JP6100664B2 - Hydrofluoric acid aqueous solution purification method, substrate processing method and substrate processing apparatus - Google Patents
Hydrofluoric acid aqueous solution purification method, substrate processing method and substrate processing apparatus Download PDFInfo
- Publication number
- JP6100664B2 JP6100664B2 JP2013206447A JP2013206447A JP6100664B2 JP 6100664 B2 JP6100664 B2 JP 6100664B2 JP 2013206447 A JP2013206447 A JP 2013206447A JP 2013206447 A JP2013206447 A JP 2013206447A JP 6100664 B2 JP6100664 B2 JP 6100664B2
- Authority
- JP
- Japan
- Prior art keywords
- hydrofluoric acid
- substrate
- hydrogen
- substrate processing
- platinum group
- 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
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 title claims description 186
- 239000000758 substrate Substances 0.000 title claims description 101
- 238000012545 processing Methods 0.000 title claims description 90
- 238000000034 method Methods 0.000 title claims description 45
- 238000003672 processing method Methods 0.000 title claims description 12
- 238000000746 purification Methods 0.000 title claims description 9
- 239000007864 aqueous solution Substances 0.000 title description 6
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims description 91
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical group [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims description 74
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 70
- 229910052751 metal Inorganic materials 0.000 claims description 62
- 239000002184 metal Substances 0.000 claims description 62
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 52
- 239000001301 oxygen Substances 0.000 claims description 52
- 229910052760 oxygen Inorganic materials 0.000 claims description 52
- 229910021642 ultra pure water Inorganic materials 0.000 claims description 51
- 239000012498 ultrapure water Substances 0.000 claims description 51
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 47
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical group [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims description 47
- 229910052739 hydrogen Inorganic materials 0.000 claims description 45
- 239000001257 hydrogen Substances 0.000 claims description 45
- 239000003054 catalyst Substances 0.000 claims description 44
- 239000000243 solution Substances 0.000 claims description 44
- 239000007788 liquid Substances 0.000 claims description 38
- 238000003860 storage Methods 0.000 claims description 31
- 239000007800 oxidant agent Substances 0.000 claims description 26
- 229910052763 palladium Inorganic materials 0.000 claims description 24
- 150000001450 anions Chemical class 0.000 claims description 22
- 230000001590 oxidative effect Effects 0.000 claims description 20
- 239000011261 inert gas Substances 0.000 claims description 11
- 238000005984 hydrogenation reaction Methods 0.000 claims description 10
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 claims description 7
- 229910001882 dioxygen Inorganic materials 0.000 claims description 7
- 239000011259 mixed solution Substances 0.000 claims description 3
- 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 claims description 2
- 150000002500 ions Chemical class 0.000 description 59
- 239000011148 porous material Substances 0.000 description 41
- 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 31
- 238000005342 ion exchange Methods 0.000 description 22
- 238000004140 cleaning Methods 0.000 description 21
- 238000004519 manufacturing process Methods 0.000 description 19
- 239000002245 particle Substances 0.000 description 15
- 230000002829 reductive effect Effects 0.000 description 15
- 239000010949 copper Substances 0.000 description 14
- NWUYHJFMYQTDRP-UHFFFAOYSA-N 1,2-bis(ethenyl)benzene;1-ethenyl-2-ethylbenzene;styrene Chemical compound C=CC1=CC=CC=C1.CCC1=CC=CC=C1C=C.C=CC1=CC=CC=C1C=C NWUYHJFMYQTDRP-UHFFFAOYSA-N 0.000 description 13
- 239000004065 semiconductor Substances 0.000 description 13
- 235000012431 wafers Nutrition 0.000 description 13
- 229910052802 copper Inorganic materials 0.000 description 12
- 230000008569 process Effects 0.000 description 12
- 229920002554 vinyl polymer Polymers 0.000 description 12
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 11
- 229920000642 polymer Polymers 0.000 description 11
- 239000000126 substance Substances 0.000 description 10
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 9
- 238000006243 chemical reaction Methods 0.000 description 9
- 238000009826 distribution Methods 0.000 description 9
- 239000002923 metal particle Substances 0.000 description 9
- -1 platinum group metals Chemical class 0.000 description 9
- 239000011550 stock solution Substances 0.000 description 9
- 238000005260 corrosion Methods 0.000 description 8
- 230000007797 corrosion Effects 0.000 description 8
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 8
- 229910052753 mercury Inorganic materials 0.000 description 8
- 239000003729 cation exchange resin Substances 0.000 description 7
- 239000010419 fine particle Substances 0.000 description 7
- 239000003456 ion exchange resin Substances 0.000 description 7
- 229920003303 ion-exchange polymer Polymers 0.000 description 7
- 239000000178 monomer Substances 0.000 description 7
- 229910052721 tungsten Inorganic materials 0.000 description 7
- 230000003197 catalytic effect Effects 0.000 description 6
- 239000000203 mixture Substances 0.000 description 6
- 238000012360 testing method Methods 0.000 description 6
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 description 6
- 239000010937 tungsten Substances 0.000 description 6
- 238000005349 anion exchange Methods 0.000 description 5
- 238000010586 diagram Methods 0.000 description 5
- 239000012528 membrane Substances 0.000 description 5
- MYRTYDVEIRVNKP-UHFFFAOYSA-N 1,2-Divinylbenzene Chemical compound C=CC1=CC=CC=C1C=C MYRTYDVEIRVNKP-UHFFFAOYSA-N 0.000 description 4
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 4
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 4
- 239000002253 acid Substances 0.000 description 4
- 125000003118 aryl group Chemical group 0.000 description 4
- 238000005341 cation exchange Methods 0.000 description 4
- 239000003431 cross linking reagent Substances 0.000 description 4
- MWKFXSUHUHTGQN-UHFFFAOYSA-N decan-1-ol Chemical compound CCCCCCCCCCO MWKFXSUHUHTGQN-UHFFFAOYSA-N 0.000 description 4
- 238000010828 elution Methods 0.000 description 4
- 238000011156 evaluation Methods 0.000 description 4
- 239000011810 insulating material Substances 0.000 description 4
- 150000002739 metals Chemical class 0.000 description 4
- 125000001453 quaternary ammonium group Chemical group 0.000 description 4
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 3
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- 150000001768 cations Chemical class 0.000 description 3
- 230000003749 cleanliness Effects 0.000 description 3
- 229920001577 copolymer Polymers 0.000 description 3
- 229910001873 dinitrogen Inorganic materials 0.000 description 3
- 238000004453 electron probe microanalysis Methods 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 238000005259 measurement Methods 0.000 description 3
- 229910021645 metal ion Inorganic materials 0.000 description 3
- 230000003647 oxidation Effects 0.000 description 3
- 238000007254 oxidation reaction Methods 0.000 description 3
- 238000005498 polishing Methods 0.000 description 3
- 238000006116 polymerization reaction Methods 0.000 description 3
- 230000009467 reduction Effects 0.000 description 3
- 239000000523 sample Substances 0.000 description 3
- 238000001878 scanning electron micrograph Methods 0.000 description 3
- 229910052710 silicon Inorganic materials 0.000 description 3
- 239000010703 silicon Substances 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- GETQZCLCWQTVFV-UHFFFAOYSA-N trimethylamine Chemical group CN(C)C GETQZCLCWQTVFV-UHFFFAOYSA-N 0.000 description 3
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 3
- 239000007762 w/o emulsion Substances 0.000 description 3
- CHRJZRDFSQHIFI-UHFFFAOYSA-N 1,2-bis(ethenyl)benzene;styrene Chemical compound C=CC1=CC=CC=C1.C=CC1=CC=CC=C1C=C CHRJZRDFSQHIFI-UHFFFAOYSA-N 0.000 description 2
- 239000005968 1-Decanol Substances 0.000 description 2
- OZAIFHULBGXAKX-UHFFFAOYSA-N 2-(2-cyanopropan-2-yldiazenyl)-2-methylpropanenitrile Chemical compound N#CC(C)(C)N=NC(C)(C)C#N OZAIFHULBGXAKX-UHFFFAOYSA-N 0.000 description 2
- WYGWHHGCAGTUCH-UHFFFAOYSA-N 2-[(2-cyano-4-methylpentan-2-yl)diazenyl]-2,4-dimethylpentanenitrile Chemical compound CC(C)CC(C)(C#N)N=NC(C)(C#N)CC(C)C WYGWHHGCAGTUCH-UHFFFAOYSA-N 0.000 description 2
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 2
- JPVYNHNXODAKFH-UHFFFAOYSA-N Cu2+ Chemical compound [Cu+2] JPVYNHNXODAKFH-UHFFFAOYSA-N 0.000 description 2
- OAKJQQAXSVQMHS-UHFFFAOYSA-N Hydrazine Chemical compound NN OAKJQQAXSVQMHS-UHFFFAOYSA-N 0.000 description 2
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 description 2
- UFWIBTONFRDIAS-UHFFFAOYSA-N Naphthalene Chemical compound C1=CC=CC2=CC=CC=C21 UFWIBTONFRDIAS-UHFFFAOYSA-N 0.000 description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 238000004220 aggregation Methods 0.000 description 2
- 230000002776 aggregation Effects 0.000 description 2
- 230000005540 biological transmission Effects 0.000 description 2
- 239000012295 chemical reaction liquid Substances 0.000 description 2
- 239000003638 chemical reducing agent Substances 0.000 description 2
- 229910001430 chromium ion Inorganic materials 0.000 description 2
- 229910001429 cobalt ion Inorganic materials 0.000 description 2
- XLJKHNWPARRRJB-UHFFFAOYSA-N cobalt(2+) Chemical compound [Co+2] XLJKHNWPARRRJB-UHFFFAOYSA-N 0.000 description 2
- 229910001431 copper ion Inorganic materials 0.000 description 2
- 238000004132 cross linking Methods 0.000 description 2
- 230000007423 decrease Effects 0.000 description 2
- 230000003247 decreasing effect Effects 0.000 description 2
- 238000007865 diluting Methods 0.000 description 2
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N diphenyl Chemical compound C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000005530 etching Methods 0.000 description 2
- 230000002209 hydrophobic effect Effects 0.000 description 2
- 238000007654 immersion Methods 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- 229910052742 iron Inorganic materials 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 229910052750 molybdenum Inorganic materials 0.000 description 2
- 239000011733 molybdenum Substances 0.000 description 2
- 229910001453 nickel ion Inorganic materials 0.000 description 2
- 229920000620 organic polymer Polymers 0.000 description 2
- PIBWKRNGBLPSSY-UHFFFAOYSA-L palladium(II) chloride Chemical compound Cl[Pd]Cl PIBWKRNGBLPSSY-UHFFFAOYSA-L 0.000 description 2
- 229910052697 platinum Inorganic materials 0.000 description 2
- ZORQXIQZAOLNGE-UHFFFAOYSA-N 1,1-difluorocyclohexane Chemical compound FC1(F)CCCCC1 ZORQXIQZAOLNGE-UHFFFAOYSA-N 0.000 description 1
- KEQGZUUPPQEDPF-UHFFFAOYSA-N 1,3-dichloro-5,5-dimethylimidazolidine-2,4-dione Chemical compound CC1(C)N(Cl)C(=O)N(Cl)C1=O KEQGZUUPPQEDPF-UHFFFAOYSA-N 0.000 description 1
- HOBGCONPBCCQHM-UHFFFAOYSA-N 2-(methylamino)ethane-1,1-diol Chemical group CNCC(O)O HOBGCONPBCCQHM-UHFFFAOYSA-N 0.000 description 1
- PYSGFFTXMUWEOT-UHFFFAOYSA-N 3-(dimethylamino)propan-1-ol Chemical group CN(C)CCCO PYSGFFTXMUWEOT-UHFFFAOYSA-N 0.000 description 1
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 description 1
- UEEJHVSXFDXPFK-UHFFFAOYSA-N N-dimethylaminoethanol Chemical group CN(C)CCO UEEJHVSXFDXPFK-UHFFFAOYSA-N 0.000 description 1
- 229910001252 Pd alloy Inorganic materials 0.000 description 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical group OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 1
- 239000004793 Polystyrene Substances 0.000 description 1
- 229910001260 Pt alloy Inorganic materials 0.000 description 1
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- 229910000577 Silicon-germanium Inorganic materials 0.000 description 1
- 238000000944 Soxhlet extraction Methods 0.000 description 1
- 238000003917 TEM image Methods 0.000 description 1
- 229910021627 Tin(IV) chloride Inorganic materials 0.000 description 1
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical group CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 1
- LEVVHYCKPQWKOP-UHFFFAOYSA-N [Si].[Ge] Chemical compound [Si].[Ge] LEVVHYCKPQWKOP-UHFFFAOYSA-N 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 239000003957 anion exchange resin Substances 0.000 description 1
- 239000012298 atmosphere Substances 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- KCXMKQUNVWSEMD-UHFFFAOYSA-N benzyl chloride Chemical compound ClCC1=CC=CC=C1 KCXMKQUNVWSEMD-UHFFFAOYSA-N 0.000 description 1
- 229940073608 benzyl chloride Drugs 0.000 description 1
- 235000010290 biphenyl Nutrition 0.000 description 1
- 239000004305 biphenyl Substances 0.000 description 1
- 125000002843 carboxylic acid group Chemical group 0.000 description 1
- 239000000969 carrier Substances 0.000 description 1
- 229940023913 cation exchange resins Drugs 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- 125000004218 chloromethyl group Chemical group [H]C([H])(Cl)* 0.000 description 1
- XTHPWXDJESJLNJ-UHFFFAOYSA-N chlorosulfonic acid Substances OS(Cl)(=O)=O XTHPWXDJESJLNJ-UHFFFAOYSA-N 0.000 description 1
- 230000015271 coagulation Effects 0.000 description 1
- 238000005345 coagulation Methods 0.000 description 1
- 238000004891 communication Methods 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 238000007872 degassing Methods 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- NKDDWNXOKDWJAK-UHFFFAOYSA-N dimethoxymethane Chemical compound COCOC NKDDWNXOKDWJAK-UHFFFAOYSA-N 0.000 description 1
- 238000004993 emission spectroscopy Methods 0.000 description 1
- 239000000839 emulsion Substances 0.000 description 1
- 125000004185 ester group Chemical group 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 239000012510 hollow fiber Substances 0.000 description 1
- 229910000040 hydrogen fluoride Inorganic materials 0.000 description 1
- NBZBKCUXIYYUSX-UHFFFAOYSA-N iminodiacetic acid Chemical group OC(=O)CNCC(O)=O NBZBKCUXIYYUSX-UHFFFAOYSA-N 0.000 description 1
- 230000010354 integration Effects 0.000 description 1
- 229910052741 iridium Inorganic materials 0.000 description 1
- GKOZUEZYRPOHIO-UHFFFAOYSA-N iridium atom Chemical compound [Ir] GKOZUEZYRPOHIO-UHFFFAOYSA-N 0.000 description 1
- 230000001678 irradiating effect Effects 0.000 description 1
- 230000000670 limiting effect Effects 0.000 description 1
- 239000004973 liquid crystal related substance Substances 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 239000012046 mixed solvent Substances 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 125000000962 organic group Chemical group 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 229910052762 osmium Inorganic materials 0.000 description 1
- SYQBFIAQOQZEGI-UHFFFAOYSA-N osmium atom Chemical compound [Os] SYQBFIAQOQZEGI-UHFFFAOYSA-N 0.000 description 1
- YJVFFLUZDVXJQI-UHFFFAOYSA-L palladium(ii) acetate Chemical compound [Pd+2].CC([O-])=O.CC([O-])=O YJVFFLUZDVXJQI-UHFFFAOYSA-L 0.000 description 1
- 238000005502 peroxidation Methods 0.000 description 1
- 125000005496 phosphonium group Chemical group 0.000 description 1
- 229920003251 poly(α-methylstyrene) Polymers 0.000 description 1
- 239000002861 polymer material Substances 0.000 description 1
- 239000003505 polymerization initiator Substances 0.000 description 1
- 230000000379 polymerizing effect Effects 0.000 description 1
- 229920002223 polystyrene Polymers 0.000 description 1
- 229920002102 polyvinyl toluene Polymers 0.000 description 1
- 238000002459 porosimetry Methods 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 238000007670 refining Methods 0.000 description 1
- 239000003870 refractory metal Substances 0.000 description 1
- 230000001172 regenerating effect Effects 0.000 description 1
- 238000001223 reverse osmosis Methods 0.000 description 1
- 229910052703 rhodium Inorganic materials 0.000 description 1
- 239000010948 rhodium Substances 0.000 description 1
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 description 1
- 229910052707 ruthenium Inorganic materials 0.000 description 1
- 238000009287 sand filtration Methods 0.000 description 1
- 238000007789 sealing Methods 0.000 description 1
- 238000004062 sedimentation Methods 0.000 description 1
- 229910052814 silicon oxide Inorganic materials 0.000 description 1
- 229940035049 sorbitan monooleate Drugs 0.000 description 1
- 239000001593 sorbitan monooleate Substances 0.000 description 1
- 235000011069 sorbitan monooleate Nutrition 0.000 description 1
- 238000004544 sputter deposition Methods 0.000 description 1
- 230000003068 static effect Effects 0.000 description 1
- 125000000542 sulfonic acid group Chemical group 0.000 description 1
- RWSOTUBLDIXVET-UHFFFAOYSA-O sulfonium group Chemical group [SH3+] RWSOTUBLDIXVET-UHFFFAOYSA-O 0.000 description 1
- 230000001629 suppression Effects 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 230000008961 swelling Effects 0.000 description 1
- HPGGPRDJHPYFRM-UHFFFAOYSA-J tin(iv) chloride Chemical compound Cl[Sn](Cl)(Cl)Cl HPGGPRDJHPYFRM-UHFFFAOYSA-J 0.000 description 1
- IMFACGCPASFAPR-UHFFFAOYSA-N tributylamine Chemical group CCCCN(CCCC)CCCC IMFACGCPASFAPR-UHFFFAOYSA-N 0.000 description 1
- 238000000108 ultra-filtration Methods 0.000 description 1
Images
Landscapes
- Treatment Of Water By Oxidation Or Reduction (AREA)
- Catalysts (AREA)
- Weting (AREA)
- Cleaning Or Drying Semiconductors (AREA)
Description
本発明は、基板の処理に使用されるフッ化水素酸水溶液の精製方法、基板処理方法および基板処理装置に関する。特に、半導体基板の枚葉式洗浄・浸漬式洗浄に用いられるフッ化水素酸水溶液の精製方法、および、その精製されたフッ化水素酸水溶液を用いた基板処理方法に関する。処理対象となる基板には、たとえば、半導体ウエハ、液晶表示装置用基板、プラズマディスプレイ用基板、電界放出ディスプレイ用基板、光ディスク用基板、磁気ディスク用基板、光磁気ディスク用基板、フォトマスク用基板、セラミック基板などが含まれる。 The present invention relates to a method for purifying a hydrofluoric acid aqueous solution used for processing a substrate, a substrate processing method, and a substrate processing apparatus. In particular, the present invention relates to a method for purifying a hydrofluoric acid aqueous solution used for single-wafer cleaning and immersion cleaning of a semiconductor substrate, and a substrate processing method using the purified hydrofluoric acid aqueous solution. Examples of substrates to be processed include semiconductor wafers, liquid crystal display substrates, plasma display substrates, field emission display substrates, optical disk substrates, magnetic disk substrates, magneto-optical disk substrates, photomask substrates, A ceramic substrate is included.
半導体集積回路素子の高集積化および高速度化は、市場の要求である。この要求に応えるために、従来から用いられてきたアルミニウム配線に代えて、より低抵抗の銅配線が用いられるようになってきた。銅配線を、低誘電率絶縁膜（いわゆるＬｏｗ−ｋ膜。比誘電率が酸化シリコンよりも小さな材料からなる絶縁膜をいう。）と組み合わせて多層配線を形成すれば、極めて高速で動作する集積回路素子を実現できる。 High integration and high speed of semiconductor integrated circuit elements are market demands. In order to meet this demand, lower resistance copper wiring has been used in place of the conventionally used aluminum wiring. If a multilayer wiring is formed by combining a copper wiring with a low dielectric constant insulating film (a so-called low-k film; an insulating film made of a material having a relative dielectric constant smaller than that of silicon oxide), an integrated circuit that operates at a very high speed. A circuit element can be realized.
このような集積回路素子の製造工程では、ウエハや基板等の被処理体の表面に付着している微粒子、有機物、金属、自然酸化膜等の除去を目的とした洗浄を行い、高度な清浄度を達成、維持することは製品の品質保持や歩留まり向上にとって重要である。この洗浄は、例えば、硫酸・過酸化水素水混合溶液、フッ化水素酸溶液等の薬液を用いて行われ、該洗浄後に超純水を用いたすすぎが行われる。また、近年では、半導体デバイスの微細化、材料の多様化、プロセスの複雑化により、洗浄回数が多くなっている。例えば、上記多層配線の形成では、基板上に第１の配線層となる金属配線を形成し該金属配線を絶縁材で埋め、該金属配線を覆った絶縁材料の表面をＣＭＰ研磨して平坦にし、次いで、該表面上に第２の配線層となる金属配線を形成し該金属配線を絶縁材で埋め、該絶縁材料の表面をＣＭＰ研磨して平坦にする、といった手順が繰り返される。こうしたプロセスにおいては研磨工程終了の度に基板の洗浄が行われる。 In the manufacturing process of such integrated circuit elements, cleaning is performed for the purpose of removing fine particles, organic substances, metals, natural oxide films, etc. adhering to the surface of an object to be processed such as a wafer or a substrate, and a high degree of cleanliness is achieved. Achieving and maintaining this is important for maintaining product quality and improving yield. This cleaning is performed, for example, using a chemical solution such as a sulfuric acid / hydrogen peroxide solution mixed solution or a hydrofluoric acid solution, and rinsing with ultrapure water is performed after the cleaning. In recent years, the number of cleanings has increased due to miniaturization of semiconductor devices, diversification of materials, and complexity of processes. For example, in the formation of the multilayer wiring, a metal wiring serving as a first wiring layer is formed on a substrate, the metal wiring is filled with an insulating material, and the surface of the insulating material covering the metal wiring is planarized by CMP. Then, a procedure is repeated in which a metal wiring serving as a second wiring layer is formed on the surface, the metal wiring is filled with an insulating material, and the surface of the insulating material is flattened by CMP. In such a process, the substrate is cleaned every time the polishing step is completed.
超純水の製造には一般に、前処理システム、一次純水システム、および二次純水システム（サブシステム）で構成される超純水製造装置が用いられている。超純水製造装置における各システムの役割は次の通りである。前処理システムは、例えば凝集沈殿や砂ろ過により、原水中に含まれる懸濁物質やコロイド物質の除去を行う工程である。一次純水システムは、例えばイオン交換樹脂や逆浸透（ＲＯ）膜等を使用して、前記前処理システムで懸濁物質等が除去された原水のイオン成分や有機成分の除去を行い、一次純水を得る工程である。サブシステムは、図１に示すように、紫外線酸化装置（ＵＶ）、膜式脱気装置（ＭＤ）、非再生型イオン交換装置（例えばカートリッジポリッシャー（ＣＰ））、膜分離装置（例えば限外ろ過装置（ＵＦ））などを連続させた通水ラインを使用して、一次純水システムで得られた一次純水の純度をさらに高めて、超純水を製造する工程である。 For the production of ultrapure water, an ultrapure water production apparatus comprising a pretreatment system, a primary pure water system, and a secondary pure water system (subsystem) is generally used. The role of each system in the ultrapure water production system is as follows. The pretreatment system is a process for removing suspended substances and colloidal substances contained in raw water by, for example, coagulation sedimentation or sand filtration. The primary pure water system uses, for example, an ion exchange resin or a reverse osmosis (RO) membrane to remove the ionic components and organic components of the raw water from which the suspended substances have been removed by the pretreatment system. This is a process for obtaining water. As shown in FIG. 1, the subsystem includes an ultraviolet oxidizer (UV), a membrane deaerator (MD), a non-regenerative ion exchanger (eg, cartridge polisher (CP)), and a membrane separator (eg, ultrafiltration). This is a process for producing ultrapure water by further increasing the purity of primary pure water obtained by the primary pure water system using a water flow line in which a device (UF)) and the like are made continuous.
このようにして得られた超純水を半導体基板の洗浄に使用する場合は、次のような種々の問題があり、それぞれの問題に対して対策方法が提案されている。 When the ultrapure water obtained in this way is used for cleaning a semiconductor substrate, there are the following various problems, and countermeasures have been proposed for each problem.
洗浄水中に含まれる溶存酸素濃度が高いと、該洗浄水によってウエハ表面に自然酸化膜が形成され、これによってゲート酸化膜の膜厚および膜質の精密制御が妨げられたり、コンタクトホール、ビア、プラグ等のコンタクト抵抗が増加したりするおそれがある。また、多層配線の形成プロセスで研磨工程後に洗浄される基板の表面には配線金属が露出する。Ｗ，Ｃｕ等の配線金属は水中に溶存する酸素により腐食を受けやすい金属のため、上記超純水での基板洗浄中に配線の膜厚が減少するおそれがある。その他には、研磨によって生じる基板表面のレジスト残渣をポリマー除去液により除去する際に、ポリマー除去液が洗浄室内の空気に触れ、このポリマー除去液中に酸素が溶け込み、酸素濃度の高いポリマー除去液が基板に供給されるという問題がある。この場合においても、ポリマー除去液中の溶存酸素により基板上の金属膜（銅膜、タングステン膜など）が酸化され、この基板から作成される集積回路素子の性能を劣化させるおそれがある。 If the concentration of dissolved oxygen contained in the cleaning water is high, a natural oxide film is formed on the wafer surface by the cleaning water, thereby preventing precise control of the film thickness and film quality of the gate oxide film, contact holes, vias, and plugs. The contact resistance such as may increase. Further, the wiring metal is exposed on the surface of the substrate that is cleaned after the polishing step in the multilayer wiring forming process. Since wiring metals such as W and Cu are metals that are easily corroded by oxygen dissolved in water, the thickness of the wiring may be reduced during the cleaning of the substrate with the ultrapure water. In addition, when the resist residue on the substrate surface caused by polishing is removed by the polymer removal liquid, the polymer removal liquid touches the air in the cleaning chamber, and oxygen dissolves in the polymer removal liquid, so that the polymer removal liquid having a high oxygen concentration. Is supplied to the substrate. Even in this case, the metal film (copper film, tungsten film, etc.) on the substrate is oxidized by the dissolved oxygen in the polymer removing solution, and there is a possibility that the performance of the integrated circuit element formed from the substrate is deteriorated.
これらの対策として、前述したサブシステムでは膜式脱気装置を用いて脱ガス処理を行い、水中に溶存するガス量を減少させているが、それだけでなく、特許文献１や特許文献２に記載されるように、脱ガスした超純水に不活性ガスや水素ガスを添加して水中の溶存酸素を低減する方法も採られている。特許文献１では洗浄される基板の表面付近の雰囲気を不活性ガスで置換する方法も採られている。 As a countermeasure against these problems, the above-described subsystem performs degassing using a membrane deaerator to reduce the amount of gas dissolved in water, but it is described in Patent Document 1 and Patent Document 2 as well. In order to reduce dissolved oxygen in water, an inert gas or hydrogen gas is added to degassed ultrapure water. Patent Document 1 also employs a method of replacing the atmosphere near the surface of the substrate to be cleaned with an inert gas.
また、前述したサブシステムでは紫外線酸化装置により水に紫外線を照射して水中の有機物を分解・除去しているため、この紫外線照射で水分子も酸化され、酸化性物質である過酸化水素が生成される。即ち、超純水は過酸化水素を含有することになる。過酸化水素を含む洗浄液を用いて、タングステン等の高融点金属を含むゲート電極を有する半導体デバイスを洗浄すると、タングステンと過酸化水素との間で化学反応が触媒的に進むため、タングステンが溶解してしまう虞がある。 In the above-mentioned subsystem, water is also decomposed and removed by irradiating water with ultraviolet rays using an ultraviolet oxidizer, so that water molecules are also oxidized by this ultraviolet irradiation, producing hydrogen peroxide, an oxidizing substance. Is done. That is, the ultrapure water contains hydrogen peroxide. When a semiconductor device having a gate electrode containing a refractory metal such as tungsten is cleaned with a cleaning solution containing hydrogen peroxide, the chemical reaction between tungsten and hydrogen peroxide proceeds catalytically, so that tungsten dissolves. There is a risk that.
水中の過酸化水素を取り除く方法としては、Ｐｄ等の白金族系金属触媒を用いて水中の過酸化水素を除去する方法が知られている。特に、特許文献３に記載されるように、モノリス状有機多孔質アニオン交換体に白金族系金属が担持されてなる触媒と、過酸化水素を含む被処理水とを接触させることで、被処理水から過酸化水素を高効率で分解除去する方法もある。また特許文献４には、酸素溶存水に水素を溶解した後、その水素溶解水を、モノリス状有機多孔質アニオン交換体に白金族系金属が担持されてなる触媒と接触させる方法が開示されており、特許文献４記載の方法では、溶存過酸化水素と酸素とが高効率に除去された被処理水を製造することができる。 As a method of removing hydrogen peroxide in water, a method of removing hydrogen peroxide in water using a platinum group metal catalyst such as Pd is known. In particular, as described in Patent Document 3, a catalyst in which a platinum group metal is supported on a monolithic organic porous anion exchanger and a water to be treated containing hydrogen peroxide are brought into contact with each other. There is also a method for efficiently decomposing and removing hydrogen peroxide from water. Patent Document 4 discloses a method in which hydrogen is dissolved in oxygen-dissolved water and then the hydrogen-dissolved water is contacted with a catalyst in which a platinum group metal is supported on a monolithic organic porous anion exchanger. In the method described in Patent Document 4, water to be treated from which dissolved hydrogen peroxide and oxygen are removed with high efficiency can be produced.
半導体装置には、ますます微細化、高機能化が要求されており、様々な加工プロセスのなかで半導体シリコン基板の洗浄の重要性が非常に高くなっている。このため、酸化膜除去だけでなく、微粒子付着の抑制、ウエハ表面の平坦性などといった様々な清浄性や機能性を発揮する薬液として、フッ化水素酸がよく用いられている。また、極めて高いクリーン度が要求される装置部材の洗浄にフッ化水素酸が用いられることもある。フッ化水素酸（HF）は、シリコンやシリコン−ゲルマニウムなどの基板から表面酸化物を除去し、表面を疎水性状態にする特質を持つからである。 Semiconductor devices are increasingly required to be miniaturized and highly functional, and the importance of cleaning a semiconductor silicon substrate has become very high in various processing processes. For this reason, hydrofluoric acid is often used as a chemical solution that exhibits not only oxide film removal but also various cleanliness and functionality such as suppression of particulate adhesion and flatness of the wafer surface. Also, hydrofluoric acid may be used for cleaning apparatus members that require extremely high cleanliness. This is because hydrofluoric acid (HF) has the property of removing surface oxides from a substrate such as silicon or silicon-germanium to make the surface hydrophobic.
一般にフッ化水素酸は原液のまま使用されず、半導体基板の洗浄薬液としては、フッ化水素酸を超純水で希釈した希フッ酸（DHF）が用いられている。当該超純水は上述した超純水製造装置で製造され、超純水中の酸素または過酸化水素は上記特許文献１〜４等に記載の技術で除去もしくは低減しえる。 In general, hydrofluoric acid is not used as a stock solution, and dilute hydrofluoric acid (DHF) obtained by diluting hydrofluoric acid with ultrapure water is used as a cleaning chemical for a semiconductor substrate. The ultrapure water is produced by the above-described ultrapure water production apparatus, and oxygen or hydrogen peroxide in the ultrapure water can be removed or reduced by the techniques described in Patent Documents 1 to 4 and the like.
しかしながら、薬液タンク内のフッ化水素酸を被処理体へ供給する過程では、現在のところ、当該フッ化水素酸中の酸素濃度や過酸化水素濃度は管理されていない。したがって、半導体デバイスの高度化、微細化、高密度化が進むにつれて、フッ化水素酸中の溶存酸素や溶存過酸化水素が、希フッ酸を用いた基板処理時に予期せぬ酸化や腐食（例えば基板表面に露出したＣｕ、タングステン、モリブデン等の溶出）を起こし、歩留りを低下させる虞がある。したがって、フッ化水素酸中の溶存酸素濃度や過酸化水素濃度を出来るだけ低減したい要求が生じている。 However, in the process of supplying hydrofluoric acid in the chemical tank to the object to be processed, the oxygen concentration and hydrogen peroxide concentration in the hydrofluoric acid are not managed at present. Therefore, as semiconductor devices become more sophisticated, miniaturized, and higher in density, dissolved oxygen and dissolved hydrogen peroxide in hydrofluoric acid are subject to unexpected oxidation and corrosion during substrate processing using dilute hydrofluoric acid (for example, Elution of Cu, tungsten, molybdenum, etc. exposed on the substrate surface) may occur, and the yield may be reduced. Therefore, there is a demand for reducing the dissolved oxygen concentration and hydrogen peroxide concentration in hydrofluoric acid as much as possible.
そこで本発明は、上述した懸念に鑑みて、溶存酸素および溶存過酸化水素が所定濃度以下に抑制されたフッ化水素酸溶液の精製方法を提供することを目的とする。 In view of the above-described concerns, an object of the present invention is to provide a method for purifying a hydrofluoric acid solution in which dissolved oxygen and dissolved hydrogen peroxide are suppressed to a predetermined concentration or less.
本発明の一態様は、フッ化水素酸溶液の精製方法に係る。この精製方法は、少なくともフッ化水素酸を含む溶液に水素を添加し、白金族系金属触媒に通液することにより、溶存酸素濃度が２μｇ／Ｌ以下かつ過酸化水素濃度が２μｇ／Ｌ以下の処理液を得ることを含む。 One embodiment of the present invention relates to a method for purifying a hydrofluoric acid solution. In this purification method, hydrogen is added to a solution containing at least hydrofluoric acid and passed through a platinum group metal catalyst, so that the dissolved oxygen concentration is 2 μg / L or less and the hydrogen peroxide concentration is 2 μg / L or less. Including obtaining a treatment solution.
本発明の他の態様は、基板処理装置の処理室内に基板を配置し、該基板を処理液で処理する基板処理方法に係る。 Another aspect of the present invention relates to a substrate processing method in which a substrate is disposed in a processing chamber of a substrate processing apparatus, and the substrate is processed with a processing liquid.
この基板処理方法は、基板処理装置に水素添加装置および白金族系金属触媒を設置し、
少なくともフッ化水素酸を含む溶液に水素添加装置から水素を添加し、
該水素が添加された溶液を白金族系金属触媒に通水して得た、溶存酸素濃度が２μｇ／Ｌ以下、過酸化水素濃度が２μｇ／Ｌ以下の処理液によって、基板を処理することを含む。
In this substrate processing method, a hydrogenation apparatus and a platinum group metal catalyst are installed in a substrate processing apparatus,
Add hydrogen from a hydrogenation device to a solution containing at least hydrofluoric acid,
Treating the substrate with a treatment solution obtained by passing the hydrogen-added solution through a platinum group metal catalyst and having a dissolved oxygen concentration of 2 μg / L or less and a hydrogen peroxide concentration of 2 μg / L or less. Including.
このような各種の態様は、溶存酸素濃度が２μｇ／Ｌ以下、過酸化水素濃度が２μｇ／Ｌ以下に精製されたフッ化水素酸を含む処理液によって基板を処理するので、被処理基板の表面に露出した酸化や腐食（例えば基板表面に露出したＣｕ、タングステン、モリブデン等の溶出）を従来のＨＦ処理に比べて一層抑制することができる。 In such various aspects, the substrate is treated with a treatment liquid containing hydrofluoric acid purified to a dissolved oxygen concentration of 2 μg / L or less and a hydrogen peroxide concentration of 2 μg / L or less. Oxidation and corrosion exposed to (eg, elution of Cu, tungsten, molybdenum, etc. exposed on the substrate surface) can be further suppressed as compared with the conventional HF treatment.
また本発明の他の態様は、上記基板処理方法を実施する基板処理装置に係る。 Another embodiment of the present invention relates to a substrate processing apparatus for performing the substrate processing method.
この基板処理装置は、基板を処理する処理室と、槽内でフッ化水素酸と超純水とを混合して希フッ酸を調製し貯留する混合水貯留槽と、フッ化水素酸を混合水貯留槽に供給するフッ化水素酸供給手段と、超純水を混合水貯留槽に供給する超純水供給手段と、希フッ酸を基板の処理液として処理室に送る処理液供給手段と、を有する。 This substrate processing apparatus mixes hydrofluoric acid with a processing chamber for processing substrates, a mixed water storage tank for preparing and storing dilute hydrofluoric acid by mixing hydrofluoric acid and ultrapure water in the tank. Hydrofluoric acid supply means for supplying water to the water storage tank; ultrapure water supply means for supplying ultrapure water to the mixed water storage tank; and processing liquid supply means for sending dilute hydrofluoric acid as a substrate processing liquid to the processing chamber; Have.
前記フッ化水素酸供給手段は、フッ化水素酸に水素を添加する水素添加装置と、当該水素が添加されたフッ化水素酸中の溶存酸素および過酸化水素を除去するための酸化剤除去装置とを備えている。水素が添加されたフッ化水素酸を酸化剤除去装置に通して溶存酸素および過酸化水素を除去した後に混合水貯留槽に供給して得た、溶存酸素濃度が２μｇ／Ｌ以下、溶存過酸化水素濃度が２μｇ／Ｌ以下の処理液によって、前記基板が処理される。 The hydrofluoric acid supply means includes a hydrogen adding device for adding hydrogen to hydrofluoric acid, and an oxidant removing device for removing dissolved oxygen and hydrogen peroxide in hydrofluoric acid to which the hydrogen has been added. And. Hydrogen fluoride added with hydrogen was passed through an oxidant removal device to remove dissolved oxygen and hydrogen peroxide, and then supplied to the mixed water storage tank. The dissolved oxygen concentration was 2 μg / L or less, and dissolved peroxidation. The substrate is treated with a treatment liquid having a hydrogen concentration of 2 μg / L or less.
あるいは、前記処理液供給手段は、希フッ酸に水素を添加する水素添加装置と、当該水素が添加された希フッ酸中の溶存酸素および過酸化水素を除去するための酸化剤除去装置とを備えていてもよい。この場合は、水素が添加された希フッ酸を酸化剤除去装置に通して溶存酸素および過酸化水素を除去して得た、溶存酸素濃度が２μｇ／Ｌ以下、溶存過酸化水素濃度が２μｇ／Ｌ以下の処理液によって、前記基板が処理される。 Alternatively, the treatment liquid supply means includes a hydrogen adding device for adding hydrogen to dilute hydrofluoric acid, and an oxidant removing device for removing dissolved oxygen and hydrogen peroxide in dilute hydrofluoric acid to which the hydrogen is added. You may have. In this case, dilute hydrofluoric acid to which hydrogen has been added is passed through an oxidant removing device to remove dissolved oxygen and hydrogen peroxide, and the dissolved oxygen concentration is 2 μg / L or less, and the dissolved hydrogen peroxide concentration is 2 μg / L. The substrate is processed with a processing solution of L or less.
本発明によれば、半導体装置製造プロセスの基板処理液として、半導体基板製品の歩留まりや性能を下げないような濃度に溶存酸素および溶存過酸化水素が抑制されたフッ化水素酸溶液を提供することが出来る。 According to the present invention, there is provided a hydrofluoric acid solution in which dissolved oxygen and dissolved hydrogen peroxide are suppressed to a concentration that does not lower the yield and performance of semiconductor substrate products as a substrate processing solution for a semiconductor device manufacturing process. I can do it.
以下、本発明の実施の形態について図面を参照して説明する。 Hereinafter, embodiments of the present invention will be described with reference to the drawings.
［第一実施形態］
図２は、本発明の第一実施形態に係る基板処理装置の概略構成を示す模式図である。
[First embodiment]
FIG. 2 is a schematic diagram showing a schematic configuration of the substrate processing apparatus according to the first embodiment of the present invention.
本実施形態では、半導体ウエハの洗浄やエッチング等の目的で、フッ化水素酸（ＨＦ）と超純水とを混合して希フッ酸を調製し、基板処理装置２１の処理室１０１に供給する。本明細書では「フッ化水素酸」を「フッ酸」と略称することがある。また本発明では、処理液原液のフッ化水素酸（ＨＦ）に替えて、主に絶縁膜の洗浄やエッチングに用いられるバッファードフッ酸（ＢＨＦ）を使用してもよい。バッファードフッ酸は、フッ化水素酸（ＨＦ）とフッ化アンモニウム溶液の混合溶液である。
In the present embodiment, dilute hydrofluoric acid is prepared by mixing hydrofluoric acid (HF) and ultrapure water for the purpose of cleaning or etching the semiconductor wafer, and supplying the diluted hydrofluoric acid to the
基板処理装置２１は、槽内でＨＦと超純水とを混合して希フッ酸（ＤＨＦ）を調製し貯留する混合水貯留槽２２と、薬液タンク（不図示）内のＨＦを混合水貯留槽２２に供給するＨＦ供給ライン３１（フッ化水素酸供給手段）と、混合水貯留槽２２に超純水を供給する超純水供給ライン３２（超純水供給手段）と、ＤＨＦを基板処理液として処理室１０１に送る処理液供給ライン２３と、を有している。
The
ＨＦ供給ライン３１上には、本発明によるフッ化水素酸溶液の精製方法を実施するＨＦ精製ユニット１０が設置されている。ＨＦ精製ユニット１０は、ＨＦに水素を添加する水素添加装置２５と、当該水素が添加されたＨＦ中の溶存酸素および過酸化水素を除去するための酸化剤除去装置２９とを備えている。
On the
水素添加装置２５により水素を添加したＨＦの原液を酸化剤除去装置に通液させることによって、該ＨＦ中の溶存酸素濃度および過酸化水素濃度を低減することができる。添加する水素の濃度は１０μｇ／Ｌ以上であることが望ましい。
By passing the HF stock solution to which hydrogen has been added by the
酸化剤除去装置２９は白金族系金属触媒を充填した態様を有する。例えば、パラジウム触媒を充填した触媒ユニットや、パラジウム触媒をモノリスに担持した触媒ユニットが挙げられるが、当該白金族系金属触媒のより詳細な具体例については後で記載することにする（第三実施形態を参照）。
The oxidizing
なお、ＨＦの原液が水素添加装置２５および酸化剤除去装置２９を順次通水することにより、当該ＨＦは溶存酸素濃度が２μｇ／Ｌ以下、過酸化水素濃度が２μｇ／Ｌ以下の液体に精製される。この事は、後述する実施例中に示した評価結果に基づく。
As the HF stock solution is sequentially passed through the
混合水貯留槽２２は酸化剤除去装置２９及び超純水供給ライン３２の後段に位置しており、ＨＦ精製ユニット１０で精製されたＨＦと超純水供給ライン３２から供給された超純水とを槽内で混合してＤＨＦを調製し貯留する。混合水貯留槽２２に対する精製ＨＦの供給量と超純水の供給量とを調整することにより、所定の濃度に希釈されたＤＨＦを作ることができる。
The mixed
超純水供給ライン３２は、例えば、背景技術の欄で述べたような超純水製造装置のサブシステム（図１参照）からの超純水を混合水貯留槽２２へ供給する配管である。超純水供給ライン３２から供給される超純水はあらかじめ、溶存酸素濃度が２μｇ／Ｌ以下、過酸化水素濃度が２μｇ／Ｌ以下に低減された超純水を用いる必要がある。
The ultrapure
混合水貯留槽２２は、密閉容器からなるものであり、混合水貯留槽２２内に窒素ガス等の不活性ガスを供給する不活性ガス供給ライン２７を備えている。混合水貯留槽２２に不活性ガスを供給することにより、混合水貯留槽２２内から空気を追い出すことができる。したがって、混合水貯留槽２２内の空気に含まれる酸素が、混合水貯留槽２２に貯留されたＤＨＦに溶け込んで、当該ＤＨＦ中の溶存酸素量が増加することを抑制または防止することができる。また、不活性ガスによって混合水貯留槽２２内を加圧することにより、混合水貯留槽２２内に貯留されたＤＨＦを処理液供給ライン２３に圧送することができる。
The mixed
なお、ＨＦ精製ユニット１０で精製されたＨＦ原液を、混合水貯留槽２２を経由させないで処理室１０１へ直接供給するラインを設けてもよい。
In addition, you may provide the line which supplies the HF stock solution refine | purified by the HF refinement |
また、処理室１０１は、被処理基板を保持して該被処理基板にノズルよりＤＨＦを吐出する枚葉式の処理機構、あるいは、被処理基板を処理槽内に収容し、該処理槽内にＤＨＦを供給して被処理基板を浸漬させるバッチ式の処理機構のいずれかを備えることができる。さらに、被処理体表面の金属の腐食抑制および酸化抑制の観点で、基板処理の工程中は処理室１０１内に不活性ガスを充填して、処理室１０１内における酸素ガス濃度を２％以下にしておくことが望ましい。
The
［第二実施形態］
図３は、本発明の第二実施形態に係る基板処理装置の概略構成を示す模式図である。この図では上述した第一実施形態の構成要素と同じものには同一符号を付してあり、その説明は割愛する。
[Second Embodiment]
FIG. 3 is a schematic diagram showing a schematic configuration of the substrate processing apparatus according to the second embodiment of the present invention. In this figure, the same components as those of the first embodiment described above are denoted by the same reference numerals, and description thereof is omitted.
本実施形態に係る基板処理装置３１では、前述したＨＦ精製ユニット１０が処理液供給ライン２３上に設置されている。つまり、第一実施形態では、ＨＦの原液から溶存酸素および溶存過酸化水素を除去する態様を示したが、第二実施形態では、ＨＦの原液を超純水で希釈してなるＤＨＦ（希フッ酸）から酸素および溶存過酸化水素を除去する態様を示す。
In the
図３を参照すると、混合水貯留槽２２には、ＨＦの原液を供給するＨＦ供給ライン３１と、混合水貯留槽２２に超純水を供給する超純水供給ライン３２とがそれぞれ直接、接続されている。混合水貯留槽２２に対するＨＦ原液の供給量と超純水の供給量とを調整することにより、所定の濃度に希釈されたＤＨＦを作ることができる。
Referring to FIG. 3, an
酸化剤除去装置２９は、混合水貯留槽２２内で調製されたＤＨＦを処理室１０１へ供給する処理液供給ライン２３上に設置されている。さらに、水素添加装置２５は、混合水貯留槽２２から酸化剤除去装置２９の間の処理液供給ラインに接続されている。
The
水素添加装置２５により、ＤＨＦに水素を添加することによって、水素が該ＤＨＦ中の溶存酸素と反応して水を生成するため、該ＤＨＦ中の溶存酸素濃度を低減することができる。添加する水素の濃度は１０μｇ／Ｌ以上であることが、溶存酸素の除去にとって望ましい。
By adding hydrogen to DHF by the
さらに、溶存酸素が低減されたＤＨＦが酸化剤除去装置２９を順次通水することにより、当該ＤＨＦは溶存酸素濃度が２μｇ／Ｌ以下、過酸化水素濃度が２μｇ／Ｌ以下の液体に精製される。この事は、後述する実施例中に示した評価結果に基づく。
Further, the DHF in which dissolved oxygen is reduced sequentially passes through the
この形態では、超純水供給ライン３２から供給される超純水は、溶存酸素濃度が２μｇ／Ｌ以下、過酸化水素濃度が２μｇ／Ｌ以下に低減されていない超純水を用いてもよい。
In this embodiment, the ultrapure water supplied from the ultrapure
第一実施形態と同様、酸化剤除去装置２９には、パラジウム触媒を充填した触媒ユニットや、パラジウム触媒をモノリスに担持した触媒ユニットが挙げられる。
As in the first embodiment, the
この第二実施形態は第一実施形態と同様の効果を奏する。その上、第二実施形態では、前述した第一実施形態と比べてＨＦ精製ユニット１０が処理室１０１の近くに配置されるため、処理室１０１内により清浄なＤＨＦを供給できる。
This second embodiment has the same effects as the first embodiment. In addition, in the second embodiment, since the
［第三実施形態］
上述した基板処理装置２１，３１の酸化剤除去装置２９に使用される、溶存酸素除去と過酸化水素除去のための触媒の具体例について詳述する。
[Third embodiment]
A specific example of a catalyst for removing dissolved oxygen and removing hydrogen peroxide used in the
＜溶存酸素除去と過酸化水素除去のための触媒＞
当該触媒としては、白金族金属が担持された粒状のイオン交換樹脂、金属イオン型の粒状の陽イオン交換樹脂、白金族金属が担持された非粒状の有機多孔質体又は白金族金属が担持された非粒状の有機多孔質イオン交換体が挙げられる。
<Catalyst for removing dissolved oxygen and hydrogen peroxide>
The catalyst includes a granular ion exchange resin carrying a platinum group metal, a metal ion type granular cation exchange resin, a non-particulate organic porous material carrying a platinum group metal or a platinum group metal. Non-particulate organic porous ion exchangers.
＜白金族金属担持非粒状有機多孔質体、白金族金属担持非粒状有機多孔質イオン交換体＞
白金族金属担持非粒状有機多孔質体としては、非粒状有機多孔質体に、平均粒子径１〜１０００ｎｍの白金族金属の微粒状が担持されており、非粒状有機多孔質体が、連続骨格相と連続空孔相からなり、連続骨格の厚みは１〜１００μｍ、連続空孔の平均直径は１０〜２００μｍ、全細孔容積は０．５〜５０ｍｌ／ｇであり、白金族金属の担持量が、乾燥状態で０．００４〜２０重量％である白金族金属担持非粒状有機多孔質体が挙げられる。
<Platinum group metal-supported non-particulate organic porous body, platinum group metal-supported non-particulate organic porous ion exchanger>
As the platinum group metal-supported non-particulate organic porous body, fine particles of platinum group metal having an average particle diameter of 1 to 1000 nm are supported on the non-particulate organic porous body, and the non-particulate organic porous body is a continuous skeleton. It consists of a phase and a continuous pore phase, the thickness of the continuous skeleton is 1-100 μm, the average diameter of the continuous pores is 10-200 μm, the total pore volume is 0.5-50 ml / g, and the supported amount of platinum group metal However, a platinum group metal carrying non-granular organic porous material which is 0.004 to 20% by weight in a dry state.
また、白金族金属担持非粒状有機多孔質イオン交換体としては、非粒状有機多孔質イオン交換体に、平均粒子径１〜１０００ｎｍの白金族金属の微粒状が担持されており、非粒状有機多孔質イオン交換体は、連続骨格相と連続空孔相からなり、連続骨格の厚みは１〜１００μｍ、連続空孔の平均直径は１０〜２００μｍ、全細孔容積は０．５〜５０ｍｌ／ｇであり、乾燥状態での重量当りのイオン交換容量は１〜６ｍｇ当量／ｇであり、イオン交換基が有機多孔質イオン交換体中に均一に分布しており、白金族金属の担持量が、乾燥状態で０．００４〜２０重量％である白金族金属担持非粒状有機多孔質イオン交換体が挙げられる。 Further, as the platinum group metal-supported non-particulate organic porous ion exchanger, fine particles of platinum group metal having an average particle diameter of 1 to 1000 nm are supported on the non-particulate organic porous ion exchanger. The ion exchanger comprises a continuous skeleton phase and a continuous pore phase, the thickness of the continuous skeleton is 1 to 100 μm, the average diameter of the continuous pores is 10 to 200 μm, and the total pore volume is 0.5 to 50 ml / g. Yes, the ion exchange capacity per weight in the dry state is 1 to 6 mg equivalent / g, the ion exchange groups are uniformly distributed in the organic porous ion exchanger, and the supported amount of platinum group metal is The platinum group metal carrying non-particulate organic porous ion exchanger which is 0.004-20 weight% in a state is mentioned.
なお、非粒状有機多孔質体又は非粒状有機多孔質イオン交換体の開口の平均直径は、水銀圧入法により測定され、水銀圧入法により得られた細孔分布曲線の極大値を指す。また、非粒状有機多孔質体又は非粒状有機多孔質イオン交換体の構造、及び連続骨格の厚みは、ＳＥＭ観察により求められる。非粒状有機多孔質体又は非粒状有機多孔質イオン交換体に担持されている白金族金属の微粒状の粒子径は、ＴＥＭ観察により求められる。 In addition, the average diameter of the opening of a non-particulate organic porous body or a non-particulate organic porous ion exchanger is measured by the mercury intrusion method, and indicates the maximum value of the pore distribution curve obtained by the mercury intrusion method. Further, the structure of the non-particulate organic porous body or the non-particulate organic porous ion exchanger and the thickness of the continuous skeleton are determined by SEM observation. The fine particle diameter of the platinum group metal supported on the non-particulate organic porous body or the non-particulate organic porous ion exchanger is determined by TEM observation.
上記の白金族金属担持非粒状有機多孔質体又は白金族金属担持非粒状有機多孔質イオン交換体は、非粒状有機多孔質体又は非粒状有機多孔質イオン交換体に、平均粒子径１〜１０００ｎｍの白金族金属が担持されているので、高い過酸化水素分解触媒活性を示し、且つ、２００〜２００００ｈ-1好ましくは２０００〜２００００ｈ-1の空間速度（ＳＶ）で被処理水を通水させることができる。 The platinum group metal-supported non-particulate organic porous material or the platinum group metal-supported non-particulate organic porous ion exchanger has an average particle diameter of 1 to 1000 nm to the non-particulate organic porous material or the non-particulate organic porous ion exchanger. since the platinum group metal is supported, it shows a high hydrogen peroxide decomposition catalytic activity, and, 200～20000H -1 preferably be passed through the treated water at a space velocity (SV) of 2000～20000H -1 Can do.
白金族金属担持非粒状有機多孔質体において、白金族金属が担持されている担体は、非粒状有機多孔質体であるが、この非粒状有機多孔質交換体とは、モノリス状有機多孔質交換体である。また、白金族金属担持非粒状有機多孔質イオン交換体において、白金族金属が担持されている担体は、非粒状有機多孔質イオン交換体であるが、この非粒状有機多孔質イオン交換体とは、モノリス状有機多孔質イオン交換体であり、モノリス状有機多孔質体にイオン交換基が導入されたものである。 In the platinum group metal-supported non-particulate organic porous body, the carrier on which the platinum group metal is supported is a non-particulate organic porous body. This non-particulate organic porous exchanger is a monolithic organic porous exchange. Is the body. In the platinum group metal-supported non-particulate organic porous ion exchanger, the carrier on which the platinum group metal is supported is a non-particulate organic porous ion exchanger. A monolithic organic porous ion exchanger, in which an ion exchange group is introduced into the monolithic organic porous body.
モノリス状有機多孔質体は、骨格が有機ポリマーにより形成されており、骨格間に反応液の流路となる連通孔を多数有する多孔質体である。そして、モノリス状有機多孔質イオン交換体は、このモノリス状有機多孔質体の骨格中にイオン交換基が均一に分布するように導入されている多孔質体である。なお、本明細書中、「モノリス状有機多孔質体」を単に「モノリス」と、「モノリス状有機多孔質イオン交換体」を単に「モノリスイオン交換体」とも言い、また、モノリスの製造における中間体（前駆体）である「モノリス状有機多孔質中間体」を単に「モノリス中間体」とも言う。 The monolithic organic porous body is a porous body having a skeleton formed of an organic polymer and a large number of communication holes serving as a flow path for a reaction solution between the skeletons. The monolithic organic porous ion exchanger is a porous body introduced so that ion exchange groups are uniformly distributed in the skeleton of the monolithic organic porous body. In the present specification, “monolithic organic porous material” is also simply referred to as “monolith”, and “monolithic organic porous ion exchanger” is also simply referred to as “monolith ion exchanger”, and is also an intermediate in the production of monoliths. The “monolithic organic porous intermediate” that is the body (precursor) is also simply referred to as “monolith intermediate”.
このようなモノリス又はモノリスイオン交換体の構造例としては、特開２００２−３０６９７６号公報や特開２００９−６２５１２号公報に開示されている連続気泡構造や、特開２００９−６７９８２号公報に開示されている共連続構造や、特開２００９−７５５０号公報に開示されている粒子凝集型構造や、特開２００９−１０８２９４号公報に開示されている粒子複合型構造等が挙げられる。 Examples of the structure of such a monolith or monolith ion exchanger are disclosed in Japanese Patent Application Laid-Open No. 2002-306976 and Japanese Patent Application Laid-Open No. 2009-62512, and Japanese Patent Application Laid-Open No. 2009-67982. A co-continuous structure, a particle aggregation type structure disclosed in JP 2009-7550 A, a particle composite type structure disclosed in JP 2009-108294 A, and the like.
上記モノリス、すなわち、白金族金属粒子の担体となるモノリスの形態例（以下、モノリス（１）とも記載する。）及び上記モノリスイオン交換体、すなわち、白金族金属粒子の担体となるモノリスイオン交換体の形態例（以下、モノリスイオン交換体（１）とも記載する。）としては、特開２００９−６７９８２号公報に開示されている共連続構造を有するモノリス及びモノリスイオン交換体が挙げられる。 Examples of monoliths serving as carriers for the above monolith, that is, platinum group metal particles (hereinafter also referred to as monolith (1)) and monolith ion exchangers, that is, monolith ion exchangers serving as the carrier for platinum group metal particles Examples of the form (hereinafter also referred to as monolith ion exchanger (1)) include monoliths and monolith ion exchangers having a co-continuous structure disclosed in JP-A No. 2009-67982.
つまり、モノリス（１）は、イオン交換基が導入される前のモノリスであり、全構成単位中、架橋構造単位を０．１〜５．０モル％含有する芳香族ビニルポリマーからなる平均太さが乾燥状態で１〜１００μｍの三次元的に連続した骨格と、その骨格間に平均直径が乾燥状態で１０〜２００μｍの三次元的に連続した空孔とからなる共連続構造体であって、乾燥状態での全細孔容積が０．５〜５０ｍｌ／ｇである有機多孔質体であるモノリスである。 That is, the monolith (1) is a monolith before the ion exchange group is introduced, and has an average thickness composed of an aromatic vinyl polymer containing 0.1 to 5.0 mol% of a crosslinked structural unit among all the structural units. Is a co-continuous structure comprising a three-dimensionally continuous skeleton of 1 to 100 μm in a dry state and three-dimensionally continuous pores having an average diameter of 10 to 200 μm between the skeletons, It is a monolith that is an organic porous body having a total pore volume of 0.5 to 50 ml / g in a dry state.
また、モノリスイオン交換体（１）は、全構成単位中、架橋構造単位を０．１〜５．０モル％含有する芳香族ビニルポリマーからなる平均太さが乾燥状態で１〜１００μｍの三次元的に連続した骨格と、その骨格間に平均直径が乾燥状態で１０〜２００μｍの三次元的に連続した空孔とからなる共連続構造体であって、乾燥状態での全細孔容積が０．５〜５０ｍｌ／ｇであり、イオン交換基を有しており、乾燥状態での重量当りのイオン交換容量が１〜６ｍｇ当量／ｇであり、イオン交換基が有機多孔質イオン交換体中に均一に分布しているモノリスイオン交換体であるモノリスイオン交換体である。 In addition, the monolith ion exchanger (1) has a three-dimensional average thickness of 1 to 100 μm in a dry state of an aromatic vinyl polymer containing 0.1 to 5.0 mol% of a crosslinked structural unit among all the structural units. A continuous structure and three-dimensionally continuous pores having an average diameter of 10 to 200 μm in the dry state between the skeletons, and the total pore volume in the dry state is 0 5 to 50 ml / g, having an ion exchange group, an ion exchange capacity per weight in a dry state of 1 to 6 mg equivalent / g, and the ion exchange group in the organic porous ion exchanger It is a monolith ion exchanger that is a monolith ion exchanger that is uniformly distributed.
モノリス（１）又はモノリスイオン交換体（１）は、平均太さが乾燥状態で１〜１００μｍ、好ましくは３〜５８μｍの三次元的に連続した骨格と、その骨格間に平均直径が乾燥状態で１０〜２００μｍ、好ましくは１５〜１８０μｍ、特に好ましくは２０〜１５０μｍの三次元的に連続した空孔とからなる共連続構造体である。共連続構造とは、連続する骨格相と連続する空孔相とが絡み合ってそれぞれが共に３次元的に連続する構造である。この連続した空孔は、従来の連続気泡型モノリスや粒子凝集型モノリスに比べて空孔の連続性が高くてその大きさに偏りがない。また、骨格が太いため機械的強度が高い。 The monolith (1) or the monolith ion exchanger (1) has a three-dimensional continuous skeleton having an average thickness of 1 to 100 μm, preferably 3 to 58 μm in a dry state, and an average diameter between the skeletons in a dry state. It is a co-continuous structure composed of three-dimensionally continuous pores of 10 to 200 μm, preferably 15 to 180 μm, particularly preferably 20 to 150 μm. The co-continuous structure is a structure in which a continuous skeleton phase and a continuous vacancy phase are intertwined, and both are three-dimensionally continuous. The continuous pores have higher continuity of the pores than the conventional open-cell type monolith and the particle aggregation type monolith, and the size thereof is not biased. Moreover, since the skeleton is thick, the mechanical strength is high.
三次元的に連続した空孔の平均直径が乾燥状態で１μｍ未満であると、通液時の圧力損失が大きくなってしまうため好ましくなく、１０００μｍを超えると、反応液とモノリス又はモノリスイオン交換体との接触が不十分となり、その結果、触媒活性が不十分となるため好ましくない。また、骨格の平均太さが乾燥状態で１μｍ未満であると、高流速で通液した際にモノリス又はモノリスイオン交換体が大きく変形してしまうため好ましくない。更に、反応液とモノリス又はモノリスイオン交換体との接触効率が低下し、触媒効果が低下するため好ましくない。一方、骨格の太さが１００μｍを越えると、骨格が太くなり過ぎ、通液時の圧力損失が増大するため好ましくない。 If the average diameter of the three-dimensionally continuous pores is less than 1 μm in the dry state, it is not preferable because the pressure loss at the time of passing the liquid increases, and if it exceeds 1000 μm, the reaction solution and the monolith or monolith ion exchanger As a result, the contact with the catalyst becomes insufficient, resulting in insufficient catalytic activity. Moreover, when the average thickness of the skeleton is less than 1 μm in a dry state, the monolith or the monolith ion exchanger is greatly deformed when the liquid is passed at a high flow rate. Furthermore, the contact efficiency between the reaction liquid and the monolith or monolith ion exchanger is lowered, and the catalytic effect is lowered, which is not preferable. On the other hand, if the thickness of the skeleton exceeds 100 μm, the skeleton becomes too thick, and the pressure loss during liquid passage increases, which is not preferable.
乾燥状態のモノリス（１）の開口の平均直径、モノリスイオン交換体（１）の開口の平均直径及び以下に述べるモノリスの製造のＩ処理で得られる、乾燥状態のモノリス中間体（１）の開口の平均直径は、水銀圧入法により測定され、水銀圧入法により得られた細孔分布曲線の極大値を指す。また、モノリス（１）又はモノリスイオン交換体（１）の骨格の乾燥状態での平均太さは、乾燥状態のモノリス（１）又はモノリスイオン交換体（１）のＳＥＭ観察により求められる。具体的には、乾燥状態のモノリス（１）又はモノリスイオン交換体（１）のＳＥＭ観察を少なくとも３回行い、得られた画像中の骨格の太さを測定し、それらの平均値を平均太さとする。なお、骨格は棒状であり円形断面形状であるが、楕円断面形状等異径断面のものが含まれていてもよい。この場合の太さは短径と長径の平均である。 The average diameter of the opening of the monolith (1) in the dry state, the average diameter of the opening of the monolith ion exchanger (1) and the opening of the monolith intermediate (1) in the dry state obtained by the I treatment in the production of the monolith described below The average diameter is measured by the mercury intrusion method and refers to the maximum value of the pore distribution curve obtained by the mercury intrusion method. The average thickness of the skeleton of the monolith (1) or the monolith ion exchanger (1) in the dry state is determined by SEM observation of the dry monolith (1) or the monolith ion exchanger (1). Specifically, the SEM observation of the dried monolith (1) or monolith ion exchanger (1) is performed at least three times, the thickness of the skeleton in the obtained image is measured, and the average value thereof is calculated as the average thickness. Say it. The skeleton has a rod-like shape and a circular cross-sectional shape, but may have a cross-section with a different diameter such as an elliptical cross-sectional shape. The thickness in this case is the average of the minor axis and the major axis.
また、モノリス（１）又はモノリスイオン交換体（１）の乾燥状態での重量当りの全細孔容積は、０．５〜５０ｍｌ／ｇである。全細孔容積が０．５ｍｌ／ｇ未満であると、通液時の圧力損失が大きくなってしまうため好ましくなく、更に、単位断面積当りの透過量が小さくなり、処理量が低下してしまうため好ましくない。一方、全細孔容積が５０ｍｌ／ｇを超えると、機械的強度が低下して、特に高流速で通液した際にモノリス又はモノリスイオン交換体が大きく変形してしまうため好ましくない。更に、反応液とモノリス（１）又はモノリスイオン交換体（１）との接触効率が低下するため、触媒効率も低下してしまうため好ましくない。三次元的に連続した空孔の大きさ及び全細孔容積が上記範囲にあれば、反応液との接触が極めて均一で接触面積も大きく、かつ低圧力損失下での通液が可能となる。 Moreover, the total pore volume per weight in the dry state of the monolith (1) or the monolith ion exchanger (1) is 0.5 to 50 ml / g. If the total pore volume is less than 0.5 ml / g, the pressure loss at the time of liquid passing is increased, which is not preferable. Further, the permeation amount per unit cross-sectional area is decreased, and the processing amount is decreased. Therefore, it is not preferable. On the other hand, if the total pore volume exceeds 50 ml / g, the mechanical strength is lowered, and the monolith or the monolith ion exchanger is greatly deformed particularly when the liquid is passed at a high flow rate. Furthermore, since the contact efficiency between the reaction liquid and the monolith (1) or the monolith ion exchanger (1) is lowered, the catalyst efficiency is also lowered, which is not preferable. If the three-dimensionally continuous pore size and total pore volume are within the above ranges, the contact with the reaction solution is extremely uniform, the contact area is large, and the solution can be passed under a low pressure loss. .
モノリス（１）又はモノリスイオン交換体（１）において、骨格を構成する材料は、全構成単位中、０．１〜５モル％、好ましくは０．５〜３．０モル％の架橋構造単位を含んでいる芳香族ビニルポリマーであり疎水性である。架橋構造単位が０．１モル％未満であると、機械的強度が不足するため好ましくなく、一方、５モル％を越えると、多孔質体の構造が共連続構造から逸脱しやすくなる。芳香族ビニルポリマーの種類に特に制限はなく、例えば、ポリスチレン、ポリ（α-メチルスチレン）、ポリビニルトルエン、ポリビニルベンジルクロライド、ポリビニルビフェニル、ポリビニルナフタレン等が挙げられる。上記ポリマーは、単独のビニルモノマーと架橋剤を共重合させて得られるポリマーでも、複数のビニルモノマーと架橋剤を重合させて得られるポリマーであってもよく、また、二種類以上のポリマーがブレンドされたものであってもよい。これら有機ポリマー材料の中で、共連続構造形成の容易さ、イオン交換基導入の容易性と機械的強度の高さ、および、酸又はアルカリに対する安定性の高さから、スチレン−ジビニルベンゼン共重合体やビニルベンジルクロライド−ジビニルベンゼン共重合体が好ましい。 In the monolith (1) or the monolith ion exchanger (1), the material constituting the skeleton is 0.1 to 5 mol%, preferably 0.5 to 3.0 mol% of a crosslinked structural unit in all the structural units. It is an aromatic vinyl polymer containing and is hydrophobic. If the cross-linking structural unit is less than 0.1 mol%, the mechanical strength is insufficient, which is not preferable. On the other hand, if it exceeds 5 mol%, the structure of the porous body tends to deviate from the bicontinuous structure. There is no restriction | limiting in particular in the kind of aromatic vinyl polymer, For example, a polystyrene, poly ((alpha) -methylstyrene), polyvinyl toluene, polyvinyl benzyl chloride, polyvinyl biphenyl, polyvinyl naphthalene etc. are mentioned. The polymer may be a polymer obtained by copolymerizing a single vinyl monomer and a crosslinking agent, a polymer obtained by polymerizing a plurality of vinyl monomers and a crosslinking agent, or a blend of two or more types of polymers. It may be what was done. Among these organic polymer materials, styrene-divinylbenzene copolymer has the advantage of easy co-continuous structure formation, ease of ion exchange group introduction and high mechanical strength, and high stability to acids or alkalis. A polymer or vinylbenzyl chloride-divinylbenzene copolymer is preferred.
モノリスイオン交換体（１）において、導入されているイオン交換基は、モノリスの表面のみならず、モノリスの骨格内部にまで均一に分布している。ここで言う「イオン交換基が均一に分布している」とは、イオン交換基の分布が少なくともμｍオーダーで表面および骨格内部に均一に分布していることを指す。イオン交換基の分布状況は、ＥＰＭＡを用いることで簡単に確認される。また、イオン交換基が、モノリスの表面のみならず、モノリスの骨格内部にまで均一に分布していると、表面と内部の物理的性質及び化学的性質を均一にできるため、膨潤及び収縮に対する耐久性が向上する。 In the monolith ion exchanger (1), the introduced ion exchange groups are uniformly distributed not only on the surface of the monolith but also inside the skeleton of the monolith. Here, “ion exchange groups are uniformly distributed” means that the distribution of ion exchange groups is uniformly distributed on the surface and inside the skeleton in the order of at least μm. The distribution status of the ion exchange groups can be easily confirmed by using EPMA. In addition, if the ion exchange groups are uniformly distributed not only on the surface of the monolith but also within the skeleton of the monolith, the physical and chemical properties of the surface and the interior can be made uniform, so that they are resistant to swelling and shrinkage. Improves.
モノリスイオン交換体（１）に導入されているイオン交換基は、カチオン交換基又はアニオン交換基である。カチオン交換基としては、カルボン酸基、イミノ二酢酸基、スルホン酸基、リン酸基、リン酸エステル基等が挙げられる。アニオン交換基としては、トリメチルアンモニウム基、トリエチルアンモニウム基、トリブチルアンモニウム基、ジメチルヒドロキシエチルアンモニウム基、ジメチルヒドロキシプロピルアンモニウム基、メチルジヒドロキシエチルアンモニウム基等の四級アンモニウム基や、第三スルホニウム基、ホスホニウム基等が挙げられる。 The ion exchange group introduced into the monolith ion exchanger (1) is a cation exchange group or an anion exchange group. Examples of the cation exchange group include a carboxylic acid group, an iminodiacetic acid group, a sulfonic acid group, a phosphoric acid group, and a phosphoric ester group. Examples of anion exchange groups include trimethylammonium group, triethylammonium group, tributylammonium group, dimethylhydroxyethylammonium group, dimethylhydroxypropylammonium group, methyldihydroxyethylammonium group, quaternary ammonium group, tertiary sulfonium group, phosphonium group. Etc.
モノリスイオン交換体（１）は、乾燥状態での重量当りのイオン交換容量が１〜６ｍｇ当量／ｇのイオン交換容量を有する。モノリスイオン交換体（１）は、三次元的に連続した空孔の連続性や均一性が高いため、全細孔容積を低下させても圧力損失はさほど増加しない。そのため、圧力損失を低く押さえたままで体積当りのイオン交換容量を飛躍的に大きくすることができる。重量当りのイオン交換容量が上記範囲にあることにより、触媒内部のｐＨなど触媒活性点の周りの環境を変えることができ、これにより触媒活性が高くなる。モノリスイオン交換体（１）がモノリスアニオン交換体の場合は、モノリスアニオン交換体（１）には、アニオン交換基が導入されており、乾燥状態での重量当りのアニオン交換容量は、１〜６ｍｇ当量／ｇである。また、モノリスイオン交換体（１）がモノリスカチオン交換体の場合は、モノリスカチオン交換体（１）には、カチオン交換基が導入されており、乾燥状態での重量当りのカチオン交換容量は、１〜６ｍｇ当量／ｇである。 The monolith ion exchanger (1) has an ion exchange capacity of 1 to 6 mg equivalent / g of ion exchange capacity per weight in a dry state. Since the monolith ion exchanger (1) has high continuity and uniformity of three-dimensionally continuous pores, the pressure loss does not increase so much even if the total pore volume is reduced. Therefore, it is possible to dramatically increase the ion exchange capacity per volume while keeping the pressure loss low. When the ion exchange capacity per weight is in the above range, the environment around the catalyst active point such as the pH inside the catalyst can be changed, and thereby the catalyst activity is increased. When the monolith ion exchanger (1) is a monolith anion exchanger, an anion exchange group is introduced into the monolith anion exchanger (1), and the anion exchange capacity per weight in the dry state is 1 to 6 mg. Equivalent / g. When the monolith ion exchanger (1) is a monolith cation exchanger, a cation exchange group is introduced into the monolith cation exchanger (1), and the cation exchange capacity per weight in a dry state is 1 ~ 6 mg equivalent / g.
モノリス（１）は、特開２００９−６７９８２号公報に開示されているモノリス状有機多孔質体の製造方法行うことにより得られる。つまり、当該製法は、イオン交換基を含まない油溶性モノマー、界面活性剤及び水の混合物を撹拌することにより油中水滴型エマルジョンを調製し、次いで油中水滴型エマルジョンを重合させて全細孔容積が１６ｍｌ／ｇを超え、３０ｍｌ／ｇ以下の連続マクロポア構造のモノリス状の有機多孔質中間体（以下、モノリス中間体（１）とも記載する。）を得るＩ処理、芳香族ビニルモノマー、一分子中に少なくとも２個以上のビニル基を有する全油溶性モノマー中、０．３〜５モル％の架橋剤、芳香族ビニルモノマーや架橋剤は溶解するが芳香族ビニルモノマーが重合して生成するポリマーは溶解しない有機溶媒及び重合開始剤からなる混合物を調製するＩＩ処理、ＩＩ処理で得られた混合物を静置下、且つＩ処理で得られたモノリス中間体（１）の存在下に重合を行い、共連続構造体である有機多孔質体であるモノリス（１）を得るＩＩＩ処理、を含む。 Monolith (1) can be obtained by carrying out the method for producing a monolithic organic porous material disclosed in JP-A-2009-66792. That is, the production method prepares a water-in-oil emulsion by stirring a mixture of an oil-soluble monomer that does not contain an ion-exchange group, a surfactant, and water, and then polymerizes the water-in-oil emulsion to form all pores. I treatment for obtaining a monolithic organic porous intermediate (hereinafter also referred to as monolith intermediate (1)) having a continuous macropore structure having a volume of more than 16 ml / g and 30 ml / g or less, an aromatic vinyl monomer, one In all oil-soluble monomers having at least two vinyl groups in the molecule, 0.3 to 5 mol% of the crosslinking agent, aromatic vinyl monomer and crosslinking agent are dissolved, but the aromatic vinyl monomer is polymerized to form. Preparation of a mixture comprising an organic solvent in which the polymer does not dissolve and a polymerization initiator II treatment, a monolith intermediate obtained by standing the mixture obtained by the II treatment and by the I treatment Polymerization was conducted in the presence of 1), including III treatment, to obtain a monolith (1) is an organic porous material is a co-continuous structure.
白金族金属担持非粒状有機多孔質体又は白金族金属担持非粒状有機多孔質イオン交換体には、白金族金属が担持されている。白金族金属とは、ルテニウム、ロジウム、パラジウム、オスミウム、イリジウム、白金である。これらの白金族金属は、一種類を単独で用いても、二種類以上の金属を組み合わせて用いても良く、更に、二種類以上の金属を合金として用いても良い。これらの中で、白金、パラジウム、白金／パラジウム合金は触媒活性が高く、好適に用いられる。 A platinum group metal is supported on the platinum group metal-supported non-particulate organic porous body or the platinum group metal-supported non-particulate organic porous ion exchanger. The platinum group metal is ruthenium, rhodium, palladium, osmium, iridium, or platinum. These platinum group metals may be used alone or in combination of two or more metals, and more than one metal may be used as an alloy. Among these, platinum, palladium, and platinum / palladium alloys have high catalytic activity and are preferably used.
白金族金属担持非粒状有機多孔質体又は白金族金属担持非粒状有機多孔質イオン交換体に担持されている白金族金属粒子の平均粒子径は、１〜１０００ｎｍであり、好ましくは１〜５０ｎｍ、更に好ましくは１〜２０ｎｍである。平均粒子径が１ｎｍ未満であると、白金族金属粒子が担体から脱離する可能性が高くなるため好ましくなく、一方、平均粒子径が１０００ｎｍを超えると、金属の単位質量当たりの表面積が少なくなり触媒効果が効率的に得られなくなるため好ましくない。なお、白金族金属粒子の平均粒子径は、透過型電子顕微鏡（ＴＥＭ）分析により得られるＴＥＭ画像を、画像解析することにより求められる。 The average particle diameter of the platinum group metal particles supported on the platinum group metal-supported non-particulate organic porous material or platinum group metal-supported non-particulate organic porous ion exchanger is 1-1000 nm, preferably 1-50 nm, More preferably, it is 1-20 nm. If the average particle diameter is less than 1 nm, the possibility that the platinum group metal particles will be detached from the carrier increases, which is not preferable. On the other hand, if the average particle diameter exceeds 1000 nm, the surface area per unit mass of the metal decreases. This is not preferable because the catalytic effect cannot be obtained efficiently. In addition, the average particle diameter of a platinum group metal particle is calculated | required by image-analyzing the TEM image obtained by a transmission electron microscope (TEM) analysis.
白金族金属担持非粒状有機多孔質体又は白金族金属担持非粒状有機多孔質イオン交換体中の白金族金属粒子の担持量（（白金族金属粒子／乾燥状態の白金族金属担持触媒）×１００）は、０．００４〜２０重量％、好ましくは０．００５〜１５重量％である。白金族金属粒子の担持量が０．００４重量％未満であると、触媒活性が不十分になるため好ましくない。一方、白金族金属粒子の担時量が２０重量％を超えると、水中への金属溶出が認められるようになるため好ましくない。 Platinum group metal-supported non-particulate organic porous material or platinum group metal-supported non-particulate organic porous ion exchanger supported amount of platinum group metal particles ((platinum group metal particles / platinum group metal-supported catalyst in dry state) × 100 ) Is 0.004 to 20% by weight, preferably 0.005 to 15% by weight. If the supported amount of platinum group metal particles is less than 0.004% by weight, the catalytic activity becomes insufficient, such being undesirable. On the other hand, when the amount of platinum group metal particles is more than 20% by weight, metal elution into water is observed, which is not preferable.
白金族金属担持非粒状有機多孔質体又は白金族金属担持非粒状有機多孔質イオン交換体の製造方法には特に制約はない。公知の方法により、モノリス又はモノリスイオン交換体に、白金族金属の微粒状を担持させることにより、白金族金属担持触媒が得られる。非粒状有機多孔質体又は非粒状有機多孔質イオン交換体に白金族金属を担持する方法としては、例えば、特開２０１０−２４０６４１号公報に開示されている方法が挙げられる。例えば、乾燥状態のモノリスイオン交換体を酢酸パラジウム等の白金族金属化合物のメタノール溶液に浸漬し、パラジウムイオンをイオン交換によりモノリスイオン交換体に吸着させ、次いで、還元剤と接触させてパラジウム金属微粒状をモノリスイオン交換体に担持する方法や、モノリスイオン交換体をテトラアンミンパラジウム錯体等の白金族金属化合物の水溶液に浸漬し、パラジウムイオンをイオン交換によりモノリスイオン交換体に吸着させ、次いで、還元剤と接触させてパラジウム金属微粒状をモノリスイオン交換体に担持する方法である。 There are no particular restrictions on the method for producing the platinum group metal-supported non-particulate organic porous material or the platinum group metal-supported non-particulate organic porous ion exchanger. A platinum group metal-supported catalyst is obtained by supporting platinum group metal fine particles on a monolith or a monolith ion exchanger by a known method. Examples of the method for supporting the platinum group metal on the non-particulate organic porous body or the non-particulate organic porous ion exchanger include the method disclosed in JP 2010-240641 A. For example, a dried monolith ion exchanger is immersed in a methanol solution of a platinum group metal compound such as palladium acetate, and palladium ions are adsorbed on the monolith ion exchanger by ion exchange, and then contacted with a reducing agent to form palladium metal fine particles. In the form of a monolithic ion exchanger, the monolithic ion exchanger is immersed in an aqueous solution of a platinum group metal compound such as a tetraamminepalladium complex, and the palladium ions are adsorbed on the monolithic ion exchanger by ion exchange, and then the reducing agent. In which the palladium metal fine particles are supported on the monolith ion exchanger.
白金族金属が担持された粒状のイオン交換樹脂は、粒状のイオン交換樹脂に、白金族金属が担持されたものである。白金族金属の担体となる粒状のイオン交換樹脂としては、特に制限されず、例えば、強塩基性アニオン交換樹脂等が挙げられる。そして、粒状のイオン交換樹脂に、公知の方法により白金族金属が担持されて、白金族金属が担持された粒状のイオン交換樹脂が得られる。 The granular ion exchange resin carrying a platinum group metal is one in which a platinum group metal is carried on a granular ion exchange resin. The particulate ion exchange resin that serves as the platinum group metal carrier is not particularly limited, and examples thereof include strongly basic anion exchange resins. Then, the granular ion exchange resin is loaded with a platinum group metal by a known method to obtain a granular ion exchange resin loaded with the platinum group metal.
金属が担持された金属イオン型の粒状の陽イオン交換樹脂は、粒状の陽イオン交換樹脂に、鉄イオン、銅イオン、ニッケルイオン、クロムイオン、コバルトイオンなどの金属が担持されたものである。担体となる粒状の陽イオン交換樹脂としては、特に制限されず、例えば、強酸性陽イオン交換樹脂等が挙げられる。そして、粒状の陽イオン交換樹脂に、公知の方法により鉄イオン、銅イオン、ニッケルイオン、クロムイオン、コバルトイオンなどの金属が担持されて、金属イオン型の粒状の陽イオン交換樹脂が得られる。 The metal ion type granular cation exchange resin on which a metal is supported is obtained by supporting a metal such as iron ion, copper ion, nickel ion, chromium ion or cobalt ion on a granular cation exchange resin. The granular cation exchange resin to be a carrier is not particularly limited, and examples thereof include strongly acidic cation exchange resins. And metal, such as an iron ion, copper ion, nickel ion, chromium ion, and cobalt ion, is carry | supported by a granular cation exchange resin by a well-known method, and a metal ion type granular cation exchange resin is obtained.
以下に、本発明に使用される触媒ユニット２１の触媒を、より具体的に説明するが、これは単に例示であって、本発明を制限するものではない。
Hereinafter, the catalyst of the
＜白金族金属担持非粒状有機多孔質イオン交換体の製造＞
（モノリス中間体の製造（Ｉ処理））
スチレン９．２８ｇ、ジビニルベンゼン０．１９ｇ、ソルビタンモノオレエート（以下ＳＭＯと略す）０．５０ｇおよび２,２'-アゾビス（イソブチロニトリル）０．２５ｇを混合し、均一に溶解させた。次に、当該スチレン/ジビニルベンゼン/ＳＭＯ/２,２'-アゾビス（イソブチロニトリル）混合物を１８０ｇの純水に添加し、遊星式撹拌装置である真空撹拌脱泡ミキサー（イーエムイー社製）を用いて減圧下撹拌して、油中水滴型エマルションを得た。このエマルションを速やかに反応容器に移し、密封後静置下で６０℃、２４時間重合させた。重合終了後、内容物を取り出し、メタノールで抽出した後、減圧乾燥して、連続マクロポア構造を有するモノリス中間体を製造した。このようにして得られたモノリス中間体（乾燥体）の内部構造をＳＥＭにより観察した。ＳＥＭ画像から、隣接する２つのマクロポアを区画する壁部は極めて細く棒状であるものの、連続気泡構造を有しており、水銀圧入法により測定したマクロポアとマクロポアが重なる部分の開口（メソポア）の平均直径は４０μｍ、全細孔容積は１８．２ｍｌ／ｇであった。
<Production of platinum group metal-supported non-particulate organic porous ion exchanger>
(Production of monolith intermediate (I treatment))
9.28 g of styrene, 0.19 g of divinylbenzene, 0.50 g of sorbitan monooleate (hereinafter abbreviated as SMO) and 0.25 g of 2,2′-azobis (isobutyronitrile) were mixed and dissolved uniformly. Next, the styrene / divinylbenzene / SMO / 2,2′-azobis (isobutyronitrile) mixture was added to 180 g of pure water, and a vacuum stirring defoaming mixer (manufactured by EM Co.) as a planetary stirring device. Was stirred under reduced pressure to obtain a water-in-oil emulsion. This emulsion was quickly transferred to a reaction vessel and allowed to polymerize at 60 ° C. for 24 hours in a static state after sealing. After completion of the polymerization, the content was taken out, extracted with methanol, and then dried under reduced pressure to produce a monolith intermediate having a continuous macropore structure. The internal structure of the monolith intermediate (dry body) thus obtained was observed by SEM. From the SEM image, although the wall part that divides two adjacent macropores is very thin and rod-shaped, it has an open cell structure, and the average of the openings (mesopores) where the macropores and macropores overlap measured by the mercury intrusion method The diameter was 40 μm and the total pore volume was 18.2 ml / g.
（モノリスの製造）
次いで、スチレン２１６．６ｇ、ジビニルベンゼン４．４ｇ、１-デカノール２２０ｇ、２,２'-アゾビス（２,４-ジメチルバレロニトリル）０．８ｇを混合し、均一に溶解させた（ＩＩ処理）。次に上記モノリス中間体を反応容器に入れ、当該スチレン/ジビニルベンゼン/1-デカノール/２,２'-アゾビス（２,４-ジメチルバレロニトリル）混合物に浸漬させ、減圧チャンバー中で脱泡した後、反応容器を密封し、静置下５０℃で２４時間重合させた。重合終了後内容物を取り出し、アセトンでソックスレー抽出した後、減圧乾燥した（ＩＩＩ処理）。
(Manufacture of monoliths)
Subsequently, 216.6 g of styrene, 4.4 g of divinylbenzene, 220 g of 1-decanol, and 0.8 g of 2,2′-azobis (2,4-dimethylvaleronitrile) were mixed and dissolved uniformly (II treatment). Next, the above monolith intermediate is placed in a reaction vessel, immersed in the styrene / divinylbenzene / 1-decanol / 2,2′-azobis (2,4-dimethylvaleronitrile) mixture, and degassed in a vacuum chamber. The reaction vessel was sealed and allowed to polymerize at 50 ° C. for 24 hours. After completion of the polymerization, the content was taken out, subjected to Soxhlet extraction with acetone, and then dried under reduced pressure (III treatment).
このようにして得られたスチレン/ジビニルベンゼン共重合体よりなる架橋成分を１．２モル％含有したモノリス（乾燥体）の内部構造を、ＳＥＭにより観察した。ＳＥＭ観察から、当該モノリスは骨格及び空孔はそれぞれ３次元的に連続し、両相が絡み合った共連続構造であった。また、ＳＥＭ画像から測定した骨格の平均太さは２０μｍであった。また、水銀圧入法により測定した、当該モノリスの三次元的に連続した空孔の平均直径は７０μｍ、全細孔容積は４．４ｍｌ／ｇであった。なお、空孔の平均直径は、水銀圧入法により得られた細孔分布曲線の極大値から求めた。 The internal structure of the monolith (dry body) containing 1.2 mol% of the crosslinking component composed of the styrene / divinylbenzene copolymer thus obtained was observed by SEM. From the SEM observation, the monolith has a co-continuous structure in which the skeleton and the vacancies are three-dimensionally continuous, and both phases are intertwined. Moreover, the average thickness of the skeleton measured from the SEM image was 20 μm. Further, the average diameter of the three-dimensionally continuous pores of the monolith measured by mercury porosimetry was 70 μm, and the total pore volume was 4.4 ml / g. The average diameter of the pores was determined from the maximum value of the pore distribution curve obtained by the mercury intrusion method.
（モノリスアニオン交換体の製造）
上記の方法で製造したモノリスをカラム状反応器に入れ、クロロスルホン酸１６００ｇと四塩化スズ４００ｇ、ジメトキシメタン２５００ｍｌからなる溶液を循環・通液して、３０℃、５時間反応させ、クロロメチル基を導入した。反応終了後、クロロメチル化モノリスをＴＨＦ/水＝２/１の混合溶媒で洗浄し、更にＴＨＦで洗浄した。このクロロメチル化モノリスにＴＨＦ１６００ｍｌとトリメチルアミン３０％水溶液１４００ｍｌを加え、６０℃、６時間反応させた。反応終了後、生成物をメタノールで洗浄し、次いで純水で洗浄してモノリスアニオン交換体を得た。
(Production of monolith anion exchanger)
The monolith produced by the above method is put into a column reactor, and a solution consisting of 1600 g of chlorosulfonic acid, 400 g of tin tetrachloride and 2500 ml of dimethoxymethane is circulated and passed through, and reacted at 30 ° C. for 5 hours to give a chloromethyl group. Was introduced. After completion of the reaction, the chloromethylated monolith was washed with a mixed solvent of THF / water = 2/1, and further washed with THF. To this chloromethylated monolith, 1600 ml of THF and 1400 ml of 30% aqueous solution of trimethylamine were added and reacted at 60 ° C. for 6 hours. After completion of the reaction, the product was washed with methanol and then with pure water to obtain a monolith anion exchanger.
得られたモノリスアニオン交換体のアニオン交換容量は、乾燥状態で４．２ｍｇ当量/ｇであり、四級アンモニウム基が定量的に導入されていることを確認した。また、ＳＥＭ画像から測定した乾燥状態での骨格の太さは２０μｍであり、水銀圧入法による測定から求めた、当該モノリスアニオン交換体の三次元的に連続した空孔の乾燥状態での平均直径は７０μｍ、乾燥状態での全細孔容積は４．４ｍｌ／ｇであった。 The obtained monolith anion exchanger had an anion exchange capacity of 4.2 mg equivalent / g in a dry state, and it was confirmed that quaternary ammonium groups were quantitatively introduced. Further, the thickness of the skeleton in the dry state measured from the SEM image is 20 μm, and the average diameter in the dry state of the three-dimensional continuous pores of the monolith anion exchanger determined from the measurement by the mercury intrusion method. Was 70 μm and the total pore volume in the dry state was 4.4 ml / g.
次に、モノリスアニオン交換体中の四級アンモニウム基の分布状態を確認するため、モノリスアニオン交換体を塩酸水溶液で処理して塩化物型とした後、ＥＰＭＡにより塩化物イオンの分布状態を観察した。その結果、塩化物イオンはモノリスアニオン交換体の骨格表面のみならず、骨格内部にも均一に分布しており、四級アンモニウム基がモノリスアニオン交換体中に均一に導入されていることが確認できた。 Next, in order to confirm the distribution state of the quaternary ammonium group in the monolith anion exchanger, the monolith anion exchanger was treated with an aqueous hydrochloric acid solution to form a chloride form, and then the distribution state of chloride ions was observed by EPMA. . As a result, it was confirmed that the chloride ions were uniformly distributed not only on the skeleton surface of the monolith anion exchanger but also inside the skeleton, and the quaternary ammonium groups were uniformly introduced into the monolith anion exchanger. It was.
（白金族金属の担持）
上記モノリスアニオン交換体をＣｌ形にイオン交換した後、乾燥状態で円柱状に切り出し、減圧乾燥した。乾燥後のモノリスアニオン交換体の重量は、１．２ｇであった。この乾燥状態のモノリスアニオン交換体を、塩化パラジウム１００ｍｇを溶解した希塩酸に２４時間浸漬し、塩化パラジウム酸形にイオン交換した。浸漬終了後、モノリスアニオン交換体を純水で数回洗浄し、ヒドラジン水溶液中に２４時間浸漬して還元処理を行った。塩化パラジウム酸形モノリスアニオン交換体が茶色であったのに対し、還元処理終了後のモノリスアニオン交換体は黒色に着色しており、パラジウム微粒状の生成が示唆された。還元後の試料は、数回純水で洗浄した後、検圧乾燥により乾燥させた。
(Supporting platinum group metals)
The monolith anion exchanger was ion-exchanged into Cl form, cut into a cylindrical shape in a dry state, and dried under reduced pressure. The weight of the monolith anion exchanger after drying was 1.2 g. This dried monolith anion exchanger was immersed in dilute hydrochloric acid in which 100 mg of palladium chloride was dissolved for 24 hours, and ion-exchanged to the palladium chloride acid form. After completion of the immersion, the monolith anion exchanger was washed several times with pure water, and immersed in an aqueous hydrazine solution for 24 hours for reduction treatment. While the chloropalladium acid type monolith anion exchanger was brown, the monolith anion exchanger after completion of the reduction treatment was colored black, suggesting the formation of fine palladium particles. The sample after the reduction was washed several times with pure water and then dried by pressure detection drying.
パラジウムの担持量をICP発光分光分析法で求めたところ、パラジウム担持量は３．９重量％であった。モノリスカチオン交換体に担持されたパラジウムの分布状態を確認するため、ＥＰＭＡによりパラジウムの分布状態を観察した。パラジウムはモノリスアニオン交換体の骨格表面のみならず、骨格内部にも分布しており、内部の方か濃度が若干高いものの、比較的均一に分布していることが確認できた。また、担持されたパラジウム粒子の平均粒子径を測定するため、透過型電子顕微鏡（ＴＥＭ）観察を行った。パラジウム微粒状の平均粒子径は、８ｎｍであった。 When the amount of palladium supported was determined by ICP emission spectroscopy, the amount of palladium supported was 3.9% by weight. In order to confirm the distribution state of palladium supported on the monolith cation exchanger, the distribution state of palladium was observed by EPMA. It was confirmed that palladium was distributed not only on the surface of the skeleton of the monolith anion exchanger but also inside the skeleton, and it was relatively uniformly distributed inside, although the concentration was slightly higher. In order to measure the average particle diameter of the supported palladium particles, observation with a transmission electron microscope (TEM) was performed. The average particle diameter of the fine palladium particles was 8 nm.
以下では、本発明によって精製されたフッ化水素酸溶液で基板を処理することにより得られた測定結果について説明する。 Below, the measurement result obtained by processing a board | substrate with the hydrofluoric acid solution refine | purified by this invention is demonstrated.
［処理される基板（サンプル）］
４インチのシリコンウェハに銅を２００ｎｍの厚みとなるようにスパッタリングで成膜した試験ウエハを使用した。
[Substrate to be processed (sample)]
A test wafer in which copper was deposited on a 4-inch silicon wafer by sputtering so as to have a thickness of 200 nm was used.
［評価方法］
エヌピイエス社製４探針法シート抵抗測定器Σ−５＋を用いて洗浄処理前後のシート抵抗を測定し、その差を記録した。銅が溶出し膜厚が減少するとシート抵抗は増加する。 ［基板処理装置］
基板処理装置としては、全協化成工業製枚葉式洗浄装置を用いた。不活性ガスとしては９９．９９９％の窒素ガスを用い、ウエハの回転数は５００ｒｐｍで一定とし、処理液ノズルから処理水を１５分間供給し試験ウエハを洗浄処理した。
[Evaluation method]
The sheet resistance before and after the cleaning treatment was measured using a 4-probe sheet resistance measuring device Σ-5 + manufactured by NPIS, and the difference was recorded. As copper elutes and the film thickness decreases, the sheet resistance increases. [Substrate processing equipment]
As the substrate processing apparatus, a single wafer cleaning apparatus manufactured by Zenkyo Kasei Kogyo was used. 99.999% nitrogen gas was used as the inert gas, the wafer rotation speed was kept constant at 500 rpm, and the test wafer was cleaned by supplying process water from the process liquid nozzle for 15 minutes.
［原水（超純水）］
超純水については、オルガノ株式会社開発センター内に設置されている超純水製造装置の二次純水を使用した。超純水製造装置の出口での水質は次の表１のとおりである。
[Raw water (ultra pure water)]
As for ultrapure water, secondary pure water of an ultrapure water production apparatus installed in Organo Corporation Development Center was used. The water quality at the outlet of the ultrapure water production apparatus is as shown in Table 1 below.
［測定］
溶存酸素濃度についてはオービスフェア製ｍｏｄｅｌ４１０型を、溶存水素濃度については東亜ディーケーケー社製溶存水素計ＤＨＤＩ−１を用いて測定した。
[Measurement]
The dissolved oxygen concentration was measured using an Orbis Fair model 410, and the dissolved hydrogen concentration was measured using a dissolved hydrogen meter DHDI-1 manufactured by Toa DK Corporation.
［実施例１］
９９．９９９％の窒素ガスを充填した混合水貯留槽に５０％フッ化水素酸溶液と超純水を容積比で１：１００となるように投入し、希フッ酸溶液を調製した。この希フッ酸溶液に中空糸膜を介して水素ガスを添加した後、酸化剤除去装置として準備したパラジウム担持モノリスに通液し酸素および過酸化水素を除去した後、酸素ガス濃度を２％以下に保った基板処理装置の処理室に導入し、試験ウエハの洗浄を行った。水素を添加しない場合、およびパラジウム担持モノリスに通液しない場合についても試験を行った。洗浄前後で試験ウエハのシート抵抗を測定し、その増分を算出した。なお溶存酸素濃度、溶存水素濃度は処理室直前にて測定を行っている。結果を表２に示す。
[Example 1]
A 50% hydrofluoric acid solution and ultrapure water were introduced into a mixed water storage tank filled with 99.999% nitrogen gas so that the volume ratio was 1: 100 to prepare a diluted hydrofluoric acid solution. Hydrogen gas is added to this dilute hydrofluoric acid solution through a hollow fiber membrane, and then passed through a palladium-supported monolith prepared as an oxidant removing device to remove oxygen and hydrogen peroxide. The oxygen gas concentration is 2% or less. The substrate was introduced into the processing chamber of the substrate processing apparatus, and the test wafer was cleaned. The test was also performed when no hydrogen was added and when the liquid was not passed through the palladium-supported monolith. The sheet resistance of the test wafer was measured before and after cleaning, and the increment was calculated. The dissolved oxygen concentration and dissolved hydrogen concentration are measured immediately before the treatment chamber. The results are shown in Table 2.
水素を添加したのみ、あるいは水素を添加せず酸化剤除去装置を通液したのみでは銅の腐食が起きている。また溶存水素濃度が１０μｇ／Ｌ以下、かつ溶存酸素濃度が２μｇ／Ｌ以上では、銅の腐食は完全には抑制されていない。しかし、上記希フッ酸に水素を添加し、溶存酸素濃度を２μｇ／Ｌ以下、かつ過酸化水素濃度を２μｇ／Ｌ以下とした希フッ酸で処理すると、銅の腐食はほぼ抑制されることは明らかである。また、さらに溶存水素濃度を１０μｇ／Ｌとすると、銅の腐食は完全に抑制された。 Corrosion of copper occurs only when hydrogen is added, or when hydrogen is not added and only the liquid is passed through the oxidant removing device. Further, when the dissolved hydrogen concentration is 10 μg / L or less and the dissolved oxygen concentration is 2 μg / L or more, the corrosion of copper is not completely suppressed. However, when hydrogen is added to the dilute hydrofluoric acid and treated with dilute hydrofluoric acid with a dissolved oxygen concentration of 2 μg / L or less and a hydrogen peroxide concentration of 2 μg / L or less, corrosion of copper is substantially suppressed. it is obvious. Further, when the dissolved hydrogen concentration was 10 μg / L, copper corrosion was completely suppressed.
［実施例２］
上記枚葉式洗浄装置の処理室内の酸素ガス濃度を調整し、実施例１と同じ試験を行った。結果を表３に示す。
[Example 2]
The same test as in Example 1 was performed by adjusting the oxygen gas concentration in the processing chamber of the single wafer cleaning apparatus. The results are shown in Table 3.
処理室内の酸素ガス濃度を２％以下とすれば、完全に銅の腐食を抑制できた。この評価結果から、次の事が分かる。上記の希フッ酸に水素を添加し、酸化剤除去装置を通液して酸素および過酸化水素を除去した処理液を用い基板処理を行う際、処理室内の酸素ガス濃度は２％以下にすると、基板表面に露出した銅の溶出を完全に抑制できることが分かった。 If the oxygen gas concentration in the processing chamber was 2% or less, copper corrosion could be completely suppressed. From this evaluation result, the following can be understood. When substrate processing is performed using a processing solution in which hydrogen is added to the dilute hydrofluoric acid and oxygen and hydrogen peroxide are removed by passing through an oxidizing agent removing apparatus, the oxygen gas concentration in the processing chamber is set to 2% or less. It was found that elution of copper exposed on the substrate surface can be completely suppressed.
１０・・・ＨＦ精製ユニット ２１，３１・・・基板処理装置 ２２・・・混合水貯留槽
２３・・・処理液供給ライン ２５・・・水素添加装置 ２７・・・不活性ガス供給ライン
２９・・・酸化剤除去装置 ３１・・・ＨＦ供給ライン ３２・・・超純水供給ライン
１０１・・・処理室
DESCRIPTION OF
Claims (17)
前記基板処理装置に水素添加装置および白金族系金属触媒を設置し、
少なくともフッ化水素酸を含む溶液に前記水素添加装置から水素を添加し、
該水素が添加された前記溶液を前記白金族系金属触媒に通水して得た、溶存酸素濃度が２μｇ／Ｌ以下、溶存過酸化水素濃度が２μｇ／Ｌ以下の処理液によって、前記基板を処理することを特徴とする基板処理方法。 A substrate processing method for disposing a substrate in a processing chamber of a substrate processing apparatus and processing the substrate with a processing liquid,
A hydrogenation device and a platinum group metal catalyst are installed in the substrate processing apparatus,
Adding hydrogen from the hydrogenation device to a solution containing at least hydrofluoric acid,
The substrate was treated with a treatment solution obtained by passing the hydrogen-added solution through the platinum group metal catalyst and having a dissolved oxygen concentration of 2 μg / L or less and a dissolved hydrogen peroxide concentration of 2 μg / L or less. A substrate processing method characterized by processing.
前記基板を処理する処理室と、
槽内でフッ化水素酸と超純水とを混合して希フッ酸を調製し貯留する混合水貯留槽と、
前記フッ化水素酸を前記混合水貯留槽に供給するフッ化水素酸供給手段と、
前記超純水を前記混合水貯留槽に供給する超純水供給手段と、
前記希フッ酸を基板処理液として前記処理室に送る処理液供給手段と、を有し、
前記フッ化水素酸供給手段は、前記フッ化水素酸に水素を添加する水素添加装置と、当該水素が添加されたフッ化水素酸中の溶存酸素および過酸化水素を除去するための酸化剤除去装置とを備えており、
前記水素が添加された前記フッ化水素酸を前記酸化剤除去装置に通して溶存酸素および過酸化水素を除去した後に前記混合水貯留槽に供給して得た、溶存酸素濃度が２μｇ／Ｌ以下、溶存過酸化水素濃度が２μｇ／Ｌ以下の処理液によって、前記基板を処理することを特徴とする基板処理装置。 A substrate processing apparatus for processing a substrate with a processing liquid,
A processing chamber for processing the substrate;
A mixed water storage tank that mixes hydrofluoric acid and ultrapure water in the tank to prepare and store dilute hydrofluoric acid,
Hydrofluoric acid supply means for supplying the hydrofluoric acid to the mixed water storage tank;
Ultrapure water supply means for supplying the ultrapure water to the mixed water storage tank;
Processing liquid supply means for sending the dilute hydrofluoric acid to the processing chamber as a substrate processing liquid,
The hydrofluoric acid supply means includes a hydrogen addition device for adding hydrogen to the hydrofluoric acid, and an oxidant removal for removing dissolved oxygen and hydrogen peroxide in the hydrofluoric acid to which the hydrogen has been added. Equipment,
The hydrofluoric acid to which the hydrogen has been added is passed through the oxidant removing device to remove dissolved oxygen and hydrogen peroxide, and then supplied to the mixed water storage tank, and the dissolved oxygen concentration is 2 μg / L or less. A substrate processing apparatus, wherein the substrate is processed with a processing solution having a dissolved hydrogen peroxide concentration of 2 μg / L or less.
前記基板を処理する処理室と、
槽内でフッ化水素酸と超純水とを混合して希フッ酸を調製し貯留する混合水貯留槽と、
前記フッ化水素酸を前記混合水貯留槽に供給するフッ化水素酸供給手段と、
前記超純水を前記混合水貯留槽に供給する超純水供給手段と、
前記希フッ酸を基板処理液として前記処理室に送る処理液供給手段と、を有し、
前記処理液供給手段は、前記希フッ酸に水素を添加する水素添加装置と、当該水素が添加された希フッ酸中の溶存酸素および過酸化水素を除去するための酸化剤除去装置とを備えており、
前記水素が添加された前記希フッ酸を前記酸化剤除去装置に通して溶存酸素および過酸化水素を除去して得た、溶存酸素濃度が２μｇ／Ｌ以下、溶存過酸化水素濃度が２μｇ／Ｌ以下の処理液によって、前記基板を処理することを特徴とする基板処理装置。 A substrate processing apparatus for processing a substrate with a processing liquid,
A processing chamber for processing the substrate;
A mixed water storage tank that mixes hydrofluoric acid and ultrapure water in the tank to prepare and store dilute hydrofluoric acid,
Hydrofluoric acid supply means for supplying the hydrofluoric acid to the mixed water storage tank;
Ultrapure water supply means for supplying the ultrapure water to the mixed water storage tank;
Processing liquid supply means for sending the dilute hydrofluoric acid to the processing chamber as a substrate processing liquid,
The treatment liquid supply means includes a hydrogen adding device for adding hydrogen to the diluted hydrofluoric acid, and an oxidant removing device for removing dissolved oxygen and hydrogen peroxide in the diluted hydrofluoric acid to which the hydrogen has been added. And
The diluted hydrofluoric acid to which the hydrogen has been added is passed through the oxidant removing device to remove dissolved oxygen and hydrogen peroxide. The dissolved oxygen concentration is 2 μg / L or less, and the dissolved hydrogen peroxide concentration is 2 μg / L. A substrate processing apparatus for processing the substrate with the following processing liquid.
Priority Applications (8)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2013206447A JP6100664B2 (en) | 2013-10-01 | 2013-10-01 | Hydrofluoric acid aqueous solution purification method, substrate processing method and substrate processing apparatus |
| PCT/JP2014/074481 WO2015045975A1 (en) | 2013-09-25 | 2014-09-17 | Substrate treatment method and substrate treatment device |
| CN201480052961.5A CN105593976B (en) | 2013-09-25 | 2014-09-17 | Substrate processing method and substrate processing apparatus |
| KR1020167006545A KR101914843B1 (en) | 2013-09-25 | 2014-09-17 | Substrate treatment method and substrate treatment device |
| US15/023,161 US11004674B2 (en) | 2013-09-25 | 2014-09-17 | Substrate treatment method and substrate treatment equipment |
| SG11201602220TA SG11201602220TA (en) | 2013-09-25 | 2014-09-17 | Substrate treatment method and substrate treatment device |
| TW103132823A TWI623031B (en) | 2013-09-25 | 2014-09-23 | Substrate processing method and substrate processing device |
| US17/241,522 US11901174B2 (en) | 2013-09-25 | 2021-04-27 | Substrate treatment method and substrate treatment equipment |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2013206447A JP6100664B2 (en) | 2013-10-01 | 2013-10-01 | Hydrofluoric acid aqueous solution purification method, substrate processing method and substrate processing apparatus |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JP2015067532A JP2015067532A (en) | 2015-04-13 |
| JP6100664B2 true JP6100664B2 (en) | 2017-03-22 |
Family
ID=52834586
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP2013206447A Active JP6100664B2 (en) | 2013-09-25 | 2013-10-01 | Hydrofluoric acid aqueous solution purification method, substrate processing method and substrate processing apparatus |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP6100664B2 (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2017119233A (en) * | 2015-12-28 | 2017-07-06 | オルガノ株式会社 | Method of purifying organic solvent |
Family Cites Families (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP3105902B2 (en) * | 1990-06-19 | 2000-11-06 | 株式会社東芝 | Surface treatment method and surface treatment device |
| JP2003136077A (en) * | 2001-10-31 | 2003-05-13 | Nec Corp | Cleaning water or immersion water production equipment used for semiconductor production |
| JP5390808B2 (en) * | 2008-08-27 | 2014-01-15 | 大日本スクリーン製造株式会社 | Substrate processing apparatus and substrate processing method |
| JP5231300B2 (en) * | 2009-03-18 | 2013-07-10 | オルガノ株式会社 | Platinum group metal supported catalyst, method for producing hydrogen peroxide decomposition treatment water, method for producing dissolved oxygen removal treatment water, and method for cleaning electronic components |
-
2013
- 2013-10-01 JP JP2013206447A patent/JP6100664B2/en active Active
Also Published As
| Publication number | Publication date |
|---|---|
| JP2015067532A (en) | 2015-04-13 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| JP6117348B2 (en) | Method and system for cleaning copper exposed substrate | |
| US11901174B2 (en) | Substrate treatment method and substrate treatment equipment | |
| JP6423211B2 (en) | Substrate processing method and substrate processing apparatus | |
| JP5329463B2 (en) | Production method for hydrogen peroxide decomposition treated water, production apparatus for hydrogen peroxide decomposition treated water, treatment tank, production method for ultra pure water, production apparatus for ultra pure water, production method for hydrogen dissolved water, production apparatus for hydrogen dissolved water , Ozone-dissolved water manufacturing method, ozone-dissolved water manufacturing apparatus, and electronic component cleaning method | |
| TWI476048B (en) | Method for producing treated water of platinum group metal, catalytic water for decomposing hydrogen peroxide, method for producing water for removing dissolved oxygen, and method for cleaning electronic parts | |
| JP5604143B2 (en) | Dissolved oxygen-removed water production method, dissolved oxygen-removed water production device, dissolved oxygen treatment tank, ultrapure water production method, hydrogen-dissolved water production method, hydrogen-dissolved water production device, and electronic component cleaning method | |
| JP5231299B2 (en) | Platinum group metal supported catalyst, method for producing hydrogen peroxide decomposition treatment water, method for producing dissolved oxygen removal treatment water, and method for cleaning electronic components | |
| JP5525754B2 (en) | Platinum group metal supported catalyst, method for producing hydrogen peroxide decomposition treatment water, method for producing dissolved oxygen removal treatment water, and method for cleaning electronic components | |
| JP5421689B2 (en) | Platinum group metal supported catalyst, method for producing hydrogen peroxide decomposition treatment water, method for producing dissolved oxygen removal treatment water, and method for cleaning electronic components | |
| JP6100664B2 (en) | Hydrofluoric acid aqueous solution purification method, substrate processing method and substrate processing apparatus | |
| JP6529793B2 (en) | Method of treating liquid to be treated and treatment apparatus of liquid to be treated | |
| JP2014079722A (en) | Ozone water manufacturing method | |
| JP6415100B2 (en) | Method for treating exposed molybdenum substrate | |
| JP6433577B2 (en) | Manufacturing method of organic acid ester liquid, and manufacturing method of resist solvent for electronic component manufacturing or rinsing liquid for electronic component manufacturing |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| A621 | Written request for application examination |
Free format text: JAPANESE INTERMEDIATE CODE: A621 Effective date: 20160516 |
|
| TRDD | Decision of grant or rejection written | ||
| A01 | Written decision to grant a patent or to grant a registration (utility model) |
Free format text: JAPANESE INTERMEDIATE CODE: A01 Effective date: 20170131 |
|
| A61 | First payment of annual fees (during grant procedure) |
Free format text: JAPANESE INTERMEDIATE CODE: A61 Effective date: 20170223 |
|
| R150 | Certificate of patent or registration of utility model |
Ref document number: 6100664 Country of ref document: JP Free format text: JAPANESE INTERMEDIATE CODE: R150 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |