KR101627422B1 - Transparent electrode by metal nanowire with graphene oxide using complex light source with full range wavelenth and fabrication method of thereof - Google Patents
Transparent electrode by metal nanowire with graphene oxide using complex light source with full range wavelenth and fabrication method of thereof Download PDFInfo
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Abstract
The present invention relates to a substrate; Graphene layer; And a transparent electrode including a metal nanowire, wherein the metal nanowire layer is formed on the graphene layer through a composite light irradiation which irradiates any one selected from ultraviolet rays, infrared rays, And is optically bonded at a room temperature and an atmospheric condition at a short time within a range of 1 to 100 ms, and exhibits excellent sheet resistance and transmittance.
Description
The present invention relates to a flexible transparent electrode that exhibits excellent sheet resistance and transmittance through optical junctions between the points of contact between graphene and metal nanowires using a composite light source, and a method for manufacturing the same.
Transparent electrodes are widely used in transparent electronic devices such as touch screens, organic light emitting diodes, flat panel displays, solar cells, and transparent displays. In general, indium tin oxide (ITO) is mainly used as a transparent electrode. ITO has excellent transparency over visible light region, relatively low sheet resistance, has a work function suitable for charge carrier injection and collection in organic semiconductors It is because.
However, most of the ITO is deposited through a thin film deposition process such as sputtering, so that not only the process cost is high but also it can not be used in a plastic substrate, and since a dense thin film having a crystalline structure is formed, cracks occur in the repeated warping process, There is a drawback that the electrode is peeled off from the lower substrate and thus it is not suitable as a flexible transparent electrode having a flexible performance and the increase of the price due to the problem of the exhaustion of indium and the concentration of indium reserves in a specific country There is a sense of burden.
A method of using carbon nanotubes (CNTs) as an alternative material to overcome these problems has been proposed. Carbon nanotubes are advantageous in that they exhibit excellent electrical conductivity and high transmittance but are inferior in performance to ITO characteristics. If the content of carbon nanotubes exceeds a predetermined critical amount, the transparent electrode may have a dark black color, There are limitations in application.
In order to solve the above problems, research and development on graphene transparent electrodes and metal nanowire transparent electrodes have been actively conducted. However, graphene has problems such as high cost due to chemical vapor deposition process, complicated process and high electric resistance, and metal nanowires have low electrical resistance, can have high transparency even in a small amount, can be mass-synthesized, There is a problem in that it is easily oxidized in the atmosphere, and as a result, an oxide is formed and the electric conductivity is gradually decreased.
SUMMARY OF THE INVENTION It is an object of the present invention to provide a transparent electrode having improved dielectric properties by bonding a graphene and a metal nanowire using composite light irradiation which irradiates one of ultraviolet light, .
Another object of the present invention is to provide a method of manufacturing a transparent electrode including a composite of the graphene and a metal nanowire.
According to an aspect of the present invention, there is provided a transparent electrode comprising: a substrate; Graphene layer; And a metal nanowire layer,
The metal nanowire layer may be one that is impregnated and bonded to the graphene layer through a composite light irradiation which irradiates either one selected from ultraviolet light, infrared light, and composite light thereof, and extreme ultraviolet light.
The impregnation may be all or part of the impregnation.
According to the present invention, the structure of the transparent electrode may be a structure of a substrate, a graphene layer formed on the substrate, and a metal nanowire layer formed on the graphene layer, or may be a substrate, a metal nanowire Layer and a structure of the graphene layer formed on the metal nanowire layer.
According to the present invention, the metal nanowire may be one or more selected from the group consisting of silver nanowires, copper nanowires, nickel nanowires, gold nanowires, and iron nanowires, and may have a diameter of 5 to 100 nm , And a length of 5 to 100 mu m.
According to the present invention, the metal nanowire layer may further include a dispersant and a dispersion stabilizer.
According to the present invention, the content ratio of the graphene to the metal nanowire may be 1:15 to 10: 1.
According to another aspect of the present invention, there is provided a method of fabricating a transparent electrode including a composite of a graphene and a metal nanowire according to the present invention.
1) forming a graphene oxide layer and a metal nanowire layer on a substrate; And
2) The substrate on which the graphene oxide layer and the metal nanowire layer are formed is irradiated with either ultraviolet light or ultraviolet light selected from ultraviolet rays, infrared rays, and composite light rays at room temperature to reduce graphene oxide to graphene And a step of performing optical coupling so that the metal nanowire layer is impregnated and bonded to the formed graphene layer at the same time.
According to the present invention, the stacking order of the graphene oxide layer and the metal nanowire layer formed on the substrate can be changed.
The substrate, the graphene oxide layer, and the metal nanowire layer may be stacked in this order, or the substrate, the metal nanowire layer, and the graphene oxide layer may be stacked in this order.
According to the present invention, the step 1) may further include a preliminary light irradiation step for preheating or solvent drying.
The preliminary light irradiation may be irradiation with any one of a light source selected from ultraviolet rays, infrared rays, and composite light of these.
According to the present invention, the impregnation may be all or part of the impregnation.
The extreme ultraviolet white light is irradiated from a xenon flash lamp and has a pulse width of 0.1 to 100 ms, a pulse number of 1 to 100, an intensity of 0.1 to 100 J / cm 2 , a pulse gap of 0.1 to 100 ms ,
The ultraviolet light may be irradiated for 0 to 300 seconds at an intensity of 10 to 1000 mW / cm 2 ,
The infrared rays may be irradiated at an intensity of 100 to 5000 W / cm 2 for 0 to 300 seconds.
According to the present invention, the substrate may be selected from the group consisting of polyethylene naphthalate (PEN), polyethylene (PT), polyimide (PI), polyester (PET), BT epoxy / glass fiber and photopaper.
The preliminary light irradiation and the composite light irradiation in step 2) may be performed in a single step or a multi-step.
According to the present invention, the metal nanowire layer is formed by toppling a dispersion of metal nanowires, wherein the dispersion of metal nanowires comprises 0.1 to 70% by weight of metal nanowires based on 100% by weight of the total dispersion of metal nanowires; 0.1 to 50% by weight of a dispersant; 0.1 to 50% by weight of a dispersion stabilizer; And 0.1 to 99.7 wt% of a solvent.
According to the present invention, the metal nanowires may be one or more selected from the group consisting of silver nanowires, copper nanowires, nickel nanowires, gold nanowires, and iron nanowires. The nanowires may have a diameter of 5 to 100 nm , And the length may be between 5 and 100 [mu] m, and at least one point of the metal nanowires may be connected to one another in regular or irregular crossings with other metal nanowires.
According to the present invention, the content ratio of the graphene to the metal nanowire in the transparent electrode may be 1:15 to 10: 1.
The method of optically bonding graphene to metal nanowires using a complex light irradiation method for irradiating infrared light, ultraviolet light or a compound light source thereof and extreme ultraviolet light together according to the present invention is to instantaneously irradiate strong light to a wide region, And in an atmospheric state, it does not cause damage to the large-area or polymer-based substrate. In addition, there is no need for a separate vacuum equipment or a large-sized chamber, which is economical because the manufacturing cost of the flexible transparent electrode can be greatly reduced. In addition, the transparent electrode manufactured by the above method exhibits excellent sheet resistance and transmittance due to the optical junctions between the points of contact between the graphene and the metal nanowire, and thus can be used in displays such as displays, solar cells, and electronic newspapers And the like.
FIG. 1 is a process flow diagram illustrating a process for fabricating a transparent electrode including a complex of graphene and metal nanowire according to an embodiment of the present invention. Referring to FIG.
FIG. 2 is a flow chart illustrating a process of fabricating a transparent electrode including a complex of graphene and metal nanowire according to another embodiment of the present invention. Referring to FIG.
FIG. 3 is a graph showing the sheet resistance of a transparent electrode including a composite of graphene and metal nanowire according to the content ratio of graphene to metal nanowire. FIG.
FIG. 4 is a graph showing haze of a transparent electrode including a composite of graphene and metal nanowires according to the content ratio of graphene and metal nanowire. FIG.
FIG. 5 is a graph showing the transparency of a transparent electrode including a composite of graphene and metal nanowire according to the content ratio of graphene to metal nanowire. FIG.
FIG. 6 is a graph showing sheet resistance of a transparent electrode including a composite of graphene and metal nanowire when a combination of ultraviolet light and white light is irradiated.
FIG. 7A is an electron scanning microscope image of a composite of graphene and metal nanowire without performing optical bonding, FIG. 7B is an image of a combination of ultraviolet light An electron scanning microscope image of a complex of graphene and metal nanowires showing that a part of the nanowire layer is impregnated into the graphene layer through a composite light irradiation.
Hereinafter, the present invention will be described in more detail.
The transparent electrode of the present invention comprises a substrate; Graphene layer; And a metal nanowire layer.
The metal nanowire layer may be one that is impregnated and bonded to the graphene layer through a composite light irradiation which irradiates either one selected from ultraviolet light, infrared light, and composite light thereof, and extreme ultraviolet light.
The impregnation may be all or part of the impregnation.
The metal nanowires of the metal nanowire layer may be at least one point in a regular or irregularly intersecting relationship with other metal nanowires and may form a net structure and the intersections may be formed by ultraviolet, And composite light, and the extreme ultraviolet light may be optically conjugated through composite light irradiation.
The transparent electrode of the present invention may be a structure of a substrate, a graphene layer formed on the substrate, and a metal nanowire layer formed on the graphene layer. In order to prevent the metal nanowires from being oxidized, A graphene layer may be further formed.
The transparent electrode may be a structure of a substrate, a metal nanowire layer formed on the substrate, and a graphene layer formed on the metal nanowire layer. The metal nanowire may include a metal nanowire The graft layer above the layer and the substrate below the metal nanowire layer may be optically bonded.
The metal nanowires of the present invention may be one or more kinds selected from the group consisting of silver nanowires, copper nanowires, nickel nanowires, gold nanowires, and iron nanowires, preferably silver nanowires Since the silver nanowire is a metal present in a large quantity in a natural world, it is easy to supply and receive, and the electrical resistance is the lowest in the metal, and the electric conductivity comparable to ITO and the transparency of 85% .
According to an embodiment of the present invention, the metal nanowire layer may further include a dispersant and a dispersion stabilizer.
The dispersing agent may be selected from the group consisting of polyvinylpyrrolidone, polyvinyl alcohol, polyvinyl butyral, polyethylene glycol, polymethyl methacrylate, dextran, polyurethane dispersions (PUD) and hydroxypropyl methylcellulose And may be any one or a mixture of two or more selected from the group consisting of
The dispersion stabilizer may be selected from the group consisting of Disperbyk 180, Disperbyk 111, styrene maleic and hydride copolymer (SMA 1440 flake), 2-butoxy ethyl acetate, propylene glycol monomethyl ether acetate, diethylene glycol monoethyl ether acetate, ethylene glycol butyl ether But is not limited to, any one or a mixture of two or more selected from the group consisting of cyclohexanone, cyclohexanol, 2-ethoxyethyl acetate, ethylene glycol diacetate, terpineol and isobutyl alcohol no.
According to an embodiment of the present invention, the metal nanowire layer comprises 0.1 to 70% by weight of metal nanowires; 0.1 to 50% by weight of a dispersant; 0.1 to 50% by weight of a dispersion stabilizer; And 0.1 to 99.7% by weight of a solvent; and the metal nanowires may have a diameter of 5 to 100 nm and a length of 5 to 100 占 퐉.
According to an embodiment of the present invention, the graphene layer may be formed to a thickness of 1 to 300 nm. Wherein the graphene layer is coated with a graphene oxide dispersion consisting of 0.01 to 50% by weight of graphene oxide and 50 to 99.99% by weight of solvent, and is selected from ultraviolet, infrared, and composite light thereof; And then irradiated with the ultraviolet rays.
According to an embodiment of the present invention, the graphene and the metal nanowire may be composite-optically conjugated at a content ratio of 1:15 to 10: 1.
If the content of the metal nanowires is within the above range, the transparent electrode having excellent sheet resistance but high haze and low transparency can be obtained, and the content of the metal nanowires can be reduced. Below this range, the transmittance is not good.
In particular, when the content ratio of graphene to metal nanowire is in the range of 1:12 to 2: 8, the sheet resistance is similar to that in the case of using only the metal nanowire, while exhibiting low haze and high transmittance, And the metal nanowire layer are combined with each other by irradiating the metal nanowire layer with any one selected from ultraviolet rays, infrared rays, and complex light rays thereof, and extreme ultraviolet white light, the sheet resistance is further lowered, High haze and high transmittance.
The present invention also relates to a method for manufacturing a transparent electrode comprising a complex of the graphene and a metal nanowire.
A method of manufacturing a transparent electrode comprising a composite of graphene and metal nanowire of the present invention can be achieved by a method including the following steps.
1) forming a graphene oxide layer and a metal nanowire layer on a substrate; And
2) The substrate on which the graphene oxide layer and the metal nanowire layer are formed is irradiated with either ultraviolet light or ultraviolet light selected from ultraviolet rays, infrared rays, and composite light rays at room temperature to reduce graphene oxide to graphene And a step of performing optical coupling so that the metal nanowire layer is impregnated and bonded to the formed graphene layer at the same time.
The stacking order of the graphene oxide layer and the metal nanowire layer formed on the substrate may be changed.
The substrate, the graphene oxide layer, and the metal nanowire layer may be stacked in this order, or the substrate, the metal nanowire layer, and the graphene oxide layer may be stacked in this order.
First, the metal nanowire layer may be formed by toppling a dispersion of metal nanowires, and at least one point of the metal nanowires may be regularly or irregularly intersected with other metal nanowires.
Wherein the metal nanowire dispersion comprises from 0.1 to 70% by weight of metal nanowires based on the total weight of the metal nanowire dispersion; 0.1 to 50% by weight of a dispersant; 0.1 to 50% by weight of a dispersion stabilizer; And 0.1 to 99.7 wt% of a solvent.
The metal nanowires may be one or more selected from the group consisting of silver nanowires, copper nanowires, nickel nanowires, gold nanowires, and iron nanowires, and the metal nanowires may have a diameter of 5 to 100 nm , And a length of 5 to 100 mu m.
In addition, two or more kinds of metal nanowires may be mixed and used in order to improve dielectric characteristics and economical efficiency of the transparent electrode. The mixing ratio may vary depending on the kind of the metal to be mixed.
When the content of the dispersant in the metal nanowire dispersion is less than the above range, the dispersed phase is difficult to be stably maintained. If the content is above the upper limit, the dielectric property of the transparent electrode may be lowered.
The dispersion stabilizer is added to stabilize the dispersion phase of the dispersion of the metal nanowire dispersion and prevent re-clustering. If the content of the dispersion stabilizer is less than the above range, it is difficult to stably maintain the dispersed phase. If the dispersion stabilizer is above the upper limit The dielectric properties of the transparent electrode may be deteriorated.
The graphene oxide dispersion may contain 0.01 to 50 wt% of graphene oxide and 50 to 99.99 wt% of solvent based on the total weight%, preferably 0.1 to 10 wt% of graphene oxide, May be contained in the balance%.
The graphene oxide dispersion may further contain a dispersant and / or a dispersion stabilizer to facilitate dispersion.
The dispersant and the dispersion stabilizer added to the metal nanowire dispersion and the graphene oxide dispersion are as defined above.
The solvent may be selected from the group consisting of distilled water, lower alcohol having 1 to 5 carbon atoms, dimethylformamide, and tetrahydrofuran. However, the present invention is not limited thereto, and any solvent that is used in the production of a transparent electrode can be applied.
Dispersing the metal nanowire dispersion and the graphene oxide dispersion into one or two or more species selected from the group consisting of an ultrasonic disperser, a stirrer, a ball mill, and a 3-roll mill to easily disperse the metal nanowire dispersion and the graphene oxide dispersion, .
According to an embodiment of the present invention, the graphene and the metal nanowire may be in a content ratio of 1:15 to 10: 1, preferably 1:10 to 1: 1, more preferably 1: 9 to 1: 2: 8 ratio.
According to one embodiment of the present invention, the substrate may be selected from the group consisting of polyimide film (PI), BT epoxy / glass fiber, polyethylene film (PT) and photopaper, and the metal nanowire dispersion and graphene The oxide dispersions may be the same or different from each other and may be independently applied to a substrate by a screen selected from screen printing, inkjet printing, gravuring, spraying and bar coater methods .
According to the present invention, the step 1) may further include a preliminary light irradiation step for independently preheating or solvent drying.
The preliminary light irradiation may be irradiated with a light source selected from ultraviolet rays, infrared rays, and composite light rays thereof. The ultraviolet rays are irradiated at an intensity of 10 to 1000 mW / cm 2 for 5 to 300 seconds during the preliminary irradiation, For 5 to 300 seconds at an intensity of 100 to 5000 W / cm < 2 >.
If the dispersion liquid applied to the substrate is not properly dried, any one selected from the ultraviolet rays, the infrared rays, and the composite light of the step 2) and the ultrafast white light are phase-changed from the liquid phase to the solid phase upon irradiation with the composite light, The bonding between the metal nanowire layer and the graphene layer may not be easy. In addition, the preheating facilitates the impregnation of the metal nanowires into the graphene during the irradiation of the composite light, facilitates the densification of the bonding site, and is therefore preferable because a transparent electrode having improved dielectric properties can be obtained.
According to the present invention, the preliminary light irradiation and the composite light irradiation in step 2) may be performed in a single step or a multi-step.
The metal nanowires are well melted or bonded at a high temperature of 600 ° C or higher, and the higher the temperature, the better the bonding. In the present invention, in order to improve the dielectric constant of the graphene / metal nanowire composite while improving the temperature of the substrate during light irradiation, any one selected from ultraviolet rays, infrared rays, Graphene and metal nanowires by local melting; Metal nanowires and other metal nanowires; The graphene and the substrate can be optically bonded.
Particularly, it is possible to impregnate the graphene with the metal nanowire so that the graphene can be bonded to the graphene, and the dielectric property can be further improved compared to the case where the graphene is not impregnated. So that it is preferable.
The impregnation may be all or part of the impregnation.
Any one selected from the ultraviolet light, the infrared light, and the composite light thereof and the extreme ultraviolet light may be simultaneously irradiated, but may be sequentially irradiated. Sometimes, white light and / or ultraviolet light may be irradiated while increasing the temperature of the substrate and coating layer by irradiating infrared rays. However, the larger the ultraviolet ray, the infrared ray, and the ultraviolet ray energy, the more unconditionally the optical coupling efficiency is not effectively generated.
The extreme ultraviolet light is irradiated from a xenon flash lamp and has a pulse width of 0.1 to 100 ms, a pulse number of 1 to 100, an intensity of 0.1 to 100 J / cm 2 And the pulse gap may be 0.1 to 100 ms.
If the pulse width is greater than 100 ms, the energy input per unit time is reduced and the efficiency of sintering may be lowered, which is uneconomical. If the pulse gap is greater than 100 ms or the number of pulses is greater than 1000, it is difficult for the metal nanowires to sinter and optical junction due to too low energy even when the intensity is less than 0.1 J /
Pulse width (0.1 to 100 ms) in the present invention, a pulse gap (0.1 to 100 ms), the pulse number (1 to 1000), strength (0.1 J / cm 2 to 100 J / cm 2) the optical joint in accordance with the change of the The conditions are different and thus the total light energy is emitted up to 100J. Sintering and optical bonding can be performed only when sufficient light energy is irradiated. The energy range for achieving this may be various, such as PI (5 ~ 50J), photo paper (3 ~ 15J), BT (10 ~ 25J) .
The ultraviolet ray may be irradiated at an intensity of 10 to 1000 mW / cm 2 for 0 to 300 seconds, and the infrared ray may be irradiated at an intensity of 100 to 5000 W / cm 2 for 0 to 300 seconds.
When the infrared irradiation energy is irradiated below the above range, it takes a long time to improve the temperature of the substrate and the coating layer. If the infrared irradiation energy exceeds the above range, the temperature of the substrate may be excessively high.
It will be apparent to those skilled in the art that various modifications and variations can be made in the present invention without departing from the spirit or scope of the present invention. Such variations and modifications are intended to be within the scope of the appended claims.
Example
Preparation Example 1. Preparation of graphene oxide dispersion.
The graphene oxide was dispersed in ethanol to prepare a graphene oxide dispersion containing 5 wt% of graphene oxide.
Production Example 2. Preparation of silver nanowire dispersion
0.5 weight% of the nanowire, 0.1 ~ 0.5 weight% of the dispersing agent, 0.1 ~ 0.5 weight% of the dispersion stabilizer, and the balance of the solvent were mixed and dispersed to prepare a silver nanowire dispersion.
Production Example 3. Preparation of Copper Nanowire Dispersion
Copper nanowire dispersions were prepared by the method of Preparation Example 2.
Production Example 4. Preparation of nickel nanowire dispersion.
A nickel nanowire dispersion was prepared by the method of Production Example 2.
Production Example 5. Preparation of gold nanowire dispersion.
A gold nanowire dispersion was prepared by the method of Production Example 2.
Production Example 6. Preparation of iron nanowire dispersion.
An iron nanowire dispersion was prepared by the method of Production Example 2.
Preparation Example 7. Preparation of silver / copper nanowire dispersion.
A silver / copper nanowire dispersion was prepared by the method of Production Example 2.
Production Example 8. Preparation of silver / gold nanowire dispersion.
A silver / gold nanowire dispersion was prepared by the method of Production Example 2.
Example 1.
The graphene oxide dispersion prepared in Preparation Example 1 was coated on a PET substrate by a bar coater method, and dried by coating with infrared rays. The metal nanowires were coated on the graphene oxide dispersion coating layer so that the content ratio of the graphene and the metal nanowire was varied, and the coating was irradiated with infrared rays to simultaneously dry the coating. Thereafter, composite light was irradiated with extreme ultraviolet light, infrared light and ultraviolet light to prepare a transparent electrode.
Example 2.
The metal nanowire dispersion prepared in Preparation Example 1 was coated on a PET substrate by a bar coater method, and dried by coating with infrared rays. The graphene oxide dispersion was coated on the metal nanowire dispersion coating layer so that the content ratio of the graphene and the metal nanowire was varied, and the coating was irradiated with infrared rays to simultaneously dry the coating. Thereafter, composite light was irradiated with extreme ultraviolet light, infrared light and ultraviolet light to prepare a transparent electrode.
Comparative Example 1
A transparent electrode was prepared in the same manner as in Example 1 except that only the extreme ultraviolet and white light was irradiated.
Test Example 1. Setting of light irradiation condition
In order to optimize the irradiation condition of the extreme ultraviolet ray, the transparent electrode was fabricated by various irradiation energy, number of pulses, and pulse width, and the dielectric constant was changed.
It was confirmed that the extreme ultraviolet-white light has the best dielectric constant when the pulse number of the xenon lamp is 1, the intensity is 19 to 21 J / cm 2 , and the pulse width is 10 ms.
When the irradiation intensity was 25 or more, the coating layer was damaged due to excessive irradiation, resulting in a decrease in the dielectric constant.
Such irradiation conditions may vary depending on the coating layer thickness, the type of dispersant or dispersion stabilizer, the type of the metal, the type and thickness of the substrate.
Test Example 2. Measurement of Dielectric Properties
Test Example 2.1
In order to measure the content ratio and dielectric property of graphene and metal nanowire, the change of electric resistance value according to the light irradiation and optical bonding was measured. (Unit: Ω / sq)
The graphene oxide dispersion was coated on the PET substrate using an infrared lamp to dry the silver nano wire / graphene oxide film for about 20 seconds, and the silver nano wire dispersion was applied thereon and dried for about 20 seconds. The irradiation condition of the infrared ray was set to 1.75 kW of power and the irradiation time of 20 seconds.
Optical coupling was performed using extreme ultraviolet white light. The light irradiation conditions were set as 1 pulse, 21 J / cm 2 intensity, and 10 ms pulse width.
As shown in Table 1, when the silver nanowire was added only, the electrical resistance was low. Especially, when the ratio of graphene to silver nanowires was 9: 1, only silver nanowires were added before light irradiation The electrical resistivity was higher than that of silver nanowire. However, after the light irradiation, the electrical resistance was lower than that of silver nanowire alone.
Also, changes in sheet resistance, haze, and permeability according to the content ratio of graphene to metal nanowire were measured and are shown in FIGS. 3 to 5.
As shown in FIGS. 3 to 5, the transparent electrode prepared using only the silver nanowire exhibited increased haze, decreased transmittance, and a very low sheet resistance reduction rate after sintering the composite light.
On the other hand, the transparent electrode prepared by using the graphene and silver nanowire together exhibited reduced haze, increased transmittance and reduction of sheet resistance after composite light sintering, and the sheet resistance reduction rate was higher as the graphene content increased And the increase in the number of workers. Especially, when the content ratio of graphene and silver nanowire was 1: 9, the sheet resistance after composite light sintering was lower than that of transparent electrode using silver nanowire alone.
Therefore, the optimum condition was set so that the ratio of graphene to silver nano wire was 1: 9.
Test Example 2.2
In order to confirm the dielectric properties according to the light irradiation using the composite light source, the light irradiation was performed in the same manner as in Test Example 2.1, except that the ultraviolet light was irradiated at the same time as the extreme ultraviolet light The optical connection was made through irradiation. At this time, the irradiation condition of the ultraviolet ray was set to be 30 mW, and the irradiation time was set to be the same as that of the white light irradiation time.
3 and 6, in the case of the composite light irradiation for simultaneously irradiating ultraviolet light and white light, the sheet resistance (32.87? / Sq) of the silver nano wire and the graphene oxide film in a region where the white light energy is smaller than that in the case of using only white light, . ≪ / RTI > This means that when ultraviolet rays are used together with white light, the reduction of graphene oxide and the consumption of white light energy for joining the silver nano wires are consumed low.
Test Example 3. Surface Observation
The surface of the transparent electrode having the graphene-silver nanowire content ratio of 1: 9 was measured by an electron microscope, which is shown in FIG. FIG. 7A shows the image before the light irradiation, and 7B shows the image after the light irradiation. Before the light irradiation, silver nanowires were simply placed on the graphene oxide layer. After the light irradiation, silver nanowires were bonded to the graphene, .
On the other hand, when irradiated only with extreme ultraviolet light, it was confirmed that silver nanowires were optically bonded to each other but not impregnated into graphene.
Claims (11)
The metal nanowires constituting the metal nanowire layer may be one or more selected from the group consisting of silver nanowires, copper nanowires, nickel nanowires, gold nanowires, and iron nanowires, At least one point is connected to the other metal nanowires in a regular or irregular crossing manner,
Wherein the metal nanowire layer is impregnated and bonded to the graphene layer through composite light irradiation for irradiating any one selected from ultraviolet light, infrared light, and composite light thereof, and extreme ultraviolet light,
Wherein the extreme ultraviolet-white light is irradiated from a xenon flash lamp and has a pulse width of 0.1 to 100 ms, a pulse number of 1 to 100, an intensity of 0.1 to 100 J / cm 2 , a pulse gap of 0.1 Wherein the ultraviolet light is irradiated at an intensity of 10 to 1000 mW / cm 2 for 0 to 300 seconds and the infrared light is irradiated at an intensity of 100 to 5000 W / cm 2 for 0 to 300 seconds. .
Wherein the transparent electrode comprises a substrate, a graphene layer formed on the substrate, and a structure of a metal nanowire layer formed on the graphene layer; Or a structure of a substrate, a metal nanowire layer formed on the substrate, and a graphene layer formed on the metal nanowire layer.
Wherein the content ratio of the graphene to the metal nanowire is 1:15 to 10: 1.
Wherein the metal nanowire has a diameter of 5 to 100 nm and a length of 5 to 100 μm.
2) The substrate on which the graphene oxide layer and the metal nanowire layer are formed is irradiated with either ultraviolet light or ultraviolet light selected from ultraviolet rays, infrared rays, and composite light rays at room temperature to reduce graphene oxide to graphene And simultaneously bonding the metal nanowire layer so that the metal nanowire layer is impregnated and bonded to the reduced graphene layer,
The extreme-wave white light is irradiated from a xenon flash lamp and has a pulse width of 0.1 to 100 ms, a pulse number of 1 to 100, an intensity of 0.1 to 100 J / cm 2 , a pulse gap of 0.1 to 100 ms, Wherein the ultraviolet light is irradiated at an intensity of 10 to 1000 mW / cm 2 for 0 to 300 seconds and the infrared ray is irradiated at an intensity of 100 to 5000 W / cm 2 for 0 to 300 seconds. And forming a transparent electrode on the transparent electrode.
Wherein the stacking order of the graphene oxide layer and the metal nanowire layer formed on the substrate is variable.
Wherein the step 1) further comprises a preliminary light irradiation step for preheating or solvent drying, wherein the preliminary light irradiation is performed by irradiation with any one of a light source selected from an ultraviolet ray, an infrared ray and a composite light thereof. A method of manufacturing a transparent electrode comprising a complex of metal nanowires.
Wherein the metal nanowire layer is formed by applying a dispersion of metal nanowires, wherein the dispersion of metal nanowires comprises 0.1 to 70% by weight of metal nanowires based on the total weight of the dispersion of metal nanowires; 0.1 to 50% by weight of a dispersant; 0.1 to 50% by weight of a dispersion stabilizer; And 0.1 to 99.7% by weight of a solvent,
The metal nanowire may be one or more selected from the group consisting of silver nanowires, copper nanowires, nickel nanowires, gold nanowires, and iron nanowires, and has a diameter of 5 to 100 nm and a length of 5 to 100 μm ego,
Wherein at least one point of the metal nanowire is regularly or irregularly intersected with other metal nanowires and connected to each other.
Wherein the content ratio of the graphene to the metal nanowire is 1:15 to 10: 1.
Priority Applications (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| KR1020140130798A KR101627422B1 (en) | 2014-09-30 | 2014-09-30 | Transparent electrode by metal nanowire with graphene oxide using complex light source with full range wavelenth and fabrication method of thereof |
| PCT/KR2015/009457 WO2016052878A1 (en) | 2014-09-30 | 2015-09-08 | Metal nanowire and graphene oxide-based transparent electrode using combined light source, and method for manufacturing same |
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| KR101976611B1 (en) * | 2016-11-24 | 2019-05-10 | 한국화학연구원 | Graphene laminated structure and method for manufacturing the same |
| CN111029037B (en) * | 2019-11-21 | 2020-11-20 | 浙江大学 | Preparation method of high-stability silver nanowire/graphene oxide composite transparent conductive film |
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| WO2012083082A1 (en) | 2010-12-15 | 2012-06-21 | Sun Chemical Corporation | Printable etchant compositions for etching silver nanoware-based transparent, conductive film |
| WO2013121912A1 (en) | 2012-02-15 | 2013-08-22 | コニカミノルタ株式会社 | Method for manufacturing transparent electrode, transparent electrode, and organic electronic element |
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| KR20110128584A (en) | 2010-05-24 | 2011-11-30 | 웅진케미칼 주식회사 | Transparent conductor comprising nanowire and method for preparation thereof |
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| WO2013121912A1 (en) | 2012-02-15 | 2013-08-22 | コニカミノルタ株式会社 | Method for manufacturing transparent electrode, transparent electrode, and organic electronic element |
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| KR101865465B1 (en) * | 2016-06-14 | 2018-06-07 | 영남대학교 산학협력단 | Manufacturing device and method of the graphene |
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