CN1993457A - 微电子衬底的清洗组合物 - Google Patents
微电子衬底的清洗组合物 Download PDFInfo
- Publication number
- CN1993457A CN1993457A CNA2005800262427A CN200580026242A CN1993457A CN 1993457 A CN1993457 A CN 1993457A CN A2005800262427 A CNA2005800262427 A CN A2005800262427A CN 200580026242 A CN200580026242 A CN 200580026242A CN 1993457 A CN1993457 A CN 1993457A
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- CN
- China
- Prior art keywords
- composition
- water
- peeling
- compound
- weak acid
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
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- 239000000203 mixture Substances 0.000 title claims abstract description 79
- 238000004140 cleaning Methods 0.000 title claims abstract description 65
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- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 43
- 150000001412 amines Chemical class 0.000 claims abstract description 33
- 239000002253 acid Substances 0.000 claims abstract description 32
- 238000000034 method Methods 0.000 claims abstract description 28
- 230000000269 nucleophilic effect Effects 0.000 claims abstract description 27
- GIAFURWZWWWBQT-UHFFFAOYSA-N 2-(2-aminoethoxy)ethanol Chemical compound NCCOCCO GIAFURWZWWWBQT-UHFFFAOYSA-N 0.000 claims abstract description 16
- 150000001875 compounds Chemical class 0.000 claims abstract description 15
- 239000002904 solvent Substances 0.000 claims abstract description 10
- 239000007864 aqueous solution Substances 0.000 claims abstract description 9
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- 238000005260 corrosion Methods 0.000 claims description 48
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 claims description 47
- 230000007797 corrosion Effects 0.000 claims description 40
- HZAXFHJVJLSVMW-UHFFFAOYSA-N 2-Aminoethan-1-ol Chemical group NCCO HZAXFHJVJLSVMW-UHFFFAOYSA-N 0.000 claims description 33
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims description 29
- -1 1-amino-2-propyl Chemical group 0.000 claims description 23
- 229910052751 metal Inorganic materials 0.000 claims description 20
- 239000002184 metal Substances 0.000 claims description 20
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- 229910052719 titanium Inorganic materials 0.000 claims description 7
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 claims description 5
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- 239000002861 polymer material Substances 0.000 claims description 2
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 abstract 1
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- 102100032040 Amphoterin-induced protein 2 Human genes 0.000 description 14
- 101000776165 Homo sapiens Amphoterin-induced protein 2 Proteins 0.000 description 14
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- MHABMANUFPZXEB-UHFFFAOYSA-N O-demethyl-aloesaponarin I Natural products O=C1C2=CC=CC(O)=C2C(=O)C2=C1C=C(O)C(C(O)=O)=C2C MHABMANUFPZXEB-UHFFFAOYSA-N 0.000 description 7
- 125000000217 alkyl group Chemical group 0.000 description 7
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- 230000000149 penetrating effect Effects 0.000 description 5
- VILCJCGEZXAXTO-UHFFFAOYSA-N 2,2,2-tetramine Chemical compound NCCNCCNCCN VILCJCGEZXAXTO-UHFFFAOYSA-N 0.000 description 4
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- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 description 4
- 235000019441 ethanol Nutrition 0.000 description 4
- XNGIFLGASWRNHJ-UHFFFAOYSA-N phthalic acid Chemical compound OC(=O)C1=CC=CC=C1C(O)=O XNGIFLGASWRNHJ-UHFFFAOYSA-N 0.000 description 4
- WQGWDDDVZFFDIG-UHFFFAOYSA-N pyrogallol Chemical compound OC1=CC=CC(O)=C1O WQGWDDDVZFFDIG-UHFFFAOYSA-N 0.000 description 4
- GHMLBKRAJCXXBS-UHFFFAOYSA-N resorcinol Chemical compound OC1=CC=CC(O)=C1 GHMLBKRAJCXXBS-UHFFFAOYSA-N 0.000 description 4
- KCXVZYZYPLLWCC-UHFFFAOYSA-N EDTA Chemical compound OC(=O)CN(CC(O)=O)CCN(CC(O)=O)CC(O)=O KCXVZYZYPLLWCC-UHFFFAOYSA-N 0.000 description 3
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 3
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- 229920003171 Poly (ethylene oxide) Polymers 0.000 description 3
- LHIJANUOQQMGNT-UHFFFAOYSA-N aminoethylethanolamine Chemical compound NCCNCCO LHIJANUOQQMGNT-UHFFFAOYSA-N 0.000 description 3
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 3
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 3
- KWIUHFFTVRNATP-UHFFFAOYSA-N glycine betaine Chemical compound C[N+](C)(C)CC([O-])=O KWIUHFFTVRNATP-UHFFFAOYSA-N 0.000 description 3
- 239000003352 sequestering agent Substances 0.000 description 3
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 description 3
- 239000010937 tungsten Substances 0.000 description 3
- 229910052721 tungsten Inorganic materials 0.000 description 3
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- RPNUMPOLZDHAAY-UHFFFAOYSA-N Diethylenetriamine Chemical group NCCNCCN RPNUMPOLZDHAAY-UHFFFAOYSA-N 0.000 description 2
- ROSDSFDQCJNGOL-UHFFFAOYSA-N Dimethylamine Chemical class CNC ROSDSFDQCJNGOL-UHFFFAOYSA-N 0.000 description 2
- 241000282326 Felis catus Species 0.000 description 2
- YNAVUWVOSKDBBP-UHFFFAOYSA-N Morpholine Chemical compound C1COCCN1 YNAVUWVOSKDBBP-UHFFFAOYSA-N 0.000 description 2
- 125000004183 alkoxy alkyl group Chemical group 0.000 description 2
- 150000003973 alkyl amines Chemical class 0.000 description 2
- 125000004103 aminoalkyl group Chemical group 0.000 description 2
- 239000003945 anionic surfactant Substances 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 150000001721 carbon Chemical group 0.000 description 2
- BVKZGUZCCUSVTD-UHFFFAOYSA-N carbonic acid Chemical compound OC(O)=O BVKZGUZCCUSVTD-UHFFFAOYSA-N 0.000 description 2
- 238000009792 diffusion process Methods 0.000 description 2
- XBDQKXXYIPTUBI-UHFFFAOYSA-N dimethylselenoniopropionate Natural products CCC(O)=O XBDQKXXYIPTUBI-UHFFFAOYSA-N 0.000 description 2
- 150000002009 diols Chemical class 0.000 description 2
- 238000010494 dissociation reaction Methods 0.000 description 2
- 230000005593 dissociations Effects 0.000 description 2
- LNTHITQWFMADLM-UHFFFAOYSA-N gallic acid Chemical compound OC(=O)C1=CC(O)=C(O)C(O)=C1 LNTHITQWFMADLM-UHFFFAOYSA-N 0.000 description 2
- 239000004615 ingredient Substances 0.000 description 2
- 229910052500 inorganic mineral Inorganic materials 0.000 description 2
- JVTAAEKCZFNVCJ-UHFFFAOYSA-N lactic acid Chemical compound CC(O)C(O)=O JVTAAEKCZFNVCJ-UHFFFAOYSA-N 0.000 description 2
- 239000011707 mineral Substances 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 150000007524 organic acids Chemical class 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 229940079877 pyrogallol Drugs 0.000 description 2
- HXJUTPCZVOIRIF-UHFFFAOYSA-N sulfolane Chemical compound O=S1(=O)CCCC1 HXJUTPCZVOIRIF-UHFFFAOYSA-N 0.000 description 2
- 239000004094 surface-active agent Substances 0.000 description 2
- UWHCKJMYHZGTIT-UHFFFAOYSA-N tetraethylene glycol Chemical compound OCCOCCOCCOCCO UWHCKJMYHZGTIT-UHFFFAOYSA-N 0.000 description 2
- ZIBGPFATKBEMQZ-UHFFFAOYSA-N triethylene glycol Chemical compound OCCOCCOCCO ZIBGPFATKBEMQZ-UHFFFAOYSA-N 0.000 description 2
- RBNPOMFGQQGHHO-UHFFFAOYSA-N -2,3-Dihydroxypropanoic acid Natural products OCC(O)C(O)=O RBNPOMFGQQGHHO-UHFFFAOYSA-N 0.000 description 1
- NAOLWIGVYRIGTP-UHFFFAOYSA-N 1,3,5-trihydroxyanthracene-9,10-dione Chemical compound C1=CC(O)=C2C(=O)C3=CC(O)=CC(O)=C3C(=O)C2=C1 NAOLWIGVYRIGTP-UHFFFAOYSA-N 0.000 description 1
- RSBHKNDSJJBCMN-UHFFFAOYSA-N 1-(1-hydroxyethyl)pyrrolidin-2-one Chemical compound CC(O)N1CCCC1=O RSBHKNDSJJBCMN-UHFFFAOYSA-N 0.000 description 1
- RUECCIUIKFVPPR-UHFFFAOYSA-N 1-(1-hydroxypropyl)pyrrolidin-2-one Chemical compound CCC(O)N1CCCC1=O RUECCIUIKFVPPR-UHFFFAOYSA-N 0.000 description 1
- ZFPGARUNNKGOBB-UHFFFAOYSA-N 1-Ethyl-2-pyrrolidinone Chemical group CCN1CCCC1=O ZFPGARUNNKGOBB-UHFFFAOYSA-N 0.000 description 1
- GHKCSRZBNZQHKW-UHFFFAOYSA-N 1-sulfanylethanol Chemical class CC(O)S GHKCSRZBNZQHKW-UHFFFAOYSA-N 0.000 description 1
- NCFXAHBHGZLSFB-UHFFFAOYSA-N 2-methyl-2-[methyl(propan-2-yl)amino]pentanoic acid Chemical compound CCCC(C)(C(O)=O)N(C)C(C)C NCFXAHBHGZLSFB-UHFFFAOYSA-N 0.000 description 1
- PPDFQRAASCRJAH-UHFFFAOYSA-N 2-methylthiolane 1,1-dioxide Chemical compound CC1CCCS1(=O)=O PPDFQRAASCRJAH-UHFFFAOYSA-N 0.000 description 1
- NECRQCBKTGZNMH-UHFFFAOYSA-N 3,5-dimethylhex-1-yn-3-ol Chemical compound CC(C)CC(C)(O)C#C NECRQCBKTGZNMH-UHFFFAOYSA-N 0.000 description 1
- XESZUVZBAMCAEJ-UHFFFAOYSA-N 4-tert-butylcatechol Chemical compound CC(C)(C)C1=CC=C(O)C(O)=C1 XESZUVZBAMCAEJ-UHFFFAOYSA-N 0.000 description 1
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 description 1
- DHMQDGOQFOQNFH-UHFFFAOYSA-M Aminoacetate Chemical compound NCC([O-])=O DHMQDGOQFOQNFH-UHFFFAOYSA-M 0.000 description 1
- BYRJNWIHXADTSH-UHFFFAOYSA-N C(CCCCCCCCCCC)C(C(=O)O)CNCCC(=O)O Chemical class C(CCCCCCCCCCC)C(C(=O)O)CNCCC(=O)O BYRJNWIHXADTSH-UHFFFAOYSA-N 0.000 description 1
- BTKLMGGKCQZDNC-UHFFFAOYSA-N CC(C)CCCCCCC[O] Chemical compound CC(C)CCCCCCC[O] BTKLMGGKCQZDNC-UHFFFAOYSA-N 0.000 description 1
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- FCKYPQBAHLOOJQ-UHFFFAOYSA-N Cyclohexane-1,2-diaminetetraacetic acid Chemical compound OC(=O)CN(CC(O)=O)C1CCCCC1N(CC(O)=O)CC(O)=O FCKYPQBAHLOOJQ-UHFFFAOYSA-N 0.000 description 1
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- NSOXQYCFHDMMGV-UHFFFAOYSA-N Tetrakis(2-hydroxypropyl)ethylenediamine Chemical group CC(O)CN(CC(C)O)CCN(CC(C)O)CC(C)O NSOXQYCFHDMMGV-UHFFFAOYSA-N 0.000 description 1
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- CUBCNYWQJHBXIY-UHFFFAOYSA-N benzoic acid;2-hydroxybenzoic acid Chemical compound OC(=O)C1=CC=CC=C1.OC(=O)C1=CC=CC=C1O CUBCNYWQJHBXIY-UHFFFAOYSA-N 0.000 description 1
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- 239000001177 diphosphate Substances 0.000 description 1
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- GEGKMYLSPGGTQM-UHFFFAOYSA-L disodium;3-[2-(2-carboxylatoethoxy)ethyl-[2-(octanoylamino)ethyl]amino]propanoate Chemical compound [Na+].[Na+].CCCCCCCC(=O)NCCN(CCC([O-])=O)CCOCCC([O-])=O GEGKMYLSPGGTQM-UHFFFAOYSA-L 0.000 description 1
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- 125000002801 octanoyl group Chemical group C(CCCCCCC)(=O)* 0.000 description 1
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- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- HNJBEVLQSNELDL-UHFFFAOYSA-N pyrrolidin-2-one Chemical group O=C1CCCN1 HNJBEVLQSNELDL-UHFFFAOYSA-N 0.000 description 1
- IUVKMZGDUIUOCP-BTNSXGMBSA-N quinbolone Chemical compound O([C@H]1CC[C@H]2[C@H]3[C@@H]([C@]4(C=CC(=O)C=C4CC3)C)CC[C@@]21C)C1=CCCC1 IUVKMZGDUIUOCP-BTNSXGMBSA-N 0.000 description 1
- 229940071089 sarcosinate Drugs 0.000 description 1
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- 229940084106 spermaceti Drugs 0.000 description 1
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- 238000010186 staining Methods 0.000 description 1
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- 125000005402 stannate group Chemical group 0.000 description 1
- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 description 1
- XTQHKBHJIVJGKJ-UHFFFAOYSA-N sulfur monoxide Chemical compound S=O XTQHKBHJIVJGKJ-UHFFFAOYSA-N 0.000 description 1
- 229940095064 tartrate Drugs 0.000 description 1
- BFKJFAAPBSQJPD-UHFFFAOYSA-N tetrafluoroethene Chemical group FC(F)=C(F)F BFKJFAAPBSQJPD-UHFFFAOYSA-N 0.000 description 1
- 125000000383 tetramethylene group Chemical group [H]C([H])([*:1])C([H])([H])C([H])([H])C([H])([H])[*:2] 0.000 description 1
- NBOMNTLFRHMDEZ-UHFFFAOYSA-N thiosalicylic acid Chemical compound OC(=O)C1=CC=CC=C1S NBOMNTLFRHMDEZ-UHFFFAOYSA-N 0.000 description 1
- 238000009736 wetting Methods 0.000 description 1
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Abstract
本发明提供一种用于清洗微电子衬底的剥离和清洗组合物,该组合物包括:至少一种有机剥离溶剂,至少一种亲核胺,至少一种不含氮的弱酸,其量足以中和约3重量%~约75重量%的亲核胺,使得剥离组合物的水相pH为约9.6~约10.9,所述弱酸在水溶液中的pK值为2.0或更大且当量低于140,至少一种去除金属化合物选自二甘醇和二甘醇胺,和水,以及用这些组合物清洗微电子衬底的方法。
Description
技术领域
本发明涉及用于微电子衬底的清洗和剥离组合物,特别是用于清洗含铝微电子元件中的含金属残留物而不引起过度的铝腐蚀。本发明还涉及通道的清洗,该通道穿过微电子元件的金属层,如钛层或一氮化钛层,同时适合于底层铝结构,即在微电子元件上引起极少或不引起金属腐蚀。本发明另外涉及此类清洗组合物,其也能够清洗来自其它通道和金属管线的灰化后(post-ash)残留物以及清洗或剥离来自微电子衬底的未灰化(unash)光致抗蚀剂。本发明的其他方面是清洗或剥离含铝微电子元件中的光致抗蚀剂和残留物而不以引起过度铝腐蚀的方法。
背景技术
在微电子设备制造过程中,使用光致抗蚀剂转印图像到微电子衬底上以产生想要的电路层。许多微电子设备是敷铝的。另外,微电子衬底可以使用金属如钛、一氮化钛、钨等作为粘合促进剂和扩散膜(diffusion barries)。
许多碱性微电子剥离和清洗组合物已被建议用于从这些微电子衬底上去除交联的和固化的光致抗蚀剂和其它残留物(如蚀刻后残留物)。然而,此类剥离和清洗组合物存在的一个问题是,使用此类清洗组合物导致发生金属腐蚀的可能性。该腐蚀产生晶须、锈斑、金属管线缺口,至少部分因为装置衬底中的金属与所用的碱性剥离剂反应。一种此类碱性微电子剥离和清洗组合物公开于US专利No.5,308,745中。尽管该专利的剥离和清洗组合物已经在工业上用于自衬底上剥离硬化的和交联的光致抗蚀剂,但发现,尝试用该专利中的清洗组合物清洗具有敷铝和含有来自如钛、一氮化钛、钨等层的金属残留物层的微电子衬底,导致明显的铝腐蚀或不能充分清洗金属残留物。因此,该专利的清洗组合物在清洗穿过钛、一氮化钛、钨等底层的通道的应用中受到限制。
因此需要可以有效地去除此类金属残留物的微电子剥离和清洗组合物,而无任何明显的由该剥离和清洗组合物导致的铝腐蚀。除了清洗这些金属残留物之外,剥离和清洗组合物还需要有效地清洗来自其它通道和金属线的灰化后残留物,以及清洗衬底中的未灰化光致抗蚀剂残留物。
发明概述
根据本发明,提供用于清洗微电子衬底的剥离和清洗组合物,该组合物包括:至少一种有机剥离溶剂,至少一种亲核胺,至少一种不含氮的弱酸,其量足以中和约3重量%~约75重量%、优选约19重量%~约75重量%的亲核胺,使得剥离组合物的水相pH为约9.6~约10.9,所述弱酸在水溶液中的pK值为2.0或更大且当量低于140,至少一种选自二甘醇和二甘醇胺(diethylene glycolamine)的去除金属化合物,和水,以及用这些组合物清洗微电子衬底的方法。
本发明用于清洗微电子衬底的剥离和清洗组合物包含:
a)至少一种有机剥离溶剂,
b)至少一种亲核胺,
c)至少一种不含氮的弱酸,其量足以中和约重量3%~约75重量%、优选约19重量%~约75重量%的亲核胺,使得该剥离组合物的水相pH为约9.6~约10.9,所述弱酸在水溶液中的pK值为2.0或更大且当量低于140,
d)至少一种去除金属化合物,该化合物选自二甘醇和二甘醇胺,和
e)水。
组合物可以另外包含一种或多种组分如络合金属化合物/耐蚀化合物,其它腐蚀抑制剂和表面活性剂。
根据本发明清洗微电子衬底的方法包括清洗微电子衬底而不产生任何明显金属腐蚀的方法,所述衬底含有至少一种光致抗蚀剂聚合物材料、蚀刻残留物和金属残留物,该方法包括使该衬底与清洗组合物接触一段足以清洗衬底的时间,其中该清洗组合物包括:
a)至少一种有机剥离溶剂,
b)至少一种亲核胺,
c)至少一种不含氮的弱酸,其量足以中和约3重量%~约75重量%、优选约19重量%~约75重量%的亲核胺,使得该剥离组合物的水相pH为约9.6~约10.9,所述弱酸在水溶液中的pK值为2.0或更大且当量低于140,
d)至少一种去除金属化合物,选自二甘醇和二甘醇胺,和
e)水。
用于本发明方法的组合物可以另外包含一种或多种组分如络合金属化合物/耐蚀化合物,其它腐蚀抑制剂和表面活性剂。根据本发明清洗微电子衬底的方法对清洗衬底特别有用,该衬底包括具有通道和含有来自钛层和/或一氮化钛层至少之一的金属残留物的敷铝衬底。
发明详述和具体实施方案
本发明提供用于清洗微电子衬底的剥离和清洗组合物,该组合物包括:至少一种有机剥离溶剂,至少一种亲核胺,至少一种不含氮的弱酸,其量足以中和约3重量%~约75重量%、优选约19重量%~约75重量%的亲核胺,使得剥离组合物的水相pH为约9.6~约10.9,所述弱酸在水溶液中的pK值为2.0或更大且当量低于140,至少一种去除金属化合物,选自二甘醇和二甘醇胺,和水,以及用这些组合物清洗微电子衬底的方法。
本发明用于清洗微电子衬底的剥离和清洗组合物包含:
a)至少一种有机剥离溶剂,
b)至少一种亲核胺,
c)至少一种不含氮的弱酸,其量足以中和约重量3%~约75重量%、优选约19重量%~约75重量%的亲核胺,使得该剥离组合物的水相pH为约9.6~约10.9,所述弱酸在水溶液中的pK值为2.0或更大且当量低于140,
d)至少一种去除金属化合物,选自二甘醇和二甘醇胺,和
e)水。
组合物可以另外包含一种或多种组分如络合金属化合物/耐蚀化合物,其它腐蚀抑制剂和表面活性剂。
所述至少一种有机剥离溶剂一般以约20~约80wt%、优选约30~约75wt%和更优选约40~约60wt%的量存在于组合物中。有机剥离溶剂一般是一种溶解度参数为约8~约15的溶剂,该溶解度参数通过三个Hansen溶解度参数(分散、极性和氢键)的总和取平方根而获得。溶剂体系可以包含一种或多种此类溶剂。适合的溶剂包括,但不限于,2-吡咯烷酮,1-甲基-2-吡咯烷酮,1-乙基-2-吡咯烷酮,1-丙基-2-吡咯烷酮,1-羟乙基-2-吡咯烷酮,1-羟丙基-2-吡咯烷酮等; 二甘醇单烷基醚, 如通式为HO-CH2-CH2-O-CH2-CH2-O-R的这类醚,其中R是1~4个碳原子的烷基;含有硫氧化物如通式R1-S(O)(O)-R2的二烷基砜化合物,其中R1和R2是1~4个碳原子的烷基;二甲亚砜(DMSO);四氢噻吩-1,1-二氧化物化合物,如环丁砜,甲基环丁砜和烷基环丁砜,二甲基乙酰胺和二甲基甲酰胺。优选溶剂是N-甲基吡咯烷酮。
本发明组合物的至少一种亲核胺组分一般以约1~约50wt%、优选约10~约45wt%和更优选约20~约30wt%的量存在于组合物中。可用于本发明的碱性剥离剂组分还包括许多结构类型。它们的离解常数以pK值表示,一般对于β-氧或氮取代的胺为约9~约11,对于仲胺为约8.3,吗啉和羟胺和羟胺衍生物具有较低的pK值。在这些可以使用的碱性组分中,可以提到的是亲核胺,优选例如烷醇胺,特别是单乙醇胺,1-氨基-2-丙醇,2-(2-氨基乙氧基)乙醇,2-氨基乙醇,2-(2-氨基乙基氨基)乙醇,2-(2-氨基乙基氨基)乙胺等。相比胺的实际pK值更重要的是其亲核性应该高。最优选该亲核胺是单乙醇胺或1-氨基-2-丙醇。
本发明组合物的不含氮弱酸组分一般以约0.5~约10wt%、优选约1~约8wt%和更优选约2~约6wt%的量存在于组合物中。可以应用于本发明的不含氮弱酸包括有机酸如羧酸或苯酚,以及无机酸(如碳酸或氢氟酸)的盐。弱酸指在水溶液中用离解常数“pK”表示的酸强度为至少2.0或更高、优选2.5或更高。特别有用的弱酸的pK>2.0且优选当量低于约140。可用于本发明的此类不含氮的弱酸的实例可以提到,例如,羧酸如乙酸,邻苯二甲酸,苯氧基乙酸等,有机酸如2-巯基苯甲酸,2-巯基乙醇等,pK通常为在9~10的苯酚类,如苯酚,邻苯二酚,1,3,5-三羟基苯,邻苯三酚,间苯二酚,4-叔丁基邻苯二酚等,和无机酸如碳酸,氢氟酸等等。本发明剥离组合物中所用的弱酸量为中和约3重量%~约75重量%、优选约19重量%~约75重量%的存在于剥离剂组合物中胺的量,从而导致所述剥离剂组合物的水漂洗液的pH为约pH 9.6~约10.9。最优选弱酸是邻苯二酚。
所述至少一种去除金属组分是二甘醇或二甘醇胺或它们的混合物。该组分一般以约0.5~约40wt%、优选约1~约20wt%和更优选约5~约15wt%的量存在于组合物中。该组分优选是二甘醇。
本发明的清洗和剥离组合物是碱性含水组合物,水一般以约0.5~约50wt%、优选约1~约35wt%和更优选约5~约20wt%的量存在。
本发明的组合物也可以任选含有其它附加组分。该任选的附加组分包括络合金属化合物/耐蚀化合物,其它腐蚀抑制剂和表面活性剂。
有机或无机螯合剂或金属络合剂/腐蚀抑制剂不是必需的,但是可以任选包含于本发明的组合物中,而获得显著的益处,例如当引入本发明的含水清洗组合物时改善了产品稳定性。适合的螯合剂或络合剂的实例包括但不限于反式-1,2-环己二胺四乙酸(CyDTA),乙二胺四乙酸(EDTA),锡酸盐,焦磷酸盐,亚烷基-二磷酸衍生物(例如乙烷-1-羟基-1,1-二磷酸盐),含有乙二胺、二亚乙基三胺或三亚乙基四胺官能部分的膦酸盐[例如乙二胺四(亚甲基膦酸)(EDTMP),二亚乙基三胺五(亚甲基膦酸),三亚乙基四胺六(亚甲基膦酸)。以组合物的重量为准计,螯合剂可以0~约5wt%、优选约0.1~约2wt%的量存在于组合物中。
本发明的含水清洗组合物还可以任选含有其它腐蚀抑制剂和应用于微电子清洁化合物组合物的类似的无腐蚀组分。化合物可以包括间苯二酚,五倍子酸,没食子酸丙酯,邻苯三酚,氢醌,苯并三唑和苯并三唑的衍生物,和多官能团羧酸如柠檬酸,酒石酸,葡糖酸,糖二酸,甘油酸,草酸,邻苯二甲酸,马来酸,扁桃酸,丙二酸,乳酸,和水杨酸。 这些其它的腐蚀抑制剂可以任何适合的量存在,含量一般为约0~约5wt%、优选约0.1~约3wt%和更优选约0.2~约2wt%。
本发明的组合物也可以任选含有任何适合的水可溶两性、非离子、阳离子或阴离子的表面活性剂。表面活性剂的加入将降低制剂的表面张力,改善欲清洗表面的润湿,由此提高组合物的清洗作用。如果还需要抑制铝腐蚀,也可以加入表面活性剂以减少铝腐蚀速率。对本发明组合物有用的两性表面活性剂包括甜菜碱和磺基甜菜碱,如烷基甜菜碱,氨基烷基甜菜碱,烷基磺基甜菜碱和氨基烷基磺基甜菜碱;氨基羧酸衍生物如两性甘氨酸盐(酯),两性丙酸盐(酯),两性二甘氨酸盐(酯),和两性二丙酸盐(酯);亚氨基二酸如烷氧基烷基亚氨基二酸或烷氧基烷基亚氨基二酸;氧化胺如烷基胺氧化物和烷基酰胺基烷基胺氧化物;氟烷基磺酸盐和氟化烷基两性表面活性剂;和它们的混合物。优选,两性表面活性剂是椰油酰胺基丙基甜菜碱,椰油酰胺基丙基二甲基甜菜碱,椰油酰胺基丙基羟基磺基甜菜碱(cocoamidopropyl hydroxyl sultaine),辛酰基两性二丙酸盐(酯)(capryloamphodipropionate),椰油酰胺基二丙酸盐(酯)(cocoamidodipropionate),椰油基两性丙酸盐(酯)(cocoamphopropionate),椰油基两性羟乙基丙酸盐(酯),异癸氧基丙基亚氨基二丙酸,月桂基亚氨基二丙酸盐(酯),氧化椰油酰胺基丙基胺和氧化椰油胺(cocoamine oxide)和氟化烷基两性表面活性剂。对本发明组合物有用的非离子型表面活性剂包括炔二醇,乙氧基化炔二醇,氟化烷基烷氧基化物,氟化烷基酯,氟化聚氧化乙烯链烷醇,多元醇的脂肪酸酯,聚氧化乙烯单烷基醚,聚氧化乙烯二醇,硅氧烷型表面活性剂,和亚烷基二醇单烷基醚。 优选,非离子型表面活性剂是炔二醇或乙氧基化炔二醇。对本发明组合物有用的阴离子表面活性剂包括羧酸盐(酯),N-酰基肌氨酸盐(酯),磺酸盐(酯),硫酸盐(酯),和正磷酸的单酯(盐)和二酯(盐)如磷酸癸酯(盐)。优选,阴离子表面活性剂是不含金属的表面活性剂。对本发明组合物有用的阳离子表面活性剂包括胺乙氧基化物,二烷基二甲基铵盐,二烷基吗啉鎓盐,烷基苄基二甲基铵盐,烷基三甲基铵盐,和烷基吡啶鎓盐。优选,阳离子表面活性剂是不含卤素的表面活性剂。尤其适合的表面活性剂实例包括,但不限于3,5-二甲基-已炔-3-醇(Surfynol-61),乙氧基化2,4,7,9-四甲基-5-癸炔-4,7-二醇(Surfynol-465),聚四氟乙烯鲸蜡氧基丙基甜菜碱(polytetrafluoroethylenecetoxypropylbetaine)(Zonyl FSK),Zonyl FSH,Triton X-100,即辛基苯氧基聚乙氧基乙醇等。表面活性剂一般可以0~约5wt%、优选约0.001~约3wt%的量存在于组合物中,基于组合物的重量。
本发明清洗组合物的实例包括,但不限于,下面表1、2、3和4中阐述的组合物。在表1、2、3和4中以及下面表5~9中,使用的缩写如下:
NMP=N-甲基吡咯烷酮
DMSO=二甲亚砜
DMAC=二甲基乙酰胺
DMF=二甲基甲酰胺
DEG=二甘醇
DEGA=二甘醇胺
CAT=邻苯二酚
MEA=单乙醇胺
AMP=1-氨基-2-丙醇
表1
组合物/重量份
组分 | 1 | 2 | 3 | 4 | 5 |
NMP | 46 | 26 | 26 | 26 | 26 |
DMSO | |||||
DMAC | |||||
MEA | 23 | 20 | 20 | 10 | 10 |
AMP | |||||
DEG | 11 | 8 | |||
DEGA | 8 | 2 | 8 | ||
CAT | 5 | 1 | 1 | 1 | 5 |
水 | 15 | 4 | 4 | 4 | 4 |
表2
组合物/重量份
组分 | 6 | 7 | 8 | 9 | 10 |
NMP | 26 | 26 | 26 | 26 | 26 |
DMSO | |||||
DMAC | |||||
MEA | 20 | 20 | 15 | 15 | 15 |
AMP | |||||
DEG | 5 | ||||
DEGA | 2 | 8 | 5 | 5 | |
CAT | 5 | 5 | 3 | 1 | 3 |
水 | 4 | 10 | 7 | 7 | 4 |
表3
组合物/重量份
组分 | 11 | 12 | 13 | 14 | 15 |
NMP | 46 | 46 | 54 | 46 |
DMSO | |||||
DMAC | 46 | ||||
MEA | 21 | 25 | 21 | ||
AMP | 23 | 23 | |||
DEG | 13 | 9 | 11 | 11 | |
DEGA | 9 | ||||
CAT | 7 | 3 | 3 | 5 | 5 |
水 | 13 | 17 | 13 | 15 | 15 |
表4
组合物/重量份
组分 | 16 |
NMP | |
DMSO | 46 |
DMAC | |
MEA | 23 |
AMP | |
DEG | 11 |
DEGA | |
CAT | 5 |
水 | 15 |
本发明清洗组合物突出的清洗和无腐蚀性能相比用其它多羟基化合物代替DEG和DEGA的类似组合物通过下面的清洗实施例1~11说明。几种清洗组合物通过混合26g NMP,20g单乙醇胺,1g邻苯二酚,4g去离子水和8g清洁化合物而制备,该清洁化合物选自下列:二甘醇(DEG),二甘醇胺(DEGA),三甘醇,四甘醇,乙二醇,丙二醇,N-甲基乙醇胺,2-(2-氨基乙基氨基)乙醇,2-丁烯-1,4-二醇和2-(2-甲氧基乙氧基)乙醇。将具有“穿透”通道结构的图案化Al工艺薄片(wafer)样品(通道蚀刻通过Si和TiN到Al层)置于这种加热到85℃的溶液中20分钟,之后将其取出,在去离子水中漂洗两分钟,用氮气吹干。用于对比,在购买的US专利5,308,745的剥离组合物(含有NMP、环丁砜、MEA,邻苯二酚和去离子水)中清洗相同的薄片。然后评价该经清洗的薄片对灰化残留物的去除(0=没有去除,至10=100%去除)和铝腐蚀(0=没有腐蚀,至10=腐蚀)的性能,如表5所注释。
表5
实施例# | 清洗化合物 | 铝腐蚀 | 灰化残留物去除 |
1 | 二甘醇 | 0 | 10 |
2 | 二甘醇胺 | 1 | 8 |
3 | 四甘醇 | 0 | 5 |
4 | 2-丁烯-1,4-二醇 | 0 | 5 |
5 | 乙二醇 | 0 | 4 |
6 | 丙二醇 | 0 | 4 |
7 | N,N-二甲基乙醇胺 | 1 | 4 |
8 | 2-(2-氨基乙基氨基)乙醇 | 2 | 2 |
9 | 2-(2-甲氧基乙氧基)乙醇 | 0 | 2 |
10 | 三甘醇 | 0 | 1 |
11 | US专利5,308,745的商品 | 0 | 1 |
仅有DEG和DEGA提供优异的灰化残留物去除和铝腐蚀抑制。在下面实施例12~29示范性给出了在各种时间和温度以及不同制剂的清洗条件下,本发明清洗组合物的实用性。
实施例12~16
几种清洗组合物通过混合1-甲基-2-吡咯烷酮(NMP),单乙醇胺(MEA),二甘醇胺(DEGA),邻苯二酚(CAT)和去离子水而制备,其量显示如下。将与实施例1~11使用的相同类型的具有“穿透”通道的图案化Al工艺薄片样品置于加热到85℃的这些溶液中20分钟,将其取出之后,在去离子水中漂洗两分钟,用氮气吹干。然后评价该经清洗的薄片对灰化残留物的去除(0=没有去除,至10=100%去除)和铝腐蚀(0=没有腐蚀,至10=严重腐蚀),如表6注释。
表6
实施例# | NMP | MEA | DEGA | 邻苯二酚 | H2O | 铝腐蚀 | 灰化残留 |
物去除 | |||||||
12 | 26 | 10 | 2 | 1 | 4 | 0 | 10 |
13 | 26 | 10 | 8 | 5 | 4 | 0 | 8 |
14 | 26 | 20 | 2 | 5 | 4 | 0 | 10 |
15 | 26 | 20 | 8 | 5 | 10 | 2 | 10 |
16 | 26 | 15 | 5 | 3 | 7 | 1 | 10 |
实施例17~22
几种清洗组合物通过混合26g NMP,15g单乙醇胺(MEA),5g二甘醇胺(DEGA)或二甘醇(DEG),3g邻苯二酚(CAT),和7g去离子水而制备。将与先前实施例使用的相同类型的具有“穿透”通道的图案化Al工艺薄片样品置于这些加热到如下所示温度的溶液中20分钟,之后将其取出,在去离子水中漂洗两分钟,用氮气吹干。然后评价该经清洗的薄片对灰化残留物的去除(0=没有去除,至10=100%去除)和铝腐蚀(0=没有腐蚀,至10=严重腐蚀),如下面表7注释。
表7
实施例# | 溶液含有: | 温度(℃) | 铝腐蚀 | 灰化残留物去除 |
17 | DEGA | 65 | 0 | 3 |
18 | DEGA | 75 | 0 | 6 |
19 | DEGA | 85 | 1 | 9 |
20 | DEG | 65 | 0 | 6 |
21 | DEG | 75 | 0 | 8 |
22 | DEG | 85 | 0 | 10 |
实施例23~25
几种清洗组合物通过混合1-甲基-2-吡咯烷酮(NMP),单乙醇胺(MEA),二甘醇(DEG),邻苯二酚(CAT)和去离子水而制备,其量显示如下。与先前实施例使用的相同类型的、具有“穿透”通道的图案化Al工艺薄片样品置于加热到65℃的这些溶液中20分钟,将其取出之后,在去离子水中漂洗两分钟,用氮气吹干。然后评价该经清洗的薄片对灰化残留物的去除(0=没有去除,至10=100%去除)和铝腐蚀(0=没有腐蚀,至10=严重腐蚀),如下面表8注释。
表8
实施例# | NMP | MEA | DEG | 邻苯二酚 | H2O | 铝腐蚀 | 灰化残留物去除 |
23 | 46 | 21 | 13 | 7 | 13 | 0 | 10 |
24 | 46 | 25 | 9 | 7 | 13 | 2 | 10 |
25 | 54 | 21 | 9 | 3 | 13 | 1 | 10 |
实施例26~29
几种清洗组合物通过混合46g选自1-甲基-2-吡咯烷酮(NMP)、N,N-二甲基乙酰胺(DMAC)或二甲亚砜(DMSO)的溶剂,23g单乙醇胺(MEA)或1-氨基-2-丙醇(AMP);11g二甘醇(DEG),5g邻苯二酚(CAT),和15g去离子水而制备。与先前实施例使用的相同类型的、具有“穿透”通道的图案化Al工艺薄片样品置于加热到65℃的这些溶液中20分钟,之后将其取出,在去离子水中漂洗两分钟,用氮气吹干。然后评价该经清洗的薄片对灰化残留物的去除(0=没有去除,至10=100%去除)和铝腐蚀(0=没有腐蚀,至10=严重腐蚀),如下面表9注释。
表9
实施例# | 铝腐蚀 | 灰化残留物去除 | |||||
26 | NMP | MEA | DEG | 邻苯二酚 | H2O | 0 | 10 |
27 | NMP | AMP | DEG | 邻苯二酚 | H2O | 0 | 8 |
28 | DMAC | MEA | DEG | 邻苯二酚 | H2O | 2 | 10 |
29 | DMSO | MEA | DEG | 邻苯二酚 | H2O | 1 | 9 |
尽管本发明参考其特定实施方式已进行了描述,但应认识到,可以进行改变、修改和变化而不脱离本发明在此公开的实质和范围。因此,其意指本发明包含所有落入所附权利要求的精神和范围内的这些改变、修改和变化。
Claims (32)
1、一种用于清洗微电子衬底的剥离和清洗组合物,该组合物包含:
a)至少一种有机剥离溶剂,
b)至少一种亲核胺,
c)至少一种不含氮的弱酸,其量足以中和约3重量%~约75重量%的亲核胺,使得该剥离组合物的水相pH为约9.6~约10.9,所述弱酸在水溶液中的pK值为2.0或更大且当量低于140,
d)至少一种去除金属化合物,选自二甘醇和二甘醇胺,和
e)水。
2、根据权利要求1所述的组合物,其中所述至少一种亲核胺包括链烷醇胺。
3、根据权利要求1所述的组合物,其中所述至少一种有机剥离溶剂选自N-甲基吡咯烷酮,二甲基乙酰胺和二甲亚砜。
4、根据权利要求3所述的组合物,其中所述至少一种亲核胺包括链烷醇胺。
5、根据权利要求4所述的组合物,其中链烷醇胺选自单乙醇胺和1-氨基-2-丙醇。
6、根据权利要求5所述的组合物,其中所述至少一种弱酸包括邻苯二酚。
7、根据权利要求6所述的组合物,其中所述至少一种有机剥离溶剂包括N-甲基吡咯烷酮,所述链烷醇胺包括单乙醇胺,和所述至少一种去除金属化合物包括二甘醇。
8、根据权利要求1所述的组合物,该组合物还包括一种或多种选自以下的组分:络合金属化合物/耐蚀化合物,其它腐蚀抑制剂和表面活性剂。
9、根据权利要求7所述的组合物,该组合物还包括一种或多种选自以下的组分:络合金属化合物/耐蚀化合物,其它腐蚀抑制剂和表面活性剂。
10、根据权利要求1所述的组合物,该组合物还包括约20~约80wt%的所述至少一种剥离溶剂,约1~约50wt%的所述至少一种亲核胺,约0.5~约40wt%的所述至少一种去除金属化合物,约0.5~约10wt%的所述至少一种弱酸,和约0.5~约50wt%的水。
11、根据权利要求7所述的组合物,该组合物包括约20~约80wt%的N-甲基吡咯烷酮,约1~约50wt%的单乙醇胺,约0.5~约40wt%的二甘醇,约0.5~约10wt%的邻苯二酚,和约0.5~约50wt%的水。
12、根据权利要求1所述的组合物,该组合物包括约40~约60wt%的所述至少一种有机剥离溶剂,约20~约30wt%的所述至少一种亲核胺,约5~约15wt%的所述至少一种去除金属化合物,约2~约6wt%的所述至少一种弱酸,和约5~约20wt%的水。
13、根据权利要求7所述的组合物,该组合物包括约40~约60wt%的N-甲基吡咯烷酮,约20~约30wt%的单乙醇胺,约5~约15wt%的二甘醇,约2~约6wt%的邻苯二酚,和约5~约20wt%的水。
14、根据权利要求13所述的组合物,该组合物包括约46wt%的N-甲基吡咯烷酮,约23wt%的单乙醇胺,约11wt%的二甘醇,约5wt%的邻苯二酚,和约15wt%的水。
15、一种清洗微电子衬底而不产生任何明显金属腐蚀的方法,该衬底含有至少一种光致抗蚀剂聚合物材料、刻蚀残留物和金属残留物,该方法包括使衬底与清洗组合物接触一段足以清洗衬底的时间,其中清洗组合物包括:
a)至少一种有机剥离溶剂,
b)至少一种亲核胺,
c)至少一种不含氮的弱酸,其量足以中和约重量3%~约75重量%的亲核胺,使得该剥离组合物的水相pH为约9.6~约10.9,所述弱酸在水溶液中的pK值为2.0或更大且当量低于140,
d)至少一种去除金属化合物,该化合物选自二甘醇和二甘醇胺,和
e)水。
16、根据权利要求15所述的方法,其中所述至少一种亲核胺包括链烷醇胺。
17、根据权利要求15所述的方法,其中所述至少一种有机剥离溶剂选自N-甲基吡咯烷酮,二甲基乙酰胺和二甲亚砜。
18、根据权利要求17所述的方法,其中所述至少一种亲核胺包括链烷醇胺。
19、根据权利要求18所述的方法,其中链烷醇胺选自单乙醇胺和1-氨基-2-丙醇。
20、根据权利要求19所述的方法,其中所述至少一种弱酸包括邻苯二酚。
21、根据权利要求20所述的方法,其中所述至少一种有机剥离溶剂包括N-甲基吡咯烷酮,所述链烷醇胺包括单乙醇胺,和所述至少一种去除金属化合物包括二甘醇。
22、根据权利要求15所述的方法,其中所述组合物还包括一种或多种选自以下的组分:络合金属化合物/耐蚀化合物,其它腐蚀抑制剂和表面活性剂。
23、根据权利要求21所述的方法,其中所述组合物还包括一种或多种选自以下的组分:络合金属化合物/耐蚀化合物,其它腐蚀抑制剂和表面活性剂。
24、根据权利要求15所述的方法,其中所述组合物包括约20~约80wt%的所述至少一种剥离溶剂,约1~约50wt%的所述至少一种亲核胺,约0.5~约40wt%的所述至少一种去除金属化合物,约0.5~约10wt%的所述至少一种弱酸,和约0.5~约50wt%的水。
25、根据权利要求21所述的方法,其中所述组合物包括约20~约80wt%的N-甲基吡咯烷酮,约1~约50wt%的单乙醇胺,约0.5~约40wt%的二甘醇,约0.5~约10wt%的邻苯二酚,和约0.5~约50wt%的水。
26、根据权利要求15所述的方法,其中所述组合物包括约40~约60wt%的所述至少一种有机剥离溶剂,约20~约30wt%的所述至少一种亲核胺,约5~约15wt%的所述至少一种去除金属化合物,约2~约6wt%的所述至少一种弱酸,和约5~约20wt%的水。
27、根据权利要求21所述的方法,其中所述组合物包括约40~约60wt%的N-甲基吡咯烷酮,约20~约30wt%的单乙醇胺,约5~约15wt%的二甘醇,约2~约6wt%的邻苯二酚,和约5~约20wt%的水。
28、根据权利要求27所述的方法,包括约46wt%的N-甲基吡咯烷酮,约23wt%的单乙醇胺,约11wt%的二甘醇,其中所述组合物约5wt%的邻苯二酚,和约15wt%的水。
29、根据权利要求15所述的方法,其中所述衬底包括具有通道并含有金属残留物的敷铝衬底。
30、根据权利要求29所述的方法,其中所述金属残留物来自选自钛层和一氮化钛层中的至少一层。
31、根据权利要求21所述的方法,其中所述衬底包括具有通道并含有金属残留物的敷铝衬底。
32、根据权利要求31所述的方法,其中所述金属残留物来自选自钛层和一氮化钛层中的至少一层。
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CA2575991A1 (en) | 2006-03-02 |
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TWI390032B (zh) | 2013-03-21 |
PT1789527E (pt) | 2010-01-15 |
DK1789527T3 (da) | 2010-03-08 |
MY144284A (en) | 2011-08-29 |
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JP2008509554A (ja) | 2008-03-27 |
ATE450595T1 (de) | 2009-12-15 |
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IL181106A0 (en) | 2007-07-04 |
DE602005018075D1 (de) | 2010-01-14 |
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BRPI0514058A (pt) | 2008-05-27 |
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