CN102782113A - 用于镶嵌工艺侧壁聚合物的清洗溶液 - Google Patents
用于镶嵌工艺侧壁聚合物的清洗溶液 Download PDFInfo
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- 238000004140 cleaning Methods 0.000 title claims abstract description 94
- 238000000034 method Methods 0.000 title claims abstract description 16
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- 230000008569 process Effects 0.000 title claims abstract description 9
- 239000000463 material Substances 0.000 claims abstract description 21
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 24
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 claims description 21
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 claims description 13
- 239000003352 sequestering agent Substances 0.000 claims description 13
- 150000001732 carboxylic acid derivatives Chemical class 0.000 claims description 11
- NBZBKCUXIYYUSX-UHFFFAOYSA-N iminodiacetic acid Chemical compound OC(=O)CNCC(O)=O NBZBKCUXIYYUSX-UHFFFAOYSA-N 0.000 claims description 11
- 239000003989 dielectric material Substances 0.000 claims description 9
- 150000001412 amines Chemical class 0.000 claims description 8
- 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 7
- LDDQLRUQCUTJBB-UHFFFAOYSA-N ammonium fluoride Chemical group [NH4+].[F-] LDDQLRUQCUTJBB-UHFFFAOYSA-N 0.000 claims description 7
- 235000006408 oxalic acid Nutrition 0.000 claims description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 7
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 claims description 6
- 239000002253 acid Substances 0.000 claims description 6
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims description 4
- KVBCYCWRDBDGBG-UHFFFAOYSA-N azane;dihydrofluoride Chemical compound [NH4+].F.[F-] KVBCYCWRDBDGBG-UHFFFAOYSA-N 0.000 claims description 4
- 229960004418 trolamine Drugs 0.000 claims description 3
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 2
- OUUQCZGPVNCOIJ-UHFFFAOYSA-M Superoxide Chemical class [O-][O] OUUQCZGPVNCOIJ-UHFFFAOYSA-M 0.000 claims description 2
- 239000013543 active substance Substances 0.000 claims description 2
- 150000001298 alcohols Chemical class 0.000 claims description 2
- 239000003518 caustics Substances 0.000 claims description 2
- 150000002148 esters Chemical class 0.000 claims description 2
- 229910017604 nitric acid Inorganic materials 0.000 claims description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims 2
- 229910021529 ammonia Inorganic materials 0.000 claims 1
- 238000001020 plasma etching Methods 0.000 claims 1
- 239000000243 solution Substances 0.000 description 28
- 230000006872 improvement Effects 0.000 description 26
- 230000002000 scavenging effect Effects 0.000 description 19
- 239000010410 layer Substances 0.000 description 17
- 239000007789 gas Substances 0.000 description 13
- 238000004380 ashing Methods 0.000 description 12
- 230000000694 effects Effects 0.000 description 11
- 229910052751 metal Inorganic materials 0.000 description 10
- 239000002184 metal Substances 0.000 description 10
- 239000010949 copper Substances 0.000 description 8
- 229910004298 SiO 2 Inorganic materials 0.000 description 7
- QPJSUIGXIBEQAC-UHFFFAOYSA-N n-(2,4-dichloro-5-propan-2-yloxyphenyl)acetamide Chemical compound CC(C)OC1=CC(NC(C)=O)=C(Cl)C=C1Cl QPJSUIGXIBEQAC-UHFFFAOYSA-N 0.000 description 7
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 6
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 6
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 6
- 238000001312 dry etching Methods 0.000 description 6
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- 239000001301 oxygen Substances 0.000 description 6
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- 229910052802 copper Inorganic materials 0.000 description 4
- 229910052739 hydrogen Inorganic materials 0.000 description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 description 3
- 239000001257 hydrogen Substances 0.000 description 3
- 229910052757 nitrogen Inorganic materials 0.000 description 3
- 229910052710 silicon Inorganic materials 0.000 description 3
- 239000010703 silicon Substances 0.000 description 3
- -1 silicon nitrides Chemical class 0.000 description 3
- BJEPYKJPYRNKOW-REOHCLBHSA-N (S)-malic acid Chemical compound OC(=O)[C@@H](O)CC(O)=O BJEPYKJPYRNKOW-REOHCLBHSA-N 0.000 description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 2
- BJEPYKJPYRNKOW-UHFFFAOYSA-N alpha-hydroxysuccinic acid Natural products OC(=O)C(O)CC(O)=O BJEPYKJPYRNKOW-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
- 230000004888 barrier function Effects 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 238000000151 deposition Methods 0.000 description 2
- 230000008021 deposition Effects 0.000 description 2
- 230000009977 dual effect Effects 0.000 description 2
- NBVXSUQYWXRMNV-UHFFFAOYSA-N fluoromethane Chemical compound FC NBVXSUQYWXRMNV-UHFFFAOYSA-N 0.000 description 2
- 229920002313 fluoropolymer Polymers 0.000 description 2
- 150000002431 hydrogen Chemical class 0.000 description 2
- 239000002075 main ingredient Substances 0.000 description 2
- 239000001630 malic acid Substances 0.000 description 2
- 235000011090 malic acid Nutrition 0.000 description 2
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- DDFHBQSCUXNBSA-UHFFFAOYSA-N 5-(5-carboxythiophen-2-yl)thiophene-2-carboxylic acid Chemical compound S1C(C(=O)O)=CC=C1C1=CC=C(C(O)=O)S1 DDFHBQSCUXNBSA-UHFFFAOYSA-N 0.000 description 1
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 1
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- 229910000737 Duralumin Inorganic materials 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 240000007711 Peperomia pellucida Species 0.000 description 1
- 229910052581 Si3N4 Inorganic materials 0.000 description 1
- NRTOMJZYCJJWKI-UHFFFAOYSA-N Titanium nitride Chemical compound [Ti]#N NRTOMJZYCJJWKI-UHFFFAOYSA-N 0.000 description 1
- 150000003863 ammonium salts Chemical class 0.000 description 1
- LDDQLRUQCUTJBB-UHFFFAOYSA-O azanium;hydrofluoride Chemical compound [NH4+].F LDDQLRUQCUTJBB-UHFFFAOYSA-O 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 1
- 229910052794 bromium Inorganic materials 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 229910002091 carbon monoxide Inorganic materials 0.000 description 1
- 150000001735 carboxylic acids Chemical class 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000002738 chelating agent Substances 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 229960001484 edetic acid Drugs 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 238000001259 photo etching Methods 0.000 description 1
- 239000012088 reference solution Substances 0.000 description 1
- HQVNEWCFYHHQES-UHFFFAOYSA-N silicon nitride Chemical compound N12[Si]34N5[Si]62N3[Si]51N64 HQVNEWCFYHHQES-UHFFFAOYSA-N 0.000 description 1
Classifications
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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
- C11D7/34—Organic compounds containing sulfur
-
- 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
- C11D11/00—Special methods for preparing compositions containing mixtures of detergents ; Methods for using cleaning compositions
- C11D11/0094—Process for making liquid detergent compositions, e.g. slurries, pastes or gels
-
- 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
- C11D7/08—Acids
-
- 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
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23G—CLEANING OR DE-GREASING OF METALLIC MATERIAL BY CHEMICAL METHODS OTHER THAN ELECTROLYSIS
- C23G1/00—Cleaning or pickling metallic material with solutions or molten salts
- C23G1/02—Cleaning or pickling metallic material with solutions or molten salts with acid solutions
- C23G1/10—Other heavy metals
- C23G1/103—Other heavy metals copper or alloys of copper
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23G—CLEANING OR DE-GREASING OF METALLIC MATERIAL BY CHEMICAL METHODS OTHER THAN ELECTROLYSIS
- C23G1/00—Cleaning or pickling metallic material with solutions or molten salts
- C23G1/02—Cleaning or pickling metallic material with solutions or molten salts with acid solutions
- C23G1/12—Light metals
- C23G1/125—Light metals aluminium
-
- 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
- H01L21/0206—Cleaning during device manufacture during, before or after processing of insulating layers
- H01L21/02063—Cleaning during device manufacture during, before or after processing of insulating layers the processing being the formation of vias or contact holes
-
- 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 at least one potential-jump barrier or surface barrier, e.g. PN junction, depletion layer or carrier concentration layer
- H01L21/18—Manufacture or treatment of semiconductor devices or of parts thereof the devices having at least one potential-jump barrier or surface barrier, e.g. PN junction, depletion layer or carrier concentration layer the devices having semiconductor bodies comprising elements of Group IV of the Periodic System 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
- H01L21/302—Treatment of semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/26 to change their surface-physical characteristics or shape, e.g. etching, polishing, cutting
- H01L21/306—Chemical or electrical treatment, e.g. electrolytic etching
- H01L21/3065—Plasma etching; Reactive-ion etching
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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
- H01L21/70—Manufacture or treatment of devices consisting of a plurality of solid state components formed in or on a common substrate or of parts thereof; Manufacture of integrated circuit devices or of parts thereof
- H01L21/71—Manufacture of specific parts of devices defined in group H01L21/70
- H01L21/768—Applying interconnections to be used for carrying current between separate components within a device comprising conductors and dielectrics
- H01L21/76801—Applying interconnections to be used for carrying current between separate components within a device comprising conductors and dielectrics characterised by the formation and the after-treatment of the dielectrics, e.g. smoothing
- H01L21/76802—Applying interconnections to be used for carrying current between separate components within a device comprising conductors and dielectrics characterised by the formation and the after-treatment of the dielectrics, e.g. smoothing by forming openings in dielectrics
- H01L21/76814—Applying interconnections to be used for carrying current between separate components within a device comprising conductors and dielectrics characterised by the formation and the after-treatment of the dielectrics, e.g. smoothing by forming openings in dielectrics post-treatment or after-treatment, e.g. cleaning or removal of oxides on underlying conductors
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- C11D2111/22—
Abstract
此处描述了一种水性清洗溶液以及使用该清洗溶液的方法,用于去除在晶片上进行镶嵌工艺产生的侧壁聚合物,而不会损坏晶片上的任何低k材料和互连材料。
Description
本申请根据美国法35U.S.C.§119(e)要求申请号为61/311,122、名称为用于镶嵌工艺侧壁聚合物的清洗溶液、申请日为2010年3月5日的美国临时申请的优先权,此处,其全部内容通过引用方式并入。
背景技术
直到最近,才开始大规模生产具有Al/SiO2多层互连结构的半导体器件,其使用铝、铝合金或类似物作为互连材料,且使用SiO2膜作为层间绝缘膜。为了减少由器件微小型化引起的连线延迟,目前正在开发具有Cu/低k多层互连结构的半导体器件,其使用Cu作为低电阻互连材料,且使用低k膜(低介电常数膜)作为具有低互连电容的层间绝缘膜以替代SiO2膜。
在Al/SiO2多层互连结构中,布线层(wiring layers)和通孔层(via layers)单独形成;布线层水平地在整个处理过的晶片上输送电流;以及通孔层通过与布线层连接的垂直孔形成布线。每个布线层的形成是由金属干法蚀刻生成金属线(例如Al),并沉积诸如SiO2膜等层间介质层以覆盖金属线。在诸如SiO2膜等层间介质层沉积之后,对该层间介质层进行干蚀刻以形成一个孔(通孔),并用诸如Al或W等金属填充该孔,形成通孔层。
Cu/低k多层互连结构由一个被称为镶嵌的工艺所制造,其中,在低k膜中通过干蚀刻形成沟槽或孔(通孔),然后再用诸如铜等互连材料填充所述沟槽或孔,获得所述布线结构。在被称为双镶嵌(dual damascene)的技术中,用于布线和通孔的沟槽在低k膜中形成,然后填充诸如铜等互连材料。双镶嵌结构可以通过先通孔工艺形成,其中,所述通孔要早于布线沟槽形成;或相反地,通过先沟槽工艺,其中,所述沟槽要早于用于布线的通孔形成;或通过其它工艺,例如先中间层工艺或双硬掩模工艺。在双镶嵌工艺或类似工艺中,在许多情况下,都使用互连材料。在先通孔工艺中,例如,通过干蚀刻形成通孔,然后填充互连材料,接着通过光刻和蚀刻形成沟槽。此后必须选择性地去除互连材料。
在Al/SiO2多层互连结构中,使用例如氯或溴化氢等气体的金属蚀刻以形成布线,且使用混合气体的通孔蚀刻以形成通孔,所述混合气体包括碳氟化合物气体、氢氟烃气体、诸如Ar等惰性气体、氧气、诸如一氧化碳等含氧气体等等。在金属蚀刻或在层间介质层进行用以形成通孔的通孔蚀刻之后,使用含氧的等离子体执行灰化(ashing)来去除不必要的物质,例如抗蚀剂和蚀刻残渣。使用去除溶液去除灰化后剩余的残留物。在金属蚀刻的情况下,残留物由铝氧化物等构成,其含有少量的有机物质,例如抗蚀剂。由于所述残留物形成于铝布线的侧壁上,它可被称为“侧壁聚合物”,“兔耳”,等等。在通孔蚀刻的情况下,残留物由钛的氧化物或氟化物、氮化钛,或其它金属阻隔膜构成,该金属阻隔膜含有少量的有机物质,例如抗蚀剂和碳氟聚合物。该残留物也可被称为“侧壁聚合物”。在许多情况下,在金属或通孔蚀刻之后,对残留物进行灰化处理,直到使用氧等离子体去除抗蚀剂,其结果是,蚀刻残留物的主要组分是已被无机化的氧化物。
相比之下,在Cu/低k多层互连结构中,在低k膜中的沟槽或通孔镶嵌结构由使用碳氟化合物气体与氮气的混合气体等等的干蚀刻形成。在所述干蚀刻气体中使用氮气提高了加工精度。然而,气体与含硅低k膜之间的反应形成了非挥发性的氮化硅残留物。如果完全使用含氧等离子体去除抗蚀剂和蚀刻后的残留物进行灰化,那么低k膜将会损坏,导致介电常数变化。因此,在许多情况下不执行这种等离子体灰化处理;取而代之的是,用氢、氮、稀有气体、这些气体的混合物、或类似物进行灰化处理,或者用含氧等离子体轻微灰化处理。此外,在许多情况下,为了尽量减少对低k膜的损坏,抗蚀剂和互连材料并不是完全由灰化去除。如果含氮气体用于等离子灰化,残留物中进一步含有大量的氮化硅。在这样的情况下,即使在灰化之后,会存在相对大量的抗蚀剂、防反射层、互连材料和诸如氮化硅等含氮蚀刻残留物。即使灰化进行到相当程度,它还是难以去除所有的抗蚀剂、防反射层、和互连材料。因此,在镶嵌工艺中,蚀刻后存在的残留物的主要组分是源于抗蚀剂、抗反射层、互连材料、和碳氟聚合物的有机物质,还含有诸如氮化硅等无机物质。
发明内容
此处描述的是一种水性清洗溶液,其能有效地去除镶嵌工艺中产生的侧壁聚合物,同时使含有一种或多种金属互连材料和一个或多个低k层间介质材料膜的晶片上的低k膜损坏最小化,该清洗溶液含有 的氢氟酸,的硫酸,的羧酸,最多至2%(w/w)的一种或多种螯合剂,最多至15%(w/w)的一种或多种胺,和75%(w/w)或更多的水,其中,所述清洗溶液不会损坏一个或多个低k层间介质材料膜。
具体实施方式
此处描述的是用于去除镶嵌工艺侧壁聚合物的水性清洗溶液。该清洗溶液能有效去除侧壁聚合物而不会损坏低k膜或暴露的互连材料。该水性清洗溶液的例子列于表1,其中,所述各溶液的其余部分(balance)是水,并且HF、H2SO4、乙酸、柠檬酸、苹果酸、IDA、NH4F、NH4HF2和TEA的数值以w/w%形式给出。
表1
在表1中,C1-Cl2是对照组,IDA是亚氨基二乙酸,EDTA是乙二胺四乙酸,TEA是三乙醇胺。表1中的每个数值解释为以该数值为中心±10%的范围。表1中的每个溶液包括水和所列成分。
除C4之外,所有其它的对照组溶液(C1-C3和C5-C12)是各种浓度的氢氟酸(HF)和硫酸(H2SO4)的水溶液。C4仅仅是HF的水溶液。C4在室温下对低k膜造成严重损坏。C1-C3和C5-C7具有0.06%的HF浓度和3%的硫酸浓度。在30℃时,即使延长清洗时间为30秒钟,C1-C3和C5-C7仍不能非常有效地去除侧壁聚合物。在更高温度时,C1-C3和C5-C7仅仅略微有效,但会导致严重的低k膜损坏。C8-C9具有较高的HF浓度(0.2%)和3%的硫酸,清洗时间仅仅为8秒仍会导致严重的低k膜损坏。C10-C12有较高浓度的硫酸(9%),相对于C1-C9显示出了改善的清洗效果。然而,这些C1-C12对照组显示了,较高温度和/或较高HF浓度往往会导致低k膜更多的损坏。
在T1-T29一系列的测试中,为了评估清洗效果和对低k膜的损坏,把各种羧酸、胺和/或铵盐(作为螯合剂)添加到0.06%HF和3%硫酸的基准溶液中。
通过比较T1和C1中的溶液来评价乙酸的效果。相较于C1,T1并没有表现出明显改善的清洗效果。通过T2和T1中的溶液相比较来评价乙酸和氟化铵相结合的效果。当清洗时间小于30秒,相较于T1,T2并没有表现出明显改善的清洗效果。然而,当清洗时间为30秒时,相较于T1,T2表现出改善的清洗效果。
通过比较T3和C1来评价柠檬酸的效果。相较于C1,T3并没有表现出显著改善的清洗效果。通过比较T4和T3来评价柠檬酸和氟化铵相结合的效果。当清洗时间为4至30秒,相较于T3,T4没有显示出改善的清洗效果。
通过比较T5和C1来评价苹果酸的效果。当清洗时间为4秒,相较于C1,T5并没有表现出显著改善的清洗效果。当清洗时间延长(8、16和30秒),相较于C1,T5表现出显著改善的清洗效果。通过T6和T5比较来评价苹果酸和氟化铵相结合的效果。相较于T5,当清洗时间为4至16秒,T6没有显示出改善的清洗效果,当清洗时间为30秒,T6表现出一定改善的清洗效果。
T7在比T6更高的温度下进行。相较于T6,T7并没有表现出明显改善的清洗效果,但是对低k薄膜却造成了更多的损坏。T8具有比T7更高的苹果酸浓度。当清洗时间为4至30秒,相较于T7,T8表现出轻微改善的清洗效果。
通过T9与C1、T10与C5、和T11与C6的比较来评价IDA的效果。相较于C1,T9表现出显著改善的清洗效果。相较于C5,T10没有表现出显著改善的清洗效果。相较于C6,T11没有表现出显著改善的清洗效果。通过T12与T9、T14与T10、和T15与T11的比较来评价IDA和氟化铵相结合的效果。分别与T9、T10和T11相比较,当清洗时间从4增加至30秒,T12、T14和T15表现出一定改善的清洗效果。
在比T10更高温度下进行T11。相较于T10,T11表现出了轻微改善的清洗效果,并没有对低k薄膜造成更多的损坏。
通过T18与T9比较来评价氟氢化铵(NH4HF2)和IDA相结合的效果。T18表现出对低k膜的明显损坏。比较T17和T14的清洗效果,并且比较T16和T10的清洗效果表明,在T14和T10中添加EDTA可极大地改善它们的清洗效果。
比较T14和T13的清洗效果显示,在T13中增加IDA的浓度可显著地提高T13的清洗效果。
通过T19与C1、T20与C5和T21与C6比较来评价草酸的效果。当清洗时间为4、8和16秒时,相较于C1,T19并没有表现出显著改善的清洗效果。当清洗时间为30秒时,相较于C1,T19表现出显著改善的清洗效果。当清洗时间为8、16和30秒时,相较于C5,T20表现出轻微改善的清洗效果。当清洗时间为8秒时,相较于C6,T21没有表现出显著改善的清洗效果。当清洗时间为16和30秒时,相较于C6,T21表现出显著改善的清洗效果。通过T25与T21、T23与T20和T22与T19比较来评价草酸和氟化铵相结合的效果。当清洗时间为8秒时,相较于T21,T25表现出显著改善的清洗效果。8秒以上,T25表现出对低k膜的明显损坏。相较于T20,T23并没有表现出显著改善的清洗效果。当清洗时间为8秒时,相较于T19,T22并没有表现出显著改善的清洗效果。当清洗时间为16和30秒时,相较于T19,T21表现出显著改善的清洗效果。
比较T28、T29和T24的清洗效果表明,在T24组分中加入5-10%的TEA并没有显著地提高T24的清洗效果。
T27与T24和T26与T20的清洗效果比较表明,在T24以及T20的组分中加入0.2%的EDTA能显著地提高它们的清洗效果。T23和T24的清洗效果并没有表现出很大的差异,尽管它们草酸浓度不同。T21、T23和T25分别相较于T20,T22和T24在更高的温度进行,且表现出显著改善的清洗效果。
表2总结了T1-T29的清洗效果和对低k膜的损坏。
表2
在“侧壁聚合物清洗效果”一栏中,“+”、“O”、“-”分别表示非常有效,一定程度上有效,稍微有效。在“对低k膜的损坏”一栏中,“+”和“-”分别表示没有明显的损坏,严重损坏。
清洗溶液优选是不含醇类、过氧化物(例如,过氧化氢)和酯类。该清洗溶液是基于水(水性)的溶液,该溶液含有HF、 硫酸、羧酸、最多2%的一种或多种螯合剂、最多15%的一种或多种胺、和优选具有75%或更多的水。该清洗溶液也可以不含氢氧化铵、螯合剂、胺、硝酸和/或表面活性剂。该羧酸可以是乙酸(优选为更优选为)、草酸(优选更优选为)、柠檬酸(优选为更优选为)、苹果酸(优选为更优选为 )、或亚氨基二乙酸(优选为更优选)。该螯合剂可以是氟化铵(优选为)、氟氢化铵(优选为)和/或乙二胺四乙酸(优选为)。该胺优选为三乙醇胺(优选为 )。该清洗溶液优选具有与硫酸浓度相等或更高浓度的羧酸。在该清洗溶液中羧酸与螯合剂的浓度比优选至少为10:1。在该清洗溶液中硫酸与螯合剂的浓度比优选至少为10:1。
用于把含有一种或多种诸如Al或Cu等金属互连材料和一个或多个低k层间介质材料的晶片上进行镶嵌工艺产生的侧壁聚合物去除的使用该清洗溶液的方法,可包括把该晶片浸渍在该清洗溶液中保持在温度下最多40秒,更优选为8至30秒。
尽管结合具体的实施例详细地描述了该清洗溶液和使用该清洗溶液的方法,在不脱离所附的权利要求的范围的情况下,所作出的各种改变和修改以及等同方案,对于本领域的技术人员来说是显而易见的。
Claims (20)
2.根据权利要求1所述的清洗溶液,其中,所述羧酸是草酸、苹果酸或亚氨基二乙酸。
5.根据权利要求1所述的清洗溶液,其中,所述螯合剂是氟化铵、氟氢化铵和/或乙二胺四乙酸。
8.根据权利要求1所述的清洗溶液,其中,所述羧酸的浓度与所述硫酸浓度相等或比所述硫酸浓度更高。
9.根据权利要求1所述的清洗溶液,其中,所述羧酸与所述螯合剂的浓度比至少为10:1。
10.根据权利要求1所述的清洗溶液,其中,所述硫酸与所述螯合剂的浓度比至少为10:1。
11.根据权利要求1所述的清洗溶液,其中,所述清洗溶液不含醇类、过氧化物和酯类。
12.根据权利要求1所述的清洗溶液,其中,所述清洗溶液不含过氧化氢。
13.根据权利要求1所述的清洗溶液,其中,所述清洗溶液不含氨。
14.根据权利要求1所述的清洗溶液,其中,所述清洗溶液不含氢氧化铵。
15.根据权利要求1所述的清洗溶液,其中,所述清洗溶液不含一种或多种螯合剂。
16.根据权利要求1所述的清洗溶液,其中,所述清洗溶液不含一种或多种胺。
17.根据权利要求1所述的清洗溶液,其中,所述清洗溶液不含硝酸。
18.根据权利要求1所述的清洗溶液,其中,所述清洗溶液不含一种或多种表面活性剂。
19.使用权利要求1所述的清洗溶液的方法,用于把在含有一种或多种金属互连材料和一个或多个低k层间介质材料膜的晶片上进行镶嵌工艺过程中产生的等离子体蚀刻后特征上的侧壁聚合物去除,该方法包括把该晶片浸渍在该清洗溶液中保持在温度下最多40秒,该清洗溶液有效地去除该侧壁聚合物,同时使得对所述金属互连材料和所述一个或多个低k层间介质材料膜的损坏最小化。
20.权利要求19所述的方法,其中所述晶片在该清洗溶液中浸渍8~30秒。
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- 2011-03-01 KR KR1020127023266A patent/KR20130028059A/ko not_active Application Discontinuation
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- 2011-03-01 WO PCT/US2011/000376 patent/WO2011109078A2/en active Application Filing
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Also Published As
Publication number | Publication date |
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TW201144428A (en) | 2011-12-16 |
JP2013521646A (ja) | 2013-06-10 |
KR20130028059A (ko) | 2013-03-18 |
WO2011109078A3 (en) | 2012-01-26 |
US20110214688A1 (en) | 2011-09-08 |
SG183510A1 (en) | 2012-09-27 |
WO2011109078A2 (en) | 2011-09-09 |
TWI534261B (zh) | 2016-05-21 |
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