CN1108731C - 用于平面有机发光器件的薄膜电极及其制造方法 - Google Patents
用于平面有机发光器件的薄膜电极及其制造方法 Download PDFInfo
- Publication number
- CN1108731C CN1108731C CN98806758A CN98806758A CN1108731C CN 1108731 C CN1108731 C CN 1108731C CN 98806758 A CN98806758 A CN 98806758A CN 98806758 A CN98806758 A CN 98806758A CN 1108731 C CN1108731 C CN 1108731C
- Authority
- CN
- China
- Prior art keywords
- sheet resistance
- layer
- organic light
- luminous
- 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
- 238000000034 method Methods 0.000 title description 17
- 238000004519 manufacturing process Methods 0.000 title description 3
- 239000010409 thin film Substances 0.000 title 1
- 239000010410 layer Substances 0.000 description 41
- 229910052769 Ytterbium Inorganic materials 0.000 description 16
- 239000000758 substrate Substances 0.000 description 15
- NAWDYIZEMPQZHO-UHFFFAOYSA-N ytterbium Chemical compound [Yb] NAWDYIZEMPQZHO-UHFFFAOYSA-N 0.000 description 15
- 239000000463 material Substances 0.000 description 13
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 9
- 238000007747 plating Methods 0.000 description 9
- 238000004528 spin coating Methods 0.000 description 9
- 229910052751 metal Inorganic materials 0.000 description 7
- 239000002184 metal Substances 0.000 description 7
- 229920000728 polyester Polymers 0.000 description 7
- -1 poly (arylene ether Chemical compound 0.000 description 6
- 239000004065 semiconductor Substances 0.000 description 5
- 229910052772 Samarium Inorganic materials 0.000 description 4
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 4
- 238000004020 luminiscence type Methods 0.000 description 4
- 229920000642 polymer Polymers 0.000 description 4
- 238000007738 vacuum evaporation Methods 0.000 description 4
- 238000007740 vapor deposition Methods 0.000 description 4
- QENGPZGAWFQWCZ-UHFFFAOYSA-N Methylthiophene Natural products CC=1C=CSC=1 QENGPZGAWFQWCZ-UHFFFAOYSA-N 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 238000001704 evaporation Methods 0.000 description 3
- 230000008020 evaporation Effects 0.000 description 3
- AMGQUBHHOARCQH-UHFFFAOYSA-N indium;oxotin Chemical compound [In].[Sn]=O AMGQUBHHOARCQH-UHFFFAOYSA-N 0.000 description 3
- 239000011777 magnesium Substances 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 150000004767 nitrides Chemical class 0.000 description 3
- 229920000767 polyaniline Polymers 0.000 description 3
- 229920006267 polyester film Polymers 0.000 description 3
- 238000002360 preparation method Methods 0.000 description 3
- 239000010453 quartz Substances 0.000 description 3
- KZUNJOHGWZRPMI-UHFFFAOYSA-N samarium atom Chemical compound [Sm] KZUNJOHGWZRPMI-UHFFFAOYSA-N 0.000 description 3
- GKWLILHTTGWKLQ-UHFFFAOYSA-N 2,3-dihydrothieno[3,4-b][1,4]dioxine Chemical compound O1CCOC2=CSC=C21 GKWLILHTTGWKLQ-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 229910052684 Cerium Inorganic materials 0.000 description 2
- 229910052693 Europium Inorganic materials 0.000 description 2
- 229910001218 Gallium arsenide Inorganic materials 0.000 description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 2
- 229920001609 Poly(3,4-ethylenedioxythiophene) Polymers 0.000 description 2
- 229910052771 Terbium Inorganic materials 0.000 description 2
- 229910045601 alloy Inorganic materials 0.000 description 2
- 239000000956 alloy Substances 0.000 description 2
- 239000011575 calcium Substances 0.000 description 2
- 229910052729 chemical element Inorganic materials 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 230000005684 electric field Effects 0.000 description 2
- 239000007772 electrode material Substances 0.000 description 2
- 125000005678 ethenylene group Chemical group [H]C([*:1])=C([H])[*:2] 0.000 description 2
- 239000011521 glass Substances 0.000 description 2
- 229910010272 inorganic material Inorganic materials 0.000 description 2
- 239000012528 membrane Substances 0.000 description 2
- 150000002739 metals Chemical class 0.000 description 2
- 239000012044 organic layer Substances 0.000 description 2
- 230000000737 periodic effect Effects 0.000 description 2
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 2
- 238000007639 printing Methods 0.000 description 2
- 241001466460 Alveolata Species 0.000 description 1
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- 229910052692 Dysprosium Inorganic materials 0.000 description 1
- 229910052691 Erbium Inorganic materials 0.000 description 1
- 229910002601 GaN Inorganic materials 0.000 description 1
- 229910005540 GaP Inorganic materials 0.000 description 1
- 229910005542 GaSb Inorganic materials 0.000 description 1
- 229910052688 Gadolinium Inorganic materials 0.000 description 1
- 229910052689 Holmium Inorganic materials 0.000 description 1
- 229910000673 Indium arsenide Inorganic materials 0.000 description 1
- 229910000575 Ir alloy Inorganic materials 0.000 description 1
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 1
- 229910052765 Lutetium Inorganic materials 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- 229910052779 Neodymium Inorganic materials 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- 239000004642 Polyimide Substances 0.000 description 1
- 239000004734 Polyphenylene sulfide Substances 0.000 description 1
- 229910052777 Praseodymium Inorganic materials 0.000 description 1
- BUGBHKTXTAQXES-UHFFFAOYSA-N Selenium Chemical compound [Se] BUGBHKTXTAQXES-UHFFFAOYSA-N 0.000 description 1
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 1
- 229910052775 Thulium Inorganic materials 0.000 description 1
- 150000001225 Ytterbium Chemical class 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- 239000004411 aluminium Substances 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 229910052788 barium Inorganic materials 0.000 description 1
- DSAJWYNOEDNPEQ-UHFFFAOYSA-N barium atom Chemical compound [Ba] DSAJWYNOEDNPEQ-UHFFFAOYSA-N 0.000 description 1
- 229910052790 beryllium Inorganic materials 0.000 description 1
- ATBAMAFKBVZNFJ-UHFFFAOYSA-N beryllium atom Chemical compound [Be] ATBAMAFKBVZNFJ-UHFFFAOYSA-N 0.000 description 1
- 229910052797 bismuth Inorganic materials 0.000 description 1
- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical compound [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- ZMIGMASIKSOYAM-UHFFFAOYSA-N cerium Chemical compound [Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce] ZMIGMASIKSOYAM-UHFFFAOYSA-N 0.000 description 1
- 239000002800 charge carrier Substances 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- GBRBMTNGQBKBQE-UHFFFAOYSA-L copper;diiodide Chemical compound I[Cu]I GBRBMTNGQBKBQE-UHFFFAOYSA-L 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 239000000975 dye Substances 0.000 description 1
- KBQHZAAAGSGFKK-UHFFFAOYSA-N dysprosium atom Chemical compound [Dy] KBQHZAAAGSGFKK-UHFFFAOYSA-N 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- UYAHIZSMUZPPFV-UHFFFAOYSA-N erbium Chemical compound [Er] UYAHIZSMUZPPFV-UHFFFAOYSA-N 0.000 description 1
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 1
- OGPBJKLSAFTDLK-UHFFFAOYSA-N europium atom Chemical compound [Eu] OGPBJKLSAFTDLK-UHFFFAOYSA-N 0.000 description 1
- UIWYJDYFSGRHKR-UHFFFAOYSA-N gadolinium atom Chemical compound [Gd] UIWYJDYFSGRHKR-UHFFFAOYSA-N 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 239000010931 gold Substances 0.000 description 1
- 229910052735 hafnium Inorganic materials 0.000 description 1
- VBJZVLUMGGDVMO-UHFFFAOYSA-N hafnium atom Chemical compound [Hf] VBJZVLUMGGDVMO-UHFFFAOYSA-N 0.000 description 1
- KJZYNXUDTRRSPN-UHFFFAOYSA-N holmium atom Chemical compound [Ho] KJZYNXUDTRRSPN-UHFFFAOYSA-N 0.000 description 1
- 238000005286 illumination Methods 0.000 description 1
- 229910052738 indium Inorganic materials 0.000 description 1
- WPYVAWXEWQSOGY-UHFFFAOYSA-N indium antimonide Chemical compound [Sb]#[In] WPYVAWXEWQSOGY-UHFFFAOYSA-N 0.000 description 1
- RPQDHPTXJYYUPQ-UHFFFAOYSA-N indium arsenide Chemical compound [In]#[As] RPQDHPTXJYYUPQ-UHFFFAOYSA-N 0.000 description 1
- APFVFJFRJDLVQX-UHFFFAOYSA-N indium atom Chemical compound [In] APFVFJFRJDLVQX-UHFFFAOYSA-N 0.000 description 1
- 150000002484 inorganic compounds Chemical class 0.000 description 1
- 239000011147 inorganic material Substances 0.000 description 1
- 229910052746 lanthanum Inorganic materials 0.000 description 1
- FZLIPJUXYLNCLC-UHFFFAOYSA-N lanthanum atom Chemical compound [La] FZLIPJUXYLNCLC-UHFFFAOYSA-N 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- OHSVLFRHMCKCQY-UHFFFAOYSA-N lutetium atom Chemical compound [Lu] OHSVLFRHMCKCQY-UHFFFAOYSA-N 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 229910001092 metal group alloy Inorganic materials 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- QEFYFXOXNSNQGX-UHFFFAOYSA-N neodymium atom Chemical compound [Nd] QEFYFXOXNSNQGX-UHFFFAOYSA-N 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052763 palladium Inorganic materials 0.000 description 1
- 238000001259 photo etching Methods 0.000 description 1
- 238000000206 photolithography Methods 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 229920000139 polyethylene terephthalate Polymers 0.000 description 1
- 239000005020 polyethylene terephthalate Substances 0.000 description 1
- 229920001721 polyimide Polymers 0.000 description 1
- 229920000069 polyphenylene sulfide Polymers 0.000 description 1
- 229920000915 polyvinyl chloride Polymers 0.000 description 1
- 239000004800 polyvinyl chloride Substances 0.000 description 1
- PUDIUYLPXJFUGB-UHFFFAOYSA-N praseodymium atom Chemical compound [Pr] PUDIUYLPXJFUGB-UHFFFAOYSA-N 0.000 description 1
- 229910052761 rare earth metal Inorganic materials 0.000 description 1
- 150000002910 rare earth metals Chemical class 0.000 description 1
- 229910052711 selenium Inorganic materials 0.000 description 1
- 239000011669 selenium Substances 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 239000004332 silver Substances 0.000 description 1
- 238000004544 sputter deposition Methods 0.000 description 1
- 229910052712 strontium Inorganic materials 0.000 description 1
- CIOAGBVUUVVLOB-UHFFFAOYSA-N strontium atom Chemical compound [Sr] CIOAGBVUUVVLOB-UHFFFAOYSA-N 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- GZCRRIHWUXGPOV-UHFFFAOYSA-N terbium atom Chemical compound [Tb] GZCRRIHWUXGPOV-UHFFFAOYSA-N 0.000 description 1
- XOLBLPGZBRYERU-UHFFFAOYSA-N tin dioxide Chemical compound O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 description 1
- 229910001887 tin oxide Inorganic materials 0.000 description 1
- 238000001771 vacuum deposition Methods 0.000 description 1
- 230000000007 visual effect Effects 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
- H05B33/26—Light sources with substantially two-dimensional radiating surfaces characterised by the composition or arrangement of the conductive material used as an electrode
-
- 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
- H10K50/80—Constructional details
- H10K50/805—Electrodes
- H10K50/81—Anodes
- H10K50/813—Anodes characterised by their shape
-
- 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
- H10K50/80—Constructional details
- H10K50/805—Electrodes
- H10K50/82—Cathodes
-
- 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
Abstract
一种场致发光器件，该器件包括至少一个夹在两个电极层(102、104)之间的有机发光层(103)，其中，底部电极层(102)和顶部电极层(104)的表面电阻比r满足0.3≤r≤3。
Description
本发明涉及具有发光层结构的有机发光器件，所述发光层结构形成于一个分层结构中，如果有电流在外加电场的作用下从中通过就会发光，本发明尤其涉及一种有机发光二极管，在其中构制有薄膜电极(阴极和阳极)，后者适合用于大面积的平面有机发光器件。
场致发光器件(此后称为“EL器件”)是这样的一种器件，其中，通过向一种物质尤其是半导体施加电场而使其发光。发光二极管就是一种人所共知的EL器件的例子，其由化学元素周期表中的第III族到第V族元素的无机化合物半导体比如GaAs或者GaP制成。这种器件在可见光波段的长波一侧可有效地发光，被广泛地用于日常的电子设备中。但这种器件的尺寸有限，因此还没有在大面积显示器中得到简便而经济的利用。作为能够大面积生产的一种替代结构，薄膜型EL器件是众所周知的，其由无机材料制成，具体来说是这样制造的：用用作发光源(light-emitting center)的Mn或者稀土金属例如Eu、Ce、Tb或者Sm，对由化学元素周期表中的第II到第IV族元素形成的半导体化合物比如ZnS、CaS和SrS进行搀杂。但是，为了制造利用所述无机半导体的EL器件，需要使用交流电和高电压，因此这样的EL器件比较昂贵，而且，也难以获得全彩色发光器件。
为了解决上述问题，已对利用一种有机薄膜的EL器件进行了广泛的研究。例如，这种EL器件包括使用一种有机发光(荧光)染料的汽相淀积薄膜的EL器件，这样的EL器件在下述文献中有报导：
S.Hayashi等，J.Appl.Phys.25，L773(1986)
C.W.Tang等，Appl.Phys.Lett.，51，913(1987)
迄今，已经开发出了发蓝色到红色光的有机EL器件。有机场致发光的细节例如在下述文献中有说明：
″有机EL器件发展策略″，由Next Generation Display DeviceResearch Association编辑，Science Forum(1992年出版)
″场致发光材料、器件和大屏幕显示器″，SPIE Proceedings Vol.1910(1993)，E.M.Conwell and M.R.Miller
另外，近年来，例如用旋涂或者镀膜法(spin coating or coating)制造薄膜的技术得到了一些改进，并已研究出了使用热稳定的聚(亚芳基乙烯撑)(poly(arylene vinylene))聚合物的EL器件。这样的使用聚亚芳基乙烯撑聚合物的EL器件例如在下述文献中有说明：
WO-A 90/13148
Burroughes，Nature，347，539(1990)
D.Braun，Appl.Phys.Lett.，58，1982(1991)
但是，到目前为止所报导的所有高性能器件的有效器件面积的尺寸都比较小(例如2mm×2mm)。传统的有机发光器件的主要的缺点之一是难以实现高效的大面积平面显示。如果将发光面积增大，则器件的性能将急剧降低，使得器件寿命缩短，甚至导致短路而不能发光。
到目前为止，场致发光器件是由场致发光层夹在一个金属阴极和在衬底上实现的透明导电阳极之间构成的。
在这样的例如Mg：Ag阴极中，表面电阻约为0.5Ω/方(square)，其与透明导电阳极的10到100Ω/方的表面电阻相比，要小一个数量级以上。
现在，我们惊异地发现，如果在阴极和阳极的表面电阻之间保持一个特定的比例，EL器件的寿命和EL性能就可以得到改善。
因此，本发明的一个方面是提供一种EL器件，该器件包括至少一个夹在两个电极层之间的有机发光层，其特征在于底部电极层和顶部电极层的表面电阻比r满足0.3≤r≤3。
本发明的EL器件除了别的特征以外，其中部分特征是，外加电压在器件平面上均匀分布，电流也在整个器件的面积上均匀分布，并且发光效率和器件寿命都得到提高。
在一个优选实施例中，所述底部电极层和顶部电极层的表面电阻比r满足0.5≤r≤2，尤其是0.8≤r≤1.2。
首先参看图1，本发明的一种场致发光器件100依次包括一个衬底101、一个底部电极层102、一个有机层结构103和一个顶部电极层104。
衬底101是透明的，例如由下述材料制成：玻璃、石英玻璃、陶瓷、聚合物，比如聚酰亚胺、聚酯、聚对苯二甲酸乙酯、聚碳酸酯、聚乙烯和聚氯乙烯。所述衬底也可以是不透明的，例如由从下述材料中选择的单晶半导体制成：无搀杂、轻搀杂或者重搀杂的Si、Ge、GaAs、GaP、GaN、GaSb、InAs、InP、InSb，以及AlxGa1-xAs(x从0到1)或者其他任何III/V半导体。
当阳极的电势高于阴极时，场致发光器件100可以被视为正偏的二极管。在这样的条件下，底部电极层102用作空穴(正电荷载体)注入阳极，此时，该底部电极层最好由高功函数材料制成，例如镍、金、铂、钯、硒、铱或者前述元素任意组合的合金，氧化锡、氧化锡铟(ITO，indium tin oxide)或者碘化铜，以及导电的聚合物，比如聚(3-甲基噻吩)(poly(3-methylthiophene))、聚苯硫，或者聚苯胺(PANI)，或者聚3，4-亚乙二氧基噻吩(PEDOT，poly-3，4-ethylene dioxythiophene)。这些材料可以独立使用，或者将两种或多种材料层叠起来，例如在ITO上镀上PANI或者PEDOT膜。所述电极层的表面电阻最好小于100Ω/方，尤其是小于30Ω/方。
另一方面，顶部电极层104可用作电子注入阴极，此时，该顶部电极由功函数较低(与所述底部电极层相比)的材料制成，最好是一种金属或者金属合金，例如锂、铝、铍、镁、钙、锶、钡、镧、铪、铟、铋、铈、镨、钕、钐、铕、钆、铽、镝、钬、铒、铥、镱、镥，以及前述元素任意组合的合金，或者这些金属中的一种与另一种金属的合金。所述电极层的表面电阻最好小于100Ω/方，尤其是小于30Ω/方。
按照本发明，底部电极层102和顶部电极层104具有不相上下的表面电阻。实现这种目的的技术手段对于本领域技术人员来说是众所周知的，下面对这些技术手段作进一步说明。
例如，所述表面电阻比可以这样实现：改变任何一个电极的厚度，或者同时改变两个电极的厚度，所述厚度最好是从0.1nm到1000nm，尤其是从1nm到400nm。可以进行这种变化是因为存在下述公式：
R[Ω/方]＝ρ[Ω·cm]/d[cm]
其中R为表面电阻，ρ为材料电阻率，d为层厚。例如，一种钐电极(ρ(钐)＝9×10-7Ω·m)的表面电阻随层厚的变化如下：
| 层厚[nm] | 表面电阻[Ω/方] |
| 10 | 90 |
| 50 | 18 |
| 100 | 9 |
| 200 | 4.5 |
所述表面电阻比也可以通过在10-4到10-10mbar的范围内改变电极层的蒸镀背景压强而实现。用这种方法，可以改变在蒸镀过程中存在的水分和氧气或氮气或两种气体的量，从而导致(基于所用的金属)所形成的金属氧化物或氮化物的量的变化，对于恒定的层厚，所述氧化物或者氮化物具有更高的表面电阻。用这种方法，某种选定的金属的表面电阻可以在一个宽广的范围内调适。例如，可以用这种方法控制镱的表面电阻如下：(p：蒸镀背景压强[mbar]；层厚：150nm)
| 背景压强[mbar] | 表面电阻[Ω/方] |
| 1.3×10-6mbar | 2 |
| 5.9×10-6mbar | 3 |
| 2.8×10-6mbar | 5 |
| 6.5×10-6mbar | 15 |
| 8.4×10-6mbar | 120 |
所述表面电阻比也可以通过使用某种电极材料而得到满足，所述电极材料本身(与其电阻率有关)即可实现所需的表面电阻。下表罗列了一些可用于低功函数电极的有用的金属：
| 金属 | 功函数[eV vs.vac] | 层厚100nm时的R[Ω/方] |
| Li | 2.9 | 0.9 |
| Be | 5.1 | 0.5 |
| Mg | 3.7 | 0.5 |
| Ca | 2.9 | 0.3 |
| Sr | 2.6 | 2.3 |
| Ba | 2.7 | 5.0 |
| La | 3.5 | ～7.0 |
| Ce | 2.9 | 7.5 |
| Pr | 2.7 | 6.8 |
| Nd | 3.2 | 6.4 |
| Sm | 2.7 | 9.2 |
| Eu | 2.5 | 8.1 |
| Gd | 3.1 | 13.4 |
| Tb | 3.0 | 11.6 |
| Dy | 3.1 | 9.1 |
| Ho | 3.1 | 9.4 |
| Er | 3.2 | 8.6 |
| Tm | 3.2 | 9.0 |
| Yb | 2.7 | 2.8 |
| Lu | 3.3 | 6.8 |
| Al | 4.3 | 0.3 |
| Ga | 4.2 | 2.7 |
| In | 4.2 | 0.8 |
| Tl | 3.9 | 1.8 |
| Sn | 4.4 | 1.1 |
| Pb | 4.3 | 2.0 |
| Sb | 4.5 | 4.2 |
| Bi | 4.3 | 12.0 |
另外，所述表面电阻比可以通过共同蒸镀任意组合的两种或多种金属而实现。用这种方法，可以，例如，以一种容易再现的方式生成氧化物或氮化物(见上)。
在本发明的另一方面，所述表面电阻比也可以通过下述方式实现：在具有较高表面电阻的电极上以任意几何形状建构一种高导电性材料，所述几何形状例如为若干条直线、一种网格，或者一种蜂窝状结构。这种材料可以用任何已知的制备微结构的方法加工到所述电极上，所述方法比如是光刻法(photolithography)、印制(printing)、化学镀或者电镀。例如，通过添加小银条(厚100nm；宽1μm；间距10μm)，10Ω/方的ITO的表面电阻可以降到约1-2Ω/方。用这种方法，ITO的透明度仅降低10％，但其表面电阻可以降低5倍多。
还有，在用作阳极和阴极的材料中，在器件所发光的波段内，至少要有一个电极的材料最好能透过50％以上的光。
用在本发明的有机发光二极管中的所述阳极、阴极和有机层可以用已知的传统方法实现，例如真空淀积、旋涂、阴极溅镀或者凝胶-溶胶法(gel-sol method)。
本发明的EL器件的其他部件可以从现有技术中已有的部件中选用，例如US 4 539 507(Kodak)、EP-A 0 423 283、EP-A 0 443 861或者前文所引参考文献所述者。借助于用作发光层的化合物，可以改变所发光的颜色。
场致发光器件可以用作，例如自照明主动式显示元件，比如控制信号灯、字母数字显示器、高信息容量的矩阵显示器、信息标牌，并可用于光电耦合器中。
下面举例对本发明加以说明，但本发明并不限于这些例子。
例1
镀有氧化锡铟(ITO)的聚酯(PET)膜用作衬底。该聚酯膜是这样制造的：在挠性的透明PET上溅镀一薄层ITO，该ITO中Sn的浓度为20-30％(原子百分数)。所述镀ITO的PET衬底的表面电阻为50Ω/方，可见光透明度为80％。在向所述衬底镀覆有机场致发光层之前，将衬底清洗干净。用旋涂法制得厚度为100nm的活性层103。旋涂所用的是PPV共轭衍生物(conjugated PPV derivative)聚(2-甲氧基-5-(3，7-二甲基辛氧基)-p-次苯基乙烯撑)(poly[2-methoxy-5-(3，7-dimethyloctyloxy)-p-phenylene vinylene])的甲苯溶液，浓度为0.3-0.8％(重量)。镱电极104真空蒸镀时的压强为1×10-6mbar，汽相淀积速率为1nm/sec。所述镱层形成厚40nm的膜，所述膜厚使用校正石英晶体振荡器加以监控。所述表面电阻值用四点法进行测量。结果得到31.3Ω/方的表面电阻值。所述镱层与ITO层的表面电阻比为0.63。器件的发光效果是这样的：电流密度为7mA/cm2时，发光密度为100Cd/m2。器件所发光的颜色为橙色到红色。
比较例1
镱电极104以例1所述同样的方式进行真空蒸镀，但镱膜的厚度为150nm，背景压强为5×10-7mbar。用四点法测得的表面电阻值为2.5Ω/方。该镱层与ITO层的表面电阻比r为0.05。所有有效面积大于2mm×2mm的器件都短路而不发光。
例2
用镀ITO的聚酯膜作为衬底。该聚酯膜是这样制造的：在挠性的透明PET上溅镀一薄层ITO，该ITO中Sn的浓度为7-11％(原子百分数)。所述镀ITO的PET衬底的表面电阻为25Ω/方，可见光透明度为75％。在向所述衬底镀覆有机场致发光层之前，将衬底清洗干净。用旋涂法制得厚度为100nm的活性层103。旋涂所用的是PPV共轭衍生物聚(2-甲氧基-5-(3，7-二甲基辛氧基)-p-次苯基乙烯撑)的甲苯溶液，浓度为0.3-0.8％(重量)。镱电极104真空蒸镀时的压强为1×10-6mbar，汽相淀积速率为1nm/sec。所述镱层形成厚50nm的膜，所述膜厚使用校正石英晶体振荡器加以监控。所述表面电阻值用四点法进行测量。结果得到20Ω/方的表面电阻值。所述镱层与ITO层的表面电阻比为0.8。器件发光的量子效率为1.8-2.0％。
例3
用镀ITO的玻璃作为衬底。ITO膜的表面电阻为10Ω/方，可见光透明度为75％。在向所述衬底镀覆有机场致发光层之前，将衬底清洗干净。用旋涂法制得厚度为100nm的活性层103。旋涂所用的是PPV共轭衍生物聚(2-甲氧基-5-(3，7-二甲基辛氧基)-p-次苯基乙烯撑)的甲苯溶液，浓度为0.3-0.8％(重量)。镱电极104真空蒸镀时的压强为1×10-6mbar，汽相淀积速率为1nm/sec。所述镱层形成厚80nm的膜，所述膜厚使用校正石英晶体振荡器加以监控。所述表面电阻值用四点法进行测量。结果得到9.9Ω/方的表面电阻值。所述镱层与ITO层的表面电阻比为0.99。器件发光的量子效率为2-2.5％。
例4
按照例3所述的方法制备两个发光器件(LED)。器件A的面积为4mm2，器件B的面积为9cm2。两个器件均发光均一，具有在例3所给范围内的发光量子效率。在发光量子效率、亮度和发光均一性方面，没有发现两个器件之间存在明显的差别。
比较例4
按照例4所述制备两个发光器件(器件A，4mm2；器件B，9cm2)，与例4相比只有一点不同：其中的镱阴极按照比较例1所述的方法制备。此时，镱层与ITO层的表面电阻比r为0.25。器件A具有与例4中的器件A相同的性能。器件B的发光量子效率降低到0.8-1.2％，且发光不均一(亮度在整个面积上的变化超过3倍，肉眼明显可见)。
Claims (2)
1.一种场致发光器件，该器件包括至少一个夹在两个电极层(102，104)之间的有机发光层(103)，其特征在于底部电极层(102)和顶部电极层(104)的表面电阻比r满足0.3≤r≤3。
2.将权利要求1所述的场致发光器件用于自照明主动式显示元件以及光电耦合器中。
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| EP97110656A EP0924966A1 (en) | 1997-06-30 | 1997-06-30 | Thin film electrode for planar organic light-emitting devices and method for its production |
| DE97110656.2 | 1997-06-30 |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1262024A CN1262024A (zh) | 2000-08-02 |
| CN1108731C true CN1108731C (zh) | 2003-05-14 |
Family
ID=8226979
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN98806758A Expired - Fee Related CN1108731C (zh) | 1997-06-30 | 1998-06-22 | 用于平面有机发光器件的薄膜电极及其制造方法 |
Country Status (7)
| Country | Link |
|---|---|
| US (1) | US6414431B1 (zh) |
| EP (2) | EP0924966A1 (zh) |
| JP (1) | JP2002507319A (zh) |
| KR (1) | KR100732350B1 (zh) |
| CN (1) | CN1108731C (zh) |
| DE (1) | DE69815349T2 (zh) |
| WO (1) | WO1999002017A1 (zh) |
Families Citing this family (25)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB9907931D0 (en) * | 1999-04-07 | 1999-06-02 | Univ Edinburgh | An optoelectronic display |
| CN1263168C (zh) * | 2000-06-29 | 2006-07-05 | 皇家菲利浦电子有限公司 | 光电元件和用发光层覆盖光电元件的方法 |
| SG169230A1 (en) * | 2002-08-02 | 2011-03-30 | Idemitsu Kousan Co Ltd | Sputtering target, sintered body, conductive film formed by using them, organic el device, and substrate used for the organic el device |
| US6949403B2 (en) * | 2003-07-22 | 2005-09-27 | Organic Vision Inc. | Non-vacuum methods for the fabrication of organic semiconductor devices |
| US7772756B2 (en) | 2003-08-01 | 2010-08-10 | Semiconductor Energy Laboratory Co., Ltd. | Light-emitting device including a dual emission panel |
| TWI246783B (en) * | 2003-09-24 | 2006-01-01 | Matsushita Electric Works Ltd | Light-emitting device and its manufacturing method |
| TWI386103B (zh) * | 2004-06-11 | 2013-02-11 | Organic electroluminescent element and its driving method | |
| JP2010503166A (ja) * | 2006-09-07 | 2010-01-28 | サン−ゴバン グラス フランス | 有機発光デバイス用基板、基板の使用法およびを製造プロセス、ならびに有機発光デバイス |
| WO2008059185A2 (fr) * | 2006-11-17 | 2008-05-22 | Saint-Gobain Glass France | Electrode pour dispositif electroluminescent organique, sa gravure acide, ainsi que dispositif electroluminescent organique l'incorporant |
| FR2913146B1 (fr) * | 2007-02-23 | 2009-05-01 | Saint Gobain | Electrode discontinue, dispositif electroluminescent organique l'incorporant, et leurs fabrications |
| FR2924274B1 (fr) | 2007-11-22 | 2012-11-30 | Saint Gobain | Substrat porteur d'une electrode, dispositif electroluminescent organique l'incorporant, et sa fabrication |
| FR2925981B1 (fr) * | 2007-12-27 | 2010-02-19 | Saint Gobain | Substrat porteur d'une electrode, dispositif electroluminescent organique l'incorporant. |
| FR2936358B1 (fr) | 2008-09-24 | 2011-01-21 | Saint Gobain | Procede de fabrication d'un masque a ouvertures submillimetriques pour grille electroconductrice submillimetrique, masque a ouverture submillimetriques, grille electroconductrice submillimetrique. |
| FR2936362B1 (fr) | 2008-09-25 | 2010-09-10 | Saint Gobain | Procede de fabrication d'une grille submillimetrique electroconductrice revetue d'une grille surgrille, grille submillimetrique electroconductrice revetue d'une surgrille |
| KR20120025455A (ko) * | 2009-03-26 | 2012-03-15 | 코닌클리즈케 필립스 일렉트로닉스 엔.브이. | 전계 발광 장치 및 세그먼트형 조명 장치 |
| FR2944145B1 (fr) | 2009-04-02 | 2011-08-26 | Saint Gobain | Procede de fabrication d'une structure a surface texturee pour dispositif a diode electroluminescente organique et structure a surface texturee |
| JP2009302071A (ja) * | 2009-09-29 | 2009-12-24 | Idemitsu Kosan Co Ltd | 有機ｅｌ素子及びそれに用いる基板 |
| FR2955575B1 (fr) | 2010-01-22 | 2012-02-24 | Saint Gobain | Substrat verrier revetu d'une couche haut indice sous un revetement electrode et dispositif electroluminescent organique comportant un tel substrat. |
| WO2011096922A1 (en) * | 2010-02-03 | 2011-08-11 | Universal Display Corporation | Organic light emitting device with enhanced emission uniformity |
| FR2985379B1 (fr) | 2011-12-30 | 2014-01-24 | Saint Gobain | Dispositif oled a emission par l'arriere |
| FR2985380B1 (fr) | 2011-12-30 | 2014-07-11 | Saint Gobain | Dispositif oled a emission par l'arriere |
| FR2985378B1 (fr) * | 2011-12-30 | 2014-01-24 | Saint Gobain | Dispositif oled a emission par l'arriere, et procede d'homogeneisation de la luminance d'un dispositif oled a emission par l'arriere |
| US9722208B2 (en) | 2014-12-31 | 2017-08-01 | Konica Minolta Laboratory U.S.A., Inc. | Light-emitting devices using thin film electrode with refractive index optimized capping layer for reduction of plasmonic energy loss |
| WO2017023440A1 (en) | 2015-08-05 | 2017-02-09 | Proteq Technologies Llc | Light-emitting device |
| KR102601451B1 (ko) * | 2016-09-30 | 2023-11-13 | 엘지디스플레이 주식회사 | 전극 및 이를 포함하는 유기발광소자, 액정표시장치 및 유기발광표시장치 |
Family Cites Families (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| NL6415164A (zh) * | 1964-01-02 | 1965-07-05 | ||
| JPS59226500A (ja) * | 1983-06-04 | 1984-12-19 | アルプス電気株式会社 | 分散型エレクトロルミネツセンス |
| US4885211A (en) * | 1987-02-11 | 1989-12-05 | Eastman Kodak Company | Electroluminescent device with improved cathode |
| JPH02305886A (ja) * | 1989-05-19 | 1990-12-19 | Nec Corp | 有機薄膜ｅｌ素子 |
| US5061569A (en) * | 1990-07-26 | 1991-10-29 | Eastman Kodak Company | Electroluminescent device with organic electroluminescent medium |
| JPH04117485A (ja) * | 1990-09-07 | 1992-04-17 | Idemitsu Kosan Co Ltd | エレクトロルミネッセンス素子 |
| JPH05343183A (ja) * | 1992-06-10 | 1993-12-24 | Hitachi Ltd | 有機薄膜ｅｌ素子 |
| JP3242992B2 (ja) * | 1992-06-17 | 2001-12-25 | パイオニア株式会社 | 有機エレクトロルミネッセンス素子 |
| JPH0796278B2 (ja) * | 1992-09-08 | 1995-10-18 | コニカ株式会社 | 透明導電性積層体の製造方法 |
| JPH06157036A (ja) * | 1992-11-13 | 1994-06-03 | Nippon Soda Co Ltd | スズドープ酸化インジウム膜の高比抵抗化方法 |
| JPH07320868A (ja) * | 1994-05-24 | 1995-12-08 | Yazaki Corp | 電場発光素子およびその製造方法 |
-
1997
- 1997-06-30 EP EP97110656A patent/EP0924966A1/en not_active Withdrawn
-
1998
- 1998-06-22 WO PCT/EP1998/003806 patent/WO1999002017A1/en not_active Application Discontinuation
- 1998-06-22 DE DE69815349T patent/DE69815349T2/de not_active Expired - Lifetime
- 1998-06-22 JP JP50625599A patent/JP2002507319A/ja active Pending
- 1998-06-22 CN CN98806758A patent/CN1108731C/zh not_active Expired - Fee Related
- 1998-06-22 US US09/446,744 patent/US6414431B1/en not_active Expired - Fee Related
- 1998-06-22 EP EP98938623A patent/EP0997058B1/en not_active Expired - Lifetime
- 1998-06-22 KR KR1019997012466A patent/KR100732350B1/ko not_active IP Right Cessation
Also Published As
| Publication number | Publication date |
|---|---|
| DE69815349T2 (de) | 2004-04-29 |
| US6414431B1 (en) | 2002-07-02 |
| EP0997058B1 (en) | 2003-06-04 |
| EP0924966A1 (en) | 1999-06-23 |
| WO1999002017A1 (en) | 1999-01-14 |
| KR20010014324A (ko) | 2001-02-26 |
| DE69815349D1 (de) | 2003-07-10 |
| JP2002507319A (ja) | 2002-03-05 |
| CN1262024A (zh) | 2000-08-02 |
| EP0997058A1 (en) | 2000-05-03 |
| KR100732350B1 (ko) | 2007-06-27 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN1108731C (zh) | 用于平面有机发光器件的薄膜电极及其制造方法 | |
| Yang et al. | Enhanced performance of polymer light‐emitting diodes using high‐surface area polyaniline network electrodes | |
| EP0727100B1 (en) | Electroluminescent device comprising a poly-3,4-dioxythiophene layer | |
| Gao et al. | Soluble polypyrrole as the transparent anode in polymer light-emitting diodes | |
| EP0947123B1 (en) | Electroluminescent devices with electrode protection | |
| US6866946B2 (en) | High resistance polyaniline useful in high efficiency pixellated polymer electronic displays | |
| KR101261633B1 (ko) | 유기 전자 장치를 위한 금속 화합물-금속 다층 전극 | |
| US6706551B2 (en) | Thin film inorganic light emitting diode | |
| AU725250B2 (en) | Polymer light emitting diode | |
| EP1231251A1 (en) | Thin film inorganic light emitting diode | |
| JP2003505823A (ja) | 発光効率および放射輝度が向上した長寿命の重合体発光素子 | |
| KR20020069199A (ko) | 고효율 픽셀화 중합체 전자 디스플레이에 유용한 고저항의폴리아닐린 | |
| Yu et al. | Planar light-emitting devices fabricated with luminescent electrochemical polyblends | |
| US7737622B2 (en) | Light emitting element with semiconductive phosphor | |
| Pal et al. | Polymeric light‐emitting diodes from molecularly thin poly (3‐hexylthiophene) Langmuir–Blodgett films | |
| EP0793900A1 (en) | Electroluminescent device and a way to fabricate it | |
| WO2005004547A1 (ja) | 発光素子及び表示装置 | |
| JP2003501795A (ja) | 発光デバイス | |
| JP2837171B2 (ja) | 透明導電性フィルム | |
| Romero et al. | Light-emitting diodes based on copolymer organic semiconductors | |
| Ficke et al. | The bright future of organic LEDs | |
| JP3137631B2 (ja) | 発光素子 | |
| TRANSPARENT et al. | Staring et 81. | |
| Wang et al. | Application of Polymers to Electroluminescence |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| 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: COVION ORGANIC SEMICONDUCTORS GMBH Free format text: FORMER OWNER: AVENTIS RESEARCH + TECHNOLOGY GMBH + CO. KG Effective date: 20060324 |
|
| C41 | Transfer of patent application or patent right or utility model | ||
| TR01 | Transfer of patent right |
Effective date of registration: 20060324 Address after: Frankfurt, Germany Patentee after: COVION ORGANIC SEMICONDUCTORS GmbH Address before: Frankfurt, Germany Patentee before: AVENTIS RESEARCH & TECHNOLOGIES GmbH & Co.KG |
|
| ASS | Succession or assignment of patent right |
Owner name: MERCK PATENT GMBH Free format text: FORMER OWNER: MERCK ODED MATERIALS CO., LTD. Effective date: 20070202 |
|
| C41 | Transfer of patent application or patent right or utility model | ||
| C56 | Change in the name or address of the patentee |
Owner name: MERCK ODED MATERIALS CO., LTD. Free format text: FORMER NAME OR ADDRESS: COVION ORGANIC SEMICONDUCTORS GMBH |
|
| CP03 | Change of name, title or address |
Address after: Frankfurt, Germany Patentee after: Merck Olide Materials Co.,Ltd. Address before: Frankfurt, Germany Patentee before: COVION ORGANIC SEMICONDUCTORS GmbH |
|
| TR01 | Transfer of patent right |
Effective date of registration: 20070202 Address after: Darmstadt Patentee after: MERCK PATENT GmbH Address before: Frankfurt, Germany Patentee before: Merck Olide Materials Co.,Ltd. |
|
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20030514 Termination date: 20140622 |
|
| EXPY | Termination of patent right or utility model |