WO2020071875A1 - Catalyst ink for plating to form three-dimensional structure and method for manufacturing three-dimensional structure using same - Google Patents

Catalyst ink for plating to form three-dimensional structure and method for manufacturing three-dimensional structure using same

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Publication number
WO2020071875A1
WO2020071875A1 PCT/KR2019/013079 KR2019013079W WO2020071875A1 WO 2020071875 A1 WO2020071875 A1 WO 2020071875A1 KR 2019013079 W KR2019013079 W KR 2019013079W WO 2020071875 A1 WO2020071875 A1 WO 2020071875A1
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WO
WIPO (PCT)
Prior art keywords
plating
polymer
catalyst ink
ink
catalyst
Prior art date
Application number
PCT/KR2019/013079
Other languages
French (fr)
Korean (ko)
Inventor
설승권
이상현
김정현
표재연
Original Assignee
한국전기연구원
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Publication date
Application filed by 한국전기연구원 filed Critical 한국전기연구원
Publication of WO2020071875A1 publication Critical patent/WO2020071875A1/en

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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
    • C23C18/1601—Process or apparatus
    • C23C18/1603—Process or apparatus coating on selected surface areas
    • C23C18/1607—Process or apparatus coating on selected surface areas by direct patterning
    • C23C18/1608—Process or apparatus coating on selected surface areas by direct patterning from pretreatment step, i.e. selective pre-treatment
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B33—ADDITIVE MANUFACTURING TECHNOLOGY
    • B33Y—ADDITIVE MANUFACTURING, i.e. MANUFACTURING OF THREE-DIMENSIONAL [3-D] OBJECTS BY ADDITIVE DEPOSITION, ADDITIVE AGGLOMERATION OR ADDITIVE LAYERING, e.g. BY 3-D PRINTING, STEREOLITHOGRAPHY OR SELECTIVE LASER SINTERING
    • B33Y80/00—Products made by additive manufacturing
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D11/00—Inks
    • C09D11/02—Printing inks
    • C09D11/03—Printing inks characterised by features other than the chemical nature of the binder
    • C09D11/033—Printing inks characterised by features other than the chemical nature of the binder characterised by the solvent
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D11/00—Inks
    • C09D11/02—Printing inks
    • C09D11/10—Printing inks based on artificial resins
    • 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
    • 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
    • C23C18/1601—Process or apparatus
    • C23C18/1603—Process or apparatus coating on selected surface areas
    • C23C18/1607—Process or apparatus coating on selected surface areas by direct patterning
    • C23C18/161—Process or apparatus coating on selected surface areas by direct patterning from plating step, e.g. inkjet
    • 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
    • C23C18/1601—Process or apparatus
    • C23C18/1633—Process of electroless plating
    • C23C18/1655—Process features
    • C23C18/1662—Use of incorporated material in the solution or dispersion, e.g. particles, whiskers, wires
    • 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
    • C23C18/1601—Process or apparatus
    • C23C18/1633—Process of electroless plating
    • C23C18/1675—Process conditions
    • C23C18/168—Control of temperature, e.g. temperature of bath, substrate
    • 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
    • C23C18/18—Pretreatment of the material to be coated
    • C23C18/20—Pretreatment of the material to be coated of organic surfaces, e.g. resins
    • 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
    • C23C18/18—Pretreatment of the material to be coated
    • C23C18/20—Pretreatment of the material to be coated of organic surfaces, e.g. resins
    • C23C18/2006—Pretreatment of the material to be coated of organic surfaces, e.g. resins by other methods than those of C23C18/22 - C23C18/30
    • C23C18/2046—Pretreatment of the material to be coated of organic surfaces, e.g. resins by other methods than those of C23C18/22 - C23C18/30 by chemical pretreatment
    • C23C18/2053—Pretreatment of the material to be coated of organic surfaces, e.g. resins by other methods than those of C23C18/22 - C23C18/30 by chemical pretreatment only one step pretreatment
    • C23C18/206—Use of metal other than noble metals and tin, e.g. activation, sensitisation with metals
    • 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
    • C23C18/18—Pretreatment of the material to be coated
    • C23C18/20—Pretreatment of the material to be coated of organic surfaces, e.g. resins
    • C23C18/2006—Pretreatment of the material to be coated of organic surfaces, e.g. resins by other methods than those of C23C18/22 - C23C18/30
    • C23C18/2046—Pretreatment of the material to be coated of organic surfaces, e.g. resins by other methods than those of C23C18/22 - C23C18/30 by chemical pretreatment
    • C23C18/2053—Pretreatment of the material to be coated of organic surfaces, e.g. resins by other methods than those of C23C18/22 - C23C18/30 by chemical pretreatment only one step pretreatment
    • C23C18/2066—Use of organic or inorganic compounds other than metals, e.g. activation, sensitisation with polymers
    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
    • H05K3/00—Apparatus or processes for manufacturing printed circuits
    • H05K3/10—Apparatus or processes for manufacturing printed circuits in which conductive material is applied to the insulating support in such a manner as to form the desired conductive pattern
    • H05K3/18—Apparatus or processes for manufacturing printed circuits in which conductive material is applied to the insulating support in such a manner as to form the desired conductive pattern using precipitation techniques to apply the conductive material
    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
    • H05K3/00—Apparatus or processes for manufacturing printed circuits
    • H05K3/10—Apparatus or processes for manufacturing printed circuits in which conductive material is applied to the insulating support in such a manner as to form the desired conductive pattern
    • H05K3/18—Apparatus or processes for manufacturing printed circuits in which conductive material is applied to the insulating support in such a manner as to form the desired conductive pattern using precipitation techniques to apply the conductive material
    • H05K3/181—Apparatus or processes for manufacturing printed circuits in which conductive material is applied to the insulating support in such a manner as to form the desired conductive pattern using precipitation techniques to apply the conductive material by electroless plating
    • H05K3/182—Apparatus or processes for manufacturing printed circuits in which conductive material is applied to the insulating support in such a manner as to form the desired conductive pattern using precipitation techniques to apply the conductive material by electroless plating characterised by the patterning method

Definitions

  • the present invention relates to a method for manufacturing a catalyst ink for plating for forming a 3D structure and an electronic device using the same, and more specifically, to a method for manufacturing a 3D electronic device by an electrochemical method using a catalyst ink for plating. It is about.
  • Printed Electronics has the advantage of simplifying the process and manufacturing fast and inexpensive circuit elements on various substrates by directly printing the desired shape compared to the complicated and expensive conventional photolithography method.
  • printed electronics technology produces electronic devices in the form of scanning, copying, and outputting planar two-dimensional objects, and tends to more highly integrate smaller devices on flexible substrates of electrical and electronic circuits.
  • 2D high integration has already reached the physical and technical limitations, and in order to further improve the integration, it is required to manufacture 3D electric and electronic devices and circuits.
  • conventional 3D printing is based on three-dimensional design data on materials such as insulators such as rubber, nylon, and plastic, and metals such as stainless steel, titanium, and silver, based on three-dimensional design data. It has the advantage of being able to shape types, tools and components.
  • conventional 3D printing technologies such as Fused Deposit Modeling (FDM) and Selective Laser Printing (SLS) require a fine pattern to be implemented with various functional materials due to process factors due to manufacturing techniques or limitations of raw materials used. Has limitations because it can be applied to printed electronics technology.
  • 3D printing electronic technology which combines 3D printing and printing electronics
  • printed electronic technology has been limitedly applied to some areas such as circuits of printed circuit boards, semiconductor photomasks, and color filters of displays, but by expanding its scope of application, 3D printing can be used not only for 3D circuit elements but also for complete electronic products. It aims to reach manufacturing.
  • U.S. Patent No. 7922939 to Lewis et al. Discloses a silver ink comprising a short-chain capping agent with a molecular weight of 10,000 or less and a long-chain capping agent with a molecular weight of 25,000 or more adsorbed on the surface of Ag particles, have.
  • the ink in this patent exhibits shear thinning, which shows a decrease in viscosity with increasing shear rate. Therefore, the above patent uses pressure extrusion to form a three-dimensional microstructure by direct ink writing.
  • an electronic device manufactured by such a 3D printing technology has a problem of exhibiting a high resistance value.
  • An object of the present invention is to provide a catalyst ink for plating capable of forming a three-dimensional structure.
  • an object of the present invention is to provide a catalyst ink for plating to maintain a thermodynamically stable structure in a plating solution.
  • an object of the present invention is to provide a method for manufacturing a 3D structure providing a 3D structure having high conductivity.
  • the present invention to achieve the above technical problem, a polymer binder
  • Metal ions as catalysts A coupling agent coupling the polymer binder and a metal ion; Skeletal molding powder; And a solvent, wherein the polymer has a lower critical solution temperature on a solvent-polymer binary system temperature-composition phase equilibrium diagram, and the critical temperature lower limit is 30 ° C. or higher.
  • the lower limit of the critical temperature may be 50 ° C or higher, 55 ° C or higher, 60 ° C or higher, or 65 ° C or higher.
  • the solvent may be water, alcohol, or acetone.
  • the polymer includes an OH functional group.
  • the polymer may include at least one selected from the group consisting of Hydroxypropyl cellulose , Methyl cellulose , Hydroxypropylmethyle cellulose, Ethyl (hydroxyethyl) cellulose , Poly (N-isopropylacrylamide-co-acrylic acid) and Poly (propylene glycol). have.
  • the metal of the metal ion may be at least one selected from the group consisting of Ag, Fe, Co, Ni, Cu, Pd, Pt, Sn, and Au.
  • the skeleton molding powder may include at least one powder selected from the group consisting of CNT, graphite, graphene, and graphene oxide, or may include metal oxide powder or metal nitride powder.
  • the present invention to form a three-dimensional catalyst pattern by discharging a catalyst ink for plating containing a polymer binder, a metal ion as a catalyst and the polymer binder, a skeleton molding powder and a solvent on a substrate step; And immersing the substrate in which the precursor pattern is formed in a plating solution maintained at a temperature above a lower critical solution temperature on a temperature-composition phase equilibrium of the solvent-polymer binary system to form a plating pattern by electroless plating. It provides a method of manufacturing a three-dimensional structure comprising a step.
  • a method of pressurizing and discharging a plating catalyst ink through a nozzle may be applied, and the plating catalyst ink exhibits a behavior of transitioning from a solid-like behavior to a liquid-like behavior under shear stress. It is preferred.
  • the catalyst ink of the present invention can provide a precursor pattern having thermodynamic stability in a plating bath environment.
  • the present invention can further provide a three-dimensional plating pattern having good conductivity, and this pattern can be used for manufacturing wiring or a three-dimensional electronic device.
  • FIG. 1 is a view schematically showing a pattern forming mechanism of the catalyst ink for plating of the present invention.
  • FIG. 2 is a schematic phase diagram of an exemplary polymer-solvent system as a catalyst ink for plating of the present invention.
  • FIG. 3 is a view for schematically explaining the printing technique of the present invention.
  • FIG. 4 is a procedure diagram schematically illustrating a method of manufacturing a three-dimensional structure according to an embodiment of the present invention.
  • FIG. 5 is a graph showing flow characteristics of a catalyst ink for plating prepared according to an embodiment of the present invention.
  • FIG. 6 is a photograph of a sample plated by varying the immersion time in a plating solution to a three-dimensional catalyst pattern prepared according to the experimental example of the present invention.
  • FIG. 7 is a graph showing the results of measuring the electrical properties of the plating pattern obtained according to the plating time.
  • the catalyst ink for plating in the present invention includes a metal as a catalyst, a polymer as a binder, a coupling agent coupling the metal and the polymer, a skeleton molding powder as a skeleton former, and a solvent.
  • the metal includes at least one metal selected from the group consisting of Ag, Fe, Co, Ni, Cu, Pd, Pt, Sn and Au.
  • the catalyst is preferably present in an ionic form, so the metal in the ink is preferably provided as a metal salt.
  • the polymer in the present invention increases the viscosity of the ink and provides adhesion to the substrate. It is preferable that the polymer required in the present invention contains an OH group at the terminal. In addition, the polymer in the present invention requires a certain thermodynamic properties, which will be described later separately.
  • the coupling agent couples the polymer and the metal salt.
  • a silane coupling agent may be used as the coupling agent, and 3-aminopropyl trimethoxysilane (APTMS). Examples include 3-Aminopropyl triethoxysilane (APTES) and 3-aminopropyldimethylethoxysilane (APDMES).
  • APTES 3-Aminopropyl triethoxysilane
  • APIDMES 3-aminopropyldimethylethoxysilane
  • the skeleton molding powder forms a skeleton of a 3D structure and performs a function of supporting the 3D structure after pattern formation.
  • the skeleton molding powder is insoluble in solvents such as graphite, graphene, and carbonaceous material powders such as CNT, metal oxide powders such as alumina and zirconia, metal nitride powders, metal oxynitride powders, and polymer powders, and is maintained in a solid phase in a solvent. Powdered materials can be used.
  • the shape of the skeleton molding powder may have any shape such as a plate shape, a square shape, a needle shape, a spherical shape, and there is no particular limitation on particle size.
  • the particle average particle diameter may affect the resolution of a three-dimensional structure such as an electronic circuit, and has a limitation that a nozzle diameter below the particle average particle diameter cannot be used.
  • the average particle diameter of the skeleton molding powder is 10 nm to 500 ⁇ m.
  • FIG. 1 is a view schematically showing a pattern forming mechanism of the catalyst ink for three-dimensional plating of the present invention.
  • a silanization reaction in which a silane coupling agent is bonded to a terminal OH group to a polymer such as HPC (Hydroxypropyl cellulose) is performed, and a metal salt is bonded to the amino group on the formed surface to form a metal ion complex (metal ion) complex) is formed.
  • Fig. 2 is a phase equilibrium diagram of a polymer-solvent system for explaining the thermodynamic properties required for the catalyst ink for plating of the present invention.
  • the mixture of the polymer and the solvent constituting the catalyst ink for plating exhibits a change in phase depending on the composition-temperature.
  • the mixture is stable to form a completely solid solution in a liquid phase below a predetermined temperature, and this temperature is called a lower critical solution temperature (LCST).
  • LCST lower critical solution temperature
  • the composition-temperature coordinates of the mixture on the phase equilibrium diagram are located inside a spinodal curve that passes the lower limit of the critical temperature, the mixture is separated into two phases, i.e., a polymer or a phase derived therefrom is precipitated from the solvent. If the composition-temperature coordinates of the mixture on the phase equilibrium are located between the spinodal curve and the coexistence curve, partial phase separation occurs, which can be called a metastable state.
  • the properties of such polymer-solvent mixtures can provide the following desirable advantages in the present invention.
  • the mixture is stabilized to a solid solution in the liquid phase so that the polymer can be uniformly dispersed in a solvent.
  • the printed precursor pattern immersed in the plating bath does not deteriorate even when exposed to a plating solution (for example, a solvent such as water). This is because the polymer forming the precursor pattern is thermodynamically stable to be separated from the solvent.
  • a plating solution for example, a solvent such as water
  • the precursor pattern allows the plating film to firmly bond the substrate.
  • the line width of the precursor pattern formed of the plating ink can be maintained even in the plating solution, and the uniformly printed line width can be maintained throughout the plating process.
  • the polymer and the solvent constituting the plating ink of the present invention have a phase equilibrium phase relationship indicated by the above-described polymer-solvent.
  • the polymer and solvent used in the plating ink have a lower critical temperature limit (LCST) in the temperature-composition phase equilibrium of the polymer-solvent system, and the lower critical temperature limit is 30 ° C or higher, 35 ° C or higher, 40 ° C or higher, 45 ° C or higher, 50 ° C or higher, 55 ° C or higher, 60 ° C or higher, or 65 ° C or higher.
  • LCST critical temperature limit
  • Table 1 shows the polymer-solvent system and LCST values preferred in the present invention.
  • the plating operation conditions related to the content and composition of the polymer and the solvent of the plating ink may be designed by reflecting the following.
  • HPC Hydrophilic cellulose
  • the LCST is approximately 45 ° C.
  • the spinodal curve corresponding to the polymer-solvent composition is convex downward, and the LCST is the lowest point, and when the composition changes based on this, the corresponding temperature value increases. Therefore, in the polymer-solvent composition in the actual ink, the polymer can remain in the co-solvent in the solvent even at a temperature greater than LCST. Therefore, in order to suppress the dissolution of the printed precursor pattern, it is preferable to perform plating at a temperature equal to or higher than a spinodal curve corresponding to the composition, for example, at a temperature of 60 ° C or higher.
  • 3 is a view for schematically illustrating a 3D printing (meniscus-guided printing) method of the present invention.
  • the catalyst ink 20 for plating of the present invention is maintained in the printing pen 110 equipped with a nozzle.
  • the ink 20 may include the dispersion particles 22 and the solvent 24 including the aforementioned metal ions, polymers, skeleton molding powder, and the like.
  • the printing pen 110 contacts the substrate 10, and the pen 110 presses and discharges ink of the nozzle while moving a predetermined distance from the contact point in a specific direction, for example, in a direction parallel to the substrate (FIG. 3 (a)) .
  • Any method such as pneumatic or hydraulic may be used as the pressurizing method of the ink.
  • a pattern 12 corresponding to the movement trajectory of the nozzle is printed on the substrate.
  • the nozzle returns to a predetermined position on the substrate and ejects ink in the same manner to deposit a new pattern 12B on the pattern 12A.
  • a desired three-dimensional pattern can be formed by such a lamination method.
  • the nozzle moves in a horizontal direction with the substrate, but the present invention is not limited to this, and the nozzle moves in a vertical direction with respect to the substrate to emit ink to form a columnar or wire-shaped structure pattern. It may form.
  • the flow characteristics of the ink need to be controlled for seamless printing of the three-dimensional structure pattern.
  • a considerable amount of a binder and a coupling agent can be used, and since a significant amount of molding powder is used to maintain the shape of the structure, the ink viscosity of the ink according to the external force Represents the changing viscoelastic behavior.
  • the plating ink of the present invention exhibits a flow characteristic that converts from a liquid like behavior to a solid like behavior according to the magnitude of the stress.
  • the ink of the present invention exhibits liquid-like behavior under shear stress experienced while passing through the nozzle by pressurization, and exhibits solid-like behavior after being patterned on the substrate through the nozzle to form a shape as part of the three-dimensional structure. You can maintain.
  • a storage modulus loss modulus relationship exists for a specific stress value in a shear stress section of 10 1 to 10 4 Pa, and this is a smaller stress. At values, the storage modulus is greater than the loss modulus, and at higher stress values, the storage modulus is less than the loss modulus.
  • the catalyst ink for plating preferably has a viscosity of 10 0 to 10 5 Pa ⁇ s, more preferably 10 1 to 10 4 Pa ⁇ s.
  • Inks of low viscosity show good flow characteristics, but high flowability makes it difficult to maintain the shape of the three-dimensional structure, and excessive viscosity values make it difficult to eject ink continuously.
  • the flow characteristics of the plating ink can be controlled by the concentration of the molding powder, the concentration of metal ions, the concentration of the binder, and the concentration of the coupling agent.
  • the concentration of the shaping powder in the present invention is 100 to 500 g / L
  • the concentration of metal ions is 10 to 100 g / L
  • the concentration of the binder is 50 to 200 g / L
  • the concentration of the coupling agent is 10 to 100 g. It is preferable that it is / L.
  • FIG. 4 is a view for schematically illustrating a method of forming a 3D structure according to an embodiment of the present invention.
  • a predetermined three-dimensional catalyst pattern is formed on a substrate with the aforementioned catalyst ink for plating (S100).
  • the printing technique of the pressure discharge method as described with reference to FIG. 3 may be applied to the printing of the 3D catalyst pattern.
  • the three-dimensional catalyst pattern may constitute a part of the three-dimensional structure.
  • a part of the 3D structure may be implemented as a 3D catalyst pattern, and the other part may be implemented as a non-catalyst pattern.
  • the three-dimensional catalyst pattern may be formed to contact the substrate, but may alternatively be formed on another three-dimensional pattern on the substrate.
  • the substrate on which the three-dimensional catalyst pattern is printed is immersed in a plating solution to electrolessly plate the metal.
  • the plating metal is selectively plated on the surface of the catalyst pattern (S110).
  • the plating solution may be a solution containing various metals and metal alloys such as Cu, Ni, Ni-P, Ni-W-P, and Ni-W-Cu-P.
  • the polymer binder of the catalytic ink for plating exhibits LCST behavior in the plating solution. Therefore, the temperature of the plating solution is maintained above LCST.
  • the temperature of the plating solution is adjusted to be located above the spinodal curve on the composition-temperature phase equilibrium diagram of the polymer-solvent system. Accordingly, the polymer binder is not dissolved in the plating solution, and the plating film can be firmly bonded to the substrate.
  • the shape of the catalyst pattern can be transferred as it is to the pattern after plating.
  • the plating rate in electroless plating depends on the temperature of the plating solution. Specifically, the plating speed may increase exponentially with the plating temperature. Therefore, the plating method using the catalyst ink for plating of the present invention can significantly improve the growth rate of the plating film by enabling plating at a high temperature.
  • the viscosity of the catalyst ink for plating was measured with a cone-and-plate rheometer (MCR102, Anton Paar) in a shear rate range of 10 0 to 10 2 s -1 .
  • MCR102 cone-and-plate rheometer
  • the stress was continuously changed at a constant frequency of 1 Hz.
  • FIG. 5 is a graph showing the flow characteristics of the prepared catalyst ink for plating. As can be seen from the upper right graph of FIG. 5, the catalyst ink exhibits a shear thinning phenomenon in which viscosity decreases with shear rate.
  • the catalyst ink exhibits a solid-like behavior of storage modulus> loss modulus in a section with low shear stress, but storage modulus in a section with high shear stress (storage) modulus) ⁇ liquid modulus of loss modulus (storage modulus). Therefore, by properly controlling the ejection pressure of the nozzle, the ink of the present invention exhibits liquid-like behavior when passing through the nozzle, so that it is discharged seamlessly, and after passing through the nozzle and laminated on a substrate, it exhibits a solid-like behavior and shows a three-dimensional structure. As part of it, the shape can be maintained.
  • Cu electroless plating solution precured copper sulfate pentahydrate (large gold)
  • the prepared plating pattern was observed with Hitachi S-4800 FE-SEM.
  • the electrical conductivity was measured by a two-point probe method using a Keithley 2612A equipment at room temperature.
  • FIG. 6 is a photograph of a sample plated by varying the immersion time in a plating solution for a three-dimensional catalyst pattern prepared according to the experimental example.
  • 7 is a graph showing the results of measuring the electrical properties of the plating pattern obtained according to the plating time. 7 shows that the resistance decreases as the plating time elapses.
  • a catalyst pattern was formed along the surface of the substrate having a surface slope and plated.
  • FIG. 8 (a) is an image of a pattern printed on each substrate
  • FIG. 8 (b) is an image of a pattern subjected to plating.
  • Conventional printing equipment such as inkjet or aerojet can print a pattern at a gentle slope, but in the present invention, it is possible to print a pattern on a substrate having a 90 ° slope.
  • the present invention can be used for the production of 3D structures.

Abstract

Disclosed are: a catalyst ink for plating; and a method for electrochemically manufacturing a three-dimensional device using same. The present invention provides a catalyst ink for plating, comprising: a polymer binder; a metal ions as a catalyst; a coupling agent for coupling the polymer binder and the metal ion; a backbone model powder; and a solvent, wherein the polymer has a lower critical solution temperature on the temperature-composition phase equilibrium diagram of a solvent-polymer binary system, the lower critical solution temperature being 30℃ or higher. According to the present invention, a three-dimensional plating pattern can be provided having favorable conductivity.

Description

3차원 구조체 형성을 위한 도금용 촉매 잉크 및 이를 이용한 3차원 구조체의 제조 방법Catalytic ink for plating to form a three-dimensional structure and a method for manufacturing the three-dimensional structure using the same
본 발명은 3차원 구조체 형성을 위한 도금용 촉매 잉크 및 이를 이용한 전자소자의 제조 방법에 관한 것으로, 보다 상세하게는 도금용 촉매 잉크를 이용하여 전기화학적인 방법으로 3차원 전자소자를 제조하는 방법에 관한 것이다. The present invention relates to a method for manufacturing a catalyst ink for plating for forming a 3D structure and an electronic device using the same, and more specifically, to a method for manufacturing a 3D electronic device by an electrochemical method using a catalyst ink for plating. It is about.
인쇄전자기술(Printed Electronics)은 복잡하고 고비용의 종래의 사진식각기법(Photolithography)에 비해 원하는 형상을 직접 인쇄함으로써 공정을 단순화하고 빠르고 저렴한 회로 소자를 다양한 기판 상에 제조할 수 있다는 장점을 갖는다. Printed Electronics has the advantage of simplifying the process and manufacturing fast and inexpensive circuit elements on various substrates by directly printing the desired shape compared to the complicated and expensive conventional photolithography method.
통상적으로 인쇄전자 기술은 평면으로 된 2차원 개체를 스캔, 복사, 출력하는 형식으로 전자소자를 제작하며, 전기 전자 회로들을 유연한 기판 위에 더 작은 소자를 보다 고집적화하는 경향을 보이고 있다. 그러나 2차원 고집적화는 이미 물리적 기술적 한계에 봉착하였으며 집적도를 더 향상시키기 위해서는 3차원 형상의 전기 전자 소자 및 회로의 제작이 요구되고 있다. In general, printed electronics technology produces electronic devices in the form of scanning, copying, and outputting planar two-dimensional objects, and tends to more highly integrate smaller devices on flexible substrates of electrical and electronic circuits. However, 2D high integration has already reached the physical and technical limitations, and in order to further improve the integration, it is required to manufacture 3D electric and electronic devices and circuits.
이와 관련하여, 종래의 3D 프린팅은 고무, 나일론, 플라스틱과 같은 절연체, 스테인리스스틸, 티타늄, 은과 같은 금속 등의 소재를 3차원 설계 데이터를 기반으로 하여 적층 제조법(additive manufacturing)으로 실물 모형, 프로토타입, 툴 및 부품 등을 형상화할 수 있다는 장점을 갖는다. 그러나, FDM(Fused Deposit Modelling), SLS(Selective Laser Printing)과 같은 종래의 3D 프린팅 기술은 제조기법에 기인하는 공정 요소들 또는 사용되는 원료 물질의 제한 등으로 인해 다양한 기능성 재료로 미세 패턴이 구현되어야 하는 인쇄전자기술에 적용되기에 한계를 가지고 있다.  In this regard, conventional 3D printing is based on three-dimensional design data on materials such as insulators such as rubber, nylon, and plastic, and metals such as stainless steel, titanium, and silver, based on three-dimensional design data. It has the advantage of being able to shape types, tools and components. However, conventional 3D printing technologies such as Fused Deposit Modeling (FDM) and Selective Laser Printing (SLS) require a fine pattern to be implemented with various functional materials due to process factors due to manufacturing techniques or limitations of raw materials used. Has limitations because it can be applied to printed electronics technology.
최근에는 3D 프린팅 기법과 인쇄 전자 기술을 결합하는 3D 인쇄 전자 기술에 대한 관심이 높아지고 있다. 인쇄 전자 기술은 과거에는 인쇄회로기판의 회로, 반도체의 포토마스크, 디스플레이의 컬러 필터 등 일부 영역에 제한적으로 적용되어 왔지만, 그 적용 범위를 확장하여 3D 프린팅만으로 3차원 회로 소자 뿐만 아니라 완전한 전자 제품의 제조에 까지 이르는 것을 목표로 하고 있다. Recently, interest in 3D printing electronic technology, which combines 3D printing and printing electronics, has increased. In the past, printed electronic technology has been limitedly applied to some areas such as circuits of printed circuit boards, semiconductor photomasks, and color filters of displays, but by expanding its scope of application, 3D printing can be used not only for 3D circuit elements but also for complete electronic products. It aims to reach manufacturing.
이러한 3D 인쇄 전자 기술의 구현에는 전도성, 자성 또는 전기적 절연성을 갖는 다양한 기능성 소재로 3차원 구조체를 형성하는 기술이 요구되며, 또한 3D 프린팅에 적합한 잉크 및 프린팅 기법의 개발이 요구된다. In order to implement such 3D printed electronic technology, a technique for forming a 3D structure with various functional materials having conductivity, magnetic or electrical insulation is required, and development of an ink and printing technique suitable for 3D printing is also required.
루이스(Lewis) 등의 미국등록특허 제7922939호는 Ag 입자의 표면에 흡착된 분자량 10,000 이하의 쇼트-체인 캡핑 에이전트(capping agent)와 분자량 25,000 이상의 롱-체인 캡핑 에이전트를 포함하는 은 잉크를 개시하고 있다. 이 특허에서의 잉크는 전단 속도의 증가에 따라 점도의 감소를 나타내는 전단 박화 현상(shear thinning)을 보인다. 따라서, 위 특허는 가압 사출(pressure extrusion)을 이용하여 잉크 직접 인쇄법(direct ink writing)으로 3차원 미세 구조체를 형성하고 있다. U.S. Patent No. 7922939 to Lewis et al. Discloses a silver ink comprising a short-chain capping agent with a molecular weight of 10,000 or less and a long-chain capping agent with a molecular weight of 25,000 or more adsorbed on the surface of Ag particles, have. The ink in this patent exhibits shear thinning, which shows a decrease in viscosity with increasing shear rate. Therefore, the above patent uses pressure extrusion to form a three-dimensional microstructure by direct ink writing.
그러나, 이와 같은 3D 프린팅 기술에 의해 제조된 전자소자는 높은 저항값을 나타낸다는 문제점을 갖는다.However, an electronic device manufactured by such a 3D printing technology has a problem of exhibiting a high resistance value.
본 발명은 3차원 구조체의 형성이 가능한 도금용 촉매 잉크를 제공하는 것을 목적으로 한다.An object of the present invention is to provide a catalyst ink for plating capable of forming a three-dimensional structure.
또한, 본 발명은 도금 용액 내에서 열역학적으로 안정한 구조체를 유지하는 도금용 촉매 잉크를 제공하는 것을 목적으로 한다.In addition, an object of the present invention is to provide a catalyst ink for plating to maintain a thermodynamically stable structure in a plating solution.
또한, 본 발명은 높은 전도성을 갖는 3차원 구조체를 제공하는 3D 구조체의 제조 방법을 제공하는 것을 목적으로 한다.In addition, an object of the present invention is to provide a method for manufacturing a 3D structure providing a 3D structure having high conductivity.
상기 기술적 과제를 달성하기 위하여 본 발명은, 폴리머 바인더;The present invention to achieve the above technical problem, a polymer binder;
촉매로서의 금속 이온; 상기 폴리머 바인더와 금속 이온을 커플링하는 커플링제; 골격 조형 분말; 및 용매를 포함하고, 상기 폴리머는 용매-폴리머 2원계의 온도-조성 상평형도 상에서 임계 온도 하한(Lower Critical Solution Temperature)을 가지고, 상기 임계 온도 하한은 30℃ 이상인 것을 특징으로 하는 도금용 촉매 잉크를 제공한다. Metal ions as catalysts; A coupling agent coupling the polymer binder and a metal ion; Skeletal molding powder; And a solvent, wherein the polymer has a lower critical solution temperature on a solvent-polymer binary system temperature-composition phase equilibrium diagram, and the critical temperature lower limit is 30 ° C. or higher. Provides
본 발명에서 상기 임계 온도 하한은 50℃ 이상, 55℃ 이상, 60℃ 이상 또는 65℃ 이상일 수 있다. In the present invention, the lower limit of the critical temperature may be 50 ° C or higher, 55 ° C or higher, 60 ° C or higher, or 65 ° C or higher.
또한 본 발명에서 상기 용매는 물, 알코올, 또는 아세톤일 수 있다. In addition, in the present invention, the solvent may be water, alcohol, or acetone.
또한 본 발명에서 상기 폴리머는 OH 작용기를 포함하는 것이 바람직하다. 이 때, 상기 폴리머는 Hydroxypropyl cellulose, Methyl cellulose, Hydroxypropylmethyle cellulose, Ethyl(hydroxyethyl)cellulose, Poly(N-isopropylacrylamide-co-acrylic acid) 및 Poly(propylene glycol)로 이루어진 그룹 중에서 선택된 최소한 1종을 포함할 수 있다. In addition, in the present invention, it is preferable that the polymer includes an OH functional group. At this time, the polymer may include at least one selected from the group consisting of Hydroxypropyl cellulose , Methyl cellulose , Hydroxypropylmethyle cellulose, Ethyl (hydroxyethyl) cellulose , Poly (N-isopropylacrylamide-co-acrylic acid) and Poly (propylene glycol). have.
본 발명에서 상기 금속 이온의 금속은 Ag, Fe, Co, Ni, Cu, Pd, Pt, Sn, Au로 이루어진 그룹 중에서 선택된 최소한 1종일 수 있다. In the present invention, the metal of the metal ion may be at least one selected from the group consisting of Ag, Fe, Co, Ni, Cu, Pd, Pt, Sn, and Au.
또한, 본 발명에서 상기 골격 조형 분말은 CNT, 그라파이트, 그래핀 및 산화 그래핀으로 이루어진 그룹 중에서 선택된 최소한1종의 분말을 포함하거나, 금속 산화물 분말 또는 금속 질화물 분말을 포함할 수 있다. In addition, in the present invention, the skeleton molding powder may include at least one powder selected from the group consisting of CNT, graphite, graphene, and graphene oxide, or may include metal oxide powder or metal nitride powder.
상기 다른 기술적 과제를 달성하기 위하여 본 발명은, 기재 상에, 폴리머 바인더, 촉매로서의 금속 이온 및 상기 폴리머 바인더, 골격 조형 분말 및 용매를 포함하는 도금용 촉매 잉크를 토출하여 3차원 촉매 패턴을 형성하는 단계; 및 상기 전구체 패턴이 형성된 기재를 상기 용매-폴리머 2원계의 온도-조성 상평형도 상에서 임계 온도 하한(Lower Critical Solution Temperature) 이상의 온도로 유지되는 도금 용액 내에 침지하여 무전해 도금하여 도금 패턴을 형성하는 단계를 포함하는 3차원 구조체의 제조 방법을 제공한다. In order to achieve the above other technical problems, the present invention, to form a three-dimensional catalyst pattern by discharging a catalyst ink for plating containing a polymer binder, a metal ion as a catalyst and the polymer binder, a skeleton molding powder and a solvent on a substrate step; And immersing the substrate in which the precursor pattern is formed in a plating solution maintained at a temperature above a lower critical solution temperature on a temperature-composition phase equilibrium of the solvent-polymer binary system to form a plating pattern by electroless plating. It provides a method of manufacturing a three-dimensional structure comprising a step.
본 발명에서 상기 3차원 촉매 패턴 형성 단계에서는 도금용 촉매 잉크를 노즐을 통해 가압 토출하는 방식이 적용될 수 있고, 상기 도금용 촉매 잉크는 전단 응력 하에서 고체 유사 거동에서 액체 유사 거동으로 전이하는 거동을 나타내는 것이 바람직하다.In the step of forming the three-dimensional catalyst pattern in the present invention, a method of pressurizing and discharging a plating catalyst ink through a nozzle may be applied, and the plating catalyst ink exhibits a behavior of transitioning from a solid-like behavior to a liquid-like behavior under shear stress. It is preferred.
본 발명에 따르면, 높은 밀착성을 가지면서 3차원 구조체의 제조가 가능한 촉매 잉크를 제공할 수 있게 된다. 또한 본 발명의 촉매 잉크는 도금조 환경에서 열역학적인 안정성을 갖는 전구체 패턴을 제공할 수 있다. 또한 본 발명은 나아가 최종적으로 양호한 도전성을 갖는 3차원 도금 패턴을 제공할 수 있으며, 이 패턴은 배선 또는3차원 전자소자의 제조에 이용 가능하게 된다.According to the present invention, it is possible to provide a catalyst ink capable of manufacturing a three-dimensional structure while having high adhesion. In addition, the catalyst ink of the present invention can provide a precursor pattern having thermodynamic stability in a plating bath environment. In addition, the present invention can further provide a three-dimensional plating pattern having good conductivity, and this pattern can be used for manufacturing wiring or a three-dimensional electronic device.
도 1은 본 발명의 도금용 촉매 잉크의 패턴 형성 메커니즘을 모식적으로 도시한 도면이다. 1 is a view schematically showing a pattern forming mechanism of the catalyst ink for plating of the present invention.
도 2는 본 발명의 도금용 촉매 잉크로서 예시적인 폴리머-용매 시스템에 대한 모식적인 상평형도이다. FIG. 2 is a schematic phase diagram of an exemplary polymer-solvent system as a catalyst ink for plating of the present invention.
도 3은 본 발명의 프린팅 기법을 설명하기 개략적으로 설명하기 위한 도면이다.3 is a view for schematically explaining the printing technique of the present invention.
도 4는 본 발명의 일실시예에 따른 3차원 구조체의 제조 방법을 개략적으로 설명하기 위한 절차도이다. 4 is a procedure diagram schematically illustrating a method of manufacturing a three-dimensional structure according to an embodiment of the present invention.
도 5는 본 발명의 일실시예에 따라 제조된 도금용 촉매 잉크의 유동 특성을 나타낸 그래프이다.5 is a graph showing flow characteristics of a catalyst ink for plating prepared according to an embodiment of the present invention.
도 6은 본 발명의 실험예에 따라 제조된 3차원 촉매 패턴을 도금 용액 내에서 침지 시간을 달리하여 도금한 샘플의 사진이다.6 is a photograph of a sample plated by varying the immersion time in a plating solution to a three-dimensional catalyst pattern prepared according to the experimental example of the present invention.
도 7은 도금 시간에 따라 얻어진 도금 패턴의 전기적 특성을 측정한 결과를 나타낸 그래프이다.7 is a graph showing the results of measuring the electrical properties of the plating pattern obtained according to the plating time.
도 8은 본 발명의 다른 실시예에 따라 제조된 3차원 패턴의 이미지이다.8 is an image of a 3D pattern manufactured according to another embodiment of the present invention.
이하에서는 본 발명의 바람직한 실시예를 설명함으로써 본 발명을 상술한다. Hereinafter, the present invention will be described in detail by explaining preferred embodiments of the present invention.
본 발명에서 도금용 촉매 잉크는 촉매로서의 금속, 바인더로서의 폴리머, 상기 금속과 상기 폴리머를 커플링하는 커플링제, 골격 형성자로서의 골격 조형 분말 및 용매를 포함한다. The catalyst ink for plating in the present invention includes a metal as a catalyst, a polymer as a binder, a coupling agent coupling the metal and the polymer, a skeleton molding powder as a skeleton former, and a solvent.
본 발명에서 상기 금속은 Ag, Fe, Co, Ni, Cu, Pd, Pt, Sn 및 Au로 이루어진 그룹 중에서 선택된 최소한 1종의 금속을 포함한다. 본 발명의 잉크 조성물에서 촉매는 이온 형태로 존재하는 것이 바람직하므로, 상기 잉크 내의 금속은 금속염(metal salt)으로 제공되는 것이 좋다. In the present invention, the metal includes at least one metal selected from the group consisting of Ag, Fe, Co, Ni, Cu, Pd, Pt, Sn and Au. In the ink composition of the present invention, the catalyst is preferably present in an ionic form, so the metal in the ink is preferably provided as a metal salt.
또한 본 발명에서 폴리머는 잉크의 점도를 증가시키며 상기 기재와의 밀착력을 제공한다. 본 발명에서 요구되는 폴리머는 말단에 OH기를 포함하는 것이 바람직하다. 또한, 본 발명에서 폴리머는 소정의 열역학적인 특성이 요구되는데, 이에 대해서는 따로 후술한다. In addition, the polymer in the present invention increases the viscosity of the ink and provides adhesion to the substrate. It is preferable that the polymer required in the present invention contains an OH group at the terminal. In addition, the polymer in the present invention requires a certain thermodynamic properties, which will be described later separately.
또한, 본 발명에서 상기 커플링제는 폴리머와 금속염을 커플링한다. 예시적으로, 상기 커플링제로는 실란 커플링제가 사용될 수 있고, 3-aminopropyl trimethoxysilane(APTMS). 3-Aminopropyl triethoxysilane(APTES), 3-aminopropyldimethylethoxysilane (APDMES) 등이 그 예이다.Further, in the present invention, the coupling agent couples the polymer and the metal salt. Illustratively, a silane coupling agent may be used as the coupling agent, and 3-aminopropyl trimethoxysilane (APTMS). Examples include 3-Aminopropyl triethoxysilane (APTES) and 3-aminopropyldimethylethoxysilane (APDMES).
본 발명에서 상기 골격 조형 분말은 3차원 구조체의 골격을 형성하고 패턴 형성 후 3차원 구조체를 지지하는 기능을 수행한다. 상기 골격 조형 분말은 그라파이트, 그래핀, CNT 등의 탄소 소재 분말, 알루미나, 지르코니아와 같은 금속 산화물 분말, 금속 질화물 분말, 금속 산질화물 분말, 고분자 분말 등 용매에 비용해성이며 용매 내에서 고상으로 유지되는 분말형 물질이 사용될 수 있다. 본 발명에서 상기 골격 조형 분말의 형상은 판상형, 사각형, 침상형, 구형 등의 임의의 형상을 가질 수 있고, 입자 크기에 특별한 제한은 없다. 다만, 입자 평균 입경은 전자 회로와 같은 3차원 구조체의 해상도에 영향을 미칠 수 있고, 입자 평균 입경 이하의 노즐 구경은 사용할 수 없다는 제한을 갖는다. 본 발명에서 골격 조형 분말의 평균 입경이 10 nm~500 ㎛인 것이 바람직하다. In the present invention, the skeleton molding powder forms a skeleton of a 3D structure and performs a function of supporting the 3D structure after pattern formation. The skeleton molding powder is insoluble in solvents such as graphite, graphene, and carbonaceous material powders such as CNT, metal oxide powders such as alumina and zirconia, metal nitride powders, metal oxynitride powders, and polymer powders, and is maintained in a solid phase in a solvent. Powdered materials can be used. In the present invention, the shape of the skeleton molding powder may have any shape such as a plate shape, a square shape, a needle shape, a spherical shape, and there is no particular limitation on particle size. However, the particle average particle diameter may affect the resolution of a three-dimensional structure such as an electronic circuit, and has a limitation that a nozzle diameter below the particle average particle diameter cannot be used. In the present invention, it is preferable that the average particle diameter of the skeleton molding powder is 10 nm to 500 μm.
도 1은 본 발명의3차원 도금용 촉매 잉크의 패턴 형성 메커니즘을 모식적으로 도시한 도면이다.1 is a view schematically showing a pattern forming mechanism of the catalyst ink for three-dimensional plating of the present invention.
도시된 바와 같이, 예컨대, HPC(Hydroxypropyl cellulose)와 같은 폴리머에 말단 OH기에 실란 커플링제가 결합하는 실란화 반응(Silanization)이 수행되고, 형성된 표면의 아미노기에 금속염이 결합하여 금속 이온 복합체(metal ion complex)가 형성된다. As illustrated, for example, a silanization reaction in which a silane coupling agent is bonded to a terminal OH group to a polymer such as HPC (Hydroxypropyl cellulose) is performed, and a metal salt is bonded to the amino group on the formed surface to form a metal ion complex (metal ion) complex) is formed.
도 2는 본 발명의 도금용 촉매 잉크에 요구되는 열역학적인 특성을 설명하기 위한 폴리머-용매 시스템의 상평형도이다. Fig. 2 is a phase equilibrium diagram of a polymer-solvent system for explaining the thermodynamic properties required for the catalyst ink for plating of the present invention.
본 발명에서 도금용 촉매 잉크를 구성하는 폴리머와 용매의 혼합물(mixtures)은 조성-온도에 따라 상의 변화를 나타낸다. 바람직하게는 상기 혼합물은 소정 온도 이하에서 액상의 완전 고용 상태를 이루는 것이 안정하며, 이 온도는 임계 온도 하한(Lower Critical Solution Temperature; LCST)로 부른다. 반면, 상평형도 상에서 혼합물의 조성-온도 좌표가 상기 임계 온도 하한을 지나는 스피노달 곡선(spinodal curve) 내측에 위치하면 혼합물은 2개의 상으로 분리되는데 즉 폴리머 또는 그로부터 유래된 상이 용매로부터 석출된다. 상평형도 상에서 혼합물의 조성-온도 좌표가 스피노달 곡선과 공존 곡선(coexistence curve) 사이에 위치하는 경우 부분적인 상의 분리가 발생하며, 이를 준안정(metastable) 상태로 부를 수 있다. In the present invention, the mixture of the polymer and the solvent constituting the catalyst ink for plating exhibits a change in phase depending on the composition-temperature. Preferably, the mixture is stable to form a completely solid solution in a liquid phase below a predetermined temperature, and this temperature is called a lower critical solution temperature (LCST). On the other hand, if the composition-temperature coordinates of the mixture on the phase equilibrium diagram are located inside a spinodal curve that passes the lower limit of the critical temperature, the mixture is separated into two phases, i.e., a polymer or a phase derived therefrom is precipitated from the solvent. If the composition-temperature coordinates of the mixture on the phase equilibrium are located between the spinodal curve and the coexistence curve, partial phase separation occurs, which can be called a metastable state.
이러한 폴리머-용매 혼합물의 특성은 본 발명에서 다음과 같은 바람직한 이점을 제공할 수 있다. 잉크의 제조 및 보관 조건의 온도(예컨대 상온)에서 상기 혼합물은 액상의 고용상으로 안정화되어 폴리머는 용매 내에서 균일하게 분산될 수 있다. The properties of such polymer-solvent mixtures can provide the following desirable advantages in the present invention. At the temperature of the ink preparation and storage conditions (e.g., room temperature), the mixture is stabilized to a solid solution in the liquid phase so that the polymer can be uniformly dispersed in a solvent.
반면, 보다 높은 온도 예컨대 LCST 온도 이상의 상대적으로 높은 온도의 도금 조건이 유지되면, 도금조에 침지된 인쇄된 전구체 패턴은 도금 용액(예컨대 물과 같은 용매)에 노출되어도 열화되지 않는다. 이 때에는 전구체 패턴을 이루는 폴리머는 용매로부터 분리되는 것이 열역학적으로 안정적이기 때문이다. On the other hand, if the plating conditions at a relatively high temperature above the higher temperature, such as the LCST temperature, are maintained, the printed precursor pattern immersed in the plating bath does not deteriorate even when exposed to a plating solution (for example, a solvent such as water). This is because the polymer forming the precursor pattern is thermodynamically stable to be separated from the solvent.
이와 같은 잉크 특성은 전구체 패턴이 도금 용액 내에서 용해되거나 분해되지 않으므로, 전구체 패턴은 도금막이 기재를 견고히 결합하게 한다. 또한, 도금용 잉크로 형성된 전구체 패턴의 선폭은 도금 용액 내에서도 그대로 유지될 수 있으며, 균일하게 인쇄된 선폭은 도금 공정 내내 유지될 수 있다. Since such ink properties do not dissolve or decompose the precursor pattern in the plating solution, the precursor pattern allows the plating film to firmly bond the substrate. In addition, the line width of the precursor pattern formed of the plating ink can be maintained even in the plating solution, and the uniformly printed line width can be maintained throughout the plating process.
본 발명의 도금용 잉크를 구성하는 폴리머 및 용매는 전술한 폴리머-용매가 나타내는 상평형도 상의 관계를 가진다. 바람직하게는 도금용 잉크에 사용되는 폴리머와 용매는 폴리머-용매 시스템의 온도-조성 상평형도에서 임계 온도 하한(LCST)을 가지며, 임계 온도 하한은 30℃ 이상, 35℃ 이상, 40℃ 이상, 45℃ 이상, 50℃이상, 55℃ 이상, 60℃ 이상, 또는 65℃ 이상일 수 있다. The polymer and the solvent constituting the plating ink of the present invention have a phase equilibrium phase relationship indicated by the above-described polymer-solvent. Preferably, the polymer and solvent used in the plating ink have a lower critical temperature limit (LCST) in the temperature-composition phase equilibrium of the polymer-solvent system, and the lower critical temperature limit is 30 ° C or higher, 35 ° C or higher, 40 ° C or higher, 45 ° C or higher, 50 ° C or higher, 55 ° C or higher, 60 ° C or higher, or 65 ° C or higher.
본 발명에서 바람직한 폴리머-용매 시스템과 LCST값을 표 1에 나타냈다.Table 1 shows the polymer-solvent system and LCST values preferred in the present invention.
구분division 폴리머Polymer 용매menstruum LCSTLCST
1One Hydroxypropyl celluloseHydroxypropyl cellulose WaterWater 45℃45 ℃
22 Methyl celluloseMethyl cellulose WaterWater 50℃50 ℃
33 Hydroxypropylmethyle celluloseHydroxypropylmethyle cellulose WaterWater 70℃70 ℃
44 Ethyl(hydroxyethyl)celluloseEthyl (hydroxyethyl) cellulose WaterWater 65℃65 ℃
55 Poly(N-isopropylacrylamide-co-acrylic acid)Poly (N-isopropylacrylamide-co-acrylic acid) WaterWater 32~36℃32 ~ 36 ℃
66 Poly(propylene glycol)Poly (propylene glycol) WaterWater 50℃50 ℃
본 발명에서 도금용 잉크의 폴리머, 용매의 함량 및 조성과 관련한 도금 작업 조건은 다음과 같은 사항을 반영하여 설계될 수 있다. 예컨대, 표 1의 HPC(Hydroxypropyl cellulose)를 폴리머로 사용하는 경우 LCST는 대략 45℃이다. 그런데, 폴리머-용매 조성에 대응하는 스피노달 곡선은 아래로 볼록한 형태이며, LCST를 저점으로 하고, 이를 기준으로 조성이 변화하면 대응하는 온도 값이 증가한다. 따라서, 실제 잉크 내의 폴리머-용매 조성에서 폴리머는 LCST 보다 큰 온도에서도 용매 내에 공용 상태로 유지될 수 있다. 따라서, 인쇄된 전구체 패턴의 용해를 억제하기 위해서 해당 조성에 대응하는 스피노달 곡선의 온도 이상, 예를 들어 60℃ 이상의 온도에서 도금을 수행하는 것이 바람직하다. In the present invention, the plating operation conditions related to the content and composition of the polymer and the solvent of the plating ink may be designed by reflecting the following. For example, when using HPC (Hydroxypropyl cellulose) of Table 1 as a polymer, the LCST is approximately 45 ° C. However, the spinodal curve corresponding to the polymer-solvent composition is convex downward, and the LCST is the lowest point, and when the composition changes based on this, the corresponding temperature value increases. Therefore, in the polymer-solvent composition in the actual ink, the polymer can remain in the co-solvent in the solvent even at a temperature greater than LCST. Therefore, in order to suppress the dissolution of the printed precursor pattern, it is preferable to perform plating at a temperature equal to or higher than a spinodal curve corresponding to the composition, for example, at a temperature of 60 ° C or higher.
도 3은 본 발명의 3D 프린팅(meniscus-guided printing) 방법을 개략적으로 설명하기 위한 도면이다. 3 is a view for schematically illustrating a 3D printing (meniscus-guided printing) method of the present invention.
도 3을 참조하면, 본 발명의 도금용 촉매 잉크(20)가 노즐을 구비한 프린팅펜(110) 내에 유지된다. 상기 잉크(20)는 전술한 금속 이온, 폴리머, 골격 조형 분말 등을 포함하는 분산 입자(22)와 용매(24)를 포함할 수 있다. Referring to FIG. 3, the catalyst ink 20 for plating of the present invention is maintained in the printing pen 110 equipped with a nozzle. The ink 20 may include the dispersion particles 22 and the solvent 24 including the aforementioned metal ions, polymers, skeleton molding powder, and the like.
프린팅 펜(110)이 기판(10)과 접촉하고, 펜(110)이 접촉점으로부터 특정 방향 예컨대 기판과 평행한 방향으로 소정 거리만큼 이동하면서 노즐의 잉크를 가압 토출한다(도 3의 (a)). 잉크의 가압 방식은 공압 또는 유압 등 임의의 방식이 사용될 수 있다. 펜이 기판과 평행한 방향으로 소정 속도로 이동하면 그 결과 기판 상에는 노즐의 이동 궤적에 상응하는 패턴(12)이 인쇄된다. 이어서, 노즐이 기재 상의 소정 위치로 복귀하고 동일한 방식으로 잉크를 방출하여 상기 패턴(12A) 상에 새로운 패턴(12B)을 적층한다. 이러한 적층 방식에 의해 원하는 3차원 패턴이 형성될 수 있다. 3차원 구조체 패턴의 형성을 위하여 노즐이 기재와 수평 방향으로 이동하는 것을 설명하였지만, 본 발명은 이에 한정되지 않으며 노즐이 기재에 대하여 수직 방향으로 이동하면서 잉크를 방출하여 기둥 형상 또는 와이어 형상의 구조체 패턴을 형성할 수도 있다. The printing pen 110 contacts the substrate 10, and the pen 110 presses and discharges ink of the nozzle while moving a predetermined distance from the contact point in a specific direction, for example, in a direction parallel to the substrate (FIG. 3 (a)) . Any method such as pneumatic or hydraulic may be used as the pressurizing method of the ink. When the pen moves at a predetermined speed in a direction parallel to the substrate, as a result, a pattern 12 corresponding to the movement trajectory of the nozzle is printed on the substrate. Subsequently, the nozzle returns to a predetermined position on the substrate and ejects ink in the same manner to deposit a new pattern 12B on the pattern 12A. A desired three-dimensional pattern can be formed by such a lamination method. In order to form the three-dimensional structure pattern, it has been described that the nozzle moves in a horizontal direction with the substrate, but the present invention is not limited to this, and the nozzle moves in a vertical direction with respect to the substrate to emit ink to form a columnar or wire-shaped structure pattern. It may form.
본 발명에서 3차원 구조체 패턴의 끊김 없는 프린팅을 위하여 잉크의 유동 특성이 제어될 필요가 있다. 인쇄된 전구체 패턴과 기재(기판)와의 충분한 결합력을 제공하기 위하여, 상당량의 바인더 및 커플링제가 사용될 수 있으며, 구조체의 형상을 유지하기 위하여 상당량의 조형 분말이 사용되므로 잉크는 외력에 따라 잉크의 점도가 변화하는 점탄성 거동을 나타낸다. 이 때, 본 발명의 도금용 잉크는 응력의 크기에 따라 액체 유사 거동(liquid like behavior)에서 고체 유사 거동(solid like behavior)로 전환하는 유동 특성을 나타낸다. 즉, 본 발명의 잉크는 가압에 의해 노즐을 통과하는 동안 겪는 전단응력 하에서는 액체 유사 거동을 나타내고, 노즐을 통과하여 기재 상에 패턴화 된 후에는 고체 유사 거동을 나타내어 3차원 구조체의 일부분으로서 형상을 유지할 수 있게 된다. In the present invention, the flow characteristics of the ink need to be controlled for seamless printing of the three-dimensional structure pattern. In order to provide sufficient bonding strength between the printed precursor pattern and the substrate (substrate), a considerable amount of a binder and a coupling agent can be used, and since a significant amount of molding powder is used to maintain the shape of the structure, the ink viscosity of the ink according to the external force Represents the changing viscoelastic behavior. At this time, the plating ink of the present invention exhibits a flow characteristic that converts from a liquid like behavior to a solid like behavior according to the magnitude of the stress. That is, the ink of the present invention exhibits liquid-like behavior under shear stress experienced while passing through the nozzle by pressurization, and exhibits solid-like behavior after being patterned on the substrate through the nozzle to form a shape as part of the three-dimensional structure. You can maintain.
예컨대, 도금용 잉크의 유동 특성을 살피면, 101~104 Pa의 전단 응력 구간에서 특정 응력값에 대하여 저장 모듈러스(storage modulus) = 손실 모듈러스(loss modulus) 관계인 지점이 존재하며, 이 보다 작은 응력값에서는 저장 모듈러스가 손실 모듈러스에 비해 크며, 이 보다 큰 응력 값에서는 저장 모듈러스가 손실 모듈러스보다 작다.For example, when looking at the flow characteristics of the plating ink, there is a point in which a storage modulus = loss modulus relationship exists for a specific stress value in a shear stress section of 10 1 to 10 4 Pa, and this is a smaller stress. At values, the storage modulus is greater than the loss modulus, and at higher stress values, the storage modulus is less than the loss modulus.
본 발명에서 상기 도금용 촉매 잉크는 100~105 Pa·s의 점도를 갖는 것이 바람직하고, 더 바람직하게는 101~104 Pa·s인 것이 좋다. 낮은 점도의 잉크는 양호한 유동 특성을 보이지만, 흐름성이 높아 3차원 구조체의 형상을 유지하기 곤란하고, 과도한 점도값은 잉크의 끊김 없는 토출을 곤란하게 한다. In the present invention, the catalyst ink for plating preferably has a viscosity of 10 0 to 10 5 Pa · s, more preferably 10 1 to 10 4 Pa · s. Inks of low viscosity show good flow characteristics, but high flowability makes it difficult to maintain the shape of the three-dimensional structure, and excessive viscosity values make it difficult to eject ink continuously.
본 발명에서 도금용 잉크의 유동 특성은 조형 분말의 농도, 금속 이온의 농도, 바인더의 농도 및 커플링제의 농도에 의해 제어될 수 있다. 바람직하게는 본 발명에서 조형 분말의 농도는 100~500 g/L, 금속 이온의 농도는 10~100 g/L, 바인더의 농도는 50~200 g/L, 커플링제의 농도는 10~100 g/L인 것이 바람직하다. In the present invention, the flow characteristics of the plating ink can be controlled by the concentration of the molding powder, the concentration of metal ions, the concentration of the binder, and the concentration of the coupling agent. Preferably, the concentration of the shaping powder in the present invention is 100 to 500 g / L, the concentration of metal ions is 10 to 100 g / L, the concentration of the binder is 50 to 200 g / L, and the concentration of the coupling agent is 10 to 100 g. It is preferable that it is / L.
이하에서는 전술한 도금용 잉크로 배선 패턴을 형성하는 방법을 설명한다.Hereinafter, a method of forming a wiring pattern with the above-described plating ink will be described.
도 4는 본 발명의 일실시예에 따른 3차원 구조체의 형성 방법을 개략적으로 설명하기 위한 도면이다. 4 is a view for schematically illustrating a method of forming a 3D structure according to an embodiment of the present invention.
도 4를 참조하면, 전술한 도금용 촉매 잉크로 기재(substrate) 상에 소정의 3차원 촉매 패턴을 형성한다(S100). Referring to FIG. 4, a predetermined three-dimensional catalyst pattern is formed on a substrate with the aforementioned catalyst ink for plating (S100).
3차원 촉매 패턴의 인쇄에는 도 3을 참조하여 설명한 것과 같은 가압 토출 방식의 인쇄 기법이 적용될 수 있다. The printing technique of the pressure discharge method as described with reference to FIG. 3 may be applied to the printing of the 3D catalyst pattern.
본 발명에서 상기 3차원 촉매 패턴은 3차원 구조체의 일부를 구성할 수 있다. 예컨대, 3차원 구조체의 일부분은 3차원 촉매 패턴으로 구현되고, 나머지 부분은 비촉매 패턴으로 구현될 수 있다. 또한, 상기 3차원 촉매 패턴은 기재와 접촉하도록 형성될 수 있지만, 이와 달리 기재 상의 다른 3차원 패턴 위에 형성될 수도 있다. In the present invention, the three-dimensional catalyst pattern may constitute a part of the three-dimensional structure. For example, a part of the 3D structure may be implemented as a 3D catalyst pattern, and the other part may be implemented as a non-catalyst pattern. In addition, the three-dimensional catalyst pattern may be formed to contact the substrate, but may alternatively be formed on another three-dimensional pattern on the substrate.
다음, 3차원 촉매 패턴이 인쇄된 기재를 도금 용액 내에 침지하여 금속을 무전해 도금한다. 도금 금속이 촉매 패턴 표면에 선택적으로 도금된다(S110).Next, the substrate on which the three-dimensional catalyst pattern is printed is immersed in a plating solution to electrolessly plate the metal. The plating metal is selectively plated on the surface of the catalyst pattern (S110).
본 발명에서 상기 도금 용액은 Cu, Ni, Ni-P, Ni-W-P, Ni-W-Cu-P와 같은 다양한 금속 및 금속 합금을 함유하는 용액일 수 있다. In the present invention, the plating solution may be a solution containing various metals and metal alloys such as Cu, Ni, Ni-P, Ni-W-P, and Ni-W-Cu-P.
본 발명에서 도금용 촉매 잉크의 폴리머 바인더는 도금 용액 내에서 LCST 거동을 나타낸다. 따라서, 도금 용액의 온도는 LCST 이상으로 유지된다. 바람직하게는 도금 용액의 온도는 폴리머-용매 시스템의 조성-온도 상평형도 상에서 스피노달 곡선 상부에 위치하도록 조절된다. 이에 따라, 폴리머 바인더는 도금 용액 내에서 용해되지 않으며, 도금막을 기재에 견고히 결합할 수 있게 된다. 또한, 촉매 패턴의 형상은 도금 후의 패턴에 그대로 전사될 수 있다. In the present invention, the polymer binder of the catalytic ink for plating exhibits LCST behavior in the plating solution. Therefore, the temperature of the plating solution is maintained above LCST. Preferably, the temperature of the plating solution is adjusted to be located above the spinodal curve on the composition-temperature phase equilibrium diagram of the polymer-solvent system. Accordingly, the polymer binder is not dissolved in the plating solution, and the plating film can be firmly bonded to the substrate. In addition, the shape of the catalyst pattern can be transferred as it is to the pattern after plating.
무전해 도금에서의 도금 속도는 도금 용액의 온도에 의존한다. 구체적으로, 도금 속도는 도금 온도에 지수적으로 비례하여 증가할 수 있다. 따라서, 본 발명의 도금용 촉매 잉크를 이용한 도금 방법은 높은 온도에서의 도금을 가능하게 함으로써 도금막의 성장 속도를 대폭 향상시킬 수 있게 된다.The plating rate in electroless plating depends on the temperature of the plating solution. Specifically, the plating speed may increase exponentially with the plating temperature. Therefore, the plating method using the catalyst ink for plating of the present invention can significantly improve the growth rate of the plating film by enabling plating at a high temperature.
<실험예 1 : 도금용 잉크의 제조><Experimental Example 1: Preparation of plating ink>
물에 질산은(대정화금) 100 g/L, 3-아미노프로필트리엑톡시실(시그마알드리치) 100 g/L, 하이드로식프로필 셀룰로스(시그마알드리치) 200 g/L, Graphite powder 250g/L 를 각각 상온에서 물에 순차적으로 녹여 잉크를 제조하였다. 100 g / L of silver nitrate (large gold) in water, 100 g / L of 3-aminopropyl triethoxysil (Sigma Aldrich), 200 g / L of hydrosylpropyl cellulose (Sigma Aldrich), and 250 g / L of Graphite powder, respectively Ink was prepared by sequentially dissolving in water at room temperature.
도금용 촉매 잉크의 점도를 콘-앤드-플레이트 레오미터(MCR102, Anton Paar)로 100~ 102 s-1의 전단 속도 범위에서 측정하였다. 저장탄성률과 손실탄성률을 응력의 함수로 구하기 위하여 1 Hz의 일정 주파수에서 응력을 연속적으로 변화시켰다.The viscosity of the catalyst ink for plating was measured with a cone-and-plate rheometer (MCR102, Anton Paar) in a shear rate range of 10 0 to 10 2 s -1 . In order to obtain the storage modulus and the loss modulus as a function of stress, the stress was continuously changed at a constant frequency of 1 Hz.
도 5는 제조된 도금용 촉매 잉크의 유동 특성을 나타낸 그래프이다. 도 5의 우측 상단 그래프에서 알 수 있는 바와 같이, 촉매 잉크는 전단 속도에 따라 점도가 감소하는 전단박화 현상을 나타내고 있다. 5 is a graph showing the flow characteristics of the prepared catalyst ink for plating. As can be seen from the upper right graph of FIG. 5, the catalyst ink exhibits a shear thinning phenomenon in which viscosity decreases with shear rate.
또, 도 5에 도시된 바와 같이, 촉매 잉크는 전단 응력이 낮은 구간에서는 저장 모듈러스(storage modulus) > 손실 모듈러스(loss modulus)인 고체 유사 거동을 나타내지만, 전단 응력이 높은 구간에서는 저장 모듈러스(storage modulus) < 손실 모듈러스(storage modulus)인 액체 유사 거동을 나타내고 있다. 그러므로, 노즐의 토출 압력을 적절히 제어함으로써 본 발명의 잉크가 노즐을 통과할 때에는 액체 유사 거동을 나타내어 끊김 없이 방출되도록 하고, 노즐을 통과하여 기재 상에 적층된 후에는 고체 유사 거동을 나타내어 3차원 구조체의 일부분으로서 그 형상을 유지할 수 있게 된다. In addition, as shown in FIG. 5, the catalyst ink exhibits a solid-like behavior of storage modulus> loss modulus in a section with low shear stress, but storage modulus in a section with high shear stress (storage) modulus) <liquid modulus of loss modulus (storage modulus). Therefore, by properly controlling the ejection pressure of the nozzle, the ink of the present invention exhibits liquid-like behavior when passing through the nozzle, so that it is discharged seamlessly, and after passing through the nozzle and laminated on a substrate, it exhibits a solid-like behavior and shows a three-dimensional structure. As part of it, the shape can be maintained.
< 실험예 2 : 전구체 패턴의 제작><Experimental Example 2: Preparation of precursor pattern>
실험예 1에서 제조된 잉크로 노즐 팁의 개구 직경 200 ㎛인 마이크로노즐을 이용하여 폴리이미드 기재 상에 50 mm * 50 mm * 100 mm(L*W*H)인 그리드 구조의 3차원 촉매 패턴을 형성하였다. 제조된 3차원 전구체 패턴을 히타치사의 S-4800 FE-SEM으로 관찰하였다.50 mm * 50 mm * 100 on a polyimide substrate using a micronozzle having an opening diameter of 200 µm with the ink prepared in Experimental Example 1 A three-dimensional catalyst pattern having a grid structure of mm (L * W * H) was formed. The prepared 3D precursor pattern was observed with Hitachi S-4800 FE-SEM.
< 실험예 3 : 무전해 도금><Experimental Example 3: Electroless plating>
실험예 1에서 제조된 전구체 패턴을 약 60 ℃의 온도로 유지되는 Cu 무전해도금 용액(황산제이구리 5수화물 (대정화금) 6.78 g/L, 주석산수소칼륨 (대정화금) 20.04 g/L (대정화금), 수산화나트륨 (대정화금) 8g/L) 내에 3~30 분간 침지하여 도금 하였다. 제조된 도금 패턴을 히타치사의 S-4800 FE-SEM으로 관찰하였다. 또, 전기 전도도는 상온에서 케이슬리 2612A 장비를 이용하여 2점 프로브 방식으로 측정하였다.Cu electroless plating solution (precured copper sulfate pentahydrate (large gold)) 6.78 g / L, potassium hydrogen stannate (gold gold) 20.04 g / L (Daejunghwa) and sodium hydroxide (daejunghwa) 8g / L) was immersed for 3 to 30 minutes and plated. The prepared plating pattern was observed with Hitachi S-4800 FE-SEM. In addition, the electrical conductivity was measured by a two-point probe method using a Keithley 2612A equipment at room temperature.
도 6은 실험예에 따라 제조된 3차원 촉매 패턴을 도금 용액 내에서 침지 시간을 달리하여 도금한 샘플의 사진이다. 6 is a photograph of a sample plated by varying the immersion time in a plating solution for a three-dimensional catalyst pattern prepared according to the experimental example.
도 6을 참조하면, 도금 과정에서 3차원 패턴의 형상이 그대로 유지됨을 알 수 있고, 도금 시간이 경과됨에 따라 도금 입자의 크기가 증가함을 알 수 있다. Referring to FIG. 6, it can be seen that the shape of the three-dimensional pattern is maintained in the plating process, and it can be seen that the size of the plated particles increases as the plating time elapses.
도 7은 도금 시간에 따라 얻어진 도금 패턴의 전기적 특성을 측정한 결과를 나타낸 그래프이다. 도 7은 도금 시간이 경과함에 따라 저항이 감소함을 보여주고 있다. 7 is a graph showing the results of measuring the electrical properties of the plating pattern obtained according to the plating time. 7 shows that the resistance decreases as the plating time elapses.
<실험예 4 ><Experimental Example 4>
표면 경사를 가진 기재의 표면을 따라 촉매 패턴을 형성하고, 이를 도금하였다. A catalyst pattern was formed along the surface of the substrate having a surface slope and plated.
표면 경사는 140° 및 90° 경사를 가진 기재를 사용하였다. 도 8의 (a)는 각 기재 상에 인쇄된 패턴의 이미지이고, 도 8의 (b)는 도금을 거친 패턴을 촬영한 이미지이다. 잉크젯이나 에어로젯과 같은 종래의 프린팅 장비는 완만한 경사에서 패턴의 인쇄가 가능하지만 본 발명에서는 90° 경사의 기재 상에 패턴의 인쇄가 가능하게 된다For the surface inclination, substrates having inclinations of 140 ° and 90 ° were used. 8 (a) is an image of a pattern printed on each substrate, and FIG. 8 (b) is an image of a pattern subjected to plating. Conventional printing equipment such as inkjet or aerojet can print a pattern at a gentle slope, but in the present invention, it is possible to print a pattern on a substrate having a 90 ° slope.
이상, 본 발명의 실시예를 통해 본 발명을 상술하였지만 이상의 설명은 본 발명을 예시한 것으로 본 발명이 이에 한정되는 것이 아니다. 첨부된 청구범위와 본 발명의 요지를 벗어남이 없이 당해 발명이 속하는 분야에서 통상의 지식을 가진 자라면 누구든지 다양한 변경 실시가 가능한 범위까지 본 발명의 범위에 속하는 것으로 간주 되어야 할 것이다. As described above, the present invention has been described through an embodiment of the present invention, but the above description is only illustrative of the present invention, and the present invention is not limited thereto. Any person having ordinary knowledge in the field to which the present invention pertains should be regarded as belonging to the scope of the present invention to the extent that various changes can be implemented without departing from the scope of the appended claims and the present invention.
본 발명은 3D 구조체의 제조에 이용 가능하다.The present invention can be used for the production of 3D structures.

Claims (17)

  1. 폴리머 바인더;Polymer binders;
    촉매로서의 금속 이온; Metal ions as catalysts;
    상기 폴리머 바인더와 금속 이온을 커플링하는 커플링제; A coupling agent coupling the polymer binder and a metal ion;
    골격 조형 분말; 및Skeletal molding powder; And
    용매를 포함하고Contains solvent
    상기 폴리머는 용매-폴리머 2원계의 온도-조성 상평형도 상에서 임계 온도 하한(Lower Critical Solution Temperature)을 가지고, 상기 임계 온도 하한은 30℃ 이상인 것을 특징으로 하는 도금용 촉매 잉크.The polymer has a solvent-polymer binary system temperature-composed on the phase equilibrium diagram has a lower critical temperature (Lower Critical Solution Temperature), the lower critical temperature is a catalyst ink for plating, characterized in that at least 30 ℃.
  2. 제1항에 있어서, According to claim 1,
    상기 임계 온도 하한은 50℃ 이상인 것을 특징으로 하는 도금용 촉매 잉크.The lower limit of the critical temperature is a catalyst ink for plating, characterized in that more than 50 ℃.
  3. 제1항에 있어서, According to claim 1,
    상기 용매는 물, 알코올, 또는 아세톤인 것을 특징으로 하는 도금용 촉매 잉크.The solvent is water, alcohol, or a catalyst ink for plating, characterized in that acetone.
  4. 제3항에 있어서, According to claim 3,
    상기 폴리머는 OH 작용기를 포함하는 것을 특징으로 하는 도금용 촉매 잉크.The polymer ink for plating, characterized in that it comprises an OH functional group.
  5. 제3항에 있어서, According to claim 3,
    상기 폴리머는 Hydroxypropyl cellulose, Methyl cellulose, Hydroxypropylmethyle cellulose, Ethyl(hydroxyethyl)cellulose, Poly(N-isopropylacrylamide-co-acrylic acid) 및 Poly(propylene glycol)로 이루어진 그룹 중에서 선택된 최소한 1종을 포함하는 것을 특징으로 하는 도금용 촉매 잉크.The polymer is characterized in that it comprises at least one selected from the group consisting of Hydroxypropyl cellulose , Methyl cellulose , Hydroxypropylmethyle cellulose, Ethyl (hydroxyethyl) cellulose , Poly (N-isopropylacrylamide-co-acrylic acid) and Poly (propylene glycol). Catalytic ink for plating.
  6. 제1항에 있어서, According to claim 1,
    상기 금속 이온의 금속은 Ag, Fe, Co, Ni, Cu, Pd, Pt, Sn, Au로 이루어진 그룹 중에서 선택된 최소한 1종인 것을 특징으로 하는 도금용 촉매 잉크.The metal ion metal is a catalyst ink for plating, characterized in that at least one selected from the group consisting of Ag, Fe, Co, Ni, Cu, Pd, Pt, Sn, Au.
  7. 제1항에 있어서, According to claim 1,
    상기 골격 조형 분말은 CNT, 그라파이트, 그래핀 및 산화 그래핀으로 이루어진 그룹 중에서 선택된 최소한1종의 분말을 포함하는 것을 특징으로 하는 도금용 촉매 잉크.The skeleton molding powder is a catalyst ink for plating, characterized in that it comprises at least one powder selected from the group consisting of CNT, graphite, graphene and graphene oxide.
  8. 제1항에 있어서, According to claim 1,
    상기 골격 조형 분말은 금속 산화물 분말 또는 금속 질화물 분말을 포함하는 것을 특징으로 하는 도금용 촉매 잉크.The skeleton molding powder is a catalyst ink for plating, characterized in that it comprises a metal oxide powder or a metal nitride powder.
  9. 기재 상에, 폴리머 바인더, 촉매로서의 금속 이온 및 상기 폴리머 바인더, 골격 조형 분말 및 용매를 포함하는 도금용 촉매 잉크를 토출하여 3차원 촉매 패턴을 형성하는 단계; 및Forming a three-dimensional catalyst pattern by discharging a catalyst ink for plating containing a polymer binder, a metal ion as a catalyst, and the polymer binder, a skeleton molding powder, and a solvent on a substrate; And
    상기 전구체 패턴이 형성된 기재를 상기 용매-폴리머 2원계의 온도-조성 상평형도 상에서 임계 온도 하한(Lower Critical Solution Temperature) 이상의 온도로 유지되는 도금 용액 내에 침지하여 무전해 도금하여 도금 패턴을 형성하는 단계를 포함하는 3차원 구조체의 제조 방법.Forming a plating pattern by immersing the substrate on which the precursor pattern is formed in a plating solution maintained at a temperature above a lower critical solution temperature on a temperature-composition phase equilibrium of the solvent-polymer binary system to electroless plating Method of manufacturing a three-dimensional structure comprising a.
  10. 제9항에 있어서,The method of claim 9,
    상기 용매는 물이고,The solvent is water,
    상기 폴리머는 Hydroxypropyl cellulose, Methyl cellulose, Hydroxypropylmethyle cellulose, Ethyl(hydroxyethyl)cellulose, Poly(N-isopropylacrylamide-co-acrylic acid) 및 Poly(propylene glycol)로 이루어진 그룹 중에서 선택된 최소한 1종을 포함하는 것을 특징으로 하는 3차원 구조체의 제조 방법.The polymer is characterized in that it comprises at least one selected from the group consisting of Hydroxypropyl cellulose , Methyl cellulose , Hydroxypropylmethyle cellulose, Ethyl (hydroxyethyl) cellulose , Poly (N-isopropylacrylamide-co-acrylic acid) and Poly (propylene glycol). Method of manufacturing a three-dimensional structure.
  11. 제9항에 있어서,The method of claim 9,
    상기 임계 온도 하한은 30℃ 이상인 것을 특징으로 하는 3차원 구조체의 제조 방법.The lower limit of the critical temperature is a manufacturing method of a three-dimensional structure, characterized in that at least 30 ℃.
  12. 제9항에 있어서,The method of claim 9,
    상기 임계 온도 하한은 50℃ 이상인 것을 특징으로 하는 3차원 구조체의 제조 방법.The lower limit of the critical temperature is a manufacturing method of a three-dimensional structure, characterized in that 50 ℃ or more.
  13. 제9항에 있어서,The method of claim 9,
    상기 임계 온도 하한은 55℃ 이상인 것을 특징으로 하는 도금용 촉매 잉크.The lower critical temperature is a catalyst ink for plating, characterized in that 55 ℃ or more.
  14. 제9항에 있어서,The method of claim 9,
    상기 임계 온도 하한은 60℃ 이상인 것을 특징으로 하는 도금용 촉매 잉크.The lower limit of the critical temperature is a catalyst ink for plating, characterized in that at least 60 ℃.
  15. 제9항에 있어서,The method of claim 9,
    상기 임계 온도 하한은 65℃ 이상인 것을 특징으로 하는 도금용 촉매 잉크.The lower limit of the critical temperature is a catalyst ink for plating, characterized in that more than 65 ℃.
  16. 제9항에 있어서,The method of claim 9,
    상기 3차원 촉매 패턴 형성 단계는, The three-dimensional catalyst pattern forming step,
    상기 도금용 촉매 잉크를 노즐을 통해 가압 토출하는 것을 특징으로 하는 3차원 구조체의 제조 방법.A method of manufacturing a three-dimensional structure, characterized in that the plating catalyst ink is discharged under pressure through a nozzle.
  17. 제13항에 있어서,The method of claim 13,
    상기 도금용 촉매 잉크는 전단 응력 하에서 고체 유사 거동에서 액체 유사 거동으로 전이하는 것을 특징으로 하는 3차원 구조체의 제조 방법.The method of manufacturing a three-dimensional structure, characterized in that the catalyst ink for plating transitions from a solid-like behavior to a liquid-like behavior under shear stress.
PCT/KR2019/013079 2018-10-05 2019-10-04 Catalyst ink for plating to form three-dimensional structure and method for manufacturing three-dimensional structure using same WO2020071875A1 (en)

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