CN109438350A - Small organic molecule luminescent material and organic electroluminescence device - Google Patents
Small organic molecule luminescent material and organic electroluminescence device Download PDFInfo
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- CN109438350A CN109438350A CN201811378536.1A CN201811378536A CN109438350A CN 109438350 A CN109438350 A CN 109438350A CN 201811378536 A CN201811378536 A CN 201811378536A CN 109438350 A CN109438350 A CN 109438350A
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- luminescent material
- small organic
- organic molecule
- adamantane
- electroluminescence device
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- 239000000463 material Substances 0.000 title claims abstract description 91
- 238000005401 electroluminescence Methods 0.000 title claims abstract description 50
- DZBUGLKDJFMEHC-UHFFFAOYSA-N acridine Chemical compound C1=CC=CC2=CC3=CC=CC=C3N=C21 DZBUGLKDJFMEHC-UHFFFAOYSA-N 0.000 claims abstract description 74
- 239000000178 monomer Substances 0.000 claims abstract description 22
- 239000000126 substance Substances 0.000 claims description 19
- 238000006243 chemical reaction Methods 0.000 claims description 18
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N Aniline Chemical compound NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 claims description 10
- 230000027756 respiratory electron transport chain Effects 0.000 claims description 9
- 239000000758 substrate Substances 0.000 claims description 8
- 238000006443 Buchwald-Hartwig cross coupling reaction Methods 0.000 claims description 6
- OIRHKGBNGGSCGS-UHFFFAOYSA-N 1-bromo-2-iodobenzene Chemical group BrC1=CC=CC=C1I OIRHKGBNGGSCGS-UHFFFAOYSA-N 0.000 claims description 5
- 230000005540 biological transmission Effects 0.000 claims description 5
- LAQPNDIUHRHNCV-UHFFFAOYSA-N isophthalonitrile Chemical compound N#CC1=CC=CC(C#N)=C1 LAQPNDIUHRHNCV-UHFFFAOYSA-N 0.000 claims description 5
- 239000002994 raw material Substances 0.000 claims description 5
- 230000002950 deficient Effects 0.000 claims description 4
- AHZNWHRBSADGMV-UHFFFAOYSA-N 1,3,5-triphenyl-2H-pyrazine Chemical compound C1(=CC=CC=C1)N1CC(=NC(=C1)C1=CC=CC=C1)C1=CC=CC=C1 AHZNWHRBSADGMV-UHFFFAOYSA-N 0.000 claims description 3
- TZMSYXZUNZXBOL-UHFFFAOYSA-N 10H-phenoxazine Chemical compound C1=CC=C2NC3=CC=CC=C3OC2=C1 TZMSYXZUNZXBOL-UHFFFAOYSA-N 0.000 claims description 3
- 230000001680 brushing effect Effects 0.000 claims description 3
- 238000003618 dip coating Methods 0.000 claims description 3
- 238000001704 evaporation Methods 0.000 claims description 3
- 230000008020 evaporation Effects 0.000 claims description 3
- 238000002347 injection Methods 0.000 claims description 3
- 239000007924 injection Substances 0.000 claims description 3
- 238000007761 roller coating Methods 0.000 claims description 3
- 238000010020 roller printing Methods 0.000 claims description 3
- 238000005507 spraying Methods 0.000 claims description 3
- 239000007858 starting material Substances 0.000 claims description 3
- 125000001424 substituent group Chemical group 0.000 claims description 3
- OETBGSAJFWSUDM-UHFFFAOYSA-N thianthrene 5,5,10,10-tetraoxide Chemical compound C1=CC=C2S(=O)(=O)C3=CC=CC=C3S(=O)(=O)C2=C1 OETBGSAJFWSUDM-UHFFFAOYSA-N 0.000 claims description 3
- YRHRIQCWCFGUEQ-UHFFFAOYSA-N thioxanthen-9-one Chemical class C1=CC=C2C(=O)C3=CC=CC=C3SC2=C1 YRHRIQCWCFGUEQ-UHFFFAOYSA-N 0.000 claims description 3
- NVSWLAWBGNWEPN-UHFFFAOYSA-N 2,4,6-triphenyl-1h-triazine Chemical class N1N(C=2C=CC=CC=2)N=C(C=2C=CC=CC=2)C=C1C1=CC=CC=C1 NVSWLAWBGNWEPN-UHFFFAOYSA-N 0.000 claims description 2
- 238000007641 inkjet printing Methods 0.000 claims description 2
- GKWANOWBIQZOFA-UHFFFAOYSA-N CC1=C(C(=CC=C1)C)[B] Chemical compound CC1=C(C(=CC=C1)C)[B] GKWANOWBIQZOFA-UHFFFAOYSA-N 0.000 claims 1
- 238000010422 painting Methods 0.000 claims 1
- ORILYTVJVMAKLC-UHFFFAOYSA-N adamantane Chemical compound C1C(C2)CC3CC1CC2C3 ORILYTVJVMAKLC-UHFFFAOYSA-N 0.000 abstract description 18
- 238000006862 quantum yield reaction Methods 0.000 abstract description 7
- 238000005424 photoluminescence Methods 0.000 abstract description 6
- 238000000354 decomposition reaction Methods 0.000 abstract description 5
- 238000000746 purification Methods 0.000 abstract description 5
- 238000000859 sublimation Methods 0.000 abstract description 5
- 230000008022 sublimation Effects 0.000 abstract description 5
- 230000015572 biosynthetic process Effects 0.000 abstract description 4
- 230000005281 excited state Effects 0.000 abstract description 4
- 238000003786 synthesis reaction Methods 0.000 abstract description 4
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 15
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 15
- KZMAWJRXKGLWGS-UHFFFAOYSA-N 2-chloro-n-[4-(4-methoxyphenyl)-1,3-thiazol-2-yl]-n-(3-methoxypropyl)acetamide Chemical compound S1C(N(C(=O)CCl)CCCOC)=NC(C=2C=CC(OC)=CC=2)=C1 KZMAWJRXKGLWGS-UHFFFAOYSA-N 0.000 description 13
- 238000002360 preparation method Methods 0.000 description 13
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 10
- PQXKHYXIUOZZFA-UHFFFAOYSA-M lithium fluoride Chemical compound [Li+].[F-] PQXKHYXIUOZZFA-UHFFFAOYSA-M 0.000 description 10
- 239000000047 product Substances 0.000 description 10
- MFRIHAYPQRLWNB-UHFFFAOYSA-N sodium tert-butoxide Chemical compound [Na+].CC(C)(C)[O-] MFRIHAYPQRLWNB-UHFFFAOYSA-N 0.000 description 10
- 238000003756 stirring Methods 0.000 description 10
- 239000002904 solvent Substances 0.000 description 9
- 150000001875 compounds Chemical class 0.000 description 8
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 7
- 239000000741 silica gel Substances 0.000 description 7
- 229910002027 silica gel Inorganic materials 0.000 description 7
- CINYXYWQPZSTOT-UHFFFAOYSA-N 3-[3-[3,5-bis(3-pyridin-3-ylphenyl)phenyl]phenyl]pyridine Chemical compound C1=CN=CC(C=2C=C(C=CC=2)C=2C=C(C=C(C=2)C=2C=C(C=CC=2)C=2C=NC=CC=2)C=2C=C(C=CC=2)C=2C=NC=CC=2)=C1 CINYXYWQPZSTOT-UHFFFAOYSA-N 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 6
- 238000000034 method Methods 0.000 description 6
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- 238000001228 spectrum Methods 0.000 description 6
- DYHSDKLCOJIUFX-UHFFFAOYSA-N tert-butoxycarbonyl anhydride Chemical compound CC(C)(C)OC(=O)OC(=O)OC(C)(C)C DYHSDKLCOJIUFX-UHFFFAOYSA-N 0.000 description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 6
- ATTVYRDSOVWELU-UHFFFAOYSA-N 1-diphenylphosphoryl-2-(2-diphenylphosphorylphenoxy)benzene Chemical compound C=1C=CC=CC=1P(C=1C(=CC=CC=1)OC=1C(=CC=CC=1)P(=O)(C=1C=CC=CC=1)C=1C=CC=CC=1)(=O)C1=CC=CC=C1 ATTVYRDSOVWELU-UHFFFAOYSA-N 0.000 description 5
- -1 2,6- Xylyl Chemical group 0.000 description 5
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 description 5
- 239000004411 aluminium Substances 0.000 description 5
- 229910052782 aluminium Inorganic materials 0.000 description 5
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 5
- 230000008859 change Effects 0.000 description 5
- 230000000694 effects Effects 0.000 description 5
- MRNHPUHPBOKKQT-UHFFFAOYSA-N indium;tin;hydrate Chemical compound O.[In].[Sn] MRNHPUHPBOKKQT-UHFFFAOYSA-N 0.000 description 5
- 239000012074 organic phase Substances 0.000 description 5
- 239000000243 solution Substances 0.000 description 5
- AYHGAQGOMUQMTR-UHFFFAOYSA-N 2-(4-bromophenyl)-4,6-diphenyl-1,3,5-triazine Chemical class C1=CC(Br)=CC=C1C1=NC(C=2C=CC=CC=2)=NC(C=2C=CC=CC=2)=N1 AYHGAQGOMUQMTR-UHFFFAOYSA-N 0.000 description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 4
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 4
- 238000010438 heat treatment Methods 0.000 description 4
- 239000007788 liquid Substances 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 4
- 150000001335 aliphatic alkanes Chemical class 0.000 description 3
- 239000012300 argon atmosphere Substances 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 238000004821 distillation Methods 0.000 description 3
- 238000001035 drying Methods 0.000 description 3
- 238000000921 elemental analysis Methods 0.000 description 3
- 239000011521 glass Substances 0.000 description 3
- 238000004770 highest occupied molecular orbital Methods 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- IYWDFZORUJMHRV-UHFFFAOYSA-N n-bromo-n-phenylaniline Chemical compound C=1C=CC=CC=1N(Br)C1=CC=CC=C1 IYWDFZORUJMHRV-UHFFFAOYSA-N 0.000 description 3
- YJVFFLUZDVXJQI-UHFFFAOYSA-L palladium(ii) acetate Chemical compound [Pd+2].CC([O-])=O.CC([O-])=O YJVFFLUZDVXJQI-UHFFFAOYSA-L 0.000 description 3
- 239000007787 solid Substances 0.000 description 3
- 239000012265 solid product Substances 0.000 description 3
- 238000002411 thermogravimetry Methods 0.000 description 3
- CCIVUDMVXNBUCY-UHFFFAOYSA-N 4-bromo-n-phenylaniline Chemical compound C1=CC(Br)=CC=C1NC1=CC=CC=C1 CCIVUDMVXNBUCY-UHFFFAOYSA-N 0.000 description 2
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 description 2
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 2
- 229960000583 acetic acid Drugs 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 229910052796 boron Inorganic materials 0.000 description 2
- 150000007942 carboxylates Chemical class 0.000 description 2
- 238000010276 construction Methods 0.000 description 2
- GPAYUJZHTULNBE-UHFFFAOYSA-N diphenylphosphine Chemical compound C=1C=CC=CC=1PC1=CC=CC=C1 GPAYUJZHTULNBE-UHFFFAOYSA-N 0.000 description 2
- 235000013399 edible fruits Nutrition 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 230000005284 excitation Effects 0.000 description 2
- 239000012362 glacial acetic acid Substances 0.000 description 2
- 239000010931 gold Substances 0.000 description 2
- 229910052737 gold Inorganic materials 0.000 description 2
- 235000011167 hydrochloric acid Nutrition 0.000 description 2
- LELOWRISYMNNSU-UHFFFAOYSA-N hydrogen cyanide Chemical compound N#C LELOWRISYMNNSU-UHFFFAOYSA-N 0.000 description 2
- DLEDOFVPSDKWEF-UHFFFAOYSA-N lithium butane Chemical compound [Li+].CCC[CH2-] DLEDOFVPSDKWEF-UHFFFAOYSA-N 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- UHOVQNZJYSORNB-UHFFFAOYSA-N monobenzene Natural products C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 2
- MZRVEZGGRBJDDB-UHFFFAOYSA-N n-Butyllithium Substances [Li]CCCC MZRVEZGGRBJDDB-UHFFFAOYSA-N 0.000 description 2
- 230000003287 optical effect Effects 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 239000004065 semiconductor Substances 0.000 description 2
- 150000003384 small molecules Chemical class 0.000 description 2
- 238000004528 spin coating Methods 0.000 description 2
- 238000010189 synthetic method Methods 0.000 description 2
- LSAQBBSMSWPVOL-UHFFFAOYSA-N tert-butyl N-(4-bromophenyl)-N-phenylcarbamate Chemical compound C(C)(C)(C)OC(N(C1=CC=CC=C1)C1=CC=C(C=C1)Br)=O LSAQBBSMSWPVOL-UHFFFAOYSA-N 0.000 description 2
- ZGNPLWZYVAFUNZ-UHFFFAOYSA-N tert-butylphosphane Chemical compound CC(C)(C)P ZGNPLWZYVAFUNZ-UHFFFAOYSA-N 0.000 description 2
- HBQUOLGAXBYZGR-UHFFFAOYSA-N 2,4,6-triphenyl-1,3,5-triazine Chemical compound C1=CC=CC=C1C1=NC(C=2C=CC=CC=2)=NC(C=2C=CC=CC=2)=N1 HBQUOLGAXBYZGR-UHFFFAOYSA-N 0.000 description 1
- 125000004800 4-bromophenyl group Chemical group [H]C1=C([H])C(*)=C([H])C([H])=C1Br 0.000 description 1
- 238000007125 Buchwald synthesis reaction Methods 0.000 description 1
- 240000007594 Oryza sativa Species 0.000 description 1
- 235000007164 Oryza sativa Nutrition 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
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- 239000008358 core component Substances 0.000 description 1
- 238000005859 coupling reaction Methods 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 239000003599 detergent Substances 0.000 description 1
- 230000005684 electric field Effects 0.000 description 1
- 239000002305 electric material Substances 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 230000003760 hair shine Effects 0.000 description 1
- 229910001385 heavy metal Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- AMGQUBHHOARCQH-UHFFFAOYSA-N indium;oxotin Chemical compound [In].[Sn]=O AMGQUBHHOARCQH-UHFFFAOYSA-N 0.000 description 1
- 230000002401 inhibitory effect Effects 0.000 description 1
- 239000003446 ligand Substances 0.000 description 1
- IVSZLXZYQVIEFR-UHFFFAOYSA-N m-xylene Chemical compound CC1=CC=CC(C)=C1 IVSZLXZYQVIEFR-UHFFFAOYSA-N 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- VIKNJXKGJWUCNN-XGXHKTLJSA-N norethisterone Chemical compound O=C1CC[C@@H]2[C@H]3CC[C@](C)([C@](CC4)(O)C#C)[C@@H]4[C@@H]3CCC2=C1 VIKNJXKGJWUCNN-XGXHKTLJSA-N 0.000 description 1
- 239000011368 organic material Substances 0.000 description 1
- 229920000620 organic polymer Polymers 0.000 description 1
- 239000002957 persistent organic pollutant Substances 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 230000005622 photoelectricity Effects 0.000 description 1
- 239000002861 polymer material Substances 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 238000012827 research and development Methods 0.000 description 1
- 230000004044 response Effects 0.000 description 1
- 235000009566 rice Nutrition 0.000 description 1
- 238000007363 ring formation reaction Methods 0.000 description 1
- 230000003595 spectral effect Effects 0.000 description 1
- 238000005979 thermal decomposition reaction Methods 0.000 description 1
- 238000002207 thermal evaporation Methods 0.000 description 1
- 238000002604 ultrasonography Methods 0.000 description 1
- 238000007738 vacuum evaporation Methods 0.000 description 1
- 230000000007 visual effect Effects 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D221/00—Heterocyclic compounds containing six-membered rings having one nitrogen atom as the only ring hetero atom, not provided for by groups C07D211/00 - C07D219/00
- C07D221/02—Heterocyclic compounds containing six-membered rings having one nitrogen atom as the only ring hetero atom, not provided for by groups C07D211/00 - C07D219/00 condensed with carbocyclic rings or ring systems
- C07D221/20—Spiro-condensed ring systems
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D401/00—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, at least one ring being a six-membered ring with only one nitrogen atom
- C07D401/02—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, at least one ring being a six-membered ring with only one nitrogen atom containing two hetero rings
- C07D401/10—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, at least one ring being a six-membered ring with only one nitrogen atom containing two hetero rings linked by a carbon chain containing aromatic rings
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
- C09K11/06—Luminescent, e.g. electroluminescent, chemiluminescent materials containing organic luminescent materials
-
- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K50/00—Organic light-emitting devices
- H10K50/10—OLEDs or polymer light-emitting diodes [PLED]
- H10K50/11—OLEDs or polymer light-emitting diodes [PLED] characterised by the electroluminescent [EL] layers
- H10K50/12—OLEDs or polymer light-emitting diodes [PLED] characterised by the electroluminescent [EL] layers comprising dopants
-
- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
- H10K85/60—Organic compounds having low molecular weight
- H10K85/649—Aromatic compounds comprising a hetero atom
- H10K85/654—Aromatic compounds comprising a hetero atom comprising only nitrogen as heteroatom
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K2211/00—Chemical nature of organic luminescent or tenebrescent compounds
- C09K2211/10—Non-macromolecular compounds
- C09K2211/1003—Carbocyclic compounds
- C09K2211/1007—Non-condensed systems
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K2211/00—Chemical nature of organic luminescent or tenebrescent compounds
- C09K2211/10—Non-macromolecular compounds
- C09K2211/1018—Heterocyclic compounds
- C09K2211/1025—Heterocyclic compounds characterised by ligands
- C09K2211/1059—Heterocyclic compounds characterised by ligands containing three nitrogen atoms as heteroatoms
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Physics & Mathematics (AREA)
- Spectroscopy & Molecular Physics (AREA)
- Optics & Photonics (AREA)
- Electroluminescent Light Sources (AREA)
Abstract
The present invention provides a kind of small organic molecule luminescent material and organic electroluminescence device.Small organic molecule luminescent material of the invention, by a kind of novel acridine donor monomer 10H- spiral shell [acridine -9, 2 '-adamantane] it is coupled to obtain with receptor unit, its structure is single, molecular weight determines, convenient for purification, multi-stage synthesis reproducibility is good, with lower sublimation temperature and higher decomposition temperature, film morphology is stablized, and since nonaromatic rigid structure adamantane is as donor part-structure, the small organic molecule luminescent material has very high photoluminescence quantum yield under filminess, when applied in organic electroluminescence device, excited state molecule can be efficiently solved due to configuration relaxation leads to serious non-radiative decay and keeps device efficiency low problem.
Description
Technical field
The present invention relates to field of organic electroluminescence, in particular to a kind of small organic molecule luminescent material and using this is organic
The organic electroluminescence device of small molecule emitter material.
Background technique
Organic electroluminescent (OLED) device is a kind of selfluminous element, has voltage low, visual angle is wide, fast response time,
The advantages such as thermal adaptability is good are the display technologies of a new generation, and volume production goes out oled panel for a small number of certain producers at present, and more
Some companies also enter research and development and volume production stage.
The principle of organic electroluminescence device is, under electric field action, hole and electronics are infused from anode and cathode respectively
Enter, respectively by hole injection layer, hole transmission layer and electron injecting layer, electron transfer layer, be compounded to form exciton in luminescent layer,
Exciton attenuation shines.
Core component of the electroluminescent organic material as organic electroluminescence device has the service performance of device
Have a great impact.Wherein, the film forming characteristics, good of the fluorescent characteristic of high-quantum efficiency, good characteristic of semiconductor, high quality
Chemical stability and thermal stability, good processing performance etc. be its main performance factors.According to molecular structure property with
Emission wavelength range is classified, including organic small molecule emitter material, organic coordination compound luminescent material and organic polymer hair
Luminescent material.
In order to improve efficiency and the service life of organic electro-optic device, organic coordination compound luminescent material is essentially heavy metal cooperation
Object, production cost is higher, is unfavorable for being mass produced, and there are serious for organic coordination compound luminescent material at higher current densities
Efficiency roll-off phenomenon, in addition, the stability of organic coordination compound luminescent material is also and bad, and small organic molecule luminescent material is compared
For polymer material, since preparation step is few, stable structure facilitates purifying, thus can obtain higher device efficiency,
So that being more likely to get commercial applications.Currently, the flexible OLED devices prepared using small organic molecule luminescent material, because
It has the advantages that incomparable and has obtained great concern, and achieves huge progress.
So far Organic Light Emitting Diode has been achieved for considerable progress, and scientists propose various theoretical next
Explain luminous mechanism.But up to now, structure is simple and have both superperformance, meet commercialization demand organic small point
Sub-light electric material is still extremely limited, and developing new organic photoelectrical material still has very important meaning.
Summary of the invention
The purpose of the present invention is to provide a kind of small organic molecule luminescent materials, have very high light under filminess
Photoluminescence quantum yield is the light emitting guest material of the double transport properties in good electron hole.
Another object of the present invention is to provide organic electroluminescence device, luminescent layer is shone using above-mentioned small organic molecule
Material, external quantum efficiency with higher and excellent luminescent properties.
To achieve the above object, the present invention provides a kind of small organic molecule luminescent material, with 10H- spiral shell [9,2 '-gold of acridine-
Rigid alkane] it is donor monomer, it is the luminescent material by the way that receptor unit and donor monomer to be coupled；
The chemical structural formula of 10H- spiral shell [acridine -9,2 '-adamantane] is
Shown in the general formula of the chemical structure such as following formula (I) of the small organic molecule luminescent material,
In formula (I), Ar is the armaticity substituent with electron deficient.
The small organic molecule luminescent material is with 2,4,6- triphenyl triazine, 2,4,6- triphenyl pyrazine, 1,3- benzene two
Formonitrile HCN, 3,5- benzene dicarbonitrile, hexichol phosphono, diphenyl sulfide sulfuryl, phenoxazine -10,10 '-dioxide, three (2,6- dimethylbenzene
Base) boron, thianthrene -5,5,10,10- tetroxide, 9- thioxanthones or 9- Oxoxanthone be receptor unit.
In formula (I), Ar is
The chemical structural formula of the small organic molecule luminescent material is
The small organic molecule luminescent material is with receptor unit with donor monomer 10H- spiral shell [acridine -9,2 '-adamantane]
Raw material is prepared by Hartwig-Buchwald coupling reaction.
10H- spiral shell [9,2 '-adamantane of acridine -] is successively led to using aniline, adjacent bromo-iodobenzene and Buddha's warrior attendant alkanone as starting material
Cross Hartwig-Buchwald coupling reaction and (Boc)2O adds protection reaction to be prepared.
The present invention also provides a kind of organic electroluminescence devices, including transparent substrates, anode layer, the hole note being stacked
Enter layer, hole transmission layer, luminescent layer, electron transfer layer and cathode layer；
The luminescent layer includes small organic molecule luminescent material as described above.
The small organic molecule luminescent material is used as light emitting guest material in the luminescent layer.
The luminescent layer includes one or more small organic molecule luminescent materials with different structure formula.
Luminescent layer system by way of hot evaporation, spin coating, brushing, spraying, dip-coating, roller coating, printing or inkjet printing
It is standby to be formed.
Beneficial effects of the present invention: small organic molecule luminescent material of the present invention, by a kind of novel based on nonaromatic
The acridine donor monomer 10H- spiral shell [9,2 '-adamantane of acridine -] of rigid structure adamantane, is coupled to obtain with receptor unit, knot
Structure is single, and molecular weight determines, convenient for purification, multi-stage synthesis reproducibility is good, has lower sublimation temperature and higher decomposition temperature
Degree, film morphology are stablized, non-aromatic since donor monomer 10H- spiral shell [9,2 '-adamantane of acridine -] has very rigid structure
Property rigid structure adamantane as donor part-structure, the small organic molecule luminescent material under filminess have it is very high
Photoluminescence quantum yield, can be efficiently solved when applied in organic electroluminescence device excited state molecule due to configuration relax
Henan leads to serious non-radiative decay and the problem that keeps device efficiency low, and can pass through and change and 10H- spiral shell [acridine -9,2 '-gold
Rigid alkane] connection receptor unit type, the material properties such as luminescent color, molecular weight, electrophilicity of adjustable material, effectively
Ground regulates and controls its conjugate length and Intramolecular electron transfer, and adjusts highest occupied molecular orbital and minimum vacant orbital energy level and have to meet
The needs of organic electroluminescence devices can assign device superior performance when to applying in organic electroluminescence device.This
The organic electroluminescence devices of invention, luminescent layer use above-mentioned small organic molecule luminescent material, can effectively improve organic electroluminescence hair
The external quantum efficiency of optical device has excellent device performance.
For further understanding of the features and technical contents of the present invention, it please refers to below in connection with of the invention detailed
Illustrate and attached drawing, however, the drawings only provide reference and explanation, is not intended to limit the present invention.
Detailed description of the invention
With reference to the accompanying drawing, by the way that detailed description of specific embodiments of the present invention, technical solution of the present invention will be made
And other beneficial effects are apparent.
In attached drawing,
Fig. 1 is the thermogravimetric analysis figure of preparation-obtained molecule 1 in embodiment 7；
Fig. 2 is the preparation-obtained abosrption spectrogram in toluene solution of molecule 1,2,3 and 4 in embodiment 7,8,9 and 10；
Fig. 3 is the preparation-obtained fluorescence emission in toluene solution of molecule 1,2,3 and 4 in embodiment 7,8,9 and 10
Spectrogram；
Fig. 4 be using in embodiment 7 preparation-obtained molecule 1 as the organic electroluminescence for luminescent layer guest materials
The Current density-voltage of part-brightness curve figure；
Fig. 5 is organic electroluminescence device of the preparation-obtained molecule 1 as luminescent layer guest materials using in embodiment 7
Current efficiency-brightness relationship curve figure；
Fig. 6 is organic electroluminescence device of the preparation-obtained molecule 1 as luminescent layer guest materials using in embodiment 7
External quantum efficiency-brightness relationship curve figure；
Fig. 7 is the organic electroluminescence device using the preparation-obtained molecule 1 of embodiment 7 as luminescent layer guest materials
Luminescent spectrum；
Fig. 8 is the current density-of the organic electroluminescence device using compound DMAc-TRZ as luminescent layer guest materials
Voltage-brightness curve graph；
Fig. 9 is the current efficiency-of the organic electroluminescence device using compound DMAc-TRZ as luminescent layer guest materials
Brightness relationship curve figure；
Figure 10 is the outer quantum effect of the organic electroluminescence device using compound DMAc-TRZ as luminescent layer guest materials
Rate-brightness relationship curve figure；
Figure 11 is the luminescent spectrum of the organic electroluminescence device using compound DMAc-TRZ as luminescent layer guest materials.
Specific embodiment
Further to illustrate technological means and its effect adopted by the present invention, below in conjunction with preferred implementation of the invention
Example and its attached drawing are described in detail.
The present invention provides a kind of small organic molecule luminescent material, using a kind of novel based on nonaromatic rigid structure
The acridine donor monomer 10H- spiral shell [9,2 '-adamantane of acridine -] of adamantane, will be given by Hartwig-Buchwald coupling reaction
The luminescent material that body unit 10H- spiral shell [acridine -9,2 '-adamantane] and receptor unit are coupled.
Wherein, 10H- spiral shell [9,2 '-adamantane of acridine -] is to pass sequentially through Hartwig-Buchwald reaction, (Boc)2O adds
The a series of simple reaction such as reaction, low-temp reaction, room temperature or high temperature ring-closure reaction is protected to obtain, chemical structural formula is
Since the rigidity of molecule entirety can be improved in the intrinsic rigid structure of adamantane, so as to be effectively reduced its group
At small organic molecule luminescent material molecule under excitation state because of energy loss caused by geometric configuration deformation, therefore given using this
The small organic molecule luminescent material that body unit 10H- spiral shell [acridine -9,2 '-adamantane] obtains has very high under filminess
Photoluminescence quantum yield, and then help to improve the efficiency and stability of device.
Shown in the general formula of the chemical structure such as following formula (I) of the small organic molecule luminescent material,
In formula (I), Ar is the armaticity substituent with electron deficient.
Specifically, the small organic molecule luminescent material be with 2,4,6- triphenyl triazines, 2,4,6- triphenyl pyrazines, 1,
3- benzene dicarbonitrile, 3,5- benzene dicarbonitrile, hexichol phosphono, diphenyl sulfide sulfuryl, phenoxazine -10,10 '-dioxide, three (2,6-
Xylyl) the common electron deficient aromatics such as boron, thianthrene -5,5,10,10- tetroxide, 9- thioxanthones or 9- Oxoxanthone
Object and its derivative are receptor unit.
Illustratively, in formula (1), Ar can be
Then the chemical structural formula of the small organic molecule luminescent material mutually should be
Specifically, 10H- spiral shell [9,2 '-adamantane of acridine -] be using aniline, adjacent bromo-iodobenzene and Buddha's warrior attendant alkanone as starting material,
Pass sequentially through Hartwig-Buchwald coupling reaction and (Boc)2O adds a series of simple reactions such as protection reaction to be prepared.
Small organic molecule luminescent material of the invention, by a kind of novel based on nonaromatic rigid structure adamantane
Acridine donor monomer 10H- spiral shell [9,2 '-adamantane of acridine -], is coupled to obtain, structure is single, and molecular weight is true with receptor unit
Fixed, convenient for purification, multi-stage synthesis reproducibility is good, has lower sublimation temperature and higher decomposition temperature, and film morphology is stablized,
Since donor monomer 10H- spiral shell [9,2 '-adamantane of acridine -] has very rigid structure, nonaromatic rigid structure Buddha's warrior attendant
As donor part-structure, the small organic molecule luminescent material obtained using the donor monomer is had very alkane under filminess
High photoluminescence quantum yield can efficiently solve excited state molecule due to configuration when applied in organic electroluminescence device
Relaxation leads to serious non-radiative decay and the problem that keeps device efficiency low, and can pass through and change and 10H- spiral shell [acridine -9,2 ' -
Adamantane] connection receptor unit type, the material properties such as luminescent color, molecular weight, electrophilicity of adjustable material have
Effect ground regulates and controls its conjugate length and Intramolecular electron transfer, and adjusts highest occupied molecular orbital and minimum vacant orbital energy level to meet
The needs of organic electroluminescence device can assign device superior performance when to applying in organic electroluminescence device.
Based on above-mentioned small organic molecule luminescent material, the present invention also provides a kind of organic electroluminescence devices, including layer
Transparent substrates, anode layer, hole injection layer, hole transmission layer, luminescent layer, electron transfer layer and the cathode layer of folded setting；It is described
Luminescent layer includes above-described small organic molecule luminescent material.
Specifically, the small organic molecule luminescent material is used as light emitting guest material in the luminescent layer.
Specifically, the luminescent layer includes the luminous material of one or more small organic molecules with different structure formula
Material.
Specifically, the luminescent layer can be beaten by hot evaporation, spin coating, brushing, spraying, dip-coating, roller coating, printing or ink-jet
The mode of print prepares to be formed.
Organic electroluminescence device of the invention, small organic molecule luminescent material used by luminescent layer pass through Hartwig-
Donor monomer 10H- spiral shell [9,2 '-adamantane of acridine -] is coupled to obtain by Buchwald coupling reaction with receptor unit, is had higher
External quantum efficiency and excellent luminescent properties.
Below by way of specific embodiment, the present invention is described in detail, but the present invention is not limited to scope of embodiments.
Embodiment 1
The synthetic method 1 of the bromo- N- phenylaniline of 2-, chemical equation is as follows:
In the three-necked flask of 250mL, aniline (0.2mol, 18.6g), adjacent bromo-iodobenzene are sequentially added at room temperature
(0.2mol, 56.58g), palladium acetate (0.6mmol, 134.4mg), sodium tert-butoxide (0.4mol) sequentially add in flask, then plus
Enter the toluene of 150mL, leads to N220 minutes, tertiary butyl phosphine (1.2mmol, 1.2ml) then is added, continues logical N220 minutes, heating
To flowing back and stir 12 hours.It is cooled to room temperature, filters and removes sodium tert-butoxide, distillation under pressure removes solvent, uses silica gel chromatographic column
Separating-purifying obtains colourless oil liquid (27.8g, yield 56%).
Embodiment 2
The synthetic method 2 of the bromo- N- phenylaniline of 2-, chemical equation is as follows:
In the three-necked flask of 250mL, aniline (0.2mol, 18.6g), adjacent bromo-iodobenzene are sequentially added at room temperature
(0.2mol, 56.58g), palladium acetate (0.6mmol, 134.4mg), sodium tert-butoxide (0.4mol) sequentially add in flask, adjacent double
The toluene of 150mL is then added in (2- phenyl) two (diphenylphosphine) (0.6mmol, 340mg), leads to N2It 20 minutes, is heated to back
It flows and stirs 12 hours.It is cooled to room temperature, filters and removes sodium tert-butoxide, distillation under pressure removes solvent, with silica gel chromatograph post separation
Purification obtains colourless oil liquid (44.2g, yield 89%).
It can be found that by changing catalyst ligand by tertiary butyl phosphine after above embodiments 1 and embodiment 2 are compared
Become adjacent bis- (2- phenyl) two (diphenylphosphine), the bromo- N- phenylaniline yield of 2- has been increased to 89% by 56%.
Embodiment 3
The preparation method 1 of (4- bromophenyl)-Phenyl-carbamic acid tertiary butyl ester, chemical equation is as follows:
In 500 milliliters of single-necked flasks, di-tert-butyl dicarbonate (BOC) (0.2mol, 43.6g) is added at room temperature
In 400 milliliters of tetrahydrofuran, then adds to N- (dibromobenzene) aniline (0.1mol, 24.8g), be heated to flowing back and stir
24 hours.Then mixed liquor is poured into 1L water, and product is extracted with dichloromethane.Anhydrous magnesium sulfate dries organic phase, separation
After remove solvent, obtain colourless oil liquid (32.0g, yield 92%) with silica gel chromatographic column separating-purifying.
Embodiment 4
The preparation method 2 of (4- bromophenyl)-Phenyl-carbamic acid tertiary butyl ester:
In 500 milliliters of single-necked flasks, di-tert-butyl dicarbonate (BOC) (0.2mol, 43.6g) is added at room temperature
In 400 milliliters of tetrahydrofuran, then adds to N- (dibromobenzene) aniline (0.1mol, 24.8g), lead to N220 minutes and add
Heat is to flowing back and stir 24 hours.Then mixed liquor is poured into 1L water, and product is extracted with dichloromethane.Anhydrous magnesium sulfate is dry
Dry organic phase removes solvent after separation, obtains colourless oil liquid (33.0g, yield 95%) with silica gel chromatographic column separating-purifying.
It is analyzed by embodiment 3 and 4, finds logical N2With obstructed N2Reaction yield is influenced less, to illustrate the reaction to oxygen
It is insensitive.
Embodiment 5
The preparation method 1 of 10H- spiral shell [acridine -9,2'- adamantane], chemical equation is as follows:
In 200 milliliters of three-necked flasks, (4- bromophenyl)-phenyl-ammonia for will being prepared in embodiment 3 or embodiment 4
Base carboxylate (8mmol, 2.8g) is added in 60 milliliters of anhydrous tetrahydro furan, is then cooled to subzero 80 DEG C, then
It is slowly dropped into the n-BuLi (9mmol, 5.2mL) of 1.6M.Continue stirring 2 hours under an argon atmosphere.Buddha's warrior attendant alkanone is added
(8.1mmol, 1.2g) continues then to be to slowly warm up to room temperature in stirring 2 hours in the solution of 25 milliliters of tetrahydrofurans.Then it is added
15 milliliters of dilute hydrochloric acid (1M) pour into mixed liquor in 500 milliliters of water, and be extracted with dichloromethane after being further continued for stirring 12 hours
Product.Anhydrous magnesium sulfate dries organic phase, removes solvent after separation, obtains white solid with silica gel chromatographic column separating-purifying
(0.5g, 20.7%).
Embodiment 6
The preparation method 2 of 10H- spiral shell [acridine -9,2'- adamantane], chemical equation is as follows:
In 200 milliliters of three-necked flasks, (4- bromophenyl)-phenyl-ammonia for will being prepared in embodiment 3 or embodiment 4
Base carboxylate (8mmol, 2.8g) is added in 60 milliliters of anhydrous tetrahydro furan, is then cooled to subzero 80 DEG C, then
It is slowly dropped into the n-BuLi (9mmol, 5.2mL) of 1.6M.Continue stirring 2 hours under an argon atmosphere.Buddha's warrior attendant alkanone is added
(8.1mmol, 1.2g) continues then to be to slowly warm up to room temperature in stirring 2 hours in the solution of 25 milliliters of tetrahydrofurans.Distillation under pressure
Solvent is removed, 100mL glacial acetic acid is added, leads to N220 minutes, 5 milliliters of concentrated hydrochloric acids are added, and are heated to flowing back and stirring 24 hours
Afterwards, mixed liquor is poured into 500 milliliters of water, and product is extracted with dichloromethane.Anhydrous magnesium sulfate dries organic phase, goes after separation
Except solvent, white solid (1.5g, 62%) is obtained with silica gel chromatographic column separating-purifying.
By analysis comparison above-described embodiment 5 and embodiment 6, discovery is using glacial acetic acid, concentrated hydrochloric acid and the reaction side of heating
Method can be effectively facilitated the progress of reaction.
Embodiment 7
The small organic molecule luminescent material based on 10H- spiral shell [acridine -9,2 '-adamantane] donor monomer with structural formula 1
Preparation, chemical equation is as follows:
10H- spiral shell [acridine -9,2'- adamantane] (2.4mmol, 0.72g) and 2- is added into reaction flask under an argon atmosphere
(4- bromophenyl) -4,6- diphenyl -1,3,5-triazines (2.8mmol, 1.09g), 50 milliliters of toluene are as solvent, 60 milli of palladium acetate
Gram, tri-tert phosphorus (0.5mmol, 0.11g) and 0.48 gram of sodium tert-butoxide.It is heated to reflux down and is stirred to react 24 hours, after cooling,
Mixed liquor is poured into 200 milliliters of water, and product is extracted with dichloromethane.Anhydrous magnesium sulfate dries organic phase, removes after separation
Solvent obtains nattierblue solid with silica gel chromatographic column separating-purifying.High-purity is obtained in sublime under vacuum conditions after drying
Product (0.72g, 49%).Molecular formula are as follows: C43H36N4；Molecular weight are as follows: 608.29；Elemental analysis result are as follows: C, 84.84；H,
5.96；N, 9.20.
Embodiment 8
The small organic molecule luminescent material based on 10H- spiral shell [acridine -9,2 '-adamantane] donor monomer with structural formula 2
Preparation, chemical equation is as follows:
Compared with Example 7, the difference is that 2- (4- bromophenyl) -4,6- diphenyl -1,3,5-triazines is changed into
2- (4- bromophenyl) -4,6- bis- (4- aminomethyl phenyl) -1,3,5-triazines of mole, other raw materials and step with embodiment 7
It is identical, finally obtain the yield 75% of solid product.Product formula: C45H40N4；Molecular weight: 636.33；Elemental analysis knot
Fruit are as follows: C, 84.87；H, 6.33；N, 8.80.
Embodiment 9
The small organic molecule luminescent material based on 10H- spiral shell [acridine -9,2 '-adamantane] donor monomer with structural formula 3
Preparation, chemical equation is as follows:
Compared with Example 7, the difference is that 2- (4- bromophenyl) -4,6- diphenyl -1,3,5-triazines is changed into
2- (4- bromophenyl) -4,6- bis- (2- aminomethyl phenyl) -1,3,5-triazines of mole, other raw materials and step with embodiment 7
It is identical, finally obtain the yield 75% of solid product.Product formula: C45H40N4；Molecular weight: 636.32；Elemental analysis knot
Fruit are as follows: C, 84.87；H, 6.30；N, 8.83.
Embodiment 10
The small organic molecule luminescent material based on 10H- spiral shell [acridine -9,2 '-adamantane] donor monomer with structural formula 4
Preparation, chemical equation is as follows:
Compared with Example 7, the difference is that 2- (4- bromophenyl) -4,6- diphenyl -1,3,5-triazines is changed into
Bis- (2,4- the 3,5-dimethylphenyl) -1,3,5-triazines of 2- (4- bromophenyl) -4,6- of mole, other raw materials and step with implementation
Example 7 is identical, finally obtains the yield 65% of solid product.Product formula: C47H44N4；Molecular weight are as follows: 664.36；Element point
Analyse result are as follows: C, 84.90；H, 6.67；N, 8.43.
Embodiment 11
The present embodiment test that embodiment 7 is prepared based on 10H- spiral shell [acridine -9,2 '-adamantane] donor monomer
The thermal stability of small organic molecule luminescent material 1, by the stability of molecule of the clearly material and by application in a manner of vacuum evaporation
Feasibility in organic luminescent device.Specific implementation step is as follows: thermogravimetric analysis (TGA) is surveyed on Netzsch TG 209
, heating speed is 10 DEG C of min under nitrogen protection-1, heating terminal is greater than 600 DEG C, as shown in Figure 1, passing through test, molecule 1
Thermal decomposition temperature be 420 DEG C.With very high decomposition temperature, it is easy to obtain the photoelectricity of high-purity by way of gradient sublimation
Materials'use, and suitable for electroluminescent device.
Embodiment 12
Prepare organic electroluminescence device
The present embodiment prepare it is a kind of by embodiment 7 be prepared based on 10H- spiral shell [acridine -9,2 '-adamantane] donor list
The small organic molecule luminescent material molecule 1 of member is used for the organic electroluminescence device of luminescent layer guest materials, specific stepped construction
It is as follows:
Glass substrate/tin indium oxide (125 nanometers)/TAPC (40 nanometers)/20wt% or 30wt% molecule 1:DPEPO (30
Nanometer)/TmPyPB (50 nanometers)/lithium fluoride (1 nanometer)/aluminium (100 nanometers).Wherein, tin indium oxide is anode, and TAPC is as empty
Cave transport layer, TmPyPB is as electron transfer layer, and lithium fluoride is as electron injecting layer, and for aluminium as cathode, molecule 1:DPEPO is hair
Photosphere.
The preparation method is as follows: successively using acetone, micron level semiconductor dedicated the indium tin oxid glass substrate of electrically conducting transparent
Detergent, deionized water, isopropanol ultrasound are cleared up 15 minutes, to remove the dirt of substrate surface.It is subsequently placed into 80 in insulating box
Degree Celsius drying is stand-by.Tin indium oxide substrate after drying is handled 4 minutes with oxygen plasma build-up of luminance equipment, further removes table
The organic pollutant of face attachment.TAPC, emitting layer material, TmPyPB, lithium fluoride and aluminium is heat sink in a manner of vacuum thermal evaporation
Product on the light-emitting layer, obtains the organic electroluminescence device of the present embodiment.
Comparative example 13
Prepare organic electroluminescence device
The present embodiment is prepared for a kind of by 10- (4- (4,6- phenyl -1,3,5- triazine -2-yl) phenyl) -9,9- dimethyl -
Acridan (writes a Chinese character in simplified form are as follows: DMAc-TRZ) organic electroluminescent of (structure is as follows) for luminescent layer guest materials
Device.
The specific stepped construction of organic electroluminescence device is as follows: (40 receive glass substrate/tin indium oxide (125 nanometers)/TAPC
Rice)/20wt% or 30wt%DMAc-TRZ:DPEPO (40 nanometers)/TmPyPB (50 nanometers)/lithium fluoride (1 nanometer)/aluminium (100
Nanometer).Tin indium oxide is anode, and TAPC is infused as electron transfer layer, lithium fluoride as electronics as hole transmission layer, TmPyPB
Enter layer, for aluminium as cathode, DMAc-TRZ:DPEPO is luminescent layer.
Organic electroluminescence device preparation method such as 12 method of embodiment is consistent in this implementation.
The performance evaluation of organic photoelectric device
Volt test is received according to embodiment 12 and the organic electroluminescence of the preparation of comparative example 13 with 2400 number of Keithley
Electric current of the luminescent device under different voltage obtains organic electroluminescence device in different electricity divided by area with electric current with odd even
The current density of pressure.
With CS-200 spectroradio luminance meter and the test of PR745 spectral instrument according to embodiment 12 and comparative example 13
Brightness and radiant energy density of the organic electroluminescence devices of preparation under different voltages.According to organic electroluminescence device not
With the current density and brightness under voltage, the current efficiency and external quantum efficiency (EQE) of organic electroluminescence device are obtained.
The Current density-voltage of the organic electroluminescence device of embodiment 12-brightness relationship curve figure, current efficiency-are bright
Graph of relation, external quantum efficiency-brightness relationship curve figure and luminescent spectrum curve are spent respectively such as Fig. 4, Fig. 5, Fig. 6 and Fig. 7 institute
Show.
The Current density-voltage of the organic electroluminescence device of embodiment 13-brightness relationship curve figure, current efficiency-are bright
Graph of relation, external quantum efficiency-brightness relationship curve figure and luminescent spectrum curve are spent respectively such as Fig. 8, Fig. 9, Figure 10 and Figure 11
It is shown.
The starting voltage of the organic electroluminescence device of embodiment 12 and embodiment 13, maximum current efficiency, maximum outer amount
It is shown in the data summarizations such as sub- efficiency, CIE coordinate such as the following table 1.
Table 1
Such as drawn a conclusion by comparing and analyzing can get to embodiment 12 and embodiment 13: in same device conditions
Under, compared with molecule DMAc-TRZ, molecule 1 obtains more excellent external quantum efficiency and more blue electroluminescent spectrum, former
Because may be: by replacing two CH of acridine group3Hydrogen atom, significantly reduce hyperconjugation electron in molecule 1 and make
With in addition, being had by the molecule of 10H- spiral shell [9,2 '-adamantane of acridine -] donor monomer composition with very rigid molecular structure
The relaxation process for inhibiting to effect molecular configuration of molecule under the conditions of excitation state, reduces the Stokes shift of molecule 1.By
Above-mentioned two reason results in more blue electroluminescent spectrum.Compared with DMAc-TRZ, higher external quantum efficiency is obtained, it is former
The Nonradiative Decay Process that molecule is inhibited because that may be rigid structure improves molecule photoluminescence quantum yield, thus
Improve the efficiency of the device based on molecule 1.Have this demonstrate small organic molecule luminescent material of the invention and is used as luminescent layer
The effect of middle doping guest materials.Since blue emitting material shows there is very important meaning with white light photo for full light color
Justice, therefore preparing has the high efficiency blue material sense of application potential great.
The molecular structural formula difference of TAPC, mCP, DPEPO and TmPyPB described in embodiment 12 and embodiment 13 are as follows
It is shown:
The above embodiment is a preferred embodiment of the present invention, but embodiments of the present invention are not by above-described embodiment
Limitation, it is other it is any without departing from the spirit and principles of the present invention made by change, modify, substitute, combination simplifies equal
It should be equivalent substitute mode, be included within the scope of the present invention.
In conclusion small organic molecule luminescent material of the present invention, by a kind of novel based on nonaromatic rigid structure
The acridine donor monomer 10H- spiral shell [9,2 '-adamantane of acridine -] of adamantane, is coupled to obtain with receptor unit, and structure is single, point
Son amount determines that, convenient for purification, multi-stage synthesis reproducibility is good, has lower sublimation temperature and higher decomposition temperature, film shape
State is stablized, since donor monomer 10H- spiral shell [9,2 '-adamantane of acridine -] has very rigid structure, nonaromatic rigidity
For structure adamantane as donor part-structure, which has very high photic hair under filminess
Quantum yield can efficiently solve excited state molecule since configuration relaxation causes sternly when applied in organic electroluminescence device
The problem for weighing non-radiative decay and keeping device efficiency low, and can pass through to change and be connected with 10H- spiral shell [9,2 '-adamantane of acridine -]
Receptor unit type, the material properties such as luminescent color, molecular weight, electrophilicity of adjustable material effectively regulate and control it
Conjugate length and Intramolecular electron transfer, and highest occupied molecular orbital and minimum vacant orbital energy level are adjusted to meet organic electroluminescence hair
The needs of optical device can assign device superior performance when to applying in organic electroluminescence device.Machine of the invention
Electroluminescent device, luminescent layer use above-mentioned small organic molecule luminescent material, can effectively improve organic electroluminescence device
External quantum efficiency has excellent device performance.
The above for those of ordinary skill in the art can according to the technique and scheme of the present invention and technology
Other various corresponding changes and modifications are made in design, and all these change and modification all should belong to the claims in the present invention
Protection scope.
Claims (10)
1. a kind of small organic molecule luminescent material, which is characterized in that with 10H- spiral shell [9,2 '-adamantane of acridine -] for donor monomer,
It is the luminescent material by the way that receptor unit and donor monomer to be coupled；
The chemical structural formula of 10H- spiral shell [acridine -9,2 '-adamantane] is
Shown in the general formula of the chemical structure such as following formula (I) of the small organic molecule luminescent material,
In formula (I), Ar is the armaticity substituent with electron deficient.
2. small organic molecule luminescent material as described in claim 1, which is characterized in that with 2,4,6- triphenyl triazines, 2,4,
6- triphenyl pyrazine, 1,3- benzene dicarbonitrile, 3,5- benzene dicarbonitrile, hexichol phosphono, diphenyl sulfide sulfuryl, phenoxazine -10,10 '-two
Oxide, three (2,6- xylyl) boron, thianthrene -5,5,10,10- tetroxide, 9- thioxanthones or 9- Oxoxanthone are receptor list
Member.
3. small organic molecule luminescent material as claimed in claim 2, which is characterized in that in formula (1), Ar is
4. small organic molecule luminescent material as claimed in claim 2, which is characterized in that its chemical structural formula is
5. small organic molecule luminescent material as described in claim 1, which is characterized in that be with donor monomer 10H- spiral shell [acridine-
9,2 '-adamantane] with receptor unit be raw material, be prepared by Hartwig-Buchwald coupling reaction.
6. small organic molecule luminescent material as described in claim 1, which is characterized in that 10H- spiral shell [9,2 '-adamantane of acridine -]
Be using aniline, adjacent bromo-iodobenzene and Buddha's warrior attendant alkanone as starting material, pass sequentially through Hartwig-Buchwald coupling reaction and
(Boc)2O adds protection reaction to be prepared.
7. a kind of organic electroluminescence device, which is characterized in that including transparent substrates, anode layer, the hole injection being stacked
Layer, hole transmission layer, luminescent layer, electron transfer layer and cathode layer；The luminescent layer includes such as any one of claim 1-6 institute
The small organic molecule luminescent material stated.
8. organic electroluminescence device as claimed in claim 7, which is characterized in that the small organic molecule luminescent material is in institute
It states in luminescent layer as light emitting guest material.
9. organic electroluminescence device as claimed in claim 7, which is characterized in that the luminescent layer includes one or more tools
There is the small organic molecule luminescent material of different structure formula.
10. organic electroluminescence device as claimed in claim 7, which is characterized in that the luminescent layer passes through hot evaporation, rotation
Painting, brushing, spraying, dip-coating, roller coating, printing or inkjet printing mode prepare to be formed.
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| CN201811378536.1A CN109438350B (en) | 2018-11-19 | 2018-11-19 | Organic small molecule luminescent material and organic electroluminescent device |
| PCT/CN2018/124982 WO2020103294A1 (en) | 2018-11-19 | 2018-12-28 | Organic micromolecule light-emitting material and organic electroluminescent component |
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| JP2020205419A (en) * | 2019-06-14 | 2020-12-24 | シャンシー ライト オプトエレクトロニクス マテリアル カンパニー リミテッドＳｈａａｎｘｉ Ｌｉｇｈｔｅ Ｏｐｔｏｅｌｅｃｔｒｏｎｉｃｓ Ｍａｔｅｒｉａｌ Ｃｏ．，Ｌｔｄ． | Nitrogen-containing compound, organic electroluminescence device, and photoelectric conversion device |
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| WO2020103294A1 (en) | 2020-05-28 |
| CN109438350B (en) | 2020-08-04 |
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