CN102822391A - 用于含铜和钛的金属层的蚀刻液组合物 - Google Patents

用于含铜和钛的金属层的蚀刻液组合物 Download PDF

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CN102822391A
CN102822391A CN2011800164538A CN201180016453A CN102822391A CN 102822391 A CN102822391 A CN 102822391A CN 2011800164538 A CN2011800164538 A CN 2011800164538A CN 201180016453 A CN201180016453 A CN 201180016453A CN 102822391 A CN102822391 A CN 102822391A
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CN102822391B (zh
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林玟基
权五柄
李喻珍
刘仁浩
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Dongwoo Fine Chem Co Ltd
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Abstract

本发明提供一种用于含铜和钛的金属层的蚀刻液组合物，基于组合物的总量，包含：5wt％～20wt％的过硫酸盐；0.01wt％～2wt％的氟化合物；1wt％～10wt％的选自无机酸、无机酸盐及它们的混合物中的一种或多种；0.3wt％～5wt％的环状胺化合物；0.1wt％～5wt％的氯化合物；0.1wt％～5wt％的对甲苯磺酸；及其余为水。

Description

用于含铜和钛的金属层的蚀刻液组合物
技术领域
本发明涉及一种用于含铜和钛的金属层的蚀刻液组合物，该蚀刻液组合物用于栅极、源极/漏极布线，以及半导体装置和平板显示器的电极，特别是用于薄膜晶体管(TFT)的电极。
背景技术
在半导体装置和平板显示器中，在基板上形成金属布线的制程通常包括利用溅射形成金属层、涂布光刻胶、利用曝光及显影在选择的区域上形成光刻胶、以及进行蚀刻。此外，在每个单独的步骤之前或之后进行清洗步骤。蚀刻步骤利用光刻胶作为掩模，使金属层留在选择的区域上，并且通常包括使用等离子体的干蚀刻或使用蚀刻液的湿蚀刻。
对于半导体装置和平板显示器，特别是TFT，栅极和源极/漏极阵列布线由金属层组成，该金属层包括由低电阻的铝制成的导电层。然而，铝层有问题，原因在于由于在随后的步骤中形成小丘(hillock)而导致与另一导电层间的短路，并且因接触氧化物层而形成绝缘层。因此，公开了含铜和钛的双层作为栅极、源极/漏极阵列布线、及TFT的电极。
但为了蚀刻含铜和钛的双层，对于各个层应使用不同的蚀刻液组合物。具体地，用于蚀刻含铜的金属层的蚀刻液组合物应主要包含基于过氧化氢的蚀刻液组合物或基于过硫酸氢钾(oxone)的蚀刻液组合物。在基于过氧化氢的蚀刻液组合物的情况下，蚀刻液组合物可能分解则储存期短。在基于过硫酸氢钾的蚀刻液组合物的情况下，蚀刻速率慢且组合物随时间变得不稳定。
发明内容
因此，本发明的第一目的是提供一种蚀刻液组合物，所述蚀刻液组合物能够蚀刻含铜和钛的金属层，特别是能够全面湿蚀刻Cu/Ti双层。
本发明的第二目的是提供一种蚀刻液组合物，所述蚀刻液组合物即使不含过氧化氢和/或过硫酸氢钾也对铜表现出快的蚀刻速率。
本发明的第三目的是提供一种蚀刻液组合物，所述蚀刻液组合物能够简化蚀刻步骤且改进生产率。
本发明的第四目的是提供一种蚀刻液组合物，所述蚀刻液组合物可实现快的蚀刻速率和均一的蚀刻。
本发明的第五目的是提供一种蚀刻液组合物，所述蚀刻液组合物不损坏设备且蚀刻时不需要昂贵的设备。
本发明的第六目的是提供一种蚀刻液组合物，所述蚀刻液组合物可有利地应用于大尺寸显示面板，由此产生经济效益。
本发明的第七目的是提供一种蚀刻液组合物，所述蚀刻液组合物除了能够蚀刻含铜和钛的金属层外，还能够蚀刻用于像素电极的IZO或a-ITO。
本发明的一方面提供一种用于含铜和钛的金属层的蚀刻液组合物，基于组合物的总量，包含：5wt％～20wt％的过硫酸盐；0.01wt％～2wt％的氟化合物；1wt％～10wt％的选自无机酸、无机酸盐及它们的混合物中的一种或多种；0.3wt％～5wt％的环状胺化合物；0.1wt％～5wt％的氯化合物；0.1wt％～5wt％的对甲苯磺酸；及其余为水。
本发明的另一方面提供一种制造半导体装置或平板显示器的方法，包括使用所述蚀刻液组合物蚀刻含铜和钛的金属层的步骤。
本发明的又一方面提供一种使用所述蚀刻液组合物制造的半导体装置或平板显示器。
根据本发明，所述蚀刻液组合物能湿蚀刻含铜和钛的金属层，更具体地，能蚀刻Cu/Ti双层，由此简化蚀刻步骤且改进生产率。又根据本发明，所述蚀刻液组合物能表现出快的蚀刻速率且使实现均一蚀刻，由此赋予优异的蚀刻性能。又根据本发明，所述蚀刻液组合物丝毫不损坏设备且蚀刻时不需要昂贵的设备，且能有利地应用于大尺寸显示面板，由此产生经济效益。又根据本发明，所述蚀刻液组合物除了能蚀刻含铜和钛的金属层外，还能蚀刻用于像素电极的IZO或a-ITO。而且，如果将含铜和钛的金属层用于源/漏电极且将IZO或a-ITO用于像素电极，根据本发明的蚀刻液组合物能一起蚀刻源/漏电极和像素电极。又根据本发明，所述蚀刻液组合物即使不包含过氧化氢和/或过硫酸氢钾也能实现对铜快的蚀刻速率。
具体实施方式
在下文中将给出本发明的详细说明。
根据本发明的用于含铜和钛的金属层的蚀刻液组合物包括：过硫酸盐；氟化合物；选自无机酸、无机酸盐及它们的混合物中的一种或多种；环状胺化合物；氯化合物；对甲苯磺酸；及水。
包含在根据本发明的蚀刻液组合物中的过硫酸盐是用于蚀刻含铜的层的主要氧化剂，且基于组合物的总重量，过硫酸盐的用量为5wt％～20wt％，并且优选为7wt％～18wt％。当该组分的量落入上述范围内时，含铜的层以合适的量蚀刻，且蚀刻轮廓变得优异。
当过硫酸盐的量低于5wt％时，蚀刻速率降低，由此不能充分地进行蚀刻。此外，当过硫酸盐的量大于20wt％时，蚀刻速率增加过快，使得难以控制蚀刻速率，结果钛膜和铜膜可能被过度蚀刻。
过硫酸盐可选自由过硫酸铵(APS)、过硫酸钠(SPS)及过硫酸钾(PPS)组成的组。
包含在根据本发明的蚀刻液组合物中的氟化合物主要用于蚀刻含钛的层、IZO、或a-ITO，且基于组合物的总重量，以0.01wt％～2wt％，且优选以0.05wt％～1wt％的量加入。当该组分的量落入上述范围内时，含钛的层以合适的量蚀刻，且蚀刻轮廓变得优异。当该组分的含量低于上述范围的下限时，含钛的层的蚀刻速率可能降低，且可能产生蚀刻残渣。相反，当该组分的含量超出上述范围的上限时，可能损害诸如玻璃等基板以及含硅的绝缘层。
氟化合物指能解离成氟离子或多原子氟离子的化合物，选自由氟化铵、氟化钠、氟化钾、氟化氢铵、氟化氢钠及氟化氢钾组成的组。
包含在根据本发明的蚀刻液组合物中的选自无机酸、无机酸盐及它们的混合物中的一种或多种可氧化和蚀刻含铜的层，并且可氧化含钛的层。基于组合物的总重量，选自无机酸、无机酸盐及它们的混合物中的一种或多种可以1wt％～10wt％，且优选以2wt％～7wt％的量使用。当该组分的量落入上述范围内时，含铜的层和含钛的层以合适的量蚀刻，且蚀刻轮廓变得优异。如果该组分的含量低于上述范围的下限，蚀刻速率可能降低，蚀刻轮廓不期望地变坏且产生蚀刻残渣。相反，当该组分的含量超出上述范围的上限时，则可能发生过蚀刻，并且光刻胶可能裂开而形成裂缝，从而蚀刻液可渗入到裂缝中，不期望地使线路短路。
无机酸选自由硝酸、硫酸、磷酸及过氯酸组成的组。
无机酸盐可选自由硝酸、硫酸、磷酸及过氯酸的钾盐、钠盐及铵盐组成的组。
包含在根据本发明的蚀刻液组合物中的环状胺化合物当蚀刻含铜的层时可形成轮廓。基于组合物的总重量，环状胺化合物以0.3wt％～5wt％，且优选以0.5wt％～3wt％的量使用。当该组分的量落入上述范围内时，形成合适的铜蚀刻速率和锥角，且可有效地控制侧面蚀刻程度。
当环状胺化合物的量低于0.3wt％时，含铜的金属层的蚀刻速率增加，由此含铜的金属层可能被过度蚀刻。此外，当环状胺化合物的量大于5wt％时，含铜的金属层的蚀刻速率降低，由此含铜的金属层不能被适当地蚀刻。
环状胺化合物选自由5-氨基四唑、甲苯基三唑、苯并三唑及甲基三唑组成的组。
包含在根据本发明的蚀刻液组合物中的氯化合物是用于蚀刻含铜的层的助氧化剂，基于组合物的总重量，氯化合物以0.1wt％～5wt％，且优选以0.5wt％～3wt％的量使用。当氯化合物的含量为0.1wt％～5wt％时，更有效地形成锥角。
当氯化合物的量低于0.1wt％时，锥角极低，使得锥形表面变长，因而导致随后步骤中的问题。此外，当氯化合物的量大于5wt％时，锥角极高，使得随后步骤中的台阶覆盖(step coverage)变差。
氯化合物是可解离成氯离子的化合物，可以是选自由氢氯酸、氯化钠、氯化钾及氯化铵(NH4Cl)组成的组中的至少一种。
包含在根据本发明的蚀刻液组合物中的对甲苯磺酸用于防止蚀刻特性因蚀刻剂本身老化造成的蚀刻剂组成的改变而改变，并且起到允许蚀刻剂长时间储存的作用。基于组合物的总量，对甲苯磺酸的含量为0.1wt％～5wt％，优选为0.5wt％～3wt％。当对甲苯磺酸的量低于0.1wt％时，难以防止因蚀刻剂本身老化造成的蚀刻剂组成的改变。此外，当对甲苯磺酸的量大于5wt％时，能够防止因蚀刻剂本身老化造成的蚀刻剂组成的改变，但表现出过蚀刻，因而不能获得优异的轮廓。
包含在根据本发明的蚀刻液组合物中的水为适用于半导体工艺过程的去离子水，及电阻率为至少18MΩ·cm。基于组合物的总重量，水作为其余部分加入，从而使蚀刻液组合物的总重量为100wt％。
除上述组分外，根据本发明的蚀刻液组合物还可进一步包含选自蚀刻控制剂、表面活性剂、螯合剂(sequestering agent)及防蚀剂中的一种或多种。
根据本发明的蚀刻液组合物有效地用于蚀刻含铜和钛的金属层，特别是有效地用于蚀刻具有Cu/Ti结构的双层膜。此外，该蚀刻液组合物有效地用于蚀刻IZO膜或a-ITO膜。
列举下列实施例及测试例来举例说明本发明，但不解释为限制本发明，而是可提供本发明更好的理解。
实施例1及比较例1：蚀刻液组合物的制备
使用如下表1中所示组分的量制备180kg的蚀刻液组合物。
[表1]
Figure BDA00002200843900051
*APS：过硫酸铵
ABF：氟化氢铵
ATZ：5-氨基四唑
PTA：对甲苯磺酸
测试例：蚀刻液组合物性能的评估
将SiNx层沉积在玻璃上，在SiNx层上形成铜层，并且在铜层上形成钛层。将光刻胶以预定图案应用在钛层上，并且将所得到的基板用金刚石刀片切割成550mm x 650mm，由此制作测试样品。
<蚀刻性能的评估>
将实施例1及比较例1各自的蚀刻液组合物引入到喷雾型蚀刻装置内(ETCHER(TFT)，购自SEMES)，然后温热至25℃温度。随后，温度达到30±0.1℃，之后进行蚀刻。总蚀刻时间基于40％的EPD设定。将测试样品放置在装置内，并且用组合物喷雾。蚀刻完成后，用去离子水清洗测试样品并且使用热风干燥器干燥，之后用光刻胶剥离剂(stripper)将光刻胶(PR)除去。清洗并干燥后，使用扫描电子显微镜(SEM)(S-4700，购自HITACHI)评估蚀刻性能。结果示于下表2中。
<储存特性的评估>
大量制备实施例1及比较例1的蚀刻液组合物，并且用蚀刻液组合物进行参考蚀刻(reference etch)。将参考蚀刻后剩余的蚀刻液组合物在25℃下储存预定天数(这里为5天)，然后在与参考蚀刻相同条件下，用储存的蚀刻液组合物进行蚀刻。其结果与参考蚀刻结果作比较。
[表2]
  蚀刻特性   储存特性
 实施例1   ◎   ◎
 比较例1   ◎   X
<蚀刻特性>
◎：非常优异(CD扭斜(Skew)：≤1μm，锥角：40°～60°)
○：优异(CD扭斜：≤1.5μm，锥角：30°～60°)
△：良好(CD扭斜：≤2μm，锥角：30°～60°)
X：差(金属层被破坏并且形成残余渣滓)
<储存特性>
◎：非常优异(五天后，蚀刻轮廓优异)
X：差(五天后，蚀刻轮廓不好)
参考上表2，能确定本发明实施例1的蚀刻液组合物的蚀刻特性和储存特性优异，而比较例1的不包含对甲苯磺酸的蚀刻液组合物的储存特性差。

Claims (10)

1.一种用于含铜和钛的金属层的蚀刻液组合物，基于所述组合物的总量，包含：
5wt％～20wt％的过硫酸盐；
0.01wt％～2wt％的氟化合物；
1wt％～10wt％的选自无机酸、无机酸盐及它们的混合物中的一种或多种；
0.3wt％～5wt％的环状胺化合物；
0.1wt％～5wt％的氯化合物；
0.1wt％～5wt％的对甲苯磺酸；以及
其余为水。
2.根据权利要求1所述的蚀刻液组合物，其中所述过硫酸盐选自由过硫酸铵、过硫酸钠及过硫酸钾组成的组。
3.根据权利要求1所述的蚀刻液组合物，其中所述氟化合物选自由氟化铵、氟化钠、氟化钾、氟化氢铵、氟化氢钠及氟化氢钾组成的组。
4.根据权利要求1所述的蚀刻液组合物，其中所述无机酸选自由硝酸、硫酸、磷酸及过氯酸组成的组，并且所述无机酸盐选自由硝酸、硫酸、磷酸及过氯酸的钾盐、钠盐及铵盐组成的组。
5.根据权利要求1所述的蚀刻液组合物，其中所述环状胺化合物选自由5-氨基四唑、甲苯基三唑、苯并三唑及甲基苯并三唑组成的组。
6.根据权利要求1所述的蚀刻液组合物，其中所述氯化合物选自由氢氯酸、氯化钠、氯化钾及氯化铵组成的组。
7.一种用于制造半导体装置的方法，包括使用权利要求1～6中任一项所述的蚀刻液组合物蚀刻含铜和钛的金属层的步骤。
8.一种用于制造平板显示器的方法，包括使用权利要求1～6中任一项所述的蚀刻液组合物蚀刻含铜和钛的金属层的步骤。
9.一种半导体装置，使用权利要求1～6中任一项所述的蚀刻液组合物制造。
10.一种平板显示器，使用权利要求1～6中任一项所述的蚀刻液组合物制造。
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