JP2010040210A - Organic electroluminescent element, method of manufacturing the same, lighting system, planar light source, and display device - Google Patents

Abstract

An organic electroluminescence element that is easy to manufacture, has good light emission characteristics and lifetime characteristics, good electrical characteristics, little uneven emission luminance, and excellent light emission efficiency, a manufacturing method thereof, a lighting device, a planar light source, And a display device.
A transparent first electrode, which is one of an anode and a cathode, and a material having a lower electric resistance value than the first electrode are provided in contact with the first electrode. An auxiliary electrode, a second electrode which is the other of the anode and the cathode, a light emitting layer disposed between the first electrode and the second electrode, and between the anode and the light emitting layer The auxiliary electrode is disposed within the frame of the frame-shaped first auxiliary electrode and the first auxiliary electrode, and the first auxiliary electrode is electrically connected to the first auxiliary electrode. And a second auxiliary electrode having a narrower line width than the first auxiliary electrode.
[Selection] Figure 1

Description

  The present invention relates to an organic electroluminescence element, a method for producing the organic electroluminescence element, an illumination device using the organic electroluminescence element, a planar light source, and a display device.

The organic electroluminescence element includes a pair of electrodes and an organic light emitting layer. When a voltage is applied to the organic electroluminescence element, holes and electrons are injected from each electrode, and light is emitted by recombination of the injected holes and electrons in the organic light emitting layer. The organic electroluminescence element can be driven at a lower voltage and has higher luminance than the inorganic EL element. Therefore, an organic electroluminescence element has been studied as one of light-emitting elements used for display devices and lighting devices.
A predetermined layer (such as an electron injection layer and a hole injection layer) different from the light emitting layer may be provided between the anode and the cathode for the purpose of improving the device lifetime and the light emitting characteristics. For example, there is an organic electroluminescence element in which an inorganic oxide layer such as molybdenum oxide is provided as a highly efficient electron injection layer between a light emitting layer and an electron injection electrode (see, for example, Patent Document 1).

  Of the layers provided between the electrodes, a layer that can be formed by a coating method (wet process) is usually formed by a coating method from the viewpoint of manufacturing cost. However, since the molybdenum oxide layer has low durability against a wet process, there is a risk of damaging the molybdenum oxide layer when a predetermined layer is formed on the molybdenum oxide layer by a coating method. There exists a problem that an organic electroluminescent element with a high characteristic cannot be obtained.

  In the organic electroluminescence element, at least one of the pair of electrodes is a transparent electrode, and light is extracted from the transparent electrode. The transparent electrode is made of, for example, a metal thin film or an oxide thin enough to transmit light. Such a transparent electrode has a higher electric resistance than an opaque, commonly used electrode made of a metal film or the like. In a display device or lighting device using an organic electroluminescence element, a transparent electrode having a large area is required as the light emitting area increases. When a transparent electrode having a large area is used, there is a problem that the voltage drop due to the high wiring resistance of the transparent electrode becomes large, and accordingly, the unevenness of the light emission luminance due to the voltage drop becomes so large that it cannot be ignored.

  In order to solve the problem caused by the voltage drop of the transparent electrode, a planar light emitting device including an organic electroluminescence element in which an auxiliary electrode having a lower resistance than the transparent electrode is electrically connected to the transparent electrode is disclosed (for example, Patent Document 2). In this planar light emitting device, the auxiliary electrode is thickened at a portion near a connection terminal connected to a power source, and the auxiliary electrode is thinned at a portion far from the connecting terminal. In the area close to the connection terminal, the current value is high and the emission intensity is strong because of the thick auxiliary electrode, while the aperture ratio is small, and in the area far from the connection terminal, the current value is small due to the thin auxiliary electrode and light is emitted. While the strength is weak, the aperture ratio increases, and thus a planar light emitting device that suppresses unevenness in the overall light emission luminance is realized.

  However, even when an organic electroluminescence element as described in Patent Document 2 is used, the current value becomes small at a portion far from the connection terminal, and thus unevenness in emission luminance cannot be sufficiently suppressed. . Moreover, since unevenness in light emission luminance is suppressed by adjusting the aperture ratio, there is a problem that the light use efficiency is lowered.

JP 2002-367784 A Japanese Patent Laid-Open No. 2004-14128

  The present invention has been made in view of the above-described problems of the prior art, and the problem is that the voltage drop caused by a transparent electrode that can be easily manufactured, has good life characteristics, and has high electrical resistance. In addition, even when the light emitting area is large, unevenness in light emission luminance is sufficiently suppressed, uniform light emission is possible, an organic electroluminescent element excellent in luminous efficiency, a manufacturing method thereof, and an illumination device using the organic electroluminescent element, It is to provide a planar light source and a display device.

  In order to solve the above-described problems, an organic electroluminescent element according to the present invention has a transparent first electrode, which is one of an anode and a cathode, and a lower electrical resistance than the first electrode. An auxiliary electrode provided in contact with the first electrode, a second electrode which is the other of the anode and the cathode, a light emitting layer disposed between the first electrode and the second electrode, A metal-doped molybdenum oxide layer disposed between the anode and the light emitting layer, the auxiliary electrode being disposed in a frame-shaped first auxiliary electrode and a frame of the first auxiliary electrode And a second auxiliary electrode electrically connected to the first auxiliary electrode and having a line width narrower than that of the first auxiliary electrode.

  Moreover, in the organic electroluminescent element of this invention, it is preferable that the value which remove | divided the line width of the said 2nd auxiliary electrode by the line width of the said 1st auxiliary electrode is 1/1000-1/10.

  Moreover, the organic electroluminescent element of this invention WHEREIN: The said metal dope molybdenum oxide layer may be provided in contact with the said anode.

  Moreover, in the organic electroluminescent element of the present invention, it is preferable that the visible light transmittance of the metal-doped molybdenum oxide layer is 50% or more.

  In the organic electroluminescence device of the present invention, the dopant metal contained in the metal-doped molybdenum oxide layer may be selected from the group consisting of transition metals, metals of Group 13 of the periodic table, and mixtures thereof.

  In the organic electroluminescence device of the present invention, the dopant metal may be aluminum.

  Moreover, the organic electroluminescent element of this invention WHEREIN: It is preferable that the ratio of the dopant metal contained in the said metal dope molybdenum oxide layer is 0.1-20.0 mol%.

  The method for producing an organic electroluminescence device of the present invention comprises metal oxide molybdenum oxidation by simultaneously depositing molybdenum oxide and a dopant metal on one layer selected from the group consisting of an anode, a hole injection layer and a hole transport layer. It includes a step of laminating physical layers.

  The method for manufacturing an organic electroluminescence device of the present invention may further include a step of heating the metal doped molybdenum oxide layer stacked in the step of stacking the metal doped molybdenum oxide layer.

  The illuminating device of this invention is equipped with the said organic electroluminescent element, It is characterized by the above-mentioned. Moreover, the planar light source of the present invention comprises the organic electroluminescence element. Furthermore, the display device of the present invention is characterized by comprising the organic electroluminescence element.

  According to the organic electroluminescent element of the present invention, since the auxiliary electrode having an electric resistance lower than that of the transparent electrode is provided in contact with the transparent electrode, the voltage drop due to the resistance of the transparent electrode is reduced, and even when the light emitting area is wide. Unevenness of light emission luminance is sufficiently suppressed, and uniform light emission is possible.

  That is, in the organic electroluminescence element of the present invention, more specifically, a frame-shaped first auxiliary electrode and an inner side of the frame of the first auxiliary electrode are arranged on the surface of the first electrode made of a transparent electrode. In addition, a second auxiliary electrode that is electrically connected to the first auxiliary electrode and has a narrower line width than the first auxiliary electrode is disposed. In addition to the first electrode, by providing such an auxiliary electrode having an electric resistance lower than that of the transparent electrode (first electrode), a voltage drop due to the resistance of the first electrode can be reduced.

In the present invention, since the first auxiliary electrode has a wide line width and can pass a sufficient current, even the portion far from the connection terminal is hardly affected by the voltage drop due to the wiring resistance.
In addition, since the second auxiliary electrode has a small line width, the second auxiliary electrode has a small amount of blocking the light emitted from the organic layer, and has little influence on the light use efficiency. The second auxiliary electrode is easily affected by a voltage drop due to wiring resistance because the line width is thin. In the present invention, the second auxiliary electrode is disposed inside the frame of the first auxiliary electrode. In addition, since it has an electrical connection structure that is electrically connected to the first auxiliary electrode that is hardly affected by the voltage drop due to the wiring resistance, wiring is performed even in the auxiliary electrode far from the connection terminal. Voltage drop due to resistance is alleviated.

  Therefore, according to the organic electroluminescence element of the present invention, the voltage drop due to the resistance of the transparent electrode is reduced, and even when the emission area is large, unevenness in emission luminance is sufficiently suppressed, and uniform emission is possible.

  Furthermore, in the organic electroluminescence device of the present invention, since the inorganic oxide layer and the layer laminated thereon can be easily and with high quality, the production is easy, and the light emission characteristics and the lifetime are also provided. Good characteristics.

According to the present invention, it is possible to provide an organic electroluminescence device capable of reducing the voltage drop due to the resistance of the transparent electrode, sufficiently suppressing unevenness in light emission luminance even when the light emission area is large, and capable of uniform light emission. . According to the present invention, since the inorganic oxide layer and the layer laminated thereon can be easily and with high quality, the production is easy, and the light emission characteristics and the life characteristics are good. is there.
Therefore, the organic electroluminescence element of the present invention can be suitably used as a display device such as a lighting device, a planar light source as a backlight, and a flat panel display.

  Hereinafter, the organic electroluminescence element of the present invention will be described in detail in accordance with preferred embodiments thereof. Note that the scale of each member in the drawings shown in the following description may differ from the actual scale.

  The organic electroluminescent device according to the present invention includes a transparent first electrode, which is one of an anode and a cathode, and a low electric resistance compared to the first electrode, and is in contact with the first electrode. An auxiliary electrode provided; a second electrode which is the other of the anode and the cathode; a light-emitting layer disposed between the first electrode and the second electrode; and between the anode and the light-emitting layer The auxiliary electrode is disposed within the frame of the frame-shaped first auxiliary electrode and the first auxiliary electrode, and the first auxiliary electrode is electrically connected to the first auxiliary electrode. And a second auxiliary electrode having a line width smaller than that of the first auxiliary electrode.

  An organic electroluminescence device according to the first embodiment of the present invention having such a basic configuration is shown in FIG.

An auxiliary electrode 4 composed of a first auxiliary electrode 2 and a second auxiliary electrode 3 is disposed on the support substrate 1. Hereinafter, in this specification, one side in the thickness direction of the support substrate 1 may be referred to as “upper” (or upper), and the other in the thickness direction of the support substrate 1 may be referred to as “lower” (or lower). A transparent anode (first electrode) 5 is disposed on these auxiliary electrodes 4. A light emitting section 6 is disposed on the anode (first electrode) 5, and a cathode (second electrode) 7 is disposed thereon. Usually, a protective layer (sometimes referred to as an upper sealing film) that protects the entire laminate in order to protect the laminate (sometimes referred to as a light emitting function unit) disposed on the support substrate 1. Is provided.
In the first embodiment, the first electrode 5 is an anode and the second electrode 6 is a cathode. However, the stacking order of the laminate is reversed, the first electrode is the cathode, and the second electrode is You may comprise the organic electroluminescent element which is an anode.

(Auxiliary electrode)
In the organic electroluminescence element of this embodiment, the auxiliary electrode 4 is arranged on the surface of the anode (first electrode) 5 and is a frame-shaped first auxiliary electrode electrically connected to the first electrode. 2 and a second auxiliary electrode 3 disposed inside the frame of the first auxiliary electrode 2 and electrically connected to the first auxiliary electrode 2 and having a line width narrower than that of the first auxiliary electrode 2 Is provided.
In this embodiment, the first auxiliary electrode 2 and the second auxiliary electrode 3 are arranged on the surface of the anode (first electrode) 5 in the above-described form, so that the light emitting area of the organic electroluminescence element is large. Even in this case, it is possible to sufficiently suppress the unevenness of the emission luminance.

  An example of the arrangement form of the auxiliary electrode 4 composed of the first auxiliary electrode 2 and the second auxiliary electrode 3 is shown in FIGS.

  In the arrangement shown in FIG. 2, the auxiliary electrode 4 formed on the support substrate 1 is electrically integrated integrally with the first auxiliary electrode 2a having a rectangular frame shape and the inside of the frame of the first auxiliary electrode 2a. The second auxiliary electrode 3a is formed. The second auxiliary electrode 3a has a narrower line width than the first auxiliary electrode 2a, and the plurality of second auxiliary electrodes 3a are arranged in a lattice shape intersecting at right angles to each other.

  In the arrangement shown in FIG. 3, the auxiliary electrode 4 formed on the support substrate 1 is electrically integrated integrally with the first auxiliary electrode 2b having a rectangular frame shape and the inside of the frame of the first auxiliary electrode 2b. The second auxiliary electrode 3b is formed. The second auxiliary electrode 3b has a narrower line width than the first auxiliary electrode 2b, and the plurality of second auxiliary electrodes 3b are arranged in parallel to each other.

  In the arrangement shown in FIG. 4, the auxiliary electrode 4 formed on the support substrate 1 is electrically integrated integrally with the first auxiliary electrode 2c having a rectangular frame shape and the inside of the frame of the first auxiliary electrode 2c. The second auxiliary electrode 3c is formed. The second auxiliary electrode 3c has a narrower line width than the first auxiliary electrode 2c, and each of the plurality of second auxiliary electrodes 3c is arranged so as to constitute each side of each hexagon of the honeycomb structure.

  In the arrangement shown in FIG. 5, the auxiliary electrode 4 formed on the support substrate 1 is electrically integrated integrally with the first auxiliary electrode 2d having a rectangular frame shape and the inside of the frame of the first auxiliary electrode 2d. The second auxiliary electrode 3d is formed. The second auxiliary electrode 3d is composed of two types of fine line electrodes whose line width is narrower than that of the first auxiliary electrode 2d. That is, the second auxiliary electrode 3d includes a plurality of main thin-line electrodes 3d-1 intersecting at right angles to each other and the inside of the region surrounded by the first thin-line electrodes 3d-1, It consists of a second thin wire electrode 3d-2 formed inside a region surrounded by the first auxiliary electrode 2d and the first thin wire electrode 3d-1.

In the arrangement form of FIG. 5, the first thin wire electrodes 3d-1 are arranged in a lattice shape, and a plurality of second thin wire electrodes 3d-2 are arranged in a lattice shape in each lattice-shaped frame. The second thin wire electrode 3d-2 is usually preferably formed with a line width narrower than that of the first thin wire electrode 3d-1.
By taking such an arrangement form of the auxiliary electrodes, the effect of the present invention can be obtained even in an element having a larger light emitting area.

  Here, the frame shape of the frame-shaped first auxiliary electrode 2 is not particularly limited as long as the second auxiliary electrode 3 can be formed in the first auxiliary electrode 2. For example, the frame shape is rectangular or circular. Etc. are possible. The first auxiliary electrode 2 is preferably provided so as to surround a main region through which light is transmitted. The line width of the first auxiliary electrode 2 can be appropriately selected according to the electric resistance and the light emitting area of the organic electroluminescence element, and is preferably in the range of 1 to 50 mm, and more preferably in the range of 3 to 20 mm. More preferred.

  Since the inside of the frame of the first auxiliary electrode 2 where the second auxiliary electrode 3 is provided is a main region through which light from the light emitting unit 6 is transmitted, the line width of the second auxiliary electrode 3 does not hinder the transmission of light. Such dimensions are preferred. From this point of view, the line width of the thin wire electrode constituting the second auxiliary electrode 3 (hereinafter referred to as “line width of the second auxiliary electrode”) is in the range of 1 to 200 μm from the viewpoint of light utilization efficiency. Preferably, it is in the range of 10 to 100 μm.

  In the first embodiment, the value obtained by dividing the line width of the second auxiliary electrode by the line width of the first auxiliary electrode is more preferably 1/1000 to 1/10. If the ratio of the line widths is within the above range, the light utilization efficiency is further improved, and unevenness in the light emission luminance tends to be further suppressed.

As the material of the first auxiliary electrode 2 and the second auxiliary electrode 3 such, (low electric resistance) that is preferably a high electrical conductivity than the transparent anode (first electrode) 5, usually 10 ⁷ S A conductive material having an electric conductivity of not less than / cm is used. Specific examples of such a conductive material include metal materials such as aluminum, silver, chromium, gold, copper, and tantalum. Among these, aluminum, chromium, copper, and silver are more preferable from the viewpoint of high electrical conductivity and ease of material handling.

  The larger the area where the auxiliary electrode 4 composed of the first auxiliary electrode 2 and the second auxiliary electrode 3 is in contact with the transparent anode (first electrode) 5 is wider for the purpose of reducing the voltage drop due to the resistance of the first electrode 5. good. Therefore, when a metal is used as the material of the first auxiliary electrode 2 and the second auxiliary electrode 3, the auxiliary electrode 4 is made of a transparent anode (when converted to the ratio of the area covered by the auxiliary electrode 4 to the light emitting area of the element). The area in contact with the first electrode 5 is preferably at least 20%, more preferably 30% or more.

  On the other hand, since the auxiliary electrode 4 is provided in contact with the transparent anode (first electrode) 5 that transmits light from the light emitting portion 6, it is preferable that the area occupied by the auxiliary electrode 4 is as small as possible so that light is not blocked as much as possible. . From this point of view, the ratio of the area covered by the auxiliary electrode 4 to the light emitting area of the element is preferably 90% or less, and more preferably 80% or less.

  Taking these into consideration, the ratio of the area covered by the auxiliary electrode 4 to the light emitting area of the element is preferably 20% or more and 90% or less, preferably 30% or more and 80% or less. More preferred.

  Further, the thicknesses of the first auxiliary electrode 2 and the second auxiliary electrode 3 can be appropriately selected so that the sheet resistance has a desired value, and is, for example, 10 to 500 nm, preferably 20 to 300 nm. Yes, more preferably 50 to 150 nm.

  Furthermore, in the organic electroluminescence element of the present embodiment, the first auxiliary electrode 2 and the second auxiliary electrode 3 are on the surface of the transparent anode (first electrode) 5 on the light emitting unit 6 side. Although it may be arrange | positioned, from a viewpoint of making the electrical connection of the said transparent anode (1st electrode) 5, the said 1st auxiliary electrode 2, and the said 2nd auxiliary electrode 3 more reliable, the light emission part 6 is provided. It is preferable to arrange | position on the surface on the opposite side.

  As a method of forming the first auxiliary electrode 2 and the second auxiliary electrode 3 described above, a film made of the constituent material of the auxiliary electrode is formed by, for example, a vacuum deposition method, a sputtering method, or a laminating method in which a metal thin film is thermocompression bonded. Then, a method of forming a pattern by an etching method using a photoresist can be mentioned. Note that the auxiliary electrode can be patterned without etching. For example, the auxiliary electrode having a predetermined pattern can be formed by performing vacuum deposition a plurality of times using one or more masks in which openings corresponding to the shape of the auxiliary electrode are formed. Depending on the material constituting the second electrode, the second electrode may be damaged by the etchant. However, by forming the auxiliary electrode using a mask, the auxiliary electrode can be applied to the second electrode having low resistance to the etchant. Can be formed.

(Metal-doped molybdenum oxide layer)
Between the anode (first electrode) 5 and the cathode (second electrode) 7, a light emitting layer 10 and a metal-doped molybdenum oxide layer provided between the light emitting layer 10 and the anode (first electrode) 5 Is provided. A predetermined layer may be further provided between the anode (first electrode) 5 and the light emitting layer 10 and between the light emitting layer 10 and the cathode (second electrode) 7. Examples of the layer 9 provided between the anode (first electrode) 5 and the light emitting layer 10 include a hole injection layer, a hole transport layer, and an electron blocking layer, which will be described later. The light emitting layer 10 and the cathode (first electrode) Examples of 11 provided between the two electrodes 7 include an electron injection layer, an electron transport layer, and a hole blocking layer, which will be described later. That is, an element configuration in which only the metal-doped molybdenum oxide layer is provided between the light emitting layer 10 and the anode (first electrode) 5, and an element in which the metal-doped molybdenum oxide layer and other layers are provided There is a configuration.

  The metal-doped molybdenum oxide layer contains molybdenum oxide and a dopant metal, and preferably consists essentially of molybdenum oxide and dopant metal. More specifically, when the metal-doped molybdenum oxide layer is formed as a single layer, the proportion of the total of the molybdenum oxide and the dopant metal in the total amount of the substances constituting the layer is preferably 98% by mass or more, More preferably, it is 99 mass% or more, More preferably, it is 99.9 mass% or more.

The metal-doped molybdenum oxide layer is preferably a hole injection layer, or is provided in direct contact with the light emitting layer 10 or the hole injection layer. More specific arrangements of the metal-doped molybdenum oxide layer are shown in the following (i) to (v).
(Ii) provided in contact with the anode and the hole transport layer (ii) provided in contact with the anode and the electron blocking layer (iii) provided in contact with the hole injection layer and the light emitting layer (iv) the hole injection layer and (V) Provided in contact with the electron blocking layer (v) Provided in contact with the anode and the light emitting layer In the case of the organic electroluminescence device having the bottom emission structure of this embodiment, (i) or (ii) is preferable, and the metal-doped molybdenum The oxide layer usually functions as a hole injection layer. In the case of an organic electroluminescence device having a top emission structure described later, (iii) or (iv) is more preferable, and the metal-doped molybdenum oxide layer usually functions as a hole transport layer.

  The visible light transmittance of the metal-doped molybdenum oxide layer is preferably 50% or more. By having a visible light transmittance of 50% or more, it can be suitably used for an organic electroluminescence element that emits light through the metal-doped molybdenum oxide layer.

The dopant metal contained in the metal-doped molybdenum oxide layer is preferably a transition metal, a Group 13 metal of the periodic table, or a mixture thereof, more preferably aluminum, nickel, copper, chromium, titanium, silver, gallium, zinc. , Neodymium, europium, holmium, cerium, and more preferably aluminum. On the other hand, it is preferable to employ MoO ₃ as the molybdenum oxide. When forming the MoO ₃ by evaporation method such as vacuum deposition, although the stoichiometric composition ratio of Mo and O in the deposited film may sometimes deviate from MoO _3, organic this embodiment even in this case It can be preferably used for an electroluminescence element.

  It is preferable that the ratio of the dopant metal contained in the metal doped molybdenum oxide layer is 0.1 to 20.0 mol%. When the content ratio of the dopant metal is within the above range, a metal-doped molybdenum oxide layer having good process resistance can be obtained.

  Although the thickness of the said metal dope molybdenum oxide layer is not specifically limited, It is preferable that it is 1-100 nm.

  A method for forming the metal-doped molybdenum oxide layer is not particularly limited, but a preferred method is a so-called co-evaporation method in which molybdenum oxide and a dopant metal are simultaneously deposited on a layer on which the metal-doped molybdenum oxide layer is laminated. It can be illustrated as one of these. For example, deposition can be carried out on an anode or cathode layer provided on a substrate to obtain a metal-doped molybdenum oxide layer in direct contact with the electrode. Alternatively, after an electrode is provided on the substrate, one or more other layers such as a light emitting layer, a charge injection layer, a charge transport layer, or a charge blocking layer are provided on the electrode, and deposition is further performed thereon. A metal-doped molybdenum oxide layer in direct contact can be obtained.

  Deposition can be performed by vacuum evaporation, molecular beam evaporation, sputtering or ion plating, ion beam evaporation, or the like. By introducing plasma into the film formation chamber, a plasma assisted vacuum deposition method with improved reactivity and film formability can be used. Examples of the evaporation source of the vacuum deposition method include resistance heating, electron beam heating, high frequency induction heating, and laser beam heating. As a simpler method, resistance heating, electron beam heating, and high frequency induction heating are preferable. There are a DC sputtering method, an RF sputtering method, an ECR sputtering method, a conventional sputtering method, a magnetron sputtering method, an ion beam sputtering method, a counter target sputtering method, and the like, and any of these methods can be used. In order not to damage the lower layer of the metal-doped molybdenum oxide layer, it is preferable to use a magnetron sputtering method, an ion beam sputtering method, or a counter target sputtering method.

Note that during film formation, vapor deposition can be performed by introducing a gas containing oxygen or an oxygen element into the atmosphere. In addition, as a material for depositing the metal-doped molybdenum oxide layer, MoO ₃ or a dopant metal alone is usually used, but molybdenum alone, an oxide of MoO ₂ or a dopant metal, an alloy of a dopant metal and molybdenum, or these A mixture of the above can be used.

The deposited metal-doped molybdenum oxide layer is subjected to other steps such as heating, UV-O ₃ treatment, atmospheric exposure, etc. as it is or optionally, and then the metal obtained from the other layers constituting the device is obtained. An organic electroluminescence element can be completed by laminating the doped molybdenum oxide layer.

The heating can be performed at 50 to 350 ° C. for 1 to 120 minutes. The UV-O ₃ treatment can be performed by irradiating with ultraviolet rays at an intensity of 1 to 100 mW / cm ² for 5 seconds to 30 minutes and in an atmosphere having an ozone concentration of 0.001 to 99%. The exposure to the atmosphere can be performed by leaving it in the atmosphere at a humidity of 40 to 95% and a temperature of 20 to 50 ° C. for 1 to 20 days.

As described above, the organic electroluminescence element of the present embodiment is characterized in that the auxiliary electrode 4 having a specific shape is disposed in a state of being electrically connected to the first electrode that is a transparent anode or cathode, The metal doped molybdenum oxide layer is provided between the light emitting layer. The details of the auxiliary electrode 4 and the metal-doped molybdenum oxide layer are as described above.
Subsequently, components of the organic electroluminescence element other than the auxiliary electrode 4 and the metal-doped molybdenum oxide layer will be described in detail below.

(substrate)
The support substrate 1 may be any substrate that does not change in the step of forming the organic electroluminescence element, and may be a rigid substrate or a flexible substrate. For example, a glass plate, a plastic plate, a polymer film, a silicon plate, and these may be used. Laminated laminates and the like are preferably used. Further, a plastic, a polymer film or the like that has been subjected to a low water permeability treatment can also be used. A commercially available substrate can be used as the substrate. Moreover, the said board | substrate can also be manufactured by a well-known method.

In the bottom emission type organic electroluminescence element that takes out light from the light emitting unit 6 from the support substrate 1 side as shown in FIG. 1, the support substrate 1 having a high light transmittance in the visible light region is preferably used. .
In the top emission type organic electroluminescence element that takes out light from the light emitting portion 6 from the cathode 7 side as shown in the second embodiment to be described later, the support substrate 1 may be transparent or opaque. Good.

(First electrode)
The first electrode (the anode 5 in the configuration of FIG. 1) in the first embodiment is a transparent electrode that transmits light from the light emitting layer 10 and mainly serves as the anode of the organic electroluminescence element of the present invention. However, as will be described later, an organic electroluminescence element having a configuration in which a transparent first electrode is used as a cathode is also possible. As such a first electrode 5, a metal oxide, metal sulfide or metal thin film having high electrical conductivity can be used, and a material having high transmittance can be suitably used, depending on the constituent material of the light emitting unit 6. Can be appropriately selected and used. Examples of the material of the first electrode 5 include thin films such as indium oxide, zinc oxide, tin oxide, indium tin oxide (abbreviated as ITO), indium zinc oxide (abbreviated as IZO), gold, platinum, silver, and copper. Used. Among these, ITO, IZO, and tin oxide are preferable.

  Further, as a constituent material of the first electrode 5, a transparent conductive film made of an organic material such as polyaniline or a derivative thereof, polythiophene or a derivative thereof may be used.

  Further, from the viewpoint of facilitating charge injection into the light emitting layer 10, a conductive polymer such as a phthalocyanine derivative and a polythiophene derivative, Mo oxide, amorphous, etc. are formed on the surface of the first electrode 5 on the light emitting layer 10 side. A 1 to 200 nm layer such as carbon, carbon fluoride, or polyamine compound, or a layer having an average film thickness of 10 nm or less made of a metal oxide, a metal fluoride, an organic insulating material, or the like may be provided.

  The film thickness of the first electrode 5 can be appropriately selected in consideration of light transmittance and electrical conductivity, and is, for example, 5 nm to 10 μm, preferably 10 nm to 1 μm, more preferably 20 nm to 500 nm. It is.

  The first electrode may be divided into a plurality of electrically separated cells. In such a case, the interval between adjacent cells is preferably 1 μm to 50 μm, more preferably 5 μm to 30 μm. If the distance between adjacent cells is less than the lower limit, the light guided in the surface direction of the first electrode 5 tends not to be sufficiently suppressed. Since the light emission area becomes small, the light emission efficiency tends to decrease.

  In addition, the shape of the plurality of electrically separated cells is not particularly limited, and examples thereof include a stripe shape, a triangular shape, and a rectangular shape. In addition, in the case of a structure in which the first electrode is partitioned into a plurality of electrically separated cells, the first electrode is formed after the first electrode is formed in the production of the organic electroluminescence element of the present invention (for example, At least a part of the auxiliary electrode and the organic layer) is filled between adjacent cells.

Examples of the method for forming the first electrode 5 include a vacuum deposition method, a sputtering method, an ion plating method, and a plating method.
Moreover, as a method of partitioning the first electrode into a plurality of electrically separated cells, for example, a method of forming a pattern by an etching method using a photoresist after forming the first electrode can be mentioned.

(Layer provided between the anode and the light emitting layer)
At least a metal-doped molybdenum oxide layer is provided between the anode and the light emitting layer. In addition to the metal-doped molybdenum oxide layer, a hole injection layer, a hole transport layer, an electron block layer, and the like may be provided as described above.

  The hole injection layer is a layer having a function of improving the efficiency of hole injection from the anode (first electrode) 5. The hole transport layer is a layer having a function of improving hole injection from the anode, the hole injection layer, or the hole transport layer closer to the anode. The electron blocking layer is a layer having a function of blocking electron transport. In the case where the hole injection layer and / or the hole transport layer has a function of blocking electron transport, these layers may also serve as an electron blocking layer. The fact that the electron blocking layer has a function of blocking electron transport makes it possible, for example, to produce an element that allows only electron current to flow and confirm the blocking effect by reducing the current value.

(Hole injection layer)
As described above, the hole injection layer can be provided between the anode and the hole transport layer or between the anode and the light emitting layer. As a material constituting the hole injection layer, a known material can be appropriately used, and there is no particular limitation. For example, phenylamine, starburst amine, phthalocyanine, hydrazone derivative, carbazole derivative, triazole derivative, imidazole derivative, oxadiazole derivative having amino group, vanadium oxide, tantalum oxide, tungsten oxide, molybdenum oxide, ruthenium oxide And oxides such as aluminum oxide, amorphous carbon, polyaniline, polythiophene derivatives, and the like.

  As a film formation method of the hole injection layer, for example, film formation from a solution containing a material (hole injection material) that becomes the hole injection layer can be mentioned. The solvent used for film formation from a solution is not particularly limited as long as it dissolves the hole injection material. Chlorine solvents such as chloroform, methylene chloride and dichloroethane, ether solvents such as tetrahydrofuran, toluene, Mention may be made of aromatic hydrocarbon solvents such as xylene, ketone solvents such as acetone and methyl ethyl ketone, ester solvents such as ethyl acetate, butyl acetate and ethyl cellosolve acetate, and water.

  As a film forming method from a solution, a spin coating method, a casting method, a micro gravure coating method, a gravure coating method, a bar coating method, a roll coating method, a wire bar coating method, a dip coating method, a spray coating method, a screen printing method, Examples of the application method include a flexographic printing method, an offset printing method, and an ink jet printing method.

  The thickness of the hole injection layer is preferably about 5 to 300 nm. If the thickness is less than 5 nm, the production tends to be difficult. On the other hand, if the thickness exceeds 300 nm, the driving voltage and the voltage applied to the hole injection layer tend to increase.

(Hole transport layer)
The material constituting the hole transport layer is not particularly limited. For example, N, N′-diphenyl-N, N′-di (3-methylphenyl) 4,4′-diaminobiphenyl (TPD), 4 , 4′-bis [N- (1-naphthyl) -N-phenylamino] biphenyl (NPB) and other aromatic amine derivatives, polyvinylcarbazole or derivatives thereof, polysilane or derivatives thereof, aromatic amines in the side chain or main chain Polysiloxane derivative having pyrazole, pyrazoline derivative, arylamine derivative, stilbene derivative, triphenyldiamine derivative, polyaniline or derivative thereof, polythiophene or derivative thereof, polyarylamine or derivative thereof, polypyrrole or derivative thereof, poly (p-phenylene vinylene) Or its derivatives, or poly (2,5-thienylene vinylene) or a derivative thereof is exemplified.

  Among these, as the hole transport material used for the hole transport layer, polyvinyl carbazole or a derivative thereof, polysilane or a derivative thereof, a polysiloxane derivative having an aromatic amine compound group in a side chain or a main chain, polyaniline or a derivative thereof, Polymeric hole transport materials such as polythiophene or derivatives thereof, polyarylamine or derivatives thereof, poly (p-phenylene vinylene) or derivatives thereof, or poly (2,5-thienylene vinylene) or derivatives thereof are preferred, and more preferred Is polyvinyl carbazole or a derivative thereof, polysilane or a derivative thereof, and a polysiloxane derivative having an aromatic amine in the side chain or main chain. In the case of a low-molecular hole transport material, it is preferably used by being dispersed in a polymer binder.

  The method for forming the hole transport layer is not particularly limited, but in the case of a low molecular hole transport material, film formation from a mixed solution containing a polymer binder and a hole transport material can be exemplified. Examples of molecular hole transport materials include film formation from a solution containing a hole transport material.

The solvent used for film formation from a solution is not particularly limited as long as it dissolves the hole transport material, and is a chlorine-based solvent such as chloroform, methylene chloride, dichloroethane, an ether-based solvent such as tetrahydrofuran, toluene, Examples thereof include aromatic hydrocarbon solvents such as xylene, ketone solvents such as acetone and methyl ethyl ketone, and ester solvents such as ethyl acetate, butyl acetate, and ethyl cellosolve acetate.
Examples of the film forming method from a solution include the same coating method as the above-described film forming method of the hole injection layer.

  As the polymer binder to be mixed, those that do not extremely inhibit charge transport are preferable, and those that weakly absorb visible light are preferably used. For example, polycarbonate, polyacrylate, polymethyl acrylate, polymethyl methacrylate, polystyrene, poly Examples thereof include vinyl chloride and polysiloxane.

  The thickness of the hole transport layer is not particularly limited, but can be appropriately changed according to the intended design, and is preferably about 1 to 1000 nm. If the thickness is less than the lower limit value, production tends to be difficult or the effect of hole transport is not sufficiently obtained. On the other hand, if the thickness exceeds the upper limit value, the driving voltage and the hole transport layer are increased. There is a tendency that the voltage applied to is increased. Therefore, the thickness of the hole transport layer is preferably 1 to 1000 nm as described above, more preferably 2 nm to 500 nm, and still more preferably 5 nm to 200 nm.

(Light emitting layer)
The light emitting layer 10 usually has an organic substance (a low molecular compound and a high molecular compound) that mainly emits fluorescence or phosphorescence, and may further contain a dopant material. Examples of the light emitting material constituting the light emitting layer that can be used in this embodiment include the following. A plurality of light emitting layers may be arranged between the anode 5 and the cathode 7 without being limited to a single light emitting layer.

(Dye material)
Examples of dye-based materials include cyclopentamine derivatives, tetraphenylbutadiene derivative compounds, triphenylamine derivatives, oxadiazole derivatives, pyrazoloquinoline derivatives, distyrylbenzene derivatives, distyrylarylene derivatives, pyrrole derivatives, thiophene ring compounds. Pyridine ring compounds, perinone derivatives, perylene derivatives, oligothiophene derivatives, trifumanylamine derivatives, oxadiazole dimers, pyrazoline dimers, and the like.

(Metal complex materials)
Examples of the metal complex material include metal complexes that emit light from triplet excited states such as iridium complexes and platinum complexes, aluminum quinolinol complexes, benzoquinolinol beryllium complexes, benzoxazolyl zinc complexes, benzothiazole zinc complexes, azomethyls. Zinc complex, porphyrin zinc complex, europium complex, etc., which has Al, Zn, Be, etc. as the central metal or rare earth metals such as Tb, Eu, Dy, etc., and oxadiazole, thiadiazole, phenylpyridine, phenylbenzo as ligands Examples thereof include metal complexes having an imidazole or quinoline structure.

(Polymer material)
Polymeric materials include polyparaphenylene vinylene derivatives, polythiophene derivatives, polyparaphenylene derivatives, polysilane derivatives, polyacetylene derivatives, polyfluorene derivatives, polyvinylcarbazole derivatives, and polymerized chromophores and metal complex light emitting materials. Etc.

Among the light emitting materials, examples of the material that emits blue light include distyrylarylene derivatives, oxadiazole derivatives, and polymers thereof, polyvinylcarbazole derivatives, polyparaphenylene derivatives, and polyfluorene derivatives. Of these, polymer materials such as polyvinyl carbazole derivatives, polyparaphenylene derivatives, and polyfluorene derivatives are preferred.
Examples of materials that emit green light include quinacridone derivatives, coumarin derivatives, and polymers thereof, polyparaphenylene vinylene derivatives, polyfluorene derivatives, and the like. Of these, polymer materials such as polyparaphenylene vinylene derivatives and polyfluorene derivatives are preferred.
Examples of materials that emit red light include coumarin derivatives, thiophene ring compounds, and polymers thereof, polyparaphenylene vinylene derivatives, polythiophene derivatives, and polyfluorene derivatives. Among these, polymer materials such as polyparaphenylene vinylene derivatives, polythiophene derivatives, and polyfluorene derivatives are preferable.

(Dopant material)
A dopant can be added to the light emitting layer for the purpose of improving the light emission efficiency and changing the light emission wavelength. Examples of such dopants include perylene derivatives, coumarin derivatives, rubrene derivatives, quinacridone derivatives, squalium derivatives, porphyrin derivatives, styryl dyes, tetracene derivatives, pyrazolone derivatives, decacyclene, phenoxazone, and the like. In addition, the thickness of such a light emitting layer is about 20-2000 mm normally.

(Light-emitting layer deposition method)
As a method for forming a light emitting layer containing an organic substance, a method including directly applying and forming a light emitting layer on a layer (lower layer) on which a light emitting layer is applied and formed using a solution containing a light emitting material, a solution containing a light emitting material is predetermined. Examples thereof include a method of transferring a film for a light-emitting layer obtained by coating on the substrate to a lower layer of the light-emitting layer, and a vacuum deposition method. Specific examples of the solvent used for the film formation from the solution include the same solvents as those for dissolving the hole transport material when forming the hole transport layer from the above solution.

  As a method for applying a solution containing a light emitting material, a spin coating method, a casting method, a micro gravure coating method, a gravure coating method, a bar coating method, a roll coating method, a wire bar coating method, a dip coating method, a slit coating method, a capillary Coating methods such as coating methods, spray coating methods, nozzle coating methods, etc., gravure printing methods, screen printing methods, flexographic printing methods, offset printing methods, reverse printing methods, printing methods such as inkjet printing methods, etc. may be used. it can. A printing method such as a gravure printing method, a screen printing method, a flexographic printing method, an offset printing method, a reversal printing method, and an ink jet printing method is preferable in that pattern formation and multi-coloring are easy. In the case of a sublimable low-molecular compound, a vacuum deposition method can be used. Furthermore, a method of forming a light emitting layer only at a desired place by laser transfer or thermal transfer can be used.

(Layer provided between the cathode and the light emitting layer)
One or a plurality of predetermined layers 11 are provided between the light emitting layer 10 and the cathode (second electrode) 7 as necessary. As described above, for example, an electron injection layer, an electron transport layer, a hole blocking layer, and the like are provided between the light emitting layer 10 and the cathode (second electrode) 7. When both the electron injection layer and the electron transport layer are provided between the cathode 7 and the light emitting layer 10, the layer in contact with the cathode is referred to as an electron injection layer, and the layers other than the electron injection layer are referred to as an electron transport layer. There is a case.

  The electron injection layer is a layer having a function of improving electron injection efficiency from the cathode. The electron transport layer is a layer having a function of improving electron injection from the cathode, the electron injection layer, or the electron transport layer closer to the cathode. The hole blocking layer is a layer having a function of blocking hole transport. In the case where the electron injection layer and / or the electron transport layer have a function of blocking hole transport, these layers may also serve as the hole blocking layer. The fact that the hole blocking layer has a function of blocking hole transport makes it possible, for example, to produce an element that allows only a hole current to flow, and confirm the blocking effect by reducing the current value.

(Electron injection layer)
Depending on the type of the light emitting layer, the electron injection layer may be an alkali metal or alkaline earth metal, an alloy containing one or more of the above metals, an oxide, halide and carbonate of the metal, or a mixture of the substances. Etc.

  Examples of the alkali metal or its oxide, halide, carbonate include lithium, sodium, potassium, rubidium, cesium, lithium oxide, lithium fluoride, sodium oxide, sodium fluoride, potassium oxide, potassium fluoride, oxide Examples include rubidium, rubidium fluoride, cesium oxide, cesium fluoride, and lithium carbonate.

  Examples of the alkaline earth metals or oxides, halides and carbonates thereof include magnesium, calcium, barium, strontium, magnesium oxide, magnesium fluoride, calcium oxide, calcium fluoride, calcium fluoride, barium oxide, fluorine. Barium fluoride, strontium oxide, strontium fluoride, magnesium carbonate and the like.

  Furthermore, a metal, a metal oxide, an organometallic compound doped with a metal salt, an organometallic complex compound, or a mixture thereof can also be used as a material for the electron injection layer.

This electron injection layer may have a stacked structure in which two or more layers are stacked. Specifically, Li / Ca etc. are mentioned. This electron injection layer is formed by vapor deposition, sputtering, printing, or the like.
The thickness of the electron injection layer is preferably about 1 nm to 1 μm.

(Electron transport layer)
As the material for forming the electron transport layer, known materials can be used, such as oxadiazole derivatives, anthraquinodimethane or derivatives thereof, benzoquinone or derivatives thereof, naphthoquinone or derivatives thereof, anthraquinones or derivatives thereof, tetracyanoanthraquinodi. Examples include methane or its derivatives, fluorenone derivatives, diphenyldicyanoethylene or its derivatives, diphenoquinone derivatives, or metal complexes of 8-hydroxyquinoline or its derivatives, polyquinoline or its derivatives, polyquinoxaline or its derivatives, polyfluorene or its derivatives, etc. The

  Of these, oxadiazole derivatives, benzoquinone or derivatives thereof, anthraquinones or derivatives thereof, or metal complexes of 8-hydroxyquinoline or derivatives thereof, polyquinoline or derivatives thereof, polyquinoxaline or derivatives thereof, polyfluorene or derivatives thereof are preferred, 2- (4-biphenylyl) -5- (4-t-butylphenyl) -1,3,4-oxadiazole, benzoquinone, anthraquinone, tris (8-quinolinol) aluminum, and polyquinoline are more preferable.

  The electron injection layer and the hole injection layer may be collectively referred to as a charge injection layer, and the electron transport layer and the hole transport layer may be collectively referred to as a charge transport layer.

(Second electrode)
The second electrode 7 in the first embodiment is an electrode arranged to face the first electrode 5 and serves as a cathode of the organic electroluminescence element. In the present invention, the second electrode 7 described later is used. As shown in the second embodiment, it is possible to use an anode. As such a cathode material, a material having a small work function and easy electron injection into the light emitting layer is preferable. The cathode material is preferably a material having high electrical conductivity and high visible light reflectance. Specific examples of such cathode materials include metals, metal oxides, alloys, graphite or graphite intercalation compounds, and inorganic semiconductors such as zinc oxide (ZnO).

  As the metal, an alkali metal, an alkaline earth metal, a transition metal, a group 13 metal of the periodic table, or the like can be used. Specific examples of these metals include lithium, sodium, potassium, rubidium, cesium, beryllium, magnesium, calcium, strontium, barium, gold, silver, platinum, copper, manganese, titanium, cobalt, nickel, tungsten, tin, and aluminum. , Scandium, vanadium, zinc, yttrium, indium, cerium, samarium, europium, terbium, ytterbium, and the like.

  Examples of the alloy include an alloy containing at least one of the above metals. Specifically, a magnesium-silver alloy, a magnesium-indium alloy, a magnesium-aluminum alloy, an indium-silver alloy, a lithium-aluminum alloy, Examples thereof include a lithium-magnesium alloy, a lithium-indium alloy, and a calcium-aluminum alloy.

  The cathode 7 is an electrode having optical transparency as required. Examples of these materials include conductive oxides such as indium oxide, zinc oxide, tin oxide, ITO and IZO; polyaniline or derivatives thereof, polythiophene. Or electroconductive organic substances, such as its derivative (s), can be mentioned.

  The cathode (second electrode) 7 may have a laminated structure of two or more layers. Moreover, an electron injection layer may be used as a cathode.

  The film thickness of the cathode (second electrode) 7 can be appropriately selected in consideration of electric conductivity and durability, but is, for example, 10 nm to 10 μm, preferably 20 nm to 1 μm, more preferably 50 nm to 500 nm.

  Examples of the method for forming the cathode (second electrode) 7 include a vacuum deposition method, a sputtering method, and a laminating method in which a metal thin film is thermocompression bonded. Note that the second electrode may have a laminated structure of two or more layers.

In the organic electroluminescence element of the present embodiment, a combination example of layer configurations from the anode 5 to the cathode 7 is shown below.
a) Anode / hole injection layer / light emitting layer / cathode b) Anode / hole injection layer / light emitting layer / electron injection layer / cathode c) Anode / hole injection layer / light emitting layer / electron transport layer / cathode d) Anode / Hole injection layer / light emitting layer / electron transport layer / electron injection layer / cathode e) anode / hole transport layer / light emitting layer / cathode f) anode / hole transport layer / light emitting layer / electron injection layer / cathode g) Anode / hole transport layer / light emitting layer / electron transport layer / cathode h) anode / hole transport layer / light emitting layer / electron transport layer / electron injection layer / cathode i) anode / hole injection layer / hole transport layer / Emissive layer / cathode j) anode / hole injection layer / hole transport layer / emission layer / electron injection layer / cathode k) anode / hole injection layer / hole transport layer / emission layer / electron transport layer / cathode l) Anode / hole injection layer / hole transport layer / light emitting layer / electron transport layer / electron injection layer / cathode (here, the symbol “/” indicates that the layers sandwiching the symbol “/” are stacked adjacent to each other) Indicating that. Hereinafter the same.)

Moreover, the organic electroluminescent element of this Embodiment may have two or more light emitting layers, and as an organic electroluminescent element which has two light emitting layers, the layer structure shown in the following q) is shown. Can be mentioned.
q) Anode / charge injection layer / hole transport layer / light emitting layer / electron transport layer / charge injection layer / charge generation layer / charge injection layer / hole transport layer / light emitting layer / electron transport layer / charge injection layer / cathode Specifically, as an organic electroluminescence device having three or more light emitting layers, (charge generation layer / charge injection layer / hole transport layer / light emission layer / electron transport layer / charge injection layer) is repeated one time. Examples of the unit include a layer structure including two or more repeating units shown in the following r).
r) Anode / charge injection layer / hole transport layer / light emitting layer / electron transport layer / charge injection layer / (the repeating unit) / (the repeating unit) /... / cathode Is a layer that generates holes and electrons by applying. Examples of the charge generation layer include a thin film made of vanadium oxide, indium tin oxide (abbreviated as ITO), molybdenum oxide, or the like.
In an organic electroluminescence element, an anode is usually disposed on the substrate side, but a cathode may be disposed on the substrate side.

  In the organic electroluminescent element of the present embodiment, an insulating layer having a thickness of 2 nm or less may be provided adjacent to the electrode in order to further improve the adhesion with the electrode or improve the charge injection property from the electrode. In addition, a thin buffer layer may be inserted between each of the aforementioned layers in order to improve adhesion at the interface or prevent mixing.

(Protective layer)
After the cathode (second electrode) 7 is formed as described above, the light emitting function includes the auxiliary electrode 4 -first electrode (anode) 5 -light emitting portion 6 -second electrode (cathode) 7 as a basic structure. In order to protect the portion, a protective layer (upper sealing film) 8 for sealing the light emitting function portion is formed. The protective layer 8 usually has at least one inorganic layer and at least one organic layer. The number of stacked layers is determined as necessary. Basically, inorganic layers and organic layers are alternately stacked.

  Note that the plastic substrate has higher permeability of gases such as oxygen and water than the glass substrate. Since a light emitting substance such as the light emitting layer 10 is easily oxidized and easily deteriorates by contact with oxygen, water, or the like, when a plastic substrate is used as the substrate 1, a treatment for improving gas barrier properties is applied to the substrate in advance. It is preferable to apply. For example, it is preferable to stack a lower sealing film having a high barrier property against gas or the like on a plastic substrate, and then stack the light emitting function part on the lower sealing film. The lower sealing film is usually formed with the same configuration and the same material as the protective layer (upper sealing film).

  Next, a second embodiment of the organic electroluminescence element according to the present invention will be described with reference to FIG. The difference between the second embodiment and the first embodiment described above is that the organic electroluminescence element of the first embodiment transmits light from the light emitting unit 6 through the transparent anode (first electrode) 5. In contrast, in the organic electroluminescence element of the second embodiment, the light from the light emitting portion 26 is transmitted through the transparent cathode (first electrode), whereas the bottom emission type element is emitted from the transparent support substrate 1 to the outside. 27 is a top emission type element that transmits the light from the transparent protective layer 28 to the outside.

  In the second embodiment, the transparent first electrode that transmits light from the light emitting section 26 is the transparent cathode 27, and the auxiliary electrode 24 is formed on the surface of the first electrode 27 on the protective layer 28 side. . For the first electrode in the present embodiment, for example, a metal thin film exemplified as a cathode electrode can be used as a transparent cathode. In addition, since the metal thin film used for the transparent cathode is formed into a thin film to such an extent that light can be transmitted, the sheet resistance is increased. Therefore, the transparent cathode is preferably constituted by a laminate in which transparent electrodes such as ITO thin films are laminated in a metal foil film shape. Further, it is preferable to provide a reflective film having a high reflectance such as silver between the second electrode 25 and the substrate 21, and by providing such a reflective film, the light directed toward the substrate 21 is transmitted to the first electrode 27. Can be reflected to the side, and the light extraction efficiency can be improved. The auxiliary electrode 24 may be the same in shape, size, and constituent material as the auxiliary electrode 4 in the first embodiment, and is provided in contact with the transparent cathode (first electrode) 27 as described above. Is only different.

  Also in the second embodiment, the configuration in which the metal-doped molybdenum oxide layer is provided between the anode (second electrode) 25 and the light emitting layer 30 may be the same as that in the first embodiment described above. That is, the metal-doped molybdenum oxide layer is provided as at least one of a hole injection layer or a hole transport layer constituting the layer 29 provided between the anode 25 and the light emitting layer 30.

Even if the organic electroluminescence device according to the present invention is configured as in the second embodiment, the same actions and effects as those in the first embodiment can be obtained.
In other words, the organic electroluminescence device of the present invention reduces the voltage drop due to the resistance of the transparent electrode, even in the first embodiment and the second embodiment. Sufficiently suppressed and uniform light emission is possible. In addition, since the inorganic oxide layer and the layer laminated thereon can be provided easily and with high quality, the production is easy, and the light emission characteristics and the life characteristics are good.

  The organic electroluminescence element of the first embodiment has a bottom emission type element structure in which light from a light emitting part is transmitted through a transparent anode (first electrode) and emitted to the outside from a transparent support substrate. However, an organic electroluminescence device having the same bottom emission type device structure, in which a transparent cathode (first electrode) is provided on the transparent substrate side and an anode is provided on the protective layer side, can also be produced. The present invention can also be applied to an organic electroluminescence element having such a third structure.

  Furthermore, the organic electroluminescence element of the second embodiment has a top emission type element structure in which light from the light emitting part is transmitted through the transparent cathode (first electrode) and emitted from the transparent protective layer to the outside. However, an organic electroluminescence device having the same top emission type device structure, in which a transparent anode (first electrode) is provided on the transparent protective layer side and a cathode is provided on the support substrate side, can also be produced. . The present invention can also be applied to such an organic electroluminescence element having the fourth structure.

  The organic electroluminescence element of the embodiment of the present invention as described above can be suitably used for a curved or planar illumination device, for example, a planar light source used as a light source of a scanner, or a display device.

  Examples of the display device including the organic electroluminescence element include an active matrix display device, a passive matrix display device, a segment display device, a dot matrix display device, and a liquid crystal display device. The organic electroluminescence element is used as a light emitting element constituting each pixel in an active matrix display device and a passive matrix display device, and is used as a light emitting element constituting each segment in a segment display device. In liquid crystal display devices, it is used as a backlight.

Hereinafter, although this invention is demonstrated more concretely based on a manufacture example and a reference example, this invention is not limited to the following illustrations.
In addition, the compounds A to C represented by the following structural formulas (A) to (C) used in Synthesis Examples 1 and 2 were synthesized according to the method described in International Publication No. 2000/046321 pamphlet.

(Synthesis Example 1)
Polymer compound 1 represented by the following general formula (1) was synthesized by the following method.

  First, 0.91 g of methyltrioctylammonium chloride (trade name: Aliquat 336, manufactured by Aldrich), 5.23 g of the above compound A, and 4.55 g of the above compound C were charged into a reaction vessel (200 mL separable flask), and then reacted. The system was replaced with nitrogen gas. Thereafter, 70 mL of toluene was added, 2.0 mg of palladium acetate and 15.1 mg of tris (o-tolyl) phosphine were added, and the mixture was refluxed to obtain a mixed solution.

  To the obtained mixed solution, 19 mL of an aqueous sodium carbonate solution was added dropwise and stirred overnight under reflux, then 0.12 g of phenylboric acid was added and stirred for 7 hours. Thereafter, 300 ml of toluene was added, the reaction solution was separated, and the organic phase was washed with an aqueous acetic acid solution and water, and then an aqueous sodium N, N-diethyldithiocarbamate solution was added and stirred for 4 hours.

Next, after the mixed solution after stirring is separated, it is passed through a silica gel-alumina column, washed with toluene, dropped into methanol to precipitate a polymer, and then the obtained polymer is filtered and dried under reduced pressure. Dissolved in. The obtained toluene solution was again added dropwise to methanol to form a precipitate. The precipitate was filtered and dried under reduced pressure to obtain 6.33 g of polymer compound 1. The obtained polymer compound 1 had a polystyrene equivalent weight average molecular weight Mw of 3.2 × 10 ⁵ and a polystyrene equivalent number average molecular weight Mn of 8.8 × 10 ⁴ .

(Synthesis Example 2)
Polymer compound 2 represented by the following general formula (2) was synthesized by the following method.

  First, 22.5 g of compound B and 17.6 g of 2,2′-bipyridyl were charged into a reaction vessel, and the inside of the reaction system was replaced with nitrogen gas. Thereafter, 1500 g of tetrahydrofuran (dehydrated solvent) previously deaerated by bubbling with an argon gas was added to obtain a mixed solution. To the obtained mixed solution, 31 g of bis (1,5-cyclooctadiene) nickel (0) was added, stirred at room temperature for 10 minutes, and reacted at 60 ° C. for 3 hours. The reaction was performed in a nitrogen gas atmosphere.

  Next, after cooling the obtained reaction solution, a mixed solution of 25% by mass of ammonia water 200 mL / methanol 900 mL / ion-exchanged water 900 mL was poured into this solution and stirred for about 1 hour. Thereafter, the produced precipitate was collected by filtration, and this precipitate was dried under reduced pressure and then dissolved in toluene. And after filtering the obtained toluene solution and removing an insoluble matter, this toluene solution was refine | purified by passing through the column filled with the alumina.

  Next, the purified toluene solution was washed with a 1N aqueous hydrochloric acid solution, allowed to stand and separated, and then the toluene solution was recovered. And this toluene solution was wash | cleaned with about 3 mass% ammonia water, and after leaving still and liquid-separating, the toluene solution was collect | recovered. Thereafter, this toluene solution was washed with ion-exchanged water, allowed to stand and separated, and the washed toluene solution was recovered.

Next, the washed toluene solution was poured into methanol to form a precipitate. The precipitate was washed with methanol and then dried under reduced pressure to obtain polymer compound 2. The obtained polymer compound 2 had a polystyrene equivalent weight average molecular weight of 8.2 × 10 ⁵ and a polystyrene equivalent number average molecular weight of 1.0 × 10 ⁵ .

(Production Example 1)
In this production example 1, in order to confirm the effect when the auxiliary electrode is formed on the transparent first electrode, the organic electroluminescence element in which the light emitting layer has a single layer structure and the auxiliary electrode is arranged on the substrate side surface of the transparent anode. Manufactured.

  A glass substrate (100 mm × 100 mm) was used as the support substrate. The temperature of the supporting substrate was set to 120 ° C., and Cr having a film thickness of 1000 nm was deposited on the supporting substrate by a DC sputtering method using a Cr target and Ar as a sputtering gas. The film forming pressure at this time was 0.5 Pa, and the sputtering power was 2.0 kW. A photoresist was applied on the Cr film and further baked at 110 ° C. for 90 seconds. Next, in a square frame-shaped opening composed of lines with a line width of 20 mm and the frame of the opening, the vertical and horizontal pitches are 300 μm × 100 μm, and the vertical and horizontal line widths are 70 μm × 30 μm, respectively. The film was exposed at an energy of 200 mJ through a photomask having a lattice-type opening made of, developed with 0.5% by weight aqueous potassium hydroxide solution, and post-baked at 130 ° C. for 110 seconds. Next, the resist residue is peeled off by immersing in Cr etching solution at 40 ° C. for 120 seconds, patterning Cr, and then immersing in a 2% by mass aqueous potassium hydroxide solution. 1 auxiliary electrode and 2nd auxiliary electrode) were formed.

Next, a first electrode was formed on the substrate on which the auxiliary electrode was formed. Specifically, an ITO film having a thickness of 3000 nm was deposited by a DC sputtering method using a substrate temperature of 120 ° C., an ITO firing target as a first electrode material, and Ar as a sputtering gas. The film forming pressure at this time was 0.25 Pa, and the sputtering power was 0.25 kW. Thereafter, annealing was performed in an oven at 200 ° C. for 40 minutes. Thereafter, the substrate on which the first electrode is formed is ultrasonically cleaned using a weak alkaline detergent at 60 ° C., cold water, and hot water at 50 ° C., pulled up from the hot water at 50 ° C. and dried, and then washed with UV / O _{3 for} 20 minutes. Went.

  Next, using a 0.45 μm diameter filter and a 0.2 μm diameter filter, respectively, a suspension of poly (3,4) ethylenedioxythiophene / polystyrene sulfonic acid (trade name: BaytronP CH8000, manufactured by Starck Vitech). The suspension is filtered in two stages, and a thin film with a thickness of 80 nm is formed on the washed substrate by spin coating using the solution filtered in the second stage, and is heated at 200 ° C. on a hot plate in an air atmosphere. Heat treatment was performed for 15 minutes to form a hole injection layer.

  Subsequently, the polymer compound 1 and the polymer compound 2 obtained in Synthesis Examples 1 and 2 were weighed at a weight ratio of 1: 1 and dissolved in toluene to prepare a 1% by mass polymer solution. The prepared polymer solution is formed on the substrate on which the hole injection layer is formed to a thickness of 80 nm by spin coating, and then heat-treated on a hot plate in a nitrogen atmosphere at 130 ° C. for 60 minutes to emit light. A layer was formed.

Thereafter, the substrate on which the light-emitting layer was formed was introduced into a vacuum vapor deposition machine, and LiF, Ca, and Al were sequentially deposited at a thickness of 2 nm, 5 nm, and 200 nm as a cathode to form a second electrode. In this vapor deposition step, metal deposition was started after the degree of vacuum reached 1 × 10 ⁻⁴ Pa or less.

  Finally, in an inert gas, the surface of the second electrode on the substrate on which the second electrode is formed is covered with a glass plate, and further, the four sides are covered with a photo-curing resin, and then the photo-curing resin is cured to protect it. A layer was formed to obtain an organic electroluminescence element.

(Reference Example 1)
In Production Example 1, the photomask for forming the auxiliary electrode was the same as Production Example 1 except that a photomask having only a square frame-shaped opening composed of lines with a line width of 20 mm was used. Thus, a comparative organic electroluminescence element was produced.

(Reference Example 2)
In the above manufacturing example 1, as a photomask for forming the auxiliary electrode, a photomask having a lattice-type opening having a vertical and horizontal pitch of 300 μm × 100 μm and a vertical and horizontal line width of 70 μm × 30 μm, respectively. A comparative organic electroluminescence element was produced in the same manner as in Production Example 1 except that the mask was used.

(Evaluation of auxiliary electrode formation effect)
The light emission characteristics of the organic electroluminescence elements obtained in Production Example 1 and Reference Examples 1 and 2 were evaluated. Specifically, the light emission luminance when a voltage of 8 V was applied to the entire device was measured, and the state of the light emitting surface was visually observed. The obtained results are shown below (Table 1).

（表１）に示した結果から明らかなように、本発明の有機エレクトロルミネッセンス素子においては、発光面積が大きい場合でも発光輝度のムラが十分に抑制され、均一発光が可能であることが確認された。

As is clear from the results shown in (Table 1), in the organic electroluminescence device of the present invention, it was confirmed that even when the light emitting area is large, unevenness in light emission luminance is sufficiently suppressed and uniform light emission is possible. It was.

  In the following Production Examples 2 to 7 and Reference Examples 3 and 4, in order to confirm the effect of providing the metal-doped molybdenum oxide layer between the anode and the light emitting layer, the auxiliary electrode was formed on the substrate side surface of the transparent anode. An organic electroluminescence device was produced in which a metal-doped molybdenum oxide layer was provided between the anode and the light-emitting layer.

(Production Example 2)
(A: Deposition of Al-doped MoO ₃ on a glass substrate by a vacuum deposition method)
A plurality of glass substrates were prepared, one side of which was partially covered with a vapor deposition mask, and attached to the vapor deposition chamber using a substrate holder.

MoO ₃ powder (manufactured by Aldrich, purity 99.99%) was packed in a tungsten board for a box-type sublimation substance, covered with a cover with holes so that the material would not scatter, and set in a vapor deposition chamber. Al (manufactured by Koyo Chemical Co., Ltd., purity 99.999%) was put in a crucible and set in a vapor deposition chamber.

The degree of vacuum in the vapor deposition chamber is set to 3 × 10 ⁻⁵ Pa or less, MoO ₃ is gradually heated by a resistance heating method and sufficiently degassed, and Al is dissolved in the crucible by an electron beam and fully desorbed. After performing the gas, it was subjected to vapor deposition. The degree of vacuum during vapor deposition was 9 × 10 ⁻⁵ Pa or less. The film thickness and the deposition rate were constantly monitored with a crystal resonator. When the deposition rate of MoO ₃ was about 0.28 nm / second and the deposition rate of Al was about 0.01 nm / second, the main shutter was opened and film formation on the substrate was started. During deposition, the substrate was rotated so that the film thickness was uniform. Film formation was performed for about 36 seconds while controlling the vapor deposition rate to the above speed, and a substrate provided with a co-deposition film having a thickness of about 10 nm was obtained. The composition ratio of Al to the total of MoO ₃ and Al in the film was about 3.5 mol%.

(B: Durability test)
After film formation, the obtained substrate was taken out into the atmosphere and the film surface was observed with an optical microscope (500 times). As a result, no crystal structure was observed, and it was confirmed that the film was in an amorphous state.
When the obtained substrate was exposed to pure water for 1 minute and observed again with an optical microscope, there was no change and the surface was not melted. In either case, the substrate was further exposed to pure water for 3 minutes, or the film was wiped with a non-woven fabric (trade name “Bencot”, manufactured by Ozu Sangyo Co., Ltd.) containing pure water and then visually observed. The membrane remained unchanged.
Further, the substrate obtained separately from the substrate exposed to the pure water was exposed to acetone for 1 minute and observed with an optical microscope. There was no change and the surface was not melted. The substrate was further exposed to acetone for 3 minutes, or the film was wiped with a non-woven fabric containing acetone and visually confirmed. In either case, the film remained unchanged.

(C: Measurement of transmittance)
Further, the transmittance of the deposited film after film formation was measured using a transmittance / reflectance measuring apparatus (trade name “FilmTek 3000” manufactured by Scientific Computing International). The results are shown in (Table 2) below. The transmission spectrum rose from a wavelength of about 300 nm. The transmittance at a wavelength of 320 nm was 21.6%, and the transmittance at 360 nm was 56.6%. Compared to Reference Example 3 described later, the transmittance was 3.6 times at 320 nm and 1.6 times at 360 nm.

(Production Example 3)
A substrate provided with a co-deposited film was obtained in the same manner as in Production Example 2 (A) except that oxygen was introduced into the chamber during the deposition. The amount of oxygen was controlled to 15 sccm by a mass flow controller. The degree of vacuum during vapor deposition was about 2.3 × 10 ⁻³ Pa. The thickness of the obtained co-deposited film was about 10 nm, and the composition ratio of Al to the total of MoO ₃ and Al in the film was about 3.5 mol%.

  After film formation, the durability of the obtained substrate was evaluated in the same manner as in Production Example 2 (B). No change was observed when exposed to either pure water or acetone.

(Production Example 4)
A substrate provided with a co-deposited film, except that the deposition rate was controlled to about 0.37 nm / second for MoO _{3 and} about 0.001 nm / second for Al. Got. The thickness of the obtained co-deposited film was about 10 nm, and the composition ratio of Al to the total of MoO ₃ and Al in the film was about 1.3 mol%.

  After film formation, the durability of the obtained substrate was evaluated in the same manner as in Production Example 2 (C). No change was observed when exposed to either pure water or acetone.

(Production Example 5)
The substrate obtained in Production Example 2 (A) was placed in a clean oven in an air atmosphere and heat-treated at 250 ° C. for 60 minutes. After cooling, the transmittance of the deposited film was measured in the same manner as in Production Example 2 (C). The results are shown in (Table 2) below. The transmittance at a wavelength of 320 nm was 28.9%, and the transmittance at 360 nm was 76.2%. Compared with the following Reference Example 3, the transmittance was 4.7 times at 320 nm and 2.2 times at 360 nm.

(Reference Example 3)
A substrate provided with a deposited film having a thickness of about 10 nm was obtained in the same manner as in Production Example 2 except that Al was not deposited and only MoO ₃ was deposited at about 0.28 nm / second.
After film formation, the obtained substrate was taken out into the atmosphere and the film surface was observed with an optical microscope (500 times). As a result, it was confirmed that the crystal structure was not observed and the film was in an amorphous state.

  When the obtained substrate was exposed to pure water for 1 minute and observed again with an optical microscope, it was observed that a bleeding pattern was observed and the surface was melted. The substrate was further exposed to pure water for 3 minutes, or the film was wiped with a non-woven fabric soaked with pure water and visually observed. In all cases, the film disappeared.

  Another obtained substrate was exposed to acetone for 1 minute and observed with an optical microscope. As a result, a bleeding pattern was observed and the surface was melted. The substrate was further exposed to acetone for 3 minutes, or the film was wiped with a non-woven fabric containing acetone and then visually confirmed. In all cases, the film was lost.

  Further, the transmittance of the deposited film after film formation was measured in the same manner as in Production Example 2 (C). The results are shown below (Table 2). The transmittance at a wavelength of 320 nm was 6.1%, the transmittance at 360 nm was 35.4%, and it was confirmed that the transmittance was low.

(Synthesis Example 3)
2,7-bis (1,3,2-dioxaborolan-2-yl) -9,9-dioctyl was added to a separable flask equipped with a stirring blade, baffle, length-adjustable nitrogen inlet tube, cooling tube, and thermometer. Fluorene 158. 29 parts by weight of bis- (4-bromophenyl) -4- (1-methylpropyl) -benzenamine 136. 11 parts by weight, 27 parts by weight of tricaprylmethylammonium chloride (Aliquat 336 manufactured by Henkel) and 1800 parts by weight of toluene were charged, and the temperature was raised to 90 ° C. with stirring while flowing nitrogen from the nitrogen introduction tube.

  Next, 0.066 parts by weight of palladium (II) acetate and 0.45 parts by weight of tri (o-toluyl) phosphine were added, and then a 17.5% aqueous sodium carbonate solution (573 parts by weight) was added dropwise over 1 hour. did. After completion of the dropwise addition, the nitrogen inlet tube was lifted from the liquid level and kept under reflux for 7 hours, then 3.6 parts by weight of phenylboric acid was added, kept under reflux for 14 hours, and cooled to room temperature.

  After removing the reaction solution aqueous layer, the reaction solution oil layer was diluted with toluene and washed with 3% acetic acid aqueous solution and ion-exchanged water. To the separated oil layer, 13 parts by weight of sodium N, N-diethyldithiocarbamate trihydrate was added and stirred for 4 hours. Thereafter, the mixture was passed through a mixed column of activated alumina and silica gel, and toluene was passed through to wash the column.

The filtrate and washings were mixed and then added dropwise to methanol to precipitate the polymer. The obtained polymer precipitate was separated by filtration, washed with methanol, and then dried with a vacuum dryer to obtain 192 parts by weight of polymer. The resulting polymer is referred to as polymer compound P1. When the polystyrene equivalent weight average molecular weight and number average molecular weight of this polymer compound P1 were determined by the following GPC analysis method, the polystyrene equivalent weight average molecular weight was 3.7 × 10 ⁵ , and the number average molecular weight was 8.9 ×. There were 10 ⁴ .

(GPC analysis method)
The polystyrene equivalent weight average molecular weight and number average molecular weight were determined by gel permeation chromatography (GPC). Standard polystyrene made by Polymer Laboratories was used to prepare a GPC calibration curve. The polymer to be measured was dissolved in tetrahydrofuran to a concentration of about 0.02% by weight, and 10 μL was injected into the GPC apparatus.

  The GPC apparatus used was LC-10ADvp manufactured by Shimadzu Corporation. As the column, two columns manufactured by Polymer Laboratories (“PLgel” 10 μm MIXED-B column (300 × 7.5 mm)) were connected in series, and tetrahydrofuran was used as a mobile phase at 25 ° C. and 1.0 mL / min. Flowed at a flow rate. The detector used was a UV detector, and the absorbance at 228 nm was measured.

(Production Example 6)
(Production of organic electroluminescence device)
A glass substrate having an ITO thin film patterned on the surface was used as the substrate, and an Al-doped MoO ₃ layer having a thickness of 10 nm was deposited on the ITO thin film by a vacuum deposition method in the same manner as in Production Example 2.

  After the film formation, the substrate was taken out into the atmosphere, and the polymer compound P1 obtained in Synthesis Example 3 was formed on the vapor-deposited film by spin coating to form an interlayer layer having a thickness of 20 nm. The interlayer layer formed on the extraction electrode portion and the sealing area was removed, and baking was performed at 200 ° C. for 20 minutes on a hot plate.

  Thereafter, a polymer light-emitting organic material (manufactured by RP158 Summation Co., Ltd.) was formed on the interlayer layer by a spin coating method to form a light-emitting layer having a thickness of 90 nm. The light emitting layer formed on the extraction electrode portion and the sealing area was removed.

  The subsequent processes up to the sealing were performed in vacuum or nitrogen so that the elements in the process were not exposed to the atmosphere.

  The substrate was heated at a substrate temperature of about 100 ° C. for 60 minutes in a vacuum heating chamber. Thereafter, the substrate was transferred to a vapor deposition chamber, and a cathode mask was aligned on the surface of the light emitting layer so that a cathode was formed on the light emitting portion and the extraction electrode portion. Further, the cathode was deposited while rotating the mask and the substrate. As a cathode, metal Ba is heated by a resistance heating method and deposited at a deposition rate of about 0.2 nm / second and a film thickness of 5 nm, and Al is deposited thereon by using an electron beam deposition method at a deposition rate of about 0.2 nm / second. The film was deposited with a film thickness of 150 nm.

Thereafter, the substrate is bonded to a prepared sealing glass coated with UV curable resin around the substrate, kept in vacuum, then returned to atmospheric pressure, fixed by irradiation with UV, and light emitting region A 2 × 2 mm organic electroluminescence element was produced.
The obtained organic electroluminescence device had a layer structure of glass substrate / ITO film / Al-doped MoO ₃ layer / interlayer layer / light emitting layer / Ba layer / Al layer / sealing glass.

(Evaluation of organic electroluminescence device)
The manufactured element was energized so that the luminance was 1000 cd / m ^2, and current-voltage characteristics were measured. In addition, the device was driven at a constant current at 10 mA, light emission was started at an initial luminance of about 2000 cd / m ² , the light emission was continued as it was, and the light emission lifetime was measured. The results are shown in the following (Table 3) and (Table 4). Compared to Reference Example 4 to be described later, the maximum power efficiency is slightly higher, the drive voltage at the time of 1000 cd / m ² emission is reduced, and the life is extended by about 1.6 times.

(Production Example 7)
Except that the Al-doped MoO ₃ layer was formed in the same procedure as in Production Example 4, the same operation as in Production Example 6 was performed to produce an organic electroluminescence device, and current-voltage characteristics and emission lifetime were measured. The emission lifetime was measured by driving at a constant current of 10 mA, starting emission at an initial luminance of about 2000 cd / m ² , and then continuing emission. The results are shown in the following (Table 2) and (Table 3). Compared to the following Reference Example 4, higher maximum power efficiency somewhat, 1000 cd / m ² driving voltage during light emission is lowered and the lifetime is prolonged to about 2.4 times.

(Reference Example 4)
Instead of depositing the Al-doped MoO ₃ layer, other depositing the MoO ₃ layers in the same procedure as in Reference Example 3, the same procedure as in Production Example 6, to fabricate an organic electroluminescent device, the current - voltage Characteristics and luminescence lifetime were measured. The light emission lifetime was measured by driving at a constant current of 10 mA, starting light emission at an initial luminance of about 2000 cd / m ² , and continuing light emission as it was. The results are shown in the following (Table 3) and (Table 4).

It is sectional drawing of the organic electroluminescent element of the 1st Embodiment of this invention. It is a top view which shows roughly an example of the positional relationship of the 1st auxiliary electrode and the 2nd auxiliary electrode in an organic electroluminescent element. It is a top view which shows roughly an example of the positional relationship of the 1st auxiliary electrode and the 2nd auxiliary electrode in an organic electroluminescent element. It is a top view which shows roughly an example of the positional relationship of the 1st auxiliary electrode and the 2nd auxiliary electrode in an organic electroluminescent element. It is a top view which shows roughly another example of the positional relationship of the 1st auxiliary electrode and the 2nd auxiliary electrode in an organic electroluminescent element. It is sectional drawing of the organic electroluminescent element of the 2nd Embodiment of this invention.

Explanation of symbols

DESCRIPTION OF SYMBOLS 1 Transparent support substrate 2, 2a, 2b, 2c, 2d 1st auxiliary electrode 3, 3a, 3b, 3c, 3d 2nd auxiliary electrode 4 Auxiliary electrode 5 Transparent anode (1st electrode)
6 Light-emitting part 7 Cathode (second electrode)
8 Protective film (upper sealing film)
9 Layer provided between anode and light emitting layer (including metal doped molybdenum oxide layer)
DESCRIPTION OF SYMBOLS 10 Light emitting layer 11 Layer provided between a cathode and a light emitting layer 21 Support substrate 22 1st auxiliary electrode 23 2nd auxiliary electrode 24 Auxiliary electrode 25 Anode (2nd electrode)
26 Light Emitting Unit 27 Transparent Cathode (First Electrode)
28 Protective film (upper sealing film)
29 Layer provided between the anode and the light emitting layer (including metal doped molybdenum oxide layer)
30 Light emitting layer 41 Layer provided between the cathode and the light emitting layer

Claims (12)

A transparent first electrode that is one of an anode and a cathode;
An auxiliary electrode having a low electrical resistance compared to the first electrode and provided in contact with the first electrode;
A second electrode that is the other of the anode and the cathode;
A light emitting layer disposed between the first electrode and the second electrode;
A metal-doped molybdenum oxide layer disposed between the anode and the light-emitting layer,
The auxiliary electrode is
A frame-shaped first auxiliary electrode;
An organic electroluminescence device comprising: a second auxiliary electrode disposed within a frame of the first auxiliary electrode, electrically connected to the first auxiliary electrode, and having a line width narrower than the first auxiliary electrode.   2. The organic electroluminescence element according to claim 1, wherein a value obtained by dividing the line width of the second auxiliary electrode by the line width of the first auxiliary electrode is 1/1000 to 1/10.   The organic electroluminescence element according to claim 1, wherein the metal-doped molybdenum oxide layer is provided in contact with the anode.   The organic electroluminescence device according to claim 1, wherein the metal-doped molybdenum oxide layer has a visible light transmittance of 50% or more.   The organic electroluminescence according to any one of claims 1 to 4, wherein the dopant metal contained in the metal-doped molybdenum oxide layer is selected from the group consisting of transition metals, metals of Group 13 of the periodic table, and mixtures thereof. element.   The organic electroluminescence device according to claim 5, wherein the dopant metal is aluminum.   The ratio of the dopant metal contained in the said metal dope molybdenum oxide layer is 0.1-20.0 mol%, The organic electroluminescent element of any one of Claims 1-6. It is a manufacturing method of the organic electroluminescent element according to any one of claims 1 to 7,
An organic electroluminescence device comprising a step of laminating a metal-doped molybdenum oxide layer by simultaneously depositing molybdenum oxide and a dopant metal on one layer selected from the group consisting of an anode, a hole injection layer and a hole transport layer Manufacturing method.   The method for manufacturing an organic electroluminescence element according to claim 8, further comprising a step of heating the metal-doped molybdenum oxide layer laminated in the step of laminating the metal-doped molybdenum oxide layer.   An illuminating device comprising the organic electroluminescence element according to claim 1.   A planar light source comprising the organic electroluminescence element according to claim 1.   A display device comprising the organic electroluminescence element according to claim 1.

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