WO2017090899A1 - Procédé de formation de motif d'électrode à structure flottante, et procédé d'impression par transfert l'utilisant - Google Patents

Procédé de formation de motif d'électrode à structure flottante, et procédé d'impression par transfert l'utilisant Download PDF

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WO2017090899A1
WO2017090899A1 PCT/KR2016/012123 KR2016012123W WO2017090899A1 WO 2017090899 A1 WO2017090899 A1 WO 2017090899A1 KR 2016012123 W KR2016012123 W KR 2016012123W WO 2017090899 A1 WO2017090899 A1 WO 2017090899A1
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electrode pattern
substrate
buffer layer
temperature
forming
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PCT/KR2016/012123
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English (en)
Korean (ko)
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김학린
최준찬
박지섭
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경북대학교 산학협력단
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    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K77/00—Constructional details of devices covered by this subclass and not covered by groups H10K10/80, H10K30/80, H10K50/80 or H10K59/80
    • 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
    • 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
    • H01L21/30—Treatment of semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/26
    • H01L21/31—Treatment of semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/26 to form insulating layers thereon, e.g. for masking or by using photolithographic techniques; After treatment of these layers; Selection of materials for these layers
    • H01L21/3205—Deposition of non-insulating-, e.g. conductive- or resistive-, layers on insulating layers; After-treatment of these layers
    • H01L21/321—After treatment
    • H01L21/3213—Physical or chemical etching of the layers, e.g. to produce a patterned layer from a pre-deposited extensive layer
    • 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
    • H01L21/30—Treatment of semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/26
    • H01L21/324—Thermal treatment for modifying the properties of semiconductor bodies, e.g. annealing, sintering
    • 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
    • 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
    • H05K3/12—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 thick film techniques, e.g. printing techniques to apply the conductive material or similar techniques for applying conductive paste or ink patterns

Definitions

  • the present invention relates to an electrode pattern forming method, and more particularly, an electrode pattern forming method for forming an electrode pattern based on metal nanoparticle ink in a floating structure and a transfer printing method using the electrode pattern forming method of the floating structure. It is about.
  • Such conductive inks mainly use metal nanoparticles.
  • the metal nanoparticles described above can be dispersed in a solvent in order to 'ink' the material, and high resolution can be realized at the time of forming the wiring electrode. It can be expected to have a short time at relatively low temperature due to the thermodynamic size effect due to the small particle size during the sintering process.
  • the conductive ink is prepared by dispersing metal nanoparticles, that is, nano-size metal particles in a solvent (solvent).
  • metal nanoparticles that is, nano-size metal particles in a solvent (solvent).
  • the metal nanoparticles are dispersed in a very unstable state, the particles are initially dispersed in a solvent, but the metal nanoparticles aggregate again after a short time. Due to such agglomeration, there is a problem in that uniformity and conductivity characteristics of the wiring electrode are formed through the printing process and the reproducibility of the low process is low.
  • the representative conductive ink manufacturing method proposed to solve this problem is a 'steric stabilization' method, which improves dispersion stability by preventing agglomeration between particles by coating a material that enhances the dispersion degree of a solvent on the surface of metal nanoparticles. have.
  • the conductive properties of the wiring electrodes are very poor due to the insulating properties of the materials positioned between the metal nanoparticles.
  • the crosslinked material mixed with the thin film formed by the printing process to induce stable adhesive properties to the substrate and to prevent cracking and deformation of the thin film is also a material having insulation properties, the wiring electrode exhibits a poor conductivity characteristic.
  • sintering refers to a phenomenon in which a powder is solidified when a powder receives strong energy from the outside and bonds between the powder particles.
  • the sintering process simply binds the particles together, thereby increasing the particle size to ideally form a thin film free of voids and coating the surface of the metal nanoparticles to improve dispersion stability.
  • the decomposed material is decomposed and disappeared, thereby maximizing conductivity characteristics.
  • FIG. 1 is a conceptual diagram illustrating a sintering process of metal nanoparticles of a conductive ink. As shown in FIG. 1, the coated polymer is decomposed and disappeared by the sintering process, and as the bonding between the metal nanoparticles occurs and solidifies, a metal wiring having high conductivity characteristics can be formed.
  • the most typical sintering method is a sintering method in which the ink printed on the substrate is heat-treated using an oven or a furnace.
  • heat treatment sintering is a very basic treatment method has the advantage that the process is simple and excellent conductive properties can be obtained.
  • the heat treatment sintering method is slightly different for each material, but a high temperature heat treatment process of 150 ° C to 300 ° C is usually required, and when applied to flexible electronics, most of the film substrates to be used as substrates are higher than the sintering temperature. At low temperatures, deformation of the substrate occurs.
  • PET is 120 °C
  • PEN is 180 °C
  • PI is 300 °C to obtain a metal wiring having excellent conductive properties by heat treatment sintering method on a flexible film substrate, there is a problem that there is a limitation in selecting a substrate have.
  • the conductive ink when the conductive ink is printed on an arbitrary substrate and then sintered, the conductive properties of the metal thin film are changed by a crosslinking agent for bonding between the metal nanoparticles constituting the conductive ink and improving adhesion between the thin film and the substrate.
  • the thin metal film is also bonded to the substrate to increase the bonding force between the conductive ink-based metal thin film and the substrate. Therefore, in the case of forming the metal wiring through the high temperature heat sintering treatment using the conductive ink, the bonding force between the conductive ink and the substrate is increased by the sintering treatment, and it is difficult to pick up the conductive ink using a stamp by a general transfer printing method. There is a problem.
  • FIG. 2 is a cross-sectional view of the supporters 120, 122, and 124 formed by etching when the electrode patterns 110, 112, and 114 of various sizes are present on the substrate 100.
  • a support having a large cross-sectional area may be formed.
  • a support having a small cross-sectional area may be formed. In this case, when the size of the electrode pattern is extremely small, the support may not be formed, and when the size of the electrode pattern is large, the support of the large cross-sectional area is formed, and pickup may not be easy.
  • the present invention for solving the above problems is to form an electrode pattern using a conductive ink that requires a heat sintering process, even if there are electrode patterns of various sizes to provide a method of forming an electrode pattern of a floating structure easy to pick up
  • Another object of the present invention is to provide a method for transferring printing by using the above-described electrode pattern forming method of the floating structure.
  • a method of forming an electrode pattern of a floating structure comprising: (a) applying a thermoplastic polymer having a property of thermal decomposition at a predetermined temperature or more on a substrate to form a buffer layer on the substrate; Forming a; (b) forming an electrode pattern by printing conductive ink on a surface of the buffer layer; And (c) heat sintering the electrode pattern.
  • Step (c) is characterized in that the electrode pattern is thermally sintered at a temperature higher than the pyrolysis temperature of the thermoplastic polymer material, by the thermal sintering of the electrode pattern of the step (c), located between the electrode pattern and the substrate
  • the thermoplastic polymer constituting the limited area buffer layer is selectively pyrolyzed and removed, and the buffer layer is self-patterned along the edge of the electrode pattern to form a support, whereby the electrode pattern is floated on the substrate by an anchor.
  • the electrode pattern is thermally sintered at a temperature higher than the pyrolysis temperature of the thermoplastic polymer material, by the thermal sintering of the electrode pattern of the step (c), located between the electrode pattern and the substrate
  • the thermoplastic polymer constituting the limited area buffer layer is selectively pyrolyzed and removed, and the buffer layer is self-patterned along the edge of the electrode pattern to form a support, whereby the electrode pattern is floated on the substrate by an anchor.
  • the electrode layer is heated by applying heat above the thermal decomposition temperature of the buffer layer to a substrate in a state where the buffer layer is exposed to an atmosphere at room temperature.
  • the buffer layer in a limited region located between the electrode pattern and the substrate is pyrolyzed by maintaining a temperature higher than the pyrolysis temperature, and the buffer layer exposed to an ambient temperature of the atmosphere is not pyrolyzed by maintaining a temperature lower than the pyrolysis temperature. It is preferable to selectively remove only a limited region of the buffer layer by thermal decomposition.
  • the substrate is preferably a heat-resistant glass substrate or a wafer that does not deform or break even when thermally sintered to the electrode pattern.
  • the method may further include etching (d) the buffer layer after the step (c), wherein the step (d) includes etching the buffer layer, It is preferable to adjust the area of the electrode pattern and the buffer layer by etching the lower layer of the corner of the electrode by controlling the conditions.
  • the wet etching of the buffer layer may be performed, and the etching solution of the buffer layer may be made of a material that does not affect the characteristics of the electrode pattern.
  • step (d) it is more preferable to control the etching rate or the etching time with respect to the buffer layer to adjust the area where the electrode pattern and the buffer layer contact each other.
  • the conductive ink is formed by dispersing metal nanoparticles coated with a dispersant in a solvent, and the conductive ink has high conductivity by thermal sintering. Will have characteristics.
  • a transfer printing method comprising: (a) applying a thermoplastic polymer material having a property of thermal decomposition at a predetermined temperature or more on a first substrate to form a buffer layer on the first substrate; (b) forming an electrode pattern by printing conductive ink on a surface of the buffer layer; (c) heat sintering the electrode pattern, and forming a self-patterned support by pyrolysis of the buffer layer generated simultaneously with the sintering; (d) picking up the electrode pattern from the first substrate using a stamp while the electrode pattern is fixed and aligned by a support; And (e) transferring the picked up electrode pattern onto a second substrate.
  • Step (c) is characterized in that the electrode pattern is thermally sintered at a temperature higher than the pyrolysis temperature of the thermoplastic polymer material, by the thermal sintering of the electrode pattern of the step (c), between the electrode pattern and the first substrate
  • the thermoplastic polymer constituting the buffer layer of the limited region located at is selectively pyrolyzed and removed, and the support is formed along the edge of the electrode pattern, whereby the electrode pattern is floated on the first substrate by an anchor.
  • step (c) by applying heat above the thermal decomposition temperature of the buffer layer to the first substrate in a state where the buffer layer is exposed to the atmosphere of room temperature Characterized in that the electrode pattern is thermally sintered
  • the buffer layer in the limited region positioned between the electrode pattern and the first substrate is maintained at a temperature higher than the thermal decomposition temperature, and the buffer layer exposed to the ambient temperature is not pyrolyzed because the temperature higher than the thermal decomposition temperature is not maintained. It is desirable to selectively pyrolyze and remove the limited region of the buffer layer.
  • the first substrate is a heat-resistant glass substrate or a wafer which is not deformed or damaged even by thermal sintering with respect to the electrode pattern
  • the second substrate Is preferably a flexible substrate.
  • the step (e) is (e1) contact printing (print printing) the stamp to pick up the electrode pattern on the adhesive material, Forming an adhesive layer on a lower surface of the electrode pattern; (e2) disposing a stamp having the adhesive layer formed on the second substrate; (e3) separating the stamp from the electrode pattern; and preferably, transferring the electrode pattern onto the second substrate through the adhesive layer.
  • thermoplastic polymer layer is introduced between an electrode pattern and a substrate, and a heat sintering temperature is performed at a temperature higher than a pyrolysis temperature of the thermoplastic polymer, thereby simultaneously heating the electrode pattern and forming an electrode pattern. Only a limited area of the thermoplastic polymer located underneath is selectively pyrolyzed and removed. As a result, a buffer layer below the electrode pattern is self-patterned along the edge of the electrode pattern to form a support, thereby forming a floating structure in which the electrode pattern floats on the substrate by the support. .
  • thermoplastic polymer layer after the heat sintering process, by reducing the area of the electrode pattern and the contact with the buffer layer so that the electrode pattern can be more easily separated from the buffer layer during the pickup (pick-up) process.
  • the support fabricated by the electrode pattern forming method of the floating structure according to the present invention can be formed the same regardless of the size of the electrode pattern, can be utilized in the transfer printing technology of the electrode pattern based on the metal nanoparticle ink. have.
  • the transfer printing method using the electrode pattern forming method according to the present invention is formed by forming an electrode pattern using a conductive ink on a substrate having a high heat resistance, then subjected to high temperature thermal sintering process and transfer printing on a flexible substrate, thereby the conductive ink The heat sintering process can be performed, and as a result, a metal wiring having high conductivity can be formed on the flexible substrate.
  • the transfer printing method using the electrode pattern forming method according to the present invention by using a stamp having a patterned mold, not only iterative transfer printing is possible, but also lamination of the mesh structure through such a repeated transfer printing
  • the formed metal wiring can also be formed.
  • the transfer printing method using the electrode pattern forming method according to the present invention by forming an adhesive layer between the electrode pattern and the flexible substrate, the thin film separation phenomenon that the high-conductivity electrode pattern is separated from the flexible substrate by bending or the like. It can be removed.
  • FIG. 1 is a conceptual diagram illustrating a sintering process of metal nanoparticles of a conductive ink.
  • FIG. 2 is a cross-sectional view illustrating exemplary supports formed by a conventional etching process when various sizes of electrode patterns exist on a substrate.
  • FIG. 3 is a flowchart sequentially illustrating a method of forming an electrode pattern of a floating structure according to a first exemplary embodiment of the present invention.
  • FIG. 4 is a cross-sectional view illustrating electrode patterns formed of a floating structure on a substrate by a support in the method of forming an electrode pattern of a floating structure according to a first embodiment of the present invention.
  • FIG. 5 is a cross-sectional view sequentially showing a transfer printing method in order to explain the transfer printing method using the electrode pattern forming method of the floating structure according to the first embodiment of the present invention.
  • FIG. 6 is a flowchart sequentially illustrating a method of forming an electrode pattern of a floating structure according to a second exemplary embodiment of the present invention.
  • FIG. 7 is a cross-sectional view illustrating electrode patterns formed in a floating structure on a substrate by a support in the method of forming an electrode pattern of a floating structure according to a second embodiment of the present invention.
  • FIG. 8 is a cross-sectional view sequentially showing the transfer printing method in order to explain the transfer printing method using the electrode pattern forming method of the floating structure according to the second embodiment of the present invention.
  • FIG. 9 is a graph showing pick-up yields versus etching time for a buffer layer in the transfer printing method using the electrode pattern forming method according to the present invention
  • FIG. 10 is a graph illustrating each etching time. Microscopic images of the picked-up state for.
  • FIG. 11 is a graph showing pick-up yield according to pick-up velocity when the etching time is 5 minutes in the pickup of an electrode pattern using a stamp, and FIG. Microscopic images of the electrode pattern taken.
  • FIG. 13 shows photographs of stability test for bending according to whether an adhesive layer is formed when an electrode pattern is formed on a flexible substrate using a transfer printing method according to the present invention.
  • the method of forming an electrode pattern of a floating structure in the method of forming an electrode pattern of a floating structure according to the present invention, after forming a buffer layer by applying a thermoplastic polymer on a substrate, printing a conductive ink thereon to form an electrode pattern, and then forming the electrode pattern at a temperature higher than the thermal decomposition temperature of the thermoplastic polymer. Is thermally sintered.
  • the buffer layer of the limited region located under the electrode pattern is thermally decomposed and removed at the same time as the heat of the electrode pattern, so that the buffer layer is self-patterned along the edge of the electrode pattern to form a support.
  • the electrode pattern is characterized by forming a floating structure (floating structure) floating on the substrate by the support.
  • FIG. 3 is a process diagram sequentially illustrating a metal wiring forming method according to a preferred embodiment of the present invention.
  • the electrode pattern forming method of the floating structure may be formed by first applying a thermoplastic polymer material on a substrate 300 to form a buffer layer 310. Thereafter, the conductive ink 320 'is printed on the buffer layer.
  • the substrate is a substrate having excellent thermal conductivity and heat resistance, and is preferably a flat substrate that is not deformed even at a temperature at which the conductive ink is heat-sintered and sintered, and heat resistant glass or wafer may be used.
  • the buffer layer 310 is composed of a thermoplastic polymer having a property of thermally decomposing when heat above a predetermined temperature is applied, and the pyrolysis temperature should be a material lower than the sintering temperature of the conductive ink.
  • the conductive ink is a metal nanoparticles coated with a dispersant is dispersed in a solvent, it is made of a material having a conductive characteristic mixed with a binding material to enable the printing process and improve the mechanical properties do.
  • the conductive ink is printed on the surface of the buffer layer according to a preset electrode pattern.
  • the metal nanoparticles may be, for example, Au, Ag, Cu, Ni and the like.
  • a hot hot plate 350 is disposed below the substrate.
  • the conductive pattern is improved by sintering the conductive ink by applying heat from the lower portion of the substrate to the substrate by the hot plate 350, thereby forming an improved electrode pattern 320. do.
  • the upper surface of the buffer layer formed on the upper surface of the substrate is exposed to the atmosphere at room temperature, by applying heat above the thermal decomposition temperature of the buffer layer from the lower portion of the substrate to the substrate using a hot plate, heat sintering the electrode pattern It is desirable to.
  • the thermal sintering process is carried out in a vacuum oven instead of a hot plate, the whole inside of the vacuum oven maintains a high temperature environment, and thermal decomposition occurs in all regions of the buffer layer, thereby making selective polymer pyrolysis impossible.
  • the electrode pattern of the floating structure according to the present invention cannot be obtained.
  • thermoplastic polymers constituting the buffer layer are melted, and the corner portion of the electrode pattern 320 is bent downward.
  • the melted thermoplastic polymers positioned under the edges of the electrode patterns are pushed out by the bent electrode patterns, and the thermoplastic polymers under the edges of the electrode patterns are reduced in thickness to form a "reduced thickness area".
  • thermoplastic polymer in the lower part of the electrode pattern is trapped by the bent electrode, thereby forming a "confined area".
  • the buffer layer 310 of the confined area located between the electrode pattern and the substrate is kept at a temperature lower than the pyrolysis temperature so as not to be pyrolyzed, so that only a limited region of the buffer layer can be selectively pyrolyzed and removed.
  • thermoplastic polymer constituting the buffer layer when heat above a thermal decomposition temperature is applied to the buffer layer, the thermoplastic polymer constituting the buffer layer is decomposed to break the chains constituting the polymer, thereby obtaining a low molecular gas state.
  • the gaseous substance is absorbed or expelled into the pores of the conductive ink and disappears.
  • the buffer layer of the confined area located under the electrode pattern is thermally decomposed and removed at the same time as the heat of the electrode pattern, so that the buffer layer is self-patterned along the edge of the electrode pattern to form the support 312. Done.
  • the electrode pattern forms a floating structure floating on the substrate by the support.
  • the thickness and width of the supporters formed on the substrate is determined by the thickness and type of the buffer layer, and are formed to have a uniform thickness and width, regardless of the shape and size of the electrode pattern.
  • FIG. 4 is a view illustrating an electrode pattern 420, 422, 424 having a floating structure on a substrate 400 by a support 412 in the method of forming an electrode pattern of a floating structure according to a first embodiment of the present invention. It is shown in cross section.
  • electrode patterns 420, 422, and 424 of various sizes are positioned in a floating state on a substrate by supporting members 412 formed by self-patterning a buffer layer along edges of an electrode pattern.
  • each support 412 is formed to have a uniform thickness and width.
  • the conditions required for the etching process are all different according to the shape and size of the electrode pattern, there is a problem that it is difficult to transfer printing in a single process when present in the various electrode patterns on one substrate.
  • the electrode pattern forming method according to the present invention as described above, regardless of the shape and size of the electrode patterns, as each support is formed with a uniform thickness and width, regardless of the shape and size of the electrode pattern Transfer printing can be done simultaneously in a single process.
  • the electrode pattern forming method of the floating structure according to the first embodiment of the present invention described above can be used in the transfer printing process.
  • a transfer printing process may be used. It is preferable to apply the electrode pattern forming method of the floating structure according to.
  • FIG. 5 is a cross-sectional view sequentially showing a transfer printing method in order to explain the transfer printing method using the electrode pattern forming method of the floating structure according to the first embodiment of the present invention.
  • a thermoplastic polymer is coated on a first substrate to form a buffer layer, and a conductive ink is printed to form an electrode pattern.
  • high temperature heat is applied from the lower part of the substrate to the substrate using a hot plate to thermally decompose the thermoplastic polymer constituting the buffer layer.
  • the electrode pattern is thermally sintered to a temperature higher than the temperature.
  • the buffer layer in the limited region located between the electrode pattern and the first substrate is thermally decomposed and removed.
  • the buffer layer is self-patterned along the edge of the electrode pattern, resulting in a self-patterned support for the edge of the electrode pattern.
  • an electrode pattern having a structure floating on the first substrate by the support is formed. Since these processes are the same as the electrode pattern forming method of the floating structure described above, overlapping description is omitted.
  • an electrode pattern is picked up using a flat stamp 530.
  • the stamp is placed on the electrode pattern and pressure is applied, the electrode pattern can be picked up by the stamp as the electrode pattern is separated from the first substrate due to the difference in adhesion at each boundary portion.
  • an elastic stamp having viscoelasticity is required for optimizing pickup conditions, and the pickup speed of the stamp is set to 100 mm / s.
  • the stamp is preferably composed of a polymer having elasticity, for example, PDMS (polydimethylsiloxane), PUA (Polyurethane acrylate) may be used.
  • PDMS polydimethylsiloxane
  • PUA Polyurethane acrylate
  • the pickup speed of the stamp can adjust the adhesion energy (adhesion energy) between the electrode pattern and the stamp.
  • the adhesion force (W) according to the area where the two objects, that is, the electrode pattern (electrode) and the stamp (stamp) is in contact with the equation (1).
  • W electrode / stamp is the adhesion between the electrode pattern and the stamp (J)
  • w electrode / stamp is the specific adhesion energy (J / m 2 ) is determined by the characteristics of the electrode pattern and the stamp
  • f ( ⁇ ) is It is a monotonically increasing function determined by the experiment
  • S electrode / stamp means the area (m 2 ) where the electrode pattern is in contact with the stamp.
  • the pickup speed of the stamp may be increased in order to increase the adhesion between the electrode pattern and the stamp.
  • the thermoplastic polymer under the electrode pattern is removed through the selective pyrolysis of the thermoplastic polymer constituting the buffer layer, thereby reducing the contact area between the electrode pattern and the thermoplastic polymer. Giving must necessarily be preceded.
  • the adhesive material may be formed of a polymer material having strong adhesion, and a thermosetting material or a photocuring material that is thermally cured at a low temperature such as cellulose ether may be used.
  • an adhesive layer made of a polymer material having strong adhesion between the flexible substrate and the electrode pattern by forming an adhesive layer made of a polymer material having strong adhesion between the flexible substrate and the electrode pattern, stability to bending of the flexible substrate can be improved.
  • the electrode pattern 520 is completed on the surface of the second substrate 570 by separating the stamp from the electrode pattern.
  • the second substrate 570 is a flexible substrate for manufacturing flexible electronics. Since the high temperature heat sintering process does not need to be performed directly on the substrate, the second substrate 570 includes a substrate having low heat resistance. It can be used for all flexible heat resistant substrates such as poly-ethalene terephthlate (PET), poly-ethylene naphthalate (PEN), and polycarbonate (PC).
  • PET poly-ethalene terephthlate
  • PEN poly-ethylene naphthalate
  • PC polycarbonate
  • the electrode pattern forming method according to the second embodiment of the present invention is similar to the electrode pattern forming method of the first embodiment, except that after the support is formed by heat sintering, the method further comprises the step of etching the buffer layer to more easily pick up the electrode pattern. You can do it.
  • description overlapping with the first embodiment will be omitted, and the description will be mainly focused on differences.
  • FIG. 6 is a process diagram sequentially illustrating a metal wiring forming method according to a second embodiment.
  • thermoplastic polymer material is coated on a substrate 600 to form a buffer layer 610.
  • the conductive ink 620 ' is printed on the buffer layer.
  • the buffer layer 610 is composed of a thermoplastic polymer having a property of thermal decomposition when heat above a predetermined temperature is applied, and the thermal decomposition temperature must be a material lower than the sintering temperature of the conductive ink.
  • the thermoplastic polymer constituting the buffer layer may be a solution process and a material capable of chemical wet etching.
  • polymethyl methacrylate (PMMA), polystyrene (PS), or fluoropolymer may be used as an example of the thermoplastic polymer constituting the buffer layer.
  • a hot plate 650 of high temperature is disposed under the substrate.
  • an electrode pattern 620 having improved conductivity is formed by sintering the conductive ink by applying heat from the lower portion of the substrate to the substrate by the hot plate 650. do.
  • the upper surface of the buffer layer formed on the upper surface of the substrate is exposed to the atmosphere at room temperature, by applying heat above the thermal decomposition temperature of the buffer layer from the lower portion of the substrate to the substrate using a hot plate, heat sintering the electrode pattern It is desirable to.
  • the buffer layer of the limited region located under the electrode pattern is thermally decomposed and removed at the same time as the heat of the electrode pattern, so that the buffer layer is self-patterned along the edge of the electrode pattern to form a support.
  • the electrode pattern is characterized by forming a floating structure (floating structure) floating on the substrate by the support.
  • thermoplastic polymer constituting the buffer layer when heat above a thermal decomposition temperature is applied to the buffer layer, the thermoplastic polymer constituting the buffer layer is decomposed to break the chains constituting the polymer, thereby obtaining a low molecular gas state.
  • the gaseous substance is absorbed or expelled into the pores of the conductive ink and disappears.
  • the buffer layer is etched by wet etching by immersing in the buffer layer etching solution.
  • the buffer layer etching solution for etching the buffer layer should be a material that only reacts the buffer layer to etch the buffer layer and does not affect the conductive ink.
  • products with the buffer layer 3M TM's in the present embodiment "NOVEC TM 1700 Electronic Grade Coating ", methoxy-nonafluorobutane (C 4 F 9 OCH 3 ) may be used as the buffer layer etching solution, for example, 3M TM product name" NOVEC TM 7100 Engineered Fluid "may be used.
  • a buffer layer "NOVEC TM 1700 Electronic Grade Coating ", the pyrolysis temperature of this material is 250 ° C, so the thermal sintering temperature for the electrode pattern should be applied at a temperature higher than 250 ° C.
  • FIG. 7 exemplarily illustrates electrode patterns 720, 722, and 724 formed in a floating structure on a substrate 700 by a support 712 in the method of forming an electrode pattern having a floating structure according to a second embodiment. It is a cross section.
  • electrode patterns 720, 722, and 724 of various sizes are positioned in a floating state on a substrate by supporting members formed at lower ends of edges of the electrode patterns. Regardless, it can be seen that each support 712 is formed to have a uniform thickness and width.
  • FIG. 8 is a cross-sectional view sequentially showing the transfer printing method in order to explain the transfer printing method using the electrode pattern forming method of the floating structure according to the second embodiment of the present invention.
  • thermoplastic polymer is coated on a first substrate to form a buffer layer, and a conductive ink is printed to form an electrode pattern.
  • a conductive ink is printed to form an electrode pattern.
  • FIGS. 8B and 8C after forming an electrode pattern, high temperature heat is applied from the lower part of the substrate to the substrate using a hot plate to thermally decompose the thermoplastic polymer constituting the buffer layer.
  • the electrode pattern is thermally sintered to a temperature higher than the temperature. By this thermal sintering, the buffer layer in the limited region located between the electrode pattern and the first substrate is thermally decomposed and removed.
  • the buffer layer is etched while controlling the etching rate and the etching time, thereby reducing the area of the support formed by pyrolysis in the previous process to further reduce the area between the substrate and the support.
  • an electrode pattern having a structure floating on the first substrate by the support is formed. Since these processes are the same as the electrode pattern forming method of the floating structure described above, overlapping description is omitted.
  • an electrode pattern is picked up using a flat stamp 830.
  • the electrode pattern may be picked up by the stamp as the electrode pattern is separated from the first substrate due to the difference in adhesive force at each boundary portion.
  • FIG. 9 is a graph showing pick-up yields versus etching time for a buffer layer in the transfer printing method using the electrode pattern forming method according to the present invention
  • FIG. 10 is a graph illustrating each etching time. Microscopic images of the picked-up state for. 9 and 10, as the etching time increases, the pickup yield increases. By reducing the etching rate and adjusting the etching time, it is possible to precisely control the area in which the electrode pattern and the thermoplastic polymer contact each other, thereby increasing the pickup yield. On the other hand, as shown in Figs.
  • the pickup speed of the stamp may be increased.
  • FIG. 11 is a graph showing pick-up yield according to pick-up velocity when the etching time is 5 minutes in the pickup of an electrode pattern using a stamp, and FIG. Microscopic images of the electrode pattern taken. 11 and 12, it can be seen that the pickup yield increases as the pickup speed increases.
  • the contact area is reduced through selective pyrolysis and etching of the thermoplastic polymer constituting the buffer layer. Giving must necessarily be preceded.
  • the adhesive layer 860 is formed.
  • the electrode pattern of the stamp is transferred and printed on the surface of the second substrate 870.
  • the adhesive material may be formed of a polymer material having strong adhesion, and a thermosetting material or a photocuring material that is thermally cured at a low temperature such as cellulose ether may be used.
  • an adhesive layer made of a polymer material having strong adhesion between the flexible substrate and the electrode pattern by forming an adhesive layer made of a polymer material having strong adhesion between the flexible substrate and the electrode pattern, stability to bending of the flexible substrate can be improved.
  • the electrode pattern 820 is completed on the surface of the second substrate 870 by separating the stamp from the electrode pattern.
  • the most important factor when forming a functional element or a thin film on a flexible substrate is stability by bending of the substrate (Bending).
  • the thin film formed on the flexible substrate is subjected to bending stress, cracks may occur in the thin film or peeled from the flexible substrate.
  • the conductive ink has a crosslinking agent added thereto, the pick-up process is difficult due to the excellent adhesion between the metal wiring thin film and the substrate.
  • the adhesive property due to the crosslinking agent disappears, so that the crack can be reduced, but the thin film peeling phenomenon is present again.
  • FIG. 13 shows photographs of stability test for bending according to whether an adhesive layer is formed when an electrode pattern is formed on a flexible substrate using a transfer printing method according to the present invention.
  • FIG. 13A illustrates the case where the adhesive layer is not formed.
  • Figure 13 (b) is a case where the adhesive layer is formed, it can be seen that the thin film peeling phenomenon does not occur even if the flexible substrate is bent.
  • the method according to the invention can be widely used in the manufacturing process of flexible electronics using a flexible substrate.
  • it can be widely used when forming a highly conductive metal wiring on a flexible substrate using a conductive ink.

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  • Engineering & Computer Science (AREA)
  • Manufacturing & Machinery (AREA)
  • Microelectronics & Electronic Packaging (AREA)
  • Physics & Mathematics (AREA)
  • Condensed Matter Physics & Semiconductors (AREA)
  • General Physics & Mathematics (AREA)
  • Computer Hardware Design (AREA)
  • Power Engineering (AREA)
  • Manufacturing Of Printed Wiring (AREA)

Abstract

La présente invention concerne un procédé de formation d'un motif d'électrode comportant une structure flottante. Le procédé de formation d'un motif d'électrode comportant une structure flottante comprend : (a) une étape de formation d'une couche tampon sur un substrat par application d'un revêtement d'un matériau polymère thermoplastique, qui se décompose thermiquement à une température prédéterminée ou au-dessus, sur le substrat ; (b) une étape de formation d'un motif d'électrode par impression d'une encre conductrice sur la surface de la couche tampon ; et (c) une étape de frittage thermique du motif d'électrode à une température supérieure ou égale à la température de décomposition thermique de la couche tampon. Le matériau polymère thermoplastique constituant la couche tampon dans une zone limitée située entre le motif d'électrode et le substrat est sélectivement décomposé thermiquement et éliminé par le frittage thermique du motif d'électrode de manière à former, le long du bord du motif d'électrode, une ancre dans laquelle la couche tampon est soumise à un auto-modelage. En résultat, le motif d'électrode est formé dans une structure dans laquelle le motif d'électrode est fait flotter sur le substrat par l'ancre.
PCT/KR2016/012123 2015-11-23 2016-10-27 Procédé de formation de motif d'électrode à structure flottante, et procédé d'impression par transfert l'utilisant WO2017090899A1 (fr)

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KR10-2015-0163947 2015-11-23
KR1020150163947A KR101660908B1 (ko) 2015-11-23 2015-11-23 플로팅 구조의 전극 패턴 형성 방법 및 상기 방법을 이용한 전사 인쇄 방법

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KR102015383B1 (ko) 2017-08-07 2019-08-29 한국생산기술연구원 고 신축성 배선구조 및 이의 제조방법
KR101996870B1 (ko) 2017-08-07 2019-07-09 한국생산기술연구원 신축성 기판에 사용되는 전선 구조체의 제조방법

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KR20150073374A (ko) * 2013-12-23 2015-07-01 한국기계연구원 신축성을 가지는 유연 전자소자의 접속방법 및 이에 의해 제조된 유연 전자소자
KR20150083529A (ko) * 2014-01-10 2015-07-20 한국기계연구원 저온 소결법을 이용한 전극 제조방법
KR20150127843A (ko) * 2012-06-29 2015-11-18 서강대학교산학협력단 염료감응 태양전지용 광전극, 그의 제조 방법, 및 그를 포함하는 염료감응 태양전지

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KR20150127843A (ko) * 2012-06-29 2015-11-18 서강대학교산학협력단 염료감응 태양전지용 광전극, 그의 제조 방법, 및 그를 포함하는 염료감응 태양전지
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KR20150073374A (ko) * 2013-12-23 2015-07-01 한국기계연구원 신축성을 가지는 유연 전자소자의 접속방법 및 이에 의해 제조된 유연 전자소자
KR20150083529A (ko) * 2014-01-10 2015-07-20 한국기계연구원 저온 소결법을 이용한 전극 제조방법

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