JP2009184987A - New pyrimidine-based or triazine-based derivative, electron transport material comprising the same and organic electroluminescent element including the same - Google Patents
New pyrimidine-based or triazine-based derivative, electron transport material comprising the same and organic electroluminescent element including the same Download PDFInfo
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- JP2009184987A JP2009184987A JP2008028099A JP2008028099A JP2009184987A JP 2009184987 A JP2009184987 A JP 2009184987A JP 2008028099 A JP2008028099 A JP 2008028099A JP 2008028099 A JP2008028099 A JP 2008028099A JP 2009184987 A JP2009184987 A JP 2009184987A
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- electron transport
- organic
- examples
- organic electroluminescent
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- 239000000463 material Substances 0.000 title claims abstract description 59
- CZPWVGJYEJSRLH-UHFFFAOYSA-N Pyrimidine Chemical compound C1=CN=CN=C1 CZPWVGJYEJSRLH-UHFFFAOYSA-N 0.000 title claims abstract description 20
- JYEUMXHLPRZUAT-UHFFFAOYSA-N 1,2,3-triazine Chemical compound C1=CN=NN=C1 JYEUMXHLPRZUAT-UHFFFAOYSA-N 0.000 title claims abstract description 19
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical group N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 30
- 238000005401 electroluminescence Methods 0.000 claims description 27
- 125000004432 carbon atom Chemical group C* 0.000 claims description 23
- 229910052757 nitrogen Chemical group 0.000 claims description 21
- 125000000217 alkyl group Chemical group 0.000 claims description 11
- 125000004435 hydrogen atom Chemical class [H]* 0.000 claims description 10
- 229910052739 hydrogen Inorganic materials 0.000 claims description 9
- 239000001257 hydrogen Substances 0.000 claims description 9
- 125000003545 alkoxy group Chemical group 0.000 claims description 7
- 125000003282 alkyl amino group Chemical group 0.000 claims description 7
- 125000004076 pyridyl group Chemical group 0.000 claims description 4
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 3
- 229910052799 carbon Inorganic materials 0.000 claims description 3
- 239000010410 layer Substances 0.000 description 133
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 50
- 230000005525 hole transport Effects 0.000 description 37
- 239000002904 solvent Substances 0.000 description 36
- PQXKHYXIUOZZFA-UHFFFAOYSA-M lithium fluoride Chemical compound [Li+].[F-] PQXKHYXIUOZZFA-UHFFFAOYSA-M 0.000 description 34
- 238000002347 injection Methods 0.000 description 30
- 239000007924 injection Substances 0.000 description 30
- 230000000052 comparative effect Effects 0.000 description 28
- 238000000034 method Methods 0.000 description 26
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 24
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 24
- 150000001875 compounds Chemical class 0.000 description 24
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 21
- 238000006243 chemical reaction Methods 0.000 description 19
- 239000010408 film Substances 0.000 description 19
- 230000015572 biosynthetic process Effects 0.000 description 18
- 238000000862 absorption spectrum Methods 0.000 description 17
- 239000000243 solution Substances 0.000 description 17
- 238000003786 synthesis reaction Methods 0.000 description 15
- 238000001194 electroluminescence spectrum Methods 0.000 description 14
- -1 4,6-difluorophenyl Chemical group 0.000 description 12
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 description 12
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 12
- 238000000746 purification Methods 0.000 description 12
- HPALAKNZSZLMCH-UHFFFAOYSA-M sodium;chloride;hydrate Chemical class O.[Na+].[Cl-] HPALAKNZSZLMCH-UHFFFAOYSA-M 0.000 description 12
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 12
- 238000004440 column chromatography Methods 0.000 description 11
- 238000002189 fluorescence spectrum Methods 0.000 description 11
- 238000007740 vapor deposition Methods 0.000 description 10
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 9
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 9
- NSABRUJKERBGOU-UHFFFAOYSA-N iridium(3+);2-phenylpyridine Chemical compound [Ir+3].[C-]1=CC=CC=C1C1=CC=CC=N1.[C-]1=CC=CC=C1C1=CC=CC=N1.[C-]1=CC=CC=C1C1=CC=CC=N1 NSABRUJKERBGOU-UHFFFAOYSA-N 0.000 description 9
- 239000000758 substrate Substances 0.000 description 9
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 8
- 230000009477 glass transition Effects 0.000 description 8
- 239000000843 powder Substances 0.000 description 8
- VFUDMQLBKNMONU-UHFFFAOYSA-N 9-[4-(4-carbazol-9-ylphenyl)phenyl]carbazole Chemical group C12=CC=CC=C2C2=CC=CC=C2N1C1=CC=C(C=2C=CC(=CC=2)N2C3=CC=CC=C3C3=CC=CC=C32)C=C1 VFUDMQLBKNMONU-UHFFFAOYSA-N 0.000 description 7
- 101150003085 Pdcl gene Proteins 0.000 description 7
- 230000000903 blocking effect Effects 0.000 description 7
- 238000000354 decomposition reaction Methods 0.000 description 7
- 230000005281 excited state Effects 0.000 description 7
- 230000008018 melting Effects 0.000 description 7
- 238000002844 melting Methods 0.000 description 7
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 description 6
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 6
- 239000007983 Tris buffer Substances 0.000 description 6
- JUJWROOIHBZHMG-UHFFFAOYSA-N c1ccncc1 Chemical compound c1ccncc1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 6
- 239000007772 electrode material Substances 0.000 description 6
- 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 6
- NFHFRUOZVGFOOS-UHFFFAOYSA-N palladium;triphenylphosphane Chemical compound [Pd].C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 NFHFRUOZVGFOOS-UHFFFAOYSA-N 0.000 description 6
- SCVFZCLFOSHCOH-UHFFFAOYSA-M potassium acetate Chemical compound [K+].CC([O-])=O SCVFZCLFOSHCOH-UHFFFAOYSA-M 0.000 description 6
- ZOKIJILZFXPFTO-UHFFFAOYSA-N 4-methyl-n-[4-[1-[4-(4-methyl-n-(4-methylphenyl)anilino)phenyl]cyclohexyl]phenyl]-n-(4-methylphenyl)aniline Chemical compound C1=CC(C)=CC=C1N(C=1C=CC(=CC=1)C1(CCCCC1)C=1C=CC(=CC=1)N(C=1C=CC(C)=CC=1)C=1C=CC(C)=CC=1)C1=CC=C(C)C=C1 ZOKIJILZFXPFTO-UHFFFAOYSA-N 0.000 description 5
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 5
- JUSDBSXSLHCSJX-DGROORMDSA-N C/C=C\C=C(/C=C)\c1cc(/C(/C=C\C=C)=C/C)nc(-c2cc(-c3nc(-c4ccccc4)cc(-c4ccccc4)n3)ccc2)n1 Chemical compound C/C=C\C=C(/C=C)\c1cc(/C(/C=C\C=C)=C/C)nc(-c2cc(-c3nc(-c4ccccc4)cc(-c4ccccc4)n3)ccc2)n1 JUSDBSXSLHCSJX-DGROORMDSA-N 0.000 description 5
- 229910052751 metal Inorganic materials 0.000 description 5
- 239000002184 metal Substances 0.000 description 5
- PIBWKRNGBLPSSY-UHFFFAOYSA-L palladium(II) chloride Chemical compound Cl[Pd]Cl PIBWKRNGBLPSSY-UHFFFAOYSA-L 0.000 description 5
- 239000000126 substance Substances 0.000 description 5
- WRAIDDFUXFHKBB-UHFFFAOYSA-N CC1=CC=C(C=C1)C2=CN(C(N=C2)C3=CC(=CC=C3)C4N=CC(=CN4C5=CC=C(C=C5)C)C6=CC=C(C=C6)C)C7=CC=C(C=C7)C Chemical compound CC1=CC=C(C=C1)C2=CN(C(N=C2)C3=CC(=CC=C3)C4N=CC(=CN4C5=CC=C(C=C5)C)C6=CC=C(C=C6)C)C7=CC=C(C=C7)C WRAIDDFUXFHKBB-UHFFFAOYSA-N 0.000 description 4
- XTHFKEDIFFGKHM-UHFFFAOYSA-N Dimethoxyethane Chemical compound COCCOC XTHFKEDIFFGKHM-UHFFFAOYSA-N 0.000 description 4
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 4
- 229910052782 aluminium Inorganic materials 0.000 description 4
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 4
- 238000000576 coating method Methods 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 4
- KDLHZDBZIXYQEI-UHFFFAOYSA-N palladium Substances [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 4
- 238000001953 recrystallisation Methods 0.000 description 4
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 4
- KZPYGQFFRCFCPP-UHFFFAOYSA-N 1,1'-bis(diphenylphosphino)ferrocene Chemical compound [Fe+2].C1=CC=C[C-]1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=C[C-]1P(C=1C=CC=CC=1)C1=CC=CC=C1 KZPYGQFFRCFCPP-UHFFFAOYSA-N 0.000 description 3
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 3
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 3
- ZZAWUFPWOMBKJM-UHFFFAOYSA-N C1C(=CN(NN1C2=CC=CC=C2)C3=CC(=CC(=C3)C4=CN=CC=C4)N5C=C(CN(N5)C6=CC=CC=C6)C7=CC=CC=C7)C8=CC=CC=C8 Chemical compound C1C(=CN(NN1C2=CC=CC=C2)C3=CC(=CC(=C3)C4=CN=CC=C4)N5C=C(CN(N5)C6=CC=CC=C6)C7=CC=CC=C7)C8=CC=CC=C8 ZZAWUFPWOMBKJM-UHFFFAOYSA-N 0.000 description 3
- PVVJGOKWJAOHSR-UHFFFAOYSA-N CC1=CC=C(C=C1)C2=CN(C(N=C2)C3=CC(=CC(=C3)C4=CN=CC=C4)C5N=CC(=CN5C6=CC=C(C=C6)C)C7=CC=C(C=C7)C)C8=CC=C(C=C8)C Chemical compound CC1=CC=C(C=C1)C2=CN(C(N=C2)C3=CC(=CC(=C3)C4=CN=CC=C4)C5N=CC(=CN5C6=CC=C(C=C6)C)C7=CC=C(C=C7)C)C8=CC=C(C=C8)C PVVJGOKWJAOHSR-UHFFFAOYSA-N 0.000 description 3
- XPRSBKDFPGVWNH-UHFFFAOYSA-N CC1=CC=C(C=C1)C2=CN(CN(C2)C3=CC=C(C=C3)C)C4=CC(=CN=C4)N5CN(CC(=C5)C6=CC=C(C=C6)C)C7=CC=C(C=C7)C Chemical compound CC1=CC=C(C=C1)C2=CN(CN(C2)C3=CC=C(C=C3)C)C4=CC(=CN=C4)N5CN(CC(=C5)C6=CC=C(C=C6)C)C7=CC=C(C=C7)C XPRSBKDFPGVWNH-UHFFFAOYSA-N 0.000 description 3
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 3
- 239000007864 aqueous solution Substances 0.000 description 3
- IPWKHHSGDUIRAH-UHFFFAOYSA-N bis(pinacolato)diboron Chemical compound O1C(C)(C)C(C)(C)OB1B1OC(C)(C)C(C)(C)O1 IPWKHHSGDUIRAH-UHFFFAOYSA-N 0.000 description 3
- 239000003795 chemical substances by application Substances 0.000 description 3
- 239000004210 ether based solvent Substances 0.000 description 3
- MILUBEOXRNEUHS-UHFFFAOYSA-N iridium(3+) Chemical compound [Ir+3] MILUBEOXRNEUHS-UHFFFAOYSA-N 0.000 description 3
- 150000002739 metals Chemical class 0.000 description 3
- 235000011056 potassium acetate Nutrition 0.000 description 3
- 238000005215 recombination Methods 0.000 description 3
- 230000006798 recombination Effects 0.000 description 3
- 239000011734 sodium Substances 0.000 description 3
- 239000007787 solid Substances 0.000 description 3
- 239000010409 thin film Substances 0.000 description 3
- 238000001771 vacuum deposition Methods 0.000 description 3
- BDOOZZQGKBKQCH-UHFFFAOYSA-N 3-(3,5-dibromophenyl)pyridine Chemical compound BrC1=CC(Br)=CC(C=2C=NC=CC=2)=C1 BDOOZZQGKBKQCH-UHFFFAOYSA-N 0.000 description 2
- 125000003349 3-pyridyl group Chemical group N1=C([H])C([*])=C([H])C([H])=C1[H] 0.000 description 2
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 2
- ZEKDMMSGYGBFQU-UHFFFAOYSA-N CC1=CC=C(C=C1)C2=CN(NN(C2)C3=CC=C(C=C3)C)C4=CC5=C(C=C4)C6=C(C5(C)C)C=C(C=C6)N7C=C(CN(N7)C8=CC=C(C=C8)C)C9=CC=C(C=C9)C Chemical compound CC1=CC=C(C=C1)C2=CN(NN(C2)C3=CC=C(C=C3)C)C4=CC5=C(C=C4)C6=C(C5(C)C)C=C(C=C6)N7C=C(CN(N7)C8=CC=C(C=C8)C)C9=CC=C(C=C9)C ZEKDMMSGYGBFQU-UHFFFAOYSA-N 0.000 description 2
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 2
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 2
- 229910000846 In alloy Inorganic materials 0.000 description 2
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 2
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 2
- ATHHXGZTWNVVOU-UHFFFAOYSA-N N-methylformamide Chemical compound CNC=O ATHHXGZTWNVVOU-UHFFFAOYSA-N 0.000 description 2
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 2
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 2
- 229910052783 alkali metal Inorganic materials 0.000 description 2
- 229910001508 alkali metal halide Inorganic materials 0.000 description 2
- 150000008045 alkali metal halides Chemical class 0.000 description 2
- 150000001340 alkali metals Chemical class 0.000 description 2
- 229910001615 alkaline earth metal halide Inorganic materials 0.000 description 2
- 229910045601 alloy Inorganic materials 0.000 description 2
- 239000000956 alloy Substances 0.000 description 2
- XJHCXCQVJFPJIK-UHFFFAOYSA-M caesium fluoride Chemical compound [F-].[Cs+] XJHCXCQVJFPJIK-UHFFFAOYSA-M 0.000 description 2
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 description 2
- 239000011248 coating agent Substances 0.000 description 2
- 239000004020 conductor Substances 0.000 description 2
- NXQGGXCHGDYOHB-UHFFFAOYSA-L cyclopenta-1,4-dien-1-yl(diphenyl)phosphane;dichloropalladium;iron(2+) Chemical compound [Fe+2].Cl[Pd]Cl.[CH-]1C=CC(P(C=2C=CC=CC=2)C=2C=CC=CC=2)=C1.[CH-]1C=CC(P(C=2C=CC=CC=2)C=2C=CC=CC=2)=C1 NXQGGXCHGDYOHB-UHFFFAOYSA-L 0.000 description 2
- 238000000151 deposition Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 229910052736 halogen Inorganic materials 0.000 description 2
- 150000002367 halogens Chemical group 0.000 description 2
- AOZVYCYMTUWJHJ-UHFFFAOYSA-K iridium(3+) pyridine-2-carboxylate Chemical compound [Ir+3].[O-]C(=O)C1=CC=CC=N1.[O-]C(=O)C1=CC=CC=N1.[O-]C(=O)C1=CC=CC=N1 AOZVYCYMTUWJHJ-UHFFFAOYSA-K 0.000 description 2
- KWGKDLIKAYFUFQ-UHFFFAOYSA-M lithium chloride Chemical compound [Li+].[Cl-] KWGKDLIKAYFUFQ-UHFFFAOYSA-M 0.000 description 2
- 150000002894 organic compounds Chemical class 0.000 description 2
- 125000001037 p-tolyl group Chemical group [H]C1=C([H])C(=C([H])C([H])=C1*)C([H])([H])[H] 0.000 description 2
- 238000001296 phosphorescence spectrum Methods 0.000 description 2
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 2
- 229920000123 polythiophene Polymers 0.000 description 2
- NROKBHXJSPEDAR-UHFFFAOYSA-M potassium fluoride Chemical compound [F-].[K+] NROKBHXJSPEDAR-UHFFFAOYSA-M 0.000 description 2
- 239000011241 protective layer Substances 0.000 description 2
- VLRICFVOGGIMKK-UHFFFAOYSA-N pyrazol-1-yloxyboronic acid Chemical compound OB(O)ON1C=CC=N1 VLRICFVOGGIMKK-UHFFFAOYSA-N 0.000 description 2
- 238000007789 sealing Methods 0.000 description 2
- 239000002356 single layer Substances 0.000 description 2
- 229910052708 sodium Inorganic materials 0.000 description 2
- PUZPDOWCWNUUKD-UHFFFAOYSA-M sodium fluoride Chemical compound [F-].[Na+] PUZPDOWCWNUUKD-UHFFFAOYSA-M 0.000 description 2
- 238000004544 sputter deposition Methods 0.000 description 2
- 239000008096 xylene Substances 0.000 description 2
- DQVXWCCLFKMJTQ-UHFFFAOYSA-N (4-methylphenoxy)boronic acid Chemical compound CC1=CC=C(OB(O)O)C=C1 DQVXWCCLFKMJTQ-UHFFFAOYSA-N 0.000 description 1
- NRHIIVAOUQAGJS-UHFFFAOYSA-M (4-phenylphenoxy)aluminum Chemical compound C1=CC(O[Al])=CC=C1C1=CC=CC=C1 NRHIIVAOUQAGJS-UHFFFAOYSA-M 0.000 description 1
- JIHQDMXYYFUGFV-UHFFFAOYSA-N 1,3,5-triazine Chemical compound C1=NC=NC=N1 JIHQDMXYYFUGFV-UHFFFAOYSA-N 0.000 description 1
- YWDUZLFWHVQCHY-UHFFFAOYSA-N 1,3,5-tribromobenzene Chemical compound BrC1=CC(Br)=CC(Br)=C1 YWDUZLFWHVQCHY-UHFFFAOYSA-N 0.000 description 1
- JSRLURSZEMLAFO-UHFFFAOYSA-N 1,3-dibromobenzene Chemical compound BrC1=CC=CC(Br)=C1 JSRLURSZEMLAFO-UHFFFAOYSA-N 0.000 description 1
- OCJBOOLMMGQPQU-UHFFFAOYSA-N 1,4-dichlorobenzene Chemical compound ClC1=CC=C(Cl)C=C1 OCJBOOLMMGQPQU-UHFFFAOYSA-N 0.000 description 1
- DURPTKYDGMDSBL-UHFFFAOYSA-N 1-butoxybutane Chemical compound CCCCOCCCC DURPTKYDGMDSBL-UHFFFAOYSA-N 0.000 description 1
- JPDUPGAVXNALOL-UHFFFAOYSA-N 1-n,1-n,4-n,4-n-tetraphenylbenzene-1,4-diamine Chemical compound C1=CC=CC=C1N(C=1C=CC(=CC=1)N(C=1C=CC=CC=1)C=1C=CC=CC=1)C1=CC=CC=C1 JPDUPGAVXNALOL-UHFFFAOYSA-N 0.000 description 1
- SPDPTFAJSFKAMT-UHFFFAOYSA-N 1-n-[4-[4-(n-[4-(3-methyl-n-(3-methylphenyl)anilino)phenyl]anilino)phenyl]phenyl]-4-n,4-n-bis(3-methylphenyl)-1-n-phenylbenzene-1,4-diamine Chemical compound CC1=CC=CC(N(C=2C=CC(=CC=2)N(C=2C=CC=CC=2)C=2C=CC(=CC=2)C=2C=CC(=CC=2)N(C=2C=CC=CC=2)C=2C=CC(=CC=2)N(C=2C=C(C)C=CC=2)C=2C=C(C)C=CC=2)C=2C=C(C)C=CC=2)=C1 SPDPTFAJSFKAMT-UHFFFAOYSA-N 0.000 description 1
- DPVIABCMTHHTGB-UHFFFAOYSA-N 2,4,6-trichloropyrimidine Chemical compound ClC1=CC(Cl)=NC(Cl)=N1 DPVIABCMTHHTGB-UHFFFAOYSA-N 0.000 description 1
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- 125000003229 2-methylhexyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 description 1
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- NBVXSUQYWXRMNV-UHFFFAOYSA-N fluoromethane Chemical compound FC NBVXSUQYWXRMNV-UHFFFAOYSA-N 0.000 description 1
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- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
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- 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 1
- 125000003187 heptyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
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- LHJOPRPDWDXEIY-UHFFFAOYSA-N indium lithium Chemical compound [Li].[In] LHJOPRPDWDXEIY-UHFFFAOYSA-N 0.000 description 1
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- GKOZUEZYRPOHIO-UHFFFAOYSA-N iridium atom Chemical compound [Ir] GKOZUEZYRPOHIO-UHFFFAOYSA-N 0.000 description 1
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 description 1
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- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
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- FQHFBFXXYOQXMN-UHFFFAOYSA-M lithium;quinolin-8-olate Chemical compound [Li+].C1=CN=C2C([O-])=CC=CC2=C1 FQHFBFXXYOQXMN-UHFFFAOYSA-M 0.000 description 1
- 125000000040 m-tolyl group Chemical group [H]C1=C([H])C(*)=C([H])C(=C1[H])C([H])([H])[H] 0.000 description 1
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- SJCKRGFTWFGHGZ-UHFFFAOYSA-N magnesium silver Chemical compound [Mg].[Ag] SJCKRGFTWFGHGZ-UHFFFAOYSA-N 0.000 description 1
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- 125000001298 n-hexoxy group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])O* 0.000 description 1
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Images
Abstract
Description
本発明は、新規なリン光材料、とくに青色リン光材料に適したワイドギャップな電子輸送層を形成するのに有用な新規なピリミジン系またはトリアジン系誘導体、それよりなる電子輸送材料およびそれを含む有機エレクトロルミネッセンス素子に関する。 The present invention relates to a novel phosphorescent material, particularly a novel pyrimidine-based or triazine-based derivative useful for forming a wide gap electron transport layer suitable for a blue phosphorescent material, an electron transport material comprising the same, and the like The present invention relates to an organic electroluminescence element.
有機エレクトロルミネッセンス素子は、電極から注入されたホールと電子の再結合によって生成した励起エネルギーが、発光過程を経て基底状態に緩和されることにより自発光する。しかしながら、ホールと電子の再結合によって生成する励起状態には、一重項励起状態と三重項励起状態の２種類がそれぞれ１対３の割合で存在する。これまでの多くは、一重項励起状態からの発光を利用した蛍光材料が発光材料に利用されていたため、内部量子効率が最大で２５％であり、この時の取り出し効率を２０％とすると、最大外部量子効率は５％が理論限界であった。 An organic electroluminescence element emits light by itself, when excitation energy generated by recombination of holes and electrons injected from an electrode is relaxed to a ground state through a light emission process. However, there are two types of excited states generated by recombination of holes and electrons, a singlet excited state and a triplet excited state in a ratio of 1: 3. In many cases, a fluorescent material that utilizes light emission from a singlet excited state has been used as a light emitting material. Therefore, the internal quantum efficiency is 25% at the maximum. If the extraction efficiency at this time is 20%, the maximum is The external quantum efficiency was 5%, which was the theoretical limit.
近年、イリジウムやプラチナなどの重原子効果を利用した錯体化合物を用い、三重項励起状態からの発光、例えばリン光発光を用いる事により発光効率の向上が報告されるようになった（例えば非特許文献１）。一重項励起状態に加え、三重項励起状態からの発光を利用する事で最大量子効率は理論上１００％に到達する事が可能で、リン光材料は発光材料として注目を浴びている（非特許文献３）。 In recent years, it has been reported that the emission efficiency is improved by using light emission from a triplet excited state, for example, phosphorescence emission, using a complex compound utilizing a heavy atom effect such as iridium or platinum (for example, non-patented). Reference 1). In addition to the singlet excited state, the maximum quantum efficiency can theoretically reach 100% by utilizing the light emission from the triplet excited state, and phosphorescent materials are attracting attention as light emitting materials (non-patented). Reference 3).
例えば緑色材料として、下記式
また安達らの発表にかかる非特許文献２などにより青色リン光材料である下記式
その結果、最近ではＳ．Ｒ．Ｆｏｒｒｅｓｔらによる非特許文献１では下記式
これら発光材料を効率よく発光させるには、ホールと電子の注入バランスを整えて、発光層の中で十分にキャリアーの結合が行えるように、ホール輸送剤や電子輸送剤などの選択を行わなければならない。
特に青色リン材料については、エネルギーギャップが大きいために、ワイドギャップ化されたホール輸送材料や電子輸送剤が必要になってくる。現在これらリン光材料としては、従来から電子輸送材料に使用されているＡｌｑ３［トリス（８−ヒドロキシキノリノラト）アルミニウム］やＢＡｌｑ２［ビス（２−メチル−８−ヒドロキシキノリノラト）（４−フェニルフェノキシ）アルミニウム］等が使用されているが、リン光材料に使用するには十分なエネルギーギャップを持ち合わせていないため新規なワイドギャップな電子輸送材料の開発が必要である。
In order for these luminescent materials to emit light efficiently, it is necessary to select a hole transport agent or an electron transport agent so that the injection balance of holes and electrons is adjusted and carriers can be sufficiently combined in the light emitting layer. Don't be.
In particular, for blue phosphorous materials, since the energy gap is large, hole transport materials and electron transport agents having a wide gap are required. Currently, these phosphorescent materials include Alq 3 [tris (8-hydroxyquinolinolato) aluminum] and BAlq 2 [bis (2-methyl-8-hydroxyquinolinolato) ( 4-phenylphenoxy) aluminum] and the like are used, but since it does not have a sufficient energy gap for use in phosphorescent materials, it is necessary to develop a new wide gap electron transport material.
本発明の目的は、新規なピリミジン系またはトリアジン系誘導体、それよりなる電子輸送材料およびそれを含む有機エレクトロルミネッセンス素子を提供する点にある。 An object of the present invention is to provide a novel pyrimidine-based or triazine-based derivative, an electron transport material comprising the same, and an organic electroluminescence device including the same.
本発明の第１は、下記一般式（１）
Ｒ１〜Ｒ５、Ｒ１０〜Ｒ２２は、水素、炭素数１〜６の直鎖または分枝のアルキル基、炭素数１〜６の直鎖または分枝のアルコキシ基、炭素数１〜６の直鎖または分枝のアルキルアミノ基よりなる群からそれぞれ独立して選ばれた基であり、
Ｒ６〜Ｒ９は、水素、炭素数１〜６の直鎖または分枝のアルキル基、炭素数１〜６の直鎖または分枝のアルコキシ基、炭素数１〜６の直鎖または分枝のアルキルアミノ基およびピリジル基よりなる群からそれぞれ独立して選ばれた基であり、
Ｒ２３、Ｒ２４は、水素、炭素数１〜６の直鎖又は分岐のアルキル基からなる群からそれぞれ独立して選ばれた基であり、
Ｘは炭素又は窒素である）
で示されるピリミジン系またはトリアジン系誘導体に関する。
本発明の第２は、請求項１のピリミジン系またはトリアジン系誘導体よりなる電子輸送材料に関する。
本発明の第３は、請求項１のピリミジン系またはトリアジン系誘導体を用いた有機エレクトロルミネッセンス素子に関する。
本発明の第４は、請求項１のピリミジン系またはトリアジン系誘導体を電子輸送層に用いた有機エレクトロルミネッセンス素子に関する。
The first of the present invention is the following general formula (1)
R 1 to R 5 and R 10 to R 22 are hydrogen, a linear or branched alkyl group having 1 to 6 carbon atoms, a linear or branched alkoxy group having 1 to 6 carbon atoms, or 1 to 6 carbon atoms. Each independently selected from the group consisting of linear or branched alkylamino groups,
R 6 to R 9 are hydrogen, a linear or branched alkyl group having 1 to 6 carbon atoms, a linear or branched alkoxy group having 1 to 6 carbon atoms, a linear or branched group having 1 to 6 carbon atoms. Each independently selected from the group consisting of an alkylamino group and a pyridyl group,
R 23 and R 24 are groups independently selected from the group consisting of hydrogen and a linear or branched alkyl group having 1 to 6 carbon atoms,
X is carbon or nitrogen)
The pyrimidine type or triazine type derivative represented by
The second aspect of the present invention relates to an electron transport material comprising the pyrimidine-based or triazine-based derivative of
A third aspect of the present invention relates to an organic electroluminescence device using the pyrimidine-based or triazine-based derivative of
A fourth aspect of the present invention relates to an organic electroluminescence device using the pyrimidine-based or triazine-based derivative of
本発明におけるＲ１〜Ｒ２２およびＲ２３、Ｒ２４における炭素数１〜６の直鎖あるいは分枝のアルキル基としては、メチル、エチル、プロピル、イソプロピル、ｎ−ブチル、イソブチル、ｔ−ブチル、ヘプチル、イソヘプチル、ｎ−ヘキシル等を挙げることができる。 Examples of the linear or branched alkyl group having 1 to 6 carbon atoms in R 1 to R 22 and R 23 and R 24 in the present invention include methyl, ethyl, propyl, isopropyl, n-butyl, isobutyl, t-butyl, Examples include heptyl, isoheptyl, n-hexyl and the like.
本発明におけるＲ１〜Ｒ２２における炭素数１〜６の直鎖あるいは分枝のアルコキシ基としては、メトキシ、エトキシ、プロポキシ、イソプロポキシ、ｎ−ブトキシ、ｔ−ブトキシ、ｎ−へプトキシ、イソへプトキシ、ｎ−ヘキシロキシ等を挙げることができる。 Examples of the linear or branched alkoxy group having 1 to 6 carbon atoms in R 1 to R 22 in the present invention include methoxy, ethoxy, propoxy, isopropoxy, n-butoxy, t-butoxy, n-heptoxy, isohetero Examples thereof include putoxy and n-hexyloxy.
本発明におけるＲ１〜Ｒ２２における炭素数１〜６の直鎖あるいは分枝のアルキルアミノ基としては、−ＮＨ２の水素の一個もしくは全部が前記アルキル基で置換されたタイプのものである。 The linear or branched alkylamino group having 1 to 6 carbon atoms in R 1 to R 22 in the present invention is a type in which one or all of —NH 2 hydrogens are substituted with the alkyl group.
本発明におけるＲ６〜Ｒ９におけるピリジル基としては、２−ピリジル基、３−ピリジル基および４−ピリジル基を挙げることができる。 Examples of the pyridyl group in R 6 to R 9 in the present invention include a 2-pyridyl group, a 3-pyridyl group and a 4-pyridyl group.
本発明の化合物は、下記の反応により製造することができる。
Ａ法で用いる溶媒としては、テトラヒドロフラン、ジエチルエーテル、１，４−ジオキサン、ジメトキシエタンのようなエーテル系の溶媒を単独もしくはこれらの混合した形で使用できる。またトルエン、キシレン、メシチレンのような芳香族炭化水素とメタノール、エタノール、イソプロパノール、ｎ−ブタノールなどのアルコール系溶媒との混合溶媒を用いる事もできる。 As the solvent used in Method A, ether solvents such as tetrahydrofuran, diethyl ether, 1,4-dioxane, and dimethoxyethane can be used alone or in the form of a mixture thereof. A mixed solvent of an aromatic hydrocarbon such as toluene, xylene, or mesitylene and an alcohol solvent such as methanol, ethanol, isopropanol, or n-butanol can also be used.
カップリングのところで用いられる溶媒に関してもＡ法で用いる溶媒に準ずる事ができる。 The solvent used in the coupling can be the same as the solvent used in Method A.
Ｂ法で用いる溶媒としては、ジエチルエーテル、テトラヒドロフラン、１，４−ジオキサン、ジメトキシエタンのようなエーテル系の溶媒を単独もしくはこれらの混合した形で使用できる。 As the solvent used in Method B, ether solvents such as diethyl ether, tetrahydrofuran, 1,4-dioxane and dimethoxyethane can be used singly or as a mixture thereof.
本発明化合物の具体例を以下に例示する。
Specific examples of the compound of the present invention are illustrated below.
本発明の新規なピリミジン系またはトリアジン系誘導体は高い電子輸送性能を有する。従って電子輸送材料として使用することができる。 The novel pyrimidine-based or triazine-based derivative of the present invention has high electron transport performance. Therefore, it can be used as an electron transport material.
本発明の新規なピリミジン系またはトリアジン系誘導体を電子輸送層に用いる場合、本発明の化合物は電子輸送材料として使用できる。また他の電子輸送材料と組み合わせて使用することもできる。 When the novel pyrimidine-based or triazine-based derivative of the present invention is used for an electron transport layer, the compound of the present invention can be used as an electron transport material. It can also be used in combination with other electron transport materials.
次に本発明の有機エレクトロルミネッセンス素子（有機ＥＬ素子）について説明する。本発明の有機ＥＬ素子は、陽極と陰極間にそれぞれの機能を有した多層の有機化合物を積層した素子であり、該有機化合物層の電子輸送層に本発明のピリミジン系またはトリアジン系誘導体を含有する。
多層型の有機ＥＬ素子の構成例としては、例えば陽極（例えばＩＴＯ）／ホール輸送層（正孔輸送層）／発光層／電子輸送層／陰極、陽極（例えばＩＴＯ）／ホール輸送層／発光層／電子輸送層／電子注入層／陰極、陽極（例えばＩＴＯ）／ホール輸送層／発光層／ホールブロック層（正孔ブロック層）／電子輸送層／陰極、陽極（例えばＩＴＯ）／ホール輸送層／発光層／ホールブロック層／電子輸送層／電子注入層／陰極、陽極（例えばＩＴＯ）／ホール注入層（正孔注入層）／ホール輸送層／発光層／ホールブロック層／電子輸送層／電子注入層／陰極等の多層構成で積層したものが挙げられる。また、必要に応じて陰極上に封止層を有していても良い。
Next, the organic electroluminescence element (organic EL element) of the present invention will be described. The organic EL device of the present invention is a device in which multiple organic compounds having respective functions are laminated between an anode and a cathode, and the electron transport layer of the organic compound layer contains the pyrimidine-based or triazine-based derivative of the present invention. To do.
Examples of the configuration of the multilayer organic EL element include, for example, an anode (for example, ITO) / a hole transport layer (a hole transport layer) / a light emitting layer / an electron transport layer / a cathode, an anode (for example, ITO) / a hole transport layer / a light emitting layer. / Electron transport layer / electron injection layer / cathode, anode (for example ITO) / hole transport layer / light emitting layer / hole block layer (hole block layer) / electron transport layer / cathode, anode (for example ITO) / hole transport layer / Light emitting layer / hole block layer / electron transport layer / electron injection layer / cathode, anode (for example, ITO) / hole injection layer (hole injection layer) / hole transport layer / light emitting layer / hole block layer / electron transport layer / electron injection A layered structure having a multilayer structure such as a layer / cathode may be used. Moreover, you may have a sealing layer on a cathode as needed.
正孔輸送層、電子輸送層、および発光層のそれぞれの層は一層構造であっても、多層構造であっても良い。また正孔輸送層、電子輸送層はそれぞれの層で注入機能を受け持つ層（正孔注入層および電子注入層）と輸送機能を受け持つ層（正孔輸送層および電子輸送層）を別々に設けることもできる。 Each of the hole transport layer, the electron transport layer, and the light emitting layer may have a single layer structure or a multilayer structure. In addition, the hole transport layer and the electron transport layer should be provided separately with a layer responsible for the injection function (hole injection layer and electron injection layer) and a layer responsible for the transport function (hole transport layer and electron transport layer). You can also.
本発明の有機エレクトロルミネッセンス素子は、上記構成例に限らず、種々の構成とすることができる。必要に応じて、正孔輸送成分と発光層成分、あるいは電子輸送層成分と発光層成分を混合した層を設けても良い。 The organic electroluminescence element of the present invention is not limited to the above configuration example, and can have various configurations. If necessary, a layer in which a hole transport component and a light emitting layer component or an electron transport layer component and a light emitting layer component are mixed may be provided.
以下本発明の有機エレクトロルミネッセンス素子の構成要素に関して、陽極／正孔輸送層／発光層／電子輸送層／陰極からなる素子構成を例として取り上げて説明する。本発明の有機エレクトロルミネッセンス素子は、基板に支持されていることが好ましい。 Hereinafter, the constituent elements of the organic electroluminescence element of the present invention will be described by taking, as an example, an element configuration comprising an anode / hole transport layer / light emitting layer / electron transport layer / cathode. The organic electroluminescence device of the present invention is preferably supported on a substrate.
基板の素材については特に制限はなく、従来の有機エレクトロルミネッセンス素子に慣用されているものであれば良く、例えば、ガラス、石英ガラス、透明プラスチックなどからなるものを用いることができる。 There is no restriction | limiting in particular about the raw material of a board | substrate, What is necessary is just used conventionally for the conventional organic electroluminescent element, For example, what consists of glass, quartz glass, a transparent plastic etc. can be used.
本発明の有機エレクトロルミネッセンス素子の陽極としては、仕事関数の大きな金属単体（４ｅＶ以上）、仕事関数の大きな金属同士の合金（４ｅＶ以上）または導電性物質およびこれらの混合物を電極材料とすることが好ましい。このような電極材料の具体例としては、金、銀、銅等の金属、ＩＴＯ（インジウム−スズオキサイド）、酸化スズ（ＳｎＯ２）、酸化亜鉛（ＺｎＯ）などの導電性透明材料、ポリピロール、ポリチオフェン等の導電性高分子材料が挙げられる。陽極はこれらの電極材料を、例えば蒸着、スパッタリング、塗布などの方法により形成することができる。陽極のシート電気抵抗は数百Ω／ｃｍ２以下が好ましい。陽極の膜厚は材料にもよるが、一般に５〜１，０００ｎｍ程度、好ましくは１０〜５００ｎｍである。 As an anode of the organic electroluminescence device of the present invention, an electrode material may be a single metal having a high work function (4 eV or more), an alloy of metals having a high work function (4 eV or more), a conductive substance, or a mixture thereof. preferable. Specific examples of such electrode materials include metals such as gold, silver, and copper, conductive transparent materials such as ITO (indium-tin oxide), tin oxide (SnO 2 ), and zinc oxide (ZnO), polypyrrole, and polythiophene. Examples thereof include conductive polymer materials such as For the anode, these electrode materials can be formed by a method such as vapor deposition, sputtering, or coating. The sheet electrical resistance of the anode is preferably several hundred Ω / cm 2 or less. The thickness of the anode depends on the material, but is generally about 5 to 1,000 nm, preferably 10 to 500 nm.
陰極としては、仕事関数の小さな金属単体（４ｅＶ以下）、仕事関数の小さな金属同士の合金（４ｅＶ以下）または導電性物質およびこれらの混合物を電極材料とすることが好ましい。このような電極材料の具体例としては、リチウム、リチウム−インジウム合金、ナトリウム、ナトリウム−カリウム合金、マグネシウム、マグネシウム−銀合金、マグネシウム−インジウム合金、アルミニウム、アルミニウム−リチウム合金、アルミニウム−マグネシウム合金などが挙げられる。陰極はこれらの電極材料を、例えば蒸着、スパッタリングなどの方法により、薄膜を形成させることにより作成することができる。陰極のシート電気抵抗は数百Ω／ｃｍ２以下が好ましい。陰極の膜厚は材料にもよるが、一般に５〜１，０００ｎｍ程度、好ましくは１０〜５００ｎｍである。本発明の有機ＥＬ素子の発光を効率よく取り出すために、陽極または陰極の少なくとも一方の電極は透明もしくは半透明であることが好ましい。 As the cathode, an electrode material is preferably a single metal having a small work function (4 eV or less), an alloy of metals having a small work function (4 eV or less), a conductive substance, or a mixture thereof. Specific examples of such electrode materials include lithium, lithium-indium alloy, sodium, sodium-potassium alloy, magnesium, magnesium-silver alloy, magnesium-indium alloy, aluminum, aluminum-lithium alloy, and aluminum-magnesium alloy. Can be mentioned. The cathode can be produced by forming a thin film of these electrode materials by a method such as vapor deposition or sputtering. The sheet electrical resistance of the cathode is preferably several hundred Ω / cm 2 or less. The thickness of the cathode depends on the material, but is generally about 5 to 1,000 nm, preferably 10 to 500 nm. In order to efficiently extract light emitted from the organic EL device of the present invention, at least one of the anode and the cathode is preferably transparent or translucent.
本発明の有機エレクトロルミネッセンス素子の正孔輸送層は、正孔伝達化合物からなるもので、陽極より注入された正孔を発光層に伝達する機能を有している。電界が与えた２つの電極の間に正孔伝達化合物が配置されて陽極から正孔が注入された場合、少なくとも１０−６ｃｍ２／Ｖ・秒以上の正孔移動度を有する正孔伝達物質が好ましい。本発明の有機エレクトロルミネッセンス素子の正孔輸送層に使用する正孔伝達物質は、前記の好ましい性能を有するものであれば特に制限はない。従来から光導電材料において正孔の電荷注入材料として慣用されているものや有機エレクトロルミネッセンス素子の正孔輸送層に使用されている公知の材料の中から任意のものを選択して用いることができる。 The hole transport layer of the organic electroluminescence device of the present invention is made of a hole transfer compound and has a function of transferring holes injected from the anode to the light emitting layer. A hole transport material having a hole mobility of at least 10 −6 cm 2 / V · sec when a hole transport compound is disposed between two electrodes to which an electric field is applied and holes are injected from an anode Is preferred. The hole transport material used for the hole transport layer of the organic electroluminescence device of the present invention is not particularly limited as long as it has the above-mentioned preferable performance. Any one of materials conventionally used as hole charge injection materials in photoconductive materials and known materials used in hole transport layers of organic electroluminescent elements can be selected and used. .
前記の正孔伝達物質としては、例えば銅フタロシアニンなどのフタロシアニン誘導体、Ｎ，Ｎ，Ｎ′，Ｎ′−テトラフェニル−１，４−フェニレンジアミン、Ｎ，Ｎ′−ジ（ｍ−トリル）−Ｎ，Ｎ′−ジフェニル−４，４−ジアミノフェニル（ＴＰＤ）、Ｎ，Ｎ′−
ジ（１−ナフチル）−Ｎ，Ｎ′−ジフェニル−４，４−ジアミノフェニル（α−ＮＰＤ）等のトリアリールアミン誘導体、ポリフェニレンジアミン誘導体、ポリチオフェン誘導体、および水溶性のＰＥＤＯＴ−ＰＳＳ（ポリエチレンジオキサチオフェン−ポリスチレンスルホン酸）などが挙げられる。正孔輸送層は、これらの他の正孔伝達化合物一種または二種以上からなる一層で構成されたものでよく、前記の正孔伝達物質とは別の化合物からなる正孔輸送層を積層したものでも良い。
正孔注入材料としては、下記化学式に示されるＰＥＤＯＴ−ＰＳＳ（ポリマー混合物）やＤＮＴＰＤを挙げることができる。
Triarylamine derivatives such as di (1-naphthyl) -N, N′-diphenyl-4,4-diaminophenyl (α-NPD), polyphenylenediamine derivatives, polythiophene derivatives, and water-soluble PEDOT-PSS (polyethylenedioxa Thiophene-polystyrene sulfonic acid). The hole transport layer may be composed of one or more of these other hole transport compounds, and a hole transport layer composed of a compound different from the hole transport material is laminated. Things can be used.
Examples of the hole injection material include PEDOT-PSS (polymer mixture) and DNTPD represented by the following chemical formula.
発光材料としては、ペリレン誘導体、ナフタセン誘導体、キナクリドン誘導体、クマリン誘導体（例えばクマリン１、クマリン５４０、クマリン５４５など）ピラン誘導体（例えばＤＣＭ−１、ＤＣＭ−２、ＤＣＪＴＢなど）、有機金属錯体、例えばトリス（８−ヒドロキシキノリノラト）アルミニウム錯体（Ａｌｑ３）、トリス（４−メチル−８−ヒドロキシキノリノラト）アルミニウム錯体（Ａｌｍｑ３）等の蛍光材料や［２−（４，６−ジフルオロフェニル）ピリジネート−Ｎ，Ｃ２′］イリジウム（III）ピコリネート（ＦＩｒｐｉｃ）、トリス｛１−［４−（トリフルオロメチル）フェニル］−１Ｈ−ピラゾラート−Ｎ，Ｃ２′｝イリジウム（III）（Ｉｒｔｆｍｐｐｚ３）、ビス［２−（４′，６′−ジフルオロフェニル）ピリジナト−Ｎ，Ｃ２′］イリジウム（III）テトラキス（１−ピラゾリル）ボレート（ＦＩｒ６）、トリス（２−フェニルピリジナト）イリジウム（III）〔Ｉｒ（ｐｐｙ）３〕などのリン光材料などを挙げることができる。
Examples of the light-emitting material include perylene derivatives, naphthacene derivatives, quinacridone derivatives, coumarin derivatives (eg,
発光層は、ホスト材料とゲスト材料（ドーパント）から形成することもできる［Ａｐｐｌ．Ｐｈｙｓ．Ｌｅｔｔ．，６５ ３６１０ （１９８９）］。特にリン光材料を発光層に使用する場合、ホスト材料の使用が必要であり、この時使用されるホスト材料としては４，４′−ジ（Ｎ−カルバゾリル）−１，１′−ビフェニル（ＣＢＰ）、１，４−ジ（Ｎ−カルバゾリル）ベンゼン−２，２′−ジ［４″−（Ｎ−カルバゾリル）フェニル］−１，１′−ビフェニル（４ＣｚＰＢＰ）等が挙げられる。 The light-emitting layer can also be formed of a host material and a guest material (dopant) [Appl. Phys. Lett. , 65 3610 (1989)]. In particular, when a phosphorescent material is used for the light emitting layer, it is necessary to use a host material. As the host material used at this time, 4,4′-di (N-carbazolyl) -1,1′-biphenyl (CBP) ), 1,4-di (N-carbazolyl) benzene-2,2′-di [4 ″-(N-carbazolyl) phenyl] -1,1′-biphenyl (4CzPBP) and the like.
ゲスト材料は、ホスト材料に対して好ましくは０．０１〜４０重量％であり、より好ましくは０．１〜２０重量％である。ゲスト材料としては、下記に示す従来公知のＦＩｒｐｉｃ、〔Ｉｒ（ｐｐｙ）３〕、ＦＩｒ６等を挙げることができる。
本発明の有機エレクトロルミネッセンス素子の電子輸送層の材料としては、本発明の新規なピリミジン系またはトリアジン系誘導体が好ましい。このものは単独で使用できるが他の電子輸送材料と併用しても構わない。 As the material for the electron transport layer of the organic electroluminescence device of the present invention, the novel pyrimidine-based or triazine-based derivative of the present invention is preferable. Although this thing can be used independently, you may use together with another electron transport material.
本発明の有機エレクトロルミネッセンス素子は、電子注入性をさらに向上させる目的で陰極と有機層（電子輸送層）の間に導電体から構成される電子注入層をさらに設けても良い。ここで使用される導電体としては、アルカリ金属ハロゲン化物、アルカリ土類金属ハロゲン化物、アルカリ金属有機錯体から選択される少なくとも一つの金属化合物を使用することが好ましい。アルカリ金属ハロゲン化物としては、フッ化リチウム、フッ化ナトリウム、フッ化カリウム、フッ化セシウム、塩化リチウムなどが挙げられる。アルカリ土類金属ハロゲン化物としては、フッ化マグネシウム、フッ化カルシウム、フッ化バリウム、フッ化ストロンチウムなどが挙げられる。アルカリ金属有機錯体としては、８−ヒドロキシキノリノラトリチウム、８−ヒドロキシキノリノラトセシウムなどが挙げられる。 In the organic electroluminescence device of the present invention, an electron injection layer composed of a conductor may be further provided between the cathode and the organic layer (electron transport layer) for the purpose of further improving the electron injection property. As the conductor used here, it is preferable to use at least one metal compound selected from alkali metal halides, alkaline earth metal halides, and alkali metal organic complexes. Examples of the alkali metal halide include lithium fluoride, sodium fluoride, potassium fluoride, cesium fluoride, and lithium chloride. Examples of the alkaline earth metal halide include magnesium fluoride, calcium fluoride, barium fluoride, and strontium fluoride. Examples of the alkali metal organic complex include 8-hydroxyquinolinolatolithium and 8-hydroxyquinolinolatocesium.
正孔輸送層、発光層の形成方法については特に限定されるものではない。例えば乾式製膜法（例えば真空蒸着法、イオン化蒸着法など）、湿式製膜法［溶媒塗布法（例えばスピンコート法、キャスト法、インクジェット法など）］を使用することができる。本発明の新規なピリミジン系またはトリアジン系誘導体は、乾式製膜法（例えば真空蒸着法、イオン化蒸着法など）が好ましい。電子輸送層の製膜については、湿式製膜法で行うと下層が溶出する恐れがあるため乾式製膜法（例えば真空蒸着法、イオン化蒸着法など）に限定される。素子の作成については上記の製膜法を併用しても構わない。 The method for forming the hole transport layer and the light emitting layer is not particularly limited. For example, a dry film forming method (for example, a vacuum vapor deposition method, an ionization vapor deposition method) or a wet film forming method [a solvent coating method (for example, a spin coating method, a casting method, an ink jet method, etc.)] can be used. The novel pyrimidine-based or triazine-based derivative of the present invention is preferably a dry film forming method (for example, a vacuum deposition method, an ionization deposition method, etc.). The film formation of the electron transport layer is limited to a dry film formation method (for example, a vacuum vapor deposition method, an ionization vapor deposition method, etc.) because the lower layer may be eluted when the wet film formation method is used. For the production of the element, the above film forming method may be used in combination.
真空蒸着法により正孔輸送層、発光層、電子輸送層などの各層を形成する場合、真空蒸着条件は特に限定されるものではない。通常１０−５Ｔｏｒｒ程度以下の真空下で５０〜５００℃程度のボート温度（蒸着原温度）、−５０〜３００℃程度の基板温度で、０．０１〜５０ｎｍ／ｓｅｃ．程度蒸着することが好ましい。正孔輸送層、発光層、電子輸送層の各層を複数の化合物を使用して形成する場合、化合物を入れたボートをそれぞれ温度制御しながら共蒸着することが好ましい。 When forming each layer such as a hole transport layer, a light emitting layer, and an electron transport layer by a vacuum deposition method, the vacuum deposition conditions are not particularly limited. Usually, under a vacuum of about 10 −5 Torr or less, a boat temperature (deposition source temperature) of about 50 to 500 ° C., a substrate temperature of about −50 to 300 ° C., and 0.01 to 50 nm / sec. Vapor deposition is preferred. When each of the hole transport layer, the light emitting layer, and the electron transport layer is formed using a plurality of compounds, it is preferable to co-evaporate the boats containing the compounds while controlling the temperatures of the boats.
正孔輸送層、発光層を溶媒塗布法で形成する場合、各層を構成する成分を溶媒に溶解または分散させて塗布液とする。溶媒としては、炭化水素系溶媒（例えばヘプタン、トルエン、キシレン、シクロヘキサン等）、ケトン系溶媒（例えばアセトン、メチルエチルケトン、メチルイソブチルケトン等）、ハロゲン系溶媒（例えばジクロロメタン、クロロホルム、クロロベンゼン、ジクロロベンゼン等）、エステル系溶媒（例えば酢酸エチル、酢酸ブチル等）、アルコール系溶媒（例えばメタノール、エタノール、ブタノール、メチルセロソルブ、エチルセロソルブ等）、エーテル系溶媒（例えばジブチルエーテル、テトラヒドロフラン、１，４−ジオキサン、１，２−ジメトキシエタン等）、非プロトン性溶媒（例えばＮ，Ｎ′−ジメチルアセトアミド、ジメチルスルホキシド等）、水等が挙げられる。溶媒は単独で使用しても良く、複数の溶媒を併用しても良い。 When forming the hole transport layer and the light emitting layer by a solvent coating method, the components constituting each layer are dissolved or dispersed in a solvent to obtain a coating solution. Solvents include hydrocarbon solvents (eg, heptane, toluene, xylene, cyclohexane, etc.), ketone solvents (eg, acetone, methyl ethyl ketone, methyl isobutyl ketone, etc.), halogen solvents (eg, dichloromethane, chloroform, chlorobenzene, dichlorobenzene, etc.) Ester solvents (eg, ethyl acetate, butyl acetate, etc.), alcohol solvents (eg, methanol, ethanol, butanol, methyl cellosolve, ethyl cellosolve, etc.), ether solvents (eg, dibutyl ether, tetrahydrofuran, 1,4-dioxane, 1 , 2-dimethoxyethane, etc.), aprotic solvents (eg, N, N′-dimethylacetamide, dimethyl sulfoxide, etc.), water and the like. The solvent may be used alone, or a plurality of solvents may be used in combination.
正孔輸送層、発光層、電子輸送層等の各層の膜厚は、特に限定されるものではないが、通常５〜５，０００ｎｍになるようにする。 The thickness of each layer such as the hole transport layer, the light emitting layer, and the electron transport layer is not particularly limited, but is usually 5 to 5,000 nm.
本発明の有機エレクトロルミネッセンス素子は、酸素や水分等の接触を遮断する目的で保護層（封止層）を設けたり、不活性物質中に素子を封入して保護することができる。不活性物質としては、パラフィン、シリコンオイル、フルオロカーボン等が挙げられる。保護層に使用する材料としては、フッ素樹脂、エポキシ樹脂、シリコーン樹脂、ポリエステル、ポリカーボネート、光硬化性樹脂等がある。 The organic electroluminescence device of the present invention can be protected by providing a protective layer (sealing layer) for the purpose of blocking contact with oxygen, moisture, etc., or by enclosing the device in an inert material. Examples of the inert substance include paraffin, silicon oil, and fluorocarbon. Examples of the material used for the protective layer include fluororesin, epoxy resin, silicone resin, polyester, polycarbonate, and photocurable resin.
本発明の有機エレクトロルミネッセンス素子は、通常直流駆動の素子として使用できる。直流電圧を印加する場合、陽極をプラス、陰極をマイナスの極性として通常１．５〜２０Ｖ程度印加すると発光が観察される。また本発明の有機エレクトロルミネッセンス素子は交流駆動の素子としても使用できる。交流電圧を印加する場合には、陽極がプラス、陰極がマイナスの状態になった時に発光する。本発明の有機エレクトロルミネッセンス素子は、例えば電子写真感光体、フラットパネルディスプレイなどの平面発光体、複写機、プリンター、液晶ディスプレイのバックライト、計器等の光源、各種発光素子、各種表示装置、各種標識、各種センサー、各種アクセサリーなどに使用することができる。 The organic electroluminescence device of the present invention can be used as a normal DC drive device. When a DC voltage is applied, light emission is usually observed when about 1.5 to 20 V is applied with the positive polarity of the anode and the negative polarity of the cathode. The organic electroluminescence device of the present invention can also be used as an AC drive device. When an AC voltage is applied, light is emitted when the anode is in a positive state and the cathode is in a negative state. The organic electroluminescence element of the present invention is, for example, a flat light emitter such as an electrophotographic photosensitive member or a flat panel display, a copying machine, a printer, a backlight of a liquid crystal display, a light source such as an instrument, various light emitting elements, various display devices, and various signs. It can be used for various sensors and various accessories.
図４１〜５０に、本発明の有機エレクトロルミネッセンス素子の好ましい例を示す。 The preferable example of the organic electroluminescent element of this invention is shown in FIGS.
図４１は、本発明の有機エレクトロルミネッセンス素子における他の例を示す断面図である。図４１は、基板１上に陽極２、発光層３、電子輸送層６および陰極４を順次設けた構成のものである。この場合、発光層は正孔輸送性の機能を有している場合に有用である。
FIG. 41 is a cross-sectional view showing another example of the organic electroluminescence element of the present invention. FIG. 41 shows a configuration in which an
図４２は、本発明の有機エレクトロルミネッセンス素子における他の例を示す断面図である。図４２は、基板１上に陽極２、正孔輸送層５、発光層３、電子輸送層６および陰極４を順次設けた構成のものである。これはキャリア輸送と発光の機能を分離したものであり、材料選択の自由度が増すために、発光の高効率化や発光色の自由度が増すことになる。
FIG. 42 is a cross-sectional view showing another example of the organic electroluminescence element of the present invention. FIG. 42 shows a structure in which an
図４３は、本発明の有機エレクトロルミネッセンス素子における他の例を示す断面図である。図４３は、基板１上に陽極２、正孔注入層７、正孔輸送層５、発光層３、電子輸送層６および陰極４を順次設けた構成のものである。この場合、正孔注入層７を設けることにより、陽極２と正孔輸送層５の密着性を高めたり、陽極からの正孔の注入を良くし、発光素子の低電圧化に効果がある。
FIG. 43 is a cross-sectional view showing another example of the organic electroluminescence element of the present invention. FIG. 43 shows a configuration in which an
図４４は、本発明の有機エレクトロルミネッセンス素子における他の例を示す断面図である。図４４は、基板１上に陽極２、正孔輸送層５、発光層３、電子輸送層６、電子注入層８および陰極４を順次設けた構成のものである。この場合、陰極４から電子の注入を良くし、発光素子の低電圧化に効果がある。
FIG. 44 is a cross-sectional view showing another example of the organic electroluminescence element of the present invention. FIG. 44 shows a configuration in which an
図４５は、本発明の有機エレクトロルミネッセンス素子における他の例を示す断面図である。図４５は、基板１上に陽極２、正孔注入層７、正孔輸送層５、発光層３、電子輸送層６、電子注入層８および陰極４を順次設けた構成のものである。この場合、陽極２から正孔の注入を良くし、陰極４から電子注入を良くし、最も低電圧駆動に効果がある構成である。
FIG. 45 is a cross-sectional view showing another example of the organic electroluminescence element of the present invention. FIG. 45 shows a configuration in which an
図４６〜５０は素子の中に正孔ブロック層を挿入したものの断面図である。正孔ブロック層は、陽極から注入された正孔、あるいは発光層３で再結合により生成した励起子が、陰極４に抜けることを防止する効果があり、有機エレクトロルミネッセンス素子の発光効率の向上に効果がある。正孔ブロック層９については、発光層３と陰極４の間もしくは発光層３と電子輸送層６の間あるいは発光層３と電子注入層８の間に挿入することができる。より好ましいものは発光層３と電子輸送層６の間である。
46 to 50 are sectional views of a device in which a hole blocking layer is inserted. The hole blocking layer has an effect of preventing holes injected from the anode or excitons generated by recombination in the
図４１〜５０で、正孔輸送層５、正孔注入層７、電子輸送層６、電子注入層８、発光層３、正孔ブロック層９のそれぞれの層は、一層構造であっても多層構造であっても良い。
41 to 50, each of the
図４１〜５０は、あくまでも基本的な素子構成であり、本発明の化合物を用いた有機エレクトロルミネッセンス素子の構成はこれに限定されるものではない。 41 to 50 are basic device configurations to the last, and the configuration of the organic electroluminescence device using the compound of the present invention is not limited to this.
前記電子注入層に用いる電子注入材料としては、本出願の特願２００６−２９２０３２号にかかる化合物、例えば下記化合物群を例示することができる。
本発明の新規なピリミジン系またはトリアジン系誘導体は、例えば実施例１４、１５と比較例３、４を対比すると明らかなように、Ａｌｑ３等の従来の電子輸送層に比べ電子輸送能が非常に大きい。また移動度も大きく素子中でのホールとのキャリアバランスにも優れている。また発光材料として使用した場合、青色から緑色にかけての発光を示し素子のフルカラー用あるいは白色用材料として適しているので、本発明の新規なピリミジン系またはトリアジン系誘導体は工業的に極めて重要なものである。 The novel pyrimidine-based or triazine-based derivative of the present invention has a very high electron transporting ability as compared with conventional electron transporting layers such as Alq 3 as is apparent from the comparison between Examples 14 and 15 and Comparative Examples 3 and 4, for example. large. Also, the mobility is high and the carrier balance with holes in the element is excellent. In addition, when used as a luminescent material, it emits light from blue to green and is suitable as a full-color or white material for the device. Therefore, the novel pyrimidine or triazine derivative of the present invention is extremely important industrially. is there.
以下に実施例を挙げて本発明を説明するが、本発明はこれにより何ら限定されるものではない。 Hereinafter, the present invention will be described with reference to examples, but the present invention is not limited thereto.
実施例１
１，３−ビス〔３，５−ジ（４−トリル）ピリミジル〕ベンゼン（略称ＢＤＴＰｍＢ）の合成
１）２−クロロ−４，６−（４−トリル）ピリミジンの（略称ＣＤＴＰｍ）合成
精製はカラムクロマトグラフィー法（展開溶媒：クロロホルム／ｎ−ヘキサン＝２／１）を行い、メタノールによる再結晶を行い白色の粉末を得た。収率：８０．２％
２）１，３−フェニレンジ（４，４，５，５−テトラメチル−１，３，２−ジオキサボロラン−２−イル）（略称ｍＢＤＯＢＢ）の合成
精製はカラムクロマトグラフィー法（展開溶媒：クロロホルム）を行い、薄い緑色の固体を得た。収率：５６．９％
精製はカラムクロマトグラフィー法（展開溶媒：クロロホルム／ｎ−ヘキサン＝２／１）を行い、アセトンによる再結晶を行い白色の粉末を得た。収率：３１．４％
図１にＢＤＴＰｍＢの蒸着膜の吸収スペクトルおよび図２に蛍光スペクトルを示す。また紫外−可視吸収スペクトルおよびイオン化ポテンシャル（例えば理研計器ＡＣ−３）を測定し電気化学特性を評価した。その結果を表１に示す。
Ｅｇ：エネルギーギャップ
Ｅａ：エネルギーアフィニティ（電子親和力）
エネルギーギャップ（Ｅｇ）については、蒸着機で作成した薄膜を紫外−可視吸光度計で薄膜の吸収曲線を測定する。その薄膜の短波長側の立ち上がりのところに接線を引き、求まった交点の波長Ｗ（ｎｍ）を次の式に代入し目的の値を求める。それによって得た値がＥｇになる。
Ｅｇ＝１２４０÷Ｗ
例えば接線を引いて求めた値Ｗ（ｎｍ）が４７０ｎｍだったとしたらこの時のＥｇの値は
Ｅｇ＝１２４０÷４７０＝２．６３（ｅＶ）
と言うことになる。
ＩＰ（イオン化ポテンシャル）はイオン化ポテンシャル測定装置（例えば理研計器ＡＣ−３）を使用して測定し、測定するサンプルがイオン化を開始したところの電圧（ｅＶ）の値を読む。
Ｅａ（電子親和力）は、ＩｐからＥｇを引いた値である。
実施例１の化合物の融点（Ｔｍ）、ガラス転移温度（Ｔｇ）および分解温度（Ｔｄ）を表２に示す。
Ｔｍ（融点）は、ＤＳＣ（Ｄｉｆｆｅｒｅｎｔｉａｌ Ｓｃａｎｎｉｎｇ Ｃａｌｏｒｉｍｅｔｅｒ 示差熱量計）にサンプルを加え、昇温してゆくと吸熱カーブが現れるので、その極大のところの温度を読んでその温度をＴｍとする。
Ｔｇ（ガラス転移温度）については、同じくＤＳＣの中にサンプルを加え、溶融させたものを急冷し、２〜３回繰り返すとガラス転移を表すカーブがチャート上に現れるので、そのカーブを接線で結び、その交点をＴｇとして採用する。
Ｔｄ（分解温度）はＤＴＡ（Ｄｉｆｆｅｒｅｎｔｉａｌ Ｔｈｅｒｍａｌ Ａｎａｌｙｚｅｒ 示差熱分析装置）にサンプルを加え加熱してゆくと、サンプルの熱によって分解し重量が減少しだす。その現象が開始しだしたところの温度を読んで、その温度をＴｄとする。
Example 1
Synthesis of 1,3-bis [3,5-di (4-tolyl) pyrimidyl] benzene (abbreviation BDTPmB) 1) Synthesis (abbreviation CDTPm) of 2-chloro-4,6- (4-tolyl) pyrimidine
Purification was performed by column chromatography (developing solvent: chloroform / n-hexane = 2/1), and recrystallization from methanol was performed to obtain a white powder. Yield: 80.2%
2) Synthesis of 1,3-phenylenedi (4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl) (abbreviation mBDOBB)
Purification was performed by column chromatography (developing solvent: chloroform) to obtain a pale green solid. Yield: 56.9%
Purification was performed by column chromatography (developing solvent: chloroform / n-hexane = 2/1) and recrystallized with acetone to obtain a white powder. Yield: 31.4%
FIG. 1 shows an absorption spectrum of a deposited film of BDTPmB, and FIG. 2 shows a fluorescence spectrum. In addition, an ultraviolet-visible absorption spectrum and an ionization potential (for example, Riken Keiki AC-3) were measured to evaluate electrochemical characteristics. The results are shown in Table 1.
Eg: Energy gap
Ea: Energy affinity (electron affinity)
Regarding the energy gap (Eg), an absorption curve of the thin film prepared with a vapor deposition machine is measured with an ultraviolet-visible absorptiometer. A tangent line is drawn at the short-wavelength rising edge of the thin film, and the target wavelength is obtained by substituting the obtained wavelength W (nm) of the intersection into the following equation. The value obtained thereby becomes Eg.
Eg = 1240 ÷ W
For example, if the value W (nm) obtained by drawing the tangent is 470 nm, the value of Eg at this time is
Eg = 1240 ÷ 470 = 2.63 (eV)
It will be said.
IP (ionization potential) is measured using an ionization potential measuring device (for example, Riken Keiki AC-3), and the value of the voltage (eV) at which the sample to be measured starts ionization is read.
Ea (electron affinity) is a value obtained by subtracting Eg from Ip.
Table 2 shows the melting point (Tm), glass transition temperature (Tg), and decomposition temperature (Td) of the compound of Example 1.
As Tm (melting point), an endothermic curve appears when a sample is added to DSC (Differential Scanning Calorimeter) and the temperature is raised, and the temperature at the maximum is read and Tm is taken as Tm.
As for Tg (glass transition temperature), a sample is added to DSC, the melted material is rapidly cooled, and if it is repeated 2 to 3 times, a curve representing the glass transition appears on the chart. The intersection is adopted as Tg.
When Td (decomposition temperature) is heated by adding a sample to DTA (Differential Thermal Analyzer differential thermal analyzer), it decomposes by the heat of the sample and begins to decrease in weight. Read the temperature at which the phenomenon started, and let that temperature be Td.
実施例２
５−（ピリジン−３−イル）−１，３−ビス〔３，５−ジ（４−トリル）ピリミジル〕ベンゼン（略称ＢＤＴＰｍＰｙＢ）の合成
１）３−（３，５−ジブロモフェニル）ピリジン（略称ＤＢｒＰｙＢ）の合成
精製はカラムクロマトグラフィー法〔展開溶媒：（１回目）クロロホルム／酢酸エチル＝１／２、（２回目）クロロホルム／酢酸エチル／メタノール＝１０／２０／１〕を行った。３−（３，５−ジブロモフェニル）ピリジン（ＤＢｒＰｙＢ）、収量：９．３３ｇ、収率：４９．７％
２）１−（ピリジン−３−イル）−３，５−ジ〔４，４，５，５−テトラメチル−（１，３，２）−ボロラン−２−イル〕ベンゼン（略称ＢＤＯＢＰｙＢ）の合成
精製はカラムクロマトグラフィー法（展開溶媒：クロロホルム／酢酸エチル＝４／１）で行い、白色の粉末を得た。収率：５２．５％
３）５−（ピリジン−３−イル）−１，３−ビス〔３，５−ジ（４−トリル）ピリミジル〕ベンゼン（略称ＢＤＴＰｍＰｙＢ）の合成
精製はカラムクロマトグラフィー法〔展開溶媒：（１回目）クロロホルム／酢酸エチル／メタノール＝２０／１０／１、（２回目）クロロホルム／メタノール＝１００／３〕を行い、白色の粉末を得た。収率：８３．９％
図３にＢＤＴＰｍＰｙＢの蒸着膜の吸収スペクトル（Ａｂｓ）と蛍光スペクトル（ＰＬ）を示す。また紫外−可視吸収スペクトルおよびイオン化ポテンシャル（例えば理研計器ＡＣ−３）を測定し、電気化学特性を評価した。その結果を表３に示す。
Synthesis of 5- (pyridin-3-yl) -1,3-bis [3,5-di (4-tolyl) pyrimidyl] benzene (abbreviation BDTPmPyB) 1) 3- (3,5-dibromophenyl) pyridine (abbreviation) Synthesis of DBrPyB)
Purification was performed by column chromatography [developing solvent: (first time) chloroform / ethyl acetate = 1/2, (second time) chloroform / ethyl acetate / methanol = 10/20/1]. 3- (3,5-dibromophenyl) pyridine (DBrPyB), yield: 9.33 g, yield: 49.7%
2) Synthesis of 1- (pyridin-3-yl) -3,5-di [4,4,5,5-tetramethyl- (1,3,2) -borolan-2-yl] benzene (abbreviation BDOBPyB)
Purification was performed by a column chromatography method (developing solvent: chloroform / ethyl acetate = 4/1) to obtain a white powder. Yield: 52.5%
3) Synthesis of 5- (pyridin-3-yl) -1,3-bis [3,5-di (4-tolyl) pyrimidyl] benzene (abbreviation BDTPmPyB)
Purification was performed by column chromatography [developing solvent: (first time) chloroform / ethyl acetate / methanol = 20/10/1, (second time) chloroform / methanol = 100/3] to obtain a white powder. Yield: 83.9%
FIG. 3 shows an absorption spectrum (Abs) and a fluorescence spectrum (PL) of the deposited film of BDTPmPyB. In addition, an ultraviolet-visible absorption spectrum and an ionization potential (for example, Riken Keiki AC-3) were measured to evaluate electrochemical characteristics. The results are shown in Table 3.
実施例３
３，５−ビス〔３，５−ビス（ｐ−トリル）ピリミジン−１−イル〕ピリジン（略称ＢＤＴＰｍＰｙ）の合成
１）３，５−ビス〔４，４，５，５−テトラメチル−（１，３，２）−ジオキサボロラン−２−イル〕ピリジン（略称ＢＤＯＢＰｙ）の合成
精製はカラムクロマトグラフィー法（展開溶媒：クロロホルム）を行い、白色の粉末を得た。収率：２７．８％
２）３，５−ビス〔３，５−ビス（ｐ−トリル）ピリミジン−１−イル〕ピリジン（略称ＢＤＴＰｍＰｙ）の合成
精製はカラムクロマトグラフィー法（展開溶媒：クロロホルム）を行い、白色の粉末を得た。収率：２０．５％
図４にＢＤＴＰｍＰｙ蒸着膜の吸収スペクトル（Ａｂｓ）と蛍光スペクトル（ＰＬ）を示す。また紫外−可視吸収スペクトルおよびイオン化ポテンシャル（例えば理研計器ＡＣ−３）を測定し、電気化学特性を評価した。その結果を表５に示す。
Synthesis of 3,5-bis [3,5-bis (p-tolyl) pyrimidin-1-yl] pyridine (abbreviation BDTPmPy) 1) 3,5-bis [4,4,5,5-tetramethyl- (1 , 3,2) -Dioxaborolan-2-yl] pyridine (abbreviation BDOBPy)
Purification was performed by column chromatography (developing solvent: chloroform) to obtain a white powder. Yield: 27.8%
2) Synthesis of 3,5-bis [3,5-bis (p-tolyl) pyrimidin-1-yl] pyridine (abbreviation BDTPmPy)
Purification was performed by column chromatography (developing solvent: chloroform) to obtain a white powder. Yield: 20.5%
FIG. 4 shows an absorption spectrum (Abs) and a fluorescence spectrum (PL) of the BDTPmPy deposited film. In addition, an ultraviolet-visible absorption spectrum and an ionization potential (for example, Riken Keiki AC-3) were measured to evaluate electrochemical characteristics. The results are shown in Table 5.
実施例４
１，３−ビス〔３，５−ビス（ｐ−トリル）トリアジン−１−イル〕ベンゼン（略称ＢＤＴＴｚＢ）の合成
１）１−クロロ−３，５−ジ（ｐ−トリル）トリアジン（略称ＣＤＴＴｚ）の合成
クロロホルム／メタノール＝５／１による再結晶を行い、薄い黄色固体を得た。収率：６６．４％
２）１，３−ビス〔３，５−ビス（ｐ−トリル）トリアジン−１−イル〕ベンゼン（略称ＢＤＴＴｚＢ）の合成
精製はカラムクロマトグラフィー法（展開溶媒：クロロホルム）で行い、クロロホルムによる再結晶を行い白色の粉末を得た。収率：８５．９％
図１にＢＤＴＴｚＢの蒸着膜の吸収スペクトルおよび図２に蛍光スペクトルを示す。また紫外−可視吸収スペクトルおよびイオン化ポテンシャル（例えば理研計器ＡＣ−３）を測定し、電気化学特性を評価した。その結果を表７に示す。
Synthesis of 1,3-bis [3,5-bis (p-tolyl) triazin-1-yl] benzene (abbreviation BDTTzB) 1) 1-chloro-3,5-di (p-tolyl) triazine (abbreviation CDTTz) Synthesis of
Recrystallization with chloroform / methanol = 5/1 gave a pale yellow solid. Yield: 66.4%
2) Synthesis of 1,3-bis [3,5-bis (p-tolyl) triazin-1-yl] benzene (abbreviation BDTTzB)
Purification was performed by a column chromatography method (developing solvent: chloroform), and recrystallization with chloroform gave a white powder. Yield: 85.9%
FIG. 1 shows an absorption spectrum of a deposited film of BDTTzB, and FIG. 2 shows a fluorescence spectrum. In addition, an ultraviolet-visible absorption spectrum and an ionization potential (for example, Riken Keiki AC-3) were measured to evaluate electrochemical characteristics. The results are shown in Table 7.
実施例５
１−（ピリジン−３−イル）−３，５−ビス（３，５−ジフェニルトリアジン−１−イル）ベンゼン（略称ＢＤＰＴｚＰｙＢ）の合成
精製はカラムクロマトグラフィー法（展開溶媒：クロロホルム／メタノール＝３０／１）で行い、白色の粉末を得た。収率：４８．６％
図５にＢＤＰＴｚＰｙＢ蒸着膜の吸収スペクトル（Ａｂｓ）と蛍光スペクトル（ＰＬ）を示す。図６にＢＤＰＴｚＰｙＢの低温リン光スペクトルを示す。また紫外−可視吸収スペクトルおよびイオン化ポテンシャル（例えば理研計器ＡＣ−３）を測定し、電気化学特性を評価した。その結果を表９に示す。
Synthesis of 1- (pyridin-3-yl) -3,5-bis (3,5-diphenyltriazin-1-yl) benzene (abbreviation BDPTzPyB)
Purification was performed by a column chromatography method (developing solvent: chloroform / methanol = 30/1) to obtain a white powder. Yield: 48.6%
FIG. 5 shows an absorption spectrum (Abs) and a fluorescence spectrum (PL) of the BDPTzPyB deposited film. FIG. 6 shows a low-temperature phosphorescence spectrum of BDPTzPyB. In addition, an ultraviolet-visible absorption spectrum and an ionization potential (for example, Riken Keiki AC-3) were measured to evaluate electrochemical characteristics. The results are shown in Table 9.
実施例６
９，９−ジメチル−２，７−ビス〔３，５−ビス（ｐ−トリル）トリアジン−１−イル〕フルオレン（略称ＤＴＴｚＦ）の合成
精製はカラムクロマトグラフィー法（展開溶媒：クロロホルム）で行った。クロロホルムにより再結晶を行い、薄い黄色の固体を得た。収率：８３．６％
さらに、昇華精製を行い、薄い黄色の結晶を得た。
図７にＤＴＴｚＦ蒸着膜の吸収スペクトル（Ａｂｓ）と蛍光スペクトル（ＰＬ）を示す。また紫外−可視吸収スペクトルおよびイオン化ポテンシャル（例えば理研計器ＡＣ−３）を測定し、電気化学特性を評価した。その結果を表１１に示す。
Synthesis of 9,9-dimethyl-2,7-bis [3,5-bis (p-tolyl) triazin-1-yl] fluorene (abbreviation DTTzF)
Purification was performed by a column chromatography method (developing solvent: chloroform). Recrystallization from chloroform gave a pale yellow solid. Yield: 83.6%
Furthermore, sublimation purification was performed to obtain pale yellow crystals.
FIG. 7 shows an absorption spectrum (Abs) and a fluorescence spectrum (PL) of the DTTzF deposited film. In addition, an ultraviolet-visible absorption spectrum and an ionization potential (for example, Riken Keiki AC-3) were measured to evaluate electrochemical characteristics. The results are shown in Table 11.
実施例７、８および９
実施例１で合成したＢＤＴＰｍＢ、実施例２で合成したＢＤＴＰｍＰｙＢおよび実施例３で合成したＢＤＴＰｍＰｙを電子輸送層に用いた素子を作成し、電子輸送性の評価を行った。
作成した素子構成は以下の通りである。
＜素子構造＞
実施例７
○：ＩＴＯ／ＮＰＤ（５０ｎｍ）／Ａｌｑ３（４０ｎｍ）／ＢＤＴＰｍＰｙＢ（実施例２の化合物）（３０ｎｍ）／ＬｉＦ（０．５ｎｍ）／Ａｌ（１００ｎｍ）；
実施例８
□：ＩＴＯ／ＮＰＤ（５０ｎｍ）／Ａｌｑ３（４０ｎｍ）／ＢＤＴＰｍＰｙ（実施例３の化合物）（３０ｎｍ）／ＬｉＦ（０．５ｎｍ）／Ａｌ（１００ｎｍ）；
実施例９
△：ＩＴＯ／ＮＰＤ（５０ｎｍ）／Ａｌｑ３（４０ｎｍ）／ＢＤＴＰｍＢ（実施例１の化合物）（３０ｎｍ）／ＬｉＦ（０．５ｎｍ）／Ａｌ（１００ｎｍ）．
電流密度−電圧特性は図８に、
輝 度−電圧特性は図９に、
視感効率−電圧特性は図１０に、
電流効率−電圧特性は図１１に、
視感効率−輝度特性は図１２に、
ＥＬスペクトルは 図１３に、
それぞれ示す。
これら素子の１００ｃｄ／ｍ２における電圧（Ｖｏｌｔａｇｅ）、電流密度（Ｃｕｒｒｅｎｔ ｄｅｎｓｉｔｙ）、電力効率（Ｐ．Ｅ．）、量子効率（Ｑ．Ｅ．）を表１３に示す。
Devices using BDTPmB synthesized in Example 1, BDTPmPyB synthesized in Example 2, and BDTPmPy synthesized in Example 3 for the electron transport layer were prepared, and the electron transport property was evaluated.
The created device configuration is as follows.
<Element structure>
Example 7
○: ITO / NPD (50 nm) / Alq 3 (40 nm) / BDTPmPyB (compound of Example 2) (30 nm) / LiF (0.5 nm) / Al (100 nm);
Example 8
□: ITO / NPD (50 nm) / Alq 3 (40 nm) / BDTPmPy (compound of Example 3) (30 nm) / LiF (0.5 nm) / Al (100 nm);
Example 9
Δ: ITO / NPD (50 nm) / Alq 3 (40 nm) / BDTPmB (compound of Example 1) (30 nm) / LiF (0.5 nm) / Al (100 nm).
The luminance-voltage characteristics are shown in FIG.
The luminous efficiency vs. voltage characteristics are shown in FIG.
The current efficiency vs. voltage characteristics are shown in FIG.
The luminous efficiency-luminance characteristics are shown in FIG.
The EL spectrum is shown in FIG.
Each is shown.
Table 13 shows the voltage (Voltage), current density (Current density), power efficiency (PE), and quantum efficiency (QE) of these elements at 100 cd / m 2 .
実施例１０、１１
実施例３で合成したＢＤＴＰｍＰｙおよび実施例２で合成したＢＤＴＰｍＰｙＢを電子輸送層に用いた緑色リン光素子を作成し、特性を評価した。
作成した素子構成は以下の通りである。
＜素子構造＞
実施例１０
○：ＩＴＯ／ＴＰＤＰＥＳ（２０ｎｍ）／ＴＡＰＣ（３０ｎｍ）／ＣＢＰ：〔Ｉｒ（ｐｐｙ）３〕（８ｗｔ％）（３０ｎｍ）／ＢＤＴＰｍＰｙ（実施例３の化合物）（４０ｎｍ）／ＬｉＦ（０．５ｎｍ）／Ａｌ（１００ｎｍ）；
実施例１１
●：ＩＴＯ／ＴＰＤＰＥＳ（２０ｎｍ）／ＴＡＰＣ（３０ｎｍ）／ＣＢＰ：〔Ｉｒ（ｐｐｙ）３〕（８ｗｔ％）（３０ｎｍ）／ＢＤＴＰｍＰｙＢ（実施例２の化合物）（４０ｎｍ）／ＬｉＦ（０．５ｎｍ）／Ａｌ（１００ｎｍ）．
電流密度 −電圧特性は 図１４に、
輝 度 −電圧特性は 図１５に、
視感効率 −電圧特性は 図１６に、
電流効率 −電圧特性は 図１７に、
視感効率 −輝度特性は 図１８に、
外部量子効率−輝度特性は 図１９に、
ＥＬスペクトルは 図２０に、
ＥＬスペクトル（拡大図）は図２１に、
それぞれ示す。
これらの素子の１００ｃｄ／ｍ２における電圧、電流密度、電力効率、量子効率を表１５に示す。
A green phosphor element using BDTPmPy synthesized in Example 3 and BDTPmPyB synthesized in Example 2 for the electron transport layer was prepared, and the characteristics were evaluated.
The created device configuration is as follows.
<Element structure>
Example 10
○: ITO / TPDPES (20 nm) / TAPC (30 nm) / CBP: [Ir (ppy) 3 ] (8 wt%) (30 nm) / BDTPmPy (compound of Example 3) (40 nm) / LiF (0.5 nm) / Al (100 nm);
Example 11
●: ITO / TPDPES (20 nm) / TAPC (30 nm) / CBP: [Ir (ppy) 3 ] (8 wt%) (30 nm) / BDTPmPyB (compound of Example 2) (40 nm) / LiF (0.5 nm) / Al (100 nm).
The luminance-voltage characteristics are shown in FIG.
The luminous efficiency vs. voltage characteristics are shown in FIG.
The current efficiency vs. voltage characteristics are shown in FIG.
The luminous efficiency vs. luminance characteristics are shown in FIG.
The external quantum efficiency vs. luminance characteristics are shown in FIG.
The EL spectrum is shown in FIG.
The EL spectrum (enlarged view) is shown in FIG.
Each is shown.
Table 15 shows the voltage, current density, power efficiency, and quantum efficiency at 100 cd / m 2 of these elements.
実施例１２、１３および比較例１、２
実施例１で合成したＢＤＴＰｍＢと実施例４で合成したＢＤＴＴｚＢとの電子輸送性を既知の電子輸送材料ＴｍＰｙＰｈＴＡＺとＴｍ５ＰｍＰｈＢの間で比較検討を行った。
作成した素子構成は以下の通りである。
＜素子構造＞
実施例１２
○：ＩＴＯ／α−ＮＰＤ（５０ｎｍ）／Ａｌｑ３（４０ｎｍ）／ＢＤＴＴｚＢ（３０ｎｍ）／ＬｉＦ（０．５ｎｍ）／Ａｌ（１００ｎｍ）；
比較例１
□：ＩＴＯ／α−ＮＰＤ（５０ｎｍ）／Ａｌｑ３（４０ｎｍ）／ＴｍＰｙＰｈＴＡＺ（３０ｎｍ）／ＬｉＦ（０．５ｎｍ）／Ａｌ（１００ｎｍ）；
実施例１３
△：ＩＴＯ／α−ＮＰＤ（５０ｎｍ）／Ａｌｑ３（４０ｎｍ）／ＢＤＴＰｍＢ（３０ｎｍ）／ＬｉＦ（０．５ｎｍ）／Ａｌ（１００ｎｍ）；
比較例２
◇：ＩＴＯ／α−ＮＰＤ（５０ｎｍ）／Ａｌｑ３（４０ｎｍ）／Ｔｍ５ＰｍＰｈＢ（３０ｎｍ）／ＬｉＦ（０．５ｎｍ）／Ａｌ（１００ｎｍ）．
電流密度−電圧特性は図２２に、
輝 度−電圧特性は図２３に、
電流効率−電圧特性は図２４に、
視感効率−電圧特性は図２５に、
ＥＬスペクトルは 図２６に、
それぞれ示す。
これら素子の１００ｃｄ／ｍ２における電圧、電流密度、電力効率、量子効率を表１７に示す。
The electron transport properties of BDTPmB synthesized in Example 1 and BDTTzB synthesized in Example 4 were compared between known electron transport materials TmPyPhTAZ and Tm5PmPhB.
The created device configuration is as follows.
<Element structure>
Example 12
O: ITO / α-NPD (50 nm) / Alq 3 (40 nm) / BDTTzB (30 nm) / LiF (0.5 nm) / Al (100 nm);
Comparative Example 1
□: ITO / α-NPD (50 nm) / Alq 3 (40 nm) / TmPyPhTAZ (30 nm) / LiF (0.5 nm) / Al (100 nm);
Example 13
Δ: ITO / α-NPD (50 nm) / Alq 3 (40 nm) / BDTPmB (30 nm) / LiF (0.5 nm) / Al (100 nm);
Comparative Example 2
◇: ITO / α-NPD (50 nm) / Alq 3 (40 nm) / Tm5PmPhB (30 nm) / LiF (0.5 nm) / Al (100 nm).
Luminance-voltage characteristics are shown in FIG.
The current efficiency vs. voltage characteristics are shown in FIG.
The luminous efficiency vs. voltage characteristics are shown in FIG.
The EL spectrum is shown in FIG.
Each is shown.
Table 17 shows the voltage, current density, power efficiency, and quantum efficiency at 100 cd / m 2 of these elements.
実施例１４、１５および比較例３、４
実施例２で合成したＢＤＴＰｍＰｙＢと実施例５で合成したＢＤＰＴｚＰｙＢの電子輸送性の評価を行うため、公知の材料Ａｌｑ３とｍＢＰｙＰＰｙＢを電子輸送層に使用した素子をそれぞれ作成し、これらの比較を行った。
作成した素子構成は以下の通りである。
＜素子構造＞
実施例１４
▽：ＩＴＯ／ＮＰＤ（５０ｎｍ）／Ａｌｑ３（４０ｎｍ）／ＢＤＴＰｍＰｙＢ（３０ｎｍ）／ＬｉＦ（０．５ｎｍ）／Ａｌ（１００ｎｍ）．
実施例１５
◇：ＩＴＯ／ＮＰＤ（５０ｎｍ）／Ａｌｑ３（４０ｎｍ）／ＢＤＰＴｚＰｙＢ（３０ｎｍ）／ＬｉＦ（０．５ｎｍ）／Ａｌ（１００ｎｍ）；
比較例３
△：ＩＴＯ／ＮＰＤ（５０ｎｍ）／Ａｌｑ３（７０ｎｍ）／ＬｉＦ（０．５ｎｍ）／Ａｌ（１００ｎｍ）；
比較例４
○：ＩＴＯ／ＮＰＤ（５０ｎｍ）／Ａｌｑ３（４０ｎｍ）／ｍＢＰｙＰＰｙＢ（３０ｎｍ）／ＬｉＦ（０．５ｎｍ）／Ａｌ（１００ｎｍ）；
電流密度−電圧特性は図２７に、
輝 度−電圧特性は図２８に、
視感効率−電圧特性は図２９に、
電流効率−電圧特性は図３０に、
視感効率−輝度特性は図３１に、
ＥＬスペクトルは 図３２に、
それぞれ示す。
これら素子の１００ｃｄ／ｍ２における電圧、電流密度、電力効率、量子効率を表１９に示す。
Order to evaluate the electron transporting BDPTzPyB synthesized in BDTPmPyB Example 5 synthesized in Example 2, to create each element using a known material Alq 3 and mBPyPPyB the electron transport layer, performing these comparisons It was.
The created device configuration is as follows.
<Element structure>
Example 14
ＩＴＯ: ITO / NPD (50 nm) / Alq 3 (40 nm) / BDTPmPyB (30 nm) / LiF (0.5 nm) / Al (100 nm).
Example 15
◇: ITO / NPD (50 nm) / Alq 3 (40 nm) / BDPTzPyB (30 nm) / LiF (0.5 nm) / Al (100 nm);
Comparative Example 3
Δ: ITO / NPD (50 nm) / Alq 3 (70 nm) / LiF (0.5 nm) / Al (100 nm);
Comparative Example 4
○: ITO / NPD (50 nm) / Alq 3 (40 nm) / mBPyPPyB (30 nm) / LiF (0.5 nm) / Al (100 nm);
The current density-voltage characteristics are shown in FIG.
Luminance-voltage characteristics are shown in FIG.
The luminous efficiency vs. voltage characteristics are shown in FIG.
The current efficiency vs. voltage characteristics are shown in FIG.
The luminous efficiency-luminance characteristics are shown in FIG.
The EL spectrum is shown in FIG.
Each is shown.
Table 19 shows the voltage, current density, power efficiency, and quantum efficiency of these elements at 100 cd / m 2 .
実施例１６、１７および比較例５
実施例２で合成したＢＤＴＰｍＰｙＢおよび実施例５で合成したＢＤＰＴｚＰｙＢを電子輸送層に用いた緑色リン光素子を作成し特性を評価した。また比較のため従来から用いている電子輸送材料ｍＢＰｙＰＰｙＢを用いた素子も作成した。
作成した素子構成は以下の通りである。
＜素子構造＞
実施例１６
◇：ＩＴＯ／ＴＰＤＰＥＳ（２０ｎｍ）／ＴＡＰＣ（３０ｎｍ）／ＣＢＰ：〔Ｉｒ（ｐｐｙ）３〕（８ｗｔ％）（３０ｎｍ）／ＢＤＴＰｍＰｙＢ（３０ｎｍ）／ＬｉＦ（０．５ｎｍ）／Ａｌ（１００ｎｍ）．
実施例１７
○：ＩＴＯ／ＴＰＤＰＥＳ（２０ｎｍ）／ＴＡＰＣ（３０ｎｍ）／ＣＢＰ：〔Ｉｒ（ｐｐｙ）３〕（８ｗｔ％）（３０ｎｍ）／ＢＤＰＴｚＰｙＢ（３０ｎｍ）／ＬｉＦ（０．５ｎｍ）／Ａｌ（１００ｎｍ）；
比較例５
△：ＩＴＯ／ＴＰＤＰＥＳ（２０ｎｍ）／ＴＡＰＣ（３０ｎｍ）／ＣＢＰ：〔Ｉｒ（ｐｐｙ）３〕（８ｗｔ％）（３０ｎｍ）／ｍＢＰｙＰＰｙＢ（３０ｎｍ）／ＬｉＦ（０．５ｎｍ）／Ａｌ（１００ｎｍ）；
これらの素子の
電流密度 −電圧特性は 図３３に、
輝 度 −電圧特性は 図３４に、
視感効率 −電圧特性は 図３５に、
電流効率 −電圧特性は 図３６に、
視感効率 −輝度特性は 図３７に、
外部量子効率−輝度特性は 図３８に、
ＥＬスペクトルは 図３９に、
ＥＬスペクトル（拡大図）は図４０に、
それぞれ示す。
これら素子の１００ｃｄ／ｍ２における電圧、電流密度、電力効率、量子効率を表２１に示す。
A green phosphor element using BDTPmPyB synthesized in Example 2 and BDPTzPyB synthesized in Example 5 as the electron transport layer was prepared and the characteristics were evaluated. For comparison, an element using an electron transport material mBPyPPyB which has been conventionally used was also prepared.
The created device configuration is as follows.
<Element structure>
Example 16
◇: ITO / TPDPES (20 nm) / TAPC (30 nm) / CBP: [Ir (ppy) 3 ] (8 wt%) (30 nm) / BDTPmPyB (30 nm) / LiF (0.5 nm) / Al (100 nm).
Example 17
○: ITO / TPDPES (20 nm) / TAPC (30 nm) / CBP: [Ir (ppy) 3 ] (8 wt%) (30 nm) / BDPTzPyB (30 nm) / LiF (0.5 nm) / Al (100 nm);
Comparative Example 5
Δ: ITO / TPDPES (20 nm) / TAPC (30 nm) / CBP: [Ir (ppy) 3 ] (8 wt%) (30 nm) / mBPyPPyB (30 nm) / LiF (0.5 nm) / Al (100 nm);
The current density vs. voltage characteristics of these elements are shown in FIG.
Luminance-voltage characteristics are shown in FIG.
Luminous efficiency vs. voltage characteristics are shown in FIG.
The current efficiency vs. voltage characteristics are shown in FIG.
The luminous efficiency vs. luminance characteristics are shown in FIG.
The external quantum efficiency vs. luminance characteristics are shown in FIG.
The EL spectrum is shown in FIG.
The EL spectrum (enlarged view) is shown in FIG.
Each is shown.
Table 21 shows voltage, current density, power efficiency, and quantum efficiency at 100 cd / m 2 of these elements.
１ 基板
２ 陽極（ＩＴＯ）
３ 発光層
４ 陰極
５ 正孔輸送層（ホール輸送層）
６ 電子輸送層
７ 正孔注入層（ホール注入層）
８ 電子注入層
９ 正孔ブロック層（ホールブロック層）
1
3
6
8
Claims (4)
Ｒ１〜Ｒ５、Ｒ１０〜Ｒ２２は、水素、炭素数１〜６の直鎖または分枝のアルキル基、炭素数１〜６の直鎖または分枝のアルコキシ基、炭素数１〜６の直鎖または分枝のアルキルアミノ基よりなる群からそれぞれ独立して選ばれた基であり、
Ｒ６〜Ｒ９は、水素、炭素数１〜６の直鎖または分枝のアルキル基、炭素数１〜６の直鎖または分枝のアルコキシ基、炭素数１〜６の直鎖または分枝のアルキルアミノ基およびピリジル基よりなる群からそれぞれ独立して選ばれた基であり、
Ｒ２３、Ｒ２４は、水素、炭素数１〜６の直鎖又は分岐のアルキル基からなる群からそれぞれ独立して選ばれた基であり、
Ｘは炭素又は窒素である）
で示されるピリミジン系またはトリアジン系誘導体。 The following general formula (1)
R 1 to R 5 and R 10 to R 22 are hydrogen, a linear or branched alkyl group having 1 to 6 carbon atoms, a linear or branched alkoxy group having 1 to 6 carbon atoms, or 1 to 6 carbon atoms. Each independently selected from the group consisting of linear or branched alkylamino groups,
R 6 to R 9 are hydrogen, a linear or branched alkyl group having 1 to 6 carbon atoms, a linear or branched alkoxy group having 1 to 6 carbon atoms, a linear or branched group having 1 to 6 carbon atoms. Each independently selected from the group consisting of an alkylamino group and a pyridyl group,
R 23 and R 24 are groups independently selected from the group consisting of hydrogen and a linear or branched alkyl group having 1 to 6 carbon atoms,
X is carbon or nitrogen)
A pyrimidine-based or triazine-based derivative represented by:
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