WO2020122370A1 - 투명전도막의 제조방법 - Google Patents

투명전도막의 제조방법 Download PDF

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Publication number
WO2020122370A1
WO2020122370A1 PCT/KR2019/011686 KR2019011686W WO2020122370A1 WO 2020122370 A1 WO2020122370 A1 WO 2020122370A1 KR 2019011686 W KR2019011686 W KR 2019011686W WO 2020122370 A1 WO2020122370 A1 WO 2020122370A1
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Prior art keywords
seed layer
forming
layer
substrate
photoresist layer
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PCT/KR2019/011686
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English (en)
French (fr)
Korean (ko)
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이석재
민우식
오찬권
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하이엔드테크놀로지(주)
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Priority claimed from KR1020190026171A external-priority patent/KR102260382B1/ko
Application filed by 하이엔드테크놀로지(주) filed Critical 하이엔드테크놀로지(주)
Publication of WO2020122370A1 publication Critical patent/WO2020122370A1/ko

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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
    • H01B13/0026—Apparatus for manufacturing conducting or semi-conducting layers, e.g. deposition of metal
    • 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
    • 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
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
    • H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
    • H01L21/027—Making masks on semiconductor bodies for further photolithographic processing not provided for in group H01L21/18 or H01L21/34
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
    • H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
    • H01L21/04—Manufacture or treatment of semiconductor devices or of parts thereof the devices having potential barriers, e.g. a PN junction, depletion layer or carrier concentration layer
    • H01L21/18—Manufacture or treatment of semiconductor devices or of parts thereof the devices having potential barriers, e.g. a PN junction, depletion layer or carrier concentration layer the devices having semiconductor bodies comprising elements of Group IV of the Periodic Table or AIIIBV compounds with or without impurities, e.g. doping materials
    • H01L21/28—Manufacture of electrodes on semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/268
    • H01L21/283—Deposition of conductive or insulating materials for electrodes conducting electric current
    • H01L21/288—Deposition of conductive or insulating materials for electrodes conducting electric current from a liquid, e.g. electrolytic deposition
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
    • H01L21/70—Manufacture or treatment of devices consisting of a plurality of solid state components formed in or on a common substrate or of parts thereof; Manufacture of integrated circuit devices or of parts thereof
    • H01L21/71—Manufacture of specific parts of devices defined in group H01L21/70
    • H01L21/768—Applying interconnections to be used for carrying current between separate components within a device comprising conductors and dielectrics
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L31/00—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
    • H01L31/02—Details
    • H01L31/0224—Electrodes
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L31/00—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
    • H01L31/18—Processes or apparatus specially adapted for the manufacture or treatment of these devices or of parts thereof
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
    • Y02P70/50—Manufacturing or production processes characterised by the final manufactured product

Definitions

  • the present invention relates to a method for manufacturing a transparent conductive film.
  • the transparent conductive film manufactured by the manufacturing method according to the embodiment of the present invention can be widely applied to fields such as a touch panel, an electromagnetic shielding film, a solar cell, and a window.
  • the transparent conductive film can produce a product having a large area, and can have a high permeability and a response speed.
  • the transparent conductive film means a film that has electrical conductivity while simultaneously transmitting light. Recently, as electronic devices such as smartphones have been developed, they have been applied to various fields. Since the transparent conductive film can sense a change in electrical properties (resistance, etc.) according to the contact of the upper part, it can be applied to a touch panel, a sensor, and the like, and can be applied to a display applied thereto. In addition, it can be applied to solar cells and windows requiring light transmission, and recently, its use has been expanded to an electromagnetic wave shielding film that blocks electromagnetic waves.
  • ITO indium tin oxide
  • An object of the present invention is to provide a method for manufacturing a transparent conductive film having a large area. In addition, it is possible to provide a transparent conductive film having high transmittance and high response speed.
  • the method of manufacturing a transparent conductive film according to an embodiment of the present invention provides a means for effectively removing the seed layer on the photoresist layer. Through this, it is possible to prevent the seed layer from remaining on unnecessary portions on the substrate, and the electroless plating process can be stably performed, thereby improving process yield and efficiency. In addition, after forming a copper thin film by an electroless plating process, it is possible to improve productivity by more easily forming a copper thin film by using the electroplating process.
  • a method of manufacturing a transparent conductive film according to an embodiment of the present invention includes forming a photoresist layer on a substrate; Forming a pattern by removing a portion of the photoresist layer so that a portion of the substrate is exposed to the outside; Forming a seed layer on the substrate and the photoresist layer where the part is exposed to the outside; Modifying at least a portion of the surface of the seed layer; Forming a first plating film on a seed layer formed on a substrate on which a portion is exposed to the outside by performing electroless plating; And removing the photoresist layer.
  • a method of manufacturing a transparent conductive film includes forming a photoresist layer on a substrate; Forming a pattern by removing a portion of the photoresist layer so that a portion of the substrate is exposed to the outside; Forming a first seed layer on the substrate and the photoresist layer where the part is exposed to the outside; Modifying at least a portion of the surface of the first seed layer; Forming a second seed layer on the first seed layer formed on the substrate where the part is exposed to the outside; Forming a first plating film on the second seed layer by performing electroless plating; And removing the photoresist layer.
  • a method of manufacturing a transparent conductive film according to another embodiment of the present invention includes forming a photoresist layer on a substrate; Forming a pattern by removing a portion of the photoresist layer so that a portion of the substrate is exposed to the outside; Forming a seed layer on the substrate and the photoresist layer where the part is exposed to the outside; Modifying at least a portion of the surface of the seed layer; Removing the photoresist layer; And performing electroless plating to form a first plated film on the seed layer formed on the substrate where the part is exposed to the outside.
  • a method of manufacturing a transparent conductive film according to another embodiment of the present invention includes forming a photoresist layer on a substrate;
  • Forming a first plating film on the second seed layer by performing electroless plating It includes.
  • the step of modifying at least a portion of the surface may be to selectively remove the seed layer or the first seed layer on the photoresist layer.
  • the step of modifying at least a portion of the surface may be performed by spraying a mass on the seed layer or the first seed layer on the photoresist layer.
  • the method of injecting the mass may be to inject the mass so as to have a predetermined angle from a direction perpendicular to the photoresist layer.
  • the mass body may be a sublimation material, and preferably, the sublimation material may be any one of dry ice, naphthalene, and iodine.
  • the second seed layer may include palladium (Pd).
  • the method for manufacturing a transparent conductive film according to an embodiment of the present invention may further include a step of forming a second plating film on the first plating film by performing an electroplating process.
  • the method for manufacturing a transparent conductive film according to an embodiment of the present invention may provide a method for manufacturing a transparent conductive film having a large area. Further, it is possible to provide a transparent conductive film having high transmittance and high response speed.
  • the method of manufacturing a transparent conductive film according to an embodiment of the present invention provides a means for effectively removing the seed layer on the photoresist layer. Through this, it is possible to prevent the seed layer from remaining on unnecessary portions on the substrate, and the electroless plating process can be stably performed, thereby improving process yield and efficiency.
  • the electroless plating process can be performed efficiently and economically.
  • 1 to 6 illustrate a method of manufacturing a transparent conductive film according to an embodiment of the present invention.
  • FIG. 7 to 13 illustrate a method of manufacturing a transparent conductive film according to another embodiment of the present invention.
  • 16 and 17 illustrate a method of manufacturing a transparent conductive film according to another embodiment of the present invention.
  • Forming a first plating film on the second seed layer by performing electroless plating may include.
  • the seed layer or the first seed layer on the photoresist layer may be selectively removed.
  • It may be performed by spraying a mass on the seed layer or the first seed layer on the photoresist layer.
  • the mass body may be sprayed to have a predetermined angle from a direction perpendicular to the photoresist layer.
  • the mass body may be a sublimation material.
  • the sublimation material may be any one of dry ice, naphthalene and iodine.
  • the second seed layer may include palladium (Pd).
  • Forming a second plating film on the first plating film by performing an electroplating process may further include a.
  • a method of manufacturing a transparent conductive film according to an embodiment of the present invention includes forming a photoresist layer 120 on a substrate 110; Forming a pattern by removing a portion of the photoresist layer 120 so that a portion of the substrate 110 is exposed to the outside; Forming a seed layer 130 on the substrate 110 and the photoresist layer 120 where the part is exposed to the outside; Modifying at least a portion of the surface of the seed layer 130; Forming a first plating layer 150 on the substrate 110 partially exposed by performing electroless plating; And removing the photoresist layer 120.
  • the substrate 110 is not particularly limited as long as the conductive wiring (conductive film) can be disposed thereon, and may be formed of a material that can transmit light.
  • the substrate 110 may be a rigid substrate 110, such as glass, sapphire, or silicon wafer, such as polyimide, polyethylene terephthalate, and propylene glycol polycarbonate (PC). It may be a flexible substrate 110 including plastic.
  • the step of forming the photoresist layer 120 on the substrate 110 may be performed by applying a photoresist that is a photosensitive material on the substrate 110.
  • the coating method may be a solution coating of a liquid photoresist, and is not particularly limited.
  • the photoresist is aromatic bis-azide, methacrylic acid ester, cinnamic acid ester, polymethyl methacrylate, naphthoquinone diazide (Naphthoquinonediazide), polybutene-1 sulfone (Polybutene-1 sulfone) and diazonaphthoquinone (diazonaphthoquinone)-may include at least one of novolak resin (DNQ/NR).
  • DNQ/NR novolak resin
  • a step of forming a pattern by removing a portion of the photoresist layer 120 is performed so that a portion of the substrate 110 is exposed to the outside (see FIG. 1 ).
  • This step includes disposing a mask on the photoresist layer 120, reacting a portion of the photoresist layer 120 by shining light of a specific wavelength on the mask (exposure step) and the photoresist layer And removing the reacted portion of the 120 (development step).
  • the mask may include a pattern groove in which a portion in which conductive wiring is formed is perforated.
  • the light used in the exposure step may be of UV wavelength and may be selected as suitable for photoresist.
  • the method of removing the photoresist layer 120 in the developing step may be performed by treating the reacted photoresist layer 120 with a developer.
  • the developer may include a developer, a composition agent, and an oxidation inhibitor.
  • the developer may function to reduce silver halide.
  • a post treatment with dilute acid may be further included to suppress the development reaction.
  • an intaglio pattern may be formed such that a region of the substrate 110 corresponding to the pattern groove of the mask is exposed to the outside between the photoresist layers 120.
  • the intaglio pattern may be a lattice shape or a mesh shape, and is not particularly limited.
  • the depth of the intaglio pattern may be 2 to 50 ⁇ m, preferably 5 to 30 ⁇ m, if necessary, the width of the intaglio pattern may be 2 to 50 ⁇ m, preferably 5 to 30 ⁇ m, and the interval between the intaglio patterns is 50 To 1000 ⁇ m, preferably 200 to 800 ⁇ m.
  • the seed layer 130 is a base for forming the first plating layer 150 afterwards, and may be formed of a conductive material that can stably form the first plating layer 150.
  • the seed layer 130 may include any one of TiN, TiW, and Cu conductive materials.
  • Methods for forming the seed layer 130 include a sputtering method, a chemical vapor deposition (CVD) method, a spin coating method, and an electroless plating method.
  • a sputtering method by forming the seed layer 130 using a sputtering method, the thickness of the thin film can be accurately controlled and a thin film can be formed.
  • Cu is used as the seed layer 130 by using an electroless plating method.
  • a step of modifying at least a portion of the surface of the seed layer 130 is performed (see FIG. 3 ).
  • the "modifying at least a part of the surface” means physically or chemically changing the properties of the surface of the seed layer 130, and is separated from the crack or photoresist layer 120 in a part of the seed layer 130. It may mean that such a phenomenon has occurred. Through this, the seed layer 130 on the photoresist layer 120 may be selectively removed.
  • the step of modifying at least a portion of the surface may be performed by spraying the mass 140 on the seed layer 130 or the seed layer 130 on the photoresist layer 120.
  • the method of injecting the mass body 140 may be to inject the mass body 140 to have a predetermined angle from a direction perpendicular to the photoresist layer. Referring to FIG. 3, it can be seen that the mass body 140 is injected in a direction inclined at a predetermined angle ⁇ with respect to a direction (dotted line) perpendicular to the photoresist layer 120. Through this, the mass body 140 may be controlled to collide with the seed layer 130 disposed on the photoresist layer 120, but not collide with the seed layer 130 disposed on the substrate 110.
  • the angle at which the mass body 140 is incident may be 20 to 70° with respect to a direction perpendicular to the photoresist layer 120.
  • the angle at which the mass body 140 is incident is less than 20°, a problem that the mass body 140 collides with the seed layer 130 on the substrate 110 may occur.
  • the angle at which the mass body 140 is incident is greater than 70°, the surface modification of the seed layer 130 may not sufficiently occur because the mass body 140 does not transmit a sufficient amount of impact to the seed layer 130.
  • the mass body 140 may have a mass capable of delivering an impact amount sufficient to modify the surface of the seed layer 130, and when entering at a predetermined angle, does not flow between patterns formed in the photoresist layer 120. It is desirable to have a size that is unlikely. To this end, the average diameter of the mass 140 entering the seed layer 130 in this step may be 5 ⁇ m or more, more preferably 10 ⁇ m or more.
  • the mass body 140 may be a sublimation material, and preferably, the sublimation material may be any one of dry ice, naphthalene, and iodine.
  • the sublimation material may be any one of dry ice, naphthalene, and iodine.
  • the mass body 140 since the mass body 140 is vaporized after colliding with the seed layer 130, byproducts may not be present on the seed layer 130. Therefore, only the seed layer 130 on the photoresist layer 120 can be modified by a simple process, and an additional cleaning process due to by-product generation is unnecessary.
  • the method of injecting the mass body 140 may be a method of transporting the mass body 140 in a powder state through a carrier gas and radiating it with a nozzle.
  • the step of modifying at least a portion of the surface may be performed through plasma treatment.
  • the plasma may be using O 2 .
  • a step of removing the modified seed layer 130 formed on the photoresist layer 120 may be performed. This step may be performed by contacting an etching solution to the modified seed layer 130 formed on the photoresist layer 120. To this end, only a part of the seed layer 130 and the photoresist layer 120 modified in the etching solution may be soaked to prevent the seed layer 130 disposed on the substrate from being removed.
  • the etching solution may be any one of ammonia, hydrogen peroxide, hydrofluoric acid, nitric acid and sulfuric acid, but is not limited thereto, and a solution used for wet etching may be used.
  • a step of forming a first plating layer 150 on the seed layer 130 may be performed through the electroless plating process (see FIG. 4 ).
  • the first plating layer 150 may be formed in the region where the pattern is formed through the electroless plating method.
  • unnecessary parts have to be removed through etching, but there is a problem of low realization due to high cost and time and technical difficulty.
  • the first plating film 150 is faster and more economical than that of forming the conductive wiring using the conventional sputtering method or the like. Can form.
  • the first plating film 150 formed through the electroless plating method includes a conductive material, and preferably includes copper.
  • the electroless plating method may be performed by supplying a plating solution 170 on the seed layer 130.
  • the electroless plating method may be performed by a conventional method performed to form a metal layer.
  • the plating solution used for electroless plating may include a metal salt such as copper sulfate, an oxidizing agent such as formalin, a complexing agent such as Roxel salt, and sodium hydroxide.
  • the electroless plating method can be performed in two ways.
  • first electroless plating may be performed to form a first plated film having excellent adhesion to the seed layer 130.
  • the primary electroless plating may form a part of the first plating layer 150 in a manner excellent in bonding characteristics with the seed layer 130.
  • secondary electroless plating may be performed to increase the thickness of the first plating layer 150.
  • the second electroless plating may rapidly increase the thickness of the first plating film in a manner that can realize a fast plating speed. That is, while the primary electroless plating is an excellent bonding method, production efficiency may deteriorate when a thick plating film is formed due to a slow plating speed. Accordingly, production efficiency may be improved by performing the second electroless plating.
  • a step of forming a second plating layer 180 on the first plating layer 150 by performing electroplating may be further included (see FIG. 6 ).
  • the second plating layer 180 may be the same material as the first plating layer 150 or may be a different material.
  • this step may increase production efficiency by reducing the time taken to form the plating layer having a desired thickness.
  • metal ions can be formed on various substrates having a catalytic surface capable of being reduced, and a dense and uniform film can be formed, while the plating speed can be slow. Accordingly, after forming the first plating film 150 having a predetermined thickness, for example, 100 to 1000 ⁇ , through the electroless plating process, the second plating film of the same material as the first plating film is electrolytically plated. Formation can quickly form a plating film.
  • a plating film (wiring) having a thickness of 5 or more or 100 umm or more can be formed more quickly.
  • a plated film including heterogeneous materials may be formed through this step.
  • nickel may be plated through electroplating on the copper plating film to form a plating film including copper and nickel.
  • the electroplating may be performed by a conventional electroplating method of forming a metal layer on a metal surface by supplying electricity.
  • a step of removing the photoresist layer 120 is performed (see FIG. 5).
  • This step may be performed by a lift-off method, which typically removes the photoresist layer 120, and is not particularly limited.
  • this step may be performed by a wet method, and an amine-based solution may be used as the wet stripper for removing the photoresist layer 120.
  • a method of manufacturing a transparent conductive film according to another embodiment of the present invention includes forming a photoresist layer 120 on a substrate 110; Forming a pattern by removing a portion of the photoresist layer 120 so that a portion of the substrate 110 is exposed to the outside; Forming a first seed layer (130A) on the substrate 110 and the photoresist layer 120, the part of which is exposed to the outside; Modifying at least a portion of the surface of the first seed layer 130A; Forming a second seed layer (130B) on the first seed layer (130A) formed on the substrate 110 partially exposed to the outside; Forming a first plating layer 150 from the second seed layer 130B by performing electroless plating; And removing the photoresist layer 120.
  • Forming a second seed layer 130B, and forming the first plating layer 150 may include forming a first plating layer 150 on the second seed layer 130B. It is characterized by forming.
  • the substrate 110 is not particularly limited as long as the conductive wiring can be disposed thereon, and may be formed of a material that can transmit light.
  • the substrate 110 may be a rigid substrate 110, such as glass, sapphire, or silicon wafer, such as polyimide, polyethylene terephthalate, and propylene glycol polycarbonate (PC). It may be a flexible substrate 110 including plastic.
  • the step of forming the photoresist layer 120 on the substrate 110 may be performed by applying a photoresist that is a photosensitive material on the substrate 110.
  • the coating method may be a solution coating of a liquid photoresist, and is not particularly limited.
  • the photoresist is aromatic bis-azide, methacrylic acid ester, cinnamic acid ester, polymethyl methacrylate, naphthoquinone diazide (Naphthoquinonediazide), polybutene-1 sulfone (Polybutene-1 sulfone) and diazonaphthoquinone (diazonaphthoquinone)-may include at least one of novolak resin (DNQ/NR).
  • DNQ/NR novolak resin
  • a step of forming a pattern by removing a portion of the photoresist layer 120 is performed so that a portion of the substrate 110 is exposed to the outside (see FIG. 7 ).
  • This step includes disposing a mask on the photoresist layer 120, reacting a portion of the photoresist layer 120 by shining light of a specific wavelength on the mask (exposure step) and the photoresist layer And removing the reacted portion of the 120 (development step).
  • the mask may include a pattern groove in which a portion in which conductive wiring is formed is perforated.
  • the light used in the exposure step may be of UV wavelength and may be selected as suitable for photoresist.
  • the method of removing the photoresist layer 120 in the developing step may be performed by treating the reacted photoresist layer 120 with a developer.
  • the developer may include a developer, a composition agent, and an oxidation inhibitor.
  • the developer may function to reduce silver halide.
  • a post treatment with dilute acid may be further included to suppress the development reaction.
  • an intaglio pattern may be formed such that a region of the substrate 110 corresponding to the pattern groove of the mask is exposed to the outside between the photoresist layers 120.
  • the intaglio pattern may be a lattice shape or a mesh shape, and is not particularly limited.
  • the depth of the intaglio pattern may be 2 to 50 ⁇ m, preferably 5 to 30 ⁇ m, if necessary, the width of the intaglio pattern may be 2 to 50 ⁇ m, preferably 5 to 30 ⁇ m, and the interval between the intaglio patterns is 50 To 1000 ⁇ m, preferably 200 to 800 ⁇ m.
  • the first seed layer 130A is a base for forming the second seed layer 130B afterwards, and may be formed of a conductive material that can stably form the second seed layer 130B.
  • the first seed layer 130A may include any one of TiN, TiW, and Cu conductive materials.
  • Methods of forming the first seed layer 130A include a sputtering method, a chemical vapor deposition (CVD) method, and a spin coating method.
  • CVD chemical vapor deposition
  • spin coating method Preferably, by forming the first seed layer 130A using a sputtering method, the thickness of the thin film can be accurately controlled and a thin film can be formed.
  • a step of modifying at least a portion of the surface of the first seed layer 130A is performed (see FIG. 9 ).
  • the "modifying at least a part of the surface” means physically or chemically changing the properties of the surface of the first seed layer 130A, and a crack or photoresist layer 120 is formed in a part of the first seed layer 130A. ) May mean that a phenomenon such as separation has occurred. Accordingly, the first seed layer 130A on the photoresist layer 120 may be selectively removed.
  • the step of modifying at least a portion of the surface may be performed by spraying the mass 140 on the seed layer 130 or the first seed layer 130A on the photoresist layer 120.
  • the method of injecting the mass body 140 may be to inject the mass body 140 to have a predetermined angle from a direction perpendicular to the photoresist layer. Referring to FIG. 8, it can be seen that the mass body 140 is injected in a direction inclined at a predetermined angle ⁇ with respect to a direction (dotted line) perpendicular to the photoresist layer 120. Through this, the mass body 140 is controlled to collide with the first seed layer 130A disposed on the photoresist layer 120, but not to collide with the first seed layer 130A disposed on the substrate 110. Can be.
  • the angle at which the mass body 140 is incident may be 20 to 70° with respect to a direction perpendicular to the photoresist layer 120.
  • the angle at which the mass body 140 is incident is less than 20°, a problem may occur in which the mass body 140 collides with the first seed layer 130A on the substrate 110.
  • the angle at which the mass body 140 is incident is greater than 70°, the surface modification of the first seed layer 130A does not sufficiently occur because the mass body 140 cannot transmit a sufficient amount of impact to the first seed layer 130A. It may not.
  • the mass body 140 may have a mass capable of transmitting an impact amount such that the surface of the first seed layer 130A can be modified, and when incident at a predetermined angle, between patterns formed in the photoresist layer 120 It is desirable to have a size that does not flow. To this end, the average diameter of the mass 140 incident on the first seed layer 130A in this step may be 5 ⁇ m or more, and more preferably 10 ⁇ m or more.
  • the mass body 140 may be a sublimation material, and preferably, the sublimation material may be any one of dry ice, naphthalene, and iodine.
  • the mass body 140 collides with the first seed layer 130A and vaporizes, there may not be a by-product on the first seed layer 130A. Therefore, only the first seed layer 130A on the photoresist layer 120 can be modified by a simple process, and an additional cleaning process due to by-product generation is unnecessary.
  • the method of injecting the mass body 140 may be a method of transporting the mass body 140 in a powder state through a carrier gas and radiating it with a nozzle.
  • this step may be performed through plasma treatment.
  • the plasma may be using O 2 .
  • a step of removing the modified first seed layer 130A disposed on the photoresist layer 120 may be performed. This step may be performed by contacting the modified first seed layer 130A disposed on the photoresist layer 120 by contacting an etching solution. To this end, only a portion of the first seed layer 130A and the photoresist layer 120 modified in the etching solution may be soaked to prevent the first seed layer 130A disposed on the substrate from being removed.
  • the etching solution may be any one of ammonia, hydrogen peroxide, hydrofluoric acid, nitric acid and sulfuric acid, but is not limited thereto, and a solution used for wet etching may be used.
  • the second seed layer 130B serves as a seed layer for forming a conductive film using an electroless plating process.
  • the conductive film may be formed of a conductive material that can be efficiently formed, and may include a catalyst to improve the efficiency of electroless plating.
  • the catalyst may include a palladium (Pd) element 160.
  • the method for forming the second seed layer 130B includes a sputtering method, a chemical vapor deposition (CVD) method, a spin coating method, and an electroless plating method.
  • the second seed layer 130B may be performed by an electroless plating method, for example, a second seed layer including palladium (Pd) may be formed by an electroless plating method. At this time, palladium (Pd) may be formed in the form of small particles.
  • the second seed layer 130B may be formed only on the first seed layer 130A on the substrate 110. .
  • a step of forming a first plating layer 150 on the second seed layer 130B may be performed through the electroless plating process (see FIG. 11 ).
  • the first plating layer 150 may be formed in the region where the pattern is formed through the electroless plating method.
  • unnecessary parts have to be removed through etching, but there is a problem of low realization due to high cost and time and technical difficulty.
  • the first plating film 150 since the first plating film 150 (wiring) is formed in the region where the pattern is formed by using the electroless plating method, it is faster and more economical than forming the conductive wiring by using the conventional sputtering method or the like.
  • the first plating film 150 may be formed.
  • the first plating film 150 formed through the electroless plating method includes a conductive material, and preferably includes copper.
  • the electroless plating method may be performed by supplying a plating solution 170 on the first seed layer 130A or the second seed layer 130B.
  • the electroless plating method may be performed by a conventional method performed to form a metal layer.
  • the plating solution used for electroless plating may include a metal salt such as copper sulfate, an oxidizing agent such as formalin, a complexing agent such as Roxel salt, and sodium hydroxide.
  • 14 and 15 show the electroless plating process. 14 and 15, it can be seen that palladium (Pd) included in the second seed layer 130B in the plating solution 170 acts as a catalyst, thereby improving the growth efficiency of the copper first plating film 150. have.
  • palladium (Pd) included in the second seed layer 130B in the plating solution 170 acts as a catalyst, thereby improving the growth efficiency of the copper first plating film 150. have.
  • palladium acts as a reducing agent to reduce copper ions on the copper plating solution to form a first plating film on the second seed layer, and when copper is plated, the copper surface itself is palladium ( It can act as a reducing agent that provides electrons in place of Pd).
  • the electroless plating method can be performed in two ways.
  • first electroless plating may be performed to form a first plated film having excellent adhesion to the seed layer 130.
  • the primary electroless plating may form a part of the first plating layer 150 in a manner excellent in bonding characteristics with the seed layer 130.
  • secondary electroless plating may be performed to increase the thickness of the first plating layer 150.
  • the second electroless plating may rapidly increase the thickness of the first plating film in a manner that can realize a fast plating speed. That is, while the primary electroless plating is an excellent bonding method, production efficiency may deteriorate when a thick plating film is formed due to a slow plating speed. Accordingly, production efficiency may be improved by performing the second electroless plating.
  • a step of forming a second plating layer 180 on the first plating layer 150 by performing electroplating may be further included (see FIG. 13 ).
  • the second plating layer 180 may be the same material as the first plating layer 150 or may be a different material.
  • this step may increase production efficiency by reducing the time taken to form the plating layer having a desired thickness.
  • metal ions can be formed on various substrates having a catalytic surface capable of being reduced, and a dense and uniform film can be formed, while the plating speed can be slow. Accordingly, after forming the first plating film 150 having a predetermined thickness, for example, 100 to 1000 ⁇ , through the electroless plating process, the second plating film of the same material as the first plating film is electrolytically plated. Formation can quickly form a plating film.
  • a plating film (wiring) having a thickness of 5 or more or 100 umm or more can be formed more quickly.
  • a plated film including heterogeneous materials may be formed through this step.
  • nickel may be plated through electroplating on the copper plating film to form a plating film including copper and nickel.
  • the electroplating may be performed by a conventional electroplating method of forming a metal layer on a metal surface by supplying electricity.
  • a step of removing the photoresist layer 120 is performed (see FIG. 12 ).
  • This step may be performed by a lift-off method, which typically removes the photoresist layer 120, and is not particularly limited.
  • this step may be performed by a wet method, and an amine-based solution may be used as the wet stripper for removing the photoresist layer 120.
  • a method of manufacturing a transparent conductive film according to another embodiment of the present invention includes forming a photoresist layer on a substrate; Forming a pattern by removing a portion of the photoresist layer so that a portion of the substrate is exposed to the outside; Forming a seed layer on the substrate and the photoresist layer where the part is exposed to the outside; Modifying at least a portion of the surface of the seed layer; Removing the photoresist layer; And performing electroless plating to form a first plated film on the seed layer.
  • electroless plating is performed to form a first plating film on the seed layer.
  • the seed layer which may remain partially on the photoresist layer, is removed together, so that only the seed layer formed on the substrate may remain (see FIG. 16). Thereafter, electroless plating may be performed to form a first plating film on the seed layer.
  • a method of manufacturing a transparent conductive film includes forming a photoresist layer on a substrate; Forming a pattern by removing a portion of the photoresist layer so that a portion of the substrate is exposed to the outside; Forming a first seed layer on the substrate and the photoresist layer where the part is exposed to the outside; Modifying at least a portion of the surface of the first seed layer; Forming a second seed layer on the first seed layer formed on the substrate where the part is exposed to the outside; Removing the photoresist layer; And performing electroless plating to form a first plating layer on the second seed layer. It includes.
  • electroless plating is performed to form a first plating film on the second seed layer.
  • the first seed layer or the second seed layer which may partially remain on the photoresist layer, is removed together, and only the first seed layer and the second seed layer formed on the substrate are removed. May remain (see FIG. 17). Thereafter, electroless plating may be performed to form a first plating film on the first seed layer or the second seed layer.
  • the transparent conductive film manufactured according to the embodiment of the present invention can be used for a touch panel and a sensor, and can be applied to a display to which it is applied. In addition, it can be applied to solar cells and windows requiring light transmission, and recently it can be used as an electromagnetic wave shielding film to block electromagnetic waves.

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  • Engineering & Computer Science (AREA)
  • Manufacturing & Machinery (AREA)
  • Physics & Mathematics (AREA)
  • Condensed Matter Physics & Semiconductors (AREA)
  • General Physics & Mathematics (AREA)
  • Computer Hardware Design (AREA)
  • Microelectronics & Electronic Packaging (AREA)
  • Power Engineering (AREA)
  • Electromagnetism (AREA)
  • Chemically Coating (AREA)
  • Manufacturing Of Printed Wiring (AREA)
  • Internal Circuitry In Semiconductor Integrated Circuit Devices (AREA)
PCT/KR2019/011686 2018-12-14 2019-09-10 투명전도막의 제조방법 WO2020122370A1 (ko)

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KR10-2018-0161733 2018-12-14
KR1020190026171A KR102260382B1 (ko) 2018-12-14 2019-03-07 투명전도막의 제조방법
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