CN106601598B - 半导体元件的清洗用液体组合物、半导体元件的清洗方法及半导体元件的制造方法 - Google Patents
半导体元件的清洗用液体组合物、半导体元件的清洗方法及半导体元件的制造方法 Download PDFInfo
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- CN106601598B CN106601598B CN201610890141.4A CN201610890141A CN106601598B CN 106601598 B CN106601598 B CN 106601598B CN 201610890141 A CN201610890141 A CN 201610890141A CN 106601598 B CN106601598 B CN 106601598B
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- cobalt
- copper
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- phosphonic acid
- semiconductor element
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Classifications
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- H01L21/76814—Applying interconnections to be used for carrying current between separate components within a device comprising conductors and dielectrics characterised by the formation and the after-treatment of the dielectrics, e.g. smoothing by forming openings in dielectrics post-treatment or after-treatment, e.g. cleaning or removal of oxides on underlying conductors
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- H01L21/033—Making masks on semiconductor bodies for further photolithographic processing not provided for in group H01L21/18 or H01L21/34 comprising inorganic layers
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Abstract
本发明涉及半导体元件的清洗用液体组合物、半导体元件的清洗方法及半导体元件的制造方法,其目的在于,提供在半导体元件制造中抑制铜或铜合金、钴或钴合金的损伤、并且将氮化钛硬掩模去除的清洗用液体组合物及使用其的清洗方法、以及半导体元件的制造方法。本发明的半导体元件的制造中使用的清洗用液体组合物包含1~30质量%的过氧化氢、0.01~1质量%的氢氧化钾、0.0001~0.01质量%的氨基多亚甲基膦酸、0.0001~0.1质量%的锌盐、以及水。
Description
技术领域
本发明涉及半导体集成电路的制造工序中使用的半导体元件的清洗用液体组合物、使用其的半导体元件的清洗方法、以及半导体元件的制造方法。
背景技术
在高集成化的半导体元件的制造中,通常在硅晶圆等元件上形成作为导电用布线原材料的金属膜等导电薄膜、以进行导电薄膜间的绝缘为目的的层间绝缘膜后,在其表面上均匀涂布光致抗蚀剂而设置感光层,对其实施选择性的曝光和显影处理,制成期望的光致抗蚀图案。接着,将该光致抗蚀图案作为掩模对层间绝缘膜实施干蚀刻处理,由此在该薄膜上形成期望的图案。然后,通常采用如下一系列的工序进行:利用基于氧等离子体的灰化、清洗液等将光致抗蚀图案和因干蚀刻处理产生的残渣物(以下称为“干蚀刻残渣”)完全去除。
近年来,设计标准的微细化推进,信号传输延迟已经支配高速运算处理的极限。因此,层间绝缘膜从硅氧化膜向低介电常数层间绝缘膜(使用相对介电常数小于3的材料的膜。以下称为“低介电常数层间绝缘膜”)的转变推进。另外,在形成0.2μm以下的图案的情况下,对于膜厚1μm的光致抗蚀剂而言,图案的长宽比(光致抗蚀膜厚除以光致抗蚀剂线宽度而得到的比值)变得过大、产生图案倒塌等问题。为了解决该问题,有时使用如下的硬掩模法:在实际希望形成的图案与光致抗蚀膜之间***钛(Ti)系、硅(Si)系的膜(以下称为硬掩模),暂时通过干蚀刻将光致抗蚀图案转印到硬掩模上并将光致抗蚀剂去除,然后将该硬掩模作为蚀刻掩模,通过干蚀刻在实际希望形成的膜上转印图案。该方法能够更换蚀刻硬掩模时的气体和蚀刻实际希望形成的膜时的气体、能够选择在蚀刻硬掩模时光致抗蚀剂与硬掩模的选择比、在蚀刻实际的膜时确保硬掩模与实际上蚀刻的膜的选择比的气体,因此具有能够极力减少给实际的膜带来的损伤、形成图案的优点。
进而,由于设计标准的微细化的推进,金属布线的电流密度增大,因此电流在金属布线材料中流动时,更强烈要求针对金属布线材料移动从而能够在金属布线上产生孔的电迁移(electromigration)的对策。作为其对策,有在铜布线上以帽金属(cap metal)的形式形成钴、钴合金的方法,如专利文献1所记载的使用钴、钴合金作为金属布线材料的方法。因此不仅现有的铜布线成为抑制损伤的对象,钴、钴合金也成为抑制损伤的对象。
因此,要求在半导体元件制造中抑制铜或铜合金及钴或钴合金的损伤、并且将硬掩模去除的方法。针对该要求提出了各种技术。
专利文献2中提出了利用包含过氧化氢、氨基多亚甲基膦酸类、氢氧化钾及水的清洗用组合物的清洗方法。
专利文献3中提出了在水性介质中含有选自由氨、具有氨基的化合物及具有含有氮原子的环状结构的化合物组成的组中的至少1种和过氧化氢、且pH超过8.5的蚀刻用组合物。
专利文献4中提出了如下清洗用组合物,其包含选自由二甲基哌啶酮、砜类及环丁砜类等组成的组中的极性有机溶剂;选自由四烷基氢氧化铵、氢氧化胆碱、氢氧化钠及氢氧化钾等组成的组中的碱性盐;水;以及选自由反式-1,2-环己二胺四乙酸、乙烷-1-羟基-1,1-二膦酸盐及乙二胺四(亚甲基膦酸)等组成的组中的螯合剂或金属络合剂。
专利文献5中提出了用70℃以上的硫酸水溶液进行清洗从而将氮化钛(TiN)膜去除、不蚀刻硅化钴(Cobalt disilicide)的半导体元件的清洗方法。
专利文献6中提出了包含六氟硅酸化合物和氧化剂的蚀刻液。
专利文献7中提出了包含盐酸等卤素化合物、氧化剂、以及选自含氮杂芳香族化合物和季鎓化合物等的金属层防蚀剂的蚀刻液。
专利文献8中提出了应用包含氢氟酸等氟化合物和氧化剂的蚀刻液,将包含氮化钛(TiN)的层去除、不去除过渡金属层的蚀刻方法。
专利文献9中提出了应用包含有机鎓化合物和氧化剂的蚀刻液,将包含氮化钛(TiN)的层去除、不去除过渡金属层的蚀刻方法。
专利文献10中提出了通过使用包含选自由氢氟酸的金属盐及氢氟酸的铵盐组成的组中的特定的氟化合物和氧化剂的pH为1以上的蚀刻液,对于包含过渡金属的层优先将包含氮化钛(TiN)的层去除的蚀刻方法。
现有技术文献
专利文献
专利文献1:日本特开2013-187350号公报
专利文献2:国际公开第2008/114616号
专利文献3:日本特开2010-232486号公报
专利文献4:日本特表2005-529363号公报
专利文献5:日本特开2003-234307号公报
专利文献6:日本特开2014-84489号公报
专利文献7:日本特开2014-93407号公报
专利文献8:日本特开2014-99498号公报
专利文献9:日本特开2014-99559号公报
专利文献10:日本特开2014-146623号公报
发明内容
发明要解决的问题
但是,近年来,金属布线的微细化进一步推进,对于抑制对金属布线材料的损伤的要求也变得更严格。对于这样的要求,本申请发明人进行了深入研究,结果发现,专利文献2~10中记载的组合物或方法如下所述存在各种技术课题和问题。
对于专利文献2中记载的清洗用液体组合物(包含过氧化氢、氨基多亚甲基膦酸类、氢氧化钾及水的清洗用组合物),无法充分抑制铜和钴的损伤、无法用于本目的(参照比较例1)。
对于专利文献3中记载的蚀刻用组合物(水性介质中含有选自由氨、具有氨基的化合物及具有含有氮原子的环状结构的化合物组成的组中的至少1种和过氧化氢、且pH超过8.5的蚀刻用组合物),TiN硬掩模的去除性不充分、无法充分抑制铜的损伤、无法达成本目的(参照比较例2)。
对于专利文献4中记载的清洗用组合物(包含选自由二甲基哌啶酮、砜类及环丁砜类等组成的组中的极性有机溶剂;选自由四烷基氢氧化铵、氢氧化胆碱、氢氧化钠及氢氧化钾等组成的组中的碱性盐;水;以及选自由反式-1,2-环己二胺四乙酸、乙烷-1-羟基-1,1-二膦酸盐及乙二胺四(亚甲基膦酸)等组成的组中的螯合剂或金属络合剂的清洗用组合物),无法充分抑制铜和钴的损伤、无法用于本目的(参照比较例3)。
对于专利文献5中记载的硫酸水溶液(70℃以上的硫酸水溶液),TiN硬掩模的去除性不充分、无法充分抑制铜和钴的损伤、无法用于本目的(参照比较例4)。
对于专利文献6中记载的蚀刻液(包含六氟硅酸化合物和氧化剂的蚀刻液),TiN硬掩模的去除性不充分、无法充分抑制铜和钴的损伤、无法用于本目的(参照比较例5)。
对于专利文献7中记载的蚀刻液(包含盐酸等卤素化合物、氧化剂、以及选自含氮杂芳香族化合物和季鎓化合物等的金属层防蚀剂的蚀刻液),TiN硬掩模的去除性不充分、无法充分抑制铜和钴的损伤、无法用于本目的(参照比较例6)。
对于专利文献8中记载的蚀刻方法(使用包含氢氟酸等氟化合物和氧化剂的蚀刻液),无法充分抑制铜和钴的损伤、无法用于本目的(参照比较例7)。
对于专利文献9中记载的蚀刻方法(使用包含有机鎓化合物和氧化剂的蚀刻液),无法充分抑制铜和钴的损伤、无法用于本目的(参照比较例8)。
对于专利文献10中记载的蚀刻液(包含选自由氢氟酸的金属盐及氢氟酸的铵盐组成的组中的特定的氟化合物和氧化剂的pH为1以上的蚀刻液),TiN硬掩模的去除性不充分、无法用于本目的(参照比较例9)。
本发明的目的在于,提供在半导体元件制造中抑制铜或铜合金、或者钴或钴合金的损伤、并且将TiN硬掩模去除的清洗用液体组合物及使用其的清洗方法、以及使用该方法得到的半导体元件。
用于解决问题的方案
本发明提供解决上述课题的方法。本发明如下。
1.一种清洗用液体组合物,其抑制选自由包含钴元素的材料和包含铜元素的材料组成的组中的1种以上材料的腐蚀,并且将氮化钛硬掩模去除,所述清洗用液体组合物包含1~30质量%的过氧化氢、0.01~1质量%的氢氧化钾、0.0001~0.01质量%的氨基多亚甲基膦酸、0.0001~0.1质量%的锌盐、以及水。
2.根据第1项所述的清洗用液体组合物,其中,前述锌盐为选自由硫酸锌和硝酸锌组成的组中的1种以上。
3.根据第1项所述的清洗用液体组合物,其中,前述氨基多亚甲基膦酸为选自由氨基三(亚甲基膦酸)、二亚乙基三胺五(亚甲基膦酸)及1,2-丙二胺四(亚甲基膦酸)组成的组中的1种以上。
4.根据第1项所述的清洗用液体组合物,其中,前述包含钴元素的材料为钴或钴合金,前述包含铜元素的材料为铜或铜合金。
5.一种清洗方法,其是对于半导体基板使用前述清洗用液体组合物将氮化钛硬掩模去除的清洗方法,所述半导体基板具有包含钴元素的材料和包含铜元素的材料中的1种以上材料,前述清洗用液体组合物包含1~30质量%的过氧化氢、0.01~1质量%的氢氧化钾、0.0001~0.01质量%的氨基多亚甲基膦酸、0.0001~0.1质量%的锌盐、以及水。即,一种清洗方法,其是将半导体元件中的氮化钛硬掩模去除的半导体元件的清洗方法,所述半导体元件至少具有选自由包含钴元素的材料和包含铜元素的材料组成的组中的1种以上材料和氮化钛硬掩模,所述清洗方法包含使清洗用液体组合物和前述半导体元件接触的工序,所述清洗用液体组合物包含1~30质量%的过氧化氢、0.01~1质量%的氢氧化钾、0.0001~0.01质量%的氨基多亚甲基膦酸、0.0001~0.1质量%的锌盐、以及水。
6.根据第5项所述的清洗方法,其中,前述锌盐为选自由硫酸锌和硝酸锌组成的组中的1种以上。
7.根据第5项所述的清洗方法,其中,前述氨基多亚甲基膦酸为选自由氨基三(亚甲基膦酸)、二亚乙基三胺五(亚甲基膦酸)及1,2-丙二胺四(亚甲基膦酸)组成的组中的1种以上。
8.根据第5项所述的清洗方法,其中,前述包含钴元素的材料为钴或钴合金,前述包含铜元素的材料为铜或铜合金。
9.一种半导体元件的制造方法,所述半导体元件具有选自由包含钴元素的材料和包含铜元素的材料组成的组中的1种以上材料,
所述制造方法包含使用清洗用液体组合物,抑制选自由前述包含钴元素的材料和包含铜元素的材料组成的组中的1种以上材料的腐蚀,并且将氮化钛硬掩模去除的工序,所述清洗用液体组合物包含1~30质量%的过氧化氢、0.01~1质量%的氢氧化钾、0.0001~0.01质量%的氨基多亚甲基膦酸、0.0001~0.1质量%的锌盐、以及水。
10.根据第9项所述的制造方法,其中,前述锌盐为选自由硫酸锌和硝酸锌组成的组中的1种以上。
11.根据第9项所述的制造方法,其中,前述氨基多亚甲基膦酸为选自由氨基三(亚甲基膦酸)、二亚乙基三胺五(亚甲基膦酸)及1,2-丙二胺四(亚甲基膦酸)组成的组中的1种以上。
12.根据第9项所述的制造方法,其中,前述包含钴元素的材料为钴或钴合金,前述包含铜元素的材料为铜或铜合金。
发明的效果
通过使用本发明的清洗用液体组合物及清洗方法,能够在半导体元件的制造工序中抑制金属布线和包含钴(Co)的帽金属的损伤,并且将被处理物表面的包含氮化钛(TiN)的硬掩模去除,能够成品率良好地稳定地制造高精度、高质量的半导体元件。
附图说明
图1为包含势垒金属、金属布线、帽金属、势垒绝缘膜、低介电常数层间绝缘膜及硬掩模的半导体元件的概略剖视图。
附图标记说明
1:势垒金属
2:金属布线
3:帽金属
4:势垒绝缘膜
5:低介电常数层间绝缘膜
6:硬掩模
具体实施方式
本发明的清洗用液体组合物(以下有时简称为“清洗液”)包含过氧化氢、氢氧化钾、氨基多亚甲基膦酸、锌盐、以及水。
本发明中的用于去除TiN硬掩模的半导体元件的清洗用液体组合物在制作半导体元件的工序中使用,因此必须抑制金属布线的损伤。
本发明中所使用的过氧化氢的浓度范围为1~30质量%、优选为3~25质量%、特别优选为10~25质量%。为上述范围内时,能够有效地将TiN硬掩模去除、抑制金属布线的损伤。
本发明中所使用的氢氧化钾的浓度范围为0.01~1质量%、优选为0.05~0.7质量%、特别优选为0.07~0.5质量%。为上述范围内时,能够有效地将TiN硬掩模去除、抑制金属布线的损伤。
作为本发明中所使用的氨基多亚甲基膦酸的例子,例如可以举出:氨基三(亚甲基膦酸)、乙二胺四(亚甲基膦酸)、二亚乙基三胺五(亚甲基膦酸)、1,2-丙二胺四(亚甲基膦酸)等,特别优选可以举出:氨基三(亚甲基膦酸)、二亚乙基三胺五(亚甲基膦酸)、1,2-丙二胺四(亚甲基膦酸)等。这些氨基多亚甲基膦酸可以单独或组合2种以上而配混。
本发明中所使用的氨基多亚甲基膦酸的浓度范围为0.0001~0.01质量%、优选为0.0003~0.003质量%、特别优选为0.0005~0.002质量%。为上述范围内时,能够有效地抑制金属布线的损伤。
作为本发明中所使用的锌盐的例子,例如可以举出:锌的硫酸盐、硝酸盐、盐酸盐、乙酸盐、或乳酸盐等,优选为硫酸锌或硝酸锌。这些锌盐可以单独或组合2种以上而配混。
本发明中所使用的锌盐的浓度范围为0.0001~0.1质量%、优选为0.0005~0.05质量%、特别优选为0.005~0.03质量%。为上述范围内时,能够有效地抑制金属布线的损伤。
本发明的清洗用液体组合物中可以根据期望在不损害本发明的目的的范围内配混以往以来半导体元件的清洗用液体组合物中使用的添加剂。例如,作为添加剂,可以添加表面活性剂、消泡剂等。
本发明的清洗用液体组合物中可以根据期望在不损害本发明的目的的范围内配混唑类。
作为唑类,尤其优选选自1-甲基咪唑、1-乙烯基咪唑、2-苯基咪唑、2-乙基-4-咪唑、N-苄基-2-甲基咪唑、2-甲基苯并咪唑、吡唑、4-甲基吡唑、3,5-二甲基吡唑、1,2,4-***、1H-苯并***、5-甲基-1H-苯并***及1H-四唑中的1种以上的唑,特别优选3,5-二甲基吡唑,但不限定于这些。
本发明的清洗方法是将半导体元件中的氮化钛硬掩模去除的清洗方法,所述半导体元件至少具有选自由包含钴元素的材料和包含铜元素的材料组成的组中的材料和氮化钛硬掩模,所述清洗方法包含使本发明的清洗用液体组合物和前述半导体元件接触的工序。根据本发明的优选的方式,通过使用本发明的清洗方法,能够抑制选自由包含钴元素的材料和包含铜元素的材料组成的组中的材料的腐蚀,并且将氮化钛硬掩模去除。此处“抑制选自由包含钴元素的材料和包含铜元素的材料组成的组中的材料的腐蚀”是指前述材料的蚀刻速率为/分钟(0.01nm/分钟)以下。
对使本发明的清洗用液体组合物和半导体元件接触的方法没有特别限制。例如可以采用使半导体元件浸渍于本发明的清洗用液体组合物的方法;通过滴加、喷雾等使其与清洗用液体组合物接触的方法等。
使用本发明的清洗用液体组合物的温度优选为20~80℃、更优选为25~70℃、特别优选为40~60℃的范围,根据蚀刻的条件、所使用的半导体基体进行适宜选择即可。
本发明的清洗方法可以根据需要组合使用超声波。
使用本发明的清洗用液体组合物的时间优选为0.3~30分钟、更优选为0.5~20分钟、特别优选为1~10分钟的范围,根据蚀刻的条件、所使用的半导体基体进行适宜选择即可。
作为使用本发明的清洗用液体组合物后的冲洗液,可以使用醇那样的有机溶剂,但仅用水冲洗就足够。
图1为具有势垒金属1、金属布线2、帽金属3、势垒绝缘膜4、低介电常数层间绝缘膜5及硬掩模6的半导体元件的概略剖视图,表示利用本发明的清洗用液体组合物清洗的半导体元件的一例。此处,在具有势垒金属1、金属布线2、帽金属3和低介电常数层间绝缘膜5的基板上依次层叠势垒绝缘膜4、低介电常数层间绝缘膜5、硬掩模6,形成规定的图案。
通常半导体元件和显示元件包含硅、非晶硅、多晶硅、玻璃等基板材料;氧化硅、氮化硅、碳化硅及它们的衍生物等绝缘材料;钽、氮化钽、钌、氧化钌等势垒材料;铜、铜合金、钴、钴合金等布线材料;镓-砷、镓-磷、铟-磷、铟-镓-砷、铟-铝-砷等化合物半导体;以及铬氧化物等氧化物半导体等。
通常作为低介电常数层间绝缘膜,使用羟基倍半氧烷(HSQ)系、甲基倍半氧烷(MSQ)系的OCD(商品名、东京应化工业株式会社制)、掺碳氧化硅(SiOC)系的Black Diamond(商品名、Applied Materials公司制)、Aurora(商品名、ASM International公司制)、Coral(商品名、Novellus Systems公司制)等。低介电常数层间绝缘膜不限定于这些。
通常作为势垒金属,使用钽、氮化钽、钌、锰、镁、钴以及它们的氧化物等。势垒金属不限定于这些。
通常作为势垒绝缘膜,使用氮化硅、碳化硅、氮化碳化硅等。势垒绝缘膜不限定于这些。
作为本发明可以应用的硬掩模,使用钛、氮化钛等。本发明中特别使用氮化钛。
作为本发明可以应用的金属布线,使用铜或铜合金、在铜或铜合金上以帽金属的形式形成钴或钴合金的物质、钴或钴合金等。此处“铜合金”是指以质量基准计包含50%以上、优选60%以上、更优选70%以上的铜的合金。“钴合金”是指以质量基准计包含50%以上、优选60%以上、更优选70%以上的钴的合金。
在半导体元件的制造工序的一例中,首先,在具有势垒金属、金属布线、低介电常数层间绝缘膜、根据需要的帽金属的基板上层叠势垒绝缘膜、低介电常数层间绝缘膜、硬掩模及光致抗蚀剂,然后对该光致抗蚀剂实施选择性的曝光和显影处理,形成光致抗蚀图案。接着,通过干蚀刻将该光致抗蚀图案转印到硬掩模上。然后,去除光致抗蚀图案,将该硬掩模作为蚀刻掩模,对低介电常数层间绝缘膜和势垒绝缘膜实施干蚀刻处理。接着,去除硬掩模,从而能够得到具有期望的金属布线图案的半导体元件。本发明的清洗用液体组合物在如这样形成期望的金属布线图案后去除不需要的硬掩模时适合使用。
根据本发明的优选的方式,通过使用本发明的清洗用液体组合物对半导体元件进行清洗,能够抑制金属布线的损伤,并且将氮化钛硬掩模去除,因此能够成品率良好地制造高精度、高质量的半导体元件。
[实施例]
接着,通过实施例和比较例更具体地说明本发明。但是,本发明不受这些实施例的任何限制。
使用晶圆
本实施例中,使用在硅晶圆上具有氮化钛层的“带氮化钛膜的晶圆”(表中记为TiN。Advantech Co.,Ltd.制。)、及在硅晶圆上具有铜层的“带铜膜的晶圆”(表中记为Cu。Advantech Co.,Ltd.制。)、以及在硅晶圆上具有钴层的“带钴膜的晶圆”(表中记为Co。Advantech Co.,Ltd.制。)。
氮化钛膜厚测定
带氮化钛膜的晶圆的氮化钛膜厚使用SII NanoTechnology Inc.制荧光X射线装置SEA1200VX来测定。
氮化钛的蚀刻速率的测定和判定
铜和钴的蚀刻速率的测定和判定
使用Thermo Scientific公司制电感耦合等离子体发射光谱分析装置iCAP6300对带铜或钴膜的晶圆处理后的清洗液中的铜或钴浓度进行测定。由测定结果的浓度和使用的清洗液量算出溶解的铜或钴量,用该溶解的铜或钴量除以密度来算出溶解的铜或钴的体积。将该溶解的铜或钴的体积除以处理过的带膜的晶圆的面积和处理时间而得到的值定义为蚀刻速率来算出。将铜或钴的蚀刻速率为/分钟(0.01nm/分钟)以下记为合格。
实施例1~9
使用带氮化钛膜的晶圆,对氮化钛的去除性进行研究。使用表1中所记的1A~1I的清洗用液体组合物,在表2所示的温度下浸渍3分钟,然后,进行利用超纯水的冲洗、基于干燥氮气喷射的干燥。通过荧光X射线装置求出浸渍前后的膜厚,算出蚀刻速率,将结果总结于表2。
接着,使用带铜和钴膜的晶圆,使用表1中所记的1A~1I的清洗用液体组合物,对铜和钴的防蚀性进行研究。在表2所示的温度下浸渍30分钟,然后,进行利用超纯水的冲洗、基于干燥氮气喷射的干燥。通过电感耦合等离子体发射光谱分析装置求出浸渍后的清洗液中的铜或钴浓度,算出蚀刻速率、将结果示于表2。
在实施例1的使用清洗用液体组合物1A(过氧化氢15质量%、氢氧化钾0.2质量%、1,2-丙二胺四(亚甲基膦酸)(PDTP)0.002质量%、硫酸锌0.01质量%的水溶液)的情况下,氮化钛的蚀刻速率为/分钟(21nm/分钟)、为合格,铜和钴的蚀刻速率为/分钟(0.01nm/分钟)以下,判定为合格。
在实施例2~9的应用表2所示的本发明的清洗用液体组合物的情况下,可知氮化钛的蚀刻速率为/分钟(10nm/分钟)以上、为合格,能够良好地去除氮化钛。另外可知,铜和钴的蚀刻速率为/分钟(0.01nm/分钟)以下、能够抑制铜和钴的损伤。
比较例1~21
使用表3中所记的清洗液2A~2U,在表4所示的温度下使带氮化钛、铜、钴膜的晶圆浸渍,除此以外,进行与实施例1~9同样的操作,算出氮化钛、铜、钴各自的蚀刻速率。
对于比较例1、3、7、8、10~12、15~21,氮化钛的蚀刻速率为/分钟(10nm/分钟)以上,但铜和钴的蚀刻速率超过/分钟(0.01nm/分钟)。使用清洗液2A、2C、2G、2H、2J、2K、2L、2O、2P、2Q、2R、2S、2T、2U的清洗方法能够良好地去除氮化钛,但由于给铜和钴带来损伤,因此无法用于本申请目的。
[表1]
需要说明的是,表中PDTP是指1,2-丙二胺四(亚甲基膦酸)、DTPP是指二亚乙基三胺五(亚甲基膦酸)、ATP是指氨基三(亚甲基膦酸)。
[表2]
[表3]
需要说明的是,表中PDTP是指1,2-丙二胺四(亚甲基膦酸)、DTPP是指二亚乙基三胺五(亚甲基膦酸)、ATP是指氨基三(亚甲基膦酸)、TMAH是指四甲基氢氧化铵、EDTA是指乙二胺四乙酸、DGME是指二乙二醇单甲基醚。
[表4]
Claims (6)
1.一种清洗用液体组合物,其抑制包含钴元素的材料和包含铜元素的材料的腐蚀,并且将氮化钛硬掩模去除,所述清洗用液体组合物包含1~30质量%的过氧化氢、0.07~0.5质量%的氢氧化钾、0.0003~0.002质量%的氨基多亚甲基膦酸、0.0001~0.1质量%的锌盐、以及水,所述锌盐为选自由硫酸锌和硝酸锌组成的组中的1种以上,所述氨基多亚甲基膦酸为选自由氨基三(亚甲基膦酸)、二亚乙基三胺五(亚甲基膦酸)及1,2-丙二胺四(亚甲基膦酸)组成的组中的1种以上。
2.根据权利要求1所述的清洗用液体组合物,其中,所述包含钴元素的材料为钴或钴合金,所述包含铜元素的材料为铜或铜合金。
3.一种清洗方法,其是将半导体元件中的氮化钛硬掩模去除的半导体元件的清洗方法,所述半导体元件至少具有包含钴元素的材料和包含铜元素的材料和氮化钛硬掩模,
所述清洗方法包含使清洗用液体组合物和所述半导体元件接触的工序,所述清洗用液体组合物包含1~30质量%的过氧化氢、0.07~0.5质量%的氢氧化钾、0.0003~0.002质量%的氨基多亚甲基膦酸、0.0001~0.1质量%的锌盐、以及水,所述锌盐为选自由硫酸锌和硝酸锌组成的组中的1种以上,所述氨基多亚甲基膦酸为选自由氨基三(亚甲基膦酸)、二亚乙基三胺五(亚甲基膦酸)及1,2-丙二胺四(亚甲基膦酸)组成的组中的1种以上。
4.根据权利要求3所述的清洗方法,其中,所述包含钴元素的材料为钴或钴合金,所述包含铜元素的材料为铜或铜合金。
5.一种半导体元件的制造方法,所述半导体元件具有包含钴元素的材料和包含铜元素的材料,
所述制造方法包含使用清洗用液体组合物,抑制所述包含钴元素的材料和包含铜元素的材料的腐蚀,并且将氮化钛硬掩模去除的工序,所述清洗用液体组合物包含1~30质量%的过氧化氢、0.07~0.5质量%的氢氧化钾、0.0003~0.002质量%的氨基多亚甲基膦酸、0.0001~0.1质量%的锌盐、以及水,所述锌盐为选自由硫酸锌和硝酸锌组成的组中的1种以上,所述氨基多亚甲基膦酸为选自由氨基三(亚甲基膦酸)、二亚乙基三胺五(亚甲基膦酸)及1,2-丙二胺四(亚甲基膦酸)组成的组中的1种以上。
6.根据权利要求5所述的制造方法,其中,所述包含钴元素的材料为钴或钴合金,所述包含铜元素的材料为铜或铜合金。
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