CN103965440B - A kind of organic semiconducting materials - Google Patents
A kind of organic semiconducting materials Download PDFInfo
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- CN103965440B CN103965440B CN201310037657.0A CN201310037657A CN103965440B CN 103965440 B CN103965440 B CN 103965440B CN 201310037657 A CN201310037657 A CN 201310037657A CN 103965440 B CN103965440 B CN 103965440B
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- semiconducting materials
- organic semiconducting
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- diyl
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- 239000004065 semiconductor Substances 0.000 title claims abstract description 65
- 239000000126 substance Substances 0.000 claims abstract description 3
- 239000000463 material Substances 0.000 abstract description 61
- 230000005540 biological transmission Effects 0.000 abstract description 9
- 238000000034 method Methods 0.000 abstract description 8
- 230000008569 process Effects 0.000 abstract description 8
- 230000005525 hole transport Effects 0.000 abstract description 4
- 238000004020 luminiscence type Methods 0.000 abstract description 4
- 239000002994 raw material Substances 0.000 abstract description 3
- 230000007423 decrease Effects 0.000 abstract description 2
- 238000004519 manufacturing process Methods 0.000 abstract description 2
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 39
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 30
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 28
- 239000010410 layer Substances 0.000 description 26
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 25
- 238000012360 testing method Methods 0.000 description 20
- 238000002360 preparation method Methods 0.000 description 19
- 239000000243 solution Substances 0.000 description 18
- 229910052757 nitrogen Inorganic materials 0.000 description 17
- 238000000862 absorption spectrum Methods 0.000 description 15
- 229910052763 palladium Inorganic materials 0.000 description 15
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 14
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 14
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 13
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 10
- 229940126062 Compound A Drugs 0.000 description 10
- NLDMNSXOCDLTTB-UHFFFAOYSA-N Heterophylliin A Natural products O1C2COC(=O)C3=CC(O)=C(O)C(O)=C3C3=C(O)C(O)=C(O)C=C3C(=O)OC2C(OC(=O)C=2C=C(O)C(O)=C(O)C=2)C(O)C1OC(=O)C1=CC(O)=C(O)C(O)=C1 NLDMNSXOCDLTTB-UHFFFAOYSA-N 0.000 description 10
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Natural products CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 10
- 238000010521 absorption reaction Methods 0.000 description 10
- 229910052741 iridium Inorganic materials 0.000 description 10
- GKOZUEZYRPOHIO-UHFFFAOYSA-N iridium atom Chemical compound [Ir] GKOZUEZYRPOHIO-UHFFFAOYSA-N 0.000 description 10
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 10
- -1 4,6-difluorophenyl Chemical group 0.000 description 9
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 9
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 8
- 238000005859 coupling reaction Methods 0.000 description 8
- SIOXPEMLGUPBBT-UHFFFAOYSA-N picolinic acid Chemical compound OC(=O)C1=CC=CC=N1 SIOXPEMLGUPBBT-UHFFFAOYSA-N 0.000 description 8
- 150000001875 compounds Chemical class 0.000 description 7
- 239000007789 gas Substances 0.000 description 7
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 6
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 6
- 239000003054 catalyst Substances 0.000 description 6
- 239000003446 ligand Substances 0.000 description 6
- 239000007788 liquid Substances 0.000 description 6
- IMRWILPUOVGIMU-UHFFFAOYSA-N 2-bromopyridine Chemical compound BrC1=CC=CC=N1 IMRWILPUOVGIMU-UHFFFAOYSA-N 0.000 description 5
- 229910052786 argon Inorganic materials 0.000 description 5
- 238000006243 chemical reaction Methods 0.000 description 5
- 239000004020 conductor Substances 0.000 description 5
- 230000000694 effects Effects 0.000 description 5
- 230000009477 glass transition Effects 0.000 description 5
- MILUBEOXRNEUHS-UHFFFAOYSA-N iridium(3+) Chemical compound [Ir+3] MILUBEOXRNEUHS-UHFFFAOYSA-N 0.000 description 5
- 229920000642 polymer Polymers 0.000 description 5
- 229910000027 potassium carbonate Inorganic materials 0.000 description 5
- 239000000843 powder Substances 0.000 description 5
- 238000000746 purification Methods 0.000 description 5
- 238000001228 spectrum Methods 0.000 description 5
- 239000000758 substrate Substances 0.000 description 5
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 4
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 description 4
- 229910052782 aluminium Inorganic materials 0.000 description 4
- 239000004411 aluminium Substances 0.000 description 4
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 4
- 238000001816 cooling Methods 0.000 description 4
- 238000001938 differential scanning calorimetry curve Methods 0.000 description 4
- PQXKHYXIUOZZFA-UHFFFAOYSA-M lithium fluoride Chemical compound [Li+].[F-] PQXKHYXIUOZZFA-UHFFFAOYSA-M 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- 239000003960 organic solvent Substances 0.000 description 4
- 239000007787 solid Substances 0.000 description 4
- 238000000638 solvent extraction Methods 0.000 description 4
- 239000012298 atmosphere Substances 0.000 description 3
- 239000001273 butane Substances 0.000 description 3
- 238000001704 evaporation Methods 0.000 description 3
- 230000008020 evaporation Effects 0.000 description 3
- 239000008246 gaseous mixture Substances 0.000 description 3
- IJDNQMDRQITEOD-UHFFFAOYSA-N n-butane Chemical compound CCCC IJDNQMDRQITEOD-UHFFFAOYSA-N 0.000 description 3
- OFBQJSOFQDEBGM-UHFFFAOYSA-N n-pentane Natural products CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 3
- PIBWKRNGBLPSSY-UHFFFAOYSA-L palladium(II) chloride Chemical compound Cl[Pd]Cl PIBWKRNGBLPSSY-UHFFFAOYSA-L 0.000 description 3
- 238000010926 purge Methods 0.000 description 3
- 230000027756 respiratory electron transport chain Effects 0.000 description 3
- 229910000029 sodium carbonate Inorganic materials 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-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
- XYFCBTPGUUZFHI-UHFFFAOYSA-N Phosphine Chemical compound P XYFCBTPGUUZFHI-UHFFFAOYSA-N 0.000 description 2
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 2
- JYMITAMFTJDTAE-UHFFFAOYSA-N aluminum zinc oxygen(2-) Chemical compound [O-2].[Al+3].[Zn+2] JYMITAMFTJDTAE-UHFFFAOYSA-N 0.000 description 2
- 239000010405 anode material Substances 0.000 description 2
- 229910052796 boron Inorganic materials 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
- 238000007599 discharging Methods 0.000 description 2
- 230000005611 electricity Effects 0.000 description 2
- 238000005401 electroluminescence Methods 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
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 2
- 229910052737 gold Inorganic materials 0.000 description 2
- 239000010931 gold Substances 0.000 description 2
- 238000002347 injection Methods 0.000 description 2
- 239000007924 injection Substances 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 239000000178 monomer Substances 0.000 description 2
- 229910052759 nickel Inorganic materials 0.000 description 2
- 230000001376 precipitating effect Effects 0.000 description 2
- 229910052709 silver Inorganic materials 0.000 description 2
- 239000004332 silver Substances 0.000 description 2
- 125000003831 tetrazolyl group Chemical group 0.000 description 2
- 125000003944 tolyl group Chemical group 0.000 description 2
- TUQOTMZNTHZOKS-UHFFFAOYSA-N tributylphosphine Chemical compound CCCCP(CCCC)CCCC TUQOTMZNTHZOKS-UHFFFAOYSA-N 0.000 description 2
- COIOYMYWGDAQPM-UHFFFAOYSA-N tris(2-methylphenyl)phosphane Chemical compound CC1=CC=CC=C1P(C=1C(=CC=CC=1)C)C1=CC=CC=C1C COIOYMYWGDAQPM-UHFFFAOYSA-N 0.000 description 2
- YVTHLONGBIQYBO-UHFFFAOYSA-N zinc indium(3+) oxygen(2-) Chemical compound [O--].[Zn++].[In+3] YVTHLONGBIQYBO-UHFFFAOYSA-N 0.000 description 2
- DHDHJYNTEFLIHY-UHFFFAOYSA-N 4,7-diphenyl-1,10-phenanthroline Chemical compound C1=CC=CC=C1C1=CC=NC2=C1C=CC1=C(C=3C=CC=CC=3)C=CN=C21 DHDHJYNTEFLIHY-UHFFFAOYSA-N 0.000 description 1
- DADZIMNFQANSAN-UHFFFAOYSA-N C(C1=CC=CC=C1)CC(C)=O.[Ar] Chemical class 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
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- 238000006069 Suzuki reaction reaction Methods 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 150000004696 coordination complex Chemical class 0.000 description 1
- 238000012937 correction Methods 0.000 description 1
- 238000006392 deoxygenation reaction Methods 0.000 description 1
- 230000005284 excitation Effects 0.000 description 1
- 239000000284 extract Substances 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- MRNHPUHPBOKKQT-UHFFFAOYSA-N indium;tin;hydrate Chemical compound O.[In].[Sn] MRNHPUHPBOKKQT-UHFFFAOYSA-N 0.000 description 1
- 238000012544 monitoring process Methods 0.000 description 1
- ZTLUNQYQSIQSFK-UHFFFAOYSA-N n-[4-(4-aminophenyl)phenyl]naphthalen-1-amine Chemical class C1=CC(N)=CC=C1C(C=C1)=CC=C1NC1=CC=CC2=CC=CC=C12 ZTLUNQYQSIQSFK-UHFFFAOYSA-N 0.000 description 1
- 239000012044 organic layer Substances 0.000 description 1
- 239000011368 organic material Substances 0.000 description 1
- 229910000073 phosphorus hydride Inorganic materials 0.000 description 1
- 238000007540 photo-reduction reaction Methods 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000006722 reduction reaction Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 230000004044 response 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
- 229910000030 sodium bicarbonate Inorganic materials 0.000 description 1
- 235000017557 sodium bicarbonate Nutrition 0.000 description 1
- 238000002207 thermal evaporation Methods 0.000 description 1
- 230000001052 transient effect Effects 0.000 description 1
- 238000001771 vacuum deposition Methods 0.000 description 1
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- 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
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- C07D—HETEROCYCLIC COMPOUNDS
- C07D417/00—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and sulfur atoms as the only ring hetero atoms, not provided for by group C07D415/00
- C07D417/14—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and sulfur atoms as the only ring hetero atoms, not provided for by group C07D415/00 containing three or more hetero rings
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- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
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- H10K50/10—OLEDs or polymer light-emitting diodes [PLED]
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- H10K85/111—Organic polymers or oligomers comprising aromatic, heteroaromatic, or aryl chains, e.g. polyaniline, polyphenylene or polyphenylene vinylene
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- 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
- C08G2261/322—Monomer units or repeat units incorporating structural elements in the main chain incorporating heteroaromatic structural elements in the main chain non-condensed
- C08G2261/3221—Monomer units or repeat units incorporating structural elements in the main chain incorporating heteroaromatic structural elements in the main chain non-condensed containing one or more nitrogen atoms as the only heteroatom, e.g. pyrrole, pyridine or triazole
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- 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
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- C08G2261/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
- C08G2261/40—Polymerisation processes
- C08G2261/41—Organometallic coupling reactions
- C08G2261/411—Suzuki reactions
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- C08G2261/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
- C08G2261/50—Physical properties
- C08G2261/51—Charge transport
- C08G2261/512—Hole transport
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- C08G2261/90—Applications
- C08G2261/95—Use in organic luminescent diodes
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Abstract
The invention provides a kind of organic semiconducting materials, the chemical formula of described organic semiconducting materials is as follows:Wherein, R is C1~C20Alkyl, n is the integer of 10 ~ 100, the present invention provides organic semiconducting materials to have hole transport character and electronic transport property simultaneously, the transmission making hole and electronics in luminescent layer balances, also there is higher triplet, triplet is more than 2.78eV, effectively prevents energy in luminescence process from returning to material of main part, is greatly improved luminous efficiency.This organic semiconducting materials have employed better simply synthetic route, decreases technological process, and raw material are cheap and easy to get, and manufacturing cost is reduced.
Description
Technical field
The invention belongs to field of photovoltaic materials, be specifically related to a kind of organic semiconducting materials.
Background technology
Organic electroluminescence device has that driving voltage is low, fast response time, angular field of view width and can pass through
Chemical constitution fine setting changes luminescent properties makes rich color, easily realizes that resolution ratio is high, lightweight, large area
The advantages such as FPD, are described as " 21 century flat panel display ", become material, information, physics etc. and learn
Section and the focus of FPD area research.Following efficient commercialization Organic Light Emitting Diode will be likely to
Containing organic metal phosphor, because singlet and triplet excitons can all be captured by they, thus realize
The internal quantum efficiency of 100%.But, owing to the excitation state exciton lifetime of transient metal complex is the most long,
Cause unwanted triplet state-triplet state (T1-T1) cancellation in device real work.In order to overcome this to ask
Topic, triplet emission thing is often doped in organic host material by researchers.
In recent years, green and red phosphorescent OLED shows gratifying electroluminescent efficiency.And
Efficient blue phosphorescent device is little, and main cause is a lack of having preferable carrier transmission performance simultaneously
Higher triplet (ET) material of main part.
Summary of the invention
For solving the problems referred to above, the invention provides a kind of organic semiconducting materials, this organic semiconducting materials
There is hole transport character and electronic transport property, make the transmission of hole and electronics in luminescent layer balance,
Also having higher triplet, triplet is more than 2.78eV, effectively prevents energy in luminescence process
Amount returns to material of main part, is greatly improved luminous efficiency, and organic semiconducting materials of the present invention is bipolarity blue light
Phosphorescent light body material provides new selectable kind.Present invention also offers this organic semiconducting materials
Preparation method, and comprise the electroluminescent device of this organic semiconducting materials.
On the one hand, the invention provides a kind of organic semiconducting materials, the chemistry of described organic semiconducting materials
Formula is as follows:
Wherein, R is C1～C20Alkyl, n be 10～100 whole
Number.
Second aspect, the invention provides the preparation method of a kind of organic semiconducting materials, comprises the steps:
Offer compound A:With compound B:
Wherein, R is C1～C20Alkyl；Under an inert atmosphere, by compound A and compound B according to mol ratio
It is in 1: 1～1: 1.2 organic solvent being added into containing catalyst and aqueous slkali, carries out at 70～130 DEG C
Suzuki coupled reaction 12～96 hours, described catalyst is organic palladium or for organic palladium and organophosphor ligand
Mixture, obtains the organic semiconducting materials P that following structural formula represents:
Wherein, n is the integer of 10～100.
Preferably, the preparation method of described organic semiconducting materials also includes carrying out organic semiconducting materials P
Isolated and purified step, described purification procedures is as follows: carry out to described compound A and compound B
Solution after Suzuki coupled reaction adds methyl alcohol precipitating and filters, the solid being filtrated to get is used first successively
Alcohol and n-hexane are stripped, and by the solid chloroform after extracting, evaporate after collecting chloroformic solution
Solvent obtains organic semiconducting materials P after purification.
Preferably, during described organic solvent is selected from toluene, DMF, oxolane at least
A kind of.
Preferably, during described aqueous slkali is selected from sodium carbonate liquor, solution of potassium carbonate and sodium bicarbonate solution extremely
Few one, the solute in described aqueous slkali is 20: 1～50: 1 with the mol ratio of compound A.
Preferably, described organic palladium is bis-triphenylphosphipalladium palladium dichloride, tetra-triphenylphosphine palladium, palladium or three
Dibenzalacetone two palladium, described organophosphorus ligand is that tri-butyl phosphine, tri-o-tolyl phosphine or 2-dicyclo are own
Base phosphorus-2 ', 6 '-dimethoxy-biphenyl, described organic palladium is 1: 4～1: 8 with the mol ratio of described organophosphorus ligand.
Preferably, the organic palladium in described catalyst is 1: 20～1: 100 with the mol ratio of described compound A.
The third aspect, the invention provides a kind of electroluminescent device, including the anode that has stacked gradually
Substrate, luminescent layer and cathode layer, described luminescent layer is the mixture of material of main part and guest materials, wherein
The organic semiconducting materials that material of main part is as follows:Wherein, R is
C1～C20Alkyl, n is the integer of 10～100, and guest materials is three [1-phenyl isoquinolin quinoline-C2, N] iridium, double
(4,6-difluorophenyl pyridinato-N, C2) pyridinecarboxylic closes iridium, [two (2 ', 4 '-difluorophenyl) pyridine] [four (1-pyrazolyls)
Boron] close iridium or [two (2 ', 4 '-difluorophenyl) pyridine] (tetrazolium pyridine) conjunction iridium.
Preferably, described material of main part is 5%～20% with the mass percent of described guest materials.
Preferably, anode material is indium zinc oxide or zinc oxide aluminum, and negative electrode is metallic aluminium, silver, gold or nickel.
The invention provides a kind of organic semiconducting materials, preparation method and electroluminescent device, have following
Beneficial effect: simultaneously have hole transport character and electronic transport property, makes hole and electronics in luminescent layer
Transmission balance, also there is higher triplet, triplet be more than 2.78eV, effectively prevent send out
In photoreduction process, energy returns to material of main part, is greatly improved luminous efficiency.This material have employed better simply conjunction
Becoming route, decrease technological process, raw material are cheap and easy to get, and manufacturing cost is reduced.
Accompanying drawing explanation
Fig. 1 is the organic electroluminescent that the organic semiconducting materials prepared in embodiment 1 prepares for material of main part
The structural representation of device；
Fig. 2 is the differential scanning calorimetric curve of the organic semiconducting materials prepared in embodiment 1.
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 invention provides a kind of organic semiconducting materials, the following institute of chemical formula of described organic semiconducting materials
Show:
Wherein, R is C1～C20Alkyl, n be 10～100 whole
Number.
This organic semiconducting materials has bipolarity carrier transport ability, makes the hole in luminescent layer and electricity
Son transmission balance；There is hole transport character and electronic transport property simultaneously, make hole and electricity in luminescent layer
The transmission balance of son, also has higher triplet, and triplet is more than 2.78eV, effectively prevents
Only in luminescence process, energy returns to material of main part, is greatly improved luminous efficiency, and therefore the present invention is organic partly leads
Body material has bipolarity blue emitting phosphor material of main part.
The invention provides the preparation method of a kind of organic semiconducting materials, comprise the steps:
Offer compound A:With compound B:
Wherein, R is C1～C20Alkyl；Under an inert atmosphere, by compound A and compound B according to mol ratio
It is in 1: 1～1: 1.2 organic solvent being added into containing catalyst and aqueous slkali, carries out at 70～130 DEG C
Suzuki coupled reaction 12～96 hours, described catalyst is organic palladium or for organic palladium and organophosphor ligand
Mixture, obtains the organic semiconducting materials P that following structural formula represents:
Wherein, n is the integer of 10～100.
In a particular embodiment, the preparation method of described organic semiconducting materials further comprises organic half
Conductor material P carries out isolated and purified step, and described purification procedures is as follows: to described compound A and
Compound B carry out Suzuki coupled reaction after solution in add methyl alcohol precipitating filtering, by be filtrated to get
Solid is stripped with methyl alcohol and n-hexane successively, by the solid chloroform after extracting, collects chlorine
Evaporate solvent after imitative solution and obtain organic semiconducting materials P after purification.
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 P after purification
50 DEG C～70 DEG C are dried 24 hours～48 hours under vacuo.
In a particular embodiment, described organic solvent is selected from toluene, DMF, oxolane
In at least one.
In a particular embodiment, described aqueous slkali is molten selected from sodium carbonate liquor, solution of potassium carbonate and sodium acid carbonate
At least one in liquid, the solute in described aqueous slkali is 20: 1～50: 1 with the mol ratio of compound A.
In a particular embodiment, described organic palladium be bis-triphenylphosphipalladium palladium dichloride, 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, described organic palladium with the mol ratio of described organophosphorus ligand is
1: 4～1: 8.
In a particular embodiment, the organic palladium in described catalyst with the mol ratio of described compound A is
1: 20～1: 100.
Have employed better simply synthetic route, thus reduce technological process, raw material are cheap and easy to get so that system
Cause this reduction.
The invention provides a kind of electroluminescent device, including stack gradually, there is the substrate of anode, luminescence
Layer and cathode layer, described luminescent layer is the mixture of material of main part and guest materials, and wherein material of main part is such as
Organic semiconducting materials shown in lower:Wherein, R is C1～C20's
Alkyl, n is the integer of 10～100, and guest materials is three [1-phenyl isoquinolin quinoline-C2, N] iridium, double (4,6-difluoros
Phenylpyridine-N, C2) pyridinecarboxylic close iridium, [two (2 ', 4 '-difluorophenyl) pyridine] [four (1-pyrazolyl) boron] close iridium or
Person's [two (2 ', 4 '-difluorophenyl) pyridine] (tetrazolium pyridine) closes iridium.
In a particular embodiment, described guest materials is 5%～20% with the mass percent of described material of main part.
In a particular embodiment, anode material is indium zinc oxide or zinc oxide aluminum, negative electrode be metallic aluminium, silver,
Gold or nickel.
Organic luminescent device based on this material launches blue light, and luminous efficiency is high.
Embodiment 1:
Present embodiment discloses structural formula following poly-N-n-hexane base-3,7-diyl-phenthazine-co-2,6-diyl-
Pyridine } (organic semiconducting materials P1):
The preparation process of above-mentioned organic semiconducting materials P1 is as follows:
Under argon shield, by N-n-hexane base-3, and 7-bis-pinacol borate phenthazine (107mg, 0.2
Mmol), 2, the bromo-pyridine of 6-bis-(47mg, 0.2mmol) adds and fills in the flask of 10ml toluene solvant, fully
After dissolving, potassium carbonate (2mL, 2mol/L) solution is joined in flask, vacuumize deoxygenation and be filled with argon gas, so
Rear addition bis-triphenylphosphipalladium palladium dichloride (5.6mg, 0.008mmol)；Flask is heated to 100 DEG C carry out
Suzuki coupled reaction 48h.Stop polymerisation after cooling, drip in 50ml methyl alcohol in flask and sink
Fall；Successively with methyl alcohol and n-hexane extracting 24h after being filtered by apparatus,Soxhlet's.Then it is molten with chloroform
Agent extracting, to colourless, collected chloroformic solution and is spin-dried for obtaining red powder, obtaining this poly-{ N-n-hexane base-3,7-
Diyl-phenthazine-co-2,6-diyl-pyridine } organic semiconducting materials, the lower 50 DEG C of dry 24h of last vacuum.Produce
Rate is 83%.
The above-mentioned reaction equation preparing organic semiconducting materials P1 is as follows:
Molecule measuring test result is: Molecular weight (GPC, THF, R.I): Mn=21.8kDa,
Mw/Mn=2.2.
See the differential scanning calorimetric curve that accompanying drawing 2 is organic semiconducting materials prepared by the present embodiment, differential
Scanning calorimetric curve test is carried out on Perkin Elmer DSC-7, glass transition temperature as seen from the figure
(Tg) it is 118 DEG C.
The uv-visible absorption spectra figure of the organic semiconducting materials P1 of preparation, ultraviolet-visible in embodiment 1
Absorption spectrum is measured on Jasco-570 uv analyzer.As seen from the figure: Inventive polymers
Having absorption wider relatively greatly between 300nm～700nm, wherein maximum absorption band is positioned at 583nm, wide absorption
Spectrum shows that P1 is a kind of photovoltaic material.
By test antenna effect spectrum, instrument is FS modular fluorometer/pectrophosphorimeter, to investigate embodiment 1
The organic semiconducting materials P1 triplet emission characteristic of middle preparation.Under the liquid nitrogen of 77K, organic semiconductor material
Material P1 shows the strongest phosphorescent emissions, and emission peak is at 442nm, and corresponding triplet energy state is 2.80eV,
It is much higher than double (4,6-difluorophenyl pyridinato-N, the C2) pyridinecarboxylic of phosphor material and closes the triplet state of iridium (III) FIrpic
Energy (2.65eV), test data result shows that our material can be as blue emitting phosphor material of main part.
Embodiment 2:
Present embodiment discloses poly-{ N-methyl-3,7-diyl-phenthazine-co-2,6-diyl-pyrrole that structural formula is following
Pyridine } (organic semiconducting materials P2):
Under nitrogen and argon gas gaseous mixture are protected, by N-methyl-3,7-bis-pinacol borate phenthazine (140
Mg, 0.3mmol), 2, the bromo-pyridine of 6-bis-(71mg, 0.3mmol) and 15mL oxolane add 50mL rule
In the two-mouth bottle of lattice, after being passed through the gaseous mixture air-discharging about 20min of nitrogen and argon gas after fully dissolving, then
Tetra-triphenylphosphine palladium (4mg, 0.003mmol) is added thereto, add after fully dissolving sodium acid carbonate (3mL,
2mol/L) solution.After the most fully leading to the gaseous mixture air-discharging about 10min of nitrogen and argon gas, two-mouth bottle is added
Suzuki coupled reaction 96h is carried out to 70 DEG C.Stop polymerisation after cooling, in flask, drip 40ml
Methyl alcohol settles；Successively with methyl alcohol and n-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 red powder, obtain poly-{ N-first
Alkyl-3,7-diyl-phenthazine-co-2,6-diyl-pyridine } organic semiconducting materials, lower 50 DEG C of last vacuum is dried
24h.Productivity is 80%.
The above-mentioned reaction equation preparing organic semiconducting materials P2 is as follows:
Molecule measuring test result is: Molecular weight (GPC, THF, R.I): Mn=13.4kDa,
Mw/Mn=2.4.
The differential scanning calorimetric curve of the organic semiconducting materials P2 of the present embodiment 2 preparation, means of differential scanning calorimetry
Curve test is carried out on Perkin Elmer DSC-7, glass transition temperature (Tg) it is 131 DEG C.
The uv-visible absorption spectra figure of the organic semiconducting materials P2 of preparation, ultraviolet-visible in embodiment 2
Absorption spectrum is measured on Jasco-570 uv analyzer.As seen from the figure: Inventive polymers
Having absorption wider relatively greatly between 300nm～700nm, wherein maximum absorption band is positioned at 584nm, wide absorption
Spectrum shows that P2 is a kind of photovoltaic material.
By test antenna effect spectrum, instrument is FS modular fluorometer/pectrophosphorimeter, to investigate organic half
Conductor material P2 triplet emission characteristic.Under the liquid nitrogen of 77K, organic semiconducting materials P2 shows very
Strong phosphorescent emissions, emission peak is at 437nm, and corresponding triplet energy state is 2.84eV, is much higher than phosphorescence
Double (4,6-difluorophenyl pyridinato-N, the C2) pyridinecarboxylic of material closes the triplet energy state of iridium (III) FIrpic
(2.65eV), test data result shows that our material can be as blue emitting phosphor material of main part.
Embodiment 3:
Present embodiment discloses poly-{ N-methyl-3,7-diyl-phenthazine-co-2,6-diyl-pyrrole that structural formula is following
Pyridine } (organic semiconducting materials P3):
Under nitrogen protection, by N-n-eicosane base-3, and 7-bis-pinacol borate phenthazine (220mg, 0.3
Mmol), 2, the bromo-pyridine of 6-bis-(78mg, 0.33mmol), palladium (3.5mg, 0.015mmol) and three are (adjacent
Methoxyphenyl) phosphine (21mg, 0.06mmol) joins the DMF filling 12mL
In flask, add potassium carbonate (3mL, 2mol/L) solution after fully dissolving, subsequently toward nitrogen purge logical in flask
After gas about 30min；Flask is heated to 130 DEG C and carries out Suzuki coupled reaction 12h.Stop reacting and cold
But arrive room temperature, drip in 40ml methyl alcohol in flask and settle；After being filtered by apparatus,Soxhlet's successively
24h is extracted with methyl alcohol and n-hexane.Then with chloroform for solvent extraction to colourless, collect chloroformic solution and revolve
Dry obtain red powder, obtain that poly-{ N-methyl-3,7-diyl-phenthazine-co-2,6-diyl-pyridine } is organic partly leads
Body material, the lower 50 DEG C of dry 24h of last vacuum.Productivity is 75%.
The above-mentioned reaction equation preparing organic semiconducting materials P3 is as follows:
Molecule measuring test result is: Molecular weight (GPC, THF, R.I): Mn=50.1kDa,
Mw/Mn=2.0.
The differential scanning calorimetric curve of the organic semiconducting materials P3 of the present embodiment 3 preparation, means of differential scanning calorimetry
Curve test is carried out on Perkin Elmer DSC-7, glass transition temperature (Tg) it is 92 DEG C.
The uv-visible absorption spectra figure of the organic semiconducting materials P3 of preparation, ultraviolet-visible in embodiment 3
Absorption spectrum is measured on Jasco-570 uv analyzer.As seen from the figure: Inventive polymers
Having absorption wider relatively greatly between 300nm～700nm, wherein maximum absorption band is positioned at 579nm, wide absorption
Spectrum shows that P3 is a kind of photovoltaic material.
By test antenna effect spectrum, instrument is FS modular fluorometer/pectrophosphorimeter, to investigate organic half
Conductor material P triplet emission characteristic.Under the liquid nitrogen of 77K, organic semiconducting materials P shows the strongest
Phosphorescent emissions, emission peak is at 444nm, and corresponding triplet energy state is 2.79eV, is much higher than phosphorescence material
Double (4,6-difluorophenyl pyridinato-N, the C2) pyridinecarboxylic of material closes the triplet energy state (2.65eV) of iridium (III) FIrpic,
Test data result shows that our material can be as blue emitting phosphor material of main part.
Embodiment 4:
Present embodiment discloses poly-{ N-normal butane base-3,7-diyl-phenthazine-2,7-diyl click that structural formula is following
Azoles-co-2,6-diyl-pyridine } (organic semiconducting materials P4):
Under nitrogen protection, by N-normal butane base-3, and 7-bis-pinacol borate phenthazine (152mg, 0.3
Mmol), 2, the bromo-pyridine of 6-bis-(85mg, 0.36mmol), three or two argon benzylacetones two palladium (9mg, 0.009mmol)
With 2-dicyclohexyl phosphine-2 ', 6 '-dimethoxy-biphenyl (29mg, 0.072mmol) joins and fills 12mL
DMF flask in, add sodium carbonate (3mL, 2mol/L) solution after fully dissolving.With
Afterwards toward after nitrogen purge gas about 30min logical in flask；Flask is heated to 120 DEG C and carries out Suzuki coupling instead
Answer 36h.Stop polymerisation after cooling, drip in 40ml methyl alcohol in flask and settle；Pass through Soxhlet
Extractor extracts 24h with methyl alcohol and n-hexane after filtering successively.Then with chloroform for solvent extraction to colourless,
Collect chloroformic solution and be spin-dried for obtaining red powder, obtaining poly-{ N-normal butane base-3,7-diyl-phenthazine-2,7-
Diyl carbazole-co-2,6-diyl-pyridine } organic semiconducting materials, the lower 50 DEG C of dry 24h of last vacuum.Productivity
It is 82%.
The above-mentioned reaction equation preparing organic semiconducting materials P4 is as follows:
Molecule measuring test result is: Molecular weight (GPC, THF, R.I): Mn=43.4kDa,
Mw/Mn=2.1.
The differential scanning calorimetric curve of the organic semiconducting materials P4 of the present embodiment 4 preparation, means of differential scanning calorimetry
Curve test is carried out on Perkin Elmer DSC-7, glass transition temperature (Tg) it is 126 DEG C.
The uv-visible absorption spectra figure of the organic semiconducting materials P4 of preparation, ultraviolet-visible in embodiment 4
Absorption spectrum is measured on Jasco-570 uv analyzer.As seen from the figure: Inventive polymers
Having absorption wider relatively greatly between 300nm～700nm, wherein maximum absorption band is positioned at 586nm, wide absorption
Spectrum shows that P4 is a kind of photovoltaic material.
By test antenna effect spectrum, instrument is FS modular fluorometer/pectrophosphorimeter, to investigate organic half
Conductor material P4 triplet emission characteristic.Under the liquid nitrogen of 77K, organic semiconducting materials P4 shows very
Strong phosphorescent emissions, emission peak is at 438nm, and corresponding triplet energy state is 2.82eV, is much higher than phosphorescence
Double (4,6-difluorophenyl pyridinato-N, the C2) pyridinecarboxylic of material closes the triplet energy state of iridium (III) FIrpic
(2.65eV), test data result shows that our material can be as blue emitting phosphor material of main part.
Embodiment 5:
Present embodiment discloses poly-{ N-dodecyl-3,7-diyl-phenthazine-co-2,6-bis-that structural formula is following
Base-pyridine } (organic semiconducting materials P5):
Under nitrogen protection, by N-dodecyl-3, and 7-bis-pinacol borate phenthazine (186mg, 0.3
Mmol), 2, the bromo-pyridine of 6-bis-(71mg, 0.36mmol), tetra-triphenylphosphine palladium (8mg, 0.006mmol) add
Enter in the twoport flask filling 15mL toluene and adding 50mL, add after fully dissolving potassium carbonate (3mL,
2mol/L) solution.Subsequently toward after nitrogen purge gas about 10min logical in flask；Flask is heated to 90 DEG C enter
Row Suzuki coupled reaction 60h.Stop polymerisation after cooling, drip in 40ml methyl alcohol in flask
Row sedimentation；Successively with methyl alcohol and n-hexane extracting 24h after being filtered by apparatus,Soxhlet's.Then with chloroform
For solvent extraction to colourless, collect chloroformic solution and be spin-dried for obtaining red powder, obtaining poly-{ N-dodecyl
-3,7-diyl-phenthazine-co-2,6-diyl-pyridine } the lower 50 DEG C of dry 24h of the last vacuum of organic semiconducting materials.
Productivity is 76%.
The above-mentioned reaction equation preparing organic semiconducting materials P5 is as follows:
Molecule measuring test result is: Molecular weight (GPC, THF, R.I): Mn=22.6kDa,
Mw/Mn=2.3.
The differential scanning calorimetric curve of the organic semiconducting materials P5 of the present embodiment 5 preparation, means of differential scanning calorimetry
Curve test is carried out on Perkin Elmer DSC-7, glass transition temperature (Tg) it is 105 DEG C.
The uv-visible absorption spectra figure of the organic semiconducting materials P5 of preparation, ultraviolet-visible in embodiment 5
Absorption spectrum is measured on Jasco-570 uv analyzer.As seen from the figure: Inventive polymers
Having absorption wider relatively greatly between 300nm～700nm, wherein maximum absorption band is positioned at 585nm, wide absorption
Spectrum shows that P5 is a kind of photovoltaic material.
By test antenna effect spectrum, instrument is FS modular fluorometer/pectrophosphorimeter, to investigate organic half
Conductor material P5 triplet emission characteristic.Under the liquid nitrogen of 77K, organic semiconducting materials P5 shows very
Strong phosphorescent emissions, emission peak is at 444nm, and corresponding triplet energy state is 2.79eV, is much higher than phosphorescence
Double (4,6-difluorophenyl pyridinato-N, the C2) pyridinecarboxylic of material closes the triplet energy state of iridium (III) FIrpic
(2.65eV), test data result shows that our material can be as blue emitting phosphor material of main part.
Application Example
Organic electroluminescence device 300, its structure such as Fig. 1 it include substrate 301, anode 302, hole is noted
Enter layer 303, hole transmission layer 304, luminescent layer 305, electron transfer layer 306, electronics 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 poly-(3,4-rthylene dioxythiophene)-polystyrolsulfon acid, and thickness is 30nm,
Hole transmission layer 304 uses N, N '-diphenyl-N, N '-(1-naphthyl)-1,1 '-biphenyl-4,4 '-diamines, and thickness is
20nm, luminescent layer 305 main body luminescent material uses the present invention to implement poly-{ the N-n-hexane base of compound of 1 preparation
-3,7-diyl-phenthazine-co-2,6-diyl-pyridine }, and doping mass percent is on the basis of material of main part
Double (4,6-difluorophenyl pyridinato-N, the C2) pyridinecarboxylic of the guest emitting material of 10% closes iridium (III), luminescent layer 305
Thickness is 20nm, electron transfer layer 306 use 5 (thickness is 30nm for 4,7-diphenyl-1,10-phenanthroline,
Electronics injecting layer 307 uses lithium fluoride, and 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, film
Thickness use film thickness monitoring instrument monitor, in addition to guest materials, the evaporation rate of all organic materials is The evaporation rate of lithium fluoride isThe evaporation rate of metallic aluminium is
This electroluminescent device has higher luminous efficiency, can be widely used in the luminous neck such as blueness or white
Territory.Current versus brightness-the voltage characteristic of device is to be surveyed by the Keithley source with correction silicon photoelectric diode
All surveys that amount system (Keithley 2400Sourcemeter, Keithley 2000Cuirrentmeter) completes
Amount all completes in atmosphere at room temperature.Result shows: the maximum electrical efficiency of device is 10.8cd/A, high-high brightness
For 24710cd/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. an organic semiconducting materials, it is characterised in that the chemical formula of described organic semiconducting materials is as follows
Shown in:
Wherein, R is C1～C20Alkyl, n be 10～100 whole
Number.
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| CN101809117A (en) * | 2007-11-01 | 2010-08-18 | 第一毛织株式会社 | Material for organic photoelectric device, and organic photoelectric device thereby |
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| CN101809117A (en) * | 2007-11-01 | 2010-08-18 | 第一毛织株式会社 | Material for organic photoelectric device, and organic photoelectric device thereby |
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