KR20130111486A - Substrate for organic electronic device - Google Patents

Abstract

PURPOSE: A substrate for an organic electronic device is provided to prevent interlayer delamination by effectively relieving a stress generated in a scattering layer and a high refractive layer. CONSTITUTION: A scattering layer (102) is formed on a base material layer (101). An elastic layer (103) is formed between the scattering layer and the base material layer or on the scattering layer. The average thickness of the elastic layer is 10 nm or more. The high refractive layer is formed on the scattering layer or the elastic layer. The refractive index of the high refractive layer for a beam of a wavelength of 550 nm is 1.8 to 3.5.

Description

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

The present application relates to a substrate for an organic electronic device, an organic electronic device, a method of manufacturing the device or the substrate, and an illumination.

An organic electronic device (OED) is a device including one or more layers of organic materials capable of conducting current. 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.

Accordingly, in order to increase the light emission efficiency, a technique using a scattering layer, a scattering layer, and a flat layer formed thereon is known. Typically, the scattering layer and / or flat layer are formed of a material having a high refractive index. However, due to the characteristics of the high refractive index material, high stress is generated in the driving process of the device, and thus, the durability of the device may be degraded due to peeling or cracking between layers.

The present application provides a substrate for an organic electronic device, an organic electronic device, a method of manufacturing the substrate or the device, and an illumination.

An exemplary substrate for an organic electronic device may include a base layer and a scattering layer formed on the base layer. The substrate may further include an elastic layer formed between the scattering layer and the base layer or on the scattering layer. As used herein, the term elastic layer refers to a layer formed of a material having a Modulus of Elasticity of 50 GPa to 400 GPa at a temperature of 23 ° C. In one example, the elastic layer may include a material having an elastic modulus within a range between the elastic modulus of the scattering layer described above and the elastic modulus of the high refractive layer described later. Another lower limit of the modulus of elasticity of the material forming the elastic layer may be, for example, about 70 GPa, 90 GPa, 110 GPa, 130 GPa, 150 GPa, 170 GPa, or 190 GPa. In addition, another upper limit of the modulus of elasticity of the material forming the elastic layer may be, for example, about 390 GPa, 380 GPa, 370 GPa, 360 GPa, or 350 GPa. The elastic layer formed of such a material can improve the durability by relieving stress generated in the device.

FIG. 1 is an exemplary view illustrating a case in which the scattering layer 102 and the elastic layer 103 are sequentially formed on the base layer 101. In FIG. 1, the elastic layer 103 is formed on the scattering layer 102, but the elastic layer 103 may be present between the scattering layer 102 and the base layer 101. .

As the base layer, an appropriate material may be used without particular limitation. For example, when applied to a bottom emission device, a light transmissive base layer, for example, a base layer having a transmittance of 50% or more for light in the visible region may be used. As a light transmissive base material layer, a glass base material layer, a transparent polymer base material layer, etc. can be illustrated. Examples of the glass base layer include base layers such as soda lime glass, barium / strontium-containing glass, lead glass, aluminosilicate glass, borosilicate glass, barium borosilicate glass, or quartz, and as the polymer base layer, PI ( Substrate layers including polyimide, polyethylene naphthalate (PEN), polycarbonate (PC), acrylic resin, poly (ethylene terephthatle) (PET), poly (ether sulfide) (PES) or polysulfone (PS) may be exemplified. However, the present invention is not limited thereto. As needed, the said base material layer may be a TFT substrate in which a driving TFT exists. When the substrate is applied to a top emission type device, the base layer does not necessarily need to be a light transmissive base layer. If necessary, a reflective layer made of aluminum or the like may be formed on the surface of the substrate layer or the like. For example, when the pencil hardness of the electrode layer on the base layer should be maintained at a high level as described above, a base layer having rigidity such as a glass base layer may be used.

The scattering layer formed on the substrate is, for example, a layer capable of scattering, refracting, or diffracting light incident on the layer, and any type of layer can be applied as long as it has such a function.

For example, the scattering layer can be a layer comprising a matrix material and scattering regions. 2 shows a form in which an exemplary scattering layer comprising a scattering region 1021 formed of scattering particles and a matrix material 1022 is formed in the base layer 101. As used herein, the term “scattering region” has a refractive index different from that of a surrounding material such as, for example, a matrix material or the elastic layer or a flat layer described later, and also has an appropriate size to scatter, refract, or diffract incident light. It can mean an area that can be made. The scattering region may be, for example, a particle having the refractive index and the size, or an empty space. For example, scattering regions can be formed using particles that are different from the surrounding material and have a higher or lower refractive index than the surrounding material. The refractive index of the scattering particles may have a difference in refractive index between the surrounding material, for example, the matrix material, the elastic layer, and / or the flat layer, greater than 0.3 or greater than 0.3. For example, the scattering particles may have a refractive index of about 1.0 to 3.5 or about 1.0 to 3.0. As used herein, the term "refractive index" is a refractive index measured for light having a wavelength of about 550 nm. The refractive index of the scattering particles may be, for example, 1.0 to 1.6 or 1.0 to 1.3. In another example, the refractive index of the scattering particles may be about 2.0 to 3.5 or about 2.2 to 3.0. As the scattering particles, for example, particles having an average particle diameter of 50 nm or more, 100 nm or more, 500 nm or more or 1,000 nm or more can be exemplified. The average particle diameter of the scattering particles may be, for example, 10,000 nm or less. The scattering region may also be formed by a space filled with air as an empty space having such a size.

The scattering particles or regions may have a shape such as a spherical shape, an ellipsoid, a polyhedron, or an amorphous form, but the shape is not particularly limited. As the scattering particles, for example, organic materials such as polystyrene or derivatives thereof, acrylic resins or derivatives thereof, silicone resins or derivatives thereof, or novolak resins or derivatives thereof, or silica, alumina, titanium oxide or zirconium oxide Particles containing an inorganic material and the like can be exemplified. The scattering particles may be formed of only one of the above materials or two or more of the above materials. For example, hollow particles such as hollow silica or particles having a core / cell structure may be used as the scattering particles.

The scattering layer may further comprise a matrix material that retains the scattering region, such as scattering particles. As the matrix material, for example, a material having a refractive index similar to that of another adjacent material such as a base material layer or a material having a higher refractive index may be formed. The matrix material is, for example, a polyimide, a cardo resin having a fluorene ring, a urethane, an epoxide, a polyester or an acrylate-based thermal or photocurable monomeric, oligomeric or polymeric organic A material, an inorganic material such as silicon oxide, silicon nitride, silicon oxynitride or polysiloxane, or an organic-inorganic composite material can be used.

The matrix material may comprise polysiloxane, polyamic acid or polyimide. The polysiloxane may be formed by, for example, polycondensing a condensable silane compound or a siloxane oligomer, and may form a matrix material based on a bond between silicon and oxygen (Si-O) through the above. It is also possible to control the condensation conditions and the like in the process of forming the matrix material so that the polysiloxane is based only on the siloxane bond (Si-O), or the condensed functional group such as an organic group such as an alkyl group or an alkoxy group remains.

As the polyamic acid or polyimide, for example, a polyamic acid or 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 high refractive polyamic acid or polyimide can be produced using, for example, a monomer into which a halogen atom, a sulfur atom or a phosphorus atom other than fluorine is introduced. For example, a polyamic acid capable of improving the dispersion stability of the particles may be used because there is 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.

[Formula 1]

In formula 1 n is a positive number.

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)

N in the formula (2) is a positive number.

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 scattering layer may be, for example, a layer having an uneven structure. 3 is a diagram illustrating a scattering layer 102 having an uneven structure formed on the base layer 101. Incident light can be scattered when the uneven structure of the scattering layer is appropriately adjusted. The scattering layer having a concave-convex structure, for example, hardens the material or forms a scattering layer in contact with a mold capable of transferring the concave-convex structure of a desired shape in the course of curing the heat or photocurable material. After forming a layer of the material to be formed in advance, it can be produced by forming an uneven structure through an etching process or the like. Alternatively, it may be formed by incorporating particles having a suitable size and shape into the binder forming the scattering layer. In this case, the particles need not necessarily be particles having a scattering function, but particles having a scattering function may be used.

The scattering layer may be, for example, a material coated by a wet coating method, a method of applying heat or irradiating light, or a method of curing the material by a sol-gel method, a chemical vapor deposition (CVD) or a physical PVD (Physical method). Vapor Deposition) may be formed through a deposition method such as a method or nanoimprinting or a microembossing method.

The scattering layer may further comprise high refractive particles, if necessary. The term "high refractive particles" may mean, for example, particles having a refractive index of 1.5 or more, 2.0 or more, 2.5 or more, 2.6 or more, or 2.7 or more. The upper limit of the refractive index of the high refractive particles may be selected, for example, in a range capable of satisfying the refractive index of the desired scattering layer. The high refractive particles may, for example, have a smaller average particle diameter than the scattering particles. 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. As the high refractive particles, alumina, aluminosilicate, titanium oxide or zirconium oxide and the like can be exemplified. As the high refractive index particles, for example, rutile titanium oxide can be used as the particles having a refractive index of 2.5 or more. The rutile-type titanium oxide has a higher refractive index than other particles, and therefore, it is possible to adjust the refractive index to a desired value at a relatively small ratio.

The elastic layer is formed on the scattering layer or between the scattering layer and the base layer. The elastic layer can be formed, for example, by forming a layer of a material having an elastic modulus in the above-described range on top of the scattering layer or on the base layer before the scattering layer is formed. As the material having the elastic modulus, for example, TiO ₂ , Si ₃ N ₄ , MgO, Al ₂ O ₃ , ZnO, or ZrO ₂ may be used, but is not limited thereto. The layer of such material may be formed, for example, by depositing the material in a conventional deposition manner. The thickness of the elastic layer formed as described above is not particularly limited, and may be changed in consideration of, for example, stress relaxation efficiency. For example, the average thickness of the elastic layer can be adjusted within the range of 10 nm or more, but is not limited thereto. The upper limit of the average thickness is not particularly limited and may be adjusted in consideration of desired transparency or elastic properties.

Meanwhile, as the material for forming the elastic layer in consideration of light extraction efficiency, a material having a refractive index in a range similar to that of an adjacent electrode layer or a high refractive layer described later may be used.

For example, the elastic layer may be formed using a material having a refractive index of 1.7 or more, 1.8 to 3.5, or 2.2 to 3.0 among the materials having the above-described elastic modulus. By adjusting the refractive index of the material as described above can provide a device having a better light extraction efficiency.

If necessary, a high refractive layer may be formed on the scattering layer or the elastic layer. As used herein, the term high refractive index layer may mean a layer having a refractive index of 1.7 or more, 1.8 to 3.5, or 2.2 to 3.0 for a wavelength of 550 nm. The high refractive layer may be, for example, a flat layer providing a flat surface on which other elements such as an electrode layer to be described later may be formed.

The high refractive layer can be formed using, for example, a material in which the matrix material and the high refractive particles described in the scattering layer section are mixed.

In another example, the high refractive layer may be formed using a material in which a compound such as alkoxide or acylate of a metal such as zirconium, titanium or cerium is combined with a binder having a polar group such as a carboxyl group or a hydroxy group. Compounds such as alkoxides or acylates may be condensed with the polar groups in the binder, and the high refractive index may be realized by including the metal in the binder. Examples of the alkoxide or acylate compound include titanium alkoxides such as tetra-n-butoxy titanium, tetraisopropoxy titanium, tetra-n-propoxy titanium or tetraethoxy titanium, titanium stearate and the like. Zirconium such as zirconium alkoxide, zirconium tributoxy stearate such as titanium acylate, titanium chelates, tetra-n-butoxy zirconium, tetra-n-propoxy zirconium, tetraisopropoxy zirconium or tetraethoxy zirconium Acylate, zirconium chelates, etc. can be illustrated. The high refractive index layer may also be formed by a sol-gel coating method in which a metal alkoxide such as titanium alkoxide or zirconium alkoxide and a solvent such as alcohol or water are prepared to prepare a coating liquid, and then applied and fired at an appropriate temperature.

The substrate for an organic electronic device may further include an electrode layer formed on the scattering layer, the elastic layer and / or the high refractive layer (hereinafter, these layers will be referred to simply as the functional layer).

4 and 5 show an exemplary substrate including a structure in which the functional layer 301 and the electrode layer 302 are sequentially formed on the substrate layer 101. As shown in the drawing, the functional layer 301 may have a smaller projected area than the base layer 101, and the electrode layer 302 may have a larger projected area than the functional layer 301. As used herein, the term "projection area" refers to the area of the projection of the object recognized when the substrate is observed from the top of the substrate surface in the normal direction, for example, the area of the base layer, the functional layer, or the electrode layer. . Therefore, for example, when the surface of the functional layer is formed in an uneven shape, the actual surface area is larger than that of the electrode layer, but the area recognized when the functional layer is observed from above is observed from the top. The functional layer is interpreted to have a smaller projected area than the electrode layer if it is smaller than the area perceived as.

The functional layer may exist in various forms as long as the projected area is smaller than that of the base layer and the projected area is smaller than that of the electrode layer. For example, the functional layer 301 may be formed only at a portion excluding the edge of the base layer 101 as shown in FIG. 4, or part of the functional layer 302 may remain at the edge of the base layer 101 as shown in FIG. 5. It may be.

6 is a diagram illustrating a case where the substrate of FIG. 4 is observed from the top. As shown in FIG. 6, the area A of the electrode layer 302 perceived when the substrate is viewed from above, that is, the projected area A of the electrode layer 302, is the projected area of the functional layer 301 below it. Wider than B) The ratio A / B of the projected area A of the electrode layer and the projected area B of the functional layer may be, for example, 1.04 or more, 1.06 or more, 1.08 or more, 1.1 or more, or 1.15 or more. If the projected area of the functional layer is smaller than the projected area of the electrode layer, the upper limit of the ratio A / B of the projected area is not particularly limited because a structure in which the functional layer described later is not exposed to the outside can be implemented. In consideration of a general substrate manufacturing environment, the upper limit of the ratio A / B may be, for example, about 2.0, about 1.5, about 1.4, about 1.3, or about 1.25. In the substrate, the electrode layer may be formed on an upper portion of the base layer on which the functional layer is not formed. The electrode layer may be formed in contact with the base layer, or may include an additional element. By such a structure, it is possible to implement a structure in which the functional layer is not exposed to the outside when the organic electronic device is implemented.

For example, as shown in FIG. 6, the electrode layer 302 may be formed up to an area including an area deviating from all peripheral portions of the functional layer 301 when viewed from above. In this case, for example, when there are a plurality of functional layers on the substrate layer as shown in FIG. 5, at least one functional layer among the functional layers, for example, a functional layer in which an organic layer is formed at least thereon as described below. The electrode layer may be formed up to an area including an area beyond all periphery of the. For example, in the structure of FIG. 5, if the organic layer is formed on the top of the functional layer existing on the right and left edges, the structure of FIG. 5 extends to the left and right sides of the functional layer existing on the right and left edges. The structure can be changed so that the electrode layer is formed up to an area beyond all peripheral circumferences. In the above structure, when the encapsulation structure described below is attached to the electrode layer on which the functional layer is not formed, the functional layer may not be exposed to the outside.

The electrode layer may be a conventional hole injecting or electron injecting electrode layer used for manufacturing an organic electronic device.

The electrode layer capable of injecting holes can be formed using, for example, a material having a relatively high work function, and can be formed using a transparent material when necessary. For example, the hole-injecting electrode layer may comprise a metal, an alloy, an electrically conductive compound or a mixture of two or more thereof having a work function of about 4.0 eV or more. As such a material, metal such as gold, CuI, indium tin oxide (ITO), indium zinc oxide (IZO), zinc tin oxide (ZTO), zinc oxide doped with aluminum or indium, magnesium indium oxide, nickel tungsten oxide, Metal oxides such as ZnO, SnO ₂ or In ₂ O ₃ , metal serrides such as gallium nitride and zinc selenide, and metal sulfides such as zinc sulfide. The transparent positive hole injecting electrode layer can also be formed using a metal thin film of Au, Ag or Cu and a laminate of a transparent material of high refractive index such as ZnS, TiO ₂ or ITO.

The hole injecting electrode layer may be formed by any means such as vapor deposition, sputtering, chemical vapor deposition or electrochemical means. In addition, the electrode layer formed according to need may be patterned through a process using known photolithography, shadow mask, or the like.

The electron injecting transparent electrode layer can be formed using, for example, a transparent material having a relatively small work function. For example, a material suitable for forming the hole injecting electrode layer can be formed using a suitable material But is not limited thereto. The electron injecting electrode layer can also be formed using, for example, a vapor deposition method or a sputtering method, and can be appropriately patterned when necessary.

The thickness of the electrode layer is not particularly limited, but in consideration of the above-mentioned resistance between the electrode layers, for example, to have a thickness of about 90 nm to 200 nm, 90 nm to 180 nm or about 90 nm to 150 nm. Can be formed.

The present application also relates to an organic electronic device. Exemplary organic electronic devices of the present application, the substrate for an organic electronic device described above; And an organic layer formed on the substrate, for example, on the scattering layer, elastic layer, high refractive layer, or electrode layer; And an electrode layer formed on the organic layer. In the following description, an electrode layer formed on a substrate may be referred to as a first electrode layer, and an electrode layer formed on the organic layer may be referred to as a second electrode layer. In the organic electronic device including the substrate, the projected area of the first electrode layer may be larger than the projected area of the functional layer of the substrate, and the electrode layer may be formed on the surface of the base layer on which the functional layer is not formed. .

The organic layer may include at least a light emitting layer. For example, when the first electrode layer is transparently formed and the second electrode layer is a reflective electrode layer, a lower light emitting device in which light generated in the light emitting layer of the organic layer is radiated to the base layer side through the functional layer may be implemented.

In the organic electronic device, the functional layer may have, for example, a projection area corresponding to or larger than the emission area of the emission layer. For example, the difference B-C between the length B of the formation region of the functional layer and the length C of the emission region of the light emitting layer may be about 10 μm to about 2 mm. In the above, the length B of the formation region of the functional layer is a length in an arbitrary direction in the region recognized when the functional layer is observed from the top, in which case the length C of the light emitting region is also observed from the top. The length measured in the same direction when measuring the length (B) of the formation region of the functional layer on the basis of the region recognized when the. The functional layer may also be formed at a position corresponding to the light emitting region. The formation of the functional layer at a position corresponding to the emission area may mean, for example, that the emission area and the functional layer substantially overlap each other when the organic electronic device is observed from above or below.

In one example, the organic electronic device may be an organic light emitting diode (OLED). In the case of an organic light emitting device, for example, the organic electronic device may have a structure in which an organic layer including at least a light emitting layer is interposed between the hole injection electrode layer and the electron injection electrode layer. For example, if the electrode layer included in the substrate is a hole injection electrode layer, the second electrode layer may be an electron injection electrode layer. On the contrary, if the electrode layer included in the substrate is an electron injection electrode layer, the second electrode layer may be a hole 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. Materials that can be used for the light emitting layer include tris (4-methyl-8-quinolinolate) aluminum (III) (tris (4-methyl-8-quinolinolate) aluminum (III)) (Alg3), 4-MAlq3 or Alq-based materials such as Gaq3, C-545T (C ₂₆ H ₂₆ N ₂ O ₂ S), DSA-amine, TBSA, BTP, PAP-NPA, Spiro-FPA, Ph ₃ Si (PhTDAOXD), PPCP (1, Cyclopenadiene derivatives such as 2,3,4,5-pentaphenyl-1,3-cyclopentadiene), DPVBi (4,4'-bis (2,2'-diphenylyinyl) -1,1'-biphenyl) , Distyryl benzene or its derivatives 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 Ir ₂ (acac), Ir F ₂ (bpy), F Ir ₂ (acac), op ₂ Ir (acac), ppy ₂ Ir (acac), Ir ₂ tpy (acac), FIrppy (fac-tris [2- ( 4,5'-difluorophenyl) pyridine-C'2, N] iridium (III)) or Btp ₂ Ir (acac) (bis (2- (2'-benzo [4,5-a] thienyl) pyridinato-N, Phosphorescent materials such as C3 '-) iridium (acetylactonate)) and the like can be exemplified, but 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 and derivatives thereof, silane disclosed in Japanese Patent Application Laid-Open No. 1994-49079 or Japanese Patent Application Laid-Open No. 1994-293778 Silanamine derivatives, Japanese Patent Application Laid-Open No. 1994-279322 or Japanese Patent Laid-Open Publication 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, Coumarin derivatives disclosed in JP-A-1990-191694 and the like, perylene derivatives disclosed in JP-A-1990-196885 and the like, naphthalene derivatives 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 prevents 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 injection layer or the hole transport layer may be formed by dispersing the organic compound in a polymer or using a polymer derived from the organic compound. Also, such as polyparaphenylenevinylene and derivatives thereof, so-called hole transporting nonconjugated polymers such as π-conjugated polymers, poly (N-vinylcarbazole), or σ conjugated polymers of polysilane may be used. have.

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.

FIG. 7 illustrates that the organic layer 701 and the second electrode layer 702 formed on a substrate including the sequentially formed base layer 101, the functional layer 301, and the first electrode layer 302 may be formed of a glass can, a metal can, or the like. The shape protected by the encapsulation structure 703 of the can structure is exemplarily shown. The encapsulation structure 703 of FIG. 7 may be attached by an adhesive, for example. The encapsulation structure 703 may be adhered to, for example, an electrode layer in which a functional layer does not exist below the substrate. For example, as shown in FIG. 7, the sealing structure 703 may be attached to the end of the substrate by an adhesive. In this way it is possible to maximize the protective effect through the encapsulation structure.

The encapsulation structure may be, for example, a film covering the entire surface of the organic layer and the second electrode layer. 8 exemplarily shows a film-like encapsulation structure 703 covering the entire surface of the organic layer 701 and the second electrode layer 702. For example, the encapsulation structure 703 in the form of a film covers the entire surface of the organic layer 701 and the second electrode layer 702 as shown in FIG. 8, while the base layer 101, the functional layer 301, and the electrode layer ( The substrate including the 302 and the upper second substrate 801 may be bonded to each other. As the second substrate 801, for example, a glass substrate, a metal substrate, a polymer film or a barrier layer may be exemplified. The encapsulation structure in the form of a film is formed by applying, curing, and curing a liquid material that is cured by heat or ultraviolet (UV) irradiation or the like, for example, an epoxy resin, or by using the epoxy resin or the like beforehand It can be formed by laminating the substrate and the upper substrate using an adhesive sheet prepared in the form.

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, or the like.

For example, as shown in FIG. 7 or 8, the encapsulation structure may be attached to an upper portion of the first electrode layer 302 in which the functional layer 301 is not formed. Accordingly, it is possible to implement a sealing structure in which the functional layer is not exposed to the outside. The sealing structure is, for example, the entire surface of the functional layer is surrounded by the base layer, the electrode layer and / or the sealing structure, or surrounded by a sealing structure formed including the base layer, the electrode layer and / or the sealing structure. This may mean a state that is not exposed to the outside. The sealing structure may be formed of only the base layer, the electrode layer and / or the encapsulation structure, or as long as the functional layer is formed so as not to be exposed to the outside, the base layer, the electrode layer and the encapsulation structure, and may also be formed including other elements. have. For example, other elements may be present in a portion where the base layer 101 and the electrode layer 302 contact each other, or a portion where the electrode layer 302 and the encapsulation structure 703 contact each other or other positions in FIG. 7 or 8. The other element may be a low moisture-permeable organic material, an inorganic material or an organic-inorganic composite material, an insulating layer or an auxiliary electrode.

The present application also relates to a substrate for an organic electronic device or a method for manufacturing the organic electronic device. An exemplary method may include forming a scattering layer on the substrate layer. The method may include forming the elastic layer comprising a material having a modulus of elasticity of 50 GPa to 400 GPa at a temperature of 23 ° C. before or after forming the scattering layer. If necessary, the step of forming the above-mentioned high refractive layer on top of the elastic layer or after the scattering layer is formed may also be performed.

The method of forming the scattering layer, the elastic layer and / or the high refractive layer in the above is not particularly limited, and each of the methods described above may be applied, or other known forming methods may be applied.

If necessary, the method may include processing the formed functional layer, ie, the scattering layer, the elastic layer and / or the high refractive layer, to have a smaller transparent area than the base layer. This process can be performed, for example, by removing at least a portion of the functional layer formed on the substrate layer. Through the above processing, the functional layer may be patterned to exist only at a position corresponding to the emission region, for example. For example, a part of the functional layer formed after the functional layer is formed on the entire surface of the substrate layer can be removed. The method of removing a part of the functional layer is not particularly limited, and an appropriate method may be applied in consideration of the type of the functional layer.

For example, the method may be applied to a wet or dry etching treatment of the functional layer with an etchant capable of dissolving the functional layer, or the like to remove the layer, or a method such as laser processing or waterjet injection may also be applied.

Alternatively, a method of removing a part of the functional layer by photolithography or forming a functional layer having a smaller projected area than the base layer by using offset printing or other pattern printing may be considered. Can be.

The processing form of the functional layer is not particularly limited and may be changed according to the purpose. For example, the processing corresponds to the light emitting area of the light emitting layer in which the position of the functional layer whose projection area is smaller than that of the base layer is subsequently formed, and the projected area corresponds to the light emitting layer or the light emitting area formed by the light emitting layer, or It may be performed to be larger than that. In addition, the functional layer may be processed in various patterns as necessary. In addition, the functional layer present in the region corresponding to the region where the adhesive is applied or the terminal region of the device may be removed for bonding to the encapsulation structure.

The manufacturing method may further include forming an electrode layer after formation of the functional layer or after processing of the formed functional layer. The method of forming the electrode layer is not particularly limited, and may be formed by any method such as known deposition, sputtering, chemical vapor deposition, or electrochemical method.

The method of manufacturing an organic electronic device may include forming an organic layer and a second electrode layer including a light emitting layer after forming the electrode layer as described above, and further forming an encapsulation structure. In this case, the organic layer, the second electrode layer and the encapsulation 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 backlight of a liquid crystal display (LCD), an illumination device, a light source such as various sensors, a printer, a copying machine, a vehicle instrument light source, a traffic light, a display, A light source, 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.

In the present application, while exhibiting excellent light extraction efficiency, the stress generated in the scattering layer and / or high refractive layer which is a structure that improves the light extraction efficiency is effectively alleviated to provide a device capable of stable driving without the occurrence of interlayer peeling and cracks, etc. can do.

1 is a view showing an exemplary substrate for an organic electronic device.
2 and 3 show the shape of an exemplary scattering layer.
4 to 6 are diagrams showing the relationship between the projected area between the functional layer and the electrode layer.
7 and 8 illustrate exemplary organic electronic devices.

Hereinafter, the organic electronic device substrate and the like will be described in detail with reference to Examples and Comparative Examples, but the scope of the substrate and the like is not limited to the following examples.

Example  One.

Fabrication of Substrate for Organic Electronic Device

A sol-gel coating solution was prepared by sufficiently dispersing 1 g of polymer beads (XX75BO, average diameter: about 3 μm, manufactured by Sekisui) having a refractive index of about 1.52 in 10 g of tetramethoxy silane. Subsequently, the prepared coating solution was coated on a glass substrate, and a sol-gel reaction was performed to form a scattering layer. Subsequently, Al ₂ O ₃ having a modulus of elasticity of about 270 to 320 GPa and a refractive index of about 1.726 was deposited on the scattering layer to a thickness of about 30 nm to form an elastic layer. Thereafter, a high refractive coating solution containing high refractive index titanium oxide particles having an average particle diameter of about 10 nm and a refractive index of about 2.5 in a sol-gel coating solution containing tetramethoxy silane was coated on the top of the scattering layer in the same manner as the coating solution. In the same manner, the sol-gel reaction was performed to form a high refractive index layer having a refractive index of about 1.8. Subsequently, a portion of the high refractive layer and the like was removed by irradiating a laser to the formed layer so that the remaining positions of the high refractive layer and the like correspond to the light emitting regions of the organic layer. After removal, a hole injection electrode layer including ITO (Indium Tin Oxide) was formed on the entire surface of the glass substrate by a known sputtering method to prepare a substrate.

Manufacture of organic light emitting device

Alpha-NPD (N, N'-Di-[(1-naphthyl) -N, N'-diphenyl] -1,1'-biphenyl) -4,4'- through the deposition method on the electrode layer of the prepared substrate A hole injection layer and a light emitting layer (4,4 ', 4 "-tris (N-carbazolyl) -triphenylamine (TCTA): Firpic, TCTA: Fir6) containing diamine) were sequentially formed. TCTA (4,4 ', 4 "-tris (N-carbazolyl) -triphenylamine), a transporting compound, was deposited to form an electron transport layer having a thickness of about 70 nm. Subsequently, an aluminum (Al) electrode as an electron injecting reflective electrode was formed on the electron transport layer by a vacuum deposition method to manufacture a device. Subsequently, the device was manufactured by attaching a sealing structure to the device in a glove box in an Ar gas atmosphere.

Comparative Example  One.

An organic light emitting diode was manufactured in the same manner as in Example 1, except that the elastic layer was not formed.

Test Example  One.

After driving the organic light emitting diodes manufactured in Example 1 and Comparative Example 1 under the same conditions, peeling and / or cracking were observed at the interface between the scattering layer and the high refractive layer. As a result, in the device of Comparative Example 1, fine peeling and cracking were observed between the scattering layer and the high refractive layer, but such defects were not observed in the device of Example 1.

101: base material layer 102: scattering layer
103: elastic layer 1022: matrix material
1021: scattering region 301: functional layer
302: electrode layer, first electrode layer 701: organic layer
702: second electrode layer 703: sealing structure
801: second substrate

Claims (15)

A base layer; A scattering layer formed on the substrate layer; And an elastic layer formed between the scattering layer and the substrate layer or on the scattering layer, the elastic layer including a material having a modulus of elasticity of 50 GPa to 400 GPa at a temperature of 23 ° C. The substrate of claim 1, wherein the material having a modulus of elasticity of 50 GPa to 400 GPa at a temperature of 23 ° C. is TiO ₂ , Si ₃ N ₄ , MgO, Al ₂ O ₃ , ZnO, or ZrO ₂ . The substrate for an organic electronic device according to claim 1, wherein the average thickness of the elastic layer is 10 nm or more. The substrate of claim 1, wherein the material having an elastic modulus of 50 GPa to 400 GPa at a temperature of 23 ° C. has a refractive index of 1.8 to 3.5 for a wavelength of 550 nm. The organic electronic device substrate of claim 1, further comprising a high refractive layer present on the scattering layer or the elastic layer. The substrate of claim 5, wherein the refractive index of the high refractive index layer is about 1.8 to 3.5. A substrate for an organic electronic device according to claim 1; A first electrode layer formed on the substrate; An organic layer formed on the first electrode layer; And a second electrode layer. The organic electronic device of claim 7, wherein the organic layer comprises a light emitting layer. The method of claim 7, wherein the projected area of the scattering layer and the elastic layer of the organic electronic device is smaller than the projected area of the first electrode layer, and the first electrode layer is formed on the top of the base layer on which the scattering layer and the elastic layer are not formed. Organic electronic device formed. 10. The organic electronic device of claim 9, further comprising an encapsulation structure protecting the organic layer and the second electrode layer, wherein the encapsulation structure is attached to an upper portion of the first electrode layer on which the scattering layer and the elastic layer are not formed. . The organic electronic device of claim 10, wherein the encapsulation structure is a glass can or a metal can. The organic electronic device of claim 10, wherein the encapsulation structure is a film covering entire surfaces of the organic layer and the second electrode layer. Organic electrons comprising forming a scattering layer on a substrate layer, and forming an elastic layer comprising a material having a modulus of elasticity of 50 GPa to 400 GPa at a temperature of 23 ° C. before or after forming the scattering layer. The manufacturing method of the board | substrate for elements. The method of claim 13, further comprising forming a high refractive layer on the scattering layer or the elastic layer. A lighting device comprising the organic electronic device of claim 7.

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