JP2002319488A - Organic electroluminescent element - Google Patents
Organic electroluminescent elementInfo
- Publication number
- JP2002319488A JP2002319488A JP2001123343A JP2001123343A JP2002319488A JP 2002319488 A JP2002319488 A JP 2002319488A JP 2001123343 A JP2001123343 A JP 2001123343A JP 2001123343 A JP2001123343 A JP 2001123343A JP 2002319488 A JP2002319488 A JP 2002319488A
- Authority
- JP
- Japan
- Prior art keywords
- organic
- layer
- cal
- solvent
- light emitting
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- 239000002904 solvent Substances 0.000 claims abstract description 56
- 239000010410 layer Substances 0.000 claims description 166
- 239000000126 substance Substances 0.000 claims description 74
- 230000000903 blocking effect Effects 0.000 claims description 21
- 238000005401 electroluminescence Methods 0.000 claims description 20
- 239000012044 organic layer Substances 0.000 claims description 20
- 239000000758 substrate Substances 0.000 claims description 17
- 239000002019 doping agent Substances 0.000 claims description 15
- 239000003795 chemical substances by application Substances 0.000 claims description 12
- 125000001424 substituent group Chemical group 0.000 claims description 5
- 229910052739 hydrogen Inorganic materials 0.000 claims description 4
- 239000011368 organic material Substances 0.000 claims description 4
- 125000003118 aryl group Chemical group 0.000 claims 3
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims 1
- 239000001257 hydrogen Substances 0.000 claims 1
- 239000005416 organic matter Substances 0.000 abstract description 4
- 239000000243 solution Substances 0.000 description 52
- 229920000642 polymer Polymers 0.000 description 28
- 150000001875 compounds Chemical class 0.000 description 27
- 238000004090 dissolution Methods 0.000 description 24
- 230000005525 hole transport Effects 0.000 description 22
- 238000000034 method Methods 0.000 description 19
- 239000011230 binding agent Substances 0.000 description 14
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 13
- 229910052744 lithium Inorganic materials 0.000 description 13
- 238000004528 spin coating Methods 0.000 description 12
- 239000010409 thin film Substances 0.000 description 11
- 229910052760 oxygen Inorganic materials 0.000 description 10
- 229920003227 poly(N-vinyl carbazole) Polymers 0.000 description 10
- 125000000217 alkyl group Chemical group 0.000 description 9
- 229910052782 aluminium Inorganic materials 0.000 description 9
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 9
- 229920002857 polybutadiene Polymers 0.000 description 9
- 229920002098 polyfluorene Polymers 0.000 description 9
- YNQLUTRBYVCPMQ-UHFFFAOYSA-N Ethylbenzene Chemical compound CCC1=CC=CC=C1 YNQLUTRBYVCPMQ-UHFFFAOYSA-N 0.000 description 8
- 230000015572 biosynthetic process Effects 0.000 description 8
- 238000000151 deposition Methods 0.000 description 8
- UEEXRMUCXBPYOV-UHFFFAOYSA-N iridium;2-phenylpyridine Chemical compound [Ir].C1=CC=CC=C1C1=CC=CC=N1.C1=CC=CC=C1C1=CC=CC=N1.C1=CC=CC=C1C1=CC=CC=N1 UEEXRMUCXBPYOV-UHFFFAOYSA-N 0.000 description 8
- 238000004519 manufacturing process Methods 0.000 description 8
- -1 silver and chromium Chemical compound 0.000 description 8
- 239000004793 Polystyrene Substances 0.000 description 7
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 7
- 230000008021 deposition Effects 0.000 description 7
- 238000002474 experimental method Methods 0.000 description 7
- 239000001301 oxygen Substances 0.000 description 7
- 229920002223 polystyrene Polymers 0.000 description 7
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N diphenyl Chemical compound C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 description 6
- 239000000463 material Substances 0.000 description 6
- 238000005259 measurement Methods 0.000 description 6
- 229920002554 vinyl polymer Polymers 0.000 description 6
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 5
- 238000004020 luminiscence type Methods 0.000 description 5
- WSLDOOZREJYCGB-UHFFFAOYSA-N 1,2-Dichloroethane Chemical compound ClCCCl WSLDOOZREJYCGB-UHFFFAOYSA-N 0.000 description 4
- UJOBWOGCFQCDNV-UHFFFAOYSA-N Carbazole Natural products C1=CC=C2C3=CC=CC=C3NC2=C1 UJOBWOGCFQCDNV-UHFFFAOYSA-N 0.000 description 4
- 238000000576 coating method Methods 0.000 description 4
- 238000001704 evaporation Methods 0.000 description 4
- 238000002347 injection Methods 0.000 description 4
- 239000007924 injection Substances 0.000 description 4
- 229920001088 polycarbazole Polymers 0.000 description 4
- ZVFQEOPUXVPSLB-UHFFFAOYSA-N 3-(4-tert-butylphenyl)-4-phenyl-5-(4-phenylphenyl)-1,2,4-triazole Chemical compound C1=CC(C(C)(C)C)=CC=C1C(N1C=2C=CC=CC=2)=NN=C1C1=CC=C(C=2C=CC=CC=2)C=C1 ZVFQEOPUXVPSLB-UHFFFAOYSA-N 0.000 description 3
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 3
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 3
- 235000010290 biphenyl Nutrition 0.000 description 3
- 239000004305 biphenyl Substances 0.000 description 3
- 238000010549 co-Evaporation Methods 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 239000010408 film Substances 0.000 description 3
- 229910052741 iridium Inorganic materials 0.000 description 3
- GKOZUEZYRPOHIO-UHFFFAOYSA-N iridium atom Chemical compound [Ir] GKOZUEZYRPOHIO-UHFFFAOYSA-N 0.000 description 3
- 239000008096 xylene Substances 0.000 description 3
- SCYULBFZEHDVBN-UHFFFAOYSA-N 1,1-Dichloroethane Chemical compound CC(Cl)Cl SCYULBFZEHDVBN-UHFFFAOYSA-N 0.000 description 2
- AFFLGGQVNFXPEV-UHFFFAOYSA-N 1-decene Chemical compound CCCCCCCCC=C AFFLGGQVNFXPEV-UHFFFAOYSA-N 0.000 description 2
- OVSKIKFHRZPJSS-UHFFFAOYSA-N 2,4-D Chemical compound OC(=O)COC1=CC=C(Cl)C=C1Cl OVSKIKFHRZPJSS-UHFFFAOYSA-N 0.000 description 2
- MWPLVEDNUUSJAV-UHFFFAOYSA-N anthracene Chemical compound C1=CC=CC2=CC3=CC=CC=C3C=C21 MWPLVEDNUUSJAV-UHFFFAOYSA-N 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 230000008020 evaporation Effects 0.000 description 2
- NIHNNTQXNPWCJQ-UHFFFAOYSA-N fluorene Chemical compound C1=CC=C2CC3=CC=CC=C3C2=C1 NIHNNTQXNPWCJQ-UHFFFAOYSA-N 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 239000011521 glass Substances 0.000 description 2
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 2
- 229910052737 gold Inorganic materials 0.000 description 2
- 239000010931 gold Substances 0.000 description 2
- RBTKNAXYKSUFRK-UHFFFAOYSA-N heliogen blue Chemical compound [Cu].[N-]1C2=C(C=CC=C3)C3=C1N=C([N-]1)C3=CC=CC=C3C1=NC([N-]1)=C(C=CC=C3)C3=C1N=C([N-]1)C3=CC=CC=C3C1=N2 RBTKNAXYKSUFRK-UHFFFAOYSA-N 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 239000012280 lithium aluminium hydride Substances 0.000 description 2
- PQXKHYXIUOZZFA-UHFFFAOYSA-M lithium fluoride Chemical compound [Li+].[F-] PQXKHYXIUOZZFA-UHFFFAOYSA-M 0.000 description 2
- UAEPNZWRGJTJPN-UHFFFAOYSA-N methylcyclohexane Chemical compound CC1CCCCC1 UAEPNZWRGJTJPN-UHFFFAOYSA-N 0.000 description 2
- BKIMMITUMNQMOS-UHFFFAOYSA-N nonane Chemical compound CCCCCCCCC BKIMMITUMNQMOS-UHFFFAOYSA-N 0.000 description 2
- WCPAKWJPBJAGKN-UHFFFAOYSA-N oxadiazole Chemical compound C1=CON=N1 WCPAKWJPBJAGKN-UHFFFAOYSA-N 0.000 description 2
- HDBWAWNLGGMZRQ-UHFFFAOYSA-N p-Vinylbiphenyl Chemical group C1=CC(C=C)=CC=C1C1=CC=CC=C1 HDBWAWNLGGMZRQ-UHFFFAOYSA-N 0.000 description 2
- YNPNZTXNASCQKK-UHFFFAOYSA-N phenanthrene Chemical compound C1=CC=C2C3=CC=CC=C3C=CC2=C1 YNPNZTXNASCQKK-UHFFFAOYSA-N 0.000 description 2
- 238000006116 polymerization reaction Methods 0.000 description 2
- 229910052709 silver Inorganic materials 0.000 description 2
- 239000004332 silver Substances 0.000 description 2
- 150000003384 small molecules Chemical class 0.000 description 2
- TVIVIEFSHFOWTE-UHFFFAOYSA-K tri(quinolin-8-yloxy)alumane Chemical compound [Al+3].C1=CN=C2C([O-])=CC=CC2=C1.C1=CN=C2C([O-])=CC=CC2=C1.C1=CN=C2C([O-])=CC=CC2=C1 TVIVIEFSHFOWTE-UHFFFAOYSA-K 0.000 description 2
- 150000003852 triazoles Chemical class 0.000 description 2
- 238000001771 vacuum deposition Methods 0.000 description 2
- 238000007740 vapor deposition Methods 0.000 description 2
- 238000009834 vaporization Methods 0.000 description 2
- 230000008016 vaporization Effects 0.000 description 2
- ZSYMVHGRKPBJCQ-UHFFFAOYSA-N 1,1'-biphenyl;9h-carbazole Chemical group C1=CC=CC=C1C1=CC=CC=C1.C1=CC=C2C3=CC=CC=C3NC2=C1 ZSYMVHGRKPBJCQ-UHFFFAOYSA-N 0.000 description 1
- LCAKAXJAQMMVTQ-UHFFFAOYSA-N 1-(2,2-diphenylethenyl)-2-phenylbenzene Chemical group C=1C=CC=C(C=2C=CC=CC=2)C=1C=C(C=1C=CC=CC=1)C1=CC=CC=C1 LCAKAXJAQMMVTQ-UHFFFAOYSA-N 0.000 description 1
- UHXOHPVVEHBKKT-UHFFFAOYSA-N 1-(2,2-diphenylethenyl)-4-[4-(2,2-diphenylethenyl)phenyl]benzene Chemical compound C=1C=C(C=2C=CC(C=C(C=3C=CC=CC=3)C=3C=CC=CC=3)=CC=2)C=CC=1C=C(C=1C=CC=CC=1)C1=CC=CC=C1 UHXOHPVVEHBKKT-UHFFFAOYSA-N 0.000 description 1
- DLKQHBOKULLWDQ-UHFFFAOYSA-N 1-bromonaphthalene Chemical compound C1=CC=C2C(Br)=CC=CC2=C1 DLKQHBOKULLWDQ-UHFFFAOYSA-N 0.000 description 1
- PXRPXTORPZOTRT-UHFFFAOYSA-N 10-[4-(4-phenothiazin-10-ylphenyl)phenyl]phenothiazine Chemical group C12=CC=CC=C2SC2=CC=CC=C2N1C1=CC=C(C=2C=CC(=CC=2)N2C3=CC=CC=C3SC3=CC=CC=C32)C=C1 PXRPXTORPZOTRT-UHFFFAOYSA-N 0.000 description 1
- IVVYVRLKDGGUEL-UHFFFAOYSA-N 2,5-bis(4-phenylphenyl)-1,3,4-oxadiazole Chemical compound C1=CC=CC=C1C1=CC=C(C=2OC(=NN=2)C=2C=CC(=CC=2)C=2C=CC=CC=2)C=C1 IVVYVRLKDGGUEL-UHFFFAOYSA-N 0.000 description 1
- MUNFOTHAFHGRIM-UHFFFAOYSA-N 2,5-dinaphthalen-1-yl-1,3,4-oxadiazole Chemical compound C1=CC=C2C(C3=NN=C(O3)C=3C4=CC=CC=C4C=CC=3)=CC=CC2=C1 MUNFOTHAFHGRIM-UHFFFAOYSA-N 0.000 description 1
- STTGYIUESPWXOW-UHFFFAOYSA-N 2,9-dimethyl-4,7-diphenyl-1,10-phenanthroline Chemical compound C=12C=CC3=C(C=4C=CC=CC=4)C=C(C)N=C3C2=NC(C)=CC=1C1=CC=CC=C1 STTGYIUESPWXOW-UHFFFAOYSA-N 0.000 description 1
- CRGSMSNUTNRNQM-UHFFFAOYSA-N 2-(4-tert-butylphenyl)-1,3,4-oxadiazole Chemical compound C1=CC(C(C)(C)C)=CC=C1C1=NN=CO1 CRGSMSNUTNRNQM-UHFFFAOYSA-N 0.000 description 1
- ONKCIMOQGCARHN-UHFFFAOYSA-N 3-methyl-n-[4-[4-(3-methylanilino)phenyl]phenyl]aniline Chemical compound CC1=CC=CC(NC=2C=CC(=CC=2)C=2C=CC(NC=3C=C(C)C=CC=3)=CC=2)=C1 ONKCIMOQGCARHN-UHFFFAOYSA-N 0.000 description 1
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 description 1
- LPKVSKJMSDTMSX-UHFFFAOYSA-N CC1=CC=C(C=C1)C(=CC1=C(C=CC=C1)C1=CC=CC=C1)C1=CC=C(C=C1)C Chemical group CC1=CC=C(C=C1)C(=CC1=C(C=CC=C1)C1=CC=CC=C1)C1=CC=C(C=C1)C LPKVSKJMSDTMSX-UHFFFAOYSA-N 0.000 description 1
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-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
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- 229920001157 Poly(2-vinylnaphthalene) Polymers 0.000 description 1
- 229920001054 Poly(ethylene‐co‐vinyl acetate) Polymers 0.000 description 1
- 239000005062 Polybutadiene Substances 0.000 description 1
- 239000002202 Polyethylene glycol Substances 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 1
- XSTXAVWGXDQKEL-UHFFFAOYSA-N Trichloroethylene Chemical group ClC=C(Cl)Cl XSTXAVWGXDQKEL-UHFFFAOYSA-N 0.000 description 1
- 239000007983 Tris buffer Substances 0.000 description 1
- ULGYAEQHFNJYML-UHFFFAOYSA-N [AlH3].[Ca] Chemical compound [AlH3].[Ca] ULGYAEQHFNJYML-UHFFFAOYSA-N 0.000 description 1
- CUJRVFIICFDLGR-UHFFFAOYSA-N acetylacetonate Chemical compound CC(=O)[CH-]C(C)=O CUJRVFIICFDLGR-UHFFFAOYSA-N 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- 230000001174 ascending effect Effects 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
- 229910052796 boron Inorganic materials 0.000 description 1
- NTXGQCSETZTARF-UHFFFAOYSA-N buta-1,3-diene;prop-2-enenitrile Polymers C=CC=C.C=CC#N NTXGQCSETZTARF-UHFFFAOYSA-N 0.000 description 1
- XZCJVWCMJYNSQO-UHFFFAOYSA-N butyl pbd Chemical compound C1=CC(C(C)(C)C)=CC=C1C1=NN=C(C=2C=CC(=CC=2)C=2C=CC=CC=2)O1 XZCJVWCMJYNSQO-UHFFFAOYSA-N 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
- 238000005266 casting Methods 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
- 239000011651 chromium Substances 0.000 description 1
- 229920001940 conductive polymer Polymers 0.000 description 1
- 239000004020 conductor Substances 0.000 description 1
- 239000013256 coordination polymer Substances 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- OMZSGWSJDCOLKM-UHFFFAOYSA-N copper(II) sulfide Chemical compound [S-2].[Cu+2] OMZSGWSJDCOLKM-UHFFFAOYSA-N 0.000 description 1
- GBRBMTNGQBKBQE-UHFFFAOYSA-L copper;diiodide Chemical compound I[Cu]I GBRBMTNGQBKBQE-UHFFFAOYSA-L 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 238000003618 dip coating Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 230000005284 excitation Effects 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 238000005227 gel permeation chromatography Methods 0.000 description 1
- 238000010438 heat treatment 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
- 238000010030 laminating Methods 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- GYNNXHKOJHMOHS-UHFFFAOYSA-N methyl-cycloheptane Natural products CC1CCCCCC1 GYNNXHKOJHMOHS-UHFFFAOYSA-N 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- IBHBKWKFFTZAHE-UHFFFAOYSA-N n-[4-[4-(n-naphthalen-1-ylanilino)phenyl]phenyl]-n-phenylnaphthalen-1-amine Chemical compound C1=CC=CC=C1N(C=1C2=CC=CC=C2C=CC=1)C1=CC=C(C=2C=CC(=CC=2)N(C=2C=CC=CC=2)C=2C3=CC=CC=C3C=CC=2)C=C1 IBHBKWKFFTZAHE-UHFFFAOYSA-N 0.000 description 1
- SNMVRZFUUCLYTO-UHFFFAOYSA-N n-propyl chloride Chemical compound CCCCl SNMVRZFUUCLYTO-UHFFFAOYSA-N 0.000 description 1
- MCSAJNNLRCFZED-UHFFFAOYSA-N nitroethane Chemical compound CC[N+]([O-])=O MCSAJNNLRCFZED-UHFFFAOYSA-N 0.000 description 1
- JZRYQZJSTWVBBD-UHFFFAOYSA-N pentaporphyrin i Chemical compound N1C(C=C2NC(=CC3=NC(=C4)C=C3)C=C2)=CC=C1C=C1C=CC4=N1 JZRYQZJSTWVBBD-UHFFFAOYSA-N 0.000 description 1
- 125000002080 perylenyl group Chemical group C1(=CC=C2C=CC=C3C4=CC=CC5=CC=CC(C1=C23)=C45)* 0.000 description 1
- 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 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 238000009832 plasma treatment Methods 0.000 description 1
- 229920005593 poly(benzyl methacrylate) Polymers 0.000 description 1
- 229920001200 poly(ethylene-vinyl acetate) Polymers 0.000 description 1
- 229920003229 poly(methyl methacrylate) Polymers 0.000 description 1
- 229920000553 poly(phenylenevinylene) Polymers 0.000 description 1
- 229920000767 polyaniline Polymers 0.000 description 1
- 229920001223 polyethylene glycol Polymers 0.000 description 1
- 239000004926 polymethyl methacrylate Substances 0.000 description 1
- 229920000128 polypyrrole Polymers 0.000 description 1
- 229920000123 polythiophene Polymers 0.000 description 1
- 229920002689 polyvinyl acetate Polymers 0.000 description 1
- 239000011118 polyvinyl acetate Substances 0.000 description 1
- 229920000036 polyvinylpyrrolidone Polymers 0.000 description 1
- 239000001267 polyvinylpyrrolidone Substances 0.000 description 1
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- HJWLCRVIBGQPNF-UHFFFAOYSA-N prop-2-enylbenzene Chemical compound C=CCC1=CC=CC=C1 HJWLCRVIBGQPNF-UHFFFAOYSA-N 0.000 description 1
- 229910052701 rubidium Inorganic materials 0.000 description 1
- IGLNJRXAVVLDKE-UHFFFAOYSA-N rubidium atom Chemical compound [Rb] IGLNJRXAVVLDKE-UHFFFAOYSA-N 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 238000004544 sputter deposition Methods 0.000 description 1
- 229910052712 strontium Inorganic materials 0.000 description 1
- CIOAGBVUUVVLOB-UHFFFAOYSA-N strontium atom Chemical compound [Sr] CIOAGBVUUVVLOB-UHFFFAOYSA-N 0.000 description 1
- 229920000638 styrene acrylonitrile Polymers 0.000 description 1
- XOLBLPGZBRYERU-UHFFFAOYSA-N tin dioxide Chemical compound O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 description 1
- 229910001887 tin oxide Inorganic materials 0.000 description 1
- 239000012780 transparent material Substances 0.000 description 1
- 238000011282 treatment Methods 0.000 description 1
- UBOXGVDOUJQMTN-UHFFFAOYSA-N trichloroethylene Natural products ClCC(Cl)Cl UBOXGVDOUJQMTN-UHFFFAOYSA-N 0.000 description 1
- LENZDBCJOHFCAS-UHFFFAOYSA-N tris Chemical compound OCC(N)(CO)CO LENZDBCJOHFCAS-UHFFFAOYSA-N 0.000 description 1
- 238000007738 vacuum evaporation Methods 0.000 description 1
Landscapes
- Electroluminescent Light Sources (AREA)
Abstract
Description
【0001】[0001]
【発明の属する技術分野】本発明は、高輝度での発光が
可能な有機エレクトロルミネッセンス素子に関する。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an organic electroluminescence device capable of emitting light with high luminance.
【0002】[0002]
【従来の技術】従来、米国特許第6097147号によ
り、燐光を放射する物質を含有する発光層を備えた多層
積層構造で形成され、発光効率を向上させた有機エレク
トロルミネッセンス素子が知られている。2. Description of the Related Art Conventionally, there is known an organic electroluminescent device formed of a multilayer laminated structure having a light emitting layer containing a substance emitting phosphorescence and having improved luminous efficiency, from US Pat. No. 6,097,147.
【0003】このものにおいて、多層から成る薄膜の積
層形成に際して発光性物質の蒸着工程を用いる、いわゆ
る乾式法を採用しているため、製造工程が複雑になり生
産効率が悪い。In this method, since a so-called dry method is employed, in which a luminescent substance is deposited during the formation of a multilayer thin film, the manufacturing process is complicated and the production efficiency is poor.
【0004】[0004]
【発明が解決しようとする課題】本発明では上記問題点
に鑑み、簡易な多層積層構造を有する有機エレクトロル
ミネッセンス素子を提供することを課題としている。SUMMARY OF THE INVENTION In view of the above problems, it is an object of the present invention to provide an organic electroluminescence device having a simple multilayered structure.
【0005】[0005]
【課題を解決するための手段】上記課題を解決するた
め、本発明は、陽極層及び陰極層の両電極層と、ホスト
剤と燐光を放射するドープ剤とを有する発光層と、前記
両電極層の間で該発光層に積層する有機層とを具備し、
前記電極層の一方が基板上に形成される有機エレクトロ
ルミネッセンス素子において、前記有機層を構成する有
機物が、該有機層の前記基板側に積層する前記発光層を
構成する有機物に対して溶解範囲外の溶解度パラメータ
を有する溶媒に可溶とした。SUMMARY OF THE INVENTION In order to solve the above-mentioned problems, the present invention provides an anode layer and a cathode layer, a light emitting layer having a host agent and a dopant emitting phosphorescence, An organic layer laminated to the light emitting layer between the layers,
In an organic electroluminescence device in which one of the electrode layers is formed on a substrate, an organic substance constituting the organic layer is out of a dissolving range with respect to an organic substance constituting the light emitting layer laminated on the substrate side of the organic layer. Was dissolved in a solvent having a solubility parameter of
【0006】ここで、モル蒸発熱ΔH、モル体積Vの液
体の絶対温度Tにおける溶解度パラメータSPは、 SP={(ΔH−RT)/V}1/2 で定義される。ただし、上記式中、SPは溶解度パラメ
ータ(単位:(cal/cm3)1/2)であり、ΔHはモ
ル蒸発熱(単位:cal/mol)であり、Rは気体定
数(単位:cal/(mol・K))であり、Tは絶対
温度(単位:K)であり、Vはモル体積(単位:cm3
/mol)である。Here, the solubility parameter SP of the liquid having the molar evaporation heat ΔH and the molar volume V at the absolute temperature T is defined as SP = {(ΔH-RT) / V} 1/2 . Here, in the above formula, SP is a solubility parameter (unit: (cal / cm 3 ) 1/2 ), ΔH is molar heat of vaporization (unit: cal / mol), and R is a gas constant (unit: cal / mol / mol). (Mol · K)), T is the absolute temperature (unit: K), and V is the molar volume (unit: cm 3)
/ Mol).
【0007】本発明では、有機層を構成する有機物を、
発光層を構成する有機物に対して溶解範囲外の溶解度パ
ラメータを有する溶媒に溶解して、有機エレクトロルミ
ネッセンス素子を多層積層構造として形成する。この
際、発光層を構成する有機物は、有機層を構成する有機
物の溶解に用いた溶媒に対して溶解度が僅小であるの
で、発光層と有機層とは、互いに隣接して積層した場
合、各薄膜層を構成する有機物が溶解・混合することな
く薄膜層を形成できる。即ち、発光層や有機層の各薄膜
層を構成する有機物を溶解する溶媒をそれぞれ用いた湿
式法により簡便な薄膜形成が可能である。In the present invention, the organic substance constituting the organic layer is
The organic electroluminescent element is formed as a multilayer laminate structure by dissolving in a solvent having a solubility parameter outside the solubility range for the organic substance constituting the light emitting layer. At this time, since the organic substance constituting the light emitting layer has a very low solubility in the solvent used for dissolving the organic substance constituting the organic layer, when the light emitting layer and the organic layer are laminated adjacent to each other, The thin film layer can be formed without dissolving and mixing the organic substances constituting each thin film layer. That is, a simple thin film can be formed by a wet method using a solvent that dissolves an organic substance constituting each thin film layer of the light emitting layer and the organic layer.
【0008】この場合、前記有機層を構成する有機物
を、電子注入性物質、電子輸送性物質、正孔ブロック性
物質のうち一種類以上から構成することが望ましい。In this case, it is desirable that the organic material constituting the organic layer is composed of at least one of an electron injecting substance, an electron transporting substance, and a hole blocking substance.
【0009】そして、この場合、前記発光層を構成する
有機物は、室温において8.9(cal/cm3)1/2未
満の溶解度パラメータを有する溶媒に不溶であり、前記
有機層を構成する有機物は、室温において7.0(ca
l/cm3)1/2以上8.9(cal/cm3)1/2未満の
溶解度パラメータを有する溶媒に可溶であるように構成
することが望ましい。In this case, the organic substance constituting the light emitting layer is insoluble in a solvent having a solubility parameter of less than 8.9 (cal / cm 3 ) 1/2 at room temperature, and the organic substance constituting the organic layer is not dissolved. Is 7.0 (ca) at room temperature
It is desirable that the composition be configured to be soluble in a solvent having a solubility parameter of 1 / cm 3 ) 1/2 or more and less than 8.9 (cal / cm 3 ) 1/2 .
【0010】また、前記発光層を構成する有機物は、室
温において8.3(cal/cm3)1/2以下の溶解度パ
ラメータを有する溶媒に不溶であり、前記有機層を構成
する有機物は、室温において7.0(cal/cm3)
1/2以上8.3(cal/cm3)1/2以下の溶解度パラ
メータを有する溶媒に可溶であるように構成することも
可能である。The organic substance constituting the light emitting layer is insoluble in a solvent having a solubility parameter of 8.3 (cal / cm 3 ) 1/2 or less at room temperature, and the organic substance constituting the organic layer is not dissolved at room temperature. 7.0 (cal / cm 3 )
It is also possible to constitute so as to be soluble in a solvent having a solubility parameter of 1/2 or more and 8.3 (cal / cm 3 ) 1/2 or less.
【0011】また、前記発光層を構成する有機物は、室
温において11.5(cal/cm 3)1/2以上13.0
(cal/cm3)1/2以下の溶解度パラメータを有する
溶媒に不溶であり、前記有機層を構成する有機物は、室
温において11.5(cal/cm3)1/2以上13.0
(cal/cm3)1/2以下の溶解度パラメータを有する
溶媒に可溶であるように構成することも可能である。The organic substance constituting the light-emitting layer may be
11.5 (cal / cm Three)1/2Above 13.0
(Cal / cmThree)1/2Has the following solubility parameters
The organic matter that is insoluble in the solvent and constitutes the organic layer is
11.5 (cal / cmThree)1/2Above 13.0
(Cal / cmThree)1/2Has the following solubility parameters
It is also possible to configure so as to be soluble in a solvent.
【0012】これらの場合、前記ドープ剤は、化学式
[化1]又は[化2]で表される化合物を用いるのが好
適である。In these cases, it is preferable to use a compound represented by the chemical formula [Chemical Formula 1] or [Chemical Formula 2] as the dopant.
【0013】[0013]
【発明の実施の形態】図1は、発光効率の向上を目的と
して多層に積層された素子構造を有する有機エレクトロ
ルミネッセンス素子の基本構造を示す。有機エレクトロ
ルミネッセンス素子の素子構造は、陽極層10と陰極層
70との両電極層の間に、図外の基板上に形成された陽
極層10に、正孔輸送層20、電子ブロック層30、発
光層40、正孔ブロック層50及び電子輸送層60の各
薄膜層が順次積層されて成る多層積層構造であり、発光
層40は、発光層ドープ剤41と発光層ホスト剤42と
を有している。FIG. 1 shows a basic structure of an organic electroluminescence device having a multilayered device structure for the purpose of improving luminous efficiency. The element structure of the organic electroluminescence element is such that a hole transport layer 20, an electron block layer 30, a hole transport layer 20, and an anode layer 10 formed on a substrate (not shown) The light emitting layer 40, the hole blocking layer 50, and the electron transport layer 60 have a multilayer laminated structure in which thin film layers are sequentially stacked. The light emitting layer 40 has a light emitting layer dopant 41 and a light emitting layer host ing.
【0014】図1乃至図4で示される各素子構造におい
て、陽極層10は、例えばガラス基板のような透明絶縁
性支持体に形成された透明な導電性物質が用いられ、そ
の材料としては、酸化錫、酸化インジウム、酸化錫イン
ジウム(ITO)などの導電性酸化物、あるいは、金、
銀、クロムなどの金属、よう化銅、硫化銅などの無機導
電性物質、ポリチオフェン、ポリピロール、ポリアニリ
ン等の導電性ポリマーなどを用いることができる。In each element structure shown in FIGS. 1 to 4, the anode layer 10 is made of a transparent conductive material formed on a transparent insulating support such as a glass substrate. Conductive oxides such as tin oxide, indium oxide, indium tin oxide (ITO), or gold,
Metals such as silver and chromium, inorganic conductive substances such as copper iodide and copper sulfide, and conductive polymers such as polythiophene, polypyrrole, and polyaniline can be used.
【0015】また、陰極層70が透明な材料で形成され
ている場合には、陽極層10は不透明な材料で形成され
ても良い。When the cathode layer 70 is formed of a transparent material, the anode layer 10 may be formed of an opaque material.
【0016】また、図1乃至図4で示される各素子構造
において、陰極層70には、リチウム、ナトリウム、カ
リウム、ルビジウム、セシウム、マグネシウム、カルシ
ウム、ストロンチウム、バリウム、硼素、アルミニウ
ム、銅、銀、金などの単体または合金が使用できる。さ
らに、これらを積層して使用することもできる。また、
テトラヒドロアルミン酸塩により湿式で形成することも
できる。この場合、陰極層70に用いられるテトラヒド
ロアルミン酸塩としては、特に、水素化アルミニウムリ
チウム、水素化アルミニウムカリウム、水素化アルミニ
ウムマグネシウム、水素化アルミニウムカルシウムを挙
げることができる。この中で、水素化アルミニウムリチ
ウムが、特に電子輸送層への電子注入性に優れている。In each of the device structures shown in FIGS. 1 to 4, the cathode layer 70 has lithium, sodium, potassium, rubidium, cesium, magnesium, calcium, strontium, barium, boron, aluminum, copper, silver, A simple substance such as gold or an alloy can be used. Further, these can be used in a laminated state. Also,
It can also be formed wet with tetrahydroaluminate. In this case, examples of the tetrahydroaluminate used for the cathode layer 70 include lithium aluminum hydride, aluminum potassium hydride, aluminum magnesium hydride, and calcium aluminum hydride. Among them, lithium aluminum hydride is particularly excellent in the electron injection property to the electron transport layer.
【0017】また、正孔輸送層20は、陽極から注入さ
れる正孔を輸送するための層であり、正孔輸送性有機物
を含む有機層である。正孔輸送層性有機物の例として、The hole transport layer 20 is a layer for transporting holes injected from the anode, and is an organic layer containing a hole transporting organic substance. As an example of the hole transport layer organic material,
【0018】[0018]
【化3】 Embedded image
【0019】[化3]に示すポリ(N−ビニルカルバゾ
ール)(以下PVKともいう。)、Poly (N-vinylcarbazole) (hereinafter also referred to as PVK) represented by Chemical Formula 3;
【0020】[0020]
【化4】 Embedded image
【0021】[化4]に示すポリ(パラ−フェニレンビ
ニレン)、A poly (para-phenylene vinylene) represented by the following formula:
【0022】[0022]
【化5】 Embedded image
【0023】(化学式[化5]中、RはC,H,O,Nで
構成する置換基である)[化5]を繰り返し単位として有
するポリカルバゾール化合物などの高分子からなること
が好ましい。あるいは、(In the chemical formula [Chemical Formula 5], R is a substituent composed of C, H, O, and N). Or,
【0024】[0024]
【化6】 Embedded image
【0025】[化6]に示すN,N’−ジフェニル−
N,N’−ビス(3−メチルフェニル)−1,1’−ビ
フェニル−4,4’−ジアミン(以下TPDともい
う。)、N, N'-diphenyl- represented by the formula
N, N′-bis (3-methylphenyl) -1,1′-biphenyl-4,4′-diamine (hereinafter also referred to as TPD),
【0026】[0026]
【化7】 Embedded image
【0027】[化7]に示すカルバゾールビフェニル
(以下、CBPとも言う。)、Carbazole biphenyl (hereinafter, also referred to as CBP) shown in [Formula 7],
【0028】[0028]
【化8】 Embedded image
【0029】[化8]に示すN,N’−ジフェニル−
N,N’−ビス(1−ナフチル)―1,1’−ビフェニ
ル−4,4’−ジアミン(以下、NPDとも言う。)N, N'-diphenyl-
N, N'-bis (1-naphthyl) -1,1'-biphenyl-4,4'-diamine (hereinafter also referred to as NPD)
【0030】[0030]
【化9】 Embedded image
【0031】[化9]に示す4,4’−ビス(10−フ
ェノチアジニル)ビフェニル、4,4'-bis (10-phenothiazinyl) biphenyl represented by the following formula:
【0032】[0032]
【化10】 Embedded image
【0033】[化10]に示すカッパーフタロシアニン
等が挙げられる。Copper phthalocyanine shown in Chemical Formula 10 is exemplified.
【0034】また、電子ブロック層30は、陰極層70
から発光層40へ注入された電子がそのまま陽極層10
へ通過してしまうことを防ぐため電子をブロックするた
めの層であり、電子ブロック性物質で構成される。電子
ブロック性物質としては、例えば、[化3]、[化4]、
[化6]乃至[化9]で示される化合物や、Further, the electron block layer 30 is formed of the cathode layer 70.
The electrons injected into the light emitting layer 40 from the anode layer 10
It is a layer for blocking electrons in order to prevent the electrons from passing through, and is made of an electron blocking substance. Examples of the electron blocking substance include [Chemical Formula 3], [Chemical Formula 4],
Compounds represented by the following formulas 6 to 9;
【0035】[0035]
【化11】 Embedded image
【0036】[化11]に示す2,4,6−トリフェニル
−1,3,5−トリアゾール、2,4,6-triphenyl-1,3,5-triazole represented by the following formula:
【0037】[0037]
【化12】 Embedded image
【0038】[化12]に示すフローレン、などを挙げる
ことができる。Fluorene shown in Chemical Formula 12 can be used.
【0039】また、発光層40はドープ剤41とホスト
剤42とを有し、これらドープ剤41とホスト剤42と
を均一に分散させるため、バインダ高分子を添加するこ
とも可能である。ホスト剤42は、陽極層10及び陰極
層70からそれぞれ注入された正孔と電子とが発光層4
0において再結合する際に賦活されて励起子として作用
する物質であり、The light emitting layer 40 has a dopant 41 and a host agent 42, and a binder polymer can be added to uniformly disperse the dopant 41 and the host agent 42. The host agent 42 is formed by the holes and electrons injected from the anode layer 10 and the cathode layer 70, respectively.
A substance that is activated when recombining at 0 and acts as an exciton,
【0040】[0040]
【化13】 Embedded image
【0041】[化13]に示す1,3,5−トリ(5−
(4−tert−ブチルフェニル)−1,3,4−オキ
サジアゾール))フェニル(以下OXD−1ともい
う。)The 1,3,5-tri (5-
(4-tert-butylphenyl) -1,3,4-oxadiazole)) phenyl (hereinafter also referred to as OXD-1)
【0042】[0042]
【化14】 Embedded image
【0043】(化学式[化14]中、RはC,H,O,N
で構成する置換基を示す。)[化14]を繰り返し単位と
して有するポリフルオレン化合物、などが挙げられる。(Wherein R is C, H, O, N
Represents a substituent composed of And polyfluorene compounds having [Formula 14] as a repeating unit.
【0044】一方、発光層40のドープ剤41は、励起
子たるホスト剤の励起エネルギーにより燐光を放射する
物質であり、On the other hand, the dopant 41 of the light emitting layer 40 is a substance which emits phosphorescence by the excitation energy of the host agent which is an exciton.
【0045】[0045]
【化15】 Embedded image
【0046】[化15]に示すトリ(2フェニルピリジ
ン)イリジウム錯体(以下Ir(ppy)3とも言
う。)、A tri (2phenylpyridine) iridium complex (hereinafter also referred to as Ir (ppy) 3 ) shown in [Formula 15],
【0047】[0047]
【化16】 Embedded image
【0048】[0048]
【化17】 Embedded image
【0049】[0049]
【化18】 Embedded image
【0050】[0050]
【化19】 Embedded image
【0051】[0051]
【化20】 Embedded image
【0052】[0052]
【化21】 Embedded image
【0053】(化学式[化21]中、acacは、(In the chemical formula [Chemical Formula 21], acac is
【0054】[0054]
【化22】 Embedded image
【0055】[化22]で示される官能基を示す。下記
[化23]乃至[化27]に示す化学式において同じ。)The functional group represented by the formula [22] is shown. following
The same applies to the chemical formulas shown in [Formula 23] to [Formula 27]. )
【0056】[0056]
【化23】 Embedded image
【0057】[0057]
【化24】 Embedded image
【0058】[0058]
【化25】 Embedded image
【0059】[0059]
【化26】 Embedded image
【0060】[0060]
【化27】 Embedded image
【0061】[化16]乃至[化21]、[化23]乃至[化
27]で示されるイリジウム錯体化合物、An iridium complex compound represented by any one of Chemical Formulas 16 to 21 and Chemical Formulas 23 to 27,
【0062】[0062]
【化28】 Embedded image
【0063】[化28]に示す2,3,7,8,12,
13,17,18−オクタエチル−21H,23H−白
金(II)ポルフィン(以下PtOEPとも言う。)など
を挙げることができる。2, 3, 7, 8, 12,
13, 17, 18-octaethyl-21H, 23H-platinum (II) porphine (hereinafter also referred to as PtOEP) and the like.
【0064】また、発光層40に添加可能なバインダ高
分子の例として、ポリスチレン、ポリビニルビフェニ
ル、ポリビニルフェナントレン、ポリビニルアントラセ
ン、ポリビニルペリレン、ポリ(エチレン−co−ビニ
ルアセテート)、ポリブタジエンのcisとtran
s、ポリ(2−ビニルナフタレン)、ポリビニルピロリ
ドン、ポリスチレン、ポリ(メチルメタクリレート)、
ポリ(ビニルアセテート)、ポリ(2−ビニルピリジン
−co−スチレン)、ポリアセナフチレン、ポリ(アク
リロニトリル−co−ブタジエン)、ポリ(ベンジルメ
タクリレート)、ポリ(ビニルトルエン)、ポリ(スチ
レン−co−アクリロニトリル)、ポリ(4−ビニルビ
フェニル)、ポリエチレングリコールなどが挙げられ
る。Examples of the binder polymer that can be added to the light emitting layer 40 include polystyrene, polyvinyl biphenyl, polyvinyl phenanthrene, polyvinyl anthracene, polyvinyl perylene, poly (ethylene-co-vinyl acetate), and cis and tran of polybutadiene.
s, poly (2-vinylnaphthalene), polyvinylpyrrolidone, polystyrene, poly (methyl methacrylate),
Poly (vinyl acetate), poly (2-vinylpyridine-co-styrene), polyacenaphthylene, poly (acrylonitrile-co-butadiene), poly (benzyl methacrylate), poly (vinyltoluene), poly (styrene-co-styrene) Acrylonitrile), poly (4-vinylbiphenyl), polyethylene glycol and the like.
【0065】また、正孔ブロック層50は、陽極層10
から発光層40へ注入された正孔がそのまま陰極層70
へ通過してしまうことを防ぐため正孔をブロックするた
めの層であり、正孔ブロック性物質で構成される。正孔
ブロック性物質としては、例えば、The hole blocking layer 50 is formed on the anode layer 10
The holes injected into the light emitting layer 40 from the cathode layer 70
This is a layer for blocking holes in order to prevent the holes from passing through, and is made of a hole-blocking substance. As the hole blocking substance, for example,
【0066】[0066]
【化29】 Embedded image
【0067】[化29] に示す2−(4−ビフェニリ
ル)−5−(4−tert−ブチルフェニル)−1,
3,4−オキサジアゾール、(以下PBDともい
う。)、2- (4-biphenylyl) -5- (4-tert-butylphenyl) -1,
3,4-oxadiazole, (hereinafter also referred to as PBD),
【0068】[0068]
【化30】 Embedded image
【0069】[化30]に示すバソキュプロイン(以下B
CPともいう。)、[化13]に示すOXD−1、[化2
9]に示すPBD、The bathocuproin (hereinafter referred to as B)
Also called CP. ), OXD-1 shown in [formula 13], [formula 2]
PBD shown in 9],
【0070】[0070]
【化31】 Embedded image
【0071】[化31]に示すトリス(8−ヒドロキシ
キノリナート)アルミニウム(以下Alq3ともい
う。)、Tris (8-hydroxyquinolinato) aluminum (hereinafter also referred to as Alq3) shown in [Chemical Formula 31],
【0072】[0072]
【化32】 Embedded image
【0073】[化32]に示す3−(4−ビフェニリ
ル)−5−(4−tert−ブチルフェニル)−4−フ
ェニル−1,2,4−トリアゾール(以下、TAZとも
いう。)、3- (4-biphenylyl) -5- (4-tert-butylphenyl) -4-phenyl-1,2,4-triazole (hereinafter also referred to as TAZ) shown in [Formula 32].
【0074】[0074]
【化33】 Embedded image
【0075】[化33]に示す4,4’−ビス(1,1
−ジフェニルエテニル)ビフェニル(以下にDPVBi
ともいう。)、The 4,4'-bis (1,1
-Diphenylethenyl) biphenyl (hereinafter referred to as DPVBi
Also called. ),
【0076】[0076]
【化34】 Embedded image
【0077】[化34]に示す2,5−ビス(1−ナフ
チル)−1.3.4−オキサジアゾール(以下にBND
ともいう。)The 2,5-bis (1-naphthyl) -1.3.4-oxadiazole represented by the following formula:
Also called. )
【0078】[0078]
【化35】 Embedded image
【0079】[化35]に示される4,4’−ビス
(1,1−ビス(4−メチルフェニル)エテニル)ビフ
ェニル(以下DTVBiとも言う。)、4,4′-bis (1,1-bis (4-methylphenyl) ethenyl) biphenyl (hereinafter also referred to as DTVBi) represented by the following formula:
【0080】[0080]
【化36】 Embedded image
【0081】[化36]に示される2,5−ビス(4−
ビフェニリル)−1,3,4−オキサジアゾール(以下
BBDともいう。)、The 2,5-bis (4-
Biphenylyl) -1,3,4-oxadiazole (hereinafter also referred to as BBD),
【0082】[0082]
【化37】 Embedded image
【0083】[0083]
【化38】 Embedded image
【0084】[化37]、[化38]に示すようなオキ
サジアゾール系高分子化合物、An oxadiazole polymer compound as shown in [Formula 37] or [Formula 38],
【0085】[0085]
【化39】 Embedded image
【0086】[0086]
【化40】 Embedded image
【0087】[化39]、[化40]で示すようなトリ
アゾール系高分子化合物、などを挙げることができる。Examples of the compound include triazole-based polymer compounds represented by Chemical Formula 39 and Chemical Formula 40.
【0088】また、電子輸送層60は、陰極層70から
注入される電子を輸送するための層であり、電子輸送剤
を含む。電子輸送剤は、電子輸送性高分子で構成され、
さらに電子輸送性低分子を含む構成が可能である。The electron transporting layer 60 is a layer for transporting electrons injected from the cathode layer 70 and contains an electron transporting agent. The electron transport agent is composed of an electron transport polymer,
Further, a configuration containing an electron transporting small molecule is possible.
【0089】ここで、電子輸送性低分子の例として、
[化29]に示すPBD、[化31]に示すAlq3、
[化32]に示すTAZ、[化33]に示すDPVB
i、[化34]に示すBND、[化35]に示すDTV
Bi、[化36]に示すBBDなどを挙げることができ
る。Here, as an example of the electron transporting small molecule,
PBD shown in [Chemical formula 29], Alq3 shown in [Chemical formula 31],
TAZ shown in [Formula 32], DPVB shown in [Formula 33]
i, BND shown in [Formula 34], DTV shown in [Formula 35]
Bi, BBD shown in [Formula 36], and the like.
【0090】また、電子輸送性高分子の例として、[化
37]、[化38]で示されるようなオキサジアゾール
系高分子化合物、[化39]、[化40]で示されるよ
うなトリアゾール系高分子化合物、Examples of the electron-transporting polymer include oxadiazole-based polymer compounds represented by [Formula 37] and [Formula 38], and those represented by [Formula 39] and [Formula 40]. Triazole polymer compound,
【0091】[0091]
【化41】 Embedded image
【0092】(化学式[化41]中、RはC,H,O,N
で構成する置換基を示す。)[化41]を繰り返し単位に
有するポリフルオレン化合物、などが挙げられる。(In the chemical formula [Formula 41], R is C, H, O, N
Represents a substituent composed of A) a polyfluorene compound having [Formula 41] as a repeating unit.
【0093】発光効率のさらなる向上や構造の簡素化の
ため、図1に示す有機エレクトロルミネッセンス素子の
基本構造に変更を加えたものとして、図2乃至図5に示
す素子構造が可能である。For further improving the luminous efficiency and simplifying the structure, the element structure shown in FIGS. 2 to 5 can be obtained by modifying the basic structure of the organic electroluminescence element shown in FIG.
【0094】図2で示される有機エレクトロルミネッセ
ンス素子の素子構造は、本発明の有機エレクトロルミネ
ッセンス素子の第1の実施形態を示す。図1の正孔輸送
層20と電子ブロック層30と電子輸送層60とが省略
されているが、図2において、発光層40に正孔輸送効
果と電子ブロック効果とを持たせ、正孔ブロック層50
に電子輸送効果を持たせて、発光効率を維持させること
ができる。The element structure of the organic electroluminescence element shown in FIG. 2 shows the first embodiment of the organic electroluminescence element of the present invention. Although the hole transport layer 20, the electron block layer 30, and the electron transport layer 60 of FIG. 1 are omitted, in FIG. 2, the light emitting layer 40 has a hole transport effect and an electron block effect, Layer 50
Has an electron transport effect to maintain luminous efficiency.
【0095】図3で示される有機エレクトロルミネッセ
ンス素子の素子構造は、図1で示す素子構造において、
電子ブロック層30と電子輸送層60とを省略したもの
である。The device structure of the organic electroluminescence device shown in FIG. 3 is different from the device structure shown in FIG.
The electron block layer 30 and the electron transport layer 60 are omitted.
【0096】図4で示される有機エレクトロルミネッセ
ンス素子の素子構造は、図1で示す素子構造から、電子
ブロック層30と正孔ブロック層50とを省略したもの
である。The element structure of the organic electroluminescence element shown in FIG. 4 is such that the electron block layer 30 and the hole block layer 50 are omitted from the element structure shown in FIG.
【0097】次に、図2を本発明の第1の実施形態とし
て、有機エレクトロルミネッセンス素子の製造方法を説
明する。Next, a method for manufacturing an organic electroluminescence device will be described with reference to FIG. 2 as a first embodiment of the present invention.
【0098】まず、図外の基板となる透明絶縁性支持
体、例えばガラス基板上に陽極層10を蒸着法またはス
パッタ法にて形成する。First, an anode layer 10 is formed on a transparent insulating support serving as a substrate (not shown), for example, a glass substrate by an evaporation method or a sputtering method.
【0099】次に、発光層40を構成するドープ剤41
とホスト剤42とを溶媒に溶解または分散した第1の溶
液を作成する。ここで、第1の溶液に、さらにバインダ
高分子を溶解または分散することも可能である。そし
て、その第1の溶液を用いた湿式法によって、上記陽極
層10上に発光層40を形成する。Next, the dopant 41 constituting the light emitting layer 40
And a host agent 42 dissolved or dispersed in a solvent to form a first solution. Here, the binder polymer can be further dissolved or dispersed in the first solution. Then, the light emitting layer 40 is formed on the anode layer 10 by a wet method using the first solution.
【0100】さらに、正孔ブロック性物質を溶媒に溶解
または分散した第2の溶液を作成する。ここで、第2の
溶液に、さらにバインダ高分子を溶解または分散するこ
とも可能である。その第2の溶液を用いた湿式法によっ
て、発光層40上に正孔ブロック層50を形成する。Further, a second solution is prepared by dissolving or dispersing the hole blocking substance in a solvent. Here, the binder polymer can be further dissolved or dispersed in the second solution. The hole blocking layer 50 is formed on the light emitting layer 40 by a wet method using the second solution.
【0101】また、第2の溶液に用いる溶媒の溶解度パ
ラメータは、正孔ブロック層50の成膜温度において、
発光層40に含まれる物質(ドープ剤41、ホスト剤4
2及びバインダ高分子など)に対して可溶範囲外を示す
値を有する。このような溶媒を用いた、湿式法による正
孔ブロック層50の形成において、下層の発光層40に
含まれる有機物を溶解することがない。The solubility parameter of the solvent used for the second solution is determined by the temperature at which the hole blocking layer 50 is formed.
The substances (doping agent 41, host agent 4
2 and a binder polymer). In the formation of the hole blocking layer 50 by a wet method using such a solvent, an organic substance contained in the lower light emitting layer 40 is not dissolved.
【0102】例えば、発光層40に含まれるドープ剤4
1が[化12]に示すOXD−1であり、ホスト剤42が
[化15]に示すIr(ppy)3であり、バインダ高分
子としてポリ(4-ビニルビフェニル)を用いる時、こ
れらの発光層を構成する有機物の可溶範囲を示す溶解度
パラメータは、室温において8.7(cal/cm3)
1/2以上11.1(cal/cm3)1/2以下である。し
たがって、第2の溶液に用いる溶媒として、この溶解度
パラメータの範囲外にある溶媒を用いると、発光層40
に含まれる有機物を溶解することなく正孔ブロック層5
0を形成する事が出来る。このような、溶媒の例として
n−ノナン(溶解度パラメータ7.64(cal/cm
3)1/2)、1-デセン(溶解度パラメータ7.85(ca
l/cm 3)1/2)、メチルシクロヘキサン(溶解度パラ
メータ8.13(cal/cm3)1/2)、シクロヘキサ
ン(溶解度パラメータ8.20(cal/c
m3)1/2)、1−クロロプロパン(溶解度パラメータ
8.30(cal/cm3)1/2)、アセトニトリル(溶
解度パラメータ11.8(cal/cm3)1/2)などが
挙げられる。For example, the dopant 4 contained in the light emitting layer 40
1 is OXD-1 shown in [Chemical Formula 12], and the host agent 42 is
Ir (ppy) shown in [Formula 15]ThreeAnd binder high
When using poly (4-vinylbiphenyl) as a
Solubility indicating the solubility range of the organic substances constituting these light-emitting layers
The parameters were 8.7 (cal / cm) at room temperature.Three)
1/2Above 11.1 (cal / cmThree)1/2It is as follows. I
Therefore, as a solvent used for the second solution, this solubility
If a solvent outside the parameter range is used, the light emitting layer 40
Blocking layer 5 without dissolving organic matter contained in
0 can be formed. Examples of such solvents
n-nonane (solubility parameter 7.64 (cal / cm
Three)1/2), 1-decene (solubility parameter 7.85 (ca)
l / cm Three)1/2), Methylcyclohexane (solubility para
Meter 8.13 (cal / cmThree)1/2), Cyclohexa
(Solubility parameter 8.20 (cal / c
mThree)1/2), 1-chloropropane (solubility parameter
8.30 (cal / cmThree)1/2), Acetonitrile (solvent
Resolution parameter 11.8 (cal / cmThree)1/2)etc
No.
【0103】この時、上記の第1及び第2の溶液に用い
る溶媒は自然乾燥によって蒸発することにより、発光層
40と正孔ブロック層50とが形成される。この場合、
加熱、紫外線の照射による重合、硬化等の処理を行う必
要がなく、従って、製造工程が簡単であり、生産効率を
向上させることができる。At this time, the solvent used for the first and second solutions is evaporated by natural drying, so that the light emitting layer 40 and the hole blocking layer 50 are formed. in this case,
There is no need to carry out treatments such as polymerization and curing by heating and irradiation of ultraviolet rays. Therefore, the production process is simple and the production efficiency can be improved.
【0104】本発明で使用される湿式法には、たとえば
キャスティング法、ブレードコート法、浸漬塗工法、ス
ピンコート法、スプレイコート法、ロール塗工法、イン
クジェット塗工法などの通常の塗工法が含まれる。The wet method used in the present invention includes ordinary coating methods such as a casting method, a blade coating method, a dip coating method, a spin coating method, a spray coating method, a roll coating method, and an ink jet coating method. .
【0105】最後に、正孔ブロック層50上に、蒸着法
などを用いて陰極層70を形成し、本発明の有機エレク
トロルミネッセンス素子が得られる。Finally, the cathode layer 70 is formed on the hole blocking layer 50 by using a vapor deposition method or the like, and the organic electroluminescent device of the present invention is obtained.
【0106】なお、溶解度パラメータSPは、モル蒸発
熱ΔH、モル体積Vの液体の絶対温度Tにおいて、 SP={(ΔH−RT)/V}1/2 で定義される。ただし、上記式中、SPは溶解度パラメ
ータ(単位:(cal/cm3)1/2)であり、ΔHはモ
ル蒸発熱(単位:cal/mol)であり、Rは気体定
数(単位:cal/(mol・K))であり、Tは絶対
温度(単位:K)であり、Vはモル体積(単位:cm3
/mol)である。The solubility parameter SP is defined as SP = {(ΔH−RT) / V} 1/2 at a molar evaporation heat ΔH and an absolute temperature T of a liquid having a molar volume V. Here, in the above formula, SP is a solubility parameter (unit: (cal / cm 3 ) 1/2 ), ΔH is molar heat of vaporization (unit: cal / mol), and R is a gas constant (unit: cal / mol / mol). (Mol · K)), T is the absolute temperature (unit: K), and V is the molar volume (unit: cm 3)
/ Mol).
【0107】また、図3は、本発明の有機エレクトロル
ミネッセンス素子の第2の実施形態であり、上記図2で
示される素子構造の製造工程中、発光層40を形成する
前に、陽極層10上にPVKなどの正孔輸送性物質を湿
式法により成膜して正孔輸送層20を形成した後、図2
と同様に発光層40と正孔ブロック層50と陰極層70
を順次形成する製造工程を経て得られる。FIG. 3 shows a second embodiment of the organic electroluminescence device of the present invention. In the manufacturing process of the device structure shown in FIG. 2, the anode layer 10 is formed before the light emitting layer 40 is formed. After a hole transporting substance such as PVK is formed thereon by a wet method to form a hole transporting layer 20, FIG.
Light emitting layer 40, hole blocking layer 50, and cathode layer 70
Are sequentially obtained.
【0108】また、図4は、本発明の有機エレクトロル
ミネッセンス素子の第3の実施形態であり、上記図2で
示される素子構造の製造工程中、発光層40を形成する
前に、陽極層10上にPVKなどの正孔輸送性物質を湿
式法により成膜して正孔輸送層20を形成した後、図2
と同様に発光層40を形成し、該発光層40上にポリフ
ルオレン化合物などの電子輸送性高分子または、ポリカ
ルバゾール化合物などの電子輸送性低分子を湿式法によ
り成膜して電子輸送層60を形成した後に、該電子輸送
層60上に、上記図2と同様に陰極層70を形成する製
造工程を経て得られる。FIG. 4 shows a third embodiment of the organic electroluminescence device of the present invention. In the manufacturing process of the device structure shown in FIG. 2, the anode layer 10 is formed before the light emitting layer 40 is formed. After a hole transporting substance such as PVK is formed thereon by a wet method to form a hole transporting layer 20, FIG.
A light emitting layer 40 is formed in the same manner as described above, and an electron transporting polymer such as a polyfluorene compound or an electron transporting low molecule such as a polycarbazole compound is formed on the light emitting layer 40 by a wet method. Is formed, a cathode layer 70 is formed on the electron transport layer 60 in the same manner as in FIG.
【0109】[0109]
【実施例】[実験1]所定の膜厚を有する薄膜を基板上に
積層したテストピースを作成し、所定の溶解度パラメー
タを有する溶媒に対する溶解範囲を測定した。EXAMPLE [Experiment 1] A test piece was prepared by laminating a thin film having a predetermined thickness on a substrate, and the dissolution range in a solvent having a predetermined solubility parameter was measured.
【0110】有機エレクトロルミネッセンス素子を構成
する、正孔輸送層、電子ブロック層、発光層、正孔ブロ
ック層、電子輸送層、電子注入層などの薄膜層の材料6
mgを、可溶な溶媒1mlに溶解して、溶液を作成す
る。この溶液を用いて、酸素プラズマ処理を施した市販
のITO基板(旭硝子社製:20Ω/□)上に、スピン
コート法により膜厚が50nmとなるように、回転数及
び時間を調整して、薄膜付の基板を作成し、テストピー
スとする。Materials 6 for the thin film layers such as the hole transport layer, the electron block layer, the light emitting layer, the hole block layer, the electron transport layer, and the electron injection layer which constitute the organic electroluminescence element.
mg is dissolved in 1 ml of a soluble solvent to make a solution. Using this solution, the number of revolutions and the time were adjusted on a commercially available ITO substrate (manufactured by Asahi Glass Co., Ltd .: 20Ω / □) subjected to oxygen plasma treatment so that the film thickness became 50 nm by spin coating. A substrate with a thin film is prepared and used as a test piece.
【0111】[0111]
【表1】 [Table 1]
【0112】[表1]に示す溶解度パラメータを有する溶
媒を、これら溶解度パラメータ値の昇順に用意し、図5
(a)及び図5(b)に示すように、それらの溶媒1で
満たされたビーカー2にテストピース3をそれぞれ10
秒間浸漬させ、その後、図5(c)に示すように、テス
トピース3を取り出して薄膜が溶解したか否かを目視で
確認する。Solvents having the solubility parameters shown in Table 1 were prepared in ascending order of these solubility parameter values.
As shown in FIG. 5A and FIG. 5B, test pieces 3 were placed in beakers 2 filled with the solvent 1 for 10 times, respectively.
Then, as shown in FIG. 5C, the test piece 3 is taken out, and it is visually confirmed whether or not the thin film is dissolved.
【0113】薄膜が溶解する溶媒の溶解度パラメータの
うち、最小値と最大値とをテストピースの溶解範囲と定
義する。[0113] Of the solubility parameters of the solvent in which the thin film dissolves, the minimum value and the maximum value are defined as the test piece dissolution range.
【0114】[実施例1]ゲルパーエイションクロマト
グラフィーにより測定したポリスチレン換算重量平均量
(以下分子量という。)が1,100,000のPVK
として6mgとIr(ppy)3として0.5mgとを
1mlの1,2ジクロロエタンで溶解して、溶液1を作
成した。Example 1 PVK having a polystyrene equivalent weight average molecular weight (hereinafter referred to as molecular weight) of 1,100,000 as measured by gel permeation chromatography.
And 0.5mg as 6mg and Ir (ppy) 3 was dissolved in 1,2 dichloroethane 1ml as to prepare a solution 1.
【0115】PBDとして2.5mgと[化21]で示す
イリジウム錯体化合物として0.17mgとバインダ高
分子としてポリスチレン(分子量10,000)2.5
mgとをシクロヘキサン(溶解度パラメータ8.2(c
al/cm3)1/2)1mlに溶解して、溶液2を作成し
た。2.5 mg of PBD, 0.17 mg of an iridium complex compound represented by the following formula, and 2.5 of polystyrene (molecular weight 10,000) as a binder polymer.
mg with cyclohexane (solubility parameter 8.2 (c
al / cm 3 ) 1/2 ) was dissolved in 1 ml to prepare solution 2.
【0116】酸素プラズマ処理を行なったITO基板上
(市販ITO、旭硝子社製:20Ω/□以下)に溶液1
を回転数1000rpm、1秒間スピンコートする事に
より50nmの発光層を形成した。この発光層の溶解範
囲は8.9〜10.0(cal/cm3)1/2であった。The solution 1 was placed on an oxygen-treated plasma ITO substrate (commercially available ITO, manufactured by Asahi Glass Co., Ltd .: 20Ω / □ or less).
Was spin-coated at 1000 rpm for 1 second to form a 50 nm light emitting layer. The dissolution range of this light emitting layer was 8.9 to 10.0 (cal / cm 3 ) 1/2 .
【0117】さらに、発光層上に溶液2を回転数100
0rpm、1秒間でスピンコートする事により50nm
の正孔ブロック層を得た。Further, the solution 2 was put on the light emitting layer at a rotation speed of 100.
50 nm by spin coating at 0 rpm for 1 second
Was obtained.
【0118】真空蒸着装置により真空度10-3Paでア
ルミニウムとリチウムを、リチウムが1%となるように
蒸着速度1nm/secの速度で共蒸着して陰極を形成
した。A cathode was formed by co-evaporating aluminum and lithium at a degree of vacuum of 10 −3 Pa at a deposition rate of 1 nm / sec so that the lithium content was 1%.
【0119】この時、9V、1mA/cm2で160c
d/m2の緑色の発光を得た。At this time, 160 c at 9 V and 1 mA / cm 2
A green light emission of d / m 2 was obtained.
【0120】[比較例1]分子量1,100,000の
PVK6mgとIr(ppy)3を0.5mgとを1m
lの1,2ジクロロエタンで溶解して、溶液1を作成し
た。[Comparative Example 1] 6 mg of PVK having a molecular weight of 1,100,000 and 0.5 mg of Ir (ppy) 3 were mixed for 1 m.
Solution 1 was prepared by dissolving with 1 of 1,2 dichloroethane.
【0121】酸素プラズマ処理を行なったITO基板上
(市販ITO、旭硝子社製:20Ω/□以下)に溶液1
を回転数1000rpm、1秒間スピンコートする事に
より50nmの発光層を形成した。The solution 1 was placed on the oxygen-treated ITO substrate (commercially available ITO, manufactured by Asahi Glass Co., Ltd .: 20Ω / □ or less).
Was spin-coated at 1000 rpm for 1 second to form a 50 nm light emitting layer.
【0122】さらに、真空蒸着装置により真空度10-3
PaでPBDを蒸着速度1nm/secの速度で50n
m蒸着し正孔ブロック層を形成し、最後にアルミニウム
とリチウムを、リチウムが1%となるように蒸着速度1
nm/secの速度で共蒸着して陰極を形成して図2に
示す素子構造を作成した。Further, the degree of vacuum was set to 10 −3 by a vacuum evaporation apparatus.
PBD 50n at a deposition rate of 1 nm / sec with Pa
m to form a hole blocking layer, and finally deposit aluminum and lithium at a deposition rate of 1% so that the lithium content is 1%.
A cathode was formed by co-evaporation at a speed of nm / sec to form an element structure shown in FIG.
【0123】この時、9V、1mA/cm2で170c
d/m2の緑色の発光を得た。At this time, 170 c at 9 V, 1 mA / cm 2
A green light emission of d / m 2 was obtained.
【0124】[実施例1]と[比較例1]とを比較すると正
孔ブロック層の形成を湿式のスピンコートで行っても、
蒸着で形成する時より、若干性能が下がるだけである事
が判る。A comparison between [Example 1] and [Comparative Example 1] shows that the formation of the hole blocking layer is performed by wet spin coating.
It can be seen that the performance is only slightly lower than when formed by vapor deposition.
【0125】[実施例2] [実施例1]の溶液2の溶媒を
下記に示す[表2]の溶媒にした以外は[実施例1]と同様
に図2に示す素子構造を作成したところ、[表2]のよう
な発光効率の発光が得られた。Example 2 An element structure shown in FIG. 2 was prepared in the same manner as in [Example 1] except that the solvent of the solution 2 of [Example 1] was changed to the solvent of [Table 2] shown below. And light emission with luminous efficiency as shown in [Table 2] was obtained.
【0126】[0126]
【表2】 [Table 2]
【0127】[実施例3] 分子量1,100,000の
PVKとして6mgを1mlの1,2ジクロロエタンで
溶解して、溶液1を作成した。Example 3 A solution 1 was prepared by dissolving 6 mg of PVK having a molecular weight of 1,100,000 with 1 ml of 1,2-dichloroethane.
【0128】OXD−1として2.5mgとIr(pp
y)3として0.17mgとバインダ高分子として分子
量100,000のポリビニルビフェニル2.5mgを
キシレン(溶解度パラメータ8.8(cal/cm3)
1/2)1mlに溶解して、溶液2を作成した。2.5 mg of OXD-1 and Ir (pp
y) 0.17 mg as 3 and 2.5 mg of polyvinyl biphenyl having a molecular weight of 100,000 as a binder polymer in xylene (solubility parameter 8.8 (cal / cm 3 ))
1/2 ) Dissolved in 1 ml to prepare solution 2.
【0129】PBDとして2.5mgと[化21]で示す
イリジウム錯体化合物として0.17mgとバインダ高
分子としてポリスチレン(分子量10,000)2.5
mgとをシクロヘキサン(溶解度パラメータ8.2(c
al/cm3)1/2)の溶媒1mlに溶解して、溶液3を
作成した。2.5 mg as PBD, 0.17 mg as an iridium complex compound represented by the following formula, and 2.5 as polystyrene (molecular weight 10,000) as a binder polymer.
mg with cyclohexane (solubility parameter 8.2 (c
Al / cm 3 ) 1/2 ) was dissolved in 1 ml of a solvent to prepare a solution 3.
【0130】酸素プラズマ処理を行なったITO基板上
(市販ITO、旭硝子社製:20Ω/□以下)に溶液1
を回転数1500rpm、1秒間スピンコートする事に
より50nmの正孔輸送層を形成した。この正孔輸送層
の溶解範囲は8.9〜10.0(cal/cm3)1/2で
あった。The solution 1 was placed on an oxygen-treated ITO substrate (commercially available ITO, manufactured by Asahi Glass Co., Ltd .: 20Ω / □ or less).
Was spin coated at 1500 rpm for 1 second to form a 50 nm hole transport layer. The dissolution range of this hole transport layer was 8.9 to 10.0 (cal / cm 3 ) 1/2 .
【0131】さらに、正孔輸送層上に溶液2を回転数1
000rpm、1秒間でスピンコートする事により20
nmの発光層を得た。この発光層の溶解範囲は8.7〜
11.1(cal/cm3)1/2であった。Further, the solution 2 was placed on the hole transport layer at a rotation speed of 1
2,000 rpm for 1 second by spin coating for 20
nm was obtained. The dissolution range of this light emitting layer is 8.7 to
11.1 (cal / cm 3 ) 1/2 .
【0132】さらに、発光層上に溶液3を回転数100
0rpm、1秒間でスピンコートする事により50nm
の正孔ブロック層を得た。Further, the solution 3 was put on the light emitting layer at a rotation speed of 100.
50 nm by spin coating at 0 rpm for 1 second
Was obtained.
【0133】真空蒸着装置により真空度10-3Paでア
ルミニウムとリチウムを、リチウムが1%となるように
蒸着速度1nm/secの速度で共蒸着して陰極を形成
して図3に示す素子構造を作成した。A cathode was formed by co-depositing aluminum and lithium at a degree of vacuum of 10 −3 Pa and a deposition rate of 1 nm / sec so that the lithium content was 1% using a vacuum deposition apparatus to form a cathode. It was created.
【0134】この時、9V、1mA/cm2で480c
d/m2の緑色の発光を得た。At this time, 480 c at 9 V and 1 mA / cm 2
A green light emission of d / m 2 was obtained.
【0135】[実施例4] [実施例3]の溶液3の溶媒を
下表の溶媒にした以外は[実施例3]と同様に図3に示す
素子構造を作成したところ下記[表3]に示す発光効率の
発光が得られた。Example 4 An element structure shown in FIG. 3 was prepared in the same manner as in [Example 3] except that the solvent of the solution 3 of [Example 3] was changed to the solvent shown in the following table. The luminescence with the luminous efficiency shown in (1) was obtained.
【0136】[0136]
【表3】 [Table 3]
【0137】[実施例5] [実施例3]で発光層ドープ剤
をIr(ppy)3に替え、下記[表4]のドープ剤を使
用した以外は[実施例3]と同様に図3に示す素子構造を
作成したところ下記[表4]に示す発光効率の発光が得ら
れた。[Example 5] In the same manner as in [Example 3] except that the dopant in the light emitting layer was changed to Ir (ppy) 3 in [Example 3] and the dopants shown in [Table 4] below were used. When the device structure shown in Table 4 was prepared, light emission having the luminous efficiency shown in Table 4 below was obtained.
【0138】[0138]
【表4】 [Table 4]
【0139】[実施例6] [実施例3]で正孔ブロック層
と陰極との間に電子注入層として、フッ化リチウムを真
空蒸着で真空度10-3Pa、速度0.1nm/secで
5nm成膜し、陰極をアルミニウムに替えた以外は[実
施例3]と同様に図3に示す素子構造を作成した。Example 6 In Example 3, lithium fluoride was vacuum-deposited at a degree of vacuum of 10 −3 Pa and a speed of 0.1 nm / sec as an electron injection layer between the hole blocking layer and the cathode. An element structure shown in FIG. 3 was formed in the same manner as in [Example 3] except that a film was formed to a thickness of 5 nm and the cathode was changed to aluminum.
【0140】この時、8.7V、1mA/cm2で52
0cd/m2の緑色の発光であった。At this time, 8.7 V, 1 mA / cm 2 and 52
It emitted green light of 0 cd / m 2 .
【0141】[実施例7] [実施例3]のITO陽極と正
孔輸送層との間に正孔注入層として、カッパーフタロシ
アニンを真空蒸着で、真空度10-3Pa、速度0.1n
m/secで5nm成膜した以外は[実施例3]と同様に
図3に示す素子構造を作成した。[Example 7] Copper phthalocyanine was vacuum-deposited as a hole injection layer between the ITO anode and the hole transport layer of [Example 3] at a degree of vacuum of 10 -3 Pa and a speed of 0.1 n.
An element structure shown in FIG. 3 was prepared in the same manner as in [Example 3] except that a film was formed to a thickness of 5 nm at m / sec.
【0142】この時、8.4V、1mA/cm2で52
0cd/m2の緑色の発光であった。At this time, 8.4 V, 1 mA / cm 2 and 52
It emitted green light of 0 cd / m 2 .
【0143】[実施例8] [化41]で示すポリフルオレ
ン化合物のRを直鎖のアルキル(−CnH2n+1)とし分
子量は1,000,000とした時の溶解度パラメータ
での溶解範囲を[実験1]にしたがい測定したときの溶解
範囲の測定結果を下記[表5]に示す。[0143] [Example 8] and molecular weight R alkyl straight polyfluorene compound represented by Formula 41] (-C n H 2n + 1) is dissolved in solubility parameter when 1,000,000 [Table 5] below shows the measurement results of the dissolution range when the range was measured according to [Experiment 1].
【0144】[0144]
【表5】 [Table 5]
【0145】Rに付くアルキル基の長さで溶解範囲が調
整できる事が判る。It can be seen that the range of dissolution can be adjusted by the length of the alkyl group attached to R.
【0146】この時、溶解範囲が8.4(cal/cm
3)1/2未満又は11.5(cal/cm3)1/2以上の範
囲にすれば、下層に位置する発光層の材料の選択範囲が
広くなる。At this time, the dissolution range was 8.4 (cal / cm).
3 ) When the ratio is less than 1/2 or 11.5 (cal / cm 3 ) 1/2 or more, the range of selection of the material of the light emitting layer located below is widened.
【0147】そこでPVK(分子量1,100,00
0)として6mgを1mlの1,2ジクロロエタンで溶
解して、溶液1を作成した。Then, PVK (molecular weight 1,100,00
6 mg was dissolved in 1 ml of 1,2 dichloroethane as 0) to prepare a solution 1.
【0148】OXD−1として2.5mgとIr(pp
y)3として0.17mgとバインダ高分子としてポリ
ビニルビフェニル(分子量115,000)2.5mg
をキシレン1mlに溶解して、溶液2を作成した。2.5 mg of OXD-1 and Ir (pp
y) 0.17 mg as 3 and 2.5 mg of polyvinyl biphenyl (molecular weight 115,000) as a binder polymer
Was dissolved in 1 ml of xylene to prepare a solution 2.
【0149】[化41]で示すポリフルオレン化合物のR
を直鎖のアルキル(−CnH2n+1)としたくり返し単位を
持つ分子量1,000,000の重合体5mgをシクロ
ヘキサン1mlに溶解して、溶液3を作成した。R of the polyfluorene compound represented by the formula
Was dissolved polymer 5mg of molecular weight 1,000,000 having repeating units and an alkyl straight chain (-C n H 2n + 1) in cyclohexane 1 ml, was prepared a solution 3.
【0150】酸素プラズマ処理を行なったITO基板上
(市販ITO、旭硝子社製:20Ω/□以下)に溶液1
を回転数1000rpm、1秒間でスピンコートする事
により50nmの正孔輸送層を得た。The solution 1 was placed on the oxygen-treated ITO substrate (commercially available ITO, manufactured by Asahi Glass Co., Ltd .: 20Ω / □ or less).
Was spin-coated at 1,000 rpm for 1 second to obtain a 50 nm hole transport layer.
【0151】正孔輸送層上に溶液2を回転数1000r
pm、1秒間でスピンコートする事により20nmの発
光層を得た。この、発光層の溶解範囲は8.6〜11.
1(cal/cm3)1/2であった。The solution 2 was put on the hole transport layer at a rotation speed of 1000 r.
A 20 nm light emitting layer was obtained by spin coating at pm for 1 second. The dissolution range of the light emitting layer is 8.6-11.
1 (cal / cm 3 ) 1/2 .
【0152】さらに、発光層上に溶液3を回転数100
0rpm、1秒間でスピンコートする事により50nm
の電子輸送層を得た。Further, the solution 3 was put on the light emitting layer at a rotation speed of 100.
50 nm by spin coating at 0 rpm for 1 second
Was obtained.
【0153】最後に、真空蒸着装置によりアルミニウム
とリチウムを真空度10-3Pa で、リチウムが1%と
なるように蒸着速度1nm/secの速度で共蒸着して
陰極を形成して図4に示す素子構造を作成したところ、
下記[表6]に示す発光効率の発光が得られた。[0153] Finally, aluminum and lithium in vacuum 10 -3 Pa by a vacuum deposition apparatus, lithium to form a cathode were co-deposited at a rate of deposition rate of 1 nm / sec to be 1 percent 4 After creating the element structure shown,
The luminescence with the luminous efficiency shown in the following [Table 6] was obtained.
【0154】[0154]
【表6】 [Table 6]
【0155】[実施例9][実施例8]の溶液2のバイン
ダ高分子をPVK(分子量50,000)に、溶媒をト
リクロロエチレンに替え、溶液3の溶媒をエチルベンゼ
ンに替えた以外は、[実施例8]と同様に図4に示す素子
構造を作成した。Example 9 The procedure of Example 8 was repeated except that the binder polymer of solution 2 was changed to PVK (molecular weight: 50,000), the solvent was changed to trichloroethylene, and the solvent of solution 3 was changed to ethylbenzene. An element structure shown in FIG. 4 was prepared in the same manner as in [Example 8].
【0156】この時、発光層の溶解範囲は、8.9〜1
0.6(cal/cm3)1/2であり、下記[表7]に示す
発光効率の発光が得られた。At this time, the dissolution range of the light emitting layer was 8.9 to 1
0.6 (cal / cm 3 ) 1/2 , and light emission having the luminous efficiency shown in the following [Table 7] was obtained.
【0157】[0157]
【表7】 [Table 7]
【0158】溶液3の溶媒をエチルベンゼンに替え、発
光層のバインダ高分子をエチルベンゼンに不溶なPVK
(分子量50,000)に替えた事により、1mA/c
m2での輝度が低下した。The solvent of solution 3 was changed to ethylbenzene, and the binder polymer of the light emitting layer was changed to PVK insoluble in ethylbenzene.
(Molecular weight: 50,000), resulting in 1 mA / c
The luminance at m 2 decreased.
【0159】[実施例10][化41]で示すポリフル
オレン化合物のRを直鎖の−C10H 21とした時の各分子
量で溶解度パラメータでの溶解範囲を[実験1]にした
がい測定したときの溶解範囲の測定結果を下記[表8]に
示す。Example 10 Polyfur represented by Chemical Formula 41
The R of the orene compound is represented by a linear -CTenH twenty oneEach molecule when
The solubility range in the solubility parameter was set to [Experiment 1].
Table 8 below shows the results of the measurement of the dissolution range when measuring the length.
Show.
【0160】[0160]
【表8】 [Table 8]
【0161】分子量で溶解範囲が調整できる事が判る。It can be seen that the dissolution range can be adjusted by the molecular weight.
【0162】これらの材料を使用して、[実施例8]と同
様に図4に示す素子構造を作成したところ、下記[表9]
に示す発光効率の発光が得られた。Using these materials, an element structure shown in FIG. 4 was prepared in the same manner as in [Example 8].
The luminescence of the luminous efficiency shown in the following was obtained.
【0163】[0163]
【表9】 [Table 9]
【0164】[実施例11][化41]で示すポリフル
オレン化合物のRを直鎖の−C10H 21(分子量10,0
00)として、溶媒による性能の差を調査した。素子作
成方法は、[実施例8]において電子輸送層に用いた重合
体と溶媒とを換えた以外は[実施例8]と同様に図4に示
す素子構造を作成したところ、下記[表10]に示す発光
効率の発光が得られた。[Example 11] Polyfur represented by the formula [41]
The R of the orene compound is represented by a linear -CTenH twenty one(Molecular weight 10,0
00), the difference in performance depending on the solvent was investigated. Element production
The formation method is the same as that of the polymerization used for the electron transport layer in [Example 8].
FIG. 4 shows the same procedure as in [Example 8] except that the body and solvent were changed.
When the device structure was fabricated, the light emission shown in [Table 10] below was obtained.
Efficient light emission was obtained.
【0165】[0165]
【表10】 [Table 10]
【0166】溶媒が変化しても、下層が不溶範囲の溶媒
を使用すれば、1mA/cm2での輝度ばらつきが10
%以内になる。Even if the solvent changes, if the solvent in the insoluble range of the lower layer is used, the luminance variation at 1 mA / cm 2 is 10
%.
【0167】[実施例12][化14]で示すポリフルオ
レン化合物のRを直鎖のアルキル(−CnH2n+1)とし
た分子量100,000の重合体の溶解範囲を[実験
1]にしたがい測定したところ、下記[表11]に示す測
定結果が得られた。Example 12 The solubility range of a polymer having a molecular weight of 100,000 in which R in the polyfluorene compound represented by Chemical Formula 14 is linear alkyl (—C n H 2n + 1 ) is shown in [Experiment 1]. As a result, the measurement results shown in the following [Table 11] were obtained.
【0168】[0168]
【表11】 [Table 11]
【0169】Rに付くアルキル基の長さで溶解範囲が調
整できる事が判る。この時、溶解範囲を8.9(cal
/cm3)1/2未満に調整すると、下層の正孔輸送層の材
料選択範囲が広がる。It can be seen that the dissolution range can be adjusted by the length of the alkyl group attached to R. At this time, the dissolution range was 8.9 (cal).
/ Cm 3 ) When adjusted to less than 1/2 , the material selection range of the lower hole transport layer is widened.
【0170】又、8.4(cal/cm3)1/2未満又は
10(cal/cm3)1/2より大きい溶媒に不溶である
ように調整すると上層成膜時の溶媒の選択範囲が広くな
る。Further, if the solvent is adjusted so as to be insoluble in a solvent of less than 8.4 (cal / cm 3 ) 1/2 or more than 10 (cal / cm 3 ) 1/2 , the selection range of the solvent in forming the upper layer is reduced. Become wider.
【0171】ここで、分子量1,100,000のPV
K6mgを1mlのジクロロエタンで溶解して、溶液1
を作成した。Here, PV having a molecular weight of 1,100,000
Dissolve 6 mg of K in 1 ml of dichloroethane to obtain solution 1.
It was created.
【0172】[化14]で示すポリフルオレン化合物の
Rを直鎖のアルキル(−CnH2n+1)とした分子量10
0,000の重合体として5mgとIr(ppy)3と
して0.17mgとをエチルベンゼン1mlに溶解し
て、溶液2を作成した。A compound having a molecular weight of 10 wherein R is a straight-chain alkyl (—C n H 2n + 1 ) of the polyfluorene compound represented by the following formula:
A solution 2 was prepared by dissolving 5 mg of a 0000 polymer and 0.17 mg of Ir (ppy) 3 in 1 ml of ethylbenzene.
【0173】PBD2.5mgとバインダ高分子として
分子量50,000のポリスチレン2.5mlとをシク
ロヘキサン1mlに溶解して、溶液3を作成した。A solution 3 was prepared by dissolving 2.5 mg of PBD and 2.5 ml of polystyrene having a molecular weight of 50,000 as a binder polymer in 1 ml of cyclohexane.
【0174】酸素プラズマ処理を行なったITO基板上
(市販ITO、旭硝子社製:20Ω/□以下)に溶液1
を回転数1500rpm、1秒間スピンコートする事に
より50nmの正孔輸送層を形成した。この、正孔輸送
層の溶解範囲は8.9〜10.0(cal/cm3)1/2
であった。The solution 1 was placed on an oxygen-treated ITO substrate (commercially available ITO, manufactured by Asahi Glass Co., Ltd .: 20Ω / □ or less).
Was spin coated at 1500 rpm for 1 second to form a 50 nm hole transport layer. The dissolution range of the hole transport layer is 8.9 to 10.0 (cal / cm 3 ) 1/2.
Met.
【0175】さらに、正孔輸送層上に溶液2を回転数1
000rpm、1秒間でスピンコートする事により20
nmの発光層を得た。Further, the solution 2 was placed on the hole transport layer at a rotation speed of 1
2,000 rpm for 1 second by spin coating for 20
nm was obtained.
【0176】さらに、発光層上に溶液3を回転数100
0rpm、1秒間でスピンコートする事により50nm
の電子輸送層を得た最後に、アルミニウムとリチウム
を、リチウムが1%となるように蒸着速度1nm/se
cの速度で共蒸着して陰極を形成した。この時、下記
[表12]に示す発光効率の発光が得られた。Further, the solution 3 was put on the light emitting layer at a rotation speed of 100.
50 nm by spin coating at 0 rpm for 1 second
Finally, aluminum and lithium were deposited at a deposition rate of 1 nm / sec so that the lithium content was 1%.
A cathode was formed by co-evaporation at a rate of c. At this time, luminescence with luminous efficiency shown in the following [Table 12] was obtained.
【0177】[0177]
【表12】 [Table 12]
【0178】N≦8では、電子輸送層成膜時に発光層が
溶解してしまう為、素子は作成できなかった。When N ≦ 8, the light emitting layer was dissolved during the formation of the electron transporting layer, so that no device could be prepared.
【0179】[実施例13] [実施例12]の溶液3の溶
媒をαブロモナフタリンに替えた以外は、[実施例12]
と同様に図4に示す素子構造を作成したところ、下記
[表13]に示す発光効率の発光が得られた。[Example 13] [Example 12] except that the solvent of the solution 3 of [Example 12] was changed to α-bromonaphthalene.
When the element structure shown in FIG.
Light emission having the luminous efficiency shown in Table 13 was obtained.
【0180】[0180]
【表13】 [Table 13]
【0181】Nが12〜15では、電子輸送層成膜時に
発光層が溶解してしまう為、素子は作成できなかった。When N was 12 to 15, the light emitting layer was dissolved during the formation of the electron transporting layer, so that no device could be prepared.
【0182】[実施例14][化14]で示すポリフル
オレン化合物のRを直鎖の−C8H1 7とした時の各分子
量で溶解度パラメータでの溶解範囲を[実験1]にした
がい測定したところ、下記[表4]に示す測定結果が得ら
れた。[0182] measure dissolution range in the solubility parameter in the molecular weight when the R of Example 14 polyfluorene compound represented by Chemical Formula 14] was -C 8 H 1 7 straight accordance Experiment 1 As a result, the measurement results shown in the following [Table 4] were obtained.
【0183】[0183]
【表14】 [Table 14]
【0184】分子量で溶解範囲が調整できる事が判る。It can be seen that the dissolution range can be adjusted by the molecular weight.
【0185】ここで、上記の分子量を調整した重合体を
使用して、[実施例12]と同様に図4に示す素子構造を
作成したところ、下記[表15]に示す発光効率の発光が
得られた。Here, an element structure shown in FIG. 4 was prepared in the same manner as in [Example 12] using the polymer having the adjusted molecular weight. Obtained.
【0186】[0186]
【表15】 [Table 15]
【0187】[実施例15][化14]で示すポリフルオ
レン化合物のRを直鎖の−C9H19とした分子量10
0,000の重合体5mgとIr(ppy)3として
0.17mgとを下記[表16]の溶媒各1mlに溶解し
て、[実施例12]の溶液2に替えた以外は[実施例1
2]と同様に図4に示す素子構造を作成したところ、下
記[表16]に示す発光効率の発光が得られた。[Example 15] The molecular weight of the polyfluorene compound represented by the formula [Chemical Formula 14], where R is a straight-chain -C 9 H 19 , is 10
[Example 1] Except that 5 mg of a 0000 polymer and 0.17 mg of Ir (ppy) 3 were dissolved in 1 ml of each of the solvents shown in [Table 16] below and the solution 2 of [Example 12] was used.
When the device structure shown in FIG. 4 was prepared in the same manner as in [2], light emission with luminous efficiency shown in [Table 16] below was obtained.
【0188】[0188]
【表16】 [Table 16]
【0189】溶媒が変化しても、1mA/cm2での輝
度のばらつきは10%以内である。Even if the solvent changes, the variation in luminance at 1 mA / cm 2 is within 10%.
【0190】[実施例16][化5]に示すポリカルバゾ
ール化合物のRを直鎖のアルキル(−CnH2n+1)とし
た時の溶解範囲を[実験1]にしたがい測定したとこ
ろ、下記[表17]に示す測定結果が得られた。Example 16 When the dissolution range of the polycarbazole compound shown in [Chemical Formula 5] in which R was a straight-chain alkyl (—C n H 2n + 1 ) was measured according to [Experiment 1], The measurement results shown in the following [Table 17] were obtained.
【0191】[0191]
【表17】 [Table 17]
【0192】Rに付くアルキル基の長さで溶解範囲が調
整できる事が判る。It can be seen that the range of dissolution can be adjusted by the length of the alkyl group attached to R.
【0193】この時、溶解範囲を8.9(cal/cm
3)1/2未満に調整すると、下層の正孔輸送層の材料選択
範囲が広がる。At this time, the dissolution range was 8.9 (cal / cm).
3 ) Adjusting to less than 1/2 widens the material selection range of the lower hole transport layer.
【0194】又、8.4(cal/cm3)1/2未満又は
10(cal/cm3)1/2より大きい溶媒に不溶である
ように調整すると上層成膜時の溶媒の選択範囲が広くな
る。If the solvent is adjusted so as to be insoluble in a solvent of less than 8.4 (cal / cm 3 ) 1/2 or more than 10 (cal / cm 3 ) 1/2 , the selection range of the solvent at the time of forming the upper layer is reduced. Become wider.
【0195】ここで、分子量1,100,000のPV
K6mgを1mlのジクロロエタンで溶解して、溶液1
を作成した。Here, PV having a molecular weight of 1,100,000
Dissolve 6 mg of K in 1 ml of dichloroethane to obtain solution 1.
It was created.
【0196】[化5]に示すポリカルバゾール化合物のR
を直鎖のアルキル(−CnH2n+1)とした分子量10,
000の重合体として5mgとIr(ppy)3として
0.17mgとをキシレン1mlに溶解して、溶液2を
作成した。R of the polycarbazole compound represented by the following formula
Alkyl straight (-C n H 2n + 1) and the molecular weight 10,
A solution 2 was prepared by dissolving 5 mg of 000 polymer and 0.17 mg of Ir (ppy) 3 in 1 ml of xylene.
【0197】PBDとして2.5mgとバインダ高分子
として分子量50,000のポリスチレン2.5mlと
をシクロヘキサン1mlに溶解して、溶液3を作成し
た。A solution 3 was prepared by dissolving 2.5 mg of PBD and 2.5 ml of polystyrene having a molecular weight of 50,000 as a binder polymer in 1 ml of cyclohexane.
【0198】酸素プラズマ処理を行なったITO基板上
(市販ITO、旭硝子社製:20Ω/□以下)に溶液1
を回転数1500rpm、1秒間スピンコートする事に
より50nmの正孔輸送層を形成した。この正孔輸送層
の溶解範囲は8.9〜10.0(cal/cm3)1/2で
あった。The solution 1 was placed on an oxygen-treated plasma ITO substrate (commercially available ITO, manufactured by Asahi Glass Co., Ltd .: 20Ω / □ or less).
Was spin coated at 1500 rpm for 1 second to form a 50 nm hole transport layer. The dissolution range of this hole transport layer was 8.9 to 10.0 (cal / cm 3 ) 1/2 .
【0199】さらに、正孔輸送層上に溶液2を回転数1
000rpm、1秒間でスピンコートする事により20
nmの発光層を得た。Further, the solution 2 was placed on the hole transport layer at a rotation speed of 1
2,000 rpm for 1 second by spin coating for 20
nm was obtained.
【0200】さらに、発光層上に溶液3を回転数100
0rpm、1秒間でスピンコートする事により50nm
の電子輸送層を得た最後に、アルミニウムとリチウム
を、リチウムが1%となるように蒸着速度1nm/se
cの速度で共蒸着して陰極を形成した。この時、下記
[表18]に示す発光効率の発光が得られた。Further, the solution 3 was put on the light emitting layer at a rotation speed of 100.
50 nm by spin coating at 0 rpm for 1 second
Finally, aluminum and lithium were deposited at a deposition rate of 1 nm / sec so that the lithium content was 1%.
A cathode was formed by co-evaporation at a rate of c. At this time,
Light emission with the luminous efficiency shown in [Table 18] was obtained.
【0201】[0201]
【表18】 [Table 18]
【0202】N=15では、電子輸送層成膜時に発光層
が溶解してしまう為、素子は作成できなかった。When N = 15, the light emitting layer was dissolved during the formation of the electron transporting layer, so that no device could be prepared.
【0203】[実施例17][実施例16]の溶液3の溶
媒をニトロエタンに替えた以外は、[実施例16]と同様
に図4に示す素子構造を作成したところ、下記[表19]
に示す発光効率の発光が得られた。Example 17 An element structure shown in FIG. 4 was prepared in the same manner as in [Example 16] except that the solvent of solution 3 in [Example 16] was changed to nitroethane.
The luminescence of the luminous efficiency shown in the following was obtained.
【0204】[0204]
【表19】 [Table 19]
【0205】N≧8では、電子輸送層成膜時に発光層が
溶解してしまう為、素子は作成できなかった。When N ≧ 8, the light emitting layer was dissolved during the formation of the electron transporting layer, so that no device could be prepared.
【0206】[実施例18] [化5]に示すポリカルバ
ゾール化合物のRを直鎖の−C8H17とした時の各分子
量での溶解範囲を[実験1]にしたがい測定したとこ
ろ、下記[表20]に示す測定結果が得られた。[Example 18] The dissolution range at each molecular weight when R of the polycarbazole compound shown in [Chemical Formula 5] is -C 8 H 17 was measured according to [Experiment 1]. The measurement results shown in [Table 20] were obtained.
【0207】[0207]
【表20】 [Table 20]
【0208】分子量で溶解範囲が調整できる事が判る。It can be seen that the dissolution range can be adjusted by the molecular weight.
【0209】ここで、上記の各分子量に調整した重合体
を使用して、[実施例16]と同様に図4に示す素子構造
を作成したところ、下記[表21]に示す発光効率の発光
が得られた。Here, an element structure shown in FIG. 4 was prepared in the same manner as in [Example 16] using the polymer adjusted to each of the above-mentioned molecular weights. was gotten.
【0210】[0210]
【表21】 [Table 21]
【0211】100,000〜1,000,000の分
子量では溶液2が作成できなかった。Solution 2 could not be prepared with a molecular weight of 100,000 to 1,000,000.
【0212】[実施例19][化5]に示すポリカルバ
ゾール化合物のRを直鎖の−C12H 25とした分子量1
0,000の重合体として5mgとIr(ppy)3と
して0.17mgとを下記[表22]に示す溶媒各1ml
に溶解したものを溶液2として用いた以外は[実施例1
6]と同様に図4に示す素子構造を作成したところ、[表
22]に示す発光効率の発光が得られた。Example 19 Polycarba represented by Chemical Formula 5
R of the sol compound is represented by a linear -C12H twenty fiveMolecular weight 1
5 mg as a 000 polymer and Ir (ppy)ThreeWhen
0.17 mg to 1 ml each of the solvents shown in the following [Table 22].
Example 1 except that the solution dissolved in
6], the device structure shown in FIG.
22].
【0213】[0213]
【表22】 [Table 22]
【0214】溶媒が変化しても、正孔輸送層の溶解範囲
外では、1mA/cm2での輝度のばらつきが10%以
内となる。Even if the solvent changes, the variation in luminance at 1 mA / cm 2 is within 10% outside the melting range of the hole transport layer.
【0215】[0215]
【発明の効果】以上の説明から明らかなように、本発明
により、有機エレクトロルミネッセンス素子を構成する
発光層と該発光層に積層する有機層とを溶液にした状
態、すなわち湿式法で、簡易に多層積層を形成し得る素
子構造を有する有機エレクトロルミネッセンス素子が得
られる。As is clear from the above description, according to the present invention, the light-emitting layer constituting the organic electroluminescence element and the organic layer laminated on the light-emitting layer are in a solution state, that is, simply by a wet method. An organic electroluminescence element having an element structure capable of forming a multilayer stack is obtained.
【図1】有機エレクトロルミネッセンス素子の素子構造FIG. 1 shows an element structure of an organic electroluminescence element.
【図2】本発明の素子構造の第1の実施形態FIG. 2 shows a first embodiment of an element structure of the present invention.
【図3】本発明の素子構造の第2の実施形態FIG. 3 shows a second embodiment of the device structure of the present invention.
【図4】本発明の素子構造の第3の実施形態FIG. 4 shows a third embodiment of the device structure of the present invention.
【図5】(a)〜(c)サンプルピースの溶解範囲の溶
解度パラメータの測定手順FIG. 5 (a) to (c) Procedures for measuring solubility parameters in the dissolution range of a sample piece
10 陽極層 40 発光層 41 ドープ剤 42 ホスト剤 50 正孔ブロック層(有機層) 70 陰極層 Reference Signs List 10 anode layer 40 light emitting layer 41 doping agent 42 host agent 50 hole blocking layer (organic layer) 70 cathode layer
Claims (7)
と燐光を放射するドープ剤とを有する発光層と、前記両
電極層の間で該発光層に積層する有機層とを具備し、前
記電極層の一方が基板上に形成される有機エレクトロル
ミネッセンス素子において、前記有機層を構成する有機
物が、該有機層の前記基板側に積層する前記発光層を構
成する有機物に対して溶解範囲外の溶解度パラメータを
有する溶媒に可溶であることを特徴とする有機エレクト
ロルミネッセンス素子。1. An electrode layer comprising both an anode layer and a cathode layer, a light emitting layer having a host agent and a dopant emitting phosphorescence, and an organic layer laminated between the two electrode layers on the light emitting layer. In an organic electroluminescence device in which one of the electrode layers is formed on a substrate, an organic substance constituting the organic layer dissolves in an organic substance constituting the light emitting layer laminated on the substrate side of the organic layer. An organic electroluminescent device characterized by being soluble in a solvent having a solubility parameter outside the range.
性物質、電子輸送性物質、正孔ブロック性物質のうち一
種類以上から成ることを特徴とする請求項1に記載の有
機エレクトロルミネッセンス素子。2. The organic electroluminescent device according to claim 1, wherein the organic material constituting the organic layer comprises at least one of an electron injecting substance, an electron transporting substance, and a hole blocking substance. element.
いて8.9(cal/cm3)1/2未満の溶解度パラメー
タを有する溶媒に不溶であり、前記有機層を構成する有
機物は、室温において7.0(cal/cm3)1/2以上
8.9(cal/cm3)1/2未満の溶解度パラメータを
有する溶媒に可溶であることを特徴とする請求項1また
は2に記載の有機エレクトロルミネッセンス素子。3. The organic substance forming the light emitting layer is insoluble in a solvent having a solubility parameter of less than 8.9 (cal / cm 3 ) 1/2 at room temperature, and the organic substance forming the organic layer is at room temperature. 3. It is soluble in a solvent having a solubility parameter of 7.0 (cal / cm 3 ) 1/2 or more and less than 8.9 (cal / cm 3 ) 1/2. Organic electroluminescence device.
いて8.3(cal/cm3)1/2以下の溶解度パラメー
タを有する溶媒に不溶であり、前記有機層を構成する有
機物は、室温において7.0(cal/cm3)1/2以上
8.3(cal/cm3)1/2以下の溶解度パラメータを
有する溶媒に可溶であることを特徴とする請求項1また
は2に記載の有機エレクトロルミネッセンス素子。4. The organic substance constituting the light emitting layer is insoluble in a solvent having a solubility parameter of 8.3 (cal / cm 3 ) 1/2 or less at room temperature, and the organic substance constituting the organic layer is at room temperature. 3. It is soluble in a solvent having a solubility parameter of 7.0 (cal / cm 3 ) 1/2 or more and 8.3 (cal / cm 3 ) 1/2 or less. Organic electroluminescence device.
いて11.5(cal/cm3)1/2以上13.0(ca
l/cm3)1/2以下の溶解度パラメータを有する溶媒に
不溶であり、前記有機層を構成する有機物は、室温にお
いて11.5(cal/cm3)1/2以上13.0(ca
l/cm3)1/2以下の溶解度パラメータを有する溶媒に
可溶であることを特徴とする請求項1または2に記載の
有機エレクトロルミネッセンス素子。5. The organic material constituting the light emitting layer is 11.5 (cal / cm 3 ) 1/2 or more and 13.0 (ca) at room temperature.
1 / cm 3 ) 1/2 , which is insoluble in a solvent having a solubility parameter of at most 11.5 (cal / cm 3 ) 1/2 at room temperature and 13.0 (ca) at room temperature.
The organic electroluminescent device according to claim 1, wherein the organic electroluminescent device is soluble in a solvent having a solubility parameter of 1 / cm 3 ) 1/2 or less.
はそれぞれ独立に任意の置換基を示し、ArとX12とに
おいて芳香環が縮合しても良く、nは1以上3以下の整
数である。)として示されることを特徴とする請求項1
乃至5のいずれか1項に記載の有機エレクトロルミネッ
センス素子。6. The molecular structure of the dopant is as follows: (In the chemical formula [Formula 1], Ar is an aryl group, X 12 and X 13
Each independently represents an arbitrary substituent, and an aromatic ring may be condensed between Ar and X 12, and n is an integer of 1 or more and 3 or less. ).
6. The organic electroluminescent device according to any one of items 1 to 5,
素または任意の置換基を示し、あるいは/および隣接す
るRn(nは1以上8以下のいずれかから成る整数)に
おいて芳香環が縮合しても良い。)として示されること
を特徴とする請求項1乃至5のいずれか1項に記載の有
機エレクトロルミネッセンス素子。7. The molecular structure of the dopant is as follows: (In the chemical formula [Chemical formula 2], R1 to R8 each independently represent hydrogen or an arbitrary substituent, and / or an aromatic ring is condensed in adjacent Rn (n is an integer of 1 or more and 8 or less) The organic electroluminescent device according to claim 1, wherein the organic electroluminescent device is represented by the following formula:
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