CN109970806B - Organic metal iridium complex, preparation method thereof and application thereof in OLED - Google Patents
Organic metal iridium complex, preparation method thereof and application thereof in OLED Download PDFInfo
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- 238000002360 preparation method Methods 0.000 title claims abstract description 57
- GKOZUEZYRPOHIO-UHFFFAOYSA-N iridium atom Chemical compound [Ir] GKOZUEZYRPOHIO-UHFFFAOYSA-N 0.000 title claims abstract description 37
- 229910052741 iridium Inorganic materials 0.000 title claims abstract description 36
- 229910052751 metal Inorganic materials 0.000 title claims abstract description 22
- 239000002184 metal Substances 0.000 title claims abstract description 22
- 239000000463 material Substances 0.000 claims abstract description 50
- 238000004519 manufacturing process Methods 0.000 claims abstract description 9
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 42
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 36
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 24
- 238000003756 stirring Methods 0.000 claims description 16
- 238000001035 drying Methods 0.000 claims description 15
- 239000000243 solution Substances 0.000 claims description 15
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 13
- 238000006243 chemical reaction Methods 0.000 claims description 12
- 238000001914 filtration Methods 0.000 claims description 12
- 239000002994 raw material Substances 0.000 claims description 12
- 125000000217 alkyl group Chemical group 0.000 claims description 11
- 238000001816 cooling Methods 0.000 claims description 10
- 239000012065 filter cake Substances 0.000 claims description 10
- 229910052757 nitrogen Inorganic materials 0.000 claims description 10
- 125000002524 organometallic group Chemical group 0.000 claims description 10
- 239000007787 solid Substances 0.000 claims description 10
- XNWFRZJHXBZDAG-UHFFFAOYSA-N 2-METHOXYETHANOL Chemical compound COCCO XNWFRZJHXBZDAG-UHFFFAOYSA-N 0.000 claims description 9
- 239000012153 distilled water Substances 0.000 claims description 9
- LNJXVUXPFZKMNF-UHFFFAOYSA-K iridium(3+);trichloride;trihydrate Chemical compound O.O.O.Cl[Ir](Cl)Cl LNJXVUXPFZKMNF-UHFFFAOYSA-K 0.000 claims description 9
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N diphenyl Chemical compound C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 claims description 8
- 229910052739 hydrogen Inorganic materials 0.000 claims description 8
- 239000001257 hydrogen Substances 0.000 claims description 8
- 239000000047 product Substances 0.000 claims description 8
- CZKMPDNXOGQMFW-UHFFFAOYSA-N chloro(triethyl)germane Chemical compound CC[Ge](Cl)(CC)CC CZKMPDNXOGQMFW-UHFFFAOYSA-N 0.000 claims description 7
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 7
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 6
- 229910052799 carbon Inorganic materials 0.000 claims description 6
- 125000001624 naphthyl group Chemical group 0.000 claims description 6
- 239000002019 doping agent Substances 0.000 claims description 5
- 239000000741 silica gel Substances 0.000 claims description 5
- 229910002027 silica gel Inorganic materials 0.000 claims description 5
- 235000010290 biphenyl Nutrition 0.000 claims description 4
- 239000004305 biphenyl Substances 0.000 claims description 4
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims description 4
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 claims description 4
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 4
- 239000011259 mixed solution Substances 0.000 claims description 4
- 125000004076 pyridyl group Chemical group 0.000 claims description 4
- 239000000376 reactant Substances 0.000 claims description 4
- 239000002904 solvent Substances 0.000 claims description 4
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 claims description 4
- 229910052760 oxygen Inorganic materials 0.000 claims description 3
- 229910052717 sulfur Inorganic materials 0.000 claims description 3
- 150000005840 aryl radicals Chemical class 0.000 claims description 2
- 239000012298 atmosphere Substances 0.000 claims description 2
- 125000004432 carbon atom Chemical group C* 0.000 claims description 2
- 125000000113 cyclohexyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 claims description 2
- 239000000706 filtrate Substances 0.000 claims description 2
- 125000000524 functional group Chemical group 0.000 claims description 2
- 238000002386 leaching Methods 0.000 claims description 2
- 125000001570 methylene group Chemical group [H]C([H])([*:1])[*:2] 0.000 claims description 2
- 125000004435 hydrogen atom Chemical class [H]* 0.000 claims 2
- 238000005086 pumping Methods 0.000 claims 1
- 230000000694 effects Effects 0.000 abstract description 5
- 239000010410 layer Substances 0.000 description 57
- VQGHOUODWALEFC-UHFFFAOYSA-N 2-phenylpyridine Chemical compound C1=CC=CC=C1C1=CC=CC=N1 VQGHOUODWALEFC-UHFFFAOYSA-N 0.000 description 21
- 238000001514 detection method Methods 0.000 description 15
- 238000004128 high performance liquid chromatography Methods 0.000 description 15
- 238000010438 heat treatment Methods 0.000 description 13
- 239000007858 starting material Substances 0.000 description 12
- VZSRBBMJRBPUNF-UHFFFAOYSA-N 2-(2,3-dihydro-1H-inden-2-ylamino)-N-[3-oxo-3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)propyl]pyrimidine-5-carboxamide Chemical compound C1C(CC2=CC=CC=C12)NC1=NC=C(C=N1)C(=O)NCCC(N1CC2=C(CC1)NN=N2)=O VZSRBBMJRBPUNF-UHFFFAOYSA-N 0.000 description 10
- 238000001704 evaporation Methods 0.000 description 10
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 8
- 230000000052 comparative effect Effects 0.000 description 8
- 238000005406 washing Methods 0.000 description 7
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 6
- 230000000903 blocking effect Effects 0.000 description 6
- 230000008020 evaporation Effects 0.000 description 6
- 238000004770 highest occupied molecular orbital Methods 0.000 description 6
- 238000002347 injection Methods 0.000 description 6
- 239000007924 injection Substances 0.000 description 6
- 238000010992 reflux Methods 0.000 description 6
- 230000005525 hole transport Effects 0.000 description 5
- 238000012360 testing method Methods 0.000 description 5
- 238000007738 vacuum evaporation Methods 0.000 description 5
- 230000005284 excitation Effects 0.000 description 4
- 150000002431 hydrogen Chemical class 0.000 description 4
- 239000000758 substrate Substances 0.000 description 4
- 239000012295 chemical reaction liquid Substances 0.000 description 3
- 239000003153 chemical reaction reagent Substances 0.000 description 3
- 230000009849 deactivation Effects 0.000 description 3
- 239000007772 electrode material Substances 0.000 description 3
- 238000005401 electroluminescence Methods 0.000 description 3
- 230000009477 glass transition Effects 0.000 description 3
- 230000006872 improvement Effects 0.000 description 3
- 239000008204 material by function Substances 0.000 description 3
- 239000000843 powder Substances 0.000 description 3
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 3
- 238000011160 research Methods 0.000 description 3
- YLZOPXRUQYQQID-UHFFFAOYSA-N 3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)-1-[4-[2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidin-5-yl]piperazin-1-yl]propan-1-one Chemical compound N1N=NC=2CN(CCC=21)CCC(=O)N1CCN(CC1)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F YLZOPXRUQYQQID-UHFFFAOYSA-N 0.000 description 2
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- HGTJNNZFQJIZII-UHFFFAOYSA-M CO.FC(S(=O)(=O)[O-])(F)F.[Ag+] Chemical compound CO.FC(S(=O)(=O)[O-])(F)F.[Ag+] HGTJNNZFQJIZII-UHFFFAOYSA-M 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 2
- 125000003118 aryl group Chemical group 0.000 description 2
- 238000004140 cleaning Methods 0.000 description 2
- 238000000354 decomposition reaction Methods 0.000 description 2
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- 230000002035 prolonged effect Effects 0.000 description 2
- 125000000714 pyrimidinyl group Chemical class 0.000 description 2
- 238000001228 spectrum Methods 0.000 description 2
- VFMUXPQZKOKPOF-UHFFFAOYSA-N 2,3,7,8,12,13,17,18-octaethyl-21,23-dihydroporphyrin platinum Chemical compound [Pt].CCc1c(CC)c2cc3[nH]c(cc4nc(cc5[nH]c(cc1n2)c(CC)c5CC)c(CC)c4CC)c(CC)c3CC VFMUXPQZKOKPOF-UHFFFAOYSA-N 0.000 description 1
- YASXBDJBCBUIHT-UHFFFAOYSA-N 2,4-diphenylpyridine Chemical compound C1=CC=CC=C1C1=CC=NC(C=2C=CC=CC=2)=C1 YASXBDJBCBUIHT-UHFFFAOYSA-N 0.000 description 1
- NLVDIPIEDWNILG-UHFFFAOYSA-N 2-dibenzofuran-4-ylpyridine Chemical compound N1=CC=CC=C1C1=CC=CC2=C1OC1=CC=CC=C12 NLVDIPIEDWNILG-UHFFFAOYSA-N 0.000 description 1
- LNJZJDLDXQQJSG-UHFFFAOYSA-N 2-phenylpyrazine Chemical compound C1=CC=CC=C1C1=CN=CC=N1 LNJZJDLDXQQJSG-UHFFFAOYSA-N 0.000 description 1
- LGMAQUKSVXFRJG-UHFFFAOYSA-N 2-pyridin-4-ylpyrazine Chemical compound C1=NC=CN=C1C1=CC=NC=C1 LGMAQUKSVXFRJG-UHFFFAOYSA-N 0.000 description 1
- RMHQDKYZXJVCME-UHFFFAOYSA-N 2-pyridin-4-ylpyridine Chemical compound N1=CC=CC=C1C1=CC=NC=C1 RMHQDKYZXJVCME-UHFFFAOYSA-N 0.000 description 1
- GGPHNFIDPNYSPE-UHFFFAOYSA-N 3,5-dimethyl-2-phenylpyridine Chemical compound CC1=CC(C)=CN=C1C1=CC=CC=C1 GGPHNFIDPNYSPE-UHFFFAOYSA-N 0.000 description 1
- RTNPJCQBMCRDSE-UHFFFAOYSA-N 3,5-diphenylpyridazine Chemical compound C1=CC=CC=C1C1=CN=NC(C=2C=CC=CC=2)=C1 RTNPJCQBMCRDSE-UHFFFAOYSA-N 0.000 description 1
- XWSSUYOEOWLFEI-UHFFFAOYSA-N 3-phenylpyridazine Chemical compound C1=CC=CC=C1C1=CC=CN=N1 XWSSUYOEOWLFEI-UHFFFAOYSA-N 0.000 description 1
- CUBIMBZVFXQWCD-UHFFFAOYSA-N 3-pyridin-4-ylpyridazine Chemical group C1=CN=NC(C=2C=CN=CC=2)=C1 CUBIMBZVFXQWCD-UHFFFAOYSA-N 0.000 description 1
- AWXGSYPUMWKTBR-UHFFFAOYSA-N 4-carbazol-9-yl-n,n-bis(4-carbazol-9-ylphenyl)aniline Chemical compound C12=CC=CC=C2C2=CC=CC=C2N1C1=CC=C(N(C=2C=CC(=CC=2)N2C3=CC=CC=C3C3=CC=CC=C32)C=2C=CC(=CC=2)N2C3=CC=CC=C3C3=CC=CC=C32)C=C1 AWXGSYPUMWKTBR-UHFFFAOYSA-N 0.000 description 1
- MKLQPIYLZMLAER-UHFFFAOYSA-N 4-phenylpyrimidine Chemical compound C1=CC=CC=C1C1=CC=NC=N1 MKLQPIYLZMLAER-UHFFFAOYSA-N 0.000 description 1
- UACHOGFPFNIAIG-UHFFFAOYSA-N 4-pyridin-4-ylpyrimidine Chemical compound C1=NC=CC(C=2N=CN=CC=2)=C1 UACHOGFPFNIAIG-UHFFFAOYSA-N 0.000 description 1
- 125000000882 C2-C6 alkenyl group Chemical group 0.000 description 1
- 101000837344 Homo sapiens T-cell leukemia translocation-altered gene protein Proteins 0.000 description 1
- NIPNSKYNPDTRPC-UHFFFAOYSA-N N-[2-oxo-2-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)ethyl]-2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carboxamide Chemical compound O=C(CNC(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)N1CC2=C(CC1)NN=N2 NIPNSKYNPDTRPC-UHFFFAOYSA-N 0.000 description 1
- 102100028692 T-cell leukemia translocation-altered gene protein Human genes 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 125000002947 alkylene group Chemical class 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000011203 carbon fibre reinforced carbon Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 125000000753 cycloalkyl group Chemical group 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- 238000011982 device technology Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000000113 differential scanning calorimetry Methods 0.000 description 1
- DKHNGUNXLDCATP-UHFFFAOYSA-N dipyrazino[2,3-f:2',3'-h]quinoxaline-2,3,6,7,10,11-hexacarbonitrile Chemical compound C12=NC(C#N)=C(C#N)N=C2C2=NC(C#N)=C(C#N)N=C2C2=C1N=C(C#N)C(C#N)=N2 DKHNGUNXLDCATP-UHFFFAOYSA-N 0.000 description 1
- 239000000975 dye Substances 0.000 description 1
- 230000005684 electric field Effects 0.000 description 1
- 238000000295 emission spectrum Methods 0.000 description 1
- 125000005678 ethenylene group Chemical class [H]C([*:1])=C([H])[*:2] 0.000 description 1
- 239000007850 fluorescent dye Substances 0.000 description 1
- 238000005286 illumination Methods 0.000 description 1
- 125000000879 imine group Chemical class 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 239000003446 ligand Substances 0.000 description 1
- 239000004973 liquid crystal related substance Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
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- 239000010413 mother solution Substances 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- 239000012044 organic layer Substances 0.000 description 1
- 239000011368 organic material Substances 0.000 description 1
- 238000006862 quantum yield reaction Methods 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 230000003595 spectral effect Effects 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000001161 time-correlated single photon counting Methods 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
- 238000002834 transmittance Methods 0.000 description 1
- 230000004580 weight loss Effects 0.000 description 1
- 229910052724 xenon Inorganic materials 0.000 description 1
- FHNFHKCVQCLJFQ-UHFFFAOYSA-N xenon atom Chemical compound [Xe] FHNFHKCVQCLJFQ-UHFFFAOYSA-N 0.000 description 1
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F15/00—Compounds containing elements of Groups 8, 9, 10 or 18 of the Periodic Table
- C07F15/0006—Compounds containing elements of Groups 8, 9, 10 or 18 of the Periodic Table compounds of the platinum group
- C07F15/0033—Iridium compounds
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
- C09K11/06—Luminescent, e.g. electroluminescent, chemiluminescent materials containing organic luminescent materials
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- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K50/00—Organic light-emitting devices
- H10K50/10—OLEDs or polymer light-emitting diodes [PLED]
- H10K50/11—OLEDs or polymer light-emitting diodes [PLED] characterised by the electroluminescent [EL] layers
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- 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
- H10K85/30—Coordination compounds
- H10K85/341—Transition metal complexes, e.g. Ru(II)polypyridine complexes
- H10K85/342—Transition metal complexes, e.g. Ru(II)polypyridine complexes comprising iridium
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- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
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- C09K2211/00—Chemical nature of organic luminescent or tenebrescent compounds
- C09K2211/18—Metal complexes
- C09K2211/185—Metal complexes of the platinum group, i.e. Os, Ir, Pt, Ru, Rh or Pd
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- H—ELECTRICITY
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- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K2102/00—Constructional details relating to the organic devices covered by this subclass
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- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K2102/00—Constructional details relating to the organic devices covered by this subclass
- H10K2102/301—Details of OLEDs
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Abstract
The invention discloses an organic metal iridium complex, a preparation method thereof and application thereof in OLED (organic light emitting diode), wherein the complex is applied to the manufacture of an OLED light emitting device and can obtain good device performance, when the organic metal iridium complex is used as a light emitting layer doping material of the OLED light emitting device, the driving voltage of the device can be obviously reduced, and simultaneously the current efficiency, the external quantum efficiency and the service life of the device are greatly improved. The organic metal iridium complex has good application effect in an OLED luminescent device and has good industrialization prospect.
Description
Technical Field
The invention belongs to the technical field of semiconductors, and particularly relates to an organic metal iridium complex, a preparation method thereof and application thereof in an OLED (organic light emitting diode).
Background
The Organic Light Emission Diodes (OLED) device technology can be used for manufacturing novel display products and novel lighting products, is expected to replace the existing liquid crystal display and fluorescent lamp lighting, and has a very wide application prospect. The OLED device is just like a sandwich structure and comprises electrode material film layers and organic functional materials clamped between different electrode film layers, and various different functional materials are mutually overlapped together according to purposes to form the OLED device. When voltage is applied to two end electrodes of the OLED light-emitting device as a current device, positive and negative charges in the organic layer functional material film layer are acted through an electric field, and the positive and negative charges are further compounded in the light-emitting layer, namely OLED electroluminescence is generated.
Currently, the OLED display technology has been applied in the fields of smart phones, tablet computers, and the like, and will further expand to large-size application fields such as televisions, but compared with actual product application requirements, the light emitting efficiency, the service life, and other performances of the OLED device need to be further improved. The research on the improvement of the performance of the OLED device includes: the driving voltage of the device is reduced, the luminous efficiency of the device is improved, the service life of the device is prolonged, and the like. In order to realize the continuous improvement of the performance of the OLED device, not only the innovation of the structure and the manufacturing process of the OLED device but also the continuous research and innovation of the OLED photoelectric functional material are needed to create the functional material of the OLED with higher performance.
Research by Forrest et al at the university of princeton, 1998, has found that organic light-emitting devices prepared using common organic materials or using fluorescent dye doping techniques have a maximum light-emitting internal quantum efficiency of 25% due to the constraint of the quantum mechanical transition law of spin conservation. They dope the phosphorescent dye octaethylporphyrin platinum in a main luminescent material to prepare a luminescent device with the external quantum efficiency of 4 percent and the internal quantum efficiency of 23 percent, thereby opening up a new field of phosphorescent electroluminescence. The organic phosphorescent complex has very high efficiency and brightness, so the organic phosphorescent complex has a strong application prospect in the field of organic solid-state lighting. However, the phosphorescent complexes reported at present have serious triplet-triplet annihilation and poor carrier transport capability, and the complexes can realize high-performance electroluminescence only in a very low and very narrow doping concentration range, which requires harsh device preparation conditions, thereby resulting in high cost in industrial production and affecting the quality and commercial competitiveness of products.
Therefore, aiming at the industrial application requirements of the current OLED device and the photoelectric characteristic requirements of the OLED device, a more suitable light-emitting layer doping material with high performance must be selected to realize the comprehensive characteristics of high efficiency, long service life and low voltage of the device. In terms of the actual demand of the current OLED display illumination industry, the development of the current OLED material is far from enough, and lags behind the requirements of panel manufacturing enterprises, and the development of the current OLED material as a material enterprise for developing higher-performance organic functional materials is very important.
Disclosure of Invention
In order to solve the problems in the prior art, the invention provides an organic metal iridium complex, a preparation method thereof and application thereof in an OLED. The organic metal iridium complex is used as a light-emitting layer doping material of an OLED device, and the manufactured OLED device has good photoelectric property. When the organic metal iridium complex is used as a luminescent layer doping material of an OLED luminescent device, the driving voltage of the device can be obviously reduced, the current efficiency, the external quantum efficiency and the service life of the device are greatly improved, and the requirements of panel manufacturing enterprises can be met.
The invention is realized by the following technical scheme:
an organometallic iridium complex having a structure represented by general formula (1):
wherein n is 1 or 2;
r in right side structure of metallic iridium1＇～R8Each independently represents hydrogen, C1-C6Alkyl of (C)3-C6Cycloalkyl, C substituted or unsubstituted by alkyl or aryl3-C30Heteroaryl, C substituted or unsubstituted by alkyl or aryl6-C30One of aryl groups;
the left structure of the iridium metal is a functional group which forms a coordination bond with the iridium metal through C, N element, and the specific structural formula is shown as a general formula (2) or a general formula (3):
wherein Y is independently C or N, and the number of N is at most 2; when Y represents C, i ═ 1; when Y represents N, i ═ 0;
indicates a site of attachment to iridium;
z represents O or S;
R1～R8independently represent hydrogen and C1-C6Alkyl of (C)3-C6Cycloalkyl of, C2-C6Alkenyl, C substituted or unsubstituted by alkyl or aryl3-C30Heteroaryl, C substituted or unsubstituted by alkyl or aryl6-C30An aryl group;
in the general formula (1), X represents Ar1、Ar2A substituted methylene group; wherein Ar is1、Ar2Each independently represents C substituted or unsubstituted by alkyl or aryl3-C30Heteroaryl, C substituted or unsubstituted by alkyl or aryl6-C30One of aryl radicals, and Ar1、Ar2Connected by a single bond, O, S, a carbon-carbon double bond, an aryl-substituted vinylene, an aryl-substituted alkylene, or an aryl-substituted imine group and forming a five-, six-, or seven-membered ring structure with the left C atom;
further, in the general formula (1), R1＇～R8Each independently represents hydrogen, C1-C6Straight or branched alkyl of (2), C3-C6Any of cycloalkyl, phenyl, alkyl-substituted phenyl, biphenyl, alkyl-substituted biphenyl, naphthyl, alkyl-substituted naphthyl, pyrimidinyl, alkyl-or aryl-substituted pyrimidinyl, pyridinyl, alkyl-or aryl-substituted pyridinyl.
Further, in the general formula (1), R1＇～R8Each independently represents any of hydrogen, methyl, ethyl, isopropyl, tert-butyl, cyclohexyl, phenyl, biphenyl, and naphthyl.
Further, in the general formulae (2) and (3), R1～R8Independently represent hydrogen and C1-C6A straight or branched alkyl group, a substituted or unsubstituted phenyl group.
Further, R1～R8Can pass throughThe C-C bond and the C-N bond are bonded to each other to form a five-membered ring, a six-membered ring or a seven-membered ring.
Further, in the general formulae (2) and (3), R1～R8Each independently represents one of hydrogen, methyl, ethyl, isopropyl, tert-butyl, phenyl, naphthyl or pyridyl.
Further, the specific structural formula of the complex is any one of the following:
a method for preparing the metal iridium complex comprises the following steps:
(1) preparation of intermediate D: sequentially putting the raw material I and iridium trichloride trihydrate into a reaction container, reacting a mixed solution of reactants at 110-120 ℃ for 10-24 h in an inert atmosphere by using ethylene glycol monomethyl ether and distilled water as solvents, cooling, filtering to obtain a solid, leaching the solid with ethanol, draining, and drying to obtain an intermediate D;
(2) preparation of intermediate S: putting the intermediate D into a reaction container, adding dichloromethane, stirring for dissolving, dripping a methanol solution of silver trifluoromethanesulfonate at room temperature, stirring for 10-24 hours at room temperature after dripping is finished, filtering the obtained solution, and spin-drying the filtrate to obtain an intermediate S;
(3) preparation of a target product: and sequentially putting the intermediate S and the raw material II into a reaction container, taking methanol and ethanol as solvents, reacting the mixed solution of the reactants at 70-80 ℃ for 10-24 h, cooling, filtering to obtain a filter cake, and passing the filter cake through a silica gel column to obtain a target product.
Further, in the step (1), the molar ratio of the raw material I to the iridium trichloride trihydrate is that the raw material I: iridium trichloride trihydrate is 2-2.5: 1; the volume ratio of the ethylene glycol methyl ether to the distilled water is ethylene glycol methyl ether: distilled water is 3: 1; in the step (2), the molar ratio of the intermediate D to the silver trifluoromethanesulfonate is that the intermediate D: 1: 2-2.5 of silver trifluoromethanesulfonate; in the step (3), the molar ratio of the intermediate S to the raw material II is that the intermediate S: 1: 1-1.5 of a raw material II; the volume ratio of methanol to ethanol is methanol: ethanol is 1: 1.
An organic electroluminescent device comprising a light-emitting layer comprising a host material and a dopant material, the dopant material being an organometallic iridium complex as described above.
A lighting or display element comprising an organic electroluminescent device as described above.
The invention has the following beneficial technical effects:
in the organometallic iridium complex, the right ligand of the metallic iridium enhances the stability of the whole molecule and greatly improves the color purity of the molecule. The organic metal iridium complex can be applied to the manufacture of an OLED device, and enables the OLED device to have good performance, and when the organic metal iridium complex is used as a luminescent layer doping material of the OLED luminescent device, the current efficiency and the external quantum efficiency of the device are greatly improved; meanwhile, the service life of the device is obviously prolonged.
According to the metal iridium complex, the HOMO orbital proportion of metal iridium in a compound is high, so that the material has high luminous efficiency, the metal iridium complex has a narrow half-wave wide spectrum, and a manufactured device is high in color purity, so that the metal iridium complex has a higher industrial application prospect.
In conclusion, the organic metal iridium complex has a good application effect in an OLED light-emitting device and has a good industrialization prospect.
Drawings
FIG. 1 is a schematic structural diagram of an organometallic iridium complex applied to an OLED device according to the present invention;
description of reference numerals: 1-a transparent substrate layer; 2-an ITO anode layer; 3-a hole injection layer; 4-a hole transport layer; 5-a hole transporting/electron blocking layer; 6-a light-emitting layer; 7-hole blocking/electron transporting layer; 8-electron injection layer; 9-cathode reflective electrode layer.
Detailed Description
The embodiments of the present invention will be described in detail below with reference to the accompanying drawings, which are provided for illustration only and are not intended to limit the scope of the invention.
In the following examples and comparative examples, the reagents, materials and instruments used were all commercially available as conventional reagents, conventional materials and conventional instruments unless otherwise specified, and the reagents mentioned therein were also prepared by conventional preparation methods.
EXAMPLE 1 preparation of organometallic Iridium Complex
EXAMPLE 1 preparation of Complex 1
Step (1): preparation of intermediate D1
Introducing nitrogen into a 150mL three-neck flask, adding 3.53g (10mmol) of iridium trichloride trihydrate, 3.41g (22mmol) of 2-phenylpyridine, 60mL of ethylene glycol monomethyl ether and 20mL of distilled water, stirring, heating to 120 ℃, carrying out reflux reaction for 17h, stopping heating after the solution is yellow and turbid, naturally cooling, filtering, washing a filter cake with 50mL of ethanol, 50mL of water and 50mL of ethanol in sequence, and carrying out suction drying and drying to obtain a yellow powder intermediate D1;
step (2): preparation of intermediate S1
Adding 2.14g (2mmol) of intermediate D1 and 100mL of dichloromethane into a 250mL three-necked bottle, stirring at room temperature for dissolving, slowly dropping 50mL of silver trifluoromethanesulfonate methanol solution (0.084M) at room temperature in a dark place for 0.5h, stirring at room temperature for 18h, enabling the solution to be yellow and turbid, enabling the solution to pass through a diatomite sand core funnel, sequentially washing the obtained filter cake with 50mL of dichloromethane and 50mL of ethanol, and performing rotary drying on the mother liquor to obtain a tan solid intermediate S1;
and (3): preparation of Complex 1
Adding 0.71g (1mmol) of intermediate S1, 0.48g (1.5mmol) of 2- (9-phenylfluorene) -pyridine, 20mL of methanol and 20mL of ethanol into a 100mL reaction bottle, stirring, heating to 75 ℃, refluxing for 21h, changing the reaction liquid from brown transparent to yellow turbid, stopping heating, naturally cooling, filtering, and allowing the solid to pass through a silica gel column to obtain a target complex with the HPLC purity of 99.50%;
the use of DEI-MS for the recognition of the complex, formula C46H32IrN3Detection value [ M +1 ]]+819.42, calculate value 819.22.
EXAMPLE 1 preparation of Complex 5
Step (1): preparation of intermediate D2
Introducing nitrogen into a 150mL three-neck flask, adding 3.53g (10mmol) of iridium trichloride trihydrate, 4.03g (22mmol) of 3, 5-dimethyl-2-phenylpyridine, 60mL of ethylene glycol monomethyl ether and 20mL of distilled water, stirring, heating to 120 ℃, refluxing for 17h, stopping heating after the solution is yellow and turbid, naturally cooling, filtering, washing a filter cake with 50mL of ethanol, 50mL of water and 50mL of ethanol in sequence, and performing suction drying and drying to obtain a yellow powder intermediate D2;
step (2): preparation of intermediate S2
Adding 2.38g (2mmol) of intermediate D2 and 100mL of dichloromethane into a 250mL three-necked bottle, stirring at room temperature for dissolving, slowly dropping 50mL of silver trifluoromethanesulfonate methanol solution (0.084M) at room temperature in a dark place for 0.5h, stirring at room temperature for 18h, enabling the solution to be yellow and turbid, enabling the solution to pass through a diatomite sand core funnel, sequentially washing the obtained filter cake with 50mL of dichloromethane and 50mL of ethanol, and performing rotary drying on the mother liquor to obtain a tan solid intermediate S2;
and (3): preparation of Complex 5
Adding 0.77g (1mmol) of intermediate S2, 0.48g (1.5mmol) of 2- (9-phenylfluorene) -pyridine, 20mL of methanol and 20mL of ethanol into a 100mL reaction bottle, stirring, heating to 75 ℃, refluxing for 21h, changing the reaction liquid from brown transparent to yellow turbid, stopping heating, naturally cooling, filtering, and allowing the solid to pass through a silica gel column to obtain a target complex with the HPLC purity of 99.55%;
the use of DEI-MS for the recognition of the complex, formula C50H40IrN3Detection value [ M +1 ]]+875.41, calculate value 875.29.
EXAMPLE 1-3 preparation of Complex 10
Step (1): intermediate D3 preparation
Introducing nitrogen into a 150mL three-neck flask, adding 3.53g (10mmol) of iridium trichloride trihydrate, 5.09g (22mmol) of 2, 4-diphenylpyridine, 60mL of ethylene glycol monomethyl ether and 20mL of distilled water, stirring, heating to 120 ℃, refluxing for reaction for 17h, stopping heating after the solution is yellow and turbid, naturally cooling, filtering, washing a filter cake with 50mL of ethanol, 50mL of water and 50mL of ethanol in sequence, and performing suction drying and drying to obtain a yellow powder intermediate D3;
step (2): preparation of intermediate S3
Adding 2.76g (2mmol) of intermediate D3 and 100mL of dichloromethane into a 250mL three-necked bottle, stirring at room temperature for dissolving, slowly dropping 50mL of methanol solution (0.084M) of silver trifluoromethanesulfonate at the dark room temperature for 0.5h, stirring at room temperature for 18h to obtain a yellow turbid solution, passing through a diatomite sand core funnel, washing the obtained filter cake with 50mL of dichloromethane and 50mL of ethanol in sequence, and performing rotary drying on the mother solution to obtain a tan solid intermediate S3;
and (3): preparation of Complex 10
Adding 0.86g (1mmol) of intermediate S3, 0.48g (1.5mmol) of 2- (9-phenylfluorene) -pyridine, 20mL of methanol and 20mL of ethanol into a 100mL reaction bottle, stirring, heating to 75 ℃, refluxing for 21h, changing the reaction liquid from brown transparent to yellow turbid, stopping heating, naturally cooling, filtering, and allowing the solid to pass through a silica gel column to obtain a target complex with the HPLC purity of 99.50%;
the use of DEI-MS for the recognition of the complex, formula C58H40IrN3Detection value [ M +1 ]]+971.51, calculate value 971.29.
EXAMPLES 1-4 preparation of Complex 26
Complex 26 is prepared in the same manner as in example 1-1, except that 2-phenylpyridine is replaced with the starting material 3-phenylpyridazine.
The HPLC purity of the target complex is 99.55 percent; the use of DEI-MS for the recognition of the complex, formula C44H30IrN5Detection value [ M +1 ]]+821.31, calculate value 821.21.
EXAMPLES 1-5 preparation of Complex 30
Complex 30 was prepared in the same manner as in example 1-1, except that 3, 5-diphenylpyridazine was used as a starting material in place of 2-phenylpyridine.
The purity of the target complex HPLC is 99.59%; the use of DEI-MS for the recognition of the complex, formula C56H38IrN5Detection value [ M +1 ]]+973.35, calculate value 973.28.
EXAMPLES 1-6 preparation of Complex 31
Complex 31 was prepared in the same manner as in example 1-1, except that 4-phenylpyrimidine was used as a starting material in place of 2-phenylpyridine.
The HPLC purity of the target complex is 99.52 percent; the use of DEI-MS for the recognition of the complex, formula C44H30IrN5Detection value [ M +1 ]]+＝821.35，Calculated 821.21.
EXAMPLES 1-7 preparation of Complex 36
Complex 36 is prepared in the same manner as in example 1-1, except that 2- (4-pyridyl) pyridine is used as a starting material in place of 2-phenylpyridine.
The HPLC purity of the target complex is 99.58 percent; the use of DEI-MS for the recognition of the complex, formula C44H30IrN5Detection value [ M +1 ]]+821.33, calculate value 821.21.
EXAMPLES 1-8 preparation of Complex 41
Complex 41 is prepared in the same manner as in example 1-1, except that 2-phenylpyridine is replaced with 3- (4-pyridyl) pyridazine as a starting material.
The purity of the target complex HPLC is 99.50%; the use of DEI-MS for the recognition of the complex, formula C42H28IrN7Detection value [ M +1 ]]+823.30, calculate value 823.20.
EXAMPLES 1-9 preparation of Complex 44
The preparation of complex 44 was carried out in the same manner as in example 1-1 except that 2-phenylpyrazine as a starting material was used in place of 2-phenylpyridine.
The HPLC purity of the target complex is 99.54 percent; the use of DEI-MS for the recognition of the complex, formula C44H30IrN5Detection value [ M +1 ]]+821.31, calculate value 821.21.
EXAMPLES 1-10 preparation of Complex 47
Complex 47 is prepared in the same manner as in example 1-1, except that 4- (4-pyridyl) pyrimidine as a starting material is used in place of 2-phenylpyridine.
The HPLC purity of the target complex is 99.58 percent; the use of DEI-MS for the recognition of the complex, formula C44H30IrN5Detection value [ M +1 ]]+821.33, calculate value 821.21.
EXAMPLES 1 preparation of complexes 50 to 11
The preparation of complex 50 was carried out in the same manner as in example 1-1 except that 2- (4-pyridyl) pyrazine was used as a starting material in place of 2-phenylpyridine.
The HPLC purity of the target complex is 99.52 percent; use of DEI-MS to identify the complex, formula C42H28IrN7Detection value [ M +1 ]]+823.32, calculate value 823.20.
EXAMPLES 1-12 preparation of Complex 53
Complex 53 is prepared in the same manner as in example 1-1, except that 4- (2-pyridyl) dibenzofuran as a starting material is used in place of 2-phenylpyridine.
The HPLC purity of the target complex is 99.56%; the use of DEI-MS for the recognition of the complex, formula C56H36IrN3O2Detection value [ M +1 ]]+999.36, calculate value 999.24.
EXAMPLES 1-13 preparation of Complex 66
Complex 66 is prepared in the same manner as in example 1-1, except that 2- (7-phenyl-7-H-benzo [ c ] furan-7-yl) pyridine, which is a starting material, is used in place of 2- (9-phenylfluorene) -pyridine.
The purity of the target complex HPLC is 99.57%; the use of DEI-MS for the recognition of the complex, formula C50H34IrN3Detection value [ M +1 ]]+869.32, calculate value 869.24.
EXAMPLES 1-14 preparation of Complex 75
Complex 75 was prepared in the same manner as in examples 1 to 3, except that 2- (7-phenyl-7-H-benzo [ c ] furan-7-yl) pyridine was used as a starting material in place of 2- (9-phenylfluorene) -pyridine.
The HPLC purity of the target complex is 99.52 percent; the use of DEI-MS for the recognition of the complex, formula C62H42IrN3Detection value [ M +1 ]]+1021.42, calculate value 1021.30.
EXAMPLES 1-15 preparation of Complex 128
Complex 128 was prepared in the same manner as in examples 1 to 12, except that 2- (7-phenyl-7-H-benzo [ c ] furan-7-yl) pyridine was used as a starting material in place of 2- (9-phenylfluorene) -pyridine.
The HPLC purity of the target complex is 99.56%; the complex is identified by DEI-MS, formula C62H38IrN3O2Detection value [ M +1 ]]+1049.36, calculate value 1049.26.
The complex is used in a light-emitting device, has high glass transition temperature (Tg) and decomposition temperature (Td), has proper HOMO energy level, and can be used as a light-emitting layer material. The complexes prepared in the above examples of the present invention were respectively tested for thermal performance and HOMO level, and the results are shown in table 1.
TABLE 1
Note: the glass transition temperature Tg is determined by differential scanning calorimetry (DSC, DSC204F1 DSC, Germany Chi corporation), the heating rate is 10 ℃/min; the thermogravimetric temperature Td is a temperature at which the weight loss is 0.5% in a nitrogen atmosphere, and is measured on a TGA-50H thermogravimetric analyzer of Shimadzu corporation, Japan, and the nitrogen flow rate is 20 mL/min; the highest occupied molecular orbital HOMO energy level was tested by the ionization energy test system (IPS-3) in a vacuum environment.
As can be seen from table 1, the complex of the present invention has a suitable HOMO energy level, and can be used as a dopant light emitting material. Relative to the conventional phosphorescent doped material Ir (ppy)3The material has higher glass transition temperature and decomposition temperature, so that the material has better thermal stability and chemical stability, and on one hand, the film crystallization of the material can be effectively inhibited, and on the other hand, the luminous material can be prevented from being decomposed by heat generated by long-time work of a device.
The complex is used in a luminescent device, has higher fluorescence quantum yield (PLQY), narrower spectral half-peak width (FWHM) and very short phosphorescence deactivation life (tau), and has good application potential when being used as a luminescent layer doping material. The complex prepared in the above example of the present invention was subjected to fluorescence quantum efficiency, emission spectrum and phosphorescence deactivation lifetime tests, and the results are shown in table 2.
TABLE 2
Note: the FWHM and the generation spectrum adopt FLS1000 equipment of Edinburgh university, the excitation wavelength is 380nm, and the excitation light source is a 450w continuous xenon lamp. The PLQY adopts an integrating sphere test system of FLS1000 equipment of Edinburgh university, and the excitation wavelength is 380 nm; the phosphorescence deactivation lifetime adopts TCSPC technology of FLS1000 equipment of Edinburgh university, and the laser excitation wavelength is 375 nm. The test sample is a material with the thickness of 80nm evaporated on a high-transmittance quartz glass substrate in vacuum and packaged in a glove box.
As can be seen from Table 2, compared to the conventional phosphorescent material Ir (ppy)3The complex has higher fluorescence quantum efficiency. The higher the fluorescence quantum efficiency is, the more sufficient the energy is converted into the light energy, and after the organic electroluminescent device is applied, the luminous efficiency of the device is improved. Maximum emission wavelength ratio of inventive complexes Ir (ppy)3Short, FWHM ratio Ir (ppy)3Narrow, the shorter the emission wavelength, the higher its color purity; the smaller the FWHM, the more efficient the use of light energy. Therefore, after the complex prepared by the invention is used for an organic electroluminescent device, the luminous efficiency of the device can be improved.
The application effect of the organometallic iridium complex prepared by the invention in an OLED device is described in detail by example 2. In each example and comparative example included in example 2, the manufacturing process of the device was completely the same, and the same substrate material and electrode material were used, and the film thickness of the electrode material was also kept the same, except that the doping material used for the light emitting layer in the device was changed.
Example 2 preparation of OLED device
Example 2-1 preparation of device 1
As shown in fig. 1, an electroluminescent device is prepared by the following steps:
a) cleaning the ITO anode layer 2 on the transparent substrate layer 1, sequentially ultrasonically cleaning the ITO anode layer 2 with alkali liquor, deionized water, acetone and ethanol for 15 minutes respectively, drying the ITO anode layer, and then washing the ITO anode layer for 2 minutes with ultraviolet rays-ozone to remove organic residues on the surface of the transparent ITO;
b) evaporating HAT-CN as a hole injection layer 3 on the cleaned ITO anode layer 2 in a vacuum evaporation mode, wherein the evaporation thickness is 10 nm;
c) evaporating NPD on the hole injection layer 3 in a vacuum evaporation mode to form a hole transport layer 4, wherein the evaporation thickness is 50 nm;
d) TCTA is evaporated on the hole transport layer 4 in a vacuum evaporation mode to be used as a hole transport/electron blocking layer 5, and the evaporation thickness is 60 nm;
e) evaporating a light-emitting layer 6 on the hole transport/electron blocking layer 5, wherein CBP is used as a main material of the light-emitting layer 6, the complex 1 is used as a doping material, the mass ratio of the CBP to the complex 1 is 94:6, and the evaporation thickness of the light-emitting layer 6 is 40 nm;
f) TPBi is evaporated on the luminescent layer 6 in a vacuum evaporation mode to be used as a hole blocking/electron transporting layer 7, and the evaporation thickness is 30 nm;
g) evaporating LiF as an electron injection layer 8 on the hole blocking/electron transport layer 7 in a vacuum evaporation mode, wherein the evaporation thickness is 1 nm;
h) on the electron injection layer 8, a cathode Al was vacuum-deposited as a cathode reflective electrode layer 9, and the thickness was 80nm, thereby obtaining a device 1.
The structural formula of the material used in example 2 is as follows:
example 2-2 preparation of device 2
Example 2-2 differs from example 2-1 in that: the light-emitting layer doping material of the OLED device adopts the complex 5 prepared by the invention.
Examples 2-3 preparation of device 3
Examples 2-3 differ from example 2-1 in that: the complex 10 prepared by the invention is adopted as the doping material of the light-emitting layer of the OLED device.
Examples 2-4 preparation of device 4
Examples 2-4 differ from example 2-1 in that: the complex 26 prepared by the invention is adopted as the doping material of the light-emitting layer of the OLED device.
Examples 2-5 preparation of device 5
Examples 2-5 differ from example 2-1 in that: the light-emitting layer doping material of the OLED device adopts the complex 30 prepared by the invention.
Examples 2-6 preparation of device 6
Examples 2-6 differ from example 2-1 in that: the light-emitting layer doping material of the OLED device adopts the complex 31 prepared by the invention.
Examples 2-7 preparation of device 7
Examples 2-7 differ from example 2-1 in that: the complex 36 prepared by the invention is adopted as the doping material of the light-emitting layer of the OLED device.
Examples 2-8 preparation of device 8
Examples 2-8 differ from example 2-1 in that: the light-emitting layer doping material of the OLED device adopts the complex 41 prepared by the invention.
Examples 2-9 preparation of device 9
Examples 2-9 differ from example 2-1 in that: the complex 44 prepared by the invention is adopted as the doping material of the light-emitting layer of the OLED device.
Examples 2-10 preparation of device 10
Examples 2-10 differ from example 2-1 in that: the complex 47 prepared by the invention is adopted as the doping material of the light-emitting layer of the OLED device.
Examples 2-11 preparation of device 11
Examples 2 to 11 differ from example 2 to 1 in that: the light-emitting layer doping material of the OLED device adopts the complex 50 prepared by the invention.
Examples 2-12 preparation of device 12
Examples 2-12 differ from example 2-1 in that: the complex 53 prepared by the invention is adopted as the doping material of the light-emitting layer of the OLED device.
Examples 2-13 preparation of device 13
Examples 2-13 differ from example 2-1 in that: the complex 66 prepared by the invention is adopted as the doping material of the light-emitting layer of the OLED device.
Examples 2-14 preparation of device 14
Examples 2 to 14 differ from example 2 to 1 in that: the light-emitting layer doping material of the OLED device adopts the complex 75 prepared by the invention.
Examples 2-15 preparation of device 15
Examples 2-15 differ from example 2-1 in that: the complex 128 prepared by the invention is adopted as the doping material of the light-emitting layer of the OLED device.
Comparative example
The comparative example is different from example 2-1 in that: the light emitting layer of the OLED device is made of Ir (ppy)3。
After the electroluminescent device was prepared, the anode and the cathode were connected by a driving circuit, and the device was measured at 10mA/cm2The results of the drive voltage, external quantum efficiency, decay life, and color at the current density are shown in table 3.
TABLE 3
| Device code | Driving voltage (v) | Colour(s) | External quantum efficiency (%) | LT95 Life (hr) |
| Device 1 | 0.91 | Green light | 1.29 | 2.7 |
| |
0.92 | Green light | 1.26 | 2.5 |
| |
0.89 | Green light | 1.33 | 2.6 |
| |
0.93 | Green light | 1.23 | 2.9 |
| |
0.98 | Green light | 1.28 | 2.8 |
| |
0.97 | Green light | 1.39 | 3.1 |
| |
0.95 | Green light | 1.20 | 2.7 |
| |
0.97 | Green light | 1.19 | 2.4 |
| Device 9 | 0.96 | Green light | 1.17 | 2.2 |
| Device 10 | 0.92 | Green light | 1.16 | 2.9 |
| Device 11 | 0.88 | Green light | 1.22 | 2.6 |
| Device 12 | 0.90 | Green light | 1.27 | 2.5 |
| Device 13 | 0.93 | Green light | 1.31 | 2.6 |
| Device 14 | 0.96 | Green light | 1.25 | 2.8 |
| Device 15 | 0.95 | Green light | 1.27 | 2.5 |
| Comparative example | 1.0 | Green light | 1.0 | 1.0 |
Note that the device test performance was referred to as comparative example, and each performance index of the comparative example device was set to 1.0.
The results in table 3 show that the organometallic iridium complex prepared by the invention can be applied to the fabrication of an OLED light-emitting device, and compared with the comparative example of the device, the driving voltage and the external quantum efficiency of the device are both greatly improved, and meanwhile, the service life of the device is also obviously improved. The organic metal iridium complex prepared by the invention has good application effect in OLED devices and has good industrialization prospect.
The above description is only for the purpose of illustrating the preferred embodiments of the present invention and is not to be construed as limiting the invention, and any modifications, equivalents, improvements and the like that fall within the spirit and principle of the present invention are intended to be included therein.
Claims (5)
1. An organometallic iridium complex, characterized in that the complex has a structure represented by general formula (1):
wherein n is 2;
R1＇～R8each independently represents any of hydrogen, methyl, ethyl, isopropyl, tert-butyl, cyclohexyl, phenyl, biphenyl, and naphthyl;
the left structure of the iridium metal is a functional group which forms a coordination bond with the iridium metal through C, N element, and the specific structural formula is shown as a general formula (2) or a general formula (3):
wherein Y represents C or N, and the number of N is at most 2; when Y represents C, i ═ 1; when Y represents N, i ═ 0;
indicates a site of attachment to iridium;
z represents O or S;
R1～R8each independently represents one of hydrogen, methyl, ethyl, isopropyl, tert-butyl, phenyl substituted or unsubstituted by alkyl, naphthyl or pyridyl; in the general formulae (2) and (3), R1～R8Can be bonded with each other through C-C bonds and C-N bonds to form a five-membered ring, a six-membered ring or a seven-membered ring;
in the general formula (1), X represents Ar1、Ar2A substituted methylene group; wherein Ar is1、Ar2Each independently represents C substituted or unsubstituted by alkyl or aryl3-C30Heteroaryl, C substituted or unsubstituted by alkyl or aryl6-C30One of aryl radicals, and Ar1、Ar2Connected by a single bond and forming a five-membered ring structure with the left C atom.
2. The organometallic iridium complex according to claim 1, wherein a specific structural formula of the complex is any one of:
3. a method for producing the metallic iridium complex according to claim 1 or 2, wherein the reaction equation is as follows:
the preparation method comprises the following steps:
(1) preparation of intermediate D: sequentially putting the raw material I and iridium trichloride trihydrate into a reaction container, reacting a mixed solution of reactants at 110-120 ℃ for 10-24 h in an inert atmosphere by using ethylene glycol monomethyl ether and distilled water as solvents, cooling, filtering to obtain a solid, leaching the solid with ethanol, drying by pumping, and drying to obtain an intermediate D;
(2) preparation of intermediate S: putting the intermediate D into a reaction container, adding dichloromethane, stirring for dissolving, dripping a methanol solution of silver trifluoromethanesulfonate at room temperature, stirring for 10-24 hours at room temperature after dripping is finished, filtering the obtained solution, and spin-drying the filtrate to obtain an intermediate S;
(3) preparation of a target product: putting the intermediate S and the raw material II into a reaction container in sequence, taking methanol and ethanol as solvents, reacting the mixed solution of the reactants at 70-80 ℃ for 10-24 h, cooling, filtering to obtain a filter cake, and passing the filter cake through a silica gel column to obtain a target product;
in the step (1), the molar ratio of the raw material I to the iridium trichloride trihydrate is that the raw material I: iridium trichloride trihydrate is 2-2.5: 1; the volume ratio of the ethylene glycol methyl ether to the distilled water is ethylene glycol methyl ether: distilled water is 3: 1; in the step (2), the molar ratio of the intermediate D to the silver trifluoromethanesulfonate is that the intermediate D: 1: 2-2.5 of silver trifluoromethanesulfonate; in the step (3), the molar ratio of the intermediate S to the raw material II is that the intermediate S: 1: 1-1.5 of a raw material II; the volume ratio of methanol to ethanol is methanol: ethanol is 1: 1.
4. An organic electroluminescent device comprising a light-emitting layer, wherein the light-emitting layer comprises a host material and a dopant material, and the dopant material adopts the organometallic iridium complex according to any one of claims 1 to 2.
5. A lighting or display element comprising the organic electroluminescent device according to claim 4.
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| WO2016025921A1 (en) * | 2014-08-15 | 2016-02-18 | Arizona Board Of Regents On Behalf Of Arizona State University | Non-platinum metal complexes for excimer based single dopant white organic light emitting diodes |
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| US9865825B2 (en) * | 2014-11-10 | 2018-01-09 | Arizona Board Of Regents On Behalf Of Arizona State University | Emitters based on octahedral metal complexes |
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| CN101115818A (en) * | 2005-01-17 | 2008-01-30 | 葛来西雅帝史派有限公司 | Phosphors with high luminous efficiency and display device containing them |
| WO2016025921A1 (en) * | 2014-08-15 | 2016-02-18 | Arizona Board Of Regents On Behalf Of Arizona State University | Non-platinum metal complexes for excimer based single dopant white organic light emitting diodes |
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