CN103965446A - Organic semiconductor material polymer and preparation method thereof, and organic electroluminescent device - Google Patents
Organic semiconductor material polymer and preparation method thereof, and organic electroluminescent device Download PDFInfo
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- CN103965446A CN103965446A CN201310038647.9A CN201310038647A CN103965446A CN 103965446 A CN103965446 A CN 103965446A CN 201310038647 A CN201310038647 A CN 201310038647A CN 103965446 A CN103965446 A CN 103965446A
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- 239000000463 material Substances 0.000 title claims abstract description 103
- 239000004065 semiconductor Substances 0.000 title claims abstract description 90
- 229920000642 polymer Polymers 0.000 title claims abstract description 56
- 238000002360 preparation method Methods 0.000 title claims abstract description 39
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims description 54
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 48
- 239000000126 substance Substances 0.000 claims description 46
- 239000000243 solution Substances 0.000 claims description 30
- 229910052763 palladium Inorganic materials 0.000 claims description 27
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 26
- 238000006069 Suzuki reaction reaction Methods 0.000 claims description 18
- 230000027756 respiratory electron transport chain Effects 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
- 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 15
- 238000005401 electroluminescence Methods 0.000 claims description 15
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 claims description 14
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 13
- 238000006243 chemical reaction Methods 0.000 claims description 12
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 claims description 12
- 239000003446 ligand Substances 0.000 claims description 11
- 239000000203 mixture Substances 0.000 claims description 11
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 10
- 239000012670 alkaline solution Substances 0.000 claims description 9
- 238000001914 filtration Methods 0.000 claims description 8
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 claims description 8
- 239000007787 solid Substances 0.000 claims description 8
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 7
- 239000003960 organic solvent Substances 0.000 claims description 7
- 230000001376 precipitating effect Effects 0.000 claims description 7
- 229910000030 sodium bicarbonate Inorganic materials 0.000 claims description 7
- 235000017557 sodium bicarbonate Nutrition 0.000 claims description 7
- 238000000746 purification Methods 0.000 claims description 5
- 230000035484 reaction time Effects 0.000 claims description 5
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 5
- 239000002904 solvent Substances 0.000 claims description 5
- 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 4
- 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
- 229910000027 potassium carbonate Inorganic materials 0.000 claims description 4
- TUQOTMZNTHZOKS-UHFFFAOYSA-N tributylphosphine Chemical compound CCCCP(CCCC)CCCC TUQOTMZNTHZOKS-UHFFFAOYSA-N 0.000 claims description 4
- 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
- 238000000926 separation method Methods 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
- 230000005540 biological transmission Effects 0.000 abstract description 7
- 125000003837 (C1-C20) alkyl group Chemical group 0.000 abstract 1
- 238000004020 luminiscence type Methods 0.000 abstract 1
- 239000010410 layer Substances 0.000 description 47
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 36
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 25
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 16
- 239000007789 gas Substances 0.000 description 15
- 238000002347 injection Methods 0.000 description 12
- 239000007924 injection Substances 0.000 description 12
- 238000000862 absorption spectrum Methods 0.000 description 11
- 239000000872 buffer Substances 0.000 description 11
- 229920000144 PEDOT:PSS Polymers 0.000 description 10
- 239000005864 Sulphur Substances 0.000 description 10
- 238000010521 absorption reaction Methods 0.000 description 10
- 125000003983 fluorenyl group Chemical class C1(=CC=CC=2C3=CC=CC=C3CC12)* 0.000 description 10
- 229910052757 nitrogen Inorganic materials 0.000 description 10
- 239000001301 oxygen Substances 0.000 description 10
- 229910052760 oxygen Inorganic materials 0.000 description 10
- 238000001894 space-charge-limited current method Methods 0.000 description 10
- 238000012360 testing method Methods 0.000 description 10
- 239000004411 aluminium Substances 0.000 description 8
- 229910052782 aluminium Inorganic materials 0.000 description 8
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 8
- 229910052786 argon Inorganic materials 0.000 description 8
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 7
- MRNHPUHPBOKKQT-UHFFFAOYSA-N indium;tin;hydrate Chemical compound O.[In].[Sn] MRNHPUHPBOKKQT-UHFFFAOYSA-N 0.000 description 7
- 238000004458 analytical method Methods 0.000 description 6
- PQXKHYXIUOZZFA-UHFFFAOYSA-M lithium fluoride Chemical compound [Li+].[F-] PQXKHYXIUOZZFA-UHFFFAOYSA-M 0.000 description 6
- 239000000758 substrate Substances 0.000 description 6
- 239000002253 acid Substances 0.000 description 5
- 239000004327 boric acid Substances 0.000 description 5
- 238000001816 cooling Methods 0.000 description 5
- 229910001873 dinitrogen Inorganic materials 0.000 description 5
- 150000002148 esters Chemical class 0.000 description 5
- 238000000638 solvent extraction Methods 0.000 description 5
- 230000004580 weight loss Effects 0.000 description 5
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N diphenyl Chemical compound C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 description 4
- 238000007599 discharging Methods 0.000 description 4
- 229910052741 iridium Inorganic materials 0.000 description 4
- GKOZUEZYRPOHIO-UHFFFAOYSA-N iridium atom Chemical compound [Ir] GKOZUEZYRPOHIO-UHFFFAOYSA-N 0.000 description 4
- 235000015320 potassium carbonate Nutrition 0.000 description 4
- 150000005224 alkoxybenzenes Chemical class 0.000 description 3
- 229940094933 n-dodecane Drugs 0.000 description 3
- 235000011181 potassium carbonates Nutrition 0.000 description 3
- 239000000843 powder Substances 0.000 description 3
- 0 CC1(C)OB(c(cc2)cc3c2-c2ccc(B4OC(C)(C)C(C)(C)O4)cc2C3(c2ccc(*)cc2)c(cc2)ccc2O*)OC1(C)C Chemical compound CC1(C)OB(c(cc2)cc3c2-c2ccc(B4OC(C)(C)C(C)(C)O4)cc2C3(c2ccc(*)cc2)c(cc2)ccc2O*)OC1(C)C 0.000 description 2
- SHGUVJPXKKRMRP-UHFFFAOYSA-N [O].CCCC Chemical compound [O].CCCC SHGUVJPXKKRMRP-UHFFFAOYSA-N 0.000 description 2
- 239000004305 biphenyl Substances 0.000 description 2
- 235000010290 biphenyl Nutrition 0.000 description 2
- 230000003197 catalytic effect Effects 0.000 description 2
- XCJYREBRNVKWGJ-UHFFFAOYSA-N copper(II) phthalocyanine Chemical compound [Cu+2].C12=CC=CC=C2C(N=C2[N-]C(C3=CC=CC=C32)=N2)=NC1=NC([C]1C=CC=CC1=1)=NC=1N=C1[C]3C=CC=CC3=C2[N-]1 XCJYREBRNVKWGJ-UHFFFAOYSA-N 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 239000011521 glass Substances 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 238000000034 method Methods 0.000 description 2
- 239000000178 monomer Substances 0.000 description 2
- 125000001624 naphthyl group Chemical group 0.000 description 2
- 238000007747 plating Methods 0.000 description 2
- 238000010926 purge Methods 0.000 description 2
- JUJWROOIHBZHMG-UHFFFAOYSA-N pyridine Substances C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 2
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 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
- YXPUNWKYPJPPFC-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 YXPUNWKYPJPPFC-UHFFFAOYSA-N 0.000 description 1
- 229940126062 Compound A Drugs 0.000 description 1
- 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 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- 239000012298 atmosphere Substances 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 238000012937 correction Methods 0.000 description 1
- 238000006392 deoxygenation reaction Methods 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
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- 239000012044 organic layer Substances 0.000 description 1
- 230000000630 rising effect Effects 0.000 description 1
- 238000004062 sedimentation Methods 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 238000002207 thermal evaporation Methods 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
-
- 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
- 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
- C08G2261/52—Luminescence
- C08G2261/522—Luminescence fluorescent
- C08G2261/5222—Luminescence fluorescent electrofluorescent
-
- 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
- C08G2261/90—Applications
- C08G2261/95—Use in organic luminescent diodes
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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)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Electroluminescent Light Sources (AREA)
- Polyoxymethylene Polymers And Polymers With Carbon-To-Carbon Bonds (AREA)
Abstract
The invention relates to an organic semiconductor material polymer, which has the following structural formula, wherein R1 is C1-C20 alkyl, and n is an integer of 10-100. The organic semiconductor material polymer has high electron mobility, excellent film forming performance and excellent morphology stability, is suitable as an electronic transmission layer so as to be applied in organic electroluminescent devices, and can be provided for improving luminescence efficiency of the organic electroluminescent device, wherein the electron mobility of the polymer is about 10<-5> cm<2>V<-1>S<-1> so as to solve the problem of low efficiency of the organic electroluminescent device. The present invention further provides a preparation method for the organic semiconductor material polymer, and an organic electroluminescent device applying the organic semiconductor material.
Description
[technical field]
The present invention relates to photoelectric field, relate in particular to a kind of polymkeric substance and preparation method thereof and the organic electroluminescence device that uses the polymkeric substance of this organic semiconductor material of organic semiconductor material.
[background technology]
That organic electroluminescence device has is light, thin, luminous, low consumpting power, do not need light source, without angle limitations, high reaction rate and can be produced on the good characteristics such as flexible base plate, be regarded as the rising star of flat-panel screens and flexible display.The carrier mobility of traditional electron transport material is the thousandth of hole mobile material, and thermostability is not good, therefore, often cause the problems such as the not good or component life of luminous efficiency is long, the electron transport material of therefore developing a kind of high carrier is the nowadays emphasis of organic electroluminescence device developing material.
[summary of the invention]
Based on this, be necessary to provide the polymkeric substance of the organic semiconductor material that a kind of energy conversion efficiency is higher.
In addition, be also necessary to provide a kind of preparation method of polymkeric substance of organic semiconductor material.
In addition, be also necessary to provide the organic electroluminescence device of the polymkeric substance that uses organic semiconductor material.
A polymkeric substance for organic semiconductor material, has following structural formula:
Wherein, R
1for C
1~ C
20alkyl, the integer that n is 10 ~ 100.
A preparation method for the polymkeric substance of organic semiconductor material, comprises the steps:
The compd A and the compd B that provide following structural formula to represent,
A is:
b is:
wherein, R
1for C
1~ C
20alkyl;
In oxygen-free environment, the compd A that is 1:1 ~ 1:1.2 by mol ratio and compd B are added in the organic solvent that contains catalyzer and alkaline solution, at 70 ℃～130 ℃, carry out Suzuki coupling reaction 12 hours～96 hours, described catalyzer is organic palladium or is the mixture of organic palladium and organophosphor ligand, obtains the polymer P of the organic semiconductor material that following structural formula represents:
Wherein, the integer that n is 10 ~ 100.
Described organic solvent is selected from least one in toluene, DMF and tetrahydrofuran (THF).
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.
Organic palladium in described catalyzer and the mol ratio of described compd A are 1:20 ~ 1: 100.
The temperature of reaction of described Suzuki coupling reaction is 90 ℃ ~ 120 ℃, and the reaction times is 24 hours ~ 72 hours.
Described alkaline solution is selected from least one in sodium carbonate solution, solution of potassium carbonate and sodium hydrogen carbonate solution.
Solute in described alkaline solution and the mol ratio of compd A are 20:1 ~ 50:1.
Also comprise the step of the polymer P of organic semiconductor material 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 polymer P of the organic semiconductor material after purifying.
Described extracting adopts apparatus,Soxhlet's to carry out.
An organic electroluminescence device, comprises electron transfer layer, and described electron transfer layer has the polymer P of the organic semiconductor material of following structural formula:
Wherein, R
1for C
1~ C
20alkyl, the integer that n is 10 ~ 100.
The polymkeric substance of above-mentioned organic semiconductor material has high electronic mobility and good film forming properties and stable appearance, is suitable as electron transfer layer and is applied in organic electronic light emitting device, and can improve the luminous efficiency of organic electronic light emitting device.The electronic mobility of this polymkeric substance is 10
-5cm
2v
-1s
-1left and right, and then solve organic semiconductor luminescent device low efficiency problem.The present invention also provide a kind of above-mentioned organic semiconductor material polymkeric substance preparation method and use the organic electroluminescence device of this organic semiconductor material.
The preparation method of the polymkeric substance of above-mentioned organic semiconductor material, has adopted better simply synthetic route, thereby reduces technical process, and starting material are cheap and easy to get, and manufacturing cost is reduced; And worth polymeric material novel structure, solubility property is good, and film forming properties is good, applicable to organic electroluminescence device.
[accompanying drawing explanation]
Fig. 1 is preparation method's the schema of polymkeric substance of the organic semiconductor material of an embodiment;
Fig. 2 is the structural representation of the organic electroluminescence device of an embodiment;
Fig. 3 is the uv-visible absorption spectra figure of polymkeric substance of the organic semiconductor material of embodiment 1 preparation;
Fig. 4 is the thermogravimetic analysis (TGA) figure of polymkeric substance of the organic semiconductor material of embodiment 1 preparation.
[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, and monomers B is bought and obtained from the market.
The polymkeric substance of the organic semiconductor material of one embodiment, has following structural formula:
Wherein, R
1for C
1~ C
20alkyl, the integer that n is 10 ~ 100.
The polymkeric substance of above-mentioned this organic semiconductor material has high electronic mobility and good film forming properties and stable appearance, is suitable as electron transfer layer and is applied in organic electronic light emitting device, and can improve the luminous efficiency of organic electronic light emitting device.The electronic mobility of this polymkeric substance is 10
-5cm
2v
-1s
-1left and right, and then solve organic semiconductor luminescent device low efficiency problem.The present invention also provide a kind of above-mentioned organic semiconductor material polymkeric substance preparation method and use the organic electroluminescence device of this organic semiconductor material.
The preparation method of the polymkeric substance of the organic semiconductor material of one embodiment, as shown in Figure 1, comprises the following steps:
Step S1, provide compd A and compd B.
The structural formula of compd A is:
wherein, R
1for C
1~ C
20alkyl.
The structural formula of compd B is:
Step S2, prepare the polymer P of organic semiconductor material.
In oxygen-free environment, the compd A that is 1:1 ~ 1:1.2 by mol ratio and compd B are added in the organic solvent that contains catalyzer and alkaline solution, at 70 ℃～130 ℃, carry out Suzuki coupling reaction 12 hours～96 hours, described catalyzer is the mixture of organic palladium or organic palladium and organophosphor ligand, obtains the polymer P of the organic semiconductor material that following structural formula represents:
Wherein, the integer that n is 10 ~ 100.
In present embodiment, Suzuki coupling reaction carries out under nitrogen atmosphere.
In present embodiment, organic solvent is selected from least one in toluene, DMF and tetrahydrofuran (THF).Be appreciated that organic solution also can be used other solvents, as long as can dissolved compound A and compd B.
In present embodiment, organic palladium is bi triphenyl phosphine dichloride palladium, tetra-triphenylphosphine palladium, palladium or three dibenzalacetone two palladiums, and organophosphorus ligand is tri-butyl phosphine, tri-o-tolyl phosphine or 2-dicyclohexyl phosphorus-2 ', 6 '-dimethoxy-biphenyl.In the mixture of organic palladium and organophosphor ligand, the mol ratio of organic palladium and organophosphor ligand is 1:4 ~ 1:8.Preferably, adopt the mixture of three dibenzalacetone two palladiums and tri-butyl phosphine as catalyzer.Be appreciated that organic palladium, organophosphor ligand are all not limited to cited kind, as long as energy catalytic cpd A and compd B carry out Suzuki coupling reaction.
In present embodiment, in catalyzer, the mol ratio of organic palladium and compd A is 1:20 ~ 1:100.The mol ratio that is appreciated that organic palladium and compd A is not limited to 1:20 ~ 1:100, to adding the catalyzer that adds catalytic amount in the organic solvent of compd A and compd B.
In present embodiment, the temperature of reaction of Suzuki coupling reaction is 70 ℃ ~ 130 ℃, and the reaction times is 12 hours ~ 96 hours.Preferably, the temperature of reaction of Suzuki coupling reaction is 90 ℃ ~ 120 ℃, and the reaction times is 24 hours ~ 72 hours.The temperature of reaction that is appreciated that Suzuki coupling reaction is not limited to 70 ℃ ~ 130 ℃, as long as can make compd A and compd B react; Reaction times is also not limited to 12 hours ~ and 96 hours, as long as can make compd A and compd B react completely as far as possible.
In present embodiment, described alkaline solution is selected from least one in sodium carbonate solution, solution of potassium carbonate and sodium hydrogen carbonate solution, wherein the solute of sodium carbonate solution is sodium carbonate, and the solute of solution of potassium carbonate is that the solute of salt of wormwood and sodium hydrogen carbonate solution is sodium bicarbonate;
In present embodiment, the solute in described alkaline solution and the mol ratio of compd A are 20:1 ~ 50:1.
The polymer P of step S3, separation and purification organic semiconductor material.
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 polymer P of the organic semiconductor material after purifying.
In present embodiment, extracting is used apparatus,Soxhlet's to carry out.
In present embodiment, by collect polymer P that evaporating solvent after chloroformic solution obtains the organic semiconductor material after purifying under vacuum 50 ℃～70 ℃ dry 24 hours～48 hours.
The preparation method of the polymkeric substance of above-mentioned organic semiconductor material, synthetic route is comparatively simple, has reduced manufacturing cost.
A kind of organic electroluminescence device 300 in one embodiment, as Fig. 2, 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 CuPc, thickness is 30nm, hole transmission layer 304 adopts 4, two [N-(1-the naphthyl)-N-phenylamino] biphenyl of 4'-, thickness is 20nm, luminescent layer 305 main body luminescent materials adopt 9, 9'-(1, 3-phenyl) two-9H-carbazole, and take the object luminescent material two (4 that material of main part is 5% as benchmark doping mass percent, 6-difluorophenyl pyridine-N, C2) pyridine formyl closes iridium (III), luminescent layer 305 thickness are 20nm, the polymkeric substance of the organic semiconductor material that the electron transfer layer 306 employing embodiment of the present invention provide, thickness is 30nm, electronic injection buffer layer 307 adopts lithium fluoride, thickness is 1nm, negative electrode 308 adopts metallic aluminium, thickness is 100nm.
Described electron transfer layer has the polymer P of the organic semiconductor material of following structural formula:
Wherein, R
1for C
1~ C
20alkyl, the integer that n is 10 ~ 100.
Be specific embodiment below.
Embodiment 1
The present embodiment discloses following poly-{ 3,7-, bis-bases-sulphur dibenzofuran-co-2,7-bis--Ji-9,9-bis-(4-normal hexane oxygen base benzene) fluorenes } (polymer P 1 of organic semiconductor material) of structural formula:
The preparation process of the polymer P 1 of above-mentioned organic semiconductor material is as follows:
Under argon shield, by 3,7-dibromo sulphur dibenzofuran (75mg, 0.2mmol), 9,9-bis-(4-normal hexane oxygen base benzene) fluorenes-2,7-bis-tetramethyl ethylene ketone boric acid esters (154mg, 0.2mmol) add in the flask that fills 10ml toluene solvant, after fully dissolving by salt of wormwood (2mL, 2mol/L) solution joins 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.Subsequently, 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, and under vacuum pump, taking out spends the night obtains product poly-{ 3,7-, bis-bases-sulphur dibenzofuran-co-2,7-bis-base-9,9-bis-(4-normal hexane oxygen base benzene) fluorenes }, productive rate 76%.
The reaction formula of the above-mentioned polymer P 1 of preparing organic semiconductor material is as follows:
Molecule measuring test result is: Molecular weight (GPC, THF, R.I): M
n=43.5kDa, M
w/ M
n=2.2.
Referring to accompanying drawing 3, be the uv-visible absorption spectra figure of the polymer P 1 of the organic semiconductor material 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 ~ 700nm, have large wider absorption, wherein maximum absorption band is positioned at 609nm.
Referring to accompanying drawing 4, be the thermogravimetic analysis (TGA) figure of polymer P 1 of the organic semiconductor material of the present embodiment 1 preparation, 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 (T as seen from the figure
d) be 412 ℃.
The polymer P 1/Au of ITO/PEDOT:PSS/ the present embodiment 1 organic semiconductor material of take is device architecture, the structure anode of this device adopts tin indium oxide, Hole-injecting Buffer Layer for Improvement adopts poly-(3,4-ethene dioxythiophene)-polystyrolsulfon acid (PEDOT:PSS), the polymer P 1 of organic semiconductor material prepared by electron transfer layer employing the present embodiment, negative electrode adopts metallic aluminium, and the electronic mobility of polymkeric substance that adopted space charge limited current (SCLC) model determination, the electronic mobility that obtains the polymer P 1 of organic semiconductor material is 2.3 * 10
-5cm
2/ Vs.
Embodiment 2
The present embodiment discloses following poly-{ 3,7-, bis-bases-sulphur dibenzofuran-co-2,7-bis-base-9,9-bis-(4-first alkoxy benzene) fluorenes } (polymer P 2 of organic semiconductor material) of structural formula:
The preparation process of the polymer P 2 of above-mentioned organic semiconductor material is as follows:
Under nitrogen and the protection of argon gas gas mixture, by 3, 7-dibromo sulphur dibenzofuran (112mg, 0.3mmol), 9, 9-bis-(4-first alkoxy benzene) fluorenes-2, 7-bis-tetramethyl ethylene ketone boric acid ester (189mg, 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, again 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 60h.Subsequently, after cooling, stop polyreaction, in two-mouth bottle, add 40mL methyl alcohol precipitating, 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 solid, obtains product poly-{ 3,7-, bis-bases-sulphur dibenzofuran-co-2,7-bis-base-9,9-bis-(4-first alkoxy benzene) fluorenes } after collection under vacuum after 50 ℃ of dry 24h.Productive rate is 82%.
The reaction formula of the above-mentioned polymer P 2 of preparing organic semiconductor material is as follows:
Molecule measuring test result is: Molecular weight (GPC, THF, R.I): M
n=58.7kDa, M
w/ M
n=2.0.
The uv-visible absorption spectra figure of the polymer P 2 of the organic semiconductor material of preparation in the present 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 ~ 700nm, have large wider absorption, wherein maximum absorption band is positioned at 607nm.
The thermogravimetic analysis (TGA) of the polymer P 2 of the organic semiconductor material 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 (T
d) be 451 ℃.
The polymer P 2/Au of ITO/PEDOT:PSS/ the present embodiment 2 organic semiconductor material of take is device architecture, the structure anode of this device adopts tin indium oxide, Hole-injecting Buffer Layer for Improvement adopts poly-(3,4-ethene dioxythiophene)-polystyrolsulfon acid (PEDOT:PSS), the polymer P 2 of organic semiconductor material prepared by electron transfer layer employing the present embodiment, negative electrode adopts metallic aluminium, and the electronic mobility of polymkeric substance that adopted space charge limited current (SCLC) model determination, the electronic mobility that obtains polymkeric substance is 2.8 * 10
-5cm
2/ Vs.
Embodiment 3
The present embodiment discloses following poly-{ 3,7-, bis-bases-sulphur dibenzofuran-co-2,7-bis-base-9,9-bis-(4-NSC 62789 oxygen base benzene) fluorenes } (polymer P 3 of organic semiconductor material) of structural formula:
The preparation process of the polymer P 3 of above-mentioned organic semiconductor material is as follows:
Under nitrogen protection, by 3,7-dibromo sulphur dibenzofuran (112mg, 0.3mmol), 9,9-bis-(4-NSC 62789 oxygen base benzene) fluorenes-2,7-bis-tetramethyl ethylene ketone boric acid ester (384mg, 0.33mmol), palladium (3.5mg, 0.015mmol) He three (o-methoxyphenyl) phosphine (21mg, 0.06mmol) join in the flask of the DMF that fills 12mL, after fully dissolving, add salt of wormwood (3mL, 2mol/L) solution leads to after the about 20min of nitrogen purge gas subsequently in flask; Flask is heated to 130 ℃ and carries out Suzuki coupling reaction 12h.Subsequently, after cooling, stop polyreaction, in flask, add 40mL methyl alcohol precipitating, 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, after collection under vacuum after 50 ℃ of dry 24h, be product poly-{ 3,7-, bis-bases-sulphur dibenzofuran-co-2,7-bis-base-9,9-bis-(4-NSC 62789 oxygen base benzene) fluorenes }, productive rate is 75%.
The reaction formula of the above-mentioned polymer P 3 of preparing organic semiconductor material is as follows:
Molecule measuring test result is: Molecular weight (GPC, THF, R.I): M
n=16.1kDa, M
w/ M
n=2.4.
The uv-visible absorption spectra figure of the polymer P 3 of the organic semiconductor material of preparation in the present 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 ~ 700nm, have large wider absorption, wherein maximum absorption band is positioned at 613nm.
The thermogravimetic analysis (TGA) of the polymer P 3 of the organic semiconductor material 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 (T
d) be 398 ℃.
The polymer P 3/Au of ITO/PEDOT:PSS/ the present embodiment 3 organic semiconductor material of take is device architecture, the structure anode of this device adopts tin indium oxide, Hole-injecting Buffer Layer for Improvement adopts poly-(3,4-ethene dioxythiophene)-polystyrolsulfon acid (PEDOT:PSS), the polymer P 3 of organic semiconductor material prepared by electron transfer layer employing the present embodiment, negative electrode adopts metallic aluminium, and the electronic mobility of polymkeric substance that adopted space charge limited current (SCLC) model determination, the electronic mobility that obtains polymkeric substance is 2.7 * 10
-5cm
2/ Vs.
Embodiment 4
The present embodiment discloses following poly-{ 3,7-, bis-bases-sulphur dibenzofuran-co-2,7-bis--Ji-9,9-bis-(4-normal butane oxygen base benzene) fluorenes } (polymer P 4 of organic semiconductor material) of structural formula:
The preparation process of the polymer P 4 of above-mentioned organic semiconductor material is as follows:
Under nitrogen protection, by 3,7-dibromo sulphur dibenzofuran (112mg, 0.3mmol), 9,9-bis-(4-NSC 62789 oxygen base benzene) fluorenes-2,7-bis-tetramethyl ethylene ketone boric acid ester (257mg, 0.36mmol), three or two argon benzyl acetone two palladium (9mg, 0.009mmol), with 2-dicyclohexyl phosphine-2 ', 6 '-dimethoxy-biphenyl (29mg, 0.072mmol) joins the N that fills 12mL, in the flask of dinethylformamide, after fully dissolving, add sodium bicarbonate (3mL, 2mol/L) solution, in flask, lead to after the about 20min of nitrogen purge gas subsequently; Flask is heated to 120 ℃ and carries out Suzuki coupling reaction 36h.Subsequently, after cooling, stop polyreaction, in flask, add 40mL methyl alcohol precipitating, 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, after collection under vacuum after 50 ℃ of dry 24h, be product poly-{ 3,7-, bis-bases-sulphur dibenzofuran-co-2,7-bis-base-9,9-bis-(4-normal butane oxygen base benzene) fluorenes }, productive rate is 78%.
The reaction formula of the above-mentioned polymer P 4 of preparing organic semiconductor material is as follows:
Molecule measuring test result is: Molecular weight (GPC, THF, R.I): M
n=23.7kDa, M
w/ M
n=2.3.
The uv-visible absorption spectra figure of the polymer P 4 of the organic semiconductor material of preparation in the present 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 ~ 700nm, have large wider absorption, wherein maximum absorption band is positioned at 610nm.
The thermogravimetic analysis (TGA) of the polymer P 4 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 (T
d) be 421 ℃.
The polymer P 4/Au of ITO/PEDOT:PSS/ the present embodiment 4 organic semiconductor material of take is device architecture, the structure anode of this device adopts tin indium oxide, Hole-injecting Buffer Layer for Improvement adopts poly-(3,4-ethene dioxythiophene)-polystyrolsulfon acid (PEDOT:PSS), the polymer P 4 of organic semiconductor material prepared by electron transfer layer employing the present embodiment, negative electrode adopts metallic aluminium, and the electronic mobility of polymkeric substance that adopt to have adopted space charge limited current (SCLC) model determination, the electronic mobility that obtains polymkeric substance is 2.5 * 10
-5cm
2/ Vs.
Embodiment 5
The present embodiment discloses following poly-{ 3,7-, bis-bases-sulphur dibenzofuran-co-2,7-bis--Ji-9,9-bis-(4-n-dodecane oxygen base benzene) fluorenes } (polymer P 5 of organic semiconductor material) of structural formula:
The preparation process of the polymer P 5 of above-mentioned organic semiconductor material is as follows:
Under nitrogen and the protection of argon gas gas mixture, by 3, 7-dibromo sulphur dibenzofuran (112mg, 0.3mmol), 9, 9-bis-(4-n-dodecane oxygen base benzene) fluorenes-2, 7-bis-tetramethyl ethylene ketone boric acid ester (282mg, 0.3mmol) add in the two-mouth bottle of 50mL specification with 15mL toluene, after fully dissolving, pass into after the about 20min of gas mixture air-discharging of nitrogen and argon gas, then by tetra-triphenylphosphine palladium (8mg, 0.006mmol) add wherein, add again salt of wormwood (7.5mL, 2mol/L) solution, pass into after the about 10min of gas mixture air-discharging of nitrogen and argon gas, two-mouth bottle is joined to 90 ℃ and carry out Suzuki coupling reaction 60h.Subsequently, after cooling, stop polyreaction, in two-mouth bottle, add 40mL methyl alcohol precipitating, 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 solid, obtains product poly-{ 3,7-, bis-bases-sulphur dibenzofuran-co-2,7-bis-base-9,9-bis-(4-n-dodecane oxygen base benzene) fluorenes } after collection under vacuum after 50 ℃ of dry 24h.Productive rate is 84%.
The reaction formula of the above-mentioned polymer P 5 of preparing organic semiconductor material is as follows:
Molecule measuring test result is: Molecular weight (GPC, THF, R.I): M
n=49.6kDa, M
w/ M
n=2.1.
The uv-visible absorption spectra figure of the polymer P 5 of the organic semiconductor material of preparation in the present 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 ~ 700nm, have large wider absorption, wherein maximum absorption band is positioned at 608nm.
The thermogravimetic analysis (TGA) of the polymer P 5 of the organic semiconductor material 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 (T
d) be 403 ℃.
The polymer P 5/Au of ITO/PEDOT:PSS/ the present embodiment 5 organic semiconductor material of take is device architecture, the structure anode of this device adopts tin indium oxide, Hole-injecting Buffer Layer for Improvement adopts poly-(3,4-ethene dioxythiophene)-polystyrolsulfon acid (PEDOT:PSS), the polymer P 5 of organic semiconductor material prepared by electron transfer layer employing the present embodiment, negative electrode adopts metallic aluminium, and the electronic mobility of polymkeric substance that adopted space charge limited current (SCLC) model determination, the electronic mobility that obtains polymkeric substance is 2.5 * 10
-5cm
2/ Vs.
Embodiment 6
Refer to Fig. 2, 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 CuPc, thickness is 30nm, hole transmission layer 304 adopts 4, two [N-(1-the naphthyl)-N-phenylamino] biphenyl of 4'-, thickness is 20nm, luminescent layer 305 main body luminescent materials adopt 9, 9'-(1, 3-phenyl) two-9H-carbazole, and take the object luminescent material two (4 that material of main part is 5% as benchmark doping mass percent, 6-difluorophenyl pyridine-N, C2) pyridine formyl closes iridium (III), luminescent layer 305 thickness are 20nm, the polymkeric substance of the organic semiconductor material that the electron transfer layer 306 employing embodiment of the present invention provide, what in the present embodiment, adopt is the polymer P 1 of organic semiconductor material, 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
/ second, the vaporator rate of lithium fluoride is
/ second, the vaporator rate of metallic aluminium is
/ second.
This organic electroluminescence 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 organic electroluminescence device is 10.5cd/A, and high-high brightness is 20730cd/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. a polymkeric substance for organic semiconductor material, is characterized in that, has following structural formula:
Wherein, R
1for C
1~ C
20alkyl, the integer that n is 10 ~ 100.
2. a preparation method for the polymkeric substance of organic semiconductor material, is characterized in that, comprises the steps:
The compd A and the compd B that provide following structural formula to represent,
A is:
b is:
wherein, R
1for C
1~ C
20alkyl;
In oxygen-free environment, the compd A that is 1:1 ~ 1:1.2 by mol ratio and compd B are added in the organic solvent that contains catalyzer and alkaline solution, at 70 ℃～130 ℃, carry out Suzuki coupling reaction 12 hours～96 hours, described catalyzer is organic palladium or is the mixture of organic palladium and organophosphor ligand, obtains the polymer P of the organic semiconductor material that following structural formula represents:
Wherein, the integer that n is 10 ~ 100.
3. the preparation method of the polymkeric substance of organic semiconductor material according to claim 2, is characterized in that, described organic solvent is selected from least one in toluene, DMF and tetrahydrofuran (THF).
4. the preparation method of the polymkeric substance of organic semiconductor material according to 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.
5. the preparation method of the polymkeric substance of organic semiconductor material according to 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.
6. the preparation method of the polymkeric substance of organic semiconductor material according to claim 2, is characterized in that, the temperature of reaction of described Suzuki coupling reaction is 90 ℃ ~ 120 ℃, and the reaction times is 24 hours ~ 72 hours.
7. the preparation method of the polymkeric substance of organic semiconductor material according to 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.
8. the preparation method of the polymkeric substance of organic semiconductor material according to claim 7, is characterized in that, the solute in described alkaline solution and the mol ratio of compd A are 20:1 ~ 50:1.
9. the preparation method of the polymkeric substance of organic semiconductor material according to claim 2, it is characterized in that, also comprise the step of the polymer P of organic semiconductor material 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 polymer P of the organic semiconductor material after purifying.
10. an organic electroluminescence device, comprises electron transfer layer, it is characterized in that, described electron transfer layer has the polymer P of the organic semiconductor material of following structural formula:
Wherein, R
1for C
1~ C
20alkyl, the integer that n is 10 ~ 100.
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| CN106633004A (en) * | 2017-01-04 | 2017-05-10 | 华南理工大学 | Conjugated polymer based on naphthothio dibenzofuran unit as well as preparation method and application thereof |
| CN107629196A (en) * | 2017-09-30 | 2018-01-26 | 华南协同创新研究院 | Side chain is poly- containing anthracene derivant（Fluorenes co S, S dioxydibenze bithiophenes）Derivative and preparation method and application |
| CN107739428A (en) * | 2017-09-04 | 2018-02-27 | 华南理工大学 | Side chain is poly- containing hole transporting unit（Fluorenes co S, S dioxydibenze bithiophenes）Derivative and its preparation method and application |
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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 |
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN106633004A (en) * | 2017-01-04 | 2017-05-10 | 华南理工大学 | Conjugated polymer based on naphthothio dibenzofuran unit as well as preparation method and application thereof |
| CN107739428A (en) * | 2017-09-04 | 2018-02-27 | 华南理工大学 | Side chain is poly- containing hole transporting unit（Fluorenes co S, S dioxydibenze bithiophenes）Derivative and its preparation method and application |
| CN107629196A (en) * | 2017-09-30 | 2018-01-26 | 华南协同创新研究院 | Side chain is poly- containing anthracene derivant（Fluorenes co S, S dioxydibenze bithiophenes）Derivative and preparation method and application |
| CN107629196B (en) * | 2017-09-30 | 2019-12-03 | 华南协同创新研究院 | Poly- (fluorenes-co-S, S- dioxo-dibenzothiophene) derivative and the preparation method and application thereof of the side chain containing anthracene derivant |
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| Publication number | Publication date |
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| CN103965446B (en) | 2016-12-07 |
| CN105622900A (en) | 2016-06-01 |
| CN105622900B (en) | 2018-10-26 |
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