KR101642606B1 - Substrate for organic electronic device - Google Patents

Abstract

The present invention relates to a substrate for an organic electronic device, an organic electronic device, a method for manufacturing the substrate or the device, a light source for a display, and a lighting device. The substrate for organic electronic devices of the present application can prevent organic substances such as moisture and oxygen from flowing into the organic electronic device substrate to improve durability and form organic electronic devices having excellent performance including light extraction efficiency .

Description

BACKGROUND OF THE INVENTION 1. Field of the Invention [0001] The present invention relates to a substrate for organic electronic devices,

The present invention relates to a substrate for an organic electronic device, an organic electronic device, a method for manufacturing the substrate or the device, a light source, and a lighting device.

An organic electronic device (OED) is an element including at least one layer of an organic material capable of conducting electric current, for example, as disclosed in Patent Document 1. [ Examples of the organic electronic device include an organic light emitting diode (OLED), an organic solar cell, an organic photoconductor (OPC), or an organic transistor.

An organic light emitting device, which is a typical organic electronic device, typically includes a substrate, a first electrode layer, an organic layer, and a second electrode layer sequentially. In a structure referred to as a so-called bottom emitting device, the first electrode layer may be formed of a transparent electrode layer, and the second electrode layer may be formed of a reflective electrode layer. In a structure referred to as a top emitting device, the first electrode layer may be formed as a reflective electrode layer, and the second electrode layer may be formed as a transparent electrode layer. Electrons and holes injected by the electrode layer can be recombined in the light emitting layer existing in the organic layer to generate light. Light can be emitted toward the substrate in the bottom emission type device and toward the second electrode layer side in the top emission type device.

Refractive indices of ITO (Indium Tin Oxide), an organic layer and a glass substrate, which are generally used as a transparent electrode layer in the structure of an organic light emitting device, are approximately 2.0, 1.8 and 1.5, respectively. Due to the relationship of the refractive indexes, for example, the light generated in the light emitting layer of the bottom emission type device is trapped by the total internal reflection phenomenon or the like at the interface between the organic layer and the first electrode layer or within the substrate, Only a small amount of light is emitted.

In recent years, and the increasing demand for technology to replace a glass substrate in the structure of a high As the organic light emitting element of interest to the flexible element (flexible device) to a flexible material such as a polymer substrate. However, in the case of such a polymer substrate, it is more vulnerable to heat and humidity environment than a glass-based substrate, and thus it is difficult to apply it to an organic electronic device.

Japanese Laid-Open Patent Publication No. 1996-176293

The present application provides a substrate for an organic electronic device, an organic electronic device, a method for manufacturing the substrate or the device, a light source, and a lighting device.

An exemplary organic electronic element substrate of the present application may include a flexible substrate layer, a barrier layer, and an electrode layer. The substrate for an organic electronic device may have a structure in which the flexible base layer, the barrier layer, and the transparent electrode layer are sequentially laminated. Fig. 1 exemplarily shows an organic electronic element substrate 1 including a flexible substrate layer 101, a barrier layer 102 and a transparent electrode layer 103 in sequence.

The flexible substrate layer may exhibit an appropriate haze in terms of the implementation of the substrate for an organic electronic device having excellent light extraction performance. The flexible substrate layer may exhibit haze, for example, in the range of 30% to 80%. More specifically, the lower limit of the haze of the flexible substrate layer is 30% or more, 32.5% or more, 35% or more, 37.5% or more, 40% or more, 42.5% or more, 45% or more, 47.5% or more, 50% or more, 52.5% Or more and 55% or more and the upper limit of the haze is 80% or less, 77.5% or less, 75% or less, 72.5% or less, 70% or less, 67.5% or less, 65% or less, 62.5% or less, Or 55% or less. The haze in the present application may be a numerical value measured through a known haze measuring instrument, for example, a value measured in accordance with JIS K 7105 using an HM-150 apparatus. When the haze of the flexible base layer is in the above range, the light transmitted from the organic layer can be appropriately scattered, refracted or diffracted to reduce the total reflection phenomenon in the substrate, and thus an organic electronic device having excellent light extraction performance can be realized .

As the flexible base layer, a light-transmitting base layer can be used. When the flexible substrate layer is a light-transmitting substrate layer, it may be advantageous when the substrate for organic electronic devices is applied to a bottom emission type organic electronic device. The flexible substrate layer may have a transmittance of 80% or more, 82% or more, 84% or more, 86% or more, 88% or more, or 90% or more of the light of at least one wavelength in the visible light region or the entire visible light region .

The flexible substrate layer may include a base material and high refractive index particles. The high-refraction particles may be dispersed in the base material. Figure 2 illustrates by way of example a flexible substrate layer 101 comprising a substrate material 201 and high refractive index particles 202. The thickness of the flexible base layer can be suitably selected within a range not to impair the purpose of the present application, and can have a thickness in the range of, for example, 10 mu m to 100 mu m.

The flexible substrate layer can exhibit appropriate haze by selectively including the refractive indexes of the base material and the high-refraction particles so as to be different from each other. For example, the refractive index difference between the base material and the high refractive index particles may be within the range of 0.1 to 0.5. More specifically, the refractive index difference is at least 0.1, at least 0.12, at least 0.14, at least 0.16, at least 0.18, at least 0.2, at least 0.22, at least 0.24, at least 0.26, at least 0.28, at least 0.30, at least 0.32, at least 0.34, at least 0.36, More than 0.38. 0.40 or more, 0.40 or more, 0.40 or more, 0.46 or more, or 0.48 or more, and 0.5 or less, 0.48 or less, 0.46 or less, 0.44 or less, 0.42 or less, 0.40 or less, 0.28 or less, 0.26 or less, 0.24 or less, 0.22 or less, 0.20 or less, 0.18 or less, 0.16 or less, 0.14 or less or 0.12 or less. The refractive index difference may be a value obtained by subtracting the refractive index of the base material from the refractive index of the high-refractive index particles. When the refractive index difference between the base material and the high refractive index particles is within the above range, not only the desired haze can be exhibited, but also an organic electronic device having excellent light extraction performance can be realized. The refractive index referred to herein may be a refractive index measured for light of at least one wavelength in the visible light region, for example, a refractive index measured for light of a wavelength of about 550 nm.

The ratio of the content of the base material and the high refractive index particles in the flexible base layer can be appropriately selected within a range that does not impair the desired physical properties. For example, the high-refraction particles may be contained in a proportion of 0.5% by weight to 30% by weight based on 100% by weight of the base material. More specifically, the high-refraction particles may be used in an amount of 0.5 wt% or more, 1 wt% or more, 2 wt% or more, 4 wt% or more, 6 wt% or more, 8 wt% or more, 10 wt% or more, At least 14 weight percent, at least 16 weight percent, at least 18 weight percent, at least 20 weight percent, at least 22 weight percent, at least 24 weight percent, at least 26 weight percent, at least 28 weight percent, or at least 29 weight percent Up to 30 weight percent, up to 28 weight percent, up to 26 weight percent, up to 24 weight percent, up to 22 weight percent, up to 20 weight percent, up to 18 weight percent, up to 16 weight percent, up to 14 weight percent, 12 Up to 10% by weight, up to 8% by weight, up to 6% by weight, up to 4% by weight, up to 2% by weight or up to 1% by weight. When the content ratio of the base material and the high-refraction particle in the flexible base material layer is within the above range, it may be advantageous to realize a substrate for an organic electronic device exhibiting an appropriate haze so as to exhibit excellent light extraction performance. The method for forming the flexible substrate layer is not particularly limited. For example, the composition including the base material and the high-refractive-index particles may be coated and then formed through heat application or light irradiation.

The base material may have an appropriate refractive index to the extent that the purpose of the present application is not impaired. The base material may have a refractive index, for example, in the range of 1.5 to 1.9. More specifically, the base material may have a refractive index of at least 1.5, at least 1.55, at least 1.6, at least 1.65, at least 1.7, at least 1.75, at least 1.8 or at least 1.85 and may have a refractive index of 1.9 or less, 1.85 or less, 1.8 or less, A refractive index of 1.65 or less, 1.6 or less, or 1.55 or less. Examples of the base material include, but are not limited to, polyamic acid, polyimide, polyethylene naphthalate, polyether ether ketone, polycarbonate, polyethylene terephthalate, polyether sulfide, polysulfone or acrylic resin no. As the base material, polyimide may be used in terms of process temperature or light extraction performance.

When a polyimide is used as the base material, a polyimide having a refractive index of about 1.5 or more, about 1.6 or more, about 1.65 or more, or about 1.7 or more can be used. Such a high refractive index polyimide can be produced, for example, by using a monomer into which a halogen atom other than fluorine, a sulfur atom or a phosphorus atom is introduced.

As the polyimide having high refractive index, a polyimic acid having a refractive index of about 1.5 or more, about 1.6 or more, about 1.65 or more, or about 1.7 or more may be used. As the polyamic acid, there can be used, for example, a polyamic acid capable of improving the dispersion stability of the particles due to existence of a site capable of bonding with the particles such as a carboxyl group. As the polyamic acid, for example, a compound containing a repeating unit represented by the following formula (1) can be used.

[Chemical Formula 1]

In formula (1), n may be a positive number, for example, a number in an amount of 1 or more.

The repeating unit may be optionally substituted by one or more substituents. Examples of the substituent include functional groups including a halogen atom other than fluorine, a halogen atom such as a phenyl group, a benzyl group, a naphthyl group or a thiophenyl group, a sulfur atom or a phosphorus atom.

The polyamic acid may be a homopolymer formed only from the repeating unit represented by the formula (1), or may be a block or a random copolymer including units other than the repeating unit represented by the formula (1). In the case of a copolymer, the kind and ratio of other repeating units can be appropriately selected within a range that does not impair the desired refractive index, heat resistance, and light transmittance, for example.

Specific examples of the repeating unit of the formula (1) include repeating units of the following formula (2).

(2)

In the formula (2), n may be a positive number, for example, a number in an amount of 1 or more.

The polyamic acid may have a weight average molecular weight of about 10,000 to about 100,000 or about 10,000 to about 50,000, for example, in terms of standard polystyrene measured by GPC (Gel Permeation Chromatograph). The polyamic acid having the repeating unit represented by the formula (1) has a light transmittance of not less than 80%, not less than 85%, or not less than 90% in the visible light region and is excellent in heat resistance.

The index of refraction of the high refractive index particles can be selected higher than the refractive index of the base material. The refractive index of the high refractive index particles can be suitably selected within a range that does not impair the object of the present application. The high refractive index particles may have refractive indices in the range of 1.8 to 2.4, for example. More specifically, the high refractive index particles may have a refractive index of 1.8 or more, 1.85 or more, 1.9 or more, 1.95 or more, 2.0 or more, 2.05 or more, 2.1 or more, 2.15 or more, 2.2 or more, 2.25 or more, 2.3 or more, The refractive index may be 2.35 or less, 2.3 or less, 2.25 or less, 2.2 or less, 2.15 or less, 2.1 or less, 2.05 or less, 2.0 or less, 1.95 or less, 1.9 or less or 1.85 or less.

The high refractive index particles may have a shape such as spherical, elliptical, polyhedral or amorphous, but the shape is not particularly limited. Further, the size of the high-refraction particles can be suitably selected within a range not to impair the purpose of the present application. The high refractive index particles may be, for example, from 1 nm to 100 nm, from 10 nm to 90 nm, from 10 nm to 80 nm, from 10 nm to 70 nm, from 10 nm to 60 nm, from 10 nm to 50 nm, Of the average particle diameter.

Examples of the high-refractive index particles include organic materials such as polystyrene or a derivative thereof, an acrylic resin or a derivative thereof, a silicone resin or a derivative thereof, or a novolak resin or a derivative thereof, or an organic material such as alumina, aluminosilicate, titanium oxide or zirconium oxide And the like can be exemplified. The high-refraction particles may include only one of the above-mentioned materials, or may be formed of two or more of the above materials. According to one embodiment of the present application, aluminum oxide (Al ₂ O ₃ ) having a refractive index of about 1.8 can be used as high refractive index particles.

A barrier layer may be formed on the flexible base layer. The term " barrier layer " in the present application may mean a layer having a function of preventing permeation of oxygen, moisture, nitrogen oxides, sulfur oxides or ozone in the atmosphere. The barrier layer may exhibit an appropriate refractive index in terms of good light extraction of the organic electronic device. The barrier layer may exhibit refractive indices in the range of, for example, 1.7 to 1.9. When the refractive index of the barrier layer satisfies the above range, for example, the total reflection phenomenon can be reduced in the substrate, so that an organic electronic device having excellent light extraction performance can be realized.

As the barrier layer, a material having a function of preventing the entry of substances promoting deterioration of elements such as moisture and oxygen into the device, which represents the refractive index range, can be selected and used. The barrier layer may comprise an inorganic or organic material. The barrier layer may comprise, for example, a metal, a metal oxide, a metal nitride, a metal oxynitride or a metal fluoride. More specifically, the barrier layer may be formed of a metal such as In, Sn, Pb, Au, Cu, Ag, Al, Ti, and Ni; _{TiO, TiO 2, Ti 3 O} 3, Al 2 O 3, MgO, SiO, SiO 2, GeO, NiO, CaO, BaO, Fe 2 O 3, Y2O 3, ZrO 2, Nb 2 O 3 and, CeO _2, and ; Metal nitrides such as SiN; Metal oxynitrides such as SiON; MgF ₂ , LiF, AlF _3, and CaF ₂ . The barrier layer may also comprise at least one organic material selected from the group consisting of polyacrylate, polymethacrylate, polyethylene, polypropylene, polymethylmethacrylate, polyimide, polyurea, polytetrafluoroethylene, polychlorotrifluoroethylene, Ethylene, or copolymers of chlorotrifluoroethylene and dichlorodifluoroethylene; A copolymer obtained by copolymerizing tetrafluoroethylene with a comonomer mixture comprising at least one comonomer; A fluorine-containing copolymer having a cyclic structure in the copolymer main chain; An absorbent material having an absorption rate of 1% or more; And a moisture-proof material having an absorption coefficient of 0.1% or less. According to one embodiment of the present application, a composite film of Al ₂ O ₃ and TiO ₂ having a refractive index of about 1.75 or a laminated structure of the same inorganic film and organic film can be used as the barrier layer.

The barrier layer may be a single layer structure or a multi-layer structure. The single-layer structure may include a material of one kind of barrier layer, or may include a mixture of two or more kinds of materials of the barrier layer. The multi-layer structure may be a structure in which two or more single-layer structures are stacked, and may be a multi-layer structure in which, for example, a TiO ₂ layer and an Al ₂ O ₃ layer are sequentially stacked.

The thickness of the barrier layer can be suitably selected within a range not to impair the purpose of the present application. For example, the thickness of the barrier layer may be from 5 nm to 1000 nm, from 7 nm to 750 nm, or from 10 nm to 500 nm. When the thickness of the barrier layer satisfies the above numerical range, a barrier function for preventing permeation of oxygen and moisture in the atmosphere is sufficient, and transparency of the transparent substrate can be maintained with an appropriate light transmittance. The light transmittance of the barrier layer is not particularly limited and may be appropriately selected depending on the intended use. For example, the light transmittance of the barrier layer may be at least about 80%, at least 85%, or at least 90%.

The organic electronic device substrate having the barrier layer formed thereon may have a water vapor transmission rate (WVTR) of 10 ^-4 g / m ² / day or less. The water vapor transmission rate may be, for example, a value measured at a temperature of 40 DEG C and a relative humidity of 90%. The water vapor transmission rate can be measured using, for example, a water vapor permeability meter (PERMATRAN-W3 / 31, manufactured by MOCON, Inc.). When the barrier layer satisfies the above numerical range, curl phenomenon or the like does not occur due to penetration of extraneous substances such as moisture and oxygen even in a high temperature and high humidity environment, and therefore, the barrier layer has excellent durability, An electronic device can be realized.

The barrier layer may be formed by any one of ALD (Atomic Layer Deposition) method, vacuum deposition, sputtering, reactive sputtering, MBE (molecular beam epitaxy), cluster ion beam method, ion plating method, plasma polymerization method, plasma CVD method, Method, a gas source CVD method, or a coating method. According to one embodiment of the present application, the barrier layer may be an atomic layer deposition layer formed by the ALD method.

A transparent electrode layer may be formed on the barrier layer. The transparent electrode layer can exhibit an appropriate refractive index in terms of excellent light extraction of the organic electronic device. The transparent electrode layer may exhibit a refractive index within a range of, for example, 1.8 to 2.0. When the refractive index of the transparent electrode layer satisfies the above range, for example, the total reflection phenomenon can be reduced in the substrate, so that an organic electronic device having excellent light extraction performance can be realized. The transparent electrode layer may include a transparent conductive oxide. Examples of the transparent conductive oxide include, but are not limited to, ITO, IZO, GaZO, ZnO, or SnO ₂ .

The thickness of the transparent electrode layer may be suitably selected within a range not to impair the purpose of the present application and may be, for example, about 90 nm to 200 nm, 90 nm to 180 nm, or about 90 nm to 150 nm thick . The method of forming the transparent electrode layer is not particularly limited and may be formed by any means such as, for example, vapor deposition, sputtering, chemical vapor deposition, or electrochemical means. If necessary, the transparent electrode layer may be patterned through a process using known photolithography, shadow mask, or the like.

The present application also relates to organic electronic devices. The organic electronic device may include the substrate for the organic electronic device described above. Organic electronic devices include, for example, a flexible substrate layer having a haze in the range of 30% to 80%; A barrier layer formed on the flexible base layer and having a refractive index within a range of 1.7 to 1.9; And a transparent electrode layer formed on the barrier layer and having a refractive index within a range of 1.8 to 2.0; And a second electrode layer formed on the organic layer, wherein the flexible substrate layer includes a base material and high refractive index particles having a refractive index difference of 0.1 to 0.5 with the base material have. In the above, specific details regarding the flexible substrate layer, the barrier layer, and the transparent electrode layer can be applied to the same items as described above in the item of the organic electronic element substrate.

The organic layer may include, for example, a light emitting layer. In this case, if a two-electrode layer is formed as a reflective electrode layer, a bottom emission type device in which light generated in the emission layer of the organic layer is emitted toward the substrate layer through the optically functional layer can be realized.

The organic electronic device may be an organic light emitting diode (OLED). In this case, the organic electronic device may have, for example, a structure in which an organic layer including a light emitting layer is interposed between the hole injection electrode layer and the electron injection electrode layer. In this case, the transparent electrode layer may be a hole injection electrode layer and the second electrode layer may be an electron injection electrode layer.

The organic layer present between the electron and hole injecting electrode layers may include at least one luminescent layer. The organic layer may include a plurality of light emitting layers of two or more layers. When two or more light emitting layers are included, the light emitting layers may have a structure in which the light emitting layers are divided by an intermediate electrode layer having charge generating characteristics, a charge generating layer (CGL) or the like.

The light-emitting layer can be formed, for example, by using various fluorescent or phosphorescent organic materials known in the art. Examples of the material of the light-emitting layer include tris (4-methyl-8-quinolinolate) aluminum (III) (aluminum (III)) (Alg3), 4-MAlq3 or Gaq3 Alq series materials, C-545T (C ₂₆ H ₂₆ N ₂ O ₂ S), DSA-amine, TBSA, BTP, PAP-NPA, Spiro-FPA, Ph ₃ Si (PhTDAOXD), PPCP , 4,5-pentaphenyl-1,3-cyclopentadiene), cyclopenadiene derivatives such as 4,4'-bis (2,2'-diphenylyinyl) -1,1'-biphenyl, Benzene or a derivative thereof or DCJTB (4- (Dicyanomethylene) -2-tert-butyl-6- (1,1,7,7, -tetramethyljulolidyl-9-enyl) -4H-pyran), DDP, AAAP, NPAMLI; Or Firpic, m-Firpic, N- Firpic, bon 2 Ir (acac), (C 6) 2 Ir (acac), bt 2 Ir (acac), dp 2 Ir (acac), bzq 2 Ir (acac), bo _{2 Ir (acac), F 2} Ir (bpy), F 2 Ir (acac), op 2 Ir (acac), ppy 2 Ir (acac), tpy 2 Ir (acac), FIrppy (fac-tris [2- ( 4,5-difluorophenyl) pyridine-C'2, N] iridium (III)) or Btp ₂ Ir (acac) ') iridium (acetylacetonate)), and the like, but the present invention is not limited thereto. The light emitting layer may contain the above material as a host and may also include perylene, distyrylbiphenyl, DPT, quinacridone, rubrene, BTX, ABTX or DCJTB. And may have a host-dopant system including a dopant.

The light-emitting layer can be formed by suitably employing a kind that exhibits luminescence characteristics among electron-accepting organic compounds or electron-donating organic compounds described below.

The organic layer may be formed with various structures, including various other functional layers known in the art, as long as the layer includes a light emitting layer. Examples of the layer that can be included in the organic layer include an electron injecting layer, a hole blocking layer, an electron transporting layer, a hole transporting layer, and a hole injecting layer.

The electron injection layer or the electron transport layer can be formed using, for example, an electron accepting organic compound. As the electron-accepting organic compound in the above, any known compound can be used without any particular limitation. Examples of such organic compounds include polycyclic compounds or derivatives thereof such as p-terphenyl or quaterphenyl, naphthalene, tetracene, pyrene, coronene, ), Polycyclic hydrocarbon compounds or derivatives thereof such as chrysene, anthracene, diphenylanthracene, naphthacene or phenanthrene, phenanthroline, Heterocyclic compounds or derivatives thereof such as bathophenanthroline, phenanthridine, acridine, quinoline, quinoxaline, or phenazine may be exemplified. It is also possible to use at least one of fluoroceine, perylene, phthaloperylene, naphthaloperylene, perynone, phthaloferrinone, naphthoferrinone, diphenylbutadiene ( diphenylbutadiene, tetraphenylbutadiene, oxadiazole, aldazine, bisbenzoxazoline, bisstyryl, pyrazine, cyclopentadiene, and the like. Oxine, aminoquinoline, imine, diphenylethylene, vinyl anthracene, diaminocarbazole, pyrane, thiopyrane, polymethine, Quinacridone or rubrene or derivatives thereof, Japanese Patent Application Laid-Open No. 1988-295695, Japanese Patent Application Laid-Open No. 1996-22557, Japanese Patent Application Laid-Open No. 1996-81472, Japanese Patent Application Laid-Open No. 1993-009470 or Japanese Patent Application Laid- For example, tris (8-quinolinolato) aluminum, a metal chelated oxanoid compound, bis (8-quinolinolato) aluminum, Bis (benzo (f) -8-quinolinolato] zinc}, bis (2-methyl-8-quinolinolato) aluminum, Tris (8-quinolinolato) indium], tris (5-methyl-8-quinolinolato) aluminum, 8- quinolinolato lithium, tris (5- Quinolinolato) gallium, bis (5-chloro-8-quinolinolato) calcium and the like, metal complexes having at least one of 8-quinolinolato or a derivative thereof as an arbiter, Japanese Patent Laid- Oxadiazole compounds disclosed in Japanese Patent Application Laid-Open Nos. 1995-179394, 1995-278124, and 1995-228579, Stilbene derivatives, distyrylarylene derivatives, and the like disclosed in Japanese Patent Application Laid-Open (kokai) No. 1994-132080 Styryl derivatives disclosed in JP-A-1994-88072 and the like, diolefin derivatives disclosed in JP-A-1994-100857 and JP-A-1994-207170, and the like; Fluorescent brightening agents such as benzooxazole compounds, benzothiazole compounds or benzoimidazole compounds; Bis (4-methylstyryl) benzene, distyrylbenzene, 1,4-bis (2-methylstyryl) benzene, Bis (2-methylstyryl) benzene, 1,4-bis (3-ethylstyryl) benzene, Methylstyryl) -2-ethylbenzene, and the like; Bis (4-methylstyryl) pyrazine, 2,5-bis (4-methylstyryl) pyrazine, 2,5- Bis [2- (4-biphenyl) vinyl] pyrazine such as bis (4-methoxystyryl) pyrazine, 2,5-bis [2- Distyrylpyrazine compounds, 1,4-phenylenedimethylidene, 4,4'-phenylenedimethylidyne, 2,5-xylenedimethylidyne, 2,6-naphthylenedimethylidyne, 1,4-biphenylene dimethyl (9,10-anthracenediyldimethylidine) or 4,4 '- (2,2-di-t-butylphenylvinyl) biphenyl , Dimethylidine compounds such as 4,4- (2,2-diphenylvinyl) biphenyl or derivatives thereof, silanamine disclosed in Japanese Patent Application Laid-Open No. 1994-49079 or Japanese Patent Laid-Open Publication No. 1994-293778 silanamine derivatives, Japanese Patent Application Laid-Open No. 1994-279322 or Japanese Patent Application Laid-Open No. 1994-279323 Oxadiazole derivatives disclosed in Japanese Patent Laid-Open Publication No. 1994-109264, Japanese Patent Laid-Open Publication No. 1994-206865 and the like, an anthracene compound disclosed in Japanese Patent Oxynate derivatives disclosed in JP-A-1994-145146 and the like, tetraphenylbutadiene compounds disclosed in JP-A-1992-96990 and the like, organic trifunctional compounds disclosed in JP-A-1991-296595, A coumarin derivative disclosed in JP-A-1990-191694, a perylene derivative disclosed in JP-A-1990-196885, a naphthalene derivative disclosed in JP-A-1990-255789, Phthaloperynone derivatives disclosed in JP-A No. 1990-289676 or JP-A No. 1990-88689 or a derivative of phthaloperynone derivatives disclosed in JP-A No. 1990-25029 Styrylamine derivatives disclosed in, for example, Japanese Patent Laid-open Publication No. 2 (1990) can also be used as electron-accepting organic compounds contained in the low refractive layer. In addition, the electron injection layer may be formed using a material such as LiF or CsF.

The hole blocking layer is a layer which can prevent the injected holes from entering the electron injecting electrode layer through the light emitting layer to improve the lifetime and efficiency of the device. If necessary, the hole blocking layer can be formed using a known material, As shown in FIG.

The hole injecting layer or the hole transporting layer may include, for example, an electron donating organic compound. Examples of the electron donating organic compound include N, N ', N'-tetraphenyl-4,4'-diaminophenyl, N, N'- N, N ', N'-tetra-p-tolyl-4,4'-diaminobiphenyl, Phenyl, N, N'-di (4-methoxyphenyl) -4,4'-diaminobiphenyl, N, N'- (N, N ', N'-tetraphenyl-4,4'-diaminodiphenyl ether, 4,4'-bis (diphenylamino) quadriphenyl] 4-N, N-diphenylaminostilbene, N-phenylcarbazole, 1,1-bis (4-methoxy- Bis (4-dimethylamino-2-methylphenyl) phenylmethanesulfonate, 1,1-bis (4-di- N, N, N-tri (p-tolyl) amine, 4- (di-p- tolylamino) -4 ' N ', N'-tetraphenyl-4,4'-diaminobis N-phenylcarbazole, 4,4'-bis [N- (1-naphthyl) -N-phenylamino] biphenyl, Phenylamino] biphenyl, 4,4'-bis [N- (3-acenaphthenyl) -N (2-naphthyl) Phenylamino] biphenyl, 1,5-bis [N- (1-naphthyl) -N-phenylamino] naphthalene, 4,4'- Bis [N- (2-phenanthryl) -biphenylphenylamino] biphenyl, 4,4'-bis [N- N-phenylamino] biphenyl, 4,4'-bis [N- (2-pyrenyl) - N-phenylamino] biphenyl, 4,4'-bis [N- (1-choronenyl) - N-phenylamino] biphenyl), 2,6-bis (di-p-tolylamino) naphthalene, 2,6-bis (1-naphthyl) amino] naphthalene, 2,6-bis [N- (1-naphthyl) Bis [N, N-di (2-naphthyl) amino] terphenyl, 4,4'-bis { Bis [N, N-di- (2-naphthyl) amino] fluorene or 4,4'-bis (N, N-di-p-tolylamino) terphenyl and bis (N-1-naphthyl) (N-2-naphthyl) amine and the like are exemplified. It is not.

The hole injecting layer or the hole transporting layer may be formed by dispersing an organic compound in a polymer or by using a polymer derived from the organic compound. Further, a hole-transporting non-conjugated polymer such as a? -Conjugated polymer, poly (N-vinylcarbazole), or a? -Conjugated polymer of a polysilane, such as polyparaphenylenevinylene and its derivatives, .

The hole injection layer may be formed by using a metal phthalocyanine such as copper phthalocyanine, a nonmetal phthalocyanine, a carbon film and an electrically conductive polymer such as polyaniline, or by reacting the arylamine compound with an Lewis acid using the arylamine compound as an oxidizing agent You may.

Illustratively, the organic light emitting device includes (1) a form of a hole injection electrode layer / an organic light emitting layer / electron injecting electrode layer formed sequentially; (2) a form of a hole injection electrode layer / a hole injection layer / an organic light emitting layer / an electron injection electrode layer; (3) a form of a hole injection electrode layer / an organic light emitting layer / an electron injection layer / an electron injection electrode layer; (4) a form of a hole injection electrode layer / a hole injection layer / an organic light emitting layer / an electron injection layer / an electron injection electrode layer; (5) a form of a hole injection electrode layer / an organic semiconductor layer / an organic light emitting layer / an electron injecting electrode layer; (6) the form of the hole injection electrode layer / organic semiconductor layer / electron barrier layer / organic light emitting layer / electron injection electrode layer; (7) Forms of hole injecting electrode layer / organic semiconductor layer / organic light emitting layer / adhesion improving layer / electron injecting electrode layer; (8) Forms of hole injecting electrode layer / hole injecting layer / hole transporting layer / organic light emitting layer / electron injecting layer / electron injecting electrode layer; (9) Forms of hole injecting electrode layer / insulating layer / organic light emitting layer / insulating layer / electron injecting electrode layer; (10) Forms of hole injecting electrode layer / inorganic semiconductor layer / insulating layer / organic light emitting layer / insulating layer / electron injecting electrode layer; (11) Forms of hole injecting electrode layer / organic semiconductor layer / insulating layer / organic light emitting layer / insulating layer / electron injecting electrode layer; (12) Hole injection electrode layer / Insulation layer / Hole injection layer / Hole transport layer / Organic light emitting layer / Insulation layer / Electron injection electrode layer or (13) Hole injection electrode layer / Insulating layer / Hole injection layer / Hole transport layer / The light emitting layer may have a shape of an injection layer / electron injecting electrode layer, and in some cases, at least two light emitting layers may be disposed between the hole injecting electrode layer and the electron injecting electrode layer as an intermediate electrode layer or a charge generating layer (CGL) But the present invention is not limited thereto.

In this field, various materials for forming a hole or electron injection electrode layer and an organic layer such as a light emitting layer, an electron injection or transport layer, a hole injection or transport layer, and a forming method thereof are known. All of the same methods can be applied.

The organic electronic device may further include an encapsulation structure. The encapsulation structure may be a protective structure that prevents foreign substances such as moisture, oxygen and the like from being introduced into the organic layer of the organic electronic device. The sealing structure may be a can, such as a glass can or a metal can, or may be a film covering the entire surface of the organic layer. The encapsulation structure may include, if necessary, a metal oxide such as calcium oxide or beryllium oxide, a moisture absorbent such as a metal halide such as calcium chloride or phosphorous pentoxide, or a getter material. The moisture adsorbent or getter material may be contained in, for example, a film-type sealing structure or may exist at a predetermined position of the sealing structure of the can structure. The encapsulation structure may further include a barrier film, a conductive film, and the like.

The present application also relates to a substrate for an organic electronic device or a method of manufacturing an organic electronic device. The manufacturing method may be, for example, the substrate for an organic electronic device or the manufacturing method of an organic electronic device described above.

The substrate for an organic electronic device may be formed by forming a barrier layer having a refractive index within a range of 1.7 to 1.9 on a flexible base layer having a haze within a range of 30% to 80%, forming a transparent layer having a refractive index within a range of 1.8 to 2.0 on the barrier layer And the flexible substrate layer is formed by forming the electrode layer so as to include the base material and the high refractive index particles having a refractive index difference of 0.1 to 0.5 with the base material. In the above, specific details regarding the flexible substrate layer, the barrier layer, and the transparent electrode layer can be applied to the same items as described above in the item of the organic electronic element substrate.

The method of forming the flexible substrate layer is not particularly limited. For example, the substrate material and the composition including the high-refractive-index particles may be coated and then formed by heat application or light irradiation. The method of forming the barrier layer is not particularly limited. For example, the barrier layer may be formed by using the above-mentioned material of the barrier layer, such as ALD (Atomic Layer Deposition) method, vacuum deposition method, sputtering method, reactive sputtering method, MBE (molecular beam epitaxy) It can be formed by ion beam method, ion plating method, plasma polymerization method, plasma CVD method, laser CVD method, thermal CVD method, gas source CVD method, and coating method. According to one embodiment of the present application, Can be used. The method of forming the transparent electrode layer is not particularly limited, and can be formed by any of known methods such as vapor deposition, sputtering, chemical vapor deposition or electrochemical method using the material of the above-described transparent electrode layer.

An organic electronic device is manufactured by sequentially forming an organic layer and a second electrode layer, which may include at least a light emitting layer, on a substrate for an organic electronic device manufactured according to the above-described method, Lt; RTI ID = 0.0 > a < / RTI > The method of forming the second electrode layer is not particularly limited, and the second electrode layer may be formed by any known method such as evaporation, sputtering, chemical vapor deposition, or electrochemical method using the material of the second electrode layer. Further, the organic layer and the sealing structure can be formed in a known manner.

The present application also relates to the use of the above-described organic electronic devices, for example, organic light emitting devices. The organic light emitting device may be a light source for a display, for example, a backlight of a liquid crystal display (LCD), an illuminator, a light source such as various sensors, a printer or a copying machine, a vehicle instrument light source, , A display device, a light source of a planar light-emitting body, a display, a decoration, or various lights. In one example, the present application relates to a lighting device comprising the organic light-emitting device. In the case where the organic light emitting device is applied to the illumination device or other use, the other components constituting the device or the like and the constitution method of the device are not particularly limited. As long as the organic light emitting device is used, Any of the materials or methods may be employed.

The substrate for organic electronic devices of the present application can prevent organic substances such as moisture and oxygen from flowing into the organic electronic device substrate to improve durability and form organic electronic devices having excellent performance including light extraction efficiency .

Fig. 1 exemplarily shows a substrate for an organic electronic device.
Fig. 2 exemplarily shows a flexible substrate layer.
Figure 3 illustrates an exemplary organic electronic device.
4 is a graph of the emission spectral results for the wavelengths of Examples and Comparative Examples.

Hereinafter, the present application will be described in more detail by way of examples according to the present application, but the scope of the present application is not limited by the following examples.

Example  One

On the glass substrate, a coating material in which a polyimide having a refractive index of 1.6 as a base material and Al ₂ O ₃ (average particle diameter: 20 to 30 nm) having a refractive index of 1.8 as a high-refractive index particle were dispersed in a weight ratio of 5% Thereby forming a flexible base layer having a thickness of about 25 to 30 um. Subsequently, a barrier layer was formed on the flexible substrate layer so that the composite film of Al ₂ O ₃ and TiO ₂ having a refractive index of 1.75 was made to have a thickness of about 30 to 50 nm by an ALD (Atomic Layer Deposition) method. Then, an ITO transparent electrode layer having a refractive index of about 1.8 to 1.9 was formed on the barrier layer to a thickness of about 100 to 150 nm by a sputtering method. The haze of the formed flexible substrate layer was evaluated by the JIS K 7105 method using HM-150, and the haze was measured at 60%. Then, on the transparent electrode layer, an alpha-NPD (N, N'-Di- [(1-naphthyl) -N, N'- diphenyl] (4,4 ', 4 "-tris (N-carbazolyl) -triphenylamine (TCTA): Firpic, TCTA: Fir6) was sequentially formed on the light emitting layer. A transporting compound TCTA (4,4 ', 4 "-tris (N-carbazolyl) -triphenylamine) was added to form an electron transport layer having a thickness of about 70 nm. Subsequently, an aluminum (Al) electrode was formed as an electron injecting reflective electrode on the electron transporting layer by a vacuum vapor deposition method to manufacture a device. Subsequently, a sealing structure was attached to the device in a glove box in an Ar gas atmosphere to prepare an organic light emitting device.

Example  2

An organic light emitting device was fabricated in the same manner as in Example 1, except that Al ₂ O ₃ was added at a weight ratio of 1% as high refractive index particles at the time of forming the flexible base layer. HM-150 was added to the formed flexible substrate layer And the haze was evaluated by the JIS K 7105 method. As a result, the haze was measured to be 30%.

Comparative Example  One

An organic light emitting device was manufactured in the same manner as in Example 1 except that high refractive index particles were not used at the time of forming the flexible base layer. The HMIS 150 was used to evaluate the haze of the formed flexible substrate layer in accordance with JIS K 7105 As a result, haze was measured at 2%.

Comparative Example  2

Except that refractive index particles having a refractive index of 1.5 (Silica, average particle diameter: 300 to 500 nm) were compounded at a weight ratio of 10% in place of the high-refractive index particles at the time of forming the flexible base layer, . The haze of the formed flexible substrate layer was evaluated by the JIS K 7105 method using HM-150, and the haze was measured at 60%.

Comparative Example  3

An organic light emitting device was produced in the same manner as in Example 1 except that a glass substrate on which a flexible substrate layer was not formed was used as a base layer.

Test Example  1: Performance evaluation of organic light emitting device

Quantum Efficiency, CCT (Correlated Color Temperature), CRI (Color Rendering Index), and Duv (Delta uv color) were measured for the organic light emitting devices of Examples 1 and 2 and Comparative Examples 1 to 3, And CIE color (x, y) were evaluated in a known manner. The results are shown in Table 1, and the emission spectrum for the wavelength was measured in a known manner, and the results are shown in FIG.

As shown in the following Table 1, when the quantum efficiency was about 35% or more in Example 1 (haze: 60%, Δn: 0.2) and Example 2 (haze: 30%, Δn: 0.2) Performance. In particular, Example 1 exhibited quantum efficiency of about 45% and exhibited remarkably excellent light extraction performance.

It was found that Comparative Example 1 (haze: 2%, Δn: 0.2) and Comparative Example 2 (haze: 60%, Δn: -0.1) have. On the other hand, the comparative example 3 shows a quantum efficiency similar to that of the example 2, but is unsuitable for the implementation of a flexible device because the glass substrate itself is used as a base layer.

4, the luminescence intensities were increased in almost all spectral regions as compared with Comparative Examples 1 and 2 in Examples 1 and 2. Particularly, Comparative Example 1 (haze: 60%, Δn: 0.2) It can be seen that the luminescence intensity is remarkably increased as compared with Examples 1 and 2.

Base layer Haze (%) Refractive index
Difference
(? N) quantum
efficiency
(%) CCT CRI Duv CIE color
(x, y) Example 1 60 0.2 44.8 3722 86 -0.0009 (0.393, 0.382) Example 2 30 0.2 35.6 3708 86 0.0006 (0.395, 0.386) Comparative Example 1 2 0.2 28,2 3694 87 0.0009 (0.396, 0.388) Comparative Example 2 60 -0.1 33.0 3807 87 0.0023 (0.391, 0.388) Comparative Example 3 Glass substrate 35.4 4064 89 0.0052 (0.381, 0.388)

101: Flexible substrate layer
102: barrier layer
103: transparent electrode layer
1011: Base material
1012: high-refraction particle
301: organic layer
302: second electrode layer

Claims (18)

A flexible base layer having a haze within a range of 30% to 80% and a barrier layer formed on the flexible base layer and having a refractive index within a range of 1.7 to 1.9; And a transparent electrode layer formed on the barrier layer and having a refractive index in a range of 1.8 to 2.0, wherein the flexible base layer has a refractive index difference of 0.1 to 0.5 with respect to the base material and the base material, a refractive index in a range of 1.8 to 2.15 A substrate for an organic electronic device comprising high refractive index particles. The method according to claim 1,
Wherein the flexible base layer has a light transmittance of 80% or more with respect to at least one wavelength in a visible light region. The method according to claim 1,
Wherein the base material has a refractive index in the range of 1.5 to 1.9. The method according to claim 1,
Wherein the substrate material comprises polyamic acid, polyimide, polyethylene naphthalate, polyether ether ketone, polycarbonate, polyethylene terephthalate, polyether sulfide, polysulfone acrylic resin, polystyrene or epoxy resin. The method according to claim 1,
Wherein the refractive index of the high refractive index particles is higher than that of the base material. delete The method according to claim 1,
The high-refractive-index particle may be at least one selected from the group consisting of polystyrene or a derivative thereof, an acrylic resin or a derivative thereof, a silicone resin or a derivative thereof, or a novolak resin or a derivative thereof, an alumina, an aluminosilicate, a titanium oxide or a zirconium oxide. Substrate for device. The substrate for an organic electronic device according to claim 1, wherein the barrier layer comprises an inorganic material or an organic material. 9. The method of claim 8,
Wherein the inorganic material comprises at least one selected from the group consisting of a metal, a metal oxide, a metal nitride, a metal oxynitride, and a metal fluoride. 9. The method of claim 8,
The organic material is selected from polyacrylates, polymethacrylates, polyethylene, polypropylene, polymethylmethacrylate, polyimide, polyurea, polytetrafluoroethylene, polychlorotrifluoroethylene and polydichlorinated difluoroethylene And at least one organic metal compound. The method according to claim 1,
Wherein the transparent electrode layer comprises a transparent conductive oxide. 12. The method of claim 11,
Wherein the transparent conductive oxide is ITO, IZO, GaZO, ZnO or SnO ₂ . Forming a barrier layer having a refractive index within a range of 1.7 to 1.9 on a flexible base layer having a haze within a range of 30% to 80%, forming a transparent electrode layer having a refractive index within a range of 1.8 to 2.0 on the barrier layer, Wherein the base material and the base material are formed so as to include high refractive index particles having a refractive index difference within a range of 0.1 to 0.5 and a refractive index within a range of 1.8 to 2.15. A flexible substrate layer having a haze within a range of 30% to 80%; A barrier layer formed on the flexible base layer and having a refractive index within a range of 1.7 to 1.9; And a transparent electrode layer formed on the barrier layer and having a refractive index within a range of 1.8 to 2.0; And a second electrode formed on the organic layer, wherein the flexible substrate layer has a refractive index difference of 0.1 to 0.5 with respect to the base material and the base material, RTI ID = 0.0 > 2.15. ≪ / RTI > 15. The method of claim 14,
Wherein the organic layer comprises a light emitting layer. A method for manufacturing an organic electronic device, comprising sequentially forming an organic layer and a second electrode on a transparent electrode layer of a substrate for an organic electronic device manufactured according to the method of claim 13. A light source for a display comprising the organic electronic device of claim 14. 14. A lighting device comprising the organic electronic device of claim 14.

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