KR102345793B1 - Barrier film structure and organic electronic device having the same - Google Patents

Abstract

The present invention relates to a barrier film structure with improved bending resistance while effectively preventing the inflow of moisture or oxygen in the atmosphere, and an organic electronic device having the same, and relates to a base film, a barrier layer disposed on the base film and made of an inorganic compound _{and a silicon oxynitride layer (Si x} O _y N _z ) formed on at least one of an upper surface and a lower surface of the barrier layer in order to improve the bending resistance of the barrier layer, wherein x, y and z are A barrier film structure having a positive real value and satisfying all of Equations 1 to 3 at the same time is provided.
[Equation 1]
2/3 < (y+z)/(x+y+z) < 1
[Equation 2]
1/3 < y/(x+y+z) < 1
[Equation 3]
1/3 < z/(x+y+z) < 1

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, and at the same time providing a barrier film structure with improved bending resistance and an organic electronic device having the same aim to 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 formed on the base film and made of an inorganic compound, and a silicon acid formed on at least one of an upper surface and a lower surface of the barrier layer in order to improve bending resistance of the barrier layer. and a nitride layer (Si _x O _y N _z ). The silicon oxynitride layer is characterized in that it is a silicon oxynitride layer in which x, y, and z have positive real values, and all of the following Equations 1 to 3 are satisfied.

[Equation 1]

2/3 < (y+z)/(x+y+z) < 1

[Equation 2]

1/3 < y/(x+y+z) < 1

[Equation 3]

1/3 < z/(x+y+z) < 1

In the barrier film structure, the silicon oxynitride layer is formed on a lower surface of the barrier layer, a first silicon oxynitride layer interposed between the base film and the barrier layer, and a second silicon formed on the upper surface of the barrier layer It may include an oxynitride layer. In this case, a silicon oxide layer formed on the second silicon oxynitride layer may be further included.

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 oxide, silicon nitride, silicon oxynitride, aluminum oxide, and aluminum oxynitride.

A method of manufacturing a barrier film structure according to another aspect of the present invention is provided. The method for manufacturing the barrier film structure includes the steps of providing a base film, forming a barrier layer disposed on the base film and made of an inorganic compound, and upper and lower surfaces of the barrier layer to improve bending resistance of the barrier layer and forming a _{silicon oxynitride layer (Si x} O _y N _z ) satisfying all of Equations 1 to 3 at the same time on at least one surface.

The step of forming the silicon oxynitride layer in the method for manufacturing the barrier film structure includes adding oxygen and nitrogen gas in a supersaturated state into a chamber equipped with a silicon target and forming a silicon oxynitride layer by reactive sputtering. can

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 with improved 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 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.
6 is a view illustrating a composition _{of a silicon oxynitride layer (Si x} O _y N _z ) in the method of manufacturing a barrier film structure according to an embodiment 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 barrier layer formed on the base film and made of an inorganic compound, and a silicon acid formed on at least one of an upper surface and a lower surface of the barrier layer in order to improve bending resistance of the barrier layer. and a nitride layer (Si _x O _y N _z ).

The silicon oxynitride layer (Si _x O _y N _z ) is supersaturated with oxygen and nitrogen so that the ratio of oxygen and nitrogen constituting the silicon oxynitride layer is higher than a typical stoichiometric ratio. Specifically, in the silicon oxynitride layer, x, y, and z have positive real values, and all of the following Equations 1 to 3 are simultaneously satisfied.

[Equation 1]

2/3 < (y+z)/(x+y+z) < 1

[Equation 2]

1/3 < y/(x+y+z) < 1

[Equation 3]

1/3 < z/(x+y+z) < 1

The inventors have found that the silicon oxynitride layer supersaturated with oxygen and nitrogen is softer and less cracked than a conventional silicon oxynitride layer, and the silicon acid on at least one side of the barrier layer When the nitride layer was disposed, it was confirmed that the bending resistance of the barrier film structure including the barrier layer was remarkably improved.

6 is a view illustrating a composition _{of a silicon oxynitride layer (Si x} O _y N _z ) in the method of manufacturing a barrier film structure according to an embodiment of the present invention.

delete

In some embodiments of the present invention, the silicon oxynitride layer having a light transmittance of 91% or more was implemented by a reactive sputtering process in which nitrogen gas and oxygen gas were added to a supersaturated state using a silicon target.

Meanwhile, 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 oxide, silicon oxynitride, silicon nitride, and aluminum oxide. For example, the barrier layer may be a single layer made of silicon oxide, silicon oxynitride, silicon nitride, or aluminum oxide, or a plurality of layers in which silicon oxide/silicon nitride/silicon oxide are sequentially stacked. In particular, when the barrier layer includes a silicon oxynitride layer, the ratio of oxygen and nitrogen in the composition of silicon oxynitride constituting the barrier layer has a conventional stoichiometric ratio, so it is a composition that is not supersaturated. should understand

The barrier layer comprising a thin film made of an inorganic compound such as silicon oxide 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 oxide 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 thick, for example, about 500 to 1000 angstroms. However, when the thickness of the barrier layer is increased, it is accompanied by another problem that cracks easily occur due to poor ductility.

In the barrier film structure according to the embodiments of the present invention, by disposing a silicon oxynitride layer supersaturated with oxygen and nitrogen on at least one surface of the upper surface and the lower surface of the barrier layer, a barrier film with improved bending resistance can be implemented. can be expected

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, the step of providing the base film 110 ( S110 ), the first silicon on the base film 110 . Forming an oxynitride layer (120a) (S120), forming a barrier layer 130 on the first silicon oxynitride layer (120a) (S130), a second silicon oxynitride on the barrier layer (130) Forming the layer 120b (S140) may be included. Furthermore, the method may further include forming a silicon oxide layer 150 on the second silicon oxynitride layer 120b ( S150 ).

For example, the step of forming the first silicon oxynitride layer 120a ( S120 ) and the step of forming the second silicon oxynitride layer 120b ( S140 ) may include oxygen and nitrogen gas in a vacuum chamber in which a silicon target is mounted. It can be implemented by adding up to a supersaturated state and using a reactive sputtering process. Furthermore, the step of forming the silicon oxide layer 150 ( S150 ) may also be implemented by a sputtering process.

The barrier film structure 100 implemented thereby includes the base film 110 , the first silicon oxynitride layer 120a , the barrier layer 130 , the second silicon oxynitride layer 120b and the silicon oxide layer 150 . It is a transparent film structure laminated sequentially.

_{The silicon oxynitride layer Si x} O _y N _z including the first silicon oxynitride layer 120a and the second silicon oxynitride layer 120b has a composition in which oxygen and nitrogen are supersaturated, for example, It has a composition that satisfies all of Equations 1 to 3 at the same time. According to an embodiment of the present invention, by forming the silicon oxynitride layer 120 having the above-described composition on the upper surface and the lower surface of the barrier layer 130, respectively, the bending resistance of the barrier layer 130 is supplemented, and the ductility is remarkable. It is possible to implement an improved barrier film structure.

On the other hand, the silicon oxynitride layer 120 having a composition in which oxygen and nitrogen are supersaturated has relatively few cracks, but the film quality is soft and thus the surface exposed to the outside is easily damaged. Accordingly, the surface of the second silicon oxynitride layer 120b may be protected from scratches by additionally forming the silicon oxide layer 150 on the second silicon oxynitride layer 120b.

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 is a transparent substrate replacing the glass substrate and has flexibility.

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

The barrier layer 130 may be a single layer or a plurality of stacked layers including at least one selected from the group consisting of silicon oxide, silicon nitride, silicon oxynitride, and aluminum oxide.

For example, the barrier layer 130 may be a single layer made of silicon oxide, silicon oxynitride, silicon nitride, or aluminum oxide, or a plurality of layers in which silicon oxide/silicon nitride/silicon oxide are sequentially stacked. In particular, when the barrier layer 130 includes a silicon oxynitride layer, the ratio of oxygen and nitrogen in the composition of the silicon oxynitride constituting the barrier layer 130 has a typical stoichiometric ratio. It should be understood that the composition is not supersaturated.

Since the barrier layer 130 including a thin film made of an inorganic compound such as silicon oxide or aluminum oxide is deposited on a substrate, 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. It may not be possible, and it is necessary to form a thickness of, for example, about 500 to 1000 Å thick. However, when the thickness of the barrier layer 130 is increased, the ductility is deteriorated and cracks are likely to occur.

In the barrier film structure 100 according to an embodiment of the present invention, bending resistance is improved by disposing the silicon oxynitride layer 120 supersaturated with oxygen and nitrogen on at least one of the upper and lower surfaces of the barrier layer 130 . The effect of implementing an improved barrier film can be expected.

Furthermore, 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 the manufacturing cost can be reduced. effect can be expected.

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

Referring to FIG. 3 , the barrier film structure 100 according to another embodiment of the present invention includes a base film 110 , a barrier layer 130 , a second silicon oxynitride layer 120b and a silicon oxide layer 150 . It is a sequentially laminated film structure. That is, it is a structure in which the silicon oxynitride layer 120b is formed only on the upper surface of the barrier layer 130 . A detailed description of each of the components overlaps with those described with reference to FIGS. 1 and 2 , and thus will be omitted herein.

The second silicon oxynitride layer 120b, having a composition in which oxygen and nitrogen are supersaturated, has, for example, a composition that simultaneously satisfies Equations 1 to 3 above. A silicon oxynitride layer having the above composition is formed on the upper surface of the barrier layer 130 to supplement the bending resistance of the barrier layer 130 to improve the bending resistance of the barrier film structure 100 .

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 structure in which the base film 110, the first silicon oxynitride layer 120a, and the barrier layer 130 are sequentially stacked. to be. That is, it is a structure in which the silicon oxynitride layer 120a is formed only on the lower surface of the barrier layer 130 . A detailed description of each of the components overlaps with those described with reference to FIGS. 1 and 2 , and thus will be omitted herein.

The first silicon oxynitride layer 120a having a composition in which oxygen and nitrogen are supersaturated has, for example, a composition that simultaneously satisfies Equations 1 to 3 above. A silicon oxynitride layer having the above composition is formed on the lower surface of the barrier layer 130 to supplement the bending resistance of the barrier layer 130 to improve the bending resistance of the barrier film structure 100 .

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.

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

On the other hand, the barrier film structure 100 shown in FIG. 5 may correspond to the upside-down state of the barrier film structure 100 shown in FIGS. 1, 3 or 4 . For example, when the barrier film structure 100 shown in FIG. 1 is applied to the organic light emitting diode 200 , the silicon oxide layer 150 is disposed directly on the light-transmitting cathode 240 , and the silicon oxide layer A second silicon oxynitride layer 120b, a barrier layer 130, a first silicon oxynitride layer 120a, and a base film 110 may be sequentially disposed on the 150 .

Recently, in order to apply an organic light emitting diode (OLED) to a flexible display device, the demand for securing flexibility of components constituting the organic light emitting diode 200 is increasing. , 120b), the barrier film structure 100 as an encapsulant having improved bending resistance is expected to expand the application range of the organic light emitting diode (OLED).

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 backmost side of the solar cell module generally has not only mechanical strength but also structures such as solar cells 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
120a, 120b, 120: silicon oxynitride layer
130: barrier layer
150: silicon oxide layer
200: organic light emitting diode

Claims (9)

base film;
a barrier layer disposed on the base film and made of an inorganic compound; and
In order to improve the flex resistance of the barrier layer at least a silicon oxynitride layer formed on any one surface (Si _x O _y N _z) of the upper and lower surfaces of the barrier layer, and including,
The silicon oxynitride layer is a silicon oxynitride layer that is supersaturated with oxygen and nitrogen, wherein x, y, and z have positive real values and satisfy all of the following Equations 1 to 3 simultaneously. film structure.
[Equation 1]
2/3 < (y+z)/(x+y+z) < 1
[Equation 2]
1/3 < y/(x+y+z) < 1
[Equation 3]
1/3 < z/(x+y+z) < 1 The method of claim 1,
The silicon oxynitride layer may include a first silicon oxynitride layer formed on a lower surface of the barrier layer and interposed between the base film and the barrier layer; and a second silicon oxynitride layer formed on an upper surface of the barrier layer. 3. The method of claim 2,
Further comprising a silicon oxide layer formed on the second silicon oxynitride layer, barrier film structure. The method of claim 1,
The base film is any one selected from a cyclic olefin polymer (COP, cyclic olefin polymer) film, a polyethyleneterephthalate (PET, polyethyleneterephthalate) film, a polyethylenenaphthalate (PEN, polyethylenenaphthalate) film, and a polycarbonate (PC, polycarbonate) film. A barrier film structure comprising: The method of claim 1,
The barrier layer is a single layer or a plurality of laminated layers including at least one selected from the group consisting of silicon oxide, silicon nitride, and aluminum oxide, the barrier film structure. An organic electronic device comprising the barrier film structure according to any one of claims 1 to 5. 7. The method of claim 6,
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 disposed on the base film and made of an inorganic compound; and
Forming a _{silicon oxynitride layer (Si x} O _y N _z ) on at least one of the upper and lower surfaces of the barrier layer in order to improve the bending resistance of the barrier layer;
The silicon oxynitride layer is a silicon oxynitride layer that is supersaturated with oxygen and nitrogen, wherein x, y, and z have positive real values, and both Equations 1 to 3 are simultaneously satisfied. A method of manufacturing a film structure.
[Equation 1]
2/3 < (y+z)/(x+y+z) < 1
[Equation 2]
1/3 < y/(x+y+z) < 1
[Equation 3]
1/3 < z/(x+y+z) < 1 9. The method of claim 8,
The step of forming the silicon oxynitride layer; the step of introducing oxygen and nitrogen gas into a chamber equipped with a silicon target and forming a silicon oxynitride layer by reactive sputtering; comprising, a method of manufacturing a barrier film structure.

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