CN1982426B - 用于半导体晶片清洗的缓蚀剂体系 - Google Patents
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Abstract
本发明公开了一种半导体晶片清洗的缓蚀剂体系,其中,该缓蚀剂体系包括水和/或溶剂,其特征在于还包括一种含羧基的聚合物,其中,合成该聚合物的至少一种单体含有羧基。本发明的用于半导体晶片清洗的缓蚀剂体系具有对环境友善、安全无毒、有利于健康的特点,可在室温至85℃之间使用,而且在含氟和不含氟的体系中对金属或非金属腐蚀均有很好的抑制效果。
Description
技术领域
本发明涉及一种半导体制造过程中用于半导体晶片清洗的缓蚀剂体系。
背景技术
在半导体元器件制造过程中,光阻层的涂敷、曝光和成像对元器件的图案制造来说是必要的工艺步骤。在图案化的最后(即在光阻层的涂敷、成像、离子植入和蚀刻之后)进行下一工艺步骤之前,光阻层材料的残留物需彻底除去。在掺杂步骤中离子轰击(ion bombardment)会硬化光阻层聚合物,因此使得光阻层变得不易溶从而更难于除去。至今在半导体制造工业中一般使用两步法(干法灰化和湿蚀刻)除去这层光阻层膜。第一步利用干法灰化除去光阻层的大部分;第二步利用缓蚀剂组合物湿蚀刻/清洗工艺除去且清洗掉剩余的光阻层。在第二步的清洗工艺过程中,缓蚀剂组合物只能除去聚合物光阻层(PR)和无机残留物,而不能攻击损害金属层如铝层,通常该步骤需要很长时间;且为了有助于光阻层的除去,常需要在高温下进行。
如现有技术中US 5334332(Lee,EKC),US 5417877(Ward,Ashland)US6030932(Leon,Olin)和US 6635186(Small,EKC)等专利都公开了一些用于湿蚀刻除去光阻层的缓蚀剂组合物,这些缓蚀剂组合物包括邻苯二酚或8-羟基喹啉等毒性物质。尽管这些含有邻苯二酚或其衍生物、8-羟基喹啉或其它缓蚀剂的缓蚀剂组合物缓蚀效果良好,但该缓蚀剂组合物通常浓度高且毒性强,而且需要在高温下使用,对环境不友善、产生很大的危害,对人体健康不利。因此迫切需要开发出新型的缓蚀液体系。
发明内容
本发明的目的在于提供一种用于半导体晶片清洗的缓蚀剂体系,该缓蚀剂体系包括水和/或溶剂,其特征在于还包括一种含羧基的聚合物,其中,合成该聚合物的至少一种单体含有羧基。
本发明的用于半导体晶片清洗的缓蚀剂体系包括含羧基的聚合物,其可以对金属如Al等、或非金属Si、或非金属氧化物SiO2等的腐蚀产生抑制作用;该缓蚀剂体系中的含羧基的聚合物可以起到腐蚀抑制剂、表面活性剂和螯合剂等的作用;本发明的用于半导体晶片清洗的缓蚀剂体系不但具有对环境友善、安全无毒、有利于健康的特点;而且在含氟和不含氟的体系中均有很好的抑制效果;使用本发明的缓蚀剂体系可以降低铝的蚀刻速率,而且几乎不攻击SiO2和Si。本发明的用于半导体晶片清洗的缓蚀剂体系可在室温至85℃之间使用,可用于再循环***、喷镀工具和单晶片处理。
在本发明中,所述的含羧基的聚合物是含羧基的均聚物和/或含羧基的共聚物和/或含羧基的均聚物盐和/或含羧基的共聚物盐。
在本发明的一较佳实施例中,所述的含羧基的均聚物是聚马来酸酐(HPMA)、聚丙烯酸(PAA)和/或聚甲基丙烯酸,优选聚马来酸酐和/或聚丙烯酸;在本发明的另一较佳实施例中,所述的含羧基的共聚物是含羧基的单体之间的共聚物(如:丙烯酸与马来酸共聚物,甲基丙烯酸与马来酸共聚物),或乙烯基单体与含羧基的单体之间的共聚物(如:苯乙烯与丙烯酸共聚物、苯乙烯与马来酸共聚物、丙烯腈与马来酸共聚物、乙烯与丙烯酸共聚物、丙烯腈与丙烯酸共聚物、苯乙烯与甲基丙烯酸共聚物、乙烯与甲基丙烯酸共聚物和/或丙烯腈与甲基丙烯酸共聚物等等),优选丙烯酸与马来酸共聚物;在本发明的再一较佳实施例中,所述的盐是铵盐、钾盐和/或钠盐,优选铵盐,如聚丙烯酸铵(SD)。
在本发明中,只要是现有技术中已有的含羧基的聚合物均可用于本发明的缓蚀剂体系中,含羧基的聚合物分子量大小并不影响实现本发明的目的。若本发明的缓蚀剂体系中具有一定质量浓度的聚合物,该缓蚀剂体系中也相应地具有一定浓度的羧基。这是因为对于一定质量浓度的聚合物而言,若聚合物的分子量大,缓蚀剂体系中聚合物的摩尔数就相应地少;若聚合物的分子量小,缓蚀剂体系中聚合物的摩尔数也就相应地多,也就是说,组成一定的聚合物,其一定质量浓度的聚合物上也就相应地含有一定浓度的羧基。不管该聚合物的分子量大小,只要该聚合物上的羧基在缓蚀剂体系中达到一定的浓度即可,即含羧基聚合物的缓蚀剂体系用于清洗半导体晶片均可以抑制金属如Al、非金属如Si和废金属氧化物如SiO2等的腐蚀。在本发明的缓蚀剂体系中,聚合物上的羧基的浓度较佳地为25ppm~50,000ppm。
在本发明的进一步较佳实施例中,该缓蚀剂体系还可以包含小分子酸和/或小分子碱。
该小分子酸可以是各种小分子酸,优选有机酸,更优选含有单或多羧基的小分子酸;该有机酸较佳地是2-膦酸丁烷-1,2,4-三羧酸(PBTCA)、草酸(OA)、柠檬酸和/或没食子酸,更佳地是2-膦酸丁烷-1,2,4-三羧酸(PBTCA)和/或草酸。
该小分子碱可以是各种小分子碱,优选含有单或多羟基的小分子碱,更优选氨水和/或四甲基氢氧化铵(TMAH)。
在本发明的缓蚀剂体系中,该含羧基的聚合物的浓度可以是各种浓度,优选0.00001~10%,更优选0.01~3%;该小分子酸和/或小分子碱的浓度优选0~10%,更优选0~5%;该水和/或溶剂的浓度可以是现有技术中的各种浓度,优选80~99.99999%,更优选92~99.99%,以上浓度均指占整个缓蚀剂体系的质量浓度。
在本发明中,所述的溶剂是指有机溶剂,可为各种有机溶剂或其混合物,如:N-甲基吡咯烷酮(NMP)、γ-丁内酯(GBL)、N,N-二甲基乙酰胺(DMAC)、一缩二乙二醇单丁醚(DGMBE)和/或乙醇胺(EA),更佳地是NMP、DGMBE和/或EA。
本发明的用于半导体晶片清洗的缓蚀剂体系还可以包括其它腐蚀抑制剂、表面活性剂和/或螯合剂。
本发明的积极进步效果在于:本发明的用于半导体晶片清洗的缓蚀剂体系具有对环境友善、安全无毒、有利于健康的特点,可在室温至85℃之间使用,而且在含氟和不含氟的体系中对金属或非金属均有很好的抑制效果。
具体实施方式
对比实施例1’~4’及实施例1~22
表1 本发明的缓蚀剂体系及对比体系(不含氟体系)
DI:去离子水;NA是没有加入该成份。
表2 本发明的缓蚀剂体系及对比体系(含氟体系)
实施例 | DI% | NMP% | SD% | NH3H2O% | PBTCA% | HPMA% | NH4F% |
4’ | 29 | 70 | NA | NA | NA | NA | 1.0 |
15 | 29.4 | 70 | NA | NA | 0.1 | 0.1 | 0.4 |
16 | 29.8 | 70 | NA | NA | 0.1 | 0.1 | NA |
17 | 28.3 | 70 | NA | 0.5 | 0.1 | 0.1 | 1.0 |
18 | 28.4 | 70 | NA | 0.5 | NA | 0.1 | 1.0 |
19 | 28.2 | 70 | 0.1 | 0.5 | 0.2 | NA | 1.0 |
20 | 28.8 | 70 | 0.1 | NA | 0.1 | NA | 1.0 |
21 | 28.9 | 70 | 0.1 | NA | NA | NA | 1.0 |
22 | 28.4 | 70 | 0.1 | 0.5 | NA | NA | 1.0 |
DI:去离子水;NA是没有加入该成份。
将上述表1和表2中的各成份按照比例混合均匀,制得本发明的缓蚀剂体系及对比的体系。
效果实施例1
将对比实施例1’~3’的体系及实施例1~9的缓蚀剂体系在不含氟的体系中用于清洗蚀刻空白Al晶片。测试方法和条件:25℃,摇床为60转每分钟,时间为30分钟。蚀刻速率是通过四极探针仪测试其蚀刻前后表面电阻变化后计算而得,结果如表3所示。
表3 缓蚀剂体系在不含氟的体系中对空白Al晶片的蚀刻速率
缓蚀剂体系 | 1’ | 2’ | 3’ | 1 | 2 | 3 | 4 | 5 | 6 | 7 | 8 | 9 |
Rate,A/min | 2.94 | 3.89 | 5.89 | 0.80 | -0.19 | 2.5 | 1.96 | -0.57 | -0.76 | 1.95 | 1.55 | 1.3 |
注:Rate表示蚀刻速率;蚀刻速率为负值,表示蚀刻速率几乎为零。
在半导体清洗工艺中,若金属蚀刻速率小于或等于2.0A/min,则说明缓蚀剂体系具有相当好的腐蚀抑制作用。从表3可以看出,不含含羧基聚合物的缓蚀剂体系对空白Al晶片的蚀刻速率大于2.0A/min;本发明的含羧基的聚合物的缓蚀剂体系用于清洗空白Al晶片,Al蚀刻速率都小于2.0A/min,可以明显降低Al的蚀刻速率,甚至达到0A/min,完全抑制了Al腐蚀作用。从而说明本发明的含羧基的聚合物的缓蚀剂体系可以显著地抑制Al腐蚀,从而有利于Al晶片的光阻层有机残留物和/或无机残留物有效去除。
效果实施例2
将上述实施例4缓蚀剂体系用于清洗蚀刻空白SiO2晶片,测试方法和条件:25℃,摇床为60转每分钟,时间为30分钟,用NANOSPEC薄膜测厚仪(购于NANO metrics公司)测试SiO2晶片蚀刻前后表面膜厚变化计算得蚀刻速率。
结果表明:在本发明中,SiO2的蚀刻速率为0.78A/min,其蚀刻速率小于2A/min,说明本发明的缓蚀剂体系也可以抑制SiO2腐蚀。
效果实施例3
将对比实施例4’的体系及实施例15~22的缓蚀剂体系用于清洗蚀刻空白Al晶片。测试方法和条件:25℃,摇床为60转每分钟,时间为30分钟。蚀刻速率是通过四极探针仪测试其蚀刻前后表面电阻变化后计算而得,结果如表4所示。
表4 本发明的缓蚀剂体系用于含氟体系对空白Al晶片的蚀刻速率
缓蚀剂体系 | 4’ | 15 | 16 | 17 | 18 | 19 | 20 | 21 | 22 |
Rate,A/min | 3.09 | 1.70 | 0.80 | -0.01 | -0.36 | 1.16 | 1.60 | 1.88 | 0.79 |
注:Rate表示蚀刻速率;蚀刻速率为负值,表示蚀刻速率几乎为零。
在半导体清洗工艺中,常用氟化物来辅助除去晶片上的残留物,但氟化物往往同时也增加金属的蚀刻速率。如表4数据表明,在含有氟化物的体系中,本发明的缓蚀剂体系用于清洗空白Al晶片,Al蚀刻速率也很小,也可以将Al的蚀刻速率降至2.0A/min以下,即使只含有含羧基聚合物而不含小分子酸和小分子碱的缓蚀剂体系(如实施例21)也可以将Al蚀刻速率降至1.88A/min,Al的腐蚀得到了完全的抑制。
结论:本发明的用于半导体晶片清洗的含羧基聚合物的缓蚀剂体系具有对环境友善、安全无毒、有利于健康的特点,可在室温至85℃之间使用,而且在含氟和不含氟的体系中对金属或非金属均有很好的抑制效果。
Claims (2)
1.一种用于半导体晶片清洗的缓蚀剂体系,该缓蚀剂体系由水、有机溶剂、含羧基的聚合物,以及小分子酸和/或小分子碱组成,其特征在于,
合成该聚合物的至少一种单体含有羧基,所述有机溶剂为N-甲基吡咯烷酮、γ-丁内酯、N,N-二甲基乙酰胺、和/或乙醇胺;
所述小分子酸为2-膦酸丁烷-1,2,4-三羧酸、草酸、柠檬酸和/或没食子酸,所述小分子碱为氨水和/或四甲基氢氧化铵;其中:
所述的含羧基的聚合物为聚丙烯酸、聚甲基丙烯酸、丙烯酸与马来酸共聚物、苯乙烯与丙烯酸共聚物、苯乙烯与马来酸共聚物和/或丙烯腈与马来酸共聚物;
该小分子酸和/或小分子碱的浓度为不超过10%,该水和有机溶剂的浓度为80~99.99999%,该含羧基的聚合物的浓度为0.00001~10%,以上浓度均指占整个缓蚀剂体系的质量浓度。
2.根据权利要求1所述的缓蚀剂体系,其特征在于:该小分子酸和/或小分子碱的浓度为不超过5%,该水和有机溶剂的浓度为92~99.99%,该含羧基的聚合物的浓度为0.01~3%,以上浓度均指占整个缓蚀剂体系的质量浓度。
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