JP2020097758A - Particle for vacuum deposition - Google Patents
Particle for vacuum deposition Download PDFInfo
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- JP2020097758A JP2020097758A JP2018235361A JP2018235361A JP2020097758A JP 2020097758 A JP2020097758 A JP 2020097758A JP 2018235361 A JP2018235361 A JP 2018235361A JP 2018235361 A JP2018235361 A JP 2018235361A JP 2020097758 A JP2020097758 A JP 2020097758A
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- Prior art keywords
- particles
- vapor deposition
- particle
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- 239000002245 particle Substances 0.000 title claims abstract description 218
- 238000001771 vacuum deposition Methods 0.000 title abstract description 13
- 239000000463 material Substances 0.000 claims abstract description 63
- 238000000034 method Methods 0.000 claims abstract description 54
- 150000001875 compounds Chemical class 0.000 claims abstract description 15
- 229910052783 alkali metal Inorganic materials 0.000 claims abstract description 10
- 150000001340 alkali metals Chemical group 0.000 claims abstract description 10
- 229910052784 alkaline earth metal Inorganic materials 0.000 claims abstract description 10
- 150000001342 alkaline earth metals Chemical group 0.000 claims abstract description 10
- 238000001704 evaporation Methods 0.000 claims abstract description 10
- 230000008020 evaporation Effects 0.000 claims abstract description 10
- 125000005843 halogen group Chemical group 0.000 claims abstract description 9
- 238000007740 vapor deposition Methods 0.000 claims description 102
- 239000010410 layer Substances 0.000 claims description 84
- 239000008187 granular material Substances 0.000 claims description 43
- 239000002346 layers by function Substances 0.000 claims description 43
- 230000002093 peripheral effect Effects 0.000 claims description 23
- 238000004519 manufacturing process Methods 0.000 claims description 22
- 238000007738 vacuum evaporation Methods 0.000 claims description 15
- PUZPDOWCWNUUKD-UHFFFAOYSA-M sodium fluoride Chemical compound [F-].[Na+] PUZPDOWCWNUUKD-UHFFFAOYSA-M 0.000 claims description 13
- 239000011775 sodium fluoride Substances 0.000 claims description 6
- 235000013024 sodium fluoride Nutrition 0.000 claims description 6
- 239000002585 base Substances 0.000 claims description 3
- 238000005019 vapor deposition process Methods 0.000 claims description 2
- 239000010408 film Substances 0.000 description 48
- 239000000758 substrate Substances 0.000 description 21
- 238000002347 injection Methods 0.000 description 18
- 239000007924 injection Substances 0.000 description 18
- 239000013078 crystal Substances 0.000 description 14
- 238000000576 coating method Methods 0.000 description 13
- 238000010298 pulverizing process Methods 0.000 description 12
- 238000010304 firing Methods 0.000 description 11
- 230000005525 hole transport Effects 0.000 description 11
- -1 polyethylene terephthalate Polymers 0.000 description 11
- 239000000126 substance Substances 0.000 description 11
- 229940125904 compound 1 Drugs 0.000 description 9
- 238000005245 sintering Methods 0.000 description 8
- 238000010586 diagram Methods 0.000 description 6
- 239000002019 doping agent Substances 0.000 description 6
- 239000002994 raw material Substances 0.000 description 6
- 150000004696 coordination complex Chemical class 0.000 description 5
- 229910052751 metal Inorganic materials 0.000 description 5
- 239000002184 metal Substances 0.000 description 5
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 5
- 239000002904 solvent Substances 0.000 description 5
- 230000004888 barrier function Effects 0.000 description 4
- ZYGHJZDHTFUPRJ-UHFFFAOYSA-N coumarin Chemical compound C1=CC=C2OC(=O)C=CC2=C1 ZYGHJZDHTFUPRJ-UHFFFAOYSA-N 0.000 description 4
- 238000007641 inkjet printing Methods 0.000 description 4
- 238000005259 measurement Methods 0.000 description 4
- 229920000123 polythiophene Polymers 0.000 description 4
- 238000005096 rolling process Methods 0.000 description 4
- 239000010409 thin film Substances 0.000 description 4
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 3
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 3
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 238000000151 deposition Methods 0.000 description 3
- 238000011156 evaluation Methods 0.000 description 3
- 230000003287 optical effect Effects 0.000 description 3
- 229910052697 platinum Inorganic materials 0.000 description 3
- 229920000767 polyaniline Polymers 0.000 description 3
- 230000008569 process Effects 0.000 description 3
- 229910052710 silicon Inorganic materials 0.000 description 3
- 239000010703 silicon Substances 0.000 description 3
- 238000002834 transmittance Methods 0.000 description 3
- VQGHOUODWALEFC-UHFFFAOYSA-N 2-phenylpyridine Chemical compound C1=CC=CC=C1C1=CC=CC=N1 VQGHOUODWALEFC-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 2
- 229910052693 Europium Inorganic materials 0.000 description 2
- 229920001609 Poly(3,4-ethylenedioxythiophene) Polymers 0.000 description 2
- 239000004698 Polyethylene Substances 0.000 description 2
- 239000004743 Polypropylene Substances 0.000 description 2
- KAESVJOAVNADME-UHFFFAOYSA-N Pyrrole Chemical compound C=1C=CNC=1 KAESVJOAVNADME-UHFFFAOYSA-N 0.000 description 2
- NRCMAYZCPIVABH-UHFFFAOYSA-N Quinacridone Chemical compound N1C2=CC=CC=C2C(=O)C2=C1C=C1C(=O)C3=CC=CC=C3NC1=C2 NRCMAYZCPIVABH-UHFFFAOYSA-N 0.000 description 2
- SMWDFEZZVXVKRB-UHFFFAOYSA-N Quinoline Chemical compound N1=CC=CC2=CC=CC=C21 SMWDFEZZVXVKRB-UHFFFAOYSA-N 0.000 description 2
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 2
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 2
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 2
- 150000004982 aromatic amines Chemical class 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 238000007611 bar coating method Methods 0.000 description 2
- 239000011324 bead Substances 0.000 description 2
- 229910052790 beryllium Inorganic materials 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 229960000956 coumarin Drugs 0.000 description 2
- 235000001671 coumarin Nutrition 0.000 description 2
- DMBHHRLKUKUOEG-UHFFFAOYSA-N diphenylamine Chemical compound C=1C=CC=CC=1NC1=CC=CC=C1 DMBHHRLKUKUOEG-UHFFFAOYSA-N 0.000 description 2
- 229910052741 iridium Inorganic materials 0.000 description 2
- WCPAKWJPBJAGKN-UHFFFAOYSA-N oxadiazole Chemical compound C1=CON=N1 WCPAKWJPBJAGKN-UHFFFAOYSA-N 0.000 description 2
- 150000004866 oxadiazoles Chemical class 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 125000002080 perylenyl group Chemical group C1(=CC=C2C=CC=C3C4=CC=CC5=CC=CC(C1=C23)=C45)* 0.000 description 2
- CSHWQDPOILHKBI-UHFFFAOYSA-N peryrene Natural products C1=CC(C2=CC=CC=3C2=C2C=CC=3)=C3C2=CC=CC3=C1 CSHWQDPOILHKBI-UHFFFAOYSA-N 0.000 description 2
- 229920003227 poly(N-vinyl carbazole) Polymers 0.000 description 2
- 229920000548 poly(silane) polymer Polymers 0.000 description 2
- 229920000573 polyethylene Polymers 0.000 description 2
- 229920000139 polyethylene terephthalate Polymers 0.000 description 2
- 239000005020 polyethylene terephthalate Substances 0.000 description 2
- 229920002098 polyfluorene Polymers 0.000 description 2
- 229920001155 polypropylene Polymers 0.000 description 2
- 150000004032 porphyrins Chemical class 0.000 description 2
- 238000007639 printing Methods 0.000 description 2
- XOLBLPGZBRYERU-UHFFFAOYSA-N tin dioxide Chemical compound O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 description 2
- 229910001887 tin oxide Inorganic materials 0.000 description 2
- 229910052725 zinc Inorganic materials 0.000 description 2
- 239000011701 zinc Substances 0.000 description 2
- SCYULBFZEHDVBN-UHFFFAOYSA-N 1,1-Dichloroethane Chemical compound CC(Cl)Cl SCYULBFZEHDVBN-UHFFFAOYSA-N 0.000 description 1
- DHKHKXVYLBGOIT-UHFFFAOYSA-N 1,1-Diethoxyethane Chemical compound CCOC(C)OCC DHKHKXVYLBGOIT-UHFFFAOYSA-N 0.000 description 1
- NGQSLSMAEVWNPU-YTEMWHBBSA-N 1,2-bis[(e)-2-phenylethenyl]benzene Chemical compound C=1C=CC=CC=1/C=C/C1=CC=CC=C1\C=C\C1=CC=CC=C1 NGQSLSMAEVWNPU-YTEMWHBBSA-N 0.000 description 1
- SHXCHSNZIGEBFL-UHFFFAOYSA-N 1,3-benzothiazole;zinc Chemical compound [Zn].C1=CC=C2SC=NC2=C1 SHXCHSNZIGEBFL-UHFFFAOYSA-N 0.000 description 1
- KLCLIOISYBHYDZ-UHFFFAOYSA-N 1,4,4-triphenylbuta-1,3-dienylbenzene Chemical compound C=1C=CC=CC=1C(C=1C=CC=CC=1)=CC=C(C=1C=CC=CC=1)C1=CC=CC=C1 KLCLIOISYBHYDZ-UHFFFAOYSA-N 0.000 description 1
- AZQWKYJCGOJGHM-UHFFFAOYSA-N 1,4-benzoquinone Chemical compound O=C1C=CC(=O)C=C1 AZQWKYJCGOJGHM-UHFFFAOYSA-N 0.000 description 1
- UIWLITBBFICQKW-UHFFFAOYSA-N 1h-benzo[h]quinolin-2-one Chemical compound C1=CC=C2C3=NC(O)=CC=C3C=CC2=C1 UIWLITBBFICQKW-UHFFFAOYSA-N 0.000 description 1
- VFBJMPNFKOMEEW-UHFFFAOYSA-N 2,3-diphenylbut-2-enedinitrile Chemical group C=1C=CC=CC=1C(C#N)=C(C#N)C1=CC=CC=C1 VFBJMPNFKOMEEW-UHFFFAOYSA-N 0.000 description 1
- DWYHDSLIWMUSOO-UHFFFAOYSA-N 2-phenyl-1h-benzimidazole Chemical compound C1=CC=CC=C1C1=NC2=CC=CC=C2N1 DWYHDSLIWMUSOO-UHFFFAOYSA-N 0.000 description 1
- DDTHMESPCBONDT-UHFFFAOYSA-N 4-(4-oxocyclohexa-2,5-dien-1-ylidene)cyclohexa-2,5-dien-1-one Chemical class C1=CC(=O)C=CC1=C1C=CC(=O)C=C1 DDTHMESPCBONDT-UHFFFAOYSA-N 0.000 description 1
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 description 1
- 239000005725 8-Hydroxyquinoline Substances 0.000 description 1
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 description 1
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 1
- DKPFZGUDAPQIHT-UHFFFAOYSA-N Butyl acetate Natural products CCCCOC(C)=O DKPFZGUDAPQIHT-UHFFFAOYSA-N 0.000 description 1
- AJWRRBADQOOFSF-UHFFFAOYSA-N C1=CC=C2OC([Zn])=NC2=C1 Chemical compound C1=CC=C2OC([Zn])=NC2=C1 AJWRRBADQOOFSF-UHFFFAOYSA-N 0.000 description 1
- UXYHZIYEDDINQH-UHFFFAOYSA-N C1=CNC2=C3C=NN=C3C=CC2=C1 Chemical compound C1=CNC2=C3C=NN=C3C=CC2=C1 UXYHZIYEDDINQH-UHFFFAOYSA-N 0.000 description 1
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- 241000284156 Clerodendrum quadriloculare Species 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- 229910052692 Dysprosium Inorganic materials 0.000 description 1
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- 229930192627 Naphthoquinone Natural products 0.000 description 1
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 1
- 229920012266 Poly(ether sulfone) PES Polymers 0.000 description 1
- 229920000265 Polyparaphenylene Polymers 0.000 description 1
- 229920000292 Polyquinoline Polymers 0.000 description 1
- 239000004372 Polyvinyl alcohol Substances 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- 229910052581 Si3N4 Inorganic materials 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 1
- PJANXHGTPQOBST-VAWYXSNFSA-N Stilbene Natural products C=1C=CC=CC=1/C=C/C1=CC=CC=C1 PJANXHGTPQOBST-VAWYXSNFSA-N 0.000 description 1
- 229910052771 Terbium Inorganic materials 0.000 description 1
- XBDYBAVJXHJMNQ-UHFFFAOYSA-N Tetrahydroanthracene Natural products C1=CC=C2C=C(CCCC3)C3=CC2=C1 XBDYBAVJXHJMNQ-UHFFFAOYSA-N 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- DGEZNRSVGBDHLK-UHFFFAOYSA-N [1,10]phenanthroline Chemical compound C1=CN=C2C3=NC=CC=C3C=CC2=C1 DGEZNRSVGBDHLK-UHFFFAOYSA-N 0.000 description 1
- XHCLAFWTIXFWPH-UHFFFAOYSA-N [O-2].[O-2].[O-2].[O-2].[O-2].[V+5].[V+5] Chemical compound [O-2].[O-2].[O-2].[O-2].[O-2].[V+5].[V+5] XHCLAFWTIXFWPH-UHFFFAOYSA-N 0.000 description 1
- 239000011354 acetal resin Substances 0.000 description 1
- 229910001515 alkali metal fluoride Inorganic materials 0.000 description 1
- HSFWRNGVRCDJHI-UHFFFAOYSA-N alpha-acetylene Natural products C#C HSFWRNGVRCDJHI-UHFFFAOYSA-N 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- 229910003481 amorphous carbon Inorganic materials 0.000 description 1
- 150000001448 anilines Chemical class 0.000 description 1
- PYKYMHQGRFAEBM-UHFFFAOYSA-N anthraquinone Natural products CCC(=O)c1c(O)c2C(=O)C3C(C=CC=C3O)C(=O)c2cc1CC(=O)OC PYKYMHQGRFAEBM-UHFFFAOYSA-N 0.000 description 1
- 150000004056 anthraquinones Chemical class 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 1
- 229910052788 barium Inorganic materials 0.000 description 1
- DSAJWYNOEDNPEQ-UHFFFAOYSA-N barium atom Chemical compound [Ba] DSAJWYNOEDNPEQ-UHFFFAOYSA-N 0.000 description 1
- ATBAMAFKBVZNFJ-UHFFFAOYSA-N beryllium atom Chemical compound [Be] ATBAMAFKBVZNFJ-UHFFFAOYSA-N 0.000 description 1
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 1
- 229910052794 bromium Inorganic materials 0.000 description 1
- 150000001649 bromium compounds Chemical class 0.000 description 1
- 229910052792 caesium Inorganic materials 0.000 description 1
- TVFDJXOCXUVLDH-UHFFFAOYSA-N caesium atom Chemical compound [Cs] TVFDJXOCXUVLDH-UHFFFAOYSA-N 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- 239000011575 calcium Substances 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 150000001805 chlorine compounds Chemical class 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 239000011365 complex material Substances 0.000 description 1
- 239000004020 conductor Substances 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- HFXKQSZZZPGLKQ-UHFFFAOYSA-N cyclopentamine Chemical compound CNC(C)CC1CCCC1 HFXKQSZZZPGLKQ-UHFFFAOYSA-N 0.000 description 1
- 229960003263 cyclopentamine Drugs 0.000 description 1
- CUIWZLHUNCCYBL-UHFFFAOYSA-N decacyclene Chemical compound C12=C([C]34)C=CC=C4C=CC=C3C2=C2C(=C34)C=C[CH]C4=CC=CC3=C2C2=C1C1=CC=CC3=CC=CC2=C31 CUIWZLHUNCCYBL-UHFFFAOYSA-N 0.000 description 1
- 238000006073 displacement reaction Methods 0.000 description 1
- 239000003822 epoxy resin Substances 0.000 description 1
- 239000003759 ester based solvent Substances 0.000 description 1
- 239000004210 ether based solvent Substances 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 239000005038 ethylene vinyl acetate Substances 0.000 description 1
- OGPBJKLSAFTDLK-UHFFFAOYSA-N europium atom Chemical compound [Eu] OGPBJKLSAFTDLK-UHFFFAOYSA-N 0.000 description 1
- 230000005281 excited state Effects 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 150000008376 fluorenones Chemical class 0.000 description 1
- 150000004673 fluoride salts Chemical class 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- JVZRCNQLWOELDU-UHFFFAOYSA-N gamma-Phenylpyridine Natural products C1=CC=CC=C1C1=CC=NC=C1 JVZRCNQLWOELDU-UHFFFAOYSA-N 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 239000010931 gold Substances 0.000 description 1
- 230000005484 gravity Effects 0.000 description 1
- 238000007756 gravure coating Methods 0.000 description 1
- FUZZWVXGSFPDMH-UHFFFAOYSA-N hexanoic acid Chemical compound CCCCCC(O)=O FUZZWVXGSFPDMH-UHFFFAOYSA-N 0.000 description 1
- 238000005286 illumination Methods 0.000 description 1
- 229910003437 indium oxide Inorganic materials 0.000 description 1
- PJXISJQVUVHSOJ-UHFFFAOYSA-N indium(iii) oxide Chemical compound [O-2].[O-2].[O-2].[In+3].[In+3] PJXISJQVUVHSOJ-UHFFFAOYSA-N 0.000 description 1
- AMGQUBHHOARCQH-UHFFFAOYSA-N indium;oxotin Chemical compound [In].[Sn]=O AMGQUBHHOARCQH-UHFFFAOYSA-N 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 229910010272 inorganic material Inorganic materials 0.000 description 1
- 239000011147 inorganic material Substances 0.000 description 1
- 150000004694 iodide salts Chemical class 0.000 description 1
- 239000011630 iodine Substances 0.000 description 1
- 229910052740 iodine Inorganic materials 0.000 description 1
- 238000007733 ion plating Methods 0.000 description 1
- GKOZUEZYRPOHIO-UHFFFAOYSA-N iridium atom Chemical compound [Ir] GKOZUEZYRPOHIO-UHFFFAOYSA-N 0.000 description 1
- 239000005453 ketone based solvent Substances 0.000 description 1
- 150000002605 large molecules Chemical class 0.000 description 1
- 239000003446 ligand Substances 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 229910052976 metal sulfide Inorganic materials 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 229910000476 molybdenum oxide Inorganic materials 0.000 description 1
- DCZNSJVFOQPSRV-UHFFFAOYSA-N n,n-diphenyl-4-[4-(n-phenylanilino)phenyl]aniline Chemical compound C1=CC=CC=C1N(C=1C=CC(=CC=1)C=1C=CC(=CC=1)N(C=1C=CC=CC=1)C=1C=CC=CC=1)C1=CC=CC=C1 DCZNSJVFOQPSRV-UHFFFAOYSA-N 0.000 description 1
- 150000002791 naphthoquinones Chemical class 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 238000007645 offset printing Methods 0.000 description 1
- 239000011368 organic material Substances 0.000 description 1
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 1
- PQQKPALAQIIWST-UHFFFAOYSA-N oxomolybdenum Chemical compound [Mo]=O PQQKPALAQIIWST-UHFFFAOYSA-N 0.000 description 1
- 229960003540 oxyquinoline Drugs 0.000 description 1
- 238000000059 patterning Methods 0.000 description 1
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- FIZIRKROSLGMPL-UHFFFAOYSA-N phenoxazin-1-one Chemical compound C1=CC=C2N=C3C(=O)C=CC=C3OC2=C1 FIZIRKROSLGMPL-UHFFFAOYSA-N 0.000 description 1
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- 235000021286 stilbenes Nutrition 0.000 description 1
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- CIOAGBVUUVVLOB-UHFFFAOYSA-N strontium atom Chemical compound [Sr] CIOAGBVUUVVLOB-UHFFFAOYSA-N 0.000 description 1
- 125000005504 styryl group Chemical group 0.000 description 1
- WGPCGCOKHWGKJJ-UHFFFAOYSA-N sulfanylidenezinc Chemical compound [Zn]=S WGPCGCOKHWGKJJ-UHFFFAOYSA-N 0.000 description 1
- IFLREYGFSNHWGE-UHFFFAOYSA-N tetracene Chemical compound C1=CC=CC2=CC3=CC4=CC=CC=C4C=C3C=C21 IFLREYGFSNHWGE-UHFFFAOYSA-N 0.000 description 1
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- VLLMWSRANPNYQX-UHFFFAOYSA-N thiadiazole Chemical compound C1=CSN=N1.C1=CSN=N1 VLLMWSRANPNYQX-UHFFFAOYSA-N 0.000 description 1
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- ODHXBMXNKOYIBV-UHFFFAOYSA-N triphenylamine Chemical compound C1=CC=CC=C1N(C=1C=CC=CC=1)C1=CC=CC=C1 ODHXBMXNKOYIBV-UHFFFAOYSA-N 0.000 description 1
- 229910001935 vanadium oxide Inorganic materials 0.000 description 1
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- YVTHLONGBIQYBO-UHFFFAOYSA-N zinc indium(3+) oxygen(2-) Chemical compound [O--].[Zn++].[In+3] YVTHLONGBIQYBO-UHFFFAOYSA-N 0.000 description 1
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- 229910052984 zinc sulfide Inorganic materials 0.000 description 1
Landscapes
- Electroluminescent Light Sources (AREA)
- Physical Vapour Deposition (AREA)
Abstract
Description
本発明は、真空蒸着用粒体およびその製造方法、並びに真空蒸着用粒体から形成された蒸着膜を有する有機電子デバイスに関する。 TECHNICAL FIELD The present invention relates to a particle for vacuum vapor deposition, a method for manufacturing the same, and an organic electronic device having a vapor deposition film formed from the particle for vacuum vapor deposition.
特許文献1には、2元素以上からなる物質を、物質が蒸着する温度まで加熱された蒸着源に粒径が100〜1000μmの粉体を少量ずつ供給して基板上に成膜する蒸着方法が提案されている。特許文献2には、蒸発材料からなる等寸法球形材料が同時に1個だけ通過可能な孔を設けた円盤を備える蒸着材料の供給装置が提案されている。 Patent Document 1 discloses a vapor deposition method in which a substance consisting of two or more elements is supplied little by little to a vapor deposition source heated to a temperature at which the substance is vapor-deposited and a powder having a particle size of 100 to 1000 μm is formed on a substrate. Proposed. Patent Document 2 proposes a vapor deposition material supply apparatus including a disk provided with a hole through which only one equal-sized spherical material made of an evaporation material can pass at the same time.
特許文献1に記載の蒸着方法では、粒体を供給する供給装置に閉塞が発生する場合がある。特許文献2に記載の真空蒸着用材料は入手容易性に優れるものではない。 In the vapor deposition method described in Patent Document 1, the supply device that supplies the particles may be clogged. The material for vacuum vapor deposition described in Patent Document 2 is not easily available.
本発明の目的は、真空蒸着装置の供給部において閉塞を生じさせず、入手容易性に優れた真空蒸着用粒体を提供することである。 An object of the present invention is to provide a granular material for vacuum vapor deposition that does not cause blockage in the supply portion of the vacuum vapor deposition apparatus and is easily available.
本発明には以下の態様[1]〜[9]が含まれる。
[1] 式(1):
ABx (1)
[式中、Aは、アルカリ金属原子またはアルカリ土類金属原子を示し、Bは、ハロゲン原子を示し、およびxは1または2である]
で表される化合物を含有する粒子から構成される真空蒸着用粒体であって、下記条件(a)を満たす前記粒子の個数の割合が80%を超える、真空蒸着用粒体。
条件(a):前記粒子の垂直投影図により示される形状の輪郭を面積相当近似法により楕円形へ変換したときの該楕円形の下記式(i)で定義される扁平率が40%以下である。
扁平率=〔(長軸寸法−短軸寸法)/長軸寸法〕×100 (i)
[2] 下記条件(b)を満たす前記粒子の個数の割合が70%以上である、[1]に記載の真空蒸着用粒体。
条件(b):前記楕円形の外周寸法に対する前記粒子の垂直投影図により示される形状の外周寸法の割合が150%以下である。
[3] 下記条件(c)を満たす前記粒子を含む、[1]または[2]に記載の真空蒸着用粒体。
条件(c):前記粒子の垂直投影図により示される形状を、前記長軸寸法を10等分した長さを単位格子の1辺の長さとする正方格子により分割したときに、前記単位格子を構成する1辺において、該1辺と前記粒子の垂直投影図により示される形状の輪郭との交点を2つ有する単位格子であって、前記2つの交点における前記輪郭についての接線がなす角度の前記1辺側の角度が100度以下である単位格子の数が3未満である。
[4] 前記粒子は、粒子の質量を基準に前記式(1)で表される化合物を99質量%以上含有する、[1]〜[3]のいずれかに記載の真空蒸着用粒体。
[5] 前記式(1)で表される化合物はフッ化ナトリウムである、[1]〜[4]のいずれかに記載の真空蒸着用粒体。
[6] 基材、第1電極層、有機機能層、[1]〜[5]のいずれかに記載の真空蒸着用粒体から構成される蒸着膜、および第2電極層がこの順に積層された有機電子デバイス。
[7] [6]に記載の有機電子デバイスの製造方法であって、
真空蒸着法により蒸着膜を形成する工程
を含む製造方法。
[8] 前記蒸着膜を形成する工程は、
前記真空蒸着用粒体を蒸着源に連続的に供給する供給工程と、
前記蒸着源から真空蒸着用材料を真空蒸着する蒸着工程と
を含む、[7]に記載の製造方法。
[9] 式(1):
ABx (1)
[式中、Aは、アルカリ金属原子またはアルカリ土類金属原子を示し、Bは、ハロゲン原子を示し、xは1または2である]
で表される化合物を含有する粒子であって、下記条件(a1)および(c1)を満たす粒子。
条件(a1):前記粒子の垂直投影図により示される形状の輪郭を面積相当近似法により楕円形へ変換したときの該楕円形の下記式(i)で定義される扁平率が50%以下である。
扁平率=〔(長軸寸法−短軸寸法)/長軸寸法〕×100 (i)
条件(c1):前記粒子の垂直投影図により示される形状を、前記長軸寸法の10等分した長さを単位格子の1辺の長さとする正方格子により分割したときに、前記単位格子を構成する1辺において、該1辺と前記粒子の垂直投影図により示される形状の輪郭との交点を2つ有する単位格子であって、前記2つの交点における前記輪郭についての接線がなす角度の前記1辺側の角度が100度以下である単位格子の数が3未満である。
The present invention includes the following aspects [1] to [9].
[1] Formula (1):
AB x (1)
[In the formula, A represents an alkali metal atom or an alkaline earth metal atom, B represents a halogen atom, and x is 1 or 2.]
A particle for vacuum vapor deposition composed of particles containing a compound represented by: wherein the ratio of the number of the particles satisfying the following condition (a) exceeds 80%.
Condition (a): When the contour of the shape shown by the vertical projection of the particles is converted into an ellipse by the area equivalent approximation method, the oblateness defined by the following formula (i) is 40% or less. is there.
Flatness = [(major axis dimension-minor axis dimension)/major axis dimension] x 100 (i)
[2] The particle for vacuum vapor deposition according to [1], wherein the ratio of the number of particles satisfying the following condition (b) is 70% or more.
Condition (b): The ratio of the outer peripheral dimension of the shape shown by the vertical projection of the particles to the outer peripheral dimension of the ellipse is 150% or less.
[3] The particle for vacuum vapor deposition according to [1] or [2], which contains the particles satisfying the following condition (c).
Condition (c): When the shape shown by the vertical projection of the particle is divided by a square lattice having a length obtained by dividing the major axis dimension into 10 equal to one side length of the unit lattice, A unit cell having, on one side, two intersections of the one side and a contour of a shape shown by a vertical projection view of the particle, the unit grid having an angle formed by a tangent line to the contour at the two intersections. The number of unit cells whose angle on one side is 100 degrees or less is less than 3.
[4] The particles for vacuum vapor deposition according to any one of [1] to [3], wherein the particles contain 99% by mass or more of the compound represented by the formula (1) based on the mass of the particles.
[5] The particle for vacuum vapor deposition according to any one of [1] to [4], wherein the compound represented by the formula (1) is sodium fluoride.
[6] A base material, a first electrode layer, an organic functional layer, a vapor deposition film composed of the particles for vacuum vapor deposition according to any one of [1] to [5], and a second electrode layer are laminated in this order. Organic electronic devices.
[7] The method for manufacturing an organic electronic device according to [6],
A manufacturing method including a step of forming a vapor deposition film by a vacuum vapor deposition method.
[8] In the step of forming the vapor deposition film,
A supplying step of continuously supplying the particles for vacuum evaporation to an evaporation source,
The vapor deposition process of vacuum-depositing the material for vacuum vapor deposition from the said vapor deposition source, The manufacturing method as described in [7].
[9] Formula (1):
AB x (1)
[In the formula, A represents an alkali metal atom or an alkaline earth metal atom, B represents a halogen atom, and x is 1 or 2.]
Particles containing a compound represented by the following formula, which satisfy the following conditions (a1) and (c1).
Condition (a1): when the contour of the shape shown by the vertical projection of the particles is converted into an ellipse by the area equivalent approximation method, the oblateness defined by the following formula (i) of the ellipse is 50% or less. is there.
Flatness = [(major axis dimension-minor axis dimension)/major axis dimension] x 100 (i)
Condition (c1): When the shape shown by the vertical projection view of the particles is divided by a square lattice having a length obtained by dividing the major axis dimension into 10 equal to one side length of the unit lattice, A unit cell having, on one side, two intersections of the one side and a contour of a shape shown by a vertical projection view of the particle, the unit grid having an angle formed by a tangent line to the contour at the two intersections. The number of unit cells whose angle on one side is 100 degrees or less is less than 3.
本発明の一態様によれば、真空蒸着用材料を真空蒸着装置の蒸着源に供給して充填する際に真空蒸着装置の供給部の閉塞を生じさせず、入手容易性に優れた真空蒸着用粒体を提供することができる。 According to one embodiment of the present invention, when a material for vacuum evaporation is supplied to an evaporation source of a vacuum evaporation apparatus and filled, a supply portion of the vacuum evaporation apparatus is not clogged, and thus the availability is high. Granules can be provided.
<真空蒸着用粒体>
本発明の一態様に係る真空蒸着用粒体(以下、粒体ともいう)は、式(1):
ABx (1)
[式中、Aは、アルカリ金属原子またはアルカリ土類金属原子を示し、Bは、ハロゲン原子を示し、およびxは1または2である]
で表される化合物(以下、化合物1ともいう)を含有する粒子(以下、単に「粒子」ともいう)から構成される集合体であり、通常2以上の粒子から構成される。粒子とは、光学顕微鏡観察により観察される形状で判別できる、粒体の最小構成単位をいう。光学顕微鏡観察は、粒子の外形が最も鮮明となる条件で、通常5倍の対物倍率で落射光により行う。通常、粒子は、化合物1の単結晶体、多結晶体またはそれらの集合体若しくは焼結体から構成される。
<Vacuum deposition particles>
A particle for vacuum vapor deposition (hereinafter, also referred to as a particle) according to one embodiment of the present invention has the formula (1):
AB x (1)
[In the formula, A represents an alkali metal atom or an alkaline earth metal atom, B represents a halogen atom, and x is 1 or 2.]
It is an aggregate composed of particles (hereinafter, also simply referred to as “particles”) containing a compound represented by (hereinafter, also referred to as compound 1), and usually composed of two or more particles. The particles refer to the smallest constitutional unit of granules that can be discriminated by the shape observed by optical microscope observation. The observation with an optical microscope is carried out by epi-illumination with an objective magnification of usually 5 times under the condition that the outer shape of the particle becomes the clearest. Usually, the particles are composed of a single crystal body, a polycrystal body of Compound 1, or an aggregate or sintered body thereof.
式(1)におけるアルカリ金属原子としては、例えばリチウム、ナトリウム、カリウム、ルビジウム、セシウム等が挙げられる。 Examples of the alkali metal atom in the formula (1) include lithium, sodium, potassium, rubidium and cesium.
式(1)におけるアルカリ土類金属原子としては、例えばマグネシウム、カルシウム、バリウム、ストロンチウム等が挙げられる。 Examples of the alkaline earth metal atom in the formula (1) include magnesium, calcium, barium and strontium.
式(1)におけるハロゲン原子としては、例えばフッ素、臭素、塩素、ヨウ素等が挙げられる。 Examples of the halogen atom in the formula (1) include fluorine, bromine, chlorine, iodine and the like.
化合物1としては、例えばアルカリ金属またはアルカリ土類金属のフッ化物、臭化物、塩化物、ヨウ化物等が挙げられる。中でも入手し易い傾向にあることから、アルカリ金属のフッ化物が好ましく、フッ化ナトリウムがより好ましい。 Examples of compound 1 include fluorides, bromides, chlorides and iodides of alkali metals or alkaline earth metals. Of these, alkali metal fluorides are preferable, and sodium fluoride is more preferable because they tend to be easily available.
粒子中の化合物1の含有量は例えば99質量%以上であってよく、好ましくは99.5質量%以上であり、より好ましくは99.9質量%以上である。上記含有量が99質量%以上である場合、真空蒸着の際に不純ガスが発生しにくい傾向にある。 The content of the compound 1 in the particles may be, for example, 99% by mass or more, preferably 99.5% by mass or more, and more preferably 99.9% by mass or more. When the content is 99% by mass or more, an impure gas tends to be less likely to be generated during vacuum vapor deposition.
粒体は、下記条件(a)を満たす粒子の個数の割合が80%以上である。
条件(a):粒子の垂直投影図により示される形状の輪郭を面積相当近似法により楕円形へ変換したときの楕円形の下記式(i)で定義される扁平率(以下、扁平率ともいう)が40%以下である。
扁平率=〔(長軸寸法−短軸寸法)/長軸寸法〕×100 (i)
面積相当近似法により変換された楕円形(以下、楕円形ともいう)には、円形も含まれる。楕円形が円形である場合、式(i)における長軸寸法および短軸寸法は同一となる。扁平率は、後述する実施例の欄において説明する方法に従って測定することができる。
なお、粒体が条件(a)、および後述の条件(a’)、(a’’)、(b)および(b’)を満たすかどうかの判断は、粒体を構成する全粒子について、または粒体が35個を超える粒子から構成される場合は35個の粒子について測定を行い、判断を行う。例えば粒体が35個を超える粒子から構成される場合、粒体から35個の粒子を任意に採取して測定し、上記条件を満たすかどうか判断し、その結果に基づいて上記条件を満たす粒子の個数の割合を求める。したがって、条件(a)、および後述の条件(a’)、(a’’)、(b)および(b’)を満たす粒子の個数の割合とは、粒体を構成する全粒子に対する、または粒体が35個を超える粒子から構成される場合は35個の粒子に対する割合をいう。
In the granules, the ratio of the number of particles satisfying the following condition (a) is 80% or more.
Condition (a): the flatness defined by the following equation (i) of the ellipse when the contour of the shape shown by the vertical projection diagram of the particles is converted into the ellipse by the area equivalent approximation method (hereinafter, also referred to as flattening rate) ) Is 40% or less.
Flatness = [(major axis dimension-minor axis dimension)/major axis dimension] x 100 (i)
The ellipse converted by the area equivalent approximation method (hereinafter, also referred to as an ellipse) includes a circle. When the ellipse is circular, the major axis dimension and the minor axis dimension in formula (i) are the same. The flatness can be measured according to the method described in the section of Examples described later.
It should be noted that the judgment as to whether or not the particles satisfy the condition (a) and the conditions (a′), (a″), (b) and (b′) described later is performed for all particles constituting the particles. Alternatively, when the granules are composed of more than 35 particles, 35 particles are measured and judged. For example, when a particle is composed of more than 35 particles, 35 particles are arbitrarily sampled from the particle and measured to determine whether the above condition is satisfied, and based on the result, the particle satisfying the above condition is satisfied. Calculate the ratio of the number of Therefore, the ratio of the number of particles satisfying the condition (a) and the conditions (a′), (a″), (b), and (b′) described later is based on all particles constituting the particle, or When the granules are composed of more than 35 particles, it means the ratio to 35 particles.
条件(a)を満たす粒子の個数の割合が80%未満である場合、真空蒸着装置の蒸着源に蒸着材料を供給する際、供給部内で粒子同士が引っ掛かり、供給部の閉塞が発生し、安定的に蒸着源へ材料を供給することができなくなる。これは、扁平率が40%を超える粒子は粒体の流動性が低く、その扁平率が40%を超える粒子の割合が多くなることで供給部の閉塞が発生するためであると推定される。 When the ratio of the number of particles satisfying the condition (a) is less than 80%, when the vapor deposition material is supplied to the vapor deposition source of the vacuum vapor deposition apparatus, the particles are caught in the feed section, clogging of the feed section occurs, and stable. Therefore, the material cannot be supplied to the vapor deposition source. It is presumed that this is because particles having an oblateness of more than 40% have low fluidity of the particles and the proportion of particles having an oblateness of more than 40% increases, thereby causing clogging of the supply unit. ..
粒体中の条件(a)を満たす粒子の個数の割合を80%以上とするには、粒子の原料の選定や、粒子の製造条件、例えば焼成温度・時間の調節、粉砕法の選定等により行うことができる。例えば、粉砕粒子を焼結する際の焼成温度を高くすると粒子の扁平率は下がる傾向にある。 In order to make the ratio of the number of particles satisfying the condition (a) in the granules to 80% or more, it is necessary to select the raw material of the particles and the production conditions of the particles, for example, adjusting the firing temperature and time, selecting the pulverization method, etc. It can be carried out. For example, if the firing temperature for sintering the crushed particles is increased, the oblateness of the particles tends to decrease.
粒体は、条件(a)を満たす粒子の個数の割合が好ましくは82%以上であり、より好ましくは85%以上であり、さらに好ましくは90%以上であり、特に好ましくは92%以上である。 In the granules, the ratio of the number of particles satisfying the condition (a) is preferably 82% or more, more preferably 85% or more, further preferably 90% or more, and particularly preferably 92% or more. ..
粒体は、例えば下記条件(a’)を満たす粒子の個数の割合が55%以上であってよい。
条件(a’):扁平率が30%以下である。
In the granule, for example, the ratio of the number of particles satisfying the following condition (a′) may be 55% or more.
Condition (a′): Flatness is 30% or less.
粒体は、下記条件(a’)を満たす粒子の個数の割合が好ましくは65%以上であり、より好ましくは70%以上であり、さらに好ましくは75%以上であり、特に好ましくは80%以上である。 In the granules, the ratio of the number of particles satisfying the following condition (a′) is preferably 65% or more, more preferably 70% or more, further preferably 75% or more, particularly preferably 80% or more. Is.
粒体は、下記条件(a’’)を満たす粒子の個数の割合が25%以上であってよい。
条件(a’’):扁平率が20%以下である。
The granules may have a ratio of the number of particles satisfying the following condition (a″) of 25% or more.
Condition (a″): Flatness is 20% or less.
粒体は、下記条件(a’’)を満たす粒子の個数の割合が好ましくは28%以上であり、より好ましくは30%以上であり、さらに好ましくは32%以上であり、特に好ましくは35%以上である。 In the granule, the ratio of the number of particles satisfying the following condition (a″) is preferably 28% or more, more preferably 30% or more, further preferably 32% or more, and particularly preferably 35%. That is all.
粒体は、好ましくは下記条件(b)を満たす粒子の個数の割合が70%以上である。
条件(b):粒子の垂直投影図により示される形状の輪郭を面積相当近似法により楕円形へ変換したときの楕円形の外周寸法に対する粒子の垂直投影図により示される形状の外周寸法の割合(以下、外周比ともいう)が150%以下である。
外周比は、後述する実施例の欄において説明する方法に従って測定することができる。
In the granules, the ratio of the number of particles satisfying the following condition (b) is preferably 70% or more.
Condition (b): Ratio of the outer peripheral dimension of the shape shown by the vertical projection diagram of the particle to the outer peripheral dimension of the ellipse when the contour of the shape shown by the vertical projection diagram of the particle is converted into the elliptical shape by the area equivalent approximation method ( Hereinafter, also referred to as an outer peripheral ratio) is 150% or less.
The peripheral ratio can be measured according to the method described in the section of Examples described later.
有機電子デバイスの蒸着膜に用いられるイオン結晶化合物は、一般に、閃亜鉛鉱型構造や塩化ナトリウム型構造等の立方晶系の結晶構造を有するため、その粒子は角張った形状を有していることが多い。本発明者らは、この角張った形状が、供給部の閉塞を起こす1つの原因であることを突止め、粒子が条件(b)および/または後述する条件(c)を満たす場合であれば、粒子において上記角張った部分が少ない傾向にあることを見出した。条件(b)および/または条件(c)を満たす粒子は、輪郭が、平滑な輪郭を有する楕円形の形状に近づくため、粒子表面の微細な凹凸や角張った部分が少なく、粒子の流動性に優れる傾向にあると推定される。その結果、粒子が条件(b)および/または条件(c)を満たす場合、真空蒸着装置の供給部内での粒子同士の引っ掛かりが起こりにくくなり、安定的に材料供給し易くなる傾向にある。 The ionic crystal compound used for the vapor deposition film of the organic electronic device generally has a cubic crystal structure such as a zinc blende type structure or a sodium chloride type structure, so that the particles have an angular shape. There are many. The present inventors have found that this angular shape is one of the causes of blockage of the supply part, and if the particles satisfy the condition (b) and/or the condition (c) described later, It has been found that there is a tendency for the above-mentioned angular portions in the particles to be small. Particles satisfying the condition (b) and/or the condition (c) have an outline close to an elliptical shape having a smooth outline, and therefore, there are few fine irregularities or angular portions on the particle surface, and the fluidity of particles is improved. It is estimated to be excellent. As a result, when the particles satisfy the condition (b) and/or the condition (c), the particles are less likely to be caught in the supply unit of the vacuum evaporation apparatus, and the material tends to be stably supplied.
粒子が条件(b)を満たすようにするには、粒子の原料の選定や、粒子の製造条件、例えば焼成温度・時間の調節、粉砕法の選定等により行うことができる。 In order to satisfy the condition (b), the particles can be selected by selecting the raw material of the particles, adjusting the manufacturing conditions of the particles, for example, adjusting the firing temperature and time, selecting the pulverization method, and the like.
粒体は、条件(b)を満たす粒子の個数の割合が好ましくは80%以上であり、より好ましくは90%以上である。 In the granules, the ratio of the number of particles satisfying the condition (b) is preferably 80% or more, more preferably 90% or more.
粒体は、条件(a)および条件(b)を満たす粒子の個数の割合が好ましくは50%以上であり、より好ましくは60%以上であり、さらに好ましくは70%以上であり、特に好ましくは80%以上である。 In the granules, the ratio of the number of particles satisfying the conditions (a) and (b) is preferably 50% or more, more preferably 60% or more, further preferably 70% or more, and particularly preferably It is 80% or more.
粒体は、好ましくは下記条件(b)を満たす粒子の個数の割合が45%を超える。
条件(b’):外周比が140%以下である。
In the granules, the ratio of the number of particles satisfying the following condition (b) is preferably more than 45%.
Condition (b'): The outer peripheral ratio is 140% or less.
粒体は、条件(a)および条件(b’)を満たす粒子の個数の割合が好ましくは35%以上であり、より好ましくは40%以上であり、さらに好ましくは50%以上であり、特に好ましくは60%以上である。 In the granule, the ratio of the number of particles satisfying the conditions (a) and (b′) is preferably 35% or more, more preferably 40% or more, further preferably 50% or more, and particularly preferably Is 60% or more.
粒体は、好ましくは下記条件(c)を満たす粒子を含む。
条件(c):粒子の垂直投影図により示される形状を、楕円形の長軸寸法を10等分した長さを単位格子の1辺の長さとする正方格子により分割したときに、単位格子を構成する1辺において、この1辺と粒子の垂直投影図により表される形状の輪郭との交点を2つ有する単位格子であって、この2つの交点における輪郭についての接線がなす角度の1辺側の角度が100度以下である単位格子(以下、特定単位格子ともいう)の数が3未満である。
特定単位格子数は、後述する実施例の欄において説明する方法に従って測定することができる。
The granules preferably include particles satisfying the following condition (c).
Condition (c): When the shape shown by the vertical projection view of the particles is divided by a square lattice having a length obtained by dividing the major axis dimension of the ellipse into 10 equal to one side of the unit lattice, A unit cell having two intersections between one side and a contour of a shape represented by a vertical projection view of a particle on one side, and one side of an angle formed by a tangent to the contour at the two intersections. The number of unit lattices having a side angle of 100 degrees or less (hereinafter, also referred to as a specific unit lattice) is less than 3.
The number of specific unit lattices can be measured according to the method described in the section of Examples below.
粒体が条件(c)を満たす粒子を含む場合、真空蒸着装置の蒸着源に粒体を供給する際に、供給部内で粒子同士が引っ掛かりにくくなり、安定的に材料供給し易くなる傾向にある。これは、特定単位格子数が3未満である場合、粒子表面の微細な凹凸や角張った部分が少なくなり、粒子の流動性が向上する傾向にあることが推定される。
粒体を構成する粒子は、条件(c)を満たす粒子の個数の割合が、例えば20%以上であってよく、より好ましくは40%以上、さらに好ましくは60%以上、特に好ましくは80%以上であり、とりわけ好ましくは全ての粒子が条件(c)を満たす。条件(c)を満たす粒子の割合は、粒体を構成する全粒子について、または粒体が5個を超える粒子から構成される場合は5個の粒子について測定を行い、その結果に基づいて割合を求める。したがって、条件(c)を満たす粒子の個数の割合とは、粒体を構成する全粒子に対する、または粒体が55個を超える粒子から構成される場合は5個の粒子に対する割合をいう。
When the particles contain particles satisfying the condition (c), when the particles are supplied to the vapor deposition source of the vacuum evaporation apparatus, the particles are less likely to be caught in the supply section, and the material tends to be stably supplied. .. It is presumed that when the number of specific unit lattices is less than 3, fine irregularities and angular portions on the particle surface are reduced, and the fluidity of particles tends to be improved.
The particles constituting the granules may have a ratio of the number of particles satisfying the condition (c) to, for example, 20% or more, more preferably 40% or more, further preferably 60% or more, particularly preferably 80% or more. And particularly preferably all particles satisfy the condition (c). The proportion of particles satisfying the condition (c) is measured for all the particles constituting the granules, or for 5 particles when the granules are composed of more than 5 particles, and the proportion is based on the result. Ask for. Therefore, the ratio of the number of particles satisfying the condition (c) means the ratio with respect to all the particles forming the particles, or the ratio with respect to 5 particles when the particles include more than 55 particles.
粒子が条件(c)を満たすようにするには、粒子の原料の選定や、粒子の製造条件、例えば焼成温度・時間の調節、粉砕法の選定等により行うことができる。 In order to satisfy the condition (c), the particles can be selected by selecting the raw material of the particles, adjusting the manufacturing conditions of the particles, for example, adjusting the firing temperature and time, selecting the pulverizing method, and the like.
なお、粒体が条件(c)を満たすかどうか判断を行う際には、粒体から任意の1個の粒子を採取して、その粒子の測定結果に基づいて判断を行う。 When determining whether or not the particles satisfy the condition (c), any one particle is sampled from the particle and the determination is made based on the measurement result of the particles.
粒体は、真空蒸着法により形成される蒸着膜の材料として好適である。粒体は、とりわけ有機ELデバイス、有機太陽電池、有機フォトディテクタ、有機トランジスタ等の有機電子デバイスの蒸着膜用材料として好ましく用いられる。 Granules are suitable as a material for a vapor deposition film formed by a vacuum vapor deposition method. Granules are particularly preferably used as a material for a vapor deposition film of organic electronic devices such as organic EL devices, organic solar cells, organic photodetectors, and organic transistors.
<粒子>
本発明の一態様に係る粒子は、式(1):
ABx (1)
[式中、Aは、アルカリ金属原子またはアルカリ土類金属原子を示し、Bは、ハロゲン原子を示し、およびxは1または2である]
で表される化合物を含有する粒子であって、下記条件(a1)および(c1)を満たす。
条件(a1):粒子の垂直投影図により示される形状の輪郭を面積相当近似法により楕円形へ変換したときの該楕円形の下記式(i)で定義される扁平率(以下、扁平率ともいう)が50%以下である。
扁平率=〔(長軸寸法−短軸寸法)/長軸寸法〕×100 (i)
条件(c1):粒子の垂直投影図により示される形状の輪郭を面積相当近似法により楕円形へ変換し、この輪郭を、楕円形の長軸寸法の10等分した長さを単位格子の1辺の長さとする正方格子により分割したときに、単位格子を構成する1辺において、この1辺と粒子の垂直投影図により表される形状の輪郭との交点を2つ有する単位格子であって、この2つの交点における輪郭についての接線がなす角度の1辺側の角度が100度以下である単位格子(以下、特定単位格子ともいう)の数が3未満である。
扁平率および特定単位格子は、後述する実施例の欄において説明する方法に従って測定することができる。
<Particles>
The particles according to one embodiment of the present invention have the formula (1):
AB x (1)
[In the formula, A represents an alkali metal atom or an alkaline earth metal atom, B represents a halogen atom, and x is 1 or 2.]
A particle containing a compound represented by the following conditions (a1) and (c1) are satisfied.
Condition (a1): the flatness defined by the following equation (i) of the ellipse when the contour of the shape shown by the vertical projection diagram of the particles is converted into the ellipse by the area equivalent approximation method (hereinafter, both flatness Is 50% or less.
Flatness = [(major axis dimension-minor axis dimension)/major axis dimension] x 100 (i)
Condition (c1): The contour of the shape shown by the vertical projection view of the particles is converted into an ellipse by the area equivalent approximation method, and the contour is divided into 10 equal parts of the major axis dimension of the ellipse to obtain 1 of the unit cell. When divided by a square lattice having a side length, one side forming a unit lattice has two intersections between the one side and the contour of the shape represented by the vertical projection view of the particles. The number of unit lattices (hereinafter, also referred to as specific unit lattices) whose angle on one side of the angle formed by the tangents of the contours at these two intersections is 100 degrees or less is less than three.
The flatness and the specific unit cell can be measured according to the method described in the section of Examples described later.
式(1)におけるアルカリ金属原子、アルカリ土類金属原子およびハロゲン原子、並びに式(1)で表される化合物の例は、上述の粒体における説明で例示したものと同じである。 Examples of the alkali metal atom, the alkaline earth metal atom and the halogen atom in the formula (1), and the compound represented by the formula (1) are the same as those exemplified in the description of the particles.
扁平率が50%を超えるか、または特定単位格子数が3以上である粒子の場合、真空蒸着装置の蒸着源に粒体を供給する際、供給部内で粒子同士が引っ掛かり易くなり、安定的に材料供給できなくなる傾向にある。これは、扁平率が50%を超えるか、または特定単位格子数が3以上である粒子は流動性が低い傾向にあり、粒子が供給部内で滑らかに流動できなくなるためであると推定される。これに対し、扁平率が50%以下であり、かつ特定単位格子数が3未満である場合、粒子が供給部内で滑らかに流動でき、供給部内で粒子同士の引っ掛かりが起こりにくくなると推定される。 In the case of particles having an oblateness of more than 50% or a specific unit lattice number of 3 or more, when the particles are supplied to the evaporation source of the vacuum evaporation apparatus, the particles are likely to be caught in the supply unit, and the particles are stably stabilized. There is a tendency that materials cannot be supplied. It is estimated that this is because particles having an oblateness of more than 50% or having a specific unit lattice number of 3 or more tend to have low fluidity, and the particles cannot flow smoothly in the supply unit. On the other hand, when the flatness is 50% or less and the number of specific unit lattices is less than 3, it is presumed that the particles can smoothly flow in the supply unit and the particles are less likely to be caught in the supply unit.
条件(a1)を満たす粒子を得るには、原料の選定や、粒子の製造条件、例えば焼成温度・時間の調節、粉砕法の選定等により行うことができる。例えば、焼成温度を高くすると粒子の扁平率は下がる傾向にあり、焼成時間を長くする粒子の扁平率は下がる傾向にある。 In order to obtain particles satisfying the condition (a1), selection of raw materials, production conditions of particles such as adjustment of firing temperature and time, selection of pulverization method and the like can be performed. For example, when the firing temperature is increased, the oblateness of the particles tends to decrease, and the oblateness of the particles that elongates the firing time tends to decrease.
条件(c1)を満たす粒子を得るには、原料の選定や、粒子の製造条件、例えば焼成温度・時間の調節、粉砕法の選定等により行うことができる。例えば、焼成温度を高くすると粒子の扁平率は下がる傾向にあり、焼成時間を長くする粒子の扁平率は下がる傾向にある。 In order to obtain particles satisfying the condition (c1), selection of raw materials, production conditions of particles, for example, adjustment of firing temperature and time, selection of pulverization method and the like can be performed. For example, when the firing temperature is increased, the oblateness of the particles tends to decrease, and the oblateness of the particles that elongates the firing time tends to decrease.
条件(a1)における扁平率は、好ましくは0%を超え40%以下であり、より好ましくは0.1〜30%であり、特に好ましくは1〜20%である。 The oblateness under the condition (a1) is preferably more than 0% and 40% or less, more preferably 0.1 to 30%, and particularly preferably 1 to 20%.
条件(c1)における特定単位格子数は、好ましくは2未満であり、より好ましくは0でる。 The number of specific unit lattices under the condition (c1) is preferably less than 2, and more preferably 0.
長軸寸法は、例えば0.01〜50mmであってよく、好ましくは0.1〜20mm、より好ましくは0.2〜10mmである。短軸寸法は、例えば0.005〜25mmであってよく、好ましくは0.05〜10mm、より好ましくは0.1〜5mmである。 The major axis dimension may be, for example, 0.01 to 50 mm, preferably 0.1 to 20 mm, more preferably 0.2 to 10 mm. The minor axis dimension may be, for example, 0.005 to 25 mm, preferably 0.05 to 10 mm, and more preferably 0.1 to 5 mm.
粒子は、好ましくは下記条件(b1)を満たす。
条件(b1):粒子の垂直投影図により示される形状の輪郭を面積相当近似法により楕円形へ変換したときの楕円形の外周寸法に対する粒子の垂直投影図により示される形状の外周寸法の割合(以下、外周比ともいう)が150%以下である。
外周比は、後述する実施例の欄において説明する方法に従って測定することができる。
The particles preferably satisfy the following condition (b1).
Condition (b1): Ratio of the outer peripheral dimension of the shape shown by the vertical projection diagram of the particle to the outer peripheral dimension of the ellipse when the contour of the shape shown by the vertical projection diagram of the particle is converted into the ellipse by the area equivalent approximation method ( Hereinafter, also referred to as an outer peripheral ratio) is 150% or less.
The peripheral ratio can be measured according to the method described in the section of Examples described later.
粒子が条件(b1)を満たす場合、真空蒸着装置の蒸着源に粒体を供給する際に、供給部内での粒子同士が引っ掛かりにくくなり、安定的に材料供給し易くなる傾向にある。外周比が100%に近づく場合、粒子表面の微細な凹凸や角張った部分が少なくなり、粒子の流動性が向上し易くなる傾向にあることが推定される。 When the particles satisfy the condition (b1), when the particles are supplied to the vapor deposition source of the vacuum vapor deposition apparatus, the particles are less likely to be caught in the supply unit, and the material tends to be stably supplied. When the peripheral ratio approaches 100%, it is presumed that fine irregularities and angular portions on the particle surface are reduced, and the fluidity of the particles tends to be improved.
粒子が条件(b1)を満たすようにするには、粒子の原料の選定や、粒子の製造条件、例えば焼成温度・時間の調節、粉砕法の選定等により行うことができる。 To satisfy the condition (b1), the particles can be selected by selecting the raw material of the particles, adjusting the manufacturing conditions of the particles, for example, adjusting the firing temperature and time, selecting the pulverizing method, and the like.
条件(b1)における外周比は好ましくは140%以下であり、より好ましくは130%以下であり、特に好ましくは120%以下である。 The outer peripheral ratio under the condition (b1) is preferably 140% or less, more preferably 130% or less, and particularly preferably 120% or less.
<粒体の製造方法>
粒体の製造方法は、化合物1の結晶を粉砕する工程(以下、粉砕工程ともいう)、および粉砕した結晶を焼結する工程(以下、焼結工程ともいう)を含む。
<Method for producing granules>
The method for producing granules includes a step of pulverizing crystals of compound 1 (hereinafter, also referred to as a pulverizing step), and a step of sintering the pulverized crystals (hereinafter, also referred to as a sintering step).
粉砕工程において、化合物1の結晶を粉砕する方法としては、特に限定されないが例えば乾式ボールミル、湿式ボールミル、乾式ビーズミル、湿式ビーズミル、ジェットミル、遊星ボールミル、ヘンシェルミキサー等を用いた粉砕法が挙げられる。粉砕法や粉砕時間等は、粉砕する化合物1の結晶の大きさや量に応じて適宜選択することができる。粉砕時間としては、例えば30秒間〜120分間であってよい。化合物1を粉砕した後、粉砕した結晶は、焼結前に乾燥することができる。 In the pulverizing step, the method of pulverizing the crystals of compound 1 is not particularly limited, and examples thereof include a dry ball mill, a wet ball mill, a dry bead mill, a wet bead mill, a jet mill, a planetary ball mill and a Henschel mixer. The pulverizing method, pulverizing time, and the like can be appropriately selected depending on the size and amount of the crystal of Compound 1 to be pulverized. The crushing time may be, for example, 30 seconds to 120 minutes. After crushing Compound 1, the crushed crystals can be dried before sintering.
焼結工程において、粉砕した結晶の焼結は、真空中または不活性ガス雰囲気中で行うことができる。焼結温度としては、例えば200℃〜1800℃であってよく、好ましくは400℃〜1500℃、より好ましくは600℃〜1200℃である。焼結時間としては、例えば0.5〜20時間であってよく、好ましくは1〜10時間、より好ましくは1.5〜5時間である。 In the sintering step, the crushed crystals can be sintered in vacuum or in an inert gas atmosphere. The sintering temperature may be, for example, 200°C to 1800°C, preferably 400°C to 1500°C, and more preferably 600°C to 1200°C. The sintering time may be, for example, 0.5 to 20 hours, preferably 1 to 10 hours, and more preferably 1.5 to 5 hours.
粒体の製造方法は、焼結工程後、焼結した結晶を分級するための分級工程をさらに含んでよい。分級は、例えば振動ふるい機等を用いて行うことができる。 The method for producing granules may further include a classification step for classifying the sintered crystals after the sintering step. The classification can be performed using, for example, a vibration sieving machine.
<有機電子デバイス>
有機電子デバイスは、基材、第1電極層、有機機能層、真空蒸着用粒体から構成される蒸着膜、および第2電極層がこの順に積層されたものである。真空蒸着用粒体としては、上述の本発明の一態様に係る真空蒸着用粒体を用いることができる。有機電子デバイスとしては、有機ELデバイス、有機太陽電池、有機フォトディテクタ、有機トランジスタ等が挙げられる。
<Organic electronic device>
The organic electronic device includes a base material, a first electrode layer, an organic functional layer, a vapor deposition film composed of particles for vacuum vapor deposition, and a second electrode layer, which are laminated in this order. As the particles for vacuum evaporation, the particles for vacuum evaporation according to one embodiment of the present invention can be used. Examples of organic electronic devices include organic EL devices, organic solar cells, organic photodetectors, and organic transistors.
以下では、本発明の一態様に係る有機電子デバイスが有機ELデバイスである場合について説明する。図1に示す本発明の一態様に係る有機ELデバイス10は、基板11上に、陽極12(第1電極層)、有機機能層13、蒸着膜14、陰極15(第2電極層)を順に備える。有機ELデバイスは、陽極側から光を出射する形態、または陰極側から光を出射する形態を取り得る。以下では、断らない限り、陽極側から光を出射する形態について説明する。 Hereinafter, a case where the organic electronic device according to one aspect of the present invention is an organic EL device will be described. An organic EL device 10 according to one embodiment of the present invention shown in FIG. 1 has an anode 12 (first electrode layer), an organic functional layer 13, a vapor deposition film 14, and a cathode 15 (second electrode layer) on a substrate 11 in order. Prepare The organic EL device may have a form of emitting light from the anode side or a form of emitting light from the cathode side. Hereinafter, unless otherwise specified, a mode in which light is emitted from the anode side will be described.
[基板]
基板11は、可視光(波長400nm〜800nmの光)に対して透光性を有する。基板11は、ガラス基板またはフィルム状の基板であり得る。基板11の厚みは、例えば30μm以上700μm以下である。基板11は、長尺状であっても、枚葉状であってもよい。
[substrate]
The substrate 11 has a property of transmitting visible light (light having a wavelength of 400 nm to 800 nm). The substrate 11 may be a glass substrate or a film-shaped substrate. The thickness of the substrate 11 is, for example, 30 μm or more and 700 μm or less. The substrate 11 may have a long shape or a sheet shape.
フィルム状の基板としては、プラスチックフィルムまたは高分子フィルムである。フィルム状の基板の材料としては、例えばポリエーテルスルホン(PES);ポリエチレンテレフタレート(PET)、ポリエチレンナフタレート(PEN)等のポリエステル樹脂;ポリエチレン(PE)、ポリプロピレン(PP)、環状ポリオレフィン等のポリオレフィン樹脂;ポリアミド樹脂;ポリカーボネート樹脂;ポリスチレン樹脂;ポリビニルアルコール樹脂;エチレン−酢酸ビニル共重合体のケン化物;ポリアクリロニトリル樹脂;アセタール樹脂;ポリイミド樹脂;エポキシ樹脂等が挙げられる。 The film-like substrate is a plastic film or a polymer film. Examples of the material of the film-like substrate include polyether sulfone (PES); polyester resin such as polyethylene terephthalate (PET) and polyethylene naphthalate (PEN); polyolefin resin such as polyethylene (PE), polypropylene (PP), cyclic polyolefin. Polyamide resin; Polycarbonate resin; Polystyrene resin; Polyvinyl alcohol resin; Saponified ethylene-vinyl acetate copolymer; Polyacrylonitrile resin; Acetal resin; Polyimide resin; Epoxy resin and the like.
基板11には、有機ELデバイスを駆動するための駆動回路(例えば、薄膜トランジスタなどを含む回路)が形成されていてもよい。このような駆動回路は、通常、透明材料から構成される。 A drive circuit (for example, a circuit including a thin film transistor) for driving the organic EL device may be formed on the substrate 11. Such a drive circuit is usually made of a transparent material.
基板11の表面上には、バリア膜が形成されていてもよい。バリア膜は、例えば、ケイ素、酸素および炭素からなる膜、または、ケイ素、酸素、炭素および窒素からなる膜であり得る。具体的には、バリア膜の材料の例は、酸化ケイ素、窒化ケイ素、酸窒化ケイ素等である。バリア膜の厚みの例は、100nm〜10μmである。 A barrier film may be formed on the surface of the substrate 11. The barrier film can be, for example, a film made of silicon, oxygen and carbon, or a film made of silicon, oxygen, carbon and nitrogen. Specifically, examples of the material of the barrier film are silicon oxide, silicon nitride, silicon oxynitride, and the like. An example of the thickness of the barrier film is 100 nm to 10 μm.
[陽極]
陽極12は、基板の表面上に設けられている。陽極12には、光透過性を示す電極が用いられる。光透過性を示す電極としては、電気伝導度の高い金属酸化物、金属硫化物および金属等の薄膜を用いることができ、光透過率の高い薄膜が好適に用いられる。陽極12は、導電体(例えば金属)からなるネットワーク構造を有してもよい。
[anode]
The anode 12 is provided on the surface of the substrate. For the anode 12, an electrode having a light transmitting property is used. A thin film of metal oxide, metal sulfide, metal or the like having high electric conductivity can be used as the electrode having light transmittance, and a thin film having high light transmittance is preferably used. The anode 12 may have a network structure made of a conductor (for example, metal).
陽極12の材料としては、例えば酸化インジウム、酸化亜鉛、酸化スズ、インジウム錫酸化物(Indium Tin Oxide:略称ITO)、インジウム亜鉛酸化物(Indium Zinc Oxide:略称IZO)、金、白金、銀、銅等が挙げられ、これらの中でもITO、IZO、または酸化スズが好ましい。陽極12は、例示した材料からなる薄膜として形成され得る。陽極12の材料には、ポリアニリンおよびその誘導体、ポリチオフェンおよびその誘導体等の有機物を用いてもよい。この場合、陽極12は、透明導電膜として形成され得る。 Examples of the material of the anode 12 include indium oxide, zinc oxide, tin oxide, indium tin oxide (abbreviated as ITO), indium zinc oxide (abbreviated as IZO), gold, platinum, silver, and copper. And the like. Among these, ITO, IZO, or tin oxide is preferable. The anode 12 can be formed as a thin film made of the exemplified material. As the material of the anode 12, organic substances such as polyaniline and its derivative, polythiophene and its derivative, etc. may be used. In this case, the anode 12 can be formed as a transparent conductive film.
陽極12の厚みは、光の透過性や、電気伝導度等を考慮して決定することができる。陽極12の厚みは、通常、10nm〜10μmであり、好ましくは20nm〜1μmであり、さらに好ましくは50nm〜500nmである。 The thickness of the anode 12 can be determined in consideration of light transmittance, electric conductivity and the like. The thickness of the anode 12 is usually 10 nm to 10 μm, preferably 20 nm to 1 μm, and more preferably 50 nm to 500 nm.
[有機機能層]
有機機能層13は、陽極および陰極に印加された電力(例えば電圧)に応じて、電荷の移動および電荷の再結合などの有機ELデバイスの発光に寄与する機能部である。
有機機能層13は、光を発する機能層である発光層を有する。発光層の厚さは、例えば1nm〜1μmであり、好ましくは2nm〜500nmであり、さらに好ましくは10nm〜300nmである。
[Organic functional layer]
The organic functional layer 13 is a functional part that contributes to light emission of the organic EL device such as movement of electric charges and recombination of electric charges according to electric power (for example, voltage) applied to the anode and the cathode.
The organic functional layer 13 has a light emitting layer that is a functional layer that emits light. The thickness of the light emitting layer is, for example, 1 nm to 1 μm, preferably 2 nm to 500 nm, and more preferably 10 nm to 300 nm.
発光層は、通常、主として蛍光およびりん光の少なくとも一方を発光する有機物、または、その有機物とその有機物を補助するドーパント材料とから形成される。ドーパント材料は、例えば発光効率の向上や、発光波長を変化させるために加えられる。発光層に含まれる有機物は、低分子化合物でも高分子化合物でもよい。
発光層は、陽極上に設けられており、所定の波長の光を発光する機能を有する機能層である。発光層の厚さは、用いる材料によって最適値が異なり、駆動電圧と発光効率が適度な値となるように適宜設定される。発光層の厚さは、例えば1nm〜1μmであり、好ましくは2nm〜500nmであり、さらに好ましくは10nm〜200nmである。
発光層の材料は、公知の発光層用の材料であればよい。発光層は、通常、主として蛍光および/またはりん光を発光する有機物、或いは、該有機物とこれを補助するドーパントを含む。ドーパントは、例えば発光効率の向上や、発光波長を変化させるために加えられる。発光層16に含まれる有機物は、低分子化合物でも高分子化合物でもよい。発光層16を構成する発光材料としては、下記の色素系材料、金属錯体系材料、高分子系材料等の主として蛍光および/またはりん光を発光する有機物、ドーパント材料等が挙げられる。
The light emitting layer is usually formed mainly of an organic substance which emits at least one of fluorescence and phosphorescence, or an organic substance and a dopant material which assists the organic substance. The dopant material is added, for example, to improve the emission efficiency or change the emission wavelength. The organic substance contained in the light emitting layer may be a low molecular weight compound or a high molecular weight compound.
The light emitting layer is a functional layer provided on the anode and having a function of emitting light having a predetermined wavelength. The thickness of the light emitting layer has an optimum value that differs depending on the material used, and is appropriately set so that the drive voltage and the light emission efficiency have appropriate values. The thickness of the light emitting layer is, for example, 1 nm to 1 μm, preferably 2 nm to 500 nm, and more preferably 10 nm to 200 nm.
The material of the light emitting layer may be any known material for the light emitting layer. The light emitting layer usually contains an organic substance which mainly emits fluorescence and/or phosphorescence, or the organic substance and a dopant which assists the organic substance. The dopant is added, for example, to improve the luminous efficiency or change the emission wavelength. The organic substance contained in the light emitting layer 16 may be a low molecular compound or a high molecular compound. Examples of the light-emitting material that constitutes the light-emitting layer 16 include organic materials that mainly emit fluorescence and/or phosphorescence, such as the following pigment-based materials, metal complex-based materials, and polymer-based materials, and dopant materials.
色素系材料としては、例えばシクロペンダミン若しくはその誘導体、テトラフェニルブタジエン若しくはその誘導体、トリフェニルアミン若しくはその誘導体、オキサジアゾール若しくはその誘導体、ピラゾロキノリン若しくはその誘導体、ジスチリルベンゼン若しくはその誘導体、ジスチリルアリーレン若しくはその誘導体、ピロール若しくはその誘導体、チオフェン環化合物、ピリジン環化合物、ペリノン若しくはその誘導体、ペリレン若しくはその誘導体、オリゴチオフェン若しくはその誘導体、オキサジアゾールダイマー若しくはその誘導体、ピラゾリンダイマー若しくはその誘導体、キナクリドン若しくはその誘導体、クマリン若しくはその誘導体等が挙げられる。 Examples of the dye-based material include cyclopentamine or its derivative, tetraphenylbutadiene or its derivative, triphenylamine or its derivative, oxadiazole or its derivative, pyrazoloquinoline or its derivative, distyrylbenzene or its derivative, and diphenylamine. Styrylarylene or its derivative, pyrrole or its derivative, thiophene ring compound, pyridine ring compound, perinone or its derivative, perylene or its derivative, oligothiophene or its derivative, oxadiazole dimer or its derivative, pyrazoline dimer or its derivative, Examples include quinacridone or its derivative, coumarin or its derivative, and the like.
金属錯体系材料としては、例えばTb、Eu、Dyなどの希土類金属、またはAl、Zn、Be、Pt、Ir等を中心金属に有し、オキサジアゾール、チアジアゾール、フェニルピリジン、フェニルベンゾイミダゾール、キノリン構造等を配位子に有する金属錯体等が挙げられる。金属錯体としては、例えばイリジウム錯体、白金錯体等の三重項励起状態からの発光を有する金属錯体、アルミニウムキノリノール錯体、ベンゾキノリノールベリリウム錯体、ベンゾオキサゾリル亜鉛錯体、ベンゾチアゾール亜鉛錯体、アゾメチル亜鉛錯体、ポルフィリン亜鉛錯体、フェナントロリンユーロピウム錯体等が挙げられる。 Examples of the metal complex-based material include rare earth metals such as Tb, Eu and Dy, or Al, Zn, Be, Pt, Ir and the like as central metals, and oxadiazole, thiadiazole, phenylpyridine, phenylbenzimidazole, quinoline. Examples thereof include metal complexes having a structure and the like as a ligand. As the metal complex, for example, an iridium complex, a metal complex having light emission from a triplet excited state such as a platinum complex, an aluminum quinolinol complex, a benzoquinolinol beryllium complex, a benzoxazolyl zinc complex, a benzothiazole zinc complex, an azomethylzinc complex, Examples thereof include porphyrin zinc complex and phenanthroline europium complex.
高分子系材料としては、例えばポリパラフェニレンビニレン若しくはその誘導体、ポリチオフェン若しくはその誘導体、ポリパラフェニレン若しくはその誘導体、ポリシラン若しくはその誘導体、ポリアセチレン若しくはその誘導体、ポリフルオレン若しくはその誘導体、ポリビニルカルバゾール若しくはその誘導体、上記色素材料および金属錯体材料の少なくとも一方を高分子化した材料等が挙げられる。 As the polymer material, for example, polyparaphenylene vinylene or its derivative, polythiophene or its derivative, polyparaphenylene or its derivative, polysilane or its derivative, polyacetylene or its derivative, polyfluorene or its derivative, polyvinylcarbazole or its derivative, Examples thereof include a material obtained by polymerizing at least one of the dye material and the metal complex material.
ドーパント材料としては、例えばペリレン若しくはその誘導体、クマリン若しくはその誘導体、ルブレン若しくはその誘導体、キナクリドン若しくはその誘導体、スクアリウム若しくはその誘導体、ポルフィリン若しくはその誘導体、スチリル色素、テトラセン若しくはその誘導体、ピラゾロン若しくはその誘導体、デカシクレン若しくはその誘導体、フェノキサゾン若しくはその誘導体等が挙げられる。 Examples of the dopant material include perylene or its derivative, coumarin or its derivative, rubrene or its derivative, quinacridone or its derivative, squalium or its derivative, porphyrin or its derivative, styryl dye, tetracene or its derivative, pyrazolone or its derivative, decacyclene. Alternatively, a derivative thereof, phenoxazone or a derivative thereof and the like can be mentioned.
有機機能層13は、発光層と、他の機能層を含む積層体でもよい。陽極12と発光層との間に設けられる機能層としては、例えば正孔注入層、正孔輸送層等が挙げられる。陰極15と発光層との間に設けられる機能層としては、例えば電子輸送層等が挙げられる。正孔注入層、正孔輸送層、電子輸送層の厚みは、有機ELデバイスのデバイス性能などに応じて適宜設定され得る。 The organic functional layer 13 may be a laminated body including a light emitting layer and another functional layer. Examples of the functional layer provided between the anode 12 and the light emitting layer include a hole injection layer and a hole transport layer. Examples of the functional layer provided between the cathode 15 and the light emitting layer include an electron transport layer and the like. The thickness of the hole injection layer, the hole transport layer, and the electron transport layer can be appropriately set according to the device performance of the organic EL device.
正孔注入層は、陽極12から発光層への正孔注入効率を改善する機能を有する機能層である。正孔注入層の材料には、公知の正孔注入材料が用いられ得る。正孔注入材料としては、例えば酸化バナジウム、酸化モリブデン、酸化ルテニウム、および酸化アルミニウム等の酸化物、フェニルアミン化合物、スターバースト型アミン化合物、フタロシアニン化合物、アモルファスカーボン、ポリアニリン、およびポリエチレンジオキシチオフェン(PEDOT)等のポリチオフェン誘導体が挙げられる。 The hole injection layer is a functional layer having a function of improving hole injection efficiency from the anode 12 to the light emitting layer. A known hole injection material can be used as the material of the hole injection layer. Examples of the hole injection material include oxides such as vanadium oxide, molybdenum oxide, ruthenium oxide, and aluminum oxide, phenylamine compounds, starburst amine compounds, phthalocyanine compounds, amorphous carbon, polyaniline, and polyethylenedioxythiophene (PEDOT). ) And other polythiophene derivatives.
正孔輸送層は、陽極12、正孔注入層または陽極12により近い正孔輸送層から発光層への正孔注入効率を改善する機能を有する機能層である。正孔輸送層の材料には、公知の正孔輸送材料が用いられ得る。正孔輸送層の材料としては、例えばポリビニルカルバゾール若しくはその誘導体、ポリシラン若しくはその誘導体、側鎖若しくは主鎖に芳香族アミンを有するポリシロキサン若しくはその誘導体、ピラゾリン若しくはその誘導体、アリールアミン若しくはその誘導体、スチルベン若しくはその誘導体、トリフェニルジアミン若しくはその誘導体、ポリアニリン若しくはその誘導体、ポリチオフェン若しくはその誘導体、ポリアリールアミン若しくはその誘導体、ポリピロール若しくはその誘導体、ポリ(p−フェニレンビニレン)若しくはその誘導体、またはポリ(2,5−チエニレンビニレン)若しくはその誘導体等が挙げられる。正孔輸送層の材料としては、例えば特開2012−144722号公報に開示されている正孔輸層材料も挙げられる。 The hole transport layer is a functional layer having a function of improving the efficiency of hole injection from the anode 12, the hole injection layer or the hole transport layer closer to the anode 12 to the light emitting layer. A known hole transport material can be used as the material of the hole transport layer. Examples of the material of the hole transport layer include polyvinylcarbazole or its derivative, polysilane or its derivative, polysiloxane having an aromatic amine in its side chain or main chain or its derivative, pyrazoline or its derivative, arylamine or its derivative, stilbene. Or a derivative thereof, triphenyldiamine or a derivative thereof, polyaniline or a derivative thereof, polythiophene or a derivative thereof, polyarylamine or a derivative thereof, polypyrrole or a derivative thereof, poly(p-phenylenevinylene) or a derivative thereof, or poly(2,5 -Thienylene vinylene) or its derivatives. Examples of the material for the hole transport layer also include the hole transport layer material disclosed in JP 2012-144722 A.
電子輸送層は、陰極15または陰極15により近い電子輸送層から発光層への電子注入効率を改善する機能を有する機能層である。電子輸送層を構成する電子輸送材料には、公知の材料が用いられ得る。電子輸送層を構成する電子輸送材料としては、オキサジアゾール誘導体、アントラキノジメタン若しくはその誘導体、ベンゾキノン若しくはその誘導体、ナフトキノン若しくはその誘導体、アントラキノン若しくはその誘導体、テトラシアノアントラキノジメタン若しくはその誘導体、フルオレノン誘導体、ジフェニルジシアノエチレン若しくはその誘導体、ジフェノキノン誘導体、または8−ヒドロキシキノリン若しくはその誘導体の金属錯体、ポリキノリン若しくはその誘導体、ポリキノキサリン若しくはその誘導体、ポリフルオレン若しくはその誘導体などが挙げられる。 The electron transport layer is a functional layer having a function of improving electron injection efficiency from the cathode 15 or the electron transport layer closer to the cathode 15 to the light emitting layer. A known material may be used as the electron transport material forming the electron transport layer. The electron transport material constituting the electron transport layer, oxadiazole derivative, anthraquinodimethane or its derivative, benzoquinone or its derivative, naphthoquinone or its derivative, anthraquinone or its derivative, tetracyanoanthraquinodimethane or its derivative, Examples thereof include fluorenone derivatives, diphenyldicyanoethylene or its derivatives, diphenoquinone derivatives, metal complexes of 8-hydroxyquinoline or its derivatives, polyquinoline or its derivatives, polyquinoxaline or its derivatives, polyfluorene or its derivatives.
上述した各種の機能層を含む有機機能層13の層構成の例を以下に示す。
(a)(陽極)/正孔注入層/発光層/(蒸着膜/陰極)
(b)(陽極)/正孔注入層/発光層/電子輸送層/(蒸着膜/陰極)
(c)(陽極)/正孔注入層/正孔輸送層/発光層/(蒸着膜/陰極)
(d)(陽極)/正孔注入層/正孔輸送層/発光層/電子輸送層/(蒸着膜/陰極)
(e)(陽極)/発光層/(蒸着膜/陰極)
(f)(陽極)/発光層/電子輸送層/(蒸着膜/陰極)
記号「/」は、記号「/」の両側の層同士が接合していることを意味する。
An example of the layer structure of the organic functional layer 13 including the various functional layers described above is shown below.
(A) (Anode)/hole injection layer/light emitting layer/(deposited film/cathode)
(B) (Anode)/hole injection layer/light emitting layer/electron transport layer/(deposited film/cathode)
(C) (Anode)/hole injection layer/hole transport layer/light emitting layer/(deposited film/cathode)
(D) (Anode)/hole injection layer/hole transport layer/light emitting layer/electron transport layer/(deposited film/cathode)
(E) (anode)/light-emitting layer/(evaporated film/cathode)
(F) (anode)/light-emitting layer/electron transport layer/(evaporated film/cathode)
The symbol “/” means that the layers on both sides of the symbol “/” are joined together.
有機機能層13は単層の発光層を有していても2層以上の発光層を有していてもよい。電荷発生層を設けずに、複数の発光層を直接的に積層させて有機機能層13を構成してもよい。なお、電荷発生層とは、電極の役割をする層である。 The organic functional layer 13 may have a single light emitting layer or two or more light emitting layers. The organic functional layer 13 may be formed by directly stacking a plurality of light emitting layers without providing the charge generation layer. Note that the charge generation layer is a layer which functions as an electrode.
[蒸着膜]
蒸着膜14は、真空蒸着用粒体から形成される膜であり、無機物から形成される無機膜である。蒸着膜14の厚みは、例えば0.5nm〜20nmであり、好ましくは1nm〜10nmである。真空蒸着用粒体は、上述の本発明の一態様に係る真空蒸着用粒体を用いることができる。蒸着膜14は、電子注入層として働くことができる。蒸着膜14は、陰極15側の有機機能層13上に形成してよく、有機機能層13側の陰極15上に形成してもよい。
[Vaporized film]
The vapor deposition film 14 is a film formed of particles for vacuum vapor deposition, and is an inorganic film formed of an inorganic material. The thickness of the vapor deposition film 14 is, for example, 0.5 nm to 20 nm, preferably 1 nm to 10 nm. As the particles for vacuum vapor deposition, the particles for vacuum vapor deposition according to one embodiment of the present invention described above can be used. The vapor deposition film 14 can function as an electron injection layer. The vapor deposition film 14 may be formed on the organic functional layer 13 on the cathode 15 side, or may be formed on the cathode 15 on the organic functional layer 13 side.
電子注入層は、陰極15から発光層への電子注入効率を改善する機能を有する。電子注入層の材料には、上述の真空蒸着用粒体が用いられる。 The electron injection layer has a function of improving electron injection efficiency from the cathode 15 to the light emitting layer. As the material of the electron injection layer, the above-mentioned particles for vacuum vapor deposition are used.
[陰極]
陰極15は、発光層上に設けられている。陰極15の厚みは、用いる材料によって最適値が異なり、電気伝導度、耐久性等を考慮して設定される。陰極15の厚みは、通常、10nm〜10μmであり、好ましくは20nm〜1μmであり、さらに好ましくは50nm〜500nmである。
[cathode]
The cathode 15 is provided on the light emitting layer. The optimum thickness of the cathode 15 differs depending on the material used, and is set in consideration of electrical conductivity, durability and the like. The thickness of the cathode 15 is usually 10 nm to 10 μm, preferably 20 nm to 1 μm, and more preferably 50 nm to 500 nm.
有機ELデバイス10は、少なくとも有機機能層13を封止する封止部を備えてもよい。また、引出電極を備えていてもよい。 The organic EL device 10 may include a sealing portion that seals at least the organic functional layer 13. Moreover, you may provide the extraction electrode.
<有機電子デバイスの製造方法>
本発明の一態様に係る有機電子デバイスの製造方法は、真空蒸着法により蒸着膜を形成する工程(以下、蒸着膜形成工程ともいう)を含む。蒸着膜形成工程は、真空蒸着用粒体を蒸着源に連続的に供給する供給工程、および蒸着源から真空蒸着用材料を真空蒸着する蒸着工程を含み得る。
<Method for manufacturing organic electronic device>
A method for manufacturing an organic electronic device according to an aspect of the present invention includes a step of forming a vapor deposition film by a vacuum vapor deposition method (hereinafter, also referred to as a vapor deposition film forming step). The vapor deposition film forming step may include a supply step of continuously supplying the particles for vacuum vapor deposition to the vapor deposition source, and a vapor deposition step of vacuum vapor depositing the material for vacuum vapor deposition from the vapor deposition source.
有機電子デバイスの製造方法は、基板上に陽極(第1電極層)を形成する工程(陽極形成工程)、有機機能層を形成する工程(有機機能層形成工程)、上記蒸着膜形成工程、および陰極(第2電極層)を形成する工程(陰極形成工程)を含む製造方法であってよい。 The method of manufacturing an organic electronic device includes a step of forming an anode (first electrode layer) on a substrate (anode forming step), a step of forming an organic functional layer (organic functional layer forming step), the above vapor deposition film forming step, and The manufacturing method may include a step of forming a cathode (second electrode layer) (cathode forming step).
[陽極形成工程]
陽極形成工程では、基板上に陽極を形成する。基板上に陽極を形成する方法としては、例えば真空成膜法、イオンプレーティング法、メッキ法、塗布法等が挙げられる。塗布法としては、例えばインクジェット印刷法が挙げられるが、陽極14を形成可能な塗布法であれば、他の公知の塗布法でもよい。インクジェット印刷法以外の公知の塗布法としては、例えばマイクログラビアコート法、グラビアコート法、バーコート法、ロールコート法、ワイヤーバーコート法、スプレーコート法、スクリーン印刷法、フレキソ印刷法、オフセット印刷法およびノズルプリント法等が挙げられる。
陽極は、例えば基板の主面上に導電膜を作製した後に、その導電膜を、陽極のパターンにパターニングすることによって形成され得る。
[Anode forming process]
In the anode forming step, an anode is formed on the substrate. Examples of the method for forming the anode on the substrate include a vacuum film forming method, an ion plating method, a plating method, and a coating method. Examples of the coating method include an inkjet printing method, but other known coating methods may be used as long as they can form the anode 14. Known coating methods other than the inkjet printing method include, for example, a microgravure coating method, a gravure coating method, a bar coating method, a roll coating method, a wire bar coating method, a spray coating method, a screen printing method, a flexographic printing method, an offset printing method. And a nozzle printing method and the like.
The anode can be formed, for example, by forming a conductive film on the main surface of the substrate and then patterning the conductive film into a pattern of the anode.
陽極の材料を含む塗布液の溶媒は、陽極の材料を溶解できる溶媒であればよい。溶媒としては、例えばクロロホルム、塩化メチレン、ジクロロエタン等の塩化物溶媒、テトラヒドロフラン等のエーテル溶媒、トルエン、キシレン等の芳香族炭化水素溶媒、アセトン、メチルエチルケトン等のケトン溶媒、酢酸エチル、酢酸ブチル、エチルセルソルブアセテート等のエステル溶媒等が挙げられる。 The solvent of the coating liquid containing the material of the anode may be any solvent that can dissolve the material of the anode. Examples of the solvent include chloride solvents such as chloroform, methylene chloride and dichloroethane, ether solvents such as tetrahydrofuran, aromatic hydrocarbon solvents such as toluene and xylene, ketone solvents such as acetone and methyl ethyl ketone, ethyl acetate, butyl acetate and ethyl cells. Examples thereof include ester solvents such as sorb acetate.
[有機機能層形成工程]
有機機能層形成工程では、陽極上に有機機能層を形成する。有機機能層が有する発光層を形成する場合を例にして説明する。発光層の形成方法としては、例えば真空成膜法、塗布法等が挙げられる。塗布法としては、例えばインクジェット印刷法が挙げられるが、発光層を形成可能な塗布法であれば、他の公知の塗布法でもよい。インクジェット印刷法以外の公知の塗布法としては、陽極を塗布法で形成する場合の説明で例示した塗布法が挙げられる。
有機機能層が発光層以外の機能層を含む場合、有機機能層の層構成に応じて陽極側から順に機能層を形成すればよい。各機能層の形成方法は、発光層の場合と同様とし得る。
[Organic functional layer forming process]
In the organic functional layer forming step, the organic functional layer is formed on the anode. The case of forming the light emitting layer included in the organic functional layer will be described as an example. Examples of the method for forming the light emitting layer include a vacuum film forming method and a coating method. Examples of the coating method include an inkjet printing method, but other known coating methods may be used as long as they can form the light emitting layer. As a known coating method other than the ink jet printing method, the coating method exemplified in the description of forming the anode by the coating method can be mentioned.
When the organic functional layer includes a functional layer other than the light emitting layer, the functional layers may be sequentially formed from the anode side according to the layer structure of the organic functional layer. The method for forming each functional layer may be the same as that for the light emitting layer.
[蒸着膜形成工程]
蒸着膜形成工程では、蒸着源から真空蒸着用材料を真空蒸着し、有機機能層上に蒸着膜を形成する。具体的には、蒸着源を備えた真空蒸着装置を用い、真空下で、陽極および有機機能層が形成された基板に対して、蒸着源から真空蒸着用材料を排出し、蒸着膜を形成する。
[Vaporized film forming process]
In the vapor deposition film forming step, a vacuum vapor deposition material is vacuum vapor deposited from a vapor deposition source to form a vapor deposition film on the organic functional layer. Specifically, using a vacuum vapor deposition apparatus equipped with a vapor deposition source, the material for vacuum vapor deposition is discharged from the vapor deposition source to form a vapor deposition film on the substrate on which the anode and the organic functional layer are formed under vacuum. ..
蒸着膜形成工程は、真空蒸着用粒体を蒸着源に連続的に供給する供給工程、および蒸着源から真空蒸着用材料を真空蒸着する蒸着工程を含み得る。蒸着膜形成工程では、蒸着源に安定して供給でき、生産効率を向上させることができる点から、蒸着源に真空蒸着用材料を連続的に供給することが好ましい。 The vapor deposition film forming step may include a supply step of continuously supplying the particles for vacuum vapor deposition to the vapor deposition source, and a vapor deposition step of vacuum vapor depositing the material for vacuum vapor deposition from the vapor deposition source. In the vapor deposition film forming step, it is preferable to continuously supply the vacuum vapor deposition material to the vapor deposition source from the viewpoint that the vapor deposition film can be stably supplied to the vapor deposition source and the production efficiency can be improved.
蒸着源に真空蒸着用材料を連続的に供給する方法としては、例えば真空蒸着装置の蒸着源に供給機構を備えた供給部を設置し、所定の量の真空蒸着用材料を供給部から蒸着源に充填する方法が挙げられる。供給部に充填された真空蒸着用材料は、蒸着源へと連続的に供給することができる。真空蒸着用材料としては、上述の本発明の一態様に係る真空蒸着用粒体が用いられる。 As a method of continuously supplying the material for vacuum evaporation to the evaporation source, for example, a supply unit having a supply mechanism is installed in the evaporation source of the vacuum evaporation apparatus, and a predetermined amount of the material for vacuum evaporation is supplied from the supply unit to the evaporation source. There is a method of filling. The vacuum evaporation material filled in the supply unit can be continuously supplied to the evaporation source. As the material for vacuum vapor deposition, the above-mentioned particles for vacuum vapor deposition according to one embodiment of the present invention are used.
蒸着膜は、陰極側の有機機能層上に形成してよく、有機機能層側の陰極上に形成してもよい。 The vapor deposition film may be formed on the organic functional layer on the cathode side or may be formed on the cathode on the organic functional layer side.
[陰極形成工程]
陰極形成工程では、有機機能層上に陰極を形成する。陰極は、陽極の形成方法と同様にして形成され得る。ロールツーロール方式で陰極を形成してもよい。すなわち、電極付き基板をその長手方向に搬送しながら発光層上に陰極を形成してもよい。
[Cathode forming step]
In the cathode forming step, a cathode is formed on the organic functional layer. The cathode can be formed in the same manner as the method for forming the anode. The cathode may be formed by a roll-to-roll method. That is, the cathode may be formed on the light emitting layer while the substrate with electrodes is transported in the longitudinal direction.
有機電子デバイスの製造方法では、陽極形成工程、有機機能層形成工程、蒸着膜形成工程および陰極形成工程のうち少なくとも一つの工程をロールツーロール方式で実施してもよい。例えば、有機機能層形成工程をロールツーロール方式で実施してもよいし、有機機能層形成工程、蒸着膜形成工程および陰極形成工程を連続的にロールツーロール方式で実施してもよい。 In the method of manufacturing an organic electronic device, at least one of the step of forming an anode, the step of forming an organic functional layer, the step of forming a deposited film, and the step of forming a cathode may be performed by a roll-to-roll method. For example, the organic functional layer forming step may be performed by a roll-to-roll method, or the organic functional layer forming step, the vapor deposition film forming step and the cathode forming step may be continuously performed by a roll-to-roll method.
本発明の有機電子デバイスは、第1電極層を陰極とし、第2電極層を陽極としてもよい。 In the organic electronic device of the present invention, the first electrode layer may be the cathode and the second electrode layer may be the anode.
以下、実施例により本発明をさらに詳細に説明する。 Hereinafter, the present invention will be described in more detail with reference to Examples.
扁平率、外周比及び特定単位格子数の評価方法について、図2、図3及び図4を用いて以下に説明する。図2、図3及び図4は、後述の粒体A〜Cからそれぞれ採取した5個の粒子1〜5についての各画像処理イメージを示す。 A method of evaluating the flatness ratio, the outer peripheral ratio, and the number of specific unit lattices will be described below with reference to FIGS. 2, 3, and 4. 2, FIG. 3 and FIG. 4 show respective image processing images of five particles 1 to 5 respectively collected from particles A to C described later.
[扁平率]
まず、粒体A〜Cからそれぞれ35個の粒子を採取し、各粒子につき以下の操作を行った。粒子を光学顕微鏡(OLYMPUS製MX61L)のステージ上に置き、ステージに変位1cmにて1Hzの振動を10回繰り返し与え、真空蒸着用粒子がステージ上で最も安定して配置された状態(最安定面配置)とした。投影画像は、対物レンズ(LMPLFLN ×5)を通してカメラユニット(接眼ユニット:DP72)により落射光観察にてステージ面に対して鉛直方向に撮影を行い、真空蒸着用粒子の垂直投影図をパーソナルコンピュータ上に取り込んだ(図2a、図3a及び図4a)。画像の焦点は、粒子の外形が最も鮮明になるように合わせた。
[Flatness]
First, 35 particles were collected from each of the particles A to C, and the following operation was performed on each particle. The particles are placed on the stage of an optical microscope (MX61L made by OLYMPUS), the vibration of 1 Hz is repeatedly applied to the stage at a displacement of 1 cm 10 times, and the particles for vacuum deposition are most stably arranged on the stage (most stable surface). Arrangement). The projection image is taken vertically through the objective lens (LMPLFLN × 5) by the camera unit (eyepiece unit: DP72) by observing the incident light, and a vertical projection view of the particles for vacuum deposition is displayed on the personal computer. (FIGS. 2a, 3a and 4a). The image was focused so that the outline of the particles was the sharpest.
次に得られた真空蒸着用粒子の垂直投影図を画像解析ソフト(ImageJ:オープンソースによる画像解析ソフト)を用いて2値化し(図2b、図3b及び図4b)、これを面積相当近似法により楕円形の形状へと変換し(図2c、図3c及び図4c)、その形状の輪郭を得た(図2d、図3d及び図4d)。得られた楕円形の長軸および短軸を求め、以下の式(i)にしたがって扁平率を算出した。
扁平率[%]=〔(長軸寸法−短軸寸法)/長軸寸法〕×100 (i)
Next, the obtained vertical projection view of the particles for vacuum vapor deposition was binarized using image analysis software (ImageJ: image analysis software by open source) (FIGS. 2b, 3b and 4b), and this was converted into an area equivalent approximation method. Was converted into an elliptical shape by (FIG. 2c, FIG. 3c and FIG. 4c) and a contour of the shape was obtained (FIG. 2d, FIG. 3d and FIG. 4d). The major axis and the minor axis of the obtained ellipse were obtained, and the oblateness was calculated according to the following formula (i).
Flatness [%]=[(long axis dimension-short axis dimension)/long axis dimension]×100 (i)
[外周比]
上記扁平率の測定において得られた真空蒸着用粒子の垂直投影図において、2値化した真空蒸着用粒子の形状(図2b、図3b及び図4b)の外周寸法と、その形状を面積相当近似法により変換した楕円形(図2c、図3c及び図4c)の外周寸法とを、画像解析ソフト(ImageJ:オープンソースによる画像解析ソフト)を用いて求め、楕円形の外周寸法に対する前記真空蒸着用粒子の垂直投影図により示される形状の外周寸法の割合を算出した。
[Perimeter ratio]
In the vertical projection view of the particles for vacuum vapor deposition obtained in the above-mentioned measurement of the flatness, the outer peripheral dimension of the shape (FIGS. 2b, 3b and 4b) of the binarized particles for vacuum vapor deposition and the shape are approximated by an area equivalent. The outer peripheral dimension of the elliptical shape (FIGS. 2c, 3c and 4c) converted by the method is obtained by using image analysis software (ImageJ: image analysis software by open source), and the above-mentioned vacuum deposition for the elliptical outer peripheral dimension is performed. The ratio of the outer peripheral dimension of the shape shown by the vertical projection view of the particles was calculated.
[特定単位格子数]
上記扁平率の測定において得られた真空蒸着用粒子の垂直投影図(図2a、図3a及び図4a)において、真空蒸着用粒子の形状を、画像解析ソフト(ImageJ:オープンソースによる画像解析ソフト)を用いて上記扁平率の測定において求めた楕円形(図2c、図3c及び図4c)の長軸寸法の10等分した長さを単位格子の1辺の長さとする正方格子により分割し、分割垂直投影図とした(図2e、図3e及び図4e)。この1辺と粒子の垂直投影図により表される形状の輪郭との交点を2つ有し、かつこの2つの交点における輪郭についての接線がなす角度の上記1辺側の角度が100度以下である単位格子(特定単位格子)の数を測定した。
[Specific unit grid number]
In the vertical projection views (FIGS. 2a, 3a and 4a) of the particles for vacuum vapor deposition obtained in the measurement of the flatness, the shape of the particles for vacuum vapor deposition is analyzed by image analysis software (ImageJ: image analysis software by open source). The elliptical shape (FIG. 2c, FIG. 3c and FIG. 4c) obtained in the above-mentioned oblateness measurement using is divided into 10 equal lengths of the major axis dimension by a square lattice having the length of one side of the unit lattice, The views were divided vertical projections (FIGS. 2e, 3e and 4e). If there are two intersections between this one side and the contour of the shape represented by the vertical projection view of the particle, and the angle formed by the tangents to the contours at these two intersections on the one side is 100 degrees or less. The number of certain unit cells (specific unit cells) was measured.
[化合物1]
フッ化ナトリウム(NaF)結晶(比重:2.8g/cm3)
[Compound 1]
Sodium fluoride (NaF) crystal (specific gravity: 2.8 g/cm 3 )
[真空蒸着用粒体]
粒体A(NaF結晶からなる粒子から構成される真空蒸着用粒体):採取した35個の粒子についての扁平率および外周寸法の割合の評価結果を表1及び2に示す。粒体Aから採取した5個の粒子は全て特定単位格子の数が3未満であった。
粒体B(NaF結晶からなる粒子から構成される真空蒸着用粒体):採取した35個の粒子についての扁平率および外周寸法の割合の評価結果を表1及び2に示す。粒体Bから採取した5個の粒子は全て特定単位格子の数が3未満であった。
粒体C(NaF結晶からなる粒子から構成される真空蒸着用粒体、Alfa Aesar株式会社製):採取した35個の粒子についての扁平率および外周寸法の割合の評価結果を表1及び2に示す。粒体Cから採取した5個の粒子は全て特定単位格子の数が3以上であった。
[Vacuum deposition particles]
Granules A (Vacuum vapor deposition granules composed of particles composed of NaF crystals): Tables 1 and 2 show the evaluation results of the flatness and the ratio of the outer peripheral dimension of the 35 particles collected. All of the 5 particles collected from the granules A had the number of specific unit cells less than 3.
Granules B (Vacuum vapor deposition granules composed of particles made of NaF crystals): Tables 1 and 2 show the evaluation results of the flatness and the ratio of the outer peripheral dimension of the 35 particles collected. All the five particles collected from the granule B had the number of specific unit cells less than 3.
Granules C (Vacuum deposition granules composed of particles made of NaF crystals, manufactured by Alfa Aesar Co., Ltd.): Tables 1 and 2 show the evaluation results of the oblateness and the ratio of the outer peripheral dimension for the 35 particles collected. Show. All of the 5 particles collected from the granule C had the number of specific unit cells of 3 or more.
実施例1
粒体Aについて、真空蒸着装置の供給部を模擬したφ6mmの開口を持つ平板を通して供給を行い、閉塞が生じるか確認した。供給中、粒体の閉塞が起こることなく連続的に供給することができた。
Example 1
The granules A were supplied through a flat plate having an opening of φ6 mm simulating the supply part of a vacuum vapor deposition device, and it was confirmed whether or not blockage occurred. During the feeding, the particles could be fed continuously without clogging of the granules.
実施例2
粒体Aに代えて粒体Bを用いたこと以外は、実施例1と同様にして閉塞が生じるか確認した。供給中、粒体の閉塞が起こることなく連続的に供給することができた。
Example 2
It was confirmed in the same manner as in Example 1 except that the granules B were used in place of the granules A and whether clogging occurred. During the feeding, the particles could be fed continuously without clogging of the granules.
比較例1
粒体Aに代えて粒体Cを用いたこと以外は、実施例1と同様にして閉塞が生じるか確認した。供給中、粒子が引っかかることによって開口部の閉塞が生じ、連続的に供給することができなかった。
Comparative Example 1
It was confirmed whether clogging occurred in the same manner as in Example 1 except that the granules C were used instead of the granules A. During the feeding, particles were caught and the opening was blocked, so that the feeding could not be continuously performed.
10 有機ELデバイス、11 基板、12 陽極、13 有機機能層、14 蒸着膜、15 陰極 10 organic EL device, 11 substrate, 12 anode, 13 organic functional layer, 14 vapor deposition film, 15 cathode
Claims (9)
ABx (1)
[式中、Aは、アルカリ金属原子またはアルカリ土類金属原子を示し、Bは、ハロゲン原子を示し、およびxは1または2である]
で表される化合物を含有する粒子から構成される真空蒸着用粒体であって、下記条件(a)を満たす前記粒子の個数の割合が80%を超える、真空蒸着用粒体。
条件(a):前記粒子の垂直投影図により示される形状の輪郭を面積相当近似法により楕円形へ変換したときの該楕円形の下記式(i)で定義される扁平率が40%以下である。
扁平率=〔(長軸寸法−短軸寸法)/長軸寸法〕×100 (i) Formula (1):
AB x (1)
[In the formula, A represents an alkali metal atom or an alkaline earth metal atom, B represents a halogen atom, and x is 1 or 2.]
A particle for vacuum vapor deposition composed of particles containing a compound represented by: wherein the ratio of the number of the particles satisfying the following condition (a) exceeds 80%.
Condition (a): When the contour of the shape shown by the vertical projection of the particles is converted into an ellipse by the area equivalent approximation method, the oblateness defined by the following formula (i) is 40% or less. is there.
Flatness = [(major axis dimension-minor axis dimension)/major axis dimension] x 100 (i)
条件(b):前記楕円形の外周寸法に対する前記粒子の垂直投影図により示される形状の外周寸法の割合が150%以下である。 The granular material for vacuum vapor deposition according to claim 1, wherein a ratio of the number of the particles satisfying the following condition (b) is 70% or more.
Condition (b): The ratio of the outer peripheral dimension of the shape shown by the vertical projection of the particles to the outer peripheral dimension of the ellipse is 150% or less.
条件(c):前記粒子の垂直投影図により示される形状を、前記長軸寸法を10等分した長さを単位格子の1辺の長さとする正方格子により分割したときに、前記単位格子を構成する1辺において、該1辺と前記粒子の垂直投影図により示される形状の輪郭との交点を2つ有する単位格子であって、前記2つの交点における前記輪郭についての接線がなす角度の前記1辺側の角度が100度以下である単位格子の数が3未満である。 The particle for vacuum vapor deposition according to claim 1 or 2, comprising the particle satisfying the following condition (c).
Condition (c): When the shape shown by the vertical projection of the particle is divided by a square lattice having a length obtained by dividing the major axis dimension into 10 equal to one side length of the unit lattice, A unit cell having, on one side, two intersections of the one side and a contour of a shape shown by a vertical projection view of the particle, the unit grid having an angle formed by a tangent line to the contour at the two intersections. The number of unit cells whose angle on one side is 100 degrees or less is less than 3.
真空蒸着法により蒸着膜を形成する工程
を含む製造方法。 The method of manufacturing an organic electronic device according to claim 6, wherein
A manufacturing method including a step of forming a vapor deposition film by a vacuum vapor deposition method.
前記真空蒸着用粒体を蒸着源に連続的に供給する供給工程と、
前記蒸着源から真空蒸着用材料を真空蒸着する蒸着工程と
を含む、請求項7に記載の製造方法。 The step of forming the deposited film includes
A supplying step of continuously supplying the particles for vacuum evaporation to an evaporation source,
The vapor deposition process which vacuum-deposits the material for vacuum vapor deposition from the said vapor deposition source, The manufacturing method of Claim 7.
ABx (1)
[式中、Aは、アルカリ金属原子またはアルカリ土類金属原子を示し、Bは、ハロゲン原子を示し、xは1または2である]
で表される化合物を含有する粒子であって、下記条件(a1)および(c1)を満たす粒子。
条件(a1):前記粒子の垂直投影図により示される形状の輪郭を面積相当近似法により楕円形へ変換したときの該楕円形の下記式(i)で定義される扁平率が50%以下である。
扁平率=〔(長軸寸法−短軸寸法)/長軸寸法〕×100 (i)
条件(c1):前記粒子の垂直投影図により示される形状を、前記長軸寸法の10等分した長さを単位格子の1辺の長さとする正方格子により分割したときに、前記単位格子を構成する1辺において、該1辺と前記粒子の垂直投影図により示される形状の輪郭との交点を2つ有する単位格子であって、前記2つの交点における前記輪郭についての接線がなす角度の前記1辺側の角度が100度以下である単位格子の数が3未満である。 Formula (1):
AB x (1)
[In the formula, A represents an alkali metal atom or an alkaline earth metal atom, B represents a halogen atom, and x is 1 or 2.]
Particles containing a compound represented by the following formula, which satisfy the following conditions (a1) and (c1).
Condition (a1): When the contour of the shape shown by the vertical projection of the particle is converted into an ellipse by the area equivalent approximation method, the oblateness defined by the following formula (i) is 50% or less. is there.
Flatness = [(major axis dimension-minor axis dimension)/major axis dimension] x 100 (i)
Condition (c1): When the shape shown by the vertical projection view of the particles is divided by a square lattice having a length obtained by dividing the major axis dimension into 10 equal to one side of the unit lattice, A unit cell having two intersections of the one side and the contour of the shape shown by the vertical projection view of the particle on one side, and the angle of the tangent to the contour at the two intersections The number of unit cells whose angle on one side is 100 degrees or less is less than 3.
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JP2004169098A (en) * | 2002-11-19 | 2004-06-17 | Toshiba Corp | Vapor depositing material, and optical thin film and optical component obtained by using the same |
WO2013190847A1 (en) * | 2012-06-20 | 2013-12-27 | パナソニック株式会社 | Organic light-emitting element and production method therefor |
JP2017088468A (en) * | 2015-11-17 | 2017-05-25 | デンカ株式会社 | Spherical calcium fluoride |
WO2018174117A1 (en) * | 2017-03-23 | 2018-09-27 | コニカミノルタ株式会社 | Coating liquid for forming organic film, organic film, organic electronic device, and method for producing coating liquid for forming organic film |
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JPS4829045U (en) * | 1971-08-13 | 1973-04-10 | ||
JP2004169098A (en) * | 2002-11-19 | 2004-06-17 | Toshiba Corp | Vapor depositing material, and optical thin film and optical component obtained by using the same |
WO2013190847A1 (en) * | 2012-06-20 | 2013-12-27 | パナソニック株式会社 | Organic light-emitting element and production method therefor |
JP2017088468A (en) * | 2015-11-17 | 2017-05-25 | デンカ株式会社 | Spherical calcium fluoride |
WO2018174117A1 (en) * | 2017-03-23 | 2018-09-27 | コニカミノルタ株式会社 | Coating liquid for forming organic film, organic film, organic electronic device, and method for producing coating liquid for forming organic film |
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