KR102056469B1 - Transparent structure capable of blocking ultraviolet rays and infrared rays - Google Patents

Abstract

The present invention provides a UV blocking film that can block ultraviolet rays by repeatedly stacking first and second thin films having different refractive indices from each other; An infrared blocking film capable of blocking infrared rays; And a transparent barrier film, wherein the ultraviolet blocking film, the infrared blocking film, and the transparent barrier film are disposed in a sequentially stacked form in any order to provide a transparent structure capable of blocking ultraviolet light and infrared light.

Description

Transparent structure capable of blocking ultraviolet rays and infrared rays

The present invention relates to a transparent structure, and more particularly, a transparent structure capable of blocking ultraviolet rays and infrared rays, for example, a transparent passivation structure for organic electronic devices capable of blocking ultraviolet rays and infrared rays, a transparent electrode structure for organic electronic devices Or it relates to a transparent tinting film for a vehicle.

Since organic electronic devices exposed to the outside for a long time are made of reactive gases such as moisture and oxygen, and materials which are very susceptible to ultraviolet rays and heat caused by sunlight, deterioration is easily caused by exposure to such an external environment. Therefore, it is important to apply an encapsulation film or an additional filter to prevent direct exposure from such an external environment in order to manufacture a highly efficient and reliable organic electronic device.

Korean Patent Registration No. 0682963 (Invention name: Organic light emitting display with UV blocking film)

The present invention has been made to solve various problems including the above problems, and an object thereof is to provide a transparent structure that can block light in the ultraviolet and infrared regions and can block moisture and oxygen. However, these problems are exemplary, and the scope of the present invention is not limited thereby.

Provided is a transparent structure that can block ultraviolet rays and infrared rays according to an aspect of the present invention for solving the above problems. The transparent structure capable of blocking ultraviolet rays and infrared rays may include an ultraviolet blocking layer capable of blocking ultraviolet rays by alternately repeatedly stacking a first thin film and a second thin film having different refractive indices; An infrared blocking film capable of blocking infrared rays; And a transparent barrier film, wherein the UV blocking film, the infrared blocking film, and the transparent barrier film are sequentially stacked in any order.

It provides a transparent structure that can block ultraviolet rays and infrared rays according to another aspect of the present invention for solving the above problems. The transparent structure capable of blocking ultraviolet rays and infrared rays may include an ultraviolet blocking layer capable of blocking ultraviolet rays by alternately repeatedly stacking a first thin film and a second thin film having different refractive indices; An infrared blocking film capable of blocking infrared rays; And a transparent conductive electrode, wherein the ultraviolet blocking film, the infrared blocking film, and the transparent conductive electrode are sequentially stacked in any order.

In the transparent structures capable of blocking ultraviolet rays and infrared rays, the first thin film of the UV blocking film may be a ZnS thin film and the second thin film may be a LiF thin film.

In the transparent structures capable of blocking ultraviolet rays and infrared rays, the first thin film and the second thin film of the ultraviolet light blocking film include any one material selected from indium oxide, zinc oxide, tin oxide, indium tin oxide, and indium zinc oxide, respectively. The difference in refractive index between the material constituting the first thin film and the material constituting the second thin film may be at least 0.5.

In the transparent structures capable of blocking the ultraviolet rays and the infrared rays, the ultraviolet blocking layer may be a distributed brag reflector (DBR) filter.

In the transparent structures capable of blocking ultraviolet rays and infrared rays, the infrared ray blocking layer may be a metal thin film including any one material selected from Ag, Au, Cu, and Al.

In the transparent structures capable of blocking the ultraviolet and infrared rays, the transparent barrier film is an aluminum oxide film, aluminum nitride film, silicon oxide, silicon nitride film, silicon oxynitride film, magnesium oxide film, magnesium fluoride film, titanium oxide film, titanium nitride film, hafnium oxide film, hafnium It may be at least one single thin film or a laminated thin film selected from a nitride film, a zirconium oxide film, a zirconium nitride film, a tungsten oxide film, a zinc sulfide film, a zinc oxide film and a yttrium oxide film.

In the transparent structures capable of blocking the ultraviolet and infrared rays, the transparent barrier film includes at least one hybrid unit structure film formed by stacking a stress reducing thin film, a barrier thin film and a moisture absorbing thin film, wherein the stress reducing thin film includes ZnO, SiO ₂ , SiN _x , A thin film including at least one selected from Ag and Al, the barrier thin film is a thin film including at least one of AlN, Al ₂ O ₃ , AlO _x N _y and SnO _x , The hygroscopic thin film is an alkali metal (Li , Na, K, Rb, Cs, Fr), alkaline earth metals (Be, Mg, Ca, Sr, Ba, Ra), Ti, Zr, Hf and may be a thin film comprising at least one material selected from oxides thereof. .

In the transparent structures capable of blocking the ultraviolet rays and infrared rays, the transparent barrier layer is a transparent barrier layer that can improve the transmittance of visible light, and at least one hybrid unit formed by stacking a ZnO thin film, an Al ₂ O ₃ thin film, and an MgO thin film. A structural film can be provided.

In the transparent structures capable of blocking ultraviolet rays and infrared rays, the transparent conductive electrode is based on a metal oxide formed by stacking a plurality of metal oxide unit films by atomic layer deposition (ALD) or chemical vapor deposition (CVD). The substrate may be a transparent conductive electrode doped with a dopant.

In the transparent structures capable of blocking ultraviolet rays and infrared rays, the metal oxide may be at least one of indium oxide, zinc oxide, tin oxide, indium tin oxide, and indium zinc oxide.

In the transparent structures capable of blocking the ultraviolet rays and the infrared rays, the dopant may be doped relatively concentrated in a plurality of unit film stack boundary regions in the substrate.

In transparent structures capable of blocking ultraviolet rays and infrared rays, the dopant may have an amorphous form by inhibiting crystal growth of each unit film.

In the transparent structures capable of blocking the ultraviolet rays and infrared rays, the transparent conductive electrode is based on ZnO formed by stacking a plurality of ZnO unit layers by atomic layer deposition (ALD) or chemical vapor deposition (CVD). At least one of magnesium (Mg) and aluminum (Al) as a dopant therein may be a transparent conductive electrode doped.

The transparent structure capable of blocking ultraviolet rays and infrared rays may be a transparent passivation structure for an organic electronic device.

The transparent structure capable of blocking ultraviolet rays and infrared rays may be a transparent tinting film for a vehicle.

The transparent structure capable of blocking ultraviolet rays and infrared rays may be a transparent electrode structure for an organic electronic device.

According to some embodiments of the present invention made as described above, it is possible to block the light in the ultraviolet and infrared region, and at the same time, the transparent passivation structure for an organic electronic device, a transparent electrode for an organic electronic device, which can block moisture and oxygen. A transparent tinting film for a structure or a vehicle can be implemented. Some embodiments of the present invention are directed to the fabrication of a functional passivation film or electrode capable of blocking ultraviolet rays and infrared rays, and having a high barrier function in order to improve the reliability and stability of the transparent flexible organic electronic device. It can be utilized as an optimized functional film of an organic solar cell or an organic light emitting diode. If existing traditional passivation or electrodes have only performed a barrier or conductivity function against simple moisture and oxygen, the proposed invention provides transparent, low-light simultaneously, selectively blocking harmful light on electronic devices such as UV and infrared. Providing moisture permeability can greatly contribute to improving the life and efficiency of the organic electronic device. In addition, when the user is directly exposed to sunlight, such as a car, in the past has been protected from the outside through the dark tinting of the car glass, the passivation film according to the embodiments of the present invention the skin through effective ultraviolet and infrared blocking It prevents photoaging and effectively prevents the temperature increase inside the car, while providing high visibility transparency, contributing to the driver's safety. Of course, the scope of the present invention is not limited by these effects.

1A is a diagram conceptually illustrating a configuration and a function of a transparent structure capable of blocking ultraviolet rays and infrared rays according to embodiments of the present invention.
1B is a TEM photograph showing a cross section of a transparent structure capable of blocking ultraviolet rays and infrared rays according to embodiments of the present invention.
2 is a diagram illustrating a configuration of an ultraviolet blocking film in a transparent structure that can block ultraviolet rays and infrared rays according to embodiments of the present invention.
3 and 4 are graphs showing light transmittance in a wavelength range of 350 to 800 nm according to the thickness and dyad of ZnS / LiF in a transparent structure capable of blocking ultraviolet rays and infrared rays according to embodiments of the present invention.
5 to 9 are photographs confirming that an Ag thin film having a thickness of 7 nm to 9 nm is grown on various thin films.
FIG. 10 is a diagram illustrating a comparison of paths through which moisture and / or oxygen penetrate in the transparent barrier film according to one embodiment (a) and the comparative example (b) of the present invention.
11 is a diagram sequentially illustrating a method of manufacturing a transparent barrier film according to an embodiment of the present invention.
12 is a diagram illustrating a transparent barrier film according to various embodiments of the present disclosure.
FIG. 13 conceptually illustrates a cross section of a transparent conductive electrode 50 according to an embodiment of the present invention.
FIG. 14 is a diagram illustrating a comparison of a path through which moisture and / or oxygen penetrate in the transparent conductive electrode according to Comparative Examples (a) and (b) of the present invention.
15 to 18 are graphs showing the transmittance of a transparent structure that can block ultraviolet rays and infrared rays according to Examples and Comparative Examples of the present invention.
19 to 21 are graphs showing environmental reliability of transparent structures capable of blocking ultraviolet rays and infrared rays according to Examples and Comparative Examples of the present invention.
22 is a graph showing the results of an ultraviolet reflection test (UV reflection test) of the structure according to the Examples and Comparative Examples of the present invention.
23 to 24 are schematic diagrams and results of a heat reflection test of a structure according to examples and comparative examples of the present invention.

Hereinafter, various embodiments of the present invention will be described with reference to the accompanying drawings. Throughout the specification, when referring to one component, such as a film, pattern, region, or substrate, being located "on" another component, the one component directly "contacts" the other component, or It may be interpreted that there may be other components intervening therebetween. On the other hand, when referring to one component located directly on another component, it is interpreted that there are no other components 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 inventive concept should not be construed as limited to the specific shapes of the regions shown herein, but should include, for example, changes in shape resulting from manufacturing. In addition, the thickness or size of each layer in the drawings may be exaggerated for convenience and clarity of description. Like numbers refer to like elements.

As used herein, the term 'transparent' includes not only the case where all the light is absorbed or reflected by 100%, but also the case where all of the light is passed, as well as a translucent case where at least a portion of the light is passed.

1A is a diagram conceptually illustrating a configuration and a function of a transparent structure capable of blocking ultraviolet rays and infrared rays according to embodiments of the present invention.

Referring to FIG. 1A, the transparent structure 100 that may block ultraviolet rays and infrared rays according to an embodiment of the present invention alternately repeatedly stacks a first thin film and a second thin film having different refractive indices to generate ultraviolet (UV) light. UV blocking film 170 that can block; An infrared ray blocking layer 160 capable of blocking infrared rays; And a transparent barrier film 20. The transparent barrier layer 20 may block moisture (H ₂ O) and oxygen (O ₂ ).

The ultraviolet blocking film 170, the infrared blocking film 160, and the transparent barrier film 20 may be arranged in a stacked form in any order, for example, as illustrated in FIG. 1, ultraviolet light. In addition, the transparent structure 100 capable of blocking infrared rays may be disposed in such a manner that the ultraviolet blocking film 170, the infrared blocking film 160, and the transparent barrier film 20 are sequentially stacked on the object 190. On the other hand, for example, the transparent structure 100 capable of blocking ultraviolet rays and infrared rays may be provided in a form in which the transparent barrier layer 20, the infrared ray blocking layer 160, and the ultraviolet ray blocking layer 170 are sequentially stacked. The order in which the UV blocking film 170, the infrared blocking film 160, and the transparent barrier film 20 are stacked may be provided in any order combination according to the function, use, and surrounding environment of the object 190. The object 190 may include, for example, an organic electronic device, an organic solar cell, a vehicle glass, a building glass, an airplane glass, or a ship glass.

The material of the object 190 may be, for example, any one of a polymer, a fabric, a fiber, and a glass. Polymer substrates include polyethersulphone (PES), polyacrylate (PAR, polyacrylate), polyether imide (PEI, polyetherimide), polyethylene naphthalate (PEN, polyethyelenen napthalate), polyethylene terephthalate (PET, polyethyeleneterepthalate), At least among polyphenylene sulfide (PPS), polyallylate, polyimide, polycarbonate (PC), cellulose tri acetate (TAC) and cellulose acetate propionate (CAP) It can be formed including one. The woven substrate may be formed by intersecting natural fibers such as cotton and silk at right angles by two regular yarns of horizontal and vertical yarns. The fiber substrate may be formed of at least one of natural fibers such as cotton, silk, circular, oval, and polygonal shapes, and artificial fibers such as PET, PP, PI, PS, PES, PEEK, PMMA, Parylene, and Acryl-based polymers. have.

The transparent structure 100 that can block ultraviolet rays and infrared rays prevents penetration of moisture and oxygen from or through the substrate when the organic electronic device is manufactured using a flexible substrate (polymer, fabric or fiber substrate) or glass substrate. In addition, it may be a passivation film of an organic electronic device provided in a multilayer form on one surface of the substrate or on the last electrode of the device.

Referring to FIG. 1A, a transparent structure 100 capable of blocking ultraviolet rays and infrared rays according to another embodiment of the present invention alternately repeatedly stacks a first thin film and a second thin film having different refractive indices to generate ultraviolet (UV) light. UV blocking film 170 that can block; An infrared ray blocking layer 160 capable of blocking infrared rays; And a transparent conductive electrode 50. The transparent conductive electrode 50 may block moisture (H ₂ O) and oxygen (O ₂ ).

The ultraviolet blocking film 170, the infrared blocking film 160, and the transparent conductive electrode 50 may be arranged in a sequentially stacked form in any order, for example, as illustrated in FIG. 1, ultraviolet light. In addition, the transparent structure 100 capable of blocking infrared rays may be disposed in such a manner that the ultraviolet blocking film 170, the infrared blocking film 160, and the transparent conductive electrode 50 are sequentially stacked on the object 190. On the other hand, for example, the transparent structure 100 capable of blocking ultraviolet rays and infrared rays may be provided in a form in which the transparent conductive electrode 50, the infrared ray blocking layer 160 and the ultraviolet ray blocking layer 170 are sequentially stacked. The order in which the UV blocking film 170, the infrared blocking film 160, and the transparent conductive electrode 50 are stacked may be provided in any order combination according to the function, use, and surrounding environment of the object 190. The object 190 may include, for example, an organic electronic device, an organic solar cell, a vehicle glass, a building glass, an airplane glass, or a ship glass.

The material of the object 190 may be, for example, any one of a polymer, a fabric, a fiber, and a glass. The transparent structure 100 capable of blocking ultraviolet rays and infrared rays is a single transparent conductive layer or a transparent conductive layer as one side of the substrate or the last electrode of the device when fabricating an organic electronic device using a flexible substrate (polymer, fabric, and fiber substrate). The electrode may be formed as an electrode of a cathode or an anode of an organic electronic device in the form of a multilayer.

The present invention can be applied to the fabrication of a transparent functional passivation film or electrode that can block light in the ultraviolet and infrared regions for improving the reliability of organic electronic devices. Since organic electronic devices exposed to the outside for a long time are made of reactive gases such as moisture and oxygen, and materials which are very susceptible to ultraviolet rays and heat caused by sunlight, deterioration is easily caused by exposure to such an external environment. Therefore, it is important to apply an encapsulation film or an additional filter to prevent direct exposure from such an external environment in order to manufacture a highly efficient and reliable organic electronic device. In the past, there was no passivation film or electrode that blocks ultraviolet rays and heat and at the same time has a high barrier performance. The functional passivation film according to the embodiment of the present invention is expected to be used not only as an organic electronic device but also as a transparent tinting film for a vehicle. Current tinting films are too black to obstruct the driver's vision for effective ultraviolet and heat shielding, which can lead to accidents. However, according to the present embodiment, it is possible to prevent the rapid temperature rise inside the vehicle by blocking heat inflow in the vehicle, which is particularly effective in seasons such as summer. In addition, in humans, ultraviolet light is the leading cause of eye and skin diseases, and the exposure should be minimized. Such a transparent functional passivation film may effectively block exposure to ultraviolet light.

Existing passivation (encapsulation) films or electrodes have provided only the role of protecting organic electronic devices from moisture and oxygen, or the role of electrical contacts. However, organic electronic devices are not only exposed to moisture and oxygen when exposed to the atmospheric environment, but also deteriorated by sunlight, and thus, it is very important to prevent such deterioration. Since ultraviolet light and infrared light in the sunlight are very deadly to organic materials, it has a direct relationship to the deterioration phenomenon of the device. Existing passivation films or electrodes, which have shown such a big functional limit, need to be manufactured by imparting new optical functions to improve the reliability of the organic electronic device.

1B is a TEM photograph showing a cross section of a transparent structure capable of blocking ultraviolet rays and infrared rays according to embodiments of the present invention.

1A and 1B, a transparent structure capable of blocking ultraviolet rays and infrared rays according to embodiments of the present invention is a UV filter as the UV blocking film 170, an Ag thin film as the infrared blocking film 160, and transparent. The barrier film 20 includes a ZAM structure. The UV filter is composed of alternating layers of 33 nm thick ZnS thin films and 62 nm thick LiF thin films alternately. Infrared shielding layer 160 is made of 8 nm thick Ag thin film. _It is a 60 nm thick structure in which a plurality of hybrid unit structure films formed by stacking ₂ O ₃ thin films and MgO thin films are stacked.

Hereinafter, the transparent structure 100 capable of blocking light in the ultraviolet and infrared regions and blocking the ultraviolet and infrared rays that can be applied to a passivation film or electrode that can block moisture and oxygen will be described in detail.

2 is a diagram illustrating a configuration of an ultraviolet blocking film in a transparent structure that can block ultraviolet rays and infrared rays according to embodiments of the present invention.

Referring to FIG. 2, in the ultraviolet blocking film 170, the first thin film 171 and the second thin film 172 having different refractive indices may be alternately repeatedly stacked to block ultraviolet rays (UV). The UV blocking film 170 may be a filter film having a structure in which a single film formed by atomic layer deposition, chemical vapor deposition, or physical vapor deposition is alternately stacked between two materials.

The ultraviolet blocking film 170 may be a distributed brag reflector (DBR) filter. The distributed bracket reflector (DBR) structure is a multi-layered multi-layer structure in which a first thin film 171 having a high refractive index and a second thin film 172 having a low refractive index are repeatedly stacked by using a large difference in refractive index between thin films. As shown in FIG. 2, when light is incident, reflection occurs at each interface, and if the wavelength is designed to be 1/4 of the wavelength to be reflected, all reflected light constructively interferes with reflectance close to 100% at a desired wavelength. You can get it. The DBR filter can be configured through optical simulation to effectively block light in the ultraviolet region while exhibiting high visible light transmittance. The first thin film 71 and the second thin film 72 may each have a thickness of 5 nm to 200 nm.

For example, the first thin film 171 and the second thin film 172 in the UV blocking film 170 may include any one material selected from indium oxide, zinc oxide, tin oxide, indium tin oxide, and indium zinc oxide, respectively. The difference in refractive index between the material constituting the first thin film 171 and the material constituting the second thin film 172 may be at least 0.5. The two materials having a refractive index difference of 0.5 or more may be optimized to a multilayer structure through optical simulation based on optical properties of each material.

As another example, in the UV blocking film 170, the first thin film 171 may be a ZnS thin film and the second thin film 172 may be a LiF thin film. In order to confirm the effect of the present invention, the inventors formed a ZnS thin film having a refractive index of 2.67 and a LiF thin film having a refractive index of 1.32 in a stacked structure of 4.5 layers to optimize the thickness configuration.

As another example, the UV blocking film 170 may be implemented by spin-coating deposition of a material containing a functional nanopowder such as TiO ₂ , WO ₃ , or ZnO.

3 and 4 are graphs showing light transmittance in a wavelength range of 350 to 800 nm according to the thickness and dyad of ZnS / LiF in a transparent structure capable of blocking ultraviolet rays and infrared rays according to embodiments of the present invention. 3 and 4, the unit of the thin film thickness is nm. In the case of designating a lamination structure of one ZnS thin film and one LiF thin film as 1 dyad, 3.5 dyad means a lamination structure of ZnS / LiF / ZnS / LiF / ZnS / LiF / ZnS.

3 and 4, it can be seen that the multi-structure of such ZnS / LiF can selectively configure the transmittance of a desired shape according to the thickness or dyad.

Subsequently, an infrared blocking film 160 introduced in a transparent structure capable of blocking ultraviolet rays and infrared rays according to embodiments of the present invention will be described. The infrared blocking layer 160 may be a metal thin film including any one material selected from Ag, Au, Cu, and Al. The metal thin film may have a thickness of 3 nm to 100 nm.

For example, a very thin Ag thin film may be formed on a distributed brag reflector (DBR) filter to utilize infrared reflection by a metal. However, in order to secure the optimum transmittance, the thickness of the Ag thin film was first filmed after the thickness showing island growth, and the Ag film showed the highest transmittance at a thickness of about 9 nm.

5 to 9 are photographs confirming that an Ag thin film having a thickness of 7 nm to 9 nm is grown on various thin films.

5 to 9, when the Ag thin film is formed on various thin films (Al ₂ O ₃ , ITO, ZnO, LiF, ZnS thin films) at a deposition rate of 2 μs / s, having a thickness of 7 nm to 9 nm, The Ag thin films formed on the Al ₂ O ₃ thin film, the ITO thin film, the ZnO thin film, and the LiF thin film may be separated from each other in an island form, whereas the Ag thin films formed on the ZnS thin film are 7 nm to 9 nm. It can be seen that the first filmation appears after the thickness showing island growth in the thickness of. ZnS is capable of forming a thin metal film due to the high surface energy compared to other thin films in general, has a good advantage in securing high visible light transmittance. 3 and 4, the ZnS / LiF dyad is not a positive integer but has a value such as 1.5, 2.5, 3.5. Also, the Ag film is filmed past the thickness showing island growth on the ZnS film rather than the LiF film. This is because it is advantageous in terms of implementation.

On the other hand, the inventors confirmed that the deposition process of the Au thin film as well as the Ag thin film as shown in Figs. That is, the Au, Cu, or Al thin films formed on the Al ₂ O ₃ thin film, the ITO thin film, the ZnO thin film, and the LiF thin film may be identified as thin films separated from each other in an island form at a thickness of 7 nm to 9 nm. , Au, Cu or Al thin film formed on the ZnS thin film can be seen that the first filming is shown past the thickness showing island (island) growth in the thickness of 7nm to 9nm.

Hereinafter, the transparent barrier film 20 introduced from the transparent structure capable of blocking ultraviolet rays and infrared rays according to embodiments of the present invention will be described. The transparent barrier film 20 may have a thickness of 5 nm to 1 μm.

As an example, the transparent barrier film 20 may include an aluminum oxide film, aluminum nitride film, silicon oxide, silicon nitride film, silicon oxynitride film, magnesium oxide film, magnesium fluoride film, titanium oxide film, titanium nitride film, hafnium oxide film, hafnium nitride film, zirconium oxide film, and zirconium oxide. It may be at least one single thin film or a laminated thin film selected from a nitride film, a tungsten oxide film, a zinc sulfide film, a zinc oxide film and a yttrium oxide film.

As another example, the transparent barrier film 20 includes at least one hybrid unit structure film formed by stacking a stress reducing thin film, a barrier thin film and a moisture absorbing thin film, wherein the stress reducing thin film includes ZnO, SiO ₂ , SiN _x ,. A thin film including at least one selected from Ag and Al, the barrier thin film is a thin film including at least one of AlN, Al ₂ O ₃ , AlO _x N _y and SnO _x , The hygroscopic thin film is an alkali metal (Li , Na, K, Rb, Cs, Fr), alkaline earth metals (Be, Mg, Ca, Sr, Ba, Ra), Ti, Zr, Hf and may be a thin film comprising at least one material selected from oxides thereof. .

As another example, the transparent barrier layer 20 may be a transparent barrier layer capable of improving transmittance of visible light, and may include at least one hybrid unit structure layer formed by stacking a ZnO thin film, an Al ₂ O ₃ thin film, and an MgO thin film. have.

The transparent barrier layer 20 may be a thin film having a high barrier property having a low water vapor transmission rate as well as a high transmittance, high flexibility, and low stress of 95% or more. For example, the transparent flexible encapsulation structure Can be applied as

FIG. 10 is a diagram illustrating a comparison of paths through which moisture and / or oxygen penetrate in the transparent barrier film according to one embodiment (a) and the comparative example (b) of the present invention.

Referring to FIG. 10A, the transparent barrier layer 20 according to an embodiment of the present invention includes at least one hybrid unit structure layer formed on at least one surface of the base layer 10.

The hybrid unit structure film is formed by stacking an Al ₂ O ₃ thin film 22, a ZnO thin film 24, and an MgO thin film 26. The stacked form of the Al ₂ O ₃ thin film 22, the ZnO thin film 24, and the MgO thin film 26 constituting the hybrid unit structure film may have any stacking order. For example, the hybrid unit structure film may include ZnO / Al ₂ O ₃ / MgO, ZnO / MgO / Al ₂ O ₃ , MgO / Al ₂ O ₃ / ZnO, MgO / ZnO / Al ₂ O ₃ , Al ₂ O on the base film. ₃ / ZnO / MgO or Al ₂ O ₃ / MgO / ZnO can be configured in the stacking order. In the hybrid unit structure film, the Al ₂ O ₃ thin film 22 functions as a main barrier thin film to prevent the penetration of moisture and / or oxygen, and the ZnO thin film 24 is formed of a stress relief thin film that relaxes the stress of the hybrid unit structure film. The MgO thin film 26 may function as a hygroscopic thin film for preventing hydrolysis of the Al ₂ O ₃ thin film 22. The Al ₂ O ₃ thin film 22, the ZnO thin film 24, and the MgO thin film 26 each have a defect such as a pinhole.

In the transparent barrier film 20 according to an embodiment of the present invention, at least one hybrid unit structure film may be provided. For example, in FIG. 10A, the first hybrid unit structure film 20_1 is provided. A plurality of hybrid unit structure films may be stacked, such as the second hybrid unit structure film 20_2, the third hybrid unit structure film 20_3, and the fourth hybrid unit structure film 20_4.

In each hybrid unit structure film, the Al ₂ O ₃ thin film 22, the ZnO thin film 24, and the MgO thin film 26 each have pinholes 22a, 24a, and 26a, but adjacent Al ₂ O ₃ thin films 22. ), The other one of the ZnO thin film 24 and the MgO thin film 26 and the positions of the pinholes are disposed to be offset from each other to have a pinhole-decoupling structure.

For example, the pinhole 24a of the ZnO thin film 24 in the first hybrid unit structure film 20_1 may be a pinhole in the Al ₂ O ₃ thin film 22 and the MgO thin film 26 adjacent to the ZnO thin film 24. The positions 24a and 26a and the relative positions are shifted from each other to have a pinhole-decoupling structure. The pinhole decoupling structure is present in not only the first hybrid unit structure film 20_1 but also in the second hybrid unit structure film 20_2, the third hybrid unit structure film 20_3, and the fourth hybrid unit structure film 20_4. Also shown in the boundary region of the hybrid unit structure film 20_1, the second hybrid unit structure film 20_2, the third hybrid unit structure film 20_3, and the fourth hybrid unit structure film 20_4.

In each hybrid unit structure film, the Al ₂ O ₃ thin film 22 is an ultra thin film having a thickness of 0.1 nm to 2 nm, the MgO thin film 26 is an ultra thin film having a thickness of 0.1 nm to 2 nm, and the ZnO thin film 24 has a thickness It may be an ultra thin film having a thickness of 0.1nm to 30nm.

The inventors have found that when very thin films of different thin films having pinholes are provided in a plurality of stacked structures, a pinhole-decoupling structure can be implemented to make the penetration of moisture and / or oxygen very slow. It was.

Referring to FIG. 10B, the transparent barrier film according to the comparative example of the present invention includes a protective film 70 formed of a single material film on one surface of the base film 10.

In the process of forming the protective film 70 formed of a single material film, the pinhole 70a grows together with the protective film along the first place where the protective film 70 is initially formed, and thus has a relatively large size, thereby facilitating the penetration of moisture and / or oxygen. That is, the length of the penetration path P of water and / or oxygen in the transparent barrier film shown in FIG. 10A is a penetration path of water and / or oxygen in the transparent barrier film shown in FIG. P) longer than length Therefore, the transparent barrier film shown in FIG. 10A can effectively prevent the penetration of moisture and / or oxygen than the transparent barrier film shown in FIG. 10B.

11 is a diagram sequentially illustrating a method of manufacturing a transparent barrier film according to an embodiment of the present invention.

Referring to FIGS. 11A and 11B, an Al ₂ O ₃ thin film 22 is formed on the base film 10. The Al ₂ O ₃ thin film 22 can be formed using, for example, atomic layer deposition (ALD), chemical vapor deposition (CVD), molecular layer deposition (MLD), or physical vapor deposition (PVD). The Al ₂ O ₃ thin film 22 may be an ultra-thin film having a thickness of 0.1 nm to 2 nm. In this case, the first pinhole 22a may be formed to penetrate the Al ₂ O ₃ thin film 22. Subsequently, a ZnO thin film 24 is formed on the Al ₂ O ₃ thin film 22. The ZnO thin film 24 can be formed using, for example, atomic layer deposition (ALD), chemical vapor deposition (CVD), molecular layer deposition (MLD), or physical vapor deposition (PVD). In atomic layer deposition (ALD) or chemical vapor deposition (CVD), the ZnO thin film 24 may be formed by providing a ZnO precursor 24p on the Al ₂ O ₃ thin film 22. The ZnO thin film 24 may be an ultra-thin film having a thickness of 0.1 nm to 30 nm, and in this case, a second pin hole 24a penetrating the ZnO thin film 24 may be formed. There is a relatively high probability that the first pinhole 22a and the second pinhole 24a are staggered from each other, rather than the first pinhole 22a and the second pinhole 24a are arranged to be aligned with each other. high.

Referring to FIGS. 11C and 11D, the MgO thin film 26 is formed on the ZnO thin film 24. The MgO thin film 26 can be formed using, for example, atomic layer deposition (ALD), chemical vapor deposition (CVD), molecular layer deposition (MLD), or physical vapor deposition (PVD). In atomic layer deposition (ALD) or chemical vapor deposition (CVD), the MgO precursor 26p may be provided on the ZnO thin film 24 to form the MgO thin film 26. The MgO thin film 26 may be an ultra-thin film having a thickness of 0.1 nm to 2 nm, and in this case, a third pin hole 26a penetrating the MgO thin film 26 may be formed. There is a relatively high probability that the second pinhole 24a and the third pinhole 26a are staggered from each other, rather than the possibility that the second pinhole 24a and the third pinhole 26a are aligned with each other. high.

12 is a diagram illustrating a transparent barrier film according to various embodiments of the present disclosure. In FIG. 12, the description of the above-described thickness and pinhole-decoupling structure of the thin film is applied, but it is omitted in the drawing for convenience.

Referring to FIG. 12A, each of the hybrid unit structure films constituting the transparent barrier film includes an Al ₂ O ₃ thin film 22, a ZnO thin film 24, and an MgO thin film 26 sequentially on the base film 10. It can be laminated.

Referring to FIG. 12B, the ZnO thin film 24, the Al ₂ O ₃ thin film 22, and the MgO thin film 26 are sequentially formed on each of the hybrid unit structure films constituting the transparent barrier film. It can be laminated.

In addition, although not shown in the drawings, the laminated structure of each hybrid unit structure film constituting the transparent barrier film according to the modified embodiment of the present invention is Al ₂ O ₃ thin film 22, ZnO thin film 24 and MgO thin film ( Any order combination of 26) is possible. For example, each hybrid unit structure film may be formed by sequentially stacking the MgO thin film 26, the Al ₂ O ₃ thin film 22, and the ZnO thin film 24 on the base film 10.

Meanwhile, the plurality of hybrid unit structure layers may include two or more hybrid unit structure layers having different combinations of components. For example, in the plurality of hybrid unit structure films constituting the transparent barrier film, the first hybrid unit structure film 20_1 may be formed on the base film 10 by the Al ₂ O ₃ thin film 22, the ZnO thin film 24, and the MgO thin film. (26) is sequentially stacked, the second hybrid unit structure film (20_2) is a ZnO thin film 24, Al ₂ O ₃ thin film 22 and MgO thin film 26 sequentially on the base film 10 The third hybrid unit structure film 20_3 is formed by sequentially stacking an Al ₂ O ₃ thin film 22, an MgO thin film 26, and a ZnO thin film 24 on the base film 10. The 4 hybrid unit structure film 20_3 may be formed by sequentially stacking the MgO thin film 26, the Al ₂ O ₃ thin film 22, and the ZnO thin film 24 on the base film 10.

A plurality of hybrid unit structure films constituting the transparent barrier film according to an embodiment of the present invention to prevent the crystal growth of each thin film to produce a thin film of a complete amorphous structure to achieve a thin film of high density compared to a general single thin film and moisture and / or oxygen By changing the moisture permeation mechanism of, it makes the penetration of moisture and / or oxygen difficult. In addition, due to the dispersion of stress by the thin film internal pinholes, the flexibility is improved, and the hardness and elastic modulus are lowered due to the very thin layer of different single materials, thereby improving the brittleness and the flexibility. . The transparent barrier film implemented through the structural and material manipulations described above improves the long-term reliability applicable to organic electronic devices based on various beneficial effects.

Devices made of organic materials (e.g., OLEDs) generally consist of metal electrodes and organic materials that are sensitive to moisture and / or oxygen, and are easily reacted by moisture and / or oxygen during operation, resulting in dark spots that degrade the performance of the device. do. Therefore, a protective layer is necessary to ensure stable operation and long life without deterioration for a long time.

In the transparent barrier film proposed by the present patent, the disadvantages of each thin film are complemented by using layers having an effective advantage for the production of the encapsulation film for the multifunctional organic device, and each thin film has a defect inside each other. The barrier properties were greatly improved by providing a hybrid film containing a mixture of very thin films having a thin film). For example, ZnO, Al ₂ O ₃ and MgO materials are sequentially stacked to produce a hybrid thin film having a defect, and a water vapor transmission rate of 10 ^-6 g / m ² / day In addition to achieving a high barrier characteristic having a rate), a thin film having a high transmittance, high flexibility, and zero stress of more than 95% is realized. To explain the advantages of the materials used in the ZnO / Al ₂ O ₃ / MgO hybrid thin film structure, Al ₂ O ₃ thin film is used to improve the barrier properties inside the thin film. Since the very thin different thin films having pinholes are a mixture of thin films in turn, barrier properties can be reduced by making it easier to penetrate very small moisture and / or oxygen molecules. In general, the pinholes of thin films caused by defects grow based on the origin of the defects. If these problems are taken with very thin layers, defect decoupling of the pinholes and defects of each film is changed. The decoupling phenomenon occurs, and as a result, as shown in FIG. 10, the penetration of moisture and / or oxygen is very slow, and thus has a different moisture permeation mechanism from a thin film made of a simple single material. In addition, the moisture-absorbing layers present in the middle capture moisture to contribute to improvement of barrier properties. In addition, ZnO thin films help to reduce stress of the hybrid thin film, and have TMA (Trimethyl Aluminum) used to form Al ₂ O ₃ between the Al ₂ O ₃ and ZnO interfaces to etch the ZnO surface. As the etching occurs and deposition occurs, strong bonding is formed between the Al ₂ O ₃ and ZnO interface, thereby improving barrier function. Since the high density film of the ultra-thin mixed diffraction structure manufactured as described above has a low modulus of elasticity and a low value even in hardness, the brittleness of the existing single films can be improved to give flexible properties, and furthermore, It is an advantage that the dual effect is that the stress is dispersed by defects so that the flexibility of the encapsulation film is improved. Based on these measurement results and various theories, the transparent barrier film proposed in the present invention is mixed with functional thin films having various advantages to solve degradation problems such as barrier properties and hydrolysis seen in conventional encapsulation films and structures. At the same time, due to the ultra-thin mixed diffraction structure for stable application to flexible devices, it is manufactured to reduce elastic modulus and hardness, and to distribute stress through defects throughout the membrane. It is possible to manufacture a sealing film that can be applied. The Al ₂ O ₃ thin film 22 described above is understood as a barrier thin film, and the barrier thin film may be a thin film including at least one of AlN, AlO _x N _y, and SnO _x in addition to the Al ₂ O ₃ thin film 22. The above-described ZnO thin film 24 is understood as a stress reducing thin film, and the stress reducing thin film is SiO ₂ , SiN _x , in addition to the ZnO thin film 24. It may be a thin film including at least one selected from Ag and Al. The above-described MgO thin film 26 is understood as a moisture absorbing thin film, and the moisture absorbing thin film is an alkali metal (Li, Na, K, Rb, Cs, Fr), alkaline earth metals (Be, Ca, Sr, in addition to the MgO thin film 26). It may be a thin film including at least one of a material selected from Ba, Ra), Ti, Zr, Hf and oxides thereof.

In the transparent structure capable of blocking ultraviolet rays and infrared rays, each of the first thin film and the second thin film has a thickness of 5nm to 200nm, the infrared blocking film has a thickness of 3nm to 100nm, one hybrid unit structure film The Al ₂ O ₃ thin film may be an ultra thin film having a thickness of 0.1 nm to 2 nm, the MgO thin film may be an ultra thin film having a thickness of 0.1 nm to 2 nm, and the ZnO thin film may be an ultra thin film having a thickness of 0.1 nm to 30 nm.

Hereinafter, a transparent conductive electrode 50 introduced from a transparent structure capable of blocking ultraviolet rays and infrared rays according to embodiments of the present invention will be described. The transparent conductive electrode 50 may have a thickness of 10 nm to 300 nm.

As an example, the transparent conductive electrode 50 is based on a metal oxide formed by stacking a plurality of metal oxide unit films by an atomic layer deposition process (ALD) or a chemical vapor deposition process (CVD), wherein dopants are doped in the base. It may be a transparent conductive electrode.

The metal oxide may be at least one of indium oxide, zinc oxide, tin oxide, indium tin oxide, and indium zinc oxide, and the dopant may be doped relatively concentrated in a plurality of unit film stack boundary regions in the matrix. As the dopant inhibits crystal growth of each unit film, the matrix may have an amorphous form.

As another example, the transparent conductive electrode 50 is based on ZnO formed by stacking a plurality of ZnO unit films by atomic layer deposition (ALD) or chemical vapor deposition (CVD), but does not include magnesium (Mg) as a dopant in the matrix. And at least one of aluminum (Al) may be a doped transparent conductive electrode.

FIG. 13 conceptually illustrates a cross section of a transparent conductive electrode 50 according to an embodiment of the present invention.

Referring to FIG. 13, a transparent conductive electrode according to an embodiment of the present invention has ZnO as a matrix and is doped with at least one of magnesium (Mg) and aluminum (Al) as dopants in the matrix. A transparent conductive electrode 50 is provided. The matrix may be formed by stacking a plurality of ZnO unit films 52 by an atomic layer deposition process (ALD) or a chemical vapor deposition process (CVD). Each ZnO unit layer 52 has the same defect as the pinhole 55, but one unit layer has a pinhole-decoupling structure in which the positions of the other adjacent unit layer and the pinhole are shifted from each other. It can have That is, such pinhole decoupling occurs at a plurality of ZnO unit film stack boundaries. Meanwhile, the dopant, which is at least one of magnesium (Mg) and aluminum (Al), may be doped by being concentrated in a plurality of ZnO unit layer stack boundary regions in the ZnO matrix. As the dopant inhibits crystal growth of each ZnO unit film, the matrix may have an amorphous form. The structure shown in FIG. 13 is based on i) ZnO, which is composed of a plurality of ZnO unit films stacked by atomic layer deposition (ALD) or chemical vapor deposition (CVD), and ii) dopant in the matrix. As doped with magnesium (Mg) and aluminum (Al), the dopant may be a transparent conductive electrode that is doped relatively concentrated in a plurality of unit film stack boundary regions in the matrix. For example, magnesium (Mg) is relatively concentrated and doped in the first unit film stacking boundary region, and aluminum (Al) is relatively in the second unit film stacking boundary region immediately adjacent to the first unit film stacking boundary region. The concentrated and doped components may be structures that are repeatedly arranged a plurality of times. In the transparent conductive electrode, the transparent conductive electrode has a water vapor transmission rate of 10 ⁻⁴ g / m 2 / day or less, an optical transmittance of 90% or more, and a conductivity change even with a bending of 1 mm. It may be an integral structure of the sealing film and the electrode capable of performing the sealing function for the device without a separate sealing film by providing a physical property without. The transparent conductive electrode 50 is disposed on the base film 10. For example, the transparent conductive electrode can be disposed in direct contact with the transparent flexible substrate. As another example, the transparent conductive electrode may be disposed in direct contact with an element on the transparent flexible substrate without directly contacting the transparent flexible substrate.

The transparent conductive electrode according to the embodiment of the present invention described above corresponds to a case in which ZnO is used as a base, but at least one of magnesium (Mg) and aluminum (Al) is doped as a dopant in the base. However, the technical spirit of the present invention may be expanded without being limited thereto. That is, the transparent conductive electrode 50 according to another embodiment of the present invention is based on a metal oxide, but provided with a transparent conductive electrode doped with a dopant in the base, the base is an atomic layer deposition process (ALD) or chemical vapor phase The plurality of metal oxide unit films may be stacked by a deposition process (CVD). In this case, the transparent conductive electrode may include at least one of indium oxide, zinc oxide, tin oxide, indium tin oxide, and indium zinc oxide.

Hereinafter, a method of manufacturing the transparent conductive electrode 50 of the present invention described above will be described. The manufacturing method includes a first step of depositing a unit film of a metal oxide film by an atomic layer deposition process (ALD) or a chemical vapor deposition process (CVD); And a second step of doping the dopant on the unit film of the metal oxide film. As a result, a transparent conductive electrode doped with a dopant is formed in a matrix formed by stacking unit films of a plurality of metal oxide films. The first step may include a precursor, a source gas, a reaction gas or the like for forming a metal oxide film after loading a transparent flexible substrate in a chamber in which an atomic layer deposition process (ALD) or chemical vapor deposition process (CVD) is performed. The source gas is injected and heat or plasma is applied to induce a chemical reaction to deposit a metal oxide film. Specifically, in the case of an atomic layer deposition process (ALD), providing a source gas on a transparent flexible substrate to adsorb; Purging the remaining gas adsorbed; Providing a reaction gas on the transparent flexible substrate to form a reaction unit film; Reacting and purging the remaining reaction gas; may be performed at least one unit cycle including a metal oxide film. In the case of chemical vapor deposition (CVD), the source gas may be decomposed using external energy to form a metal oxide film by chemical vapor reaction. The second step may include a precursor, a source gas, a reaction gas, or a precursor for providing a dopant material in a chamber in which an atomic layer deposition process (ALD) or chemical vapor deposition process (CVD) is performed after the first step. The dopant is doped into the surface portion of the metal oxide film by injecting the source gas and applying heat or plasma. Specifically, in the case of an atomic layer deposition process (ALD), providing a source gas on the metal oxide to adsorb; Purging the remaining gas adsorbed; Providing a reaction gas on the metal oxide to form a dopant material; Doping the dopant on the surface of the metal oxide may be performed by performing at least one or more unit cycles. In the case of chemical vapor deposition (CVD), the source gas may be decomposed using external energy to dope the dopant on the surface of the metal oxide by chemical vapor reaction. The dopant doped on the metal oxide may be formed in a discontinuously dispersed state, not a thin film connected to all on the metal oxide. That is, the dopant to be doped may be formed on the metal oxide while having a thickness lower than that of the thin film. According to the above-described method for manufacturing a transparent conductive electrode, the first step and the second step are in-situ in the same chamber performing an atomic layer deposition process (ALD) or chemical vapor deposition process (CVD). Can be done with Alternatively, the first step and the second step may be performed in-situ with different chambers in the same equipment performing the atomic layer deposition process (ALD) or chemical vapor deposition process (CVD). . Proceeding in-situ may mean that the transparent flexible substrate performs the first step and the second step sequentially before moving from the low pressure state in the chamber to the atmospheric pressure outside the chamber or equipment. have. By performing the cycle including the first step and the second step a plurality of times, the dopant may be doped relatively concentrated in a boundary region in which a plurality of unit films are stacked among the plurality of unit films constituting the matrix. For example, magnesium (Mg) is relatively concentrated and doped in the first ZnO unit layer stack boundary region, and aluminum (Al) is disposed in the second ZnO unit layer stack boundary region immediately adjacent to the first ZnO unit layer stack boundary region. Is relatively concentrated and doped, and magnesium (Mg) is relatively concentrated and doped in the third ZnO unit layer stack boundary region immediately adjacent to the second ZnO unit layer stack boundary region, and the third ZnO unit layer stack boundary region is doped. Aluminum (Al) may be relatively concentrated and doped in the fourth ZnO unit layer stack boundary region immediately adjacent to the fourth ZnO unit layer stack boundary region. In addition, by performing the cycle including the first step and the second step a plurality of times, the dopant inhibits the crystal growth of each unit film so that the matrix may have an amorphous form.

FIG. 14 is a diagram illustrating a comparison of a path through which moisture and / or oxygen penetrate in the transparent conductive electrode according to Comparative Examples (a) and (b) of the present invention.

Referring to FIG. 14A, the transparent conductive electrode according to the comparative example of the present invention includes a transparent conductive electrode 50 made of only a ZnO base that is not doped with a dopant on one surface of the base film. That is, the ZnO base is formed by continuously performing only the first step without performing the above-described second step on the base film. In this process, the pinhole 55 grows together with the base along the first place where the pinhole is relatively large, thereby facilitating the penetration of moisture and / or oxygen.

Referring to (b) of FIG. 14, the transparent conductive electrode according to the embodiment of the present invention is based on ZnO on one surface of the organic bottom layer, but at least one of magnesium (Mg) and aluminum (Al) as a dopant in the base. And doped transparent conductive electrode 50. The matrix is formed by stacking a plurality of ZnO unit films 52 by atomic layer deposition (ALD) or chemical vapor deposition (CVD). Each of the unit membranes 52 has a pinhole 55, and one unit membrane is disposed with the positions of the other adjacent unit membranes and the pinholes deviated from each other so that a pinhole decoupling structure is implemented to provide moisture and / or It makes the penetration of oxygen very slow. In addition, the pinholes are relatively small in size since they do not grow along with the matrix along their initial formation. Arrangement of the pinhole position of one unit film and the pinhole positions of the other unit film adjacent to each other is the first steps of depositing the unit oxide film of the metal oxide film by an atomic layer deposition process (ALD) or chemical vapor deposition process (CVD). This is because the second step of doping the dopant on the unit film of the metal oxide film is performed in between.

The penetration path length of moisture and / or oxygen in the transparent conductive electrode shown in FIG. 14B is longer than the penetration path length of moisture and / or oxygen in the transparent conductive electrode shown in FIG. Therefore, the transparent conductive electrode shown in FIG. 14B can effectively prevent the penetration of moisture and / or oxygen than the transparent conductive electrode shown in FIG. 14A.

Until now, a transparent structure capable of blocking ultraviolet rays and infrared rays according to embodiments of the present invention has been described. Such a transparent structure capable of blocking ultraviolet rays and infrared rays may block light in the ultraviolet and infrared regions, and at the same time, may also block moisture and oxygen, and a transparent passivation structure for an organic electronic device, a transparent electrode structure for an organic electronic device, or a vehicle transparent It may be implemented as a tinting film.

Hereinafter, various characteristics of the transparent structure that can block ultraviolet rays and infrared rays according to an embodiment of the present invention will be described with a comparative example.

15 to 18 are graphs showing the transmittance of a transparent structure that can block ultraviolet rays and infrared rays according to Examples and Comparative Examples of the present invention.

Specifically, FIG. 15 shows transmittance measurement values and simulation values in a wavelength band of 350 nm to 800 nm for an ultraviolet shielding film having a DBR (Distributed Brag Reflector) filter structure in which ZnS thin films and LiF thin films are alternately stacked of 3.5 layers. 16 shows transmittance measurements and simulation values in a wavelength band of 350 nm to 800 nm for a structure in which an Ag thin film having a thickness of 9 nm is disposed as an infrared blocking film on the ultraviolet blocking film of FIG. 15, and FIG. 17 shows a transparent barrier on the structure of FIG. 16. In the final 60nm-thick ZAM structure in which a ZnO thin film, an Al ₂ O ₃ thin film and a MgO thin film were laminated as a film, transmittance measurement values and simulation values in a wavelength range of 350 nm to 800 nm are shown. In addition, FIG. 18 shows a case in which there is a UV blocking film (UV filter), a UV blocking film and an infrared blocking film (UV filter / Ag), and a UV blocking film, an infrared blocking film and a transparent barrier film (UV filter / Ag / ZAM). The transmittance measurement value in the wavelength range of 350 nm to 2000 nm is shown.

15 to 18, it can be seen how the transmittances change in the ultraviolet, visible and infrared regions by the sequential formation of the films having respective functions. The DBR filter effectively blocks ultraviolet rays below 400nm and exhibits high transmittance in the visible and infrared regions. When a 9 nm Ag thin film is formed on the DBR filter, the overall transmittance is lowered, and the blocking is particularly effective in the infrared region. To increase this lowered transmission, a final 60nm thick barrier film is formed to improve transmission in the visible region using interference and resonance effects of light due to dielectric / metal / dielectric structures. It can be seen that the optical effect between each layer and the layer is blocked by UV and infrared rays, and the transparent passivation film is possible.

19 to 21 are graphs showing environmental reliability of transparent structures capable of blocking ultraviolet rays and infrared rays according to Examples and Comparative Examples of the present invention.

Specifically, FIG. 19 illustrates the difference in transmittance before and after the test maintained for 48 hours in a harsh environment of 60 ° C./90% with respect to the above-described UV blocking film, and FIG. 20 shows an Ag thin film as an infrared blocking film on the UV blocking film. The difference in transmittance before and after the test maintained for 48 hours in a harsh environment of 60 ° C./90% for one structure is shown. FIG. 21 shows 60 ° C. / for the structure in which the above-mentioned transparent barrier film is formed on the structure of FIG. 20. The difference in permeability was seen before and after the test for 48 hours in 90% of harsh environments.

19 to 21, the transparent structure capable of blocking ultraviolet rays and infrared rays (see FIG. 21) according to an embodiment of the present invention has a difference in transmittance even after being stored for 2 days in a harsh environment of 60 ° C./90%. On the other hand, the DBR filter / Ag membrane without the transparent barrier film described above showed a large change in permeability. This is because a sudden deterioration phenomenon occurs due to the high reactivity of the Ag film.

22 is a graph showing the results of an ultraviolet reflection test (UV reflection test) of the structure according to the Examples and Comparative Examples of the present invention.

Referring to FIG. 22, a PET substrate (Bare PET), a glass substrate (Bare glass), an ITO film (ITO), a semi-transparent Ag thin film (Semi transparent Ag), an ultraviolet filter (UV filter), an Ag thin film on the ultraviolet filter (UV filter) / Ag) and the transparent barrier film (UHGDM) disposed on the Ag thin film structure formed on the ultraviolet filter, respectively, irradiated with ultraviolet rays to confirm the intensity of the transmitted ultraviolet rays. As a result, the UV filter, the Ag thin film (UV filter / Ag) on the UV filter, and the transparent barrier film (UHGDM) disposed on the Ag thin film structure formed on the UV filter showed a significant ultraviolet blocking effect. Able to know. Among them, it can be seen that the UV blocking effect is most excellent in the transparent structure (UHGDM) that can block ultraviolet rays and infrared rays according to an embodiment of the present invention.

23 to 24 are schematic diagrams and results of a heat reflection test of a structure according to examples and comparative examples of the present invention.

Specifically, FIG. 23 illustrates a schematic configuration of a heat reflection test, and a left side of FIG. 24 is an optical picture of a heat reflection test object, and a right side is a measurement picture showing a temperature profile of the heat reflection test object. The heat reflection test object on the left side of FIG. 24 is a PET substrate (Bare PET), an ultraviolet filter (UV filter) on the PET substrate, an ultraviolet block and an infrared filter on the PET substrate (UV filter / Ag), an ultraviolet block and an infrared block on the PET substrate. And a transparent barrier film (UV filter / Ag / ZAM).

Referring to the results of FIG. 24, it can be seen that the heat blocking effect is most excellent in the transparent structure (UV filter / Ag / ZAM) capable of blocking ultraviolet rays and infrared rays according to an embodiment of the present invention.

Until now, a transparent structure capable of blocking ultraviolet rays and infrared rays according to the technical idea of the present invention has been described. The present invention relates to the fabrication of a functional passivation film or electrode capable of blocking ultraviolet rays and infrared rays, and having a high barrier function in order to improve the reliability and stability of the transparent flexible organic electronic device. It can be utilized as an optimized functional film of a cell or an organic light emitting diode. If the conventional traditional passivation or electrodes have only performed a simple moisture and oxygen barrier function or conductive function, the proposed invention selectively and transparently blocks harmful light to electronic devices such as UV and infrared light, Providing moisture permeability can greatly contribute to improving the life and efficiency of the organic electronic device. In addition, when the user is directly exposed to sunlight, such as a car, in the past has been protected from the outside through the dark tinting of the car glass, the passivation film of the present invention is effective to prevent skin photoaging and interior of the car through the effective ultraviolet and infrared blocking It can effectively prevent temperature rise, while at the same time providing high visibility transparency, contributing to driver safety. Overall, the transparent passivation film of the present invention exhibits high blocking properties in the ultraviolet and infrared regions, high visible light transmittance, a barrier property of 10 ⁻⁵ g / m ² / day, and is a technology that can be applied to practical industries. In addition, when the barrier film is replaced with a transparent conductive film, it can be used as a functional electrode, which can block ultraviolet rays required by the display industry, and has a high transparency at a blue wavelength (especially 450 nm). It can be used as an electrode to expand its application.

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

20: transparent barrier film
50: transparent conductive electrode
160: infrared cut film
170: UV blocking film
100: transparent structure that can block ultraviolet rays and infrared rays

Claims (17)

A UV blocking film capable of blocking ultraviolet rays by repeatedly stacking first and second thin films having different refractive indices;
An infrared blocking film capable of blocking infrared rays; And
Including; transparent barrier film,
The ultraviolet blocking film, the infrared blocking film and the transparent barrier film are arranged in a stacked form in any order,
The transparent barrier film includes at least one hybrid unit structure film formed by stacking a stress reducing thin film, a barrier thin film and a moisture absorbing thin film,
The stress relief thin film is ZnO, SiO ₂ , SiN _x , A thin film including at least one selected from Ag and Al, the barrier thin film is a thin film including at least one of AlN, Al ₂ O ₃ , AlO _x N _y and SnO _x , The hygroscopic thin film is an alkali metal (Li , Na, K, Rb, Cs, Fr), alkaline earth metals (Be, Mg, Ca, Sr, Ba, Ra), Ti, Zr, Hf and a thin film containing at least one material selected from oxides thereof Made,
Transparent structure that can block ultraviolet rays and infrared rays. A UV blocking film capable of blocking ultraviolet rays by repeatedly stacking first and second thin films having different refractive indices;
An infrared blocking film capable of blocking infrared rays; And
Including; transparent conductive electrode;
The ultraviolet blocking film, the infrared blocking film and the transparent conductive electrode are arranged in a stacked form in any order,
The transparent conductive electrode is a transparent conductive electrode based on a metal oxide composed of a plurality of metal oxide unit films stacked by an atomic layer deposition process (ALD) or chemical vapor deposition process (CVD), doped with a dopant in the base,
The dopant may be doped relatively concentrated in a plurality of unit film stack boundary regions in the matrix.
Transparent structure that can block ultraviolet rays and infrared rays. A UV blocking film capable of blocking ultraviolet rays by repeatedly stacking first and second thin films having different refractive indices;
An infrared blocking film capable of blocking infrared rays; And
Including; transparent conductive electrode;
The ultraviolet blocking film, the infrared blocking film and the transparent conductive electrode are arranged in a stacked form in any order,
The transparent conductive electrode is a transparent conductive electrode based on a metal oxide composed of a plurality of metal oxide unit films stacked by an atomic layer deposition process (ALD) or chemical vapor deposition process (CVD), doped with a dopant in the base,
The dopant inhibits crystal growth of each unit film, so that the matrix has an amorphous form,
Transparent structure that can block ultraviolet rays and infrared rays. The method according to any one of claims 1 to 3,
In the UV blocking film, the first thin film is a ZnS thin film and the second thin film is characterized in that the LiF thin film,
Transparent structure that can block ultraviolet rays and infrared rays. The method according to any one of claims 1 to 3,
In the UV blocking film, the first thin film and the second thin film may be thin films including any one material selected from among indium oxide, zinc oxide, tin oxide, indium tin oxide, and indium zinc oxide, and a material constituting the first thin film; The refractive index difference of the material constituting the second thin film is characterized in that at least 0.5 or more,
Transparent structure that can block ultraviolet rays and infrared rays. The method according to any one of claims 1 to 3,
The UV blocking film is characterized in that the DBR (Distributed Brag Reflector) filter,
Transparent structure that can block ultraviolet rays and infrared rays. The method according to any one of claims 1 to 3,
The infrared blocking film is a metal thin film comprising any one selected from Ag, Au, Cu and Al,
Transparent structure that can block ultraviolet rays and infrared rays. The method of claim 1,
The transparent barrier film is a transparent barrier film capable of improving the transmittance of visible light, and comprises at least one hybrid unit structure film formed by stacking a ZnO thin film, an Al ₂ O ₃ thin film, and an MgO thin film,
Transparent structure that can block ultraviolet rays and infrared rays. The method according to any one of claims 2 and 3,
The metal oxide is at least one of indium oxide, zinc oxide, tin oxide, indium tin oxide, and indium zinc oxide,
Transparent structure that can block ultraviolet rays and infrared rays. The method according to any one of claims 2 and 3,
The transparent conductive electrode is based on ZnO formed by stacking a plurality of ZnO unit films by atomic layer deposition (ALD) or chemical vapor deposition (CVD), and includes magnesium (Mg) and aluminum (Al) as dopants in the matrix. At least one of which is a doped transparent conductive electrode,
Transparent structure that can block ultraviolet rays and infrared rays. The method according to any one of claims 1 to 3,
The transparent structure is characterized in that the transparent passivation structure for an organic electronic device,
Transparent structure that can block ultraviolet rays and infrared rays. The method according to any one of claims 1 to 3,
The transparent structure is characterized in that the vehicle is a transparent tinting film,
Transparent structure that can block ultraviolet rays and infrared rays. The method according to any one of claims 1 to 3,
The transparent structure is characterized in that the transparent electrode structure for an organic electronic device,
Transparent structure that can block ultraviolet rays and infrared rays. delete delete delete delete

Images