CN103429789B - 蚀刻用锡或锡合金填充的凹形结构的方法 - Google Patents

蚀刻用锡或锡合金填充的凹形结构的方法 Download PDF

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CN103429789B
CN103429789B CN201280014050.4A CN201280014050A CN103429789B CN 103429789 B CN103429789 B CN 103429789B CN 201280014050 A CN201280014050 A CN 201280014050A CN 103429789 B CN103429789 B CN 103429789B
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tin
concave structure
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N.伍德
D.特夫斯
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Atotech Deutschland GmbH and Co KG
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Abstract

本发明公开避免形成微坑的用锡或锡合金填充的凹形结构的平面化方法。这些结构可作为焊接沉积物用于电子器件中的稳定可靠焊接接头。

Description

蚀刻用锡或锡合金填充的凹形结构的方法
发明领域
本发明涉及制造印刷电路板、IC基片等，更具体涉及锡和锡合金的蚀刻。
发明背景
长期以来，在电子器件的制造中，例如印刷电路板(PCB)和IC基片，一直用锡和锡合金作为可焊接表面或焊料。
更近的研究是锡和锡合金作为焊料通过电镀到电子器件的凹陷结构沉积。锡或锡合金沉积物可通过图形电镀或全板电镀来电镀。
制造焊接沉积物所用的全板电镀方法公开于EP2180770A1。
具有由例如铜制成的焊盘的基片表面用阻焊料涂覆，并且使空隙形成进入阻焊料，以使焊盘暴露。在本文中，将这些空隙称为凹形结构。通过电子器件的介电基片到电阻材料或通过多于一个这些层形成其它类型凹形结构。
下一步，使导电晶种层沉积于基片的整个表面和凹形结构的表面上。然后，为了填充凹形结构，通过电镀到导电晶种层上沉积锡或锡合金。
然而，在用锡或锡合金完全填充凹形结构时，也同时在不覆盖凹形结构的导电晶种层表面上沉积一定量锡或锡合金。完全填充凹形结构总是需要过量锡或锡合金层。
下一步，去除用锡或锡合金填充的凹形结构顶上的所述过量锡或锡合金。
完成这一工作可通过在与凹形结构对准的锡或锡合金的表面上沉积抗蚀剂，随后蚀刻掉未由抗蚀剂覆盖的过量锡或锡合金层。这一方法公开于US2006/0219567A1。此方法的缺点有多个：a)用锡或锡合金填充的所得凹形结构具有超过周围阻焊料的高度。这导致在连续工艺步骤中另外的焊料的(丝网)印刷沉积的焊料不对准，并且b)此方法需要多几个工艺步骤。
EP2180770A1中公开的焊接沉积物制造所用的全板电镀方法需要可在不需要抗蚀剂的程度控制的用于锡或锡合金的蚀刻溶液。蚀刻侵蚀必须很均匀，以在去除过量锡或锡合金层时产生用锡或锡合金填充的凹形结构的光滑平表面。
在本领域已知的锡和锡合金所用的蚀刻水溶液(Jordan：TheElectrodepositionofTinanditsAlloys，1995，p.373-377)不能用，电镀进入凹形结构的锡或锡合金以比阻焊料顶上过量锡或锡合金层更高的速度去除。结果是用锡或锡合金填充的凹形结构中的微坑(图1)。这些微坑必须避免，因为它们在以后工艺步骤中产生不稳定不可靠的焊接接头。
发明目的
因此，本发明的目的是提供避免形成微坑的用锡或锡合金填充的凹形结构的平面化方法。
本发明的第二目的是提供用于制造稳定可靠焊接接头的用平面化锡或锡合金焊接沉积物填充的凹形结构。
发明概述
这些目的通过蚀刻过量锡和锡合金沉积物的方法达到，所述方法包括以下步骤：
a.提供具有用锡或锡合金填充的凹形结构和过量锡或锡合金层的基片，
b.提供蚀刻水溶液，所述水溶液由氢氧根离子源和硝基取代的芳族磺酸组成，并且具有大于7的pH值，
c.使所述基片与所述蚀刻水溶液接触，用于去除用锡或锡合金填充的所述凹形结构顶上的所述过量锡或锡合金层。
附图简述
图1显示从现有技术已知的蚀刻方法得到的用锡填充的凹形结构的蚀刻。
图2显示本发明的用锡填充的凹形结构的蚀刻。
发明详述
基片(101)包含由例如铜制成的焊盘(102)和阻焊料(103)，并具有使焊盘(102)暴露的空隙。包含铜的导电晶种层(104)覆盖阻焊料(103)和焊盘(102)的表面。空隙用锡或锡合金填充，并且类似于用锡或锡合金填充的凹形结构(105a)和高于经填充的凹形结构(105a)并且在阻焊料(103)顶上的过量锡或锡合金层(106)。
使过量锡或锡合金层(106)与蚀刻水溶液接触，所述水溶液由氢氧根离子源和硝基取代的芳族磺酸组成，并且具有大于7的pH值。pH值为7至14，更优选11至14。
氢氧根离子源选自LiOH、NaOH、KOH、NH4OH和有机氢氧化物源，例如，乙醇胺、二乙醇胺和三乙醇胺及其混合物。最优选的氢氧根离子源为NaOH。氢氧根离子的浓度为0.5至100g/l，更优选10至40g/l，最优选20至30g/l。
硝基取代的芳族磺酸优选选自邻硝基苯磺酸、间硝基苯磺酸、对硝基苯磺酸及其具有钠和钾的相应盐及其混合物。硝基取代的芳族磺酸、其盐及其混合物的浓度为1至100g/l，更优选20至80g/l，最优选40至60g/l。
蚀刻水溶液可进一步包含湿润剂。优选湿润剂选自烷基化或芳基化氧化乙烯-氧化丙烯共聚物、烷基硫酸盐、烷基磺酸盐、芳基烷基磺酸盐和低起泡非离子或阴离子表面活性剂。
在步骤c期间，含水蚀刻剂的温度保持在20至90℃，更优选30至70℃。
在步骤c中，基片与蚀刻水溶液接触10至240秒，更优选60至120秒。
通过基片浸入蚀刻水溶液，用水溶液水平淹没处理基片，或者在基片上喷涂蚀刻水溶液，可使基片与蚀刻水溶液接触。用于使基片与蚀刻水溶液接触的最优选的方法是用喷或淹没应用水平处理。
在经过电镀时，具有凹形结构的基片显示宽范围电流密度，尤其在锡或锡合金电镀进入凹形结构和电镀到此基片的顶上时。在电镀期间宽电流密度范围的结果是初沉积锡或锡合金的不均匀晶粒结构。凹形结构内和此凹形结构顶上的晶粒粒径显著大于阻焊料顶上的晶粒粒径。在本领域已知的蚀刻水溶液侵蚀锡或锡合金的较大粒径晶粒比小粒径晶粒更快。利用在本领域已知的锡和锡合金所用蚀刻溶液的蚀刻方法的结果显示于图1中。由于在较大粒径晶粒上较快蚀刻侵蚀，在用具有较大晶粒粒径的锡或锡合金填充的凹形结构中形成微坑。用锡或锡合金填充的凹形结构中的这些微坑不是可接受的，并且在连续工艺步骤中产生不稳定不可靠的焊接接头。
本发明的方法导致不依赖晶粒粒径对锡和锡合金沉积物的均匀蚀刻侵蚀。本发明的方法的结果显示于图2中。由于均匀蚀刻侵蚀，在用锡或锡合金填充的凹形结构中没有不希望有的微坑。
实施例
现在将参考以下非限制实施例说明本发明。
在全部这些实施例中使用的基片包括具有100μm直径和30μm深度的圆柱形凹形结构。凹形结构壁由铜焊盘102(底部)和阻焊料103(侧壁)组成。
由铜制成的导电晶种层104沉积进入凹形结构并沉积到阻焊料103的顶上。下一步，用锡105a通过电镀填充凹形结构。为了完全填充凹形结构，需要电镀过量锡或锡合金层106(全板电镀)。
过量锡层106通过不同的蚀刻水溶液去除，如下所述。
用光学显微镜研究用不同蚀刻溶液处理的基片的横截面。用微坑作为蚀刻过量锡或锡合金层(106)的量度。通过测量凹形结构顶部和凹形结构中锡或锡合金沉积物顶部之间的距离对微坑定量。距离在凹形结构的中心测量。微坑是必须避免的缺陷。
实施例1(比较性)
使用由50g/l硝酸和50g/l硝酸铁组成的酸性蚀刻水溶液。将基片在蚀刻水溶液中在30℃温度浸入60秒。完全去除过量锡层106。
用锡105b填充的凹形结构具有20μm微坑。因此，不能得到稳定可靠的焊接接头。
实施例2(比较性)
使用由50g/l甲磺酸和50g/l间硝基苯磺酸钠盐组成的酸性蚀刻水溶液。将基片在蚀刻水溶液中在30℃温度浸入60秒。完全去除过量锡层106。
用锡105b填充的凹形结构具有20μm微坑。因此，不能得到稳定可靠的焊接接头。
实施例3(发明)
使用由50g/l氢氧化钠和50g/l间硝基苯磺酸钠盐组成的碱性蚀刻水溶液。将基片在蚀刻水溶液中在50℃温度浸入60秒。完全去除过量锡层106。
用锡105b填充的凹形结构显示没有微坑。因此，可得到稳定可靠的焊接接头。

Claims (9)

1.一种蚀刻过量锡或锡合金沉积物的方法，所述方法包括以下步骤：
a.提供具有用锡或锡合金(105a)填充的凹形结构和过量锡或锡合金层(106)的基片(101)，
b.提供蚀刻水溶液，所述水溶液由氢氧根离子源和硝基取代的芳族磺酸组成，并且具有大于7的pH值，其中氢氧根离子的浓度为20至30g/l，
c.使所述基片与所述蚀刻水溶液接触，用于去除用锡或锡合金(105a)填充的所述凹形结构顶上的所述过量锡或锡合金层。
2.权利要求1的方法，其中氢氧根离子源选自LiOH、NaOH、KOH和NH4OH。
3.权利要求1或2的方法，其中硝基取代的芳族磺酸选自邻硝基苯磺酸、间硝基苯磺酸、对硝基苯磺酸及其混合物。
4.权利要求1或2的方法，其中硝基取代的芳族磺酸的浓度为30至60g/l。
5.权利要求1或2的方法，其中pH值为11至14。
6.权利要求1或2的方法，其中蚀刻水溶液进一步包含湿润剂。
7.权利要求1或2的方法，其中在步骤c期间含水蚀刻剂的温度保持在30至70℃。
8.权利要求1或2的方法，其中在步骤c使基片与蚀刻水溶液接触60至120秒。
9.权利要求1或2的方法，其中基片通过用喷或淹没施加水平处理与蚀刻水溶液接触。
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