CN1272402C - 场致发光材料 - Google Patents
场致发光材料 Download PDFInfo
- Publication number
- CN1272402C CN1272402C CNB998129496A CN99812949A CN1272402C CN 1272402 C CN1272402 C CN 1272402C CN B998129496 A CNB998129496 A CN B998129496A CN 99812949 A CN99812949 A CN 99812949A CN 1272402 C CN1272402 C CN 1272402C
- Authority
- CN
- China
- Prior art keywords
- electroluminescence device
- iii
- hole
- electroluminescent
- electrode
- 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.)
- Expired - Fee Related
Links
- 239000000463 material Substances 0.000 title claims description 35
- 150000001875 compounds Chemical class 0.000 claims abstract description 19
- 238000005401 electroluminescence Methods 0.000 claims description 22
- 229910052757 nitrogen Inorganic materials 0.000 claims description 11
- 239000011159 matrix material Substances 0.000 claims description 9
- 239000000203 mixture Substances 0.000 claims description 9
- 230000005525 hole transport Effects 0.000 claims description 8
- 238000012546 transfer Methods 0.000 claims description 8
- 229910052751 metal Inorganic materials 0.000 claims description 7
- 239000002184 metal Substances 0.000 claims description 7
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 5
- 239000004411 aluminium Substances 0.000 claims description 5
- 229910052782 aluminium Inorganic materials 0.000 claims description 5
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical group [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 5
- 239000001257 hydrogen Substances 0.000 claims description 5
- 229910052739 hydrogen Inorganic materials 0.000 claims description 5
- 238000001228 spectrum Methods 0.000 claims description 5
- 229910052693 Europium Inorganic materials 0.000 claims description 4
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 claims description 4
- OGPBJKLSAFTDLK-UHFFFAOYSA-N europium atom Chemical compound [Eu] OGPBJKLSAFTDLK-UHFFFAOYSA-N 0.000 claims description 4
- 239000013110 organic ligand Substances 0.000 claims description 4
- 125000004076 pyridyl group Chemical group 0.000 claims description 4
- 229910052727 yttrium Inorganic materials 0.000 claims description 4
- VWQVUPCCIRVNHF-UHFFFAOYSA-N yttrium atom Chemical compound [Y] VWQVUPCCIRVNHF-UHFFFAOYSA-N 0.000 claims description 4
- ZSLUVFAKFWKJRC-IGMARMGPSA-N 232Th Chemical compound [232Th] ZSLUVFAKFWKJRC-IGMARMGPSA-N 0.000 claims description 3
- 229910052688 Gadolinium Inorganic materials 0.000 claims description 3
- 229910052776 Thorium Inorganic materials 0.000 claims description 3
- UIWYJDYFSGRHKR-UHFFFAOYSA-N gadolinium atom Chemical compound [Gd] UIWYJDYFSGRHKR-UHFFFAOYSA-N 0.000 claims description 3
- 229910001316 Ag alloy Inorganic materials 0.000 claims description 2
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 claims description 2
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 claims description 2
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims description 2
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims description 2
- 229910052771 Terbium Inorganic materials 0.000 claims description 2
- 150000004982 aromatic amines Chemical class 0.000 claims description 2
- 239000011575 calcium Substances 0.000 claims description 2
- XQTIWNLDFPPCIU-UHFFFAOYSA-N cerium(3+) Chemical compound [Ce+3] XQTIWNLDFPPCIU-UHFFFAOYSA-N 0.000 claims description 2
- ITZXULOAYIAYNU-UHFFFAOYSA-N cerium(4+) Chemical compound [Ce+4] ITZXULOAYIAYNU-UHFFFAOYSA-N 0.000 claims description 2
- 238000000975 co-precipitation Methods 0.000 claims description 2
- 239000011737 fluorine Substances 0.000 claims description 2
- 229910052731 fluorine Inorganic materials 0.000 claims description 2
- 229910052749 magnesium Inorganic materials 0.000 claims description 2
- 239000011777 magnesium Substances 0.000 claims description 2
- 229920003227 poly(N-vinyl carbazole) Polymers 0.000 claims description 2
- 229920000767 polyaniline Polymers 0.000 claims description 2
- GZCRRIHWUXGPOV-UHFFFAOYSA-N terbium atom Chemical compound [Tb] GZCRRIHWUXGPOV-UHFFFAOYSA-N 0.000 claims description 2
- 229910052791 calcium Inorganic materials 0.000 claims 1
- 229910052744 lithium Inorganic materials 0.000 claims 1
- SJCKRGFTWFGHGZ-UHFFFAOYSA-N magnesium silver Chemical compound [Mg].[Ag] SJCKRGFTWFGHGZ-UHFFFAOYSA-N 0.000 claims 1
- 125000002524 organometallic group Chemical group 0.000 claims 1
- DHDHJYNTEFLIHY-UHFFFAOYSA-N 4,7-diphenyl-1,10-phenanthroline Chemical compound C1=CC=CC=C1C1=CC=NC2=C1C=CC1=C(C=3C=CC=CC=3)C=CN=C21 DHDHJYNTEFLIHY-UHFFFAOYSA-N 0.000 abstract description 5
- 229910052768 actinide Inorganic materials 0.000 abstract description 3
- 150000001255 actinides Chemical class 0.000 abstract description 3
- OBOSXEWFRARQPU-UHFFFAOYSA-N 2-n,2-n-dimethylpyridine-2,5-diamine Chemical compound CN(C)C1=CC=C(N)C=N1 OBOSXEWFRARQPU-UHFFFAOYSA-N 0.000 abstract 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 abstract 1
- 229910052747 lanthanoid Inorganic materials 0.000 abstract 1
- 150000002602 lanthanoids Chemical class 0.000 abstract 1
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 12
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 12
- -1 europium (III) triphenylenyl diamine Chemical class 0.000 description 8
- 239000011521 glass Substances 0.000 description 7
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 6
- 239000011248 coating agent Substances 0.000 description 6
- 238000000576 coating method Methods 0.000 description 6
- 238000005424 photoluminescence Methods 0.000 description 6
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 5
- 150000003222 pyridines Chemical class 0.000 description 5
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 4
- 238000002360 preparation method Methods 0.000 description 4
- 239000011541 reaction mixture Substances 0.000 description 4
- 238000001291 vacuum drying Methods 0.000 description 4
- ZVGCGHVMJAECEG-UHFFFAOYSA-N Chinol Natural products COC1=C(O)C(C)=C(C)C(O)=C1OC ZVGCGHVMJAECEG-UHFFFAOYSA-N 0.000 description 3
- 238000005660 chlorination reaction Methods 0.000 description 3
- 239000005357 flat glass Substances 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- 238000011160 research Methods 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 238000005406 washing Methods 0.000 description 3
- YRAJNWYBUCUFBD-UHFFFAOYSA-N 2,2,6,6-tetramethylheptane-3,5-dione Chemical compound CC(C)(C)C(=O)CC(=O)C(C)(C)C YRAJNWYBUCUFBD-UHFFFAOYSA-N 0.000 description 2
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- 125000000217 alkyl group Chemical group 0.000 description 2
- OSGAYBCDTDRGGQ-UHFFFAOYSA-L calcium sulfate Chemical compound [Ca+2].[O-]S([O-])(=O)=O OSGAYBCDTDRGGQ-UHFFFAOYSA-L 0.000 description 2
- 229920001940 conductive polymer Polymers 0.000 description 2
- 125000005594 diketone group Chemical group 0.000 description 2
- GNTDGMZSJNCJKK-UHFFFAOYSA-N divanadium pentaoxide Chemical compound O=[V](=O)O[V](=O)=O GNTDGMZSJNCJKK-UHFFFAOYSA-N 0.000 description 2
- 238000000034 method Methods 0.000 description 2
- 239000012299 nitrogen atmosphere Substances 0.000 description 2
- 239000004033 plastic Substances 0.000 description 2
- 229920003023 plastic Polymers 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 238000005507 spraying Methods 0.000 description 2
- WEQHQGJDZLDFID-UHFFFAOYSA-J thorium(iv) chloride Chemical compound Cl[Th](Cl)(Cl)Cl WEQHQGJDZLDFID-UHFFFAOYSA-J 0.000 description 2
- 229910052723 transition metal Inorganic materials 0.000 description 2
- 150000003624 transition metals Chemical class 0.000 description 2
- BWLBGMIXKSTLSX-UHFFFAOYSA-N 2-hydroxyisobutyric acid Chemical compound CC(C)(O)C(O)=O BWLBGMIXKSTLSX-UHFFFAOYSA-N 0.000 description 1
- 101100150353 Arabidopsis thaliana SRS8 gene Proteins 0.000 description 1
- 229910000882 Ca alloy Inorganic materials 0.000 description 1
- 229920000742 Cotton Polymers 0.000 description 1
- 150000000921 Gadolinium Chemical class 0.000 description 1
- 229910003317 GdCl3 Inorganic materials 0.000 description 1
- 229910000733 Li alloy Inorganic materials 0.000 description 1
- 229910000861 Mg alloy Inorganic materials 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- 239000004743 Polypropylene Substances 0.000 description 1
- 239000004793 Polystyrene Substances 0.000 description 1
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 1
- 150000001218 Thorium Chemical class 0.000 description 1
- 125000002777 acetyl group Chemical group [H]C([H])([H])C(*)=O 0.000 description 1
- 239000013543 active substance Substances 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- IUFDZNVMARBLOJ-UHFFFAOYSA-K aluminum;quinoline-2-carboxylate Chemical compound [Al+3].C1=CC=CC2=NC(C(=O)[O-])=CC=C21.C1=CC=CC2=NC(C(=O)[O-])=CC=C21.C1=CC=CC2=NC(C(=O)[O-])=CC=C21 IUFDZNVMARBLOJ-UHFFFAOYSA-K 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 150000008280 chlorinated hydrocarbons Chemical class 0.000 description 1
- 239000005321 cobalt glass Substances 0.000 description 1
- 239000004020 conductor Substances 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 238000007334 copolymerization reaction Methods 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 150000003983 crown ethers Chemical class 0.000 description 1
- 238000000151 deposition Methods 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 239000002019 doping agent Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000004070 electrodeposition Methods 0.000 description 1
- 238000001194 electroluminescence spectrum Methods 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- MGVUQZZTJGLWJV-UHFFFAOYSA-N europium(2+) Chemical compound [Eu+2] MGVUQZZTJGLWJV-UHFFFAOYSA-N 0.000 description 1
- NNMXSTWQJRPBJZ-UHFFFAOYSA-K europium(iii) chloride Chemical compound Cl[Eu](Cl)Cl NNMXSTWQJRPBJZ-UHFFFAOYSA-K 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 239000000706 filtrate Substances 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 238000005755 formation reaction Methods 0.000 description 1
- MEANOSLIBWSCIT-UHFFFAOYSA-K gadolinium trichloride Chemical compound Cl[Gd](Cl)Cl MEANOSLIBWSCIT-UHFFFAOYSA-K 0.000 description 1
- 230000003760 hair shine Effects 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 125000000623 heterocyclic group Chemical group 0.000 description 1
- AMGQUBHHOARCQH-UHFFFAOYSA-N indium;oxotin Chemical compound [In].[Sn]=O AMGQUBHHOARCQH-UHFFFAOYSA-N 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- 239000004922 lacquer Substances 0.000 description 1
- 239000000990 laser dye Substances 0.000 description 1
- 239000004973 liquid crystal related substance Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 238000013508 migration Methods 0.000 description 1
- 230000005012 migration Effects 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- 229920000620 organic polymer Polymers 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 239000002861 polymer material Substances 0.000 description 1
- 229920000098 polyolefin Polymers 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 229920002223 polystyrene Polymers 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 238000006862 quantum yield reaction Methods 0.000 description 1
- 238000002310 reflectometry Methods 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 239000004332 silver Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- HKCRVXUAKWXBLE-UHFFFAOYSA-N terbium(3+) Chemical compound [Tb+3] HKCRVXUAKWXBLE-UHFFFAOYSA-N 0.000 description 1
- YMURPAJPLBCAQW-UHFFFAOYSA-N thorium(4+) Chemical compound [Th+4] YMURPAJPLBCAQW-UHFFFAOYSA-N 0.000 description 1
- 238000001771 vacuum deposition Methods 0.000 description 1
- 238000007738 vacuum evaporation Methods 0.000 description 1
- 230000000007 visual effect Effects 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- PCMOZDDGXKIOLL-UHFFFAOYSA-K yttrium chloride Chemical compound [Cl-].[Cl-].[Cl-].[Y+3] PCMOZDDGXKIOLL-UHFFFAOYSA-K 0.000 description 1
Images
Classifications
-
- 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
-
- 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
- H10K85/351—Metal complexes comprising lanthanides or actinides, e.g. comprising europium
-
- 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
- C09K2211/182—Metal complexes of the rare earth metals, i.e. Sc, Y or lanthanide
-
- 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
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10S428/00—Stock material or miscellaneous articles
- Y10S428/917—Electroluminescent
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Physics & Mathematics (AREA)
- Optics & Photonics (AREA)
- Electroluminescent Light Sources (AREA)
- Pyridine Compounds (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Luminescent Compositions (AREA)
Abstract
一种新的场致发光化合物，其发出的光是蓝色或蓝紫色光，是一种镧系元素或锕系元素的配合物，例如是氯化单(红菲绕啉)钍IV或氯化单(三吡啶基)钇的有机配合物。
Description
本发明涉及场致发光材料和它们构成的装置。
当电流通过时可发光的材料是公知的并且广泛用于显示应用领域。液晶装置和基于无机半导体体系的装置被广泛地使用。但是，它们受到下列缺点的困扰：高能耗，高生产费用，低量子效率和不能制成平板显示，反射率问题，即，在明亮条件下的低可见度和例如+/-45°的窄视角。
已建议使用有机聚合物作为场致发光材料，但是不能得到纯色，它们制备昂贵并且效率较低。
另一种已经建议使用的混合物是醌醇铝(aluminium quinolate)，但是这要求使用掺杂剂以得到一定的颜色范围并且效率较低。
在1990年的“化学快报(Chemistry letter)”pp 657-660中Kido等人的一篇文章公开了乙酰基醋酮酸铽(III)配合物是绿色的场致发光材料，在1994年10月24日的“应用物理快报(Applied Physicsletters)”65(17)中Kido等人的一篇文章公开了铕(III)三亚苯基二胺配合物是红色的场致发光材料，但是它们在大气压条件下不稳定并且很难制成薄膜。
这些文章公开的配合物有较低的光致发光效率，并且只能产生绿光或红光而不能产生其它颜色。
现在我们发现了光致发光和场致发光化合物以及发蓝光和蓝紫光的材料。
根据本发明，提供了一种光致发光的化合物，其含有过渡金属、镧系元素或锕系元素和有机配体的有机配合物，该光致发光化合物发出在蓝色或蓝紫色光谱的光。
已经惊奇地发现能够通过选择金属和有机配体形成一种配合物，当电流通过时，其发出蓝光或蓝紫光。
本发明还提供一种场致发光化合物，其含有过渡金属、镧系元素或锕系元素和有机配体的有机配合物，当电流通过时，该场致发光化合物发出蓝色或蓝紫色(purplish blue)光谱的光。
光的颜色是主观的，颜色可通过其中颜色在其各自区域的在二维图上的坐标定义，在本发明中，蓝色和蓝紫色光谱定义为在色图CIEI931中坐标界定的区域，其一份复印件如图1所示。本发明的配合物可产生在坐标(0，0)(0，0.3)(0.3，0)中的光。
光谱中蓝色区域的光很难生成，迄今还不可能用场致发光的方法产生蓝光。
优选的金属是钍(IV)、钇(III)、钆(III)、铕(II)、铽(IV)、铈(IV)和铈(III)。可使用金属混合物形成混合的螯合物。
优选的配体是
其中R’在分子的不同部分相同或不同，每个R”和R’是取代的或未取代的芳环或杂环结构或烃基或氟碳基，或R”是氟或氢或R”与例如单体共聚，或R’是叔丁基且R”是氢。
优选每个R’、R”和R’是烷基，优选-C(CH3)基。
优选的配合物是TMHD(三(2，2，6，6-四甲基-3，5-庚二酮根合(heptanedionato))、α’，α”，α三吡啶、红菲绕啉(4，7-二苯基-1，1-菲绕啉)、冠醚和cryptans的配合物。
特别优选的配合物是红菲绕啉钍、三吡啶基钇和Y-TMHD以及Eu-TMHD配合物。
具有强光致发光和场致发光性质的新配合物是Eu(II)(TMHD)2配合物，其在空气中稳定。曾认为这类Eu(II)配合物在有氧气存在下是不稳定的，令人惊奇的是该配合物在空气中稳定。
本发明的配合物可用于构成场致发光装置。
本发明的场致发光装置包括一种透明的基质，其为导电玻璃或塑料，用作阳极，优选的基质是导电玻璃，诸如铟锡氧化物涂敷的玻璃，但是任何可导电的玻璃或具有导电层的玻璃均可使用。还可以使用导电聚合物和导电聚合物涂敷的玻璃或塑料作为该基质。可通过从场致发光物质在有机溶剂中的溶液蒸发将该物质直接沉积在基质上。使用的溶剂取决于该场致发光物质，例如在许多情况下适用的有醇类，诸如乙醇；酮类，诸如丙酮和乙酰醋酮酸甲酯；和氯化烃类，诸如二氯甲烷。
或者，场致发光物质的沉积可以通过喷涂或真空沉淀，例如从固体状态通过喷射，或可以使用任何其它的常规方法。
在本发明的一个实施方案中，在透明基质上沉积了一个空穴传递层，场致发光物质沉积在空穴传递层上。空穴传递层用于传递空穴和阻断电子，从而防止电子移动到电极而不再与空穴结合。因此载体的再结合主要发生在发光层。
空穴传递层用于聚合物场致发光、装置，可以使用任何已知的薄膜形式的空穴传递材料。
空穴传递层可以由芳胺配合物的薄膜制备，诸如聚(乙烯基咔唑)、N，N’-二苯基-N，N’-二(3-甲基苯基)-1，1’-联苯基-4，4’-二胺(TPD)、聚苯胺等。
可任选地包括诸如荧光激光染料、发光激光染料等染料用于改进发射光的色谱。
优选场致发光材料与惰性聚合物材料混合，诸如聚烯烃，例如聚乙烯、聚丙烯等，优选聚苯乙烯。优选在混合物中场致发光材料的量为95％-5％重量活性物质，更优选25-20％重量。
空穴传递化合物可任选地与场致发光材料以5-95％场致发光材料比95-5％空穴传递化合物的比例混合。在本发明的另一个实施方案中，在阴极和场致发光材料层之间有一个电子注入材料层，优选该电子注入材料是金属配合物，诸如醌醇金属盐，如醌醇铝，当电流通过时，传递电子。或者电子注入材料可以与场致发光材料混合并与之共沉淀。
在一个优选的结构中，透明的导体材料形成的基质是阳极，在其上相继沉积了一个空穴传递层、电场发光材料层和一个与阳极接触的电子注入层。阳极可以是任何低功函的金属，例如铝、镁、钙、锂、银/镁合金等。
本发明优选化合物的制备方法如下列实施例所示。
实施例1
氯化单(红菲绕啉)钍(IV)。氯化钍(IV)(5mmol，1.87g)在50℃溶于乙醇/水混合物(2∶1v/v)(75ml)中。红菲绕啉(5mmol，1.66g)溶于乙醇/二氯甲烷(2∶1v/v)(75ml)的混合物中，将其分批加入到钍盐的溶液中。混合物在电炉上100℃下还原1小时。过滤沉淀物得到灰白色固体，用二乙醚(2×25ml)洗涤，真空干燥，得到产物(1.9g)。
实施例2
氯化单(α’，α”，α三吡啶基)钇(III)。氯化钇(III)(2mmol，0.61g)溶于乙醇(100ml)，加入α’，α”，α三吡啶(2mmol，0.47g)。反应混合物在50℃温热60分钟，除去溶剂。残留物用二乙醚(2×25ml)洗涤，真空干燥，得到产物(0.80g)。
实施例3
单(α’，α”，α三吡啶)三(2，2，6，6-四甲基-3，5-庚二酮根合)钇(III)。将该三-螯合物(1mmol，0.64g)溶于乙醇(100ml)，加入α’，α”，α三吡啶(1mmol，0.23g)。反应混合物在50℃温热60分钟，除去溶剂。残留物用二乙醚(2×25ml)洗涤，真空干燥，得到产物(0.50g)。产率57％。
实施例4
氯化单(α’，α”，α三吡啶基)钆(III)。氯化钆(III)(0.37g，1mmol)溶于乙醇(150ml)，加入α’，α”，α三吡啶(0.23g，1mmol)。反应混合物回流加热1小时，真空下除去溶剂，得到钆加合物(产量0.50g)。
实施例5
二(2，2，6，6-四甲基-3，5-庚二酮根合)铕(II)。反应在无水条件下使用干燥的玻璃器具在干氮气下进行，使用在五氧化二磷上新鲜蒸馏的乙酰腈。氯化铕(II)(1.0g，5mmol)置于250ml安装了冷凝器、两个滴液漏斗和氮气鼓泡器的三颈圆底烧瓶中。二酮(1.84g，10mmol)在乙酰腈(50ml)中的去氧的溶液置于第一个滴液漏斗中，去氧的乙酰腈(150ml)置于第二个滴液漏斗。两个漏斗在氮气气氛下并且安装了氮气鼓泡器。将乙酰腈加入烧瓶中，混合物在50℃(油浴)搅拌直至溶解。然后将二酮溶液加入烧瓶中，反应混合物回流1小时，在氮气气氛下冷却过夜。干燥二乙醚，在60℃真空干燥(产量0.82g)。干燥滤液，得到浅黄色三(2，2，6，6-四甲基-3，5-庚二酮根合)铕(II)(产量0.90g)。
制造场致发光装置并进行测试。
1装置的制备
ITO涂敷的玻璃片(1×1cm2，从瑞士Balzers购买的大片材上裁下)一部分用浓盐酸腐蚀除去ITO并进行清洁，置于旋涂机上(CPS 10BM，Semitec.德国)，在2000rpm旋转30秒，期间用吸移管将场致发光化合物的溶液滴加到该玻璃片上面。
或者将场致发光化合物真空蒸发到ITO涂敷的玻璃片上，通过将基质置于真空涂敷器中，在10-5-10-6托将场致发光化合物蒸发到基质上。
在已经被浓盐酸腐蚀的部分上的有机涂层用棉线擦除。
涂敷的电极在使用硫酸钙的真空干燥器中储存直到将其加到真空涂料器中(Edwards，10-6托)并制成铝端触点。LED的活性区域每0.1cm2为0.08cm2，然后将元件保存在真空干燥器中直到进行场致发光研究。
ITO电极总是和负端接触。电流对电压的研究在计算机控制的Keithly 2400源计量器上进行。
场致发光光谱通过计算机控制的在77II2型Insta Spec光电二极管矩阵体系(Oriel Co.，Surrey，英国)上的电荷耦合装置记录。
2光致发光的测量
使用Liconix 4207NB，He/Cd激光器的325mn光线激发光致发光。在样品上照射的激光能量(0.3mWcm-2)通过Liconix 55PM激光能量计量器测量。使用Bentham发光标准(Bentham SRS8，灯电流4000A，英国国家物理实验室标准)。PL研究在样品或薄膜上进行。对实施例的配合物进行测试，结果如表和附图2-6的光谱所示。
表
| 实施例 | PL％ | λmax/nm | CIE | 颜色 | |
| x | y | ||||
| 1 | 1.0 | 450 | 0.17 | 0.15 | 紫 |
| 2 | 6.0 | 410，520 | 0.21 | 0.32 | 蓝绿 |
| 3 | 0.03 | 460 | 0.21 | 0.29 | 白 |
| 4 | 16 | 320，450 | 紫 | ||
| 5 | 0.9 | 420 | 0.18 | 0.05 | 紫 |
Claims (11)
1.一种场致发光装置，其包括(i)第一电极，(ii)非必须的空穴传递材料层，(iii)包含金属与有机配体的有机金属配合物的发出蓝色或蓝紫色光谱的光的场致发光化合物层，其中金属选自钍(IV)、钇(III)、钆(III)、铕(II)、铽(III)、铈(IV)和铈(III)或其混合物，所述配体选自以下(a)至(d)中任意一项：
(a)下式的β-二酮：
其中R’在分子的不同部分相同或不同，R’分别选自叔丁基和-C(CH3)基，R”选自氢和氟；(b)三(2，2，6，6-四甲基-3，5-庚二酮根合)；(c)α’，α”，α三吡啶基；(d)4，7-二苯基-1，1-菲绕啉；(iv)非必须的电子注入材料层；和(v)第二电极。
2.权利要求1的场致发光装置，其中R’表示叔丁基或-C(CH3)基和R”表示氢。
3.权利要求1的场致发光装置，其中R’表示叔丁基和R”表示氢。
4.权利要求1的场致发光装置，其中所述场致发光化合物是二(三(2，2，6，6-四甲基-3，5-庚二酮根合))铕(II)。
5.权利要求1的场致发光装置，其中第一电极含有透明的基质，该基质是其上有空穴传递层的阳极，空穴传递层上面沉积了所述的场致发光化合物。
6.根据权利要求1的场致发光装置，其中有一种空穴传递材料与场致发光化合物以5-95％场致发光化合物比95-5％空穴传递材料的比例混合。
7.根据权利要求5或6的场致发光装置，其中空穴传递材料是聚(乙烯基咔唑)、N，N’-二苯基-N，N’-二(3-甲基苯基)-1，1’-联苯基-4，4’-二胺或聚苯胺。
8.根据权利要求5或6的场致发光装置，其中空穴传递材料是芳胺配合物。
9.根据权利要求5的场致发光装置，其中在作为阴极的第二电极和场致发光材料层之间有一个电子注入材料层。
10.根据权利要求6的场致发光装置，其中电子注入材料与场致发光材料混合并与之共沉淀。
11.根据权利要求1的场致发光装置，其中阳极是铝、镁、锂、钙或镁银合金。
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| GB9823761.3 | 1998-11-02 | ||
| GBGB9823761.3A GB9823761D0 (en) | 1998-11-02 | 1998-11-02 | Novel electroluminescent materials |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1325431A CN1325431A (zh) | 2001-12-05 |
| CN1272402C true CN1272402C (zh) | 2006-08-30 |
Family
ID=10841558
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNB998129496A Expired - Fee Related CN1272402C (zh) | 1998-11-02 | 1999-11-02 | 场致发光材料 |
Country Status (11)
| Country | Link |
|---|---|
| US (1) | US7183008B1 (zh) |
| EP (1) | EP1131388A1 (zh) |
| JP (1) | JP4320387B2 (zh) |
| KR (1) | KR20010080930A (zh) |
| CN (1) | CN1272402C (zh) |
| AU (1) | AU754481B2 (zh) |
| BR (1) | BR9915252A (zh) |
| CA (1) | CA2348878A1 (zh) |
| GB (1) | GB9823761D0 (zh) |
| ID (1) | ID28852A (zh) |
| WO (1) | WO2000026323A1 (zh) |
Families Citing this family (23)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB0128074D0 (en) * | 2001-11-23 | 2002-01-16 | Elam T Ltd | Doped lithium quinolate |
| GB9826407D0 (en) | 1998-12-02 | 1999-01-27 | South Bank Univ Entpr Ltd | Novel electroluminescent materials |
| US6366033B1 (en) * | 2000-10-18 | 2002-04-02 | General Electric Company | Molecular lanthanide complexes for phosphor applications |
| GB0028439D0 (en) * | 2000-11-21 | 2001-01-10 | South Bank Univ Entpr Ltd | Elecroluminescent device |
| WO2002075820A1 (en) * | 2001-03-16 | 2002-09-26 | Elam-T Limited | Electroluminescent devices |
| GB0109755D0 (en) | 2001-04-20 | 2001-06-13 | Elam T Ltd | Devices incorporating mixed metal organic complexes |
| WO2002090466A1 (en) * | 2001-05-04 | 2002-11-14 | Elam-T Limited | Electroluminescent devices |
| US8058797B2 (en) | 2001-05-18 | 2011-11-15 | Cambridge University Technical Services Limited | Electroluminescent device |
| TWI303533B (en) * | 2001-06-15 | 2008-11-21 | Oled T Ltd | Electroluminescent devices |
| DE60232415D1 (de) | 2001-06-20 | 2009-07-02 | Showa Denko Kk | Licht emittierendes material und organische leuchtdiode |
| GB0116644D0 (en) | 2001-07-09 | 2001-08-29 | Elam T Ltd | Electroluminescent materials and devices |
| US7303824B2 (en) | 2001-08-04 | 2007-12-04 | Oled-T Limited | Electroluminescent device |
| KR100478522B1 (ko) * | 2001-11-28 | 2005-03-28 | 삼성에스디아이 주식회사 | 유기 화합물 유도체막층을 포함하고 있는 고분자 유기전계 발광 소자 및 그 제조 방법 |
| GB0219253D0 (en) * | 2002-08-19 | 2002-09-25 | Elam T Ltd | Electroluminescent materials and device |
| AU2003290341A1 (en) | 2002-12-24 | 2004-07-22 | Elam-T Limited | Electroluminescent materials and devices |
| US6908045B2 (en) * | 2003-01-28 | 2005-06-21 | Casio Computer Co., Ltd. | Solution spray apparatus and solution spray method |
| CN100349908C (zh) * | 2003-02-14 | 2007-11-21 | 株式会社半导体能源研究所 | 有机金属配合物、及使用其的场致发光材料和场致发光元件 |
| JP2008509238A (ja) | 2004-08-07 | 2008-03-27 | オーエルイーディー−ティー リミテッド | エレクトロルミネセンス物質およびデバイス |
| GB2440368A (en) * | 2006-07-26 | 2008-01-30 | Oled T Ltd | Cathode coating for an electroluminescent device |
| JP5542547B2 (ja) * | 2010-06-29 | 2014-07-09 | 日本ポリエチレン株式会社 | 太陽電池モジュール、太陽電池封止材用組成物及びそれからなる太陽電池封止材 |
| GB201306365D0 (en) | 2013-04-09 | 2013-05-22 | Kathirgamanathan Poopathy | Heterocyclic compounds and their use in electro-optical or opto-electronic devices |
| US11041119B2 (en) | 2017-11-30 | 2021-06-22 | Jonathan Melman | Europium beta-diketonate luminescent material |
| KR20220062026A (ko) * | 2019-09-11 | 2022-05-13 | 크레독시스 게엠베하 | 세륨(iv) 착물 및 유기 전자공학에서의 용도 |
Family Cites Families (38)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS56104986A (en) * | 1980-01-25 | 1981-08-21 | Mitsubishi Chem Ind Ltd | Production of fluorescent material |
| US4356429A (en) | 1980-07-17 | 1982-10-26 | Eastman Kodak Company | Organic electroluminescent cell |
| US4455364A (en) | 1981-11-14 | 1984-06-19 | Konishiroku Photo Industry Co., Ltd. | Process for forming metallic image, composite material for the same |
| DE3375029D1 (en) | 1982-02-22 | 1988-02-04 | Minnesota Mining & Mfg | Protected vapor-deposited metal layers |
| JPS6137887A (ja) | 1984-07-31 | 1986-02-22 | Canon Inc | Ｅｌ素子 |
| JPH0637421B2 (ja) * | 1987-01-14 | 1994-05-18 | 松下電工株式会社 | ユウロピウム系錯体化合物の製造方法 |
| JPS63186844A (ja) | 1987-01-30 | 1988-08-02 | Hitachi Maxell Ltd | 非晶質性材料 |
| US4885211A (en) | 1987-02-11 | 1989-12-05 | Eastman Kodak Company | Electroluminescent device with improved cathode |
| US4720432A (en) | 1987-02-11 | 1988-01-19 | Eastman Kodak Company | Electroluminescent device with organic luminescent medium |
| JP2505244B2 (ja) * | 1988-04-07 | 1996-06-05 | 出光興産株式会社 | 薄膜ｅｌ素子 |
| JP2672325B2 (ja) * | 1988-05-07 | 1997-11-05 | 出光興産株式会社 | 薄膜ｅｌ素子 |
| US5128587A (en) | 1989-12-26 | 1992-07-07 | Moltech Corporation | Electroluminescent device based on organometallic membrane |
| JPH03196493A (ja) * | 1989-12-26 | 1991-08-27 | Mitsui Toatsu Chem Inc | 積層薄膜発光素子 |
| JP3069139B2 (ja) | 1990-03-16 | 2000-07-24 | 旭化成工業株式会社 | 分散型電界発光素子 |
| US5364654A (en) | 1990-06-14 | 1994-11-15 | Idemitsu Kosan Co., Ltd. | Process for production of a thin film electrode and an electroluminescence device |
| JP2828821B2 (ja) * | 1992-01-31 | 1998-11-25 | 三洋電機株式会社 | 電界発光素子 |
| DE69302192T2 (de) | 1992-02-14 | 1996-11-14 | Amersham Int Plc | Fluoreszente Verbindungen |
| EP0688849B1 (en) | 1992-02-14 | 2000-01-12 | Nycomed Amersham plc | Fluorescent compounds |
| EP0569827A2 (en) | 1992-05-11 | 1993-11-18 | Idemitsu Kosan Company Limited | Organic electroluminescence device |
| JPH06145146A (ja) | 1992-11-06 | 1994-05-24 | Chisso Corp | オキシネイト誘導体 |
| FI92897C (fi) * | 1993-07-20 | 1995-01-10 | Planar International Oy Ltd | Menetelmä kerrosrakenteen valmistamiseksi elektroluminenssikomponentteja varten |
| US5834053A (en) * | 1994-11-30 | 1998-11-10 | The Regents Of The University Of California | Blue light emitting thiogallate phosphor |
| US5707745A (en) | 1994-12-13 | 1998-01-13 | The Trustees Of Princeton University | Multicolor organic light emitting devices |
| EP0805143B1 (en) * | 1995-01-19 | 2001-12-05 | Idemitsu Kosan Company Limited | Organic electroluminescent element, organic thin film, and triamine compounds |
| EP0913448B1 (en) | 1995-05-25 | 2003-06-18 | AEA Technology plc | Fluorescent compound |
| DE19627070A1 (de) * | 1996-07-05 | 1998-01-08 | Bayer Ag | Elektrolumineszierende Anordnungen unter Verwendung von Blendsystemen |
| JP3845941B2 (ja) * | 1997-03-25 | 2006-11-15 | 三菱化学株式会社 | イミダゾール金属錯体及びそれを用いた有機電界発光素子 |
| US6025677A (en) * | 1997-04-11 | 2000-02-15 | The Regents Of The University Of California | Blue light emitting thiogallate phosphor including a thin nucleation layer of strontium sulfide |
| JP3832018B2 (ja) * | 1997-04-30 | 2006-10-11 | 東洋インキ製造株式会社 | 有機エレクトロルミネッセンス素子材料およびそれを使用した有機エレクトロルミネッセンス素子 |
| US5882548A (en) * | 1997-05-08 | 1999-03-16 | International Business Machines Corporation | Luminescent organic-inorganic perovskites with a divalent rare earth metal halide framework |
| US5755999A (en) | 1997-05-16 | 1998-05-26 | Eastman Kodak Company | Blue luminescent materials for organic electroluminescent devices |
| GB9711237D0 (en) * | 1997-06-02 | 1997-07-23 | Isis Innovation | Organomettallic Complexes |
| GB9712483D0 (en) | 1997-06-17 | 1997-08-20 | Kathirgamanathan Poopathy | Fabrication of light emitting devices from chelates of transition metals, lanthanides and actinides |
| US5932363A (en) * | 1997-10-02 | 1999-08-03 | Xerox Corporation | Electroluminescent devices |
| JP4514841B2 (ja) | 1998-02-17 | 2010-07-28 | 淳二 城戸 | 有機エレクトロルミネッセント素子 |
| DE19825737A1 (de) * | 1998-06-09 | 1999-12-16 | Bayer Ag | Elektrolumineszierende Anordnungen mit N-Alkyl-2,2'-imino-bis-(8-hydroxychinolin)-Metallkomplexen |
| GB9826405D0 (en) * | 1998-12-02 | 1999-01-27 | South Bank Univ Entpr Ltd | Method for forming films or layers |
| GB9826407D0 (en) * | 1998-12-02 | 1999-01-27 | South Bank Univ Entpr Ltd | Novel electroluminescent materials |
-
1998
- 1998-11-02 GB GBGB9823761.3A patent/GB9823761D0/en not_active Ceased
-
1999
- 1999-11-02 JP JP2000579697A patent/JP4320387B2/ja not_active Expired - Fee Related
- 1999-11-02 WO PCT/GB1999/003619 patent/WO2000026323A1/en not_active Application Discontinuation
- 1999-11-02 BR BR9915252-5A patent/BR9915252A/pt not_active Application Discontinuation
- 1999-11-02 CN CNB998129496A patent/CN1272402C/zh not_active Expired - Fee Related
- 1999-11-02 US US09/830,897 patent/US7183008B1/en not_active Expired - Fee Related
- 1999-11-02 AU AU10562/00A patent/AU754481B2/en not_active Ceased
- 1999-11-02 EP EP99954123A patent/EP1131388A1/en not_active Withdrawn
- 1999-11-02 CA CA002348878A patent/CA2348878A1/en not_active Abandoned
- 1999-11-02 ID IDW00200101115A patent/ID28852A/id unknown
- 1999-11-02 KR KR1020017005447A patent/KR20010080930A/ko not_active Application Discontinuation
Also Published As
| Publication number | Publication date |
|---|---|
| KR20010080930A (ko) | 2001-08-25 |
| ID28852A (id) | 2001-07-05 |
| WO2000026323A1 (en) | 2000-05-11 |
| EP1131388A1 (en) | 2001-09-12 |
| AU1056200A (en) | 2000-05-22 |
| CN1325431A (zh) | 2001-12-05 |
| JP4320387B2 (ja) | 2009-08-26 |
| US7183008B1 (en) | 2007-02-27 |
| GB9823761D0 (en) | 1998-12-23 |
| BR9915252A (pt) | 2001-12-04 |
| AU754481B2 (en) | 2002-11-14 |
| JP2002528633A (ja) | 2002-09-03 |
| CA2348878A1 (en) | 2000-05-11 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN1272402C (zh) | 场致发光材料 | |
| US6717354B1 (en) | Electroluminescent materials | |
| US6312835B1 (en) | Luminescent compounds and methods of making and using same | |
| KR20010013809A (ko) | 전자 발광 물질 | |
| US20130264518A1 (en) | Singlet harvesting with organic molecules for optoelectronic devices | |
| CN1684564A (zh) | 含有金属茂的光－电活性设备和方法 | |
| Gutiérrez et al. | Electroluminescent guest@ MOF nanoparticles for thin film optoelectronics and solid‐state lighting | |
| Kalinowski | Optical materials for organic light-emitting devices | |
| US6565995B1 (en) | Electroluminescent materials | |
| Brannan et al. | Deep‐Blue and Fast Delayed Fluorescence from Carbene‐Metal‐Amides for Highly Efficient and Stable Organic Light‐Emitting Diodes | |
| CN108315010A (zh) | 二苯并吩嗪作为磷光材料的用途及包含二苯并吩嗪的电致发光器件 | |
| Teotonio et al. | Novel electroluminescent devices containing Eu3+-(2-acyl-1, 3-indandionate) complexes with TPPO ligand | |
| CN111690018A (zh) | 一种有机铱金属配合物及其制备方法与应用 | |
| Wang et al. | Intermolecular pi-pi-packing-induced thermally activated delayed fluorescence: a novel pathway toward luminescence efficiency of nearly 100% | |
| Schütz et al. | Exciton dynamics in blends of phosphorescent emitters | |
| CN1288222C (zh) | 磷光发光材料 | |
| MXPA01004402A (en) | Electrolumiscent materials | |
| KR20030044451A (ko) | 전계 발광소자의 발광재료용 플로렌계 중합체 및 이를이용한 전계 발광소자 |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| C10 | Entry into substantive examination | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| ASS | Succession or assignment of patent right |
Owner name: MERCK PATENT GMBH Free format text: FORMER OWNER: SOUTH BANK UNIVERSITY ENTERPRISES CO., LTD. Effective date: 20090515 |
|
| C41 | Transfer of patent application or patent right or utility model | ||
| TR01 | Transfer of patent right |
Effective date of registration: 20090515 Address after: Darmstadt Patentee after: Merck Patent GmbH Address before: London, England Patentee before: South Bank University Enterprises Ltd. |
|
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20060830 Termination date: 20141102 |
|
| EXPY | Termination of patent right or utility model |