KR102343768B1 - Barrier film structure and organic electronic device having the same - Google Patents

Abstract

The present invention relates to a barrier film structure having improved bending resistance and light transmittance while effectively preventing the inflow of moisture or oxygen in the atmosphere, and an organic electronic device having the same, comprising a base film and an inorganic compound disposed on the base film. A barrier layer made of, a metal layer in contact with at least one surface of the barrier layer to supplement the ductility of the barrier layer, and silicon oxide in contact with at least one surface of the metal layer to supplement light transmittance of the metal layer (SiO _x ) A barrier film structure comprising a layer is provided.

Description

Barrier film structure and organic electronic device having the same

The present invention relates to a barrier film structure and an organic electronic device having the same, and more particularly, to a barrier film structure capable of preventing the inflow of moisture or oxygen in the atmosphere, and an organic electronic device having the same.

In general, an organic light emitting diode such as an organic light emitting diode is a light emitting device that emits light by itself without the need for an external light source. However, as a gas such as oxygen is introduced into the light emitting device, the electrode is oxidized or the device itself deteriorates, the lifespan is shortened, and the light emitting luminance, light emitting efficiency and light emitting uniformity are gradually deteriorated. In order to prevent these problems, various techniques for sealing the organic light emitting device to suppress contact between moisture and oxygen are being studied.

For example, a barrier film structure having an aluminum thin layer on a substrate has been tried. However, although such a structure can obtain a stable gas barrier function, since the aluminum foil layer is provided as a barrier layer, incineration ability is inferior, and there existed a problem that disposal after use was not easy. Moreover, since the aluminum foil layer is provided, there also existed a problem that the barrier film structure which has transparency cannot be obtained.

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

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

Korean Patent Publication No. 2010-0056421

The present invention is to solve various problems including the above problems, effectively preventing the inflow of moisture or oxygen in the atmosphere, while at the same time improving permeability and bending resistance, a barrier film structure and an organic electronic device having the same intended to provide However, these problems are exemplary, and the scope of the present invention is not limited thereto.

A barrier film structure according to an 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, a metal layer in contact with at least one surface of the barrier layer, and a silicon oxide (SiO _x ) layer in contact with at least one surface of the metal layer. includes For example, the barrier film structure includes a barrier layer made of a base film, a silicon oxide layer on the base film, a metal layer on the silicon oxide layer, and an inorganic compound on the metal layer.

In the barrier film structure, the metal layer may be a thin film layer made of gold (Au), silver (Ag), or copper (Cu). The metal layer may have a thickness of 5 nm to 20 nm.

In the barrier film structure, in the silicon oxide (SiO _x ), x may have a positive real value of 1.3 to 1.9. The silicon oxide layer may have a thickness of 75 nm to 200 nm.

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

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

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 on the base film, forming a metal layer that can be in contact with at least one surface of the barrier layer, and the metal layer. and forming a _{silicon oxide (SiO x} ) layer in contact with at least one surface. For example, the method of manufacturing the barrier film structure includes providing a base film, forming a silicon oxide layer on the base film, forming a metal layer on the silicon oxide layer, and an inorganic compound on the metal layer and forming a barrier layer made of

In the method of manufacturing the barrier film structure, the forming of the silicon oxynitride layer, the forming of the metal layer, and the forming of the barrier 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 above-described barrier film structure.

According to an embodiment of the present invention made as described above, it is possible to provide a barrier film structure having improved light transmittance and bending resistance while effectively preventing the inflow of moisture or oxygen in the atmosphere, and an organic electronic device having the same. 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 according to 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 graph showing light transmittance in a visible ray region according to a change in thickness of a silver (Ag) thin film.
4 is a diagram illustrating a cross-section of a barrier film structure according to another embodiment of the present invention.
5 is a diagram illustrating a cross-section of a barrier film structure according to another embodiment of the present invention.
6 is a cross-sectional view schematically illustrating a portion of an organic light emitting 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 moisture or oxygen from entering the atmosphere. The barrier film structure includes a base film, a silicon oxide (SiO _x ) layer, a transparent metal layer, and a barrier layer made of an inorganic compound. The metal layer may be disposed to be in contact with at least one surface of the barrier layer in order to supplement the ductility and malleability of the barrier layer. The silicon oxide layer may be disposed to be in contact with at least one surface of the metal layer in order to supplement light transmittance of the metal layer.

The barrier layer may include a single layer or a plurality of stacked layers including at least one selected from the group consisting of silicon nitride, silicon oxynitride, aluminum oxide, aluminum nitride, and aluminum oxynitride. For example, the barrier layer may be a single layer made of silicon nitride, silicon oxynitride, aluminum oxide, aluminum nitride, or aluminum oxynitride, or a plurality of layers in which silicon oxynitride/silicon nitride/silicon oxynitride are sequentially stacked. .

The barrier layer comprising a thin film made of an inorganic compound such as silicon nitride or aluminum oxide is attached and formed on a substrate by vacuum deposition, there is no environmental problem at the time of disposal, and there is also no dependence on humidity for gas barrier properties, so it is conventionally used It can overcome the problems of polyvinylidene chloride (PVDC) or ethylene-vinyl alcohol copolymer (EVOH).

However, since the barrier layer including a thin film made of an inorganic compound such as silicon nitride or aluminum oxide is deposited on a substrate with inorganic particles, there is a gap called a grain boundary between the inorganic particles, so that the gas barrier function of the thin film is not sufficient. not. Therefore, it is necessary to form the barrier layer made of the inorganic compound as thick as, for example, about 500 angstroms to about 1000 angstroms. However, when the thickness of the barrier layer made of the inorganic compound is increased, it is accompanied by another problem that cracks easily occur due to poor ductility.

In the barrier film structure according to the technical idea of the present invention, the ductility of the barrier layer made of an inorganic compound is supplemented by introducing a transparent metal layer having ductility. Furthermore, the metal layer may also contribute to a barrier property that prevents the inflow of moisture or oxygen in the atmosphere.

However, since the metal layer is disadvantageous in terms of light transmittance, it is preferable to have a thickness thin enough to transmit light. For example, the metal layer is a thin film layer made of gold (Au), silver (Ag), or copper (Cu), and may have a thickness of, for example, 5 nm to 15 nm.

However, even if the thickness of the metal layer is thinned to a nano size and configured to be transparent, the light transmittance appears to be less than 80%, so in the barrier film structure according to the technical idea of the present invention, silicon oxide (SiO _{x ) in contact with at least one surface of the metal layer} ) layer to complement the light transmittance of the metal layer.

The present inventors have confirmed that, in the silicon oxide (SiO _x ) layer, when x has a positive real value of 1.3 to 1.9, it is advantageous to improve the above-described light transmittance. For example, when x has a value of 1.8 in a silicon oxide (SiO _x ) layer, it is advantageous to improve light transmittance. On the other hand, there is not much difference in light transmittance within the range where x is above, but the deposition rate of the silicon oxide having the composition in which x is 1.3 is about 2 times higher than that of the silicon oxide having the composition in which x is 1.9. As it was confirmed, the case where x is 1.3 may be advantageous in terms of film-forming speed.

Furthermore, it was confirmed that when the thickness of the silicon oxide layer having the above composition was 75 nm to 200 nm, the improvement in light transmittance was remarkable. Strictly, when the thickness of the silicon oxide layer is 100 nm to 130 nm, the improvement of the light transmittance becomes more remarkable.

The barrier film structure according to the embodiments of the present invention can implement barrier properties that simultaneously improve ductility and light transmittance by introducing a transparent metal layer and a silicon oxide layer separately from the barrier layer made of an inorganic compound.

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

Hereinafter, examples are provided to help the understanding of the present invention.

The embodiments of the present invention are provided to more completely explain the present invention to those of ordinary skill in the art, and the following examples may be modified in various other forms, and the scope of the present invention is as follows It is not limited to an Example. Rather, these embodiments are provided so as to more fully and complete the present disclosure, and to fully convey the spirit of the present invention to those skilled in the art. In addition, in the drawings, the thickness or size of each layer is exaggerated for convenience and clarity of description.

Like numbers refer to like elements throughout. As used herein, the term “and/or” includes any one and all combinations of one or more of those listed items. The terminology used herein is used to describe specific embodiments, not to limit the present invention. As used herein, the singular form may include the plural form unless the context clearly dictates otherwise. Also, the expression "comprise" as used herein specifies the presence of the recited shapes, numbers, steps, actions, members, elements, and/or groups of these, and includes one or more other shapes, numbers, and numbers. , does not exclude the presence or addition of acts, members, elements and/or groups.

Throughout the specification, when it is stated that one component, such as a film, region, or substrate, is disposed "on" another component, the one component is directly bonded "on" the other component, or in between. It may be construed that there may be other components intervening in the . On the other hand, when it is stated that one element is located "directly on" another element, it is construed that other elements interposed therebetween do not exist.

In the drawings, variations of the illustrated shape can be expected, for example depending on manufacturing technology and/or tolerances. Accordingly, embodiments of the present invention should not be construed as limited to the specific shape of the region shown herein, but should include, for example, changes in shape caused by manufacturing.

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

1 is a diagram illustrating a cross-section 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.

1 and 2 , in the method of manufacturing the barrier film structure 100 according to an embodiment of the present invention, providing a base film 110 ( S110 ), a silicon oxide layer on the base film 110 . Forming 120 (S120), forming the metal layer 130 on the silicon oxide layer 120 (S130), forming the barrier layer 140 on the metal layer 130 (S140) may include

The barrier film structure 100 implemented by this is a transparent film structure in which the base film 110 , the silicon oxide layer 120 , the metal layer 130 , and the barrier layer 140 are sequentially stacked.

The barrier layer 140 may include a single layer or a plurality of stacked layers including at least one selected from the group consisting of silicon nitride, silicon oxynitride, aluminum oxide, aluminum nitride, and aluminum oxynitride.

For example, the barrier layer 140 may be a single layer made of silicon nitride, silicon oxynitride, aluminum oxide, aluminum nitride, or aluminum oxynitride, or a plurality of layers in which silicon oxynitride/silicon nitride/silicon oxynitride are sequentially stacked. can

In order to strengthen the barrier properties of the barrier layer 140 made of an inorganic compound, an increase in the thickness of the barrier layer 140 is inevitably required. In order to compensate for the problem of ductility deterioration accompanying an increase in the thickness of the barrier layer 140 , the metal layer 130 disposed adjacent to the barrier layer 140 is provided. The metal layer 130 may be, for example, a thin film layer made of gold (Au), silver (Ag), or copper (Cu).

Since the metal layer 130 has excellent ductility and malleability, the malleability of the barrier layer 140 may be supplemented, and may also contribute to a barrier property preventing moisture or oxygen from entering the atmosphere. However, since the metal layer 130 is disadvantageous in terms of light transmittance, it is preferable to have a thickness thin enough to transmit light.

3 is a graph showing light transmittance in a visible ray region according to a change in thickness of a silver (Ag) thin film.

Referring to FIG. 3 , as the thickness of the silver thin film decreases from 40 nm to 5 nm, it can be seen that the light transmittance in the visible ray region tends to be higher, but the light transmittance is generally less than 80%. In particular, when the thickness of the silver thin film is 20 nm or more, there is a problem in that the light transmittance is lowered to 20% or less according to the wavelength of visible light.

Accordingly, when the metal layer 130 is introduced into the barrier film structure 100 , the thickness of the metal layer 130 may be preferably 5 nm to 15 nm. When the thickness of the metal layer 130 is less than 5 nm, it is advantageous in terms of light transmittance, but there is little effect of supplementing the ductility of the barrier layer 140, and when the thickness of the metal layer 130 exceeds 15 nm, the barrier layer ( 140) is advantageous in terms of complementing the ductility, but there is a problem in that the light transmittance is significantly lowered.

However, even if the thickness of the metal layer 130 is thinned to a nano size and configured to be transparent, as shown in FIG. 3 , the light transmittance appears to be less than 90%, so in the barrier film structure 100 according to the technical idea of the present invention, The light transmittance of the metal layer 130 is supplemented by introducing the silicon oxide layer 120 in contact with the metal layer.

The present inventors have confirmed that, in the silicon oxide (SiO _x ) layer, when x has a positive real value of 1.3 to 1.9, it is advantageous to improve the above-described light transmittance. For example, when x has a value of 1.8 in the silicon oxide (SiO _x ) layer, it may be advantageous to improve light transmittance.

In addition, it was confirmed that when the thickness of the silicon oxide layer 120 having the above composition was 75 nm to 200 nm, the improvement in light transmittance was remarkable. Strictly, when the thickness of the silicon oxide layer 120 is 100 nm to 130 nm, the improvement of the light transmittance becomes more remarkable. For example, it was confirmed that when the thickness of the silicon oxide layer 120 was 100 nm, the light transmittance in the visible ray region was about 97% or more.

Base film 110 is a cyclic olefin polymer (COP, cyclic olefin polymer) film, polyethylene terephthalate (PET, polyethyleneterephthalate) film, polyethylene naphthalate (PEN, polyethylenenaphthalate) film and a group consisting of a polycarbonate (PC, polycarbonate) film Any single film selected from or may be a multilayer film in which at least two or more films selected from the group are laminated. The base film 110 may be understood as a transparent substrate replacing the glass substrate.

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

Meanwhile, the above-described silicon oxide layer 120 , the metal layer 130 , and the barrier layer 140 may be formed by a sputtering process. For example, the silicon oxide layer 120 may be formed on the substrate by a reactive sputtering process in which oxygen gas is injected into a silicon target.

Therefore, the barrier film structure 100 according to an embodiment of the present invention can be implemented by performing film formation in a vacuum chamber only with an inorganic compound without using an organic material on the base film 110, so that manufacturing costs can be reduced. 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.

4, the barrier film structure 100 according to another embodiment of the present invention is a film in which a base film 110, a barrier layer 140, a metal layer 130, and a silicon oxide layer 120 are sequentially stacked. is a structure That is, a structure in which the metal layer 130 is formed on the upper surface of the barrier layer 140 and the silicon oxide layer 120 is formed on the upper surface of the metal layer 130 . A detailed description of each of the components overlaps with those described with reference to FIGS. 1 to 3 , and thus will be omitted herein.

According to the barrier film structure 100 according to another embodiment of the present invention, the metal layer 130 is disposed in contact with the barrier layer 140 to supplement the ductility of the barrier layer 140, the silicon oxide layer 120 ) may be disposed in contact with the metal layer 130 to supplement the light transmittance of the metal layer 130 .

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

Referring to FIG. 5 , the barrier film structure 100 according to another embodiment of the present invention includes a base film 110 , a silicon oxide layer 120 , a metal layer 130 , a barrier layer 140 , and a metal layer 130 . , a film structure in which the silicon oxide layer 120 is sequentially stacked. That is, it is a structure in which the metal layer 130 in contact with the upper and lower surfaces of the barrier layer 140 is formed, and the silicon oxide layer 120 is formed so as to be in contact with one surface of the metal layer 130 . A detailed description of each of the components overlaps with those described with reference to FIGS. 1 to 3 , and thus will be omitted herein.

According to the barrier film structure 100 according to another embodiment of the present invention, since the metal layer 130 is disposed in contact with both surfaces of the barrier layer 140, respectively, the ductility of the barrier layer 140 can be more effectively supplemented. , the silicon oxide layer 120 is disposed in contact with each metal layer 130 to effectively supplement the light transmittance of the metal layer 130 .

The above-described 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), which will be described below.

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

Referring to FIG. 6 , 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 are stacked thereon. 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 exemplary and can be modified.

On the other hand, the barrier film structure 100 shown in FIG. 6 may correspond to an upside-down state of the barrier film structure 100 shown in FIGS. 1, 4 or 5 . For example, when the barrier film structure 100 shown in FIG. 1 is applied to the organic light emitting diode 200 , the barrier layer 140 is disposed directly on the light transmissive cathode 240 , and the barrier layer 140 ) on the metal layer 130 , the silicon oxide layer 120 , and the base film 110 may be sequentially disposed.

Recently, in order to apply an organic light emitting diode (OLED) to a flexible display device, the demand for securing the flexibility of components constituting the organic light emitting diode 200 is increasing. By doing so, the barrier film structure 100 as an encapsulant, which has improved bending resistance and improved light transmittance by including the above-described silicon oxide layer 120, is expected to be able to expand the application range of organic light emitting diodes (OLEDs). do.

On the other hand, it is expected that the barrier film structure 100 according to the embodiments of the present invention can be applied not only to the organic light emitting device but also to the organic solar cell. In other words, the back sheet located at the rearmost side of the solar cell module is generally not only mechanical strength, but also structures such as solar cells that are vulnerable to moisture located inside the solar cell module from external factors such as oxygen, moisture, and chemicals. A function to protect is required, and it is expected that the above-described barrier film structure 100 can be applied to the back sheet.

Although the present invention has been described with reference to the embodiments shown in the drawings, which are merely exemplary, those skilled in the art will understand that various modifications and equivalent other embodiments are possible therefrom. Therefore, the true technical protection scope of the present invention should be determined by the technical spirit of the appended claims.

100: barrier film structure
110: base film
120: silicon oxide layer
130: metal layer
140: barrier layer
200: organic light emitting diode

Claims (11)

base film;
a barrier layer formed of an inorganic compound disposed on the base film;
a metal layer in contact with at least one surface of the barrier layer; and
_{a silicon oxide (SiO x} ) layer in contact with at least one surface of the metal layer;
including,
The barrier layer is a single layer or a plurality of stacked layers including at least one selected from the group consisting of silicon nitride, silicon oxynitride, aluminum oxide, aluminum nitride, and aluminum oxynitride. The method of claim 1,
The metal layer is a thin film layer made of gold (Au), silver (Ag) or copper (Cu), a barrier film structure. The method of claim 1,
The metal layer has a thickness of 5 nm to 15 nm, a barrier film structure. The method of claim 1,
In the silicon oxide (SiO _x ) layer, x has a positive real value of 1.3 to 1.9, a barrier film structure. The method of claim 1,
The silicon oxide layer has a thickness of 75 nm to 200 nm, a barrier film structure. The method of claim 1,
The base film is at least one selected from a cyclic olefin polymer (COP) film, a polyethyleneterephthalate (PET) film, a polyethylenenaphthalate (PEN, polyethylenenaphthalate) film, and a polycarbonate (PC, polycarbonate) film A barrier film structure comprising a. delete An organic electronic device comprising the barrier film structure according to any one of claims 1 to 6. 9. The method of claim 8,
The organic electronic device includes an organic light emitting diode (OLED) or an organic solar cell (OPV). providing a base film;
forming a barrier layer made of an inorganic compound on the base film;
forming a metal layer in contact with at least one surface of the barrier layer; and
_{forming a silicon oxide (SiO x} ) layer in contact with at least one surface of the metal layer;
including,
The barrier layer is a single layer or a plurality of stacked layers including at least one selected from the group consisting of silicon nitride, silicon oxynitride, aluminum oxide, aluminum nitride and aluminum oxynitride. Method of manufacturing a barrier film structure. 11. The method of claim 10,
The forming of the silicon oxide layer, the forming of the metal layer, and the forming of the barrier layer are performed by a sputtering process, a method of manufacturing a barrier film structure.

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