KR102252956B1 - Electrode for electronic device with transparent substrate comprising bus electrode originated from metal catalyst layer for graphene growth and method of manufacturing the same - Google Patents

Abstract

An electrode for an electronic device based on a high-reliability transparent substrate having excellent properties using high-quality graphene and a transparent conductive layer and a method for manufacturing the same are proposed. The method of manufacturing an electrode for an electronic device based on a transparent substrate according to the present invention comprises: a graphene growing step of growing graphene on a conductive growth substrate; Forming an atomic layer by performing an atomic layer deposition process on the graphene layer; A transparent conductive layer forming step of forming a transparent conductive layer on the atomic layer; Forming a bus electrode by removing a portion of the conductive growth substrate; And attaching the bus electrode to the flexible substrate.

Description

Electrode for electronic device with transparent substrate comprising bus electrode originated from metal catalyst layer for graphene growth and method of manufacturing the same}

The present invention relates to an electrode for a transparent substrate-based electronic device comprising a bus electrode using a graphene growth metal catalyst layer and a method for manufacturing the same, and more particularly, to a part of the growth substrate used to construct a graphene composite electrode. The present invention relates to an electrode for an electronic device based on a highly reliable transparent substrate including a configured bus electrode and a method of manufacturing the same.

Transparent electronic devices based on transparent substrates include smart windows based on electrochromic, thermochromic, photochromic and heat generation, automotive room mirrors using electrochromic, transparent displays, and display devices. With the development, the area is getting wider. In addition, as the demand for electronic products with maximum device flexibility, such as curved or foldable displays, is gradually increasing, the flexibility of electrodes, which is the basis of electronic devices, is becoming an essential factor. have.

Among the various materials that can be used as flexible transparent substrates, transparent conducting oxide (TCO) such as indium tin oxide (ITO) and graphene are the most influential. A transparent conductive oxide is a material having high transparency and conductivity, but has low flexibility, and graphene has a disadvantage in that it has excellent transparency and flexibility, but has a lower conductivity than a transparent conductive oxide.

An electrochromic device, which is one of the electronic devices based on a transparent substrate, is a device in which a color change material is stimulated by an external stimulus such as electricity to cause a chemical reaction, and a color change effect is visibly generated. An electrochromic device based on a transparent substrate is configured such that a first electrode formed on a first transparent substrate and a second electrode formed on a second transparent substrate face each other, and an ion storage layer and an electrolyte are formed between the first and second electrodes. The layer and the electrochromic layer have a laminated structure. When a potential difference occurs between the first and second electrodes of the electrochromic element, the ions contained in the electrolyte layer move to the inside of the electrochromic layer or the ion storage layer and undergo an oxidation/reduction reaction, thereby visually changing color or color. The shade of the picture changes, and by using this light transmission characteristic, it is widely used as a light-shielding plate of a smart window, a car room mirror, and a transparent display, as well as a display element.

For the operation of not only electrochromic devices but also electronic devices based on transparent substrates, electricity of a certain size must be applied. It is also possible to directly apply electricity to the graphene composite electrode, but it is essential to form a bus electrode through an additional process in order to ensure the structure and electrical and physical stability of the device.

The present invention was conceived to solve the above problems, and an object of the present invention is to provide an electrode for an electronic device based on a highly reliable transparent substrate having excellent properties and a method of manufacturing the same, in which a bus electrode is formed using a graphene growth metal catalyst layer. It is in the offering.

A method of manufacturing an electrode for an electronic device based on a transparent substrate according to an embodiment of the present invention for achieving the above object comprises: a graphene growing step of growing graphene on a conductive growth substrate; Forming an atomic layer by performing an atomic layer deposition process on the graphene layer; A transparent conductive layer forming step of forming a transparent conductive layer on the atomic layer; Forming a bus electrode by removing a portion of the conductive growth substrate; And attaching the bus electrode to the flexible substrate.

The step of forming the atomic layer may be performed by arranging atoms in a defect region existing on the graphene layer.

Conductive growth substrates are Ni, Co, Fe, Pt, Au, Al, Cr, Cu, Mg, Mn, Mo, Rh, Si, Ta, Ti, W, U, V, Zr, brass, bronze, brass, stainless steel And one or more metals selected from the group consisting of Ge or alloys thereof.

The forming of the bus electrode may be performed by removing a part of the conductive growth substrate so that the graphene layer is exposed.

The forming of the bus electrode may include placing a mask on the conductive growth substrate; And etching the conductive growth substrate.

Flexible substrates include poly(methyl methacrylate, PMMA), polyethyleneterephthalate (PET), polyethylenenaphthalate (PEN), polycarbonate (PC), and polyimide (PI). ) May include any one of.

According to another aspect of the present invention, a graphene growth step of growing graphene on a conductive growth substrate; Forming an atomic layer by performing an atomic layer deposition process on the graphene layer; A first transparent conductive layer forming step of forming a transparent conductive layer on the atomic layer; Forming an electrochromic part including an electrochromic layer, an electrolyte layer, and an ion storage layer on the first transparent conductive layer; A second transparent conductive layer forming step of forming a transparent conductive layer on the outermost layer of the electrochromic part; Forming a bus electrode by removing a portion of the conductive growth substrate; And attaching the bus electrode to the flexible substrate.

According to another aspect of the present invention, a flexible substrate; A bus electrode formed on the flexible substrate; A graphene layer formed on the electrical connection portion; An atomic layer formed on the graphene layer; And a transparent conductive layer formed on the atomic layer.

As described above, when using the electrode for a transparent substrate-based electronic device and a method of manufacturing the same, which constitutes a bus electrode using a graphene growth metal catalyst layer according to embodiments of the present invention, defects possessed by graphene are Since it is healed by applying an atomic layer of similar size, high-quality graphene can be used as an electrode substrate, and the quality deterioration due to defects is minimized even in the process of applying high energy such as the transparent conductive layer, for example, the ITO layer formation process As a result, there is an effect of maintaining the quality of the transparent electrode used in the electrochromic device.

In addition, the high-quality graphene ensures the conductivity of the device, thereby minimizing the thickness of the transparent conductive layer, thereby obtaining an electrode having excellent flexibility and transparency of the device. In addition, graphene acts as a barrier between the transparent conductive layer and the growth substrate, preventing the constituents of the growth substrate from spreading to the transparent conductive layer, thereby maintaining the conductivity and transparency of the transparent conductive layer, making it possible to manufacture a high-quality, highly reliable transparent substrate. There is an effect.

In addition, additional formation of a bus electrode for applying electricity is essential for the operation of the device using the graphene composite electrode. In order to construct a flexible transparent substrate, the conductive substrate used for graphene growth must be removed and the flexible substrate must be attached.According to the embodiments of the present invention, in the removing step of the conductive substrate, a part of the graphene growth substrate remains only a desired pattern. By removing it, it is possible to form the bus electrode required for driving the device even without the configuration step of the additional bus electrode.

1 to 7 are views provided to explain a method for manufacturing an electrode for an electronic device based on a transparent substrate according to an embodiment of the present invention, and FIG. 8 is a cross-sectional view taken along AA′ of FIG.
9 to 11 are views provided to explain a method of manufacturing an electrochromic device among electronic devices based on a transparent substrate according to another embodiment of the present invention.

Hereinafter, embodiments of the present invention will be described with reference to the accompanying drawings. However, embodiments of the present invention may be modified in various other forms, and the scope of the present invention is not limited to the embodiments described below. Embodiments of the present invention are provided to more completely describe the present invention to those of ordinary skill in the art. In the accompanying drawings, there may be components having a specific pattern or having a predetermined thickness, but this is for convenience of description or distinction. It is not limited to just that.

1 to 7 are views provided to explain a method of manufacturing an electrode for an electronic device based on a transparent substrate according to an embodiment of the present invention, and FIG. 8 is a cross-sectional view taken along line A-A' of FIG. 7. The method of manufacturing an electrode for an electronic device based on a transparent substrate according to the present embodiment includes a graphene growth step of growing a graphene layer 120 on a conductive growth substrate 110; Forming an atomic layer 130 by performing an atomic layer deposition process on the graphene layer 120; A transparent conductive layer forming step of forming a transparent conductive layer 140 on the atomic layer 130; Forming a bus electrode 110 ′ by removing a portion of the conductive growth substrate 110; And attaching the bus electrode 110 ′ to the flexible substrate 150.

In the present invention, a method of manufacturing an electrode for an electronic device based on a transparent substrate using a part of a graphene growth metal catalyst layer as a bus electrode in a graphene composite electrode in which physical properties of an electrode are supplemented by using a transparent conductive layer and a graphene layer together is disclosed. .

In order to manufacture an electrode for an electronic device based on a transparent substrate according to the present invention, a graphene growth step of growing a graphene layer 120 on a conductive growth substrate 110 is first performed (FIG. 1). Graphene can be synthesized in various ways, and in this embodiment, it is synthesized by a direct growth method in which graphene is synthesized directly on a conductive growth substrate. The conductive growth substrate 110 functions as a seed layer for growing graphene, and is not limited to a specific material, but contains a conductive material because a part is removed in the next step to function as the bus electrode 110 ′. It is desirable to do it. For example, the conductive growth substrate 110 is Ni, Co, Fe, Pt, Au, Al, Cr, Cu, Mg, Mn, Mo, Rh, Si, Ta, Ti, W, U, V, Zr, brass, It may comprise one or more metals or alloys thereof selected from the group consisting of bronze, brass, stainless steel, and Ge.

The conductive growth substrate 110 may further include a catalyst layer (not shown) that adsorbs carbon well in order to facilitate the growth of graphene. The catalyst layer is not limited to a specific material, and may be formed of the same or different material as the conductive growth substrate 110. Meanwhile, the thickness of the catalyst layer is also not limited, and the shape may also be a thin film or a thick film.

When the conductive growth substrate is prepared, a graphene growth step of growing graphene on the conductive growth substrate 110 is performed. As a method of forming the graphene layer 120 on the conductive growth substrate 110, chemical vapor deposition (CVD) may be used. Here, the chemical vapor deposition method is high temperature chemical vapor deposition (RTCVD), inductively coupled plasma chemical vapor deposition (ICP-CVD), low pressure chemical vapor deposition (LPCVD), atmospheric pressure chemical vapor deposition (APCVD), metal organic chemical vapor deposition (MOCVD). Alternatively, it may be subdivided into chemical vapor deposition (PECVD) or the like.

The conductive growth substrate 110 is introduced into the reactor, and graphene is grown through atmospheric pressure heat treatment under conditions of supplying a reaction gas used as a carbon source to form the graphene layer 120.

The heat treatment temperature for graphene growth may be 300°C to 2,000°C. When the conductive growth substrate 110 is reacted with a carbon source at high temperature and atmospheric pressure in this way, the supplied carbon is dissolved or adsorbed on the conductive growth substrate 110, and then the dissolved and adsorbed carbon atoms are crystallized on the surface of the growth substrate 110. Graphene crystal structure is formed.

Meanwhile, in the above-described process, the number of layers of the graphene layer 120 may be controlled by controlling the type and thickness of the conductive growth substrate 110 (including the catalyst layer), reaction time, cooling rate, and reaction gas concentration.

Examples of carbon sources include carbon monoxide, carbon dioxide, methane, ethane, ethylene, ethanol, acetylene, propane, butane, butadiene, pentane, pentene, cyclopentadiene, hexane, cyclohexane, benzene, toluene, and the like.

Graphene is synthesized while supplying a reaction gas including a carbon source in the gas phase and controlling the temperature to form a hexagonal plate-like structure on the surface of the conductive growth substrate 110 of the carbon atoms of the reaction gas (FIG. 1).

When the graphene layer 120 is formed, a step of forming the atomic layer 130 by performing an atomic layer 130 deposition process on the graphene layer 120 is performed. Referring to FIG. 1, a graphene crystal structure 121 having a hexagonal structure is formed on the graphene layer 120, and a graphene domain boundary 122 is also formed by colliding three graphene domains. The graphene domain boundary 122 destroys the ideal hexagonal crystal structure of the graphene layer 120, which soon acts as a defect of graphene. That is, the conductivity of the graphene layer 120 is deteriorated and a leakage current is generated, resulting in a problem of deteriorating product reliability when manufacturing a transparent substrate using the graphene layer 120. In addition, the graphene defect 122 becomes a region where energy or the like aggregates under a high temperature and high pressure condition when performing a post process, thereby further damaging the graphene layer 120.

In the method of manufacturing an electrode for an electronic device based on a transparent substrate including a bus electrode according to the present invention, as a method of healing the graphene defect 122, an atomic layer 130 is formed by performing an atomic layer deposition process on the graphene layer. The step is performed. Referring to FIG. 2, the atomic layer is deposited on the graphene defect 122. In the present invention, the atomic layer 130 is formed on the graphene layer 120. A state in which an atomic line is arranged to apply the defect to the portion of the graphene defect 122 located on the upper surface of the graphene layer 120, including the state in which the layer is arranged, that is, a part of one layer is formed. It is a concept that also includes an atomic arrangement. This form of atomic arrangement can be realized by performing an atomic layer deposition (ALD) process.

In the ALD process, a precursor gas of an atom to be deposited is injected and a reaction gas is injected together to form a thin film by laminating atoms in a layer on a substrate to be deposited.

3 is a cross-sectional view of a graphene layer in which an atomic layer is formed in FIG. 2. The atomic layer 130 is intensively arranged on the graphene defect 122 of the graphene layer 120, which is preferentially deposited on the graphene defect 122 where the energy is relatively condensed in the atomic arrangement according to the ALD process. It can be interpreted as because it becomes. As such, the graphene defect 122 is an area where energy is easily collected, so if a process of applying high energy (heat or plasma) is performed in a subsequent process, damage may be intensified in the defect area, but the atomic layer 130 is like this. When applied to the pin defect 122, it is possible to prevent deterioration of the properties of the graphene layer 120 by preventing energy from being concentrated to the defective portion of the graphene.

As the atomic layer 130, an atomic layer of a metal or a metal oxide may be formed. For example, an atomic layer of a metal oxide such as aluminum oxide or zinc oxide may be formed. In the case of aluminum oxide, since the diameter of the atomic layer is about 0.67Å, in the case of the graphene layer 120 of 1 to 10 nm, an aluminum oxide atomic layer is formed inside the graphene defect 122 or near the graphene defect 122 It may be gathered together and formed in a line shape along the graphene domain boundary 122.

The atomic layer 130 may be formed by repeating an atomic layer deposition process a plurality of times. The number of times the atomic layer is deposited may be selected in consideration of the thickness of the graphene layer 120 and the size or frequency of the graphene defects 122.

When the atomic layer deposition process is repeatedly performed a plurality of times, the atomic layer 130 may be implemented as a single layer. As described above, the atomic layer 130 may include a metal or a metal oxide, but may be formed so as not to adversely affect the conductivity of the graphene layer 120 or the transparent conductive layer 140. That is, a slight decrease in conductivity may occur in the graphene layer 120 due to the introduction of a heterogeneous material of an oxide type, but does not adversely affect the conductivity of the transparent conductive layer 140 and while forming the transparent conductive layer 140 Since the generated defects are minimized, the effect of the atomic layer on the graphene composite electrodes 120 to 140 can be neglected.

When the atomic layer 130 is formed, a transparent conductive layer is formed on the atomic layer 130 to form the transparent conductive layer 140, which functions as one electrode (FIG. 4). The transparent conductive layer 140 is implemented with a conductive material of a transparent material, for example, indium tin oxide (ITO), indium zinc oxide (IZO), F-doped tin oxide (FTO), antimony tin oxide (ATO), AZO(ZnO:Al), GZO(ZnO:Ga), a-IGZO(In ₂ O ₃ :Ga ₂ O ₃ :ZnO), MgIn ₂ O ₄ , Zn ₂ SnO ₄ , ZnSnO ₃ , (Ga,In) ₂ O ₃ , Zn ₂ In ₂ O ₅ , InSn ₃ O ₁₂ , In ₂ O ₃ , SnO ₂ , Cd ₂ SnO ₄ , CdSnO ₃ And one or more metal oxides selected from _{CdIn 2} O _{4 or Cu, Al, Sn,} It may be at least one metal selected from Ni, W, Ti, Cr, Co, Zn, Ta, V, Au, Ag, TiN, and Pt, or may include nanowires such as Cu nanowires or Ag.

The transparent conductive layer 140 may be formed using a physical or chemical vapor deposition process such as thermal deposition, chemical vapor deposition, or sputtering.

The graphene layer 120, the atomic layer 130, and the transparent conductive layer 140 on the conductive growth substrate 110 according to the present invention may be used as a transparent substrate for an electrochromic device. The graphene layer 120 may be used as a transparent substrate by taking advantage of the flexibility, transparency, and thin thickness of the graphene layer 120, but it is difficult to use it alone because it is difficult to achieve the required level of conductivity as an electrode. The transparent conductive layer 140 exhibits high transparency and conductivity, but it is difficult to implement as a flexible electrode due to its low flexibility. In order to secure high conductivity, the thickness of the electrode becomes thicker, thereby reducing transparency and flexibility, thereby reducing the desired quality when used alone. It is difficult to achieve.

The electrode of the electrochromic device including the bus electrode according to the present invention includes a transparent conductive layer 140 on the graphene layer 120 together, supplementing the low conductivity of the graphene layer 120, and the transparent conductive layer 140 ) To increase the transparency and secure the flexibility of the electrode.

In addition, since the transparent conductive layer 140 is formed on the graphene layer 120 and transferred to a flexible substrate, it is possible to crystallize the transparent conductive layer 140 through high-temperature treatment, thereby achieving high conductivity, as well as conductivity. The graphene layer 120 between the growth substrate 110 and the transparent conductive layer 140 prevents impurities from entering from the growth substrate 110 to maintain conductivity and transparency of the transparent conductive layer 140.

When the transparent conductive layer 140 is formed, a part of the conductive growth substrate 110 is removed to form the bus electrode 110 ′. The bus electrode 110 ′ is a path through which voltage or current can be applied to the electrochromic element. The applied voltage or current is applied to the entire surface of the graphene composite electrodes 120 to 140 through the bus electrode, and the voltage or current applied through the graphene layer 120 is applied on the transparent conductive layer 140. That is, the electric signal for the operation of the transparent substrate-based electronic device is transmitted to the entire surface of the graphene layer 120 through the bus electrode, and through the transparent conductive layer 140 through the graphene layer 120 to the upper part of the transparent conductive layer 140. The bus electrode connects only the outer portion of the graphene layer 120 as shown in FIG. 6 and may be formed only in a partial area.

The structure of the bus electrode is not limited to the shape as shown in FIG. 6, but may be formed in various patterns in consideration of the size of the electrode or device, distribution of electric field, and the like.

In the present invention, the bus electrode 110 ′ is not separately formed through an additional process, but after the graphene layer 120, the atomic layer 130, and the transparent conductive layer 140 are formed, the conductivity to be removed before transferring to the flexible substrate. A portion of the growth substrate 110 is not removed, but a portion thereof is left to form the shape of the bus electrode 110 ′. This is to use the characteristics of the conductive growth substrate 110 having conductivity. Therefore, since the bus electrode 110 ′ can be manufactured in a single process without configuring a separate process for forming the bus electrode 110 ′, the process can be facilitated and manufacturing cost can be reduced. In addition, since the graphene layer 120 is grown on the bus electrode, a process of separately attaching the bus electrode 110 ′ to the graphene layer 120 is unnecessary, so formation of an adhesive layer or the like can be omitted.

The removal of the conductive growth substrate 110 for forming the bus electrode 110 ′ uses an etching solution capable of selectively removing the conductive growth substrate 110. The etching solution may be selected according to the type of the conductive growth substrate 110, and examples of the etching solution include hydrogen fluoride (HF), buffered oxide etch (BOE), ferric chloride (FeCl ₃ ) solution, or nitric acid. Ferric (Fe(NO ₃ ) ₃ ) solutions.

For the formation of the bus electrode 110 ′ by removing the conductive growth substrate 110, use a mask M made of a pattern to form the bus electrode 110 ′, or use an etching solution and a conductive growth substrate 110. After masking the conductive growth substrate 110 with a desired pattern in order to limit the contact of the bus electrode 110 ′, a pattern of the bus electrode 110 ′ may be formed by etching the conductive growth substrate 110 (FIG. 5 ).

As shown in FIG. 6, the bus electrode 110 ′ is formed in a state in which a portion thereof is removed, thereby exposing the graphene layer 120 in contact with the conductive growth substrate 110 to the outside. Thereafter, a flexible substrate 150 is attached to the bus electrode 110' to manufacture a flexible electrode for an electrochromic device. 7 and 8, a part of the conductive growth substrate 110 has been removed to form an empty space 111 in the bus electrode 110', which is formed in a state surrounded by the flexible substrate 150. .

The electrode 100 for an electronic device based on a transparent substrate according to FIG. 7 includes a flexible substrate 150; A bus electrode 110' formed on the flexible substrate 150; A graphene layer 120 on the bus electrode 110 ′; An atomic layer 130 formed on the graphene layer 120; And a transparent conductive layer 140 formed on the atomic layer 130.

The flexible substrate 150 that can be used in the present invention is a substrate exhibiting flexibility, for example, poly(methyl methacrylate), PMMA, polyethylene terephthalate (PET), polyethylene or It may contain any one of phthalate (polyethylenenaphthalate, PEN), polycarbonate (PC), and polyimide (PI).

9 to 11 are views provided to explain a method of manufacturing an electrochromic device among electronic devices based on a transparent substrate according to another embodiment of the present invention. The method of manufacturing an electrochromic device according to the present embodiment includes a graphene growth step of growing a graphene layer 220 on a conductive growth substrate 210; Forming an atomic layer 230 by performing an atomic layer 230 deposition process on the graphene layer 220; Forming a first transparent conductive layer 241 of forming a transparent conductive layer on the atomic layer 230; Forming an electrochromic portion 260 including an ion storage layer 261, an electrolyte layer 262, and an electrochromic layer 263 on the first transparent conductive layer 241; And a second transparent conductive layer 242 forming step of forming a transparent conductive layer on the outermost layer of the electrochromic part 260. Forming a bus electrode 210 ′ by removing a portion of the conductive growth substrate 210; And bonding the bus electrode 210 ′ to the flexible substrate 250. Hereinafter, descriptions of the same contents as described with reference to FIGS. 1 to 8 will be omitted.

On the first transparent conductive layer 241, an electrochromic part 260 capable of discoloration through application of a voltage is formed. The electrochromic unit 260 may be sequentially formed with an ion storage layer 261, an electrolyte layer 262, and an electrochromic layer 263 on the first transparent conductive layer 241, as mentioned above. Alternatively, the electrochromic layer 263, the electrolyte layer 262, and the ion storage layer 261 may be formed on the first transparent conductive layer 241 in this order.

The ion storage layer 261 is involved in the entrance/exit of ions participating in the electrochromic reaction. In the case of reacting to emit ions from the electrochromic layer 263, when the ion from the electrochromic layer 263 is received in the ion storage layer 261 and the ions are received in the electrochromic layer 263 In the ion storage layer 261, the corresponding ions are provided. The ion storage layer 261 may be formed of an ion storage material or an oxidation/reduction coloring material for storing a plurality of cations such as hydrogen ions or lithium ions, or other types of ions participating in electrochromism.

In addition to the electrochromic layer 263, the ion storage layer 261 may function as another electrochromic layer to increase the color change efficiency of the device. The ion storage layer 261 of the electrochromic device may be formed of an electrochromic material having a reaction corresponding to the electrochromic layer 263 and the redox reaction. That is, when the electrochromic layer 263 is a reducing color change material, the ion storage layer 261 may be an oxidation color change material, and vice versa. When the ion storage layer 261 of the electrochromic element is composed of another electrochromic layer, the color transmittance of the element decreases, thereby increasing the color change efficiency. The electrochromic layer 263 may be formed using an electrochromic material whose color changes according to an electric signal, and the electrochromic material may be an inorganic material or an organic material.

The electrochromic material used as the ion storage layer 261 and the electrochromic layer 263 can be selected fluidly depending on whether the color is changed by either an oxidation reaction or a reduction reaction, and the ion storage layer 261 and the electrochromic material change color. When the layer 263 is connected to the device, it may be selected so that the redox reaction can be responded to. When the electrochromic material used as the ion storage layer 261 and the electrochromic layer 263 is an inorganic material, a transition metal oxide deposited in the form of a thin film may be used. NiO, Cr ₂ O ₃ , MnO ₂ , Rh ₂ At least one selected from O ₃ , CoO _x , Ir(OH) _x , Fe ₂ O ₃ , WO ₃ , ZnO, NbO ₅ , V ₂ O ₅ , TiO ₂ , MoO ₃ and the like may be used. In addition, the electrochromic material, which is an organic material, is based on a viologen compound, a diphtahlocyanine compound, a tetrathiafulvalene compound, and polyaniline, polythiophene, PEDOT (3,4-ethylenedioxythiophene), etc. There is one variety of polymeric compounds. Organic electrochromic materials are decomposed by sunlight and have a disadvantage in that their lifespan may be shortened, but they can be widely used because they can produce a desired color if they are properly mixed.

When the electrochromic part 260 is formed, a second transparent conductive layer 242 is formed as an electrode facing the first transparent conductive layer 241 (FIG. 9). The second transparent conductive layer 242 may be implemented as a transparent and conductive metal oxide that is the same or similar to the first transparent conductive layer 241.

The electrolyte layer 262 is formed between the ion storage layer 261 and the electrochromic layer 263, and a material containing ions involved in the electrochromic reaction may be used. For example, the electrolyte layer 262 is Ta ₂ O ₅ , LiClO ₄ , LiNbO ₃ , Li _3+x PO _4-x N _x (LiPON), LiVO ₃ /SiO ₂ /Li ₄ SiO ₄ -Li ₃ VO ₄ It may be formed using at least one selected from (LVSO), LiPF ₆ , Li ₃ PO _{4, and the like.} The electrolyte may be a solid electrolyte or a gel electrolyte.

When the electrolyte layer 262 is a solid electrolyte, the electrochromic unit 260 sequentially includes an ion storage layer 261, an electrolyte layer 262, and an electrochromic layer 263 on the first transparent conductive layer 241. It can be formed by stacking.

Unlike the first transparent conductive layer 241, the graphene layer 220 is not formed together with the second transparent conductive layer 242. Accordingly, the second transparent conductive layer 242 may be formed to have a larger thickness than the first transparent conductive layer 241 or may be formed of a material having higher conductivity, if necessary.

When the second transparent conductive layer 242 is formed, since the formation of the graphene layer 220, the first transparent conductive layer 241, the electrochromic part 260, and the second transparent conductive layer 242 is completed, the conductive growth substrate The bus electrode 210' is formed by partially removing 210 (FIG. 10). Thereafter, the flexible substrate 250 is attached to the bus electrode 210' (FIG. 11).

When the electrolyte layer 262 is a gel electrolyte, forming the electrochromic part 260 and forming the second transparent conductive layer 242 may include an electrochromic layer on the first transparent conductive layer 241 ( 263) and forming any one of the ion storage layer 261; Forming the other one of the electrochromic layer 263 and the ion storage layer 261 on the second transparent conductive layer 242; And a laminating step of coating and laminating the electrolyte layer 262 between the electrochromic layer 263 and the ion storage layer 261.

That is, when using a gel electrolyte, the electrochromic layer, the electrolyte layer, and the ion storage layer are not sequentially formed to form an electrochromic part, but an ion storage layer is formed on the first transparent conductive layer, and the second transparent conductive layer is formed. After the remaining electrochromic layer is formed on the top, an electrolyte layer is applied therebetween, and then both are laminated to manufacture an electrochromic device.

In the present invention, the gel electrolyte is a material containing a polymer in a solvent in which a salt containing ions participating in the electrochromic reaction is dissolved, and may additionally include additives such as an initiator and a crosslinking agent so that it can be cured with light or heat in a subsequent process. have. As salts contained in the gel electrolyte, ^Li+ _{systems such as LiClO 4} , LiPF ₆ , LiTFSI (CF ₃ SO ₂ NLiSO ₂ CF ₃ ), LiFSI (F ₂ LiNO ₄ S ₂ ), etc. are commonly used, but participate in the electrochromic reaction. It can be used in various ways depending on the type of ions. The polymer material used in the gel electrolyte may be a polymer based on polyethylene oxide (PEO), poly(ethylene glycol) (PEG), poly acrylonitrile (PAN), or other types of polymers. As a solvent, organic solvents that are stable in electrochemical reactions and have low volatility are mainly used, and include PC (propylene carbonate) and EC (ethylene carbonate).

The material used for the electrolyte layer 262 may be selected in various ways in connection with the oxidation-reduction reaction occurring in the electrochromic layer 263 and the ion storage layer 261 as well as the above example, and the electrochromic reaction is smooth. Various other types of additives may be introduced to achieve this.

As described above, in the embodiments of the present invention, an electrode for an electronic device based on a transparent substrate including a bus electrode can be manufactured using a graphene composite electrode with improved conductivity and flexibility, while the growth substrate of the graphene layer is used as it is. By using the bus electrode, it is possible to obtain an electrochromic device of excellent quality in a simpler method without an additional bus electrode configuration step.

In the above, embodiments of the present invention have been described, but those of ordinary skill in the relevant technical field add, change, delete or add components within the scope not departing from the spirit of the present invention described in the claims. It will be possible to variously modify and change the present invention by means of the like, and it will be said that this is also included within the scope of the present invention.

100 Electrochromic device 110, 210 Conductive growth substrate
110', 210' Bus electrode 111, 211 Space in bus electrode
120, 220 graphene layer 130, 230 atomic layer
140, 241 First transparent conductive layer 150, 250 Flexible substrate
242 Second transparent conductive layer 260 Electrochromic part
261 Ion storage layer 262 Electrolyte layer
263 Electrochromic layer

Claims (8)

A graphene layer forming step of forming a graphene layer by growing graphene on a conductive growth substrate;
Forming an atomic layer by performing an atomic layer deposition process on the graphene layer;
A transparent conductive layer forming step of forming a transparent conductive layer on the atomic layer;
Forming a bus electrode by removing a portion of the conductive growth substrate; And
A method for manufacturing an electrode for an electronic device based on a transparent substrate comprising: attaching the bus electrode to the flexible substrate so that a part of the conductive growth substrate is removed in the bus electrode to form an empty space surrounded by the flexible substrate.
The method according to claim 1,
The step of forming the atomic layer,
A method for manufacturing an electrode for an electronic device based on a transparent substrate, which is performed by arranging atoms in a defect region existing on the graphene layer.
The method according to claim 1,
The conductive growth substrate is Ni, Co, Fe, Pt, Au, Al, Cr, Cu, Mg, Mn, Mo, Rh, Si, Ta, Ti, W, U, V, Zr, brass, bronze, brass, stainless steel A method for manufacturing an electrode for an electronic device based on a transparent substrate comprising at least one metal selected from the group consisting of steel and Ge or an alloy thereof.
The method according to claim 1,
Forming the bus electrode,
The method of manufacturing an electrode for an electronic device based on a transparent substrate, which is performed by removing a part of the conductive growth substrate so that the graphene layer is exposed.
The method according to claim 1,
Forming the bus electrode,
Positioning a mask on the conductive growth substrate; And
The method of manufacturing an electrode for an electronic device based on a transparent substrate comprising a; step of etching the conductive growth substrate.
The method according to claim 1,
The flexible substrate is poly(methyl methacrylate), PMMA, polyethyleneterephthalate (PET), polyethylenenaphthalate (PEN), polycarbonate (PC), and polyimide. PI) a method of manufacturing an electrode for an electronic device based on a transparent substrate comprising any one of.
A graphene layer forming step of forming a graphene layer by growing graphene on a conductive growth substrate;
Forming an atomic layer by performing an atomic layer deposition process on the graphene layer;
A first transparent conductive layer forming step of forming a transparent conductive layer on the atomic layer;
Forming an electrochromic part including an electrochromic layer, an electrolyte layer, and an ion storage layer on the first transparent conductive layer;
A second transparent conductive layer forming step of forming a transparent conductive layer on the outermost layer of the electrochromic part;
Forming a bus electrode by removing a portion of the conductive growth substrate; And
A method for manufacturing an electrochromic device comprising: attaching the bus electrode to the flexible substrate so that a part of the conductive growth substrate is removed in the bus electrode to form an empty space surrounded by the flexible substrate.
Flexible substrate;
A bus electrode formed on the flexible substrate;
A graphene layer formed on the bus electrode;
An atomic layer formed on the graphene layer; And
As an electrode for a transparent substrate-based electronic device comprising; a transparent conductive layer formed on the atomic layer,
The bus electrode is formed by removing a part of the conductive growth substrate used when growing the graphene layer,
The bus electrode is an electrode for a transparent substrate-based electronic device, characterized in that a part of the conductive growth substrate is removed in the bus electrode and attached to the flexible substrate to form an empty space surrounded by the flexible substrate.

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