CN1096703C - 晶片处理液及其制造方法 - Google Patents
晶片处理液及其制造方法 Download PDFInfo
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- CN1096703C CN1096703C CN96198370A CN96198370A CN1096703C CN 1096703 C CN1096703 C CN 1096703C CN 96198370 A CN96198370 A CN 96198370A CN 96198370 A CN96198370 A CN 96198370A CN 1096703 C CN1096703 C CN 1096703C
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- salt
- represents hydrogen
- phenylene
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- cleaning solution
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- 238000004140 cleaning Methods 0.000 title claims abstract description 33
- 238000000034 method Methods 0.000 title claims abstract description 24
- 238000004519 manufacturing process Methods 0.000 title claims description 10
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 claims abstract description 98
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 49
- 150000003839 salts Chemical group 0.000 claims abstract description 43
- 239000001257 hydrogen Substances 0.000 claims abstract description 42
- 239000004094 surface-active agent Substances 0.000 claims abstract description 39
- 125000000843 phenylene group Chemical group C1(=C(C=CC=C1)*)* 0.000 claims abstract description 33
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 26
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical group [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 38
- 239000012530 fluid Substances 0.000 claims description 19
- 125000000217 alkyl group Chemical group 0.000 claims description 7
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 6
- 229910052799 carbon Inorganic materials 0.000 claims description 6
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 6
- 239000003513 alkali Substances 0.000 claims 2
- 125000003277 amino group Chemical group 0.000 claims 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 abstract description 17
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 abstract description 11
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 abstract description 10
- 229910017604 nitric acid Inorganic materials 0.000 abstract description 8
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 abstract description 6
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 abstract description 5
- 150000001875 compounds Chemical class 0.000 abstract description 3
- 125000004435 hydrogen atom Chemical group [H]* 0.000 abstract description 3
- LDDQLRUQCUTJBB-UHFFFAOYSA-N ammonium fluoride Chemical compound [NH4+].[F-] LDDQLRUQCUTJBB-UHFFFAOYSA-N 0.000 abstract 2
- 125000004169 (C1-C6) alkyl group Chemical group 0.000 abstract 1
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 abstract 1
- 239000000908 ammonium hydroxide Substances 0.000 abstract 1
- 229910000040 hydrogen fluoride Inorganic materials 0.000 abstract 1
- 235000011007 phosphoric acid Nutrition 0.000 abstract 1
- 235000012431 wafers Nutrition 0.000 description 36
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 30
- 229910052710 silicon Inorganic materials 0.000 description 30
- 239000010703 silicon Substances 0.000 description 30
- 229960002050 hydrofluoric acid Drugs 0.000 description 29
- 239000007864 aqueous solution Substances 0.000 description 23
- 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 23
- 239000011734 sodium Substances 0.000 description 18
- 239000002245 particle Substances 0.000 description 16
- 239000000243 solution Substances 0.000 description 16
- 230000000052 comparative effect Effects 0.000 description 15
- 238000011010 flushing procedure Methods 0.000 description 8
- 239000004793 Polystyrene Substances 0.000 description 7
- 239000004816 latex Substances 0.000 description 7
- 229920000126 latex Polymers 0.000 description 7
- 229920002223 polystyrene Polymers 0.000 description 7
- 229910021642 ultra pure water Inorganic materials 0.000 description 7
- 239000012498 ultrapure water Substances 0.000 description 7
- 239000002585 base Substances 0.000 description 6
- 238000001035 drying Methods 0.000 description 6
- 230000000694 effects Effects 0.000 description 6
- 125000001453 quaternary ammonium group Chemical group 0.000 description 6
- 239000000758 substrate Substances 0.000 description 4
- 239000003599 detergent Substances 0.000 description 3
- 238000005530 etching Methods 0.000 description 3
- 230000003647 oxidation Effects 0.000 description 3
- 238000007254 oxidation reaction Methods 0.000 description 3
- XWROUVVQGRRRMF-UHFFFAOYSA-N F.O[N+]([O-])=O Chemical compound F.O[N+]([O-])=O XWROUVVQGRRRMF-UHFFFAOYSA-N 0.000 description 2
- 229910019142 PO4 Inorganic materials 0.000 description 2
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 2
- 150000003863 ammonium salts Chemical class 0.000 description 2
- 229960001231 choline Drugs 0.000 description 2
- 230000003749 cleanliness Effects 0.000 description 2
- 238000010790 dilution Methods 0.000 description 2
- 239000012895 dilution Substances 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- -1 hydrofluoric acid peroxide Chemical class 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 2
- 239000010452 phosphate Substances 0.000 description 2
- 239000004065 semiconductor Substances 0.000 description 2
- 229910052708 sodium Inorganic materials 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 150000003866 tertiary ammonium salts Chemical class 0.000 description 2
- 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
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- 229910004298 SiO 2 Inorganic materials 0.000 description 1
- RGTYLICFMNSKMS-UHFFFAOYSA-N [Si].[Si].[Si] Chemical compound [Si].[Si].[Si] RGTYLICFMNSKMS-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 230000001154 acute effect Effects 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 239000003945 anionic surfactant Substances 0.000 description 1
- 230000005587 bubbling Effects 0.000 description 1
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- OEYIOHPDSNJKLS-UHFFFAOYSA-N choline Chemical compound C[N+](C)(C)CCO OEYIOHPDSNJKLS-UHFFFAOYSA-N 0.000 description 1
- 239000004020 conductor Substances 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 238000007598 dipping method Methods 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 239000004744 fabric Substances 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 125000004051 hexyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- GTNCDQPGIIXNLN-UHFFFAOYSA-N hydrogen peroxide dihydrochloride Chemical compound Cl.Cl.OO GTNCDQPGIIXNLN-UHFFFAOYSA-N 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 150000003242 quaternary ammonium salts Chemical class 0.000 description 1
- 238000001039 wet etching Methods 0.000 description 1
Classifications
-
- 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
- H01L21/302—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
- H01L21/304—Mechanical treatment, e.g. grinding, polishing, cutting
-
- 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
- H01L21/02043—Cleaning before device manufacture, i.e. Begin-Of-Line process
- H01L21/02052—Wet cleaning only
-
- 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
- C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
- C11D1/02—Anionic compounds
- C11D1/12—Sulfonic acids or sulfuric acid esters; Salts thereof
- C11D1/22—Sulfonic acids or sulfuric acid esters; Salts thereof derived from aromatic compounds
- C11D1/24—Sulfonic acids or sulfuric acid esters; Salts thereof derived from aromatic compounds containing ester or ether groups directly attached to the nucleus
-
- 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
- C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
- C11D1/02—Anionic compounds
- C11D1/12—Sulfonic acids or sulfuric acid esters; Salts thereof
- C11D1/29—Sulfates of polyoxyalkylene ethers
-
- 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
- C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
- C11D3/02—Inorganic compounds ; Elemental compounds
- C11D3/04—Water-soluble compounds
- C11D3/042—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
- C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
- C11D3/39—Organic or inorganic per-compounds
- C11D3/3947—Liquid compositions
-
- 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
- C11D2111/00—Cleaning compositions characterised by the objects to be cleaned; Cleaning compositions characterised by non-standard cleaning or washing processes
- C11D2111/10—Objects to be cleaned
- C11D2111/14—Hard surfaces
- C11D2111/22—Electronic devices, e.g. PCBs or semiconductors
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- Chemical & Material Sciences (AREA)
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- Condensed Matter Physics & Semiconductors (AREA)
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- Power Engineering (AREA)
- Microelectronics & Electronic Packaging (AREA)
- Physics & Mathematics (AREA)
- Computer Hardware Design (AREA)
- Manufacturing & Machinery (AREA)
- Cleaning Or Drying Semiconductors (AREA)
- Weting (AREA)
- Detergent Compositions (AREA)
Abstract
晶片处理液,及在该处理液中添加水,H2O2,HNO3,CH3COOH,NH4F等,制造低浓度晶片处理液的方法。
Description
技术领域
本发明涉及硅晶片处理及制造晶片处理液的方法,更详细地说,是防止因硅晶片表面微粒所致污染的硅晶片处理液及其制造方法。
背景技术
在由硅单晶组成的半导体基片(晶片)上形成的LSI(大规模集成电路)半导体集成电路装置的制造工序中,在使基片表面的氧化膜(SiO2)形成图案,或在热处理工序中去除基片表面形成的自然氧化膜时,需要使用氟化氢的水溶液(HF)进行湿法蚀刻处理。此外,在SiO2表面的蚀刻处理时,需用氢氟酸(HF)水溶液或缓冲氢氟酸水溶液(HF-NH4F-H2O)进行处理。还有,在Si3N4蚀刻处理时,可用磷酸(H3PO4)水溶液进行处理。再有,在硅表面蚀刻处理时,用氢氟酸(HF)-硝酸(HNO3)水溶液或氢氟酸(HF)-硝酸(HNO3)-醋酸(CH3COOH)水溶液进行处理。此外,在布线工序等中,在去除附着于基片表面的金属时,用氢氟酸(HF)水溶液,氢氟酸(HF)-过氧化氢(H2O2)水溶液或盐酸(HCl)-过氧化氢(H2O2)水溶液进行湿法洗净处理。在这些湿法洗净处理中,为了防止在去除了上述氧化膜或金属后的活性基片表面上附着异物,为使蚀刻液或洗净液循环过滤,保持蚀刻液或洗净液的清净度,需采取措施。
然而,随着集成电路的微型化,对于上述蚀刻液或洗净液不仅提出更高的清净度要求,而且出现由于晶片工艺的增加或晶片尺寸变大,因而使得带入处理槽中的异物增加的问题。
为此,至今开发了在上述处理液中添加表面活性剂的技术。在所有的这些方法中均存在这样的问题,即即使在高浓度的HF或H2O2,HNO3,CH3COOH,NH4F,HCl,H3PO4及用通式[(R1)(R2)(R3)(R4)N]+OH-(R1,R2,R3,R4分别表示可具有羟基,碳数为1~6的烷基)表示的季铵碱中使表面活性剂溶解至溶解度,但在稀释或与其它化学药品混合时,表面活性剂变稀,得不到减少粒子附着的效果。此外,在表面活性剂稀释或与其它化学药品混合时需添加表面活性剂的场合下,不仅花费时间,而且为了达到充分减少粒子的附着效果,需大量添加表面活性剂,因而产生激剧起泡的问题。
本发明者从这一观点考虑,提出了在低浓度的氢氟酸等中,通过添加阴离子表面活性剂或非离子表面活性剂的处理液进行处理,防止硅晶片表面微粒的污染方法(特开平6-41770号),但又产生了保管及运输效率低的问题。此外,在特开平6-41770号中记载的表面活性剂在高浓度氢氟酸中是否高浓度地溶解尚不清楚。
本发明的目的是提供晶片处理液,在晶片表面清洗处理或蚀刻处理时,即使在高浓度的HF或H2O2,HNO3,CH3COOH,NH4F,HCl,H3PO4及用通式[(R1)(R2)(R3)(R4)N]+OH-(R1,R2,R3,R4分别表示可具有羟基,碳数为1~6的烷基)表示的季铵碱中含有特定的表面活性剂,也不会产生起泡问题,而且溶解性好,保管及运输效率高,使用时即使稀释成低浓度时,也有优良的防止因晶片表面微粒所致的污染的作用。
此外,本发明的目的是提供晶片处理液,在晶片表面洗净处理或蚀刻处理时,具有优良的防止硅晶片表面微粒所致污染的作用。
发明内容
本发明涉及晶片处理液,以及在该处理液中添加水,H2O2,HNO3,CH3COOH,NH4F等,制造低浓度晶片处理液的方法,是在20~60wt%的氢氟酸(HF)中,将CnH2n+1ph(SO3M)Oph(SO3M)(ph为亚苯基,n为5~20,M表示氢或盐),CnH2n+1phO(CH2CH2O)mSO3M(ph为亚苯基,n为5~20,m为0~20,M表示氢或盐)及CnH2n+1O(CH2CH2O)mSO3M(n为5~20,m为0~20,M表示氢或盐)中的至少一种溶解0.1~1000ppm,剩余部分为水(合计100wt%)所组成的。
此外,本发明涉及晶片处理液,是在HF或H2O2,HNO3,CH3COOH,NH4F,HCl,H3PO4及以式[(R1)(R2)(R3)(R4)N]+OH-(R1,R2,R3,R4分别表示可具有羟基,碳数为1~6的烷基)表示的季铵碱中的至少一种中,将以CnH2n+1ph(SO3M)Oph(SO3M)(ph为亚苯基,n为5~20,M表示氢或盐),CnH2n+1phO(CH2CH2O)mSO3M(ph为亚苯基,n为5~20,m为0~20,M表示氢或盐)表示的表面活性剂中的至少一种溶解0.01~1000ppm,剩余部分为水(合计100wt%)所组成的。
在本发明中,添加上述特定的表面活性剂后,可制得氢氟酸水溶液(HF-H2O),氢氟酸过氧化氢水溶液(HF-H2O2-H2O),氢氟酸硝酸水溶液(HF-HNO3-H2O),氢氟酸硝酸醋酸水溶液(HF-HNO3-CH3COOH-H2O),缓冲氢氟酸水溶液(HF-NH4F-H2O),盐酸过氧化氢水溶液(HCl-H2O2-H2O),磷酸水溶液(H3PO4-H2O),季铵碱过氧化氢水溶液[(R1)(R2)(R3)(R4)N]+OH-H2O2H2O)等洗净及蚀刻处理液。
本发明能制得含有特定表面活性剂的高浓度氢氟酸水溶液(HF-H2O)类的晶片处理液,在该处理液中添加水,H2O2,HNO3,CH3COOH,NH4F等,调制上述各种晶片处理液时,也能取得同样效果。
本发明中含有上述表面活性剂的氢氟酸水溶液所组成的晶片处理液,优选氢氟酸的浓度为20~60wt%,表面活性剂的浓度范围为0.1~1000ppm。
在这些晶片处理液中,添加水,H2O2,HNO3,CH3COOH,NH4F等调制各种晶片处理液时,氢氟酸水溶液(HF-H2O)中优选氢氟酸浓度为0.1~5wt%;氢氟酸过氧过氢水溶液(HF-H2O2-H2O)中优选氢氟酸浓度为0.1~10wt%,H2O2的浓度为0.01~30wt%;氢氟酸硝酸水溶液(HF-HNO3-H2O)中优选氢氟酸浓度0.1~50wt%,HNO3浓度为0.1~70wt%;氢氟酸硝酸醋酸水溶液(HF-HNO3-CH3COOH-H2O)中,优选氢氟酸浓度为0.1~50wt%,硝酸浓度为0.1~70wt%,CH3COOH浓度为0.1~50wt%;在缓冲氢氟酸水溶液(HF-NH4F-H2O)中,优选氢氟酸浓度为0.1~10wt%,NH4F的浓度为1~40wt%;在盐酸过氧化氢水溶液(HCl-H2O2-H2O)中,优选盐酸浓度为0.1~36wt%,H2O2浓度为0.1~30wt%;在磷酸水溶液(H3PO4-H2O)中,优选磷酸浓度为1~90wt%;在季铵盐过氧化氢水溶液([(R1)(R2)(R3)(R4)N]+OH--H2O2-H2O)中,优选季铵碱浓度为0.01~10wt%,H2O2浓度为0.01~30wt%。
本发明所用季铵碱用式[(R1)(R2)(R3)(R4)N]+OH-表示,其中R1,R2,R3,R4分别表示可具有羟基,碳数为1~6的烷基。烷基可以是甲基,乙基,丙基,丁基,己基,具体的化合物例如有〔HOCH2CH2N(CH3)〕+OH-(胆碱),〔(CH3)4N〕+OH-,〔(C2H5)4N〕+OH-等。
本发明所用表面活性剂优选以式CnH2n+1ph(SO3M)Oph(SO3M)(ph为亚苯基,n为5~20,M表示氢或盐),CnH2n+1phO(CH2CH2O)mSO3M(ph为亚苯基,n为5~20,m为0~20,M为氢或盐)及CnH2n+1O(CH2CH2O)mSO3M(n为5~20,m为0~20,M为氢或盐)表示的表面活性剂。这里的盐可以是钠、钾等碱金属盐,铵盐,伯、仲或叔胺盐等。胺如CH3NH2,(CH3)2NH,(CH3)3N等。
具体例如C12H25ph(SO3H)Oph(SO3H),C12H25O(CH2CH2O)2SO3H,C9H19phO(CH2CH2O)4SO3H,C12H25O(CH2CH2O)4SO3Na,C9H19phO(CH2CH2O)6SO3H及它们的金属盐,铵盐,伯、仲或叔胺盐等。表面活性剂的浓度均优选0.01~1000ppm,尤其在0.01~100ppm范围内特优选。
具体实施方式
以下举实施例及比较例加以说明。
实施例1~5及比较例1~5。
0.5%的HF水溶液中加入标准粒子粒径约0.6μm的聚苯乙烯胶乳至微粒子数为105个/ml,进而添加如表1所示的各种表面活性剂,将附有自然氧化膜的4英寸硅晶片置于调制成的这种处理液中浸渍10分钟,其后用超纯水冲洗干燥后,使用激光表面检测装置(日立电子Engineering制的LS-5000)测定硅晶片表面附着的微粒子数,结果如表1所示。表1所示的附着粒子数为每处理二片硅晶片的平均值。【表1】
表面活性剂 | 0.5%HF | 50%HF | |||||
浓度(ppm) | 附着粒子数(个/片) | 消泡性 | 浓度(ppm) | 溶解性 | |||
实施例 | 1 | C12H25ph(SO3H)Oph(SO3H) | 0.1 | 120 | ○ | 10 | ○ |
2 | 同上 | 11 | 180 | ○ | 100 | ○ | |
3 | 同上 | 22 | 180 | ○ | 200 | ○ | |
4 | C9H19phO(CH2CH2O)4SO3Na | 1 | 110 | ○ | 100 | ○ | |
5 | C9H19phO(CH2CH2O)6SO3NH4 | 1 | 230 | ○ | 100 | ○ | |
比较例 | 1 | 未加入 | 0 | 6000 | - | 0 | - |
2 | C12H25phSO3Na | 11 | 1300 | ○ | 100 | ○ | |
3 | 同上 | 200 | 72 | × | 20000 | × | |
4 | C12H25OSO3Na | 1 | 4000 | ○ | 100 | ○ | |
5 | C12H25N(CH2CH2OH)2 | 1 | 6000 | ○ | 100 | ○ |
实施例6~9及比较例6~9。
稀氟酸过氧化氢水溶液〔HF(0.5%)-H2O2(10%)-H2O〕中加入标准粒子粒径约为0.6μm的聚苯乙烯胶乳至微粒子数为105个/ml,进而添加表2所示的各种表面活性剂。将附有自然氧化膜的4英寸硅晶片置于调制后的这种处理液中浸渍10分钟,其后用超纯水冲洗干燥后,用激光表面检测装置(LS-5000)测定附着在硅晶片表面的微粒子数,其结果如表2所示。表2中记载的附着粒子数为每处理二片硅晶片的平均值。【表2】
表面活性剂 | HF(0.5%)-H2O2(10%)-H2O | 50%HF | ||||
浓度(ppm) | 附着粒子数(个/片) | 消泡性 | 浓度(ppm) | 溶解性 | ||
实施例 | ||||||
6 | C12H25ph(SO3H)Oph(SO3H) | 0.5 | 840 | ○ | 50 | ○ |
7 | 同上 | 1 | 660 | ○ | 11000 | ○ |
8 | C9H19phO(CH2CH2O)4SO3Na | 1 | 950 | ○ | 100 | ○ |
9 | C9H19phO(CH2CH2O)6SO3NH4 | 1 | 800 | ○ | 100 | ○ |
比较例 | ||||||
6 | 未加入 | 0 | 2400 | - | 0 | - |
7 | C12H25phSO3Na | 1 | 1900 | ○ | 100 | ○ |
8 | C12H25OSO3Na | 11 | 4500 | ○ | 11000 | ○ |
9 | C12H25N(CH2CH2OH)2 | 1 | >10000 | ○ | 100 | ○ |
实施例10~11及比较例10~13
氢氟酸硝酸水溶液〔HF(1%)-HNO3(5%)-H2O〕中添加标准粒子粒径约为0.6μm的聚苯乙烯胶乳至微粒子数为105个/ml。进而添加表3所示的各种表面活性剂,将附有自然氧化膜的4英寸硅晶片置于调制成的这种处理液中浸渍10分钟,其后用超纯水冲洗干燥后,用激光表面检测装置(LS-5000)测定其附着在硅晶片表面的微粒子数,其结果如表3所示。表3所记载的附着粒子数是每处理二片硅晶片的平均值。【表3】
表面活性剂 | HF(1%)-HNO3(5%)-H2O | 50%HF | ||||
浓度(ppm) | 附着粒子数(个/片) | 消泡性 | 浓度(ppm) | 溶解性 | ||
实施例 | ||||||
10 | C12H25ph(SO3H)Oph(SO3H) | 1 | 2800 | ○ | 100 | ○ |
11 | C9H19phO(CH2CH2O)4SO3Na | 1 | 1900 | ○ | 100 | ○ |
比较例 | ||||||
10 | 未加入 | 0 | 7800 | - | 0 | - |
11 | C12H25phSO3Na | 1 | 8900 | ○ | 100 | ○ |
12 | C12H25OSO3Na | 1 | 6600 | ○ | 100 | ○ |
13 | C12H25N(CH2CH2OH)2 | 1 | 6400 | ○ | 100 | ○ |
实施例12~14及比较例14~17
缓冲氢氟酸水溶液〔HF(6%)-NNO3(5%)-H2O〕中添加标准粒子粒径约为0.6μm的聚苯乙烯胶乳至微粒子数为105个/ml。进而添加表3所示的各种表面活性剂,将附有自然氧化膜的4英寸硅晶片置于调制成的这种处理液中浸渍10分钟,其后用超纯水冲洗干燥后,用激光表面检测装置(LS-5000)测定其附着在硅晶片表面的微粒子数,其结果如表4所示。表4所记载的附着粒子数是每处理二片硅晶片的平均值。【表4】
表面活性剂 | HF(6%)-NH4F(30%)-H2O | 50%HF | ||||
浓度(ppm) | 附着粒子数(个/片) | 消泡性 | 浓度(ppm) | 溶解性 | ||
实施例 | ||||||
12 | C12H25ph(SO3H)Oph(SO3H) | 11 | 1300 | ○ | 8.3 | ○ |
13 | 同上 | 10 | 1100 | ○ | 83 | ○ |
14 | C9H19phO(CH2CH2O)4SO3Na | 10 | 600 | ○ | 83 | ○ |
比较例 | ||||||
14 | 未加入 | 00 | 4000 | - | 0 | - |
15 | C12H25phSO3Na | 1 | 3900 | ○ | 8.3 | ○ |
16 | C12H25OSO3Na | 1 | 4200 | ○ | 8.3 | ○ |
17 | C12H25N(CH2CH2OH)2 | 1 | 5800 | ○ | 8.3 | ○ |
实施例15及比较例18~21
盐酸过氧化氢水溶液〔HCl(36%)∶H2O2(30%)∶H2O=1∶1∶6(容量比)〕中加入标准粒子粒径约为0.6μm的聚苯乙烯胶乳的微粒子至微粒子数为105个/ml。进而添加表4所示的各种表面活性剂。再将调制成的处理液加热至80℃,将去除了自然氧化膜的4英寸硅晶片于其中浸渍10分钟,其后用超纯水冲洗→用0.5%的HF除去自然氧化膜→超纯水冲洗→干燥后,用激光表面检测装置(LS-5000)测定附着在硅晶片表面的微粒子数,结果如表5所示,表5所记载的附着粒子数是每处理二片硅晶片的平均值。【表5】
表面活性剂 | HCl(36%)∶H2O2(30%)∶H2O=1∶1∶6(体积比) | |||
濃度(ppm) | 附着粒子数(个/片) | 消泡性 | ||
实施例 | ||||
15 | C12H25ph(SO3H)Oph(SO3H) | 1 | 710 | ○ |
比较例 | ||||
18 | 未加入 | 0 | 4100 | - |
19 | C12H25phSO3Na | 1 | 8900 | ○ |
20 | C12H25OSO3Na | 1 | >10000 | ○ |
21 | C12H25N(CH2CH2OH)2 | 1 | >10000 | ○ |
实施例16及比较例22~25
85wt%的H3PO4中,再将标准粒子粒径约为0.6μm的聚苯乙烯胶乳添加成微粒子数为105个/ml。进而添加表6所示的各种表面活性剂,再将调制成的处理液加热至150℃,将附有膜厚100nmSi3N4膜的5英寸硅晶片置于其中浸渍10分钟,其后用纯超水冲洗干燥后用激光表面检测装置(LS-5000)测定附着在硅晶片表面的微粒子数,结果如表6所示。表6所记载的附着粒子数是每处理二片硅晶片的平均值。【表6】
表面活性剂 | 85%H3PO4(150℃) | |||
浓度(ppm) | 附着粒子数(个/片) | 消泡性 | ||
实施例 | ||||
16 | C12H25ph(SO3H)Oph(SO3H) | 1 | 3200 | ○ |
比较例 | ||||
22 | 未加入 | 0 | 8000 | - |
23 | C12H25phSO3Na | 1 | >10000 | ○ |
24 | C12H25OSO3Na | 1 | >10000 | ○ |
25 | C12H25N(CH2CH2OH)2 | 1 | >10000 | ○ |
实施例17~22及比较例26~29
60~70℃的胆碱过氧化氢水溶液(〔HOCH2CH2(CH3)3〕+OH-(0.1%)-H2O2(2%)-H2O中加入标准粒子粒径约为0.6μm的聚苯乙烯胶乳至粒子数为105个/ml。进而添加表7所示的各种表面活性剂,将去除了自然氧化膜的4英寸硅晶片及附有热氧化膜的4英寸硅晶片置于调制成的这种处理液中浸渍10分钟,其后用超纯水冲洗干燥后,用激光表面检测装置(LS-5000)测定附着在硅晶片表面的微粒子数,结果如表7所示,表7记载的附着粒子数是每处理三片晶片的平均值。【表7】
表面活性剂 | 浓度(ppm) | 晶片表面 | 附着粒子数(个/片) | 消泡性 | ||
实施例 | 171819202122 | C12H25ph(SO3H)Oph(SO3H)C12H25ph(SO3H)Oph(SO3H)C12H25ph(SO3H)Oph(SO3H)C12H25ph(SO3H)Oph(SO3H)C12H25ph(SO3H)Oph(SO3H)C12H25ph(SO3H)Oph(SO3H) | 15101510 | 硅硅硅热氧化膜热氧化膜热氧化膜 | 100357000 | ○○○○○○ |
比较例 | 26272829 | 未加入未加入C12H25N(CH2CH2OH)2C12H25N(CH2CH2OH)2 | 00300300 | 硅热氧化膜硅热氧化膜 | 2101969002000 | --×× |
本发明的晶片处理液是针对半导体元件的微型化,高集成化的发展,在洗净或采用湿法蚀刻时极为有效。本发明的处理液即使在高浓度的氢氟酸中含有特定的表面活性剂,也不发生起泡问题,溶解性优良,且保管及运输效率高。使用时即使稀释成低浓度时也能发挥极好的防止因晶片表面微粒子所致的污染。此外,使用本发明的处理液,减少了附着晶片表面的微粒子数,所以可有效地利用。
Claims (15)
1.晶片处理液,是在20~60wt%的氢氟酸中,是将以下至少一种以0.1~1000ppm溶解,剩余部分为水,合计100wt%所组成的,CnH2n+1ph(SO3M)Oph(SO3M),其中ph为亚苯基,n为5~20,M表示氢或盐;CnH2n+1phO(CH2CH2O)mSO3M,其中ph为亚苯基,n为5~20,m为0~20,M表示氢或盐;和CnH2n+1O(CH2CH2O)mSO3M,其中n为5~20,m为0~20,M表示氢或盐。
2.晶片处理液的制造方法,是将权利要求1中的处理液用水稀释,在0.1~5wt%的氢氟酸中,将以下至少一种溶解0.1~100ppm,剩余部分为水,合计100wt%所组成的,CnH2n+1ph(SO3M)Oph(SO3M),其中ph为亚苯基,n为5~20,M表示氢或盐;CnH2n+1phO(CH2CH2O)mSO3M,其中ph为亚苯基,n为5~20,m为0~20,M表示氢或盐;和CnH2n+1O(CH2CH2O)mSO3M,其中n为5~20,m为0~20,M表示氢或盐。
3.晶片处理液的制造方法,是在权利要求1的处理液中添加水,H2O2,在0.1~10wt%的氢氟酸,0.01~30wt%的H2O2中,将以下至少一种溶解0.1~100ppm,剩余部分为水,合计100wt%所组成的,CnH2n+1ph(SO3M)Oph(SO3M),其中ph为亚苯基,n为5~20,M表示氢或盐;CnH2n+1phO(CH2CH2O)mSO3M,其中ph为亚苯基,n为5~20,m为0~20,M表示氢或盐;和CnH2n+1O(CH2CH2O)mSO3M,其中n为5~20,m为0~20,M表示氢或盐。
4.晶片处理液的制造方法,是在权利要求1的处理液中添加水,HNO3,在0.1~50wt%的氢氟酸,0.1~70wt%的HNO3中,将以下至少一种溶解0.1~100ppm,剩余部分为水,合计100wt%所组成的,CnH2n+1ph(SO3M)Oph(SO3M),其中ph为亚苯基,n为5~20,M表示氢或盐;CnH2n+1phO(CH2CH2O)mSO3M,其中ph为亚苯基,n为5~20,m为0~20,M表示氢或盐;和CnH2n+1O(CH2CH2O)mSO3M,其中n为5~20,m为0~20,M表示氢或盐。
5.晶片处理液的制造方法,是在权利要求4的处理液中,进一步添加CH3COOH至0.1~50wt%而组成的。
6.晶片处理液的制造方法,是在权利要求1的处理液中,添加水,NH4F,在0.1~10wt%的氢氟酸,1~40wt%的NH4F中,将以下至少一种以0.1~100ppm溶解,剩余部分为水,合计100wt%所组成的,CnH2n+1ph(SO3M)Oph(SO3M),其中ph为亚苯基,n为5~20,M表示氢或盐;CnH2n+1phO(CH2CH2O)mSO3M,其中ph为亚苯基,n为5~20,m为0~20,M表示氢或盐;和CnH2n+1O(CH2CH2O)mSO3M(n为5~20,m为0~20,M表示氢或盐。
7.晶片处理液,是在0.1~5wt%的氢氟酸中,将以下至少一种以0.1~1000ppm溶解,剩余部分为水,合计100wt%所组成的,CnH2n+1ph(SO3M)Oph(SO3M),其中ph为亚苯基,n为5~20,M表示氢或盐);CnH2n+1phO(CH2CH2O)mSO3M,其中ph为亚苯基,n为5~20,m为0~20,M表示氢或盐。
8.晶片处理液,是在0.1~10wt%的氢氟酸,0.01~30wt%的H2O2中,将以下至少一种表面活性剂溶解0.1~1000ppm,剩余部分为水,合计100wt%所组成的,CnH2n+1ph(SO3M)Oph(SO3M),其中ph为亚苯基,n为5~20,M表示氢或盐;CnH2n+1phO(CH2CH2O)mSO3M,其中ph为亚苯基,n为5~20,m为0~20,M表示氢或盐。
9.晶片处理液,是在0.1~50wt%的氢氟酸,0.1~70wt%的HNO3中,将以下表面活性剂中的至少一种溶解0.1~1000ppm,剩余部分为水,合计100wt%所组成的,CnH2n+1ph(SO3M)Oph(SO3M),其中ph为亚苯基,n为5~20,M表示氢或盐;CnH2n+1phO(CH2CH2O)mSO3M,其中ph为亚苯基,n为5~20,m为0~20,M表示氢或盐。
10.根据权利要求9的晶片处理液,进一步含有0.1~50wt%的CH3COOH。
11.晶片处理液,是在0.1~10wt%的氢氟酸,1~40wt%的NH4F中,将以下表面活性剂中的至少一种溶解0.1~1000ppm,剩余部分为水,合计100wt%所组成的,CnH2n+1ph(SO3M)Oph(SO3M),其中ph为亚苯基,n为5~20,M表示氢或盐;CnH2n+1phO(CH2CH2O)mSO3M,其中ph为亚苯基,n为5~20,m为0~20,M表示氢或盐。
12.晶片处理液,是在0.1~36wt%的HCl,0.1~30wt%的H2O2中,将以下表面活性剂中的至少一种溶解0.1~1000ppm,剩余部分为水,合计100wt%所组成的,CnH2n+1ph(SO3M)Oph(SO3M),其中ph为亚苯基,n为5~20,M表示氢或盐;CnH2n+1phO(CH2CH2O)mSO3M,其中ph为亚苯基,n为5~20,m为0~20,M表示氢或盐。
13.晶片处理液,是在1~90wt%的H3PO4中,将以下表面活性剂中的至少一种溶解0.1~1000ppm,剩余部分为水,合计100wt%所组成的,CnH2n+1ph(SO3M)Oph(SO3M),其中ph为亚苯基,n为5~20,M表示氢或盐;CnH2n+1phO(CH2CH2O)mSO3M,其中ph为亚苯基,n为5~20,m为0~20,M表示氢或盐。
14.晶片处理液,是在0.01~10wt%的以式[(R1)(R2)(R3)(R4)N]+OH-表示的季胺碱和0.01~30wt%的H2O2中,将以下表面活性剂中的至少一种溶解0.1~1000ppm,剩余部分为水,合计100wt%所组成的,CnH2n+1ph(SO3M)Oph(SO3M),其中ph为亚苯基,n为5~20,M表示氢或盐;CnH2n+1phO(CH2CH2O)mSO3M,其中ph为亚苯基,n为5~20,m为0~20,M表示氢或盐;和CnH2n+1O(CH2CH2O)mSO3M(n为5~20,m为0~20,M表示氢或盐;式[(R1)(R2)(R3)(R4)N]+OH-中,R1,R2,R3,R4分别表示可具有羟基,碳数为1~6的烷基。
15.晶片处理液,是在H2O2,HNO3,CH3COOH,NH4F,HCl和以式[(R1)(R2)(R3)(R4)N]+OH-表示的季胺碱中的至少一种中,将以下表面活性剂中的至少一种溶解0.1~1000ppm,剩余部分为水,合计100wt%所组成的,CnH2n+1ph(SO3M)Oph(SO3M),其中ph为亚苯基,n为5~20,M表示氢或盐;CnH2n+1phO(CH2CH2O)mSO3M,其中ph为亚苯基,n为5~20,m为0~20,M表示氢或盐;式[(R1)(R2)(R3)(R4)N]+OH-中,R1,R2,R3,R4分别表示可具有羟基,碳数为1~6的烷基。
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EP (1) | EP0871209A4 (zh) |
JP (1) | JP3972133B2 (zh) |
KR (1) | KR100269013B1 (zh) |
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Also Published As
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EP0871209A4 (en) | 2006-02-08 |
EP0871209A1 (en) | 1998-10-14 |
CN1202274A (zh) | 1998-12-16 |
WO1997018582A1 (fr) | 1997-05-22 |
KR100269013B1 (ko) | 2000-11-01 |
KR19990063592A (ko) | 1999-07-26 |
JP3972133B2 (ja) | 2007-09-05 |
US6159865A (en) | 2000-12-12 |
US6068788A (en) | 2000-05-30 |
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