CN1107087A - 金属表面处理的方法 - Google Patents
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Abstract
通过用能量低于可以改变金属表面结构的能量
的激光束照射金属表面,可以在不用复杂步骤并对电
子部件或电子装置没有不利影响的情况下从金属表
面将氧化膜(和残留有机物、碳等,如果有的话)简单
除去,从而清洁金属表面。
Description
本发明涉及金属表面处理的方法,更具体地说是涉及当例如通过焊接将电路基片和半导体集成电路(LSI)等结合起来或对金属表面施加镀层时,从焊接表面或要处理的金属表面除去氧化膜,和残留有机物、碳等(如果有的话)的有效方法。
迄今为止,当电路基片和半导体集成电路等通过焊接相互结合起来时,都要求被焊接的金属表面保持清洁并没有阻碍焊接浸润性(solder wettability-inhibiting)物质存在。此外,还要求被镀的金属表面上没有氧化膜等,并且金属表面要保持清洁。当金线或金带通过超声波焊焊接在金属表面上时,金属表面上存在氧化膜是一个严重的问题,因而金属表面必须保持干净。
那些阻碍焊接浸润性的物质包括例如:氧化物、氯化物、硫化物、碳酸盐和有机化合物。特别是在焊接、镀、或用超声波焊焊接金线或金带的过程中,最严重的阻碍物质是存在于要处理的金属例如焊料、镍(Ni)、镍合金(镍和一种或多种其它元素的合金)表面上的氧化膜。
通常,氧化膜是通过焊剂被化学转化为波相物质的,因此金属表面的金属原子和焊料中的金属原子有一个相互直接碰撞的机会,通过分享它们的外层电子轨道形成金属键,进而形成合金。
在镀的时候,如果金属表面上存在氧化膜,镀就无法进行。例如,在电镀(镀的一种典型方式)的时候,氧化膜作为一层绝缘膜,阻止对电镀而言是必须的电传导,导致镀层的失败。
在置换镀的时候,氧化膜也起到阻碍层的作用,并且使要处理的金属表面和镀液之间不能发生置换反应,导致镀层的失败。
在镀之前,可以用盐酸等处理金属的表面来除去氧化膜,但是盐酸等残留在处理后的表面,并且这样的残留物成了降低焊接可靠性的因素。因此,迄今为止,在用酸处理以后,都是用碳氟化合物来清洗金属表面。
最近,已经建议使用少量的松香酸(松香)和己二酸等为焊剂而不对焊剂残留物进行任何清洗,但是提议的方法在焊接可靠性方面仍然不是令人满意的。[见“Alumit Techn ical Journal 19”(1992)和K.K.Nihon Kogyo Gizyutsukaihatsu Kenkusho (Industrial Technology Development Research Institute of Japan,Ltd.)的N.Kubota的一篇文章:“Working mechanism and Problems of flux for unnecessitating washing”]。
另一方面,提出了一种用激光束照射金属材料、钢、碳化物等的表面,因而制造具有均匀微细结构或非晶态结构并且有好的耐蚀性和耐磨性的材料的抛光方法,这种方法已经被用于要暴露在高温和高压环境下的金属材料例如用于汽车透平的材料的加工中[见“Laser Processing”(Contnuned Part),Page164,by A.Kobayashi,Published by Kaihatsu-sha]。
还提出在不使用任何焊剂或盐酸的情况下,用氩气溅射从金属表面除去氧化膜。
此外,还提出了用喷砂法使金属表面粗糙,再用合金元素对粗糙的金属表面进行镀层处理,然后用激光束照射镀层,由此使镀层熔化,从而形成一层没有针眼的具有很好粘结性的涂层(JP-A-63-97382)。
另外,还提出了通过在铝或铝合金的表面形成一层阳极氧化膜,从而形成一层具有好的耐蚀性和可焊接性的表面层(JP-A-62-256961)。
对上述现有技术进行广泛研究的结果,本发明人发现了下面的问题:
(1)当电路基片和集成电路等通过焊接相互结合起来时,在焊接前它们的表面上的氧化膜必须通过焊剂除去,并且焊剂残留物必须从它们的表面清洗掉。在镀之前用酸洗从金属表面除去氧化膜的情况下,残留的酸和金属表面产生后续的腐蚀。此外,在清洗之后还不可避免要进行干燥处理。
(2)当氧化膜是通过氩气溅射从金属表面除去时,溅射必须在真空中进行。因此,需要另外的溅射装置和它的复杂的操作控制系统。还存在这样的问题,就是氩气溅射对电子部件或电子装置的工作元件有不利影响。
(3)在上述的JP-A-63-97382中公开的使用激光束的抛光方法和激光照射方法中,通过高能量的激光束的照射和后来的熔化,表面金属结构被迫改变,因此赋予金属表面高的耐磨性和高的紧密性,但是在表面固化的过程中在金属表面上不可避免要形成一层氧化膜。
(4)在上述的JP-A-62-256961中公开的表面处理中没有涉及除去氧化膜的技术。
本发明的一个目的提供一种用于清洗金属表面的金属表面处理的方法,即在不使用任何复杂步骤和对电子部件或电子装置没有任何不利影响的情况下从金属表面除去氧化膜和残留的有机物、碳等(如果有的话)。
从下面公开的内容和附图可以看出本发明的其它目的。
根据本发明,提供了(1)一种金属表面处理的方法,包括用能量低于可以改变金属表面结构的能量的激光束照射金属表面,因而清洗金属表面,其中(2)激光束的脉宽不超过1μS;(3)激光束的波长为150nm-400nm;(4)金属是焊料、镍和镍合金的一种,其中(5)激光束的能量密度为0.5J/cm2-4.0J/cm2;和(6)在用激光束对金属表面照射以后,在清洁的金属表面上形成一层防止二次氧化的镀层。
在本发明中,要处理的金属表面被能量低于可以改变金属表面结构能量的激光束照射。更具体地说,照射是用能量高于金属表面的金属原子和氧原子之间的键能,但又低于金属原子之间的键能的激光束来进行的,因此只有金属表面的金属原子和氢原子之间的键被打开从而使氧化膜从金属表面上除去,同时残留的有机物、碳等(如果有的话)也从金属表面除去。即金属表面可以被清洗干净。
也就是说,用激光束照射的主要目的是打开金属表面金属原子和氧原子之间的键,并且最好使用脉宽不超过1μS的脉冲激光束。由于金属表面的金属原子和氧原子的键是被脉宽不超过1μS的脉冲激光束打开的,最好使用例如有短波长的准分子激光(eximer laser)(即高的光子能量)作为激光束。
用激光照射的气氛可以是空气、真空和氦气氛的任何一种,氧化膜都可以毫无问题地从金属表面上除去。
图1是垂直截面图,解释根据本发明实施例1的用于金属表面处理的方法。
图2是垂直截面图,解释本发明实施例1的一种改进,即在制造电子装置例如半导体集成电路(LSI)时用激光束经镜面反射又经透镜后照射焊料突起,来代替图1所示的焊料层。
图3是在用激光束照射之前,本发明实施例1的焊料层表面的照片,是用扫描电子显微镜照的。
图4是图3照片的放大。
图5是用激光束照射以后,本发明实施例1的焊料层表面的照片,是用扫描电子显微镜照的。
图6是图5照片的放大。
图7是曲线图,表明了在用激光束照射Sn-Pb焊料表面相同区域6次(常数)以后存在于Sn-Pb焊料表面的氧化膜的重量百分数(wt.%)(表示在纵座标上)和用来照射的激光束每个脉冲的能量密度(J/cm2)(表示在横座标上)之间的关系。
图8是曲线图,表明了当每脉冲能量密度恒定为1.5J/cm2时,用激光束照射以后存在于Sn-Pb焊料表面的氧化膜的重量百分数(wt.%)(表示在纵座标上)和激光束照射焊料金属表面相同区域的次数(表示在横座标上)之间的关系。
图9是一个垂直截面图,表明了本发明实施例1中通过焊接而结合的电子装置的一个实施方案。
图10是一个垂直截面图,表明了本发明实施例1中通过焊接而结合的电子装置的另一实施方案。
图11是解释根据本发明实施例2的用于金属表面处理的方法的垂直截面图。
图12是曲线图,表明了根据本发明实施例2设定激光束照射镍层相同区域的次数恒定为10时,存在于镍层表面的氧化膜的厚度(nm)(表示在纵座标上)和每脉冲激光束能量密度(J/cm2)(表示在横座标上)之间的关系。
图13是曲线图,表明了根据本发明的实施例2设定每脉冲激光束能量密度为0.75(J/cm2)(常数)时,存在于镍层表面的氧化膜的厚度(nm)(表示在纵座标上)和激光束照到镍层表面相同区域的次数(表示为横座标)之间的关系。
图14是垂直截面图,解释根据本发明实施例3用于制造电子装置的本方法。
图15是垂直截面图,表明了根据本发明实施例3使用了防止二次氧化措施的电子装置。
图16是垂直截面图,表示了电子装置和陶瓷基片上的镍层(Ni)或镍合金层之间的电连接,是不使用图15所示的任何输入/输出(I/O)引线而用焊料或软焊料直接焊接的。
图17A和17B分别是方案图和沿图17A的B-B的垂直截面图,表明了本方法应用于制造根据本发明实施例4的电子装置。
下面将参考实施例和附图对本发明进行详细描述,为了省略重复解释,其中解释本发明的实施例的附图中功能相同的部分用同样的标记数码来表示。
实施例1
图1是解释用于金属表面处理的本发明方法的垂直截面图。其中氧化膜4(和残留有机物、碳等,如果有的话)从焊料层3a的表面除去,其中焊料层3a是在作为陶瓷基片1的覆盖层的金属化层2上。金属化层2是一层例如钛(Ti)、镍(Ni)、镍合金等的薄膜。
激光束5经镜面7反射并通过透镜6后照射到焊料层3a的表面,由此从焊料层3a的表面除去氧化膜4(和残留的有机物、碳等,如果有的话)。
图2表示了图1中所示的上述实施例的改进,其中在制造例如半导体集成电路(LSI)时,激光束5经镜面7反射并通过透镜6照射焊料凸起3b的表面,代替图1中的焊料层3a。
实施例1中所用的激光束5是能量低于能够改变焊料层3a或焊料凸起3b的金属结构能量的激光束,更具体地说,是能量高于焊料层3a或焊料凸起3b表面的Sn-Pb原子和氧原子之间的键能,但又低于Sn-Pb原子之间的键能的激光束。
当焊料层3a或焊料凸起3b的表面被激光束5照射时,在不熔化焊料层3a或焊料凸起3b的前提下只有表面的Sn-Pb原子和氧原子之间的键被激光束5的能量打开,因此氧化膜4能从焊料层3a或焊料凸起3b的表面除去。同时,残留的有机物、碳等(如果有的话)也被从金属表面除去。
在这种情况下,用激光束5照射的主要目的是打开表面上的Sn-Pb原子和氧原子之间的键,因此优选的激光束5是脉宽不超过1μS的脉冲激光束。此外,由于表面上的Sn-Pb原子和氧原子这间的键是被脉宽不超过1μS的脉冲激光束打开的,例如具有短波长的准分子激光(高的光子能量)优选作为激光束5。
用激光束5照射的气氛可以是空气、真空和氦气的任何一种,由此氧化膜4可以从焊料层3a或焊料凸起3b的表面除去。
图3是焊料层3a或焊料凸起3b在用激光束照射之前的表面状态的照片,是用扫描电子显微镜照的,图4是图3的放大照片,从中可以发现在焊料层3a或焊料凸起3b的表面有氧化膜和残留有机物、碳等黑色残留物。
图5是用激光束照射以后焊料层3a或焊料凸起3b的表面状态的照片,也是用扫描电子显微镜照的,图6是图5的放大照片,从中可以看出氧化膜和残留有机物、碳等基本上从表面除去了。
图7是曲线图,表明了在用激光束6次照射Sn-Pb表面上同样区域以后残留在Sn-Pb表面上的氧化膜的重量百分数(%)(表示在纵座标上)(是以照射前表面上的氧化膜为100为基础的);和以每个脉冲的激光束能量密度(J/cm2)(表示在横座标上)之间的关系,从中明显看出在用能量密度在0.5J/cm2-4.0J/cm2范围的激光束来照射后残留氧化膜的重量百分数比照射前的低,而其中具有能量密度为1.5J/cm2的激光束最佳。
图7的纵座标上的氧化膜的重量百分数是基于由能量色散X射线分析(EDX)得出的氧浓度确定的。
图8表示了用激光束照射后存在于Sn-Pb表面上的氧化膜的重量百分数(以照射前表面上存在的化膜为100)(表示在纵座标上)和用恒定的能量密度为每脉冲1.5J/cm2的激光束照射金属表面相同区域的次数(表示在横座标上)之间的关系,从中显然看出通过大约八次照射存在于Sn-Pb表面的氧化膜的重量百分数达到最小值。即用具有恒定的能量密度为每脉冲1.5J/cm2的激光束照射八次以后存在于Sn-Pb表面上的氧化膜的重量百分数达到最小值,因此,料层3a或焊料凸起3b的浸润性得到改善。
图9是垂直截面图表明了半导体装置结构的基本部分包括:由形成在集成电路和陶瓷基片两个表面的作为覆盖层的金属化层2通过焊料突起3b用焊接方法与陶瓷基片1结合的集成电路(LSI)8,它们表面上的氧化膜都根据实施例1的本方法以一种不用焊剂的方式除去了。
图10是一个垂直截面图表明了通过焊料突起3b用焊接方法与图9所示的半导体装置结构结合的密封罩9的基本部分,它们的表面上的氧化膜已经根据实施例1的本方法以不用焊剂的方式除去了。
实施例2
图11是垂直截面图,解释根据本发明实施例2的用于金属表面处理的方法,其中氧化膜4(和残留有机物、碳等,如果有的话)从形成在陶瓷基片1上的作为覆盖层的镍(Ni)层或镍合金层2a上除去。
通常,镍(Ni)层或镍合金层2a容易发生氧化,因此很容易在镍(Ni)层或镍合金层表面形成一层氧化膜4。
可以通过用激光束5经镜面7反射再经过透镜6来照射镍层或镍合金层的表面而使氧化膜4从镍层或镍合金层的表面除去。
图12表示了用激光束5照射10次以后存在于镍层2a表面的氧化膜4的厚度(表示在纵座标上)和每个脉冲的激光束5的能量密度(J/cm2)(表示在横座标上)之间的关系。即用激光束5照射镍层2a上同样区域的次数恒定为10次。从图12明显看出不同起始厚度的氧化膜4(40nm和25nm,分别用黑点和白点表示)随着激光束5能量密度的增加能被除去。
图13表示了用具有恒定能量密度每脉冲0.75J/cm2的激光束5照射以后存在于镍层2a表面的氧化膜厚度(nm)(表示在纵座标上)和激光束照射镍层2a同样区域的次数(表示在横座标上)之间的关系。即激光束5的能量密度恒定为每脉冲0.75J/cm2。从图13明显看出氧化膜的厚度随着激光束的照射次数增加而减小。
实施例3
图14是一个垂直截面图表示根据实施例3实施的本发明的电子装置例如半导体集成电路(LSI)等的基本部分。
图14所示的电子装置通过如下来制造:根据实施例1和实施例2所示的用于金属表面处理的本方法从形成在陶瓷基片1上的作为覆盖层的镍层或镍合金层2a的表面将一层氧化膜(和残留有机物、碳等,如果有的话)除去,然后通过电镀、无电敷镀或置换镀在表面处理后的(即清洁的)镍层或镍合金2a上形成一层镀层10,它的镀层材料通常是金(Au)以避免清洁的镍层或镍合金层的二次氧化。即根据实施例3的实施方案、从作为金属化层的镍层或镍合金层2a的表面上除去了氧化膜(和残留的有机物、碳等,如果有的话),为了防止得到的清洁金属化层2a的二次氧化,在清洁的金属化层10上形成了镀层10。
图15是垂直截面图表示了一个电子装置结构的基本部分,它根据实施例3的实施方案特别采用了防止二次氧化的措施。其中镍(Ni)层和镍合金层作为一层金属化层形成在陶瓷基片1的一部分上;在金属化层2a和陶瓷基片1的表面上全部形成一层有机绝缘层15;在绝缘层15上形成一个洞以便使镍(Ni)层或镍合金层2a暴露出来;根据实施例1和2的用于金属表面处理的本方法从金属化层2a的暴露表面上除去了氧化膜(和残留有机物、碳等,如果有的话);然后在得到的清洁的金属化层2b上形成一层防止金属化层2b二次氧化的镀层10;并通过焊料或软焊料11将输入/输出(I/O)引线12固定在镀层10上。
如图1和11所示,通过激光束5的照射可以从镍层或镍合金层2a表面除去氧化膜4(和残留有机物、碳等,如果有的话),然后根据本发明在得到的清洁金属化层2a上形成镀层10以防止发生二次氧化,可以改善电子装置例如半导体集成电路(LSI)等的输入/输出(I/O)引线12和陶瓷基片1之间的电连接性。在用激光束5照射从金属化层2a表面将氧化膜4(和残留物,如果有的话)除去后1周之内,电子装置的输入/输出(I/O)引线12可以通过焊料或软焊料11与陶瓷基片1上的金属化层2a发生直接的电连接,而不用在它们之间使用防止二次氧化的镀层(例如金镀层)。
图16是垂直截面图,表示了电子装置8和陶瓷基片1上的金属化层2a之间发生直接电连接的结构的基本部分,这种电连接是不使用如图15所示的输入/输出(I/O)引线而是通过焊料或软焊料层11直接发生的。
在本发明的上述实施方案中没有必要使用焊剂等。
实施例4
图17A和17B分别是一个方案图和沿图17A的B-B线的垂直截面图,表明了根据实施例4实施的本发明的电子装置例如半导体集成电路等的基本部分,其中金属膜13与有机绝缘层15的良好的粘结性,例如铬(Cr)或钛(Ti)层,并作为一层覆盖层形成于有机绝缘层15上;一层镍层(Ni)或镍合金层2a作为一层金属化层形成在金属膜13的表面上;根据实施例1和2用于金属表面处理的方法通过激光束的照射将氧化膜(和残留的有机物、碳等,如果有的话)从金属化层2a的表面除去;然后用超声波焊将金(Au)带或金线焊接在清洁的金属化层2a上。
通常,由于在金属化层2a的表面有氧化膜(和残留有机物等,如果有的话),很难在金带或金线14和金属化层2a之间进行焊接。通常根据实施例1和2用于金属表面处理的方法从金属化层2a的表面将氧化膜(和残留的有机物等,如果有的话)除去,可以在它们之间获得好的结合。
在上述的实施例中,根据本发明进行表面处理的金属列举了镍(Ni)层或镍合金层2a和焊料层3a或焊料凸起3b,但是不仅局限于这些金属。即本发明可以应用于任何有必要从其表面除去氧化膜(和残留有机物等,如果有的话)的金属,但应该根据要处理的金属的性质选择合适能量的激光束。
在上述实施例中,激光束是列举脉冲激光来来说明的。在不熔化金属本身的前提下,可以使用具有较长波长的激光例如CO2激光,通过连续照射可以达到与这些脉冲激光束相似的效果。
本发明通过参考实施例得到了详细描述,但并不局限于实施例所示的实施方案,并可以在不背离本发明精神和范围的前提下进行不同程度的改进。
Claims (6)
1、一种金属表面处理的方法,包括用能量低于能够改变金属表面结构能量的激光束照射金属表面,由此来清洗金属表面。
2、一种根据权利要求1的方法,其中激光束的脉宽不超过1μS。
3、一种根据权利要求1的方法,其中激光束的波长为150nm-400nm。
4、一种根据权利要求1的方法,其中金属是焊料、镍和镍合金的一种。
5、一种根据权利要求4的方法,其中激光束的能量密度为每脉冲0.5J/cm2-4.0J/cm2。
6、一种根据权利要求1的方法,其中在用激光束照射金属表面后,在金属表面形成一层防止二次氧化的镀层。
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- 1994-10-04 JP JP23981394A patent/JP3355251B2/ja not_active Expired - Lifetime
- 1994-10-27 US US08/330,380 patent/US5499668A/en not_active Expired - Lifetime
- 1994-10-29 TW TW083110018A patent/TW316864B/zh active
- 1994-11-02 CN CN94118330A patent/CN1043414C/zh not_active Expired - Fee Related
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CN114249897A (zh) * | 2020-09-24 | 2022-03-29 | 深圳市鸿信顺电子材料有限公司 | 一种含浸液及其在片式元件的表面处理工艺方面的应用 |
CN115351424A (zh) * | 2022-02-15 | 2022-11-18 | 深圳市艾贝特电子科技有限公司 | 一种无助焊剂激光焊接方法 |
CN115178881A (zh) * | 2022-08-01 | 2022-10-14 | 成都科宁达材料有限公司 | 一种氧化铝陶瓷的表面处理方法、氧化铝陶瓷/金属异质钎焊方法 |
Also Published As
Publication number | Publication date |
---|---|
JP3355251B2 (ja) | 2002-12-09 |
CN1043414C (zh) | 1999-05-19 |
US5499668A (en) | 1996-03-19 |
JPH07171689A (ja) | 1995-07-11 |
TW316864B (zh) | 1997-10-01 |
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