CN100488689C - 金属-陶瓷复合衬底的生产方法和用于这种方法的钎焊料 - Google Patents

金属-陶瓷复合衬底的生产方法和用于这种方法的钎焊料 Download PDF

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CN100488689C
CN100488689C CNB021514305A CN02151430A CN100488689C CN 100488689 C CN100488689 C CN 100488689C CN B021514305 A CNB021514305 A CN B021514305A CN 02151430 A CN02151430 A CN 02151430A CN 100488689 C CN100488689 C CN 100488689C
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metallic plate
cored solder
weight
active metal
ceramic substrate
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CN1422721A (zh
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樱庭正美
木村正美
高原昌也
中村润二
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Tonghe Holding Group Co ltd
Dowa Metaltech Co Ltd
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Dowa Metaltech Co Ltd
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    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
    • H05K3/00—Apparatus or processes for manufacturing printed circuits
    • H05K3/38—Improvement of the adhesion between the insulating substrate and the metal
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
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    • C04B37/00—Joining burned ceramic articles with other burned ceramic articles or other articles by heating
    • C04B37/02—Joining burned ceramic articles with other burned ceramic articles or other articles by heating with metallic articles
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B23—MACHINE TOOLS; METAL-WORKING NOT OTHERWISE PROVIDED FOR
    • B23K—SOLDERING OR UNSOLDERING; WELDING; CLADDING OR PLATING BY SOLDERING OR WELDING; CUTTING BY APPLYING HEAT LOCALLY, e.g. FLAME CUTTING; WORKING BY LASER BEAM
    • B23K35/00—Rods, electrodes, materials, or media, for use in soldering, welding, or cutting
    • B23K35/22—Rods, electrodes, materials, or media, for use in soldering, welding, or cutting characterised by the composition or nature of the material
    • B23K35/24—Selection of soldering or welding materials proper
    • B23K35/30—Selection of soldering or welding materials proper with the principal constituent melting at less than 1550 degrees C
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B23—MACHINE TOOLS; METAL-WORKING NOT OTHERWISE PROVIDED FOR
    • B23K—SOLDERING OR UNSOLDERING; WELDING; CLADDING OR PLATING BY SOLDERING OR WELDING; CUTTING BY APPLYING HEAT LOCALLY, e.g. FLAME CUTTING; WORKING BY LASER BEAM
    • B23K35/00—Rods, electrodes, materials, or media, for use in soldering, welding, or cutting
    • B23K35/22—Rods, electrodes, materials, or media, for use in soldering, welding, or cutting characterised by the composition or nature of the material
    • B23K35/24—Selection of soldering or welding materials proper
    • B23K35/30—Selection of soldering or welding materials proper with the principal constituent melting at less than 1550 degrees C
    • B23K35/3006—Ag as the principal constituent
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B15/00—Layered products comprising a layer of metal
    • B32B15/04—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
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    • C04B37/026—Joining burned ceramic articles with other burned ceramic articles or other articles by heating with metallic articles characterised by the interlayer used consisting of metals or metal salts
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    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
    • H05K1/00—Printed circuits
    • H05K1/02—Details
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    • B23—MACHINE TOOLS; METAL-WORKING NOT OTHERWISE PROVIDED FOR
    • B23K—SOLDERING OR UNSOLDERING; WELDING; CLADDING OR PLATING BY SOLDERING OR WELDING; CUTTING BY APPLYING HEAT LOCALLY, e.g. FLAME CUTTING; WORKING BY LASER BEAM
    • B23K35/00—Rods, electrodes, materials, or media, for use in soldering, welding, or cutting
    • B23K35/02—Rods, electrodes, materials, or media, for use in soldering, welding, or cutting characterised by mechanical features, e.g. shape
    • B23K35/0222—Rods, electrodes, materials, or media, for use in soldering, welding, or cutting characterised by mechanical features, e.g. shape for use in soldering, brazing
    • B23K35/0244—Powders, particles or spheres; Preforms made therefrom
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    • B32B2311/12—Copper
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  • Structural Engineering (AREA)
  • Organic Chemistry (AREA)
  • Microelectronics & Electronic Packaging (AREA)
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Abstract

本发明通过使用糊状钎焊料将金属板接合到陶瓷衬底上生产金属-陶瓷复合衬底，上述钎焊料通过将10-14重量份的液料添加到100重量份的粉末中制备，上述粉末固体物包括90.0-99.5%的Ag粉末、0-9.5%的Cu粉末和0.5-4.0%的活泼金属粉末，如果需要，以及0.0-0.9%的氧化钛粉末。

Description

金属-陶瓷复合衬底的生产方法和用于这种方法的钎焊料
技术领域
本发明涉及金属-陶瓷复合衬底的生产方法。本发明还涉及可有效用于将金属接合到陶瓷衬底上的钎焊料。
背景技术
在将金属，如铜板接合到陶瓷衬底上，如氮化铝(AlN)上的技术中已知几种方法，两种典型的例子是叙述于日本专利公开No.166165/1985题为“氮化物基陶瓷接合到金属上的方法”的活泼金属钎焊法和将铜板直接接合到氮化铝衬底改性表面的方法(如典型述于日本专利公开No.163093/1981)。
活泼金属钎焊法比直接接合法提供更高强度的组件，且得到的组件具有需要的特性，如对反复热循环的高耐久性。因此，目前活泼金属纤焊法在铜板与非氧化物基陶瓷衬底，即氮化物陶瓷衬底的接合中广泛使用。
在活泼金属纤焊法的实践中工业上使用两种钎焊料；其中之一由Ag、Cu、和选自Ti、Zr和Hf的活泼金属组成(如日本专利公开No.166165/1985中所述)，而另一种是由Ag、Cu和氢化钛组成的活泼金属糊料(如日本专利公开No.101153/1991中所述)。
借助于这些钎焊料由铜板接合到氮化铝衬底两侧而生产的电路衬底已经商品化。
在许多钎焊料中，将活泼金属添加到由72％的Ag和28％的Cu组成的结构中，所以接合法在高于共晶点780℃的温度下，更好在约850℃温度下进行。
但是，最新的电路衬底需要在更大的电功率上运行，要满足这种需要，需要发展电路衬底，它不仅具备好的热散失和电绝缘性，而且还呈现更高的强度和抗热冲击性。
发明内容
所以，本发明的目的是提供一种钎焊料，它适用于制造不具有非接触部分的动力模件复合衬底，并与普通钎焊料相比可改进其性能。
本发明另一个目的是提供一种使用该钎焊料生产金属-陶瓷复合衬底的方法。
为了达到上述目的，本发明人进行了充分的研究并发现通过使用添加90％的Ag和9.5％的Cu或0.5％的活泼金属(TiO)的活泼金属钎焊料，接合法可在低于共晶点875℃的780-870℃温度下进行，并且接合的复合衬底不具有非接触部分。
本发明在这个发现的基础上完成。
按照本发明的第一方面，提供通过使用一种钎焊料将金属板接合到陶瓷衬底上生产的金属-陶瓷复合衬底，上述钎焊料固体物(重量％)包括90.0-99.5％的Ag，0～9.5％的Cu，0.5～4.0％的活泼金属。
上述陶瓷衬底是至少一种选自Al2O3、AlN和Si3N4的陶瓷衬底
上述活泼金属是至少一种选自Ti、Zr和Hf的活泼金属
按照本发明的第二方面，提供一种通过将金属板接合到陶瓷衬底上生产金属-陶瓷复合衬底的方法，它包括步骤：
将10-14重量份的液料添加到100重量份的粉末中，该粉末固体物(重量％)包括90.0-99.5％的Ag粉末、0～9.5％的Cu粉末和0.5-4.0％的活泼金属粉末；
混合各成分以使形成糊状的钎焊料；
将该钎焊料涂敷到陶瓷衬底上；
将金属板叠加在已涂敷的钎焊料上，并在不高于钎焊料熔点的温度下加热装配件，以形成金属板和陶瓷衬底的组件；和
将腐蚀保护层涂敷在组件的金属板上，以使形成电路图形，腐蚀金属板，以使形成金属化电路。
上述装配件的加热温度在780-870℃范围内，它不高于钎焊料熔点的温度。
按照本发明的第三个方面，提供用于将金属板接合到陶瓷衬底上的钎焊料，它是由10-14重量份的液料与100重量份粉末混合制备的糊状物，上述粉末固体物(重量％)包括90.0-99.5％的Ag粉末、0～9.5％的Cu粉末和0.5～4.0％的活泼金属粉末。
按照本发明的第四个方面，提供用于将金属板接合到陶瓷衬底上的钎焊料，它是由10-14重量份的液料与100重量份粉末混合制备的糊状物，上述粉末固体物(重量％)包括90.0-99.5％的Ag粉末、0～9.5％的Cu粉末、0.5～4.0％的活泼金属粉末和0.0～0.9％的氧化钛粉末。
用于本发明的钎焊料Ag含量为90.0-99.5％(重量)。如果Ag含量小于90％(重量)，不适合生产具有非接触部分的复合衬底。
钎焊料的Cu含量小于9.5％(重量)。Cu含量小于普通Ag-Cu钎焊料的Cu含量的理由是：当装配件加热时，Ag组分和Cu板的接触面反应，结果产生共晶结晶。
可用于本发明的活泼金属是至少一种周期表IVa族的元素，如举例Ti、Zr或Hf。
这些活泼金属可以元素形式添加，或作为氢化物添加，较好的添加量范围为0.5-4.0％(重量)。
低于0.5％(重量)，氮化物层将以不足以提供所需粘附强度的量形成；超出4.0％(重量)，粘附强度增加，但是，另一方面，金属板接合到陶瓷衬底上后易于出现破裂。
氧化钛以TiO或TiO2形式添加，添加量范围为0.0-0.9％(重量)。氧化钛可以是非晶体或者晶体。
本发明人通过实验证明：添加这些量的氧化钛到上述成分的钎焊料中有助于改进所得复合衬底的各种性能，如抗反复热循环性，抗挠强度、挠度和抗通过炉加热性。这些促进的大概理由是：添加到钎焊料中的TiO2或TiO均匀地分散，以减小应力集中。
具有上述确定成分的合金可直接用作本发明钎焊料。另一方面，包括各成分颗粒的粉末可与有机溶剂混合以形成钎焊料的糊。如果金属件简单地接合到陶瓷件上，可使用薄片状的钎焊合金料。如果要在陶瓷衬底上形成电路，最好使用钎焊料糊。
为了制备钎焊料糊，将55-75体积份的有机溶剂，如松油醇、甲苯、甲基纤维素或乙基纤维素与25-45体积份的有机粘合剂，如PMMA、甲基纤维素或乙基纤维素混合，以形成液料，然后以10-14重量份的量将其添加到100重量份的包括各钎料成分颗粒的粉末中。
如果使用小于10重量份的液料，得到的糊如此粘稠，以致将趋于出现模糊印刷。如果使用大于14重量份的液料，得到的糊如此低粘度，以致将容易出现印刷冲刷。
本发明特征在于由于下述原因按照钎焊料的成分在小于钎焊料共晶熔点的温度下，最好在780-870℃的炉中加热装配件。
在使用用活泼金属Ti添加的72％的Ag和28％的Cu形成的普通钎焊料的情况下，接合在高于Ag-Cu共晶熔点的温度，即780℃开始。因此，实际上，接合在约850℃温度下进行。在本发明中，Ag的量大于90％(重量)。如果Ag是90％(重量)，Cu是9.5％(重量)，而Ti是0.5％(重量)，考虑到银-铜相图，该共晶熔点温度应大于875℃，以使在普通方法中为获得理想的组件接合必须在约900℃温度下进行。
如果本发明钎焊料仅在低于上述共晶熔点(875℃)温度下加热，它不能熔化而仅仅被烧结。但是，对于本发明动力模件在使用铜板作为衬底的情况下，上述钎焊料和铜板相互接触，以使当装配件被加热时钎焊料中的Ag和铜板中的Cu从所述接触部分以微米级逐渐发生共晶反应，Ag逐渐扩散到所述反应开始的铜板，并且共晶组织在接触面上形成。
具体实施方式
为进一步说明本发明的目的提供下述实施例，但是不作为限制。
实施例1
提供尺寸53×29×0.635mm的AlN衬底作为陶瓷衬底。将100重量份，其固体物含量示于表1(试样1-8)的粉末与12.4重量份液料混合以制备钎焊料糊。将该糊涂敷到整个AlN衬底表面上后，分别将厚度0.3mm和0.15mm的两铜板叠加到相应侧面，并在表1所示的温度下烧制装配件来生产组件。
表1
Figure C02151430D00081
为测定非接触部分在许多烧制温度下每个试样试验100件。
结果表明具有非接触部分的试样不多。
比较例1
提供如实施例1所述同样尺寸的AlN衬底作为陶瓷衬底。
将100重量份，其固体物含量示于表2(比较试样1-6)的粉末与12.4重量份液料混合以制备钎焊料糊。将该糊涂敷到整个AlN衬底表面上后，分别将厚度为0.3mm和0.15mm的两铜板叠加到相应侧面，在表2所示的温度下烧制装配件来生产组件。
表2
Figure C02151430D00091
象实施例一样为确定非接触部分在许多烧制温度下每个试样试验100件。
结果表明按照Ag密度的减小和如表2所示的烧制温度产生许多具有非接触部分的试样。
如上页所述，使用本发明钎焊料生产的金属-陶瓷复合衬底在减小非接触部分方面得到充分地改进，并可以低成本经济地制造。
参照其优选实施例本发明被特别展示和说明的同时，本技术中的那些熟练技术人员将清楚在形式和细节上可做各种变化而不脱离由所附权利要求确定的本发明的精神和范围。

Claims (6)

1.一种通过将金属板接合到陶瓷衬底上生产金属-陶瓷复合衬底的方法，它包括步骤：
添加10-14重量份的液料到100重量份的粉末中，该粉末固体物包括：以重量计，90.0-99.5％的Ag、0～9.5％的Cu、0.25～4.0％的活泼金属和0～0.9％的氧化钛，所述活泼金属是周期表IVa族元素Ti、Zr和Hf中的至少一种元素；
混合各成分以形成薄片状钎焊料；
涂敷该钎焊料到陶瓷衬底上；
叠加金属板到涂敷的钎焊料上，并在不高于钎焊料熔点的温度下加热装配件，以形成金属板和陶瓷衬底的组件；和
涂敷抗蚀剂到组件的金属板上，以形成电路图形，蚀刻金属板，以形成金属化电路。
2.一种用于将金属板接合到陶瓷衬底上的钎焊料，它是通过将10-14重量份的液料与100重量份的粉末混合制备的薄片，上述粉末固体物包括：以重量计，90.0～99.5％的Ag、0～9.5％的Cu、0.25～4.0％的活泼金属和0～0.9％的氧化钛，所述活泼金属是周期表IVa族元素Ti、Zr和Hf中的至少一种元素。
3.一种通过将金属板接合到陶瓷衬底上生产金属-陶瓷复合衬底的方法，它包括步骤：
添加10-14重量份的液料到100重量份的粉末中，该粉末固体物包括：以重量计，90.0-99.5％的Ag、0～9.5％的Cu、0.25～4.0％的活泼金属和0～0.25％的氧化钛，所述活泼金属是周期表IVa族元素Ti、Zr和Hf中的至少一种元素；
混合各成分以形成薄片状钎焊料；
涂敷该钎焊料到陶瓷衬底上；
叠加金属板到涂敷的钎焊料上，并在不高于钎焊料熔点的温度下加热装配件，以形成金属板和陶瓷衬底的组件；和
涂敷抗蚀剂到组件的金属板上，以形成电路图形，蚀刻金属板，以形成金属化电路。
4.一种用于将金属板接合到陶瓷衬底上的钎焊料，它是通过将10-14重量份的液料与100重量份的粉末混合制备的薄片，上述粉末固体物包括：以重量计，90.0～99.5％的Ag、0～9.5％的Cu、0.25～4.0％的活泼金属和0～0.25％的氧化钛，所述活泼金属是周期表IVa族元素Ti、Zr和Hf中的至少一种元素。
5.一种通过将金属板接合到陶瓷衬底上生产金属-陶瓷复合衬底的方法，它包括步骤：
添加10-14重量份的液料到100重量份的粉末中，该粉末固体物包括：以重量计，90.0-99.5％的Ag、0～9.5％的Cu、0.25～4.0％的活泼金属和0～0.9％的氧化钛，所述活泼金属是Ti；
混合各成分以形成薄片状钎焊料；
涂敷该钎焊料到陶瓷衬底上；
叠加金属板到涂敷的钎焊料上，并在不高于钎焊料熔点的温度下加热装配件，以形成金属板和陶瓷衬底的组件；和
涂敷抗蚀剂到组件的金属板上，以形成电路图形，蚀刻金属板，以形成金属化电路。
6.一种用于将金属板接合到陶瓷衬底上的钎焊料，它是通过将10-14重量份的液料与100重量份的粉末混合制备的薄片，上述粉末固体物包括：以重量计，90.0～99.5％的Ag、0～9.5％的Cu、0.25～4.0％的活泼金属和0～0.9％的氧化钛，所述活泼金属是Ti。
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CN1099120C (zh) 2003-01-15
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CN1201241A (zh) 1998-12-09
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DE69817648D1 (de) 2003-10-09
US6399019B1 (en) 2002-06-04
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