KR20210067680A - Organic electronic device having barrier film - Google Patents

Abstract

The present application relates to an organic electronic device having a barrier film. The barrier film improves barrier properties of the organic electronic device. According to an embodiment of the present invention, an organic electronic device includes a barrier film including an inorganic layer, a first electrode layer, an organic layer including a light emitting layer, and a second electrode layer.

Description

Organic electronic device having barrier film

This application relates to an organic electronic device. Specifically, the present application relates to an organic electronic device having a barrier film excellent in blocking properties against external substances such as oxygen or moisture.

An organic electronic device or device such as an organic light emitting device (OLED), an organic solar cell, an organic photoconductor (OPC), or an organic transistor includes an organic layer vulnerable to external factors such as moisture. In particular, as the thickness of the substrate used in the device becomes thinner in accordance with the trend toward thinning, and as a plastic substrate is applied instead of a glass substrate to secure flexible characteristics, barrier properties against moisture etc. are becoming more important in the field of organic light emitting devices.

An object of the present application is to provide an organic electronic device.

Another object of the present application is to provide an organic electronic device including a barrier film having excellent blocking properties against external substances such as oxygen or moisture.

Another object of the present application is to provide an organic electronic device including a barrier film in which barrier properties against external substances such as oxygen or moisture do not deteriorate even after being stored in high temperature and/or high humidity conditions.

The above and other objects of the present application can all be solved by the present application described in detail below.

In an example related to the present application, the present application relates to an organic electronic device. The organic electronic device may include a barrier film; a first electrode layer; and an organic layer including a light emitting layer; and a second electrode layer.

For convenience, the barrier film among the components constituting the organic electronic device is referred to as a barrier part, and the remainder (the first electrode layer; the organic layer including the light emitting layer; and the structure including the second electrode layer) except for the barrier part may be called an organic device part.

In the present application, the barrier film means a film that satisfies the intended light transmittance and barrier properties.

In relation to light transmittance, the barrier film may refer to a film having a transmittance of 90% or more or 95% or more of visible light within a wavelength range of 380 to 780 nm, specifically, light having a wavelength of 550 nm. The upper limit of the transmittance is, for example, about 100%, and the film may have a transmittance of less than 100%.

With respect to barrier properties, the barrier film may have excellent moisture permeability.

In one example, the barrier film may have a moisture permeability of 10 × 10 ⁻⁴ g/m ² ·day or less measured at a temperature of 38° C. and 100% relative humidity. More specifically, the barrier film has a moisture permeability measured under the above conditions of 9 × 10 ^-4 g/m ² ·day or less, 8 × 10 ^-4 g/m ² ·day or less, 7 × 10 ^-4 g/m ^{2 or less.} ·day or less, 6 × 10 ^-4 g/m ² ·day or less, 5 × 10 ^-4 g/m ² ·day or less, 4 × 10 ^-4 g/m ² ·day or less, 3 × 10 ^-4 g/ m ² ·day or less, 2 × 10 ^-4 g/m ² ·day or less, or 1 × 10 ^-4 g/m ² ·day or less. The lower the water vapor permeability value is, the better the barrier properties are, so the lower limit of the water vapor permeability is not particularly limited. In one example, the lower limit of the moisture permeability is 0.001 × 10 ^-4 g/m ² ·day or more, 0.005 × 10 ^-4 g/m ² ·day or more, 0.01 × 10 ^-4 g/m ² ·day or more, 0.05 × 10 ^-4 g/m ² ·day or more, 0.1 × 10 ^-4 g/m ² ·day or more, or 0.5 × 10 ^-4 g/m ² ·day or more. As a representative standard for measuring moisture permeability, ASTM F1249 or ISO15506-3 is known, and the moisture permeability of the present application may be measured according to an appropriate method among the above.

The barrier film satisfying the light transmittance and barrier properties in the above-described ranges may include an inorganic layer. And, the inorganic layer includes Si, N, and O, and has the properties and configuration described below.

In one example, the barrier film may include a base layer in addition to the inorganic layer.

The base layer may include, for example, a glass or polymer film capable of providing light-transmitting properties.

In one example, the base layer may include a polymer film. For example, a polyester film such as a polyethylene terephthalate (PET) film, a polycarbonate film, a polyethylene naphthalate film or a polyarylate film, a polyether film such as a polyethersulfone film, a cycloolefin polymer film, a polyethylene film, or a poly A polyolefin film such as a propylene film, a diacetyl cellulose film, a cellulose resin film such as a triacetyl cellulose film or an acetyl cellulose butyrate film, a polyimide film, an acrylic film, an epoxy resin film, etc. can be used for the base layer. In the present application, the base layer may have a single-layer or multi-layer structure.

In one example, a film known to be used in the implementation of a flexible device may be used for the base layer. Specifically, PI (polyimide), PA (polyamide), or a copolymer or blend thereof may be used as the base layer component.

The thickness of the base layer is not particularly limited. For example, the thickness of the base layer may be about 1 μm or more, 5 μm or more, 10 μm or more, 20 μm or more, 30 μm or more, 40 μm or more, or 50 μm or more. When the thickness is satisfied, the inorganic layer may be stably formed on the base layer. The upper limit of the thickness of the base layer is not particularly limited, but may be, for example, 500 μm or less, 400 μm or less, 300 μm or less, 200 μm or less, or 100 μm or less.

The inorganic layer may be formed through plasma modification of the polysilazane composition applied on the object to be coated (eg, the base layer), that is, the polysilazane layer.

In the present application, the polysilazane composition refers to a composition including polysilazane as a main component. For example, the proportion of polysilazane in the polysilazane composition may be 55% or more, 60% or more, 65% or more, 70% or more, 75% or more, 80% or more, 85% or more by weight. Or it may mean a case of 90% or more. The weight ratio may be, for example, 100% or less, 99% or less, 98% or less, 97% or less, 96% or less, or 95% or less.

In the present application, polysilazane may refer to a polymer in which silicon element (Si) and nitrogen element (N) are repeated to form a basic backbone. Such polysilazane may be modified through a predetermined treatment (eg, plasma treatment) to form silicon oxide or silicon oxynitride having barrier properties. Accordingly, the inorganic layer may include Si, N, and O.

In one example, the polysilazane used in the present application may include a unit represented by the following Chemical Formula 1.

[Formula 1]

In Formula 1, R1, R2 and R3 may each independently represent a hydrogen atom, an alkyl group, an alkenyl group, an alkynyl group, an aryl group, an alkylsilyl group, an alkylamino group, or an alkoxy group.

In the present application, 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, unless otherwise specified. 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 application, the term "alkenyl group", unless otherwise specified, may mean 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 application, the term "alkynyl group", unless otherwise specified, 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. The alkynyl group may be linear, branched, or cyclic, and may be optionally substituted with one or more substituents.

In the present application, the term "aryl group", unless otherwise specified, a benzene ring or two or more benzene rings are connected, or a compound containing a condensed or bonded structure while sharing one or two or more carbon atoms Or it may mean a monovalent residue derived from its derivative. In the present application, the scope 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 a phenyl group, a dichlorophenyl group, a chlorophenyl group, a phenylethyl group, a phenylpropyl group, a benzyl group, a tolyl group, a xylyl group, or a naphthyl group.

In the present application, the term “alkoxy group” may refer to 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.

If the unit represented by Formula 1 is included, specific types of polysilazane are not particularly limited.

In one example, the polysilazane may be a polysilazane including a unit of Formula 1 in which R1 to R3 are all hydrogen atoms, for example, perhydropolysilazane.

In one example, the polysilazane layer composition may be prepared by dissolving polysilazane in an appropriate organic solvent, for example. For example, the polysilazane may be a commercially available product dissolved in an organic solvent. Such commercially available products include Aquamica (registered trademark) NN120-10, NN120-20, NAX120-10, NAX120-20, NN110, NN310, NN320, NL110A manufactured by AZ Electronic Materials (or Merck), NL120A, NL150A, NP110, NP140, or SP140 may be exemplified, but are not limited thereto.

In another example, the polysilazane layer composition may be a composition diluted to a predetermined concentration. The diluted concentration is not particularly limited, and, for example, the weight ratio of the total solid content may be in the range of 1 to 95%. In one example, the composition may have a weight ratio of total solids of 1 to 10% or less.

In the present application, the layer formed from polysilazane, that is, the inorganic layer has durability and density sufficient to satisfy the moisture permeability. In the present application, the density may be expressed through an etching rate. For example, the inorganic layer may have an etching rate that satisfies a predetermined value with respect to a reference condition. In the present application, the term “etching rate” refers to a value obtained by dividing the etched thickness (unit: nm) by the etching progress time (unit: seconds) on the assumption that etching is performed under the same conditions as the reference conditions described below. . The etching for measuring the etching rate is so-called dry etching, and is etching using a plasma state of a reactive gas. Ar is used as the reactive gas.

With respect to the etching rate of the inorganic layer, the inventors of the present application have found that the inorganic layer is formed from polysilazane, and even if its constituent elements are similar, such as including Si, N and O, elements constituting the inorganic layer in the inorganic layer thickness direction It was confirmed that the degree of firmness or density of the layer may be different depending on the content, distribution tendency, and/or conditions for forming the inorganic layer, and as a result, the etching rate for the reference condition may also vary. Specifically, in the prior art related to the barrier film, the type of element in the inorganic layer or the content of an element expressed as a numerical value were mainly considered as important factors for determining the barrier properties, but the content of the element forming the inorganic layer and the distribution tendency The density of the inorganic layer may vary depending on the change and/or conditions for forming the inorganic layer, and as a result, the moisture permeability of the barrier film may be remarkably improved.

Specifically, the inorganic layer may satisfy a reference condition, that is, an etching rate of 0.17 nm/s or less for an Ar ion etching condition in _{which Ta 2} O _{5 (film) is etched at a rate of 0.09 nm/s.} The etching rate may indicate the density of the inorganic layer. That is, it can be seen that the inorganic layer having the etching rate has a denser structure than the inorganic layer that does not satisfy the etching rate, for example, when the etching rate is 0.19 nm/s. For example, the inorganic layer has an etching rate of 0.165 nm/s or less, 0.160 nm/s or less, 0.155 nm/s or less, 0.150 nm/s or less, 0.145 nm/s or less, 0.140 nm/s or less for the above conditions. , 0.135 nm/s or less, 0.130 nm/s or less, 0.125 nm/s or less, or 0.120 nm/s or less. When the etching rate range is satisfied, the lower limit of the etching rate is not particularly limited, but may be, for example, 0.05 nm/s or more or 0.10 nm/s or more.

The inorganic layer includes a first region and a second region. In the present application, the first region may exist closer to the base layer than the second region.

In the present application, the element content (atomic%) of Si, N, and O measured or analyzed by X-ray photoelectron spectroscopy (XPS) in the thickness direction of the first region and the second region constituting one inorganic layer is mutually different That is, the first region and the second region can be distinguished from each other due to the difference in the element content distribution of Si, N, and O. For example, the element content of each region can be analyzed according to the etching depth in the thickness direction of the inorganic layer. Since the degree of change in the content of each element according to the depth is relatively small, a flat section is observed or the magnitude of the content of each element is relatively small. When a section with a common tendency is observed, the median or average value of the content of each element in the section can be viewed as the element content (range) in the section. In addition, in relation to region discrimination according to element content, the element content at the interface of the first region and the second region may be continuously or stepwise changed. As a result of such content change, the element content ratio defined by each region The extent to which a satisfactory region is observed is sufficient to distinguish the first region from the second region, and the interface between the first region and the second region is not necessarily clearly demarcated. This distinction can be clearly performed by those skilled in the art through a graph of the element content distribution according to the etching depth, which is confirmed using XPS.

The first region and the second region may have the same density as described above. Specifically, each of the first region and/or the second region may be a region in which an etching rate measured under Ar ion etching conditions for etching _{Ta 2} O _{5 at a rate of 0.09 nm/s satisfies 0.17 nm/s or less.} . For example, the first region and/or the second region may have an etch rate of 0.165 nm/s or less, 0.160 nm/s or less, 0.155 nm/s or less, 0.150 nm/s or less, 0.145 nm/s or less for the reference condition. s or less, 0.140 nm/s or less, 0.135 nm/s or less, 0.130 nm/s or less, 0.125 nm/s or less, or 0.120 nm/s or less may be satisfied. The lower limit of the etching rate of the first region and/or the second region is not particularly limited, but may be, for example, 0.05 nm/s or more or 0.10 nm/s or more.

In the present application, the second region is a high nitrogen concentration region in the inorganic layer. That is, the second region may be a region having a higher nitrogen content than the first region. The inventor of the present application provided that the density of the inorganic layer confirmed through the etching rate is secured, such that the etching rate for the reference condition is 0.17 nm/s or less, the thicker the second region, the nitrogen-rich region, the greater the barrier It was confirmed that properties (eg, moisture permeability) were improved. These results are confirmed through the following experimental examples.

In one example, the thickness of the second region may have a thickness of 10% or more compared to the thickness of the entire inorganic layer. For example, the thickness of the second region may be 15% or more, 20% or more, 25% or more, 30% or more, 35% or more, 40% or more, 45% or more, 50% or more based on the thickness of the entire inorganic layer. or more, 55% or more, 60% or more, 65% or more, or 70% or more. For example, when the thickness of the inorganic layer is 150 nm, the thickness of the second region may be 15 nm or more, 16 nm or more, 17 nm or more, 19 nm or more, or 20 nm or more. The upper limit of the thickness of the second region is not particularly limited, and for example, may be 80% or less, 70% or less, 60% or less, or 50% or less of the thickness of the entire inorganic layer.

In one example, the first region may be a region satisfying O content > Si content > N content. That is, the first region means a region satisfying the element content as described above.

In the present application, the element content is a value when the total amount of the content of Si, O, and N and the content of impurities (eg, C) that can be measured in each layer or region is 100 as a whole. Unless otherwise specified, the content of C is a value excluding the content of Si, O, and N, and thus may be omitted.

Specifically, in the first region, the O content may be in the range of 50 to 65 atomic%, the Si content may be in the range of 35 to 45 atomic%, and the N content may be in the range of 1 to 15 atomic%. It is considered that the above element content can ensure the density of the inorganic layer expressed by the etching rate described above, and can improve the moisture barrier properties of the barrier film.

In one example, the ratio (a/b) between the O content (a) and the Si content (b) in the first region may satisfy a range of 1.1 to 1.8. Preferably, it may be 1.2 or more, 1.3 or more, or 1.4 or more. In the first region where the content of Si, N and O satisfies the above range, when the ratio (a/b) value is in the range of 1.1 to 1.8, it is possible to secure the density of the inorganic layer expressed by the above-described etching rate. and it is thought that the moisture barrier properties of the barrier film can be improved.

In one example, the thickness of the first region satisfying the element content ratio may be 40 nm or more. When the thickness of the first region satisfies the above range, the inorganic layer or the first region may be stably formed and have sufficient density, and higher durability may be provided to the barrier film. For example, since the substrate layer adjacent to the first region or the intermediate layer described below may have a predetermined roughness on its surface, the first region has a minimum thickness so that the inorganic layer can be stably formed. can have More specifically, the thickness of the first region satisfying the element content is, for example, 45 nm or more, 50 nm or more, 55 nm or more, 60 nm or more, 65 nm or more, 70 nm or more, 75 nm or more, 80 nm or more. nm or greater, 85 nm or greater, 90 nm or greater, 95 nm or greater, or 100 nm or greater. The upper limit of the thickness of the first region is not particularly limited, but may be, for example, 300 nm or less, 250 nm or less, or 200 nm or less.

In one example, the second region may be a region satisfying Si content > N content > O content. That is, the second region means a region satisfying the above element content. As a result of experimental confirmation, when the second region satisfies Si content > N content > O content than when the second region has Si content > O content > N content, the density of the inorganic layer is increased, and the barrier properties of the film are improved could be adjusted

Specifically, in the second region, the Si content may be in the range of 45 to 60 atomic%, the N content may be in the range of 20 to 35 atomic%, and the O content may be in the range of 10 to 30 atomic%. The element content as described above is considered to be advantageous in securing the density of the inorganic layer expressed by the etching rate described above.

In one example, the thickness of the second region satisfying the element content ratio is not particularly limited. For example, it may be 10 nm or more, 20 nm or more, 30 nm or more, 40 nm or more, or 50 nm or more. The upper limit is not particularly limited, but may be, for example, about 250 nm or less or about 200 nm or less. As confirmed in the following experimental examples, the thickness of the second region, which is a high nitrogen concentration region, seems to affect the improvement of the barrier properties of the film. A barrier property superior to that may be provided. More specifically, the thickness of the second region satisfying the element content is, for example, 190 nm or less, 185 nm or less, 180 nm or less, 175 nm or less, 170 nm or less, 165 nm or less, 160 nm or less, 155 or less. nm or less, 150 nm or less, 145 nm or less, 140 nm or less, or 135 nm or less

In one example, the difference (d) between the maximum value of the Si content of the second region and the maximum value of the O content of the first region may be 15 atomic% or less. In each region where the content of Si, N and O satisfies the above range, if the difference (d) is satisfied, the density of the inorganic layer expressed in the etching rate described above can be secured, and the barrier film is blocked from moisture It is thought that the characteristics can be improved.

The first region and the second region may be formed by plasma treatment of a composition including polysilazane, that is, the polysilazane layer.

In one example, the first region and the second region may be regions in the inorganic layer formed through one plasma treatment performed on one polysilazane composition, that is, one polysilazane layer to be coated. That is, the inorganic layer may be divided into a first region and a second region formed therein. It is considered that the N-rich second region is formed through the plasma treatment, and the first region and the second region are distinguished.

In another example, the first region and the second region may be adjacent regions formed through plasma treatment of different polysilazane layers. For example, the first region may be a region formed through plasma treatment of the polysilazane layer (A), and the second region is a region for the polysilazane layer (B) applied on the inorganic layer in which the first region is formed. It may be a region formed through plasma treatment. These first and second regions contain Si, N and O, and constitute an inorganic layer. As described above, an N-rich region is located in the surface layer of the plasma-treated polysilazane layer through plasma treatment, which is the same in the case of the plasma-treated polysilazane layer (A), and thereby the polysilazane layer It is considered that the second region having the same element content distribution as that of the surface layer portion of the polysilazane layer (A) is formed even if a separate plasma treatment is performed for (B). In this case, the interface of each of the plasma-treated polysilazane layers A and B may be observed as a section in which an element content change occurs between the first region and the second region, for example, as in FIG. 1 . As can be seen in Examples 1 to 5 below, when the inorganic layer is formed in this way, a larger thickness of the second region can be secured, and accordingly, the high nitrogen concentration region in the inorganic layer increases while the barrier properties of the film are increased. This can be improved.

In one example, a modified layer having a high carbon content may exist between the inorganic layer and the base layer. The denatured layer may be an interface between the plasma-treated inorganic layer and the base layer. Alternatively, the denatured layer may be an interface between the plasma-treated inorganic layer and the intermediate layer described below. The denatured layer may be a region having a greater carbon content than the first region and the second region. For example, the denatured layer may be a region satisfying C content > O content > Si content > N content.

Specifically, in the modified layer, the C content is in the range of 40 to 50 atomic%, the O content is in the range of 30 to 40 atomic%, the Si content is in the range of 15 to 30 atomic%, and the N content is 1 to 5 atomic % can be within the range.

The thickness of the inorganic layer having the first region and the second region may be, for example, 600 nm or less or 500 nm or less. More specifically, the thickness of the inorganic layer may be 450 nm or less, 400 nm or less, 350 nm or less, 300 nm or less, 250 nm or less, or 200 nm or less. The inorganic layer of the above-described configuration may have sufficient barrier properties even with a thin thickness. The lower limit of the thickness of the inorganic layer is not particularly limited, but may be, for example, 50 nm or more.

In one example, the barrier film may further include an intermediate layer. Specifically, the barrier film may sequentially include a base layer, an intermediate layer, and an inorganic layer. The intermediate layer may be formed for the purpose of improving adhesion between the inorganic layer and the base layer or controlling the dielectric constant. The intermediate layer may be referred to as an under coating layer (UC).

The intermediate layer includes, for example, at least one selected from the group consisting of an acrylic resin, a urethane resin, a melamine resin, an alkyd resin, an epoxy resin, a siloxane polymer, and/or a condensate of an organosilane compound represented by the following formula (2). can do.

[Formula 2]

In Formula 2, X is hydrogen, halogen, alkoxy group, acyloxy group, alkylcarbonyl group, alkoxycarbonyl group, or -N(R2) ₂ , wherein R2 is hydrogen or an alkyl group, R1 is an alkyl group, an alkenyl group, Alkynyl group, aryl group, arylalkyl group, alkylaryl group, arylalkenyl group, alkenylaryl group, arylalkynyl group, alkynylaryl group, halogen, amino group, amide group, aldehyde group, alkylcarbonyl group, carboxyl group, mercapto group, cyano group No group, hydroxyl group, alkoxy group, alkoxycarbonyl group, sulfonyl group, phosphoryl group, acryloyloxy group, methacryloyloxy group or epoxy group, Q is a single bond, an oxygen atom or -N (R2 )-, wherein R2 is a hydrogen atom or an alkyl group, and m may be a number within the range of 1 to 3.

As the organosilane, one or more types may be selected from the group consisting of compounds represented by Formula 2, and in this case, crosslinking may be possible when one type of organosilane compound is used.

Examples of the organosilane include methyltrimethoxysilane, methyltriethoxysilane, phenyltrimethoxysilane, phenyltriethoxysilane, dimethyldimethoxysilane, dimethyldiethoxysilane, diphenyldimethoxysilane, diphenyldiethoxysilane , phenyldimethoxysilane, phenyldiethoxysilane, methyldimethoxysilane, methyldiethoxysilane, phenylmethyldimethoxysilane, phenylmethyldiethoxysilane, trimethylmethoxysilane, trimethylethoxysilane, triphenylmethoxysilane, triphenylmethoxysilane Phenylethoxysilane, phenyldimethylmethoxysilane, phenyldimethylethoxysilane, diphenylmethylmethoxysilane, diphenylmethylethoxysilane, dimethylethoxysilane, dimethylethoxysilane, diphenylmethoxysilane, diphenyl Toxysilane, 3-aminopropyltriethoxysilane, 3-glycidoxypropyltrimethoxysilane, p-aminophenylsilane, allyltrimethoxysilane, n-(2-aminoethyl)-3-aminopropyltrime Toxysilane, 3-Aminepropyltriethoxysilane, 3-Aminopropyltrimethoxysilane, 3-Glycidoxypropyldiisopropylethoxysilane, (3-glycidoxypropyl)methyldiethoxysilane, 3-Gly Cydoxypropyltrimethoxysilane, 3-mercaptopropyltrimethoxysilane, 3-mercaptopropyltriethoxysilane, 3-methacryloxypropylmethyldiethoxysilane, 3-methacryloxypropylmethyldimethoxysilane, 3-methacryloxypropyltrimethoxysilane, n-phenylaminopropyltrimethoxysilane, vinylmethyldiethoxysilane, vinyltriethoxysilane, vinyltrimethoxysilane, and mixtures thereof can be used. have.

In another example, the intermediate layer may be prepared by polymerizing one or more polyfunctional acrylates. Examples of the polyfunctional acrylate include 1,4-butanediol di(meth)acrylate, 1,6-hexanediol di(meth)acrylate, neopentylglycol di(meth)acrylate, polyethylene glycol di(meth)acrylate, neopentylglycol adipate di(meth)acrylate, hydroxyl puivalic acid neopentylglycol di(meth)acrylate, dicyclopentanyl di (meth)acrylate, caprolactone-modified dicyclopentenyl di(meth)acrylate, ethylene oxide-modified di(meth)acrylate, di(meth)acryloxyethyl isocyanurate, allylated cyclohexyl Di (meth) acrylate, tricyclodecane dimethanol (meth) acrylate, dimethylol dicyclopentane di (meth) acrylate, ethylene oxide-modified hexahydrophthalic acid di (meth) acrylate, tricyclodecane dimethanol ( Meth) acrylate, neopentyl glycol-modified trimethylpropane di(meth)acrylate, adamantane di(meth)acrylate or 9,9-bis[4-(2-acryloyloxyethoxy)phenyl ] a bifunctional acrylate such as fluorine; Trimethylolpropane tri(meth)acrylate, dipentaerythritol tri(meth)acrylate, propionic acid modified dipentaerythritol tri(meth)acrylate, pentaerythritol tri(meth)acrylate, propylene oxide trifunctional acrylates such as modified trimethylolpropane tri(meth)acrylate, trifunctional urethane (meth)acrylate, or tris(meth)acryloxyethyl isocyanurate; tetrafunctional acrylates such as diglycerin tetra(meth)acrylate or pentaerythritol tetra(meth)acrylate; pentafunctional acrylates such as propionic acid-modified dipentaerythritol penta(meth)acrylate; and dipentaerythritol hexa(meth)acrylate, caprolactone-modified dipentaerythritol hexa(meth)acrylate or urethane (meth)acrylate (ex. isocyanate monomer and trimethylolpropane tri(meth)acrylate) A hexafunctional acrylate such as a reactant may be used, but is not limited thereto.

In one example, the intermediate layer may include a fluorine-based compound. For example, a fluorine-based (meth)acrylate or a fluorine-based siloxane compound may be used. Although not particularly limited, a perfluorine compound such as perfluoropolyether acrylate may be used as the fluorine-based (meth)acrylate, and an alkoxysilane compound substituted with a fluorine-containing chain may be used as the fluorine-based siloxane compound.

As the epoxy-based resin applicable to the formation of the intermediate layer, at least one selected from the group consisting of an alicyclic epoxy resin and an aromatic epoxy resin may be used.

As the alicyclic epoxy resin, for example, at least one selected from the group consisting of an alicyclic glycidyl ether type epoxy resin and an alicyclic glycidyl ester type epoxy resin may be used. In addition, for example, Celloxide 2021P (Daicel), 3,4-epoxycyclohexyl-methyl-3,4-epoxycyclohexane carboxylate (3,4-epoxycyclohexyl-methyl-3,4-epoxycyclohexane carboxylate) and its Derivatives can be used, which are stable even at high temperatures, colorless and transparent, tough, and have excellent adhesion and adhesion for lamination. In particular, when used for coating, the surface hardness is excellent.

Examples of the aromatic epoxy resin include bisphenol A epoxy resin, brominated bisphenol A epoxy resin, bisphenol F type epoxy resin, bisphenol AD type epoxy resin, fluorene-containing epoxy resin, and triglycidyl isocyanurate. One or more aromatic epoxy resins selected from the group may be used.

The intermediate layer may be, for example, a coating layer formed by a sol-gel reaction. For example, SiOx (where x is an integer of 1 to 4), SiOxNy (where x and y are each an integer of 1 to 3), Al ₂ O ₃ , TiO ₂ , ZrO and ITO selected from the group consisting of One or more types may be included in the intermediate layer.

In addition, the intermediate layer may include a metal alkoxide represented by the following Chemical Formula 3 or a condensate thereof.

[Formula 3]

In Formula 3, M is any one metal selected from the group consisting of aluminum, zirconium and titanium, R3 is halogen, an alkyl group, an alkoxy group, an acyloxy group or a hydroxyl group, and z may be 3 or 4.

In one example, the intermediate layer may further include a filler. The filler, for example, may be used in consideration of the control of the refractive index and/or the mechanical strength of the intermediate layer. In one example, the filler is CaO, CaF ₂ , MgO, ZrO ₂ , TiO ₂ , SiO ₂ , In ₂ O ₃ , SnO ₂ , CeO ₂ , BaO, Ga ₂ O ₃ , ZnO, Sb ₂ O ₃ , At least one selected from the group consisting of NiO and Al ₂ O _{3 may be used.}

A method of forming the intermediate layer using the above material is not particularly limited, and various dry and/or wet coating methods such as a known method, for example, a deposition method and a sol-gel coating method, may be used depending on the material used. have.

The thickness of the intermediate layer is not particularly limited. For example, it may be 50 μm or less. Specifically, the upper limit of the thickness may be 40 µm or less, 30 µm or less, 20 µm or less, 10 µm or less, or 5 µm or less, and the lower limit thereof may be 0.5 µm or more or 1 µm or more.

In one example, the intermediate layer may be a layer that provides a flat surface on which an inorganic layer may be formed. That is, the intermediate layer may be a planarization layer. The planarization layer may be a layer having an average surface roughness (Rt) of a surface opposite to the surface facing the base layer, that is, a surface on which the inorganic layer is formed in a range of 15 to 45 nm. The surface roughness of the intermediate layer refers to an average value of the difference in height between the highest portion and the lowest portion in a predetermined region having roughness, and may be measured in the same manner as described in Experimental Examples below.

In one example, the first region of the inorganic layer may have a thickness of at least twice or more than the average surface roughness (Rt) of the planarization layer. For example, when the average surface roughness (Rt) of the planarization layer is 20 nm, the thickness of the first region may be 40 nm or more, and in another example, when the average surface roughness (Rt) of the planarization layer is 30 nm, the The thickness of the first region may be 60 nm or more. When the planarization layer and the first region in the barrier film satisfy the thickness relationship, the inorganic layer may be stably formed. In addition, the stably formed inorganic layer may provide excellent moisture permeability. Although not particularly limited, in general, when the planarization layer having the above composition is formed, considering that the surface roughness formed on one surface thereof is about 20 nm or more, 25 nm or more, or 30 nm or more, the thickness of the first region is about It may be desirable to be at least 60 nm, at least 65 nm, at least 70 nm or at least 75 nm. Even in this case, the upper limit of the thickness of the first region may be, for example, in the range of 300 nm.

The barrier film may be manufactured according to a predetermined method.

For example, the method for manufacturing the barrier film may include applying a polysilazane composition on a body to be coated including a base layer; and performing plasma treatment on the polysilazane layer formed on the body to be coated. The manufacturing method will be described in detail as follows.

Plasma treatment generates plasma in an atmosphere containing a plasma generating gas such as Ar, and injects positive ions in the plasma into the polysilazane layer. Plasma can be generated by, for example, an external electric field or a negative high voltage pulse. have. Such plasma treatment may be performed using a known apparatus.

The plasma treatment may be performed under the following conditions.

In one example, the plasma treatment may be performed by adjusting a distance of the plasma treatment object from the electrode. In this case, the plasma treatment target refers to a laminate in which the polysilazane composition is coated on an object to be coated (eg, a substrate layer), or a predetermined heating (heating) state for the composition applied on the object to be coated. It may mean a laminate in a state in which the polysilazane layer is formed through it. Such a laminate may be referred to as a barrier film precursor. For example, during the plasma treatment, the distance of the barrier film precursor from the electrode (positive and/or negative electrode) may be adjusted to 150 mm or less. As the distance between the precursor sample and the positive electrode is closer to the range satisfying the above distance, plasma energy can be transferred to the barrier film precursor while reducing plasma energy loss, and thermal energy generated during plasma discharge is reduced to the barrier film It is thought that the possibility of denaturation of polysilazane may increase as it is effectively delivered to the precursor. For example, the distance may be 140 mm or less, 130 mm or less, 120 mm or less, 110 mm or less, 100 mm or less, 90 mm or less, or 80 mm or less. The lower limit of the distance is not particularly limited, but if the distance between the negative electrode and the barrier film precursor is too close, there is a possibility of damage to the base layer, for example, the lower limit of the distance may be 15 mm or more or 20 mm or more.

In one example, the plasma treatment may be performed under a predetermined power density. Specifically, in the plasma treatment, the power density per unit area of the electrode may be about 0.05 W/cm ² or 0.10 W/cm ^{2 or} more. In another example, the power density is about 0.2 W/cm ² or more, about 0.3 W/cm ² or more, about 0.4 W/cm ² or more, about 0.5 W/cm ² or more, about 0.6 W/cm ² or more, about 0.7 W /cm ² or more, about 0.8 W/cm ² or more, or about 0.9 W/cm ^{2 or} more. Within the range that satisfies the power density, in the case of the positive electrode, the higher the power density, the higher the degree of plasma treatment for a short time, and the higher the degree of polysilazane denaturation due to the application of a high voltage. In the case of a negative electrode, an excessively high power density may cause damage to the substrate layer due to high voltage. Considering this, the upper limit of the power density is about 2 W/cm ² or less, 1.5 W/cm ² or less, or 1.0 W /cm ² or less.

In one example, in the case of having the power density, the processing energy during plasma treatment determined by the product of the power density and the processing time ^{may be 50 J/cm 2} or less. Specifically, the energy may be 45 J/cm ² or less, 40 J/cm ² or less, 35 J/cm ² or less, 30 J/cm ² or less, 25 J/cm ² or less, or 20 J/cm ² or less, The lower limit may be 5 J/cm ² or more, 10 J/cm ² or more, or 15 J/cm ² or more.

In one example, the plasma treatment may be performed under a predetermined process pressure. Specifically, the process pressure during the plasma treatment may be 350 mTorr or less. In the case of the positive electrode, since it is easier to secure a mean free path as the process pressure is lower, plasma treatment can be performed without energy loss due to collision with gas molecules. For example, the process pressure may be 340 mTorr or less, 330 mTorr or less, 320 mTorr or less, 310 mTorr or less, 300 mTorr or less, 290 mTorr or less, 280 mTorr or less, 270 mTorr or less, 260 mTorr or less, 250 mTorr or less, 240 mTorr or less It may be 230 mTorr or less, 220 mTorr or less, 210 mTorr or less, or 200 mTorr or less. On the other hand, in the case of a negative electrode, the lower the process pressure, the fewer gas molecules, so a high voltage and power may be required to generate plasma. The lower limit is 50 mTorr or more, 60 mTorr or more, 70 mTorr or more, 80 mTorr or more, 90 mTorr or more, 100 mTorr or more, 110 mTorr or more, 120 mTorr or more, 130 mTorr or more, 140 mTorr or more, 150 mTorr or more, 160 mTorr or more, 170 mTorr or more, 180 mTorr or more, or 190 mTorr or more. The pressure may be a pressure at the start of the process, and the pressure may be maintained within the range during the process.

In one example, the plasma treatment may be performed while adjusting the type and flow rate of the process gas. Specifically, the plasma treatment may be performed while injecting water vapor, a discharge gas (Ar), and oxygen into the processing space. When plasma treatment is performed under the process gas atmosphere as described above, hydrogen radicals dissociated from water vapor in the processing space remove and combine hydrogen elements _{of polysilazane to form hydrogen (H 2} ), thereby increasing the reactivity of polysilazane. It is thought that the barrier properties can be improved as a result.

When water vapor, discharge gas, and oxygen are used as process gases, the vapor pressure of water vapor in the processing space may be 5% or more. The water vapor vapor pressure is a percentage of an injection flow rate of water vapor injected to a total flow rate of gases injected into the processing space, and the plasma treatment is performed while water vapor, discharge gas, and reaction gas are injected at flow rates of A sccm, B sccm, and C sccm, respectively. In the case of performing the above, the vapor pressure of water vapor may be calculated as 100×A/(A+B+C). In another example, the water vapor vapor pressure may be about 10% or more, about 15% or more, about 20% or more, about 25% or more, or about 30% or more. The upper limit of the vapor pressure of water vapor is not particularly limited, and for example, about 90% or less, about 85% or less, about 80% or less, about 75% or less, about 70% or less, about 65% or less, about 60% or less, about 55% or less, about 50% or less, about 45% or less, about 40% or less, or about 35% or less.

In order to maintain the water vapor vapor pressure at the above level, plasma treatment may be performed while introducing water vapor at a predetermined flow rate or more into the space. For example, the modification treatment may be performed while injecting water vapor at a flow rate of 50 sccm or more into the processing space. In another example, the injection flow rate of the water vapor may be 60 sccm or more, 70 sccm or more, 80 sccm or more, 90 sccm or more, 100 sccm or more, 110 sccm or more, or 120 sccm or more. The upper limit of the injection flow rate is not particularly limited, and for example, the upper limit of the injection flow rate may be about 500 sccm or less, 400 sccm or less, 300 sccm or less, 200 sccm or less, or about 150 sccm or less.

By maintaining the water vapor vapor pressure as described above, the hydrogen partial pressure in the processing space can be controlled.

When the type and vapor pressure of the process gas are adjusted as described above, hydrogen desorption of the polysilazane layer by hydrogen radicals generated from water vapor may be achieved, and thus, the partial pressure of hydrogen in the processing space may be adjusted. For example, the partial pressure of hydrogen (H2) in the processing space may be in the range of ^{about 2.00×10 −5} Pa to 1.00×10 ^{−4 Pa.}

In one example, in relation to the plasma treatment conditions, the injection flow rates of the discharge gas and water vapor may be adjusted. Specifically, the ratio (H/N) of the injection flow rate (N) of the discharge gas to the injection flow rate (H) of the water vapor into the processing space may be maintained at 0.4 or more. The ratio (H/N) may be maintained at about 0.45 or more or about 0.5 or more in another example. The upper limit of the ratio (H/N) is not particularly limited, and may be, for example, about 5 or less, about 4 or less, about 3 or less, about 2 or less, about 1 or less, or about 0.9 or less. The denaturation treatment can be effectively performed under this range.

In one example, in relation to the plasma treatment conditions, the injection flow rates of water vapor and oxygen may be adjusted. Specifically, the ratio (H/O) of the injection flow rate (O) of the oxygen gas to the injection flow rate (H) of the water vapor into the processing space may be 0.4 or more. The ratio (H/O) may be maintained at about 0.45 or more or about 0.5 or more in another example. The upper limit of the ratio (H/O) is not particularly limited, and may be, for example, about 5 or less, about 4 or less, about 3 or less, about 2 or less, about 1 or less, or about 0.9 or less. The denaturation treatment can be effectively performed under this range.

The temperature at which the plasma treatment is performed is not particularly limited, but when the temperature is increased, the reaction for forming the barrier layer may become more smooth, so it may be appropriate to perform the plasma treatment at room temperature or higher. For example, the process temperature during the denaturation treatment may be 30°C or higher, 40°C or higher, 50°C or higher, 60°C or higher, 70°C or higher, or 80°C or higher. The process temperature may be about 85 ℃ or more, about 90 ℃ or more, about 95 ℃ or more, about 100 ℃ or more, about 105 ℃ or more, or about 110 ℃ or more in another example. The process temperature is maintained at about 200 °C or less, about 190 °C or less, about 180 °C or less, about 170 °C or less, about 160 °C or less, about 150 °C or less, about 140 °C or less, about 130 °C or less, or about 120 °C or less. can be

The plasma treatment time may be appropriately adjusted at a level that does not interfere with the barrier properties of the film. For example, the plasma treatment may be performed for about 10 seconds to 10 minutes.

The polysilazane layer formed on the object to be coated can be modified through plasma treatment under the above conditions, and thus the properties of the barrier film described above can be imparted. For example, when the inorganic layer is formed, polysilazane undergoes a dehydrogenation crosslinking reaction or a silica formation reaction. It is thought that silica formation predominantly occurs due to the supply of residual moisture or oxygen from the derived organic material portion. In addition, when the second region is formed, the supply of residual moisture or oxygen derived from the base layer or the intermediate layer is limited by the already formed first region, so it is considered that the nitrogen content increases while the dehydrogenation crosslinking reaction proceeds considerably. And, it is thought that density is imparted to the inorganic layer having such element content (distribution).

In one example, the method of manufacturing the barrier film may further include heating the film precursor before performing plasma treatment. The heating may be performed, for example, within a range of 40 to 150° C. for several minutes to several hours. After evaporating the solvent through the heating, plasma treatment may be performed.

The barrier film formed in the above manner may improve the vulnerability of the organic electronic device to external substances (eg, moisture).

The first electrode layer may be formed on the barrier film. As the electrode layer, for example, a conventional hole-injecting or electron-injecting electrode layer used for manufacturing an organic electronic device such as an organic light emitting device may be formed.

The hole-injecting electrode layer may be formed using, for example, a material having a relatively high work function, and, if necessary, may be formed using a transparent material. For example, the hole injection electrode layer may include a metal, an alloy, an electrically conductive compound having a work function of about 4.0 eV or more, or a mixture of two or more thereof. Examples of 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 serenide, metal sulfides such as zinc sulfide, and the like can be exemplified. 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 transparent material having high refractive index such as ZnS, TiO2 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, if necessary, the formed electrode layer may be patterned through a process using known photolithography or a shadow mask. The film thickness of the hole injection electrode layer varies depending on light transmittance, surface resistance, etc., but may typically be 500 nm or less or in the range of 10 nm to 200 nm.

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

Since the description of the configuration and characteristics of the second electrode layer is the same as that of the above-described first electrode layer, it is omitted.

The organic layer may include at least one light emitting layer. The organic layer may include a plurality of light emitting layers of two or more layers. When the light emitting layer includes two or more light emitting layers, the light emitting layers may have a structure in which an intermediate electrode having charge generating characteristics or a charge generating layer (CGL) is divided, but is not limited thereto.

The light emitting layer can be formed using, for example, 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(C26H26N2O2S), DSA-amine, TBSA, BTP, PAP-NPA, spiro-FPA, Ph3Si(PhTDAOXD), PPCP(1,2,3,4,5-pentaphenyl- cyclopenadiene derivatives such as 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, bon2Ir(acac), (C6)2Ir(acac), bt2Ir(acac), dp2Ir(acac), bzq2Ir(acac), bo2Ir(acac), F2Ir(bpy), F2Ir (acac), op2Ir(acac), ppy2Ir(acac), tpy2Ir(acac), FIrppy(fac-tris[2-(4,5'-difluorophenyl)pyridine-C'2,N]iridium(III)) or Btp2Ir Phosphorescent materials such as (acac)(bis(2-(2'-benzo[4,5-a]thienyl)pyridinato-N,C3'-)iridium(acetylactonate)) may be exemplified, but are limited thereto no. The light emitting layer includes the material as a host, and also includes perylene, distyrylbiphenyl, DPT, quinacridone, rubrene, BTX, ABTX or DCJTB. It may have a host-dopant system including a dopant.

The light-emitting layer can also be formed by appropriately employing a type exhibiting light-emitting properties from among the electron-accepting organic compounds or electron-donating organic compounds described later.

The organic layer may be formed in various structures including other various functional layers known in the art as long as it includes a light emitting layer. Examples of the layer that may be included in the organic layer include an electron injection layer, a hole blocking layer, an electron transport layer, a hole transport layer, and a hole injection 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 may be used without any particular limitation. Examples of such organic compounds include polycyclic compounds such as p-terphenyl or quaterphenyl or derivatives thereof, naphthalene, tetracene, pyrene, and coronene. ), polycyclic hydrocarbon compounds or derivatives thereof such as chrysene, anthracene, diphenylanthracene, naphthacene or phenanthrene, phenanthroline, vasophenantrol Heterocyclic compounds or derivatives thereof, such as bathophenanthroline, phenanthridine, acridine, quinoline, quinoxaline, or phenazine, may be exemplified. In addition, fluoroceine, perylene, phthaloperylene, naphthaloperylene, perynone, phthaloperinone, naphtharoperinone, diphenylbutadiene ( diphenylbutadiene, tetraphenylbutadiene, oxadiazole, aldazine, bisbenzoxazoline, bisstyryl, pyrazine, cyclopentadiene , oxine, aminoquinoline, imine, diphenylethylene, vinylanthracene, diaminocarbazole, pyrane, thiopyrane, polymethine, mero Cyanine, quinacridone, rubrene, etc. or derivatives thereof, Japanese Patent Application Laid-Open No. 1988-295695, Japanese Patent Application Laid-Open No. 1996-22557, Japanese Patent Laid-Open No. 1996-81472, A metal chelate complex compound disclosed in Japanese Patent Application Laid-Open No. 1993-009470 or Japanese Patent Application Laid-Open No. 1993-017764, for example, tris(8-quinolinolato)aluminum [ tris(8-quinolinolato)aluminium], bis(8-quinolinolato)magnesium, bis[benzo(f)-8-quinolinolato]zinc {bis[benzo(f)-8-quinolinolato]zinc}, Bis(2-methyl-8-quinolinolato)aluminum, tris(8-quinolinolato)indium [tris(8-quinolinolato)indium], tris(5-methyl-8-quinolinolato)aluminum , 8-quinolinolato or derivatives thereof, such as 8-quinolinolatolithium, tris(5-chloro-8-quinolinolato)gallium, and bis(5-chloro-8-quinolinolato)calcium a metal complex having one or more particles, Japanese Patent Laid-Open No. 1993-202011, Japanese Patent Application Laid-Open No. 1995-179394, Japanese Patent Application Laid-Open No. 1995-278124, or Japanese Patent Application Laid-Open No. 1995-228579 oxadiazole compound disclosed in Japanese Patent A triazine compound disclosed in Japanese Patent Laid-Open No. 1995-157473, etc., a stilbene derivative or a distyrylarylene derivative disclosed in Japanese Patent Application Laid-Open No. 1994-203963, and Japanese Patent Application Laid-Open No. 1994- styryl derivatives disclosed in Japanese Patent Laid-Open No. 132080 or 1994-88072, and the like, diolefin derivatives disclosed in Japanese Patent Laid-Open Nos. 1994-100857 and 1994-207170; a fluorescent whitening agent 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; 2,5-bis(4-methylstyryl)pyrazine, 2,5-bis(4-ethylstyryl)pyrazine, 2,5-bis[2-(1-naphthyl)vinyl]pyrazine, 2,5- Distyryl 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 Ridine, 1,4-para-terephenylenedimethelidine, 9,10-anthracenediyldimethylidine or 4,4'-(2,2-di-t-butylphenylvinyl)biphenyl , 4,4'-(2,2-diphenylvinyl)biphenyl, etc. or a dimethylidine compound or a derivative thereof, sila disclosed in Japanese Patent Laid-Open No. 1994-49079 or Japanese Patent Laid-Open No. 1994-293778 A silanamine derivative, a polyfunctional styryl compound disclosed in Japanese Patent Application Laid-Open No. 1994-279322 or Japanese Patent Laid-Open No. 1994-279323, etc., Japanese Patent Application Laid-Open No. 1994-107648 or Japanese Patent Application Laid-Open No. 1994-092947 The oxadiazole derivatives disclosed in et al., the anthracene compounds disclosed in Japanese Patent Application Laid-Open No. 1994-206865, etc., the oxynate derivatives disclosed in Japanese Patent Laid-Open No. 1994-145146, etc., and Japanese Patent Laid-Open No. 1992-96990 The tetraphenylbutadiene compound disclosed in et al., the organic trifunctional compound disclosed in Japanese Patent Application Laid-Open No. 1991-296595, etc., the coumarin derivative disclosed in Japanese Patent Application Laid-Open No. 1990-191694, and the like, and the like. The disclosed perylene derivative, the naphthalene derivative disclosed in Japanese Patent Application Laid-Open No. 1990-255789, etc., the phthaloperinone disclosed in Japanese Patent Application Laid-Open No. 1990-289676 or 1990-88689, etc. operynone) derivatives or styrylamine derivatives disclosed in Japanese Patent Laid-Open No. 1990-250292, etc. may also be used as the electron-accepting organic compound included in the low refractive index layer. In addition, the electron injection layer in the above, for example, may be formed using a material such as LiF or CsF.

The hole blocking layer is a layer capable of improving the lifespan and efficiency of the device by preventing injected holes from entering the electron injecting electrode layer through the light emitting layer, and, if necessary, using a known material for the light emitting layer and the electron injecting electrode layer It may be formed in an appropriate portion between the.

The hole injection layer or the hole transport 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'-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'-diaminobi 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'-diaminodiphenyl ether, 4,4'-bis(diphenylamino)quadriphenyl [4,4'-bis(diphenylamino)quadriphenyl], 4-N,N-diphenylamino-(2-diphenylvinyl)benzene, 3-methoxy-4'-N,N-diphenylaminostylbenzene, 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'-diaminobiphenyl 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-anthryl)-N-phenylamino]-p-ter Phenyl, 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-coronenyl)-N-phenylamino]biphenyl (4,4'-bis[N-(1-coronenyl)-N-phenylamino]biphenyl), 2,6 -bis(di-p-tolyl Amino)naphthalene, 2,6-bis[di-(1-naphthyl)amino]naphthalene, 2,6-bis[N-(1-naphthyl)-N-(2-naphthyl)amino]naphthalene, 4 ,4'-bis[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, Aryl amine compounds such as 4'-bis(N,N-di-p-tolylamino)terphenyl, and bis(N-1-naphthyl)(N-2-naphthyl)amine may be exemplified. , but is not limited thereto.

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. In addition, so-called π-conjugated polymers such as polyparaphenylenevinylene and derivatives thereof, hole-transporting non-conjugated polymers such as poly(N-vinylcarbazole), or σ-conjugated polymers of polysilane may also be used. have.

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

Illustratively, the organic device portion is sequentially formed in the form of (1) a hole injection electrode layer/organic emission layer/electron injection electrode layer; (2) the shape of the hole injection electrode layer/hole injection layer/organic light emitting layer/electron injection electrode layer; (3) the shape of the hole injection electrode layer/organic light emitting layer/electron injection layer/electron injection electrode layer; (4) the shape of the hole injection electrode layer/hole injection layer/organic light emitting layer/electron injection layer/electron injection electrode layer; (5) the shape of the hole injection electrode layer/organic semiconductor layer/organic light emitting layer/electron injection electrode layer; (6) the shape of the hole injection electrode layer/organic semiconductor layer/electron barrier layer/organic light emitting layer/electron injection electrode layer; (7) the shape of the hole injection electrode layer/organic semiconductor layer/organic light emitting layer/adhesion improving layer/electron injection electrode layer; (8) the shape of the hole injection electrode layer/hole injection layer/hole transport layer/organic light emitting layer/electron injection layer/electron injection electrode layer; (9) the shape of the hole injection electrode layer/insulating layer/organic light emitting layer/insulating layer/electron injection electrode layer; (10) the shape of the hole injection electrode layer/inorganic semiconductor layer/insulating layer/organic light-emitting layer/insulating layer/electron injection electrode layer; (11) the shape of the hole injection electrode layer/organic semiconductor layer/insulating layer/organic light-emitting layer/insulating layer/electron injection electrode layer; (12) hole injection electrode layer/insulating layer/hole injection layer/hole transporting layer/organic light-emitting layer/insulating layer/electron injection electrode layer or (13) hole injection electrode layer/insulating layer/hole injection layer/hole transporting layer/organic light-emitting layer/electron It may have the form of an injection layer/electron injection electrode layer, and in some cases, an intermediate electrode layer or a charge generating layer (CGL) in which at least two light emitting layers between the hole injection electrode layer and the electron injection electrode layer have charge generation characteristics. It may have a form including an organic layer of a structure divided by, but is not limited thereto.

In this field, various materials for forming a hole or electron injection electrode layer and an organic layer, for example, a light emitting layer, an electron injection or transport layer, a hole injection or transport layer, and a method for forming the same are known, and the production of the organic electronic device includes the above All of the same methods can be applied.

In one example, the organic device unit may further include a base layer for an organic device. The composition of the base layer for an organic device may be the same as that introduced for the base layer of the barrier film described above.

In one example, the organic electronic device may include a first electrode layer on a barrier film; an organic layer including a light emitting layer; and a second electrode layer in sequence. Specifically, the organic electronic device may include an inorganic layer; a first electrode layer; an organic layer including a light emitting layer; and a second electrode layer in sequence.

In one example, the inorganic layer and the first electrode layer may be attached to each other through an adhesive or an adhesive.

In one example, the inorganic layer and the first electrode layer may be in direct contact. Specifically, the organic electronic device may have a structure in which the inorganic layer and the first electrode layer directly contact each other without using a medium such as an adhesive between the inorganic layer and the first electrode layer. Such a laminated structure, for example, may be provided through a method in which the first electrode layer is directly formed on the inorganic layer of the barrier film prepared first, and the organic layer including the light emitting layer and the second electrode layer are sequentially formed. . Alternatively, after forming the organic element part including the first electrode layer, the organic layer including the light emitting layer, and the second electrode layer in sequence, the method of directly forming the inorganic layer of the barrier film on the first electrode layer, as described above A layered structure may be provided. Although not particularly limited, in this laminate structure, the second region of the barrier film may be adjacent to the first electrode layer, or the first region of the barrier film may be adjacent to the first electrode layer.

In one example, the organic electronic device may include an upper barrier film and a lower barrier film. Specifically, the organic electronic device may include a lower barrier film; a first electrode layer; an organic layer including a light emitting layer; a second electrode layer; and an upper barrier film in sequence. In this case, the inorganic layer of the lower barrier film and the first electrode layer may be in direct contact, and the second electrode layer and the inorganic layer of the upper barrier film may also be in direct contact with each other. A structure in which the second electrode layer and the inorganic layer of the upper barrier film directly contact each other may be provided according to the method of forming a structure in which the first electrode layer and the inorganic layer directly contact each other. Further, although not particularly limited, in such a laminated structure, the second region of the lower barrier film may be adjacent to the first electrode layer, or the first region of the lower barrier film may be adjacent to the first electrode layer. Likewise, a second region of the top barrier film can be adjacent to the second electrode layer, or a first region of the top barrier film can be adjacent to the second electrode layer.

In one example, the organic electronic device may include a base layer; inorganic layer; and an organic element unit.

In another example, the organic electronic device may have a structure having an organic device portion between the upper and lower barrier films. For example, the organic electronic device may include a base layer; inorganic layer; organic element unit; inorganic layer; It may have a laminated structure of the base layer.

In one example, the organic electronic device may further include a protective film in addition to the organic device part and the barrier part. The protective film may be, for example, provided on one surface of the organic element part on which the barrier film is not formed, and may be a metal (foil) coating.

In another example related to the present application, the present application relates to a method of manufacturing an organic electronic device.

In one example, the method comprises the steps of applying a polysilazane composition, and plasma-treating to form a barrier portion; and sequentially forming a first electrode layer, an organic material layer containing an emission layer, and a second electrode layer on the barrier part. In this case, the first electrode layer may be directly formed on one surface of the barrier part. A method of forming the first electrode layer, the organic material layer containing the emission layer, and the second electrode layer is not particularly limited, and may be formed using a known method known in the art.

In another example, the method includes the steps of: providing an organic device portion in which an organic material layer containing a light emitting layer is positioned between the first electrode layer and the second electrode layer; and coating a polysilazane composition on one surface of the first or second electrode layer and performing plasma treatment to form a barrier part. In this case, the first electrode layer may be directly formed on one surface of the barrier part. A method of forming the first electrode layer, the organic material layer containing the emission layer, and the second electrode layer is not particularly limited, and may be formed using a known method known in the art.

In the manufacturing method as described above, specific features and configurations of the barrier part or the organic element part are the same as those described above, and the above-described contents may be equally applied to the plasma processing method for forming the inorganic layer of the barrier part.

According to an example of the present application, an organic electronic device having a barrier film having excellent barrier properties and light transmittance may be provided.

1 shows the XPS analysis result of the inorganic layer of Example 1. FIG.
Figure 2 shows the XPS analysis results for the inorganic layer of Example 4.
FIG. 3 shows XPS analysis results for the inorganic layer of Comparative Example 1. FIG.
4 is a view of TEM analysis of a cross-section of the barrier film of Example 4;
5 is a schematic diagram illustrating an organic electronic device according to an example of the present application.
6 is an image showing the results of Experimental Example 3

Hereinafter, an organic electronic device including a barrier film according to the present application will be described through Examples and Comparative Examples according to the present application, but the scope of the present application is not limited by the following Examples.

<Check the blocking characteristics of the barrier part>

How to measure

* Moisture permeability: Using MOCON Aquatron II, the moisture permeability of the prepared barrier film was measured at 38 °C and 100% relative humidity.

* Etching rate and element content analysis: Element distribution analysis in the depth (thickness) direction from the surface of the inorganic layer to the substrate was carried out while gradually removing the inorganic layer using Ar ions. As the etching conditions, an Ar ion setting with an etching rate of 0.09 nm/s for _{Ta 2} O _{5 as a reference material was used.} In addition, the element content of the inorganic layer was analyzed using X-ray photoelectron spectroscopy (XPS) (C may be detected as an impurity derived from the substrate).

Experimental Example 1

Examples and Comparative Examples

For the barrier film prepared as follows, thickness, etching rate and moisture permeability were measured, and the results are shown in Table 1.

Example 1

A planarization layer having a thickness of 1 µm was laminated on a poly(ethylene terephthalate) (PET) (product made by Teijin) film having a thickness of about 50 µm, and an inorganic material layer was formed on the planarization layer. The specific process is as follows.

* Formation of a planarization layer : A composition containing 2 weight ratios of a photocuring initiator in a mixture having a content (weight) ratio of fluorene-based acrylate HR6060: PETA (pentaerythritol triacrylate): DPHA (dipentaerythritol hexaacrylate) of 80:10:10 (Propylene glycol methyl ether) was diluted to 25% to prepare a coating solution for the flattening layer. The coating solution was applied on a PET film as a substrate using a Mayer bar and dried at 100° C. for 5 minutes. Then, ultraviolet rays were irradiated with a mercury lamp at 0.6 J/cm ² , and the coating layer was cured to form a planarization layer.

Formation of the inorganic coating layer (1): Polysilazane was diluted to 3.7% with Merck's NL grade dibutylether, applied on the planarization layer using a Mayer bar, and dried at 100° C. for 5 minutes. Plasma treatment was performed on the polysilazane coating layer under the following conditions, and an inorganic coating layer was formed. With respect to the concentration of the diluted polysilazane, % means the weight ratio of the total solid content.

- Pressure 250 mTorr (Based on flow sccm Ar : O ₂ : H ₂ O = 1.5 : 1 : 1 atmosphere)

- 25 mm distance between the polysilazane coated surface and the electrode

- Power density: DC power 0.8 W/cm ² supplied for 25 seconds

Example 2

On the inorganic coating layer (1) prepared in Example 1, a polysilazane layer was additionally formed using a coating solution having a silazane concentration of 1%, and plasma treatment was performed under the same conditions as in Example 1 to form the inorganic coating layer (2) was further laminated.

Example 3

On the inorganic coating layer (1) prepared in Example 1, a polysilazane layer was further formed using a coating solution having a silazane concentration of 2.4%, and plasma treatment was performed under the same conditions as in Example 1 to perform the inorganic coating layer (2- 1) was further laminated.

Example 4

On the inorganic coating layer (1) prepared in Example 1, a polysilazane layer was further formed using a coating solution having a silazane concentration of 3.7%, and plasma treatment was performed under the same conditions as in Example 1 to perform the inorganic coating layer (2- 2) was further laminated.

Example 5

Base layer/planarization layer/inorganic coating layer (1) in the same manner as in Example 1, except that a coating solution having a silizane concentration of 2.4% was applied on the planarization layer during the manufacture of the inorganic layer, and the plasma treatment conditions were changed as follows. A barrier film containing -1) was prepared. Thereafter, a coating solution having a silizane concentration of 2.4% is applied on the inorganic coating layer 1-1, and plasma treatment is performed under the following conditions to perform a plasma treatment for the substrate layer/planarization layer/inorganic coating layer 1-1/inorganic coating layer 2-3 ) was prepared with a barrier film containing.

- Pressure 150 mTorr (Based on flow sccm Ar : O ₂ : H ₂ O = 1.5 : 1 : 1 atmosphere)

- 40 mm distance between the polysilazane coated surface and the electrode

- Power density: DC power 0.45 W/cm ² supplied for 45 seconds

Comparative Example 1

A barrier film was prepared in the same manner as in Example 1, except that a polysilazane solution diluted to 4.5% was used and plasma conditions were changed as follows.

- Pressure 100 mTorr (Based on flow sccm Ar : O ₂ = 1:1 atmosphere)

- 10 mm distance between the polysilazane coated surface and the electrode

- Power density: DC power 0.3 W/cm ² supplied for 65 seconds

Comparative Example 2

A barrier film was prepared in the same manner as in Comparative Example 1, except that a polysilazane solution diluted to 4.9% was used and the distance from the electrode was 175 mm.

[Table 1]

As shown in Table 1, it can be seen that the embodiment including the inorganic layer satisfying the etching rate of 0.17 nm/s or less has very low moisture permeability compared to the comparative example that does not satisfy the etching rate. In particular, in the case of Example 1 of the present case, it can be confirmed that although the thickness of the inorganic layer is thinner than that of Comparative Example, excellent barrier properties can be secured. This means that the inorganic layer of the barrier film of Example is denser than the inorganic layer of the barrier film of Comparative Example. Also, a 4.9% silazane solution was used to form the barrier film in Comparative Example 2, and a 2.4% silazane solution was used twice to form the barrier film in Example 5, although the concentrations of the silazane solutions are almost the same. (The concentration of the comparative example is higher) It can be seen that the difference in water permeability occurred. This suggests that the denseness of the film is not due to the concentration of the coating solution.

Under the premise of having a similar density, as the thickness of the layer increases, the barrier properties against gas or moisture generally increase (refer to the moisture permeability of Comparative Examples 1 and 2). In this regard, when Example 2 and Example 5 are compared, it can be seen that the water permeability of Example 5, which has a lower thickness, is lower. This is because the thickness of the second region, which is a region of high nitrogen concentration, is larger in the film of Example 5. This is also confirmed when comparing the thicknesses of the second regions of Examples 1 to 5. That is, as the etching rate for the reference condition is 0.17 nm/s or less, on the premise that the density of the inorganic layer confirmed through the etching rate is secured, as the thickness of the second region, which is a high nitrogen concentration region, is thicker ( decrease) can be seen.

Meanwhile, the second region of the films of Examples 3 and 5 was formed from the same 2.4% silazane solution, but the thickness of the second region was different. That is, by appropriately controlling the above-mentioned conditions during plasma treatment, the thickness of the second region, which is a region of high nitrogen concentration, may be increased, and the barrier properties of the barrier film may be further improved.

<Confirmation of driving characteristics of organic electronic devices>

Experimental Example 2

(1) Manufacture of organic element part

A first electrode layer, an organic layer containing a light emitting layer, and a second electrode layer were sequentially formed on a commercially available polyimide (PI) substrate. Specifically, a hole injection electrode layer containing ITO (Indium Tin Oxide) is formed on a PI substrate by a known sputtering method, and alpha-NPD (N,N'-Di-[(1- naphthyl)-N,N'-diphenyl]-1,1'-biphenyl)-4,4'-diamine) containing a hole injection layer and a light emitting layer (4,4',4'-tris(N-carbazolyl)- triphenylamine (TCTA):Firpic, TCTA:Fir6) were sequentially formed. Next, an electron transporting compound TCTA (4,4',4'-tris(N-carbazolyl)-triphenylamine) and a low refractive material LiF (refractive index: about 1.39) were added on the light emitting layer so that the refractive index of the entire layer was about 1.66 A low refractive organic layer was formed to a thickness of about 70 nm by co-deposition. Then, an aluminum (Al) electrode as an electron injecting reflective electrode was formed on the low refractive organic layer by vacuum deposition to manufacture a device.

(2) manufacture of barrier part

An inorganic coating layer 1 (ie, an inorganic layer of a barrier part) was formed directly on the aluminum (Al) electrode of the prepared organic device part in the same way as those used in Example 1.

(3) Confirmation of driving of organic electronic devices

A voltage of 5 V was connected to the organic electronic device (PI/organic device part/inorganic layer) prepared as described above, and it was confirmed that the light emitting area (3 X 3 mm 2 ) was lit. Even if the inorganic layer was directly formed on the organic device, the device was lit with appropriate brightness.

Experimental Example 3

An organic device part prepared as in Experimental Example 2 was prepared, and a copper foil film was formed on the aluminum (Al) electrode. Then, the same adhesive was attached to the inorganic layer of each barrier film in Example 1 and Comparative Example 1, and the adhesive was attached to the PI film of the organic device part to form an organic electronic device (barrier film/adhesive/PI/organic device part/copper) foil film) was prepared.

After the organic electronic device was stored at 85° C. and 85% relative humidity for 365 hours, a voltage of 5 V was connected, and the lighting of the emission area (30 X 150 mm 2 ) was confirmed. Example 1 The lighting state when using the film is the same as Figure 6 (a), Comparative Example 1 The lighting mode when using the film is the same as Figure 6 (b). In FIG. 6( a ), light emission is clear because there is no degradation due to water penetration, but in FIG. 6( b ), black spots appear due to degradation due to water penetration. For reference, in FIG. 6( a ), markers are arbitrarily marked in order to avoid confusion between the inorganic layer and the base layer of the barrier film during device manufacturing.

100: barrier part
200: organic element unit
300: protective film
400: adhesive layer or adhesive

Claims (13)

a barrier film comprising an inorganic layer; a first electrode layer; an organic layer including a light emitting layer; And an organic electronic device comprising a second electrode layer,
The inorganic layer includes a first region and a second region having different element contents (atomic%) of Si, N, and O measured by XPS, and _{Ar etching Ta 2} O ₅ at a rate of 0.09 nm/s The etching rate in the thickness direction with respect to the ion etching condition is 0.17 nm/s or less,
The second region has an element content of N higher than that of the first region,
The second region is an organic electronic device having a thickness of 10% or more of the total thickness of the inorganic layer. The organic electronic device according to claim 1, wherein the barrier film has a water vapor transmission rate of 10 × 10 ^-4 g/m ² ·day or less, measured at a temperature of 38°C and 100% relative humidity. According to claim 1, wherein the barrier film further comprises a base layer,
base layer; inorganic layer; a first electrode layer; an organic layer including a light emitting layer; and a second electrode layer sequentially. The organic electronic device of claim 3 , wherein the inorganic layer is in direct contact with the first electrode layer. The organic electronic device of claim 4, wherein the first region is closer to the base layer than the second region. The organic electronic device of claim 4 , wherein the second region is closer to the base layer than the first region. The organic electronic device of claim 1 , wherein the first region satisfies an O content > Si content > N content. The organic electronic device of claim 7, wherein the O content of the first region is in the range of 50 to 65 atomic%, the Si content is in the range of 35 to 45 atomic%, and the N content is in the range of 1 to 15 atomic%. The organic electronic device of claim 8 , wherein the first region has an O content (a) and a Si content (b) ratio (a/b) within a range of 1.1 to 1.9. The organic electronic device of claim 9 , wherein the second region satisfies Si content > N content > O content. The organic electronic device according to claim 10, wherein the Si content of the second region is in the range of 45 to 60 atomic%, the N content is in the range of 20 to 35 atomic%, and the O content is in the range of 10 to 30 atomic%. The organic electronic device of claim 11 , wherein a difference between the maximum value of the Si content of the second region and the maximum value of the O content of the first region is 15 atomic% or less. The organic electronic device according to claim 1, wherein the inorganic layer is obtained by plasma-treating polysilazane having a unit represented by the following formula (1):
[Formula 1]

In Formula 1, R ¹ , R ² and R ³ are each independently a hydrogen atom, an alkyl group, an alkenyl group, an alkynyl group, an aryl group, an alkylsilyl group, an alkylamino group, or an alkoxy group.

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