KR20150022495A - Substrate laminate, electronic device having the substrate laminate and method of manufacturing the same - Google Patents

Abstract

The present invention relates to a substrate laminate, to an electronic device having a substrate laminate, and to a method for manufacturing the same. The present invention includes the steps of: forming an inorganic film by using oxide or nitride on a substrate; and forming a metal film or a metal oxide film in an atom layer deposition method on the substrate on which the inorganic film is formed.

Description

BACKGROUND OF THE INVENTION 1. Field of the Invention [0001] The present invention relates to a substrate laminate, an electronic device including the substrate laminate, and a method of manufacturing the substrate laminate.

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a substrate laminate, an electronic device including the same, and a method of manufacturing the same.

Display devices and lighting devices using liquid crystal devices, electronic ink devices, organic light emitting devices (OLED) and the like are widely used or appearing on the market, and photovoltaic devices using organic or inorganic materials are also being used for pollution-free energy production.

Electronic devices and metal wires constituting such devices are vulnerable to chemical substances widely present in living environments such as moisture, oxygen, etc., and are denatured or oxidized. Therefore, it is very difficult to block such substances from approaching electronic devices existing in the device It is important.

Korean Patent Laid-Open No. 10-2008-0105832

The present specification is intended to provide a substrate laminate, an electronic device including the same, and a method of manufacturing the same.

The present invention relates to a method of forming an inorganic film using an oxide or a nitride on a substrate, And

And forming a metal film or a metal oxide film by atomic layer deposition on the substrate on which the inorganic film is formed.

The present invention also relates to a method of manufacturing an electronic device including forming an organic light emitting portion in which a first electrode, at least one organic material layer, and a second electrode are sequentially laminated on a substrate laminate manufactured by the method for manufacturing a substrate laminate .

The present disclosure also relates to a substrate comprising: a substrate; An inorganic film provided on the substrate and containing an oxide or a nitride; And a metal film or a metal oxide film provided on the inorganic film.

Further, the present specification relates to the substrate laminate; And

And an organic light emitting portion in which a first electrode, at least one organic material layer, and a second electrode are sequentially stacked on the substrate laminate.

Further, the present specification provides a display device including the electronic device.

Further, the present specification provides a lighting apparatus including the electronic device.

The substrate laminate according to one embodiment of the present invention has the advantage that the film formed on the substrate is uniform and stable.

The substrate laminate according to one embodiment of the present invention has an excellent barrier performance for blocking moisture, oxygen, and the like.

1 is a flowchart of a method of manufacturing a substrate laminate and an electronic device according to an embodiment of the present invention.
Fig. 2 shows test results of the barrier performance under the environment of 85 deg. C and 85% relative humidity in Comparative Example 1. Fig.
Fig. 3 shows test results of the barrier performance under the environment of 85 deg. C and 85% relative humidity in Example 1. Fig.
FIG. 4 is a view showing a bonding relationship between an inorganic film and a metal oxide film in a substrate laminate according to an embodiment of the present invention.

Hereinafter, the present invention will be described in detail.

The present invention relates to a method of forming an inorganic film using an oxide or a nitride on a substrate, And

And forming a metal film or a metal oxide film by atomic layer deposition (ALD) on the substrate having the inorganic film formed thereon.

In one embodiment of the present invention, the substrate is not particularly limited, and a substrate common in the art can be used. For example, a glass substrate, a plastic substrate, or the like.

When the substrate laminate is applied to a flexible element, the substrate laminate includes a flexible material. For example, a substrate of glass, plastic or film type in the form of a thin film which can be bent can be used.

The material of the plastic substrate is not particularly limited, but may be selected from the group consisting of polyacrylate, polypropylene (PP), polyethylene terephthalate (PET), polyethylene ether phthalate, polyethylene phthalate ), Polybuthylene phthalate, polyethylene naphthalate (PEN), polycarbonate (PC), polystyrene (PS), polyether imide, polyether sulfone ), Polydimethyl siloxane (PDMS), polyether etherketone (PEEK), polyimide (PI), and combinations thereof. The plastic substrate may be used in the form of a single layer or a multilayer.

The method for forming the inorganic film is not particularly limited, and a general method in the art can be used. For example, by a sputtering method, a wet coating method, or a chemical vapor deposition (CVD) method.

The inorganic film may be made of an oxide or nitride of Si. For example, SiO ₂ , SiN, SiO _x N _y and the like, and preferably SiO ₂ .

In this case, the oxide means a binary compound of oxygen and another element, and the nitride means a binary compound with an element having a higher ionization tendency than nitrogen and nitrogen.

The formation of the inorganic film on the substrate using the oxide or nitride is a surface modification for introducing a reactive group capable of chemically reacting with the metal deposited on the substrate by atomic layer deposition, which will be described later. When an inorganic film is formed using an oxide or a nitride on a substrate, a reactive group is present at the interface of the inorganic film.

The reactive group varies depending on the kind of the oxide and the nitride used, but may be, for example, a hydroxyl group (-OH), an amine (-NH ₂ ), a nitro group (-NO ₂ ), or the like. Preferably a hydroxy group (-OH).

The metal film or the metal oxide film may be deposited by atomic layer deposition on a substrate on which an inorganic film is formed.

According to one embodiment of the present invention, if the metal film or the metal oxide film includes an element other than the nonmetal element in the periodic table, the kind thereof is not particularly limited, but may include, for example, a metal element, a transition element or a typical element . Specifically, the metal film or the metal oxide film may include at least one of Al, Ti, Mn, Mg, Zr, Ce, Nb, La, Ta, In, Zn, Sn and oxides thereof. More specifically, the metal film may include at least one of Al, Ti, Mn, Mg, Zr, Ce, Nb, La, Ta, In, Zn, and Sn. The metal oxide film may include TiO ₂ , Al ₂ O ₃ , _{Ta 2 O 3, Ti 3 O} 3, ZrO 2, Nb 2 O 3, NbO, Nb 2 O 5, CeO 2, ZnO, MgO, La 2 O 3, MnO 2 And In ₂ O ₃ .

In the atomic layer deposition method, vapor of a metal film or a precursor of a metal oxide film is absorbed on a substrate in which an inorganic film is formed in a vacuum chamber. At this time, the precursor chemically reacts with the reactive group in the inorganic film formed on the substrate. Subsequently, the reaction product is introduced into the chamber under the condition promoting the reaction with the precursor adsorbed on the substrate to form a desired metal film or metal oxide film.

When the metal film or the metal oxide film is multi-layered, the step of exposing the substrate to the vapor of the precursor and the step of reacting the precursor absorbed in the substrate with the reactant may be repeated at least twice. When a multilayer metal film or a metal oxide film is repeatedly formed as described above, the respective layers may be formed of the same material or different materials.

The growth by the atomic layer deposition method is in contrast to the growth by a physical vapor deposition (PVD) method such as a general chemical vapor deposition (CVD) method, a vacuum deposition method, a sputtering method, and an ion plating method. Specifically, the growth by the chemical vapor deposition method and the physical vapor deposition method starts and proceeds at a limited number of nucleation sites on the surface of the substrate, so that a columnar microstructure having a boundary line between the columns is formed, Can happen. On the other hand, the atomic layer deposition method can produce a very thin film adhering to the surface of the substrate without gaps, and thus can have extremely low gas permeability.

When a metal film or a metal oxide film is formed on a substrate, if there is no reactive group that chemically reacts with the metal, the film is physically bonded and deposited, so that the film can not be deposited stably and the characteristics of the interface are weak. It can penetrate.

In this specification, the metal film or the metal oxide film can chemically bond with the reactive group present in the expression of the inorganic film, so that the metal film or the metal oxide film can be deposited uniformly on the substrate stably. Therefore, it has an advantage of being able to protect against penetration of moisture, oxygen and the like because of its excellent interface characteristics.

At this time, the bond between the reactive group and the metal may be any one of coordination bond, covalent bond, and covalent bond.

In the present specification, the metal film or the metal oxide film is a barrier layer that protects against penetration of moisture, oxygen, and the like.

In this specification, it is preferable that the refractive index of the metal film or the metal oxide film is equal to or larger than the refractive index of the substrate. For example, the refractive index of the metal film or the metal oxide film may be 1.5 or more and 2.5 or less.

For example, as shown in FIG. 4, Al ₂ O ₃ is chemically bonded to a hydroxyl group present on the surface of the inorganic film, and Al ₂ O ₃ is uniformly deposited.

1 (a) and 1 (b), an inorganic film of SiO ₂ is formed on a plastic substrate by a sputtering method, and as shown in FIG. 1 (c) A metal film or a metal oxide film of two layers can be formed thereon by an atomic layer deposition method.

In one embodiment of the present invention, the method may further include forming a light extracting layer on one surface of at least one of the manufactured substrate stacks.

In this specification, the light extracting layer is not particularly limited as long as it can induce light scattering and improve light extraction efficiency of the device. In one embodiment, the light extracting layer may be a structure in which scattering particles are dispersed in the binder. In another embodiment, the light extracting layer may be a structure for scattering light by a projection structure such as a plurality of lenses or the like.

The light extracting layer may be formed directly by a method such as spin coating, bar coating or slit coating, or may be formed in a film form.

According to an embodiment of the present invention, the method may further include forming a flat layer on the light extracting layer.

In one embodiment of the present invention, the method may further include the step of providing a substrate on a carrier substrate before forming an inorganic film on the substrate.

The carrier substrate may be made of materials known in the art. More specifically, the carrier substrate may be a glass substrate, a metal substrate, a plastic substrate, or the like, but is not limited thereto.

The thickness of the carrier substrate may be 0.5 mm or more and 0.7 mm or less, but is not limited thereto.

When the substrate is a plastic substrate, it may be formed by laminating a plastic substrate on the carrier substrate, or by coating a composition for forming a plastic substrate on the carrier substrate and curing the substrate.

For example, when the plastic substrate is a polyimide film, a polyimide film may be laminated on the carrier substrate to form a substrate, or a polyamic acid composition may be coated on the carrier substrate and cured to form a substrate.

In one embodiment of the present disclosure, the step of providing a substrate, an inorganic film, a light extracting layer or a flat layer on a carrier substrate may be performed by a plate-to-plate process or a roll-to-plate process ) Process, as well as a roll-to-roll process. In particular, in the present specification, a roll-to-roll process can be used to reduce the process cost.

The present invention provides a method of manufacturing an electronic device including forming an organic light emitting portion in which a first electrode, at least one organic material layer, and a second electrode are sequentially laminated on a substrate laminate manufactured according to the method for manufacturing a substrate laminate, to provide.

The method of forming the first electrode, the at least one organic material layer, and the second electrode is not particularly limited and may be manufactured by a technique commonly used in the art.

A metal oxide or a metal oxide having conductivity or an alloy thereof is deposited on the substrate stack by using a physical vapor deposition (PVD) method such as sputtering or e-beam evaporation, And an organic material layer including a hole injecting layer, a hole transporting layer, a light emitting layer and an electron transporting layer is formed thereon by a solution coating method such as a vacuum evaporation method, spin coating, dip coating, inkjet printing, screen printing, spraying or roll coating And thereafter depositing a material usable as a second electrode thereon.

The material of the first electrode, the organic material layer, and the second electrode is not particularly limited, and materials commonly used in the art can be used.

And forming a sealing portion covering the outside of the organic light emitting portion.

If the sealing portion covers the outside of the organic light emitting portion and the organic light emitting portion can be sealed, the sealing method and material are not particularly limited.

For example, it can be pressed with an encapsulating film, or a metal or metal oxide can be deposited and sealed.

In one embodiment of the present invention, as shown in FIG. 1D, a first electrode, at least one organic material layer, and a second electrode are sequentially laminated on a substrate provided with an inorganic film and a metal layer to form an organic light emitting portion As shown in Fig. 1 (e), a sealing portion covering the outside of the organic inventive part can be formed.

The method of manufacturing an electronic device according to an embodiment of the present invention includes the steps of manufacturing a substrate stack according to a method of manufacturing the substrate stack on a carrier substrate before forming an organic light emitting portion on the substrate stack As shown in FIG.

The method of manufacturing an electronic device according to one embodiment of the present disclosure may further include separating the carrier substrate after forming the organic light emitting portion on the substrate stack. At this time, the method of separating the carrier substrate can use a method known in the art such as a knife, a laser, etc., and can be easily separated even with a knife.

In one embodiment of the present invention, the method may further include forming a sealing portion that covers the outside of the organic light emitting portion before separating the carrier substrate.

The material is not particularly limited as long as the sealing portion covers the outside of the organic light emitting portion and can seal the organic light emitting portion. For example, it can be pressed by a sealing film, vapor-deposited with a metal or a metal oxide, or coated and cured by sealing the resin composition.

In one embodiment of the present disclosure, the seal may be formed by depositing a metal or a metal oxide by atomic layer deposition.

In one embodiment of the present disclosure, the sealing portion may be a metal layer or a metal oxide layer of two or more layers formed by atomic layer deposition.

In one embodiment of the present disclosure, the sealing portion seals at least the outside of the organic light emitting portion, and may seal the outside of the organic light emitting portion as well as the exposed portion of the substrate stacked body.

In one embodiment of the present invention, there is provided a method of manufacturing a light emitting device, comprising: floating a substrate laminate formed with an organic light emitting portion from a ground using a fin after forming an organic light emitting portion or after separating a carrier substrate; And forming a metal layer or a metal oxide layer on the outer side of the organic light emitting portion and the outer side of the substrate stacked body by atomic layer deposition and sealing.

At this time, the outer side of the substrate stack includes a portion where the organic light emitting portion is not formed, a surface opposite to the surface where the organic light emitting portion is formed, and a side face. Specifically, the outside of the organic light emitting portion and the outside of the substrate laminate mean the front surface of the electronic device.

In this specification, the step of sequentially forming the substrate laminate and the organic light emitting portion on the carrier substrate is not limited to a plate-to-plate process or a roll-to-plate process, A roll-to-roll process can be used. Particularly, since the present invention can manufacture an electronic device by using a roll-to-roll process, there is a feature that the process cost can be reduced.

Examples of the electronic device include, but are not limited to, an organic light emitting device, an organic solar cell, an organic photoconductor (OPC), and an organic transistor.

In one embodiment of the present invention, the electronic device may be an organic light emitting device.

The electronic device may be a flexible organic light emitting device. In this case, the substrate laminate includes a flexible material. For example, a substrate of glass, plastic or film type in the form of a thin film which can be bent can be used.

The material of the plastic substrate is not particularly limited, but may be selected from the group consisting of polyacrylate, polypropylene (PP), polyethylene terephthalate (PET), polyethylene ether phthalate, polyethylene phthalate ), Polybuthylene phthalate, polyethylene naphthalate (PEN), polycarbonate (PC), polystyrene (PS), polyether imide, polyether sulfone ), Polydimethyl siloxane (PDMS), polyether etherketone (PEEK), polyimide (PI), and combinations thereof. The plastic substrate may be used in the form of a single layer or a multilayer.

The present disclosure also relates to a substrate comprising: a substrate; An inorganic film provided on the substrate and containing an oxide or a nitride; And a metal film or a metal oxide film provided on the inorganic film.

As used herein, the term "substrate laminate" means that two or more layers are laminated and used as a substrate of an electronic device or the like. Specifically, the substrate laminate may include at least a substrate, and may further include a functional layer formed on at least one side of the substrate. The functional layer may be an inner barrier layer, an outer barrier layer, a light extraction layer, a flat layer, an adhesive layer, or the like.

According to one embodiment of the present disclosure, the thickness of the substrate may be 10 nm or more and 10 cm or less.

The description overlapping with those described above in the method of manufacturing the substrate laminate is the same as the description of the components of the substrate laminate.

A reactive group is present on the surface of the inorganic film containing the oxide or nitride, and the reactive group of the inorganic film and the metal of the metal film or the metal oxide film can be chemically bonded.

The reactive group is not particularly limited as long as it is capable of chemically reacting with a metal film or a metal oxide film. For example, the reactive group may be at least one of a hydroxyl group, an amine group and a nitro group.

The inorganic film may be made of an oxide or nitride of Si. For example, SiO ₂ , SiN, SiO _x N _y and the like, and preferably SiO ₂ .

The thickness of the inorganic film may be 1 nm or more and 500 nm or less. If necessary, it may be 5 nm or more and 50 nm or less.

According to one embodiment of the present invention, if the metal film or the metal oxide film includes an element other than a non-metal element in the periodic table, the kind thereof is not particularly limited, but may include a metal element, a transition element, or a typical element. Specifically, the metal film or the metal oxide film may include at least one of Al, Ti, Mn, Mg, Zr, Ce, Nb, La, Ta, In, Zn, Sn and oxides thereof. More specifically, the metal film may include at least one of Al, Ti, Mn, Mg, Zr, Ce, Nb, La, Ta, In, Zn, and Sn. The metal oxide film may include TiO ₂ , Al ₂ O ₃ , _{Ta 2 O 3, Ti 3 O} 3, ZrO 2, Nb 2 O 3, NbO, Nb 2 O 5, CeO 2, ZnO, MgO, La 2 O 3, MnO 2 And In ₂ O ₃ . For example, Al ₂ O ₃ .

The metal film or the metal oxide film may include two or more layers, and each layer may be formed of the same or different materials.

The thickness of the metal film or the metal oxide film may be 10 nm or more and 100 nm or less.

When the metal film or the metal oxide film is formed of two or more layers, the thickness of each layer may be 0.2 nm or more and 50 nm or less. If necessary, it may be 0.3 nm or more and 10 nm or less, specifically, 1 nm or more and 10 nm or less.

When the metal film or the metal oxide film is formed in multiple layers, a metal film or a metal oxide film may be formed to have a thickness of 6 to 100, depending on the required thickness.

According to an embodiment of the present invention, the substrate laminate may have a water vapor transmission rate of 10 ^-1 g / m ² Day or less, specifically 10 ^-3 g / m ² Day or less, specifically 10 ^-5 g / m ² Day or less. In this case, the organic light emitting portion provided on the substrate stack body described later can be protected from moisture.

According to one embodiment of the present disclosure, the light transmittance of the substrate laminate may be 50% or more, specifically 80% or more. In this case, even when the substrate laminate is applied to a substrate of an electronic device through which light should pass, there is an advantage that light can be transmitted.

The present specification relates to the substrate laminate; And

And an organic light emitting portion in which a first electrode, at least one organic material layer, and a second electrode are sequentially stacked on the substrate laminate.

The first electrode may be an anode or a cathode, and the second electrode may be an anode or a cathode, as opposed to the first electrode. That is, when the first electrode is an anode, the second electrode is a cathode, and when the first electrode is a cathode, the second electrode may be an anode.

When the voltage is applied between the two electrodes, holes are injected in the anode, electrons are injected into the organic layer in the anode, and electrons are injected into the organic layer when the injected holes and electrons meet each other An exciton is formed, and light is emitted when the exciton falls back to the ground state.

The organic material layer may have a multi-layer structure composed of different materials in order to improve the efficiency and stability of the organic electronic device. For example, the organic material layer may include a hole injection layer, a hole transport layer, a light emitting layer, an electron transport layer, and an electron injection layer.

The materials of the anode, cathode, and organic layer are not particularly limited as long as they can function as an anode, a cathode, and an organic layer, respectively. Materials commonly used in the art can be used.

And a sealing part covering the outside of the organic light emitting part.

If the sealing portion covers the outside of the organic light emitting portion and the organic light emitting portion can be sealed, the material used for the sealing portion is not particularly limited.

In the present specification, the electronic device may further include a light extracting layer.

And a light extracting layer provided between the substrate stack and the first electrode.

And a light extracting layer provided on a surface of the substrate stack opposite to the surface on which the first electrode is formed.

And a light extracting layer disposed between the substrate stack and the first electrode and on a surface of the substrate stack opposite to the surface on which the first electrode is formed.

In this specification, the light extracting layer is not particularly limited as long as it can induce light scattering and improve light extraction efficiency of the device. In one embodiment, the light extracting layer may be a structure in which scattering particles are dispersed in the binder. In another embodiment, the light extracting layer may be a structure for scattering light by a projection structure such as a plurality of lenses or the like.

According to an embodiment of the present invention, the light extracting layer may be formed directly on the substrate by spin coating, bar coating, slit coating, or the like, or may be formed in the form of a film.

In this specification, a flat layer provided on the light extracting layer may be included.

Further, the present specification provides a display device including the electronic device.

The display device includes a backlight unit and a pixel portion, and the electronic device may be included in at least one of the backlight unit and the pixel portion.

Further, the present specification provides a lighting apparatus including the electronic device.

The illumination device may be a white illumination device or a colored illumination device. At this time, according to the required illumination color, the emission color of the electronic device of the present specification can be adjusted and included in the illumination device.

Claims (25)

Forming an inorganic film using an oxide or nitride on a substrate; And
And forming a metal film or a metal oxide film by atomic layer deposition on the substrate on which the inorganic film is formed. The method according to claim 1, wherein the substrate is a plastic substrate. The method of manufacturing a substrate laminate according to claim 1, wherein the inorganic film is formed by a sputtering method, a wet coating method, or a chemical vapor deposition method. The method according to claim 1, wherein the inorganic film is made of an oxide or nitride containing Si. The substrate laminate according to claim 1, wherein the metal film or the metal oxide film includes at least one of Al, Ti, Mn, Mg, Zr, Ce, Nb, La, Ta, In, Zn, Sn, Gt; [2] The method of claim 1, wherein forming the metal film or the metal oxide film comprises forming a metal film or a metal oxide film on the substrate having the inorganic film formed thereon at least twice by atomic layer deposition. A method of manufacturing an electronic device, comprising: forming an organic light emitting portion in which a first electrode, at least one organic material layer, and a second electrode are sequentially laminated on a substrate laminate manufactured according to any one of claims 1 to 6. 8. The method of manufacturing an electronic device according to claim 7, further comprising forming a sealing portion covering the outside of the organic light emitting portion. Board; An inorganic film provided on the substrate and containing an oxide or a nitride; And a metal film or a metal oxide film provided on the inorganic film. The substrate stack according to claim 9, wherein the substrate is a plastic substrate. The substrate laminate according to claim 9, wherein a reactive group is present on the surface of the inorganic film, and the reactive group of the inorganic film and the metal of the metal film or the metal oxide film are chemically bonded. 12. The substrate laminate of claim 11, wherein the reactive group is at least one of a hydroxyl group, an amine group, and a nitro group. The substrate laminate according to claim 9, wherein the inorganic film is made of an oxide or nitride containing Si. The substrate laminate according to claim 9, wherein the metal film or the metal oxide film includes at least one of Al, Ti, Mn, Mg, Zr, Ce, Nb, La, Ta, In, Zn, Sn and oxides thereof. The substrate laminate according to claim 9, wherein the metal film or the metal oxide film comprises two or more layers. A substrate laminate according to any one of claims 9 to 15; And
And an organic light emitting portion in which a first electrode, at least one organic material layer, and a second electrode are sequentially stacked on the substrate laminate. 18. The electronic device according to claim 16, further comprising a sealing portion covering the outside of the organic light emitting portion. 17. The electronic device of claim 16, further comprising a light extraction layer disposed between the substrate stack and the first electrode. 19. The electronic device of claim 18, further comprising a planarizing layer disposed on the light extracting layer. 17. The electronic device according to claim 16, further comprising a light extracting layer provided on a side of the substrate stack opposite to the side where the first electrode is provided. 21. The electronic device of claim 20, further comprising a planar layer disposed on the light extraction layer. 17. The electronic device according to claim 16, wherein the electronic device is an organic light emitting device. 23. The electronic device according to claim 22, wherein the organic light emitting element is a flexible organic light emitting element. A display device comprising an electronic device according to claim 16. A lighting device comprising the electronic device of claim 16.

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