KR20160020841A - Barrier film structure and organic electronic device having the same - Google Patents

Abstract

The present invention relates to: a barrier film structure which secures long-term reliability, and can effectively prevent inflow of moisture or oxygen from the atmosphere; and an organic electronic device having the same. The barrier film structure comprises: a base film; and a barrier layer which is disposed on the base film, and whose electron affinity is greater than 0 eV and less than 4 eV.

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 the Invention The present invention provides a barrier film structure and an organic electronic device including the barrier film structure, which can effectively prevent moisture and oxygen from entering the atmosphere while securing long-term reliability and at the same time to solve various problems including the above- . 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 and a barrier layer disposed on the base film and having an electron affinity greater than 0 eV and less than 4 eV.

In the barrier film structure, the barrier layer may be made of a material including SiAlON, AlON or SiON.

The barrier film structure may further include a silicon oxynitride layer (Si _x O _y N _z ) formed on at least one of the upper surface and the lower surface of the barrier layer to improve the bending resistance of the barrier layer . Wherein x, y, and z in the silicon oxynitride layer have positive real valued values and satisfy the following relationship: < EMI ID = 1.0 &gt; 3 <y / (x + y + z) <1 and Equation 3: 1/3 <z / (x + y + z) <1.

The barrier film structure has at least one surface and the tangent of the barrier layer, a gold (Au), silver (Ag) or copper (Cu) metal layer and a silicon oxide (SiO _x) in contact with at least one surface of the metal layer made of a layer As shown in FIG. In the silicon oxide (SiO _x ) layer, x may have a positive real value of 1.5 to 1.9.

The upper surface of the barrier layer in the barrier film structure may be argon plasma treated or helium and argon plasma treated.

The barrier film structure may further include at least one titanium oxide (TiO _x ) layer disposed on the base film. In the titanium oxide layer, x may be greater than 0.1 and less than 2.

The barrier film structure may further include at least one layer of a silicon oxide (SiO _x ) layer facing at least one surface of the barrier layer to relieve stress generated in the barrier layer. The value of x in the silicon oxide (SiO _x ) layer may range from 1.5 to 1.9.

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 and an organic electronic device including the barrier film structure, which can effectively prevent moisture and oxygen from entering the atmosphere while ensuring long-term reliability. Of course, the scope of the present invention is not limited by these effects.

1 is a cross-sectional view 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 SiAlON material capable of forming a barrier layer in a barrier film structure according to embodiments of the present invention.
4 is a cross-sectional view illustrating a cross-section of a barrier film structure according to another embodiment of the present invention.
5 is a cross-sectional view illustrating a cross-section of a barrier film structure according to another embodiment of the present invention.
6 is a cross-sectional view illustrating a cross-section of a barrier film structure according to another embodiment of the present invention.
7 is a cross-sectional view illustrating a cross-section of a barrier film structure according to another embodiment of the present invention.
8 is a cross-sectional view illustrating a cross-section of a barrier film structure according to another embodiment of the present invention.
9 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 has a base film and a barrier layer disposed on the base film and having an electron affinity greater than 0 eV and less than 4 eV.

The present inventors have found that when the electron affinity of the barrier layer is greater than 0 eV and less than 4 eV, the barrier layer has stability to temperature and humidity and long-term reliability to the barrier property. Such a barrier layer may be made of a material including SiAlON, AlON or SiON.

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. It 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 &quot; transparent &quot; 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. As used herein, the term "electron affinity" refers to the energy required to remove electrons from a monovalent anion of an atom or molecule.

FIG. 1 is a cross-sectional view illustrating a cross-section of a barrier film structure according to an embodiment of the present invention, FIG. 2 is a flowchart illustrating a method of manufacturing a barrier film structure according to an embodiment of the present invention, Lt; RTI ID = 0.0 &gt; SiAlON &lt; / RTI &gt; material capable of forming a barrier layer in a barrier film structure according to embodiments of the present invention.

Referring to FIGS. 1 to 3, 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 planarization layer Forming a barrier layer 130 on the planarization layer 120, wherein the barrier layer 130 comprises an SiAlON layer having an electron affinity greater than 0 eV and less than 4 eV (step S30) . The SiAlON layer constituting the barrier layer 130 may be replaced with, for example, an AlON layer or a SiON layer.

 The base film 110 may be formed of a material selected from the group consisting of a cyclic olefin polymer (COP) film, a cyclic olefin copolymer (COC) film, a polyether sulfone (PES) film, a polyethylene terephthalate (PET) a single layer film selected from the group consisting of polyethyleneterephthalate (PEN), polyethylenenaphthalate (PEN) film and polycarbonate (PC) polycarbonate, or a multilayer film in which at least two films selected from the above group are laminated. The base film 110 has ductility 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.

The planarization layer 120 is formed directly on the base film 110 so that the barrier layer 130 on the base film 110 can be uniformly deposited by the planarization layer 120. For example, the planarization layer 120 may be formed by coating an acrylate with a microgravure coater or a bar coater.

The barrier film structure 100 thus constructed includes a structure in which a barrier film 130 composed of a base film 110, a planarization layer 120 and a SiAlON layer are sequentially arranged. The SiAlON material shown in FIG. 3 is a material having a relatively low electron affinity and has stability to a temperature and a humidity, thereby securing long-term reliability in the barrier property of the barrier film. Particularly, in the case of a flexible electronic device that can be highly exposed to the external environment, long-term reliability can have an important meaning, and therefore, an advantageous effect can be expected when the barrier film structure 100 according to an embodiment of the present invention is applied . The barrier layer 130 comprised of the SiAlON layer may be formed by a physical vapor deposition process such as a chemical vapor deposition process or reactive sputtering.

Although not shown in the drawing, in the barrier film structure 100 according to the modified embodiment of the present invention, the unit laminate composed of the planarization layer 120 and the barrier layer 130 composed of the SiAlON layer is repeatedly formed . In this case, since the unit laminate is repeatedly arranged, the long-term reliability can be further improved.

Hereinafter, modified embodiments of the barrier film structure 100 disclosed in FIG. 1 will be described. Therefore, the description of the constituent elements having the same reference numerals as those of the constituent elements shown in Fig. 1 is omitted because they are the same as those described above.

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

Referring to FIG. 4, the barrier film structure 100 according to another embodiment of the present invention may be formed on at least one of the upper surface and the lower surface of the barrier layer 130 in order to improve the bending resistance of the barrier layer 130 And a silicon oxynitride layer 140 formed thereon.

Since the barrier layer 130 comprising a thin film made of an inorganic compound such as SiAlON, AlON or SiON is deposited on a substrate, there is a gap called a grain boundary between the inorganic particles and the gas barrier function of the thin film is not sufficient And it is necessary to form the thickness to be as thick as, for example, 500 to 1000 ANGSTROM. However, if the thickness of the barrier layer 130 is increased, the spreadability of the barrier layer 130 is lowered, and cracks tend to occur.

In the barrier film structure 100 according to the modified embodiment of the present invention, the silicon oxynitride layer 140 in which oxygen and nitrogen are supersaturated is disposed on at least one of the upper and lower surfaces of the barrier layer 130, It is possible to expect the effect that the improved barrier film can be realized.

The present inventors have found that when oxygen and nitrogen are supersaturated such that the ratio of oxygen to nitrogen constituting the silicon oxynitride layer in the silicon oxynitride layer 140 is higher than a typical stoichiometric ratio, This remarkable improvement was confirmed. More specifically, in the silicon oxynitride layer (Si _x O _y N _z , 140), x, y and z have positive real numbers and satisfy all of the following equations (1) to have.

[Equation 1]

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

&Quot; (2) &quot;

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

&Quot; (3) &quot;

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

The present inventors have found that the oxygen and nitrogen supersaturated silicon oxynitride layer 140 is less cracked and soft than a conventional silicon oxynitride layer and is more flexible than at least one surface of the barrier layer 130 The bending resistance of the barrier film structure 100 including the barrier layer 130 is remarkably improved when the silicon oxynitride layer 140 is disposed on the barrier film structure 100.

In some embodiments of the present invention, a silicon oxynitride layer 140 having a light transmittance of 91% or more is formed by a reactive sputtering process in which nitrogen gas and oxygen gas are introduced into a supersaturated state using a silicon target. That is, since the barrier film structure 100 according to the modified embodiment of the present invention can be formed by performing film formation in a vacuum chamber using only an inorganic compound without using an organic substance on the base film 110, The effect can be expected.

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

Referring to FIG. 5, a barrier film structure 100 according to another embodiment of the present invention includes at least one surface of barrier layer 130, which is made of gold (Au), silver (Ag), or copper (Cu) And a silicon oxide layer 150 in contact with at least one surface of the metal layer 160 and the metal layer 160. In the silicon oxide layer 150 having the formula SiO _x , _x may have a positive real number value of 1.5 to 1.9.

An increase in the thickness of the barrier layer 130 is inevitably required to enhance the barrier properties of the barrier layer 130 made of an inorganic compound. A metal layer 160 is disposed adjacent to the barrier layer 130 to compensate for the lowering of the tortuosity that is accompanied by an increase in the thickness of the barrier layer 130. The metal layer 160 may be a thin film layer made of, for example, gold (Au), silver (Ag), or copper (Cu).

Since the metal layer 160 is excellent in ductility and electrical conductivity, the metal layer 160 can supplement the barrier properties of the barrier layer 130 and also contribute to barrier properties that prevent moisture and oxygen from entering the atmosphere. However, since the metal layer 160 is disadvantageous from the viewpoint of light transmittance, it is preferable that the metal layer 160 has a thickness thin enough to transmit light.

For example, as the thickness of the silver thin film is thinned from 40 nm to 5 nm, the light transmittance in the visible light region is 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 arises a problem that the light transmittance is lowered to 20% or less according to the visible light wavelength.

Therefore, when the metal layer 160 is introduced into the barrier film structure 100, it is preferable that the thickness of the metal layer 160 is 5 nm to 15 nm. When the thickness of the metal layer 160 is less than 5 nm, it is advantageous in terms of light transmittance but has no effect of supplementing the flexibility of the barrier layer 130. When the thickness of the metal layer 160 exceeds 15 nm, 130), it is advantageous in terms of complementary properties, but the light transmittance is remarkably lowered.

In the barrier film structure 100 according to the modified embodiment of the present invention, however, even if the thickness of the metal layer 160 is reduced to a nanosize, the light transmittance is less than 90% The light transmittance of the metal layer 160 is compensated by introducing the silicon oxide layer 150.

The present inventors have confirmed that when the _{x value} in the silicon oxide layer 150 having the formula SiO _x has a positive real number value of 1.5 to 1.9, it is advantageous in improving the light transmittance described above. For example, when _{x in} the silicon oxide (SiO _x ) layer has a value of 1.8, it may be advantageous to improve the light transmittance.

Further, it was confirmed that the improvement in light transmittance was remarkable when the thickness of the silicon oxide layer 150 having the above composition was 50 nm to 200 nm. Strictly, when the thickness of the silicon oxide layer 150 is 100 nm to 130 nm, improvement of light transmittance becomes more remarkable. For example, when the thickness of the silicon oxide layer 150 is 100 nm, it is confirmed that the light transmittance in the visible light region is about 97% or more.

6 is a cross-sectional view illustrating a cross-section of a barrier film structure according to another embodiment of the present invention.

Referring to FIG. 6, in the barrier film structure 100 according to another embodiment of the present invention, the upper surface of the barrier layer 130 may be subjected to argon plasma treatment or helium and argon plasma treatment. That is, the surface of the barrier layer 130 made of an inorganic compound is subjected to a plasma treatment using a mixed gas of helium and argon or using argon gas, thereby improving the surface roughness of the barrier layer 130, increasing the density of the film, The characteristics may be improved.

The plasma treatment may be performed after the barrier layer 130 is formed in advance to a final thickness, but the barrier layer 130 may be partially formed and the plasma treatment may be performed at each step as shown in FIG. 6 . For example, after the first barrier layer 130a is formed and the plasma treatment is performed on the upper surface of the first barrier layer 130a, a second barrier layer 130b is formed on the first barrier layer 130a And the plasma treatment may be performed on the upper surface of the second barrier layer 130b. In this case, the barrier layer 130 is composed of the first barrier layer 130a and the second barrier layer 130b. By performing the plasma treatment stepwise over the entire barrier layer 130, The film density and the moisture permeability characteristics can be remarkably improved.

7 is a cross-sectional view illustrating a cross-section of a barrier film structure according to another embodiment of the present invention.

Referring to FIG. 7, the barrier film structure 100 according to another embodiment of the present invention may further include at least one titanium oxide layer 170 disposed on the base film 110. In the titanium oxide layer 170 having the formula TiO _x , x may be greater than 0.1 and less than 2.

The titanium oxide layer 170 having the above composition can be understood as an oxygen-unsaturated titanium oxide layer in view of the stoichiometric ratio because the proportion of oxygen is relatively lower than that of titanium dioxide (TiO ₂ ) From a different theoretical point of view, titanium can be understood as a supersaturated titanium oxide layer.

The titanium oxide layer 170 having the above composition may serve as a getter for separating oxygen from the oxygen-containing compound to trap the oxygen. In addition, in the titanium oxide layer 170 having the above-described composition, permeation of moisture or oxygen gas is relatively difficult. The titanium oxide layer 170 having the above composition may be formed by physical vapor deposition or chemical vapor deposition, for example, with a thickness of 50 nm or more.

8 is a cross-sectional view illustrating a cross-section of a barrier film structure according to another embodiment of the present invention.

Referring to FIG. 8, a barrier film structure 100 according to another embodiment of the present invention includes at least one barrier layer 130, at least one of which faces at least one side of the barrier layer 130, And may further include a silicon oxide layer 180. For example, the barrier layer 130 composed of the SiAlON layer increases in magnitude of the stress caused as the thickness increases. By arranging the silicon oxide layer 180 on each of the upper and lower surfaces of the barrier layer 130, Can be mitigated.

It has been confirmed that when the value of x is in the range of 1.5 to 1.9 in the silicon oxide layer 180 having the formula SiO _x , the light transmittance is advantageously improved. For example, when the value of n in the silicon oxide (SiO _x ) layer has a value of 1.8, it is advantageous to improve light transmittance. However, the modified embodiment of the present invention is not limited to the composition of the silicon oxide layer 180, for example, the silicon oxide layer 180 having the formula SiO _x , Layer.

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).

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

9, 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. 9 is illustrative and can be modified.

Meanwhile, the barrier film structure 100 shown in FIG. 9 may correspond to a state in which the barrier film structure 100 shown in FIGS. 1 and 4 to 8 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 barrier layer 130 is disposed directly on the light-transmitting cathode 240, and the barrier layer 130 The planarization layer 120 and the base film 110 may be sequentially disposed on the planarization layer 120. [

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: planarization layer
130: barrier layer
140: Silicon oxynitride layer
150, 180: silicon oxide layer
160: metal layer
170: titanium oxide layer
200: organic light emitting diode

Claims (9)

A base film; And
A barrier layer disposed on the base film, the barrier layer having an electron affinity greater than 0 eV and less than 4 eV. The method according to claim 1,
Wherein the barrier layer is comprised of a material comprising SiAlON, AlON or SiON. The method according to claim 1,
And a silicon oxynitride layer (Si _x O _y N _z ) formed on at least one of the upper surface and the lower surface of the barrier layer to improve the bending resistance of the barrier layer,
Wherein x, y, and z in the silicon oxynitride layer have positive real valued values and satisfy all of the following equations (1) to (3) simultaneously.
[Equation 1]
2/3 <(y + z) / (x + y + z) <1
&Quot; (2) &quot;
1/3 <y / (x + y + z) <1
&Quot; (3) &quot;
1/3 &lt; z / (x + y + z) &lt; 1 The method according to claim 1,
A metal layer that is in contact with at least one surface of the barrier layer and is made of gold (Au), silver (Ag), or copper (Cu); And
A silicon oxide (SiO _x ) layer in contact with at least one surface of the metal layer;
Further comprising:
Wherein in the silicon oxide (SiO _x ) layer, x has a positive real value in the range of 1.5 to 1.9. The method according to claim 1,
Wherein the upper surface of the barrier layer is subjected to argon plasma treatment or helium and argon plasma treatment. The method according to claim 1,
At least one titanium oxide (TiO _x ) layer disposed on the base film, wherein x in the titanium oxide layer is greater than 0.1 and less than 2. The method according to claim 1,
Further comprising at least one layer of silicon oxide (SiO _x ) facing at least one side of the barrier layer to relieve stresses induced in the barrier layer,
Wherein the value of x in the silicon oxide (SiO _x ) layer ranges from 1.5 to 1.9. 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).

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