumina ceramics of 28W/(m·K).

实施例4Example 4

本申请实施例提供第四种复合陶瓷基板，其具体步骤如下：The embodiment of the application provides a fourth composite ceramic substrate, and the specific steps are as follows:

d1：内芯层材料制备(Al ₂O ₃造粒)，将99.5重量份的氧化铝与0.5重量份的氧化镁加入无水乙醇中，搅拌均匀后超声分散10min，然后置于球磨罐中球磨24h；然后将球磨后的浆料放入旋转蒸发仪，加热温度为60℃，干燥后过150目筛，造粒制得Al ₂O ₃粉体； d1: Preparation of inner core layer material (Al ₂ O ₃ granulation), add 99.5 parts by weight of alumina and 0.5 parts by weight of magnesium oxide to absolute ethanol, stir uniformly, and ultrasonically disperse for 10 minutes, then place in a ball mill tank 24h; then put the ball-milled slurry into a rotary evaporator at a heating temperature of 60°C, and then pass through a 150-mesh sieve after drying to obtain Al ₂ O ₃ powder by granulation;

d2：表面层材料制备(Al ₂O ₃/AlN造粒)，将80重量份的氧化铝、17重量份的氮化铝与3重量份的氧化钇加入无水乙醇中，搅拌均匀后超声分散10min，然后置于球磨罐中球磨24h；然后将球磨后的浆料放入旋转蒸发仪，加热温度为60℃，干燥后过150目筛，造粒制得Al ₂O ₃/AlN粉体； d2: Preparation of surface layer material (Al ₂ O ₃ /AlN granulation), 80 parts by weight of alumina, 17 parts by weight of aluminum nitride and 3 parts by weight of yttrium oxide are added to absolute ethanol, and the mixture is uniformly stirred and ultrasonically dispersed 10min, then ball mill in a ball milling tank for 24 hours; then put the ball milled slurry into a rotary evaporator at a heating temperature of 60°C, pass through a 150-mesh sieve after drying, and granulate to obtain Al ₂ O ₃ /AlN powder;

d3：陶瓷浆料制备，将上述制得的73重量份的Al ₂O ₃粉体或Al ₂O ₃/AlN粉体加入27重量份的甲基丙烯酸羟丙酯，同时加入1.46重量份的SOLSPERSE8000后，球磨4h，然后加入0.81重量份的Irgacure 127，再次球磨3min，即可制得Al ₂O ₃浆料与Al ₂O ₃/AlN浆料。所制得的Al ₂O ₃陶瓷浆料的固含量约为40.4vol％，Al ₂O ₃/AlN陶瓷浆料固含量约为41.4vol％。 d3: Preparation of ceramic slurry, adding 73 parts by weight of Al ₂ O ₃ powder or Al ₂ O ₃ /AlN powder prepared above into 27 parts by weight of hydroxypropyl methacrylate, while adding 1.46 parts by weight of SOLSPERSE8000 Then, ball mill for 4 hours, then add 0.81 parts by weight of Irgacure 127, and ball mill again for 3 minutes to obtain Al ₂ O ₃ slurry and Al ₂ O ₃ /AlN slurry. The prepared Al ₂ O ₃ ceramic slurry has a solid content of about 40.4 vol%, and the Al ₂ O ₃ /AlN ceramic slurry has a solid content of about 41.4 vol%.

d4：3D打印成型层状生坯，将上述制得的Al ₂O ₃浆料与Al ₂O ₃/AlN浆料置于多物料3D打印机中，按照预先设计的模型进行光固化打印成型。紫外光光源波长为250nm，曝光量为100mJ/cm2，打印层厚为20μm，单层固化时间为3s。将打印制得的层状生坯置于紫外光辐照条件下进行进一步固化，辐照时间为24h。 d4: 3D printing and forming the layered green body, placing the Al ₂ O ₃ slurry and Al ₂ O ₃ /AlN slurry prepared above in a multi-material 3D printer, and performing light-curing printing and forming according to the pre-designed model. The wavelength of the ultraviolet light source is 250nm, the exposure is 100mJ/cm2, the printing layer thickness is 20μm, and the single-layer curing time is 3s. The printed layered green body is placed under ultraviolet light irradiation conditions for further curing, and the irradiation time is 24h.

d5：真空脱脂，将固化完全后的层状生坯置于真空炉内，以0.5℃/min升至400℃，其中分别在100℃、200℃、300℃、400℃温度下保温2h，再以0.5℃/min降至室温即可完成真空脱脂。d5: Vacuum degreasing, place the cured layered green body in a vacuum furnace and raise it to 400℃ at a rate of 0.5℃/min. The temperature is kept at 100℃, 200℃, 300℃, and 400℃ for 2h, and then Vacuum degreasing can be completed by reducing to room temperature at 0.5°C/min.

d6：空气脱脂，真空脱脂完成后，将坯体置于马弗炉内，在空气气氛下以0.5℃/min升至400℃，其中分别在100℃、200℃、300℃、400℃温度下保温2h，再以3℃/min降至室温即可完成空气脱脂，制得层状坯体。d6: Air degreasing. After the vacuum degreasing is completed, place the green body in a muffle furnace and raise it to 400°C at 0.5°C/min in an air atmosphere, which are respectively at 100°C, 200°C, 300°C, and 400°C After keeping the temperature for 2 hours, and then reducing to room temperature at 3°C/min, air degreasing can be completed, and a layered body is obtained.

d7：确定表层与内芯层层厚比，按照GB/T 10700-2006、GB/T 6569-2006、GB/T 16535-2008的试样尺寸要求打印制备Al ₂O ₃与Al ₂O ₃/AlN陶瓷坯体。然后将制得的陶瓷坯体置于石墨模具内，将石墨模具置于热压炉内，在流动的氮气气氛下，以10℃/min升温至1300℃后，开始施加轴向压力，轴向压力为10MPa，然后再以10℃/min升温至1500℃，保温4h后即可得Al2O3陶瓷与Al ₂O ₃/AlN陶瓷。分别利用三点弯曲试验与热膨胀仪测试二者的弹性模量、弯曲强度与热膨胀系数(室温～1300℃)。将测试值代入式(1)可得内芯层与表层热膨胀系数差值Δα需满足0.10×10-6K ^-1<Δα<0.81×10-6K ^-1，Al ₂O ₃陶瓷热膨胀系数8.4×10-6K ^-1与Al ₂O ₃/AlN陶瓷热膨胀系数7.8×10-6K ^-1之差满足上述要求，即说明Al ₂O ₃/AlN粉体中AlN的掺量是适宜的，将其设置为氧化铝陶瓷的表层材料可以起到增强效果。进一步利用式(2)可得最佳层厚比的范围为0.37<h/H<0.57，在此范围内进行上、下表层与内芯层打印层数的设计。本实施例中设计上、下表层Al ₂O ₃/AlN的打印层数设置为9层，内芯层Al2O3的打印层数设置为20层。 d7: Determine the thickness ratio of the surface layer to the inner core layer, and print and prepare Al ₂ O ₃ and Al ₂ O ₃ / according to the sample size requirements of GB/T 10700-2006, GB/T 6569-2006, and GB/T 16535-2008 AlN ceramic body. Then the prepared ceramic body is placed in a graphite mold, the graphite mold is placed in a hot pressing furnace, and the temperature is raised to 1300°C at 10°C/min under a flowing nitrogen atmosphere, and then the axial pressure is applied. The pressure is 10MPa, and then the temperature is increased to 1500°C at 10°C/min, and the Al2O3 ceramics and Al ₂ O ₃ /AlN ceramics can be obtained after holding for 4 hours. The elastic modulus, flexural strength and thermal expansion coefficient (room temperature ~ 1300°C) of the two were tested by a three-point bending test and a thermal expansion meter. Substituting the test value into formula (1), the difference Δα between the thermal expansion coefficient of the inner core layer and the surface layer needs to meet 0.10×10-6K ^-1 <Δα<0.81×10-6K ^-1 , the thermal expansion coefficient of Al ₂ O ₃ ceramics is 8.4×10 The difference between -6K ^-1 and Al ₂ O ₃ /AlN ceramic thermal expansion coefficient of 7.8×10-6K ^-1 satisfies the above requirements, which means that the content of AlN in Al ₂ O ₃ /AlN powder is appropriate. Set it to The surface layer material of alumina ceramic can play a reinforcing effect. Further using formula (2), the range of the optimal layer thickness ratio can be obtained as 0.37<h/H<0.57, and the number of printing layers of the upper and lower layers and the inner core layer is designed within this range. In this embodiment, the number of printed layers of Al ₂ O ₃ /AlN on the upper and lower layers of the design is set to 9 layers, and the number of printed layers of the inner core layer Al ₂ O _{3 is} set to 20 layers.

d8：流动热压烧结，将制得的层状坯体置于石墨模具内，且坯体的几何尺寸(45mm×5mm或25mm×25mm)较石墨模具模腔尺寸(Φ50mm)小。然后将石墨模具置于热压炉内，在流动的氮气气氛下，以10℃/min升温至1300℃后，开始施加轴向压力，轴向压力为10MPa，然后再以10℃/min升温至1500℃，保温4h后随炉冷却至室温即可制得厚度约为0.6mm的复合陶瓷基板(结构如图1所示)，即为氧化铝基复合陶瓷基板。d8: Flow hot pressing sintering, the prepared layered body is placed in a graphite mold, and the geometric size of the body (45mm×5mm or 25mm×25mm) is smaller than that of the graphite mold cavity (Φ50mm). Then the graphite mold is placed in a hot pressing furnace, and the temperature is raised to 1300°C at 10°C/min under a flowing nitrogen atmosphere, and then the axial pressure is applied. The axial pressure is 10MPa, and then the temperature is raised to 10°C/min. A composite ceramic substrate with a thickness of about 0.6 mm (structure as shown in Figure 1) can be prepared after being kept at 1500°C for 4 hours and then cooled to room temperature, which is an alumina-based composite ceramic substrate.

d9：性能测试，利用光学显微镜测得氧化铝基复合陶瓷基板的上、下表面层厚度约为0.15mm，内芯层厚度约为0.31mm，即表面层与内芯层层厚比为0.48；利用三点弯曲试验结合拟涂层法测得氧化铝基复合陶瓷基板的弯曲强度为437MPa，较单相氧化铝陶瓷的弯曲强度355MPa提高了约23.1％；利用闪光法测得氧化铝基复合陶瓷基板的热导率为32.9W/(m·K)，较单相氧化铝陶瓷的热导率28W/(m·K)提高了约17.5％。d9: Performance test, using an optical microscope to measure the thickness of the upper and lower surface layers of the alumina-based composite ceramic substrate is about 0.15mm, and the thickness of the inner core layer is about 0.31mm, that is, the thickness ratio of the surface layer to the inner core layer is 0.48; The bending strength of the alumina-based composite ceramic substrate measured by the three-point bending test combined with the pseudo-coating method is 437MPa, which is about 23.1% higher than the bending strength of the single-phase alumina ceramic of 355MPa; the alumina-based composite ceramic measured by the flash method The thermal conductivity of the substrate is 32.9W/(m·K), which is about 17.5% higher than the thermal conductivity of single-phase alumina ceramics of 28W/(m·K).

实施例5Example 5

本申请实施例提供第五种复合陶瓷基板，其具体步骤如下：The embodiment of the present application provides a fifth composite ceramic substrate, and the specific steps are as follows:

e1：内芯层材料制备(氮化铝造粒)，将95重量份的氮化铝与5重量份的氟化钇加入无水乙醇中，搅拌均匀后超声分散10min，然后置于球磨罐中球磨24h；然后将球磨后的浆料放入旋转蒸发仪，加热温度为60℃，干燥后过150目筛，造粒制得氮化铝粉体；e1: Preparation of inner core layer material (aluminum nitride granulation), add 95 parts by weight of aluminum nitride and 5 parts by weight of yttrium fluoride to absolute ethanol, stir well, and ultrasonically disperse for 10 minutes, then place in a ball mill tank Ball mill for 24 hours; then put the ball milled slurry into a rotary evaporator at a heating temperature of 60°C, pass through a 150-mesh sieve after drying, and granulate to obtain aluminum nitride powder;

e2：表面层材料制备(氮化铝/氮化硅造粒)，将84重量份的氮化铝、10重量份的氮化硅与6重量份的氧化钇加入无水乙醇中，搅拌均匀后超声分散10min，然后置于球磨罐中球磨24h；然后将球磨后的浆料放入旋转蒸发仪，加热温度为60℃，干燥后过150目筛，造粒制得氮化铝/氮化硅复合粉体；e2: Preparation of surface layer material (aluminum nitride/silicon nitride granulation), 84 parts by weight of aluminum nitride, 10 parts by weight of silicon nitride and 6 parts by weight of yttrium oxide are added to absolute ethanol, and after stirring uniformly Disperse ultrasonically for 10 minutes, then place it in a ball milling tank and ball mill for 24 hours; then put the ball milled slurry into a rotary evaporator at a heating temperature of 60°C, and pass through a 150-mesh sieve after drying to obtain aluminum nitride/silicon nitride. Composite powder

e3：陶瓷浆料制备，将上述制得的71重量份的氮化铝粉体或Al ₂O ₃/AlN粉体加入29重量份的甲基丙烯酸羟丙酯，同时加入1.46重量份的SOLSPERSE8000后，球磨4h，然后加入0.81重量份的Irgacure 127，再次球磨3min，即可制得氮化铝浆料与氮化铝/氮化硅复合浆料。所制得的氮化铝陶瓷浆料的固含量约为42.9vol％，氮化铝/氮化硅复合陶瓷浆料固含量约为43.1vol％。 e3: Preparation of ceramic slurry, after adding 71 parts by weight of aluminum nitride powder or Al ₂ O ₃ /AlN powder prepared above into 29 parts by weight of hydroxypropyl methacrylate, and adding 1.46 parts by weight of SOLSPERSE8000 , Ball milling for 4 hours, then adding 0.81 parts by weight of Irgacure 127, ball milling again for 3 minutes, then aluminum nitride slurry and aluminum nitride/silicon nitride composite slurry can be prepared. The solid content of the prepared aluminum nitride ceramic slurry is about 42.9 vol%, and the solid content of the aluminum nitride/silicon nitride composite ceramic slurry is about 43.1 vol%.

e4：3D打印成型层状生坯，将上述制得的氮化铝浆料与氮化铝/氮化硅复合浆料置于多物料3D打印机中，按照预先设计的模型进行光固化打印成型。紫外光光源波长为250nm，曝光量为100mJ/cm ²，打印层厚为20μm，单层固化时间为3s。将打印制得的层状生坯置于紫外光辐照条件下进行进一步固化，辐照时间为6h。 e4: 3D printing and forming a layered green body, placing the aluminum nitride slurry and aluminum nitride/silicon nitride composite slurry prepared above in a multi-material 3D printer, and performing light curing printing and molding according to the pre-designed model. UV light source wavelength is 250nm, the exposure amount of 100mJ / cm ^2, the print layer thickness of 20μm, a cured monolayer and 3s. The printed layered green body is placed under ultraviolet light irradiation conditions for further curing, and the irradiation time is 6 hours.

e5：真空脱脂，将固化完全后的层状生坯置于真空炉内，以0.5℃/min升至400℃，其中分别在100℃、200℃、300℃、400℃温度下保温2h，再以0.5℃/min降至室温即可完成真空脱脂。e5: Vacuum degreasing, place the cured layered green body in a vacuum furnace and raise it to 400℃ at a rate of 0.5℃/min, and keep it at 100℃, 200℃, 300℃ and 400℃ for 2h, and then Vacuum degreasing can be completed by reducing to room temperature at 0.5°C/min.

e6：空气脱脂，真空脱脂完成后，将坯体置于马弗炉内，在空气气氛下以0.5℃/min升至400℃，其中分别在100℃、200℃、300℃、400℃温度下保温2h，再以3℃/min降至室温即可完成空气脱脂，制得层状坯体。e6: Air degreasing. After the vacuum degreasing is completed, place the green body in a muffle furnace and raise it to 400°C at 0.5°C/min in an air atmosphere, which are respectively at 100°C, 200°C, 300°C, and 400°C After keeping the temperature for 2 hours, and then reducing to room temperature at 3°C/min, air degreasing can be completed, and a layered body is obtained.

e7：确定表层与内芯层层厚比，按照GB/T 10700-2006、GB/T 6569-2006、GB/T 16535-2008的试样尺寸要求打印制备氮化铝与氮化铝/氮化硅复合陶瓷坯体。然后将制得的陶瓷坯体置于石墨模具内，将石墨模具置于热压炉内，在流动的氮气气氛下，以10℃/min升温至1300℃后，开始施加轴向压力，轴向压力为10MPa，然后再以10℃/min升温至1800℃，保温4h后即可得氮化铝陶瓷与氮化铝/氮化硅复相陶瓷。分别利用三点弯曲试验与热膨胀仪测试二者的弹性模量、弯曲强度与热膨胀系数(室温～1200℃)。将测试值代入式(1)可得内芯层与表层热膨胀系数差值Δα需满足0<Δα<0.60×10 ^-6K ^-1，氮化铝陶瓷热膨胀系数4.6×10 ^-6K ^-1与氮化铝/氮化硅复相陶瓷热膨胀系数4.4×10 ^-6K ^-1之差满足上述要求，即说明氮化铝/氮化硅复合粉体中氮化硅的掺量是适宜的，将其设置为氮化铝陶瓷的表层材料可以起到增强效果。进一步利用式(2)可得最佳层厚比的范围为0.13<h/H<0.33，在此范围内进行上、下表层与内芯层打印层数的设计。本实施例中设计上、下表层氮化铝/氮化硅的打印层数设置为24层，内芯层氮化铝的打印层数设置为102层。 e7: Determine the thickness ratio of the surface layer to the inner core layer, and print and prepare aluminum nitride and aluminum nitride/nitride according to the sample size requirements of GB/T 10700-2006, GB/T 6569-2006, and GB/T 16535-2008 Silicon composite ceramic body. Then the prepared ceramic body is placed in a graphite mold, the graphite mold is placed in a hot pressing furnace, and the temperature is raised to 1300°C at 10°C/min under a flowing nitrogen atmosphere, and then the axial pressure is applied. The pressure is 10MPa, and then the temperature is raised to 1800°C at 10°C/min, and the aluminum nitride ceramics and aluminum nitride/silicon nitride composite ceramics can be obtained after holding for 4 hours. The elastic modulus, flexural strength and thermal expansion coefficient of the two were tested by three-point bending test and thermal dilatometer (room temperature ~ 1200℃). Substituting the test value into formula (1), the difference Δα between the thermal expansion coefficient of the inner core layer and the surface layer needs to satisfy 0<Δα<0.60×10 ^-6 K ^-1 , and the thermal expansion coefficient of aluminum nitride ceramics is 4.6×10 ^-6 K ^-1 and The difference in thermal expansion coefficient of aluminum nitride/silicon nitride composite ceramics of 4.4×10 ^-6 K ^-1 meets the above requirements, which means that the content of silicon nitride in the aluminum nitride/silicon nitride composite powder is appropriate. The surface layer material set as aluminum nitride ceramic can play a reinforcing effect. Further using formula (2), the range of the optimal layer thickness ratio can be obtained as 0.13<h/H<0.33, and the design of the number of printing layers of the upper and lower layers and the inner core layer is carried out within this range. In this embodiment, the number of printed layers of aluminum nitride/silicon nitride on the lower and lower layers is set to 24, and the number of printed layers of aluminum nitride for the inner core layer is set to 102 layers.

e8：流动热压烧结，将制得的层状坯体置于石墨模具内，且坯体的几何尺寸(45mm×5mm或25mm×25mm)较石墨模具模腔尺寸(Φ50mm)小。然后将石墨模具置于热压炉内，在流动的氮气气氛下，以10℃/min升温至1300℃后，开始施加轴向压力，轴向压力为10MPa，然后再以10℃/min升温至1800℃，保温4h后随炉冷却至室温即可制得厚度约为3mm的复合陶瓷基板(结构如图1所示)，即为氮化铝基复合陶瓷基板。e8: Flow hot pressing sintering, place the prepared layered blank in a graphite mold, and the geometric size of the blank (45mm×5mm or 25mm×25mm) is smaller than the graphite mold cavity size (Φ50mm). Then the graphite mold is placed in a hot pressing furnace, and the temperature is raised to 1300°C at 10°C/min under a flowing nitrogen atmosphere, and then the axial pressure is applied. The axial pressure is 10MPa, and then the temperature is raised to 10°C/min. After being kept at 1800°C for 4 hours and then cooled to room temperature with the furnace, a composite ceramic substrate with a thickness of about 3 mm (structure as shown in Figure 1) can be prepared, which is an aluminum nitride-based composite ceramic substrate.

e9：性能测试，利用光学显微镜测得氧化铝基复合陶瓷基板的上、下表面层厚度约为0.48mm，内芯层厚度约为2.04mm，即表面层与内芯层层厚比为0.24；利用三点弯曲试验测得氮化铝基复合陶瓷基板的弯曲强度为462MPa，较单相氮化铝陶瓷的弯曲强度350MPa提高了约32.0％。e9: Performance test, using an optical microscope to measure the thickness of the upper and lower surface layers of the alumina-based composite ceramic substrate to be about 0.48mm, and the thickness of the inner core layer to be about 2.04mm, that is, the thickness ratio of the surface layer to the inner core layer is 0.24; Using a three-point bending test, the bending strength of the aluminum nitride-based composite ceramic substrate is 462MPa, which is about 32.0% higher than the 350MPa single-phase aluminum nitride ceramic.

实施例6Example 6

本申请实施例提供第六种复合陶瓷基板，其具体步骤如下：The embodiment of the present application provides a sixth composite ceramic substrate, and the specific steps are as follows:

f1：内芯层材料制备(氮化硅造粒)，将92重量份的氮化硅、3重量份的氧化镁与5重量份的氧化钇加入无水乙醇中，搅拌均匀后超声分散10min，然后置于球磨罐中球磨24h；然后将球磨后的浆料放入旋转蒸发仪，加热温度为60℃，干燥后过150目筛，造粒制得氮化硅粉体；f1: Preparation of inner core layer material (silicon nitride granulation), add 92 parts by weight of silicon nitride, 3 parts by weight of magnesium oxide and 5 parts by weight of yttrium oxide into absolute ethanol, stir well and ultrasonically disperse for 10 minutes, Then place the ball milled in a ball milling tank for 24 hours; then place the ball milled slurry in a rotary evaporator at a heating temperature of 60°C, and pass through a 150-mesh sieve after drying to obtain silicon nitride powder by granulation;

f2：表面层材料制备(氮化硅/金刚石造粒)，将87重量份的氮化硅、5重量份的金刚石微粉、1重量份的氧化铝、2重量份的氧化镁与5重量份的氧化钇加入无水乙醇中，搅拌均匀后超声分散10min，然后置于球磨罐中球磨24h；然后将球磨后的浆料放入旋转蒸发仪，加热温度为60℃，干燥后过150目筛，造粒制得氮化硅/金刚石粉体；f2: Preparation of surface layer material (silicon nitride/diamond granulation), 87 parts by weight of silicon nitride, 5 parts by weight of diamond powder, 1 part by weight of alumina, 2 parts by weight of magnesium oxide and 5 parts by weight of The yttrium oxide was added to absolute ethanol, stirred uniformly, and dispersed ultrasonically for 10 minutes, and then placed in a ball milling tank for ball milling for 24 hours; then the ball milled slurry was placed in a rotary evaporator at a heating temperature of 60°C, dried and passed through a 150-mesh sieve. Granulation to obtain silicon nitride/diamond powder;

f3：确定表层与内芯层层厚比，在氮气气氛下对氮化硅与氮化硅/金刚石粉体进行热压烧结，轴向压力为50MPa，烧结温度为1700℃，保温时间为4h，然后降至室温，即可得氮化硅陶瓷与氮化硅/金刚石复相陶瓷。分别利用三点弯曲试验与热膨胀仪测试二者的弹性模量、弯曲强度与热膨胀系数(室温～1200℃)。将测试值代入第一约束条件可得内芯层与表面层的热膨胀系数差值Δα需满足0.07×10 ^-6K ^-1<Δα<1.74×10 ^-6K ^-1，氮化硅陶瓷热膨胀系数2.8×10 ^-6K ^-1与氮化硅/金刚石复相陶瓷热膨胀系数2.6×10 ^-6K ^-1之差满足上述要求，即说明氮化硅/金刚石粉体中金刚石的掺量是适宜的，将其设置为氮化硅陶瓷的表层材料可以起到增强效果。进一步利用第二约束条件可得最佳层厚比的范围为0<h/H<0.14，在此范围内进行上、下表层与内芯层铺粉量的设计。 f3: Determine the thickness ratio of the surface layer to the inner core layer, hot-press sintering silicon nitride and silicon nitride/diamond powder in a nitrogen atmosphere, the axial pressure is 50MPa, the sintering temperature is 1700°C, and the holding time is 4h. Then it is lowered to room temperature to obtain silicon nitride ceramic and silicon nitride/diamond composite ceramic. The elastic modulus, flexural strength and thermal expansion coefficient of the two were tested by three-point bending test and thermal dilatometer (room temperature ~ 1200℃). Substituting the test value into the first constraint condition, the difference Δα between the thermal expansion coefficient of the inner core layer and the surface layer must satisfy 0.07×10 ^-6 K ^-1 <Δα<1.74×10 ^-6 K ^-1 , the thermal expansion coefficient of silicon nitride ceramics The difference between 2.8×10 ^-6 K ^-1 and the thermal expansion coefficient of silicon nitride/diamond composite ceramics of 2.6×10 ^-6 K ^-1 meets the above requirements, which means that the content of diamond in silicon nitride/diamond powder is appropriate , Setting it as the surface material of silicon nitride ceramic can play a strengthening effect. Further using the second constraint condition, the optimal layer thickness ratio can be obtained in the range of 0<h/H<0.14, and the powder spreading amount of the upper and lower layers and the inner core layer is designed within this range.

f4：下表面层铺粉预压，称取0.70g氮化硅/金刚石复合粉体，并铺设于直径50mm的石墨模具中，振实均匀后进行预压，预压压力为20MPa；f4: Pre-pressing the lower surface layer with powder, weighing 0.70g of silicon nitride/diamond composite powder, and laying it in a graphite mold with a diameter of 50mm, pre-pressing after being evenly tapped, the pre-pressing pressure is 20MPa;

f5：内芯层铺粉预压，称取17.35g氮化硅粉体，并铺设于石墨模具中下表层氮化硅/金刚石预压坯体表面，振实均匀后进行预压，预压压力为20MPa；f5: Pre-pressing the inner core layer with powder, weighing 17.35g silicon nitride powder, and laying it on the surface of the lower silicon nitride/diamond pre-compacted body in the graphite mold, pre-compacting after vibrating, and pre-pressing pressure 20MPa;

f6：上表面层铺粉预压，称取0.70g氮化硅/金刚石复合粉体，并铺设于石墨模具中内芯层氮化硅预压坯体表面，振实均匀后进行预压，预压压力为20MPa，预压完成后即制得层状预压坯体；f6: Pre-pressing with powder on the upper surface layer, weighing 0.70g of silicon nitride/diamond composite powder, and laying it on the surface of the inner core layer of silicon nitride pre-compacted body in the graphite mold, and pre-compacting after being evenly tapped. The pressing pressure is 20MPa, and the layered pre-compacted body will be obtained after the pre-pressing is completed;

f7：热压烧结，将上述制得的层状预压坯体与石墨模具置于热压炉内，在流动的氮气气氛下进行烧结，轴向压力为50MPa，烧结温度为1700℃，保温时间为4h，然后降至室温即可制得厚度约为3mm的复合陶瓷基板(结构如图1所示)，即为氮化硅基复合陶瓷基板。f7: Hot-press sintering, the layered pre-compacted body and graphite mold prepared above are placed in a hot-pressing furnace, and sintered in a flowing nitrogen atmosphere, the axial pressure is 50MPa, the sintering temperature is 1700℃, and the holding time For 4 hours, and then lower to room temperature, a composite ceramic substrate with a thickness of about 3 mm (structure shown in Figure 1) can be prepared, which is a silicon nitride-based composite ceramic substrate.

f8：性能测试。利用光学显微镜测得氧化铝基复合陶瓷基板的上、下表面层厚度均为0.11mm，内芯层厚度约为2.78mm，即表层与内芯层层厚比为0.04；利用三点弯曲试验测得氮化硅基复合陶瓷基板的弯曲强度为862MPa，较单相氮化硅陶瓷的弯曲强度805MPa提高了约7.1％；利用闪光法测得氮化硅基复合陶瓷基板的热导率为70.3W/(m·K)，与单相氮化硅陶瓷的热导率71.5W/(m·K)相近。f8: performance test. The thickness of the upper and lower surface layers of the alumina-based composite ceramic substrate were measured by an optical microscope as 0.11mm, and the thickness of the inner core layer was about 2.78mm, that is, the thickness ratio of the surface layer to the inner core layer was 0.04; the three-point bending test was used to measure The bending strength of the silicon nitride-based composite ceramic substrate is 862MPa, which is about 7.1% higher than the bending strength of the single-phase silicon nitride ceramic of 805MPa; the thermal conductivity of the silicon nitride-based composite ceramic substrate is 70.3W measured by the flash method /(m·K), which is similar to the thermal conductivity of single-phase silicon nitride ceramics of 71.5W/(m·K).

本申请的说明书及上述附图中的术语“第一”、“第二”、“第三”、“第四”等(如果存在)是用于区别类似的对象，而不必用于描述特定的顺序或先后次序。应该理解这样使用的数据在适当情况下可以互换，以便这里描述的本申请的实施例例如能够以除了在这里图示或描述的那些以外的顺序实施。此外，术语“包括”和“具有”以及他们的任何变形，意图在于覆盖不排他的包含，例如，包含了一系列步骤或单元的过程、方法、***、产品或设备不必限于清楚地列出的那些步骤或单元，而是可包括没有清楚地列出的或对于这些过程、方法、产品或设备固有的其它步骤或单元。The terms “first”, “second”, “third”, “fourth”, etc. (if any) in the specification of this application and the above-mentioned drawings are used to distinguish similar objects, and are not necessarily used to describe specific Order or precedence. It should be understood that the data used in this way can be interchanged under appropriate circumstances, so that the embodiments of the present application described herein, for example, can be implemented in a sequence other than those illustrated or described herein. In addition, the terms "including" and "having" and any variations of them are intended to cover non-exclusive inclusions. For example, a process, method, system, product or device that includes a series of steps or units is not necessarily limited to the clearly listed Those steps or units may include other steps or units that are not clearly listed or are inherent to these processes, methods, products, or equipment.

以上所述仅是本申请的优选实施方式，应当指出，对于本技术领域的普通技术人员来说，在不脱离本申请原理的前提下，还可以做出若干改进和润饰，这些改进和润饰也应视为本申请的保护范围。The above are only the preferred embodiments of this application. It should be pointed out that for those of ordinary skill in the art, without departing from the principle of this application, several improvements and modifications can be made, and these improvements and modifications are also Should be regarded as the scope of protection of this application.

Claims

一种复合陶瓷基板，其特征在于，包括：内芯层和复合于所述内芯层的两侧的等厚表面层；A composite ceramic substrate, which is characterized by comprising: an inner core layer and a surface layer of equal thickness compounded on both sides of the inner core layer;

其中，所述内芯层与所述表面层的热膨胀系数之差为Δα，所述内芯层的厚度为H，所述表面层的厚度为h；Wherein, the difference between the thermal expansion coefficient of the inner core layer and the surface layer is Δα, the thickness of the inner core layer is H, and the thickness of the surface layer is h;

所述Δα同时符合第一约束条件：The Δα also meets the first constraint condition:

所述第一约束条件为：Δα<第一预置数值，且Δα<第二预置数值，且Δα>第三预置数值；The first constraint condition is: Δα<first preset value, and Δα<second preset value, and Δα>third preset value;

所述
符合第二约束条件： Said
Meet the second constraint:

所述第二约束条件为：
The second constraint condition is:
根据权利要求1所述的复合陶瓷基板，其特征在于，所述于第一预置数值为
σ _内芯层为内芯层的弯曲强度；E ₂为内芯层的弹性模量；ΔT为所述复合陶瓷基板的软化温度与室温之差，所述复合陶瓷基板的软化温度为所述复合陶瓷的弹性模量开始出现急剧降低的温度点； The composite ceramic substrate of claim 1, wherein the first preset value is
σ _{inner core layer} is the bending strength of the inner core layer; E ₂ is the elastic modulus of the inner core layer; ΔT is the difference between the softening temperature of the composite ceramic substrate and room temperature, and the softening temperature of the composite ceramic substrate is the composite The elastic modulus of ceramics begins to show a sharp decrease in temperature;

所述第二预置数值为
σ _表面层为表面层的弯曲强度，σ _内芯层为内芯层的弯曲强度，E ₁为表面层的弹性模量；E ₂为内芯层的弹性模量；ΔT为所述复合陶瓷基板的软化温度与室温之差，所述复合陶瓷基板的软化温度为所述复合陶瓷的弹性模量开始出现急剧降低的温度点； The second preset value is
σ _{surface layer} is the bending strength of the surface layer, σ _{inner core layer} is the bending strength of the inner core layer, E ₁ is the elastic modulus of the surface layer; E ₂ is the elastic modulus of the inner core layer; ΔT is the composite ceramic substrate The difference between the softening temperature of the composite ceramic substrate and the room temperature, the softening temperature of the composite ceramic substrate is the temperature point at which the elastic modulus of the composite ceramic begins to decrease sharply;

所述第三预置数值为
σ _表面层为表面层的弯曲强度，σ _内 _芯层为内芯层的弯曲强度，E ₁为表面层的弹性模量；E ₂为内芯层的弹性模量；ΔT为所述复合陶瓷基板的软化温度与室温之差，所述复合陶瓷基板的软化温度为所述复合陶瓷的弹性模量开始出现急剧降低的温度点。 The third preset value is
σ _{surface layer} is the bending strength of the surface layer, σ _inner _{core layer} is the bending strength of the inner core layer, E ₁ is the elastic modulus of the surface layer; E ₂ is the elastic modulus of the inner core layer; ΔT is the composite ceramic substrate The difference between the softening temperature of the composite ceramic substrate and the room temperature, the softening temperature of the composite ceramic substrate is the temperature point at which the elastic modulus of the composite ceramic begins to decrease sharply.
根据权利要求1所述的复合陶瓷基板，其特征在于，所述第四预置数值为
所述第五预置数值为
其中κ ₁＝4β(E ₁σ _内芯层-E ₁E ₂ΔTΔα)； The composite ceramic substrate of claim 1, wherein the fourth preset value is
The fifth preset value is
Where κ ₁ = 4β (E ₁ σ _{inner core layer-} E ₁ E ₂ ΔTΔα);

κ ₂＝2(βE ₁σ _内芯层-βE ₁E ₂ΔTΔα+βE ₂σ _内芯层-E ₁σ _表面层)； κ ₂ = 2 (βE ₁ σ _{inner core layer-} βE ₁ E ₂ ΔTΔα + βE ₂ σ _{inner core layer-} E ₁ σ _{surface layer} );

κ ₃＝βE ₂σ _内芯层-E ₁E ₂ΔTΔα-E ₂Δ _表面层； κ ₃ = βE ₂ σ _{inner core layer-} E ₁ E ₂ ΔTΔα-E ₂ Δ _{surface layer} ;

其中，σ _表面层为表面层的弯曲强度，σ _内芯层为内芯层的弯曲强度，E ₁为表面层的弹性模量；E ₂为内芯层的弹性模量；ΔT为所述复合陶瓷基板的软化温度与室温之差，所述复合陶瓷基板的软化温度为所述复合陶瓷的弹性模量开始出现急剧降低的温度点；Δα为所述内芯层与所述表面层的热膨胀系数之差；β为所述表面层与所述内芯层的弹性模量之比，β＝E ₁/E ₂；x为表征理论计算获得的最优层厚比
与实际实验获得的最优层厚比
之间区别的经验参数。 Wherein, σ _{surface layer} is the bending strength of the surface layer, σ _{inner core layer} is the bending strength of the inner core layer, E ₁ is the elastic modulus of the surface layer; E ₂ is the elastic modulus of the inner core layer; ΔT is the composite The difference between the softening temperature of the ceramic substrate and the room temperature, the softening temperature of the composite ceramic substrate is the temperature point at which the elastic modulus of the composite ceramic begins to decrease sharply; Δα is the thermal expansion coefficient of the inner core layer and the surface layer The difference; β is the ratio of the elastic modulus of the surface layer to the inner core layer, β=E ₁ /E ₂ ; x is the optimal layer thickness ratio obtained by characterizing theoretical calculations
Compared with the best layer thickness obtained by actual experiment
Empirical parameters for the difference between.
根据权利要求1所述的复合陶瓷基板，其特征在于，所述表面层的材料为内芯层的材料与低膨胀组元混合而制备得到的复合陶瓷。The composite ceramic substrate according to claim 1, wherein the material of the surface layer is a composite ceramic prepared by mixing the material of the inner core layer and the low expansion component.
根据权利要求4所述的复合陶瓷基板，其特征在于，所述内芯层的材料选自氧化铝陶瓷混合物、氮化铝陶瓷混合物、氮化硅陶瓷混合物中的一种；所述表面层的材料选自：氮化铝和氧化铝的复合陶瓷混合物、氮化铝和氮化硅的复合陶瓷混合物、或氮化硅和金刚石的复合陶瓷混合物。The composite ceramic substrate according to claim 4, wherein the material of the inner core layer is selected from one of alumina ceramic mixture, aluminum nitride ceramic mixture, and silicon nitride ceramic mixture; The material is selected from: a composite ceramic mixture of aluminum nitride and alumina, a composite ceramic mixture of aluminum nitride and silicon nitride, or a composite ceramic mixture of silicon nitride and diamond.
一种如权利要求5所述复合陶瓷基板的制备方法，其特征在于，包括以下步骤：A method for preparing a composite ceramic substrate according to claim 5, characterized by comprising the following steps:

步骤1、按照权利要求1-5任一项所述的第一约束条件和所述第二约束条件，将氧化铝、烧结助剂A、光敏树脂、分散剂和光引发剂混合，得到所述氧化铝陶瓷混合物；Step 1. According to the first constraint condition and the second constraint condition of any one of claims 1 to 5, alumina, sintering aid A, photosensitive resin, dispersant and photoinitiator are mixed to obtain the oxidation Aluminum ceramic mixture;

以及，按照权利要求1-5任一项所述的第一约束条件和所述第二约束条件，将氮化铝、氧化铝、烧结助剂B、光敏树脂、分散剂和光引发剂混合，得到所述氮化铝和氧化铝的复合陶瓷混合物；And, according to the first constraint condition and the second constraint condition of any one of claims 1-5, aluminum nitride, alumina, sintering aid B, photosensitive resin, dispersant and photoinitiator are mixed to obtain The composite ceramic mixture of aluminum nitride and aluminum oxide;

步骤2、按照权利要求1-5任一项所述的第一约束条件和所述第二约束条件，基于光固化3D打印的制备方法，将所述氧化铝陶瓷混合物和所述氮化铝和氧化铝的复合陶瓷混合物制得复合陶瓷基板的层状坯体，然后经固化、脱脂后进行无压烧结或流动热压烧结，得到复合陶瓷基板。Step 2. According to the first constraint condition and the second constraint condition according to any one of claims 1-5, based on the preparation method of light curing 3D printing, the alumina ceramic mixture and the aluminum nitride are combined with The composite ceramic mixture of alumina is used to prepare the laminated body of the composite ceramic substrate, which is then solidified and degreased and then subjected to pressureless sintering or flow hot pressing sintering to obtain the composite ceramic substrate.
一种如权利要求5所述复合陶瓷基板的制备方法，其特征在于，所述复合陶瓷基板的厚度>1mm，采用分层铺粉与预压制的方法制备复合陶瓷基板，所述分层铺粉与预压制的方法包括以下步骤：A method for preparing a composite ceramic substrate according to claim 5, wherein the thickness of the composite ceramic substrate is greater than 1 mm, and the composite ceramic substrate is prepared by a method of layered powder spreading and pre-pressing. The method with pre-pressing includes the following steps:

步骤一、按照权利要求1-5任一项所述的第一约束条件和所述第二约束条件，将氧化铝和烧结助剂C混合，造粒得到所述氧化铝陶瓷混合物；Step 1. According to the first constraint condition and the second constraint condition of any one of claims 1 to 5, the alumina and the sintering aid C are mixed to obtain the alumina ceramic mixture by granulation;

以及，按照权利要求1-5任一项所述的第一约束条件和所述第二约束条件，将氮化铝、氧化铝和烧结助剂D混合，造粒得到所述氮化铝和氧化铝的复合陶瓷混合物；And, according to the first constraint condition and the second constraint condition of any one of claims 1 to 5, aluminum nitride, aluminum oxide and sintering aid D are mixed, and granulated to obtain the aluminum nitride and oxide Composite ceramic mixture of aluminum;

步骤二、按照权利要求1-5任一项所述的第一约束条件和所述第二约束条件，利用分层铺粉与预压制的制备方法，将所述氧化铝陶瓷混合物和所述氮化铝和氧化铝的复合陶瓷混合物铺粉干压制得复合陶瓷基板的层状坯体，然后烧结制得复合陶瓷基板。Step 2. According to the first constraint condition and the second constraint condition of any one of claims 1 to 5, the preparation method of layered powder spreading and pre-pressing is used to combine the alumina ceramic mixture and the nitrogen The composite ceramic mixture of aluminum oxide and alumina is powdered and dry pressed to obtain a layered body of the composite ceramic substrate, and then sintered to obtain the composite ceramic substrate.
一种如权利要求5所述复合陶瓷基板的制备方法，其特征在于，包括以下步骤：A method for preparing a composite ceramic substrate according to claim 5, characterized by comprising the following steps:

步骤1、按照权利要求1-5任一项所述的第一约束条件和所述第二约束条件，将氮化铝、烧结助剂E、光敏树脂、分散剂和光引发剂混合，得到所述氮化铝陶瓷混合物；Step 1. According to the first constraint condition and the second constraint condition of any one of claims 1-5, aluminum nitride, sintering aid E, photosensitive resin, dispersant and photoinitiator are mixed to obtain said Aluminum nitride ceramic mixture;

以及，按照权利要求1-5任一项所述的第一约束条件和所述第二约束条件，将氮化铝、氮化硅、烧结助剂F、光敏树脂、分散剂和光引发剂混合，得到所述氮化铝和氮化硅的复合陶瓷混合物；And, according to the first constraint condition and the second constraint condition of any one of claims 1 to 5, aluminum nitride, silicon nitride, sintering aid F, photosensitive resin, dispersant and photoinitiator are mixed, Obtaining the composite ceramic mixture of aluminum nitride and silicon nitride;

步骤2、按照权利要求1-5任一项所述的第一约束条件和所述第二约束条件，基于光固化3D打印的制备方法，将所述氮化铝陶瓷混合物和所述氮化铝和氮化硅的复合陶瓷混合物制得复合陶瓷基板的层状坯体，然后经固化、脱脂后进行流动热压烧结，得到复合陶瓷基板。Step 2. According to the first constraint condition and the second constraint condition of any one of claims 1 to 5, the aluminum nitride ceramic mixture and the aluminum nitride The composite ceramic mixture of silicon nitride and silicon nitride is used to prepare a layered body of a composite ceramic substrate, which is then solidified and degreased and then subjected to flow hot pressing sintering to obtain a composite ceramic substrate.
一种如权利要求5所述复合陶瓷基板的制备方法，其特征在于，所述复合陶瓷基板的厚度>1mm，采用分层铺粉与预压制的方法制备复合陶瓷基板，所述分层铺粉与预压制的方法包括以下步骤：A method for preparing a composite ceramic substrate according to claim 5, wherein the thickness of the composite ceramic substrate is greater than 1 mm, and the composite ceramic substrate is prepared by a method of layered powder spreading and pre-pressing. The method with pre-pressing includes the following steps:

步骤一、按照权利要求1-5任一项所述的第一约束条件和所述第二约束条件，将氮化铝和烧结助剂G混合，造粒得到的所述氮化铝陶瓷混合物；Step 1. The aluminum nitride ceramic mixture is obtained by mixing aluminum nitride and sintering aid G according to the first constraint condition and the second constraint condition of any one of claims 1 to 5;

以及，按照权利要求1-5任一项所述的第一约束条件和所述第二约束条件，将氮化铝、氮化硅和烧结助剂H混合，造粒得到所述氮化铝和氮化硅的复合陶瓷混合物；And, according to the first constraint condition and the second constraint condition of any one of claims 1 to 5, aluminum nitride, silicon nitride, and sintering aid H are mixed to obtain the aluminum nitride and Composite ceramic mixture of silicon nitride;

步骤二、按照权利要求1-5任一项所述的第一约束条件和所述第二约束条件，基于利用分层铺粉与预压制的制备方法，将氮化铝陶瓷混合物和所述氮化铝和氮化硅的复合陶瓷混合物铺粉干压制得复合陶瓷基板的层状坯体，然后进行热压烧结或流动热压烧结，即可制得复合陶瓷基板。Step 2. According to the first constraint condition and the second constraint condition of any one of claims 1-5, based on the preparation method of layered powder spreading and pre-pressing, the aluminum nitride ceramic mixture and the nitrogen The composite ceramic mixture of aluminum oxide and silicon nitride is powdered and dry pressed to obtain a layered body of the composite ceramic substrate, and then hot-press sintering or flow hot-press sintering is performed to obtain the composite ceramic substrate.
一种如权利要求5所述复合陶瓷基板的制备方法，其特征在于，包括以下步骤：A method for preparing a composite ceramic substrate according to claim 5, characterized by comprising the following steps:

步骤1、按照权利要求1-5任一项所述的第一约束条件和所述第二约束条件，将氮化硅、烧结助剂J、光敏树脂、分散剂和光引发剂混合，得到所述氮化硅陶瓷混合物；Step 1. According to the first constraint condition and the second constraint condition according to any one of claims 1-5, silicon nitride, sintering aid J, photosensitive resin, dispersant and photoinitiator are mixed to obtain said Silicon nitride ceramic mixture;

以及，按照权利要求1-5任一项所述的第一约束条件和所述第二约束条件，将氮化硅、金刚石微粉、烧结助剂K、光敏树脂、分散剂和光引发剂混合，得到所述氮化硅和金刚石的复合陶瓷混合物；And, according to the first constraint condition and the second constraint condition of any one of claims 1 to 5, silicon nitride, diamond fine powder, sintering aid K, photosensitive resin, dispersant and photoinitiator are mixed to obtain The composite ceramic mixture of silicon nitride and diamond;

步骤2、按照权利要求1-5任一项所述的第一约束条件和所述第二约束条件，基于光固化3D打印的制备方法，将所述氮化硅陶瓷混合物和所述氮化硅和金刚石的复合陶瓷混合物制得复合陶瓷基板的层状坯体，然后经固化、脱脂后进行流动热压烧结，得到复合陶瓷基板。Step 2. According to the first constraint condition and the second constraint condition of any one of claims 1 to 5, the silicon nitride ceramic mixture and the silicon nitride The composite ceramic mixture with diamond is used to prepare the laminated body of the composite ceramic substrate, which is then solidified and degreased and then subjected to flow hot pressing sintering to obtain the composite ceramic substrate.
一种如权利要求5所述复合陶瓷基板的制备方法，其特征在于，所述复合陶瓷基板的厚度>1mm，采用分层铺粉与预压制的方法制备复合陶瓷基板，所述分层铺粉与预压制的方法包括以下步骤：A method for preparing a composite ceramic substrate according to claim 5, wherein the thickness of the composite ceramic substrate is greater than 1 mm, and the composite ceramic substrate is prepared by a method of layered powder spreading and pre-pressing. The method with pre-pressing includes the following steps:

步骤一、按照权利要求1-5任一项所述的第一约束条件和所述第二约束条件，将氮化硅和烧结助剂M混合，造粒得到所述氮化硅陶瓷混合物；Step 1. According to the first constraint condition and the second constraint condition of any one of claims 1 to 5, silicon nitride and sintering aid M are mixed to obtain the silicon nitride ceramic mixture by granulation;

以及，按照权利要求1-5任一项所述的第一约束条件和所述第二约束条件，将氮化硅、金刚石微粉和烧结助剂N混合，造粒得到所述氮化硅和金刚石的复合陶瓷混合物；And, according to the first constraint condition and the second constraint condition of any one of claims 1 to 5, silicon nitride, fine diamond powder and sintering aid N are mixed to obtain the silicon nitride and diamond by granulation Composite ceramic mixture;

步骤二、按照权利要求1-5任一项所述的第一约束条件和所述第二约束条件，利用分层铺粉与预压制的制备方法，将所述氮化硅陶瓷混合物和所述氮化硅和金刚石的复合陶瓷混合物铺粉干压制得复合陶瓷基板的层状坯体，然后利用热压烧结或流动热压烧结可制得复合陶瓷基板。Step 2. According to the first constraint condition and the second constraint condition of any one of claims 1-5, the silicon nitride ceramic mixture and the The composite ceramic mixture of silicon nitride and diamond is powdered and dry pressed to obtain a layered body of the composite ceramic substrate, and then the composite ceramic substrate can be prepared by hot pressing sintering or flow hot pressing sintering.