JP5427527B2 - Organic light emitting display device and method for manufacturing organic light emitting display device - Google Patents

Description

  The present invention relates to an organic light emitting display device and a method for manufacturing the organic light emitting display device.

  Various techniques for displaying in full color using organic electroluminescence have been disclosed. For example, Patent Document 1 discloses an OLED device for producing white light that more effectively matches the response of a multi-color filter in the OLED device. In this OLED device, the spectrum of white light is changed by two or more dopants contained in the organic EL element, and the white light is selected so as to more effectively match the response of the color filter. That is, in this OLED device, white light is efficiently emitted by adjusting the responsiveness of the color filter. However, with such a configuration, there is a problem that the control is complicated. In addition, there is a problem that the configuration is not optimal in order to further improve the optical characteristics by increasing the intensity of a specific wavelength.

  In order to solve such a problem, various techniques using a resonance structure that increases the intensity of a specific wavelength by adjusting the optical path length of each color or repeating light reflection and interference are disclosed.

  In Patent Document 2, direct output light that passes through a transparent sealing plate having a partial reflection function that protects an organic thin film and directly goes to the upper part, and light that returns to the element side once by reflection of the transparent sealing plate An organic light emitting display having a structure in which light is reflected by a reflective film such as a metal electrode and a total reflection mirror provided on the lower substrate side, and is emitted to the upper part of the transparent sealing plate in a separate optical path from the direct output light. An apparatus is disclosed. This document discloses that the optical distance is adjusted by providing a step for each color pixel on the insulating substrate side having the organic light emitting layer or inserting a spacer. With such a configuration, there is a problem that accuracy is required to adjust the optical distance. Further, since an insulating substrate having an organic light emitting layer is manufactured and further provided with a step, a spacer, etc., there is a problem that man-hours increase.

  Further, Patent Document 3 is a display element having a light emitting layer, having a resonator structure between a first end and a second end sandwiching the light emitting layer, and the first end and the light emitting layer. And a distance between the second end portion and the light emitting layer satisfy a predetermined mathematical formula. However, there is a problem that a specific structure is not disclosed.

Special table 2007-520060 gazette Japanese Patent No. 3898163 Japanese Patent No. 3770328

  An object of the present invention is to solve the above-described problems and achieve the following objects. That is, an object of the present invention is to provide an organic light emitting display device having good light emission characteristics, which can be manufactured by a simple method, has an increased intensity at a specific wavelength, and a method for manufacturing the organic light emitting display device. .

As a result of intensive studies to achieve the above object, the inventors of the present invention form an optical resonator between a light transmitting layer having a recess having a predetermined shape and a light reflecting electrode in which an organic EL layer is laminated. It has been found that the above-mentioned problems can be solved by configuring the present invention, and the present invention has been completed. That is,
<1> An organic light-emitting display device having a substrate, a light reflection electrode, an organic EL layer, a light transmission electrode, and a light transmission layer having a recess in this order,
An optical resonator is formed between the light reflecting electrode and the surface of the recess facing the light reflecting electrode,
In the organic light emitting display device, light transmitted from the light transmission layer through the optical resonator is light of at least one of red, green, and blue.
<2> The organic light-emitting display device according to <1>, wherein the light transmission layer is formed as a single member.
<3> The organic light-emitting display device according to <2>, wherein the material of one member is a photocurable resin, a thermoplastic resin, or a thermosetting resin.
<4> The organic light-emitting display device according to any one of <1> to <3>, wherein the light-transmitting layer includes a light semi-transmissive reflective layer on a concave surface.
<5> The organic light-emitting display device according to any one of <1> to <4>, wherein the refractive index of the concave portion of the light transmission layer is equal to the refractive index of the light transmission electrode.
<6> The organic light-emitting display device according to <5>, wherein the concave portion of the light transmission layer is filled with an adhesive.
<7> The organic light-emitting device according to any one of <1> to <6>, wherein the depths of the plurality of concave portions of the light transmission layer are different so as to emit at least one light of red, green, and blue It is a display device.
<8> The organic light-emitting display device according to any one of <1> to <7>, wherein the light reflecting electrode exists on the same plane.
<9> The organic light-emitting display device according to any one of <1> to <8>, wherein the organic EL layer emits white light.
<10> The organic light-emitting display device according to any one of <1> to <9>, further including a color filter layer on a light emission side of the light transmission layer.
<11> a step of sequentially laminating a light reflecting electrode, an organic EL layer, and a light transmitting electrode on a substrate;
Forming a light transmissive layer having a recess on a light transmissive substrate different from the substrate;
The light transmission layer is formed such that an optical resonator that emits light of at least one of red, green, and blue is formed between the light reflection electrode and a surface of the recess facing the light reflection electrode. And fixing the light transmitting electrode opposite to each other;
Is a method for manufacturing an organic light emitting display device.
<12> The step of forming the concave portion of the light transmission layer is the method for manufacturing the organic light emitting display device according to <11>, wherein the step is performed by mold transfer.
<13> The step of fixing the light transmissive layer and the light transmissive electrode so as to face each other is performed using a coupling agent. Production of an organic light emitting display device according to any one of <11> to <12> Is the method.
<14> The step of fixing the light transmitting layer and the light transmitting electrode so as to face each other is performed by filling a concave portion of the light transmitting layer with an adhesive, and the method according to any one of <11> to <13>. It is a manufacturing method of an organic light emitting display device.
<15> The organic light emitting display device according to any one of <1> to <10>, wherein the refractive index of the concave portion of the light transmission layer is smaller than the refractive index of the light transmission electrode.
<16> The organic light-emitting display device according to <15>, wherein the concave portion of the light transmission layer is a gap.
<17> The organic light-emitting display device according to any one of <1> to <10> and <15> to <16>, wherein an adhesive portion is formed between the light transmission layer and the light transmission electrode. .
<18> The optical resonance length L of the optical resonator is a multiple of a half wavelength of the peak wavelength λ of the emitted light ((λ / 2) × m; m is a natural number). The organic light emitting display device according to any one of 15> to <17>.
<19> The light emitting layer of the organic EL layer is disposed at a distance of optical length L ′ = (λ / 4) × (2n−1) (λ is a peak wavelength of emitted light; n is a natural number) from the light reflecting electrode. The organic light-emitting display device according to any one of <1> to <10> and <15> to <18>.
<20> There are a plurality of light reflecting electrodes,
The switching drive circuit for supplying a current to each light reflecting electrode is any one of the items <1> to <10> and <15> to <19> arranged between the substrate and the light reflecting electrode. An organic light emitting display device.
<21> The organic light-emitting display device according to any one of <1> to <10> and <15> to <20>, wherein the organic EL layer contains a phosphorescent material.
<22> Consists of a plurality of pixels,
The organic light-emitting display according to any one of <1> to <10> and <15> to <21>, wherein one pixel includes subpixels that are controlled to be lit in correspondence with the three primary colors red, blue, and green Device.
<23> The organic light emitting display device according to <22>, wherein one pixel includes subpixels corresponding to the three primary colors red, blue, and green and subpixels that are controlled to be lit in response to white. .
<24> The organic light-emitting display device according to <1>, wherein at least one of the substrate and the light transmission layer has flexibility.
<25> The method for producing an organic light-emitting display device according to <14>, wherein the adhesive is disposed in the concave portion by coating, printing, or an inkjet method.

  According to the present invention, it is possible to solve the above-mentioned problems in the prior art, achieve the above-mentioned object, and can be manufactured by a simple method, and an organic light-emitting display having good light-emitting characteristics with increased intensity of a specific wavelength. A device and a method for manufacturing the organic light emitting display device can be provided.

FIG. 1 is a schematic cross-sectional view illustrating an example of an organic light emitting display device according to the present invention. FIG. 2 is a schematic cross-sectional view illustrating an example of an organic light emitting display device according to the present invention. FIG. 3 is a schematic cross-sectional view illustrating an example of an organic light emitting display device according to the present invention. FIG. 4 is a schematic cross-sectional view illustrating an example of an organic light emitting display device according to the present invention. FIG. 5 is a light emission output characteristic diagram of Example 1 of the organic light emitting display device according to the present invention. FIG. 6 is a light emission output characteristic diagram of Example 2 of the organic light emitting display device according to the present invention. FIG. 7 is a light emission output characteristic diagram of an organic light emitting display device according to a comparative example. FIG. 8 is an optical characteristic diagram of the color filter used in Examples and Comparative Examples of the present invention. FIG. 9 is a light emission output characteristic diagram of the OLED substrate used in Examples and Comparative Examples of the present invention.

(Organic light emitting display)
The organic light-emitting display device according to the present invention includes a substrate, a light reflection electrode, an organic EL layer, a light transmission electrode, and a light transmission layer having a recess, and includes other members as necessary.

  The shape, structure, and size of the organic light-emitting display device are not particularly limited as long as they have the above-described configuration, and may be appropriately selected depending on the purpose. An example of the aspect of the organic light emitting display device will be described with reference to the drawings.

  1 to 4 are schematic cross-sectional views illustrating an example of an organic light emitting display device according to the present invention. The organic light emitting display device 100 includes an OLED substrate 20 that is a light source, and an optical member 10 having a concavo-convex portion including a convex portion 14 and a concave portion 15 on the surface.

  The optical member 10 includes a light-transmitting substrate 19 having light transmittance, which is different from a substrate 22 of an OLED substrate 20 described later, and a light-transmitting layer 12 laminated on the light-transmitting substrate 19. The upper surface of the layer 12 has a concavo-convex portion including a convex portion 14 and a concave portion 15.

  The OLED substrate 20 includes a substrate 22 made of glass or the like, a light reflecting electrode 24 having light reflectivity stacked on the substrate 22, an organic EL layer 26 that generates light stacked on the light reflecting electrode 24, and A light transmissive electrode 28 having a light transmissive property laminated on the organic EL layer 26.

  1 to 4, reference numeral 32 denotes a pixel circuit that controls the energization of electrodes, reference numeral 34 denotes a contact hole, and reference numeral 36 denotes one pixel or one sub-electrode by electrically separating adjacent electrodes. Each of the insulating layers defining the pixels is shown. In addition, arrows indicated by R, G, B, and W indicate the emission direction of light from the organic light emitting display device. Further, the optical member 10 and the OLED substrate 20 are described as being separated from each other, but this is described for convenience in order to explain the configuration of the organic light emitting display device.

<Adhesive part>
In the organic light emitting display device 100, the optical member 10 and the OLED substrate 20 are fixed to be opposed to each other through the bonding portion 30 between the light transmission electrode 28 and the light transmission layer 12. The facing mode is not particularly limited and may be appropriately determined depending on the purpose. For example, the convex portion 14 of the light transmitting layer 12 of the optical member 10 and the light transmitting electrode 28 of the OLED substrate 20 may face each other. . As a method of fixing them facing each other, as shown in FIGS. 1 and 3, the convex portions 14 of the light transmitting layer 12 and the light transmitting electrodes 28 of the OLED substrate 20 are fixed facing each other via the adhesive portion 30. Also good. Further, as shown in FIGS. 2 and 4, the convex portion 14 of the light transmission layer 12 and the light transmission electrode 28 of the OLED substrate 20 are connected via the material of the adhesive portion 30 filled in the concave portion 15 of the optical member 10. You may fix facing. With this configuration, the organic light emitting display device 100 is formed by the optical member 10 and the OLED substrate 20.

  In the configuration of FIGS. 1 and 3, there is no particular limitation on the method of fixing the convex portion 14 of the light transmission layer 12 and the light transmission electrode 28 of the OLED substrate 20 opposite to each other via the bonding portion 30. It may be appropriately selected according to the above, but is preferably a means for bonding at the molecular level in terms of easy adjustment of the optical distance such as the optical path length in the organic light emitting display device of the light emitted from the OLED substrate. Examples include bonding using a silane coupling agent.

  2 and 4, the convex portion 14 of the light transmission layer 12 and the light transmission electrode 28 of the OLED substrate 20 are opposed to each other through the material of the adhesive portion 30 filled in the concave portion 15 of the optical member 10. The fixing method is not particularly limited and may be appropriately selected depending on the purpose. For example, a method of filling the concave portion 15 of the optical member 10 with an adhesive such as acrylic, epoxy, or polyvinyl alcohol and bonding the optical member 10 and the OLED substrate 20 through the adhesive may be used. There is no restriction | limiting in particular as a method of filling an adhesive agent, What is necessary is just to select suitably according to the objective, For example, application | coating, printing, or the inkjet method is mentioned. Among these, the inkjet method is preferable because a desired amount can be filled into a predetermined portion by a simple method.

  The amount of the adhesive filled in the recess according to the inkjet method is not particularly limited and may be appropriately selected depending on the purpose. However, the adhesive is bonded so that the adhesive does not leak from the recess depending on the volume of the formed recess. The filling amount of the agent may be adjusted. Examples of the adjustment of the filling amount are as follows. That is, when the pixel size is 200 μm × 50 μm and the recess depths of the R, G, and B colors are R part = 33 to 60 nm, G part = 17 to 30 nm, and B part = 6 to 10 nm, The volumes of the concave portions of the G and B colors are R part = 0.33 to 0.6 pl, G part = 0.17 to 0.3 pl, and B part = 0.06 to 0.1 pl. Therefore, the amount may be adjusted so that this amount is filled in each recess.

  The aspect of filling the concave portion with the adhesive according to the ink jet method is not particularly limited and may be appropriately selected depending on the purpose, but when the concave portion corresponding to each formed color pixel is arranged adjacent to the same row. May be filled with the same amount of adhesive between the recesses corresponding to successive pixels of the same color. In this case, for example, if the recesses for 100 pixels are communicated, the volume of each recess is R part = 33 to 60 pl, G part = 17 to 30 pl, and B part = 6 to 10 pl. This amount of adhesive may be ejected an appropriate number of times according to the amount of ink jet applied. In the case of an inkjet of 1 pl per unit discharge, the R part = 33 to 60 times, the G part = 17 to 30 times, and the B part = 6 to 10 times in each concave part, so that it fits the volume of each concave part. Adhesive can be filled. In this way, it is only necessary to connect the pixel recesses in the same color row by the multiple of the pixel recesses so that each pixel recess volume is a multiple of the minimum unit of the adhesive droplet.

-Optical resonator-
In the organic light emitting display device 100, the OLED substrate 20 extends from the surface facing the light transmitting electrode 28 in the recess 15 formed in the light transmitting layer 12 in the optical member 10 and the light transmitting electrode 28 of the OLED substrate 20. A so-called optical resonator structure (microcavity structure) generated by the reflection / interference of the emitted light is formed. The optical resonator is not particularly limited as long as it can reflect / interfer light from the OLED substrate, and may be appropriately selected according to the purpose. For example, the optical resonator is laminated on the substrate 22 of the OLED substrate 20. The light reflecting electrode 24 may be formed between the light reflecting electrode 24 and the light semi-transmissive reflecting layer 16 described later formed in the recess 15 on the light transmitting layer 12 of the optical member 10. Among them, the optical resonance length L of the optical resonator is a multiple of a half wavelength of the peak wavelength λ of the emitted light ((λ / 2) × m; m A natural number). As a result, the color intensity due to multiple interference increases, and an organic light emitting display device capable of emitting higher light intensity is obtained. By forming the optical resonator in this manner, light of at least one specific color such as red, green, and blue is transmitted from the light transmission layer through the optical resonator, and the light of the organic light emitting display device The light is emitted in the emission direction.

<Optical member>
The optical member is a member disposed on the light emitting side in the organic light emitting display device according to the present invention, and is formed on the light transmissive substrate different from the substrate 22 of the OLED substrate 20 described above. The light transmission layer 12 having the recessed portion 15 and other members as necessary.

  The structure, shape, size, and the like of the optical member are not particularly limited as long as they can be used in the above-described organic light emitting display device, and may be appropriately selected according to the purpose. The optical member will be described with reference to FIGS. 1 and 2 that describe an organic light-emitting display device that is one embodiment of the use of the optical member. In the optical member 10, on the light transmission layer, as shown by reference numerals 14 and 15 in FIGS.

  The shape of the concave portion is not particularly limited as long as it is provided so as to correspond to each pixel, and can be appropriately selected according to the purpose. For example, the concave portion is arranged in a row along the width direction and / or the length direction of the optical member. It may be formed in a zigzag manner with respect to the width direction and / or the length direction of the optical member. The height of the convex portion 14 or the depth of the concave portion 15 is not particularly limited and may be appropriately selected according to the purpose. However, the light intensity from the above-mentioned OLED substrate is optimized, and the light emission intensity at a specific wavelength. It is preferable that they are different so as to emit at least one light of red, green and blue.

  In the organic light emitting display device, the configuration of the concave portion of the light transmission layer of the optical member is not particularly limited as long as it does not affect the optical characteristics of light emission from the organic EL layer of the organic light emitting display device. The refractive index of the concave portion of the light transmission layer is preferably smaller than the refractive index of the light transmission electrode in terms of relaxing processing accuracy of the depth of the concave portion forming the optical resonance length L. It is preferable that the refractive index of the concave portion of the light transmitting layer is equal to the refractive index of the light transmitting electrode so that the optical resonator can be formed stably. In the organic light emitting display device, the concave portion of the light transmission layer of the optical member has a processing accuracy of the depth of the concave portion forming the optical resonance length L, and reduces the refractive reflection loss of the outgoing light passing through the optical member. In this respect, it is preferable that the concave portion of the light transmission layer is a void equivalent to a refractive index 1 of air on the emission side. The range equivalent to the refractive index 1 of air is not particularly limited and may be appropriately selected, but is preferably 1.0 to 1.1 from the viewpoint of suppressing the refractive index difference between the front and back of the optical member. The refractive index is measured by ellipsometry using, for example, an Abbe refractometer (manufactured by Atago Co., Ltd.).

  There is no restriction | limiting in particular as a formation method of a recessed part, What is necessary is just to select suitably according to the objective, For example, the injection | emission molding method using a mold (mold | die, plate | version | printing), the mold transfer method, and the imprint method are mentioned. Among these, an imprint method using a mold is preferable in terms of high accuracy and good workability. The form for forming the recess is not particularly limited and may be appropriately selected depending on the purpose. For example, when the imprint method using the above-described mold is performed, a light-transmitting substrate or a color filter described later is used. On the light transmission layer or light semi-transmissive reflection layer formed on the layer, a concave / convex portion forming mold described later may be pressed to form a desired concave / convex shape. The formed light-transmitting layer having an uneven shape may be cured under appropriate conditions (for example, UV irradiation, heating). In particular, since the light-transmitting substrate of the optical member is light-transmitting, it may be cured by performing UV irradiation through this light-transmitting substrate. When the optical member has a color filter layer, positioning is performed so as to correspond to the red filter portion, the green filter portion, the blue filter portion, and the white filter portion constituting the color filter layer 18, and a predetermined recess is formed. You may make it do.

-Mold for uneven parts-
There is no restriction | limiting in particular as a formation method of the uneven | corrugated | grooved part formation mold used for formation of the recessed part in an optical member, According to the objective, it can select suitably, For example, electron beam (EB) lithography and etching, laser drawing, etc. Is mentioned. Among these, the lithography method and the dry etching method for the quartz substrate are preferable in that UV irradiation from the mold side is obtained regardless of the UV transmission characteristics of the light-transmitting substrate. These methods may be used alone or in combination of two or more.

  As an example of a method for forming a mold for forming an uneven portion, for example, a method is used in which a quartz substrate surface at a predetermined position is opened by a photolithography process using a photosensitive resist on a quartz substrate, and etching is performed to a predetermined depth by dry etching. There may be. When forming a recess in the optical member so as to have two or more depths, the etching depth is adjusted by adjusting the dry etching conditions after opening the quartz substrate surface by the photolithography process as described above. May be. For example, in the case of forming a multi-stage uneven portion like the optical member shown in FIGS. 1 and 2, in the uneven portion forming mold, the portion corresponding to the concave portion in the green position is etched by 16 to 30 nm from the surface of the quartz substrate. The portion corresponding to the concave portion at the blue position is etched from 27 to 50 nm from the quartz substrate surface, and the portion corresponding to the convex portion separating the pixels is etched from 33 to 60 nm from the quartz substrate surface to form the concave portion at the red position. For the corresponding portion, the quartz substrate surface may be left without being etched. Moreover, about the part corresponded to the recessed part of a white position, it may be set as a recessed part deeper than the recessed part of a red position, or a recessed part may not be provided. If it is deeper than the concave portion in the red position, the surface of the quartz substrate remains as it is. In addition, when there is no concave portion, processing may be similarly performed on a portion corresponding to a convex portion that partitions pixels. In this way, a mold for forming an uneven portion is obtained. In addition, the part which forms a recessed part and a convex part after imprinting an optical member using this uneven | corrugated | grooved part formation mold WHEREIN: In the uneven | corrugated | grooved part formation mold, respectively, the convex part and recessed part formed in the quartz substrate surface, respectively Correspond.

<< light transmission layer >>
In the optical member, the light transmission layer is not particularly limited as long as it transmits light emitted from an OLED substrate described later, and may be appropriately selected according to the purpose. The light transmission layer is preferably formed of one member. With this configuration, the convex portion and the concave portion are integrally formed, which is preferable from the viewpoint of ease of manufacturing in that the arrangement of the concave and convex portions and the step size can be easily controlled. There is no restriction | limiting in particular as thickness of a light transmissive layer, What is necessary is just to select suitably according to the objective, and 1 micrometer-several micrometers may be sufficient. In particular, what is necessary is just to be thicker than the maximum step of the unevenness of the mold for forming the uneven portion described later.

  There is no restriction | limiting in particular as a material of a light transmissive layer, What is necessary is just to select suitably according to the objective, For example, various photocurable resins, various thermoplastic resins, various thermosetting resins, etc. are mentioned. Examples of the photocurable resin include unsaturated polyester resin, polyester acrylate resin, urethane acrylate resin, silicone acrylate resin, and epoxy acrylate resin. Examples of the thermoplastic resin include polyethylene, polyester, polystyrene, and polycarbonate. Examples of the functional resin include silicone resins, phenoxy resins, and epoxy resins. As the material for the light transmission layer, other materials having a polymerization initiator may be used.

  In the optical member, the method for producing the light transmission layer is not particularly limited as long as it satisfies the above requirements, and may be appropriately selected according to the purpose. For example, a light transmitting layer described later is laminated on a light transmitting substrate described later or a color filter layer described later by spin coating, extrusion coating, bar coating, gravure coating, roll coating, and on this light transmitting layer, A method of forming an uneven portion may be used.

<< light transmissive substrate >>
In the optical member, the light transmissive substrate is not particularly limited as long as it transmits light emitted from an OLED substrate, which will be described later, and may be appropriately selected according to the purpose. The light-transmitting substrate is not particularly limited as long as this purpose is satisfied, and the shape, structure, size, and the like may be appropriately selected. In general, the shape of the substrate is preferably a plate shape. The structure of the substrate may be a single layer structure, a laminated structure, may be formed of a single member, or may be formed of two or more members. The substrate may be colorless and transparent or may be colored and transparent, but is preferably colorless and transparent in that it does not scatter or attenuate light emitted from the OLED substrate. Moreover, it is preferable that it is flexible from the point of convenience.

  The arrangement position of the light-transmitting substrate is not particularly limited as long as the light-transmitting layer is supported and unevenness is formed on the upper surface of the layer. Especially, it is outside the optical path of the optical resonator composed of the OLED substrate and the concave portion of the light transmission layer, and does not affect the characteristics of the light from the light emitting layer. It is preferable that the light emitting display device is disposed in the light emitting direction.

  The material of the light-transmitting substrate is not particularly limited and can be appropriately selected according to the purpose. Specific examples thereof include inorganic materials such as glass, polyethylene terephthalate, polybutylene phthalate, and polyethylene naphthalate. Examples include organic materials such as polyester, polystyrene, polycarbonate, polyethersulfone, polyarylate, polyimide, polycycloolefin, norbornene resin, and poly (chlorotrifluoroethylene).

  For example, when glass is used as the light-transmitting substrate, it is preferable to use alkali-free glass for the material in order to reduce ions eluted from the glass. Moreover, when using soda-lime glass, it is preferable to use what gave barrier coatings, such as a silica. In the case of an organic material, it is preferable that it is excellent in heat resistance, dimensional stability, solvent resistance, electrical insulation and workability.

  When a thermoplastic substrate is used, a hard coat layer, an undercoat layer, or the like such as a barrier film substrate may be further provided as necessary.

<< Other parts >>
<<< Light transflective layer >>>
In the optical member, a light transflective layer that transmits a part of the light traveling in the light emitting direction of the organic light-emitting display device as viewed from the OLED substrate, which will be described later, and reflects the other part is used as the light of the optical member. You may provide in the surface of a permeation | transmission layer. That is, as indicated by reference numeral 16 in FIGS. 1 and 2, the light semi-transmissive reflective layer may be provided on the surface of the light transmissive layer 12 having a concavo-convex portion including the convex portion 14 and the concave portion 15. The structure, shape, size, and the like of the light transflective layer are not particularly limited and may be appropriately selected depending on the purpose. There is no restriction | limiting in particular, What is necessary is just to select suitably according to the objective, For example, Ag and Al of a thin film are mentioned. The thickness of the light transflective layer is not particularly limited and may be appropriately selected depending on the intended purpose, but is preferably 10 nm to 30 nm in terms of the balance between transmittance and reflectance. The method for providing the light transflective layer is not particularly limited as long as it is a known method in this technical field, and may be appropriately selected according to the purpose. For example, a dry film forming method such as a vapor deposition method or a sputtering method, Examples thereof include a transfer method, a printing method, a coating method, an ink jet method, and a spray method. Among these, a dry film forming method is preferable from the viewpoint of uniform film thickness control, and a vapor deposition method is more preferable from the viewpoint of less damage to the light transmission layer.

<< Color filter layer >>
In the optical member, there may be provided a color filter layer that transmits light having a specific wavelength out of light traveling in the light emitting direction of the organic light emitting display device as viewed from the OLED substrate described later. There is no restriction | limiting in particular as a shape, a structure, a magnitude | size, etc. of a color filter layer, What is necessary is just to select suitably according to the objective, For example, as shown by the code | symbol 18 of FIGS. The thickness of the color filter layer is not particularly limited and may be appropriately selected depending on the intended purpose, but is preferably 10 nm to 10 μm in terms of color density adjustment. The position where the color filter layer is provided is not particularly limited and may be appropriately selected depending on the purpose. However, in terms of the protective structure of the color filter layer and manufacturability, the light transmissive substrate and the light transmissive layer of the optical member It is preferable to provide between. The method for forming the color filter layer is not particularly limited and may be appropriately selected according to the purpose. The fine pattern is obtained by exposing and developing the photosensitive composition on the light-transmitting substrate of the optical member. Examples thereof include a photolithography method and an ink jet method.

  The configuration of the organic light emitting display device is preferably composed of a plurality of pixels in that it can be displayed in full color. The configuration of one of the plurality of pixels is not particularly limited and may be appropriately selected depending on the purpose, and may include sub-pixels corresponding to the three primary colors red, blue, and green. Sub-pixels corresponding to the three primary colors red, blue and green, and sub-pixels corresponding to white may be included. There is no restriction | limiting in particular as a structure of a color filter layer, What is necessary is just to select suitably according to the objective, You may comprise so that it may respond | correspond to the structure of said pixel, for example, as shown to FIGS. Further, the configuration may include a red filter portion 18r, a green filter portion 18g, a blue filter portion 18b, and a white filter portion 18w.

<OLED substrate>
The OLED substrate is formed by sequentially laminating a light reflecting electrode, an organic EL layer, and a light transmitting electrode on the substrate, and has other members as necessary. In the present invention, the “OLED substrate” is a general term for substrates having at least a light reflecting electrode and an organic EL layer and having a layer that emits light in an organic light emitting display device. Means different members.

<< Organic EL layer >>
The organic EL layer is not particularly limited as long as it emits light by applying an electric field, and may be appropriately selected according to the purpose. In particular, an organic EL layer that emits white light is preferable because it is not necessary to adjust the white balance and is easy to manufacture.

  The organic EL layer may be made of an organic light emitting material or an inorganic light emitting material. Among them, the light emitting efficiency, the size of the apparatus can be increased, the low voltage driving, the low temperature manufacturing process can be performed. In this respect, an organic light emitting material is preferable. Hereinafter, an organic compound layer having a light emitting layer using an organic light emitting material will be described.

-Organic compound layer-
As an organic compound layer having an organic light emitting layer using an organic light emitting material, an aspect in which a hole transport layer, an organic light emitting layer, and an electron transport layer are stacked in this order from the anode side as a stacked form of the organic compound layer. preferable. Further, a hole injection layer may be provided between the hole transport layer and the anode, and / or an electron transporting intermediate layer may be provided between the organic light emitting layer and the electron transport layer. In addition, a hole transporting intermediate layer may be provided between the organic light emitting layer and the hole transport layer, and similarly, an electron injection layer may be provided between the cathode and the electron transport layer. Each layer may be divided into a plurality of secondary layers. Each layer other than the anode, the cathode, and the organic light emitting layer corresponds to the other layer / member.

  Each layer constituting the organic compound layer can be suitably formed by any of dry film forming methods such as vapor deposition and sputtering, transfer methods, printing methods, coating methods, ink jet methods, and spray methods. Of these, the vapor deposition method is preferable in terms of device life and throughput.

  The production of the organic light emitting layer by the vapor deposition method is not particularly limited as long as the above-described configuration can be achieved, and may be appropriately selected according to the purpose. The deposition conditions are not particularly limited and may be appropriately selected depending on the purpose. However, the deposition rate is preferably 8 nm / second or more, more preferably 10 nm / second or more, and 15 nm / second or more. It is particularly preferred that If it is less than 8 nm / second, the amount of trapped carriers in the organic light emitting layer is reduced, and the external quantum efficiency and the half-life are reduced.

  The organic light emitting display device has at least one organic compound layer including an organic light emitting layer, and other organic compound layers other than the organic light emitting layer include a hole transport layer, an electron transport layer, a hole block layer, Examples thereof include an electron blocking layer, a hole injection layer, and an electron injection layer.

  In the organic light emitting display device, each layer constituting the organic compound layer can be suitably formed by any of a dry film forming method such as a vapor deposition method and a sputtering method, a wet coating method, a transfer method, a printing method, and an ink jet method. .

  When an electric field is applied, the organic light emitting layer receives holes from the anode, hole injection layer or hole transport layer, receives electrons from the cathode, electron injection layer or electron transport layer, and recombines holes with electrons. It is a layer which has the function to provide and to emit light.

  The organic light emitting layer may be composed of only a light emitting material, or may be a mixed layer of a host material and a dopant material. The dopant material may be a light-emitting dopant, and the light-emitting dopant may be a fluorescent light-emitting material or a phosphorescent light-emitting material, or two or more kinds. The host material is preferably a charge transport material. The host material may be one kind or two or more kinds, and examples thereof include a configuration in which an electron transporting host material and a hole transporting host material are mixed. Furthermore, the organic light emitting layer may contain a material that does not have charge transporting properties and does not emit light.

Further, the organic light emitting layer may be a single layer or two or more layers, and each layer may emit light in different emission colors. Especially, each layer which comprises the light emitting layer of an organic electroluminescent layer is arrange | positioned in the distance which optical length L 'from the light reflection electrode of an OLED board | substrate satisfy | fills the following formula by the point which can achieve favorable luminous efficiency. Preferably it is.
L ′ = (λ / 4) × (2n−1)
(Λ is the peak wavelength of the emitted light; n is a natural number)

  There are no particular limitations on the configuration so that the optical length L ′ satisfies the above relationship, and it may be appropriately selected according to the purpose, but the thickness of the organic EL layer constituting the OLED substrate may be appropriately adjusted. For example, the thickness of the hole injection layer and the thickness of each light emitting layer may be adjusted.

  As the luminescent dopant, any of a phosphorescent luminescent material, a fluorescent luminescent material, and the like can be used as a dopant (phosphorescent dopant, fluorescent luminescent dopant).

  The organic light emitting layer can also contain two or more kinds of luminescent dopants in order to improve color purity or extend the light emission wavelength region. The luminescent dopant further has an ionization potential difference (ΔIp) and an electron affinity difference (ΔEa) of 1.2 eV> ΔIp> 0.2 eV and / or 1.2 eV> with the host compound. A dopant satisfying the relationship of ΔEa> 0.2 eV is preferable from the viewpoint of driving durability.

  There is no restriction | limiting in particular as said phosphorescent dopant, According to the objective, it can select suitably, The complex containing a transition metal atom or a lanthanoid atom can be mentioned.

  The transition metal atom is not particularly limited and may be appropriately selected depending on the intended purpose, but is preferably ruthenium, rhodium, palladium, tungsten, rhenium, osmium, iridium, gold, silver, copper, and platinum, and rhenium. , Iridium, and platinum are more preferable, and iridium and platinum are particularly preferable.

  The lanthanoid atom is not particularly limited and may be appropriately selected according to the purpose.For example, lanthanum, cerium, praseodymium, neodymium, samarium, europium, gadolinium, terbium, dysprosium, holmium, erbium, thulium, ytterbium, and Lutesium. Of these, neodymium, europium, and gadolinium are preferable.

  Examples of the ligand of the complex include G.I. Wilkinson et al., Comprehensive Coordination Chemistry, Pergamon Press, 1987, H.C. Examples include ligands described in Yersin's "Photochemistry and Photophysics of Coordination Compounds" published by Springer-Verlag 1987, Akio Yamamoto "Organic Metal Chemistry-Fundamentals and Applications-" .

  Examples of the ligand include a halogen ligand (preferably a chlorine ligand), an aromatic carbocyclic ligand (for example, a cyclopentadienyl anion, a benzene anion, a naphthyl anion, etc.). Preferably 6 to 30 carbon atoms, more preferably 6 to 20 carbon atoms, still more preferably 6 to 12 carbon atoms), a nitrogen-containing heterocyclic ligand (for example, phenylpyridine, benzoquinoline, quinolinol, Bipyridyl, phenanthroline, etc. are mentioned, C5-C30 is preferable, C6-C30 is more preferable, C6-C20 is still more preferable, C6-C12 is especially preferable, and diketone ligand ( Examples thereof include acetylacetone and the like, and carboxylic acid ligands (for example, acetic acid ligands and the like, preferably having 2 to 30 carbon atoms). C2-20 is more preferable, C2-16 is particularly preferable), an alcoholate ligand (for example, a phenolate ligand, etc.), C1-30 is preferable, and C1-20. Are more preferable, and those having 6 to 20 carbon atoms are more preferable), silyloxy ligands (for example, trimethylsilyloxy ligand, dimethyl-tert-butylsilyloxy ligand, triphenylsilyloxy ligand, etc.) 3 to 40 carbon atoms are preferable, 3 to 30 carbon atoms are more preferable, and 3 to 20 carbon atoms are particularly preferable), carbon monoxide ligand, isonitrile ligand, cyano ligand, phosphorus ligand (for example, , Triphenylphosphine ligand and the like, preferably having 3 to 40 carbon atoms, more preferably 3 to 30 carbon atoms, still more preferably 3 to 20 carbon atoms, And a thiolato ligand (e.g., a phenylthiolato ligand), preferably having 1 to 30 carbon atoms, more preferably 1 to 20 carbon atoms, and 6 to 20 carbon atoms. Particularly preferred), phosphine oxide ligands (for example, triphenylphosphine oxide ligands, etc.), 3 to 30 carbon atoms are preferred, 8 to 30 carbon atoms are more preferred, and 18 to 30 carbon atoms are particularly preferred. Is preferable, and a nitrogen-containing heterocyclic ligand is more preferable.

  The complex may have one transition metal atom in the compound, or may be a so-called binuclear complex having two or more. Different metal atoms may be contained at the same time.

  Among these, as the luminescent dopant, for example, US 6,303,238B1, US 6,097,147, WO00 / 57676, WO00 / 70655, WO01 / 08230, WO01 / 39234A2, WO01 / 41512A1, WO02 / 02714A2, WO02 / 15645A1, WO02 / 44189A1, WO05 / 19373A2, JP2001-247859, JP2002-302671, JP2002-117978, JP2003-133074, JP2002-235076, JP2003-123982, JP2002 -170684, EP12112257, JP2002-226495, JP2002-234894, JP2001247478, JP2001-298470, JP2002 173674, JP 2002-203678, JP 2002-203679, JP 2004-357799, JP 2006-256999, JP 2007-19462, JP 2007-84635, JP 2007-96259, and the like. Examples include phosphorescent light emitting compounds. Among them, Ir complex, Pt complex, Cu complex, Re complex, W complex, Rh complex, Ru complex, Pd complex, Os complex, Eu complex, Tb complex, Gd complex, Dy complex, and Ce complex are preferable, and Ir complex, Pt complex and Re complex are more preferable. Among these, Ir complexes, Pt complexes, and Re complexes containing at least one coordination mode of metal-carbon bond, metal-nitrogen bond, metal-oxygen bond, and metal-sulfur bond are even more preferable. Furthermore, from the viewpoints of luminous efficiency, driving durability, chromaticity, etc., an Ir complex, a Pt complex, and a Re complex containing a tridentate or higher multidentate ligand are particularly preferable.

  The fluorescent light emitting dopant is not particularly limited and may be appropriately selected depending on the intended purpose. Benzoxazole, benzimidazole, benzothiazole, styrylbenzene, polyphenyl, diphenylbutadiene, tetraphenylbutadiene, naphthalimide, coumarin , Pyran, perinone, oxadiazole, aldazine, pyralidine, cyclopentadiene, bisstyrylanthracene, quinacridone, pyrrolopyridine, thiadiazolopyridine, cyclopentadiene, styrylamine, aromatic dimethylidin compound, condensed polycyclic aromatic compound (anthracene, Phenanthroline, pyrene, perylene, rubrene, or pentacene), 8-quinolinol metal complexes, various metal complexes represented by pyromethene complexes and rare earth complexes, polythiol Emissions, polyphenylene, polyphenylene vinylene polymer compounds such as organosilanes, and the like derivatives thereof.

  Examples of the luminescent dopant include the following, but are not limited thereto.

  The light-emitting dopant in the organic light-emitting layer is contained in an amount of 0.1% by mass to 50% by mass with respect to the total compound mass generally forming the organic light-emitting layer in the organic light-emitting layer. From the viewpoint of efficiency, the content is preferably 1% by mass to 50% by mass, and more preferably 2% by mass to 40% by mass.

  The thickness of the organic light-emitting layer is not particularly limited, but is usually preferably 2 nm to 500 nm, and more preferably 3 nm to 200 nm from the viewpoint of external quantum efficiency. 100 nm is particularly preferred.

  As the host material, a hole-transporting host material having excellent hole-transporting property (may be described as a hole-transporting host) and an electron-transporting host compound having excellent electron-transporting property (described as an electron-transporting host) May be used).

  Examples of the hole transporting host in the organic light emitting layer include the following materials. Pyrrole, indole, carbazole, azaindole, azacarbazole, triazole, oxazole, oxadiazole, pyrazole, imidazole, thiophene, polyarylalkane, pyrazoline, pyrazolone, phenylenediamine, arylamine, amino-substituted chalcone, styrylanthracene, fluorenone Hydrazone, stilbene, silazane, aromatic tertiary amine compound, styrylamine compound, aromatic dimethylidin compound, porphyrin compound, polysilane compound, poly (N-vinylcarbazole), aniline copolymer, thiophene oligomer, Examples thereof include conductive polymer oligomers such as polythiophene, organic silanes, carbon films, and derivatives thereof.

  Of these, indole derivatives, carbazole derivatives, aromatic tertiary amine compounds, and thiophene derivatives are preferable, those having a carbazole group in the molecule are more preferable, and compounds having a t-butyl-substituted carbazole group are particularly preferable.

  The electron transporting host in the organic light emitting layer preferably has an electron affinity Ea of 2.5 eV or more and 3.5 eV or less from the viewpoint of improving durability and lowering driving voltage, and is 2.6 eV or more and 3.4 eV or less. More preferably, it is 2.8 eV or more and 3.3 eV or less. Further, from the viewpoint of improving durability and reducing driving voltage, the ionization potential Ip is preferably 5.7 eV or more and 7.5 eV or less, more preferably 5.8 eV or more and 7.0 eV or less, and 5.9 eV or more. It is particularly preferable that it is 6.5 eV or less.

  Specific examples of such an electron transporting host include the following materials. Pyridine, pyrimidine, triazine, imidazole, pyrazole, triazole, oxazole, oxadiazol, fluorenone, anthraquinodimethane, anthrone, diphenylquinone, thiopyran dioxide, carbodiimide, fluorenylidenemethane, distyryl Metal complexes of pyrazine, fluorine-substituted aromatic compounds, heterocyclic tetracarboxylic anhydrides such as naphthaleneperylene, phthalocyanines, and derivatives thereof (which may form condensed rings with other rings), 8-quinolinol derivatives And various metal complexes represented by metal complexes having metal phthalocyanine, benzoxazole or benzothiazol as a ligand.

  As the electron transporting host, metal complexes, azole derivatives (benzimidazole derivatives, imidazopyridine derivatives, etc.), and azine derivatives (pyridine derivatives, pyrimidine derivatives, triazine derivatives, etc.) are preferable. Compounds are more preferred. The metal complex compound (A) is preferably a metal complex having a ligand having at least one of a nitrogen atom, an oxygen atom and a sulfur atom coordinated to a metal.

  The metal ion in the metal complex is not particularly limited and can be appropriately selected depending on the purpose, but beryllium ion, magnesium ion, aluminum ion, gallium ion, zinc ion, indium ion, tin ion, platinum ion, or Palladium ions are preferable, beryllium ions, aluminum ions, gallium ions, zinc ions, platinum ions, or palladium ions are more preferable, and aluminum ions, zinc ions, or palladium ions are particularly preferable.

  The ligand contained in the metal complex may be any of various known ligands. For example, “Photochemistry and Photophysics of Coordination Compounds”, Springer-Verlag, H.C. Examples include the ligands described in Yersin, published in 1987, “Organometallic Chemistry: Fundamentals and Applications”, Sakai Hanafusa, Yamamoto Akio, published in 1982, and the like.

  As said ligand, a nitrogen-containing heterocyclic ligand (C1-C30 is preferable, C2-C20 is more preferable, C3-C15 is especially preferable). Further, the ligand may be a monodentate ligand or a bidentate or more ligand, but is preferably a bidentate or more and a hexadentate or less ligand. Also preferred are bidentate to hexadentate ligands and monodentate mixed ligands.

  Examples of the ligand include an azine ligand (for example, a pyridine ligand, a bipyridyl ligand, a terpyridine ligand, etc.), a hydroxyphenylazole ligand (for example, hydroxyphenylbenzimidazole). Ligands, hydroxyphenylbenzoxazole ligands, hydroxyphenylimidazole ligands, hydroxyphenylimidazopyridine ligands, etc.), alkoxy ligands (eg, methoxy, ethoxy, butoxy, 2-ethylhexyl). Siloxy etc. are mentioned, C1-C30 is preferable, C1-C20 is more preferable, C1-C10 is especially preferable.), An aryloxy ligand (for example, phenyloxy, 1-naphthyloxy, 2-naphthyloxy, 2,4,6-trimethylphenyloxy, 4- Such as phenyloxy and the like, 6 to 30 carbon atoms, more preferably 6 to 20 carbon atoms, particularly preferably 6 to 12 carbon atoms) and the like.

  Heteroaryloxy ligands (for example, pyridyloxy, pyrazyloxy, pyrimidyloxy, quinolyloxy, etc. are mentioned, preferably having 1 to 30 carbon atoms, more preferably 1 to 20 carbon atoms, and particularly preferably 1 to 12 carbon atoms). Alkylthio ligands (for example, methylthio, ethylthio and the like are mentioned, preferably having 1 to 30 carbon atoms, more preferably having 1 to 20 carbon atoms, and particularly preferably having 1 to 12 carbon atoms), arylthio ligands (for example, Phenylthio etc. are mentioned, C6-C30 is preferable, C6-C20 is more preferable, C6-C12 is especially preferable,) heteroarylthio ligand (for example, pyridylthio, 2-benzimidazole). Ruthio, 2-benzoxazolylthio, 2-benzthiazolylthio and the like, and those having 1 to 30 carbon atoms More preferably, carbon number 1-20 is more preferable, and carbon number 1-12 is particularly preferable.), Siloxy ligand (for example, triphenylsiloxy group, triethoxysiloxy group, triisopropylsiloxy group, etc.) Numbers 1 to 30 are preferred, carbon numbers 3 to 25 are more preferred, and carbon numbers 6 to 20 are particularly preferred.), Aromatic hydrocarbon anion ligands (eg, phenyl anion, naphthyl anion, anthranyl anion, etc.) 6 to 30 carbon atoms, more preferably 6 to 25 carbon atoms, and particularly preferably 6 to 20 carbon atoms), an aromatic heterocyclic anion ligand (for example, a pyrrole anion, a pyrazole anion, a pyrazole anion, Triazole anion, oxazole anion, benzoxazole anion, thiazole anio Benzothiazole anion, thiophene anion, benzothiophene anion, etc., preferably having 1 to 30 carbon atoms, more preferably 2 to 25 carbon atoms, and particularly preferably 2 to 20 carbon atoms.), Indolenine anion coordination Preferred are nitrogen-containing heterocyclic ligands, aryloxy ligands, heteroaryloxy groups, siloxy ligands, etc., nitrogen-containing heterocyclic ligands, aryloxy ligands, siloxy coordination More preferred are a child, an aromatic hydrocarbon anion ligand, an aromatic heterocyclic anion ligand, and the like.

  Examples of the metal complex electron transporting host include, for example, JP-A-2002-2335076, JP-A-2004-214179, JP-A-2004-221106, JP-A-2004-221105, JP-A-2004-221068, JP-A-2004-327313, etc. And the compounds described.

  In the organic light emitting layer, the triplet lowest excitation level (T1) of the host material is preferably higher than T1 of the phosphorescent light emitting material in terms of color purity, light emission efficiency, and driving durability.

  In addition, the content of the host compound is not particularly limited, but may be 15% by mass or more and 95% by mass or less with respect to the total compound mass forming the light emitting layer from the viewpoint of luminous efficiency and driving voltage. preferable.

--- Hole injection layer, hole transport layer-
The hole injection layer and the hole transport layer are layers having a function of receiving holes from the anode or the anode side and transporting them to the cathode side. The hole injection material and the hole transport material used for these layers may be a low molecular compound or a high molecular compound.

  Specifically, pyrrole derivatives, carbazole derivatives, triazole derivatives, oxazole derivatives, oxadiazole derivatives, imidazole derivatives, polyarylalkane derivatives, pyrazoline derivatives, pyrazolone derivatives, phenylenediamine derivatives, arylamine derivatives, amino-substituted chalcone derivatives, styryl Anthracene derivatives, fluorenone derivatives, hydrazone derivatives, stilbene derivatives, silazane derivatives, aromatic tertiary amine compounds, styrylamine compounds, aromatic dimethylidin compounds, phthalocyanine compounds, porphyrin compounds, thiophene derivatives, organosilane derivatives, carbon, And the like.

  An electron-accepting dopant can be contained in the hole injection layer or the hole transport layer of the organic electroluminescence device. As the electron-accepting dopant introduced into the hole-injecting layer or the hole-transporting layer, an inorganic compound or an organic compound can be used as long as it has an electron-accepting property and oxidizes an organic compound.

  Specifically, examples of the inorganic compound include metal halides such as ferric chloride, aluminum chloride, gallium chloride, indium chloride, and antimony pentachloride, metal oxides such as vanadium pentoxide, and molybdenum trioxide. .

  In the case of an organic compound, a compound having a nitro group, halogen, cyano group, trifluoromethyl group or the like as a substituent, a quinone compound, an acid anhydride compound, fullerene, or the like can be preferably used.

  In addition, JP-A-6-212153, JP-A-11-111463, JP-A-11-251067, JP-A-2000-196140, JP-A-2000-286054, JP-A-2000-315580, JP-A-2001-102175, JP-A-2001-2001. -160493, JP2002-252085, JP2002-56985, JP2003-157981, JP2003-217862, JP2003-229278, JP2004-342614, JP2005-72012, JP20051666667 The compounds described in JP-A-2005-209643 and the like can be preferably used.

  Among these, hexacyanobutadiene, hexacyanobenzene, tetracyanoethylene, tetracyanoquinodimethane, tetrafluorotetracyanoquinodimethane, p-fluoranyl, p-chloranil, p-bromanyl, p-benzoquinone, 2,6-dichlorobenzoquinone, 2,5-dichlorobenzoquinone, 1,2,4,5-tetracyanobenzene, 1,4-dicyanotetrafluorobenzene, 2,3-dichloro-5,6-dicyanobenzoquinone, p-dinitrobenzene, m-dinitrobenzene O-dinitrobenzene, 1,4-naphthoquinone, 2,3-dichloronaphthoquinone, 1,3-dinitronaphthalene, 1,5-dinitronaphthalene, 9,10-anthraquinone, 1,3,6,8-tetranitrocarbazole 2,4,7-trinitro-9 Fluorenone, 2,3,5,6-tetracyanopyridine, or fullerene C60 is preferable, and hexacyanobutadiene, hexacyanobenzene, tetracyanoethylene, tetracyanoquinodimethane, tetrafluorotetracyanoquinodimethane, p-fluoranyl, p- Chloranil, p-bromanyl, 2,6-dichlorobenzoquinone, 2,5-dichlorobenzoquinone, 2,3-dichloronaphthoquinone, 1,2,4,5-tetracyanobenzene, 2,3-dichloro-5,6-dicyano Benzoquinone or 2,3,5,6-tetracyanopyridine is more preferred, and tetrafluorotetracyanoquinodimethane is particularly preferred.

  These electron-accepting dopants may be used alone or in combination of two or more. Although the usage-amount of an electron-accepting dopant changes with kinds of material, it is preferable that it is 0.01 mass%-50 mass% with respect to hole transport layer material, and it is 0.05 mass%-20 mass%. More preferably, it is especially preferable that it is 0.1 mass%-10 mass%.

  The thicknesses of the hole injection layer and the hole transport layer are each preferably 500 nm or less from the viewpoint of lowering the driving voltage. The thickness of the hole transport layer is preferably 1 nm to 500 nm, more preferably 5 nm to 200 nm, and particularly preferably 10 nm to 100 nm. Further, the thickness of the hole injection layer is preferably 0.1 nm to 200 nm, more preferably 0.5 nm to 100 nm, and particularly preferably 1 nm to 100 nm.

  The hole injection layer and the hole transport layer may have a single layer structure composed of one or more of the above materials, or a multilayer structure composed of a plurality of layers having the same composition or different compositions. Good.

--Electron injection layer, electron transport layer--
The electron injection layer and the electron transport layer are layers having a function of receiving electrons from the cathode or the cathode side and transporting them to the anode side. The electron injection material and the electron transport material used for these layers may be a low molecular compound or a high molecular compound.

  Specifically, pyridine derivatives, quinoline derivatives, pyrimidine derivatives, pyrazine derivatives, phthalazine derivatives, phenanthroline derivatives, triazine derivatives, triazole derivatives, oxazole derivatives, oxadiazole derivatives, imidazole derivatives, fluorenone derivatives, anthraquinodimethane derivatives, anthrone Derivatives, diphenylquinone derivatives, thiopyran dioxide derivatives, carbodiimide derivatives, fluorenylidenemethane derivatives, distyrylpyrazine derivatives, naphthalene, perylene and other aromatic ring tetracarboxylic acid anhydrides, phthalocyanine derivatives, 8-quinolinol derivative metal complexes, Metal phthalocyanines, various metal complexes represented by metal complexes with benzoxazole and benzothiazole as ligands, organosilane derivatives represented by siloles Body, or the like is preferably a layer containing.

  The electron injection layer or the electron transport layer of the organic electroluminescence device according to the present invention may contain an electron donating dopant. The electron-donating dopant introduced into the electron-injecting layer or the electron-transporting layer is not limited as long as it has an electron-donating property and has a property of reducing an organic compound. Alkali metals such as Li and alkaline-earth metals such as Mg Transition metals including rare earth metals and reducing organic compounds are preferably used. As the metal, a metal having a work function of 4.2 eV or less can be preferably used. Specifically, Li, Na, K, Be, Mg, Ca, Sr, Ba, Y, Cs, La, Sm, Gd , And Yb. Examples of the reducing organic compound include nitrogen-containing compounds, sulfur-containing compounds, and phosphorus-containing compounds.

  In addition, materials described in JP-A-6-212153, JP-A-2000-196140, JP-A-2003-68468, JP-A-2003-229278, JP-A-2004-342614, and the like can be used.

  These electron donating dopants may be used alone or in combination of two or more. The amount of the electron donating dopant varies depending on the type of material, but is preferably 0.1% by mass to 99% by mass, and 1.0% by mass to 80% by mass with respect to the electron transport layer material. Is more preferable, and 2.0 mass% to 70 mass% is particularly preferable.

  The thicknesses of the electron injection layer and the electron transport layer are each preferably 500 nm or less from the viewpoint of lowering the driving voltage. The thickness of the electron transport layer is preferably 1 nm to 500 nm, more preferably 5 nm to 200 nm, and particularly preferably 10 nm to 100 nm. Further, the thickness of the electron injection layer is preferably 0.1 nm to 200 nm, more preferably 0.2 nm to 100 nm, and particularly preferably 0.5 nm to 50 nm.

  The electron injection layer and the electron transport layer may have a single-layer structure composed of one or more of the materials described above, or a multilayer structure composed of a plurality of layers having the same composition or different compositions.

--Hole blocking layer--
The hole blocking layer is a layer having a function of preventing holes transported from the anode side to the light emitting layer from passing through to the cathode side. As the organic compound layer adjacent to the light emitting layer on the cathode side, a hole blocking layer can be provided.

  Examples of the compound constituting the hole blocking layer include aluminum complexes such as bis- (2-methyl-8-quinonylphenolate) aluminum (BAlq), triazole derivatives, phenanthroline derivatives such as BCP, and the like.

  The thickness of the hole blocking layer is preferably 1 nm to 500 nm, more preferably 5 nm to 200 nm, and particularly preferably 10 nm to 100 nm.

  The hole blocking layer may have a single-layer structure composed of one or more of the materials described above, or a multilayer structure composed of a plurality of layers having the same composition or different compositions.

--Electronic block layer--
The electron blocking layer is a layer having a function of preventing electrons transported from the cathode side to the light emitting layer from passing through to the anode side. In the present invention, an electron blocking layer can be provided as the organic compound layer adjacent to the light emitting layer on the anode side.

  As examples of the compound constituting the electron blocking layer, for example, those mentioned as the hole transport material described above can be applied.

  The thickness of the electron blocking layer is preferably 1 nm to 500 nm, more preferably 5 nm to 200 nm, and particularly preferably 10 nm to 100 nm.

  The hole blocking layer may have a single-layer structure composed of one or more of the materials described above, or a multilayer structure composed of a plurality of layers having the same composition or different compositions.

  In order to further improve the light emission efficiency, the light emitting layer can have a structure in which a charge generation layer is provided between a plurality of light emitting layers.

  The charge generation layer is a layer having a function of generating charges (holes and electrons) when an electric field is applied and a function of injecting the generated charges into a layer adjacent to the charge generation layer.

  The material for forming the charge generation layer is not particularly limited as long as the material has the above function, and may be formed of a single compound or a plurality of compounds.

  Specifically, it may be a conductive material, a semiconductive material such as a doped organic layer, or an electrically insulating material. 11-329748, Unexamined-Japanese-Patent No. 2003-272860, and the material of Unexamined-Japanese-Patent No. 2004-39617 are mentioned.

  More specifically, transparent conductive materials such as ITO and IZO (indium zinc oxide), fullerenes such as C60, conductive organic materials such as oligothiophene, metal phthalocyanines, metal-free phthalocyanines, metal porphyrins, Conductive organic materials such as metal porphyrins, metal materials such as Ca, Ag, Al, Mg: Ag alloy, Al: Li alloy, Mg: Li alloy, hole conductive materials, electron conductive materials, and mixtures thereof Can be mentioned.

Examples of the hole conductive material include 4,4 ′, 4 ″ -tris (2-naphthylphenylamino) triphenylamine (2-TNATA), N′-dinaphthyl-N, N′-diphenyl- [1. , 1′-biphenyl] -4,4′-diamine (NPD) and the like, F2,3,5,6-tetrafluoro-7,7,8,8-tetracyanoquinodimethane (4 -TCNQ), TCNQ, those doped with an oxidant having an electron withdrawing property such as FeCl ₃ , P-type conductive polymers, P-type semiconductors, etc., and the electron conductive material is an electron transport organic material And those doped with a metal or metal compound having a work function of less than 4.0 eV, N-type conductive polymers, and N-type semiconductors. Examples of the N-type semiconductor include N-type Si, N-type CdS, and N-type ZnS. Examples of the P-type semiconductor include P-type Si, P-type CdTe, and P-type CuO.

Further, an electrically insulating material such as V ₂ O ₅ can be used for the charge generation layer.

  The charge generation layer may be a single layer or a stack of a plurality of layers. As a structure in which a plurality of layers are stacked, a conductive material such as a transparent conductive material or a metal material and a hole conductive material, or a structure in which an electron conductive material is stacked, the above hole conductive material and electron conductive And a layer having a structure in which a functional material is laminated.

  In general, it is preferable to select a film thickness and a material for the charge generation layer so that the visible light transmittance is 50% or more. The film thickness is not particularly limited and can be appropriately selected according to the purpose, but is preferably 0.5 to 200 nm, more preferably 1 to 100 nm, further preferably 3 to 50 nm, and particularly preferably 5 to 30 nm. .

  The method for forming the charge generation layer is not particularly limited, and the method for forming the organic compound layer described above can be used.

The charge generation layer is formed between the two or more light emitting layers, and the anode side and the cathode side of the charge generation layer may include a material having a function of injecting charges into adjacent layers. In order to improve the electron injection property to the layer adjacent to the anode side, for example, an electron injection compound such as BaO, SrO, Li ₂ O, LiCl, LiF, MgF ₂ , MgO, and CaF _{2 is} added to the anode side of the charge generation layer. May be laminated.

  In addition to the contents mentioned above, the descriptions are based on JP 2003-45676 A, US Pat. No. 6,337,492, US Pat. No. 6,107,734, US Pat. No. 6,872,472, etc. Thus, the material for the charge generation layer can be selected.

<< Electrode >>
In the present invention, the electrode is not particularly limited as long as an electric field can be applied to the light emitting layer. The arrangement position of the electrodes is not particularly limited and may be appropriately selected depending on the purpose. For example, as shown in FIGS. 1 and 2, the electrodes having light reflectivity forming the optical resonator are in the same plane. It is preferably present above. The electrodes may be appropriately selected from transparent, translucent, light-reflective or light-transmissive anodes and cathodes, etc., depending on the form of arrangement in the organic light-emitting display device.

-Anode-
The anode usually has a function as an electrode for supplying holes to the organic light emitting layer constituting the organic compound layer, and there is no particular limitation on the shape, structure, size, etc. Organic electroluminescence According to the use and purpose of the element, it can be appropriately selected from known electrode materials. As described above, the anode is usually provided as a transparent anode.

  Suitable examples of the material for the anode include metals, alloys, metal oxides, conductive compounds, and mixtures thereof. Specific examples of the anode material include conductive metals such as tin oxide doped with antimony and fluorine (ATO, FTO), tin oxide, zinc oxide, indium oxide, indium tin oxide (ITO), and indium zinc oxide (IZO). Metals such as oxides, gold, silver, chromium, nickel, and mixtures or laminates of these metals and conductive metal oxides, inorganic conductive materials such as copper iodide and copper sulfide, polyaniline, polythiophene, polypyrrole, etc. Organic conductive materials, and a laminate of these and ITO. Among these, a conductive metal oxide is preferable, and ITO is particularly preferable from the viewpoint of productivity, high conductivity, transparency, and the like.

  The anode is composed of, for example, a wet method such as a printing method and a coating method, a physical method such as a vacuum deposition method, a sputtering method, and an ion plating method, and a chemical method such as a CVD method and a plasma CVD method. It can be formed on the substrate according to a method appropriately selected in consideration of suitability with the material to be processed. For example, when ITO is selected as the anode material, the anode can be formed according to a direct current or high frequency sputtering method, a vacuum deposition method, an ion plating method, or the like.

  In the present invention, the arrangement position of the anode is not particularly limited as long as it is provided so as to be in contact with the organic compound layer, and can be appropriately selected according to the use and purpose of the organic electroluminescence device. It may be formed on the entire surface of one of the compound layers, or may be formed on a part thereof.

  The patterning for forming the anode may be performed by chemical etching such as photolithography, or may be performed by physical etching such as laser, or vacuum deposition or sputtering with a mask overlapped. It may be performed by a lift-off method or a printing method.

  The thickness of the anode can be appropriately selected depending on the material constituting the anode and cannot be generally defined, but is usually about 10 nm to 50 μm, and preferably 50 nm to 20 μm.

The resistance value of the anode is preferably 10 ³ Ω / □ or less, and more preferably 10 ² Ω / □ or less. When the anode is transparent, it may be colorless and transparent or colored and transparent. In order to emit light from the transparent anode side, the transmittance is preferably 60% or more, and more preferably 70% or more.

  The transparent anode is detailed in Yutaka Sawada's “New Development of Transparent Conductive Film” published by CMC (1999), and the matters described here can be applied to the present invention. In the case of using a plastic substrate having low heat resistance, a transparent anode formed using ITO or IZO at a low temperature of 150 ° C. or lower is preferable.

-Cathode-
The cathode usually has a function as an electrode for injecting electrons into the organic light emitting layer constituting the organic compound layer described above, and there is no particular limitation on the shape, structure, size, etc. According to the use and purpose of the light emitting element, it can be appropriately selected from known electrode materials.

  Examples of the material constituting the cathode include metals, alloys, metal oxides, electrically conductive compounds, and mixtures thereof. Specific examples include alkali metals (eg, Li, Na, K, Cs, etc.), alkaline earth metals (eg, Mg, Ca, etc.), gold, silver, lead, aluminum, sodium-potassium alloys, lithium-aluminum alloys, magnesium. -Rare earth metals such as silver alloys, indium and ytterbium. These may be used alone, but two or more can be suitably used in combination from the viewpoint of achieving both stability and electron injection.

  Among these, the material constituting the cathode is preferably an alkali metal or an alkaline earth metal from the viewpoint of electron injection, and a material mainly composed of aluminum is preferable from the viewpoint of excellent storage stability. The material mainly composed of aluminum is aluminum alone, an alloy of aluminum and 0.01% by mass to 10% by mass of alkali metal or alkaline earth metal, or a mixture thereof (for example, lithium-aluminum alloy, magnesium-aluminum alloy). Etc.).

  The cathode materials are described in detail in JP-A-2-15595 and JP-A-5-121172, and the materials described in these publications can also be applied in the present invention.

  There is no restriction | limiting in particular about the formation method of a cathode, According to a well-known method, it can carry out. For example, the above-described cathode is configured from a wet method such as a printing method or a coating method, a physical method such as a vacuum deposition method, a sputtering method, or an ion plating method, or a chemical method such as CVD or plasma CVD method. It can be formed according to a method appropriately selected in consideration of suitability with the material. For example, when a metal or the like is selected as the material of the cathode, one kind or two or more kinds thereof can be simultaneously or sequentially performed according to a sputtering method or the like.

  Patterning when forming the cathode may be performed by chemical etching such as photolithography, physical etching by laser, or the like, or by vacuum deposition or sputtering with the mask overlaid. It may be performed by a lift-off method or a printing method.

  In the present invention, the arrangement position of the cathode is not particularly limited as long as it is provided so that an electric field can be applied to the light emitting layer, and may be formed on the entire light emitting layer or a part thereof. Also good.

  Further, a dielectric layer made of an alkali metal or alkaline earth metal fluoride or oxide may be inserted between the cathode and the organic compound layer with a thickness of 0.1 nm to 5 nm. This dielectric layer can also be regarded as a kind of electron injection layer. The dielectric layer can be formed by, for example, a vacuum deposition method, a sputtering method, an ion plating method, or the like.

  The thickness of the cathode can be appropriately selected depending on the material constituting the cathode and cannot be generally defined, but is usually about 10 nm to 5 μm, and preferably 50 nm to 1 μm.

  Further, the cathode may be transparent, translucent, or opaque. The transparent cathode can be formed by depositing a thin cathode material to a thickness of 1 nm to 10 nm and further laminating a transparent conductive material such as ITO or IZO.

<< Board >>
In the OLED substrate, the shape, structure, size, material, and the like of the substrate may be appropriately selected according to the purpose. In general, the shape of the substrate is preferably a plate shape. The structure of the substrate may be a single layer structure, a laminated structure, may be formed of a single member, or may be formed of two or more members. The substrate may be colorless and transparent or colored and transparent, but is preferably colorless and transparent in that it does not scatter or attenuate light emitted from the light emitting layer. Moreover, it is preferable that it is flexible from the point of convenience. The material of the OLED substrate may be the same as the light transmissive substrate of the optical member described above. As an aspect of the arrangement of the OLED substrate, as long as it does not affect the light emission and light transmission from the OLED substrate, it may be appropriately selected according to the purpose, but it is not arranged on the optical path of the light from the OLED substrate. Thus, it may be arranged on the opposite side of the organic EL layer as seen from the light reflecting electrode.

<Drive>
The organic light emitting display device can obtain light emission by applying a direct current (which may include an alternating current component as necessary) voltage (usually 2 to 15 volts) or a direct current between the anode and the cathode. it can.

  Regarding the driving method of the organic light emitting display device, JP-A-2-148687, JP-A-6-301355, JP-A-5-290080, JP-A-7-134558, JP-A-8-234485, and JP-A-8-2441047, The driving methods described in Japanese Patent No. 2784615, US Pat. Nos. 5,828,429, 6,023,308, etc. can be applied.

(Method for manufacturing organic light-emitting display device)
The method for manufacturing an organic light emitting display device according to the present invention includes a step of sequentially laminating a light reflecting electrode, an organic EL layer, and a light transmitting electrode on a substrate, and a light transmission having a recess on a light transmitting substrate different from the substrate. An optical resonator that emits light of at least one color of red, green, and blue is formed between the step of forming a layer and the light-reflecting electrode and the surface of the recess facing the light-reflecting electrode. As described above, a step of fixing the light transmission layer and the light transmission electrode to face each other is included, and other steps are included as necessary.

  There is no restriction | limiting in particular as a process of laminating | stacking a light reflection electrode, an organic electroluminescent layer, and a light transmissive electrode in order on the said board | substrate, What is necessary is just to select suitably according to the objective, For example, in said <OLED board | substrate> The method mentioned may be performed. The step of forming the light-transmitting layer having a recess on the light-transmitting substrate is not particularly limited and may be appropriately selected depending on the intended purpose. For example, the method mentioned in the above section <Optical member> It may be performed by. The step of fixing the light transmissive layer and the light transmissive electrode so as to face each other is not particularly limited and may be appropriately selected depending on the purpose. For example, by the method mentioned in the section of <Adhesion> above Just do it.

  EXAMPLES Next, although an Example and a comparative example are given and this invention is demonstrated more concretely, this invention is not restrict | limited to the following Example.

Example 1
<Creation of optical member>
<< Creation of mold for optical member >>
A photosensitive resist is applied onto a quartz substrate by a spin coating method, and pattern exposure is performed on the quartz substrate so as to correspond to a pixel composed of any one of red, green, blue, and white sub-pixels. A quartz substrate surface at a predetermined position was opened. Thereafter, the opening was further etched by a predetermined amount by dry etching. Further, resist patterning and dry etching were repeated so as to correspond to other subpixels and pixels. Etching the concave portion corresponding to the green pixel from the quartz substrate surface to 98 nm, the concave portion corresponding to the blue pixel from the quartz substrate surface to 258 nm, the portion corresponding to the convex portion separating the pixels and the position corresponding to the white pixel from the quartz substrate surface by etching at 278 nm. However, the recess corresponding to the red pixel was not etched. Thus, the mold used for formation of an uneven part was obtained. In addition, the recessed part depth of the obtained mold for uneven | corrugated | grooved part formation is as follows.

[Recess depth of mold for optical member]
Red equivalent part: depth 0nm
Green equivalent part: depth 98nm
Blue equivalent part: Depth 258nm
White equivalent part and between pixels: depth 278 nm

<< Optical member >>
<<< Light-transmissive substrate having a color filter layer >>>
Black color resist CK-8400 (manufactured by FUJIFILM Electronics Materials Co., Ltd.) was applied onto a glass substrate for color filter production using a spin coater so that the dry film thickness was 1.0 μm, and at 120 ° C. It was dried for 2 minutes to form a black uniform coating film.

Next, using an exposure apparatus, the coating film was irradiated with an exposure dose of 300 mJ / cm ² through a 100 μm mask at a wavelength of 365 nm. After irradiation, the film was developed at 26 ° C. for 90 seconds using a 10% CD-1 (Fuji Film Electronics Materials Co., Ltd.) developer. Subsequently, the substrate was rinsed with running water for 20 seconds, dried with an air knife, and heat-treated at 220 ° C. for 60 minutes to form a black matrix pattern image.

  Next, the following three color curable compositions were dispersed with a sand mill all day and night. The dispersions obtained in green, red, and blue are also referred to as dispersions (A-1), (A-2), and (A-3), respectively.

[Green: Dispersion (A-1)]
80 parts by mass of benzyl methacrylate / methacrylic acid copolymer (weight average molecular weight 30,000, acid value 120)
Propylene glycol monomethyl ether acetate 500 parts by weight Copper phthalocyanine pigment 33 parts by weight C.I. I. Pigment Yellow 185 67 parts by mass

[Red: Dispersion (A-2)]
80 parts by mass of benzyl methacrylate / methacrylic acid copolymer (weight average molecular weight 30,000, acid value 120)
Propylene glycol monomethyl ether acetate 500 parts by mass Pigment Red 254 50 parts by mass Pigment Red PR177 50 parts by mass

[Blue: Dispersion (A-3)]
80 parts by mass of benzyl methacrylate / methacrylic acid copolymer (weight average molecular weight 30,000, acid value 120)
Propylene glycol monomethyl ether acetate 500 parts by mass Pigment Blue 15: 6 95 parts by mass Pigment Violet 23 5 parts by mass

  Next, the following components are added to 60 parts by mass of the curable composition for each color (that is, dispersions (A-1), (A-2) and (A-3)), and A composition was obtained.

Dipentaerythritol hexaacrylate (DPHA) 80 parts by mass 4- [o-bromo-pN, N-di (ethoxycarbonyl) aminophenyl] 2,6-di (trichloromethyl) -S-triazine 5 parts by mass 7-[{4-Chloro-6- (diethylamino) -S-triazin-2-yl} amino] -3-phenylcoumarin 2 parts by mass Hydroquinone monomethyl ether 0.01 parts by mass Propylene glycol monomethyl ether acetate 500 parts by mass

  The composition for each color obtained by adding as described above was uniformly mixed and then filtered through a filter having a pore diameter of 5 μm to obtain the three-color curable composition of the present invention. Among these, the green curable composition was applied on a glass substrate on which a black matrix was formed using a spin coater so that the dry film thickness was 1.0 μm, and dried at 120 ° C. for 2 minutes to obtain a uniform green color. A coating film was formed.

Next, using an exposure apparatus, the coating film was irradiated with an exposure dose of 300 mJ / cm ² through a 100 μm mask at a wavelength of 365 nm. After irradiation, development was performed at 26 ° C. for 60 seconds using a 10% CD-1 (Fuji Film Electronics Materials Co., Ltd.) developer. Subsequently, after rinsing with running water for 20 seconds, it was dried with an air knife, and heat-treated at 220 ° C. for 60 minutes to form a green pattern image (green pixel). This operation is similarly performed on the same glass substrate for the red curable composition and the blue curable composition, and a red pattern image (red pixel) and a blue pattern image (blue pixel) are sequentially formed. did. The optical characteristics of this color filter substrate are shown in FIG.

<<< Light Transmission Layer >>>
Next, on the light transmissive substrate having the color filter layer thus formed, the following components were applied by spin coating to form a light transmissive layer (thickness: 1,000 nm).

[Light transmission layer]
It was prepared using PAK-02 (Toyo Gosei Co., Ltd.).

  On the light transmission layer obtained as described above, an uneven portion was formed by a transfer method using the uneven portion forming mold obtained as described above. The mold was pressed against the light transmission layer, and UV irradiation was performed from the mold side made of a quartz substrate to cure the material of the light transmission layer, thereby forming a recess on the surface of the same layer.

  On the uneven surface of the light transmissive layer thus obtained, Ag was deposited by a vacuum vapor deposition method to form a light semi-transmissive reflective layer (film thickness 10 nm) to obtain an optical member.

[Conditions for forming a light transflective layer]
A general Ag vacuum deposition method is used to selectively form a film with a metal mask so that the film is formed in a necessary range. In particular, since the white sub-pixel emits the spectrum of the light source, a light transflective layer is not formed so as not to have an optical resonator structure. In addition, in the case of a configuration in which the convex portions formed on the light transmission layer of the optical member as shown in FIGS. 1 and 3 are combined with a coupling agent described later, the organic material remains on the convex portion top surface, which is an adhesive surface. The light-transmitting layer is also exposed at the location, and the light transflective layer is not formed.

  A step between the surface of the light transmission layer in the convex portion of the optical member and the surface of the light semi-transmissive reflection layer in the concave portion acts as a part of the optical resonance length. This step amount is shown below as a recess depth dimension.

[Optical member recess]
Red part: depth 268nm
Green equivalent part: depth 170nm
Blue equivalent part: Depth 10nm
White equivalent part and between pixels: Depth 0 nm

<Creation of OLED substrate>
On the substrate on which the reflective electrode made of Al was formed, an OLED substrate was prepared by sequentially performing vacuum deposition film formation of an organic layer and ion plating film formation of a transparent electrode. The light emission characteristics of this OLED substrate are shown in FIG.

[Electron injection layer]
Material: LiF
Deposition rate: 0.1 liter / sec
Deposition time: 100 sec
Film thickness: 10 mm = 1 nm

[Electron transport layer]
Material: BAlq
Deposition rate: 1cm / sec
Deposition time: 100 sec
Film thickness: 100 mm = 10 nm

[Light emitting layer (blue)]
Material: Co-evaporation of mCP (host) and luminescent material (D-24) (guest) Deposition rate: mCP = 0.9 Å / sec, luminescent material B = 0.1 Å / sec
Deposition time: 100 sec
Film thickness: 100 mm = 10 nm

[Light emitting layer (green)]
Material: Co-evaporation of mCP (host) and luminescent material (above D-22) (guest) Deposition rate: mCP = 0.9 Å / sec, luminescent material G = 0.1 Å / sec
Deposition time: 150 sec
Film thickness: 150mm = 15nm

[Light emitting layer (red)]
Material: Co-evaporation of BAlq (host) and luminescent material (above D-7) (guest) Deposition rate: BAlq = 0.9 Å / sec, luminescent material R = 0.1 Å / sec
Deposition time: 200 sec
Film thickness: 200mm = 20nm

[Hole transport layer]
Material: a-NPD
Deposition rate: 1cm / sec
Deposition time: 100 sec
Film thickness: 100 mm = 10 nm

[Hole injection layer]
Material: Co-evaporation of 2-TNATA (host) and F4-TCNQ (guest) Deposition rate: 2-TNATA = 2Å / sec, F4-TCNQ = 0.1Å / sec
Deposition time: 48 sec
Film thickness: 100 mm = 10 nm

[Transparent electrode layer]
Material: ITO
Deposition rate: 50cm / sec
Deposition time: 200 sec
Film thickness: 1,000 mm = 100 nm

<Adhesion between optical member and OLED substrate>
[Synthesis of Compound A]
Compound A for bonding the optical member and the OLED substrate was synthesized as follows. This synthesis was performed by the following two steps.

1. Step 1 (Synthesis of Compound a)
24.5 g (0.12 mol) of 1-hydroxycyclohexyl phenyl ketone is dissolved in a mixed solvent of DMAc 50 g and THF 50 g, and 7.2 g (0.18 mol) of NaH (60% in oil) is gradually added in an ice bath. It was. Thereto, 44.2 g (0.18 mol) of 11-bromo-1-undecene (95%) was added dropwise and reacted at room temperature for 1 hour. The reaction solution was poured into ice water and extracted with ethyl acetate to obtain a mixture containing compound a in the form of a yellow solution. 37 g of this mixture was dissolved in 370 mL of acetonitrile, and 7.4 g of water was added. 1.85 g of p-toluenesulfonic acid monohydrate was added and stirred at room temperature for 20 minutes. The organic phase was extracted with ethyl acetate and the solvent was distilled off. Compound a was isolated by column chromatography (filler: Wakogel C-200, developing solvent: ethyl acetate / hexane = 1/80). This synthesis scheme is as follows.

¹ H NMR (300 MHz CDCl ₃ )
δ = 1.2-1.8 (mb, 24H), 2.0 (q, 2H), 3.2 (t, J = 6.6, 2H), 4.9-5.0 (m, 2H) 5.8 (ddt, J = 24.4, J = 10.5, J = 6.6, 1H.), 7.4 (t, J = 7.4, 2H), 7.5 (t, J = 7.4, 1H), 8.3 (d, 1H)

2. Step 2 (Synthesis of Compound A by Hydrosilylation of Compound a)
Compounds of 5.0 g a (0.014 mol) in _{Speir catalyst (H 2 PtCl 6 ·} 6H 2 O / 2-PrOH, 0.1 mol / L) 2 drops of trichlorosilane 2.8g in an ice bath (0.021 mol) was added dropwise and stirred. After 1 hour, 1.6 g (0.012 mol) of trichlorosilane was added dropwise, and the temperature was returned to room temperature. The reaction was complete after 3 hours. After completion of the reaction, unreacted trichlorosilane was distilled off under reduced pressure to obtain Compound A.
A synthesis scheme is shown below.

¹ H NMR (300 MHz CDCl ₃ )
δ = 1.2−1.8 (m, 30H), 3.2 (t, J = 6.3, 2H), 7.3-7.7 (m, 3H), 8.3 (d, 2H) )

(Coating process to OLED substrate)
A dehydrated toluene solution of 12.5% by mass of Compound A was applied to the surface of the transparent electrode layer of the OLED substrate and dried at room temperature (air-dried).

(Adhesion with optical members)
The following 1. Or 2. In particular, when UV irradiation cannot be applied to the bonded part (shadowed by a color filter, etc.) Glue by the method of. When the black matrix in the color filter layer is not configured, By this method, UV irradiation is performed from the light-transmitting substrate side of the optical member through the substrate and the light-transmitting layer and bonded.

1. The transparent electrode surface (inorganic material surface) of the OLED substrate coated with Compound A and the convex top surface (organic material surface) of the light transmission layer of the optical member are brought into close contact with each other, UV-exposed and bonded.
2. Transparent electrode surface (inorganic material surface) of OLED substrate coated with 0.1% AIBN (azobisbutyronitrile) methanol solution on the top surface (organic material surface) of the light transmission layer of the optical member and compound A ), And reacted at 80 ° C. for 12 hours to bond.

(Example 2)
In Example 1, it replaced with having bonded the optical member and the OLED board | substrate using the coupling agent, and it carried out similarly to Example 1 except having performed on the following conditions, and obtained the organic light emitting display apparatus. It was.

  In order to form the recesses in the light transmission layer of the optical member, an optical member having the recess dimensions of the following dimensions was obtained using a mold for optical members having the recess dimensions of the following dimensions.

[Mold recess for optical member]
Red equivalent part: depth 0nm
Green equivalent part: depth 97nm
Blue equivalent part: Depth 293nm
White equivalent part and between pixels: Depth 313 nm

[Recess depth of optical member]
Red equivalent part: Depth 303nm
Green equivalent part: depth 206nm
Blue equivalent part: Depth 10nm
White equivalent part and between pixels: Depth 0 nm

  An epoxy adhesive having a refractive index equivalent to that of the transparent electrode layer of the OLED substrate was dispersed in the recesses of the obtained optical member in accordance with an ink jet method. The filling conditions were such that the adhesive was filled into a volume defined by the bottom of the formed recess and the surface of the optical member defined by the formed protrusion.

(Comparative example)
An organic light emitting display device was obtained by superimposing an optical member that does not form a light transmission layer on the OLED substrate, that is, a simple color filter substrate. Both the OLED substrate and the color filter have the same configuration and characteristics as described above.

<Evaluation>
Using the organic light emitting display devices obtained in Examples 1 and 2 and the comparative example, the front intensity spectrum of the light emitted from each pixel was measured under the following conditions. The results are shown in FIG. 5, FIG. 6 and FIG. Here, the maximum intensity (peak intensity) of white (W) is set to 1, and the front intensity is normalized and compared.

  In the comparative example, the wavelength of white light from the light source is selected by a color filter, but the maximum transmittance of each color of blue (B), green (G), and red (R) is 1 or less, so the front intensity of each color is 1 or less, and the wavelength distribution is a wide band according to the characteristics of the color filter. That is, the output is weak and the color is poor.

  On the other hand, in each embodiment, blue (B), green (G), and red (R) are strengthened at a predetermined wavelength to narrow the band by the structure of the optical resonator. In other words, the output is strong and has a good color, and an organic light-emitting display device with improved display characteristics can be obtained by using the optical member according to the present invention.

  Since the organic light emitting display device according to the present invention is capable of high-definition full-color display, it can be used in a wide range of fields including mobile phone displays, personal digital assistants (PDAs), computer displays, automobile information displays, TV monitors, or general lighting. It can be suitably used.

DESCRIPTION OF SYMBOLS 10 Optical member 12 Light transmissive layer 14 Convex part 15 Concave 16 Light semi-transmissive reflective layer 18 Color filter layer 18r Red filter part 18g Green filter part 18b Blue filter part 18w White filter part 19 Light transmissive substrate 20 OLED substrate 22 Substrate 24 Light Reflective electrode 26 Organic EL layer 28 Light transmissive electrode 30 Adhesion part 32 Pixel circuit 34 Contact hole 36 Insulating layer 100 Organic light emitting display device

Claims (13)

An organic light-emitting display device having a substrate, a light reflection electrode, an organic EL layer, a light transmission electrode, and a light transmission layer having a concave portion and a convex portion on the upper surface in this order,
The refractive index of the concave portion of the light transmission layer is equal to the refractive index of the light transmission electrode,
The convex portion of the light transmission layer and the light transmission electrode are fixed to face each other,
An optical resonator is formed between the light reflecting electrode and the surface of the recess facing the light reflecting electrode,
An organic light emitting display device, wherein light transmitted from the light transmission layer through the optical resonator is light of at least one of red, green, and blue.   The organic light emitting display device according to claim 1, wherein the light transmission layer is formed of a single member.   The organic light emitting display device according to claim 2, wherein the material of one member is a photocurable resin, a thermoplastic resin, or a thermosetting resin.   The organic light-emitting display device according to any one of claims 1 to 3, further comprising a light semi-transmissive reflective layer on a concave surface of the light transmissive layer. The organic light-emitting display device according to claim 4, wherein the concave portion of the light transmission layer is filled with an adhesive. 6. The organic light emitting display device according to claim 1, wherein the depth of the plurality of concave portions of the light transmission layer is different so that at least one light of red, green and blue is emitted. The organic light emitting display device according to claim 1, wherein the light reflecting electrode is present on the same plane. The organic light emitting display device according to claim 1, wherein the organic EL layer emits white light. The organic light emitting display device according to claim 1, further comprising a color filter layer on a light emitting side of the light transmission layer. A step of sequentially laminating a light reflecting electrode, an organic EL layer and a light transmitting electrode on a substrate;
Forming a light transmissive layer having a concave portion and a convex portion on an upper surface on a light transmissive substrate different from the substrate;
The light transmission layer is formed such that an optical resonator that emits light of at least one of red, green, and blue is formed between the light reflection electrode and a surface of the recess facing the light reflection electrode. A step of fixing the convex portion and the light transmitting electrode opposite to each other,
A method for manufacturing an organic light emitting display device, comprising: The method of manufacturing an organic light emitting display device according to claim 10, wherein the step of forming the concave portion of the light transmission layer is performed by mold transfer. The method of manufacturing an organic light emitting display device according to claim 10, wherein the step of fixing the light transmission layer and the light transmission electrode so as to face each other is performed using a coupling agent. The manufacturing of the organic light emitting display device according to any one of claims 10 to 12, wherein the step of fixing the light transmitting layer and the light transmitting electrode so as to face each other is performed by filling a concave portion of the light transmitting layer with an adhesive. Method.