CN106906474A - 铜蚀刻液组合物 - Google Patents

铜蚀刻液组合物 Download PDF

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CN106906474A
CN106906474A CN201611197242.XA CN201611197242A CN106906474A CN 106906474 A CN106906474 A CN 106906474A CN 201611197242 A CN201611197242 A CN 201611197242A CN 106906474 A CN106906474 A CN 106906474A
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acid
liquid composition
copper
etching liquid
percentage
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CN106906474B (zh
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金涩琪
金世训
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Yi Xiang Fu Technology Co Ltd
ENF Technology CO Ltd
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Abstract

本发明涉及铜蚀刻液组合物，尤其涉及进行铜蚀刻时具有处理量增加及蚀刻均匀性的铜蚀刻液组合物，上述铜蚀刻液组合物包含：第一有机酸，含有一种以上胺基及一种以上羧酸基；第二有机酸；胺化合物；过氧化氢；以及磷酸盐化合物。

Description

铜蚀刻液组合物
技术领域
本发明涉及用于铜或铜合金的蚀刻的铜蚀刻液组合物。
背景技术
为了在制备半导体封装基板时实现基板的微细配线化、高密度化、高可靠性，目前在导体的形成方面常用着使用镀金的半加成法(semi additive process)。
然而，在现有的半加成法的铜蚀刻液组合物的情况下，随着进行蚀刻工序，蚀刻液组合物内的金属含量变高或者工序处理时间增加，导致蚀刻速度和蚀刻均匀性减少等蚀刻特性变化，因此发生如铜籽晶层(seed layer)的不均匀的蚀刻及残渣的诱发等不良现象。
因此，持续需要开发蚀刻均匀性优秀且蚀刻特性不随着处理量及蚀刻时间的变化的铜蚀刻液组合物。
就半加成法而言，为了去除作为籽晶层的铜镀金膜而所使用的铜蚀刻液，硫酸/过氧化氢类(日本授权专利第4430990号)、盐酸/二价铜类(日本公开专利第2006-111953号)、盐酸/一价铁类(日本授权专利第3962239号)公开了铜蚀刻液。
现有技术文献
专利文献
日本授权专利第4430990号(2009年12月25日)
日本公开专利第2006-111953号(2006年04月27日)
日本授权专利第3962239号(2007年05月25日)
发明内容
本发明提供具有优秀的铜蚀刻性能并在进行铜蚀刻时处理量增加且具有蚀刻均匀性的铜蚀刻液组合物。
本发明涉及铜蚀刻液组合物，其包含第一有机酸，含有一种以上胺基及一种以上羧酸基；第二有机酸；胺化合物；过氧化氢；以及磷酸盐化合物。
本发明的铜蚀刻液组合物可在利用半加成法时均匀地去除作为籽晶层的铜镀金，即使处理量和处理时间增加也不会导致蚀刻速度、蚀刻均匀性等蚀刻特性的变化，从而具有优秀的蚀刻性能。
附图说明
图1示出利用本发明的铜蚀刻液组合物来蚀刻铜之前的半导体器件。
图2示出利用本发明的铜蚀刻液组合物来蚀刻铜之后的半导体器件。
附图标记的说明：
100：硅晶片
200：钛(Ti)籽晶层
300：铜(Cu)籽晶层
400：铜(Cu)金属层
500：镍(Ni)金属层
600：锡球(SD)。
具体实施方式
以下，参照附图对本发明的铜蚀刻液组合物进行详细说明。以下介绍的附图是为了使本领域普通技术人员能够充分地理解本发明的思想而提供的例。因此，本发明不局限于以下所提出的附图，而是能够以其他形态具体化，并且，以下所提出的附图可能会用于明确说明本发明的思想而有所夸张。并且，在整篇说明书中，相同的附图标记表示相同的结构要素。
其中，若没有其他定义，则所使用的技术术语及科学术语具有本发明所属领域的普通技术人员通常理解的意思，并且在以下的说明及附图中将省略对可能不必要地混淆本发明的主旨的公知功能及结构的说明。
本发明涉及用于去除在半导体硅贯通电极(TSV，Through Silicon Via)制备工序中所使用的铜籽晶层(Cu seed layer)的铜蚀刻液组合物，本发明所述的铜蚀刻液可以仅蚀刻铜和/或铜合金。
在现有的半加成法的铜蚀刻液组合物的情况下，随着进行蚀刻工序，蚀刻液组合物内的金属含量变高或者工序处理时间增加，导致蚀刻速度和蚀刻均匀性减少等蚀刻特性变化，因此发生如铜籽晶层(seed layer)的不均匀的蚀刻及残渣的诱发等不良现象。
本发明用于改善这种问题，发明的铜蚀刻液组合物可在利用半加成法时均匀地去除作为籽晶层的铜镀金膜，即使处理量和处理时间增加也不会导致蚀刻速度、蚀刻均匀性等蚀刻特性的变化，从而具有优秀的蚀刻性能。并且，由于具有对铜的高的蚀刻性能，因此不会蚀刻除了铜以外的金属，作为一例，钛(Ti)、镍(Ni)、锡(Sn)、银(Ag)、金(Au)、铝(Al)、锡-银合金等金属和氮化硅、氧化硅等，因此在制备器件时能够确保高可靠性。
在铜溶解于蚀刻液组合物而以铜离子存在的情况下，铜离子在配位(coordination)数为4至6个时以最稳定的形态的配位化合物存在于蚀刻液组合物内。因此，与铜离子进行配位结合时，本发明人同时使用作为螯合剂的第一有机酸和胺化合物，上述螯合剂能够形成三位以上的配位，胺化合物与铜离子的一位以上形成配位，从而能够形成总共4位以上的配位，优选地形成4至6位的配位，由此使铜离子能够更加稳定地存在于蚀刻液组合物内。因此，本发明的铜蚀刻液组合物即使将处理量增加到200个或者将蚀刻时间增加到72小时也可维持蚀刻液组合物的蚀刻特性。
详细地，本发明一例的铜蚀刻液组合物可包含：第一有机酸，含有一种以上胺基及一种以上羧酸基；第二有机酸；胺化合物；过氧化氢；以及磷酸盐化合物。由于具有如上所述的组份的组合，本发明的铜蚀刻液组合物不仅具有优秀的铜和/或铜合金的蚀刻性能，而且即使处理量和处理时间增加也具有优秀的蚀刻均匀性。相反，不包含第一有机酸或胺化合物的情况下，铜离子难以在蚀刻液组合物内稳定地存在，因此蚀刻量的增加可能导致蚀刻性能的减少，并且不包含第二有机酸的情况下，铜的蚀刻速度可能非常慢，因此优选使用上述组合的铜蚀刻液组合物来进行铜的蚀刻。
为此的铜蚀刻液组合物中，相对于上述铜蚀刻液组合物的总重量，包含0.01重量百分比至5重量百分比的第一有机酸、0.01重量百分比至5重量百分比的第二有机酸、0.01重量百分比至10重量百分比的胺化合物、0.5重量百分比至10重量百分比的过氧化氢以及0.01重量百分比至10重量百分比的磷酸盐化合物，未记载的其余组成成分可以为超纯水或去离子水等水。在上述范围内能够以优秀的效率进行铜的蚀刻。更优选地，铜蚀刻液组合物中，相对于上述铜蚀刻液组合物的总重量，可以包含0.5重量百分比至3重量百分比的第一有机酸、0.5重量百分比至3重量百分比的第二有机酸、0.01重量百分比至1重量百分比的胺化合物、3重量百分比至10重量百分比的过氧化氢以及0.05重量百分比至3重量百分比的磷酸盐化合物，未记载的其余组成成分可以为超纯水或去离子水等水。同时使用0.5重量百分比至3重量百分比的第一有机酸和0.01重量百分比至1重量百分比的胺化合物，来进一步与铜离子的一位以上形成配位，从而如上所述地，能够形成总共4位以上，优选地形成4至6位的配位的胺化合物。由此，能够使铜离子更加稳定地存在于蚀刻液组合物内，即使将处理量增加到200个或者将蚀刻时间增加到72小时也可维持蚀刻液组合物的蚀刻特性。并且，使用0.5重量百分比至3重量百分比的第二有机酸来提高铜的蚀刻速度，并且可对铜膜的中心部和外围部均执行均匀的蚀刻。
本发明一例的第一有机酸含有一种以上胺基及一种以上羧酸基，具体地，可含有1个至4个胺基及1个至6个羧酸基。更详细的，第一有机酸可使用能够与铜离子的形成三位以上的配位的螯合剂。如上所述，铜离子在配位数为4个至6个时以最稳定的形态存在于配位化合物来蚀刻液组合物内，因此随着第一有机酸与铜离子进行配位结合来形成配位化合物，即使处理量或处理时间增加，也可通过第一有机酸抑制蚀刻液组合物内自由铜离子(free copper ion)的浓度增加来维持蚀刻液组合物的蚀刻特性。
作为一具体例，第一有机酸可以为选自亚氨基二乙酸(iminodiacetic acid)、亚氨基二琥珀酸(iminodisuccinic acid)、乙二胺四乙酸(EDTA，ethylenediaminetetraacetic acid)、二乙烯三胺五乙酸(DTPA，diethylenetriaminepentaacetic acid)、次氮基三乙酸(NTA，nitrilotriacetic acid)、2-羟乙基乙二胺三乙酸(HEDTA，(2-hydroxyethyl)-ethylenediaminetriacetic acid)、乙二醇双(2-氨基乙醚)四乙酸(EGTA，ethylenebis(oxyethylenenitrilo)tetraaceticacid)及它们的盐等的一种或两种以上，但并不局限于此。
本发明一例的第二有机酸不含有胺基并含有一种以上羧酸基，具体地可以含有1至6个羧酸基。第二有机酸能够提高铜的溶解性来提高蚀刻速度。详细地，如后述内容，第二有机酸与被过氧化氢氧化的氧化铜结合来使其溶解，从而能够更加易于进行铜的蚀刻。
尤其，为了铜的蚀刻，第二有机酸优选使用满足以下关系式1的酸，在不满足关系式1的情况下，第二有机酸不与氧化铜想结合而溶解于蚀刻液内，从而无法期待铜的蚀刻速度增加效果。并且，可能蚀刻除了铜以外的金属，作为一例，与铜一同蚀刻钛(Ti)、镍(Ni)、锡(Sn)、银(Ag)、金(Au)、铝(Al)、锡-银合金等金属和氮化硅、氧化硅等而不好。
关系式1
B-2≤A≤B+2
上述关系式1中，A为第二有机酸的pKa，B为蚀刻液组合物的pH。此时，B的pH为4至6.5。
像这样满足关系式1的第二有机酸具体例为选自蚁酸(formic acid)、乙酸(acetic acid)、丁酸(butanoic acid)、戊酸(pentanoic acid)、丙二酸、乙醇酸(glycollic acid)、琥珀酸、柠檬酸、戊二酸、酒石酸、丙酸(propionic acid)、葡萄糖酸(gluconic acid)及它们的盐等的一种或两种以上，但并不局限于此。
如上所述，本发明一例的胺化合物，基于作为螯合剂的第一有机酸来形成三位以上的配位，并与追加的铜离子形成一位以上的配位，从而能够形成总共4位以上的配位，优选地形成4至6位的配位，由此能够使铜离子以作为最稳定的形态的配位化合物存在于蚀刻液组合物内。
并且，胺化合物通过减少表面张力来在流量及物理力差异引起的母晶片(wafer)上使蚀刻速度均匀，从而提高蚀刻均匀性。在表面张力高的情况下，流量少或物理力小的部位蚀刻速度下降，流量多活物理力大的部位蚀刻速度快，因此根据器件的部位发生蚀刻速度的差异。这种部分的蚀刻速度差异导致凸点(bump)的直径不均匀。
作为一具体例，胺化合物可以为选自C4至C9的直链型烷基胺、C4至C20的支链型烷基胺、C4至C20的环烷基胺急C6至C20的芳胺的一种或两种以上。在直链型烷基胺的碳数为3个以下的情况下，蒸汽压力及沸点低而容易挥发，在碳数为10个以上的情况下，蚀刻液组合物中有泡沫而不好。优选地，胺化合物可以为选自丁胺(n-butylamie)、戊胺(n-pentylamie)、己胺(n-hexylamie)、庚胺(n-heptylamie)、辛胺(n-octylamie)、2-乙基丁胺(2-ethyl-1-butanamine)、2-己胺(2-hexylamine)及2-乙基己胺(2-ethyl-1-hexylamine)、环己胺的一种或两种以上，尤其优选地，使用戊胺、己胺、庚胺、辛胺或2-乙基己胺有助于提高蚀刻均匀性。
本发明一例的过氧化氢(H2O2)起到使铜氧化的作用，铜被氧化而成氧化铜，从而基于蚀刻液组合物而进行蚀刻。
本发明一例的磷酸盐化合物为过氧化氢稳定剂，抑制因蚀刻工序的反复而在蚀刻液内铜离子的含量变高而导致的过氧化氢的分解反应，并且与第二有机酸一起与被氧化的铜相结合来使其溶解，从而执行对氧化铜进行蚀刻的作用，由此能够提高铜的蚀刻速度。作为一具体例，磷酸盐化合物为选自H3PO4、NaH2PO4、Na2HPO4、Na3PO4、NH4H2PO4、(NH4)2HPO4、(NH4)3PO4、KH2PO4、K2HPO4、K3PO4、Ca(H2PO4)2、Ca2HPO4及Ca3PO4的一种或两种以上，但并不局限于此。
以下，通过实施例对本发明的铜蚀刻液组合物进行更详细的说明。但是以下实施例仅仅是用于详细说明本发明的一种参照，本发明并不局限于此，能够以多种形态体现。并且，若没有其他定义，则所有技术术语及科学术语具有与本发明所属领域的普通技术人员通常理解的意思相同的意思。并且在本说明书中所使用的术语仅仅用于有效记述特定实施例，并不用于限制本发明。并且，在没有特殊指示的情况下，说明书及所附的发明要求保护范围中所使用的单数的形态包括复数的形态。并且，说明书中未特意记载的添加物的单位可以是重量百分比。
实施例1至实施例29以及比较例1至比较例8
以表1中记载的成分及含量(重量百分比)准备铜蚀刻液组合物。
表1
KP2：磷酸氢二钾(dipotassium phosphate)
IDA：亚氨基二乙酸(iminodiacetic acid)
EDTA：乙二胺四乙酸(ethylenediaminetetraacetic acid)
MA：丙二酸(malonic acid)
GA：乙醇酸(glycolic acid)
SA：琥珀酸(succinic acid)
CA：柠檬酸(citric acid)
GTA：戊二酸(glutaric acid)
TA：酒石酸(tartaric acid)
b-AM：丁胺(n-butylamine)
p-AM：戊胺(n-pentylamine)
hx-AM：己胺(n-hexylamine)
hp-AM：庚胺(n-heptylamine)
o-AM：辛胺(n-octylamine)
2-et-1-b-AM：2-乙基丁胺(2-ethyl-1-butanamine)
2-hxa-AM：2-己胺(2-hexanamine)
2-et-1-hx-AM：2-乙基己胺(2-ethyl-1-hexylamine)
cyhx-AM：环己胺(cyclohexylamine)
蚀刻均匀性评价
为了评价本发明的铜蚀刻液组合物的蚀刻均匀性效果，在直径为300mm的硅晶片基板上蒸镀厚度为4000的铜(Cu)籽晶层。之后，通过影印石版术在能够进行(Photolithography)工序在铜籽晶层上形成图案来制备试片。在能够进行单独旋转蚀刻(single spin etch)的设备进行蚀刻。
铜籽晶层的蚀刻均匀性评价以如下方式进行，利用实施例1至实施例29以及比较例1至比较例8的蚀刻液组合物来在单独旋转蚀刻机(Single spin etcher)进行35秒的蚀刻之后，为了观察铜籽晶层的蚀刻均匀性，而利用扫描电子显微镜(日立社制造，S-4800)来观察在晶片的中央隔开0.100mm的厚度的位置蚀刻的铜籽晶层的厚度，观察结果请参照表2。并且，利用表面张力测定仪(KRUSS社制造，K-100)来测定各个实施例和比较例的蚀刻液组合物的表面张力，该结果也参照表2。
表2
从表2可确认到，在本发明的实施例1至实施例29的情况下，使用了第一有机酸、第二有机酸及胺化合物而与比较例1至比较例8相比具有非常优秀的蚀刻均匀性。
蚀刻特性评价
为了评价本发明的铜蚀刻液组合物的根据处理量及处理时间的蚀刻特性，准备具有如图1所示的结构的凸点。详细地，在直径为300mm的硅晶片基板上蒸镀厚度为的钛(Ti)籽晶层后，在钛籽晶层上蒸镀厚度为的铜(Cu)籽晶层。之后，通过电镀法来依次形成厚度为的铜金属层、的镍(Ni)层、的锡银(SnAg)合金锡球(SD，solder ball)。
在实施例1至实施例29的蚀刻液组合物及比较例1至比较例8的蚀刻液组合物溶解0、500、1000、2000ppm的铜粉后，进行蚀刻处理来执行根据铜籽晶层的处理量增加的蚀刻特性评价。蚀刻时间为以在0ppm铜的蚀刻液组合物中去除的铜籽晶层的时间为基准，以进一步执行70％时间的蚀刻的过度蚀刻时间(over etch time)进行蚀刻。结束蚀刻过程后，利用刻蚀偏差(etch bias)指定基于蚀刻液组合物蚀刻的电镀铜层和未进行蚀刻的镍层的差异来测定，并将其结果表示在表3。
并且，在实施例1至实施例29的蚀刻液组合物及比较例1至比较例8的蚀刻液组合物溶解1000ppm的铜粉后，以12小时的时间间距进行0、12、24、36、48、60、72时间的蚀刻工序来测定蚀刻程度变化，并将其结果表示在表3。
表3
从表3可确认到，在本发明的实施例1至实施例29的情况下，使用了第一有机酸、第二有机酸及胺化合物而即使铜离子的浓度或蚀刻时间增加也位置铜蚀刻性能，相反，在比较例1至比较例8的情况下，随着铜离子的浓度或蚀刻时间增加而蚀刻性能大幅下降。
以上，通过特定事项和限定的实施例及比较例来说明了本发明，然而这仅仅是为了有助于本发明的整体上的理解而提供的，本发明并不局限于上述实施例，本发明所属领域普通技术人员可在上述记载的基础上进行多种修改及变形。
因此，本发明的思想并不局限于所说明的实施例，发明要求保护范围及其等同或等价变形均属于本发明的思想范围。

Claims (8)

1.一种铜蚀刻液组合物，其特征在于，包含：
第一有机酸，含有一种以上胺基及一种以上羧酸基；
第二有机酸；
胺化合物；
过氧化氢；以及
磷酸盐化合物。
2.根据权利要求1所述的铜蚀刻液组合物，其特征在于，相对于上述铜蚀刻液组合物的总重量，包含0.01重量百分比至5重量百分比的第一有机酸、0.01重量百分比至5重量百分比的第二有机酸、0.01重量百分比至10重量百分比的胺化合物、0.5重量百分比至10重量百分比的过氧化氢以及0.01重量百分比至10重量百分比的磷酸盐化合物。
3.根据权利要求1所述的铜蚀刻液组合物，其特征在于，上述第一有机酸为选自亚氨基二乙酸、亚氨基二琥珀酸、乙二胺四乙酸、二乙烯三胺五乙酸、次氮基三乙酸、2-羟乙基乙二胺三乙酸、乙二醇双(2-氨基乙醚)四乙酸及它们的盐的一种或两种以上。
4.根据权利要求1所述的铜蚀刻液组合物，其特征在于，上述第二有机酸不含有胺基并含有一种以上羧酸基。
5.根据权利要求4所述的铜蚀刻液组合物，其特征在于，上述第二有机酸满足以下关系式1，
关系式1：B-2≤A≤B+2，
上述关系式1中，A为第二有机酸的pKa，B为蚀刻液组合物的pH，此时，B的pH为4至6.5。
6.根据权利要求5所述的铜蚀刻液组合物，其特征在于，上述第二有机酸为选自蚁酸、乙酸、丁酸、戊酸、丙二酸、乙醇酸、琥珀酸、柠檬酸、戊二酸、酒石酸、丙酸、葡萄糖酸及它们的盐的一种或两种以上。
7.根据权利要求1所述的铜蚀刻液组合物，其特征在于，上述胺化合物为选自C4至C9的直链型烷基胺、C4至C20的支链型烷基胺、C4至C20的环烷基胺及C6至C20的芳胺的一种或两种以上。
8.根据权利要求1所述的铜蚀刻液组合物，其特征在于，上述磷酸盐化合物为选自H3PO4、NaH2PO4、Na2HPO4、Na3PO4、NH4H2PO4、(NH4)2HPO4、(NH4)3PO4、KH2PO4、K2HPO4、K3PO4、Ca(H2PO4)2、Ca2HPO4及Ca3PO4的一种或两种以上。
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Publication number Priority date Publication date Assignee Title
CN107385442B (zh) * 2017-07-26 2020-06-16 苏州天承化工有限公司 一种铜面有机酸型超粗化剂及制备方法
CN111032235B (zh) * 2017-10-23 2021-06-22 Mec株式会社 膜形成基材的制造方法、膜形成基材及表面处理剂
KR102493061B1 (ko) * 2019-02-28 2023-01-31 주식회사 이엔에프테크놀로지 금속막 식각 조성물
KR102494016B1 (ko) * 2019-02-28 2023-02-01 주식회사 이엔에프테크놀로지 금속막 식각 조성물 및 이를 이용한 식각 방법
JP7274221B2 (ja) * 2020-11-11 2023-05-16 メック株式会社 エッチング剤及び回路基板の製造方法
US20230243041A1 (en) * 2022-01-28 2023-08-03 Texas Instruments Incorporated Etching compositions

Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3773577A (en) * 1971-05-13 1973-11-20 Nippon Peroxide Co Ltd Composition for etching copper with reduced sideways-etching
CN1510169A (zh) * 2002-12-12 2004-07-07 Lg.菲利浦Lcd株式会社 用于多层铜和钼的蚀刻溶液及使用该蚀刻溶液的蚀刻方法
US20090301382A1 (en) * 2008-06-04 2009-12-10 Patel Gordhanbhai N Monitoring System Based on Etching of Metals
CN103282549A (zh) * 2010-11-12 2013-09-04 Oci有限公司 用于刻蚀金属层的组合物
US20140038348A1 (en) * 2012-08-03 2014-02-06 Samsung Display Co., Ltd. Etchant composition and manufacturing method for thin film transistor using the same
CN103911613A (zh) * 2012-12-28 2014-07-09 东友精细化工有限公司 用于含铜金属层的蚀刻剂组合物及制造阵列基板的方法

Family Cites Families (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP3962239B2 (ja) 2001-10-30 2007-08-22 株式会社Ａｄｅｋａ エッチング剤組成物及びパターン形成方法
JP4430990B2 (ja) 2004-06-29 2010-03-10 株式会社荏原電産 セミアディティブ工法用回路形成エッチング液
JP2006111953A (ja) 2004-10-18 2006-04-27 Mec Kk 銅又は銅合金のエッチング剤、その製造法、補給液及び配線基板の製造法
KR101495683B1 (ko) * 2008-09-26 2015-02-26 솔브레인 주식회사 액정표시장치의 구리 및 구리/몰리브데늄 또는 구리/몰리브데늄합금 전극용 식각조성물
WO2013015322A1 (ja) * 2011-07-26 2013-01-31 三菱瓦斯化学株式会社 銅／モリブデン系多層薄膜用エッチング液
KR101333551B1 (ko) * 2011-11-24 2013-11-28 주식회사 이엔에프테크놀로지 구리와 몰리브덴 합금막의 식각액 조성물

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3773577A (en) * 1971-05-13 1973-11-20 Nippon Peroxide Co Ltd Composition for etching copper with reduced sideways-etching
CN1510169A (zh) * 2002-12-12 2004-07-07 Lg.菲利浦Lcd株式会社 用于多层铜和钼的蚀刻溶液及使用该蚀刻溶液的蚀刻方法
US20090301382A1 (en) * 2008-06-04 2009-12-10 Patel Gordhanbhai N Monitoring System Based on Etching of Metals
CN103282549A (zh) * 2010-11-12 2013-09-04 Oci有限公司 用于刻蚀金属层的组合物
US20140038348A1 (en) * 2012-08-03 2014-02-06 Samsung Display Co., Ltd. Etchant composition and manufacturing method for thin film transistor using the same
CN103911613A (zh) * 2012-12-28 2014-07-09 东友精细化工有限公司 用于含铜金属层的蚀刻剂组合物及制造阵列基板的方法

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN110029348A (zh) * 2018-08-09 2019-07-19 苏州纳勒电子科技有限公司 一种用于处理铜表面的微蚀液
CN110205630A (zh) * 2018-08-09 2019-09-06 苏州纳勒电子科技有限公司 一种能用于杂质清除的微蚀液
CN110219003A (zh) * 2019-07-01 2019-09-10 江苏和达电子科技有限公司 用于蚀刻由铜层及钼层构成的金属层的蚀刻液及其应用
CN115786915A (zh) * 2022-11-23 2023-03-14 江阴江化微电子材料股份有限公司 一种半导体封装用铜蚀刻液及蚀刻方法

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