WO2018194389A1 - Procédé de fabrication de particule de photo-frittage, procédé de fabrication de cible de photo-frittage et procédé de photo-frittage - Google Patents

Procédé de fabrication de particule de photo-frittage, procédé de fabrication de cible de photo-frittage et procédé de photo-frittage Download PDF

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WO2018194389A1
WO2018194389A1 PCT/KR2018/004547 KR2018004547W WO2018194389A1 WO 2018194389 A1 WO2018194389 A1 WO 2018194389A1 KR 2018004547 W KR2018004547 W KR 2018004547W WO 2018194389 A1 WO2018194389 A1 WO 2018194389A1
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substrate
nanoparticles
oxide film
thickness
thermal conductivity
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PCT/KR2018/004547
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English (en)
Korean (ko)
Inventor
김학성
황현준
오경환
김덕중
Original Assignee
한양대학교 산학협력단
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Priority to CN201880026021.7A priority Critical patent/CN110536800B/zh
Publication of WO2018194389A1 publication Critical patent/WO2018194389A1/fr
Priority to US16/657,489 priority patent/US20200061704A1/en

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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B22—CASTING; POWDER METALLURGY
    • B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
    • B22F3/00—Manufacture of workpieces or articles from metallic powder characterised by the manner of compacting or sintering; Apparatus specially adapted therefor ; Presses and furnaces
    • B22F3/10—Sintering only
    • B22F3/1003—Use of special medium during sintering, e.g. sintering aid
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
    • B41M—PRINTING, DUPLICATING, MARKING, OR COPYING PROCESSES; COLOUR PRINTING
    • B41M7/00—After-treatment of prints, e.g. heating, irradiating, setting of the ink, protection of the printed stock
    • B41M7/0081—After-treatment of prints, e.g. heating, irradiating, setting of the ink, protection of the printed stock using electromagnetic radiation or waves, e.g. ultraviolet radiation, electron beams
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B22—CASTING; POWDER METALLURGY
    • B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
    • B22F1/00—Metallic powder; Treatment of metallic powder, e.g. to facilitate working or to improve properties
    • B22F1/05—Metallic powder characterised by the size or surface area of the particles
    • B22F1/052—Metallic powder characterised by the size or surface area of the particles characterised by a mixture of particles of different sizes or by the particle size distribution
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B22—CASTING; POWDER METALLURGY
    • B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
    • B22F1/00—Metallic powder; Treatment of metallic powder, e.g. to facilitate working or to improve properties
    • B22F1/05—Metallic powder characterised by the size or surface area of the particles
    • B22F1/054—Nanosized particles
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B22—CASTING; POWDER METALLURGY
    • B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
    • B22F1/00—Metallic powder; Treatment of metallic powder, e.g. to facilitate working or to improve properties
    • B22F1/14—Treatment of metallic powder
    • B22F1/145—Chemical treatment, e.g. passivation or decarburisation
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B22—CASTING; POWDER METALLURGY
    • B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
    • B22F1/00—Metallic powder; Treatment of metallic powder, e.g. to facilitate working or to improve properties
    • B22F1/16—Metallic particles coated with a non-metal
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B22—CASTING; POWDER METALLURGY
    • B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
    • B22F3/00—Manufacture of workpieces or articles from metallic powder characterised by the manner of compacting or sintering; Apparatus specially adapted therefor ; Presses and furnaces
    • B22F3/10—Sintering only
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B22—CASTING; POWDER METALLURGY
    • B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
    • B22F3/00—Manufacture of workpieces or articles from metallic powder characterised by the manner of compacting or sintering; Apparatus specially adapted therefor ; Presses and furnaces
    • B22F3/10—Sintering only
    • B22F3/105—Sintering only by using electric current other than for infrared radiant energy, laser radiation or plasma ; by ultrasonic bonding
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B22—CASTING; POWDER METALLURGY
    • B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
    • B22F7/00—Manufacture of composite layers, workpieces, or articles, comprising metallic powder, by sintering the powder, with or without compacting wherein at least one part is obtained by sintering or compression
    • B22F7/02—Manufacture of composite layers, workpieces, or articles, comprising metallic powder, by sintering the powder, with or without compacting wherein at least one part is obtained by sintering or compression of composite layers
    • B22F7/04—Manufacture of composite layers, workpieces, or articles, comprising metallic powder, by sintering the powder, with or without compacting wherein at least one part is obtained by sintering or compression of composite layers with one or more layers not made from powder, e.g. made from solid metal
    • 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
    • C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
    • C23C14/22—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the process of coating
    • C23C14/223—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the process of coating specially adapted for coating particles
    • 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
    • C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
    • C23C16/22—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the deposition of inorganic material, other than metallic material
    • C23C16/30—Deposition of compounds, mixtures or solid solutions, e.g. borides, carbides, nitrides
    • C23C16/40—Oxides
    • 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
    • C23C20/00—Chemical coating by decomposition of either solid compounds or suspensions of the coating forming compounds, without leaving reaction products of surface material in the coating
    • C23C20/06—Coating with inorganic material, other than metallic material
    • 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
    • C23C8/00—Solid state diffusion of only non-metal elements into metallic material surfaces; Chemical surface treatment of metallic material by reaction of the surface with a reactive gas, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals
    • C23C8/06—Solid state diffusion of only non-metal elements into metallic material surfaces; Chemical surface treatment of metallic material by reaction of the surface with a reactive gas, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using gases
    • C23C8/08—Solid state diffusion of only non-metal elements into metallic material surfaces; Chemical surface treatment of metallic material by reaction of the surface with a reactive gas, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using gases only one element being applied
    • C23C8/10—Oxidising
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B22—CASTING; POWDER METALLURGY
    • B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
    • B22F2301/00—Metallic composition of the powder or its coating
    • B22F2301/10—Copper
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B22—CASTING; POWDER METALLURGY
    • B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
    • B22F2301/00—Metallic composition of the powder or its coating
    • B22F2301/25—Noble metals, i.e. Ag Au, Ir, Os, Pd, Pt, Rh, Ru
    • B22F2301/255—Silver or gold
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B22—CASTING; POWDER METALLURGY
    • B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
    • B22F2999/00—Aspects linked to processes or compositions used in powder metallurgy
    • 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
    • C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
    • C23C16/44—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the method of coating
    • C23C16/48—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the method of coating by irradiation, e.g. photolysis, radiolysis, particle radiation

Definitions

  • the present invention relates to a method for producing an optical sintered particle, a method for manufacturing an optical sintered target and an optical sintering method, and more specifically, an optical sintered particle manufacturing method for improving the optical sintering efficiency by controlling the oxide film on the surface of the nanoparticles, an optical sintering target It relates to a manufacturing method and a light sintering method.
  • Printed electronic refers to an electronic product having a pattern formed by a printing technique such as screen printing or gravure printing. It consists of three simple steps of printing, drying, and sintering, and it is a technology that is in the limelight because it has advantages such as low cost, eco-friendliness, flexibility, large-scale mass production, low temperature / simple process, etc., compared to the conventional photolithography process. Therefore, printed electronics can be applied to various electronic products such as flexible electronic products and solar cells.
  • a printing technique such as screen printing or gravure printing. It consists of three simple steps of printing, drying, and sintering, and it is a technology that is in the limelight because it has advantages such as low cost, eco-friendliness, flexibility, large-scale mass production, low temperature / simple process, etc., compared to the conventional photolithography process. Therefore, printed electronics can be applied to various electronic products such as flexible electronic products and solar cells.
  • Sintering is one of the core technologies of printed electronic devices. Depending on the sintering method and conditions, the electrical conductivity of the pattern after the sintering and the quality of the pattern may be influenced. Conventional methods for sintering conductive inks are currently thermally sintered, but they cannot be applied to flexible substrates, which are next-generation substrates, because they are sintered at high temperatures above 300oC.
  • the laser sintering method the plasma sintering method, the microwave sintering method, etc. have been proposed as a new sintering method.
  • this method is also not suitable for mass production.
  • One technical problem to be solved by the present invention is to provide an optical sintered particle manufacturing method, optical sintering target manufacturing method and optical sintering method having high efficiency by considering the characteristics of the substrate.
  • Another technical problem to be solved by the present invention is to provide an optical sintered particle manufacturing method, an optical sintering target manufacturing method, and an optical sintering method which are optically sintered even in a silicon substrate.
  • Another technical problem to be solved by the present invention is to provide an optical sintered particle manufacturing method, an optical sintering target manufacturing method and an optical sintering method excellent in process convenience.
  • Another technical problem to be solved by the present invention is to provide an optical sintered particle manufacturing method, an optical sintering target manufacturing method and an optical sintering method having excellent price competitiveness.
  • Another technical problem to be solved by the present invention is to provide an optical sintered particle manufacturing method, an optical sintering target manufacturing method and an optical sintering method that is easy to mass production.
  • the technical problem to be solved by the present invention is not limited to the above.
  • preparing the nanoparticles and forming oxide films having different thicknesses on the surface of the nanoparticles based on thermal conductivity of the substrate on which the nanoparticles are to be formed may include the step.
  • the thermal conductivity of the substrate when the thermal conductivity of the substrate is less than a predetermined reference value, an oxide film of a first thickness is formed on the surface of the nanoparticles, the thermal conductivity of the substrate in advance
  • an oxide film having a second thickness is formed on the surface of the nanoparticle, and the first thickness may be thinner than the second thickness.
  • the predetermined reference value may be 1W / mK.
  • the first thickness may be 1 to 3% of the nanoparticle diameter
  • the second thickness may be 3 to 10% of the nanoparticle diameter
  • preparing the nanoparticles may include forming oxide films having different thicknesses on the surface of the nanoparticles based on thermal conductivity of a substrate on which the nanoparticles are to be formed. And preparing a conductive target by including a binder resin in the nanoparticles having the oxide film formed thereon.
  • the thermal conductivity of the substrate when the thermal conductivity of the substrate is less than a predetermined reference value, an oxide film of a first thickness is formed on the surface of the nanoparticles, the thermal conductivity of the substrate in advance
  • an oxide film having a second thickness is formed on the surface of the nanoparticle, and the first thickness may be thinner than the second thickness.
  • the predetermined reference value may be 1W / Mk.
  • the first thickness may be 1 to 3% of the nanoparticle diameter
  • the second thickness may be 3 to 10% of the nanoparticle diameter
  • forming an oxide film having a different thickness based on the thermal conductivity of the substrate on which the nanoparticles are to be formed, on the surface of the nanoparticles may include the step of preparing a conductive target by including a binder resin, forming the prepared conductive target on the substrate and photosintering the conductive target formed on the substrate.
  • the thermal conductivity of the substrate when the thermal conductivity of the substrate is less than a predetermined reference value, an oxide film of a first thickness is formed on the surface of the nanoparticles, the thermal conductivity of the substrate in advance When larger than a predetermined reference value, an oxide film having a second thickness is formed on the surface of the nanoparticles, wherein the first thickness is thinner than the second thickness, and in the photosintering step, the thermal conductivity of the substrate is predetermined.
  • light of a first intensity is irradiated to the substrate, and if the thermal conductivity of the substrate is greater than a predetermined reference value, light of a second intensity is irradiated to the substrate, wherein the first intensity is equal to the It may be weaker than the second strength.
  • a method of manufacturing optical sintered particles according to the characteristics of a substrate on which nanoparticles are to be formed, and determining whether an oxide film is required on the surface of the nanoparticles and when oxide film formation is required on the surface of the nanoparticles. It may comprise the step of forming an oxide film on the surface of the nanoparticles.
  • the characteristic of the substrate is thermal conductivity, and when the thermal conductivity is 1W / mK or more, it may be determined that an oxide film is required on the surface of the nanoparticles.
  • the substrate when the substrate includes silicon, it may be determined that an oxide film needs to be formed on the surface of the nanoparticles.
  • a method of manufacturing an optical sintering target according to the characteristics of a substrate on which nanoparticles are to be formed may include forming an oxide film on the surface of the nanoparticles and preparing a conductive target by including a binder resin in the nanoparticles on which the oxide film is formed.
  • the characteristic of the substrate is thermal conductivity, and when the thermal conductivity is 1W / mK or more, it may be determined that an oxide film is required on the surface of the nanoparticles.
  • the substrate when the substrate includes silicon, it may be determined that an oxide film needs to be formed on the surface of the nanoparticles.
  • the light sintering method determining whether the oxide film is required on the surface of the nanoparticles according to the characteristics of the substrate on which the nanoparticles are to be formed, and when the oxide film is required on the surface of the nanoparticles, Forming an oxide film on a surface of the nanoparticle, preparing a conductive target by including a binder resin in the nanoparticle on which the oxide film is formed, forming the prepared conductive target on the substrate, and forming a conductive target formed on the substrate. Photo sintering.
  • the optical sintering method comprises the steps of forming and controlling the oxide film of the copper nanoparticles to have an optimum optical sintering characteristics according to the substrate type, preparing a conductive ink containing a polymer binder resin, the conductive Printing and drying the ink on the substrate and photosintering the printed pattern using white light emitted from the xenon flash lamp.
  • an oxide film can be reduced and sintered at a very short time within a few milliseconds (1 to 1000 ms) at room temperature / standby conditions, and a large quantity of electronic devices with high electrical conductivity and reliability can be obtained. Easy to produce
  • the light sintering process is also possible for the silicon substrate, which has been difficult to perform the conventional light sintering process, it is possible to extend the type of substrate to be applied.
  • FIG. 1 is a flowchart illustrating a light sintering method according to an embodiment of the present invention.
  • FIG. 2 is a view for explaining the step S150 of the optical sintering method according to an embodiment of the present invention.
  • FIG. 3 is a view for explaining a light sintering method according to another embodiment of the present invention.
  • FIG. 4 is a graph illustrating resistance according to substrate type and thickness of an oxide film.
  • FIG. 5 is a HR-TEM photograph for explaining an oxide film formed according to a type of substrate.
  • FIG. 6 is a graph showing the XRD change before and after sintering according to the oxide film thickness of the conductive target formed on the PI substrate.
  • FIG. 7 is a graph showing the XRD change before and after sintering according to the oxide film thickness of the conductive target formed on the silicon substrate.
  • FIG. 8 shows an SEM image according to an oxide film thickness of a conductive target formed on a PI substrate.
  • FIG. 9 illustrates a SEM photograph according to an oxide film thickness of a conductive target formed on a silicon substrate.
  • first, second, and third are used to describe various components, but these components should not be limited by these terms. These terms are only used to distinguish one component from another. Thus, what is referred to as a first component in one embodiment may be referred to as a second component in another embodiment.
  • first component in one embodiment may be referred to as a second component in another embodiment.
  • second component in another embodiment.
  • Each embodiment described and illustrated herein also includes its complementary embodiment.
  • the term 'and / or' is used herein to include at least one of the components listed before and after.
  • connection is used herein to mean both indirectly connecting a plurality of components, and directly connecting.
  • FIG. 1 is a flowchart illustrating a light sintering method according to an embodiment of the present invention. With reference to FIG. 1, the method for manufacturing the optical sintered particles and the method for manufacturing the optical sintered target are also described. 2 is a view for explaining the step S150 of the optical sintering method according to an embodiment of the present invention.
  • nanoparticles may be provided.
  • the nanoparticles may be made of at least one material of gold, silver, and copper. Unless otherwise specified, it is assumed that the nanoparticles are copper nanoparticles.
  • oxide films having different thicknesses may be formed on the surface of the nanoparticles based on the thermal conductivity of the substrate on which the nanoparticles are to be formed.
  • the substrate may be, for example, a flexible substrate or may be a rigid substrate.
  • the substrate may be photo paper, PET, paper, polybutylene terephthalate, polyethylene terephthalate, polysulfone, polyether, polyetherimide, polyethylene naphthalate (PEN), acrylic resin, heat resistant epoxy, BT It may be composed of at least one material of epoxy / glass fiber, vinyl acetate resin (EVA), butyl rubber resin, polyarylate, polyimide.
  • the solar cell and the semiconductor device may be made of at least one of glass, amorphous silicon (armophous silicon), mono-crystal silicon (mono-crystaline silicon), poly-crystalline silicon (silicon) and ceramic.
  • the thickness of the oxide film to be formed on the surface of the prepared nanoparticles can be controlled according to the characteristics of the substrate, for example, thermal conductivity, flexibility, and the like.
  • the substrate may have thermal conductivity and flexibility characteristics as shown in Table 1, depending on the kind thereof.
  • an oxide film having a first thickness may be formed on the surface of the nanoparticle, and when the thermal conductivity is larger than the predetermined reference, the second thickness thicker than the first thickness Oxide film can be formed. More specifically, when the thermal conductivity of the substrate is less than 1W / mK, an oxide film having a thickness of less than 1 to 3% of the nanoparticle diameter can be formed on the surface of the nanoparticles, when the thermal conductivity of the substrate is greater than 1W / mK, An oxide film having a thickness of 3% to 10% of the nanoparticle diameter may be formed on the surface of the nanoparticle.
  • an oxide film may be formed on the surface of the nanoparticles in various ways. For example, a method of heating and oxidizing in air using a chamber, a hot plate, or the like may be used, and a plasma treatment or a separate post treatment immediately after the nanoparticles are manufactured. Oxidation through may be used, but is not limited thereto.
  • the oxide thickness may be controlled by adjusting one or a combination of two or more of a heating temperature, an oxidation time, or an oxygen partial pressure.
  • Step S110 and step S120 the optical sintered particles according to an embodiment of the present invention can be produced.
  • Step S130 is described below.
  • a conductive target may be manufactured by including a binder resin in the nanoparticles on which the oxide film is formed.
  • the conductive target means an optical sintered target and can be understood as a concept including an optical sintered ink and a paste.
  • a binder resin may be added to improve the dispersibility and the reducing property of the prepared optical sintered ink.
  • the binder resin is, for example, at least one of polyvinylpyrrolidone (PVP), polyvinyl alcohol (PVA), polyvinyl butyral, polyethylene glycol, polymethyl methacrylate, dextran, azobis and sodium dodecylbenzene sulfate It may contain one substance. In this case, the fraction of the binder may be 1 to 50% by weight. If the weight average molecular weight of the binder is too low, the effect of dispersion or reduction is inferior, and if it exceeds 500,000, it is preferable to use 10,000 to 500,000 because it forms an aggregate.
  • the type and amount of the binder may vary depending on the thickness of the oxide film of the copper nanoparticles.
  • Step S140 is described below.
  • step S140 the prepared optical sintered target may be formed on the substrate.
  • the optical sintered target may be formed on the substrate in various ways. For example, screen printing, inkjet printing, micro-contact printing, imprinting, gravure printing, gravure-offset printing ), At least one method of flexography printing and spin coating can be used.
  • the optical sintered target formed on the substrate may be dried by a drying process.
  • the light sintering target formed on the substrate may be dried by a hot air blower, an oven (heat chamber), a hot plate, an infrared ray, or a combination thereof.
  • the drying temperature can be set so as not to damage the substrate. If the substrate is a polymer substrate, the drying temperature may range from 60 to 150C.
  • the light sintering target formed on the substrate may be photosintered.
  • the optical sintered target may be sintered while being subjected to light energy by microwave white light emitted from the xenon lamp to have conductivity.
  • the white light irradiation can be a stepwise light sintering technique for gradual oxide film reduction to increase the sintering effect.
  • the light 50 is transferred to the optical sintering target through the xenon flash lamp 30. 20).
  • a reflector 40 reflecting light to an object may be provided on one side of the xenon flash lamp 30.
  • the light provided to the light sintering target may be combined by various variables.
  • variables such as light providing time, light intensity, light pulse, and the like may be controlled.
  • the light provided is subject to changes in pulse width (0.01 to 50 ms), pulse gap (0.01 to 100 ms), number of pulses (1 to 100 times), and light intensity (0.1 J / cm2 to 100 J / cm2).
  • Conditions vary and thus the total light energy can have a light energy of up to 100 J / cm 2.
  • the energy range for sintering may vary depending on the substrate.
  • the thermal conductivity of the substrate is less than a predetermined reference value
  • light of the first intensity is irradiated onto the substrate
  • the thermal conductivity of the substrate is greater than the predetermined reference value
  • Light of two intensities can be irradiated onto the substrate. More specifically, when the thermal conductivity of the substrate is less than 1W / mK, the light intensity may have a range of less than 0.1 to 20J / cm2, when the thermal conductivity of the substrate is greater than 1W / mK, the light intensity is 20 to 100J / It may have a range of cm2.
  • the mechanism of the rapid light sintering process using the microwave white light is that when the light energy of the white light pulse irradiated from the xenon lamp reaches the target, the light energy is converted into thermal energy so that the temperature of the target layer rises momentarily and is very short. It is the mechanism by which the target layer is sintered in time. Therefore, the light sintering characteristics of the target layer are different according to the physical properties of the substrate as well as the light absorption, heat capacity and thermal conductivity of the target layer. Control is required.
  • the physical properties of the substrate were not recognized as light sintering parameters, it was difficult to improve the light sintering efficiency.
  • the optical sintering method for substrates with high thermal conductivity has been difficult to research.
  • the present inventors have proposed a technical solution considering the characteristics of the substrate.
  • the temperature of the light sintering target and / or nanoparticles must reach a certain temperature level.
  • the thickness of the oxide film may be increased to improve the photosintering characteristics.
  • the light energy required for sintering should be minimized in order to minimize damage to the substrate. Can be improved.
  • the thermal conductivity of the substrate when the thermal conductivity of the substrate is low, a thin oxide film and a low intensity sintered light are provided. In contrast, when the thermal conductivity of the substrate is high, a thick oxide film and a high intensity sintered light are provided.
  • the conductivity characteristics of the optical sintered target can be improved and the stability of the substrate can be achieved.
  • FIG. 3 is a view for explaining a light sintering method according to another embodiment of the present invention. Referring to FIG. 3, the method of manufacturing the optical sintered particles and the method of manufacturing the optical sintered target are also described.
  • a step of providing nanoparticles (S210), determining whether an oxide film is required on the surface of the nanoparticles according to the characteristics of the substrate on which the nanoparticles are to be formed (S220), and an oxide film on the surface of the nanoparticles If formation is required, forming an oxide film on the surface of the nanoparticles (S230), preparing a conductive target by including a binder resin in the nanoparticles on which the oxide film is formed (S240), and preparing the conductive target on the substrate Forming a (S250) and the step of photosintering the conductive target formed on the substrate (S260) can be made.
  • S230 preparing a conductive target by including a binder resin in the nanoparticles on which the oxide film is formed
  • S250 the step of photosintering the conductive target formed on the substrate
  • step S210 corresponds to step S110, a detailed description thereof will be omitted.
  • step S220 it may be determined whether an oxide film is required on the surface of the nanoparticles according to the characteristics of the substrate on which the nanoparticles are to be formed.
  • the thermal conductivity of the substrate when the thermal conductivity of the substrate is greater than a predetermined reference, it may be determined that an oxide film is required on the surface of the nanoparticle.
  • the thermal conductivity according to a predetermined criterion may be 1W / mK.
  • the substrate contains silicon, for example, it may be determined that an oxide film needs to be formed on the surface of the nanoparticles.
  • the oxide film may be provided on the surface of the nanoparticles.
  • steps S240, S250, and S260 correspond to steps S130, S140, and S150, respectively, detailed descriptions thereof will be omitted.
  • the optical sintering may be performed in consideration of the characteristics of the substrate by determining whether an oxide film is required according to the characteristics of the substrate.
  • FIG. 4 is a graph illustrating resistance according to a substrate type and an oxide film thickness
  • FIG. 5 is an HR-TEM photograph for describing an oxide film formed according to a substrate type
  • FIG. 6 is an oxide film of a conductive target formed on a PI substrate.
  • Figure 7 is a graph showing the XRD change before and after sintering according to the thickness
  • Figure 7 is a graph showing the XRD change before and after sintering according to the oxide film thickness of the conductive target formed on the silicon substrate
  • Figure 8 is a SEM according to the oxide film thickness of the conductive target formed on the PI substrate A photo is shown
  • FIG. 9 shows a SEM picture according to the oxide film thickness of the conductive target formed on the silicon substrate.
  • Copper nanoparticles with an average diameter of 100 nm are mixed in an oven with a temperature of 200 ° and oxidized for 1 minute.
  • 0.9 g of PVP was mixed with 4 g of DGBE (diethylene glycol butyl ether) solvent and dispersed for 30 minutes using a sonicator.
  • 12 g of oxidized copper particles were added to the mixed solution and dispersed for 40 minutes using a 3-roll mill to prepare a copper paste.
  • the electrode pattern is completed by drying for 15 minutes using infrared light at a temperature of 100 °.
  • Microwave white light is irradiated to the electrode pattern.
  • the number of pulses of the microwave white light is 40, the pulse width is 1 ms, the pulse interval is 20 ms, and the total irradiation energy is 60 J / cm2.
  • Copper nanoparticles with an average diameter of 100 nm are mixed in an oven with a temperature of 200 ° and oxidized for 4 minutes.
  • 0.9 g of PVP is mixed with 4.5 g of DEG (Diethylene glycol) solvent and dispersed for 30 minutes using a sonicator.
  • 11.4 g of oxidized copper particles were added to the mixed solution, and then dispersed for 45 minutes using a 3-roll mill to prepare a copper paste.
  • the electrode pattern is completed by drying for 15 minutes using infrared light at a temperature of 100 °.
  • Microwave white light is irradiated to the electrode pattern. In this case, the number of microwave white light has 30 pulses, the pulse width is 1 ms, the pulse interval is 30 ms, and the total irradiation energy is 55 J / cm2.
  • Copper nanoparticles with an average diameter of 100 nm are mixed in an oven with a temperature of 200 ° and oxidized for 7 minutes.
  • 0.9 g of PVP is mixed with 4.5 g of DEG (Diethylene glycol) solvent and dispersed for 30 minutes using a sonicator.
  • 11.4 g of oxidized copper particles were added to the mixed solution, and then dispersed for 50 minutes using a 3-roll mill to prepare a copper paste.
  • the electrode pattern is completed by drying for 15 minutes using infrared rays at 120 °.
  • Microwave white light is irradiated to the electrode pattern. At this time, the number of pulses of the microwave white light is 25, the pulse width is 1.5 ms, the pulse interval is 25 ms, and the total irradiation energy is 50 J / cm2.
  • Copper nanoparticles having an average diameter of 40 nm were dispersed in 4.5 g of DEG (Diethylene glycol) solvent with 0.9 g of PVP and dispersed for 30 minutes using a sonicator. 11.4 g of oxidized copper particles were added to the mixed solution, and then dispersed for 45 minutes using a 3-roll mill to prepare a copper paste.
  • the electrode pattern is completed by drying for 20 minutes using an infrared ray at 100 ° temperature. Microwave white light is irradiated to the electrode pattern. At this time, the irradiation time is 10 ms, the number of pulses is one, and the pulse energy is 12.5 J / cm 2.
  • Copper nanoparticles with an average diameter of 40 nm are mixed in an oven with a temperature of 100 ° and oxidized for 3 hours.
  • 0.9 g of PVP is mixed with 4.5 g of DEG (Diethylene glycol) solvent and dispersed for 30 minutes using a sonicator.
  • 11.4 g of oxidized copper particles were added to the mixed solution, and then dispersed for 50 minutes using a 3-roll mill to prepare a copper paste.
  • the electrode pattern is completed by drying for 1 hour using a hot plate at a temperature of 100 °.
  • Microwave white light is irradiated to the electrode pattern. At this time, the irradiation time is 10 ms, the number of pulses is one, and the pulse energy is 15 J / cm 2.
  • Copper nanoparticles with an average diameter of 40 nm are mixed in an oven with a temperature of 200 ° and oxidized for 2 hours.
  • 0.9 g of PVP is mixed with 4.5 g of DEG (Diethylene glycol) solvent and dispersed for 30 minutes using a sonicator.
  • 11.4 g of oxidized copper particles were added to the mixed solution, and then dispersed for 50 minutes using a 3-roll mill to prepare a copper paste.
  • the electrode pattern is completed by drying for 1 hour using a hot plate at a temperature of 100 °.
  • Microwave white light is irradiated to the electrode pattern. At this time, the irradiation time is 20 ms, the number of pulses is one, and the pulse energy is 15 J / cm 2.
  • the resistance when the thickness of the surface oxide film of the copper nanoparticles is changed depending on whether the substrate is a PI substrate or a silicon substrate having low thermal conductivity can be confirmed.
  • the thinner the thickness of the oxide film the better the conductivity.
  • the conductivity is still excellent.
  • the conductivity can be significantly improved by forming an oxide on the optical sintered target.
  • the photo shows that the oxide film according to Examples 2 and 4 has a predetermined thickness on the surface of the copper nanoparticles, and no amorphous (oxide layer) was observed before the process for forming the oxide film.
  • the PI substrate was 0.8 nm and the silicon substrate was 5.8 nm.
  • an optical sintering target is formed on the PI substrate, and the XRD graph according to the thickness of the oxide layer may be confirmed.
  • the copper oxide film reduction reaction occurred by reaction with polymer surface modifiers coated on the outside of the copper nanoparticles, thereby confirming that the copper oxide of the copper nanoparticles having an oxide thickness of 3.6 nm or less was reduced and sintered to pure copper. Can be.
  • copper oxide (II) CuO
  • Fig. 8 shows that the electrical resistance is high. Therefore, proper oxide film control is essential for improving the optical sintering characteristics of copper nano ink.
  • the XRD graph of the light sintering target is formed on the silicon substrate and the thickness of the oxide film is changed.
  • the sintering could not be performed by forming an oxide film having a thickness of 0.2 nm (natural oxidation), and the sintering process may be performed when the thickness of the oxide film is thickened such as 5.8 nm and 7.1 nm. That is, it can be confirmed experimentally that the oxide film should be thick in the case of a substrate having high thermal conductivity.
  • the thickness of the oxide film increases, so that the pores increase, so that the conductivity characteristics deteriorate.
  • the conductivity of the oxide film is 2.7 nm to 7.1 nm. No significant difference was found in the properties.
  • nanoparticles having an oxide film it is possible to provide nanoparticles having an oxide film to have an optimal optical sintering characteristics according to the type of substrate. This enables the optical sintering process to the substrate of high thermal conductivity, which has been extremely difficult to implement in the past.
  • the light sintering efficiency can be improved by controlling the thickness of the oxide film and the light sintering conditions differently according to the characteristics of the substrate.

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Abstract

L'invention concerne un procédé de fabrication d'une particule de photo-frittage. Selon un mode de réalisation, le procédé peut comprendre les étapes suivantes : préparation de nanoparticules ; et formation, sur la surface des nanoparticules, de films d'oxyde ayant des épaisseurs différentes sur la base de la conductivité thermique d'un substrat sur lequel les nanoparticules doivent être formées.
PCT/KR2018/004547 2017-04-20 2018-04-19 Procédé de fabrication de particule de photo-frittage, procédé de fabrication de cible de photo-frittage et procédé de photo-frittage WO2018194389A1 (fr)

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CN201880026021.7A CN110536800B (zh) 2017-04-20 2018-04-19 光烧结粒子制备方法、光烧结靶制备方法及光烧结方法
US16/657,489 US20200061704A1 (en) 2017-04-20 2019-10-18 Method for manufacturing photo-sintering particle, method for manufacturing photo-sintering target, and photo-sintering method

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KR1020170050928A KR101930159B1 (ko) 2017-04-20 2017-04-20 광 소결 입자 제조방법, 광 소결 타겟 제조방법 및 광 소결 방법

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KR101350507B1 (ko) * 2013-01-09 2014-01-17 (주)쎄미시스코 금속 나노입자를 포함하는 전기전도성 잉크 및 이의 광 소결 방법
KR20160077412A (ko) * 2014-12-23 2016-07-04 전자부품연구원 나노구리 잉크 조성물, 그를 이용한 배선기판 및 그의 제조 방법
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WO2015152625A1 (fr) * 2014-04-01 2015-10-08 전자부품연구원 Composition d'encre de frittage par la lumière, carte de câblage l'utilisant et son procédé de fabrication

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KR20120013350A (ko) * 2009-03-27 2012-02-14 어플라이드 나노테크 홀딩스, 인크. 광 및／또는 레이저 소결을 향상시키기 위한 버퍼층
KR101350507B1 (ko) * 2013-01-09 2014-01-17 (주)쎄미시스코 금속 나노입자를 포함하는 전기전도성 잉크 및 이의 광 소결 방법
KR101689679B1 (ko) * 2014-05-30 2016-12-26 한국화학연구원 금속 나노입자 및 이의 제조방법
KR20160077412A (ko) * 2014-12-23 2016-07-04 전자부품연구원 나노구리 잉크 조성물, 그를 이용한 배선기판 및 그의 제조 방법
KR20160116076A (ko) * 2015-03-25 2016-10-07 한화첨단소재 주식회사 구리 인쇄회로기판 제조방법

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KR20180117864A (ko) 2018-10-30

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