JP2016054097A - Organic electroluminescent element and substrate - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide an organic electroluminescent element capable of striking a balance between light extraction efficiency and storage stability.SOLUTION: The organic electroluminescent element includes a resin substrate 1, a gas barrier layer 2 provided on the resin substrate 1, a light-scattering layer 3 provided on the gas barrier layer 2, a smoothing layer 4 provided on the light-scattering layer 3, a cap layer 12 provided on the smoothing layer 4 and mainly composed of silicon nitride, and a light-emitting unit 6 comprising organic functional layers held between a pair of electrodes. The amount of outgassing from a laminate of the resin substrate 1, the light-scattering layer 3, the smoothing layer 4, and the cap layer 12 is 0.2 mg/mor less.SELECTED DRAWING: Figure 1

Description

  The present invention relates to an organic electroluminescence device including a light extraction layer and a substrate including a light extraction layer in order to improve light extraction efficiency.

  In recent years, in the electronic device field, in addition to demands for weight reduction and size increase, long-term reliability and a high degree of freedom in shape, and the ability to display curved surfaces have been added. Resin base materials such as transparent plastics have begun to be used in place of difficult glass substrates.

  However, a resin base material such as transparent plastic has a problem that gas barrier properties are inferior to a glass substrate. It has been found that if a substrate with inferior gas barrier properties is used, water vapor or oxygen will permeate, for example, deteriorating the function in the electronic device.

  Therefore, it is generally known that a film having a gas barrier property (gas barrier layer) is formed on a resin substrate and used as a gas barrier film. For example, it has been proposed to form a gas barrier layer including an inorganic layer and an organic layer disposed between the inorganic layers on a resin substrate (see, for example, Patent Document 1).

  In addition, in an organic electroluminescence (EL) element which is one of electronic devices, it is also known that a configuration in which a light extraction layer composed of a light scattering layer is effective in order to improve light emission efficiency. .

However, when a gas barrier layer or a light extraction layer is formed on a resin base material, the surface becomes uneven, and as a result, when a light emitting unit having an organic functional layer as an upper layer is formed, in a high temperature and high humidity atmosphere. It has been a problem that deterioration of storage stability and short circuit (electrical short circuit) are likely to occur.
Further, when the light extraction layer is formed on the resin base material, impurities remaining in the light extraction layer and the gas barrier layer have an adverse effect on the organic functional layer. In the first place, organic EL elements are known to be very sensitive to trace amounts of moisture / oxygen / other organic substances (residual solvent, etc.), and a configuration having a gas barrier layer directly under the organic functional layer has also been proposed. (For example, refer to Patent Document 2).

Japanese translation of PCT publication No. 2004-510373 Japanese Patent No. 4186688

  As described above, in an organic EL element, it is difficult to achieve both light extraction efficiency and storage stability. The present invention provides an organic electroluminescence device and a substrate capable of achieving both light extraction efficiency and storage stability.

The organic electroluminescence device of the present invention includes a resin base material, a gas barrier layer provided on the resin base material, a light scattering layer provided on the gas barrier layer, and a smoothing layer provided on the light scattering layer. And a cap layer mainly composed of silicon nitride provided on the smoothing layer, and a light emitting unit comprising an organic functional layer sandwiched between a pair of electrodes. And the amount of outgas emitted from the laminated body of a resin base material, a light-scattering layer, a smoothing layer, and a cap layer is 0.2 mg / m < ² > or less.

The substrate of the present invention includes a resin base material, a light scattering layer provided on the resin base material, a smoothing layer provided on the light scattering layer, and a silicon nitride provided on the smoothing layer. And a cap layer containing as a main component. And the amount of outgas emitted from the laminated body of a resin base material, a light-scattering layer, a smoothing layer, and a cap layer is 0.2 mg / m < ² > or less.

  ADVANTAGE OF THE INVENTION According to this invention, the organic electroluminescent element and board | substrate which can make light extraction efficiency and storage stability compatible can be provided.

It is sectional drawing which shows schematic structure of an organic EL element. It is a graph which shows each element profile of the thickness direction of the layer by the composition analysis of the depth direction using XPS of a gas barrier layer. It is the schematic which shows an example of the manufacturing apparatus of a gas barrier film. It is the schematic of the position setting of a gas supply port. It is a graph which shows each element profile of the thickness direction of the layer by the composition analysis of the depth direction using XPS of a gas barrier layer. It is a graph which shows each element profile of the thickness direction of the layer by the composition analysis of the depth direction using XPS of a gas barrier layer.

Hereinafter, although the example of the form for implementing this invention is demonstrated, this invention is not limited to the following examples.
The description will be given in the following order.
1. Embodiments of organic electroluminescence device and substrate

<1. Embodiments of Organic Electroluminescence Device and Substrate>
Hereinafter, specific embodiments of the organic electroluminescence element (organic EL element) and the substrate of the present invention will be described.

[Configuration of organic EL element]
The organic EL element includes a substrate, a pair of electrodes including a transparent electrode provided on the substrate, and a counter electrode, and an organic functional layer provided between the electrodes. The substrate includes at least a resin base material, a light scattering layer provided on the resin base material, a smoothing layer, and a cap layer mainly composed of silicon nitride. The organic EL element includes at least a gas barrier layer, a light scattering layer, a smoothing layer, a cap layer containing silicon nitride as a main component, and an organic functional layer sandwiched between a pair of electrodes on a resin substrate. Is provided.
Furthermore, in the organic EL element and the substrate, the amount of outgas emitted from the laminate of the resin base material, the light scattering layer, the smoothing layer, and the cap layer is 0.2 mg / m ² or less.

The outgas amount was measured when a sample having a cut measurement shape was measured under a gas generation condition at a heating temperature of 190 ° C. and a heating time of 30 minutes using a headspace-GC / MS (Headspace-Gas Chromatography / Mass Spectrometry) method. Of outgas per m ² .

In the organic EL element and substrate described above, the cap layer preferably has a refractive index of 1.8 to 2.5.
The surface roughness Ra of the cap layer is preferably 0 nm or more and 3 nm or less.
The cap layer is preferably formed by a plasma CVD method.
It is preferable that the resin base material, the light scattering layer, the smoothing layer, and the cap layer have a smaller refractive index as the layer is closer to the resin base material and a higher refractive index as the layer is closer to the electrode.
The resin base material, the light scattering layer, the smoothing layer, and the cap layer preferably have a surface roughness Ra that is larger as the layer is closer to the resin base material and a surface roughness Ra that is lower as the layer is closer to the electrode.
It is preferable that the haze value (ratio of the scattering transmittance to the total light transmittance) of the laminate of the resin base material, the light scattering layer, the smoothing layer, and the cap layer is 50% or more and 75% or less.

In FIG. 1, the structure of the organic EL element and board | substrate of embodiment is shown.
The organic EL element has at least one gas barrier layer 2 (first gas barrier layer 2a, second gas barrier layer 2b), light scattering layer 3, smoothing layer 4, cap layer 12, and transparent on the resin substrate 1. A light emitting unit 6 having an organic functional layer sandwiched between the electrode 5 (underlying layer 5a, conductive layer 5b) and the counter electrode 7 is laminated in this order.

In the organic EL element, the light scattering layer 3, the smoothing layer 4, and the cap layer 12 correspond to the light extraction layer.
Moreover, in the organic EL element shown in FIG. 1, the structure from the resin base material 1 to the cap layer 12 including the light scattering layer 3 and the smoothing layer 4 corresponds to the substrate of this embodiment.

Here, the “light emitting unit” refers to a light emitting body (unit) composed mainly of an organic functional layer containing at least various organic compounds, such as a light emitting layer 6c, a hole transport layer 6b, and an electron transport layer 6d. Say. The luminous body is sandwiched between a pair of electrodes composed of an anode and a cathode, and the holes supplied from the anode and the electrons supplied from the cathode are recombined in the luminous body. Emits light. The organic EL element may include a plurality of the light emitting units according to the desired emission color. Only the portion where the light emitting unit 6 is sandwiched between the transparent electrode 5 and the counter electrode 7 is the organic EL element. It becomes a light emitting area. The organic EL element is configured as a bottom emission type in which generated light (hereinafter referred to as emitted light h) is extracted from at least the resin base material 1 side. Transparent (translucent) means that the light transmittance at a wavelength of 550 nm is 50% or more. The main component is a component having the highest ratio in the entire configuration.

  An extraction electrode 8 is provided at the end of the transparent electrode 5 (conductive layer 5b). The transparent electrode 5 and an external power source (not shown) are electrically connected via the extraction electrode 8. Further, for the purpose of reducing the resistance of the transparent electrode 5, the auxiliary electrode 9 may be provided in contact with the conductive layer 5 b of the transparent electrode 5.

  Further, the layer structure of the organic EL element is not limited and may be a general layer structure. Here, the transparent electrode 5 functions as an anode (that is, an anode), and the counter electrode 7 functions as a cathode (that is, a cathode). In this case, for example, the light emitting unit 6 has a configuration in which a hole injection layer 6a / a hole transport layer 6b / a light emitting layer 6c / an electron transport layer 6d / an electron injection layer 6e are stacked in this order from the transparent electrode 5 side that is an anode. However, among these, it is essential to have at least the light emitting layer 6c composed of an organic material. The hole injection layer 6a and the hole transport layer 6b may be provided as a hole transport injection layer. The electron transport layer 6d and the electron injection layer 6e may be provided as an electron transport injection layer. Of these light emitting units 6, for example, the electron injection layer 6e may be made of an inorganic material.

  In addition to these layers, the light-emitting unit 6 may have a hole blocking layer, an electron blocking layer, and the like stacked as necessary. Furthermore, the light emitting layer 6c may have a structure in which each color light emitting layer that generates light emitted in each wavelength region is laminated, and each of these color light emitting layers is laminated via a non-light emitting auxiliary layer. The auxiliary layer may function as a hole blocking layer or an electron blocking layer. Furthermore, the counter electrode 7 as a cathode may also have a laminated structure as required. In such a configuration, only a portion where the light emitting unit 6 is sandwiched between the transparent electrode 5 and the counter electrode 7 becomes a light emitting region in the organic EL element.

  The organic EL element having the above configuration is sealed on the resin base material 1 with a sealing member 10 to be described later for the purpose of preventing deterioration of the light emitting unit 6 configured using an organic material or the like. Yes. The sealing member 10 is fixed to the resin base material 1 side with an adhesive 11. However, the terminal portions of the transparent electrode 5 (extraction electrode 8) and the counter electrode 7 are provided on the resin base material 1 in a state where they are exposed from the sealing member 10 while being insulated from each other by the light emitting unit 6. Yes.

The organic EL element may be an element having a so-called tandem structure in which a plurality of light emitting units 6 including at least one light emitting layer are stacked. Examples of typical element configurations of the tandem structure include the following configurations.
Anode / first light emitting unit / intermediate connector layer / second light emitting unit / intermediate connector layer / third light emitting unit / cathode

Here, the first light emitting unit, the second light emitting unit, and the third light emitting unit may all be the same or different. Further, the two light emitting units may be the same, and the remaining one may be different.
The plurality of light emitting units 6 may be directly stacked or may be stacked via an intermediate connector layer.

The intermediate connector layer is also commonly referred to as an intermediate electrode, intermediate conductive layer, charge generation layer, electron extraction layer, connection layer, or intermediate insulating layer. Electrons are transferred to the anode side adjacent layer and holes are connected to the cathode side adjacent layer. A known material structure can be used as long as the layer has a function of supplying. Examples of materials used for the intermediate connector layer include ITO (indium tin oxide), IZO (indium zinc oxide), ZnO ₂ , TiN, ZrN, HfN, TiO _x , VO _x , CuI, InN, and GaN. , CuAlO ₂ , CuGaO ₂ , SrCu ₂ O ₂ , LaB ₆ , RuO ₂ , Al and other conductive inorganic compound layers, Au / Bi ₂ O _{3 and} other two-layer films, SnO ₂ / Ag / SnO ₂ , ZnO / Ag / ZnO, Bi ₂ O ₃ / Au / Bi ₂ O ₃ , TiO ₂ / TiN / TiO ₂ , TiO ₂ / ZrN / TiO _{2 and} other multilayer films, C _{60 and} other fullerenes, oligothiophene and other conductive materials Conductive organic compound layers such as conductive organic layers, metal phthalocyanines, metal-free phthalocyanines, metal porphyrins, metal-free porphyrins, etc. It is, but is not limited thereto.

Examples of a preferable configuration in the light emitting unit 6 include, but are not limited to, a configuration in which the anode and the cathode are removed from the configuration described in the representative element configuration.
Specific examples of the tandem organic EL element include, for example, US Pat. No. 6,337,492, US Pat. No. 7,420,203, US Pat. No. 7,473,923, US Pat. No. 6,872,472, US Pat. No. 6,107,734. Specification, US Pat. No. 6,337,492, International Publication No. 2005/009087, JP-A 2006-228712, JP-A 2006-24791, JP-A 2006-49393, JP-A 2006-49394 JP-A-2006-49396, JP-A-2011-96679, JP-A-2005-340187, JP-A-4711424, JP-A-34966681, JP-A-3848564, JP-A-4421169, JP 2010-192719, JP 009-076929, JP 2008-078414 A, JP 2007-059848 A, JP 2003-272860 A, JP 2003-045676 A, International Publication No. 2005/094130, etc. Although a structure, a constituent material, etc. are mentioned, it is not limited to these.

  Hereinafter, main components and methods for manufacturing the organic EL element will be described.

[Cap layer]
The cap layer 12 is mainly composed of a nitride of silicon (Si). Thereby, while preventing efficiently the transmission of the gas discharge | released from the light-scattering layer 3 mentioned later and the smoothing layer 4, the water | moisture content in air | atmosphere, etc., the high temperature resulting from the unevenness | corrugation of the surface of the gas barrier layer 2 or the light-scattering layer 3 -It is possible to prevent adverse effects such as deterioration of storage stability and electrical short circuit (short circuit) in a high humidity atmosphere.
Here, the main component refers to a component having the highest constituent ratio among the components constituting the cap layer 12.

The cap layer 12 preferably has a water vapor permeability of less than 0.1 g / (m ² · 24 h). The water vapor permeability of the cap layer 12 is a value measured by a method based on JIS K 7129-1992. The cap layer 12 has a water vapor transmission rate (25 ± 0.5 ° C., relative humidity 90 ± 2% RH) of less than 0.1 g / (m ² · 24 h) and 0.01 g / (m ² · 24 h) or less. And is more preferably 0.001 g / (m ² · 24 h) or less.

  The refractive index of the cap layer 12 is preferably in the range of 1.7 to 3.0, more preferably in the range of 1.8 to 2.5, and particularly preferably in the range of 1.8 to 2.2. Is within. As the refractive index, a value at a wavelength of 633 nm measured at 25 ° C. with an ellipsometer is treated as a representative value.

  When the cap layer 12 is made of a low refractive index material (with a refractive index of less than 1.7), the layer thickness is preferably as thin as possible, and more preferably less than 100 nm. However, the cap layer 12 preferably has a certain gas barrier property, and the layer thickness at which a continuous film is formed is the lower limit. In this respect, 5 nm or more is necessary, preferably 10 nm or more, and particularly preferably 30 nm or more.

  On the other hand, when the cap layer 12 is made of a high refractive index material (refractive index of 1.7 or more), the upper limit of the layer thickness is not particularly limited, and is preferably 100 nm or more in consideration of gas barrier properties, for example, 200 nm. More preferably, the above is used. The lower limit of the layer thickness is the same as that of the low refractive index material. However, in the case where the cap layer 12 has visible light absorption, it is preferable that the layer thickness is as small as possible, and an optimum layer thickness can be set in view of necessary gas barrier properties and extraction efficiency.

  Further, the cap layer 12 preferably has a higher refractive index than the smoothing layer 4 which is the lower layer of the cap layer 12. The emitted light h from the light emitting unit 6 enters the cap layer 12, and further, the light transmitted through the cap layer 12 passes through the smoothing layer 4 and the like, and the light is extracted from the resin substrate 1 side. In general, the resin base material 1 is made of a material having a lower refractive index than that of the light emitting unit 6. For this reason, when the refractive index of the layer on the resin base material 1 side is smaller than the refractive index of the layer relatively close to the light emitting unit 6, light reflection at the interface of each layer is suppressed, and the light extraction efficiency is improved. .

  Specifically, since an organic material having a high refractive index is generally used for the light emitting unit 6, the average refractive index nc of the cap layer 12 is a value close to the refractive index of the organic functional layer included in the light emitting unit 6. Preferably there is. The cap layer 12 is a high refractive index layer having an average refractive index nc of 1.5 or more, particularly 1.8 or more and 2.5 or less at the shortest emission maximum wavelength among the emission maximum wavelengths of the emitted light h from the light emitting unit 6. It is preferable that If the average refractive index nc is 1.8 or more and 2.5 or less, it may be formed of a single material or a mixture. In the case of such a mixed system, the average refractive index nc of the cap layer 12 uses a calculated refractive index calculated by a total value obtained by multiplying the refractive index specific to each material by the mixing ratio. In this case, the refractive index of each material may be 1.8 or less, or 2.5 or more, as long as the average refractive index nc of the mixed film satisfies 1.8 or more and 2.5 or less. Good.

  Here, the “average refractive index nc” is the refractive index of a single material when it is formed of a single material, and in the case of a mixed system, the refractive index specific to each material is multiplied by the mixing ratio. It is the calculated refractive index calculated by the combined value. The refractive index is measured by irradiating a light beam having the shortest light emission maximum wavelength among the light emission maximum wavelengths of the emitted light h from the light emitting unit 6 in an atmosphere at 25 ° C., and by using an Abbe refractometer (manufactured by ATAGO, DR -M2).

  Further, the absorption in the entire visible light region of the 100 nm-thick layer (value obtained by dividing the total value of T% R% in the spectral wavelength measurement with an integrating sphere) is preferably small, preferably less than 10%, more preferably Is less than 5%, more preferably less than 3%, most preferably less than 1%.

  In addition, it is important that the cap layer 12 has flatness to satisfactorily form the transparent electrode 5 thereon, and the surface property is preferably such that the arithmetic average roughness Ra is in the range of 0 to 50 nm. More preferably, it is 30 nm or less, particularly preferably 10 nm or less, and most preferably 3 nm or less. Further, the cap layer 12 preferably has an arithmetic average roughness Ra smaller than that of the smoothing layer 4 which is the lower layer of the cap layer 12.

  By reducing the arithmetic average roughness Ra, it is possible to suppress defects such as a short circuit of the organic EL elements to be stacked. In particular, by forming the cap layer 12, the arithmetic average roughness Ra can be made smaller than that of the smoothing layer 4, and the flatness of the surface on which the transparent electrode 5 is formed is further improved. The occurrence of defects can be suppressed. The arithmetic average roughness Ra is preferably 0 nm, but the practical level limit is, for example, 0.5 nm.

  Here, the arithmetic average roughness Ra of the surface represents arithmetic average roughness based on JIS B 0601-2001. The surface roughness (arithmetic mean roughness Ra) was measured by using an atomic force microscope (AFM) manufactured by Digital Instruments and continuously measured with a detector having a stylus with a minimum tip radius. It was calculated from the cross-sectional curve, measured three times in a section having a measurement direction of 10 μm with a stylus having a minimal tip radius, and obtained from the average roughness regarding the amplitude of fine irregularities.

  Hereinafter, a method for forming the cap layer 12 will be described.

(Film formation by dry process)
Examples of the silicon nitride contained in the cap layer 12 include a reaction product of an inorganic silicon compound or an organic silicon compound.

  Examples of the reaction product of the inorganic silicon compound include silicon oxynitride, silicon nitride, and silicon nitride carbide.

  Examples of the organosilicon compound include hexamethyldisiloxane, 1,1,3,3-tetramethyldisiloxane, vinyltrimethylsilane, methyltrimethylsilane, hexamethyldisilane, methylsilane, dimethylsilane, trimethylsilane, diethylsilane, propyl Examples thereof include silane, phenylsilane, vinyltriethoxysilane, vinyltrimethoxysilane, tetramethoxysilane, tetraethoxysilane, phenyltrimethoxysilane, methyltriethoxysilane, and octamethylcyclotetrasiloxane. Among these, hexamethyldisiloxane and 1,1,3,3-tetramethyldisiloxane are preferable from the viewpoint of characteristics such as gas barrier properties of the cap layer 12 to be obtained during film formation. Moreover, these organosilicon compounds can be used individually by 1 type or in combination of 2 or more types.

For example, when the cap layer 12 containing the reaction product of hexamethyldisiloxane is formed by plasma CVD, the mole of oxygen as the reaction gas with respect to the molar amount (flow rate) of hexamethyldisiloxane as the source gas. The amount (flow rate) is preferably an amount of 12 times or less (more preferably 10 times or less) which is a stoichiometric ratio.
By containing hexamethyldisiloxane and oxygen at such a ratio, carbon atoms and hydrogen atoms in hexamethyldisiloxane that have not been completely oxidized are taken into cap layer 12, and desired cap layer 12 is formed. It becomes possible to form, and it becomes possible to exhibit the gas barrier property and bending resistance which were excellent in the gas barrier film obtained.
In addition, the lower limit of the molar amount (flow rate) of oxygen relative to the molar amount (flow rate) of hexamethyldisiloxane in the film forming gas should be greater than 0.1 times the molar amount (flow rate) of hexamethyldisiloxane. It is more preferable that the amount be more than 0.5 times.

  Further, as a film forming apparatus, there is a magnetron sputtering apparatus that includes an RF magnetron plasma generation unit and a silicon target for performing sputtering by the generated plasma, and these are connected to a vacuum processing chamber by an introduction unit. In the film forming apparatus, an RF magnetron sputtering source is constituted by an RF magnetron plasma generation unit and a target. A plasma of argon gas is generated by the RF magnetron plasma generation unit, and RF is applied to the disk-shaped target, so that silicon atoms of the target are sputtered (RF magnetron sputtering), and the smoothing layer 4 positioned downstream thereof. It can be formed by adhering to the surface.

Further, in film formation using a dry process, it is rare that a component as in the stoichiometry is present due to the presence of a small amount of gas other than the introduced gas. Specifically, Si ₃ N ₄ is the stoichiometric representative value, but there is a certain ratio of width in an actual film, and these are included and handled as SiN.
The above-mentioned atomic ratio can be determined by a conventionally known method, and can be measured by, for example, an analyzer using X-ray photoelectron spectroscopy (XPS).

  Examples of the dry process include a vapor deposition method (resistance heating, EB method, etc.), a plasma CVD method, a sputtering method, an ion plating method, etc., but a water vapor permeability is small and a dense film with low film stress is used. Any of them can be suitably used as long as they can be formed. Moreover, the plasma CVD method used for formation of the 1st gas barrier layer 2a mentioned later can also be used conveniently.

Thus, although the cap layer 12 is formed by a dry process, it is also a very preferable aspect to use a combination of the same composition or different compositions. In the case of such a composite film or laminated film, the function / action as the cap layer 12 is expressed as a whole.
Moreover, since the above viewpoints can be satisfied in total, silicon oxynitride and silicon nitride are particularly advantageous and preferable in the dry process.

[Smoothing layer]
When the light emitting unit 6 is provided on the light scattering layer 3, the smoothing layer 4 is deteriorated in storability or electrical short-circuit in a high temperature / high humidity atmosphere due to unevenness on the surface of the light scattering layer 3 ( This layer is provided mainly for the purpose of preventing adverse effects such as short circuit, and is provided between the light scattering layer 3 and the cap layer 12.

  It is important that the smoothing layer 4 has a flatness that allows the transparent electrode 5 to be satisfactorily formed thereon, and the surface property is such that the arithmetic average roughness Ra is in the range of 0.5 to 50 nm. More preferably, it is 30 nm or less, particularly preferably 10 nm or less, and most preferably 5 nm or less. By setting the arithmetic average roughness Ra within the range of 0.5 to 50 nm, it is possible to suppress defects such as a short circuit of the organic EL element to be stacked. As for the arithmetic average roughness Ra, 0 nm is preferable, but 0.5 nm is set as a lower limit value as a practical level limit value.

  Light that has passed through the cap layer 12 is incident on the smoothing layer 4. For this reason, the average refractive index nf of the smoothing layer 4 is preferably a value lower than the refractive index of the cap layer 12. Specifically, when the average refractive index nc of the cap layer 12 is 1.8 or more and 2.5 or less as described above, the smoothing layer 4 has the emission maximum wavelength of the emitted light h from the light emitting unit 6. Among these, at the shortest light emission maximum wavelength, it is preferable that the average refractive index nf is 1.5 or more, particularly a high refractive index layer having a value of 1.65 and less than 2.5. As long as the average refractive index nf is greater than 1.65 and less than 2.5, it may be formed of a single material or a mixture. In the case of such a mixed system, the average refractive index nf of the smoothing layer 4 uses a calculated refractive index calculated by a total value obtained by multiplying the refractive index specific to each material by the mixing ratio. In this case, the refractive index of each material may be 1.65 or less, or 2.5 or more, and the average refractive index nf of the mixed film is larger than 1.65 and less than 2.5. That's fine.

  As the binder used for the smoothing layer 4, known resins can be used without particular limitation. For example, acrylic ester, methacrylic ester, polyethylene terephthalate (PET), polybutylene terephthalate, polyethylene naphthalate (PEN), Polycarbonate (PC), polyarylate, polyvinyl chloride (PVC), polyethylene (PE), polypropylene (PP), polystyrene (PS), nylon (Ny), aromatic polyamide, polyether ether ketone, polysulfone, polyether sulfone, Silsesquioxane, polysiloxane, polysilazane, polysiloxazan, perfluoroalkyl group-containing silane compounds having a polyimide, polyetherimide, organic-inorganic hybrid structure (for example, (heptadecuff Oro-1,1,2,2-tetradecyl) triethoxysilane) other fluorine-containing copolymer to monomer constituent unit for imparting a crosslinking group and a fluorine-containing monomer. These resins can be used in combination of two or more. Among these, those having an organic-inorganic hybrid structure are preferable.

The following hydrophilic resins can also be used. Examples of the hydrophilic resin include water-soluble resins, water-dispersible resins, colloid-dispersed resins, and mixtures thereof. Examples of the hydrophilic resin include acrylic resins, polyester resins, polyamide resins, polyurethane resins, fluorine resins, etc., for example, polyvinyl alcohol, gelatin, polyethylene oxide, polyvinyl pyrrolidone, casein, starch, agar, carrageenan, polyacrylic. Polymers such as acid, polymethacrylic acid, polyacrylamide, polymethacrylamide, polystyrene sulfonic acid, cellulose, hydroxyl ethyl cellulose, carboxyl methyl cellulose, hydroxyl ethyl cellulose, dextran, dextrin, pullulan, water-soluble polyvinyl butyral can be mentioned, but these Among these, polyvinyl alcohol is preferable.
As the polymer used as the binder resin, one type may be used alone, or two or more types may be mixed and used as necessary.

  Similarly, conventionally known resin particles (emulsion) and the like can also be suitably used as the binder.

Further, as the binder, a resin curable mainly by ultraviolet rays / electron beams, that is, a mixture of an ionizing radiation curable resin and a thermoplastic resin and a solvent, or a thermosetting resin can be suitably used.
Such a binder resin is preferably a polymer having a saturated hydrocarbon or polyether as a main chain, and more preferably a polymer having a saturated hydrocarbon as a main chain.
The binder is preferably crosslinked. The polymer having a saturated hydrocarbon as the main chain is preferably obtained by a polymerization reaction of an ethylenically unsaturated monomer. In order to obtain a crosslinked binder, it is preferable to use a monomer having two or more ethylenically unsaturated groups.

  Examples of the high refractive index nanoparticles contained in the binder used for the smoothing layer 4 include the following nanoparticles.

Examples of the nanoparticles having a high refractive index include inorganic oxide particles composed of at least one oxide selected from zirconium, titanium, aluminum, indium, zinc, tin, antimony, and the like. Specific examples of the inorganic oxide particles include ZrO ₂ , TiO ₂ , BaTiO ₃ , Al ₂ O ₃ , In ₂ O ₃ , ZnO, SnO ₂ , Sb ₂ O ₃ , ITO, SiO ₂ , ZrSiO ₄ , zeolite. Among them, TiO ₂ , BaTiO ₃ , ZrO ₂ , ZnO and SnO ₂ are preferable, and TiO ₂ is most preferable. Of TiO _2, the rutile type is preferable to the anatase type because the catalytic activity is low, and the weather resistance of the smoothing layer 4 and the adjacent layer is high, and the refractive index is high.

It is preferable that the nanoparticles have a refractive index in the range of 1.7 to 3.0 and are included in a binder as a medium to form a film. If the refractive index of the nanoparticles is 1.7 or more, the intended effect can be sufficiently exerted. If the refractive index of a nanoparticle is 3.0 or less, the multiple scattering in a layer will be suppressed and transparency will not be reduced.
Nanoparticles are defined as fine particles (colloidal particles) having a particle size dispersed in a dispersion medium of the order of nanometers. The particles include discrete particles (primary particles) and agglomerated particles (secondary particles), which are defined as nanoparticles including secondary particles.

  The lower limit of the particle diameter of the nanoparticles is usually preferably 5 nm or more, more preferably 10 nm or more, and further preferably 15 nm or more. Moreover, as an upper limit of the particle diameter of a nanoparticle, it is preferable that it is 70 nm or less, It is more preferable that it is 60 nm or less, It is further more preferable that it is 50 nm or less. It is preferable at the point from which high transparency is acquired because the particle diameter of a nanoparticle exists in the range of 5-60 nm. As long as the effect is not impaired, the particle size distribution is not limited and may be wide or narrow and may have a plurality of distributions.

  As a method for preparing the titanium dioxide sol, reference can be made to, for example, JP-A-63-17221, JP-A-7-819, JP-A-9-165218, JP-A-11-43327, and the like.

  The layer thickness of the smoothing layer 4 needs to be thick to some extent in order to reduce the surface roughness of the light scattering layer 3, but on the other hand, it needs to be thin enough not to cause energy loss due to absorption.

As a method for forming the smoothing layer 4, for example, after forming the light scattering layer 3, a dispersion in which nano TiO ₂ particles are dispersed and a resin solution are mixed, and filtered through a filter to obtain a smoothing layer preparation solution. Subsequently, the smoothing layer 4 can be prepared by applying the smoothing layer preparation solution onto the light scattering layer 3, drying it, and then irradiating it with ultraviolet rays.

[Light scattering layer]
The organic EL element includes a light scattering layer 3.
The average refractive index ns of the light scattering layer 3 is preferably as close as possible to the smoothing layer 4 and lower than the smoothing layer 4 because the emitted light h from the light emitting unit 6 enters through the smoothing layer 4. preferable. The light scattering layer 3 has an average refractive index ns of 1.5 or more, particularly 1.6 or more and less than 2.5 at the shortest emission maximum wavelength among the emission maximum wavelengths of the emitted light h from the light emitting unit 6. A high refractive index layer is preferred. In this case, the light scattering layer 3 may form a film with a single material having an average refractive index of ns 1.6 or more and less than 2.5, or may be mixed with two or more kinds of compounds to have an average refractive index ns 1.6 of. A film of less than 2.5 may be formed. In the case of such a mixed system, the average refractive index ns of the light scattering layer 3 uses a calculated refractive index calculated by a total value obtained by multiplying the refractive index specific to each material by the mixing ratio. In this case, the refractive index of each material may be less than 1.6 or 2.5 or more as long as the average refractive index ns of the mixed film satisfies 1.6 or more and less than 2.5. Good.
Here, the “average refractive index ns” is the refractive index of a single material when formed of a single material, and in the case of a mixed system, the refractive index specific to each material is multiplied by the mixing ratio. It is the calculated refractive index calculated by the combined value.

  Further, the light scattering layer 3 is a scattering film made of a mixture using a difference in refractive index between a binder having a low refractive index as a layer medium and light scattering particles having a high refractive index contained in the layer medium. Is preferred.

The binder having a low refractive index has a refractive index nb of less than 1.9, particularly preferably less than 1.6.
Here, the refractive index nb of the binder is the refractive index of a single material when formed of a single material, and in the case of a mixed system, the refractive index specific to each material is multiplied by the mixing ratio. It is a calculated refractive index calculated by the sum value.

The light scattering particles having a high refractive index have a refractive index np of 1.5 or more, preferably 1.8 or more, and particularly preferably 2.0 or more.
Here, the refractive index np of the light scattering particles is the refractive index of a single material when it is formed of a single material, and in the case of a mixed system, the mixing ratio is set to the refractive index specific to each material. It is a calculated refractive index calculated by the summed value.

  Further, the role of the light scattering particles having a high refractive index of the light scattering layer 3 includes a scattering function of guided light. For this purpose, it is necessary to improve the scattering property. In order to improve the scattering property, it is conceivable to increase the refractive index difference between the light scattering particles and the binder, to increase the layer thickness, and to increase the particle density. Among them, the one with the smallest trade-off with other performances is to increase the refractive index difference between the inorganic particles and the binder.

  The refractive index difference | nb−np | between the refractive index nb of the resin material (binder) which is the layer medium and the refractive index np of the light scattering particles having a high refractive index contained is preferably 0.2 or more. Particularly preferred is 0.3 or more. If the refractive index difference | nb−np | between the layer medium and the light scattering particles is 0.03 or more, a scattering effect occurs at the interface between the layer medium and the light scattering particles. The larger the refractive index difference | nb−np |, the greater the refraction at the interface and the better the scattering effect.

  Specifically, since the average refractive index ns of the light scattering layer 3 is preferably a high refractive index layer in the range of 1.6 or more and less than 2.5, for example, the refractive index nb of the binder is 1 It is preferable that the refractive index np of the light scattering particle having a high refractive index smaller than .6 is larger than 1.8.

  The refractive index is measured in the same manner as the smoothing layer 4 by irradiating the light having the shortest light emission maximum wavelength among the light emission maximum wavelengths of the emitted light h from the light emitting unit 6 in an atmosphere at 25 ° C. A rate meter (manufactured by ATAGO, DR-M2) can be used.

As described above, the light scattering layer 3 is a layer that diffuses light by the difference in refractive index between the layer medium and the light scattering particles. Therefore, the contained light scattering particles are required to scatter the emitted light h from the light emitting unit 6 without adversely affecting other layers.
Here, the scattering is a state in which the haze value (ratio of the scattering transmittance to the total light transmittance) is 60% or more, more preferably 70% or more, and particularly preferably 80% or more in the light scattering layer 3 single film. Represents. If the haze value is 60% or more, the luminous efficiency can be improved.
The haze value is a physical property value calculated under the influence of (i) the influence of the refractive index difference of the composition in the film and (ii) the influence of the surface shape. That is, by measuring the haze value while suppressing the surface roughness below a certain level, the haze value excluding the influence of (ii) is measured. Specifically, it can be measured using a haze meter (Nippon Denshoku Industries Co., Ltd., NDH-5000, etc.).

For example, by adjusting the particle diameter, the scattering property can be improved, and defects such as a short circuit can be suppressed. Specifically, it is preferable to use transparent particles having a particle diameter equal to or larger than a region that causes Mie scattering in the visible light region. Preferably, the average particle diameter is 0.2 μm or more.
On the other hand, as the upper limit of the average particle diameter, when the particle diameter is larger, the thickness of the adjacent cap layer 12 or the smoothing layer 4 for flattening the roughness of the light scattering layer 3 containing the light scattering particles is also increased. Preferably, the average particle size is less than 1 μm because there is a disadvantage in terms of process load and film absorption.

When a plurality of types of particles are used for the light scattering layer 3, the other particles excluding the light scattering particles include at least one particle having an average particle diameter in the range of 100 nm to 3 μm and 3 μm or more. In particular, it is preferable that at least one kind of particles within a range of 200 nm to 1 μm is included and no particles of 1 μm or more are included.
Here, the average particle diameter of the high refractive index particles can be measured by, for example, an apparatus using a dynamic light scattering method such as Nanotrack UPA-EX150 manufactured by Nikkiso Co., Ltd., or image processing of an electron micrograph.

  Such light scattering particles are not particularly limited and may be appropriately selected depending on the purpose, and may be organic fine particles or inorganic fine particles. Among them, inorganic fine particles having a high refractive index may be used. Preferably there is.

  Examples of organic fine particles having a high refractive index include polymethyl methacrylate beads, acrylic-styrene copolymer beads, melamine beads, polycarbonate beads, styrene beads, crosslinked polystyrene beads, polyvinyl chloride beads, benzoguanamine-melamine formaldehyde beads, and the like. Can be mentioned.

Examples of the inorganic fine particles having a high refractive index include inorganic oxide particles made of at least one oxide selected from zirconium, titanium, aluminum, indium, zinc, tin, antimony and the like. Specific examples of the inorganic oxide particles include ZrO ₂ , TiO ₂ , BaTiO ₃ , Al ₂ O ₃ , In ₂ O ₃ , ZnO, SnO ₂ , Sb ₂ O ₃ , ITO, SiO ₂ , ZrSiO ₄ , zeolite. Among them, TiO ₂ , BaTiO ₃ , ZrO ₂ , ZnO and SnO ₂ are preferable, and TiO ₂ is most preferable. Of TiO _2, the rutile type is more preferable than the anatase type because the weather resistance of the light scattering layer 3 and adjacent layers is high because the catalytic activity is low, and the refractive index is high.

  These light scattering particles are used after being subjected to a surface treatment from the viewpoint of improving dispersibility and stability in the case of using a dispersion liquid described later in order to be contained in the light scattering layer 3 having a high refractive index, or It can be selected whether to use it without surface treatment.

  When performing the surface treatment, specific materials for the surface treatment include different inorganic oxides such as silicon oxide and zirconium oxide, metal hydroxides such as aluminum hydroxide, organic acids such as organosiloxane and stearic acid, and the like. It is done. These surface treatment materials may be used individually by 1 type, and may be used in combination of multiple types. Among these, from the viewpoint of the stability of the dispersion, the surface treatment material is preferably a different inorganic oxide and / or metal hydroxide, more preferably a metal hydroxide.

  When the inorganic oxide particles are surface-coated with a surface treatment material, the coating amount (in general, this coating amount is indicated by the mass ratio of the surface treatment material used on the surface of the particle to the mass of the particles). Is preferably 0.01 to 99% by mass. By making it within this range, the effect of improving the dispersibility and stability by the surface treatment can be sufficiently obtained, and the light extraction efficiency can be improved by the high refractive index of the light scattering layer 3.

  In addition, as a material having a high refractive index, quantum dots described in International Publication No. 2009/014707 and US Pat. No. 6,608,439 can be suitably used.

  The light scattering particles having a high refractive index are preferably arranged so as to be in contact with or close to the interface between the light scattering layer 3 and the adjacent cap layer 12 and smoothing layer 4. Accordingly, the evanescent light that oozes out to the light scattering layer 3 when total reflection occurs in the cap layer 12 or the smoothing layer 4 can be scattered by the particles, and the light extraction efficiency is improved.

  The content of the high refractive index particles in the light scattering layer 3 is preferably a volume filling factor in the range of 1.0 to 70%, and more preferably in the range of 5.0 to 50%. This makes it possible to create a distribution of refractive index density at the interface between the light scattering layer 3 and the gas barrier layer 2 or the smoothing layer 4 adjacent to the light scattering layer 3, thereby increasing the amount of light scattering and improving the light extraction efficiency. it can.

As a method for forming the light scattering layer 3, for example, when the layer medium is a resin material, the light scattering particles are dispersed in a resin material (polymer) solution (a solvent in which particles are not dissolved) used as a medium. It is formed by coating on the resin substrate 1 or the gas barrier layer 2.
Since these light scattering particles are actually polydisperse particles and difficult to arrange regularly, they have a diffraction effect locally. Improve extraction efficiency.

(binder)
Examples of the binder in the light scattering layer 3 include the same resin as that in the smoothing layer 4.

In the light scattering layer 3, a compound capable of forming a metal oxide, a metal nitride, or a metal oxynitride by ultraviolet irradiation under a specific atmosphere is particularly preferably used. As such a compound, a compound which can be modified at a relatively low temperature described in JP-A-8-112879 is preferable.
Specifically, polysiloxane (including polysilsesquioxane) having Si—O—Si bond, polysilazane having Si—N—Si bond, both Si—O—Si bond and Si—N—Si bond And polysiloxazan containing These can be used in combination of two or more. Moreover, it can be used even if different compounds are sequentially laminated or simultaneously laminated.
The layer thickness of the light scattering layer 3 needs to be thick to some extent in order to ensure the optical path length for causing scattering, but it needs to be thin enough not to cause energy loss due to absorption. Specifically, it is preferably in the range of 0.1 to 2 μm, and more preferably in the range of 0.2 to 1 μm.

(Polysiloxane)
The polysiloxane used in the light scattering layer 3 can include R ₃ SiO _1/2 , R ₂ SiO, RSiO _3/2 and SiO ₂ as general structural units. Here, R is independent of the group consisting of a hydrogen atom, an alkyl group containing 1 to 20 carbon atoms such as methyl, ethyl, propyl, an aryl group such as phenyl, and an unsaturated alkyl group such as vinyl. Selected. Examples of specific polysiloxane groups include PhSiO _3/2 , MeSiO _3/2 , HSiO _3/2 , MePhSiO, Ph ₂ SiO, PhViSiO, ViSiO _3/2 , MeHSiO, MeViSiO, Me ₂ SiO, Me ₃ SiO _{1 / 2} etc. Mixtures and copolymers of polysiloxanes can also be used. Vi represents a vinyl group.

(Polysilsesquioxane)
In the light scattering layer 3, it is preferable to use polysilsesquioxane among the above-mentioned polysiloxanes. Polysilsesquioxane is a compound containing silsesquioxane in a structural unit. “Silsesquioxane” is a compound represented by RSiO _3/2 , usually RSiX ₃ (R is a hydrogen atom, an alkyl group, an alkenyl group, an aryl group, an aralkyl group (also referred to as an aralkyl group), etc. And X is a halogen, an alkoxy group or the like.
The molecular arrangement of polysilsesquioxane is typically an amorphous structure, a ladder structure, a cage structure, or a partially cleaved structure (a structure in which a silicon atom is missing from a cage structure or a cage structure). A structure in which the silicon-oxygen bond in the structure is partially broken) is known.

Among these polysilsesquioxanes, it is preferable to use a so-called hydrogen silsesquioxane polymer. Examples of the hydrogen silsesquioxane polymer include a hydridosiloxane polymer represented by HSi (OH) _x (OR) _y O _{z / 2} . Each R is an organic group or a substituted organic group, and forms a hydrolyzable substituent when bonded to silicon by an oxygen atom. x = 0 to 2, y = 0 to 2, z = 1 to 3, and x + y + z = 3. Examples of R include an alkyl group (eg, methyl group, ethyl group, propyl group, butyl group), an aryl group (eg, phenyl group), and an alkenyl group (eg, allyl group, vinyl group). These resins are either fully condensed (HSiO _3/2 ) _n , or only partially hydrolyzed (ie, including some Si—OR) and / or partially condensed (ie, one Part of Si-OH).

(Polysilazane)
The polysilazane used in the light scattering layer 3 is a polymer having a silicon-nitrogen bond, and is composed of Si—N, Si—H, N—H, etc., SiO ₂ , Si ₃ N ₄ and both intermediate solid solutions SiO _x N _y. An inorganic precursor polymer such as (x = 0.1 to 1.9, y = 0.1 to 1.3).

  As polysilazane preferably used for the light scattering layer 3, polysilazane represented by the following general formula (A) can be used.

In the formula, R ¹ , R ² and R ³ each represent a hydrogen atom, an alkyl group, an alkenyl group, a cycloalkyl group, an aryl group, an alkylsilyl group, an alkylamino group or an alkoxy group.

Perhydropolysilazane (PHPS), in which all of R ¹ , R ² and R ^{3 in} the general formula (A) are hydrogen atoms, is particularly preferable from the viewpoint of the denseness of the resulting light scattering layer 3 as a film.

  Perhydropolysilazane is presumed to have a linear structure and a ring structure centered on a 6-membered ring and an 8-membered ring. Its molecular weight is about 600 to 2000 in terms of number average molecular weight (Mn) (gel Polystyrene conversion by permeation chromatography), which is a liquid or solid substance.

  Polysilazane is commercially available in the form of a solution dissolved in an organic solvent, and a commercially available product can be used as it is as a polysilazane-containing coating solution. Examples of commercially available polysilazane solutions include NN120-20, NAX120-20, and NL120-20 manufactured by AZ Electronic Materials Co., Ltd.

As the binder, an ionizing radiation curable resin composition can be used. As a curing method of the ionizing radiation curable resin composition, an ordinary curing method of the ionizing radiation curable resin composition, that is, irradiation with an electron beam or ultraviolet rays. Can be cured.
For example, in the case of electron beam curing, 10 to 1000 keV emitted from various electron beam accelerators such as a cockrowalton type, a bandegraph type, a resonant transformation type, an insulating core transformer type, a linear type, a dynamitron type, and a high frequency type. Preferably, an electron beam or the like having an energy of 30 to 300 keV is used. In the case of ultraviolet curing, ultraviolet rays emitted from rays of ultra-high pressure mercury lamp, high pressure mercury lamp, low pressure mercury lamp, carbon arc, xenon arc, metal halide lamp, etc. Available.

(Vacuum ultraviolet irradiation device with excimer lamp)
Examples of the ultraviolet irradiation device include a rare gas excimer lamp that emits vacuum ultraviolet rays within a range of 100 to 230 nm.
Atoms of noble gases such as xenon (Xe), krypton (Kr), argon (Ar), neon (Ne) and the like are called inert gases because they do not form molecules by chemically bonding. However, rare gas atoms (excited atoms) that have gained energy by discharge or the like can be combined with other atoms to form molecules.
For example, when the rare gas is Xe (xenon), excimer light of 172 nm is emitted when the excited excimer molecule Xe ₂ ^* transitions to the ground state, as shown in the following reaction formula.

e + Xe → Xe ^*
Xe ^* + 2Xe → Xe ₂ ^* + Xe
Xe ₂ ^* → Xe + Xe + hν (172 nm)

  A feature of the excimer lamp is that the radiation is concentrated on one wavelength, and since only the necessary light is not emitted, the efficiency is high. Moreover, since extra light is not radiated | emitted, the temperature of a target object can be kept comparatively low. Furthermore, since no time is required for starting and restarting, instantaneous lighting and blinking are possible.

As a light source for efficiently irradiating excimer light, a dielectric barrier discharge lamp can be cited.
A dielectric barrier discharge lamp has a structure in which a discharge is generated between electrodes via a dielectric. Generally, at least one electrode is disposed between a discharge vessel made of a dielectric and the outside thereof. That's fine. As a dielectric barrier discharge lamp, for example, a rare gas such as xenon is enclosed in a double cylindrical discharge vessel composed of a thick tube and a thin tube made of quartz glass, and a net-like second discharge vessel is formed outside the discharge vessel. There is one in which one electrode is provided and another electrode is provided inside the inner tube. A dielectric barrier discharge lamp generates a dielectric barrier discharge inside a discharge vessel by applying a high frequency voltage between electrodes, and generates excimer light when excimer molecules such as xenon generated by the discharge dissociate. .

  Since the excimer lamp has high light generation efficiency, it can be lit with low power. In addition, since light having a long wavelength that causes a temperature rise is not emitted and energy is emitted at a single wavelength in the ultraviolet region, the temperature rise of the irradiation object due to the irradiation light itself is suppressed.

  In order to further capture the light taken into the adjacent cap layer 12 or the smoothing layer 4 into the light scattering layer 3, the refractive index difference between the cap layer 12 or the smoothing layer 4 adjacent to the binder of the light scattering layer 3. Is preferably small. Specifically, the difference in refractive index between the cap layer 12 or the smoothing layer 4 adjacent to the binder of the light scattering layer 3 is preferably 0.1 or less. Moreover, it is preferable to use the same material for the binder contained in the adjacent smoothing layer 4 and the binder contained in the light scattering layer 3.

  Further, by adjusting the thickness of the cap layer 12 and the smoothing layer 4 to which the light scattering layer 3 is added, it is possible to suppress the wiring defect due to the ingress of moisture or the edge step when patterning, and to improve the scattering property. Can do. Specifically, the layer thickness obtained by adding the light scattering layer 3 to the cap layer 12 and the smoothing layer 4 is preferably in the range of 100 nm to 3 μm, and more preferably in the range of 300 nm to 2 μm.

[Gas barrier layer]
The gas barrier layer 2 is composed of a first gas barrier layer 2a and a second gas barrier layer 2b having different constituent element compositions or distribution states. The gas barrier layer 2 is composed of at least two or more kinds of gas barrier layers having different compositions or distribution states of the constituent elements, so that the permeation of oxygen and water vapor can be efficiently prevented. Note that the gas barrier layer 2 may be formed of a single layer as long as the permeation of oxygen and water vapor can be efficiently prevented.

The gas barrier layer 2 has a water vapor permeability (25 ± 0.5 ° C., relative humidity 90 ± 2% RH) measured by a method according to JIS K 7129-1992, 0.01 g / (m ² · 24 h) or less. The gas barrier film (also referred to as a gas barrier film) is preferably used. Furthermore, the oxygen permeability measured by a method according to JIS K 7126-1987 is 1 × 10 ⁻³ ml / (m ² · 24 h · atm) or less, and the water vapor permeability is 1 × 10 ⁻ It is preferably ⁵ g / (m ² · 24 h) or less.

  When the gas barrier layer 2 is composed of at least two kinds of layers, it is preferable that one of the at least two kinds of gas barrier layers contains silicon dioxide which is a reaction product of an inorganic silicon compound. . Moreover, it is preferable that one of the gas barrier layers of at least two gas barrier layers contains a reaction product of an organosilicon compound. That is, it is preferable that the at least one gas barrier layer contains an element derived from an organosilicon compound, for example, oxygen, silicon, carbon, or the like as a constituent element.

  The composition or distribution state of the elements constituting the gas barrier layer 2 in the gas barrier layer 2 may be uniform or may be different in the layer thickness direction. As a method for making the composition or distribution state of the constituent elements different, it is preferable to make the formation method and the formation material of the gas barrier layer 2 different as described later.

  Further, the water vapor transmission rate Wg of the gas barrier layer 2, the water vapor transmission rate Ws of the light scattering layer 3, and the water vapor transmission rate Wf of the cap layer 12 preferably satisfy the following conditional expressions.

  Wg ≦ Wf <Ws

[First gas barrier layer]
The constituent elements of the first gas barrier layer 2a include at least an element that constitutes a compound that prevents permeation of oxygen and water vapor, and may be different from constituent elements of the second gas barrier layer 2b described later.
For example, the first gas barrier layer 2 a can be provided as a layer containing silicon, oxygen, and carbon as constituent elements on one surface of the resin base material 1. In this case, in the distribution curve of each constituent element based on the element distribution measurement in the depth direction by X-ray photoelectron spectroscopy for the first gas barrier layer 2a, the following requirements (i) to (iv) are all satisfied. However, it is preferable from the viewpoint of improving gas barrier properties.

(I) In the distance region where the silicon atomic ratio, oxygen atomic ratio, and carbon atomic ratio are 90% or more in the layer thickness direction from the surface of the first gas barrier layer 2a, they have the following order of magnitude relationship.
(Carbon atom ratio) <(silicon atom ratio) <(oxygen atom ratio)
(Ii) The carbon distribution curve has at least two extreme values.
(Iii) The absolute value of the difference between the maximum value and the minimum value of the carbon atom ratio in the carbon distribution curve is 5 at% or more.
(Iv) In the oxygen distribution curve, the maximum value of the oxygen distribution curve closest to the surface of the first gas barrier layer 2a on the resin substrate 1 side is the maximum value among the maximum values of the oxygen distribution curve in the first gas barrier layer 2a. Take.

The first gas barrier layer 2a uses a belt-shaped flexible resin base material 1 to convey the resin base material 1 while being in contact between a pair of film forming rollers, and is formed between the pair of film forming rollers. It is preferably a thin film layer formed on the resin substrate 1 by a plasma chemical vapor deposition method in which plasma discharge is performed while supplying a film gas.
In addition, the above-mentioned extreme value means the maximum value or the minimum value of the atomic ratio of each element with respect to the distance from the surface of the first gas barrier layer 2a in the layer thickness direction of the first gas barrier layer 2a.

(Definition of maximum and minimum values)
The maximum value is a point where the value of the atomic ratio of the element changes from increasing to decreasing when the distance from the surface of the first gas barrier layer 2a is changed, and is larger than the value of the atomic ratio of the element at that point. From this point, the atomic ratio value of the element at a position where the distance from the surface of the first gas barrier layer 2a in the layer thickness direction of the first gas barrier layer 2a is further changed by 20 nm is reduced by 3 at% or more.
The minimum value is a point where the value of the atomic ratio of the element changes from decreasing to increasing when the distance from the surface of the first gas barrier layer 2a is changed, and the value of the atomic ratio of the element at that point Rather, the atomic ratio value of the element at a position where the distance from the surface of the first gas barrier layer 2a in the layer thickness direction of the first gas barrier layer 2a is further changed by 20 nm from that point increases by 3 at% or more. Say.

(Average value of carbon atom ratio and relationship between maximum and minimum values)
From the viewpoint of flexibility, the carbon atom ratio in the first gas barrier layer 2a is preferably in the range of 8 to 20 at% as an average value of the entire layer, and more preferably in the range of 10 to 20 at%. By setting it within the range, it is possible to form the first gas barrier layer 2a that sufficiently satisfies the gas barrier property and the flexibility.

  Further, in the first gas barrier layer 2a, it is preferable that the absolute value of the difference between the maximum value and the minimum value of the carbon atom ratio in the carbon distribution curve is 5 at% or more. In the first gas barrier layer 2a, the absolute value of the difference between the maximum value and the minimum value of the carbon atom ratio is more preferably 6 at% or more, and particularly preferably 7 at% or more. When the absolute value is 3 at% or more, the gas barrier property when the obtained first gas barrier layer 2a is bent is sufficient.

(Position of extreme value of oxygen atom ratio and relationship between maximum and minimum values)
From the viewpoint of preventing intrusion of water molecules from the resin base material 1 side, in the oxygen distribution curve of the first gas barrier layer 2a, the maximum value of the oxygen distribution curve closest to the surface of the first gas barrier layer 2a on the resin base material 1 side is It is preferable to take the maximum value among the maximum values of the oxygen distribution curve in the first gas barrier layer 2a.

FIG. 2 is a graph showing each element profile in the layer thickness direction according to the XPS depth profile (distribution in the depth direction) of the first gas barrier layer 2a.
In FIG. 2, the oxygen distribution curve is shown as A, the silicon distribution curve as B, and the carbon distribution curve as C.

  Between each interface of the first gas barrier layer 2a on the light emitting unit 6 side (distance 0 nm, hereinafter referred to as “front surface”) to an interface on the resin base material 1 side (distance approximately 300 nm, hereinafter referred to as “back surface”). Although the atomic ratio continuously changes, the maximum value of the oxygen atomic ratio closest to the surface of the first gas barrier layer 2a in the oxygen distribution curve A is X, and the oxygen atomic ratio closest to the back surface of the first gas barrier layer 2a is From the viewpoint of preventing water molecules from entering from the resin base material 1 side, it is preferable that the value of the oxygen atomic ratio is Y> X, where Y is the maximum value.

  As the oxygen atomic ratio, the oxygen atomic ratio Y that becomes the maximum value of the oxygen distribution curve closest to the back surface of the first gas barrier layer 2a is the oxygen that becomes the maximum value of the oxygen distribution curve closest to the surface of the first gas barrier layer 2a. The atomic ratio X is preferably 1.05 times or more. That is, it is preferable that 1.05 ≦ Y / X. The upper limit is not particularly limited, but is preferably in the range of 1.05 ≦ Y / X ≦ 1.30, and more preferably in the range of 1.05 ≦ Y / X ≦ 1.20. preferable. Within this range, intrusion of water molecules can be prevented, gas barrier properties are not deteriorated under high temperature and high humidity, and this is preferable from the viewpoint of productivity and cost.

  In the oxygen distribution curve of the first gas barrier layer 2a, the absolute value of the difference between the maximum value and the minimum value of the oxygen atom ratio is preferably 5 at% or more, more preferably 6 at% or more, and 7 at%. The above is particularly preferable.

(Relationship between maximum and minimum silicon atom ratio)
The absolute value of the difference between the maximum value and the minimum value of the silicon atomic ratio in the silicon distribution curve of the first gas barrier layer 2a is preferably less than 5 at%, more preferably less than 4 at%, and less than 3 at%. It is particularly preferred. If the absolute value is within the above range, the gas barrier property of the obtained first gas barrier layer 2a and the mechanical strength of the gas barrier layer 2 are sufficient.

(About composition analysis in the depth direction of the gas barrier layer by XPS)
The carbon distribution curve, oxygen distribution curve and silicon distribution curve in the layer thickness (depth) direction of the gas barrier layer 2 can be obtained by combining the measurement of X-ray photoelectron spectroscopy and rare gas ion sputtering such as argon. It can be created by so-called XPS depth profile (distribution in the depth direction) measurement in which surface composition analysis is sequentially performed while being exposed. A distribution curve obtained by such XPS depth profile measurement can be created, for example, with the vertical axis as the atomic ratio (unit: at%) of each element and the horizontal axis as the etching time (sputtering time).
In the element distribution curve with the horizontal axis as the etching time in this way, the etching time generally correlates with the distance from the surface of the gas barrier layer 2 in the layer thickness direction of the gas barrier layer 2 in the layer thickness direction. As the “distance from the surface of the gas barrier layer in the thickness direction of the gas barrier layer”, the distance from the surface of the gas barrier layer 2 calculated from the relationship between the etching rate and the etching time employed in the XPS depth profile measurement is adopted. Can do.
In addition, as a sputtering method employed for such XPS depth profile measurement, a rare gas ion sputtering method using argon (Ar ⁺ ) as an etching ion species is employed, and the etching rate (etching rate) is 0.05 nm / It is preferable to set to sec (SiO ₂ thermal oxide film conversion value).

Further, from the viewpoint of forming a gas barrier layer that is uniform over the entire surface of the first gas barrier layer 2a and has excellent gas barrier properties, the surface direction of the first gas barrier layer 2a (direction parallel to the surface of the first gas barrier layer 2a) ) Is preferably substantially uniform.
The fact that the first gas barrier layer 2a is substantially uniform in the surface direction means that an oxygen distribution curve and a carbon distribution curve are created for any two measurement points on the surface of the first gas barrier layer 2a by XPS depth profile measurement. Furthermore, the number of extreme values of the carbon distribution curve obtained at any two measurement points is the same, and the absolute value of the difference between the maximum value and the minimum value of the carbon atomic ratio in each carbon distribution curve is , Which are the same as each other or within 5 at%.

The gas barrier layer 2 preferably includes at least one first gas barrier layer 2a that satisfies all of the above conditions (i) to (iv), but may include two or more layers that satisfy such a condition.
Further, when two or more first gas barrier layers 2a are provided, the materials of the plurality of first gas barrier layers 2a may be the same or different. Moreover, such a gas barrier layer 2 may be formed on one surface of the resin base material 1, or may be formed on both surfaces of the resin base material 1.

Further, in the silicon distribution curve, oxygen distribution curve, and carbon distribution curve, the silicon atom ratio, oxygen atom ratio, and carbon atom ratio are in the above condition (i) in a region that is 90% or more of the layer thickness of the first gas barrier layer 2a. When the conditions shown are satisfied, the silicon atom ratio in the first gas barrier layer 2a is preferably in the range of 25 to 45 at%, and more preferably in the range of 30 to 40 at%.
The oxygen atom ratio in the first gas barrier layer 2a is preferably in the range of 33 to 67 at%, and more preferably in the range of 45 to 67 at%.
Furthermore, the carbon atom ratio in the first gas barrier layer 2a is preferably in the range of 3 to 33 at%, and more preferably in the range of 3 to 25 at%.

(Layer thickness of the first gas barrier layer)
The layer thickness of the first gas barrier layer 2a is preferably in the range of 5 to 3000 nm, more preferably in the range of 10 to 2000 nm, still more preferably in the range of 100 to 1000 nm, and 300 to 1000 nm. It is particularly preferable that the value falls within the range. If the layer thickness of the first gas barrier layer 2a is within the above range, the gas barrier properties such as oxygen gas barrier properties and water vapor barrier properties are excellent, and no deterioration of the gas barrier properties due to bending is observed.

(Method for forming first gas barrier layer)
The first gas barrier layer 2a is preferably a layer formed by plasma enhanced chemical vapor deposition. More specifically, as the first gas barrier layer 2a formed by the plasma chemical vapor deposition method, the resin substrate 1 is conveyed while being in contact with a pair of film forming rollers, and a film forming gas is supplied between the pair of film forming rollers. However, it is preferably a layer formed by plasma chemical vapor deposition by plasma discharge.
Further, when discharging between the pair of film forming rollers in this way, it is preferable to reverse the polarities of the pair of film forming rollers alternately. As a film forming gas used in the plasma chemical vapor deposition method, a gas containing an organosilicon compound and oxygen is preferable. The content of oxygen in the film forming gas to be supplied is the total amount of the organosilicon compound in the film forming gas. It is preferable that the amount be less than the theoretical oxygen amount necessary for complete oxidation. Moreover, it is preferable that the 1st gas barrier layer 2a is a layer formed on the resin base material 1 by the continuous film-forming process. The plasma chemical vapor deposition method may be a Penning discharge plasma type chemical vapor deposition method.

In order to form a layer in which the carbon atomic ratio has a concentration gradient and continuously changes in the layer as in the first gas barrier layer 2a, a plurality of plasma chemical vapor deposition methods are used when generating plasma. It is preferable to generate plasma discharge in the space between the film forming rollers. A pair of film forming rollers is used, and the resin base material 1 is conveyed in contact with each of the pair of film forming rollers. It is preferable to generate plasma by discharging between film rollers.
In this way, a pair of film forming rollers are used, and the resin base material 1 is conveyed while contacting the pair of film forming rollers, and plasma discharge is performed between the pair of film forming rollers. By changing the distance between the film discharge roller and the plasma discharge position between the film forming rollers, it is possible to form a gas barrier layer in which the carbon atom ratio has a concentration gradient and continuously changes in the layer.

  In addition, the surface portion of the resin base material 1 existing on the other film forming roller is simultaneously formed while forming the surface portion of the resin base material 1 existing on the one film forming roller at the time of film formation. This makes it possible to efficiently produce a thin film, double the deposition rate, and also to form a film with the same structure, so that it is possible to at least double the extreme value in the carbon distribution curve, which is efficient. It is possible to form a gas barrier layer that satisfies all of the above conditions (i) to (iv).

  Moreover, it is preferable that a gas barrier film forms the gas barrier layer 2 on the surface of the resin base material 1 by the roll to roll system from a viewpoint of productivity.

  An apparatus that can be used when producing a gas barrier film by plasma enhanced chemical vapor deposition is not particularly limited, and includes at least a pair of film forming rollers and a plasma power source, and a pair of film forming rollers. For example, when the manufacturing apparatus shown in FIG. 3 is used, it is preferable to use a roll-to-roll method while utilizing a plasma chemical vapor deposition method. It can also be manufactured.

  Hereinafter, the method of forming the first gas barrier layer 2a will be described in more detail with reference to FIG. FIG. 3 is a schematic diagram showing an example of a manufacturing apparatus that can be suitably used for forming the first gas barrier layer 2 a on the resin base material 1.

3 includes a feed roller 20, transport rollers 21, 22, 23, 24, film forming rollers 31, 32, a gas supply port 41, a power source 51 for generating plasma, a film forming roller 31, 32 includes magnetic field generators 61 and 62 installed inside 32 and a winding roller 25.
In such a manufacturing apparatus, at least the film forming rollers 31, 32, the gas supply port 41, the plasma generation power source 51, and the magnetic field generators 61, 62 made of permanent magnets are contained in a vacuum chamber (not shown). ). Further, in such a manufacturing apparatus, the vacuum chamber is connected to a vacuum pump (not shown), and the pressure in the vacuum chamber can be appropriately adjusted by such a vacuum pump.

In such a manufacturing apparatus, each film-forming roller has a power source for plasma generation so that the pair of film-forming rollers (the film-forming roller 31 and the film-forming roller 32) can function as a pair of counter electrodes. 51 is connected. Therefore, in such a manufacturing apparatus, it is possible to discharge into the space between the film forming roller 31 and the film forming roller 32 by supplying electric power from the plasma generating power source 51, thereby forming the film. Plasma can be generated in the space between the roller 31 and the film forming roller 32.
In addition, when using the film-forming roller 31 and the film-forming roller 32 as electrodes as described above, the material and design may be changed as appropriate so that the film-forming roller 31 and the film-forming roller 32 can be used as electrodes. Moreover, in such a manufacturing apparatus, it is preferable to arrange | position a pair of film-forming rollers (film-forming rollers 31 and 32) so that the central axis may become parallel on the same plane. By arranging a pair of film forming rollers (film forming rollers 31, 32) in this way, the film forming rate can be doubled and a film having the same structure can be formed. It becomes possible to double.

  Further, the magnetic field generators 61 and 62 are fixed inside the film forming roller 31 and the film forming roller 32 so as not to rotate even when the film forming roller rotates.

  As the film forming roller 31 and the film forming roller 32, known rollers can be used as appropriate. As such film forming rollers 31 and 32, it is preferable to use ones having the same diameter from the viewpoint of forming a thin film more efficiently. Further, the diameters of the film forming rollers 31 and 32 are preferably in the range of 300 to 1000 mmφ, particularly in the range of 300 to 700 mmφ, from the viewpoint of discharge conditions, chamber space, and the like. If it is larger than 300 mmφ, the plasma discharge space will not be reduced, so there will be no deterioration in productivity, and it will be possible to avoid applying the total amount of heat of the plasma discharge to the film in a short time, thus reducing damage to the resin substrate 1. preferable. On the other hand, if it is smaller than 1000 mmφ, it is preferable because practicality can be maintained in terms of device design including uniformity of plasma discharge space.

  Further, as the feed roller 20 and the transport rollers 21, 22, 23, and 24 used in such a manufacturing apparatus, known rollers can be used as appropriate. Further, the take-up roller 25 is not particularly limited as long as it can take up the resin base material 1 (gas barrier film) on which the first gas barrier layer 2a is formed, and a known roller can be used as appropriate. .

  As the gas supply port 41, a gas supply port that can supply or discharge a raw material gas at a predetermined speed can be used as appropriate.

As the plasma generating power source 51, a known power source of a plasma generating apparatus can be used as appropriate. Such a power source 51 for generating plasma supplies power to the film forming roller 31 and the film forming roller 32 connected thereto, and makes it possible to use these as counter electrodes for discharge.
As such a plasma generating power source 51, it is possible to more efficiently carry out the plasma CVD method, so that the polarity of the pair of film forming rollers can be alternately reversed (AC power source or the like). Is preferably used. Further, it is more preferable that the applied power can be in the range of 100 W to 10 kW and the AC frequency can be in the range of 50 Hz to 500 kHz.

  As the magnetic field generators 61 and 62, known magnetic field generators can be used as appropriate.

Using such a manufacturing apparatus shown in FIG. 3, for example, the type of source gas, the power of the electrode drum of the plasma generator, the pressure in the vacuum chamber, the diameter of the film forming roller, and the transport speed of the resin substrate 1 are set. A gas barrier layer can be manufactured by adjusting suitably.
That is, using the manufacturing apparatus shown in FIG. 3, plasma discharge is generated between a pair of film forming rollers (film forming rollers 31 and 32) while supplying a film forming gas (such as a raw material gas) into the vacuum chamber. As a result, the film formation gas (raw material gas or the like) is decomposed by plasma, and the first gas barrier layer 2a is formed on the surface of the resin base material 1 on the film formation roller 31 and on the surface of the resin base material 1 on the film formation roller 32. Is formed by plasma CVD.
In such film formation, the resin base material 1 is conveyed by the feed roller 20 and the film formation roller 31, respectively, so that the resin base material 1 is formed by a roll-to-roll continuous film formation process. A first gas barrier layer 2a is formed on the surface.

In the first gas barrier layer 2a, (iv) in the oxygen distribution curve, the maximum value of the oxygen distribution curve closest to the surface of the first gas barrier layer 2a on the resin substrate 1 side is the oxygen distribution curve in the first gas barrier layer 2a. It is preferable to take the maximum value among the maximum values.
Further, as the oxygen atomic ratio, the oxygen atomic ratio that is the maximum value of the oxygen distribution curve closest to the surface of the first gas barrier layer 2a on the resin base material 1 side is opposite to the resin base material 1 across the first gas barrier layer 2a. It is preferable that the oxygen atom ratio be 1.05 times or more of the maximum value of the oxygen distribution curve closest to the surface of the second gas barrier layer 2b on the side.

  Thus, the method for forming the oxygen atomic ratio so as to have a desired distribution in the first gas barrier layer 2a is not particularly limited, and a method for changing the film forming gas concentration during film formation, a gas supply port A method of changing the position of 41, a method of supplying gas at a plurality of locations, a method of controlling a gas flow by installing a baffle (shield) plate in the vicinity of the gas supply port 41, and a plurality of times by changing the deposition gas concentration Although it can be formed by a method of performing plasma CVD or the like, a method of performing plasma CVD while keeping the position of the gas supply port 41 close to either between the film forming rollers 31 or 32 is simple and favorable in terms of reproducibility.

  FIG. 4 is a schematic diagram illustrating the movement of the position of the gas supply port 41 of the CVD apparatus.

When the distance from the gas supply port 41 to the film forming roller 31 or the film forming roller 32 is 100%, the gas supply port 41 is moved from the perpendicular bisector m connecting the film forming rollers 31 and 32. By approaching the film forming roller 31 or 32 within a range of 5 to 20%, the extreme value condition of the oxygen distribution curve can be controlled.
That is, the distance between (t ₁ -p) in the direction from the point p on the vertical bisector m of the line segment connecting the film forming rollers 31 and 32 to the point t ₁ or the point t ₂ , or (t ₂ When the distance between -p) is 100%, it means that the distance between the positions of the points p is closer to the film forming roller side in a range of 5 to 20%.

  In this case, the magnitude of the extreme value of the oxygen distribution curve can be controlled by the distance traveled by the gas supply port 41. For example, in order to increase the extreme value of the oxygen distribution curve on the surface of the first gas barrier layer 2a closest to the resin substrate 1, the gas supply port 41 is brought closer to the film forming roller 31 or 32 with a moving distance close to 20%. Can be formed.

  The movement range of the gas supply port 41 is preferably close within a range of 5 to 20%, but more preferably within a range of 5 to 15%. If within this range, an in-plane oxygen distribution curve and others It is possible to form a desired distribution uniformly and with good reproducibility.

FIG. 2 shows an example of each element profile in the layer thickness direction based on the XPS depth profile formed in the first gas barrier layer 2a with the gas supply port 41 approaching the film forming roller 31 in the direction of 5%.
Further, FIG. 5 shows an example of each element profile in the layer thickness direction by an XPS depth profile formed by bringing the gas supply port 41 closer to the film forming roller 32 direction by 10%.
2 and 5, the maximum value of the oxygen distribution curve closest to the surface of the first gas barrier layer 2a in the oxygen distribution curve A is X, and the maximum value of the oxygen distribution curve closest to the back surface of the first gas barrier layer 2a is Y. Sometimes it turns out that Y> X.

  FIG. 6 shows an example of each element profile in the layer thickness direction based on the XPS depth profile of the gas barrier layer. The gas barrier layer is formed by installing the gas supply port 41 on the vertical bisector m connecting the film forming rollers 31 and 32 to form a gas barrier layer, which is the most on the back surface of the first gas barrier layer 2a. The oxygen atomic ratio at which the local oxygen distribution curve has the maximum value is almost equal to the oxygen atomic ratio at which the local oxygen distribution curve has the maximum value closest to the surface of the first gas barrier layer 2a, and oxygen on the back surface of the first gas barrier layer 2a. It can be seen that the extreme value of the distribution curve does not become the maximum value in the layer.

(Raw material gas)
The source gas in the deposition gas used for forming the first gas barrier layer 2a can be appropriately selected and used according to the material of the gas barrier layer to be formed. As such a source gas, for example, it is preferable to use an organosilicon compound containing silicon.
Examples of the organosilicon compound include hexamethyldisiloxane, 1,1,3,3-tetramethyldisiloxane, vinyltrimethylsilane, methyltrimethylsilane, hexamethyldisilane, methylsilane, dimethylsilane, trimethylsilane, diethylsilane, propyl Examples thereof include silane, phenylsilane, vinyltriethoxysilane, vinyltrimethoxysilane, tetramethoxysilane, tetraethoxysilane, phenyltrimethoxysilane, methyltriethoxysilane, and octamethylcyclotetrasiloxane.
Among these organosilicon compounds, hexamethyldisiloxane and 1,1,3,3-tetramethyldisiloxane are preferable from the viewpoints of characteristics such as gas barrier properties of the obtained first gas barrier layer 2a and handling in film formation. . Moreover, these organosilicon compounds can be used individually by 1 type or in combination of 2 or more types.

Further, as a film forming gas, a reactive gas may be used in combination with the source gas. As such a reactive gas, a gas that reacts with the raw material gas to become an inorganic compound such as an oxide or a nitride can be appropriately selected and used.
As a reaction gas for forming an oxide, for example, oxygen or ozone can be used. Moreover, as a reactive gas for forming nitride, nitrogen and ammonia can be used, for example.
These reaction gases can be used singly or in combination of two or more. For example, when forming an oxynitride, the reaction gas for forming an oxide and a nitride are formed. It can be used in combination with a reaction gas.

  As the film forming gas, a carrier gas may be used as necessary in order to supply the source gas into the vacuum chamber. Further, as a film forming gas, a discharge gas may be used as necessary in order to generate plasma discharge. As such a carrier gas and a discharge gas, known ones can be used as appropriate, and for example, rare gas elements such as helium, argon, neon, and xenon can be used.

  When such a film forming gas contains a raw material gas and a reactive gas, the ratio of the raw material gas and the reactive gas is the reaction gas that is theoretically required to completely react the raw material gas and the reactive gas. It is preferable not to make the ratio of the reaction gas excessive rather than the ratio of the amount. If the ratio of the reaction gas is excessive, it is difficult to obtain the desired first gas barrier layer 2a. Therefore, in order to obtain the desired performance as a gas barrier film, it is necessary to completely oxidize the entire amount of the organosilicon compound in the deposition gas when the deposition gas contains an organosilicon compound and oxygen. It is preferable that the amount be less than the theoretical amount of oxygen.

As typical examples, hexamethyldisiloxane (organosilicon compound: HMDSO, (CH ₃ ) ₆ Si ₂ O) as a source gas and oxygen (O ₂ ) as a reaction gas will be described below.

A film-forming gas containing hexamethyldisiloxane (HMDSO, (CH ₃ ) ₆ Si ₂ O) as a source gas and oxygen (O ₂ ) as a reaction gas is reacted by a plasma CVD method to form a silicon-oxygen system When the thin film is produced, the reaction represented by the following reaction formula (1) occurs by the film forming gas, and silicon dioxide is produced.

(CH ₃ ) ₆ Si ₂ O + 12O ₂ → 6CO ₂ + 9H ₂ O + 2SiO ₂ (1)

  In such a reaction, the amount of oxygen required to completely oxidize 1 mol of hexamethyldisiloxane is 12 mol. Therefore, when the film forming gas contains 12 moles or more of oxygen with respect to 1 mole of hexamethyldisiloxane and is completely reacted, a uniform silicon dioxide film is formed. The ratio is controlled to a flow rate that is equal to or less than the theoretical reaction raw material ratio, and the incomplete reaction proceeds. That is, the oxygen amount needs to be less than the stoichiometric ratio of 12 moles per mole of hexamethyldisiloxane.

In the actual reaction in the plasma CVD chamber, the source gas hexamethyldisiloxane and the reaction gas oxygen are supplied from the gas supply port to the film formation region to form a film. Even if the amount (flow rate) is 12 times the molar amount (flow rate) of hexamethyldisiloxane as the raw material gas, the reaction cannot actually proceed completely, and oxygen content It is considered that the reaction is completed only when the amount is supplied in a large excess compared to the stoichiometric ratio. For example, in order to obtain silicon oxide by complete oxidation by the CVD method, the molar amount (flow rate) of oxygen may be about 20 times or more the molar amount (flow rate) of hexamethyldisiloxane as a raw material gas. For this reason, the molar amount (flow rate) of oxygen in the reaction gas with respect to the molar amount (flow rate) of hexamethyldisiloxane as the raw material gas is preferably 12 times or less, more preferably 10 times or less, which is the stoichiometric ratio.
By containing hexamethyldisiloxane and oxygen at such a ratio, carbon atoms and hydrogen atoms in hexamethyldisiloxane that have not been completely oxidized are taken into the first gas barrier layer, and the desired first gas barrier is formed. The layer 2a can be formed, and the obtained gas barrier film can exhibit excellent gas barrier properties and bending resistance.
In addition, the lower limit of the molar amount (flow rate) of oxygen relative to the molar amount (flow rate) of hexamethyldisiloxane in the film forming gas should be greater than 0.1 times the molar amount (flow rate) of hexamethyldisiloxane. It is more preferable that the amount be more than 0.5 times.

(Degree of vacuum)
Although the pressure (degree of vacuum) in a vacuum chamber can be suitably adjusted according to the kind etc. of source gas, it is preferable to set it as the range of 0.5-100 Pa.

(Roller film formation)
In such a plasma CVD method, in order to discharge between the film forming rollers 31 and 32, an electrode drum connected to a plasma generating power source 51 (in this embodiment, installed on the film forming rollers 31 and 32). The electric power applied to can be adjusted as appropriate according to the type of source gas, the pressure in the vacuum chamber, and the like, and cannot be generally specified, but is preferably in the range of 0.1 to 10 kW.
If the applied power is in such a range, no generation of particles is observed, and the amount of heat generated during film formation is within the control. Therefore, the resin base material 1 due to a temperature rise on the surface of the resin base material 1 during film formation. There is no heat loss or wrinkling during film formation. In addition, there is little possibility that the resin base material 1 is melted by heat and a large current discharge is generated between the bare film forming rollers to damage the film forming roller itself.

  Although the conveyance speed (line speed) of the resin base material 1 can be suitably adjusted according to the kind of raw material gas, the pressure in a vacuum chamber, etc., it is preferable to set it as the range of 0.25-100 m / min. More preferably, it is in the range of 0.5 to 20 m / min. If the line speed is within the above range, wrinkles due to the heat of the resin base material 1 are hardly generated, and the thickness of the first gas barrier layer 2a to be formed can be sufficiently controlled.

[Second gas barrier layer]
A coating film of a coating-type polysilazane-containing liquid is provided on the first gas barrier layer 2a, and the second gas barrier layer 2b formed by irradiating vacuum ultraviolet light (VUV light) having a wavelength of 200 nm or less and performing a modification treatment Is preferably provided. By providing the second gas barrier layer 2b on the first gas barrier layer 2a provided by the CVD method, minute defects remaining in the first gas barrier layer 2a can be filled with the gas barrier component of polysilazane from above, and further Since gas barrier property and flexibility can be improved, it is preferable.

  The layer thickness of the second gas barrier layer 2b is preferably in the range of 1 to 500 nm, more preferably in the range of 10 to 300 nm. When the layer thickness is thicker than 1 nm, gas barrier performance can be exhibited, and when it is within 500 nm, cracks are not easily formed in the dense silicon oxide film.

(Polysilazane)
In the second gas barrier layer 2b, polysilazane represented by the general formula (A) can be used. Perhydropolysilazane in which all of R ¹ , R ² and R ^{3 in} the above general formula (A) are hydrogen atoms is particularly preferable from the viewpoint of the denseness as the film of the obtained second gas barrier layer 2b.

  The second gas barrier layer 2b can be formed by applying a coating liquid containing polysilazane onto the first gas barrier layer 2a by the CVD method and drying it, followed by irradiation with vacuum ultraviolet rays.

  As an organic solvent for preparing a coating liquid containing polysilazane, it is preferable to avoid using a lower alcohol or water-containing one that easily reacts with polysilazane. For example, hydrocarbon solvents such as aliphatic hydrocarbons, alicyclic hydrocarbons, aromatic hydrocarbons, halogenated hydrocarbon solvents, aliphatic ethers, ethers such as alicyclic ethers can be used, specifically, There are hydrocarbons such as pentane, hexane, cyclohexane, toluene, xylene, solvesso and turben, halogen hydrocarbons such as methylene chloride and trichloroethane, ethers such as dibutyl ether, dioxane and tetrahydrofuran. These organic solvents may be selected according to purposes such as the solubility of polysilazane and the evaporation rate of the solvent, and a plurality of organic solvents may be mixed and used.

  The concentration of polysilazane in the coating liquid containing polysilazane varies depending on the layer thickness of the second gas barrier layer 2b and the pot life of the coating liquid, but is preferably about 0.2 to 35% by mass.

  In order to promote modification to silicon oxynitride, metal catalysts such as amine catalysts, Pt compounds such as Pt acetylacetonate, Pd compounds such as propionic acid Pd, and Rh compounds such as Rh acetylacetonate are added to the coating solution. You can also It is particularly preferable to use an amine catalyst. Specific amine catalysts include N, N-diethylethanolamine, N, N-dimethylethanolamine, triethanolamine, triethylamine, 3-morpholinopropylamine, N, N, N ′, N′-tetramethyl-1 , 3-diaminopropane, N, N, N ′, N′-tetramethyl-1,6-diaminohexane and the like.

  The amount of these catalysts added to the polysilazane is preferably in the range of 0.1 to 10% by mass, more preferably in the range of 0.2 to 5% by mass, based on the entire coating solution. More preferably, it is in the range of 5 to 2% by mass. By making the addition amount of the catalyst within this range, it is possible to avoid excessive silanol formation, film density reduction, film defect increase, and the like due to rapid progress of the reaction.

  Any appropriate method can be adopted as a method of applying the coating liquid containing polysilazane. Specific examples include a roll coating method, a flow coating method, an ink jet method, a spray coating method, a printing method, a dip coating method, a cast film forming method, a bar coating method, and a gravure printing method.

  The thickness of the coating film can be appropriately set according to the purpose. For example, the thickness of the coating film is preferably in the range of 50 nm to 2 μm, more preferably in the range of 70 nm to 1.5 μm, and still more preferably in the range of 100 nm to 1 μm.

(Excimer processing)
The second gas barrier layer 2b is a step of irradiating the layer containing polysilazane with vacuum ultraviolet rays, and at least a part of the polysilazane is modified into silicon oxynitride.

Here, the presumed mechanism in which the coating film containing polysilazane is modified in the vacuum ultraviolet irradiation step and becomes a specific composition of SiO _x N _y will be described by taking perhydropolysilazane as an example.

Perhydropolysilazane can be represented by a composition of “— (SiH ₂ —NH) _n —”. In the case of SiO _x N _y , x = 0 and y = 1. In order to satisfy x> 0, an external oxygen source is required. This is because (i) oxygen and moisture contained in the polysilazane coating solution, and (ii) oxygen taken into the coating film from the atmosphere during the coating and drying process. And (iii) Oxygen, moisture, ozone, singlet oxygen taken into the coating film from the atmosphere in the vacuum ultraviolet irradiation process, and (iv) heat applied in the vacuum ultraviolet irradiation process, etc. Oxygen and moisture that move into the coating as a gas, (v) When the vacuum ultraviolet irradiation process is performed in a non-oxidizing atmosphere, when moving from the non-oxidizing atmosphere to the oxidizing atmosphere, Oxygen, moisture, etc. taken into the coating film from the atmosphere serve as an oxygen source.
On the other hand, for y, the condition under which nitriding proceeds rather than the oxidation of Si is considered to be very special, so basically 1 is the upper limit.
Also, from the relationship of Si, O, and N bond, x and y are basically in the range of 2x + 3y ≦ 4. In the state of y = 0 where the oxidation has progressed completely, the coating film contains silanol groups, and there are cases where 2 <x <2.5.

  The reaction mechanism presumed to produce silicon oxynitride and further silicon oxide from perhydropolysilazane in the vacuum ultraviolet irradiation step will be described below.

(1) Dehydrogenation and accompanying Si-N bond formation Si-H bonds and N-H bonds in perhydropolysilazane are relatively easily cleaved by excitation by vacuum ultraviolet irradiation and the like. It is considered that it is recombined as -N (a dangling bond of Si may be formed). That is, the cured as SiN _y composition without oxidizing. In this case, the polymer main chain is not broken. The breaking of Si—H bonds and N—H bonds is promoted by the presence of a catalyst and heating. The cut H is released out of the membrane as H ₂ .

(2) Formation of Si—O—Si Bonds by Hydrolysis / Dehydration Condensation Si—N bonds in perhydropolysilazane are hydrolyzed by water, and the polymer main chain is cleaved to form Si—OH. Two Si—OHs are dehydrated and condensed to form Si—O—Si bonds and harden. This is a reaction that occurs in the atmosphere, but during vacuum ultraviolet irradiation in an inert atmosphere, water vapor generated as a gas released from the substrate by the heat of irradiation is considered to be the main moisture source. When the moisture is excessive, Si—OH that cannot be dehydrated and condensed remains, and a cured film having a low gas barrier property represented by a composition of SiO _2.1 to _2.3 is obtained.

(3) Direct oxidation by singlet oxygen, formation of Si-O-Si bond When a suitable amount of oxygen is present in the atmosphere during irradiation with vacuum ultraviolet rays, singlet oxygen having a very strong oxidizing power is formed. H and N in perhydropolysilazane are replaced with O to form a Si—O—Si bond and harden. It is thought that recombination of the bond may occur due to cleavage of the polymer main chain.

(4) Oxidation with Si-N bond cleavage by vacuum ultraviolet irradiation / excitation Since the energy of vacuum ultraviolet light is higher than the bond energy of Si-N in perhydropolysilazane, the Si-N bond is cleaved, and oxygen, If an oxygen source such as ozone or water is present, it is considered that it is oxidized to form a Si—O—Si bond or a Si—O—N bond. It is thought that recombination of the bond may occur due to cleavage of the polymer main chain.

  Adjustment of the composition of the silicon oxynitride of the layer subjected to vacuum ultraviolet irradiation on the layer containing polysilazane can be performed by appropriately controlling the oxidation state by appropriately combining the oxidation mechanisms (1) to (4) described above. .

In vacuum ultraviolet irradiation step, illuminance of the vacuum ultraviolet rays in the coating film surface for receiving polysilazane coating film is preferably in the range of 30~200mW / cm ^2, it is in the range of 50~160mW / cm ² Is more preferable. If it is 30 mW / cm ² or more, there is no concern that the reforming efficiency is reduced, and if it is 200 mW / cm ² or less, the coating film is not ablated and the resin substrate 1 is not damaged.

Irradiation energy amount of the VUV in the polysilazane coating film surface is preferably in the range of 200~10000mJ / cm ^2, and more preferably in a range of 500~5000mJ / cm ^2. The 200 mJ / cm ² or more, can reforming sufficiently, 10000 mJ / cm ² not to excessively reforming below, without cracking or thermal deformation of the substrate.

  As the vacuum ultraviolet light source, the above rare gas excimer lamp is preferably used.

  In order to obtain excimer light emission, a method using dielectric barrier discharge is known. Dielectric barrier discharge is a gas space that is generated in a gas space by applying a high frequency high voltage of several tens of kHz to the electrode by placing a gas space between both electrodes via a dielectric such as transparent quartz. It is a discharge called a thin micro discharge. When the micro discharge streamer reaches the tube wall (derivative), electric charges accumulate on the dielectric surface, and the micro discharge disappears. This micro discharge spreads over the entire tube wall, and is a discharge that is repeatedly generated and extinguished. For this reason, flickering of light that can be confirmed with the naked eye occurs. Moreover, since a very high temperature streamer reaches a pipe wall directly locally, there is a possibility that deterioration of the pipe wall may be accelerated.

  As a method for efficiently obtaining excimer light emission, electrodeless electric field discharge is possible in addition to dielectric barrier discharge. Electrodeless electric field discharge by capacitive coupling, also called RF discharge. The lamp, the electrode, and the arrangement thereof may be basically the same as those of the dielectric barrier discharge, but the high frequency applied between the two electrodes is lit at several MHz. In the electrodeless field discharge, since a spatially and temporally uniform discharge can be obtained in this way, a long-life lamp without flickering can be obtained.

  In the case of dielectric barrier discharge, micro discharge occurs only between the electrodes, so that the outer electrode covers the entire outer surface and transmits light to extract light to the outside in order to discharge in the entire discharge space. Must be a thing.

  For this reason, an electrode in which a fine metal wire is formed in a net shape is used. Since this electrode uses as thin a line as possible so as not to block light, it is easily damaged by ozone generated by vacuum ultraviolet light in an oxygen atmosphere. In order to prevent this, it is necessary to provide an atmosphere of an inert gas such as nitrogen around the lamp, that is, the inside of the irradiation apparatus, and provide a synthetic quartz window to extract the irradiation light. Synthetic quartz windows are not only expensive consumables, but also cause light loss.

  Since the double cylindrical lamp has an outer diameter of about 25 mm, the difference in distance to the irradiation surface cannot be ignored between the position directly below the lamp axis and the side surface of the lamp, resulting in a large difference in illuminance. Therefore, even if the lamps are closely arranged, a uniform illuminance distribution cannot be obtained. If the irradiation device is provided with a synthetic quartz window, the distance in the oxygen atmosphere can be made uniform, and a uniform illuminance distribution can be obtained.

  When electrodeless field discharge is used, it is not necessary to make the external electrodes mesh. The glow discharge spreads over the entire discharge space simply by providing an external electrode on a part of the lamp outer surface. As the external electrode, an electrode that also serves as a light reflector made of an aluminum block is usually used on the back of the lamp. However, since the outer diameter of the lamp is as large as in the case of the dielectric barrier discharge, synthetic quartz is required to obtain a uniform illuminance distribution.

  The biggest feature of the capillary excimer lamp is its simple structure. The quartz tube is closed at both ends, and only gas for excimer light emission is sealed inside.

  The outer diameter of the tube of the thin tube lamp is about 6 to 12 mm, and if it is too thick, a high voltage is required for starting.

  As the form of discharge, either dielectric barrier discharge or electrodeless field discharge can be used. The electrode may have a flat surface in contact with the lamp, but if the shape is matched to the curved surface of the lamp, the lamp can be firmly fixed, and the discharge is more stable when the electrode is in close contact with the lamp. Also, if the curved surface is made into a mirror surface with aluminum, it also becomes a light reflector.

  The Xe excimer lamp emits ultraviolet light having a short wavelength of 172 nm at a single wavelength, and thus has excellent luminous efficiency. Since this light has a large oxygen absorption coefficient, it can generate radical oxygen atom species and ozone at a high concentration with a very small amount of oxygen.

  Moreover, it is known that the energy of light having a short wavelength of 172 nm has a high ability to dissociate organic bonds. The modification of the polysilazane layer can be realized in a short time by the active oxygen or ozone and the high energy of ultraviolet radiation.

  Therefore, compared with low-pressure mercury lamps with wavelengths of 185 nm and 254 nm and plasma cleaning, it is possible to shorten the process time associated with high throughput, reduce the equipment area, and irradiate organic materials and plastic substrates that are easily damaged by heat. .

  Since the excimer lamp has high light generation efficiency, it can be turned on with low power. In addition, light having a long wavelength that causes a temperature increase due to light is not emitted, and energy is irradiated in the ultraviolet region, that is, in a short wavelength, so that the increase in the surface temperature of the target object is suppressed. For this reason, it is suitable for flexible film materials such as PET that are easily affected by heat.

  Oxygen is required for the reaction at the time of ultraviolet irradiation, but since vacuum ultraviolet rays are absorbed by oxygen, the efficiency in the ultraviolet irradiation process tends to decrease, so the irradiation of vacuum ultraviolet rays is as low as possible in the oxygen concentration state. Preferably it is done. That is, the oxygen concentration at the time of vacuum ultraviolet irradiation is preferably in the range of 10 to 10000 ppm, more preferably in the range of 50 to 5000 ppm, and still more preferably in the range of 1000 to 4500 ppm.

  The gas satisfying the irradiation atmosphere used at the time of vacuum ultraviolet irradiation is preferably a dry inert gas, and particularly preferably a dry nitrogen gas from the viewpoint of cost. The oxygen concentration can be adjusted by measuring the flow rates of oxygen gas and inert gas introduced into the irradiation chamber and changing the flow rate ratio.

[Resin substrate]
Examples of the resin substrate 1 on which the transparent electrode 5 is formed include, but are not limited to, a resin film. Examples of the resin substrate 1 that is preferably used include a transparent resin film.

  Examples of the resin film include polyesters such as polyethylene terephthalate (PET) and polyethylene naphthalate (PEN), polyethylene, polypropylene, cellophane, cellulose diacetate, cellulose triacetate (TAC), cellulose acetate butyrate, cellulose acetate propionate ( CAP), cellulose esters such as cellulose acetate phthalate, cellulose nitrate or derivatives thereof, polyvinylidene chloride, polyvinyl alcohol, polyethylene vinyl alcohol, syndiotactic polystyrene, polycarbonate, norbornene resin, polymethylpentene, polyether ketone, polyimide , Polyethersulfone (PES), polyphenylene sulfide, polysulfones, Cycloolefin resins such as polyetherimide, polyetherketoneimide, polyamide, fluororesin, nylon, polymethylmethacrylate, acrylic or polyarylate, Arton (trade name, manufactured by JSR) or Appel (trade name, manufactured by Mitsui Chemicals) Is mentioned.

[electrode]
The organic EL element has a light emitting unit 6 having an organic functional layer sandwiched between a pair of electrodes composed of the following anode and cathode. Hereinafter, the electrode will be described in detail.

[Anode (transparent electrode)]
As the anode (transparent electrode 5) in the organic EL element, an electrode material made of a metal, an alloy, an electrically conductive compound, or a mixture thereof having a high work function (4 eV or more) is preferably used. Specific examples of such an electrode substance include conductive transparent materials such as metals such as Au and Ag, CuI, indium tin oxide (ITO), SnO ₂ , and ZnO. Alternatively, an amorphous material such as IDIXO (In ₂ O ₃ —ZnO) capable of forming a transparent conductive film may be used.
For the anode, a thin film may be formed by depositing these electrode materials by a method such as vapor deposition or sputtering, and a pattern having a desired shape may be formed by photolithography, or when the pattern accuracy is not so high (about 100 μm or more) ), A pattern may be formed through a mask having a desired shape when the electrode material is deposited or sputtered.
Or when using the substance which can be apply | coated like an organic electroconductivity compound, wet film-forming methods, such as a printing system and a coating system, can also be used. When light emission is extracted from this anode, it is desirable that the transmittance be greater than 10%, and the sheet resistance as the anode is several hundred Ω / sq. The following is preferred. Although the film thickness depends on the material, it is usually selected within the range of 10 to 1000 nm, preferably within the range of 10 to 200 nm.

In the organic EL element, it is preferable to use a transparent electrode 5 as shown in FIG. 1 as the anode.
As shown in FIG. 1, the transparent electrode 5 has a two-layer structure in which a base layer 5a and a conductive layer 5b formed thereon are sequentially laminated from the resin substrate 1 side. Among these, the conductive layer 5b is a layer comprised using silver or the alloy which has silver as a main component, and the base layer 5a is a layer comprised using the compound containing a nitrogen atom, for example.
The transparent of the transparent electrode 5 means that the light transmittance at a wavelength of 550 nm is 50% or more.

(1) Underlayer The underlayer 5a is a layer provided on the resin substrate 1 side of the conductive layer 5b. The material constituting the underlayer 5a is not particularly limited as long as it can suppress the aggregation of silver when forming the conductive layer 5b made of silver or an alloy containing silver as a main component. And compounds containing a nitrogen atom or a sulfur atom.

When the underlayer 5a is made of a low refractive index material (refractive index less than 1.7), the upper limit of the layer thickness needs to be less than 50 nm, preferably less than 30 nm, and preferably less than 10 nm. Is more preferable, and it is especially preferable that it is less than 5 nm. By making the layer thickness less than 50 nm, optical loss can be minimized. On the other hand, the lower limit of the layer thickness is required to be 0.05 nm or more, preferably 0.1 nm or more, and particularly preferably 0.3 nm or more. By setting the layer thickness to 0.05 nm or more, the underlayer 5a can be formed uniformly, and the effect (inhibition of silver aggregation) can be made uniform.
When the underlayer 5a is made of a high refractive index material (refractive index of 1.7 or more), the upper limit of the layer thickness is not particularly limited, and the lower limit of the layer thickness is the same as that of the low refractive index material. is there.
However, as a simple function of the base layer 5a, it is sufficient if the base layer 5a is formed with a necessary layer thickness that allows uniform film formation.

  The compound containing a nitrogen atom constituting the underlayer 5a is not particularly limited as long as it is a compound containing a nitrogen atom in the molecule, but is preferably a compound having a heterocycle having a nitrogen atom as a heteroatom. . Examples of the heterocycle having a nitrogen atom as a hetero atom include aziridine, azirine, azetidine, azeto, azolidine, azole, azinane, pyridine, azepan, azepine, imidazole, pyrazole, oxazole, thiazole, imidazoline, pyrazine, morpholine, thiazine, indole, Examples include isoindole, benzimidazole, purine, quinoline, isoquinoline, quinoxaline, cinnoline, pteridine, acridine, carbazole, benzo-C-cinnoline, porphyrin, chlorin, choline and the like.

  As a method for forming the underlying layer 5a, a wet process such as a coating method, an ink jet method, a coating method, or a dip method, a dry process such as a vapor deposition method (resistance heating, EB method, etc.), a sputtering method, or a CVD method is used. And the like. Among these, the vapor deposition method is preferably applied.

(2) Conductive layer The conductive layer 5b is a layer formed using silver or an alloy containing silver as a main component, and is a layer formed on the base layer 5a.
Here, the main component refers to a component having the highest constituent ratio among the components constituting the conductive layer 5b.

  Examples of the alloy mainly composed of silver (Ag) constituting the conductive layer 5b include silver magnesium (AgMg), silver copper (AgCu), silver palladium (AgPd), silver palladium copper (AgPdCu), and silver indium (AgIn). ) And the like.

  The conductive layer 5b as described above may have a configuration in which silver or an alloy layer mainly composed of silver is divided into a plurality of layers as necessary.

  Furthermore, the thickness of the conductive layer 5b is preferably in the range of 2 to 15 nm, more preferably in the range of 3 to 12 nm, and particularly preferably in the range of 4 to 9 nm. When the layer thickness is less than 15 nm, the absorption component or reflection component of the layer is small, and the light transmittance of the conductive layer 5b is increased. Further, when the layer thickness is thicker than 2 nm, the conductivity of the layer can be sufficiently ensured.

  Note that the transparent electrode 5 having a laminated structure including the base layer 5a and the conductive layer 5b formed on the base layer 5a as described above may have the upper part of the conductive layer 5b covered with a protective film. Layers may be stacked. In this case, it is preferable that the protective film and another conductive layer have light transmittance so that the light transmittance of the transparent electrode 5 is not impaired.

As a method for forming such a conductive layer 5b, a method using a wet process such as a coating method, an ink jet method, a coating method, a dip method, a vapor deposition method (resistance heating, EB method, etc.), a sputtering method, a CVD method, etc. And a method using the dry process. Among these, the vapor deposition method is preferably applied.
In addition, the conductive layer 5b is formed on the base layer 5a, so that the conductive layer 5b is sufficiently conductive without high-temperature annealing after the formation of the conductive layer 5b. The film may be subjected to high-temperature annealing after film formation.

  As described above, the transparent electrode 5 has, for example, a configuration in which the conductive layer 5b made of silver or an alloy containing silver as a main component is provided on the base layer 5a formed using a compound containing nitrogen atoms. . As a result, when the conductive layer 5b is formed on the base layer 5a, the silver atoms constituting the conductive layer 5b interact with the compound containing nitrogen atoms constituting the base layer 5a. The diffusion distance on the surface of the formation 5a is reduced, and silver aggregation is suppressed.

  Here, in general, in the formation of the conductive layer 5b containing silver as a main component, a thin film is grown by a nucleus growth type (Volumer-Weber: VW type). When the thickness is thin, it is difficult to obtain conductivity, and the sheet resistance value becomes high. Therefore, it is necessary to increase the layer thickness in order to ensure conductivity. However, if the layer thickness is increased, the light transmittance is lowered, so that it is not suitable as a transparent electrode.

  However, according to the transparent electrode 5, since aggregation of silver is suppressed on the base layer 5a as described above, in the formation of the conductive layer 5b made of silver or an alloy containing silver as a main component, the single layer growth type is used. (Frank-van der Merwe: FM type).

  Here, the transparent of the transparent electrode 5 means that the light transmittance at a wavelength of 550 nm is 50% or more. However, each of the above materials used as the base layer 5a is mainly composed of silver or silver. Compared with the conductive layer 5b made of an alloy, the film is sufficiently light transmissive. On the other hand, the conductivity of the transparent electrode 5 is mainly ensured by the conductive layer 5b. Therefore, as described above, the conductive layer 5b made of silver or an alloy containing silver as a main component has a thinner layer to ensure conductivity, thereby improving the conductivity of the transparent electrode 5 and light. It becomes possible to achieve a balance with the improvement of permeability.

[cathode]
The cathode (counter electrode 7) is an electrode film that functions as a cathode (cathode) that supplies electrons to the light emitting unit 6. As the cathode, a material having a work function (4 eV or less) metal (referred to as an electron injecting metal), an alloy, an electrically conductive compound, and a mixture thereof as an electrode material is used.
Specific examples of such electrode materials include sodium, sodium-potassium alloy, magnesium, lithium, magnesium / copper mixture, magnesium / silver mixture, magnesium / aluminum mixture, magnesium / indium mixture, aluminum / aluminum oxide (Al ₂ O ₃ ) Mixtures, indium, lithium / aluminum mixtures, rare earth metals and the like.
Among these, from the point of durability against electron injection and oxidation, etc., a mixture of an electron injecting metal and a second metal which is a stable metal having a larger work function than this, for example, a magnesium / silver mixture, A magnesium / aluminum mixture, a magnesium / indium mixture, an aluminum / aluminum oxide (Al ₂ O ₃ ) mixture, a lithium / aluminum mixture, aluminum, or the like is preferable.

The sheet resistance as a cathode is several hundred Ω / sq. The following is preferable, and the film thickness is usually selected in the range of 10 nm to 5 μm, preferably in the range of 50 to 200 nm. In order to transmit the emitted light, if either the anode or the cathode of the organic EL element is transparent or translucent, the light emission luminance is improved, which is convenient.
Moreover, after producing the said metal by the film thickness of 1-20 nm as a cathode, the transparent or semi-transparent cathode can be produced by producing the electroconductive transparent material quoted by description of the anode on it, By applying this, an element in which both the anode and the cathode are transmissive can be manufactured.
If this organic EL element is one that takes out the emitted light h from the cathode (counter electrode 7) side, a conductive material having good light transmittance is selected from the conductive materials described above. What is necessary is just to comprise a cathode (counter electrode 7).

  The cathode can be produced by forming a thin film of these electrode materials by a method such as vapor deposition or sputtering.

[Auxiliary electrode]
The auxiliary electrode 9 is provided for the purpose of reducing the resistance of the transparent electrode 5, and is preferably provided in contact with the conductive layer 5 b of the transparent electrode 5.
As a material for forming the auxiliary electrode 9, a metal having a low resistance such as gold, platinum, silver, copper, and aluminum is preferable. Since these metals have low light transmittance, a pattern is formed in a range that does not affect the extraction of the emitted light h from the light extraction surface.
The line width of the auxiliary electrode 9 is preferably 50 μm or less from the viewpoint of the aperture ratio for extracting light, and the thickness of the auxiliary electrode 9 is preferably 1 μm or more from the viewpoint of conductivity.

  Examples of the method for forming the auxiliary electrode 9 include a vapor deposition method, a sputtering method, a printing method, an ink jet method, and an aerosol jet method.

[Extraction electrode]
The extraction electrode 8 is for electrically connecting the transparent electrode 5 and an external power source, and the material thereof is not particularly limited, and a known material can be suitably used. A metal film such as a MAM electrode (Mo / Al · Nd alloy / Mo) can be used.

[Light emitting unit]
The light emitting unit 6 refers to a light emitting body (unit) composed mainly of an organic functional layer such as a light emitting layer, a hole transport layer, and an electron transport layer containing at least various organic compounds described later. The luminous body is sandwiched between a pair of electrodes composed of an anode and a cathode, and holes supplied from the anode and electrons supplied from the cathode are recombined in the luminous body. Emits light.
The light emitting unit 6 has a configuration in which, for example, a hole injection layer 6a / a hole transport layer 6b / a light emitting layer 6c / an electron transport layer 6d / an electron injection layer 6e are stacked in this order from the transparent electrode 5 side that is an anode. Is done. Hereinafter, each layer will be described in detail.

[Light emitting layer]
The light emitting layer 6c preferably contains a phosphorescent light emitting compound as a light emitting material.

  The light emitting layer 6c is a layer that emits light by recombination of electrons injected from the electrode or the electron transport layer 6d and holes injected from the hole transport layer 6b, and the light emitting portion is the light emitting layer 6c. Even within the layer, it may be the interface between the light emitting layer 6c and the adjacent layer.

  The light emitting layer 6c is not particularly limited in its configuration as long as the light emitting material contained satisfies the light emission requirements. Moreover, there may be a plurality of layers having the same emission spectrum and emission maximum wavelength. In this case, it is preferable to have a non-light emitting auxiliary layer (not shown) between the light emitting layers 6c.

The total thickness of the light emitting layer 6c is preferably in the range of 1 to 100 nm, and more preferably in the range of 1 to 30 nm because a lower driving voltage can be obtained.
In addition, the sum total of the layer thickness of the light emitting layer 6c is a layer thickness also including the said intermediate | middle layer, when a nonluminous intermediate | middle layer exists between the light emitting layers 6c.

  In the case of the light emitting layer 6c having a structure in which a plurality of layers are laminated, the thickness of each light emitting layer is preferably adjusted within a range of 1 to 50 nm, and more preferably adjusted within a range of 1 to 20 nm. When the plurality of stacked light emitting layers correspond to the respective emission colors of blue, green, and red, there is no particular limitation on the relationship between the thicknesses of the blue, green, and red light emitting layers.

  The light emitting layer 6c may be a mixture of a plurality of light emitting materials, or a phosphorescent light emitting material and a fluorescent light emitting material (fluorescent dopant, fluorescent compound) may be mixed and used in the same light emitting layer 6c. Good.

  As a structure of the light emitting layer 6c, it is preferable to contain a host compound (light emitting host etc.) and a light emitting material (light emitting dopant), and to emit light from the light emitting material.

  The light emitting layer 6c as described above is formed by forming a light emitting material or a host compound described later by a known thin film forming method such as a vacuum deposition method, a spin coating method, a casting method, an LB method, or an ink jet method. be able to.

(1) Host compound As the host compound contained in the light emitting layer 6c, a compound having a phosphorescence quantum yield of phosphorescence emission at room temperature (25 ° C) of less than 0.1 is preferable. More preferably, the phosphorescence quantum yield is less than 0.01. Moreover, it is preferable that the volume ratio in the layer is 50% or more in the compound contained in the light emitting layer 6c.

  As a host compound, a well-known host compound may be used independently, or multiple types may be used. By using a plurality of types of host compounds, it is possible to adjust the movement of charges, and the organic EL element can be made highly efficient. In addition, by using a plurality of kinds of light emitting materials described later, it is possible to mix different light emission, thereby obtaining an arbitrary light emission color.

  The host compound used may be a conventionally known low molecular compound, a high molecular compound having a repeating unit, or a low molecular compound having a polymerizable group such as a vinyl group or an epoxy group (evaporation polymerizable light emitting host). .

The known host compound is preferably a compound that has a hole transporting ability and an electron transporting ability, prevents the emission of light from becoming longer, and has a high Tg (glass transition temperature).
The glass transition point (Tg) here is a value determined by a method based on JIS K 7121 using DSC (Differential Scanning Calorimetry).

  As specific examples of known host compounds, compounds described in the following documents can be used. For example, JP2010-251675A, JP2001-257706A, 2002-308855, 2001-313179, 2002-319491, 2001-357777, 2002-334786. Gazette, 2002-8860 gazette, 2002-334787 gazette, 2002-15871 gazette, 2002-334788 gazette, 2002-43056 gazette, 2002-334789 gazette, 2002-75645 gazette. Gazette, 2002-338579, 2002-105445, 2002-343568, 2002-141173, 2002-352957, 2002-203683, 2002-363227 Gazette, 2002-231453, 2003-3165, 2002-234888, 2003-27048, 2002-255934, 2002-260861, 2002-280183 No. 2002-299060, No. 2002-302516, No. 2002-305083, No. 2002-305084, No. 2002-308837, and the like.

(2) Luminescent material Examples of the luminescent material include phosphorescent compounds (phosphorescent compounds, phosphorescent luminescent materials) and fluorescent compounds (fluorescent compounds, fluorescent luminescent materials).

(Phosphorescent compound)
A phosphorescent compound is a compound in which light emission from an excited triplet is observed. Specifically, it is a compound that emits phosphorescence at room temperature (25 ° C.), and the phosphorescence quantum yield is 0 at 25 ° C. A preferred phosphorescence quantum yield is 0.1 or more, although it is defined as 0.01 or more compounds.

  The phosphorescence quantum yield can be measured by the method described in Spectroscopic II, page 398 (1992 edition, Maruzen) of Experimental Chemistry Course 4 of the 4th edition. The phosphorescence quantum yield in solution can be measured using various solvents, but when using a phosphorescent compound, the above phosphorescence quantum yield (0.01 or more) can be achieved in any solvent. That's fine.

There are two types of light emission principle of the phosphorescent compound.
One is that recombination of carriers occurs on the host compound to which carriers are transported to generate an excited state of the host compound, and this energy is transferred to the phosphorescent compound to emit light from the phosphorescent compound. Energy transfer type.
The other is a carrier trap type in which a phosphorescent compound serves as a carrier trap, carrier recombination occurs on the phosphorescent compound, and light emission from the phosphorescent compound is obtained.
In either case, the condition is that the excited state energy of the phosphorescent compound is lower than the excited state energy of the host compound.

  The phosphorescent compound can be appropriately selected from known compounds used for the light emitting layer of a general organic EL device, but preferably contains a group 8-10 metal in the periodic table of elements. More preferably, it is an iridium compound, an osmium compound, a platinum compound (platinum complex compound), or a rare earth complex, and most preferably an iridium compound.

  The at least one light emitting layer 6c may contain two or more types of phosphorescent compounds, and the concentration ratio of the phosphorescent compounds in the light emitting layer 6c changes in the thickness direction of the light emitting layer 6c. Also good.

  The phosphorescent compound is preferably 0.1% by volume or more and less than 30% by volume with respect to the total amount of the light emitting layer 6c.

  The phosphorescent compound can be appropriately selected from known compounds used for the light emitting layer of the organic EL device.

  Specific examples of the phosphorescent compound include, but are not limited to, compounds described in JP2010-251675A.

(Fluorescent compound)
Fluorescent compounds include coumarin dyes, pyran dyes, cyanine dyes, croconium dyes, squalium dyes, oxobenzanthracene dyes, fluorescein dyes, rhodamine dyes, pyrylium dyes, perylene dyes, stilbene dyes. System dyes, polythiophene dyes, rare earth complex phosphors, and the like.

[Injection layer: hole injection layer, electron injection layer]
The injection layer is a layer provided between the electrode and the light emitting layer 6c in order to lower the driving voltage and improve the light emission luminance. “The organic EL element and its industrialization front line (November 30, 1998 2) Chapter 2 “Electrode Materials” (pages 123 to 166) of “T. S. Co., Ltd.”, which includes a hole injection layer 6a and an electron injection layer 6e.

  The injection layer can be provided as necessary. In the case of the hole injection layer 6a, between the anode (anode) and the light emitting layer 6c or the hole transport layer 6b, and in the case of the electron injection layer 6e, between the cathode (cathode) and the light emitting layer 6c or the electron transport layer 6d. May be present.

  The details of the hole injection layer 6a are also described in JP-A-9-45479, JP-A-9-260062, JP-A-8-288069 and the like. As a specific example, phthalocyanine represented by copper phthalocyanine Examples thereof include a layer, an oxide layer typified by vanadium oxide, an amorphous carbon layer, and a polymer layer using a conductive polymer such as polyaniline (emeraldine) or polythiophene.

  The details of the electron injection layer 6e are described in JP-A-6-325871, JP-A-9-17574, JP-A-10-74586, and the like, and specifically represented by strontium, aluminum and the like. Examples thereof include a metal layer, an alkali metal halide layer typified by potassium fluoride, an alkaline earth metal compound layer typified by magnesium fluoride, and an oxide layer typified by molybdenum oxide. The electron injection layer 6e is preferably a very thin layer, and the layer thickness is preferably in the range of 1 nm to 10 μm, depending on the material.

[Hole transport layer]
The hole transport layer 6b is made of a hole transport material having a function of transporting holes, and in a broad sense, the hole injection layer 6a and the electron blocking layer are also included in the hole transport layer 6b.
The hole transport layer 6b can be provided as a single layer or a plurality of layers.

  The hole transport material has any of hole injection or transport and electron barrier properties, and may be either organic or inorganic. For example, triazole derivatives, oxadiazole derivatives, imidazole derivatives, polyarylalkane derivatives, pyrazoline derivatives and pyrazolone derivatives, phenylenediamine derivatives, arylamine derivatives, amino-substituted chalcone derivatives, oxazole derivatives, styrylanthracene derivatives, fluorenone derivatives, hydrazone derivatives, Examples thereof include stilbene derivatives, silazane derivatives, aniline copolymers, conductive polymer oligomers, particularly thiophene oligomers.

  Although the above-mentioned thing can be used as a positive hole transport material, It is preferable to use a porphyrin compound, an aromatic tertiary amine compound, and a styryl amine compound, especially an aromatic tertiary amine compound.

  Representative examples of aromatic tertiary amine compounds and styrylamine compounds include N, N, N ′, N′-tetraphenyl-4,4′-diaminophenyl, N, N′-diphenyl-N, N′— Bis (3-methylphenyl)-[1,1′-biphenyl] -4,4′-diamine (TPD), 2,2-bis (4-di-p-tolylaminophenyl) propane, 1,1-bis (4-di-p-tolylaminophenyl) cyclohexane, N, N, N ′, N′-tetra-p-tolyl-4,4′-diaminobiphenyl, 1,1-bis (4-di-p-tolyl) Aminophenyl) -4-phenylcyclohexane, bis (4-dimethylamino-2-methylphenyl) phenylmethane, bis (4-di-p-tolylaminophenyl) phenylmethane, N, N'-diphenyl-N, N ' − (4-methoxyphenyl) -4,4'-diaminobiphenyl, N, N, N ', N'-tetraphenyl-4,4'-diaminodiphenyl ether, 4,4'-bis (diphenylamino) quadriphenyl, N, N, N-tri (p-tolyl) amine, 4- (di-p-tolylamino) -4 '-[4- (di-p-tolylamino) styryl] stilbene, 4-N, N-diphenylamino- (2-diphenylvinyl) benzene, 3-methoxy-4'-N, N-diphenylaminostilbenzene, N-phenylcarbazole, and two condensed aromatics described in US Pat. No. 5,061,569 Having a ring in the molecule, for example, 4,4'-bis [N- (1-naphthyl) -N-phenylamino] biphenyl (NPD), JP-A-4-30868 4,4 ', 4 "-tris [N- (3-methylphenyl) -N-phenylamino] triphenylamine (MTDATA) in which three triphenylamine units described in Japanese Patent Publication are linked in a starburst type ) And the like.

  Furthermore, a polymer material in which these materials are introduced into a polymer chain or these materials are used as a polymer main chain can also be used. In addition, inorganic compounds such as p-type-Si and p-type-SiC can also be used as the hole injection material and the hole transport material.

  JP-A-11-251067, J. Org. Huang et. al. , Applied Physics Letters, 80 (2002), p. A so-called p-type hole transport material as described in 139 can also be used. These materials are preferably used because a light emitting element with higher efficiency can be obtained.

  In addition, the hole transport layer 6b can be doped with impurities to increase the p property. Examples thereof include JP-A-4-297076, JP-A-2000-196140, 2001-102175, J.A. Appl. Phys. 95, 5773 (2004), and the like.

  Thus, it is preferable to increase the p property of the hole transport layer 6b because an element with lower power consumption can be manufactured.

  The hole transport layer 6b may have a single layer structure composed of one or more of the above materials.

  Although there is no restriction | limiting in particular about the layer thickness of the positive hole transport layer 6b, Usually, 5 nm-about 5 micrometers, Preferably it exists in the range of 5-200 nm.

  The hole transport layer 6b is formed by thinning the hole transport material by a known method such as a vacuum deposition method, a spin coating method, a casting method, a printing method including an inkjet method, or an LB method. be able to.

[Electron transport layer]
The electron transport layer 6d is made of a material having a function of transporting electrons. In a broad sense, the electron injection layer 6e and a hole blocking layer (not shown) are also included in the electron transport layer 6d.
The electron transport layer 6d can be provided as a single layer structure or a multilayer structure of a plurality of layers.

In the electron transport layer 6d having a single layer structure and the electron transport layer 6d having a multilayer structure, an electron transport material (also serving as a hole blocking material) constituting a layer portion adjacent to the light emitting layer 6c is used as an electron injected from the cathode. As long as it has a function of transmitting the light to the light emitting layer 6c. As such a material, any one of conventionally known compounds can be selected and used.
Examples thereof include nitro-substituted fluorene derivatives, diphenylquinone derivatives, thiopyran dioxide derivatives, carbodiimides, fluorenylidenemethane derivatives, anthraquinodimethane, anthrone derivatives, oxadiazole derivatives, and the like. Further, in the above oxadiazole derivative, a thiadiazole derivative in which the oxygen atom of the oxadiazole ring is substituted with a sulfur atom, and a quinoxaline derivative having a quinoxaline ring known as an electron withdrawing group are also used as the material for the electron transport layer 6d Can do. Furthermore, a polymer material in which these materials are introduced into a polymer chain or these materials are used as a polymer main chain can also be used.

In addition, metal complexes of 8-quinolinol derivatives such as tris (8-quinolinol) aluminum (Alq ₃ ), tris (5,7-dichloro-8-quinolinol) aluminum, tris (5,7-dibromo-8-quinolinol) The central metals of aluminum, tris (2-methyl-8-quinolinol) aluminum, tris (5-methyl-8-quinolinol) aluminum, bis (8-quinolinol) zinc (Znq), etc. and these metal complexes are In, Mg, Metal complexes replaced with Cu, Ca, Sn, Ga, or Pb can also be used as the material for the electron transport layer 6d.

  In addition, metal-free or metal phthalocyanine or those whose terminal is substituted with an alkyl group or a sulfonic acid group can be preferably used as the material for the electron transport layer 6d. Further, a distyrylpyrazine derivative that is also used as a material for the light emitting layer 6c can be used as a material for the electron transport layer 6d, and similarly to the hole injection layer 6a and the hole transport layer 6b, n-type-Si, n-type. An inorganic semiconductor such as -SiC can also be used as the material of the electron transport layer 6d.

  In addition, the electron transport layer 6d can be doped with impurities to increase the n property. Examples thereof include JP-A-4-297076, JP-A-10-270172, JP-A-2000-196140, 2001-102175, J.A. Appl. Phys. 95, 5773 (2004), and the like. Furthermore, the electron transport layer 6d preferably contains potassium, a potassium compound, or the like. As the potassium compound, for example, potassium fluoride can be used. Thus, when the n property of the electron transport layer 6d is increased, an element with lower power consumption can be manufactured.

  Further, as the material (electron transporting compound) of the electron transport layer 6d, the same material as that of the base layer 5a described above may be used. This is the same for the electron transport layer 6d that also serves as the electron injection layer 6e, and the same material as that for the base layer 5a described above may be used.

Although there is no restriction | limiting in particular about the layer thickness of 6 d of electron carrying layers, Usually, 5 nm-about 5 micrometers, Preferably it exists in the range of 5-200 nm.
The electron transport layer 6d may have a single-layer structure made of one or more of the above materials.

  The electron transport layer 6d can be formed by thinning the above material by a known method such as a vacuum deposition method, a spin coating method, a casting method, a printing method including an ink jet method, or an LB method.

[Blocking layer: hole blocking layer, electron blocking layer]
As described above, the blocking layer is provided as necessary in addition to the basic constituent layer of the organic compound thin film. For example, as described in JP-A Nos. 11-204258 and 11-204359, and “Organic EL elements and the forefront of industrialization” (issued by NTT, Inc. on November 30, 1998). There is a hole blocking layer.

  The hole blocking layer has the function of the electron transport layer 6d in a broad sense. The hole blocking layer is made of a hole blocking material that has a function of transporting electrons but has a very small ability to transport holes, and recombines electrons and holes by blocking holes while transporting electrons. Probability can be improved. Moreover, the structure of the electron carrying layer 6d can be used as a hole-blocking layer as needed. The hole blocking layer is preferably provided adjacent to the light emitting layer 6c.

  On the other hand, the electron blocking layer has the function of the hole transport layer 6b in a broad sense. The electron blocking layer is made of a material that has a function of transporting holes but has a very small ability to transport electrons. By blocking holes while transporting holes, the electron recombination probability is improved. Can be made. Moreover, the structure of the positive hole transport layer 6b can be used as an electron blocking layer as needed. The thickness of the hole blocking layer is preferably in the range of 3 to 100 nm, and more preferably in the range of 5 to 30 nm.

[Sealing member]
The sealing member 10 covers the organic EL element, and may be a plate-like (film-like) sealing member that is fixed to the resin substrate 1 side by the adhesive 11. It may be a stop film. Such a sealing member 10 is provided in a state in which the terminal portions of the transparent electrode 5 and the counter electrode 7 in the organic EL element are exposed and at least the light emitting unit 6 is covered. Moreover, an electrode may be provided on the sealing member 10 so that the transparent electrode 5 and the terminal portion of the counter electrode 7 of the organic EL element are electrically connected to this electrode.

  Specific examples of the plate-like (film-like) sealing member 10 include a glass substrate, a polymer substrate, a metal substrate, and the like. These substrate materials may be used in the form of a thin film. Examples of the glass substrate include soda lime glass, barium / strontium-containing glass, lead glass, aluminosilicate glass, borosilicate glass, barium borosilicate glass, and quartz. Examples of the polymer substrate include polycarbonate, acrylic, polyethylene terephthalate, polyether sulfide, and polysulfone. Examples of the metal substrate include those made of one or more metals or alloys selected from the group consisting of stainless steel, iron, copper, aluminum, magnesium, nickel, zinc, chromium, titanium, molybdenum, silicon, germanium, and tantalum.

  Among them, since the element can be thinned, a thin film-like polymer substrate or metal substrate can be preferably used as the sealing member.

Furthermore, the polymer substrate in the form of a film has an oxygen permeability measured by a method according to JIS K 7126-1987 of 1 × 10 ⁻³ ml / (m ² · 24 h · atm) or less, JIS K 7129-1992. The water vapor permeability (25 ± 0.5 ° C., relative humidity (90 ± 2)% RH) measured by a method based on the above is 1 × 10 ⁻³ g / (m ² · 24 h) or less. It is preferable.

  Further, the above substrate material may be processed into a concave plate shape and used as the sealing member 10. In this case, the substrate member described above is subjected to processing such as sandblasting and chemical etching to form a concave shape.

  The adhesive 11 for fixing the plate-shaped sealing member 10 to the resin base material 1 side seals the organic EL element sandwiched between the sealing member 10 and the resin base material 1. It is used as a sealing agent. Specifically, such an adhesive 11 is a photocuring and thermosetting adhesive having a reactive vinyl group of an acrylic acid-based oligomer, a methacrylic acid-based oligomer, a moisture-curing type such as 2-cyanoacrylic acid ester, or the like. Can be mentioned.

  Moreover, as such an adhesive agent 11, heat | fever and chemical curing types (two-component mixing), such as an epoxy type, can be mentioned. Moreover, hot-melt type polyamide, polyester, and polyolefin can be mentioned. Moreover, a cationic curing type ultraviolet curing epoxy resin adhesive can be mentioned.

  In addition, the organic material which comprises an organic EL element may deteriorate with heat processing. For this reason, the adhesive 11 is preferably one that can be adhesively cured from room temperature (25 ° C.) to 80 ° C. A desiccant may be dispersed in the adhesive 11.

  Application | coating of the adhesive agent 11 to the adhesion part of the sealing member 10 and the resin base material 1 may use a commercially available dispenser, and may print like screen printing.

  Further, when a gap is formed between the plate-shaped sealing member 10, the resin base material 1, and the adhesive 11, in this gap, in the gas phase and the liquid phase, an inert gas such as nitrogen or argon, It is preferable to inject an inert liquid such as fluorinated hydrocarbon or silicon oil. A vacuum can also be used. Moreover, a hygroscopic compound can also be enclosed inside.

  Examples of the hygroscopic compound include metal oxides (for example, sodium oxide, potassium oxide, calcium oxide, barium oxide, magnesium oxide, aluminum oxide) and sulfates (for example, sodium sulfate, calcium sulfate, magnesium sulfate, cobalt sulfate). Etc.), metal halides (eg calcium chloride, magnesium chloride, cesium fluoride, tantalum fluoride, cerium bromide, magnesium bromide, barium iodide, magnesium iodide etc.), perchloric acids (eg perchloric acid) Barium, magnesium perchlorate, and the like), and anhydrous salts are preferably used in sulfates, metal halides, and perchloric acids.

  On the other hand, when a sealing film is used as the sealing member 10, the resin base material is completely covered with the light emitting unit 6 in the organic EL element and the terminal portions of the transparent electrode 5 and the counter electrode 7 in the organic EL element are exposed. 1 is provided with a sealing film.

  Such a sealing film is configured using an inorganic material or an organic material. In particular, it is made of a material having a function of suppressing intrusion of a substance that causes deterioration of the light emitting unit 6 in the organic EL element, such as moisture and oxygen. As such a material, for example, inorganic materials such as silicon oxide, silicon dioxide, and silicon nitride are used. Furthermore, in order to improve the brittleness of the sealing film, a laminated structure may be formed by using a film made of an organic material together with a film made of these inorganic materials.

  The method for forming these films is not particularly limited. For example, vacuum deposition method, sputtering method, reactive sputtering method, molecular beam epitaxy method, cluster ion beam method, ion plating method, plasma polymerization method, atmospheric pressure plasma A polymerization method, a plasma CVD method, a laser CVD method, a thermal CVD method, a coating method, or the like can be used.

[Protective film, protective plate]
In addition, although illustration is abbreviate | omitted here, you may provide a protective film or a protection board on both sides of the organic EL element and the sealing member 10 between the resin base materials 1. FIG. This protective film or protective plate is for mechanically protecting the organic EL element, and in particular, when the sealing member 10 is a sealing film, mechanical protection for the organic EL element is not sufficient. Therefore, it is preferable to provide such a protective film or protective plate.

  As the above protective film or protective plate, a glass plate, a polymer plate, a polymer film thinner than this, a metal plate, a metal film thinner than this, a polymer material film or a metal material film is applied. Among these, it is particularly preferable to use a polymer film because it is lightweight and thin.

[Method of manufacturing organic EL element]
Here, as an example, a method for manufacturing the organic EL element shown in FIG. 1 will be described.

  First, the first gas barrier layer 2a is formed on the resin substrate 1 by a plasma chemical vapor deposition method, a polysilazane-containing liquid is applied on the first gas barrier layer 2a, and modified by irradiation with vacuum ultraviolet rays. A two-gas barrier layer 2b is formed.

Next, a resin material solution in which light scattering particles having an average particle diameter of 0.2 μm or more are dispersed is applied to form the light scattering layer 3. Next, the smoothing layer 4 is formed on the light scattering layer 3 by a dry process or a wet process.
Further, a cap layer 12 containing silicon nitride as a main component is formed on the smoothing layer 4 by a dry process.

Next, on the cap layer 12, for example, an underlayer 5a made of a compound containing a nitrogen atom is deposited by an appropriate method such as an evaporation method so as to have a layer thickness of 1 μm or less, preferably 10 to 100 nm. Form.
Next, the conductive layer 5b made of silver (or an alloy containing silver as a main component) is formed on the base layer 5a by an appropriate method such as vapor deposition so that the layer thickness is 12 nm or less, preferably 4 to 9 nm. A transparent electrode 5 is formed to be an anode. At the same time, an extraction electrode 8 connected to an external power source is formed at the end of the transparent electrode 5 by an appropriate method such as a vapor deposition method.

Next, a hole injection layer 6 a, a hole transport layer 6 b, a light emitting layer 6 c, an electron transport layer 6 d, and an electron injection layer 6 e are formed thereon in this order to form the light emitting unit 6. As a film forming method of each of these layers, there are a spin coat method, a cast method, an ink jet method, a vapor deposition method, a printing method, etc., but from the point that a uniform film is easily obtained and pinholes are difficult to generate, etc. Vacuum deposition or spin coating is particularly preferred. Further, different film formation methods may be applied for each layer. When employing a vapor deposition method for forming each of these layers, the vapor deposition conditions vary depending on the type of compound used, but generally a boat heating temperature of 50 to 450 ° C. and a degree of vacuum of 1 × 10 ⁻⁶ to 1 × 10 ^−2. It is desirable to appropriately select each condition within the ranges of Pa, vapor deposition rate of 0.01 to 50 nm / second, substrate temperature of −50 to 300 ° C., and layer thickness of 0.1 to 5 μm.

  After the light emitting unit 6 is formed as described above, the counter electrode 7 serving as a cathode (cathode) is formed thereon by an appropriate film forming method such as a vapor deposition method or a sputtering method. At this time, the counter electrode 7 is patterned in a shape in which a terminal portion is drawn from the upper side of the light emitting unit 6 to the periphery of the resin base material 1 while being kept insulated from the transparent electrode 5 by the light emitting unit 6. Thereby, an organic EL element is obtained. After that, a sealing member 10 that covers at least the light emitting unit 6 to the light scattering layer 3 is provided in a state where the terminal portions of the transparent electrode 5 (extraction electrode 8) and the counter electrode 7 in the organic EL element are exposed. .

  As described above, a desired organic EL element is obtained on the resin substrate 1. In the production of such an organic EL element, it is preferable that the light emitting unit 6 is consistently produced from the light emitting unit 6 to the counter electrode 7 by a single evacuation, but different film formation is performed by taking out the resin substrate 1 from the vacuum atmosphere in the middle. You may apply the law. At that time, it is necessary to consider that the work is performed in a dry inert gas atmosphere.

  When a DC voltage is applied to the organic EL element thus obtained, the voltage of about 2 to 40 V is applied with the transparent electrode 5 serving as the anode having a positive polarity and the counter electrode 7 serving as the cathode having a negative polarity. When applied, light emission can be observed. An alternating voltage may be applied. The alternating current waveform to be applied may be arbitrary.

[Effect of organic EL element]
The organic EL element of the above-described embodiment includes a cap layer made of silicon nitride as a light extraction layer between the light scattering layer and the light emitting unit. The cap layer can prevent impurities from entering the light emitting unit from the light scattering layer or the smoothing layer. For this reason, the reliability and storability of the organic EL element can be improved.
In addition, since the outgas amount from the laminate of the resin base material, the light scattering layer, the smoothing layer, and the cap layer is 0.2 mg / m ² or less, the generation of impurities that adversely affect the light emitting unit is reduced. The influence on the storage stability of the organic EL element is very small.
Therefore, by providing the cap layer, there is no adverse effect on the light emitting unit by the light extraction layer, so that both improvement in light extraction efficiency by the light scattering structure and improvement in storage stability of the organic EL element can be achieved.
Further, by using the above-described substrate having the light scattering layer, the smoothing layer, and the cap layer on the resin base material, the light extraction effect is very small, so that the light extraction is performed. A light-emitting device that achieves both improved efficiency and improved storage stability can be configured.

[Uses of organic EL elements]
Since the organic EL elements having the above-described configurations are surface light emitters as described above, they can be used as various light emission sources. For example, lighting devices such as home lighting and interior lighting, backlights for clocks and liquid crystals, lighting for billboard advertisements, light sources for traffic lights, light sources for optical storage media, light sources for electrophotographic copying machines, light sources for optical communication processors, Examples include, but are not limited to, a light source of an optical sensor, and can be effectively used as a backlight of a liquid crystal display device combined with a color filter and a light source for illumination.

  The organic EL element may be used as a kind of lamp such as an illumination or exposure light source, a projection device that projects an image, or a display device that directly recognizes a still image or a moving image. (Display) may be used. In this case, with the recent increase in the size of lighting devices and displays, the light emitting surface may be enlarged by so-called tiling, in which light emitting panels provided with organic EL elements are joined together in a plane.

  The driving method when used as a display device for moving image reproduction may be either a simple matrix (passive matrix) method or an active matrix method. In addition, a color or full-color display device can be manufactured by using two or more organic EL elements having different emission colors.

  Hereinafter, a lighting device will be described as an example of the application, and then a lighting device in which the light emitting surface is enlarged by tiling will be described.

[Lighting device]
The organic EL element can be applied to a lighting device.

  The lighting device using the organic EL element may be designed such that each organic EL element having the above-described configuration has a resonator structure. Examples of the purpose of use of the organic EL element configured as a resonator structure include, but are not limited to, a light source of an optical storage medium, a light source of an electrophotographic copying machine, a light source of an optical communication processor, a light source of an optical sensor, and the like. . Moreover, you may use for the said use by making a laser oscillation.

  Note that the material used for the organic EL element can be applied to an organic EL element that emits substantially white light (also referred to as a white organic EL element). For example, a plurality of light emitting materials can simultaneously emit a plurality of light emission colors to obtain white light emission by color mixing. As a combination of a plurality of emission colors, those containing the three emission maximum wavelengths of the three primary colors of red, green and blue may be used, or two emission using the complementary colors such as blue and yellow, blue green and orange, etc. It may contain a maximum wavelength.

  In addition, a combination of light emitting materials for obtaining a plurality of emission colors is a combination of a plurality of phosphorescent or fluorescent materials, a light emitting material that emits fluorescence or phosphorescence, and excitation of light from the light emitting materials. Any combination with a pigment material that emits light as light may be used, but in a white organic EL element, a combination of a plurality of light-emitting dopants may be used.

  Such a white organic EL element is different from a configuration in which organic EL elements each emitting light are individually arranged in parallel in an array to obtain white light emission, and the organic EL element itself emits white light. For this reason, a mask is not required for film formation of most layers constituting the element, and deposition can be performed on one side by vapor deposition, casting, spin coating, ink jet, printing, etc., and productivity is also improved. To do.

  Moreover, there is no restriction | limiting in particular as a light emitting material used for the light emitting layer of such a white organic EL element, For example, if it is a backlight in a liquid crystal display element, it will fit in the wavelength range corresponding to CF (color filter) characteristic. As described above, any one of the above-described metal complexes and known light-emitting materials may be selected and combined to be whitened.

  If the white organic EL element demonstrated above is used, it is possible to produce the illuminating device which produces substantially white light emission.

  EXAMPLES Hereinafter, the present invention will be specifically described with reference to examples, but the present invention is not limited thereto. In addition, although the display of "%" is used in an Example, unless otherwise indicated, "mass%" is represented.

[Production of Organic EL Element 101]
(1) Production of Substrate (1-1) Film Base As a film base, a biaxially stretched polyethylene naphthalate film (PEN film, thickness: 100 μm, width: 350 mm, manufactured by Teijin DuPont Films Ltd., trade name “ Teonex Q65FA ") was used.

(1-2) Preparation of primer layer Wire is applied so that the layer thickness after application and drying of UV curable organic / inorganic hybrid hard coat material OPSTAR Z7501 manufactured by JSR Corporation is 4 μm on the easy adhesion surface of the film substrate. After coating with a bar, drying conditions: 80 ° C., drying at 3 minutes, and then using a high-pressure mercury lamp in an air atmosphere and curing conditions: 1.0 J / cm ² to form a primer layer.

(1-3) Production of first gas barrier layer A film base material is attached to a CVD apparatus, and each element profile shown in FIG. 6 is formed on the film base material under the following film forming conditions (plasma CVD conditions). A first gas barrier layer was prepared with a layer thickness of 300 nm.

<Film forming conditions>
Feed rate of raw material gas (hexamethyldisiloxane (HMDSO, (CH ₃ ) ₆ SiO)): 50 sccm (Standard Cubic Centimeter per Minute)
Supply amount of oxygen gas (O ₂ ): 500 sccm
Degree of vacuum in the vacuum chamber: 3Pa
Applied power from the power source for plasma generation: 0.8 kW
Frequency of power source for plasma generation: 80 kHz
Film conveyance speed: 0.5 to 1.66 m / min

(1-4) Production of Second Gas Barrier Layer A 10 mass% dibutyl ether solution of perhydropolysilazane (PHPS) (Aquamica NN120-10, non-catalytic type, manufactured by AZ Electronic Materials Co., Ltd.) was used as the coating solution.
The coating solution is applied with a wire bar so that the (average) layer thickness after drying is 300 nm, dried by treatment for 1 minute in an atmosphere at a temperature of 85 ° C. and a humidity of 55% RH, and further at a temperature of 25 The polysilazane layer was formed by holding for 10 minutes in an atmosphere of 10 ° C. and humidity of 10% RH (dew point temperature −8 ° C.) to perform dehumidification.
Subsequently, the polysilazane layer formed above was subjected to a silica conversion treatment under atmospheric pressure using the following ultraviolet irradiation apparatus.

<Ultraviolet irradiation device>
Apparatus: Ex D irradiation apparatus MODEL MECL-M-1-200 manufactured by M.D.
Irradiation wavelength: 172 nm
Lamp filled gas: Xe

<Reforming treatment conditions>
The base material on which the polysilazane layer fixed on the operation stage was formed was modified under the following conditions to form a second gas barrier layer.

Excimer lamp light intensity: 130 mW / cm ² (172 nm)
Distance between sample and light source: 1mm
Stage heating temperature: 70 ° C
Oxygen concentration in the irradiation device: 1.0%
Excimer lamp irradiation time: 5 seconds

The substrate produced as described above had a water vapor permeability of less than 1 × 10 ⁻⁴ g / (m ² · 24 h), and exhibited very good water vapor barrier performance.
In this example, the water vapor permeability is a value measured at a temperature of 25 ± 0.5 ° C. and a relative humidity of 90 ± 2% RH by a method based on JIS K 7129-1992.

(2) Production of Transparent Electrode The produced substrate was cut into a size of 5 cm × 5 cm and fixed to a substrate holder of a commercially available vacuum deposition apparatus, and the exemplified compound (1-6) was placed in a tantalum resistance heating boat. These substrate holder and resistance heating boat were attached to the first vacuum chamber of the vacuum evaporation apparatus. Moreover, silver (Ag) was put into the resistance heating boat made from tungsten, and it attached in the 2nd vacuum chamber.

Next, after depressurizing the first vacuum tank to 4 × 10 ⁻⁴ Pa, the resistance heating boat containing the exemplary compound (1-6) was energized and heated, and the deposition rate was 0.1 to 0.2 nm / A base layer of a transparent electrode made of the exemplary compound (1-6) was formed on the substrate within a range of seconds. The layer thickness of the underlayer was 50 nm.

Next, the substrate formed up to the base layer was transferred to a second vacuum chamber under vacuum. After depressurizing the second vacuum tank to 4 × 10 ⁻⁴ Pa, the resistance heating boat containing silver is energized and heated, and the deposition rate is 0.1 to 0.2 nm / sec. A conductive layer made of silver having a layer thickness of 8 nm was formed, and a transparent electrode (anode) having a laminated structure of a base layer and a conductive layer was formed.

(3) Production of organic functional layer The crucible for vapor deposition in the vacuum vapor deposition apparatus was filled with the constituent material of each layer of the organic functional layer in an amount optimal for the production of the organic EL element. The evaporation crucible used was made of a resistance heating material such as molybdenum or tungsten.

  As the constituent material of each layer of the organic functional layer, the following compounds α-NPD, BD-1, GD-1, RD-1, H-1, H-2, and E-1 were used.

First, the pressure is reduced to a vacuum degree of 1 × 10 ⁻⁴ Pa, the deposition crucible filled with the compound α-NPD is energized and heated, and deposited on the transparent electrode at a deposition rate of 0.1 nm / second, A hole injection transport layer having a layer thickness of 40 nm was formed.

Similarly, the compounds BD-1 and H-1 are co-evaporated at a deposition rate of 0.1 nm / second so that the concentration of the compound BD-1 is 5%, and a fluorescent light-emitting layer exhibiting a blue color with a layer thickness of 15 nm Formed.
Next, the compounds GD-1, RD-1, and H-2 were deposited at 0.1 nm / second so that the concentration of the compound GD-1 was 17% and the concentration of the compound RD-1 was 0.8%. Co-evaporation was carried out at a speed to form a phosphorescent light emitting layer having a layer thickness of 15 nm and exhibiting yellow.

  Thereafter, Compound E-1 was deposited at a deposition rate of 0.1 nm / second to form an electron transport layer having a layer thickness of 30 nm.

(4) Production of counter electrode Further, lithium fluoride (LiF) was formed at a layer thickness of 1.5 nm, and aluminum 110 nm was evaporated to form a counter electrode (cathode). The counter electrode was formed in a shape in which the terminal portion was drawn to the periphery of the substrate in a state where it was insulated by the organic functional layer from the hole injection layer to the electron injection layer.

  In addition, a vapor deposition mask is used for the formation of each layer, and a 4.5 cm × 4.5 cm region located in the center of a 5 cm × 5 cm substrate is used as a light emitting region, and a width of 0.25 cm is formed on the entire circumference of the light emitting region. A non-light emitting area was provided.

(5) Sealing (5-1) Preparation of pressure-sensitive adhesive composition 100 parts by mass of Opanol B50 (manufactured by BASF, Mw: 340,000) as a polyisobutylene resin, and Nisseki polybutene grade HV-1900 as a polybutene resin (Shin Nippon Oil Co., Ltd.) 30 parts by mass, Mw: 1900), 0.5 parts by mass of TINUVIN 765 (manufactured by Ciba Japan, having a tertiary hindered amine group) as a hindered amine light stabilizer, and IRGANOX 1010 (Ciba. 0.5 parts by mass (made in Japan, both β-positions of hindered phenol groups have tertiary butyl groups), and Eastotac H-100L Resin (manufactured by Eastman Chemical Co.) as a cyclic olefin polymer 50 masses Part dissolved in toluene, solid content concentration about 25% by mass The pressure-sensitive adhesive composition was prepared.

(5-2) Preparation of pressure-sensitive adhesive sheet for sealing The above pressure-sensitive adhesive composition prepared using polyethylene terephthalate film Alpet 12/34 (produced by Asia Aluminum Co., Ltd.) on which aluminum (Al) was deposited as a gas barrier layer. The product solution was coated on the aluminum side (gas barrier layer side) so that the thickness of the pressure-sensitive adhesive layer formed after drying was 20 μm, and dried at 120 ° C. for 2 minutes to form a pressure-sensitive adhesive layer. Next, the release treatment surface of a polyethylene terephthalate film having a thickness of 38 μm was applied as a release sheet to the pressure-sensitive adhesive layer surface to prepare an adhesive sheet for sealing.

(5-3) Sealing The pressure-sensitive adhesive sheet for sealing produced by the method described above was removed for 10 minutes on a hot plate heated to 120 ° C. in a nitrogen atmosphere and then dried at room temperature (25 ° C. ), And then laminated so as to completely cover the cathode, and heated at 90 ° C. for 10 minutes. Thus, the organic EL element 101 was produced.

[Production of Organic EL Element 102]
In the organic EL element 101 described above, a light extraction layer composed of a light scattering layer and a smoothing layer described below was formed on the second gas barrier layer of the substrate, and an organic EL element 102 was produced.

(6) Production of Light Extraction Layer (6-1) Production of Light Scattering Layer TiO ₂ particles (JR600A manufactured by Teika Co., Ltd.) having a refractive index of 2.4 and an average particle size of 0.25 μm and a resin solution (ED230AL manufactured by APM) The solid content ratio with (organic / inorganic hybrid resin) was 20 vol% / 80 vol%, and the solid content concentration in propylene glycol monomethyl ether (PGME) was 15 mass%.
To the solid content (effective mass component), 0.4% by mass of an additive (Disperbyk-2096 manufactured by Big Chemie Japan Co., Ltd.) was added and the formulation was designed at a ratio of 10 ml.

Specifically, the the TiO ₂ particles and a solvent and additives were mixed with 10% by weight ratio with respect to TiO ₂ particles, while cooling at room temperature (25 ° C.), an ultrasonic dispersing machine (manufactured by SMT Co. UH- 50) was added for 10 minutes under the standard conditions of the microchip step (MS-3 3 mmφ manufactured by SMT) to prepare a dispersion of TiO ₂ .
Next, while stirring the TiO ₂ dispersion at 100 rpm, the resin solution is mixed and added little by little. After the addition is completed, the stirring speed is increased to 500 rpm and mixing is performed for 10 minutes, and then a hydrophobic PVDF 0.45 μm filter (manufactured by Whatman) ) To obtain the desired scattering layer coating solution.

  After applying the coating solution on the second gas barrier layer of the substrate by the inkjet coating method, it is simply dried (80 ° C., 2 minutes), and further, the output condition is that the substrate temperature is less than 80 ° C. by the wavelength control IR described later. The drying process was performed for 5 minutes.

  Next, the curing reaction was accelerated under the following modification treatment conditions to obtain a light scattering layer having a layer thickness of 0.3 μm. In this way, a light scattering layer having a refractive index n of 1.66 was produced.

<Modification processing equipment>
Apparatus: Ex D irradiation apparatus MODEL MEIRH-M-1-200-222-H-KM-G manufactured by M.D.
Wavelength: 222nm
Lamp filled gas: KrCl

<Reforming treatment conditions>
Excimer light intensity: 8 J / cm ² (222 nm)
Stage heating temperature: 60 ° C
Oxygen concentration in the irradiation device: Air

(6-2) Production of smoothing layer Next, as a coating solution for the smoothing layer, a high refractive index UV curable resin (manufactured by Toyo Ink Co., Ltd., Rioduras TYT82-01, nanosol particles: TiO ₂ ), The solid content concentration in an organic solvent in which the solvent ratio of propylene glycol monomethyl ether (PGME) and 2-methyl-2,4-pentanediol (PD) is 90% by mass / 10% by mass is 12% by mass. The formulation was designed at a ratio of 10 ml.

Specifically, the high refractive index UV curable resin and the solvent are mixed, mixed at 500 rpm for 1 minute, and then filtered through a hydrophobic PVDF 0.2 μm filter (manufactured by Whatman) for the intended smoothing layer. A coating solution was obtained.
After applying the above coating solution on the scattering layer by the inkjet coating method, simple drying (80 ° C., 2 minutes), and further performing a drying process for 5 minutes under an output condition with a substrate temperature of less than 80 ° C. by wavelength control IR. did.

The drying process was performed by attaching two quartz glass plates that absorb infrared rays having a wavelength of 3.5 μm or more to an IR irradiation device (ultimate heater / carbon, manufactured by Meidyo Kogyo Co., Ltd.) using a wavelength-controlled infrared heater. Flowing cooling air between the plates).
At this time, the cooling air was set at 200 L / min, and the tube surface quartz glass temperature was suppressed to less than 120 ° C. The substrate temperature was measured by placing K thermocouples on the upper and lower surfaces of the substrate and 5 mm from the upper surface of the substrate and connecting them to NR2000 (manufactured by Keyence Corporation).

  Next, the curing reaction was promoted under the following modification treatment conditions, a smoothing layer having a layer thickness of 0.5 μm was formed, and a light extraction layer having a two-layer structure of a light scattering layer and a smoothing layer was produced.

<Modification processing equipment>
Apparatus: Ex D irradiation apparatus MODEL MEIRH-M-1-200-222-H-KM-G manufactured by M.D.
Wavelength: 222nm
Lamp filled gas: KrCl

<Reforming treatment conditions>
Excimer light intensity: 8 J / cm ² (222 nm)
Stage heating temperature: 60 ° C
Oxygen concentration in the irradiation device: Air

  The organic EL element 102 was produced as described above.

[Production of Organic EL Element 103]
In the above-mentioned organic EL element 102, the following cap layer was provided on the smoothing layer of the substrate to form a light extraction layer, and the organic EL element 103 was produced.

(7) Production of Cap Layer First, a substrate on which a smoothing layer was formed was mounted in the chamber of a magnetron sputtering apparatus (manufactured by Anelva, SPF-730H). Next, the inside of the chamber of the magnetron sputtering apparatus was depressurized to an ultimate vacuum of 3.0 × 10 ⁻⁴ Pa with an oil rotary pump and a cryopump. Using Si as a target, introducing 10 sccm of argon gas and 3 sccm of oxygen gas, applying high-frequency power with a frequency of 13.56 MHz (input power of 1.2 kW), and smoothing at a film-forming pressure of 0.4 Pa and a film thickness of 80 nm A silicon dioxide film was formed on the layer. A film having a refractive index n of 1.47 was obtained. Thus, the organic EL element 103 was produced.

[Production of Organic EL Element 104]
An organic EL element 104 was produced in the same manner as the organic EL element 103 except that the cap layer of the organic EL element 103 was changed as follows.

A substrate on which a smoothing layer was formed was mounted in the chamber of a magnetron sputtering apparatus (manufactured by Anelva, SPF-730H). Next, the inside of the chamber of the magnetron sputtering apparatus was depressurized to an ultimate vacuum of 3.0 × 10 ⁻⁴ Pa with an oil rotary pump and a cryopump. Si is used as a target, argon gas 10 sccm, oxygen gas 1.4 sccm, and nitrogen gas 17.5 sccm are introduced, high-frequency power with a frequency of 13.56 MHz (input power 1.2 kW) is applied, and the deposition pressure is set to 0. A silicon oxynitride film was formed on the smoothing layer at 4 Pa and a film thickness of 80 nm. A film having a refractive index n of 1.48 was obtained. Thus, the organic EL element 104 was produced.

[Production of Organic EL Element 105]
An organic EL element 105 was produced in the same manner as the organic EL element 103 except that the cap layer of the organic EL element 103 was changed as follows.

A substrate on which a smoothing layer was formed was mounted in the chamber of a magnetron sputtering apparatus (manufactured by Anelva, SPF-730H). Next, the inside of the chamber of the magnetron sputtering apparatus was depressurized to an ultimate vacuum of 3.0 × 10 ⁻⁴ Pa with an oil rotary pump and a cryopump. Niobium oxide (NbOx) is used as a target, argon gas 20 sccm and oxygen gas 3.3 sccm are introduced, high-frequency power with a frequency of 13.56 MHz (input power 1.2 kW) is applied, and a deposition pressure of 0. A niobium oxide film was formed on the smoothing layer at 4 Pa and a film thickness of 80 nm. A film having a refractive index n of 2.34 was obtained. Thus, the organic EL element 105 was produced.

[Production of Organic EL Element 106]
An organic EL element 106 was produced in the same manner as the organic EL element 103 except that the cap layer of the organic EL element 103 was changed as follows.

A substrate on which a smoothing layer was formed was mounted in the chamber of a magnetron sputtering apparatus (manufactured by Anelva, SPF-730H). Next, the inside of the chamber of the magnetron sputtering apparatus was depressurized to an ultimate vacuum of 3.0 × 10 ⁻⁴ Pa with an oil rotary pump and a cryopump. Si is used as a target, argon gas 7 sccm and nitrogen gas 26 sccm are introduced, high-frequency power with a frequency of 13.56 MHz (input power 1.2 kW) is applied, and the film formation pressure is 0.4 Pa and the film thickness is 80 nm. A silicon nitride film was formed on the activated layer. A film having a refractive index n of 1.75 was obtained. Thus, the organic EL element 106 was produced.

[Production of Organic EL Element 107]
An organic EL element 107 was produced in the same manner as the organic EL element 106 except that the cap layer of the organic EL element 106 was changed as follows.
Film formation was performed by changing the film thickness of silicon nitride from 80 nm to 300 nm.

[Production of Organic EL Element 108]
An organic EL element 108 was produced in the same manner as the organic EL element 107 except that the cap layer of the organic EL element 107 was changed as follows.
Si was used as a target in a magnetron sputtering apparatus, argon gas 7 sccm and nitrogen gas 18 sccm were introduced, and a silicon nitride film was formed on the smoothing layer with a film thickness of 300 nm. A film having a refractive index n of 2.53 was obtained. Thus, the organic EL element 108 was produced.

[Production of Organic EL Element 109]
An organic EL element 109 was produced in the same manner as the organic EL element 107 except that the cap layer of the organic EL element 107 was changed as follows.
Si was used as a target in a magnetron sputtering apparatus, argon gas 7 sccm and nitrogen gas 25 sccm were introduced, and a silicon nitride film was formed on the smoothing layer with a film thickness of 300 nm. A film having a refractive index n of 1.91 was obtained. Thus, the organic EL element 109 was produced.

[Production of Organic EL Element 110]
An organic EL element 110 was produced in the same manner as the organic EL element 109 except that the cap layer of the organic EL element 109 was changed as follows.
The film formation time for the sputtering treatment was 1.5 times. Thus, the organic EL element 109 was produced.

[Production of Organic EL Element 111]
An organic EL element 111 was produced in the same manner as the organic EL element 103 except that the cap layer of the organic EL element 103 was changed as follows.

Using a parallel plate type plasma CVD apparatus (manufactured by Anelva, PED-401), the substrate on which the smoothing layer was formed was mounted on the lower electrode side of the chamber of the plasma CVD apparatus. Next, the chamber of the plasma CVD apparatus was decompressed to an ultimate vacuum of 1.0 × 10 ⁻² Pa by an oil rotary pump and a turbo molecular pump. Thereafter, SiH ₄ gas, NH ₃ gas, H ₂ gas, and N ₂ gas were introduced into the chamber via the raw material supply nozzle. The pressure adjusting valve between the chamber and the vacuum pump was adjusted to adjust the pressure in the chamber to 20 Pa. Next, power having a frequency of 90 kHz (applied power: 200 W) is applied to the lower electrode, and between the lower electrode and the upper electrode (in the vicinity of the opening (gas inlet) of the raw material supply nozzle in the chamber), A glow discharge plasma was generated. Plasma treatment was performed for 3 minutes to form a cap layer having a layer thickness of 300 nm made of silicon nitride having a nitrogen ratio of 41%. A film having a refractive index n of 1.92 was obtained. Thus, the organic EL element 111 was produced.

[Production of Organic EL Element 112]
An organic EL element 112 was produced in the same manner as the organic EL element 111 except that the smoothing layer and cap layer of the organic EL element 111 were changed as follows.
As a smoothing layer coating solution, the high refractive index UV curable resin is changed from Rio Duras TYT82-01 (manufactured by Toyo Ink Co., Ltd.) to Rio Duras TYT92-01 (manufactured by Toyo Ink Co., Ltd.), and the cap layer Was made of silicon nitride having a nitrogen ratio of 46% and a thickness of 300 nm, and a refractive index n of 1.60 was obtained. Thus, the organic EL element 112 was produced.

[Production of Organic EL Element 113]
An organic EL element 113 was produced in the same manner as the organic EL element 111 except that the light scattering layer and the smoothing layer of the organic EL element 111 were replaced and formed.

[Production of Organic EL Element 114]
An organic EL element 114 was produced in the same manner as the organic EL element 111 except that the scattering layer of the organic EL element 111 was changed as follows.
As the composition of the light scattering layer, the solid content of TiO ₂ particles (JR600A manufactured by Teica Co., Ltd.) having a refractive index of 2.4 and an average particle size of 0.25 μm and a resin solution (ED230AL (organic / inorganic hybrid resin) manufactured by APM) The ratio was 5% by volume / 95% by volume, and the solid content concentration in propylene glycol monomethyl ether (PGME) was 15% by mass.
To the solid content (effective mass component), 0.4% by mass of an additive (Disperbyk-2096 manufactured by Big Chemie Japan Co., Ltd.) was added and the formulation was designed at a ratio of 10 ml. Thus, the organic EL element 114 was produced.

[Production of Organic EL Element 115]
An organic EL element 115 was produced in the same manner as the organic EL element 111 except that the scattering layer of the organic EL element 111 was changed as follows.
The film thickness of the light scattering layer was 400 nm. Thus, the organic EL element 115 was produced.

[Evaluation method]
(Outgas amount)
A base material having a size of 100 cm ² including the light extraction layer is finely cut and sealed in a vial. HS-GC / MS (Headspace-Gas Chromatography / Mass Spectrometry) was used, and J & W Scientific DB-624 (30M × 0.25 mm ID) was used as a column. The vial was heated at 190 ° C. for 30 minutes, and the generated gas was injected into the column. The oven temperature started from 40 ° C., heated at 10 ° C./min, and heated to 230 ° C. The gas detected at that time was taken as outgas, and converted to the value of toluene set in advance as a reference to obtain the outgas amount. The amount of outgas was indicated by the amount per m ² , and 0.2 mg / m ² or less was accepted.

(Surface roughness (Ra))
The surface roughness (arithmetic average roughness Ra) is calculated from an uneven sectional curve continuously measured with a detector having a stylus having a minimum tip radius using an atomic force microscope (manufactured by Digital Instruments). Measurement was performed three times in a section having a measurement direction of 30 μm with a stylus having a tip radius, and the average roughness related to the amplitude of fine irregularities was obtained.

(Refractive index (n))
The refractive index of the smoothing layer and the cap layer was measured using a spectroscopic ellipsometer (alpha-SE) manufactured by JA Woollam Japan. Measurements were made with a film thickness of about 100 nm. The measurement wavelength was 633 nm.
The light scattering layer is a mixed opaque film and cannot be measured with a spectroscopic ellipsometer. Therefore, as the refractive index of the light scattering layer, a calculated refractive index calculated by a total value obtained by multiplying a refractive index specific to each material by a mixing ratio is used.

(Haze)
It measured using the Nippon Denshoku Industries Co., Ltd. make and a haze meter (NDH5000). The value of the base material formed up to the cap layer was measured with the setting conforming to ISO14782.

(Film thickness)
It measured using the stylus type surface shape measuring apparatus (Dektak XT) made from BRUKER. The stylus type was 12.5 μm, the stylus force was 5 mg, and the resolution was 0.666 μm / pt. In the film thickness measurement, the light scattering layer, the smoothing layer, and the cap layer were each formed as a single film on the substrate, and a portion where a part of the film was removed was measured, and this thickness was defined as the film thickness.

(Luminescence efficiency)
With respect to each produced organic EL element, lighting was performed under a constant current density condition of ^2.5 mA / cm ² at room temperature (25 ° C.), and using a spectral radiance meter CS-2000 (manufactured by Konica Minolta), The light emission luminance of each organic EL element was measured, and the light emission efficiency (power efficiency) at the current value was determined.
The luminous efficiency was expressed as a relative value with the luminous efficiency of the organic EL element 101 as 100. A relative light emission efficiency of 120 or more was accepted.

(Storability)
Each organic EL element was put into an 85 ° C. (dry) thermostat, and the voltage increase rate before and after storage at the same constant current density as in the above-described luminous efficiency evaluation was evaluated every 24 hours. A voltage increase exceeding 1.0 V from the beginning of the evaluation was made unacceptable, and the period up to which the voltage was made unusable was defined as storability.

As is clear from Table 1, the organic EL elements 106 to 115 each having a cap layer made of silicon nitride and having an outgas amount of 0.2 mg / m ² or less have no light extraction layer. Compared to 101, power efficiency is improved. Further, the storage stability is greatly improved as compared with the organic EL element 102 having no cap layer.

  In addition, as compared with the organic EL elements 106 to 110 in which the cap layer is formed using a magnetron sputtering apparatus, the organic EL elements 111 to 115 in which the cap layer is formed using a plasma CVD apparatus has improved storability as a whole. ing. By forming a dense layer using the plasma CVD method, it is considered that impurities such as moisture from the light extraction layer can be prevented from entering, and the storage stability is improved.

The organic EL element 103 and the organic EL element 105 whose cap layers are silicon oxide or niobium oxide have extremely low storage stability compared to the organic EL elements 106 to 115 using silicon nitride as a cap layer. From this result, it can be seen that the storage stability is improved by using nitride for the cap layer.
The organic EL element 102 has a light scattering layer, and thus has higher power efficiency than the organic EL element 101. However, since the amount of outgas from the light scattering layer or the like is large, the storage stability is greatly reduced.

  The organic EL element 107 with a cap layer of 300 nm has improved storage stability compared to the organic EL element 106 with a cap layer of 80 nm. This is because the gas barrier property is improved by forming the cap layer thick. Further, there is almost no difference in power efficiency between the two organic EL elements. For this reason, even when the cap layer is formed to a thickness of about 300 nm in order to improve the gas barrier property, there is almost no optical influence.

The organic EL element 109 and the organic EL element 110 have a refractive index of the cap layer of about 1.9, an organic EL element 107 having a refractive index of the cap layer of 1.75, and a refractive index of the cap layer of about 2.5. Compared with the organic EL element 108, the power efficiency is improved. Since the refractive index is in the order of increasing in the order of the resin base material, the light scattering layer, the smoothing layer, and the cap layer, and the refractive index of the cap layer is 1.8 to 2.5, the light extraction efficiency Therefore, the power efficiency of the organic EL element is improved.
Similarly, the organic EL element 111 has an order in which the refractive index increases in the order of the resin base material, the light scattering layer, the smoothing layer, and the cap layer, and the refractive index of the cap layer is 1.8 to 2.5. Therefore, the power efficiency is better than that of an organic EL element having another configuration, for example, an organic EL element 112 having a cap layer having a refractive index of 1.60.

  Even when the light scattering layer and the smoothing layer are interchanged as in the organic EL element 113, the cap layer ensures flatness and gas barrier properties, so that both power efficiency and storage stability are good. was gotten.

  In the organic EL element 114 having a haze value of 47% and the organic EL element 115 having a haze value of 78%, the power efficiency is lower than that of the organic EL element 111 having a haze value of 63%. This is because the light extraction efficiency of the organic EL element is lowered due to the haze value being too high or too low. From this result, by setting the haze value to 50 to 75%, the light extraction efficiency of the organic EL element is improved, and the power efficiency of the organic EL element is improved.

  The present invention is not limited to the configuration described in the above-described embodiment, and various modifications and changes can be made without departing from the configuration of the present invention.

  DESCRIPTION OF SYMBOLS 1 Resin base material, 2 Gas barrier layer, 2a 1st gas barrier layer, 2b 2nd gas barrier layer, 3 Light scattering layer, 4 Smoothing layer, 12 Cap layer, 5 Transparent electrode, 5a Underlayer, 5b Conductive layer, 6 Light emitting unit , 6a hole injection layer, 6b hole transport layer, 6c light emitting layer, 6d electron transport layer, 6e electron injection layer, 7 counter electrode, 8 take-out electrode, 9 auxiliary electrode, 10 sealing member, 11 adhesive, 20 delivery Roller, 21, 22, 23, 24 Transport roller, 25 Winding roller, 31, 32 Film forming roller, 41 Gas supply port, 51 Power source for plasma generation, 61, 62 Magnetic field generator, A oxygen distribution curve, B silicon distribution Curve, C carbon distribution curve, local maximum of X, Y oxygen atomic ratio

Claims (8)

A resin substrate;
A gas barrier layer provided on the resin substrate;
A light scattering layer provided on the gas barrier layer;
A smoothing layer provided on the light scattering layer;
A cap layer mainly composed of silicon nitride provided on the smoothing layer;
A light emitting unit composed of an organic functional layer sandwiched between a pair of electrodes,
The organic electroluminescent element whose outgas amount emitted from the laminated body of the said resin base material, the said light-scattering layer, the said smoothing layer, and the said cap layer is 0.2 mg / m < ² > or less.   The organic electroluminescence device according to claim 1, wherein the cap layer has a refractive index of 1.8 to 2.5.   The organic electroluminescence device according to claim 1, wherein the cap layer has a surface roughness Ra of 0 nm or more and 3 nm or less.   The organic electroluminescence device according to claim 1, wherein the cap layer is formed by a plasma CVD method.   The refractive index of the resin base material, the light scattering layer, the smoothing layer, and the cap layer is smaller as the layer is closer to the resin base material, and the refractive index is higher as the layer is closer to the electrode. Organic electroluminescence element.   The surface roughness Ra of the said light-scattering layer, the said smoothing layer, and the said cap layer is so large that the layer close | similar to the said resin base material, and surface roughness Ra is small as the layer close | similar to the said electrode. Organic electroluminescence device.   The organic electroluminescence device according to claim 5 or 6, wherein the haze value is 50% or more and 75% or less. A resin substrate;
A light scattering layer provided on the resin substrate;
A smoothing layer provided on the light scattering layer;
A cap layer mainly composed of silicon nitride provided on the smoothing layer,
The amount of outgas emitted from the laminate of the resin base material, the light scattering layer, the smoothing layer, and the cap layer is 0.2 mg / m ² or less.

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