CN105742519B - A kind of electroluminescent device - Google Patents
A kind of electroluminescent device Download PDFInfo
- Publication number
- CN105742519B CN105742519B CN201610114326.6A CN201610114326A CN105742519B CN 105742519 B CN105742519 B CN 105742519B CN 201610114326 A CN201610114326 A CN 201610114326A CN 105742519 B CN105742519 B CN 105742519B
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- Prior art keywords
- semiconducting materials
- organic semiconducting
- main part
- organic
- luminescent layer
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- 239000000463 material Substances 0.000 claims abstract description 72
- 239000004065 semiconductor Substances 0.000 claims abstract description 68
- 239000000758 substrate Substances 0.000 claims abstract description 7
- 239000000203 mixture Substances 0.000 claims abstract description 6
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 claims description 14
- 229910052741 iridium Inorganic materials 0.000 claims description 14
- GKOZUEZYRPOHIO-UHFFFAOYSA-N iridium atom Chemical compound [Ir] GKOZUEZYRPOHIO-UHFFFAOYSA-N 0.000 claims description 14
- -1 4,6- difluorophenyl Chemical group 0.000 claims description 9
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 claims description 9
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 6
- 229910052782 aluminium Inorganic materials 0.000 claims description 6
- 239000004411 aluminium Substances 0.000 claims description 6
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 6
- 150000003222 pyridines Chemical class 0.000 claims description 4
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 claims description 3
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 claims description 3
- 239000010405 anode material Substances 0.000 claims description 3
- 229910052796 boron Inorganic materials 0.000 claims description 3
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 claims description 3
- 229910052737 gold Inorganic materials 0.000 claims description 3
- 239000010931 gold Substances 0.000 claims description 3
- 229910052759 nickel Inorganic materials 0.000 claims description 3
- 229910052709 silver Inorganic materials 0.000 claims description 3
- 239000004332 silver Substances 0.000 claims description 3
- 125000003831 tetrazolyl group Chemical group 0.000 claims description 3
- YVTHLONGBIQYBO-UHFFFAOYSA-N zinc indium(3+) oxygen(2-) Chemical compound [O--].[Zn++].[In+3] YVTHLONGBIQYBO-UHFFFAOYSA-N 0.000 claims description 3
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 claims 2
- 239000011787 zinc oxide Substances 0.000 claims 1
- 230000005540 biological transmission Effects 0.000 abstract description 8
- 238000000034 method Methods 0.000 abstract description 8
- 230000008569 process Effects 0.000 abstract description 7
- 238000004020 luminiscence type Methods 0.000 abstract description 4
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 42
- 229910052757 nitrogen Inorganic materials 0.000 description 39
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 38
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 32
- 239000010410 layer Substances 0.000 description 21
- TXCDCPKCNAJMEE-UHFFFAOYSA-N dibenzofuran Chemical compound C1=CC=C2C3=CC=CC=C3OC2=C1 TXCDCPKCNAJMEE-UHFFFAOYSA-N 0.000 description 18
- 239000000243 solution Substances 0.000 description 18
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 17
- 229910052763 palladium Inorganic materials 0.000 description 16
- 238000012360 testing method Methods 0.000 description 16
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 15
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N Aniline Chemical compound NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 description 14
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 14
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 12
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 10
- 229940126062 Compound A Drugs 0.000 description 10
- NLDMNSXOCDLTTB-UHFFFAOYSA-N Heterophylliin A Natural products O1C2COC(=O)C3=CC(O)=C(O)C(O)=C3C3=C(O)C(O)=C(O)C=C3C(=O)OC2C(OC(=O)C=2C=C(O)C(O)=C(O)C=2)C(O)C1OC(=O)C1=CC(O)=C(O)C(O)=C1 NLDMNSXOCDLTTB-UHFFFAOYSA-N 0.000 description 10
- 238000010521 absorption reaction Methods 0.000 description 10
- 238000000862 absorption spectrum Methods 0.000 description 10
- 239000007789 gas Substances 0.000 description 10
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 10
- 238000001228 spectrum Methods 0.000 description 10
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 9
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 9
- 239000005864 Sulphur Substances 0.000 description 9
- 238000002360 preparation method Methods 0.000 description 9
- 238000005859 coupling reaction Methods 0.000 description 8
- 238000006243 chemical reaction Methods 0.000 description 7
- IVDFJHOHABJVEH-UHFFFAOYSA-N HOCMe2CMe2OH Natural products CC(C)(O)C(C)(C)O IVDFJHOHABJVEH-UHFFFAOYSA-N 0.000 description 6
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 6
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 6
- 238000004458 analytical method Methods 0.000 description 6
- 239000003054 catalyst Substances 0.000 description 6
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- 238000001704 evaporation Methods 0.000 description 6
- 230000008020 evaporation Effects 0.000 description 6
- 239000003446 ligand Substances 0.000 description 6
- 239000007788 liquid Substances 0.000 description 6
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 description 5
- 229910052786 argon Inorganic materials 0.000 description 5
- 230000000694 effects Effects 0.000 description 5
- 238000002347 injection Methods 0.000 description 5
- 239000007924 injection Substances 0.000 description 5
- MILUBEOXRNEUHS-UHFFFAOYSA-N iridium(3+) Chemical compound [Ir+3] MILUBEOXRNEUHS-UHFFFAOYSA-N 0.000 description 5
- 229920000642 polymer Polymers 0.000 description 5
- 229910000027 potassium carbonate Inorganic materials 0.000 description 5
- 239000000843 powder Substances 0.000 description 5
- 238000000746 purification Methods 0.000 description 5
- 230000004580 weight loss Effects 0.000 description 5
- IGIIERRCOSRSLT-UHFFFAOYSA-N C1=CC=CC=2OC3=C(C21)C=CC=C3.[S] Chemical compound C1=CC=CC=2OC3=C(C21)C=CC=C3.[S] IGIIERRCOSRSLT-UHFFFAOYSA-N 0.000 description 4
- 241001062009 Indigofera Species 0.000 description 4
- 238000001816 cooling Methods 0.000 description 4
- 238000005401 electroluminescence Methods 0.000 description 4
- PQXKHYXIUOZZFA-UHFFFAOYSA-M lithium fluoride Chemical compound [Li+].[F-] PQXKHYXIUOZZFA-UHFFFAOYSA-M 0.000 description 4
- 239000003960 organic solvent Substances 0.000 description 4
- 150000003233 pyrroles Chemical class 0.000 description 4
- 239000007787 solid Substances 0.000 description 4
- 238000000638 solvent extraction Methods 0.000 description 4
- 0 CC(C)(C)c(cc1)cc(SC2C3)c1C2=CC=C3c(cc1)ccc1N(c(cc1)ccc1O*)c1cc(C2(C)C)c2cc1 Chemical compound CC(C)(C)c(cc1)cc(SC2C3)c1C2=CC=C3c(cc1)ccc1N(c(cc1)ccc1O*)c1cc(C2(C)C)c2cc1 0.000 description 3
- 238000011049 filling Methods 0.000 description 3
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Natural products C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 3
- VAMFXQBUQXONLZ-UHFFFAOYSA-N n-alpha-eicosene Natural products CCCCCCCCCCCCCCCCCCC=C VAMFXQBUQXONLZ-UHFFFAOYSA-N 0.000 description 3
- CBFCDTFDPHXCNY-UHFFFAOYSA-N octyldodecane Natural products CCCCCCCCCCCCCCCCCCCC CBFCDTFDPHXCNY-UHFFFAOYSA-N 0.000 description 3
- PIBWKRNGBLPSSY-UHFFFAOYSA-L palladium(II) chloride Chemical compound Cl[Pd]Cl PIBWKRNGBLPSSY-UHFFFAOYSA-L 0.000 description 3
- 238000010926 purge Methods 0.000 description 3
- 230000027756 respiratory electron transport chain Effects 0.000 description 3
- IJDNQMDRQITEOD-UHFFFAOYSA-N sec-butylidene Natural products CCCC IJDNQMDRQITEOD-UHFFFAOYSA-N 0.000 description 3
- 229910000029 sodium carbonate Inorganic materials 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- QBBOCSNLIYAOFH-UHFFFAOYSA-N COC1=C(C(=CC=C1)OC)C1=CC=CC=C1.[P] Chemical group COC1=C(C(=CC=C1)OC)C1=CC=CC=C1.[P] QBBOCSNLIYAOFH-UHFFFAOYSA-N 0.000 description 2
- GSNUFIFRDBKVIE-UHFFFAOYSA-N DMF Natural products CC1=CC=C(C)O1 GSNUFIFRDBKVIE-UHFFFAOYSA-N 0.000 description 2
- 206010013786 Dry skin Diseases 0.000 description 2
- XYFCBTPGUUZFHI-UHFFFAOYSA-N Phosphine Chemical compound P XYFCBTPGUUZFHI-UHFFFAOYSA-N 0.000 description 2
- YTPLMLYBLZKORZ-UHFFFAOYSA-N Thiophene Chemical compound C=1C=CSC=1 YTPLMLYBLZKORZ-UHFFFAOYSA-N 0.000 description 2
- JYMITAMFTJDTAE-UHFFFAOYSA-N aluminum zinc oxygen(2-) Chemical compound [O-2].[Al+3].[Zn+2] JYMITAMFTJDTAE-UHFFFAOYSA-N 0.000 description 2
- 239000012298 atmosphere Substances 0.000 description 2
- 238000007599 discharging Methods 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 230000005611 electricity Effects 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 239000000284 extract Substances 0.000 description 2
- 239000008246 gaseous mixture Substances 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- UHOVQNZJYSORNB-UHFFFAOYSA-N monobenzene Natural products C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 2
- 239000000178 monomer Substances 0.000 description 2
- 229940094933 n-dodecane Drugs 0.000 description 2
- 230000001376 precipitating effect Effects 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 229910000030 sodium bicarbonate Inorganic materials 0.000 description 2
- 235000017557 sodium bicarbonate Nutrition 0.000 description 2
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 2
- TUQOTMZNTHZOKS-UHFFFAOYSA-N tributylphosphine Chemical compound CCCCP(CCCC)CCCC TUQOTMZNTHZOKS-UHFFFAOYSA-N 0.000 description 2
- RIOQSEWOXXDEQQ-UHFFFAOYSA-N triphenylphosphine Chemical compound C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 RIOQSEWOXXDEQQ-UHFFFAOYSA-N 0.000 description 2
- COIOYMYWGDAQPM-UHFFFAOYSA-N tris(2-methylphenyl)phosphane Chemical compound CC1=CC=CC=C1P(C=1C(=CC=CC=1)C)C1=CC=CC=C1C COIOYMYWGDAQPM-UHFFFAOYSA-N 0.000 description 2
- DHDHJYNTEFLIHY-UHFFFAOYSA-N 4,7-diphenyl-1,10-phenanthroline Chemical class C1=CC=CC=C1C1=CC=NC2=C1C=CC1=C(C=3C=CC=CC=3)C=CN=C21 DHDHJYNTEFLIHY-UHFFFAOYSA-N 0.000 description 1
- DADZIMNFQANSAN-UHFFFAOYSA-N C(C1=CC=CC=C1)CC(C)=O.[Ar] Chemical compound C(C1=CC=CC=C1)CC(C)=O.[Ar] DADZIMNFQANSAN-UHFFFAOYSA-N 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- 241000790917 Dioxys <bee> Species 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- 238000006069 Suzuki reaction reaction Methods 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 150000001335 aliphatic alkanes Chemical class 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 150000004696 coordination complex Chemical class 0.000 description 1
- 238000012937 correction Methods 0.000 description 1
- 238000006392 deoxygenation reaction Methods 0.000 description 1
- WMKGGPCROCCUDY-PHEQNACWSA-N dibenzylideneacetone Chemical compound C=1C=CC=CC=1\C=C\C(=O)\C=C\C1=CC=CC=C1 WMKGGPCROCCUDY-PHEQNACWSA-N 0.000 description 1
- 230000005284 excitation Effects 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 238000005286 illumination Methods 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- MRNHPUHPBOKKQT-UHFFFAOYSA-N indium;tin;hydrate Chemical compound O.[In].[Sn] MRNHPUHPBOKKQT-UHFFFAOYSA-N 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012544 monitoring process Methods 0.000 description 1
- 239000012044 organic layer Substances 0.000 description 1
- 239000011368 organic material Substances 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 229910000073 phosphorus hydride Inorganic materials 0.000 description 1
- SIOXPEMLGUPBBT-UHFFFAOYSA-N picolinic acid Chemical compound OC(=O)C1=CC=CC=N1 SIOXPEMLGUPBBT-UHFFFAOYSA-N 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 230000004044 response Effects 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 238000002207 thermal evaporation Methods 0.000 description 1
- 229930192474 thiophene Natural products 0.000 description 1
- 230000001052 transient effect Effects 0.000 description 1
- 238000001771 vacuum deposition Methods 0.000 description 1
Classifications
-
- 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
- H10K85/10—Organic polymers or oligomers
- H10K85/111—Organic polymers or oligomers comprising aromatic, heteroaromatic, or aryl chains, e.g. polyaniline, polyphenylene or polyphenylene vinylene
- H10K85/113—Heteroaromatic compounds comprising sulfur or selene, e.g. polythiophene
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G61/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
- C08G61/12—Macromolecular compounds containing atoms other than carbon in the main chain of the macromolecule
- C08G61/122—Macromolecular compounds containing atoms other than carbon in the main chain of the macromolecule derived from five- or six-membered heterocyclic compounds, other than imides
- C08G61/123—Macromolecular compounds containing atoms other than carbon in the main chain of the macromolecule derived from five- or six-membered heterocyclic compounds, other than imides derived from five-membered heterocyclic compounds
- C08G61/126—Macromolecular compounds containing atoms other than carbon in the main chain of the macromolecule derived from five- or six-membered heterocyclic compounds, other than imides derived from five-membered heterocyclic compounds with a five-membered ring containing one sulfur atom in the ring
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G2261/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
- C08G2261/10—Definition of the polymer structure
- C08G2261/14—Side-groups
- C08G2261/142—Side-chains containing oxygen
- C08G2261/1424—Side-chains containing oxygen containing ether groups, including alkoxy
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G2261/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
- C08G2261/10—Definition of the polymer structure
- C08G2261/22—Molecular weight
- C08G2261/228—Polymers, i.e. more than 10 repeat units
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G2261/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
- C08G2261/30—Monomer units or repeat units incorporating structural elements in the main chain
- C08G2261/32—Monomer units or repeat units incorporating structural elements in the main chain incorporating heteroaromatic structural elements in the main chain
- C08G2261/324—Monomer units or repeat units incorporating structural elements in the main chain incorporating heteroaromatic structural elements in the main chain condensed
- C08G2261/3243—Monomer units or repeat units incorporating structural elements in the main chain incorporating heteroaromatic structural elements in the main chain condensed containing one or more sulfur atoms as the only heteroatom, e.g. benzothiophene
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G2261/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
- C08G2261/40—Polymerisation processes
- C08G2261/41—Organometallic coupling reactions
- C08G2261/411—Suzuki reactions
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G2261/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
- C08G2261/50—Physical properties
- C08G2261/51—Charge transport
- C08G2261/512—Hole transport
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G2261/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
- C08G2261/50—Physical properties
- C08G2261/51—Charge transport
- C08G2261/514—Electron transport
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G2261/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
- C08G2261/50—Physical properties
- C08G2261/52—Luminescence
- C08G2261/524—Luminescence phosphorescent
- C08G2261/5242—Luminescence phosphorescent electrophosphorescent
-
- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K2101/00—Properties of the organic materials covered by group H10K85/00
- H10K2101/10—Triplet emission
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- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Physics & Mathematics (AREA)
- Optics & Photonics (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Electroluminescent Light Sources (AREA)
Abstract
The invention provides the substrate with anode, luminescent layer and the cathode layer that a kind of electroluminescent device includes stacking gradually, the luminescent layer is the mixture of material of main part and guest materials, wherein material of main part organic semiconducting materials as follows：Wherein, R is C1~C20Alkyl, n is 10~100 integer, the present invention provides organic semiconducting materials has hole transporting property and electronic transport property simultaneously, balance the transmission of the organic semiconducting materials hole and electronics in luminescent layer, also there is higher triplet, triplet is more than 2.75eV, effectively prevents that energy returns to material of main part in luminescence process, greatly improves luminous efficiency.
Description
It Application No. 2013100383697, the applying date is on 01 31st, 2013 that the application, which is, invention and created name for "
A kind of divisional application of the application of organic semiconducting materials, preparation method and electroluminescent device ".
Technical field
The invention belongs to field of photovoltaic materials, and in particular to a kind of electroluminescent device.
Background technology
Organic electroluminescence device has low driving voltage, fast response time, angular field of view wide and can be by chemistry knot
Structure fine setting, which changes luminescent properties, makes rich color, easily realizes the advantages of high resolution, lightweight, large-area flat-plate are shown, quilt
" 21 century flat panel display " is described as, the focus as the subjects such as material, information, physics and flat display field research.Not
Efficiently being commercialized Organic Light Emitting Diode will be likely to containing organic metal phosphor, because they can be by singlet
Captured with triplet excitons, so as to realize 100% internal quantum efficiency.However, due to the excitation state of transient metal complex
Exciton lifetime is relatively long, causes unwanted triplet state-triplet state (T1-T1) be quenched in device real work.In order to overcome
Triplet emission thing is often doped in organic host material by this problem, researchers.
In recent years, green and red phosphorescent OLED show gratifying electroluminescent efficiency.And it is efficient blue
But seldom, main cause is a lack of while having preferable carrier transmission performance and higher triplet color phosphorescent devices
(ET) material of main part.
The content of the invention
To solve the above problems, the invention provides a kind of organic semiconducting materials, the organic semiconducting materials have sky
Cave transport property and electronic transport property, balance the transmission of the semi-conducting material hole and electronics in luminescent layer, also have
Higher triplet, triplet is more than 2.75eV, effectively prevents that energy returns to material of main part in luminescence process,
Luminous efficiency is greatly improved, organic semiconducting materials of the present invention provide new may be selected for bipolarity blue emitting phosphor material of main part
Kind.Present invention also offers the preparation method of the organic semiconducting materials, and the electricity comprising the organic semiconducting materials
Electroluminescence device.
On the one hand, the invention provides a kind of organic semiconducting materials, the chemical formula of the organic semiconducting materials is as follows
It is shown：
Wherein, R is C1~C20Alkyl, n for 10~100 it is whole
Number.
Second aspect, the invention provides a kind of preparation method of organic semiconducting materials, comprises the following steps：
Compound A is provided：Positive compound B：
Wherein, R is C1~C20Alkyl；Under an inert atmosphere, compound A and compound B are added according to mol ratio for 1: 1~1: 1.2
Add in the organic solvent containing catalyst and aqueous slkali, Suzuki coupled reactions carried out at 70~130 DEG C 12~96 hours,
The catalyst is organic palladium or is the mixture of organic palladium and organophosphor ligand, and obtain that following structural formula represents organic partly leads
Body material P：
Wherein, n is 10~100 integer.
Preferably, the preparation method of the organic semiconducting materials also includes organic semiconducting materials P progress separation is pure
The step of change, the purification procedures are as follows：Carried out to the compound A and compound B molten after Suzuki coupled reactions
Methanol precipitating is added in liquid and is filtered, the solid being filtrated to get is stripped with methanol and n-hexane successively, will be by extracting
Evaporation solvent obtains organic semiconducting materials P after purification after solid chloroform afterwards, collection chloroformic solution.
Preferably, at least one of the organic solvent in toluene, DMF, tetrahydrofuran.
Preferably, at least one of the aqueous slkali in sodium carbonate liquor, solution of potassium carbonate and sodium bicarbonate solution,
Solute and compound A mol ratio in the aqueous slkali are 20: 1~50: 1.
Preferably, the organic palladium is bis-triphenylphosphipalladium palladium dichloride, tetra-triphenylphosphine palladium, palladium or three dibenzylidenes
The palladium of acetone two, the organophosphorus ligand is tri-butyl phosphine, tri-o-tolyl phosphine or 2- dicyclohexyls phosphorus -2 ', 6 '-dimethoxy
Biphenyl, the organic palladium is 1: 4~1: 8 with the mol ratio of the organophosphorus ligand.
Preferably, the organic palladium in the catalyst and the mol ratio of the compound A are 1: 20~1: 100.
The third aspect, the invention provides a kind of electroluminescent device, including stack gradually the substrate with anode, hair
Photosphere and cathode layer, the luminescent layer are the mixture of material of main part and guest materials, and wherein material of main part is as follows
Organic semiconducting materials：Wherein, R is C1~C20Alkyl, n be 10~100
Integer, guest materials be three [1- phenyl isoquinolin quinolines-C2, N] iridium, double (4,6- difluorophenyl pyridinato-N, C2) pyridinecarboxylics close
Iridium, [two (2 ', 4 '-difluorophenyl) pyridines] [four (1- pyrazolyls) boron] close iridium or [two (2 ', 4 '-difluorophenyl) pyridines]
(tetrazolium pyridine) closes iridium.
Preferably, the material of main part and the mass percent of the guest materials are 5%~15%.
Preferably, anode material is indium zinc oxide or zinc oxide aluminum, and negative electrode is metallic aluminium, silver, gold or nickel.
The invention provides a kind of organic semiconducting materials, preparation method and electroluminescent device, with following beneficial effect
Really：There is hole transporting property and electronic transport property simultaneously, make organic semiconducting materials hole and electronics in luminescent layer
Transmission balance, also with higher triplet, triplet is more than 2.75eV, effectively prevents energy in luminescence process
Material of main part is returned to, luminous efficiency is greatly improved.The material employs better simply synthetic route, reduces technological process,
Raw material are cheap and easy to get, and manufacturing cost is reduced.
Brief description of the drawings
Fig. 1 is obtained organic semiconducting materials organic electroluminescence device made from material of main part using in embodiment 1
Structural representation；
Fig. 2 is the thermogravimetic analysis (TGA) figure of obtained organic semiconducting materials in embodiment 1.
Embodiment
The content of patent, this is further illustrated below by specific example and legend for a better understanding of the present invention
The technology case of invention, specifically includes material and prepares and device preparation, but these embodiments are not intended to limit the present invention, wherein monomer
A is commercially obtained, method disclosed in monomer B reference literatures (J.AM.CHEM.SOC.9VOL.125, NO.44,2003)
Synthesis is obtained.
The invention provides a kind of organic semiconducting materials, the chemical formula of the organic semiconducting materials is as follows：
Wherein, R is C1~C20Alkyl, n be 10~100 integer.
The organic semiconducting materials have bipolarity carrier transport ability, make the hole in luminescent layer and electric transmission
Balance；There is hole transporting property and electronic transport property simultaneously, make the organic semiconducting materials hole and electricity in luminescent layer
The transmission balance of son, also with higher triplet, triplet is more than 2.75eV, effectively prevents in luminescence process
Energy returns to material of main part, greatly improves luminous efficiency, therefore organic semiconducting materials of the present invention have bipolarity blue light phosphorus
Light material of main part.
The invention provides a kind of preparation method of organic semiconducting materials, comprise the following steps：
Compound A is provided：With compound B：
Wherein, R is C1~C20Alkyl；Under an inert atmosphere, compound A and compound B are added according to mol ratio for 1: 1~1: 1.2
Add in the organic solvent containing catalyst and aqueous slkali, Suzuki coupled reactions carried out at 70~130 DEG C 12~96 hours,
The catalyst is organic palladium or is the mixture of organic palladium and organophosphor ligand, and obtain that following structural formula represents organic partly leads
Body material P：
Wherein, n is 10~100 integer.
In a particular embodiment, the preparation method of the organic semiconducting materials further comprises organic semiconductor material
The step of material P is isolated and purified, the purification procedures are as follows：Suzuki couplings are carried out to the compound A and compound B
Close and added in reacted solution methanol precipitating and filter, the solid being filtrated to get is taken out with methanol and n-hexane successively
Carry, by the solid chloroform after extracting, collect evaporation solvent after chloroformic solution and obtain organic semiconductor after purification
Material P.
In present embodiment, extracting is carried out using apparatus,Soxhlet's.
In present embodiment, evaporation solvent after chloroformic solution will be collected and obtain organic semiconducting materials P after purification true
Empty lower 50 DEG C~70 DEG C dryings 24 hours~48 hours.
In a particular embodiment, the organic solvent in toluene, DMF, tetrahydrofuran at least
It is a kind of.
In a particular embodiment, the aqueous slkali is in sodium carbonate liquor, solution of potassium carbonate and sodium bicarbonate solution
Solute and compound A mol ratio at least one, the aqueous slkali are 20: 1~50: 1.
In a particular embodiment, the organic palladium is bis-triphenylphosphipalladium palladium dichloride, tetra-triphenylphosphine palladium, palladium or three
The palladium of dibenzalacetone two, the organophosphorus ligand be tri-butyl phosphine, tri-o-tolyl phosphine or 2- dicyclohexyls phosphorus -2 ', 6 ' -
Dimethoxy-biphenyl, the organic palladium is 1: 4~1: 8 with the mol ratio of the organophosphorus ligand.
In a particular embodiment, the mol ratio of the organic palladium in the catalyst and the compound A is 1: 20~1:
100。
Better simply synthetic route is employed, so as to reduce technological process, raw material are cheap and easy to get so that manufacturing cost drops
It is low.
The invention provides a kind of electroluminescent device, including stack gradually the substrate with anode, luminescent layer and
Cathode layer, the luminescent layer is the mixture of material of main part and guest materials, and wherein as follows organic of material of main part partly leads
Body material：Wherein, R is C1~C20Alkyl, n be 10~100 integer, visitor
Body material is three [1- phenyl isoquinolin quinolines-C2, N] iridium, double (4,6- difluorophenyl pyridinato-N, C2) pyridinecarboxylics close iridium, [two (2 ',
4 '-difluorophenyl) pyridine] [four (1- pyrazolyls) boron] closes iridium or [two (2 ', 4 '-difluorophenyl) pyridines] (tetrazolium pyridine) is closed
Iridium.
In a particular embodiment, the guest materials and the mass percent of the material of main part are 5%~15%.
In a particular embodiment, anode material is indium zinc oxide or zinc oxide aluminum, and negative electrode is metallic aluminium, silver, gold or nickel.
Organic luminescent device transmitting blue light based on the material, and luminous efficiency is high.
Embodiment 1：
Present embodiment discloses following poly- { 4- n-hexane oxygen-N, N- bis- (4- bases-phenyl) aniline-co-3,7- of structural formula
Diyl sulphur dibenzofuran } (organic semiconducting materials P1)：
Above-mentioned organic semiconducting materials P1 preparation process is as follows：
Argon gas protection under, by 4- n-hexane oxygen-N, N- bis- (4- pinacol borates phenyl) aniline (119mg,
0.2mmol), 3,7- dibromos sulphur dibenzofuran (75mg, 0.2mmol) is added in the flask for filling 10ml toluene solvants, fully after dissolving
Potassium carbonate (2mL, 2mol/L) solution is added in flask, deoxygenation is vacuumized and is filled with argon gas, bi triphenyl phosphine is then added
Palladium chloride (5.6mg, 0.008mmol)；Flask is heated to 100 DEG C and carries out Suzuki coupled reactions 48h.Stop after cooling poly-
Reaction is closed, is added dropwise in 50ml methanol and is settled into flask；Methanol and just oneself are used after being filtered by apparatus,Soxhlet's successively
Alkane extracts 24h.Then collect chloroformic solution to colourless by solvent extraction of chloroform and be spin-dried for obtaining red powder, obtain this and gather
Under { 4- n-hexane oxygen-N, N- bis- (4- bases-phenyl) aniline-co-3,7- diyl sulphur dibenzofuran } organic semiconducting materials, last vacuum
50 DEG C of dry 24h.Yield is 83%.
The above-mentioned reaction equation for preparing organic semiconducting materials P1 is as follows：
Molecule measuring test result is：Molecular weight (GPC, THF, R.I)：Mn=32.7kDa, Mw/Mn=2.2.
It is the thermogravimetic analysis (TGA) figure of organic semiconducting materials manufactured in the present embodiment, thermogravimetric curve (TGA) referring to accompanying drawing 2
Test is carried out on TA SDT 2960instruments, and under nitrogen stream protection, programming rate is 10K/min.Can be with by figure
The thermal weight loss temperature for finding out 5% is 403 DEG C.
The organic semiconducting materials P1 prepared in embodiment 1 UV-visible absorption spectrum, ultraviolet-ray visible absorbing light
Spectrum is measured on Jasco-570 uv analyzers.As seen from the figure：Inventive polymers have between 300nm~800nm
Larger wider absorption, wherein maximum absorption band are located at 582nm, and wide absorption spectrum shows that P1 is a kind of photovoltaic material.
By testing antenna effect spectrum, instrument is FS modular fluorometers/pectrophosphorimeter, is made with investigating in embodiment 1
Standby organic semiconducting materials P1 triplet emission characteristics.Under 77K liquid nitrogen, organic semiconducting materials P1 shows very strong
Phosphorescent emissions, emission peak is in 446nm, and corresponding triplet energy state is 2.78eV, is much higher than double (4, the 6- difluorobenzenes of phosphor material
Yl pyridines-N, C2) pyridinecarboxylic closes iridium (III) FIrpic triplet energy state (2.65eV), and test data result shows us
Material can be used as blue emitting phosphor material of main part.
Embodiment 2：
Present embodiment discloses following poly- { 4- methane epoxides-N, N- bis- (4- bases-phenyl) aniline-co-3,7- of structural formula
Diyl sulphur dibenzofuran } (organic semiconducting materials P2)：
Under nitrogen and argon gas mixing gas shielded, by 4- methane oxygen-N, N- bis- (4- pinacol borates phenyl) aniline
(158mg, 0.3mmol), 3,7- dibromo sulphur dibenzofuran (112mg, 0.3mmol) and 15mL tetrahydrofurans add two mouthfuls of 50mL specifications
Bottle in, fully dissolving after be passed through after the gaseous mixture air-discharging about 20min of nitrogen and argon gas, then by tetra-triphenylphosphine palladium (4mg,
0.003mmol) it is added thereto, fully adds sodium acid carbonate (3mL, 2mol/L) solution after dissolving.Fully lead to nitrogen and argon again
After the gaseous mixture air-discharging about 10min of gas, two-mouth bottle is added to 70 DEG C and carries out Suzuki coupled reactions 96h.Stop after cooling
Polymerisation, is added dropwise in 40ml methanol into flask and is settled；Successively with methanol and just after being filtered by apparatus,Soxhlet's
Hexane extraction 24h.Then collect chloroformic solution to colourless by solvent extraction of chloroform and be spin-dried for obtaining red powder, gathered
Under { 4- methane epoxides-N, N- bis- (4- bases-phenyl) aniline-co-3,7- diyl sulphur dibenzofuran } organic semiconducting materials, last vacuum
50 DEG C of dry 24h.Yield is 76%.
The above-mentioned reaction equation for preparing organic semiconducting materials P2 is as follows：
Molecule measuring test result is：Molecular weight (GPC, THF, R.I)：Mn=45.1kDa, Mw/Mn=2.1.
Organic semiconducting materials P2 prepared by the present embodiment 2 thermogravimetic analysis (TGA) figure, thermogravimetric curve (TGA) is tested in TA
Carried out on SDT 2960instruments, under nitrogen stream protection, programming rate is 10K/min.As seen from the figure 5%
Thermal weight loss temperature is 447 DEG C.
The organic semiconducting materials P2 prepared in embodiment 2 UV-visible absorption spectrum, ultraviolet-ray visible absorbing light
Spectrum is measured on Jasco-570 uv analyzers.As seen from the figure：Inventive polymers have between 300nm~800nm
Larger wider absorption, wherein maximum absorption band are located at 584nm, and wide absorption spectrum shows that P2 is a kind of photovoltaic material.
By testing antenna effect spectrum, instrument is FS modular fluorometers/pectrophosphorimeter, to investigate organic semiconductor material
Expect P2 triplet emission characteristics.Under 77K liquid nitrogen, organic semiconducting materials P2 shows very strong phosphorescent emissions, emission peak
In 449nm, corresponding triplet energy state is 2.76eV, is much higher than double (4,6- difluorophenyl pyridinato-N, the C2) pyrroles of phosphor material
Pyridine formyl closes iridium (III) FIrpic triplet energy state (2.65eV), and test data result shows that our material can be as indigo plant
Light phosphorescent light body material.
Embodiment 3：
Present embodiment discloses following poly- { 4- n-eicosane epoxides-N, N- bis- (4- bases-phenyl) aniline-co- of structural formula
3,7- diyl sulphur dibenzofuran } (organic semiconducting materials P3)：
Under nitrogen protection, by 4- n-eicosane epoxides-N, N- bis- (4- pinacol borates phenyl) aniline (238mg,
0.3mmol), 3,7- dibromos sulphur dibenzofuran (123mg, 0.33mmol), palladium (3.5mg, 0.015mmol) and three (O-methoxies
Phenyl) phosphine (21mg, 0.06mmol) is added in the flask for the DMF for filling 12mL, fully added after dissolving
Potassium carbonate (3mL, 2mol/L) solution, then toward after logical nitrogen purge gas about 30min in flask；Flask is heated into 130 DEG C to enter
Row Suzuki coupled reactions 12h.Stop reacting and be cooled to room temperature, be added dropwise in 40ml methanol and settled into flask；Pass through
Successively with methanol and n-hexane extracting 24h after apparatus,Soxhlet's filtering.Then chlorine is collected to colourless by solvent extraction of chloroform
Imitative solution simultaneously is spin-dried for obtaining red powder, obtains poly- { 4- n-eicosane epoxides-N, N- bis- (4- bases-phenyl) aniline-co-3,7-
Diyl sulphur dibenzofuran } organic semiconducting materials, the last dry 24h of lower 50 DEG C of vacuum.Yield is 80%.
The above-mentioned reaction equation for preparing organic semiconducting materials P3 is as follows：
Molecule measuring test result is：Molecular weight (GPC, THF, R.I)：Mn=75.8kDa, Mw/Mn=2.0.
Organic semiconducting materials P3 prepared by the present embodiment 3 thermogravimetic analysis (TGA) figure, thermogravimetric curve (TGA) is tested in TA
Carried out on SDT 2960instruments, under nitrogen stream protection, programming rate is 10K/min.As seen from the figure 5%
Thermal weight loss temperature is 386 DEG C.
The organic semiconducting materials P3 prepared in embodiment 3 UV-visible absorption spectrum, ultraviolet-ray visible absorbing light
Spectrum is measured on Jasco-570 uv analyzers.As seen from the figure：Inventive polymers have between 300nm~800nm
Larger wider absorption, wherein maximum absorption band are located at 580nm, and wide absorption spectrum shows that P3 is a kind of photovoltaic material.
By testing antenna effect spectrum, instrument is FS modular fluorometers/pectrophosphorimeter, to investigate organic semiconductor material
Expect P3 triplet emission characteristics.Under 77K liquid nitrogen, organic semiconducting materials P3 shows very strong phosphorescent emissions, emission peak
In 443nm, corresponding triplet energy state is 2.80eV, is much higher than double (4,6- difluorophenyl pyridinato-N, the C2) pyrroles of phosphor material
Pyridine formyl closes iridium (III) FIrpic triplet energy state (2.65eV), and test data result shows that our material can be as indigo plant
Light phosphorescent light body material.
Embodiment 4：
Present embodiment discloses structural formula it is following it is poly- 4- normal butane epoxides-N, N- bis- (4- bases-phenyl) aniline-co-3,
7- diyl sulphur dibenzofuran } (organic semiconducting materials P4)：
Under nitrogen protection, by 4- normal butane epoxides-N, N- bis- (4- pinacol borates phenyl) aniline (171mg,
0.3mmol), 3,7- dibromos sulphur dibenzofuran (135mg, 0.36mmol), the palladium of three or two argon benzylacetone two (9mg, 0.009mmol) and 2-
Dicyclohexyl phosphine -2 ', 6 '-dimethoxy-biphenyl (29mg, 0.072mmol) is added to the DMF for filling 12mL
Flask in, fully dissolving after add sodium carbonate (3mL, 2mol/L) solution.Then toward logical nitrogen purge gas about 30min in flask
Afterwards；Flask is heated to 120 DEG C and carries out Suzuki coupled reactions 36h.Stop polymerisation after cooling, 40ml is added dropwise into flask
Settled in methanol；Successively with methanol and n-hexane extracting 24h after being filtered by apparatus,Soxhlet's.Then using chloroform to be molten
Agent is extracted to colourless, is collected chloroformic solution and simultaneously is spin-dried for obtaining red powder, obtain it is poly- 4- normal butane epoxides-N, N- bis- (4- bases-
Phenyl) aniline-co-3,7- diyl sulphur dibenzofuran } organic semiconducting materials, the last dry 24h of lower 50 DEG C of vacuum.Yield is 87%.
The above-mentioned reaction equation for preparing organic semiconducting materials P4 is as follows：
Molecule measuring test result is：Molecular weight (GPC, THF, R.I)：Mn=51.3kDa, Mw/Mn=2.1.
The thermogravimetic analysis (TGA) figure of organic semiconducting materials prepared by the present embodiment 4, thermogravimetric curve (TGA) is tested in TA
Carried out on SDT 2960instruments, under nitrogen stream protection, programming rate is 10K/min.As seen from the figure 5%
Thermal weight loss temperature is 430 DEG C.
The organic semiconducting materials P4 prepared in embodiment 4 UV-visible absorption spectrum, ultraviolet-ray visible absorbing light
Spectrum is measured on Jasco-570 uv analyzers.As seen from the figure：Inventive polymers have between 300nm~800nm
Larger wider absorption, wherein maximum absorption band are located at 582nm, and wide absorption spectrum shows that P4 is a kind of photovoltaic material.
By testing antenna effect spectrum, instrument is FS modular fluorometers/pectrophosphorimeter, to investigate organic semiconductor material
Expect P4 triplet emission characteristics.Under 77K liquid nitrogen, organic semiconducting materials P4 shows very strong phosphorescent emissions, emission peak
In 444nm, corresponding triplet energy state is 2.79eV, is much higher than double (4,6- difluorophenyl pyridinato-N, the C2) pyrroles of phosphor material
Pyridine formyl closes iridium (III) FIrpic triplet energy state (2.65eV), and test data result shows that our material can be as indigo plant
Light phosphorescent light body material.
Embodiment 5：
Present embodiment discloses following poly- { (the 4- pinacol borate benzene of 4- n-dodecane epoxides-N, N- bis- of structural formula
Base) aniline } (organic semiconducting materials P5)：
Under nitrogen protection, by 4- n-dodecane epoxides-N, N- bis- (4- pinacol borates phenyl) aniline (205mg,
0.3mmol), 3,7- dibromos sulphur dibenzofuran (112mg, 0.3mmol), tetra-triphenylphosphine palladium (8mg, 0.006mmol) are added to and filled
15mL toluene is added in 50mL twoport flask, fully adds potassium carbonate (3mL, 2mol/L) solution after dissolving.Then toward flask
In lead to after nitrogen purge gas about 10min；Flask is heated to 90 DEG C and carries out Suzuki coupled reactions 60h.Stop polymerization after cooling
Reaction, is added dropwise in 40ml methanol into flask and is settled；Methanol and n-hexane are used after being filtered by apparatus,Soxhlet's successively
Extract 24h.Then by solvent extraction of chloroform to colourless, collect chloroformic solution and simultaneously be spin-dried for obtaining red powder, obtain that poly- { 4- is just
Dodecyloxy-N, N- bis- (4- pinacol borates phenyl) aniline } organic semiconducting materials, the last lower 50 DEG C of dryings of vacuum
24h.Yield is 73%.
The above-mentioned reaction equation for preparing organic semiconducting materials P5 is as follows：
Molecule measuring test result is：Molecular weight (GPC, THF, R.I)：Mn=4.3kDa, Mw/Mn=2.4.
Organic semiconducting materials P5 prepared by the present embodiment 5 thermogravimetic analysis (TGA) figure, thermogravimetric curve (TGA) is tested in TA
Carried out on SDT 2960instruments, under nitrogen stream protection, programming rate is 10K/min.As seen from the figure 5%
Thermal weight loss temperature is 395 DEG C.
The organic semiconducting materials P5 prepared in embodiment 5 UV-visible absorption spectrum, ultraviolet-ray visible absorbing light
Spectrum is measured on Jasco-570 uv analyzers.As seen from the figure：Inventive polymers have between 300nm~800nm
Larger wider absorption, wherein maximum absorption band are located at 584nm, and wide absorption spectrum shows that P5 is a kind of photovoltaic material.
By testing antenna effect spectrum, instrument is FS modular fluorometers/pectrophosphorimeter, to investigate organic semiconductor material
Expect P5 triplet emission characteristics.Under 77K liquid nitrogen, organic semiconducting materials P5 shows very strong phosphorescent emissions, emission peak
In 448nm, corresponding triplet energy state is 2.77eV, is much higher than double (4,6- difluorophenyl pyridinato-N, the C2) pyrroles of phosphor material
Pyridine formyl closes iridium (III) FIrpic triplet energy state (2.65eV), and test data result shows that our material can be as indigo plant
Light phosphorescent light body material.
Application Example
Organic electroluminescence device 300, it includes substrate 301 to its structure such as Fig. 1, and anode 302, hole injection layer 303 is empty
Cave transmitting layer 3 04, luminescent layer 305, electron transfer layer 306, electron injection cushion 307, negative electrode 308.
The material of substrate 301 is glass in the present embodiment, the vacuum coating anode 302 successively in substrate 301, hole injection
Layer 303, hole transmission layer 304, luminescent layer 305, electron transfer layer 306, electron injection cushion 307, negative electrode 308, anode 302
Square resistance is used for 10~20 Ω/ tin indium oxide, thickness is 150nm, hole injection layer 303 uses poly- (3,4- ethene
Dioxy thiophene)-polystyrolsulfon acid, thickness is 30nm, and hole transmission layer 304 uses N, N '-diphenyl-N, N '-(1- naphthyls)-
1,1 '-biphenyl -4,4 '-diamines, thickness is 20nm, and the main body luminescent material of luminescent layer 305 implements 1 chemical combination prepared using the present invention
Thing is poly- { 4- n-hexane oxygen-N, N- bis- (4- bases-phenyl) aniline-co-3,7- diyl sulphur dibenzofuran }, and is mixed on the basis of material of main part
Impurity level percentage closes iridium (III), hair for 10% double (4,6- difluorophenyl pyridinato-N, C2) pyridinecarboxylics of guest emitting material
The thickness of photosphere 305 is 20nm, and (4,7- diphenyl -1,10- phenanthrolines, thickness is 30nm, electronics note for the use of electron transfer layer 306 5
Enter cushion 307 and use lithium fluoride, thickness is 1nm, and negative electrode 308 uses metallic aluminium, and thickness is 100nm.
Organic layer and metal level are deposited using thermal evaporation process and completed, and vacuum is 10-3~10-5Pa, the thickness of film
Monitor that the evaporation rate of all organic materials is in addition to guest materials using film thickness monitoring instrument The evaporation of lithium fluoride
Speed isThe evaporation rate of metallic aluminium is
The electroluminescent device has higher luminous efficiency, can be widely used in the illumination fields such as blueness or white.Device
Current versus brightness-voltage characteristic of part is by the Keithley sources measuring system with correction silicon photoelectric diode
All measurements that (Keithley 2400Sourcemeter, Keithley 2000Cuirrentmeter) is completed are big in room temperature
Completed in gas.As a result show：The maximum electrical efficiency of device is 11.8cd/A, and high-high brightness is 26290cd/m2。
Embodiment described above only expresses the several embodiments of the present invention, and it describes more specific and detailed, but simultaneously
Therefore the limitation to the scope of the claims of the present invention can not be interpreted as.It should be pointed out that for one of ordinary skill in the art
For, without departing from the inventive concept of the premise, various modifications and improvements can be made, these belong to the guarantor of the present invention
Protect scope.Therefore, the protection domain of patent of the present invention should be determined by the appended claims.
Claims (3)
1. a kind of electroluminescent device, it is characterised in that including the substrate with anode, luminescent layer and the negative electrode stacked gradually
Layer, the luminescent layer is the mixture of material of main part and guest materials, wherein material of main part organic semiconductor material as follows
Material：
Wherein, R is C1~C20Alkyl, n be 10~100 integer, object material
Expect for three [1- phenyl isoquinolin quinolines-C2, N] iridium, double (4,6- difluorophenyl pyridinato-N, C2) pyridinecarboxylics close iridium, [two (2 ', 4 '-
Difluorophenyl) pyridine] [four (1- pyrazolyls) boron] closes iridium or [two (2 ', 4 '-difluorophenyl) pyridines] (tetrazolium pyridine) closes iridium.
2. electroluminescent device as claimed in claim 1, it is characterised in that the guest materials and the material of main part
Mass percent is 5%~15%.
3. electroluminescent device as claimed in claim 1, it is characterised in that the anode material is indium zinc oxide or zinc oxide
Aluminium, negative electrode is metallic aluminium, silver, gold or nickel.
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| CN101712674A (en) * | 2009-11-13 | 2010-05-26 | 华南理工大学 | Alkyl substituted-S,S-dioxo-dibenzothiophene monomer, preparation method and polymer thereof |
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| CN101429274A (en) * | 2008-09-17 | 2009-05-13 | 中国科学院长春应用化学研究所 | Poly-fluorene single-component white radiation macromolecule material containing phosphoric acid ester group, preparation method and application thereof |
| CN101712674A (en) * | 2009-11-13 | 2010-05-26 | 华南理工大学 | Alkyl substituted-S,S-dioxo-dibenzothiophene monomer, preparation method and polymer thereof |
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