KR20150049279A - Electrode and method of manufacturing the same - Google Patents
Electrode and method of manufacturing the same Download PDFInfo
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- KR20150049279A KR20150049279A KR1020130129593A KR20130129593A KR20150049279A KR 20150049279 A KR20150049279 A KR 20150049279A KR 1020130129593 A KR1020130129593 A KR 1020130129593A KR 20130129593 A KR20130129593 A KR 20130129593A KR 20150049279 A KR20150049279 A KR 20150049279A
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Abstract
Description
Electrode and a method of manufacturing the same.
Graphene has attracted attention as a transparent electrode material due to its advantages such as high conductivity and high transmittance. When such graphenes are fabricated on a transparent substrate, they can be used variously as electrode materials for display and illumination. However, in the case of transferring a high-quality graphene to a glass substrate or a flexible substrate which is actually used, it is difficult to realize high graphene-specific high conductivity, and manufacturing cost may increase.
In this context, oxidized graphene has been attracting attention, and graphene oxide has the advantage of mass production through various methods. In addition, the oxidized graphene produced by various methods can be directly coated on a large-area substrate after being dispersed in water or an organic solvent.
However, the electrical conductivity of oxidized graphene is very low compared to that of intrinsic graphene, and the reduction process of oxidized graphene is needed.
The reduction process of the graphene graphene can be performed by various methods such as heat treatment, chemical solvent treatment, photocatalytic reaction, and plasma treatment. Most reduction processes involve high heat treatment temperatures or the use of highly toxic, high-risk chemicals to remove oxygen from the oxidized graphene.
One embodiment of the present invention can provide an electrode comprising reduced oxidized graphene and a metal oxide layer.
One embodiment of the present invention can provide a method of manufacturing an electrode comprising reduced oxidized graphene and a metal oxide layer.
In one embodiment of the invention, reduced Graphene Oxide (rGO); And a metal oxide layer positioned on the reduced oxidized graphene.
The thickness of the metal oxide layer may be 0.1 nm to 100 nm.
The metal oxide layer may be a completely oxidized metal oxide layer or a gradient structure in which a metal and a metal oxide layer are mixed.
The reduced graphene oxide and the metal oxide layer may be formed through a simultaneous oxidation-reduction reaction.
The substrate may be located under the reduced oxidized graphene.
The reduced oxidized graphene and the metal oxide layer on the substrate may be formed by simultaneous oxidation-reduction directly from the oxidized graphene and the metal layer formed on the substrate.
The metal may be selected from the group consisting of Ag, Cu, Ni, Al, Fe, Co, Si, Zn, Sn, Pd, Ti, V, Cr, Zr, In, or combinations thereof.
The metal oxide layer may be used as a buffer layer in the device, an active material layer in the device, a photocatalyst in the device, or a filler in the device.
In another embodiment of the present invention, there is provided a method of manufacturing a semiconductor device, comprising: preparing a substrate; Forming an oxidized graphene layer on the substrate; Forming a metal layer on the oxide graphene layer; And a step of obtaining a reduced oxidized graphene layer and a metal oxide layer by simultaneous oxidation-reduction reaction between the oxidized graphene layer and the metal layer.
Forming an oxidized graphene layer on the substrate; Thereafter, stabilizing the formed oxide graphene layer may be further included.
Forming an oxidized graphene layer on the substrate; And / or forming a metal layer on the oxide graphene layer, wet or dry methods may be used.
Forming an oxidized graphene layer on the substrate; And / or forming a metal layer on the oxide graphene layer may be performed by sputtering deposition, spray coating, spin coating, slot-die coating, or a combination thereof.
The step of stabilizing the formed oxidized graphene layer may be treatment using heat, ultraviolet rays, laser, infrared rays, plasma, electron beams, or a combination thereof.
The step of forming the metal layer on the oxide graphene layer may be performed by an electroplating method, a plasma chemical vapor deposition method, a magnetron sputtering method, a vacuum evaporation method, an arc vapor deposition method, an atomic layer deposition method, or a combination thereof.
The step of obtaining a reduced oxidized graphene layer and a metal oxide layer through simultaneous oxidation-reduction reaction between the oxidized graphene layer and the metal layer may be performed by using a method of heat, ultraviolet ray, laser, infrared ray, plasma, electron beam or a combination thereof .
In the step of forming the metal layer on the oxidized graphene layer, the thickness of the formed metal layer may be 0.1 nm to 100 nm.
The method comprising: preparing the substrate; forming an oxidized graphene layer on the substrate; And forming a metal layer on the oxide graphene layer, the method comprising: preparing a substrate; forming a metal layer on the substrate; And forming an oxidized graphene layer on the metal layer.
The wet process is performed at atmospheric pressure, and the dry process may be performed at a pressure of 10 -7 torr to 760 Torr.
The method of manufacturing the electrode may be a continuous process.
The continuous process may be an in-line or a roll-to-roll process.
According to an embodiment of the present invention, it is possible to replace the high-temperature and high-risk reduction process in the graphene oxide (GO) reduction process of oxidized grains, and to use the reduced graphene oxide (rGO) The necessary metal oxide film can be formed simultaneously with the reduction of the oxidized graphene GO.
Also, it is possible to provide a device such as a solar cell, an OLED, a touch panel, a sensor, or the like containing a reduced oxide graphene (rGO) / metal oxide layer as an electrode.
1 is an overall process flow diagram of a manufacturing method according to an embodiment of the present invention.
2 is a schematic process diagram of an entire manufacturing method according to an embodiment of the present invention.
FIG. 3 is an X-ray diffraction (XRD) graph for the structure (2) including the GO coating film (1) prepared in Example 1 and the rGO / Cu oxide film as the final material prepared in Example 1.
Fig. 4 is a graph showing the current density of an organic solar cell including a transparent electrode composed of an electrode including a reduced oxidized graphene (rGO) layer / Cu oxide layer prepared in Example 1 containing only reduced oxidized graphene (rGO) And a current density of a solar cell including a transparent electrode made of an electrode.
Hereinafter, one embodiment of the present invention will be described in detail. However, it should be understood that the present invention is not limited thereto, and the present invention is only defined by the scope of the following claims.
The term '/' used to express the laminated structure of the reduced graphene (rGO) and the metal or metal oxide layer in this specification means that in the arrangement between the elements immediately before and after '/' / 'And' / 'are in direct contact with each other at an interface with each other, as well as when the intermediate layer contains substances other than those listed before or after the' / ' But it is also possible to interpret it as including the case where it is made.
One embodiment of the present invention may provide an electrode comprising reduced Graphene Oxide (rGO) and a metal oxide layer.
In addition, the thickness of the metal oxide layer may be 0.1 nm to 100 nm. The range is such that the surface resistance or the sheet resistance can be sufficiently reduced while minimizing the decrease in the transmittance of the electrode including the reduced Graphene Oxide (rGO) and the metal oxide layer. However, the present invention is not limited thereto.
The metal oxide layer may be a completely oxidized metal oxide layer or a gradient structure in which a metal and a metal oxide layer are mixed.
More specifically, the reduced graphene oxide and the metal oxide layer may be formed through a simultaneous oxidation-reduction reaction. That is, reduced graphene grains and a metal oxide layer can be formed without a separate transfer process.
More specifically, the substrate may be located under the reduced oxidized graphene.
The reduced oxidized graphene and the metal oxide layer on the substrate may be formed by simultaneous oxidation-reduction directly from the oxidized graphene and the metal layer formed on the substrate.
More specifically, it is possible to provide a substrate / reduced oxide graphene / metal oxide layer structure electrode without any separate transfer process, while minimizing damage to the substrate. In this structure, the metal oxide layer can serve as a buffer layer in the device.
Specifically, the metal may be at least one of Ag, Cu, Ni, Al, Fe, Co, Si, Zn, (Sn), Pd, Ti, V, Cr, Zr, In, or combinations thereof. However, the present invention is not limited thereto.
The electrode according to one embodiment of the present invention is applicable to various devices.
Examples of the field in which the electrode is utilized include various display devices such as a liquid crystal display device, an electronic paper display device, and an organic / inorganic photoelectric device, and can be used for a battery field, for example, a lithium secondary battery, .
When the electrode according to one embodiment of the present invention is used for various devices, the thickness of the electrode is preferably adjusted in consideration of transparency. For example, when the thickness of the electrode is more than 100 nm, transparency may be deteriorated and the light efficiency may be deteriorated. When the thickness is less than 0.1 nm, It may be too low or the film of the graphene sheet may become uneven.
The dye-sensitized solar cell may include a semiconductor electrode, an electrolyte layer, and an opposite electrode. The semiconductor electrode may include a conductive transparent substrate, And a light absorbing layer. A colloid solution of a nanoparticle oxide is coated on a conductive glass substrate, heated in a high-temperature electric furnace, and then adsorbed on a dye.
As the semiconductor electrode and / or the counter electrode, an electrode according to an embodiment of the present invention may be used.
Such an electrode can be obtained according to one embodiment of the present invention. As the transparent substrate, for example, a transparent polymer material such as polyethylene terephthalate, polycarbonate, polyimide, polyamide or polyethylene naphthalate or a copolymer thereof, or A glass substrate can be used. The nanoparticle oxide used in the solar cell is preferably an n-type semiconductor that serves as an electron current carrier under the photoexcitation as a semiconductor fine particle and provides an anode current. Specific examples thereof include TiO 2 , SnO 2 , ZnO 2 , WO 3 , Nb 2 O 5 , Al 2 O 3 , MgO, and TiSrO 3 , and particularly preferred is anatase TiO 2 . The metal oxides are not limited to these, and they may be used alone or in combination of two or more thereof.
It is preferable that the semiconductor particulates have a large surface area in order to allow the dye adsorbed on the surface to absorb more light. For this purpose, it is preferable that the particle diameter of the semiconductor fine particles is about 20 nm or less.
The dye may be used without limitation as long as it is generally used in the field of solar cells or photovoltaic cells, but a ruthenium complex is preferable. As the ruthenium complex, RuL 2 (SCN) 2 , RuL 2 (H 2 O) 2 , RuL 3 , RuL 2 and the like can be used (in the formula, L represents 2,2'-bipyridyl-4,4'- And the like). However, such a dye is not particularly limited as long as it has a charge-separating function and exhibits a sensitizing action. In addition to ruthenium complexes, for example, xanthine based pigments such as rhodamine B, rose bengal, eosin and erythrosine, Basic dyes such as cyanine dye, cyanine dye, cyan dye, cyanine dye, cyanine dye, cyanine dye, cyanine dye, Bipyridyl and the like, anthraquinone type pigments, and polycyclic quinone type pigments, and these may be used singly or in combination of two or more.
The thickness of the light absorbing layer including the nanoparticle oxide and the dye is 15 mm or less, preferably 1 to 15 mm. This is because the light absorption layer has a large series resistance for its structural reasons and an increase in series resistance results in a reduction in conversion efficiency. By keeping the film thickness to 15 mm or less, Can be prevented from being lowered.
The electrolyte layer used in the dye-sensitized solar cell may be a liquid electrolyte, an ionic liquid electrolyte, an ionic gel electrolyte, a polymer electrolyte, and a complex between them.
Typically, it is made of an electrolytic solution, and includes the light absorbing layer or is formed so that the electrolyte is infiltrated into the light absorbing layer. As the electrolytic solution, for example, acetonitrile solution of iodine or the like can be used, but it is not limited thereto, and any electrolytic solution may be used as long as it has a hole conduction function.
In addition, the dye-sensitized solar cell may further include a catalyst layer. The catalyst layer is for promoting the redox reaction of the dye-sensitized solar cell, and may be formed of platinum, carbon, graphite, carbon nanotubes, carbon black, A complex among them, and the like, which are located between the electrolyte layer and the counter electrode. It is preferable that the catalyst layer has a fine structure with an increased surface area. For example, if the catalyst layer is platinum, it is preferable that the catalyst layer is in a platinum black state and the carbon layer is in a porous state. The platinum black state can be formed by the anodic oxidation of platinum, the treatment with chloroplatinic acid, or the like, and the porous carbon can be formed by a method such as sintering of carbon microparticles or firing of an organic polymer.
Examples of the display device using the graphene sheet-containing electrode according to an embodiment of the present invention include an electronic paper display device, an optoelectronic device (organic or inorganic), and a liquid crystal display device. Among the organic optoelectronic devices, the organic optoelectronic device is an active light-emitting display device that uses a phenomenon in which light is generated while electrons and holes are combined in an organic film when a current is supplied to a fluorescent or phosphorescent organic compound thin film. A typical organic optoelectronic device has a structure in which an anode is formed on a substrate, and a hole transport layer, a light emitting layer, an electron transport layer, and a cathode are sequentially formed on the anode. In order to facilitate injection of electrons and holes, an electron injection layer and a hole injection layer may be further provided. If necessary, a hole blocking layer, a buffer layer, and the like may be further provided. The anode is preferably a transparent and highly conductive material, and the electrode according to an embodiment of the present invention may be usefully used. At this time, the metal oxide layer included in the electrode according to an embodiment of the present invention may serve as a buffer layer.
Therefore, since the electrode according to the present invention includes a buffer layer, a separate organic buffer layer may not be formed.
As a material of the hole transporting layer, a commonly used material may be used, and polytriphenylamine may be preferably used, but the present invention is not limited thereto.
As the material of the electron transporting layer, a commonly used material can be used, and preferably polyoxadiazole can be used, but the present invention is not limited thereto.
As the luminescent material used in the luminescent layer, fluorescent or phosphorescent materials generally used may be used without limitation, but they may be selected from the group consisting of at least one polymer host, a mixture host of a polymer and a small molecule, a low molecular host, and a non-luminescent polymer matrix And may further include one or more. Here, the polymer host, the low molecular weight host, and the non-light emitting polymer matrix may be any of those conventionally used for forming the light emitting layer for the organic electroluminescent device. Examples of the polymer host include poly (vinylcarbazole), polyfluorene, poly (p-phenylenevinylene), polythiophene and the like. Examples of the low molecular weight host include CBP (4,4'-N, N'-dicarbazole-biphenyl), 4,4'- (3,6-biphenylcarbazolyl)] - 1-1, 1'-biphenyl {4,4'-bis [9- Phenyl], 9,10-bis [(2 ', 7'-t-butyl) -9', 9 "-spirobifluorenyl anthracene, tetrafluorene, But are not limited to, polymethyl methacrylate, polystyrene, and the like. The above-described light emitting layer can be formed by a vacuum deposition method, a sputtering method, a printing method, a coating method, an inkjet method, or the like.
The fabrication of the organic optoelectronic device according to an embodiment of the present invention does not require a special device or method and can be manufactured according to a method of manufacturing an organic optoelectronic device using a conventional light emitting material.
In addition, the electrode manufactured according to one embodiment of the present invention can be used as an active layer of an electronic device.
The active layer may be used for a solar cell. The solar cell may include at least one active layer between a lower electrode layer and an upper electrode layer stacked on a substrate.
The substrate may be selected from any one of, for example, a polyethylene terephthalate substrate, a polyethylene naphthalate substrate, a polyether sulfone substrate, an aromatic polyester substrate, a polyimide substrate, a glass substrate, a quartz substrate, a silicon substrate, .
The lower electrode layer may be selected from, for example, a graphene sheet, indium-tin-oxide (ITO), or fluorine-tin-oxide (FTO).
The electronic device may be a transistor, a sensor, or an organic semiconductor device.
In the case of conventional transistors, sensors, and semiconductor devices, IV-group semiconductor heterostructure, III-V, and II-VI compound semiconductor heterostructures are formed and the electron movement is limited to two dimensions through band gap engineering It was possible to have a high electron mobility of about 100 to 1,000 cm 2 / Vs.
The electrode according to an embodiment of the present invention may be used in a battery.
A specific example of the battery may be a lithium secondary battery.
The lithium secondary battery can be classified into a lithium ion battery, a lithium ion polymer battery, and a lithium polymer battery depending on the type of the separator and electrolyte used. The lithium secondary battery can be classified into a cylindrical shape, a square shape, a coin shape, Depending on the size, it can be divided into bulk type and thin type. The structure and the manufacturing method of these cells are well known in the art, and detailed description thereof will be omitted.
The lithium secondary battery includes a negative electrode, a positive electrode, a separator disposed between the negative electrode and the positive electrode, an electrolyte impregnated in the negative electrode, the positive electrode and the separator, a battery container, and a sealing member for sealing the battery container . Such a lithium secondary battery is constituted by stacking a negative electrode, a positive electrode and a separator in this order, and then winding it in a spiral wound state in a battery container.
The positive electrode and the negative electrode may include a current collector, an active material, a binder, and the like.
More specifically, the metal oxide layer can be used as an active material in a device. A specific example of the element is a lithium secondary battery. The description of the lithium secondary battery is as described above.
The metal oxide layer may be used as the active material, and in this case, the reduced graphene graphene may be used as a current collector.
As described above, in the case of a lithium secondary battery including an electrode (anode or cathode) according to an embodiment of the present invention, the electron mobility is excellent and the efficiency and lifetime characteristics of the battery can be improved.
More specifically, the metal oxide layer can be used as a photocatalyst in the device. As a specific example of the device, there is a water decomposition apparatus using a photocatalyst.
The water decomposition apparatus using the photocatalyst includes a container for accommodating water to be decomposed by photocatalysis, an electrically conductive separator layer extending in an inner space of the container used for contacting water contained in the container, .
Specifically, one surface of the electrically conductive separator layer may be an apparatus in which an oxygen-generating photocatalyst is provided in at least one portion thereof extended from water and the other surface is provided with a hydrogen-generating photocatalyst. In order to allow water to be oxidized by the oxygen-generating photocatalyst in order to decompose water, and to allow water to be reduced by the hydrogen-generating photocatalyst at the same time, in order to allow light to reach the oxygen generating photocatalyst and the hydrogen generating photocatalyst, And a separator layer is arranged in the container.
In this case, for example, in the case of a water decomposition apparatus using a photocatalyst including an electrode according to an embodiment of the present invention, O 2 adsorbed on the surface of the TiO 2 metal oxide layer is transformed into O - and OH radicals upon ultraviolet irradiation Substances such as benzaldehyde in contact with the TiO 2 metal oxide layer surface can be broken down into water and carbon dioxide by breaking the benzene ring by O - radicals.
More specifically, the metal oxide layer can be used as a filler in the device. As a specific example of the device, there is a super capacitor.
The cell of the supercapacitor may typically comprise a pair of electrodes comprising particulate activated carbon and a uniformly dispersed electrolyte component. Specifically, the supercapacitor may have a bilayer structure in which the pair of electrodes are separated by a spacer element having microporous, electron-insulating, and / or ionic conductivity. In addition, the pair of electrodes may be individually composed of a current collector and a filler.
At this time, in the case of a super capacitor including an electrode according to an embodiment of the present invention, the distance between the graphene layers is larger than that of graphite and the specific surface area can be easily controlled compared to graphite, When the conductivity is improved by applying the rGO structure, the charging capacity and the output density can be improved.
In another embodiment of the present invention, there is provided a method of manufacturing a semiconductor device, comprising: preparing a substrate; Forming an oxidized graphene layer on the substrate; Forming a metal layer on the oxide graphene layer; And a step of obtaining a reduced oxidized graphene layer and a metal oxide layer by simultaneous oxidation-reduction reaction between the oxidized graphene layer and the metal layer.
Hereinafter, one embodiment of the present invention will be described in detail with reference to FIGS. 1 and 2.
First, forming an oxide graphene layer on the substrate; And / or forming a metal layer on the oxide graphene layer may be a wet or dry method.
More specifically, the wet process is performed at atmospheric pressure, and the dry process can be performed at a pressure of 10 -7 Torr to 760 Torr. However, the present invention is not limited thereto.
As an example, the case where the wet method is used may be the following method. A graphene oxide layer may be coated on the substrate using a mixed solution containing graphene oxide. More specifically, a mixed solution can be prepared by mixing graphite, oxidized graphene (GO) powder and the like with a solvent capable of easily dissolving or dispersing these substances, and the mixed solution can be coated on the substrate.
Specifically, the substrate may be glass or a flexible polymer material, or a material such as graphene, carbon nanotube, silver nanowire, ITO, FTO, IZO, AZO, ITO-Ag-ITO, IZO-Ag-IZO, IZTO- -Ag-AZO, and the like.
More specifically, there is provided a method comprising: forming an oxide graphene layer on a substrate; And / or forming a metal layer on the oxide graphene layer may be performed by sputtering deposition, spray coating, spin coating, slot-die coating, or a combination thereof. However, the present invention is not limited thereto.
Forming an oxidized graphene layer on the substrate; Thereafter, stabilizing the formed oxide graphene layer may be further included.
In the case of the above-mentioned wet process, the mixed solution containing the graphene oxide may be coated on the substrate, followed by cleaning and drying to stabilize the oxide graphene layer coated on the substrate.
As a specific method, there are thermal, ultraviolet, laser, infrared, plasma, electron beam, or a combination thereof. Thus, adhesion between the oxide graphene layer formed on the substrate and the substrate can be secured, and interface control between the metal layer formed thereafter can be facilitated.
Next, the step of forming a metal layer on the oxide graphene layer may be performed by using an electroplating method, a plasma chemical vapor deposition method, a magnetron sputtering method, a vacuum evaporation method, an arc vapor deposition method, an atomic layer deposition method, or a combination thereof . However, the present invention is not limited thereto.
For example, since the description of the metal is the same as that of the embodiment of the present invention described above, the description thereof will be omitted.
The step of obtaining a reduced oxidized graphene layer and a metal oxide layer through simultaneous oxidation-reduction reaction between the oxidized graphene layer and the metal layer may be performed by using a method of heat, ultraviolet ray, laser, infrared ray, plasma, electron beam or a combination thereof . Various methods can be applied as long as the method can minimize damage to the substrate.
Specifically, the heat treatment may be performed at a temperature of 200 DEG C or lower. At this time, since the oxidation-reduction reaction can be performed within a temperature range of 200 ° C or lower, a reduced oxide graphene (rGO) / metal oxide layer structure can be easily applied to a substrate material which can not be subjected to high temperature heat treatment such as a flexible polymer substrate have.
Specifically, the metal of the metal layer may be Cu. Further, even when a metal other than Cu is used, it is possible to form an electrode having a reduced oxidized graphene (rGO) / metal oxide layer structure as the electron affinity is lower.
For example, Al (42 kJ / mol), Ti (8 kJ / mol), V (51 kJ / mol), Cr (65 kJ / mol), Fe ), 119 kJ / mol of metals such as Zr (41 kJ / mol), Mo (72 kJ / mol), Pd (54 kJ / mol), In (RGO) / metal oxide film reduced than Cu having electron affinity. Also, since the various metals can form an rGO / metal oxide layer structure, they can play a role of controlling work function between interfaces and photocatalyst. Accordingly, the electrode including the reduced oxidized graphene (rGO) / metal oxide film according to an embodiment of the present invention can be applied to various devices, and a detailed description thereof has been described above, and thus will not be described.
More specifically, the method includes: preparing the substrate; forming an oxidized graphene layer on the substrate; And forming a metal layer on the oxide graphene layer, the method comprising: preparing a substrate; forming a metal layer on the substrate; And forming an oxidized graphene layer on the metal layer. That is, the order of each layer can be reversed or repeated.
The order of the steps of forming each layer on the substrate may be reversed according to the purpose to which the finally formed reduced graphene oxide (rGO) / metal oxide layer electrode is applied. In addition, the steps of forming each layer for multilayer formation can be repeatedly performed.
Also, specifically, the method of manufacturing the electrodes including the reduced graphene oxide (rGO) and the metal oxide layer may be a continuous process. More specifically, an in-line or roll-to-roll process can be used.
Hereinafter, specific embodiments of the present invention will be described. It is to be understood, however, that the embodiments described below are only for illustrative purposes or to illustrate the present invention, and the present invention should not be limited thereby.
Example 1: Reduced oxidation Grapina ( reduced Graphene Oxide , rGO ) And metal The oxide layer Manufacture of electrodes containing
The oxide graphene layer is formed using a solution of Ultra Highly Concentrated Single-Layer Graphene Oxide (6.2 g / L).
A mixed solution containing the above-prepared oxidized graphene (GO) is coated on the Si substrate to a thickness of 5 to 10 nm by spray coating.
The substrate coated with the mixed solution containing the oxidized graphene (GO) is subjected to plasma treatment. Thereafter, the specimen having the Cu layer of 3 nm thickness formed by sputtering deposition was heat-treated at 200 ° C. for 30 minutes using a heat treatment oven to form reduced graphene oxide (rGO) and metal oxide layer ≪ / RTI >
The XRD analysis results of the electrode thus prepared are shown in FIG.
Referring to FIG. 3, in (1), a mixed solution containing the prepared graphene oxide (GO) is coated on the Si substrate to a thickness of 5 to 10 nm by spray coating Ray diffraction pattern of an oxidized graphene (GO) coating layer after performing only the step of FIG.
(2) is an X-ray diffraction pattern of an electrode including reduced graphene oxide (rGO) and a metal oxide layer prepared by performing all the steps of Example 1.
GO (002) peaks are observed at a diffraction angle of 10 DEG C in the case of (1) in which only a graphene oxide (GO) coating layer is laminated. However, when the Cu (metal) film is deposited on the oxide graphene coating layer, the GO (002) peak disappears and the reduced graphene graphene (rGO) peak appears at 12.5 and 25 ° C. In addition, diffraction peaks of the Cu 2 O metal oxide layer produced by redox reaction between oxidized graphene and Cu appear at 37 ° C and 74 ° C. As a result, it can be confirmed that a reduced oxide graphene / metal oxide layer structure is formed through the formation of the oxide graphene / metal layer structure.
Example 2: Reduced oxidation Grapina ( reduced Graphene Oxide , rGO ) And metal The oxide layer Manufacture of electrodes containing
In the same manner as in Example 1 except that the thickness of the Cu layer to be laminated was changed to 1 nm in Example 1, an electrode including reduced Graphene Oxide (rGO) and a metal oxide layer .
Comparative Example 1: Oxidation Graffin (GO) Manufacture of electrodes containing
In Example 1, the electrode was manufactured in the same manner as in Example 1, except that the step of laminating the Cu layer was omitted.
Comparative Example 2: Reduced oxidation Grapina ( reduced Graphene Oxide , rGO ) And metal The oxide layer Manufacture of electrodes containing
In Example 1, the electrode was manufactured in the same manner as in Example 1, except that the thickness of the Cu layer to be laminated was 1 nm and the heat treatment step was omitted.
Comparative Example 3: Reduced oxidation Grapina ( reduced Graphene Oxide , rGO ) And metal The oxide layer Manufacture of electrodes containing
In Example 1, the electrode was manufactured in the same manner as in Example 1, except that the heat treatment step was omitted.
Experimental Example One: Cu Layer thickness and transmittance according to presence or absence of heat treatment and Sheet resistance evaluation
In one embodiment of the present invention, the following experiment is conducted to investigate the light transmittance and the sheet resistance change depending on the metal layer thickness and the heat treatment for the oxidation-reduction reaction.
First, the specimens prepared in Examples 1, 2 and Comparative Examples 1 to 3 were irradiated with ultraviolet rays at wavelengths of 200 to 800 nm using a UV-Vis-NIR Spectrophotometer (Cary 5000, Varian) Measure the permeability.
For each of the specimens prepared in Examples 1, 2 and Comparative Examples 1 to 3, the sheet resistance was measured using a 4-point probe (MCP-T600, Mitsubishi Chemical Corporation).
The measurement results are shown in Table 1 below.
As a result of the experiment, when the thickness of the Cu metal layer is 1 or 3 nm (Examples 1 and 2), the sheet resistance characteristics are improved after the Cu metal layer is laminated, and the sheet resistance can be further improved through the heat treatment.
In the case of a GO without Cu metal layer (Comparative Example 1), a low conductivity of 10 8 ohm / sqr. Or more. Therefore, it can not be measured beyond the measurement range of the equipment used in Experimental Example 1.
Through this, the oxidized graphene / metal layer structure can be effectively used for the oxidized graphene reduction process, and the sheet resistance can be reduced. The decrease in transmittance due to the increase in the thickness of the metal layer generally has a tendency similar to the decrease in transmittance due to the lamination of metal layers of several nm thickness used for the transparent electrode and can be utilized as a transparent electrode and other materials through maintenance of appropriate transmittance characteristics.
Experimental Example 2: Evaluation of current density of solar cell
In order to compare and evaluate the performance (current density) of a solar cell including an electrode including a reduced oxidation graphene (rGO) / metal oxide layer manufactured according to an embodiment of the present invention, the following experiment is performed.
First, an electrode including the reduced graphene oxide (rGO) and the metal oxide layer prepared in Example 1 was formed on a glass substrate. For comparison, only the oxide graphene was spin-coated on a glass substrate, For 30 minutes to fabricate an organic solar cell device including the electrode.
The photoactive layer of the organic solar cell includes poly [(4,8-bis- (2-ethylhexyloxy) -benzo [1,2-b: 4,5-b '] dithiophene) -2,6- (2-ethylhexanoyl) -thieno [3,4-b] thiophene) -2,6-diyl] and [6,6] -phenyl-C 61 -butyric acid methyl ester in a ratio of 1: , 2-dichlorobenzene was spin-coated at 800 RPM to form a thin film of 100 nm thickness. Aluminum was used as a top electrode to form a 100 nm thin film by thermal evaporation at 5 × 10 -6 Torr.
Each of the organic solar cell devices manufactured above is measured for current-voltage curve and efficiency through a Keithley 2400 current-voltage source meter under a light amount of 1.5G using a solar simulator (PECELL Technologies Inc. PEC-L11).
The results are shown in Fig.
Referring to FIG. 4, in the case of an organic solar cell including a transparent electrode including only a GO layer, the resistance of the GO layer is very high and the work function matching between the electrode and the photoactive layer is not achieved, And thus shows a low efficiency of less than 1%. On the other hand, in the case of the organic solar cell manufactured using the electrode of rGO / Cu x O structure prepared in Example 1, a high curvature factor of 0.5 was shown due to the resistance of the relatively low transparent electrode, It has an open-circuit voltage of 0.74 V. Therefore, the efficiency is higher than 3%. The results show that the transparent electrode of the rGO / CuxO structure can achieve a resistance value lower than that of rGO only, and can simultaneously control the work function at the same time.
It will be understood by those skilled in the art that various changes in form and details may be made therein without departing from the spirit and scope of the present invention as defined by the following claims. As will be understood by those skilled in the art. It is therefore to be understood that the above-described embodiments are illustrative in all aspects and not restrictive.
Claims (20)
And a metal oxide layer positioned on the reduced oxidized graphene.
Wherein the metal oxide layer has a thickness of 0.1 nm to 100 nm.
Wherein the metal oxide layer is a completely oxidized metal oxide layer or a gradient structure in which a metal and a metal oxide layer are mixed.
Wherein the reduced graphene oxide and the metal oxide layer are formed through a simultaneous oxidation-reduction reaction.
Wherein the substrate is positioned below the reduced oxidized graphene.
The reduced graphene grains and the metal oxide layer on the substrate may be,
Oxidizing-reducing directly from the oxidized graphene and the metal layer formed on the substrate.
The metal,
The metal layer may be formed of a metal such as silver (Ag), copper (Cu), nickel (Ni), aluminum (Al), iron (Fe), cobalt (Co), silicon (Si), zinc (Zn), molybdenum (Mo) (Pd), titanium (Ti), vanadium (V), chromium (Cr), zirconium (Zr), indium (In), or combinations thereof.
Wherein the metal oxide layer is used as a buffer layer in the device, an active material layer in the device, a photocatalyst in the device, or a filling material in the device.
Forming an oxidized graphene layer on the substrate;
Forming a metal layer on the oxide graphene layer; And
Obtaining a reduced oxidized graphene layer and a metal oxide layer through simultaneous oxidation-reduction reaction between the oxidized graphene layer and the metal layer;
Wherein the electrode is formed of a metal.
Forming an oxidized graphene layer on the substrate; Since the,
And stabilizing the formed oxidized graphene layer.
Stabilizing the formed oxide graphene layer,
Wherein the treatment is a thermal, ultraviolet, laser, infrared, plasma, electron beam, or a combination thereof.
Forming an oxidized graphene layer on the substrate; And / or forming a metal layer on the oxide graphene layer,
Wherein a wet or dry method is used.
Forming an oxidized graphene layer on the substrate; And / or forming a metal layer on the oxide graphene layer,
Wherein a method of chemical vapor deposition, sputter deposition, spray coating, spin coating, slot-die coating, or a combination thereof is used.
Forming a metal layer on the oxide graphene layer,
Wherein the sputtering is performed using a method of electroplating, plasma chemical vapor deposition, magnetron sputtering, vacuum evaporation, arc evaporation, atomic layer deposition, ion beam sputtering, or a combination thereof.
The step of obtaining a reduced oxidized graphene layer and a metal oxide layer through simultaneous oxidation-reduction reaction between the oxidized graphene layer and the metal layer,
Wherein the method uses heat, ultraviolet, laser, infrared, plasma, electron beam, or a combination thereof.
Forming a metal layer on the oxide graphene layer,
And the thickness of the formed metal layer is 0.1 nm to 100 nm.
The method comprising: preparing the substrate; forming an oxidized graphene layer on the substrate; And forming a metal layer on the oxide graphene layer,
A method of manufacturing a semiconductor device, comprising: preparing a substrate; forming a metal layer on the substrate; And forming an oxide graphene layer on the metal layer.
The wet process is carried out at atmospheric pressure,
Wherein the dry method is performed under a pressure of 10 < -7 > torr to 760 Torr.
Wherein the electrode manufacturing method is a continuous process.
Wherein the continuous process is an in-line or roll-to-roll process.
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