TW201242761A - Laminated body for solder joint and jointed body - Google Patents

Abstract

This laminated body for solder joint includes in series: a sintered body layer of metal nanoparticles; a barrier containing metal particles or metal oxide particles; and a solder joint layer. This jointed body includes in series: a first jointed object; the above-described laminated body for solder joint; and a second jointed object.

Description

201242761 VI. Description of the Invention: [Technical Field of the Invention] The present invention relates to a welding combined laminate and a welded laminate-bonded body. This welding combined laminate and joined body are particularly suitable for a light source or a solar cell such as a led light source. [Prior Art] In recent years, LED light sources have been used in various fields in accordance with high brightness. In particular, since a white LED light source can be realized, the LED light source is used for a backlight of a lighting fixture or a liquid crystal display. In order to further increase the brightness and the like of the LED light source, it is reviewed to utilize the light emission from the LED element more efficiently. For example, there is disclosed an LED light source having a titanium thin film on an Ag-plated electrode film, comprising: a (support) substrate, an LED element mounted on the substrate, and a sealant containing a fluorescent agent, between the substrate and the LED element An Ag-plated electrode film that reflects the light emission of the LED element (Patent Document 1). In the LED light source, a conductive reflective film layer containing an Ag-plated electrode film is provided between the substrate and the LED element to efficiently reflect light from the illuminant to increase the luminescence intensity. Here, the Ag thin film (Ag plating electrode film) and the titanium thin film are formed by a vacuum film forming method such as a plating method or a sputtering method. Generally, in the plating method, complicated steps and waste liquid are expected to occur. In the vacuum film forming method, a large cost is required in order to maintain and operate a large vacuum film forming apparatus. In the above-mentioned LED light source, since only the Ag scraping -5-201242761 electrode film may undergo thermal degradation or photodegradation, a titanium film is required, and a plating method and a vacuum film forming method must be used. The structure in which the substrate and the LED element are bonded to each other is generally bonded by using a metal paste or solder, and the heat dissipation property obtained by using an Au-Sn alloy solder or the like (Patent Document 2). In the method of Document 2, in order to prevent solder leaching of the electrode of the LED element, it is necessary to provide a plurality of barrier layers such as Ni and Ti by a plating method or a vacuum film forming method, which requires a large film forming cost. Disadvantages. Further, it is also required to prevent the barrier layer for solder etching from using lead-free solder other than Au-Sn alloy solder. Further, in the back surface of the LED element, a conventional sputtering method or a vacuum film formation method is used, and a reflection film having a reflection-increasing structure including a transparent film of a plurality of layers is provided, and a metal bonding structure having high heat dissipation characteristics is provided. . At this time, there is a problem that it is difficult to improve the adhesion due to poor bonding between the transparent film and the metal film of the metal bonded structure. [PRIOR ART DOCUMENT] [Patent Document 1] JP-A-2009-231568 (Patent Document 2) JP-A-2002-001A [Problem] The object of the present invention is to provide a welding-use laminate which can be manufactured by a simple process, which can greatly improve the cost of lining from 6 to 201242761, and a laminate for welding, which can be used for high reliability of LED elements and the like. In the above-described welding-use laminate, it is possible to use a metal paste containing a metal particle as a main component instead of a high-priced Ni barrier layer formed by a conventional shovel method or a film formation method. The manufacturing steps are simple and the lining costs are greatly improved. This welding-use laminate can also be used in a joint body for other uses, and is often suitable for a joint body used in a solar battery using a reflective film. [Means for Solving the Problems] The aspect of the present invention relates to a welding-use laminate and a joined body which can solve the problems by the configuration shown below. (1) A welding-use laminate comprising a sintered body layer of a nanoparticle in sequence, containing a metal particle or a metal oxide grain barrier layer, and a welded layer. (2) The welding-use laminate according to the above aspect, wherein the barrier layer is provided on the Γ-main surface side of the sintered body layer of the precursor nanoparticle, and the other main surface side of the sintered layer of the metal nanoparticle is further provided. (3) The welding-use laminate according to the above (2), wherein the layer contains at least one of a polymer-type binder or a non-polymer type agent which is cured by heating. (4) The welding combined lamination according to any one of the above aspects, wherein the metal nanoparticle sintered body layer and the barrier layer are bonded to each other. Vacuum and solution can be entered, especially the above: gold deposits mentioned above, transparent bonding, and 201242761 has a layer of adhesive. (5) The solder-bonding laminate according to the above (4), wherein the binder layer contains at least one of a polymer binder or a non-polymer binder which is cured by heating. (6) The welded composite laminate according to any one of the above aspects, wherein the sintered metal nanoparticle sintered body layer contains 75 mass% or more of silver, and contains gold, copper, tin, and zinc. At least one of the group consisting of molybdenum and manganese. (7) The welding combined laminate according to any one of the above aspects, wherein the sintered metal nanoparticle sintered body layer contains a binder. The welding combined laminate according to any one of the above aspects, wherein the thickness of the sintered body layer of the metal nanoparticles is 0.01 to 0.5 μηι ^ (9) as in the above (1) to (8) The solder-use laminate according to any one of the preceding claims, wherein the film is formed by a wet coating method, and then each layer is formed by firing at 130 to 250 °C. (10) The welding-use laminate according to the above (9), wherein the wet coating method is a spray coating method, a dispenser coating method, a spin coating method, a knife coating method, a slit coating method, or an inkjet coating method. Any of a method, a screen printing method, a lithography method, or a die coating method. (Π)—The bonded body ′ is characterized by the first joined body, the welding combined laminate of the above (1) to (10), and the second joined body. (12) The bonded body according to the above (11), wherein the first bonded system is capable of emitting light or photoelectrically convertible, and the sintered metal laminate sintered body layer is reflective from the first bonded body. Body -8 - 201242761 Light, the second bonded system substrate. (13) The joined body according to the above (12), wherein the element capable of emitting light in the first bonded system is used as a light source. (14) The joined body according to the above (I2), wherein the element that can be photoelectrically converted by the first bonded system is used as a solar cell. [Effects of the Invention] According to the aspect described in the above (1), high joint reliability due to solder (welded layer) can be obtained. Further, since the number of film formation layers is small, an expensive film formation apparatus is not required, and a large cost can be achieved. Further, in the aspect described in the above (2), the refractive index of the transparent layer can be arbitrarily set in comparison with the plating method or the vacuum film forming method because the degree of freedom of the material which can be used for the transparent layer is high. Thereby, the effect of enhancing the reflection by the sintered body layer of the metal nanoparticles can be controlled. According to the aspect described in the above (11), the bonded body having high joint reliability due to the solder can be easily provided. Further, according to the aspect described in the above (13), it is possible to provide a light-emitting source having high utilization efficiency of light emitted from the LED element. According to the aspect described in the above (1), a solar cell having high photoelectric conversion efficiency can be provided. [Embodiment] [Embodiment of the Invention] Hereinafter, the present invention will be specifically described based on an embodiment. However, the % of the unit indicating the content is % by mass unless otherwise indicated.

S-9-201242761 [Welding laminated layer] The welding combined lamination system of the present embodiment includes a sintered layer of a metal nanoparticle, a barrier layer containing metal particles or metal oxide particles, and a welded layer in this order. Hereinafter, the description will be given in the order of the sintered body layer of the metal nanoparticles, the barrier layer, and the welded layer. <<Metal Nanoparticle Sintered Body Layer>> The metal nanoparticle sintered body layer imparts conductivity, reflectivity, and adhesion to the welded joint layer. The sintered metal layer of the metal nanoparticles can be formed by the following method. The metal nanoparticle sintered body layer is formed into a film by a wet coating method to form a coating film. Then, the coating film is dried, followed by baking. From the above, a sintered body layer of a metal nanoparticle can be formed. From the viewpoint of conductivity and reflectivity, the sintered body layer of the metal nanoparticle contains 75% by mass or more of silver, and contains a metal selected from the group consisting of gold, platinum 'palladium, rhodium, nickel, copper, tin, indium, zinc, iron, and chromium. At least one of the group consisting of molybdenum and manganese. More preferably, it contains at least one selected from the group consisting of gold, copper, tin, zinc, molybdenum and manganese. The thickness of the sintered body layer of the metal nanoparticles is preferably from 0.01 to 0.5 μm from the viewpoint of conductivity. The metal nanoparticle sintered body layer composition contains metal nanoparticles. The metal nanoparticles preferably contain 75% by mass or more, more preferably 80% by mass or more of silver nanoparticles. With respect to the sintered body layer of the metal nanoparticle: 100% by mass, when the content of the silver nanoparticle is less than 75% by mass, the conductivity (reflection of the electrode (metal nanoparticle sintered body layer) formed using the composition) The rate will decrease. Therefore, the content of the silver nanoparticles is preferably 75% by mass or more based on 100% by mass of the layer of the sintered metal nanoparticle sintered body-10-201242761. The metal nanoparticle is preferably chemically modified by a protective agent of an organic molecular main chain having a carbon number of 1 to 3 carbon atoms. In order to form a sintered body layer of a metal nanoparticle, a composition for a sintered body layer of a metal nanoparticle is coated on a substrate to form a coating film, and then, if the coating film is fired, the organic layer in the protective agent for protecting the surface of the metal nanoparticle is protected. The molecular system is detached or decomposed, or detached and decomposed. Therefore, it is easy to obtain an organic material residue which does not substantially adversely affect the conductivity and reflectance of the counter electrode (the metal nanoparticle sintered body layer), and an electrode (metal nanoparticle sintered body layer) mainly composed of a metal. When the carbon number of the carbon skeleton of the organic molecular main chain of the protective agent chemically modified with the metal nanoparticles is 4 or more, the heat system at the time of baking is difficult to detach or decompose the protective agent (separation and combustion) in the metal nano Many organic residues are likely to remain in the sintered body layer of the particles. This organic residual paint adversely affects the electrical conductivity and reflectance of the sintered body layer of the metal nanoparticles. Therefore, it is preferred that the carbon number of the carbon skeleton of the organic molecular main chain of the protective agent chemically modifying the metal nanoparticles is in the range of 1 to 3. Further, the protective agent, i.e., the protective molecule which chemically modifies the surface of the metal nanoparticles, more preferably contains either or both of a hydroxyl group (-OH) or a carbonyl group (-C = 0). When the hydroxyl group (-OH) is contained in a protective agent for chemically modifying metal nanoparticles such as silver nanoparticles, the composition is excellent in dispersion stability, and functions effectively even at low temperature sintering of the coating film. The carbonyl group (-C = 0) is contained in a protective agent for chemically modifying metal nanoparticles such as silver nanoparticles, and the metal nanoparticle sintered body layer composition is excellent in dispersion stability, -11 - 201242761 even in metal In the low-temperature sintering of the sintered body layer of the nanoparticle, it is preferable that the metal nanoparticle is preferably a metal nanoparticle having a primary particle diameter of 10% or more in a range of 10 to 50 nm, more preferably contained. 7 5 % or more. Here, the so-called number average means the amount in the particle size distribution of the number basis. The content of the metal nanoparticles in the range of primary particle diameters from 1 〇 to 50 nm is, in terms of number average, relative to the total of 1% of the metal nanoparticles, when less than 70%, the metal nanoparticles The specific surface area increases, and the proportion of the protective agent becomes large. The organic molecules which are easily separated or decomposed (separated/burned) by the heat at the time of calcination also have a large proportion of organic molecules, and many organic residues remain in the electrodes. Therefore, the organic residue is deteriorated or deteriorated, and the conductivity and reflectance of the electrode are lowered. Further, the particle size distribution of the metal nanoparticles is widened, the density of the electrode is liable to lower, and the conductivity and reflectance of the electrode are lowered. Therefore, the content of the metal nanoparticles in the range of the primary particle diameter of 10 to 5 〇 nm is preferably 70% or more in terms of the number average of 100% of all the metal nanoparticles. Further, when the primary particle diameter of 70% or more of the metal nanoparticles is in the range of 10 to 50 nm, good stability with time (year-old stability) can be obtained. Here, the primary particle diameter was measured by a dynamic light scattering method of LB-55 0 manufactured by Horiba, Ltd. Hereinafter, the average particle diameter is measured in the same manner unless otherwise specified. As described above, the metal nanoparticle contains 75% by mass or more of silver nanoparticles, and more preferably contains gold, platinum, palladium, rhodium, nickel, copper, tin, indium, zinc, iron, chromium, molybdenum and A nanoparticle of one type of nano-12-201242761 particles or a mixture of two or more kinds of nanoparticles, or an alloy composed of two or more elements selected from the group. The content of the nanoparticles of the nanoparticles other than the silver nanoparticles is preferably 0.02% by mass or more and less than 25% by mass, and more preferably 0.03% by mass based on 100% by mass of the total of the metal nanoparticles. 20% by mass. When the content of the nanoparticles other than the silver nanoparticles is less than 0.02% by mass, it is not particularly problematic with respect to 100% by mass of all the metal nanoparticles. When the content of the nanoparticles other than the silver nanoparticles is 〇.〇2% by mass or less and less than 25% by mass, the conductivity and reflectance of the sintered body layer of the metal nanoparticles after the weather resistance test, and the weather resistance test Before the comparison, the effect is not deteriorated. Here, the so-called weather resistance test is a test which is maintained for 1 000 hours in a constant temperature and humidity chamber having a temperature of 10 ° C and a humidity of 50%. When the content of the nanoparticles other than the silver nanoparticles is 25 mass% or more, the electrical conductivity and reflectance of the sintered body layer of the metal nanoparticles immediately after the calcination are lowered. Further, the electrical conductivity and reflectance of the sintered body layer of the metal nanoparticles after the weather resistance test were lower than those before the weather resistance test. In addition, the metal nanoparticle sintered body layer composition may further contain one or more additives selected from the group consisting of metal oxides, metal hydroxides, organometallic compounds, and polyoxygenated oils. When the metal nanoparticle sintered body layer composition contains the above-mentioned one or more kinds of additives, 'the grain growth caused by the sintering between the metal nanoparticles is further suppressed' can be produced to achieve a desired surface shape. The addition ratio of the additive is preferably in the range of 0.1 to 20% by mass, more preferably in the range of 1 to 5% by mass, based on 100% by mass of the composition for the sintered body layer of the metal nanoparticle. 201242761 The metal oxide used as an additive preferably contains a group selected from the group consisting of aluminum, tantalum, titanium, chromium, manganese, iron, cobalt 'nickel, silver, copper 'zinc, molybdenum, tin, indium and antimony. At least one oxide or composite oxide of the group. The composite oxide is specifically an indium tin oxide-based composite oxide (Indium Tin Oxide: ITO), an oxidized chain-tin oxide-based composite oxide (Antimony Tin Oxide: AT^O), or indium oxide-zinc oxide. A composite oxide (Indium Zinc Oxide: IZO) or the like. The metal hydroxide used as the additive preferably contains a group selected from the group consisting of aluminum, tantalum, titanium, chromium, manganese, iron, cobalt, nickel, silver, copper, zinc, molybdenum, tin, indium, and antimony. At least one of the hydroxides. The organometallic compound used as an additive is preferably a metal containing at least one selected from the group consisting of sand, chin, ketone, bell, iron, agar, yttrium, silver, copper, yttrium, yttrium, and tin. Soap, metal complex or metal alkoxide. For example, examples of the metal soap include chromium acetate, manganese formate, iron citrate, cobalt formate, nickel acetate, silver citrate, copper acetate, copper citrate, tin acetate, zinc acetate, zinc oxalate, and molybdenum acetate. The metal complex compound may, for example, be an ethyl acetoacetate zinc complex or an acetonitrile acetone chromium complex, and examples thereof include an ethyl acetonate nickel complex. Examples of the metal alkoxide include titanium isopropoxide, methyl decanoate, isocyanatopropyltrimethoxydecane, and aminopropyltrimethoxydecane. As the polyoxygenated oil to be used as an additive, either or both of a linear polysiloxane oil and a modified polyoxyxylene oil can be used. As the modified polyoxyxene oil, those in which an organic group is introduced into one side chain of the polyoxyalkylene (side-14-201242761 chain type) and an organic group introduced at both ends of the polyoxyalkylene can be used. (both end type), an organic group introduced at either end of both ends of the polyoxyalkylene (one end type), and one of the side chains of the polyoxyalkylene and an organic group introduced at both ends (side chain) Both end types). Among the modified polyoxyxides, there are reactive polyoxygenated oils and non-reactive polyasoxylated oils, which can be used simultaneously. Furthermore, the so-called reactive polyoxyxide oil means an amine-modified polyoxyxide oil, an epoxy-modified polyoxyxene oil, a carboxyl-modified polyoxyxene oil, a carbitol-modified polyoxyxide oil. , fluorenyl modified polyoxyxide oil and heterofunctional functional group modified (epoxy, amine, polyether based) polyoxygenated oil. The so-called non-reactive polyoxo-oxygen oil is a polyether modified polyoxyxide oil, a methylstyryl modified polyoxyxide oil, an alkyl modified polyoxyxene oil, a higher fatty acid ester modified polyfluorene. Oxygen oil, fluorine modified polyoxyxide oil and hydrophilic special modified polyoxyxide oil. The content of the metal nanoparticles in the composition for the sintered body layer of the metal nanoparticles is preferably from 2.5 to 95.0% by mass based on 100% by mass of the dispersion of the metal nanoparticles and the dispersion medium. Preferably, it is 3.5 to 90.0% by mass of the dispersion of the metal nanoparticles and the dispersion medium: when the content of the metal nanoparticles is less than 2.5% by mass, particularly The characteristics of the electrode (the sintered metal nanoparticle sintered body layer) after baking have no effect, but it is difficult to obtain an electrode having a necessary thickness. When the content of the metal nanoparticles is more than 95.0% by mass, the wet flow of the composition for the sintered body layer of the metal nanoparticles is lost, and the necessary fluidity as an ink or a paste is lost. Therefore, the content of the metal nanoparticles is preferably in the range of 2.5 to 95.0% by mass based on the dispersion of the metal nanoparticles and the dispersion medium: 1% by mass. -15-201242761 Further, the dispersion medium constituting the composition for the sintered body layer of the metal nanoparticles contains 1% by mass or more, preferably 2% by mass or more of water and 2% by mass based on 100% by mass of the entire dispersion medium. An alcohol of more than % and preferably more than 3% by mass is suitable. For example, when the dispersion medium is composed only of water and an alcohol, if it contains 2% by mass of water, it contains 98% by mass of an alcohol. When it contains 2 mass % of alcohol, it contains 98 mass % of water. When the content of water is less than 1% by mass based on 1% by mass of the entire dispersion medium, the film obtained by coating the composition by the wet coating method is difficult to be sintered at a low temperature, and after baking The electrical conductivity and reflectance of the sintered body layer of the metal nanoparticles are lowered. Therefore, the content of water is suitably in the range of 1% by mass or more based on 100% by mass of the entire dispersion medium. When the content of the alcohol is less than 2% by mass based on 100% by mass of the entire dispersion medium, the film obtained by coating the composition by the wet coating method in the same manner as described above is difficult to be sintered at a low temperature. Moreover, the electrical conductivity and reflectance of the sintered metal nanoparticle sintered body layer are lowered. Therefore, the content of the alcohol is suitably in the range of 2% by mass or more based on 100% by mass of the entire dispersion medium. The alcohol used as the dispersion medium is preferably selected from the group consisting of methanol, ethanol, propanol, butanol, ethylene glycol, propylene glycol, diethylene glycol 'glycerol' isobornyl hexanol, and erythritol. One or two or more. The addition of the alcohol is carried out in order to improve the wettability with the substrate, and the mixing ratio of water and alcohol can be freely changed in accordance with the type of the substrate. A composition for sintering a metal nanoparticle sintered body layer can be produced by mixing a desired component with a paint shaker, a ball mill, a sand mill, a centrifugal mill 'three rolls, or the like in a usual manner to disperse metal nanoparticles or the like. . Of course, -16-201242761 can also be manufactured by a usual stirring operation. The wet coating method for forming a metal nanoparticle sintered body layer composition film is preferably a spray coating method, a dispenser coating method, a spin coating method, a knife coating method, a slit coating method, or an inkjet coating method. Any of the screen printing method, the lithography method, or the die coating method' is not limited thereto, and all methods can be utilized. In the spray coating method, the metal nanoparticle sintered body layer composition is applied to the substrate by a compressed air by a compressed air, or the dispersion (the metal nanoparticle sintered body layer composition) itself is pressurized into a mist. A method of coating on a substrate. In the dispenser coating method, for example, a composition for sintering a metal nanoparticle sintered body layer is placed in a syringe, and a piston of the syringe is pressed to discharge a dispersion from a fine nozzle at the tip end of the syringe (a composition for a sintered body layer of a metal nanoparticle) , a method of coating on a substrate. In the spin coating method, a composition for sintering a metal nanoparticle sintered body layer is dropped onto a rotating substrate, and the molten metal nanoparticle sintered body layer is diffused to the periphery of the substrate by centrifugal force. The knife coating method is capable of moving a substrate having a predetermined gap with a predetermined gap at the front end of the blade to move in the horizontal direction. On the substrate on the upstream side of the blade, a composition for sintering a layer of the metal nanoparticle is supplied to orient the substrate. The method of horizontal movement on the downstream side. The slit coating method is a method in which a composition for sintering a metal nanoparticle sintered body layer is applied from a slit and applied to a substrate. The inkjet coating method is a method in which a composition for sintering a metal nanoparticle sintered body layer is filled in an ink cartridge of a commercially available ink jet printer, and inkjet printing is performed on a substrate. The screen printing method uses a yarn as a pattern indicating material, and a method of transferring a composition for sintering a metal nanoparticle sintered body layer to a substrate by using a plate image produced thereon. The lithographic printing method is such that the composition for sintering the metal nanoparticle sintered body layer attached to the plate is not directly attached to the substrate, but is transferred from the plate to the rubber sheet and then transferred from the rubber sheet to the substrate. The printing method utilizes the water repellency of the composition for sintering the body layer of the metal nanoparticle. The die coating method is a method in which a sintered body layer of a metal nanoparticle supplied to a die is distributed by a manifold, and is extruded onto a film by a slit, and is applied onto a surface of a traveling substrate. . Among the die coating methods, there are a slit coating method or a slide coating method 'curtain coating method. The drying temperature of the coating film of the composition for forming a metal nanoparticle sintered body layer to be formed is a temperature which does not affect the LED element or the like of the bonded body, and is preferably 60 ° C or less. The baking temperature of the dried coating film is preferably in the range of 130 to 250 °C. If it is less than 130 °C, a problem of insufficient hardening occurs in the sintered layer of the metal nanoparticles. Further, if it exceeds 250 °C, the production advantage of the low-temperature process does not occur. That is, the manufacturing cost increases and the productivity is lowered. Further, the LED element as a candidate for the bonded body, the amorphous germanium, the microcrystalline germanium, or the hybrid solar cell using the same is weak under heat, and the conversion efficiency is lowered by the baking step. The baking time of the coating film is preferably in the range of 5 to 60 minutes. When the calcination time is less than 5 minutes of the lower limit 値, a problem of insufficient baking is caused in the sintered layer of the metal nanoparticles. When the baking time exceeds the upper limit of 〇6 minutes, the manufacturing cost is increased and the productivity is lowered. In addition, the luminous efficiency of the LED element or the conversion efficiency of the solar cell unit is lowered. "Baffle Layer" -18- 201242761 The barrier layer suppresses the solder leach of the sintered layer of the metal nanoparticles when the weld layer is formed or aged. This barrier layer can be formed by the following method. A coating film is formed by forming a film for a barrier layer by a wet coating method. Then, the coating film is dried, followed by baking. With the above, a barrier layer can be formed. Further, the barrier layer may be formed by a vacuum film formation method such as a plating method or a sputtering method. The thickness of the barrier layer is preferably from 0.1 to 10 μm from the viewpoint of solder erosion prevention and adhesion of the sintered body layer of the metal nanoparticles. As the composition for the barrier layer, any one or both of the composition for a barrier layer based on the metal nanoparticles and the composition for the barrier layer based on the metal compound can be used. Hereinafter, the composition for the barrier layer based on the (N) metal nanoparticles and the composition for the barrier layer based on the (metal) metal compound will be described. (Α) Metal nanoparticle-based barrier layer composition (Α) Metal nanoparticle-based barrier layer composition contains metal nanoparticles. Examples of the metal contained in the metal nanoparticles include metals of Group 8 of the periodic table such as iron, nickel, cobalt, rhodium, ruthenium, palladium rhodium, and platinum; and the fourth group of the periodic table of titanium, pin, and the like. Metal: Group 5 metal of the periodic table such as vanadium, niobium, molybdenum, etc.; metal of the 6th group of the periodic table of chromium, molybdenum, tungsten, etc.: metal of the seventh group of the periodic table of manganese, etc.; periodic table of copper, silver, gold, etc. 1 lanthanum metal; zinc, cadmium, etc. periodic table 2 lanthanum metal; aluminum, gallium, indium, etc. periodic table 3 lanthanum metal: lanthanum, tin, lead, etc. periodic table 4 Β group metal; 锑 '铋 cycle Table 5 metal and the like. The metal nanoparticles of the metal -19-201242761 may be any of the metal nanoparticles formed by the metal nanoparticles or the alloy of two or more of the metals. Among these metals or alloys, it can be appropriately selected depending on the material of the solder or the like. For example, for the Au-Sn solder, nickel, silver, gold, titanium, or the like is preferable. The metal nanoparticle system may be used alone or in combination of two or more. The metal nanoparticle has a particle size of a nanometer size. For example, the average particle diameter (average primary particle diameter) of the metal nanoparticles is preferably from 1 to 10 nm, more preferably from 1.5 to 80 nm, still more preferably from 2 to 70 nm, particularly preferably from 3 to 50 nm, usually 1 ~40nm (for example, 2~30nm) or so. The metal nanoparticle is preferably coated with a protective colloid. Thereby, the dispersibility at room temperature and the storage stability are improved. As the protective colloid, an organic compound or a polymer dispersant can be given. The organic compound used as the protective colloid is preferably an organic compound having 1 to 3 carboxyl groups, more preferably a carboxylic acid such as a monocarboxylic acid, a polycarboxylic acid or a hydroxycarboxylic acid. The polymer dispersant used as the protective colloid includes a resin (or a water-soluble resin or a water-dispersible resin) containing a hydrophilic unit (or a hydrophilic block) composed of a hydrophilic monomer. The hydrophilic monomer may, for example, be an addition polymerization monomer such as a carboxyl group or an acid anhydride group-containing monomer or a hydroxyl group-containing monomer; or a condensation monomer such as an alkylene oxide. Examples of the monomer having a carboxyl group or an acid anhydride group include a (meth)acrylic acid monomer such as acrylic acid or methacrylic acid, an unsaturated polycarboxylic acid such as maleic acid, and maleic anhydride. The hydroxyl group-containing monomer may, for example, be a hydroxyalkyl (meth)acrylate such as 2-hydroxyethyl (meth)acrylate or a vinyl phenol. As the alkylene oxide, -20-201242761 may be exemplified by ethylene oxide or the like. When the composition for a barrier layer of the metal nanoparticle-based composition contains a dispersion medium, it can be easily applied by a wet coating method. The dispersion medium is not particularly limited as long as it is a solvent which can produce a sufficient viscosity by a combination with a metal nanoparticle or a protective colloid. A general-purpose solvent can be used. Examples of the solvent include water and alcohol. The ratio of the dispersion medium can be appropriately selected in accordance with the ease of coating by a wet coating method or the like. The ratio of the metal nanoparticle to the entire solid content in the composition for the barrier layer of the metal nanoparticle based on the ease of coating by the wet coating method, the sintered density of the metal nanoparticle, etc. Come to choose. As an example, the ratio of the metal nanoparticle to the solid content of the composition for the barrier layer based on the metal nanoparticle is preferably 70 to 99% by mass, more preferably 85 to 99% by mass. Good for 90 to 99% by mass. The proportion of the protective colloid can be appropriately selected in accordance with the dispersibility of the metal nanoparticles or the like. For example, the ratio of the protective colloid is preferably from 0.5 to 20 parts by mass, more preferably from 1 to 15 parts by mass, per 100 parts by mass of the metal nanoparticles. The ratio of the organic compound to the polymer dispersant can be appropriately selected depending on the dispersibility of the metal nanoparticles or the like. Metal nanoparticle or the like produced by a well-known method is dispersed in the same manner as in the method for producing a composition for sintering a metal nanoparticle sintered body layer, and a composition for a barrier layer based on a metal nanoparticle can be produced. (B) Metal compound-based barrier layer composition -21 - 201242761 The metal compound-based barrier layer composition contains a metal compound. The metal compound 'is a metal oxide, a metal hydroxide, a metal sulfide, a metal carbide, a metal nitride, a metal boride or the like. The metal constituting the metal compound is the same as the metal of the metal nanoparticle in the composition for the barrier layer constituting the metal nanoparticle base of the above (A). These metal compounds may be used alone or in combination of two or more. The metal constituting the metal compound is preferably a metal (metal monomer and metal alloy) containing at least a noble metal such as silver (particularly a metal of Group 1B of the periodic table), and more preferably a noble metal monomer (e.g., a silver monomer or the like). Hereinafter, the case of the silver compound will be described. Examples of the silver compound include silver oxide, silver oxide, silver carbonate, silver acetate, and silver acetylacetate complex. These silver compounds may be used alone or in combination of two or more. As the silver compound, a commercially available one can be used. The average particle diameter of the silver compound is preferably from 0.01 to Ιμηη, more preferably from 0.01 to 0.5 μm, and may be appropriately selected depending on the reduction reaction conditions, heating temperature and the like. The composition for a barrier layer based on a metal compound contains a dispersion medium. As the dispersion medium, water, an alcohol such as methanol, ethanol or propanol: an organic solvent such as isophorone, terpineol, triethylene glycol monobutyl ether or butyl cellosolve acetate can be used. The ratio of the dispersion medium can be appropriately selected in accordance with the easiness of coating by a wet coating method or the like. In order to disperse the silver compound well in the dispersion medium, it is preferred to add a dispersant. Examples of the dispersant include hydroxypropylcellulose, polyvinylpyrrolidone, and polyvinyl alcohol. The content of the dispersant is generally 0 to 300 parts by mass relative to the silver compound -22-201242761: 100 parts by mass. In order to improve the easiness of coating by the wet coating method, the composition for a barrier layer of a metal compound may further contain a binder resin. Examples of the binder resin include a acryl oleic acid resin, an ethyl styrene resin, a polyester resin, a polyurethane resin, a phenol resin, an epoxy resin, and the like. Further, the composition for the barrier layer of the metal compound may also contain a reducing agent capable of reducing the metal compound. Examples of the reducing agent include ethylene glycol, formalin, hydrazine, ascorbic acid, and various alcohols. In the same manner as in the production method of the composition for the sintered body layer of the metal nanoparticles, a commercially available metal compound or the like can be dispersed to produce a composition for a barrier layer based on a metal compound. (Method for Producing a Barrier Layer) A method for forming a film by using a composition for a barrier layer of a (N) metal nanoparticle base or a barrier layer for a (metal) compound based on a wet coating method to form a coating film The method of drying the coating film and the method of baking are the same as the method of producing the sintered body layer of the metal nanoparticle. "Welding the layer" The solder layer is preferably formed by melting a solder paste. This allows precise control of thickness. Further, when the solder joint layer is composed of a solder paste, the solder joint layer of the solder joint laminate is melted, and the solder joint laminate is bonded to the joint body ′ to form a joint body. Thus, by melting the solder paste, the bonded body can be formed, so that the process can be simplified.

S -23- 201242761 The solder paste includes Au-Sn alloy solder, tin-based lead-free solder, etc., and Au-Sn solder which is excellent in heat dissipation characteristics is preferable.

The Au-Sn alloy solder preferably contains Sn: 15 to 25% by mass, more preferably a composition having a eutectic composition of Sn of approximately 20% by mass (Sn: 17 to 23% by mass). When the weld layer is formed by melting the Au-Sn alloy solder paste, the flux is contained in the Au-Sn alloy solder powder having the above composition. The fluxing agent is commercially available and generally contains rosin, an active agent, a solvent and a tackifier in the flux. As a commercially available flux, an RMA type rosin-based flux can be mentioned. The melting temperature of the Au-Sn alloy solder is preferably 270 to 400 ° C, more preferably 300 to 350 ° C. "Welding laminated body" The welding combined laminate is described in more detail. Fig. 1 shows a model diagram of a cross section of a welding combined laminate 1. As is apparent from Fig. 1, the welding combined laminate 1 includes the metal nanoparticle sintered body layer 11, the barrier layer 12, and the welded layer 13 in this order. In FIG. 1, a barrier layer 12 that is in contact with a main surface is provided on one main surface side of the sintered metal oxide layer 1 1 , and a welded layer that is in contact with a main surface is provided on one main surface side of the barrier layer 12 1 3. It is preferable that the welding-use laminate further has a transparent layer on the other main surface side of the sintered metal oxide layer (the main surface side not in contact with the barrier layer). Thereby, the antireflection effect by the sintered body layer of the metal nanoparticle can be controlled. The thickness of the transparent layer is preferably from 0.01 to 0.5 μm - 24 to 201242761 from the viewpoint of improvement in reflectance. Fig. 2 shows an example of a model diagram of a cross section of the welded composite laminate 2 containing the transparent layer 24. As shown in Fig. 2, a barrier layer 22 that is in contact with one main surface is provided on one main surface side of the sintered metal oxide layer 21, and is disposed on the other main surface side of the sintered metal oxide layer 21 and the other main surface. The transparent layer 24 is joined to the surface. The transparent layer 24 is formed on the other main surface of the sintered metal oxide body layer 21, and is formed on the main surface opposite to the barrier layer 22. Preferably, the solder-bonded laminate has a binder layer between the sintered layer of the metal nanoparticles and the barrier layer. Thereby, the solder corrosion of the sintered body layer of the metal nanoparticles can be more reliably suppressed. The thickness of the binder layer is preferably from 0.001 to Ιμιη from the viewpoint of improving the adhesion. Fig. 3 shows an example of a model diagram of a cross section of the welded composite laminate 3 containing the adhesive layer 35. In Fig. 3, a binder layer 35 which is in contact with a main surface is provided on one main surface side of the sintered metal layer 31 of the metal nanoparticle, and a main surface is provided on the main surface side of the binder layer 35. The barrier layer 32 is provided with a solder joint layer 33 that is in contact with a main surface on one main surface side of the barrier layer 32. As is apparent from Fig. 3, the adhesive layer 35 is formed between the sintered metal oxide layer 31 and the barrier layer 32. <<Transparent Layer and Adhesive Layer>> Each of the transparent layer 24 and the adhesive layer 35 is produced as follows. The coating composition is formed into a film by a wet coating method to form a coating film. Then, the coating film was dried, followed by baking. By the above, the transparent layer 24 and the adhesive layer 35 can be formed. Here, the transparent layer 24 and the adhesive layer 35 contain a binder. It is preferable to contain at least one of a polymer type binder which is hardened by heating and a non-polymer type -25-201242761 type binder. Therefore, the transparent layer 24 and the binder layer 35 can be easily produced by the wet coating method. Examples of the polymer type binder include acrylic resin, polycarbonate, polyester, alkyd resin, polyurethane, acrylic urethane, polystyrene polyacetal, and polyamine. , polyvinyl alcohol, polyvinyl acetate, cellulose and siloxane polymers. Further, the polymer type binder preferably contains a metal soap selected from the group consisting of aluminum, barium, titanium, chromium, manganese, iron, cobalt, nickel, silver, copper, zinc, molybdenum, and tin, metal complex, and metal alkoxide. At least one of the group of the hydrolyzate of the metal alkoxide and the metal alkoxide is a non-polymer type binder, and examples thereof include a metal soap, a metal complex, a metal alkoxide, an alkoxy decane, and a halogenated decane. Classes, 2-alkoxyethanol, β-diketone, and alkyl acetate. Further, the metal contained in the metal soap, the metal complex or the metal alkoxide is preferably aluminum, bismuth, titanium, chromium, manganese, iron, cobalt, nickel, silver, copper, zinc, molybdenum, tin, indium or Helium, more preferably an alkoxide of bismuth or titanium. Examples of the alkoxide of ruthenium include tetraethoxy decane, tetramethoxy decane, and butoxy decane. Examples of the halodecanes include trichlorodecane. These polymer type binders and non-polymer type binders can be hardened by heating to form an antireflection film having high adhesion. When the metal alkoxide is hardened, it is preferable to contain a hydrochloric acid, a nitric acid, a phosphoric acid (η3ρο4), an acid such as sulfuric acid, or a base such as ammonia or sodium hydroxide as a catalyst. It is more preferably nitric acid from the viewpoint that the catalyst is easily volatilized and does not easily remain after heat hardening, the halogen does not remain, the water resistance is weak, and the like, and the adhesion after curing is preferable. The content of the binder in the binder composition is preferably from 1 90 to 90 parts by mass, more preferably from 3 parts by mass, based on the binder composition other than the dispersion medium -26-201242761. 0 to 80 parts by mass. When the amount is 10 parts by mass or more, the adhesion to the transparent conductive film is good, and when it is 90 parts by mass or less, film unevenness is less likely to occur at the time of film formation. Further, when a metal alkoxide is used as a binder and nitric acid is used as a catalyst, the curing rate of the binder is 1 to 10 parts by mass with respect to the metal alkoxide: 100 parts by mass. The viewpoint of the residual amount of nitric acid is preferred. Further, the binder composition preferably contains transparent oxide fine particles. Thereby, the refractive index of the transparent layer can be adjusted, and the effect of enhancing the reflection by the sintered body layer of the metal nanoparticles can be suppressed. When the transparent oxide fine particles have a high refractive index, the refractive index of the transparent film after baking or curing can be easily adjusted by the content of the transparent oxide fine particles. Examples of the transparent oxide fine particles include micro SiO 2 'Ti〇 2 ' Zr 〇 2 ' ITO (Indium Tin Oxide), ZnO, ATO (Antimony Tin Oxide), and the like. The powder is preferably ITO or Ti〇2 from the viewpoint of refractive index. Further, the average particle diameter of the transparent oxide fine particles is preferably in the range of 1 Å to 10 nm, more preferably in the range of 20 to 60 nm, in order to maintain stability in the dispersion medium. Here, the average particle diameter is measured by a dynamic light scattering method. Further, it is preferred that the transparent oxide fine particles are dispersed in the dispersion medium in advance, and then the other components of the binder composition are mixed. Thereby, the transparent oxide fine particles can be uniformly dispersed. The content of the transparent oxide fine particles is preferably 10 to 90 parts by mass, more preferably 20 to 70 parts by mass, per 100 parts by mass of the binder composition other than the dispersion medium. When the content of the transparent oxide fine particles is from 10 -27 to 201242761 parts by mass, the effect of returning light from the transparent conductive film (transparent layer) back to the transparent conductive film side can be expected. When the content of the transparent oxide fine particles is 90 parts by mass or less, the strength of the transparent layer itself, the adhesion between the transparent layer and the sintered body layer of the metal nanoparticles, and the adhesion between the transparent layer and the bonded body can be maintained. Further, the binder composition preferably contains a coupling agent in combination with other components used. Thereby, the low haze of the transparent layer, the adhesion between the transparent layer and the sintered body layer of the metal nanoparticles, and the adhesion between the transparent layer and the joined body can be improved. Further, when the transparent oxide fine particles are contained, the adhesion between the transparent oxide fine particles and the light-transmitting adhesive (adhesive) is also improved. Examples of the coupling agent include a decane coupling agent, an aluminum coupling agent, and a titanium coupling agent. Examples of the decane coupling agent include vinyl triethoxy decane, γ-glycidoxypropyl trimethoxy decane, γ-methyl propylene methoxy propyl trimethoxy decane, and the like as an aluminum coupling agent. 'A compound containing an ethoxylated alkoxy group represented by the following chemical formula (1) is mentioned. [Chemical 1] 3 _ CIC I _3 c o-a, 0, ◦ = 0〆

Η3 C 3 -Η Η CIC \/

H3C

c-H 35 8h C1 1 Equation 2 Under the chemical chemistry of the following and the combination of the object, the base acid phosphate phosphorus pyrolysis titanium base is an alkane two, there is also a description of the -28- (2) 201242761 shows a compound having a dialkyl phosphate group [Chemical 2] 0II C-0-Ti

H2C • 0

Ο 0II II 〇—Ρ—Ο-Ρ~^0〇8Ηΐ7^

OH 2 【化3】 H2C—Ο—Τί h2c-ο

ο οII II ί—o-p-o-p-^oc8h17) )OH 2 (3) 2 [Chemical 4] CH3 H3C-CH~0-Ti. 0 0II II 〇-P-〇-ρ· OC8H17 (4)

OH [Chemical 5] (〇8Η! 7〇) 4Ti [P (0C13H27)2〇Η] (5) The content of the coupling agent is preferably 0.01 to 5 by mass based on the composition of the binder: 100 parts by mass. More preferably, it is 0.1 to 2 parts by mass. When the content of the coupling agent is 0.1 part by mass or more, the adhesion between the transparent layer (or the binder layer) and the sintered body layer of the metal nanoparticles, the adhesion between the transparent layer and the bonded body, and the particles are remarkably improved. The effect of dispersibility. When the content of the coupling agent is more than 5 parts by mass, film unevenness is likely to occur. In order to form a film well, the binder composition preferably contains a dispersion medium. Examples of the dispersion medium include water; alcohols such as methanol, ethanol, isopropanol, and butanol-29 to 201242761; and ketones such as acetone, methyl ethyl ketone, cyclohexanone, and isophorone: toluene Hydrocarbons such as xylene, hexane, cyclohexane, etc.; amides such as N,N-dimethylformamide, N,N-dimethylacetamide; Glycols such as ethylene glycol; glycol ethers such as ethyl cellosolve; The content of the dispersion medium is preferably from 80 to 99 parts by mass based on 100 parts by mass of the binder composition in order to obtain good film formability. Further, it is preferred to add a water-soluble cellulose derivative in accordance with the components used. Although the water-soluble cellulose derivative is a nonionic surfactant, it has a very high ability to disperse conductive oxide powder (transparent oxide fine particles) even when added in a small amount compared with other surfactants, and is soluble in water. The addition of the cellulose derivative also increases the transparency of the formed transparent layer. Examples of the water-soluble cellulose derivative include hydroxypropylcellulose and hydroxypropylmethylcellulose. The amount of the water-soluble cellulose derivative to be added is preferably 0.2 to 5 parts by mass based on 100 parts by mass of the binder composition. Further, the binder composition preferably also contains a low resistance agent. As the low resistance agent, a metal salt selected from mineral salts and organic acid salts of Co, Fe, In, Ni, Pb, Sn, Ti, and Zn can be used. Examples of the mineral acid salt include a hydrochloride, a sulfate, and a nitrate. The organic acid salt may, for example, be an acetate, a propionate, a butyrate, an octylate, an acetamidine acetate, a naphthenate or a benzoate. The amount of the low-resistance agent to be added is preferably 0.5 to 10 parts by mass based on 100 parts by mass of the binder composition. A method for producing a binder composition, a method for forming a film by a wet coating method to form a coating film, a method for drying a coating film, and a baking method, and a method for baking a metal film with a metal -30-201242761 The composition for the sintered particle layer and the method for producing the sintered body layer of the metal nanoparticles are the same. Further, in the case where the sintered body layer of the metal nanoparticles has holes, when the binder composition is applied to the sintered layer of the metal nanoparticles, the binder composition saturates the pores of the sintered layer of the metal nanoparticles. Further, after the binder composition is hardened, the sintered body layer of the metal nanoparticles contains a binder. The sintered body layer of the metal nanoparticle containing the binder is preferable because it suppresses solder etching of the sintered layer of the metal nanoparticle. [Joining body] The joining system of the present embodiment includes the first joined body, the welded joint laminate of the present embodiment, and the second joined body in this order. Fig. 4 shows an example of a model diagram of a cross section of the joined body 4 of the present embodiment. 4 shows an example in which the transparent layer 44 and the adhesive layer 45 are provided. As is apparent from Fig. 4, the joined body 4 includes the first joined body 46, the welded joint laminate 40, and the second joined body 47 in this order. The welding combined laminate 4 is provided with a transparent layer 44, a sintered metal layer 4 1 , a binder layer 45, a barrier layer 42 and a welded layer 43 in this order. Specifically, a metal nanoparticle sintered body layer 4 1 that is in contact with a main surface is provided on one main surface side of the transparent layer 44, and a main surface side of the sintered metal oxide layer 41 is provided on the main surface side of the transparent layer 44. Adhesive layer 45. A barrier layer 42 that is in contact with a main surface is provided on one main surface side of the adhesive layer 45, and a solder joint layer 43 that is in contact with a main surface is provided on one main surface side of the barrier layer 42. Therefore, the transparent layer 44 is formed on the other main surface side of the sintered metal body layer 41 to be connected to the other main surface -31 - 201242761. Further, the binder layer 45 is provided between the metal nanoparticle sintered body layer 41 and the barrier layer 42. In FIG. 4, the first joined body 46 is provided so as to be in contact with the other main surface on the other main surface side of the transparent layer 44 of the welding combined laminate 40, and the second joined body 47 is attached thereto. One of the welded joint layers 43 of the welding-use laminated body 40 is provided on the main surface side so as to be in contact with one main surface. Here, the 'first bonded system can emit light or photoelectrically convertible elements, and the metal nanoparticle sintered body layer can reflect light from the first bonded body. When the second bonded body is a substrate, it is suitable for bonding. The body is used for optical purposes. Specifically, when the first joined body is an element capable of emitting light, the bonded body can be used as a light-emitting source such as an LED. When the second joined body is a photo-electrically convertible element, the bonded body can be used as a solar cell. [Examples] Hereinafter, the present invention will be described in detail by way of examples, but the invention is not limited thereto. <<Preparation of a binder composition for a transparent layer>> [Preparation of a material 1-1] Mixing 1 〇 by mass of a non-polymeric binder as a binder, 2-n-oxyethanol and 3-isopropyl-2 A mixture of 4 pentanediol (mass ratio 5'5) and 90 parts by mass of isopropyl alcohol as a dispersion medium. The material 1-1 was prepared by stirring the mixture at room temperature for 2 hours at a rotation speed of 200 rpm. -32- 201242761 [Preparation of Material 1-2] Mixing 10 parts by mass of 2-n-propoxyethanol as a non-polymer type binder as a binder and 90 parts by mass of isopropyl alcohol and butanol as a dispersion medium Mixture (mass ratio 40:60). Stir the mixture at room temperature with a rotation speed of 200 rpm! Hours to make 1〇g material ι_2. [Preparation of materials 1-3] by mixing 10 parts by mass of a Si〇2 binder as a binder and 90 parts by mass of a mixture of ethanol and butanol (mass ratio 98:2) as a dispersion medium to prepare L〇g material 1-3. Further, the Si〇2 binder used as the binder was produced by the following method. First, 11. 〇g HC1 (concentration: 12 mol/l) was dissolved in 25 g of pure water to prepare an aqueous HCl solution. A 500-cm3 glass 4-necked flask was used, and 140 g of tetraethoxy decane and 240 g of ethanol were mixed. The above aqueous HCl solution was added at once while stirring the mixture. Then, the reaction was carried out at 80 ° C for 6 hours to produce a SiO 2 binder. The polymer of the alkoxide of this S i Ο 2 binder is a non-polymeric binder. [Preparation of the materials 1 - 4] 5 parts by mass of gelatin as a binder, 1 part by mass of hydroxypropylcellulose as a water-soluble cellulose derivative, and 94 parts by mass of water as a dispersion medium were mixed. The mixture was stirred at a rotation speed of 200 rpm for 1 hour at a temperature of 30 ° C to prepare 10 g of materials 1-4. -33- ☆ 201242761 "Production of a barrier layer composition" [Modulation of material 4-1] As a composition for a barrier layer based on (A) metal nanoparticles, silver nanoparticle and gold nanoparticles are contained. The mixed metal nanoparticle dispersion (Ag: Au = 80%: 20%) was centrifuged. Polyethylene glycol was added to the precipitate after centrifugation to prepare a mixture in such a manner that the polyethylene glycol was 5 parts by mass based on 95 parts by mass of the metal nanoparticles. The mixture was further mixed by a planetary agitating mixer to modulate the composition for the barrier layer. Here, a mixed metal nanoparticle dispersion containing silver nanoparticles and gold nanoparticles is produced as follows. <<Preparation of Silver Nanoparticle Dispersion>> Silver nitrate was dissolved in deionized water to prepare a metal salt aqueous solution having a concentration of 25 mass%. Further, sodium citrate was dissolved in deionized water to prepare a sodium citrate aqueous solution having a concentration of 26% by mass. In this aqueous sodium citrate solution, granulated ferrous sulfate is directly added and dissolved in a nitrogen stream maintained at 35 Torr, and a reducing agent containing citrate ions and ferrous ions in a molar ratio of 3:2 is prepared. Aqueous solution. Next, a stir bar of a magnetic stirrer was placed in the aqueous solution of the reducing agent. The above-mentioned nitrogen gas stream was kept at 35 ° C, and while stirring at a rotation speed of a stirring bar of 100 rpm, the aqueous metal salt solution was dropped into the aqueous reducing agent solution and mixed. Here, the amount of the aqueous solution of the metal salt to be added to the aqueous solution of the reducing agent is adjusted so that the concentration of each solution is equal to or less than 1 / 1 Torr of the amount of the reducing agent aqueous solution. Thereby, even if the room temperature metal salt -34-201242761 aqueous solution was dropped, the reaction temperature was maintained at 40t. Further, the number of moles of citrate ions and the number of moles of ferrous ions in the aqueous solution of the reducing agent are three times the number of moles of the reducing agent required to reduce all of the metal ions in the aqueous solution of the metal salt. In this manner, the mixing ratio of the reducing agent aqueous solution to the metal salt aqueous solution is adjusted. After the dropwise addition of the aqueous solution of the metal salt to the aqueous solution of the reducing agent, the mixture was further stirred for 15 minutes. Thereby, silver nanoparticles are generated inside the mixed solution. Through the above, a silver nanoparticle dispersion in which silver nanoparticles were dispersed at 100 cm3 was obtained. The pH of the silver nanoparticle dispersion was 5.5, and the amount of the stoichiometric amount of the silver nanoparticles in the dispersion was 5 g/liter. The obtained silver nanoparticle dispersion was allowed to stand at room temperature to precipitate the silver nanoparticles in the dispersion, and the agglomerates of the settled silver nanoparticles were separated by decantation. Deionized water was added to the separated silver nanoparticle aggregates to form a dispersion, and desalting treatment was carried out by ultrafiltration. Next, the silver nanoparticle aggregates were washed with methanol to have a silver content of 50% by mass. Then, the centrifugal force of the centrifugal separator was adjusted using a centrifugal separator to separate the particles having a particle diameter of more than 1 〇〇 nm. Compare large silver particles. Thereby, the content of the silver nanoparticles in the range of the primary particle diameter of 10 to 50 nm was adjusted to 71% by the number average. In other words, 100% of all the silver nanoparticles with respect to the number average are adjusted so that the ratio of the silver nanoparticles in the range of 10 to 50 nm in the primary particle diameter is 71%, and silver nanoparticles are obtained. Particle dispersion. The obtained silver nanoparticles were chemically modified with a sodium citrate protective agent. -35- 3 201242761 "Preparation of a gold nanoparticle dispersion liquid" In addition to the use of chloroauric acid instead of silver nitrate, in the same manner as in the production method of the silver nanoparticle dispersion liquid, the average particle diameter of l〇〇cm3 is obtained as lOnm. Gold nanoparticle dispersion of 5 mass% of the gold nanoparticles. <<Preparation of Mixed Metal Nanoparticle Dispersion Liquid>> A silver nanoparticle dispersion liquid and a gold nanoparticle dispersion liquid obtained by mixing Ag 80% and Au 20% by mass ratio to obtain a mixed metal naphthalene of 100 cm 3 Rice particle dispersion liquid [Production of material 4-2] As a composition for a barrier layer based on (B) a metal compound, Ag particles (average particle diameter: 0·1μηι) 7 () parts by mass, silver oxide (average Particle size: Ο.ίμιη) : 5 parts by mass, silver carbonate (average particle diameter: 〇·4μιη): 5 parts by mass, terpineol: 20 parts by mass. In detail, each raw material is premixed, followed by planetary stirring. The mixture was further mixed to obtain a paste-like barrier layer composition. "Material for welding layer and production of welded layer" [Production of material 5-1] Au-Sn alloy solder (solder for needle transfer) made of Mitsubishi material was used. The group becomes Au:Sn = 22:78 (mass ratio). The solder paste of the material 5-1 was formed on the surface of the element (the surface of the barrier layer or the sintered body layer of the metal nanoparticles) by a needle transfer method to form a coating film. In a state where the coating film is brought into contact with the substrate -36-201242761, the coating film is heated to 310 ° C to bond the device to the substrate. [Production of Material 5-2.] Au-Sn alloy solder (solder for needle transfer) made of Mitsubishi material was used. The group becomes Au:Sn = 78:22 (mass ratio). The solder paste of the material 5-2 is formed on the surface of the element (the surface of the barrier layer or the sintered body layer of the metal nanoparticles) by a needle transfer method to form a coating film. The coating film was heated to 350 ° C in a state where the coating film was brought into contact with the substrate to bond the device to the substrate. <<Preparation of Composition for Sintered Layer of Metal Nanoparticles>> The compositions for the sintered metal nanoparticles were prepared by mixing the compositions described in Tables 1 and 2. Here, the silver nanoparticle and the gold nanoparticle are produced in the same manner as the method for producing the nanoparticle used in the material 4-1. Furthermore, chloroauric acid was used as a raw material for Au, and silver nitrate was used as a raw material for Ag. [Example 1] An element in which a light-emitting layer was formed on a sapphire substrate having a length of 5 mm, a width of 5 mm, and a thickness of 5 mm was prepared. On the support substrate, a Si substrate having a length of 20 mm' width: 20 mm and a thickness of 0.5 mm and having Ni/Au plating on the surface was prepared. First, a composition for sintering a metal nanoparticle sintered body layer was applied by a spin coating method on a bonding surface of a device, and 13 (TC was baked for 10 minutes to form a sintered metal nanoparticle layer having a thickness of 0.3 μm. On the sintered body layer of the metal nanoparticle, the coating material was coated by -43-201242761 cloth material 4-1' at 200 eC for 20 minutes to form a barrier layer having a thickness of ΐμηι. On the barrier layer, the needle was used. In the transfer method, the material 5-1 was formed into a film. Next, the film formation surface was bonded to the Ni surface of the substrate, and heated at 310 ° C for 10 minutes to bond the device to the substrate. [Example 2 EXAMPLES 2] The bonded bodies of Example 2 and Comparative Examples 1 and 2 were produced in the same manner as in Example 1 except for the conditions described in Tables 1 and 2. As is apparent from Tables 1 and 2, Example 2 was further improved. A transparent layer is formed. First, a transparent layer binder composition (material 1-1) is applied by spin coating on the bonding surface of the element, and baked at 130 ° C for 30 minutes to form a thickness: Ο.ΟΙμπι a transparent layer. Then, on the transparent layer, a sintered layer of metal nanoparticles is formed in sequence. Comparative Example 1 does not form a barrier layer and a binder layer, and Comparative Example 2 does not form a sintered body layer of a metal nanoparticles and a binder layer. [Example 3] The same components as in Example 1 were used. First, a composition for sintering a metal nanoparticle sintered body layer is applied on a bonding surface of a device by a screen printing method, and baked at 15 Torr for 5 minutes to form a metal nanoparticle having a thickness of Ο.ίμιη. A sintered body layer is coated on the sintered metal layer of the metal nanoparticle by a dip coating method, and then dried to form a layer of a binder having a thickness of 0.1 μm. On the layer of the binder, by an inkjet method The coating material 4-1 was baked at 200 ° C for 20 minutes to form a barrier layer having a thickness of Ιμιη. On the barrier layer of -38 to 201242761, the material 5-1 was formed into a film by a needle transfer method. In the state where the film formation surface is bonded to the Ni surface of the substrate, the element is bonded to the substrate by heating at 310 ° C for 1 minute. [Examples 4 and 5] Except the conditions described in Tables 1 and 2 The joined bodies of Examples 4 and 5 were produced in the same manner as in Examples 2 and 3. [Joint strength Evaluation] The joint strength (shear strength) of the joined bodies of Examples 1 to 5 and Comparative Examples 1 and 2 was measured by a precision universal testing machine Autograph AG-Xplus. The measurement conditions were based on JI SZ 3 1 9 8 _ 5 [Evaluation of Luminous Intensity] The luminous intensity (relative intensity) of the bonded bodies of Examples 1 to 5 and Comparative Examples 1 and 2 was measured by a Labsphere LSA-3000 apparatus. ^ -39- 201242761 [Example] Example 5 CO 1 inch d Ο &lt;Ν ο τ~ lil S ® a- u inch 〇Ο οα CM ΙΟ r— C0 1 04 〇1 1 eg 1 inch 10 CN4 300 Ο Φ τ- Ι u&gt; in 产 CO Ο R— ο ο ο CO τ-* Example 4 &lt;N 1 τ- τ- Ο 2 0 0 ο &lt;Μ e W 13⁄43⁄4 ^c;ti〇1 CM 6 Ο Is- r- eg τ- 1 in 〇 〇1 1 CSI 1 inch in CM 3 0 0 Ο (D τ- Ι ΙΟ in ο Ύ - CO Ο r* Ι 广Ι-* ο CS4 r- Example 3 m 1 1 ι g^Sg H thorn® lfS| 〇00的黎5 -|1 r- 6 Ο \Ρ ι— U5 inch ' T— τ— 6 1 1 1 inch η· Ο ο CM Ο OJ production 1 to in ο τ-· C0 Ο τ— ο Ν τ — Ο Strictly Example 2 1 T- Τ Ο d ο τ — Ο C0 e 5? £ i&quot;JSS Mai? g: 〇® &lt;&gt; 2 ft- CO to ο 1 200 1 Ο &lt;NJ m 1 1 1 T-1 r- 2 00 Ο CSI CVJ 1 to o 严ο in (Ο ιό to σ&gt; Ο ¢0 Τ^· Example 1 m 1 1 I 1 Ag 100% by mass (0 d 1__130__1 Ο r- destroy 1 1 1 Τ Ι 2 00 Ο CSJ r* 1 l〇LO ο τ—(0 ο Τ—' 00 σ&gt; ο τ—Classification material film thickness (μιη) Calcination temperature (°c) Calcination time (minutes) Material film thickness (μπι&gt; Calcination temperature rc) Calcination time (minutes) Material film® (μ«!) Calcination temperature re) Calcination time (minutes) Abdominal thickness (μιη) Roasting temperature (Art) Roasting time (minutes) Material thickness _) Roasting temperature 焙 Roasting time (minutes) Shear strength (_2) Relative strength Transparent layer Metal nanoparticle Sintered layer binder Layer barrier layer solder joint bonding strength Luminous intensity-40-201242761 [Table 2] Classification Comparative Example 1 Comparative Example 2 Transparent layer material 1-2 Film thickness (μιη) 0.06 One calcination temperature (°C) 170 — Baking time (minutes 5 — Metal nanoparticle sintered body layer material Ag 100% by mass Μ /1, film thickness (μηι) 0.05 — roasting Temperature (.〇180 - calcination time (minutes) 5 - binder layer material Μ j\wy μ, film thickness (μιη) — roasting temperature (°C) — roasting time (minutes) — — barrier layer material Μ 4 -2 Film thickness (μιη) — 2.5 Calcination temperature (°C) — 300 Calcination time (minutes) — 60 Welding layer material 5-1 5-1 Film thickness (μηι) 5 5 Calcination temperature (°C) 310 310 Calcination Time (minutes) 20 10 Bonding strength Shear strength (N/mm2) 10 90 Luminous intensity relative strength (solder etch) 100 As can be seen from Tables 1 and 2, in all of Examples 1 to 5, joint strength and luminescence In Comparative Example 1 in which the barrier layer was not formed, the bonding strength was low, and the luminescence intensity could not be measured by the solder immersion (s ο 1 der 1 each). Further, in Comparative Example 2, the bonding strength was obtained. And the light-emitting intensity is slightly lower. - 41 - 201242761 [Industrial Applicability] The welding-use laminate of the present invention is a metal paste containing metal particles and a solvent as a main component instead of the conventional high-priced Ni barrier. form. Therefore, it can be manufactured in a simple step, and the lining cost can be greatly improved. The bonded body including the solder-use laminate has high reliability and can be applied to LED elements and the like. BRIEF DESCRIPTION OF THE DRAWINGS Fig. 1 is a view showing an example of a model diagram of a cross section of a welding combined laminate of the present invention. Fig. 2 is a view showing an example of a cross section of a cross section of a welded composite laminate containing a transparent layer of the present invention. Fig. 3 is a view showing an example of a cross section of a cross section of a welded composite laminate containing a barrier layer of the present invention. Fig. 4 is a view showing a model of a cross section of the joined body of the present invention. [Description of main component symbols] I, 2, 3, 40: Soldering laminated body 4: joined body II, 21, 31, 41: sintered metal layers of ceramic nanoparticles 12, 22, 32, 42: barrier layers 13, 23, 33, 43: welded joint layer 24, 44: transparent layer 35' 45: adhesive layer 46: first joined body 47: second joined body - 42-

Claims (1)

201242761 VII. Patent application scope: 1. A welding combined laminate, which is characterized by: a sintered layer of a metal nanoparticle, a barrier layer containing metal particles or metal oxide particles, and a welded layer. 2. The welding-use laminate according to the first aspect of the invention, wherein the barrier layer is provided on one main surface side of the sintered metal nanoparticle sintered body layer, and the other main surface side of the sintered metal nanoparticle sintered body layer is further provided. The transparent layer 〇3, wherein the transparent layer contains at least one of a polymer type binder or a non-polymer type binder which is hardened by heating, according to the second aspect of the invention. 4. The welding-use laminate according to the first aspect of the invention, further comprising a binder layer between the sintered metal nanoparticle sintered body layer and the barrier layer. 5. The welding-use laminate according to claim 4, wherein the binder layer contains at least one of a polymer-type binder or a non-polymerization-type binder which is hardened by heating. 6. The welding-use laminate according to claim 1, wherein the sintered body layer of the metal nanoparticle contains 75% by mass or more of silver, and is selected from the group consisting of gold, copper, tin, zinc, molybdenum and manganese. At least 7. The combination of the welding composition of claim 1, wherein the sintered body layer of the metal nanoparticle contains a binder. The welding composition laminate according to the first aspect of the invention, wherein the thickness of the sintered body layer of the metal nanoparticles is 0.01 to 0.5 μm. 9_ The welding-use laminate according to claim 1, wherein the film is formed by a wet coating method, and then each layer is formed by firing at 130 to 250 °C. 10. The welding-use laminate according to claim 9, wherein the wet coating method is a spray coating method, a dispenser coating method, a spin coating method, a knife coating method, a slit coating method, or an inkjet coating method. Any of a method, a screen printing method, a lithography method, or a die coating method. 11. A joined body, comprising: a first joined body, wherein the welded joint laminate according to any one of claims 1 to 1 and the second joined body. The bonded body according to the first aspect of the invention, wherein the first bonded system is capable of emitting light or photoelectrically convertible, and the sintered metal laminate sintered body layer is reflective from the first The light of the bonded body is the second bonded system substrate. 13. The joined body of claim 12, wherein the element capable of emitting light in the i-th bonded system is used as a light source. 14. The joint body of claim 12, wherein the first component that can be photoelectrically converted by the system is used as a solar cell ^ -44-