WO2020215739A1 - 一种纳米金属膜模块制备方法及其基板制备方法 - Google Patents

一种纳米金属膜模块制备方法及其基板制备方法 Download PDF

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WO2020215739A1
WO2020215739A1 PCT/CN2019/123826 CN2019123826W WO2020215739A1 WO 2020215739 A1 WO2020215739 A1 WO 2020215739A1 CN 2019123826 W CN2019123826 W CN 2019123826W WO 2020215739 A1 WO2020215739 A1 WO 2020215739A1
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nano
metal
metal film
film module
nano metal
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PCT/CN2019/123826
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English (en)
French (fr)
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刘旭
叶怀宇
张卫红
敖日格力
李俊
张国旗
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深圳第三代半导体研究院
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Publication of WO2020215739A1 publication Critical patent/WO2020215739A1/zh

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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
    • H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
    • H01L21/04—Manufacture or treatment of semiconductor devices or of parts thereof the devices having potential barriers, e.g. a PN junction, depletion layer or carrier concentration layer
    • H01L21/48—Manufacture or treatment of parts, e.g. containers, prior to assembly of the devices, using processes not provided for in a single one of the subgroups H01L21/06 - H01L21/326
    • H01L21/4814—Conductive parts
    • H01L21/4846—Leads on or in insulating or insulated substrates, e.g. metallisation
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
    • H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
    • H01L21/04—Manufacture or treatment of semiconductor devices or of parts thereof the devices having potential barriers, e.g. a PN junction, depletion layer or carrier concentration layer
    • H01L21/48—Manufacture or treatment of parts, e.g. containers, prior to assembly of the devices, using processes not provided for in a single one of the subgroups H01L21/06 - H01L21/326
    • H01L21/4814—Conductive parts
    • H01L21/4846—Leads on or in insulating or insulated substrates, e.g. metallisation
    • H01L21/4867—Applying pastes or inks, e.g. screen printing
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L23/00—Details of semiconductor or other solid state devices
    • H01L23/48—Arrangements for conducting electric current to or from the solid state body in operation, e.g. leads, terminal arrangements ; Selection of materials therefor
    • H01L23/488—Arrangements for conducting electric current to or from the solid state body in operation, e.g. leads, terminal arrangements ; Selection of materials therefor consisting of soldered or bonded constructions
    • H01L23/498—Leads, i.e. metallisations or lead-frames on insulating substrates, e.g. chip carriers
    • H01L23/49866—Leads, i.e. metallisations or lead-frames on insulating substrates, e.g. chip carriers characterised by the materials
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L2224/00—Indexing scheme for arrangements for connecting or disconnecting semiconductor or solid-state bodies and methods related thereto as covered by H01L24/00
    • H01L2224/80—Methods for connecting semiconductor or other solid state bodies using means for bonding being attached to, or being formed on, the surface to be connected
    • H01L2224/83—Methods for connecting semiconductor or other solid state bodies using means for bonding being attached to, or being formed on, the surface to be connected using a layer connector
    • H01L2224/838—Bonding techniques
    • H01L2224/8384—Sintering

Definitions

  • the invention relates to the field of chip packaging interconnection, and more specifically to the preparation technology of a composite substrate.
  • semiconductor devices In the semiconductor fields such as power electronics and optoelectronic communications, semiconductor devices often need to carry extreme conditions such as high voltage, high current, high switching speed, and high operating temperature during operation. With the continuous recording of operating voltage and current of power devices in recent years Refreshing, as well as the continuous reduction of chip size, the power density of the power device as a whole will increase dramatically, which poses new challenges to the various components of the chip package. As the part that is in direct contact with the chip, the substrate plays a variety of functions such as mechanical support, conductive interconnection, heat dissipation management, and breakdown prevention, and its development is closely related to the performance of the chip.
  • the mainstream solutions for preparing cermet substrates currently mainly include: direct copper coating (DCB or DBC) and active metal brazing (AMB).
  • DCB direct copper coating
  • AMB active metal brazing
  • the DCB process uses the eutectic reaction of copper and aluminum oxide at low oxygen concentration (less than 5ppm) and about 1065°C to form a eutectic phase at the interface to achieve cermet connection.
  • the DCB process is relatively simple, but the disadvantage is that the process temperature is too high, and there is a large difference in thermal expansion coefficient between copper and aluminum oxide, which makes the metal-ceramic interface produce large thermal stress and cause cracks during the preparation process and use process Risks: At the same time, the thermal conductivity, bending strength, and fracture toughness of alumina materials are relatively poor, which makes it unsuitable for future automotive electronics, electric locomotives and smart grid applications.
  • the AMB process uses active metal solder to weld metal and ceramics together under vacuum or protective atmosphere conditions. This process improves the strength of the cermet connecting layer, and through the use of titanium-containing brazing material, it is possible to weld copper and silicon nitride ceramics with higher performance.
  • vacuum conditions are indispensable, which limits its application in mass production.
  • the metal-ceramic substrate plays a variety of functions such as mechanical support, conductive interconnection, heat dissipation management and prevention of breakdown, which directly affects the performance and working life of the device.
  • Copper-ceramic substrates have been widely used in the power electronics industry because they combine the high electrical conductivity, high thermal conductivity, and low cost characteristics of copper, as well as the high dielectric coefficient and high fracture toughness of ceramics. Among them, the process of using thick film to prepare cermet substrates is widely used due to its ease of operation, design flexibility, and material saving.
  • the first prior art is a patent application with a patent publication number of US2005/0051253A, which discloses a ceramic substrate directly coated with a plurality of metal conductive coatings. A ceramic paste is printed between these metal coatings to fill the gaps between the metal conductive coatings.
  • the second prior art is a patent application with a patent publication number of US2004/0163555A, which discloses a ceramic substrate with a metal conductive coating, in which a ceramic slurry is additionally used to fill the gap between the circuits formed by the metal conductive coating. The corresponding ceramic slurry is prepared by mixing ceramic powder with an organic carrier.
  • the third prior art is a patent application with a patent publication number EP3419390A1, which discloses a bonding process in which a conductive copper paste is used as a connecting layer between a copper foil and a ceramic, in which glass etc. are used as bonding auxiliary additives.
  • organic additives and solvents will volatilize, causing the copper paste to form a dense copper layer.
  • the glass additive will reach the metal-ceramic interface through diffusion or flow, and wet the two surfaces to form a bond. Through this process, the reliability of thermal cycling has been improved more than ten times.
  • the above-mentioned copper-clad substrate preparation process is limited by the process on the one hand, and the steps of printing, drying, and baking must be performed continuously and uninterrupted; and the thick copper substrate preparation unit needs to constantly purchase new printing screens to meet the needs of its pattern design update. The old design screen will produce unnecessary waste.
  • the present invention provides a nano metal film module, including:
  • the nano metal auxiliary connection module includes first metal particles and second metal particles, and the first metal particles and the second metal particles have different diameters.
  • the diameter of the first metal particles is 0.1 um-100 ⁇ m; the diameter of the second metal particles is 0.5 nm-100 nm.
  • the nano-metal auxiliary connection module is continuous or discontinuous discretely arranged small pieces; the nano-metal auxiliary connection module has a single-layer, double-layer, three-layer or multi-layer structure.
  • the thickness of the nano-metal auxiliary connection module is 1 micrometer to 500 micrometers in thickness.
  • the nano metal film module further includes a connection auxiliary additive, an organic carrier and a solvent.
  • the first metal particles account for 45wt.% to 95wt.% of the auxiliary module material; the second metal particles account for 5wt.% to 55wt.% of the auxiliary layer material; the connection auxiliary additive accounts for auxiliary 0.1wt% to 9.9wt% of the layer material.
  • the materials of the first metal particles and the second metal particles are: three-group elements including aluminum and indium, four-group elements including carbon, silicon, tin, and lead, and five-group elements including phosphorus, bismuth, and antimony.
  • connection auxiliary additive includes: a glass or ceramic phase composed of bismuth oxide, silicon oxide, aluminum oxide, calcium oxide, sodium oxide, cesium oxide, yttrium oxide, zinc oxide, magnesium oxide, boron oxide, and titanium oxide; or/and includes : Silver, copper, titanium, tin, indium, lead.
  • the shapes of the first metal particles and the second metal particles are spherical, fibrous, snowflake, flake, and/or linear.
  • the base material and the nano-metal auxiliary connection module have weak adhesion or no adhesion at all.
  • a method for preparing a nano metal film module includes:
  • Step 1 Use micron-level metal particles or micron/nano-level mixed metal particles to configure the metal solder slurry
  • Step 2 Printing the metal paste on the substrate to form a thick film
  • Step 3 Form a thick film preform by screen printing or laser cutting
  • Step 4 Spraying or packaging the thick film preform by anti-oxidation.
  • the configuration method of step 1 is:
  • the second metal particles are mixed into the first paste by a mechanical mixing method;
  • the mechanical mixing method is to prepare the metal slurry by magnetic stirring, vacuum defoaming, and evaporation;
  • the substrate is a carbonized glass, ceramic, metal, or organic polymer substrate.
  • the step 2 includes:
  • Step 2.1 Design the printing screen according to the shape and size of the required discrete preforms
  • Step 2.2 Print the paste on the substrate by screen printing.
  • the step 2 includes:
  • the step 3 is: cutting the thick film prefabricated module by laser cutting or forging.
  • the screen is a screen printed with a non-specific area metal film.
  • the metal slurry in step 1 includes first metal particles, second metal particles, connection auxiliary additives, organic vehicles and solvents.
  • the step 1 further includes a metal slurry pretreatment process, and the metal slurry pretreatment process includes:
  • the metal slurry is processed by defoaming, stirring, and grinding methods.
  • the step 3 also includes a drying process.
  • the drying process is: the drying temperature is 100-150°C and the duration is 5-30 minutes.
  • a method for preparing a substrate using a nano metal film module includes:
  • Step 1 Coating adhesive on the bottom of the nano metal film module
  • Step 2 Place the nano metal film module on a substrate
  • Step 3 Place metal foil on the surface of the nano metal film module
  • Step 4 Bake according to the set temperature curve and atmosphere
  • Step 5 Cool to form a metal-clad substrate.
  • the binder is alcohol or an organic solvent
  • the substrate is a ceramic substrate.
  • At least one nano metal film module is distributed on at least one surface of the substrate
  • the set temperature curve is: a peak temperature of 400-900°C, and a duration of 30 seconds to 30 minutes; the atmosphere is: a nitrogen atmosphere or a reducing atmosphere with an oxygen content of less than 6ppm
  • the method for preparing the nano metal film module and the substrate preparation method provided by the present invention can be customized and updated from the preform manufacturer according to the requirements, avoiding the waste generated by the new screen, and improving thermal stability, heat dissipation efficiency, and The technical effect of bonding strength and improving package reliability.
  • Fig. 1 is a schematic diagram of the process of preparing a cermet substrate using the nano metal membrane module of the present invention.
  • Figure 2 is a flow chart of the preparation and application of the nano metal film module of the present invention.
  • Fig. 3 is a schematic diagram of the single-layer prefabricated module of the present invention and its preparation process.
  • Discrete multi-position storage box 1 unused nano metal film module 2, nano metal film module 3 to be connected, ceramic substrate 4, metal foil 5, connecting layer 6 formed after baking, first material Metal paste 7, first material particles 8, nanoparticle generator 9, electric or magnetic field 10, second material particles 10, mixed paste 11, printing squeegee 12, printing screen (A) 13, printing screen (B ) 14, non-adhesive substrate 15, discrete prefabricated module 16, to be cut prefabricated module 17, laser 18
  • This embodiment provides a single-layer prefabricated module structure and a preparation method thereof, as shown in FIGS. 2 and 3.
  • the first material is silver copper titanium active brazing material
  • the second material is nano copper particles.
  • the preparation method is:
  • solder is screen printed on a non-sticky carbonized glass carrier through a specific pattern to form a separate prefabricated module to be dried;
  • the final prefabricated module is formed by drying the thick film.
  • the use of small-size nano-copper particles mixed with the first material effectively reduces the welding temperature; secondly, the small-size nano-copper particles effectively fill the original gaps between the first material particles, which can effectively improve the The density of the connection auxiliary layer during segment welding.
  • This embodiment provides a single-layer prefabricated module structure and a preparation method thereof, as shown in FIGS. 2 and 3.
  • the main body (first material) is silver copper titanium active brazing material slurry
  • the second material is nano copper particles.
  • the preparation method is:
  • solder is screen printed with a specific pattern onto a non-sticky carbonized glass carrier to form a complete prefabricated module to be dried;
  • a laser is used to cut a complete prefabricated module to form a discrete module with a specific shape and size. Compared with the traditional screen printing process, it has a higher degree of design freedom.
  • This embodiment provides a multilayer prefabricated module structure and a preparation method thereof.
  • a slurry containing large-size metal particles and a slurry containing small-size nano copper particles are sequentially printed on the surface of a non-sticky substrate to form a stack A prefabricated module with a layer structure; the large and small metal particles in the multi-layer material of the module will merge with each other along with the diffusion phenomenon in the subsequent welding metal-ceramic substrate process, and fill the gaps with each other, thereby increasing the density of the auxiliary layer and increasing Connection strength.
  • the first material also includes gold, palladium, silver, copper, aluminum, silver-palladium alloy, gold-palladium alloy, copper-silver alloy, copper-silver-nickel alloy Or copper-aluminum alloy.);
  • step 4) Printing the second material slurry on the surface of the first slurry in step 3) using screen printing technology; drying;
  • This embodiment provides a method for preparing a metal-ceramic substrate using a prefabricated module, and the steps for preparing a metal-clad substrate by using the nano metal film module are shown in FIG. 1:
  • Cooling system to form a metal-ceramic substrate.
  • the organic solvent will be completely volatilized during the baking process.
  • the baking process parameters can be set to the peak temperature of 400 ⁇ 900°C, 30 seconds to 10 minutes) and nitrogen (control the oxygen content below 6ppm) atmosphere bake.
  • the combination of nano-copper + micro-copper reduces the overall average particle size of the copper material, thereby achieving the effect of reducing the sintering temperature.
  • the traditional sintering temperature is 900-1100°C, while the sintering temperature of the present invention is 400 ⁇ 900°C; on the other hand, the nano-copper particles will be uniformly mixed with the micron copper in the copper paste, so that the voids generated by the original micron copper paste will be filled during sintering, thereby increasing the density of the sintered copper layer.
  • the invention provides a nano metal film module and a preparation method thereof:
  • the metal solder connection auxiliary layer is improved from the traditional "slurry” state to the "prefabricated module” state, which is easy to store; the metal solder connection auxiliary layer has a use effect similar to "double-sided tape", which can be taken and used at any time .
  • the nano metal membrane module can be customized and designed according to requirements, its shape, size, material matching, etc., through the implementation of this scheme, avoid the disadvantages of the traditional metal ceramic connection process that must be performed continuously, and have a high degree of freedom in use.
  • the complete metal solder film is cut to form a prefab module by using laser cutting, forging, etc., which can avoid the waste of buying a new printing screen; the metal ceramic substrate preparation unit can also customize the prefab from the nano metal film module manufacturer according to demand , which simplifies the complexity of production.
  • the present invention uses metal particles with a mixture of large and small sizes to fill the gaps of the particles that originally existed.
  • the specific selection of the size of the larger and smaller particles of the nano metal particles of the present invention is not possible with the combination of other diameter size metal particles.
  • the present invention improves the density after soldering, so that the metal solder connection aid of the present invention has the technical effects of improving thermal stability, enhancing heat dissipation efficiency, enhancing bonding strength and improving packaging reliability.

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Abstract

一种纳米金属膜模块制备方法及其基板制备方法，所述纳米金属膜模块包括纳米金属辅助连接模块(3)，基底(4)，所述纳米金属辅助连接模块(3)包括第一金属颗粒(8)、第二金属颗粒(10)；所述制备步骤包括：步骤1：采用微米级金属颗粒或微米/纳米级混合金属颗粒配置金属浆料；步骤2：将所述金属浆料印制在无粘性基底上，形成待干燥厚膜；步骤3：通过干燥形成厚膜预制件。可按照需求从预制件制造商定制、更新预制件，避免了新丝网产生的浪费，具有改善热稳定性、提升散热效率、提升键合强度和改善封装可靠性的技术效果。

Description

一种纳米金属膜模块制备方法及其基板制备方法 技术领域
本发明涉及芯片封装互连领域，更具体地涉及复合基板的制备技术。
背景技术
在功率电子、光电通讯等半导体领域中，半导体器件在工作时往往需承载高电压、大电流、高开关速率、高工作节温度等极端条件，随着近年来功率器件的工作电压和电流记录不断刷新，以及芯片尺寸的不断减小，功率器件整体所承受的功率密度将随之急剧增加，这对芯片封装的各个部件提出了新的挑战。作为与芯片直接接触的部分，基板(substrate)起着机械支撑、导电互联、散热管理和防止击穿等多种功能，其发展与芯片性能紧密相关。传统柔性基板或金属基板已无法满足宽禁带半导体高性能要求；与之相比金属-陶瓷复合基板(metal-ceramic substrate)具有良好的导热性、高绝缘性、低热膨胀系数、以及高机械强度，是功率电子关键材料。其中覆铜陶瓷基板(copper-ceramic substrate)因结合了铜的高导电、高导热、低成本特点，以及陶瓷高介电系数、高断裂韧性等优势，在电力电子行业获得了广泛的应用。
制备金属陶瓷基板主流方案目前主要有：直接覆铜工艺(DCB或DBC)和活性金属钎焊(AMB)。其中DCB工艺是利用铜和氧化铝在低氧气浓度(低于5ppm)和1065℃左右的共晶反应在界面形成共晶相而实现金属陶瓷连接的。DCB工艺相对简单，但缺点是工艺温度过高，铜与氧化铝有较大的热膨胀系数差异，使得在制备工艺和使用过程中，金属陶瓷界面处都有产生较大热应力并导致裂纹产生的风险；同时氧化铝材料的导热率、抗弯强度、断裂韧性相对较差，导致其并不适用于未来汽车电子、电动机车和智能电网的应用。AMB工艺是利用活性金属焊料在真空或保护性气氛条件下将金属和陶瓷焊接在一起的。此工艺提高了金属陶瓷连接层的强度，并且通过使用含钛的钎焊料，使得焊接铜和具有更高性能的氮化硅陶瓷成为了可能。然而由于AMB活性钎料极易氧化，使得真空条件必不可少，因而限制了其大规模生产中的应用。
金属陶瓷基板(metal-ceramic substrate)作为与功率芯片直接接触的部分，起着机械支撑、导电互联、散热管理和防止击穿等多种功能，因而直接影响着器件的性能 表现和工作寿命。覆铜陶瓷基板(copper-ceramic substrate)因结合了铜的高导电、高导热、低成本特点，以及陶瓷高介电系数、高断裂韧性等优势，在电力电子行业获得了广泛的应用。其中利用厚铜技术(thick film)制备金属陶瓷基板的工艺因其操作简易性、设计灵活性、材料节约等特点被广泛使用。
现有技术一为专利公开号为US2005/0051253A的专利申请，其公开了直接涂覆有若干金属导电涂层的陶瓷基板。在这些金属涂层之间印刷陶瓷浆料从而填充金属导电涂层之间的间隙。现有技术二为专利公开号为US2004/0163555A的专利申请，其公开了具有金属导电涂层的陶瓷基板，其中额外使用陶瓷浆料填充在金属导电涂层形成的电路之间的间隙。相应的陶瓷浆料的制备，是将陶瓷粉末与有机载体混合而获得。现有技术三为专利公开号为EP3419390A1的专利申请，其公开了一种在铜箔与陶瓷之间使用导电铜浆作为连接层的键合工艺，其中使用玻璃等作为键合辅助添加剂。在烘烤过程中，有机添加剂和溶剂将会挥发，使铜浆形成致密的铜层。其中铜浆中的铜颗粒具有D 50＝0.1到20um的粒径。在烧结过程中，玻璃添加剂会通过扩散或流动等方式到达金属-陶瓷界面，并润湿二者表面，从而形成键合。通过该工艺，热循环可靠性得到十倍以上的提升。
然而上述覆铜基板制备工艺一方面受到工艺限制，印刷、干燥、烘烤等步骤需连续不间断进行；且厚铜基板制备单位需不断购置新的印刷丝网以满足其图案设计更新的需要，而旧的设计丝网会产生不必要的浪费。
发明内容
传统覆铜陶瓷基板制备工艺一方面受到工艺限制，印刷、干燥、烘烤等步骤需连续不间断进行；且厚铜基板制备单位需不断购置新的印刷丝网以满足其图案设计更新的需要，而旧的设计丝网会产生不必要的浪费。为解决上述技术问题，本发明提供一种纳米金属膜模块，包括：
纳米金属辅助连接模块，
基底，
所述纳米金属辅助连接模块包括第一金属颗粒、第二金属颗粒，所述第一金属颗粒与所述第二金属颗粒直径不同。
优选的，所述第一金属颗粒直径为0.1um～100μm；所述第二金属颗粒直径为0.5nm～100nm。
优选的，所述纳米金属辅助连接模块是连续式，或，非连续式的离散排布的小块；所述纳米金属辅助连接模块具有单层、双层、三层或多层结构。
优选的，所述纳米金属辅助连接模块厚度为：1微米～500微米厚度。
优选的，所述纳米金属膜模块还包括连接辅助添加剂、有机载体和溶剂。
优选的，所述第一金属颗粒，占有辅助模块材料的45wt.％～95wt.％；所述第二金属颗粒，占有辅助层材料的5wt.％～55wt.％；所述连接辅助添加剂占有辅助层材料的0.1wt％～9.9wt％。
优选的，所述第一金属颗粒及所述第二金属颗粒材料为：包括铝、铟的三族元素，包括碳、硅、锡、铅的四族元素，包括磷、铋、锑的五族元素，包括铜、金、银的第一副族，包括钛、锆的第四副族，包括锰、钨、钼的第六副族，银钯合金、金钯合金、铜银合金、铜银镍合金、银铜钛、银铜铟、银铜锡、铝硅铜、铝硅、铝铜、铟锡；
所述连接辅助添加剂包括：氧化铋、氧化硅、氧化铝、氧化钙、氧化钠、氧化铯、氧化钇、氧化锌、氧化镁、氧化硼、氧化钛组成的玻璃或陶瓷相；或/和包括：银、铜、钛、锡、铟、铅。
优选的，所述第一金属颗粒及所述第二金属颗粒形状为：球型、纤维状、雪花状、片状和/或线状形状。
优选的，所述基底材料与所述纳米金属辅助连接模块有微弱粘结力、或完全无粘结力。
一种纳米金属膜模块的制备方法，包括：
步骤1：采用微米级金属颗粒或微米/纳米级混合金属颗粒配置金属焊料的浆料；
步骤2：将所述金属浆料印制在基底上，形成厚膜；
步骤3：通过丝网印刷方式或激光切割方式，形成厚膜预制件；
步骤4：通过防氧化喷涂或包装所述厚膜预制件。
优选的，所述步骤1的配置方法为：
采用机械混合的方法将第二金属颗粒混入第一膏体；所述机械混合方法为通过磁力搅拌、真空去泡，蒸发制备所述金属浆料；
或，利用电场、磁场或气流给第二纳米金属颗粒赋予动能，以物理冲击方式将第二纳米金属颗粒打入所述第一膏体，填充第一膏体中第一金属颗粒之间的间隙，形成多尺寸纳米颗粒混合的金属浆料。
优选的，所述基底为碳化玻璃、陶瓷、金属、或有机聚合基材。
优选的，通过丝网印刷方式，所述步骤2包括：
步骤2.1：根据所需离散型预制件的形状、尺寸设计印刷丝网；
步骤2.2：将所述浆料通过丝网印刷方式印制在所述基底上。
优选的，通过激光切割方式，所述步骤2包括：
将所述浆料通过丝网印制在所述基底上；
所述步骤3为：激光切割或锻压方式切割所述厚膜预制模块。
优选的，所述丝网为印制非特定面积金属膜的丝网。
优选的，所述步骤1的金属浆料包含第一金属颗粒、第二金属颗粒、连接辅助添加剂、有机载体和溶剂。
优选的，所述步骤1还包括金属浆料预处理过程，所述金属浆料预处理过程包括：
使用脱泡、搅拌、研磨方式处理所述金属浆料。
优选的，所述步骤3还包括干燥过程。
优选的，所述干燥过程为：干燥温度100～150℃，持续时间5～30分钟。
一种使用纳米金属膜模块的基板制备方法，包括：
步骤1：将所述纳米金属膜模块底部涂覆粘结剂；
步骤2：将所述纳米金属膜模块置于基板上；
步骤3：在纳米金属膜模块表面放置金属箔；
步骤4：按照设定温度曲线和气氛烘烤；
步骤5：冷却形成覆金属基板。
优选的，所述粘结剂为酒精或有机溶剂；所述基板为陶瓷基板。
优选的，所述步骤2中，所述基板上的至少一面分布至少一个所述纳米金属膜模块；
优选的，所述设定温度曲线为：峰值温度400～900℃，持续时间30秒～30分钟；所述气氛为：含氧量低于6ppm氧气含量的氮气气氛或还原性气氛
本发明提供的纳米金属膜模块制备方法及其基板制备方法，可按照需求从预制件制造商定制、更新预制件，避免了新丝网产生的浪费，具有改善热稳定性、提升散热效率、提升键合强度和改善封装可靠性的技术效果。
附图说明
图1为使用本发明的纳米金属膜模块制备金属陶瓷基板流程示意图。
图2为本发明的纳米金属膜模块制备及应用流程图。
图3本发明的单层预制模块及其制备流程示意图。
图中序号：离散多位置存储盒1，未取用纳米金属膜模块2，待连接的纳米金属膜模块3，陶瓷基底4，金属箔片5，烘烤后形成的连接层6，第一材料金属浆料7，第一材料颗粒8，纳米粒子发生器9，电场或磁场10，第二材料颗粒10，混合浆料11，印刷刮刀12，印刷丝网(A)13，印刷丝网(B)14，无粘性基底15，离散式预制模块16，待切割预制模块17，激光18
具体实施方式
下面详细说明本发明的具体实施，有必要在此指出的是，以下实施只是用于本发明的进一步说明，不能理解为对本发明保护范围的限制，该领域技术熟练人员根据上述本发明内容对本发明做出的一些非本质的改进和调整，仍然属于本发明的保护范围。
实施例一
本实施例提供了一种单层预制模块结构及其制备方法，如图2、3所示。单层结构中，第一材料是银铜钛活性钎焊料，第二材料是纳米铜颗粒。
制备方式为：
1)配置银铜钛活性钎焊料浆体第一材料；
2)使用物理冲击的将纳米铜颗粒(平均粒径在1nm-100nm)方式打入第一材料焊料主体中；
3)将所述焊料通过特定图案的丝网印刷到无粘性碳化玻璃载体上，形成待干燥的分离式预制模块；
4)干燥；
5)形成预制模块；
6)将所述预制模块转移到离散多位置存储盒。
具体步骤为：
1)使用40wt.％伊士曼公司生产的Texanol酯醇，25wt.％二乙二醇二丁醚，35wt.％丙烯酸系树脂制备有机载体，重量10g；
2)在所述有机载体中混入80g银(70～80wt.％)-铜(15～30wt.％)-钛(0.5～85wt.％)混合粉；
3)磁力搅拌、真空去泡，蒸发；制备成焊料浆体；
4)使用脱泡、搅拌、研磨等方式处理浆料；
5)将所述浆料通过丝网印刷方式印制在碳化玻璃上；丝网设计为每个预制件尺寸25mm x 25mm，按照9x9排列；
6)将所述基板干燥，干燥温度设定100～130℃，持续时间10～30分钟，使得有机介质挥发；
7)通过干燥厚膜，形成最终预制模块。
该实施例中，使用小尺寸纳米铜颗粒混入第一材料，一方面有效的降低了焊接温度；其次，小尺寸纳米铜颗粒有效的填充了第一材料颗粒间原有的空隙，可以有效提升后段焊接时连接辅助层的致密度。
实施例二
本实施例提供了一种单层预制模块结构及其制备方法，如图2、3所示。单层结构中，主体(第一材料)是银铜钛活性钎焊料浆体，第二材料是纳米铜颗粒。
制备方式为：
1)配置银铜钛活性钎焊料浆体第一材料；
2)使用物理冲击的将纳米铜颗粒(平均粒径在1nm-100nm)方式打入第一材料焊料主体中；
3)将所述焊料通过特定图案的丝网印刷到无粘性碳化玻璃载体上，形成待干燥的完整预制模块；
4)干燥；
5)激光切割；
6)形成预制模块；
7)将所述预制模块转移到离散多位置存储盒。
该实施例中，使用激光切割完整的预制模块，从而形成具备特定形状和尺寸的离散式模块，比起传统丝网印刷工艺，具备更高的设计自由度。
实施例三
本实施例提供了一种多层预制模块结构及其制备方法，该结构中，含有大尺寸金属颗粒的浆料和小尺寸纳米铜颗粒的浆料分别依次印刷到无粘性基材表面，形成叠层结构的预制模块；该模块的多层材料中的大小尺寸金属颗粒会在后续的焊接金属-陶瓷基板工艺中随着扩散现象相互融合，相互填充空隙，从而提升连接辅助层的致密度，提升连接强度。具体步骤：
1)使用微米铜(0.1-100um)制备的浆料作为第一材料(第一材料也包括金、钯、银、铜、铝、银钯合金、金钯合金、铜银合金、铜银镍合金或铜铝合金。)；
2)使用纳米铜颗粒(1-100nm)制备的浆料作为第二材料；
3)将第一材料浆料使用丝网印刷技术印刷到无粘性碳化玻璃载体表面；干燥；
4)将第二材料浆料使用丝网印刷技术印刷到步骤3)所述第一浆料表面；干燥；
5)形成预制模块；
6)将所述预制模块转移到离散多位置存储盒。
实施例四
本实施例提供了一种使用预制模块制备金属陶瓷基板的方法，利用该纳米金属膜模块制备覆金属基板的步骤如图1所示：
1)将所述纳米金属膜模块从离散式多位置存储盒取出；
2)使用pick&place装置将所属纳米金属膜模块置于陶瓷基板表面；
3)加热该金属陶瓷基板，使得预制模块软化并与陶瓷基板微弱粘连；
4)放置金属箔片于所述预制模块表面；可选有无夹具固定；
5)烘烤所述[金属箔片-预制模块-陶瓷]体系；
6)冷却体系，形成金属-陶瓷基板。
烘烤过程中，所述有机溶剂会在烘烤过程中全部挥发，烘烤工艺参数可设为峰值温度400～900℃，30秒～10分钟)和氮气(将氧气含量控制在6ppm以下)气氛烘烤。在烘烤过程中，一方面纳米铜+微米铜组合使得铜材料的整体平均粒度降低，从而达到降低烧接温度的效果，传统烧接温度为900-1100℃，而本发明的烧结温度为400～900℃之间；另一方面，纳米铜颗粒在铜浆中会与微米铜均匀混合，从而使得烧结时填充原微米铜浆会产生的空隙，从而提高烧结铜层致密度。
本发明提供的一种纳米金属膜模块及其制备方法：
1)将金属焊料连接辅助层从传统的“浆料”状态改进为“预制模块”状态，易于保存；所述金属焊料连接辅助层具备了类似“双面胶”的使用效果，随取随用。
2)该纳米金属膜模块可按需求定制、设计其形貌、尺寸、材料搭配等,通过该方案的实施，避免传统金属陶瓷连接工艺必须连续进行的弊端，使用自由度高。
3)同时通过使用激光切割、锻造等方式剪裁完整金属焊料膜形成预制模块，可以避免购买新印刷丝网产生的浪费；金属陶瓷基板制备单位也可以按照需求从纳米金属膜模块制造商定制预制件，更加简化了生产复杂性。
4)本发明使用大小尺寸混合的金属颗粒，使得原本存在的颗粒间隙被填充，本发明的纳米金属颗粒的较大和较小颗粒的尺寸的具体选择，是其他直径尺寸的纳米金属颗粒组合所不能达到的，本发明提高了焊接后的致密度，使得本发明的金属焊料连接辅助具有改善热稳定性、提升散热效率、提升键合强度和改善封装可靠性的技术效果。
尽管为了说明的目的，已描述了本发明的示例性实施方式，但是本领域的技术人员将理解，不脱离所附权利要求中公开的发明的范围和精神的情况下，可以在形式和细节上进行各种修改、添加和替换等的改变，而所有这些改变都应属于本发明所附权利要求的保护范围，并且本发明要求保护的产品各个部门和方法中的各个步骤，可以以任意组合的形式组合在一起。因此，对本发明中所公开的实施方式的描述并非为了限制本发明的范围，而是用于描述本发明。相应地，本发明的范围不受以上实施方式的限制，而是由权利要求或其等同物进行限定。

Claims (23)

  1. 一种纳米金属膜模块，其特征在于，包括：
    纳米金属辅助连接模块，
    基底，
    所述纳米金属辅助连接模块包括第一金属颗粒、第二金属颗粒，所述第一金属颗粒与所述第二金属颗粒直径不同。
  2. 根据权利要求1所述纳米金属膜模块，其特征在于，所述第一金属颗粒直径为0.1μm～100μm；所述第二金属颗粒直径为0.5nm～100nm。
  3. 根据权利要求1所述纳米金属膜模块，其特征在于，所述纳米金属辅助连接模块是连续式，或，非连续式的离散排布的小块；所述纳米金属辅助连接模块具有单层、双层、三层或多层结构。
  4. 根据权利要求1所述纳米金属膜模块，其特征在于，所述纳米金属辅助连接模块厚度为：1μm～500μm厚度。
  5. 根据权利要求1所述纳米金属膜模块，其特征在于，所述纳米金属膜模块还包括连接辅助添加剂、有机载体和溶剂。
  6. 根据权利要求1所述纳米金属膜模块，其特征在于，所述第一金属颗粒，占有辅助模块材料的45wt.％～95wt.％；所述第二金属颗粒，占有辅助层材料的5wt.％～55wt.％；所述连接辅助添加剂占有辅助层材料的0.1wt％～9.9wt％。
  7. 根据权利要求1所述纳米金属膜模块，其特征在于，所述第一金属颗粒及所述第二金属颗粒材料为：包括铝、铟的三族元素，包括碳、硅、锡、铅的四族元素，包括磷、铋、锑的五族元素，包括铜、金、银的第一副族；包括钛、锆的第四副族，包括锰、钨、钼的第六副族，银钯合金、金钯合金、铜银合金、铜银镍合金、银铜钛、银铜铟、银铜锡、铝硅铜、铝硅、铝铜、铟锡；
    所述连接辅助添加剂为：氧化铋、氧化硅、氧化铝、氧化钙、氧化钠、氧化铯、氧化钇、氧化锌、氧化镁、氧化硼、氧化钛组成的玻璃或陶瓷相；或/和包括：银、铜、钛、锡、铟、铅；
    所述基底材料为：碳化玻璃、陶瓷、金属、或有机聚合基材。
  8. 根据权利要求1所述纳米金属膜模块，其特征在于，所述第一金属颗粒及所述第二金属颗粒形状为：球型、纤维状、雪花状、片状和/或线状形状；
  9. 根据权利要求1所述纳米金属膜模块，其特征在于，所述基底材料与所述纳米金属辅助连接模块有微弱粘结力、或完全无粘结力。
  10. 一种纳米金属膜模块的制备方法，其特征在于，包括：
    步骤1：采用微米级金属颗粒或微米/纳米级混合金属颗粒配置金属焊料的浆料；
    步骤2：将所述金属浆料印制在基底上，形成厚膜；
    步骤3：通过丝网印刷方式或激光切割方式，形成厚膜预制件；
    步骤4：通过防氧化喷涂或包装所述厚膜预制件。
  11. 根据权利要求10所述纳米金属膜模块的制备方法，其特征在于，所述步骤1的配置方法为：
    采用机械混合的方法将第二金属颗粒混入第一膏体；所述机械混合方法为通过磁力搅拌、真空去泡，蒸发制备所述金属浆料；
    或，利用电场、磁场或气流给第二纳米金属颗粒赋予动能，以物理冲击方式将第二纳米金属颗粒打入所述第一膏体，填充第一膏体中第一金属颗粒之间的间隙，形成多尺寸纳米颗粒混合的金属浆料。
  12. 根据权利要求10所述纳米金属膜模块的制备方法，其特征在于，所述基底为碳化玻璃、陶瓷、金属、或有机聚合基材。
  13. 根据权利要求10所述纳米金属膜模块的制备方法，其特征在于，通过丝网印刷方式，所述步骤2包括：
    步骤2.1：根据所需离散型预制件的形状、尺寸设计印刷丝网；
    步骤2.2：将所述浆料通过丝网印刷方式印制在所述基底上。
  14. 根据权利要求10所述纳米金属膜模块的制备方法，其特征在于，通过激光切割方式，所述步骤2包括：
    将所述浆料通过丝网印制在所述基底上；
    所述步骤3为：激光切割或锻压方式切割所述厚膜预制模块。
  15. 根据权利要求14所述纳米金属膜模块的制备方法，其特征在于，所述丝网为印制非特定面积金属膜的丝网。
  16. 根据权利要求10所述纳米金属膜模块的制备方法，其特征在于，所述步骤1的金属浆料包含第一金属颗粒、第二金属颗粒、连接辅助添加剂、有机载体和溶剂。
  17. 根据权利要求10所述纳米金属膜模块的制备方法，其特征在于，所述步骤1还包括金属浆料预处理过程，所述金属浆料预处理过程包括：
    使用脱泡、搅拌、研磨方式处理所述金属浆料。
  18. 根据权利要求10所述纳米金属膜模块的制备方法，其特征在于，所述步骤3还包括干燥过程。
  19. 根据权利要求18所述纳米金属膜模块的制备方法，其特征在于，所述干燥过程为：干燥温度100～150℃，持续时间5～30分钟。
  20. 一种使用权利要求1-9所述纳米金属膜模块的基板制备方法，其特征在于，包括：
    步骤1：将所述纳米金属膜模块底部涂覆粘结剂；
    步骤2：将所述纳米金属膜模块置于基板上；
    步骤3：在纳米金属膜模块表面放置金属箔；
    步骤4：按照设定温度曲线和气氛烘烤；
    步骤5：冷却形成覆金属基板。
  21. 根据权利要求20所述使用所述纳米金属膜模块的制备金属陶瓷基板的方法，其特征在于，所述粘结剂为酒精或有机溶剂；所述基板为陶瓷基板。
  22. 根据权利要求20所述使用所述纳米金属膜模块的制备金属陶瓷基板的方法，其特征在于，所述步骤2中，所述基板上的至少一面分布至少一个所述纳米金属膜模块。
  23. 根据权利要求20所述厚使用所述纳米金属膜模块的制备金属陶瓷基板的方法，其特征在于，所述设定温度曲线为：峰值温度400～900℃，持续时间30秒～30分钟；所述气氛为：含氧量低于6ppm氧气含量的氮气气氛或还原性气氛。
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