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CN109834404A - 接合材料、使用了该接合材料的半导体装置的制造方法和半导体装置 - Google Patents

接合材料、使用了该接合材料的半导体装置的制造方法和半导体装置 Download PDF

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Publication number
CN109834404A
CN109834404A CN201811422049.0A CN201811422049A CN109834404A CN 109834404 A CN109834404 A CN 109834404A CN 201811422049 A CN201811422049 A CN 201811422049A CN 109834404 A CN109834404 A CN 109834404A
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CN
China
Prior art keywords
grafting material
tin
semiconductor device
carbon
light
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CN201811422049.0A
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English (en)
Inventor
北浦秀敏
古泽彰男
日根清裕
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Panasonic Intellectual Property Management Co Ltd
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Panasonic Intellectual Property Management Co Ltd
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Priority claimed from JP2018144143A external-priority patent/JP7108907B2/ja
Application filed by Panasonic Intellectual Property Management Co Ltd filed Critical Panasonic Intellectual Property Management Co Ltd
Publication of CN109834404A publication Critical patent/CN109834404A/zh
Pending legal-status Critical Current

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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L33/00—Semiconductor devices having potential barriers specially adapted for light emission; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
    • H01L33/48—Semiconductor devices having potential barriers specially adapted for light emission; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof characterised by the semiconductor body packages
    • H01L33/64—Heat extraction or cooling elements
    • H01L33/641—Heat extraction or cooling elements characterized by the materials
    • 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
    • B23K35/26—Selection of soldering or welding materials proper with the principal constituent melting at less than 400 degrees C
    • B23K35/262—Sn as the principal constituent
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Abstract

本发明提供一种接合材料，其具有高放热性和高可靠性，且包含以锡为主要成分的焊料合金。接合材料包含0.1wt％以上且30wt％以下的能够与锡和碳形成化合物的至少1种元素，余量中作为主要成分而包含锡。

Description

接合材料、使用了该接合材料的半导体装置的制造方法和半 导体装置
技术领域
本发明涉及为了将氮化镓等放热量大的半导体冷却而能够连接于散热器或散热片等的接合材料、使用了该接合材料的半导体装置、以及使用了该接合材料的半导体装置的制造方法。
背景技术
作为化合物半导体的氮化镓被广泛用作高亮度发光元件。使用了氮化镓的发光二极管(LED)与白炽灯泡相比，具有寿命长、耗电量低、快速响应性、节省空间等优点，正在快速普及。为了进行进一步的高亮度化，使驱动电流增加即可，但发光元件的放热量变大，需要冷却机构。因此，使用放热片、银糊剂、焊料合金将发光元件粘接或接合于放热性良好的基台(例如参照专利文献1)。
图3是以往的半导体装置301的示意图。发光元件302利用银糊剂304而粘接于具有导热性的铜合金的基台303。基台303的表面形成电极305，通过引线306将发光元件302与电极305连接，由此进行了电连接。发光元件302和引线306的周围被密封树脂307密封。
换言之，以往的半导体装置301中，利用作为填料而添加有热导率高的银的银糊剂304使发光元件302粘接于基台303，从而使发光元件302所产生的热高效地逸散至基台303。
现有技术文献
专利文献
专利文献1：日本特开2004-265986号公报
发明内容
发明要解决的问题
一般来说，银糊剂的热导率为30w/m·K左右，铜合金的热导率为400W/m·K左右。使用专利文献1中记载的银糊剂而接合于铜合金的基台时，由于银糊剂的热导率不那么高，因此，若为了高亮度化而使驱动电流逐渐增加，则存在发光元件的温度上升、发光效率降低的问题。
此外，通过使用银糊剂而存在下述问题：因银的迁移、硫化、糊剂树脂的热劣化等而导致可靠性试验后在界面产生裂纹，放热性降低。
近年来，作为无铅焊料而进行了以具有高放热性的锡为主要成分的焊料合金的研究开发。但是，截止至今以锡为主要成分的焊料合金尚未获得充分的可靠性。
本发明是为了解决上述课题而进行的，其目的在于，提供具有高放热性和高可靠性且包含以锡为主要成分的焊料合金的接合材料。
用于解决问题的方法
为了解决上述课题，本发明所述的接合材料包含0.1wt％以上且30wt％以下的能够与锡和碳形成化合物的至少1种元素，余量中作为主要成分而包含锡。
本说明书中，“能够与锡和碳形成化合物的至少1种元素(化合物形成性元素)”是指与锡和碳形成化合物的任意元素。化合物形成性元素存在两种以上时，接合材料中的化合物形成性元素的含有率(wt％)表示接合材料所包含的两种以上化合物形成性元素的重量之和相对于接合材料的总重量的比例。
本说明书中，“主要成分”是指接合材料所包含的元素之中存在比率最高的元素。
此外，一个实施方式的接合材料中，化合物形成性元素包含钛、锆、钒中的至少1种。
此外，一个实施方式的接合体的制造方法中，通过使用上述实施方式的接合材料将发光元件与基台进行接合，从而提供半导体装置。
发明的效果
根据本发明所述的接合材料，能够将发光元件接合于热导率高的碳基台。并且，通过利用接合材料的耐高温高湿性来维持高热导率，能够提供可确保高放热性的半导体装置。
附图说明
图1A是实施方式1所述的半导体装置的制造方法的一个工序的示意图。
图1B是实施方式1所述的半导体装置的制造方法的一个工序的示意图。
图1C是实施方式1所述的半导体装置的制造方法的一个工序的示意图。
图1D是实施方式1所述的半导体装置的制造方法的一个工序的示意图。
图1E是实施方式1所述的半导体装置的制造方法的一个工序的示意图。
图1F是实施方式1所述的半导体装置的制造方法的一个工序的示意图。
图2是将半导体装置设置于放热板的示意图。
图3是以往的发光装置的示意图。
具体实施方式
第一方式所述的接合材料包含0.1wt％以上且30wt％以下的能够与锡和碳形成化合物的至少1种元素，余量中作为主要成分而包含锡。
第二方式所述的接合材料是在上述第一方式中可以包含0.1wt％以上且10wt％以下的上述元素。
第三方式所述的接合材料是在上述第一方式或第二方式中，上述至少1种元素可以为比锡容易氧化的元素。
第四方式所述的接合材料是在上述第一方式～第三方式的任意方式中，上述元素与锡形成的化合物的熔点可以为1000℃以上。
第五方式所述的接合材料是在上述第一方式～第五方式的任意方式中，上述至少1种元素可以包含选自钛、锆、钒的组中的至少1种。
第六方式所述的半导体装置的制造方法中，使用上述第一方式～第五方式的任意方式的上述接合材料，
通过将发光元件与碳基台进行接合而制造半导体装置。
第七方式所述的半导体装置包括：
发光元件；
碳基台；以及
将上述发光元件与上述碳基台进行接合的上述第一方式～第五方式的任意方式的上述接合材料。
第八方式所述的接合材料是在上述第一方式中可以包含大于5wt％且为10wt％以下的上述元素。
以下，针对本实施方式所述的接合材料，一边参照附图一边进行说明。需要说明的是，在附图中，针对实质相同的部件标注相同的符号。
(实施方式1)
<接合材料>
实施方式1所述的接合材料是含有0.1wt％以上且30wt％以下的能够与锡和碳形成化合物的元素(化合物形成性元素)，余量中作为主要成分而包含锡的合金。
化合物形成性元素只要是与锡和碳形成化合物，且比锡容易氧化的元素，就没有特别限定。
表1是作为化合物形成性元素的各元素与锡、碳、氧形成的化合物的例子以及氧化物的标准生成吉布斯自由能的表。需要说明的是，化合物的化学式是例示，不表示全部化合物。
[表1]
如表1所示，作为能够与锡和碳形成化合物的元素(“化合物形成性元素”)，可列举出例如Ti、Y、Nb、Pr、La、V、Mn、Th、Fe、Zr、Mo、Li。这些元素与锡和碳这两者形成化合物，且氧化物的标准生成吉布斯自由能比锡低，因此，即使在与锡一同存在的情况下也比锡容易形成氧化物。作为化合物形成性元素，可以包含选自钛、锆、钒的组中的至少1种。
此处，选择钛、锆、钒的理由是因为：如表1所示，与Sn形成的化合物的熔点高。熔点越高，则越可长时间保持接合材料的强度。化合物具有至少1000℃以上的熔点即可。
此外，通过使接合材料的化合物形成性元素的含量为0.1wt％以上，能够在接合材料与碳基台的界面形成充分量的化合物，在碳基台与接合材料的界面形成强度高且良好的接合层。
需要说明的是，化合物形成性元素的含量可以高于5wt％。含量高于5wt％时，合金层生长而能够更牢固地进行接合。
此外，通过使接合材料中的化合物形成性元素的含量为30wt％以下，在将接合材料与碳基台进行接合时的加热时，液相成分的锡会残留并润湿扩展于碳基台，由此形成无孔隙的良好接合。
需要说明的是，化合物形成性元素的含量优选为10wt％以下。
进而，接合材料的余量可以仅由锡构成。此时，若接合材料所包含的化合物形成性元素为1种，则接合材料是包含1种化合物形成性元素和作为主要成分的锡的二元系合金。
此外，接合材料的余量可以包含含有主要成分即锡在内的多种元素。此时，接合材料是包含化合物形成性元素和含有主要成分即锡在内的多种元素的多元系合金。
需要说明的是，与锡和碳这两者形成化合物的元素(化合物形成性元素)和作为主要成分的锡之外的其它元素的含量优选为0.01wt％以下，更优选为0.005wt％以下。此外，与锡和碳这两者形成化合物的元素(化合物形成性元素)优选为1种。
<发光元件>
发光元件可以使用例如一般的氮化镓的二极管。例如，在蓝宝石基板的上表面形成n型氮化镓和P型氮化镓，并在其上表面形成P型电极和N型电极，从而能够利用引线进行电连接。蓝宝石基板的下表面进行了能够与接合材料相连接的金属化(形成金属层)。金属化在施加镍后，为了抗氧化而形成了金。需要说明的是，金属化只要是与接合材料的锡形成合金层的元素即可。
<碳基台>
作为碳基台，使用了利用成型机将碳粉末成形并烧固而得的基台。碳粉末通过成形而排列，碳基台的厚度方向的热导率达到600W/m·K、面方向的热导率达到200W/m·K。
<工艺>
以下，针对实施方式1所述的接合体及其制造方法，一边参照附图一边进行说明。图1A～图1F是实施方式1所述的半导体装置的制造方法的各工序的示意图。
(1)首先，如图1A所示，准备接合材料101和碳基台102，进行接合。接合条件如下所示。首先，在氮气气氛的炉中设置接合材料101和碳基台102，以50℃/分钟的升温速度加热至1200℃。由此，如图1B所示，在接合材料101与碳基台102的界面形成碳接合层103。碳接合层103通过包含与锡和碳均形成化合物的化合物形成性元素而牢固地接合。
(2)接着，如图1C那样，形成电极层104。电极层104是为了与后续要接合的发光元件进行电连接而形成的。电极层104通过具有绝缘性的粘接层105而粘接于碳基台102。
(3)接着，如图1D所示，将发光元件106进行接合。将发光元件106与接合材料101进行接合的条件如下所示。首先，在氮气气氛的炉中设置发光元件106和图1C的状态的碳基台102，以50℃/分钟的升温速度加热至350℃。接着，在加热中使内部压力减压至10Pa，去除孔隙后，恢复至大气压并进行冷却。如上操作，从而将发光元件106与接合材料101进行接合。
需要说明的是，在接合后的接合材料101与发光元件106的界面形成了镍/锡的发光元件接合层107，该接合层是在发光元件106的背面进行了金属化的镍/金层与接合材料101的锡反应而得的。
(4)接着，如图1E所示，将发光元件106的P型电极和N型电极与电极层104通过引线108进行连接。
(5)接着，如图1F所示，利用密封树脂109将发光元件106的周围进行密封，制作半导体装置110。
实施例
如下述实施例1～12所示地制作本申请的接合体。将制作条件、评价结果示于表2。
[表2]
[实施例1]
作为接合材料101，使用含有0.1wt％的钛且余量为锡的锡-钛合金。接合材料101是成形体形状，尺寸为1mm×1mm、厚度为0.2mm。碳基台102使用了尺寸为4mm×4mm且厚度为1mm的碳基台。
使用该接合材料，如下操作来制造半导体装置。
(1)将接合材料101设置于碳基台102，用炉加热至1200℃并冷却，利用碳接合层103将接合材料101接合于碳基台102。
(2)接着，在碳基台102上隔着粘接层105形成电极层104。电极层是Cu，尺寸设为1mm×2mm、厚度设为0.05mm。
(3)形成电极层104后，将尺寸为1mm×1mm、厚度为0.1mm的发光元件106承载于接合材料101，在炉中以350℃进行加热冷却，从而进行接合。
(4)接着，对发光元件106和电极层104配置铝制的引线108，从而获得电连接。
(5)其后，用密封树脂109将发光元件106密封，从而制作半导体装置110。
为了确认可靠性试验后的放热性，首先将所制作的半导体装置110在温度85℃、湿度85％的恒温恒湿槽中放置3000hr。
<评价方法>
其后，如图2所示，通过将半导体装置110设置于放热板201并通电而使其发光，在发光元件106的上部的密封树脂109表面的温度测定部T设置热电偶，从而进行温度测定。
若密封树脂109表面的温度高，则可知热未从发光元件106的下表面逸散而发生蓄积。
[实施例2]
作为接合材料101，使用了含有1wt％的钛且余量为锡的锡-钛合金。除此之外的条件与实施例1同样地制作半导体装置，在温度85℃、湿度85％的恒温恒湿槽中放置3000hr后，进行温度测定。
[实施例3]
作为接合材料101，使用了含有10wt％的钛且余量为锡的锡-钛合金。除此之外的条件与实施例1同样地制作半导体装置，在温度85℃、湿度85％的恒温恒湿槽中放置3000hr后，进行温度测定。
[实施例4]
作为接合材料101，使用了含有15wt％的钛且余量为锡的锡-钛合金。除此之外的条件与实施例1同样地制作半导体装置，在温度85℃、湿度85％的恒温恒湿槽中放置3000hr后，进行温度测定。
[实施例5]
作为接合材料101，使用了含有30wt％的钛且余量为锡的锡-钛合金。除此之外的条件与实施例1同样地制作半导体装置，在温度85℃、湿度85％的恒温恒湿槽中放置3000hr后，进行温度测定。
[实施例6]
作为接合材料101，使用了含有0.1wt％的钒且余量为锡的锡-钒合金。除此之外的条件与实施例1同样地制作半导体装置，在温度85℃、湿度85％的恒温恒湿槽中放置3000hr后，进行温度测定。
[实施例7]
作为接合材料101，使用了含有30wt％的钒且余量为锡的锡-钒合金。除此之外的条件与实施例1同样地制作半导体装置，在温度85℃、湿度85％的恒温恒湿槽中放置3000hr后，进行温度测定。
[实施例8]
作为接合材料101，使用了含有0.1wt％的锆且余量为锡的锡-锆合金。除此之外的条件与实施例1同样地制作半导体装置，在温度85℃、湿度85％的恒温恒湿槽中放置3000hr后，进行温度测定。
[实施例9]
作为接合材料101，使用了含有30wt％的锆且余量为锡的锡-锆合金。除此之外的条件与实施例1同样地制作半导体装置，在温度85℃、湿度85％的恒温恒湿槽中放置3000hr后，进行温度测定。
[比较例1]
作为接合材料，使用了含有0.01wt％的钛且余量为锡的锡-钛合金。除此之外的条件与实施例1同样地制作半导体装置，在温度85℃、湿度85％的恒温恒湿槽中放置3000hr后，进行温度测定。
[比较例2]
作为接合材料，使用了含有35wt％的钛且余量为锡的锡-钛合金。除此之外的条件与实施例1同样地制作半导体装置，在温度85℃、湿度85％的恒温恒湿槽中放置3000hr后，进行温度测定。
[比较例3]
作为接合材料，使用了含有0.01wt％的钒且余量为锡的锡-钒合金。除此之外的条件与实施例1同样地制作半导体装置，在温度85℃、湿度85％的恒温恒湿槽中放置3000hr后，进行温度测定。
[比较例4]
作为接合材料，使用了含有35wt％的钒且余量为锡的锡-钒合金。除此之外的条件与实施例1同样地制作半导体装置，在温度85℃、湿度85％的恒温恒湿槽中放置3000hr后，进行温度测定。
[比较例5]
作为接合材料，使用了含有0.01wt％的钛且余量为锡的锡-钛合金。除此之外的条件与实施例1同样地制作半导体装置，在温度85℃、湿度85％的恒温恒湿槽中放置3000hr后，进行温度测定。
[比较例6]
作为接合材料，使用了含有35wt％的钛且余量为锡的锡-钛合金。除此之外的条件与实施例1同样地制作半导体装置，在温度85℃、湿度85％的恒温恒湿槽中放置3000hr后，进行温度测定。
[比较例7]
作为接合材料，使用了银糊剂。碳基台102使用了尺寸为4mm×4mm且厚度为1mm的碳基台。
(1)在碳基台102上以厚度为0.1mm且尺寸为1mm×1mm涂布银糊剂，将发光元件载置在所涂布的银糊剂上，在大气气氛中以100℃使其固化1小时，从而进行粘接。
(2)接着，在碳基台上隔着粘接层形成电极层。电极层是Cu，尺寸设为1mm×2mm、厚度设为0.05mm。
(3)接着，通过对发光元件和电极层配置铝制的引线而获得电连接。
(4)其后，用密封树脂将发光元件密封，制作半导体装置。
为了确认可靠性试验后的放热性，首先，将所制作的半导体装置在温度85℃、湿度85％的恒温恒湿槽中放置3000hr，在与实施例1相同的部位进行温度测定。
<结果和考察>
表2示出实施例1～9和比较例1～6的制作条件、温度测定结果和判定结果。
关于判定结果，在80℃以下因发光亮度的降低非常少而记作◎，在100℃以下至80℃为止因发光亮度的降低少而记作○，在高于100℃的情况下因发光亮度显著降低而记作×。
实施例1～3中，温度低至70℃、75℃、80℃，判定为◎。其可推测如下。首先，在碳基台102与接合材料的界面形成锡·钛·碳的化合物作为碳接合层103，此外，在发光元件106与接合材料101的界面还形成镍·锡的化合物作为发光元件接合层107。因此可推测：与粘接不同，界面的热阻减少，能够将发光元件106的热高效地传导至碳基台102，进而，热从热导率高的碳基台102逸散至放热板201。
实施例4、5中，温度为89℃、97℃和100℃以下，判定为○。
可以认为：在该情况下，热也与之前同样地逸散，但与锡的热导率50W/m·K相比，热导率为20W/m·K的钛的含量增加，因此，与实施例1～3相比冷却性能略微降低。
同样地，作为化合物形成性元素而使用钒、锆的实施例6、8中，温度低至69℃、70℃，判定为◎。此外，实施例7、9中，温度为95℃、96℃和100℃以下，判定为○。
这些结果也可知：与作为化合物形成性元素而添加了钛的情况同样地，通过形成化合物而使热高效地逸散至碳基台102。另一方面，钒的热导率为30W/m·K、锆的热导率为22.6W/m·K，可推测：若添加量增加，则接合层的热导率降低，温度略微上升。
比较例1～7中，温度均达到100℃以上，判定为×。比较例1、3、5中，作为化合物形成性元素的钛、钒、锆的含量少至0.01wt％，可推测在碳基台与接合材料的界面未形成化合物层，因此无法进行热传导，温度上升。
此外，比较例2、4中，作为化合物形成性元素的钛、钒、锆的含量多达30wt％，因此可推测：在发光元件的接合时接合材料未完全熔解，孔隙未被去除而呈现在接合层残留有空隙的状态。该空隙成为热阻，温度未下降。
实施例1～9和比较例1～6中，在温度85℃、湿度85％的恒温恒湿槽中放置3000hr，接合层的状态也未变化。对接合材料的侧面进行分析的结果，作为化合物形成性元素的钛、钒、锆以氧化物的形式稠化在侧面的表面层100nm左右。可推测：通过添加比锡容易形成氧化物的钛、钒、锆(上述第二方式所述的构成)，钛、钒、锆向与氧接触的表面移动，形成为牢固的氧化物层，由此抑制一定以上的氧向内部的侵入。
但是，比较例7中将银糊剂用作接合材料，因此，通过在温度85℃、湿度85％的恒温恒湿槽中放置3000hr，氧、水蒸气会侵入至树脂内部，树脂发生劣化而产生空隙。因此，热导率降低，导致温度上升，判定为×。
根据这些结果可知：作为接合材料，优选为含有0.1wt％以上且30wt％以下的化合物形成性元素，且余量中作为主要成分而包含锡的合金。此外，优选使用该接合材料将石墨基台与发光元件进行接合来制造半导体装置。由此，在恒温恒湿时接合材料的化合物形成性元素以氧化物的形式稠化在侧面的密封树脂界面，由此能够以钝态的形式发挥功能，抑制氧化的进行，确保高可靠性。
需要说明的是，根据实施例1～3的结果，化合物形成性元素的浓度优选为0.1wt％以上且10wt％以下。这不仅针对于Ti，对于V、Zr也同样。这是因为：Ti、V、Zr与Sn相比导热性差，若大量加入则热特性变差。
需要说明的是，本申请中包括将上述各种实施方式和/或实施例之中的任意实施方式和/或实施例适当组合而得的产物，能够起到各个实施方式和/或实施例所具有的效果。
产业上的可利用性
由利用本发明所述的接合材料而接合的发光元件和碳基台构成的半导体装置可确保高放热性和高可靠性，对于高亮度的驱动电流也能够使用。
附图标记说明
101 接合材料
102 碳基台
103 碳接合层
104 电极层
105 粘接层
106 发光元件
107 发光元件接合层
108 引线
109 密封树脂
110 半导体装置
201 放热板
301 半导体装置
302 发光元件
303 基台
304 银糊剂
305 电极
306 引线
307 密封树脂

Claims (8)

1.一种接合材料，其包含0.1wt％以上且30wt％以下的能够与锡和碳形成化合物的至少1种元素，余量中作为主要成分而包含锡。
2.根据权利要求1所述的接合材料，其包含0.1wt％以上且10wt％以下的所述元素。
3.根据权利要求1或2所述的接合材料，其中，所述至少1种元素是比锡容易氧化的元素。
4.根据权利要求1～3中任一项所述的接合材料，其中，所述元素与锡形成的化合物的熔点为1000℃以上。
5.根据权利要求1～4中任一项所述的接合材料，其中，所述至少1种元素包含选自钛、锆、钒的组中的至少1种。
6.根据权利要求1所述的接合材料，其包含大于5wt％且为10wt％以下的所述元素。
7.一种半导体装置的制造方法，其使用权利要求1～5中任一项所述的所述接合材料，通过将发光元件与碳基台进行接合而制造半导体装置。
8.一种半导体装置，其包括：
发光元件；
碳基台；以及
将所述发光元件与所述碳基台进行接合的权利要求1～5中任一项所述的所述接合材料。
CN201811422049.0A 2017-11-29 2018-11-26 接合材料、使用了该接合材料的半导体装置的制造方法和半导体装置 Pending CN109834404A (zh)

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