JP2008218343A - Manufacturing method of organic electroluminescent light-emitting device - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a manufacturing method of an organic electroluminescent light-emitting device having a patterned layer with a high refractive index in which emitted light from the organic EL layer can be efficiently discharged outside. <P>SOLUTION: The manufacturing method of an organic electroluminescent light-emitting device includes a process in which an organic EL element, a color conversion layer by a vapor depositing method and a barrier layer are formed on a supporting body, and a patterned high refractive index layer is formed on the barrier layer by dry etching with a discontinuous film formed by a dry process as a mask and the barrier layer as an etching-stop layer and is stuck to a color filter. <P>COPYRIGHT: (C)2008,JPO&INPIT

Description

  The present invention relates to a method for manufacturing an organic EL light emitting device. More specifically, the present invention relates to a method for manufacturing an organic EL light emitting device having a patterned high refractive index layer for efficiently emitting light emitted from an organic EL layer to the outside.

  In recent years, organic EL devices have been actively researched for practical use. Organic EL elements are expected to achieve high luminance and luminous efficiency because they can achieve high current density at low voltage, and the practical application of organic multi-color EL displays capable of high-definition multi-color or full-color display is expected. Expected. However, in addition to the non-directional light emission in the organic EL layer, not all of the light emitted from the organic EL layer can be taken out due to the refractive index structure of the light emitter, resulting in a decrease in light emission efficiency. Is inviting.

  In order to improve the external extraction efficiency of light emission, it has been proposed to form a diffraction grating structure on a substrate (see Patent Document 1). Further, as a manufacturing method of the diffraction grating structure, a method by pattern doping of a high refractive index material with respect to a low refractive index material (see Patent Document 2), or a method by baking or wet etching of a patterned photoresist material (Patent Document 2) Document 3) has been proposed. Furthermore, a structure in which a high refractive index portion made of an inorganic compound and a fine space layer containing gas or vacuum are arranged in a pattern has been proposed (see Patent Document 4).

Japanese Patent Laid-Open No. 11-283951 JP 2003-257620 A JP 2006-12826 A JP 2004-273416 A

  However, regarding the introduction of the diffraction grating structure, there is a problem in that the manufacturing process for forming fine irregularities is complicated, or the durability and reliability are lowered due to the formation of the organic EL element on the irregular structure forming the diffraction grating. Is being viewed.

  When an attempt is made to produce a proposed diffraction grating structure on an organic EL element that extracts light emission on the surface opposite to the substrate, etching (wet and dry) conditions during pattern formation or severe conditions such as doping or baking There is a concern that the characteristics of the organic EL element may deteriorate due to various manufacturing conditions. In particular, in a color conversion type organic EL light emitting device in which a color conversion layer is provided on the light extraction side surface of an organic EL element, there is a concern that the characteristics of the color conversion layer may deteriorate in addition to the organic EL element.

  Therefore, the problem to be solved by the present invention is to provide a high refractive index layer having a pattern-like (preferably diffraction grating-like) structure composed of a plurality of portions without deteriorating the characteristics of the organic EL element and the color conversion layer. It is providing the manufacturing method of the organic electroluminescent light emitting device which can provide.

The manufacturing method of the organic EL light emitting device of the present invention is as follows:
(A) forming an organic EL element having a reflective electrode, an organic EL layer and a transparent electrode in this order on a support;
(B) forming a color conversion layer on the organic EL element by vapor deposition;
(C) forming a barrier layer on the color conversion layer;
(D) laminating a high refractive index material layer on the barrier layer;
(E) patterning the high-refractive index material layer to form a high-refractive index layer having a plurality of portions, and the step (e) is performed on the upper surface of the high-refractive index material layer by a dry process. The present invention is carried out by forming a continuous film and etching the high refractive index material layer using the discontinuous film as a mask. Here, the discontinuous film and / or the barrier layer may be formed using a compound selected from the group consisting of an oxide containing indium or zinc, Al ₂ O ₃ , ZrO ₂ , and TiO ₂ . The high refractive index material layer may be formed using metal nitride, metal oxide, or metal oxynitride.

  As a modification of the method for manufacturing the organic EL light emitting device of the present invention, the barrier layer includes a first barrier layer formed on the color conversion layer, and a second barrier layer formed on the first barrier layer. You may comprise. In this modification, the second barrier layer can be formed using an oxide containing indium or zinc, or an oxide containing an element selected from the group consisting of Al, Zr and Ti, and the first barrier layer Can be formed using metal nitride, metal oxide, or metal oxynitride.

In the manufacturing method of the organic EL light emitting device of the present invention, following the step (e),
(F) forming a color filter layer on the transparent support to obtain a color filter;
(G) You may further include the process of bonding the laminated body obtained at the process (e), and the color filter obtained at the process (f) so that a color filter layer and a high refractive index layer may oppose. .

  By taking the above-described configuration, a pattern formed of a plurality of parts can be formed by a simple method without damaging a layer formed by an evaporation method such as an underlying organic EL layer or a color conversion layer. It is possible to form a high refractive index layer.

The manufacturing method of the organic EL light emitting device of the present invention is as follows:
(A) forming an organic EL element having a reflective electrode, an organic EL layer and a transparent electrode in this order on a support;
(B) forming a color conversion layer on the organic EL element by vapor deposition;
(C) forming a barrier layer on the color conversion layer;
(D) laminating a high refractive index material layer on the barrier layer;
(E) patterning the high-refractive index material layer to form a high-refractive index layer having a plurality of portions, and the step (e) is performed on the upper surface of the high-refractive index material layer by a dry process. The present invention is characterized in that a continuous film is formed and the high refractive index material layer is etched using the discontinuous film as a mask. Hereinafter, the present invention will be described with reference to FIG.

  In FIG. 1A, the organic EL element 20, the color conversion layer 30, the barrier layer 40, and the non-patterned high refractive index material layer 52 are laminated on the support 10 at the end of the step (d). It is a figure which shows the state performed.

  In the step (a), the organic EL element 20 including the reflective electrode, the organic EL layer, and the transparent electrode in this order is formed on the support 10.

(Support)
In the present invention, the support 10 is made of cellulose ester such as diacetylcellulose, triacetylcellulose (TAC), propionylcellulose, butyrylcellulose, acetylpropionylcellulose, nitrocellulose; polyamide; polycarbonate; polyethylene terephthalate, polyethylene naphthalate, polybutylene. Polyester such as terephthalate, poly-1,4-cyclohexanedimethylene terephthalate, polyethylene-1,2-diphenoxyethane-4,4′-dicarboxylate, polybutylene terephthalate; polystyrene; polyethylene, polypropylene, polymethylpentene, etc. Polyolefin; Acrylic resin such as polymethyl methacrylate; Polycarbonate; Polysulfone; Polyethersulfone; Poly Ether ketone; polyether imide; polyoxyethylene; can be formed using polymeric materials such as norbornene resin; and glass; semiconductors such as silicon; or formed using optically opaque materials such as ceramics You can also In the case of using a polymer material, the support 10 may be rigid or flexible.

(Reflective electrode)
The reflective electrode is vapor-deposited using a highly reflective metal (Al, Ag, Mo, W, Ni, Cr, etc.), an amorphous alloy (NiP, NiB, CrP, CrB, etc.), or a microcrystalline alloy (NiAl, etc.). It can be formed by a dry process such as sputtering or sputtering.

(Organic EL layer)
The organic EL layer includes at least an organic light emitting layer and has a structure in which a hole injection layer, a hole transport layer, an electron transport layer and / or an electron injection layer are interposed as required. Specifically, an organic EL element having the following layer structure is adopted (the anode and the cathode are either a reflective electrode or a transparent electrode).

(1) Anode / organic light emitting layer / cathode (2) Anode / hole injection layer / organic light emitting layer / cathode (3) Anode / organic light emitting layer / electron injection layer / cathode (4) Anode / hole injection layer / organic Light emitting layer / electron injection layer / cathode (5) Anode / hole transport layer / organic light emitting layer / electron injection layer / cathode (6) Anode / hole injection layer / hole transport layer / organic light emitting layer / electron injection layer / Cathode (7) Anode / hole injection layer / hole transport layer / organic light emitting layer / electron transport layer / electron injection layer / cathode

  As a material of each layer constituting the organic EL layer, known materials are used. Moreover, each layer which comprises an organic EL layer can be formed using the arbitrary methods known in the said techniques, such as a vapor deposition method. For example, organic light-emitting layer materials for obtaining blue to blue-green light emission include fluorescent brighteners such as benzothiazole, benzimidazole, and benzoxazole, metal chelated oxonium compounds, and styrylbenzene. Materials such as compounds and aromatic dimethylidin compounds are preferably used.

(Transparent electrode)
The transparent electrode is made of ITO, tin oxide, indium oxide, IZO, zinc oxide, zinc-aluminum oxide, zinc-gallium oxide, or a conductive transparent metal obtained by adding a dopant such as F or Sb to these oxides. It can be formed using an oxide. The transparent electrode is formed using a vapor deposition method, a sputtering method, or a chemical vapor deposition (CVD) method, and is preferably formed using a sputtering method.

(Cathode buffer layer)
Note that a cathode buffer layer may be provided at the interface between the cathode (either the reflective electrode or the transparent electrode) and the organic EL layer to improve the electron injection efficiency. As a material for the cathode buffer layer, an alkali metal such as Li, Na, K, or Cs, an alkaline earth metal such as Ba or Sr, an alloy containing them, a rare earth metal, or a fluoride of these metals may be used. Yes, but not limited to them. The thickness of the cathode buffer layer can be appropriately selected in consideration of the driving voltage, transparency, and the like, but in a normal case, the thickness is preferably 10 nm or less.

The organic EL element 20 of the present invention may have a plurality of light emitting units controlled independently. For example, both the reflective electrode and the transparent electrode are formed from a plurality of stripe-shaped partial electrodes, and the direction in which the stripe-shaped partial electrodes constituting the reflective electrode extend and the direction in which the stripe-shaped partial electrodes constituting the transparent electrode extend (preferably Can be formed to form an organic EL element 20 having a plurality of independent light emitting units driven in a passive matrix manner. Alternatively, a plurality of switching elements are formed on the support 10, a reflective electrode composed of a plurality of parts connected to the switching elements in a one-to-one relationship is formed, and an integrated transparent electrode that functions as a common electrode By forming it, the organic EL element 20 having a plurality of light emitting portions of an active matrix driving type may be formed. Further, when forming a reflective electrode composed of a plurality of partial electrodes for passive and active matrix driving, an insulating metal oxide (TiO ₂ , ZrO ₂ , AlO _x etc.) or an insulating metal nitride (AlN, An insulating film may be formed in the gap between the plurality of partial electrodes using SiN or the like.

  In the step (b), the color conversion layer 30 is formed on the organic EL element 20.

(Color conversion layer)
The color conversion layer 30 in the present invention is a layer formed from one or a plurality of color conversion dyes, and preferably has a thickness of 1 μm or less, more preferably 200 nm to 1 μm. The color conversion layer 30 is formed by a dry process, preferably a vapor deposition method (including resistance heating and electron beam heating). When the color conversion layer 30 is formed using a plurality of types of color conversion dyes, a preliminary mixture obtained by mixing a plurality of types of color conversion dyes at a predetermined ratio may be prepared in advance, and co-evaporation may be performed using the preliminary mixture. Good. Alternatively, a plurality of types of color conversion dyes may be disposed in separate heating portions, and the respective color conversion dyes may be separately heated to perform co-evaporation. In particular, the latter method is effective when there is a large difference in characteristics (evaporation rate, vapor pressure, etc.) among a plurality of types of color conversion dyes.

  Examples of the color conversion dye for forming the color conversion layer 30 include 3- (2-benzothiazolyl) -7-diethylaminocoumarin (coumarin 6), 3- (2-benzimidazolyl) -7-diethylaminocoumarin (coumarin 7), and coumarin. Coumarin dyes such as 135; naphthalimide dyes such as Solvent Yellow 43 and Solvent Yellow 44; 4-dicyanomethylene-2-methyl-6- (p-dimethylaminostyryl) -4H-pyran (DCM-1, ( I)), cyanine dyes such as DCM-2 (II) and DCJTB (III); xanthene dyes such as rhodamine B and rhodamine 6G; pyridine dyes such as pyridine 1; 4,4-difluoro-1,3, 5,7-tetraphenyl-4-bora-3a, 4a-diaza-s-indacene (IV), lumogen F red, Nile red (V), etc. can be used.

  In step (c), the barrier layer 40 is formed on the color conversion layer 30.

(Barrier layer)
The barrier layer 40 is a layer in which the etching does not proceed during the dry etching of the high refractive index material layer 52 or the etching progresses slower than the high refractive index material layer 52 (that is, the selection ratio is high). . In addition, the barrier layer 40 is desirably optically transparent in order to finally pass through the organic EL layer and pass through the color conversion layer 30. Depending on the dry etching conditions of the high refractive index material layer 52, for example, when dry etching is performed by reactive ion etching (RIE) using an etching gas containing fluorine, an oxide containing indium or zinc, The barrier layer 40 can be formed using a compound selected from the group consisting of Al ₂ O ₃ , ZrO ₂ and TiO ₂ . Preferred oxides include transparent conductive oxides such as indium oxide, zinc oxide, indium-zinc oxide (IZO), indium-tin oxide (ITO). The barrier layer 40 can be formed by depositing an oxide film containing indium or zinc by using any method known in the art such as sputtering or CVD. In order to stop the dry etching and protect the layer formed thereunder, the barrier layer 40 of the present invention has a thickness of 5 nm or more, preferably 10 nm or more.

  In step (d), a high refractive index material layer 52 is deposited on the barrier layer 40 without patterning.

(High refractive index material layer, high refractive index layer)
The high refractive index material layer 52 of the present invention includes metal nitride, metal oxide, and metal oxynitride, and can be preferably formed using silicon oxide, silicon nitride, silicon oxynitride, or the like. More preferably, silicon nitride is used. These materials can be deposited using a dry process such as a CVD method or an evaporation method. The high refractive index material layer 52 is usually deposited with a film thickness of 1 μm or more, more preferably 1 to 5 μm.

  In the step (e), the high refractive index material layer 52 is patterned to form the high refractive index layer 50 to obtain an organic EL light emitting device.

  As a patterning method of the high refractive index material layer 52, there is a method of etching using a mask made of a material having an etching selectivity. Since a high-definition shape can be easily formed, a method using a photoresist as a mask is generally widely used. However, in the configuration of the present invention, although the organic EL element 20 exists under the high refractive index material layer 52 and the barrier layer 40 is provided, the influence of pinholes is completely eliminated. Since it is difficult, it is preferable to avoid wet processes containing moisture as much as possible.

Therefore, in the present invention, the discontinuous film 60 formed using a dry process is used as an etching mask. The material for forming the discontinuous film 60 is required to have an etching selectivity with respect to the material for forming the high refractive index material layer 52 and to be capable of forming a discontinuous film by a method described later. . For example, when the high refractive index material layer 52 (high refractive index layer 50) is formed using SiN, it is selected from the group consisting of oxides containing indium or zinc, Al ₂ O ₃ , ZrO ₂ and TiO _2. It is possible to form the discontinuous film 60 using a compound. By using such a material, the discontinuous film 60 can be made transparent and have a high refractive index. Therefore, the light emitting device can be functioned without intentionally removing the discontinuous film 60 after etching. Needless to say, the discontinuous film 60 may be removed.

  Examples of the method for forming the discontinuous film 60 include a method using an initial stage of film formation by a dry process such as sputtering, vapor deposition, or CVD. Among these methods, the sputtering method is considered to be more suitable from the viewpoints of ensuring adhesion to the substrate and forming a fine grain. However, the sputtering method requires a strict control of the film thickness because the critical film thickness of the thin film from the island-like structure to the continuous structure is small compared to other film forming methods. The film thickness of the discontinuous film 60 in the present invention means a thickness obtained by averaging the discontinuous film thickness. The critical film thickness in the sputtering method depends on the material used. For example, in the sputtering method using ITO, the discontinuous film 60 can be formed by controlling the film thickness to about 10 to 30 nm.

  The discontinuous film 60 in the present invention is composed of a plurality of island-shaped portions. Each of the plurality of island-like portions preferably has a circular top surface having a diameter of 200 to 500 nm or a corresponding elliptical top surface shape. Each of the plurality of island-shaped portions is desirably arranged with an interval of 200 to 500 nm from the adjacent island-shaped portions. In the present invention, the plurality of island-shaped portions need not be aligned with uniform dimensions and intervals over the entire surface of the high refractive index material layer 52, and have dimensions and intervals that vary within the aforementioned range. May be arranged.

Next, using the obtained discontinuous film 60 as a mask and using the barrier layer 40 as an etch stop and a layer, the high refractive material layer 52 is etched into a pattern. Of the various etching methods, it is convenient to use dry etching, particularly reactive ion etching (RIE) using an etching gas containing fluorine. Etching gas containing fluorine that can be used is, for example, CF ₄ , CHF ₃ , CClF ₃ , CCl ₃ F, C ₂ F ₆ , C ₃ F ₈ , C ₃ F ₆ , C ₄ F ₁₀ , NF ₃ , SF ₆ and HF are included.

  The obtained high refractive index layer 50 is composed of a plurality of portions in which columnar shapes having a diameter of 200 to 500 nm and a height of 1 μm or more are arranged with a gap of 200 to 500 nm. As shown in FIG. 2, the plurality of portions constituting the high refractive index layer 50 do not have to be aligned with uniform dimensions and intervals over the entire surface of the barrier layer 40, and the dimensions vary within the aforementioned range. And may be arranged at intervals. The high refractive index layer 50 obtained by the above-described method exhibits a function of deflecting light emitted from the organic EL element 20 in an oblique direction in a direction closer to vertical by primary diffraction.

In the present invention, following the step (e),
(F) forming a color filter layer on the transparent support to obtain a color filter;
(G) performing the step of bonding the laminate obtained in the step (e) and the color filter obtained in the step (f) so that the color filter layer and the high refractive index layer face each other; An organic EL light emitting device including a color filter can also be manufactured.

  First, in step (f), a color filter layer 80 is formed on a separate transparent support 70. The color filter layer 80 may be one type, or a plurality of types may be arranged. The color filter layer 70 can be formed using commercially available materials and known methods for flat panel displays. The transparent support 70 in the present embodiment is made of glass, diacetylcellulose, triacetylcellulose (TAC), propionylcellulose, butyrylcellulose, acetylpropionylcellulose, nitrocellulose, or other cellulose ester; polyamide; polycarbonate; polyethylene terephthalate, polyethylene. Polyesters such as naphthalate, polybutylene terephthalate, poly-1,4-cyclohexanedimethylene terephthalate, polyethylene-1,2-diphenoxyethane-4,4′-dicarboxylate, polybutylene terephthalate; polystyrene; polyethylene, polypropylene, Polyolefin such as polymethylpentene; Acrylic resin such as polymethyl methacrylate; Polycarbonate; Polysulfone; Poly Terusuruhon; polyether ketone; polyetherimides; may be a polymer material such as norbornene resins; polyoxyethylene. In the case of using a polymer material, the support 60 may be rigid or flexible. Optically transparent means having a transmittance of 80% or more, preferably 86% or more with respect to visible light.

  Finally, in the step (g), the laminate including the high refractive index layer 50 obtained in the step (e) and the laminate of the color filter layer 80 / transparent support 70 obtained in the step (f), The organic EL light emitting device shown in FIG. 1D is formed by bonding the high refractive index layer 50 (discontinuous film 60) and the color filter layer 80 so as to face each other.

  Bonding can be performed by using the adhesive layer 90 provided on the peripheral portion of the transparent support 70 or the support 10. Adhesive layer 90 includes a suitable adhesive (such as a UV curable adhesive) and optionally spacer particles (such as glass beads) that define the distance between support 10 / transparent support 70. May be included. Alternatively, both laminates may be bonded using a known method other than the adhesive layer 90 provided at the peripheral edge.

By selecting the atmosphere in which the step (g) is performed, it is possible to select the gas that fills the gaps in the pattern of the high refractive index layer 50. For example, an inert gas such as air, N ₂ , or Ar can be used. Alternatively, it may be filled with a liquid or solid having a smaller refractive index than the material of the high refractive index layer.

  In the method of the present invention, when the organic EL element 20 having a plurality of independent light emitting portions as described above is used, a plurality of types of color filter layers 70 are arranged in alignment with the positions of the light emitting portions. Thus, a display device capable of multicolor display can be manufactured.

  As a modification of the present invention, as shown in FIGS. 3A to 3D, the barrier layer 40 can be composed of a plurality of layers. For example, the first barrier layer 42 and the second barrier layer 44 can be stacked on the color conversion layer 30 to function as the barrier layer 40. In this modification, the other steps ((a), (b), (d) to (g)) except the formation of the barrier layer 40 in the step (c) can be performed as described above.

  After the formation of the color conversion layer 30, the first barrier layer 42 is formed. The first barrier layer 42 can be deposited under mild conditions, and is a layer for protecting the underlying color conversion layer 30 and the like. The first barrier layer 42 is desirably optically transparent in order to finally pass through the light that passes through the color conversion layer 30 from the organic EL layer. However, the first barrier layer 42 does not need to function as an etch stop layer in patterning the high refractive index material layer 52 and includes metal nitride, metal oxide, metal oxynitride, and preferably silicon oxide. , Silicon nitride, silicon oxynitride, or the like can be used by a dry process such as a CVD method or an evaporation method. In the present invention, silicon nitride is preferably used, and silicon nitride is more preferably deposited by a CVD method. The first barrier layer 42 may have a thickness of 1 to 5 μm. The first barrier layer 42 may be formed so as to cover the layers below the color conversion layer 30 below it.

Next, the second barrier layer 44 is laminated on the first barrier layer 42. The second barrier layer 44 is a layer that functions as an etch stop layer when the high refractive index material layer 52 is patterned, like the barrier layer 40 in the case of a single layer. Further, in order to finally pass through the organic EL layer and pass through the color conversion layer 30, it is desirable that the second barrier layer 44 is also optically transparent. Depending on the dry etching conditions of the high refractive index material layer 52, for example, when dry etching is performed by reactive ion etching (RIE) using an etching gas containing fluorine, an oxide containing indium or zinc, The second barrier layer 44 can be formed using a compound selected from the group consisting of Al ₂ O ₃ , ZrO ₂ and TiO ₂ . Preferred oxides include transparent conductive oxides such as indium oxide, zinc oxide, indium-zinc oxide (IZO), indium-tin oxide (ITO). The second barrier layer 44 can be formed by depositing an oxide film containing indium or zinc by any method known in the art, such as sputtering or CVD. In order to stop the dry etching and protect the layer formed thereunder, the second barrier layer 44 of the present invention has a thickness of 5 nm or more, preferably 10 nm or more.

  In this modification, the barrier layer 40 has a laminated structure of the first barrier layer 42 and the second barrier layer 44, so that the second barrier layer 44 has a lower layer protection function with respect to the first barrier layer 42. On the other hand, by sharing the etch stop function, it becomes easier to satisfy both functions at a high level.

(Example 1)
On the glass as the support 10, an Ag film having a thickness of 30 nm was deposited by sputtering and patterned by photolithography to form a stripe-shaped reflective electrode having a width of 2 mm.

Next, the support on which the reflective electrode was formed was placed in a resistance heating vapor deposition apparatus, and a 1.5-nm-thick Li film was deposited on the reflective electrode using a mask to form a cathode buffer layer. Subsequently, four layers of an electron transport layer / a light-emitting layer / a hole transport layer / a hole injection layer were sequentially deposited using a resistance heating vapor deposition apparatus to obtain an organic EL layer. The pressure inside the vacuum chamber during film formation was reduced to 1 × 10 ⁻⁴ Pa. Each layer is deposited at a deposition rate of 0.1 nm / s, and Alq3 with a thickness of 20 nm as an electron transport layer, DPVBi with a thickness of 30 nm as a light emitting layer, α-NPD with a thickness of 10 nm as a hole transport layer, and positive As the hole injection layer, copper phthalocyanine (CuPc) having a thickness of 100 nm was used. Subsequently, MgAg having a film thickness of 5 nm was deposited to form a damage mitigating layer when forming the transparent electrode.

  The laminate on which the organic EL layer was formed was moved to the counter sputtering apparatus without breaking the vacuum. A metal mask is disposed to deposit IZO having a thickness of 100 nm to form a transparent electrode having a stripe shape with a width of 2 mm extending in a direction orthogonal to the stripe of the reflective electrode, and a laminated structure of the reflective electrode / organic EL layer / transparent electrode Thus, an organic EL element 20 having a 2 mm × 2 mm light-emitting portion was obtained.

  Next, the laminate in which the organic EL element 20 was formed without breaking the vacuum was conveyed to a resistance heating vapor deposition apparatus, and a color conversion layer 30 composed of coumarin 6 and DCM-2 was produced. A color conversion film having a film thickness of 300 nm was produced by co-evaporation in which coumarin 6 and DCM-2 were heated in separate crucibles in the vapor deposition apparatus. At this time, the heating temperature of each crucible was controlled so that the deposition rate of coumarin 6 was 0.3 nm / s and the deposition rate of DCM-2 was 0.005 nm / s. The color conversion layer 30 of this example contained 2 mol% of DCM-2 based on the total number of constituent molecules of the color conversion layer 30 (coumarin 6: DCM-2 molar ratio is 49: 1).

  The laminated body including the color conversion layer 30 was moved to the counter sputtering apparatus without breaking the vacuum, and IZO having a thickness of 1 μm was deposited on the color conversion layer 30 to form the barrier layer 40.

Further, the laminated body including the barrier layer 40 is moved to the plasma CVD apparatus without breaking the vacuum, and the plasma CVD method using monosilane (SiH ₄ ), ammonia (NH ₃ ), and nitrogen (N ₂ ) as source gases. The high refractive index material layer 52 was formed by depositing silicon nitride (SiN, refractive index 1.8) having a thickness of 1 μm. Here, when depositing SiN, the temperature of the stacked body on which the barrier layer 40 was formed was maintained at 100 ° C. or lower.

  Next, an island-like discontinuous film 60 made of IZO with a film thickness of 15 nm was formed on the upper surface of the high refractive index material layer 52 by DC magnetron sputtering. The discontinuous film 60 was formed while transporting the laminate on which the high refractive index material layer 52 was formed at a transport speed of 460 mm / min. At this time, the temperature of the laminate on which the high refractive index material layer 52 was formed was maintained at 60 ° C. or lower, and a gas having an oxygen partial pressure of 0.5% was used as the sputtering gas.

Next, the high refractive index material layer 52 was patterned by reactive ion etching using CF ₄ as an etching gas to form a high refractive index layer structure having an average diameter of 300 nm, an average gap of 200 nm, and a film thickness of 0.6 μm. .

  Next, a red color filter material (CR7001, manufactured by FUJIFILM Electronics Materials) is applied to the transparent glass substrate 70, and the film thickness 1 having a dimension of 2 mm × 2 mm is provided at a position corresponding to the light emitting portion of the organic EL element 20. A red color filter layer 80 having a thickness of 5 μm was formed.

  Then, in the bonding apparatus having an oxygen concentration of 5 ppm or less and a moisture concentration of 5 ppm or less, an adhesive layer 90 is formed using an epoxy-based ultraviolet curable adhesive on the periphery of the transparent glass substrate of the laminate including the red color filter layer. Then, a low-viscosity thermosetting epoxy adhesive was dropped on the red color filter layer 80. The laminated body including the organic EL element 20 is disposed so that the high refractive index layer 50 faces downward and faces the red color filter layer 80. After reducing the pressure in the apparatus to about 10 Pa, the light emitting portion of the organic EL element 20 And the red color filter layer 80 were aligned, and both laminates were bonded together, and the inside of the apparatus was returned to atmospheric pressure. Thereby, the low-viscosity thermosetting epoxy adhesive spread over the entire inner surface of the adhesive layer 90.

  Next, after only the adhesive layer 90 was irradiated with ultraviolet rays and temporarily cured using a mask, it was placed in a heating furnace and heated to 80 ° C. for 1 hour, and after natural cooling in the furnace for 30 minutes, the organic layer was taken out. An EL light emitting device was obtained. In addition, the refractive index after hardening of the low-viscosity thermosetting epoxy adhesive separately cured under the same conditions was 1.5. Moreover, the space | interval of the support body 10 and the transparent support body 70 was 5 micrometers.

(Comparative Example 1)
An organic EL light emitting device was obtained in the same manner as in Example 1 except that the high refractive index layer 50 was not formed.

(Evaluation)
The efficiency (cd / A) when the same current density (0.1 A / cm ² ) was passed was measured for the organic EL elements obtained in the above Examples and Comparative Examples. In Table 1, relative values with the current efficiency of Comparative Example 1 as 1 are shown.

  From the above results, it can be seen that the organic EL light-emitting device of the present invention having a high refractive index layer can obtain a higher current efficiency than a comparative device having no high refractive index layer. This is considered to be a result of improved light extraction efficiency due to the presence of the high refractive index layer.

It is a figure which shows the example of the manufacturing method of the organic electroluminescent light emitting device of this invention, (a)-(d) is a figure which shows each step. It is a perspective view which shows the shape of the high refractive index layer of this invention. It is a figure which shows the modification of the manufacturing method of the organic electroluminescent light emitting device of this invention, (a)-(d) is a figure which shows each step.

Explanation of symbols

DESCRIPTION OF SYMBOLS 10 Support 20 Organic EL element 30 Color conversion layer 40 Barrier layer 42 1st barrier layer 44 2nd barrier layer 50 High refractive index layer 52 High refractive index material layer 60 Discontinuous film 70 Transparent support 80 Color filter layer 90 Adhesive layer

Claims (8)

A method of manufacturing an organic EL light emitting device,
(A) forming an organic EL element having a reflective electrode, an organic EL layer and a transparent electrode in this order on a support;
(B) forming a color conversion layer on the organic EL element by vapor deposition;
(C) forming a barrier layer on the color conversion layer;
(D) laminating a high refractive index material layer on the barrier layer;
(E) patterning the high refractive index material layer to form a high refractive index layer comprising a plurality of portions,
The step (e) is carried out by forming a discontinuous film on the upper surface of the high refractive index material layer by a dry process and etching the high refractive index material layer using the discontinuous film as a mask. A method for manufacturing an organic EL light emitting device. _2. The organic material according to claim 1, wherein the discontinuous film is formed using a compound selected from the group consisting of an oxide containing indium or zinc, Al ₂ O ₃ , ZrO ₂ , and TiO _2. Manufacturing method of EL light emitting device.   2. The organic EL light emitting device according to claim 1, wherein the barrier layer is formed using an oxide containing indium or zinc or an oxide containing an element selected from the group consisting of Al, Zr and Ti. Manufacturing method.   2. The method of manufacturing an organic EL light emitting device according to claim 1, wherein the high refractive index material layer is formed using metal nitride, metal oxide, or metal oxynitride.   The organic material according to claim 1, wherein the barrier layer is composed of a first barrier layer formed on the color conversion layer and a second barrier layer formed on the first barrier layer. Manufacturing method of EL light emitting device.   6. The organic EL according to claim 5, wherein the second barrier layer is formed using an oxide containing indium or zinc or an oxide containing an element selected from the group consisting of Al, Zr and Ti. Manufacturing method of light-emitting device.   6. The method of manufacturing an organic EL light emitting device according to claim 5, wherein the first barrier layer is formed using metal nitride, metal oxide, or metal oxynitride. Following the step (e),
(F) forming a color filter layer on the transparent support to obtain a color filter;
(G) The method further includes a step of bonding the laminate obtained in the step (e) and the color filter obtained in the step (f) so that the color filter layer and the high refractive index layer face each other. The manufacturing method of the organic electroluminescent light emitting device of Claim 1 characterized by the above-mentioned.

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