CN1326256C - 热电组件的制造及制造过程中所使用的焊料 - Google Patents
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Abstract
用热电元件(12，14)与连接导体(24，26)之间的焊料结点(28，30)制作了一种热电模块(10)，此焊料含有大约50-99%重量比的铋和大约50-1%重量比的锑。还提供了一种带有导体材料(16，18)涂覆的碲化铋元件(12，14)的热电模块(10)，它不需要镍或其它扩散阻挡层。还提供了带有具磷镍表面(20，22)的导体(24，26)的模块(10)。并提供了这种热电模块(10)的制造和使用方法。
Description
这是1995年10月3日提出的申请号为08/535,449的题为“热电组件的制造及制造过程中所使用的焊料”的申请的部分继续申请。
本发明涉及到改进了的热电器件及其改进了的制造方法。更确切地说，本发明涉及到一种用于热电组件的基于铋锑合金的改进了的连接焊料，涉及到焊接于铜之类导体上的磷镍表面以形成热电组件的热电元件，并涉及到这种热电组件的应用。
热电组件是一种可用作热泵或发电机的小型固态器件。当被用来发电时，此组件被称为热电发电机(TEG)。TEG在被施加温差时，利用塞贝克效应来产生电压。
当被用作热泵时，此组件被称为热电致冷器(TEC)或热电加热器(TEH)并呈现珀尔帖效应。当电流通过二个不同类型的半导体构成的结时，由珀尔帖效应引起一个温度变化。这种半导体通常装配在热电组件中，当施加电流时，其中的热就从组件的一侧传输到另一侧。当从致冷侧取出的热耗散在另一侧上的热沉时，此组件可用作致冷器件。组件的这两侧通常由陶瓷材料组成。
位于两侧陶瓷之间的是由铋、碲、硒和锑组成的铋碲化物所制成的半导体元件。半导体元件被掺杂以产生过剩的电子(n型)或导致缺乏电子(P型)。在Gelb等人的美国专利4,855,810中描述了这种类型的典型组件。根据现有技术，这类组件含有用含铋与锡的焊料焊接于导体的半导体元件。在Haba的美国专利3,079,455中描述了一种这样的焊料。Haba描述了一种由锡、锑与铋组成的焊料。铋含量为40-50％重量比，而锑含量为1.5-3.5％重量比。
用铋碲化物元件构成的热电组件被用于温度范围约-80℃至250℃的应用中。这种用含锡焊料制成的热电组件由于长期暴露于很宽的温度范围而受到损害。实际上已发现，组件的性能每年降低大约15％或更多。在大体高于80℃的温度下，用含锡焊料制成的热电组件事实上被认为是不可用的。
缺乏可用性的一个理由是标准铋锡焊料在138℃下熔化。在高于80℃的温度下，焊料中的锡趋于急剧扩散进入半导体元件并进入半导体元件的晶格中，成为其中的掺杂剂或与元件材料起反应。同时，在邻近于焊接端的材料表面上，锡形成薄膜，起跨接于元件的电阻器的作用，引起IR下降和/或造成短路。
Gelb等人借助于用铅锑焊料取代锡基焊料，寻求克服锡扩散及形成电阻器的问题。但在升高的温度下，铅也扩散并与热电半导体材料起反应，形成一个热电性能很差的区域。
为了防止铅或锡的扩散，工业上的标准做法是在元件与焊料之间采用一个诸如层叠在元件上的镍之类的扩散阻挡层。在例如Fuschetti的美国专利5,429,680中描述了这样一个系统。但这种方法是非常复杂而昂贵的，而且不能完全防止铅或锡的扩散。而且，由涂覆有镍的材料所制成的元件在结构上很脆弱，在涉及长时间功率或温度循环的各种应用中无法持续保持有效。
对“包锡”半导体已描述了由铋和锑组成的焊料。例如，Kolenko，Ye A.的“热电致冷器件”(Foreign Science and Technology Center，U.S.Army Material Command，Department of the Army(AD691974)，PP131-138，1967年)在表15中描述了一种用于半导体包锡的含90％铋和10％锑的焊料和一种BiSn连接焊料。在表15中还描述了一种用于半导体包锡的含80％铋和20％锑的焊料。但并未建议将其用作连接焊料或与磷镍表面一起用来连接导体。
本发明的一个目的是提供一种不与热电材料发生反应而形成扩散源、掺杂剂和反应物的焊料。
本发明的另一目的是提供一种在提高了的温度(包括高达275℃)下具有改进了的寿命和低的失效率的热电组件。
本发明的又一目的是提供一种带有焊料不在热电元件之间形成电阻器的焊接结构的热电组件。
本发明的再一目的是提供一种无需昂贵的扩散阻挡层的热电组件。
本发明包含一种焊料，用来将诸如由铜、铝或其它熟知的导电材料制成的那些导体(例如汇流条)连结到淀积在热电组件中热电元件一端的导电材料上，其中所述的焊料含有大约50-99％重量比的铋和大约1-50％重量比的锑，其中铋和锑的综合重量百分比约为100％，特别是当导体配备有磷镍表面时更是如此。
本发明还提供了一种制造热电组件的方法，此方法包含：
1)在铋碲化物热电元件二端上淀积不需要扩散阻挡层的导电材料；
2)在诸如铜或铝之类的导体上制作磷镍表面；以及
3)用含有大约50-99％重量比的铋和大约1-50％重量比的锑的焊料，将上述导电材料连接到上述磷镍表面，其中铋和锑的综合重量百分比约为100。
第一步骤中的导电材料含有大约50-100％重量比的铋，其余主要是锑。
为利用热梯度发电，对器件施加一个跨过热电元件的温度梯度，且连接导电元件以形成电路。为了产生热电致冷或加热所需的热梯度，对器件加电流。由于珀尔帖效应沿流过热电元件的电流的方向产生温度梯度，并在冷端处达到致冷功能而在热端处达到加热功能。
本发明提供的热电组件能够使用于具有高达并包括约275℃的宽广工作温度的各种应用中。
附图中的图1是热电组件的等角图，二个陶瓷侧中的一个已移去以更清楚地示出组件元件；
图2是沿图1中2-2线的热电组件剖面图；
图3是适用于本发明的铋锑二元焊料合金系统的相图。
根据本发明，提供了一种热电组件，它包含一个由半导体材料，确切地说是由铋碲化物材料组成的n型和p型热电元件的阵列。这些元件有一个第一端和一个第二端，并如现有技术中所知的那样被排列在交替地置有n型和p型元件的行和列中。
这些元件在各端上淀积有导电材料构成的薄涂层，其中所述的涂层基本上没有镍之类的扩散阻挡层。适合用作涂层的材料为铋锑合金或纯铋。这样，导电材料含有大约50-100％重量比的铋，其余主要是锑。这种提供了可焊表面的涂层的厚度达0.001英寸。
制作在不导电衬底上的导体被用来连接各元件。这种导体配备有一个至少含有3.5％的磷的磷镍表面。制作此表面的一种方法是在导体顶部提供一层磷镍。磷镍表面中所含的磷量范围一般为大约3.5-18％。磷量最好是7-13％，8-12％更好。磷镍层的厚度通常为约20-约400微英寸。此导体最好是铜。
用含有大约50-99％重量比的铋和大约50-1％重量比的锑的焊料，将磷镍表面焊接到热电元件上导体材料的薄涂层上。特别是对于高温应用，此焊料应不含有诸如锡、铜、银、金、铅、锌、镉、铟、镓、碘、氯、钠和钾之类的起掺杂剂作用的元素。在本发明的一个最佳实施例中，焊料含有大约75-96％重量比的铋和大约25-4％重量比的锑。在本发明的一个最好的最佳实施例中，焊料含有大约80-95％重量比的铋和大约20-5％重量比的锑。
参照附图，图1和2示出了一种改进了的热电组件(10)，它有一个n型(Bi2Te3-Bi2Se3)和P型(Bi2Te3-Sb2Te3)铋碲化物热电元件(12，14)构成的阵列。n型和p型元件在其端部淀积有纯铋或铋锑合金构成的薄涂层(16，18)。此涂层被焊接于制作在导体(24，26)上的磷镍层(20，22)。由铋锑焊料形成连结结点(28，30)。导体制作在诸如氧化铝或氧化铍的不导电或绝缘的陶瓷衬底(32，34)上。
本发明由于提供了能够耐高达275℃的高温的组件而成为对标准组件的一种改进。此一改进使组件能够使用于高压灭菌蒸锅或其它类型的消毒设备中例如200℃的温度下。在高于200℃的温度下，此组件可用于油田井下设备及汽车发动机中。
借助于使器件相对于实际或所需的热梯度恰当地取向并借助于提供电连接使器件与负载或电源串联，可实现能量转换。当取向成热电元件彼此平行且都平行于热梯度的方向时，只要保持温度梯度，电能就会馈向电路中的负载或能源。
同样，若将电流加于器件，则通过珀尔帖效应将产生热梯度。器件对电流方向的恰当取向将如所述导致加热或致冷。
下面的例子说明了根据本发明的最佳实施例的制造过程：
例子
采用带有与含磷约为10％(8％-12％)的磷镍层金属化的铜的氧化铝板，制作了热电组件。铜合金化如下面所述被连接到n型与p型元件。
提供了由Bi2Te3-Bi2Se3(n型)和Bi2Te3-Sb2Te3(P型)制成的半导体元件。半导体元件的二端用厚度约为0.001英寸的Bi∶Sb＝95∶5的合金薄层涂覆。用铋锑连结焊料将半导体元件上的涂层连接到磷镍层。采用了本技术熟知的标准酸基焊剂和标准焊接技术。
所使用的连结焊料具有下列的铋锑重量比：
98.5∶1.5 95∶5
97.5∶2.5 90∶10
94.25∶4.75 80∶20
然后，在涂连结焊料之前，在半导体元件上制作一个纯铋涂层，来代替半导体元件上的铋锑涂层。
采用95∶5连结焊料的组件在165℃-200℃下测试了7000小时，其性能令人满意且其热电性质无剧烈改变。此组件通过了瞬时功率反转测试中的75,000个循环和1000次温度循环而无任何失效。采用所公开的连结焊料范围内的其它的铋锑比率与半导体元件上的铋或铋锑涂层，获得了比现有技术有改进的结果。
用7-13％之间的磷含量获得了优于现有技术产品的结果，而用约3.5-18％之间的磷含量获得了比现有技术有改进的结果。
作为比较，含有镍阻挡层和含锡焊料的标准组件连有限数目的功率循环都通不过。
上述描述仅仅是本发明最佳实施例的示例，本发明的范围并不局限于此。本技术领域的熟练人员将很容易地对本发明作出额外的修改而不超越本发明的范围。
Claims (17)
1.一种热电组件，它包含：
a.由半导体材料制成的n型和p型热电元件阵列；
b.淀积在元件二端的由导电材料构成的薄涂层，所述材料包含大约50-100％重量比的铋，其余主要是锑；
c.带有磷镍表面的汇流条，其中所述表面的磷含量至少为3.5％重量比；
d.将上述涂覆过的热电元件连接到上述汇流条上的上述磷镍的焊料，此焊料含有50-99％重量比的铋和50-1％重量比的锑。
2.权利要求1的组件，其中的焊料含有大约75-96％重量比的铋和大约25-4％重量比的锑。
3.权利要求2的组件，其中的焊料含有大约80-95％重量比的铋和大约20-5％重量比的锑。
4.权利要求1的组件，其中的磷含量约为3.5-18％重量比。
5.权利要求4的组件，其中的磷含量约为7-13％重量比。
6.权利要求5的组件，其中的磷含量约为8-12％重量比。
7.权利要求1的组件，其中的汇流条由铜制成。
8.权利要求1的组件，其中汇流条上的磷镍表面是制作在汇流条上的磷镍层。
9.一种耐高温应用的热电组件的制造方法，它包含下列步骤：
a.在热电元件二端淀积一种导电材料，上述材料含有大约50-100％重量比的铋，其余主要是锑；
b.在汇流条上制作磷镍表面；
c.用一种由大约50-99％重量比的铋和大约50-1％重量比的锑组成的焊料，将上述导电材料连接于上述磷镍表面，其中铋和锑的综合重量百分比约为100％。
10.权利要求9的方法，其中的焊料含有大约75-96％重量比的铋和大约25-4％重量比的锑。
11.权利要求10的方法，其中的焊料含有大约80-95％重量比的铋和大约20-5％重量比的锑。
12.权利要求9的方法，其中的磷镍层至少含有3.5％重量比的磷。
13.权利要求12的方法，其中的磷含量大约为3.5-18％重量比。
14.权利要求13的方法，其中的磷含量大约为7-13％重量比。
15.权利要求14的方法，其中的磷含量大约为8-12％重量比。
16.权利要求9的方法，其中的汇流条由铜制成。
17.权利要求9的方法，其中的磷镍表面是制作在上述汇流条上的层。
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US53844995A | 1995-10-03 | 1995-10-03 | |
| US08/538,449 | 1995-10-03 |
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| Publication Number | Publication Date |
|---|---|
| CN1211342A CN1211342A (zh) | 1999-03-17 |
| CN1326256C true CN1326256C (zh) | 2007-07-11 |
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| Application Number | Title | Priority Date | Filing Date |
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| CNB961974478A Expired - Fee Related CN1326256C (zh) | 1995-10-03 | 1996-09-30 | 热电组件的制造及制造过程中所使用的焊料 |
Country Status (22)
| Country | Link |
|---|---|
| US (1) | US5817188A (zh) |
| EP (1) | EP0870337B1 (zh) |
| JP (1) | JP3862179B2 (zh) |
| KR (1) | KR19990066931A (zh) |
| CN (1) | CN1326256C (zh) |
| AT (1) | ATE228270T1 (zh) |
| AU (1) | AU702453B2 (zh) |
| BR (1) | BR9610829A (zh) |
| CA (1) | CA2233979C (zh) |
| CZ (1) | CZ102898A3 (zh) |
| DE (1) | DE69624936T2 (zh) |
| DK (1) | DK0870337T3 (zh) |
| EA (1) | EA000388B1 (zh) |
| ES (1) | ES2183979T3 (zh) |
| HU (1) | HUP9902023A3 (zh) |
| IL (1) | IL123773A (zh) |
| MX (1) | MX9802673A (zh) |
| NO (1) | NO981507L (zh) |
| PT (1) | PT870337E (zh) |
| TR (1) | TR199800606T1 (zh) |
| UA (1) | UA51672C2 (zh) |
| WO (1) | WO1997013283A1 (zh) |
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Also Published As
| Publication number | Publication date |
|---|---|
| PT870337E (pt) | 2003-03-31 |
| EP0870337B1 (en) | 2002-11-20 |
| IL123773A (en) | 2001-03-19 |
| JP2002507321A (ja) | 2002-03-05 |
| CZ102898A3 (cs) | 1998-08-12 |
| NO981507D0 (no) | 1998-04-02 |
| DK0870337T3 (da) | 2003-03-03 |
| HUP9902023A3 (en) | 2002-11-28 |
| CA2233979C (en) | 2005-09-27 |
| DE69624936D1 (de) | 2003-01-02 |
| UA51672C2 (uk) | 2002-12-16 |
| AU702453B2 (en) | 1999-02-18 |
| KR19990066931A (ko) | 1999-08-16 |
| BR9610829A (pt) | 1999-12-21 |
| CA2233979A1 (en) | 1997-04-10 |
| ES2183979T3 (es) | 2003-04-01 |
| EA199800303A1 (ru) | 1998-10-29 |
| US5817188A (en) | 1998-10-06 |
| JP3862179B2 (ja) | 2006-12-27 |
| CN1211342A (zh) | 1999-03-17 |
| ATE228270T1 (de) | 2002-12-15 |
| MX9802673A (es) | 1998-11-30 |
| TR199800606T1 (xx) | 1998-06-22 |
| EA000388B1 (ru) | 1999-06-24 |
| EP0870337A1 (en) | 1998-10-14 |
| EP0870337A4 (en) | 1999-02-17 |
| DE69624936T2 (de) | 2003-03-27 |
| IL123773A0 (en) | 1999-11-30 |
| WO1997013283A1 (en) | 1997-04-10 |
| HUP9902023A2 (hu) | 1999-11-29 |
| AU7394796A (en) | 1997-04-28 |
| NO981507L (no) | 1998-04-02 |
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