WO2015102402A1 - Dispositif électronique flexible ayant une couche barrière multifonctionnelle - Google Patents

Dispositif électronique flexible ayant une couche barrière multifonctionnelle Download PDF

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WO2015102402A1
WO2015102402A1 PCT/KR2014/013089 KR2014013089W WO2015102402A1 WO 2015102402 A1 WO2015102402 A1 WO 2015102402A1 KR 2014013089 W KR2014013089 W KR 2014013089W WO 2015102402 A1 WO2015102402 A1 WO 2015102402A1
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hybrid
graphene
region
layer
platelets
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Korean (ko)
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남보애
채기성
심동훈
조성희
이신우
강지연
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엘지디스플레이 주식회사
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L29/00—Semiconductor devices specially adapted for rectifying, amplifying, oscillating or switching and having potential barriers; Capacitors or resistors having potential barriers, e.g. a PN-junction depletion layer or carrier concentration layer; Details of semiconductor bodies or of electrodes thereof ; Multistep manufacturing processes therefor
    • H01L29/66—Types of semiconductor device ; Multistep manufacturing processes therefor
    • H01L29/68—Types of semiconductor device ; Multistep manufacturing processes therefor controllable by only the electric current supplied, or only the electric potential applied, to an electrode which does not carry the current to be rectified, amplified or switched
    • H01L29/76—Unipolar devices, e.g. field effect transistors
    • H01L29/772—Field effect transistors
    • H01L29/78—Field effect transistors with field effect produced by an insulated gate
    • H01L29/786—Thin film transistors, i.e. transistors with a channel being at least partly a thin film
    • H01L29/78684—Thin film transistors, i.e. transistors with a channel being at least partly a thin film having a semiconductor body comprising semiconductor materials of Group IV not being silicon, or alloys including an element of the group IV, e.g. Ge, SiN alloys, SiC alloys
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
    • H01B13/00—Apparatus or processes specially adapted for manufacturing conductors or cables
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
    • H01B5/00—Non-insulated conductors or conductive bodies characterised by their form
    • H01B5/14—Non-insulated conductors or conductive bodies characterised by their form comprising conductive layers or films on insulating-supports
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L29/00—Semiconductor devices specially adapted for rectifying, amplifying, oscillating or switching and having potential barriers; Capacitors or resistors having potential barriers, e.g. a PN-junction depletion layer or carrier concentration layer; Details of semiconductor bodies or of electrodes thereof ; Multistep manufacturing processes therefor
    • H01L29/66—Types of semiconductor device ; Multistep manufacturing processes therefor
    • H01L29/68—Types of semiconductor device ; Multistep manufacturing processes therefor controllable by only the electric current supplied, or only the electric potential applied, to an electrode which does not carry the current to be rectified, amplified or switched
    • H01L29/76—Unipolar devices, e.g. field effect transistors
    • H01L29/772—Field effect transistors
    • H01L29/78—Field effect transistors with field effect produced by an insulated gate
    • H01L29/786—Thin film transistors, i.e. transistors with a channel being at least partly a thin film
    • H01L29/78696—Thin film transistors, i.e. transistors with a channel being at least partly a thin film characterised by the structure of the channel, e.g. multichannel, transverse or longitudinal shape, length or width, doping structure, or the overlap or alignment between the channel and the gate, the source or the drain, or the contacting structure of the channel
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K2102/00—Constructional details relating to the organic devices covered by this subclass
    • H10K2102/301—Details of OLEDs
    • H10K2102/311—Flexible OLED
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K59/00—Integrated devices, or assemblies of multiple devices, comprising at least one organic light-emitting element covered by group H10K50/00
    • H10K59/80—Constructional details
    • H10K59/805—Electrodes
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
    • H10K85/20—Carbon compounds, e.g. carbon nanotubes or fullerenes

Definitions

  • 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.
  • ITO indium tin oxide
  • transparent conductive oxides such as ITO
  • transparent electrodes 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.
  • 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.
  • 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.
  • 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 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.
  • one component has a multi-function barrier layer capable of implementing not only the moisture barrier protection performance but also the electrode performance as needed, it is possible to meet the functions required for the implementation of transparent and flexible electronic devices in the future. 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.
  • 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.
  • the hybrid-graphene layer is composed of a polymer, a plurality of reduced graphene platelets dispersed in the polymer, and a plurality of metal nanoparticles interconnecting the plurality of reduced graphene platelets of the polymer.
  • the hybrid graphene layer has a first region and a second region each having a different sheet resistance value.
  • the plurality of reduced graphene platelets located in the first region are interconnected through a plurality of metal nanoparticles in an unoxidized state.
  • the plurality of reduced graphene platelets located in the second region having a higher sheet resistance value than the first region are interconnected through the metal nanoparticles in the oxidized state.
  • the first region has a sheet resistance value of 1 k ⁇ / square or more
  • the second region has a sheet resistance value of 10 k ⁇ / square or more.
  • the first region and the second region have a sheet resistance difference of at least 100 m 3 / square or more.
  • the hybrid-graphene layer is a filler composed of a plurality of reduced graphene platelets and metal nanoparticles is applied onto a substrate or dispersed in a polymer matrix to form a hybrid-graphene layer.
  • the metal nanoparticles may be attached to the surface of the at least one reduced graphene platelet through the furnace in aerosol droplets with the reduced graphene platelet.
  • the present specification provides an electronic device including a substrate, an organic light emitting element formed on the substrate, a conductive layer electrically connected to the organic light emitting element, and a barrier layer for suppressing the penetration of gas / moisture of the organic light emitting element.
  • the conductive layer and the barrier layer are formed of a layer including a carbon-based first filler having a two-dimensional planar shape and a metal-based second filler having a three-dimensional shape.
  • the second filler located in the first region of the multifunctional membrane is not oxidized, but the second filler in the second region of the multifunctional membrane is oxidized.
  • a novel solution type hybrid-graphene composition capable of forming a film on a desired surface by various solution processes composed of a plurality of reduced graphene platelets, a plurality of metal nanoparticles, and a polymer is disclosed.
  • the solution type hybrid-graphene composition further comprises a surfactant that facilitates dispersion of the plurality of reduced graphene platelets and the plurality of oxidizable metal nanoparticles.
  • the present disclosure further provides a method of making a novel device using such a novel composition.
  • a method for manufacturing a novel device using the novel composition comprises a hybrid-graphene layer in which a carbon-based filler having a two-dimensional planar shape and a metal-based filler having a three-dimensional particle shape are dispersed and connected in a polymer matrix. Is formed on the target surface. A protective layer is formed on the hybrid graphene layer to protect the first region and expose the second region of the hybrid graphene layer. Thereafter, the three-dimensional particle-shaped filler located in the second region of the hybrid-graphene layer is oxidized. The protective film is then removed to expose the first region over the protective layer to form a hybrid-graphene layer that can be used as barrier performance and as an electrode.
  • 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.
  • FIG. 2 is a flow chart illustrating an exemplary method of forming a hybrid-graphene layer in accordance with an embodiment of the present invention.
  • FIG. 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.
  • FIG. 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.
  • FIG. 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.
  • 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.
  • 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.
  • 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.
  • 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.
  • 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 ⁇ 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.
  • 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.
  • 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.
  • graphene collectively refers to graphene oxide, reduced graphene oxide as well as pristine graphene.
  • 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.
  • 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.
  • the reduced graphene oxide platelet 12 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
  • 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.
  • FIG. 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.
  • 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.
  • 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.
  • 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.
  • 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.
  • 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.
  • 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.
  • 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.
  • 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).
  • CNTs carbon nanotubes
  • 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
  • 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.
  • 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.
  • 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.
  • 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.
  • 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.
  • 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.
  • 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.
  • the reduced graphene oxide platelets 12 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.
  • 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.
  • 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,
  • the patterning device may be patterned into at least one conductive region and at least one non-conductive region.
  • 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.
  • the aforementioned electrical defects may be repaired by the plurality of metal nanoparticles 14 included in the hybrid-graphene composition 10.
  • 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
  • the overall sheet resistance of the hybrid graphene layer 100 is improved.
  • 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).
  • the hybrid-graphene layer 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.
  • 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.
  • 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.
  • 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.
  • 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.
  • the metal nanoparticles 14 located in the region-treated region may be oxidized by treating the hybrid-graphene layer 100 with an acid.
  • 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.
  • 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.
  • 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.
  • 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.
  • the oxidation process will be performed after the hybrid-graphene layer 100 is coated or applied onto the surface.
  • 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.
  • 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.
  • the strength of the acid in the oxidation method with acid 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 is 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.
  • the thickness of the fin composition 10 it should be determined in consideration of various factors.
  • 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.
  • an acid oxidation method and a laser oxidation method.
  • the precise oxidation of the metal nanoparticles 14 can be achieved in a faster time than when using one oxidation method.
  • 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.
  • FIGS 2 and 3 are flowcharts illustrating an exemplary method of forming hybrid-graphene layer 100.
  • 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.
  • 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.
  • 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.
  • 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.
  • 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 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.
  • 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.
  • 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.
  • the dispersion of the sonicated graphite comprises expanded graphite crystals that can be removed through centrifugation.
  • centrifugation at 500 rpm can remove graphite crystals that did not exfoliate while leaving dispersed graphene oxide platelets.
  • 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.
  • 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.
  • 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 ⁇ -electrons resulting in much lower carrier mobility and carrier concentration. Even though there are conjugated regions in graphene oxide, the far (> ⁇ m) 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 ⁇ / square or more.
  • 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, the graphene oxide platelets are chemically reduced in solution with reducing agents such as hydrazine hydrate, dimethylhydrazine, hydroquinone and NaBH4, resulting in conjugated structures and other molecular units. The lattice defects are partially recovered and oxygen functionalities are removed, converting 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.
  • reducing agents such as hydrazine hydrate, dimethylhydrazine, hydroquinone and NaBH4
  • the hybrid-graphene composition comprises a polymer matrix, reduced graphene oxide platelets as filler and metal nanoparticles.
  • 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 ( ⁇ -caprolactone).
  • 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.
  • the graphene oxide platelets reduced in the hybrid-graphene composition 10 ( The metal nanoparticles 14 interconnecting 12 should be oxidizable metal nanoparticles 14.
  • 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.
  • metal nanoparticles 14 usable in the hybrid-graphene composition 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.
  • 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.
  • 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.
  • 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.
  • 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
  • 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.
  • 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.
  • 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.
  • the hybrid graphene layer 100 may be restricted.
  • 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.
  • 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.
  • 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.
  • graphene oxide platelets 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.
  • Polar groups of reduced graphene oxide sheets in reduced graphene oxide platelets 12 provide compatibility to the polymer.
  • 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.
  • 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.
  • fin oxide platelets 12 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.
  • 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.
  • 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.
  • 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).
  • 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.
  • 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.
  • 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).
  • S320 airgel droplets
  • 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.
  • a furnace a tubular furnace may be used.
  • the sprayed airgel droplets can be transferred to the furnace using gas.
  • 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.
  • 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.
  • 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.
  • 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.
  • 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.
  • a reducing gas having hydrogen (H 2 ) or other active or volatile characteristics in the furnace may be 50%, respectively.
  • the ratio of H 2 and N 2 in the reducing atmosphere in the entire furnace may be 50:50, respectively.
  • 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 at 50% or less, more preferably at 25% or less.
  • 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.
  • 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. It can also be injected into the furnace with the.
  • the graphene 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.
  • 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.
  • 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.
  • 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).
  • an aqueous solution eg, an organic solvent
  • a surfactant that is easy to inhibit re-agglomeration between the platelets and collecting it directly in the solution (S340).
  • 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.
  • 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).
  • 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.
  • 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.
  • 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.
  • the vapor in which the reduced graphene oxide platelets are dispersed may be collected using a solution containing metal nanoparticles and a liquid polymer.
  • 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.
  • 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.
  • 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.
  • 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.
  • 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).
  • the insulating layer 450 is not illustrated, and hatching of the hybrid graphene layer 410 is illustrated.
  • 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.
  • 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.
  • 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.
  • 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.
  • 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
  • the second direction sensing electrode pattern is a second for the user's touch input.
  • 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.
  • 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.
  • 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.
  • 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.
  • 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 include a hybrid-graphene layer having a non-conductive area on the insulating layer 460 having an opening.
  • the hybrid graphene layer 410 is used as a sensing electrode for sensing a user's touch input.
  • 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.
  • 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.
  • 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.
  • 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.
  • the thin film transistor 500 includes a gate electrode 530, an active layer 520, and a hybrid graphene layer 510.
  • 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.
  • the second region 560 of the hybrid-graphene layer 510 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.
  • 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.
  • 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.
  • a crystallization process through high temperature heat treatment of 200 ° C. or more is required to improve oxide characteristics.
  • 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.
  • 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.
  • 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.
  • a hybrid-graphene layer 510 coated using a solution process is used instead of using a metal electrode as a source electrode and a drain electrode formed through deposition. Therefore, it is not necessary to form an etch stopper, thereby reducing manufacturing cost and manufacturing process time.
  • 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.
  • 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.
  • 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.
  • 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.
  • 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.
  • 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.
  • FIG. 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.
  • 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.
  • 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. The illustration is omitted.
  • the organic light emitting diode display 600 is a top emission organic light emitting diode display.
  • 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.
  • hybrid-graphene composition 10 comprising unoxidized metal nanoparticles 14.
  • 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.
  • 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).
  • 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.
  • the metal layer 656 of the cathode 653 may also be formed by the inverse tapered partition wall 660. Disconnected.
  • 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.
  • 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.
  • 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.
  • TFE thin film encapsulation
  • 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.
  • 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.
  • the plurality of metal nanoparticles interconnecting the plurality of reduced graphene platelets are capable of oxidizing the plurality of reduced graphene platelets of the hybrid-graphene layer by a method that does not create a defect. It is characterized in that the metal material.
  • the plurality of metal nanoparticles is characterized by having a smaller area than the plurality of reduced graphene platelets.
  • the metal nanoparticles are characterized in that the metal nanoparticles capable of oxidation by acid or laser treatment having a pKa of about 4 to about 11.
  • the plurality of metal nanoparticles is characterized in that one of platinum (Pt), nickel (Ni), copper (Cu), silver (Ag), gold (Au) and combinations thereof. .
  • the first region of the hybrid-graphene layer has a sheet resistance value of 1 k ⁇ / square or more
  • the second region of the hybrid-graphene layer has a sheet resistance value of 10 k ⁇ / square or more.
  • the sheet resistance difference between the first region and the second region is characterized in that more than 100 ⁇ / square.
  • the plurality of reduced graphene platelets are characterized by having an aspect ratio of 1: 10000.
  • the hybrid-graphene layer is characterized in that it has a thickness of about 10nm to 100 ⁇ m.
  • the plurality of reduced graphene platelets are characterized in that the reduced graphene platelets are substantially free of oxygen functional groups.
  • the average value of the number of layers included in the plurality of reduced graphene platelets is characterized in that 2 to 10.
  • the average lateral length of the plurality of reduced graphene platelets is about 0.1 ⁇ m to about 10 ⁇ m, and the average diameter of the metal nanoparticles is about 1 nm to about 50 nm. do.
  • the plurality of reduced graphene platelets are characterized by having an aspect ratio of 1.5: 5000.
  • the ratio of the plurality of reduced graphene platelets and the metal nanoparticles included in the hybrid-graphene layer is characterized in that 50:50.
  • the solution type hybrid-graphene composition is further characterized by further comprising a surfactant which facilitates dispersion of the plurality of reduced graphene platelets and the plurality of oxidizable metal nanoparticles.
  • At least one of the plurality of metal nanoparticles is characterized in that it is attached to the surface of at least one reduced graphene platelet.
  • At least 50% or more of the plurality of reduced graphene platelets included in the hybrid-graphene composition is composed of two or more reduced graphene oxide sheets.
  • the reduced graphene platelets are characterized by grafting of functional groups to facilitate dispersion in the polymer chain.
  • the second filler in the second region is a metal nanoparticle with a molecular formula of MxOy, where M is platinum (Pt), nickel (Ni), copper (Cu), silver (Ag), Gold (Au), or a combination thereof, wherein x and y are positive integers.
  • the first filler having a two-dimensional planar shape is characterized in that connected to the second filler having a three-dimensional shape.
  • the length of the first pillar having a two-dimensional planar shape to the longest axis is about 0.1 ⁇ m to about 10 ⁇ m, and the diameter of the second filler having a three-dimensional shape is about 1 nm to about 50 nm.
  • 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.
  • 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 is characterized by oxidizing the filler.
  • 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.

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Abstract

L'invention porte sur une couche de graphène hybride qui consiste : en un polymère ; en une pluralité de plaquettes de graphène réduites, dispersées dans le polymère ; en une pluralité de nanoparticules métalliques pour connecter mutuellement la pluralité de plaquettes de graphène réduites. La couche de graphène hybride possède une première région et une seconde région ayant chacune des valeurs de résistance de surface différentes. Une pluralité de plaquettes de graphène réduites, qui sont positionnées au niveau de la première région, sont mutuellement connectées par une pluralité de nanoparticules métalliques qui ne sont pas oxydées. Une pluralité de plaquettes de graphène réduites, qui sont positionnées au niveau de la seconde région ayant une valeur de résistance de surface supérieure à celle de la première région, sont mutuellement connectées par une pluralité de nanoparticules métalliques qui sont oxydées.
PCT/KR2014/013089 2013-12-30 2014-12-30 Dispositif électronique flexible ayant une couche barrière multifonctionnelle WO2015102402A1 (fr)

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KR102522012B1 (ko) 2015-12-23 2023-04-13 삼성전자주식회사 전도성 소자 및 이를 포함하는 전자 소자
KR102543984B1 (ko) 2016-03-15 2023-06-14 삼성전자주식회사 도전체, 그 제조 방법, 및 이를 포함하는 전자 소자

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