CN101959977B - 微电子基底清洁组合物 - Google Patents
微电子基底清洁组合物 Download PDFInfo
- Publication number
- CN101959977B CN101959977B CN2009801068386A CN200980106838A CN101959977B CN 101959977 B CN101959977 B CN 101959977B CN 2009801068386 A CN2009801068386 A CN 2009801068386A CN 200980106838 A CN200980106838 A CN 200980106838A CN 101959977 B CN101959977 B CN 101959977B
- Authority
- CN
- China
- Prior art keywords
- composition
- cleaning compositions
- weight
- component
- microelectronic substrate
- 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.)
- Active
Links
- 239000000203 mixture Substances 0.000 title claims abstract description 91
- 238000004140 cleaning Methods 0.000 title claims abstract description 50
- 238000004377 microelectronic Methods 0.000 title claims abstract description 25
- 239000000758 substrate Substances 0.000 title claims abstract description 22
- 239000003989 dielectric material Substances 0.000 claims abstract description 12
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 10
- 150000003457 sulfones Chemical class 0.000 claims abstract description 9
- 239000011248 coating agent Substances 0.000 claims description 24
- 238000000576 coating method Methods 0.000 claims description 24
- 239000002253 acid Substances 0.000 claims description 18
- 238000005530 etching Methods 0.000 claims description 17
- 238000000034 method Methods 0.000 claims description 16
- HXJUTPCZVOIRIF-UHFFFAOYSA-N sulfolane Chemical compound O=S1(=O)CCCC1 HXJUTPCZVOIRIF-UHFFFAOYSA-N 0.000 claims description 12
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 10
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 claims description 8
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 claims description 8
- 150000003462 sulfoxides Chemical class 0.000 claims description 8
- 238000004380 ashing Methods 0.000 claims description 5
- 235000011187 glycerol Nutrition 0.000 claims description 4
- 230000003042 antagnostic effect Effects 0.000 claims description 2
- 230000011514 reflex Effects 0.000 claims description 2
- 239000006117 anti-reflective coating Substances 0.000 abstract 1
- 150000005846 sugar alcohols Polymers 0.000 abstract 1
- 239000010949 copper Substances 0.000 description 16
- 239000002585 base Substances 0.000 description 13
- -1 tetrafluoroborate Chemical compound 0.000 description 11
- 229910052802 copper Inorganic materials 0.000 description 10
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 9
- 239000010432 diamond Substances 0.000 description 9
- 239000002904 solvent Substances 0.000 description 8
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 description 6
- 239000000463 material Substances 0.000 description 6
- 238000001465 metallisation Methods 0.000 description 5
- 150000007522 mineralic acids Chemical class 0.000 description 4
- 229920002120 photoresistant polymer Polymers 0.000 description 4
- 238000002360 preparation method Methods 0.000 description 4
- BTBUEUYNUDRHOZ-UHFFFAOYSA-N Borate Chemical compound [O-]B([O-])[O-] BTBUEUYNUDRHOZ-UHFFFAOYSA-N 0.000 description 3
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 3
- 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
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 3
- 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 description 3
- 229910052782 aluminium Inorganic materials 0.000 description 3
- 238000000637 aluminium metallisation Methods 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 239000004411 aluminium Substances 0.000 description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- HEBKCHPVOIAQTA-UHFFFAOYSA-N meso ribitol Natural products OCC(O)C(O)C(O)CO HEBKCHPVOIAQTA-UHFFFAOYSA-N 0.000 description 2
- 238000000206 photolithography Methods 0.000 description 2
- 238000012545 processing Methods 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- 239000003352 sequestering agent Substances 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- 238000009987 spinning Methods 0.000 description 2
- HHVIBTZHLRERCL-UHFFFAOYSA-N sulfonyldimethane Chemical compound CS(C)(=O)=O HHVIBTZHLRERCL-UHFFFAOYSA-N 0.000 description 2
- RWRDLPDLKQPQOW-UHFFFAOYSA-N tetrahydropyrrole Natural products C1CCNC1 RWRDLPDLKQPQOW-UHFFFAOYSA-N 0.000 description 2
- MEIRRNXMZYDVDW-MQQKCMAXSA-N (2E,4E)-2,4-hexadien-1-ol Chemical compound C\C=C\C=C\CO MEIRRNXMZYDVDW-MQQKCMAXSA-N 0.000 description 1
- HRSFRSLKOPFWMZ-UHFFFAOYSA-N (3,4,5-trifluorophenyl)methanol Chemical compound OCC1=CC(F)=C(F)C(F)=C1 HRSFRSLKOPFWMZ-UHFFFAOYSA-N 0.000 description 1
- AIDFJGKWTOULTC-UHFFFAOYSA-N 1-butylsulfonylbutane Chemical compound CCCCS(=O)(=O)CCCC AIDFJGKWTOULTC-UHFFFAOYSA-N 0.000 description 1
- MBDUIEKYVPVZJH-UHFFFAOYSA-N 1-ethylsulfonylethane Chemical compound CCS(=O)(=O)CC MBDUIEKYVPVZJH-UHFFFAOYSA-N 0.000 description 1
- 229910016553 CuOx Inorganic materials 0.000 description 1
- 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
- FBPFZTCFMRRESA-KVTDHHQDSA-N D-Mannitol Chemical compound OC[C@@H](O)[C@@H](O)[C@H](O)[C@H](O)CO FBPFZTCFMRRESA-KVTDHHQDSA-N 0.000 description 1
- HEBKCHPVOIAQTA-QWWZWVQMSA-N D-arabinitol Chemical compound OC[C@@H](O)C(O)[C@H](O)CO HEBKCHPVOIAQTA-QWWZWVQMSA-N 0.000 description 1
- LCGLNKUTAGEVQW-UHFFFAOYSA-N Dimethyl ether Chemical group COC LCGLNKUTAGEVQW-UHFFFAOYSA-N 0.000 description 1
- UNXHWFMMPAWVPI-UHFFFAOYSA-N Erythritol Natural products OCC(O)C(O)CO UNXHWFMMPAWVPI-UHFFFAOYSA-N 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 1
- 229930195725 Mannitol Natural products 0.000 description 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- TVXBFESIOXBWNM-UHFFFAOYSA-N Xylitol Natural products OCCC(O)C(O)C(O)CCO TVXBFESIOXBWNM-UHFFFAOYSA-N 0.000 description 1
- 239000013543 active substance Substances 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- 150000003863 ammonium salts Chemical class 0.000 description 1
- 239000000010 aprotic solvent Substances 0.000 description 1
- 229910003460 diamond Inorganic materials 0.000 description 1
- KZTYYGOKRVBIMI-UHFFFAOYSA-N diphenyl sulfone Chemical compound C=1C=CC=CC=1S(=O)(=O)C1=CC=CC=C1 KZTYYGOKRVBIMI-UHFFFAOYSA-N 0.000 description 1
- 238000001312 dry etching Methods 0.000 description 1
- 230000009977 dual effect Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- UNXHWFMMPAWVPI-ZXZARUISSA-N erythritol Chemical compound OC[C@H](O)[C@H](O)CO UNXHWFMMPAWVPI-ZXZARUISSA-N 0.000 description 1
- VBQUDDWATQWCPP-UHFFFAOYSA-N ethylsulfonylbenzene Chemical compound CCS(=O)(=O)C1=CC=CC=C1 VBQUDDWATQWCPP-UHFFFAOYSA-N 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- 239000000594 mannitol Substances 0.000 description 1
- 235000010355 mannitol Nutrition 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- JCDWETOKTFWTHA-UHFFFAOYSA-N methylsulfonylbenzene Chemical compound CS(=O)(=O)C1=CC=CC=C1 JCDWETOKTFWTHA-UHFFFAOYSA-N 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- 229960003330 pentetic acid Drugs 0.000 description 1
- 238000001020 plasma etching Methods 0.000 description 1
- 229920005862 polyol Polymers 0.000 description 1
- 150000003077 polyols Chemical class 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 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
- 238000012546 transfer Methods 0.000 description 1
- 238000011179 visual inspection Methods 0.000 description 1
- 239000000811 xylitol Substances 0.000 description 1
- HEBKCHPVOIAQTA-SCDXWVJYSA-N xylitol Chemical compound OC[C@H](O)[C@@H](O)[C@H](O)CO HEBKCHPVOIAQTA-SCDXWVJYSA-N 0.000 description 1
- 235000010447 xylitol Nutrition 0.000 description 1
- 229960002675 xylitol Drugs 0.000 description 1
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
- C11D7/00—Compositions of detergents based essentially on non-surface-active compounds
- C11D7/02—Inorganic compounds
- C11D7/04—Water-soluble compounds
- C11D7/10—Salts
-
- 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
- C11D7/34—Organic compounds containing sulfur
-
- 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
-
- 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
- H01L21/04—Manufacture or treatment of semiconductor devices or of parts thereof the devices having potential barriers, e.g. a PN junction, depletion layer or carrier concentration layer
- H01L21/18—Manufacture or treatment of semiconductor devices or of parts thereof the devices having potential barriers, e.g. a PN junction, depletion layer or carrier concentration layer the devices having semiconductor bodies comprising elements of Group IV of the Periodic Table or AIIIBV compounds with or without impurities, e.g. doping materials
- H01L21/30—Treatment of semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/26
- H01L21/31—Treatment of semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/26 to form insulating layers thereon, e.g. for masking or by using photolithographic techniques; After treatment of these layers; Selection of materials for these layers
- H01L21/3105—After-treatment
- H01L21/311—Etching the insulating layers by chemical or physical means
- H01L21/31127—Etching organic layers
- H01L21/31133—Etching organic layers by chemical means
-
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Life Sciences & Earth Sciences (AREA)
- Condensed Matter Physics & Semiconductors (AREA)
- Computer Hardware Design (AREA)
- Microelectronics & Electronic Packaging (AREA)
- Power Engineering (AREA)
- Physics & Mathematics (AREA)
- General Physics & Mathematics (AREA)
- Manufacturing & Machinery (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Wood Science & Technology (AREA)
- Organic Chemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Inorganic Chemistry (AREA)
- Cleaning Or Drying Semiconductors (AREA)
- Detergent Compositions (AREA)
- Drying Of Semiconductors (AREA)
Abstract
微电子清洁组合物，其包含：a)该组合物约80％至约99％重量的至少一种有机砜；b)该组合物约0.5％至约19％重量的水；和c)该组合物约0.5％至约10％重量的至少一种提供四氟硼酸根离子的组分，和d)任选至少一种多元醇。其尤其用于从具有Si基抗反射涂层和低k电介质的微电子基底或设备清洁蚀刻/灰化残余物。
Description
技术领域
本发明涉及组合物，其用于通过去除等离子蚀刻后或蚀刻/灰化后残余物清洁微电子基底以及硅基抗反射涂层，且能够在与铝、铜和低k电介质，且特别是多孔低k电介质相容的情况下进行清洁。特别地，本发明提供基本上基于溶剂的去除剂组合物，且还提供使用该组合物清洁微电子基底和设备的方法。
背景技术
半导体设备已通过以下步骤而制备：用光致抗蚀剂涂覆无机基底；通过暴露于光且随后显影而使光致抗蚀剂膜形成图案；使用该形成图案的光致抗蚀剂膜作为掩模蚀刻该无机基底的暴露区域以形成微小电路；和从无机基底去除该形成图案的光致抗蚀剂膜。或者，以上述相同方式形成微小电路后，将该形成图案的光致抗蚀剂膜灰化，然后将剩余的抗蚀剂残余物从无机基底去除。
随着更小电路线的进步，以及使用更先进的光刻术(例如，193nm，ArF)获得该电路线，需要抗反射涂层以控制临界尺寸(CD)和保持高图象质量。因此，最近扩大了Si基旋压(spin-on)抗反射涂层的作用以加入图像转移职责。使用该旋压Si基抗反射涂层的优点通常至少为双重的：它们易于平面化，且与使用ArF在193nm的光刻术所需的光致抗蚀剂的化学组成差别足够大，以使得促进了干法刻蚀过程中高分辨图像转移。然而，在干法刻蚀步骤之后，需要去除任何光致抗蚀剂或光致抗蚀剂残余物和剩余的抗反射涂层，而不损坏下面的电介质层或任何已进行的金属化。
因此需要提供去除蚀刻/灰化残余物、光致抗蚀剂和抗反射涂层的清洁组合物，且同时不损坏任何下面的电介质层或微电子设备的金属化(metallization)。特别需要提供用于去除蚀刻/灰化残余物、光致抗蚀剂和Si-抗反射涂层的清洁组合物，同时不损坏任何潜在的低k电介质层，特别是任何多孔低k电介质层，它们本身为化学类似的材料，且不损坏任何微电子设备的金属化，特别是铜或铝金属化。
发明内容
本发明的去除残余物的清洁组合物为基于含酸性四氟硼酸根的溶剂的组合物。这些组合物具有的pH为3或更小，且包含约80％至约99％重量的砜溶剂，约0.25％至19％重量水，约0.25％至10％重量的至少一种提供四氟硼酸根离子(BF4 -)的组分。该组合物可包含螯合剂，多元醇，表面活性剂和酸。本发明的组合物可用于清洁微电子基底以去除蚀刻/灰化残余物，特别是从包括含Si抗反射涂层以及下面的低k电介质层(特别是任何多孔低k电介质层)的那些微电子基底清洁。为实现清洁微电子基底或设备，该微电子基底或设备与本发明的组合物在足以实现该清洁的温度下接触足以实现该清洁的时间。
发明详述
本发明的去除残余物的清洁组合物为基于包含酸性四氟硼酸根的有机砜溶剂的组合物。这些组合物具有的pH为3或更小，且包含约80％至约99％重量的至少一种砜溶剂，约0.25％至约19％水和约0.25％至约10％重量的至少一种提供四氟硼酸根离子(BF4 -)的组分。
任何合适的有机砜可在本发明的组合物中使用。合适的砜包括，但不限于，二甲基砜，二乙基砜，二苯基砜，2-(甲基锍)乙醇，甲基苯基砜，乙基苯基砜，二丁基砜，二苄基砜和四氢噻吩-1，1-二氧化物(环丁砜)。优选环丁砜。本发明的清洁组合物中存在的砜组分的量的范围通常为该组合物的约80％至约99％重量，优选约85％至约95％，且更优选约89％至约93％。
本发明的清洁组合物中存在的水的量通常为该组合物的约0.25％至约19％重量，优选约2％至约14％，且更优选约4％至约10％。
提供四氟硼酸根离子的组分可为任何合适的可离子化的含四氟硼酸根的化合物，如，但不限于四氟硼酸HBF4，及其盐与强无机酸的组合。合适的盐包括，但不限于四氟硼酸铵(NH4BF4)，N-甲基-N-烷基吡咯烷鎓四氟硼酸盐，烷基四氟硼酸铵盐，碱金属四氟硼酸盐如锂、钠或钾四氟硼酸盐。任何合适的强无机酸可与四氟硼酸盐一起使用，且包括，但不限于，强无机酸如盐酸，硫酸，磷酸和硝酸。用于本发明的清洁组合物以提供四氟硼酸根离子优选为四氟硼酸，HBF4。四氟硼酸通常为商购的48％的水溶液，且可原样使用。四氟硼酸经历水解产生一些量的HF。组合物中HF的存在使得可选择性蚀刻Si基材料。提供四氟硼酸根离子的组分在本发明的清洁组合物中存在的量通常为该组合物的约0.25％至约10％重量，优选约1.5％至约7％，且更优选约2.5％至约4.5％。
本发明的清洁组合物的pH为pH 3或更小，优选pH约为2。本发明的清洁组合物的高酸性可通常归因于砜组分的特性。环丁砜为非质子溶剂，其在强酸的存在下不质子化。该特征使得相比于强无机酸水溶液，在低酸浓度下有非常高的酸性。
用备选Lewis碱溶剂，例如DMSO和乙二醇醚制备类似组合物的尝试是不成功的。上述制剂不具有去除Si基抗反射涂层的选择性，且它们也不保持与Cu的相容性。砜和BF3形成稳定的络合物。已报道四氟硼酸根离子(BF4 -)将离解为BF3和F-。在本发明中，认为砜-BF3络合物有助于将铜蚀刻速率减少为可接受的值。
本发明的清洁组合物可任选包含至少一种多元醇。如果本发明的清洁组合物中存在多元醇组分，其存在量可为清洁组合物的约1wt％至约10wt％，优选约2wt％至约8wt％，且更优选约3wt％至约6wt％。合适的多元醇包括，但不限于，乙二醇，甘油，赤藓醇，阿糖醇，木糖醇，甘露醇和山梨醇，且优选甘油。已证明(表X)使用多元醇的制剂具有增加的Cu相容性和光致抗蚀剂残余物去除能力。
相对于低k电介质，对抗反射涂层，本发明的清洁组合物能保持特别高(高达约70∶1)的蚀刻选择性，尽管它们本身是有些类似的材料。本发明的清洁组合物的pH为3或更小，其将上述蚀刻选择性赋予该清洁组合物，因为pH值大于3，清洁组合物将不可接受地蚀刻低k电介质材料。
本发明的清洁组合物可有效用于去除/清洁等离子刻蚀/灰化后残余物，金属基硬掩模和Si基抗反射涂层。本发明的组合物还具有铜和低k电介质相容性。本发明的一些组合物还具有铝相容性。
本发明的清洁组合物的理想的蚀刻速率选择性通过表1中对于Si基抗反射涂层、铜和铝金属化(metallization)和电介质(包括低k电介质)的蚀刻速率数据阐述。在该蚀刻实施例中，使用的本发明的清洁组合物包含3wt％HBF4，3.25wt％水和93.75wt％环丁砜。表中所列的材料用该清洁组合物在60℃处理10分钟，且观察到以下蚀刻速率。
表1
已对现有技术清洁组合物测试了是否它们在Si基抗反射涂层和电介质之间具有Si基蚀刻选择性。
美国专利申请公开号US 2006/0014656中实施例1的组合物相对Honeywell Duotm-193Si基抗反射涂层、铜和TEOS和Black Diamond 2电介质在50℃测试10分钟，且观察到的蚀刻速率(埃/分钟)如下。
表2
| CU | TEOS | DUOTM193 | Black Diamond 2 |
| ＜1 | ＞100 | ＞140. | ＞250 |
该现有技术制剂将以良好蚀刻速率蚀刻和去除Si基抗反射涂层，但也会不可接受地蚀刻低k Black Diamond电介质。
美国专利申请公开号US 2006/199749的表4中实施例23的组合物相对Honeywell Duotm-193Si基抗反射涂层、铜和TEOS和Black Diamond 2电介质在25℃和35℃测试10分钟，且观察到的蚀刻速率(埃/分钟)如下。
表3
| 温度℃ | Cu | TEOS | DUOtm-193 | Black Diamond 2 |
| 25℃ | 1 | 3 | 1 | 31 |
| 35℃ | 2 | 3 | 5 | 1 |
该基于主要含水和乙二醇醚(glycolic ether)酸性氟化物的制剂不能从基底去除Si基抗反射材料。
本发明的清洁组合物具有砜溶剂作为溶剂的关键性以及在该清洁组合物中避免存在乙二醇醚的必要性通过以下测试证实。制备以下三种清洁组合物。组合物A(本发明)包含92.7％环丁砜，3.8％水和3.5％四氟硼酸。在对比组合物B中，一部分环丁砜用卡必醇(二甘醇单甲基醚)代替，且在对比组合物C中，环丁砜完全被卡必醇代替。这些组合物的每一种相对Honeywell Duotm-193 Si基抗反射涂层、铜和TEOS和Black Diamond 2电介质在60℃测试30分钟。蚀刻结果(埃/分钟)如下。
表4
| 组合物 | Cu | TEOS | DUOTM-193 | Black Diamond 2 |
| A | ＜3 | 3 | ＞140 | ＜2 |
| B | 18 | 2 | 43 | 0 |
| C | 300 | 3 | 41 | 0 |
当与Cu相比，在本发明的组合物中部分或完全加入乙二醇醚破坏了Si基抗反射涂层的选择性蚀刻。
本发明的清洁组合物的理想的蚀刻速率选择性通过表1中对于Si基抗反射涂层、DUOTM-193、铜和铝金属化和电介质(包括低k电介质)的蚀刻速率数据阐述。所有化学品按供应商提供的使用。该研究在使用的HBF4为48％重量水溶液。所有蚀刻速率(埃/分钟)在60℃测定。处理Cu、Al和BlackDiamond 2(BD2)的基底30分钟。DUOTM处理10分钟(初始厚度为约1400埃)。pH测量从组合物的10％重量水溶液确定。CuOx的去除基于可视检查Cu涂覆的晶片而判断，该晶片浸没在30％H2O2中约30分钟，然后用以下所列的组合物进行1分钟的处理。
表5
*螯合剂的量为约0.25％重量：DTPA＝二亚乙基三胺五乙酸，EDTA＝乙二胺四乙酸，且CyDTA＝1，2-二氨基环己烷-N，N，N′，N′-四乙酸；
BD2＝Applied Material，Inc.的Black Diamond 2-低K电介质
尽管本发明已参考其具体实施方案进行了描述，应理解可进行改变、修饰和变化而不偏离本文公开的发明构思的精神和范围。因此，预期其包括落入所附权利要求的精神和范围内的所有这些改变、修饰和变化。
Claims (20)
1.微电子基底清洁组合物，其包含：
a)该组合物80％至99％重量的至少一种有机砜；
b)该组合物0.25％至19％重量的水；和
c)该组合物0.25％至10％重量的至少一种提供四氟硼酸根离子的组分
其中该组合物作为10％重量水溶液的pH为3或更小，且其中该组合物不包含乙二醇醚。
2.根据权利要求1的微电子基底清洁组合物，还包含1％至10％重量的至少一种多元醇，其中该组合物所述各组分含量的总和不大于100％。
3.根据权利要求1的微电子基底清洁组合物，其中所述砜包括环丁砜。
4.根据权利要求1的微电子基底清洁组合物，其中所述至少一种提供四氟硼酸根离子的组分包括四氟硼酸。
5.根据权利要求3的微电子基底清洁组合物，其中所述至少一种提供四氟硼酸根离子的组分包括四氟硼酸。
6.根据权利要求2的微电子基底清洁组合物，其中至少一种多元醇包括甘油。
7.根据权利要求6的微电子基底清洁组合物，其中所述至少一种砜包括环丁砜，且所述至少一种提供四氟硼酸根离子的组分包括四氟硼酸。
8.清洁微电子基底或设备的蚀刻/灰化后残余物的方法，其包括将微电子基底或设备与清洁组合物接触，该清洁组合物包含：
a)该组合物80％至99％重量的至少一种有机砜；
b)该组合物0.25％至19％重量的水；和
c)该组合物0.25％至10％重量的至少一种提供四氟硼酸根离子的组分
其中该组合物作为10％重量水溶液的pH为3或更小，且其中该组合物不包含乙二醇醚。
9.根据权利要求8的方法，其中该清洁组合物还包含1％至10％重量的至少一种多元醇。
10.根据权利要求8的方法，其中所述砜包括环丁砜。
11.根据权利要求8的方法，其中所述至少一种提供四氟硼酸根离子的组分包括四氟硼酸。
12.根据权利要求10的方法，其中所述至少一种提供四氟硼酸根离子的组分包括四氟硼酸。
13.根据权利要求9的方法，其中至少一种多元醇包括甘油。
14.根据权利要求13的方法，其中所述至少一种砜包括环丁砜，且所述至少一种提供四氟硼酸根离子的组分包括四氟硼酸。
15.根据权利要求8的方法，其中所述微电子基底或设备包括Si基抗反射涂层和低k电介质。
16.根据权利要求14的方法，其中所述微电子基底或设备包括Si基抗反射涂层和低k电介质。
17.清洁微电子基底或设备的蚀刻/灰化后残余物、光致抗蚀剂和Si基抗反射涂层的方法，其包括将微电子基底或设备与清洁组合物接触，其中相对于低k电介质，对抗反射涂层，所述清洁组合物能保持高达70∶1的蚀刻选择性，该清洁组合物包含：
d)该组合物80％至99％重量的至少一种有机砜；
e)该组合物0.25％至19％重量的水；和
f)该组合物0.25％至10％重量的至少一种提供四氟硼酸根离子的组分
其中该组合物作为10％重量水溶液的pH为3或更小，且其中该组合物不包含乙二醇醚。
18.根据权利要求17的方法，其中该组合物的pH为2。
19.根据权利要求17的方法，其中所述电介质层为多孔低k电介质层。
20.根据权利要求19的方法，其中所述清洁组合物包含HBF4、环丁砜和水。
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US3244908P | 2008-02-29 | 2008-02-29 | |
| US61/032,449 | 2008-02-29 | ||
| PCT/US2009/033148 WO2009108474A1 (en) | 2008-02-29 | 2009-02-05 | Microelectronic substrate cleaning compositions |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN101959977A CN101959977A (zh) | 2011-01-26 |
| CN101959977B true CN101959977B (zh) | 2013-12-04 |
Family
ID=40419175
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN2009801068386A Active CN101959977B (zh) | 2008-02-29 | 2009-02-05 | 微电子基底清洁组合物 |
Country Status (11)
| Country | Link |
|---|---|
| US (1) | US8168577B2 (zh) |
| EP (1) | EP2247672B1 (zh) |
| JP (1) | JP5512554B2 (zh) |
| KR (1) | KR101570256B1 (zh) |
| CN (1) | CN101959977B (zh) |
| BR (1) | BRPI0908905A2 (zh) |
| CA (1) | CA2716641A1 (zh) |
| IL (1) | IL207605A (zh) |
| TW (1) | TW200942608A (zh) |
| WO (1) | WO2009108474A1 (zh) |
| ZA (1) | ZA201005419B (zh) |
Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101838483B (zh) * | 2010-05-11 | 2012-07-04 | 华北电网有限公司北京超高压公司 | 一种溶解型防污闪涂层清除剂及其制备方法 |
| JP7173959B2 (ja) * | 2017-03-31 | 2022-11-16 | 関東化学株式会社 | 洗浄液組成物 |
| CN115386954A (zh) * | 2022-09-17 | 2022-11-25 | 中国科学院新疆理化技术研究所 | 化合物氟硼酸锂钠和氟硼酸锂钠双折射晶体及制备方法和用途 |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6773873B2 (en) * | 2002-03-25 | 2004-08-10 | Advanced Technology Materials, Inc. | pH buffered compositions useful for cleaning residue from semiconductor substrates |
| CN1659480A (zh) * | 2002-06-07 | 2005-08-24 | 马林克罗特贝克公司 | 用于微电子基底的清洁组合物 |
| WO2006065256A1 (en) * | 2004-12-10 | 2006-06-22 | Mallinckrodt Baker, Inc. | Non-aqueous, non-corrosive microelectronic cleaning compositions containing polymeric corrosion inhibitors |
| WO2006107517A2 (en) * | 2005-04-04 | 2006-10-12 | Mallinckrodt Baker, Inc. | Composition for cleaning ion implanted photoresist in front end of line applications |
Family Cites Families (34)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4401747A (en) | 1982-09-02 | 1983-08-30 | J. T. Baker Chemical Company | Stripping compositions and methods of stripping resists |
| US4491530A (en) | 1983-05-20 | 1985-01-01 | Allied Corporation | Brown stain suppressing phenol free and chlorinated hydrocarbons free photoresist stripper |
| US5480585A (en) | 1992-04-02 | 1996-01-02 | Nagase Electronic Chemicals, Ltd. | Stripping liquid compositions |
| US5568461A (en) * | 1994-04-20 | 1996-10-22 | Matsushita Electric Industrial Co., Ltd. | Optical information recording and reproducing apparatus |
| JPH07311469A (ja) * | 1994-05-17 | 1995-11-28 | Hitachi Chem Co Ltd | ポリイミド系樹脂膜のレジスト剥離残り除去液およびポリイミド系樹脂膜パターンの製造法 |
| US5571447A (en) | 1995-03-20 | 1996-11-05 | Ashland Inc. | Stripping and cleaning composition |
| JPH1055993A (ja) | 1996-08-09 | 1998-02-24 | Hitachi Ltd | 半導体素子製造用洗浄液及びそれを用いた半導体素子の製造方法 |
| US6043206A (en) | 1996-10-19 | 2000-03-28 | Samsung Electronics Co., Ltd. | Solutions for cleaning integrated circuit substrates |
| KR100248113B1 (ko) * | 1997-01-21 | 2000-03-15 | 이기원 | 전자 표시 장치 및 기판용 세정 및 식각 조성물 |
| US6150282A (en) | 1997-11-13 | 2000-11-21 | International Business Machines Corporation | Selective removal of etching residues |
| US6432209B2 (en) | 1998-03-03 | 2002-08-13 | Silicon Valley Chemlabs | Composition and method for removing resist and etching residues using hydroxylazmmonium carboxylates |
| JPH11323394A (ja) | 1998-05-14 | 1999-11-26 | Texas Instr Japan Ltd | 半導体素子製造用洗浄剤及びそれを用いた半導体素子の製造方法 |
| KR100288769B1 (ko) | 1998-07-10 | 2001-09-17 | 윤종용 | 포토레지스트용스트리퍼조성물 |
| US6828289B2 (en) | 1999-01-27 | 2004-12-07 | Air Products And Chemicals, Inc. | Low surface tension, low viscosity, aqueous, acidic compositions containing fluoride and organic, polar solvents for removal of photoresist and organic and inorganic etch residues at room temperature |
| US6761835B2 (en) | 2000-07-07 | 2004-07-13 | Tdk Corporation | Phosphor multilayer and EL panel |
| US6777380B2 (en) | 2000-07-10 | 2004-08-17 | Ekc Technology, Inc. | Compositions for cleaning organic and plasma etched residues for semiconductor devices |
| US20030022800A1 (en) | 2001-06-14 | 2003-01-30 | Peters Darryl W. | Aqueous buffered fluoride-containing etch residue removers and cleaners |
| US7192860B2 (en) | 2002-06-20 | 2007-03-20 | Honeywell International Inc. | Highly selective silicon oxide etching compositions |
| US6677286B1 (en) | 2002-07-10 | 2004-01-13 | Air Products And Chemicals, Inc. | Compositions for removing etching residue and use thereof |
| US7166419B2 (en) | 2002-09-26 | 2007-01-23 | Air Products And Chemicals, Inc. | Compositions substrate for removing etching residue and use thereof |
| CN1875325B (zh) * | 2003-10-29 | 2011-01-26 | 马林克罗特贝克公司 | 含有金属卤化物腐蚀抑制剂的碱性后等离子体蚀刻/灰化残余物去除剂和光致抗蚀剂剥离组合物 |
| US8030263B2 (en) | 2004-07-01 | 2011-10-04 | Air Products And Chemicals, Inc. | Composition for stripping and cleaning and use thereof |
| JP2006041446A (ja) * | 2004-07-30 | 2006-02-09 | Sumitomo Chemical Co Ltd | 電子部品洗浄液 |
| EP1853973A1 (en) | 2005-02-25 | 2007-11-14 | Ekc Technology, Inc. | Method to remove resist, etch residue, and copper oxide from substrates having copper and low-k dielectric material |
| JP2006310603A (ja) * | 2005-04-28 | 2006-11-09 | Nissan Chem Ind Ltd | ホウ素化合物を含む半導体用洗浄液組成物及び洗浄方法 |
| EP1894230A2 (en) | 2005-06-13 | 2008-03-05 | Advanced Technology Materials, Inc. | Compositions and methods for selective removal of metal or metal alloy after metal silicide formation |
| KR100655647B1 (ko) * | 2005-07-04 | 2006-12-08 | 삼성전자주식회사 | 반도체 기판용 세정액 조성물, 이의 제조 방법, 이를이용한 반도체 기판의 세정 방법 및 반도체 장치의 제조방법 |
| CN101356629B (zh) * | 2005-11-09 | 2012-06-06 | 高级技术材料公司 | 用于将其上具有低k介电材料的半导体晶片再循环的组合物和方法 |
| US7582508B2 (en) * | 2006-05-31 | 2009-09-01 | Byoung-Choo Park | Method for manufacturing an organic semiconductor device that utilizes ionic salt |
| WO2008023858A1 (en) | 2006-08-25 | 2008-02-28 | Hanwha Chemical Corporation | Manufacturing methods of fine cerium oxide particles and its slurry for shallow trench isolation process of semiconductor |
| US20080139436A1 (en) * | 2006-09-18 | 2008-06-12 | Chris Reid | Two step cleaning process to remove resist, etch residue, and copper oxide from substrates having copper and low-K dielectric material |
| US20080125342A1 (en) * | 2006-11-07 | 2008-05-29 | Advanced Technology Materials, Inc. | Formulations for cleaning memory device structures |
| SG10201610631UA (en) | 2006-12-21 | 2017-02-27 | Entegris Inc | Liquid cleaner for the removal of post-etch residues |
| US8026201B2 (en) * | 2007-01-03 | 2011-09-27 | Az Electronic Materials Usa Corp. | Stripper for coating layer |
-
2009
- 2009-02-05 CA CA2716641A patent/CA2716641A1/en not_active Abandoned
- 2009-02-05 KR KR1020107019104A patent/KR101570256B1/ko active IP Right Grant
- 2009-02-05 WO PCT/US2009/033148 patent/WO2009108474A1/en active Application Filing
- 2009-02-05 CN CN2009801068386A patent/CN101959977B/zh active Active
- 2009-02-05 JP JP2010548782A patent/JP5512554B2/ja active Active
- 2009-02-05 US US12/811,257 patent/US8168577B2/en not_active Expired - Fee Related
- 2009-02-05 BR BRPI0908905A patent/BRPI0908905A2/pt not_active IP Right Cessation
- 2009-02-05 EP EP09714861.3A patent/EP2247672B1/en not_active Not-in-force
- 2009-02-25 TW TW098106023A patent/TW200942608A/zh unknown
-
2010
- 2010-07-29 ZA ZA2010/05419A patent/ZA201005419B/en unknown
- 2010-08-12 IL IL207605A patent/IL207605A/en not_active IP Right Cessation
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6773873B2 (en) * | 2002-03-25 | 2004-08-10 | Advanced Technology Materials, Inc. | pH buffered compositions useful for cleaning residue from semiconductor substrates |
| CN1659480A (zh) * | 2002-06-07 | 2005-08-24 | 马林克罗特贝克公司 | 用于微电子基底的清洁组合物 |
| WO2006065256A1 (en) * | 2004-12-10 | 2006-06-22 | Mallinckrodt Baker, Inc. | Non-aqueous, non-corrosive microelectronic cleaning compositions containing polymeric corrosion inhibitors |
| WO2006107517A2 (en) * | 2005-04-04 | 2006-10-12 | Mallinckrodt Baker, Inc. | Composition for cleaning ion implanted photoresist in front end of line applications |
Also Published As
| Publication number | Publication date |
|---|---|
| EP2247672B1 (en) | 2013-06-05 |
| US8168577B2 (en) | 2012-05-01 |
| ZA201005419B (en) | 2011-04-28 |
| CA2716641A1 (en) | 2009-09-03 |
| BRPI0908905A2 (pt) | 2015-09-22 |
| IL207605A0 (en) | 2010-12-30 |
| CN101959977A (zh) | 2011-01-26 |
| TW200942608A (en) | 2009-10-16 |
| JP2011516620A (ja) | 2011-05-26 |
| JP5512554B2 (ja) | 2014-06-04 |
| WO2009108474A1 (en) | 2009-09-03 |
| EP2247672A1 (en) | 2010-11-10 |
| IL207605A (en) | 2014-02-27 |
| KR101570256B1 (ko) | 2015-11-18 |
| US20110046036A1 (en) | 2011-02-24 |
| KR20100125270A (ko) | 2010-11-30 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| JP4819429B2 (ja) | 残留物を除去するための組成物及び方法 | |
| US6773873B2 (en) | pH buffered compositions useful for cleaning residue from semiconductor substrates | |
| TWI548738B (zh) | 用於移除蝕刻後殘餘物之水性清潔劑 | |
| TWI516574B (zh) | 金屬及介電相容犠牲抗反射塗層清洗及移除組成物 | |
| US6455479B1 (en) | Stripping composition | |
| CN100543590C (zh) | 剥离聚合物的组合物 | |
| CN1985217B (zh) | 含果糖的非水性微电子清洁组合物 | |
| JP2005525706A (ja) | 二酸化炭素中でマイクロエレクトロニクス基板をエッチング洗浄するための方法及び組成物 | |
| EP1610185A2 (en) | Composition and method using same for removing residue from a substrate | |
| JP3679753B2 (ja) | レジスト剥離剤組成物 | |
| CN103782368A (zh) | 对铜、钨和多孔低κ电介质具有增强的相容性的半水性聚合物移除组合物 | |
| KR20080005408A (ko) | 포스트-에치 및 애싱된 포토레지스트 잔류물 및 벌크포토레지스트의 제거를 위한 조성물 | |
| US20040220066A1 (en) | Stripper | |
| CN101959977B (zh) | 微电子基底清洁组合物 | |
| KR100363271B1 (ko) | 포토레지스트 리무버 조성물 | |
| JP3742624B2 (ja) | フッ化アンモニウムを含有するフォトレジスト除去剤組成物 | |
| JP4651269B2 (ja) | 洗浄液およびそれを用いた洗浄法 | |
| KR100378552B1 (ko) | 레지스트 리무버 조성물 | |
| KR100862988B1 (ko) | 포토레지스트 리무버 조성물 | |
| JP4415228B2 (ja) | レジスト剥離液用組成物 | |
| JP2009111409A (ja) | 洗浄液およびそれを用いた洗浄法 | |
| KR20150077929A (ko) | 레지스트 박리액 조성물 및 이를 이용한 레지스트의 박리방법 | |
| KR20020019813A (ko) | 암모늄 플로라이드를 함유하는 포토레지스트 리무버조성물 | |
| KR20150077928A (ko) | 레지스트 박리액 조성물 및 이를 이용한 레지스트의 박리방법 | |
| KR20090080226A (ko) | 포토레지스트 잔류물 제거용 박리액 조성물 및 이를 이용한박리 방법 |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| TR01 | Transfer of patent right | ||
| TR01 | Transfer of patent right |
Effective date of registration: 20170425 Address after: American Pennsylvania Patentee after: Anwantuo materials limited liability company Address before: new jersey Patentee before: Anwantuo Spcial Materials Co., Ltd. |