CN103620753B - 清洁引线框以改善导线接合工艺 - Google Patents

清洁引线框以改善导线接合工艺 Download PDF

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Publication number
CN103620753B
CN103620753B CN201280030395.9A CN201280030395A CN103620753B CN 103620753 B CN103620753 B CN 103620753B CN 201280030395 A CN201280030395 A CN 201280030395A CN 103620753 B CN103620753 B CN 103620753B
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acid
composition
weight
lead frame
salt
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CN201280030395.9A
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CN103620753A (zh
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T·Q·科利尔
D·B·瑞内
R·拉玛默希
G·E·帕里斯
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Versum Materials US LLC
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Air Products and Chemicals Inc
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    • H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
    • H01L21/04—Manufacture or treatment of semiconductor devices or of parts thereof the devices having potential barriers, e.g. a PN junction, depletion layer or carrier concentration layer
    • H01L21/48—Manufacture or treatment of parts, e.g. containers, prior to assembly of the devices, using processes not provided for in a single one of the subgroups H01L21/06 - H01L21/326
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Abstract

处理半导体衬底以从其除去不想要的物质或为后续接合准备所述半导体衬底的表面的方法，其中所述衬底包含引线框，所述引线框包含管芯、接合焊盘、触头、和导线，所述方法包括将所述衬底与可用于所述方法的液体清洁组合物相接触的步骤。

Description

清洁引线框以改善导线接合工艺
本申请要求2011年4月25日提交的美国临时申请61/478,582的优先权，所述申请以其全部内容通过引用并入本文。
技术领域
本发明涉及清洁半导体芯片和引线框上的金属表面以改善导线接合(wirebonding)工艺的方法。具体而言，本发明涉及包括将所述金属表面暴露于水基清洗液以从所述芯片和引线框的金属表面上除去金属氧化物、污染物和其它残余物的方法。
背景技术
生产半导体器件期间，引线框传统上作为成本有效的方式用于同时安装和处理多个半导体管芯（die）或芯片。每个引线框通常具有多个用于安装芯片的管芯焊盘(diepad)。所述引线框还充当将芯片通过引线框的引线与外部设备电连接的工具。在被称为导线接合的工艺中，接合导线与存在于芯片和引线框的所述引线上的电触头连接。接合焊盘通常由Al构成，但它们也可以是Cu。导线的其它端与引线框上的触头（contact）引线（可以是Ag、Au等）相连。
图1描绘了制造管芯封装的典型常规方法中的相关部分。首先，在步骤10，管芯从已经形成它的晶圆（wafer）上被切割或锯下。在从晶圆上切下管芯之后，在管芯接合或管芯连接步骤12中，将所述管芯的背面与载体或引线框牢固相连。通常，在管芯接合步骤12中，利用有机粘合剂、例如环氧树脂将所述管芯与引线框相连，然后通过烘烤而固化。一旦环氧树脂已经固化，在步骤14中，将所述管芯接合到引线框。
上述将所述金属导线连接到接合焊盘和触头的工艺被称作“导线接合”。导线接合期间可能出现的一个问题是金属导线没有粘住接合焊盘和/或触头。导线和接合焊盘/触头之间的差的粘附可能有若干原因，例如，金属表面氧化，以及在金属表面上有污染物。金属导线与接合焊盘/触头之间的差的粘附可通过诸如NSOP（未粘上焊盘）、NSOL（未粘上引线）、短尾、焊球起翘缺陷、金属互化物均匀性差、接合焊盘陷坑、空洞等，直接或间接地引起工艺故障。这些不仅导致接合工艺低效，而且还可以引起器件可靠性差。为了改善粘附，需要在导线接合之前清洁所述金属表面。
过去，在导线接合步骤14之前，通过例如使引线框和相连的管芯经受氩等离子体，来清洁管芯的正面。然而，这种氩等离子体法有几个缺点。例如，氩等离子体法没有彻底清洁Cu和Al接合焊盘上的残余物和微粒。此外，所述氩等离子体法没有从接合焊盘上有效除去铜或氧化铝。作为最后的例子，所述氩等离子体法不能在不造成所处理元件损害的情况下，从Al接合焊盘有效除去其它污染物例如氟。因此，需要一种清洁导线接合工艺中涉及的金属表面的方法，所述金属表面例如导线、接合焊盘和引线框触头，所述方法不具有上面提到的缺点。
发明内容
本发明通过提供处理引线框组件以从其除去不想要的物质或为后续接合准备引线框组件的表面的方法而满足了这一需要，其中引线框组件包含以下部件或元件中的一种或多种：引线框、管芯、其上具有接合焊盘的管芯、触头、触头引线、和导线，所述方法包括将引线框组件的至少一部分或引线框组件的部件与包含水和至少一种酸或至少一种盐的组合物相接触的步骤。所述接触步骤中使用的组合物可以包含0.003至约25重量%的一种或多种羧酸。
处理引线框组件或衬底的方法，所述引线框组件或衬底包含引线框和至少一个下面列举的部件或元件中的一种或多种：管芯、接合焊盘、管芯附着（die-attach）材料、塑模化合物、触头和导线，所述方法包括以下步骤：将所述引线框组件（半导体衬底）或其部分与包含以下物质、基本由以下物质组成或由以下物质组成的组合物接触：具有选自羧酸或多元酸的酸和所述酸的盐（例如铵盐）的酸缓冲液，酸与盐（例如铵盐）的摩尔比从10:1至1:10；和任选的有机极性溶剂，所述溶剂可以按所有比例在水中混溶；和任选的氟化物、以及水，其中在一些实施方式中，所述组合物具有约3至约7的pH，并且其中所述引线框可以在至少一个表面上包含铝金属；并且所述方法可以包括干燥所述半导体衬底的附加步骤。
在另一个方面，本发明提供了处理半导体衬底或引线框组件或衬底以从其除去不想要的物质或为后续接合准备所述引线框组件或衬底的表面的方法，其中所述引线框组件包括引线框,所述引线框包含至少一个下面列出的元件中的一种或多种：管芯、接合焊盘、管芯附着材料、塑模化合物、触头和导线，所述方法包括以下步骤：将所述引线框或引线框的部分与包含以下物质、基本由以下物质组成、或由以下物质组成的组合物接触：约0.005至约16重量%的至少一种羧酸、其盐或其混合物或者含胺基的羧酸、其盐或其混合物；约0.003至约4重量%的至少一种羟基羧酸、其盐或其混合物或者含胺基的羟基羧酸、其盐或其混合物；并且其余基本上是水，并具有约1至约4的pH，其中所述半导体衬底在至少一个表面上包含铜金属；以及干燥所述半导体衬底。在一些实施方式中，二羧酸是优选的。
在又一个方面，本发明提供了处理包含引线框的引线框组件的方法，所述方法包括：将一个或多个个体管芯与包含触头引线的引线框相连，以形成具有暴露的（例如铝、铜、Ni、Pd、Au、Ag和Mg）金属表面的组件；将所述引线框组件与包含以下物质、基本由以下物质组成或由以下物质组成的组合物接触：具有选自羧酸或多元酸和所述酸的盐（例如铵盐）的酸缓冲液，其中酸与盐（例如铵盐）的摩尔比从10:1至1:10；和任选的有机极性溶剂（其可按所有比例在水中混溶）；和任选的氟化物，以及水，其中所述组合物可具有约3至约7的pH；干燥所述衬底；进行导线接合步骤，包括将接合焊盘之间的导线连接在管芯上以及将触头引线连接在引线框上以形成管芯和引线框组件；以及在管芯和引线框组件上形成塑模，以形成封装电路。
在又一个方面，本发明提供了处理包含引线框的微电子器件衬底的方法，所述方法包括：将个体管芯与包含触头引线的引线框相连，以形成具有暴露的铝金属表面的衬底；将所述半导体衬底与包含以下物质、基本由以下物质组成、或由以下物质组成的组合物接触：约0.005至约16重量%的至少一种羧酸、其盐或其混合物；约0.003至约4重量%的至少一种羟基羧酸、其盐或其混合物或者含胺基的酸、其盐或其混合物；并且其余基本上是水，并具有约1至约4的pH；干燥所述衬底；进行导线接合步骤，包括将接合焊盘之间的导线连接在管芯上以及将触头引线连接在引线框上以形成管芯和引线框组件；以及在管芯和引线框组件上形成塑模，以形成封装电路。
本发明的其它方面、特征和实施方式将从接下来的公开内容和所附的权利要求书中更充分地明白。本文中描述的所有重量%都基于组合物的总重量，除非另作说明。“基本由...组成”是指所述组合物可含有未要求的组分，只要那些未要求的组分在添加到其他方面一致的要求的清洁组合物中时，在用于相同的清洁工艺时不实质影响从引线框组件的接合焊盘除去金属氧化物即可。从引线框组件除去金属氧化物优选是约或更高。上述氧化物清除速率不意欲指示所述引线框清洁工艺的限度。例如，在分批清洁工艺中，可以将许多引线框浸入含有本文中描述的清洁溶液的清洁浴中，所述溶液长时间期间、例如100分钟提供的氧化物清除速率，并仍然得到清洁的引线框。
本发明还提供了可用于本文描述的方法的引线框清洁组合物。
附图说明
前述的概要，以及下面优选实施方式的详细说明，在结合附图阅读时将更好理解。为了说明本发明，在图中显示了当前优选的实施方式。然而，应该理解，本发明不限于所显示的精确布置和手段。在图中：
图1是说明制备集成电路器件所包括的常规步骤的框图；
图2是说明本发明方法的步骤的框图；
图3是说明本发明实施方式的铝表面处理性能的图；
图4是说明本发明实施方式的性能的图；
图5是说明本发明实施方式的性能的图；
图6是说明本发明的实施方式在铜氧化物清除和再生长方面的性能的图；
图7是说明本发明的实施方式在铜氧化物清除和再生长方面的性能的图；
具体实施方式
本发明涉及用于处理微电子器件衬底和封装的组合物，包括在导线接合工艺期间将金属导线从接合焊盘连接到引线框的过程期间可用于准备金属表面的组合物。可以使用术语“引线框”，然而它不意味着是限制，并且包括所有类型的半导体封装衬底，例如镀过或未镀过的BGA以及有机衬底和引线框。本发明还涉及处理引线框组件或半导体衬底以从其中除去不想要的物质或为后续接合准备引线框组件或半导体衬底的表面的方法。术语“引线框组件”或“引线框衬底”可以用于意指，但不意味着是限制，具有至少一个或多个与其结合的管芯并还可以包含其它部件的任何类型的引线框，所述其它部件是与其连接例如粘合或焊接的部分。
为了便于参考，“微电子器件”对应于为了用于微电子、集成电路或计算机芯片应用而制造的半导体衬底和封装、平板显示器和微型机电系统（MEMS）。要理解，术语“微电子器件”不意味着以任何方式的限制，并且包括将最终变成微电子器件或微电子组件的任何衬底。优选地，所述微电子器件包括引线框组件或半导体衬底。
在本文中使用时“羧酸”是指（除非另有定义或从上下文明白）单-、二-或多-羧酸，包括含胺基的单-、二-或多-羧酸、其盐或其混合物，包括含羟基的单-、二-或多-羧酸、其盐或其混合物和/或含其它基团的单-、二-或多-羧酸。
在本文中使用时，术语“半导体衬底”包括将最终变成微电子器件或微电子组件的任何衬底或部分形成的封装。优选地，所述半导体衬底包括包含与引线框连接的管芯的引线框组件。
在本文中使用时，“约”意欲指相当于指定值的±5%。
在本文中使用时，对于从其上具有污染物（包括金属氧化物）的微电子器件清洁所述污染物的“适用性”对应于从所述微电子器件、更具体地说引线框组件或引线框组件的部件、例如管芯或所述管芯上的接合焊盘至少部分清除所述残留物/污染物。优选地，利用本发明的组合物和方法从所述微电子器件、更具体地说引线框组件或所述引线框组件的部件、例如管芯或所述管芯上的接合焊盘除去至少90%的残留物/污染物，更优选地，除去至少99%的残留物/污染物。
利用铜或铝互连金属化技术制造集成电路，由于电性能和成本的优点，已经变得流行。为了防止金属间相，所述IC设有铜或铝焊盘。通常，利用金和铜导线材料进行IC与芯片载体或引线框的导线接合，但是铝和银也已被利用。将这些导线与不同的焊盘材料接合产生不同的冶金体系。近来，主要由于成本明显较低的推动，已有从金导线转向铜导线的趋势。
不幸的是，铜和铝二者的氧化都非常迅速，使得更难以实现可靠的导线接合。因此，为了确保导线接合的接合性和可靠性，一个关键的条件是接合表面应该没有或基本上没有任何污染物，所述污染物包括氧化物。通常，在单个晶圆上在一个地方形成多个电路，然后将所述晶圆运输到另一个地方，在此从所述晶圆上切出管芯并封装。因为在所述晶圆制造和封装工艺之间可能经过相当长的时间，在这种时间期间可发生所述管芯上铜或铝接合焊盘的氧化。因此，本发明提供了在晶圆上制造电路之后、但是在已经包封或彻底封装所述管芯之前，对集成电路的铜和铝焊盘的有效清洁。
现在参考图2，制备在其上形成多个集成电路的半导体晶圆的方法。所述集成电路可以具有铜或铝形成的接合焊盘。在硅晶圆上用这种焊盘形成电路的方法是已知的，并且不需要对其详细论述来理解本发明。要理解，本发明的处理在所述晶圆上已经形成集成电路之后进行。通常，它是在已经向所述晶圆施加所有层并且已经在去离子水中清洗所述晶圆并且已经打磨所述晶圆的背面以除去不必要的物质之后。随后，所述晶圆在试验/组装/封装机构加工，在此每个芯片或管芯在仍然作为晶圆时进行测试；在这个被称为晶圆级测试的步骤下，对好管芯进行鉴定。然后所述晶圆通过切块过程被切成小块或切成单颗。每个由此产生的已经确定通过所述晶圆级测试的芯片或管芯（“已知的好管芯”）可以通过一个或多个管芯连接加工步骤与引线框相连，所述步骤包括将环氧树脂、焊膏或其它粘合材料施加到引线框和/或表面，所述表面可以是一个或多个管芯的背面，并将所述一个或多个管芯与所述引线框连接。所述引线框可以具有在其上形成的用于接收管芯的焊接凸点或柱形凸点或类似的连接部件，它们之上施加或接受了环氧树脂、焊膏或其它粘合材料。通常，可以是条或连续的带/卷形式的引线框含有许多相连的管芯，所述管芯以后将形成为封装。如果施加环氧树脂的话，所述引线框或衬底然后可以以高温处理固化环氧树脂，以确保管芯与衬底的适当粘附。如果使用焊膏的话，将接着进行焊接步骤。随后，在管芯上的接合焊盘和引线框上的触头之间连接导线。这些引线框或引线框组件（以后）将单颗化，以形成将被模塑和包封的个体封装。本发明涉及在所述引线框组件上进行的清洁，其可以发生在高温环氧树脂固化或其它管芯连接步骤之后、和导线接合之前，和涉及提供用于从所述金属接合焊盘和引线框或衬底触头和表面上除去氧化物及其他污染物。
现在参考图2，显示了制备在其上形成多个集成电路的半导体晶圆的方法。所述集成电路可以具有铜或铝形成的接合焊盘。在硅晶圆上用这种焊盘形成电路的方法是已知的，并且不需要对其详细论述用于理解本发明。要理解，本发明的处理在所述晶圆上已经形成集成电路之后进行。通常，它是在已经向所述晶圆施加所有层并且已经在去离子水中清洗所述晶圆并且已经打磨所述晶圆背面以除去不必要的物质之后，并且还优选在已经进行过每个芯片或管芯的测试之后。通常，在测试之后和切块之前进行，所述晶圆利用溶剂例如去离子水、异丙醇、丙酮和甲醇再次清洁。本发明涉及在晶圆通常已经经受测试、切块之后、和形成引线框组件之前或之后进行的清洁，并提供从金属接合焊盘除去氧化物以及然后将引线与所述接合焊盘相接。那些步骤之后，接着可以是通常在真空下模塑在引线框组件上的封装。虽然图2中未显示，但本发明的方法包括以下方法：所述方法中，在马上要形成引线框组件之前发生清洗步骤，然后形成所述引线框组件（亦即管芯与引线框连接），然后将引线与接合焊盘连接。
更具体地，在被分成步骤20A和步骤20B的步骤20开始，晶圆并且特别是每个管芯的金属接合焊盘与清洁组合物接触，所述清洁组合物如所示的两种清洁组合物——组合物A或组合物B任何一种，所述清洁组合物的每种将在下面更详细地描述。（图2中的方法可以用单个清洗步骤显示。）优选地，本发明方法的清洗步骤包括将引线框组件或引线框组件的至少一部分、例如可以已经连接到引线框的管芯或管芯上的接合焊盘与组合物A（优选用于含Al衬底）或组合物B（优选用于含Al或含Cu衬底）任一种接触。所述引线框组件的至少一部分优选在室温或升高的温度下在包含所述组合物的浴中浸渍或浸泡约1分钟至约40分钟之间的时间段，优选约5分钟至约30分钟，并更优选约20至约30分钟。
用于清洁引线框组件的接合焊盘的组合物包括包含酸或盐或者酸和盐的混合物的水溶液。用于清洁引线框组件的接合焊盘的组合物包括包含酸、优选一种或多种羧酸或多元酸的水溶液。所述组合物可以包含水和约0.003重量%至约25重量%的一种或多种酸。所述组合物的一些实施方式可以具有1至7的pH。在一些实施方式中，所述组合物包含酸缓冲液；酸是所述酸缓冲液的部分。在其它实施方式中，所述组合物包含一种或多种羧酸。所述组合物可以包含一种或多种酸、和/或一种或多种溶剂和/或一种或多种氟化物（也称为含氟化合物）和/或一种或多种添加剂。所述添加剂可以包括表面活性剂和/或腐蚀抑制剂。例如，可用于本发明方法的组合物的一些实施方式包含柠檬酸和任选的表面活性剂。所述组合物的一些实施方式除了一种或多种酸之外，还可以包含0%或30重量%至90重量%的有机极性溶剂、0.0005重量%至20重量%的氟化物、0.5重量%至40重量%的水、最多15重量%的任选的腐蚀抑制剂和/或表面活性剂。可用于本发明方法的一些组合物的实例包含水、乙酸或柠檬酸、氟化铵和二甲基乙酰胺、以及任选的丙二醇和任选的腐蚀抑制剂。
组合物A将用来指称可用于本发明方法中用于清洁引线框组件的包含酸缓冲液的那些组合物。组合物B将指称可用于本发明方法中用于清洁引线框组件的不包含酸缓冲液的那些组合物。
组合物A
在本发明的一种实施方式中，所述清洁组合物是组合物A。组合物A是包含酸缓冲液和水并且也可以包含极性溶剂（其优选可按所有比例在水中混溶）、和/或氟化物的清洁组合物。在某些实施方式中，将所述组合物的pH调节到约3至约7并任选包含腐蚀抑制剂和/或其它添加剂。组合物A的一些实施方式可以没有腐蚀抑制剂、和/或没有添加剂和/或没有表面活性剂和/或没有溶剂。作为酸缓冲液的一部分的酸优选包括羧酸和/或多元酸。
优选地，组合物A由获得pH为3至7的组合物所需要量的酸缓冲液、0重量%至90重量%或30重量%至90重量%的可按所有比例在水中混溶的有机极性溶剂、0.001重量%至20重量%的氟化物、0.5重量%至40重量%的水、和最多15重量%的腐蚀抑制剂（和/或其它添加剂）组成。在可替代实施方式中，所述组合物可以包含最多90重量%或大于90重量%的水。
如前所述，本文中描述的组合物A包含酸缓冲液。所述酸缓冲液当添加到本文公开的组合物中时，提供了pH被调节成对敏感金属例如铝、铜、钛等的腐蚀最小化的缓冲组合物。所述酸缓冲液以获得想要的组合物的pH范围所需要的量进行添加。术语“酸缓冲液”在本文中使用时，是抵抗由于向所述组合物少量添加酸或碱而导致pH改变的溶液。向本文中公开的组合物添加酸缓冲溶液防止了由于用水稀释或被碱或酸污染引起的pH摇摆。
为了提供所述组合物内的这种缓冲效应，所述酸缓冲液中酸与其共轭碱的摩尔比在10:1至1:10、或基本上1:1、或1:1内，其中基本上是指所述等摩尔浓度的±2重量%。缓冲液通常被认为是弱酸并且针对酸或碱的最宽缓冲范围是弱酸基团的pKa的任一侧约一个pH单位。可以通过使酸与所述酸的共轭碱（或者在某些实施方式中是质子化的碱）的酸与碱的摩尔比为10:1至1:10或基本上1:1，来设定缓冲液的pH，所述酸对于想要的pH范围具有合适的pKa。
另外，pKa小于约6的某些盐当溶解在水中时可以与或不与所述溶解在水中的酸一起用于制造所述清洁组合物。
在某些优选实施方式中，所述酸缓冲液含有羧酸或多元酸、例如磷酸的铵盐。示例性的酸缓冲液可以包括乙酸/乙酸盐（例如铵盐、胺盐等）、苯甲酸/苯甲酸盐（例如铵盐、胺盐等）、和酚酸/酚盐（例如铵盐、胺盐等）。铵盐的例子是乙酸或磷酸的铵盐。在一种实施方式中，酸缓冲液是乙酸铵和乙酸的水溶液。在又一种实施方式中，酸缓冲液是苯甲酸和苯甲酸铵。
所述组合物可以包含0.003至30重量%或0.5至25重量%或0.5至20重量%或0.5至15重量%的酸，其是用于所述缓冲液的酸。在某些实施方式中，所述酸缓冲液可以含有弱酸例如三羟基苯、氢醌和/或水杨羟肟酸。在这些实施方式中，添加的弱酸的量可以为从0.003至30重量%或0.5至25重量%或0.5至20重量%或0.5至3重量%。共轭碱的量随添加到所述组合物的酸量变化，以向所述组合物提供缓冲溶液。
虽然本发明的组合物的pH可以从1至11，但在某些实施方式中，pH从约3至约9、或从约3至约7、或从约3至约6将使最敏感金属钝化，使腐蚀最低。优选地，所述pH范围是约3至约7。
可以添加到本文中公开的组合物中的一种或多种有机极性溶剂是在水中可混溶的那些溶剂。这些溶剂可以单独或以任何组合使用。所述组合物中可以存在于其中的所述一种或多种溶剂占约0重量%至约90重量%，或30重量%至约90重量%，或约30重量%至约70重量%，并可以是可按所有比例在水中混溶的有机极性溶剂。有机极性溶剂的例子包括但是不限于二甲基乙酰胺（DMAC）、单乙醇胺、n-甲基乙醇胺、甲酰胺、n-甲基甲酰胺、γ-丁内酯、N-甲基吡咯烷酮等等。其它的溶剂包括二羟醇和多羟醇例如二醇和多元醇例如（C2-C20）烷烃二醇和（C3-C20）烷烃三醇、环醇和取代醇。其它溶剂包括脲类，例如二甲脲、四甲脲等等。这些有机极性溶剂的具体例子是丙二醇、四氢糠醇（THFA）、二丙酮醇和1,4-环己烷二甲醇。优选的溶剂包括以下一种或多种：二甲基乙酰胺，二甲脲，丙二醇，单独使用或者彼此组合或与其它溶剂组合使用。
在某些实施方式中，所述有机极性溶剂可以是一种或多种二醇醚类。所述二醇醚类通常与水混溶并可以包括二醇单（C1-C6）烷基醚和二醇二（C1-C6）烷基醚，例如但不限于（C1-C20）烷烃二醇、（C1-C6）烷基醚和（C1-C20）烷烃二醇二（C1-C6）烷基醚。二醇醚类的例子是乙二醇单甲醚、乙二醇单乙醚、乙二醇单丁醚、乙二醇二甲醚、乙二醇二乙醚、二乙二醇单甲醚、二乙二醇单乙醚、二乙二醇单丙醚、二乙二醇单异丙醚、二乙二醇单丁醚、二乙二醇单异丁醚、二乙二醇单苄醚、二乙二醇二甲醚、二乙二醇二乙醚、三乙二醇单甲醚、三乙二醇二甲醚、聚乙二醇单甲醚、二乙二醇甲乙醚、三乙二醇甲乙醚、乙二醇单甲醚乙酸酯、乙二醇单乙醚乙酸酯、丙二醇单甲醚、丙二醇二甲醚、丙二醇单丁醚、丙二醇单丙醚、二丙二醇单甲醚、二丙二醇单丙醚、二丙二醇单异丙醚、二丙烯单丁醚、二丙二醇二异丙醚、三丙二醇单甲醚、1-甲氧基-2-丁醇、2-甲氧基-1-丁醇、2-甲氧基-2-甲基丁醇、1,1-二甲氧基乙烷和2-(2-丁氧基乙氧基)乙醇。更典型的二醇醚的例子是丙二醇单甲醚、丙二醇单丙醚、三(丙二醇)单甲醚和2-(2-丁氧基乙氧基)乙醇。一个例子是二丙二醇单甲醚，单独或与其它溶剂组合使用于本发明的组合物中。
在本文中描述的组合物A的组合物中优选存在氟化物。氟化物，也称为含氟化合物，包括通式R1R2R3R4NF的那些，其中R1、R2、R3和R4独立地是氢、醇基、烷氧基、烷基或其混合。这种化合物的例子是氟化铵（NH4F）、四甲基氟化铵、四乙基氟化铵、四丁基氟化铵和氟化胆碱。含氟化合物的其它例子包括氟硼酸和氢氟酸。所述氟化物优选以从0.0005或0.001重量%至20重量%或从0.1重量%至10重量%的量存在。氟化铵是优选的。在这些实施方式中，氟化铵可以作为40%水溶液商购。
水作为本发明组合物的组成部分存在并用于本发明的方法。它可以作为本发明其它组成部分例如氟化铵水溶液或水性酸缓冲液的组分同时存在，或者它可以被单独添加。优选地，水的存在量是0.5重量%至40重量%。在某些实施方式中，水的存在可以改善本发明组合物中氟化铵的溶解度并有助于清除污染物。
可以向本发明的组合物添加最多20重量%的量的腐蚀抑制剂。优选地，所述抑制剂浓度是约0.5重量%至8重量%。可以使用本领域已知用于类似应用的任何腐蚀抑制剂，例如在美国专利No.5,417,877中公开的那些，所述专利通过引用并入本文。在某些实施方式中已经发现，在pH范围为约3至约6的体系中，pKa大于6的抑制剂组合物起不到与pKa小于约6的抑制剂组合物同样好的作用。因此，优选的抑制剂组合物是pKa约6或更低的那些。对于pH更低的清洁液，可以优选pKa小于约4。腐蚀抑制剂可以是有机酸、有机酸盐、酚、三唑或羟胺。优选的抑制剂组合物的例子包括氨茴酸、水杨酸、没食子酸、苯甲酸、间苯二甲酸、马来酸、富马酸、D,L-苹果酸、丙二酸、邻苯二甲酸、马来酸酐、邻苯二甲酸酐、羧基苯并三唑、二乙基羟胺、和乳酸及其柠檬酸盐，等等。可以使用的腐蚀抑制剂的其它例子包括儿茶酚、叔丁基儿茶酚、连苯三酚、和没食子酸的酯，或儿茶酚、水杨酸、连苯三酚、和没食子酸的酯。
所述组合物还可以包括一种或多种以下任选的添加剂：表面活性剂，螯合剂，化学改性剂，染料，杀生物剂，和其它添加剂。所述添加剂可以添加到它们不会不利地影响所述组合物的pH范围的程度。代表性添加剂的一些例子包括炔醇及其衍生物、炔二醇（非离子型烷氧基化和/或可自乳化的炔二醇表面活性剂）及其衍生物、醇、季胺和二胺、酰胺（包括非质子溶剂例如二甲基甲酰胺和二甲基乙酰胺）、烷基烷醇胺（例如二乙醇乙胺）、和螯合剂例如β-二酮、β-酮亚胺、羧酸、苹果酸和酒石酸基酯和二酯及其衍生物、以及叔胺、二胺和三胺。在此还包括下面针对组合物B描述的表面活性剂，其量是针对表面活性剂和其它添加剂描述的量。在某些实施方式中，可以在酸缓冲液中添加到所述组合物的羧酸还可以起到螯合剂的作用。
适合用作本发明的组合物A的制剂在美国专利No.6,828,289和美国专利No.7,361,631中公开，所述公开以其全部通过引用并入本文。
组合物B
组合物B将指称在本发明的方法中可用于清洁引线框组件的那些组合物，所述组合物包含一种或多种酸，但是不包含酸缓冲液。
组合物B是无氟或含氟水性组合物。术语“无氟”是指至少基本上无氟（例如含有不超过约100ppb的氟化物）。组合物B可以包含约0.003至约25重量%的酸（优选一种或多种羧酸）和水（在水溶液中）。在一些实施方式中，所述组合物可以包含约0.003至约25重量%的酸、水、和最多20重量%的一种或多种表面活性剂和/或一种或多种腐蚀抑制剂。在一些实施方式中，所述表面活性剂包括一种或多种磺酸表面活性剂。
在一些实施方式中，组合物B可以包含0.005至约16重量%的至少一种羧酸、其盐或其混合物，它可以是含胺基的羧酸、其盐或其混合物；和/或约0.003至约4重量%的至少一种羟基羧酸、其盐或其混合物或者含胺基的羧酸、其盐或其混合物，其余基本上是水，并具有约1至约4的pH。
在其它实施方式中，组合物B可以包含0.005至约16重量%的至少一种二羧酸、其盐或其混合物，约0.003至约4重量%的至少一种羟基羧酸、其盐或其混合物；或含胺基的羧酸、其盐或其混合物，其余基本上是水，并具有约1至约4的pH。
典型的羧酸包括二羧酸，包括具有二至六个碳原子的那些，并包括草酸、丙二酸、琥珀酸、戊二酸、己二酸、马来酸和富马酸。优选的酸是柠檬酸。适合的盐包括碱金属和铵盐。组合物B中可以使用包含柠檬酸和草酸和任选的丙二酸的混合物。含胺基的二羧酸的例子包括谷氨酸和天冬氨酸。
羟基羧酸的例子包括苹果酸、酒石酸和柠檬酸。优选的羟基羧酸是柠檬酸。适合的盐包括碱金属盐和铵盐。
优选的羟基羧酸的盐是柠檬酸铵。
含胺的羧酸可以是甘氨酸、缬氨酸、丙氨酸、苯丙氨酸等等。
优选的单羧酸包括甲酸、乙酸和丙酸。
在某些实施方式中，组合物B还可以包含一种或多种溶剂，优选有机溶剂或有机极性溶剂，优选其在水中可混溶。这些溶剂可以单独或以组合使用。以前描述过可用于组合物A的所有溶剂均可用于本发明的任何组合物。用于组合物B的优选溶剂是，但是不限于，二甲基乙酰胺（DMAC）、单乙醇胺、n-甲基乙醇胺、甲酰胺、n-甲基甲酰胺、γ-丁内酯、N-甲基吡咯烷酮等、二羟基和多羟基醇例如二醇和多元醇例如（C2-C20）烷烃二醇和（C3-C20）烷烃三醇、环醇和取代醇脲，例如二甲脲、四甲脲等等。这些有机极性溶剂的具体例子是丙二醇、四氢糠醇（THFA）、二丙酮醇和1,4-环己烷二甲醇和丙二醇单甲醚。所述溶剂如果存在的话，优选存在量从0重量%至60重量%，或从0重量%至40重量%，或从10重量%至40重量%。
组合物B还可以包含上面针对组合物A描述的一种或多种氟化物（即含氟化合物）。这种化合物的例子是氟化铵、四甲基氟化铵、四乙基氟化铵、四丁基氟化铵和氟化胆碱。含氟化合物的其它例子包括氢氟酸。所述含氟化合物如果存在的话，优选存在量是从0.0005重量%至20重量%，或0.001重量%至20重量%，或从0.1重量%至10重量%，或从0.001重量%至5重量%，或从0.001重量%至2重量%。氟化铵是优选的。在一些实施方式中，氟化铵可以作为40%水溶液商购。在包含氟化物的组合物中，优选其中还存在有机溶剂，但是也存在具有氟化物并且没有有机溶剂的组合物B的实施方式，以及在其中具有有机溶剂并且不存在氟化物的其它实施方式。
除了水、优选去离子水之外，组合物B还可以包含一种或多种以下任选的添加剂：表面活性剂，杀生物剂，腐蚀抑制剂，螯合剂，化学改性剂，染料，和其它添加剂。添加剂的一个例子包括最多约0.002重量%的有效份额的杀生物剂。典型的杀生物剂是Kathan。Kathan包含：
1.2%5-氯-2-甲基-4-异噻唑啉-3-酮
0.4%2-甲基-4-异噻唑啉-3-酮
1.1%MgCl2
1.75%Mg(NO3)2
0.16%三水硝酸铜
95.85%水。这种杀生物剂可以用于本发明的任何组合物中。
所述添加剂可以添加到它们不会不利地影响想要的组合物pH范围的程度。代表性添加剂的一些例子包括表面活性剂例如炔醇及其衍生物、炔二醇（非离子型烷氧基化和/或可自乳化的炔二醇表面活性剂）及其衍生物、磺酸表面活性剂例如直链烷基苯磺酸盐（LAS）、直链脂肪酸和/或其盐、椰油脂肪酸衍生物、妥尔油酸衍生物、肌氨酸盐、乙酰化多肽、仲烷基苯磺酸盐、木质素磺酸盐、N-酰基-N-烷基牛磺酸盐、脂肪醇硫酸盐（FAS）、石油磺酸盐、仲烷基磺酸盐（SAS）、石蜡磺酸盐、脂肪醇醚硫酸盐（FAES）、α-烯烃磺酸盐、磺基琥珀酸酯、烷基萘磺酸盐、羟乙基磺酸盐、硫酸酯、硫酸化线性伯醇、硫酸化聚氧乙烯化直链醇、硫酸化甘油三酯油、磷酸酯和多磷酸酯以及全氟化阴离子型和这些的其混合物以及在此公开的任何表面活性剂与其他已知表面活性剂，醇，季胺和二胺，酰胺（包括非质子溶剂例如二甲基甲酰胺和二甲基乙酰胺），烷基烷醇胺（例如二乙醇乙胺），和螯合剂例如β-二酮、β-酮亚胺，羧酸、苹果酸和酒石酸基酯和二酯及其衍生物，以及叔胺、二胺和三胺。在某些实施方式中，可以添加到所述组合物的羧酸还可以起到螯合剂的作用。添加剂可以作为比较纯的形式或作为在水或其它溶剂中的稀释组分商购。例如，SAS-10可作为10wt%浓度的SAS水溶液得到。添加剂还可以包括腐蚀抑制剂并优选之前针对组合物A描述的腐蚀抑制剂；然而，在某些实施方式中，pKa大于约4的抑制剂组合物在pH范围为约1至约4的体系中起不到与pKa小于约4的抑制剂组合物一样好的作用。添加剂如果存在的话，其总量通常从约0.001至约10、或从约0.005至约5、或从约0.01至约1重量%。优选的添加剂是一种或多种表面活性剂和/或腐蚀抑制剂。在包含羧酸、表面活性剂和水的实施方式中，优选的表面活性剂是一种或多种磺酸表面活性剂。
一种优选的实施方式包含在本文中针对组合物B限定的重量范围内的一种或多种酸、一种或多种氟化物、一种或多种有机溶剂和一种或多种表面活性剂。其它优选实施方式是包含在本文中针对组合物B限定的重量范围内的一种或多种酸、一种或多种氟化物、一种或多种有机溶剂和一种或多种腐蚀抑制剂的组合物。其它组合物包含水和酸，并且氟化物、溶剂和添加剂各自是任选的组分。
组合物B通常包含大于35wt%的水。在没有溶剂的实施方式中，组合物B通常包含大于约50、或大于约75、或大于约90、或大于约95.5、或大于约98wt%的水。当组合物B包含一种或多种溶剂时，组合物B通常包含35至95wt%的水或40至90wt%的水或45至85wt%的水。
羧酸或二羧酸和/或盐通常的存在量为约0.005至约16重量%，更通常约0.1至约3重量%，并优选约0.3至约0.5重量%。当使用酸的混合物时，例子是草酸和丙二酸、或柠檬酸和草酸的混合物，每一种的存在量通常约0.003至约8重量%，更通常约0.05至约1.5重量%，并优选约0.1至约0.3重量%。
羟基羧酸如果存在于所述组合物中的话，通常在所述组合物中的存在量为约0.003至约8重量%，更通常约0.05至约1.5重量%，并优选约0.1重量%至约0.3重量%。
当使用时，含氨基的酸例如甘氨酸如果存在于所述组合物中的话，通常用量为约0.003至约4重量%，更通常约0.005至约1.5重量%并优选约0.005至约0.05重量%。
虽然本发明的组合物的pH可以从1至11，但优选对于组合物B来说，pH优选从约1至约4并更优选约1至约3，具体的例子是约2。所述pH通常使用pH试纸或合适的pH参比电极测量。根据本发明已经发现，pH在实现本发明的目标中是重要的。具体而言，所述组合物能够除去金属和非金属颗粒状氧化物，以及二氧化硅；金属离子污染物例如K、Ca、Ti、Cr、Mn、Fe、Ni、Cu和Zn；吸附在所述管芯或衬底上存在的各种表面材料上的各种硫和氯化物杂质。
本发明的另一个特征是所述组合物甚至在浓缩形式中也是比较稳定的。例如，可以提供所述组合物的浓缩物并运送给最终用户，所述浓缩物包含约0.1至约16重量%并优选约6至约10重量%的所述二羧酸、约0.05至约8重量%，并优选约3至约5重量%的所述二羟基羧酸或氨基酸、并且其余基本上是水，用户然后可以为了方便起见和为了经济原因在加工工具下将其以例如约19:1的重量稀释度稀释。
适合用作本发明的组合物B的制剂公开在美国专利No.6,627,546和美国专利No.7,524,801中，所述公开以其全部内容通过引用并入本文。
本发明的清洁处理产生更清洁的金属表面，因此，提供了金属导线与所述管芯和引线框触头上的接合焊盘之间的更好附着。
返回参考图2，在步骤20A或20B的任一个中将衬底或一部分引线框清洁组件暴露于（接触）所述清洁组合物，干燥所述衬底并进行导线接合步骤14。所述衬底可以利用可相对于引线框组件移动的环境空气或暖空气主动或被动干燥，例如通过商业吹风机或通过移动所述引线框组件。或者，所述衬底可以利用压缩空气或气体例如氮气干燥。干燥时间可以从数秒至几分钟不等。然而，优选所述衬底不长时间暴露于环境空气中，因为这将使所述金属焊盘氧化。
在所述清洁步骤之后和所述干燥步骤之前，可以进行用去离子水清洗的步骤。
一旦完成导线接合，就将所述衬底在步骤16处模塑。优选地，所述衬底在步骤16处真空封装。所述真空封装可以利用通常已知的可商购的真空封装设备进行。优选地，所述衬底被封装在由非反应性材料制成的防震容器中。
显而易见，本发明提供了制备具有金属焊盘的管芯的方法，使得当准备封装晶圆上的管芯时，所述金属焊盘具有较少的氧化和其它污染物，并因此使所述焊盘的导线接合产生更可靠的接合。本发明还提供了在管芯封装处理期间制备具有金属接合焊盘的管芯的方法，所述方法减少了所述金属接合焊盘上的氧化和其它污染物，使得所述焊盘的导线接合产生更可靠的接合。应当理解，本发明涉及制备用于导线接合的金属接合焊盘，例如铜和铝焊盘。本发明不限于使用铜导线进行导线接合，因为也能使用其它导线，例如金或铝。此外，虽然本发明已经采用焊球接合进行，但它不限于焊球接合，并可以用楔形接合实施。
虽然本发明已经主要就清洁半导体衬底方面进行了描述，但本发明的清洁组合物可以用于清洁包含有机和无机残留物的任何基材。
实施例
以下实施例说明了清洁液A1、A2、B1和B2将除去接合焊盘和触头上的金属氧化物。这些清洁液还将除去所述接合焊盘和触头上的污染物、氟、及其他残留物。这些清洁液将产生更清洁状态的金属表面，使得导线接合期间金属导线将有良好的附着。对应上述组合物A的清洁液A1和A2，将从Al接合焊盘除去金属氧化物。对应上述组合物B的清洁液B1和B2将从Cu接合焊盘除去金属氧化物。所评价的组合物如下：
清洁液A1：二甲基乙酰胺（57.5%）；去离子水（13.9%）；乙酸铵（15.6%）；乙酸（12.0%）；氟化铵（1.0%）。
清洁液A2：N-甲基-2-吡咯烷酮（63.9%）；去离子水（30.0%）；乙酸铵（2.6%）；乙酸（2.0%）；氟化铵（0.50%）；羧基苯并三唑（1.0%）。
清洁液B1：去离子水（98.333%）；柠檬酸（0.667%）；丙二酸（0.333%）；草酸（0.667%）。
清洁液B2：去离子水（98.27%）；柠檬酸（0.667%）；丙二酸（0.333%）；草酸（0.667%）；SAS-10（0.063%）。
在清洁液A1、A2、B1和B2中清洁引线框（具有相连的管芯）的过程如下。在管芯连接固化步骤之后和导线接合步骤之前将所述清洁液施加于引线框。所述清洁液以这些方式的任一种施加于引线框：1）将引线框浸入清洁液槽中，2）将清洁液喷洒到引线框上。所述清洁液的最适温度范围从25℃至50℃。暴露于所述清洁液的最适时间为从5分钟至30分钟。暴露于所述清洁液之后，用去离子水漂洗引线框。去离子水清洗的最适温度是25℃（室温）。去离子水漂洗的最适时间范围从30秒至3分钟。在去离子水中漂洗引线框之后，将它们干燥。一旦所述引线框已经干燥，它们可以去往导线接合步骤。
组合物A除去氧化铝的能力
下面显示的是利用X-射线光电子能谱法（XPS）收集的数据。该数据在整个晶圆的管芯上的Al接合焊盘上收集。在暴露于清洁液A之前，Al接合焊盘上的氧化铝层厚度约暴露于清洁液A1和A2之后，氧化铝的厚度降低到约这是在Al表面上天然形成的自然氧化层的典型厚度。该数据表明，清洁液A1和A2除去氧化铝，并然后长回到自然氧化铝层。暴露于清洁液A1和A2之后氧化铝厚度的净减少是大的，并将改善导线接合期间金属导线与Al接合焊盘之间的附着。
表1：氧化铝厚度的XPS数据/图案化的Al接合焊盘晶圆
处理条件：清洁液→去离子水，25℃，30秒→N2吹干
参考图3，提供了显示清洁液A1除去氧化铝的附加数据。该数据是利用俄歇（Auger）深度剖析收集的。在暴露于清洁液A1之前，Al金属中存在的氧深至约的深度。因此，这是氧化铝厚度的度量。暴露于清洁液A1之后，氧只渗透到铝中约的深度。氧化铝厚度已经显著降低。并且这是让暴露的Al接合焊盘在空气中放置3天之后。还显示了让Al接合焊盘在空气中放置14天之后的附加数据。再次，氧水平的渗透深度比暴露于清洁液A1之前低得多。
组合物A除去Al接合焊盘上的氟的能力
铝接合焊盘上可导致附着差的另一种污染物是嵌入的氟（F）。F可在例如等离子体蚀刻过程期间到达Al接合焊盘，所述蚀刻过程用于刻蚀整个钝化层并显露Al接合焊盘。所述等离子体通常基于CF4，因此来自等离子体的F可以到达Al表面。F可以与空气中的水分反应，导致Al接合焊盘的腐蚀。只要F仍然在Al上，这种腐蚀将持续发生。因此除去该F将最小化当Al接合焊盘放置在空气中而发生的腐蚀。如果发生的腐蚀较少，那么Al表面将更清洁并且金属导线将与接合焊盘具有更好的附着。图4和5显示了清洁液A1从Al接合焊盘除去F的能力。
组合物A保护底下的Al
清洁液A1和A2在除去氧化铝中非常有效，但是它们还需要对底下的Al金属具有很小的蚀刻速率。如果它们除去氧化铝并且严重蚀刻底下的Al金属，那么可能不会改善导线接合性能。下表2的数据显示了清洁液A1和A2对Al具有非常低的蚀刻速率。
表2：Al蚀刻速率
组合物B除去铜氧化物和最小化再生长速率的能力
图6和7示出的数据利用椭圆光度法收集。在暴露于清洁液之前测量Cu的无图形(blanket)晶圆上的初始铜氧化物厚度。数据显示，铜氧化物的这种初始厚度（在图中时间=-1天处显示）约厚。暴露于清洁液B1和B2之后，铜氧化物厚度降低到约该数据表明，清洁液B1和B2除去大部分铜氧化物。Cu将自然钝化并形成自然氧化层。每两天重新测量铜氧化物的厚度，直至14天。这14天期间，Cu晶圆暴露于环境空气。所述数据显示在这14天期间铜氧化物的再生长缓慢。因此清洁液B1和B2不仅除去铜氧化物，它们还最小化了铜氧化物的再生长速率。
组合物B保护底下的Cu
清洁液B1和B2在除去铜氧化物中非常有效，但是它们还需要对底下的Cu金属具有很小的蚀刻速率。如果它们除去铜氧化物并且严重蚀刻底下的Cu金属，那么可能不会改善导线接合性能。下表3的数据显示了清洁液B1和B2对Cu具有非常低的蚀刻速率。
表3：Cu蚀刻速率
清洁液A的其他实施例
利用具有搅拌棒的烧杯模拟引线框清洁过程，进行以下试验。
清洁液A1（上面公开的）如下制备：向1升HDPE聚合瓶添加575克二甲基乙酰胺（DMAc）、139克去离子水（DIW）、156克乙酸铵、120克乙酸、和10克氟化铵。盖住所述述瓶并振摇。将清洁液A1的样品用DIW稀释，以制成5%溶液并测得所述溶液pH为4.9。
在该试验中测试的Al或Al2O3晶圆是无图形晶圆。晶圆在所述烧杯中浸泡设定为持续90分钟。
氮化钛（TiN）担载Al（0.5%Cu）金属衬底，电阻率为得自SVMI并具有标称的Al厚度。储存期间，所述Al衬底可以生长到的氧化层。因此在蚀刻速率测定之前，所述Al衬底通过在25℃下将2“x2”的铝片浸入42.5wt%的H3PO4在去离子水中的水溶液中2分钟进行预处理。浸泡2分钟之后，用去离子水漂洗所述Al片3分钟，用N2枪干燥30秒，然后测量Al膜厚度。以这种方式预处理的Al片立即用于进行蚀刻速率测量中。
Al或Al2O3清除试验如下进行。每个2"x2"的Al或Al2O3衬底片浸泡在500ml玻璃烧杯中的330ml清洁溶液A1中，并将所述溶液在搅拌板上以300rpm搅拌。记录温度是25℃。在时间为0、20、40、60和90分钟之后一式三份进行厚度测量，单位为。
Al厚度测量利用ResMap四点探测器完成。然后将膜厚度对时间数据进行回归。确定了清洁液A1对Al的蚀刻速率是
利用FilmTek SCI椭圆偏振仪进行椭圆光度法试验，测量Al2O3氧化物厚度。然后将膜厚度对时间数据进行回归。确定了清洁液A1对Al2O3的蚀刻速率是
其他清洁液A94B、A94E、A97E、A97F和A97G的制备如同A1，但是组分的浓度不同。在这些溶液中，去离子水构成组合物的余量，以达到100wt%。这些溶液组成，它们的pH测量值和它们的蚀刻速率结果归纳在表I中。对Al和Al2O3的这些蚀刻速率表明，改变Al和Al2O3的相对蚀刻速率可通过改变组分浓度来达到。A1溶液显示Al2O3蚀刻速率高于Al蚀刻速率。
表I.
清洁液A96G的制备如同清洁液A1，但是用丙二醇（PG）代替DMAC。表II中归纳了组成、它的pH测量值和蚀刻速率结果，并与清洁液A1相比较。
表II.
清洁液A94A、A94D、A96A和A96B的制备如同A1，但用PG代替DMAC。在这些溶液中，去离子水构成组合物的余量，以达到100wt%。表III中归纳了组成、它的pH测量值和蚀刻速率结果。所述实施例显示，Al和AI2O3的相对蚀刻速率可通过改变组分和缓冲液浓度进行改变，以达到想要的清洁性能。
表III.
清洁液A96E和A96F的制备如同A1，但是用PG替代DMAC。在这些溶液中，去离子水构成组合物的余量，以达到100wt%。表IV中归纳了组成、它的pH测量值和蚀刻速率结果，并与A96A和A97E相比较。因为有时可能优选溶剂浓度较低的水基制剂，所以使用较低的溶剂量。对具体应用的最佳清洁将由溶剂对水的相对量、氟化物的量和溶液pH提供。溶剂类型还将允许精细调节清洁结果。
表IV.
清洁液A96C、A96D、A97B和A97D的制备如同A1，但是用二甲脲（DMU）溶剂并显示向PG添加二丙二醇单甲醚（DPM）共溶剂的效果。在这些溶液中，去离子水构成组合物的余量，以达到100wt%。表V中归纳了组成、它的pH测量值和蚀刻速率结果，并与A96A和A97B相比较。
表V.
清洁液B的其他实施例
清洁液B91A、B92A、B92D、B92E和B92F的制备和测试如同A1，但是利用表VI中显示的组分基质。在这些溶液中，去离子水构成组合物的余量，以达到100wt%。利用0.45wt%柠檬酸和0.0017wt%NH4F加上水基质，测定0、10、30、和40wt%PG制剂的蚀刻速率。
表VI.
清洁液B92F、B92H、B92I和B92J的制备和测试如同A1，但是利用表VII中显示的组分基质。在这些溶液中，去离子水构成组合物的余量，以达到100wt%。
表VII.
其他试验在B100A、B100B、B100C、B100D和B101A的B1清洁液中使用其它腐蚀抑制剂分子进行。柠檬酸是0.45wt%绝对量。
*AKYPO LF表面活性剂是二醇醚羧酸表面活性剂
**HEDTA是羟基乙二胺三乙酸
前述实施例和优选实施方式的描述应该视为举例说明，而不是限制由权利要求书限定的本发明。容易理解，可以利用上面阐述的组合物中特征和组分的各种变化和组合，但不背离如权利要求书中阐明的本发明。这样的变化不认为背离了本发明的精神和范围，并且所有这样的变化意图包含在以下权利要求书的范围内。本文中描述的所有组分可以用所公开的任何范围进行组合。在任何一个那些组合物中，组合物A和B的组分在对于其任何一个所描述的范围内可以互换。所有包含性语言包括基本由...组成和由...组成。

Claims (24)

1.处理引线框组件以从其除去不想要的物质或为后续接合准备所述引线框组件的表面的方法，其中引线框组件包含以下部件中的一种或多种：引线框、管芯、其上具有接合焊盘的管芯、触头、触头引线、和导线，所述方法包括以下步骤：
将其上具有接合焊盘的一个或多个管芯与引线框相连以形成引线框组件，所述引线框包括具有暴露的金属表面的触头引线；
将所述接合焊盘和所述触头引线与包含水、和至少一种羧酸或多元酸或至少一种羧酸或多元酸的盐、或至少一种羧酸或多元酸和至少一种羧酸或多元酸的盐的混合物的组合物相接触，以清洁所述接合焊盘和所述触头引线；
干燥所述引线框组件；以及
进行导线接合步骤，所述导线接合步骤包括在所述一个或多个管芯上的接合焊盘与所述引线框上的触头引线之间连接导线。
2.权利要求1的方法，其中所述接触步骤从所述接合焊盘和所述触头引线除去金属氧化物。
3.权利要求1或2的方法，其还包括在进行所述导线接合步骤之后，在引线框组件上形成塑模以形成封装电路的步骤。
4.权利要求1或2的方法，其中用于所述接触步骤的所述组合物具有从约1至约7的pH。
5.权利要求1或2的方法，其中用于所述接触步骤的所述组合物包含0.003至约25重量％的一种或多种羧酸。
6.权利要求1或2的方法，其中用于所述接触步骤的所述组合物包含酸缓冲液，所述酸缓冲液包含所述羧酸或所述多元酸以及所述羧酸或所述多元酸的盐，其中所述羧酸或所述多元酸与所述盐的摩尔比为从10:1至1:10。
7.权利要求6的方法，其中用于所述接触步骤的所述组合物中的所述酸缓冲液包含如下至少一种：乙酸/乙酸盐，苯甲酸/苯甲酸盐，和酚酸/酚盐。
8.权利要求1或2的方法，其中用于所述接触步骤的所述组合物包含约0.003至约4重量％的至少一种羟基羧酸、其盐或其混合物或者含胺基的羧酸、其盐或其混合物。
9.权利要求1或2的方法，其中用于所述接触步骤的所述组合物包含选自柠檬酸、草酸、丙二酸、琥珀酸、戊二酸、己二酸、马来酸和富马酸及其盐或其混合物的一种或多种羧酸、其盐或其混合物。
10.权利要求1或2的方法，其中用于所述接触步骤的所述组合物包含柠檬酸。
11.权利要求1或2的方法，其中用于所述接触步骤的所述组合物包含：
约0.005至约16重量％的至少一种羧酸、其盐或其混合物；
约0.003至约4重量％的至少一种羟基羧酸、其盐或其混合物或者含胺基的酸、其盐或其混合物；以及其余是水。
12.权利要求1或2的方法，其中用于所述接触步骤的所述组合物包含选自柠檬酸、草酸、丙二酸、琥珀酸、戊二酸、己二酸、马来酸和富马酸、及其盐或其混合物的两种或更多种羧酸、其盐或其混合物，并且还包含一种或多种溶剂、一种或多种氟化物、和任选的一种或多种表面活性剂。
13.权利要求1或2的方法，其中用于所述接触步骤的所述组合物包含氟化物，所述氟化物选自通式R1R2R3R4NF的化合物，其中R1、R2、R3和R4独立地是氢、醇基、烷氧基、烷基或其混合。
14.权利要求1或2的方法，其中用于所述接触步骤的所述组合物还包含选自有机极性溶剂、氟化物、表面活性剂和腐蚀抑制剂的一种或多种组分。
15.权利要求1或2的方法，其中用于所述接触步骤的所述组合物还包含有机极性溶剂和氟化物。
16.权利要求1或2的方法，其中用于所述接触步骤的所述组合物还包含选自如下的溶剂：二甲基乙酰胺(DMAC)、单乙醇胺、n-甲基乙醇胺、甲酰胺、n-甲基甲酰胺、γ-丁内酯、N-甲基吡咯烷酮、二羟醇、多羟醇、二醇和多元醇、环醇和取代醇和二醇类、二醇醚、四氢糠醇(THFA)、二丙酮醇、1,4-环己烷二甲醇、和脲类、及其混合物。
17.权利要求1或2的方法，其中用于所述接触步骤的所述组合物还包含选自如下的溶剂：二甲基乙酰胺(DMAC)、单乙醇胺、n-甲基乙醇胺、甲酰胺、n-甲基甲酰胺、γ-丁内酯、N-甲基吡咯烷酮、二羟醇、多羟醇、(C2-C20)烷烃二醇和(C3-C20)烷烃三醇、环醇和取代醇和二醇类、二醇醚、四氢糠醇(THFA)、二丙酮醇、1,4-环己烷二甲醇、和脲类、及其混合物。
18.权利要求1或2的方法，其中用于所述接触步骤的所述组合物还包含30重量％至90重量％的有机极性溶剂；0.0005重量％至20重量％的氟化物；0.5重量％至40重量％的水；最多15重量％的任选的腐蚀抑制剂。
19.权利要求1或2的方法，其中用于所述接触步骤的所述组合物具有从3至7的pH；并且所述组合物还包含30重量％至90重量％的有机极性溶剂；0.001重量％至20重量％的氟化物；和最多15重量％的任选的表面活性剂，并且另外其中所述水以0.5重量％至40重量％存在。
20.权利要求1或2的方法，其中用于所述接触步骤的所述组合物包含铵盐。
21.权利要求1或2的方法，其中用于所述接触步骤的所述组合物包含丙二醇或二甲基乙酰胺或其混合物。
22.权利要求1或2的方法，其中用于所述接触步骤的所述组合物还包含一种或多种表面活性剂。
23.权利要求1或2的方法，其中用于所述接触步骤的所述组合物包含：
约0.1至约3重量％的至少一种二羧酸、其盐或其混合物；
约0.05至约1.5重量％的至少一种羟基羧酸、其盐或其混合物；
并且其余是水，并且所述组合物具有约1至约4的pH。
24.用于清洁引线框组件或引线框组件的部件的组合物，所述组合物用于前述方法权利要求任一项中的接触步骤。
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