WO2019114048A1 - Self-heat-release pressureless sintered conductive silver paste and preparation method therefor - Google Patents

Self-heat-release pressureless sintered conductive silver paste and preparation method therefor Download PDF

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WO2019114048A1
WO2019114048A1 PCT/CN2017/120301 CN2017120301W WO2019114048A1 WO 2019114048 A1 WO2019114048 A1 WO 2019114048A1 CN 2017120301 W CN2017120301 W CN 2017120301W WO 2019114048 A1 WO2019114048 A1 WO 2019114048A1
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silver paste
self
conductive silver
pressureless sintered
sintered conductive
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PCT/CN2017/120301
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French (fr)
Chinese (zh)
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孙蓉
张保坦
李金泽
朱朋莉
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中国科学院深圳先进技术研究院
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Publication of WO2019114048A1 publication Critical patent/WO2019114048A1/en

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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
    • H01B1/00—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors
    • H01B1/14—Conductive material dispersed in non-conductive inorganic material
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
    • H01B1/00—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors
    • H01B1/20—Conductive material dispersed in non-conductive organic material
    • H01B1/22—Conductive material dispersed in non-conductive organic material the conductive material comprising metals or alloys
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
    • H01B13/00—Apparatus or processes specially adapted for manufacturing conductors or cables

Definitions

  • the invention relates to an electronic packaging material, in particular to a self-heating pressureless sintering conductive silver paste and a preparation method thereof.
  • the third generation of wide bandgap semiconductor materials is an important support for enhancing the core competitiveness of next-generation information technology.
  • the third-generation semiconductor materials represented by silicon carbide (SiC), gallium nitride (GaN) and zinc oxide (ZnO) have large forbidden band width, high breakdown field strength, large thermal conductivity, and electron saturation drift speed.
  • microwave RF devices High dielectric constant, high radiation resistance, good chemical stability, high voltage, high temperature, high frequency, high power, radiation resistant microwave millimeter wave device and short wavelength optoelectronic semiconductor device, solid state light source and power electronics
  • the "core" of microwave RF devices has broad application prospects in the fields of semiconductor lighting, 5G communication, smart grid, high-speed rail transit, new energy vehicles, artificial intelligence, consumer electronics, etc., and is expected to break through the bottleneck of traditional semiconductor technology. Complementing the first-generation and second-generation semiconductor technologies will play an important role in energy conservation and emission reduction, industrial transformation and upgrading, and the creation of new economic growth points.
  • Wide bandgap semiconductor devices typically operate continuously at temperatures around 300 ° C or higher, requiring good switching characteristics and workability. This also imposes more stringent requirements on the related power chip package connection materials and technologies, not only has the outstanding characteristics of small on-resistance and strong electrical conductivity, but also has sufficient high-temperature mechanical strength and small thermal expansion mismatch. To ensure the reliability of the connection in high temperature environment. In addition, in order to prevent the accumulation of heat at a high power density, the chip connection material is required to have low thermal resistance and high heat dissipation efficiency, so as to facilitate the maximum temperature resistance of the connection layer material.
  • nano silver paste has a high melting point of 960 ° C, excellent electrical and thermal conductivity, and can achieve sintering interconnection at low temperature, becoming the preferred high-temperature electronic package interconnection for wide bandgap semiconductor devices. material.
  • auxiliary pressure to increase the sintering driving force, thereby lowering the sintering temperature and limiting the wide application of the nano silver paste.
  • the low temperature sintered nano silver paste can withstand high working temperature (greater than 300 ° C) after sintering because of its high metal thermal conductivity and electrical conductivity. ), with good reliability, has become a research hotspot of current power chip interconnection.
  • the present invention provides a self-heating pressureless sintered conductive silver paste and a preparation method thereof, so that the self-heating pressureless sintered conductive silver paste has low post-treatment temperature, high temperature resistance and high thermal conductivity. And high bonding characteristics, can significantly improve the reliability of packaged devices, suitable for the bonding and heat dissipation of the third generation of wide bandgap semiconductor chips.
  • a self-heating pressureless sintered conductive silver paste comprising the following weight percentages of raw materials: 20% to 60% nano silver powder, 30% to 70% solvent, 2% to 10% nano aluminum heat agent, 0.1% to 2% dispersion Auxiliary and 0.1% to 5% organic carrier.
  • the size of the nano silver powder is preferably less than 100 nm, and more preferably, the size of the nano silver powder is 5 nm to 100 nm, and the morphology thereof is irregular granular or spherical.
  • the solvent is methanol, ethanol, benzyl alcohol, ethylene glycol, acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol single Butyl ether, petroleum ether, tetrahydrofuran, benzene, methyl, xylene, carbon tetrachloride, ethyl acetate, butyl acetate, pentane, hexane, octane, cyclohexane, ethylene glycol butyl ether acetate, At least one of propylene glycol methyl ether acetate, diethylene glycol monobutyl ether acetate, terpineol, dimethyl carbonate, and diphenyl carbonate.
  • the dispersing agent is polyethylene glycol, polyvinyl alcohol, polyvinyl pyrrolidone, cetyl ammonium bromide, myristyl alcohol, dodecylamine, oleylamine, octyl mercaptan, dodecyl mercaptan And at least one of hexadecyl mercaptan.
  • the nano-alumina is at least one of Al/Fe 2 O 3 , Al/CuO, Al/MoO 3 , Al/WO 3 , Al/PbO, and Al/SiO 2 .
  • the nano-alumina has a size of 3 nm to 20 nm.
  • the organic carrier is a polypyrrolidone, an epoxy resin, a phenolic resin, an acrylic, a urethane, a silicone, a polyalkylene carbonate, a polyvinyl acetal, and a cellulose. At least one of the classes.
  • the invention also provides a preparation method of self-heating pressureless sintered conductive silver paste, comprising the following steps:
  • the preparation method is preferably carried out under normal temperature and normal pressure.
  • the rotational speed of the rotation is 500 rpm to 1000 rpm.
  • the rotational speed of the rotation is 300 rpm to 500 rpm.
  • the present invention adds a nano-aluminothermic agent having an exothermic effect to the nano-silver solution, and the redox reaction of such materials can release a large amount of heat (ie, the exothermic can be induced at 200 ° C to 250 ° C).
  • the reaction is absorbed by the nano silver particles to achieve the thermal amplification effect of the sintered layer of the nano silver particles, lowering the sintering temperature of the silver paste, and improving the compactness, strength and adhesion to the matrix of the bonding layer (ie, It is said that the self-heating pressureless sintered conductive silver paste has low post-treatment temperature, high temperature resistance, high thermal conductivity and high bonding property).
  • the method not only overcomes the problem of poor post-treatment temperature of the existing conductive silver paste and the non-densified diffusion of the sintering process, but also simplifies the post-processing process, and can significantly improve the reliability of the packaged device, especially for the first Bonding and heat dissipation of three generations of wide bandgap semiconductor chips.
  • the invention provides a self-heating pressureless sintered conductive silver paste with novel structure, which provides a new idea for the bonding and heat dissipation design of the third generation wide band gap semiconductor chip.
  • a preparation method of self-heating pressureless sintered conductive silver paste comprising the following steps:
  • the self-heating pressureless sintered conductive silver paste obtained in this embodiment is sintered at 250 ° C for 30 min, and has a volume resistivity of 3.17 ⁇ 10 -6 ohm ⁇ cm, a thermal conductivity of 209 W/(m ⁇ K), and a bonding strength greater than 43.5 MPa.
  • a preparation method of self-heating pressureless sintered conductive silver paste comprising the following steps:
  • the self-heating pressureless sintered conductive silver paste obtained in this embodiment is sintered at 250 ° C for 30 min, and has a volume resistivity of 1.86 ⁇ 10 -6 ohm ⁇ cm, a thermal conductivity of 226 W/(m ⁇ K), and a bonding strength greater than 41.3 MPa.
  • a preparation method of self-heating pressureless sintered conductive silver paste comprising the following steps:
  • the self-heating pressureless sintered conductive silver paste obtained in this embodiment is sintered at 250 ° C for 30 min, and has a volume resistivity of 6.19 ⁇ 10 -6 ohm ⁇ cm and a thermal conductivity of 192 W/(m ⁇ K), and the bonding strength is greater than 37.7MPa.
  • a preparation method of self-heating pressureless sintered conductive silver paste comprising the following steps:
  • the self-heating pressureless sintered conductive silver paste obtained in this embodiment is sintered at 250 ° C for 30 min, and has a volume resistivity of 4.76 ⁇ 10 -6 ohm ⁇ cm, a thermal conductivity of 201 W/(m ⁇ K), and a bonding strength greater than 40.3 MPa.
  • a method for preparing a conductive silver paste comprising the steps of:
  • the conductive silver paste obtained in the comparative example was sintered at 250 ° C for 30 min, and had a volume resistivity of 5.96 ⁇ 10 -6 ohm ⁇ cm, a thermal conductivity of 15.2 W/(m ⁇ K), and a bond strength of more than 4.5 MPa.
  • Example 1 to Example 4 According to the comparison of Example 1 to Example 4 with Comparative Example 1, it can be seen that in the embodiment 1 to the embodiment 4 of the present invention, since the above-described component formulation was employed, it was compared with Comparative Example 1 as an existing product.
  • the self-heating pressureless sintered conductive silver paste prepared by the invention has high temperature resistance, high thermal conductivity and high bonding property, and plays an important role in the bonding and heat dissipation of the third generation wide band gap semiconductor chip.

Abstract

Disclosed are a self-heat-release pressureless sintered conductive silver paste and a preparation method therefor. The self-heat-release pressureless sintered conductive silver paste comprises the following raw materials in weight percentage: 20% to 60% of a nano silver powder, 30% to 70% of a solvent, 2% to 10% of a nano thermite, 0.1% to 2% of a dispersing auxiliary, and 0.1% to 5% of an organic carrier. By introducing the nano thermite having a redox exothermic effect in the nano silver paste, an exothermic reaction can be initiated at 200℃ to 250℃, such that the self-heat-release pressureless sintered conductive silver paste has a low post-treatment temperature, high temperature resistance, high thermal conductivity, and high bonding properties, can significantly improve the reliability of packaged devices, and is suitable for bonding and heat dissipation of the third generation of wide-gap semiconductor chips.

Description

一种自放热无压烧结导电银浆及其制备方法Self-heating pressureless sintered conductive silver paste and preparation method thereof 技术领域Technical field
本发明涉及电子封装材料，尤其涉及一种自放热无压烧结导电银浆及其制备方法。The invention relates to an electronic packaging material, in particular to a self-heating pressureless sintering conductive silver paste and a preparation method thereof.
背景技术Background technique
第三代宽禁带半导体材料是提升新一代信息技术核心竞争力的重要支撑。以碳化硅(SiC)、氮化镓(GaN)和氧化锌(ZnO)为代表的第三代半导体材料，因具有禁带宽度大、击穿场强高、热导率大、电子饱和漂移速度高、介电常数小、抗辐射能力强、化学稳定性良好等特性，可实现高压、高温、高频、大功率、抗辐射微波毫米波器件和短波长光电半导体器件，是固态光源和电力电子、微波射频器件的“核芯”，在半导体照明、5G通信、智能电网、高速轨道交通、新能源汽车、人工智能、消费类电子等领域有广阔的应用前景，有望突破传统半导体技术的瓶颈，与第一代、第二代半导体技术互补，对节能减排、产业转型升级、催生新的经济增长点将发挥重要作用。The third generation of wide bandgap semiconductor materials is an important support for enhancing the core competitiveness of next-generation information technology. The third-generation semiconductor materials represented by silicon carbide (SiC), gallium nitride (GaN) and zinc oxide (ZnO) have large forbidden band width, high breakdown field strength, large thermal conductivity, and electron saturation drift speed. High dielectric constant, high radiation resistance, good chemical stability, high voltage, high temperature, high frequency, high power, radiation resistant microwave millimeter wave device and short wavelength optoelectronic semiconductor device, solid state light source and power electronics The "core" of microwave RF devices has broad application prospects in the fields of semiconductor lighting, 5G communication, smart grid, high-speed rail transit, new energy vehicles, artificial intelligence, consumer electronics, etc., and is expected to break through the bottleneck of traditional semiconductor technology. Complementing the first-generation and second-generation semiconductor technologies will play an important role in energy conservation and emission reduction, industrial transformation and upgrading, and the creation of new economic growth points.
宽禁带半导体器件通常会在300℃左右甚至更高温环境下持续工作，要求具有良好的转换特性和工作能力。这对相关的功率芯片封装连接材料和技术也提出了更加苛刻的要求，不仅要具有导通电阻小、导电能力强的突出特点，还要具有足够的高温力学强度和较小的热膨胀失配，以保证在高温环境下连接的可靠性。另外，为了防止高功率密度下热量的积聚，要求芯片连接材料热阻低，散热效率高，以便利于充分发挥连接层材料最大耐温能力。然而，目前常用的芯片无铅互连材料主要是合金焊料或导电胶，但绝大多数无铅焊料和导电胶的可靠工作温度远低于250℃，这严重限制了宽带隙半导体功率电子器件的应用。纳米银浆作为一种新型的绿色无铅封装材料，具有960℃的高熔点，且导电、导热性能优异，可在低温下实现烧结互连，成为宽禁带半导体器件的首选高温电子封装互连材料。但是在连接大面积芯 片时，一般需要施加辅助压力来提高烧结驱动力，从而降低烧结温度，限制了纳米银浆的广泛应用。因此，研究可高温应用的大功率宽带隙半导体器件的新型无铅化互连材料和技术就显得十分必要，已经成为当前微电子领域的重要课题。而针对第三代半导体芯片互联材料的高导热、高耐热、高强度需求，低温烧结纳米银浆因为具有高的金属热导率及电导率，烧结后能承受高的工作温度(大于300℃)，具有良好的可靠性，成为当前功率芯片互联的研究热点。Wide bandgap semiconductor devices typically operate continuously at temperatures around 300 ° C or higher, requiring good switching characteristics and workability. This also imposes more stringent requirements on the related power chip package connection materials and technologies, not only has the outstanding characteristics of small on-resistance and strong electrical conductivity, but also has sufficient high-temperature mechanical strength and small thermal expansion mismatch. To ensure the reliability of the connection in high temperature environment. In addition, in order to prevent the accumulation of heat at a high power density, the chip connection material is required to have low thermal resistance and high heat dissipation efficiency, so as to facilitate the maximum temperature resistance of the connection layer material. However, the commonly used chip lead-free interconnect materials are mainly alloy solder or conductive paste, but the reliable operating temperature of most lead-free solders and conductive pastes is much lower than 250 ° C, which severely limits the wide band gap semiconductor power electronic devices. application. As a new type of green lead-free packaging material, nano silver paste has a high melting point of 960 ° C, excellent electrical and thermal conductivity, and can achieve sintering interconnection at low temperature, becoming the preferred high-temperature electronic package interconnection for wide bandgap semiconductor devices. material. However, when connecting large-area chips, it is generally necessary to apply auxiliary pressure to increase the sintering driving force, thereby lowering the sintering temperature and limiting the wide application of the nano silver paste. Therefore, it is necessary to study new lead-free interconnect materials and technologies for high-power wide-bandgap semiconductor devices for high-temperature applications, which has become an important topic in the field of microelectronics. For the high thermal conductivity, high heat resistance and high strength requirements of the third generation semiconductor chip interconnection materials, the low temperature sintered nano silver paste can withstand high working temperature (greater than 300 ° C) after sintering because of its high metal thermal conductivity and electrical conductivity. ), with good reliability, has become a research hotspot of current power chip interconnection.
然而，当前纳米导电银浆制备过程中普遍存在纳米颗粒团聚和分散问题以及低温烧结过程存在非致密扩散问题，影响到纳米导电银浆的应用。However, the current problem of nanoparticle agglomeration and dispersion is common in the preparation of nano-conductive silver paste and the non-dense diffusion problem in the low-temperature sintering process affects the application of nano-conductive silver paste.
发明内容Summary of the invention
为了克服现有技术的不足，本发明提供了一种自放热无压烧结导电银浆及其制备方法，使得该自放热无压烧结导电银浆具有后处理温度低，耐高温、高导热以及高粘结特性，可显著提高封装器件的可靠性，适用于第三代宽禁带半导体芯片的粘结及散热。In order to overcome the deficiencies of the prior art, the present invention provides a self-heating pressureless sintered conductive silver paste and a preparation method thereof, so that the self-heating pressureless sintered conductive silver paste has low post-treatment temperature, high temperature resistance and high thermal conductivity. And high bonding characteristics, can significantly improve the reliability of packaged devices, suitable for the bonding and heat dissipation of the third generation of wide bandgap semiconductor chips.
一种自放热无压烧结导电银浆，包括以下重量百分比的原料：20％～60％纳米银粉、30％～70％溶剂、2％～10％纳米铝热剂、0.1％～2％分散助剂和0.1％～5％有机载体。A self-heating pressureless sintered conductive silver paste comprising the following weight percentages of raw materials: 20% to 60% nano silver powder, 30% to 70% solvent, 2% to 10% nano aluminum heat agent, 0.1% to 2% dispersion Auxiliary and 0.1% to 5% organic carrier.
优选地，所述纳米银粉的尺寸优选小于100nm，更优选地，所述纳米银粉的尺寸为5nm～100nm，其形貌为不规则颗粒状或球型。Preferably, the size of the nano silver powder is preferably less than 100 nm, and more preferably, the size of the nano silver powder is 5 nm to 100 nm, and the morphology thereof is irregular granular or spherical.
优选地，所述溶剂为甲醇、乙醇、苯甲醇、乙二醇、丙酮、甲乙酮、甲基异丁基酮、环己酮、乙二醇单甲醚、乙二醇单乙醚、乙二醇单丁醚、石油醚、四氢呋喃、苯、甲笨、二甲苯、四氯化碳、乙酸乙酯、乙酸丁酯、戊烷、己烷、辛烷、环己烷、乙二醇丁醚醋酸酯、丙二醇甲醚醋酸酯、二乙二醇单丁醚醋酸酯、松油醇、碳酸二甲酯以及碳酸二苯酯中的至少一种。Preferably, the solvent is methanol, ethanol, benzyl alcohol, ethylene glycol, acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol single Butyl ether, petroleum ether, tetrahydrofuran, benzene, methyl, xylene, carbon tetrachloride, ethyl acetate, butyl acetate, pentane, hexane, octane, cyclohexane, ethylene glycol butyl ether acetate, At least one of propylene glycol methyl ether acetate, diethylene glycol monobutyl ether acetate, terpineol, dimethyl carbonate, and diphenyl carbonate.
优选地，所述分散剂为聚乙二醇、聚乙烯醇、聚乙烯吡咯烷酮、十六烷基溴化铵、肉豆蔻醇、十二胺、油胺、辛硫醇、十二烷基硫醇以及十六烷基硫醇中的至少一种。Preferably, the dispersing agent is polyethylene glycol, polyvinyl alcohol, polyvinyl pyrrolidone, cetyl ammonium bromide, myristyl alcohol, dodecylamine, oleylamine, octyl mercaptan, dodecyl mercaptan And at least one of hexadecyl mercaptan.
优选地，所述纳米铝热剂为Al/Fe 2O 3、Al/CuO、Al/MoO 3、Al/WO 3、Al/PbO和Al/SiO 2中的至少一种。 Preferably, the nano-alumina is at least one of Al/Fe 2 O 3 , Al/CuO, Al/MoO 3 , Al/WO 3 , Al/PbO, and Al/SiO 2 .
优选地，所述纳米铝热剂的尺寸在3nm～20nm。Preferably, the nano-alumina has a size of 3 nm to 20 nm.
优选地，所述有机载体为聚吡咯烷酮类、环氧树脂类、酚醛树脂类、丙烯酸类、氨基甲酸酯类、硅树脂类、聚亚烷基碳酸酯类、聚乙烯醇缩醛类和纤维素类中的至少一种。Preferably, the organic carrier is a polypyrrolidone, an epoxy resin, a phenolic resin, an acrylic, a urethane, a silicone, a polyalkylene carbonate, a polyvinyl acetal, and a cellulose. At least one of the classes.
本发明还提供了一种自放热无压烧结导电银浆的制备方法，包括如下步骤：The invention also provides a preparation method of self-heating pressureless sintered conductive silver paste, comprising the following steps:
S1、将以下重量百分比的原料：30％～70％溶剂、0.1％～2％分散助剂、0.1％～5％有机载体进行旋转混匀，形成粘结载体；S1, the following weight percentage of raw materials: 30% to 70% solvent, 0.1% to 2% dispersing aid, 0.1% to 5% organic carrier is rotated and mixed to form a binding carrier;
S2、将以重量百分比计20％～60％纳米银粉和2％～10％纳米铝热剂加入到所述粘结载体中，进行旋转混匀，得到所述自放热无压烧结导电银浆。S2, adding 20% to 60% nano silver powder and 2% to 10% nano aluminum heat agent in a weight percentage to the bonding carrier, and rotating and mixing to obtain the self-heating pressureless sintered conductive silver paste .
本制备方法优选在常温常压下进行。The preparation method is preferably carried out under normal temperature and normal pressure.
优选地，在步骤S1中，旋转的转速为500rpm～1000rpm。Preferably, in step S1, the rotational speed of the rotation is 500 rpm to 1000 rpm.
优选地，在步骤S2中，旋转的转速为300rpm～500rpm。Preferably, in step S2, the rotational speed of the rotation is 300 rpm to 500 rpm.
有益效果：Beneficial effects:
适用于第三代宽禁带半导体芯片的粘结及散热。Suitable for bonding and heat dissipation of the third generation of wide bandgap semiconductor chips.
与现有技术相比，本发明在纳米银溶液中加入了具有放热效应的纳米铝热剂，此类材料发生氧化还原反应可以释放大量的热量(即在200℃～250℃即可引发放热反应)，并被纳米银颗粒所吸收，实现纳米银颗粒烧结层的热增幅效应，降低了银浆的烧结温度，提高了粘结层的致密性、强度以及与基质的附着力(也即是说，使得该自放热无压烧结导电银浆具有后处理温度低，耐高温、高导热以及高粘结特性)。该法不仅克服了现有导电银浆后处理温度相对较高及烧结过程非致密化扩散引起的粘结性差问题，而且简化了后处理工艺，可显著提高封装器件的可靠性，尤其适用于第三代宽禁带半导体芯片的粘结及散热使用。本发明提供一种新颖结构组成的自放热无压烧结导电银浆， 为第三代宽禁带半导体芯片的粘结及散热设计提供新思路。Compared with the prior art, the present invention adds a nano-aluminothermic agent having an exothermic effect to the nano-silver solution, and the redox reaction of such materials can release a large amount of heat (ie, the exothermic can be induced at 200 ° C to 250 ° C). The reaction is absorbed by the nano silver particles to achieve the thermal amplification effect of the sintered layer of the nano silver particles, lowering the sintering temperature of the silver paste, and improving the compactness, strength and adhesion to the matrix of the bonding layer (ie, It is said that the self-heating pressureless sintered conductive silver paste has low post-treatment temperature, high temperature resistance, high thermal conductivity and high bonding property). The method not only overcomes the problem of poor post-treatment temperature of the existing conductive silver paste and the non-densified diffusion of the sintering process, but also simplifies the post-processing process, and can significantly improve the reliability of the packaged device, especially for the first Bonding and heat dissipation of three generations of wide bandgap semiconductor chips. The invention provides a self-heating pressureless sintered conductive silver paste with novel structure, which provides a new idea for the bonding and heat dissipation design of the third generation wide band gap semiconductor chip.
具体实施方式Detailed ways
下面结合实施例对本发明作进一步说明。The invention is further illustrated by the following examples.
实施例1Example 1
一种自放热无压烧结导电银浆的制备方法，包括如下步骤：A preparation method of self-heating pressureless sintered conductive silver paste, comprising the following steps:
S1、依次称取30g松油醇、20g乙二醇丁醚醋酸酯、0.3g十二烷基硫醇、0.2g聚乙烯吡咯烷酮加入到反应釜中，在1000rpm转速下搅拌60min，直至聚乙烯吡咯烷酮完全溶解。S1, weighed 30 g of terpineol, 20 g of ethylene glycol butyl ether acetate, 0.3 g of dodecyl mercaptan, 0.2 g of polyvinylpyrrolidone into the reaction kettle, and stirred at 1000 rpm for 60 min until polyvinylpyrrolidone completely dissolved.
S2、分批加入45g银粉(粒径50nm)和4.5g Al/MoO 3纳米铝热剂(粒径10nm)，在300rpm转速下继续混合混匀，即可得到自放热无压烧结导电银浆。 S2, 45g silver powder (particle size 50nm) and 4.5g Al/MoO 3 nano-aluminothermic agent (particle size 10nm) were added in batches, and mixing and mixing were continued at 300 rpm to obtain self-heating pressureless sintered conductive silver paste. .
本实施例获得的该自放热无压烧结导电银浆在250℃烧结30min，其体积电阻率为3.17×10 -6ohm·cm，导热系数为209W/(m·K)，粘结强度大于43.5MPa。 The self-heating pressureless sintered conductive silver paste obtained in this embodiment is sintered at 250 ° C for 30 min, and has a volume resistivity of 3.17×10 -6 ohm·cm, a thermal conductivity of 209 W/(m·K), and a bonding strength greater than 43.5 MPa.
实施例2Example 2
一种自放热无压烧结导电银浆的制备方法，包括如下步骤：A preparation method of self-heating pressureless sintered conductive silver paste, comprising the following steps:
S1、依次称取10g甲乙酮、10g醋酸丁酯、15g乙二醇丁醚醋酸酯、0.2g油胺、2.0g聚乙烯醇缩甲醛加入到反应釜中，在1000rpm转速下搅拌60min，直至聚乙烯醇缩甲醛完全溶解分散。S1, weigh 10 g of methyl ethyl ketone, 10 g of butyl acetate, 15 g of ethylene glycol butyl ether acetate, 0.2 g of oleylamine, 2.0 g of polyvinyl formal, and added to the reaction kettle, and stirred at 1000 rpm for 60 min until the polyethylene The formal is completely dissolved and dispersed.
S2、分批加入60g银粉(粒径30nm)和2.8g Al/MoO 3纳米铝热剂(粒径10nm)，在300rpm转速下继续混合混匀，即可得到自放热无压烧结导电银浆。 S2, 60g silver powder (particle size 30nm) and 2.8g Al/MoO 3 nano-aluminothermic agent (particle size 10nm) were added in batches, and mixing and mixing were continued at 300 rpm to obtain self-heating pressureless sintered conductive silver paste. .
本实施例获得的该自放热无压烧结导电银浆在250℃烧结30min，其体积电阻率为1.86×10 -6ohm·cm，导热系数为226W/(m·K)，粘结强度大于41.3MPa。 The self-heating pressureless sintered conductive silver paste obtained in this embodiment is sintered at 250 ° C for 30 min, and has a volume resistivity of 1.86×10 -6 ohm·cm, a thermal conductivity of 226 W/(m·K), and a bonding strength greater than 41.3 MPa.
实施例3Example 3
一种自放热无压烧结导电银浆的制备方法，包括如下步骤：A preparation method of self-heating pressureless sintered conductive silver paste, comprising the following steps:
S1、依次称取10g甲乙酮、15g乙二醇、15g碳酸二苯酯、0.1g油胺、0.1g聚乙烯吡咯烷酮和1.5g聚丙烯酸酯加入到反应釜中，在1000rpm转速下搅拌60min，直至聚乙烯吡咯烷酮和聚丙烯酸酯完全溶解分散。S1, 10 g of methyl ethyl ketone, 15 g of ethylene glycol, 15 g of diphenyl carbonate, 0.1 g of oleylamine, 0.1 g of polyvinylpyrrolidone and 1.5 g of polyacrylate were sequentially weighed into the reaction vessel, and stirred at 1000 rpm for 60 min until the polymerization was completed. The vinylpyrrolidone and polyacrylate are completely dissolved and dispersed.
S2、分批加入55g银粉(粒径30nm)和3.3g Al/Fe 2O 3纳米铝热剂(粒径15nm)，在300rpm转速下继续混合混匀，即可得到自放热无压烧结导电银浆。 S2, 55g silver powder (particle size 30nm) and 3.3g Al/Fe 2 O 3 nano-aluminum heat agent (particle size 15nm) were added in batches, and mixing and mixing were continued at 300 rpm to obtain self-heating pressureless sintered conductive Silver paste.
本实施例获得的该自放热无压烧结导电银浆在250℃烧结30min，其体积电阻率为6.19×10 -6ohm·cm、导热系数为192W/(m·K)，粘结强度大于37.7MPa。 The self-heating pressureless sintered conductive silver paste obtained in this embodiment is sintered at 250 ° C for 30 min, and has a volume resistivity of 6.19×10 -6 ohm·cm and a thermal conductivity of 192 W/(m·K), and the bonding strength is greater than 37.7MPa.
实施例4Example 4
一种自放热无压烧结导电银浆的制备方法，包括如下步骤：A preparation method of self-heating pressureless sintered conductive silver paste, comprising the following steps:
S1、依次称取10g甲乙酮、15g乙二醇、15g碳酸二苯酯、0.1g油胺、0.1g聚乙烯吡咯烷酮和1.5g聚丙烯酸酯加入到反应釜中，在1000rpm转速下搅拌60min，直至聚乙烯吡咯烷酮和聚丙烯酸酯完全溶解分散。S1, 10 g of methyl ethyl ketone, 15 g of ethylene glycol, 15 g of diphenyl carbonate, 0.1 g of oleylamine, 0.1 g of polyvinylpyrrolidone and 1.5 g of polyacrylate were sequentially weighed into the reaction vessel, and stirred at 1000 rpm for 60 min until the polymerization was completed. The vinylpyrrolidone and polyacrylate are completely dissolved and dispersed.
S2、分批加入55g银粉(粒径30nm)和3.3g Al/CuO纳米铝热剂(粒径10nm)，在300rpm转速下继续混合混匀，即可得到自放热无压烧结导电银浆。S2, 55g silver powder (particle size 30nm) and 3.3g Al/CuO nano-aluminum heat agent (particle size 10nm) were added in batches, and mixing and mixing were continued at 300 rpm to obtain self-heating pressureless sintered conductive silver paste.
本实施例获得的该自放热无压烧结导电银浆在250℃烧结30min，其体积电阻率为4.76×10 -6ohm·cm，导热系数为201W/(m·K)，粘结强度大于40.3MPa。 The self-heating pressureless sintered conductive silver paste obtained in this embodiment is sintered at 250 ° C for 30 min, and has a volume resistivity of 4.76×10 -6 ohm·cm, a thermal conductivity of 201 W/(m·K), and a bonding strength greater than 40.3 MPa.
对比例1Comparative example 1
一种导电银浆的制备方法，包括如下步骤：A method for preparing a conductive silver paste, comprising the steps of:
S1、依次称取10g甲乙酮、15g乙二醇、15g碳酸二苯酯、0.1g油胺、0.1g聚乙烯吡咯烷酮和1.5g聚丙烯酸酯加入到反应釜中，在1000rpm转速下搅拌60min，直至聚乙烯吡咯烷酮和聚丙烯酸酯完全溶解分散。S1, 10 g of methyl ethyl ketone, 15 g of ethylene glycol, 15 g of diphenyl carbonate, 0.1 g of oleylamine, 0.1 g of polyvinylpyrrolidone and 1.5 g of polyacrylate were sequentially weighed into the reaction vessel, and stirred at 1000 rpm for 60 min until the polymerization was completed. The vinylpyrrolidone and polyacrylate are completely dissolved and dispersed.
S2、分批加入58.3g银粉(粒径30nm)，在300rpm转速下继续搅拌120min直至分散均匀，即可得到导电银浆。S2, 58.3 g of silver powder (particle size 30 nm) was added in portions, and stirring was continued for 120 min at 300 rpm until the dispersion was uniform, and a conductive silver paste was obtained.
本比较实施例获得的该导电银浆在250℃烧结30min，其体积电阻率为5.96×10 -6ohm·cm、导热系数为15.2W/(m·K)，粘结强度大于4.5MPa。 The conductive silver paste obtained in the comparative example was sintered at 250 ° C for 30 min, and had a volume resistivity of 5.96×10 -6 ohm·cm, a thermal conductivity of 15.2 W/(m·K), and a bond strength of more than 4.5 MPa.
根据实施例1至实施例4与对比例1的比较可以看出，在本发明的实施例1至实施例4中，由于采用了上述组分配方，与作为现有产品的对比实施例1相比，本发明制备的自放热无压烧结导电银浆具有耐高温、高导热以及高粘结特性，在第三代宽禁带半导体芯片的粘结及散热中将发挥重要作用。According to the comparison of Example 1 to Example 4 with Comparative Example 1, it can be seen that in the embodiment 1 to the embodiment 4 of the present invention, since the above-described component formulation was employed, it was compared with Comparative Example 1 as an existing product. In contrast, the self-heating pressureless sintered conductive silver paste prepared by the invention has high temperature resistance, high thermal conductivity and high bonding property, and plays an important role in the bonding and heat dissipation of the third generation wide band gap semiconductor chip.
以上内容是结合具体的优选实施方式对本发明所作的进一步详细说明，不能认定本发明的具体实施只局限于这些说明。对于本发明所属技术领域的普通技术人员来说，在不脱离本发明构思的前提下，还可以做出若干简单推演或替换，都应当视为属于本发明由所提交的权利要求书确定的专利保护范围。The above is a further detailed description of the present invention in connection with the specific preferred embodiments, and the specific embodiments of the present invention are not limited to the description. For those skilled in the art to which the present invention pertains, a number of simple derivations or substitutions may be made without departing from the inventive concept, and should be considered as belonging to the invention as defined by the appended claims. protected range.

Claims (10)

  1. 一种自放热无压烧结导电银浆，其中，包括以下重量百分比的原料：20％～60％纳米银粉、30％～70％溶剂、2％～10％纳米铝热剂、0.1％～2％分散助剂和0.1％～5％有机载体。A self-heating pressureless sintered conductive silver paste, comprising: the following weight percentage of raw materials: 20% to 60% nano silver powder, 30% to 70% solvent, 2% to 10% nano aluminum heat agent, 0.1% to 2 % dispersing aid and 0.1% to 5% organic carrier.
  2. 如权利要求1所述的自放热无压烧结导电银浆，其中，所述纳米银粉的尺寸为5nm～100nm。The self-heating pressureless sintered conductive silver paste according to claim 1, wherein the nano silver powder has a size of 5 nm to 100 nm.
  3. 如权利要求1所述的自放热无压烧结导电银浆，其中，所述溶剂为甲醇、乙醇、苯甲醇、乙二醇、丙酮、甲乙酮、甲基异丁基酮、环己酮、乙二醇单甲醚、乙二醇单乙醚、乙二醇单丁醚、石油醚、四氢呋喃、苯、甲笨、二甲苯、四氯化碳、乙酸乙酯、乙酸丁酯、戊烷、己烷、辛烷、环己烷、乙二醇丁醚醋酸酯、丙二醇甲醚醋酸酯、二乙二醇单丁醚醋酸酯、松油醇、碳酸二甲酯以及碳酸二苯酯中的至少一种。The self-heating pressureless sintered conductive silver paste according to claim 1, wherein the solvent is methanol, ethanol, benzyl alcohol, ethylene glycol, acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, and B. Glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, petroleum ether, tetrahydrofuran, benzene, methyl bromide, xylene, carbon tetrachloride, ethyl acetate, butyl acetate, pentane, hexane At least one of octane, cyclohexane, ethylene glycol butyl ether acetate, propylene glycol methyl ether acetate, diethylene glycol monobutyl ether acetate, terpineol, dimethyl carbonate, and diphenyl carbonate. .
  4. 如权利要求1所述的自放热无压烧结导电银浆，其中，所述分散剂为聚乙二醇、聚乙烯醇、聚乙烯吡咯烷酮、十六烷基溴化铵、肉豆蔻醇、十二胺、油胺、辛硫醇、十二烷基硫醇以及十六烷基硫醇中的至少一种。The self-heating pressureless sintered conductive silver paste according to claim 1, wherein the dispersing agent is polyethylene glycol, polyvinyl alcohol, polyvinylpyrrolidone, cetyl ammonium bromide, myristyl alcohol, ten At least one of a diamine, oleylamine, octyl mercaptan, dodecyl mercaptan, and cetyl mercaptan.
  5. 如权利要求1所述自放热无压烧结导电银浆，其中，所述纳米铝热剂为Al/Fe 2O 3、Al/CuO、Al/MoO 3、Al/WO 3、Al/PbO和Al/SiO 2中的至少一种。 The self-heating pressureless sintered conductive silver paste according to claim 1, wherein the nano-alumina is Al/Fe 2 O 3 , Al/CuO, Al/MoO 3 , Al/WO 3 , Al/PbO, and At least one of Al/SiO 2 .
  6. 如权利要求5所述自放热无压烧结导电银浆，其中，所述纳米铝热剂的尺寸在3nm～20nm。A self-heating pressureless sintered conductive silver paste according to claim 5, wherein said nanoaluminum heat agent has a size of from 3 nm to 20 nm.
  7. 如权利要求1所述的自放热无压烧结导电银浆，其中，所述有机载体为聚吡咯烷酮类、环氧树脂类、酚醛树脂类、丙烯酸类、氨基甲酸酯类、硅树脂类、聚亚烷基碳酸酯类、聚乙烯醇缩醛类和纤维素类中的至少一种。The self-heating pressureless sintered conductive silver paste according to claim 1, wherein the organic carrier is a polypyrrolidone, an epoxy resin, a phenol resin, an acrylic, a urethane, a silicone, or a poly At least one of an alkylene carbonate, a polyvinyl acetal, and a cellulose.
  8. 一种自放热无压烧结导电银浆的制备方法，其中，包括如下步骤：A preparation method of self-heating pressureless sintered conductive silver paste, comprising the following steps:
    S1、将以下重量百分比的原料：30％～70％溶剂、0.1％～2％分散助剂、0.1％～5％有机载体进行旋转混匀，形成粘结载体；S1, the following weight percentage of raw materials: 30% to 70% solvent, 0.1% to 2% dispersing aid, 0.1% to 5% organic carrier is rotated and mixed to form a binding carrier;
    S2、将以重量百分比计20％～60％纳米银粉和2％～10％纳米铝热剂加入到所述粘结载体中，进行旋转混匀，得到所述自放热无压烧结导电银浆。S2, adding 20% to 60% nano silver powder and 2% to 10% nano aluminum heat agent in a weight percentage to the bonding carrier, and rotating and mixing to obtain the self-heating pressureless sintered conductive silver paste .
  9. 如权利要求8所述的制备方法，其中，在步骤S1中，旋转的转速为500rpm～1000rpm。The production method according to claim 8, wherein in step S1, the rotation speed of the rotation is 500 rpm to 1000 rpm.
  10. 如权利要求8所述的制备方法，其中，在步骤S2中，旋转的转速为300rpm～500rpm。The production method according to claim 8, wherein in step S2, the number of rotations of the rotation is from 300 rpm to 500 rpm.
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