TW493289B - Long lifetime polymer light-emitting devices with high luminous efficiency and high radiance - Google Patents

Abstract

The luminous efficiency and radiance of light emitting diodes (LEDs) fabricated from organic emissive materials can be increased by using a multilayer cathode including a low work function layer and a high work function high reflectivity layer, in combination with a high work function, high reflectivity anode material in the device.

Description

493289 A7 ---------- --_ Β7 ____ V. Description of the invention (1) ~~: The collar of the invention

The present invention relates to an organic photodiode with improved luminous efficiency and improved irradiation. · Milk I related technology is described in the following three parts: "Composite layers made of diodes, # material photodiodes (LEDs) because of their potential use in the display caused by heavy &. The standard polymer LED structure includes the following layers of contact sequence: indium oxide tin (tin) coating 4 substrate, passivation layer, light-emitting polymer, followed by a single-layer cathode. In the range of organic polymer-based LEDs, higher working function metals are often used as anodes for the injection of semiconductive electroluminescent polymers and other filled π-light band holes. The relatively low working function metal rhenium is used as the cathode material, and the injection-electron enters the other full π * _ band of the semi-conductive electroluminescent polymer. The holes injected at the anode and the cathode are radiatively recombined in the active layer to emit light. Typical higher work function materials for anode materials include transparent conductive films of indium oxide / tin. Alternatively, a conductive emerald salt type polyaniline film can be used. The hafnium oxide / tin film and the conductive emerald salt polyaniline film are more commonly used, because when used as transparent electrodes, both allow the device to emit an effective amount of light from the LED. Typical lower work function metals suitable as cathode materials are such as calcium, magnesium and barium. Salty metals are prone to move too much, and they are used to coat the light-emitting layer (such as electroluminescent polymer), which causes short-circuit and unqualified short-term installation life. -

It is known in the art that ultra-thin layers or low-working low-working-function metal [see CaO, Y; PCT WO 98/57381 and Pichler, K., International-International Patent Electronic Reading Case WO 98/10621]. Functional metal oxides [Ca〇, γ ·; PCT application No. 99 US / 23775] in the form of ultra-thin layers can produce LED contributions that can be compared or better. -4- This paper size applies Chinese National Standards (CNS) A4 specification (21〇X 297 public love) (Please read the precautions on the back and write this page first) Pack -1 line. Printed by the Consumer Cooperative of Intellectual Property Bureau of the Ministry of Economic Affairs

V. Description of the invention (2) The similar performance of the printed cathodes (such as brightness and efficiency) in the consumer co-operatives of the Intellectual Property Bureau of the Ministry of Economic Affairs is similar to that of the LEDs. The long-term operation is better than the traditional thick film. Result example; = 's efficiency is sufficient for some display purposes. But in; private {home in the light-emitting government rate system: critical parameters. High light-emitting efficiency straight = long pass-through problem without having to charge the battery. More Commonly, the luminous efficiency is wider than the practical range of display. Therefore, the efficiency of 2 is necessary! The specific material M should be tapered in the forward direction. The high rolling degree is particularly important in such applications. Off-LED , Including-including the first cathode layer with high reflectivity and: number: translucent, and-containing at least one low step function material selected from the group consisting of metals, metal oxides :::, and temple compounds, and at least A directional reflectivity and high work function of the first: the cathode layer. Transparent: :: to improve the luminous efficiency and improve the irradiation. The first-specific examples of semi-transparent: layer: Gedi second cathode layer has a reflectance of at least 91.4% and Working function

Vv. In the second specific example, the translucent layer and / or the second cathode layer have a reflectivity of. Ί :: 二 彻 ⑽ 与 50. nm emission wavelength. In the preferred embodiment, both the translucent layer and the second cathode layer are silver. The expression ‘’ adjacency here does not necessarily mean that one or several intermediate layers can be set between one. Floor. So, the term "reflectivity at the emission wavelength ..." in Zheng layer text refers to the reflectance of a layer at a specific length. The wavelength of the cited reflectance is the sharp emission from the device. The reflectivity is not From the standard book J. H Weaver, H Μ --- 1 .-- I J ------- install ... (Please read the note on the back to write this page first)-line. This paper size Shicaiguan Family Mark ^ 7cNS) A4 Specification ⑽χ 2 ^^ 493289 Printed by A7 B7, Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs V. Invention Description (3)! ^ (^ 1 * 丨 1 ^ 01 (: Take 11〇113) (^ Pages 12-117, "Metal and semiconductor properties, found in the table.-" The term "translucent, defined here as able to transmit at least some light," preferably at about 4% and 2 of the specific wavelength. The amount of light between 5%. Brief description of the figure U? / Schematic diagram of the configuration of a polymer LED device of the present invention. Not to scale 0 Figure 2 shows the human eye's sensitivity to light as a function of wavelength. Figure 3 shows A comparison of the electrical lighting spectrum of a polymer LED, 〆 and LbD are made with COWon PD0 122, and there is an IT0 electrode and a _Ba / A 丨 electrode (that is, Comparative Example A).-..., Figure 4 shows the first invention polymerization The electrical lighting spectrum of the LED has -300 A silver anode and a Ba / Ag electrode (ie, Example 3). Figure 5 shows the electrical lighting spectrum of a control polymer LED, which is made with CoViOnPDY 131 and has a The IT0 electrode and the electrode are the same as in Example C.…, Figure 6 shows the electrical lighting spectrum of a polymer LED of the present invention. It is made using covion PDY m, and has a 300A silver anode and a Ba / Ag electrode (ie, 4) 0, Figure 7 shows the brightness versus voltage curve of the device according to Example 4 and Comparative Example c: the standard line of the line. "'The best specific example is best shown in Figure 1, an LED device 100 includes a substrate 11 〇 and anode anode 120 contains a highly reflective metal translucent layer 122 and _ random passivation layer-6 ----- Γ .---- ^ ------- install --- (Please read first Note on the reverse side of this page)-· Line-This paper size is applicable to the national standard of China (210 XA Lane 493289 A7 B7 Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs V. Invention Note (4) 128. Translucent The layer 122 has a first surface 124 adjacent to the substrate 110 and an opposite second surface 126. At least one emitting layer 130 is disposed between the anode 12o and the cathode 14o. The cathode 140 contains The first cathode layer M2 of a low work function substance and the second cathode layer 144 of a highly reflective metal. Light is emitted through the substrate 110 as shown by arrow 150. The substrate 'Suitable materials that can be used for the substrate 110 include, for example, glass and Polymer film Although the conventional anode electrode uses a transparent electrode such as IT0 on the side of the light emitting device to reduce transmission loss through the electrode, the present invention uses a thin layer of high reflectivity metal layer i26 to replace or increase the transparent electrode to lift the device. Rate. As can be clearly seen in the figure, the anode 120 can be a composite layer composed of a semi-transparent layer 126 and a passivation layer 128 coated with a conductive polymer on the second surface 124 of the semi-transparent layer 126. In the first alternate embodiment (not shown), the anode contains only a conductive current-carrying layer and can be used as a perforation layer without a passivation layer. In a second alternative (not shown), the anode contains a transparent conductive layer such as IT0 adjacent to the first side of the translucent layer 126 and the passivation layer 128. In the third specific example (not shown), the inner anode contains a transparent conductive layer such as nro adjacent to the first surface 124 of the translucent layer 126 without a passivation layer. The composite electrode 120 or other translucent layer 126 of a single anode layer (not shown) is made of an anode material selected from a high reflectance metal group with an internal working function (typically about 4.0 eV). Examples of suitable metals include fluorine, gold, aluminum and copper. A preferred specific inner translucent layer 126 is good if its reflectance is at least 914% at the emission wavelength = bulk (having a conductivity from about 102 to about 108 irWl). 4 can form a smooth joint. The second preferred embodiment is half. The transparent layer has about 92% or more at the wavelength emission.

(Please read the note on the back first to write this page) Assembly · 丨 Line-493289 A7

5. Description of the invention (5) Reflectivity. In the third preferred embodiment, the translucent layer has a reflectance between about 92% and about 96.5% at the wavelength emission. In the fourth preferred embodiment, the translucent layer has a reflectance at the wavelength emission between about 94% and about 965%. In the fifth preferred embodiment, the translucent layer 126 has a reflectance at the wavelength emission of greater than about 96%. In another preferred embodiment, the translucent layer 126 has a reflectance of at least s6% at an emission wavelength of 400 to 5000 nm. Examples of these materials include silver, aluminum, gold and copper, and alloys of these metal layers. The translucent layer 126 can be typically fabricated using any technique known in the art of depositing thin films including, for example, vacuum evaporation, sputtering deposition, electron beam deposition, or chemical radon deposition, such as using pure metals or alloys or other thin film precursor Wait. Metal layer: The thickness can be controlled by the rate and time of the eruption / deposition. A typical rate of evaporation / deposition is about 0.5 to ιOA / sec. The translucent layer should be thin enough to transmit at least some light (make it translucent) and thick enough to form a continuous layer. The translucent metal layer 126 typically has a thickness of about 100 A to about 500 people. In the first preferred embodiment, the semi-transparent layer has a thickness of about 250 to about 400A. In the second preferred embodiment, the translucent layer has a thickness of about 275 to about 350A. In the third preferred embodiment, the thickness of the translucent layer is about 2 to about 325A. Printed by the Consumers' Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs, the random passivation layer 128 of electric energy materials can work inaccurately with the emission polymer, which can be used for high-reflectivity metals. The present invention's applicable private guide can be widely varied rather than strictly limited. Examples of suitable conductive materials include, but are not limited to, poly (aniline), poly (aniline) blends, polypyrimidines, and polypyrimidine blends. Suitable conductive poly (anilines) include homopolymers, transporters, and blends with bulk polymers. Examples of combined poly (aniline) include those published in US patents 5,232,63, and 5,723,873. Suitable conductive polyfluorenes include homopolymers, -8- A7 -----------— B7 —_____ V. Description of the invention (6) and blends with the overall polymer. Examples of suitable polythiophenes include poly (ethylenedioxythiophene MPEDT) such as poly (3,4-ethylenedioxythiophene), and US patents 5'766,5 15 and 5,035,926. The terms "polyamine," and "polyphenone '" are used herein collectively to include substituted and unsubstituted materials. It is also used to broadly include any incidental dosing ', especially acidic materials used to make the material conductive. The first cathode layer 142 is selected from a low work function metal or a low work function metal oxide (typically less than about 3.5 eV). Suitable for low-power substances including salt, salty soil and lanthanide metals and salt, salty soil and lanthanide heavy layer oxides. The term "salt metal" refers to elements of Group A of the Periodic Table 1 in the customary sense. The term "salt metal oxide '" here refers to the compound of salt metal and oxygen. For the sake of convenience, the salt metal oxides are indicated by the chemical formulas of fairly simple oxides (such as Li20, Na20, K20, Rb20, and Cs20); however, this simple oxide data is intended to cover other oxides, including mixed oxidation And non-stoichiometric oxides (such as Lix0, Nax0, Kx0, RbxO, and CsxO, where X is from about 0.1 to about 2). The term "salt earth metal" is used to refer to the element IIA of the periodic table. Preferred salt earth metals include magnesium (ie, M g), calcium (ie, C a), gills (ie, S r), and barium (ie, B a). The term "salt earth metal oxides" here often refers to compounds that generate oxygen from salt earth metals. For convenience, the salt earth metal oxides are indicated by the chemical formulas of fairly simple oxides (eg MgO, BaO, CaO, SrO); however, this simple oxide data is intended to cover other oxides, including mixed oxides and non-chemicals. Calculated amounts of oxides (such as MgxO, BaxO, CaxO, and SrxO, where X is from about 0.1 to about 1) 0 The term "lanthanide metal" is used in the text to refer to the lanthanide element of the periodic table. (Ie -9-This paper size applies to China National Standard (CNS) A4 specifications (210 ^ 297mm) (Please read the notes on the back first and fill in this page) ι ^, ί $-Line · Employees of Intellectual Property Bureau, Ministry of Economic Affairs Printed by the Consumer Cooperative 493289 A7 B7 V. Description of Invention (7) Please read the notes on the back first (write this page)

Ce) to (ie Lu). Preferred lanthanide metals include praseodymium (ie, Sm), yttrium (ie, Yb), and neodymium (ie, Nd). As used herein, "lanthanide metal oxides are conventionally referred to as lanthanide metal and oxygen foot compounds. For convenience, lanthanide metal oxides are indicated with a chemical formula equivalent to a +3 valence oxide (for example, Sm2 03, Yb2 0 ^ Nd2〇3); but this simple oxide data is intended to cover other oxides, including mixed oxides and non-stoichiometric oxides (for example, Smx〇, Ybx〇, and Ndy〇), whose X is about 0.1 to about 1.5). In a preferred embodiment, the first cathode layer 142 contains a low work function metal oxide. The first cathode layer 142 can typically be deposited by heating and evaporating. The first cathode layer 142 typically has a thickness from about 10 to 200 people. Typical evaporation / deposition rate is about 0.2 to about 4 A per second.-Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs, similar to the translucent layer 1 26, and the second cathode layer i 44 has a high reflectance and High work function, made of materials that can form smooth continuous films. The second cathode layer 144 typically has a work function greater than 4 eV. In a preferred embodiment, the second cathode layer 144 has a reflectance of at least 91.4% at the emission wavelength. Emission wavelength of the second cathode layer in two preferred embodiments There is a reflectance between 92% and 96.5%. The third preferred /, the first cathode layer in the group has a reflectance at the emission wavelength between 94% and 9 6.5 0 / 〇. Within the fourth preferred specific example The reflectance of the second cathode layer is greater than 96/0 at the emission wavelength. In another specific example, a metal having an reflectance of at least 86% at an emission wavelength from 400 nm to 500 nm is used as the second cathode layer 144 For example, the same translucent layer 126 and the second cathode layer 144 contain a cathode material selected from metals and metal alloys. Examples of suitable working function metals include aluminum, silver, copper, gold and the like and alloys of these metals A preferred specific example is a metal with a reflectance of at least 9 丨 4% at j emission wavelength -10- 297 mm) This paper size is applicable to the Chinese National Standard (CNS) A4 specification (21〇493289 A7 B7) V. Description of the invention (8 or a metal alloy that doubles as a translucent layer 126 and a second cathode layer 144. Another preferred embodiment is a metal that has a reflectance of at least 86% at an emission wavelength from 400 nm to 5000 nm and also serves as a translucent layer. n6 and used as the second cathode layer 144. Generally, the second cathode layer 144 need not be the same material used for the translucent layer 126. For example, gold can be used as a semi-transparent anode with a high work function, and silver can be used as a retroreflective metal layer in a double-layer cathode. Better—In the specific example, the high reflectance layer 丄 42 has a reflectance of at least 91.4% or 400- A metal with an reflectance of at least 86% at an emission wavelength of 500 nm is used as both the second cathode layer 144 and the translucent layer 126. In a more specific embodiment, silver (Ag) is also used as a high reflectivity metal layer in a double-layer cathode. It can be used as a semi-bright cathode. Alternatively, a multilayer cathode system (not shown) can be used. For example, the first high-reflectivity cathode layer (preferably thick enough to be opaque) can be the layer of another high-reverse cathode layer. The cover can be higher than the first and the cathode layer may or may not be more reflective: in the three-layer cathode capping configuration, the top metal may form a smooth connection. Any stable metal such as aluminum or aluminum alloy. Subsequent levels can perform specific functions = heart plus, for example for passivation and closed I placement. The routine G used to close the device level includes a stable capping layer. "窆 i is stable, the term refers to a protective cover layer that prevents the surrounding oxygen and moisture that may be present around the device. Suitable materials for the 蛊 layer include metals or metal alloys. Only as the ~ translucent layer 126, The second cathode layer 144 can be manufactured by known technology. The typical rate of evaporation / distillation is from about 1-20 A / sec. The second cathode layer 144 < thickness ^ should be sufficient to cover the first cathode Layer is sufficiently opaque at the relevant wavelength to produce high reflectance. The second cathode layer typically has a thickness of at least about 800A. The emission t is 11-(210 x 297 mm) (please read the note on the back first to write this page) Printed by the Consumers' Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs 493289 A7 V. Description of the invention (9) At least the emission layer 13 of the LED of the present invention (also referred to as a light-emitting layer or electro-optic containing-electro-luminous, semi-conductive organic substance. Within ㈣ The materials used for the working layer usually include polymer or molecular materials that exhibit electroluminescence. More specific materials that exhibit electroluminescence are those whose soluble JL can be processed from solution to form a uniform film. Examples of combined molecular emitting materials include simple Organic molecules such as Hui, Diazole derivatives and humorin derivatives are known to exhibit electroluminescence. In addition, complexes such as 8-hydroxyquinolate with trivalent metal ions and especially aluminum are also suitable = emitting materials, such as in Tang, etc. US patent M52,6 ". Examples of effective polymer emitting materials include semiconducting conjugated polymers. Suitable semiconducting package conjugated polymers include poly (phenylene vinylene), pPV, and soluble derivatives of pPV, such as Poly (2-methoxy-5_ (2, / ethylhexyloxy) phenylene vinylene), MEH-PPV, a semi-conductive polymer with energy gap Eg ~ 21 eV. This material is in Wudl, F ·, H〇ger, s, Zhang, c, pakbaz, κ,

Heeger, A.J., Polymer Prepdnts, 1993, 34 (n〇1), i97 are described in more detail. Another effective material mentioned in this application is poly (2,5_bis (cholestaneoxyb 1,4-phenylene vinylene BCHA_PPV, a semi-conductive polymer with an energy gap Eg ~ 2.2 ~. This material is in the United States More detailed descriptions are found in Patent No. 5,189,136. Other 'common polymers include, for example, poly (3-alkylpyrimidine) by β_η, D.,

Gustafsson, G., McBranch D., and Heeger, A. J., "Po (3-mouth stopphene) a #g luminous Yudean transport," J. Appl Phys, 1992, 72, · 564 states' yong ( Paraphenylene) Grem, G., Leditzky, G., Ullrich; B., and Leising, G. "Under benzene) to achieve blue light emission Adv. Mater., 1992,4,36 'and its soluble derivative Objects such as ¥ dagger 2;., 8 (^ 〇 仙, 1., and Karasz, FE ·, "mutually emitting blue light polymer" Macromolecules, -12- This paper size applies to China National Standard (CNS) A4 specifications (210 x 297 mm) II IJ II — — — — — — · I 1 (Please read this article on the back of moxibustion and write this page first) II. • Consumer Consumption Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs Printed by the Intellectual Property Bureau of the Ministry of Economic Affairs Printed by the cooperative 493289 V. Description of the invention (10) 1993, 26, 1 188; and poly p-quinoline such as M%! D ^, ys · Let · '1994, 65, m2. Conjugated semiconducting polymers and Blends of non-conjugated groups or carrier polymers can also be used as active layers in LED polymers, such as

Zhang, C „von Seggern: H., Pakbaz, K„ Kraabel, B., ScLdt, I ger 'A. J ·' Phenyl) in poly (9_ blue electrochromic diodes ” Synthetic

Methals, 1994, 62, 35. It is also possible to use a blend of λλ and s, one or more conjugated polymers, such as Yu ·, G ·, and Heeger A J. "Natively take people g, A. J., efficient production

Synthetic Metals, 1997, 85, 1 183. In a specific example, the electroluminescent organic substance system is an electroluminescent semiconductive organic polymer whose polymer is a π-conjugated polymer or a copolymer having a conjugated moiety = segment therein. Conjugated polymers are well known in the art. Suitable dendron 2 semiconducting organic polymers include, but are not limited to, poly (p-phenylene ethene) and its derivatives substituted on phenylene; (ii) polyphenylene phenylene B and its substituted derivatives on the fluorenyl group; (iii) poly (P-phenylenevinylene) and its substituted on the phenylene group, and also on acetylene; Derivatives; Luju (Zifanglou Yiyi), where Zifang can be Fan 1 '. "Fuman", xenazine, 4-diazole and other groups; Derivatives of poly (subaryleneacetamidine), in which the subaryl can be as above (w) and those with other substituents on the subaryl; -13- This paper size applies to China National Standard (CNS) A4 specification (210 X 297 public love) ---- Γ.ί ^ ------- installation-(Please read the note on the back first to write this page) * 1 ^. • line · 493289 • A7 B7 V. Description of the invention (11 (Vi) poly (subarylene vinylene) derivatives, in which the subaryl can be the same as above (iv) and those with other substituents on vinylidene; ^ (vii) Derivatives of poly (subarylene), in which the subaryl may be the same as (iv) and those on the subaryl and ethylene have other substituents; (viii) the subarylene ethylene oligomer Copolymers such as (iv), (vi) and (vii) without conjugated oligomers; (IX) poly (p-phenylene) and substituted derivatives of phenylene, including ladders Polymer derivatives such as poly (9,9-dialkylidene) and the like; (X) poly (subarylene) where the sub-aromatics can be fluorene, anthracene, furanene, thionine, p-one, etc. ; And its derivatives substituted on the subaromatic moiety; (xi) oligomeric sub-aromatic copolymers such as those without conjugated oligomers in (x); (xii) polyjunlin and its derivatives; (X111) polyoxoline and phenylene have, for example, alkyl groups or P-phenylene copolymers substituted with alkoxy groups and the like to provide solubility; (xiv) rigid rod polymers such as poly (p-phenylene_2 winterbenzobispyrazole), poly (p-phenylene-2, 6-benzimidin); poly (p_phenylene_2,6_benzimidazole), and its derivatives; etc. It is also suitable for semi-conductive conjugated soaps with separate molecules and different Molecular compounds blended with semiconductive conjugated polymers or covalently linked via covalent bonds. Poly (fluorene) derivatives are also effective. See, for example, US patents 5,777, _; 5,708,130; and 5,900,327. Etc. -Specific The electroluminescent semi-conductive organic materials in the example are-electroluminescent, semi-organic polyliths. In the preferred embodiment, the electro-conductive semi-conductive organic materials are selected from the group consisting of poly (P-phenylene ethylene), Poly (secondary acetamidine / inch bamboo) is selected from; (P _ subphenylene) and poly-14 This paper size is applicable to China National Standard (CNS) A4 specifications (210 X 297 public ^ 7-/ --- r J ---------- (please first Read the note on the back and write this page). -I line · Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs, printed 493289 V. Description of the invention (12) (sub-fragrant), etc. The t-layer of hair can also contain other substances such as carriers Polymers and additives. Emission screen ii ——.------- ^ i — (Please read the note on the back first to write this page) "Health: thickness of about 600 to about 1100A, depending on the wavelength required by the user and The holes are small. 7 The emission layer can typically be made by any method known in the art, especially in organic and organic polymers] methods known in LED technology, such as: direct washing and casting, and reacting the polymer after it has been polymerized. …) Yicheng's desired polymerization " I have found that a polyacoustic cathode covering a high reflectivity metal with at least one ultra-thin layer of low work function metal or metal emulsion (for effective electron injection) together with-including translucent , High reflectance, rate-metal layer m II: Thunderbolt injection, high reflection t high Q in the micro-mold groove structure, from ^ to two efficiency and improved irradiation. It is believed that a micromode slot effect # ^ * light ~ the next day ~ to promote the luminous efficiency and brightness β device semi-transparent metal anode and cathode double-layer high relative rate of the device · formation of high-performance polymer LED. Micro-mold slot_ The f-band of the band is generated first. The narrowing results change the wavelength of the emitted most photons to the more sensitive area of the human eye (see Figure 2), so that the light emitting structure's emission = efficiency is greatly increased. The broad electroluminescence spectrum of a polymer LED made with a homo-luminescent polymer in a conventional structure is shown in Fig. 3 for comparison. Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economics Encapsulation The LEDs of the present invention are typically encapsulated to prevent long-term degradation. Techniques are well known in the art for multi-encapsulation methods. For example, the device can be sealed between glass slides, or between barrier polymer layers. Rare Earth 15

493289 Α7 Β7 Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs 5. Description of the Invention (13) Examples The following examples illustrate some of the features and advantages of the present invention. It is intended to illustrate the invention and not to limit it. * In the examples and comparative examples below, the following measurements are determined according to the following procedure:: The efficiency is measured with a UDT S370 visual acuity meter (available from CA, Gamma Scientific Division of San Dieg0), which contains a photodiode and is calibrated with the following procedure . The photodiode is calibrated as follows: A 1 ^ 13 D-corrected light source has a known uniform light emission. A reticle is used to emit only the size of the pixel active area. The photodiode is placed at a set distance from the light and the volts are recorded. Then you know the number of volts corresponding to a specific luminosity (34 cd / m2). _ _ Irradiation: Newport photodiodes (available from Irvine, Xinxin ⑽corp⑽) were used to measure the exposure. The LED was sealed with an epoxy resin and a glass cover during the life test of the job. A life test was performed on individual pixels in the air. The current in the device does not change, 0.5 msc pulsation, 0.5% duty cycle, 5 mA per pixel. One pixel decays to zero light yield:!: The required time is measured with a calibrated photodiode using UDT S370. Comparative Example A. A polymer LED device was made as follows: · On a part of a glass substrate coated with IT0, a poly (benzylamine) blend solution was spin-coated in air at 6000 rpm (for general manufacturing method, see US patent) No. 5,626,795). The obtained film is on 5〇hot hot plate -16- (Please read the note on the back-write this page first).-丨 line. This paper size applies to China National Standard (CNS) A4 specification (210 X 297 mm) 493289 A7 B7 V. Description of the invention (14 for 30 minutes after drying for 30 minutes at 70 ° C. overnight. Covion PD0 122 toluene solution from Covion Organic Semiconductor Company, Frankfurt, Germany was spin-coated at 1800 rpm Covered in (nitrogen glove box ) On pAni film. The film was dried at room temperature for 2 hours. Vapor deposition was performed on the polymer film of Covion PDO 122 to a thickness of 30 angstroms. 3,000 A thick aluminum was vapor deposited on the barium layer. • Comparative Example B A polymer LED device was made as in Comparative Example A, but the aluminum was replaced by a vapor layer of 3,000 A thick vapor. Example 1 An employee's cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs printed a polymer as in Comparative Example A. The silver layer of the physical LED device replaces ITO. — Example 2 A polymer LED device with a silver thickness of 300A is made as in Comparative Example A. The performance of this device is similar to that of Examples 1 and 3, as described below. Example 3 According to Example 1 or 2 A polymer LED device was fabricated, but the silver layer was replaced by a vapor deposited silver layer with a thickness of 3,000 A. The efficiency of these devices was measured and summarized in Table 1: Table 1 0.3 mA device efficiency (cd / A ) And working voltage instance number—0.3 mA efficiency (cd / A) ___— Volt. But with 300A thick vapor deposition, but on ITO vapor deposition I JI —J ------- installation— (please First read the Note Boxing on the back to write this page). Ί Line-Comparative Example A Comparative Example B Example 1 Example 3 5.25 4.54 5.9 9.5 11.3 9.6 10.2 10.4 -17- this The paper size applies the Chinese National Standard (CNS) A4 specification (210 X 297 public love) 493289 A7 ----— R7___ V. Description of the invention (15) The above table 丨 certificate replaces IT with 300A silver month (but keep the name In-place) How much improved the light output f, resulting in a 12% increase in party level (ie, comparative example A relative example 丨). However, the most remarkable progress has been achieved in the device of the structure described in Example 3, in which a silver anode is used, and silver is a highly reflective metal used in a double-layer cathode structure. The device of Example 3 was more than 80% brighter than the device of Comparative Example A. Table i also illustrates that simply replacing the button on the cathode side with silver (Comparative Example A vs. B) and leaving the anode side unchanged does not improve the efficiency of the device. The amount of light actually decreases. The emissions in the devices of Examples 1 and 3 have also been measured in units of radiation quantity (w / Sr / m2). The measurement ignores the influence of human eye induction and measures the amount of light in absolute terms. The results are summarized in Table 2 below. Note that the irradiation from a device made according to the present invention (Example 3) is 2.5 times larger than that emitted from a conventional polymer LED structure using the same light-emitting polymer. Figure 4 shows the electroluminescence spectrum of the device of Example 3. Note that the relative electro-optical emission seen in Figure 3 is narrower, although the same emitting polymer is used in both devices. It is believed that the limitation of the Covion PDO 122 in the micromould slot in Example 3 results in emission narrowing. Table 2 Irradiation example number of the device _ Irradiation of 0.3 mA (W / Sr / m2) of the device Comparative Example A, 32 Comparative Example B 28 Example 1 41 Example 3 102 Comparative Example c A polymer LED device was manufactured according to Comparative Example A. Only use semi-conductive conjugated polymer-18- This paper size is applicable to China National Standard (CNS) A4 specification (210 X 297 public love) (Please read the note on the back-write this page) Order the intellectual property of the Ministry of Economic Affairs Printed by the Bureau's Consumer Cooperatives ^ 3289 A7

V. Description of the invention (16) CoWcm PDY 131, available from Covion Organic Semiconductor Company (Frankfurt, Germany) 'Covion PDY 131 film was spin-coated at 3,000 rpm. The barium layer is 15A thick. The electroluminescence spectrum of this device is shown in FIG. Example 4 A polymer LED device was made according to Example 3 except that the semiconductive conjugated polymer used was CoWon PDY 131, and the Covion PDY 131 film was spin-coated at 3,000 rpm. B a is 15A thick. The electroluminescence spectrum of this device is shown in FIG. 6. Table 3 The efficiency (cd / A) of the device installed at 0.3 mA and the numbering efficiency of the operating voltage instance (cd / A) ϋ n. IJ IB ·· I MB · I (Please read the note on the back first and write this page) Comparative example C Example 4 Voltage (V) Example number Comparative example C Example 4 10.8 27.4 Table 4 0.3 mA (W / Sr7m2 >) · irradiation of the irradiation device of the example 8.9 10 Order: 36 83

Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs. Tables 3 and 4 above show the results obtained for the devices of Comparative Example C and Example 4. However, the invention is not limited to a semi-conductive polymer, but it is important to change the cover due to the amount of light. 2 The cathode-capping metal is changed from aluminum: silver, and the ITO at the anode is replaced by silver. The device in Example 4 exerts bright light # 二 马 Comparative device C is 2.5 times larger than that of the device in Table C (Table 3) The undercharge rate is greater than the measured luminescence versus voltage (l_) line of the devices of Example 4 and Comparative Example C. The paper size is applicable to China Standard (CNS) A4 Specification (210 -19- 493289

Fifth, the description of the invention (17) is shown in Figure 7. The figure 7 in Figure 7 is a device made with a high brightness of 4 points. -Table 5 below demonstrates that the devices of Examples 1 and 3 have a longer lifetime and are more stable than the control device containing the ITO anode layer. ^ __ 5_ * ㈣,% lifetime of the device under high current (stress) conditions——ίΐ ^ bluff -______ intertemporal ratio is zero ^^ Example 8, 2.5 hours Example 1 The test terminal (15 hours) has not yet arrived Example 3 The subtraction test terminal (15 hours) has not yet reached the example 丨 The devices of 3 and Comparative Example A were tested under the condition of very high current (0msec pulsation, 0.5% duty cycle, 5 mA per pixel) to accelerate the aging The process can be tested on many devices. Among the three devices, the device of Comparative Example A emits light with the least light and the fastest reduction to zero (no light emission after 2.5 hours). Examples 丨 and 3 packs show very different situations during their full survival. The brightness decreases in each case "about 50% of the initial threshold and then maintained at its level. In the case of the devices of Examples 1 and 3, the regression point has not been reached before testing is complete. Therefore, although ITO is generally used as the anode layer over silver, the present invention achieves an improved operating life time using an ITO device with a silver and hafnium ratio. — ^ ——-------- Equipped · --- (Please read the note on the back to write this page) Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economy --------- 线- ---------: — -20 This paper size applies to China National Standard (CNS) A4 (210 X 297 mm) -n I nn ϋ III nn ·

Claims (1)

D8. Patent application scope L—A kind of light-emitting device (100), including an anode (120) containing a semi-transparent layer (122) with a high reflectance and a function as a function, and a cathode (14) containing At least one first cathode layer (142) of a metal oxide and a combination thereof with a low work function material and a _species having a high reflectance and a high work function =: layer (144). 2. According to item i of the scope of the patent application, the translucent layer is working and the number is greater than 4 eV. ^ 3. The device according to item 丨 of the patent application, wherein the translucent layer comprises an anode material selected from metals and metal alloys. ^ 4. The device according to item 1 of the scope of patent application, wherein the second cathode layer has a working function greater than 4 & V. · 5. The device according to the scope of the patent application, wherein the second cathode layer contains an anode material selected from a metal and a metal alloy. 6. The device according to item i of the scope of patent application, wherein at least one of the device components is selected from a translucent layer and at least a second cathode layer having a reflectance at the emission wavelength of at least 91.4%. Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economy Reflectance at 00 nm is at least 86%. 8. The device according to item 1 of the patent application scope, wherein at least one of the device components is selected from the group consisting of a translucent layer and at least one second cathode layer containing silver. · 9. The device according to item 1 of the scope of patent application, in which the translucent layer has a first flat surface (124) adjacent to the cathode and an opposite second surface (126), and an anode containing a purification layer (128) adjacent to the first surface 'Purification layer contains purified material selected from poly 21-This paper size applies to China National Standard (CNS) A4 (210 X 297 public love) 493289 A8 B8 C8 D8 t, patent application scope (aniline), poly (aniline) Blends, polythiophene, and polyfluorene blends. 10. The device according to item 1 of the scope of patent application, wherein the translucent layer has a first surface adjacent to the cathode and an opposite second surface, and the anode further comprises an indium / tin oxide transparent layer adjacent to the second surface of the translucent layer. (Please read the notes on the back first to write this page) LINE Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs -22- This paper size applies to China National Standard (CNS) A4 (210 X 297 mm)