WO2015102403A1

WO2015102403A1 - Flexible electronic device having multi-functional barrier layer

Info

Publication number: WO2015102403A1
Application number: PCT/KR2014/013090
Authority: WO
Inventors: 남보애; 채기성; 심동훈; 조성희; 이신우; 강지연
Original assignee: 엘지디스플레이 주식회사
Priority date: 2013-12-30
Filing date: 2014-12-30
Publication date: 2015-07-09
Also published as: KR20150078509A

Abstract

The present specification relates to an organic light-emitting display device and, more specifically, to an organic light-emitting display device which is transparent and flexible and which comprises: an electrode; and a multi-functional layer having a function of a gas/moisture barrier layer, and a method for manufacturing the organic light-emitting display device. The organic light-emitting display device comprises a substrate; an organic light-emitting element formed on the substrate; a hybrid-graphene layer, electrically connected with the organic light-emitting element, for suppressing penetration of gas/moisture of the organic light-emitting element. The hybrid-graphene layer comprises: a carbon-based first filler having a two-dimensional plane shape; and a metal-based second filler having a three-dimensional shape, wherein the second filler of a first region of the hybrid-graphene layer is not oxidized, and the second filler of a second region of the hybrid-graphene layer is oxidized.

Description

Flexible electronic device with a multi-function barrier layer

The present invention relates to an electronic device having a multi-functional barrier layer, and more particularly to an electronic device comprising a barrier layer that also functions as an electrode of the electronic devices.

Currently, one of the most popular research topics is the manufacture of transparent and flexible electronic devices. However, there are still many challenges for implementing transparent and flexible electronic devices. First, indium tin oxide (ITO), the most widely used material for current transparent electrodes, has many limitations in implementing transparent electrodes that can withstand mechanical stress caused by repeated bending of flexible electronic devices. have. In general, transparent conductive oxides, such as ITO, should be formed to a predetermined thickness or more to ensure the low resistance value required by electronic devices. In such a case, although it is possible to provide sufficient transparency as the transparent electrode, when the bending occurs due to the brittleness of the transparent conductive oxide and the thickness of the formed electrode, the transparent electrode is more easily broken. The electrical resistance value, which is greatly increased as it is bent, is also one of the factors that makes it difficult to apply a transparent electrode formed of a transparent conductive oxide to a flexible electronic device. In addition, the ever-increasing price of indium, the additional processing steps and time to form additional transparent electrodes increases the total manufacturing cost of electronic devices employing existing transparent electrodes. Thus, there is a need for new materials that can produce transparent electrodes that meet the optical, electrical, and mechanical requirements of transparent and flexible electronic devices.

Second, there are many difficulties in preventing penetration of gas (eg, oxygen) and moisture into the device in flexible electronic devices. For example, the organic light emitting layer of the organic light emitting diode (OLED) used in the flexible display is susceptible to moisture and oxygen enough to lose its light emitting function upon contact with oxygen or moisture particles. Encapsulation is required. Although protective films are commonly used to prevent the penetration of oxygen / moisture particles using encapsulations made of glass or metal, most of these encapsulations do not provide sufficient ductility, so the protective film awakens when the flexible electronic devices are bent or stretched. Various defects can occur, such as cracking, cracking, or the creation of pin-holes. Encapsulations formed from organic substrates and plastic substrates, on the other hand, provide sufficient ductility required by flexible electronic devices, but have relatively low moisture permeability compared to encapsulations formed from glass / metal, so that all sides of a portion that require protection are protected. It should be surrounded by multiple layers or by a few layers with a high thickness. In other words, increasing the thickness of the encapsulation film or the number of additional layers to obtain sufficient gas / moisture particle moisture permeation prevention rate may eventually lead to an increase in thickness and transparency of the electronic device itself.

[Related Technical Documents]

1. Manufacturing method of graphene film, manufacturing method of touch device using the same (Patent Application No. 10-2011-0120656)

Although much research is being done to realize thinner and lighter electronic devices, the fundamental limitations of the continuous miniaturization of electronic devices using existing components will soon be reached. The inventors of the present invention simply increase the size or number of existing components to improve certain specific performances required by transparent and flexible electronic devices, which not only leads to other specific performance degradation, but also further reduces electronic device miniaturization. I realized it was hard.

In addition, if one component has a multi-function barrier layer that can implement not only moisture barrier protection performance but also electrode performance as needed, it can meet the functions required for the implementation of future transparent and flexible electronic devices, It has been recognized that elimination and size reduction can solve the limit of miniaturization of electronic devices. In order for such an ideal multi-functional barrier layer to be practically commercialized, even relatively favorable production costs and processing times must be considered over other conventional methods or materials. In particular, in order to be applied to a transparent flexible display device, it is required to provide high mechanical strength, optical transparency, electrical properties, heat conduction properties, and moisture permeation prevention properties, as well as chemical stability with other components of the device.

Accordingly, there is a need in the art for developing new materials and methods for producing the materials that can overcome the problems present in implementing the above-mentioned transparent and flexible electronic devices. More specifically, new materials capable of providing not only the gas / moisture barrier layer required by the transparent flexible electronic devices but also functioning as the transparent flexible electrode as needed without specific performance degradation and unnecessary thickness increase, and methods and applications for producing the material. There is a need in the art for developing methods.

The objects of the present invention are not limited to the above-mentioned objects, and other objects that are not mentioned will be clearly understood by those skilled in the art from the following description.

Accordingly, the present specification provides a novel composition consisting of reduced graphene platelets, metal nanoparticles and a polymer. The present disclosure further provides novel methods of making such novel compositions and novel devices utilizing the unique properties of the compositions.

According to one embodiment of the present invention, an electronic device is provided. The electronic device comprises a hybrid-graphene layer comprising a first region and a second region having a sheet resistance different from the sheet resistance of the first region, the first region comprising a plurality of non-oxidized metal nanoparticles. And a plurality of graphene platelets interconnected through the second region, and the second region includes a plurality of graphene platelets interconnected through the plurality of oxidized metal nanoparticles.

An electronic device according to an embodiment of the present invention is provided. The electronic device includes a hybrid-graphene layer comprising a substrate or polymer matrix and a filler consisting of a plurality of reduced graphene platelets and a plurality of metal nanoparticles. The filler is dispersed in a polymer matrix or formed on a substrate, wherein at least some of the at least a plurality of metal nanoparticles are in contact with the surface of at least some of the reduced graphene platelets of the plurality of reduced graphene platelets. .

An organic light emitting display device according to an embodiment of the present invention is provided. The organic light emitting display device includes a substrate, an organic light emitting element formed on the substrate, and a hybrid-graphene layer electrically connected to the organic light emitting element and suppressing penetration of gas / moisture of the organic light emitting element. Hybrid-graphene layer comprising a carbon-based first filler having a two-dimensional planar shape and a metal-based second filler having a three-dimensional shape, wherein the second filler of the first region of the hybrid-graphene layer is not oxidized The second filler in the second region of the hybrid graphene layer is oxidized.

An electronic device manufacturing method according to an embodiment of the present invention is provided. An electronic device manufacturing method includes a step of forming a interconnected hybrid-graphene layer on a target surface by dispersing a carbon-based filler having a two-dimensional planar shape and a metal-based filler having a three-dimensional particle shape in a polymer matrix. Protecting a first region of the fin layer, forming a resist that exposes a second region of the hybrid-graphene layer, and oxidizing a three-dimensional particle shaped filler located in the second region of the hybrid-graphene layer And removing the protective film.

A hybrid graphene layer for an electronic device according to an embodiment of the present invention is provided. The hybrid-graphene layer has a first region and a second region, wherein the first region is a repaired graphene platelet and a plurality of repaired graphene platelets composed of at least two layers of reduced graphene oxide sheets dispersed in the polymer. A plurality of metal nanoparticles that improve the electrical connection between the graphene platelets of the second region, the second region being a polymer, a plurality of graphene oxide composed of at least two layers of reduced graphene oxide sheets dispersed in the polymer And a plurality of oxidized metal nanoparticles that interfere with the electrical connection between the platelets and the plurality of graphene platelets.

An electronic device manufacturing method according to an embodiment of the present invention is provided. An electronic device providing method comprises a polymer, a plurality of reduced graphene oxide platelets composed of one or more reduced graphene sheets and a plurality of metal nanoparticles, a hybrid-graphene layer having a first region and a second region Forming metal oxide particles and selectively oxidizing the metal nano particles included in the second region of the plurality of metal nano particles of the hybrid-graphene layer. The second region has a sheet resistance value higher than that of the first region.

Specific details of other embodiments are included in the detailed description and drawings.

1A is a plan view illustrating a hybrid-graphene layer including regions formed to have selectively different sheet resistance values according to an embodiment of the present invention.

1b (a) and 1b (b) are formed of unoxidized metal nanoparticles and graphene platelets to have a relatively low sheet resistance (conductive area) and oxidized metal nanoparticles and graphene platelets An enlarged cross-sectional view for describing a hybrid-graphene layer including a region (non-conductive region) formed of a ridge and having a relatively high sheet resistance value.

2 is a flow chart illustrating an exemplary method of forming a hybrid-graphene layer in accordance with an embodiment of the present invention.

3 is a flow chart illustrating an exemplary method of forming a hybrid-graphene layer in accordance with an embodiment of the present invention.

4A is a plan view illustrating an exemplary touch screen panel using a hybrid-graphene layer in accordance with one embodiment of the present invention.

4B is a cross-sectional view along IVb-IVb ′ of FIG. 4A.

5 is a cross-sectional view illustrating an exemplary thin film transistor using a hybrid-graphene layer in accordance with an embodiment of the present invention.

6 is a cross-sectional view illustrating an exemplary organic light emitting display device using a hybrid-graphene layer according to an embodiment of the present invention.

Advantages and features of the present invention and methods for achieving them will be apparent with reference to the embodiments described below in detail with the accompanying drawings. However, the present invention is not limited to the embodiments disclosed below, but will be implemented in various forms, and only the present embodiments are intended to complete the disclosure of the present invention, and the general knowledge in the art to which the present invention pertains. It is provided to fully convey the scope of the invention to those skilled in the art, and the present invention is defined only by the scope of the claims.

When an element or layer is referred to as “on” another element or layer, it encompasses both the case where another layer or other element is interposed over or in the middle of another element.

Although the first, second, etc. are used to describe various components, it is only used to distinguish a particular component among a plurality of components corresponding to the first and second components. Therefore, of course, the first component mentioned below may be a second component within the technical spirit of the present invention.

Like reference numerals refer to like elements throughout.

The size and thickness of each component shown in the drawings are shown for convenience of description, and the present invention is not necessarily limited to the size and thickness of the illustrated configuration.

Each of the features of the various embodiments of the present invention may be combined or combined with each other in part or in whole, various technically interlocking and driving as can be understood by those skilled in the art, each of the embodiments may be implemented independently of each other It may be possible to carry out together in an association.

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

1A is a plan view illustrating a hybrid-graphene layer having at least one conductive region and at least one non-conductive region according to an embodiment of the present invention. The hybrid-graphene layer 100 was formed of a hybrid-graphene composition 10 composed of reduced graphene oxide (rGO) platelets and metal nanoparticles dispersed in a polymer matrix. As shown in FIG. 1A, the hybrid-graphene layer 100 may include at least one first region 110 as a conductive region and at least one second region 120 as a non-conductive region. In the present specification, the conductive region and the non-conductive region are expressed by relative sheet resistance values between the two regions. In other words, the non-conductive region has a relatively high sheet resistance value compared to the conductive region, and thus refers to a region having a relatively low electrical conductivity compared to the conductive region. As described above, the hybrid-graphene layer 100 has a sheet resistance value different from that of other portions of the hybrid-graphene layer 100 by the metal nanoparticles in the hybrid-graphene composition 10 located at the specific region of the hybrid-graphene layer 100. It depends on the oxidation state.

Graphene is an allotrope of carbon with a thickness of one atom consisting of carbon atoms linked together in a hexagonal lattice. Graphene honeycomb lattice consists of two equal sub-lattices of carbon atoms linked together by σ bonds. These links, known as covalent bonds, are extremely strong and the carbon atoms are only 0.142 nm apart. Graphite can be thought of as a structure in which several graphene sheets are bonded by van der Waals bonding in a stacked form at intervals of 0.335 nm between planes. Graphene has various advantages over conventional metals due to its unique two-dimensional crystal structure and structural characteristics such as a strong sp ² carbon bond network. Graphene has a charge mobility close to 100 times that of silicon, a current density close to 100 times that of copper, high thermal conductivity, and low heat generation. It also has chemical resistance and high mechanical strength. It is flexible and flexible and can be easily patterned. These features, combined with flexible polymer structures, provide excellent combinations of mechanical, electrical, and optical properties suitable for transparent and flexible electronic devices.

Stable and evenly dispersed reduced graphene oxide platelets 12 and metal nanoparticles 16 in the polymer matrix 16 have significantly improved electrical properties than graphene or graphene composites obtained by conventional more complex methods, It can be used to make a multi-functional hybrid-graphene layer 100 having mechanical and gas / moisture barrier properties. In addition, the hybrid-graphene composition 10 of the present specification may be prepared in a liquid form, so that various solution processable methods such as spin coating, slot coating, spray coating, screen printing, dip coating method, etc. It is possible to apply to the desired surface using a) to form the hybrid-graphene layer 100.

In addition, graphene exhibits an excellent ability to passivate certain surfaces, so graphene can be made into an ideal gas / moisture barrier layer. The properties of graphene as described above make graphene a very useful material for a variety of applications in transparent and flexible devices. Hybrid-graphene composition 10 can provide excellent optical properties, gas / moisture barrier properties as well as electrical conductivity for transparent and flexible devices.

As used herein, the term “graphene” collectively refers to graphene oxide, reduced graphene oxide as well as pristine graphene. Although the graphene is theoretically composed of one layer, the graphene used in the embodiments herein is not only a graphene sheet composed of one layer but also a plurality of layers (for example, 2 to 20 layers). It may be configured as. For this reason, the graphene oxide platelet or the reduced graphene oxide platelet of the embodiments herein using the expression "platelet" is used to stack not only a single layer structure but also a plurality of layers. Emphasis was placed on including the structure in question. Thus, although each of the reduced graphene oxide platelets 12 in FIG. 1 is shown as having a single layer structure, herein among the reduced graphene oxide platelets 12 in the hybrid-graphene composition 10, Some may have a structure of a single layer reduced graphene oxide sheet, and some may have a stack structure in which the reduced graphene oxide sheets overlap. Furthermore, when the reduced graphene oxide platelet 12 is formed of a stack of multiple sheets, some reduced graphene oxide platelets 12 are not fully reduced between the reduced graphene oxide sheets contained therein. It may also include some graphene oxide sheet. In other words, the graphene sheets included in the reduced graphene oxide platelet 12 are not necessarily all reduced graphene oxide sheets. However, at least the sheets located on the outside of the reduced graphene oxide platelet 12 are preferably graphene oxide sheets. When the reduced graphene oxide platelet 12 is formed of a stack of multiple sheets, the thickness of the reduced graphene oxide platelet 12 is greater than the thickness of the single layer reduced graphene oxide sheet (ie, 0.34 nm). It may be large.

At least 25%, more preferably at least 50% of the reduced graphene oxide platelets included in each of the hybrid-graphene compositions and hybrid-graphene layers described herein are at least two layers of reduced graphene It is preferably a reduced graphene oxide platelet composed of an oxide sheet.

1B (a) and 1B (b) are enlarged cross-sectional views illustrating a hybrid-graphene layer having at least one conductive region and at least one non-conductive region according to an embodiment of the present invention. Referring to FIG. 1B (a), in the first region 110 of the hybrid-graphene layer 100, reduced graphene oxide platelets 12 and non-oxidized metal nanoparticles 14 are formed of a polymer matrix 16. Is dispersed in On the other hand, in the second region 120 of the hybrid-graphene layer 100, the reduced graphene oxide platelets 12 and the oxidized metal nanoparticles 18, as shown in FIG. It is dispersed and formed at 16.

It is known that most gas and moisture particles cannot penetrate through reduced graphene oxide sheets. As such, a network made by connecting reduced graphene oxide platelets 12 in the polymer matrix 16 can also be used as an excellent barrier to prevent gas and moisture ingress. In order for gas and moisture particles to penetrate through the hybrid-graphene layer 100 formed of the hybrid-graphene composition 10, the particles first pass through a defect site on the upper surface of the hybrid-graphene layer 100. You must enter. After entry, it must enter through a tortuous path between the polymer matrix 16 along the surface of the graphene platelets 12 spread inside the polymer matrix 16. Graphene oxide is hydrophilic in the various oxygen functional groups on the surface thereof as compared to the reduced graphene oxide from which most of the oxygen functional groups are removed, because the moisture particles can move better through the path in the polymer matrix (16) Most or all of the graphene platelets included in the hybrid-graphene composition 10 and the hybrid-graphene layer 100 of the embodiments of the preferred embodiment are reduced graphene oxide platelets 12. However, the hybrid-graphene composition 10 and the hybrid-graphene layer 100 of the embodiments herein may include a few unreduced graphene oxide platelets due to process variations.

As noted above, gas / moisture molecules can migrate along the relatively permeable polymer channels around the infiltrated reduced graphene oxide platelets 12 and penetrate through the hybrid-graphene layer 100. . Therefore, in improving the gas / moisture barrier property of the hybrid-graphene layer 100 formed of the hybrid-graphene composition 10, it is most important to establish a path as long as possible so that gas / moisture particles are difficult to penetrate. Is the point. In this regard, the factors that greatly influence the gas / moisture intrusion prevention properties of the hybrid-graphene composition 10 are the aspect ratio defined as the ratio of the longest dimension to the shortest dimension of the reduced graphene oxide platelet 12. aspect ratio, about 1.5: 5000), the dispersion rate of the reduced graphene oxide platelets 12 in the composition and the alignment form of the platelets 12, the reduced graphene oxide platelets 12 and the polymer matrix 16 Interfacial bonds and crystallinities of the polymer matrix 16. The stacking direction of the reduced graphene oxide platelets 12 of the polymer matrix 16 and the self-aggregation between the reduced graphene oxide platelets 12 and also the hybrid-graphene composition 10. Should be considered as an important factor influencing the gas / moisture intrusion prevention properties of

Considering all the above factors, the very large aspect ratio and the two-dimensional planar shape of the reduced graphene oxide platelets 12 combine with the polymer matrix 16 to establish a long tortuous path therein. It is a very suitable material.

The reduced graphene oxide platelets 12 of the hybrid-graphene composition 10 not only provide good gas / moisture barrier properties, but also combine with the polymer matrix 16 to provide the required tension in flexible devices. It also provides a strong tolerance to withstand mechanical stresses such as stress and compression stress.

In normal nano-compositions, the interface strength between the nano-filler and the surrounding polymer matrix plays an important role in the transfer of stress from the polymer matrix to the nano-filler via shear-activated mechanisms. . The higher the shear force of the interface, the greater the load it can withstand before interfacing failures occur. If the bond / adhesion between the polymer matrix and the nano-pillars is weak, the strength of the interfacing between them may decrease and eventually result in defects. Therefore, the strong bonding / adhesion between the polymer matrix and the nano-filler is important for improving the mechanical properties of the hybrid-graphene layer 100 formed of the hybrid-graphene composition 10.

The reduced graphene oxide platelets 12 are very suitable nano-fillers as nano-fillers for improving the tensile modulus and strength of the hybrid-graphene composition 10. The reduced graphene oxide platelet 12 has a larger interfacing contact area within the polymer matrix 16 compared to other carbon based nano-fillers such as carbon nanotubes (CNTs). Also, polymer chains with large molecules cannot penetrate through the inner holes of the carbon nanotubes to the inside of the tube and only the outer surface of the carbon nanotubes contacts the polymer matrix 16, but the reduced graphene oxide platelet 12 Larger interfacing contact area with the polymer because both sides of the reduced graphene oxide platelet 12 can interface with the polymer because they have a stack of single or sheets of reduced graphene oxide in planar form. Will have

In addition, the reduced graphene oxide platelets 12 are polymer chains, in contrast to other types of nano-fillers that have smooth surfaces that do not aid in mechanical interlocking. It has a rough and corrugated surface topology that can make the bond stronger. In addition, since the reduced graphene oxide platelets 12 support mechanical loads in both longitudinal and transverse directions because they have a two-dimensional planar shape, the reduced graphene oxide platelets 12 are also present in flexible devices. May serve as a gas / moisture barrier.

In addition, the improved elastic modulus of the hybrid-graphene composition 10 also leads to improved buckling stability at compression loads. Buckling is a very difficult structural instability in the structural design of flexible devices. The improved buckling stability of the hybrid-graphene composition 10 described herein is characterized by the two-dimensional planar shape of the reduced graphene oxide platelets 12 and the reduced graphene oxide platelets used in each example. 12) Most of these relate to all of the structural features that consist of a plurality of sheets. As such, in the reduced graphene oxide platelet 12 composed of a plurality of sheets, only the outer sheets of the plurality of sheets included therein are combined with the polymer matrix such that the hybrid-graphene layer 100 is formed. Contributes to the load transfer of the received tensile stress. On the other hand, the load of compressive stress is equally distributed not only to the outer sheets but also between the outer sheets, contributing to the load transfer.

Each sheet in the reduced graphene oxide platelet 12 may be buckled and bent when subjected to compressive stress due to their atomic scale thickness. At this time, the buckling or bending of the sheet in the reduced graphene oxide platelet 12 increases the friction between adjacent sheets so that better load transfer between the sheets in the reduced graphene oxide platelet 12 is achieved. do. As such, the hybrid-graphene composition 10 made using reduced graphene oxide platelets 12 composed of one or more sheets provides both tensile and compressive load transfer properties, which are important considerations in implementing flexible electronic devices. Improve.

Embodiments of the hybrid-graphene composition 10 described herein utilize a reduced graphene oxide platelets 12 and a polymer matrix 16 to make long and complicated torrent paths difficult to penetrate gas / moisture molecules. In addition to generating), the metal nanoparticles 14 may be further dispersed in the polymer matrix 16 to further improve the gas / moisture barrier properties of the hybrid-graphene composition 10. The metal nanoparticles 14 may function as a crosslinking agent that pulls the reduced graphene oxide platelets 12 and connects them to each other. When the reduced graphene oxide platelets 12 are connected by the metal nanoparticles 14, the path through which gas / moisture particles must pass is longer, so that the gas / moisture barrier performance is improved. However, the crosslinking properties of the metal nanoparticles 14 are reduced graphene oxide sheets and reduced graphene oxide platelets when forming the hybrid-graphene layer 100 using the hybrid-graphene composition 10. May cause re-agglomeration of the fields 12. Re-agglomeration of such reduced graphene oxide sheets and reduced graphene oxide platelets 12 results in uneven dispersion of the reduced graphene oxide platelets 12 in the hybrid-graphene composition 10. Phenomenon may occur, which may lead to the generation of a low density region of the reduced graphene oxide platelet 12 in the hybrid-graphene layer 100. In areas where the density of the reduced graphene oxide platelet 12 is relatively lower than other areas, gas / moisture penetration may be easier.

For this reason, the hybrid-graphene composition 10 facilitates uniform distribution of the reduced graphene oxide platelets 12 and the metal nanoparticles 14 therein and temporarily between the graphene oxide platelets 12. Re-agglomeration of and inhibits the aggregation of the graphene oxide platelet 12 and the metal nanoparticles (14) and a surfactant may be added. While the hybrid-graphene composition 10 is in a liquid state, the added surfactant inhibits the aggregation of the nano-fillers in the hybrid-graphene composition 10, while the hybrid-graphene composition 10 is a hybrid-graphene layer. When the surfactant is evaporated and dried after being applied to the surface to be formed (100), the reduced graphene oxide platelets 12, which are more strongly connected by the metal nanoparticles 14, remain uniform on the surface. In some embodiments, the reduced graphene oxide platelet 12 may be negatively charged to further enhance the bond between the reduced graphene oxide platelet 12 and the metal nanoparticles 14. The metal nanoparticles 14 may be positively charged.

The hybrid-graphene composition 10 described above is a hybrid formed of the hybrid-graphene composition 10 in addition to the optical properties, gas / moisture barrier properties, and mechanical strength properties required for use as encapsulation of transparent and flexible devices. Optional portions of the graphene layer 100 also provide a special function that may have a different sheet resistance than other portions of the hybrid-graphene layer 100. In other words, two regions, i.e., all portions of the hybrid-graphene layer 100 formed of the same hybrid-graphene composition 10, maintain substantially the same gas / moisture barrier properties but exhibit a difference of more than a predetermined sheet resistance value from each other, that is, For example, the patterning device may be patterned into at least one conductive region and at least one non-conductive region. This feature of the hybrid-graphene composition 10 herein is a true multi, which can serve not only as an encapsulation layer to inhibit penetration of gas / moisture molecules but also as an electrode of transparent and flexible electronic devices. Make the functional layer possible

This particular function is feasible because the hybrid-graphene composition 10 includes metal nanoparticles 14 that can be oxidized. More specifically, the two-dimensional planar sheet geometry and wide surface area of the reduced graphene oxide platelets 12 are connected to the conductive network by the connection between the reduced graphene oxide platelets 12 within the polymer matrix 16. It can be very effective for the formation of. However, the sheet resistance of a layer made of a composition consisting of simple reduced graphene oxide and polymer is required to drive electronic devices such as LCD and OLED displays that require intensive charge injection and / or large area coverage. It may be very high compared to. Of course, reduced graphene oxide sheets by removal of oxygen functional groups and restoration of conjugated structures have significantly better electrical conductivity than non-reduced graphene oxide sheets, but mechanically exfoliated graphene or chemical vapor phase Compared with graphene obtained in the same way as chemical vapor deposition (CVD), it contains more lattice defects that can degrade the electrical properties relatively. Also, even though each reduced graphene oxide sheet in the reduced graphene oxide platelet 12 exhibits sufficiently low sheet resistance, the surface of the hybrid-graphene layer 100 made up of a network of reduced graphene oxide platelets 12 Since the sheet resistance at can be higher than the sheet resistance of a single reduced graphene oxide sheet, it may not play a sufficient role as an electrode in electrically demanding applications. This is because unconnected portions and connections between the reduced graphene oxide platelets are affected by contact resistance at the portions where the reduced graphene oxide platelets are connected. .

However, the aforementioned electrical defects may be repaired by the plurality of metal nanoparticles 14 included in the hybrid-graphene composition 10. As shown in FIG. 1B, the conductive metal nanoparticle 14 is disposed between the reduced graphene oxide platelets 12 and the reduced graphene oxide platelets 12 in the hybrid-graphene composition 10. Acts as a bridge for interconnection between them. The metal nanoparticle 14 also creates a longer and more tightly coupled conductive network with the reduced graphene oxide platelets 12, creating more paths of electricity in the hybrid-graphene layer 100 In addition, the overall sheet resistance of the hybrid graphene layer 100 is improved.

As described above, the simple graphene platelets-polymer composition has a much lower electrical conductivity (ie, higher than the hybrid-graphene layer 100 formed from the hybrid-graphene composition 10 of the embodiments described herein. Sheet resistance). As described above, since the low sheet resistance in the hybrid-graphene layer 100 is mainly improved by the metal nanoparticles 14 interconnected with the reduced graphene oxide platelets 12, the hybrid-graphene layer ( When the conductive metal nanoparticles 14 interconnecting the reduced graphene oxide platelets 12 after formation of 100 are converted to insulating particles, the insulating particles are separated between the reduced graphene oxide platelets 12. Not only does it help the connection, but in some cases, rather than act as a spacer to disconnect the connection, the sheet resistance in the portion containing the insulating particles is significantly increased.

1A and 1B, the hybrid graphene layer 100 has a first region 110 and a second region 120. The second region 120 of the hybrid graphene layer 100 has a lower electrical conductivity than the first region 110 of the hybrid graphene layer 100. Changing the metal nanoparticle 14 from a conductive state to an insulated state can be implemented by oxidizing the metal nanoparticle 14 in the hybrid-graphene composition 10. The first region 110 of the hybrid-graphene layer 100 includes reduced graphene oxide platelets 12 and metal nanoparticles 14 dispersed in the polymer matrix 16, and hybrid-graphene layer 100 The second region 120) includes reduced graphene oxide platelets 12 and oxidized metal nanoparticles 18 dispersed in the polymer matrix 16. Here, the first region 110 of the hybrid-graphene layer 100 has a predetermined sheet resistance value low enough to be used as an electrode, and the difference in the sheet resistance value between the first region 110 and the second region 120 is also predetermined. It is preferable that a sufficient amount of the metal nanoparticles 14 are uniformly dispersed in the hybrid-graphene composition 10 so as to be larger than the value of.

The gas / moisture tolerant pathway formed by the reduced graphene oxide platelets 12 and the metal nanoparticles 14 and the polymer matrix 16 is present in the hybrid-graphene layer 100. As long as it remains intact, oxidizing the metal nanoparticles 14 at a specific site to alter the sheet resistance of a portion of the hybrid-graphene layer 100 depends on the gas / moisture barrier properties of the hybrid-graphene layer 100. Does not affect Accordingly, the metal nanoparticle 14 must be a metal capable of oxidizing the reduced graphene oxide platelet 12 and the polymer matrix 16 of the hybrid-graphene layer 10 without damage. As the metal nanoparticles, platinum (Pt), nickel (Ni), copper (Cu), silver (Ag), gold (Au), and combinations thereof may be used.

The metal nanoparticles 14 embedded in the hybrid-graphene layer 100 may be oxidized in various ways. For example, the metal nanoparticles 14 located in the region-treated region may be oxidized by treating the hybrid-graphene layer 100 with an acid. In the case where the acid is used to oxidize the metal nanoparticle 14, the acid for oxidizing the metal nanoparticle 14 should not create defects in the reduced graphene oxide platelet 12, and therefore, hybrid-graph. The metal nanoparticle 14 included in the fin composition 10 is preferably a metal that is easily oxidizable with a weak acid having a pKa acidity of about 4-11. Acids that can be used to oxidize the metal nanoparticles 14 include acetic acid, formic acid, carboxylic acid, phenol, carbonic acid, nitroalkane, Ethyl acetoacetate, diethyl malonate, 2,4-pentanedione, may be included, but is not limited thereto. The acid with pKa described above will not cause defects of the reduced graphene oxide platelet 12 in the hybrid-graphene layer 100, but reduced graphene in the second region 120 of the hybrid-graphene layer 100. It will oxidize the metal nanoparticles 14 interconnecting the fin oxide platelets 12 and transform the metal nanoparticles 14 into oxidized metal nanoparticles 18, which are electrically insulated particles. In addition, an acid for oxidizing the metal nanoparticles 14 should be selected in consideration of the polymer matrix 16. Some acids may react with the polymer matrix 16 and may interfere with the bond between the reduced graphene oxide platelet 12 and the polymer chain. In addition, since any acid may cause yellowing of the polymer matrix 16, an acid that does not occur in consideration of the polymer matrix 16 used when an optically clear multi-functional hybrid-graphene layer 100 is required. Preference is given to using.

As described above, the selective oxidation method using an aqueous solution containing an acid is completely up to the metal nanoparticles 14 embedded deep in the hybrid-graphene layer 100 due to the excellent gas / moisture barrier property of the hybrid-graphene layer 100. It can be difficult to oxidize. When not only forming the electrode on the surface of the hybrid-graphene layer 100 but also forming the electrode by oxidizing the metal nanoparticles 14 deep inside the hybrid-graphene layer 100, a laser treatment method may be used. have. The penetration level and oxidation level of the laser through the desired area of the hybrid-graphene layer 100 can adjust various parameters related to the laser processing such as duty cycle, power, wavelength, exposure time, density, etc. This enables oxidation even up to the metal nanoparticles 14 located at the desired depth of the hybrid-graphene layer 100. Depending on the polymer used in the hybrid-graphene composition 10, curing of the polymer matrix 16 is also possible at the same time when the metal nanoparticles 14 are oxidized using a laser.

Note that the oxidation process will be performed after the hybrid-graphene layer 100 is coated or applied onto the surface. In one embodiment, the hybrid-graphene composition 10 is applied to a surface such as a metal substrate, a polymeric layer, or a film to form a hybrid-graphene layer 100, followed by a selective oxidation process. This can be done. However, in another embodiment, a selective oxidation process may be performed after the hybrid-graphene layer 100 is formed on a sensitive portion of devices such as an organic light emitting layer of an organic light emitting device or an active layer of a thin film transistor. Thus, the strength of the acid in the oxidation method with acid, the strength of the laser in the oxidation method with laser, is the material of the metal nanoparticle 14, hybrid-graphene, so as not to damage the weak parts of such a device. The amount of metal nanoparticles 14 in the composition 10, the number of sheets that the reduced graphene oxide platelets 12 contain on average, the hybrid-graph applied to form the hybrid-graphene layer 100. In addition to the thickness of the fin composition 10, it should be determined in consideration of various factors.

In addition, in one embodiment, the metal nanoparticles 14 of the hybrid graphene layer 100 may be oxidized by using a combination of an acid oxidation method and a laser oxidation method. When the metal nanoparticles 14 are oxidized in such a complex manner, the precise oxidation of the metal nanoparticles 14 can be achieved in a faster time than when using one oxidation method. In another embodiment, a laser oxidation method is first used to further perform a second oxidation process using a weak acid after curing the polymer matrix 16 of the hybrid-graphene layer 100 and oxidation of the metal nanoparticles 14. It can prevent damage to weak areas.

Graphene Oxide 용액의 생성Generation of Graphene Oxide Solution

2 and 3 are flowcharts illustrating an exemplary method of forming hybrid-graphene layer 100. In both of the exemplary methods, a dispersed liquid phase of graphene oxide platelets formed mostly of a plurality of layers of graphene oxide sheets is included (S210, S310). The most common technique used for liquid phase dispersion of graphene oxide is to oxidize graphite to form graphite oxide, which is then stripped off to produce platelets of graphene oxide.

As such graphene oxide platelets are produced from graphite oxide, each of the graphene sheets of graphite oxide has a hydroxyl functional group, an epoxide functional group, a carbonyl functional group, and a carboxyl ( It is heavily functionalized by oxygen-functional groups, including carboxylic) functional groups, and the graphene sheet-to-sheet spacing extends from the original 0.34 nm to about 0.72 nm or more. In addition, functional groups make the graphene sheets hydrophilic, so that intercalation of water molecules between the graphene sheets easily occurs. Therefore, it is much easier to peel graphene from graphite oxide than to directly peel graphene from graphite. Thus, in order to produce a dispersion of graphene oxide platelets consisting of single or multiple layers of graphene oxide sheets, the graphite oxide is subjected to sonication and centrifugation (eg, about 30 minutes at 4000 rpm). Can be exfoliated in distilled water and the remaining expanded graphite oxide can also be removed from the dispersion.

The term “platelet” herein may be composed of a single graphene sheet, but the thickness of the graphene oxide platelets is single-layered, remembering that multiple (2-10 layers) sheets represent an overlapping structure. It may be larger than reduced graphene (ie 0.72 nm), or may be formed of multiple layers and consequently 1 to 8 nm.

The solvent for carrying out the oxidation of the graphite for producing the graphite oxide is not particularly limited. Preferred media is water, but co-solvents or additives may be used to enhance the wetting of hydrophobic graphite flakes. Solvents and / or activators may be used alone or in combination. Preferred active agents are methanol, ethanol, butanol, propanol, glycols, water soluble ethers and esters, non-ionic ethylene oxide , Surfactants such as propylene oxide and their copolymers, alkyl surfactants such as Tergitol based or Triton based surfactants, or ethylene oxide and propylene oxide Or surfactants with butylene oxide units. Co-solvents and surfactants can be used at levels from 0.0001% to 10% by weight in solution. The amount of cosolvents and surfactants is 0.001, 0.005, 0.01, 0.05, 0.1, 0.5, 1, 1.5, 2, 2.5, 3, 3.5, 4, 4.5, 5, 5.5, 6, 6.5, 7, based on the solution phase All values including 7.5, 8, 8.5, 9 and 9.5 weight percent are included and subvalues there between. Intercalants include, but are not limited to, inorganic acids or salts thereof, alone or in mixtures, preferably HNO ₃ , H ₂ SO ₄ , HCl, HCl, KCl.

Polar functional groups on graphene oxide sheets are preferably hydroxyl, epoxy and carboxylic acid groups or derivatives thereof. Such polar functional groups can be functionalized using molecules that are reactive toward polar functional groups. One or more types of functional groups may be included. For example, alkyl amines and dialkyl amines may be used to add hydrophobicity to the surface by reaction to epoxides, so Fin oxide sheet surfaces can be used to crosslink covalently. Acid chlorides can react with hydroxyls to add alkyl groups. The reaction of amines or hydroxyls with carboxylic acids can be used to attach functional groups to add alkyl groups to make the graphene oxide sheet surface more hydrophobic. Graphene oxide sheet surfaces can be made more hydrophobic by adding ethylene oxide, primary and secondary amines, and acid functionalities, for example using the compounds described above.

In one embodiment altering the functional groups of the graphene oxide platelets may later grafting functional groups that may further increase the mutual bonding force between the surface of the reduced graphene oxide platelets 12 and the polymer matrix 16. May be). The material used for this grafting may be a polymer having a molecular weight similar to the low molecular weight of the polymer when matrixed or having a reactive function of the polymer when matrixed. They are polyethylene or polypropylene copolymers of vinyl acetate or maleic anhydride to induce compatibility between functional graphene oxide platelets and olefin polymers. Or a mixture thereof.

As mentioned above, longer gas / moisture penetration inhibition pathways can be produced by graphene with increased transverse larger size. The maximum size of the graphene oxide platelets is determined by the size of the source used to produce them, i.e., the graphite itself, but the average size of the graphene oxide platelets in the graphene oxide solution is during the formation of the graphene oxide solution. Can be controlled in nano units by adjustment of oxidation, sonication time, and centrifugation rate. For example, the higher the centrifugation rate (rpm), the smaller the size of the graphene oxide platelets layered at the top. As described above, the dispersion of the sonicated graphite comprises expanded graphite crystals that can be removed through centrifugation. As an example, centrifugation at 500 rpm can remove graphite crystals that did not exfoliate while leaving dispersed graphene oxide platelets. However, the centrifugation rate may be reduced or increased depending on the size of the graphene oxide platelets to be obtained. Centrifugation using 500 rpm to remove only the expanded graphite crystals includes the first supernatant containing small platelets, sediment from which other sized platelets are re-dispersed, and centrifuged. It may be a second supernatant containing precipitates and graphite crystals. However, higher centrifugation rates can be selected for re-dispersed precipitates. This removes the crystals and the largest size platelets, leaving only the medium size platelets to be dispersed. With this higher centrifugation rate, a supernatant containing small platelets, a precipitate containing medium sized platelets centrifuged, and a second precipitate containing large platelets and graphite crystals can be obtained. In this way it is possible to obtain a solution in which graphene oxide platelets having a lateral length of between 0.5 μm and 10 μm are dispersed.

GO의 화학적 환원Chemical reduction of GO

Graphene oxide sheets of graphene oxide platelets have electrical and gas / moisture barrier properties that are much worse than the various properties of raw graphene. The electrical properties are one of the biggest differences between graphene oxide and raw graphene. The conductivity of graphene depends on the far conjugated network of the graphene lattice. However, the chemical process in the production of graphene oxide breaks the conjugated structure and confines π-electrons resulting in much lower carrier mobility and carrier concentration. Even though there are conjugated regions in graphene oxide, the far (> µm) conductivity is blocked such that carrier movement does not occur as inherently graphene by the absence of a path between sp ² carbon clusters. For this reason, graphene oxide sheets are typically insulating materials having a sheet resistance of about 10 ¹² Ω / square or more.

As shown in FIG. 2, the method 200 for forming the hybrid-graphene layer 100 may include obtaining a solution in which the reduced graphene oxide platelets are dispersed through reduction of the graphene oxide platelets (S220). It includes. Reduction of graphene oxide platelets can be performed in a variety of ways. In one embodiment, graphene oxide platelets are chemically reduced in solution with reducing agents such as hydrazine hydrate, dimethylhydrazine, hydroquinone, and NaBH ₄ , resulting in conjugated structures and other molecules. Partial lattice defects are partially recovered and oxygen functionalities are removed to convert the graphene oxide sheets into native graphene-like reduced graphene platelets. Recovery of the sp ² carbon bond network helps to partially restore electrical conductivity and other properties.

하이브리드-그래핀 조성물의 형성Formation of Hybrid-Graphene Compositions

As mentioned above, the hybrid-graphene composition comprises a polymer matrix, reduced graphene oxide platelets as filler and metal nanoparticles. Thus, the method 200 of forming the hybrid-graphene layer 100 comprises mixing polymer and metal nanoparticles with reduced graphene oxide platelets (rGO colloidal solution) to obtain a hybrid-graphene composition. (S230).

The polymer matrix of the hybrid-graphene composition herein may comprise thermoplastic polymers, elastic polymers, and mixtures thereof. Suitable thermoplastic polymers include polyimide, polyvinylpyrrolidone (PVP), polyurethane, methacrylates such as polymethyl methacrylate, epoxy resins Polypropylenes include, but are not limited to, polyolefins, polystyrene, and poly (ε-caprolactone). Also suitable elastomeric polymers are acrylonitrile butadiene copolymers, elastomers with a triple block copolymer architecture, poly (styrene-b-butadiene copolymers, BR and Styrene-Butadiene Copolymer (SBR) Vulcanizer, Natural and Synthetic Rubber, Butadiene and Acrylonitrile Copolymer (NBR), Polybutadiene, Polyesteramide, Chloroprene ) Rubbers (CR) and mixtures thereof, including but not limited to, amorphous or crystalline plastics such as PMMA or PE may also be used as polymers, in addition, graphene reduced using monomer precursors of these polymers. It is also possible to synthesize the hybrid-graphene composition 10 by causing a polymerization reaction in the presence of oxide platelets. And / or their precursors may be used alone or in combination.

The large aspect ratios of the reduced graphene oxide platelets and the very high surface area interfacing with the polymer matrix enable the production of hybrid-graphene compositions with improved gas / moisture barrier properties as well as mechanical properties. The aspect ratio of the reduced graphene oxide platelets can be from about 10 to about 10000, but preferably greater than about 100, which increases the tensile modulus at load levels as low as 3%. The interfacial properties of the reduced graphene oxide platelets as described above can be controlled by surfactants that enhance the dispersion and interfacial strength in the polymer matrix and these surfactants may be the gas / gas of the hybrid-graphene layer 100. Change the moisture barrier properties. Surfactants include, but are not limited to, anionic surfactants, cationic surfactants, nonionic surfactants, and mixtures thereof.

Since the metal nanoparticles 14 in the selective region of the hybrid-graphene layer 100 must be changed by oxidation to change the electrical properties of the corresponding region, the graphene oxide platelets reduced in the hybrid-graphene composition 10 ( The metal nanoparticles 14 interconnecting 12 should be oxidizable metal nanoparticles 14. As described above, the metal nanoparticles 14 of the hybrid-graphene layer 100 are oxidizable by weak acids that do not create defects in the reduced graphene oxide platelets 12 of the hybrid-graphene layer 100. Metal material. For example, the metal nanoparticles 14 in the hybrid-graphene layer 100 may be oxidized with a weak acid having a pKa of about 4-11. Acids usable herein are acetic acid, formic acid, carboxylic acid, phenol, carbonic acid, nitroalkane, ethyl acetoacetate , Diethyl malonate, 2,4-pentanedione (2,4-pentanedione) may include, but is not limited thereto. The acids with pKa described above will not cause defects in the reduced graphene oxide platelets 12 of the hybrid-graphene layer 100, but the metal nano interconnects the reduced graphene oxide platelets 12. It is sufficient to oxidize the particles 14 and transform the metal nanoparticles 14 in an optional region of the hybrid-graphene layer 100 into electrically insulating particles.

As the metal nanoparticles 14 usable in the hybrid-graphene composition 10, platinum (Pt), nickel (Ni), copper (Cu), silver (Ag), gold (Au), and combinations thereof may be used. . The metal nanoparticles 14 of the hybrid-graphene composition 10 are not limited to these materials, and the metal nanoparticles 14 may be a conductive and oxidizable metal material.

The method 200 of forming the hybrid-graphene layer 100 includes applying a hybrid-graphene composition onto a target surface (S240) to form a hybrid-graphene layer. In addition, the hybrid-graphene composition may be applied by a variety of solution based methods including those such as spin coating, spray coating, slot coating, screen printing, dip coating methods and the like. In some embodiments, the surface coated with the hybrid-graphene composition 10 may be functionalized to assist in the adhesion of the hybrid-graphene composition 10 on the surface. In addition, when coating the target surface, the hybrid-graphene layer 100 is reduced to the reduced graphene oxide platelets 12, below the density of solids only for the reduced graphene oxide platelets 12. It may be formed at a density of solids or above the density of solids for the reduced graphene oxide platelets 12.

The method 200 of forming the hybrid-graphene layer 100 also includes oxidizing the metal nanoparticles 14 in an optional region of the hybrid-graphene layer 100 (S250). The region of the hybrid-graphene layer 100 composed of reduced graphene oxide platelets 12 interconnected through oxidized metal nanoparticles 18 is reduced interconnected through unoxidized metal nanoparticles 14. It has a sheet resistance much larger than that of the graphene oxide platelets 12. Oxidation of the metal nanoparticles 14 can be accomplished in a variety of ways.

In one embodiment, an oxidation process is performed on the selected region of the hybrid-graphene layer 100 to oxidize the metal nanoparticles 14 in the selected region of the hybrid-graphene layer 100. The resists (protective films) are formed in regions where low sheet resistance is required, that is, conductive regions for functioning as electrodes. The resists prevent the metal nanoparticles 14 from being oxidized by acid in the protected area, while the metal nanoparticles 14 in the remaining area of the hybrid-graphene layer 100 are oxidized. The acid treatment process time is based on the type of the metal nanoparticles 14 and the polymer included in the hybrid-graphene layer 100, the density of the solids of the acid and the reduced graphene oxide platelets 12 used in the treatment process. However, it may vary depending on various factors such as the shape, density and size of the electrode pattern to be formed on the hybrid-graphene layer 100. The resist member may be removed when the oxidation of the metal nanoparticles 14 in the region not protected by the resist member is completed. However, as described above, acid may penetrate between the polymer matrix 16 and oxidize all of the metal nanoparticles 14 located at the lower end of the hybrid graphene layer 100, and thus, the hybrid graphene layer 100 may be restricted. When only the upper part is oxidized, it may be difficult to use except for an electrode that is energized to the lower part and simply uses a difference in sheet resistance of the complete electrode.

In one embodiment, laser oxidation may be performed on selected areas of the hybrid-graphene layer 100 to oxidize the metal nanoparticles 14 in selected areas of the hybrid-graphene layer 100. Each optional region of the hybrid-graphene layer 100 may be individually lasered to oxidize the metal nanoparticles 14 within the region. For more complex patterning, a pattern of the hybrid-graphene layer 100 coated on the target surface may be exposed to the laser at one time by using a metal mask. The penetration level of the laser for oxidizing the metal nanoparticles 14 in the hybrid-graphene 100 layer through the hybrid-graphene layer 100 is determined by various parameters related to laser processing such as duty cycle, power, wavelength, exposure time, and the like. Can be controlled by adjusting them.

In contrast to layers made of conventional graphene compositions having uniform electrical properties on the front, either conductive or non-conductive, the hybrid-graphene layer 100 of the present invention is characterized in that the selective regions of the layers differ in electrical properties from other regions. It is possible to pattern to have. By selectively having different sheet resistance values in the regions in the hybrid-graphene layer 100, it is possible to directly form the electrode patterns directly in the hybrid-graphene layer 100 without forming a separate electrode layer on the gas / moisture barrier layer. It is possible. As such, the hybrid-graphene layer 100 may be used as a true multi-functional layer, that is, a true multi-functional layer that simultaneously serves as a transparent and flexible electrode pattern and serves as a gas / moisture barrier layer.

화학적 환원 방법Chemical reduction method

While chemically reducing graphene oxide platelets can partially restore the electrical and gas / moisture barrier properties, chemical reduction methods mostly cause defects in graphene oxide platelets. In addition, graphene oxide platelets reduced by chemical reduction method reduce dispersibility in common organic solvents, causing re-stacking and re-aggregation of the reduced graphene oxide platelets. do.

These phenomena are related to the interface between the polymer matrix 16 and the reduced graphene oxide platelets 12. Polar groups of reduced graphene oxide sheets in reduced graphene oxide platelets 12 provide compatibility to the polymer. In particular, the reduced graphene oxide platelets 12 due to the bi-planar polar groups are highly compatible with the surrounding polymer matrix 16 and thus with a relatively small amount of reduced graphene oxide platelets 12. To evenly disperse the hybrid-graphene composition 10. As a result, it is possible to form a longer gas / moisture suppression path than the conventional one, thereby realizing a hybrid-graphene layer 100 having improved gas / moisture barrier properties.

On the other hand, reduced graphene oxide platelets 12 with reduced compatibility with the polymer matrix 16 exhibit re-agglomeration and re-lamination phenomena, resulting in higher amounts of reduced graphene to form gas / moisture suppression pathways. Not only are fin oxide platelets 12 needed, but also the light transmittance is poor due to re-agglomeration and re-lamination phenomena. Reducing the amount of reduced graphene oxide platelets 12 in the hybrid-graphene composition 10 to ensure sufficient light transmittance makes it difficult to create a gas / moisture suppression path of sufficient length, thus making the hybrid-graphene layer 100 The gas / moisture barrier property of C) deteriorates inevitably.

Graphene oxide platelets (12) are also reduced by several filtration, drying and re-dispersion processes during the reduction of graphene oxide platelets using chemical reduction. Their re-agglomeration and re-lamination are one of the great reasons. Surfactant may be added to the hybrid-graphene composition 10 to assist in the dispersion of the reduced graphene oxide platelets 12 in the hybrid-graphene composition 10 water, but once aggregated The reduced graphene oxide graphene platelets 12 are difficult to separate again by using a surfactant. Again, reagglomeration / relamination of the reduced graphene oxide platelets 12 is more likely to permeate the gas / moisture than seeping through the gas / moisture penetration inhibition path generated by the reduced graphene oxide platelets 12. The gas / moisture barrier properties of the hybrid-graphene layer 100 can be reduced by increasing the likelihood of seeping through the polymer matrix 16 directly without a penetration inhibition pathway.

에어로졸(aerosol) 방법Aerosol method

Thus, in one embodiment, graphene oxide platelets are reduced via an aerosol pyrolysis method. 3 shows an exemplary method 300 for preparing hybrid-graphene composition 10 using the aerosol pyrolysis method according to one embodiment of the invention. As shown in FIG. 3, the method for preparing the hybrid-graphene composition 10 using the aerosol pyrolysis method is a graphene oxide platelet composed of graphene oxide sheets composed of single or several layers (2 to 10 layers). Preparing a dispersed precursor solution (S310). In one embodiment, the precursor solution may be a colloidal solution of graphene oxide platelets prepared in a similar manner as the colloidal solution in which the graphene oxide platelets described with reference to FIG. 2 are dispersed. In another embodiment, the precursor solution may be made by mixing a colloidal solution in which the above-described graphene oxide platelets are dispersed and a solution in which the metal nanoparticles are dispersed. In addition, ultrasonic grinding may be performed in combination to stir the precursor solution and obtain a homogeneous dispersion.

The method of preparing the hybrid-graphene composition 10 using the aerosol pyrolysis method includes transforming the precursor solution into the form of airgel droplets (S320). As a step of deforming in the form of aerogel droplets, for example, an ultrasonic nebulizer may be used to deform and spray the precursor solution into a form of aerosol droplets having a diameter of several tens of microns.

The method for preparing the hybrid-graphene composition 10 using the aerosol pyrolysis method includes passing the airgel droplets through a furnace to evaporate water molecules and reduce graphene oxide platelets (S330). do. As an example of a furnace, a tubular furnace may be used. The sprayed airgel droplets can be transferred to the furnace using gas. At this time, as the gas used, one or other various reducing gases such as argon gas and nitrogen (N ₂ ) gas may be mixed and used. You can also use an additional fan for faster movement.

The temperature of the furnace may range from 300 ° C to 2000 ° C. The temperature of the furnace may be a temperature capable of simply reducing the graphene oxide platelets in the aerosol droplets, but the temperature of the furnace may be determined in consideration of various factors in order to facilitate the reduction of the graphene oxide platelets. For example, the temperature of a furnace may vary within the furnace structure of the furnace, the volume and rate of aerosol droplets passing through the furnace in a particular section, and the aerosol droplets determined by these. It can be determined according to the residence time of. As an example, the furnace may be heated to a temperature between 300 ° C. and 600 ° C. to sufficiently reduce graphene oxide platelets with a residence time of 0.1 seconds to 10 minutes.

In addition, the composition and composition ratio of the aerosolized precursor solution are also important factors in determining the temperature of the furnace and the appropriate residence time of the aerosol droplets. More specifically, when the aerosolized precursor solution contains metal nanoparticles together, the reducing atmosphere in the furnace reduces graphene oxide platelets but does not oxidize the metal nanoparticles. However, depending on the temperature of the furnace and the residence time of the aerosol droplets, metal nanoparticles can adhere to the surface of the reduced graphene platelets. Metal nanoparticles adhering to the surface of the reduced graphene platelets are more tightly bonded to the surrounding polymer matrix with the reduced graphene platelets in the hybrid-graphene layer and furthermore an electrical network between the reduced graphene platelets. It can act more easily to form. However, when the temperature of the furnace and the residence time of the aerosol droplets are excessive, metal nanoparticles may be formed in a form surrounding the reduced graphene platelets. In this case, the phenomenon of losing the characteristics of the reduced graphene platelets may result. Since the temperature and residence time at which the above-described phenomena occur may vary depending on the type of the metal nanoparticles, in some embodiments in which the metal nanoparticles are included in the aerosol droplets, the temperature and the aerosol of the heating furnace depend on the type of the metal nanoparticles included. The residence time of the droplets can be adjusted. For example, in the case of including one of the metal nanoparticles described above, the temperature of the heating furnace is preferably 900 ° C. or lower.

It may further comprise the step (S325) of further adding a reducing gas having hydrogen (H ₂ ) or other active or volatile characteristics in the furnace to create a more efficient reducing atmosphere. In this case, the ratio of the reducing gas and the inert gas in the reducing atmosphere in the furnace may be 50%, respectively. For example, the ratio of H ₂ and N ₂ in the reducing atmosphere in the entire furnace may be 50:50, respectively. However, there may be various limitations in using a high ratio of reducing gas having a high volatility such as H ₂ . Even when a volatile reducing gas such as H ₂ is used, the ratio of H ₂ in the reducing atmosphere in the heating furnace can be used only 50% or less, more preferably 25% or less. As such, the proportion of nitrogen, argon or such an inert reducing gas in the reducing atmosphere in the furnace may be 50% or more, and more preferably 75% or more. In FIG. 3, the step of injecting additional reducing gas (S325) is shown as a separate process, but the inert gas in the step (S330) of reducing the graphene oxide platelets by passing the airgel droplets through a furnace (furnace). It can also be injected into the furnace with the. In addition, in another embodiment of preparing the hybrid-graphene composition 10 using the aerosol pyrolysis method, unlike the method described in FIG. 3, the graphene may be formed using only an inert gas and heat without using additional reducing gas. The platelets may be reduced to prepare the hybrid-graphene composition 10.

By reducing the graphene oxide platelets in the manner described above, it is possible to obtain reduced graphene oxide platelets having significantly fewer defects than the chemically reduced graphene oxide platelets in the liquid phase. In particular, the reducing atmosphere in the furnace reacts with the oxygen functionalities of the graphene oxide platelets to obtain high quality reduced graphene oxide platelets with substantially all remaining functional groups removed.

However, even when using the above-mentioned aerosol pyrolysis reduction method, van der Waals binding force is reduced by collecting the reduced graphene oxide platelet using a common filtration membrane such as a Teflon filtration membrane and dispersing it into a solution for the solution process. The process may cause reaggregation / relamination of the reduced graphene oxide platelets, resulting in a phenomenon that the reduced graphene oxide platelets are not uniformly dispersed in the hybrid-graphene composition. As described above, if the dispersion of the reduced graphene oxide platelets in the hybrid-graphene composition is not uniform, this results in a reduction of the gas / moisture barrier and electrical properties of the hybrid-graphene layer.

Accordingly, embodiments of the method for preparing the hybrid-graphene composition 10 using the aerosol pyrolysis method described herein, reduce the graphene oxide reduced steam through the heating furnace in which the reduced graphene oxide platelets are dispersed. And passing directly through an aqueous solution (eg, an organic solvent) mixed with a surfactant that is easy to inhibit re-agglomeration between the platelets and collecting it directly in the solution (S340). When the reduced graphene oxide platelets in the gas are collected immediately using an aqueous solution containing a surfactant, re-agglomeration and re-lamination of the reduced graphene oxide platelets such as filtration, drying process and re-dispersion are performed. A reduced graphene oxide platelet solution can be obtained that can be applied directly to the desired surface through various process processes without causing the processes to be caused, and the frequency of reaggregation / relamination is much lower. In one example, the aqueous solution may be DI mixed with 1% to 5% surfactant with the ability to inhibit aggregation of reduced graphene oxide platelets, and the temperature of the aqueous solution may be between 20 ° C and 100 ° C. have.

Hybrid-graphene composition (10) manufacturing method using the aerosol pyrolysis method is a method for producing a hybrid-graphene composition by mixing a reduced graphene oxide platelet solution, a metal nanoparticle, and a polymer obtained by the method described above ( S350). In an exemplary embodiment of the present invention, the step S350 of mixing the metal nanoparticles and the polymer in an aqueous solution containing the reduced graphene oxide platelets to generate the hybrid-graphene composition 10 (S350) is described above. It was described as a separate step from the step (S340) of directly collecting the vapor in which the reduced graphene oxide platelets are dispersed into an aqueous solution containing a surfactant. However, the step of producing a hybrid-graphene composition by mixing the reduced graphene oxide platelet solution, the metal nanoparticles, and the polymer (S350) may be made in various ways.

For example, as described above, among the embodiments, the metal nanoparticles are dispersed in the precursor solution, passed through the furnaces in the form of aerosol droplets, and then dispersed in steam together with the reduced graphene oxide platelets using the solution. It is also possible to obtain a reduced graphene oxide platelet solution that already contains metal nanoparticles by collecting. In addition, even if a precursor solution in which the metal nanoparticles are not dispersed is used, the vapor in which the reduced graphene oxide platelets are dispersed may be collected using a solution in which the metal nanoparticles are dispersed. When using a precursor solution containing metal nanoparticles or a solution in which metal nanoparticles have already been dispersed to capture steam from the furnace, additional polymers can be added to the collected solution to create a hybrid-graphene composition. Can be. Of course, the vapor in which the reduced graphene oxide platelets are dispersed may be collected using a solution containing metal nanoparticles and a liquid polymer. In this case, the polymer may include a polymer that serves as a stabilizer capable of suppressing the aggregation of the reduced graphene oxide platelets and the metal nanoparticles with each other.

In addition to the above-described methods, it is also possible to prepare a solution in which the metal nanoparticles are dispersed and a solution in which the polymer is dissolved, and then mix the reduced graphene oxide platelet solution with the hybrid graphene composition. Do. The polymer added to the hybrid-graphene composition may be separately prepared in solution and then mixed with the reduced graphene oxide platelet solution to produce the hybrid-graphene composition.

Since the metal nanoparticles may also cause re-agglomeration of the reduced graphene oxide platelets in the hybrid-graphene composition generation, the type and ratio of the surfactant included in the aqueous solution used for trapping the vapor may be Reduced by addition of metal nanoparticles in consideration of various factors such as the weight ratio of the metal nanoparticles, the ratio of the reduced graphene platelet as well as the type of polymer to be added to the hybrid-graphene composition and the temperature of the aqueous solution. It may also be adjusted to inhibit re-agglomeration of graphene oxide platelets.

4A is a plan view illustrating an exemplary touch screen panel using a hybrid-graphene layer in accordance with one embodiment of the present invention. 4B is a cross-sectional view along IVb-IVb ′ of FIG. 4A. 4A and 4B illustrate a touch screen panel 400 as an electronic device of the present invention. 4A and 4B, in the touch screen panel 400, the hybrid-graphene layer 410, the first touch detector 420, the second touch detector 430, and the insulating layer 440 are formed of a substrate ( On the 450). In FIG. 4A, for convenience of description, the insulating layer 450 is not illustrated, and hatching of the hybrid graphene layer 410 is illustrated.

4A and 4B, a hybrid graphene layer 410 is formed on the substrate 450. Hybrid-graphene layer 410 has a first region 412 and a second region 414. The second region 414 of the hybrid graphene layer 410 has a higher sheet resistance value than the first region 412 of the hybrid graphene layer 410. The hybrid-graphene layer 410 may implement the touch screen panel 400 by using the difference between the sheet resistance values of the first region 412 and the second region 414. The difference in the sheet resistance values between the first region 412 and the second region 414 is sufficiently different so that the first region 412 and the second region 414 can be distinguished by the device, respectively. The hybrid-graphene composition constituting the first region 412 and the second region 414 of the hybrid-graphene layer 410 may include the first region (1) of the hybrid-graphene layer 100 described with reference to FIGS. 1A and 1B. 110 and the second region 120 are the same as the hybrid-graphene composition 10, respectively.

An insulating layer 440 is formed on the hybrid graphene layer 410. The insulating layer 440 has an opening that opens a portion of each first region 412 of the hybrid-graphene layer 410. The insulating layer 440 is configured to insulate the first region 412 of the hybrid-graphene layer 410 from the first touch sensing unit 420. The insulating layer 440 is formed of an insulating material and may be formed of a flexible transparent insulating material. Can be.

The first touch sensing unit 420 is formed on the insulating layer 440. The first touch sensing unit 420 is formed of a conductive material. For example, the first touch sensing unit 420 may be formed of a transparent conductive material such as ITO, or may be formed of a metal material having a mesh structure. The first touch sensing unit 420 has a plurality of sensing electrodes, and the plurality of sensing electrodes of the first touch sensing unit 420 are formed to be connected to each other in a first direction. For example, as illustrated in FIG. 4A, the plurality of sensing electrodes of the first touch sensing unit 420 are formed to be connected to each other in a vertical direction on a plane, and the first touch sensing unit 420 also extends in the vertical direction. .

The second touch sensing unit 430 is formed on the hybrid graphene layer 410 and the insulating layer 440. The second touch sensing unit 430 may be formed of a conductive material, and may be formed of the same material as the first touch sensing unit 420. The second touch sensing unit 430 has a plurality of sensing electrodes, and the plurality of sensing electrodes of the second touch sensing unit 430 are formed to be separated from each other in a second direction. Although the plurality of sensing electrodes of the second touch sensing unit 430 are formed to be separated from each other, as illustrated in FIG. 4B, sensing electrodes of the second touch sensing unit 430 adjacent to each other may be openings of the insulating layer 440. Contact the same first region 412 of the hybrid-graphene layer 410, and are electrically connected through the first region 412 of the hybrid-graphene layer 410. Therefore, all of the sensing electrodes of the second touch sensing unit 430 located in the same row are electrically connected.

The touch screen panel 400 detects a touch input from a user by using the first touch detector 420 and the second touch detector 430. For example, one of the first touch sensing unit 420 and the second touch sensing unit 430 may be a first direction sensing electrode pattern, and the other may be a second direction sensing electrode pattern. The first direction sensing electrode pattern is a sensing electrode pattern for sensing a first direction (eg, Y-axis direction) coordinates of the user's touch input, and the second direction sensing electrode pattern is a second for the user's touch input. A sensing electrode pattern for sensing a direction (eg, X-axis direction) coordinate. Therefore, when a user's touch occurs at a predetermined position of the touch screen panel 400, the touch screen panel 400 detects the first direction coordinates and the second direction sensing electrode pattern detected by the first direction sensing electrode pattern. The touched position of the user may be sensed by combining the second direction coordinates.

Meanwhile, in the present specification, although both the first touch detector 420 and the second touch detector 430 are described as including a sensing electrode, the first touch detector 420 and the second touch detector 430 are described. One may be a sensing electrode pattern for sensing a change in capacitance, and the other may be a driving electrode pattern for supplying a sensing signal for detecting a touch position. In this case, when the detection signal for detecting the touch position is applied to the driving electrode pattern near the position where the user's touch actually occurred, the amount of change in capacitance generated in the sensing electrode pattern near the position where the user's touch actually occurred is the most. It can be measured largely. Therefore, the touch screen panel 400 may detect the touch position of the user based on the sensing signal supplied by the driving electrode pattern and the amount of change in capacitance sensed in the sensing electrode pattern.

In FIGS. 4A and 4B, although the first touch detector 420 and the second touch detector 430 are separated from each other and formed of a conductive material, the first touch detector 420 and the second touch detector are illustrated. 430 may also be formed using a hybrid-graphene layer. For example, the regions corresponding to the first touch detector 420 and the second touch detector 430 as shown in FIGS. 4A and 4B are conductive regions, and the first touch detector 420 and the first touch detector 420 are formed. The space between the two touch sensing units 430 may be a non-conductive region in which a hybrid-graphene layer, which is a non-conductive region, may be formed on the insulating layer 460 having an opening.

In the touch screen panel 400 according to an exemplary embodiment, the hybrid graphene layer 410 is used as a sensing electrode for sensing a user's touch input. As described above, since the solution process is used to form the hybrid-graphene layer 410 on the substrate 450, a process such as vacuum deposition for forming a conventional conductive material may not be performed, thereby processing costs. This has the effect of being reduced. In addition, the hybrid graphene layer 410 used as the sensing electrode in the touch screen panel 400 may function as an excellent gas / moisture barrier layer as described above. Accordingly, the touch screen panel 400 performs not only a user's touch input sensing function but also a barrier function, so that a separate barrier film is not required to prevent the penetration of gas or moisture, thereby simplifying the manufacturing process and the final product. There is an effect of reducing the thickness of. In addition, the flexible electronic device may be implemented by replacing the ITO material of the touch screen panel 400 with the hybrid graphene layer 400.

5 is a cross-sectional view illustrating an exemplary thin film transistor using a hybrid-graphene layer in accordance with an embodiment of the present invention. 5 shows a thin film transistor 500 as an electronic device of the present invention. Referring to FIG. 5, the thin film transistor 500 includes a gate electrode 530, an active layer 520, and a hybrid graphene layer 510. In FIG. 5, the thin film transistor 500 is a thin film transistor having an inverted staggered structure.

The gate electrode 530 is formed on the substrate 590. The gate electrode 530 is formed of a conductive material, for example, molybdenum (Mo), aluminum (Al), chromium (Cr), gold (Au), titanium (Ti), nickel (Ni), and neodymium (Nd). And copper (Cu), or an alloy thereof. A gate insulating layer 591 is formed on the gate electrode 530 to insulate the gate electrode 530 from the active layer 520. The gate insulating layer 591 may be formed of a silicon oxide film, a silicon nitride film, or a multilayer thereof. The active layer 530 is formed on the gate insulating layer 591 so as to overlap the gate electrode 520. The active layer 530 is a layer in which a channel is formed when the thin film transistor 500 is driven and may be formed of an oxide semiconductor.

The hybrid graphene layer 510 is formed on the gate insulating layer 591 in which the active layer 530 is formed. Hybrid-graphene layer 510 has a

first region

540, 550 and a second region 560. The second region 560 of the hybrid graphene layer 510 has a higher sheet resistance value than the

first regions

540 and 550 of the hybrid graphene layer 510. The

first regions

540 and 550 of the hybrid-graphene layer 510 are used as electrodes, and the

second regions

560 and 560 are used as insulating portions. The difference in electrical characteristics between them is large enough. The hybrid-graphene composition constituting the

first region

540, 550 and the second region 560 of the hybrid-graphene layer 510 is the first of the hybrid-graphene layer 100 described in FIGS. 1A and 1B. It is the same as the hybrid-graphene composition 10 constituting the region 110 and the second region 120, respectively.

In order for the second region 560 of the hybrid-graphene layer 510 to have a higher sheet resistance value than the

first regions

540 and 550, the second region 560 of the hybrid-graphene layer 510 as described above. Acid treatment methods can be used for the present invention. In this case, the acid treatment of the second region 560 of the hybrid graphene layer 510 may be performed after the hybrid graphene layer 510 is coated on the active layer 520 and the gate insulating layer 591. After the acid treatment is first performed, the hybrid graphene layer 510 may be coated. In addition, as described above, the metal nanoparticles, which are surfaced and embedded in the second region 560, may be oxidized with respect to the second region 560 of the hybrid-graphene layer 510 using a laser treatment method.

Each of the

first regions

540 and 550 of the hybrid graphene layer 510 is in contact with the active layer 520, and the second region 560 of the hybrid graphene layer 500 is the first region 540 and the first region. Insulate region 560. One of the

first regions

540 and 560 of the hybrid-graphene layer 510 serves as a source electrode of the thin film transistor 500, and the other serves as a drain electrode of the thin film transistor 500.

In the case of a thin film transistor including an active layer formed of an oxide semiconductor, a crystallization process through high temperature heat treatment of 200 ° C. or more is required to improve oxide characteristics. However, in the process of performing the high temperature heat treatment, the source layer and the drain electrode, which are generally formed of metal, and the active layer formed of the oxide semiconductor may be oxidized, thereby causing difficulty in high temperature heat treatment. However, in the thin film transistor 500 according to the exemplary embodiment of the present invention, the hybrid-graphene layer 510 is used instead of the metal electrode as the source electrode and the drain electrode. Electrode oxidation may be prevented, and thus stable electrical characteristics of the thin film transistor 500 may be secured, and stable ohmic contact between the active layer 520 and the source electrode and the drain electrode may also be secured.

In addition, when forming a source electrode and a drain electrode of a thin film transistor including an active layer formed of an oxide semiconductor, a deposition method such as sputtering a metal material used as the source electrode and the drain electrode is used. The active layer may be damaged. Therefore, in order to prevent damage to the active layer, a method of forming a source electrode and a drain electrode after forming an etch stopper on the active layer is generally used. However, in the thin film transistor 500 according to an embodiment of the present invention, instead of using a metal electrode as a source electrode and a drain electrode formed through deposition, a hybrid-graphene layer 510 coated using a solution process is used. Therefore, it is not necessary to form an etch stopper, thereby reducing manufacturing cost and manufacturing process time.

In addition, a passivation layer formed on the thin film transistor is generally used to protect each of the electrodes and the active layer of the thin film transistor from gas and moisture from the outside. However, in the thin film transistor 500 according to the exemplary embodiment of the present invention, since the hybrid-graphene layer 510 used as the source electrode and the drain electrode has the excellent gas / moisture barrier characteristics as described above, the hybrid-graphene layer 510 may perform a function such as a passivation layer. Therefore, since a separate passivation layer does not need to be formed, it is possible to reduce additional costs required for forming the passivation layer.

In FIG. 5, only the source electrode and the drain electrode are illustrated as being formed of the hybrid graphene layer 510, but the gate electrode may also be formed of the hybrid graphene layer. In addition, although the thin film transistor 500 is shown as an inverted staggered thin film transistor in FIG. 5, the hybrid-graphene layer 510 may be used in forming a coplanar thin film transistor. In addition, the active layer 520 may be formed of a material such as amorphous silicon, polycrystalline silicon, and the like instead of an oxide semiconductor.

The device using the hybrid-graphene layer according to the embodiment of the present invention replaces the conventional semiconductor process of fabricating an electric device by doping silicon impurities at a high temperature through a diffusion process. In addition, since a graphene electric device can be embedded in a hybrid-graphene layer without a high temperature process, it can be applied to various fields such as a transparent and flexible display field. The manufacturing method of such a transparent polymer structure is also applicable to the field of polymer MEMS.

6 is a cross-sectional view illustrating an exemplary organic light emitting display device using a hybrid-graphene layer according to an embodiment of the present invention. 6 illustrates an organic light emitting display 600 as an electronic device of the present invention. Referring to FIG. 6, the organic light emitting diode display 600 includes an organic light emitting diode 650 including an anode 651, an organic emission layer 652, and a cathode 653, an auxiliary electrode 640, and a partition 660. Include. In FIG. 6, only the organic light emitting diode 650, the auxiliary electrode 640, and the partition wall 660 formed on the planarization layer 611 are illustrated for convenience of description, and the thin film transistor required for driving the organic light emitting diode display 600 is illustrated. The illustration is omitted. In the present specification, the organic light emitting diode display 600 is a top emission organic light emitting diode display.

An organic light emitting element 650 including an anode 651, an organic emission layer 652, and a cathode 653 is formed on the planarization layer 611. The anode 651 formed on the planarization layer 611 is formed on the reflective layer 655 and the reflective layer 655, which are conductive layers having excellent reflectance, and has a work function for supplying holes to the organic light emitting layer 652. Transparent conductive layer 654 made of a highly conductive material. An organic emission layer 652 is formed on the anode 651. The cathode 653 formed on the organic light emitting layer 652 is formed on the metal layer 656 and the metal layer 656 made of a conductive material having a low work function to supply electrons to the organic light emitting layer 652. Hybrid-graphene layer 610. The hybrid-graphene composition constituting the hybrid-graphene layer 610 includes the hybrid-graphene composition 10 constituting the first region 110 of the hybrid-graphene layer 100 described in FIGS. 1A and 1B, That is, hybrid-graphene composition 10 comprising unoxidized metal nanoparticles 14. Although two organic light emitting diodes 650 are shown in FIG. 6, for convenience of description, reference numerals are given only to the organic light emitting diodes 650 positioned on the right side of FIG. 6.

The auxiliary electrode 640 is formed between the two organic light emitting diodes 650 on the planarization layer 611. The auxiliary electrode 640 is an electrode for compensating for a voltage drop that may occur in the top emission type organic light emitting diode display and is formed of the same material as the anode 651. In detail, the auxiliary electrode 640 is formed of the transparent conductive layer 641 and the reflective layer 642.

The bank 620 is formed on the planarization layer 611. As illustrated in FIG. 6, the bank 620 is formed to cover one side of the auxiliary electrode 640 and one side of the anode 651 of the organic light emitting element 650.

The partition wall 660 is formed on the auxiliary electrode 640. The partition wall 660 is formed in an inverse taper shape, and the organic light emitting layer 651 of the organic light emitting element 650 shown on the right side and the organic light emitting layer of the organic light emitting element shown on the left side of the partition wall 660 ( 652). In detail, a method of depositing an organic light emitting material on the entire surface of the planarization layer 611 is used to form the organic light emitting layer 652. Since the organic light emitting material has poor step coverage, the organic light emitting device 650 may be formed. The organic light emitting layer 652 is disconnected by the inverse tapered partition wall 660, and the organic light emitting layer 662 is formed on the partition wall 660. In addition, in the case of metal materials, which are materials used as the metal layer 656 of the cathode 653, since the step coverage is generally poor, the metal layer 656 of the cathode 653 may also be formed by the inverse tapered partition wall 660. Disconnected.

In the organic light emitting diode display 600 according to the exemplary embodiment, the cathode 653 includes a hybrid graphene layer 610, and the hybrid graphene layer 610 is formed by a solution process. Step coverage of the hybrid-graphene layer 610 may be determined according to the viscosity of the hybrid-graphene composition forming the hybrid-graphene layer 610. Therefore, in order to achieve the desired coverage of the hybrid-graphene layer 610, the viscosity may be controlled by adjusting the composition ratio of the polymer, metal nanoparticles, and reduced graphene platelets added at the time of preparing the hybrid-graphene composition. It is also possible to further add a binder to obtain viscosity. Thus, as shown in FIG. 6, the hybrid-graphene layer 610 is not disconnected by the partition wall 660, but the auxiliary electrode 640 exposed between the partition wall 660 and the bank 620 under the partition wall 660. ) And provide an electrical connection between the metal layer 656 of the cathode 650 and the auxiliary electrode 640.

In addition, since the materials constituting the organic light emitting layer 652 are very vulnerable to moisture and oxygen, a configuration for minimizing moisture and oxygen penetration from the outside to the organic light emitting layer 652 is required. Thus, a separate encapsulation unit such as a thin film encapsulation (TFE) may be used in the organic light emitting display device 600, but additional equipment is required to additionally form such an encapsulation unit, resulting in additional equipment cost and increased manufacturing time. Since there is a problem in using a separate encapsulation. In addition, currently used encapsulation such as TFE, glass encapsulation, metal encapsulation does not have enough flexibility required for the flexible device. In the organic light emitting diode display 600 according to the exemplary embodiment, since the hybrid-graphene layer 610 included in the cathode 653 has the excellent gas / moisture barrier characteristics as described above, the hybrid-graphene layer ( 610 may perform the same function as the encapsulation. Therefore, there is no advantage in terms of manufacturing process, since the separate sealing portion does not have to be formed.

In FIG. 6, the cathode 653 has been described as including a metal layer 656 and a hybrid-graphene layer 600. However, the cathode 653 includes only the metal layer 656 that provides electrons to the organic emission layer 652. Hybrid-graphene layer 600 may be defined as not being included in cathode 653.

Hereinafter, various features of an electronic device according to an embodiment of the present invention will be described.

According to another feature of the invention, the hybrid-graphene layer functions as a barrier layer of the electronic device, and the first region of the hybrid-graphene layer functions as an electrode of the electronic device.

According to another feature of the invention, the difference in sheet resistance between the first region and the second region is characterized in that at least 100 Ω / square or more.

According to another feature of the invention, the first region of the hybrid-graphene layer has a sheet resistance value of 1 kΩ / square or more, and the second region of the hybrid-graphene layer has a sheet resistance value of 10 kΩ / square or more It is done.

According to another feature of the invention, the plurality of metal nanoparticles interconnecting the plurality of reduced graphene platelets does not create a defect in the plurality of reduced graphene platelets of the hybrid-graphene layer. It is characterized in that the oxidizable metal material.

According to another feature of the invention, the electronic device is a touch screen panel, characterized in that the first region of the hybrid-graphene layer is composed of a touch sensing electrode of the touch screen panel.

According to another feature of the invention, the electronic device is a touch screen panel, characterized in that the first region of the hybrid-graphene layer provides electrical connection between the touch sensing electrodes of the touch screen panel.

According to another feature of the invention, the electronic device is a thin film transistor, and wherein the first region of the hybrid-graphene layer functions as at least one of a source electrode, a drain electrode and a gate electrode of the thin film transistor.

According to another feature of the invention, the electronic device is an organic light emitting display device including an organic light emitting device, wherein the first region of the hybrid-graphene layer is in direct contact with at least one of the anode and the cathode of the organic light emitting device. .

According to another feature of the invention, the electronic device is an organic light emitting display device including an organic light emitting element, the first region of the hybrid-graphene layer is characterized in that it functions as at least one of an anode and a cathode of the organic light emitting element.

According to another feature of the invention, the plurality of metal nanoparticles is characterized in that one of platinum (Pt), nickel (Ni), copper (Cu), silver (Ag), gold (Au) and combinations thereof.

Hereinafter, various features of the organic light emitting display device according to the exemplary embodiment will be described.

According to another feature of the invention, the hybrid-graphene layer is characterized in that formed in a thickness of about 10nm to 100㎛.

Hereinafter, various features of an electronic device manufacturing method according to an embodiment of the present invention will be described.

According to another feature of the invention, the step of oxidizing the three-dimensional particle shaped filler located in the second region of the hybrid-graphene layer is to expose the second region to an acid having a pKa in the range of about 4-11. By oxidizing the three-dimensional particle shape filler located in the second region.

According to another feature of the present invention, the step of oxidizing the three-dimensional particle shape filler located in the second region of the hybrid-graphene layer, the three-dimensional particle shape located in the second region by irradiating the laser to the second region. It is characterized by oxidizing the filler.

According to another feature of the invention, the step of oxidizing the three-dimensional particle-shaped filler located in the second region of the hybrid-graphene layer, the three-dimensional particles embedded in the second region by irradiating the laser to the second region Three-dimensionally located on top of the hybrid-graphene layer of the second region by first oxidation process to oxidize the filler and exposing the second region of the hybrid-graphene layer to an acid having a pKa in the range of about 4-11. And a second oxidation step of oxidizing the particle-shaped filler.

Although the embodiments of the present invention have been described in more detail with reference to the accompanying drawings, the present invention is not necessarily limited to these embodiments, and various modifications can be made without departing from the spirit of the present invention. . Therefore, the embodiments disclosed in the present invention are not intended to limit the technical idea of the present invention but to describe the present invention, and the scope of the technical idea of the present invention is not limited by these embodiments. Therefore, it should be understood that the embodiments described above are exemplary in all respects and not restrictive. The protection scope of the present invention should be interpreted by the following claims, and all technical ideas within the equivalent scope should be interpreted as being included in the scope of the present invention.

Claims

An electronic device comprising a hybrid-graphene layer comprising a first region and a second region having a sheet resistance different from the sheet resistance of the first region.

The first region includes a plurality of graphene platelets interconnected through a plurality of non-oxidized metal nanoparticles, and the second region includes a plurality of interconnected via a plurality of oxidized metal nanoparticles. An electronic device, characterized in that it comprises graphene platelets.
The method of claim 1,

The hybrid-graphene layer functions as a barrier layer of the electronic device,

The first region of the hybrid-graphene layer serves as an electrode of the electronic device.
The method of claim 1,

And the sheet resistance difference between the first region and the second region is at least 100 m 3 / square or more.
The method of claim 1,

The first region of the hybrid-graphene layer has a sheet resistance value of 1 kΩ / square or greater,

And the second region of the hybrid-graphene layer has a sheet resistance value of 10 kΩ / square or greater.
The method of claim 1,

The plurality of metal nanoparticles interconnecting the plurality of reduced graphene platelets are metal materials oxidizable by a method that does not create defects in the plurality of reduced graphene platelets of the hybrid-graphene layer. An electronic device, characterized in that.
The method of claim 1,

The electronic device is a touch screen panel,

And said first region of said hybrid-graphene layer is comprised of a touch sensing electrode of said touch screen panel.
The method of claim 1,

The electronic device is a touch screen panel,

And wherein said first region of said hybrid-graphene layer provides electrical connection between touch sensing electrodes of said touch screen panel.
The method of claim 1,

The electronic device is a thin film transistor,

And the first region of the hybrid-graphene layer functions as at least one of a source electrode, a drain electrode and a gate electrode of the thin film transistor.
The method of claim 1,

The electronic device is an organic light emitting display device including an organic light emitting element,

The first region of the hybrid-graphene layer is in direct contact with at least one of an anode and a cathode of the organic light emitting element.
The method of claim 1,

The electronic device is an organic light emitting display device including an organic light emitting element,

And the first region of the hybrid-graphene layer functions as at least one of an anode and a cathode of the organic light emitting element.
Substrate or polymer matrix; And

An electronic device comprising a hybrid-graphene layer comprising a filler consisting of a plurality of reduced graphene platelets and a plurality of metal nanoparticles,

The filler is dispersed in the polymer matrix or formed on the substrate, wherein at least some of the plurality of metal nanoparticles are on the surface of at least some of the reduced graphene platelets of the plurality of reduced graphene platelets. In contact with, an electronic device.
The method of claim 11,

Wherein the plurality of metal nanoparticles is one of platinum (Pt), nickel (Ni), copper (Cu), silver (Ag), gold (Au), and combinations thereof.
Board;

An organic light emitting element formed on the substrate; And

In an electronic device comprising a hybrid-graphene layer electrically connected to the organic light emitting device and suppressing the penetration of gas / moisture of the organic light emitting device,

The hybrid-graphene layer includes a carbon-based first filler having a two-dimensional planar shape and a metal-based second filler having a three-dimensional shape, wherein the second filler of the first region of the hybrid-graphene layer is oxidized. And the second filler of the second region of the hybrid-graphene layer is oxidized.
The method of claim 13,

And the hybrid-graphene layer is formed to a thickness of about 10 nm to 100 um.
Dispersing a carbon-based filler having a two-dimensional planar shape and a three-dimensional particle-shaped metal-based filler in a polymer matrix to form an interconnected hybrid-graphene layer on the target surface;

Protecting the first region of the hybrid graphene layer and forming a resist that exposes the second region of the hybrid graphene layer;

Oxidizing a three-dimensional particle shaped filler located in said second region of said hybrid-graphene layer; And

Removing the protective film.
The method of claim 15,

Oxidizing a three-dimensional particle shaped filler located in said second region of said hybrid-graphene layer, said second region by exposing said second region to an acid having a pKa in the range of about 4-11. A method of manufacturing an electronic device, comprising oxidizing a three-dimensional particle shaped filler located at.
The method of claim 15,

Oxidizing the three-dimensional particle-shaped filler located in the second region of the hybrid-graphene layer, irradiating a laser to the second region to oxidize the three-dimensional particle-shaped filler located in the second region. An electronic device manufacturing method, characterized in that.
The method of claim 15,

Oxidizing the three-dimensional particle-shaped filler located in the second region of the hybrid-graphene layer, irradiating a laser to the second region to oxidize the three-dimensional particle-shaped filler embedded in the second region. To a first oxidation process; And

Exposing the second region of the hybrid-graphene layer to an acid having a pKa in the range of about 4 to 11 to oxidize a three-dimensional particle shaped filler located above the hybrid-graphene layer of the second region. And a second oxidation process.
As a hybrid-graphene layer for an electronic device,

The hybrid graphene layer has a first region and a second region,

The first region is an electrical connection between the polymer, a plurality of reduced graphene platelets composed of at least two layers of reduced graphene oxide sheets dispersed in the polymer and the plurality of reduced graphene platelets. A plurality of metal nanoparticles to improve,

The second region is a plurality of graphene oxide platelets composed of a polymer, at least two layers of reduced graphene oxide sheets dispersed in the polymer, and a plurality of blocks preventing electrical connection between the plurality of graphene platelets. A hybrid-graphene layer for an electronic device, characterized in that it comprises oxidized metal nanoparticles of.
Forming a hybrid-graphene layer comprising a polymer, a plurality of reduced graphene oxide platelets composed of one or more reduced graphene sheets and a plurality of metal nanoparticles, the first graph having a first region and a second region; And

A method of manufacturing an electronic device comprising selectively oxidizing a metal nanoparticle included in the second region of the plurality of metal nanoparticles of the hybrid-graphene layer.

And the second region has a sheet resistance value higher than the sheet resistance of the first region.