CN103965441A - Organic semiconductor material, preparation method and electroluminescent device - Google Patents
Organic semiconductor material, preparation method and electroluminescent device Download PDFInfo
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- CN103965441A CN103965441A CN201310038369.7A CN201310038369A CN103965441A CN 103965441 A CN103965441 A CN 103965441A CN 201310038369 A CN201310038369 A CN 201310038369A CN 103965441 A CN103965441 A CN 103965441A
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- semiconductor material
- organic semiconductor
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- 239000000463 material Substances 0.000 title claims abstract description 137
- 239000004065 semiconductor Substances 0.000 title claims abstract description 80
- 238000002360 preparation method Methods 0.000 title claims abstract description 30
- 239000000126 substance Substances 0.000 claims abstract description 11
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 48
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims description 46
- JUJWROOIHBZHMG-UHFFFAOYSA-N pyridine Substances C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 claims description 27
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 26
- 239000000243 solution Substances 0.000 claims description 26
- 229910052763 palladium Inorganic materials 0.000 claims description 23
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 claims description 18
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 claims description 16
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 15
- 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
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 13
- -1 4,6-difluorophenyl Chemical group 0.000 claims description 12
- 238000006069 Suzuki reaction reaction Methods 0.000 claims description 11
- 239000012670 alkaline solution Substances 0.000 claims description 9
- OMFXVFTZEKFJBZ-HJTSIMOOSA-N corticosterone Chemical compound O=C1CC[C@]2(C)[C@H]3[C@@H](O)C[C@](C)([C@H](CC4)C(=O)CO)[C@@H]4[C@@H]3CCC2=C1 OMFXVFTZEKFJBZ-HJTSIMOOSA-N 0.000 claims description 9
- 239000003446 ligand Substances 0.000 claims description 9
- 239000000203 mixture Substances 0.000 claims description 9
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 claims description 9
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 8
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 claims description 8
- 238000001914 filtration Methods 0.000 claims description 8
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 claims description 8
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 6
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 6
- 239000003960 organic solvent Substances 0.000 claims description 6
- 238000000746 purification Methods 0.000 claims description 6
- 239000007787 solid Substances 0.000 claims description 6
- 239000000758 substrate Substances 0.000 claims description 6
- 229910052782 aluminium Inorganic materials 0.000 claims description 5
- 239000004411 aluminium Substances 0.000 claims description 5
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 5
- ASWXNYNXAOQCCD-UHFFFAOYSA-N dichloro(triphenyl)-$l^{5}-phosphane Chemical compound C=1C=CC=CC=1P(Cl)(C=1C=CC=CC=1)(Cl)C1=CC=CC=C1 ASWXNYNXAOQCCD-UHFFFAOYSA-N 0.000 claims description 4
- 238000001704 evaporation Methods 0.000 claims description 4
- 229910000030 sodium bicarbonate Inorganic materials 0.000 claims description 4
- 235000017557 sodium bicarbonate Nutrition 0.000 claims description 4
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 4
- 239000002904 solvent Substances 0.000 claims description 4
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 claims description 3
- 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 claims description 3
- GSNUFIFRDBKVIE-UHFFFAOYSA-N DMF Natural products CC1=CC=C(C)O1 GSNUFIFRDBKVIE-UHFFFAOYSA-N 0.000 claims description 3
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 claims description 3
- JYMITAMFTJDTAE-UHFFFAOYSA-N aluminum zinc oxygen(2-) Chemical compound [O-2].[Al+3].[Zn+2] JYMITAMFTJDTAE-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
- 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 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
- 229910000027 potassium carbonate Inorganic materials 0.000 claims description 3
- 230000001376 precipitating effect Effects 0.000 claims description 3
- 238000000926 separation method Methods 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
- TUQOTMZNTHZOKS-UHFFFAOYSA-N tributylphosphine Chemical compound CCCCP(CCCC)CCCC TUQOTMZNTHZOKS-UHFFFAOYSA-N 0.000 claims description 3
- 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 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
- 238000000034 method Methods 0.000 abstract description 9
- 230000008569 process Effects 0.000 abstract description 8
- 238000004020 luminiscence type Methods 0.000 abstract description 6
- 238000004519 manufacturing process Methods 0.000 abstract description 3
- 125000003837 (C1-C20) alkyl group Chemical group 0.000 abstract 1
- 230000015572 biosynthetic process Effects 0.000 abstract 1
- 239000002994 raw material Substances 0.000 abstract 1
- 238000003786 synthesis reaction Methods 0.000 abstract 1
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 33
- 229910052757 nitrogen Inorganic materials 0.000 description 30
- 239000010410 layer Substances 0.000 description 26
- 238000012360 testing method Methods 0.000 description 20
- TXCDCPKCNAJMEE-UHFFFAOYSA-N dibenzofuran Chemical compound C1=CC=C2C3=CC=CC=C3OC2=C1 TXCDCPKCNAJMEE-UHFFFAOYSA-N 0.000 description 18
- 238000000862 absorption spectrum Methods 0.000 description 15
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N Aniline Chemical compound NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 description 14
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 12
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 10
- 238000010521 absorption reaction Methods 0.000 description 10
- 239000007789 gas Substances 0.000 description 10
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 9
- 239000005864 Sulphur Substances 0.000 description 9
- 230000005540 biological transmission Effects 0.000 description 8
- 239000004327 boric acid Substances 0.000 description 7
- 238000004458 analytical method Methods 0.000 description 6
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 6
- 238000006243 chemical reaction Methods 0.000 description 6
- 238000002347 injection Methods 0.000 description 6
- 239000007924 injection Substances 0.000 description 6
- 239000001301 oxygen Substances 0.000 description 6
- 229910052760 oxygen Inorganic materials 0.000 description 6
- 229910052786 argon Inorganic materials 0.000 description 5
- 229910001873 dinitrogen Inorganic materials 0.000 description 5
- MILUBEOXRNEUHS-UHFFFAOYSA-N iridium(3+) Chemical compound [Ir+3] MILUBEOXRNEUHS-UHFFFAOYSA-N 0.000 description 5
- 239000007788 liquid Substances 0.000 description 5
- 238000001296 phosphorescence spectrum Methods 0.000 description 5
- 239000000843 powder Substances 0.000 description 5
- 238000004062 sedimentation Methods 0.000 description 5
- 238000000638 solvent extraction Methods 0.000 description 5
- 230000004580 weight loss Effects 0.000 description 5
- 238000001816 cooling Methods 0.000 description 4
- PQXKHYXIUOZZFA-UHFFFAOYSA-M lithium fluoride Chemical compound [Li+].[F-] PQXKHYXIUOZZFA-UHFFFAOYSA-M 0.000 description 4
- SHGUVJPXKKRMRP-UHFFFAOYSA-N [O].CCCC Chemical compound [O].CCCC SHGUVJPXKKRMRP-UHFFFAOYSA-N 0.000 description 3
- 239000000872 buffer Substances 0.000 description 3
- 238000005401 electroluminescence Methods 0.000 description 3
- 230000005525 hole transport Effects 0.000 description 3
- 229940094933 n-dodecane Drugs 0.000 description 3
- 235000015320 potassium carbonate Nutrition 0.000 description 3
- 238000010926 purge Methods 0.000 description 3
- 230000027756 respiratory electron transport chain Effects 0.000 description 3
- 0 CC(C)(C)c(cc1)cc2c1-c(ccc(-c(cc1)ccc1N(c(cc1)ccc1O*)c1ccc(C3(C)C)c3c1)c1)c1S2(=O)=O Chemical compound CC(C)(C)c(cc1)cc2c1-c(ccc(-c(cc1)ccc1N(c(cc1)ccc1O*)c1ccc(C3(C)C)c3c1)c1)c1S2(=O)=O 0.000 description 2
- 125000003545 alkoxy group Chemical group 0.000 description 2
- 238000007599 discharging Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 239000000178 monomer Substances 0.000 description 2
- 235000011181 potassium carbonates Nutrition 0.000 description 2
- 239000007858 starting material Substances 0.000 description 2
- ORPNDFMZTDVBGA-UHFFFAOYSA-N (2-methoxyphenyl)phosphane Chemical compound COC1=CC=CC=C1P ORPNDFMZTDVBGA-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
- LUDZJVZEBHTEBB-UHFFFAOYSA-N O=S1(c(cc(cc2)Br)c2-c(cc2)c1cc2Br)=O Chemical compound O=S1(c(cc(cc2)Br)c2-c(cc2)c1cc2Br)=O LUDZJVZEBHTEBB-UHFFFAOYSA-N 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- FFBHFFJDDLITSX-UHFFFAOYSA-N benzyl N-[2-hydroxy-4-(3-oxomorpholin-4-yl)phenyl]carbamate Chemical compound OC1=C(NC(=O)OCC2=CC=CC=C2)C=CC(=C1)N1CCOCC1=O FFBHFFJDDLITSX-UHFFFAOYSA-N 0.000 description 1
- 239000004305 biphenyl Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000012937 correction Methods 0.000 description 1
- 238000006392 deoxygenation reaction Methods 0.000 description 1
- 230000005281 excited state Effects 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 230000006872 improvement Effects 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
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 238000012544 monitoring process Methods 0.000 description 1
- ZTLUNQYQSIQSFK-UHFFFAOYSA-N n-[4-(4-aminophenyl)phenyl]naphthalen-1-amine Chemical class C1=CC(N)=CC=C1C(C=C1)=CC=C1NC1=CC=CC2=CC=CC=C12 ZTLUNQYQSIQSFK-UHFFFAOYSA-N 0.000 description 1
- 239000012044 organic layer Substances 0.000 description 1
- 125000002524 organometallic group Chemical group 0.000 description 1
- 238000007747 plating Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 230000004044 response Effects 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 238000002207 thermal evaporation Methods 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
- 230000004304 visual acuity Effects 0.000 description 1
Classifications
-
- 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
-
- 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
-
- 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
-
- 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
- H10K85/151—Copolymers
-
- 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
- C08G2261/12—Copolymers
-
- 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
- C08G2261/31—Monomer units or repeat units incorporating structural elements in the main chain incorporating aromatic structural elements in the main chain
- C08G2261/316—Monomer units or repeat units incorporating structural elements in the main chain incorporating aromatic structural elements in the main chain bridged by heteroatoms, e.g. N, P, Si or B
- C08G2261/3162—Arylamines
-
- 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
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
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- 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
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
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- 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
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- 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
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- C—CHEMISTRY; METALLURGY
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- C08G2261/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
- C08G2261/90—Applications
- C08G2261/95—Use in organic luminescent diodes
Abstract
The present invention provides an organic semiconductor material having the following chemical formula, wherein R is C1-C20 alkyl, and n is an integer of 10-100. According to the present invention, the organic semiconductor material concurrently has hole transporting property and electron transporting property so as to achieve hole and electron transporting balance of the organic semiconductor material in the luminescence layer, and further has a high triplet energy level of greater than 2.75 eV, such that the condition that energy is returned to the main body material during the luminescence process can be effectively prevented so as to substantially increase the luminescence efficiency; and the organic semiconductor material preparation method adopts the simple synthesis route, and has characteristics of process reducing, easily available raw materials and manufacturing cost reducing.
Description
Technical field
The invention belongs to field of photovoltaic materials, be specifically related to a kind of organic semiconductor material, preparation method and electroluminescent device.
Background technology
Organic electroluminescence device has that driving voltage is low, fast response time, angular field of view is wide and can be finely tuned and be changed luminescent properties and make rich color by chemical structure, easily realize the advantages such as resolving power is high, lightweight, large-area flat-plate demonstration, be described as " 21 century flat panel display ", become the focus of the subjects such as material, information, physics and flat pannel display area research.Following commercialization Organic Light Emitting Diode efficiently will contain organo-metallic phosphorescent substance possibly, because they can all catch singlet and triplet excitons, thereby realize 100% internal quantum efficiency.Yet, because the excited state exciton life-span of transition metal complex is relatively long, cause unwanted triplet state-triplet state (T
1-T
1) cancellation in device real work.In order to overcome this problem, investigators are often doped to triplet state shiner in organic main body material.
In recent years, green and red phosphorescent OLED device exhibits goes out gratifying electroluminescent efficiency.And efficient blue phosphorescent device seldom, major cause is to lack to have good carrier transmission performance and higher triplet (E simultaneously
t) material of main part.
Summary of the invention
For addressing the above problem, the invention provides a kind of organic semiconductor material, this organic semiconductor material has hole transport character and electronic transport property, make the transmission balance of this semiconductor material hole and electronics in luminescent layer, also there is higher triplet, triplet is greater than 2.75eV, effectively prevent that in luminescence process, energy returns to material of main part, greatly improve luminous efficiency, organic semiconductor material of the present invention provides new selectable kind for bipolarity blue emitting phosphor material of main part.The present invention also provides the preparation method of this organic semiconductor material, and the electroluminescent device that comprises this organic semiconductor material.
On the one hand, the invention provides a kind of organic semiconductor material, the chemical formula of described organic semiconductor material is as follows:
wherein, R is C
1~ C
20alkyl, the integer that n is 10 ~ 100.
Second aspect, the invention provides a kind of preparation method of organic semiconductor material, comprises the steps:
Compd A is provided:
and compd B:
wherein, R is C
1~ C
20alkyl; Under inert atmosphere, by compd A and compd B, according to mol ratio, be within 1: 1 ~ 1: 1.2, to be added in the organic solvent that contains catalyzer and alkaline solution, at 70～130 ℃, carry out Suzuki coupling reaction 12～96 hours, described catalyzer is organic palladium or is the mixture of organic palladium and organophosphor ligand, obtains the organic semiconductor material P that following structural formula represents:
wherein, the integer that n is 10 ~ 100.
Preferably, the preparation method of described organic semiconductor material also comprises the step of organic semiconductor material P being carried out to separation and purification, described purification procedures is as follows: to described compd A and compd B, carry out adding methyl alcohol precipitating also to filter in the solution after Suzuki coupling reaction, the solid that filtration is obtained carries out extracting with methyl alcohol and normal hexane successively, by the chloroform extracting of the solid after extracting, after collection chloroformic solution, evaporating solvent obtains the organic semiconductor material P after purifying.
Preferably, described organic solvent is selected from least one in toluene, DMF, tetrahydrofuran (THF).
Preferably, described alkaline solution is selected from least one in sodium carbonate solution, solution of potassium carbonate and sodium hydrogen carbonate solution, and the solute in described alkaline solution and the mol ratio of compd A are 20:1 ~ 50:1.
Preferably, described organic palladium is bi triphenyl phosphine dichloride palladium, tetra-triphenylphosphine palladium, palladium or three dibenzalacetone two palladiums, described organophosphorus ligand is tri-butyl phosphine, tri-o-tolyl phosphine or 2-dicyclohexyl phosphorus-2 ', 6 '-dimethoxy-biphenyl, the mol ratio of described organic palladium and described organophosphorus ligand is 1:4 ~ 1:8.
Preferably, the mol ratio of the organic palladium in described catalyzer and described compd A is 1:20 ~ 1:100.
The third aspect, the invention provides a kind of electroluminescent device, comprise the substrate with anode, luminescent layer and the cathode layer that stack gradually, described luminescent layer is the mixture of material of main part and guest materials, wherein material of main part organic semiconductor material as follows:
wherein, R is C
1~ C
20alkyl, n is 10 ~ 100 integer, guest materials is three [1-phenyl isoquinolin quinoline-C2, N] iridium, two (4,6-difluorophenyl pyridine-N, C2) pyridine formyl closes that iridium, [two (2 ', 4 '-difluorophenyl) pyridine] [four (1-pyrazolyl) boron] close iridium or [two (2 ', 4 '-difluorophenyl) pyridine] (tetrazolium pyridine) closes iridium.
Preferably, the mass percent of described material of main part and described guest materials is 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 semiconductor material, preparation method and electroluminescent device, there is following beneficial effect: there is hole transport character and electronic transport property simultaneously, make the transmission balance of organic semiconductor material hole and electronics in luminescent layer, also there is higher triplet, triplet is greater than 2.75eV, effectively prevent that in luminescence process, energy returns to material of main part, greatly improve luminous efficiency.This material has adopted better simply synthetic route, has reduced technical process, and starting material are cheap and easy to get, and manufacturing cost is reduced.
Accompanying drawing explanation
Fig. 1 be take the structural representation of the organic electroluminescence device that the organic semiconductor material that makes in embodiment 1 makes as material of main part;
Fig. 2 is the thermogravimetic analysis (TGA) figure of the organic semiconductor material that makes in embodiment 1.
Embodiment
In order to understand better the content of patent of the present invention, below by concrete example and legend, further illustrate technology case of the present invention, specifically comprise material preparation and device preparation, but these embodiments do not limit the present invention, wherein monomer A is bought and is obtained from the market, the disclosed method of monomers B reference literature (J.AM.CHEM.SOC.9VOL.125, NO.44,2003) is synthetic to be obtained.
The invention provides a kind of organic semiconductor material, the chemical formula of described organic semiconductor material is as follows:
wherein, R is C
1~ C
20alkyl, the integer that n is 10 ~ 100.
This organic semiconductor material has bipolarity carrier transport ability, makes hole and electric transmission balance in luminescent layer; There is hole transport character and electronic transport property simultaneously, make the transmission balance of this organic semiconductor material hole and electronics in luminescent layer, also there is higher triplet, triplet is greater than 2.75eV, effectively prevent that in luminescence process, energy returns to material of main part, greatly improve luminous efficiency, so organic semiconductor material of the present invention has bipolarity blue emitting phosphor material of main part.
The preparation method who the invention provides a kind of organic semiconductor material, comprises the steps:
Compd A is provided:
and compd B:
wherein, R is C
1~ C
20alkyl; Under inert atmosphere, by compd A and compd B, according to mol ratio, be 1:1 ~ 1: 1.2 are added in the organic solvent that contains catalyzer and alkaline solution, at 70～130 ℃, carry out Suzuki coupling reaction 12～96 hours, described catalyzer is organic palladium or is the mixture of organic palladium and organophosphor ligand, obtains the organic semiconductor material P that following structural formula represents:
wherein, the integer that n is 10 ~ 100.
In specific embodiment, the preparation method of described organic semiconductor material further comprises the step of organic semiconductor material P being carried out to separation and purification, described purification procedures is as follows: to described compd A and compd B, carry out adding methyl alcohol precipitating also to filter in the solution after Suzuki coupling reaction, the solid that filtration is obtained carries out extracting with methyl alcohol and normal hexane successively, by the chloroform extracting of the solid after extracting, after collection chloroformic solution, evaporating solvent obtains the organic semiconductor material P after purifying.
In present embodiment, extracting is used apparatus,Soxhlet's to carry out.
In present embodiment, by collect evaporating solvent after chloroformic solution obtain organic semiconductor material P after purifying under vacuum 50 ℃～70 ℃ dry 24 hours～48 hours.
In specific embodiment, described organic solvent is selected from least one in toluene, DMF, tetrahydrofuran (THF).
In specific embodiment, described alkaline solution is selected from least one in sodium carbonate solution, solution of potassium carbonate and sodium hydrogen carbonate solution, and the solute in described alkaline solution and the mol ratio of compd A are 20:1 ~ 50:1.
In specific embodiment, described organic palladium is bi triphenyl phosphine dichloride palladium, tetra-triphenylphosphine palladium, palladium or three dibenzalacetone two palladiums, described organophosphorus ligand is tri-butyl phosphine, tri-o-tolyl phosphine or 2-dicyclohexyl phosphorus-2 ', 6 '-dimethoxy-biphenyl, the mol ratio of described organic palladium and described organophosphorus ligand is 1:4 ~ 1:8.
In specific embodiment, the organic palladium in described catalyzer and the mol ratio of described compd A are 1:20 ~ 1:100.
Adopted better simply synthetic route, thereby reduced technical process, starting material are cheap and easy to get, and manufacturing cost is reduced.
The invention provides a kind of electroluminescent device, comprise the substrate with anode, luminescent layer and the cathode layer that stack gradually, described luminescent layer is the mixture of material of main part and guest materials, wherein material of main part organic semiconductor material as follows:
wherein, R is the alkyl of C1 ~ C20, n is 10 ~ 100 integer, guest materials is three [1-phenyl isoquinolin quinoline-C2, N] iridium, two (4,6-difluorophenyl pyridine-N, C2) pyridine formyl close iridium, [two (2 ', 4 '-difluorophenyl) pyridine] [four (1-pyrazolyl) boron] closes iridium or [two (2 ', 4 '-difluorophenyl) pyridine] (tetrazolium pyridine) closes iridium.
In specific embodiment, the mass percent of described guest materials and described material of main part is 5%～15%.
In specific 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 this material, and luminous efficiency is high.
Embodiment 1:
The present embodiment discloses following poly-{ 4-normal hexane oxygen-N, N-bis-(4-base-phenyl) aniline-co-3,7-bis-base sulphur dibenzofuran } (the organic semiconductor material P1) of structural formula:
The preparation process of above-mentioned organic semiconductor material P1 is as follows:
Under argon shield, by 4-normal hexane oxygen-N, N-bis-(4-tetramethyl ethylene ketone boric acid ester phenyl) aniline (119mg, 0.2mmol), 3,7-dibromo sulphur dibenzofuran (75mg, 0.2mmol) add in the flask that fills 10ml toluene solvant, after fully dissolving, salt of wormwood (2mL, 2mol/L) solution is joined in flask, vacuumize deoxygenation and be filled with argon gas, then add bi triphenyl phosphine dichloride palladium (5.6mg, 0.008mmol); Flask is heated to 100 ℃ and carries out Suzuki coupling reaction 48h.After cooling, stop polyreaction, to dripping in flask, in 50ml methyl alcohol, carry out sedimentation; After filtering by apparatus,Soxhlet's, use successively methyl alcohol and normal hexane extracting 24h.Then the chloroform of take is extremely colourless as solvent extraction, collects chloroformic solution and be spin-dried for to obtain red powder, obtains this poly-{ 4-normal hexane oxygen-N, N-bis-(4-base-phenyl) aniline-co-3,7-bis-base sulphur dibenzofuran } organic semiconductor material, the last lower 50 ℃ of dry 24h of vacuum.Productive rate is 83%.
The above-mentioned reaction formula of preparing organic semiconductor material P1 is as follows:
Molecule measuring test result is: Molecular weight (GPC, THF, R.I): M
n=32.7kDa, M
w/ M
n=2.2.
Referring to accompanying drawing 2, are thermogravimetic analysis (TGA) figure of the organic semiconductor material prepared of the present embodiment, thermogravimetric curve (TGA) test is carried out on TA SDT2960instruments, and under nitrogen gas stream protection, heat-up rate is 10K/min.5% thermal weight loss temperature is 403 ℃ as seen from the figure.
The uv-visible absorption spectra figure of the organic semiconductor material P1 of preparation in embodiment 1, uv-visible absorption spectra is measured on Jasco-570 uv analyzer.As seen from the figure: polymkeric substance of the present invention between 300nm ~ 800nm, have large wider absorption, wherein maximum absorption band is positioned at 582nm, wide absorption spectrum shows that P1 is a kind of photovoltaic material.
By test for low temperature phosphorescence spectrum, instrument is FS modular fluorometer/pectrophosphorimeter, to investigate the organic semiconductor material P1 triplet state emission characteristic of preparation in embodiment 1.Under the liquid nitrogen of 77K, organic semiconductor material P1 shows very strong phosphorescent emissions, emission peak is at 446nm, corresponding triplet energy state is 2.78eV, be much higher than phosphor material two (4,6-difluorophenyl pyridine-N, C2) pyridine formyl closes the triplet energy state (2.65eV) of iridium (III) FIrpic, and test data result shows that our material can be used as blue emitting phosphor material of main part.
Embodiment 2:
The present embodiment discloses following poly-{ 4-first alkoxyl group-N, N-bis-(4-base-phenyl) aniline-co-3,7-bis-base sulphur dibenzofuran } (the organic semiconductor material P2) of structural formula:
Under nitrogen and the protection of argon gas gas mixture; by 4-methane oxygen-N; N-bis-(4-tetramethyl ethylene ketone boric acid ester phenyl) aniline (158mg; 0.3mmol), 3; 7-dibromo sulphur dibenzofuran (112mg; 0.3mmol) add in the two-mouth bottle of 50mL specification with 15mL tetrahydrofuran (THF); after fully dissolving, pass into after the about 20min of gas mixture air-discharging of nitrogen and argon gas; then by tetra-triphenylphosphine palladium (4mg; 0.003mmol) add wherein; after fully dissolving, add again sodium bicarbonate (3mL, 2mol/L) solution.After the about 10min of gas mixture air-discharging of fully logical nitrogen and argon gas, two-mouth bottle is joined to 70 ℃ and carry out Suzuki coupling reaction 96h again.After cooling, stop polyreaction, to dripping in flask, in 40ml methyl alcohol, carry out sedimentation; After filtering by apparatus,Soxhlet's, use successively methyl alcohol and normal hexane extracting 24h.Then the chloroform of take is extremely colourless as solvent extraction, collects chloroformic solution and be spin-dried for to obtain red powder, is gathered { 4-first alkoxyl group-N, N-bis-(4-base-phenyl) aniline-co-3,7-bis-base sulphur dibenzofuran } organic semiconductor material, the last lower 50 ℃ of dry 24h of vacuum.Productive rate is 76%.
The above-mentioned reaction formula of preparing organic semiconductor material P2 is as follows:
Molecule measuring test result is: Molecular weight (GPC, THF, R.I): M
n=45.1kDa, M
w/ M
n=2.1.
The thermogravimetic analysis (TGA) figure of the organic semiconductor material P2 of the present embodiment 2 preparations, thermogravimetric curve (TGA) test is carried out on TA SDT2960instruments, and under nitrogen gas stream protection, heat-up rate is 10K/min.5% thermal weight loss temperature is 447 ℃ as seen from the figure.
The uv-visible absorption spectra figure of the organic semiconductor material P2 of preparation in embodiment 2, uv-visible absorption spectra is measured on Jasco-570 uv analyzer.As seen from the figure: polymkeric substance of the present invention between 300nm ~ 800nm, have large wider absorption, wherein maximum absorption band is positioned at 584nm, wide absorption spectrum shows that P2 is a kind of photovoltaic material.
By test for low temperature phosphorescence spectrum, instrument is FS modular fluorometer/pectrophosphorimeter, to investigate organic semiconductor material P2 triplet state emission characteristic.Under the liquid nitrogen of 77K, organic semiconductor material P2 shows very strong phosphorescent emissions, emission peak is at 449nm, corresponding triplet energy state is 2.76eV, be much higher than phosphor material two (4,6-difluorophenyl pyridine-N, C2) pyridine formyl closes the triplet energy state (2.65eV) of iridium (III) FIrpic, and test data result shows that our material can be used as blue emitting phosphor material of main part.
Embodiment 3:
The present embodiment discloses following poly-{ 4-NSC 62789 oxygen base-N, N-bis-(4-base-phenyl) aniline-co-3,7-bis-base sulphur dibenzofuran } (the organic semiconductor material P3) of structural formula:
Under nitrogen protection, by 4-NSC 62789 oxygen base-N, N-bis-(4-tetramethyl ethylene ketone boric acid ester phenyl) aniline (238mg, 0.3mmol), 3,7-dibromo sulphur dibenzofuran (123mg, 0.33mmol), palladium (3.5mg, 0.015mmol) He three (o-methoxyphenyl) phosphine (21mg, 0.06mmol) join the N that fills 12mL, in the flask of dinethylformamide, after fully dissolving, add salt of wormwood (3mL, 2mol/L) solution, in flask, lead to after the about 30min of nitrogen purge gas subsequently; Flask is heated to 130 ℃ and carries out Suzuki coupling reaction 12h.Stopped reaction cool to room temperature, carry out sedimentation to dripping in flask in 40ml methyl alcohol; After filtering by apparatus,Soxhlet's, use successively methyl alcohol and normal hexane extracting 24h.Then take chloroform as solvent extraction is to colourless, collect chloroformic solution and be spin-dried for and obtain red powder, gathered { 4-NSC 62789 oxygen base-N, N-bis-(4-base-phenyl) aniline-co-3,7-bis-base sulphur dibenzofuran } organic semiconductor material, the last lower 50 ℃ of dry 24h of vacuum.Productive rate is 80%.
The above-mentioned reaction formula of preparing organic semiconductor material P3 is as follows:
Molecule measuring test result is: Molecular weight (GPC, THF, R.I): M
n=75.8kDa, M
w/ M
n=2.0.
The thermogravimetic analysis (TGA) figure of the organic semiconductor material P3 of the present embodiment 3 preparations, thermogravimetric curve (TGA) test is carried out on TA SDT2960instruments, and under nitrogen gas stream protection, heat-up rate is 10K/min.5% thermal weight loss temperature is 386 ℃ as seen from the figure.
The uv-visible absorption spectra figure of the organic semiconductor material P3 of preparation in embodiment 3, uv-visible absorption spectra is measured on Jasco-570 uv analyzer.As seen from the figure: polymkeric substance of the present invention between 300nm ~ 800nm, have large wider absorption, wherein maximum absorption band is positioned at 580nm, wide absorption spectrum shows that P3 is a kind of photovoltaic material.
By test for low temperature phosphorescence spectrum, instrument is FS modular fluorometer/pectrophosphorimeter, to investigate organic semiconductor material P3 triplet state emission characteristic.Under the liquid nitrogen of 77K, organic semiconductor material P3 shows very strong phosphorescent emissions, emission peak is at 443nm, corresponding triplet energy state is 2.80eV, be much higher than phosphor material two (4,6-difluorophenyl pyridine-N, C2) pyridine formyl closes the triplet energy state (2.65eV) of iridium (III) FIrpic, and test data result shows that our material can be used as blue emitting phosphor material of main part.
Embodiment 4:
The present embodiment discloses following poly-{ 4-normal butane oxygen base-N, N-bis-(4-base-phenyl) aniline-co-3,7-bis-base sulphur dibenzofuran } (the organic semiconductor material P4) of structural formula:
Under nitrogen protection; by 4-normal butane oxygen base-N, N-bis-(4-tetramethyl ethylene ketone boric acid ester phenyl) aniline (171mg, 0.3mmol), 3; 7-dibromo sulphur dibenzofuran (135mg; 0.36mmol), three or two argon benzyl acetone two palladiums (9mg, 0.009mmol) and 2-dicyclohexyl phosphines-2 ', 6 '-dimethoxy-biphenyl (29mg; 0.072mmol) join the N that fills 12mL; in the flask of dinethylformamide, after fully dissolving, add sodium carbonate (3mL, 2mol/L) solution.In flask, lead to after the about 30min of nitrogen purge gas subsequently; Flask is heated to 120 ℃ and carries out Suzuki coupling reaction 36h.After cooling, stop polyreaction, to dripping in flask, in 40ml methyl alcohol, carry out sedimentation; After filtering by apparatus,Soxhlet's, use successively methyl alcohol and normal hexane extracting 24h.Then the chloroform of take is extremely colourless as solvent extraction, collects chloroformic solution and be spin-dried for to obtain red powder, is gathered { 4-normal butane oxygen base-N, N-bis-(4-base-phenyl) aniline-co-3,7-bis-base sulphur dibenzofuran } organic semiconductor material, the last lower 50 ℃ of dry 24h of vacuum.Productive rate is 87%.
The above-mentioned reaction formula of preparing organic semiconductor material P4 is as follows:
Molecule measuring test result is: Molecular weight (GPC, THF, R.I): M
n=51.3kDa, M
w/ M
n=2.1.
The thermogravimetic analysis (TGA) figure of the organic semiconductor material of the present embodiment 4 preparations, thermogravimetric curve (TGA) test is carried out on TA SDT2960instruments, and under nitrogen gas stream protection, heat-up rate is 10K/min.5% thermal weight loss temperature is 430 ℃ as seen from the figure.
The uv-visible absorption spectra figure of the organic semiconductor material P4 of preparation in embodiment 4, uv-visible absorption spectra is measured on Jasco-570 uv analyzer.As seen from the figure: polymkeric substance of the present invention between 300nm ~ 800nm, have large wider absorption, wherein maximum absorption band is positioned at 582nm, wide absorption spectrum shows that P4 is a kind of photovoltaic material.
By test for low temperature phosphorescence spectrum, instrument is FS modular fluorometer/pectrophosphorimeter, to investigate organic semiconductor material P4 triplet state emission characteristic.Under the liquid nitrogen of 77K, organic semiconductor material P4 shows very strong phosphorescent emissions, emission peak is at 444nm, corresponding triplet energy state is 2.79eV, be much higher than phosphor material two (4,6-difluorophenyl pyridine-N, C2) pyridine formyl closes the triplet energy state (2.65eV) of iridium (III) FIrpic, and test data result shows that our material can be used as blue emitting phosphor material of main part.
Embodiment 5:
The present embodiment discloses following poly-{ 4-n-dodecane oxygen base-N, N-bis-(4-tetramethyl ethylene ketone boric acid ester phenyl) aniline } (the organic semiconductor material P5) of structural formula:
Under nitrogen protection; by 4-n-dodecane oxygen base-N; N-bis-(4-tetramethyl ethylene ketone boric acid ester phenyl) aniline (205mg; 0.3mmol), 3; 7-dibromo sulphur dibenzofuran (112mg, 0.3mmol), tetra-triphenylphosphine palladium (8mg, 0.006mmol) join and fill in the twoport flask that 15mL toluene adds 50mL; after fully dissolving, add salt of wormwood (3mL, 2mol/L) solution.In flask, lead to after the about 10min of nitrogen purge gas subsequently; Flask is heated to 90 ℃ and carries out Suzuki coupling reaction 60h.After cooling, stop polyreaction, to dripping in flask, in 40ml methyl alcohol, carry out sedimentation; After filtering by apparatus,Soxhlet's, use successively methyl alcohol and normal hexane extracting 24h.Then the chloroform of take is extremely colourless as solvent extraction, collects chloroformic solution and be spin-dried for to obtain red powder, is gathered { 4-n-dodecane oxygen base-N, N-bis-(4-tetramethyl ethylene ketone boric acid ester phenyl) aniline } organic semiconductor material, the last lower 50 ℃ of dry 24h of vacuum.Productive rate is 73%.
The above-mentioned reaction formula of preparing organic semiconductor material P5 is as follows:
Molecule measuring test result is: Molecular weight (GPC, THF, R.I): M
n=4.3kDa, M
w/ M
n=2.4.
The thermogravimetic analysis (TGA) figure of the organic semiconductor material P5 of the present embodiment 5 preparations, thermogravimetric curve (TGA) test is carried out on TA SDT2960instruments, and under nitrogen gas stream protection, heat-up rate is 10K/min.5% thermal weight loss temperature is 395 ℃ as seen from the figure.
The uv-visible absorption spectra figure of the organic semiconductor material P5 of preparation in embodiment 5, uv-visible absorption spectra is measured on Jasco-570 uv analyzer.As seen from the figure: polymkeric substance of the present invention between 300nm ~ 800nm, have large wider absorption, wherein maximum absorption band is positioned at 584nm, wide absorption spectrum shows that P5 is a kind of photovoltaic material.
By test for low temperature phosphorescence spectrum, instrument is FS modular fluorometer/pectrophosphorimeter, to investigate organic semiconductor material P5 triplet state emission characteristic.Under the liquid nitrogen of 77K, organic semiconductor material P5 shows very strong phosphorescent emissions, emission peak is at 448nm, corresponding triplet energy state is 2.77eV, be much higher than phosphor material two (4,6-difluorophenyl pyridine-N, C2) pyridine formyl closes the triplet energy state (2.65eV) of iridium (III) FIrpic, and test data result shows that our material can be used as blue emitting phosphor material of main part.
Application Example
Organic electroluminescence device 300, as Fig. 1, it comprises substrate 301 to its structure, anode 302, hole injection layer 303, hole transmission layer 304, luminescent layer 305, electron transfer layer 306, electronic injection buffer layer 307, negative electrode 308.
In the present embodiment, the material of substrate 301 is glass, vacuum plating anode 302 successively in substrate 301, hole injection layer 303, hole transmission layer 304, luminescent layer 305, electron transfer layer 306, electronic injection buffer layer 307, negative electrode 308, anode 302 adopts the tin indium oxide that square resistance is 10 ~ 20 Ω/, thickness is 150nm, hole injection layer 303 adopts poly-(3, 4-ethene dioxythiophene)-polystyrolsulfon acid, thickness is 30nm, hole transmission layer 304 adopts N, N '-phenylbenzene-N, N '-(1-naphthyl)-1, 1 '-biphenyl-4, 4 '-diamines, thickness is 20nm, luminescent layer 305 main body luminescent materials adopt poly-{ the 4-normal hexane oxygen-N of the compound of the invention process 1 preparation, N-bis-(4-base-phenyl) aniline-co-3, 7-bis-base sulphur dibenzofuran }, and take the object luminescent material two (4 that material of main part is 10% as benchmark doping mass percent, 6-difluorophenyl pyridine-N, C2) pyridine formyl closes iridium (III), luminescent layer 305 thickness are 20nm, electron transfer layer 306 adopts 5 (4, 7-phenylbenzene-1, 10-phenanthroline, thickness is 30nm, electronic injection buffer layer 307 adopts lithium fluoride, thickness is 1nm, negative electrode 308 adopts metallic aluminium, thickness is 100nm.
Organic layer and metal level all adopt thermal evaporation process deposits to complete, and vacuum tightness is 10
-3～10
-5pa, the thickness of film adopts film thickness monitoring instrument to monitor, and except guest materials, the vaporator rate of all organic materialss is
the vaporator rate of lithium fluoride is
the vaporator rate of metallic aluminium is
This electroluminescent device has higher luminous efficiency, can be widely used in the luminous fields such as blueness or white.Electric current-the brightness-voltage characteristic of device is that all measurements that completed by the Keithley source measuring system (Keithley2400Sourcemeter, Keithley2000Cuirrentmeter) with correction silicon photoelectric diode all complete in atmosphere at room temperature.Result shows: the maximum electrical efficiency of device is 11.8cd/A, and high-high brightness is 26290cd/m
2.
The above embodiment has only expressed several embodiment of the present invention, and it describes comparatively concrete and detailed, but can not therefore be interpreted as the restriction to the scope of the claims of the present invention.It should be pointed out that for the person of ordinary skill of the art, without departing from the inventive concept of the premise, can also make some distortion and improvement, these all belong to protection scope of the present invention.Therefore, the protection domain of patent of the present invention should be as the criterion with claims.
Claims (10)
1. an organic semiconductor material, is characterized in that, the chemical formula of described organic semiconductor material is as follows:
wherein, R is C
1~ C
20alkyl, the integer that n is 10 ~ 100.
2. a preparation method for organic semiconductor material, is characterized in that, comprises the steps:
Compd A is provided:
and compd B:
wherein, R is C
1~ C
20alkyl; Under inert atmosphere, by compd A and compd B, according to mol ratio, be 1:1 ~ 1: 1.2 are added in the organic solvent that contains catalyzer and alkaline solution, at 70～130 ℃, carry out Suzuki coupling reaction 12～96 hours, described catalyzer is organic palladium or is the mixture of organic palladium and organophosphor ligand, obtains the organic semiconductor material P that following structural formula represents:
wherein, the integer that n is 10 ~ 100.
3. preparation method as claimed in claim 2, it is characterized in that, also comprise the step of organic semiconductor material P being carried out to separation and purification, described purification procedures is as follows: to described compd A and compd B, carry out adding methyl alcohol precipitating also to filter in the solution after Suzuki coupling reaction, the solid that filtration is obtained carries out extracting with methyl alcohol and normal hexane successively, by the chloroform extracting of the solid after extracting, after collection chloroformic solution, evaporating solvent obtains the organic semiconductor material P after purifying.
4. preparation method as claimed in claim 2, is characterized in that, described organic solvent is selected from least one in toluene, DMF, tetrahydrofuran (THF).
5. preparation method as claimed in claim 2, is characterized in that, described alkaline solution is selected from least one in sodium carbonate solution, solution of potassium carbonate and sodium hydrogen carbonate solution, and the solute in described alkaline solution and the mol ratio of compd A are 20:1 ~ 50:1.
6. preparation method as claimed in claim 2, it is characterized in that, described organic palladium is bi triphenyl phosphine dichloride palladium, tetra-triphenylphosphine palladium, palladium or three dibenzalacetone two palladiums, described organophosphorus ligand is tri-butyl phosphine, tri-o-tolyl phosphine or 2-dicyclohexyl phosphorus-2 ', 6 '-dimethoxy-biphenyl, the mol ratio of described organic palladium and described organophosphorus ligand is 1:4 ~ 1:8.
7. preparation method as claimed in claim 2, is characterized in that, the organic palladium in described catalyzer and the mol ratio of described compd A are 1:20 ~ 1:100.
8. an electroluminescent device, is characterized in that, comprises the substrate with anode, luminescent layer and the cathode layer that stack gradually, and described luminescent layer is the mixture of material of main part and guest materials, wherein material of main part organic semiconductor material as follows:
wherein, R is C
1~ C
20alkyl, n is 10 ~ 100 integer, guest materials is three [1-phenyl isoquinolin quinoline-C2, N] iridium, two (4,6-difluorophenyl pyridine-N, C2) pyridine formyl closes that iridium, [two (2 ', 4 '-difluorophenyl) pyridine] [four (1-pyrazolyl) boron] close iridium or [two (2 ', 4 '-difluorophenyl) pyridine] (tetrazolium pyridine) closes iridium.
9. electroluminescent device as claimed in claim 8, is characterized in that, the mass percent of described material of main part and described guest materials is 5%～15%.
10. electroluminescent device as claimed in claim 8, is characterized in that, described anode material is indium zinc oxide or zinc oxide aluminum, and negative electrode is metallic aluminium, silver, gold or nickel.
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| CN106633002A (en) * | 2016-12-09 | 2017-05-10 | 华南理工大学 | Triarylamine-end-group-content-adjustable polymer containing S,S-dioxo-dibenzothiophene in main chain, and preparation method and application thereof |
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| CN102775398B (en) * | 2012-07-25 | 2016-01-06 | 中节能万润股份有限公司 | A kind of Novel bipolar material and application thereof |
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| CN1976883A (en) * | 2004-06-28 | 2007-06-06 | 出光兴产株式会社 | Polycyclic aromatic compound, material for forming light-emitting coating film using the same, and organic electroluminescent device |
| 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 |
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| CN106633002A (en) * | 2016-12-09 | 2017-05-10 | 华南理工大学 | Triarylamine-end-group-content-adjustable polymer containing S,S-dioxo-dibenzothiophene in main chain, and preparation method and application thereof |
| CN106633002B (en) * | 2016-12-09 | 2020-06-19 | 华南理工大学 | Triarylamine end group content-adjustable polymer with main chain containing S, S-dioxo-dibenzothiophene as well as preparation method and application thereof |
Also Published As
| Publication number | Publication date |
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| CN103965441B (en) | 2016-08-17 |
| CN105694006B (en) | 2018-01-23 |
| CN105694006A (en) | 2016-06-22 |
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