CN108299283A - A kind of TADF materials and its application - Google Patents
A kind of TADF materials and its application Download PDFInfo
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- CN108299283A CN108299283A CN201810123867.4A CN201810123867A CN108299283A CN 108299283 A CN108299283 A CN 108299283A CN 201810123867 A CN201810123867 A CN 201810123867A CN 108299283 A CN108299283 A CN 108299283A
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- 239000000463 material Substances 0.000 title claims abstract description 77
- 125000003118 aryl group Chemical group 0.000 claims abstract description 14
- 125000000217 alkyl group Chemical group 0.000 claims abstract description 7
- 230000005525 hole transport Effects 0.000 claims abstract description 7
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims abstract description 5
- 125000004429 atom Chemical group 0.000 claims abstract description 4
- 125000004432 carbon atom Chemical group C* 0.000 claims abstract description 4
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 claims abstract description 4
- 230000005540 biological transmission Effects 0.000 claims description 13
- -1 D-atom Chemical group 0.000 claims description 9
- 230000027756 respiratory electron transport chain Effects 0.000 claims description 8
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 3
- 239000010409 thin film Substances 0.000 claims description 3
- 238000013086 organic photovoltaic Methods 0.000 claims description 2
- 239000002096 quantum dot Substances 0.000 claims description 2
- 239000000758 substrate Substances 0.000 abstract description 16
- 125000000524 functional group Chemical group 0.000 abstract description 6
- 238000000605 extraction Methods 0.000 abstract description 5
- 238000005401 electroluminescence Methods 0.000 abstract description 3
- 238000004020 luminiscence type Methods 0.000 abstract description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 39
- 239000010410 layer Substances 0.000 description 39
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 31
- IAZDPXIOMUYVGZ-WFGJKAKNSA-N Dimethyl sulfoxide Chemical compound [2H]C([2H])([2H])S(=O)C([2H])([2H])[2H] IAZDPXIOMUYVGZ-WFGJKAKNSA-N 0.000 description 24
- 239000002904 solvent Substances 0.000 description 23
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 20
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 20
- 229910052757 nitrogen Inorganic materials 0.000 description 19
- 238000000034 method Methods 0.000 description 17
- 150000001875 compounds Chemical class 0.000 description 12
- 238000005160 1H NMR spectroscopy Methods 0.000 description 11
- 238000001704 evaporation Methods 0.000 description 11
- 238000004768 lowest unoccupied molecular orbital Methods 0.000 description 11
- 239000011368 organic material Substances 0.000 description 11
- 238000000425 proton nuclear magnetic resonance spectrum Methods 0.000 description 11
- CZDYPVPMEAXLPK-UHFFFAOYSA-N tetramethylsilane Chemical compound C[Si](C)(C)C CZDYPVPMEAXLPK-UHFFFAOYSA-N 0.000 description 11
- 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 10
- BRUOAURMAFDGLP-UHFFFAOYSA-N 9,10-dibromoanthracene Chemical class C1=CC=C2C(Br)=C(C=CC=C3)C3=C(Br)C2=C1 BRUOAURMAFDGLP-UHFFFAOYSA-N 0.000 description 10
- 238000013019 agitation Methods 0.000 description 10
- 239000003054 catalyst Substances 0.000 description 10
- 238000006243 chemical reaction Methods 0.000 description 10
- 235000019441 ethanol Nutrition 0.000 description 10
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- 239000000843 powder Substances 0.000 description 10
- 238000001953 recrystallisation Methods 0.000 description 10
- 238000010992 reflux Methods 0.000 description 10
- 229910002666 PdCl2 Inorganic materials 0.000 description 9
- 230000008020 evaporation Effects 0.000 description 9
- PIBWKRNGBLPSSY-UHFFFAOYSA-L palladium(II) chloride Chemical compound Cl[Pd]Cl PIBWKRNGBLPSSY-UHFFFAOYSA-L 0.000 description 9
- 238000004770 highest occupied molecular orbital Methods 0.000 description 8
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- 0 B*1c(CCCCCCC[C@@]2IC2)c(*=CCC(*)*)*(*)c2c1CCC(C)(*C)CCC2 Chemical compound B*1c(CCCCCCC[C@@]2IC2)c(*=CCC(*)*)*(*)c2c1CCC(C)(*C)CCC2 0.000 description 6
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 6
- HXITXNWTGFUOAU-UHFFFAOYSA-N phenylboronic acid Chemical compound OB(O)C1=CC=CC=C1 HXITXNWTGFUOAU-UHFFFAOYSA-N 0.000 description 6
- JKQOBWVOAYFWKG-UHFFFAOYSA-N molybdenum trioxide Chemical compound O=[Mo](=O)=O JKQOBWVOAYFWKG-UHFFFAOYSA-N 0.000 description 5
- 230000006798 recombination Effects 0.000 description 5
- 238000005215 recombination Methods 0.000 description 5
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- 239000000243 solution Substances 0.000 description 4
- 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 3
- UJOBWOGCFQCDNV-UHFFFAOYSA-N 9H-carbazole Chemical class C1=CC=C2C3=CC=CC=C3NC2=C1 UJOBWOGCFQCDNV-UHFFFAOYSA-N 0.000 description 3
- 150000001450 anions Chemical class 0.000 description 3
- WUICPPBYLKNKNS-UHFFFAOYSA-N benzene-1,2,3-tricarbonitrile Chemical compound N#CC1=CC=CC(C#N)=C1C#N WUICPPBYLKNKNS-UHFFFAOYSA-N 0.000 description 3
- JFDZBHWFFUWGJE-UHFFFAOYSA-N benzonitrile Chemical compound N#CC1=CC=CC=C1 JFDZBHWFFUWGJE-UHFFFAOYSA-N 0.000 description 3
- 239000004327 boric acid Substances 0.000 description 3
- 235000010338 boric acid Nutrition 0.000 description 3
- 230000008859 change Effects 0.000 description 3
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- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- 238000004057 DFT-B3LYP calculation Methods 0.000 description 2
- 238000005481 NMR spectroscopy Methods 0.000 description 2
- MWPLVEDNUUSJAV-UHFFFAOYSA-N anthracene Chemical compound C1=CC=CC2=CC3=CC=CC=C3C=C21 MWPLVEDNUUSJAV-UHFFFAOYSA-N 0.000 description 2
- 235000010290 biphenyl Nutrition 0.000 description 2
- 239000004305 biphenyl Substances 0.000 description 2
- 238000001460 carbon-13 nuclear magnetic resonance spectrum Methods 0.000 description 2
- 125000002091 cationic group Chemical group 0.000 description 2
- 150000001768 cations Chemical class 0.000 description 2
- 230000005284 excitation Effects 0.000 description 2
- 239000000284 extract Substances 0.000 description 2
- 230000005283 ground state Effects 0.000 description 2
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- 230000036961 partial effect Effects 0.000 description 2
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- ZUOUZKKEUPVFJK-UHFFFAOYSA-N phenylbenzene Natural products C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 description 2
- 238000000016 photochemical curing Methods 0.000 description 2
- 238000010791 quenching Methods 0.000 description 2
- 239000000376 reactant Substances 0.000 description 2
- 238000007740 vapor deposition Methods 0.000 description 2
- ZQWJZVCRQDBHBQ-UHFFFAOYSA-N 1-butyl-9h-carbazole Chemical group C12=CC=CC=C2NC2=C1C=CC=C2CCCC ZQWJZVCRQDBHBQ-UHFFFAOYSA-N 0.000 description 1
- 238000001644 13C nuclear magnetic resonance spectroscopy Methods 0.000 description 1
- GEQBRULPNIVQPP-UHFFFAOYSA-N 2-[3,5-bis(1-phenylbenzimidazol-2-yl)phenyl]-1-phenylbenzimidazole Chemical compound C1=CC=CC=C1N1C2=CC=CC=C2N=C1C1=CC(C=2N(C3=CC=CC=C3N=2)C=2C=CC=CC=2)=CC(C=2N(C3=CC=CC=C3N=2)C=2C=CC=CC=2)=C1 GEQBRULPNIVQPP-UHFFFAOYSA-N 0.000 description 1
- PCMKGEAHIZDRFL-UHFFFAOYSA-N 3,6-diphenyl-9h-carbazole Chemical class C1=CC=CC=C1C1=CC=C(NC=2C3=CC(=CC=2)C=2C=CC=CC=2)C3=C1 PCMKGEAHIZDRFL-UHFFFAOYSA-N 0.000 description 1
- IZACZIFCDGQRNZ-UHFFFAOYSA-N 3-tert-butyl-9-phenylcarbazole Chemical class C12=CC=CC=C2C2=CC(C(C)(C)C)=CC=C2N1C1=CC=CC=C1 IZACZIFCDGQRNZ-UHFFFAOYSA-N 0.000 description 1
- AWXGSYPUMWKTBR-UHFFFAOYSA-N 4-carbazol-9-yl-n,n-bis(4-carbazol-9-ylphenyl)aniline Chemical compound C12=CC=CC=C2C2=CC=CC=C2N1C1=CC=C(N(C=2C=CC(=CC=2)N2C3=CC=CC=C3C3=CC=CC=C32)C=2C=CC(=CC=2)N2C3=CC=CC=C3C3=CC=CC=C32)C=C1 AWXGSYPUMWKTBR-UHFFFAOYSA-N 0.000 description 1
- MHYIMOTVICWDTI-UHFFFAOYSA-N C1=CC=CC=2SC3=CC=CC=C3C(C12)=O.C1=CC=CC2=CC3=CC=CC=C3C=C12.C1(=CC=CC=C1)N(C1=CC=CC=C1)C1=CC=CC=C1 Chemical compound C1=CC=CC=2SC3=CC=CC=C3C(C12)=O.C1=CC=CC2=CC3=CC=CC=C3C=C12.C1(=CC=CC=C1)N(C1=CC=CC=C1)C1=CC=CC=C1 MHYIMOTVICWDTI-UHFFFAOYSA-N 0.000 description 1
- GNPIAMMWQDOQNW-UHFFFAOYSA-N C1C=Cc2cc(cccc3)c3c(-c3ccccc3)c2C1 Chemical compound C1C=Cc2cc(cccc3)c3c(-c3ccccc3)c2C1 GNPIAMMWQDOQNW-UHFFFAOYSA-N 0.000 description 1
- HNACKJNPFWWEKI-UHFFFAOYSA-N Cc(cc1)cc2c1[nH]c1c2cc(C)cc1 Chemical compound Cc(cc1)cc2c1[nH]c1c2cc(C)cc1 HNACKJNPFWWEKI-UHFFFAOYSA-N 0.000 description 1
- 101000837344 Homo sapiens T-cell leukemia translocation-altered gene protein Proteins 0.000 description 1
- 101150003085 Pdcl gene Proteins 0.000 description 1
- 102100028692 T-cell leukemia translocation-altered gene protein Human genes 0.000 description 1
- 101100115701 Theileria annulata TACP gene Proteins 0.000 description 1
- 238000000862 absorption spectrum Methods 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 125000005577 anthracene group Chemical group 0.000 description 1
- 230000004888 barrier function Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- SGLGUTWNGVJXPP-UHFFFAOYSA-N benzene-1,3,5-tricarbonitrile Chemical compound N#CC1=CC(C#N)=CC(C#N)=C1 SGLGUTWNGVJXPP-UHFFFAOYSA-N 0.000 description 1
- 230000000903 blocking effect Effects 0.000 description 1
- 238000004364 calculation method Methods 0.000 description 1
- 125000000609 carbazolyl group Chemical group C1(=CC=CC=2C3=CC=CC=C3NC12)* 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 238000000205 computational method Methods 0.000 description 1
- 230000021615 conjugation Effects 0.000 description 1
- 238000003851 corona treatment Methods 0.000 description 1
- 230000008878 coupling Effects 0.000 description 1
- 238000010168 coupling process Methods 0.000 description 1
- 238000005859 coupling reaction Methods 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 125000004093 cyano group Chemical group *C#N 0.000 description 1
- 208000002925 dental caries Diseases 0.000 description 1
- HEDRZPFGACZZDS-MICDWDOJSA-N deuterated chloroform Substances [2H]C(Cl)(Cl)Cl HEDRZPFGACZZDS-MICDWDOJSA-N 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 230000009977 dual effect Effects 0.000 description 1
- 239000000428 dust Substances 0.000 description 1
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- JMANVNJQNLATNU-UHFFFAOYSA-N glycolonitrile Natural products N#CC#N JMANVNJQNLATNU-UHFFFAOYSA-N 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 239000010931 gold Substances 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 230000003760 hair shine Effects 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 239000002346 layers by function Substances 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 239000007769 metal material Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen(.) Chemical compound [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 238000005457 optimization Methods 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- OSCBARYHPZZEIS-UHFFFAOYSA-N phenoxyboronic acid Chemical class OB(O)OC1=CC=CC=C1 OSCBARYHPZZEIS-UHFFFAOYSA-N 0.000 description 1
- 238000007540 photo-reduction reaction Methods 0.000 description 1
- 238000000103 photoluminescence spectrum Methods 0.000 description 1
- 238000009832 plasma treatment Methods 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 230000000171 quenching effect Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 230000002000 scavenging effect Effects 0.000 description 1
- 150000003384 small molecules Chemical class 0.000 description 1
- 238000007711 solidification Methods 0.000 description 1
- 230000008023 solidification Effects 0.000 description 1
- 125000001424 substituent group Chemical group 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 230000003746 surface roughness Effects 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 238000002834 transmittance Methods 0.000 description 1
- 230000000007 visual effect Effects 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D209/00—Heterocyclic compounds containing five-membered rings, condensed with other rings, with one nitrogen atom as the only ring hetero atom
- C07D209/56—Ring systems containing three or more rings
- C07D209/80—[b, c]- or [b, d]-condensed
- C07D209/82—Carbazoles; Hydrogenated carbazoles
- C07D209/86—Carbazoles; Hydrogenated carbazoles with only hydrogen atoms, hydrocarbon or substituted hydrocarbon radicals, directly attached to carbon atoms of the ring system
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D209/00—Heterocyclic compounds containing five-membered rings, condensed with other rings, with one nitrogen atom as the only ring hetero atom
- C07D209/56—Ring systems containing three or more rings
- C07D209/80—[b, c]- or [b, d]-condensed
-
- 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
- H10K10/00—Organic devices specially adapted for rectifying, amplifying, oscillating or switching; Organic capacitors or resistors having potential barriers
- H10K10/20—Organic diodes
-
- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K10/00—Organic devices specially adapted for rectifying, amplifying, oscillating or switching; Organic capacitors or resistors having potential barriers
- H10K10/40—Organic transistors
- H10K10/46—Field-effect transistors, e.g. organic thin-film transistors [OTFT]
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- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K30/00—Organic devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation
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- 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
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- 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]
- H10K50/14—Carrier transporting layers
- H10K50/15—Hole transporting layers
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- 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]
- H10K50/14—Carrier transporting layers
- H10K50/16—Electron transporting layers
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- 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
- H10K85/615—Polycyclic condensed aromatic hydrocarbons, e.g. anthracene
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- 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
- H10K85/657—Polycyclic condensed heteroaromatic hydrocarbons
- H10K85/6572—Polycyclic condensed heteroaromatic hydrocarbons comprising only nitrogen in the heteroaromatic polycondensed ring system, e.g. phenanthroline or carbazole
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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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- 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
- C09K2211/1011—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
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- 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
- C09K2211/1029—Heterocyclic compounds characterised by ligands containing one nitrogen atom as the heteroatom
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E10/00—Energy generation through renewable energy sources
- Y02E10/50—Photovoltaic [PV] energy
- Y02E10/549—Organic PV cells
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Physics & Mathematics (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Optics & Photonics (AREA)
- Spectroscopy & Molecular Physics (AREA)
- Electromagnetism (AREA)
- Electroluminescent Light Sources (AREA)
Abstract
The present invention relates to organic electroluminescence device technical field, a kind of TADF materials and application in the devices are disclosed.This kind of material has structure shown in general formula (I)：X1、X2It is each independently C atoms or Si atoms；Z1、Z2It is each independently unsubstituted or substituted 5-membered aromatic ring, hexa-atomic aromatic rings or condensed ring, and R1、R2It is each independently alkyl, amino, imido grpup, deuterated object or phenyl ring；A is electron attractive functional group, and B is supplied for electronic functional group.The material has the function of TADF and light extraction function simultaneously, and it is a kind of guest materials of hole transport and electron transport ability balance, using it as the luminescent layer of OLED device, photon direction is perpendicular to ito substrate during can making mulecular luminescence, more multi-photon is promoted to be projected from ito substrate direction, OLED device reduced performance effectively is avoided, and is conducive to improve exciton balance in luminescent layer, reduces roll-offing for device efficiency.
Description
Technical field
The present invention relates to organic electroluminescence device technical field, more particularly to a kind of TADF materials and application.
Background technology
Organic electroluminescence device (OLED) comes into being as the flat panel display of a new generation and has progressed into people
The visual field.Initial OLED structure is very simple, is exactly a kind of anode/luminescent layer (including luminescent material) EML/ cathodes, this
The device performance of kind simple structure is poor, and required opens bright voltage height, and luminous efficiency is low.Hereafter, a variety of device architectures are by phase
Basic device structure after proposition, such as present OLED is：Anode/hole injection layer HIL/ hole transmission layers HTL/EML hairs
Photosphere (host-guest system system)/ETL electron transfer layers/electron injecting layer EIL/ cathodes.In such multilayer device structure,
Each functional layer is responsible for single function, to make the performance of OLED be greatly improved.
In the multilayered structure of above-mentioned OLED device, exciton concentration quenching is to reduce OLED device performance in luminescent layer
A key factor.The molecule of EML layers of each luminescent material can be seen as being that a vibration is even in OLED device
It is extremely sub.When light light direction is vertical with dipole moment direction, light can more escape and distribute；When the light extraction of light
When direction is parallel with dipole moment direction, light goes out luminous intensity and will be substantially reduced.For OLED, luminescence vibrator
Dipole moment direction is very big to the light extraction intensity effect in PWM (practical waveguide modes).Therefore, OLED light extraction efficiencies are improved most
Direct method be exactly allow an OLED light emitting molecule transition dipole away from parallel with its light direction, that is to say, that actual
In OLED device, it is desirable that the transition dipole of OLED light emitting molecules is parallel to the direction of ito substrate away from TDM.
In traditional TADF OLED device, material of main part and an object TADF material containing there are one, but due to TADF
The scattering direction of photon is random direction, and only the light perpendicular to ito substrate direction has an opportunity to escape out device exterior, other
The photon in direction quenches the waveguide mode in device inside by multiple reflections.In order to improve the luminous efficiency of OLED device, pass
Way of uniting is exactly that one layer of light spe membrane will be attached outside OLED device, and this way not only increases production cost, but also does not have
Have substantive close to the low problem of OLED external light emission efficiencies.
Invention content
The purpose of the present invention is to provide a kind of TADF materials and its application in organic light emitting diode device, this kinds
TADF materials have the function of TADF and light extraction function as the luminescent material in Organic Light Emitting Diode.
In order to solve the above technical problems, embodiments of the present invention provide a kind of TADF materials, have shown in general formula (I)
Structure：
Wherein,
X1、X2It is each independently C atoms or Si atoms；
Z1、Z2It is each independently unsubstituted or substituted 5-membered aromatic ring, hexa-atomic aromatic rings or condensed ring, and R1、R2Respectively
It independently is alkyl, amino, imido grpup, deuterated object or phenyl ring；
A is electron attractive functional group, and B is supplied for electronic functional group.
A has the general formula structure shown in one of following：
Wherein,
B has structure shown in general formula (III) or general formula (IV)：
Wherein, B1、B2、B3It is each independently hydrogen atom, D-atom, alkyl, deuterated object, aromatic rings or condensed ring；
Z3、Z4、Z5、Z6、Z7、Z8It is each independently aromatic rings or condensed ring.
It is further preferred that the TADF materials that embodiments of the present invention are provided, have selected from one of following knot
Structure：
Embodiments of the present invention also provide the application of above-mentioned TADF materials in the devices.
Specifically, embodiments of the present invention provide a kind of device, and it includes above-mentioned TADF materials.
Preferably, the device is Organic Light Emitting Diode, Organic Thin Film Transistors (OFT), organic photovoltaic battery (OPV)
Or quantum dot organic diode (QLED), in the device, above-mentioned TADF materials are the luminescent material in device, hole transport
Material or electron transport material.
It is further preferred that in embodiments of the present invention also provide a kind of organic light emitting diode device, including：The
One electrode, the luminescent layer formed on the hole transport layer, is formed the hole transmission layer formed on the first electrode on the light-emitting layer
Electron transfer layer, and covering second electrode on the electron transport layer, and the luminescent layer, hole transmission layer or electronics pass
Defeated layer includes the TADF materials.
In terms of existing technologies, the TADF materials that embodiments of the present invention are provided have following technology outstanding
Effect：In traditional TADF OLED device, material of main part and an object TADF material containing there are one, but due to TADF photons
Scattering direction be random direction, only the light perpendicular to ito substrate direction has an opportunity to escape out device exterior, other directions
Photon by multiple reflections quench in device inside, influence device efficiency.In order to improve the luminous efficiency of OLED device, tradition
Way is exactly that one layer of light spe membrane will be attached outside OLED device, and this way not only increases production cost, but also does not have
Substance solves the problems, such as that OLED external light emission efficiencies are low.And using TADF materials provided by the present invention as OLED devices
Luminescent material the control of molecular transition dipole moment is being parallel to orientation substrate so that molecule is sent out using the flatness of anthracene structure
It is projected from ito substrate method to have more photons, therefore can have perpendicular to ito substrate in photon direction in photoreduction process
Effect avoids OLED device reduced performance.In addition, novel TADF materials provided by the present invention are triphenylamine-anthracene-thioxanthone
Object structure, hole transport and electron-transport extremely balance, thus are also beneficial to improve exciton balance in luminescent layer, reduce device
Efficiency is roll-offed.
Specific implementation mode
To make the object, technical solutions and advantages of the present invention clearer, below will to the embodiments of the present invention into
The detailed elaboration of row.However, it will be understood by those skilled in the art that in each embodiment of the present invention, in order to make reading
Person more fully understands the present invention and proposes many technical details.But even if without these technical details and based on following
The various changes and modifications of embodiment can also realize each claim technical solution claimed of the present invention.
Compound
Some specific embodiments of the present invention are related to a kind of TADF materials, with structure shown in general formula (I)：
Wherein, X1、X2It is each independently C atoms or Si atoms；Z1、Z2It is each independently unsubstituted or substituted five
First aromatic rings, hexa-atomic aromatic rings or condensed ring, and R1、R2It is each independently alkyl, amino, imido grpup, deuterated object or phenyl ring； A
For electron attractive functional group, B is supplied for electronic functional group.
In some specific embodiments of the present invention, A has the general formula structure shown in one of following：
Wherein,
B has structure shown in general formula (III) or general formula (IV)：
Wherein, B1、B2、B3It is each independently hydrogen atom, D-atom, alkyl, deuterated object, aromatic rings or condensed ring；
Z3、Z4、Z5、Z6、Z7、Z8It is each independently aromatic rings or condensed ring.
M1With selected from one of following structure：
In some specific embodiments of the present invention, TADF materials provided by the present invention have selected from one of following
Structure：
General synthetic routes
The preparation method of disclosed compound of present invention provided below.But present disclosure is not intended to be limited to institute herein
The method of narration it is any.Those skilled in the art can easily change described method or utilize different sides
Method prepares the one or more of disclosed compound.Following aspect is merely exemplary, and is not intended to limit in the disclosure
The range of appearance.Temperature, catalyst, concentration, reactant composition and other process conditions are changeable, and match for desired
Object is closed, present disclosure those skilled in the art can readily select suitable reactant and condition.
In CDCl on VarianLiquid State NMR instruments3Or DMS0-d6It is recorded with 400MHz in solution1H schemes
Spectrum, is recorded with 100MHz13C NMR spectras, chemical shift is with reference to remaining deuterated (protiated) solvent.If CDCl3It is used as
Solvent then uses tetramethylsilane (δ=0.00ppm) to be recorded as internal standard1H NMR spectras；Using DMSO-d6(δ=77.00
Ppm) internal standard is used as to record13C NMR spectras.If by H2O (δ=3.33ppm) is used as solvent, then uses remaining H2O (δ=
3.33ppm) internal standard is used as to record1H NMR spectras；Using DMSO-d6(δ=39.52ppm) is recorded as internal standard13C NMR figures
Spectrum.It is explained using following abbreviations (or combinations thereof)1The multiplicity of H NMR：S=substances, d=is dual, and t=is triple, q=tetra-
Weight, five weights of P=, m=is multiple, br=wide.
The versatility synthetic route of compound disclosed in the present invention is as follows：
Synthesize example：
(1) material number L1
9,10-, bis- bromo anthracenes, 4- (9H- carbazoles -9-) phenyl boric acid/4- (1,3,5- tricyano benzene)-are put into there-necked flask
Phenyl boric acid, solvent 50ml install mechanical agitation stick, are passed through nitrogen 10min, and catalyst PdCl is added under the protection of nitrogen2
(dppf) 0.25mol%-3mol%, 2M aqueous slkali 0.018mol, are heated to reflux, and react 4 hours.It is filtered after reaction, toluene
It washes, ethyl alcohol is washed.The powder L1 of 99% or more purity, product yield 71% are obtained after dimethylbenzene recrystallization.
Using CDCL3As solvent, tetramethylsilane (δ=0.00ppm) is noted down as internal standard1HNMR collection of illustrative plates.
1H NMR(400MHZ,DMSO-d6)：
7.0ppm(2H,t),7.08ppm(2H,t),7.3-7.32ppm(6H,p),7.40ppm(2H,d),7.54-
7.55ppm(6H,d),7.5ppm(2H,d ),8.10ppm(2H,s),7.67pp(4H,p)。
(2) material number L2
9,10-, bis- bromo anthracenes, 4- (3,6- diphenyl -9H- carbazoles -9-) phenyl boric acid/4- (1,3,5- are put into there-necked flask
Tricyano benzene)-phenyl boric acid, solvent 50ml installs mechanical agitation stick, is passed through nitrogen 10min, be added under the protection of nitrogen
Catalyst PdCl2 (dppf) 0.25mol%-3mol%, 2M aqueous slkali 0.018mol, is heated to reflux, and reacts 4 hours.After reaction
It filters, toluene is washed, and ethyl alcohol is washed.The powder L1 of 99% or more purity, product yield 65% are obtained after dimethylbenzene recrystallization.
Using CDCL3As solvent, tetramethylsilane (δ=0.00ppm) is noted down as internal standard1H NMR spectras.
1H NMR(400MHZ,DMSO-d6)：
7.22ppm(2H,m),7.3-7.32ppm(12H,m),7.46-7.54ppm(12H,q),7.67ppm(4H,p),
7.77ppm(2H,s),8.10pp m(2H,s)。
(3) material number L3
9,10-, bis- bromo anthracenes, 4- (3,6- methyl -9H- carbazoles -9-) phenyl boric acid/4- (1,3,5- tri- are put into there-necked flask
Cyano benzene)-phenyl boric acid, solvent 50ml installs mechanical agitation stick, is passed through nitrogen 10min, be added and urge under the protection of nitrogen
Agent PdCl2 (dppf) 0.25mol%-3mol%, 2M aqueous slkali 0.018mol, is heated to reflux, and reacts 4 hours.It is taken out after reaction
Filter, toluene are washed, and ethyl alcohol is washed.The powder L1 of 99% or more purity, product yield 51% are obtained after dimethylbenzene recrystallization.
Solvent is used as using CDCL3, tetramethylsilane (δ=0.00ppm) is noted down as internal standard1H NMR spectras.
1H NMR(400MHZ,DMSO-d6)：
2.35ppm(6H,s),6.88ppm
(2H,d),7.28-7.35ppm(10H,p),7.5ppm(2H,d),7.54ppm(4H,s),7.67ppm(4H,p),
8.10ppm(2H,s)。
(4) material number L4
9,10-, bis- bromo anthracenes, 4- (3,6- tertiary butyl -9H- carbazoles -9-) phenyl boric acid/4- (1,3,5- are put into there-necked flask
Tricyano benzene)-phenyl boric acid, solvent 50ml installs mechanical agitation stick, is passed through nitrogen 10min, be added under the protection of nitrogen
Catalyst PdCl2 (dppf) 0.25mol%-3mol%, 2M aqueous slkali 0.018mol, is heated to reflux, and reacts 4 hours.After reaction
It filters, toluene is washed, and ethyl alcohol is washed.The powder L1 of 99% or more purity, product yield 53% are obtained after dimethylbenzene recrystallization.
Using CDCL3As solvent, tetramethylsilane (δ=0.00ppm) is noted down as internal standard1H NMR spectras.
1H NMR(400MHZ,DMSO-d6)：
1.34ppm(18H,s),7.11ppm(2H,d),7.3-7.32ppm(8H,p),7.5ppm(4H,d),7.54ppm
(2H,s),7.58ppm(2Hs),7. 67ppm(4H,p),8.10ppm(2H,s)。
(5) material number L5
9,10-, bis- bromo anthracenes, 9- phenyl -9H- carbazyls -3- boric acid/4- (1,3,5- tricyanos are put into there-necked flask
Benzene)-phenyl boric acid, solvent 50ml installs mechanical agitation stick, is passed through nitrogen 10min, and catalyst is added under the protection of nitrogen
PdCl2 (dppf) 0.25mol%-3mol%, 2M aqueous slkali 0.018mol, is heated to reflux, and reacts 4 hours.It is filtered after reaction,
Toluene is washed, and ethyl alcohol is washed.The powder L1 of 99% or more purity, product yield 56% are obtained after dimethylbenzene recrystallization.
Using CDCL3As solvent, tetramethylsilane (δ=0.00ppm) is noted down as internal standard1H NMR spectras.
1H NMR(400MHZ,DMSO-d6)：
8.10ppm(2H,s),7.77ppm(1H,s),7.67PPM(4H,p),7.54-7.55ppm(5H,d),7.46ppm
(1H,d),7.4ppm(1H,d),7 .3-7.32ppm(10H,m),7.08(1H,t),7.0ppm(1H,t)。
(6) material number L6
9,10-, bis- bromo anthracenes, 6,9- diphenyl -9H- carbazyls -3- boric acid/4- (1,3,5- tri- cyanogen are put into there-necked flask
Base benzene)-phenyl boric acid, solvent 50ml installs mechanical agitation stick, is passed through nitrogen 10min, and catalyst is added under the protection of nitrogen
PdCl2 (dppf) 0.25mol%-3mol%, 2M aqueous slkali 0.018mol, is heated to reflux, and reacts 4 hours.It is filtered after reaction,
Toluene is washed, and ethyl alcohol is washed.The powder L1 of 99% or more purity, product yield 53% are obtained after dimethylbenzene recrystallization.
Using CDCL3As solvent, tetramethylsilane (δ=0.00ppm) is noted down as internal standard1H NMR spectras.
1H NMR(400MHZ,DMSO-d6)：
7.22-7.32ppm(15H,m),7.46-7.48ppm(4H,t),7.54ppm(4H,s),7.67ppm(4H,p)
7.77ppm(2H,s),8.10ppm( 2H,s)。
(7) material number L7
9,10-, bis- bromo anthracenes, 6- tertiary butyl -9- phenyl -9H- carbazoles -3- boric acid/4- (1,3,5- are put into there-necked flask
Tricyano benzene)-phenyl boric acid, solvent 50ml installs mechanical agitation stick, is passed through nitrogen 10min, be added under the protection of nitrogen
Catalyst PdCl2 (dppf) 0.25mol%-3mol%, 2M aqueous slkali 0.018mol, is heated to reflux, and reacts 4 hours.After reaction
It filters, toluene is washed, and ethyl alcohol is washed.The powder L1 of 99% or more purity, product yield 65% are obtained after dimethylbenzene recrystallization.
Solvent is used as using CDCL3, tetramethylsilane (δ=0.00ppm) is noted down as internal standard1H NMR spectras.
1H NMR(400MHZ,DMSO-d6)：
1.34ppm(9H,s),7.11ppm(1H,d),7.3-7.32ppm(12H,m),7.46ppm(1H,d),7.54-
7.58ppm(5H,d),7.67ppm( 4H,m),7.77ppm(1H,s),8.10ppm(2H,s)。
(8) material number L8
9,10-, bis- bromo anthracenes, 4- (9H- carbazoles -9-)-phenyl boric acid/4- (4- cyano benzene)-benzene boron are put into there-necked flask
Acid, solvent 50ml install mechanical agitation stick, are passed through nitrogen 10min, and catalyst PdCl2 is added under the protection of nitrogen
(dppf) 0.25mol%-3mol%, 2M aqueous slkali 0.018mol, are heated to reflux, and react 4 hours.It is filtered after reaction, toluene
It washes, ethyl alcohol is washed.The powder L1 of 99% or more purity, product yield 71% are obtained after dimethylbenzene recrystallization.
Using CDCL3As solvent, tetramethylsilane (δ=0.00ppm) is noted down as internal standard1H NMR spectras.
1H NMR(400MHZ,DMSO-d6)：
7.66-7.67ppm(6H,q),7.54-7.57ppm(8H,t),7.5ppm(2H,d),7.4ppm(2H,d),7.3-
7.32ppm(6H,m),7.0-7.08 ppm(4H,m)。
(9) material number L9
It is put into 9,10-, bis- bromo anthracenes in there-necked flask, 4- (9H- carbazoles -9-)-phenyl boric acid/2,4,6- tricyano phenyl boric acids,
Solvent 50ml installs mechanical agitation stick, is passed through nitrogen 10min, and catalyst PdCl2 (dppf) is added under the protection of nitrogen
0.25mol%-3mol%, 2M aqueous slkali 0.018mol, are heated to reflux, and react 4 hours.It is filtered after reaction, toluene is washed, ethyl alcohol
It washes.The powder L1 of 99% or more purity, product yield 71% are obtained after dimethylbenzene recrystallization.
Solvent is used as using CDCL3, tetramethylsilane (δ=0.00ppm) is noted down as internal standard1H NMR spectras.
1H NMR(400MHZ,DMSO-d6)：
7.0-7.08ppm(4H,m),7.3-7.32ppm(6H,q),7.4ppm(2H,d),7.5ppm(2H,d),7.55ppm
(2H,d),7.67ppm(4H,p ),8.10ppm(2H,s)。
(10) material number L10
9,10-, bis- bromo anthracenes, 4- (3,6- diphenyl -9H- carbazyls -9)-phenyl boric acid/2,4,6- are put into there-necked flask
Tricyano phenyl boric acid, solvent 50ml install mechanical agitation stick, are passed through nitrogen 10min, and catalyst is added under the protection of nitrogen
PdCl2 (dppf) 0.25mol%-3mol%, 2M aqueous slkali 0.018mol, is heated to reflux, and reacts 4 hours.It is filtered after reaction,
Toluene is washed, and ethyl alcohol is washed.The powder L1 of 99% or more purity, product yield 53% are obtained after dimethylbenzene recrystallization.
Solvent is used as using CDCL3, tetramethylsilane (δ=0.00ppm) is noted down as internal standard1H NMR spectras.
1H NMR(400MHZ,DMSO-d6)：
8.10ppm(2H,s),7.77ppm(2H,s),7.67ppm(4H,p),7.46-7.5ppm(8H,t),7.3-
7.32ppm(12H,p),7.22ppm(2H ,t)。
Optical physics information：
When studying the electronic structure of fluorescent small molecule compound, influences each other and be very important between electronics, density is general
Letter theory (DFT) has been widely used for studying pi-conjugated system, and the result of the compound using the DFT method research disclosure
It is more more accurate than other methods.To the geometry under the ground state for the compound molecule studied, cation state and cloudy particle state
The optimization of structure, using the method for DFT//B3LYP/6-31G (d), the trip lake geometry of the excitation state of these compounds uses
What the method for DFT//B3LYP/6-31G (d) obtained.It is general using density containing when on the basis of ground state and excitation state geometry
Letter theory (TDDFT) method calculates the Absorption and emission spectra of these compounds.By above-mentioned computational methods, can obtain
The various properties of studied compound, including ionization energy IP, electron affinity EA, Reorganization Energy λ, highest occupied molecular orbital HOMO, most
It is low to occupy track LUMO, energy gap Eg.
For organic luminescent device, injects to hole and electronics energy active balance and transmission is very important.Molecule
Ionization energy and electron affinity be injectability for assessing hole and electronics respectively.Following table, which lists, to be calculated
The vertical and Adiabatic ionization potential of studied compound, vertical and Adiabatic electron affinity, energy is extracted in hole and electronics extracts energy.It hangs down
Straight ionization energy IP (v) refers to the energy difference of cation and molecule under neutral molecule geometric configuration；Adiabatic ionization potential IP (A) is
Refer to the energy difference under neutral and cationic geometric configuration；It refers to molecule and sun under cationic geometric configuration that energy HEP is extracted in hole
The energy difference of ion；Vertical electron affinity EA (v) refers to the energy difference under neutral and anion geometric configuration；Electronics extracts
Energy EEP refers to the energy difference of molecule and anion under anion geometric configuration.Generally for, Small molecule organic materials, ionization
Can be smaller, the injection in hole is easier；And electron affinity is bigger, the injection of electronics is easier.
Usually, in terms of microcosmic angle, the transporting mechanism of charge can be described as from the process transmitted in organic film.Its
In, an electronics or hole are transferred to from a having electronic molecule on adjacent neutral molecule.It is theoretical according to Marcus, charge
Mobility can be expressed as：
Wherein, T represents temperature；V represents pre-exponential factor, is the Coupling matrix element between two kinds of particles；λ is Reorganization Energy；Kb
It is Boltzmann constant.Obviously, λ and V is to determine KetAn important factor for value.Usually, under amorphous state charge transfer range
It is limited, V values vary less.So the speed of mobility is mainly determined by the λ on index.λ is smaller, transmission speed
Rate is faster.In order to study conveniently, the influence of external environment can be ignored, what is mainly discussed is reorganization energy.
It is derived according to calculating, reorganization energy may finally be expressed as：
λhole=IP (v)-HEP
λelectron=EEP-EA (v)
The compound L 1-L11HOMO energy levels, the LUMO energy that are prepared in the specific embodiment of the invention are calculated in method as above
Grade, the Cloud Distribution and S1 energy levels and PL spectrum main peaks of HOMO and LUMO：
According to above-mentioned result of calculation, the advantages of the technical solution of the disclosure, being can be according to the practical need of OLED device
It asks, the HOMO/LUMO/S1 of entire molecule can be adjusted in turn by adjusting the type of the luxuriant and rich with fragrance substituent group in molecular structure and obtains
Preferable hole/electron injection ability/level-density parameter.For example, the HOMO=5.33eV of L1, LUMO=2.56eV, PL=
511nm is unfavorable for electron injection, and the photochromic inclined blue-green that shines, after carrying out phenyl substitution in carbazole functional group in L1
After forming L2 molecules so that the LUMO of L2 pulls down to LUMO=2.75eV, and PL=520nm does not influence the energy level of HOMO not only in this way
(being conducive to stop hole jump), and the LUMO of L2 is made to facilitate electron injection (energy level is more preferably matched with electron transfer layer),
Meanwhile PL=520nm is conducive to obtain more preferably pure green light material.
The second advantage of disclosed technique, be can by adjusting cyano in molecular structure quantity and its position into
And adjust the HOMO/LUMO/S1 energy levels of ideal molecule.For example, by by 1 on L1,3,5- tricyano benzene are adjusted to L8 points
After the MOLECULE DESIGN of the 4- cyano benzene of son, HOMO is kept approximately constant, and LUMO is increased to the 1.9eV of L8 by the 2.56eV of L1,
PL, to 464nm, while being conducive to keep the hole blocking ability of organic material in this way, is suitably adjusted by the 511NM blue shifts of L1
LUMO can and it is photochromic with PL.
The third advantage of disclosed technique, be can very simple MOLECULE DESIGN so that the disclosure material
Reach the bipolar nature of hole/electron-transport balance.Below in disclosed compound L1 and L5 carry out specifically
The technological merit that bright the technical program is brought.
From the hole recombination of calculating can and electron recombination can judge, for L1 molecules：[the holes electron recombination energy λ e- weight
Group energy λ h]=0.05eV, therefore, L1 molecules are that the bipolarity that a cavity transmission ability is slightly better than electron transport ability is organic
Material.Such molecule benefit is to be conducive to balance the transmission balance of hole/electronic carrier of OLED device, to carry
High OLED luminous efficiencies and service life.
For L5 molecules：[electron recombination energy λ e- hole recombination energy λ h] 0.14eV, therefore, L5 is an electron-transport energy
Power is more than the organic photoelectrical material of hole transport.The difference of the carrier transport ability of L1 and L5, key factor are direct with anthracene
Caused by the position of connected different carbazyls, the link position of the latter is more advantageous to the conjugation of pi-electron system, this is from L5
The spectrum of PL=540nm red shifts can be seen that.
Organic light emitting diode device
The specific implementation mode of the present invention also provides a kind of device, which includes the TADF materials in above-described embodiment,
The device is Organic Light Emitting Diode, OFT, OPV or QLED.
In some specific embodiments provided by the present invention, TADF materials of the invention are organic light emitting diode device
In luminescent material, hole mobile material or electron transport material.
In some specific embodiments of the present invention, the organic light emitting diode device provided includes：First electrode,
The hole transmission layer that is formed in first electrode, the luminescent layer formed on the hole transport layer, the electronics formed on the light-emitting layer pass
Defeated layer, and the second electrode of covering on the electron transport layer, and luminescent layer, hole transmission layer or electron transfer layer include this hair
TADF materials in bright.
Device prepares example：
Ito substrate is taken, the bottom emitting glass of 30mm*30mm sizes, there are four light-emitting zones, and the areas light-emitting area AA are
The light transmittance of 2mm*2mm, ito thin film are 90%@550nm, surface roughness Ra<1nm, ito film thickness are 1300A, and resistance per square is
10 ohms per squares.
To cleaning for ito substrate：It is first placed in the container for filling acetone soln, which is positioned over super
Sound wave cleaning machine is cleaned by ultrasonic, and scavenging period is 30 minutes, mainly dissolves the organic matter for being attached to the surfaces ITO
And removal；Then the ito substrate taking-up that cleaning finishes is placed on hot plate and carries out high temperature of 120 DEG C baking half an hour, mainly
It is the organic solvent and steam for removing ito substrate surface；Then the ito substrate that baking finishes UV-ZONE is quickly transferred to set
Standby middle carry out O3The surfaces ITO are difficult to the organic matter eliminated or foreign matter further use plasma treatment 15 by corona treatment
Minute, the ITO being disposed is quickly transferred in OLED evaporated devices film forming room.
Prepare before OLED vapor depositions：Clean processing is carried out to OLED evaporated devices first, wiping film forming room is carried out using IPA
Cavity inner wall ensures that entire film forming cavity does not have foreign matter or dust.Then, by equipped with OLED organic materials crucible and equipped with gold
The crucible for belonging to aluminum shot is placed sequentially on organic evaporating source and inorganic evaporation source position.Cavity is closed, just vacuumize and take out
High vacuum step so that vapor deposition degree reaches 10E-7Torr. inside OLED evaporated devices
OLED evaporation film-formings：OLED organic evaporatings source is opened, 100 DEG C of preheatings, preheating time are carried out to OLED organic materials
It is 15 minutes, ensures further to remove the steam in OLED organic materials.Then the organic material that needs are deposited is carried out quick
Heating heat treatment, and opens the baffle above evaporation source, until the evaporation source of the material has organic material to run out of, while crystal oscillator
It when piece detector detects evaporation rate, is then slowly heated up, increasing extent of temperature is 1-5 DEG C, until evaporation rate is stablized
At 1A/ seconds, the baffle immediately below mask plate plate is opened, OLED film forming is carried out, when computer end observes the organic film on ito substrate
When reaching default film thickness, baffle right over mask plate baffle and evaporation source is closed, the evaporation source heater of the organic material is closed.
The evaporation process of other organic materials and cathodic metal material is as described above.
OLED encapsulates flow：The cleaning treatment mode of the cap of 20mm*20mm such as ito substrate pretreatment mode.Clear
The clean cap extension surrounding finished carries out the coating of UV glue materials or then the cap for having put UV glue materials is transferred to very by dispensing
It is vacuum abutted with the ito substrate progress of film forming OLED organic films in empty abutted equipment, then, it is transferred in UV solidification cavitys, makes
Photocuring is carried out with the ultraviolet light of 365nm wave bands.The ITO devices of photocuring, it is also necessary to the rear heat treatment of 80 DEG C of half an hour is carried out,
So that UV glue materials are fully cured.
Device example：
The multilayer organic light emitting diode device of ITO/HIL/HTL/ light orientations luminescent layer/ETL/EIL/ cathodes presented below
Example.The example is not to be taken as limitation of the invention, and the technical advantage and device of the present invention are understood in order to facilitate technical staff
Part principle, the example in the present invention is illustrated with simplest device architecture.
Device architecture：
ITO/MoO3(10nm)/TAPC(30nm)/mCP：L, 4wt%, 30nm/TPBi (30nm)/LiF (1nm)/Al.
Wherein, using MoO3As hole injection layer, using TAPC as hole transmission layer, using mCP as main body material
Material, L is as guest materials, and using TPBI as electron transfer layer and hole barrier layer material, LiF is as electron injecting layer material
Material, Al is as cathode.
The chemical structural formula of part organic material is as follows：
Due to triplet T1=2.74eV, the CBP of the triplet T1=2.87eV, TPBi of TACP, three lines
State energy level is respectively the triplet that 2.56eV is above L1/L2/L3, and the singlet energy level of L1/L2/L3 is again less than above-mentioned
The singlet energy level of material.Therefore, the exciton of luminescent layer can be limited in luminescent layer by hole transmission layer and electron transfer layer.
In order to compare the technical advantage of device provided by the present invention, comparison of design device architecture ITO/HIL/HTL/CBP：
4CZTPN-Ph/ETL/EIL/ cathodes (number R1).Comparative device R1 is a traditional TADF device architecture, contains single master
Object doping system.
The partial properties of 1. device 1 of the present invention of table and parametric device R1 compare
| Device number | Maximum external quantum efficiency EQE | Efficiency roll-off * |
| 1(L2) | 6.2% | 10.1% |
| 2(L7) | 7.1% | 9.8% |
| 3(L9) | 6.1% | 14.2% |
* efficiency roll-off this is defined herein as 0.1mA/cm2When efficiency to 100mA/cm2When performance change rate.
As shown in Table 1, the OLED device performance of disclosed technique is roll-offed all smaller, and maximum EQE>5%.
Embodiment of the material of the technology of the disclosure illustrated below as material of main part and guest materials.
Using L2 and L8 as illustrating：
ITO/MoO3(10nm)/TAPC(30nm)/TCTA(10nm)/L8:L2,4wt%, 30nm/TPBi (30nm)/LiF
(1nm)/Al, device number 4
The partial properties of 2. device 4 of table compare
| Device number | Maximum external quantum efficiency EQE | Efficiency roll-off * |
| 4 | 7.3% | 11.1% |
| 1(L2) | 6.2% | 10.1% |
* efficiency roll-off, performance change rate when efficiency when this is defined herein as 0.1mA/cm2 is to 100mA/cm2.
As shown in Table 2, the luminous efficiency of device 4 is higher than the luminous efficiency of device 1, this is the material of main part in device 4
L8 is an ambipolar material of main part, and the CBP in device 1 is the material of main part in a biography hole.
It will be understood by those skilled in the art that the respective embodiments described above are to realize specific embodiments of the present invention,
And in practical applications, can to it, various changes can be made in the form and details, without departing from the spirit and scope of the present invention.
Claims (8)
1. a kind of TADF materials, which is characterized in that have structure shown in general formula (I)：
Wherein,
X1、X2It is each independently C atoms or Si atoms；
Z1、Z2It is each independently unsubstituted or substituted 5-membered aromatic ring, hexa-atomic aromatic rings or condensed ring, and R1、R2It is respectively independent
Ground is alkyl, amino, imido grpup, deuterated object or phenyl ring；
A has the general formula structure shown in one of following：
Wherein,
B has structure shown in general formula (III) or general formula (IV)：
Wherein,
B1、B2、B3It is each independently hydrogen atom, D-atom, alkyl, deuterated object, aromatic rings or condensed ring；
Z3、Z4、Z5、Z6、Z7、Z8It is each independently aromatic rings or condensed ring.
2. TADF materials according to claim 1, which is characterized in that M1With selected from one of following structure：
3. TADF materials according to claim 1, which is characterized in that have selected from one of following structure：
4. the application of TADF materials in the devices described in any one of claims 1 to 3.
5. a kind of device, which is characterized in that include the TADF materials described in any one of claims 1 to 3.
6. device according to claim 5, which is characterized in that the device is Organic Light Emitting Diode, polycrystalline organic thin film
Body pipe, organic photovoltaic battery or quantum dot organic diode.
7. device according to claim 6, which is characterized in that the TADF materials be the device in luminescent material,
Hole mobile material or electron transport material.
8. a kind of organic light emitting diode device, which is characterized in that include：First electrode is on the first electrode formed
Hole transmission layer, the luminescent layer formed on the hole transport layer, the electron transfer layer formed on the light-emitting layer, and
The second electrode of covering on the electron transport layer, and the luminescent layer, hole transmission layer or electron transfer layer include described
TADF materials.
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109369652A (en) * | 2018-11-15 | 2019-02-22 | 武汉华星光电半导体显示技术有限公司 | A kind of blue light thermal activation delayed fluorescence material and its application |
| CN111303009A (en) * | 2018-12-12 | 2020-06-19 | 华中科技大学 | Anthracene-based deep blue light organic electroluminescent material with high efficiency and low roll-off |
| WO2022039365A1 (en) * | 2020-08-21 | 2022-02-24 | 주식회사 엘지화학 | Organic light-emitting device comprising organic compound |
| CN114561212A (en) * | 2020-11-27 | 2022-05-31 | 三星显示有限公司 | Quantum dot-containing material, preparation method thereof, composition and light-emitting device |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100530741C (en) * | 2003-02-19 | 2009-08-19 | 乐金显示有限公司 | Organic electroluminescent device and method for fabricating the same |
| TW200936567A (en) * | 2008-02-08 | 2009-09-01 | Toyo Ink Mfg Co | Compound having carbazolyl group and use thereof |
| KR20100119077A (en) * | 2009-04-30 | 2010-11-09 | 주식회사 엘지화학 | New compounds and organic electronic device using the same |
| KR20160123508A (en) * | 2015-04-16 | 2016-10-26 | 에스에프씨 주식회사 | An electroluminescent compound and an electroluminescent device comprising the same |
-
2018
- 2018-02-07 CN CN201810123867.4A patent/CN108299283A/en not_active Withdrawn
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100530741C (en) * | 2003-02-19 | 2009-08-19 | 乐金显示有限公司 | Organic electroluminescent device and method for fabricating the same |
| TW200936567A (en) * | 2008-02-08 | 2009-09-01 | Toyo Ink Mfg Co | Compound having carbazolyl group and use thereof |
| KR20100119077A (en) * | 2009-04-30 | 2010-11-09 | 주식회사 엘지화학 | New compounds and organic electronic device using the same |
| KR20160123508A (en) * | 2015-04-16 | 2016-10-26 | 에스에프씨 주식회사 | An electroluminescent compound and an electroluminescent device comprising the same |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109369652A (en) * | 2018-11-15 | 2019-02-22 | 武汉华星光电半导体显示技术有限公司 | A kind of blue light thermal activation delayed fluorescence material and its application |
| CN111303009A (en) * | 2018-12-12 | 2020-06-19 | 华中科技大学 | Anthracene-based deep blue light organic electroluminescent material with high efficiency and low roll-off |
| CN111303009B (en) * | 2018-12-12 | 2022-02-15 | 华中科技大学 | Anthracene-based deep blue light organic electroluminescent material with high efficiency and low roll-off |
| WO2022039365A1 (en) * | 2020-08-21 | 2022-02-24 | 주식회사 엘지화학 | Organic light-emitting device comprising organic compound |
| CN114561212A (en) * | 2020-11-27 | 2022-05-31 | 三星显示有限公司 | Quantum dot-containing material, preparation method thereof, composition and light-emitting device |
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