CN1203163C - 洗涤液 - Google Patents
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- CN1203163C CN1203163C CNB981162703A CN98116270A CN1203163C CN 1203163 C CN1203163 C CN 1203163C CN B981162703 A CNB981162703 A CN B981162703A CN 98116270 A CN98116270 A CN 98116270A CN 1203163 C CN1203163 C CN 1203163C
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- 238000005406 washing Methods 0.000 title claims description 75
- 239000007788 liquid Substances 0.000 title description 9
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 claims abstract description 78
- 229910052751 metal Inorganic materials 0.000 claims abstract description 28
- 239000002184 metal Substances 0.000 claims abstract description 28
- 235000006408 oxalic acid Nutrition 0.000 claims abstract description 26
- 239000000758 substrate Substances 0.000 claims abstract description 20
- VBIXEXWLHSRNKB-UHFFFAOYSA-N ammonium oxalate Chemical compound [NH4+].[NH4+].[O-]C(=O)C([O-])=O VBIXEXWLHSRNKB-UHFFFAOYSA-N 0.000 claims abstract description 14
- KCXVZYZYPLLWCC-UHFFFAOYSA-N EDTA Chemical compound OC(=O)CN(CC(O)=O)CCN(CC(O)=O)CC(O)=O KCXVZYZYPLLWCC-UHFFFAOYSA-N 0.000 claims description 18
- 150000001732 carboxylic acid derivatives Chemical class 0.000 claims description 11
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 10
- QPCDCPDFJACHGM-UHFFFAOYSA-N N,N-bis{2-[bis(carboxymethyl)amino]ethyl}glycine Chemical compound OC(=O)CN(CC(O)=O)CCN(CC(=O)O)CCN(CC(O)=O)CC(O)=O QPCDCPDFJACHGM-UHFFFAOYSA-N 0.000 claims description 7
- 125000004435 hydrogen atom Chemical class [H]* 0.000 claims description 6
- 150000003863 ammonium salts Chemical group 0.000 claims description 4
- MGFYIUFZLHCRTH-UHFFFAOYSA-N nitrilotriacetic acid Chemical compound OC(=O)CN(CC(O)=O)CC(O)=O MGFYIUFZLHCRTH-UHFFFAOYSA-N 0.000 claims description 4
- 229960003330 pentetic acid Drugs 0.000 claims description 3
- 239000000203 mixture Substances 0.000 claims description 2
- 150000001735 carboxylic acids Chemical class 0.000 claims 1
- 239000012535 impurity Substances 0.000 abstract description 13
- 239000002253 acid Substances 0.000 abstract description 5
- 238000004140 cleaning Methods 0.000 abstract description 4
- 150000007513 acids Chemical class 0.000 abstract 1
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 33
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 23
- 230000000052 comparative effect Effects 0.000 description 13
- 239000007864 aqueous solution Substances 0.000 description 11
- 239000004065 semiconductor Substances 0.000 description 9
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- 238000004519 manufacturing process Methods 0.000 description 5
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 description 5
- 229910052721 tungsten Inorganic materials 0.000 description 5
- 239000010937 tungsten Substances 0.000 description 5
- 238000005260 corrosion Methods 0.000 description 4
- 230000007797 corrosion Effects 0.000 description 4
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- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 description 3
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 3
- 239000011229 interlayer Substances 0.000 description 3
- MVFCKEFYUDZOCX-UHFFFAOYSA-N iron(2+);dinitrate Chemical compound [Fe+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O MVFCKEFYUDZOCX-UHFFFAOYSA-N 0.000 description 3
- 229910052814 silicon oxide Inorganic materials 0.000 description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- 208000019901 Anxiety disease Diseases 0.000 description 2
- NRTOMJZYCJJWKI-UHFFFAOYSA-N Titanium nitride Chemical compound [Ti]#N NRTOMJZYCJJWKI-UHFFFAOYSA-N 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 2
- 229910052782 aluminium Inorganic materials 0.000 description 2
- 230000036506 anxiety Effects 0.000 description 2
- 238000013329 compounding Methods 0.000 description 2
- 238000011109 contamination Methods 0.000 description 2
- 238000007598 dipping method Methods 0.000 description 2
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- 238000002360 preparation method Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 229910000838 Al alloy Inorganic materials 0.000 description 1
- 229910052684 Cerium Inorganic materials 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- RRZQGXJZXXSBMQ-UHFFFAOYSA-N [Al+3].[O-2].[Fe+2].[N+](=O)([O-])[O-] Chemical compound [Al+3].[O-2].[Fe+2].[N+](=O)([O-])[O-] RRZQGXJZXXSBMQ-UHFFFAOYSA-N 0.000 description 1
- 239000012670 alkaline solution Substances 0.000 description 1
- 239000004411 aluminium Substances 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 238000004380 ashing Methods 0.000 description 1
- 239000008139 complexing agent Substances 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 239000000428 dust Substances 0.000 description 1
- 229910000040 hydrogen fluoride Inorganic materials 0.000 description 1
- VSFGYNFCJOQAIL-UHFFFAOYSA-N hydrogen peroxide hydrate hydrochloride Chemical compound O.Cl.OO VSFGYNFCJOQAIL-UHFFFAOYSA-N 0.000 description 1
- XEMZLVDIUVCKGL-UHFFFAOYSA-N hydrogen peroxide;sulfuric acid Chemical compound OO.OS(O)(=O)=O XEMZLVDIUVCKGL-UHFFFAOYSA-N 0.000 description 1
- 230000008595 infiltration Effects 0.000 description 1
- 238000001764 infiltration Methods 0.000 description 1
- 238000009413 insulation Methods 0.000 description 1
- 239000010808 liquid waste Substances 0.000 description 1
- 229910052748 manganese Inorganic materials 0.000 description 1
- 239000007769 metal material Substances 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 150000007524 organic acids Chemical class 0.000 description 1
- 235000005985 organic acids Nutrition 0.000 description 1
- XEEVLJKYYUVTRC-UHFFFAOYSA-N oxomalonic acid Chemical compound OC(=O)C(=O)C(O)=O XEEVLJKYYUVTRC-UHFFFAOYSA-N 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 238000005498 polishing Methods 0.000 description 1
- 238000003825 pressing Methods 0.000 description 1
- 238000012797 qualification Methods 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 235000012976 tarts Nutrition 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
Classifications
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
- H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
- H01L21/02041—Cleaning
- H01L21/02057—Cleaning during device manufacture
- H01L21/02068—Cleaning during device manufacture during, before or after processing of conductive layers, e.g. polysilicon or amorphous silicon layers
- H01L21/02074—Cleaning during device manufacture during, before or after processing of conductive layers, e.g. polysilicon or amorphous silicon layers the processing being a planarization of conductive layers
-
- 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
- C11D7/26—Organic compounds containing oxygen
- C11D7/265—Carboxylic acids or salts thereof
-
- 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
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- 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
- C11D7/3245—Aminoacids
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
- H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
- H01L21/02041—Cleaning
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- 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
- C11D2111/00—Cleaning compositions characterised by the objects to be cleaned; Cleaning compositions characterised by non-standard cleaning or washing processes
- C11D2111/10—Objects to be cleaned
- C11D2111/14—Hard surfaces
- C11D2111/22—Electronic devices, e.g. PCBs or semiconductors
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- H—ELECTRICITY
- H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
- H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
- H05K3/00—Apparatus or processes for manufacturing printed circuits
- H05K3/22—Secondary treatment of printed circuits
- H05K3/26—Cleaning or polishing of the conductive pattern
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
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- Oil, Petroleum & Natural Gas (AREA)
- Manufacturing & Machinery (AREA)
- Microelectronics & Electronic Packaging (AREA)
- Health & Medical Sciences (AREA)
- Physics & Mathematics (AREA)
- Condensed Matter Physics & Semiconductors (AREA)
- General Physics & Mathematics (AREA)
- Emergency Medicine (AREA)
- Computer Hardware Design (AREA)
- Power Engineering (AREA)
- Cleaning Or Drying Semiconductors (AREA)
- Detergent Compositions (AREA)
Abstract
提供一种不腐蚀金属、可以容易地去除基板表面的金属杂质的洗涤液，即在环境负荷、保存性等方面没有问题的、布设了金属配线后的基板洗涤用的洗涤液。布设了金属配线后的基板洗涤用洗涤液，其特征在于含有草酸、草酸铵、多氨基羧酸类中至少一种。
Description
本发明涉及洗涤液，尤其涉及用于去除布设了金属配线后的基板的金属污染的洗涤液。
此外，本发明还特别涉及半导体制造工艺中有化学机械研磨(CMP)后使用的金属配线的基板的洗涤液。
伴随着集成电路(IC)的高集成化，微量杂质会对器件的性能、合格率产生很大影响，因而要求严格的沾污控制(contamination control)。即，要求把基板表面的金属杂质浓度控制在1010个原子/cm2以下，为此，在半导体制造的各步骤中要使用各种洗涤液。
一般来说，作为半导体用基板洗涤液，有硫酸-双氧水、氨水-双氧水-水(SC-1)、盐酸-双氧水-水(SC-2)、稀氢氟酸等，因目的而异，各洗涤液可以单独使用也可以组合使用。另一方面，近年来，在半导体制造工艺中引进了绝缘膜平坦化、接线孔平坦化、金属镶嵌(damascene)配线等化学机械研磨(CMP)技术，但作为CMP后基板表面上吸附的金属杂质的清洗，例如，在《半导体世界》(Semiconductor World)月刊1997年第3期第92页记载了使用柠檬酸水溶液的情况，进而在国际专利申请公开公报WO 96/26538中记载了柠檬酸水溶液或乙二胺四乙酸(EDTA)等与氟化氢一起使用的情况。此外，与本申请的优先权日前申请有关、优先权日后公开的特开平10-72594(欧洲专利公开第812011号)中，也记载了含有柠檬酸等有机酸和络合剂的洗涤液。
上述一般用于洗涤布设了金属配线后的基板的洗涤液的液体性质，在有氧化性的同时还有强酸或强碱性，因而会腐蚀(etching)该基板表面上露出的金属，当然，即使在用绝缘层等覆盖埋设金属的情况下，洗涤液也会通过渗透来腐蚀金属，因而有时不能用于半导体制造工艺中。例如，在作为CMP应用技术、现在最受瞩目的称为钨栓(W-Plug)的层间连接等技术中，就不能使用这样的洗涤液。
一般来说，金属的CMP是一边供给研磨剂微粒与化学药品的混合物即一种浆状物，一边用一种称为抛光布(buff)的布压着薄片(wafer)，通过旋转兼用化学作用和物理作用来磨蚀层间绝缘膜或金属材料从而使膜平整化的技术，但研磨后的硅氧化膜表面等上有吸附了大量金属杂质这样的问题。因此，对能高效率地除去金属杂质的洗涤液是有需求的。
具体地说，在W(钨)的CMP中，一般可以使用从研磨速度、加工精度方面来看优异的氧化铝-硝酸铁浆状物，但由于在氧化剂中使用了硝酸铁，因而有在除去掩蔽W之后露出的硅氧化膜表面上大量吸附Fe这样的问题发生。而且，由于这里使用的硝酸铁浓度高，因而硅氧化膜表面上吸附的Fe的表面浓度非常高，达到1014个原子/cm2以上，不仅薄片(wafer)而且生产线的二次污染也成为问题。因此，在进入下一步骤之前，把来自CMP的基板上吸附的Fe去除到1010个原子/cm2是所希望的。
用上述先有技术上含氟化氢的洗涤液，虽然可以期待金属杂质的去除，但没有解决对金属的腐蚀和使层间绝缘膜腐蚀的问题。
另一方面，为了解决对金属的腐蚀问题，作为钨栓的CMP后等可以使用的洗涤液，在采用上述先有技术中的柠檬酸水溶液的方法时，虽然对金属的腐蚀没有了，但用柠檬酸水溶液洗涤后基板表面上Fe的浓度为约1013个原子/cm2左右，决不能说是令人满意的。
进而，在使用了柠檬酸的洗涤液中，为了达到令人满意的洗涤效果，有必要配成20～30％的高浓度，使得废液处理等对环境的负荷增大，而且容易发生霉变，保存性方面也有问题。
如以上所述，综合性解决上述诸问题的手段迄今为止还无人知晓。
因此，本发明的课颗是提供一种洗涤液，即一种不腐蚀金属、能容易且高效率地去除基板表面的金属杂质的洗涤液，没有环境负荷、保存性等方面的问题，而且能洗涤布设了金属配线后的基板。
本发明者等人为解决上述课题而反复进行锐意研究的结果，发现含有草酸、草酸铵、多氨基羧酸类中至少一种而且不含氟化氢的洗涤液在半导体基板的洗涤方面是良好的，特别是能良好地洗涤CMP后薄片(wafer)上吸附的金属杂质。即，本发明是用来洗涤布设了金属配线后的基板的洗涤液，其特征在于含有草酸、草酸铵、多氨基羧酸类中至少一种，而且不含氟化氢。本发明中的草酸、草酸铵或多氨基羧酸类由于能与Fe生成配合物而且稳定性常数也大，因而可以用于Fe的洗涤，尤其通过并用草酸或草酸铵和多氨基羧酸类可以获得高洗净力。这可以认为，由于Fe和草酸及多氨基羧酸形成溶解性更好的三元配合物，因而进一步提高了洗净性。
进而，本发明的洗涤液也能有效地洗涤来源于其它浆状物的、诸如Mn、Al、Ce等金属杂质。其理由可以考虑如下：
①Mn与草酸的配合物的稳定性常数大，其盐在草酸水溶液中溶解性高；
②Al与草酸的配合物的稳定性常数，同柠檬酸比较而言，是非常大的；
③Ce除能与乙二胺四乙酸(EDTA)制成稳定配合物外，Ce的草酸盐还良溶于EDTA的碱溶液中。
从以上情况来看，不仅对Fe，即使对源于其它浆状物的金属杂质等，也能发挥令人满意的效果。
而且，本发明洗涤液的溶液性质即使是酸性的，也有不腐蚀铝、铝合金、铜、钨、钛、氮化钛等金属的好特性。因此，本发明由于对布设了金属配线后的基板，无论其表面露出了金属还是没有露出金属，都不腐蚀该金属，因而能有效地洗涤CMP后基板表面上吸附的金属杂质，进而，即使对于构成电子部件的印刷基板和具有锦段结构的金属配线，由于不刻蚀金属配线部分，因而也能有效地去除基板上残留的金属杂质。
而且，本发明的洗涤液，与柠檬酸洗涤液相比，以其1/10的浓度就能发挥令人满意的洗涤效果，而且无发生霉变之虞，还可以大幅度改善对环境的负荷。
本发明用于洗涤布设了金属配线后的基板的洗涤液，是洗涤液中草酸或草酸铵的浓度为0.1～10％(重量)，特别好的是1.0～6％(重量)的洗涤液。
草酸浓度太低时，洗涤效果不能充分发挥，而在达到高浓度的情况下不能期待与浓度相称的效果，进而还有析出结晶之虞。
此外，作为多氨基羧酸类，较好的是乙二胺四乙酸(EDTA)、反式-1，2-环己烷二胺四乙酸(CyDTA)、次氮基三乙酸(NTA)、二亚乙基三胺五乙酸(DTPA)、N-(2-羟基乙基)乙二胺-N，N’，N’-三乙酸(EDTA-OH)等化合物及其铵盐。一般来说，这些化合物是以游离酸或盐的形式使用的，但游离酸对水或酸的溶解性低，因而不适合于配制高浓度的溶液。因此，为了配制高浓度的溶液，有必要用水溶性的盐，而且对于半导体制造用途来说，最好的是对特性不产生有害铵盐等不含金属的盐。
作为多氨基羧酸的浓度，较好的是0.0001～5％(重量)，特别好的是0.001～0.1％(重量)。在浓度低的情况下，洗涤效果不能令人满意，而即使太高，也不能期待与其相称的效果。本发明的洗涤液可以在室温下使用。此外，其洗涤液的pH可以使用3～5。
以下，连同比较例一起显示了本发明的实施例，以详细地说明本发明，但本发明不限定于这些实施例。
[比较例]
比较例1
对于浸渍硝酸铁水溶液而预污染的带氧化膜的硅薄片，用全反射荧光X射线装置(テクノス公司制TREX-610T)测定薄片表面的Fe浓度。然后，把200g柠檬酸溶解在800g水中，作为20％(重量)水溶液，在40℃洗涤3分钟，水洗，干燥后再次测定薄片表面的Fe浓度，评价去除Fe的能力(表4)。
[实施例]
实施例1(草酸浓度与去除能力)
作为洗涤液，把草酸溶解在水中，分别配制0.1、1.0、3.4％(重量)的水溶液。用各洗涤液，同比较例1一样评价液温40℃、3分钟洗涤的去除Fe的能力(表1)。
[表1]
表1
| 草酸浓度 | Fe表面浓度(×1010个原子/cm2) | |
| 洗涤前 | - | 20000 |
| 洗涤后 | 0.1％ | 473 |
| 1.0％ | 23 | |
| 3.4％ | 11 |
实施例2(处理温度与去除能力)
作为洗涤液，用草酸34g溶解在水966g中配制的3.4％(重量)水溶液，处理温度改变为23、30、40℃，同比较例1一样评价洗涤3分钟的去除Fe能力(表2)。
[表2]
表2
| 处理温度 | Fe表面浓度(×1010个原子/cm2) | |
| 洗涤前 | - | 20000 |
| 洗涤后 | 23℃ | 17 |
| 30℃ | 16 | |
| 40℃ | 11 |
实施例3(pH与去除能力)
向3.4％(重量)草酸水溶液中添加氨，配制pH3.0、4.0、5.0、6.5的洗涤液。用各洗涤液，同比较例1一样评价液温40℃、洗涤3分钟的去Fe的能力(表3)。
[表3]
表3
| pH | Fe表面浓度(×1010个原子/cm2) | |
| 洗涤前 | - | 20000 |
| 洗涤后 | 0.8 | 11 |
| 3.0 | 17 | |
| 4.0 | 18 | |
| 5.0 | 14 | |
| 6.5 | 25 |
实施例4
作为洗涤液，配制3.4％(重量)草酸铵水溶液，同比较例1一样评价液温40℃、洗涤3分钟的去除Fe的能力(表4)。
实施例5
作为洗涤液，用草酸5.0g、草酸铵29g溶解在水966g中配制的草酸与草酸铵混合液，同比较例1一样评价液温40℃、洗涤3分钟的去除Fe的能力(表4)。
实施例6
以草酸34g、乙二胺四乙酸0.1g溶解在水965.9g中配制的水溶液作为洗涤液，同比较例1一样评价液温40℃、洗涤3分钟的去除Fe的能力(表4)。
实施例7
以草酸34g、反式-1，2-环己烷二胺四乙酸0.1g溶解在水965.9g中配制的水溶液作为洗涤液，同比较例1一样评价液温40℃、洗涤3分钟的去除Fe的能力(表4)。
实施例8
作为洗涤液，使用乙二胺四乙酸0.1g溶解在水999.9g中配制的水溶液，同比较例1一样评价液温40℃、洗涤3分钟的去除Fe的能力(表4)。
比较例1、实施例4～8的结果列于表4中。
[表4]
表4
| Fe表面浓度(×1010个原子/cm2) | |
| 洗涤前 | 11996 |
| 比较例1 | 2209 |
| 实施例4 | 25.1 |
| 实施例5 | 10.6 |
| 实施例6 | 1.9 |
| 实施例7 | 2.3 |
| 实施例8 | 6.7 |
实施例9(对各种金属的腐蚀性)
附有各金属膜的基板在3.4％草酸水溶液或10％柠檬酸水溶液中于40℃浸渍60分钟后，水洗，甩干后，用荧光X射线膜厚计测定金属膜的膜厚，求出膜减量(表5)
[表5]
表5
| 膜减量(埃) | ||
| 钨(W) | 氮化钛(Tin) | |
| 草酸 | 25 | 7 |
| 柠檬酸 | 117 | 8 |
Claims (11)
1.一种洗涤液，其特征在于它是用来洗涤布设了金属配线后的基板的洗涤液，含有0.1～10重量％的草酸、0.1～10重量％的草酸铵、以及0.0001～5重量％的多氨基羧酸类这3种中至少一种，且不含氟化氢。
2.权利要求1所述的洗涤液，其特征在于含有草酸与多氨基羧酸类、草酸铵与多氨基羧酸类、草酸与草酸铵和多氨基羧酸类组合中的任何一种。
3.权利要求2所述的洗涤液，其特征在于含有
(a)0.1～10重量％选自由草酸和草酸铵组成的一组中的至少1种，以及
(b)0.0001～5重量％选自由乙二胺四乙酸、反式-1，2-环己烷二胺四乙酸、次氮基三乙酸、二亚乙基三胺五乙酸、N-(2-羟基乙基)乙二胺-N，N，N-三乙酸、以及它们的铵盐组成的一组中的至少1种，
且不含氟化氢。
4.权利要求2所述的洗涤液，其特征在于含有
(a)选自由草酸以及草酸铵组成的一组中的至少1种，
(b)0.0001～5重量％选自由乙二胺四乙酸、反式-1，2-环己烷二胺四乙酸、次氮基三乙酸、二亚乙基三胺五乙酸、N-(2-羟基乙基)乙二胺-N，N，N-三乙酸、以及它们的铵盐组成的一组中的至少1种，以及
(c)水，
且不含氟化氢。
5.权利要求4所述的洗涤液，其中含有0.1～10重量％权利要求4所述的(a)成分。
6.权利要求1所述的洗涤液，其特征在于在室温使用。
7.权利要求1所述的洗涤液，其特征在于含有多氨基羧酸，且pH为3～5。
8.权利要求1所述的洗涤液，其特征在于在化学机械研磨后使用。
9.权利要求8所述的洗涤液，其特征在于在化学机械研磨之后，在表面上有金属露出的基板上使用。
10.权利要求8所述的洗涤液，其特征在于在化学机械研磨之后，在表面上没有金属露出的基板上使用。
11.权利要求8所述的洗涤液，其特征在于在金属塞的化学机械研磨之后使用。
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| Application Number | Priority Date | Filing Date | Title |
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| JP228943/97 | 1997-08-12 | ||
| JP22894397 | 1997-08-12 | ||
| JP228943/1997 | 1997-08-12 |
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| CN1210886A CN1210886A (zh) | 1999-03-17 |
| CN1203163C true CN1203163C (zh) | 2005-05-25 |
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| CNB981162703A Expired - Fee Related CN1203163C (zh) | 1997-08-12 | 1998-08-10 | 洗涤液 |
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| US (1) | US6080709A (zh) |
| EP (1) | EP0897975B1 (zh) |
| KR (1) | KR100533194B1 (zh) |
| CN (1) | CN1203163C (zh) |
| DE (1) | DE69823283T2 (zh) |
| TW (1) | TW387936B (zh) |
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| US6755989B2 (en) * | 1997-01-09 | 2004-06-29 | Advanced Technology Materials, Inc. | Aqueous cleaning composition containing copper-specific corrosion inhibitor for cleaning inorganic residues on semiconductor substrate |
| US6896826B2 (en) * | 1997-01-09 | 2005-05-24 | Advanced Technology Materials, Inc. | Aqueous cleaning composition containing copper-specific corrosion inhibitor for cleaning inorganic residues on semiconductor substrate |
| US6231677B1 (en) * | 1998-02-27 | 2001-05-15 | Kanto Kagaku Kabushiki Kaisha | Photoresist stripping liquid composition |
| US6332988B1 (en) | 1999-06-02 | 2001-12-25 | International Business Machines Corporation | Rework process |
| US6419554B2 (en) * | 1999-06-24 | 2002-07-16 | Micron Technology, Inc. | Fixed abrasive chemical-mechanical planarization of titanium nitride |
| US6436302B1 (en) * | 1999-08-23 | 2002-08-20 | Applied Materials, Inc. | Post CU CMP polishing for reduced defects |
| JP3307375B2 (ja) * | 1999-10-04 | 2002-07-24 | 日本電気株式会社 | 半導体装置の製造方法 |
| US6592433B2 (en) * | 1999-12-31 | 2003-07-15 | Intel Corporation | Method for defect reduction |
| JP4821082B2 (ja) * | 2000-03-21 | 2011-11-24 | 和光純薬工業株式会社 | 半導体基板洗浄剤及び洗浄方法 |
| US6627546B2 (en) | 2001-06-29 | 2003-09-30 | Ashland Inc. | Process for removing contaminant from a surface and composition useful therefor |
| JP3787085B2 (ja) * | 2001-12-04 | 2006-06-21 | 関東化学株式会社 | フォトレジスト残渣除去液組成物 |
| TWI339680B (en) * | 2002-02-19 | 2011-04-01 | Kanto Kagaku | Washing liquid composition for semiconductor substrate |
| AU2003225178A1 (en) * | 2002-04-24 | 2003-11-10 | Ekc Technology, Inc. | Oxalic acid as a cleaning product for aluminium, copper and dielectric surfaces |
| JP4221191B2 (ja) * | 2002-05-16 | 2009-02-12 | 関東化学株式会社 | Ｃｍｐ後洗浄液組成物 |
| EP1562225A4 (en) * | 2002-11-08 | 2007-04-18 | Wako Pure Chem Ind Ltd | CLEANING COMPOSITION AND METHOD FOR CLEANING WITH THE COMPOSITION |
| JP4375991B2 (ja) * | 2003-04-09 | 2009-12-02 | 関東化学株式会社 | 半導体基板洗浄液組成物 |
| US20060293199A1 (en) | 2003-06-04 | 2006-12-28 | Kao Corporation | Removing agent composition and removing/cleaning method using same |
| JP4628209B2 (ja) * | 2004-11-18 | 2011-02-09 | 花王株式会社 | 剥離剤組成物 |
| KR20090073376A (ko) * | 2007-12-31 | 2009-07-03 | 삼성전자주식회사 | 위상 반전 마스크 세정용 조성물, 위상 반전 마스크의 세정방법 및 위상 반전 마스크의 제조 방법 |
| SG175830A1 (en) * | 2009-04-08 | 2011-12-29 | Sunsonix | Process and apparatus for removal of contaminating material from substrates |
| WO2011063353A2 (en) * | 2009-11-23 | 2011-05-26 | Metcon, Llc | Electrolyte solution and electropolishing methods |
| KR20130028059A (ko) * | 2010-03-05 | 2013-03-18 | 램 리써치 코포레이션 | 다마신 프로세스들의 측벽 폴리머에 대한 세정 용액 |
| CN102985596B (zh) * | 2010-06-18 | 2016-08-10 | 三菱瓦斯化学株式会社 | 用于包含铜层和钼层的多层结构膜的蚀刻液 |
| US8580103B2 (en) | 2010-11-22 | 2013-11-12 | Metcon, Llc | Electrolyte solution and electrochemical surface modification methods |
| JP6066552B2 (ja) | 2011-12-06 | 2017-01-25 | 関東化學株式会社 | 電子デバイス用洗浄液組成物 |
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| US4209418A (en) * | 1978-07-18 | 1980-06-24 | Union Carbide Corporation | Gelatin benzimidazole blends as inhibitors for carboxylic acids |
| US4226640A (en) * | 1978-10-26 | 1980-10-07 | Kraftwerk Union Aktiengesellschaft | Method for the chemical decontamination of nuclear reactor components |
| CA1136398A (en) * | 1979-12-10 | 1982-11-30 | William A. Seddon | Decontaminating reagents for radioactive systems |
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| US4452643A (en) * | 1983-01-12 | 1984-06-05 | Halliburton Company | Method of removing copper and copper oxide from a ferrous metal surface |
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| FR2722511B1 (fr) * | 1994-07-15 | 1999-04-02 | Ontrak Systems Inc | Procede pour enlever les metaux dans un dispositif de recurage |
| TW416987B (en) * | 1996-06-05 | 2001-01-01 | Wako Pure Chem Ind Ltd | A composition for cleaning the semiconductor substrate surface |
| US5759437A (en) * | 1996-10-31 | 1998-06-02 | International Business Machines Corporation | Etching of Ti-W for C4 rework |
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1998
- 1998-08-04 TW TW087112784A patent/TW387936B/zh not_active IP Right Cessation
- 1998-08-10 CN CNB981162703A patent/CN1203163C/zh not_active Expired - Fee Related
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- 1998-08-11 EP EP98115097A patent/EP0897975B1/en not_active Expired - Lifetime
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Also Published As
| Publication number | Publication date |
|---|---|
| DE69823283T2 (de) | 2005-04-28 |
| EP0897975A1 (en) | 1999-02-24 |
| US6080709A (en) | 2000-06-27 |
| DE69823283D1 (de) | 2004-05-27 |
| EP0897975B1 (en) | 2004-04-21 |
| KR100533194B1 (ko) | 2006-09-20 |
| KR19990023555A (ko) | 1999-03-25 |
| CN1210886A (zh) | 1999-03-17 |
| TW387936B (en) | 2000-04-21 |
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