Background
In the electronic packaging process, the substrate mainly plays a role of mechanical support protection and electrical interconnection (insulation). As electronic packaging technology gradually develops toward miniaturization, high density, multiple functions and high reliability, power density of electronic systems increases, and heat dissipation problem becomes more and more serious. Poor heat dissipation can lead to device performance degradation, structural damage, delamination, or burn-out. Good device heat dissipation depends on optimized heat dissipation structure design, packaging material selection (thermal interface material and heat dissipation substrate), packaging manufacturing process, and the like. The selection of the substrate material is a key link, and the cost, the performance and the reliability of the device are directly influenced.
The electronic package has the following requirements on the performance of the substrate material: high thermal conductivity, low dielectric constant, high mechanical strength, good processing performance, low cost and the like, and is matched with the thermal expansion coefficient of a chip material. In fact, the above performances are difficult to satisfy simultaneously, sometimes contradict each other, and in practical applications, the selection can be performed only according to specific packaging objects. The commonly used substrate materials mainly include four major types, namely a plastic substrate, a metal substrate, a ceramic substrate and a composite substrate. At present, ceramic substrates, although not dominant, are increasingly used in electronic packaging, particularly in power electronic devices such as IGBT (insulated gate bipolar transistor), LD (laser diode), high power LED (light emitting diode), CPV (focus photovoltaic) packaging, due to their good thermal conductivity, heat resistance, insulation properties, low thermal expansion coefficient and continuous reduction in cost. For a long time, most ceramic substrate materials are made of alumina and beryllium oxide, but alumina substrates have low thermal conductivity and thermal expansion coefficients not matched with those of silicon; although beryllium oxide has excellent comprehensive performance, the application and popularization of beryllium oxide are limited by the defects of high production cost and high toxicity of beryllium oxide. Therefore, from the aspects of performance, cost and environmental protection, the two cannot fully meet the development requirements of modern electronic devices.
Therefore, how to improve the defects of poor mechanical property and poor heat conductivity of the traditional ceramic substrate to obtain a ceramic substrate with higher comprehensive performance is a problem to be solved urgently by popularizing and applying the ceramic substrate to a wider field and meeting the industrial production requirement.
Disclosure of Invention
The invention mainly solves the technical problems that: aiming at the defects of poor mechanical property and poor heat conducting property of the traditional ceramic substrate, the high-heat-conductivity ceramic substrate and the preparation method thereof are provided.
In order to solve the technical problems, the technical scheme adopted by the invention is as follows:
a high-thermal-conductivity ceramic substrate is composed of the following raw materials in parts by weight:
70-80 parts of alumina powder
10-15 parts of iron oxide powder
20-25 parts of copper oxide powder
20-25 parts of carbon powder
13-18 parts of boron oxide powder
12-16 parts of modified glass fiber
8-14 parts of metal oxide whisker
3-5 parts of cryolite
The preparation method of the modified glass fiber comprises the following steps:
mixing nano silicon dioxide and a silane coupling agent according to a mass ratio of 8: 11-10: 11, adding anhydrous ethanol with the mass 10-12 times of that of the nano silicon dioxide, stirring and mixing to obtain a treatment solution, and mixing the glass fiber and the treatment solution according to the mass ratio of 1: 6-1: 8, mixing, ultrasonically oscillating, filtering and drying to obtain modified glass fiber;
the preparation method of the high-thermal-conductivity ceramic substrate comprises the following steps:
(1) weighing the components according to the composition of the raw materials;
(2) mixing carbon powder, boron oxide powder, cryolite and modified glass fiber, ball milling, sieving to obtain mixed powder, mixing the mixed powder, alumina powder, iron oxide powder, copper oxide powder and metal oxide whiskers, adding the mixture into a mold, pressing and molding in the mold to obtain a blank, and transferring the blank into a sintering furnace for sintering to obtain the high-thermal-conductivity ceramic substrate.
The metal oxide whisker is any one of magnesium oxide whisker or copper oxide whisker.
The glass fiber is any one of alkali-free glass fiber or medium-alkali glass fiber.
The silane coupling agent is any one of a silane coupling agent KH-560, a silane coupling agent KH-550 or a silane coupling agent KH-570.
The condition of the pressing and forming in the step (2) is that the pressing and forming are carried out for 30-45 s at the pressure of 80-90 MPa, and then the pressing and forming are carried out for 100-110 s at the pressure of 100-110 MPa.
The invention has the beneficial effects that:
(1) the invention adds iron oxide powder, copper oxide powder and carbon powder when preparing the high-thermal conductivity ceramic substrate, firstly, the addition of the iron oxide powder and the copper oxide powder can be used as fluxing agent, so that the sintering temperature of the ceramic substrate is reduced, the compactness of the alumina ceramic is improved, and the mechanical property of the product is improved, secondly, in the sintering process, the carbon in the carbon powder can reduce the iron and the copper in the iron oxide powder and the copper oxide powder, and the density of the iron and the copper is larger than that of the alumina, therefore, part of the iron and the copper replaced in the sintering process can be deposited on the bottom layer of the substrate, in the subsequent compounding process with the copper foil, the welding of the substrate and the copper foil is facilitated, the compatibility of the two is improved, the contact thermal resistance is effectively reduced, the integral thermal conductivity is improved, in addition, two uniform copper layers and iron layers can be formed on the surface of the alumina ceramic by part, the carbon powder can react with silicon dioxide to generate silicon carbide which is distributed in a ceramic substrate system, so that the heat-conducting property of the product is improved;
(2) according to the invention, the modified glass fiber and the metal oxide whisker are added when the high-thermal-conductivity ceramic substrate is prepared, on one hand, the surface activity of the modified glass fiber is improved, the contact sites are increased, and after the modified glass fiber and the metal oxide whisker are added into a ceramic substrate system, the bonding force among substances in the system can be enhanced, so that the mechanical property of the product is improved, on the other hand, the carbon powder can be filled in the pores left after the reaction, so that the density of the ceramic substrate system is improved, and further the mechanical property of the product is improved.
Detailed Description
Mixing nano silicon dioxide and a silane coupling agent according to a mass ratio of 8: 11-10: mixing the glass fiber and the treatment solution in a beaker, adding absolute ethyl alcohol which is 10-12 times of the mass of the nano silicon dioxide into the beaker, moving the beaker into a digital display speed measurement constant-temperature magnetic stirrer, stirring and mixing the mixture at the temperature of 45-60 ℃ and the rotating speed of 300-360 r/min to obtain the treatment solution, and mixing the glass fiber and the treatment solution according to the mass ratio of 1: 6-1: 8, mixing the mixture in a flask, moving the flask into an ultrasonic oscillator, carrying out ultrasonic oscillation for 15-22 min under the condition that the frequency is 45-55 kHz, filtering to obtain a filter cake, moving the filter cake into a drying oven, and drying for 60-80 min under the condition that the temperature is 75-90 ℃ to obtain modified glass fibers; weighing 70-80 parts of alumina powder, 10-15 parts of ferric oxide powder, 20-25 parts of cupric oxide powder, 20-25 parts of carbon powder, 13-18 parts of boron oxide powder, 12-16 parts of modified glass fiber, 8-14 parts of metal oxide whisker and 3-5 parts of cryolite in sequence according to parts by weight; adding carbon powder, boron oxide powder, cryolite and modified glass fiber into a stirrer, stirring and mixing to obtain a mixture, adding the mixture into a ball mill, adding zirconia ball grinding beads with the mass being 4-5 times of that of the mixture into the ball mill, ball-milling for 2-3 h, sieving with a 100-120-mesh sieve to obtain mixture powder, mixing the mixture powder, alumina powder, iron oxide powder, copper oxide powder and metal oxide whiskers, adding the mixture powder into a mold, moving the mold into a press, performing compression molding at the temperature of 70-80 ℃ to obtain a blank, moving the blank into a sintering furnace, introducing argon into the furnace at the rate of 80-120 mL/min, performing sintering molding at the temperature of 1150-1300 ℃ under the protection of argon, and taking out the blank after cooling to room temperature along with the furnace to obtain the high-thermal-conductivity ceramic substrate. The metal oxide whisker is any one of magnesium oxide whisker or copper oxide whisker. The glass fiber is any one of alkali-free glass fiber or medium-alkali glass fiber. The silane coupling agent is any one of a silane coupling agent KH-560, a silane coupling agent KH-550 or a silane coupling agent KH-570. The pressing and forming conditions are that the pressing and forming are carried out for 30-45 s at the pressure of 80-90 MPa, and then the pressing and forming are carried out for 100-110 s at the pressure of 100-110 MPa.
Example 1
Mixing nano silicon dioxide and a silane coupling agent according to the mass ratio of 10: mixing 11 and the glass fiber in a beaker, adding absolute ethyl alcohol with the mass of 12 times that of the nano silicon dioxide into the beaker, moving the beaker into a digital display speed measurement constant-temperature magnetic stirrer, stirring and mixing under the conditions that the temperature is 60 ℃ and the rotating speed is 360r/min to obtain a treatment solution, and mixing the glass fiber and the treatment solution according to the mass ratio of 1: 8, mixing the mixture in a flask, moving the flask into an ultrasonic oscillator, carrying out ultrasonic oscillation for 22min under the condition of the frequency of 55kHz, filtering to obtain a filter cake, moving the filter cake into a drying box, and drying for 80min under the condition of the temperature of 90 ℃ to obtain modified glass fiber; weighing 80 parts of alumina powder, 15 parts of iron oxide powder, 25 parts of copper oxide powder, 25 parts of carbon powder, 18 parts of boron oxide powder, 16 parts of modified glass fiber, 14 parts of metal oxide whisker and 5 parts of cryolite in sequence; adding carbon powder, boron oxide powder, cryolite and modified glass fiber into a stirrer, stirring and mixing to obtain a mixture, adding the mixture into a ball mill, adding zirconia balls with 5 times of the mass of the mixture into the ball mill, ball-milling for 3 hours, sieving by a 120-mesh sieve to obtain mixture powder, mixing the mixture powder, alumina powder, iron oxide powder, copper oxide powder and metal oxide whiskers, adding the mixture powder into a mold, transferring the mold into a press machine, pressing and molding at the temperature of 80 ℃ to obtain a blank, transferring the blank into a sintering furnace, introducing argon into the furnace at the speed of 120mL/min, sintering and molding at the temperature of 1300 ℃ under the protection of argon, cooling along with the furnace to room temperature, and discharging to obtain the high-thermal-conductivity ceramic substrate. The metal oxide whisker is a magnesium oxide whisker. The glass fiber is alkali-free glass fiber. The silane coupling agent is a silane coupling agent KH-560. The pressing molding condition is that the pressing is performed for 45s at the pressure of 90MPa, and then the pressing is performed for 110s at the pressure of 110 MPa.
Example 2
Mixing nano silicon dioxide and a silane coupling agent according to the mass ratio of 10: mixing 11 and the glass fiber in a beaker, adding absolute ethyl alcohol with the mass of 12 times that of the nano silicon dioxide into the beaker, moving the beaker into a digital display speed measurement constant-temperature magnetic stirrer, stirring and mixing under the conditions that the temperature is 60 ℃ and the rotating speed is 360r/min to obtain a treatment solution, and mixing the glass fiber and the treatment solution according to the mass ratio of 1: 8, mixing the mixture in a flask, moving the flask into an ultrasonic oscillator, carrying out ultrasonic oscillation for 22min under the condition of the frequency of 55kHz, filtering to obtain a filter cake, moving the filter cake into a drying box, and drying for 80min under the condition of the temperature of 90 ℃ to obtain modified glass fiber; weighing 80 parts of alumina powder, 18 parts of boron oxide powder, 16 parts of modified glass fiber, 14 parts of metal oxide whisker and 5 parts of cryolite in sequence according to parts by weight; adding boron oxide powder, cryolite and modified glass fiber into a stirrer, stirring and mixing to obtain a mixture, adding the mixture into a ball mill, adding zirconia ball grinding beads with 5 times of the mass of the mixture into the ball mill, performing ball milling for 3 hours, sieving by a 120-mesh sieve to obtain mixture powder, mixing the mixture powder, alumina powder and metal oxide whiskers, adding the mixture powder into a mold, transferring the mold into a press machine, performing compression molding at the temperature of 80 ℃ to obtain a blank, transferring the blank into a sintering furnace, introducing argon into the furnace at the speed of 120mL/min, performing sintering molding at the temperature of 1300 ℃ under the protection of argon, cooling to room temperature along with the furnace, and taking out of the furnace to obtain the high-thermal-conductivity ceramic substrate. The metal oxide whisker is a magnesium oxide whisker. The glass fiber is alkali-free glass fiber. The silane coupling agent is a silane coupling agent KH-560. The pressing molding condition is that the pressing is performed for 45s at the pressure of 90MPa, and then the pressing is performed for 110s at the pressure of 110 MPa.
Example 3
Weighing 80 parts of alumina powder, 15 parts of iron oxide powder, 25 parts of copper oxide powder, 25 parts of carbon powder, 18 parts of boron oxide powder, 16 parts of glass fiber, 14 parts of metal oxide whisker and 5 parts of cryolite in sequence; adding carbon powder, boron oxide powder, cryolite and glass fiber into a stirrer, stirring and mixing to obtain a mixture, adding the mixture into a ball mill, adding zirconia ball grinding beads with 5 times of the mass of the mixture into the ball mill, carrying out ball milling for 3 hours, sieving by a 120-mesh sieve to obtain mixture powder, mixing the mixture powder, alumina powder, iron oxide powder, copper oxide powder and metal oxide whiskers, adding the mixture powder into a mold, transferring the mold into a press machine, carrying out compression molding at the temperature of 80 ℃ to obtain a blank, transferring the blank into a sintering furnace, introducing argon into the furnace at the speed of 120mL/min, carrying out sintering molding at the temperature of 1300 ℃ in an argon protection state, cooling along with the furnace to room temperature, and taking out the furnace to obtain the high-thermal-conductivity ceramic substrate. The metal oxide whisker is a magnesium oxide whisker. The glass fiber is alkali-free glass fiber. The silane coupling agent is a silane coupling agent KH-560. The pressing molding condition is that the pressing is performed for 45s at the pressure of 90MPa, and then the pressing is performed for 110s at the pressure of 110 MPa.
Example 4
Mixing nano silicon dioxide and a silane coupling agent according to the mass ratio of 10: mixing 11 and the glass fiber in a beaker, adding absolute ethyl alcohol with the mass of 12 times that of the nano silicon dioxide into the beaker, moving the beaker into a digital display speed measurement constant-temperature magnetic stirrer, stirring and mixing under the conditions that the temperature is 60 ℃ and the rotating speed is 360r/min to obtain a treatment solution, and mixing the glass fiber and the treatment solution according to the mass ratio of 1: 8, mixing the mixture in a flask, moving the flask into an ultrasonic oscillator, carrying out ultrasonic oscillation for 22min under the condition of the frequency of 55kHz, filtering to obtain a filter cake, moving the filter cake into a drying box, and drying for 80min under the condition of the temperature of 90 ℃ to obtain modified glass fiber; weighing 80 parts of alumina powder, 15 parts of iron oxide powder, 25 parts of copper oxide powder, 25 parts of carbon powder, 18 parts of boron oxide powder, 16 parts of modified glass fiber and 5 parts of cryolite in sequence according to parts by weight; adding carbon powder, boron oxide powder, cryolite and modified glass fiber into a stirrer, stirring and mixing to obtain a mixture, adding the mixture into a ball mill, adding zirconia balls with 5 times of the mass of the mixture into the ball mill, ball-milling for 3 hours, sieving by a 120-mesh sieve to obtain mixture powder, mixing the mixture powder, alumina powder, iron oxide powder and copper oxide powder, adding the mixture powder into a mold, moving the mold into a press machine, performing compression molding at the temperature of 80 ℃ to obtain a blank, moving the blank into a sintering furnace, introducing argon into the furnace at the speed of 120mL/min, performing sintering molding at the temperature of 1300 ℃ under the protection of argon, cooling along with the furnace to room temperature, and discharging to obtain the high-thermal-conductivity ceramic substrate. The silane coupling agent is a silane coupling agent KH-560. The pressing molding condition is that the pressing is performed for 45s at the pressure of 90MPa, and then the pressing is performed for 110s at the pressure of 110 MPa.
Comparative example: shenzhen ceramic substrate produced by a certain circuit board company Limited.
The high thermal conductivity ceramic substrates obtained in examples 1 to 4 and comparative example products were subjected to performance tests, specifically, the test methods were as follows:
1. heat conductivity: detecting the comprehensive thermal conductivity of the test piece by using a thermal resistance tester (capable of measuring the bulk thermal resistance and the interface thermal resistance of a multi-interface system);
2. mechanical properties: the tensile strength of the test piece is detected according to GB/T14619.
The specific detection result is shown in the accompanying drawing, and as can be seen from the detection result shown in fig. 1, the high-thermal-conductivity ceramic substrate prepared by the technical scheme of the invention has the advantages that the thermal conductivity is improved, the mechanical property is also obviously improved, and the high-thermal-conductivity ceramic substrate has a wide prospect in the development of the technical field of ceramic electronic packaging materials.