KR20170121543A - Flexible transparent encapsulation member and Method of forming the same - Google Patents

Abstract

A transparent encapsulation body which is flexible by newly introducing a graphene layer and a polymer layer structure into the encapsulation body, and a manufacturing method thereof are disclosed. The flexible transparent encapsulation body having a structure, in which a graphene layer is formed on a flexible transparent substrate and a polymer layer is introduced on the graphene layer, is formed. In addition, a nanostructure or a moisture absorbent is introduced into the polymer layer to enhance heat dissipation and moisture absorption of an electronic device, and an organic adhesive layer is introduced on the side of a substrate when sealing the encapsulation body and the electronic device to block gas and water inflow from the side. In addition, since the graphene layer is formed on the flexible transparent substrate, the flexible transparent encapsulation body in the form of a continuous film capable of a roll-to-roll process is manufactured.

Description

TECHNICAL FIELD [0001] The present invention relates to a flexible transparent encapsulation member and a method of manufacturing the same,

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a flexible transparent encapsulant of an organic electronic device and a method of manufacturing the same. More particularly, the present invention relates to a method of forming a graphene layer and a polymer layer on a flexible transparent substrate.

Flexible organic electronic devices are mainly fabricated on flexible substrates such as plastic. When these devices are exposed to oxygen or moisture, the performance and lifetime of the devices are greatly shortened. Therefore, organic electronic devices using a flexible encapsulation member Bagging is essential.

Generally, in the sealing process of an organic electronic device, a sealing using a glass lid, a thin film encapsulation with atomic layer deposition (ALD), a laminated barrier coating lead, and a bag with a perfluorinated polymer And the like.

There are various sealing techniques such as atomic layer deposition method and laminated barrier coating lead. However, since most of them are complicated, their processing time is long, and vacuum condition is required, productivity is lowered in terms of cost rise and production index . There is also a distinct performance limitation in applying them to organic electronic devices that require high levels of sealing properties.

Recently, a technology for mass production of a flexible organic electronic device at a low price has been demanded. In order to satisfy this demand, an organic electronic device encapsulation process is performed by a roll-to- Roll process.

A graphene layer is formed on a base substrate and an organic film is bonded on a graphene layer in the method of manufacturing a graphene layer bag in the prior art Korean Patent Laid-Open No. 10-2015-0086037 (published on July 27, 2017). Thereafter, the process of transferring the graphene layer onto the organic film of the target substrate is repeated to form a multilayer structure of a graphene layer and an organic film in which a graphene layer and an organic film are alternately laminated. However, there is a serious problem of an increase in high cost.

Since epoxy is a thermosetting plastic, the adhesive force is strong. However, the substrate is easily deformed because it is a high-temperature curing material. Therefore, a roll-to- It is very difficult to apply it to the process, and there is a problem in that a high process defect rate arises due to the organic film alternately adhering thereto.

A problem to be solved by the present invention is to provide a bag having a low-cost cost by manufacturing a bag having a graphene layer and a polymer layer structure on a flexible substrate.

In addition, a polymer having a functional material added thereto is provided to provide a plug having improved moisture adsorption characteristics and cooling characteristics of device-generated heat.

According to an aspect of the present invention, there is provided a flexible transparent bag comprising a flexible substrate, a graphene layer formed on the substrate, a polymer layer formed on the graphene layer, and an organic adhesive layer spaced apart from the graphene layer, Chain.

The substrate is characterized by being a flexible transparent resin which is a hard polymer resin or a soft polymer resin having heat resistance and flexibility.

The polymer resin may have at least one selected from the group consisting of polyethylene terephthalate (PET), polydimethylsiloxane (PDMS), poly (methyl methacrylate), polyimide, polycarbonate, polyvinylidene fluoride (PVDF), and polyaniline .

The polymer layer may have at least one selected from the group consisting of a silicone polymer, a polyisoprene, a natural rubber, a polybutadiene, a polyurethane, a polydimethylsiloxane (PDMS), a derivative thereof, and a mixture thereof, which is a curable elastic polymer.

And a flexible transparent bag further comprising a nanostructure or a moisture absorbent dispersed in the polymer layer.

The nanostructure may have at least one selected from the group consisting of metal nanoparticles, carbon nanotubes, carbon-dots, and reduced graphene oxide (RGO).

The moisture absorber may have at least one selected from the group consisting of BaO, SrO, CaO, MgO, and silica gel.

Wherein the organic adhesive layer is a flexible transparent bag further comprising a photo-curable UV (Ultra Violet) epoxy resin or a thermosetting thermal resin.

According to an aspect of the present invention, there is provided a method of manufacturing a semiconductor device, including: growing a graphene layer on a transfer substrate having a catalyst metal; removing the catalyst metal by introducing an etching solution into the transfer substrate on which the graphene layer is grown; Transferring the graphene layer onto a substrate, forming a polymer layer on the graphene layer of the substrate, and applying an organic adhesive layer on the substrate in the substrate outer region. .

And further comprising forming a polymer resin layer on the graphene layer after the step of growing the graphene layer.

And then removing the polymer resin layer using acetone or TMAH (Tetramethyl ammounium hydroxide) after the step of transferring the graphene layer having the polymer resin layer formed thereon to the substrate. .

Further comprising forming an adhesive resin layer on the graphene layer after the step of growing the graphene layer.

Wherein the step of transferring the graphene layer to a substrate is a flexible transparent bag to which the adhering resin layer having the graphene layer adhered is adhered to the substrate.

The flexible bag produced by forming the polymer layer on the graphene layer is closely attached to the electronic device and sealed, whereby gas and moisture permeation can be suppressed. Synthesis of a graphene layer and a manufacturing process of forming a polymer layer are advantageous in that a manufacturing cost and a manufacturing time can be greatly reduced by a simple process.

In order to apply this method to a roll-to-roll process, a flexible transparent sealing material in the form of a roll is formed by continuously forming a graphene layer, a polymer layer and an organic adhesive layer on a flexible transparent substrate in the form of a roll, It is possible to innovate the process of encapsulating the organic electronic device by using it.

Further, by dispersing various functional materials of the nanostructure and the moisture absorber in the polymer layer, it is possible to improve the water absorption property of the permeable transparent encapsulant and to improve the lifetime of the organic electronic device by increasing the cooling characteristic effect of the organic electronic device have.

1 is a cross-sectional view of a plug according to an embodiment of the present invention.
FIG. 2 is a cross-sectional view of a bag made up of a plurality of graphene layers having a structure in which a plurality of graphene layers are laminated through a plurality of transfer processes according to an embodiment of the present invention.
FIG. 3 is a flow chart of assembling a plug and an electronic device according to an embodiment of the present invention.
4 is a cross-sectional view of an electronic device and a plug bonded with an organic adhesive layer according to an embodiment of the present invention.
5 is a cross-sectional view of an organic electronic device according to an embodiment of the present invention.
FIG. 6 is a Raman mapping image of a randomly stacked graphene layer and a light transmittance of a graphene film including a graphene layer depending on the number of graphene layers according to an exemplary embodiment of the present invention.
FIG. 7 is an image of a PLEDs electronic device structure, a plug 300, and an encapsulated state of a plug 300 and a PLEDs device according to an embodiment of the present invention.
FIG. 8 is a graph showing an electrical characteristic evaluation of PLEDs (polymer light emitting diodes) encapsulated using a bag having various structures according to an embodiment of the present invention.
9 is a graph showing luminance decay characteristics of a PLEDs device encapsulated using a bag body having various structures according to an exemplary embodiment of the present invention and an emission characteristic of PLEDs exposed without a bag body.
FIG. 10 is a time-normalized conductance evaluation graph for a Ca test for oxidation of a Ca test electronic device encapsulated using a bag having various structures according to an embodiment of the present invention.
11 is an image of a luminescent image of a large area organic electronic device to which a bag including a graphene layer is applied and a transparent characteristic image of a flexible transparent electronic device.

While the invention is susceptible to various modifications and alternative forms, specific embodiments thereof are shown by way of example in the drawings and will herein be described in detail. It should be understood, however, that the invention is not intended to be limited to the particular embodiments, but includes all modifications, equivalents, and alternatives falling within the spirit and scope of the invention.

The terms first, second, etc. may be used to describe various components, but the components should not be limited by the terms. The terms are used only for the purpose of distinguishing one component from another. For example, without departing from the scope of the present invention, the first component may be referred to as a second component, and similarly, the second component may also be referred to as a first component. And / or < / RTI > includes any combination of a plurality of related listed items or any of a plurality of related listed items.

It is to be understood that when an element is referred to as being "connected" or "connected" to another element, it may be directly connected or connected to the other element, . On the other hand, when an element is referred to as being "directly connected" or "directly connected" to another element, it should be understood that there are no other elements in between.

The terminology used in this application is used only to describe a specific embodiment and is not intended to limit the invention. The singular expressions include plural expressions unless the context clearly dictates otherwise. In the present application, the terms "comprises" or "having" and the like are used to specify that there is a feature, a number, a step, an operation, an element, a component or a combination thereof described in the specification, But do not preclude the presence or addition of one or more other features, integers, steps, operations, elements, components, or combinations thereof.

Unless defined otherwise, all terms used herein, including technical or scientific terms, have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. Terms such as those defined in commonly used dictionaries should be interpreted as having a meaning consistent with the meaning in the context of the relevant art and are to be interpreted in an ideal or overly formal sense unless explicitly defined in the present application Do not.

Hereinafter, embodiments of the present invention will be described in detail with reference to the accompanying drawings.

1 is a cross-sectional view of a plug according to an embodiment of the present invention.

1, a graphene layer 120 is formed on a substrate 110, a polymer layer 130 is wrapped on a graphene layer 120, and an organic adhesive layer 150 (not shown) ) Of the plug body 140. As shown in Fig.

The surface of the substrate 110 may be embossed or engraved or may be flat and may be of any shape.

The substrate 110 may be a material having heat resistance or flexibility and may be, for example, a hard polymer resin or a soft polymer resin, but is not limited thereto.

The polymer resin may be at least one selected from the group consisting of polyethylene terephthalate (PET), polydimethylsiloxane (PDMS), poly (methyl methacrylate), polyimide, polycarbonate, polyvinylidene fluoride (PVDF), and polyaniline. For example, PET can be used as the substrate 110, and flexibility and transparency can be secured when PET is used. Therefore, when the polymer is used as the substrate 110 in the production of the plugs 140, It is possible to manufacture the plug body 140 of the present invention.

The thickness of the substrate 110 is not particularly limited as long as it is flexible enough. However, if the thickness of the substrate 110 is thin, it is difficult to apply tension to the substrate 110, If it is considerably thick, it is difficult to secure flexibility, which makes it difficult to use. Therefore, it is preferable to use the substrate 110 having a thickness of 30 to 300 mu m or less.

The polymer layer 130 is formed on the graphene layer 120 transferred to the substrate 110 so that the graphene layer 120 is not electrically connected to the device 330 at the position where the graphene layer 120 abuts.

FIG. 2 is a cross-sectional view illustrating a state in which a plurality of graft layers 212, 215, 218, 222, 225, and 228 are stacked through a plurality of transfer processes according to an exemplary embodiment of the present invention, 260).

Referring to FIGS. 2 (a), 2 (b) and 2 (c), a plurality of graphene layers 270, 275 and 280 are provided on a substrate 110, A second graphene layer 215, a third graphene layer 218, and a fourth graphene layer 222, which are composed of a second graphene layer 215, a first graphene layer 212, a second graphene layer 215, The second graphene layer 214 and the fourth graphene layer 222 are formed on the first graphene layer 225 and the second graphene layer 214. The graphene layer 275 and the first graphene layer 212, the second graphene layer 215, the third graphene layer 218, the fourth graphene layer 222, Lt; RTI ID = 0.0 > 228 < / RTI >

Referring to FIGS. 2 (d), 2 (e), and 2 (f), the polymer layer 230 covers the upper portions of the graphene layers 270, 275 and 280. The graphene layer 210 is separated from the graphene layer 210 The polymer layer 230 is removed from the edge of the sealing member 260 and the organic adhesive layer 250 is applied.

As the number of layers of the graphene layer 120 formed on the substrate 110 increases, the visible light transmittance decreases, but the visible light transmittance based on one layer of the graphene layer 120 is 97%.

Production Example 1 : Graphene layer  making

As the transfer substrate for growing the graphene layer, a substrate having a catalyst metal or a thin metal plate having a catalyst metal may be used, but the present invention is not limited thereto.

As the substrate for transfer, silicon, silicon oxide, metal foil, metal oxide (for example, MgO, TiO ₂ , NiO, etc.), HOPG (Highly Ordered Pyrolytic Graphite), Hexagonal Boron Nitride -BN, c-plane sapphire wafer, ZnS (zinc sulphide), and polymer substrate may be used.

Also, at least one selected from the group consisting of Ni foil, Cu foil, Pd foil, MgO, ZnS, c-plane sapphire and h-BN can be used as a transfer substrate having a crystal structure.

The catalytic metal may be at least one selected from the group consisting of Ni, Co, Fe, Au, Pd, Al, Cr, Cu, At least one selected from the group consisting of Mo, ruthenium, silicon, tantalum, titanium, tungsten, uranium, vanadium and zirconium .

A catalyst metal having a thickness of 100 nm to 1000 nm may be formed on a flat substrate by a vacuum vapor deposition method and used to grow the graphene layer 120. Alternatively, foil-shaped metal foil may be used as the catalyst metal.

A hydrocarbon raw material is provided on a copper foil which is a metal thin plate and a hydrocarbon raw material is decomposed by a heat treatment method to form a graphene layer 120 on which carbon is grown on a copper foil. The hydrocarbon raw material includes gas having a gaseous or solid form, and the gaseous hydrocarbon raw material includes at least one selected from the group consisting of methane, ethane, propane, butane and acetylene, and the like.

The heat treatment method is as follows. The hydrocarbon feed gas is introduced into the furnace under an inert gas atmosphere or a vacuum atmosphere in a furnace and the temperature inside the furnace is set to a temperature within the range of 200 ° C to 2000 ° C, And the graphene layer 120 can be formed on the copper foil.

The graphene layer 120 is cooled to room temperature and then the unloaded copper foil / graphene layer 120 is immersed in the copper etching solution to remove the copper foil, and the remaining graphene layer 120 is vacuum- Lt; / RTI > The temperature in the vacuum condition is 40 to 150 캜.

Or the copper foil / graphene layer 120 and immersed in a copper etching solution to remove the copper foil and dry the remaining graphene layer 120 / polymer resin thin film under vacuum conditions. The temperature in the vacuum condition is 40 to 150 캜. When the vacuum drying temperature exceeds 150 ° C, there is a problem that the polymer resin thin film may be damaged or deformed by heat.

Manufacturing example  2 : Graphene layer On the substrate  Warrior

In the step of transferring the graphene layer 120, the copper foil is removed from the copper foil / graphene layer 120, and the graphene layer 120 is transferred onto the substrate 110, followed by drying under vacuum conditions. A graphene layer 120 is formed on the substrate 110 and a graphene layer 120 is deposited on the substrate 110 by a van der Waals force.

or The step of transferring the graphene layer 120 includes forming a polymer resin thin film on the copper foil / graphene layer 120, removing the copper foil using a copper etching solution, / Polymer resin thin film is transferred and dried, and dried under vacuum condition. Subsequently, the polymer resin thin film is removed to form a graphene layer 120 on the substrate 110.

The polymer resin thin film may be at least one selected from the group consisting of polyethylene terephthalate (PET), polydimethylsiloxane (PDMS), polyethylene naphthalate (PEN), poly (methyl methacrylate), polyimide, polycarbonate, polyvinylidene fluoride (PVDF), and PANI You can have either one.

Manufacturing example  3: Multi-layered Graphene layer  making

The transferred graphene layer 120 on the substrate 110 may be a single layer or may be more than one layer of graphene layers 270, 275, 280 with reference to FIG.

The step of transferring the graphene layer 120 onto the substrate 110 from the transfer substrate of the copper foil / graphene layer 120 / polymer resin thin film is repeated a plurality of times to form a plurality of graphene layers 270, 275 and 280. When the graft layer 120 is transferred twice from the transfer substrate, the first graphene layer and the second graphene layer 2G graphene layer 270 are formed.

Or 6 transfer of the graphene layer 120 from the transfer substrate, the first graphene layer, the second graphene layer, the third graphene layer, the fourth graphene layer, the fifth graphene layer, and the sixth graphene layer 6G A graphene layer 280 is formed.

Manufacturing example  4: Graphene layer  Polymer layer formation

The graphene layer 120 formed on the substrate 110 can be used as an encapsulating material because of its flexibility and transparency.

FIG. 3 is a flow chart of the manufacturing process of the plug 300 and the electronic device 350 according to an embodiment of the present invention.

3, a graphene layer 120 is transferred to form a graphene layer 120 on a substrate 110, a polymer layer 130 is formed on a graphene layer 120, An organic adhesive layer 250 is formed by a coating method on a portion where the polymer layer 130 of the phase-to-position bonding portion 320 is removed, and the plug 300 is manufactured.

The coating of the polymer layer 130 on the graphene layer 120 is followed by a heat treatment for curing. The heat treatment may be performed at 60 to 100 ° C for 2 to 8 hours, preferably at 80 ° C for 3 hours, But is not limited thereto.

The polymer layer 130 formed on the graphene layer 120 may be formed using a conventional solution coating method such as spin coating, dipping or gravure roll coating. coating method can be used.

When the graphene layer 120 is in direct contact with the device 330, an electrical short may occur within the device 330. In addition, a physical impact may cause a fatal defect in the device 330. In order to prevent this, a polymer layer 130 of an insulating characteristic material is formed on the graphene layer 120.

The polymer layer 130 is preferably made of a hardenable elastic polymer material that functions as a buffer layer that minimizes physical damage by alleviating stress generated between the substrate 110 and the graphene layer 120 and the device 330.

The curable elastic polymer may be formed using a silicone-based polymer, polyisoprene, natural rubber, polybutadiene, polyurethane and derivatives thereof, and at least one selected from the group consisting of these may be used. A silicone-based polymer can be preferably used, and polydimethylsiloxane (PDMS) can be more preferably used.

The thickness of the polymer layer 130 formed from the curable elastic polymer may be 5 to 50 탆, but is not limited thereto.

Manufacturing example  5: nanostructure or The moisture absorber  Polymer layer included

A nanostructure or a powdery moisture absorbent is dispersed in the polymer layer and a polymer layer 130 containing a functional material is formed on the graphene layer 120.

The shape of the nanostructure is preferably a diameter in the case of a 0-dimensional shape, a length in a case of a one-dimensional shape, a diameter in a case of a two-dimensional shape, and a height and a circumference in a case of a three-dimensional shape smaller than a thickness of the polymer layer 130, Is more preferable.

The nanostructure may be at least one selected from the group consisting of nanoparticles, carbon nanotubes, carbon-dots, and reduced graphene oxide (RGO).

The nanoparticle may be at least one selected from the group consisting of Ag, Ni, Cu, Ti, Cr and Fe.

The moisture absorbent may be at least one selected from the group consisting of BaO, SrO, CaO, MgO and silica gel.

Manufacturing example  6: Graphene layer The bag  Manufacture of applied electronic devices

3, the organic bonding layer 250 is applied to the bonding portion 320 on the substrate of the plug 300, and then the graphene layer 120 of the plug 300 coated with the organic bonding layer 250 and the electron And is aligned and assembled with the element 330 of the element 350.

The organic bonding layer 250 is formed on the bonding portion 320 so that the bonding member 300 and the electronic device 350 can be easily coupled to each other. .

4 is a cross-sectional view of an electronic device 350 and a plug 300 bonded with an organic adhesive layer 250 according to an embodiment of the present invention.

Referring to FIG. 4, it is preferable to use an epoxy resin as the organic adhesive layer 250, and a photo-curing UV epoxy resin or a thermosetting thermal resin may be used as the epoxy resin. The organic adhesive layer 250 is formed on the connecting portion 320 of the plug 300 and then the bag 300 and the electronic device 350 are melted and pressed so as to be brought into contact with each other, And cured to produce an electronic device.

The method may further include a step of applying heat and pressure in the curing step, or applying heat and pressure before and after the curing step, but is not limited thereto.

When heat and pressure are applied in the curing step, the laminated structure composed of the graphene layer 120, the polymer layer 130, the element 330 and the element substrate 340 becomes more closely contacted, and the sealing process can be completed. Here, the process of applying heat and the process of applying pressure may be performed simultaneously or separately.

Manufacturing example  7: Roll to roll (ROLL TO ROLL) process

The graphene layer 120 is formed on the flexible substrate 110 and the polymer layer 130 is formed on the graphene layer 120. The polymer layer 130 is then separated from the polymer layer 130, Thereby forming a plug 300 having an organic adhesive layer 250 formed on the joint 320. Then, a single number of the plugs 300 are continued to manufacture a roll ROLL including a plurality of the plugs 300.

For the continuous process, the roll-like graphene layer 330 and the polymer layer 130 are aligned with the device 330, heat and pressure are applied, and the curing step is performed using the organic adhesive layer 250.

The graphene layer 120 and the polymer layer 130 can be formed by a roll-to-roll process until the transfer process on the flexible substrate is completed. There is an advantage that a roll-to-roll process using a roll including the plug 300 can be performed.

The element substrate 340 can be used without limitation as long as it is generally used in an electronic device. For example, glass, polymer film, plastic, or the like can be used, but the present invention is not limited thereto.

Electronic devices capable of applying the flexible transparent encapsulant 300 include inorganic light emitting diodes, organic light emitting diodes (OLED), inorganic solar cells, organic solar cell devices An organic thin film transistor (OTFT), an organic thin film transistor (OPV), an organic thin film transistor (TFT), a memory, an electrochemical / biosensor, an RF device, a rectifier, a CMOS device and an organic thin film transistor May be applied. But is not limited thereto.

Manufacturing example  8: Organic electronic device

5 is a cross-sectional view of an organic electronic device according to an embodiment of the present invention.

5, the organic electronic device includes a substrate 510, a first electrode 520 and a second electrode 580, and an organic layer and an electron injection layer 530 are formed between the first electrode 510 and the second electrode 580. [ Layers may be sequentially provided. Here, the organic layer may include a hole injection layer 530, a hole transport layer 540, and a light emitting layer 550, and the electron-related layer may include an electron transport layer 560 and an electron injection layer 570.

Evaluation example  One: Graphene layer  evaluation

Figure 6 is a graph of the transmittance of the graphene films 610, 620, 630 including the graphene layers 270, 275, 280 relative to the number of graphene layers 120 according to an embodiment of the present invention, the Raman spectra of the graphene layers 270, 275, Is a Raman mapped image of the graphene layers 270, 275,

Referring to FIG. 6 (a), graphs of light transmittance of the graphene films 610, 620 and 630 manufactured according to the number of graphene layers 120 manufactured in Production Example 3 are shown.

6 (a), an image of graphene films 610, 620, and 630 including a plurality of graphene layers 120 on a PET substrate 110 of an internal image includes graphene layers 120 including six graphene layers 120, It can be observed that the film 630 appears darkest. It can be seen that the light transmittance of the graphene film 630 based on 550 nm is 85.5%, which is a considerable level of transmittance. That is, as the number of graphene layers 270, 275 and 280 decreases, the light transmittance of the graphene films 610, 620 and 630 increases.

Referring to FIG. 6 (b), Raman spectroscopic measurement data using a 532 nm laser is shown. The measurement sample includes a graphene film 610 comprising two layers of graphene layers 120, a graphene film 620 comprising four layers of graphene layers 120 and six layers of graphene layers 120 Is a graphene film 630. Since the defect peaks of the plurality of graphene layers 270, 275 and 280 in the graphene films 610, 620 and 630 are maintained at a very low level, the high quality graphene layers 270, 275 and 280 having almost no surface defects on the graphene layers 270, Respectively.

Referring to FIG. 6C, a Raman Mapping image for the intensity ratio of I _D / I _G to the randomly stacked graphene layers 270, 275, 280 in the graphene films 610, 620, to be. It can be seen that there are almost no defects in the graphene layers 270, 275 and 280 and that there is almost no defect change due to the stacking of the graphene layers 270, 275 and 280. [ The I _D / I _G value is measured to be 0.1 or less, which indicates that the surface defects of the graphene layers 270, 275 and 280 are almost absent.

Manufacturing example  9: PLEDs  Structure and The bag body

FIG. 7 is an image of a PLEDs electronic device structure, a plug 300, and an encapsulated state of a plug 300 and a PLEDs device according to an embodiment of the present invention.

Referring to FIG. 7A, a 50 nm thick GraHIL, which is a hole injection layer 730, is spin-coated on a substrate 710 coated with ITO which is a first electrode 720. The hole injection layer is annealed at 150 ° C for 30 minutes in a nitrogen atmosphere after coating. GraHIL is a poly (3,4-ethylenedioxythiophene): poly (styrenesulfonate) (PEDOT: PSS, Clevios P VP AI4083), tetrafluoroethylene-perfluoro-3,6-dioxa-4-methyl- (CAS Number: 31175-20-9) (Sigma-Aldrich Inc.).

Then, a polyfluorene copolymer (80 nm, Dow Lumation Green-B, manufactured by Dow Chemical Co.) was spin-coated on the hole injection layer 730 at 3000 rpm for 90 seconds as a green light emitting layer 740, and then annealed in a nitrogen atmosphere at 80 C for 20 minutes do. Next, LiF as the EIL and Al as the cathode are deposited to form the second electrode 750.

Referring to FIG. 7B, a bag body 300 manufactured and manufactured as in Production Example 4 is formed. A graphene layer 770 is formed on a PET (760) substrate, and a polymeric resin material Is an image of the plugs 140 and 260 formed by the PDMS 780 as shown in FIG.

7 (c), the plug 300 of FIG. 9 (b) coated with the electronic element of FIG. 7 (a) and the organic adhesive layer 790 is sealed by the process shown in FIG. 7 (c) PLEDs Electronic devices are manufactured.

Evaluation example 2  : PLEDs  evaluation

The PLEDs, which are the devices manufactured in Production Example 9, are evaluated.

FIG. 8 is a graph showing an electrical characteristic evaluation of PLEDs (polymer light emitting diodes) encapsulated using a bag having various structures according to an embodiment of the present invention.

Referring to Fig. 8, the terms shown in Figs. 8 (a), 8 (b), and 8 (c) represent structures of various plugs. PET is a film without graphene layer, and PET + PDMS is a film coated with PDMS in the absence of a graphene layer. PET + 2LG + PDMS is a plug 300 having two layers of graphene layers 270 and PET + 4LG + PDMS is a plug 300 having four layers of graphene layers 275, PET + 6LG + PDMS is a plug 300 having six layers of graphene layers 280.

Referring to FIG. 8A, there is shown a graph of current density (mA / Cm2) change with voltage change of a PLEDs device. The same current density is exhibited in the encapsulated electronic device using the plug 300 according to the number of graphene layers 120 so that the device sealed with the plug 300 including the graphene layer 120 The contact phenomenon between the graphene layer 120 and the device does not occur.

Referring to (b) of FIG. 8, there is shown a graph of a change in luminance (cd / m2) according to a voltage change of the PLEDs device. The turn-on voltage of all devices in the devices encapsulated with various structures of encapsulation, including single PET bag, is 2.5 V and shows the same level of brightness at 10,000V cd / m2 at 7.5V.

Referring to (c) of FIG. 8, there is shown a graph of change in current efficiency (cd / A) according to the voltage change of the PLEDs device. The current efficiency of all devices is comparable, with the exception of the device using a single PET bag, showing stable results. In the case of a device encapsulated with a single PET, moisture or air is likely to pass through the PET and the encapsulation is incomplete, resulting in a lower current density compared to other devices.

Evaluation example 3  : PLEDs  Luminance evaluation

The organic electronic devices PLEDs manufactured as in Production Example 9 are evaluated. Evaluate the brightness of PLEDs according to the structure of various plugs to check the sealing characteristics.

9 is a graph showing luminance decay characteristics of a PLEDs device encapsulated using a bag body having various structures according to an exemplary embodiment of the present invention and an emission characteristic of PLEDs exposed without a bag body.

Referring to FIG. 9 (a), the term shown in FIG. 9 (a) expresses the structure of various plugs. air means that the device is exposed to air without a plug, PET is a film without graphene layer, and PET + PDMS is a film coated with PDMS without graphene layer.

PET + 2LG + PDMS is a plug 300 that includes two layers of graphene layers 270 and PET + 4LG + PDMS is a plug 300 that includes four layers of graphene layers 275, , And PET + 6LG + PDMS is a plug 300 that includes six layers of graphene layers 280.

Referring to FIG. 9 (a), a graph illustrating changes in luminance of the device versus time according to various types of plugs. The initial luminance equals 1000 cd / m 2 for all electronic devices. As the number of graphene layers 120 increases, the decrease in luminance is delayed. In the case of an electronic device using a plug 300 having six layers of graphene layers 280, The longest time is 70.7 hour. That is, the more the graphene layer 120 is, the better the luminance holding property (or the lifetime characteristic) is, but the light transmittance is lowered, so the increase of the graphene layer 120 and the light transmittance are in a tradeoff relation. In addition, it can be seen that the brightness of the organic electronic device is rapidly lowered in the case of an electronic device made of an unsealed electronic device (air) or a graphene-free bag (PET or PET + PDMS).

Referring to FIG. 9 (b), when an unsealed device is operated by exposure to air, the electronic device emits light uniformly at an initial stage and operates (image at the top) You can see that the area is much shrunk (the image below).

Evaluation example 4  : Using Ca Homogenized  Conductance evaluation

FIG. 10 is a time-normalized conductance evaluation graph for a Ca test for oxidation of a Ca test electronic device encapsulated using a bag having various structures according to an embodiment of the present invention.

Referring to Fig. 10, the term displayed inside represents the structure of the plug. PET is a film without graphene layer, and PET + PDMS is a film coated with PDMS in the absence of a graphene layer.

PET + 2LG + PDMS is a plug 300 that includes two layers of graphene layers 270 and PET + 4LG + PDMS is a plug 300 that includes four layers of graphene layers 275, , And PET + 6LG + PDMS is a plug 300 that includes six layers of graphene layers 280.

The Ca oxidation test is carried out at 25 ° C, 45% humidity condition and at 0.05V. The smoothed conductance value of the plug 300 including the graphene layer 120 is determined by the moisture content due to the gap between the lag region of the linear gradient and the plug 300 and the device substrate 340 And a fall off region generated due to horizontal diffusion of air.

PET + 6LG + PDMS had the longest lag time of 65h in the lag region. This is because the stacked graphene layer 120 has a small gap of 0.34 nm in the gap of the graphene layer and is sealed due to the effect of overlapping the region of the graphene layer having the defects by the graphene layer immediately above.

The water vapor transmission rate (WVTR) of the plug 300 of the PET + 6LG + PDMS structure in the fall-off region is 1.78 × 10-2 g.m -2 · d-1 and the 6LG + PDMS structure The WVTR of the graphene layer is 4.8 × 10 -1 g · m -2 · d -1. As a result, it can be seen that the PDMS buffer functions as a sticking layer which removes a space that can be generated in order to prevent gas from accumulating in the space between the Ca film and the plug.

Evaluation example  5: Bending  Character rating

11 is an image of a luminescent image of an organic electronic device and a transparent characteristic image of a flexible transparent electronic device to which a plug 300 including a graphene layer 120 is applied as in Production Example 3 and Production Example 4

11 (a), a plug 300 including a graphene layer is applied to an organic electronic device. A large area flexible organic electronic device FOLED was fabricated using the ITO electrode-based PET substrate 110. The area of the light emitting area having a light emitting area of 3 × 3 cm 2 was 4 × 4 cm 2 of PET + 6LG + PDMS Lt; / RTI > Even if the bending is enlarged, the flexible organic electronic device exhibits stable operation. Also, referring to Figure 11 (a), the internal image shows an aluminum cathode (110 nm in thickness of Al cathode) on the top side of the flexible organic electronic device.

11 (b), the structure of the flexible transparent organic electronic device, FOLED, is ITO (100 nm) / ZnO (22 nm) / polyethyleneimine ethoxylated (PEIE) (8 nm) / Super Yellow (5 nm) / Ag (15 nm) / MoO3 (45 nm). FOLED is fabricated and the top side is sealed with the plug 300. FIG. Flexible characteristics of a flexible transparent organic electronic device with a double-sided light emitting type FOLED structure can be confirmed. Referring to FIG. 11 (b), in the image 820 in the inside, a bright character shown through the light emitting area 830, which is an active area in the non-light emitting state in which the FOLED is turned off, The transparency characteristics can be confirmed. In the case of a flexible transparent electronic device of a double-sided light emitting type, MoO 3 / Ag / MoO 3, which is a transparent material, is applied to a hole injection layer and a transparent cathode.

Evaluation example  6: Evaluation of polymer layer

PLEDs fabricated using the plug body 140 having a structure in which a nanostructure is formed in the polymer layer 130 formed on the graphene layer 120 manufactured in Production Example 5 are evaluated. The temperature characteristics of the PLEDs with the nano-structured plugs 140 are shown in Table 1. The PLEDs are degraded in temperature due to the continuous rise in temperature over a period of 10 hours and a temperature increase of more than 50% relative to the initial device temperature. In contrast, the temperature characteristics of the PLEDs using the nanostructured plugs 140 were saturated at a temperature 30% higher than the initial device temperature over a period of 10 hours, and the luminescent characteristics of the PLEDs were maintained.

It should be noted that the embodiments of the present invention disclosed in the present specification and drawings are only illustrative of specific examples for the purpose of understanding and are not intended to limit the scope of the present invention. It will be apparent to those skilled in the art that other modifications based on the technical idea of the present invention are possible in addition to the embodiments disclosed herein.

110: substrate 120: graphene layer
130: polymer layer 140:
212: first graphene layer 215: second graphene layer
218: Third graphene layer 222: Fourth graphene layer
225: fifth graphene layer 228: sixth graphene layer
230: polymer layer 250: organic adhesive layer
260: plug 270: 2G graphene layer
275: 4G graphene layer 280: 6G graphene layer
300: Plug 310: Device junction receiving part
320: connecting portion 330: element
340: element substrate 350: electronic element
580: second electrode 570: electron injection layer
560: electron transport layer 550: light emitting layer
540: hole transport layer 530: hole injection layer
520: first electrode 510: substrate
610: Graphene film 620: Graphene film
630: Graphene film 700: PLEDs
750: second electrode 740: green light emitting layer
730: Hole injection layer 720: First electrode
710: substrate 760: PET
770: Graphene layer 780: PDMS
790: organic adhesive layer 810: aluminum surface
820: cathode side 830: light emitting area

Claims (13)

Flexible substrate;
A graphene layer formed on the substrate;
A polymer layer formed on the graphene layer; And
And an organic adhesive layer formed on the substrate outer region and spaced apart from the graphene layer. The method according to claim 1,
Wherein the substrate is a hard polymer resin or a soft polymer resin having heat resistance and flexibility. 3. The method of claim 2,
The polymer resin may be at least one selected from the group consisting of polyethylene terephthalate (PET), polydimethylsiloxane (PDMS), polyethylene naphthalate (PEN), poly (methyl methacrylate), polyimide, polycarbonate, polyvinylidene fluoride (PVDF) Wherein the flexible transparent bag has one of the following. The method according to claim 1,
The polymer layer is characterized by having at least any one selected from the group consisting of a silicone polymer, a polyisoprene, a natural rubber, a polybutadiene, a polyurethane, a polydimethylsiloxane (PDMS), a derivative thereof, and a mixture thereof, which is a curable elastic polymer Flexible transparent sealing material. The method according to claim 1,
Wherein the polymer layer further comprises a nanostructure or a moisture absorbent dispersed in the polymer layer. 6. The method of claim 5,
Wherein the nanostructure has at least one selected from the group consisting of metal nanoparticles, carbon nanotubes, carbon-dots, and reduced graphene oxide (RGO). 6. The method of claim 5,
Wherein the moisture absorber has at least one selected from the group consisting of BaO, SrO, CaO, MgO and silica gel. The method according to claim 1,
Wherein the organic adhesive layer further comprises a photo-curable UV (Ultra Violet) epoxy resin or a thermosetting thermal resin. Growing a graphene layer on a transfer substrate provided with a catalytic metal;
Introducing an etching solution into the transfer substrate on which the graphene layer has been grown to remove the catalyst metal;
Transferring the graphene layer to a substrate;
Forming a polymer layer on the graphene layer of the substrate; And
And applying an organic adhesive layer on the substrate in the outer region of the substrate. 10. The method of claim 9,
After the step of growing the graphene layer,
And forming a polymer resin layer on the graphene layer. 11. The method of claim 10,
After the step of transferring the graphene layer having the polymer resin layer formed thereon to the substrate,
Further comprising the step of removing the polymer resin layer using acetone or TMAH (Tetramethyl ammounium hydroxide). 10. The method of claim 9,
After the step of growing the graphene layer,
And forming an adhering resin layer on the graphene layer. ≪ RTI ID = 0.0 > 11. < / RTI > 10. The method of claim 9,
Wherein the step of transferring the graphene layer to the substrate comprises attaching the adhering resin layer having the graphene layer to the substrate.

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