CN86107676A - 具有改进玻璃密封性的防相互扩散的铁—镍合金 - Google Patents
具有改进玻璃密封性的防相互扩散的铁—镍合金 Download PDFInfo
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Abstract
本发明涉及一种铁—镍合金,它含有大约30—60%镍,大约0.001—0.15%氮、至少一种选自由大约1—10%钼和大约0.001—2%铝组成的元素,剩余部分主要是铁。该合金显示了改进的防金属间化合物形成性,改善了玻璃与金属的密封性,并且改善了线焊接性能。本发明的合金作为半导体密封装置(10)的导线框架材料具有特殊用途。
Description
本发明是关于在电子和电器应用中具有特殊用途的铁-镍合金。该铁-镍合金含有氮和至少一种选自由钼和铝组成的元素。
铁-镍合金,特别是铁-镍-钼合金,是十分有名的磁性合金。这些合金是以这样的所需要的特性,诸如高的初始导磁性、高的电阻率、良好的导磁率一致性(相容性)以及良好的磁稳定性为特征的。
美国专利1,757,178(Elmer),2,407,234(Guthrie等人),2,891,883(Howe),3,024,142(Parkin),4,082,580(Pfeifer等人)以及4,536,229(Jin等人)说明了这些铁-镍和铁-镍-钼磁性合金。
还发明铁合金,包括铁-镍合金,可用于电子应用。例如,陶瓷封装(CERDIPs)中的导线框架和起罐头用的销,已用铁-镍合金制成。但是,使用这些合金不是没有严重问题,在半导体器件中,铁-镍合金的导线框架典型地是通过许多铝和/或铝合金导线连接到一集成线路片上的。铁合金的导线框架与铝引线之间的接合位是典型的位置,在此由于暴露在热之中,例如封装半导体器件涉及的热处理,铁和铝之间相互扩散的强烈倾向性的结果,形成了脆性金属间化合物。
这种金属间化合物问题,一般是通过在一个或多个铁合金导线框架的表面形成一薄铝条加以处理的。铝条可以是涂覆到表面的薄涂层或一种镶嵌物。在某些情况下,该铝条包含一涂层在整个导线框架上。然后导线被焊接到铝条上,以便形成一种铝/铝电偶。美国专利3,559,285(Kauffman)说明了具有一种镶嵌铝条的铁合金导线框架材料。
使用铁合金作为导线框架材料带来的另一个问题与玻璃密封有关。许多半导体集成线路片用陶瓷封装,称作CERDIP。为了提供密封封装结构,导线框架用玻璃密封材料诸如具有氧化铝底座的那些材料焊接到一层或多层陶瓷材料上。Fe-42Ni一类铁合金不能很好地与密封玻璃材料焊接。另一方面,在导线框架材料上或中的一铝条被用来克服这种焊接问题,因为铝一般与玻璃密封焊接很好。
半导体器件和/或密封装置的制造者已表明需要这样的合金,它们可用作导线框架的材料而不必涂覆或给导线框架镶嵌。通过避免导线框架的涂覆和/或镶嵌,降低了制造成本。所需要的合金的特征在于:改进耐金属间化合物的形成并提高与玻璃密封材料的焊结能力。
因此,本发明的一个目的是提供具有改进耐金属间化合物形成的一种铁-镍合金。
本发明的又一个目的是提供具有改进玻璃粘结性能的一种上述合金。
本发明的另一个目的是提供具有改进线连接特性的上述合金。
本发明的又一个目的是提供适于用作半导体器件的导线框架的上述铁-镍合金。
从下面的说明和附图中将对这些和其它目的以及优点变得更加明瞭,其中参考数字说明对应元件。
本发明通过将氮和至少一种选自由钼和铝组成的元素加至铁-镍合金,以达到前述目的。已经发现,将氮和钼(有或没有铝)加至铁-镍合金,以改进合金对金属间化合物的形成的阻力,尤其是在典型的半导体制造和/或封装技术涉及的热处理过程中更是如此。此外,业已发明含有这些添加物的合金具有改进了与玻璃密封材料的焊接附着性,而且使用标准工业超声波焊接技术易于焊接到铝或铝合金导线上。
按照本发明的合金含有大约30%-60%的镍,大约0.001%-0.15%的氮,至少一种选自由大约1%-10%的钼和大约0.001%-2%的铝组成的元素,剩下部分主要是铁,该合金的特征是具有单相和单面的立方金属结构。该合金最好还具有铁与镍之比在大约1.1∶1-1.6∶1的范围内,推荐的合金含有大约39%-55%的镍,大约0.005%-0.05%的氮,至少一种选自由大约1%-4%的钼和大约0.3%-1%的铝组成的元素,剩下的主要是铁。
附图是一个半导体密封装置的横截面图。
本发明是关于具有改进的防金属间化合物的形成性和/或与玻璃密封材料的附着力得到提高的铁-镍合金。这些合金在电器和电子的应用中央具有特殊用途。例如,它们可用作在半导体密封装置中的导线框架或类似元件。另外,它们可用于起罐头的销,玻璃对金属的电源馈线,或其它类似应用。
现在参考附图来说明典型的半导体密封装置10。它包括一个陶瓷底座口,第一玻璃层16和来自导线框架的大量导线18,此导线框架通过玻璃层16焊接到陶瓷底座12上。半导体器件20既可使用芯片(die)连接垫,也可使用含金材料层14固定在底座口上。含金材料被用于许多现代密封装置中,以使层14和小片20之间有可能形成金-硅易熔焊接。含金属层14可包含一镀金板或一喷射到陶瓷底座上的金粉涂料。器件20用大量的引线22连接到导线18上。一般地说,引线由铝或诸如Al-1%Si的铝合金制成。第二玻璃层24置于导线框架组件的导线18上。为了完成密封装置,由陶瓷或金属材料制成的盖26置在玻璃层24上。
在某些密封装置中,玻璃层24和盖26每个具有中心孔或窗孔,以使器件20焊接到垫或层14上,并且在玻璃层24和/或盖26熔合玻璃层16以后进行导线连接。配有一个盖板(未示出),在器件置于垫上并在进行线连接后封闭窗孔。盖板可用一种陶瓷材料、一种金属材料,例如镀金科伐(Kovar),或玻璃材料制成。
为了加工图中所示的半导体密封装置,首先将芯片连接垫或含金属层14焊接或镀到陶瓷底座口上。然后将玻璃层16丝网印刷到陶瓷底座上并用空气燃烧,留下用于把半导体器件20连接到垫或层14的孔或窗孔23。此后,将具有导线18的导线框架置于玻璃层16上并熔合。最好,第二玻璃层24与盖26先连接,然后再与层16熔合。随后,玻璃层24与玻璃层16熔合,形成密封装置结构。但在这之前,器件20被连接到垫或层14上,并且进行器件20与导线18之间的线连接。典型的线连接是在环境压力下使用热压,超声或热声连接器进行。这种线连接操作常导致在导线18上形成表面氧化物。
用于封装集成电路片或半导体器件的有代表性的陶瓷材料包括氧化铍。在这些密封装置中的玻璃层16和24可由任何适宜的玻璃材料,诸如85%氧化铝-15%硼酸组合物组成。
应当承认,图中所示的密封装置以及所讨论的附属物只是用来做 图示,而决不意味着限制本发明。本发明的合金可连同各种各样的密封装置构件和材料一起使用。
如前文讨论,在许多现代密封装置中,导线18和导线框架可由诸如Fe-42Ni的铁合金制成。用这些合金作导线框架材料已产生几种明显的问题。这些问题包括:(1)在导线18和引线22的连接处形成金属间化合物,尤其是当导线用铝或铝合金制成时;(2)导线18和玻璃层16和24之间的附着力差。金属间化合物问题具有特殊意义,因为它有害地影响了导线连接的质量。许多半导体器件的损坏都是由于导线互相连接处变脆或断裂造成的。附着性差的问题也很重要,因为它使装置的密封性变差,并且导致密封装置破裂。曾试图克服这些问题,包括用象铝、金、及其合金一类的材料对导线框架的导线18进行涂覆和/或镶嵌。但涂覆和/或镶嵌必然合增加密封装置的制造成本。
按照本发明,这些问题可通过使用铁合金的导线和导线框架加以解决,而所述的铁合金显示出改进了防金属间化合物的形成和/或改进了对玻璃密封材料的附着力。本发明的合金包括这样的合金:它们主要是由大约30%-60%镍、大约0.001%-0.15%氮、至少一种选自大约1%-10%钼和大约0.001%-2%铝组成的元素、剩下部分主要是铁构成的一种组合物。最好,合金中铁与镍之比在大约1.1∶1-1.6∶1的范围内。
已经发现,氮是特别有用的添加剂,因为它明显降低了不需要的铁-铝金属间化合物的形成。钼和铝添加物的益处在于,它们改进玻璃的附着性和合金的线连接特性。钼也是有用的,它提高了本发明铁-镍合金中的氮溶解度和/或扩散度,并且据信,它与表面氧化物作用,有助于提高本发明的合金与玻璃密封材料之间的焊接性。
尤其有用的实施方案包括:(a)一种主要由大约39%-55%镍、大约0.005-0.05%氮、大约1%-4%钼和主要是铁的剩余部分构成的合金;(b)一种主要由大约39%-55%镍、大约0.005%-0.05%氮、大约0.3%-1.0%铝和主要是铁的剩余部分构成的合金。当材料受到足以生成金属间化合物的高温时,合金(a)特别有用;而当温度未达到足以形成金属间化合物的高温时,合金(b)特别有用。如果需要,合金(a)中可加入大约0.3%-1.0%范围的铝添加剂,以便进一步改善合金的玻璃密封性。
从金属学的角度看,本发明的合金特征是面心立方结构。另外,该合金为单相合金。
当钼被加入铁-镍合金中、而且铁-镍合金被焊接到纯铝组件时,合金的最小钼含量可用下面的公式确定:
%Mo≥(86±5-%Ni)/(7.25±1.25)(1)
对于本发明的某些钼实施例的合金来说,也能确定合金的最小氮含量。例如,含大约39%-47%范围的镍和约1%-5.1%范围的钼的合金,推荐按下面的公式制定最小氮添加剂的用量。
%N=(0.0001)×(34l-7.5Ni+7.4Mo)(2)
如果需要,本发明的合金还可含有近大约1.0%有效量的锰和/或近大约0.1%有效量的镁。据信,锰和/或镁添加剂对降低铸造过程中硫杂质的作用特别有效。
为了改善金属间化合物的抑制特性,合金中应不含硅。这是由于硅与氮结合形成氮化硅,降低了氮在金属间的作用。在本发明的合金中,可允许常规普通的杂质存在,但应保持在杂质量级。
本文所使用的前述合金组份的百分比为重量百分比。
本发明的合金可以任何所需方式铸造,包括但不局限于Durville铸造、连续铸造和直接冷铸,以形成铸锭或条状。铸造后,可通过诸如热轧对合金进行热加工,和/或通过诸如冷轧进行具有至少一次中间退火的冷加工。最好对合金进行冷加工强化而不用预先热加工。冷加工强化时,用标准冷轧技术获得的压缩量在大约20%-40%范围内。
中间退火可在96%-4%H2气氛下进行,而温度在大约800℃-1000%范围内,时间在大约1小时-24小时的范围内。最好,在所述气氛下,在大约2小时-8小时的时间范围并在大约900℃-975℃的温度范围进行中间退火。如果需要,中间退火可采用将合金充氮。另一方面,可通过将氮气吹入含铁、镍、钼和/或铝的熔体的方法加氮。任何本技术领域已知的适宜的技术手段,诸如喷枪都可以被使用,以使氮进入到熔体中。在另一个替换方法中,合金可在裂化氨气氛下,通过使铸锭或铸条退火而充氮。
在加工后,铁-镍带材可按照任何本技术领域已知的标准加工技术手段加工成所需要的产品,例如导线框架。
为了显示本发明的改进之处,进行了下面的实施例。
实施例1
为了证明用本发明的合金改进了防金属间化合物所具有的形成作用。制备了一组具有表Ⅰ所示组分的合金。在950℃下,于60%N2-4%H2气氛下加热合金使它充氮。
表Ⅰ
合 Ni Mo Al N Fe
金 (重量%) (重量%) (重量%) (重量%) (重量%)
A 42 - - 0.01 剩余部分
B 42 0.7-6 - - 剩余部分
C 42 2.8-9.1 - 0.01 剩余部分
D 41 - 0.7-2.1 0.01 剩余部分
E 40 2.5 0.8-1.8 0.01 剩余部分
将每一种合金的2″×4″试样焊接到铝合金试样上。铝合金含有1.25%硅。用POSIT-BOND焊接技术进行焊接,其中试样受到60%冷加工压缩。试样用机械清洗并在焊接前除油。经焊接的试样在500℃下暴露16小时。测量在这种热处理过程中形成的金属间化合物的厚度。表Ⅱ报导了这些测量结果。
表Ⅱ
合金 金属间的厚度(μm)
A 12
B 11-10
C 2
D 11
E 2
表Ⅱ的数据表明,通过将具有或没有铝的氮和钼加入铁-镍合金,则在Fe-Ni和Al-Si组份之间形成的金属间化合物的厚度减低。这通过使用合金C和E得到的结果证实。
为了在半导体密封装置中使生产者免除使用镀铝或镶铝条的铁-镍合金组件,替换的铁-镍合金应显示出等同的或基本等同的玻璃密封性。下面的实施例说明了用本发明的合金可以得到的改进的玻璃密封性。
实施例Ⅱ
制备一组具有表Ⅲ所示组份的铁-镍合金。为了便于比较,也制备镀铝的Fe-42Ni合金试样。每一种合金试样焊接到市售的氧化铝陶瓷封装(CERIP)材料上,以便形成玻璃-金属-玻璃的复合层。在焊接前,将铁合金试样除油。
在焊接后,玻璃-金属-玻璃复合层受到用于和集成线路密封装置一起的标准扭距试验。在这个试验中,试样扭曲直至破裂。表Ⅲ报导了这个试验的结果。
表Ⅲ
合金 扭距强度(吋-磅)
镀铝Fe-42Ni 74-82
Fe-42Ni-0.0027N 0
Fe-40Ni-2.8Mo-0.0058N >50
Fe-41Ni-2.7Mo-0.8Al-0.01N >50
Fe-42Ni-0.7Al-0.01N >50
从表Ⅲ可以看出,按照本发明形成的那些合金,显示的扭距强度可与镀铝的F2-42N2达到的强度相比。表Ⅲ还表明,仅把氮加入Fe-42Ni中不能改善合金的玻璃密封性。据信,本发明的合金提供的玻璃密封附着性的改进,是玻璃和金属之间形成的化学键的结果,而不是用先有技术材料所发现的机械压实型接合。
为了免除Fe-42Ni导线框架用铝镀/镶铝条,还必须把铝或铝合金引线直接线焊接到裸露合金导线框架上,而且要得到用镀铝合金所得到的疲劳载荷。下面的实施例说明了在用本发明合金得到的线连接的改进。
实施例Ⅲ
制备一组具有表Ⅳ报导的组份的铁-镍基体。为了模拟典型的线连接操作,使用Kulicke和Soffa Model#484-8线连接器,在基体上线连接一个由Al-1%Si合金组成的1.25密耳的导线。所有基体在峰温493℃下进行空气框架沉降处理8分钟。表Ⅳ报导了使线和各种基体间断开连接所需的平均载荷的结果。
表Ⅳ
基体 平均导线拉力载荷(克)
镶铝条的Fe-42Ni 12
裸露的Fe-42Ni 9
Fe-40Ni-2.8No-0.01N 10
Fe-42Ni-0.7Al-0.01N 10
Fe-41Ni-2.1Al-0.01N 9
Fe-41Ni-2.6Mo-0.45Al-0.01N 12
Fe-42Ni-2.5Mo-1.8Al-0.01N 10
从表Ⅳ可以看出,本发明合金制成的基体与裸露的铁-镍合金基体比较,一般显示出改进的线连接特性。
当本发明的合金在电子和电器应用中具有特殊用途时,它们还在其它需要提高防金属间化合物形成性和/或改进的玻璃附着性的应用中具有特殊用途。例如,本发明的合金可用于复合结构中,例如铁-镍/玻璃复合物和铁-镍合金/铝或铝合金复合物。
显然,按照本发明提供的防相互扩散的铁-镍合金具有改进的玻璃密封性,这完全满足了目的、手段以及前述的优点。在结合其具体实施例说明了本发明之后,很明显,根据前面的描述,多种替换物、改型、和变换,对本技术领域专业人员是显而易见的。因此,打算把所有这些替换物,改型和变换包括在所附权利要求的精神实质和较宽的范围内。
Claims (16)
1、一种具有改进的防金属间化合物形成性的铁-镍合金,其特征在于所述合金主要包括大约30%-60镍、大约0.005-0.15%氮、至少一种选自由大约1%-10%钼和大约0.001-2%铝组成的元素,剩下部分主要是铁组成。
2、根据权利要求1的合金,其进一步的特征在于所述至少一种元素包含钼,所述的钼提高了合金的氮溶解度和/或扩散性,并按照下述公式的量存在:
%Mo≥(86±5-%Ni)/(7.25±1.25)。
3、根据权利要求1的合金,其进一步的特征在于:
所述至少一种元素包含大约1%-4%的钼;
所述氮以大约0.005%-0.05%的量存在。
4、根据权利要求3的合金,其进一步的特征在于所述合金另外主要包括大约0.3%-1.0%铝。
5、根据权利要求1的合金,其进一步的特征在于:
所述至少一种元素包含大约0.3%-1.0%铝;
所述氮以大约0.005%-0.05%的量存在。
6、根据权利要求1的合金,其特征在于铁与镍在所述合金中的比例在大约1.1∶1-1.6∶1范围内。
7、根据权利要求1的合金,其进一步特征在于所述合金另外主要包括选自有效量近大约1.0%锰和有效量近大约0.1%镁的至少一种添加元素,以便在铸造过程中降低硫杂质的作用。
8、根据权利要求1的合金,其进一步特征在于所述镍以大约30%和小于约60%的量存在,所述钼以大约1%-5.1%的量存在,而氮的量按下面的公式给定。
%N=(0.0001)×(34l-7.5Ni+7.4Mo)。
9、一种导线框架,其特征在于所述导线框架由权利要求1的合金制成。
10、一种半导体密封装置(10),其特征在于:
至少一个导线框架的导线(18)由一种合金制成,该合金主要包括大约30%-60%镍、大约0.005%-0.15%氮、至少一种选自由大约1%-10%钼和大约0.001-2%铝组成的元素、剩余部分主要是铁。
11、根据权利要求10的半导体密封装置(10),其进一步的特征在于:
至少一种铝或铝合金1线(22)焊接到每种所述铁-镍合金导线(18)的第一部分上;及
玻璃材料(16、24)连接到每种所述导线(18)的第二部分上。
12、根据权利要求11的半导体密封装置,其进一步特征在于:
一个半导体器件(20);
通过至少一种所述引线(22),将每种所述导线(18)连接到所述器件(20)上;及
至少一个组件(12,26)由陶瓷材料制成,用所述玻璃材料(16,24)将所述陶瓷材料组件焊接到每个所述导线(18)上,以便形成密封结构。
13、一种形成铁镍合金的方法,其特征在于:
形成一种熔体,它含有大约30%-60%镍、至少一种选自由大约1%-10%钼和大约0.001%-2%铝组成的元素、剩余部分是铁;及
将大约0.005%-0.15%氮加入所述熔体。
14、根据权利要求13的方法,其进一步特征在于所述氮加入步骤中,包括将氮气吹入所述熔体。
15、一种形成铁-镍合金的方法,其特征在于:
铸造一种铁-镍合金,它主要包括大约30%-60%镍,至少一种选自由大约1%-10%钼和大约0.001%-2%铝组成的元素,剩余部分是铁;
在含氮气氛下使所述铸造合金退火,由此使所述合金充入大约0.005%-0.15%氮。
16、根据权利要求15的方法,其进一步特征在于:
在所述退火步骤前,将所述合金加工成条状;及
在所述含氮气氛下,使所述合金条在大约800℃-1000℃下退火约1-24小时。
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US4649083A (en) * | 1983-02-17 | 1987-03-10 | Olin Corporation | Electrical component forming process |
US4500605A (en) * | 1983-02-17 | 1985-02-19 | Olin Corporation | Electrical component forming process |
JPS6025262A (ja) * | 1983-07-21 | 1985-02-08 | Sumitomo Electric Ind Ltd | Ic用リ−ドフレ−ム |
US4536229A (en) * | 1983-11-08 | 1985-08-20 | At&T Bell Laboratories | Fe-Ni-Mo magnet alloys and devices |
JPS61149461A (ja) * | 1984-12-25 | 1986-07-08 | Nippon Mining Co Ltd | シヤドウマスク材及びシヤドウマスク |
US4711826A (en) * | 1986-01-27 | 1987-12-08 | Olin Corporation | Iron-nickel alloys having improved glass sealing properties |
-
1985
- 1985-11-29 US US06/803,021 patent/US4816216A/en not_active Expired - Fee Related
-
1986
- 1986-11-27 EP EP86116486A patent/EP0224263A3/en not_active Withdrawn
- 1986-11-28 JP JP61284109A patent/JPS62133039A/ja active Pending
- 1986-11-28 CN CN198686107676A patent/CN86107676A/zh active Pending
- 1986-11-29 KR KR860010144A patent/KR870005113A/ko not_active Application Discontinuation
Also Published As
Publication number | Publication date |
---|---|
KR870005113A (ko) | 1987-06-04 |
EP0224263A3 (en) | 1987-10-07 |
EP0224263A2 (en) | 1987-06-03 |
US4816216A (en) | 1989-03-28 |
JPS62133039A (ja) | 1987-06-16 |
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