KR20160020836A - Barrier film structure and organic electronic device having the same - Google Patents

Abstract

The present invention relates to: a barrier film structure which can effectively prevent inflow of moisture or oxygen from the atmosphere, and has improved bending resistance and improved light transmittance; and an organic electronic device having the same. In addition, the barrier film structure comprises: a base film; a barrier layer consisting of an inorganic compound disposed on the base film; and a metal layer which comes in contact with at least one surface of the barrier layer.

Description

[0001] The present invention relates to a barrier film structure and an organic electronic device having the barrier film structure,

BACKGROUND OF THE INVENTION 1. Field of the Invention [0001] The present invention relates to a barrier film structure and an organic electronic device having the barrier film structure. More particularly, the present invention relates to a barrier film structure and an organic electronic device including the barrier film structure.

In general, an organic light emitting diode, such as an organic light emitting diode, is a light emitting device that does not need an external light source but emits itself, has an advantage of high luminous efficiency, excellent luminance and viewing angle and fast response speed, Or oxygen is introduced to the inside of the light emitting device to oxidize the electrodes or deteriorate the device itself, shortening the life span and gradually degrading the light emitting luminance, the light emitting efficiency and the light emitting uniformity. In order to prevent these problems, various techniques for sealing the organic light emitting device to suppress contact between moisture and oxygen have been studied.

For example, a barrier film structure having an aluminum foil layer on a substrate has been attempted. However, although such a structure can obtain a stable gas barrier function, there is a problem in that the aluminum thin layer is provided as the barrier layer, so the incineration suitability is poor and the disposal after use is not easy. Further, since the aluminum foil layer is provided, there is a problem that a barrier film structure having transparency can not be obtained.

In order to solve such a problem, a barrier film structure having a barrier layer made of polyvinylidene chloride (PVDC) or an ethylene-vinyl alcohol copolymer (EVOH) has been developed.

However, since polyvinylidene chloride contains chlorine, if it is incinerated after use, chlorine gas is generated, which is harmful to the environment. On the other hand, the ethylene-vinyl alcohol copolymer has an advantage of excellent barrier function against oxygen gas and low adsorption of flavor components, but the oxygen gas barrier function is deteriorated in a high humidity atmosphere. Further, the ethylene-vinyl alcohol copolymer has a problem that the barrier function against water vapor is low. For this reason, the barrier layer containing an ethylene-vinyl alcohol copolymer needs to introduce an additional laminated structure for blocking from water vapor, which increases the manufacturing cost.

Korean Patent Publication No. 2010-0056421

Disclosure of Invention Technical Problem [8] The present invention has been made to solve the above-mentioned problems, and it is an object of the present invention to provide a barrier film structure and an organic electronic device having the barrier film structure with improved permeability and bending resistance while effectively preventing moisture and oxygen from entering the atmosphere. The purpose is to provide. However, these problems are exemplary and do not limit the scope of the present invention.

A barrier film structure according to one aspect of the present invention is provided. The barrier film structure includes a base film, a barrier layer made of an inorganic compound disposed on the base film, and a metal layer in contact with at least one surface of the barrier layer.

In the barrier film structure, the metal layer may be a thin film layer made of aluminum (Al), gold (Au), silver (Ag), or copper (Cu). The metal layer may have a thickness of 1 nm to 5 nm.

In the barrier film structure, the barrier layer may be formed of a silicon oxynitride layer.

In the barrier film structure, the barrier layer may be a single layer or a plurality of laminated layers including at least one selected from the group consisting of silicon oxide, silicon oxynitride, silicon nitride and aluminum oxide, aluminum nitride and aluminum oxynitride have.

In the barrier film structure, the base film may include any one selected from an annular olefin polymer film, a polyethylene terephthalate film, a polyethylene naphthalate film, and a polycarbonate film.

A method of manufacturing a barrier film structure according to another aspect of the present invention is provided. The method of manufacturing the barrier film structure includes the steps of providing a base film, forming a barrier layer made of an inorganic compound disposed on the base film, and forming a metal layer in contact with at least one surface of the barrier layer .

In the method of manufacturing a barrier film structure, the step of forming the barrier layer and the step of forming the metal layer may be performed by a sputtering process.

An organic electronic device according to another aspect of the present invention is provided. The organic electronic device may include an organic light emitting diode (OLED) or an organic solar cell (OPV) having the barrier film structure described above.

According to one embodiment of the present invention as described above, it is possible to provide a barrier film structure having improved light transmittance and bending resistance while effectively preventing moisture or oxygen from being introduced into the atmosphere, and an organic electronic device having the barrier film structure. Of course, the scope of the present invention is not limited by these effects.

1 is a diagram illustrating a cross-section of a barrier film structure in accordance with an embodiment of the present invention.
2 is a flowchart illustrating a method of manufacturing a barrier film structure according to an embodiment of the present invention.
3 is a diagram illustrating a cross-section of a barrier film structure according to another embodiment of the present invention.
4 is a diagram illustrating a cross-section of a barrier film structure according to another embodiment of the present invention.
5 is a cross-sectional view schematically illustrating a part of an organic light emitting diode diode having a barrier film structure according to embodiments of the present invention.

The barrier film structure according to the technical idea of the present invention is a transparent structure while preventing water or oxygen from being introduced into the atmosphere. The barrier film structure may include a base film, a barrier layer made of an inorganic compound disposed on the base film, and a metal layer in contact with at least one surface of the barrier layer.

The barrier layer may be formed of a silicon oxynitride layer having a high barrier property, and may be formed, for example, by a sputtering process. In modified embodiments, the barrier layer may comprise a single layer comprising at least one or more selected from the group consisting of silicon oxide, silicon oxynitride, silicon nitride and aluminum oxide, aluminum nitride and aluminum oxynitride, Layer.

The stress of the barrier layer made of the inorganic compound is relaxed. The metal layer may be arranged to contact at least one surface of the barrier layer to compensate for the ductility and the toughness of the barrier layer.

The barrier layer comprising a thin film made of an inorganic compound such as silicon oxynitride is adhered and formed on the substrate by vacuum evaporation, there is no environmental problem at the time of disposal, and there is no gas barrier property and no humidity dependency, The problems of vinylidene chloride (PVDC) and ethylene-vinyl alcohol copolymer (EVOH) can be overcome.

However, since the above-mentioned barrier layer containing a thin film made of an inorganic compound such as silicon oxynitride is deposited on a substrate, there is a gap called a grain boundary between inorganic particles, so that the gas barrier function of the thin film is not sufficient. For this reason, it is necessary to form the barrier layer made of the above-mentioned inorganic compound to have a thickness of, for example, about 500 Å to 1000 Å. However, when the thickness of the barrier layer made of an inorganic compound is increased, a problem of cracking is liable to occur due to a decrease in spreadability.

In the barrier film structure according to the technical idea of the present invention, a transparent metal layer having a flame-resisting property is introduced so as to compensate the fl exibility of the barrier layer made of an inorganic compound. That is, the metal layer can prevent cracks that may occur due to the residual stress in the barrier layer made of the inorganic compound through stress relaxation due to excellent ductility under the condition that the influence on the permeability is minimized. Furthermore, the metal layer can also contribute to barrier properties that prevent water or oxygen from entering the atmosphere.

However, since the metal layer is disadvantageous from the viewpoint of light transmittance, it is preferable that the metal layer has a thickness thin enough to transmit light. For example, the metal layer is a thin film layer made of aluminum (Al), gold (Au), silver (Ag), or copper (Cu), and may have a thickness of 1 nm to 5 nm, for example.

However, even if the thickness of the metal layer is reduced to a nanosize, even if the transparent film is formed, the light transmittance is less than 80%. Thus, in the barrier film structure according to the technical idea of the present invention, the silicon oxynitride layer, which is in contact with at least one surface of the metal layer, Thereby enhancing the light transmittance of the metal layer. The present inventors have confirmed that when the thickness of the silicon oxynitride layer is 20 nm to 300 nm, it is possible to effectively prevent the moisture from being introduced into the interior along with the improvement of light transmittance.

The barrier film structure according to the embodiments of the present invention can realize a barrier property that simultaneously enhances the ductility and the light transmittance by introducing the transparent metal layer and the silicon oxynitride layer.

Further, since the barrier film structure according to the embodiments of the present invention can form a film in a vacuum chamber using only an inorganic compound without using an organic material on the base film, the manufacturing cost can be expected to be reduced.

Hereinafter, embodiments are provided to facilitate understanding of the present invention.

It is to be understood that both the foregoing general description and the following detailed description are exemplary and explanatory and are intended to provide further explanation of the invention as claimed. The present invention is not limited to the embodiment. Rather, these embodiments are provided so that this disclosure will be more thorough and complete, and will fully convey the concept of the invention to those skilled in the art. In the drawings, the thickness and size of each layer are exaggerated for convenience and clarity of explanation.

Like numbers refer to like elements throughout the specification. As used herein, the term "and / or" includes any and all combinations of one or more of the listed items. The terminology used herein is for the purpose of describing particular embodiments only and is not intended to be limiting of the invention. As used herein, the singular forms "a," "an," and "the" include singular forms unless the context clearly dictates otherwise. Also, the phrase "comprise" when used herein is intended to specify the presence of stated features, integers, steps, operations, elements, elements, and / or groups thereof, , Operation, absence, presence of elements and / or groups.

It is to be understood that throughout the specification, when an element such as a film, an area, or a substrate is referred to as being "on " another element, the element may be directly" on " It is to be understood that there may be other components intervening in the system. On the other hand, when an element is referred to as being "directly on" another element, it is understood that there are no other elements intervening therebetween.

In the figures, for example, variations in the shape shown may be expected, depending on manufacturing techniques and / or tolerances. Accordingly, embodiments of the present invention should not be construed as limited to any particular shape of the regions illustrated herein, including, for example, variations in shape resulting from manufacturing.

As used herein, the expression " transparent " includes not only the case where the light transmittance is 100% but also the concept of translucency, except for a case where the light is completely blocked, which is completely opaque.

FIG. 1 is a cross-sectional view of a barrier film structure according to an embodiment of the present invention, and FIG. 2 is a flowchart illustrating a method of manufacturing a barrier film structure according to an embodiment of the present invention.

Referring to FIGS. 1 and 2, a method of manufacturing a barrier film structure 100 according to an embodiment of the present invention includes providing a base film 110 (S10), forming a barrier layer A step S20 of forming a silicon oxynitride layer 120 and a step S30 of forming an aluminum layer 130 which is a metal layer on the silicon oxynitride layer 120.

The barrier film structure 100 thus formed is a transparent film structure in which a base film 110, a silicon oxynitride layer 120, and an aluminum layer 130 are sequentially laminated. That is, a silicon oxynitride layer 120 which is a barrier layer is formed on the upper surface of the base film 110, and an aluminum layer 130 which is a metal layer is formed on the upper surface of the silicon oxynitride layer 120.

In a modified embodiment of the present invention, the silicon oxynitride layer 120 is a single layer comprising at least one selected from the group consisting of silicon oxide, silicon nitride, silicon oxynitride, aluminum oxide, aluminum nitride and aluminum oxynitride. Layer or stacked layers.

An increase in the thickness of the silicon oxynitride layer 120 is inevitably required to enhance the barrier properties of the silicon oxynitride layer 120 made of an inorganic compound. An aluminum layer 130 is disposed adjacent to the silicon oxynitride layer 120 to compensate for the problem of the lowering of the tortuosity that accompanies an increase in the thickness of the silicon oxynitride layer 120. In a modified embodiment of the present invention, the aluminum layer 130 may be replaced by a thin film layer of gold (Au), silver (Ag), or copper (Cu).

Since the aluminum layer 130 is excellent in ductility and electrical conductivity, the aluminum oxynitride layer 130 can compensate for the conductivity of the silicon oxynitride layer 120 and contribute to the barrier properties of preventing moisture and oxygen from being introduced into the atmosphere. However, since the aluminum layer 130 is disadvantageous from the viewpoint of light transmittance, it is preferable that the aluminum layer 130 has a thickness thin enough to transmit light.

The inventors have found that as the thickness of the aluminum thin film is reduced from 40 nm to 1 nm, the light transmittance tends to be higher in the visible light region, but the light transmittance is generally less than 80%. Particularly, when the thickness of the aluminum thin film is 5 nm or more, the light transmittance may be lowered to 20% or less according to the visible light wavelength.

Accordingly, when the aluminum layer 130 is introduced into the barrier film structure 100, the thickness of the aluminum layer 130 may be preferably 1 nm to 5 nm. When the thickness of the aluminum layer 130 is less than 1 nm, it is advantageous in terms of light transmittance but has no effect of complementing the toughness of the silicon oxynitride layer 120. When the thickness of the aluminum layer 130 exceeds 5 nm There arises a problem that the softness of the silicon oxynitride layer 120 is compensated for but the light transmittance is remarkably lowered.

On the other hand, it has been confirmed that when the thickness of the silicon oxynitride layer 120 is 20 nm to 300 nm, it is possible to effectively prevent the moisture from flowing into the inside of the silicon oxynitride layer 120 together with the improvement of light transmittance.

The base film 110 is formed of a film made of a cyclic olefin polymer (COP), a polyethylene terephthalate (PET) film, a polyethylene terephthalate (PEN) film, and a polycarbonate (PC) , Or a multilayer film in which at least two films selected from the above group are laminated. This base film 110 can be understood as a transparent substrate replacing a glass substrate.

For example, the cyclic olefin polymer (COP) is a polymer obtained from a cyclic monomer such as norbornene, which is superior in transparency, heat resistance, and chemical resistance to conventional olefin polymers and has a very low birefringence and water absorption rate Can be used as the material of the film 110.

Meanwhile, the silicon oxynitride layer 120 and the aluminum layer 130 may be formed by a sputtering process. For example, the silicon oxynitride layer 120 may be formed on a substrate by a reactive sputtering process in which an oxygen gas and a nitrogen gas are introduced into a silicon target.

Accordingly, since the barrier film structure 100 according to an embodiment of the present invention can be formed by performing deposition in a vacuum chamber using only an inorganic compound without using an organic substance on the base film 110, the manufacturing cost can be reduced The effect can be expected.

 4 is a diagram illustrating a cross-section of a barrier film structure according to another embodiment of the present invention.

Referring to FIG. 4, a barrier film structure 100 according to another embodiment of the present invention is a film structure in which a base film 110, an aluminum layer 130, and a silicon oxynitride layer 120 are sequentially stacked. That is, an aluminum layer 130, which is a metal layer, is formed on the upper surface of the base film 110, and a silicon oxynitride layer 120 is formed on the upper surface of the aluminum layer 130.

In a modified embodiment of the present invention, the silicon oxynitride layer 120 is a single layer comprising at least one selected from the group consisting of silicon oxide, silicon nitride, silicon oxynitride, aluminum oxide, aluminum nitride and aluminum oxynitride. Layer or stacked layers. In a modified embodiment of the present invention, the aluminum layer 130 may be replaced by a thin film layer of gold (Au), silver (Ag), or copper (Cu).

Since the aluminum layer 130 is excellent in ductility and electrical conductivity, the aluminum oxynitride layer 130 can compensate for the conductivity of the silicon oxynitride layer 120 and contribute to the barrier properties of preventing moisture and oxygen from being introduced into the atmosphere. However, since the aluminum layer 130 is disadvantageous from the viewpoint of light transmittance, it can have a thickness thin enough to transmit light, for example, 1 nm to 5 nm.

When the thickness of the aluminum layer 130 is less than 1 nm, it is advantageous in terms of light transmittance but has no effect of complementing the toughness of the silicon oxynitride layer 120. When the thickness of the aluminum layer 130 exceeds 5 nm There arises a problem that the softness of the silicon oxynitride layer 120 is compensated for but the light transmittance is remarkably lowered. On the other hand, it has been confirmed that when the thickness of the silicon oxynitride layer 120 is 20 nm to 300 nm, it is possible to effectively prevent the moisture from flowing into the inside of the silicon oxynitride layer 120 together with the improvement of light transmittance.

Further description and effect of each of the components are the same as those described with reference to FIGS. 1 and 2, and thus will not be described here.

4 is a diagram illustrating a cross-section of a barrier film structure according to another embodiment of the present invention.

Referring to FIG. 4, a barrier film structure 100 according to another embodiment of the present invention includes a base film 110, a silicon oxynitride layer 120 as a barrier layer, and an aluminum layer 130 as a metal layer, Stacked structure.

For example, the barrier film structure 100 according to another embodiment of the present invention includes a plurality of unit laminations (n: n is a positive integer of 2 or more) composed of the silicon oxynitride layer 120 and the aluminum layer 130, ≪ / RTI > laminated structure. In this case, the upper surface of the base film 110 is in direct contact with the silicon oxynitride layer 120.

Although not shown in the drawings, the barrier film structure according to another modified embodiment of the present invention includes a plurality of unit laminations (n: n is a positive integer of 2 or more) formed of the aluminum layer 130 and the silicon oxynitride layer 120 ). ≪ / RTI > In this case, the upper surface of the base film 110 is in direct contact with the aluminum layer 130.

The inventor measured transmittance, stress and moisture permeability (WVTR), and the like for the experimental examples having the aluminum layer 130 and the silicon oxynitride layer 120 and the comparative examples not having the aluminum layer 130 , And the results are shown in Table 1.

[Table 1]

Experimental Example 1 relates to a barrier film structure 100 in which an aluminum layer 130 and a silicon oxynitride layer 120 are sequentially formed on a COP film base film 110 as shown in FIG. Example 2 is a modification of Fig. 4 in which an aluminum layer 130, a silicon oxynitride layer 120, an aluminum layer 130, and a silicon oxynitride layer 120 are sequentially formed on a base film 110, which is a COP film To a barrier film multi-stack structure.

Referring to Comparative Examples 1 to 3, it can be understood that silicon oxynitride is more effective in preventing moisture inflow than silicon oxide and silicon nitride. Referring to Experimental Example 1 and Comparative Example 3, introduction of the aluminum layer 130 The light transmittance was reduced by about 2%, but the moisture permeability was improved by 50% or more. Experimental Example 1 and Experimental Example 2 showed that the moisture permeability was remarkably improved in the case of multiple layers of a multi-stack rather than a single layer of the aluminum layer 130 can confirm.

The barrier film structure 100 may be applied to an organic electronic device such as an organic light emitting diode (OLED) or an organic solar cell (OPV).

5 is a schematic cross-sectional view illustrating a portion of an organic light emitting diode (OLED) having a barrier film structure according to embodiments of the present invention.

5, the organic light emitting diode 200 includes a substrate 210, an anode 220 stacked on the substrate 210, an organic layer 230, and a light-transmitting cathode 240, The above-described barrier film structure 100 is disposed. Of course, the configuration of the organic light emitting diode 200 shown in FIG. 6 is illustrative and can be modified.

Meanwhile, the barrier film structure 100 shown in FIG. 5 may correspond to a state in which the barrier film structure 100 shown in FIG. 1, FIG. 3, or 4 is turned upside down. For example, when the barrier film structure 100 shown in FIG. 1 is applied to the organic light emitting diode 200, the aluminum layer 130 is disposed directly on the light-transmitting cathode 240, and the aluminum layer 130 The silicon oxynitride layer 120 and the base film 110 may be sequentially arranged.

In recent years, in order to apply the organic light emitting diode (OLED) to the flexible display device, there is a growing demand for securing the flexibility of the components constituting the organic light emitting diode diode 200, The barrier film structure 100 as an encapsulating material having improved light transmittance with the silicon oxynitride layer 120 described above can expand the application range of the organic light emitting diode OLED .

Meanwhile, the barrier film structure 100 according to the embodiments of the present invention is expected to be applicable not only to organic light emitting devices but also to organic solar cells. That is, the back sheet positioned at the rear most side of the solar cell module generally has structures such as a solar cell cell vulnerable to moisture located inside the solar cell module from external factors such as oxygen, water, It is expected that the barrier film structure 100 described above can be applied to the back sheet.

While the present invention has been described with reference to exemplary embodiments, it is to be understood that the invention is not limited to the disclosed exemplary embodiments, but, on the contrary, is intended to cover various modifications and equivalent arrangements included within the spirit and scope of the invention. Accordingly, the true scope of the present invention should be determined by the technical idea of the appended claims.

100: barrier film structure
110: base film
120: Silicon oxynitride layer
130: Aluminum layer
200: organic light emitting diode

Claims (11)

A base film;
A barrier layer made of an inorganic compound disposed on the base film; And
A metal layer in contact with at least one surface of the barrier layer;
≪ / RTI > The method according to claim 1,
Wherein the metal layer is a thin film layer made of aluminum (Al). 3. The method of claim 2,
Wherein the metal layer has a thickness of 1 nm to 5 nm. The method according to claim 1,
Wherein the barrier layer is comprised of a silicon oxynitride layer. The method according to claim 1,
Wherein the barrier layer is a single layer or a plurality of stacked layers comprising at least one selected from the group consisting of silicon oxide, silicon oxynitride, silicon nitride and aluminum oxide, aluminum nitride and aluminum oxynitride. The method according to claim 1,
Wherein the barrier layer and the metal layer are formed by repeatedly laminating a plurality of unit laminations each comprising one barrier layer and one metal layer. The method according to claim 1,
The base film may be at least one selected from the group consisting of a cyclic olefin polymer (COP) film, a polyethylene terephthalate (PET) film, a polyethylenenaphthalate (PEN) film, and a polycarbonate ≪ / RTI > An organic electronic device comprising the barrier film structure according to any one of claims 1 to 7. 9. The method of claim 8,
Wherein the organic electronic device comprises an organic light emitting diode (OLED) or an organic solar cell (OPV). Providing a base film;
Forming a barrier layer of an inorganic compound disposed on the base film; And
Forming a metal layer in contact with at least one surface of the barrier layer;
≪ / RTI > 11. The method of claim 10,
Wherein the step of forming the barrier layer and the step of forming the metal layer are performed by a sputtering process.

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