CN105732722A - 一种有机电致磷光化合物及一种电致发光器件 - Google Patents
一种有机电致磷光化合物及一种电致发光器件 Download PDFInfo
- Publication number
- CN105732722A CN105732722A CN201610137124.3A CN201610137124A CN105732722A CN 105732722 A CN105732722 A CN 105732722A CN 201610137124 A CN201610137124 A CN 201610137124A CN 105732722 A CN105732722 A CN 105732722A
- Authority
- CN
- China
- Prior art keywords
- phosphor material
- compound
- material according
- substituted
- atom
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 150000001875 compounds Chemical class 0.000 title claims abstract description 28
- 125000001424 substituent group Chemical group 0.000 claims abstract description 9
- 229910052741 iridium Inorganic materials 0.000 claims abstract description 6
- GKOZUEZYRPOHIO-UHFFFAOYSA-N iridium atom Chemical compound [Ir] GKOZUEZYRPOHIO-UHFFFAOYSA-N 0.000 claims abstract description 6
- 125000005842 heteroatom Chemical group 0.000 claims abstract description 5
- 239000003446 ligand Substances 0.000 claims abstract description 3
- 239000000463 material Substances 0.000 claims description 55
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims description 17
- UJOBWOGCFQCDNV-UHFFFAOYSA-N Carbazole Natural products C1=CC=C2C3=CC=CC=C3NC2=C1 UJOBWOGCFQCDNV-UHFFFAOYSA-N 0.000 claims description 8
- IOJUPLGTWVMSFF-UHFFFAOYSA-N benzothiazole Chemical class C1=CC=C2SC=NC2=C1 IOJUPLGTWVMSFF-UHFFFAOYSA-N 0.000 claims description 4
- ODHXBMXNKOYIBV-UHFFFAOYSA-N triphenylamine Chemical group C1=CC=CC=C1N(C=1C=CC=CC=1)C1=CC=CC=C1 ODHXBMXNKOYIBV-UHFFFAOYSA-N 0.000 claims description 4
- JYEUMXHLPRZUAT-UHFFFAOYSA-N 1,2,3-triazine Chemical group C1=CN=NN=C1 JYEUMXHLPRZUAT-UHFFFAOYSA-N 0.000 claims description 2
- VDULMXJUOWIPGE-UHFFFAOYSA-N 1-phenylisoquinoline quinoline Chemical class N1=CC=CC2=CC=CC=C12.C1(=CC=CC=C1)C1=NC=CC2=CC=CC=C12 VDULMXJUOWIPGE-UHFFFAOYSA-N 0.000 claims description 2
- FMSSKCBYHCEFQE-UHFFFAOYSA-N 1h-indole;pyrimidine Chemical compound C1=CN=CN=C1.C1=CC=C2NC=CC2=C1 FMSSKCBYHCEFQE-UHFFFAOYSA-N 0.000 claims description 2
- OXPDQFOKSZYEMJ-UHFFFAOYSA-N 2-phenylpyrimidine Chemical class C1=CC=CC=C1C1=NC=CC=N1 OXPDQFOKSZYEMJ-UHFFFAOYSA-N 0.000 claims description 2
- WZHKCFDUDKJGBA-UHFFFAOYSA-N N1CCNCC1.S1C=CC=C1 Chemical group N1CCNCC1.S1C=CC=C1 WZHKCFDUDKJGBA-UHFFFAOYSA-N 0.000 claims description 2
- 125000000217 alkyl group Chemical group 0.000 claims description 2
- 125000004429 atom Chemical group 0.000 claims description 2
- 125000000609 carbazolyl group Chemical group C1(=CC=CC=2C3=CC=CC=C3NC12)* 0.000 claims description 2
- 229910052799 carbon Inorganic materials 0.000 claims description 2
- 125000004432 carbon atom Chemical group C* 0.000 claims description 2
- 230000007812 deficiency Effects 0.000 claims description 2
- KZTYYGOKRVBIMI-UHFFFAOYSA-N diphenyl sulfone Chemical group C=1C=CC=CC=1S(=O)(=O)C1=CC=CC=C1 KZTYYGOKRVBIMI-UHFFFAOYSA-N 0.000 claims description 2
- 125000000623 heterocyclic group Chemical group 0.000 claims description 2
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 claims description 2
- 229910052757 nitrogen Inorganic materials 0.000 claims description 2
- 125000004433 nitrogen atom Chemical group N* 0.000 claims description 2
- 150000004866 oxadiazoles Chemical group 0.000 claims description 2
- 125000004430 oxygen atom Chemical group O* 0.000 claims description 2
- 229910052717 sulfur Inorganic materials 0.000 claims description 2
- 125000004434 sulfur atom Chemical group 0.000 claims description 2
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 claims description 2
- 239000003086 colorant Substances 0.000 abstract description 2
- 230000002950 deficient Effects 0.000 abstract 1
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 15
- HEDRZPFGACZZDS-MICDWDOJSA-N Trichloro(2H)methane Chemical compound [2H]C(Cl)(Cl)Cl HEDRZPFGACZZDS-MICDWDOJSA-N 0.000 description 15
- 238000002360 preparation method Methods 0.000 description 15
- 229920000642 polymer Polymers 0.000 description 14
- 239000010410 layer Substances 0.000 description 13
- 238000000034 method Methods 0.000 description 12
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 8
- FQJQNLKWTRGIEB-UHFFFAOYSA-N 2-(4-tert-butylphenyl)-5-[3-[5-(4-tert-butylphenyl)-1,3,4-oxadiazol-2-yl]phenyl]-1,3,4-oxadiazole Chemical compound C1=CC(C(C)(C)C)=CC=C1C1=NN=C(C=2C=C(C=CC=2)C=2OC(=NN=2)C=2C=CC(=CC=2)C(C)(C)C)O1 FQJQNLKWTRGIEB-UHFFFAOYSA-N 0.000 description 7
- 238000005516 engineering process Methods 0.000 description 7
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 6
- 230000008901 benefit Effects 0.000 description 5
- 230000005540 biological transmission Effects 0.000 description 5
- 239000010408 film Substances 0.000 description 5
- 238000001644 13C nuclear magnetic resonance spectroscopy Methods 0.000 description 4
- 238000005160 1H NMR spectroscopy Methods 0.000 description 4
- 229920000144 PEDOT:PSS Polymers 0.000 description 4
- 229910052786 argon Inorganic materials 0.000 description 4
- 238000004440 column chromatography Methods 0.000 description 4
- 238000013461 design Methods 0.000 description 4
- 238000004519 manufacturing process Methods 0.000 description 4
- 238000001840 matrix-assisted laser desorption--ionisation time-of-flight mass spectrometry Methods 0.000 description 4
- 230000008569 process Effects 0.000 description 4
- 239000000047 product Substances 0.000 description 4
- 238000010992 reflux Methods 0.000 description 4
- 150000003384 small molecules Chemical class 0.000 description 4
- 239000007787 solid Substances 0.000 description 4
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 3
- 238000000151 deposition Methods 0.000 description 3
- 238000005286 illumination Methods 0.000 description 3
- 238000002347 injection Methods 0.000 description 3
- 239000007924 injection Substances 0.000 description 3
- 239000000243 solution Substances 0.000 description 3
- 239000010409 thin film Substances 0.000 description 3
- FIHILUSWISKVSR-UHFFFAOYSA-N 3,6-dibromo-9h-carbazole Chemical compound C1=C(Br)C=C2C3=CC(Br)=CC=C3NC2=C1 FIHILUSWISKVSR-UHFFFAOYSA-N 0.000 description 2
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- 208000035126 Facies Diseases 0.000 description 2
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 description 2
- 238000000137 annealing Methods 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- FJDQFPXHSGXQBY-UHFFFAOYSA-L caesium carbonate Chemical compound [Cs+].[Cs+].[O-]C([O-])=O FJDQFPXHSGXQBY-UHFFFAOYSA-L 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 description 2
- 230000021615 conjugation Effects 0.000 description 2
- 230000008021 deposition Effects 0.000 description 2
- 238000000605 extraction Methods 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 230000000704 physical effect Effects 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 238000012546 transfer Methods 0.000 description 2
- LWIHDJKSTIGBAC-UHFFFAOYSA-K tripotassium phosphate Chemical compound [K+].[K+].[K+].[O-]P([O-])([O-])=O LWIHDJKSTIGBAC-UHFFFAOYSA-K 0.000 description 2
- 229910000404 tripotassium phosphate Inorganic materials 0.000 description 2
- DKEGCUDAFWNSSO-UHFFFAOYSA-N 1,8-dibromooctane Chemical compound BrCCCCCCCCBr DKEGCUDAFWNSSO-UHFFFAOYSA-N 0.000 description 1
- GKWLILHTTGWKLQ-UHFFFAOYSA-N 2,3-dihydrothieno[3,4-b][1,4]dioxine Chemical compound O1CCOC2=CSC=C21 GKWLILHTTGWKLQ-UHFFFAOYSA-N 0.000 description 1
- QPTWWBLGJZWRAV-UHFFFAOYSA-N 2,7-dibromo-9-H-carbazole Natural products BrC1=CC=C2C3=CC=C(Br)C=C3NC2=C1 QPTWWBLGJZWRAV-UHFFFAOYSA-N 0.000 description 1
- VSMDINRNYYEDRN-UHFFFAOYSA-N 4-iodophenol Chemical compound OC1=CC=C(I)C=C1 VSMDINRNYYEDRN-UHFFFAOYSA-N 0.000 description 1
- 241000555268 Dendroides Species 0.000 description 1
- 229920005601 base polymer Polymers 0.000 description 1
- 230000000740 bleeding effect Effects 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 229910000024 caesium carbonate Inorganic materials 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 229940125904 compound 1 Drugs 0.000 description 1
- 229940125782 compound 2 Drugs 0.000 description 1
- -1 compounds compounds Chemical class 0.000 description 1
- 229920000547 conjugated polymer Polymers 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 230000001808 coupling effect Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000011982 device technology Methods 0.000 description 1
- 239000002019 doping agent Substances 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 239000000284 extract Substances 0.000 description 1
- 239000000706 filtrate Substances 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 230000005283 ground state Effects 0.000 description 1
- 229910001385 heavy metal Inorganic materials 0.000 description 1
- AMGQUBHHOARCQH-UHFFFAOYSA-N indium;oxotin Chemical compound [In].[Sn]=O AMGQUBHHOARCQH-UHFFFAOYSA-N 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- 239000002346 layers by function Substances 0.000 description 1
- 238000004020 luminiscence type Methods 0.000 description 1
- 239000008204 material by function Substances 0.000 description 1
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 1
- 229910052753 mercury Inorganic materials 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 1
- 239000012044 organic layer Substances 0.000 description 1
- 229920001467 poly(styrenesulfonates) Polymers 0.000 description 1
- 229960002796 polystyrene sulfonate Drugs 0.000 description 1
- 239000011970 polystyrene sulfonate Substances 0.000 description 1
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Substances [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 1
- 229910000027 potassium carbonate Inorganic materials 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 238000010791 quenching Methods 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
- 239000011541 reaction mixture Substances 0.000 description 1
- 230000006798 recombination Effects 0.000 description 1
- 238000005215 recombination Methods 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 239000002356 single layer Substances 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 238000004528 spin coating Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000007738 vacuum evaporation Methods 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
- 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
- C09K2211/10—Non-macromolecular compounds
- C09K2211/1018—Heterocyclic compounds
- C09K2211/1025—Heterocyclic compounds characterised by ligands
- C09K2211/1029—Heterocyclic compounds characterised by ligands containing one nitrogen atom as the heteroatom
-
- 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
- C09K2211/10—Non-macromolecular compounds
- C09K2211/1018—Heterocyclic compounds
- C09K2211/1025—Heterocyclic compounds characterised by ligands
- C09K2211/1029—Heterocyclic compounds characterised by ligands containing one nitrogen atom as the heteroatom
- C09K2211/1033—Heterocyclic compounds characterised by ligands containing one nitrogen atom as the heteroatom with oxygen
-
- 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
- C09K2211/10—Non-macromolecular compounds
- C09K2211/1018—Heterocyclic compounds
- C09K2211/1025—Heterocyclic compounds characterised by ligands
- C09K2211/1029—Heterocyclic compounds characterised by ligands containing one nitrogen atom as the heteroatom
- C09K2211/1037—Heterocyclic compounds characterised by ligands containing one nitrogen atom as the heteroatom with sulfur
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E10/00—Energy generation through renewable energy sources
- Y02E10/50—Photovoltaic [PV] energy
- Y02E10/549—Organic PV cells
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Crystallography & Structural Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Electroluminescent Light Sources (AREA)
Abstract
本发明提供了一种有机电致磷光化合物,所述电致磷光化合物的结构式如下式所示:其中,A和B分别独立地为给电子或者缺电子的光电单元重复得到的树枝状取代基;A与B可以相同或不同;C为含有杂原子的共轭光电单元;n为整数,且2≤n≤8;D为具有不同发光颜色的含N杂环配体与铱的配合物。本发明还提供了使用所述电致磷光化合物制备的电致发光器件;优选的,所述器件发射层包含所述的电致磷光化合物。
Description
技术领域
本发明涉及光电领域,具体而言,涉及一种有机电致磷光化合物及一种电致发光器件。
背景技术
有机发光二极管(OLED)具有主动发光、高对比度、超薄、发热量低、低功耗、可柔性加工等诸多优点,已被广泛用于显示和照明技术。与传统光源(荧光灯、白炽灯等)相比它是一种固态面光源,同时避免了白炽灯泡高耗电、易碎及荧光灯废弃物含汞污染、启动电压高的问题,被称之为“绿色环保”光源。虽然OLED照明起步晚于显示,但是近些年OLED照明技术不断完善,已经成为未来新型照明领域的重要发展方向,在今后一段时间里OLED照明产品有望将逐步进入到人们的日常生活。
在OLED中,材料和器件制备技术是OLED的核心关键。材料的特性极大地影响OLED的性能,目前来说发光材料主要有荧光材料和磷光材料两大类,但是荧光材料的理论最大内量子效率仅为25%,因此以荧光材料制备的OLED的效率较低,难以满足高效率照明的要求。含有重金属(如Ir)的电致磷光材料,由于金属5d离子结构上强烈的自旋轨道偶合作用导致单线态和三线态混合,使单线态激子(25%)和三线态激子(75%),之都可以辐射跃迁回到基态,从而发出高效磷光,所以该类材料的理论内量子效率可以达到100%。基于铱配合物发光的磷光OLED具有最高的发光效率,达到甚至超过了无机发光二极管(LED)和荧光灯的发光效率。以磷光材料在制备OLED器件虽然能够获得较高的效率,但是这类材料并不是直接用于制备有机薄膜,而是通常会掺杂在主体材料中制备成多层器件,以便减少自淬灭和三线态-三线态湮灭。掺杂体系一般有:小分子-小分子体系、小分子-聚合物体系、聚合物-聚合物体系。对于小分子-小分子体系来讲,受到成膜性以及可溶性等物理性能的限制,在制备器件时一般会采用真空蒸镀法。由于在共蒸镀多种组分时难以精确控制薄膜的组成成分,同时为了实现制备不同的功能层,该类器件通常会采用多种小分子的多层发光结构(尤其是白光器件)。该类器件具有以下两点明显的缺点:1)真空蒸镀法对设备真空度的要求较高,所以制备时间较长,增加产品的生产周期。同时,多层结构增加了制备工艺的复杂性。2)器件多发光层结构导致在不同的外加电压下载流子在器件发光层中的复合区域会发生改变,导致某一发光材料层中的激子生成比例增加而另一些发光材料层中的激子生成比例减少,影响器件发光颜色的稳定性。3)器件稳定性和可重复性差。对于聚合物体系,因为具有成良好的成膜性、形貌稳定等特征,这类体系经常采用溶液法(湿法)制备有机薄膜。相对于真空蒸镀的器件而言,通过溶液法制备的OLED器件,可有效缩减制备工艺和降低生产成本,且可精确的薄膜中材料掺杂比例,有效的提高材料的利用率。该方法可用于制备单一发光层白光OLED,可有效避免发光颜色不稳定的弊端。但是,以上这两种主客体掺杂体系中,由于聚合物和掺杂材料之间粘性和沸点等物理性能存在的差异,导致器件在使用中或者制备过程中立即产生相分离。众所周知,相分离会严重影响器件各方面的物理过程,例如电荷的注入/传输,激子的形成/复合,及能量传递等过程。但是,这一缺点并没有得到足够广泛的重视。为了达到克服相分离的缺点和简化制备工艺的目的,许多研究者试图将不同的荧光或者磷光材料通过化学键/配位键连接到聚合物的主链或者支链上达到获得不同颜色的发光。尤其是在获得白光发射时,需要将蓝、绿、红等不同的发光基团连接到聚合物分子上。例如,已报到的文献中同时将蓝、绿、红三种不同荧光发射基团同时引入到一个聚合物中实现了白光发射,也可以将不同发光的磷光基团引入到聚合物中实现白光或者其他光的发射。这类聚合物具有很好的溶液加工性,但是该类单一聚合物体系也具备一些需要1)该类单一聚合物器件的发光效率很低,功率效率一般都小于10lm/W,尤其是全荧光发射单一聚合物。这类器件目前还不能满足高效照明的要求。在这类单一聚合物材料中,以蓝色电致磷光材料的效率最低。最主要的原因是,共轭聚合物主链的三线态能级通常会低于蓝色磷光材料的三线态能级,所以就会导致三线态能量回传。2)含有不同发色基团的单一聚合物材料在制备上很复杂,而且不容易提纯。
相对于以上两种体系,湿法制膜的有机小分子电致发光器件能够结合小分子和聚合物的优点,同时具备材料易于合成和提纯、制备工艺简单及成本较低的特点。另一个优点是小分子主体材料可控设计性高,例如,可以通过连接方式的设计实现高三线态的要求,通过不同基团的设计可以实现空穴及电荷的传输。本项目拟构建可溶液法加工的自掺杂型有机电致磷光材料,设计具备多种功能的小分子主体,将不同的磷光材料接枝到小分子主体材料上形成自掺杂,这样有效的避免了相分离的问题。主体材料和磷光材料之间通过非共轭的方式连接,以阻断两者之间的共轭,使两者之间能发生有效的能量传递和激子传输。此类材料还可以用于制备单一发射层的白光器件,由于具有相似的主体结构可以有效的减小相分离。因此,此类材料的制备有望提高溶液法制备器件的效率,同时与小分子和聚合物体系相比有利于简化器件和材料制备过程。
发明内容
本发明的第一目的在于提供一种有机电致磷光化合物,所述电致磷光化合物能够结合小分子和聚合物的优点,同时具备材料易于合成和提纯、制备工艺简单及成本较低的特点。
本发明的第二目的在于提供使用电致磷光化合物制备的电致发光器件。
为了实现本发明的上述目的,特采用以下技术方案:
本发明的一个方面涉及一种有机电致磷光化合物,所述电致磷光化合物的结构式如下式所示:
其中,A和B分别独立地为给电子或者缺电子的光电单元重复得到的树枝状取代基;A与B可以相同或不同;C为含有杂原子的共轭光电单元;n为整数,且2≤n≤8;D为具有不同发光颜色的含N杂环配体与铱的配合物。
本发明的有机电致磷光化合物包含各种连接在小分子主体材料上的磷光单元,其可以在主体材料上形成自掺杂,有效地避免了相分离。另一方面,主体材料和磷光材料之间通过非共轭的方式连接,以阻断两者之间的共轭,使两者之间能发生有效的能量传递和激子传输。
优选地,所述A和B分别独立地具有以下结构:
其中R’是具有1-3个取代基X的R基,所述取代基X为1-4个碳原子的直链或支链烷基。
优选地,所述R是咔唑、三苯胺、噻吩嗪、恶二唑、三嗪、二苯基砜、P=O或嘧啶吲哚;
所述取代基X是异丙基或叔丁基。
优选地,所述C部分含有的杂原子是N、S或O原子,优选地,所述杂原子是N原子,更优选地,所述C部分是咔唑或三苯胺。
优选地,所述D部分是含有取代或非取代的苯基嘧啶、取代或非取代的苯基异喹啉、或者取代或非取代的苯并噻唑的含铱配合物。
优选地,所述A和B选自以下结构:
优选地,所述C选自以下结构:
优选地,所述D选自以下结构:
优选地,所述磷光材料的结构如下:
本发明的另一方面涉及使用权利要求1-9任一项所述的电致磷光化合物制备的电致发光器件;优选的,所述器件发射层包含所述的电致磷光化合物。
本发明提供器件该的发射层可以是单层也可以是多层,且本发明的磷光化合物化合物既可以单独作为发射层,也可以与电子传输材料或其他功能材料共混作为发射层
与现有技术相比,本发明的有益效果为:
(1)本发明的磷光化合物因为具有足够大的分子量,可以采用溶液法制备薄膜,可以避免蒸镀法带来的工艺复杂性,简化器件制备工艺;
(2)本发明的磷光化合物具有自掺杂性可以单独作为一个发射层,避免了主体材料的使用,有效的减小相分离。
附图说明
为了更清楚地说明本发明实施例或现有技术中的技术方案,以下将对实施例或现有技术描述中所需要使用的附图作简单地介绍。
图1为器件结构图;
图2为器件的电致发光光谱;
图3为器件的电流密度-电压-亮度曲线;
图4为器件的电流密度-电流效率曲线。
具体实施方式
下面将结合实施例对本发明的实施方案进行详细描述,但是本领域技术人员将会理解,下列实施例仅用于说明本发明,而不应视为限制本发明的范围。实施例中未注明具体条件者,按照常规条件或制造商建议的条件进行。所用试剂或仪器未注明生产厂商者,均为可以通过市售购买获得的常规产品。
实施例1
化合物7CzC8FIrpic的制备
向4-碘苯酚(11.0g,50.0mmol),1,8-二溴辛烷(13.60g,50.0mmol)和K2CO3(6.90g,50.0mmol)中加入100mL丙酮,然后将混合物在氩气保护下回流24h。除掉溶剂后,将剩余残渣用二氯甲烷萃取三次,滤液经过干燥后浓缩。采用柱层析法提纯得到白色固体1(15.6g,产率76%)。1HNMR(400MHz,CDCl3)δ7.51(d,J=8.7Hz,2H),6.65(d,J=8.7Hz,2H),3.89(t,J=6.5Hz,2H),3.39(t,J=6.8Hz,2H),1.90–1.79(m,4H),1.78–1.69(m,2H),1.33(d,J=4.2Hz,6H).13CNMR(101MHz,CDCl3)δ159.19,138.27,116.76,82.30,68.07,33.86,32.76,29.24,28.48,28.16,25.90.MS(MALDI-TOF)m/zC14H20BrIO:理论值411.12;实测值411[M]+。
将3,6-二溴咔唑(6.50g,20mmol)、化合物1(9.0g,24mmol)、CuI(0.19g,1.0mmol)和K3PO4(8.50g,40.0mmol)加入到100mL甲苯中,用氩气脱气30分钟后,加入反式-1,2-环己二胺(0.245mL,2.0mmol),反应混合液在回流条件下反应48小时。除去溶剂后残余物用二氯甲烷(3×100mL)萃取三次,合并有机相并用无水硫酸镁干燥,浓缩得到的剩余物以二氯甲烷:正己烷作为洗脱剂采用柱层析方法提纯得到白色固体2约6.10g,产率50%。1HNMR(400MHz,CDCl3)δ8.36(s,0.4H),8.16(s,1.6H),7.63(d,J=8.7Hz,0.4H),7.46(d,J=8.6Hz,1.6H),7.34(d,J=8.1Hz,2H),7.15(d,J=8.7Hz,1.6H),7.07(d,J=8.0Hz,2.4H),4.03(t,J=6.3Hz,2H),3.41(t,J=6.8Hz,1.3H),3.19(t,J=7.0Hz,0.7H),1.84(td,J=13.4,6.7Hz,4H),1.63–1.30(m,8H).13CNMR(101MHz,CDCl3)δ158.88,140.36,134.86,129.29,128.30,123.75,123.14,115.57,112.79,111.31,68.16,33.98,33.50,32.78,30.43,29.21,28.71,28.49,28.11,25.99.MS(MALDI-TOF)m/zC26H26Br3NO:理论值608.2;实测值607.2[M-1]+。
将化合物2(0.47g,0.76mmol)、FIrpicOH(0.50g,0.71mmol)、Cs2CO3(1.10g,3.50mmol)和CuI(0.134g,0.71mmol)加入到10mL二甲基甲酰胺中,脱气30分钟后在氩气保护下回流48小时。用二氯甲烷萃取、干燥、浓缩后通过柱层析提纯得到黄色固体Br2CzC8FIrpic0.50g产率52.6%。1HNMR(400MHz,CDCl3)δ8.79(d,J=5.7Hz,1H),8.36(s,0.5H),8.22(dd,J=15.6,8.1Hz,2.5H),8.16(s,1.5H),7.73(s,2H),7.62(d,J=7.7Hz,0.5H),7.46(d,J=7.0Hz,3H),7.41(s,0.5H),7.37(d,J=4.9Hz,1H),7.32(d,J=8.3Hz,2H),7.16(t,J=8.6Hz,2H),7.06(d,J=8.5Hz,2.5H),6.95(t,J=6.5Hz,1H),6.43(t,J=10.6Hz,1H),6.38–6.31(t,1H),5.78(d,J=8.6Hz,1H),5.51(d,J=8.5Hz,1H),4.09(dd,J=12.8,6.8Hz,2H),4.01(t,J=6.2Hz,2H),1.98–1.89(m,2H),1.85–1.78(m,2H),1.51(m,4H),1.41(m,4H).13CNMR(101MHz,CDCl3)δ171.13,165.61,164.33,162.30,159.42,158.77,153.07,148.98,148.03,140.37,139.71,138.00,134.84,129.28,128.88,128.34,128.05,124.36,123.66,123.13,122.92,122.72,122.54,122.40,122.22,115.84,114.45,112.77,111.43,68.14,29.12,25.98.MS(MALDI-TOF)m/zC54H41Br2F4IrN4O4理论值1237.9;实测值1238[M]+.
将化合物3Cz(0.67g,0.92mmol)、Br2CzC8FIrpic(0.50g,0.4mmol)、CuI(0.0076g,0.04mmol)和K3PO4(1.0g,4.70mmol)加入到10mL甲苯中,然后经过抽气/充氩气反复三次后,加入(±)-反式-1,2环己二胺(0.10mL,0.80mmol),在氩气保护下回流48小时。反应完毕后,用二氯甲烷(3×50mL)萃取,有机相用无水硫酸镁干燥,浓缩厚粗产品经过柱层析提纯得到黄色固体7Cz-C8-FIrpic0.21g,产率20.8%。1HNMR(400MHz,CDCl3)δ8.80(d,J=4.6Hz,1H),8.52(s,2H),8.25(s,6H),8.14(s,9H),7.80(d,J=8.9Hz,3H),7.71(t,J=11.2Hz,5H),7.63(d,J=8.7Hz,6H),7.59(d,J=8.5Hz,5H),7.44(d,J=8.5Hz,12H),7.33(d,J=8.5Hz,10H),4.14–4.09(m,4H),1.58(d,J=9.5Hz,4H),1.44(s,72H),1.31–1.18(m,8H).13CNMR(101MHz,CDCl3)δ171.02,165.01,164.46,161.92,159.29,157.96,151.43,148.85,147.75,142.53,141.53,140.26,137.93,137.46,130.75,129.67,129.07,128.59,127.75,126.31,125.82,123.78,123.54,123.14,122.51,119.92,119.39,116.18,111.68,111.10,109.06,68.33,35.13,31.71,29.59,25.94.MS(MALDI-TOF)m/zC158H149F4IrN10O4理论值2520.2;实测值2544.3[M+Na]+
实施例2:器件制备与表征
以7Cz-C8-FIrpic为发光材料的有机发光二极管的器件结构为ITO/PEDOT:PSS/7CzC8FIrpic(60nm):OXD-7/Ca(10nm)/Al(80nm),其中:ITO为氧化铟锡阳极;PEDOT:PSS是聚3,4-乙撑二氧噻吩/聚苯乙烯磺酸盐,在器件中作为空穴注入层;7CzC8FIrpic为发光材料;OXD-7全称为2,2'-(1,3-苯基)二[5-(4-叔丁基苯基)-1,3,4-恶二唑],在器件中作为电子传输材料;Ca(10nm)/Al(100nm)作为金属阴极。器件的主要制备过程如下:
1.在ITO上3000r/s旋涂空穴注入层以PEDOT:PSS,40s后取下,150℃退火10min;
2.将7CzC8FIrpic:OXD-7配置成15mg/mL的氯苯溶液,以1500r/s旋涂到PEDOT:PSS的上层,30s后取下,120℃退火10min;
3.在上述有机层之上蒸镀Ca(10nm)/Al(100nm)作为金属阴极。
所得有机发光二极管器件的电致发光谱图如图2所示,谱图中的发射峰位于497nm和500nm,是典型的蓝色磷光材料FIrpic的发射峰,说明该类自掺杂磷光材料的树枝状咔唑主体将能量全部转移到发光材料FIrpic上。
从图3电流密度-电压-亮度曲线得知,器件的启亮电压较低,在4-5V之间,随着电子传输材料OXD-7含量增加,器件的亮度逐渐增加,当OXD-7掺杂为40%时,器件的最大零度为1739cd/m2。
从图4可以看出,随着电子传输材料OXD-7掺杂量增加,器件的电流效率逐渐增加,当OXD-7掺杂为40%时,器件的最大零度为0.92cd/A。
尽管已用具体实施例来说明和描述了本发明,然而应意识到,在不背离本发明的精神和范围的情况下可以作出许多其它的更改和修改。因此,这意味着在所附权利要求中包括属于本发明范围内的所有这些变化和修改。
Claims (10)
1.一种有机电致磷光化合物,其特征在于,所述电致磷光化合物的结构式如下式所示:
其中,A和B分别独立地为给电子或者缺电子的光电单元重复得到的树枝状取代基;A与B可以相同或不同;C为含有杂原子的共轭光电单元;n为整数,且2≤n≤8;D为具有不同发光颜色的含N杂环配体与铱的配合物。
2.根据权利要求1所述的电致磷光化合物,其特征在于,所述A和B分别独立地具有以下结构:
其中R’是具有1-3个取代基X的R基,所述取代基X为1-4个碳原子的直链或支链烷基。
3.根据权利要求2所述的电致磷光化合物,其特征在于,所述R是咔唑、三苯胺、噻吩嗪、恶二唑、三嗪、二苯基砜、P=O或嘧啶吲哚;
所述取代基X是异丙基或叔丁基。
4.根据权利要求1所述的磷光材料,其特征在于,所述C部分含有的杂原子是N、S或O原子,优选地,所述杂原子是N原子,更优选地,所述C部分是咔唑或三苯胺。
5.根据权利要求1所述的磷光材料,其特征在于,所述D部分是含有取代或非取代的苯基嘧啶、取代或非取代的苯基异喹啉、或者取代或非取代的苯并噻唑的含铱配合物。
6.根据权利要求1所述的磷光材料,其特征在于,所述A和B选自以下结构:
7.根据权利要求1所述的磷光材料,其特征在于,所述C选自以下结构:
8.根据权利要求1所述的磷光材料,其特征在于,所述D选自以下结构:
9.根据权利要求1所述的磷光材料,其特征在于,所述磷光材料的结构如下:
10.使用权利要求1-9任一项所述的电致磷光化合物制备的电致发光器件;优选的,所述器件发射层包含所述的电致磷光化合物。
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN201610137124.3A CN105732722B (zh) | 2016-03-10 | 2016-03-10 | 一种有机电致磷光化合物及一种电致发光器件 |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN201610137124.3A CN105732722B (zh) | 2016-03-10 | 2016-03-10 | 一种有机电致磷光化合物及一种电致发光器件 |
Publications (2)
Publication Number | Publication Date |
---|---|
CN105732722A true CN105732722A (zh) | 2016-07-06 |
CN105732722B CN105732722B (zh) | 2019-05-17 |
Family
ID=56251603
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
CN201610137124.3A Active CN105732722B (zh) | 2016-03-10 | 2016-03-10 | 一种有机电致磷光化合物及一种电致发光器件 |
Country Status (1)
Country | Link |
---|---|
CN (1) | CN105732722B (zh) |
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN106380454A (zh) * | 2016-08-16 | 2017-02-08 | 盐城工学院 | 有机电致发光材料、发光器件及该器件的制备方法 |
Citations (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN102993180A (zh) * | 2012-12-21 | 2013-03-27 | 中国科学院长春应用化学研究所 | 树枝状蓝光金属配合物及其应用与有机发光二极管器件 |
-
2016
- 2016-03-10 CN CN201610137124.3A patent/CN105732722B/zh active Active
Patent Citations (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN102993180A (zh) * | 2012-12-21 | 2013-03-27 | 中国科学院长春应用化学研究所 | 树枝状蓝光金属配合物及其应用与有机发光二极管器件 |
Non-Patent Citations (5)
Title |
---|
GUO-GANG SHAN等: ""A cationic iridium(iii) complex showing aggregation-induced phosphorescent emission (AIPE) in the solid state: synthesis,characterization and properties"", 《DALTON TRANSACTIONS》 * |
JUNQIAO DING等: ""Solution-processible red iridium dendrimers based on oligocarbazole host dendrons : synthesis, properties, and their applications in organic light-emitting diodes"", 《ADV. FUNCT. MATER.》 * |
LINGCHENG CHEN等: ""Bipolar Heteroleptic Green Iridium Dendrimers Containing Oligocarbazole and Oxadiazole Dendrons for Bright and Efficient Nondoped Electrophosphorescent Devices"", 《ELECTROPHOSPHORESCENT DEVICES》 * |
LINGCHENG CHEN等: ""Effect of dendron generation on properties of self-host heteroleptic green light-emitting iridium dendrimers"", 《ORGANIC ELECTRONICS》 * |
赵南: ""基于咔唑树枝的深蓝光树枝状铱配合物的合成与表征"", 《中国优秀硕士学位论文全文数据库 工程科技I辑》 * |
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN106380454A (zh) * | 2016-08-16 | 2017-02-08 | 盐城工学院 | 有机电致发光材料、发光器件及该器件的制备方法 |
Also Published As
Publication number | Publication date |
---|---|
CN105732722B (zh) | 2019-05-17 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
CN101743650B (zh) | 有机发光器件和显示装置 | |
CN106831884A (zh) | 有机金属铱络合物、及其有机电致发光器件应用 | |
CN111848689A (zh) | 一种含苯并呋喃的有机铱配合物及其制备方法和光电器件 | |
CN106611823B (zh) | 一种可交联有机半导体主体材料及其有机发光二极管应用 | |
CN106816544B (zh) | 一种可交联双极性有机半导体及其有机发光二极管应用 | |
CN106749197A (zh) | 一种芳香族胺类衍生物及其制备方法和应用 | |
CN111747932B (zh) | 一种化合物及其应用、有机电致发光器件 | |
CN112375071B (zh) | 一种有机发光化合物及其制备方法与应用 | |
CN112341466A (zh) | 一种有机化合物及使用该化合物的有机发光器件 | |
CN101759685A (zh) | 一种有机电致发光铱配合物及其制备方法和应用 | |
CN107602568A (zh) | 一种基于吲哚并喹喔啉的三芳胺类衍生物及其有机发光器件 | |
CN105384759B (zh) | 芳香杂环衍生物和使用该化合物的有机发光二极管器件 | |
CN106977527A (zh) | 一种有机半导体化合物和使用该化合物的有机电致发光器件 | |
CN105237519A (zh) | 深蓝色电致发光化合物及其制备方法和应用 | |
CN106749341A (zh) | 平衡电荷注入有机半导体及其有机发光二极管应用 | |
CN106654035B (zh) | 一种有机半导体主体材料及其有机发光二极管应用 | |
CN111978292B (zh) | 一种化合物及其应用、包含其的有机电致发光器件 | |
CN112341460A (zh) | 一种有机化合物及使用该化合物的有机发光器件 | |
CN105131940B (zh) | 含有螺双芴和二苯并噻吩的有机发光材料及发光器件 | |
Cao et al. | Bipolar fluorophores based on intramolecular charge-transfer moieties of sulfone for nondoped deep blue solution-processed organic light-emitting diodes | |
CN105732722A (zh) | 一种有机电致磷光化合物及一种电致发光器件 | |
CN105968100A (zh) | 一种咪唑类衍生物化合物及其制备方法和发光器件 | |
Thiyagarajan et al. | Human-eyes-friendly white electroluminescence from solution-processable hybrid OLEDs exploiting new iridium (III) complex containing benzoimidazophenanthridine ligand | |
CN106784359B (zh) | 可交联平衡电荷注入有机半导体及其有机发光二极管应用 | |
CN105085551A (zh) | 芳香杂环衍生物和使用该化合物的有机发光二极管器件 |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
C06 | Publication | ||
PB01 | Publication | ||
C10 | Entry into substantive examination | ||
SE01 | Entry into force of request for substantive examination | ||
GR01 | Patent grant | ||
GR01 | Patent grant |