CN1995271A - 具有磷光有机金属络合物封端的共轭聚合物及其发光元件 - Google Patents
具有磷光有机金属络合物封端的共轭聚合物及其发光元件 Download PDFInfo
- Publication number
- CN1995271A CN1995271A CNA2006101562143A CN200610156214A CN1995271A CN 1995271 A CN1995271 A CN 1995271A CN A2006101562143 A CNA2006101562143 A CN A2006101562143A CN 200610156214 A CN200610156214 A CN 200610156214A CN 1995271 A CN1995271 A CN 1995271A
- Authority
- CN
- China
- Prior art keywords
- substituted
- replacement
- complex
- pyridines
- conjugated polymers
- 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.)
- Pending
Links
- 229920000547 conjugated polymer Polymers 0.000 title claims abstract description 31
- 125000002524 organometallic group Chemical group 0.000 title claims abstract description 22
- 229910052702 rhenium Inorganic materials 0.000 claims abstract description 16
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims abstract description 15
- 229910052741 iridium Inorganic materials 0.000 claims abstract description 10
- 125000000623 heterocyclic group Chemical group 0.000 claims abstract description 9
- 229910052757 nitrogen Inorganic materials 0.000 claims abstract description 8
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims abstract description 5
- 229910052707 ruthenium Inorganic materials 0.000 claims abstract description 5
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 claims description 16
- 239000000463 material Substances 0.000 claims description 15
- WUAPFZMCVAUBPE-UHFFFAOYSA-N rhenium atom Chemical group [Re] WUAPFZMCVAUBPE-UHFFFAOYSA-N 0.000 claims description 15
- 150000003222 pyridines Chemical class 0.000 claims description 14
- 150000002220 fluorenes Chemical class 0.000 claims description 13
- GKOZUEZYRPOHIO-UHFFFAOYSA-N iridium atom Chemical compound [Ir] GKOZUEZYRPOHIO-UHFFFAOYSA-N 0.000 claims description 9
- 150000001875 compounds Chemical class 0.000 claims description 8
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical group [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims description 8
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 claims description 8
- SMWDFEZZVXVKRB-UHFFFAOYSA-N Quinoline Chemical compound N1=CC=CC2=CC=CC=C21 SMWDFEZZVXVKRB-UHFFFAOYSA-N 0.000 claims description 6
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical group [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 claims description 4
- 239000012327 Ruthenium complex Substances 0.000 claims description 4
- 229910052762 osmium Inorganic materials 0.000 claims description 4
- SYQBFIAQOQZEGI-UHFFFAOYSA-N osmium atom Chemical group [Os] SYQBFIAQOQZEGI-UHFFFAOYSA-N 0.000 claims description 4
- 229910052697 platinum Inorganic materials 0.000 claims description 4
- DGEZNRSVGBDHLK-UHFFFAOYSA-N [1,10]phenanthroline Chemical compound C1=CN=C2C3=NC=CC=C3C=CC2=C1 DGEZNRSVGBDHLK-UHFFFAOYSA-N 0.000 claims description 3
- 229910052799 carbon Inorganic materials 0.000 claims description 3
- 125000000118 dimethyl group Chemical group [H]C([H])([H])* 0.000 claims description 3
- 229910052751 metal Inorganic materials 0.000 abstract description 5
- 239000002184 metal Substances 0.000 abstract description 5
- 229910052745 lead Inorganic materials 0.000 abstract 1
- 125000001424 substituent group Chemical group 0.000 abstract 1
- 239000010410 layer Substances 0.000 description 15
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 9
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 9
- 229920000642 polymer Polymers 0.000 description 7
- 238000001228 spectrum Methods 0.000 description 7
- 239000000758 substrate Substances 0.000 description 7
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 6
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 6
- 238000002360 preparation method Methods 0.000 description 6
- 239000004411 aluminium Substances 0.000 description 5
- 230000005284 excitation Effects 0.000 description 5
- 239000011521 glass Substances 0.000 description 5
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 4
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 4
- 229910052782 aluminium Inorganic materials 0.000 description 4
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 4
- 230000005611 electricity Effects 0.000 description 4
- AMGQUBHHOARCQH-UHFFFAOYSA-N indium;oxotin Chemical compound [In].[Sn]=O AMGQUBHHOARCQH-UHFFFAOYSA-N 0.000 description 4
- 238000000034 method Methods 0.000 description 4
- 230000003287 optical effect Effects 0.000 description 4
- 238000005191 phase separation Methods 0.000 description 4
- 239000007787 solid Substances 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- 238000005160 1H NMR spectroscopy Methods 0.000 description 3
- AGBXYHCHUYARJY-UHFFFAOYSA-N 2-phenylethenesulfonic acid Chemical compound OS(=O)(=O)C=CC1=CC=CC=C1 AGBXYHCHUYARJY-UHFFFAOYSA-N 0.000 description 3
- 229920000144 PEDOT:PSS Polymers 0.000 description 3
- 239000002019 doping agent Substances 0.000 description 3
- 238000005401 electroluminescence Methods 0.000 description 3
- 238000007639 printing Methods 0.000 description 3
- 239000000243 solution Substances 0.000 description 3
- 238000012546 transfer Methods 0.000 description 3
- 239000004912 1,5-cyclooctadiene Substances 0.000 description 2
- NYPYPOZNGOXYSU-UHFFFAOYSA-N 3-bromopyridine Chemical compound BrC1=CC=CN=C1 NYPYPOZNGOXYSU-UHFFFAOYSA-N 0.000 description 2
- ROFVEXUMMXZLPA-UHFFFAOYSA-N Bipyridyl Chemical group N1=CC=CC=C1C1=CC=CC=N1 ROFVEXUMMXZLPA-UHFFFAOYSA-N 0.000 description 2
- 206010013786 Dry skin Diseases 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- 238000005481 NMR spectroscopy Methods 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 239000003153 chemical reaction reagent Substances 0.000 description 2
- 239000011248 coating agent Substances 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- 230000008878 coupling Effects 0.000 description 2
- 238000010168 coupling process Methods 0.000 description 2
- 238000005859 coupling reaction Methods 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 238000001704 evaporation Methods 0.000 description 2
- 230000008020 evaporation Effects 0.000 description 2
- 229910001385 heavy metal Inorganic materials 0.000 description 2
- 239000012046 mixed solvent Substances 0.000 description 2
- 150000002894 organic compounds Chemical class 0.000 description 2
- 229920003023 plastic Polymers 0.000 description 2
- DOTRUAJWPIILAO-UHFFFAOYSA-N pyridine;rhenium Chemical compound [Re].C1=CC=NC=C1 DOTRUAJWPIILAO-UHFFFAOYSA-N 0.000 description 2
- 239000011541 reaction mixture Substances 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 230000003595 spectral effect Effects 0.000 description 2
- 230000007704 transition Effects 0.000 description 2
- 238000001291 vacuum drying Methods 0.000 description 2
- 230000000007 visual effect Effects 0.000 description 2
- VYXHVRARDIDEHS-UHFFFAOYSA-N 1,5-cyclooctadiene Chemical compound C1CC=CCCC=C1 VYXHVRARDIDEHS-UHFFFAOYSA-N 0.000 description 1
- FHVZHQUVPVQZFG-UHFFFAOYSA-N 2-bromopyridine 3-bromopyridine Chemical compound BrC=1C=NC=CC1.BrC1=NC=CC=C1 FHVZHQUVPVQZFG-UHFFFAOYSA-N 0.000 description 1
- XFZCSYNEWJRWCU-UHFFFAOYSA-N 3,4-dibromo-1,2-dioctyl-9h-fluorene Chemical compound C1=CC=C2C3=C(Br)C(Br)=C(CCCCCCCC)C(CCCCCCCC)=C3CC2=C1 XFZCSYNEWJRWCU-UHFFFAOYSA-N 0.000 description 1
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 description 1
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 1
- 229910001051 Magnalium Inorganic materials 0.000 description 1
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 description 1
- 229920001609 Poly(3,4-ethylenedioxythiophene) Polymers 0.000 description 1
- 229910021607 Silver chloride Inorganic materials 0.000 description 1
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 1
- ULGYAEQHFNJYML-UHFFFAOYSA-N [AlH3].[Ca] Chemical compound [AlH3].[Ca] ULGYAEQHFNJYML-UHFFFAOYSA-N 0.000 description 1
- NGZDRKMHQSPGHD-UHFFFAOYSA-N [Ni].C1CCC=CC=CC1 Chemical compound [Ni].C1CCC=CC=CC1 NGZDRKMHQSPGHD-UHFFFAOYSA-N 0.000 description 1
- 210000002659 acromion Anatomy 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 230000004888 barrier function Effects 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 239000011575 calcium Substances 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- 229910002091 carbon monoxide Inorganic materials 0.000 description 1
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000005660 chlorination reaction Methods 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- UUZZJNLPJWDNIQ-UHFFFAOYSA-N cycloocta-1,3-diene;cycloocta-1,5-diene Chemical compound C1CCC=CC=CC1.C1CC=CCCC=C1 UUZZJNLPJWDNIQ-UHFFFAOYSA-N 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 125000005594 diketone group Chemical group 0.000 description 1
- -1 dioxoethyl Chemical group 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- 238000004817 gas chromatography Methods 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 150000002367 halogens Chemical class 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 230000002045 lasting effect Effects 0.000 description 1
- 239000004973 liquid crystal related substance Substances 0.000 description 1
- 238000004020 luminiscence type Methods 0.000 description 1
- 229920002521 macromolecule Polymers 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical class [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 1
- 239000012044 organic layer Substances 0.000 description 1
- 239000011368 organic material Substances 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 238000000059 patterning Methods 0.000 description 1
- TZMFJUDUGYTVRY-UHFFFAOYSA-N pentane-2,3-dione Chemical compound CCC(=O)C(C)=O TZMFJUDUGYTVRY-UHFFFAOYSA-N 0.000 description 1
- 229920000172 poly(styrenesulfonic acid) Polymers 0.000 description 1
- 229920002098 polyfluorene Polymers 0.000 description 1
- 239000002861 polymer material Substances 0.000 description 1
- NROKBHXJSPEDAR-UHFFFAOYSA-M potassium fluoride Chemical compound [F-].[K+] NROKBHXJSPEDAR-UHFFFAOYSA-M 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 238000012827 research and development Methods 0.000 description 1
- 230000027756 respiratory electron transport chain Effects 0.000 description 1
- 230000004044 response Effects 0.000 description 1
- SDLBJIZEEMKQKY-UHFFFAOYSA-M silver chlorate Chemical compound [Ag+].[O-]Cl(=O)=O SDLBJIZEEMKQKY-UHFFFAOYSA-M 0.000 description 1
- HKZLPVFGJNLROG-UHFFFAOYSA-M silver monochloride Chemical compound [Cl-].[Ag+] HKZLPVFGJNLROG-UHFFFAOYSA-M 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000000935 solvent evaporation Methods 0.000 description 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
- 238000002604 ultrasonography Methods 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Images
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
- C07F13/00—Compounds containing elements of Groups 7 or 17 of the Periodic Table
- C07F13/005—Compounds without a metal-carbon linkage
-
- 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
- C07F15/0046—Ruthenium compounds
- C07F15/0053—Ruthenium compounds without a metal-carbon linkage
-
- 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
- H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
- H05B—ELECTRIC HEATING; ELECTRIC LIGHT SOURCES NOT OTHERWISE PROVIDED FOR; CIRCUIT ARRANGEMENTS FOR ELECTRIC LIGHT SOURCES, IN GENERAL
- H05B33/00—Electroluminescent light sources
- H05B33/12—Light sources with substantially two-dimensional radiating surfaces
- H05B33/14—Light sources with substantially two-dimensional radiating surfaces characterised by the chemical or physical composition or the arrangement of the electroluminescent material, or by the simultaneous addition of the electroluminescent material in or onto the light source
-
- 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
- H10K85/10—Organic polymers or oligomers
- H10K85/111—Organic polymers or oligomers comprising aromatic, heteroaromatic, or aryl chains, e.g. polyaniline, polyphenylene or polyphenylene vinylene
- H10K85/115—Polyfluorene; Derivatives thereof
-
- 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
-
- 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
-
- 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
- H10K85/361—Polynuclear complexes, i.e. complexes comprising two or more metal centers
-
- 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
- C09K2211/1003—Carbocyclic compounds
- C09K2211/1011—Condensed systems
-
- 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
- C09K2211/18—Metal complexes
- C09K2211/185—Metal complexes of the platinum group, i.e. Os, Ir, Pt, Ru, Rh or Pd
-
- 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
- C09K2211/188—Metal complexes of other metals not provided for in one of the previous groups
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Crystallography & Structural Chemistry (AREA)
- Physics & Mathematics (AREA)
- High Energy & Nuclear Physics (AREA)
- Optics & Photonics (AREA)
- Electroluminescent Light Sources (AREA)
Abstract
本发明提供一种具有磷光有机金属络合物封端的共轭聚合物。该封端共轭聚合物的部份结构如下列结构式I所示：其中M选自铱、锇、铂、铅、铼或钌；R1及R2可以相同或相异，且各代表一氢原子或一取代基；Ar1及Ar2可以相同或相异，且各代表经取代或无取代的杂环基团，该杂环基团含有用以与M形成配位键的氮；及n为20至50之间的正整数。本发明的封端共轭聚合物可作为发光元件或发光装置的电致发光介质。
Description
技术领域
本发明涉及具有两个磷光有机金属络合物封端的共轭聚合物，以及使用该封端共轭聚合物的发光元件。
背景技术
由于较传统液晶显示器视角广以及反应时间快，使用有机发光材料的发光元件的研发近来相当活跃。详细言之，当使用有机化合物作为发光材料时，其可预期实现一种自发光源以及不论视角为何皆有高反应速度的平面显示器。当这些发光元件结合在消费电子装置例如数码摄影机、个人数码助理(PDA)以及视讯电话之中时，可提供例如低消耗功率、高亮度以及设计轻薄的优点。
发光元件的代表例子为发光二极管装置，例如有机发光二极管(OrganicLight-Emitting Diode；OLED)以及聚合物发光二极管(PLED)。一般而言，有机发光二极管装置具有一薄膜配置于一透明阳极以及一金属阴极之间，该薄膜包含可经由外加电流发光的发光材料。而要制造全彩的发光二极管显示面板，就必须要有具有足够发光效率以及适当色度(chromaticity)的高效率红、绿、蓝电致发光材料。
含有机金属络合物的电致磷光材料，由于其高发光效率的性质，使得其在有机发光二极管装置的应用研究上引起极大的注意。由于重金属离子在磷光络合物中有强烈的自旋-轨道偶合(spin-orbital coupling)，单重态与三重态激发子(exciton)皆能完全被利用在电致磷光。因此，理论上可达到百分之百的内量子效率(quantum efficiency)。
已有数个研究报告利用有机金属络合物作为主发光材料(host material)(例如共轭聚合物)中的掺杂剂(dopant)而制得具有良好外量子效率的有机发光二极管管。所制造的装置虽然效率有显著提升，然而在掺杂剂与共轭聚合物之间可能有相分离的问题。将有机金属络合物合成至共轭聚合物的主链上成为磷光聚合物材料亦属已知。例如将铼络合物接在聚芴(polyfluorene)的主链(J.Phys.Chem.B2004，108，13185)，以及将铱络合物接在聚芴的支链(J.Am.Chem.Soc.2003，125，636；Macromolecules 2005，38，4072)。
然而，将有机金属络合物合成至共轭聚合物的主链上时，产物的分子量相当不易控制。将共轭聚合物用于制造LED装置时，聚合物的分子量是重要的条件。如果分子量太低不易形成良好的薄膜。另一方面，如果分子量太高则很难将聚合物溶于溶剂中。
因此，本领域持续需求一种不会有相分离问题(发生在有机金属络合物直接掺杂法)以及制备时可有效控制分子量的电致发光材料。
发明内容
因此，本发明的主要目的在提供一种电致发光材料，其不会有发生在有机金属络合物直接掺杂法的相分离问题，并且在制备时可有效控制分子量。
为达上述以及其他目的，本发明提供一种具有两个磷光有机金属络合物(例如铼络合物、钌络合物或铱络合物)封端的共轭聚合物。该共轭聚合物的主链可包含芴的重复单元。本发明的封端共轭聚合物可作为用于制造发光元件的电致发光材料。
详细言之，该封端共轭聚合物的部份结构系如下列结构式I所示：
其中：
M选自由铱、锇、铂、铅、铼或钌；
R1及R2可以相同或相异，且各代表一氢原子或一取代基；
Ar1及Ar2可以相同或相异，且各代表经取代或无取代的杂环基团，该杂环基团含有用以与M形成配位键的氮；及
n为20至50之间的正整数。
为达上述以及其他目的，本发明另提供一种用结构式I所代表的化合物制成的发光元件。
本发明系使用一种封端剂(例如3-溴吡啶)来控制聚芴的分子量。封端的其他目的是通过吡啶-铼络合物，将电致发光有机金属(例如铼)合成在聚合物分子上。这是一种新颖的电致发光聚合物制备方式，其不会有发生在有机金属络合物直接掺杂法的相分离问题，并且在制备时可有效控制分子量。
附图说明
图1：PFO-endpy与PFO-end2pyRe的紫外-可见光光谱。
图2：PFO-endpy与PFO-end2pyRe的光激发(PL)光谱。
图3：PFO-endpy与PFO-end2pyRe的电激发(EL)光谱。
具体实施方式
本发明系有关于一种具有两个磷光有机金属络合物(例如铼络合物、钌络合物或铱络合物)封端的共轭聚合物。该共轭聚合物的主链可包含芴的重复单元。本发明的封端共轭聚合物可作为用于制造发光元件的电致发光材料，该发光元件可适用于发光装置，例如显示器(电视或荧幕)、背光件、发光源及其类似物。
本发明封端共轭聚合物的部份结构系如下列结构式I所示：
其中n为20至50之间的正整数。
在结构式I中，M代表一重金属例如铱、锇、铂、铅、铼或钌。
结构式I的R1及R2可以相同或相异，且各代表一氢原子或一取代基(较佳为六至十二碳烷基)。
结构式I的Ar1及Ar2可以相同或相异，且各代表经取代或无取代的杂环基团，该杂环基团含有用以与M形成配位键的氮。该含氮基团可以是经取代或无取代的吡啶、经取代或无取代的二吡啶、经取代或无取代的三吡啶、经取代或无取代的菲咯啉、二甲基二吡啶或经取代或无取代的二喹啉。
值得注意的是，结构式I中的磷光有机金属络合物的其他配位基(未示于图中)没有特别限定。适用于本发明的配位基包含卤素配位基、含氮杂环配位基、二酮配位基(例如乙酰丙酮)以及一氧化碳配位基。在有机金属络合物中，可使用一种、两种或多种的配位基。在过渡金属络合物中的配位基较佳为一至两种。
用于本发明实施例的封端共轭聚合物将列于下，但是本发明不应被推断为仅限于这些聚合物。
其中
代表二吡啶。
本发明的封端共轭聚合物可用以作为一发光元件的电致发光介质(electroluminescent medium)。本发明的发光元件可包含一对包含阳极与阴极的电极，以及设于该对电极间以该发光介质形成的发光层或是含有该发光层的复数个有机化合物层。此外，可以形成一元件，其中本发明的封端共轭聚合物系作为夹设于电子传导层以及电洞传导层之间的电致发光层。本发明的发光元件并不受限于其系统、驱动方式以及利用形式，只要其包含本发明的化合物。发光元件的代表例子为一发光二极管装置，例如有机发光二极管(OrganicLight-Emitting Diode；OLED)以及聚合物发光二极管(PLED)。
发光二极管装置的结构一般分为(1)阳极透光型(Bottom Emission type)及(2)阴极透光型(Top Emission type)。阳极透光(Bottom Emission)型装置的阳极为透明电极例如在一基板(例如玻璃或塑胶基板)上的铟锡氧化物(ITO)电极；阴极为不透明或具反射性的低功函数金属如铝或钙铝合金等；电致发光层设于阳极与阴极之间，而光从透明阳极面射出。阴极透光(Top Emission)型装置的阳极为在一基板(例如玻璃或塑胶基板)上的不透明或具反射性金属例如铝/镍或铝/氧化钛；阴极为在薄厚度下为透明的低功函数金属如钙、铝、镁铝合金、ITO等；电致发光层设于阳极与阴极之间，而光从透明阴极面射出。
阳极透光(Bottom Emission)型装置可以下列的方式制作：在一玻璃基板形成该装置，基板上依序形成透明阳极、电洞注入修饰层(可省略)、电洞传递层、发光层、电洞阻隔层、电子传递层及电子注入层(KF，氟化钾)(可省略)与阴极。蒸镀有机层之前先进行ITO玻璃基板的清洁，使用购买的清洁剂与有机溶剂清洗，最后以紫外线臭氧清洁机(UV-ozone cleaner)处理。
实施例1
吡啶封端聚芴(PFO-endpy)的合成
合成反应式如下式1所示。在100毫升的圆底烧瓶中，将二环辛二烯镍(Bis(1，5-cyclooctadiene)nickel(0)Ni(COD)2)(2克，7.11毫摩尔)、二吡啶(2，2-dipyridyl)(1.11克，7.11毫摩尔)以及环辛二烯(1，5-cyclooctadiene)(0.768克，7.11毫摩尔)在氮气环境下溶解于10毫升的二甲基甲酰胺(DMF)。将溶液加热至80℃并持续半小时而形成一紫色络合物。将溶于甲苯(30毫升)与二甲基甲酰胺(5毫升)混合溶剂中的二溴二辛基茀(2，7-Dibromo-9，9-dioctylfluorene)(1.64克，3毫摩尔)及溴吡啶(3-bromopyridine)(0.1克，0.6毫摩尔)加入前述溶液，然后再于80℃加热3天。之后冷却至室温，并将反应混合物倒入盐酸(200毫升)、丙酮(200毫升)与甲醇(200毫升)的混合溶剂中搅拌两小时。将固体滤出并且再溶于氯仿中，然后加入大量甲醇以沉淀出灰黄色固体，将其置于在真空烘箱中以60℃干燥整夜而获得0.9克产物，产率为74％。以核磁共振波谱仪(1H-NMR)(600MHz，CDCl3，ppm)鉴定得：9.09(s，ArH)，8.68(s，ArH)，7.99(s，ArH)，7.93(s，ArH)，7.83(m，ArH)，7.68(m，ArH)，2.12(t，4H)，1.14(m，24H)，0.82(t，6H).以气相层析法(四氢氟喃，THF)鉴定得：数目平均分子量(Mn)＝7073克/摩尔，重量平均分子量(Mw)＝13770克/摩尔，多散性(PDI)＝1.95。
式1
实施例2
化合物II-1的合成
具有两个铼络合物吡啶封端的聚芴(PFO-end2pyRe)(化合物II-1)的合成反应式如下式2所示。将实施例1的PFO-endpy(50毫克)在氮气环境及黑暗状态中，溶解于以100毫升的圆底烧瓶中盛装的甲苯(50毫升)中)。将二吡啶三羰基氯化铼(2，2-Bipyridyl(tricarbonyl)rhenium(I)chloride)(14毫克，0.03毫摩尔)以及过氯酸银(10毫克，0.05毫摩尔)接续加入反应混合物中，并且整夜回流。在冷却至室温之后，过滤去除氯化银。在将溶剂蒸发掉之后，将聚合物固体重新溶解在氯仿中，并且加入大量的甲醇使其产生沉淀物。将聚合物固体在真空烘箱中以60℃干燥整夜。平均分子量为13,770克/摩尔，多散性(polydispersity)为1.95。以核磁共振波谱仪(1H-NMR)(600MHz，CDCl3，ppm)鉴定得：9.12(s，ArH)，8.74(d，ArH)，8.14(s，ArH)，7.93(d，ArH)，7.83(m，ArH)，7.68(m，ArH)，7.55(d，ArH)，2.12(t，4H)，1.14(m，24H)，0.82(t，6H).1H-NMR数据证实在共聚合物中吡啶含量为11.4mol-％。
PFO-endpy与PFO-end2pyRe的紫外-可见光光谱系示于图1。在380nm的强吸收带系来自聚芴的π→π*跃迁，而在430nm的低吸收带系来自金属至配位基电荷转移(MLCT)的跃迁。如图2所示，固态PFO-end2pyRe的光激发(PL)光谱系与PFO-endpy不同在于515nm的波峰。此波峰系来自铼-二吡啶络合物的发光，并显示相当多的能量由激发聚芴转移至铼-二吡啶。
图3所示为PFO-endpy与PFO-end2pyRe的电激发(EL)光谱。电激发(EL)装置的结构为铟锡氧化物(ITO)/聚对苯乙烯磺酸/聚二氧乙基塞吩(PEDOT：PSS)/发光层/钙-铝(Ca-Al)。最高峰系在516nm，且在424nm有一肩峰。光激发(PL)光谱亦可观察到该516nm峰，其系来自铼络合物的发光。在光激发下，主链将能量传递至该金属有机络合物，但因其含量较少，所以光谱呈现以聚芴为主的蓝光。相对地，当电子与电洞自电极注入时，大量的电荷被铼络合物捕捉而在此位置结合放光，因此电激发(EL)光谱显示PFO-end2pyRe系变为绿色，且发射峰变得较宽。
式2
实施例3：发光元件
铟锡氧化物(ITO)/聚对苯乙烯磺酸/聚二氧乙基塞吩(PEDOT：PSS)/发光层/钙铝合金(Ca-Al)
将已图案化的铟锡氧化物(ITO)玻璃以丙酮、异丙醇以及去离子水进行超音波清洗。旋转涂布一薄电洞注入层(聚对苯乙烯磺酸掺杂聚二氧乙基塞吩(polyethylenedioxythiophene doped with poly(styrenesulfonic acid)[PEDOT：PSS]))于ITO上。将溶解在氯仿中的PFO-end2pyRe(化合物II-1)溶液旋转涂布在其上形成一电致发光介质。最后，在10-5torr真空下，热蒸镀形成钙-铝阴极。
本发明使用一种封端剂(例如3-溴吡啶)来控制聚芴的分子量。封端的其他目的是通过形成吡啶-铼络合物，而在聚合物中加入电致发光有机金属(例如铼)。这是一种新颖的电致发光聚合物制备方式，其不会有发生在有机金属络合物直接掺杂法的相分离问题，并且在制备时可有效控制分子量。
虽然本发明已以至少一较佳实施例揭露如上，然其并非用以限定本发明，任何本领域技术人员，在不脱离本发明的精神和范围内，当可作各种的更动与润饰，因此本发明的保护范围当视后附的权利要求所界定者为准。
Claims (10)
1.一种电致发光材料，其特征在于，包含具有两个磷光有机金属络合物封端的共轭聚合物。
2.如权利要求第1项所述的电致发光材料，其特征在于，该有机金属络合物为铼络合物、钌络合物或铱络合物。
3.如权利要求第1项所述的电致发光材料，其特征在于，该共轭聚合物的主链包含芴的重复单元。
4.如权利要求第1项所述的电致发光材料，其特征在于，该封端共轭聚合物的部份结构如下列结构式I所示：
其中：
M选自铱、锇、铂、铅、铼或钌；
R1及R2可以相同或相异，且各代表一氢原子或一取代基，其中该取代基代表六至十二碳烷基；
Ar1及Ar2可以相同或相异，且各代表经取代或无取代的杂环基团，该杂环基团含有用以与M形成配位键的氮，其中Ar1及Ar2选自经取代或无取代的吡啶、经取代或无取代的二吡啶、经取代或无取代的三吡啶、经取代或无取代的菲咯啉、二甲基二吡啶或经取代或无取代的二喹啉；及
n为20至50之间的正整数。
5.如权利要求第1项所述的电致发光材料，其特征在于，该封端共轭聚合物为以下列结构式I-1、II-2或II-3表示的化合物：
其中
代表二吡啶。
6.一种发光元件，其包含：
一阳极与一阴极；以及
一夹设于该阳极与阴极之间的电致发光介质，
其中该电致发光介质包含具有两个磷光有机金属络合物封端的共轭聚合物。
7.如权利要求第6项所述的发光元件，其特征在于，该有机金属络合物为铼络合物、钌络合物或铱络合物。
8.如权利要求第6项所述的发光元件，其特征在于，该共轭聚合物的主链包含芴的重复单元。
9.如权利要求第6项所述的发光元件，其特征在于，该封端共轭聚合物的部份结构如下列结构式I所示：
其中：
M选自铱、锇、铂、铅、铼或钌；
R1及R2可以相同或相异，且各代表一氢原子或一取代基，其中该取代基代表六至十二碳烷基；
Ar1及Ar2可以相同或相异，且各代表经取代或无取代的杂环基团，该杂环基团含有用以与M形成配位键的氮，其中Ar1及Ar2选自经取代或无取代的吡啶、经取代或无取代的二吡啶、经取代或无取代的三吡啶、经取代或无取代的菲咯啉、二甲基二吡啶或经取代或无取代的二喹啉；及
n为20至50之间的正整数。
10.如权利要求第6项所述的发光元件，其特征在于，该封端共轭聚合物为以下列结构式I-1、II-2或II-3表示的化合物：
其中
代表二吡啶。
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US11/313,938 US20070148491A1 (en) | 2005-12-22 | 2005-12-22 | Conjugated polymer end-capped with phosphorescent organometallic complex, light-emitting element and light-emitting device |
| US11/313,938 | 2005-12-22 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN1995271A true CN1995271A (zh) | 2007-07-11 |
Family
ID=38194197
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNA2006101562143A Pending CN1995271A (zh) | 2005-12-22 | 2006-12-21 | 具有磷光有机金属络合物封端的共轭聚合物及其发光元件 |
Country Status (2)
| Country | Link |
|---|---|
| US (1) | US20070148491A1 (zh) |
| CN (1) | CN1995271A (zh) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101880525A (zh) * | 2009-05-07 | 2010-11-10 | 财团法人工业技术研究院 | 液态荧光剂组合物及发光组件 |
| CN102309106A (zh) * | 2010-07-08 | 2012-01-11 | 富士迈半导体精密工业（上海）有限公司 | 发光太阳能伞 |
| WO2021143690A1 (zh) * | 2020-01-16 | 2021-07-22 | 厦门大学 | 一种含锇共轭聚合物及其制备方法与应用 |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR102153447B1 (ko) * | 2015-12-01 | 2020-09-08 | 엘티소재주식회사 | 헤테로고리 화합물 및 이를 이용한 유기 발광 소자 |
| CN109516979B (zh) * | 2018-10-25 | 2021-03-12 | 中国科学院上海微系统与信息技术研究所 | 一种利用荧光检测二硝酸酯类爆炸物的方法 |
Family Cites Families (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6548836B1 (en) * | 1999-04-29 | 2003-04-15 | Massachusetts Institute Of Technology | Solid state light-emitting device |
| TW528789B (en) * | 2000-12-22 | 2003-04-21 | Koninkl Philips Electronics Nv | Electroluminescent device comprising an electroluminescent material of at least two metal chelates |
| US20060093852A1 (en) * | 2002-06-04 | 2006-05-04 | Dirk Marsitzky | Phosphorescent and luminescent conjugated polymers and their use in electroluminescent assemblies |
-
2005
- 2005-12-22 US US11/313,938 patent/US20070148491A1/en not_active Abandoned
-
2006
- 2006-12-21 CN CNA2006101562143A patent/CN1995271A/zh active Pending
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101880525A (zh) * | 2009-05-07 | 2010-11-10 | 财团法人工业技术研究院 | 液态荧光剂组合物及发光组件 |
| WO2010127548A1 (en) * | 2009-05-07 | 2010-11-11 | Industrial Technology Research Institute | Liquid fluorescent composition and light emitting device |
| CN101880525B (zh) * | 2009-05-07 | 2013-10-16 | 财团法人工业技术研究院 | 液态荧光剂组合物及发光组件 |
| CN102309106A (zh) * | 2010-07-08 | 2012-01-11 | 富士迈半导体精密工业（上海）有限公司 | 发光太阳能伞 |
| WO2021143690A1 (zh) * | 2020-01-16 | 2021-07-22 | 厦门大学 | 一种含锇共轭聚合物及其制备方法与应用 |
Also Published As
| Publication number | Publication date |
|---|---|
| US20070148491A1 (en) | 2007-06-28 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| KR100997069B1 (ko) | 아릴아민 단위를 포함하는 공액 중합체, 그의 제조방법 및용도 | |
| CN100422236C (zh) | 包含螺二芴单元的共轭聚合物及其应用 | |
| CN101805266B (zh) | 有机电致发光化合物和使用该化合物的有机电致发光器件 | |
| US7098295B2 (en) | Electroluminescent conjugated polymers containing phosphorescent moieties and the application thereof in led | |
| CN101743650B (zh) | 有机发光器件和显示装置 | |
| CN1818009B (zh) | 蓝光电致发光化合物和使用其的有机电致发光器件 | |
| CN102924217A (zh) | 新型有机电致发光化合物及使用该化合物的有机电致发光装置 | |
| Park et al. | Synthesis and electroluminescence of new polyfluorene copolymers with phenothiazine derivative. Their application in white-light-emitting diodes | |
| JP2018508626A (ja) | ポリマー主鎖中に発光繰り返し単位を含む有機発光ポリマーおよびそれを用いたデバイス | |
| Mei et al. | Synthesis and characterization of white‐light‐emitting polyfluorenes containing orange phosphorescent moieties in the side chain | |
| CN102984840A (zh) | 发白光材料 | |
| CN101230127A (zh) | 具有1,8-萘二甲酰亚胺基的聚合物及有机发光器件 | |
| JP5771612B2 (ja) | 電界発光材料および素子 | |
| JP2015506403A (ja) | ポリマー | |
| TW201218478A (en) | Organic electroluminance element and method for manufacturing the same | |
| CN1995271A (zh) | 具有磷光有机金属络合物封端的共轭聚合物及其发光元件 | |
| Lo et al. | Synthesis and electroluminescence properties of white‐light single polyfluorenes with high‐molecular weight by click reaction | |
| JP5732042B2 (ja) | 有機発光材料および素子 | |
| JP2018522820A (ja) | 発光化合物 | |
| JP4416074B2 (ja) | 電荷輸送性材料、有機エレクトロルミネッセンス素子、および表示用パネル | |
| Zhuang et al. | High‐efficiency, electrophosphorescent polymers with porphyrin–platinum complexes in the conjugated backbone: Synthesis and device performance | |
| CN101243156A (zh) | 含有金属配合物的发光材料以及使用该材料的光电器件 | |
| CN102169969A (zh) | 有机电致发光器件的阳极修饰方法 | |
| Tsujimoto et al. | Pure red electroluminescence from novel heteroleptic cyclometalated platinum (II) emitters embedded in polyvinylcarbazole | |
| US20130029448A1 (en) | Methods for producing materials with photo- and electroluminescence properties and systems using such materials |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C02 | Deemed withdrawal of patent application after publication (patent law 2001) | ||
| WD01 | Invention patent application deemed withdrawn after publication |
Open date: 20070711 |