KR102028142B1 - Substrate for organic electronic device - Google Patents

Abstract

The present application relates to a substrate for an organic electronic device and its use. In the present application, it is possible to provide a substrate having excellent interfacial adhesion that can be applied to the construction of a flexible device including a structure in which an organic material layer and an inorganic material layer are mixed to prevent peeling between the organic material layer and the inorganic material layer. The present application may also provide an organic electronic device having excellent durability and excellent properties such as light extraction efficiency by using the substrate for an organic electronic device as described above.

Description

Substrate for Organic Electronic Device {SUBSTRATE FOR ORGANIC ELECTRONIC DEVICE}

The present application relates to a substrate for an organic electronic device and its use.

An organic electronic device such as an organic light emitting device (OLED), an organic solar cell, an organic photoconductor (OPC), or an organic transistor includes an organic material layer vulnerable to external factors such as moisture. For example, Patent Documents 1 to 4 propose structures that can protect an organic electronic device from foreign materials.

In a flexible structure to which a plastic substrate or the like, which is vulnerable to penetration of foreign materials, is applied, a layer such as a barrier layer may be further included. Typically the barrier layer is implemented with an inorganic material. The organic electronic device including the barrier layer has a structure in which a layer of an organic material and a layer of an inorganic material, such as a plastic substrate, are mixed. In general, the inorganic layer and the organic layer have different thermal expansion characteristics, so that stresses may easily occur in the device, and such stress may occur even more when the flexible device is bent.

U.S. Patent 6,226,890 U.S. Patent 6,808,828 Japanese Laid-Open Patent No. 2000-145627 Japanese Laid-Open Patent No. 2001-252505

In a structure in which the organic material layer and the inorganic material layer are mixed due to factors such as stress generated as described above, interlayer peeling occurs easily, which adversely affects durability of the organic electronic device. Accordingly, one application of the present application is to provide a substrate for an organic electronic device that does not cause the above problem. The present application also includes an object of providing an organic electronic device having excellent durability and excellent properties such as light extraction efficiency by using the organic electronic device substrate as described above.

An exemplary substrate for an organic electronic device may include a flexible substrate film and an inorganic layer. In the inorganic layer may be formed on one surface of the base film. In the organic electronic device substrate, the base film and the inorganic layer exhibit excellent interfacial adhesion, and thus peeling due to a change in the surrounding environment or bending may be prevented. The interfacial adhesion between the base film and the inorganic layer can be quantified, for example, by a cross cut test based on ASTM D3359. That is, the peeling area measured by performing the cross cut test on the inorganic layer on the substrate may be 5% or less. The cross cut test can be performed in the manner described in the Examples. In accordance with the standard of ASTM D3359, Nichiban was formed on the inorganic layer of the substrate with a knife of 11 rows in the horizontal and vertical directions at intervals of 1 mm to form 100 square grids each having a length of 1 mm. The peeling area can be measured by measuring the state of the surface peeled together while attaching the CT-24 adhesive tape of the company to the cutting surface and then peeling.

Since the peeling area according to such a test means that the lower the value, the higher the adhesive force, the lower limit is not particularly limited, and may be, for example, 0%.

In the present application, in order to reduce the peeling area according to the test performed on the substrate to 5% or less, a method of forming an inorganic layer as described below in an ALD (Atomic Layer Deposition) method, a method of applying a specific substrate film, and a specific One or more of the methods of placing the buffer layer between the base film and the inorganic layer are applied.

The kind of base film applied to the board | substrate of this application is not specifically limited. For example, as a base film, what is known in the art can be used for implementation of a flexible element can be used. Representative examples of such a base film include a polymer film. Specific examples of the polymer film include polyimide (PI), polyethylene naphthalate (PEN), polycarbonate (PC), acrylic resin, poly (ethylene terephthatle) (PET), poly (ether sulfide) (PES), or polysulfone (PS). It may be illustrated, but is not limited thereto.

As the base film, those into which a functional group capable of reacting with the inorganic material layer can be used so that the above-mentioned adhesion can be achieved. For example, a functional group such as a hydroxy group, an amino group, or a carboxyl group may react chemically with the inorganic layer formed by the ALD method described later in the ALD process, thereby ensuring the excellent adhesion described above. The manner in which the functional group is introduced into the base film is not particularly limited, and for example, the polymer itself forming the base film may be one containing such functional group, or the polymer may not have the functional group. In the case where the ratio is small, the functional group can also be introduced by corona discharge or plasma treatment of the surface of the base film. The rate at which the functional group is introduced may be controlled to ensure proper interfacial adhesion.

A translucent film can be used as a base film. As used herein, the term translucent film may refer to a film having a transmittance of 50% or more, 60% or more, 70% or more, or 80% or more, for example, light in any one of the visible regions or light in the entire visible region. . Depending on the structure of the organic electronic device to which the substrate is applied, a film other than a light transmissive film may be used as the base film. If necessary, a reflective layer may be formed on the surface of the film or the like using a reflective material such as aluminum. The base film may be a TFT base film in which a driving TFT (Thin Film Transistor) exists.

The base film may have a coefficient of thermal expansion (CTE) in the range of about 5 ppm / ° C to 70 ppm / ° C. This range may be advantageous for preventing defects such as interlayer peeling that may occur in a structure in which an organic material layer and an inorganic material layer are mixed.

The base film may have a glass transition temperature of about 200 ° C. or more. The glass transition temperature may be a glass transition temperature of the base film itself, or may be a glass transition temperature of the base film having a buffer layer described later. This range may be suitable for high temperature processes for deposition or patterning in the manufacture of organic electronic devices. In another example, the glass transition temperature may be at least about 210 ° C, at least about 220 ° C, at least about 230 ° C, at least about 240 ° C, or at least about 250 ° C. The upper limit of the glass transition temperature is not particularly limited, and may be, for example, about 400 ° C, 350 ° C, or about 300 ° C.

The base film may have a surface roughness (RMS) within a range of about 0.1 nm to 5 nm. Such surface roughness may be with respect to the surface of the base film itself, or may be with respect to the surface of the buffer layer of the base film on which the buffer layer described later is formed. Such a range of surface roughness may be advantageous for improving the performance of the layer formed thereon. For example, when the first inorganic material layer is formed to have a barrier property, when the first inorganic material layer is formed on the surface having the surface roughness in the above range, a layer having more excellent moisture barrier property or the like can be formed. have. The surface roughness may, in other examples, be about 4 nm or less, about 3 nm or less, about 2.5 nm or less, or about 2 nm or less.

The base film may have a refractive index of about 1.5 or more, about 1.6 or more, about 1.7 or more, or about 1.75 or more. As used herein, the term refractive index is a refractive index measured for light having a wavelength of about 550 nm, unless otherwise specified. When the organic electronic device is an organic light emitting device, the range of the refractive index of the base film may be advantageous to increase the light efficiency of the device. The upper limit of the refractive index of the base film is not particularly limited, and may be, for example, about 2.0.

The high refractive index of the base film may be achieved by preparing the base film through a polymer having a high refractive index, or by mixing a component having a high refractive index in the film in the process of manufacturing the base film.

The thickness of the base film is not particularly limited and may be selected in an appropriate range in consideration of desired performance, for example, flexibility, light extraction efficiency or barrier properties. For example, the thickness of the base film may be in the range of about 10 μm to about 50 μm or in the range of about 20 μm to about 30 μm.

An inorganic layer exists on a base film. As used herein, the term inorganic layer may be, for example, a layer containing 50% or more or 60% of inorganic material by weight. The inorganic layer may include only an inorganic material or may include other components such as an organic material if the inorganic material is included in the above range.

The inorganic layer may be, for example, a barrier layer. As used herein, the term barrier layer may be a layer capable of blocking, inhibiting or mitigating the penetration of external factors that may adversely affect the performance of devices such as organic layers such as moisture or moisture. For example, the barrier layer may be a layer having a water vapor transmission rate (WVTR) of 10 ⁻⁴ g / m ² / day or less. WVTR herein may be a value to be measured using a meter (eg, PERMATRAN-W3 / 31, MOCON, Inc.) at 40 ° C. and 90% relative humidity conditions.

The barrier layer can be formed using a material known to be able to mitigate, prevent or inhibit the penetration of external factors such as moisture and oxygen. Such materials include metals 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 oxides such as; Metal nitrides such as SiN; Metal oxynitrides such as SiON; Or metal fluorides such as MgF ₂ , LiF, AlF _3, and CaF ₂ , or other materials known as absorbent materials having an absorption rate of 1% or more, or moisture-proof materials having an absorption coefficient of 0.1% or less.

The inorganic layer may be appropriate as small as possible the difference in refractive index with the base film. Such a case can contribute to the formation of a substrate having particularly excellent light extraction efficiency. For example, the absolute value of the difference in refractive index between the inorganic layer and the base film may be about 1 or less, about 0.7 or less, about 0.5 or less, or about 0.3 or less. Therefore, when the base film has a high refractive index as described above, the inorganic film layer should have a refractive index equivalent to that of the same. For example, the refractive index of the inorganic layer may be about 1.5 or more, about 1.6 or more, about 1.7 or more, or about 1.75 or more. When the organic electronic device to which the substrate of the present application is applied is an organic light emitting device, the range of the refractive index of the base film may be advantageous to increase the light efficiency of the device. The upper limit of the refractive index of the inorganic layer is not particularly limited, and may be, for example, about 2.0.

The thickness of the inorganic layer may be determined according to the effect according to the intended use, and the range is not particularly limited, but in one example, about 10 nm to 100 nm, 10 nm to 90 nm, 10 nm to 80 nm, 10 nm to It may be in the range of 70 nm, 10 nm to 60 nm, 10 nm to 50 nm or 20 nm to 50 nm.

The inorganic layer may be a single layer or a multilayer structure, but may be required to have a multilayer structure to satisfy the crystallinity as described above. The multilayer structure may include a structure in which the same type or different types of inorganic layers are stacked. Forming the inorganic layer in a multi-layered structure has the above-described interfacial adhesion and may contribute to forming the inorganic layer having the above-mentioned crystallinity. In addition, forming the inorganic layer in a multilayer structure may contribute to the formation of the inorganic layer having the aforementioned refractive index.

In the case of a multilayer structure, the inorganic layer may include a laminated structure of at least a first sublayer and a second sublayer. The thicknesses of the first and second sublayers may be adjusted in consideration of interfacial adhesion, crystallinity, barrier property, or refractive index required for the inorganic layer. For example, the thicknesses of the first and second sublayers can all be adjusted in the range of 5 nm or less, 4 nm or less, 3 nm or less, or 2 nm or less. The lower limit of the thickness of the sublayer is not particularly limited. As the thickness of the sublayer is thinner, the contribution to interface adhesion, crystallinity, barrier property, and refractive index is increased. However, when the thickness of the sublayer is thin, the number of processes required to reach the target thickness may be increased. Therefore, the lower limit of the thickness of the sub layer may be set in an appropriate range in consideration of the desired thickness and the like, and may be adjusted in a range of about 0.1 nm or more, for example.

 In consideration of interfacial adhesion, crystallinity, barrier property and refractive index, the thicknesses of all the sublayers included in the inorganic layer of the multilayer structure may be adjusted within the above range. In this case, the inorganic layer may not include a sublayer having a thickness greater than 5 nm.

The number of sublayers included in the inorganic layer is not particularly limited and may be determined according to the thickness of the sublayer and the thickness of the desired inorganic layer. In one example, the inorganic layer may include 2 to 50 sublayers. In the above range, the sub layer may include 4 or more, 6 or more, 8 or more, or 10 or more. In addition, within the above range, the sub-layer may include 45 or less, 40 or less, 35 or less, 30 or less, 25 or less, 20 or less, or 15 or less. When the inorganic layer includes three or more sublayers, each sublayer may be the first or second sublayer, and may also include a third sublayer or more.

The sublayer may be formed of various materials, but may be formed of an oxide such as a metal oxide in terms of contributing to interfacial adhesion, crystallinity, barrier property, and refractive index. If necessary, all the sub layers included in the inorganic layer may be formed of the oxide. The kind of oxide that can be used in this case is not particularly limited, and may be appropriately selected from oxides capable of forming the above-mentioned barrier layer. Sublayers in contact with each other among the sublayers may be formed of different materials to contribute to interfacial adhesion, crystallinity, barrier property, refractive index, and the like. Thus, if the first and second sublayers are in contact with each other, they may be formed of different materials, for example different oxides. Even when the inorganic layer includes a third sublayer, a fourth sublayer or more sublayers as described above, it may be advantageous that the sublayers which are also in contact with each other are formed of different materials, for example, different oxides.

The first sublayer may have a first refractive index, and the second sublayer may have a second refractive index different from the first refractive index. By laminating such layers, it may be advantageous to adjust the refractive index of the inorganic layer to the above-mentioned range while securing the above-described effects. The absolute value of the difference between the first refractive index and the second refractive index may be, for example, 0.1 or more. In another example, the absolute value may be 0.2 or more, 0.3 or more, 0.4 or more, 0.5 or more or 0.6 or more. In addition, the absolute value may be in a range of 2 or less, 1.8 or less, 1.6 or less, 1.4 or less, or 1.2 or less in another example. The range of each of the first and second refractive indices is not particularly limited as long as the range of the refractive indices is secured. For example, the refractive index of the first sublayer is in the range of 1.4 to 1.9, and the refractive index of the second sublayer is 2.0 to May be in the range of 2.6. The first and second sub-layers as described above may be metal oxide layers, respectively. For example, suitable materials for the first sublayer include Al ₂ O ₃ and the like, and suitable materials for the second sublayer include TiO ₂ , but the final laminated structure has the aforementioned refractive indices, respectively. If it can have a barrier property, a variety of other materials can be applied in addition.

The inorganic material layer or each sublayer can be formed through a known method, but it is advantageous to form the ALD (Atomic Layer Deposition) method from the viewpoint of securing interfacial adhesion. The ALD method includes, for example, alternately depositing a precursor such as an organic metal and a precursor such as water on a surface to be deposited, and in this process, monolayers of the precursors are alternately formed to react with each other to form an inorganic layer. This can be formed. When the layer formed by the ALD method has a predetermined functional group, for example, the aforementioned hydroxyl group or the like in the base film, the functional group may react with the functional group in the formation process, and thus, the desired interfacial adhesion may be secured. . Unless otherwise specified herein, the term ALD layer may mean an inorganic layer formed by the ALD method.

In addition to the ALD method, a method of forming an inorganic layer or a sub layer may include sputtering, pulsed laser deposition, electron beam evaporation, thermal evaporation, or laser molecular L-MBE. Chemical Vapor Deposition (PVD) or Metal Organic Chemical Vapor Deposition (MOCVD), Hybrid Vapor Phase Epitaxy (HVPE), Initiated Chemical Vapor Deposition (iCVD) or Plasma Enhanced Chemical Vapor Deposition (PECVD) Vapor Deposition) may be exemplified. If necessary, the performance of the inorganic layer may be maximized by selecting an appropriate method according to the material used among the above methods.

The substrate of the present application may include additional layers. For example, the substrate of the present application may further include a buffer layer between the inorganic layer and the base film in order to achieve the interface adhesion between the inorganic layer and the base film described above. However, the buffer layer is not an essential configuration and, for example, the buffer layer may not be required if the desired interfacial adhesion is achieved through the substrate into which the specific functional group described above is introduced.

When the buffer layer is present, the buffer layer may be selected as a material capable of achieving the above-described interface adhesion.

In one example, the buffer layer may be an oxide, nitride or oxy nitride of a metal or a nonmetal. Examples of the metal or nonmetal include silicon (Si) or titanium (Ti), but are not limited thereto.

In another example, the buffer layer may be a layer including an organic-inorganic composite material.

In another example, the buffer layer may be a layer including polysilazane including a repeating unit of Formula A below.

[Formula A]

R ₁ to R ₃ in formula (A) are each independently hydrogen, an alkyl group unsubstituted or substituted with a silyl group, an alkoxy group or an aryl group unsubstituted or substituted with a silyl group, and at least one of R ₁ to R ₃ is hydrogen.

In another example, the buffer layer may be a layer including a repeating unit represented by Formula B below.

[Formula B]

R ₁ to R ₃ in Formula B are each independently hydrogen or an alkyl group, X is a single bond, an alkylene group, -C (= 0)-, -OC (= 0)-, or -C (= 0) O- , A is an alkylene group, m is a number in the range of 0 to 10, Z is a hydroxy group, a carboxyl group or an amine group.

The substrate of the present application may also include an electrode layer present on the inorganic layer as an additional layer.

As the electrode layer, a hole injectable or electron injecting electrode layer commonly used in organic electronic devices may be used. The electrode layer may be a transparent electrode layer or a reflective electrode layer.

The hole injection electrode layer may be formed using a material having a relatively high work function, for example, and may be formed using a transparent or reflective material if necessary. For example, the hole injection electrode layer may comprise a metal, alloy, electrically conductive compound, or a mixture of two or more thereof, having a work function of about 4.0 eV or more. Such materials include metals 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, Oxide materials such as ZnO, SnO ₂ or In ₂ O ₃ , metal nitrides such as gallium nitride, metal serenides such as zinc serenides, metal sulfides such as zinc sulfides, and the like. The transparent hole injection electrode layer can also be formed using a laminate of a metal thin film such as Au, Ag or Cu, and a high refractive transparent material such as ZnS, TiO ₂ or ITO.

The hole injection 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 as needed may be patterned through a process using known photolithography, shadow mask, or the like.

The electron injection electrode layer may be formed using, for example, a material having a relatively small work function. For example, an appropriate transparent or reflective material may be used among materials used for forming the hole injection electrode layer. It may be formed by, but is not limited thereto. The electron injection electrode layer can also be formed using, for example, a vapor deposition method or a sputtering method, and can be appropriately patterned if necessary.

The thickness of the electrode layer may be formed to have a thickness of, for example, about 90 nm to 200 nm, 90 nm to 180 nm, or about 90 nm to 150 nm.

The substrate may further include an intermediate layer between the electrode layer and the inorganic layer when the electrode layer is formed, between the inorganic layer and the base film, or between predetermined sublayers when the inorganic layer is a multilayer structure. Such an intermediate layer may have, for example, a modulus of elasticity of 20 GPa or more at a temperature of 23 ° C. In another example, the modulus of elasticity may be 30 GPa or more, 40 GPa or more, or 50 GPa or more. The upper limit of the elastic modulus is not particularly limited, but may be, for example, about 200 GPa or less, 180 GPa or less, 160 GPa or less, 140 GPa or less, 120 GPa or less, or 100 GPa or less. Such an intermediate layer may serve to alleviate stress that may occur between the inorganic layer and the electrode layer, thereby contributing to durability.

The intermediate layer may be formed of an inorganic material, an organic material, or an organic-inorganic composite material having the above elastic modulus.

Examples of the inorganic material that may be used to form the intermediate layer include TiO ₂ , Si ₃ N ₄ , MgO, Al ₂ O ₃ , ZnO, or ZrO ₂ , but are not limited thereto.

Such intermediate layers can be formed in a variety of ways. However, the intermediate layer may be formed by the above-described ALD method, or may be formed by MLD (Molecular Layer Deposition) or iCVD (Initiated Chemical Vapor Deposition) in terms of easy access to the above-described elastic modulus, film quality, interfacial adhesion, refractive index, and the like. Can be formed in a manner. Thus, the intermediate layer may be an ALD layer, MLD layer or iCVD layer. As described above, the ALD layer means a layer formed by ALD, and the MLD layer or iCVD layer means a layer formed by MLD or iCVD. The MLD method is very similar to the ALD method, and in this process, a molecular fragment including an organic material or an inorganic material may be deposited. For example, it is possible to efficiently control the elastic modulus by forming an organic-inorganic composite material by alternately depositing a material capable of forming an inorganic component with an MLD method and an oxygen source or a liquid such as ethylene glycol. . The iCVD method is a polymer vapor deposition process using an initiator, and depending on the material, it is possible to form an excellent intermediate layer through the application of this method.

The intermediate layer may be, for example, a material having a low refractive index within a range of about 1.47 to 1.7, or a material having a high refractive index of 1.8 or more. When the intermediate layer has a low refractive index, the inorganic layer may have a high refractive index, for example, a refractive index of about 1.8 or more, in terms of light extraction efficiency.

The present application also relates to organic electronic devices. The organic electronic device includes a substrate for an organic electronic device described above; And an element region having a first electrode layer, an organic material layer, and a second electrode layer on the inorganic material layer of the substrate. However, when the substrate for an organic electronic device includes the aforementioned electrode layer, the electrode layer may serve as the first electrode layer.

An exemplary organic electronic device includes a substrate including the base film 101 and the inorganic material layer 102 sequentially present in an upward direction as shown in FIG. 1, a first electrode layer 103, an organic material layer 104, and a second electrode layer ( 105), the second inorganic layer 106 and the cover film 107 may be included. Each of the layers may be directly stacked without another layer between adjacent layers, or may be stacked via another layer.

As used herein, the term upward direction means a direction from the first electrode layer to the second electrode layer unless otherwise specified, and the term downward direction refers to a direction from the second electrode layer toward the first electrode layer unless otherwise specified. it means.

Hereinafter, for convenience of description, a region including all elements (except the first electrode layer) existing under the first electrode layer in the structure will be referred to as a substrate region, and the first electrode layer and the second electrode layer and between The region containing all the elements present is called an element region, and the region containing all elements (except the second electrode layer) present on top of the second electrode layer is called an upper region.

The substrate region may have a haze in a range of 3% to 90%, 3% to 85%, 3% to 50%, or 3% to 30%. Such a haze range may contribute, for example, to light extraction efficiency. If necessary, other factors such as spacing with the electrode layer of the light emitting unit may be adjusted as described below for higher light extraction efficiency. However, when designing a structure in which light from the organic layer is emitted upward, the haze of the substrate region does not necessarily belong to the above-described range. In order to adjust the haze of the substrate region, the haze of the base film included in the substrate region may be adjusted, or a scattering layer, a scattering adhesive, or the like described later may be applied.

In consideration of the haze of the substrate region, a substrate having a haze can be used as the base film described above. However, when the haze of a board | substrate area is ensured by another layer mentioned later, a base film does not necessarily need to have haze. In the case of haze, the haze of the base film may be in the range of 3% to 90%. Another lower limit of the haze may be, for example, about 5% or 10%. In addition, another upper limit of haze may be, for example, about 85%, 80%, 75%, 70%, 65%, 60%, 55%, 50%, 45%, 40%, 35%, or 30%. . The method for causing the substrate to have haze is not particularly limited, and a method commonly applied to generate haze may be applied. For example, in the case of a polymer film, a method of adding scattering particles having a refractive index different from the surrounding polymer matrix and having an appropriate average particle diameter, or a monomer such as a main chain of a polymer that allows haze to appear in the polymer itself. A method of polymerizing a monomer having a refractive index different from that of a polymer and forming a film using such a polymer may be applied.

The substrate region may include additional layers. As a layer that may additionally be present in the substrate region, a scattering layer, a carrier substrate, a barrier film, or an adhesive layer may be exemplified.

In order to secure the haze, the substrate region may further include a scattering layer. As used herein, the term scattering layer may refer to any kind of layer formed to be able to scatter, refract or diffract light incident on the layer. The scattering layer is not particularly limited as long as the scattering layer is implemented to exhibit such a function.

For example, the scattering layer can be a layer comprising a matrix material and scattering regions. As used herein, the term “scattering region” refers to a region having a refractive index different from a surrounding material such as, for example, a matrix material or the buffer layer, and having an appropriate size to scatter, refract, or diffract incident light. Can be. The scattering region may be, for example, a particle 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 and / or the buffer 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. 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. The kind of matrix material that can be used is not particularly limited, and for example, an appropriate material may be selected and used from among the materials mentioned to be used in the formation of the buffer layer.

In another example, the scattering layer may be a layer having an uneven structure. The concave-convex structure of the scattering layer can be appropriately adjusted, and if necessary, the incident light can be scattered when a buffer layer having an appropriate refractive index is formed thereon. 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 formed by, for example, a coating method such as a wet or dry coating, or a deposition method such as PVD or CVD. Alternatively, the scattering layer may be applied by nanoimprinting or microembossing.

As another layer that can be included in the substrate region, a barrier film can be exemplified. In the flexible structure, a substrate film having a relatively low barrier property is used as compared with a rigid structure in which a substrate having excellent barrier property is used, such as a glass substrate, and thus, an additional barrier film is used, for example, to provide a barrier property. May be present at the bottom of The barrier film may be any one capable of ensuring appropriate barrier properties and light transmittance when necessary.

The barrier film may be attached to the base film by, for example, an adhesive layer. In this case, the barrier film may be attached to a surface opposite to the surface on which the inorganic layer is formed. As used herein, the term adhesive layer is a term encompassing not only a material commonly referred to as an adhesive but also a layer formed by using a material referred to as an adhesive or a material referred to as an adhesive. The material for forming the adhesive layer is not particularly limited, and for example, a known point / adhesive material such as an acrylic polymer, a silicone polymer, a rubber polymer, an ethylene polymer such as EVA (Ethylene vinyl acetate) polymer or a polyisobutylene (PIB) may be used. Can be used.

An appropriate moisture barrier material may be blended in the adhesive layer. Hereinafter, the adhesive layer in which the moisture barrier material is blended herein may be referred to as a barrier adhesive layer. As used herein, the term "moisture barrier material" may be used as a generic term for a component capable of absorbing or removing moisture or moisture introduced from the outside through a physical or chemical reaction. The specific kind of the moisture barrier material that can be blended into the adhesive layer is not particularly limited, and examples thereof include one kind or a mixture of two or more kinds of metal oxides, organometallic oxides, metal salts, or phosphorus pentoxide (P ₂ O ₅ ). . Specific examples of the metal oxide may include lithium oxide (Li ₂ O), sodium oxide (Na ₂ O), barium oxide (BaO), calcium oxide (CaO), magnesium oxide (MgO), and the like. Examples include lithium sulfate (Li ₂ SO ₄ ), sodium sulfate (Na ₂ SO ₄ ), calcium sulfate (CaSO ₄ ), magnesium sulfate (MgSO ₄ ), cobalt sulfate (CoSO ₄ ), gallium sulfate (Ga ₂ (SO ₄ ) ₃ ), sulfates such as titanium sulfate (Ti (SO ₄ ) ₂ ) or nickel sulfate (NiSO ₄ ), etc., calcium chloride (CaCl ₂ ), magnesium chloride (MgCl ₂ ), strontium chloride (SrCl ₂ ), yttrium chloride (YCl ₃ ) , Copper chloride (CuCl ₂ ), cesium fluoride (CsF), tantalum fluoride (TaF ₅ ), niobium fluoride (NbF ₅ ), lithium bromide (LiBr), calcium bromide (CaBr ₂ ), cesium bromide (CeBr ₃ ), selenium bromide Metal halides such as (SeBr ₄ ), vanadium bromide (VBr ₃ ), magnesium bromide (MgBr ₂ ), barium iodide (BaI ₂ ) or magnesium iodide (MgI ₂ ); Or metal chlorates such as barium perchlorate (Ba (ClO ₄ ) ₂ ) or magnesium perchlorate (Mg (ClO ₄ ) ₂ ), and the like, but is not limited thereto.

Appropriate scattering particles may be blended in the adhesive layer, whereby the adhesive layer itself may exhibit a suitable haze. Light extraction efficiency can be improved when the adhesive layer exhibits haze. The kind of scattering particles that can be blended into the adhesive layer is not particularly limited, and an appropriate kind may be selected and used from the scattering particles included in the scattering layer in consideration of the refractive index of the resin forming the adhesive layer.

Other layers that may be present in the substrate region may also be exemplified by a carrier substrate that may be temporarily or permanently attached to the bottom of the base film. In general, a rigid substrate such as a glass substrate may be applied to the carrier substrate.

The substrate region may be formed in various structures. For example, the substrate region may include a structure in which the inorganic layer and the base film are sequentially formed in a downward direction, a structure in which the above-described buffer layer or scattering layer is formed between the inorganic layer and the base film, and a lower portion of the base film. If a carrier film or a barrier film is needed, it can have a structure etc. which are attached by the adhesive bond layer.

An organic material layer exists between the first and second electrode layers. The organic material layer may include at least two light emitting units. In such a structure, light generated in the light emitting unit may be emitted to the transparent electrode layer through a process of being reflected by the reflective electrode layer.

The distance between the transparent electrode layer and the reflective electrode layer may be adjusted in consideration of appropriate light extraction efficiency. The adjusted interval may be organically combined with the above-described haze of the base region or the distance between the reflective electrode layer and the light emitting unit, which will be described later, to greatly increase the light extraction efficiency of the organic electronic device.

The organic layer may include a first light emitting unit having a first light emitting center wavelength and a second light emitting unit having a second light emitting center wavelength. The first emission center wavelength may be in a range different from the second emission center wavelength. In consideration of light extraction efficiency, the distance between each light emitting unit and the reflective electrode layer may be adjusted. In this specification, an interval between an object and another object may mean the shortest distance connecting the opposite surfaces between the objects. For example, the ratio B / A of the distance A between the first light emitting unit and the reflective electrode layer and the distance B between the second light emitting unit and the reflective electrode layer may be in a range of about 1.5 to 20. have. In other examples, the ratio (B / A) is 19 or less, 18 or less, 17 or less, 16 or less, 15 or less, 14 or less, 13 or less, 12 or less, 11 or less, 10 or less, 9 or less, 8 or less, 7 or less, 6 or less, 5 or less, 4 or less, or 3.5 or less. In addition, the ratio (B / A) may be 2 or more or 2.5 or more in another example. As such, an organic layer including each light emitting unit having the adjusted interval may be formed on the base region having the above-described haze to improve light extraction efficiency of the organic electronic device.

In the above, the first light emitting unit may be adjusted to emit light having a shorter wavelength than the second light emitting unit, and thus the first light emitting center wavelength may be shorter than the second light emitting center wavelength. In this case, the first light emitting unit may be disposed closer to the reflective electrode layer than the second light emitting unit, so that the distance A between the first light emitting unit and the reflective electrode layer is the distance B between the second light emitting unit and the reflective electrode layer. It may be arranged shorter than).

The distance between the emission center wavelength and the reflective electrode layer of each light emitting unit is not particularly limited, and may be adjusted in consideration of, for example, the desired emission wavelength. For example, the emission center wavelength of the first light emitting unit may be in the range of 380 nm to 500 nm or 400 nm to 500 nm, and the distance between the first light emitting unit and the reflective electrode layer is 150 nm to 200 nm or 50. It may be in the range of nm to 70 nm. In addition, the emission center wavelength of the second light emitting unit may be in the range of 500 nm to 700 nm, and the gap between the second light emitting unit and the reflective electrode layer may exist at a level that satisfies the above-mentioned ratio (B / A). have.

An intermediate electrode layer or charge generating layer may further be present between the first light emitting unit and the second light emitting unit for proper light emission. Therefore, the light emitting units may have a structure divided by an intermediate electrode layer or a charge generating layer (CGL) having charge generation characteristics.

If necessary, the organic layer may include other light emitting units in addition to the first and second light emitting units.

Even when there are light emitting units further different from the first and second light emitting units, an intermediate electrode layer or a charge generating layer may exist between each light emitting unit. In addition, when two or more light emitting units exist, it may be appropriate that the light emission center wavelengths of each light emitting unit exist so that the long wavelength and the short wavelength are alternately repeated. For example, if the emission center wavelength of the light emitting unit closest to the reflective electrode layer is a short wavelength, the center wavelength of the light emitting unit that follows thereafter may be repeated in the order of long wavelength, short wavelength, long wavelength and short wavelength. In the above, the range of the long wavelength and the short wavelength is not particularly limited, but the short wavelength may be a wavelength in the range of 380 nm to 500 nm or 400 nm to 500 nm, and the long wavelength may be a wavelength in the range of 500 nm to 700 nm. In addition, the light emitting unit having the short emission center wavelength and the foot and the unit having the long emission center wavelength may not overlap the emission center wavelengths.

Accordingly, for example, the organic layer may further include a third light emitting unit. In this case, the ratio C / A of the distance A between the first light emitting unit and the reflective electrode layer and the distance C between the third light emitting unit and the reflective electrode layer may be in the range of 3.5 to 4.5, or about 4. . In addition, the emission center wavelength of the third light emitting unit may be in the range of 400 to 500 nm.

In addition, the organic layer that may further include the third light emitting unit may further include a fourth light emitting unit. In this case, the ratio D / A of the distance A between the first light emitting unit and the reflective electrode layer of the organic layer and the distance D between the fourth light emitting unit and the reflective electrode layer may be in the range of 4.5 to 5.5 or about 5 degrees. have.

In addition, the emission center wavelength of the fourth light emitting unit may be in the range of 500 to 700 nm.

The organic layer may further include a fifth light emitting unit. In this case, the ratio E / A of the distance A between the first light emitting unit and the reflective electrode layer of the organic layer and the distance E between the fifth light emitting unit and the reflective electrode layer may be in the range of about 5.5 to 6.5 or about 6 days. In addition, the emission center wavelength of the fifth light emitting unit may be in the range of 400 to 500 nm.

That is, the organic layer has a structure (structure 1) including first and second light emitting units sequentially from the reflective electrode layer, a structure (structure 2) including first to third light emitting units, and first to fourth light emitting units. It may have a structure (structure 3) comprising or a structure (structure 4) comprising the first to fifth light emitting units, and may include additional light emitting units if necessary.

In the structure 1, the distance between the first light emitting unit and the reflective electrode layer may be in a range of about 150 nm to 200 nm or 50 nm to 70 nm as described above. In addition, the ratio B / A of the distance A between the first light emitting unit and the reflective electrode layer and the distance B between the second light emitting unit and the reflective electrode layer may be about 2.5 to 3.5, about 2.6 to 3.4, or about 3. have. In addition, the emission center wavelengths of the first light emitting unit may be in the range of about 400 to 500 nm, and the emission center wavelengths of the second light emitting unit may be in the range of about 500 nm to 700 nm and may not overlap each other.

Further, in the structure 2, the distance between the first light emitting unit and the reflective electrode layer may be in the range of about 150 nm to 200 nm or 50 nm to 70 nm as described above. In addition, the ratio B / A of the distance A between the first light emitting unit and the reflective electrode layer and the distance B between the second light emitting unit and the reflective electrode layer may be about 2.5 to 3.5, about 2.6 to 3.4, or about 3. have. Further, the ratio C / A of the distance A between the first light emitting unit and the reflective electrode layer and the distance C between the third light emitting unit and the reflective electrode layer may be about 3.5 to 4.5, about 3.6 to 4.4, or about 4. have. Further, the emission center wavelength of the first light emitting unit is in the range of about 400 to 500 nm, the emission center wavelength of the second light emitting unit is in the range of about 500 nm to 700 nm, and the emission center wavelength of the third light emitting unit is It may be in the range of about 400 to 500 nm and not overlap with each other.

Further, in the structure 3, the distance between the first light emitting unit and the reflective electrode layer may be in the range of about 150 nm to 200 nm or 50 nm to 70 nm as described above. In addition, the ratio B / A of the distance A between the first light emitting unit and the reflective electrode layer and the distance B between the second light emitting unit and the reflective electrode layer may be about 2.5 to 3.5, about 2.6 to 3.4, or about 3. have. Further, the ratio C / A of the distance A between the first light emitting unit and the reflective electrode layer and the distance C between the third light emitting unit and the reflective electrode layer may be about 3.5 to 4.5, about 3.6 to 4.4, or about 4. have. Further, the ratio D / A of the distance A between the first light emitting unit and the reflective electrode layer and the distance D between the fourth light emitting unit and the reflective electrode layer may be about 4.5 to 5.5, about 4.6 to 5.4, or about 5 degrees. have. Further, the emission center wavelength of the first light emitting unit is in the range of about 400 to 500 nm, the emission center wavelength of the second light emitting unit is in the range of about 500 nm to 700 nm, and the emission center wavelength of the third light emitting unit is It is in the range of about 400 to 500 nm, the emission center wavelength of the fourth light emitting unit is in the range of about 500 nm to 700 nm and may not overlap each other.

Further, in the structure 4, the distance between the first light emitting unit and the reflective electrode layer may be in the range of about 150 nm to 200 nm or 50 nm to 70 nm as described above. In addition, the ratio B / A of the distance A between the first light emitting unit and the reflective electrode layer and the distance B between the second light emitting unit and the reflective electrode layer may be about 2.5 to 3.5, about 2.6 to 3.4, or about 3. have. Further, the ratio C / A of the distance A between the first light emitting unit and the reflective electrode layer and the distance C between the third light emitting unit and the reflective electrode layer may be about 3.5 to 4.5, about 3.6 to 4.4, or about 4. have. Further, the ratio D / A of the distance A between the first light emitting unit and the reflective electrode layer and the distance D between the fourth light emitting unit and the reflective electrode layer may be about 4.5 to 5.5, about 4.6 to 5.4, or about 5 degrees. have. Further, the ratio E / A of the distance A between the first light emitting unit and the reflective electrode layer and the distance E between the fifth light emitting unit and the reflective electrode layer may be about 5.5 to 6.5, about 5.6 to 6.4, or about 6. In addition, the emission center wavelength of the first light emitting unit is in the range of about 400 to 500 nm, the emission center wavelength of the second light emitting unit is in the range of about 500 nm to 700 nm, and the emission center wavelength of the third light emitting unit. Is in the range of about 400 to 500 nm, the emission center wavelength of the fourth light emitting unit is in the range of about 500 nm to 700 nm, and the emission center wavelength of the fifth light emitting unit is in the range of about 400 to 500 nm, There may be no duplication.

The material constituting the light emitting unit is not particularly limited. Fluorescent or phosphorescent organic materials having various emission center wavelengths are known in the art, and an appropriate kind can be selected from these known materials to form the light emitting unit. Examples of the material of the light emitting unit include tris (4-methyl-8-quinolinolate) aluminum (III) (tris (4-methyl-8-quinolinolate) aluminum (III)) (Alg3), 4-MAlq3, Gaq3 and the like. Alq series of 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 (1,2, Cyclopenadiene derivatives such as 3,4,5-pentaphenyl-1,3-cyclopentadiene), DPVBi (4,4'-bis (2,2'-diphenylyinyl) -1,1'-biphenyl), disti Yl 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 _{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) (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 unit includes the material as a host and further includes perylene, distyrylbiphenyl, DPT, quinacridone, rubrene, BTX, ABTX, DCJTB and the like. It may have a host-dopant system including a as a dopant.

The light emitting unit can also be formed by appropriately adopting a kind exhibiting light emission characteristics among the electron-accepting organic compound or electron donating organic compound described later.

The organic material layer may be formed in various structures further including various other functional layers known in the art, as long as the light emitting unit includes a light emitting unit. Examples of the layer that may be included in the organic material layer include an electron injection layer, a hole blocking layer, an electron transport layer, a hole transport layer, a hole injection layer, and the like.

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 compound known without particular limitation may be used. Such organic compounds include polycyclic compounds such as p-terphenyl or quaterphenyl or derivatives thereof, naphthalene, tetratracene, pyrene, coronene, and coronene. ), Polycyclic hydrocarbon compounds or derivatives thereof, such as chrysene, anthracene, diphenylanthracene, naphthacene or phenanthrene, phenanthroline, vasophenanthrol Heterocyclic compounds or derivatives thereof, such as lean (bathophenanthroline), phenanthridine, acridine (acridine), quinoline (quinoline), quinoxaline or phenazine (phenazine) and the like. In addition, fluoroceine, perylene, phthaloperylene, naphthaloperylene, naphthaloperylene, perynone, phthaloperinone, naphtharoferinone, diphenylbutadiene ( diphenylbutadiene, tetraphenylbutadiene, oxadiazole, ardazine, bisbenzoxazoline, bisstyryl, pyrazine, cyclopentadiene , Oxine, aminoquinoline, imine, diphenylethylene, vinylanthracene, diaminocarbazole, pyrane, thiopyrane, polymethine, mero Cyanine (merocyanine), quinacridone or rubrene, or derivatives thereof, JP-A-1988-295695, JP-A-1996-22557, JP-A-1996-81472, Japanese Patent Laid-Open Publication No. 1993-009470 or Japanese Patent Laid-Open Publication No. Metal chelate complex compounds disclosed in Japanese Patent Application Publication No. 017764, for example, tris (8-quinolinolato) aluminium, which is a metal chelated oxanoid compound, and bis (8-quinolin) Norato) magnesium, bis [benzo (f) -8-quinolinolato] zinc {bis [benzo (f) -8-quinolinolato] zinc}, bis (2-methyl-8-quinolinolato) aluminum, Tris (8-quinolinolato) indium, tris (5-methyl-8-quinolinolato) aluminum, 8-quinolinolatorium, tris (5-chloro- Metal complex having one or more 8-quinolinolato or derivatives thereof, such as 8-quinolinolato) gallium, bis (5-chloro-8-quinolinolato) calcium, as derivatives, Japanese Patent Application Laid-Open No. 1993-202011 Oxadiazole compounds disclosed in Japanese Patent Laid-Open No. 195-179394, Japanese Patent Laid-Open Publication No. 195-278124, or Japanese Patent Publication No. 195-228579, and Japanese Patent Publication Triazine compounds disclosed in Japanese Patent Application Laid-Open Nos. 195-157473, Stilbene Derivatives, Distyrylarylene Derivatives, and Japanese Patent Publication No. 194-132080 Styryl derivatives disclosed in Japanese Patent Application Laid-Open No. 1944-88072 and the like, diolefin derivatives disclosed in Japanese Patent Laid-Open No. 194-100857 and Japanese Patent Application Laid-Open No. 194-207170; Fluorescent brighteners such as a benzooxazole compound, a benzothiazole compound or a benzoimidazole compound; 1,4-bis (2-methylstyryl) benzene, 1,4-bis (3-methylstyryl) benzene, 1,4-bis (4-methylstyryl) benzene, distyrylbenzene, 1,4- Bis (2-ethylstyryl) benzyl, 1,4-bis (3-ethylstyryl) benzene, 1,4-bis (2-methylstyryl) -2-methylbenzene or 1,4-bis (2- Distyrylbenzene compounds such as methylstyryl) -2-ethylbenzene and the like; 2,5-bis (4-methylstyryl) pyrazine, 2,5-bis (4-ethylstyryl) pyrazine, 2,5-bis [2- (1-naphthyl) vinyl] pyrazine, 2,5- Distyryls such as bis (4-methoxystyryl) pyrazine, 2,5-bis [2- (4-biphenyl) vinyl] pyrazine or 2,5-bis [2- (1-pyrenyl) vinyl] pyrazine Pyrazine (distyrylpyrazine) compound, 1,4-phenylenedimethylidine, 4,4'-phenylenedimethylidine, 2,5-xylenedimethylidine, 2,6-naphthylenedimethylidine, 1,4-biphenylenedimethyl Lidine, 1,4-para-terphenylenedimethellidine, 9,10-anthracenediyldimethylidine or 4,4 '-(2,2-di-thi-butylphenylvinyl) biphenyl Dimethylidine compounds or derivatives thereof such as 4,4- (2,2-diphenylvinyl) biphenyl, and the like, and the silanamines disclosed in Japanese Patent Application Laid-Open No. 194-49079 or Japanese Patent Application Laid-Open No. 1994-9393778. (silanamine) derivatives, disclosed in Japanese Patent Application Laid-Open No. 194-279322 or Japanese Patent Application Laid-Open No. 194-279323 Polyfunctional styryl compound, an oxadiazole derivative disclosed in Japanese Patent Application Laid-Open No. 194-107648 or Japanese Patent Application Laid-Open No. 194-092947, an anthracene compound disclosed in Japanese Patent Application Laid-Open No. 194-206865, Japanese Patent Oxynate derivative disclosed in Japanese Patent Application Laid-Open No. 194-145146, tetraphenylbutadiene compound disclosed in Japanese Patent Application Laid-Open No. 1992-96990, organic trifunctional compound disclosed in Japanese Patent Application Laid-Open No. 1991-296595, Japanese Patent A coumarin derivative disclosed in Japanese Patent Application Laid-Open No. 1990-191694, a perylene derivative disclosed in Japanese Patent Application Laid-Open No. 1990-196885, a naphthalene derivative disclosed in Japanese Patent Application Laid-Open No. 1990-255789, and Japanese Patent Publication A phthaloperynone derivative disclosed in Japanese Patent Application Laid-Open No. 1990-289676 or Japanese Patent Application Laid-Open No. 1990-88689, or Japanese Patent Application Laid-Open No. 1990-25029 Styrylamine derivatives disclosed in Japanese Patent No. 2 and the like can also be used as the electron-accepting organic compound included in the low refractive layer. In addition, the electron injection layer may be formed using, for example, a material such as LiF or CsF.

The hole blocking layer is a layer capable of preventing the injected holes from entering the electron injecting electrode layer through the light emitting unit and improving the life and efficiency of the device. If necessary, a light blocking unit and an electron It can be formed in an appropriate part between the granular electrode layers.

The hole injection layer or hole transport layer may comprise, for example, an electron donating organic compound. Examples of the electron donating organic compound include N, N ', N'-tetraphenyl-4,4'-diaminophenyl, N, N'-diphenyl-N, N'-di (3-methylphenyl) -4, 4'-diaminobiphenyl, 2,2-bis (4-di-p-tolylaminophenyl) propane, N, N, N ', N'-tetra-p-tolyl-4,4'-diamino ratio Phenyl, bis (4-di-p-tolylaminophenyl) phenylmethane, N, N'-diphenyl-N, N'-di (4-methoxyphenyl) -4,4'-diaminobiphenyl, N , N, N ', N'-tetraphenyl-4,4'-diaminodiphenylether, 4,4'-bis (diphenylamino) quadriphenyl [4,4'-bis (diphenylamino) quadriphenyl], 4-N, N-diphenylamino- (2-diphenylvinyl) benzene, 3-methoxy-4'-N, N-diphenylaminosteelbenzene, N-phenylcarbazole, 1,1-bis (4 -Di-p-triaminophenyl) cyclohexane, 1,1-bis (4-di-p-triaminophenyl) -4-phenylcyclohexane, bis (4-dimethylamino-2-methylphenyl) phenylmethane , N, N, N-tri (p-tolyl) amine, 4- (di-p-tolylamino) -4 '-[4- (di-p-tolylamino) styryl] stilbene, N, N, N ', N'-tetraphenyl-4,4'-diamino ratio Nyl N-phenylcarbazole, 4,4'-bis [N- (1-naphthyl) -N-phenyl-amino] biphenyl, 4,4'-bis [N- (1-naphthyl) -N- Phenylamino] p-terphenyl, 4,4'-bis [N- (2-naphthyl) -N-phenylamino] biphenyl, 4,4'-bis [N- (3-acenaphthenyl) -N -Phenylamino] biphenyl, 1,5-bis [N- (1-naphthyl) -N-phenylamino] naphthalene, 4,4'-bis [N- (9-anthryl) -N-phenylamino] Biphenylphenylamino] biphenyl, 4,4'-bis [N- (1-antryl) -N-phenylamino] -p-terphenyl, 4,4'-bis [N- (2-phenanthryl) -N-phenylamino] biphenyl, 4,4'-bis [N- (8-fluoranthenyl) -N-phenylamino] biphenyl, 4,4'-bis [N- (2-pyrenyl)- N-phenylamino] biphenyl, 4,4'-bis [N- (2-perylenyl) -N-phenylamino] biphenyl, 4,4'-bis [N- (1-coroneyl)- N-phenylamino] biphenyl (4,4'-bis [N- (1-coronenyl) -N-phenylamino] biphenyl), 2,6-bis (di-p-tolylamino) naphthalene, 2,6-bis [Di- (1-naphthyl) amino] naphthalene, 2,6-bis [N- (1-naphthyl) -N- (2-naphthyl) amino] naphthalene, 4,4'-ratio S [N, N-di (2-naphthyl) amino] terphenyl, 4,4'-bis {N-phenyl-N- [4- (1-naphthyl) phenyl] amino} biphenyl, 4,4 '-Bis [N-phenyl-N- (2-pyrenyl) amino] biphenyl, 2,6-bis [N, N-di- (2-naphthyl) amino] fluorene or 4,4'-bis Aryl amine compounds such as (N, N-di-p-tolylamino) terphenyl, and bis (N-1-naphthyl) (N-2-naphthyl) amine may be representatively exemplified, but are not limited thereto. It is not.

The hole injection layer or the hole transport layer may be formed by dispersing an 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 is formed by using electrically conductive polymers such as metal phthalocyanine such as copper phthalocyanine, non-metal phthalocyanine, carbon film and polyaniline, or by reacting the aryl amine compound with Lewis acid as an oxidizing agent. You may.

The specific structure of the organic material layer is not particularly limited. In this field, various materials for forming a hole or electron injection electrode layer and an organic material layer, for example, a light emitting unit, an electron injection or transport layer, a hole injection or transport layer, and a method of forming the same are known. All of these methods can be applied.

The upper region of the organic electronic device may include an inorganic layer and a cover film sequentially formed in an upward direction. In order to distinguish the inorganic layer from the organic electronic device substrate, the inorganic layer included in the upper region may be referred to as a second inorganic layer, and the inorganic layer included in the substrate may be referred to as a first inorganic layer.

The second inorganic material layer is present in order to block, suppress or mitigate the penetration of the foreign material to ensure durability, and the specific material and formation method may be similar to those mentioned in the item of the first inorganic material layer. However, when the light is designed to emit toward the substrate region side, the second inorganic material layer does not need to be formed to have a high refractive index like the first inorganic material layer.

The cover film present on the upper portion of the second inorganic material layer may be a structure that protects the organic electronic device. For example, a known barrier film, a metal sheet, a conductive film, or the like may be a laminate structure of two or more of the above. In the upper region, the cover film may be attached to the top of the second inorganic material layer through an adhesive layer, for example, the barrier adhesive layer described above.

One or more buffer layers may be present if the top region is also required. The buffer layer included in the upper region may be referred to as a second buffer layer to distinguish it from the buffer layer included in the substrate. The location where the buffer layer may be present in the upper region may be illustrated between the second electrode layer and the second inorganic layer. In another example, the upper region may include a structure including two or more second buffer layers and two or more second barrier layers, and the layers are alternately stacked. This buffer layer serves to alleviate stress (strss) generated in the structure of the upper region, to prevent the pressing of the device when the cover film is formed on the second inorganic layer, and / or the second inorganic layer is formed It is possible to reduce the limit of the temperature to be provided, and also to provide an appropriate flat surface so that the second inorganic material layer can exhibit an excellent effect.

In one example, the specific material and the formation method of the second buffer layer may be the same as the buffer layer mentioned in the substrate.

The second buffer layer may be an iCVD layer formed in an iCVD manner so that the second buffer layer exhibits proper performance and exhibits the desired action in the overall device structure.

The second buffer layer may be, for example, a glass silicon layer or a polymer layer including poly ((meth) acrylate).

The organic silicon layer may include, for example, a compound of Formula 1 or a compound of Formula 2, or a polymer including polymerized units of one or more compounds.

[Formula 1]

R ¹ (R ¹ ₂ SiO) _n R ¹

[Formula 2]

[Formula 3]

R ¹ , R ^d and R ^e in Formulas 1 and 2 are each independently hydrogen, a hydroxy group, an epoxy group, an alkoxy group, or a monovalent hydrocarbon group, at least one of R ¹ is an alkenyl group, and at least one of R ^d and R ^e Is an alkenyl group, n is a number in the range of 1-10, o is a number in the range of 3-10.

As used herein, unless otherwise specified, the term "monohydric hydrocarbon group" may refer to a compound consisting of carbon and hydrogen or a monovalent moiety derived from a derivative of such a compound. For example, the monovalent hydrocarbon group may contain 1 to 25 carbon atoms. As a monovalent hydrocarbon group, an alkyl group, an alkenyl group, an alkynyl group, an aryl group, etc. can be illustrated.

As used herein, unless otherwise specified, the term "alkyl group" may mean an alkyl group having 1 to 20 carbon atoms, 1 to 16 carbon atoms, 1 to 12 carbon atoms, 1 to 8 carbon atoms, or 1 to 4 carbon atoms. The alkyl group may be linear, branched or cyclic. In addition, the alkyl group may be optionally substituted with one or more substituents.

In the present specification, the term "alkoxy group" may mean an alkoxy group having 1 to 20 carbon atoms, 1 to 16 carbon atoms, 1 to 12 carbon atoms, 1 to 8 carbon atoms, or 1 to 4 carbon atoms, unless otherwise specified. The alkoxy group may be linear, branched or cyclic. In addition, the alkoxy group may be optionally substituted with one or more substituents.

As used herein, unless otherwise specified, the term "alkenyl group" may refer to an alkenyl group having 2 to 20 carbon atoms, 2 to 16 carbon atoms, 2 to 12 carbon atoms, 2 to 8 carbon atoms, or 2 to 4 carbon atoms. The alkenyl group may be linear, branched, or cyclic, and may be optionally substituted with one or more substituents.

In the present specification, the term "alkynyl group" may mean an alkynyl group having 2 to 20 carbon atoms, 2 to 16 carbon atoms, 2 to 12 carbon atoms, 2 to 8 carbon atoms, or 2 to 4 carbon atoms, unless otherwise specified. The alkynyl group may be linear, branched, or cyclic, and may be optionally substituted with one or more substituents.

As used herein, unless otherwise specified, the term "aryl group" may mean a monovalent moiety derived from a compound or a derivative thereof including a structure in which a benzene ring or a structure in which two or more benzene rings are condensed or bonded. The range of the aryl group may include a functional group commonly referred to as an aryl group as well as a so-called aralkyl group or an arylalkyl group. The aryl group may be, for example, an aryl group having 6 to 25 carbon atoms, 6 to 21 carbon atoms, 6 to 18 carbon atoms, or 6 to 12 carbon atoms. Examples of the aryl group include phenyl group, dichlorophenyl, chlorophenyl, phenylethyl group, phenylpropyl group, benzyl group, tolyl group, xylyl group or naphthyl group.

As used herein, unless otherwise specified, the term epoxy group may mean a cyclic ether having three ring constituent atoms or a monovalent moiety derived from a compound containing the cyclic ether. Examples of the epoxy group include glycidyl group, epoxyalkyl group, glycidoxyalkyl group or alicyclic epoxy group. In the above, the alicyclic epoxy group may mean a monovalent moiety derived from a compound containing an aliphatic hydrocarbon ring structure, wherein the two carbon atoms forming the aliphatic hydrocarbon ring also include an epoxy group. As the alicyclic epoxy group, an alicyclic epoxy group having 6 to 12 carbon atoms can be exemplified, for example, a 3,4-epoxycyclohexylethyl group or the like can be exemplified.

Examples of the substituent that may be optionally substituted with an epoxy group, an alkoxy group or a monovalent hydrocarbon group include epoxy groups such as halogen, glycidyl group, epoxyalkyl group, glycidoxyalkyl group or alicyclic epoxy group such as chlorine or fluorine, acryloyl group, Methacryloyl group, isocyanate group, thiol group or monovalent hydrocarbon group and the like can be exemplified, but is not limited thereto.

Examples of the compound of formula (1) or (2) include trivinyltrimethylcyclosiloxane hexamethyldisiloxane, hexavinyldisiloxane, 1,1,3,3-tetravinyldimethyldisiloxane, divinyltetramethyldisiloxane, and 1,3,5 Trivinyl-1,1,3,5,5-pentamethyltrisiloxane, trivinyltrimethylcyclosiloxane, and the like can be exemplified, but is not limited thereto.

In addition, the poly ((meth) acrylate) may include, for example, a compound of Formula 3 or a polymerization unit thereof, or a polyfunctional acrylate or a polymerization unit thereof. The poly ((meth) acrylate) may be a homopolymer of the compound of Formula 3 or another comonomer together with the compound of Formula 3 It may be a copolymer.

[Formula 3]

In formula (3), R ₁ is hydrogen or an alkyl group having 1 to 4 carbon atoms, and A is a linear, branched or cyclic alkyl group, an epoxy group-containing group or an alicyclic monovalent hydrocarbon group.

Examples of the epoxy group-containing group include glycidyl group, glycidyloxy group, glycidylalkyl group, glycidoxyalkyl group or alicyclic epoxy group. In addition, the alicyclic monovalent hydrocarbon group in the above means the compound which the carbon atom couple | bonded in the ring shape, and means the monovalent residue derived from the compound which is not an aromatic compound, or its derivative. The alicyclic monovalent hydrocarbon group may be an alicyclic monovalent hydrocarbon group having 3 to 20 carbon atoms, 5 to 15 carbon atoms, or 5 to 12 carbon atoms. For example, an isobornyl group, cyclohexyl group, norbornanyl group ( norbornanyl), norbornenyl group (norbornenyl), dicyclopentadienyl group, ethynylcyclohexane group, ethynylcyclohexene group or ethynyl decahydronaphthalene group and the like may be included, but is not limited thereto.

Examples of the compound of formula (3) or polyfunctional acrylate include glycidyl (meth) acrylate, butyl (meth) acrylate, cyclohexyl (meth) acrylate, ethylene glycol di (meth) acrylate, and the like. However, the present invention is not limited thereto.

Using the material as described above, for example, the second buffer layer formed by the iCVD method can perform an excellent function in the overall device structure. The second buffer layer may be formed to an appropriate thickness in consideration of the desired function, and may have a thickness within a range of about 200 nm to 1,000 nm or about 200 nm to 500 nm, for example.

The present application also relates to the use of such organic electronic devices, for example organic light emitting devices. The organic light emitting device may be, for example, a backlight of a liquid crystal display (LCD), a light source, a light source such as various sensors, a printer, a copier, a vehicle instrument light source, a signal lamp, an indicator light, a display device, a planar light emitting body, and the like. It can be effectively applied to a light source, a display, a decoration or various lights. In one example, the present application relates to a lighting device including the organic light emitting device. When the organic light emitting device is applied to the lighting device or other uses, other components constituting the device or the like or a method of constituting the device are not particularly limited, and are known in the art as long as the organic light emitting device is used. Any material or method can be employed.

In the present application, it is possible to provide a substrate having excellent interfacial adhesion that can be applied to the construction of a flexible device including a structure in which an organic material layer and an inorganic material layer are mixed to prevent peeling between the organic material layer and the inorganic material layer. The present application may also provide an organic electronic device having excellent durability and excellent properties such as light extraction efficiency by using the substrate for an organic electronic device as described above.

1 is a schematic diagram illustrating an exemplary organic electronic device.

Hereinafter, the present application will be described in more detail through examples according to the present application and comparative examples not according to the present application, but the scope of the present application is not limited to the examples given below.

Example  One.

Fabrication of Organic Electronic Substrate

The flexible substrate film has a refractive index of about 1.7 and a PI (polyimide) film having a thickness of about 18 to 35 μm, in which scattering particles (TiO ₂ ) are dispersed therein and a haze is adjusted within a range of about 30% to 60%. Was used. The PI film was placed on a glass substrate, which is a carrier substrate, and an iCVD layer was formed on the surface of the PI film. The iCVD layer was formed by using GMA (glycidyl methacrylate) as a monomer and tert-butyl peroxide (TBPO) as an initiator. Specifically, the thermal decomposition of the initiator from the mixture of the monomer and the initiator with a filament maintained in the range of about 150 ℃ to 300 ℃, and the polymerization reaction is induced on the surface of the PI film maintained at a temperature of about 20 ℃ to 50 ℃ by iCVD The layer was formed to a thickness of about 0.5 μm to 1 μm. Thereafter, an inorganic layer was formed on the iCVD layer by ALD (Atomic Layer Deposition). The inorganic layer was prepared by repeatedly forming the first sublayer and the second sublayer by the ALD method. In the first sublayer, a layer of Al ₂ O ₃ having a refractive index of about 1.6 to 1.8 at the time of single deposition is formed, and a TiO ₂ having a refractive index of about 2.0 to 2.4 at the time of single deposition as a second sublayer. Layer was used. The first and second sublayers were alternately deposited to finally form a refractive index of about 1.7 to 2.0. The layer of Al ₂ O _{3 and} the layer of TiO ₂ were formed by a known ALD method. At the time of formation, the thickness of each Al ₂ O ₃ layer was about 20 to 60 nm, and the thickness of the TiO ₂ layer was about 20 to 60 nm, and alternately formed to finally have a thickness of about 60 to 100 nm. Formed to be mine.

Fabrication of organic electronic device (organic light emitting device)

An anode layer including ITO (Indium Tin Oxide) on the prepared inorganic layer (anode, thickness: 80 to 150 nm), NPB (N, N'-Bis (naphthalen-1-yl) -N, N'-bis a hole transport layer (thickness: 30 to 100 nm) containing (phenyl) benzidine), a first light emitting unit (thickness: 100 to 150 nm) having an emission wavelength in the range of about 380 to 500 nm, an electron transport layer (thickness: 100 To 800 nm), an n-type semiconductor layer (thickness: 10 to 50 nm), a NPB layer (thickness: 30 to 100 nm) comprising a compound represented by the following formula A, and an emission wavelength within a range of about 500 to 700 nm. A second light emitting unit (thickness: 100 to 150 nm), a hole block comprising BAlq (bis (2-methyl-8-quinolinolato-N1, C6)-(1,1'-biphenyl-4-olato) aluminium) A layer, an electron transporting layer (thickness: 100 to 800 nm), an electron injection layer (thickness: 0.5 to 1.5 nm) of LiF, and an Al reflective electrode layer (thickness: 100 to 200 nm) are sequentially formed to form an element region It was. Subsequently, an iCVD layer was formed on the Al reflective electrode layer in the device region. The iCVD layer was formed in the same manner as the iCVD layer was formed on the PI film except that GMA (glycidyl methacrylate) was used as the monomer, and the thickness was formed about 0.5 to 1 μm. Subsequently, a second barrier layer was formed to a thickness of about 20 nm to 60 nm in the same manner as above on the iCVD layer by using an epoxy-based adhesive film having a thickness of about 25 to 50 μm. The barrier film of about 50-100 micrometers in thickness was attached. Next, the PI film was peeled from the carrier substrate, and an organic adhesive device was prepared by attaching a well-known barrier film having a thickness of about 20 to 50 μm with an acrylic adhesive film having a thickness of about 20 to 50 μm.

[Formula A]

Example  2.

A substrate and an organic electronic device were manufactured in the same manner as in Example 1, except that trivinyltrimethylcyclosiloxane was used as the monomer when the iCVD layer was formed on the base film.

Example  3.

In the same manner as in Example 1, except that 1,3,5-trivinyl-1,1,3,5,5-pentamethyltrisiloxane was used as the monomer when forming the iCVD layer on the base film. An organic electronic device was manufactured.

Example  4.

A substrate and an organic electronic device were manufactured in the same manner as in Example 1, except that butyl acrylate was used as a monomer when forming an iCVD layer on a base film.

Example  5.

A substrate and an organic electronic device were manufactured in the same manner as in Example 1, except that cyclohexyl acrylate was used as the monomer when forming the iCVD layer on the base film.

101: flexible base film
102: the first inorganic layer
103: first electrode layer
104: organic layer
105: second electrode layer
106: second inorganic layer
107: cover film

Claims (18)

Flexible base film;
A first iCVD layer present on the base film;
A first inorganic material layer on the first iCVD layer;
A first electrode layer present on the first inorganic material layer;
An organic material layer on the first electrode layer;
A second electrode layer on the organic material layer;
A second iCVD layer present on the second electrode layer; And
And a second inorganic material layer present on the second iCVD layer.
The first iCVD layer and the second iCVD layer each contain a component or a polyfunctional acrylate represented by the formula of any one of the following formulas (1) to (3), or an organic unit comprising a polymer unit of the component or a multifunctional acrylate Electronic device:
[Formula 1]
R ¹ (R ¹ ₂ SiO) _n R ¹
[Formula 2]

[Formula 3]

In Formulas 1 to 3, R ¹ , R ^d, and R ^e are each independently hydrogen, a hydroxyl group, an epoxy group, an alkoxy group, or a monovalent hydrocarbon group, at least one of R ¹ is an alkenyl group, and at least one of R ^d and R ^e Is an alkenyl group, n is a number in the range of 1 to 10, o is a number in the range of 3 to 10, R ₁ is hydrogen or an alkyl group having 1 to 4 carbon atoms, A is an epoxy group-containing group or an alicyclic monovalent group It is a hydrocarbon group. delete The method of claim 1, wherein the compound of Formula 1 is hexamethyldisiloxane, hexavinyldisiloxane, 1,1,3,3-tetravinyldimethyldisiloxane, divinyltetramethyldisiloxane and 1,3,5- At least one organic electronic device selected from the group consisting of trivinyl-1,1,3,5,5-pentamethyltrisiloxane. The organic electronic device of claim 1, wherein the compound of Formula 2 is trivinyltrimethylcyclosiloxane. The method of claim 1, wherein the compound of Formula 3 or polyfunctional acrylate is glycidyl (meth) acrylate, butyl (meth) acrylate, cyclohexyl (meth) acrylate or ethylene glycol di (meth) acrylate Phosphorus organic electronic device. The organic electronic device of claim 1, wherein the first inorganic material layer is an ALD layer. The organic electronic device of claim 1, wherein a difference in refractive index between the first inorganic material layer and the flexible base film is 1 or less. The organic electronic device of claim 1, wherein the first inorganic material layer includes a stacked structure of a first sub layer and a second sub layer. The organic electronic device of claim 8, wherein a thickness of the first sublayer and a thickness of the second sublayer are 5 nm or less. delete The organic electronic device of claim 8, wherein the first sub layer and the second sub layer are metal oxide layers. The organic electronic device of claim 11, wherein the metal oxide of the first sublayer and the metal oxide of the second sublayer are different from each other. The organic electronic device of claim 12, wherein the first inorganic material layer further comprises a third sublayer including a metal oxide different from the metal oxide of the first sublayer and the metal oxide of the second sublayer. The organic electronic device of claim 8, wherein the refractive index of the first sub layer is in a range of 1.4 to 1.9, and the refractive index of the second sub layer is in a range of 2.0 to 2.6. delete delete The organic electronic device of claim 1, further comprising an intermediate layer present between the first inorganic layer and the first electrode layer and having an elastic modulus at 23 ° C. in a range of 50 GPa to 400 GPa. delete

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