CN104823267B - 半导体元件用清洗液及使用它的清洗方法 - Google Patents
半导体元件用清洗液及使用它的清洗方法 Download PDFInfo
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- CN104823267B CN104823267B CN201380062660.6A CN201380062660A CN104823267B CN 104823267 B CN104823267 B CN 104823267B CN 201380062660 A CN201380062660 A CN 201380062660A CN 104823267 B CN104823267 B CN 104823267B
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- cleaning fluid
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- dielectric film
- hard mask
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- 239000010949 copper Substances 0.000 claims abstract description 73
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- LRGJRHZIDJQFCL-UHFFFAOYSA-M tetraethylazanium;hydroxide Chemical compound [OH-].CC[N+](CC)(CC)CC LRGJRHZIDJQFCL-UHFFFAOYSA-M 0.000 claims description 6
- LPSKDVINWQNWFE-UHFFFAOYSA-M tetrapropylazanium;hydroxide Chemical compound [OH-].CCC[N+](CCC)(CCC)CCC LPSKDVINWQNWFE-UHFFFAOYSA-M 0.000 claims description 6
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- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 description 1
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- HIQXJRBKNONWAH-UHFFFAOYSA-N methylidenephosphane Chemical compound P=C HIQXJRBKNONWAH-UHFFFAOYSA-N 0.000 description 1
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- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 1
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- 238000002360 preparation method Methods 0.000 description 1
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- WOCIAKWEIIZHES-UHFFFAOYSA-N ruthenium(iv) oxide Chemical compound O=[Ru]=O WOCIAKWEIIZHES-UHFFFAOYSA-N 0.000 description 1
- 239000004576 sand Substances 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- LIVNPJMFVYWSIS-UHFFFAOYSA-N silicon monoxide Chemical compound [Si-]#[O+] LIVNPJMFVYWSIS-UHFFFAOYSA-N 0.000 description 1
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- 230000002459 sustained effect Effects 0.000 description 1
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- VDZOOKBUILJEDG-UHFFFAOYSA-M tetrabutylammonium hydroxide Chemical compound [OH-].CCCC[N+](CCCC)(CCCC)CCCC VDZOOKBUILJEDG-UHFFFAOYSA-M 0.000 description 1
- 239000010409 thin film Substances 0.000 description 1
- ZMANZCXQSJIPKH-UHFFFAOYSA-O triethylammonium ion Chemical compound CC[NH+](CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-O 0.000 description 1
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Classifications
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
- C11D3/39—Organic or inorganic per-compounds
- C11D3/3947—Liquid compositions
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D7/00—Compositions of detergents based essentially on non-surface-active compounds
- C11D7/02—Inorganic compounds
- C11D7/04—Water-soluble compounds
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D7/00—Compositions of detergents based essentially on non-surface-active compounds
- C11D7/02—Inorganic compounds
- C11D7/04—Water-soluble compounds
- C11D7/06—Hydroxides
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D7/00—Compositions of detergents based essentially on non-surface-active compounds
- C11D7/22—Organic compounds
- C11D7/32—Organic compounds containing nitrogen
- C11D7/3209—Amines or imines with one to four nitrogen atoms; Quaternized amines
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D7/00—Compositions of detergents based essentially on non-surface-active compounds
- C11D7/22—Organic compounds
- C11D7/36—Organic compounds containing phosphorus
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23G—CLEANING OR DE-GREASING OF METALLIC MATERIAL BY CHEMICAL METHODS OTHER THAN ELECTROLYSIS
- C23G1/00—Cleaning or pickling metallic material with solutions or molten salts
- C23G1/14—Cleaning or pickling metallic material with solutions or molten salts with alkaline solutions
- C23G1/20—Other heavy metals
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23G—CLEANING OR DE-GREASING OF METALLIC MATERIAL BY CHEMICAL METHODS OTHER THAN ELECTROLYSIS
- C23G1/00—Cleaning or pickling metallic material with solutions or molten salts
- C23G1/14—Cleaning or pickling metallic material with solutions or molten salts with alkaline solutions
- C23G1/20—Other heavy metals
- C23G1/205—Other heavy metals refractory metals
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Abstract
通过用包含10~30质量%过氧化氢、0.005~10质量%季铵氢氧化物、0.005~5质量%氢氧化钾、0.000005~0.005质量%氨基多亚甲基膦酸、以及水的清洗液进行清洗,从而能够去除硬掩模(5)、有机硅氧烷系薄膜(6)、干法蚀刻残渣(8)以及光致抗蚀层(7)而不腐蚀低介电常数层间绝缘膜(4)、铜或铜合金等的布线材料(2)、阻隔金属层(1)以及阻隔绝缘膜(3)。另外,根据本发明的优选的方式,即使在清洗液中添加了酸的情况下也抑制铜布线的损伤、即使在清洗液添加了钛的情况下也不引起较大的过氧化氢的分解。
Description
技术领域
本发明涉及在半导体集成电路的制造工序中使用的清洗剂及使用它的清洗方法。本发明尤其涉及清洗液及使用它的清洗方法,该清洗液对下述半导体元件进行清洗,抑制低介电常数层间绝缘膜、铜布线、阻隔金属层、以及阻隔绝缘膜的损伤,并且去除前述有机硅氧烷系薄膜、硬掩模、干法蚀刻残渣以及光致抗蚀层,所述半导体元件为:在具有阻隔金属层、铜布线或铜合金布线、和低介电常数层间绝缘膜的基板上,依次层叠了阻隔绝缘膜、低介电常数层间绝缘膜、硬掩模、有机硅氧烷系薄膜、以及光致抗蚀层后,对该光致抗蚀层实施选择性曝光和显影处理以形成光致抗蚀图案,接着将该光致抗蚀图案作为掩模,清洗对前述有机硅氧烷系薄膜、硬掩模、低介电常数层间绝缘膜、阻隔绝缘膜实施了干法蚀刻处理的半导体元件,。
背景技术
高集成化的半导体元件的制造,通常而言,一般采用在硅晶片等的元件上形成为导电用布线原材料的金属膜等的导电薄膜、以进行导电薄膜间的绝缘为目的的层间绝缘膜后,在其表面上均匀地涂布光致抗蚀剂来设置感光层,对其实施选择性曝光和显影处理来制作所希望的光致抗蚀图案。接着,通过将该光致抗蚀图案作为掩模在层间绝缘膜上实施干法蚀刻处理,从而在该薄膜上形成所希望的图案。随后,由利用氧等离子体的灰化、清洗液等完全地去除光致抗蚀图案和由干法蚀刻处理产生的残渣物(以下,称为“干法蚀刻残渣”)的一系列的工序。
近年来,随着设计标准的微细化,信号传送延迟逐渐变得决定着高速度演算处理的极限。因此,导电用布线原材料从铝向电阻更低的铜过渡,与此相伴,正在进行层间绝缘膜由硅氧化膜向低介电常数层间绝缘膜(相对介电常数比3更小的膜,以下称为“低介电常数层间绝缘膜”)的过渡。另外,为了防止铜向层间绝缘膜扩散,铜被钽、氮化钽等金属(以下称为“阻隔金属层”)和氮化硅、碳化硅等绝缘膜(以下称为“阻隔绝缘膜”)覆盖。进而,正在使用如下的膜:具有填充在光致抗蚀层与层间绝缘膜之间的基底元件的凸凹、沟等间隙而平坦化的功能、吸收由元件反射的辐射线的功能、以及在干法蚀刻时保持层间绝缘膜的形状易于精密微细加工的功能的膜。这样的膜有例如,包含光吸收化合物的有机硅氧烷薄膜(以下称为“有机硅氧烷系薄膜”)。另外,形成0.2μm以下的图案的情况下,对于膜厚1μm的抗蚀层来说图案的深宽比(抗蚀层膜厚除以抗蚀层线宽的比值)变得过大,产生图案倒塌等问题。为了解决该问题,有时使用在实际欲形成的图案膜与抗蚀层膜之间插入Ti系、Si系的膜(以下,称为“硬掩模”),先将光致抗蚀图案以干法蚀刻转印到硬掩模上,之后将该硬掩模作为蚀刻掩模,利用干法蚀刻将图案转印到实际欲形成的膜上的硬掩模法。对于该方法,能够交换蚀刻硬掩模时的气体与蚀刻实际欲形成的膜时的气体,可以选择蚀刻硬掩模时取得与抗蚀层的选择比,蚀刻实际的膜时取得与硬掩模的选择比的气体,因此存在能够以薄的抗蚀层形成图案的优点。
但是,将硬掩模、有机硅氧烷系薄膜、光致抗蚀层利用氧等离子体去除的情况下,在有机硅氧烷系薄膜之下存在的低介电常数层间绝缘膜,有由于被暴露在氧等离子体等下而受到损伤之虞。例如,利用先形成通孔的双镶嵌工艺(Via-first Dual damasceneprocess)的图案形成中,将在通孔部所填充的有机硅氧烷系薄膜用氧等离子体去除时,通孔部周围的低介电常数层间绝缘膜受到损伤,结果出现电特性显著恶化这样的问题。另一方面,在硬掩模、有机硅氧烷系薄膜的去除工序中,干法蚀刻残渣附着于硅晶片上,因此必须同时也去除干法蚀刻残渣。因此,在使用低介电常数层间绝缘膜的半导体元件制造中,要求抑制低介电常数层间绝缘膜、铜、阻隔金属层以及阻隔绝缘膜的损伤,并且与氧等离子体工序同程度地去除硬掩模、有机硅氧烷系薄膜、光致抗蚀层,同时也去除干法蚀刻残渣的方法。
近年来,在干法蚀刻中通常使用碳氟系的气体,因此干法蚀刻残渣中含有氟。因此,在干法蚀刻残渣的去除过程中,氟混入到清洗液中。氟尤其是在pH为酸性的情况下,会对低介电常数层间绝缘膜和铜造成严重的损伤。另外,即使清洗液的pH不为酸性的情况下,使用去除干法蚀刻残渣后的清洗液清洗半导体元件时,有时存在低介电常数层间绝缘膜和铜上也观察到严重的损伤的情况。该损伤的原因尚未明确,预想是在用碳氟系的气体干法蚀刻包含Si、O的低介电常数层间绝缘膜时,与用HF溶解SiO2的情况同样地,干法蚀刻残渣的一部分变为H2SiF6这样的酸。认为在干法蚀刻气体的影响下半导体元件上也存在氟,因此在用清洗液进行清洗的同时局部地形成氢氟酸,引起了低介电常数层间绝缘膜和铜的损伤。因此,需求即使在干法蚀刻残渣混入到清洗液的情况下,也不对低介电常数层间绝缘膜和铜造成损伤的清洗半导体元件的方法。
作为硬掩模存在使用钛或氮化钛的情况。该情况下,若用清洗液去除硬掩模,则在清洗液中混入了钛。包含过氧化氢的清洗液的情况下,若混入了钛,则过氧化氢的分解被加速,清洗液的保存稳定性恶化,因此需求抑制由于清洗液中混入的钛导致过氧化氢分解的方法。
专利文献1中提出了利用包含过氧化氢、氨基多亚甲基膦酸类、氢氧化钾以及水的清洗液的半导体元件的清洗方法。
专利文献2中提出了一种清洗液,其特征在于,其为含有过氧化氢、氢氧化季铵以及钨的防蚀剂、pH为7以上且10以下的、布线基板的处理液,钨的防蚀剂为选自由季铵及其盐、季吡啶鎓及其盐、季联吡啶鎓及其盐、以及季咪唑鎓及其盐组成的组中的至少一种。
专利文献3中,提出了含有10~40质量%的过氧化氢和四烷基氢氧化铵,且在25℃下的pH为6.0~8.2的氮化钛去除液。
专利文献4中,提出了包含氧化剂、金属蚀刻剂、以及表面活性剂,且pH为10~14的半导体器件用清洗剂。
专利文献5中,提出了将钛配合物作为主要的催化剂来制造的聚酯,作为该钛配合物的螯合剂可列举出羟基多元羧酸和/或含氮多元羧酸。
现有技术文献
专利文献
专利文献1:WO2008/114616
专利文献2:日本特开2008-285508号公报
专利文献3:日本特开2010-10273号公报
专利文献4:日本特开2009-231354号公报
专利文献5:日本特开2007-211035号公报
发明内容
发明要解决的问题
但是在专利文献1~5中,存在无法充分地去除硬掩模、有机硅氧烷系薄膜、光致抗蚀层、以及干法蚀刻残渣,或在清洗液中混入了酸的情况下无法充分地抑制对铜的损伤的问题点。进而,存在钛混入至清洗液的情况下过氧化氢的分解程度大等问题点(参照后述的比较例1~5)。
本发明鉴于上述现有的问题,以提供抑制低介电常数层间绝缘膜、铜布线、阻隔金属层、以及阻隔绝缘膜的损伤,并且去除有机硅氧烷系薄膜、硬掩模、干法蚀刻残渣以及光致抗蚀层的清洗液及使用它的清洗方法作为课题。进而,本发明以提供即使在清洗液中添加了酸的情况下也抑制铜布线的损伤、即使在清洗液中添加了钛的情况下也不引起较严重的过氧化氢的分解的清洗液以及使用它的清洗方法作为课题。
用于解决问题的方案
本发明包含以下的方式。
<1>一种清洗液,其为对下述半导体元件进行清洗,去除下述有机硅氧烷系薄膜、硬掩模、干法蚀刻残渣以及光致抗蚀层的清洗液,
所述半导体元件为在具有阻隔金属层、铜布线或铜合金布线、低介电常数层间绝缘膜的基板上依次层叠阻隔绝缘膜、低介电常数层间绝缘膜、硬掩模、有机硅氧烷系薄膜、以及光致抗蚀层后,对该光致抗蚀层实施选择性曝光和显影处理,形成光致抗蚀图案,接着将该光致抗蚀图案作为掩模,对前述有机硅氧烷系薄膜、硬掩模、低介电常数层间绝缘膜以及阻隔绝缘膜实施了干法蚀刻处理的半导体元件,
所述清洗液包含10~30质量%过氧化氢、0.005~10质量%季铵氢氧化物、0.005~5质量%氢氧化钾、0.000005~0.005质量%氨基多亚甲基膦酸、以及水。
<2>根据<1>记载的清洗液,其中,前述硬掩模含有氮化钛或钛。
<3>根据<1>或<2>记载的清洗液,其中,前述季铵氢氧化物为选自由氢氧化四甲基铵、氢氧化四乙基铵、氢氧化四丙基铵、氢氧化四丁基铵以及氢氧化苄基三甲基铵组成的组中的至少1种以上。
<4>根据<1>~<3>中任一项记载的清洗液,其中,前述氨基多亚甲基膦酸为选自由氨基三(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)以及1,2-丙二胺四(亚甲基膦酸)组成的组中的至少1种以上。
<5>根据<1>~<4>中任一项记载的清洗液,其中,钠浓度为0.1ppm以下。
<6>一种半导体元件的清洗方法,其特征在于,对下述半导体元件使用清洗液,去除下述硬掩模、有机硅氧烷系薄膜、干法蚀刻残渣以及光致抗蚀层,
所述半导体元件为在具有阻隔金属层、铜布线或铜合金布线、低介电常数层间绝缘膜的基板上依次层叠阻隔绝缘膜、低介电常数层间绝缘膜、硬掩模、有机硅氧烷系薄膜、以及光致抗蚀层后,对该光致抗蚀层实施选择性曝光和显影处理,形成光致抗蚀图案,接着将该光致抗蚀图案作为掩模,对前述有机硅氧烷系薄膜、硬掩模、低介电常数层间绝缘膜以及阻隔绝缘膜实施了干法蚀刻处理的半导体元件,
所述清洗液包含10~30质量%过氧化氢、0.005~10质量%季铵氢氧化物、0.005~5质量%氢氧化钾、0.000005~0.005质量%氨基多亚甲基膦酸、以及水。
<7>根据<6>记载的清洗方法,其中前述硬掩模含有氮化钛或钛。
<8>根据<6>或<7>记载的清洗方法,其中,前述季铵氢氧化物为选自由氢氧化四甲基铵、氢氧化四乙基铵、氢氧化四丙基铵、氢氧化四丁基铵以及氢氧化苄基三甲基铵组成的组中的至少1种以上。
<9>根据<6>~<8>中任一项记载的清洗方法,其中,前述氨基多亚甲基膦酸为选自由氨基三(亚甲基膦酸)、乙二胺四(亚甲基膦酸)、二亚乙基三胺五(亚甲基膦酸)以及1,2-丙二胺四(亚甲基膦酸)组成的组中的至少1种以上。
<10>根据<6>~<9>中任一项记载的清洗方法,其中,钠含量为0.1ppm以下。
发明的效果
根据本发明的优选的方式,能够提供抑制低介电常数层间绝缘膜、铜布线、阻隔金属层、以及阻隔绝缘膜的损伤,并且去除硬掩模、有机硅氧烷系薄膜、干法蚀刻残渣以及光致抗蚀层的清洗液以及使用它的清洗方法。进而,根据本发明的优选的方式,可以提供即使在清洗液中添加了酸的情况下也抑制铜布线的损伤、即使在清洗液添加了钛的情况下也不引起较大的过氧化氢的分解的清洗液以及使用它的清洗方法,能够生产率良好地制造高精度、高品质的半导体元件。
附图说明
[图1]图1为包含阻隔金属层、铜布线或铜合金布线、阻隔绝缘膜、低介电常数层间绝缘膜、硬掩模、有机硅氧烷系薄膜、干法蚀刻残渣以及光致抗蚀层的半导体元件的示意性截面图。
具体实施方式
以下,针对本发明示出实施方式和示例物等来进行详细地说明,但是本发明不受以下示出的实施方式和例示物等的限定,可以在不超出本发明的要旨的范围里任意地进行变更来实施。
本发明的清洗液包含10~30质量%过氧化氢、0.005~10质量%季铵氢氧化物、0.005~5质量%氢氧化钾、0.000005~0.005质量%氨基多亚甲基膦酸、以及水。以下,针对各成分进行详细地说明。
本发明中使用的过氧化氢的浓度范围为10~30质量%、优选为13~25质量%、特别优选为15~20质量%。为10~30质量%时,能够将硬掩模、有机硅氧烷系薄膜、干法蚀刻残渣以及光致抗蚀层有效地去除。
作为本发明中使用的季铵氢氧化物的具体例子,例如可列举出,氢氧化四甲基铵、氢氧化四乙基铵、氢氧化四丙基铵、氢氧化四丁基铵、氢氧化苄基三甲基铵等。这些季铵氢氧化物可以单独或组合2种以上地进行混合。
本发明中使用的上述季铵氢氧化物的浓度范围为0.005~10质量%、优选为0.01~8质量%、特别优选为0.05~5质量%。为0.005~10质量%的范围内时,能够抑制低介电常数层间绝缘膜以及铜布线的损伤,并且有效地进行硬掩模、有机硅氧烷系薄膜、干法蚀刻残渣以及光致抗蚀层的去除,即使在清洗液中添加了酸的情况下也抑制铜布线的损伤、即使在清洗液添加了钛的情况下也不引起较大的过氧化氢的分解。
本发明中使用的氢氧化钾的浓度范围为0.005~5质量%、优选为0.01~3质量%、特别优选为0.02~1质量%。为0.005~5质量%的范围内时,能够抑制低介电常数层间绝缘膜以及铜布线的损伤,并且有效地进行硬掩模、有机硅氧烷系薄膜、干法蚀刻残渣以及光致抗蚀层的去除。
作为本发明中使用的氨基多亚甲基膦酸的例子,例如可列举出,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。这些氨基多亚甲基膦酸可以单独或组合2种以上地进行混合。
本发明中使用的上述氨基多亚甲基膦酸的浓度范围为0.000005~0.005质量%、优选为0.00001~0.003质量%、特别优选为0.0001~0.003质量%。为0.000005~0.005质量%的范围内时,能够抑制铜布线的损伤。
在本发明的清洗液中,特别优选的组合是含有15~20质量%过氧化氢、0.01~8质量%季铵氢氧化物、0.02~1质量%氢氧化钾、0.00001~0.003质量%氨基多亚甲基膦酸。
作为本发明的清洗液中包含的杂质的钠浓度,以质量计优选为0.1ppm以下、更优选为0.05ppm以下、进一步优选为0.03ppm以下。需要说明的是,在上述氢氧化钾中钠是不可避免的杂质,因此实际上在清洗用组合物中包含了0.001ppm左右。若包含多于0.1ppm的钠,则有制造的半导体的特性降低之虞。
作为使用了本发明的清洗液的硬掩模,例如可以使用氮化钛或钛。
在本发明的清洗液中,根据期望也可以在不损害本发明的目的的范围内,混合现有的半导体用清洗液中使用的添加剂。
例如,作为添加剂,可以添加表面活性剂、消泡剂等。
使用本发明的清洗液的温度为20~80℃、优选为25~70℃的范围,根据蚀刻的条件、所使用的半导体基体进行适宜地选择即可。本发明的清洗方法,根据需要可以并用超声波。
使用本发明的清洗液的时间为0.3~20分钟、优选为0.5~10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地选择即可。
作为使用本发明的清洗液后的冲洗液,可以使用醇这样的有机溶剂,但是即使仅以水进行冲洗也是足够的。
本发明可以适用的半导体元件以及显示元件包含硅、无定形硅、多晶硅、玻璃等基板材料;氧化硅、氮化硅、碳化硅以及它们的衍生物等绝缘材料;钽、氮化钽、钌、氧化钌等阻隔材料;铜、铜合金等布线材料;镓-砷、镓-磷、铟-磷、铟-镓-砷、铟-铝-砷等化合物半导体;铬氧化物等氧化物半导体等。
一般而言作为低介电常数层间绝缘膜,可以使用氢化硅倍半氧烷(HSQ)系、甲基硅倍半氧烷(MSQ)系的OCD(商品名,东京应化工业公司制)、碳掺杂氧化硅(SiOC)系的BlackDiamond(商品名,Applied Materials Inc.制)、Aurora(商品名,ASM International制)、Coral(商品名,Novellus Systems制)、无机系的Orion(商品名,Trikon Tencnlogies制)。低介电常数层间绝缘膜不限定于这些。
通常作为阻隔金属层,可以使用钽、氮化钽、钌、锰、镁、钴以及它们的氧化物。阻隔金属层不限定于这些。
通常作为阻隔绝缘膜,可以使用氮化硅、碳化硅、氮碳化硅。阻隔绝缘膜不限定于这些。
实施例
接着,根据实施例和比较例进一步对本发明进行具体地说明。但是,本发明不受这些实施例的任何限制。
<材质的去除状态和损伤的评价方法以及评价仪器>
材质的去除状态和损伤的评价在SEM观察下进行。SEM装置使用Hitachi High-Technologies Corporation.制的超高分辨场发射扫描电子显微镜SU9000。
<添加了酸的清洗液的制备方法和用添加了酸的清洗液进行清洗的情况下的铜的损伤的评价方法>
添加了酸的清洗液是在清洗液中以质量计为100:2的比例混合10质量%氢氟酸水溶液而制备的。将具有铜布线的半导体元件以规定的温度和规定的时间浸渍于添加了氢氟酸的清洗液中,对铜的损伤进行SEM观察。
<添加了钛的清洗液的过氧化氢的分解率>
将以质量计为100:0.005的比例混合清洗液与钛粉末得到的组合物在60℃的恒温水槽中加热4小时。对加热前后的过氧化氢浓度用电位滴定法(使用高锰酸钾)进行测定,根据以下的计算式算出组合物的过氧化氢分解率。
过氧化氢分解率%=100-100×(加热后清洗液重量×加热后过氧化氢浓度)/(加热前清洗液重量×加热前过氧化氢浓度)
判定:
I.有机硅氧烷系薄膜6的去除状态
A:有机硅氧烷系薄膜完全地被去除了。
B:有机硅氧烷系薄膜基本被去除了。
C:有机硅氧烷系薄膜未被去除。
将A、B视为合格。
II.干法蚀刻残渣8的去除状态
A:干法蚀刻残渣完全地被去除了。
B:干法蚀刻残渣基本被去除了。
C:干法蚀刻残渣未被去除。
将A、B视为合格。
III.劣化光致抗蚀层7的去除状态
A:光致抗蚀层完全地被去除了。
B:光致抗蚀层基本被去除了。
C:光致抗蚀层未被去除。
将A、B视为合格。
IV.钛系硬掩模5的去除状态
A:硬掩模完全地被去除了。
B:硬掩模基本被去除了。
C:硬掩模未被去除。
将A、B视为合格。
V.铜2的损伤
A:与清洗前对比,铜上未发现变化。
B:铜表面上发现少许粗糙。
C:铜上发现较大的洞。
将A、B视为合格。
VI.低介电常数层间绝缘膜4的损伤
A:与清洗前相比,低介电常数层间绝缘膜上未发现变化。
B:低介电常数层间绝缘膜稍稍凹陷。
C:低介电常数层间绝缘膜显著凹陷。
将A、B视为合格。
VII.用添加了酸的清洗液进行清洗的情况下的铜2的损伤
A:与清洗前对比,铜上未发现变化。
B:铜表面上发现少许粗糙。
C:铜上发现较大的洞。
将A、B视为合格。
VIII.添加了钛的清洗液的过氧化氢的稳定性
A:过氧化氢分解率不足20%。
B:过氧化氢分解率为20~30%。
C:过氧化氢分解率大于30%。
-:从加热前开始就不包含过氧化氢,因此未评价。
将A、B视为合格。
(实施例1~22)
试验中,使用了具有如图1所示那样的布线结构的截面的半导体元件。为了去除为TiN的硬掩模5、有机硅氧烷系薄膜6、干法蚀刻残渣8以及光致抗蚀层7,在表1中记述的清洗液中以表2所示的温度、时间进行浸渍,之后,进行利用超纯水的冲洗、利用干燥氮气喷射的干燥。通过对清洗后的半导体元件用SEM进行观察,判断硬掩模5、有机硅氧烷系薄膜6、干法蚀刻残渣8以及光致抗蚀层7的去除状态,和铜2、作为阻隔金属层1的钽(Ta)/氮化钽(TaN)、作为阻隔绝缘膜3的碳化硅、以及作为低介电常数层间绝缘膜4的碳掺杂氧化硅的损伤。另外,即使为在表1中记述的清洗液中添加了酸的清洗液,也以表2中所示的温度、时间进行浸渍,之后,进行利用超纯水的冲洗、利用干燥氮气喷射的干燥,对清洗后的半导体元件用SEM进行观察,从而观察铜的损伤。进而,也考察了在清洗液中添加了钛的情况下的过氧化氢的稳定性。
使用了表2所示的本发明的清洗液的实施例1~22中,可知防止铜2和低介电常数层间绝缘膜4的损伤,并且完全地去除硬掩模5、有机硅氧烷系薄膜6、干法蚀刻残渣8以及光致抗蚀层7。全部的实施例中,均未观察到阻隔金属层1和阻隔绝缘膜3的损伤。另外,即使是使用添加了酸的清洗液的情况下,铜2上也未观察到损伤。清洗液中添加了钛的情况下,过氧化氢的分解为30%以下。表1所示的清洗液的钠浓度均为0.1ppm以下。
(比较例1)
使用专利文献1记载的包含15质量%过氧化氢、0.02质量%氢氧化钾、0.0005质量%1,2-丙二胺四(亚甲基膦酸)、以及84.9795质量%水的水溶液(表3的清洗液3A),清洗图1所示的半导体元件。表4中示出清洗条件和评价结果。能够去除硬掩模5、有机硅氧烷系薄膜6、干法蚀刻残渣8以及光致抗蚀层7。在低介电常数层间绝缘膜4和铜2上未观察到损伤。但是,使用添加了酸的清洗液的情况下,在铜2上观察到损伤,向清洗液中添加了钛的情况下,过氧化氢的分解程度大。
(比较例2)
使用专利文献2记载的包含15质量%过氧化氢、0.45质量%氢氧化苄基三甲基铵、0.01质量%苯扎氯胺(Benzalkoniumchloride)、以及84.54质量%水的水溶液(表3的清洗液3B),清洗图1所示的半导体元件。表4中示出清洗条件和评价结果。能够去除硬掩模5,但是不能去除有机硅氧烷系薄膜6、干法蚀刻残渣8以及光致抗蚀层7。在低介电常数层间绝缘膜4和铜2上未观察到损伤。即使是使用添加了酸的清洗液的情况下,在铜2上也未观察到损伤。即使是向清洗液添加了钛的情况下,过氧化氢的分解也较小。
(比较例3)
使用专利文献3记载的包含28.4质量%过氧化氢、1.7质量%氢氧化四甲基铵、1.4质量%乙二胺四乙酸、以及68.5质量%水的水溶液(表3的清洗液3C),清洗图1所示的半导体元件。表4中示出清洗条件和评价结果。能够去除硬掩模5,但是不能去除有机硅氧烷系薄膜6、干法蚀刻残渣8以及光致抗蚀层7。在低介电常数层间绝缘膜4上未观察到损伤,但是在铜2上观察到损伤。进而,在使用添加了酸的清洗液的情况下,在铜2上观察到损伤,向清洗液中添加了钛的情况下,过氧化氢的分解程度大。
(比较例4)
使用了专利文献4记载的包含0.2质量%过氧化氢、0.4质量%氢氧化四甲基铵、0.1质量%氢氧化钾、0.2质量%原高碘酸(Orthoperiodic Acid)、0.02质量%二亚乙基三胺、0.1质量%EMULGEN A-90、0.01质量%十六烷基三甲基氯化铵、0.05质量%十二烷基氯化吡啶(Laurylpyridinium Chloride)、0.5质量%三甲基氟化铵、以及98.42质量%水的水溶液(表3的清洗液3D),清洗图1所示的半导体元件。表4示出清洗条件和评价结果。不能去除硬掩模5、有机硅氧烷系薄膜6、干法蚀刻残渣8以及光致抗蚀层7。在低介电常数层间绝缘膜4和铜2上观察到损伤。使用添加了酸的清洗液的情况下,在铜2上观察到损伤。在清洗液中添加了钛的情况下,过氧化氢的分解较小。
(比较例5)
以专利文献5记载的作为与钛形成配位化合物的螯合剂的羟基多元羧酸代替季铵氢氧化物,使用将所述羟基多元羧酸添加到过氧化氢、氢氧化钾、氨基多亚甲基膦酸以及水中而得到的清洗液(表3的清洗液3E),清洗图1所示的半导体元件。表4示出清洗条件和评价结果。硬掩模5、有机硅氧烷系薄膜6、干法蚀刻残渣8以及光致抗蚀层7大多被去除了。在低介电常数层间绝缘膜4上未观察到损伤,但是在铜2上观察到损伤。使用添加了酸的清洗液的情况下,在铜2上观察到损伤。清洗液中添加了钛的情况下,过氧化氢的分解程度变得没那么大。因此,即便在羟基多元羧酸与过氧化氢、氢氧化钾、氨基多亚甲基膦酸以及水组合而成的清洗液中添加了酸的情况下,也对铜布线造成损伤。
专利文献1~5记载的清洗液(比较例1~5),作为抑制阻隔金属层、低介电常数层间绝缘膜、以及铜布线的损伤,并且将硬掩模、有机硅氧烷系薄膜、干法蚀刻残渣以及光致抗蚀层去除的清洗液,可知清洗是不充分的、或有铜布线的损伤、或清洗液的稳定性差,是不能使用的(表4)。
(比较例6)
使用包含17质量%过氧化氢、0.5质量%氢氧化四甲基铵、0.2质量%氢氧化钾、以及82.3质量%水的水溶液(表3的清洗液3F),清洗图1所示的半导体元件。表4示出清洗条件和评价结果。能够去除硬掩模5、有机硅氧烷系薄膜6、干法蚀刻残渣8以及光致抗蚀层7。在低介电常数层间绝缘膜4和铜2上未观察到损伤。即使是使用添加了酸的清洗液的情况下,在铜2上也未观察到损伤。但是,向清洗液添加了钛的情况下,过氧化氢的分解较大。
(比较例7)
使用包含17质量%过氧化氢、0.5质量%氢氧化四甲基铵、0.0005质量%二亚乙基三胺五(亚甲基膦酸)、以及82.4995质量%水的水溶液(表3的清洗液3G),清洗图1所示的半导体元件。表4示出清洗条件和评价结果。能够去除硬掩模5,但是不能去除有机硅氧烷系薄膜6、干法蚀刻残渣8以及光致抗蚀层7。
(比较例8)
使用包含17质量%过氧化氢、0.2质量%氢氧化钾、0.0005质量%二亚乙基三胺五(亚甲基膦酸)、以及82.7995质量%水的水溶液(表3的清洗液3H),清洗图1所示的半导体元件。表4示出清洗条件和评价结果。能够去除硬掩模5、有机硅氧烷系薄膜6、干法蚀刻残渣8以及光致抗蚀层7。在低介电常数层间绝缘膜4和铜2上未观察到损伤。但是,使用添加了酸的清洗液的情况下,在铜2上观察到损伤,向清洗液添加了钛的情况下过氧化氢的分解较大。
(比较例9)
使用包含0.5质量%氢氧化四甲基铵、0.2质量%氢氧化钾、0.0005质量%二亚乙基三胺五(亚甲基膦酸)、以及99.2995质量%水的水溶液(表3的清洗液3I),清洗图1所示的半导体元件。表4示出清洗条件和评价结果。不能去除硬掩模5、有机硅氧烷系薄膜6、干法蚀刻残渣8以及光致抗蚀层7。在低介电常数层间绝缘膜4以及铜2上观察到损伤。
因此,3F、3G、3H、以及3I的清洗液,对低介电常数层间绝缘膜、以及铜布线的损伤的抑制、以及对硬掩模、有机硅氧烷系薄膜、干法蚀刻残渣以及光致抗蚀层的去除是不充分的,或若添加酸则对铜布线造成损伤,或由于钛的添加导致过氧化氢的稳定性不足(表4)。
(比较例10)
使用包含17质量%过氧化氢、0.2质量%氢氧化钾、0.1质量%1,3-丙二胺、0.0005质量%二亚乙基三胺五(亚甲基膦酸)、以及82.6995质量%水的水溶液(表3的清洗液3J),清洗图1所示的半导体元件。表4示出清洗条件和评价结果。去除了硬掩模5、有机硅氧烷系薄膜6、干法蚀刻残渣8以及光致抗蚀层7。在低介电常数层间绝缘膜4上未观察到损伤,但是在铜2上观察到损伤。使用添加了酸的清洗液的情况下,在铜2上观察到损伤,清洗液中添加了钛的情况下,过氧化氢的分解较大。
(比较例11)
使用包含17质量%过氧化氢、0.2质量%氢氧化钾、0.04质量%氨、0.0005质量%二亚乙基三胺五(亚甲基膦酸)、以及82.7595质量%水的水溶液(表3的清洗液3K),清洗图1所示的半导体元件。表4示出清洗条件和评价结果。能够去除硬掩模5、有机硅氧烷系薄膜6、干法蚀刻残渣8以及光致抗蚀层7。在低介电常数层间绝缘膜4上未观察到损伤,但是在铜2上观察到损伤。使用添加了酸的清洗液的情况下,在铜2上观察到损伤,清洗液中添加了钛的情况下,过氧化氢的分解程度大。
(比较例12)
使用包含17质量%过氧化氢、0.2质量%氢氧化钾、0.2质量%2-(甲基氨基)乙醇、0.0005质量%二亚乙基三胺五(亚甲基膦酸)、以及82.5995质量%水的水溶液(表3的清洗液3L),清洗图1所示的半导体元件。表4示出清洗条件和评价结果。能够去除硬掩模5、有机硅氧烷系薄膜6、干法蚀刻残渣8以及光致抗蚀层7。在低介电常数层间绝缘膜4上未观察到损伤,但是在铜2上观察到损伤。使用添加了酸的清洗液的情况下,在铜2上观察到损伤、清洗液中添加了钛的情况下,过氧化氢的分解程度大。
[表1]
TMAH:氢氧化四甲基铵
TEAH:氢氧化四乙基铵
TPAH:氢氧化四丙基铵
TBAH:氢氧化四丁基铵
BTMAH:氢氧化苄基三甲基铵
[表2]
去除状态I:有机硅氧烷系薄膜6的去除状态
去除状态II:干法蚀刻残渣8的去除状态
去除状态III:劣化光致抗蚀层7的去除状态
去除状态IV:钛系硬掩模5的去除状态
损伤V:铜2的损伤
损伤VI:低介电常数层间绝缘膜4的损伤
损伤VII:用添加了酸的清洗液进行清洗的情况下的铜2的损伤
稳定性VIII:添加了钛的情况下的过氧化氢的稳定性
[表3]
[表4]
去除状态I:有机硅氧烷系薄膜6的去除状态
去除状态II:干法蚀刻残渣8的去除状态
去除状态III:劣化光致抗蚀层7的去除状态
去除状态IV:钛系硬掩模5的去除状态
损伤V:铜2的损伤
损伤VI:低介电常数层间绝缘膜4的损伤
损伤VII:用添加了酸的清洗液进行清洗的情况下的铜2的损伤
稳定性VIII:添加了钛的情况下的过氧化氢的稳定性
符号的说明
1:阻隔金属层
2:铜或铜合金布线
3:阻隔绝缘膜
4:低介电常数层间绝缘膜
5:硬掩模
6:有机硅氧烷系薄膜
7:劣化光致抗蚀层
8:干法蚀刻残渣
Claims (10)
1.一种清洗液,其为对下述半导体元件进行清洗,去除下述有机硅氧烷系薄膜、硬掩模、干法蚀刻残渣以及光致抗蚀层的清洗液,
所述半导体元件为在具有阻隔金属层、铜布线或铜合金布线、低介电常数层间绝缘膜的基板上依次层叠阻隔绝缘膜、低介电常数层间绝缘膜、硬掩模、有机硅氧烷系薄膜、以及光致抗蚀层后,对该光致抗蚀层实施选择性曝光和显影处理,形成光致抗蚀图案,接着将该光致抗蚀图案作为掩模,对所述有机硅氧烷系薄膜、硬掩模、低介电常数层间绝缘膜以及阻隔绝缘膜实施了干法蚀刻处理的半导体元件,
所述清洗液包含10~30质量%过氧化氢、0.005~10质量%季铵氢氧化物、0.005~5质量%氢氧化钾、0.000005~0.005质量%氨基多亚甲基膦酸、以及水。
2.根据权利要求1所述的清洗液,其中,所述硬掩模含有氮化钛或钛。
3.根据权利要求1或2所述的清洗液,其中,所述季铵氢氧化物为选自由氢氧化四甲基铵、氢氧化四乙基铵、氢氧化四丙基铵、氢氧化四丁基铵以及氢氧化苄基三甲基铵组成的组中的至少1种。
4.根据权利要求1或2所述的清洗液,其中,所述氨基多亚甲基膦酸为选自由氨基三(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)以及1,2-丙二胺四(亚甲基膦酸)组成的组中的至少1种。
5.根据权利要求1或2所述的清洗液,其中,钠浓度为0.1ppm以下。
6.一种半导体元件的清洗方法,其特征在于,对下述半导体元件使用清洗液,去除下述硬掩模、有机硅氧烷系薄膜、干法蚀刻残渣以及光致抗蚀层,
所述半导体元件为在具有阻隔金属层、铜布线或铜合金布线、低介电常数层间绝缘膜的基板上依次层叠阻隔绝缘膜、低介电常数层间绝缘膜、硬掩模、有机硅氧烷系薄膜、以及光致抗蚀层后,对该光致抗蚀层实施选择性曝光和显影处理,形成光致抗蚀图案,接着将该光致抗蚀图案作为掩模,对所述有机硅氧烷系薄膜、硬掩模、低介电常数层间绝缘膜以及阻隔绝缘膜实施了干法蚀刻处理的半导体元件,
所述清洗液包含10~30质量%过氧化氢、0.005~10质量%季铵氢氧化物、0.005~5质量%氢氧化钾、0.000005~0.005质量%氨基多亚甲基膦酸、以及水。
7.根据权利要求6所述的清洗方法,其中,所述硬掩模含有氮化钛或钛。
8.根据权利要求6或7所述的清洗方法,其中,所述季铵氢氧化物为选自由氢氧化四甲基铵、氢氧化四乙基铵、氢氧化四丙基铵、氢氧化四丁基铵以及氢氧化苄基三甲基铵组成的组中的至少1种。
9.根据权利要求6或7所述的清洗方法,其中,所述氨基多亚甲基膦酸为选自由氨基三(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)以及1,2-丙二胺四(亚甲基膦酸)组成的组中的至少1种。
10.根据权利要求6或7所述的清洗方法,其中,钠含量为0.1ppm以下。
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