JP4899443B2 - Conductive substrate - Google Patents

Description

  The present invention relates to a conductive substrate.

  Conventionally, transparent conductive laminates in which a transparent conductive layer is provided on the surface of a polymer film as a substrate have been widely used for transparent heat ray reflectors, transparent planar heating elements, transparent electrodes, and the like.

About the transparent conductive layer formed in this transparent conductive laminate, metal thin film type such as gold (Au), silver (Ag), palladium (Pd), indium oxide (In ₂ O ₃ ), tin oxide (SnO) ₂ ), metal oxide thin film types such as ITO (Indium Tin Oxide) and zinc oxide (ZnO) which are a mixture thereof, and multilayer thin film types of metal / metal oxide such as TiO ₂ / Ag / TiO ₂ Various things are known.

  Among these, metal oxide thin films such as ITO have the characteristics that both translucency and conductivity are very good, and the etching characteristics are also excellent, and the patterning as an electrode is easy. It is what. For this reason, the ITO thin film is suitably used for a transparent electrode of a display that requires a fine pattern.

  Such a metal oxide thin film is formed by various film forming methods such as a vacuum deposition method, a sputtering method, an ion plating method, or a CVD method. A flexible conductive substrate can be manufactured by forming such a metal oxide thin film on a flexible substrate.

  Various flexible electronic devices that can be bent and thin, such as displays, lighting, solar cells, circuit boards, semiconductors, and electronic papers, using such a flexible conductive substrate, have been developed.

  In recent years, a transparent conductive layer has been provided on the surface of a polymer film as a base material as a flexible transparent electrode substrate for an organic EL (Electroluminescence) display device, particularly for a portable, small, thin, and light-weight organic EL display device. Transparent conductive laminates have been used.

And since the EL element in an organic EL display device is very weak to moisture, especially when the light emitting layer contains moisture, deterioration is accelerated. Therefore, various structures for preventing water vapor from entering the organic EL layer have been proposed. . For example, Japanese Patent Application Laid-Open No. 2004-14287 (Patent Document 1) discloses an ITO film that has a structure with high crystallinity and a layer with a low crystallinity structure with improved water vapor permeation prevention, and the ITO film. Although there is a description of the organic EL element used, it is here for an organic EL display device having a structure using a prevention film (water vapor permeation prevention film, moisture barrier film) that prevents moisture from entering the EL element body. A substrate is also described.
JP 2004-14287 A

  As described above, in recent years, a transparent conductive laminate in which a transparent conductive layer is provided on the surface of a polymer film as a base material has been used as a flexible transparent electrode substrate particularly for an organic EL display device. . Along with this, various conductive substrates having a structure for preventing water vapor that causes deterioration of the electronic element from entering the electronic element body have been proposed.

  However, from the knowledge of the present inventors, such a conventional substrate is not capable of sufficiently extending the lifetime as an organic EL element, for example, when used in an organic EL display device. It could not be said that the performance and the durability and strength of the substrate could be sufficiently satisfied at the same time. Moreover, the occurrence of a short circuit or dark spot during light emission is not preferable as an element display defect.

  The present invention corresponds to these. For example, when used in an organic EL device, the lifetime of the organic EL element can be sufficiently increased, and the flexibility of the substrate, the durability of the substrate, It is intended to provide a substrate for an organic EL device that can sufficiently satisfy the strength at the same time. In particular, the film quality of the ITO film is improved, the lifetime as an organic EL element is increased, and the luminance-voltage (LV) characteristics and An object of the present invention is to provide a substrate for an organic EL device that improves light emission characteristics such as current-voltage (IV) characteristics and reduces dark spots and short-circuits during light emission.

In order to solve the above-described problems, a conductive substrate for an organic EL device according to the present invention has an integrated intensity A of 2θ peak corresponding to (222) plane and (440) plane by X-ray diffraction method on a transparent substrate. The integrated intensity ratio A / C with the integrated intensity C of the 2θ peak corresponding to is equal to or greater than 7.0 , and corresponds to the integrated intensity B of the 2θ peak corresponding to the (400) plane by the X-ray diffraction method and the (440) plane. The integrated intensity ratio B / C with the integrated intensity C of the 2θ peak is 0.80 or less, and the half width of the 2θ peak corresponding to the (222) plane by the X-ray diffraction method is 0.95 deg or less . A certain ITO film is formed.

  Such a conductive substrate according to the present invention preferably includes the ITO layer having an integrated intensity A of 2θ peak corresponding to (222) plane by X-ray diffraction method of 7000 counts or more.

  Such a conductive substrate according to the present invention preferably includes the ITO layer having a half-value width of 0.95 deg or less corresponding to the (222) plane by the X-ray diffraction method.

  Such a conductive substrate according to the present invention preferably includes the ITO layer whose 2θ peak angle corresponding to the (222) plane by X-ray diffraction method is 30.0 deg or more and 31.0 deg or less.

  In such a conductive substrate according to the present invention, preferably, the ITO layer is such that a crack of 1 μm or more and 1 mm or less does not occur in the film in a process of repeating a heating and cooling cycle of 160 ° C. for 1 hour three times. Include.

  Such a conductive substrate according to the present invention preferably includes one in which the ITO layer is formed by a reactive ion plating method using a pressure gradient plasma gun. Such a conductive substrate according to the present invention preferably includes a substrate in which the ITO layer is formed on a substrate under a temperature condition of −25 ° C. or more and 20 ° C. or less.

  Such a conductive substrate according to the present invention preferably includes a substrate in which the ITO layer is formed on a substrate cooled with an organic solvent containing 45 to 60% by volume of ethylene glycol.

  Such a conductive substrate according to the present invention preferably includes the ITO layer formed by a reactive ion plating method under a film forming pressure condition of 0.01 Pa or more and 0.2 Pa or less. .

  Such a conductive substrate according to the present invention preferably includes a substrate on which a transparent substrate is formed.

Such a conductive substrate according to the present invention preferably includes the transparent substrate having a water vapor transmission rate of less than 1.0 g / m ² / day.

  Such a conductive substrate according to the present invention preferably includes that the transparent base material is made of a transparent resin compound.

The conductive substrate according to the present invention preferably has a volume resistance value of 5 × 10 ⁻⁴ Ωcm or less, a total light transmittance of 75% or more, and a film density of the ITO layer of 7.0 g / It is cm ³ or more.

  Such a conductive substrate according to the present invention preferably includes a substrate in which at least one transparent inorganic compound layer is formed between the transparent substrate and the ITO layer.

  Such a conductive substrate according to the present invention preferably includes a substrate in which the transparent inorganic compound layer is made of a silicon-containing compound.

  Such a conductive substrate according to the present invention preferably includes a substrate in which at least one transparent organic compound layer is formed between the transparent substrate and the ITO layer.

  In such a conductive substrate according to the present invention, the transparent organic compound layer is preferably composed of at least one sol-gel compound obtained by hydrolysis of an acrylate resin, an epoxy resin, an ester resin, a urethane resin, or a metal alkoxide. .

  Such a conductive substrate according to the present invention preferably includes a substrate in which at least one transparent inorganic compound layer is formed on the side of the transparent base opposite to the surface on which the ITO layer is formed. To do.

  Such conductive substrates according to the present invention preferably include those used as transparent electrode substrates for organic EL elements.

  Such a conductive substrate according to the present invention preferably includes a substrate used as a transparent electrode substrate for an organic EL device having a light emission lifetime of 30000 hours or more.

Such a conductive substrate according to the present invention preferably includes a substrate used as a transparent electrode substrate for an organic EL device having a dark spot density of 1 piece / mm ² or less.

  Such a conductive substrate according to the present invention preferably includes a substrate used as a transparent electrode substrate for an organic EL element having a short frequency of 1/10 elements or less.

  Such a conductive substrate according to the present invention preferably includes a substrate used as a transparent electrode substrate for an organic EL element having a current value of 1.5 mA or more when 6 V is applied to the organic EL element.

Such a conductive substrate according to the present invention preferably includes a substrate used as a transparent electrode substrate for an organic EL device having an emission luminance of 400 cd / m ² or more when 6 V of the organic EL device is applied.

  When the conductive substrate according to the present invention is configured as described above, for example, when used in an organic EL element, the lifetime as the organic EL element can be sufficiently extended, and the flexibility of the substrate and the durability of the substrate can be achieved. It is possible to provide a substrate for an organic EL element that can sufficiently satisfy the properties and strength at the same time. In particular, it is possible to provide a substrate for an organic EL display device that can extend the life of the organic EL element to more than 100,000 hours.

<ITO film>
The ITO (Indium Tin Oxide) film of the conductive substrate according to the present invention has (1) integrated intensity A of 2θ peak corresponding to (222) plane and integrated intensity of 2θ peak corresponding to (440) plane by X-ray diffraction method. An ITO film having an integrated intensity ratio A / C with C of 5.0 or more. The integrated intensity ratio A / C is preferably 7.0 or more, particularly preferably 14.0 or more. When the integrated intensity ratio A / C is 5.0 or more, the crystalline state of ITO becomes isotropic, and the presence of vacancies between crystal lattices is drastically reduced. As a result, it is considered that electron transport (or hole transport) proceeds smoothly and the organic EL characteristics are remarkably improved.

  The ITO of the conductive substrate according to the present invention has (2) an integral of an integrated intensity B of 2θ peak corresponding to the (400) plane and an integrated intensity C of 2θ peak corresponding to the (440) plane by X-ray diffraction. The strength ratio B / C is preferably 1.0 or less. The integrated intensity ratio B / C is preferably 0.9 or less, particularly preferably 0.8 or less. When the integrated intensity ratio B / C is 1.0 or less, the crystalline state of ITO becomes more isotropic. When observed with an SEM cross-sectional photograph of ITO, the grain boundary of the crystal is not seen or becomes very large as 0.1 μm or more. This is because the growth of particles proceeds in a fractal shape. When A / C and B / C are outside the above ranges, the ITO film has many grain boundary defects.

  The ITO of the conductive substrate according to the present invention preferably has (3) an integrated intensity A of 2θ peak corresponding to (222) plane by X-ray diffraction method of 7000 counts or more. The integrated intensity A is preferably 10,000 counts or more, particularly preferably 15000 counts or more. This strong orientation provides unprecedented low resistance. In addition, the transmittance of wavelengths in the visible range is increased. Further, since the alignment planes are aligned, the surface becomes smooth.

  The ITO of the conductive substrate according to the present invention preferably has (2) a half-value width of 2θ peak corresponding to (222) plane by X-ray diffraction method of 1.0 deg or less. The half width is preferably 0.95 deg or less, particularly preferably 0.92 deg or less. The narrow half-value width indicates high crystallinity, which also has a great influence on the lifetime of the organic EL.

  The ITO of the conductive substrate according to the present invention preferably has (2) a 2θ peak angle corresponding to the (222) plane by X-ray diffraction method of 30.0 deg to 31.0 deg. This peak angle is preferably 30.0 deg or more and 30.8 deg or less, particularly preferably 30.3 deg or more and 30.6 deg or less. When the peak angle is outside the above range, the above performance can be obtained specifically.

  Here, the above (1) to (4) are conditions related to the crystal lattice arrangement of the ITO film, and (5) and (6) are conditions mainly related to the crystallinity of the ITO film. The peak integrated intensity ratio, half value, peak angle, and the like can be determined by X-ray diffraction (XRD).

  In the present invention, if the ITO film does not satisfy (1) to (4) and therefore the crystal lattice arrangement of the ITO layer is non-uniform, tin doped when an electric field is applied is introduced to the hole injection layer side. It is assumed that the energy level of hole transmission changes and holes cannot be transferred because of migration, resulting in a shortened light emission lifetime.

  Therefore, in order that tin can be stably put into the film without causing migration, it is preferable that the half width is narrow and the crystallinity is high. If the half value is narrow as in the present invention, the crystallinity is high, chemically stable, hard, and the structure is stable. That is, tin is well confined in the crystal.

The constituent components of the ITO film are arbitrary as long as the film satisfying the above (1) to (6) can be formed. In the present invention, indium oxide (In ₂ O ₃ ) and tin oxide are used. _(SnO 2) 1 to 35 made of the% by weight being preferred.

  In general, ITO is a polycrystal and thus has various light distribution surfaces. However, the ITO film satisfying the above (1) to (4) according to the present invention is particularly characterized by the (222) crystal plane, and has a crystal lattice arrangement. High uniformity and high crystallinity make it difficult to achieve with conventional ITO films. For example, it is possible to improve the lifetime of electronic devices, reduce the frequency of short circuits, and reduce dark spot defects. .

  The ITO layer satisfying the above various conditions can be formed by a method such as an ion plating method, an ion assist method, a pulsed laser deposition method, or a plasma CVD method. In addition, as long as it is a method which gives the same film quality, it is not limited to these.

  Among these, an ion plating method, particularly a reactive ion plating method using a pressure gradient plasma gun is particularly preferable. In this method, the film-forming particles are injected or accumulated on the substrate while maintaining high energy, so that the ITO thin film crystal grains become large and a high-density film can be easily and stably produced.

  As the crystal orientation of the ITO film is highly controlled or as the crystallinity increases, cracks tend to occur when stress is applied to the film. As a method for preventing this, a method of lowering the substrate temperature is preferable. When the temperature of the substrate on which the ITO film is formed is preferably −25 ° C. or higher and 20 ° C. or lower, particularly −10 ° C. or higher and 10 ° C. or lower, cracks can be prevented and a highly oriented film can be produced. For example, in a process of repeating a heating / cooling cycle of 160 ° C. for 1 hour three times, it is possible to obtain an ITO film in which no cracks of 1 μm or more and 1 mm or less occur in the film.

  As a substrate cooling medium used for maintaining the substrate temperature within the above range, an organic solvent containing ethylene glycol, particularly an organic solvent containing 45 to 60% by volume of ethylene glycol is preferable. When the ethylene glycol content is less than 45% by volume, the refrigerant is likely to condense and it becomes difficult to stably cool the substrate present in the vacuum. On the other hand, when the volume is 60% by volume or more, the viscosity of the refrigerant is high, and the circulation efficiency of the refrigerant may deteriorate, resulting in a problem.

  The film forming pressure is preferably 0.01 Pa or more and 0.2 Pa or less, particularly 0.05 Pa or more and 0.15 Pa or less. When the film forming pressure is within the above range, the performance as described above can be provided. When the film forming pressure is less than 0.01 Pa, the plasma becomes unstable, and the formed film has a strong film stress, which may cause micro defects such as cracks, or the film may have poor adhesion and may be peeled off. On the other hand, if it exceeds 0.2 Pa, it becomes difficult to obtain a crystalline film having orientation due to kinetic energy loss in the vacuum of the vapor deposition material.

<Conductive substrate>
A conductive substrate according to the present invention has the ITO film formed thereon.

  Such a conductive substrate according to the present invention comprises at least one ITO film and at least one substrate for supporting or holding the ITO film. The conductive substrate according to the present invention may have other layers on the surface of the ITO film, at an intermediate position between the ITO film and the substrate, or on the non-forming surface of the ITO film of the substrate, if necessary. One or more layers can be formed. By forming such other layers, various characteristics of the conductive substrate of the present invention can be improved, improved or controlled, whereby a conductive substrate particularly suitable for a specific application can be obtained. Such other layers, for example, are advantageous in improving the characteristics and functions of various layers, devices, etc. to which the conductive substrate of the present invention is applied, as well as layers that improve gas barrier properties and mechanical strength. Each layer is included.

  The conductive substrate according to the present invention can be widely applied to various uses. The main use of the conductive substrate of the present invention is, for example, an electronic or optical element such as a display substrate, an illumination substrate, a solar cell substrate, a circuit board substrate, a semiconductor substrate, or electronic paper. The use as an electroconductive board | substrate of a machine can be mentioned. In addition, it can be used as a conductive substrate used in, for example, industrial material use, packaging use, building material use, information recording medium, security field, publication, and bio field.

  As an application in which the effect of the conductive substrate according to the present invention is particularly remarkably exhibited, a conductive substrate for a light emitting element, particularly preferably an organic EL light emitting element can be mentioned.

The conductive substrate according to the present invention, in particular, the volume resistance value is 10 × 10 ⁻⁴ Ωcm or less, the total light transmittance is 70.0% or more, and the film density of the ITO layer is 6.8 g / cm ³ or more. A certain conductive substrate is suitable as a substrate for a light emitting element, particularly a transparent electrode substrate for an organic EL light emitting element. According to the present invention, the volume resistance value is 5.0 × 10 ⁻⁴ Ωcm or less, the total light transmittance is 75.0% or more, or the ITO layer has a film density of 7.0 g / cm ³ or more. The conductive substrate is particularly suitable as a transparent electrode substrate for the above-mentioned use, particularly an organic EL light-emitting element.
If the volume resistance exceeds 10 × 10 ⁻⁴ Ωcm, in the case of a large-area element, there may be problems such as uneven light emission, inability to withstand high-speed response, inability to withstand low-voltage driving, etc. is there. Moreover, if the total light transmittance is less than 70.0%, it is difficult to obtain sufficient luminance. And since a film density is less than 6.8 g / cm < ³ >, current efficiency is bad and the light emission defect arises, it is not preferable.

Base Material The base material in the conductive substrate according to the present invention can be used without particular limitation. Accordingly, the substrate may be (i) a glass substrate or a hard resin substrate, preferably a wafer, a printed substrate, a non-flexible substrate made of a molded resin such as various cards and bottles, or the like, depending on the specific application and purpose, or (B) Flexible resin substrate, preferably, for example, polyethylene terephthalate or polyethylene naphthalate, polycarbonate, polyacrylate, polymethacrylate, polyurethane acrylate, polyethersulfone, polyimide, polysilsesquioxane, polynorbornene, polyether It can be formed of imide, polyarylate, cyclic polyolefin or the like. In the case of a resin substrate, those having a heat resistance of preferably 100 ° C. or higher, particularly preferably 150 ° C. or higher are suitable.

  There is no particular limitation on the thickness of the substrate. In the case of a flexible substrate, the thickness of the substrate is preferably in the range of, for example, 50 to 400 μm from the viewpoints of flexibility and form retention.

  Moreover, when transparency is required for the conductive substrate according to the present invention, this substrate is preferably formed of a material having a high degree of transparency.

The base material preferably has a high gas barrier property, for example, a water vapor permeability of less than 50 g / m ² / day, particularly a material of less than 10 g / m ² / day. Here, the gas barrier property is measured using PARMATRAN 3/31 made by Mocon under the condition of 37.8 ° C. and 100% Rh.

ITO film The ITO film of the conductive substrate according to the present invention is as described above. This ITO film can function mainly as a wiring layer or an electrode for supplying electricity to various electronic elements or electronic devices constructed using this conductive substrate.

  The thickness of the ITO film is not particularly limited, but is preferably 0.05 to 0.8 [mu] m, particularly preferably 0.1 to 0.4 [mu] m, from the viewpoint of the bending resistance of the flexible substrate and the ease of etching.

Gas Barrier Layer The gas barrier layer provided as necessary in the conductive substrate according to the present invention is not particularly limited, and can be obtained, for example, by various conventionally used gas barrier layer forming materials. Examples of such a material for forming a gas barrier layer include at least one kind of inorganic compound selected from the group consisting of silicon oxide, silicon nitride, silicon carbide, aluminum oxide, aluminum nitride, and aluminum carbide. Among these, those made of silicon-containing compounds such as silicon oxide, silicon nitride, silicon carbide are particularly preferable.

  The method for forming the gas barrier layer is not particularly limited, and can be produced by using various film forming methods such as a vacuum deposition method, a sputtering method, an ion plating method, or a CVD method.

The required performance of the gas barrier layer varies depending on the application. In the present invention, the water vapor transmission rate is preferably 1.0 g / m ² / day or less, particularly 1 × 10 ⁻¹ g / m ² / day or less. The oxygen gas permeability is preferably 1.0 cc / m ² / day or less, particularly 1 × 10 ⁻¹ cc / m ² / day or less.

In particular, when the conductive substrate according to the present invention is applied to an organic EL element, the water vapor transmission rate is preferably 1 × 10 ⁻¹ g / m ² / day or less. More preferably, 1 * 10 ^<-2 > g / m ^{< 2} > / day or less is good. The gas permeability is preferably 1 × 10 ⁻¹ cc / m ² / day or less, particularly 1 × 10 ⁻² cc / m ² / day or less. Here, the gas barrier property is measured using PARMATRAN 3/31 made by Mocon under the condition of 37.8 ° C. and 100% Rh.

  Said inorganic compound layer can be formed between a base material and an ITO layer, and can be formed in the opposite surface to the ITO layer of a base material. When formed between the substrate and the ITO layer, particularly high gas barrier properties can be achieved, and when formed on the surface opposite to the ITO layer of the substrate, the inorganic compound The layer has an effect of suppressing degassing, suppresses deformation of the substrate due to stress during film formation, and also has flexibility. In particular, it is effective as an organic EL substrate.

Organic Compound Layer The organic compound layer provided as necessary in the conductive substrate according to the present invention is not particularly limited, and can be obtained by, for example, various polymer materials conventionally used. As such a polymer material, there are few selected from the group consisting of ester, urethane, amide, aramid, imide, carbonate, styrene, acetal, acrylate, methacrylate, epoxy, olefin, isocyanate, ethyleneimine, and butadiene resin. And a kind of organic compound. Of these, esters, urethanes, acrylates, and epoxies are particularly preferable. The method for forming the organic compound layer is not particularly limited. For example, a method of laminating films made of the above compound materials or applying a liquid compound material can be used.

  The type, properties, thickness, and the like of the organic compound material can be appropriately determined in consideration of the necessary performance according to the specific application of the conductive substrate. For example, it can be determined in consideration of mechanical strength, heat resistance, gas barrier properties, flexibility, chemical resistance, optical characteristics, etc. required for the conductive substrate according to the present invention.

  Said organic compound layer can be formed between a base material and an ITO layer, and can be formed in the surface opposite to the ITO layer of a base material. This organic compound layer can have both a stress relaxation function and flexibility to the conductive substrate according to the present invention. In addition, the surface shape can be changed. This makes it possible to flatten the surface of the conductive substrate and to provide an optical function.

<Electrode substrate for organic EL element>
As described above, the use of the conductive substrate according to the present invention can be exemplified by the conductive substrate for the organic EL light emitting device.

Accordingly, the conductive substrate according to the present invention includes, for example, (1) a conductive substrate used as a transparent electrode substrate for an organic EL element, and (2) a transparent electrode substrate for an organic EL element having a light emission lifetime of 30000 hours or more. Conductive substrate used (Here, the light emission lifetime is the time for which the luminance is reduced to 50% of the initial value in terms of 100 cd / m ² ) (3) Dark spot density is 1 / mm ² or less (4) a conductive substrate used as a transparent electrode substrate for an organic EL element, (4) a conductive substrate used as a transparent electrode substrate for an organic EL element having a short frequency of 1/10 elements or less, (5) organic A conductive substrate used as a transparent electrode substrate for an organic EL element having a current value of 1.5 mA or more when 6 V is applied to the EL element, (6) Light emission when 6 V of the organic EL element is applied Degrees conductive substrate used as a transparent electrode substrate for an organic EL element is 400 cd / m ² or more, etc. are included.

Organic EL device The conductive substrate according to the present invention is as described above, and the use of the conductive substrate according to the present invention is particularly remarkable in that there is a conductive substrate for an organic EL light emitting device. As described above. The configuration of the organic EL light-emitting element other than the electrode substrate is arbitrary. For example, each configuration proposed heretofore has been modified as it is or modified so that the effect of the present invention can be maximized. Can be used.

  Below, the preferable specific example of the organic electroluminescent light emitting element which can apply the electroconductive board | substrate by this invention is described.

  The organic EL element basically has a structure in which an organic EL layer containing an organic compound is sandwiched between a pair of electrodes of an anode electrode and a cathode electrode, and an anode electrode (anode electrode) / organic EL layer / cathode electrode. A laminated structure of (cathode electrode) is fundamental. Here, all the layers provided between the pair of electrodes are collectively referred to as an organic EL layer (also referred to as an organic light emitting layer), and a hole injection layer, a hole transport layer, a light emitting layer, and an electron transport layer. This includes an electron injection layer and the like.

  The pixel electrode and the counter electrode correspond to either an anode electrode or a cathode electrode, respectively, and constitute a pair of electrodes.

  In addition, as a material which comprises each layer which comprises an organic EL element, itself is well-known, For example, the following can be used in this invention.

  The cathode electrode may be made of any material as long as it is a material used for a normal organic EL element, and is particularly preferably a conductive material having a low work function so that electrons can be easily injected. Is, for example, magnesium alloy (MgAg), aluminum, silver or the like.

  In the organic EL element, at least one insulating layer can be formed partially on the substrate or the anode. Such an insulating layer is preferably made of a resin material containing a photo-curing resin such as an ultraviolet curable resin or a thermosetting resin, and has a pattern shape so that a portion with the insulating layer becomes a non-light-emitting portion when displaying. Can be formed. Moreover, an insulating layer can also be formed as a black matrix by mixing carbon black or the like with this resin material.

  A general organic EL device has a basic structure of a stacked structure in which a hole transport layer and a light-emitting layer, or a hole transport layer, a light-emitting layer, and an electron transport layer are stacked between an anode electrode and a cathode electrode. However, between the anode electrode and the cathode electrode, a light-emitting layer made of an organic light-emitting material that causes electroluminescence is an essential layer, and a hole transport layer that transports holes to the light-emitting layer as an optional layer, hole transport A hole injection layer for injecting holes into the layer, an electron transport layer, an electron injection layer, and the like can be provided.

Note that these layers that can be stacked between the anode electrode and the cathode electrode are collectively referred to as an organic EL layer.

  The organic light emitting material constituting the light emitting layer is roughly classified into various types such as a dye material, a metal complex material, or a polymer material.

  Examples of dye-based materials include cyclopentadiene derivatives, tetraphenylbutadiene derivatives, triphenylamine derivatives, oxadiazole derivatives, pyrazoloquinoline derivatives, distyrylbenzene derivatives, distyrylarylene derivatives, silole derivatives, thiophene ring compounds, Examples thereof include pyridine ring compounds, perinone derivatives, perylene derivatives, oligothiophene derivatives, trifumanylamine derivatives, oxadiazole dimers, and pyrazoline dimers.

  Examples of the metal complex material include aluminum, quinolinol complex, benzoquinolinol beryllium complex, benzoxazole zinc complex, benzothiazole zinc complex, azomethylzinc complex, porphyrin zinc complex, and europium complex. Examples of the metal complex include Be or the like, or a rare earth metal such as Tb, Eu, or Dy, and a ligand having an oxadiazole, thiadiazole, phenylpyridine, phenylbenzimidazole, quinoline structure, or the like.

  Examples of the polymer material include polyparaphenylene vinylene derivatives, polythiophene derivatives, polyparaphenylene derivatives, polysilane derivatives, polyacetylene derivatives, polyfluorene derivatives, polyvinylcarbazole derivatives, etc. A material obtained by polymerizing the material can be given.

  The light emitting layer made of the above organic light emitting material can be doped for the purpose of improving the light emission efficiency or changing the light emission wavelength, if necessary. Examples of the doping material for performing this doping include perylene derivatives, coumarin derivatives, quinacridone derivatives, squalium derivatives, porphyrin derivatives, styryl dyes, tetracene derivatives, pyrazoline derivatives, decacyclene, phenoxazone, and the like.

  The hole injection layer is provided between the anode electrode and the hole transport layer or between the anode electrode and the light emitting layer.

  As a material constituting the hole injection layer, for example, phenylamine, starburst amine, or phthalocyanine, oxide such as vanadium oxide, molybdenum oxide, ruthenium oxide, or aluminum oxide, amorphous carbon, polyaniline, Or a polythiophene derivative etc. can be mentioned.

  The electron transport layer is provided between the light emitting layer and the cathode electrode or between the light emitting layer and the electron injection layer.

  Examples of the material constituting the electron transport layer include substances that form a generally stable radical anion and have a large ionization potential, such as oxadiazoles or aluminum quinolinol complexes. A 3,4-oxadiazole derivative, a 1,2,4-triazole derivative, etc. can be mentioned.

  The electron injection layer is provided between the electron transport layer and the cathode electrode, or between the cathode electrode and the light emitting layer.

  Examples of the material constituting the electron injection layer include a Group 1A or Group 2A metal, or an oxide or halide thereof. Specific examples of the Group 1A metal, oxides thereof, and halides include fuca lithium, sodium oxide, and lithium oxide. Here, specific examples of Group 2A metals, oxides thereof, and halides include strontium, magnesium oxide, magnesium fluoride, strontium fluoride, calcium, calcium fluoride, barium fluoride, and strontium oxide. Can be mentioned.

<Measurement evaluation method>
In addition, although it is a measurement evaluation method, surface resistance is measured by the four-end needle method (Mitsubishi Yuka Lorester AP). The total light transmittance is measured with a haze meter (manufactured by Takachiho Seiki).

  The film density was measured using an X-ray diffractometer (manufactured by Rigaku Electric Industry Co., Ltd., ATX-E), and the obtained data was reflected using analysis software (manufactured by Rigaku Electric Industrial Co., Ltd., RGXR). The rate was obtained by fitting by a non-linear least square method. The R value at the time of analysis was less than 1%, which was used as a criterion for accuracy. As an X-ray, an 18 kW X-ray generator is used to generate a CuKα ray having a wavelength (λ) of 1.5405 mm by a Cu target. As a monochromator, a parabolic population multilayer mirror and a Ge (220) monochrome crystal are used. Was used. After mounting the transparent conductive sheet of the sample on the substrate holder with a magnet and adjusting the position by 0 ° using the automatic alignment function, the scan speed: 0.1000 ° / min, the sampling width: 0.002 °, and Scanning range: The reflectance was measured while scanning under a setting condition of 0 to 4.0000 °. The reflectance data obtained by the measurement is obtained by inputting the element ratio of the thin film as an initial value using the above analysis software, and fitting by a least square method under the condition of a fitting area: 0.600 ° to 4.000 °. The film density was determined.

The integral intensity ratio, half width, etc. can be measured using, for example, a Rigaku X-ray diffractometer (also referred to as an XRD apparatus) under the following measurement conditions.
・ X-ray: 50 kV, 300 mA
Scan speed: 4.0000 ° / min
・ Sampling width: 0.0400 °
Operation range: 5.0000 ° to 120.000 °
・ Incident monochrome: slit collimation ・ Counter monochromator: receiving slit

  Next, examples of the present invention and comparative examples will be given to further explain the present invention.

<Example 1>
A plastic film substrate made of 100 μm thick PEN resin (Q65 made by Teijin DuPont) dried at 160 ° C. for 1 hour with a dryer is used as a transparent film substrate, and a silicon oxynitride film with a film thickness of 100 nm is formed on both sides thereof. A film (Si ₃ N ₄ target: manufactured by Toshima Seisakusho (4N), film forming pressure: 0.3 Pa, power 5 kW) was formed by sputtering.

  Thereby, the inorganic compound layer was formed.

  Thereafter, an epoxy resin composition (V-259-EH manufactured by Nippon Steel Chemical Co., Ltd.) having a cardo skeleton on one side was applied by spin coating, and dried at 160 ° C. for 1 hour to obtain a 1 μm organic compound layer. .

  Thereafter, an inorganic compound layer made of a silicon oxynitride film having a thickness of 100 nm was formed on the organic compound layer by a sputtering method to obtain a gas barrier film.

When the gas barrier property was measured, it was a value below the measurement limit (1 × 10 ⁻² g / m ² / day or less).

  Here, the gas barrier property was measured under the conditions of 37.8 ° C. and 100% Rh using PARMATRAN 3/31 manufactured by Mocon.

  An ITO film having a film thickness of 160 nm was formed on one side of the gas barrier film by an ion plating method (Ar: 16 sccm, oxygen: 22 sccm, discharge power: 4.0 kW, film formation pressure: 0.1 Pa). At that time, the temperature of the substrate was set to 5 ° C.

  Thereafter, the film density of the ITO film, the integrated intensity ratio A / C between the integrated intensity A of the peak corresponding to the (222) plane and the integrated intensity C of the peak corresponding to the (440) plane, also corresponds to the (400) plane. Table 1 below shows other evaluation results such as an integrated intensity ratio between the integrated intensity B of the peak and the integrated intensity C of the peak corresponding to the (440) plane.

Here, a Rigaku X-ray diffractometer was used as an X-ray diffractometer (also referred to as an XRD apparatus), and measurement was performed under the following measurement conditions.
・ X-ray: 50 kV, 300 mA
Scan speed: 4.0000 ° / min
・ Sampling width: 0.0400 °
Operation range: 5.0000 ° to 120.000 °
・ Incident monochrome: slit collimation ・ Counter monochromator: receiving slit and total light transmittance were measured.

  Next, after the produced gas barrier film with an ITO thin film was washed, the ITO film was etched into a predetermined pattern to form an anode electrode to obtain a flexible transparent electrode substrate.

  Subsequently, the display part which consists of an organic EL element was produced using the flexible transparent electrode substrate produced in this way.

  After cleaning the anode surface of the obtained anode substrate, the following PEDOT / PSS dispersion was applied on the anode electrode surface by spin coating, and after application, placed on a hot plate at a temperature of 200 ° C. 30 Heated for minutes to dry.

Further, it was transferred into a glove box substituted with pure nitrogen and again placed on a hot plate at a temperature of 200 ° C. and heated for 15 minutes to dry, and an 80 nm thin film of PEDOT / PSS was obtained on the anode.
PEDOT / PSS = 1/20 (manufactured by Bayer, using Vitron P VP CH8000)

  Next, a solution for forming a light emitting layer in which a phosphor for organic EL element (manufactured by Sigma Aldrich, product number: ADS228GE) is mixed in toluene so as to be 1.0% (mass ratio) is prepared. The obtained PEDOT / PSS thin film was applied by spin coating in a glove box, and after application, it was placed on a hot plate at a temperature of 130 ° C. and dried by heating for 1 hour. A layer was formed.

  Next, vapor deposition is performed in a glove box on the light emitting layer on the substrate on which the layers up to the light emitting layer are formed, and a 3 nm thick LiF thin film and a 10 nm thick Ca thin film are sequentially formed to inject electrons. Further, an Al thin film having a thickness of 180 nm was formed on the electron injection layer to form a cathode electrode.

  Then, what applied the ultraviolet curable adhesive (Nagase Chemtech Co., Ltd. product number; XNR5516HP-B1) to the convex part of the glass for sealing which has a convex part around was formed to said cathode electrode. Laminate on the substrate, irradiate the area where the adhesive was applied with ultraviolet rays to cure the adhesive, and place the superposed substrate after irradiation on a hot plate at a temperature of 80 ° C. for 1 hour. The adhesive was sufficiently cured to form an organic EL element.

  By applying a DC voltage between the anode electrode (ITO electrode) and the cathode electrode (also referred to as a back electrode layer) of the display unit made of the organic EL element obtained as described above, both electrodes cross each other. As a result of emitting light from the light emitting layer at a desired position, good light emission was obtained at any position.

  The evaluation results are shown in Table 1.

  Here, with respect to the organic EL element formed as described above, a voltage is continuously applied so that the initial luminance becomes 100 Cd, and a change in luminance with the passage of time is measured. Is defined as the emission lifetime of the organic EL.

<Example 2 , 4-6, 8-10 and Comparative Examples 1-3 and Reference Examples 1-2 >
Samples were prepared and evaluated in the same manner as in Example 1. Table 1 summarizes the differences and results from Example 1.

Claims (21)

On the transparent substrate , the integrated intensity ratio A / C between the integrated intensity A of the 2θ peak corresponding to the (222) plane and the integrated intensity C of the 2θ peak corresponding to the (440) plane by the X-ray diffraction method is 7.0. The integrated intensity ratio B / C between the integrated intensity B of the 2θ peak corresponding to the (400) plane and the integrated intensity C of the 2θ peak corresponding to the (440) plane by the X-ray diffraction method is 0.80 or less. ones, and the and wherein the half width of 2θ peak corresponding to (222) plane by X-ray diffractometry ITO film is formed is less than 0.95Deg, conductive organic EL device substrate. 2. The organic EL device according to claim 1 , wherein when the ITO layer is measured under the following measurement conditions, the integrated intensity A of the 2θ peak corresponding to the (222) plane by the X-ray diffraction method is 7000 counts or more. conductive substrate use.
Measurement conditions: X-ray: 50 kV, 300 mA
Scan speed: 4.0000 ° / min
Sampling width: 0.0400 °
Operating range: 5.0000 ° to 120.000 °
Incident monochrome: slit collimation
Counter monochromator: Light receiving slit The ITO layer is, 2 [Theta] peak angle corresponding to (222) plane by X-ray diffraction method are: 31.0deg above 30.0Deg, conductive substrate for an organic EL device according to claim 1 or 2 . The process according to any one of claims 1 to 3 , wherein the ITO layer is one in which cracks of 1 µm or more and 1 mm or less are not generated in the process of repeating the heating and cooling cycle of 160 ° C for 1 hour three times. A conductive substrate for organic EL devices . The electroconductive board | substrate for organic EL devices of any one of Claims 1-4 whose said transparent base material is a thing with the water-vapor-permeation rate of less than 1.0 g / m < ² > / day. The electroconductive board | substrate for organic EL devices of any one of Claims 1-5 in which the said transparent base material consists of a transparent resin compound. And the volume resistivity 5 × ^{10 -4} Ωcm or less, total light transmittance of 75% or more, the film density of the ITO layer is 7.0 g / cm ³ or more, any one of claims 1 to 6 2. A conductive substrate for an organic EL device according to item 1. Transparent inorganic compound containing at least one inorganic compound selected from the group consisting of at least one layer of silicon oxide, silicon nitride, silicon carbide, aluminum oxide, aluminum nitride, and aluminum carbide between the transparent substrate and the ITO layer The electroconductive board | substrate for organic EL devices of any one of Claims 1-7 in which the layer was formed. The conductive substrate for an organic EL device according to claim 8 , wherein the transparent inorganic compound layer is made of a silicon-containing compound. At least one layer transparent organic compound layer is formed, a conductive substrate for an organic EL device according to any one of claims 1 to 9 between the ITO layer and the transparent substrate. The conductive substrate for an organic EL device according to claim 10 , wherein the transparent organic compound layer comprises at least one sol-gel compound obtained by hydrolysis of an acrylate resin, an epoxy resin, an ester resin, a urethane resin, or a metal alkoxide. . The organic EL device according to any one of claims 1 to 11 , wherein at least one transparent inorganic compound layer is formed on the opposite side of the transparent substrate from the surface on which the ITO layer is formed . conductive substrate. Conductive substrate for an organic EL device according to any one of claims 1 to 12 for use as a transparent electrode substrate for an organic EL device emission lifetime is more than 30000 hours. Dark spot density is used as a transparent electrode substrate for an organic EL element is one / mm ² or less, a conductive substrate for an organic EL device according to any one of claims 1 to 13. Short frequency is used as a transparent electrode substrate for an organic EL element is not more than once / 10 element, a conductive substrate for an organic EL device according to any one of claims 1-14. The electroconductivity for organic EL devices of any one of Claims 1-15 used as a transparent electrode substrate for organic EL elements whose current value at the time of applying 6V to an organic EL element is 1.5 mA or more. substrate. Emission luminance upon 6V application of the organic EL element is used as a transparent electrode substrate for an organic EL element is 400 cd / ^{m 2} or more, conductivity for an organic EL device according to any one of claims 1-16 Substrate. A method for producing a conductive substrate for an organic EL device having an ITO film formed on a transparent substrate,
The ITO film was subjected to a reactive ion plating method using a pressure gradient type plasma gun, and an integrated intensity A of 2θ peak corresponding to the (222) plane by X-ray diffraction and a 2θ peak corresponding to the (440) plane. The integrated intensity ratio A / C with respect to the integrated intensity C is 7.0 or more, and the integrated intensity B of the 2θ peak corresponding to the (400) plane and the integrated intensity of the 2θ peak corresponding to the (440) plane by X-ray diffraction method. An ITO film having an integrated intensity ratio B / C with C of 0.80 or less and a half-width of a 2θ peak corresponding to the (222) plane by an X-ray diffraction method of 0.95 deg or less is formed. The manufacturing method of the electroconductive board | substrate for organic EL devices characterized by the above-mentioned. The ITO layer is formed on a substrate temperature of -25 ° C. or higher 20 ° C. A method for fabricating a conductive substrate for an organic EL device according to claim 18. The ITO layer, the ethylene glycol is formed on a substrate that is cooled by organic solvent containing at 45-60% by volume, method for producing a conductive substrate for an organic EL device according to claim 19. The conductive layer for an organic EL device according to any one of claims 18 to 20 , wherein the ITO layer is formed by a reactive ion plating method under a film forming pressure condition of 0.01 Pa or more and 0.2 Pa or less. Of manufacturing a conductive substrate.