TW201600857A - Method of collecting analytic sample, and use of the method - Google Patents
Method of collecting analytic sample, and use of the method Download PDFInfo
- Publication number
- TW201600857A TW201600857A TW104117486A TW104117486A TW201600857A TW 201600857 A TW201600857 A TW 201600857A TW 104117486 A TW104117486 A TW 104117486A TW 104117486 A TW104117486 A TW 104117486A TW 201600857 A TW201600857 A TW 201600857A
- Authority
- TW
- Taiwan
- Prior art keywords
- organic film
- organic
- vapor
- analysis
- film
- Prior art date
Links
- 238000000034 method Methods 0.000 title claims abstract description 110
- 238000004458 analytical method Methods 0.000 claims abstract description 88
- 239000000463 material Substances 0.000 claims abstract description 23
- 239000000758 substrate Substances 0.000 claims description 88
- 238000011084 recovery Methods 0.000 claims description 42
- 238000004519 manufacturing process Methods 0.000 claims description 27
- 238000007726 management method Methods 0.000 claims description 25
- 239000000203 mixture Substances 0.000 claims description 18
- 239000002253 acid Substances 0.000 claims description 15
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 11
- 239000003960 organic solvent Substances 0.000 claims description 9
- 239000007789 gas Substances 0.000 claims description 8
- 238000001514 detection method Methods 0.000 claims description 6
- 239000003513 alkali Substances 0.000 claims description 3
- 239000000538 analytical sample Substances 0.000 abstract 5
- 238000011002 quantification Methods 0.000 abstract 1
- 239000010408 film Substances 0.000 description 272
- 239000002904 solvent Substances 0.000 description 57
- 239000000126 substance Substances 0.000 description 47
- 239000012535 impurity Substances 0.000 description 17
- 206010040844 Skin exfoliation Diseases 0.000 description 14
- 238000011109 contamination Methods 0.000 description 14
- 230000035945 sensitivity Effects 0.000 description 11
- 229910052707 ruthenium Inorganic materials 0.000 description 10
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 9
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 9
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 9
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 description 9
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 9
- 238000010438 heat treatment Methods 0.000 description 9
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 9
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 8
- 230000015572 biosynthetic process Effects 0.000 description 8
- 238000000354 decomposition reaction Methods 0.000 description 8
- -1 heteroaromatic hydrocarbon Chemical class 0.000 description 8
- 239000007788 liquid Substances 0.000 description 8
- 229910017604 nitric acid Inorganic materials 0.000 description 8
- 239000011368 organic material Substances 0.000 description 8
- 239000010409 thin film Substances 0.000 description 8
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 6
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 6
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 6
- 239000002585 base Substances 0.000 description 6
- 238000009835 boiling Methods 0.000 description 6
- 230000005484 gravity Effects 0.000 description 6
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 6
- 239000004810 polytetrafluoroethylene Substances 0.000 description 6
- WGTYBPLFGIVFAS-UHFFFAOYSA-M tetramethylammonium hydroxide Chemical compound [OH-].C[N+](C)(C)C WGTYBPLFGIVFAS-UHFFFAOYSA-M 0.000 description 6
- 239000007864 aqueous solution Substances 0.000 description 5
- 150000001875 compounds Chemical class 0.000 description 5
- 229910052698 phosphorus Inorganic materials 0.000 description 5
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 4
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 description 4
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 4
- 239000002033 PVDF binder Substances 0.000 description 4
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 4
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 4
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 4
- 238000004140 cleaning Methods 0.000 description 4
- 150000002500 ions Chemical class 0.000 description 4
- 238000005259 measurement Methods 0.000 description 4
- 230000003287 optical effect Effects 0.000 description 4
- VLTRZXGMWDSKGL-UHFFFAOYSA-N perchloric acid Chemical compound OCl(=O)(=O)=O VLTRZXGMWDSKGL-UHFFFAOYSA-N 0.000 description 4
- 239000011574 phosphorus Substances 0.000 description 4
- 229920002493 poly(chlorotrifluoroethylene) Polymers 0.000 description 4
- 239000005023 polychlorotrifluoroethylene (PCTFE) polymer Substances 0.000 description 4
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 4
- 239000000243 solution Substances 0.000 description 4
- 238000004528 spin coating Methods 0.000 description 4
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- 230000003373 anti-fouling effect Effects 0.000 description 3
- 238000004040 coloring Methods 0.000 description 3
- 238000010828 elution Methods 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 238000002354 inductively-coupled plasma atomic emission spectroscopy Methods 0.000 description 3
- 229910010272 inorganic material Inorganic materials 0.000 description 3
- 239000011147 inorganic material Substances 0.000 description 3
- 238000009413 insulation Methods 0.000 description 3
- 229910052741 iridium Inorganic materials 0.000 description 3
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 3
- 239000012528 membrane Substances 0.000 description 3
- 150000002894 organic compounds Chemical class 0.000 description 3
- 238000005498 polishing Methods 0.000 description 3
- 230000002265 prevention Effects 0.000 description 3
- 239000007787 solid Substances 0.000 description 3
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 3
- 230000008016 vaporization Effects 0.000 description 3
- OGGKVJMNFFSDEV-UHFFFAOYSA-N 3-methyl-n-[4-[4-(n-(3-methylphenyl)anilino)phenyl]phenyl]-n-phenylaniline Chemical compound CC1=CC=CC(N(C=2C=CC=CC=2)C=2C=CC(=CC=2)C=2C=CC(=CC=2)N(C=2C=CC=CC=2)C=2C=C(C)C=CC=2)=C1 OGGKVJMNFFSDEV-UHFFFAOYSA-N 0.000 description 2
- VFUDMQLBKNMONU-UHFFFAOYSA-N 9-[4-(4-carbazol-9-ylphenyl)phenyl]carbazole Chemical group C12=CC=CC=C2C2=CC=CC=C2N1C1=CC=C(C=2C=CC(=CC=2)N2C3=CC=CC=C3C3=CC=CC=C32)C=C1 VFUDMQLBKNMONU-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 2
- 229910021529 ammonia Inorganic materials 0.000 description 2
- 229910052796 boron Inorganic materials 0.000 description 2
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 description 2
- 238000005251 capillar electrophoresis Methods 0.000 description 2
- 238000009841 combustion method Methods 0.000 description 2
- 229920001577 copolymer Polymers 0.000 description 2
- 238000011978 dissolution method Methods 0.000 description 2
- 238000004817 gas chromatography Methods 0.000 description 2
- 238000001336 glow discharge atomic emission spectroscopy Methods 0.000 description 2
- 229910052736 halogen Inorganic materials 0.000 description 2
- 150000002367 halogens Chemical class 0.000 description 2
- QOSATHPSBFQAML-UHFFFAOYSA-N hydrogen peroxide;hydrate Chemical compound O.OO QOSATHPSBFQAML-UHFFFAOYSA-N 0.000 description 2
- TUJKJAMUKRIRHC-UHFFFAOYSA-N hydroxyl Chemical compound [OH] TUJKJAMUKRIRHC-UHFFFAOYSA-N 0.000 description 2
- 238000004255 ion exchange chromatography Methods 0.000 description 2
- GKOZUEZYRPOHIO-UHFFFAOYSA-N iridium atom Chemical compound [Ir] GKOZUEZYRPOHIO-UHFFFAOYSA-N 0.000 description 2
- 229910052747 lanthanoid Inorganic materials 0.000 description 2
- 150000002602 lanthanoids Chemical class 0.000 description 2
- 238000004811 liquid chromatography Methods 0.000 description 2
- 239000007791 liquid phase Substances 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000010453 quartz Substances 0.000 description 2
- 238000010206 sensitivity analysis Methods 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- 238000000638 solvent extraction Methods 0.000 description 2
- BFKJFAAPBSQJPD-UHFFFAOYSA-N tetrafluoroethene Chemical group FC(F)=C(F)F BFKJFAAPBSQJPD-UHFFFAOYSA-N 0.000 description 2
- 238000005011 time of flight secondary ion mass spectroscopy Methods 0.000 description 2
- 238000000624 total reflection X-ray fluorescence spectroscopy Methods 0.000 description 2
- XZZNDPSIHUTMOC-UHFFFAOYSA-N triphenyl phosphate Chemical compound C=1C=CC=CC=1OP(OC=1C=CC=CC=1)(=O)OC1=CC=CC=C1 XZZNDPSIHUTMOC-UHFFFAOYSA-N 0.000 description 2
- 238000007738 vacuum evaporation Methods 0.000 description 2
- AZFHXIBNMPIGOD-LNTINUHCSA-N (z)-4-hydroxypent-3-en-2-one;iridium Chemical compound [Ir].C\C(O)=C\C(C)=O.C\C(O)=C\C(C)=O.C\C(O)=C\C(C)=O AZFHXIBNMPIGOD-LNTINUHCSA-N 0.000 description 1
- 241000208340 Araliaceae Species 0.000 description 1
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 description 1
- XMWRBQBLMFGWIX-UHFFFAOYSA-N C60 fullerene Chemical compound C12=C3C(C4=C56)=C7C8=C5C5=C9C%10=C6C6=C4C1=C1C4=C6C6=C%10C%10=C9C9=C%11C5=C8C5=C8C7=C3C3=C7C2=C1C1=C2C4=C6C4=C%10C6=C9C9=C%11C5=C5C8=C3C3=C7C1=C1C2=C4C6=C2C9=C5C3=C12 XMWRBQBLMFGWIX-UHFFFAOYSA-N 0.000 description 1
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- 229910052684 Cerium Inorganic materials 0.000 description 1
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 description 1
- 229910052692 Dysprosium Inorganic materials 0.000 description 1
- 229910052691 Erbium Inorganic materials 0.000 description 1
- 229910052693 Europium Inorganic materials 0.000 description 1
- 229910052688 Gadolinium Inorganic materials 0.000 description 1
- 229910052689 Holmium Inorganic materials 0.000 description 1
- 229910052765 Lutetium Inorganic materials 0.000 description 1
- 229910052779 Neodymium Inorganic materials 0.000 description 1
- 235000005035 Panax pseudoginseng ssp. pseudoginseng Nutrition 0.000 description 1
- 235000003140 Panax quinquefolius Nutrition 0.000 description 1
- 229910052777 Praseodymium Inorganic materials 0.000 description 1
- 229910052772 Samarium Inorganic materials 0.000 description 1
- 229910052771 Terbium Inorganic materials 0.000 description 1
- 229910052776 Thorium Inorganic materials 0.000 description 1
- 229910052775 Thulium Inorganic materials 0.000 description 1
- 229910052770 Uranium Inorganic materials 0.000 description 1
- 229910052769 Ytterbium Inorganic materials 0.000 description 1
- OMOVVBIIQSXZSZ-UHFFFAOYSA-N [6-(4-acetyloxy-5,9a-dimethyl-2,7-dioxo-4,5a,6,9-tetrahydro-3h-pyrano[3,4-b]oxepin-5-yl)-5-formyloxy-3-(furan-3-yl)-3a-methyl-7-methylidene-1a,2,3,4,5,6-hexahydroindeno[1,7a-b]oxiren-4-yl] 2-hydroxy-3-methylpentanoate Chemical compound CC12C(OC(=O)C(O)C(C)CC)C(OC=O)C(C3(C)C(CC(=O)OC4(C)COC(=O)CC43)OC(C)=O)C(=C)C32OC3CC1C=1C=COC=1 OMOVVBIIQSXZSZ-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 150000001340 alkali metals Chemical class 0.000 description 1
- 229910052784 alkaline earth metal Inorganic materials 0.000 description 1
- 150000001342 alkaline earth metals Chemical class 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- 239000012491 analyte Substances 0.000 description 1
- 229910052787 antimony Inorganic materials 0.000 description 1
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 1
- 229910052785 arsenic Inorganic materials 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 238000001479 atomic absorption spectroscopy Methods 0.000 description 1
- 229910052788 barium Inorganic materials 0.000 description 1
- 229910052790 beryllium Inorganic materials 0.000 description 1
- 229910052797 bismuth Inorganic materials 0.000 description 1
- 229910052794 bromium Inorganic materials 0.000 description 1
- 229910052793 cadmium Inorganic materials 0.000 description 1
- 229910052792 caesium Inorganic materials 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- 239000011575 calcium Substances 0.000 description 1
- 239000000920 calcium hydroxide Substances 0.000 description 1
- 229910001861 calcium hydroxide Inorganic materials 0.000 description 1
- 229910052800 carbon group element Inorganic materials 0.000 description 1
- 238000005266 casting Methods 0.000 description 1
- 229910052798 chalcogen Inorganic materials 0.000 description 1
- 150000001787 chalcogens Chemical class 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 239000000356 contaminant Substances 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 230000006837 decompression Effects 0.000 description 1
- 238000001548 drop coating Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000005684 electric field Effects 0.000 description 1
- 238000009713 electroplating Methods 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 229910003472 fullerene Inorganic materials 0.000 description 1
- 229910052733 gallium Inorganic materials 0.000 description 1
- 229910052732 germanium Inorganic materials 0.000 description 1
- 235000008434 ginseng Nutrition 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 229910052735 hafnium Inorganic materials 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 229910052738 indium Inorganic materials 0.000 description 1
- 238000009616 inductively coupled plasma Methods 0.000 description 1
- 238000001095 inductively coupled plasma mass spectrometry Methods 0.000 description 1
- 229910052740 iodine Inorganic materials 0.000 description 1
- 238000007733 ion plating Methods 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 230000001678 irradiating effect Effects 0.000 description 1
- 229910052746 lanthanum Inorganic materials 0.000 description 1
- 238000000608 laser ablation Methods 0.000 description 1
- 229910052745 lead Inorganic materials 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- 238000004020 luminiscence type Methods 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 229910052748 manganese Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 229910052750 molybdenum Inorganic materials 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 229910052758 niobium Inorganic materials 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 229910052755 nonmetal Inorganic materials 0.000 description 1
- 150000002843 nonmetals Chemical class 0.000 description 1
- 125000002524 organometallic group Chemical group 0.000 description 1
- 229910052762 osmium Inorganic materials 0.000 description 1
- 238000006864 oxidative decomposition reaction Methods 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052763 palladium Inorganic materials 0.000 description 1
- 239000012071 phase Substances 0.000 description 1
- IEQIEDJGQAUEQZ-UHFFFAOYSA-N phthalocyanine Chemical compound N1C(N=C2C3=CC=CC=C3C(N=C3C4=CC=CC=C4C(=N4)N3)=N2)=C(C=CC=C2)C2=C1N=C1C2=CC=CC=C2C4=N1 IEQIEDJGQAUEQZ-UHFFFAOYSA-N 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 229910052696 pnictogen Inorganic materials 0.000 description 1
- 150000003063 pnictogens Chemical class 0.000 description 1
- 125000005575 polycyclic aromatic hydrocarbon group Chemical group 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 150000004032 porphyrins Chemical class 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 238000002203 pretreatment Methods 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 238000012552 review Methods 0.000 description 1
- 229910052702 rhenium Inorganic materials 0.000 description 1
- 229910052703 rhodium Inorganic materials 0.000 description 1
- 229910052701 rubidium Inorganic materials 0.000 description 1
- BPEVHDGLPIIAGH-UHFFFAOYSA-N ruthenium(3+) Chemical compound [Ru+3] BPEVHDGLPIIAGH-UHFFFAOYSA-N 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 229910052706 scandium Inorganic materials 0.000 description 1
- 229910052711 selenium Inorganic materials 0.000 description 1
- 238000012764 semi-quantitative analysis Methods 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 238000004544 sputter deposition Methods 0.000 description 1
- 229910052712 strontium Inorganic materials 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 229920003002 synthetic resin Polymers 0.000 description 1
- 239000000057 synthetic resin Substances 0.000 description 1
- 229910052715 tantalum Inorganic materials 0.000 description 1
- 229910052714 tellurium Inorganic materials 0.000 description 1
- 229910052716 thallium Inorganic materials 0.000 description 1
- 238000002230 thermal chemical vapour deposition Methods 0.000 description 1
- 238000010896 thin film analysis Methods 0.000 description 1
- 229910052718 tin Inorganic materials 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 229910052721 tungsten Inorganic materials 0.000 description 1
- 229910052720 vanadium Inorganic materials 0.000 description 1
- 239000012808 vapor phase Substances 0.000 description 1
- 238000009834 vaporization Methods 0.000 description 1
- 230000000007 visual effect Effects 0.000 description 1
- 230000003313 weakening effect Effects 0.000 description 1
- 229910052727 yttrium Inorganic materials 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- 229910052726 zirconium Inorganic materials 0.000 description 1
Classifications
-
- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K50/00—Organic light-emitting devices
- H10K50/10—OLEDs or polymer light-emitting diodes [PLED]
- H10K50/11—OLEDs or polymer light-emitting diodes [PLED] characterised by the electroluminescent [EL] layers
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J7/00—Chemical treatment or coating of shaped articles made of macromolecular substances
-
- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N1/00—Sampling; Preparing specimens for investigation
- G01N1/28—Preparing specimens for investigation including physical details of (bio-)chemical methods covered elsewhere, e.g. G01N33/50, C12Q
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Physics & Mathematics (AREA)
- Immunology (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Biochemistry (AREA)
- General Health & Medical Sciences (AREA)
- General Physics & Mathematics (AREA)
- Life Sciences & Earth Sciences (AREA)
- Pathology (AREA)
- Analytical Chemistry (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Optics & Photonics (AREA)
- Sampling And Sample Adjustment (AREA)
- Other Investigation Or Analysis Of Materials By Electrical Means (AREA)
Abstract
Description
本發明係關於分析用樣品之回收方法、分析方法、品質管理方法、製造方法及裝置。 The present invention relates to a method for recovering a sample for analysis, an analysis method, a quality management method, a manufacturing method, and an apparatus.
目前於各領域，已有利用於物品表面上形成膜的技術。此種膜係以例如，著色、拋光、防鏽、防污、防霧、絕緣、賦予導電性等各式各樣的目的被形成。例如於電子裝置、光學裝置、生物裝置、磁性裝置等之領域形成具有特定機能的膜已被進行。又，伴隨此等，為了評價物品之性能、品質等，膜中所含成分之分析成為重要。 Currently in various fields, it has been advantageous to use a technique for forming a film on the surface of an article. Such a film is formed for various purposes such as coloring, polishing, rust prevention, antifouling, antifogging, insulation, and imparting conductivity. Forming a film having a specific function, for example, in the fields of an electronic device, an optical device, a biological device, a magnetic device, or the like, has been performed. Further, along with these, in order to evaluate the performance, quality, and the like of the article, analysis of the components contained in the film is important.
例如，於許多有機電子裝置(organic electronics device)已使用含有有機物的薄膜(有機薄膜)。為了評價此類有機電子裝置之性能、品質等，分析該裝置上形成的有機薄膜之成分成為必要。例如，成為有機薄膜的材料的有機化合物係冀望對裝置特性無影響，且為雜質少的高純度品。因此，對該有機化合物的各種純化方法及分析方法正被開發。又，與成為材料的有機化合物同樣地，認為有機薄膜中之雜質亦對裝置特性有影響。除了來自材料的污染之外，藉由來自成膜步驟的污染(例如來自裝置、操作的污染)等，於有機薄膜有混入多種雜質之虞。於製作高品質的有機薄膜上，有必要於彼等雜質進行微量區域的評價。 For example, a film (organic film) containing an organic substance has been used in many organic electronic devices. In order to evaluate the performance, quality, and the like of such an organic electronic device, it is necessary to analyze the composition of the organic thin film formed on the device. For example, an organic compound which is a material of an organic thin film is a high-purity product which does not affect the device characteristics and which has few impurities. Therefore, various purification methods and analysis methods for the organic compound are being developed. Further, similarly to the organic compound to be a material, it is considered that impurities in the organic film also affect the device characteristics. In addition to contamination from materials, organic thin films are contaminated with various impurities by contamination from the film forming step (for example, contamination from equipment, handling). In the production of high-quality organic films, it is necessary to evaluate the trace regions of their impurities.
就分析於有機薄膜所含成分的方法而言，例如可列舉(1)於基板 上之有機薄膜照射離子或X射線等，而直接測定該有機薄膜中之雜質的方法(XPS、XRD、TXRF、TOF-SIMS、SIMS、GD-OES等)；(2)將有有機薄膜形成的基板浸漬於有機溶媒中，而將有機薄膜溶解於有機溶媒後，處理溶解液而測定的方法(ICP-MS、IC、LC、GC等)；(3)將基板上之有機薄膜以高溫處理後，而測定的方法(ICP-MS、GC等)。例如，(1)之方法已記載於非專利文獻1至4。 For the method of analyzing the components contained in the organic film, for example, (1) a substrate can be cited. The method of directly measuring the impurities in the organic film by irradiating ions or X-rays, etc. (XPS, XRD, TXRF, TOF-SIMS, SIMS, GD-OES, etc.); (2) forming an organic film a method in which a substrate is immersed in an organic solvent, and an organic film is dissolved in an organic solvent, and the solution is treated to measure the solution (ICP-MS, IC, LC, GC, etc.); (3) after the organic film on the substrate is treated at a high temperature And the method of measurement (ICP-MS, GC, etc.). For example, the method of (1) has been described in Non-Patent Documents 1 to 4.
附帶一提，就剝離基板表面之有機薄膜的方法而言，專利文獻1已記載對含水蒸氣的自由基原料氣體施加電場而生成含羥基自由基的氣體，藉由將含此羥基自由基的氣體供給於經加熱的基板表面，而將基板表面之有機薄膜及污染物質剝離洗淨的剝離洗淨方法。又，專利文獻2已記載作為阻膜(resist)等的有機膜之剝離前處理，使有機膜暴露於藥液的蒸氣氣體之剝離方法。 Incidentally, in the method of peeling off the organic thin film on the surface of the substrate, Patent Document 1 discloses that an electric field is applied to a radical gas source containing water vapor to generate a gas containing a hydroxyl radical, and a gas containing the hydroxyl radical is used. A peeling cleaning method for supplying the surface of the heated substrate to remove the organic thin film and the contaminant on the surface of the substrate. Further, Patent Document 2 describes a method of peeling off a vapor gas in which an organic film is exposed to a chemical liquid as a pre-peeling treatment of an organic film such as a resist.
[專利文獻1]日本國公開專利公報「特開2005-13854號(2005年1月20日公開)」 [Patent Document 1] Japanese Laid-Open Patent Publication No. 2005-13854 (published on January 20, 2005)
[專利文獻2]日本國公開專利公報「特開2002-202619號(2002年7月19日公開)」 [Patent Document 2] Japanese Laid-Open Patent Publication No. 2002-202619 (published on July 19, 2002)
[非專利文獻1]若松秀明、伊藤博人、松田敦子、「機能性薄膜解析技術」、KONICAMINOLTA TECHNOLOGY REPORT VOL.7、p.14-19(2010) [Non-Patent Document 1] Wakamatsu Hideaki, Ito Hiroki, Matsuda Atsuko, "Functional Thin Film Analysis Technology", KONICAMINOLTA TECHNOLOGY REPORT VOL.7, p.14-19 (2010)
[非專利文獻2]西鄉真理、稻葉克彦、「使用X射線的有機薄膜之分析」、化學工業、2012年11月號、p.869-877 [Non-Patent Document 2] Xixiang Truth, Inaba Yoshihiko, "Analysis of Organic Thin Films Using X-Rays", Chemical Industry, November 2012, p.869-877
[非專利文獻3]關節子、「利用SIMS的有機薄膜之測定」、表面、Vol.28、No.7、 p.508-519(1990) [Non-Patent Document 3] Joints, "Measurement of Organic Thin Films Using SIMS", Surface, Vol. 28, No. 7, P.508-519 (1990)
[非專利文獻4]平野彰弘、藤本明良、「高頻輝光放電發光分析中的最新應用」、Readout,No.41,p27-33(2013) [Non-Patent Document 4] Hirano Hirano, Fujimoto Akira, "The Latest Application in High-Frequency Glow Discharge Luminescence Analysis", Readout, No. 41, p27-33 (2013)
然而，如上述之歷來技術，有無法獲得用以高敏感度定量有機薄膜等的有機膜所含成分之分析用樣品的問題點。 However, as described above, there is a problem in that it is impossible to obtain a sample for analysis of a component contained in an organic film such as a highly sensitive organic film.
例如，前述(1)之方法，於照射的離子或X射線到達基板的情形，藉由來自基板之雜質，測定的敏感度會降低。又，(1)之方法僅為有機薄膜表面之半定量分析法，無法分析有機薄膜全體。 For example, in the method of the above (1), when the irradiated ions or X-rays reach the substrate, the sensitivity of the measurement is lowered by the impurities from the substrate. Further, the method of (1) is only a semi-quantitative analysis method of the surface of the organic film, and it is impossible to analyze the entire organic film.
前述(2)之方法，因將每個基板之有機薄膜浸漬於有機溶媒，由於來自基板及有機溶媒的污染而以高敏感度之評價為困難的。又，於高溫處理的情形，由於來自器具、環境的污染、目的成分之揮發等，以高敏感度及高回收率之評價為困難的。再者，亦可能產生來自複雜操作的操作污染。 In the method of the above (2), since the organic thin film of each substrate is immersed in the organic solvent, it is difficult to evaluate the high sensitivity due to contamination from the substrate and the organic solvent. Further, in the case of high-temperature treatment, it is difficult to evaluate high sensitivity and high recovery rate due to contamination from equipment, the environment, and volatilization of the target component. Furthermore, operational contamination from complex operations can also result.
前述(3)之方法亦同樣地，由於來自基板之污染、來自高溫處理中之器具或環境的污染、目的成分之揮發等，以高敏感度及高回收率之評價為困難的。因此，前述(1)至(3)之方法有各自的問題。 Similarly, in the method of the above (3), it is difficult to evaluate the high sensitivity and the high recovery rate due to contamination from the substrate, contamination from equipment or the environment during high-temperature treatment, and volatilization of the target component. Therefore, the methods of the above (1) to (3) have respective problems.
另一方面，專利文獻1記載之剝離洗淨方法的技術領域係以阻膜薄膜為對象的剝離洗淨方法，有機薄膜自基板被剝離的同時，被分解及去除。又，專利文獻2記載之剝離方法係使產生阻膜等之有機膜變形、或變質化後作剝離處理。即，專利文獻2記載之剝離方法亦與專利文獻1記載之剝離洗淨方 法同樣地，亦以去除有機膜為目的。據此，藉由專利文獻1及2記載之技術，無法回收高敏感度之分析用樣品。 On the other hand, the technical field of the peeling cleaning method described in Patent Document 1 is a peeling and cleaning method for a film of a resist film, and the organic film is decomposed and removed from the substrate. Further, in the peeling method described in Patent Document 2, the organic film such as the resist film is deformed or denatured, and then subjected to a peeling treatment. In other words, the peeling method described in Patent Document 2 is also the peeling and cleaning method described in Patent Document 1. In the same way, the purpose of removing the organic film is also adopted. According to this, the high-sensitivity analysis sample cannot be recovered by the techniques described in Patent Documents 1 and 2.
本發明係鑑於前述歷來之問題點而進行，其目的係提供可獲得用以高敏感度定量有機薄膜等的有機膜所含成分之分析用樣品的分析用樣品之回收方法。 The present invention has been made in view of the above-mentioned problems, and an object thereof is to provide a method for recovering a sample for analysis which can obtain a sample for analysis of a component contained in an organic film such as a highly sensitive organic film.
本發明者們為了解決前述課題而深入檢討的結果，發現藉由使用蒸氣而將有機膜自基材選擇性地剝離或溶解，可以高回收率回收可將有機膜之成分用於高敏感度之分析方法的分析用樣品。 As a result of intensive review in order to solve the above problems, the inventors have found that the organic film can be selectively stripped or dissolved from the substrate by using steam, and the organic film component can be used for high sensitivity by recovering at a high recovery rate. Analytical method for analysis of samples.
即，與本發明有關之分析用樣品之回收方法係為了解決前述課題，用以將基材上之有機膜所含成分加以分析之分析用樣品的回收方法，其特徵為包含使前述有機膜與蒸氣接觸的蒸氣接觸步驟。 In other words, the method for recovering a sample for analysis according to the present invention is a method for recovering a sample for analysis for analyzing a component contained in an organic film on a substrate, and the method for recovering the sample for analysis includes Vapor contact step for vapor contact.
於與本發明有關之分析用樣品之回收方法，前述有機膜係可設置於有機電子領域使用的物品。 In the method for recovering an analysis sample according to the present invention, the organic film may be provided in an article used in the field of organic electronics.
於本發明之分析用樣品之回收方法，前述蒸氣係可為水、酸、鹼或有機溶媒、或彼等之混合物經氣化者。 In the method for recovering a sample for analysis of the present invention, the vapor system may be water, an acid, an alkali or an organic solvent, or a mixture thereof, which is vaporized.
於與本發明有關之分析用樣品之回收方法，於前述蒸氣接觸步驟，可使前述蒸氣僅與前述有機膜之一部分區域接觸。 In the method for recovering a sample for analysis according to the present invention, in the vapor contacting step, the vapor may be brought into contact only with a partial region of the organic film.
於與本發明有關之分析用樣品之回收方法，可僅回收前述有機膜之厚度方向的一部分區域。 In the method for recovering the sample for analysis according to the present invention, only a part of the region in the thickness direction of the organic film can be recovered.
於與本發明有關之分析用樣品之回收方法，前述蒸氣接觸步驟係可於密閉容器內進行。 In the method for recovering the sample for analysis according to the present invention, the vapor contacting step can be carried out in a closed container.
與本發明有關分析方法之特徵為包含檢測步驟，其係檢測藉由本發明中分析用樣品之回收方法所回收的膜所含之成分。 The analysis method relating to the present invention is characterized by comprising a detection step of detecting a component contained in a film recovered by the recovery method of the sample for analysis of the present invention.
與本發明有關之品質管理方法係具備有機膜的物品之品質管理方法，其特徵為包含判定步驟，其係判定藉由本發明之分析方法所檢測的前述有機膜所含成分之量是否為預設的基準量以下，或是否為預設的基準量以上。 The quality management method according to the present invention is a method for quality management of an article having an organic film, characterized by comprising a determination step of determining whether the amount of the component contained in the organic film detected by the analysis method of the present invention is a preset Below the reference amount, or whether it is above the preset reference amount.
與本發明有關之製造方法係具備有機膜的物品之製造方法，其特徵為包含品質管理步驟，其係藉由本發明之品質管理方法，而管理前述物品之品質。 A manufacturing method according to the present invention is a method for producing an article comprising an organic film, characterized in that it comprises a quality management step of managing the quality of the article by the quality management method of the present invention.
與本發明有關之品質管理方法係製造具備有機膜的物品的製造裝置之品質管理方法，其特徵為包含判定步驟，其係判定藉由本發明之分析方法所檢測的前述有機膜所含成分之量是否預設的基準量以下，或是否為預設的基準量以上。 The quality management method according to the present invention is a quality management method for manufacturing an article having an organic film, and is characterized by comprising a determination step of determining the amount of the component contained in the organic film detected by the analysis method of the present invention. Whether it is below the preset reference amount or whether it is above the preset reference amount.
與本發明有關之裝置係用以實施本發明之分析用樣品之回收方法的裝置，其特徵為具備使蒸氣產生的蒸氣產生部。 The apparatus according to the present invention is an apparatus for carrying out the method for recovering a sample for analysis of the present invention, characterized by comprising a vapor generating portion for generating steam.
與本發明有關之裝置係具備密閉容器，前述蒸氣產生部可被收容前述密閉容器。 The apparatus according to the present invention includes a sealed container, and the vapor generating unit can accommodate the sealed container.
於與本發明有關之裝置，前述密閉容器亦可兼作分析容器。 In the device according to the present invention, the sealed container may also serve as an analysis container.
與本發明有關之分析用樣品之回收方法係用以分析基材上之有機膜所含成分之分析用樣品之回收方法，其係包含使前述有機膜與蒸氣接觸的蒸氣接觸步驟的構成。 The method for recovering a sample for analysis according to the present invention is a method for recovering a sample for analysis for analyzing a component contained in an organic film on a substrate, and comprises a step of contacting a vapor in contact with the vapor with the organic film.
因此，與本發明有關之分析用樣品之回收方法係產生所謂可獲 得用以高敏感度定量有機膜所含成分之分析用樣品的效果。 Therefore, the method for recovering the sample for analysis related to the present invention produces a so-called available The effect of the sample for analysis for quantifying the components contained in the organic film with high sensitivity is obtained.
以下，詳細說明本發明之實施形態之一例，但本發明並未限定於此等例。又，於本說明書只要未特別記載，表示數值範圍的「A~B」係意指「A以上、B以下」。 Hereinafter, an example of an embodiment of the present invention will be described in detail, but the present invention is not limited to these examples. In addition, unless otherwise indicated in this specification, "A~B" which shows the numerical range means "A or more and B or less."
與本發明有關之分析用樣品之回收方法(以下，亦稱為「本發明之回收方法」)係用於分析基材上之有機膜所含成分之分析用樣品之回收方法，其包含使前述有機膜與蒸氣接觸的蒸氣接觸步驟。 The method for recovering a sample for analysis according to the present invention (hereinafter also referred to as "the method for recovering the present invention") is a method for recovering a sample for analysis for analyzing a component contained in an organic film on a substrate, which comprises the aforementioned A vapor contact step in which the organic film is in contact with the vapor.
<分析用樣品> <sample for analysis>
首先，說明於本發明之回收方法，成為回收對象的分析用樣品。 First, the analysis method of the present invention will be described as a sample for analysis to be recovered.
於本說明書，分析用樣品係於有機物之分析方法中成為分析對象者。具體而言，分析用樣品係包含來自基材上形成的有機膜之成分。分析用樣品係可使用於用以檢測前述有機膜所含成分的分析方法。 In the present specification, the sample for analysis is the object of analysis in the analysis method of the organic substance. Specifically, the sample for analysis contains a component derived from an organic film formed on a substrate. The sample for analysis can be used for an analytical method for detecting a component contained in the aforementioned organic film.
前述有機膜係包含有機物的膜。於本說明書，尤其將含該有機物的薄膜稱為有機薄膜。前述有機膜可為由有機物所構成的膜，亦可為由有機物與無機物所構成的膜。 The aforementioned organic film is a film containing an organic substance. In the present specification, a film containing the organic substance is particularly referred to as an organic film. The organic film may be a film composed of an organic substance, or may be a film composed of an organic substance and an inorganic substance.
前述有機物可為單一之有機物，亦可為相異二種類以上之有機物之混合物。又，前述無機物可為單一之無機物，亦可為相異二種類以上之無 機物之混合物。前述有機膜可為一層之膜，亦可為由二層以上之膜所構成的多層膜。 The organic substance may be a single organic substance or a mixture of two or more kinds of organic substances. Further, the inorganic substance may be a single inorganic substance, or may be two or more different types. a mixture of organisms. The organic film may be a film of one layer or a multilayer film composed of two or more films.
又，前述由有機物所構成的膜係可為由不同有機物所構成的膜為二層以上形成的多層膜。即，例如，前述由有機物所構成的膜係可為於單一之有機物A所構成的膜上形成由與有機物A不同的單一有機物B所構成的膜所形成的多層膜。 Further, the film composed of the organic material may be a multilayer film formed of two or more layers of a film composed of different organic substances. In other words, for example, the film made of an organic substance may be a multilayer film formed by forming a film composed of a single organic substance B different from the organic substance A on a film composed of a single organic substance A.
再者，前述由有機物所構成的膜係可為由相異二種類以上之有機物之混合物所構成的膜為二層以上形成的多層膜。又，由有機物所構成的膜可為由單一之有機物所構成的膜、及由相異的二種類以上之有機物之混合物所構成的膜重疊的多層膜。 Further, the film composed of the organic material may be a multilayer film formed of a film composed of a mixture of two or more kinds of organic substances in two or more layers. Further, the film made of an organic material may be a film composed of a single organic substance and a multilayer film in which a film composed of a mixture of two or more kinds of different organic substances is superposed.
又，前述由有機物與無機物所構成的膜係可為由有機物與無機物之混合物所構成的膜。再者，前述由有機物與無機物所構成的膜係可為由有機物所構成的膜與由無機物所構成的膜重疊的多層膜。當然，前述由有機物與無機物所構成的膜可為由有機物與無機物之混合物所構成的膜為二層以上重疊的多層膜。又，亦可為由有機物所構成的膜、由無機物所構成的膜、由有機物與無機物之混合物所構成的膜之中的至少相異二個以上之膜重疊的多層膜。 Further, the film composed of the organic substance and the inorganic substance may be a film composed of a mixture of an organic substance and an inorganic substance. Further, the film system composed of the organic substance and the inorganic substance may be a multilayer film in which a film made of an organic substance and a film made of an inorganic substance are superposed. Needless to say, the film composed of the organic substance and the inorganic substance may be a multilayer film in which a film composed of a mixture of an organic substance and an inorganic substance is two or more layers. Further, it may be a film composed of an organic material, a film composed of an inorganic material, or a multilayer film in which at least two or more films of a mixture of an organic material and an inorganic material are superposed.
就前述有機膜而言，並未特別限定，包含於所有領域，以著色、拋光、防鏽、防污、防霧、絕緣、賦予導電性等之各式各樣目的形成於基材上的有機膜。就此例而言，可列舉由電子裝置、光學裝置、生物裝置、磁性裝置等之領域所使用的材料而形成的有機膜。又，更具體而言，例如，可列舉由有機電子領域(有機EL、有機太陽電池、有機電晶體等)所使用的材料(有機成分)所形成的有機膜。換言之，前述有機膜係可為設置於有機電子領域所使用的物 品。 The organic film is not particularly limited and is included in all fields, and is organically formed on a substrate by various purposes such as coloring, polishing, rust prevention, antifouling, antifogging, insulation, and impartivity. membrane. In this example, an organic film formed of a material used in the fields of an electronic device, an optical device, a biological device, or a magnetic device may be mentioned. Moreover, more specifically, an organic film formed of a material (organic component) used in the field of organic electronics (organic EL, organic solar cell, organic transistor, etc.) is exemplified. In other words, the aforementioned organic film may be used in the field of organic electronics. Product.
有機膜之厚度並未特別限定，但由所謂可短時間回收的觀點，例如，500nm以下為較佳，200nm以下為更佳，100nm以下為特佳。例如，尤其厚度為500nm以下的情形，稱為有機薄膜。同樣地，膜之大小並未特別限定，但由可以短時間回收的觀點，例如，1cm×1cm~10cm×10cm為較佳。又，即使為具有超過500nm的厚度，或超過10cm×10cm的面積的有機膜，藉由適當設定後述蒸氣接觸步驟中的條件(例如藉由使長時間與蒸氣接觸)，回收分析用樣品為可能的。 The thickness of the organic film is not particularly limited. From the viewpoint of recovery in a short period of time, for example, 500 nm or less is preferable, and 200 nm or less is more preferable, and 100 nm or less is particularly preferable. For example, especially in the case where the thickness is 500 nm or less, it is called an organic film. Similarly, the size of the film is not particularly limited, but from the viewpoint of being able to be recovered in a short time, for example, 1 cm × 1 cm to 10 cm × 10 cm is preferable. In addition, even if it is an organic film having a thickness of more than 500 nm or an area of more than 10 cm × 10 cm, it is possible to recover the sample for analysis by appropriately setting the conditions in the vapor contact step described later (for example, by bringing the vapor into contact with a long time). of.
又，有機膜之質量亦未特別限制，但例如，可為0.001mg~500mg，可為0.001mg~0.1mg，可為0.1mg~10mg，亦可為10mg~500mg。 Further, the quality of the organic film is not particularly limited, but may be, for example, 0.001 mg to 500 mg, and may be 0.001 mg to 0.1 mg, 0.1 mg to 10 mg, or 10 mg to 500 mg.
有機膜所含的有機物並未特別限定。例如，可列舉於有機電子領域一般使用的有機物、芳香族烴、多環芳香族烴、由雜芳香族烴或雜多環芳香族烴所衍生的化合物、環彼此藉由共價鍵而連結的化合物、於骨架含有富勒烯(fullerene)的化合物、於骨架含有紫質(porphyrin)及酞花青(phthalocyanine)的化合物、含此等構造的金屬錯合物化合物、以及含此等之構造的寡聚物及聚合物等。 The organic substance contained in the organic film is not particularly limited. For example, an organic substance generally used in the field of organic electronics, an aromatic hydrocarbon, a polycyclic aromatic hydrocarbon, a compound derived from a heteroaromatic hydrocarbon or a heteropolycyclic aromatic hydrocarbon, and a ring are bonded to each other by a covalent bond. a compound, a compound containing a fullerene in a skeleton, a compound containing a porphyrin and a phthalocyanine in a skeleton, a metal complex compound having such a structure, and a structure containing the same Oligomers and polymers.
前述有機物因大多為具有芳香環的化合物，一般而言雖為難分解性，但若使用本發明之回收方法，可自基材容易地回收。 The organic substance is often a compound having an aromatic ring, and generally has difficulty in decomposability. However, if the recovery method of the present invention is used, it can be easily recovered from a substrate.
前述有機膜所形成的基材之材質亦未特別限定，可為無機物，亦可為有機物，亦可為有機物與無機物之混合物。例如，就無機物而言，可列舉矽、玻璃等，就有機物而言，可列舉合成樹脂等。基材之材質係例如，只要於有機電子領域中一般被使用的材質即可。 The material of the substrate formed of the organic film is not particularly limited, and may be an inorganic substance, an organic substance, or a mixture of an organic substance and an inorganic substance. For example, examples of the inorganic material include ruthenium, glass, and the like, and examples of the organic material include a synthetic resin and the like. The material of the substrate is, for example, a material that is generally used in the field of organic electronics.
又，基材之形狀亦未特別限定，可包含平面，亦可包含曲面。基材例如，可為由平面所構成的立體，亦可為由曲面所構成的球體，亦可為平面與曲面混合存在的立體。又，基材係具有柔軟性，可為平面與曲面自由地變化而獲得的基材。基材係例如，可為於有機電子領域中一般被使用的基板。 Further, the shape of the substrate is not particularly limited, and may include a flat surface or a curved surface. The substrate may be, for example, a solid formed of a flat surface, a spherical body formed of a curved surface, or a solid formed by mixing a flat surface and a curved surface. Further, the substrate is flexible, and can be a substrate obtained by freely changing a plane and a curved surface. The substrate may be, for example, a substrate generally used in the field of organic electronics.
又，成膜方法並未特別限定，可為液相成膜法，亦可為氣相成膜法。就液相成膜法之例而言，可列舉電鍍、塗佈、溶膠凝膠(sol-gel)、旋轉塗佈。就氣相成膜法之例而言，可列舉真空蒸鍍、濺鍍(sputtering)、雷射剝蝕(laser ablation)、離子鍍著(ion plating)、電漿化學氣相成長、熱化學氣相成長、有機金屬化學氣相成長、光化學氣相成長。又，成膜方法係例如，可為模具塗佈法(die coat method)、噴墨法(ink jet method)、浸漬塗佈法(dip coat method)、滴下塗佈法(drop casting method)。 Further, the film formation method is not particularly limited, and may be a liquid phase film formation method or a gas phase film formation method. Examples of the liquid phase film formation method include electroplating, coating, sol-gel, and spin coating. Examples of the vapor phase film formation method include vacuum evaporation, sputtering, laser ablation, ion plating, plasma chemical vapor growth, and thermal chemical vapor deposition. Growth, organometallic chemical vapor growth, photochemical vapor growth. Further, the film formation method may be, for example, a die coat method, an ink jet method, a dip coat method, or a drop casting method.
成為分析對象的成分係可為有機膜之主成分的有機物，亦可為無機物。又，成為分析對象的成分係可為有機膜所含的微量雜質。成為分析對象的成分係可為故意添加的成分，亦可為非故意地於製造步驟等混入的成分。成為分析對象的成分係可為本來不含於有機膜為較佳的成分。成為分析對象的成分係可為與於有機膜中存在的情形相同的形態被回收，亦可以分解物、劣化物、反應物等之形態被回收。 The component to be analyzed may be an organic substance which is a main component of the organic film, or may be an inorganic substance. Further, the component to be analyzed may be a trace impurity contained in the organic film. The component to be analyzed may be a component to be intentionally added, or may be a component that is inadvertently mixed in a manufacturing step or the like. The component to be analyzed may be a component which is preferably not contained in the organic film. The component to be analyzed may be recovered in the same manner as in the case of the organic film, or may be recovered in the form of a decomposition product, a deteriorated product, a reactant, or the like.
於本發明，就成為主成分的有機物之外，成為分析對象的成分而言，例如，可包含[鹼金屬元素]Li、Na、K、Rb、Cs；[鹼土類金屬元素]Be、Mg、Ca、Sr、Ba；[鑭系元素]La、Ce、Pr、Nd、Sm、Eu、Gd、Tb、Dy、Ho、Er、Tm、Yb、Lu；[錒系元素]Th、U；[過渡金屬元素]Sc、Ti、V、Cr、Mn、Fe、Co、Ni、Cu、Zn、Y、Zr、Nb、Mo、Ru、Rh、Pd、Ag、Cd、Hf、Ta、W、Re、 Os、Ir、Pt、Au；[硼族元素]B、Al、Ga、In、Tl；[碳族元素]Si、Ge、Sn、Pb；[氮族(pnictogen)元素]P、As、Sb、Bi；[氧族(chalcogen)元素]S、Se、Te；[鹵素元素]F、Cl、Br、I；之中至少一者。前述成分可為有機形態，亦可為離子形態。 In the present invention, in addition to the organic component which is a main component, the component to be analyzed may include, for example, [alkali metal element] Li, Na, K, Rb, and Cs; [alkaline earth metal element] Be, Mg, Ca, Sr, Ba; [lanthanide] La, Ce, Pr, Nd, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, Lu; [lanthanide] Th, U; Metal elements] Sc, Ti, V, Cr, Mn, Fe, Co, Ni, Cu, Zn, Y, Zr, Nb, Mo, Ru, Rh, Pd, Ag, Cd, Hf, Ta, W, Re, Os, Ir, Pt, Au; [boron element] B, Al, Ga, In, Tl; [carbon group element] Si, Ge, Sn, Pb; [nitrogen (pnictogen) element] P, As, Sb, Bi; [oxygen (chalcogen) element] S, Se, Te; [halogen element] F, Cl, Br, I; at least one of. The aforementioned components may be in an organic form or in an ionic form.
<蒸氣接觸步驟> <Vapor contact step>
本發明之回收方法之特徵為包含蒸氣接觸步驟。於蒸氣接觸步驟，使上述有機膜與蒸氣接觸。藉由使有機膜與蒸氣接觸，可減弱構成前述有機膜的分子彼此的結合及/或前述有機膜與前述基材之表面的結合。據此，自基材剝離有機膜、或有機膜被溶解。因此，可不分解基材本身，選擇性地分析僅來自有機膜的成分而回收作為分析用樣品。據此，可最小限度地保留基材所含雜質的溶出。又，可以高回收率回收有機膜所含成分。而且，藉由將回收的有機膜以分析有機物的各種高敏感度分析方法加以分析，可以高敏感度分析有機膜所含成分而加以評價。 The recovery method of the present invention is characterized by comprising a vapor contacting step. The organic film is brought into contact with the vapor in the vapor contacting step. By bringing the organic film into contact with the vapor, the bonding of the molecules constituting the organic film and/or the bonding of the organic film to the surface of the substrate can be weakened. According to this, the organic film is peeled off from the substrate, or the organic film is dissolved. Therefore, it is possible to recover the sample for analysis without selectively decomposing the substrate itself and selectively analyzing the component derived only from the organic film. According to this, the elution of the impurities contained in the substrate can be kept to a minimum. Further, the components contained in the organic film can be recovered at a high recovery rate. Further, by analyzing the recovered organic film by various high-sensitivity analysis methods for analyzing organic substances, it is possible to evaluate the components contained in the organic film with high sensitivity.
前述蒸氣係溶媒被氣化者。該溶媒可為水、酸、鹼、或有機溶媒，亦可為此等之混合物。又，溶媒可為有機膜溶解的溶媒，亦可為雖有機膜剝離但未溶解的溶媒。又，由所謂未使有機膜所含成分之性質變化而回收的觀點，前述溶媒係不分解有機膜的溶媒為較佳。再者，由所謂防止基材所含的雜質溶出的觀點，作為前述溶媒，選擇不溶解或分解基材的溶媒為較佳。 The vapor-based solvent is vaporized. The solvent may be water, an acid, a base, or an organic solvent, or a mixture thereof. Further, the solvent may be a solvent in which the organic film is dissolved, or may be a solvent in which the organic film is peeled off but not dissolved. Moreover, it is preferable that the solvent is a solvent which does not decompose the organic film from the viewpoint that the properties of the components contained in the organic film are not changed. Further, from the viewpoint of preventing elution of impurities contained in the substrate, it is preferred to select a solvent which does not dissolve or decompose the substrate as the solvent.
就有機溶媒而言，例如，可列舉乙腈、氯仿、二氯甲烷、四氫呋喃、己烷、甲苯、甲醇。又，由所謂可將成為分析對象的成分作成水溶性之離子的觀點，溶媒為水較佳。 Examples of the organic solvent include acetonitrile, chloroform, dichloromethane, tetrahydrofuran, hexane, toluene, and methanol. Further, from the viewpoint that the component to be analyzed can be made into a water-soluble ion, the solvent is preferably water.
就酸而言，例如，可列舉氫氟酸、硝酸、鹽酸、硫酸、磷酸、過氧化氫水、及過氯酸。酸可為水溶液，亦可為二種類以上之酸的混合液。溶 液中之酸之濃度係越高越佳，例如，20%以上為較佳，50%以上為更佳，60%以上為特佳。 Examples of the acid include hydrofluoric acid, nitric acid, hydrochloric acid, sulfuric acid, phosphoric acid, hydrogen peroxide water, and perchloric acid. The acid may be an aqueous solution or a mixture of two or more kinds of acids. Dissolve The higher the concentration of the acid in the liquid, the better, for example, 20% or more is preferable, 50% or more is more preferable, and 60% or more is particularly preferable.
就鹼而言，例如，可列舉氨、氫氧化鈉、氫氧化鈣、氫氧化四甲銨。鹼可為水溶液，亦可為二種類以上之鹼的混合液。溶液中之鹼之濃度係越高越佳，例如，20%以上為較佳，50%以上為更佳，60%以上為特佳。 Examples of the base include ammonia, sodium hydroxide, calcium hydroxide, and tetramethylammonium hydroxide. The base may be an aqueous solution or a mixture of two or more kinds of bases. The higher the concentration of the alkali in the solution, the better, for example, 20% or more is preferable, 50% or more is more preferable, and 60% or more is particularly preferable.
溶媒之量係只要因應容器的大小或有機膜的量而適宜設定即可。若依據本發明，不論有機膜材料之溶解度為何，皆可回收分析用樣品。據此，與使有機膜浸漬及溶解於液體之溶媒的方法相比，因以少量溶媒即可回收分析用樣品，故可減低來自溶媒的污染。 The amount of the solvent may be appropriately set in accordance with the size of the container or the amount of the organic film. According to the present invention, the sample for analysis can be recovered regardless of the solubility of the organic film material. As a result, compared with the method of immersing and dissolving the organic film in a liquid solvent, the sample for analysis can be recovered with a small amount of solvent, so that contamination from the solvent can be reduced.
於蒸氣接觸步驟，使前述溶媒氣化的蒸氣與有機膜接觸。本發明之回收方法可包含使前述溶媒氣化而使蒸氣發生的蒸氣發生步驟。使蒸氣發生的方法可為溶媒氣化的方法，具體而言，可列舉加熱方法、減壓方法、使超音波振動的方法等。又，可適宜組合此等之方法。 In the vapor contacting step, the vaporized vapor of the solvent is brought into contact with the organic film. The recovery method of the present invention may comprise a vapor generating step of vaporizing the solvent to generate steam. The method of generating the vapor may be a method of vaporizing the solvent, and specific examples thereof include a heating method, a pressure reduction method, and a method of vibrating ultrasonic waves. Further, such methods can be suitably combined.
於加熱的方法，只要用以使有機膜剝離或溶解的充分蒸氣發生，可使溶媒沸騰，亦可不使沸騰。據此，可加熱至溶媒的沸點，亦可加熱至未達沸點的溫度。較佳地，蒸氣為飽和蒸氣。加熱溫度可因應溶媒種類等而適宜決定，但由所謂使蒸氣充分發生的觀點，接近溶媒沸點的溫度為較佳，為溶媒沸點者更佳。例如，溶媒為水的情形，於1氣壓下之加熱溫度係80℃~100℃為較佳，90℃~100℃為更佳，100℃為特佳。若依據本發明，與將有機膜於高溫氧化分解的方法相比，以低溫來處理係可能的。又，加熱時間於例如溶媒為水的情形，5分鐘~120分鐘為較佳，10分鐘~30分鐘為更佳。例如溶媒為乙腈、氯仿、二氯甲烷、四氫呋喃、己烷、甲醇等之低沸點溶媒的情形，3分鐘~60分鐘為較 佳，5分鐘~20分鐘為更佳。例如溶媒為甲苯、硝酸、氫氟酸、硝酸、鹽酸、過氧化氫水、過氯酸、氫氧化鈉水溶液、氫氧化鉀水溶液、氫氧化四甲銨水溶液等之中沸點溶媒的情形，5分鐘~120分鐘為較佳，10分鐘~30分鐘為更佳。例如溶媒為硫酸、磷酸等之高沸點溶媒的情形，10分鐘~120分鐘為較佳，20分鐘~60分鐘為更佳。若為該加熱時間，由所謂使充分產生蒸氣的觀點為較佳。 In the heating method, as long as sufficient vapor for separating or dissolving the organic film occurs, the solvent may be boiled or boiled. Accordingly, it can be heated to the boiling point of the solvent, or heated to a temperature at which the boiling point is not reached. Preferably, the vapor is a saturated vapor. The heating temperature can be appropriately determined depending on the type of the solvent, etc., but the temperature near the boiling point of the solvent is preferably from the viewpoint of sufficiently generating the vapor, and the boiling point of the solvent is more preferable. For example, in the case where the solvent is water, the heating temperature at 1 atmosphere is preferably 80 ° C to 100 ° C, more preferably 90 ° C to 100 ° C, and 100 ° C is particularly preferable. According to the present invention, it is possible to treat at a low temperature as compared with a method of oxidative decomposition of an organic film at a high temperature. Further, the heating time is, for example, a case where the solvent is water, preferably 5 minutes to 120 minutes, more preferably 10 minutes to 30 minutes. For example, when the solvent is a low-boiling solvent such as acetonitrile, chloroform, dichloromethane, tetrahydrofuran, hexane or methanol, the temperature is from 3 minutes to 60 minutes. Good, 5 minutes to 20 minutes is better. For example, the solvent is a solvent such as toluene, nitric acid, hydrofluoric acid, nitric acid, hydrochloric acid, hydrogen peroxide water, perchloric acid, aqueous sodium hydroxide solution, potassium hydroxide aqueous solution or tetramethylammonium hydroxide aqueous solution, and 5 minutes. ~120 minutes is better, and 10 minutes to 30 minutes is better. For example, in the case where the solvent is a high-boiling solvent such as sulfuric acid or phosphoric acid, it is preferably from 10 minutes to 120 minutes, more preferably from 20 minutes to 60 minutes. In the case of this heating time, it is preferable from the viewpoint of sufficiently generating vapor.
關於減壓的方法，只要至蒸氣產生的壓力為止的減壓即可。 The method of reducing the pressure may be a pressure reduction until the pressure generated by the vapor.
有機膜可直接保持膜之形狀而自基材剝離被回收，亦可以一部分或全部被溶解的狀態下被回收。例如，蒸氣浸透有機膜而到達有機膜與基材的界面，藉由減弱有機膜與基材之結合，亦可使有機膜被剝離。又，可為有機膜之表面被緩緩地溶解。有機膜係由複數層所構成的情形，可一層層地被剝離而被回收。 The organic film can be directly removed from the substrate by being held in the shape of the film, or can be recovered in a state in which some or all of it is dissolved. For example, the vapor penetrates the organic film to reach the interface between the organic film and the substrate, and the organic film can be peeled off by weakening the bonding between the organic film and the substrate. Further, the surface of the organic film may be slowly dissolved. When the organic film is composed of a plurality of layers, it can be peeled off and recovered in layers.
被溶解的有機膜可與溶媒一起被回收。被剝離的有機膜亦可與溶媒一起被回收，或者，與溶媒分離，具體而言，基板上殘留的具有膜狀的有機物可被回收。據此，溶媒可兼作有機膜之回收液的機能。本發明之回收方法亦可謂包含回收來自有機膜的成分作為分析用樣品的回收步驟。 The dissolved organic film can be recovered together with the solvent. The peeled organic film may be recovered together with the solvent or may be separated from the solvent, and specifically, the organic substance having a film shape remaining on the substrate may be recovered. Accordingly, the solvent can serve as a function of the recovery liquid of the organic film. The recovery method of the present invention may also be a recovery step including recovering a component derived from an organic film as a sample for analysis.
再者，藉由變更溶媒的種類，以含有成為分析對象的成分的揮發性之元素的回收、或該成分之形態類別(固體、液體、氣體)之回收為可能的。又，亦可將成為分析對象的成分所含的元素以離子的形態來回收。又，藉由選擇溶媒的種類，可減少操作過程的空白(blank)。 Further, by changing the type of the solvent, it is possible to recover the volatile element containing the component to be analyzed or to recover the form type (solid, liquid, gas) of the component. Further, the element contained in the component to be analyzed may be recovered in the form of ions. Further, by selecting the type of the solvent, the blank of the operation process can be reduced.
使蒸氣接觸的時間係因應溶媒的種類或蒸氣壓、有機膜的大小等，而適宜設定即可。由所謂使有機膜充分剝離或溶解的觀點，例如，使蒸氣接觸的時間係30分鐘~60分鐘為較佳，60分鐘~180分鐘為更佳，180分鐘~480 分鐘為特佳。 The time for bringing the vapor into contact may be appropriately set depending on the type of the solvent, the vapor pressure, the size of the organic film, and the like. From the viewpoint of sufficiently peeling or dissolving the organic film, for example, the time for bringing the vapor into contact is preferably 30 minutes to 60 minutes, more preferably 60 minutes to 180 minutes, and 180 minutes to 480 minutes. Minutes are especially good.
於本發明之回收方法，使有機膜與蒸氣接觸的同時，可將有機膜及/或有機膜所形成的基材加熱或冷卻。 In the recovery method of the present invention, the organic film and/or the substrate formed of the organic film may be heated or cooled while the organic film is in contact with the vapor.
又，藉由變更使蒸氣產生時之溫度或時間等之條件，例如可使有機膜之剝離強度變化。因此，具有可應用於有機膜所含成分之於深度方向(有機膜之厚度方向)之評價的可能性。據此，藉由調節剝離強度，可僅回收有機膜之厚度方向之一部分區域。據此，可選擇性地回收有機膜之厚度方向之任意區域。因此，可於有機膜之厚度方向作階段性地分析。據此，例如，可區別有機膜之表面所存在的成分之含量、及基材與有機膜之界面附近區域存在的成分之含量而加以分析。 Further, by changing the conditions such as the temperature or time at which the vapor is generated, for example, the peeling strength of the organic film can be changed. Therefore, there is a possibility that it can be applied to the evaluation of the components contained in the organic film in the depth direction (the thickness direction of the organic film). According to this, by adjusting the peeling strength, only a part of the thickness direction of the organic film can be recovered. According to this, any region in the thickness direction of the organic film can be selectively recovered. Therefore, it can be analyzed stepwise in the thickness direction of the organic film. According to this, for example, the content of the component present on the surface of the organic film and the content of the component existing in the vicinity of the interface between the substrate and the organic film can be analyzed.
因此，上述之有機膜之表面所存在的成分、及基材與有機膜之界面附近區域所存在的成分亦包含於成為本發明所致的回收對象及/或分析對象的成分(換言之，包含於有機膜的成分)。又，於本說明書，有機膜之表面所存在的成分係意指於有機膜之內部且為有機膜之表面附近的區域存在的成分及附著於有機膜之表面的成分。於有機膜之內部且為有機膜之表面附近區域係指例如，可為自有機膜之表面面向內部朝厚度方向10nm以內的區域，亦可為朝厚度方向1nm以內之區域，亦可為朝厚度方向0.1nm以內的區域。 Therefore, the component present on the surface of the organic film and the component existing in the vicinity of the interface between the substrate and the organic film are also included in the component to be recovered and/or analyzed by the present invention (in other words, included in The composition of the organic film). Moreover, in the present specification, the component existing on the surface of the organic film means a component existing inside the organic film and present in a region near the surface of the organic film, and a component adhering to the surface of the organic film. The region in the vicinity of the surface of the organic film and the surface of the organic film may be, for example, a region within 10 nm from the surface of the organic film facing the inside in the thickness direction, or a region within 1 nm in the thickness direction, or may be a thickness toward the thickness. The area within 0.1 nm direction.
使蒸氣接觸的方向亦未特別限定。將有機膜所形成的基材配置於容器內，藉由於該容器內使蒸氣產生，容器內以蒸氣填滿，可使有機膜與蒸氣接觸。又，藉由噴灑含蒸氣的氣體，可自冀望的方向使蒸氣接觸。 The direction in which the vapor is brought into contact is also not particularly limited. The substrate formed of the organic film is placed in a container, and the vapor is generated in the container, and the inside of the container is filled with steam to bring the organic film into contact with the vapor. Further, by spraying a gas containing steam, the vapor can be brought into contact in a direction in which it is viewed.
前述蒸氣接觸步驟係於密閉容器內進行者較佳。於此情形，於成為分析之對象的成分具有揮發性的情形，亦可減少回收的損失。密閉容器係 只要可防止分析對象成分向容器外側環境的揮發的容器即可，並未特別限定。亦可使用具有開口部的容器，藉由基材上之有機膜所形成的面將開口部封閉而作成密閉容器。又，於密閉容器內進行前述接觸步驟的情形，亦可防止來自操作環境的污染。 It is preferred that the vapor contacting step be carried out in a closed container. In this case, in the case where the component to be analyzed is volatile, the loss of recovery can also be reduced. Closed container The container is not particularly limited as long as it can prevent the analyte component from volatilizing into the environment outside the container. A container having an opening may be used, and the opening may be closed by a surface formed by the organic film on the substrate to form a sealed container. Further, in the case where the above-described contacting step is carried out in a sealed container, contamination from the operating environment can be prevented.
以下說明於容器內使蒸氣產生的方法之一例。首先，將對應成為回收對象的有機膜之材質的溶媒置入容器中。置入溶媒的容器係只要以具備對該溶媒有耐性(不會經溶媒而被溶解)的材質所形成者即可。具體而言，只要為以氟樹脂、石英等所形成的容器，即可不污染被回收的分析用樣品而為較佳。就氟樹脂而言，例如，可列舉聚四氟乙烯(PTFE)、四氟乙烯‧全氟烷基乙烯醚共聚物(PFA)、聚偏二氟乙烯(polyvinylidene fluoride，PVDF)、聚氯三氟乙烯(polychlorotrifluoroethylene，PCTFE)。 An example of a method of generating steam in a container will be described below. First, a solvent corresponding to the material of the organic film to be collected is placed in a container. The container in which the solvent is placed may be formed of a material having resistance to the solvent (not dissolved by the solvent). Specifically, as long as it is a container formed of a fluororesin, quartz or the like, it is preferable to not contaminate the sample for analysis to be recovered. Examples of the fluororesin include polytetrafluoroethylene (PTFE), tetrafluoroethylene, perfluoroalkyl vinyl ether copolymer (PFA), polyvinylidene fluoride (PVDF), and polychlorotrifluorocarbon. Polychlorotrifluoroethylene (PCTFE).
其次，於置入溶媒的容器中，配置有機膜所形成的基材。該基材只要安置使有機膜不與液體狀的溶媒(氣化前之溶媒)接觸的位置即可。而，藉由將容器加熱，或藉由於容器內使減壓或超音波振動而產生蒸氣，使有機膜與蒸氣接觸即可。 Next, a substrate formed of an organic film is placed in a container in which a solvent is placed. The substrate may be disposed so that the organic film does not come into contact with a liquid solvent (solvent before vaporization). Further, the organic film may be brought into contact with the vapor by heating the container or by generating a vapor by decompression or ultrasonic vibration in the container.
例如，可使有機膜所形成的面向下的方式來配置基材，使自下側與蒸氣接觸。又，可使有機膜所形成的面向上的方式來配置基材，使自上側與蒸氣接觸。又，其中，「下」係意指重力方向，「上」意指與重力方向相反的方向。又，亦可配置機材使有機膜所形成的面朝向與重力方向垂直的方向，而使與蒸氣接觸。 For example, the substrate may be disposed in a downwardly facing manner in which the organic film is formed so as to be in contact with the vapor from the lower side. Further, the substrate may be placed in such a manner that the organic film is formed to face upward, and the upper side is brought into contact with the vapor. In addition, "lower" means the direction of gravity, and "upper" means the direction opposite to the direction of gravity. Further, the machine may be arranged such that the surface formed by the organic film faces the direction perpendicular to the direction of gravity and comes into contact with the vapor.
設置基材使有機膜所形成的面向下，使自下側與蒸氣接觸的情形，亦可藉由使有機膜(或有機膜之溶解物)藉由本身重量而向重力方向落下而加 以回收。又，此情形，若將成為蒸氣之產生源的溶媒配置於下側，可使被剝離的有機膜(或有機膜之溶解物)落下至溶媒中而回收。 The substrate is disposed such that the surface formed by the organic film faces downward, and the contact with the vapor from the lower side can also be caused by causing the organic film (or the dissolved material of the organic film) to fall in the direction of gravity by its own weight. To recycle. In this case, when the solvent serving as the source of the vapor is disposed on the lower side, the peeled organic film (or the dissolved product of the organic film) can be dropped into the solvent and recovered.
又，藉由調整有機膜之與蒸氣接觸的面積，可僅使蒸氣與前述有機膜之一部分區域接觸。據此，可選擇性地回收有機膜之任意區域。據此，可選擇性地分析來自有機膜之任意區域的成分。例如，藉由遮蔽成為分析對象的任意區域以外的區域後，使與蒸氣接觸，亦可調整使有機膜之與蒸氣接觸的面積。 Further, by adjusting the area of the organic film in contact with the vapor, only the vapor can be brought into contact with a partial region of the organic film. According to this, any region of the organic film can be selectively recovered. According to this, the composition from any region of the organic film can be selectively analyzed. For example, by shielding the region other than the arbitrary region to be analyzed, the surface of the organic film in contact with the vapor can be adjusted by bringing it into contact with the vapor.
若藉由與本發明有關的分析用樣品之回收方法，因使用蒸氣，藉由調節蒸氣之接觸面積及接觸強度，可回收有機膜全體，亦可回收有機膜之一部分區域。藉由本發明之回收方法所回收的分析用樣品可使用於可評價有機膜全體的分析方法。又，若依據本發明之回收方法，例如與各基板以高溫將有機膜氧化分解的方法相比，選擇性回收有機膜中之任意區域為容易的。 According to the method for recovering an analysis sample according to the present invention, by using steam, by adjusting the contact area and contact strength of the vapor, the entire organic film can be recovered, and a part of the organic film can be recovered. The sample for analysis recovered by the recovery method of the present invention can be used for an analytical method for evaluating the entire organic film. Further, according to the recovery method of the present invention, for example, it is easy to selectively recover any region in the organic film as compared with a method in which each substrate oxidizes and decomposes the organic film at a high temperature.
本發明有關的分析方法係包含檢測步驟，該檢測步驟係檢測藉由本發明有關的分析用樣品之回收方法所回收的有機膜中所含成分。 The analysis method according to the present invention comprises a detection step of detecting a component contained in the organic film recovered by the method for recovering the sample for analysis according to the present invention.
藉由將有機膜剝離或溶解而被回收的分析用樣品中可包含成為分析對象的成分。檢測前述檢測步驟中的成分的方法係因應回收的有機膜之形態(膜狀或液體狀)及成為分析對象的成分之種類，而選擇適當方法即可。 The sample for analysis which is recovered by peeling or dissolving the organic film may contain a component to be analyzed. The method of detecting the components in the detection step may be an appropriate method depending on the form (membrane or liquid) of the organic film to be recovered and the type of the component to be analyzed.
例如，就於檢測步驟所使用的方法而言，可列舉感應耦合電漿質譜儀分析法(inductively coupled plasma-mass spectrometer，ICP-MS)、感應耦合電漿原子放射光譜儀分析法(inductively coupled plasma atomic emission spectrometer，ICP-AES)、原子吸光分析法(atomic absorption spectrometer，AAS)、 離子層析法(ion chromatography)、毛細管電泳法(capillary electrophoresis)、液體層析法(liquid chromatography)、氣體層析法(gas chromatography)。此等之方法因與例如直接分析法(XPS、XRD、TXRF、TOF-SIMS、SIMS、GD-OES等)相比，測定敏感度良好而為較佳。 For example, in terms of the method used in the detection step, an inductively coupled plasma-mass spectrometer (ICP-MS) or an inductively coupled plasma atomic spectrometer can be cited. Emission spectrometer, ICP-AES), atomic absorption spectrometer (AAS), Ion chromatography, capillary electrophoresis, liquid chromatography, gas chromatography. These methods are preferred because they have good measurement sensitivity compared to, for example, direct analysis methods (XPS, XRD, TXRF, TOF-SIMS, SIMS, GD-OES, etc.).
又，對分析的有機膜施予的前處理方法亦只要因應該有機膜之形態及成為分析對象的成分之種類，選擇適當的方法即可。例如，可使用酸分解法、燃燒法、溶媒溶解法、溶媒萃取法等，亦可將此等之方法組合。 Further, the pretreatment method for applying the organic film to be analyzed may be an appropriate method depending on the form of the organic film and the type of the component to be analyzed. For example, an acid decomposition method, a combustion method, a solvent dissolution method, a solvent extraction method, or the like can be used, and these methods can also be combined.
若依據本發明有關之分析方法，由於可因應成為分析對象的成分而應用適當方法的緣故，可將有機物、金屬、非金屬、鹵素等各式各樣的成分作為對象。又，如上述，因基材之材質及成膜方法亦未特別限制，可將多種有機膜作為對象試料。 According to the analysis method of the present invention, various components such as organic substances, metals, non-metals, and halogens can be used because appropriate methods can be applied to the components to be analyzed. Moreover, as described above, the material of the substrate and the film formation method are not particularly limited, and various organic films can be used as the target sample.
又，如上述，本發明有關的分析用樣品之回收方法係可藉由因應成為分析對象的成分而選擇容器或條件，防止來自基材及溶媒的污染、操作中之污染、以及揮發所致的損失。因此，本發明有關的分析方法變成可能以高敏感度來定量有機膜所含成分。又，於本發明有關的分析方法，因濃度已知的標準試料之調製為容易，故分析的準確度高。據此，本發明可適合使用於特別要求高純度品的電子裝置、光學裝置等之領域(更具體而言，例如有機電子領域)。 Further, as described above, the method for recovering the sample for analysis according to the present invention can prevent the contamination from the substrate and the solvent, the contamination during the operation, and the volatilization by selecting the container or the condition in accordance with the component to be analyzed. loss. Therefore, the analysis method relating to the present invention becomes possible to quantify the components contained in the organic film with high sensitivity. Further, in the analysis method according to the present invention, since the preparation of the standard sample having a known concentration is easy, the accuracy of the analysis is high. Accordingly, the present invention can be suitably used in the field of electronic devices, optical devices, and the like which are particularly required for high-purity products (more specifically, for example, in the field of organic electronics).
本發明有關的品質管理方法係具備有機膜的物品之品質管理方法，其包含判定步驟，該判定步驟係判定藉由本發明有關的分析方法所檢測的前述有機膜中所含成分之量是否為預設的基準量以下、或是否為預設的基準量以上。換言之， 本發明有關的品質管理方法係包含檢測藉由本發明有關的分析用樣品之回收方法所回收的有機膜所含成分的檢測步驟、及判定於該檢測步驟所檢測的前述有機膜所含成分之量是否為預設的基準量以下、或是否為預設的基準量以上的判定步驟。該判定步驟亦可謂是判定被檢測的成分之量是否較基準量為多、或是否低於基準量的步驟。 The quality management method according to the present invention is a quality management method for an article having an organic film, comprising a determination step of determining whether the amount of the component contained in the organic film detected by the analysis method according to the present invention is The reference amount is set to be less than or equal to the preset reference amount. In other words, The quality management method according to the present invention includes a step of detecting a component contained in the organic film recovered by the method for recovering the sample for analysis according to the present invention, and determining the amount of the component contained in the organic film detected in the detecting step. Whether it is a determination step below the preset reference amount or whether it is equal to or greater than the preset reference amount. This determination step may also be a step of determining whether the amount of the detected component is greater than the reference amount or whether it is lower than the reference amount.
就具備有機膜的物品而言，並未特別限定，可包含以著色、拋光、防鏽、防污、防霧、絕緣、賦予導電性等之各式各樣目的而形成有機膜的物品。就其例而言，可列舉於電子裝置、光學裝置、生物裝置、磁性裝置等之領域所使用的構件、或使用該構件的製品。更具體而言，例如，可列舉於有機電子領域所使用的構件、或使用該構件的製品(有機EL、有機太陽電池、有機電晶體等)等。 The article having the organic film is not particularly limited, and may include an article in which an organic film is formed for various purposes such as coloring, polishing, rust prevention, antifouling, antifogging, insulation, and impartivity. Examples thereof include members used in the fields of electronic devices, optical devices, biological devices, magnetic devices, and the like, or articles using the members. More specifically, for example, a member used in the field of organic electronics or a product (organic EL, organic solar cell, organic transistor, or the like) using the member may be mentioned.
預設的成分之基準量係只要因應冀求的物品之品質加以適宜決定即可。 The basis amount of the preset component may be appropriately determined according to the quality of the article to be requested.
若依據本發明有關的品質管理方法，藉由本發明有關的分析方法，可高回收率且高敏感度檢測有機膜所含成分。據此，基於分析結果，可判定物品之品質，而將該物品之品質保持一定。 According to the quality management method of the present invention, the composition of the organic film can be detected with high recovery and high sensitivity by the analysis method according to the present invention. According to this, based on the analysis result, the quality of the article can be determined, and the quality of the article can be kept constant.
又，本發明有關的品質管理方法係製造具備有機膜的物品的製造裝置之品質管理方法，係可為一種品質管理方法，其特徵為包含判定步驟，該判定步驟係判定藉由本發明有關的分析方法所檢測的前述有機膜所含成分之量是否為預設的基準量以下、或是否為預設的基準量以上。又，該製造裝置之品質管理方法可含有製造步驟，該製造步驟為藉由製造裝置而製造具備有機膜的物品。 Moreover, the quality management method according to the present invention is a quality management method for manufacturing an article manufacturing apparatus including an organic film, and is a quality management method characterized by including a determination step of determining an analysis related to the present invention. The amount of the component contained in the organic film detected by the method is less than a preset reference amount or is a predetermined reference amount or more. Moreover, the quality management method of the manufacturing apparatus may include a manufacturing step of manufacturing an article having an organic film by a manufacturing apparatus.
若依據上述構成，藉由分析製造裝置所製造的有機膜中所含成分，可管理製造裝置之品質使其成為製造一定品質的物品的製造裝置。 According to the above configuration, by analyzing the components contained in the organic film produced by the manufacturing apparatus, it is possible to manage the quality of the manufacturing apparatus and to manufacture the article of a certain quality.
本發明有關的製造方法係具備有機膜的物品之製造方法，其包含藉由本發明有關的品質管理方法而管理前述物品之品質的品質管理步驟。換言之，本發明有關之製造方法包含檢測藉由本發明有關的分析用樣品之回收方法而回收的有機膜所含成分的檢測步驟；判定於該檢測步驟所檢測的前述有機膜所含成分之量是否為預設的基準量以下、或是否為預設的基準量以上的判定步驟；及基於該判定步驟的判定結果，而管理前述物品之品質的品質管理步驟。又，亦可謂本發明有關的製造方法係包含製備具備有機膜的物品的製造步驟。 A manufacturing method according to the present invention is a method for producing an article comprising an organic film, which comprises a quality management step of managing the quality of the article by the quality management method according to the present invention. In other words, the manufacturing method according to the present invention includes a step of detecting a component contained in the organic film recovered by the method for recovering the sample for analysis according to the present invention, and determining whether the amount of the component contained in the organic film detected in the detecting step is a determination step of a predetermined reference amount or less, or a predetermined reference amount or more; and a quality management step of managing the quality of the article based on the determination result of the determination step. Moreover, it can be said that the manufacturing method according to the present invention includes a manufacturing step of preparing an article having an organic film.
若依據本發明有關的製造方法，因可藉由本發明有關的品質管理方法而正確地管理物品之品質，故可製造一定品質之物品。 According to the manufacturing method of the present invention, since the quality of the article can be accurately managed by the quality management method according to the present invention, it is possible to manufacture an article of a certain quality.
本發明有關的裝置係用以實施本發明有關的分析用樣品之回收方法之裝置，其具備使蒸氣產生的蒸氣產生部。因此，藉由使蒸氣產生部所產生的蒸氣與有機膜接觸，可減弱構成前述有機膜的分子彼此之結合及/或前述有機膜與基材之表面之結合。因此，可不分解基材本身，僅回收來自有機膜的成分作為分析用樣品。據此，可將來自基材的雜質之溶出降至最低限度。又，可以高回收率回收有機膜所含成分。 The apparatus according to the present invention is an apparatus for carrying out the method for recovering a sample for analysis according to the present invention, comprising a vapor generating portion for generating steam. Therefore, by bringing the vapor generated in the vapor generating portion into contact with the organic film, the bonding of the molecules constituting the organic film and/or the bonding of the organic film to the surface of the substrate can be weakened. Therefore, it is possible to recover only the component derived from the organic film as a sample for analysis without decomposing the substrate itself. According to this, the elution of impurities from the substrate can be minimized. Further, the components contained in the organic film can be recovered at a high recovery rate.
<蒸氣產生部> <Vapor Generation Department>
本發明有關的裝置係具備使蒸氣產生的蒸氣產生部。蒸氣產生部之構成係只要為使自上述溶媒產生蒸氣的構成即可，並未特別限定。例如，蒸氣產生部可 具有收容溶媒的空間。蒸氣產生部亦可具備藉由進一步對該空間進行加熱、減壓或超音波振動等之處理而自溶媒使蒸氣產生的構成。據此，可使基材上之有機膜與蒸氣接觸。例如，可具備加熱器(heater)、加熱板(hot plate)等作為用以加熱的構成。又，亦可具備真空泵、水式吸引器(aspirator)等作為用以減壓的構成。又，亦可具備超音波產生裝置等作為用以超音波振動之構成。 The apparatus according to the present invention is provided with a steam generating portion that generates steam. The configuration of the steam generating portion is not particularly limited as long as it is a configuration for generating steam from the solvent. For example, the steam generating unit can It has a space to contain the solvent. The steam generating unit may be configured to generate steam from the solvent by further heating, decompressing, or supersonic vibration of the space. Accordingly, the organic film on the substrate can be brought into contact with the vapor. For example, a heater, a hot plate, or the like may be provided as a structure for heating. Further, a vacuum pump, a water aspirator or the like may be provided as a configuration for decompressing. Further, an ultrasonic wave generating device or the like may be provided as a structure for ultrasonic vibration.
前述蒸氣產生部亦可兼作回收經剝離的有機膜(或有機膜之溶解物)的回收部。即，亦可兼作收容前述蒸氣產生部中溶媒的空間之回收部。若藉由前述構成，可將成為蒸氣的產生源的溶媒作為回收液使用。或，亦可個別設置前述蒸氣產生部與前述回收部。若藉由前述構成，可更減低溶媒中雜質所致的污染。 The vapor generating unit may also serve as a collecting portion for recovering the peeled organic film (or the dissolved material of the organic film). In other words, it can also serve as a recovery portion for storing a space in the solvent in the steam generating portion. According to the above configuration, the solvent serving as the source of the vapor can be used as the recovery liquid. Alternatively, the steam generating unit and the collecting unit may be separately provided. According to the above configuration, contamination due to impurities in the solvent can be further reduced.
本發明有關的裝置可具備密閉容器，亦可使前述蒸氣產生部收容於前述密閉容器。據此，於密閉容器內，可效率佳地使有機膜與蒸氣接觸。又，可防止外部環境所致的有機膜之污染。再者，即使有機膜所含成分具有揮發性的情形，可減少回收的損失。 The apparatus according to the present invention may include a sealed container, and the vapor generating unit may be housed in the sealed container. According to this, in the sealed container, the organic film can be efficiently brought into contact with the vapor. Moreover, it is possible to prevent contamination of the organic film by the external environment. Further, even if the components contained in the organic film are volatile, the loss of recovery can be reduced.
密閉容器係只要由具備對溶媒的耐性(不會被溶媒溶解)的材質所形成即可。具體而言，只要為氟樹脂、石英等所形成的容器，即可不污染回收的分析用樣品而為較佳。就氟樹脂而言，例如，可列舉聚四氟乙烯(PTFE)、四氟乙烯‧全氟烷基乙烯醚共聚物(PFA)、聚偏二氟乙烯(PVDF)、聚氯三氟乙烯(PCTFE)。 The sealed container may be formed of a material having resistance to a solvent (not dissolved by a solvent). Specifically, as long as it is a container formed of a fluororesin, quartz or the like, it is preferable that the sample for analysis is not contaminated. Examples of the fluororesin include polytetrafluoroethylene (PTFE), tetrafluoroethylene, perfluoroalkyl vinyl ether copolymer (PFA), polyvinylidene fluoride (PVDF), and polychlorotrifluoroethylene (PCTFE). ).
前述密閉容器亦可兼作分析容器。即，前述密閉容器可為直接被裝置於用以實施感應耦合電漿質譜儀分析法(ICP-MS)、感應耦合電漿原子放射光譜儀分析法(ICP-AES)、原子吸光分析法(AAS)、離子層析法、毛細管電泳 法、液體層析法、或氣體層析法的裝置而被使用的樣品容器，亦可為用以藉由酸分解法、燃焼法、溶媒溶解法、溶媒抽出法等進行前處理的前處理容器。即，本說明書中的分析容器可為兼具樣品容器與前處理容器者。據此，藉由各式各樣的分析方法可分析被回收於前述密閉容器內的分析用樣品。 The sealed container may also serve as an analysis container. That is, the sealed container may be directly used for performing inductively coupled plasma mass spectrometry (ICP-MS), inductively coupled plasma atomic emission spectrometry (ICP-AES), and atomic absorption spectrometry (AAS). Ion chromatography, capillary electrophoresis The sample container used in the apparatus, the liquid chromatography method, or the gas chromatography apparatus may be a pretreatment container for pretreatment by an acid decomposition method, a combustion method, a solvent dissolution method, a solvent extraction method, or the like. . That is, the analysis container in the present specification may be a sample container and a pretreatment container. Accordingly, the analysis sample recovered in the sealed container can be analyzed by various analytical methods.
本發明有關的裝置可具備配置含有機膜形成的基材之基材配置部。基材配置部之構成係只要為可配置基材的構成即可，並未特別限定。基材配置部係例如可呈現可配置基材的台而被構成。基材配置部亦可為具備可保持基材的臂或夾具之類的固定構件。 The apparatus according to the present invention may include a substrate arrangement portion in which a substrate including an organic film is disposed. The configuration of the substrate arrangement portion is not particularly limited as long as it is a configuration in which the substrate can be disposed. The substrate arrangement portion is configured to be, for example, a table in which a substrate can be disposed. The base material arrangement portion may be a fixing member including an arm or a jig capable of holding the substrate.
基材配置部可被設置於前述密閉容器內。又，密閉容器具備開口部，而前述開口部可兼作基材配置部。此情形，可藉由將基材配置於前述開口部而封閉開口部，而密閉容器。 The substrate arrangement portion may be disposed in the sealed container. Further, the sealed container has an opening, and the opening can also serve as a substrate arrangement portion. In this case, the container can be sealed by arranging the substrate on the opening to close the opening.
蒸氣產生部與有機膜之位置關係並未特別限定。例如，將膜所形成的面朝下的方式來配置基材，可使自下側與蒸氣接觸。又，將膜所形成的面朝上的方式來配置基材，可使自上側與蒸氣接觸。又，將膜所形成的面朝向與重力方向垂直的方向來配置基材，可使與蒸氣接觸。 The positional relationship between the vapor generating portion and the organic film is not particularly limited. For example, the substrate may be disposed such that the surface formed by the film faces downward, and the vapor may be brought into contact with the vapor from the lower side. Further, the substrate is placed such that the surface formed by the film faces upward, and the upper side can be brought into contact with the vapor. Further, the substrate is placed in a direction perpendicular to the direction of gravity in the direction in which the film is formed, and is brought into contact with the vapor.
將膜所形成的面朝下的方式配置基材，可於其下側設置兼作回收部的蒸氣產生部。其中，自下側使與蒸氣接觸的情形，使藉由膜(或膜之溶解物)本身重量朝重力方向落下，亦可回收於回收部。 The substrate is disposed such that the surface formed by the film faces downward, and a vapor generating portion that also serves as a collecting portion can be provided on the lower side. Among them, the contact with the vapor from the lower side is allowed to fall in the direction of gravity by the weight of the film (or the dissolved matter of the film), and may be recovered in the recovery portion.
本發明並未被限定於上述各實施形態，可有於請求項所示範圍內的各種變更，適當組合於相異的實施形態中各自揭示的技術的手段而獲得的實施形態亦包含於本發明之技術的範圍。再者，藉由組合各實施形態各自揭示的技術手段，可形成新的技術特徵。 The present invention is not limited to the above-described embodiments, and various embodiments within the scope of the claims can be combined with the embodiments disclosed in the respective embodiments. The scope of the technology. Furthermore, new technical features can be formed by combining the technical means disclosed in each embodiment.
以下說明本發明之實施例，但只要不脫離本發明之旨趣，本發明並未限定於此等實施例。 The embodiments of the present invention are described below, but the present invention is not limited to the embodiments as long as it does not depart from the gist of the present invention.
使用參(乙醯基丙酮根)銥(III)(Tris(acetylacetonato)iridium(III))作為有機膜材料，藉由滴下塗佈法於基板上形成有機膜。就基板而言，使用60mm×60mm之Si晶圓。有機膜之質量為1mg。 An organic film was formed on the substrate by a drop coating method using ruthenium (III) (Tris (acetylacetonato) iridium (III)) as an organic film material. For the substrate, a 60 mm x 60 mm Si wafer was used. The mass of the organic film was 1 mg.
於PTFE製之容器中添加作為蒸氣源之5mL之硝酸(68%)。將有機膜所形成的面朝下，將基板配置於前述容器之開口部上。使用加熱板(設定溫度：150℃)而將容器加熱，使產生的蒸氣與有機膜接觸30分鐘。 5 mL of nitric acid (68%) as a vapor source was added to a vessel made of PTFE. The substrate was placed face down, and the substrate was placed on the opening of the container. The vessel was heated using a hot plate (setting temperature: 150 ° C), and the generated vapor was brought into contact with the organic film for 30 minutes.
藉由前述蒸氣之接觸，有機膜被剝離，且被回收於前述容器內。將回收的有機膜作酸分解，之後，藉由ICP-MS(PerkinElmer公司製)，求得有機膜中之銥之回收量及回收率。又，將前述實驗重複進行2次。 The organic film is peeled off by the contact of the aforementioned vapor, and is recovered in the aforementioned container. The recovered organic film was subjected to acid decomposition, and then the amount of recovery and recovery of the ruthenium in the organic film were determined by ICP-MS (manufactured by PerkinElmer Co., Ltd.). Further, the above experiment was repeated twice.
於表1顯示銥之理論量、回收量、回收率。又，銥之理論量係藉由有機膜之質量(g)×有機膜材料中之銥之濃度(μg/g)而算出。由表1可知，若依據本發明有關的分析用樣品之回收方法，可以高回收率回收有機膜之成分。 Table 1 shows the theoretical amount, recovery amount, and recovery rate of ruthenium. Further, the theoretical amount of ruthenium was calculated from the mass (g) of the organic film × the concentration (μg/g) of ruthenium in the organic film material. As is apparent from Table 1, according to the method for recovering an analysis sample according to the present invention, the composition of the organic film can be recovered with high recovery.
除了對參(乙醯基丙酮根)銥(III)，添加50ng之已知濃度之各元素標準(SPEX 公司製)以外，與實施例1同樣地形成及回收有機膜。 In addition to the ginseng (ethyl acetonate) ruthenium (III), add 50 ng of each element standard of known concentration (SPEX An organic film was formed and recovered in the same manner as in Example 1 except for the company.
將回收的有機膜作酸分解，之後，藉由ICP-MS(PerkinElmer公司製)，求得有機膜中各元素之回收率。 The recovered organic film was subjected to acid decomposition, and then the recovery ratio of each element in the organic film was determined by ICP-MS (manufactured by PerkinElmer Co., Ltd.).
於表2呈示各元素之回收率。該回收率係表示相對於元素標準之添加量，對應該元素標準的元素之回收量的比率。任何一種元素皆可以79%以上之高回收率加以回收。 The recovery of each element is presented in Table 2. The recovery rate is a ratio indicating the amount of recovery of the element corresponding to the elemental standard with respect to the amount of addition of the elemental standard. Any element can be recovered with a high recovery rate of over 79%.
使用4,4’-雙(9H-咔唑-9-基)聯苯作為有機膜材料，藉由旋轉塗佈法於基板上形成有機膜。就基板而言，使用60mm×60mm之Si晶圓。有機膜之厚度為40nm。 4,4'-bis(9H-carbazol-9-yl)biphenyl was used as an organic film material, and an organic film was formed on the substrate by spin coating. For the substrate, a 60 mm x 60 mm Si wafer was used. The thickness of the organic film was 40 nm.
於PTFE製之容器中添加作為蒸氣源之5mL之硝酸(68%)。將有機膜所形成的面朝下，將基板配置於前述容器之開口部上。使用加熱板(設定溫度：150℃)而將容器加熱，使產生的蒸氣與有機膜接觸45分鐘。 5 mL of nitric acid (68%) as a vapor source was added to a vessel made of PTFE. The substrate was placed face down, and the substrate was placed on the opening of the container. The vessel was heated using a hot plate (setting temperature: 150 ° C), and the generated vapor was brought into contact with the organic film for 45 minutes.
藉由前述蒸氣之接觸，有機膜之厚度方向的一部分區域被剝，且被回收於前述容器內。各自使用其他容器而重複2次前述操作，並將有機膜之厚度方向的一部分區域作階段地回收。 A part of the thickness direction of the organic film is peeled off by the contact of the vapor, and is recovered in the container. The above operation was repeated twice using each other container, and a part of the thickness direction of the organic film was recovered in stages.
將被回收於各自容器的樣品作酸分解，之後，藉由ICP-MS(PerkinElmer公司製)，求得有機膜中之銫之回收量及回收率。 The sample collected in each container was subjected to acid decomposition, and then the amount of recovery and recovery in the organic film were determined by ICP-MS (manufactured by PerkinElmer Co., Ltd.).
於表3中呈示銫之理論量、回收量、回收率。又，銫之理論量係藉由有機膜之質量(g)×有機膜材料中之銫之濃度(ng/g)而算出。由表3可知可以高回收率將有機膜所含的微量雜質回收。又，已知可階段性回收有機膜所含的微量之雜質。 The theoretical amount, recovery amount, and recovery rate of ruthenium are shown in Table 3. Further, the theoretical amount of ruthenium was calculated from the mass (g) of the organic film × the concentration (ng/g) of ruthenium in the organic film material. As is clear from Table 3, trace impurities contained in the organic film can be recovered at a high recovery rate. Further, it is known that a trace amount of impurities contained in the organic film can be recovered in stages.
使用4,4’-雙(9H-咔唑-9-基)聯苯作為有機膜材料，藉由真空蒸鍍法於基板上形成有機膜。就基板而言，使用60mm×60mm之Si晶圓。有機膜之厚度為200nm。 4,4'-bis(9H-carbazol-9-yl)biphenyl was used as an organic film material, and an organic film was formed on the substrate by vacuum evaporation. For the substrate, a 60 mm x 60 mm Si wafer was used. The thickness of the organic film was 200 nm.
於PFA製之容器中添加作為蒸氣源之5mL之硝酸(68%)。將有 機膜所形成的面朝下，將基板配置於前述容器之開口部上。使用加熱板(設定溫度：150℃)而將容器加熱，使產生的蒸氣與有機膜接觸45分鐘。 5 mL of nitric acid (68%) as a vapor source was added to a container made of PFA. will have The surface formed by the film is faced downward, and the substrate is placed on the opening of the container. The vessel was heated using a hot plate (setting temperature: 150 ° C), and the generated vapor was brought into contact with the organic film for 45 minutes.
藉由前述蒸氣之接觸，有機膜被剝離，且被回收於前述容器內。將回收的有機膜作酸分解，之後，藉由ICP-MS(PerkinElmer公司製)，將有機膜中之雜質定量。 The organic film is peeled off by the contact of the aforementioned vapor, and is recovered in the aforementioned container. The recovered organic film was subjected to acid decomposition, and then the impurities in the organic film were quantified by ICP-MS (manufactured by PerkinElmer Co., Ltd.).
於表4呈示作為雜質被檢測的各元素之檢出量。又，「<1」表示檢出量低於定量下限。由表4可知，可高敏感度定量有機膜所含的微量雜質。 The amount of detection of each element detected as an impurity is shown in Table 4. Further, "<1" indicates that the detected amount is lower than the lower limit of quantitation. As can be seen from Table 4, the trace impurities contained in the organic film can be quantified with high sensitivity.
[表4]
使用N,N’-二苯基-N,N’-二(m-甲苯基)聯苯胺作為有機材料，藉由旋轉塗佈法於基板上形成有機膜。使用4吋φ之Si晶圓作為基板。又，形成有機膜之際，添加已知量之磷酸三苯酯(triphenyl phosphate)。 An organic film was formed on the substrate by spin coating using N,N'-diphenyl-N,N'-bis(m-tolyl)benzidine as an organic material. A 4 φ φ Si wafer was used as the substrate. Further, when an organic film is formed, a known amount of triphenyl phosphate is added.
於PFA製之容器中添加作為蒸氣源之1mL之硝酸(68%)及1mL之水。將有機膜所形成的面朝下，將基板配置於前述容器之開口部上。使用加熱板(設定溫度：150℃)而將容器加熱，使產生的蒸氣與有機膜接觸60分鐘。 1 mL of nitric acid (68%) as a vapor source and 1 mL of water were added to a container made of PFA. The substrate was placed face down, and the substrate was placed on the opening of the container. The vessel was heated using a hot plate (setting temperature: 150 ° C), and the generated vapor was brought into contact with the organic film for 60 minutes.
藉由前述蒸氣之接觸，有機膜被剝離，且被回收於前述容器內。將回收的有機膜作酸分解，之後，藉由ICP-MS(PerkinElmer公司製)，求得有機膜中磷之回收量及回收率。 The organic film is peeled off by the contact of the aforementioned vapor, and is recovered in the aforementioned container. The recovered organic film was subjected to acid decomposition, and then the amount of phosphorus recovered and the recovery rate in the organic film were determined by ICP-MS (manufactured by PerkinElmer Co., Ltd.).
於表5呈示磷之添加量、回收量、回收率。該回收率係表示相對於由磷酸三苯酯之添加量所求得的磷添加量之磷的回收量的比率。由表5可知，可以高回收率將有機膜所含的有機形態之雜質回收。 Table 5 shows the amount of phosphorus added, the amount recovered, and the recovery. The recovery ratio is a ratio of the amount of phosphorus recovered from the phosphorus addition amount determined from the amount of addition of triphenyl phosphate. As is clear from Table 5, the organic form impurities contained in the organic film can be recovered at a high recovery rate.
使用N,N’-二苯基-N,N’-二(m-甲苯基)聯苯胺作為有機材料，藉由旋轉塗佈法於基板上形成有機膜。使用4吋φ之Si晶圓作為基板。 An organic film was formed on the substrate by spin coating using N,N'-diphenyl-N,N'-bis(m-tolyl)benzidine as an organic material. A 4 φ φ Si wafer was used as the substrate.
於個別PFA製之容器中各添加1mL作為蒸氣源之水、硝酸(68%)、乙腈、氯仿、二氯甲烷、四氫呋喃、己烷、甲苯、甲醇、氨水(20%)、氫氧化四甲銨水溶液(15%)、氫氧化鈣水溶液(5%)。將有機膜所形成的面朝下，將基板配置於前述容器之開口部上。使用加熱板(設定溫度：150℃)而將容器加熱，使各自產生的蒸氣與有機膜接觸30分鐘。 1 mL of water as a vapor source, nitric acid (68%), acetonitrile, chloroform, dichloromethane, tetrahydrofuran, hexane, toluene, methanol, ammonia (20%), tetramethylammonium hydroxide were added to each container made of PFA. Aqueous solution (15%), aqueous calcium hydroxide solution (5%). The substrate was placed face down, and the substrate was placed on the opening of the container. The vessel was heated using a hot plate (setting temperature: 150 ° C), and the respective generated vapor was brought into contact with the organic membrane for 30 minutes.
於表6，於以目視可確認剝離的溶媒記錄圓圈。得知有機膜可使用水、酸、鹼、有機溶媒而剝離。 In Table 6, the solvent-removed circle was confirmed by visual observation. It was found that the organic film can be peeled off using water, an acid, a base, or an organic solvent.
本發明係可利用於有機電子等之各種領域中有機膜所含成分之分析。 The present invention can be utilized for analysis of components contained in an organic film in various fields such as organic electronics.
Claims (13)
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2014112237 | 2014-05-30 | ||
| JP2014-112237 | 2014-05-30 |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| TW201600857A true TW201600857A (en) | 2016-01-01 |
| TWI711823B TWI711823B (en) | 2020-12-01 |
Family
ID=54698993
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| TW104117486A TWI711823B (en) | 2014-05-30 | 2015-05-29 | Method of collecting analytic sample, and use of the method |
Country Status (4)
| Country | Link |
|---|---|
| JP (1) | JP6687518B2 (en) |
| KR (1) | KR102379619B1 (en) |
| TW (1) | TWI711823B (en) |
| WO (1) | WO2015182670A1 (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| TWI808094B (en) * | 2017-09-07 | 2023-07-11 | 美商自然科學公司 | Automated system for remote inline concentration of ultra-low concentrations in pure chemicals |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US10330573B2 (en) * | 2017-07-10 | 2019-06-25 | Cem Corporation | Rapid sample preparation for analytical analysis using dispersive energized extraction |
Family Cites Families (13)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS62209335A (en) * | 1986-03-10 | 1987-09-14 | Nec Corp | Apparatus for decomposing thin film |
| JPS63158840A (en) * | 1986-12-23 | 1988-07-01 | Toshiba Corp | Method and apparatus for decomposing thin film on semiconductor substrate |
| JPH04204035A (en) * | 1990-11-30 | 1992-07-24 | Hitachi Ltd | Sample pretreatment device |
| JP3071968B2 (en) * | 1992-11-13 | 2000-07-31 | 松下電子工業株式会社 | Manufacturing method of semiconductor integrated circuit |
| JPH0922895A (en) * | 1995-07-06 | 1997-01-21 | Toshiba Corp | Method of melting semiconductor material and melting device |
| JP2882377B2 (en) * | 1996-08-23 | 1999-04-12 | 日本電気株式会社 | Metal recovery container and metal recovery method |
| JP3409975B2 (en) * | 1996-09-11 | 2003-05-26 | 株式会社東芝 | Pollutant analyzer |
| JP3584430B2 (en) * | 1998-04-13 | 2004-11-04 | 清水建設株式会社 | Contaminant detection method |
| JP3522249B2 (en) | 2000-10-25 | 2004-04-26 | 鹿児島日本電気株式会社 | Organic film peeling method |
| JP3977761B2 (en) * | 2003-03-05 | 2007-09-19 | 株式会社東芝 | Quality control method for electronic component materials |
| JP2004347543A (en) * | 2003-05-26 | 2004-12-09 | Nec Corp | Evaluation method of semiconductor wafer and its evaluation device |
| JP4034240B2 (en) | 2003-06-25 | 2008-01-16 | シャープ株式会社 | Stripping cleaning method and stripping cleaning apparatus |
| JP2012049287A (en) * | 2010-08-26 | 2012-03-08 | National Institute Of Advanced Industrial & Technology | Surface modification silicon substrate |
-
2015
- 2015-05-27 JP JP2016523541A patent/JP6687518B2/en active Active
- 2015-05-27 KR KR1020167036306A patent/KR102379619B1/en active IP Right Grant
- 2015-05-27 WO PCT/JP2015/065286 patent/WO2015182670A1/en active Application Filing
- 2015-05-29 TW TW104117486A patent/TWI711823B/en active
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| TWI808094B (en) * | 2017-09-07 | 2023-07-11 | 美商自然科學公司 | Automated system for remote inline concentration of ultra-low concentrations in pure chemicals |
Also Published As
| Publication number | Publication date |
|---|---|
| KR102379619B1 (en) | 2022-03-25 |
| WO2015182670A1 (en) | 2015-12-03 |
| JP6687518B2 (en) | 2020-04-22 |
| TWI711823B (en) | 2020-12-01 |
| KR20170012414A (en) | 2017-02-02 |
| JPWO2015182670A1 (en) | 2017-04-20 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Chow et al. | Wetting of mono and few-layered WS2 and MoS2 films supported on Si/SiO2 substrates | |
| Luo et al. | Role of graphene in water-assisted oxidation of copper in relation to dry transfer of graphene | |
| Russo et al. | Controlling protein adsorption on graphene for cryo-EM using low-energy hydrogen plasmas | |
| US8932954B2 (en) | Impurity analysis device and method | |
| Ohnemus et al. | Laboratory intercomparison of marine particulate digestions including Piranha: a novel chemical method for dissolution of polyethersulfone filters | |
| Zahiri et al. | Active control over the wettability from superhydrophobic to superhydrophilic by electrochemically altering the oxidation state in a low voltage range | |
| Loh et al. | Impurity-induced emission in Re-doped WS2 monolayers | |
| Islam et al. | Centimeter-scale 2D van der Waals vertical heterostructures integrated on deformable substrates enabled by gold sacrificial layer-assisted growth | |
| TWI749125B (en) | Analysis method of surface impurities of polysilicon crushed material | |
| Ghosh et al. | Insights on defect-mediated heterogeneous nucleation of graphene on copper | |
| JP2017116313A (en) | Analysis device for silicon substrate | |
| TW201600857A (en) | Method of collecting analytic sample, and use of the method | |
| Ghodsi et al. | Assessment of pressure and density of confined water in graphene liquid cells | |
| KR102178251B1 (en) | Vapor phase decomposition method, analysis method, quality control method, production method, and container | |
| JP5413342B2 (en) | Silicon wafer surface layer etching method and silicon wafer metal contamination analysis method | |
| JP2002368052A (en) | Method for desorbing silicon and method for analyzing impurities in silicon wafer | |
| Seki et al. | Photoluminescence of CVD-grown MoS2 modified by pH under aqueous solutions toward potential biological sensing | |
| JP2004212261A (en) | Method of analyzing metal impurities on silicon substrate surface | |
| JP2009294091A (en) | Analyzing method of contaminant in silicon wafer | |
| TWI759274B (en) | Method of controlling apparatus for manufacturing organic electronic device | |
| JP5407609B2 (en) | Silicon wafer evaluation method | |
| Kong et al. | EGaIn microelectrode for electrical characterization of ITO-based van der Waals interface and airborne molecular contamination of ITO surface | |
| JP3890047B2 (en) | Method for analyzing metal in quartz and jig for analysis | |
| TW201335593A (en) | Container, vapor phase decomposition method, vapor phase decomposition apparatus, analytical method, and analytical apparatus | |
| JP2002184828A (en) | Method of analyzing metallic impurities in semiconductor substrate |