CN101531950A - 含有氨基苯磺酸的半水性溶脱和清洗组合物 - Google Patents
含有氨基苯磺酸的半水性溶脱和清洗组合物 Download PDFInfo
- Publication number
- CN101531950A CN101531950A CN200910128161A CN200910128161A CN101531950A CN 101531950 A CN101531950 A CN 101531950A CN 200910128161 A CN200910128161 A CN 200910128161A CN 200910128161 A CN200910128161 A CN 200910128161A CN 101531950 A CN101531950 A CN 101531950A
- Authority
- CN
- China
- Prior art keywords
- composition
- hydroxide
- ammonium
- sulfonic acid
- aniline sulfonic
- 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
Links
- 239000000203 mixture Substances 0.000 title claims abstract description 70
- ZAJAQTYSTDTMCU-UHFFFAOYSA-N 3-aminobenzenesulfonic acid Chemical compound NC1=CC=CC(S(O)(=O)=O)=C1 ZAJAQTYSTDTMCU-UHFFFAOYSA-N 0.000 title claims abstract description 12
- 238000004140 cleaning Methods 0.000 title claims description 25
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 36
- 239000003960 organic solvent Substances 0.000 claims abstract description 18
- 238000000034 method Methods 0.000 claims abstract description 13
- WGTYBPLFGIVFAS-UHFFFAOYSA-M tetramethylammonium hydroxide Chemical compound [OH-].C[N+](C)(C)C WGTYBPLFGIVFAS-UHFFFAOYSA-M 0.000 claims description 56
- ARXJGSRGQADJSQ-UHFFFAOYSA-N 1-methoxypropan-2-ol Chemical compound COCC(C)O ARXJGSRGQADJSQ-UHFFFAOYSA-N 0.000 claims description 28
- 239000000758 substrate Substances 0.000 claims description 27
- -1 glycol ethers Chemical class 0.000 claims description 17
- BEHLMOQXOSLGHN-UHFFFAOYSA-N benzenamine sulfate Chemical compound OS(=O)(=O)NC1=CC=CC=C1 BEHLMOQXOSLGHN-UHFFFAOYSA-N 0.000 claims description 16
- XPFVYQJUAUNWIW-UHFFFAOYSA-N furfuryl alcohol Chemical compound OCC1=CC=CO1 XPFVYQJUAUNWIW-UHFFFAOYSA-N 0.000 claims description 15
- 239000004065 semiconductor Substances 0.000 claims description 14
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 13
- 238000004380 ashing Methods 0.000 claims description 13
- ZMCHBSMFKQYNKA-UHFFFAOYSA-N 2-aminobenzenesulfonic acid Chemical compound NC1=CC=CC=C1S(O)(=O)=O ZMCHBSMFKQYNKA-UHFFFAOYSA-N 0.000 claims description 12
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 claims description 12
- 239000001089 [(2R)-oxolan-2-yl]methanol Substances 0.000 claims description 12
- 238000005260 corrosion Methods 0.000 claims description 12
- 230000007797 corrosion Effects 0.000 claims description 12
- 239000003112 inhibitor Substances 0.000 claims description 12
- BSYVTEYKTMYBMK-UHFFFAOYSA-N tetrahydrofurfuryl alcohol Chemical compound OCC1CCCO1 BSYVTEYKTMYBMK-UHFFFAOYSA-N 0.000 claims description 12
- 238000005530 etching Methods 0.000 claims description 11
- LYCAIKOWRPUZTN-UHFFFAOYSA-N ethylene glycol Natural products OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 11
- FENFUOGYJVOCRY-UHFFFAOYSA-N 1-propoxypropan-2-ol Chemical compound CCCOCC(C)O FENFUOGYJVOCRY-UHFFFAOYSA-N 0.000 claims description 9
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 claims description 9
- 150000003839 salts Chemical class 0.000 claims description 9
- DHMQDGOQFOQNFH-UHFFFAOYSA-N Glycine Chemical compound NCC(O)=O DHMQDGOQFOQNFH-UHFFFAOYSA-N 0.000 claims description 8
- HVBSAKJJOYLTQU-UHFFFAOYSA-N 4-aminobenzenesulfonic acid Chemical compound NC1=CC=C(S(O)(=O)=O)C=C1 HVBSAKJJOYLTQU-UHFFFAOYSA-N 0.000 claims description 7
- PQUCIEFHOVEZAU-UHFFFAOYSA-N Diammonium sulfite Chemical compound [NH4+].[NH4+].[O-]S([O-])=O PQUCIEFHOVEZAU-UHFFFAOYSA-N 0.000 claims description 7
- 150000002443 hydroxylamines Chemical class 0.000 claims description 7
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 claims description 6
- 150000007524 organic acids Chemical group 0.000 claims description 6
- LJXQPZWIHJMPQQ-UHFFFAOYSA-N pyrimidin-2-amine Chemical compound NC1=NC=CC=N1 LJXQPZWIHJMPQQ-UHFFFAOYSA-N 0.000 claims description 6
- 150000003856 quaternary ammonium compounds Chemical class 0.000 claims description 6
- VDZOOKBUILJEDG-UHFFFAOYSA-M tetrabutylammonium hydroxide Chemical compound [OH-].CCCC[N+](CCCC)(CCCC)CCCC VDZOOKBUILJEDG-UHFFFAOYSA-M 0.000 claims description 5
- KYVBNYUBXIEUFW-UHFFFAOYSA-N 1,1,3,3-tetramethylguanidine Chemical compound CN(C)C(=N)N(C)C KYVBNYUBXIEUFW-UHFFFAOYSA-N 0.000 claims description 4
- FVRSWMRVYMPTBU-UHFFFAOYSA-M 1-hydroxypropyl(trimethyl)azanium;hydroxide Chemical compound [OH-].CCC(O)[N+](C)(C)C FVRSWMRVYMPTBU-UHFFFAOYSA-M 0.000 claims description 4
- KIZQNNOULOCVDM-UHFFFAOYSA-M 2-hydroxyethyl(trimethyl)azanium;hydroxide Chemical compound [OH-].C[N+](C)(C)CCO KIZQNNOULOCVDM-UHFFFAOYSA-M 0.000 claims description 4
- ZFDNAYFXBJPPEB-UHFFFAOYSA-M 2-hydroxyethyl(tripropyl)azanium;hydroxide Chemical compound [OH-].CCC[N+](CCC)(CCC)CCO ZFDNAYFXBJPPEB-UHFFFAOYSA-M 0.000 claims description 4
- LCGLNKUTAGEVQW-UHFFFAOYSA-N Dimethyl ether Chemical compound COC LCGLNKUTAGEVQW-UHFFFAOYSA-N 0.000 claims description 4
- 229930091371 Fructose Natural products 0.000 claims description 4
- 239000005715 Fructose Substances 0.000 claims description 4
- RFSUNEUAIZKAJO-ARQDHWQXSA-N Fructose Chemical compound OC[C@H]1O[C@](O)(CO)[C@@H](O)[C@@H]1O RFSUNEUAIZKAJO-ARQDHWQXSA-N 0.000 claims description 4
- 239000004471 Glycine Substances 0.000 claims description 4
- CRAFBOZKMVZBDP-UHFFFAOYSA-N [OH-].C(C)[NH3+].C[NH+](C)C.[OH-] Chemical compound [OH-].C(C)[NH3+].C[NH+](C)C.[OH-] CRAFBOZKMVZBDP-UHFFFAOYSA-N 0.000 claims description 4
- XYXNTHIYBIDHGM-UHFFFAOYSA-N ammonium thiosulfate Chemical compound [NH4+].[NH4+].[O-]S([O-])(=O)=S XYXNTHIYBIDHGM-UHFFFAOYSA-N 0.000 claims description 4
- NDKBVBUGCNGSJJ-UHFFFAOYSA-M benzyltrimethylammonium hydroxide Chemical compound [OH-].C[N+](C)(C)CC1=CC=CC=C1 NDKBVBUGCNGSJJ-UHFFFAOYSA-M 0.000 claims description 4
- KVFVBPYVNUCWJX-UHFFFAOYSA-M ethyl(trimethyl)azanium;hydroxide Chemical compound [OH-].CC[N+](C)(C)C KVFVBPYVNUCWJX-UHFFFAOYSA-M 0.000 claims description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 claims description 4
- NBZBKCUXIYYUSX-UHFFFAOYSA-N iminodiacetic acid Chemical compound OC(=O)CNCC(O)=O NBZBKCUXIYYUSX-UHFFFAOYSA-N 0.000 claims description 4
- DZLFLBLQUQXARW-UHFFFAOYSA-N tetrabutylammonium Chemical compound CCCC[N+](CCCC)(CCCC)CCCC DZLFLBLQUQXARW-UHFFFAOYSA-N 0.000 claims description 4
- 229940073455 tetraethylammonium hydroxide Drugs 0.000 claims description 4
- LRGJRHZIDJQFCL-UHFFFAOYSA-M tetraethylazanium;hydroxide Chemical compound [OH-].CC[N+](CC)(CC)CC LRGJRHZIDJQFCL-UHFFFAOYSA-M 0.000 claims description 4
- LPSKDVINWQNWFE-UHFFFAOYSA-M tetrapropylazanium;hydroxide Chemical compound [OH-].CCC[N+](CCC)(CCC)CCC LPSKDVINWQNWFE-UHFFFAOYSA-M 0.000 claims description 4
- 150000003852 triazoles Chemical class 0.000 claims description 4
- GRNRCQKEBXQLAA-UHFFFAOYSA-M triethyl(2-hydroxyethyl)azanium;hydroxide Chemical compound [OH-].CC[N+](CC)(CC)CCO GRNRCQKEBXQLAA-UHFFFAOYSA-M 0.000 claims description 4
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 26
- GTDKXDWWMOMSFL-UHFFFAOYSA-M tetramethylazanium;fluoride Chemical compound [F-].C[N+](C)(C)C GTDKXDWWMOMSFL-UHFFFAOYSA-M 0.000 description 16
- SAOKZLXYCUGLFA-UHFFFAOYSA-N bis(2-ethylhexyl) adipate Chemical compound CCCCC(CC)COC(=O)CCCCC(=O)OCC(CC)CCCC SAOKZLXYCUGLFA-UHFFFAOYSA-N 0.000 description 14
- 239000003643 water by type Substances 0.000 description 13
- 235000015165 citric acid Nutrition 0.000 description 12
- 239000010410 layer Substances 0.000 description 11
- 239000000463 material Substances 0.000 description 10
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 9
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 7
- 229910052802 copper Inorganic materials 0.000 description 7
- 239000010949 copper Substances 0.000 description 7
- 239000008367 deionised water Substances 0.000 description 7
- 229910021641 deionized water Inorganic materials 0.000 description 7
- AFVFQIVMOAPDHO-UHFFFAOYSA-N Methanesulfonic acid Chemical compound CS(O)(=O)=O AFVFQIVMOAPDHO-UHFFFAOYSA-N 0.000 description 6
- JOXIMZWYDAKGHI-UHFFFAOYSA-N toluene-4-sulfonic acid Chemical compound CC1=CC=C(S(O)(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-N 0.000 description 6
- 239000003989 dielectric material Substances 0.000 description 5
- 125000004169 (C1-C6) alkyl group Chemical group 0.000 description 4
- LNTHITQWFMADLM-UHFFFAOYSA-N gallic acid Chemical compound OC(=O)C1=CC(O)=C(O)C(O)=C1 LNTHITQWFMADLM-UHFFFAOYSA-N 0.000 description 4
- 229910052751 metal Inorganic materials 0.000 description 4
- 239000002184 metal Substances 0.000 description 4
- 229920002120 photoresistant polymer Polymers 0.000 description 4
- GHMLBKRAJCXXBS-UHFFFAOYSA-N resorcinol Chemical compound OC1=CC=CC(O)=C1 GHMLBKRAJCXXBS-UHFFFAOYSA-N 0.000 description 4
- 229920001174 Diethylhydroxylamine Polymers 0.000 description 3
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 3
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 3
- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid Chemical compound OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 3
- FVCOIAYSJZGECG-UHFFFAOYSA-N diethylhydroxylamine Chemical compound CCN(O)CC FVCOIAYSJZGECG-UHFFFAOYSA-N 0.000 description 3
- 239000011229 interlayer Substances 0.000 description 3
- 239000011159 matrix material Substances 0.000 description 3
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- 239000010703 silicon Substances 0.000 description 3
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- 239000000126 substance Substances 0.000 description 3
- 239000010936 titanium Substances 0.000 description 3
- XNWFRZJHXBZDAG-UHFFFAOYSA-N 2-METHOXYETHANOL Chemical compound COCCO XNWFRZJHXBZDAG-UHFFFAOYSA-N 0.000 description 2
- LDMRLRNXHLPZJN-UHFFFAOYSA-N 3-propoxypropan-1-ol Chemical compound CCCOCCCO LDMRLRNXHLPZJN-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
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- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 description 2
- KRHYYFGTRYWZRS-UHFFFAOYSA-M Fluoride anion Chemical compound [F-] KRHYYFGTRYWZRS-UHFFFAOYSA-M 0.000 description 2
- VZCYOOQTPOCHFL-OWOJBTEDSA-N Fumaric acid Chemical compound OC(=O)\C=C\C(O)=O VZCYOOQTPOCHFL-OWOJBTEDSA-N 0.000 description 2
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 description 2
- OFOBLEOULBTSOW-UHFFFAOYSA-N Propanedioic acid Natural products OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 2
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- NRTOMJZYCJJWKI-UHFFFAOYSA-N Titanium nitride Chemical compound [Ti]#N NRTOMJZYCJJWKI-UHFFFAOYSA-N 0.000 description 2
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- 238000002242 deionisation method Methods 0.000 description 2
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- 229940074391 gallic acid Drugs 0.000 description 2
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- 239000011521 glass Substances 0.000 description 2
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- FPGGTKZVZWFYPV-UHFFFAOYSA-M tetrabutylammonium fluoride Chemical compound [F-].CCCC[N+](CCCC)(CCCC)CCCC FPGGTKZVZWFYPV-UHFFFAOYSA-M 0.000 description 2
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- G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
- G03F7/26—Processing photosensitive materials; Apparatus therefor
- G03F7/42—Stripping or agents therefor
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Abstract
本发明涉及用于除去高度交联的抗蚀剂和蚀刻残留物的半水性组合物及其使用方法。该组合物包含氨基苯磺酸、可与水混溶的有机溶剂和水。
Description
背景技术
在半导体或半导体微电路的制造过程中,有必要从半导体器件基板的表面除去某些物质。在某些情况中,要除去的物质是被称作光致抗蚀剂(photoresists)的聚合的合成物。在其它情况中,要除去的物质是蚀刻或灰磨处理的残留物或者仅是污染物。溶脱(strip)和/或清洗组合物的目的是从半导体基板除去不需要的物质而不腐蚀、溶解或钝化基板的暴露表面。
现有技术中有众多的涉及用于从半导体基板溶脱光致抗蚀剂和/或清洗蚀刻残留物、灰分或其它污染物的不同类型组合物的参考文献。
这一技术领域中的专利包括Torii的US 5,972,862、Inoue的US6,232,283 B1、Mayhan的US 5,534,177、McGrady的US 4,321,166、Jones的US 4,199,483、Borchert的US 3,653,931、Mey的US 4,215,005、US 4,165,295和US 4,242,218。
发明内容
本发明涉及半水性溶脱和清洗组合物及其使用方法。该组合物包含氨基苯磺酸、可与水混溶的有机溶剂和水。
在一种实施方式中,所述半水性溶脱和清洗组合物包含
a.0.5%至10%的氨基苯磺酸或其对应的盐,
b.30%至90%的可与水混溶的有机溶剂,和
c.5%至70%的水。
在另一种实施方式中,从半导体基板除去光致抗蚀剂、蚀刻和/或灰磨残留物或者污染物的方法包括:
使半导体基板与包含以下成分的组合物接触足以充分地除去光致抗蚀剂、蚀刻和/或灰磨残留物或者污染物的一段时间:
a.0.5%至10%的氨基苯磺酸或其对应的盐,
b.30%至90%的可与水混溶的有机溶剂,和
c.5%至70%的水。
对于上述实施方式中的组合物和方法,氨基苯磺酸或其对应的盐选自2-氨基苯磺酸、3-氨基苯磺酸、4-氨基苯磺酸及其混合物。
在另一种实施方式中,所述半水性溶脱和清洗组合物包含
a.0.5%至10%的2-氨基苯磺酸或其对应的盐,
b.30%至90%的可与水混溶的有机溶剂,和
c.5%至70%的水。
再在另一种实施方式中,从半导体基板除去光致抗蚀剂、蚀刻和/或灰磨残留物或者污染物的方法包括:
使半导体基板与包含以下成分的组合物接触足以充分地除去光致抗蚀剂、蚀刻和/或灰磨残留物或者污染物的一段时间:
a.0.5%至10%的2-氨基苯磺酸或其对应的盐,
b.30%至90%的可与水混溶的有机溶剂,和
c.5%至70%的水。
对于上述实施方式,可与水混溶的有机溶剂选自二醇醚、糠醇及其混合物。更具体地,可与水混溶的有机溶剂选自丙二醇甲醚(PGME)、丙二醇丙醚(PGPE)、三(丙二醇)单甲醚、2-(2-丁氧基乙氧基)乙醇、四氢糠醇(THFA)及其混合物。
所述组合物可以进一步包含最多15%的选自有机酸、有机酸盐、苯酚、***、羟胺衍生物、果糖、亚硫酸铵、2-氨基嘧啶、硫代硫酸铵、甘氨酸、四甲基胍、亚氨基二乙酸、二甲基乙酰基乙酰胺及其混合物的腐蚀抑制剂。
所述组合物可以进一步包含最多10%的选自氢氧化四甲基铵(TMAH)、氢氧化四乙基铵、氢氧化四丁基铵(TBAH)、氢氧化四丙基铵、氢氧化三甲基乙基铵、氢氧化(2-羟乙基)三甲基铵、氢氧化(2-羟乙基)三乙基铵、氢氧化(2-羟乙基)三丙基铵、氢氧化(1-羟丙基)三甲基铵、氢氧化乙基三甲基铵、氢氧化二乙基二甲基铵、氢氧化苯甲基三甲基铵及其混合物的季铵化合物。
所述组合物优选具有6-11的pH值。
具体实施方式
本发明提供一种其成分以有效地从基板(例如,举例来说,半导体基板)除去残留物的量存在的组合物。本发明还提供利用该组合物从基板除去残留物的方法。在涉及半导体基板的应用中,这类残留物包括,例如光致抗蚀剂(硬化的或其它)、填缝剂、底部抗反射涂层(BARC)及其它聚合物质(例如,含C-F的聚合物、低和高分子量聚合物)和/或工艺残渣(如由蚀刻和灰磨处理产生的残留物)、无机化合物(如金属氧化物)、来自化学机械平面化(CMP)浆料的陶瓷颗粒和其它无机蚀刻残留物、含金属的化合物(如,举例来说,有机金属残留物和金属有机化合物)。在一种实施方式中,按照本发明的组合物在从半导体基板除去含硅的BARC残留物方面特别有效。
残留物通常存在于可能包括金属、硅、硅酸盐和/或层间介电物质(例如,举例来说,沉积的硅氧化物和衍生的硅氧化物,如氢硅倍半氧烷(HSQ)、甲基硅倍半氧烷(MSQ)、场氧化物(FOX)、四乙氧基甲硅烷(TEOS)和旋涂玻璃(spin-on glass))、化学汽相淀积电介质物质、低介电(low-k)和/或高介电(high-k)物质(如硅酸铪、氧化铪、钛酸锶钡(BST)、TiO2、TaO5)的基板中,其中残留物和金属、硅、硅化物、层间介电物质、低介电和/或高介电物质都与清洗组合物接触。本发明的组合物与这些物质相容并因此可以用于选择性地除去残留物(例如,举例来说,上面描述的那些残留物)而不会明显地侵蚀所述金属、硅、二氧化硅、层间介电物质、低介电或高介电物质。在特定的实施方式中,基板可以包含金属,例如,但不限于铜、钴、铜合金、钛、氮化钛、钽、氮化钽、钨和/或钛/钨合金。
在制造过程中,光致抗蚀层涂敷在基板上。利用光刻工艺在光致抗蚀层上形成图案。因此形成图案的光致抗蚀层进行等离子蚀刻,图案通过蚀刻转印到基板上。蚀刻残留物在蚀刻阶段中产生。本发明中使用的某些基板进行灰磨处理,而某些不进行灰磨处理。当基板进行灰磨处理时,待清洗的主要残留物是蚀刻和灰磨残留物。如果基板不进行灰磨处理,则待清洗或溶脱的主要残留物是蚀刻残留物和光致抗蚀剂以及高度交联的光致抗蚀剂。
本发明公开的组合物是包含氨基苯磺酸或其对应的盐、可与水混溶的有机溶剂和水的半水性溶脱和清洗组合物。对于本发明来说,“可混溶”包括可溶解。
在特定的实施方式中,氨基苯磺酸选自2-氨基苯磺酸(也称作邻氨基苯磺酸、苯胺-2-磺酸、苯胺-邻-磺酸和邻位氨基苯磺酸(oaminobenzenesulfonic))、3-氨基苯磺酸(也称作间氨基苯磺酸)、4-氨基苯磺酸(也称作磺胺酸)及其混合物。
在特定的实施方式中,可与水混溶的有机溶剂可以是二醇醚或糠醇。二醇醚可以包括二醇单(C1-C6)烷基醚和二醇二(C1-C6)烷基醚,例如,但不限于(C1-C20)链烷二醇(C1-C6)烷基醚和(C1-C20)链烷二醇二(C1-C6)烷基醚。二醇醚的实例为乙二醇单甲醚、乙二醇单***、乙二醇单丁醚、乙二醇二甲醚、乙二醇二***、二乙二醇单甲醚、二乙二醇单***、二乙二醇单丙醚、二乙二醇单异丙醚、二乙二醇单丁醚、二乙二醇单异丁醚、二乙二醇单苯甲醚、二乙二醇二甲醚、二乙二醇二***、三乙二醇单甲醚、三乙二醇二甲醚、聚乙二醇单甲醚、二乙二醇甲基乙基醚、三乙二醇乙二醇单甲醚乙酸酯、乙二醇单***乙酸酯、丙二醇单甲醚、丙二醇二甲醚、丙二醇单丁醚、丙二醇单丙醚、二丙二醇单甲醚、二丙二醇单丙醚、二丙二醇单异丙醚、二丙二醇单丁醚、二丙二醇二异丙醚、三丙二醇单甲醚、1-甲氧基-2-丁醇、2-甲氧基-1-丁醇、2-甲氧基-2-甲基丁醇、1,1-二甲氧基乙烷和2-(2-丁氧基乙氧基)乙醇。更典型的二醇醚的实例为丙二醇单甲醚、丙二醇单丙醚、三(丙二醇)单甲醚和2-(2-丁氧基乙氧基)乙醇。糠醇的实例为四氢糠醇(THFA)。
在一些实施方式中,组合物可以包括0.5%至大约15%重量的一种或多种腐蚀抑制剂。可以使用本领域中已知的用于类似用途的任何腐蚀抑制剂。腐蚀抑制剂可以是,例如有机酸、有机酸盐、苯酚、***、羟胺衍生物或其酸盐。特定腐蚀抑制剂的实例包括邻氨基苯甲酸、没食子酸、苯甲酸、间苯二酸、马来酸、富马酸、D,L-苹果酸、丙二酸、邻苯二甲酸、马来酸酐、邻苯二甲酸酐、苯并***(BZT)、间苯二酚、羧基苯并***、二烷基羟胺衍生物、乳酸、柠檬酸等等。可以使用的腐蚀抑制剂的进一步实例包括儿茶酚、1,2,3-苯三酚和没食子酸的酯。可以使用的特定二烷基羟胺衍生物包括二乙基羟胺。合适的腐蚀抑制剂的另外的实例包括果糖、亚硫酸铵、2-氨基嘧啶、硫代硫酸铵、甘氨酸、四甲基胍、亚氨基二乙酸和二甲基乙酰基乙酰胺。在特定的实施方式中,腐蚀抑制剂可以包括具有大约4至大约7的pH值范围的弱酸。弱酸的实例包括三羟基苯、二羟基苯和/或水杨基羟肟酸。在腐蚀抑制剂为有机酸的实施方式中,有机酸可以与缓冲溶液中所使用的相同。
在一些实施方式中,组合物可以包括一种或多种季铵化合物。合适的季铵化合物的实例包括氢氧化四甲基铵(TMAH)、氢氧化四乙基铵、氢氧化四丁基铵(TBAH)、氢氧化四丙基铵、氢氧化三甲基乙基铵、氢氧化(2-羟乙基)三甲基铵、氢氧化(2-羟乙基)三乙基铵、氢氧化(2-羟乙基)三丙基铵、氢氧化(1-羟丙基)三甲基铵、氢氧化乙基三甲基铵、氢氧化二乙基二甲基铵和氢氧化苯甲基三甲基铵。季铵化合物的存在量为大约0.5%至大约10%或者大约5%至大约10%重量。
在一些实施方式中,组合物可以任选地包括氟离子源,其量通常为大约0.1%至大约10%重量或大约5%至大约10%重量。这类化合物的实例包括氟化铵、四甲基氟化铵、四乙基氟化铵、四丁基氟化铵及其混合物。氟离子源的再进一步的实例包括氟硼酸、氢氟酸、氟硼酸盐、四氟硼酸四丁基铵盐、六氟化铝和氟化胆碱。
在一些实施方式中,组合物包含0.5%至10%的氨基苯磺酸或其对应的盐、30%至90%的有机溶剂和5%至70%的水,其中组合物的pH为6-11。
在一个特定的实施方式中,组合物由0.5%至10%的2-氨基苯磺酸、30%至90%的可与水混溶的有机溶剂和5%至70%的水构成。
组合物优选具有6-11的pH值。
基板的组成
在本发明的实施例中使用的各基板包括蚀刻后抗蚀剂的顶层,紧跟着是BARC层。BARC层又位于硬掩模顶上,紧跟着是低介电的电介质。硬掩模材料的例子通常是钛和氮化钛,但不限于此。对于双重镶嵌基板,电介质层后跟着蚀刻终止层,蚀刻终止层又通常跟着铜层,但不限于铜层。
加工条件
清洗测试使用305mL的清洗组合物在400mL的烧杯中利用设置为600rpm的1/2”圆形Teflon搅拌子进行。如果必要,清洗组合物在电热板上被加热到下面给出的预定温度。尺寸为大约1/2”x1/2”的晶片片断在下面的设置条件下浸入到组合物中:
50℃温度下30分钟。
然后片断在去离子(DI)水溢流槽中冲洗3分钟,随后使用过滤氮气进行干燥。然后使用扫描电子显微镜(SEM)镜检方法对它们进行清洁度分析。
工作实施例
下面的实施例用于进一步说明本发明的目的,但不以任何方式限制本发明。
在下面的实施例中,所有的量以重量百分比给出并合计为100%重量。这里公开的组合物通过在室温下将各成分在容器中混合在一起直到所有固体溶解而制备。这里公开的特定组合物的实施例在表1中给出。
下面是表1使用的缩略词:
PGME=丙二醇甲醚
THFA=四氢糠醇
PGPE=丙二醇丙醚
DEHA=二乙基羟胺
2-ASA=2-氨基苯磺酸
3-ASA=3-氨基苯磺酸
4-ASA=4-氨基苯磺酸
p-TSA=对甲苯磺酸
MSA=甲磺酸
TMAH=氢氧化四甲基铵
TMAF=四甲基氟化铵
Amm.Sulfite=亚硫酸铵
表1:示例性的组合物
实施例A 实施例B 实施例C
PGME 46 PGME 54.8 PGME 37.7
去离子水44.4 去离子水39.5 去离子水51
2-ASA 2 2-ASA 2 2-ASA 7
TMAH 7 TMAH 2.1 TMAH 3.7
TMAF 0.6 TMAF 0.6 TMAF 0.6
2-氨基嘧啶1
实施例D 实施例E 实施例F
PGME 59 PGME 37 PGME 10
去离子水 30.9 去离子水 49.9 去离子水 49.4
2-ASA 2 2-ASA 2 2-ASA 2
亚硫酸铵1 亚硫酸铵2 苯甲酸1
TMAH 6.5 TMAH 7.5 TMAH 7
TMAF 0.6 TMAF 0.6 TMAF 0.6
2-氨基嘧啶 1 THFA 30
实施例G 实施例H 实施例1
THFA 40 PGME 33 PGME 32.8
去离子水 49.4 去离子水 49.4 去离子水 51.2
2-ASA 2 2-ASA 2 2-ASA 2.2
苯甲酸 1 丙二酸 3 柠檬酸 0.9
TMAH 7 TMAH 7 TMAH 7.3
TMAF 0.6 TMAF 0.6 TMAF 0.6
DEHA 5 DEHA 5
实施例J 实施例K 实施例L
PGME 32.8 PGME 32.8 PGME 32.8
去离子水 51.2 去离子水 51.2 去离子水 51.2
4-ASA 2.2 p-TSA 2.2 MSA 2.2
柠檬酸 0.9 柠檬酸 0.9 柠檬酸 0.9
TMAH 7.3 TMAH 7.3 TMAH 7.3
TMAF 0.6 TMAF 0.6 TMAF 0.6
DEHA 5 DEHA 5 DEHA 5
实施例M 实施例N 实施例O
PGME 40 PGME 67.6 PGPE 32.8
去离子水 52.1 去离子水 20.2 去离子水 51.2
2-ASA 2 TBAH 1.1 2-ASA 2.2
柠檬酸 0.9 2-ASA 2 柠檬酸 0.9
DEHA 5 DEHA 5 TMAH 7.3
TEA 1.1 TMAF 0.6
间苯二酚 3 DEHA 5
实施例P 实施例Q 实施例R
PGME 32.8 PGME 32.8 PGME 32.8
去离子水 46.7 去离子水 46.7 去离子水 46.7
2-ASA 2.2 p-TSA 2.2 MSA 2.2
柠檬酸 6柠 檬酸 6 柠檬酸 6
TMAH 7.3 TMAH 7.3 TMAH 7.3
DEHA 5 DEHA 5 DEHA 5
实施例S 实施例T
PGME 32.8 PGME 32.8
去离子水 46.7 去离子水 46.7
3-ASA 2.2 4-ASA 2.2
柠檬酸 6 柠檬酸 6
TMAH 7.3 TMAH 7.3
DEHA 5 DEHA 5
示例性组合物的清洗效果显示于表2中。
表2.示例性组合物的清洗效果数据
√=清洁;√-=部分清洁;X=不清洁
如表1中所示,在实施例P-T的设置中唯一变化的成分是在组合物中使用了不同的磺酸。如表2中所示,所有氨基苯磺酸都具有一定的清洗效果。看来磺酸官能团的位置对清洁效率有影响。如下面的结构中所示,当磺酸基团位于邻位时,如2-氨基苯磺酸(2-ASA,实施例P),组合物能够同时清洗基质和除去BARC物质。但是,当磺酸基团分别位于间位和对位时,如3-氨基苯磺酸(3-ASA)和4-氨基苯磺酸(4-ASA)(实施例S和T),这些组合物清洁效率较低,其中一些不能完成基板的清洗。在其它的磺酸化合物中,如对甲苯磺酸(p-TSA)和甲磺酸(MSA),也显示出弱的清洗效果,它们不能完成基板的清洗。
当氟化物加入到组合物中时,含有2-ASA的组合物的有益清洗效果出现下降。清洗效果的减弱通过实施例P和实施例I的对比可以明显地看出。实施例P和实施例I各包含2-ASA,但实施例I除了实施例P具有的所有成分外还含有氟化物。实施例P能够同时清洗基质和除去BARC物质,而很显然实施例I不能同时清洗基质和除去BARC物质(如表2中所示)。
二乙基羟胺(以及其它的羟胺衍生物)用作铜的腐蚀抑制剂。一般来说,羟胺衍生物由于其蚀刻铜的能力而被认为与铜不相容,但在那些组合物中,它们被用于防止铜腐蚀。
前述的实施例和对优选实施方式的描述应理解为对权利要求中定义的本发明的举例说明,而不是对本发明的限制。很容易理解,可以采用上述给出的特征的多种变型或组合而不会与如权利要求中所列的本发明脱离。这类变型不认为脱离本发明的精神和范围,且所有这类变型应当包括在所附权利要求的范围内。
Claims (10)
1、一种半水性溶脱和清洗组合物,包含:
a.0.5%至10%的氨基苯磺酸或其对应的盐,
b.30%至90%的可与水混溶的有机溶剂,和
c.5%至70%的水;
其中该组合物的pH值为6-11。
2、如权利要求1所述的组合物,其中所述氨基苯磺酸选自2-氨基苯磺酸、3-氨基苯磺酸、4-氨基苯磺酸及其混合物,优选所述氨基苯磺酸为2-氨基苯磺酸。
3、如权利要求1或2所述的组合物,其中所述可与水混溶的有机溶剂选自二醇醚、糠醇及其混合物,优选所述可与水混溶的有机溶剂选自丙二醇甲醚(PGME)、丙二醇丙醚(PGPE)、三(丙二醇)单甲醚、2-(2-丁氧基乙氧基)乙醇、四氢糠醇(THFA)及其混合物。
4、如权利要求1-3任一项所述的组合物,其中所述组合物进一步包含0.5%至15%的选自有机酸、有机酸盐、苯酚、***、羟胺衍生物、果糖、亚硫酸铵、2-氨基嘧啶、硫代硫酸铵、甘氨酸、四甲基胍、亚氨基二乙酸、二甲基乙酰基乙酰胺及其混合物的腐蚀抑制剂。
5、如权利要求1-4任一项所述的组合物,其中所述组合物进一步包含0.5%至10%的选自氢氧化四甲基铵(TMAH)、氢氧化四乙基铵、氢氧化四丁基铵(TBAH)、氢氧化四丙基铵、氢氧化三甲基乙基铵、氢氧化(2-羟乙基)三甲基铵、氢氧化(2-羟乙基)三乙基铵、氢氧化(2-羟乙基)三丙基铵、氢氧化(1-羟丙基)三甲基铵、氢氧化乙基三甲基铵、氢氧化二乙基二甲基铵、氢氧化苯甲基三甲基铵及其混合物的季铵化合物。
6、一种从半导体基板除去光致抗蚀剂、蚀刻和/或灰磨残留物或者污染物的方法,包括:
使半导体基板与包含以下成分的组合物接触足以充分地除去所述光致抗蚀剂、蚀刻和/或灰磨残留物或者污染物的一段时间:
a.0.5%至10%的氨基苯磺酸或其对应的盐,
b.30%至90%的可与水混溶的有机溶剂,和
c.5%至70%的水;
其中该组合物的pH值为6-11。
7、如权利要求6所述的方法,其中所述氨基苯磺酸选自2-氨基苯磺酸、3-氨基苯磺酸、4-氨基苯磺酸及其混合物,优选所述氨基苯磺酸为2-氨基苯磺酸。
8、如权利要求6或所述的方法,其中所述可与水混溶的有机溶剂选自二醇醚、糠醇及其混合物,优选所述可与水混溶的有机溶剂选自丙二醇甲醚(PGME)、丙二醇丙醚(PGPE)、三(丙二醇)单甲醚、2-(2-丁氧基乙氧基)乙醇、四氢糠醇(THFA)及其混合物。
9、如权利要求6-8任一项所述的方法,其中所述组合物进一步包含0.5%至15%的选自有机酸、有机酸盐、苯酚、***、羟胺衍生物、果糖、亚硫酸铵、2-氨基嘧啶、硫代硫酸铵、甘氨酸、四甲基胍、亚氨基二乙酸、二甲基乙酰基乙酰胺及其混合物的腐蚀抑制剂。
10、如权利要求6-9任一项所述的方法,其中所述组合物进一步包含0.5%至10%的选自氢氧化四甲基铵(TMAH)、氢氧化四乙基铵、氢氧化四丁基铵(TBAH)、氢氧化四丙基铵、氢氧化三甲基乙基铵、氢氧化(2-羟乙基)三甲基铵、氢氧化(2-羟乙基)三乙基铵、氢氧化(2-羟乙基)三丙基铵、氢氧化(1-羟丙基)三甲基铵、氢氧化乙基三甲基铵、氢氧化二乙基二甲基铵、氢氧化苯甲基三甲基铵及其混合物的季铵化合物。
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- 2009-03-10 TW TW098107781A patent/TWI405848B/zh not_active IP Right Cessation
- 2009-03-12 CN CN2009101281618A patent/CN101531950B/zh not_active Expired - Fee Related
- 2009-03-13 JP JP2009062026A patent/JP4787342B2/ja not_active Expired - Fee Related
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WO2015000211A1 (zh) * | 2013-07-03 | 2015-01-08 | 北京科华微电子材料有限公司 | 一种新型的光刻胶剥离液及其应用工艺 |
CN107109134A (zh) * | 2014-12-22 | 2017-08-29 | 巴斯夫欧洲公司 | 化学机械抛光(cmp)组合物在抛光包含钴和/或钴合金的基材中的用途 |
CN107109134B (zh) * | 2014-12-22 | 2021-04-13 | 巴斯夫欧洲公司 | 化学机械抛光(cmp)组合物在抛光包含钴和/或钴合金的基材中的用途 |
CN105573071A (zh) * | 2015-05-26 | 2016-05-11 | 叶旖婷 | 一种既高效且能保持铜面光亮又环保的褪膜液及其浓缩液 |
TWI672360B (zh) * | 2018-01-04 | 2019-09-21 | 才將科技股份有限公司 | 具有針對兩種晶格方向低選擇比(Si(100)/Si(111))及低二氧化矽蝕刻率之矽蝕刻劑組合物 |
CN114437883A (zh) * | 2020-11-06 | 2022-05-06 | 凯斯科技股份有限公司 | 用于溶解抛光粒子的组合物及使用其的清洁方法 |
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TWI405848B (zh) | 2013-08-21 |
KR20090098734A (ko) | 2009-09-17 |
JP2009224782A (ja) | 2009-10-01 |
CN101531950B (zh) | 2013-05-29 |
US20090233827A1 (en) | 2009-09-17 |
JP4787342B2 (ja) | 2011-10-05 |
US7687447B2 (en) | 2010-03-30 |
TW200938624A (en) | 2009-09-16 |
KR101101066B1 (ko) | 2011-12-30 |
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