KR102044204B1 - A method for manufacturing Electrode film and Electrode film manufactured by the same - Google Patents
A method for manufacturing Electrode film and Electrode film manufactured by the same Download PDFInfo
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- KR102044204B1 KR102044204B1 KR1020150097126A KR20150097126A KR102044204B1 KR 102044204 B1 KR102044204 B1 KR 102044204B1 KR 1020150097126 A KR1020150097126 A KR 1020150097126A KR 20150097126 A KR20150097126 A KR 20150097126A KR 102044204 B1 KR102044204 B1 KR 102044204B1
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
- H01B13/00—Apparatus or processes specially adapted for manufacturing conductors or cables
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
- C23C18/16—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by reduction or substitution, e.g. electroless plating
- C23C18/31—Coating with metals
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
- H01B5/00—Non-insulated conductors or conductive bodies characterised by their form
- H01B5/14—Non-insulated conductors or conductive bodies characterised by their form comprising conductive layers or films on insulating-supports
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Abstract
The present invention relates to a method for producing an electrode film and an electrode film produced through the same.
Description
The present invention relates to a method for producing an electrode film and an electrode film produced through the same.
Recently, a technique for implementing an electrode circuit on a flexible substrate is required to implement a flexible display. For this purpose, methods using photolithography, inkjet printing, stencil printing and / or gravure printing have been developed.
Among them, an easy approach is to coat the intaglio fine pattern of the flexible substrate and to remove residues from the surface. However, the ink coating method requires additional heat firing to secure conductivity, which may damage the flexible substrate and cause volume shrinkage of the filled ink.
As another method, a method of removing the thin film on the top surface by depositing a metal thin film on the intaglio fine pattern of the flexible substrate may be performed by surface polishing. It is difficult to realize a perfect filling form on the intaglio micropattern of the flexible substrate because it is coated only on the pattern surface, and there is a problem that a lot of cost and processing time due to mechanical polishing process are consumed. In addition to this, there is a problem that the existing method has a technical limitation in implementing a pattern of 1 μm or less on the flexible substrate. In particular, the electrode circuit or pattern of the buried structure in which the metal part is filled in the intaglio pattern is a more complicated and difficult process and has not yet been commercialized by the existing process.
The prior art electrode film production method requires additional heat firing, which may damage the flexible substrate and cause volume shrinkage of the filled ink.
Accordingly, an object of the present invention is to provide an electrode film manufacturing method capable of forming a conductive micropattern from microscale to nanoscale.
That is, an object of the present invention is to provide an electrode film manufacturing method for filling an intaglio fine pattern in a solution process without using a vacuum process such as deposition etching.
In order to achieve the above object, the present invention comprises the steps of: (1) coating the catalyst solution on the surface on which the intaglio fine pattern is formed; (2) growing the aluminum thin film on the intaglio fine pattern of the flexible substrate by reacting the coated catalyst solution with the aluminum precursor solution; And (3) arranging the grown aluminum thin film provides an electrode film manufacturing method comprising a. According to a preferred embodiment of the present invention, the manufactured electrode film may include an aluminum layer thin film or an aluminum filled thin film in the intaglio fine pattern of the flexible substrate. In addition, the catalyst solution is Ti (OC 3 H 7 ) 4 (titanium tetraisopropoxide), TiCl 3 (titanium (III) chloride), TiCl 4 (titanium (IV) chloride), Ti (OnC 4 H 9 ) 4 (titanium tetra butoxide), Al 3 Ti (titanium aluminide), TiBr 4 (titanium tetrabromide), SiCl 4 (silicone tetrachloride), Ti (OEt) 4 (titanium ethoxide), VOCl 3 (vanadiumoxytri Chloride), VOCl 2 , (vanadium chloride oxide), TiCl 2 (i-OC 3 H 7 ) 2 (titaniumdichloroisopropoxide), Ti (BH 4 ) 2 .2 (OEt 2 ) (titanium tetrahydroborate Ethoxide), (NH 4 ) 2 PtCl 6 (ammonium chloroplatinate), Pt (OH) 4 (platinum hydroxide), Pt (NO 3 ) 2 (platinum nitride), Pt (NH 3 ) 4 ( NO 3 ) 2 (platinum tetra ammonium nitrate), PtCl 4 (platinum chloride), Pt (C 2 O 4 ) 2 (platinum oxalate), Pd (NO 3 ) 2 (palladium nitrate), Pd (NH 3 ) 4 (NO 3 ) 2 (palladium tetra ammonium nitrate), PdCl 2 (palladiumchloride), PdC 2 O 4 (palladium oxalate), Na 2 PdCl 4 (palladium sodium chloride) and Na 2 PtCl 6 It may include any one or more selected from the group consisting of (platinum sodium chloride). And the aluminum precursor is H 3 Al: MP, H 2 Al (BH 4 ): N (Me) 3 , H 2 Al (BH 4 ): N (Et) 3 , H 2 Al (BH 4 ): MP, H 2 Al (BH 4 ): MeN (Et) 2 , H 2 Al (BH 4 ) :( Me) 2 NEt, and H 3 AlO (C 4 H 9 ) 2 . It may include one or more. The MP is methylpyrrolidine, Me is CH 3 , Et is C 2 H 5 , N (Me) 3 is tri-methylamine, N (Et) 3 is triethylamine (Tri- ethylamine) and N (Et) 2 represent diethylamine (Di-etylamine), respectively.
Another aspect of the present invention provides an electrode film produced by the electrode film production method of the present invention. Another aspect of the present invention provides a negative electrode plate and display for a solar cell comprising the electrode film of the present invention.
The present invention can provide an electrode film manufacturing method for easily forming a conductive micropattern from microscale to nanoscale.
That is, the present invention starts the nuclear growth by the solution process and grows into a crystal thin film in the direction parallel to the plane (in-plane direction). Therefore, it is possible to form a thin film having excellent conductivity without the thermal firing process required in the particle filling method.
In addition, the present invention can facilitate large area and mass production in combination with a continuous process such as roll-to-roll, without using a vacuum process.
Furthermore, since the process of growing a thin film on the solution, there is no limitation on the thin film growth from micro pattern to tens of nano patterns. Therefore, it is possible to contribute to the expansion of functionality of the electrode element is required to minimize the conductive line width. In conclusion, it can be used as a solar cell negative plate, FPCB and OLED lighting auxiliary electrode.
1 is a schematic view of an electrode film manufacturing method according to an embodiment of the present invention.
2 is a comparative SEM photograph of the surface of the electrode film of the example and the surface not rubbed in the electrode film of the example.
3 is a photomicrograph of the electrode film of the embodiment taken in the transmission mode and reflection mode.
Figure 4 is an SEM photograph of the top and cross-section of the electrode film of the embodiment.
5 is a SEM photograph of the electrode film surface comparison example and the electrode film surface of the comparative example.
EMBODIMENT OF THE INVENTION Hereinafter, this invention is demonstrated in detail. The following detailed description is for the description of one embodiment of the present invention, although not limited to the scope of the claims defined by the claims.
The method of manufacturing an electrode film using the ink of the prior art requires additional heating. And there is a problem that can damage the flexible substrate, can cause volume shrinkage of the filled ink. In addition, in order to have an electrode film having a buried structure, a process of removing the structural material on the top surface after ink coating or front deposition may be considered. However, it is difficult to implement a perfect filling form, and there is a problem that a lot of cost and processing time due to the mechanical polishing process are consumed. In addition, there is a problem that the existing photolithography method has a complex and technical limitation in implementing a pattern of 1 μm or less on a flexible substrate.
Accordingly, the present inventors have made diligent efforts to solve the above problems, and found that when embedding the negative fine pattern of the electrode film using a solution process, a sufficient embedded electrode film can be manufactured without additional processes and costs.
The present invention relates to an electrode film manufacturing method in which a fine conductive pattern is formed by forming an intaglio fine pattern on a flexible substrate and then growing aluminum, which is one of the conductive materials, in a solution process.
That is, the present invention comprises the steps of: (1) coating the catalyst solution on the surface on which the intaglio fine pattern is formed; (2) growing the aluminum thin film on the intaglio fine pattern of the flexible substrate by reacting the coated catalyst solution with the aluminum precursor solution; And (3) arranging the grown aluminum thin film provides an electrode film manufacturing method comprising a.
1 is a schematic view of an electrode film manufacturing method according to an embodiment of the present invention. Specifically, (a) using a hard mold of the embossed fine pattern to copy the pattern to the transparent polymer mold by the imprint process, (b) to induce the nuclear growth of the aluminum thin film on the transparent polymer mold with the pattern Coating catalyst solution. (c) The coated transparent polymer mold is immersed in an aluminum precursor ink solution, and reacted at room temperature to 140 ° C. to form an aluminum thin film. A thin film of an aluminum layer is formed along the surface of the intaglio fine pattern of the transparent polymer mold. (d) After completion of the reaction, in the state where the solvent of the precursor ink solution is not completely dried, the structure of the transparent polymer mold is removed by rubbing the structure other than the intaglio pattern, and the aluminum thin film is further polished in the intaglio fine pattern. . As a result, an unnecessary aluminum thin film on the surface other than the intaglio fine pattern may be removed, and an electrode film including an aluminum filled thin film completely filled in the intaglio fine pattern may be manufactured.
Hereinafter, the electrode film manufacturing method of this invention is demonstrated.
The present invention may include the step of forming an intaglio micropattern on the flexible substrate, and may be performed by a commonly available method. Preferably, it may be performed by an imprint process. That is, according to a preferred embodiment of the present invention, before the step (1) may include the step of forming a negative pattern by the imprint process on the flexible substrate using a hard (hard) mold formed with the relief fine pattern . In general, the method of forming the intaglio fine pattern on the flexible substrate is hardly possible by direct imprinting method, so the method of copying using the hard mold is used. In other words, the imprint process means a duplication process as a print process to be imprinted. For example, an imprint fine pattern is formed on a flexible substrate by using a hard mold, a polymer resin, or the like having an embossed fine pattern formed thereon. And this may be any method that can be used commonly.
That is, the flexible substrate on which the intaglio fine pattern is formed may have a form in which a polymer resin having an intaglio fine pattern is formed on one surface of the flexible substrate.
In the present invention, the polymer resin may be used a conventional polymer material, preferably may include any one or more selected from a photocurable polymer and a thermosetting polymer, more preferably may be a photocurable polymer. The photocurable polymer may include one or more selected from the group consisting of polyolefins, (meth) acrylate resins, urethane resins, epoxy resins, and imide resins. The hard mold may be made in various ways such as photolithography, e-beam or interferance lithography.
And the flexible substrate of the present invention may be used as usual. According to a preferred embodiment of the present invention, the flexible substrate is polyethylene terephthalate (PET), polycarbonate (PC), polymethyl methacrylate (Poly (methyl methacrylate), PMMA), polyvinyl alcohol Plastic substrates including at least one selected from the group consisting of (Polyvinylalcohol, PVA), polyethylene naphthalate (PEN), polyester sulfone (PES), and ethylene vinyl acetate (Ethylene vinylacetate, EVA); Glass substrates; It may include one or more selected from the group consisting of a quartz (Quartz) substrate.
The conditions of the imprint process in this step may be what is normally available.
The engraved fine pattern is not limited to a structural design for forming a conductive surface. In general, the intaglio fine pattern may introduce an interconnected network structure. Preferably, the intaglio fine pattern may include one or more types selected from a mesh form, a Voronoi diagram form, and a stripe form.
Specifically, when a structure having a point of contact point is required in order to impart conductivity in the front direction of the conductive substrate, it may take a mesh form or a Voronoi form, and the mesh may be an orthogonal form. The Voronoi diagram form has a random shape, and in order to form an anisotropic conductive surface, a stripe shape may be preferable.
The engraved fine pattern formed on the flexible substrate in this step is formed corresponding to the hard mold of the embossed fine pattern. The width of the intaglio fine pattern is not limited. This can make the line width wider enough by adjusting the ratio of the aperture ratio (line width to line spacing ratio) even if the width is not a problem even when the moiré phenomenon and the constant transmittance level are increased. However, the transparent electrode may be 3 μm or less, more preferably 1 μm or less in order to avoid a moire phenomenon.
According to a preferred embodiment of the present invention, the depth of the intaglio fine pattern is 50nm ~ 5um, preferably 200nm ~ 3um. If the depth of the intaglio fine pattern is less than 50 nm or more than 5um, the aluminum buried structure may not be effectively implemented.
In the present invention, the thickness of the flexible substrate and the polymer may be used.
Next, step (1) will be described.
In this step, the catalyst solution for nucleation of the aluminum thin film is coated on the surface on which the negative fine pattern of the flexible substrate is formed. The catalyst solution may be coated on the entire surface of the flexible substrate on which the intaglio pattern is formed. Alternatively, only the intaglio fine pattern portion may be coated, and an additional step may be required to coat only the intaglio fine pattern portion.
And the coating method in this step may be any method that can be used commonly, for example, it can be carried out by applying a spin coating method, dip coating method, spray coating method or bar coating method, preferably spray coating Law can be used.
According to a preferred embodiment of the present invention, the catalyst solution is Ti (OC 3 H 7 ) 4 (titanium tetraisopropoxide), TiCl 3 (titanium (III) chloride), TiCl 4 (titanium (IV) chloride) Ti (OnC 4 H 9 ) 4 (titanium tetra butoxide), Al 3 Ti (titanium aluminide), TiBr 4 (titanium tetrabromide), SiCl 4 (silicone tetrachloride), Ti (OEt) 4 (titanium ethoxide ), VOCl 3 (vanadiumoxytrichloride), VOCl 2 (vanadium chloride oxide), TiCl 2 (i-OC 3 H 7 ) 2 (titaniumdichloroisopropoxide), Ti (BH 4 ) 2 · 2 (OEt 2 ) (titanium tetrahydroborate ethoxide), (NH 4 ) 2 PtCl 6 (ammonium chloroplatinate), Pt (OH) 4 (platinum hydroxide), Pt (NO 3 ) 2 (platinum nitride), Pt (NH 3 ) 4 (NO 3 ) 2 (platinum tetra ammonium nitrate), PtCl 4 (platinum chloride), Pt (C 2 O 4 ) 2 (platinum oxalate ), Pd (NO 3 ) 2 (palladium nitrate), Pd (NH 3 ) 4 (NO 3 ) 2 (palladium tetra ammonium nitrate), PdCl 2 (palladiumchloride), PdC 2 O 4 (palladium oxalate), It may include any one or more selected from the group consisting of Na 2 PdCl 4 (palladium sodium chloride) and Na 2 PtCl 6 (platinum sodium chloride). Preferably it may include Ti (OC 3 H 7 ) 4 . The solvent may be any conventionally available one.
Next, step (2) will be described.
In the step (1), the flexible substrate coated with the catalyst solution is immersed in the aluminum precursor solution and reacted to form an aluminum thin film on the negative fine pattern of the flexible substrate. That is, in this step, an aluminum thin film may be formed along the surface of the catalyst coating regardless of the scale of the pattern due to the catalyst solution. For example, when the catalyst solution is coated on the entire surface, aluminum also grows to the entire surface.
According to a preferred embodiment of the present invention, the aluminum precursor in the total weight percentage of the aluminum precursor solution may include 0.1 to 30% by weight, preferably 1 to 10% by weight, but is not limited thereto. And the remaining amount can be 100% by weight with a solvent. If the aluminum precursor is less than 0.1 wt%, there may be a problem that a sufficient thin film may not be formed, and if the aluminum precursor exceeds 30 wt%, there may be a problem in chemical stability of a solution such as precipitation before the reaction. The aluminum precursor may be a conventional compound which may be converted into aluminum by heat treatment, and may preferably include one or more selected from aluminum hydrogen compounds and alan series compounds. For example, H 3 Al: MP, H 2 Al (BH 4 ): N (Me) 3 , H 2 Al (BH 4 ): N (Et) 3 , H 2 Al (BH 4 ): MP,
The solvent may be any conventionally available one. Preferably, an ether solvent including at least one selected from the group consisting of dimethyl ether, dibutyl ether, tetrahydrofuran and dioxane; And toluene; It may include any one or more selected from.
Specifically, in the reaction of the present step, the aluminum precursor in the aluminum precursor solution is converted to aluminum, and in the process, the aluminum bond may be increased to form an aluminum thin film. The reaction of this step is reacted at a temperature of 20 ~ 140 ℃, preferably 60 ~ 100 ℃, there is a difference in the reaction rate depending on the temperature. And if the temperature is less than 20 ℃, there may be a problem that the thin film is formed slowly and the crystal quality of the thin film is degraded, if the temperature exceeds 140 ℃ may be a problem of damage to the flexible substrate. That is, it is possible to prevent the generation of pores and the like in the aluminum thin film while sufficiently inducing the conversion and sintering of the aluminum precursor to aluminum in the above range. And the reaction time is not particularly limited, but may be adjusted according to the temperature in consideration of the conversion efficiency of the metal precursor, etc., preferably for 1 minute to 3 hours, more preferably 1 minute to 30 minutes can be carried out. .
The electrode film may include an aluminum layer thin film form or an aluminum filled thin film form in the engraved fine pattern. It can be prepared by adjusting as needed.
According to a preferred embodiment of the present invention, (3) arranging the grown aluminum thin film; may include. In the present invention, by including the step (3), it is possible to remove the aluminum thin film formed unnecessary on the flexible substrate. In addition, the electrode film may be completed by trimming or filling the aluminum thin film grown on the intaglio fine pattern. That is, after the completion of the reaction of step (2) is dried at room temperature, in the state that the solvent of the aluminum precursor solution is not completely dried, the unnecessary aluminum thin film grown on the surface other than the negative pattern of the flexible substrate by rubbing (rubbing) with a cloth can do. In addition, by performing the present step, not only the unnecessary aluminum thin film may be removed, but also aluminum particles may be additionally filled in the intaglio fine pattern of the flexible substrate to form a more compact aluminum thin film. In more detail, the aluminum thin film formed by solution growth may be easily removed since the surface of the aluminum thin film is not completely bonded to the substrate surface before drying. Therefore, in the process of removing the surface thin film surface of the top surface except the intaglio fine pattern portion, additional filling is made in the intaglio fine pattern portion. In the drying step performed as an additional step, the aluminum thin film is completely bonded to the inside or the surface of the intaglio fine pattern part.
According to a preferred embodiment of the present invention, the electrode film prepared in the present invention may include an aluminum layer thin film or an aluminum filled thin film in the intaglio fine pattern of the flexible substrate, preferably may include an aluminum filled thin film. The aluminum layer thin film refers to a shape covered along the surface of the negative fine pattern of the flexible substrate. In addition, the aluminum-filled thin film means a form completely filled in the intaglio fine pattern of the flexible substrate.
The aluminum layer thin film or the aluminum filled thin film may be adjusted according to reaction conditions, for example, time or temperature, but the aluminum filled thin film may be advantageous as the line width is narrower. At the same time, however, the depth of the intaglio must also be considered.
On the other hand, after the step (3) it may be further performed a drying treatment step. Through this, the solvent remaining in the aluminum thin film formed by solution growth can be removed. After the solvent is completely dried through this step, the surface bond of the flexible substrate is firmly maintained due to the combination of oxygen and aluminum, which is relatively high at the interface of the flexible substrate, together with the formation of a natural oxide thin film, so that separation does not occur.
And additionally, the step (1) and (2), between the step (2) and (3) and / or after step (3) may further perform a drying treatment or washing step. In the present invention, the drying treatment step and / or the washing step may be any conventionally available method.
Meanwhile, when forming an aluminum thin film using a conventional particle filling method according to the prior art, a thermoplastic firing process is required.
However, in the present invention, by performing a solution process using an aluminum precursor solution, the growth process of the aluminum thin film starts to grow the nucleus, and grows as a crystal thin film in the in-plane (in-plane) direction. Therefore, a thin film having excellent conductivity is formed without a thermal firing process.
In addition, the process of growing an aluminum thin film through the solution process of the present invention can be applied to the expansion of the functionality of the transparent electrode element, such as metal mesh that requires a minimum conductive line width because there is no limit to the growth of the aluminum thin film from micro-pattern to tens of nano-nano pattern Do.
In addition, the present invention facilitates large area and mass production in combination with a continuous process such as roll-to-roll without using a vacuum process.
That is, conventionally, vacuum deposition, such as e-beam evaporation, sputtering, or physical chemical deposition, is used to manufacture high quality metal thin films or structures. However, this process must be carried out in a vacuum, the loss of the raw material source during the deposition process is a disadvantage.
Therefore, the present invention can efficiently mass-produce an electrode film, which is a functional film, by combining a solution process for producing a high quality aluminum thin film without a vacuum process and a roll-to-roll process capable of producing a continuous process.
Another aspect of the present invention provides an electrode film produced by the electrode film production method of the present invention. Another aspect of the present invention provides a negative electrode plate and display for a solar cell comprising the electrode film of the present invention, the display may be an FPCB, OLED lighting auxiliary electrode and the like.
In conclusion, in the present invention, an electrode film may be manufactured by forming an aluminum thin film by a solution process using an aluminum precursor solution.
Hereinafter, the present invention will be described in more detail with reference to Examples, but embodiments of the present invention disclosed below are exemplified to the last, and the scope of the present invention is not limited to these embodiments. The scope of the invention is indicated in the appended claims, and moreover contains all modifications within the meaning and range equivalent to the claims. In addition, "%" and "part" which show content in a following example and a comparative example are a basis of weight unless there is particular notice.
Preparation
A quartz master with a grid spacing of 40 um x 40 um, line width of 1 um, height of 1 um, and an effective area of 110 mm x 110 mm was fabricated using photolithography to produce a hard mold with an embossed mesh pattern.
Example
(1) UV-cured polyurethane acrylate (PUA) purchased from Minuta Technology was applied to the hard mold prepared in Preparation Example by spin coating (500 rpm, 30 seconds). The PET flexible substrate, which was a film for replication, was placed on top and separated after lamination and UV curing (90 seconds exposure, 90 seconds additional exposure after substrate separation). Thereafter, a film substrate on which a 5 um PUA resin cured layer having a negative micropattern (
(2) A catalyst solution having a concentration of titanium isopropoxide (Ti (OC 3 H 7 ) 4 ) of 2 ul / ml was prepared in a solution of toluene. The catalyst solution was coated on the flexible substrate on which the negative fine pattern was formed at 1500 rpm for 20 seconds using a spin coater. The coated substrate was dried at 70 ° C. for 5 minutes to remove toluene.
(3) 3 wt% of methylpyrrolidine alane aluminum precursor solution was poured into a solution of dibutyl ether solvent in a bath and heated to 80 ° C. And the catalyst was immersed in a dry flexible substrate coated with a catalyst. Thin film firing started within a few seconds after the substrate was immersed. After 5 minutes, the thin film growth was completed with an aluminum crystal phase of about 200 nm thick on the surface of the flexible substrate.
(4) The substrate was washed with dibutyl ether and dried at room temperature for about 10 minutes. After some of the solvent was dried, the uppermost aluminum thin film was removed by rubbing with a soft cloth and further dried for about 1 hour to obtain an electrode film having a final aluminum buried structure.
Comparative example
150 nm aluminum was deposited on the PUA replica film manufactured in the same manner as in Example using an electron beam evaporator. After deposition, rubbing was attempted using a cloth as in Example.
Experimental Example One
The electrode film prepared in the above example was observed using an SEM, and is shown in FIG. 2.
Figure 2 is a surface of the electrode film of the embodiment, an image taken on an enlarged surface of the surface not rubbed in the electrode film of the embodiment, and the surface rubbed in the electrode film of the embodiment on the same substrate.
After rubbing through Figure 2 it can be seen that the aluminum thin film of the top end of the flexible substrate is completely removed, only the mesh (mesh) of the aluminum thin film remains.
Experimental Example 2
The rubbing surface of the electrode film prepared in Example was observed using a Olympus optical microscope (BX51M) to observe the transmission and reflection modes of the microscope, as shown in FIG. 3.
(A) is a 5 times transmission mode, (b) is a 100 times transmission mode and (c) is a photograph of the reflection mode at 100 times. In the photo of FIG. 3, an aluminum thin film was simultaneously formed on the intaglio fine pattern of the electrode film prepared as an example, and defects such as breakage of the mesh part were not found.
Experimental Example 3
The surface and the cross section, which are the top surface of the electrode film prepared in the above Example, were observed using SEM, and are shown in FIG.
4 (a) and 4 (b) are top and cross sections of the electrode film not rubbed. An aluminum thin film is also formed on the aluminum thin film and the intaglio fine pattern covering the entire electrode film. 4 (c) and 4 (d) are top and cross sections of the rubbed electrode film. The aluminium thin film at the top end is removed and additional aluminum filling occurs by rubbing, so that the pattern of the recess is completely filled and flatly filled.
Experimental Example 4
Surfaces of the electrode films prepared in Examples and Comparative Examples were observed using SEM, and are shown in FIG. 5.
(A) is the surface which rubbed the electrode film of an Example, (b) is the surface of the electrode film of a comparative example.
As shown in FIG. 5, in the comparative example, damage to the vertical wall thin film was found, and it may be confirmed that perfect filling did not occur. (Line width 1um, depth 1um)
Claims (9)
(2) growing the aluminum thin film on the intaglio fine pattern of the flexible substrate by reacting the coated catalyst solution with the aluminum precursor solution; And
(3) drying and arranging the grown aluminum thin film to fill aluminum with the engraved fine pattern of the flexible substrate.
Forming a negative fine pattern on the flexible substrate by an imprint process using a hard mold having an embossed fine pattern formed before the step (1).
The intaglio fine pattern is an electrode film manufacturing method characterized in that it comprises at least one type selected from the form of a mesh, a Voronoi diagram and a stripe.
The depth of the intaglio fine pattern is an electrode film manufacturing method, characterized in that 50nm ~ 5um.
The catalyst solution comprises Ti (OC 3 H 7 ) 4 (titanium tetraisopropoxide), TiCl 3 (titanium (III) chloride), TiCl 4 (titanium (IV) chloride), Ti (OnC 4 H 9 ) 4 ( Titanium tetrabutoxide), Al 3 Ti (titanium aluminide), TiBr 4 (titanium tetrabromide), SiCl 4 (silicon tetrachloride), Ti (OEt) 4 (titanium ethoxide), VOCl 3 (vanadium oxytrichloride) , VOCl 2 (vanadium chloride oxide), TiCl 2 (i-OC 3 H 7 ) 2 (titaniumdichloroisopropoxide), Ti (BH 4 ) 2 · 2 (OEt 2 ) (titanium tetrahydroborate ethoxide) , (NH 4 ) 2 PtCl 6 (ammonium chloroplatinate), Pt (OH) 4 (platinum hydroxide), Pt (NO 3 ) 2 (platinum nitride), Pt (NH 3 ) 4 (NO 3 ) 2 (platinum tetraammonium nitrate), PtCl 4 (platinum chloride), Pt (C 2 O 4 ) 2 (platinum oxalate), Pd (NO 3 ) 2 (palladium nitrate), Pd (NH 3 ) 4 (NO 3 ) Selected from the group consisting of 2 (palladium tetra ammonium nitrate), PdCl 2 (palladium chloride), PdC 2 O 4 (palladium oxalate), Na 2 PdCl 4 (palladium sodium chloride) and Na 2 PtCl 6 (platinum sodium chloride) Electrode film production method characterized in that it comprises any one or more.
The aluminum precursor in the total weight percentage of the aluminum precursor solution, the electrode film manufacturing method characterized in that it comprises 0.1 to 30% by weight.
The aluminum precursor is an electrode film manufacturing method characterized in that it comprises at least one selected from aluminum hydride and alan-based compounds.
The aluminum precursor is H 3 Al: MP, H 2 Al (BH 4 ): N (Me) 3 , H 2 Al (BH 4 ): N (Et) 3 , H 2 Al (BH 4 ): MP, H 2 At least one selected from the group consisting of Al (BH 4 ): MeN (Et) 2 , H 2 Al (BH 4 ) :( Me) 2 NEt and H 3 AlO (C 4 H 9 ) 2; Electrode film manufacturing method comprising a.
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| Publication number | Priority date | Publication date | Assignee | Title |
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| JP2001262359A (en) | 2000-03-22 | 2001-09-26 | Sumitomo Osaka Cement Co Ltd | Coating liquid for forming catalyst film, method for forming transparent conductive film and transparent conductive film |
| JP2010157427A (en) * | 2008-12-26 | 2010-07-15 | Nissha Printing Co Ltd | Transparent conductive sheet and its manufacturing method, and decorative mold goods |
| KR101345101B1 (en) * | 2012-12-10 | 2013-12-26 | 한국기계연구원 | Method for manufacturing conductive metal thin layer, electrode thereby, organic optoelectronic device, battery and solar cell including the electrode |
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| JP4616066B2 (en) | 2005-04-26 | 2011-01-19 | 株式会社リコー | Method for forming embedded fine pattern |
| KR101555015B1 (en) * | 2012-12-28 | 2015-09-22 | 주식회사 잉크테크 | Method for manufacturing conductive pattern |
| KR101624303B1 (en) * | 2013-04-26 | 2016-05-27 | 한국과학기술원 | Electrode of polymer nanofiber coated with aluminum thin film and manufacturing method thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2001262359A (en) | 2000-03-22 | 2001-09-26 | Sumitomo Osaka Cement Co Ltd | Coating liquid for forming catalyst film, method for forming transparent conductive film and transparent conductive film |
| JP2010157427A (en) * | 2008-12-26 | 2010-07-15 | Nissha Printing Co Ltd | Transparent conductive sheet and its manufacturing method, and decorative mold goods |
| KR101345101B1 (en) * | 2012-12-10 | 2013-12-26 | 한국기계연구원 | Method for manufacturing conductive metal thin layer, electrode thereby, organic optoelectronic device, battery and solar cell including the electrode |
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