US20090284141A1 - Organic electroluminescence element and manufacturing method thereof - Google Patents

Organic electroluminescence element and manufacturing method thereof Download PDF

Info

Publication number
US20090284141A1
US20090284141A1 US12/465,038 US46503809A US2009284141A1 US 20090284141 A1 US20090284141 A1 US 20090284141A1 US 46503809 A US46503809 A US 46503809A US 2009284141 A1 US2009284141 A1 US 2009284141A1
Authority
US
United States
Prior art keywords
metal oxide
oxide layer
organic electroluminescence
electroluminescence element
element according
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.)
Abandoned
Application number
US12/465,038
Other languages
English (en)
Inventor
Kei Sakanoue
Takahiro Komatsu
Takayuki Takeuchi
Kenji Harada
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Panasonic Corp
Original Assignee
Panasonic Corp
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by Panasonic Corp filed Critical Panasonic Corp
Assigned to PANASONIC CORPORATION reassignment PANASONIC CORPORATION ASSIGNMENT OF ASSIGNORS INTEREST (SEE DOCUMENT FOR DETAILS). Assignors: SAKANOUE, KEI, HARADA, KENJI, KOMATSU, TAKAHIRO, TAKEUCHI, TAKAYUKI
Publication of US20090284141A1 publication Critical patent/US20090284141A1/en
Priority to US13/362,602 priority Critical patent/US8529308B2/en
Abandoned legal-status Critical Current

Links

Images

Classifications

    • 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]
    • H10K50/17—Carrier injection layers
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K2102/00—Constructional details relating to the organic devices covered by this subclass
    • H10K2102/10—Transparent electrodes, e.g. using graphene
    • H10K2102/101—Transparent electrodes, e.g. using graphene comprising transparent conductive oxides [TCO]
    • H10K2102/103—Transparent electrodes, e.g. using graphene comprising transparent conductive oxides [TCO] comprising indium oxides, e.g. ITO
    • 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]
    • H10K50/18—Carrier blocking layers
    • 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]
    • H10K50/18—Carrier blocking layers
    • H10K50/181—Electron blocking layers
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K59/00—Integrated devices, or assemblies of multiple devices, comprising at least one organic light-emitting element covered by group H10K50/00
    • H10K59/10—OLED displays
    • H10K59/12—Active-matrix OLED [AMOLED] displays
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
    • H10K85/10—Organic polymers or oligomers
    • H10K85/111—Organic polymers or oligomers comprising aromatic, heteroaromatic, or aryl chains, e.g. polyaniline, polyphenylene or polyphenylene vinylene
    • H10K85/113—Heteroaromatic compounds comprising sulfur or selene, e.g. polythiophene
    • H10K85/1135—Polyethylene dioxythiophene [PEDOT]; Derivatives thereof
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
    • H10K85/10—Organic polymers or oligomers
    • H10K85/111—Organic polymers or oligomers comprising aromatic, heteroaromatic, or aryl chains, e.g. polyaniline, polyphenylene or polyphenylene vinylene
    • H10K85/115—Polyfluorene; Derivatives thereof
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
    • H10K85/10—Organic polymers or oligomers
    • H10K85/151—Copolymers

Definitions

  • the present invention relates to an organic electroluminescence element and a manufacturing method thereof. More specifically, the present invention relates to an organic electroluminescence element which is used, for example, in a display or display element for cellular phones or in various light sources and which is an electroluminescence element driven over a wide brightness range from low brightness to high brightness in usage for a light source or the like.
  • the organic electroluminescence element is a light-emitting device utilizing an electroluminescence phenomenon of a solid fluorescent substance and is partially put into practical use as a small display.
  • the organic electroluminescence element can be classified into several groups by the material used for the light-emitting layer.
  • One representative example is a low-molecular organic electroluminescence element using an organic compound with a low molecular weight for the light-emitting layer, which is manufactured mainly using vacuum vapor deposition.
  • Another example is a polymer organic electroluminescence element using a polymer compound for the light-emitting layer.
  • a solution prepared by dissolving materials constituting each functional layer enables film formation by a wet coating method such as spin coating, inkjet coating, nozzle coating, cap coating, spraying and printing. Thanks to this simple process, the wet coating method is attracting attention as a technique that can be expected to realize cost reduction and large screen area.
  • a typical polymer organic electroluminescence element is fabricated by stacking a plurality of functional layers such as charge injection layer and light-emitting layer. The construction and fabrication procedure of a representative polymer organic electroluminescence element are described below.
  • PEDOT:PSS a mixture of polythiophene and polystyrenesulfonic acid; hereinafter referred to as PEDT
  • PEDT is a material that is a de-facto standard as the charge injection layer, and functions as the hole injection layer when disposed on the anode side.
  • an interlayer 1124 composed of an organic polymer material is provided.
  • the interlayer is, for example, a copolymer of a triphenylamine derivative and polyfluorene.
  • polyfluorene for example, poly-(2,7(9,9-di-n-octylfluorene)-(1,4-phenylene-((4-sec-butylphenyl)imino)-1,4-phenylene)) indicated by TFB is used.
  • This compound is excellent in the hole injection property and at the same time, has an electron blocking function. Therefore use of the compound brings about elevation of the light emission efficiency and improvement of the driving lifetime.
  • polyphenylene vinylene (hereinafter, indicated by PPV) and a derivative thereof, or polyfluorene and a derivative thereof, is film-formed as the light-emitting layer 1125 by a spin coating method or the like.
  • injection of an organic material into the lowest unoccupied molecular orbital (LUMO) is efficiently performed using an electron injecting material 1126 of a material with a small work function such as an alkali metal or alkaline earth metal (e.g., Ba, Ca, Mg, Li, Cs) or a fluoride, oxide or carbonate of the metal above, e.g., LiF, BaO, CsCO 3 .
  • a metal electrode 1127 such as Al or Ag is provided as the cathode.
  • the film of these metals is formed by a vacuum vapor deposition method, a sputtering method or a wet coating method.
  • PEDT:PSS used as the hole injection layer is an acidic water-soluble chemical compound, and this incurs the following problems: first, a problem in view of apparatus, that is, the compound corrodes metal portions of the coating apparatus used; secondly, a problem ascribable to bad wettability to a partition wall formed mainly of a resist material and provided to divide a picture element; and thirdly, a serious problem that because the compound has bad wettability to a material which has a light-emitting function and is dissolved in an organic solvent, when the picture element is divided into fine pixels of a display or the like, the uniformity of the coated film within a pixel becomes insufficient to impair the light emission uniformity or allow easy occurrence of short circuiting. Also, it is known that chemical deterioration is caused by the injection of an electric charge and adversely affects the lifetime.
  • Reduction of the light emission intensity, that is, deterioration, of the polymer organic electroluminescence element proceeds in proportion to the product of the electric energization time and the current flowing in the element, but its details are not yet elucidated and intensive studies thereon are being made.
  • Reduction of the light emission intensity is presumed to be brought about by various causes, but the cause is considered to be a combination of various factors such as stability of the light-emitting material itself or a functional layer (e.g., hole injection layer, electron injection layer) against an electron or a hole, side reaction from an exciton, thermal stability, stability of interface between layers, diffusion of a material due to heat, and oxidation of a cathode material.
  • a functional layer e.g., hole injection layer, electron injection layer
  • PEDT is a mixture of two polymer substances, that is, polystyrenesulfonic acid and polythiophene.
  • the former is ionic and the latter has local polarity in the polymer chain.
  • phase separation indicates relatively easy breaking of the loose binding between two polymers.
  • the phase separation suggests that when driven in an organic electroluminescence element PEDT may be unstable.
  • a component not contributing to the binding in particular, an ionic component, may diffuse due to an electric field associated with electric energization and adversely affect other functional layers. In this way, despite excellent charge injection characteristics, PEDT is not a stable substance by any means.
  • the problem relevant to the hole injection layer is greatly improved by the above invention, but from the standpoint of light emission efficiency, more improvements are being demanded, because the light emission efficiency sometimes decreases depending on the material used.
  • MoS 2 is formed by a coating method and therefore, there is a problem that not only formation with a uniform thickness is difficult due to surface bulging in the pattern edge but also MoS 2 allows for a large leakage current to increase the leakage current with an adjacent pixel and is hard to integrally form particularly when achieving microfabrication and high integration.
  • a case of using nickel oxide is also known (see, Thin Solid Films, 515, 5099-5102 (2007)). This is a method of vapor-depositing a 10 nm-thick Ni metal and then heat-treating it at 500° C. to effect conversion into nickel oxide.
  • the publication above indicates that emission efficiency is enhanced by performing a heat treatment and the optimal condition is 4 hours.
  • the annealing temperature is high and, since metallic Ni is underlying, there is a problem that cross-talk occurs if the underlayer is entirely oxidized.
  • a hole injection layer composed of a transition metal oxide having a film thickness of approximately from 10 to 100 nm is used on an anode, and a functional layer such as light-emitting layer is formed thereon.
  • the functional layer is mainly formed from an interlayer and a light-emitting layer or an electron transport layer and since the interlayer used here is a thin film having a thickness of around about 20 nm and contains almost the same organic solvent as the light-emitting material, intermixing between layers often occurs.
  • the interlayer is required to have an electron blocking function so as to cause an electron injected from a cathode to stay in the light-emitting layer but cannot completely block an electron due to an intermixing problem between layers or a problem in view of chemical structure and a part of electrons are allowed to pass into an anode without being used for recombination, as a result, there arises a problem such as failure in obtaining sufficient emission efficiency.
  • an object of the present invention is to improve the light emission characteristics of a device when a transition metal oxide is used for the hole injection layer.
  • an object of the present invention is to enhance the electron blocking characteristics of a transition metal oxide.
  • the present invention is an electroluminescence element comprising an anode; a cathode; a plurality of functional layers formed between the anode and the cathode, the functional layer including a layer with a light-emitting function formed from at least one kind of an organic semiconductor; a charge injection layer formed between the anode and the layer with a light-emitting function and formed of at least one kind of a transition metal oxide.
  • a ratio of the transition metal to oxygen at the anode side in the transition metal oxide layer is smaller than a stoichiometric ratio and a ratio of the transition metal to oxygen at the layer with a light-emitting function side is greater than that at the anode side.
  • a transition metal oxide such as molybdenum oxide film-formed in a reducing atmosphere is oxygen-deficient based on the stoichiometric ratio and as compared with those where the ratio of the metal to oxygen is the stoichiometric ratio, the specific resistance is small enough to allow for hole transport.
  • molybdenum oxide at the stoichiometric ratio is known to be an insulator.
  • oxidation proceeds only in the surface to relatively increase the proportion of oxygen and bring about approximation to the theoretical ratio of the compound, and the insulating property is thereby enhanced, as a result, an electron blocking function is exerted.
  • a surface oxidation treatment such as heat treatment, UV treatment or oxygen plasma treatment in the atmosphere
  • oxidation proceeds only in the surface to relatively increase the proportion of oxygen and bring about approximation to the theoretical ratio of the compound, and the insulating property is thereby enhanced, as a result, an electron blocking function is exerted.
  • the specific resistance is small, cross-talk readily occurs to decrease the image contrast and therefore, although depending on the required specification of contrast, the original specific resistance at the film formation is preferably above a certain resistance.
  • this layer can be imparted with an electron blocking function, enabling omission of an electron blocking layer formed of an organic material, and thanks to more reduction in the film thickness, an organic electroluminescence element that is driven at a low voltage and has high emission efficiency can be provided.
  • the present invention includes the organic electroluminescence element according to aforementioned one that the transition metal oxide layer is a transition metal oxide layer formed by performing a surface oxidation treatment after film formation.
  • the present invention also includes the organic electroluminescence element according to aforementioned one that the transition metal oxide layer contains a transition metal oxide layer with the surface which surface is oxidized by a heat treatment.
  • the transition metal oxide layer can be formed in a short time by performing an oxidation treatment with good workability.
  • the present invention also includes the organic electroluminescence element according to aforementioned one that the transition metal oxide layer contains a transition metal oxide layer which surface is oxidized by an ultraviolet treatment.
  • the ultraviolet irradiation time is easy to control, so that the oxide depth can be controlled with high precision.
  • the present invention also includes the organic electroluminescence element according to aforementioned one that the transition metal oxide layer contains a transition metal oxide layer which surface is oxidized with an oxygen-containing plasma.
  • the oxide depth can be controlled with higher precision by controlling the plasma intensity, plasma density and accelerating time.
  • the present invention also includes the organic electroluminescence element according to aforementioned one that the transition metal oxide layer is formed by a dry process.
  • the transition metal oxide layer positioned on the anode side preferably has a specific resistance of 1 ⁇ 10 exp(5) ⁇ cm or more.
  • the transition metal oxide layer above preferably has a lower specific resistance of 10,000 ⁇ cm or less.
  • the present invention also includes the organic electroluminescence element according to aforementioned one that the transition metal-oxide layer is integrally formed across a plurality of picture elements.
  • the transition oxide layer is integrally formed across a plurality of picture elements, the problem of cross-talk does not arise by virtue of the large specific resistance and the layer with a light-emitting function formed thereon, particularly the coating-type layer, can easily have a uniform film thickness without causing variation of the contact angle, because the underlying layer is entirely formed of the same material.
  • a picture element regulating layer is preferably formed below the transition metal oxide layer.
  • the visible light transmittance of the metal oxide layer is preferably 70% or more.
  • the present invention is a method for manufacturing an electroluminescence element comprising an anode; a cathode; a plurality of functional layers formed between the anode and the cathode, the functional layer including a layer with a light-emitting function formed from at least one kind of an organic semiconductor; and a charge injection layer formed between the anode and the layer with a light-emitting function and formed of at least one kind of a transition metal oxide layer.
  • the method comprises the step of forming the transition metal oxide layer is a step of forming the transition metal oxide layer such that the ratio of the metal to oxygen at the anode side in the transition metal oxide layer is smaller than the stoichiometric ratio and the ratio of the metal to oxygen at the layer with a light-emitting function side is greater than that at the anode side
  • the transition metal oxide thin film formed to have oxygen deficiency is in an oxygen-deficient state and allows for injection of a hole, despite high specific resistance, but the light emission efficiency sometimes slightly decreases according to the light-emitting material used.
  • the reason therefor is considered because the electron blocking ability is insufficient.
  • it may be effective to shift the recombination region of a hole and an electron to the side closer to the cathode without locating it at the interface between the interlayer and the light-emitting layer, but the energy is sometimes transferred out to the cathode side depending on the diffusion distance of an exciton produced and a sufficiently high effect may not be obtained.
  • FIG. 1 A schematic explanatory view showing the structure of the organic electroluminescence element according to embodiment 1 of the present invention.
  • FIG. 2 A schematic explanatory view showing the structure of the organic electroluminescence element according to embodiment 2 of the present invention.
  • FIG. 3 A schematic explanatory view showing the structure of the organic electroluminescence element in Example 3 of the present invention.
  • FIG. 4 An equivalent circuit diagram of the display device according to embodiment 3 of the present invention.
  • FIG. 5 A layout explanatory diagram of the display device according to embodiment 3 of the present invention.
  • FIG. 6 A cross-sectional view of the display device according to embodiment 3 of the present invention.
  • FIG. 7 A top surface explanatory diagram of the display device according to embodiment 3 of the present invention.
  • FIG. 8 An explanatory view showing the organic electroluminescence element of a conventional example.
  • this embodiment is characterized in that by oxidizing the surface of a molybdenum oxide layer (MoO x ) as the transition metal oxide layer formed between an anode and a layer with a light-emitting function, the ratio of the molybdenum to oxygen on the anode side (MoO x1 ) of the molybdenum oxide layer is made smaller in terms of the oxygen content than the stoichiometric ratio and the ratio of the molybdenum to oxygen at the layer with a light-emitting function side (MoO x2 ) is made greater than that at the anode side.
  • MoO x1 molybdenum oxide layer
  • MoO x2 light-emitting function side
  • a bottom emission-type organic electroluminescence element is fabricated, where a surface oxidized molybdenum oxide thin film as the hole injection layer 3 and a polymer material as the light-emitting layer 4 are sequentially stacked on an anode 2 composed of an indium tin oxide (ITO) layer formed on a light-transmitting glass substrate 1 , an electron injection layer 5 composed of an alkaline earth metal is further formed thereon, and a cathode 6 composed of an aluminum layer is sequentially stacked as an upper layer.
  • ITO indium tin oxide
  • the organic electroluminescence element of this embodiment comprises, as shown in FIG. 1 , a substrate 1 composed of a light-transmitting glass material, an ITO thin film as the anode 2 formed on the substrate 1 , and layers further formed thereon, that is, a transition metal oxide thin film as the charge injection layer 3 , a light-emitting layer 4 composed of a polymer material, an electron injection layer 5 composed of a barium layer, and a cathode 6 composed of an aluminum layer.
  • the hole injection layer is composed of a surface-oxidized molybdenum oxide and therefore, stabilization and enhancement of injection characteristics can be achieved, which enables enhancing the light emission characteristics and prolonging the lifetime, so that a bottom emission-type organic electroluminescence element with high reliability can be fabricated.
  • an interlayer (electron blocking layer) 7 having a film thickness of about 20 nm and being composed of TFB is caused to intervene between the light-emitting layer 4 and the molybdenum oxide 3 as the hole injection layer of the organic electroluminescence element of embodiment 1 shown in FIG. 1 .
  • This interlayer has a LUMO level at a position shallower than the light-emitting layer and can be designed such that substantially no electron transfer occurs by forming a barrier to electron injection from the light-emitting layer into the interlayer or making the electron mobility smaller than the hole mobility.
  • Other parts are formed similarly to the organic electroluminescence element of embodiment 1.
  • the organic electroluminescence element of this embodiment comprises, as shown in FIG. 2 , a substrate 1 composed of a light-transmitting glass material, an indium tin oxide (ITO) thin film as the anode 2 formed on the substrate 1 , and layers further formed thereon, that is, a surface-oxidized transition metal oxide thin film as the hole injection layer 3 , an interlayer 7 , a light-emitting layer 4 composed of a polymer material, an electron injection layer 5 , and a cathode 6 composed of an aluminum layer.
  • ITO indium tin oxide
  • the interlayer 7 acts as the electron blocking layer.
  • the organic electroluminescence element of this embodiment in addition to the operation and effect of embodiment 1, owing to intervention of the interlayer 7 , the electron blocking function is more enhanced and the probability of recombination of an electron and a hole can be raised, which enables enhancing the light emission characteristics and prolonging the lifetime, so that an organic electroluminescence element with high reliability can be fabricated.
  • the electron injection layer of Examples can be composed of an alkali metal or alkaline earth metal having a small work function.
  • alkali metal or alkaline earth metal having a small work function.
  • Specific examples thereof include, but are not limited to, Ca, Ba, Li and Cs.
  • oxides e.g., CaO, BaO, Li 2 O, Cs 2 O 3 , MgO
  • halides e.g., LiF
  • titanium oxide, zinc oxide or the like having a defect level.
  • the reaction with moisture or oxygen is decreased in comparison with the case of using an alkali metal and/or an oxide, halide or carbonate thereof and driving in the atmosphere, which is supposed to be a drawback of the organic EL, becomes possible.
  • the hole injection layer of the present invention since the hole injection layer of the present invention has an electron blocking function, even when an interlayer is not used, an exciton produced undergoes recombination without allowing energy transfer to an electrode and therefore, the light emission region in the light-emitting layer can be shifted to the hole side.
  • the layer construction becomes simple, which contributes to enhancement of the yield or reduction of the cost.
  • the layer construction is anode/transition metal oxide layer/organic light-emitting layer/transition metal oxide layer/cathode and is a very simple construction.
  • the transition metal oxide layer sandwiched between the cathode and the organic light-emitting layer preferably contains, as a dopant, an alkali metal or alkaline earth metal such as CaO, BaO, Li 2 O, Cs 2 O 3 and MgO. These are unstable in the atmosphere but when doped in molybdenum oxide or the like having a defect level, the instability is decreased and at the same time, the electron injection property can be improved. Moreover, since the periphery thereof is covered with a transition metal oxide matrix, diffusion into other layers less occurs and an adverse effect is hardly given on the light emission efficiency or driving lifetime.
  • an alkali metal or alkaline earth metal such as CaO, BaO, Li 2 O, Cs 2 O 3 and MgO.
  • the impurity-containing transition metal oxide layer used as the electron injection layer in the present invention those having a work function of 4 to 6 eV are preferably used, but the present invention is not limited thereto.
  • a transition metal oxide is preferably used.
  • the transition metal oxide thin film of the present invention has multiple functions such as electron injection property, electron transport property and electron blocking property and therefore, high functionality can be obtained by a single layer, making it possible to simplify the layer construction of the element and realize a low-cost device.
  • the thickness of the surface-oxidized transition metal oxide layer is preferably from 1 nm to 1 ⁇ m.
  • the thickness exceeds 1 ⁇ m, high transmittance can be hardly ensured.
  • the thickness is more preferably 500 nm or less. Also, in the case of a thin thickness, even when the layer is not in a film state but in an island state, as long as the average thickness is about 1 nm, the same effects as above can be obtained. If the thickness is less than 1 nm, sufficient hole injection characteristics cannot be obtained.
  • molybdenum oxide for example, tungsten oxide, nickel oxide, vanadium oxide and ruthenium oxide may be used, but the present invention is not limited thereto.
  • tungsten oxide, nickel oxide, vanadium oxide and ruthenium oxide may be used, but the present invention is not limited thereto.
  • Such a compound takes a plurality of oxidation states and becomes an insulator when the ratio of metal to oxygen is the stoichiometric ratio or exhibits electrical conductivity when having an oxygen deficiency, and an electron blocking agility can be imparted to the compound by controlling the oxidation state in the film thickness direction as in the present invention.
  • the oxidation number or composition can be confirmed by XPS (X-ray photoelectron spectroscopy) analysis.
  • oxidation after film formation is simple and easy.
  • various methods such as UV irradiation or heat treatment in an oxygen-present atmosphere, oxygen plasma irradiation, and oxidation treatment by solution may be applied, and the method is not limited. It is also possible to form a film while varying the conditions such that the ratio of metal to oxygen reaches a desired value during, the film formation described later.
  • a light-emitting layer is formed by coating an organic semiconductor material.
  • an interlayer is preferably provided as the hole blocking layer between the light-emitting layer and the hole injection layer.
  • the polymer in the case of a polymer type, in addition to the polyfluorene-based and polyphenylene vinylene-based copolymers, as long as a thin film can be formed by dissolving the polymer in a solvent and coating the solution, the polymer is not limited in its kind, including a pendant type, a dendrimer type, and a type that is coated after doping a low-molecular light-emitting material into a coating-type low molecular or polymer host capable of dissolving in a solution and exhibiting good thin-film performance without causing crystallization or the like.
  • the layer with a light-emitting function is not limited to a polymer compound, and any of a low molecular compound, an oligomer and the like may be used. As for these materials, conventionally known materials may be used.
  • a representative structure of the low molecular electroluminescence device includes a layer structure of substrate/anode/hole injection layer/hole transport layer/electron blocking layer/light-emitting layer (including a doping material)/hole blocking layer/electron transport layer/electron injection layer/cathode, but other than this, the layer structure has various variations. Like this, the structure is a multilayer structure compared with the polymer-type electroluminescence device, which is a factor of rising cost. By using the hole injection layer of the present invention, a hole injection layer, a hole transport layer and an electron blocking layer can be integrated, and this is effective in reducing the cost.
  • the top emission type of extracting light from the direction opposite the substrate includes a reverse structure type where the anode and the cathode are reversely disposed, a top emission type thereof, and the like and, in terms of the material, is applicable when using various compounds such as fluorescent material and phosphorescent material.
  • the hole injection layer of the present invention generation of a so-called hillock that is readily produced when heating a reflective anode can be prevented.
  • the cathode a material capable of establishing ohmic contact with the electron injection layer of the present invention is preferred.
  • a general metal typified by Al, Ag or Au, a transparent electrically conductive oxide typified by ITO and IZO, and the like are preferably used.
  • the device of the present invention is preferably subjected to encapsulation.
  • an enormous cost is required for ensuring the reliability, for example, use of an encapsulating resin having as small moisture permeability as possible, film encapsulation by a thin film layer formed on the element, or sealing of a desiccant is employed.
  • simple encapsulation of the device is necessary, but the cost can be reduced by a conventional encapsulation method.
  • the simple encapsulating material can be widely selected from existing materials.
  • the transition metal oxide layer configured such that the ratio of the transition metal to oxygen on the anode side is small in terms of the oxygen content than the stoichiometric ratio and at the same time, the ratio of the transition metal to oxygen at the layer with a light-emitting function side is greater than that at the anode side, is preferably formed by a dry process such as vacuum vapor deposition, electron beam vapor deposition, molecular beam epitaxy, sputtering, reactive sputtering, ion plating, laser ablation, thermal CVD, plasma CVD and MOCVD.
  • a dry process such as vacuum vapor deposition, electron beam vapor deposition, molecular beam epitaxy, sputtering, reactive sputtering, ion plating, laser ablation, thermal CVD, plasma CVD and MOCVD.
  • the substrate temperature is preferably controlled.
  • enhancement of brightness and reduction of light emission initiating voltage can be achieved by setting the substrate temperature to from 60 to 100° C.
  • the film may also be formed while changing the introduced amount of oxygen in the course of sputtering a metal target by using a reactive sputtering method. That is, a continuous formation method of film-forming a first layer having an oxygen defect and then film-forming a transition metal oxide layer while increasing the oxygen content is also effective.
  • composition gradient film may also be formed by vapor co-deposition while changing the amount of evaporation from the target.
  • a film by a co-sputtering method using as a target an alloy obtained by mixing transition metal oxides differing in the composition or using a plurality of targets containing a plurality of kinds of transition metals such as molybdenum and tungsten.
  • a transition metal oxide film having a desired oxygen content can be obtained by performing the sputtering while changing the amount of oxygen or while switching the target between those differing in the oxygen content.
  • the film thickness is preferably in the range not impairing the hole injection property and is preferably from several nm to 500 nm.
  • the film thickness is preferably thin because the transmittance loss increases when the film thickness becomes thick, but the film thickness may be determined by taking into consideration the variation and the like at the mass production.
  • a nanoparticle or the like of an oxide is also applicable.
  • the film formation method may be appropriately selected also from wet processes such as sol-gel process, Langmuir-Blodgett method (LB method), layer-by-layer method, spin coating, inkjet coating, dip coating and spraying, and as long as the film can be formed to finally provide the effects of the present invention, any method may be used.
  • a functional layer a light-emitting layer or a hole or electron injection layer that is formed, if desired
  • a spin coating method, a casting method, a dipping method, a bar coating method, or a wet process such as roll coating, inkjet coating, nozzle coating and spraying is used.
  • a large-scale vacuum apparatus is not necessary, enabling film formation using inexpensive equipment, and at the same time, a large-area organic electroluminescence element can be easily manufactured.
  • the glass substrate 100 is one sheet of a colorless transparent glass.
  • the glass substrate 100 which can be used include a transition metal oxide glass such as transparent or semi-transparent soda lime glass, barium/strontium-containing glass, lead glass, aluminosilicate glass, borosilicate glass, barium borosilicate glass and quartz glass, and an inorganic glass such as inorganic fluoride glass.
  • the display device using the organic electroluminescence element in an embodiment of the present invention is described below. This embodiment is one example of the top emission-type polymer organic electroluminescence display device.
  • the display device of this embodiment is fundamentally manufactured as follows: an insulating film is provided on a driving substrate comprising a glass substrate having produced and provided thereon a transistor composed of polysilicon; an aluminum alloy is patterned thereon as the anode; and a sputtering film of molybdenum oxide and tungsten is formed thereon as the hole injection layer to extend across a plurality of picture elements. By forming the hole injection layer in this way without separating between picture elements, the process can be simplified.
  • the surface is oxidized by an annealing treatment in the atmosphere; a partition wall is provided to separate respective picture elements of RGB; an interlayer and a light-emitting layer are coated by an inkjet method; a Ba-doped low-molecular electron transport material is vapor co-deposited as the electron transport layer on the entire surface of RGB picture elements; ITO is then sputtered as the cathode; and the stack is subjected to encapsulation to manufacture a device. Thanks to the annealing treatment in the atmosphere performed here, the light emission efficiency is enhanced.
  • the surface is annealed to relatively increase the proportion of oxygen and bring about approximation to the theoretical ratio of the compound, whereby an electron blocking function is caused to be exerted in the surface.
  • a barium oxide-containing molybdenum oxide layer (electron injection layer) 5 is provided as a functional layer to intervene on the cathode 6 side, and an active matrix-type display device is fabricated using the same light-emitting device as the organic electroluminescence element of embodiment 1 shown in FIG. 1 .
  • transition metal oxide is oxygen-deficient and has a small specific resistance
  • molybdenum oxide transition metal oxide
  • this allows increasing the proportion of oxygen on the light-emitting layer side and bringing about approximation to the theoretical ratio of the compound, as a result, an electron blocking function is exerted in the surface.
  • FIG. 4 illustrating an equivalent circuit diagram of this matrix-type display device
  • FIG. 5 illustrating an layout explanatory diagram
  • FIG. 6 illustrating a cross-sectional view
  • FIG. 7 illustrating a top surface explanatory diagram
  • the display device above constitutes an active matrix-type display device where a driving circuit is formed for each picture element.
  • This display device 140 is fabricated, as shown in FIG. 4 illustrating an equivalent circuit diagram and in FIG. 5 illustrating an layout explanatory diagram, such that a plurality of driving circuits each consisting of an organic electroluminescence element (electroluminescence) 110 forming a picture element, two thin-film transistors (TFT: T 1 , T 2 ) composed of a switching transistor 130 and a current transistor 120 as the photodetection element, and a capacitor C are arrayed vertically and horizontally, a gate electrode of a first TFT (T 1 ) in each of the driving circuits arranged in a horizontal row is connected to a scanning line 143 to give a scanning signal, and a drain electrode of a first TFT in each of the driving circuits arranged in a vertical row is connected to a data line to supply a light emission signal.
  • TFT organic electroluminescence element
  • a driving power source (not shown) is connected, and one end of the capacitor C is grounded.
  • Reference numeral 143 denotes a scanning line
  • 144 denotes a signal line
  • 145 denotes a common power feeder cable
  • 147 denotes a scanning line driver
  • 148 denotes a signal line driver
  • 149 denotes a common power feeder driver.
  • FIG. 6 is a cross-sectional explanatory view of the organic electroluminescence element ( FIG. 6 is an A-A cross-sectional view of FIG. 5 ), and FIG. 7 is a top surface explanatory diagram of the display device, where on a glass substrate 400 having formed thereon driving TFTs (not shown), an anode (Al) 112 , a surface-oxidized molybdenum oxide layer (transition metal oxide layer) 113 , an organic interlayer (charge blocking layer) (not shown), a light-emitting layer 114 (a red light-emitting layer R, a green light-emitting layer G and a blue light-emitting layer B), a barium oxide-containing molybdenum oxide layer 115 and a cathode 116 are formed to fabricate a top emission-type organic electroluminescence element.
  • TFTs driving TFTs
  • Al anode
  • Ti transition metal oxide layer
  • organic interlayer charge blocking layer
  • the anode and the charge injection layer are individually formed, the light-emitting layer has an opening area defined by a protrusion composed of a silicon oxide layer as the picture element regulating layer 117 , and the cathode 116 is formed like a stripe running in a direction orthogonal to the anode.
  • the driving TFT is formed such that, for example, after an organic semiconductor layer (polymer layer) is formed on a glass substrate 100 and covered with a gate insulating film, a gate electrode is formed thereon and at the same time, a source/drain electrode is formed through a through-hole formed in the gate insulating film.
  • organic semiconductor layer polymer layer
  • a polyimide film or the like is coated to form an insulating layer (flat layer) and furthermore, an anode (ITO) 112 , a surface-oxidized molybdenum oxide layer 113 , an electron blocking layer, an organic semiconductor layer 114 such as light-emitting layer, a barium oxide-containing molybdenum oxide layer 115 and a cathode 116 (Al ultra-thin film and ITO) are formed to manufacture an organic electroluminescence element.
  • the capacitor and wiring are omitted, but these are formed on the same glass substrate.
  • a plurality of picture elements each composed such TFT and organic electroluminescence element are formed in a matrix manner on 11 e same substrate to constitute an active matrix-type display device.
  • a picture element regulating layer 117 is formed, for example, on a scanning line 143 , a signal line 144 , a switching TFT 130 and an electrode 112 composed of a pattern of aluminum constituting a picture element electrode, which are formed on a glass substrate 100 , and an opening is then provided.
  • a transition metal oxide layer 113 is formed over the entire surface by a sputtering method, and the surface is oxidized with an ultraviolet ray.
  • TFB as an interlayer is coated by an inkjet method.
  • This TFB layer may be coated over the entire surface similarly to the transition metal oxide layer or may be coated only on a portion corresponding to the opening.
  • a polymer organic electroluminescence material for a desired color (any one of RGB) is coated by an inkjet method on a position corresponding to the opening to form a light-emitting layer 114 .
  • a barium oxide-containing molybdenum layer 115 is film-formed by vapor co-deposition or the like, and finally, a cathode 116 is formed in a region where a display picture element 141 is disposed.
  • a display device capable of high-speed driving and assured of high reliability. Since a molybdenum oxide layer that is integrally formed and is an oxide of a transition metal intervenes between the light-emitting layer and the anode in the form of being surface-oxidized, no cross-talk occurs and the light-emitting layer is filled in a recess part smoothed by the molybdenum oxide layer and controlled in size with high precision. Therefore, the light-emitting layer can be unfailingly formed by an inkjet method without causing position slippage, and a light-emitting layer controlled in the film thickness and size with high precision can be obtained.
  • an integrally-formed molybdenum oxide layer is formed and therefore, the light-emitting layer is free from a sputtering damage when forming the cathode or a plasma damage in the patterning step.
  • the light-emitting layer can be formed on a uniformly-formed surface and the surface can be kept in a smooth state, so that the light-emitting layer can be uniformly formed and an electric field applied by the anode and cathode can be uniformly imparted to the light-emitting layer without occurrence of electric field concentration, succeeding in obtaining good light emission characteristics. Also, each light-emitting layer is uniformly formed, so that good light emission characteristics can be obtained without variation in the light emission characteristics.
  • FIG. 5 An example of the lighting device using a light-emitting device having two-dimensionally disposed therein a plurality of electroluminescence elements is described below by referring to FIG. 5 .
  • the two-dimensionally disposed electroluminescence elements 110 for example, such a construction as concurrently lighting on/off all electroluminescence elements can be quite easily realized. However, even in the case of such a construction as concurrently lighting on/off the electroluminescence elements, it is preferred to take a construction where at least one electrode (for example, a picture element electrode composed of Al (see, the anode 112 in FIG. 6 )) is separated for individual electroluminescence elements.
  • at least one electrode for example, a picture element electrode composed of Al (see, the anode 112 in FIG. 6 )
  • the lighting device having the above-described construction is applicable, for example, to domestic lighting equipment in general. In this application, since the lighting device can be constructed extremely thin, the lighting device can be easily installed not only on a ceiling but also on a wall.
  • the light emission pattern of the two-dimensionally disposed electroluminescence elements can be easily controlled by supplying arbitrary data
  • the electroluminescence element of the present invention can be constructed to give a light emitting region in a size of, for example, 40 ⁇ m-square, so that an application allowing the lighting device to serve also as a panel-type display device by supplying data can be constructed.
  • the display picture elements 141 need to be color-coded red, green or blue depending on the position, but multiple coloration can be very easily realized by using an inkjet method.
  • the electro-luminescence element 110 of the present invention can take a sufficiently large area and has very high light emission brightness and therefore, this element can be used as both a lighting device and a display device.
  • a mechanism for adjusting the light emission brightness is needed due to difference in the function (that is, the use mode) between the lighting device and the display device, and the mechanism therefor can be realized, for example, by employing the construction of embodiment 2 above and controlling the drive current, thereby adjusting the light emission brightness of each electroluminescence element.
  • the light emission brightness can be adjusted by, in use as a lighting device, driving all electroluminescence elements with a larger current, and in use as a display device, driving each electroluminescence element with a small current at a current value controlled according to the gradation (that is, according to the image data).
  • a single power source may be used for the power source when functioning as a lighting device and when functioning as a display device, but in the case where a drive current is controlled, for example, where the dynamic range of a digital-to-analog converter is large and the number of gradations becomes insufficient in use as a display device, it is preferred to take a construction of switching the power source between those (not illustrated) connected to a common power feeder cable 145 shown in FIGS. 4 and 5 according to the use mode.
  • the electroluminescence element of the present invention can be formed not only on a glass substrate 100 but also on a resin substrate such as PET and therefore, can be applied as a lighting device for various illuminations.
  • the thin film transistor may be composed of an organic transistor.
  • a structure where an organic electroluminescence element is stacked on a thin film transistor, or a structure where a thin film transistor is stacked on an organic electroluminescence element, is also effective.
  • an electroluminescence substrate having formed thereon an organic electro-luminescence element may be laminated together with a TFT substrate having formed thereon TFT, a capacitor, a wiring and the like, such that an electrode of the electro-luminescence substrate and an electrode of the TFT substrate are connected using a connection bank.
  • RGB coding is performed using a substrate having formed thereon a thin film transistor.
  • a flattening film is formed of an insulating organic material on a TFT substrate, a transparent electrode is formed on the substrate by sputtering ITO, image regulating layers in respective thicknesses are formed of SiN similarly to embodiment 4, and dry etching is applied to give a desired light emission region.
  • RGB coating is performed.
  • a flattening film is formed of an insulating organic material on a TFT substrate, a transparent electrode is formed on the substrate by sputtering ITO, image regulating layers in respective thicknesses are formed of SiON similarly to embodiment 1, and dry etching is applied to give a desired light emission region.
  • sputtering is performed while flowing oxygen and argon by using an alloy of tungsten and molybdenum as the target to form a hole injection layer composed of an oxide.
  • the substrate is introduced into an oxygen plasma apparatus and irradiated 200 W for 30 seconds to oxidize the outermost surface.
  • a bank composed of polyimide is formed for each row of RGB picture elements, whereby a substrate divided in a stripe manner into respective rows of elements by a bank is obtained.
  • An electroluminescence element is formed using the resulting substrate.
  • This substrate is characterized by high resistance compared with PEDT and no occurrence of cross-talk and therefore can be used in such a way.
  • TFB as an interlayer is coated to a thickness of 20 nm by an inkjet method for each of rows divided by a bank.
  • an ink prepared from a red light-emitting material, a green light-emitting material or a blue light-emitting material is coated as the light-emitting layer by using a dispenser to an average thickness of 80 nm on each of rows divided by a bank. Furthermore, a layer composed of a Ba-doped low-molecular electron transport material is formed as the electron injection layer by a resistance heating vapor deposition method, and aluminum is then vacuum vapor-deposited to a thickness of 100 nm as the cathode. The electron injection layer and cathode are formed to cover all picture elements.
  • TFT in a part of the obtained sample is operated by an external circuit and evaluated for the light emission state and lifetime. As a result, sufficient light emission state and lifetime are obtained.
  • molybdenum oxide is sputtered to a thickness of 100 nm on a 30 cm-square glass substrate having provided thereon ITO, and a polymer-type white light-emitting material is then spin-coated to a thickness of 100 nm.
  • sodium fluoride is 10% vapor co-deposited with zinc oxide of the present invention as the electron injection layer, and Ag is further formed to a thickness of 100 nm as the cathode.
  • the present invention is described below by referring to Examples.
  • the organic electroluminescence light-emitting device of the present invention is an example corresponding to embodiment 1 and is described by referring to FIG. 1 .
  • a molybdenum oxide layer was film-formed as the hole injection layer to a thickness of 10 nm by a sputtering method and irradiated for 3 minutes at an oscillation wavelength of 172 nm by using an excimer UV exposure apparatus, SNA/14, manufactured by Ushio Inc. to oxidize the surface.
  • TFB poly-2,7-9,9-di-n-octylfluorene-alt-1,4-phenylene-4-sec-butylphenylimino-1,4-phenylene
  • TFB copolymerization polymer of fluorene and triphenylamine
  • Sample 103 The element was then transferred to a vacuum vapor deposition apparatus, and Ba of 5 nm in thickness as the electron injection layer and Al of 100 nm in thickness as the cathode were vapor-deposited. After sealing a getter agent for an organic EL in a nitrogen atmosphere, the periphery of the obtained element was sealed with a UV-sensitive encapsulating resin. This was designated as Sample 103 .
  • Sample 104 was manufactured in the same manner as Sample 102 except that in Sample 102 , after forming the molybdenum oxide film, the substrate was introduced into an oxygen plasma apparatus and irradiated with a plasma of 200 W for 1 minute.
  • Comparative Sample 102 As regards Comparative Sample 102 for comparison, the sample obtained by not performing UV irradiation or oxygen plasma irradiation in Sample 103 or 104 was used directly. Also, Sample 101 was manufactured in the same manner as Samples 102 to 104 except that in the manufacture of Comparative Sample 102 , instead of vacuum vapor-depositing molybdenum oxide to a thickness of 10 nm, PEDT produced by H. C. Starck was spin-coated as the hole injection layer on a glass substrate 1 with a 0.7 mm-thick patterned ITO( 2 ) in the atmosphere to a thickness of 60 nm and dried by baking at 200° C. for 10 minutes and after transferring the element into a glove box, an interlayer and layers therebelow were coated.
  • PEDT produced by H. C. Starck was spin-coated as the hole injection layer on a glass substrate 1 with a 0.7 mm-thick patterned ITO( 2 ) in the atmosphere to a thickness of 60 nm and dried by
  • Sample 103 was manufactured in the same manner as Sample 102 except that in Sample 102 , UV irradiation was performed after forming the molybdenum oxide layer.
  • Sample 104 was manufactured in the same manner as Sample 102 except that in Sample 102 , after forming the molybdenum oxide film, the substrate was introduced into an oxygen plasma apparatus and irradiated with a plasma of 200 W for 1 minute. Samples 101 to 104 obtained were evaluated for IV characteristics and light emission brightness characteristics by using ITO and Al as the anode and the cathode, respectively.
  • a pattern having a plurality of picture elements as shown FIG. 5 was produced.
  • ITO as the anode was divided for individual picture elements, and the pattern was produced to make it possible to externally drive individual elements.
  • a photosensitive resist was coated as an insulating film, exposed and developed to form a picture element with a desired size.
  • a material used in Samples 101 to 104 was coated or vapor-deposited on the entire surface thereof. In the samples obtained, the hole injection layer, interlayer, light-emitting layer and anode each was formed across a plurality of picture elements.
  • an interlayer and a light-emitting layer are formed of an organic material and therefore, have a high resistance and even when such a layer is integrally formed across picture elements, cross-talk does not occur.
  • PEDT is originally a solution obtained by dispersing the mixture in water and even when dried, is small in the specific resistance. Accordingly, in the case of forming a film thereof across a plurality of picture elements, there raises a serious problem that when a common cathode is used, an adjacent picture element not applied with a voltage also emits light.
  • Molybdenum oxide for use in the present invention has a high specific resistance in the transverse direction and advantageously causes no cross-talk but is deficient in that when molybdenum oxide as-deposited is used, light emission efficiency equal to or greater than that in using PEDT is not obtained depending on the light-emitting material.
  • the oxidation treatment of the present invention is performed, the light emission efficiency becomes equal to or greater than that in using PEDT, and IV characteristics at an equal level are obtained.
  • a merit can be found in that thanks to enhancement of the light emission efficiency, the drive current value is decreased and the lifetime is also improved.
  • Example 1 the ratio of molybdenum to oxygen was examined by analyzing the surface composition of the molybdenum oxide thin film used in Samples 102 to 104 by the use of an X-ray photoelectron spectroscopy.
  • the ratio of Mo to oxygen was determined as 2.7. This is a value for a ratio between 3p orbital signal of Mo and 2p orbital signal of oxygen.
  • the ratio was determined as 2.9 and 3.0 in Sample 103 and Sample 104 , respectively. This apparently reveals that molybdenum oxide is oxidized by the surface oxidation treatment indicated in Example 1 and the proportion of oxygen is relatively increased in comparison with molybdenum.
  • the oxygen-deficient portion is oxidized by the oxidation treatment, as a result, the surface of oxygen-deficient molybdenum oxide comes close to the theoretical ratio of the compound.
  • oxidation is considered to proceed in the thickness direction of a thin film according to the time, power, temperature or the like of the oxidation treatment, but if oxidation proceeds and the stoichiometric ratio is established in the entire layer, conversely, the injection efficiency is greatly impaired.
  • Samples 202 to 204 were manufactured in the same manner by forming a tungsten oxide-sputtered film to a thickness of 20 nm in place of molybdenum oxide of Samples 102 to 104 of Example 1.
  • a tungsten oxide film was formed by so-called reactive sputtering of introducing oxygen by using a metal target.
  • Other steps are the same as in Example 1.
  • the same evaluations as in Example 1 were performed, almost the same results were obtained.
  • Samples 302 to 304 were manufactured and evaluated in the same manner by preparing an alloy target of molybdenum and tungsten in an element ratio of 30:70 and using the target in the samples of Example 2. The results are shown in Table 2.
  • the increase of light emission efficiency is larger than in the results when manufacturing the sample by using molybdenum alone or tungsten alone and performing the surface treatment.
  • the defect level formed in the extreme surface becomes a level suitable for an electron blocking layer.
  • molybdenum oxide may dissolve out.
  • molybdenum oxide can be prevented from dissolving out and also in this case, not only a smooth surface can be maintained without losing surface smoothness but also characteristic deterioration can be prevented.
  • Samples 402 to 404 were evaluated for the characteristics, as a result, the drive voltage was further decreased by about 0.5 V. This is considered to occur because the entire film thickness of the organic semiconductor layer is decreased due to removal of an interlayer.
  • the light emission efficiency was greatly reduced in the case of untreated molybdenum oxide, whereas in samples of the present invention subjected to an oxidation treatment, reduction of the light emission efficiency does not occur even when an interlayer is removed.
  • the oxidation treatment of the present invention can enhance the light emission efficiency without adversely affecting the IV characteristics and at the same time, the items required in terms of cross-talk are satisfied.
  • an organic electroluminescence element ensuring particularly enhanced electron blocking characteristics as well as long lifetime can be provided, and this organic electroluminescence element can be applied not only to an application requiring multicolor emission, such as television and display, but also to a device utilizing monochromatic emission, such as exposure device, printer and facsimile.

Landscapes

  • Physics & Mathematics (AREA)
  • Optics & Photonics (AREA)
  • Electroluminescent Light Sources (AREA)
US12/465,038 2008-05-13 2009-05-13 Organic electroluminescence element and manufacturing method thereof Abandoned US20090284141A1 (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
US13/362,602 US8529308B2 (en) 2008-05-13 2012-01-31 Organic electroluminescence element with enhanced electron blocking characteristics and manufacturing method thereof

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
JPP2008-126112 2008-05-13
JP2008126112A JP4931858B2 (ja) 2008-05-13 2008-05-13 有機エレクトロルミネッセント素子の製造方法

Related Child Applications (1)

Application Number Title Priority Date Filing Date
US13/362,602 Division US8529308B2 (en) 2008-05-13 2012-01-31 Organic electroluminescence element with enhanced electron blocking characteristics and manufacturing method thereof

Publications (1)

Publication Number Publication Date
US20090284141A1 true US20090284141A1 (en) 2009-11-19

Family

ID=41315524

Family Applications (2)

Application Number Title Priority Date Filing Date
US12/465,038 Abandoned US20090284141A1 (en) 2008-05-13 2009-05-13 Organic electroluminescence element and manufacturing method thereof
US13/362,602 Active US8529308B2 (en) 2008-05-13 2012-01-31 Organic electroluminescence element with enhanced electron blocking characteristics and manufacturing method thereof

Family Applications After (1)

Application Number Title Priority Date Filing Date
US13/362,602 Active US8529308B2 (en) 2008-05-13 2012-01-31 Organic electroluminescence element with enhanced electron blocking characteristics and manufacturing method thereof

Country Status (2)

Country Link
US (2) US20090284141A1 (enrdf_load_stackoverflow)
JP (1) JP4931858B2 (enrdf_load_stackoverflow)

Cited By (40)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20100102310A1 (en) * 2008-10-24 2010-04-29 Panasonic Corporation Organic electroluminescence device and manufacturing method thereof
US20100187513A1 (en) * 2008-04-23 2010-07-29 Panasonic Corporation Organic electroluminescence element
US20100276677A1 (en) * 2009-04-29 2010-11-04 Chimei Innolux Corporation Organic light-emitting device
US20100302221A1 (en) * 2008-12-18 2010-12-02 Panasonic Corporation Organic electroluminescence display device and manufacturing method thereof
US20110042703A1 (en) * 2008-09-19 2011-02-24 Panasonic Corporation Organic electroluminescence element and manufacturing method thereof
US20110108859A1 (en) * 2009-11-11 2011-05-12 Panasonic Corporation Organic electroluminescence element and manufacturing method thereof
CN102884650A (zh) * 2011-05-11 2013-01-16 松下电器产业株式会社 有机el显示面板及有机el显示装置
US8435093B2 (en) 2011-06-03 2013-05-07 Panasonic Corporation Method of manufacturing organic EL display panel
US8563994B2 (en) 2010-08-06 2013-10-22 Panasonic Corporation Light-emitting element, display device, and method for producing light-emitting element
US8664669B2 (en) 2010-06-24 2014-03-04 Panasonic Corporation Organic EL element, display apparatus, and light-emitting apparatus
US20140060648A1 (en) * 2011-01-27 2014-03-06 Vitriflex ,Inc. Inorganic multilayer stack and methods and compositions relating thereto
US20140102764A1 (en) * 2011-06-17 2014-04-17 Nitto Denko Corporation Conductive laminate, transparent conductive laminate with patterned wiring, and optical device
US8703530B2 (en) 2010-06-24 2014-04-22 Panasonic Corporation Method for producing organic EL element, display device, light-emitting apparatus, and ultraviolet irradiation device
US8822246B2 (en) 2009-02-10 2014-09-02 Panasonic Corporation Method for manufacturing a light-emitting element including a protective film for a charge injection layer
US8829510B2 (en) 2011-02-23 2014-09-09 Panasonic Corporation Organic electroluminescence display panel and organic electroluminescence display device
US8852977B2 (en) 2010-08-06 2014-10-07 Panasonic Corporation Method for producing light-emitting elements
US8866160B2 (en) 2009-02-10 2014-10-21 Panasonic Corporation Light-emitting element, device, and manufacturing method including a charge injection layer having a recess for suppressing uneven luminance
US8872164B2 (en) 2009-08-19 2014-10-28 Panasonic Corporation Organic el element
US8884281B2 (en) 2011-01-21 2014-11-11 Panasonic Corporation Organic EL element
US8890129B2 (en) 2010-08-06 2014-11-18 Panasonic Corporation Light emitting device, light emitting apparatus provided with a light emitting device, and method of manufacturing a light emitting device
US8890174B2 (en) 2009-02-10 2014-11-18 Panasonic Corporation Light-emitting element including a charge injection transport layer that includes a dissolvable metal compound, and display device and method for manufacturing thereof
US8921838B2 (en) 2010-08-06 2014-12-30 Panasonic Corporation Light emitting element, method for manufacturing same, and light emitting device
US8927975B2 (en) 2010-08-06 2015-01-06 Panasonic Corporation Light emitting element, method for manufacturing same, and light emitting device
US8927976B2 (en) 2010-08-06 2015-01-06 Panasonic Corporation Organic EL element and production method for same
US8946693B2 (en) 2010-08-06 2015-02-03 Panasonic Corporation Organic EL element, display device, and light-emitting device
US8981361B2 (en) 2011-02-25 2015-03-17 Panasonic Corporation Organic electroluminescence display panel with tungsten oxide containing hole injection layer that electrically connects electrode to auxiliary wiring, and organic electroluminescence display device
US8999832B2 (en) 2010-08-06 2015-04-07 Panasonic Corporation Organic EL element
US9000430B2 (en) 2011-11-24 2015-04-07 Panasonic Corporation EL display device and method for producing same
US9012896B2 (en) 2010-08-06 2015-04-21 Panasonic Corporation Organic EL element
US9012897B2 (en) 2010-08-06 2015-04-21 Panasonic Corporation Organic EL element, display device, and light-emitting device
US9029842B2 (en) 2010-08-06 2015-05-12 Joled Inc. Organic electroluminescence element and method of manufacturing thereof
US9029843B2 (en) 2010-08-06 2015-05-12 Joled Inc. Organic electroluminescence element
US9048448B2 (en) 2010-08-06 2015-06-02 Joled Inc. Organic electroluminescence element and method of manufacturing thereof
US9130187B2 (en) 2010-08-06 2015-09-08 Joled Inc. Organic EL element, display device, and light-emitting device
US9490445B2 (en) 2010-07-30 2016-11-08 Joled Inc. Organic el element, organic el panel, organic el light-emitting apparatus, organic el display apparatus, and method of manufacturing organic el element
US9843010B2 (en) 2010-08-06 2017-12-12 Joled Inc. Light-emitting element, light-emitting device provided with light-emitting element, and light-emitting element production method
US20180233688A1 (en) * 2016-06-06 2018-08-16 Boe Technology Group Co., Ltd. Light-Emitting Diode and Manufacturing Method Thereof, Light-Emitting Device
CN110870088A (zh) * 2017-07-06 2020-03-06 九州有机光材股份有限公司 有机发光元件
US11495761B2 (en) 2019-05-17 2022-11-08 Samsung Electronics Co., Ltd. Photoelectric conversion devices and organic sensors and electronic devices
US12069878B2 (en) 2017-11-08 2024-08-20 Toppan Inc. Display device

Families Citing this family (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPWO2011093146A1 (ja) * 2010-01-29 2013-05-30 株式会社アルバック 有機ｅｌ装置
JP5930670B2 (ja) * 2011-08-24 2016-06-08 株式会社日本触媒 有機電界発光素子
CN103109387B (zh) * 2011-09-08 2016-02-10 株式会社日本有机雷特显示器 发光装置及其制造方法
WO2013069274A1 (ja) 2011-11-10 2013-05-16 パナソニック株式会社 有機表示パネル、有機表示装置、有機発光装置、それらの製造方法、および薄膜形成方法
EP2787552A4 (en) * 2011-11-28 2015-07-29 Oceans King Lighting Science ELECTROLUMINESCENT POLYMERS DEVICE AND METHOD FOR THE PRODUCTION THEREOF
JP5861961B2 (ja) * 2012-02-01 2016-02-16 株式会社Ｊｏｌｅｄ 有機ｅｌ素子とその製造方法
JP2016171317A (ja) * 2015-03-12 2016-09-23 キヤノン電子株式会社 有機光電変換デバイス及び太陽電池

Citations (11)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6249085B1 (en) * 1999-03-17 2001-06-19 Tdk Corporation Organic electroluminescent device with a high-resistance inorganic hole injecting and transporting layer
US6373186B1 (en) * 1999-01-21 2002-04-16 Tdk Corporation Organic electroluminescent device with high resistance inorganic hole injecting layer
US20030132434A1 (en) * 2001-01-15 2003-07-17 Takashi Hirano Luminescence device and its manufacturing method
US20050170208A1 (en) * 2003-12-16 2005-08-04 Matsushita Electric Industrial Co., Ltd. Organic electroluminescent device and method for manufacturing the same
US7145824B2 (en) * 2005-03-22 2006-12-05 Spansion Llc Temperature compensation of thin film diode voltage threshold in memory sensing circuit
US20070065180A1 (en) * 2005-09-12 2007-03-22 Matsushita Electric Industrial Co., Ltd. Organic electroluminescence element, exposure device and image forming apparatus
US20070063639A1 (en) * 2005-07-29 2007-03-22 Matsushita Electric Industrial Co., Ltd. Organic electroluminescence element, exposure device and image forming
US20070108894A1 (en) * 2005-11-17 2007-05-17 Idemitsu Kosan Co., Ltd. Organic electroluminescent device
US20070241665A1 (en) * 2006-04-12 2007-10-18 Matsushita Electric Industrial Co., Ltd. Organic electroluminescent element, and manufacturing method thereof, as well as display device and exposure apparatus using the same
US20070290604A1 (en) * 2006-06-16 2007-12-20 Matsushita Electric Industrial Co., Ltd. Organic electroluminescent device and method of producing the same
US7990049B2 (en) * 2007-09-03 2011-08-02 Canon Kabushiki Kaisha Organic electroluminescent device and production method of the device, and display apparatus

Family Cites Families (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP4248853B2 (ja) * 2002-11-20 2009-04-02 大日本印刷株式会社 有機半導体素子用陽極
US20090160325A1 (en) 2003-12-16 2009-06-25 Panasonic Corporation Organic electroluminescent device and method for manufacturing the same
JP2005203340A (ja) 2003-12-16 2005-07-28 Matsushita Electric Ind Co Ltd 有機エレクトロルミネッセント素子
JP2008016868A (ja) * 2003-12-16 2008-01-24 Matsushita Electric Ind Co Ltd 有機エレクトロルミネッセント素子およびその製造方法
KR100829743B1 (ko) * 2005-12-09 2008-05-15 삼성에스디아이 주식회사 유기 박막 트랜지스터 및 이의 제조 방법, 이를 구비한평판 디스플레이 장치
JP2007287586A (ja) * 2006-04-19 2007-11-01 Matsushita Electric Ind Co Ltd 有機エレクトロルミネッセント素子の製造方法、有機エレクトロルミネッセント素子、これを用いた表示装置および露光装置
JP2007288074A (ja) * 2006-04-19 2007-11-01 Matsushita Electric Ind Co Ltd 有機エレクトロルミネッセント素子およびその製造方法
JP2009141077A (ja) * 2007-12-05 2009-06-25 Toppan Printing Co Ltd 有機エレクトロルミネッセンス素子、その製造方法および表示装置
JP4549401B2 (ja) * 2008-03-11 2010-09-22 富士通株式会社 抵抗記憶素子の製造方法

Patent Citations (12)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6373186B1 (en) * 1999-01-21 2002-04-16 Tdk Corporation Organic electroluminescent device with high resistance inorganic hole injecting layer
US6249085B1 (en) * 1999-03-17 2001-06-19 Tdk Corporation Organic electroluminescent device with a high-resistance inorganic hole injecting and transporting layer
US20030132434A1 (en) * 2001-01-15 2003-07-17 Takashi Hirano Luminescence device and its manufacturing method
US6774561B2 (en) * 2001-01-15 2004-08-10 Sony Corporation Light-emitting device and process for production thereof having an emission laser held between electrodes
US20050170208A1 (en) * 2003-12-16 2005-08-04 Matsushita Electric Industrial Co., Ltd. Organic electroluminescent device and method for manufacturing the same
US7145824B2 (en) * 2005-03-22 2006-12-05 Spansion Llc Temperature compensation of thin film diode voltage threshold in memory sensing circuit
US20070063639A1 (en) * 2005-07-29 2007-03-22 Matsushita Electric Industrial Co., Ltd. Organic electroluminescence element, exposure device and image forming
US20070065180A1 (en) * 2005-09-12 2007-03-22 Matsushita Electric Industrial Co., Ltd. Organic electroluminescence element, exposure device and image forming apparatus
US20070108894A1 (en) * 2005-11-17 2007-05-17 Idemitsu Kosan Co., Ltd. Organic electroluminescent device
US20070241665A1 (en) * 2006-04-12 2007-10-18 Matsushita Electric Industrial Co., Ltd. Organic electroluminescent element, and manufacturing method thereof, as well as display device and exposure apparatus using the same
US20070290604A1 (en) * 2006-06-16 2007-12-20 Matsushita Electric Industrial Co., Ltd. Organic electroluminescent device and method of producing the same
US7990049B2 (en) * 2007-09-03 2011-08-02 Canon Kabushiki Kaisha Organic electroluminescent device and production method of the device, and display apparatus

Cited By (53)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US8178870B2 (en) 2008-04-23 2012-05-15 Panasonic Corporation Organic electroluminescence element
US20100187513A1 (en) * 2008-04-23 2010-07-29 Panasonic Corporation Organic electroluminescence element
US20110042703A1 (en) * 2008-09-19 2011-02-24 Panasonic Corporation Organic electroluminescence element and manufacturing method thereof
US8334529B2 (en) 2008-09-19 2012-12-18 Panasonic Corporation Organic electroluminescence element and manufacturing method thereof
US8324617B2 (en) 2008-09-19 2012-12-04 Panasonic Corporation Organic electroluminescence element and manufacturing method thereof
US8174009B2 (en) 2008-10-24 2012-05-08 Panasonic Corporation Organic electroluminescence element and manufacturing method thereof
US20100102310A1 (en) * 2008-10-24 2010-04-29 Panasonic Corporation Organic electroluminescence device and manufacturing method thereof
US8094096B2 (en) 2008-12-18 2012-01-10 Panasonic Corporation Organic electroluminescence display device and manufacturing method thereof
US8289242B2 (en) 2008-12-18 2012-10-16 Panasonic Corporation Organic electroluminescence display device and manufacturing method thereof
US20100302221A1 (en) * 2008-12-18 2010-12-02 Panasonic Corporation Organic electroluminescence display device and manufacturing method thereof
US8890174B2 (en) 2009-02-10 2014-11-18 Panasonic Corporation Light-emitting element including a charge injection transport layer that includes a dissolvable metal compound, and display device and method for manufacturing thereof
US8890173B2 (en) 2009-02-10 2014-11-18 Panasonic Corporation Light-emitting element including a charge injection transport layer having a recess portion for accumulating ink, and display device and method for manufacturing thereof
US8822246B2 (en) 2009-02-10 2014-09-02 Panasonic Corporation Method for manufacturing a light-emitting element including a protective film for a charge injection layer
US8866160B2 (en) 2009-02-10 2014-10-21 Panasonic Corporation Light-emitting element, device, and manufacturing method including a charge injection layer having a recess for suppressing uneven luminance
US20100276677A1 (en) * 2009-04-29 2010-11-04 Chimei Innolux Corporation Organic light-emitting device
US8835908B2 (en) * 2009-04-29 2014-09-16 Innolux Corporation Organic light-emitting device
US8872164B2 (en) 2009-08-19 2014-10-28 Panasonic Corporation Organic el element
US8212267B2 (en) 2009-11-11 2012-07-03 Panasonic Corporation Organic electroluminescence element and manufacturing method thereof
US20110108859A1 (en) * 2009-11-11 2011-05-12 Panasonic Corporation Organic electroluminescence element and manufacturing method thereof
US8664669B2 (en) 2010-06-24 2014-03-04 Panasonic Corporation Organic EL element, display apparatus, and light-emitting apparatus
US8703530B2 (en) 2010-06-24 2014-04-22 Panasonic Corporation Method for producing organic EL element, display device, light-emitting apparatus, and ultraviolet irradiation device
US9490445B2 (en) 2010-07-30 2016-11-08 Joled Inc. Organic el element, organic el panel, organic el light-emitting apparatus, organic el display apparatus, and method of manufacturing organic el element
US9012896B2 (en) 2010-08-06 2015-04-21 Panasonic Corporation Organic EL element
US8890129B2 (en) 2010-08-06 2014-11-18 Panasonic Corporation Light emitting device, light emitting apparatus provided with a light emitting device, and method of manufacturing a light emitting device
US8563994B2 (en) 2010-08-06 2013-10-22 Panasonic Corporation Light-emitting element, display device, and method for producing light-emitting element
US9048448B2 (en) 2010-08-06 2015-06-02 Joled Inc. Organic electroluminescence element and method of manufacturing thereof
US9029842B2 (en) 2010-08-06 2015-05-12 Joled Inc. Organic electroluminescence element and method of manufacturing thereof
US9130187B2 (en) 2010-08-06 2015-09-08 Joled Inc. Organic EL element, display device, and light-emitting device
US9843010B2 (en) 2010-08-06 2017-12-12 Joled Inc. Light-emitting element, light-emitting device provided with light-emitting element, and light-emitting element production method
US8852977B2 (en) 2010-08-06 2014-10-07 Panasonic Corporation Method for producing light-emitting elements
US9029843B2 (en) 2010-08-06 2015-05-12 Joled Inc. Organic electroluminescence element
US8921838B2 (en) 2010-08-06 2014-12-30 Panasonic Corporation Light emitting element, method for manufacturing same, and light emitting device
US8927975B2 (en) 2010-08-06 2015-01-06 Panasonic Corporation Light emitting element, method for manufacturing same, and light emitting device
US8927976B2 (en) 2010-08-06 2015-01-06 Panasonic Corporation Organic EL element and production method for same
US8946693B2 (en) 2010-08-06 2015-02-03 Panasonic Corporation Organic EL element, display device, and light-emitting device
US9012897B2 (en) 2010-08-06 2015-04-21 Panasonic Corporation Organic EL element, display device, and light-emitting device
US8999832B2 (en) 2010-08-06 2015-04-07 Panasonic Corporation Organic EL element
US8884281B2 (en) 2011-01-21 2014-11-11 Panasonic Corporation Organic EL element
US10522695B2 (en) * 2011-01-27 2019-12-31 Vitriflex, Inc. Inorganic multilayer stack and methods and compositions relating thereto
US20140060648A1 (en) * 2011-01-27 2014-03-06 Vitriflex ,Inc. Inorganic multilayer stack and methods and compositions relating thereto
US8829510B2 (en) 2011-02-23 2014-09-09 Panasonic Corporation Organic electroluminescence display panel and organic electroluminescence display device
US8981361B2 (en) 2011-02-25 2015-03-17 Panasonic Corporation Organic electroluminescence display panel with tungsten oxide containing hole injection layer that electrically connects electrode to auxiliary wiring, and organic electroluminescence display device
CN102884650A (zh) * 2011-05-11 2013-01-16 松下电器产业株式会社 有机el显示面板及有机el显示装置
US8884276B2 (en) 2011-05-11 2014-11-11 Panasonic Corporation Organic EL display panel and organic EL display apparatus
US8435093B2 (en) 2011-06-03 2013-05-07 Panasonic Corporation Method of manufacturing organic EL display panel
US9674946B2 (en) * 2011-06-17 2017-06-06 Nitto Denko Corporation Conductive laminate, transparent conductive laminate with patterned wiring, and optical device
US20140102764A1 (en) * 2011-06-17 2014-04-17 Nitto Denko Corporation Conductive laminate, transparent conductive laminate with patterned wiring, and optical device
US9000430B2 (en) 2011-11-24 2015-04-07 Panasonic Corporation EL display device and method for producing same
US20180233688A1 (en) * 2016-06-06 2018-08-16 Boe Technology Group Co., Ltd. Light-Emitting Diode and Manufacturing Method Thereof, Light-Emitting Device
CN110870088A (zh) * 2017-07-06 2020-03-06 九州有机光材股份有限公司 有机发光元件
US11930654B2 (en) 2017-07-06 2024-03-12 Kyulux, Inc. Organic light-emitting element
US12069878B2 (en) 2017-11-08 2024-08-20 Toppan Inc. Display device
US11495761B2 (en) 2019-05-17 2022-11-08 Samsung Electronics Co., Ltd. Photoelectric conversion devices and organic sensors and electronic devices

Also Published As

Publication number Publication date
JP2009277788A (ja) 2009-11-26
US8529308B2 (en) 2013-09-10
JP4931858B2 (ja) 2012-05-16
US20120178191A1 (en) 2012-07-12

Similar Documents

Publication Publication Date Title
US8529308B2 (en) Organic electroluminescence element with enhanced electron blocking characteristics and manufacturing method thereof
KR100685108B1 (ko) 발광 소자 및 그의 제조 방법
US8125140B2 (en) Organic light emitting display with improved light emitting efficiency
US20110227100A1 (en) Light-emitting device and method for manufacturing thereof
US8759821B2 (en) Transparent organic electroluminescent element and production method therefor
JPWO2011040237A1 (ja) 有機エレクトロルミネセンス素子、有機エレクトロルミネセンスディスプレイパネルおよび有機エレクトロルミネセンスディスプレイパネル製造方法
US6946319B2 (en) Electrode for an electronic device
KR100620884B1 (ko) 유기 일렉트로루미네선스 장치, 유기 일렉트로루미네선스장치의 제조 방법 및 전자기기
US8569743B2 (en) Light-emitting component
US8278137B2 (en) Electroluminescent devices comprising bus bars
JP2003249353A (ja) アクティブマトリックス駆動型有機ｌｅｄ表示装置およびその製造方法
JP6387547B2 (ja) 有機ｅｌ素子とその製造方法、および金属酸化物膜の成膜方法
US20110315971A1 (en) Method for manufacturing organic electroluminescent device
JP2003303681A (ja) 有機ｌｅｄ素子およびその製造方法、有機ｌｅｄ表示装置
JP5017820B2 (ja) エレクトロルミネッセンス素子およびその製造方法
JP4736676B2 (ja) アクティブマトリクス駆動型有機エレクトロルミネッセンス表示装置
WO2011024346A1 (ja) 有機エレクトロルミネッセンス素子、有機エレクトロルミネッセンス表示装置、および有機エレクトロルミネッセンス照明装置
US10756308B2 (en) Organic electroluminescence element and method of manufacturing the same
JP2009212222A (ja) 有機エレクトロルミネッセント素子
JP4133736B2 (ja) 有機ｅｌ素子
JP5678455B2 (ja) 有機ｅｌ素子の製造方法及び有機ｅｌパネルの製造方法
JP4573592B2 (ja) 有機エレクトロルミネセンス素子及びその製造方法、並びに、有機エレクトロルミネセンス表示装置
US20080122353A1 (en) Electroluminescence element
JP5573545B2 (ja) 有機ｅｌ表示装置の製造方法
JP2011210613A (ja) 有機ｅｌディスプレイパネルの製造方法

Legal Events

Date Code Title Description
AS Assignment

Owner name: PANASONIC CORPORATION, JAPAN

Free format text: ASSIGNMENT OF ASSIGNORS INTEREST;ASSIGNORS:SAKANOUE, KEI;KOMATSU, TAKAHIRO;TAKEUCHI, TAKAYUKI;AND OTHERS;REEL/FRAME:023072/0014;SIGNING DATES FROM 20090512 TO 20090513

STCB Information on status: application discontinuation

Free format text: ABANDONED -- FAILURE TO RESPOND TO AN OFFICE ACTION