JP5178431B2 - Organic electroluminescence device - Google Patents

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.

  An organic electroluminescence element (hereinafter sometimes referred to as an organic EL element) includes a pair of electrodes and an organic light emitting layer. When a voltage is applied to the organic EL element, holes and electrons are injected from each electrode, and light is emitted by recombining the injected holes and electrons in the organic light emitting layer. Since such an organic EL element can be driven at a low voltage and has high luminance, use of the organic EL element in a display device or a lighting device has been studied.

  It is known that the performance of an organic EL element is improved by providing a predetermined layer (such as an electron injection layer and a hole injection layer) different from the organic light emitting layer between the electrodes. It has been studied to use a layer made of a metal oxide for the hole injection layer or the like. Specifically, there is an organic EL element in which an inorganic oxide layer such as molybdenum oxide is provided between a light emitting layer and an electron injection electrode (see, for example, Patent Document 1).

  In the manufacture of an organic EL element, the use of a wet process has been studied because of the ease of the process. Specifically, when the predetermined layer is formed, the predetermined layer is formed by a coating method using a coating liquid containing a material for forming the layer. However, since the molybdenum oxide layer has low resistance to a wet process, if a predetermined layer is formed on the molybdenum oxide layer using a coating method, the molybdenum oxide layer may be damaged. In some cases, the molybdenum oxide layer may be damaged. Since the layer may be eluted, the molybdenum oxide layer cannot exhibit its intended function, and as a result, there is a problem that an organic EL element having high light emission characteristics and long life characteristics cannot be obtained.

  Further, one of the important factors affecting the light emission efficiency of the organic EL element is the light extraction efficiency from the element. The light generated inside the organic EL element is totally reflected by an electrode or the like, or absorbed inside and confined inside the element, and most of the light is not effectively used. As a conventional technique, a light scattering layer is provided between a transparent substrate on which an organic EL element is provided and an electrode of the organic EL element, thereby suppressing total reflection of light and improving light extraction efficiency. (See, for example, Patent Document 2).

  However, the organic EL element according to the conventional technique described above does not necessarily have sufficient light extraction efficiency, and further improvement in light extraction efficiency is required.

JP 2002-367784 A JP 2007-035550 A

  The present invention has been made in view of the above-described problems of the prior art, and the problem is that an element having good life characteristics can be produced even by a wet process that is easy to process, and the light extraction efficiency is high. An object of the present invention is to provide a high organic EL element, a manufacturing method thereof, and an illumination device, a planar light source, and a display device using the organic EL element.

  In order to solve the above-described problems, the present invention provides an organic electroluminescence element adopting the following configuration, a method for manufacturing the organic electroluminescence element, an illumination device using the organic electroluminescence element, a planar light source, and a display device I will provide a.

[1] A transparent first electrode which is one of an anode and a cathode;
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;
A film disposed on the outermost layer on the first electrode side with respect to the light emitting layer; and
Including
An organic electroluminescence device in which a surface opposite to the light emitting layer side of the film is formed in an uneven shape, the haze value of the film is 70% or more, and the total light transmittance of the film is 80% or more .

[2] The organic electroluminescence element according to the above [1], wherein the metal-doped molybdenum oxide layer is provided in contact with the anode.

[3] The organic electroluminescence device according to the above [1] or [2], wherein the visible light transmittance of the metal-doped molybdenum oxide layer is 50% or more.

[4] Any one of [1] to [3] above, 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. The organic electroluminescent element as described in 1.

[5] The organic electroluminescent element according to the above [4], wherein the dopant metal is aluminum.

[6] The organic electroluminescence device according to any one of [1] to [5], wherein a ratio of a dopant metal contained in the metal-doped molybdenum oxide layer is 0.1 to 20.0 mol%. .

[7] The organic electroluminescence device according to any one of [1] to [6], wherein a plurality of concave surfaces are formed on a surface of the film opposite to the light emitting layer side.

[8] The method for producing an organic electroluminescence element according to any one of [1] to [7],
Providing a metal doped molybdenum oxide;
In this step, the method for producing an organic electroluminescence element, wherein molybdenum oxide and a dopant metal are simultaneously deposited on a layer on which the metal-doped molybdenum oxide layer is formed.

[9] The step of providing a metal-doped molybdenum oxide layer further includes a step of heating a layer obtained by simultaneously depositing molybdenum oxide and a dopant metal, in the organic electroluminescence device according to the above [8]. Production method.

[10] The method for producing an organic electroluminescent element according to any one of [1] to [7],
A step of producing the film, and a film installation step of providing the film obtained by the step of producing the film in the outermost layer,
In the production process of the film,
On the surface of a predetermined base, a solution containing the material to be the film is applied so that the thickness of the film is in a range of 100 μm to 200 μm,
The manufacturing method of the organic electroluminescent element which produces the said film by drying, after forming the film into a film after keeping the solution apply | coated on the surface of the said base to 80%-90% of humidity.

[11] An illumination device comprising the organic electroluminescence element according to any one of [1] to [7].

[12] A planar light source comprising the organic electroluminescence device according to any one of [1] to [7].

[13] A display device comprising the organic electroluminescence element according to any one of [1] to [7].

According to the present invention, it is possible to provide an organic electroluminescence device that is easy to manufacture, has good light emission characteristics and lifetime characteristics, has high light extraction efficiency, and high light emission efficiency.
Therefore, the organic electroluminescence element of the present invention can be preferably 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 EL element of the present invention will be described in detail according to 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 EL device according to the present invention is
A transparent first electrode that is one of an anode and a cathode;
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;
A film disposed on the outermost layer on the first electrode side with respect to the light emitting layer; and
Including
The surface opposite to the light emitting layer side of the film is formed in an uneven shape, the haze value of the film is 70% or more, and the total light transmittance of the film is 80% or more, It is said.

  An organic EL device according to the first embodiment of the present invention having such a basic configuration is shown in FIG. In the following description, 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). This notation of the vertical relationship is set for convenience of explanation, and is not necessarily applied to a process in which an organic EL element is actually manufactured and a situation in which it is used.

  The organic EL element of the present embodiment further includes a transparent support substrate 1. In the organic EL element, a transparent anode (first electrode) 2, a light emitting unit 3, and a cathode (second electrode) 4 are arranged in this order on the support substrate 1. Usually, a protective layer (also referred to as an upper sealing film) 5 that protects the entire laminated body in order to protect the laminated body (hereinafter sometimes referred to as a light emitting function unit) disposed on the support substrate 1. Is provided. The light emitting function part is surrounded by the support substrate 1 and the protective layer 5.

  The light emitting unit 3 includes a light emitting layer 7. Between the light emitting layer 7 and the anode (first electrode) 2, a predetermined one or a plurality of layers 6 such as a hole injection layer, a hole transport layer, and an electron blocking layer are provided as necessary, and at least a metal Doped molybdenum oxide is provided. Further, one or a plurality of predetermined layers 8 such as an electron injection layer, an electron transport layer, and a hole blocking layer are provided between the light emitting layer 7 and the cathode (second electrode) 4 as necessary.

  The organic EL element of the present embodiment further includes a film 9 provided in contact with the side of the support substrate 1 opposite to the light emitting layer 7 side.

  In the first embodiment, the first electrode 2 is an anode and the second electrode 4 is a cathode. However, the stacking order of the light emitting functional units is reversed, the first electrode is a cathode, and the second electrode is an anode. You may comprise the organic EL element which is.

(Metal-doped molybdenum oxide layer)
The organic EL element in the present embodiment has a metal-doped molybdenum oxide layer between the anode (first electrode) 2 and the light emitting layer 7 as an essential component. As described above, a hole injection layer, a hole transport layer, an electron block layer, and the like are provided between the anode 2 and the light emitting layer 7. And it functions as one layer of the electron block layer. In some cases, only a metal-doped molybdenum oxide layer is provided between the anode (first electrode) 2 and the light-emitting layer 7, but in addition to the metal-doped molybdenum oxide layer, it is different from the metal-doped molybdenum oxide layer. A layer may be provided.

  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, the proportion of the total of the molybdenum oxide and the dopant metal in the total amount of the material constituting the metal-doped molybdenum oxide layer is preferably 98% by mass or more, more preferably 99% by mass or more, and still more preferably Is 99.9% by mass or more.

  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 EL device 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. Moreover, it is preferable to employ MoO ₃ as the molybdenum oxide. When MoO ₃ is formed by an evaporation method such as vacuum evaporation, the stoichiometric composition ratio of Mo and O in the deposited film may deviate from MoO _3. It can be preferably used for an EL element.

  The ratio of the dopant metal contained in the metal-doped molybdenum oxide layer is preferably 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 method in which molybdenum oxide and a dopant metal are simultaneously deposited on a layer on which the metal-doped molybdenum oxide layer is formed is preferable. . For example, by simultaneously depositing molybdenum oxide and a dopant metal on an anode provided on a substrate, a metal-doped molybdenum oxide layer in direct contact with the anode can be obtained. In addition, after providing an electrode on the substrate, one or more layers different from the metal-doped molybdenum oxide layer 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 further thereon By simultaneously depositing molybdenum oxide and dopant metal, a metal-doped molybdenum oxide layer in which the metal-doped molybdenum oxide layer is in direct contact with the layer formed on the surface thereof 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, MoO ₃ or a single metal is usually used as the molybdenum oxide and the dopant metal material, but an oxide of MoO ₂ or a dopant metal, an alloy of a dopant metal and Mo, a mixture thereof, or the like can be used.

The layer in which molybdenum oxide and dopant metal are simultaneously deposited functions as a hole injection layer or hole transport layer as it is, but the layer in which molybdenum oxide and dopant metal are simultaneously deposited is further heated, UV-O ₃ treated, air It is preferable to perform a treatment such as exposure. In particular, it is preferable to perform a heat treatment on a layer in which molybdenum oxide and a dopant metal are simultaneously deposited in order to improve resistance to a wet process.

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.

  It is also possible to provide a layer containing a polymer compound on the metal doped molybdenum oxide layer and form a light emitting layer thereon. The layer containing a polymer compound can be formed by a coating method because the polymer compound is soluble in a solvent. In this case, if a metal-doped molybdenum oxide layer resistant to the wet process is provided in the lower layer, the light-emitting layer is formed by an easy coating method without impairing the function of the metal-doped molybdenum oxide layer. Can do.

  In the case of the configuration in which the metal-doped molybdenum oxide layer described above is provided, for example, in the case of a layer configuration of anode / metal-doped molybdenum oxide layer / light-emitting layer, when the light-emitting layer is formed by a coating method, the metal-doped molybdenum oxide layer is Since it is resistant to the wet process, it is less damaged and does not elute into the coating solution, and can exhibit the desired characteristics as a hole injection layer (or hole transport layer). Therefore, the organic EL element of this embodiment having a configuration in which a metal-doped molybdenum oxide layer is provided has high reliability and light emission characteristics, and has a long lifetime.

(the film)
The film 9 is provided on the surface of the support substrate 1 opposite to the light emitting layer 7 side. The film 9 has a planar surface on the light emitting layer 7 side, and a surface opposite to the light emitting layer 7 side is formed in an uneven shape. The film 9 has a haze value of 70 or more and a total light transmittance of 80% or more.

  The planar surface of the film 9 is bonded to the transparent support substrate 1. The film 9 is affixed to the support substrate 1 using bonding agents, such as a thermosetting resin, a photocurable resin, an adhesive agent, and an adhesive material, for example. When the thermosetting resin is used, the film 9 is bonded to the support substrate 1 by bonding the film 9 to the support substrate 1 and then heating at a predetermined temperature. When a photocurable resin is used, the film 9 is bonded to the support substrate 1 by, for example, irradiating the film 9 with ultraviolet rays after the film 9 is bonded to the support substrate 1. In addition, when forming the film 9 directly on the support substrate 1, and when the bonding agent is previously provided in the film 9, the said bonding agent does not need to be used.

  When an air layer is formed between the film 9 and the support substrate 1, reflection occurs at the interface of the air layer, so that the air layer is not formed between the film 9 and the support substrate 1. It is preferable to perform 9 bonding. Of the refractive index of the film 9, the refractive index of the bonding agent, and the refractive index of the layer to which the film 9 is bonded (supporting substrate 1 in the present embodiment), the maximum refractive index, and the minimum refractive index The smaller the difference is, the more preferable it is because reflection on the bonding surface can be suppressed. Specifically, the difference is preferably within 0.2, and more preferably within 0.1.

  In the film 9 of the present embodiment, the surface of the film 9 opposite to the support substrate 1 side is formed in an uneven shape, the haze value is 70% or more, and the total light transmittance is 80% or more. If the haze value is less than 70%, a sufficient light scattering effect may not be obtained, and if the total light transmittance is less than 80%, sufficient light may not be extracted. When a simple film is used for the organic EL element, there is a possibility that sufficient light extraction efficiency cannot be realized. Therefore, by using the film 9 having a haze value of 70% or more and a total light transmittance of 80% or more, an organic EL element with high extraction efficiency can be realized.

The haze value is represented by the following formula.
Haze value (cloudiness value) = (diffuse transmittance (%) / total light transmittance (%)) × 100 (%)
The haze value can be measured by the method described in JIS K 7136 “How to determine the haze of a plastic-transparent material”.
The total light transmittance can be measured by the method described in JIS K 7361-1 “Testing method of total light transmittance of plastic-transparent material”.

  If the size (width) of the convex or concave surface in the width direction perpendicular to the thickness direction of the film 9 is too large, the luminance on the surface of the film 9 becomes non-uniform, and if it is too small, the production cost of the film 9 increases. Therefore, it is preferably 0.5 μm to 20 μm, and more preferably 1 μm to 2 μm. The height of the convex surface or concave surface in the thickness direction of the film 9 is determined by the size (width) of the convex surface or concave surface in the width direction and the period in which the concave and convex shapes are formed, and usually the concave surface or convex surface in the width direction. The size (width) or less or the period or less in which the irregular shape is formed is preferably 0.25 μm to 10 μm, and preferably 0.5 μm to 1.0 μm.

  Although there is no restriction | limiting in particular in the shape of the said convex surface or a concave surface, What has a curved surface is preferable, for example, a hemispherical shape is preferable. The concave surface or the convex surface is preferably arranged regularly, for example, preferably arranged in a grid pattern. Moreover, 60% or more of the area of the surface of the film 9 is preferable in the area of the surface of the film 9 where the concave surface and the convex surface are formed.

  The material which comprises the film 9 should just be a material formed transparently, for example, you may use a polymeric material, glass, etc. Examples of the polymer material constituting the film 9 include polyarylate, polycarbonate, polycycloolefin, polyethylene naphthalate, polyethylene sulfonic acid, and polyethylene terephthalate. The film 9 includes a support made of, for example, the polymer material and glass, and a thin film formed on the surface of the support and having a surface on the side opposite to the surface in contact with the support in an uneven shape. You may be comprised with a laminated body.

  Although there is no restriction | limiting in particular in the thickness of the film 9, When it is too thin, handling will become difficult, and since a total light transmittance will become low when too thick, 20 micrometers-1000 micrometers are preferable.

  Next, the manufacturing method of the film 9 is demonstrated. The film 9 of this Embodiment is obtained by forming uneven | corrugated shape on the surface of a film. The size of the concavo-convex shape formed on the surface is approximately the same as or larger than the wavelength of light, and is preferably 0.1 μm to 100 μm.

  In the film 9 made of an inorganic material such as glass, for example, a protective film in which a photoresist is hardened is formed in advance on a base in a region where the uneven shape is not formed, and the uneven surface is formed by performing chemical etching or vapor phase etching. Can be formed. Also, in the film 9 made of a polymer material, a method of transferring the uneven surface of the metal plate by pressing the metal plate having an uneven surface on the heated film, using a roll having an uneven surface, the polymer sheet Alternatively, a method of rolling a film, a method of forming by extruding a polymer sheet from a slit having a concavo-convex shape, a solution or dispersion containing a polymer material is dropped on a base having a concavo-convex surface (hereinafter referred to as casting) And after the formation of a monomer film, a part of the film is selectively photopolymerized to remove the unpolymerized part. The concavo-convex surface can be formed by a method of casting on a table and transferring the water droplet structure to the surface.

  Among these methods, for polymer materials, a method of casting a polymer solution on a base and transferring a water droplet structure to the surface under high humidity conditions is preferable because of ease of production. This method is a known structure production method applying a dissipative process that is a kind of self-organization (see, for example, G. Widawski, M. Rawiso, B. Francois, Nature, p. 369-p. 387 (1994)). ).

  First, the polymer material to be the film 9 described above is dissolved in a solvent to prepare a solution for the film 9. Examples of the solvent include dichloromethane and chloroform. As the solution for the film 9, one having a high viscosity is preferable. Further, the solution for the film 9 is preferably a solution having a high concentration of the polymer material to be the film 9 and preferably has a concentration of 10 wt% or more with respect to the solution of the polymer material to be the film 9. In order to improve the size and shape uniformity of the uneven shape, a small amount of a surfactant such as a nonionic surfactant may be added to the solution for the film 9.

Next, the application | coating process which apply | coats the solution containing the material used as the film 9 on one surface of the base in which the film 9 is formed on the surface is performed. Specifically, the prepared solution for the film 9 is cast on one surface of the base under high humidity to form a liquid film composed of the solution for the film 9.
Examples of the base include the support substrate made of the above-described polymer material and glass.

  Next, a film forming step is performed in which the solution applied on one surface of the base is kept in a humidity range of 80% to 90% and then dried to form a film. When the liquid film is left under high humidity, water vapor in the atmosphere is liquefied and a plurality of droplets are formed on the surface of the liquid film. The plurality of droplets are substantially spherical and are discretely formed on the surface of the liquid film. The droplets formed on the surface of the liquid film have a diameter that increases with time due to further liquefaction of water vapor, and approximately half of the droplet sinks into the liquid film due to its own weight. Further, since the solvent in the liquid film evaporates with time, the shape of the droplet is transferred to the film 9 at the time of drying. The film 9 formed in this way is provided with a plurality of concave surfaces on the surface, and is formed in an uneven shape. Specifically, a plurality of hemispherical depressions having a diameter of 1 μm to 100 μm are formed on the surface of the film 9. In addition, by holding the film 9 in the range of 80% to 90% humidity, the film may be dried in a lower humidity atmosphere after a hemispherical depression is formed on the surface. The film may be dried by holding the film in the 90% range for a long time.

  In the method for producing the film 9 described above, by controlling the coating amount of the solution for the film 9 so that the film 9 has a predetermined thickness, and adjusting the humidity when drying the liquid film, The haze value of the produced film 9 can be controlled. Specifically, the thickness of the liquid film at the start of drying is controlled so that the film thickness of the film 9 formed through the film formation step becomes a predetermined film thickness within a range of 100 μm to 200 μm, and 80 By controlling the humidity so as to be a predetermined humidity within a range of% to 90%, a film 9 having a haze value of 70 or more and exhibiting a desired haze value can be formed.

The haze value of the film 9 can be controlled by controlling the humidity and the film thickness when the humidity and the film thickness are changed, depending on the concentration of the polymer material to be the film 9 in the solution. This is because the time until the surface dries is changed, which changes the size of the concave and convex shapes and the density of the concave surfaces to be formed.Humidity is also used to construct the structure of the concave surfaces to be formed, such as improving the regularity of the concave surfaces. This is presumed to have a large impact.
In addition, the film thickness of the produced film 9 can be controlled by adjusting the film thickness of the liquid film at the start of drying.
In addition, since the time until the surface of the liquid film is dried varies depending on the evaporation rate of the solvent and the boiling point of the solvent, the haze value of the film 9 can be controlled by changing the solvent used.

  By such a method, a large-area film 9 showing the intended optical characteristics can be produced easily and inexpensively.

  The film 9 can also be formed directly on the support substrate 1 by casting a solution for the film 9 on the surface of the support substrate 1.

  According to the organic EL device of the present embodiment described above, the film 9 is formed on the structure having the metal-doped molybdenum oxide layer between the anode and the light emitting layer and on the outer surface portion on the light extraction side of the organic EL device. It has an arranged configuration.

  By providing the metal-doped molybdenum oxide layer, as described above, the reliability and light emission characteristics of the element can be improved and the lifetime can be increased.

  Moreover, in the structure which arrange | positions the film 9, the following effects are acquired. That is, since the surface of the film 9 opposite to the light emitting layer 7 side is formed in an uneven shape, at least a part of the outer surface on the light extraction side of the organic EL element is formed in an uneven shape. A part of the light emitted from the light emitting layer 7 is incident on the film, is diffracted on the uneven surface or is reflected a plurality of times, and is emitted to an atmosphere such as air. If the surface of the film 9 opposite to the light emitting layer 7 side is flat, most of the light generated in the light emitting layer 7 due to total reflection occurring on the surface of the organic EL element is not extracted outside. On the other hand, by forming the surface on the side from which light is extracted in a concavo-convex shape, total reflection can be suppressed using the diffraction effect or the like, and light can be extracted efficiently. In particular, since a film having a haze value of 70% or more and a total light transmittance of 80% or more is provided, the light extraction efficiency can be improved, and an organic EL device having high light extraction efficiency can be realized. it can.

  Moreover, according to the organic EL element of this Embodiment, since the several concave surface is provided in the surface on the opposite side to the light emitting layer 7 side of the film 9, this concave surface exhibits the function similar to a concave lens. By providing such a film 9, the radiation angle of the light emitted from the organic EL element can be widened.

  Moreover, the film 9 used for the organic EL element of this Embodiment is a coating process which apply | coats the solution containing the material used as the said film 9 on one surface of a predetermined base, and dries the apply | coated liquid film. And forming a film to form a film. In particular, by applying a solution containing the material to be the film 9 so that the thickness of the film after the film forming step is 100 μm to 200 μm, and further drying the humidity in the range of 80% to 90%, the surface is uneven. A film having a haze value of 70% or more and a total light transmittance of 80% or more can be produced. For example, it has the intended optical characteristics by simple control of adjusting the application amount and humidity of the solution. A film can be manufactured easily.

  Moreover, according to the organic EL element of this Embodiment, since the film 9 used for an organic EL element can be easily produced by simple control as mentioned above, an organic EL element with high light extraction efficiency is easy. Can be manufactured.

In the organic EL element of the present embodiment described above, the film 9 is attached to the support substrate 1, but the position where the film 9 is provided is not limited to this. For example, in a top emission type organic EL device that takes out light from the side opposite to the support substrate 1 (cathode 4 side), a film 9 is pasted on the surface opposite to the light emitting layer 7 side of the light-transmitting cathode 4. May be attached. This configuration will be described later as a second embodiment of the present invention.
In a top emission type organic EL device in which the cathode is formed on the surface of the substrate and the cathode, the light emitting layer, and the anode are arranged in this order on the substrate, a film is formed on the surface opposite to the light emitting layer side of the anode. Can be pasted.

As described above, the organic EL device according to the first embodiment of the present invention has a metal-doped molybdenum oxide layer between the anode (first electrode) 2 and the light emitting layer 7, and the support substrate 1. The film 9 is provided on the surface opposite to the light emitting layer 7.
According to this embodiment having a configuration in which a metal-doped molybdenum oxide layer is provided between the anode 2 and the light emitting layer 7 and a configuration in which a film 9 is disposed on the outer surface portion on the light extraction side of the organic EL element, In addition to increasing the light emission efficiency of the EL element, the lifetime can be extended.

  Subsequently, components of the organic EL element other than the metal-doped molybdenum oxide layer and the film 9 will be described in detail below.

(substrate)
The support substrate 1 may be any substrate that does not change in the process of forming the organic EL element, that is, any substrate that does not change when the electrode is formed and the organic layer is formed, and may be a rigid substrate or a flexible substrate. For example, a glass plate, a plastic plate, a polymer film and a silicon plate, and a laminated plate obtained by laminating these 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 EL element that takes out light from the light emitting unit 3 from the support substrate 1 side as shown in FIG. 1, the support substrate 1 having high light transmittance in the visible light region is preferably used.
In the top emission type organic EL element that takes out light from the light emitting section 3 from the cathode 4 side as shown in a second embodiment to be described later, the support substrate 1 may be transparent or opaque. .

(First electrode)
The first electrode (the anode 2 in the configuration of FIG. 1) in the first embodiment is a transparent electrode that transmits light from the light emitting layer 7, and is normally the anode of the organic EL element of the present invention. However, as described later, an organic EL element having a configuration in which a transparent first electrode is used as a cathode is also possible. For the first electrode 2, 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. It can be selected and used. Examples of the material of the first electrode 2 include indium oxide, zinc oxide, tin oxide, ITO (Indium Tin Oxide), IZO (Indium Zinc Oxide), gold, platinum, silver, and copper. A thin film such as is used. Among these, ITO, IZO, and tin oxide are preferable.
In the present specification, the term “transparent” refers to the property of exhibiting light transmittance, and does not necessarily mean that the light transmittance is 100%.

  Further, as a constituent material of the first electrode 2, 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 7, on the surface of the first electrode 2 on the light emitting layer 7 side, a conductive polymer such as a phthalocyanine derivative and a polythiophene derivative, molybdenum oxide, amorphous carbon, A 1 to 200 nm layer such as carbon fluoride or a 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 2 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.

  Examples of the method for forming the first electrode 2 include a vacuum deposition method, a sputtering method, an ion plating method, and a plating method.

(Layer provided between the anode and the light emitting layer)
As described above, a hole injection layer, a hole transport layer, an electron blocking layer, and the like are provided between the anode and the light emitting layer as necessary, and as described above, the hole injection layer, the hole transport layer, and At least a metal-doped molybdenum oxide layer that functions as one of an electron blocking layer and the like is provided.

The hole injection layer is a layer having a function of improving the hole injection efficiency from the anode (first electrode) 2.
The hole transport layer is a layer having a function of improving hole injection from an anode, a hole injection layer, or a 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)
Although it is preferable to provide a metal-doped molybdenum oxide layer as a hole injection layer, a layer different from the metal-doped molybdenum oxide can also be provided as a hole injection layer, and as a material constituting the hole injection layer, A well-known material can be used suitably and there is no restriction | limiting in particular. 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, dichloroethane, ether solvents such as tetrahydrofuran, toluene, xylene And aromatic hydrocarbon solvents such as acetone, 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 metal-doped molybdenum oxide layer may be provided as a hole transport layer, but when a layer different from the metal-doped molybdenum oxide layer is provided as a hole transport layer, the material constituting the hole transport layer is particularly Although there is no limitation, 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, polysiloxane derivatives having aromatic amines in the side chain or main chain, pyrazoline derivatives, arylamine derivatives , Stilbene derivatives, triphenyldiamine derivatives, polyaniline or derivatives thereof, polythiophene or derivatives thereof , Polyarylamine or a derivative thereof, polypyrrole or a derivative thereof, poly (p-phenylenevinylene) or a derivative thereof, or poly (2,5-thienylenevinylene) or a derivative thereof.

  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 can dissolve a hole transport material. Chlorine solvents such as chloroform, methylene chloride, dichloroethane, ether solvents such as tetrahydrofuran, toluene, xylene And aromatic hydrocarbon solvents such as acetone, 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 7 usually includes an organic substance that mainly emits fluorescence or phosphorescence. The light emitting layer 7 contains a low molecular compound and / or a high molecular compound as an organic substance. Since the polymer compound is easily dissolved in a solvent, the light emitting layer is preferably configured to contain the polymer compound from the viewpoint that the light emitting layer can be easily formed by a coating method described later, and is converted into polystyrene. It is preferable to include a polymer compound having a number average molecular weight of 10 ³ to 10 ⁸ . Further, a dopant material may be included. Examples of the material for forming 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 2 and the cathode 4 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, quinacridone derivatives, coumarin derivatives, pyrazoloquinoline derivatives, distyrylbenzene derivatives, distyrylarylene derivatives, Examples include pyrrole derivatives, thiophene ring compounds, pyridine ring compounds, perinone derivatives, perylene derivatives, oligothiophene derivatives, trifumanylamine derivatives, oxadiazole dimers, and pyrazoline dimers.

(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 above light-emitting materials, examples of materials that emit 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 7 for the purpose of improving the light emission efficiency or 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. The thickness of the light emitting layer 7 is usually about 20 to 2000 mm.

(Light-emitting layer deposition method)
As a method for forming the light emitting layer 7 containing an organic substance, a method of applying a solution containing a light emitting material on or above a substrate, a vacuum deposition method, a transfer method, or the like can be used. 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 on or above a substrate, 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 Coating methods such as slit coating method, capillary coating method, spray coating method, nozzle coating method, gravure printing method, screen printing method, flexographic printing method, offset printing method, reversal printing method, inkjet printing method, etc. A coating method can be used. 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)
A layer 8 such as an electron injection layer, an electron transport layer, or a hole block layer is laminated between the light emitting layer 7 and the cathode (second electrode) 4 as necessary.

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.
When both the electron injection layer and the electron transport layer are provided between the cathode 4 and the light emitting layer 7, 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. .
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 4 in the present embodiment is an electrode disposed opposite to the first electrode 2 and serves as a cathode of the organic EL element. In the present invention, the second implementation described later is performed. As shown in the embodiment, it is possible to use an anode.
A material for the cathode is preferably a material having a small work function and easy electron injection into the light emitting layer. 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 is an electrode having optical transparency as required, for example, when light is taken out from the cathode side. Examples of such a light-transmitting cathode material include conductive oxides such as indium oxide, zinc oxide, tin oxide, ITO, and IZO; and conductive organic substances such as polyaniline or a derivative thereof, polythiophene or a derivative thereof. Can do.

  The cathode (second electrode) 4 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) 4 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, and more preferably 50 nm. ~ 500 nm.

  Examples of the method for forming the cathode (second electrode) 4 include a vacuum deposition method, a sputtering method, and a laminating method in which a metal thin film is thermocompression bonded. The second electrode 4 may have a laminated structure of two or more layers.

In the organic EL element of the present embodiment, a combination example of layer configurations from the anode 2 to the cathode 4 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.)
As described above, the metal-doped molybdenum oxide layer is provided as a hole injection layer or a hole transport layer in the layer configurations of a) to l).

The organic EL device of the present embodiment may have two or more light-emitting layers, and as an organic EL device having two light-emitting layers, any one of the layer configurations a) to l) above. In this case, when the laminate sandwiched between the anode and the cathode is referred to as “repeating unit A”, the layer configuration shown in the following m) can be exemplified.
m) Anode / (Repeating Unit A) / Charge Injection Layer / (Repeating Unit A) / Cathode As an organic EL device having three or more light emitting layers, “(Repeating Unit A) / Charge Injection Layer” As the “repeating unit B”, the layer constitution shown in the following n) can be mentioned.
n) Anode / (Repeating unit B) x / (Repeating unit A) / Cathode The symbol “x” represents an integer of 2 or more, and (Repeating unit B) x is a laminate in which the repeating unit B is laminated in x stages. Represents the body.
Here, the charge injection layer is a layer that generates holes and electrons by applying an electric field. Examples of the charge injection layer include a thin film made of vanadium oxide, indium tin oxide (abbreviated as ITO), molybdenum oxide, or the like.

  In the organic EL 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 to the electrode and 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) 4 is formed as described above, the light emitting function part having the first electrode (anode) 2 -the light emitting part 3 -the second electrode (cathode) 4 as a basic structure is protected. Therefore, a protective layer (upper sealing film) 5 for sealing the light emitting function part is formed. This protective layer 5 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.

  Since the plastic substrate has higher gas and liquid permeability than the glass substrate, and the light emitting material such as the light emitting layer 7 is easily oxidized and easily deteriorates by contact with water. When used, even if the light emitting function part is encapsulated by the substrate 1 and the protective layer 5, it is likely to change over time. Therefore, when a plastic substrate is used as the substrate 1, a lower sealing film having a high barrier property against gas and liquid is laminated on the plastic substrate, and then the light emitting function part is laminated on the lower sealing film, Further, it is preferable to seal the light emitting function part with the protective layer 5. 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 EL 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 EL element of the first embodiment transmits light from the light emitting unit 3 through the transparent anode (first electrode) 2 and is transparent. The organic EL device of the second embodiment transmits light from the light emitting portion 23 through the transparent cathode (first electrode) 24, whereas the bottom emission type device emits from the support substrate 1 to the outside. In other words, it is a top emission type element that emits from the transparent protective layer 25 to the outside.

  In the second embodiment, the transparent first electrode that transmits light from the light emitting unit 23 is the transparent cathode 24. 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 22 and the substrate 21, and by providing such a reflective film, the light directed toward the substrate 21 is transmitted to the first electrode 24. Can be reflected to the side, and the light extraction efficiency can be improved.

  And in 2nd Embodiment, the film 29 is provided in the outer surface of the protective layer 25 which is the outermost layer of the light extraction direction. The protective layer 25 in this case is preferably a sealing substrate. The film 29 is provided such that the uneven surface thereof is located on the surface opposite to the light emitting layer 27 side.

  Various characteristics such as uneven shape, thickness dimension, haze value, total light transmittance, and preparation method of the film 29 are the same as those of the film 9.

Even if the organic EL 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 EL element of the present invention is easy to manufacture according to the first embodiment and the second embodiment, has good light emission characteristics and lifetime characteristics, and has high light emission efficiency. Various characteristics can be obtained.

  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. . When the element structure of the organic electroluminescence element of the first embodiment is tentatively referred to as a first structure, it is the same bottom emission type element structure, and a transparent cathode (first electrode) is provided on the transparent substrate side, and a protective layer An organic electroluminescence element having a structure in which an anode is provided on the side (second structure) can also be produced. The present invention can also be applied to an organic electroluminescence element having such a second structure.

  The organic electroluminescence device of the second embodiment has a top emission type device 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. ing. When the element structure of the organic electroluminescence element of the second embodiment is tentatively referred to as a third structure, it is the same top emission type element structure, and a transparent anode (first electrode) is provided on the transparent protective layer side, An organic electroluminescence element having a structure in which a cathode is provided on the support substrate side (fourth structure) can also be manufactured. The present invention can also be applied to such an organic electroluminescence element having the fourth structure.

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

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

  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 the following Production Examples 1 to 6 and Reference Examples 1 and 2, in order to confirm the effect of providing the metal-doped molybdenum oxide layer between the anode and the light emitting layer, a film for increasing the light extraction efficiency is transparent. An organic EL element was produced in which a metal-doped molybdenum oxide layer was provided between the anode and the light emitting layer without being disposed on the surface opposite to the light emitting layer side of the substrate.

(Production Example 1)
(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.
Moreover, when the board | substrate obtained different from the board | substrate exposed to the said pure water was exposed to acetone for 1 minute and observed with the optical microscope, there was no change and the surface did not melt | dissolve. 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 1) 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 1 described later, the transmittance was 3.6 times at 320 nm and 1.6 times at 360 nm.

(Production Example 2)
A substrate provided with a co-deposited film was obtained in the same manner as in Production Example 1 (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 1 (B). No change was observed when exposed to either pure water or acetone.

(Production Example 3)
A substrate provided with a co-deposited film by operating in the same manner as in (A) of Production Example 1 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 1 (C). No change was observed when exposed to either pure water or acetone.

(Production Example 4)
The substrate obtained in (A) of Preparation Example 1 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 1 (C). The results are shown in (Table 1) below. The transmittance at a wavelength of 320 nm was 28.9%, and the transmittance at 360 nm was 76.2%. Compared to Reference Example 1 below, the transmittance was 4.7 times at 320 nm and 2.2 times at 360 nm.

(Reference Example 1)
Except that Al was not deposited and only MoO ₃ was deposited at about 0.28 nm / second, the same operation as in Production Example 1 was performed to obtain a substrate provided with a deposited film having a thickness of about 10 nm.
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 1 (C). The results are shown below (Table 1). 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 1)
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 5)
(Production of organic EL element)
A glass substrate having an ITO thin film patterned on the surface was used as a 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 procedure as in Production Example 1.

  After the film formation, the substrate was taken out into the atmosphere, and the polymer compound P1 obtained in Synthesis Example 1 was formed on the 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 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 Produced a 2 × 2 mm organic EL device.
The obtained organic EL 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 EL elements)
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 , light emission was continued as it was, and the light emission lifetime was measured. The results are shown in the following (Table 2) and (Table 3). Compared to Reference Example 2 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 about 1.6 times.

(Production Example 6)
Except that the Al-doped MoO ₃ layer was formed in the same procedure as in Production Example 3, the same procedure as in Production Example 5 was followed to produce an organic EL 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 Reference Example 2 below, the maximum power efficiency is slightly higher, the driving voltage at the time of 1000 cd / m ² emission is reduced, and the life is extended about 2.4 times.

(Reference Example 2)
Instead of depositing the Al-doped MoO ₃ layer, the same procedure as in Reference Example 1 was followed, except that the MoO ₃ layer was deposited in the same manner as in Reference Example 5 to produce an organic EL device, and the current-voltage characteristics The emission lifetime was 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 2) and (Table 3).

  In the following Production Examples 7 and 8 and Reference Examples 3 to 5, it was confirmed that the light extraction efficiency can be controlled by providing a film on the outer surface of the support substrate.

(Production Example 7)
As a transparent support substrate, a 30 mm × 30 mm glass substrate was used. Next, a conductor film made of ITO having a thickness of 150 nm was deposited on the surface of the support substrate by sputtering. Next, a protective film having a predetermined pattern shape was formed by applying a photoresist on the surface of the conductor film, exposing a predetermined region through a photomask, and further washing the conductive film. After further etching, rinsing was performed with water and NMP (n-methylpyrrolidone) to form an anode made of an ITO film having a predetermined pattern shape. Next, in order to remove the resist residue on the anode, oxygen plasma treatment was performed for 2 minutes at an energy of 30 W, and UV / O ₃ cleaning was performed for 20 minutes.

  Next, a suspension of poly (3,4) ethylenedioxythiophene / polystyrene sulfonic acid (trade name: BaytronP CH8000, manufactured by Starck Vitec Co., Ltd.) is subjected to two-stage filtration to obtain a solution for a hole injection layer. Got. In the first stage filtration, a 0.45 μm diameter filter was used, and in the second stage filtration, a 0.2 μm diameter filter was used. A thin film is formed by spin coating using the solution obtained by filtration, and a hole injection layer having a thickness of 70 nm is formed by heat treatment at 200 ° C. for 15 minutes on a hot plate in an air atmosphere. did.

  Next, Lumination WP1330 (manufactured by SUMATION) and xylene were mixed to prepare a xylene solution. The concentration of Lumation WP1330 in the xylene solution was 1.2 mass%. Using the prepared solution, a thin film was formed on the surface of the hole injection layer by spin coating, and then heat-treated on a hot plate at 130 ° C. for 60 minutes in a nitrogen atmosphere to form a light-emitting layer having a thickness of 80 nm. did.

Next, the support substrate on which the light emitting layer was formed was introduced into a vacuum vapor deposition machine, and Ba and Al were sequentially deposited at a thickness of 5 nm and 80 nm, respectively, to form a cathode. In addition, after the degree of vacuum reached 1 × 10 ⁻⁴ Pa or less, metal deposition was started.

  Next, in order to produce a film, first, a solution for the film was produced. 6.32 g of polycarbonate was dissolved in 20.7 g of dichloromethane to prepare a 23.4 wt% solution. Next, Novec (manufactured by Sumitomo 3M), which is a fluorine-based surfactant, was mixed with this solution. The concentration of Novec in the mixed solution was 0.8 wt% to obtain a film solution. The obtained film solution was cast on a glass base so that the film thickness after film formation was about 150 μm in a constant temperature and humidity chamber with a humidity of 85%. After being left in an atmosphere of 85% humidity for 5 minutes, the film was dried by nitrogen flow to obtain a 20 mm × 20 mm film (film A) having a concavo-convex shape on the surface.

  Next, glycerin was applied as a pressure-sensitive adhesive on the surface of the support substrate opposite to the side on which the light emitting layer was formed, and film A was bonded to produce an organic EL device. The support substrate has a refractive index of 1.50, the adhesive has a refractive index of 1.45, and the film A has a refractive index of 1.58. The average film thickness of film A is 230 μm.

(Production Example 8)
An organic EL element different from the organic EL element of Production Example 7 only in film was produced. In Production Example 8, a commercially available film (film B) showing a high haze value (82) was used. Since the film B has an adhesive layer, an organic EL element was produced by pasting the film B as it was without using an adhesive or the like.

(Reference Example 3)
An organic EL element that is different from the organic EL element of Preparation Example 7 only in film was prepared.
The same solution as that of Preparation Example 7 was used as the film solution. In a constant temperature and humidity chamber with a humidity of 50%, the film solution was cast on a glass base so that the film thickness after film formation was about 220 μm. After being left in an atmosphere of 50% humidity for 5 minutes, the film was dried by nitrogen flow to obtain a 20 mm × 20 mm film (film C). This film C was attached to a support substrate in the same manner as in Production Example 7 using the same adhesive as in Production Example 7 to produce an organic EL device.

(Reference Example 4)
An organic EL element different from the organic EL element of Production Example 7 only in film was produced. Further, the same solution as that of Preparation Example 7 was used as the film solution. In a constant temperature and humidity chamber with a humidity of 85%, the film solution was cast on a glass base so that the film thickness after film formation was about 220 μm. After leaving it in an atmosphere with a humidity of 85% for 5 minutes, the film was dried with a nitrogen flow to obtain a 20 mm × 20 mm film (film D) having an uneven shape on the surface. The obtained film D was attached to a supporting substrate in the same manner as in Production Example 7 using the same adhesive as in Production Example 7 to produce an organic EL device.

(Reference Example 5)
An organic EL element different from the organic EL element of Production Example 7 only in film was produced. The same solution as that of Preparation Example 7 was used as the film solution. In a constant temperature and humidity chamber with a humidity of 85%, the film solution was cast on a glass base so that the film thickness after film formation was about 360 μm. After being left in an atmosphere of 85% humidity for 5 minutes, the film was dried by nitrogen flow to obtain a 20 mm × 20 mm film (film E) having an uneven shape on the surface. This film E was attached to a support substrate in the same manner as in Production Example 7 using the same adhesive as in Production Example 7 to produce an organic EL device.

(Observation of film surface)
The surfaces of the films used in Production Examples 7 and 8 and Reference Examples 3, 4, and 5 were observed with a scanning electron microscope (SEM). 3 is a diagram schematically showing a cross section of the film A produced in Production Example 7, FIG. 4 is a diagram schematically showing a cross section of the film B used in Production Example 8, and FIG. It is a figure which shows typically the cross section of the film C produced in the manufacture example 3. FIG.

  In the film A produced in Production Example 7, it was confirmed that a hemispherical concave surface having an average diameter of 2 μm was formed on the surface of the film. It was confirmed that the concave surface was formed over the entire surface of the film A.

  In the film B used in Production Example 8, it was confirmed that the surface of the film was formed in an uneven shape. It was confirmed that the concave surface was formed over the entire surface of the film B.

  In the film C produced in Production Example 3, it was confirmed that no concave surface was formed on the surface and the surface was flat.

  In the film D produced in Production Example 4, it was confirmed that a hemispherical concave surface having an average diameter of 3 μm was formed on the surface of the film. Although the regularity of the arrangement of the concave surface was relatively low, it was confirmed that the concave surface was formed over the entire surface of the film D.

  In the film E produced in Reference Example 5, it was confirmed that a hemispherical concave surface having an average diameter of 4 μm was formed on the surface of the film. Although the regularity of the arrangement of the concave surface was relatively low, it was confirmed that the concave surface was formed over the entire surface of the film E.

  Table 4 shows the humidity when the films were produced in Production Example 7 and Reference Examples 3, 4, and 5, and the characteristics of the films used in Production Examples 7 and 8 and Reference Examples 3, 4, and 5. .

  As shown in Table 4, it was confirmed that a film having a high haze value can be produced by controlling the humidity and the film thickness of the produced film. Moreover, when the film thickness of the produced film became thick, it confirmed that the diameter of the concave surface became large.

(Light extraction efficiency of organic EL elements)
The light intensity of the organic EL element to which the films prepared in Production Examples 7 and 8 and Reference Examples 3, 4, and 5 were bonded was compared with the light intensity of the organic EL element to which the film was not bonded. (Table 5) shows the ratio of the light extraction efficiency obtained by dividing the light intensity of the organic EL element on which the film is bonded by the light intensity of the organic EL element on which the film is not bonded. The light intensity was measured by passing a current of 0.15 mA through the organic EL element, measuring the angle dependency of the emission intensity at that time, and integrating the emission intensity at all angles.

  In the organic EL element of Production Example 7, the light extraction efficiency was increased 1.5 times compared to before the film A was bonded. Furthermore, the organic EL element of Preparation Example 8 in which the film A of Preparation Example 7 and a film B having optical properties similar to each other were bonded together, as with the organic EL element of Preparation Example 7, significantly increased the light extraction efficiency. However, since the film C used for the organic EL element of Reference Example 3 has almost no light scattering, no improvement in light extraction efficiency was observed. In Reference Examples 4 and 5, no significant improvement in light extraction efficiency was observed. From this, it was revealed that a film having a high total light transmittance and a high haze value contributes to an improvement in light extraction efficiency. In particular, it was found that the light extraction efficiency is greatly improved when the haze value of the film is 70 or more. Thus, it was confirmed that the light extraction efficiency was improved by providing a film having predetermined optical characteristics.

  In Production Examples 1 to 6, an organic EL element in which a metal-doped molybdenum oxide layer was provided between the anode and the light emitting layer was manufactured, and the anode and the light emitting layer were formed without providing a film on the outer surface of the support substrate. The effect by providing a metal dope molybdenum oxide layer between was confirmed. In Production Examples 7 and 8, an organic EL device in which a film is provided on the outer surface of a transparent support substrate without providing a metal-doped molybdenum oxide layer between the anode and the light emitting layer is manufactured. It was confirmed that the light extraction efficiency can be improved by providing a film on the outer surface of the film.

It is sectional drawing of the organic EL element of the 1st Embodiment of this invention. It is sectional drawing of the organic EL element of the 2nd Embodiment of this invention. It is a figure which shows typically the cross section of the film A produced in the manufacture example 7. FIG. It is a figure which shows typically the cross section of the film B used for the manufacture example 8. FIG. It is a figure which shows typically the cross section of the film C produced in the reference example 3. FIG.

Explanation of symbols

1 Transparent support substrate 2 Transparent anode (first electrode)
3 Light emitting part 4 Cathode (second electrode)
5 Protective layer (upper sealing film)
6 Layer provided between anode and light emitting layer 7 Light emitting layer 8 Layer provided between cathode and light emitting layer 9, 29 Film 21 Support substrate 22 Anode (second electrode)
23 Light Emitting Unit 24 Transparent Cathode (First Electrode)
25 Protective layer (upper sealing film)
26 Layer provided between the anode and the light emitting layer 27 Light emitting layer 28 Layer provided between the cathode and the light emitting layer A Film used in Preparation Example B Film used in Preparation Example 8 C Used in Reference Example 3 the film

Claims (12)

A transparent first electrode that is one of an anode and a cathode;
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;
A film disposed on the outermost layer on the first electrode side with respect to the light emitting layer; and
Including
The visible light transmittance of the metal-doped molybdenum oxide layer is 50% or more,
An organic electroluminescence device in which a surface opposite to the light emitting layer side of the film is formed in an uneven shape, the haze value of the film is 70% or more, and the total light transmittance of the film is 80% or more .   The organic electroluminescent element according to claim 1, wherein the metal-doped molybdenum oxide layer is provided in contact with the anode. The organic electroluminescent element according to claim 1 or 2 , 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. The organic electroluminescent device according to claim 3 , wherein the dopant metal is aluminum. The metal-doped ratio of a dopant metal contained in the molybdenum oxide layer is an organic electroluminescent device according to any one of claims 1 to 4, which is a 0.1~20.0mol%. The organic electroluminescent device according to any one of claims 1 to 5, a plurality of concave is formed on the surface opposite to the light emitting layer side of the film. It is a manufacturing method of the organic electroluminescent element of any one of Claims 1-6 , Comprising:
Providing a metal doped molybdenum oxide;
In this step, the method for producing an organic electroluminescence element, wherein molybdenum oxide and a dopant metal are simultaneously deposited on a layer on which the metal-doped molybdenum oxide layer is formed. The method for producing an organic electroluminescence device according to claim 7 , wherein the step of providing the metal-doped molybdenum oxide layer further includes a step of heating a layer obtained by simultaneously depositing molybdenum oxide and a dopant metal. It is a manufacturing method of the organic electroluminescent element of any one of Claims 1-6 , Comprising:
A step of producing the film, and a film installation step of providing the film obtained by the step of producing the film in the outermost layer,
In the production process of the film,
On the surface of a predetermined base, a solution containing the material to be the film is applied so that the thickness of the film is in a range of 100 μm to 200 μm,
The manufacturing method of the organic electroluminescent element which produces the said film by drying, after forming the film into a film after keeping the solution apply | coated on the surface of the said base to 80%-90% of humidity. Lighting device characterized in that it comprises an organic electroluminescent device according to any one of claims 1-6. Planar light source characterized by comprising the organic electroluminescent element of any one of claims 1-6. Display device, characterized in that it comprises an organic electroluminescent device according to any one of claims 1-6.

Images