CN109970806A - A kind of organic metal complex of iridium, preparation method and its application in OLED - Google Patents
A kind of organic metal complex of iridium, preparation method and its application in OLED Download PDFInfo
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- CN109970806A CN109970806A CN201711444564.4A CN201711444564A CN109970806A CN 109970806 A CN109970806 A CN 109970806A CN 201711444564 A CN201711444564 A CN 201711444564A CN 109970806 A CN109970806 A CN 109970806A
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- iridium
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- 238000002360 preparation method Methods 0.000 title claims abstract description 82
- GKOZUEZYRPOHIO-UHFFFAOYSA-N iridium atom Chemical compound [Ir] GKOZUEZYRPOHIO-UHFFFAOYSA-N 0.000 title claims abstract description 43
- 229910052741 iridium Inorganic materials 0.000 title claims abstract description 42
- 150000004696 coordination complex Chemical class 0.000 title claims abstract description 28
- 239000000463 material Substances 0.000 claims abstract description 54
- 239000002019 doping agent Substances 0.000 claims abstract description 29
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 45
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 42
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 24
- 239000002994 raw material Substances 0.000 claims description 24
- 125000003118 aryl group Chemical group 0.000 claims description 21
- 235000019441 ethanol Nutrition 0.000 claims description 21
- 125000000217 alkyl group Chemical group 0.000 claims description 19
- 239000000243 solution Substances 0.000 claims description 18
- 238000006243 chemical reaction Methods 0.000 claims description 16
- UFWIBTONFRDIAS-UHFFFAOYSA-N Naphthalene Chemical compound C1=CC=CC2=CC=CC=C21 UFWIBTONFRDIAS-UHFFFAOYSA-N 0.000 claims description 14
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 13
- 229910052739 hydrogen Inorganic materials 0.000 claims description 12
- 239000001257 hydrogen Substances 0.000 claims description 12
- 229910052751 metal Inorganic materials 0.000 claims description 11
- 239000002184 metal Substances 0.000 claims description 11
- 239000012065 filter cake Substances 0.000 claims description 10
- 229910052757 nitrogen Inorganic materials 0.000 claims description 10
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 10
- 239000007787 solid Substances 0.000 claims description 10
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 9
- 238000001816 cooling Methods 0.000 claims description 9
- 239000012153 distilled water Substances 0.000 claims description 9
- QRUBYZBWAOOHSV-UHFFFAOYSA-M silver trifluoromethanesulfonate Chemical compound [Ag+].[O-]S(=O)(=O)C(F)(F)F QRUBYZBWAOOHSV-UHFFFAOYSA-M 0.000 claims description 9
- XNWFRZJHXBZDAG-UHFFFAOYSA-N 2-METHOXYETHANOL Chemical compound COCCO XNWFRZJHXBZDAG-UHFFFAOYSA-N 0.000 claims description 8
- 239000000047 product Substances 0.000 claims description 8
- 238000003756 stirring Methods 0.000 claims description 8
- DANYXEHCMQHDNX-UHFFFAOYSA-K trichloroiridium Chemical class Cl[Ir](Cl)Cl DANYXEHCMQHDNX-UHFFFAOYSA-K 0.000 claims description 8
- 229910021638 Iridium(III) chloride Inorganic materials 0.000 claims description 6
- 229910052799 carbon Inorganic materials 0.000 claims description 6
- 238000005401 electroluminescence Methods 0.000 claims description 6
- 125000004076 pyridyl group Chemical group 0.000 claims description 6
- 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
- 229910052760 oxygen Inorganic materials 0.000 claims description 4
- 239000000376 reactant Substances 0.000 claims description 4
- 229910052717 sulfur Inorganic materials 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
- 238000001035 drying Methods 0.000 claims description 3
- 238000005286 illumination Methods 0.000 claims description 3
- 239000002904 solvent Substances 0.000 claims description 3
- 125000001118 alkylidene group Chemical group 0.000 claims description 2
- 239000012298 atmosphere Substances 0.000 claims description 2
- 125000004432 carbon atom Chemical group C* 0.000 claims description 2
- 239000011203 carbon fibre reinforced carbon Substances 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
- 125000002573 ethenylidene group Chemical group [*]=C=C([H])[H] 0.000 claims description 2
- 239000000706 filtrate Substances 0.000 claims description 2
- 238000001914 filtration Methods 0.000 claims description 2
- 125000000524 functional group Chemical group 0.000 claims description 2
- 125000000325 methylidene group Chemical group [H]C([H])=* 0.000 claims description 2
- 150000002790 naphthalenes Chemical class 0.000 claims description 2
- 239000000741 silica gel Substances 0.000 claims description 2
- 229910002027 silica gel Inorganic materials 0.000 claims description 2
- 150000002431 hydrogen Chemical class 0.000 claims 5
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical class [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims 1
- 230000037429 base substitution Effects 0.000 claims 1
- 239000003795 chemical substances by application Substances 0.000 claims 1
- 229960001866 silicon dioxide Drugs 0.000 claims 1
- 230000000694 effects Effects 0.000 abstract description 5
- 239000010410 layer Substances 0.000 description 55
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 17
- 238000004128 high performance liquid chromatography Methods 0.000 description 15
- 238000007689 inspection Methods 0.000 description 11
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 8
- 230000000052 comparative effect Effects 0.000 description 8
- 238000004519 manufacturing process Methods 0.000 description 8
- VQGHOUODWALEFC-UHFFFAOYSA-N 2-phenylpyridine Chemical compound C1=CC=CC=C1C1=CC=CC=N1 VQGHOUODWALEFC-UHFFFAOYSA-N 0.000 description 7
- 238000010438 heat treatment Methods 0.000 description 7
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 7
- 238000007738 vacuum evaporation Methods 0.000 description 7
- ZJQCOVBALALRCC-UHFFFAOYSA-N 9-phenyl-9h-fluorene Chemical class C1=CC=CC=C1C1C2=CC=CC=C2C2=CC=CC=C21 ZJQCOVBALALRCC-UHFFFAOYSA-N 0.000 description 6
- 230000004888 barrier function Effects 0.000 description 6
- 230000005284 excitation Effects 0.000 description 6
- 238000004770 highest occupied molecular orbital Methods 0.000 description 6
- 125000004435 hydrogen atom Chemical class [H]* 0.000 description 6
- 238000010792 warming Methods 0.000 description 6
- 238000012360 testing method Methods 0.000 description 5
- 125000000339 4-pyridyl group Chemical group N1=C([H])C([H])=C([*])C([H])=C1[H] 0.000 description 4
- 238000001704 evaporation Methods 0.000 description 4
- 230000008020 evaporation Effects 0.000 description 4
- PGMVMQKSOQOICN-UHFFFAOYSA-N 2-phenyl-1,5-dihydropyrazole Chemical compound C1=CCNN1C1=CC=CC=C1 PGMVMQKSOQOICN-UHFFFAOYSA-N 0.000 description 3
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 3
- 241000238370 Sepia Species 0.000 description 3
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 3
- 230000005540 biological transmission Effects 0.000 description 3
- 239000003153 chemical reaction reagent Substances 0.000 description 3
- 238000004090 dissolution Methods 0.000 description 3
- 239000007772 electrode material Substances 0.000 description 3
- JEIPFZHSYJVQDO-UHFFFAOYSA-N ferric oxide Chemical compound O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 3
- 239000000499 gel Substances 0.000 description 3
- 230000009477 glass transition Effects 0.000 description 3
- 238000002347 injection Methods 0.000 description 3
- 239000007924 injection Substances 0.000 description 3
- 238000005259 measurement Methods 0.000 description 3
- 238000000034 method Methods 0.000 description 3
- 239000012452 mother liquor Substances 0.000 description 3
- 239000000843 powder Substances 0.000 description 3
- 230000027756 respiratory electron transport chain Effects 0.000 description 3
- 229910052710 silicon Inorganic materials 0.000 description 3
- 239000010703 silicon Substances 0.000 description 3
- 238000001228 spectrum Methods 0.000 description 3
- 239000000758 substrate Substances 0.000 description 3
- -1 3- phenyl pyridazine Pyridine Chemical compound 0.000 description 2
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 238000000354 decomposition reaction Methods 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 238000000113 differential scanning calorimetry Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 230000005525 hole transport Effects 0.000 description 2
- UHOVQNZJYSORNB-UHFFFAOYSA-N monobenzene Natural products C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 2
- 238000007747 plating Methods 0.000 description 2
- 150000003222 pyridines Chemical class 0.000 description 2
- 230000032258 transport Effects 0.000 description 2
- 238000005406 washing 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
- LNJZJDLDXQQJSG-UHFFFAOYSA-N 2-phenylpyrazine Chemical class C1=CC=CC=C1C1=CN=CC=N1 LNJZJDLDXQQJSG-UHFFFAOYSA-N 0.000 description 1
- YKISYRCBRZDTLK-UHFFFAOYSA-N 2-phenylpyridine;pyridine Chemical compound C1=CC=NC=C1.C1=CC=CC=C1C1=CC=CC=N1 YKISYRCBRZDTLK-UHFFFAOYSA-N 0.000 description 1
- 125000004105 2-pyridyl group Chemical group N1=C([*])C([H])=C([H])C([H])=C1[H] 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
- 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
- YQPMQYWAQQCLJO-UHFFFAOYSA-N C1=CN=CC=N1.C1=CC=CC=C1C1=CC=CC=N1 Chemical compound C1=CN=CC=N1.C1=CC=CC=C1C1=CC=CC=N1 YQPMQYWAQQCLJO-UHFFFAOYSA-N 0.000 description 1
- 101000837344 Homo sapiens T-cell leukemia translocation-altered gene protein Proteins 0.000 description 1
- CIVBYHFTERYLNX-UHFFFAOYSA-N N1=CN=CC=C1.C1(=CC=CC=C1)C1=NC=CC=C1 Chemical compound N1=CN=CC=C1.C1(=CC=CC=C1)C1=NC=CC=C1 CIVBYHFTERYLNX-UHFFFAOYSA-N 0.000 description 1
- BFPAUIVFWSCEFG-UHFFFAOYSA-N N1=NC=CC=C1.C1(=CC=CC=C1)C1=NC=CC=C1 Chemical compound N1=NC=CC=C1.C1(=CC=CC=C1)C1=NC=CC=C1 BFPAUIVFWSCEFG-UHFFFAOYSA-N 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 1
- 102100028692 T-cell leukemia translocation-altered gene protein Human genes 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 150000001335 aliphatic alkanes Chemical class 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 238000004040 coloring Methods 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 238000011982 device technology Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 150000004826 dibenzofurans Chemical class 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
- 235000013399 edible fruits Nutrition 0.000 description 1
- 230000005684 electric field Effects 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 238000000295 emission spectrum Methods 0.000 description 1
- 150000002240 furans Chemical class 0.000 description 1
- 230000003760 hair shine Effects 0.000 description 1
- JKXCZYCVHPKTPK-UHFFFAOYSA-N hydrate;trihydrochloride Chemical compound O.Cl.Cl.Cl JKXCZYCVHPKTPK-UHFFFAOYSA-N 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 230000002779 inactivation Effects 0.000 description 1
- 239000003446 ligand Substances 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000004973 liquid crystal related substance Substances 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 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
- 125000003386 piperidinyl group Chemical group 0.000 description 1
- PBMFSQRYOILNGV-UHFFFAOYSA-N pyridazine Chemical compound C1=CC=NN=C1 PBMFSQRYOILNGV-UHFFFAOYSA-N 0.000 description 1
- 230000005610 quantum mechanics Effects 0.000 description 1
- 238000006862 quantum yield reaction Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- HEMHJVSKTPXQMS-UHFFFAOYSA-M sodium hydroxide Substances [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 238000001161 time-correlated single photon counting Methods 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
- 238000002604 ultrasonography Methods 0.000 description 1
- 238000007740 vapor deposition 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
Classifications
-
- 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
-
- 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
-
- 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
-
- 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
-
- 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
- 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
-
- 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
-
- 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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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Crystallography & Structural Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Physics & Mathematics (AREA)
- Optics & Photonics (AREA)
- Electroluminescent Light Sources (AREA)
Abstract
The invention discloses a kind of organic metal complex of iridium, preparation method and its applications in OLED, the complex makes applied to OLED luminescent device, good device performance can be obtained, when the organic metal complex of iridium is used as the luminescent layer dopant material of OLED luminescent device, device drive voltage can be significantly reduced, while the current efficiency of device, external quantum efficiency and device lifetime are greatly improved.Organic metal complex of iridium of the present invention has good application effect in OLED luminescent device, has good industrialization prospect.
Description
Technical field
The invention belongs to technical field of semiconductors, and in particular to a kind of organic metal complex of iridium, preparation method and its
Application in OLED.
Background technique
Organic electroluminescent (Organic Light Emission Diodes, OLED) device technology can both be used to make
New display product is made, production novel illumination product is can be used for, is expected to substitute existing liquid crystal display and fluorescent lighting,
Application prospect is very extensive.Structure of the OLED device like sandwich, including electrode material film layer, and it is clipped in Different electrodes film
Organic functional material between layer, various different function materials are overlapped mutually depending on the application collectively constitutes OLED device together.
As current device, when the two end electrodes application voltage to OLED luminescent device, and pass through electric field action organic layer functional material
Positive and negative charge in film layer, positive and negative charge is further compound in luminescent layer, i.e. generation OLED electroluminescent.
Currently, OLED display technology is applied in fields such as smart phone, tablet computers, further will also be to electricity
Depending on etc. large scales application field extension, still with actual products application require compare, the luminous efficiency of OLED device, use
The performances such as service life also need further to be promoted.Proposing high performance research for OLED device includes: the driving voltage for reducing device,
The luminous efficiency for improving device, improves the service life etc. of device.In order to realize OLED device performance continuous promotion, not only
The innovation from OLED device structure and manufacture craft is needed, constantly studies and innovates with greater need for oled light sulfate ferroelectric functional material, is formulated
The functional material of higher performance OLED out.
Forrest of Princeton university in 1998 et al. is the study found that using general organic material or using glimmering
The organic luminescent device of photoinitiator dye doping techniques preparation, it is maximum due to the quantum mechanics transition rule constraint by spin conservation
The internal quantum efficiency that shines is 25%.They in main body luminescent material, prepare phosphorescent coloring octaethylporphyrin platinum dopant outer
Quantum efficiency is 4%, luminescent device of the internal quantum efficiency up to 23%, to open the frontier of electrophosphorescence.Due to
Phosphorescent complex has very high efficiency and brightness, and Phosphorescent complex has relatively strong in organic solid-state lighting area
Application prospect.But the phosphorescent complexes due to reporting at present there are more serious T-T annihilation and compared with
The carrier transport ability of difference, such complex often will just be able to achieve high-performance in very low, very narrow doping concentration range
Electroluminescent, this requires more harsh device preparation conditions, so as to cause the higher cost in industrialization production, shadow
Ring the quality and commercial competition ability of product.
Therefore, for the industry application requirement of current OLED device and the photoelectric characteristic demand of OLED device, it is necessary to select
It selects and is more suitable for, luminescent layer dopant material with high performance is just able to achieve high efficiency, the synthesis of long-life and low-voltage of device
Characteristic.For current OLED shows the actual demand of Lighting Industry, the development of OLED material is also far from enough at present, lags behind
The exploitation of the requirement of panel manufacturing enterprise, the organic functional material as material enterprise development higher performance is particularly important.
Summary of the invention
In view of the above-mentioned problems existing in the prior art, the present invention provides a kind of organic metal complex of iridium, its preparation side
Method and its application in OLED.The luminescent layer dopant material of organic metal complex of iridium of the invention as OLED device, system
The OLED device made has good photoelectric properties.Luminescent layer of the organic metal complex of iridium as OLED luminescent device
Dopant material is in use, device drive voltage can be significantly reduced, while the current efficiency of device, external quantum efficiency and device longevity
Life is greatly improved, and can satisfy the requirement of panel manufacturing enterprise.
The present invention is achieved by the following technical solutions:
A kind of organic metal complex of iridium, shown in the structure of the complex such as general formula (1):
Wherein, n=1 or 2；
R in metal iridium right side structure1'~R8' is separately expressed as hydrogen, C1-C6Alkyl, C3-C6Naphthenic base,
The C for replacing or being unsubstituted through alkyl or aryl3-C30Heteroaryl, replace through alkyl or aryl or the C that is unsubstituted6-C30Virtue
One of base；
Metal iridium left side structure is that the functional group of coordinate bond is formed by C, N element and metal iridium, and specific structural formula is such as
Shown in general formula (2) or general formula (3):
Wherein, Y is independent is expressed as C or N, and the number of N is up to 2；When Y is expressed as C, i=1；When Y is expressed as
When N, i=0；
* the connection site with iridium is indicated；
Z is expressed as O or S；
R1~R8Separately it is expressed as hydrogen, C1-C6Alkyl, C3-C6Naphthenic base, C2-C6Alkylene, through alkyl
Or the C that aryl replaces or is unsubstituted3-C30Heteroaryl, replace through alkyl or aryl or the C that is unsubstituted6-C30Aryl；
In general formula (1), X is expressed as Ar1、Ar2Substituted methylene；Wherein, Ar1、Ar2It is separately expressed as through alkane
The C that base or aryl replace or be unsubstituted3-C30Heteroaryl, replace through alkyl or aryl or the C that is unsubstituted6-C30In aryl
One kind, and Ar1、Ar2The alkylidene or virtue that ethenylidene, the aryl replaced by singly-bound, O, S, carbon-carbon double bond, aryl replaces
The imido grpup that base replaces connects and forms five, six or seven-members ring structure with left side C atom；
Further, in general formula (1), R1'~R8' is separately expressed as hydrogen, C1-C6Linear or branched alkyl group, C3-
C6Naphthenic base, phenyl, alkyl-substituted phenyl, xenyl, alkyl-substituted xenyl, naphthalene, alkyl-substituted naphthalene, phonetic
Any one of the pyridyl group that piperidinyl, the pyrimidine radicals of alkyl or aryl substitution, pyridyl group, alkyl or aryl replace.
Further, in general formula (1), R1'~R8' be separately expressed as hydrogen, methyl, ethyl, isopropyl, tert-butyl,
Any one of cyclohexyl, phenyl, xenyl, naphthalene.
Further, in general formula (2) and general formula (3), R1~R8Separately it is expressed as hydrogen, C1-C6Linear chain or branched chain
Alkyl, substituted or unsubstituted phenyl.
Further, R1~R8Between can mutually be bonded to form five-membered ring, hexatomic ring or seven by C-C key, C-N key
Member ring.
Further, in general formula (2) and general formula (3), R1~R8Separately be expressed as hydrogen, methyl, ethyl, isopropyl,
One of tert-butyl, phenyl, naphthalene or pyridyl group.
Further, the concrete structure formula of the complex is following any:
A kind of preparation method of metal iridium complex as described above, includes the following steps:
(1) preparation of intermediate D: raw material I, three hydrated iridium trichlorides are sequentially placed into reaction vessel, with ethylene glycol first
Ether and distilled water are as solvent, under an inert atmosphere, by the mixed solution of above-mentioned reactant in 110~120 DEG C react 10~
For 24 hours, cooling, the solid was filtered, solid ethanol rinse is drained, and drying obtains intermediate D；
(2) preparation of intermediate S: intermediate D is put into reaction vessel, methylene chloride stirring and dissolving is added, at room temperature
The methanol solution for instilling silver triflate, it is stirred at room temperature 10 after being added dropwise~for 24 hours, and acquired solution filtering, filtrate
It is spin-dried for, obtains intermediate S；
(3) preparation of target product: intermediate S, raw material II are sequentially placed into reaction vessel, using methanol and ethyl alcohol as
The mixed solution of above-mentioned reactant, is reacted in 70~80 DEG C 10~for 24 hours by solvent, cooling, filter to obtain filter cake, and filter cake crosses silica gel
Column obtains target product.
Further, in step (1), the molar ratio of the hydrated iridium trichloride of raw material I and three is I: three trichloride hydrate of raw material
Iridium=2~2.5:1；Ethylene glycol monomethyl ether and the volume ratio of distilled water are ethylene glycol monomethyl ether: distilled water=3:1；In step (2), institute
The molar ratio for stating intermediate D and silver triflate is intermediate D: silver triflate=1:2~2.5；Step (3)
In, the molar ratio of the intermediate S and raw material II is intermediate S: raw material II=1:1~1.5；The volume ratio of methanol and ethyl alcohol is
Methanol: ethyl alcohol=1:1.
A kind of organic electroluminescence device includes luminescent layer, and the luminescent layer includes material of main part and dopant material, described
Dopant material is organic metal complex of iridium as described above.
A kind of illumination or display element, including organic electroluminescence device as described above.
The present invention has following advantageous effects:
In organic metal complex of iridium of the present invention, ligand enhances the stability of entire molecule on the right side of metal iridium,
Also there is very big promotion to the excitation purity of molecule.The organic metal complex of iridium can be applied to OLED device production, and make
OLED device is with good performance, and the organic metal complex of iridium makes as the luminescent layer dopant material of OLED luminescent device
Used time, the current efficiency of device, external quantum efficiency are greatly improved；Meanwhile device lifetime is promoted clearly.
Metal iridium complex of the present invention, HOMO track of the metal iridium in compound account for it is relatively high, so material have
There is high luminous efficiency, metal iridium complex of the present invention has narrow half-wave wide spectrum, the colour purity of made device simultaneously
Degree is high, therefore has higher industrial application prospect.
To sum up, organic metal complex of iridium of the present invention has good application effect, tool in OLED luminescent device
There is good industrialization prospect.
Detailed description of the invention
Fig. 1 is the structural schematic diagram that organic metal complex of iridium of the invention is applied to OLED device；
Description of symbols: 1-transparent substrate layer；2-ito anode layers；3-hole injection layers；4-hole transmission layers；
5-hole transports/electronic barrier layer；6-luminescent layers；7-hole barriers/electron transfer layer；8-electron injecting layers；9-cathodes
Reflection electrode layer.
Specific embodiment
Carry out the embodiment that the present invention will be described in detail below with reference to attached drawing, illustrated embodiment is served only for explaining the present invention,
It is not intended to limit the scope of the present invention.
In following embodiments, comparative example, reagent, material and the instrument used such as not special explanation,
It is commercially available for conventional reagent, conventional material and conventional instrument, involved in reagent can also pass through conventional preparation
Method prepares.
The preparation of 1 organic metal complex of iridium of embodiment
The preparation of embodiment 1-1 complex 1
Step (1): the preparation of intermediate D1
In 150mL three-necked flask, it is passed through nitrogen, 3.53g (10mmol) three hydrated iridium trichloride, 3.41g is added
(22mmol) 2- phenylpyridine, 60mL ethylene glycol monomethyl ether and 20mL distilled water, stirring, are warming up to 120 DEG C, back flow reaction 17h, molten
Liquid is in stopping heating after yellow muddiness shape, is filtered after natural cooling, filter cake is successively washed with 50mL ethyl alcohol, 50mL water, 50mL ethyl alcohol
It washs, is drained, dried, obtain yellow powder intermediate D1；
Step (2): the preparation of intermediate S1
2.14g (2mmol) intermediate D1,100mL methylene chloride is added in 250mL there-necked flask, dissolution is stirred at room temperature, keeps away
Light is slowly dropped into the methanol solution (0.084M) of 50mL silver triflate at room temperature, and time for adding 0.5h is stirred at room temperature
18h, solution are in yellow muddiness shape, and solution crosses the sand core funnel of diatomite, obtained filter cake successively use 50mL methylene chloride and
50mL ethyl alcohol rinses, and mother liquor bronzing is spin-dried for, and obtains sepia solid intermediate S1；
Step (3): the preparation of complex 1
0.71g (1mmol) intermediate S1,0.48g (1.5mmol) 2- (9- phenyl fluorenes)-pyrrole is added in 100mL reaction flask
Pyridine, 20mL methanol, 20mL ethyl alcohol, stirring are warming up to 75 DEG C, and flow back 21h, and reaction solution becomes yellow muddiness from umber color is transparent
Shape stops heating, filters after natural cooling, solid crosses silicon gel column, obtains title complex, HPLC purity 99.50%；
The complex, molecular formula C are identified using DEI-MS46H32IrN3, detected value [M+1]+=819.42, calculated value
819.22。
The preparation of embodiment 1-2 complex 5
Step (1): the preparation of intermediate D2
In 150mL three-necked flask, it is passed through nitrogen, 3.53g (10mmol) three hydrated iridium trichloride, 4.03g is added
(22mmol) 3,5- dimethyl -2- phenylpyridine, 60mL ethylene glycol monomethyl ether and 20mL distilled water, stirring, are warming up to 120 DEG C, return
Stream reaction 17h, solution are in stopping heating after yellow muddiness shape, are filtered after natural cooling, filter cake successively uses 50mL ethyl alcohol, 50mL
Water, 50mL ethanol washing, are drained, are dried, and yellow powder intermediate D2 is obtained；
Step (2): the preparation of intermediate S2
2.38g (2mmol) intermediate D2,100mL methylene chloride is added in 250mL there-necked flask, dissolution is stirred at room temperature, keeps away
Light is slowly dropped into the methanol solution (0.084M) of 50mL silver triflate at room temperature, and time for adding 0.5h is stirred at room temperature
18h, solution are in yellow muddiness shape, and solution crosses the sand core funnel of diatomite, obtained filter cake successively use 50mL methylene chloride and
50mL ethyl alcohol rinses, and mother liquor bronzing is spin-dried for, and obtains sepia solid intermediate S2；
Step (3): the preparation of complex 5
0.77g (1mmol) intermediate S2,0.48g (1.5mmol) 2- (9- phenyl fluorenes)-pyrrole is added in 100mL reaction flask
Pyridine, 20mL methanol, 20mL ethyl alcohol, stirring are warming up to 75 DEG C, and flow back 21h, and reaction solution becomes yellow muddiness from umber color is transparent
Shape stops heating, filters after natural cooling, solid crosses silicon gel column, obtains title complex, HPLC purity 99.55%；
The complex, molecular formula C are identified using DEI-MS50H40IrN3, detected value [M+1]+=875.41, calculated value
875.29。
The preparation of embodiment 1-3 complex 10
Step (1): intermediate D3 preparation
In 150ml three-necked flask, it is passed through nitrogen, 3.53g (10mmol) three hydrated iridium trichloride, 5.09g is added
(22mmol) 2,4- hexichol yl pyridines, 60mL ethylene glycol monomethyl ether and 20mL distilled water, stirring, are warming up to 120 DEG C, back flow reaction
17h, solution are in stopping heating after yellow muddiness shape, are filtered after natural cooling, filter cake successively uses 50mL ethyl alcohol, 50mL water, 50mL
Ethanol washing is drained, is dried, and yellow powder intermediate D3 is obtained；
Step (2): the preparation of intermediate S3
2.76g (2mmol) intermediate D3,100mL methylene chloride is added in 250mL there-necked flask, dissolution is stirred at room temperature, keeps away
Light is slowly dropped into the methanol solution (0.084M) of 50mL silver triflate at room temperature, and time for adding 0.5h is stirred at room temperature
18h, solution are in yellow muddiness shape, cross the sand core funnel of diatomite, obtained filter cake successively uses 50mL methylene chloride and 50mL second
Alcohol rinses, and mother liquor bronzing is spin-dried for, and obtains sepia solid intermediate S3；
Step (3): the preparation of complex 10
0.86g (1mmol) intermediate S3,0.48g (1.5mmol) 2- (9- phenyl fluorenes)-pyrrole is added in 100mL reaction flask
Pyridine, 20mL methanol, 20mL ethyl alcohol, stirring are warming up to 75 DEG C, and flow back 21h, and reaction solution becomes yellow muddiness from umber color is transparent
Shape stops heating, filters after natural cooling, solid crosses silicon gel column, obtains title complex, HPLC purity 99.50%；
The complex, molecular formula C are identified using DEI-MS58H40IrN3, detected value [M+1]+=971.51, calculated value
971.29。
The preparation of embodiment 1-4 complex 26
The preparation method is the same as that of Example 1 for complex 26-1, and difference is to replace 2- phenyl pyrazoline with raw material 3- phenyl pyridazine
Pyridine.
Title complex HPLC purity 99.55%；The complex, molecular formula C are identified using DEI-MS44H30IrN5, inspection
Measured value [M+1]+=821.31, calculated value 821.21.
The preparation of embodiment 1-5 complex 30
The preparation method is the same as that of Example 1 for complex 30-1, and difference is with raw material 3, and 5- hexichol radical pyridazine replaces 2- benzene
Yl pyridines.
Title complex HPLC purity 99.59%；The complex, molecular formula C are identified using DEI-MS56H38IrN5, inspection
Measured value [M+1]+=973.35, calculated value 973.28.
The preparation of embodiment 1-6 complex 31
The preparation method is the same as that of Example 1 for complex 31-1, and difference is to replace 2- phenyl pyrazoline with raw material 4- phenyl pyrimidine
Pyridine.
Title complex HPLC purity 99.52%；The complex, molecular formula C are identified using DEI-MS44H30IrN5, inspection
Measured value [M+1]+=821.35, calculated value 821.21.
The preparation of embodiment 1-7 complex 36
The preparation method is the same as that of Example 1 for complex 36-1, and difference is to replace 2- with raw material 2- (4- pyridyl group) pyridine
Phenylpyridine.
Title complex HPLC purity 99.58%；The complex, molecular formula C are identified using DEI-MS44H30IrN5, inspection
Measured value [M+1]+=821.33, calculated value 821.21.
The preparation of embodiment 1-8 complex 41
The preparation method is the same as that of Example 1 for complex 41-1, and difference is to replace 2- with raw material 3- (4- pyridyl group) pyridazine
Phenylpyridine.
Title complex HPLC purity 99.50%；The complex, molecular formula C are identified using DEI-MS42H28IrN7, inspection
Measured value [M+1]+=823.30, calculated value 823.20.
The preparation of embodiment 1-9 complex 44
The preparation method is the same as that of Example 1 for complex 44-1, and difference is to replace 2- phenyl pyrazoline with raw material 2- phenyl pyrazines
Pyridine.
Title complex HPLC purity 99.54%；The complex, molecular formula C are identified using DEI-MS44H30IrN5, inspection
Measured value [M+1]+=821.31, calculated value 821.21.
The preparation of embodiment 1-10 complex 47
The preparation method is the same as that of Example 1 for complex 47-1, and difference is to replace 2- with raw material 4- (4- pyridyl group) pyrimidine
Phenylpyridine.
Title complex HPLC purity 99.58%；The complex, molecular formula C are identified using DEI-MS44H30IrN5, inspection
Measured value [M+1]+=821.33, calculated value 821.21.
The preparation of embodiment 1-11 complex 50
The preparation method is the same as that of Example 1 for complex 50-1, and difference is to replace 2- with raw material 2- (4- pyridyl group) pyrazine
Phenylpyridine.
Title complex HPLC purity 99.52%；The complex, molecular formula C are identified using DEI-MS42H28IrN7, inspection
Measured value [M+1]+=823.32, calculated value 823.20.
The preparation of embodiment 1-12 complex 53
The preparation method is the same as that of Example 1 for complex 53-1, and difference is with raw material 4- (2- pyridyl group) dibenzofurans
Instead of 2- phenylpyridine.
Title complex HPLC purity 99.56%；The complex, molecular formula C are identified using DEI-MS56H36IrN3O2,
Detected value [M+1]+=999.36, calculated value 999.24.
The preparation of embodiment 1-13 complex 66
The preparation method is the same as that of Example 1 for complex 66-1, and difference is with raw material 2- (7- phenyl-7-H- benzo [c] furan
Mutter -7-yl) pyridine replace 2- (9- phenyl fluorenes)-pyridine.
Title complex HPLC purity 99.57%；The complex, molecular formula C are identified using DEI-MS50H34IrN3, inspection
Measured value [M+1]+=869.32, calculated value 869.24.
The preparation of embodiment 1-14 complex 75
The preparation method is the same as that of Example 1 for complex 75-3, and difference is with raw material 2- (7- phenyl-7-H- benzo [c] furan
Mutter -7-yl) pyridine replace 2- (9- phenyl fluorenes)-pyridine.
Title complex HPLC purity 99.52%；The complex, molecular formula C are identified using DEI-MS62H42IrN3, inspection
Measured value [M+1]+=1021.42, calculated value 1021.30.
The preparation of embodiment 1-15 complex 128
The preparation method is the same as that of Example 1 for complex 128-12, and difference is with raw material 2- (7- phenyl-7-H- benzo [c]
Furans -7-yl) pyridine replace 2- (9- phenyl fluorenes)-pyridine.
Title complex HPLC purity 99.56%；The complex, molecular formula C are identified with DEI-MS62H38IrN3O2, inspection
Measured value [M+1]+=1049.36, calculated value 1049.26.
Complex of the present invention uses in luminescent device, has high glass transition temperature (Tg) and decomposition temperature (Td),
Suitable HOMO energy level can be used as emitting layer material use.Heat is carried out respectively to the complex of the above embodiment of the present invention preparation
Performance, the test of HOMO energy level, the results are shown in Table 1.
Table 1
Note: glass transition temperature Tg is by differential scanning calorimetry (DSC, German Nai Chi company DSC204F1 differential scanning calorimetry
Instrument) measurement, 10 DEG C/min of heating rate；Thermal weight loss temperature Td is the temperature of the weightlessness 0.5% in nitrogen atmosphere, in Japanese Shimadzu
It is measured on the TGA-50H thermogravimetric analyzer of company, nitrogen flow 20mL/min；Highest occupied molecular orbital HOMO energy level
It is to be tested by ionizing energy test macro (IPS-3), tests as vacuum environment.
As can be seen from Table 1, complex of the present invention has suitable HOMO energy level, can be used as dopant material luminescent material
It uses.Relative to conventional phosphorescence dopant material Ir (ppy)3, material of the present invention is with higher glass transition temperature and decomposition
On the one hand temperature can effectively inhibit the membrane crystallization of material so that material has more preferable thermal stability and chemical stability, another
Can also work long hours to avoid the device heat of generation of aspect makes luminescent material decompose.
Complex of the present invention uses in luminescent device, fluorescence quantum yield (PLQY) with higher, relatively narrow spectrum
Half-peak breadth (FWHM) and very short phosphorescence inactivation service life (τ), using as luminescent layer dopant material has good application latent
Power.Fluorescence quantum efficiency, emission spectrum and phosphorescence are carried out to the complex of the above embodiment of the present invention preparation and inactivate life test,
The results are shown in Table 2.
Table 2
Note: the FLS1000 equipment of FWHM and generation spectrum using Edinburgh University, excitation wavelength 380nm, excitation light source
For the continuous xenon lamp of 450w.PLQY uses the integrating sphere measurement system of Edinburgh University FLS1000 equipment, excitation wavelength 380nm；
Phosphorescence inactivates the service life using the TCSPC technology of the FLS1000 equipment of Edinburgh University, and laser excitation wavelength is 375nm.Test
Sample is the material of vacuum evaporation 80nm film thickness and to be packaged in glove box in high quartz glass substrate thoroughly.
As can be seen from Table 2, compared to traditional phosphor material Ir (ppy)3, complex of the present invention is with higher fluorescence
Quantum efficiency.Fluorescence quantum efficiency is higher, and it is more abundant that energy is converted to luminous energy, after applying to organic electroluminescence device, device
The luminous efficiency of part gets a promotion.The maximum emission wavelength ratio Ir (ppy) of complex of the present invention3It is short, FWHM ratio Ir (ppy)3It is narrow,
Launch wavelength is shorter, shows that its excitation purity is higher；FWHM is smaller, shows that the utilization rate of luminous energy is more abundant.Therefore present invention preparation
Complex for can be improved the luminous efficiency of device after organic electroluminescence device.
Application effect of the 2 organic metal complex of iridium that the present invention will be described in detail prepares in OLED device by the following examples
Fruit.In each embodiment and comparative example that embodiment 2 is included, the manufacture craft of device is identical, and uses identical
The film thickness of baseplate material and electrode material, electrode material is also consistent, except that used in the luminescent layer in device
Dopant material converts.
The preparation of embodiment 2OLED device
The preparation of embodiment 2-1 device 1
As shown in Figure 1, a kind of electroluminescent device, preparation step are as follows:
A) the ito anode layer 2 on transparent substrate layer 1 is cleaned, it is successively clear with lye, deionized water, acetone, each ultrasound of ethyl alcohol
It washes 15 minutes, washs 2min with ultraviolet-ozone after drying to remove the organic residue on the transparent surface ITO；
B) on ito anode layer 2 after cleaning, HAT-CN is deposited as hole injection layer 3 by vacuum evaporation mode, is steamed
Plating is with a thickness of 10nm；
C) on hole injection layer 3, NPD is deposited as hole transmission layer 4 by vacuum evaporation mode, evaporation thickness is
50nm；
D) on hole transmission layer 4, TCTA is deposited as hole transport/electronic barrier layer 5 by vacuum evaporation mode, is steamed
Plating is with a thickness of 60nm；
E) luminescent layer 6 is deposited on hole transport/electronic barrier layer 5, luminescent layer 6 uses CBP as material of main part, matches
It closes object 1 and is used as dopant material, the mass ratio of CBP and complex 1 is 94:6, and the evaporation thickness of luminescent layer 6 is 40nm；
F) on luminescent layer 6, TPBi is deposited as hole barrier/electron transfer layer 7, vapor deposition by vacuum evaporation mode
With a thickness of 30nm；
G) on hole barrier/electron transfer layer 7, LiF is deposited as electron injecting layer 8 by vacuum evaporation mode,
Evaporation thickness is 1nm；
H) on electron injecting layer 8, vacuum evaporation cathode Al is as cathode reflection electrode layer 9, evaporation thickness 80nm,
Obtain device 1.
The material structure formula used in embodiment 2 is as follows:
The preparation of embodiment 2-2 device 2
Embodiment 2-2 and embodiment 2-1 except that: the luminescent layer dopant material of OLED device is using present invention preparation
Complex 5.
The preparation of embodiment 2-3 device 3
Embodiment 2-3 and embodiment 2-1 except that: the luminescent layer dopant material of OLED device is using present invention preparation
Complex 10.
The preparation of embodiment 2-4 device 4
Embodiment 2-4 and embodiment 2-1 except that: the luminescent layer dopant material of OLED device is using present invention preparation
Complex 26.
The preparation of embodiment 2-5 device 5
Embodiment 2-5 and embodiment 2-1 except that: the luminescent layer dopant material of OLED device is using present invention preparation
Complex 30.
The preparation of embodiment 2-6 device 6
Embodiment 2-6 and embodiment 2-1 except that: the luminescent layer dopant material of OLED device is using present invention preparation
Complex 31.
The preparation of embodiment 2-7 device 7
Embodiment 2-7 and embodiment 2-1 except that: the luminescent layer dopant material of OLED device is using present invention preparation
Complex 36.
The preparation of embodiment 2-8 device 8
Embodiment 2-8 and embodiment 2-1 except that: the luminescent layer dopant material of OLED device is using present invention preparation
Complex 41.
The preparation of embodiment 2-9 device 9
Embodiment 2-9 and embodiment 2-1 except that: the luminescent layer dopant material of OLED device is using present invention preparation
Complex 44.
The preparation of embodiment 2-10 device 10
Embodiment 2-10 and embodiment 2-1 except that: the luminescent layer dopant material of OLED device is using present invention system
Standby complex 47.
The preparation of embodiment 2-11 device 11
Embodiment 2-11 and embodiment 2-1 except that: the luminescent layer dopant material of OLED device is using present invention system
Standby complex 50.
The preparation of embodiment 2-12 device 12
Embodiment 2-12 and embodiment 2-1 except that: the luminescent layer dopant material of OLED device is using present invention system
Standby complex 53.
The preparation of embodiment 2-13 device 13
Embodiment 2-13 and embodiment 2-1 except that: the luminescent layer dopant material of OLED device is using present invention system
Standby complex 66.
The preparation of embodiment 2-14 device 14
Embodiment 2-14 and embodiment 2-1 except that: the luminescent layer dopant material of OLED device is using present invention system
Standby complex 75.
The preparation of embodiment 2-15 device 15
Embodiment 2-15 and embodiment 2-1 except that: the luminescent layer dopant material of OLED device is using present invention system
Standby complex 128.
Comparative example
Comparative example and embodiment 2-1 except that: the luminescent layer dopant material of OLED device uses Ir (ppy)3。
After preparing above-mentioned electroluminescent device, anode and cathode is connected with driving circuit, measurement device exists
10mA/cm2Driving voltage, external quantum efficiency under current density, Decay, color, the results are shown in Table 3.
Table 3
| Device code name | Driving voltage (v) | Color | External quantum efficiency (%) | The LT95 service life (hr) |
| Device 1 | 0.91 | Green light | 1.29 | 2.7 |
| Device 2 | 0.92 | Green light | 1.26 | 2.5 |
| Device 3 | 0.89 | Green light | 1.33 | 2.6 |
| Device 4 | 0.93 | Green light | 1.23 | 2.9 |
| Device 5 | 0.98 | Green light | 1.28 | 2.8 |
| Device 6 | 0.97 | Green light | 1.39 | 3.1 |
| Device 7 | 0.95 | Green light | 1.20 | 2.7 |
| Device 8 | 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: for device detection performance using comparative example as reference, comparative example device performance indexes is set as 1.0.
Organic metal complex of iridium prepared by the present invention can be applied to OLED luminescent device it can be seen from the result of table 3
Production, and compared with device comparative example, the driving voltage and external quantum efficiency of device are greatly improved, meanwhile, device
Service life is also significantly improved.Illustrate that organic metal complex of iridium application effect in OLED device prepared by the present invention is good
It is good, there is good industrialization prospect.
The foregoing is merely presently preferred embodiments of the present invention, is not intended to limit the invention, it is all in spirit of the invention and
Within principle, any modification, equivalent replacement, improvement and so on be should all be included in the protection scope of the present invention.
Claims (10)
1. a kind of organic metal complex of iridium, which is characterized in that shown in the structure of the complex such as general formula (1):
Wherein, n=1 or 2；
R1'~R8' is separately expressed as hydrogen, C1-C6Alkyl, C3-C6Naphthenic base, through alkyl or aryl replace or without
Substituted C3-C30Heteroaryl, replace through alkyl or aryl or the C that is unsubstituted6-C30One of aryl；
Metal iridium left side structure is that the functional group of coordinate bond, specific structural formula such as general formula are formed by C, N element and metal iridium
(2) or shown in general formula (3):
Wherein, Y is expressed as C or N, and the number of N is up to 2；When Y is expressed as C, i=1；When Y is expressed as N, i=0；
* the connection site with iridium is indicated；
Z is expressed as O or S；
R1~R8Separately it is expressed as hydrogen, C1-C6Alkyl, C3-C6Naphthenic base, C2-C6Alkylene, through alkyl or virtue
The C that base replaces or is unsubstituted3-C30Heteroaryl, replace through alkyl or aryl or the C that is unsubstituted6-C30Aryl；
In general formula (1), X is expressed as Ar1、Ar2Substituted methylene；Wherein, Ar1、Ar2It is separately expressed as through alkyl or virtue
The C that base replaces or is unsubstituted3-C30Heteroaryl, replace through alkyl or aryl or the C that is unsubstituted6-C30One in aryl
Kind, and Ar1、Ar2The alkylidene or aryl that ethenylidene, the aryl replaced by singly-bound, O, S, carbon-carbon double bond, aryl replaces take
The imido grpup in generation connects and forms five, six or seven-members ring structure with left side C atom.
2. organic metal complex of iridium according to claim 1, which is characterized in that in general formula (1), R1'~R8' difference is only
On the spot it is expressed as hydrogen, C1-C6Linear or branched alkyl group, C3-C6Naphthenic base, phenyl, alkyl-substituted phenyl, xenyl, alkane
Pyrimidine radicals, the pyridyl group, alkyl that xenyl, naphthalene, alkyl-substituted naphthalene, pyrimidine radicals, the alkyl or aryl of base substitution replace
Or any one of the pyridyl group that aryl replaces.
3. organic metal complex of iridium according to claim 2, which is characterized in that in general formula (1), golden R1'~R8' difference
Independently it is expressed as any one of hydrogen, methyl, ethyl, isopropyl, tert-butyl, cyclohexyl, phenyl, xenyl, naphthalene.
4. organic metal complex of iridium according to claim 1, which is characterized in that in general formula (2) and general formula (3), R1~R8
Separately it is expressed as hydrogen, C1-C6Linear or branched alkyl group, substituted or unsubstituted phenyl.
5. organic metal complex of iridium according to claim 1 or 4, which is characterized in that in general formula (2) and general formula (3), R1
~R8Between can mutually be bonded to form five-membered ring, hexatomic ring or heptatomic ring by C-C key, C-N key.
6. organic metal complex of iridium according to claim 4, which is characterized in that in general formula (2) and general formula (3), R1~R8
Separately it is expressed as one of hydrogen, methyl, ethyl, isopropyl, tert-butyl, phenyl, naphthalene or pyridyl group.
7. organic metal complex of iridium according to claim 1, which is characterized in that the concrete structure formula of the complex be with
Under it is any:
8. a kind of preparation method of the metal iridium complex as described in claim 1-7, which is characterized in that reaction equation is such as
Under:
The preparation method includes the following steps:
(1) preparation of intermediate D: raw material I, three hydrated iridium trichlorides are sequentially placed into reaction vessel, with ethylene glycol monomethyl ether and
Distilled water is as solvent, under an inert atmosphere, by the mixed solution of above-mentioned reactant in 110~120 DEG C react 10~for 24 hours, it is cold
But, the solid was filtered, and solid ethanol rinse is drained, and drying obtains intermediate D；
(2) preparation of intermediate S: intermediate D is put into reaction vessel, and methylene chloride stirring and dissolving is added, instills at room temperature
The methanol solution of silver triflate, it is stirred at room temperature 10 after being added dropwise~for 24 hours, acquired solution filtering, filtrate is spin-dried for,
Obtain intermediate S；
(3) preparation of target product: intermediate S, raw material II are sequentially placed into reaction vessel, using methanol and ethyl alcohol as molten
The mixed solution of above-mentioned reactant, is reacted in 70~80 DEG C 10~for 24 hours by agent, cooling, filter to obtain filter cake, and filter cake crosses silicagel column,
Obtain target product；
Wherein, in step (1), the molar ratio of the hydrated iridium trichloride of raw material I and three be I: three hydrated iridium trichloride=2 of raw material~
2.5:1；Ethylene glycol monomethyl ether and the volume ratio of distilled water are ethylene glycol monomethyl ether: distilled water=3:1；In step (2), the intermediate
The molar ratio of D and silver triflate is intermediate D: silver triflate=1:2~2.5；In step (3), it is described in
The molar ratio of mesosome S and raw material II is intermediate S: raw material II=1:1~1.5；The volume ratio of methanol and ethyl alcohol is methanol: ethyl alcohol
=1:1.
9. a kind of organic electroluminescence device includes luminescent layer, which is characterized in that the luminescent layer includes material of main part and doping
Material, the dopant material use the described in any item organic metal complex of iridium of claim 1~7.
10. a kind of illumination or display element, which is characterized in that including organic electroluminescence device as claimed in claim 9.
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
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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 |
| US20140027716A1 (en) * | 2012-07-25 | 2014-01-30 | Universal Display Corporation (027166) | Heteroleptic cyclometallated ir(iii) complexes having a cyclometallated 6-membered ring |
| 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 |
| US20160133861A1 (en) * | 2014-11-10 | 2016-05-12 | Arizona Board Of Regents On Behalf Of Arizona State University | Emitters based on octahedral metal complexes |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
| US20140027716A1 (en) * | 2012-07-25 | 2014-01-30 | Universal Display Corporation (027166) | Heteroleptic cyclometallated ir(iii) complexes having a cyclometallated 6-membered ring |
| 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 |
| US20160133861A1 (en) * | 2014-11-10 | 2016-05-12 | Arizona Board Of Regents On Behalf Of Arizona State University | Emitters based on octahedral metal complexes |
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