CN103965446B - The polymer of organic semiconducting materials - Google Patents
The polymer of organic semiconducting materials Download PDFInfo
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- CN103965446B CN103965446B CN201310038647.9A CN201310038647A CN103965446B CN 103965446 B CN103965446 B CN 103965446B CN 201310038647 A CN201310038647 A CN 201310038647A CN 103965446 B CN103965446 B CN 103965446B
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- organic semiconducting
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- 239000004065 semiconductor Substances 0.000 title claims abstract description 80
- 229920000642 polymer Polymers 0.000 title claims abstract description 79
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims description 38
- 229940126062 Compound A Drugs 0.000 claims description 19
- 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 claims description 19
- 229910052763 palladium Inorganic materials 0.000 claims description 19
- 150000001875 compounds Chemical class 0.000 claims description 18
- 239000003446 ligand Substances 0.000 claims description 9
- 239000003054 catalyst Substances 0.000 claims description 7
- 239000003960 organic solvent Substances 0.000 claims description 6
- 239000000203 mixture Substances 0.000 claims description 5
- 239000003795 chemical substances by application Substances 0.000 claims description 3
- 238000006069 Suzuki reaction reaction Methods 0.000 claims 1
- 238000002360 preparation method Methods 0.000 abstract description 27
- 230000027756 respiratory electron transport chain Effects 0.000 abstract description 17
- 238000005401 electroluminescence Methods 0.000 abstract description 13
- 239000010410 layer Substances 0.000 description 46
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 36
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 30
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 27
- 239000000243 solution Substances 0.000 description 21
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 16
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 16
- 238000005859 coupling reaction Methods 0.000 description 15
- 239000000463 material Substances 0.000 description 15
- 229910052757 nitrogen Inorganic materials 0.000 description 15
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 14
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 13
- 238000006243 chemical reaction Methods 0.000 description 12
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 11
- 229920000144 PEDOT:PSS Polymers 0.000 description 10
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 description 10
- 238000010521 absorption reaction Methods 0.000 description 10
- 238000000862 absorption spectrum Methods 0.000 description 10
- 125000003983 fluorenyl group Chemical class C1(=CC=CC=2C3=CC=CC=C3CC12)* 0.000 description 10
- 238000001894 space-charge-limited current method Methods 0.000 description 10
- 229910052717 sulfur Inorganic materials 0.000 description 10
- 239000011593 sulfur Substances 0.000 description 10
- 238000012360 testing method Methods 0.000 description 10
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 8
- 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
- MRNHPUHPBOKKQT-UHFFFAOYSA-N indium;tin;hydrate Chemical compound O.[In].[Sn] MRNHPUHPBOKKQT-UHFFFAOYSA-N 0.000 description 7
- 229910000027 potassium carbonate Inorganic materials 0.000 description 7
- 238000004458 analytical method Methods 0.000 description 6
- 230000005540 biological transmission Effects 0.000 description 6
- 150000002118 epoxides Chemical class 0.000 description 6
- 239000008246 gaseous mixture Substances 0.000 description 6
- 238000002347 injection Methods 0.000 description 6
- 239000007924 injection Substances 0.000 description 6
- PQXKHYXIUOZZFA-UHFFFAOYSA-M lithium fluoride Chemical compound [Li+].[F-] PQXKHYXIUOZZFA-UHFFFAOYSA-M 0.000 description 6
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 6
- 239000000758 substrate Substances 0.000 description 6
- 230000004580 weight loss Effects 0.000 description 6
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 5
- 150000005224 alkoxybenzenes Chemical class 0.000 description 5
- 239000000872 buffer Substances 0.000 description 5
- 238000001816 cooling Methods 0.000 description 5
- 229940005642 polystyrene sulfonic acid Drugs 0.000 description 5
- 229910000030 sodium bicarbonate Inorganic materials 0.000 description 5
- 235000017557 sodium bicarbonate Nutrition 0.000 description 5
- 238000000638 solvent extraction Methods 0.000 description 5
- 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
- 230000001376 precipitating effect Effects 0.000 description 4
- 229910000029 sodium carbonate Inorganic materials 0.000 description 4
- 239000007787 solid Substances 0.000 description 4
- 239000002904 solvent Substances 0.000 description 4
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 3
- 238000001704 evaporation Methods 0.000 description 3
- 230000008020 evaporation Effects 0.000 description 3
- 239000001301 oxygen Substances 0.000 description 3
- 229910052760 oxygen Inorganic materials 0.000 description 3
- PIBWKRNGBLPSSY-UHFFFAOYSA-L palladium(II) chloride Chemical compound Cl[Pd]Cl PIBWKRNGBLPSSY-UHFFFAOYSA-L 0.000 description 3
- 239000000843 powder Substances 0.000 description 3
- 238000000746 purification Methods 0.000 description 3
- TUQOTMZNTHZOKS-UHFFFAOYSA-N tributylphosphine Chemical compound CCCCP(CCCC)CCCC TUQOTMZNTHZOKS-UHFFFAOYSA-N 0.000 description 3
- -1 4,6-difluorophenyl Chemical group 0.000 description 2
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- QBBOCSNLIYAOFH-UHFFFAOYSA-N COC1=C(C(=CC=C1)OC)C1=CC=CC=C1.[P] Chemical group COC1=C(C(=CC=C1)OC)C1=CC=CC=C1.[P] QBBOCSNLIYAOFH-UHFFFAOYSA-N 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- 229910052799 carbon Inorganic materials 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
- WMKGGPCROCCUDY-PHEQNACWSA-N dibenzylideneacetone Chemical compound C=1C=CC=CC=1\C=C\C(=O)\C=C\C1=CC=CC=C1 WMKGGPCROCCUDY-PHEQNACWSA-N 0.000 description 2
- 230000005611 electricity Effects 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 238000011049 filling Methods 0.000 description 2
- 238000001914 filtration Methods 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 239000011521 glass Substances 0.000 description 2
- CBFCDTFDPHXCNY-UHFFFAOYSA-N icosane Chemical compound CCCCCCCCCCCCCCCCCCCC CBFCDTFDPHXCNY-UHFFFAOYSA-N 0.000 description 2
- 238000000034 method Methods 0.000 description 2
- 239000000178 monomer Substances 0.000 description 2
- GIFAOSNIDJTPNL-UHFFFAOYSA-N n-phenyl-n-(2-phenylphenyl)naphthalen-1-amine Chemical group C1=CC=CC=C1N(C=1C2=CC=CC=C2C=CC=1)C1=CC=CC=C1C1=CC=CC=C1 GIFAOSNIDJTPNL-UHFFFAOYSA-N 0.000 description 2
- SIOXPEMLGUPBBT-UHFFFAOYSA-N picolinic acid Chemical compound OC(=O)C1=CC=CC=N1 SIOXPEMLGUPBBT-UHFFFAOYSA-N 0.000 description 2
- 238000006116 polymerization reaction Methods 0.000 description 2
- 238000001556 precipitation Methods 0.000 description 2
- 238000010926 purge Methods 0.000 description 2
- COIOYMYWGDAQPM-UHFFFAOYSA-N tris(2-methylphenyl)phosphane Chemical compound CC1=CC=CC=C1P(C=1C(=CC=CC=1)C)C1=CC=CC=C1C COIOYMYWGDAQPM-UHFFFAOYSA-N 0.000 description 2
- 238000001771 vacuum deposition Methods 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
- QVECKUGIBJOXFF-UHFFFAOYSA-N CC(C)(C)c(cc1C2(c(cc3)ccc3OC)c(cc3)ccc3OC)ccc1-c(cc1)c2cc1-c(cc1)cc2c1-c(ccc(C(C)(C)C)c1)c1S2=O Chemical compound CC(C)(C)c(cc1C2(c(cc3)ccc3OC)c(cc3)ccc3OC)ccc1-c(cc1)c2cc1-c(cc1)cc2c1-c(ccc(C(C)(C)C)c1)c1S2=O QVECKUGIBJOXFF-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
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- SNRUBQQJIBEYMU-UHFFFAOYSA-N Dodecane Natural products CCCCCCCCCCCC SNRUBQQJIBEYMU-UHFFFAOYSA-N 0.000 description 1
- ZHNUHDYFZUAESO-UHFFFAOYSA-N Formamide Chemical compound NC=O ZHNUHDYFZUAESO-UHFFFAOYSA-N 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- 235000003140 Panax quinquefolius Nutrition 0.000 description 1
- 240000005373 Panax quinquefolius Species 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
- 150000001335 aliphatic alkanes Chemical class 0.000 description 1
- 239000012298 atmosphere Substances 0.000 description 1
- 239000001273 butane Substances 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 238000012937 correction Methods 0.000 description 1
- 238000006392 deoxygenation reaction Methods 0.000 description 1
- CRBREIOFEDVXGE-UHFFFAOYSA-N dodecoxybenzene Chemical compound CCCCCCCCCCCCOC1=CC=CC=C1 CRBREIOFEDVXGE-UHFFFAOYSA-N 0.000 description 1
- 239000010408 film Substances 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 125000004435 hydrogen atom Chemical class [H]* 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 238000004519 manufacturing process 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
- IJDNQMDRQITEOD-UHFFFAOYSA-N n-butane Chemical compound CCCC IJDNQMDRQITEOD-UHFFFAOYSA-N 0.000 description 1
- 229940094933 n-dodecane Drugs 0.000 description 1
- OFBQJSOFQDEBGM-UHFFFAOYSA-N n-pentane Natural products CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 239000012044 organic layer Substances 0.000 description 1
- 239000011368 organic material Substances 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000000630 rising effect Effects 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000002207 thermal evaporation Methods 0.000 description 1
- 239000010409 thin film Substances 0.000 description 1
- 125000003944 tolyl group Chemical group 0.000 description 1
- 230000000007 visual effect 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
-
- 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
Abstract
The polymer of a kind of organic semiconducting materials, has a following structural formula:Wherein, R1For C1~C20Alkyl, n is the integer of 10 ~ 100.The polymer of this organic semiconducting materials has high electron mobility and excellent filming performance 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 electron mobility of this polymer is 10‑ 5cm2V‑1S‑1Left and right, and then solve organic semiconductor luminescent device low efficiency problem.The present invention also provides for the preparation method of the polymer of a kind of above-mentioned organic semiconducting materials and uses the organic electroluminescence device of this organic semiconducting materials.
Description
[technical field]
The present invention relates to photoelectric field, particularly relate to the polymer of a kind of organic semiconducting materials.
[background technology]
Organic electroluminescence device has light, thin, self-luminous, low consumpting power, need not light source, without visual angle
Limit, high reaction rate and the good characteristics such as flexible base plate can be produced on, be considered flat-panel screens and soft
The rising star of property display.The carrier mobility of traditional electron transport material is hole mobile material
The one of dry point, and heat stability is the best, therefore, often results in that luminous efficiency is the best or component life is long etc.
Problem, therefore developing the electron transport material of a kind of high carrier is nowadays organic electroluminescence device material
The emphasis of exploitation.
[summary of the invention]
Based on this, it is necessary to provide the polymer of the organic semiconducting materials that a kind of energy conversion efficiency is higher.
Additionally, there is a need to provide the preparation method of the polymer of a kind of organic semiconducting materials.
Additionally, there is a need to provide the organic electroluminescence device of the polymer using organic semiconducting materials.
The polymer of a kind of organic semiconducting materials, has a following structural formula:
P:
Wherein, R1For C1～C20Alkyl, n is the integer of 10～100.
The preparation method of the polymer of a kind of organic semiconducting materials, comprises the steps:
Compound A and compound B that following structural formula represents are provided,
A is:B is:Wherein,
R1For C1～C20Alkyl；
In oxygen-free environment, compound A and the compound B that mol ratio is 1: 1～1: 1.2 is added into containing urging
In the organic solvent of agent and aqueous slkali, carry out Suzuki coupled reaction 12 hours～96 at 70 DEG C～130 DEG C
Hour, described catalyst is organic palladium or the mixture for organic palladium with organophosphor ligand, obtains following structure
The polymer P of the organic semiconducting materials that formula represents:
Wherein, n is the integer of 10～100.
At least one in toluene, DMF and oxolane of described organic solvent.
Described organic palladium is bis-triphenylphosphipalladium palladium dichloride, tetra-triphenylphosphine palladium, palladium or three dibenzylidenes
Acetone two palladium, described organophosphorus ligand is tri-butyl phosphine, tri-o-tolyl phosphine or 2-dicyclohexyl phosphorus-2 ', 6 '-
Dimethoxy-biphenyl, described organic palladium is 1: 4～1: 8 with the mol ratio of described organophosphorus ligand.
Organic palladium in described catalyst is 1: 20～1: 100 with the mol ratio of described compound A.
The reaction temperature of described Suzuki coupled reaction is 90 DEG C～120 DEG C, and the response time is 24 hours～72
Hour.
At least one in sodium carbonate liquor, solution of potassium carbonate and sodium bicarbonate solution of described aqueous slkali.
Solute in described aqueous slkali is 20: 1～50: 1 with the mol ratio of compound A.
Also include the polymer P of organic semiconducting materials is carried out isolated and purified step, described isolated and purified
Step is as follows: add first in the solution after described compound A and compound B carries out Suzuki coupled reaction
Alcohol precipitation is also filtered, and is stripped with methanol and normal hexane successively by the solid being filtrated to get, will be through extracting
After solid chloroform, collect and evaporate solvent after chloroformic solution and obtain organic semiconducting materials after purification
Polymer P.
Described extracting uses apparatus,Soxhlet's to carry out.
A kind of organic electroluminescence device, including electron transfer layer, described electron transfer layer has following structure
The polymer P of the organic semiconducting materials of formula:
P:
Wherein, R1For C1～C20Alkyl, n is the integer of 10～100.
The polymer of above-mentioned organic semiconducting materials has high electron mobility and excellent filming performance and pattern
Stability, is suitable as electron transfer layer and is applied in organic electronic light emitting device, and can improve organic electronic
The luminous efficiency of luminescent device.The electron mobility of this polymer is 10-5cm2V-1S-1Left and right, so solve have
Machine light emitting semiconductor device low efficiency problem.The present invention also provides for the polymerization of a kind of above-mentioned organic semiconducting materials
The preparation method of thing and use the organic electroluminescence device of this organic semiconducting materials.
The preparation method of the polymer of above-mentioned organic semiconducting materials, have employed better simply synthetic route, from
And reducing technological process, raw material is cheap and easy to get so that manufacturing cost reduces；And the polymeric material knot being worth
Structure is novel, and solubility property is good, and filming performance is excellent, is applicable to organic electroluminescence device.
[accompanying drawing explanation]
Fig. 1 is the flow chart of the preparation method of the polymer of the organic semiconducting materials 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 the polymer of the organic semiconducting materials of embodiment 1 preparation；
Fig. 4 is the thermogravimetic analysis (TGA) figure of the polymer of the organic semiconducting materials of embodiment 1 preparation.
[detailed description of the invention]
In order to be more fully understood that the content of patent of the present invention, come further below by concrete example and legend
The technology case of the present invention is described, specifically includes material preparation and be prepared by device, but these embodiments do not limit
The present invention processed, wherein monomer A commercially obtains, and monomer B commercially obtains.
The polymer of the organic semiconducting materials of one embodiment, has a following structural formula:
P:
Wherein, R1For C1～C20Alkyl, n is the integer of 10～100.
The polymer of this organic semiconducting materials above-mentioned has high electron mobility and excellent filming performance and shape
Looks stability, is suitable as electron transfer layer and is applied in organic electronic light emitting device, and can improve Organic Electricity
The luminous efficiency of sub-luminescent device.The electron mobility of this polymer is 10-5cm2V-1S-1Left and right, and then solve
Organic semiconductor luminescent device low efficiency problem.The present invention also provides for the poly-of a kind of above-mentioned organic semiconducting materials
The preparation method of compound and use the organic electroluminescence device of this organic semiconducting materials.
The preparation method of the polymer of the organic semiconducting materials of one embodiment, as it is shown in figure 1, include with
Lower step:
Step S1, offer compound A and compound B.
The structural formula of compound A is:Wherein, R1For C1～C20Alkane
Base.
The structural formula of compound B is:
Step S2, prepare the polymer P of organic semiconducting materials.
In oxygen-free environment, compound A and the compound B that mol ratio is 1: 1～1: 1.2 is added into containing urging
In the organic solvent of agent and aqueous slkali, carry out Suzuki coupled reaction 12 hours～96 at 70 DEG C～130 DEG C
Hour, described catalyst is the mixture of organic palladium or organic palladium and organophosphor ligand, obtains following structural formula
The polymer P of the organic semiconducting materials represented:
Wherein, n is the integer of 10～100.
In present embodiment, Suzuki coupled reaction is carried out under nitrogen atmosphere.
In present embodiment, organic solvent is selected from toluene, DMF and oxolane extremely
Few one.It is appreciated that organic solution is used as other solvents, as long as can dissolved compound A and chemical combination
Thing B.
In present embodiment, organic palladium be bis-triphenylphosphipalladium palladium dichloride, tetra-triphenylphosphine palladium, palladium or
Three dibenzalacetone two palladiums, organophosphorus ligand is tri-butyl phosphine, tri-o-tolyl phosphine or 2-dicyclohexyl
Phosphorus-2 ', 6 '-dimethoxy-biphenyl.Organic palladium and organophosphor ligand in the mixture of organic palladium and organophosphor ligand
Mol ratio is 1: 4～1: 8.Preferably, the mixture work of three dibenzalacetone two palladiums and tri-butyl phosphine is used
For catalyst.It is appreciated that organic palladium, organophosphor ligand are not limited to cited kind, as long as can urge
Change compound A and compound B and carry out Suzuki coupled reaction.
In present embodiment, in catalyst, organic palladium is 1: 20～1: 100 with the mol ratio of compound A.Permissible
Understanding, organic palladium is not limited to 1: 20～1: 100 with the mol ratio of compound A, to adding compound A and change
The organic solvent of compound B adds the catalyst of catalytic amount.
In present embodiment, the reaction temperature of Suzuki coupled reaction is 70 DEG C～130 DEG C, and the response time is 12
Hour～96 hours.Preferably, the reaction temperature of Suzuki coupled reaction is 90 DEG C～120 DEG C, the response time
It it is 24 hours～72 hours.It is appreciated that the reaction temperature of Suzuki coupled reaction is not limited to 70 DEG C～130
DEG C, as long as compound A and compound B can be made to react；Response time is also not necessarily limited to be 12 hours
～96 hours, as long as compound A and compound B reaction as far as possible can be made completely.
In present embodiment, described aqueous slkali is selected from sodium carbonate liquor, solution of potassium carbonate and sodium bicarbonate solution
In at least one, wherein the solute of sodium carbonate liquor is sodium carbonate, and the solute of solution of potassium carbonate is potassium carbonate
And the solute of sodium bicarbonate solution is sodium bicarbonate；
In present embodiment, the solute in described aqueous slkali is 20: 1～50: 1 with the mol ratio of compound A.
Step S3, the polymer P of isolated and purified organic semiconducting materials.
Solution after described compound A and compound B carries out Suzuki coupled reaction adds methanol precipitating
And filter, the solid being filtrated to get is stripped with methanol and normal hexane successively, by consolidating after extracting
Body chloroform, evaporates solvent and obtains the polymerization of organic semiconducting materials after purification after collecting chloroformic solution
Thing P.
In present embodiment, extracting uses apparatus,Soxhlet's to carry out.
In present embodiment, evaporate solvent after chloroformic solution being collected and obtain organic semiconducting materials after purification
Polymer P under vacuo 50 DEG C～70 DEG C be dried 24 hours～48 hours.
The preparation method of the polymer of above-mentioned organic semiconducting materials, synthetic route is relatively simple, reduces system
Cause this.
A kind of organic electroluminescence device 300 in one embodiment, its structure such as Fig. 2 it include substrate 301,
Anode 302, hole injection layer 303, hole transmission layer 304, luminescent layer 305, electron transfer layer 306, electricity
Sub-injecting layer 307, negative electrode 308.
In the present embodiment, the material of substrate 301 is glass, vacuum coating anode 302 successively in substrate 301,
Hole injection layer 303, hole transmission layer 304, luminescent layer 305, electron transfer layer 306, electronics injects slow
Rushing layer 307, negative electrode 308, the tin indium oxide that anode 302 uses square resistance to be 10～20 Ω/, thickness is
150nm, hole injection layer 303 uses CuPc, and thickness is 30nm, and hole transmission layer 304 uses 4,4 '-
Double [N-(1-naphthyl)-N-phenylamino] biphenyl, thickness is 20nm, and luminescent layer 305 main body luminescent material uses
9,9 '-(1,3-phenyl) two-9H-carbazole, and on the basis of material of main part adulterate mass percent be 5% object send out
Double (4,6-difluorophenyl pyridinato-N, the C2) pyridinecarboxylic of luminescent material closes iridium (III), and luminescent layer 305 thickness is 20nm,
Electron transfer layer 306 uses the polymer of the organic semiconducting materials that the embodiment of the present invention provides, and thickness is
30nm, electronics injecting layer 307 uses lithium fluoride, and thickness is 1nm, and negative electrode 308 uses metallic aluminium,
Thickness is 100nm.
Described electron transfer layer has a polymer P of the organic semiconducting materials of following structural formula:
P:
Wherein, R1For C1～C20Alkyl, n is the integer of 10～100.
It is specific embodiment below.
Embodiment 1
{ 3,7-diyls-sulfur dibenzofuran-co-2,7-diyl-9, (4-is just for 9-bis-to present embodiment discloses following poly-of structural formula
Own alkoxy benzene) fluorenes } (polymer P 1 of organic semiconducting materials):
The preparation process of the polymer P 1 of above-mentioned organic semiconducting materials is as follows:
Under argon shield, by 3,7-dibromo sulfur dibenzofuran (75mg, 0.2mmol), 9,9-bis-(4-normal hexane epoxide
Benzene) fluorenes-2,7-bis-pinacol borate (154mg, 0.2mmol) adds the flask filling 10ml toluene solvant
In, after fully dissolving, potassium carbonate (2mL, 2mol/L) solution is joined in flask, evacuation deoxygenation is also filled with
Argon, is subsequently adding bis-triphenylphosphipalladium palladium dichloride (5.6mg, 0.008mmol)；Flask is heated to 100
DEG C carry out Suzuki coupled reaction 48h.Subsequently, after cooling, stop polyreaction, in flask, drip 50ml
Methanol settles；Successively with methanol and normal hexane extracting 24h after being filtered by apparatus,Soxhlet's.So
After with chloroform for solvent extraction to the most colourless, collect chloroformic solution and also be spin-dried for obtaining under red powder, vacuum pump taking out
Overnight obtain product poly-{ 3,7-diyls-sulfur dibenzofuran-co-2,7-diyl-9,9-bis-(4-normal hexane epoxide benzene) fluorenes }, produce
Rate 76%.
The reaction equation of the above-mentioned polymer P 1 preparing organic semiconducting materials is as follows:
Molecule measuring test result is: Molecular weight (GPC, THF, R.I): Mn=43.5kDa,
Mw/Mn=2.2.
See accompanying drawing 3, be the ultraviolet-visible of the polymer P 1 of the organic semiconducting materials of preparation in embodiment 1
Abosrption spectrogram, uv-visible absorption spectra is measured on Jasco-570 uv analyzer.As seen from the figure:
Inventive polymers between 300nm～700nm, have absorption wider relatively greatly, wherein maximum absorption band is positioned at
609nm。
See accompanying drawing 4, be that the thermal weight loss of the polymer P 1 of the organic semiconducting materials of the present embodiment 1 preparation divides
Analysis figure, thermogravimetric curve (TGA) test is carried out on TA SDT 2960 instruments, protects at nitrogen stream
Protecting down, programming rate is 10K/min.Thermal weight loss temperature (the T of 5% as seen from the figured) it is 412 DEG C.
With the polymer P 1/Au of ITO/PEDOT:PSS/ the present embodiment 1 organic semiconducting materials as device junction
Structure, the structure anode of this device uses tin indium oxide, Hole-injecting Buffer Layer for Improvement employing poly-(3,4-rthylene dioxythiophene)-poly-
Styrene sulfonic acid (PEDOT:PSS), electron transfer layer uses organic semiconducting materials prepared by the present embodiment
Polymer P 1, negative electrode uses metallic aluminium, and uses space charge limited current (SCLC) model determination to gather
The electron mobility of compound, the electron mobility of the polymer P 1 obtaining organic semiconducting materials is 2.3 ×
10-5cm2/Vs。
Embodiment 2
Present embodiment discloses poly-{ 3,7-diyls-sulfur dibenzofuran-co-2,7-diyl-9,9-bis-(4-first that structural formula is following
Alkoxy benzene) fluorenes } (polymer P 2 of organic semiconducting materials):
The preparation process of the polymer P 2 of above-mentioned organic semiconducting materials is as follows:
Under nitrogen and the protection of argon gaseous mixture, by 3,7-dibromo sulfur dibenzofuran (112mg, 0.3mmol), 9,9-bis-(4-
First alkoxy benzene) fluorenes-2,7-bis-pinacol borate (189mg, 0.3mmol) and 15mL oxolane add
In the two-mouth bottle of 50mL specification, after fully dissolving, it is passed through the gaseous mixture air-discharging about 20min of nitrogen and argon
After, then tetra-triphenylphosphine palladium (4mg, 0.003mmol) is added thereto, after fully dissolving, adds carbon
Acid hydrogen sodium (3mL, 2mol/L) solution, then after fully leading to the gaseous mixture air-discharging about 10min of nitrogen and argon,
Two-mouth bottle is joined 70 DEG C and carries out Suzuki coupled reaction 60h.Subsequently, after cooling, stop polyreaction,
40mL methanol precipitating is added, successively with methanol and just own after being filtered by apparatus,Soxhlet's in two-mouth bottle
Alkane extracting 24h.Then with chloroform for solvent extraction to colourless, collect chloroformic solution and be spin-dried for obtaining redness admittedly
Body, obtains product poly-{ 3,7-diyls-sulfur dibenzofuran-co-2,7-diyl after 50 DEG C of dry 24h after collection under vacuo
-9,9-bis-(4-first alkoxy benzene) fluorenes }.Productivity is 82%.
The reaction equation of the above-mentioned polymer P 2 preparing organic semiconducting materials is as follows:
Molecule measuring test result is: Molecular weight (GPC, THF, R.I): Mn=58.7kDa,
Mw/Mn=2.0.
The uv-visible absorption spectra figure of the polymer P 2 of the organic semiconducting materials of preparation in the present embodiment 2,
Uv-visible absorption spectra is measured on Jasco-570 uv analyzer.As seen from the figure: the present invention is polymerized
Thing between 300nm～700nm, have absorption wider relatively greatly, wherein maximum absorption band is positioned at 607nm.
The thermogravimetic analysis (TGA) of the polymer P 2 of the organic semiconducting materials of the present embodiment 2 preparation, thermogravimetric curve
(TGA) test is carried out on TA SDT 2960 instruments, and under nitrogen air-flow protection, programming rate is
10K/min.Thermal weight loss temperature (the T of 5%d) it is 451 DEG C.
With the polymer P 2/Au of ITO/PEDOT:PSS/ the present embodiment 2 organic semiconducting materials as device junction
Structure, the structure anode of this device uses tin indium oxide, Hole-injecting Buffer Layer for Improvement employing poly-(3,4-rthylene dioxythiophene)-poly-
Styrene sulfonic acid (PEDOT:PSS), electron transfer layer uses organic semiconducting materials prepared by the present embodiment
Polymer P 2, negative electrode uses metallic aluminium, and uses space charge limited current (SCLC) model determination to gather
The electron mobility of compound, the electron mobility obtaining polymer is 2.8 × 10-5cm2/Vs。
Embodiment 3
{ 3,7-diyls-sulfur dibenzofuran-co-2,7-diyl-9, (4-is just for 9-bis-to present embodiment discloses following poly-of structural formula
Eicosane epoxide benzene) fluorenes } (polymer P 3 of organic semiconducting materials):
The preparation process of the polymer P 3 of above-mentioned organic semiconducting materials is as follows:
Under nitrogen protection, by 3,7-dibromo sulfur dibenzofuran (112mg, 0.3mmol), 9,9-bis-(4-AI3-28404 oxygen
Base benzene) fluorenes-2,7-bis-pinacol borate (384mg, 0.33mmol), palladium (3.5mg, 0.015mmol)
N, the N-dimethyl filling 12mL is joined with three (o-methoxyphenyl) phosphine (21mg, 0.06mmol)
In the flask of Methanamide, add potassium carbonate (3mL, 2mol/L) solution after fully dissolving, subsequently toward logical in flask
After nitrogen purge gas about 20min；Flask is heated to 130 DEG C and carries out Suzuki coupled reaction 12h.Subsequently,
Stop polyreaction after cooling, in flask, add 40mL methanol precipitating, filter it by apparatus,Soxhlet's
After successively with methanol and normal hexane extracting 24h；Then with chloroform for solvent extraction to colourless, chloroform is collected molten
Liquid is also spin-dried for obtaining red powder, after collection under vacuo after 50 DEG C of dry 24h, is product poly-{ 3,7-bis-
Base-sulfur dibenzofuran-co-2,7-diyl-9,9-bis-(4-AI3-28404 epoxide benzene) fluorenes }, productivity is 75%.
The reaction equation of the above-mentioned polymer P 3 preparing organic semiconducting materials is as follows:
Molecule measuring test result is: Molecular weight (GPC, THF, R.I): Mn=16.1kDa, Mw/Mn
=2.4.
The uv-visible absorption spectra figure of the polymer P 3 of the organic semiconducting materials of preparation in the present embodiment 3,
Uv-visible absorption spectra is measured on Jasco-570 uv analyzer.As seen from the figure: the present invention is polymerized
Thing between 300nm～700nm, have absorption wider relatively greatly, wherein maximum absorption band is positioned at 613nm.
The thermogravimetic analysis (TGA) of the polymer P 3 of the organic semiconducting materials of the present embodiment 3 preparation, thermogravimetric curve
(TGA) test is carried out on TA SDT 2960 instruments, and under nitrogen air-flow protection, programming rate is
10K/min.Thermal weight loss temperature (the T of 5%d) it is 398 DEG C.
With the polymer P 3/Au of ITO/PEDOT:PSS/ the present embodiment 3 organic semiconducting materials as device junction
Structure, the structure anode of this device uses tin indium oxide, Hole-injecting Buffer Layer for Improvement employing poly-(3,4-rthylene dioxythiophene)-poly-
Styrene sulfonic acid (PEDOT:PSS), electron transfer layer uses organic semiconducting materials prepared by the present embodiment
Polymer P 3, negative electrode uses metallic aluminium, and uses space charge limited current (SCLC) model determination to gather
The electron mobility of compound, the electron mobility obtaining polymer is 2.7 × 10-5cm2/Vs。
Embodiment 4
{ 3,7-diyls-sulfur dibenzofuran-co-2,7-diyl-9, (4-is just for 9-bis-to present embodiment discloses following poly-of structural formula
Fourth alkoxy benzene) fluorenes } (polymer P 4 of organic semiconducting materials):
The preparation process of the polymer P 4 of above-mentioned organic semiconducting materials is as follows:
Under nitrogen protection, by 3,7-dibromo sulfur dibenzofuran (112mg, 0.3mmol), 9,9-bis-(4-AI3-28404 oxygen
Base benzene) fluorenes-2,7-bis-pinacol borate (257mg, 0.36mmol), three or two argon benzylacetone two palladiums (9mg,
0.009mmol) with 2-dicyclohexyl phosphine-2 ', 6 '-dimethoxy-biphenyl (29mg, 0.072mmol) joins Sheng
Have in the flask of DMF of 12mL, add after fully dissolving sodium bicarbonate (3mL,
2mol/L) solution, subsequently toward after nitrogen purge gas about 20min logical in flask；Flask is heated to 120 DEG C enter
Row Suzuki coupled reaction 36h.Subsequently, after cooling, stop polyreaction, in flask, add 40mL first
Alcohol precipitation, successively with methanol and normal hexane extracting 24h after filtering by apparatus,Soxhlet's；Then with chloroform
For solvent extraction to the most colourless, collect chloroformic solution and be also spin-dried for obtaining red powder, after collection 50 DEG C under vacuo
After being dried 24h, it is product poly-{ 3,7-diyls-sulfur dibenzofuran-co-2,7-diyl-9,9-bis-(4-normal butane epoxide benzene)
Fluorenes }, productivity is 78%.
The reaction equation of the above-mentioned polymer P 4 preparing organic semiconducting materials is as follows:
Molecule measuring test result is: Molecular weight (GPC, THF, R.I): Mn=23.7kDa, Mw/Mn
=2.3.
The uv-visible absorption spectra figure of the polymer P 4 of the organic semiconducting materials of preparation in the present embodiment 4,
Uv-visible absorption spectra is measured on Jasco-570 uv analyzer.As seen from the figure: the present invention is polymerized
Thing between 300nm～700nm, have absorption wider relatively greatly, wherein maximum absorption band is positioned at 610nm.
The thermogravimetic analysis (TGA) of the polymer P 4 of the organic semiconducting materials of the present embodiment 4 preparation, thermogravimetric curve
(TGA) test is carried out on TA SDT 2960 instruments, and under nitrogen air-flow protection, programming rate is
10K/min.Thermal weight loss temperature (the T of 5%d) it is 421 DEG C.
With the polymer P 4/Au of ITO/PEDOT:PSS/ the present embodiment 4 organic semiconducting materials as device junction
Structure, the structure anode of this device uses tin indium oxide, Hole-injecting Buffer Layer for Improvement employing poly-(3,4-rthylene dioxythiophene)-poly-
Styrene sulfonic acid (PEDOT:PSS), electron transfer layer uses organic semiconducting materials prepared by the present embodiment
Polymer P 4, negative electrode uses metallic aluminium, and uses space charge limited current (SCLC) model determination
The electron mobility of polymer, the electron mobility obtaining polymer is 2.5 × 10-5cm2/Vs。
Embodiment 5
{ 3,7-diyls-sulfur dibenzofuran-co-2,7-diyl-9, (4-is just for 9-bis-to present embodiment discloses following poly-of structural formula
Dodecyloxy benzene) fluorenes } (polymer P 5 of organic semiconducting materials):
The preparation process of the polymer P 5 of above-mentioned organic semiconducting materials is as follows:
Under nitrogen and the protection of argon gaseous mixture, by 3,7-dibromo sulfur dibenzofuran (112mg, 0.3mmol), 9,9-bis-(4-
N-dodecane epoxide benzene) fluorenes-2,7-bis-pinacol borate (282mg, 0.3mmol) and 15mL toluene add
In the two-mouth bottle of 50mL specification, after fully dissolving, it is passed through the gaseous mixture air-discharging about 20min of nitrogen and argon
After, then tetra-triphenylphosphine palladium (8mg, 0.006mmol) is added thereto, add potassium carbonate (7.5mL,
2mol/L) solution, after being passed through the gaseous mixture air-discharging about 10min of nitrogen and argon, joins 90 by two-mouth bottle
DEG C carry out Suzuki coupled reaction 60h.Subsequently, after cooling, stop polyreaction, in two-mouth bottle, add 40
ML methanol precipitating, successively with methanol and normal hexane extracting 24h after filtering by apparatus,Soxhlet's.Then with
Chloroform is that solvent extraction is the most colourless, collects chloroformic solution and is also spin-dried for obtaining red solid, after collection under vacuo
Product poly-{ 3,7-diyls-sulfur dibenzofuran-co-2,7-diyl-9,9-bis-(4-n-dodecane oxygen is obtained after 50 DEG C of dry 24h
Base benzene) fluorenes }.Productivity is 84%.
The reaction equation of the above-mentioned polymer P 5 preparing organic semiconducting materials is as follows:
Molecule measuring test result is: Molecular weight (GPC, THF, R.I): Mn=49.6kDa, Mw/Mn
=2.1.
The uv-visible absorption spectra figure of the polymer P 5 of the organic semiconducting materials of preparation in the present embodiment 5,
Uv-visible absorption spectra is measured on Jasco-570 uv analyzer.As seen from the figure: the present invention is polymerized
Thing between 300nm～700nm, have absorption wider relatively greatly, wherein maximum absorption band is positioned at 608nm.
The thermogravimetic analysis (TGA) of the polymer P 5 of the organic semiconducting materials of the present embodiment 5 preparation, thermogravimetric curve
(TGA) test is carried out on TA SDT 2960 instruments, and under nitrogen air-flow protection, programming rate is
10K/min.Thermal weight loss temperature (the T of 5%d) it is 403 DEG C.
With the polymer P 5/Au of ITO/PEDOT:PSS/ the present embodiment 5 organic semiconducting materials as device junction
Structure, the structure anode of this device uses tin indium oxide, Hole-injecting Buffer Layer for Improvement employing poly-(3,4-rthylene dioxythiophene)-poly-
Styrene sulfonic acid (PEDOT:PSS), electron transfer layer uses organic semiconducting materials prepared by the present embodiment
Polymer P 5, negative electrode uses metallic aluminium, and uses space charge limited current (SCLC) model determination to gather
The electron mobility of compound, the electron mobility obtaining polymer is 2.5 × 10-5cm2/Vs。
Embodiment 6
Refer to Fig. 2, organic electroluminescence device 300, its structure such as Fig. 1 it include substrate 301, anode
302, hole injection layer 303, hole transmission layer 304, luminescent layer 305, electron transfer layer 306, electronics is noted
Enter cushion 307, negative electrode 308.
In the present embodiment, the material of substrate 301 is glass, vacuum coating anode 302 successively in substrate 301,
Hole injection layer 303, hole transmission layer 304, luminescent layer 305, electron transfer layer 306, electronics injects slow
Rushing layer 307, negative electrode 308, the tin indium oxide that anode 302 uses square resistance to be 10～20 Ω/, thickness is
150nm, hole injection layer 303 uses CuPc, and thickness is 30nm, and hole transmission layer 304 uses 4,4 '-
Double [N-(1-naphthyl)-N-phenylamino] biphenyl, thickness is 20nm, and luminescent layer 305 main body luminescent material uses
9,9 '-(1,3-phenyl) two-9H-carbazole, and on the basis of material of main part adulterate mass percent be 5% object send out
Double (4,6-difluorophenyl pyridinato-N, the C2) pyridinecarboxylic of luminescent material closes iridium (III), and luminescent layer 305 thickness is 20nm,
Electron transfer layer 306 uses the polymer of the organic semiconducting materials that the embodiment of the present invention provides, the present embodiment
In use the polymer P 1 of organic semiconducting materials, thickness is 30nm, electronics injecting layer 307
Using lithium fluoride, thickness is 1nm, and negative electrode 308 uses metallic aluminium, and thickness is 100nm.
Organic layer and metal level all use thermal evaporation process to deposit, and vacuum is 10-3～10-5Pa, thin film
Thickness use film thickness monitoring instrument monitor, in addition to guest materials, the evaporation rate of all organic materials is/
Second, the evaporation rate of lithium fluoride is/ the second, the evaporation rate of metallic aluminium is/ the second.
This organic electroluminescence device has higher luminous efficiency, can be widely used in blueness or white etc. and sends out
Optical arena.Current versus brightness-the voltage characteristic of device is by the Keithley with correction silicon photoelectric diode
The institute that system (Keithley 2400 Sourcemeter, Keithley 2000 Cuirrentmeter) completes is measured in source
Measurement is had all to complete in atmosphere at room temperature.Result shows: the maximum electrical efficiency of organic electroluminescence device is
10.5cd/A, high-high brightness is 20730cd/m2。
Embodiment described above only have expressed the several embodiments of the present invention, and it describes more concrete and detailed,
But therefore can not be interpreted as the restriction to the scope of the claims of the present invention.It should be pointed out that, for this area
Those of ordinary skill for, without departing from the inventive concept of the premise, it is also possible to make some deformation and
Improving, these broadly fall into protection scope of the present invention.Therefore, the protection domain of patent of the present invention should be with appended
Claim is as the criterion.
Claims (1)
1. the polymer of an organic semiconducting materials, it is characterised in that there is following structural formula:
Wherein, R1For C1～C20Alkyl, n is the integer of 10～100, and described organic semiconducting materials is logical
Cross following steps to be prepared from:
Compound A and compound B that following structural formula represents are provided,
A is:B is:Wherein,
R1For C1～C20Alkyl；
In oxygen-free environment, compound A and the compound B that mol ratio is 1:1～1:1.2 is added into containing urging
In the organic solvent of agent and aqueous slkali, carry out Suzuki coupling reaction 12 hours～96 at 70 DEG C～130 DEG C
Hour, described catalyst is organic palladium or the mixture for organic palladium with organophosphor ligand, obtains following structure
The polymer P of the organic semiconducting materials that formula represents:
Wherein, n is the integer of 10～100.
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