KR101823367B1 - Method for manufacturing light-transmitting substrate comprising graphene layer and light-transmitting substrate manufactured using thereof - Google Patents
Method for manufacturing light-transmitting substrate comprising graphene layer and light-transmitting substrate manufactured using thereof Download PDFInfo
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- KR101823367B1 KR101823367B1 KR1020150177435A KR20150177435A KR101823367B1 KR 101823367 B1 KR101823367 B1 KR 101823367B1 KR 1020150177435 A KR1020150177435 A KR 1020150177435A KR 20150177435 A KR20150177435 A KR 20150177435A KR 101823367 B1 KR101823367 B1 KR 101823367B1
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Images
Classifications
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B37/00—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding
- B32B37/02—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding characterised by a sequence of laminating steps, e.g. by adding new layers at consecutive laminating stations
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
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- B—PERFORMING OPERATIONS; TRANSPORTING
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- H—ELECTRICITY
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- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L31/00—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
- H01L31/04—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof adapted as photovoltaic [PV] conversion devices
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
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- B—PERFORMING OPERATIONS; TRANSPORTING
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E10/00—Energy generation through renewable energy sources
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Abstract
The present invention provides a method of manufacturing a semiconductor device, comprising: forming a graphene layer on a separation layer; Forming a conductor on the graphene layer; Forming a polymer layer impregnating the conductor on the conductor; Forming a base layer on the polymer layer; And separating the separating layer from the graphene layer, the method comprising: forming a substrate layer, a polymer layer formed on the substrate layer, a conductor impregnated in the polymer layer, and a polymer layer impregnated with the conductor To a transparent substrate including a graphene layer formed on the transparent substrate.
Description
The present invention relates to a method of manufacturing a transparent substrate including a graphene layer that can be applied to a display device, a lighting device, a solar cell, and the like, and a transparent substrate produced thereby.
The translucent substrate is a substrate including a transparent conductive layer having both electrical conductivity and light transmittance. The translucent substrate may be a liquid crystal display, an electrochromic display (ECD), a plasma display panel, a flexible display, an electronic paper, a touch panel, a lighting device, an organic electroluminescence or a solar cell.
The translucent substrate comprises a base substrate and a translucent electrode that performs an electrode function of a light emitting element attached to the substrate. Transparent electrodes are mainly formed on a plastic base substrate using a conductive material such as ITO (tin-doped indium oxide) to form a thin film. In recent years, however, carbon that can replace ITO, which is indium- Research and development on nanotubes (CNTs), graphenes, and metal nanostructures have been actively conducted.
Graphene is a conductive material with a thickness of one layer of atoms, with the carbon atoms forming a honeycomb arrangement in two dimensions. Graphene is structurally and chemically very stable. It is also known to be an excellent conductor capable of moving
Although a method of producing graphene sheets is known, there is no known method of obtaining graphene having uniform properties over a large area so as to be industrially produced and applied, and researches on this are continuing. In addition, it is known that the quality and performance of graphene grown by a transfer process, which is essential for application of graphene to electronic devices and optical devices, are seriously degraded.
Korean Patent Laid-Open Publication No. 10-2013-0048701 discloses a transparent electrode element for a liquid crystal display including a graphene transparent electrode formed as a wiring pattern on the top surface of a transparent substrate. In the transparent electrode element for a liquid crystal display, Layer graphene transparent electrode to overcome the electrical characteristic coupling due to the formation of a metal grid or a complementary layer. However, a transparent electrode can be manufactured by directly forming a graphene layer on the upper surface of the transparent substrate, and the transparent electrode is not manufactured by transferring the transparent electrode.
The present invention provides a method for manufacturing a transparent substrate which can control the surface shape of a graphene layer and which has excellent electrical conductivity and light transmittance by growing a graphene layer on a separation layer, separating the separation layer after forming a layer in turn will be.
However, the objects of the present invention are not limited to the above-mentioned objects, and other objects not mentioned can be clearly understood by those skilled in the art from the following description.
The present invention provides a method of manufacturing a semiconductor device, comprising: forming a graphene layer on a separation layer; Forming a conductor on the graphene layer; Forming a polymer layer impregnating the conductor on the conductor; Forming a base layer on the polymer layer; And separating the separation layer from the graphene layer, wherein the transparent substrate is produced by the method.
The forming of the graphene layer may include forming a graphene layer on the transition metal substrate to form a graphene layer on the separation layer.
The step of forming the graphene layer may include forming a graphene layer on a transition metal substrate and transferring the graphene to a separation layer to form a graphene layer on the separation layer and the separation layer comprises a polydimethylsiloxane modified Urethane (PDMS) substrate, a PMMA (Polymethyl Methacrylate) substrate, or a TRT (Thermal Release Tape) substrate.
The step of forming the graphene layer may include forming a graphene layer on the separation layer by forming graphene on the transition metal substrate and transferring the graphene to the separation layer, There is provided a method of manufacturing a transparent substrate including a polyimide substrate, a polyethylene terephthalate (PET) substrate, a polyethynene naphthalate (PEN) substrate, a SiO 2 substrate, and an Al 2 O 3 substrate.
In addition, the step of separating the separation layer is a step of dissolving the separation layer using a transition metal corrosion liquid.
And separating the separation layer includes separating the separation layer by applying heat.
In addition, the step of separating the separation layer is a step of separating the separation layer by applying pressure.
The step of forming the graphene layer includes the step of forming a graphene layer on a separation layer having a curved surface pattern formed thereon.
In the step of forming the graphene layer, the surface of the separation layer may be etched by using an oxygen plasma, the surface of the separation layer may be wet-etched using an etching solution, or a liquid ink or paste having a viscosity may be used And a step of forming a graphene layer by forming a curved surface pattern by controlling the curing or drying method on the separation layer.
The step of forming the graphene layer may include at least one selected from the group consisting of fluorine (F), oxygen (O), sulfur (S), selenium (Se), and tellurium (Te) And a step of forming a graphene layer on the separated separation layer.
The step of forming the conductive material may include a step of applying an ink composition containing a metal nanostructure on the graphene layer, drying and curing the metal ink, or printing a metal mesh pattern on the graphene layer. to provide.
The forming of the polymer layer may include forming a polymer layer on the conductive material by forming metal particles or metal oxide particles on the conductive material, or forming a polymer layer on the conductive material by a method selected from the group consisting of metal oxides, metal nitrides and metal sulfides And then forming a polymer layer by coating the substrate with at least one transparent material.
The forming of the base layer may include forming a base layer on the polymer layer, the base layer including at least one substrate selected from the group consisting of a polyimide (PI) substrate, a polyethylene terephthalate (PET) substrate, and a polyethynene naphthalate And a step of forming a transparent substrate.
The present invention also provides a method of fabricating a semiconductor device, comprising: forming a graphene layer on a separation layer; Forming a conductor on the graphene layer; Forming a base layer to impregnate the conductor on the conductor; And separating the separation layer from the graphene layer, wherein the transparent substrate is produced by the method.
The present invention also relates to a substrate layer; A polymer layer formed on the base layer and impregnated with a conductor; And a graphene layer formed on the polymer layer, wherein a half region of the polymer layer which is in contact with the graphene layer is referred to as an A region, and a half region in contact with the base layer is referred to as a B region, And 40% or more of the sieve is distributed in the A region.
The surface of the graphene layer is provided with a curved surface pattern having a period of 5 to 20 탆 and a height of 1 to 5 탆.
Further, the polymer layer is impregnated with metal particles or metal oxide particles, and more than 40% of the metal particles or metal oxide particles are distributed in the A region.
And the conductor impregnated in the polymer layer is coated with one or more transparent materials selected from the group consisting of metal oxides, metal nitrides and metal sulfides.
The present invention also relates to a conductive layer-impregnated base layer; And a graphene layer formed on the base layer, wherein a half region adjacent to the graphene layer in the base layer is referred to as an A region, and another half region is referred to as a B region, % Or more is distributed in the A region.
The present invention also provides a display device including the transparent substrate.
Further, the present invention provides a lighting device comprising the above-mentioned light-transmitting substrate.
The present invention also provides a light-transmissible substrate, A light emitting material layer provided on the graphene layer of the transparent substrate; And a reflective metal layer provided on the light emitting material layer.
The present invention also provides a light-transmissible substrate, A photoactive layer provided on the graphene layer of the transparent substrate; And a metal electrode layer provided on the photoactive layer.
The present invention relates to a method for producing a transparent substrate by forming a graphene layer on a separating layer, applying a conductor, forming a polymer layer for impregnating the conductor and a substrate layer in order, and separating the separating layer from the graphene layer, It is possible to provide a process for manufacturing a transparent substrate which is simplified and can reduce the manufacturing cost since separation layers can be separated without passing through a complicated process or a lot of energy.
Unlike the method of manufacturing a transparent substrate by forming a transparent conductive oxide layer on an existing substrate layer, a translucent substrate is manufactured by forming each layer of a transparent substrate in a reverse order and separating the separated layer, thereby obtaining the following excellent effects .
The present invention is based on the fact that since each layer of the light transmitting substrate is formed in reverse order, that is, a conductor is formed on the graphene layer and a polymer layer is coated on the conductor so that the conductor is placed in contact with the graphene layer in the prepared transparent substrate, This excellent translucent substrate can be produced. Also, since the conductive material is impregnated or coated with the polymer layer, it is possible to solve the problem of reduction in reliability caused by sulfidation and oxidation between the conductive materials.
In addition, the present invention can include metal particles or metal oxide particles in the formation of a polymer layer to enable light extraction by light absorption and reflection, and thus can be used excellently in an illumination device requiring a light extraction function. Can be supplemented from the functional standpoint.
Further, the present invention can control the surface shape of the separation layer to be bent so that the surface of the graphene layer of the finally prepared transparent substrate has a curved shape. When an organic light emitting device is manufactured by laminating a light emitting layer and a reflective electrode on a light transmitting substrate including a graphene layer having a curved shape on the surface, the surface roughness is increased to increase the light emitting area, Not only the polymer layer (light extracting layer function) but also the curved shape itself can provide an effect of enhancing the light emitting efficiency by performing a light extracting function, and a photoactive layer and a metal electrode layer are laminated on the light transmitting substrate to produce an organic solar cell It is possible to provide an effect of increasing the light-receiving area of solar light and increasing the power generation efficiency by acting as a solar cell collector.
1 shows a method of manufacturing a transparent substrate according to an embodiment of the present invention.
FIG. 2 shows a transparent substrate manufactured according to a method of manufacturing a transparent substrate according to an embodiment of the present invention.
3 shows a method of manufacturing a transparent substrate according to an embodiment of the present invention.
FIG. 4 shows a transparent substrate produced by the method of manufacturing a transparent substrate according to an embodiment of the present invention.
FIG. 5 is a SEM photograph showing a metal nanowire of a transparent substrate manufactured according to Example 2 of the present invention.
FIG. 6 is a photograph of an optical image of a translucent substrate manufactured according to Example 2 of the present invention.
FIG. 7 shows a TEM image of a transparent substrate produced according to Example 2 of the present invention and a diffraction pattern image of a graphene layer.
Fig. 8 shows spectral measurement data of scattered light due to the Raman effect of the transparent substrate produced according to Example 2. Fig.
Before describing the present invention in detail, it is to be understood that the terminology used herein is for the purpose of describing particular embodiments only and is not intended to limit the scope of the invention, which is defined solely by the appended claims. shall. All technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art unless otherwise stated.
Throughout this specification and claims, the word "comprise", "comprises", "comprising" means including a stated article, step or group of articles, and steps, , Step, or group of objects, or a group of steps.
Also throughout this specification, when a member is " on " another member, it includes not only a member in contact with another member, but also another member between the two members.
On the contrary, the various embodiments of the present invention can be combined with any other embodiments as long as there is no clear counterpoint. Any feature that is specifically or advantageously indicated as being advantageous may be combined with any other feature or feature that is indicated as being preferred or advantageous. Hereinafter, embodiments of the present invention and effects thereof will be described with reference to the accompanying drawings.
A method of fabricating a transparent substrate according to an embodiment of the present invention includes forming a graphene layer on a separation layer (S20), forming a conductor on a graphene layer (S30), impregnating the conductor with a conductor A step of forming a polymer layer (S40), a step of forming a base layer (S50) on the polymer layer, and a step (S60) of separating the separation layer from the graphene layer. 1 shows a method of manufacturing a transparent substrate according to an embodiment of the present invention.
The transparent substrate produced in accordance with the present invention includes a
The present invention provides a method for manufacturing a transparent substrate which is simplified and can be manufactured with improved manufacturing efficiency by allowing a graphene layer to be transferred without complicated processes or a lot of energy and capable of a continuous process of a roll to roll process do.
In addition, unlike the method of producing a transparent substrate by forming a transparent conductive oxide layer on an existing substrate layer, a translucent substrate is manufactured by forming each layer of a transparent substrate in a reverse order and separating the separated layer, A transparent substrate having excellent effects such as transparency and light extraction function can be produced.
Step S20 of forming a graphene layer on the separation layer according to an embodiment of the present invention may include a step of forming a graphene layer on the first separation layer 11 or a step of forming a graphene layer on the first separation layer 11 (S22) of forming a graphene layer on the first separation layer 11 and transferring the graphene to the second separation layer 12 or forming a graphene layer on the first separation layer 11, (Step S23) of forming a graphene layer.
The first separation layer 11 includes a transition metal substrate, and the transition metal substrate includes at least one of a copper (Cu) substrate and a nickel (Ni) substrate.
The second separation layer 12 may include at least one of a PUA (Polydimethylsiloxane modified Urethane Acrylate), a PDMS (Polydimethylsiloxane), a PMMA (Polymethyl Methacrylate) substrate, and a TRT (Thermal Release Tape) substrate.
The third separation layer 13 is a glass (glass) substrate, an amorphous glass (glass) substrates, PI (polyimide), PC (Polycarbonate), PET (Polyethylene Phthalate) substrate, a PEN (Polyethlene Naphthalate) substrate and Al 2 O 3, And at least one substrate selected from the group consisting of Si: F, SiO 2, and a substrate.
The step of forming the graphene layer (S20) may further include a step of forming a graphene layer on the surface or on the surface of the substrate by using at least one material selected from the group consisting of fluorine (F), oxygen (O), sulfur (S), selenium (Se) And a step of forming a graphene layer on the separation layer contained therein. By including the substance on the surface or in the interior of the separation layer, separation (separation) of the separation layer, which will be described later, is possible in a more complicated process or separation (transfer) without much energy.
When two or more kinds of substrates are prepared as the
In the step S20 of forming a graphene layer on the separation layer according to an embodiment of the present invention, the surface shape of the separation layer is controlled to be bent so that the surface of the graphene layer of the transflective substrate to be finally transferred has a curved shape Can be controlled.
It is possible to form concave and convex surface patterns on the surface of the obtained
When an organic light emitting device is manufactured by laminating a light emitting layer and a reflective electrode on a translucent substrate including a
Examples of the method for forming a curved pattern on the separation layer include a method of etching the surface with a mask using atmospheric pressure and oxygen plasma, a method of wet etching using a chemical solution (etching solution) A method of controlling the curing or drying method on the separation layer using liquid ink or paste may be used to form a curved surface pattern on the surface of the separation layer, but the present invention is not limited thereto.
In step S20 of forming a graphene layer according to an embodiment of the present invention, a graphene layer is formed on the first separation layer 11 to a thickness of 0.3 nm to 3 nm. When formed to less than 0.3 nm, it has a thickness of not more than one carbon atom of graphene, which means that graphene is not formed. When it is formed in a thickness of more than 3 nm, the graphite structure shows a physical property closer to that of graphite, and there is a problem that the surface is cracked when folded due to a decrease in flexibility. And preferably 0.3 nm to 2 nm.
The method of forming the graphene layer on the first separating layer 11 employs a transition metal as a catalyst to solidify the hydrocarbon gas at a high temperature to decrease the solubility upon cooling and to arrange the surface carbon atoms to form a graphene hexagonal ring structure Structure growth method. The graphene layer may be formed on the first separation layer 11 and the next step may be performed (S21). In this case, since the shape of the graphene layer is easily changed during the roll-to-roll process (continuous process) A continuous process can be easily performed by forming a graphene on the separation layer 11 and transferring the graphene to the second separation layer 12 or the third separation layer 13 to form a graphene layer (S22, S23) have. The separation layer may be a composite layer of a composite type in which a polymer having a very low surface adhesiveness and low adhesion and a low molecular weight polymer are coated on the surface.
A step S30 of forming a conductor according to an embodiment of the present invention is a step of forming a
The step of forming the conductive material (S30) may include a step (S31) of applying an ink composition containing the metal nanostructure (31) to a graphene layer, drying and curing the metal nanostructure to form a metal nanostructure (S31) (Step S32) of forming a metal mesh pattern by printing the metal mesh pattern.
Step S31 of forming the metal nanostructure is a step of forming a metal nanostructure 31 which is a nano-sized structure having electrical conductivity on the
When the metal nanowire 311 is used as the metal nanostructure 31 in the step (S31) of forming the metal nanostructure, the average diameter of the metal nanowires 311 used is 30 nm to 100 nm, Is used. When the metal nanowires 311 having a size smaller than the above range are used, there is a problem in that the electrical conductivity is lowered. In the case of using the metal nanowires 311 exceeding the above range, the light transmittance is deteriorated.
When metal nanoparticles 312 are used as the metal nanostructure 31 in the step of forming the metal nanostructure 31, the average diameter of the metal nanoparticles 312 used is 50 to 300 nm, There is a problem of lowering the light scattering when particles are used, and in the case of using metal nanoparticles exceeding 300 nm, there is a problem of loss of transmittance due to light reflection.
Preferably, the metal nanowires 311 and the metal nanoparticles 312 are mixed and used. More preferably, the metal nanoparticles are mixed with the metal nanoparticles in an amount of 10 wt% to 40 wt% . When the metal nanoparticles are mixed in an amount of less than 10 wt%, there is a problem in optical function deterioration. When the metal nanoparticles are mixed in an amount of more than 40 wt%, there is a problem of decreased light transmittance.
The step (S31) of forming the metal nanostructure may include the steps of forming a metal nanostructure by depositing a conductive metal such as Ag, Au, Cu, Pt, Fe, Ni, At least one metal selected from the group consisting of zinc (Zn), titanium (Ti), chromium (Cr), aluminum (Al), and palladium (Pd) can be used to form the metal nanostructure. Preferably, silver (Ag) is used. Silver (Ag) reflects light as a metal and has a low transmittance. However, when the translucent substrate according to the present invention is used as a translucent electrode of an organic light emitting device, a reflective electrode (for example, an aluminum And reflects light to each other, so that light loss inside the device is actually reduced.
The step of forming the metal mesh pattern S32 is a step of forming a metal mesh pattern 32, which is a metal mesh pattern, on the
The step of forming the metal mesh pattern S32 can be performed by arranging the metal mesh pattern in the form of a mesh or a bridge using silver (Ag), copper (Cu), aluminum (Al) The light-transmitting electrode can be formed with various patterns and line widths according to requirements such as appropriate haze value and visibility according to the apparatus in which it is used. For example, when it is used in an organic light emitting device for illumination, it is preferable to form it with a line width of 100 nm to 10 μm because it exhibits a haze value of about 2% to 15% and a transmittance of about 70% to 90%.
A step S40 of forming a polymer layer according to an embodiment of the present invention includes forming a
The impregnation of the
The step of forming the polymer layer (S40) may include impregnating the
In addition, in the step of forming the polymer layer (S40), the light extracting particles 41 may be included or the pore 42 may be included to increase the light extraction efficiency due to internal scattering, Can be used.
The step (S41) of forming the polymer layer by including the light extracting particles may further include the light extracting particles 41 to increase the light extracting effect by forming the polymer layer. The light extracting particles 41 include metal particles 411, metal oxide particles 412, metal nitride particles 413, metal sulfide particles 414, and the like.
The step (S41) of forming the polymer layer by including the light extracting particles includes the light extracting particles 41 having an average particle diameter of 50 to 300 nm to form the polymer layer. If the size of the light extracting particles 41 included is less than 50 nm, there is a problem that the scattering property is lowered, and when the size is more than 300 nm, there is a problem of loss of transmittance. And preferably 100 to 300 nm.
The light extracting particles 41 may be spherical, elliptical, amorphous, or the like, and may have protrusions on the outer surface thereof. When the projections are provided on the outer surface, the size of the projections is 5 nm to 50 nm. If it is less than 5 nm, there is a problem of light scattering degradation. If it is more than 50 nm, there is a problem of loss of transmittance.
Also, the step of forming the polymer layer by including the light extracting particles (S41) may be performed by coating the conductor with any one or more transparent materials selected from the group consisting of oxides of metals, nitrides of metals and sulfides of metals A polymer impregnated with the coated conductor can be formed to form the polymer layer.
In step S40 of forming the polymer layer including the pores, the pores 42 are formed at the time of forming the
The step of forming a polymer layer (S40) is a step of forming a
The step of forming a polymer layer (S40) may be performed by laminating a polymer solution of the above type on the
The step of forming a base layer (S50) according to an embodiment of the present invention is a step of forming a base layer (50) serving as a base substrate after transfer on a polymer layer (40)
The
At this time, the step of forming the substrate layer (S50) may be performed by applying a polymer solution forming the material layer of the kind of the base layer and the polymer layer and laminating the polymer solution, and the roll- There are advantages.
In the case where PI (Polyimide), PET (Polyethylene Phthalate), or PEN (Polyethlene Naphthalate) is used as a material for forming the base layer, it is possible to produce a translucent substrate which is grafted with the polymer forming the polymer layer to strengthen the strength of the base layer have.
It is possible to use polyimide (PET), polyethylene terephthalate (PET), poly carbonate, polyether sulfone (PES), polyethylene naphthalate (PEN), polyacrylate (PA), polyurethane acrylate (PUA), polydimethyl siloxane And the
The step of separating the separation layer S60 according to an embodiment of the present invention includes separating the
In the case where a graphene layer is formed on the first separation layer (transition metal substrate) as a separation layer, step (S60) of separating the separation layer is a step of melting the transition metal substrate using the transition metal corrosion solution. The first separating layer (transition metal substrate) on which graphene is formed is dissolved and removed from the grafting layer by using a chloride or sulfate series aqueous solution such as FeCl 3 (Iron chloride) or APS (Ammonium persulfate) The transition metal substrate can be separated.
When the graphene layer is formed as the separation layer on the second separation layer, the separation step (S60) is a step of separating the second separation layer by applying heat. The TRT substrate, which is one of the second separation layers, is separated from the TRT substrate by separating the TRT substrate by using a lamination equipment or by heating to 90 to 130 ° C. by using the characteristic of losing adhesion when heat is applied have. In this case, the heating temperature is not limited because the characteristics of each TRT substrate are different.
When a graphene layer is formed on the third separation layer as a separation layer, separation of the separation layer (S60) is a step of separating the separation layer by applying external pressure to the separation layer. The
A method of fabricating a transparent substrate according to an embodiment of the present invention includes forming a graphene layer on a separation layer (S20), applying a conductor on the graphene layer (S30), impregnating the conductor with a conductor (S40-50); and separating the separating layer from the graphene layer to form a base layer, a conductor to be impregnated into the base layer, and a conductive layer formed on the base layer impregnated with the conductor A transparent substrate including a graphene layer can be manufactured. FIG. 3 shows a method of manufacturing a transparent substrate according to an embodiment of the present invention, and FIG. 4 shows a transparent substrate manufactured by a transparent substrate manufacturing method according to an embodiment of the present invention.
In this case, in the step of forming the polymer layer, the light extracting particles are included, the pores are included, or the conductor is coated with a transparent material such as an oxide of metal, a nitride of metal and a sulfide of metal, The step of imparting the extraction function may be the same in steps (S40-50) of forming the base layer.
In addition, the method of manufacturing a transparent substrate according to an embodiment of the present invention may further include a step (S70) of removing the separation layer component remaining on the separated
A
When fabricated according to the method of manufacturing a transparent substrate according to an embodiment of the present invention, a region of the
The present invention relates to a method of forming a transparent substrate by forming a transparent conductive oxide layer on an existing substrate layer and forming a transparent layer on the transparent substrate in a reverse order, So that a transparent substrate having excellent electrical conductivity can be manufactured.
Further, the present invention can use a separation layer having a curved surface and transferring the graphene layer to produce a transparent substrate including a graphene layer having a curved shape on the surface. Thus, when an organic light emitting device is manufactured by laminating a light emitting layer and a reflective electrode on a translucent substrate including a graphene layer having a curved shape on the surface, the surface roughness is increased to increase the light emitting area, and the metal particles or metal oxide particles (Photo-extracting layer function) as well as the curved shape itself can provide an effect of enhancing the luminous efficiency by performing a light extracting function, and a photoactive layer and a metal electrode layer are laminated on the transparent substrate to manufacture an organic solar cell It is possible to provide an effect of increasing the light-receiving area of solar light and increasing the power generation efficiency by acting as a solar cell collector.
For example, the separating layer may be prepared to have a curved surface pattern having a period of 5 to 20 탆 and a height of 1 to 5 탆. When the separating layer is separated, a curved shape having a period of 5 to 20 탆 and a height of 1 to 5 탆 It is possible to fabricate a transparent electrode including a graphene layer having a surface pattern, and the surface area is increased by the wave pattern, so that the light emitting area can be widened and is suitable for use as a surface illuminated panel such as an OLED.
The
When the
The material and method for forming the organic light-emitting
The reflective electrode 300 may be formed by a sputtering method, an E-beam evaporation method, a thermal evaporation method, a laser molecular beam epitaxy (L-MBE) method, Pulsed Laser Deposition (PLD); physical vapor deposition (PVD); A thermal chemical vapor deposition method, a plasma chemical vapor deposition (PECVD) method, a light chemical vapor deposition method, a laser chemical vapor deposition method, a metal- A chemical vapor deposition method selected from the group consisting of metal organic chemical vapor deposition (MOCVD), and hydride vapor phase epitaxy (HVPE); Or atomic layer deposition (ALD).
The reflective electrode 300 may be formed of at least one selected from the group consisting of magnesium, calcium, sodium, potassium, titanium, indium, yttrium, lithium, gadolinium, aluminum, platinum, gold, tungsten, tantalum, have.
Example
Example 1 - When a Cu substrate was used as a separation layer
Single-layer graphene is formed on a Cu substrate by chemical vapor deposition (CVD), a metal electrode ink is coated on the graphene, and dried and cured at 80 to 150 ° C for 5 to 10 minutes to form a metal pattern. Thereafter, the polymer solution is applied and dried to form a polymer layer impregnating the metal electrode, and then a flexible substrate such as PI (Polyimide) or PET (polyethylene terephthalate) is laminated to attach the graphene and the metal electrode to the polymer layer, do. Finally, a Cu substrate was removed by using an aqueous solution of chlirde and sulfate series such as FeCl 3 (Iron chloride) and APS (Ammonium persulfate) to obtain a translucent substrate in which a graphene layer, a polymer layer impregnated with a metal electrode, and a substrate layer were sequentially stacked.
Example 2 - When a TRT substrate was used as a separation layer
The metal electrode ink is coated on the graphene transferred to the TRT and dried and cured at 80 to 150 ° C for 5 to 10 minutes to form a metal pattern. Thereafter, a polymer layer for impregnating the metal electrode is formed by applying and drying the polymer solution, and then a flexible substrate such as PI (Polyimide) or PET (Polyethylene terephthalate) is laminated to attach the graphene and TRT to the polymer layer, do. Finally, when a hot press or laminating was performed at a temperature of 110 ° C, the adhesive force of the TRT was lost and the transparent substrate was separated from the graphene and polymer layers to obtain a translucent substrate in which the graphene layer, the polymer layer impregnated with the metal electrode and the base layer were stacked in this order.
Example 3 - When a general substrate was used as a separation layer
A metal electrode ink is formed on a glass substrate, a polyimide (PI), a polycarbonate (PC), a polyethylene terephthalate (PET) substrate, a polyethlene naphthalate (PEN) substrate and Al 2 O 3 , SiO 2, And dried and cured at 80 to 150 ° C for 5 minutes to 10 minutes to form a metal pattern. Thereafter, a polymer layer for impregnating the metal electrode is formed by applying and drying the polymer solution, and then a flexible substrate such as PI (Polyimide) or PET (Polyethylene terephthalate) is laminated to attach the graphene and the general substrate to the polymer layer It is transferred. Finally, since the surface adhesion force with the polymer layer through the impregnation is higher than the surface adhesion force between the graphene layer and the separation layer, direct pressure is applied or external pressure such as delaminating is applied to separate the general substrate from the graphene and polymer layer To obtain a translucent substrate in which a graphene layer, a polymer layer impregnated with a metal electrode, and a base layer were sequentially laminated.
Example 4 - ZnO coating after formation of AgNW on a graphene layer
When the above experimental method (Examples 1, 2, and 3) is carried out, metal oxides can be further grown on the metal pattern in a non-vacuum manner. The separation layer on which the graphene and the metal electrode are deposited is deposited in the metal oxide coating solution. At this time, if a light source having a high energy from the outside is irradiated to the substrate, the metal electrode is selectively heated to transfer energy, and the metal oxide can be selectively coated on the metal electrode through the catalytic action. The optical performance can be improved by the difference in the refractive index between the protrusion structure and the metal oxide.
Example 5 - Bending transfer to a graphene layer
When the liquid polymer material is cured by spin coating on the substrate, it is possible to selectively form a wave pattern of the curved surface on the surface. When a graphene and a metal electrode are formed on a surface having such a curvature and are cured by using a polymer and transferred, a graphene electrode having a curved pattern of the existing surface can be formed.
Experimental Example
(1) Image measurement
FIG. 5 is a SEM photograph showing a metal nanowire of a transparent substrate manufactured according to Example 2 of the present invention.
FIG. 6 is a photograph of an optical image of a translucent substrate manufactured according to Example 2 of the present invention.
FIG. 7 shows a TEM image of a transparent substrate produced according to Example 2 of the present invention and a diffraction pattern image of a graphene layer. It can be confirmed that it is a polycrystal having various crystal planes through the diffraction pattern, and it can be confirmed that it includes a graphene layer formed with high-quality graphene.
(2) Measurement of Raman spectrum
Fig. 8 shows spectral measurement data of scattered light due to the Raman effect of the transparent substrate produced according to Example 2. Fig. ~ 1343cm -1 D band (Defect peak) in the vicinity is not almost observed, the G-band (Graphite), 2D band (Graphene) in the vicinity of 2680cm -1 in the vicinity of 1581cm -1 were observed.
(3) Electrical conductivity and light transmission measurement
The surface resistivity of the light-transmitting substrate prepared according to Examples and Comparative Examples was measured to measure the electrical conductivity. The transmittance was measured by measuring the transmittance with respect to the wavelength of 550 nm. A 4-point probe (instrument name: MCP-T610, manufacturer: MITSUBISHI CHEMICAL) commonly used in surface resistance measurement was used and measured using an ESP type probe having a pin interval of 5 mm. The measurement results are shown in Table 1 below.
The features, structures, effects, and the like illustrated in the above-described embodiments can be combined and modified in other embodiments by those skilled in the art to which the embodiments belong. Therefore, it should be understood that the present invention is not limited to these combinations and modifications.
Claims (23)
Forming a conductor on the graphene layer;
Applying a polymer solution on the conductor and impregnating the conductor to form a polymer layer for bonding the conductor to the graphene layer;
Forming a base layer on the polymer layer; And
And separating the separation layer from the graphene layer, wherein the transparent substrate is produced.
Wherein the step of separating the separation layer is a step of dissolving the separation layer using a transition metal corrosion liquid.
Wherein growing the graphene layer comprises growing a graphene layer on a separation layer having a curved surface pattern.
Wherein growing the graphene layer comprises:
The surface of the separation layer is mask-etched using oxygen plasma,
Wet etching the surface of the separation layer using an etching solution,
Forming a curved surface pattern on the separation layer by using a liquid ink or paste having a viscosity, and then growing a graphene layer.
Wherein forming the conductor comprises:
Applying an ink composition containing the metal nanostructure on the graphene layer, drying and curing the ink composition,
And printing a metal mesh pattern on the graphene layer.
Wherein forming the polymer layer comprises:
Forming a metal layer or a metal oxide particle on the conductor, applying a polymer solution to impregnate and dry the conductor and the particle to form a polymer layer joining the conductor and the graphene layer,
Coating the conductive material with at least one transparent material selected from the group consisting of a metal oxide, a metal nitride, and a metal sulfide; applying a polymer solution to impregnate the conductive material and the material to dry the conductive material; And forming a polymer layer for bonding the graphene layer.
The forming of the base layer may include forming at least one substrate selected from the group consisting of a polyimide (PI) substrate, a polyethylene terephthalate (PET) substrate, and a polyethynene naphthalate (PEN) Wherein the substrate is a transparent substrate.
Forming a conductor on the graphene layer;
Forming a base layer for bonding the conductor and the graphene layer by applying a material for forming a base layer on the conductor and laminating the conductor while impregnating the conductor; And
And separating the separation layer from the graphene layer, wherein the transparent substrate is produced.
A base layer;
A polymer layer formed on the base layer and impregnated with a conductor; And
And a graphene layer formed on the polymer layer,
Wherein a half region of the polymer layer in contact with the graphene layer is referred to as A region and a half region in contact with the base layer is defined as a B region, 40% or more of the conductor is distributed in the A region,
Wherein the conductor is applied onto the graphene layer, and then the polymer solution forming the polymer layer is applied while impregnating the conductor, dried, and bonded to the graphene layer.
Wherein the surface of the graphene layer is provided with a curved surface pattern having a period of 5 to 20 占 퐉 and a height of 1 to 5 占 퐉.
The polymer layer is further impregnated with metal particles or metal oxide particles,
Wherein at least 40% of the metal particles or metal oxide particles are distributed in the A region.
Wherein the conductor impregnated in the polymer layer is coated with one or more transparent materials selected from the group consisting of metal oxides, metal nitrides and metal sulfides.
A substrate layer impregnated with a conductor;
And a graphene layer formed on the base layer,
Wherein a half region adjacent to the graphene layer in the base layer is referred to as an A region and a remaining half region is defined as a B region, at least 40% of the conductor is distributed in the A region,
Wherein the conductor is applied onto the graphene layer, and then the material forming the base layer is applied while impregnating the conductor, dried, and bonded to the graphene layer.
A light emitting material layer provided on the graphene layer of the transparent substrate; And
And a reflective metal layer provided on the light emitting material layer.
A photoactive layer provided on the graphene layer of the transparent substrate; And
And a metal electrode layer provided on the photoactive layer.
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| KR101174670B1 (en) * | 2011-05-13 | 2012-08-17 | 한국화학연구원 | Preparation of patterned graphene applicable to graphene-based device |
| KR101191865B1 (en) * | 2011-04-20 | 2012-10-16 | 한국기계연구원 | Fabrication method of flexible substrate having buried metal electrode and the flexible substrate thereby |
| JP2015170404A (en) * | 2014-03-05 | 2015-09-28 | 株式会社東芝 | Transparent conductive body and device using it |
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| KR101191865B1 (en) * | 2011-04-20 | 2012-10-16 | 한국기계연구원 | Fabrication method of flexible substrate having buried metal electrode and the flexible substrate thereby |
| KR101174670B1 (en) * | 2011-05-13 | 2012-08-17 | 한국화학연구원 | Preparation of patterned graphene applicable to graphene-based device |
| JP2015170404A (en) * | 2014-03-05 | 2015-09-28 | 株式会社東芝 | Transparent conductive body and device using it |
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