CN1298827C - 含水的溶脱和洗涤组合物 - Google Patents

含水的溶脱和洗涤组合物 Download PDF

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CN1298827C
CN1298827C CNB03802036XA CN03802036A CN1298827C CN 1298827 C CN1298827 C CN 1298827C CN B03802036X A CNB03802036X A CN B03802036XA CN 03802036 A CN03802036 A CN 03802036A CN 1298827 C CN1298827 C CN 1298827C
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马修·I·埃贝
达里尔·W·彼得斯
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Abstract

本发明涉及用于从半导体基片上去除后蚀刻有机和无机残留物及高分子残留物及污染物的含水组合物。该组合物由水溶性有机溶剂、磺酸和水组成。

Description

含水的溶脱和洗涤组合物
                      背景技术
在半导体或半导体微电路的生产中，需要从半导体器件的基片表面去除一些物质。在一些实例中，要去除的物质是被称之为光致抗蚀剂的高分子组合物。在其它实例中，要去除的物质是蚀刻或灰化工艺的残留物或只是污染物。溶脱和/或洗涤组合物的目的是在没有腐蚀、溶解或暗化基片的暴露表面的条件下，从半导体基片去除不需要的物质。
有许多不同的用于从半导体基片溶脱光致抗蚀剂和/或洗涤蚀刻残留物、灰或其它污染物的组合物。例如，Allied Signal发表的一些专利公开了非水有机溶脱组合物，包含一种或多种有机磺酸、有机溶剂和各种改进剂。第一篇专利US4,165,295公开了一种用于去除高分子有机物质如光致抗蚀剂的组合物，其包含一种或多种有机磺酸、一种或多种有机溶剂、可选择的酚和约5-250ppm的氟化物离子。第二篇专利US4,215,005提供了一种改进的组合物，其中同时含有氟化物和一种含氮的络合剂，该氮具有一可利用的未共享电子对。第三篇专利US4,221,647提供了另一改进的组合物，其中在该组合物中加入了0.01-5重量％的腈化合物。第四篇专利US4,242,218公开了一种无酚溶脱组合物，该组合物包含与氯化芳基化合物、具有1-14个烷基碳原子的烷芳基化合物、异链烷烃或它们的混合物混合的磺酸。
US5,308,745公开了溶脱光致抗蚀剂的含碱组合物，其具有降低的金属腐蚀作用，含有水溶液中PK为2.0或更高和当量小于约140的不含氮的弱酸。该弱酸的用量可中和该组合物中19％-75％的胺。US5,972,862公开了一种用于半导体器件的洗涤液，包含含氟化物的化合物、水溶性有机溶剂、无机或有机酸和可选择的四元铵盐或羧酸铵盐和/或有机羧酸胺盐。US6,231,677公开了将一种或多种羧酸用于溶脱组合物。WO00/02238公开了一种基于胆碱化合物如氢氧化胆碱的化学洗涤剂。该组合物由胆碱化合物、水和有机溶剂组成。该组合物可额外含有羟基胺和抗腐蚀剂。
                      发明内容
本发明涉及用于从半导体基片去除光致抗蚀剂、蚀刻和灰化残留物和污染物的含水组合物。该含水组合物具有低的表面张力、低的粘度，并且可与包括Al/Cu，Cu，Ti，W，Ta，TiN，W或TaN的各种基片、低-k材料如甲基硅倍半烷(methylsilsesquioxane)(MSQ)、黑钻石、SiLK和高-k材料如Pt/BST/氧化物相容，其中BST是钽酸钡锶。
本发明的组合物基本上由如下组分构成：
A)30-90重量％的选自有机胺、酰胺、亚砜、砜、内酰胺、咪唑啉酮、内酯、多元醇以及它们的混合物的水溶性有机溶剂，
B)3-20重量％的磺酸或其相应的盐，所述磺酸选自对-甲苯磺酸、1，5-萘二磺酸、4-乙基苯磺酸、十二烷基苯磺酸、异丙基苯磺酸、甲基乙基苯磺酸、二甲苯磺酸的异构体以及它们的混合物；和
C)5-50重量％的水。
该组合物还任选地含有抗腐蚀剂。
本发明的组合物不包含含氟化物的化合物和无机胺。
本发明还涉及一种从半导体基片上去除光致抗蚀剂、蚀刻和/或灰化残留物、或污染物的方法，包括：使所述半导体基片与如上所述的本发明的组合物接触足够的时间以去除所述光致抗蚀剂、蚀刻和/或灰化残留物、或污染物。
                    具体实施方式
本发明涉及用于从半导体基片去除光致抗蚀剂、蚀刻和灰化残留物和污染物的含水组合物。该组合物由水溶性有机溶剂、磺酸或其相应的盐、水和可选择的抗腐蚀剂组成。
该水溶性有机溶剂包括有机胺、酰胺、亚砜、砜、内酰胺、咪唑啉酮、内酯和多元醇等。有机胺的实例包括单乙醇胺、N-甲基乙醇胺、1，2-乙二胺、2-(2-氨基乙氨基)乙醇、二乙醇胺、二丙胺、2-乙氨基乙醇、二甲氨基乙醇、环己胺、苄胺、吡咯、吡咯烷、吡啶、吗啉、哌啶和唑等。酰胺的实例包括N，N-二甲基甲酰胺、二甲基乙酰胺和二乙基乙酰胺等。亚砜的实例包括二甲基亚砜。砜的实例包括二甲砜和二乙砜。内酰胺的实例包括N-甲基-2-吡咯烷酮和咪唑啉酮。内酯的实例包括丁内酯和戊内酯。多元醇的实例包括乙二醇、丙二醇、乙二醇一甲基醚乙酸酯等。优选的水溶性有机溶剂的实例包括单乙醇胺、N-甲基乙醇胺、二甲基亚砜和二甲基乙酰胺。这些水溶性有机溶剂可以单独或混合存在。该水溶性有机溶剂占该组合物总重量的30-90重量％，优选30-85重量％，最优选45-80重量％。
除了水溶性有机溶剂，该组合物还含有磺酸或其相应的盐。适用的磺酸的实例包括对-甲苯磺酸、1，5-萘二磺酸、4-乙基苯磺酸、十二烷基苯磺酸、异丙基苯磺酸、甲基乙基苯磺酸、二甲苯磺酸的异构体和上述磺酸的相应的盐。磺酸盐的实例包括对-甲基磺酸乙醇铵和对-甲基磺酸三乙醇铵。所述磺酸及其相应的盐可以单独的酸或盐、或以磺酸或其盐的混合物的形式存在于该组合物中。该磺酸或其相应的盐占该组合物总重量的3-20重量％，优选3-10重量％。
水是本发明的溶脱和洗涤组合物的必要组分。水占该组合物总重量的5-50重量％，优选5-35重量％，最优选10-30重量％。
可选择地，该溶脱和洗涤组合物含有抗腐蚀剂。在该溶脱和洗涤组合物中可以使用单个的抗腐蚀剂化合物或抗腐蚀剂的混合物。抗腐蚀剂的实例包括苯并三唑、苯甲酸、丙二酸、没食子酸、儿茶酚和丙二酸铵等。基于该溶脱和洗涤组合物总重量，该抗腐蚀剂在该溶脱和洗涤组合物中的量小于等于20重量％，优选为0.1-15重量％。
其它常规的已知成分如染料、抗微生物剂等也可以被包含在该溶脱和洗涤组合物中，基于该溶脱和洗涤组合物总重量，这些成分的总量小于等于5重量％。
本发明的溶脱和洗涤组合物通过在室温下将组分在容器中混合直至固体被溶解而制备。该溶脱和洗涤组合物的实例列于表1中。
                                                                          表1
  化合物/配方#   1   2   3   4   5   6   7   8   9   10   11   12   13
  MEA   70.0   71.0   70.0   -   70.0   70.0   70.0   72.0   -   -   71.0   73.5   72.0
  NMEA   -   -   -   70.0   -   -   -   -   -   -   -   -   --
  DMSO   -   -   -   -   -   -   -   -   71.0   -   -   -   -
  DMAc   -   -   -   -   -   -   -   -   -   71.0   -   -   --
  ToSA   7.0   7.0   7.0   -   7.0   7.0   7.0   7.0   7.0   7.0   -   7.0   -
  NDSA   -   -   -   5.0   -   -   -   -   -   -   -   -   -
  EBSA   -   -   -   -   -   -   -   -   -   -   7.0   -   -
  DBSA   -   -   -   -   -   -   -   -   -   -   -   -   5.0
  去离子水   20.5   19.5   19.5   23.0   22.0   21.5   21.0   19.0   19.5   19.5   19.5   19.5   20.5
  没食子酸   1.5   1.5   1.5   1.0   -   0.5   1.0   1.0   1.5   1.5   1.5   -   1.5
  苯并三唑   1.0   1.0   1.0   1.0   1.0   1.0   1.0   1.0   1.0   1.0   1.0   -   1.0
MEA＝单乙醇胺       ToSA＝对-甲苯磺酸     NMEA＝N-甲基乙醇胺    NDSA＝1，5-萘二磺酸
DMSO＝二甲基亚砜    EBSA＝4-乙苯基磺酸    DMAc＝二甲基乙酰胺    DBSA＝十二烷基苯磺酸
该含水溶脱和洗涤组合物是用于在低温及低腐蚀下，从半导体基片去除后蚀刻和灰化、有机和无机残留物和高分子残留物。通常，用本发明的组合物进行溶脱和洗涤的方法是在25-80℃下将基片浸于该溶脱/洗涤组合物中3分钟至1小时。然而，可以用本领域任何已知的利用液体去除光致抗蚀剂、蚀刻或灰化残留物和/或污染物的方法来使用本发明的组合物。
以下是本发明的组合物的应用实施例，本发明不受限于这些实施例。
实施例1
正性光致抗蚀剂被旋涂于硅晶片上的化学气相沉积Al-Cu膜的基片上。该正性光致抗蚀剂由重氮萘醌和酚醛清漆树脂组成，在90℃下将该光致抗蚀剂涂层烘烤90秒。通过将晶片曝光于穿过构图掩膜的i-线(365nm)射线及随后显影，图形被限定于该光致抗蚀剂上。用Cl2/BCl3蚀刻气体混合物在5乇压力及20℃下等离子蚀刻该构图片。将该经蚀刻的图形在0.3乇压力及65℃下经氧等离子灰化55秒。
在65℃下将该经构图及灰化的晶片浸于含有表1中的配方3的浴中浸30分钟。通过检测该晶片的SEM图来分析该经洗涤的晶片。SEM照片显示该晶片被清洗并且没有残留物和没有被腐蚀的迹象。
实施例2
将TEOS(四乙氧基硅酸盐)涂于TiN防反射涂层上(ARC)，该防反射涂层又被涂于Al-Cu层上，该Al-Cu层被化学沉积于硅晶片上。将正性光致抗蚀剂旋涂于TEOS层上。将所涂的光致抗蚀剂在90℃下烘烤90秒。通过将晶片曝光于穿过构图掩模的i-线射线及随后显影，图形被限定于该光致抗蚀剂上。用两步等离子法将该图形从光致抗蚀剂层转移至基片。第一步包括使该晶片经受针对TEOS层的CO/CF4/Ar/CHF3等离子蚀刻气体混合物，随后就地经受针对TiN ARC层的Ar/CF4/O2等离子蚀刻气体混合物。在0.3乇压力及60℃下用氧等离子灰化该经蚀刻的图形150秒。在65℃下将该经蚀刻和灰化的晶片浸于含配方3的浴中30分钟。通过检测该晶片的SEM图来分析该经洗涤的晶片。SEM显示该晶片被清洗并且没有残留物和没有被腐蚀的迹象。

Claims (9)

1.一种用于从半导体基片上去除蚀刻和/或灰化残留物或污染物的组合物，其基本上由如下组分构成：
A)30-90重量％的选自有机胺、酰胺、亚砜、砜、内酰胺、咪唑啉酮、内酯、多元醇以及它们的混合物的水溶性有机溶剂，
B)3-20重量％的磺酸或其相应的盐，所述磺酸选自对-甲苯磺酸、1，5-萘二磺酸、4-乙基苯磺酸、十二烷基苯磺酸、异丙基苯磺酸、甲基乙基苯磺酸、二甲苯磺酸的异构体以及它们的混合物；和
C)5-50重量％的水。
2.如权利要求1的组合物，进一步包含抗腐蚀剂。
3.如权利要求1的组合物，其中水溶性有机溶剂是单乙醇胺、N-甲基乙醇胺、二甲基亚砜、二甲基乙酰胺或它们的混合物。
4.如权利要求2的组合物，其中抗腐蚀剂是没食子酸、儿茶酚、苯并三唑、苯甲酸、丙二酸、丙二酸铵或它们的混合物。
5、如权利要求2的组合物，其中抗腐蚀剂的含量为小于等于20重量％。
6.如权利要求5的组合物，其中抗腐蚀剂的含量为0.1-15重量％。
7.如权利要求1-6任一项所述的组合物，其中所述的水溶性有机溶剂的含量为45-90重量％，并且所述的磺酸或其相应的盐的含量为3-10重量％。
8、如权利要求1-6任一项所述的组合物，其中所述的水溶性有机溶剂的含量为30-85重量％。
9、一种从半导体基片上去除光致抗蚀剂、蚀刻和/或灰化残留物、或污染物的方法，包括：使该半导体基片与前述任一项权利要求所述的组合物接触足够的时间以去除所述光致抗蚀剂、蚀刻和/或灰化残留物、或污染物。
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