WO2017039252A1

WO2017039252A1 - Light emitting barrier film and method of forming same

Info

Publication number: WO2017039252A1
Application number: PCT/KR2016/009559
Authority: WO
Inventors: 황재정
Original assignee: 주식회사 제이케이리서치
Priority date: 2015-08-28
Filing date: 2016-08-26
Publication date: 2017-03-09
Also published as: KR20170025379A

Abstract

The present invention relates to a transparent 2D photonic crystal-structured light emitting barrier film having excellent heat dissipating properties, extremely low permeability of gases including oxygen and moisture, and high mechanical strength and pliability, and to a method of forming the light emitting barrier film. According to the present invention, a high-efficiency light emitting barrier film may be provided which has light transfer directionality, and shows excellent optical properties and a long lifespan even in extreme environments of high heat, high humidity, and high density light irradiation.

Description

Light emitting barrier film and forming method thereof

The present invention relates to a light emitting barrier film having a transparent two-dimensional photonic crystal structure having excellent heat dissipation characteristics, extremely low transmittance of a gas containing oxygen and / or moisture, and high mechanical strength and flexibility, and a method of forming the same.

Barrier films are widely used in areas that require the blocking of moisture and oxygen in various fields from food packaging to electronic products. Among them, high barrier properties are required for applications in the display field due to the low stability of photoactive materials such as emitters. As an example, OLEDs require an oxygen transmission rate (OTR) of 1.0 X 10 ^-6 cc / m ² day bar or less, and a water vapor transmission rate (WVTR) of 1.0 X 10 ^-6 g / m ² day or less. In the display device using a quantum dot (Quantum dot) is also different depending on the application target, but also very low (1.0 X 10 ^-6 ~ 1.0 X 10 ^-2 ) oxygen transmission rate and water vapor transmission rate is required. In particular, the oxidation of photo / electric / electronic devices is known to be about 3 times faster than oxygen due to oxidation by water electrochemical reaction, so low water vapor transmission rate is essential.

The kinetic diameters of oxygen and water molecules are ~ 0.35nm and ~ 0.26nm, respectively, and are easily permeable to micro and macro defects of 1 nm or more generated during barrier layer deposition, and also low density polymers with large free volume due to weak attraction and crystallinity between the polymer chains. In this case, the mobility between the polymer chains of oxygen and water molecules is considerable, and thus it is impossible to produce a barrier film having high barrier properties required only by the polymer barrier layer.

On the other hand, inorganic matters have very low solubility and diffusivity compared to polymers such as PET or acrylic, which shows a very good blocking effect. Even a single silica layer of several tens to hundreds of nm by vapor deposition shows a water vapor transmission rate of 10 ⁻³ to 10 ⁻⁶ g / m ² · day. However, in reality, it is not easy to obtain an inorganic oxide coating layer free of cracks and defects, and economic efficiency is greatly reduced due to the construction and production problems of mass production equipment.

In addition to the vapor deposition method, the wet coating method is also applied, which can produce a high quality organic / inorganic layer barrier film if proper conditions are maintained because there is no shadow effect. Although there is no shadow effect to mitigate the defects of the substrate, this method also requires very careful management of the substrate and the adhesion between the bleed-proof layer, the flattening layer having a flatness within several nm, and the inorganic material before raising the inorganic layer. After providing the anchor layer to increase the dense inorganic layer is the wet coating. As the inorganic layer, alumina having a very low solubility and diffusion is most often used, but SiN or silica is also commonly used. However, because of the low economical efficiency, such as a barrier film produced by vapor deposition, its use is limited, and thus a high-performance barrier film with economical economy is urgently needed.

Quantum dots are easily applied to the display field because they can easily control band gap by quantum confinement effect and size, and can realize various colors as well as excellent luminescence characteristics. There are some problems to be solved.

Quantum dots are metastable materials with a large surface area and very high surface energy, and are very weak in optical, physical and chemical stability in the operating environment of quantum dot devices.

In addition to the aggregation due to inadequate dispersion, in order to lower the surface energy of the quantum dots, the growth of particles by Ostwald ripening occurs continuously, and melting or sintering at very low temperatures (~ 100 ^o C), even at room temperature This occurs and quantum dot aggregation occurs, and its progress is much faster at high temperatures. This phenomenon is more prominent in quantum dots in the smaller blue region. The aggregation of the quantum dots shows a decrease in luminous efficiency and long wavelength shift of the luminous wavelength due to the increase of particle size, self absorption and quenching. Therefore, the quantum dots must be well protected on the surface and they must be evenly distributed apart from each other over a proper distance.

In addition, quantum dots cause thermal and photochemical reactions due to moisture, oxygen, heat, and continuous strong light, which greatly deteriorate their optical properties, and in particular, physical and optical properties of quantum dots with respect to surface reactions of quantum dots such as ligand substitution and defect generation. Is very sensitive, and large luminous efficiency decreases and color changes occur. Therefore, in order to preserve the operational stability of the quantum dot device, it is essential to completely block water and oxygen from the outside, suppression of heat generation, and heat radiation.

To solve the above problems

An object of the present invention is to provide a barrier film having a very low permeability of a gas containing oxygen and / or moisture to increase the stability of oxygen and / or moisture sensitive electronic materials.

It is another object of the present invention to maintain a stable performance of a light emitting film for a long time in the harsh conditions in which high temperature, high humidity, and strong light irradiation occur for a long time.

Another object of the present invention is to provide a barrier film having a long life and high light efficiency by introducing a heat radiation structure on the barrier film.

Still another object of the present invention is to provide a barrier film having high economical efficiency at low cost by introducing an easy wet process.

It is another object of the present invention to provide a barrier film having high mechanical strength and flexibility to provide low defect rate and ease of assembly process, and to maintain high barrier properties for a long time.

Another object of the present invention is to provide a barrier film having a transparent two-dimensional photonic crystal structure to increase the light efficiency of the display device.

Another object of the present invention is to provide a transparent two-dimensional photonic crystal structure barrier film to eliminate the components for the optical path conversion in the display device.

Another object of the present invention is to increase the light efficiency of the display device by the selective transmission and reflection of light according to the wavelength by introducing an optical layer on the barrier film.

Still other objects of the present invention will be readily understood through the following description of the embodiments.

In order to achieve the object as described above, according to one aspect of the present invention, the nano-phosphor in the pores of the nanoporous metal oxide film, preferably nanoporous alumina film having a two-dimensional photonic crystal structure anodized in an acid solution The structure of the light emitting barrier film in which the pores were sealed after the introduction of H was provided.

The anodized alumina film is a hexagonal honeycomb structure in which pores are regularly arranged, and the pore diameter is 10 to 500 nm, preferably 15 to 300 nm, more preferably 30 to 120 nm, and the thickness of the anodized alumina barrier layer is 10 nm. It is -500 nm, Preferably it is 30-300 nm, More preferably, it is 50-100 nm, The thickness of the whole film is 1um-50um, Preferably it is 2-30um, More preferably, it is 10-20um.

The periphery of the anodized alumina film may be used as a support and a heat dissipation structure of the anodized alumina film, leaving a predetermined width of aluminum.

Outside the barrier layer of the anodized alumina film may be provided with a polymer coating layer having good stretch and mechanical strength, the polymer is a coating layer of acrylic, epoxy, urethane, silicone, amide, fluorine-based polymer and organic-inorganic hybrid having a high transparency Can be used.

Outside of the barrier layer of the anodized alumina film, a selective light transmission enhancement layer and a reflection layer may be formed on the outside of the barrier layer, and the region of the wavelength may be near infrared light (near IR) and far infrared light (IR) having a great influence on heat transfer as well as visible light. far IR).

In the pores of the anodized alumina film, nano phosphors such as quantum dots may be uniformly applied.

By forming a transparent passivation film inside the pores of the anodized alumina film, it is possible to inhibit energy transfer between the surface of the alumina and the nanophosphor.

* The passivation film is a material having a large band gap, and may be metal oxides, nitrides, and sulfides. The metal may be Si, Al, Ti, Zr, Hf, Nb, Mo, W, Ta, or the like.

Form a thin film of a material having the same or higher affinity as the ligand on the surface of the quantum dot in the pores of the anodized alumina film, thereby providing a binding force to the quantum dots to be stably and uniformly positioned in the pores and inhibit the ligand substitution reaction on the surface of the quantum dot have.

After the nanophosphor is introduced into the pores of the anodized alumina film, the pores may be sealed by a sealing material.

The sealant may be any one or a mixture of transparent plate-shaped nano-inorganic material, metal oxide sol, organic polymer.

On one side of the barrier film, preferably on the sealing side, an adhesive having a barrier property can be applied to enable the direct attachment to the desired substrate.

According to another aspect of the invention, the step of applying a mask for forming a pattern on one surface of aluminum foil; Forming a nanoporous film by anodizing in an acid solution; Applying a nano phosphor inside the nanoporous film pores; Provided is a method of forming a light emitting barrier film comprising sealing pores.

According to the structure and the formation method of the light emitting barrier film according to the present invention, the light emitting barrier having a transparent two-dimensional photonic crystal structure having heat dissipation characteristics and extremely low transmittance of a gas containing oxygen and moisture and having high mechanical strength and flexibility Films can be provided, which are directional to light transmission, ensuring excellent light properties and long life even in the harsh environments of high heat, high humidity and high density light irradiation.

1 is a structural diagram of a barrier film

Figure 2. Structural drawing of porous alumina.

As the inventive concept allows for various changes and numerous embodiments, particular embodiments will be illustrated in the drawings and described in detail in the written description. However, this is not intended to limit the present invention to the specific embodiments, it should be understood that it includes all changes, equivalents, and substitutes included in the spirit and scope of the present invention, and may be modified in various other forms. However, the scope of the present invention is not limited to the following example.

Hereinafter, exemplary embodiments of the present invention will be described in detail with reference to the accompanying drawings, and like reference numerals denote the same or corresponding elements regardless of reference numerals, and redundant description thereof will be omitted.

Nanoporous metal oxides through anodization of valve metals have many academic and industrial values. Nanoporous anodized alumina, the most widely used among them, is a technology that has been introduced for more than 100 years and is commonly used around the surface of aluminum chassis or aluminum tableware, and its manufacturing process is also common. Nanoporous alumina exhibits excellent optical, chemical and physical properties due to its material and structural properties, and is a material well suited for the purpose of the present invention with easy processing and low cost.

Anodization of aluminum in the acid solution simultaneously coincides with the electrochemical oxidation of aluminum and the local electrochemical dissolution of the resulting alumina, thereby forming a nanoporous alumina film on the aluminum surface. Its nanoporous structure (pore size, microspatial distance and barrier layer thickness) and film growth rate are precisely controlled by the type of electrolyte, temperature, voltage, and current density. Alumina etching solution such as can be used to finely control the size of the pore and the thickness of the barrier layer and its production and control methods are well known. (See Figure 1)

Looking at these properties, the resulting nanoporous alumina is very transparent, and the light parallel to the pore channel is an excellent optical material having a high transmittance of 90% or more from visible light to near infrared region. In addition, when the incident light deviates from the parallel direction of the channel, the transmittance of the light rapidly decreases. This is due to the anisotropy of the photonic density of state (DOS) due to the periodic change of the refractive index due to the periodic pore-arranged anodized alumina structure. This nanoporous alumina is a 2D photonic crystal. Can be seen.

The directional selectivity of the transmitted light is also applied to the transmission of the emitted light, and this property is maintained even in the light emitting device. Such light can increase the light efficiency of the device with proper use of direction selectivity, and there is no need for a separate optical component for changing an optical path such as a prism sheet or an optical waveguide.

Most importantly, alumina is known to be one of the best barrier materials due to its very good barrier properties, due to its very low solubility and diffusion into water and oxygen.

The main reason for the decrease in quantum dot light efficiency is due to the oxidation reaction of quantum dots by oxygen and water, which promotes the substitution reaction of ligands that protect the quantum dots while generating defects on the surface. The surface state of the quantum dot has an absolute influence on the luminous efficiency and the wavelength of light emission. Therefore, preservation of the surface state of the quantum dot is very important.

In addition to oxygen and moisture, continuous irradiation of heat and strong light also greatly affects the performance of quantum dots, but this is ultimately due to the oxidation reaction caused by moisture and oxygen. As is well known, the rate of reaction increases with temperature rise exponentially, and the rate of surface oxidation reaction at high temperatures also increases exponentially. The energy of the heat itself generated during operation of the device is not much lower than the chemical bond in the molecule, and does not break the bond in the molecule or contribute to the formation of a new bond, but only increases the reaction rate between the reactants. Therefore, if there is no reactant such as oxygen or moisture, this kind of heat chemical reaction does not occur.

The continuous irradiation of light produces hole-electron pairs of quantum dots, most of which recombine and are emitted as light, but some generate heat due to the disappearance of non-luminescent processes or relax to ground exciton and cause electron-phonon interactions The phonon accumulated in the quantum dots thereby heats the quantum dots and at the same time narrows the band gap of the quantum dots, causing long wavelength shift of the emission color. In addition, absorption and non-emissive extinction by surface defects are also converted to heat to heat the quantum dots. That is, unless the quantum efficiency is 100%, heat is accumulated in the quantum dots by the incident photons. The heated quantum dots promote the loss of capping ligands and the formation of surface defects by rapid oxidation reactions by moisture and oxygen. In particular, loss of ligand causes melting and low temperature sintering of the quantum dots, causing growth and aggregation of the quantum dot particles.

In addition, a very important fact is that all excited intermediates, including ground exciton, are chemically very unstable and bond very easily with the surrounding oxygen or water, causing rapid oxidation.

Therefore, the ability to block moisture and oxygen is the most important key factor in quantum dot stability. Nanoporous alumina exhibits excellent barrier properties by making it difficult to transport gases due to the repetitive structure of nanopore as well as the properties of alumina material which has excellent gas barrier properties.

Another advantage of nanoporous alumina is its very large surface area due to the nanostructures. As a result, it is very easy to obtain a uniform, high concentration quantum dot film without aggregation, which has a very large surface area and maintains an appropriate distance between the quantum dots, thereby maintaining high quantum efficiency and long wavelength shift of emission color. In addition, this structure is also advantageous in heat dissipation, which can mitigate the growth and aggregation of quantum dots due to low temperature sintering.

The light emitting barrier film using the anodized alumina film having the above advantages is produced through the following process.

1. 패턴의 형성1. Formation of patterns

In preparing the barrier film, aluminum may be used as a support and a heat dissipation structure of the nanoporous anodized alumina film by leaving a predetermined width of aluminum at the periphery of the nanoporous alumina film during anodization. Thin nanoporous alumina films of 10 μm or less are flexible but are prone to breakage as the film thickness increases. Therefore, when aluminum having high flexibility and high mechanical strength is used as a support, mechanical strength against external impact of the nanoporous alumina film can be greatly increased.

Another aspect is an improvement in heat dissipation of the nanoporous alumina film. The thermal conductivity of aluminum (237W / mK) is about 10 times higher than that of alumina (20 ~ 30W / mK), which can effectively remove the heat in the barrier film generated during the operation of the light emitting device. It can greatly increase the service life. For more effective cooling, a forced cooling means such as a thermoelectric cooler may be provided to lower the temperature of the entire barrier film by cooling the portion of the alumina through the cooling of the peripheral aluminum.

The width, line spacing, and pattern of the aluminum can be modified as appropriate depending on the application. A thin line width aluminum having a high aperture ratio is suitable for an application requiring high light transmittance, and a thick line width aluminum having a low aperture ratio is suitable for an application requiring high mechanical strength and heat dissipation. High optical transmittance is important for applications such as displays, and it is desirable to increase the aperture ratio and to have light reflecting means on the light source side to recover light reflected by the aluminum pattern.

The shape of the pattern is appropriate in the form of a mesh or honeycomb in consideration of mechanical strength and heat dissipation efficiency, but various shapes may be modified as necessary. For example, when the light emitting barrier film is applied to the light guide plate side by side in the form of a band, a ladder pattern is suitable. At this time, considering the low thermal conductivity of alumina, the width between aluminum lines should not be too wide.

The fabrication is performed by forming a desired pattern on one side of the aluminum foil by means such as screen printing or inkjet, and then selectively anodizing the unmasked portion to replace the ink-protected aluminum 12 around the nanoporous alumina film 11. Leave it as it is.

2. 나노다공성 알루미나 필름의 형성2. Formation of Nanoporous Alumina Film

Nanoporous alumina film can be obtained by electrochemical oxidation after the aluminum foil masked in the acid solution to the anode. The anodized alumina film is a hexagonal honeycomb structure in which pores are regularly arranged, and the diameter of the pores 21 is 10 to 500 nm, preferably 15 to 300 nm, more preferably 30 to 120 nm, and the anodized alumina barrier layer ( The thickness of 22) is 10 nm to 500 nm, preferably 30 to 300 nm, more preferably 50 to 100 nm, and the thickness of the entire film 23 is 1 um to 50 um, preferably 2 to 30 um, more preferably 10 to 20 um. to be. At this time, the acid solution may be used an organic acid, such as sulfuric acid, oxalic acid, phosphoric acid and hydrofluoric acid.

The size and spacing of the pores can be obtained by appropriately adjusting the applied voltage and current density and the temperature of the solution, which can be more precisely controlled by an etching process later. In order to obtain more and more regularly arranged pores, electrolytic polishing may be included to increase the flatness of the aluminum surface before anodizing, or nanoporous oxide films having irregular pores generated after the first anodization. Can be subjected to secondary anodization after etching with 5% phosphoric acid solution.

In order to obtain higher mechanical strength, a polymer coating layer having excellent elasticity and mechanical strength may be provided outside the barrier layer of the anodized alumina film, and the polymer may be acrylic, epoxy, urethane, silicone, amide, or fluorine-based polymer having high transparency. And coating layers such as organic-inorganic hybrids can be used. Considering that the refractive index of the alumina is 1.78, when the refractive index of the polymer layer is 1.4 or less, it is possible to obtain an antireflection effect, thereby increasing light transmittance. Such materials include Cytop (n = 1.34), PTEE and PFA (n = 1.35), which are fluorine-based polymers.

Outside of the barrier layer of the anodized alumina film, selective transmission of light and reflection layer can be formed according to the wavelength, and the region of the wavelength is near infrared light (near IR) and far infrared light (far) which have a great influence on heat transfer as well as visible light. IR) may be included. For example, when stimulating a quantum dot with a 450 nm blue LED to obtain white light and sending it toward the light guide plate, the light emitting barrier film has the highest transmittance in a region near 450 nm and reflects toward the light guide plate in the remaining visible light region to maximize light efficiency. Two layers of anti-reflective coating, consisting of a high and low refractive layers, can give the function of a dichroic filter. At this time, if a material such as ITO, ATO, FTO, AZO is used as the high refractive layer, it can be used as a reflective layer of near infrared (near IR) and far infrared (far IR) as well as function of the high refractive layer.

3. 나노형광체의 세공 도입3. Pore introduction of nanophosphor

The nano phosphor 24 such as a quantum dot may be uniformly applied inside the pores of the anodized alumina film. This can be achieved by a simple dip coating, and if necessary, ultrasonic waves are applied at the time of dipping to obtain a more uniform quantum dot coating film. For more effective application, we need to balance the polarity of the solvent and the surface tension when considering the wettability of nanoporous alumina. To this end, solvents require relatively high polarity and low surface tension.

A passivation film may be formed inside the pores of the anodized alumina film to suppress energy transfer between the alumina surface and the quantum dots. When anodized in an organic acid solution such as oxalic acid, singly ionized oxygen vacancy (F center) is generated in nanoporous alumina under the influence of oxalate anion, and the alumina itself shows a blue emission band. When the phosphor is introduced, the phosphor emission intensity is greatly increased along with the shift of the emission wavelength under the influence of Forster resonance energy transfer (FRET). This may be an advantage in applications requiring high quantum efficiency, but may be a significant limitation in applications in display fields where the emission wavelength is not allowed. In this case, a passivation film may be introduced on the surface of the alumina to suppress energy transfer. The passivation film is a transparent material having a large band gap, and may be a metal oxide, nitride, or sulfide, and the metal may be Si, Al, Ti, Zr, Hf, Nb, Mo, W, Ta, or the like.

A thin film of a material having the same or higher affinity as the ligand of the quantum dot surface may be formed inside the pores of the anodized alumina film to impart a bonding force between the quantum dots and the pore surface so that the quantum dots may be stably and uniformly positioned in the pores. In general, quantum dots are capped with various ligands on the surface to improve stability, and their types are various. Trioctylphosphine (TOPO), Hexadecylamine (HDA), Dodecylamine (DDA), 3-mercaptopropyl triethoxysilane (MPS), N , N -dimethyl-2- mercaptoethyl ammonium chloride (DMAC), etc. Affinity with the membrane surface is very large. The introduction of these on the surface of alumina increases the affinity between the quantum dots and the pore surface to form a more uniform and stable film of quantum dots, and can greatly suppress the substitution reaction of the quantum dot surface ligands. It is preferable to use an excess of ligand in order to suppress the quantum dot performance by the desorption and substitution reaction of the ligand surrounding the quantum dot.

As another effect thereof, the emission wavelength change due to FRET can be suppressed.

4. 세공의 밀봉4. Sealing of pore

After the quantum dots are introduced into the pores of the anodized alumina film, the pores may be sealed by a sealing material. As a result, a light emitting barrier film that can withstand harsh environments of high temperature and high humidity can be completed.

The sealant may be any one or a mixture of transparent plate-shaped nano-inorganic material, metal oxide sol, organic polymer. When the barrier layer is formed with a metal oxide sol or an organic polymer mixed with a plate-shaped nano-inorganic material, a lamellar layer is formed as shown in the following figure. Thus, the distance of gas molecules becomes very long (tortuous path). It is greatly suppressed. The plate-shaped nano-inorganic particles preferably have a high aspect ratio (thickness; 1 nm and a width of 2 μm or more) having excellent gas barrier properties and light transmittance, and are typically represented by Momoryonite and hectorite.

If the object to be attached to the barrier film is an object to be easily bonded, the sealing material layer may be omitted. For example, in the case of a light guide plate made of PMMA material, the surface of the light guide plate is heated to near Tg, and then pressed to a nanoporous light emitting barrier film to remove moisture in the pores and at the same time, bonding and sealing can be performed by infiltration of a polymer.

On one side of the barrier film, preferably on the sealing side, an adhesive having a barrier property can be applied to enable a direct attachment to the desired substrate. In the case of optical devices, the refractive index thereof is adjusted according to the characteristics of the substrate to be applied, thereby minimizing the reflection between interfaces to increase the light efficiency. For example, the refractive index of PMMA, which is commonly used as a light guide plate, is 1.49, and the refractive index of nanoporous alumina is 1.78 to 1.55 depending on porosity, and the refractive index of the sealing material is about 1.51 to 1.61.

As described above, the present invention has been described with reference to the accompanying drawings, but various modifications and changes can be made without departing from the spirit of the present invention. Therefore, the scope of the present invention should not be limited to the described embodiments, but should be defined by the claims below and equivalents thereof.

According to an aspect of the present invention, a light emitting barrier in which pores are sealed after introduction of nano phosphors into the pores of a nanoporous metal oxide film having a two-dimensional photonic crystal structure, preferably a nanoporous alumina film, by anodizing in an acid solution. The structure of the film is provided.

INDUSTRIAL APPLICABILITY The present invention can be industrially used for a method of forming a light emitting barrier film.

11: nanoporous alumina

12: aluminum

21: Handwork

22: nanoporous alumina barrier thickness

23: nanoporous alumina thickness

24: nanophosphor

Claims

A barrier film comprising a nanoporous film protecting an electronic material sensitive to any or all of moisture and oxygen,

It includes a nanoporous film having a plurality of nano-sized holes in the base material exhibiting low permeability to any one or both of water and oxygen,

An electronic material composition sensitive to any one or both of moisture and oxygen is disposed in the hole,

The barrier film of which said hole is hermetically sealed by a sealing material.
The method according to claim 1,

The nanoporous film,

The pores are arranged regularly, the diameter of the pores is 10-500nm, preferably 15-300nm, more preferably 30-120nm, the barrier layer thickness of the pores is 10nm-500nm, preferably 30-300nm, More preferably, the thickness of the whole film is 50-100 nm, 300 nm-50 micrometers, Preferably it is 2-30 micrometers, More preferably, the barrier film consists of 10-20 micrometers.
The method according to claim 1 or 2,

The nanoporous film,

A barrier film, which is a metal oxide formed by anodization of a valve metal comprising any one of Al, Ti, V, Zr, Hf, Nb, Ta, and W.
The method according to claim 1 or 2,

The nanoporous film,

A barrier film formed by using track etch or phase separation.
The method according to any one of claims 1 to 4,

On the periphery of the nanoporous film,

Barrier film improved heat dissipation formed in the form of a mesh or ladder by placing a metal wire.
The method according to any one of claims 1 to 4,

The nanoporous film,

A barrier film, wherein the surface is passivated with an oxide, nitride or sulfide of any one of Si, Al, Ti, Zr, Hf, Nb, Mo, W and Ta.
The method according to any one of claims 1 to 4,

The nanoporous film,

A barrier film whose surface is treated with a ligand of an electronic material sensitive to either or both of moisture and oxygen.
The method according to any one of claims 1 to 7,

Electronic material sensitive to any one or both of the moisture and oxygen,

A barrier film selected from any one or a combination of pigment particles, quantum dots and colloidal particles as nanoparticles.
The method according to claim 1,

The sealing material

A barrier film, which is any one or a mixture of transparent inorganic plate-like nano-inorganic, metal oxide sol and organic polymer.
The method according to claim 9,

The transparent plate-shaped nano inorganic material,

A barrier film, which is any one or a mixture of laponite, vermiculite, Montmorillonite, bentonite, and hectorite.
The method according to any one of claims 1 to 10,

A barrier film, comprising a selective wavelength enhancement transmission and a reflection layer.
The method according to any one of claims 1 to 10,

Barrier film, the adhesive is applied to one side.
An electronic device comprising an electronic material sensitive to either or both of moisture and oxygen, wherein the electronic material is arranged inside the barrier film according to claim 1.
The barrier film according to claim 11 is applied to any one of a liquid crystal display (LCD), an organic light emitting diode (OLED), a solar cell, an organic thin film transistor (OTFT), an organic / inorganic sensor and a microelectromechanical system (MEMS). device.
As a manufacturing method of the barrier film in any one of Claims 1-12,

Applying a mask for pattern formation to one surface of the metal foil;

Forming a nanoporous film by anodizing the result of applying the mask to an acid solution;

Inserting an electronic material sensitive to either or both of moisture and oxygen into the pores of the nanoporous film; And

Sealing the pores;

Forming a barrier film, including