WO2016010393A1 - 광소결을 이용한 전도성 금속박막의 제조방법 - Google Patents

광소결을 이용한 전도성 금속박막의 제조방법 Download PDF

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WO2016010393A1
WO2016010393A1 PCT/KR2015/007440 KR2015007440W WO2016010393A1 WO 2016010393 A1 WO2016010393 A1 WO 2016010393A1 KR 2015007440 W KR2015007440 W KR 2015007440W WO 2016010393 A1 WO2016010393 A1 WO 2016010393A1
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Prior art keywords
thin film
metal
metal thin
conductive
light
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PCT/KR2015/007440
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English (en)
French (fr)
Inventor
정선호
최영민
류병환
서영희
조예진
이은정
오상진
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한국화학연구원
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Publication of WO2016010393A1 publication Critical patent/WO2016010393A1/ko

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    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D11/00—Inks
    • C09D11/52—Electrically conductive inks
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
    • H01B1/00—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors
    • H01B1/20—Conductive material dispersed in non-conductive organic material
    • H01B1/22—Conductive material dispersed in non-conductive organic material the conductive material comprising metals or alloys
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
    • H01B13/00—Apparatus or processes specially adapted for manufacturing conductors or cables

Definitions

  • the present invention relates to a method of manufacturing a conductive metal thin film.
  • a substrate having a low process temperature can be produced in a conductive metal thin film having excellent electrical conductivity without damage to the substrate. It is possible to manufacture a conductive metal thin film having excellent bonding force with a substrate.
  • Inks containing metal nanoparticles can be prepared by a single printing process such as screen printing, inkjet printing, gray bar offset printing, reverse offset printing, etc., without using complicated photolithography complex processes.
  • the printing process has the advantage of simplifying the process, and the simplification of the process can not only drastically reduce the manufacturing cost, but also make it possible to manufacture with high integration and high efficiency printing by miniaturization of wiring width.
  • the present application is based on the use of metal nanoparticle ink with controlled formation of surface oxide film.
  • the present invention has been completed by developing a method for producing a conductive metal thin film having excellent electrical conductivity and excellent bonding force with a substrate.
  • the present invention enables the manufacture of conductive metal thin films having excellent electrical conductivity even without a damage to the substrate with a low process limit, and can be effectively used for flexible parts due to its excellent bonding force with the substrate. It is possible to manufacture a metal thin film, to produce a large area in a very short time in the air, to implement a two-roll process, which is excellent in commerciality, and to a method of manufacturing a conductive metal thin film that can simplify the process and reduce manufacturing costs.
  • the method for manufacturing a sintered conductive metal thin film comprises: a) a conductivity in which the metal core contains metal nanoparticles, non-aqueous organic binders and non-aqueous solvents capped with a capping layer containing an organic acid. Preparing an ink composition; b) forming a coating film by coating the conductive ink composition on an insulating substrate; and c) preparing a conductive metal thin film by irradiating light on the coating film so as to satisfy the following Equation 1.
  • Equation 1 ⁇ is the intensity of light irradiated onto the coating film, and I c is the maximum intensity of light that the non-aqueous organic binder remains in the conductive metal thin film.
  • step c) light may be irradiated to satisfy the following formula 1-1.
  • Equation 1-1 The definition of 1 in Equation 1-1 is the same as Equation 1.
  • the average diameter of the metal nanoparticles may be 20 to 300 nm.
  • the present inventors have conducted a long-term study of various methods of thinning ink containing metal nanoparticles capped with a capping layer containing an organic acid, which surprisingly prevents the formation of an oxide film by the capping layer.
  • sintering ink containing metal nanoparticles it has been found that sintering occurs at surprisingly low light intensities, and that a metal thin film can be produced which retains the binding force by non-aqueous binder even after sintering. It was found that the nonaqueous organic binder contained was not carbonized, and the binder itself could be manufactured with the same electrical conductivity as the bulk, while maintaining the properties of the binder itself.
  • Equation 1 The sintering conditions in Equation 1 are very surprising to those skilled in the art of sintering using metal nanoparticles.
  • the sintering (densification) of metal nanoparticles during photosintering is performed by the high energy exerted by light.
  • the surface area of these metals is known to be melted in an instant, and in order to sinter (densify) these metal nanoparticles, light having an intensity of lOJ / cm 2 or more is actually irradiated.
  • at least the surface area of the metal nanoparticles is investigated.
  • the manufacturing method is excellent in thermal stability, so that the metal binder and the polymer binder in common can remain. Therefore, even if the substrate has a very low process temperature of 100 ° C or less, It is possible to manufacture conductive metal thin films with excellent electrical conductivity comparable to bulk without damage, and the remaining polymer binder has excellent bonding strength between metal thin films and substrates, making it possible to manufacture conductive metal thin films which are very suitable for flexible parts.
  • step c light may be irradiated to satisfy the following Equation 1-1.
  • Equation 1-1 the definition of ⁇ is identical to Equation 1.
  • the binder of the polymer contained in the ink does not remain in the metal thin film and is carbonized, so that the binding effect between the metal thin film and the substrate by the remaining polymer binder is carbonized. You won't get it.
  • Irradiation irradiation of continuous light
  • stable light sintering can lead to stable light sintering.
  • the time of light irradiation is determined by the accumulation of heat generated by light
  • a method for manufacturing a conductive ink composition containing metal nanoparticles capped with a capping layer containing an organic acid is described in relation to Formula 1-1.
  • the manufacturing method according to the embodiment of the present invention includes organic acid before step a).
  • the particle manufacturing step may be a batch method or a continuous method.
  • the step of manufacturing the metal nanoparticles capped with a capping layer containing an organic acid in a batch method is described in Korean Patent Application Publication No. 2013-0111180 filed by the present applicant. It may be carried out by reference, the present invention includes all the contents described in the Republic of Korea Patent Publication No. 2013-0111180.
  • the particle production step is a metal precursor
  • the metal precursor may be selected from the group consisting of copper, nickel, cobalt, aluminum, tin and alloys thereof.
  • Inorganic consisting of nitrates, sulfates, acetates, phosphates, silicates and hydrochlorides of metals selected from the group consisting of It may be one or more selected from salts.
  • the organic acid has at least one of linear, branched, and cyclic carbon atoms of 6 to 30 carbon atoms, and may be one or more selected from saturated or unsaturated acids. More specifically, oleic acid, lysine oleic acid, stearic acid, Hydroxystearic acid, linoleic acid, aminodecanoic acid, hydroxydecanoic acid, lauric acid, dekenoic acid,
  • Undekenoic acid palideoleic acid, nucleated decanoic acid, hydroxy palmitic acid,
  • One or more may be selected from the group consisting of missrisoleic acid, but not limited thereto.
  • the molar ratio of the metal precursor to the organic acid may be 1 (metal precursor): 0.2 to 4 (acid).
  • Organic amines have at least one form of linear, branched, and cyclic, having 6 to 30 carbon atoms, and may be selected from one or two or more of saturated and unsaturated amines. More specifically, it may be selected from, but not limited to, nucleosilamine, heptylamine, octylamine, dodecylamine, 2-ethylnuclear amine, 1,3-dimethyl-n-butylamine, 1-aminotoridecane, etc.
  • the amount of amine in is preferably 0.2 mol or more, preferably 1 to 50 mol, and more preferably 5 to 50 mol, with respect to 1 mol of the metal precursor, but in the upper limit, the organic amine may act as a non-aqueous solvent and is not necessarily limited. .
  • the reducing agent may be one or more selected from hydrazine-based reducing agents including hydrazine, hydrazine anhydride, hydrazine hydrochloride, hydrazine sulfate, hydrazine hydrate and phenyl hydrazine.
  • a borohydride system including tetramethylammonium borohydride, tetraethylammonium borohydride, small borohydride and the like; sodium phosphate system; And ascorbic acid; may be used by selecting one or more than one.
  • the reducing agent may include a reducing agent / metal precursor molar ratio of 1 to 100.
  • the metal nanoparticles can be separated and recovered by the usual method used for nanoparticles such as centrifugal separation.
  • reaction space which is a space between the rotating cylinders having a concentric structure and spaced apart from each other.
  • the impulse shear flow reaction device is formed inside a cylinder and a cylinder.
  • the material is injected into the reaction space, which is a space between the jacket and the cylinder, which is formed in the center and is connected to the motor, the stirring rod and the stirring rod that rotate the cylinder, and formed and fixed on the outer periphery of the cylinder. It may include an inlet and an outlet for discharging the finished product.
  • the cylinder may have a rotating axis that matches the longitudinal axis of the jacket.
  • the inlet may be located at one end or one side of the jacket, and the outlet may be located at the other end or the other side of the jacket.
  • the laminar flow shear reaction device may be located outside the jacket.
  • the heating unit may further include, and of course, the heating unit may be positioned around the outer side of the jacket.
  • each of the vortices of the rotating ring pair array can form an independent semi-magnitude in the reaction space. .
  • Metal cores are produced stably, reproducibly, and with very good yields by introducing organic acids, organic amines, metal precursors and reducing agents into the micro semi-major tracts defined by the vortex and vortex of the ring pair array. Metal nanoparticles capped with a capping layer containing organic acids can be produced.
  • the inlet can be formed at one end or one side of the jacket, and the first inlet through which the first solution is injected and the second inlet through which the second solution is injected can be formed.
  • the first and second solutions can be injected through a single inlet.
  • the first solution and the second solution are continuously injected into the reaction space through an inlet formed at one end or one end of the jacket, and the metal nanoparticles capped by the capping layer through the outlet formed at the other end or the other end of the jacket.
  • the first solution through a single inlet.
  • Task 2 Solution can be injected during transfer.
  • the jacket and the cylinder can satisfy the following relation.
  • Equation 2 D is the separation distance between the jacket and the cylinder, and ri is the cylinder
  • the width of the reaction space is extremely small at 2.5 mm.
  • the width of the reaction space is extremely small (1 mm to 2.5 mm), it is advantageous for the production of metal nanoparticles of bimodal distribution with better photosintering properties.
  • the residence time in which the reaction fluid containing the injected first solution and the second solution stays in the reaction space can be controlled by the rotational speed of the cylinder and the input amount of the reaction fluid.
  • the rotational speed of the cylinder is preferably 400 rpm or more in terms of stable Taylor-Quet vortex formation.
  • homogeneous nanoparticles must be present in each swirl cell to produce homogeneous nanoparticles. Should be less than 1000 rpm.
  • the rotation speed of the cylinder is preferably 600 to 800 rpm. This rotation speed is consistent with the reactions present in the vortex cell.
  • fine grains are consumed among the grown grains and coarse grains grow, resulting in the driving force of growth in the semi-rigidity (the reaction water and the particle size remaining in the semi-rigid at that time).
  • Bimodal metal nanoparticles can be produced that consume the driving force provided by ordinary fine particles, suppress the growth of other particles or remelt the fine nuclei, and increase the fraction of finer particles.
  • the reaction temperature is not particularly limited but can be reacted in the range of 100 to 350 ° C, preferably 120 to 200 ° C, more preferably 130 to 150 ° C. Responding at has excellent resistivity
  • More than 95% high purity metal nanoparticles can be produced in yield.
  • the reaction temperature should be 130 to 150 ° C so that the metal nanoparticles of bimodal distribution with better photosintering characteristics can be produced.
  • the rate at which the overall nucleation and growth driving force in the vortex cell is consumed and It can affect the degree of nucleation.
  • Low temperatures of 130 to 150 ° C can increase the particle size difference between relatively small particles and relatively large particles, resulting in an increase in the proportion of relatively small particles and a decrease in the average size of relatively small particles.
  • reaction temperature and the rotational speed be controlled in a mutually linked manner, rather than within the ranges presented independently of each other.
  • the rotational speed and the reaction temperature are proportional to each other. If the increase in the 800rmp is 600rpm, banung temperature may be increased from 130 ° C to 150 o C.
  • the length of the jacket is advantageous for mass production, and it is the length that can stably form several vortex cells, but it is sufficient that the manufactured metal or particle does not remain in the jacket for an excessively long time.
  • the residence time of the semi-rigid fluid containing the total solution 1 and the second solution introduced through the inlet in the reaction chamber is preferably 1 to 4 minutes.
  • the injection speed of the reaction fluid injected through the inlet can be controlled, i.e. the injection speed of the first and second solutions can be such that the residence time of the reaction fluid is one to four minutes.
  • the U solution may contain metal precursors, organic acids and organic amines, and the second solution may contain reducing agents.
  • the metal precursors, organic acids, organic amines and reducing agents may be prepared by batch methods. Similar to the above, it is the same.
  • the composition ratio of the first solution is not particularly limited, but considering the capping efficiency, the acid may be 0.2 to 4 moles, preferably 1 to 4 moles with respect to 1 mole of the metal precursor, and an organic amine of 0.2 or more, preferably It may contain from 0.2 to 50, more preferably from 5 to 20 moles.
  • organic amines the upper limit is not necessarily limited as it acts as a non-aqueous solvent.
  • the metal nanoparticles of step a) may be manufactured continuously or batchwise, but are not limited by the method of manufacturing the metal nanoparticles according to the present invention. To be more productive
  • the metal nanoparticle of step a) is a metal
  • the core may be capped with a capping layer containing an organic acid.
  • the organic acid can be chemisorbed preferentially into the metal core to form a dense organic acid film
  • the capping layer can be made of organic acid. It may be a membrane of organic acids chemisorbed on the core. However, in manufacturing processes using organic acids and organic amines together, a small amount of amine may be included in the capping layer.
  • the metal core is capped with a capping layer containing organic acids, Surface oxide film formation of the metal core can be prevented, and in the case of coarse particles of practically 100 to several hundred nanometer orders, the surface oxide film may not exist.
  • the thickness of the capping layer capping the metal core may be 1 to 2 nm. If the capping layer is too thin, the anti-oxidation effect may be reduced, and if the capping layer is too thick, the metal nanoparticles may be removed. When manufacturing the metal thin film used, excessive energy and time may be consumed to remove the organic capping layer.
  • the metal (metal core) of the metal nanoparticles in the form of a capsule capped with a capping layer containing an organic acid and intended to form an oxide film may be a metal commonly used to manufacture a metal thin film. It may be one or more selected from the group consisting of copper, nickel, cobalt, aluminum, tin and their alloys.
  • the metal nanoparticles of step a) have a size distribution of at least bimodal and satisfy the following Equation 1. I like to do it.
  • Equation 3 A L is the area of the first peak having the smallest center size, based on the center size of the peak, in the size distribution of the metal nanoparticles (the size distribution of the number and the size of two axes), At is the total area of the sum of all peaks in the size distribution, i.e., equation 1 is the ratio of the number of particles forming the first peak divided by the number of particles.
  • the size distribution of the metal nanoparticles may be measured using Dynamic Light Scattering (DLS), and in detail, at temperatures of 25 0 C and concentrations of from 0.01 to 0.1% by weight. Measured by the conditions of the sample (size nanoparticle to be analyzed)
  • the size distribution of the metal nanoparticles may be a size distribution, expressed as the diameter of the particle and the number of particles having that diameter.
  • a distribution of sizes at least bimodal indicates that there is at least two peaks in the size distribution of the metal nanoparticles.
  • the size (particle diameter) corresponding to the center of the peak is the center size
  • the particles belonging to the first peak having the smallest medium size are the first particles, and the second peak having the largest center size. Particles belonging to are collectively referred to as second particles.
  • the metal nanoparticles, in which the metal core of step a) is capped with a capping layer containing an organic acid may satisfy the following Equation 4 and Equation 5.
  • Equation 4 this is the center size of one peak of the silver system, that is, the average size of one particle of the system.
  • D 2 is the incremental size of the second peak with the largest center size, based on the center size of the peak, in the same size distribution. At 5, this is the average size of one particle and D 2 is the average size of the two particles.
  • the size of the particles is very small as shown in the relation 4, even though a small amount of surface oxidation occurs even in the capping layer.
  • the nanoparticles are still able to maintain excellent photosynthesis.
  • the conductive ink composition containing the metal nanoparticles, the non-aqueous organic binder, and the non-aqueous solvent, which is capped by the capping layer containing the organic acid described above, can be prepared. have.
  • Non-aqueous solvents are not particularly limited, but may be printed with alkanes, amines, toluenes, xylenes, chloroform, dichloromethane, tetradecane, octadecene, chlorobenzene, dichlorobenzene, chlorobenzoic acid, And one or more from the group consisting of dipropylene glycol propyl ether.
  • the non-aqueous organic binder is not particularly limited, but may be used as long as it is a non-aqueous organic binder material that is generally used to improve the physical binding strength of the coating film during the manufacture of conductive ink containing metal particles.
  • the non-aqueous organic binder material may be polyvinylidene fluoride (PVDF),
  • Gelatin thixoton, starch, polystyrene, polyurethane, resins containing carboxyl groups, phenolic resins, mixtures of ethylcellulose and phenolic resins, ester polymers, methacrylates Copolymer, self-crosslinking (meth) acrylic acid copolymer, copolymer with ethylenically unsaturated group, ethyl cellulose type,
  • Aqueous organic binders play the role of binders and dispersants at the same time, but do not interfere with the binding between metal particles in the case of photonication, so that a thinner and more conductive metal thin film can be produced.
  • Copolymers of unsaturated carboxylic acids or graft copolymers thereof having an amine number of 5 to 150 mg KOH / g are copolymers of C1-C10 alkyl (meth) acrylates and unsaturated carboxylic acids,
  • Non-aqueous organic binders commercially available materials containing the above-mentioned non-aqueous organic binders
  • the conductive ink composition is 0.05 to 5 parts by weight of a non-aqueous organic binder and 20 to 800 parts by weight based on 100 parts by weight of metal nanoparticles. It may contain a non-aqueous solvent.
  • the non-aqueous organic binder can remain in the conductive metal thin film without intrinsic physical properties upon sintering. Accordingly, the content of the non-aqueous organic binder in the conductive ink composition is too high. In this case, the metal binder binds between the metal nanoparticles and the metal nanoparticles and the substrate.
  • Densification between nanoparticles can be impaired.
  • 0.05 to 5 parts by weight of non-aqueous organic binders have a physical strength that stably maintains shape when the coated ink composition dries without compromising densification between metals or nanoparticles. It is a range in which a coating film having excellent bonding strength with the substrate can be formed, and at the same time, the bonding strength between the substrate metal thin films can be remarkably improved by the polymer binder remaining in the metal thin film after sintering.
  • the conductive ink composition may contain 20 to 800 parts by weight of a non-aqueous solvent, and thus may have proper fluidity for coating or printing.
  • the conductive ink composition may further contain one or more nanostructures selected from conductive nanowires, conductive nanotubes, and conductive nanorods. have.
  • the above-described nanostructure has a role of improving the electrical conductivity of the conductive metal thin film manufactured under the light sintering condition that satisfies the relation 1 described above, and heat generated by the light when the sintering satisfies the relation 1 described above.
  • the role of the heat transfer medium can be achieved quickly and uniformly.
  • conductive nanowires, conductive nanotubes, and / or conductive nanorods have a relatively large aspect ratio relative to particles, which can improve contact between conductive materials, ie, metal nanoparticles.
  • a network between the nanostructures is formed, and the contact between the nanostructure and a large number of metal nanoparticles is formed, thereby improving the electrical conductivity of the metal thin film to be manufactured.
  • the nanostructures contained in conductive ink compositions have a high aspect ratio.
  • Nanostructures acting as heat transfer media are more important than using metal nanoparticles capped with a capping layer containing an organic acid as in one embodiment of the present invention.
  • the conductive ink composition may contain a nano structure, that is, when the metal thin film to be manufactured is less than or equal to ⁇ ,
  • organic substrates such as polyethylene terephthalate, polyethylene naphthalate, polyether ether ketone, polycarbonate, polyarylate, polyether sulfone and polyimide, inorganic substrates such as glass, and paper.
  • the present invention includes a metal thin film manufactured by the above-described manufacturing method, wherein the ink thin film is sintered by photo sintering after the ink is applied in a predetermined pattern (shape) at a predetermined position according to the purpose and purpose of the substrate.
  • a metal thin film can have a certain pattern (shape).
  • the present invention relates to a metal wire including a metal film in which conductors containing base metal nanoparticles are connected to each other in a grain boundary to form a continuous body; and an organic binder, which is common to metal nanoparticles and binds a metal film and a substrate; It includes.
  • the continuous metal film is based on a single metal nanoparticle.
  • the metal nanoparticles In contact with the nanoparticles (grain boundary), the metal nanoparticles (grain boundary), the metal nanoparticles
  • the conductors are conductive nanowires and conductive.
  • the organic binder may exist in the presence of a conductor, i.e., the organic binder may be present in a certain layer between the metal film and the substrate, or may be present in some areas of the metal film surface.
  • Inorganic binders may be present in the metal film and on the surface of the metal film, but not independently.
  • metal wiring is manufactured by ink sintering an ink containing metal nanoparticles and a polymer binder or an ink containing a metal nanoparticle, a nanostructure and a polymer binder, wherein the organic binder is a polymer binder contained in an ink. More specifically, the organic binder may be a polymer binder that is common with the photo-sintered conductor and binds between the conductors and between the conductor and the substrate and remains in the metal film after the photo-sintering.
  • the thermal conductivity of the nanostructure may be 50 W / mk or more, specifically 100 W / mK or more, and 300 to 6000 W / mK of the specific capacity of the nanostructure.
  • Nanostructures include single-walled carbon nanotubes, double-walled carbon nano-leaves, thin multi-walled carbon nano-leaves and multiples
  • Preparing a conductive ink composition containing a conductor, a non-aqueous organic binder, and a non-aqueous solvent may be a conductive ink composition prepared by the above method, and optical sintering may be performed in relation to the above-described method of manufacturing a metal thin film. Satisfying -1, light in the wavelength band from 200 to 800 nm, light in the wavelength band from 370 to 800 nm, and preferably light in the wavelength band from 400 to 800 nm can be carried out for 1 to 2 msec.
  • the metal wiring according to the embodiment of the present invention may contain an organic binder of 0.05 to 0.1 parts by weight based on 100 parts by weight of the metal nanoparticles forming the metal film.
  • the content of the organic binder impairs the electrical conductivity of the metal film. If not, it is a content that can have a strong binding force that does not cause peeling between the metal wiring and the board after 10,000 bending tests.
  • the injection rate (volume / hour) is 1.6: 1, the residence time is 1 minute, 2 minutes, 4 minutes
  • the injection speed of the first solution and the second solution was controlled to be injected through the inlet of the reaction vessel.
  • the temperature of the reaction zone was maintained at 150 ° C through the heating section, and the syringe pump was rotated at 800 rpm.
  • the prepared first solution and the second solution were continuously injected into the laminar flow shear continuous reactor to reflect the copper nanoparticles.
  • the copper nanoparticles obtained through the outlet of the reactor were washed and recovered by centrifugation.
  • a capping layer having a thickness of about 1 nm is formed on the copper core of the single crystal, and the C Is and O Is picks are analyzed by the ⁇ ray electron spectroscopy.
  • the capping layer was formed by oleic acid having an alkyl chain (CC) and a carboxylate (-COO-) moiety.
  • the samples used in the bending test have a length X width X thickness of 20 mm X 20 mm X 0.1 mm.
  • a conductive metal thin film 300 nm
  • a rectangular pattern having a length X width of 20 mm x 16 mm was used.
  • Figure 2 is a sample irradiated with light at 2.17 J / cm 2 Optical photographs showing the results of the adhesion test of Fig. 2, similar to Fig. 2, confirmed that the sample irradiated with light at 2.57 J / cm 2 or less did not come off from the metal thin film substrate during the adhesion test.
  • the metal thin film prepared in Example 1 was analyzed by X-ray photoelectron spectroscopy (XPS) to measure the content of the polymer binder remaining in the metal thin film according to the intensity of the irradiated light.
  • XPS X-ray photoelectron spectroscopy
  • Example 3 J / cm 2 is irradiated in the past rogwang
  • the polymeric binders were carbonized.
  • a film was formed on the polyethylene terephthalate substrate and irradiated with light at 4.00 J / cm 2.
  • the polymer binder was substantially carbonized in the same manner as the result of the metal thin film produced by irradiation with 3.33 J / cm 2 in the Example.
  • sintering is performed under the condition that -1 is satisfied, 6.7 to A metal thin film having a very low specific resistance of ⁇ . ⁇ is produced, and at the same time, more than 60% by weight of the polymer binder contained in the coated film dried before light irradiation remains in the metal film even after light irradiation, resulting in a surprisingly improved adhesion to the substrate. It can be seen that a thin film is produced.
  • FIG. 3 is a photograph showing a metal foil manufactured by irradiating light at 1.90 J / cm 2 and maintaining the electrical conductivity of the metal thin film after 10,000 bending tests and bending tests, even after 10,000 bending tests. It is observed that the stable electric current through the membrane emits the light bulb.
  • the specific resistance is measured after 10,000 bending tests, and the specific resistance increase rate ([specific resistance after bending test-specific resistance before bending test] / It was confirmed that the specific resistance before bending test * 100 (%)) was 60% or less. Also, as a result of performing the adhesion test between the substrate and the metal thin film, the metal thin film was kept on the tape while maintaining the strong bond state between the substrate and the metal thin film. It was confirmed that it was not peeled off.
  • a conductive ink composition was prepared in the same manner as described in Example 1.
  • the prepared conductive ink composition was cast on the polyimide plastic substrate by using a casting method.
  • the dried coating film was irradiated continuously for 1.5 msec at an intensity of 2.5 J / cm 2 to carry out photo sintering. It was confirmed that a metal thin film having a specific resistance of ⁇ was manufactured.
  • light was irradiated between 1.24 and 2.57 J / cm 2 to obtain bending test results and adhesion test results similar to those of photo-sintered metal thin films.
  • the light was irradiated at a strength of 1.5 msec or 3.0 J / cm 2 and 1.0 msec.
  • the thickness of the prepared metal thin film was 30 ⁇ and the area was 25 cm 2 .
  • Example 6 the cross section of the metal thin film manufactured by irradiating with 2.5 J / cm 2 light was prepared.

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Abstract

본 발명의 일 실시예에 따른 전도성 금속박막의 제조방법은 a)금속 코어가 유기산을 포함하는 캡핑층으로 캡핑된 금속나노입자，비수계 유기 바인더 및 비수계 용매를 함유하는 전도성 잉크조성물을 제조하는단계; b)상기 전도성 잉크조성물을 절연성 기판에 도포하여 도포막을 형성하는 단계;및 c)상기 도포막에 비수계 유기 바인더가 잔류하는 광의 강도에서 최대 광 강도 이하로 광을 조사하여 전도성 금속박막을 제조하는 단계;를 포함할 수 있다.

Description

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발명의명칭:광소결을이용한전도성금속박막의제조방법 기술분야
[1] 본발명은전도성금속박막의제조방법에관한것으로，상세하게 ,공정상한 온도가낮은기판이라도기판의손상없이우수한전기전도도를갖는전도성 금속박막의제조가가능하며，단시간내에대면적제조가가능하며，기판과의 결합력이극히우수한전도성금속박막의제조방법에관한것이다.
배경기술
[2] 금속나노입자를포함하는잉크및페이스트를기반으로다양한프린팅공정을 활용하여전자부품소자및에너지웅용부품을제작하는연구는현재의 기술개발의메가트렌드중하나이다.
[3] 금속나노입자를포함하는잉크는포토리소그라피의복잡한공정을사용하지 않고도，미세한패턴의금속배선을스크린프린팅，잉크젯프린팅，그라이바 오프셋프린팅및리버스오프셋프린팅등의단일프린팅공정을통해다양한 기재에인쇄함으로써공정을단순화할수있는장점을가진다.또한이에따른 공정의단순화로제조원가를획기적으로줄일수있을뿐만아니라，배선폭의 미세화로고집적및고효율의인쇄희로의제조를가능하게한다.
4] 본출원인^금속나노입자기반잉크에서，금속나노입자에존재하는표면 산화막에의 금속배선의전도도특성이저하됨을주목하여표면산화막의 형성이완벽히제어된금속나노입자의합성방법을제공한바있다 (대한민국 공개특허제 2013-0111180호).그러나，본출원인이출원한대한민국공개특허 제 2013-0111180호는표면산화막이제어된금속나노입자를함유하는잉크를 도포하여열소성을하며，이러한열소성을통해벌크의특성을부여하기 위해서는비활성분위기에서 300°C이상의고은에서 2시간에이르는장시간 동안고온열처리를진행해야한다는한계점을지니고있다.이러한장시간의 고온열처리에의해，플렉시블소자의기판으로각광받는유연성폴리머기판의 활용이어려우며，나아가,상업성이우수한롤투롤 (roll-to-roll)연속공정에 불리한단점이있다.
[5] 본출원인은표면산화막의형성이제어된금속나노입자잉크를이용한
전도성금속박막의제조방법에대해장시간동안연구를심화한결과,표면 산화막의형성이제어된금속나노입자잉크를이용하여공정상한은도가 100oC 이하로극히낮은기판이라도기판의손상없이벌크와비견되는우수한 전기전도도를가지면서도이와동시에기판과의결합력이놀랍도록우수한 전도성금속박막의제조방법을개발함으로써，본발명을완성하였다.
발명의상세한설명
기술적과제 [6] 본발명은공정상한은도가낮은기판이라도기판의손상없이우수한 전기전도도를갖는전도성금속박막의제조가가능하며，기판과의결합력이 극히우수하여플렉시블부품에효과적으로웅용가능하고，두꺼운후막형금속 박막의제조가가능하며，대기중매우단시간내에대면적제조가가능하고, 를투롤공정의구현이가능하여상업성이우수하며，공정의단순화및제조원가 절감이가능한전도성금속박막의제조방법에관한것이다.
과제해결수단
[7] 본발명의일실시예에따른광소결전도성금속박막의제조방법은 a)금속 코어가유기산을포함하는캡핑층으로캡핑된금속나노입자，비수계유기 바인더및비수계용매를함유하는전도성잉크조성물을제조하는단계; b) 전도성잉크조성물을절연성기판에도포하여도포막을형성하는단계;및 c) 도포막에하기관계식 1을만족하도록광을조사하여전도성금속박막을 제조하는단계;를포함할수있다.
[8] (관계식 1)
Figure imgf000004_0001
[10] 관계식 1에서 ^은도포막에조사되는광의강도 (intensity)이며， Ic는전도성 금속박막에비수계유기바인더가잔류하는광의강도의최대강도이다.
[11] 본발명의일실시예에따른광소결전도성금속박막의제조방법에있어， c) 단계에서，하기관계식 1-1을만족하도록광이조사될수있다.
[12] (관계식 1-1)
[13] ILS≤2.6(J/cm2)
[14] 관계식 1-1에서 1 의정의는관계식 1과동일하다.
[15] 본발명의일실시예에따른광소결전도성금속박막의제조방법에있어，금속 나노입자의평균직경은 20내지 300nm일수있다.
[16] 본발명의일실시예에따른광소결전도성금속박막의제조방법에있어, c)단계에서 200내지 800nm의파장대역을포함하는광이연속적으로조사될수 있다.
[17] 본발명의일실시예에따른광소결전도성금속박막의제조방법에있어， c) 단계에서 1내지 2msec동안광이연속적으로조사될수있다.
[18] 본발명의일실시예에따른광소결전도성금속박막의제조방법에있어， 비수계유기바인더는폴리불화비닐리덴 (PVDF),
폴리메틸메타크릴레이트 (PMMA),자기가교성아크릴수지에멀전， 하이드록시에틸샐를로오스，에틸하이드록시에틸셀를로오스,
카르복시메틸셀를로스，하이드록시셀를로오스,메틸셀를로오스,
니트로셀를로오스，에틸셀를로오스,스티렌부타디엔고무 (SBR),
C1-C10알킬 (메타)아크릴레이트와불포화카르복실산의공중합체,
젤라틴 (gelatine),틴소톤 (Thixoton),스타치 (starch),폴리스티렌，폴리우레탄， 카르복실기를포함하는수지 ,페놀성수지，에틸샐를로오스와페놀성수지의 흔합물，에스터증합체，메타크릴레이트증합체,자기가교성의 (메타)아크릴산 공증합체，에틸렌성불포화기를갖는공중합체，에틸샐를로스계，
아크릴레이트계，에폭시수지계및이들흔합물중에서하나또는둘이상선택될 수있다.
[19] 본발명의일실시예에따른광소결전도성금속박막의제조방법에있어， 전도성잉크조성물은금속나노입자 100증량부를기준으로, 0.05내지 5 중량부의비수계유기바인더및 20내지 800중량부의비수계용매를함유할수 있다.
[20] 본발명의일실시예에따른광소결전도성금속박막의제조방법에있어， 전도성잉크조성물은전도성나노와이어，전도성나노류브및전도성 나노로드에서하나또는둘이상선택되는나노구조체를더함유할수있다.
[21] 본발명의일실시예에따른광소결전도성금속박막의제조방법에있어， 나노구조체의열전도도는 50 W/mK이상일수있다.
[22] 본발명의일실시예에따른광소결전도성금속박막의제조방법에
있어,나노구조체의종횡비 (aspect ratio)는 10내지 10000일수있다.
[23] 본발명의일실시예에따른광소결전도성금今박막의제조방법에있어， 나노구조체는단일벽 (Single-walled)탄소나노튜브，이증벽 (Double walled) 탄소나노류브，얇은다증벽 (Thin multi- walled)탄소나노튜브및다증
벽 (Multi-walled)탄소나노튜브에서하나또는둘이상선택될수있다.
[24] 본발명의일실시예에따른광소결전도성금속박막의제조방법에있어， 전도성잉크조성물은금속나노입자 100증량부를기준으로, 1내지 10 중량부의나노구조체를함유할수있다.
[25] 본발명은상술한제조방법으로제조된전도성금속박막을포함한다.
[26] 본발명의일실시예에따른금속배선은기재상금속나노입자를포함하는 전도체가서로입계를이루며연결되어연속체를이루는금속막;및금속 나노입자와흔재하며금속막과기재를결착시키는유기바인더；를포함할수 있다.
[27] 본발명의일실시예에따른금속배선은금속코어가유기산을포함하는
캡핑층으로캡핑된금속나노입자및고분자바인더를함유하는잉크의 광소결에의해제조되며,유기바인더는잉크에함유된고분자바인더일수 있다.
[28] 본발명의일실시예에따른금속배선은금속나노입자 100중량부기준， 0.05 내지 0.1중량부의유기바인더를함유할수있다.
[29] 본발명의일실시예에따른금속배선에있어，전도체는전도성나노와이어, 전도성나노튜브및전도성나노로드에서하나또는둘이상선택되는 나노구조체를더포함할수있다.
[30] 본발명의일실시예에따른금속배선은금속나노입자 100중량부기준， 1내지 10중량부의나노구조체를포함할수있다.
[31] 본발명의일실시예에따른금속배선에있어，나노구조체는
단일벽 (Single-walled)탄소나노튜브,이증벽 (Double walled)탄소나노류브，얇은 다중벽 (Thin multi-walled)탄소나노류브및다중벽 (Multi-walled)
탄소나노류브에서하나또는둘이상선택될수있다.
발명의효과
[32] 본발명의일실시예에따른제조방법은표면산화막이제어된금속
나노입자의소결은이루어지되，고분자바인더가탄화되지않고금속박막에 잔류하는강도로광이조사되어금속박막이제조됨에따라，벌크에비견되는 매우우수한전기전도도를가지면서도기판과의결합력이극히우수한전도성 금속박막을제조할수있는장점이있다.나아가,열안정성이우수한방법임에 따라,공정상한은도가 100oC이하로매우낮은기판이라도금속박막형성 단계에서기판이손상되는것을방지할수있으며，어떠한기판이라도우수한 전기전도도와높은결착력을갖는금속박막을형성할수있는장점이있다. 도면의간단한설명
[33] 도 1은금속나노입자의제조시사용될수있는반웅장치를도시한도면이며， [34] 도 2는실시예 1에서제조된샘플의접착력테스트결과를보여주는광학
사진이며,
[35] 도 3은실시예 1에서제조된샘플의만번의굽힘시험과정및굽힘시험후의 전구발광을관찰한광학사진이며,
[36] 도 4는실시예 2에서종이를기판으로사용하여제조된샘플의광학사진이다.
[37]
발명의실시를위한형태
[38] 이하첨부한도면들을참조하여본발명의제조방법을상세히설명한다.
다음에소개되는도면들은당업자에게본발명의사상이충분히전달될수 있도록하기위해예로서제공되는것이다.따라서 ,본발명은이하제시되는 도면들에한정되지않고다른형태로구체화될수도있으며,이하제시되는 도면들은본발명의사상을명확히하기위해과장되어도시될수있다.이때, 사용되는기술용어및과학용어에있어서다른정의가없다면，이발명이 속하는기술분야에서통상의지식을가진자가통상적으로이해하고있는 의미를가지며，하기의설명및첨부도면에서본발명의요지를불필요하게 흐릴수있는공지기능및구성에대한설명은생략한다.
[39] 본출원인은우수한상업성을가지며，플렉시블부품에적합한금속박막의 제조방법에대해연구를심화한결과，산화막이제어된금속나노입자를 함유하는잉크를광소결하는경우，놀랍도록낮은광에너지에의해벌크에 비견되는전기전도도를갖는금속박막이제조됨을발견하였다.
[40] 나아가,산화막이제어된금속나노입자를함유하는잉크의광소결거동을 심화하여연구한결과，산화막이제어된금속나노입자를함유하는잉크를 광소결함으로써,놀랍게도종래의금속나노입자함유잉크를이용한
광소결시에는얻을수없는극히우수한기판과의결착력을갖는전도성 금속박막이제조될수있음을발견하여 ,본발명올완성하기에이르렀다.
[41] 상세하게，본발명의일실시예에따른광소결전도성금속박막의제조방법은 a)금속코어가유기산을포함하는캡핑층으로캡핑된금속나노입자,비수계 유기바인더및비수계용매를함유하는전도성잉크조성물을제조하는단계; b) 전도성잉크조성물을절연성기판에도포하여도포막을형성하는단계;및 c) 도포막에하기관계식 1을만족하도록광을조사하여전도성금속박막을
제조하는단계;를포함할수있다.
[42] (관계식 1)
[43] ILS<IC
[44] 관계식 1에서 1^은도포막에조사되는광의강도 (intensity)이며， Ic는전도성 금속박막에비수계유기바인더가잔류하는광의강도의최대강도이다.
[45] 금속코어가유기산을포함하는캡핑층으로캡핑된금속나노입자，즉，
캡핑층에의해표면산화막형성이방지된금속나노입자를함유하는잉크가 광소결되는경우에만가질수있는특징적이며독특한조건이다.
[46] 상세하게 ,본출원인은유기산을포함하는캡핑층으로캡핑된금속나노입자를 함유하는잉크를박막화하는다양한방법에대해장기간동안연구를수행한 결과,놀랍게도캡핑층에의해산화막형성이방지된금속나노입자를함유하는 잉크를광소결하는경우，놀랍도록낮은광강도에서도소결이이루어지며， 비수계바인더에의한결착력이소결후에도유지되는금속박막이제조될수 있음을발견하였다.상세하게，잉크에함유되는비수계유기바인더가탄화되지 않고,바인더자체의물성을그대로유지하며박막에잔류한상태로벌크에 버금가는전기전도도를갖는금속박막의제조가가능함을발견하였다.
[47] 이러한광소결조건 (관계식 1의조건)은종래의광소결을이용한금속배선 제조방법분야에서알려진바없으며,또한연구된바없는조건으로,유기산을 포함하는캡핑층으로캡핑된금속나노입자를함유하는잉크를광소결하는 경우에만가질수있는조건이다.
[48] 즉，본발명에따른제조방법은벌크에비견되는전기전도도를가질수있도록 소결되는광의강도가고분자바인더를탄화시키는광의강도보다낮은특징적 구성을가질수있다.
[49] 관계식 1의광소결조건은금속나노입자를이용한광소결분야에종사하는 당업자에게매우놀라운것이다.일반적으로광소결시금속나노입자들의 소결 (치밀화)은광에의해가해지는높은에너지에의해금속나노입자들의 표면영역이순간적으로용융되며이루어지는것으로알려져있으며，이러한 금속나노입자들의소결 (치밀화)을위해,실질적으로 lOJ/cm2이상의강도를 갖는광이조사되고있다.그러나，적어도금속나노입자들의표면영역이 순간적으로용융될정도의고온 (순간적고온)조건에서,금속나노입자를서로 결착시키며금속나노입자와흔재하는고분자바인더는그물성을잃고탄화될 수밖에없다.실질적으로， 10J/cm2이상의강도를갖는광의조사시，고분자 바인더는고유의물성을잃고완전히탄화된상태가된다.그러나，관계식 1은 금속나노입자들의표면용융이라는치밀화기작을고려할때，고분자바인더가 탄화되지않고，고분자바인더본연의물성을유지하며잔류하는상태임에도, 산화막이제어된금속나노입자의경우,놀랍게도벌크에비견되는
전기전도도를가질수있도록금속나노입자의소결 (치밀화)이이루어질수 있음을의미하는것이다.
[50] 상술한바와같이，본발명의일실시예에따른제조방법은관계식 1에따라 광을조사함으로써，벌크에비견되는전기전도도를가지면서도고분자 바인더가잔류하는전도성금속박막이제조될수있다.
[51] 본발명의일실시예에따른제조방법은금속나노입자와흔재하는고분자 바인더가잔류할수있을정도로열안정성이우수한방법임에따라,공정상한 온도가 100°C이하로매우낮은기판이라도기판의손상없이벌크에비견되는 우수한전기전도도를갖는전도성금속박막의제조가가능하며，잔류하는 고분자바인더에의해금속박막과기판간결합력이극히우수하여플렉시블 부품에매우적합한전도성금속박막의제조가가능한장점이있다.또한， 광소결공정을이용함에따라，광소결의장점인대기중매우단시간내에대면적 제조가가능하며，를투를공정의구현이가능하여상업성이우수하고,공정의 단순화및제조원가절감이가능한장점이있다.
[52] 본발명의일실시예에따른광소결전도성금속박막의제조방법에있어， c) 단계에서,하기관계식 1-1을만족하도록광이조사될수있다.
[53] (관계식 1-1)
[54] ILS≤2.6(J/cm2)
[55] 관계식 1-1에서 ^의정의는관계식 1과동일하다.
[56] 구체적으로,조사되는광의강도가 2.6 J/cm2를초과하는경우,잉크에함유된 고분자바인더가금속박막에잔류하지못하고탄화되어,잔류하는고분자 바인더에의한금속박막과기판간의결착효과를얻올수없게된다.
[57] 상세하게,본발명의일실시예에따른제조방법은수내지수백 μΩ η이하의 낮은비저항을갖는전도성금속박막이제조되며, 2.6 J/cm2이하의광이 조사되어고분자바인더가잔류하는금속박막이제조된다.
[58] 본발명의일실시예에따른제조방법에서，광소결단계는,상술한관계식 1, 구체적으로관계식 1-1을만족하며, 200내지 800nm의파장대역의광이 연속적으로조사되어수행될수있다 . 200내지 800imi파장대역의광은가시광 대역의광을포함하는파장대역으로,이러한 200내지 800nm의광이
조사됨으로써，금속입자의광소결이야기되면서기판에미치는열손상을 최소화할수있다. [59] 보다구체적으로,광소결단계는,상술한관계식 1,구체적으로관계식 1-1을 만족하며， 370내지 800nm의파장대역의광，더욱구체적으로 400내지 800nm 파장대역의광이연속적으로조사되어수행될수있다. 370내지 800nm의파장 대역의광，구체적으로 400내지 800nm파장대역의광이조사되는것은，강한 에너지를갖는자외선이아닌，가시광에의해광소결이이루어지는것을 의미한다.
[60] 가시광에의한광소결은유기산을포함하는캡핑층으로캡핑됨으로써，표면 산화막형성이방지되어，그표면이산화물이아닌금속의속성을유지하는금속 나노입자를광소결하는특성에의해가능한구성이다.가시광조사에의해 광소결이이루어짐에따라，자외선조사대비기판이열손상으로부터현저하게 자유로울수있다.
[61] 본발명의일실시예에따른제조방법은상술한관계식 1，구체적으로관계식 1一 1을만족하는강도의광이 1내지 2msec동안연속적으로조사될수있다.즉, 본발명의일실시예에따르면， 1내지 2msec라는극히짧은시간동안광이 조사되어낮은비저항을가지며기판와의결착력이극히우수한금속박막을 제조할수있다.또한,종래의금속나노입자를함유하는잉크의광소결시，금속 나노입자의소결을위해높은에너지의광이조사됨에따라기판등의손상을 방지하고최소의온도에서소결을수행하기위해극단파의필스형태로광이 조사되는것이통상적이다.
[62] 그러나，본발명의일실시예에따르면，기판별로，제조하고자하는금속박막의 두께별로，물질별로，개별적으로특화되어야하는필스폭,필스갭이나필스 수등의설계가불필요하며,단지 1내지 2msec동안연속적으로광을
조사 (연속광을조사)하는것으로안정적인광소결이이루어질수있다.
[63] 광조사의시간은광에의해발생하는열의누적에의해，광소결과정에서
박막 (광이조사되는도포막)의실질적온도및기판의실질적인온도에영향을 미칠수있다.기판의물질등을고려하여，광의조사시간이적절히변경될수 있으나，상술한관계식 1，구체적으로관계식 1-1을만족하는광,좋게는상술한 관계식 1，구체적으로관계식 1-1을만족하고， 200내지 800nm의파장대역의광， 좋게는 370내지 800nm의파장대역의광,보다좋게는 400내지 800nm파장 대역의광이 1 msec미만의시간으로연속적으로조사되는경우，불균질한 광소결이발생할수있어대면적의금속박막제조가어려울위험이있고， 2 msec를초과하는시간으로연속적으로조사되는경우，누적된열에의해 폴리에틸렌테레프탈레이트기판와같이내열특성이떨어지는기판의손상이 발생할위험이있다.
[64] 광소결시,기판상，기설계된패턴으로잉크가도포되어도포막을형성한후, 도포막의건조가이루어질수있음은물론이며，특별히한정되지않으나,건조는 상온에서수행될수있음은물론이다.도포막이형성된기판에는광이면조사될 수있다.즉，도포막이형성된기판전영역에,상술한관계식 1,구체적으로 관계식 1-1을만족하고, 200내지 800nm의파장대역의광，좋게는 370내지 800nm의파장대역의광,보다좋게는 400내지 800nm파장대역의광이，좋게는 1내지 2msec동안조사될수있다.
[65] 상술한바와같이 ,본발명의일실시예에따른제조방법은유기산을포함하는 캡핑층으로캡핑된금속나노입자를함유하는전도성잉크조성물을관계식 1의 조건,구체적으로관계식 1-1의조건을만족하도록광소결하여전기전도도가 우수하면서도기판과의결착력이극히우수한전도성금속박막을제조할수 있다.
[66] 본발명의일실시예에따른제조방법에있어,광조사시，관계식 1을만족하며， 금속나노입자의소결이발생하는강도이상의광이조사될수있다.구체적으로， 조사되는광강도가 1.2J/cm2이상인경우금속나노입자의광소결이발생할수 있다.
[67] 본발명의일실시예에따른제조방법은 a)단계전，유기산올포함하는
캡핑층으로캡핑된금속나노입자를제조하는단계 (이하，입자제조단계)를더 포함할수있다.
[68] 입자제조단계는배치식또는연속식방법일수있다.배치식으로유기산을 포함하는캡핑층으로캡핑된금속나노입자를제조하는단계는본출원인이 출원한대한민국공개특허제 2013-0111180호를참고하여수행될수있으며，본 발명은대한민국공개특허제 2013-0111180호에기재된모든내용을포함한다.
[69] 구체적으로，배치식제조를이용하는경우，입자제조단계는금속전구체,
유기산，유기아민및환원제를포함하는전구체용액을가열하여표면산화막 형성이방지되고유기산을포함하는캡핑층으로캡핑된금속나노입자를 제조하는단계;를포함할수있다.이때,가열교반은불활성분위기에서수행될 수있다.
[70] 금속전구체의금속은구리，니켈，코발트，알루미늄및이들의합금으로
이루어진군으로부터하나또는둘이상선택된것일수있다.금속전구체는 구리,니켈，코발트，알루미늄，주석및이들의합금으로이루어진군에서선택된 금속의질산염，황산염，아세트산염，인산염,규산염및염산염으로이루어진 무기염에서하나이상선택된것일수있다.
[71] 유기산은탄소수가 6 ~ 30인직쇄형，분지형및환형중적어도하나의형태를 가지며 ,포화또는불포화산에서선택된하나또는둘이상일수있다.보다 구체적으로，올레산，리신올레산，스테아릭산，히아드록시스테아릭산,리놀레산, 아미노데카노익산，하이드록시데카노익산，라우르산，데케노익산，
운데케노익산,팔리트올레산，핵실데카노익산，하이드록시팔미틱산，
하이드록시미리스트산,하이드록시데카노익산,팔미트올레산및
미스리스올레산등으로이루어진군에서하나또는둘이상선택할수있으나 이에한정되는것은아니다.전구체용액에서,금속전구체와유기산과의 몰비율은 1 (금속전구체 ): 0.2 ~ 4(산)일수있다. [72] 유기아민은탄소수가 6 ~ 30인직쇄형,분지형및환형증적어도하나의 형태를가지며，포화및불포화아민중에서하나또는둘이상을선택할수있다. 보다구체적으로핵실아민，헵틸아민，옥틸아민,도데실아민， 2-에틸핵실아민, 1,3-디메틸 -n-부틸아민， 1-아미노토리데칸등에서선택할수있으나이에 한정되는것은아니다.전구체용액에서아민의함량은금속전구체에 1몰에 대하여 0.2몰이상，좋게는 1~50몰，더욱좋게는 5~50몰이좋으나，상한에있어, 유기아민이비수계용매로작용할수있으므로굳이제한되지않는다.
[73] 환원제는하이드라진，하이드라진무수물，염산하이드라진，황산하이드라진， 하이드라진하이드레이트및페닐하이드라진을포함하는하이드라진계 환원제에서선택된하나또는둘이상일수있다.또한이밖에도
하이드라이드계;테트라부틸암모늄보로하이드라이드，
테트라메틸암모늄보로하이드라이드，테트라에틸암모늄보로하이드라이드및 소듬보로하이드라이드등을포함하는보로하이드라이드계;소듐포스페이트계; 및아스크로빅산;에서하나또는둘이상을선택하여사용할수있다.전구체 용액에서，환원제는환원제 /금속전구체몰비가 1~100이되도록포함할수있다.
[74] 배치식방법에있어，금속나노입자합성은크게제한적이지않지만환원
효율성을고려하여 100 ~ 350 °C에서，보다바람직하게는 140 ~300°C,더욱 좋게는 150~250oC에서수행될수있으며,불활성분위기에서수행될수있다. 금속나노입자는원심분리와같은나노입자희수시사용되는통상의방법을 통해분리회수될수있음은물론이다.
[75] 이와독립적으로,테일러쿠에트반웅기 (층류전단흐름반웅장치 )에기반한 연속식방법으로,유기산으로캡핑된금속나노입자를연속적으로제조할수 있다.이러한연속식제조는，고른품질의금속나노입자를단시간에대량생산할 수있으며，제조되는금속나노입자의입도분포조절에용이한장점이있다.
[76] 연속식제조의경우，입자제조단계는속빈원통형자켓및상기자켓과
동심구조를이루며이격위치하여회전하는실린더사이의공간인반웅공간에 유기산,유기아민및금속전구체를함유하는제 1용액과환원제를함유하는 제 2용액을연속적으로주입하는단계;를포함할수있다.
[77] 도 1은본발명의일실시예에따른제조방법에서사용될수있는층류전단흐름 반웅장치의일예를도시한도면이다.도 1에도시한바와같이,충류전단흐름 반웅장치는실린더，실린더의내부중앙에형성되고그일단이모터와연결되어 실린더를회전시키는교반봉，교반봉을동심으로하며，실린더의외주에 형성되어고정되는원통형자켓,자켓과실린더간의이격공간인반응공간에 물질을주입하는유입구와반웅이완료된생성물을배출하는유출구를포함할 수있다.이에따라，실린더는자켓의종축과일치하는회전축을가질수있다.
[78] 이때，도 1에도시한바와같이,유입구는자켓의일단또는일단측면에위치할 수있으며,유출구는자켓타단또는타단측면에위치할수있다.또한， 층류전단흐름반웅장치는자켓의외측에위치하여반웅공간을가열하는 가열부를더포함할수있음은물론이며,가열부가자켓의외측을둘러싼형태로 위치할수있음은물론이다.
[79] 고정되어있는자켓에실린더가회전하는경우，반웅공간을흐르는유체는 원심력에의해고정된자켓방향으로나가려는경향을가지게되며，이에의해 유체가불안정하게되어，회전축을따라규칙적이며서로반대방향으로 회전하는고리쌍배열의와류인쿠에트-테일러와류가형성될수있다.
[80] 쿠에트-테일러와류는단지내부실린더와자켓간의상대적인회전에
의해서만와류가발생함에따라,와류의유동성이잘규정될수있으며와류의 요동변화가거의발생하지않을수있다.또한，회전하는고리쌍배열의와류 각각은반웅공간내에서서로독립적인반웅장을형성할수있다.
[81] 이러한고리쌍배열의와류및와류에의해규정되는미세반웅장에유기산， 유기아민，금속전구체및환원제를투입하여금속나노입자를제조하는경우， 안정적이고재현성있게，극히우수한수율로금속코어가유기산을포함하는 캡핑층으로캡핑된금속나노입자가제조될수있다.
[82] 상세하게 ,테일러 -쿠에트와류에기반한층류전단흐름연속반웅기법은
실린더의회전에의해서만，잘규정되는흐름을갖는와류가발생하며，와류 각각이독립적은미세반웅장을형성함에따라，전구체상태의금속으로부터 금속핵이생성되고，금속핵이금속나노입자로성장하는과정에서，전구체 상태의금속과함께투입되는유기산이금속나노입자를매우안정적으로 캡핑할수있다.또한, 95%이상의매우높은수율로유기산을포함하는 캡핑층으로캡핑된금속나노입자가제조될수있다.
[83] 상술한바와유사하게，유입구는자켓의일단또는일단측면에형성될수 있으며，제 1용액이주입되는제 1유입구와제 2용액이주입되는제 2유입구가 형성될수있다.이와독립적으로，제 1용액과제 2용액이유입구로유입되며서로 흔합되도록주입함으로써，단일한유입구를통해，제 1용액과제 2용액이주입될 수있다.
[84] 즉，자켓의일단또는일단측면에형성된유입구를통해제 1용액과제 2용액이 반응공간으로연속적으로주입되어，자켓타단또는타단측면에형성된 유출구를통해캡핑층으로캡핑된금속나노입자를포함하는반웅산물이 연속적으로배출될으로써，연속적으로금속나노입자를제조할수있다.이때， 제조되는금속나노입자의입자크기분포를엄밀하고재현성있게제어하는 측면에서，단일한유입구를통해제 1용액과제 2용액이동시주입될수있다.
[85] 본발명의일실시예에따른제조방법에있어，자켓과실린더는하기관계식 2를만족할수있다.
[86] (관계식 2)
Figure imgf000012_0001
[88] 관계식 2에서， D는자켓과실린더사이의이격간격이며, ri는실린더의
반지름이다. [89] 관계식 2와같이,자켓과실린더사이의이격간격 (D=r。(자켓의내부반경) -r과 실린더의반지름 (r의비율 (D/ri)은 0.1~으4것이좋다.
[9이 자켓과실린더사이의간격은형성되는고리쌍배열의와류인와류셀의크기를 결정하게되어합성되는입자의크기및분포에영향을미칠수있다.또한，
D/ri의값이 0.1보다작으면합성된입자들이간격을메을확률이커져서 공정성을저하시키고， D/ri의값이 0.4보다크면형성되는와류샐이크기가 커져서균일한흔합효과를기대하기어렵다.
[91] 상세하게 ,관계식 2를만족하며，자켓과실린더의이격간격은 1mm내지
2.5mm로,반웅공간의폭이극히작은것이보다좋다.반웅공간의폭이 1mm 내지 2.5mm로극히작은경우,광소결특성이보다우수한바이모달분포의금속 나노입자제조에유리하다.
[92] 주입된제 1용액과계 2용액을포함하는반웅유체가반웅공간에체류하는 체류시간은실런더의회전속도와반웅유체의투입량에의해조절될수있다.
[93] 실린더의회전속도는안정적인테일러 -쿠에트와류형성측면에서 400rpm 이상인것이좋다.또한，각와류셀내에층분한반웅물이존재하여야균질한 나노입자들이제조될수있다.이에따라,실린더의회전속도는 1000 rpm이하인 것이좋다.
[94] 광소결특성이보다우수한바이모달분포의금속나노입자제조를제조하는 측면에서，실린더의회전속도는 600내지 800rpm인것이좋다.이러한회전 속도는와류샐내에존재하는반웅물들이반웅하여，지속적으로금속의핵생성 및성장이발생함과동시에，성장한입자들간에도미세한입자들이소모되며 조대한입자들이성장함으로써，반웅장내의성장구동력 (반웅물및해당 시점에서반웅장에잔류하는입자들의입도분포상미세입자들로부터 제공되는구동력)을소모하고，다른입자들의성장을억제하거나미세한핵들을 다시녹여내며보다미세한입자들의분율이증가된바이모달분포의금속 나노입자가제조될수있다.
[95] 본발명의일실시예에따른제조방법에있어，반웅온도는특별히한정하지 않지만 100내지 350°C의범주에서반웅시킬수있으며좋게는 120~200°C,더욱 좋게는 130~150°C에서반웅하는것이우수한비저항특성을가지면서
수율에서도 95%이상의고순도의금속나노입자가제조될수있다.
[96] 좋게는，광소결특성이보다우수한바이모달분포의금속나노입자가제조될 수있도록，반웅온도는 130내지 150°C인것이좋다.와류샐내에서의전체적인 핵생성및성장구동력이소모되는속도와핵생성정도에영향을미칠수있다. 130내지 150°C의낮은온도에의해，상대적으로작은입자와상대적으로큰 입자간의입자크기차를증가시킬수있으며，상대적으로작은입자들의비율 증가와상대적으로작은입자들의평균크기감소를야기할수있다.
[97] 이때，반응온도가와류셀의전체적인구동력이소모되는속도와핵생성
정도에영향을미치며，실린더의회전속도가와류셀의전체적인구동력의 크기를제어함에따라，반웅온도와회전속도가서로독립적으로제시된 범위에서조절되는것보다는，상호연계되어조절되는것이좋다.구체적인일 예로，회전속도와반웅온도는비례관계인것이좋은데，일예로，회전속도가 600rpm에서 800rmp으로증가하는경우，반웅온도는 130°C에서 150oC로 증가하는것이좋다.
[98] 자켓의길이는대량생산에유리하며，안정적으로여러개의와류샐이형성될 수있는길이이면서도，제조된금속나노입자가과도하게장시간동안자켓내에 잔류하지않는정도면무방하다.구체적이며비한정적인일예로,자켓의 길이 (반웅공간의종축길이)는 30내지 50D(D=자켓과실린더간의이격거리)일 수있다.
[99] 연속식제조에있어，유입구를통해주입되는계 1용액과제 2용액을포함하는 반웅유체가반웅공간에머무르는체류시간은 1내지 4분인것이좋다.이러한 체류시간은상술한회전속도및상술한자켓길이에서，유입구를통해 주입되는반웅유체의주입속도를통해조절할수있다.즉，제 1용액과 제 2용액의주입속도는반웅유체의체류시간이 1내지 4분이되도록하는 속도일수있다.
[100] 연속식제조에있어，자켓의내주면에는실린더의회전방향으로종축방향을 따라서나선형돌기가형성되어있을수있다.이러한나선형돌기가형성되는 경우반웅물의흔합효율이더욱증가되어더욱짧은시간내에환원반웅이 완결되어금속나노입자가신속히제조될수있다.
[101] 연속식제조에있어，겨 U용액은금속전구체，유기산및유기아민을포함할수 있으며，제 2용액은환원제를포함할수있다.금속전구체,유기산，유기아민및 환원제물질은배치식방법에서상술한바와유사내지동일하다.
[102] 제 1용액의조성비는크게제한적이지않지만，캡핑효율을고려하였을때， 금속전구체 1몰에대하여산은 0.2 - 4몰，좋게는 1내지 4몰일수있고，유기 아민은 0.2이상,좋게는 0.2 ~ 50,더욱좋게는 5~20몰을함유할수있다.유기 아민의경우，비수계용매로작용함에따라,그상한이굳이제한되지않는다.
[103] 계 1용액과제 2용액은제 1용액에서금속전구체의함량에대하여환원제 /금속 전구체몰비가 1~100이되도록주입될수있다.몰비 (환원제 /금속전구체)가 1미만인경우금속전구체의금속이온이전부환원되지못하는문제가있으며 100을초과하는경우과잉이되어환원속도에영향을주지못하므로효율및 비용측면에서유리하지않다.
[104] 상술한바와같이， a)단계의금속나노입자는연속식또는배치식으로제조될 수있으나,본발명이제시된금속나노입자를제조하는방법에의해한정되는 것은아니다.다만，금속나노입자를보다생산성있게제조하며금속
나노입자의입도분포의용이조절측면에서연속식방법으로금속나노입자를 제조할수있다.
[105] 본발명의일실시예에따른제조방법에있어， a)단계의금속나노입자는금속 코어가유기산을포함하는캡핑층으로캡핑된것일수있다.유기산은금속 코어에우선적으로화학흡착 (chemisorption)하여치밀한유기산막을형성할수 있음에따라，캡핑층은유기산으로이루어질수있다.즉，캡핑층은금속코어에 화학흡착된유기산의막일수있다.그러나，유기산과유기아민을함께 사용하는제조공정상캡핑층에미량의아민이포함될수있음은물론이다.금속 코어가유기산을포함하는캡핑층으로캡핑됨에따라，금속코어의표면산화막 형성이방지될수있으며,실질적으로 100내지수백나노미터오더의조대한 입자의경우표면산화막이존재하지않을수있다.
[106] 캡핑층의유기산은탄소수가 6 ~ 30인직쇄형，분지형및환형중적어도
하나의형태를가지며，포화또는불포화유기산에서선택된하나또는둘 이상일수있다.보다구체적으로，유기산은올레산，리신올레산,스테아릭산， 히아드록시스테아릭산,리놀레산，아미노데카노익산,하이드록시데카노익산， 라우르산，데케노익산，운데케노익산，팔리트올레산，핵실데카노익산， 하이드록시팔미틱산，하이드록시미리스트산,하이드록시데카노익산， 팔미트올레산및미스리스을레산등으로이루어진군에서하나또는둘이상 선택될수있으나，이에한정되는것은아니다.
[107] 금속코어를캡핑하는캡핑층의두께는 1내지 2nm일수있다.캡핑층이너무 얇은경우산화막형성방지효과가감소될수있으며,또한캡핑층의두께가 너무과도하게두꺼운경우，금속나노입자를이용한금속박막의제조시， 유기물인캡핑층의제거에과도한에너지와시간이소모될수있다.
[108] 유기산을포함하는캡핑층으로캡핑되고산화막형성이의제된캡슐형태의 금속나노입자의금속 (금속코어 )은금속박막을제조하는데통상적으로 사용되는금속이면무방하다.구체적인일예로，금속은구리，니켈，코발트， 알루미늄，주석및이들의합금등으로이루어진군으로부터하나또는둘이상 선택된것일수있다.
[109] 본발명의일실시예에따른제조방법에있어,보다우수한광소결특성을갖기 위해, a)단계의금속나노입자는적어도바이모달 (bimodal)이상의크기분포를 가지며，하기관계식 1을만족하는것이좋다.
[110] (관계식 3)
[111] 0.4<AJAt<0.8
[112] 관계식 3에서, AL은금속나노입자의크기분포 (갯수와크기를두축으로하는 크기분포)에서，피크의중심크기를기준으로，가장작은중심크기를갖는 제1피크의면적이며， At는크기분포를이루는모든피크의면적을합한총 면적이다.즉,관계식 1은제 1피크를이루는입자의수를총입자의수로나눈 비이다.
[113] 일구체예에있어，금속나노입자의크기분포는동적광산란법 (Dynamic Light Scattering： DLS)을이용하여측정된것일수있으며，상세하게, 250C의온도및 0.01내지 0.1중량 %농도의샘플 (크기분석대상나노입자)의조건으로측정된 것일수있다.금속나노입자의크기분포는입자의직경및해당직경을갖는 입자의수로도시되는크기분포일수있다.적어도바이모달이상의크기 분포는금속나노입자의크기분포상적어도둘이상의피크가존재함을의미할 수있다.이때,피크의중심에해당하는크기 (입자직경)가중심크기이며，가장 작은중삼크기를갖는제 1피크에속하는입자들은제 1입자로，가장큰중심 크기를갖는제 2피크에속하는입자들은제 2입자로통칭한다.
[114] 관계식 3으로제시된바와같이， a)단계의금속나노입자가상대적으로작은 제 1입자들과상대적으로큰제 2입자들중，상대적으로작은제 1입자의분율이 현저하게높은경우，관계식 1을만족하는매우낮은광강도에서도
전기전도도가현저하게우수한금속박막이제조될수있다.
[115] 또한，높은소결구동력을제공할수있도록， a)단계의금속코어가유기산을 포함하는캡핑층으로캡핑된입자인금속나노입자는하기관계식 4및관계식 5를더만족할수있다.
[116] (관계식 4)
[117] 30nm < D, < lOOnm
[118] 관계식 4에서，이은계 1피크의중심크기，즉,계 1입자의평균크기이다.
[119] (관계식 5)
[120] 3 < D2 D, < 5
[121] 관계식 5에서,이은금속나노입자의크기분포에서,피크의중심크기를
기준으로，가장작은중심크기를갖는제 1피크의중심크기이며, D2는동일크기 분포에서，피크의중심크기를기준으로，가장큰중심크기를갖는제 2피크의 증심크기이다.즉，관계식 5에서，이은게 1입자의평균크기이며, D2는계 2입자의 평균크기이다.
[122] 관계식 3의조건을만족함과동시에,관계식 4와관계식 5를만족함으로써， 계 1입자들로부터겨 12입자들로극히활발한물질이동이발생하여，우수한광 소결능을가질수있다.
[123] 보다바람직한점은，관계식 3을만족하도록제 1입자들이다량존재하는경우， 관계식 4와같이，입자의크기가매우미세하여캡핑층에도불구하고어느정도 미량의표면산화가발생하여도,금속나노입자가여전히우수한광소결능을 유지할수있다는점이다.
[124] 상술한관계식 2,좋게는관계식 2， 3및 4를만족하는금속나노입자는보다 바람직한연속식제조조건에의해제조될수있으나，본발명이이에한정되는 것은아니다.배치식제조시반웅온도나가열속도등을류닝하거나，다양한 조건에서배치식또는연속식으로제조된금속나노입자들을서로흔합하여 상술한관계식 2,좋게는관계식 2, 3및 4를만족하는금속나노입자가수득될수 있음은물론이다.
[125] a)단계에서는，상술한유기산을포함하는캡핑층으로캡핑된금속나노입자， 비수계유기바인더및비수계용매를함유하는전도성잉크조성물을제조할수 있다.
[126] 비수계용매는특별히제한되지않지만인쇄좋게는탄소수가 6 - 30인알케인， 아민,를루엔，크실렌，클로로포름，디클로로메탄，테트라데칸，옥타데센, 클로로벤젠，다이클로로벤젠，클로로벤조산，및다이프로필렌글리콜프로필 에테르로이루어진군으로부터하나또는둘이상을선택할수있다.
[127] 비수계유기바인더는특별히한정되지않으나，금속입자를함유하는전도성 잉크제조시，도포막의물리적결착력을향상시키기위해통상적으로사용되는 비수계유기바인더물질이면사용가능하다.구체적이고비한정적인일예로， 비수계유기바인더물질은폴리불화비닐리덴 (PVDF),
폴리메틸메타크릴레이트 (PMMA),자기가교성아크릴수지에멀전，
하이드록시에틸샐를로오스，에틸하이드록시에될샐를로오스,
카르복시메틸샐를로스,하이드록시샐를로오스，메틸셀를로오스,
니트로샐를로오스，에틸셀를로오스，스티렌부타디엔고무 (SBR),
C1-C10알킬 (메타)아크릴레이트와불포화카르복실산의공중합체，
젤라틴 (gelatine),틴소톤 (Thixoton),스타치 (starch),폴리스티렌，폴리우레탄， 카르복실기를포함하는수지，페놀성수지，에틸셀를로오스와페놀성수지의 혼합물，에스터중합체，메타크릴레이트증합체，자기가교성의 (메타)아크릴산 공중합체,에틸렌성불포화기를갖는공중합체，에틸샐를로스계，
아크릴레이트계,에폭시수지계및이들흔합물증에서하나또는둘이상선택될 수있다.
[128] 보다구체적인일예로，비수계유기바인더는 5 - 150 mgKOH/g의아민가를 갖는비수계고분자물질일수있다.이러한비수계고분자물질은바인더및 분산제의역할을동시에수행할수있어좋다.특히，비수계유기바인더는 블포화카르복실산의공중합체또는이의그라프트중합체일수있으며， 5 - 150 mgKOH/g의아민가를갖는불포화카르복실산의공증합체또는이의그라프트 중합체일수있다.이러한비수계유기바인더는바인더및분산제의역할을 동시에수행하면서도，광소결시금속입자간의결착을방해하지않아，보다 치밀하고보다전도도가우수한금속박막이제조될수있다. 5 - 150 mgKOH/g의 아민가를갖는，불포화카르복실산의공중합체또는이의그라프트증합체는 C1-C10알킬 (메타)아크릴레이트와불포화카르복실산의공중합체,
폴리이써케톤과불포화카르복실산의공중합체，폴리아크릴아마이드와불포화 카르복실산의공중합체，폴리에틸렌옥사이드와불포화카르복실산의공중합체， 폴리에틸렌글리콜와불포화카르복실산의공중합체또는이들의흔합물을 포함할수있다 . 5 - 150 mgKOH/g의아민가를갖는불포화카르복실산의 공중합체또는이의그라프트중합체인경우，그분자량 (중량평균분자량)은 1000내지 50000g/m이일수있다.
[129] 비수계유기바인더로，상술한비수계유기바인더물질을함유하는상용
제품을사용하여도무방한데，구체적인일예로, BYK130, BYK140, BYK160, BYK161, BYK162, BY 163, BYK164, BYK165, BYK167, BYK169, BYK170, BYK171, BYK174 EFKA 4610, EFKA 4644, EFKA 4654, EFKA 4665, EFKA 4620, EFKA 4666또는 EFKA 4642등을들수있으나，이에한정되는것은아니다ᅳ
[130] 본발명의일실시예에따른광소결전도성금속박막의제조방법에있어， 전도성잉크조성물은금속나노입자 100중량부를기준으로， 0.05내지 5 중량부의비수계유기바인더및 20내지 800중량부의비수계용매를함유할수 있다.
[131] 본발명의일실시예에따라，광소결시비수계유기바인더가고유의물성이 손상되지않은상태로전도성금속박막에잔류할수있다.이에따라，전도성 잉크조성물내비수계유기바인더의함량이너무높은경우금속나노입자간, 금속나노입자와기판간을결착시키는고분자바인더에의해,금속
나노입자간의치밀화가저해될수있다.입자대비 0.05내지 5중량부의비수계 유기바인더는금속나노입자간의치밀화를저해하지않으면서도，도포된잉크 조성물이건조되었을때안정적으로형상이유지되는물리적강도를가지며 기판과의결착력이우수한도포막이형성될수있으면서，이와동시에，광소결 후금속박막에잔류하는고분자바인더에의해기판금속박막간의결착력이 현저하게향상될수있는범위이다.
[132] 전도성잉크조성물의도포방법에따라어느정도달라질수있으나，전도성 잉크조성물이 20내지 800중량부의비수계용매를함유함으로써,코팅또는 프린팅에적절한유동성을가질수있다.
[133] 본발명의일실시예에따른광소결전도성금속박막의제조방법에있어， 전도성잉크조성물은전도성나노와이어，전도성나노튜브및전도성 나노로드에서하나또는둘이상선택되는나노구조체를더함유할수있다.
[134] 상술한나노구조체는상술한관계식 1을만족하는광소결조건에서제조되는 전도성금속박막의전기전도도를향상시키는역할및상술한관계식 1을 만족하는광소결시，광에의해발생하는열을신속하고균일하게전달하는 열전달매체의역할을동시에수행할수있다.
[135] 상세하게，전도성나노와이어，전도성나노튜브및 /또는전도성나노로드는 입자대비상대적으로매우큰종횡비 (aspect ratio)를가짐에따라，전도성 물질간의접촉을향상시킬수있다.즉，금속나노입자와나노구조체가금속 박막 (또는전도성잉크조성물의도포막)에서균일하게분산될때나노구조체 간의네트워크가형성되고，나노구조체와다수의금속나노입자간의접촉이 형성됨으로써 ,제조되는금속박막의전기전도도를향상시킬수있으며 ,나아가 대면적의금속박막에서도전기적특성의균질성을향상시킬수있다.
[136] 이와함께，상술한바와같이，전도성잉크조성물의도포막은관계식 1을
만족하는극히작은에너지에서광소결된다.이러한광소결조건에의해， 제조하고자하는금속박막의두께 (도포막의두께)가두꺼워질수록광이 입사되는영역인표면영역과기판과인접한영역인하부영역간소결특성이 상이할수있다.즉,기판과인접한도포막의하부영역에서금속나노입자의 소결이층분치못할위험이있다.
[137] 전도성잉크조성물에함유되는나노구조체는큰종횡비를가짐에따라
표면영역으로입사되는광에의해발생하는포논을하부영역으로효과적으로 전달하는열전달매체로작용할수있다.이러한나노구조체에의한보다 신속하고균일한열전달에의해，두꺼운도포막이라하더라도두께방향으로 균질한소결이이루어질수있으며,나아가대면적의도포막이라하더라도매우 균일한전기적특성을갖는금속박막이제조될수있다.
[138] 열전달매체로작용하는나노구조체는본발명의일실시예와같은유기산을 포함하는캡핑층으로캡핑된금속나노입자를이용하는경우보다중요하다.
- 구체적으로，표면산화막형성이방지된금속나노입자를이용함으로써，
현저하게낮은에너지를조사하는광소결조건에서소결이가능해진다.그러나， 금속나노입자의입자간계면및금속나노입자간의빈공간은포논
스캐터링 (phonon scattering)을일으키는주요인중하나로작용하며， 금속나노입자의크기가미세할수록이러한요인에의한포논스캐터링은더욱 심화될수있다.이에따라，전도성잉크조성물이나노구조체를함유하지않는 경우，제조되는금속박막의두께에제약이따를수있다.구체적으로， 나노구조체를함유하지않는전도성잉크조성물은 ΙΟμηι이하，보다안정적으로
3μιη이하의금속박막의제조시보다적합하다.
[139] 그러나，전도성잉크조성물이나노구조체를함유함으로써，조사되는광에 의해발생하는포논을도포막하부를포함한도포막전영역로빠르고균질하게 전달및재분배시켜,두꺼운후막형의금속박막이제조될수있으며，균일한 전기적특성을갖는대면적의후막형금속박막이제조될수있다.
[140] 실질적인일예로，제조하고자하는금속박막이 ΙΟμηι이상의두께를갖는 후막인경우，전도성잉크조성물은나노구조체를함유하는것이좋다.즉, 제조하고자하는금속박막이 ΙΟμιη이하인경우，제조되는금속박막의
전기전도도향상측면에서전도성잉크조성물이나노구조체를함유할수 있으며， ΙΟμπι이상의두께를갖는후막형금속박막을제조하고자하는경우， 금속박막이실질적으로균질하게광소결되도록전도성잉크조성물은 나노구조체를함유하는것이좋다.
[141] 또한，상술한바와같이， 1.2J/cm2이상의광강도에서금속나노입자의광소결이 발생하나，제조하고자하는금속박막의두께가수마이크로내지수십마이크로 수준인경우,균질한전기적특성을갖는금속박막을재현성있게생산하는 측면에서， 2.3J/cm2이상의광강도를갖는광이조사되는것이좋다.
[142] 상술한바와같이，나노구조체에의해면방향및두께방향으로보다균일한 소결이이루어질수있으며，또한나노구조체네트워크와나노구조체및 금속나노입자간의접촉점증가에의해전기전도도가향상될수있음에따라, 제조하고자하는금속박막의두께가수백 nm수준의얇은막이라하더라도 전도성잉크조성물이나노구조체를함유할수있음은물론이다.
[143] 본발명의일실시예에따른제조방법에있어 ,나노구조체는금속나노입자의 금속물질의열전도도이상의열전도도를갖는물질일수있다.상술한바와 같이，금속나노입자와동일한열전도도를갖는나노구조체라할지라도 나노구조체및나노구조체네트워크를통해포논의스캐터링이방지되며 열전달이가능함에따라상술한열전달매체의역할을수행할수있다.
[144] 그러나，관계식 1의광조사조건하에 , 30μηι에이르는두께의후막형금속 박막의경우에도，균질한광소결이수행되며우수하고균일한전기전도도를 갖기위해，나노구조체의열전도도는 50 W/mk이상，구체적으로 100 W/mK 이상,보다구체적으로 300내지 6000 W/mK일수있다.
[145] 본발명의일실시예에따른광소결전도성금속박막의제조방법에있어， 나노구조체는단일벽 (Single-walled)탄소나노류브，이중벽 (Double walled) 탄소나노류브，얇은다중벽 (Thin multi- walled)탄소나노튜브및다중
벽 (Multi-walled)탄소나노류브에서하나또는둘이상선택될수있다.
[146] 본발명의일실시예에따른광소결전도성금속박막의제조방법에있어， 나노구조체의종횡비 (aspect ratio)는 10내지 10000일수있다.이러한종횡비에 의해, 3μπι이상，구체적으로 ΙΟμπι이상의두께를갖는금속박막을제조하고자 하는경우에도，조사되는광에의해발생하는포논이도포막하부를포함한 도포막전영역으로전달및재분배될수있다.
[147] 본발명의일실시예에따른광소결전도성금속박막의제조방법에있어, 전도성잉크조성물은금속나노입자 100증량부를기준으로, 1내지 10 중량부의나노구조체를함유할수있다.전도성잉크조성물이 1중량부미만의 나노구조체를함유하는경우，나노구조체가연속적으로접촉하는 3차원 네트워크가형성되지못할위험이있다.전도성잉크조성물이 10중량부를 초과하는나노구조체를함유하는경우，금속나노입자의균질한공간적분포를 방해하여전기전도도가오히려낮아질수있다.
[148] 상세하게，전도성잉크조성물은금속나노입자 100증량부를기준으로, 1내지
10중량부의나노구조체， 0.05내지 5중량부의비수계유기바인더및 20내지 800중량부의비수계용매를함유할수있다.
[149] 전도성잉크조성물의도포는본발명에서도포는코팅또는프린팅의
방법으로수행될수있다.구체적인일예로，코팅은딥코팅，스핀코팅또는 캐스팅을이용하여수행될수있고，프린팅은스크린프린팅，잉크젯프린팅， 정전수력학프린팅,마이크로컨택프린팅，임프린팅，그라비아프린팅， 리버스옵셋프린팅또는그라비옵셋프린팅을이용하여수행될수있다.전도성 잉크조성물의도포는제조하고자하는제품의설계에따라，적절한패턴을 갖도록도포될수있음은물론이며,선택적으로，절연성기판에전도성잉크 조성물이도포된후，광조사전，용매를휘발제거하기위한건조가수행될수 있음은물론이다. [150] 전도성잉크조성물이도포되는절연성기판은，상술한본발명의특징에의해， 절연성을가진기판이라면어떠한기판이든사용가능하다.
[151] 일예로,폴리에틸렌테레프탈레이트기판은우수한유연성과함께,광투과도가 좋고，유기용매에대해화학적안정성이우수하며물이잘흡착되지않고, 저비용공정인용융-압출을통한필름화가가능하여상업적가치가크다.
그러나，폴리에틸렌테레프탈레이트기판의최대공정온도는 80내지 150oC의 수준임에따라,실질적으로폴리에틸렌테레프탈레이트기판에금속배선을 형성하는데매우큰어려움이따른다.그러나，본발명의일실시예에따른 제조방법은후술하는실시예로보인바와같이，극히낮은공정온도가요구되는 폴리에틸렌테레프탈레이트기판에도매우우수한전기전도도를갖는전도성 금속박막이제조될수있다.
[152] 상술한바와같이，본발명의특징에의해，기판은절연성을가진기판이라면 어떠한기판이든사용가능하며，구체적이고비한정적인일예로，
폴리에틸렌테레프탈레이트,폴리에틸렌나프탈레이트,폴리에텔에텔케톤， 폴리카보네이트,폴리아릴레이트，폴리에테르술폰，폴리이미드등의유기기판， 유리와같은무기기판,종이등을들수있다.
[153] 본발명은상술한제조방법으로제조되는금속박막을포함한다.이때，기판상 용도및목적에따라기정해진위치에기설계된패턴 (형상)으로잉크가도포된 후,광소결에의해금속박막으로제조될수있음은물론이며，이에따라금속 박막이일정한패턴 (형상)을가질수있음은물론이다.
[154] 본발명은기재상금속나노입자를포함하는전도체가서로입계를이루며 연결되어연속체를이루는금속막;및금속나노입자와흔재하며금속막과 기재를결착시키는유기바인더；를포함하는금속배선을포함한다.
[155] 상세하게，연속체인금속막은일금속나노입자를기준으로일금속
나노입자가이와이웃하는금속나노입자증적어도하나이상의금속
나노입자와입계 (grain boundary)를이루며접하여，금속나노입자들이
연속적으로이어져있는상태를의미할수있다.
[156] 제조방법에서상술한바와같이，전도체는전도성나노와이어，전도성
나노튜브및전도성나노로드에서하나또는둘이상선택되는나노구조체를더 포함할수있다.
[157] 전도체가나노구조체를더포함하는경우,연속체인금속막은일전도체 (일 금속나노입자또는일전도성나노구조체)를기준으로일전도체가이와 이웃하는금속나노입자증적어도하나이상의금속나노입자와결착되거나, 다른전도성나노구조체와접하여，전도체가연속적으로이어져있는상태를 의미할수있다.이때，연속체인금속막은전도성나노구조체의네트워크를 포함할수있다.
[158] 유기바인더는，전도체와혼재하여존재할수있다.즉，유기바인더가금속막과 기판사이에일정층을이루며존재하거나，금속막표면일부영역에금속막과 독립적으로존재하는것이아닌，금속막내부및표면에서금속막을이루는 전도체와흔재하여존재할수있다.이에따라，유기바인더는금속막
내부로부터금속막을기재에결착사킬수있어，금속막과기재간의결착력을 현저하게향상시킬수있다.
[159] 구체적으로,금속배선은금속나노입자및고분자바인더를함유하는잉크 또는금속나노입자，나노구조체및고분자바인더를함유하는잉크의광소결에 의해제조되며,유기바인더는잉크에함유된고분자바인더일수있다.보다 구체적으로,유기바인더는광소결전전도체와흔재되어전도체간및전도체와 기판간을결착시키고，광소결후금속막에잔류하는고분자바인더일수있다.
[160] 이때，금속나노입자는앞서금속박막의제조방법에서상술한유기산을
포함하는캡핑층으로캡핑된금속나노입자일수있다.
[161] 이때，나노구조체의열전도도는 50 W/mk이상,구체적으로 100 W/mK이상, 보가구체적으로 300내지 6000 W/mK일수있다.구체적인일예로，
나노구조체는단일벽 (Single-walled)탄소나노튜브，이증벽 (Double walled) 탄소나노류브，얇은다증벽 (Thin multi-walled)탄소나노류브및다중
벽 (Multi-walled)탄소나노튜브에서하나또는둘이상선택될수있다.
[162] 잉크는앞서금속박막의제조방법에서상술한금속나노입자를포함하는
전도체，비수계유기바인더및비수계용매를함유하는전도성잉크조성물을 제조하는단계;에의해제조되는전도성잉크조성물일수있으며，광소결은앞서 금속박막의제조방법에서상술한관계식 1，구체적으로관계식 1-1을만족하고, 200내지 800nm의파장대역의광，좋게는 370내지 800nm의파장대역의광, 보다좋게는 400내지 800nm파장대역의광이 1내지 2msec동안조사되어 수행될수있다.금속배선을상술함에있어，금속나노입자의크기，물질，고분자 바인더의물질，나노구조체의물질,형상，잉크의조성등앞서금속박막의 제조방법에서상술한내용과유사내지동일하다.
[163] 본발명의일실시예에따른금속배선은금속막을이루는금속나노입자 100 중량부기준， 0.05내지 0.1중량부의유기바인더를함유할수있다.이러한유기 바인더의함량은금속막고유의전기전도도를훼손하지않으면서도,만번의 굽힘시험후의금속배선과기판간의박리가발생하지않는강한결착력을 가질수있는함량이다.
[164] 본발명의일실시예에따른금속배선은그두께가 lOOnm내지 30μηι일수 있으며 , 2( Qcm이하의비저항을가질수있다.
[165] (제조예 1)
[166] 옥틸아민 (Octyl amine) 1.41 mol,올레산 (Oleic acid) 0.20 mol및
구리아세테이트 (copper(II) acetate) 0.14m이을흔합한제 1용액과
페닐하이드라진 (phenyl hydrazine) 1.96 md인제 2용액을준비하였다.실린더의 외경 19 mm,자켓의내경 23mm로서실린더와자켓사이의반응부의간극이 2mm이고길이가 90mm인층류전단흐름반응장치를자켓을감싸는히팅부를 이용하여 150°C로가열하였다.계 1용액과제 2용액의상대적
주입속도 (부피 /시간)를 1.6 : 1의비율로하고，체류시간이 1분， 2분， 4분이
되도록제 1용액과제 2용액의주입속도를조절하여반웅기의유입구를통하여 주입하였다.이때히팅부를통하여반웅영역의온도를 150°C로유지시켰으며， 800rpm으로실린더를회전시키면서,주사기펌프를이용하여준비된제 1용액과 제 2용액을층류전단흐름연속반웅기에연속적으로주입하여반웅시켜구리 나노입자를합성하였다.반웅기의유출구를통하여얻어지는구리나노입자를 원심분리법을이용하여세척및회수하였다.
[167] 제조된구리나노입자를투과전자현미경으로분석한결과，단결정체의구리 코어에약 lnm두께의캡핑층이형성됨을알수있으며 , Χ선광전자분광법을 이용하여 C Is및 O Is픽을분석한결과，알킬체인 (C-C)과카복실레이트 (-COO-) 모이어티를갖는을레산에의해캡핑층이형성됨을확인하였다.
[168] 동적광산란법을이용하여제조된구리나노입자의크기분포를측정한결과, 바이모달분포를갖는입자가제조됨을확인하였으며 , 2분의체류시간인경우， A^A 0.5, Dl=70nm및 I E = 3인나노입자가제조되며， 1분의체류시간인 경우， A A^ 0.8， Dl=50nm및 Ε^/Ε^ = 4인나노입자가제조되고， 4분의체류 시간인경우， AJAt= 0.4, Dl=100nm및 = 3인나노입자가제조되었다.
[169] (제조예 2)
[170] 제조예 1에서，반웅은도를 130°C로하고，실린더회전속도를 600rpm으로
하며,체류시간을 2분으로고정한것을제외하고,제조예 1과동일하게구리 나노입자를제조하였다.동적광산란법을이용하여제조된구리나노입자의 크기분포를측정한결과，바이모달분포를갖는입자가제조됨을확인하였으며， AJAt= 0.6, Dl=100nm및 I E = 3.5인나노입자가제조됨을확인하였다.
[171] (실시예 1)
[172] 제조예 1에서, 2분의체류시간으로제조된구리나노입자 2g,비수계용매인 물질톨루엔 8g및고분자바인더인물질로 BYK 130 0.02g을흔합하고볼밀링및 초음파조사를통해균일한분산상을가지는전도성잉크조성물을제조하였다.
[173] 드랍캐스팅방법을이용하여,제조된전도성잉크조성물을
폴리에틸렌테레프탈레이트기판에도포한후, 370-800 nm파장대역을가지는 광원 (linear B-type for Xenon PLA-2010 sintering system)을이용하여 ,
[조사시간 (msec),강도 (J/cm2)]가 [0.5, 0.36], [0.5, 0.47], [0.5， 0.56], [0.5, 0.80], [1.0, 0.80], [1.0, 1.06], [1.0, 1.24], [1.0, 1.73], [1.5, 1.26], [1.5， 1.63], [1.5, 1.90], [1.5, 2.57], [1.5, 1.67], [1.5， 2.17], [1.5, 2.53]또는 [1.5, 3.33]이되도록광을조사하여 폴리에틸렌테레프탈레이트기판상전도성금속박막을제조하였다.이때， 광조사에의해형성되는금속박막의두께는 300nm이었다.
[174] 제조된전도성금속박막의비저항은 4-point probe를이용하여측정하였다.
[175] 제조된전도성금속박막과기판간의접착력테스트를위해， ASTM D3359-97 방법에기준한테이프를이용하였다.제조된전도성금속박막과기판과의계면 특성및전도도열화를테스트하기위해，굽힘 (bending)테스트를수행하였다. 상세하게,굽힘테스트는 2점굽힘시험을통해 l-10 mm의벤딩반경하에서 실시하였다.
[176] 접착력테스트에사용된샘플은길이 X폭 X두께가 20mm X 20 mm X 0.1 mm인 폴리에틸렌테레프탈레이트기판에길이 X폭이 20mm X 16 mm인직사각형 패턴의전도성금속박막 (박막의두께 =300 nm)을형성한것을이용하였다ᅳ굽힘 테스트에사용된샘플은길이 X폭 X두께가 20mm X 20 mm X 0.1 mm인
폴리에틸렌테레프탈레이트기판에길이 X폭이 20mm x l6 mm인직사각형 패턴의전도성금속박막 (박막의두께 =300 nm)을형성한것을이용하였다.
[177] 실시예 1에서제조된전도성금속박막의비저항을측정한결과, 1.06J/cm2 이하의강도로광이조사된경우,저항이매우높아금속배선이나전극으로 사용할수없을정도로광소결이거의이루어지지않았음을알수있다.
구체적으로 1.06J/cm2이하의강도로광이조사된경우，비저항이 105μΩ(;πι 이상이었다.이때，조사광의강도가 1.24내지 2.57 J/cm2사이로광이조사된경우 6.7내지 Π.ΟμΩαη의매우낮은비저항을갖는금속박막이제조됨을
확인하였다.
[178] 또한，조사광의강도가 3.33 J/cm2이상인경우，접착력테스트시금속박막이 기판으로부터떨어져나와，매우낮은접착력을가짐을확인하였다.도 2는 2.17J/cm2로광이조사된샘플의접착력테스트결과를보여주는광학사진으로, 도 2와유사하게, 2.57 J/cm2이하로광이조사된샘플의경우,접착력테스트시 금속박막이기판으로부터떨어져나오지않는것을확인하였다.
[179] 1.24내지 2.57 J/cm2사이로광이조사되어제조된금속박막을
주사전자현미경으로관찰한결과，금속입자들이서로계면을이루며
안정적으로접촉하여，고분자바인더가잔류하는상태에서도효과적인 치밀화가이루어진것을알수있다.
[180] 실시예 1에서제조된금속박막을 X선광전자분광법 (XPS;X-ray photoelectron spectroscopy)으로분석하여，조사되는광의강도별금속박막에잔류하는 고분자바인더의함량을측정한결과,광을조사하지않고단순건조된샘플의 경우약 0.08중량 % (금속및고분자를전체로한증량 %)의고분자를
함유하였으며， 1.24~2.57J/cm2로광이조사되어제조된금속박막의경우,광 조사조건과거의무관하게약 0.05증량 «¾의고분자를함유하였다.실시예에서 3.33 J/cm2로광이조사되어제조된금속박막의경우，실질적으로고분자 바인더가모두탄화된것을확인하였다.이러한결과를재확인하고자실시예 1과동일하게폴리에틸렌테레프탈레이트기판에도포막을형성하고 4.00 J/cm2 로광을조사하여금속박막을제조하고이를 X선광전자분광법으로분석한 결과,실시예에서 3.33 J/cm2로광이조사되어제조된금속박막의결과와 마찬가지로실질적으로고분자바인더가모두탄화된것을확인하였다.이를 통해,관계식 1-1을만족하는조건으로광소결을수행하는경우， 6.7내지 Π.ΟμΩαη의매우낮은비저항을갖는금속박막이제조됨과동시에,광조사전 건조된도포막에함유된고분자바인더의 60중량 %이상이광조사후에도 금속박막내에잔류하여，기판과의결착력이놀랍도록향상된금속박막이 제조됨을알수있다.
[181] 도 3은 1.90J/cm2로광이조사되어제조된금속박막을대상으로，만번의굽힘 시험과정및굽힘시험후금속박막의전기전도도가유지됨을단적으로 보여주는사진으로，만번의굽힘시험후에도금속박막을통해안정적인전류가 홀러전구가발광하는것을관찰한것이다.만번의굽함시험후，비저항을 측정하고，굽힘시험전의제조직후비저항을기준으로비저항증가율 ([굽힘 시험후비저항 -굽힘시험전비저항 ]/굽힘시험전비저항 *100(%))이 60% 이하임을확인하였다.또한，기판과금속박막간의접착력테스트를수행한 결과,여전히기판과금속박막이강하게결합된상태를유지하여금속박막이 테이프에의해박리되지않음을확인하였다. 1.90J/cm2로광이조사되어제조된 금속박막의결과와유사하게， 1.24내지 2.57 J/cm2의범위로광이조사되어 제조된샘플모두，만번의굽힘시험에도모두안정적인전구의발광을관찰할 수있었으며，비저항증가율이 60%이하였으며,접착력테스트시제조직후와 같이테이프에의해박리되지않음을확인하였다.
[182] (실시예 2)
[183] 실시예 1과동일하게수행하되，기판을폴리에틸렌테레프탈레이트기판대신 폴리이미드기판이나종이기판을사용하여금속박막을제조하였다.
[184] 실시예 2에서제조된샘플들의비저항，접착력테스트및굽힘테스트를시험한 결과，기판과무관하게,실시예 1에서제조된샘플들과동일내지유사한결과를 얻을수있었다.도 4는종이를기판으로사용하여제조된샘플의광학사진이다.
[185] (실시예 3)
[186] 제조예 2에서제조된구리나노입자를이용하여，실시예 1에서제시된바와 동일하게전도성잉크조성물을제조하였다.준비된전도성잉크조성물을 캐스팅법을이용하여폴리이미드플라스틱기판상에두께가 3 가되도록 도포하였다.건조된도포막에실시예 1과동일한광원을이용하여, 2.5J/cm2의 강도로 1.5msec간연속적으로광조사하여광소결을수행하였다.광소결에의해 9.0μΩ.(;πι의비저항을갖는금속박막이제조됨을확인하였으며，실시예 1에서， 1.24내지 2.57 J/cm2사이로광이조사되어광소결된금속박막과유사한굽힘 테스트결과및접착력테스트결과를얻었다.
[187] (실시예 4)
[188] 제조예 1에서 2분의체류시간으로제조된구리나노입자 25g,비수계용매인 물질를루엔 7g및고분자바인더인물질로 BYK 130 0.2g을흔합하고 3롤밀링을 통해균일한분산상을가지는전도성페이스트조성물을제조하였다.제조된 페이스트를바코팅을이용하여폴리이미드기판상에도포하고건조하였다.
[189] 실시예 1과유사하게 370-800 nm파장대역을가지는광원을이용하여， 2.5J/cm2 의강도및 1.5msec의조건또는 3.0J/cm2의강도및 1.5msec의조건으로광을 조사하여전도성금속박막 (두께 = 5 μηι)을제조하였다.제조된금속박막의 두께는 5 μηι였으며， 2.5J/cm2의강도및 1.5msec의조건의광소결시금속박막의 비저항은 650μΩαη이었고，접착력테스트시금속박막이박리되지않음을 확인하였다.그러나,광조사강도가 3.0J/cm2인경우기판과금속박막간의 접착력테스트시금속박막이탈리되었다.
[190] (실시예 5)
[191] 제조예 1에서 2분의체류시간으로제조된구리나노입자 25g,비수계용매인 물질를루엔 7g,다중벽탄소나노튜브 (Applied Carbon Nano Technology,종횡비： - 1000) lg및고분자바인더인물질로 BYK 130 0.2g을흔합하고 3를밀링을통해 균일한분산상을가지는전도성페이스트조성물을제조하였다.제조된 페이스트를바코팅을이용하여폴리이미드기판상에도포하고건조하였다.
[192] 제조된도포막에， 2.5J/cm2의강도및 1.5msec의조건, 3.0J/cm2의강도및
1.5msec의조건또는 3.0J/cm2의강도및 1.0msec의조건으로광을조사하여， ΙΟμπι두께의금속박막을제조하였다. 2.5J/cm2의강도및 1.5msec의조건의 광소결시비저항이 9.38μΩαη인금속박막이제조됨을확인하였고금속박막과 기판과의접착력테스트시금속박막이탈리되지않음을확인하였다.그러나, 광조사강도가 3.0J/cm2인경우조사시간과무관하게기판과금속박막간의 접착력테스트시금속박막이탈리되었다.
[193]
[194] (실시예 6)
[195] 제조예 1에서 2분의체류시간으로제조된구리나노입자 20g,비수계용매인 물질톨루엔 80g,다층탄소나노류브 (Applied Carbon Nano Technology,종횡비： ~ 1000) lg및고분자바인더인물질로 BYK 130 0.2g을흔합하고 3롤밀링을통해 균일한분산상을가지는전도성페이스트조성물을제조하였다.제조된 페이스트를바코팅을이용하여폴리이미드기판상에도포하고건조하였다.
[196] 제조된도포막에， 2.5J/cm2의강도및 1.5msec의조건， 3.0J/cm2의강도및
1.5msec또는 3.0J/cm2의강도및 1.0msec의조건으로광을조사하였다.제조된 금속박막의두께는 30μηι였으며,면적은 25 cm2이었다.
[197] 2.5J/cm2의강도및 1.5msec의조건의광소결시비저항이 ΙΟ.ΙμΩα 인
금속박막이제조됨을확인하였다.또한제조된금속박막의서로다른표면영역 다섯곳에서표면저항을측정한결과그표면저항의편차가 5%이하로，매우 균일한전기적특성을갖는금속박막이제조됨을확인하였고，금속박막과 기판과의접착력테스트시금속박막이탈리되지않음을확인하였다.이때， 광조사강도가 3.0J/cm2인경우조사시간과무관하게기판과금속박막간의 접착력테스트시금속박막이탈리되었다.
[198] 실시예 6에서， 2.5J/cm2로광이조사되어제조된금속박막의단면을
주사전자현미경으로관찰한결과， 30μιη두께를가지는매우두꺼운후막의금속 박막일지라도,금속박막의단면중표면영역，증심영역및기판과인접한하부 영역에서모두광소결이전체적으로균일하게잘이루어진것을확인할수 있었다.
[199] 이상과같이본발명에서는특정된사항들과한정된실시예및도면에의해 설명되었으나이는본발명의보다전반적인이해를돕기위해서제공된것일 뿐,본발명은상기의실시예에한정되는것은아니며，본발명이속하는 분야에서통상의지식을가진자라면이러한기재로부터다양한수정및변형이 가능하다.
[200] 따라서，본발명의사상은설명된실시예에국한되어정해져서는아니되며， 후술하는특허청구범위뿐아니라이특허청구범위와균둥하거나등가적변형이 있는모츤것들은본발명사상의범주에속한다고할것이다.

Claims

청구범위
[청구항 1] a)금속코어가유기산을포함하는캡핑층으로캡핑된
금속나노입자,비수계유기바인더및비수계용매를함유하는 전도성잉크조성물을제조하는단계;
b)상기전도성잉크조성물을절연성기판에도포하여도포막을 형성하는단계；및
c)상기도포막에하기관계식 1올만족하도록광을조사하여 전도성금속박막을제조하는단계;
를포함하는광소결전도성금속박막의제조방법.
(관계식 1)
Figure imgf000028_0001
(관계식 1에서 1^은도포막에조사되는광의강도 (intensity)이며, Ic 는전도성금속박막에비수계유기바인더가잔류하는강도의 최대강도이다)
[청구항 2] 제 1항에있어서,
c)단계에서，하기관계식 1-1을만족하도록광이조사되는광소결 전도성금속박막의제조방법.
(관계식 1-1)
ILS≤2.6(J/cm2)
(관계식 1-1에서 1 의정의는관계식 1과동일하다)
[청구항 3] 제 2항에있어서,
상기금속나노입자의평균직경은 20내지 300nm인광소결 전도성금속박막의제조방법.
[청구항 4] 제 2항에있어서，
c)단계에서 200내지 800nm의파장대역을포함하는광이 연속적으로조사되는광소결전도성금속박막의제조방법 .
[청구항 5] 제 4항에있어서，
c)단계에서 1내지 2msec동안광이연속적으로조사되는광소결 전도성금속박막의제조방법.
[청구항 6] 제 1항에있어서，
상기비수계유기바인더는폴리불화비닐리덴 (PVDF),
폴리메틸메타크릴레이트 (PMMA)，자기가교성아크릴수지 에멀전，하이드록시에틸셀를로오스，
에틸하이드록시에틸샐를로오스，카르복시메틸셀를로스， 하이드록시셀를로오스,메틸셀를로오스，니트로샐를로오스, 에틸샐를로오스，스티렌부타디엔고무 (SBR),
C1-C10알킬 (메타)아크릴레이트와불포화카르복실산의 공중합체,젤라틴 (gelatine),틴소톤 (Thixoton),스타치 (starch), 폴리스티렌，폴리우레탄,카르복실기를포함하는수지，페놀성 수지 ,에틸셀를로오스와페놀성수지의흔합물，에스터중합체， 메타크릴레이트중합체，자기가교성의 (메타)아크릴산공증합체, 에틸렌성불포화기를갖는공중합체，에틸샐를로스계，
아크릴레이트계，에폭시수지계및이들흔합물중에서하나또는 둘이상선택되는광소결전도성금속박막의제조방법.
제 6항에있어서，
상기전도성잉크조성물은금속나노입자 100중량부를기준으로， 0.05내지 5중량부의비수계유기바인더및 20내지 800중량부의 비수계용매를함유하는광소결전도성금속박막의제조방법. 제 1항에있어서，
상기전도성잉크조성물은전도성나노와이어，전도성나노튜브 및전도성나노로드에서하나또는둘이상선택되는
나노구조체를더함유하는광소결전도성금속박막의제조방법. 제 8항에있어서，
상기나노구조체의열전도도는 50 W/mK이상인광소결전도성 금속박막의제조방법.
제 8항에있어서,
상기나노구조체의종횡비 (aspect ratio)는 10내지 10000인광소결 전도성금속박막의제조방법.
제 8항에있어서,
상기나노구초체는단일벽 (Single-walled)탄소나노튜브， 이중벽 (Double walled)탄소나노튜브,얇은다중벽 (Thin
multi-walled)탄소나노류브및다중벽 (Multi-walled)
탄소나노류브에서하나또는둘이상선택되는광소결전도성 금속박막의제조방법.
제 8항에있어서,
상기전도성잉크조성물은금속나노입자 100중량부를기준으로， 1내지 10중량부의나노구조체를함유하는광소결전도성 금속박막의제조방법.
제 1항내지제 12항중어느한항의제조방법으로제조된전도성 금속박막.
기재상금속나노입자를포함하는전도체가서로입계를이루며 연결되어연속체를이루는금속막;및상기금속나노입자와 흔재하며상기금속막과상기기재를결착시키는유기바인더；를 포함하는금속배선.
제 14항에있어서， 상기금속배선은금속코어가유기산을포함하는캡핑층으로 캡핑된금속나노입자및고분자바인더를함유하는잉크의 광소결에의해제조되며,상기유기바인더는상기잉크에함유된 고분자바인더인금속배선.
[청구항 16] 제 15항에있어서，
상기금속배선은금속나노입자 100중량부기준， 0.05내지 0.1 중량부의유기바인더를함유하는금속배선.
[청구항 17] 제 14항에있어서，
-. 상기전도체는전도성나노와이어,전도성나노튜브및전도성 나노로드에서하나또는둘이상선택되는나노구조체를더 포함하는금속배선.
[청구항 18] 제 17항에있어서,
상기금속배선은금속나노입자 100중량부기준, 1내지 10 증량부의나노구조체를포함하는금속배선.
[청구항 19] 제 17항에있어서，
상기나노구조체는단일벽 (Single-walled)탄소나노튜브， 이증벽 (Double walled)탄소나노튜브，얇은다증벽 (Thin multi-walled)탄소나노튜브및다증벽 (Multi-walled)
탄소나노튜브에서하나또는둘이상선택되는금속배선.
PCT/KR2015/007440 2014-07-18 2015-07-17 광소결을 이용한 전도성 금속박막의 제조방법 WO2016010393A1 (ko)

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Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN107312388A (zh) * 2017-07-05 2017-11-03 邹晓虎 基于环氧树脂和聚甲基丙烯酸甲酯的导电油墨组合物
CN111344813A (zh) * 2017-11-13 2020-06-26 日东电工株式会社 烧结接合用组合物、烧结接合用片、及带烧结接合用片的切割带
CN111627698A (zh) * 2020-06-08 2020-09-04 江苏国瓷泓源光电科技有限公司 一种mlcc用镍内电极浆料

Families Citing this family (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR102181570B1 (ko) * 2016-06-02 2020-11-20 한국전기연구원 내구성이 향상된 금속/이차원 나노소재/폴리머 하이브리드 전도막 및 그 제조방법
KR101893470B1 (ko) * 2017-08-22 2018-08-30 한국화학연구원 3차원 프린팅을 위한 전극형성용 페이스트 조성물 및 이를 이용한 전극
KR102088100B1 (ko) * 2018-05-02 2020-03-11 한양대학교 산학협력단 광소결 나노잉크, 광소결 방법 그리고 전도성 나노 구조체
WO2019212218A1 (ko) * 2018-05-02 2019-11-07 한양대학교 산학협력단 광소결 나노잉크, 광소결 방법 그리고 전도성 나노 구조체
KR102171531B1 (ko) * 2019-02-18 2020-10-29 (주)디엔에프 전도성 박막의 제조방법

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2006070300A (ja) * 2004-08-31 2006-03-16 Mitsubishi Materials Corp 金属微粒子含有組成物、およびその用途
JP2013206722A (ja) * 2012-03-28 2013-10-07 Fujifilm Corp 液状組成物、金属銅膜、及び導体配線、並びに金属銅膜の製造方法
KR20130111180A (ko) * 2012-03-30 2013-10-10 한국화학연구원 표면 산화막 형성이 제어된 금속 나노 입자 합성 방법 및 용액 공정을 통한 금속 전도성 박막의 제조방법
JP2014011412A (ja) * 2012-07-03 2014-01-20 Ishihara Chemical Co Ltd 導電膜形成方法及び焼結進行剤
KR20140028208A (ko) * 2012-08-27 2014-03-10 한국과학기술연구원 전도성 이온 잉크 조성물, 그 제조방법 및 이를 이용한 고전도성 패턴 또는 막의 형성방법

Family Cites Families (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US10231344B2 (en) * 2007-05-18 2019-03-12 Applied Nanotech Holdings, Inc. Metallic ink

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2006070300A (ja) * 2004-08-31 2006-03-16 Mitsubishi Materials Corp 金属微粒子含有組成物、およびその用途
JP2013206722A (ja) * 2012-03-28 2013-10-07 Fujifilm Corp 液状組成物、金属銅膜、及び導体配線、並びに金属銅膜の製造方法
KR20130111180A (ko) * 2012-03-30 2013-10-10 한국화학연구원 표면 산화막 형성이 제어된 금속 나노 입자 합성 방법 및 용액 공정을 통한 금속 전도성 박막의 제조방법
JP2014011412A (ja) * 2012-07-03 2014-01-20 Ishihara Chemical Co Ltd 導電膜形成方法及び焼結進行剤
KR20140028208A (ko) * 2012-08-27 2014-03-10 한국과학기술연구원 전도성 이온 잉크 조성물, 그 제조방법 및 이를 이용한 고전도성 패턴 또는 막의 형성방법

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN107312388A (zh) * 2017-07-05 2017-11-03 邹晓虎 基于环氧树脂和聚甲基丙烯酸甲酯的导电油墨组合物
CN111344813A (zh) * 2017-11-13 2020-06-26 日东电工株式会社 烧结接合用组合物、烧结接合用片、及带烧结接合用片的切割带
CN111627698A (zh) * 2020-06-08 2020-09-04 江苏国瓷泓源光电科技有限公司 一种mlcc用镍内电极浆料

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