WO2020256012A1 - Conductive pillar - Google Patents

Conductive pillar Download PDF

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Publication number
WO2020256012A1
WO2020256012A1 PCT/JP2020/023752 JP2020023752W WO2020256012A1 WO 2020256012 A1 WO2020256012 A1 WO 2020256012A1 JP 2020023752 W JP2020023752 W JP 2020023752W WO 2020256012 A1 WO2020256012 A1 WO 2020256012A1
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WIPO (PCT)
Prior art keywords
pillar
conductive pillar
pillars
fine particles
acid
Prior art date
Application number
PCT/JP2020/023752
Other languages
French (fr)
Japanese (ja)
Inventor
亮太 山口
真 矢田
Original Assignee
Dic株式会社
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Publication date
Application filed by Dic株式会社 filed Critical Dic株式会社
Priority to JP2021526839A priority Critical patent/JP7243827B2/en
Publication of WO2020256012A1 publication Critical patent/WO2020256012A1/en

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    • H01L24/16—Structure, shape, material or disposition of the bump connectors after the connecting process of an individual bump connector
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L24/00—Arrangements for connecting or disconnecting semiconductor or solid-state bodies; Methods or apparatus related thereto
    • H01L24/80—Methods for connecting semiconductor or other solid state bodies using means for bonding being attached to, or being formed on, the surface to be connected
    • H01L24/81—Methods for connecting semiconductor or other solid state bodies using means for bonding being attached to, or being formed on, the surface to be connected using a bump connector
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L2924/00—Indexing scheme for arrangements or methods for connecting or disconnecting semiconductor or solid-state bodies as covered by H01L24/00
    • H01L2924/30—Technical effects
    • H01L2924/35—Mechanical effects
    • H01L2924/351—Thermal stress
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L2924/00—Indexing scheme for arrangements or methods for connecting or disconnecting semiconductor or solid-state bodies as covered by H01L24/00
    • H01L2924/30—Technical effects
    • H01L2924/35—Mechanical effects
    • H01L2924/351—Thermal stress
    • H01L2924/3512—Cracking

Definitions

  • the present invention relates to a conductive pillar (Pillar), which is a flip chip mounting terminal that is a connection method between a semiconductor chip and a package interposer in a semiconductor package.
  • the present invention is a pillar produced by sintering a paste containing metal fine particles, and is a conductive pillar having a bonding layer.
  • a semiconductor device is manufactured by manufacturing an electronic circuit on a semiconductor chip and connecting an electrode on the semiconductor chip and an electrode on a semiconductor package.
  • an electrode on a semiconductor chip and an electrode on a semiconductor package have been electrically connected by using a bonding wire made of gold or copper.
  • the flip chip method is used as an electrical connection method between a semiconductor chip and a semiconductor package.
  • Gold bumps and solder bumps are known as typical connection methods in the flip chip method.
  • the flip chip mounting method which is attracting attention as a high-density mounting method, involves forming a large number of solder bumps on metal electrode pads arranged on a wafer or substrate, mounting a semiconductor chip on the electrode pads, and then heating the chips.
  • a method of melting solder bumps to perform chip bonding Patent Document 1.
  • solder bumps in the flip chip mounting method includes a method of forming bumps by electrolytic plating, a printing method such as a stencil mask method and a dry film method, a ball mounting method, a vapor deposition method, and an IMS (injection molded solder) method ( This is done by melting (reflowing) the solder supplied on the wafer or substrate according to Patent Documents 2, 3, 4) and the like. At this time, if the solvent contained in the solder is gasified at the time of melting and remains as voids in the bumps, the joint strength and the like are lowered. Therefore, solder bumps having few voids are required.
  • solder material When solder bump bonding is used, the solder material has problems such as inferior heat resistance, high volume resistivity as compared with copper and silver, and small current capacity. Copper pillar bumps are known as materials for solving these problems. Copper as a metal material used for copper pillars is also excellent in terms of heat resistance, low electrical resistance, high current capacity, high electromigration resistance, and the like (Patent Document 5).
  • the electrolytic plating method has a problem of undercutting when etching the seed layer.
  • the plating method has a high equipment installation cost and a large environmental load due to harmful waste liquid.
  • Patent Document 6 A method using metal particles and solder has been reported as a method for forming copper pillars without using the plating method.
  • Patent Document 6 does not describe in detail the particle size of the metal particles that can be used for the pillars and the composition of the conductive paste, and the effect that the present invention aims to achieve could not be obtained.
  • the plating method has a problem that it is necessary to recycle or dispose of a large amount of waste liquid, which has a large environmental load and costs for equipment maintenance.
  • Bulk copper pillars produced by a plating method or the like are three times or more larger than the elastic modulus of the solder material and eight times or more larger than the yield stress of the solder material. Therefore, the thermal stress generated when the chip and the substrate are joined. There was a problem that could not be sufficiently buffered. As a result, the chip is greatly affected by thermal stress, and cracks are likely to occur in the wiring layer that employs a dielectric constant interlayer insulating film with weak mechanical strength, resulting in a decrease in yield.
  • Document 6 discloses a method for producing a conductive pillar using metal particles as described above, but does not describe any composition of the conductive pillar, and what kind of composition is used as a raw material. It was unclear whether suitable conductivity and bonding strength could be obtained.
  • a conductive pillar using metal particles there is a problem that if the particle size of the metal particles is large, it is not possible to manufacture a fine conductive pillar.
  • a pillar (A) produced by sintering a paste containing metal fine particles having a particle size of less than 1 ⁇ m and a protective agent. And a conductive pillar (B) having a bonding layer.
  • the present invention relates to a conductive pillar used as a terminal for mounting a flip chip.
  • the conductive pillars By forming the conductive pillars on the electrode substrate using the paste according to the present invention, the conductive pillars have been made plating-less.
  • the undercut during etching which was a problem with the conventional method, has been solved, and fine copper pillars can be formed.
  • a conductive pillar By forming a conductive pillar on the electrode substrate using the paste according to the present invention, it was possible to produce a conductive pillar composed of metal fine particles and a bonding layer.
  • the obtained conductive pillars had the performance that the conductivity and the bonding strength could withstand the mounting.
  • the protective agent contained in the pillar (A) has at least one functional group among amino group, carbonyl group, thiol group, alkylthio group, alkenylthio group, thioether group and phosphoric acid group, and
  • the conductive pillar (B) according to (1) which is a compound having a molecular weight of 500 or more.
  • the bonding layer is an alloy containing tin, lead, silver, copper or one or more metals selected from these. Conductive pillars.
  • the present invention is a pillar made of metal fine particles and a conductive pillar having a bonding layer, which can be used for flip chip mounting.
  • a conductive pillar made of a paste containing metal fine particles and a protective agent is an opening portion of a resist layer in which the paste is pre-patterned with a squeegee or the like without using the plating technique which is a conventional technique in the manufacturing process. Pillars can be easily formed by filling the paste.
  • the undercut during etching which has been a problem due to the plating method, can be solved, and fine copper pillars can be formed.
  • the conductive pillar of the present invention can solve the problems of the conventional plating method.
  • the metal species that can be used as the metal fine particles of the present invention are those in which the functional groups in the protective agent described later can be physically or chemically adsorbed on the surface of the metal fine particles or chemically bonded (coordinated). If so, there is no particular limitation. However, from the viewpoint of the stability of the metal fine particles, one or more selected from gold, silver, copper and nickel can be preferably used. Particularly preferred are silver and copper.
  • the metal type may be one kind, or may be a mixture of two or more kinds or an alloy as long as it contains the metals listed above.
  • the average primary particle size of the metal fine particles is preferably less than 1 ⁇ m from the viewpoint of filling property and bondability. Further, when a conductive pillar is produced by utilizing the fusion function of fine particles without using a binder resin, it is more preferable to use metal fine particles having an average primary particle diameter of 100 nm or less. As a result, when the resist opening is filled with paste so that the resist opening is less than 100 ⁇ m to form a conductive pillar, the resist opening is densely filled with metal fine particles, and the electrode / pillar is sufficiently connected. It is possible to maintain the bonding strength and ensure the conductivity due to the contact or bonding between the metal fine particles.
  • the pillars When the pillars are formed by the fusion function of the metal, the pillars can be formed with or without the addition amount of the binder resin, and the pillars having excellent heat resistance can be formed.
  • the shape of the metal fine particles is not particularly limited, and spherical or flake-shaped fine particles can be used within a range that does not impair the effects of the present invention, but the average primary particle diameter calculated by the method for calculating the average primary particle diameter Is preferably less than 1 ⁇ m.
  • the average primary particle size can be calculated by observation with a transmission electron microscope (TEM). That is, in the present specification, the average primary particle diameter of the metal fine particles is calculated by taking a photograph of a sample with a transmission electron microscope (TEM) and analyzing the image.
  • TEM transmission electron microscope
  • the prepared metal fine particles are diluted with a good solvent to an arbitrary concentration, and the diluted solution is cast on a carbon film-coated grid and dried to obtain a sample for observation with a transmission electron microscope (TEM).
  • TEM transmission electron microscope
  • 200 fine particles are randomly extracted from the obtained TEM image, the area of each fine particle is obtained, and a value calculated based on the number of particle size when converted into a true sphere is adopted. From the randomly selected particles, those in which two particles overlap are excluded. When a large number of particles are in contact with each other or secondarily aggregated and aggregated, the particles constituting the aggregate are treated as independent particles.
  • each of the five particles constituting the aggregate is a target for calculating the average primary particle diameter of the metal fine particles.
  • the value before sintering is adopted as the average primary particle diameter. That is, the value before fusion occurs due to sintering is adopted.
  • the protective agent of the present invention is not particularly limited as long as it can protect the surface of the metal fine particles with the protective agent and has a functional group and / or a molecular structure having an affinity for the metal fine particles and the dispersion medium. Compounds having the following functional groups / molecular structures can be used.
  • the protective agent to be used can be used regardless of the size of the molecular weight, and high conductivity and dispersion stability can be imparted to the metal fine particles by designing the protective agent according to the metal type to be used and the desired physical properties. Is possible.
  • the characteristics of metal fine particles can be freely changed by selecting a protective agent according to various purposes.
  • a protective agent When a high molecular weight protective agent is used, various properties can be exhibited by changing the number and types of functional groups in the compound.
  • a low molecular weight protective agent When a low molecular weight protective agent is used, various properties can be exhibited by using two or more compounds in combination.
  • the functional group contained in the protective agent of the present invention include a thiol group, an alkylthio group, an alkenylthio group, a carboxy group, an amino group, a hydroxy group, a phosphoric acid group, a phosphoric acid ester group, a sulfonic acid group, and an aromatic group.
  • the family group is mentioned.
  • Dispersion stability can be added to the fine particles by using a protective agent having these functional groups.
  • a low molecular weight compound having a carboxyl group When a low molecular weight compound having a carboxyl group is used as the protective agent, the following substances can be used as specific examples.
  • a low molecular weight compound having an amino group When a low molecular weight compound having an amino group is used as the protective agent, the following substances can be used as specific examples.
  • any molecular structure having an affinity for the dispersion medium can be adopted as the selectable molecular structure.
  • the dispersion medium is a polar solvent such as alcohols or water
  • an organic compound containing a polyethylene oxide structure having 8 to 200 carbon atoms can be preferably used, and a polyethylene oxide structure having 8 to 100 carbon atoms can be preferably used.
  • the containing organic compound can be used more preferably. Since the polyethylene oxide moiety of the protective agent has excellent affinity with an alcohol solvent having a boiling point of 250 ° C. or lower, aggregation of metal fine particles can be strongly suppressed, and metal fine particles can be highly dispersed. As a result, the metal fine particles are packed at a high density, and voids are not generated due to the decomposition and removal of the protective agent and the solvent by the heat treatment, and the high density filling is possible.
  • metal fine particles composite of organic compound and metal fine particles
  • organic compound containing a polyethylene oxide structure having 8 to 200 carbon atoms used in the present invention
  • Japanese Patent No. 4784847 and Japanese Patent Application Laid-Open No. 2013-60637 the metal fine particles described in Japanese Patent No. 5077728 can be mentioned, and can be synthesized by the method described therein.
  • the thioether type (RSR') organic compound has an appropriate affinity adsorption effect on the surface of metal fine particles and a rapid desorption property by heating, and has low temperature fusion characteristics. It has been developed as a metal fine particle showing.
  • metal fine particles in which a polymer compound having a polyethylene oxide moiety having 8 to 200 carbon atoms is composited are included.
  • the polymer compound containing these polyethylene oxide structures can be produced according to the methods described in these publications.
  • the phosphoric acid ester type organic compound containing these polyethylene oxide structures has a thioether skeleton and also has a phosphoric acid ester group, and by having these groups, the surface of the metal fine particles is subjected to. Appropriate affinity adsorption effect and rapid desorption by heating can be added.
  • the concentration of the protective agent in the paste is not particularly limited, but is preferably in the range of 15% or less from the viewpoint of easy fusion of metal fine particles during sintering, conductivity and improvement of bonding strength. Yes, more preferably in the range of 10% or less.
  • the paste according to the present invention is composed of at least metal fine particles and a protective agent.
  • the paste according to the present invention can be produced by protecting the surface of metal fine particles with a protective agent. Any method can be adopted for the preparation of the paste. For example, in addition to the chemical reduction method, the thermal decomposition method and the electrochemical method can be adopted as the wet method, and the evaporation method in gas and the sputtering method can be adopted as the dry method.
  • a method for producing a paste when an organic compound containing a polyethylene oxide structure having 8 to 200 carbon atoms is used as a protective agent will be described.
  • the metal type is copper and / or silver
  • the metal fine particles in which an organic compound containing a polyethylene oxide structure having 8 to 200 carbon atoms is composited are prepared by mixing a divalent copper ion compound or a monovalent silver ion compound with a solvent in the presence of a thioether type organic compound. It can be easily produced by combining with a step of reducing copper ions or silver ions.
  • the divalent copper ion compound a generally available copper compound can be used, and sulfates, nitrates, carboxylates, carbonates, chlorides, acetylacetonate complexes and the like can be used.
  • a complex with zero-valent copper fine particles it may be produced from a divalent compound or a monovalent compound, or may have water or water of crystallization.
  • the divalent copper ion compound CuSO 4 , Cu (NO 3 ) 2 , Cu (OAc) 2 , Cu (CH 3 CH 2 COO) 2 , Cu (HCOO) 2 , CuCO 3 , CuCl 2 , Cu 2 O, C 5 H 7 CuO 2 , and their hydrates and the like can be used.
  • heating the salt, or a basic salt e.g. Cu (OAc) 2 ⁇ CuO obtained by such exposure to a basic atmosphere, Cu (OAc) 2 ⁇ 2CuO , Cu 2 Cl (OH) 3 or the like suitably the Can be used.
  • These basic salts may be prepared in the reaction system, or may be prepared separately outside the reaction system. Further, a general method of adding ammonia or an amine compound to form a complex to secure solubility and then using it for reduction can also be applied.
  • the monovalent silver ion compound generally available silver compounds can be used, such as silver nitrate, silver oxide, silver acetate, silver fluoride, silver acetylacetonate, silver benzoate, silver carbonate, and silver citrate.
  • silver hexafluorophosphate, silver lactate, silver nitrite, silver pentafluoropropionate, hydrates thereof, etc., and silver nitrate or silver oxide can be used from the viewpoint of ease of handling and industrial availability. preferable.
  • These copper and / or silver ion compounds are dissolved or mixed in a solvent in which a thioether type organic compound is dissolved or dispersed in advance.
  • the solvent that can be used at this time depends on the structure of the organic compound used, but alcohols such as ethanol, ethylene glycol, diethylene glycol and glycerin, polar solvents such as water and acetone, and mixtures thereof are preferable. Can be used. Of these, a water-ethylene glycol mixture is particularly preferred.
  • the concentration of the thioether-type organic compound in various solvents is preferably adjusted to the range of 0.3 to 10% from the viewpoint of facilitating the control of the subsequent reduction reaction.
  • Copper and / or silver ion compounds are added collectively or separately to the solvent prepared above and mixed.
  • a poorly soluble solvent When used, it may be dissolved in a small amount of a good solvent in advance and added to the solvent.
  • the mixing ratio of the thioether-type organic compound to be mixed with the copper and / or silver ion compound can be appropriately selected according to the protective ability of the thioether-type organic compound in the reaction solvent.
  • the thioether-type organic compound per 1 mol of the copper and / or silver ion compound is prepared in the range of 1 mmol to 30 mmol, and is particularly preferably used in the range of 15 to 30 mmol.
  • the same can be carried out by using a phosphoric acid ester type organic compound containing a polyethylene oxide structure, and the amount of the organic compound used per 1 mol of the copper and / or silver ion compound is also the same as described above.
  • Reducing agents include hydrazine compounds, hydroxylamines and derivatives thereof, metal hydrides, phosphinates, aldehydes, endiols, hydroxyketones, etc., and reduction of copper and / or silver at a temperature of 80 ° C. or lower from ice-cold temperature. Since the reaction can proceed, it can be preferably used.
  • reducing agents such as hydrazine hydrate, unsymmetrical dimethylhydrazine, aqueous hydroxylamine solution, and sodium borohydride are suitable. These reducing agents can reduce copper compounds to 0 valence, and are suitable for producing a composite of an organic compound and nano-copper particles by using divalent and monovalent copper compounds as reduced copper.
  • the conditions of the reduction reaction can be appropriately set according to the copper compound used as a raw material, the type of reducing agent, the presence or absence of complexation, the solvent, and the type of the thioether type organic compound.
  • copper (II) acetate is reduced with sodium borohydride in an aqueous solvent
  • zero-valent nanocopper particles can be prepared even at an ice-cooled temperature.
  • hydrazine is used, the reaction is slow at room temperature, and a smooth reduction reaction occurs only after heating to about 60 ° C.
  • a reaction time of about 2 hours is required at 60 ° C.
  • a reaction mixture containing a complex of an organic compound and copper-based fine particles is obtained.
  • the copper fine particles prepared in this way can be highly dispersed in the same manner as before drying even when the moisture is completely removed by the effect of the protective agent to obtain a dried body powder and then dispersed in the solvent again. is there.
  • a step of removing metal compound residue, reducing reagent residue, organic compound containing excess polyethylene oxide structure, etc. is provided as necessary.
  • Purification of the complex can be carried out by reprecipitation, centrifugal sedimentation, ultrafiltration, etc., and the above-mentioned impurities are obtained by washing the reaction mixture containing the obtained complex with water, ethanol, acetone and a mixture thereof. Can be washed away.
  • the paste according to the present invention is used for binder components such as resins, antidrying agents, antifoaming agents, adhesion imparting agents to substrates, antioxidants, and for promoting film formation, as long as the effects of the present invention are not impaired.
  • binder components such as resins, antidrying agents, antifoaming agents, adhesion imparting agents to substrates, antioxidants, and for promoting film formation, as long as the effects of the present invention are not impaired.
  • Various catalysts, various surfactants such as silicone-based surfactants and fluorine-based surfactants, leveling agents, mold release accelerators and the like can be added as auxiliary agents.
  • the concentration of the metal fine particles in the paste according to the present invention can be adjusted to an arbitrary concentration by adding a dispersion medium described later.
  • the dispersion medium can be added at the time of paste synthesis or after synthesis.
  • the concentration of the metal fine particles in the paste is not particularly limited, but is preferably in the range of 40 or more and less than 95%, more preferably 60 to 90%, in consideration of the fluidity of the paste and the filling performance in the opening portion. The range.
  • Dispersion medium Water or a solvent as a dispersion medium can be added to the paste containing the metal fine particles and the protective agent of the present invention as long as the effects of the present invention are not impaired.
  • the dispersion medium can be added for the purpose of imparting wettability to the base material and adjusting the concentration of metal fine particles in the paste.
  • the dispersion medium that can be used in the present invention it is desirable that the dispersion medium does not remain inside the pillars after sintering, and it is preferable to use a compound or mixture having a boiling point of 250 ° C. or lower.
  • the dispersion medium is not particularly limited as long as it is a compound having a boiling point of 250 ° C. or lower, and water and / or an organic solvent can be used as the dispersion medium.
  • As the dispersion medium it is preferable to use a good dispersion medium that does not agglomerate metal fine particles in order to produce a paste having a uniform particle size.
  • organic solvents that can be preferably used.
  • examples of the organic solvent containing a hydroxyl group include water, methanol, ethanol, 1-propanol, isopropanol, 1-butanol, isobutanol, sec-butanol, tert-butanol, amyl alcohol, tert-amyl alcohol, 1-hexanol, and cyclo.
  • the pillars in the present invention are not particularly limited in shape, diameter, etc. as long as the effects of the present invention are exhibited.
  • the pillar of the present invention preferably has a columnar shape because the tip bonding is stable, more preferably a substantially columnar shape, and particularly preferably a columnar shape.
  • the diameter of the pillar of the present invention is preferably 100 ⁇ m or less, more preferably 50 ⁇ m or less, and particularly preferably 30 ⁇ m or less, because the chip joining step becomes efficient.
  • the method for forming pillars in the present invention is not particularly limited, but a method for forming pillars by an embedding method will be described in detail below.
  • a resist layer is formed on a substrate having an electrode portion, a pattern (mold) having a plurality of openings is formed in the resist layer, and a paste is filled in the openings of the resist layer.
  • the pillar (A) can be easily produced by sintering.
  • the material of the substrate having the electrodes is not particularly limited, and metals, ceramics, silicon, resins, composite materials thereof and the like can be used.
  • a known method can be adopted for forming a resist layer having an opening portion on a substrate having an electrode.
  • the resin material used is not particularly limited as long as a mold having a desired pattern having an opening can be produced.
  • various dry films such as photoresist (photo-resist), polyimide, epoxy, and epoxy molding compound (EMC) can be used.
  • the resist layer may be removed after the pillar (A) is formed or the conductive pillar is formed, or may be left as a permanent film. When used as a permanent film, there is an advantage that the step of peeling the resin film can be reduced.
  • the method of filling the paste opening into the resist opening is not particularly limited, and squeegee, doctor blade, dispenser, inkjet, press injection, vacuum printing, pressing by pressurization, or the like can be used.
  • the method of filling the opening with the paste using a squeegee is adopted, there are no restrictions on the squeegee material, and a squeegee made of plastic, urethane rubber, other rubber, ceramic, metal, etc. can be used.
  • the thickness and length of the squeegee are not particularly limited.
  • the pressing during coating can be performed with a printing pressure that does not damage the opening pattern of the resist layer. Further, a metal mask or a mask for screen printing may be used.
  • the paste filling operation in the mold can be performed in an inert gas atmosphere or a reducing gas atmosphere.
  • the shape of the pillar to be produced is not particularly limited, and there is no particular limitation as long as a bonding layer can be provided at the tip of the pillar, but a cylinder or a polygonal pillar shape is preferable.
  • the firing temperature and firing time are not particularly limited as long as sufficient values can be obtained for the conductivity and bonding strength of the pillars, but preferably, the firing temperature is 150 to 350 ° C. and the firing time is 1 to 1.
  • the range is 60 minutes. More preferably, the firing temperature is in the range of 200 to 250 ° C. or less and the firing time is in the range of 5 to 15 minutes. If the paste according to the present invention is used, sufficient performance can be exhibited even when baking is performed for a short time. Further, if necessary, it is also possible to perform firing using a temperature profile, such as performing a temporary firing in which the solvent is volatilized at a low temperature and then performing a main firing in the range of 150 to 350 ° C.
  • the firing method for sintering the metal fine particles is not particularly limited as long as the metal fine particles are fused, and the firing method by heat such as a hot plate or a hot air oven, visible light, infrared light, or laser light is used. Plasma treatment such as irradiation, flash lamp, and hydrogen gas may be used.
  • the gas type used during sintering there are no particular restrictions on the gas type used during sintering.
  • a noble metal is used as the metal fine particles
  • sintering is possible not only in an inert gas environment such as nitrogen gas or argon gas but also in the atmosphere.
  • an inert gas such as nitrogen gas or argon gas.
  • a base metal is used for the metal fine particles
  • a forming gas containing hydrogen may be used, or a gas to which a reducing component such as formic acid is added may be used.
  • the shape of the upper part of the cross section is concave. It becomes a cup shape.
  • This cup shape has the effect of increasing the bonding strength of the pillars because (1) the bonding area between the pillars and the bonding layer can be increased. (2) When the linear expansion coefficients of the top chip and the bottom chip are different, distortion occurs in the horizontal direction with respect to the electrode substrate due to the heating / cooling cycle, but the bonding layer / pillar interface exists in the same direction as the strain direction. This has the effect of increasing the joint strength of the pillars. As a result, the effect of dramatically improving the adhesion and the joint strength at the time of the die shear test can be obtained. This effect cannot be realized by the conductive pillars produced by the plating method.
  • the prepared pillars are made by fusing copper particles that are finely packed in a mold and have a structure with voids. Therefore, unlike bulk metals, the stress between the base materials caused by the difference in the coefficient of thermal expansion Has the effect of being able to alleviate. Therefore, it has the effect of improving the durability during environmental tests such as the thermal shock test and improving the joint strength.
  • the conductive pillar (B) according to the present invention can be produced by forming a bonding layer at at least one tip of the pillar (A) produced by the above method (FIG. 1).
  • the conductive pillar (C) according to the present invention can also be manufactured in the same manner as the conductive pillar (B).
  • the conductive pillar (C) is different from the conductive pillar (B) in that it has an intermetallic compound layer at the interface between the pillar (A) and the bonding layer.
  • FIG. 2 shows the difference between the conductive pillars (B) and (C).
  • FIG. 2A shows a schematic view of a top view of the manufactured conductive pillar.
  • 2B and 2C are schematic cross-sectional views taken along the cross section shown by the broken line in FIG. 2A. Each configuration will be described in detail below.
  • solder alloy As the material of the bonding layer according to the present invention, Au, Ag, Cu, Sn, Ni, a solder alloy and the like can be used, and even if it is composed of only a single component, it is composed of a plurality of components. May be good.
  • a solder alloy can be more preferably used as the material of the bonding layer according to the present invention.
  • Sn—Ag alloy, Sn—Pb alloy, Sn—Bi alloy, Sn—Zn alloy, Sn—Sb alloy, Sn—Bi alloy, Sn—In alloy, Sn—Cu alloy, Sn with Au, Ag. , Bi, In and Cu, and alloys to which two elements selected from the group are added can be used.
  • a metal or alloy used for general bonding purposes can be used in addition to Sn, and it can also be used.
  • the material of the bonding layer according to the present invention a material containing no solvent and / or flux component can be more preferably used. If the bonding layer material contains a solvent or a flux component, it may be gasified during melting or reflowing and remain as voids in the bonding layer, resulting in a decrease in bonding strength.
  • the method for forming the bonding layer according to the present invention is not particularly limited as long as the bonding layer can be formed at at least one tip of a pillar made of metal fine particles.
  • the bonding layer can be formed at at least one tip of a pillar made of metal fine particles.
  • printing methods such as stencil mask method and dry film method, ball mounting method, thin film deposition method, IMS method, etc.
  • melting by melting (reflowing) the solder supplied to the tip of the pillar.
  • the IMS method can be more preferably used because the bonding layer can be produced at the tip of the pillar in the state where the bonding layer material is melted and no solvent or flux component is required.
  • the structure of the bonding layer is not particularly limited, and a multilayer structure in which two or more types of bonding layer materials are laminated may be used.
  • the bonding layer is formed at the tip of at least one of the pillars made of fine metal particles.
  • the intermetallic compound layer according to the present invention indicates an alloy layer formed between the pillar (A) and the bonding layer.
  • the composition of the intermetallic compound and its ratio are not particularly limited, and the composition ratio of the alloy varies depending on the metal type and the sintering conditions.
  • the intermetallic compound layer is formed by mutually diffusing the bonding material into the pillar (A) and the metal of the pillar (A) into the bonding material. Pillars made from metal fine particle paste are composed of metal fine particles and have a porous structure. The structure is maintained even when the metal fine particles are fused by sintering.
  • the molten bonding material invades the inside of the pores of the pillar (A) having a porous structure.
  • the impregnated bonding material forms intermetallic compounds with fine metal particles.
  • a material having a porous structure can form a uniform intermetallic compound layer more quickly than a bulk metal because of its large specific surface area.
  • This intermetallic compound layer is formed at the interface between the bonding layer and the pillar (A), and improves the bonding strength of the conductive pillar.
  • the intermetallic compound layer does not exist in parallel with the electrode substrate and has a concave shape. This concave shape improves the strength against the die shear test.
  • the conductive pillars are not particularly limited as long as the chips can be joined, but in order not to impair the conductivity, a cylindrical, triangular prism, or polygonal prism shape is used. It can be preferably used.
  • the diameter of the conductive pillar of the present invention can be calculated as follows.
  • the diameter of the "circle” which is the shape of the bottom surface of the pillar can be calculated as the diameter of the conductive pillar. it can.
  • the height of the "triangle" which is the shape of the bottom surface of the pillar should be calculated as the diameter of the conductive pillar. Can be done.
  • the conductive pillar has a polygonal pillar shape and the connecting surface between the pillar (A) and the electrode substrate is polygonal (excluding triangles), the most diagonal line of the "polygon" which is the shape of the bottom surface of the pillar.
  • the length of the long wire can be calculated as the diameter of the conductive pillar.
  • the aspect ratio of the conductive pillar is not particularly limited, but a conductive pillar having an aspect ratio of 0.5 or more can be preferably used.
  • the "height of the conductive pillar" means the height
  • the resist layer used as a mold in the pillars may be removed.
  • a known method can be used to remove the resist layer used for the mold from the substrate. It is also possible to leave the resist layer as a permanent film without removing it. When a permanent film is used, there is an advantage that the step of peeling the resin film can be reduced.
  • the conductive pillar of the present invention can be used as a mounting terminal for various electronic components / devices including flip chip mounting (Fig. 3).
  • this reaction mixture is circulated in a hollow fiber type ultrafiltration membrane module (HIT-1-FUS1582, 145 cm 2 , fractional molecular weight 150,000) manufactured by Daisen Membrane Systems, Inc., and the same amount as the exuding filtrate.
  • a 0.1% aqueous solution of hydrazine hydrate While adding a 0.1% aqueous solution of hydrazine hydrate, the mixture was circulated and purified until the filtrate from the ultrafiltration module became about 500 mL.
  • an aqueous dispersion of 2.85 g of a complex of a thioether type organic compound and copper fine particles was obtained.
  • the non-volatile content in the aqueous dispersion was 16%.
  • thermogravimetric analysis TG-DTA
  • TG-DTA thermogravimetric analysis
  • the obtained copper fine particles contained an organic substance containing a 3% polyethylene oxide structure.
  • the average primary particle size was measured by transmission electron microscopy (TEM) observation.
  • the prepared metal fine particles are diluted 100-fold with a good solvent (water, terpineol, 1-butanol or ethylene glycol), and the diluted solution is cast on a carbon film-coated grid, dried, and subjected to a transmission electron microscope (equipment). : TEMJEM-1400 (manufactured by JEOL), acceleration voltage: 120 kV).
  • 200 fine particles were randomly extracted from the obtained TEM image, the area of each fine particle was calculated, and the value calculated based on the number of particle size when converted into a true sphere was adopted.
  • the average primary particle diameter of the obtained copper fine particles was 20 nm.
  • the average primary particle size was measured in the same manner as described in Synthesis Example 1. When the obtained fine particles were observed with a transmission electron microscope (TEM), the average primary particle size of the fine particles was 6 nm.
  • TEM transmission electron microscope
  • the average primary particle size was measured in the same manner as described in Synthesis Example 1. When the obtained silver fine particles were observed with a transmission electron microscope (TEM), the average primary particle size of the silver fine particles was 17 nm.
  • TEM transmission electron microscope
  • the average primary particle size was measured in the same manner as described in Synthesis Example 1. When the obtained silver fine particles were observed with a transmission electron microscope (TEM), the average primary particle size of the silver fine particles was 25 nm.
  • TEM transmission electron microscope
  • the paste of this synthetic example is 8.26 g of copper powder (1100Y D50: 1.1 ⁇ m manufactured by Mitsui Metal Mine Co., Ltd.) and 0.190 g of TEGO (registered trademark) VARIPLUSSK (manufactured by Evonik Degussa Japan Co., Ltd.).
  • DISPER BYK-111 (Bick Chemie's phosphate group-containing polymer) 0.05 g, TRIXENE BI 7992 (Baxenden's) 0.660 g, and Denacol® EX-321 (Nagase Chemtex (registered trademark) (Manufactured by Co., Ltd.) 0.207 g, High Solve (registered trademark) MTEM (manufactured by Toho Kagaku Kogyo Co., Ltd.) 0.260 g, Diethylene glycol monobutyl ether acetate 0.323 g, and U-CAT SA 102 (Sun Appro) (Manufactured by Yasuda Seiki Co., Ltd.) was mixed with 0.050 g using an automatic Hoover Marler (manufactured by Yasuda Seiki Seisakusho Co., Ltd.) and dispersed.
  • the average primary particle size was measured in the same manner as described in Synthesis Example 1.
  • the average primary particle size of the copper fine particles was 1.2 ⁇ m.
  • Example 1 ⁇ Manufacturing conductive pillars> (Preparation of electrode substrate and mold) The method of manufacturing the electrode substrate used in the experiment will be described.
  • the substrate was prepared by the following procedure. Ti (thickness 50 nm) was sputtered on a 4-inch silicon wafer provided with an Al electrode, and then Cu (250 nm) was sputtered to prepare an electrode substrate. A resist resin was applied to the sputtered silicon substrate so that the final film thickness was 30 ⁇ m, and patterning was performed.
  • the shape of the resist pattern was a cylindrical shape, the diameter of the opening portion was 30 ⁇ m, and the depth of the opening portion was 30 ⁇ m.
  • the aspect ratio was designed to be 1.0.
  • the pillars were formed by embedding the adjusted paste in a resist opening provided in the prepared electrode substrate and sintering the paste.
  • the paste was filled using a urethane rubber squeegee for screen printing. Printing was done by hand and no printing mask was used. The printing speed at the time of filling was about 10 mm / s.
  • the paste prepared by the method described in Synthesis Example 1 was filled in an opening portion having a diameter of 30 ⁇ m with a urethane squeegee.
  • Example 2 (Example 2) ⁇ Manufacturing conductive pillars> (Preparation of electrode substrate and mold) An electrode substrate was produced in the same manner as in the method described in Example 1.
  • Pillar formation Pillars were formed in the same manner as in Example 1 using the paste prepared by the method described in Synthesis Example 2.
  • a bonding layer was prepared in the same manner as described in Example 1.
  • Example 3 (Preparation of electrode substrate and mold) An electrode substrate was produced in the same manner as in the method described in Example 1.
  • Pillar formation Pillars were formed in the same manner as in Example 1 using the paste prepared by the method described in Synthesis Example 3.
  • a bonding layer was prepared in the same manner as described in Example 1.
  • Example 4 ⁇ Manufacturing conductive pillars> (Preparation of electrode substrate and mold) An electrode substrate was produced in the same manner as in the method described in Example 1.
  • Pillar formation Pillars were formed in the same manner as in Example 1 using the paste prepared by the method described in Synthesis Example 4.
  • a bonding layer was prepared in the same manner as described in Example 1.
  • the electrode substrate used in the experiment was prepared by the following procedure.
  • An electrode substrate was prepared by providing a Ni layer on an Al electrode substrate provided on a 4-inch silicon wafer and laminating Au on the Al electrode substrate to a thickness of 4 ⁇ m by an electroless plating method.
  • the prepared electrode substrate was used in this experiment.
  • a resist resin was applied to a silicon substrate having an Au electrode so that the final film thickness was 30 ⁇ m, and patterning was performed.
  • the shape of the resist pattern was a cylindrical shape, the diameter of the opening portion was 30 ⁇ m, and the depth of the opening portion was 30 ⁇ m.
  • the aspect ratio was designed to be 1.0.
  • Pillar formation Pillars were formed in the same manner as in Example 1 using the paste prepared by the method described in Synthesis Example 1.
  • a bonding layer was prepared in the same manner as described in Example 1.
  • Pillar formation Pillars were formed in the same manner as in Example 1 using the paste prepared by the method described in Synthesis Example 5.
  • a bonding layer was prepared in the same manner as described in Example 1.
  • the prepared electrode substrate was immersed in 5 wt% sulfuric acid to perform a pretreatment for removing the oxide film of the seed layer. After the pretreatment, a copper plating solution consisting of 65 g / L of copper sulfate pentahydrate, 170 g / L of sulfuric acid, and 70 mg / L of sodium chloride was prepared. The prepared electrode substrate was immersed in a copper plating solution and polarized. The exposed cathode electrode surface of the pattern opening portion of the resist layer was plated with copper to prepare pillars. The prepared pillar was columnar, and the pillar height was 20 um.
  • a bonding layer was prepared in the same manner as described in Example 1.
  • Pillars were formed in the resist opening portion by a paste filling or plating method, and SAC305, which is a connecting layer, was formed at the tip of the pillars by the IMS method to obtain a conductive pillar.
  • the prepared conductive pillar had a pillar height (metal fine particle layer) of about 15 to 20 ⁇ m, an intermetallic compound layer of 1 to 5 ⁇ m, and a bonding layer of about 5 to 15 ⁇ m.
  • the resist thin film was removed and the bonding strength was measured. The results of the obtained joint strength measurement are shown in Table 1.
  • the evaluation criteria were as follows. ⁇ : Indicates that the maximum value of the shear strength of the produced conductive pillar is 150 MPa or more. ⁇ : Indicates that the maximum value of the shear strength of the produced conductive pillar is 80 MPa or more. ⁇ : Indicates that the maximum value of the shear strength of the produced conductive pillar is 50 MPa or more. X: Indicates that the maximum value of the shear strength of the produced conductive pillar is less than 50 MPa.
  • the pillars prepared in Examples 1 to 5 showed good bonding strength as compared with those of Comparative Example.
  • the conductive pillars prepared by using the copper paste prepared in Synthesis Example 1 showed very good results.
  • the conductive pillar in which the electrode substrate was made of Au showed a good share strength comparable to that of the copper-plated pillar described in Reference Example 1. It is considered that this is because the surface of the electrode substrate was not affected by oxidation and the bonding between the electrode and the conductive pillar was strengthened. Therefore, it is considered that removing the oxide film on the surface of the electrode substrate improves the bonding strength to the same extent as that described in Reference Example 1 in Examples 1 to 5, and the conductive pillar made of metal fine particles according to the present invention is industrially used. It shows that it can be done.
  • ⁇ Measurement of electrical resistance of conductive pillars The prepared top Si chip having a conductive pillar and the bottom Si chip having a copper electrode substrate were joined, and the electric resistance of the conductive pillar was measured by 4-terminal measurement.
  • the diameter of the conductive pillar used for the measurement was a cylindrical shape of 40 ⁇ m, and the height of the conductive pillar after chip assembly was 25 ⁇ m.
  • the resistance value was measured by joining 80 or 82 conductive pillars in series and measuring the electrical resistance (FIGS. 3 and 4). For the measurement, 16 wirings in which 80 or 82 conductive pillars were connected in series were measured. Based on the resistance value obtained by the measurement, the resistance value per conductive pillar was calculated. Table 2 shows the average value of these resistance values obtained by the measurement.
  • the pillars produced in Examples 1 to 5 showed a good resistance value, that is, conductivity as compared with those of Comparative Example.
  • the conductive pillars prepared by using the copper paste prepared in Synthesis Example 1 showed very good results. Even when compared with SAC305 of Comparative Example 2, the resistance value is about 1/10 to 1/5, which is sufficiently durable for practical use.
  • 80 or 82 conductive pillars were joined in series to evaluate the conductivity, but since this measurement method is possible, the conductive pillars of the present invention are chipped. It has few defects such as chips and has a good yield. In Comparative Example 1, measurement could not be performed due to disconnection.
  • the conductive pillar of the present invention has excellent shear strength and conductivity, and can be used as a terminal for mounting various electronic components and devices including a terminal for mounting a flip chip. Further, since the conductive pillar of the present invention can be manufactured without an etching step or a plating step, the environmental load at the time of manufacturing is small, and a fine structure can be obtained.

Abstract

Conductive pillars formed by electrolytic plating, which is a conventional method, suffer from the problem wherein it is difficult to finely form the pillars without being affected by undercut. Moreover, copper pillars in bulk have moduli of elasticity at least three times that of a solder material and have yield stresses at least eight times that of a solder material and thus suffer from the problem that a thermal stress generated during the bonding of a chip and a substrate cannot be sufficiently absorbed. The inventors have earnestly examined solutions to the problems and found a conductive pillar that contains metallic fine particles and includes a joining layer. The present invention is the conductive pillar that is usable as a flip-chip packaging terminal and shows special effect for the problems.

Description

導電性ピラーConductive pillars
　本発明は、半導体パッケージ内において、半導体チップとパッケージインターポーザの接続方式であるフリップチップ実装端子である、導電性ピラー（Ｐｉｌｌａｒ）に関する。本発明は、金属微粒子を含有するペーストを焼結することにより作製されるピラーであって、接合層を有する導電性ピラーである。 The present invention relates to a conductive pillar (Pillar), which is a flip chip mounting terminal that is a connection method between a semiconductor chip and a package interposer in a semiconductor package. The present invention is a pillar produced by sintering a paste containing metal fine particles, and is a conductive pillar having a bonding layer.
　半導体装置は、半導体チップ上に電子回路を製造し、半導体チップ上の電極と半導体パッケージ上の電極とを接続して製造される。従来、半導体チップ上の電極と半導体パッケージ上の電極との間は、金あるいは銅製のボンディングワイヤを用いて電気的に接続されていた。半導体チップと半導体パッケージの間の電気的な接続方法としてフリップチップ法が用いられている。フリップチップ法における代表的な接続方法として、金バンプやはんだバンプ法が知られている。 A semiconductor device is manufactured by manufacturing an electronic circuit on a semiconductor chip and connecting an electrode on the semiconductor chip and an electrode on a semiconductor package. Conventionally, an electrode on a semiconductor chip and an electrode on a semiconductor package have been electrically connected by using a bonding wire made of gold or copper. The flip chip method is used as an electrical connection method between a semiconductor chip and a semiconductor package. Gold bumps and solder bumps are known as typical connection methods in the flip chip method.
　高密度実装法として注目されるフリップチップ実装法は、多数のはんだバンプをウエハや基板に配置された金属製の電極パッド上に形成し、その上に半導体チップを搭載した後、加熱することにより、はんだバンプを溶融してチップ接合を行う方法である（特許文献１）。 The flip chip mounting method, which is attracting attention as a high-density mounting method, involves forming a large number of solder bumps on metal electrode pads arranged on a wafer or substrate, mounting a semiconductor chip on the electrode pads, and then heating the chips. , A method of melting solder bumps to perform chip bonding (Patent Document 1).
　フリップチップ実装法におけるはんだバンプの形成は、電解メッキによりバンプを形成する方法、ステンシルマスク法、ドライフィルム法などの印刷法、ボールマウント法、蒸着法、ＩＭＳ（インジェクション・モールデッド・ソルダー）法（特許文献２、３、４）などによってウエハや基板上に供給されたはんだを溶融（リフロー）することによりなされる。この際に、はんだに含まれる溶剤が溶融時にガス化してバンプ中にボイドとなって残留すると、接合強度等の低下を生じるため、ボイドの少ないはんだバンプが求められている。 The formation of solder bumps in the flip chip mounting method includes a method of forming bumps by electrolytic plating, a printing method such as a stencil mask method and a dry film method, a ball mounting method, a vapor deposition method, and an IMS (injection molded solder) method ( This is done by melting (reflowing) the solder supplied on the wafer or substrate according to Patent Documents 2, 3, 4) and the like. At this time, if the solvent contained in the solder is gasified at the time of melting and remains as voids in the bumps, the joint strength and the like are lowered. Therefore, solder bumps having few voids are required.
　はんだバンプ接合を用いた場合、はんだ材料は、耐熱性能が劣る、銅や銀と比較して体積抵抗率が高い、電流容量が小さい等の課題がある。これら課題を解決するための材料として、銅ピラーバンプが知られている。銅ピラーに用いられる金属材料としての銅は、耐熱性能、低い電気抵抗、高い電流容量、高いエレクトロマイグレーション耐性等の観点からも優れている（特許文献５）。 When solder bump bonding is used, the solder material has problems such as inferior heat resistance, high volume resistivity as compared with copper and silver, and small current capacity. Copper pillar bumps are known as materials for solving these problems. Copper as a metal material used for copper pillars is also excellent in terms of heat resistance, low electrical resistance, high current capacity, high electromigration resistance, and the like (Patent Document 5).
　これまで、銅ピラーは、シード層と呼ばれるメッキ下地層を電極パッド上に作製し、電解メッキにより形成していた。しかし電解メッキ工法は、シード層エッチング時のアンダーカットが課題であった。また、メッキ工法は設備導入コストが大きく、有害廃液による環境負荷も大きかった。 Until now, copper pillars have been formed by forming a plating base layer called a seed layer on the electrode pad and electroplating. However, the electrolytic plating method has a problem of undercutting when etching the seed layer. In addition, the plating method has a high equipment installation cost and a large environmental load due to harmful waste liquid.
　メッキ工法を用いずに銅ピラーを形成する方法として、金属粒子及びはんだを用いる方法が報告されている（特許文献６）。しかし、当該文献には、ピラーに用いることができる金属粒子の粒子径、導電性ペーストの組成についての詳細な記載はなく、本発明が達成しようとする効果を得ることはできなかった。 A method using metal particles and solder has been reported as a method for forming copper pillars without using the plating method (Patent Document 6). However, the document does not describe in detail the particle size of the metal particles that can be used for the pillars and the composition of the conductive paste, and the effect that the present invention aims to achieve could not be obtained.
特開２０１９－０２９４９７号公報Japanese Unexamined Patent Publication No. 2019-029497 特開２００７－２９４９５９号公報JP-A-2007-294959 特開２０１５－１０６６１７号公報JP-A-2015-106617 特開２０１８－１４４０８６号公報Japanese Unexamined Patent Publication No. 2018-1440886 特開２０１１－０２９６３６号公報Japanese Unexamined Patent Publication No. 2011-029636 ＵＳ９，８５９，２４１号公報US9,859,241
　電解メッキ技術を用いて基板上に銅ピラーを形成した場合、シード層と呼ばれるメッキ層を電極パッド上に作製する必要が生じるため、全面に導電性のシード層を設けねばならない。したがって、シード層エッチング時に銅ピラー自体も溶解することから、アンダーカットにより、微細なピラーを作製することが困難であるという課題があった。 When copper pillars are formed on a substrate using electroplating technology, it is necessary to form a plating layer called a seed layer on the electrode pad, so a conductive seed layer must be provided on the entire surface. Therefore, since the copper pillars themselves are also dissolved during the etching of the seed layer, there is a problem that it is difficult to produce fine pillars by undercutting.
　メッキ工法は、大量の廃液を再生又は処分する必要があり、環境負荷が大きく設備維持にコストも要するという課題があった。 The plating method has a problem that it is necessary to recycle or dispose of a large amount of waste liquid, which has a large environmental load and costs for equipment maintenance.
　メッキ方法等で作製したバルクの銅ピラーは、はんだ材料の弾性率に比べて３倍以上大きく、はんだ材料の降伏応力に比べて８倍以上大きいため、チップと基板を接合する際に生じる熱応力を十分に緩衝することができない課題があった。
　そのため、チップが熱応力の影響を大きく受けるようになり、機械的強度の弱い誘電率層間絶縁膜を採用する配線層にクラックが生じやすくなり歩留まりの低下を招いていた。 Bulk copper pillars produced by a plating method or the like are three times or more larger than the elastic modulus of the solder material and eight times or more larger than the yield stress of the solder material. Therefore, the thermal stress generated when the chip and the substrate are joined. There was a problem that could not be sufficiently buffered.
As a result, the chip is greatly affected by thermal stress, and cracks are likely to occur in the wiring layer that employs a dielectric constant interlayer insulating film with weak mechanical strength, resulting in a decrease in yield.
　文献６には、前記のように金属粒子を用いて導電性ピラーを作製する方法が開示されるが、導電性ピラーの組成については何ら記載されておらず、どのような組成を原料とすることで好適な導電性及び接合強度が得られるかについては不明であった。
　ここにおいて、金属粒子を用いて導電性ピラーの製造を行う場合、金属粒子の粒子径が大きいと微細な導電性ピラーを作製することができないという課題があった。 Document 6 discloses a method for producing a conductive pillar using metal particles as described above, but does not describe any composition of the conductive pillar, and what kind of composition is used as a raw material. It was unclear whether suitable conductivity and bonding strength could be obtained.
Here, when manufacturing a conductive pillar using metal particles, there is a problem that if the particle size of the metal particles is large, it is not possible to manufacture a fine conductive pillar.
　さらに、粒子径が１μｍを超える金属粒子を用いて導電性ピラーを作製する場合には、金属粒子同士の融着による接合機構を用いることができず、金属粒子同士を接合するためにバインダー樹脂を要し、耐熱性能が劣るという課題があった。 Further, when a conductive pillar is manufactured using metal particles having a particle diameter of more than 1 μm, a bonding mechanism by fusion of the metal particles cannot be used, and a binder resin is used to bond the metal particles. In short, there was a problem that the heat resistance performance was inferior.
　本発明者らは、前記諸課題を解決するために鋭意検討を重ねた結果、粒子径が１μｍ未満の金属微粒子と、保護剤と、を含有するペーストを焼結して作製したピラー（Ａ）と、接合層と、を有する導電性ピラー（Ｂ）を見出した。本発明は、フリップチップ実装用端子として用いられる導電性ピラーに関する。 As a result of diligent studies to solve the above problems, the present inventors have made a pillar (A) produced by sintering a paste containing metal fine particles having a particle size of less than 1 μm and a protective agent. And a conductive pillar (B) having a bonding layer. The present invention relates to a conductive pillar used as a terminal for mounting a flip chip.
　本発明に係るペーストを用いて電極基板上に導電性ピラーを形成することにより、導電性ピラーのメッキレス化を実現した。従来方法による課題であったエッチング時のアンダーカットを解決し、微細な銅ピラーの形成を可能とした。 By forming the conductive pillars on the electrode substrate using the paste according to the present invention, the conductive pillars have been made plating-less. The undercut during etching, which was a problem with the conventional method, has been solved, and fine copper pillars can be formed.
　本発明に係るペーストを用いて電極基板上に導電性ピラーを形成することにより、金属微粒子と接合層からなる導電性ピラーを作製することができた。得られた導電性ピラーは、導電性および接合強度が実装に耐えうる性能を有するものであった。 By forming a conductive pillar on the electrode substrate using the paste according to the present invention, it was possible to produce a conductive pillar composed of metal fine particles and a bonding layer. The obtained conductive pillars had the performance that the conductivity and the bonding strength could withstand the mounting.
　本発明に係る導電性ピラーに設けられた接合層を介して半導体パッケージの電極と接続でき、実装が可能となる。
以下に、本発明について具体的に記述する。 It can be connected to an electrode of a semiconductor package via a bonding layer provided on the conductive pillar according to the present invention, and can be mounted.
The present invention will be specifically described below.
（１）粒子径が１μｍ未満の金属微粒子と、保護剤と、を含有するペーストを焼結して作製したピラー（Ａ）と、接合層と、を有することを特徴とする導電性ピラー（Ｂ） (1) A conductive pillar (B) having a pillar (A) produced by sintering a paste containing metal fine particles having a particle diameter of less than 1 μm and a protective agent, and a bonding layer. )
（２）ピラー（Ａ）に含まれる保護剤が、アミノ基、カルボニル基、チオール基、アルキルチオ基、アルケニルチオ基、チオエーテル基、リン酸基のうち少なくとも一種以上の官能基を有し、かつ、分子量が５００以上の化合物であることを特徴とする（１）記載の導電性ピラー（Ｂ）。 (2) The protective agent contained in the pillar (A) has at least one functional group among amino group, carbonyl group, thiol group, alkylthio group, alkenylthio group, thioether group and phosphoric acid group, and The conductive pillar (B) according to (1), which is a compound having a molecular weight of 500 or more.
（３）ピラー（Ａ）に含まれる保護剤が、炭素数８～２００のポリエチレンオキシド構造を含む有機化合物であることを特徴とする（１）又は（２）記載の導電性ピラー（Ｂ）。 (3) The conductive pillar (B) according to (1) or (2), wherein the protective agent contained in the pillar (A) is an organic compound containing a polyethylene oxide structure having 8 to 200 carbon atoms.
（４）ピラー（Ａ）と、接合層と、の間に金属間化合物層を有することを特徴とする（１）から（３）のいずれかに記載の導電性ピラー。 (4) The conductive pillar according to any one of (1) to (3), wherein an intermetallic compound layer is provided between the pillar (A) and the bonding layer.
（５）接合層が、スズ、鉛、銀、銅又はこれらの内から選択される１種以上の金属を含有する合金であることを特徴とする（１）から（４）のいずれかに記載の導電性ピラー。　 (5) Described in any one of (1) to (4), wherein the bonding layer is an alloy containing tin, lead, silver, copper or one or more metals selected from these. Conductive pillars.
（６）粒子径が１μｍ未満の金属微粒子が、銀または銅から選択される１種以上の金属であることを特徴とする（１）から（５）のいずれかに記載の導電性ピラー。 (6) The conductive pillar according to any one of (1) to (5), wherein the metal fine particles having a particle diameter of less than 1 μm are one or more metals selected from silver or copper.
（７）導電性ピラーのアスペクト比が０．５以上であることを特徴とする（１）から（６）のいずれかに記載の導電性ピラー。 (7) The conductive pillar according to any one of (1) to (6), wherein the conductive pillar has an aspect ratio of 0.5 or more.
（８）フリップチップ実装用端子である（１）から（７）のいずれかに記載の導電性ピラー。 (8) The conductive pillar according to any one of (1) to (7), which is a terminal for mounting a flip chip.
　本発明は、フリップチップ実装に用いることができる、金属微粒子からなるピラーであって接合層を有する導電性ピラーである。
金属微粒子と保護剤を含有するペーストを用いて作製した導電性ピラーは、その製造工程において、従来技術であるメッキ技術を使用することなく、スキージ等であらかじめペーストをパターニングされたレジスト層の開口部分に充填させることでピラーを簡便に形成することができる。また、メッキ方法による課題であったエッチング時のアンダーカットを解決することができ、微細な銅ピラーの形成が可能となる。 The present invention is a pillar made of metal fine particles and a conductive pillar having a bonding layer, which can be used for flip chip mounting.
A conductive pillar made of a paste containing metal fine particles and a protective agent is an opening portion of a resist layer in which the paste is pre-patterned with a squeegee or the like without using the plating technique which is a conventional technique in the manufacturing process. Pillars can be easily formed by filling the paste. In addition, the undercut during etching, which has been a problem due to the plating method, can be solved, and fine copper pillars can be formed.
　本発明の導電性ピラーは、従来のメッキ方法が有していた課題も解決できる。 The conductive pillar of the present invention can solve the problems of the conventional plating method.
導電性ピラー（Ｂ）の模式図Schematic diagram of the conductive pillar (B) 導電性ピラー（Ｂ）及び（Ｃ）の上面図、及び導電性ピラー（Ｂ）、（Ｃ）それぞれの断面模式図Top view of the conductive pillars (B) and (C), and a schematic cross-sectional view of each of the conductive pillars (B) and (C). 導電性ピラー（Ｃ）を用いてフリップチップ実装をした際の断面の模式図Schematic diagram of cross section when flip-chip mounting using conductive pillar (C) 導電性ピラー（Ｃ）を用いてフリップチップ実装をした際の断面写真Cross-sectional photograph when flip-chip mounting using conductive pillar (C)
　以下、本発明を詳細に説明する。ここで単位「％」は、特に断りのない限りにおいて「質量パーセント濃度」である。 Hereinafter, the present invention will be described in detail. Here, the unit "%" is "mass percent concentration" unless otherwise specified.
＜金属微粒子＞
　本発明の金属微粒子として用いることができる金属種は、後述する保護剤中の官能基が、当該金属微粒子の表面に物理的又は化学的に吸着するか、化学的に結合（配位）できるものであれば特に制限されない。しかし、金属微粒子の安定性の観点から、金、銀、銅、ニッケルから選択される一種以上を好適に用いることができる。特に好ましくは、銀、銅である。金属種は一種類であっても、前記に列挙した金属を含んでいれば二種類以上の混合物、または、合金であっても良い。 <Metal particles>
The metal species that can be used as the metal fine particles of the present invention are those in which the functional groups in the protective agent described later can be physically or chemically adsorbed on the surface of the metal fine particles or chemically bonded (coordinated). If so, there is no particular limitation. However, from the viewpoint of the stability of the metal fine particles, one or more selected from gold, silver, copper and nickel can be preferably used. Particularly preferred are silver and copper. The metal type may be one kind, or may be a mixture of two or more kinds or an alloy as long as it contains the metals listed above.
　金属微粒子の粒子径は、充填性及び接合性の観点から、平均一次粒子径が１μｍ未満であることが好ましい。また、バインダー樹脂を用いず微粒子の融着機能を利用して導電性ピラーを作製する場合には、平均一次粒子径が１００ｎｍ以下の金属微粒子を用いることがより好ましい。これにより、レジスト開口部が１００μｍ未満となるようなレジスト開口部分にペーストを充填し導電性ピラーを形成する場合に、レジスト開口部へ密に金属微粒子を充填すること、電極／ピラー間の十分な接合強度を保つこと、金属微粒子間の接触又は接合による導電性を確保することができる。 The average primary particle size of the metal fine particles is preferably less than 1 μm from the viewpoint of filling property and bondability. Further, when a conductive pillar is produced by utilizing the fusion function of fine particles without using a binder resin, it is more preferable to use metal fine particles having an average primary particle diameter of 100 nm or less. As a result, when the resist opening is filled with paste so that the resist opening is less than 100 μm to form a conductive pillar, the resist opening is densely filled with metal fine particles, and the electrode / pillar is sufficiently connected. It is possible to maintain the bonding strength and ensure the conductivity due to the contact or bonding between the metal fine particles.
　金属の融着機能によりピラーを形成する場合には、バインダー樹脂の添加量を少なく又は添加せずにピラーを形成することができ、耐熱性にも優れたピラーを形成できる。
　金属微粒子の形状については、特に制限はなく、球状、フレーク状等の微粒子を本発明の効果を損なわない範囲で用いることができるが、平均一次粒子径の算出方法により算出される平均一次粒子径が１μｍ未満であることが好ましい。 When the pillars are formed by the fusion function of the metal, the pillars can be formed with or without the addition amount of the binder resin, and the pillars having excellent heat resistance can be formed.
The shape of the metal fine particles is not particularly limited, and spherical or flake-shaped fine particles can be used within a range that does not impair the effects of the present invention, but the average primary particle diameter calculated by the method for calculating the average primary particle diameter Is preferably less than 1 μm.
　平均一次粒子径は、透過型電子顕微鏡（ＴＥＭ）観察により算出することができる。すなわち、本明細書において、金属微粒子の平均一次粒子径は、透過型電子顕微鏡（ＴＥＭ）により試料の写真を撮影し、その画像を解析することにより算出する。 The average primary particle size can be calculated by observation with a transmission electron microscope (TEM). That is, in the present specification, the average primary particle diameter of the metal fine particles is calculated by taking a photograph of a sample with a transmission electron microscope (TEM) and analyzing the image.
　作製した金属微粒子を、良溶媒で任意の濃度に希釈し、その希釈液を、カーボン膜被覆グリッド上にキャストし、乾燥させ、透過型電子顕微鏡（ＴＥＭ）の観察用試料とする。
　平均一次粒子径は、得られたＴＥＭ像の中から無作為に微粒子を２００個抽出し、それぞれの面積を求め、真球に換算したときの粒子径を個数基準として算出した値を採用する。
　無作為に抽出される粒子からは、２個の粒子が重なったものは除外する。多数の粒子が、接触して、又は、二次凝集して、集合している場合には、集合を構成している粒子はそれぞれ独立した粒子であるものとして取り扱う。例えば、５個の一次粒子が接触又は二次凝集して１の集合を構成している場合、集合を構成する５個の粒子それぞれが金属微粒子の平均一次粒子径の算出対象となる。
　また、平均一次粒子径は、焼結前の値を採用する。すなわち、焼結されることにより融着が生じる前の値を採用する。 The prepared metal fine particles are diluted with a good solvent to an arbitrary concentration, and the diluted solution is cast on a carbon film-coated grid and dried to obtain a sample for observation with a transmission electron microscope (TEM).
For the average primary particle size, 200 fine particles are randomly extracted from the obtained TEM image, the area of each fine particle is obtained, and a value calculated based on the number of particle size when converted into a true sphere is adopted.
From the randomly selected particles, those in which two particles overlap are excluded. When a large number of particles are in contact with each other or secondarily aggregated and aggregated, the particles constituting the aggregate are treated as independent particles. For example, when five primary particles are contacted or secondarily aggregated to form one aggregate, each of the five particles constituting the aggregate is a target for calculating the average primary particle diameter of the metal fine particles.
Moreover, the value before sintering is adopted as the average primary particle diameter. That is, the value before fusion occurs due to sintering is adopted.
＜保護剤＞
　本発明の保護剤は、金属微粒子表面を保護剤により保護することができ、金属微粒子や分散媒との親和性を有する官能基及び／又は分子構造を有する化合物であれば特に制限はなく、例えば以下に示す官能基・分子構造を有する化合物を用いることができる。
　使用する保護剤は、分子量の大小にかかわらず使用することができ、使用する金属種や所望する物性に応じて保護剤を設計することで高導電性や分散安定性を金属微粒子に付与することが可能である。 <Protective agent>
The protective agent of the present invention is not particularly limited as long as it can protect the surface of the metal fine particles with the protective agent and has a functional group and / or a molecular structure having an affinity for the metal fine particles and the dispersion medium. Compounds having the following functional groups / molecular structures can be used.
The protective agent to be used can be used regardless of the size of the molecular weight, and high conductivity and dispersion stability can be imparted to the metal fine particles by designing the protective agent according to the metal type to be used and the desired physical properties. Is possible.
　種々の目的に応じて保護剤を選択することで金属微粒子の特性を自在に変更することができる。高分子量の保護剤を用いる場合は、化合物中の官能基の数及び種類を変更することで様々な特性を発現できる。低分子量の保護剤を用いる場合は、二種以上の化合物を併用することで様々な特性を発現できる。 The characteristics of metal fine particles can be freely changed by selecting a protective agent according to various purposes. When a high molecular weight protective agent is used, various properties can be exhibited by changing the number and types of functional groups in the compound. When a low molecular weight protective agent is used, various properties can be exhibited by using two or more compounds in combination.
　本発明の保護剤に含まれる官能基として、具体的には、チオール基、アルキルチオ基、アルケニルチオ基、カルボキシ基、アミノ基、ヒドロキシ基、リン酸基、リン酸エステル基、スルホン酸基、芳香族基が挙げられる。これら官能基を有する保護剤を使用することにより、微粒子に分散安定性を付加することができる。
　中でも、アルキルチオ基、アルケニルチオ基、リン酸エステル基、アミノ基、ヒドロキシ基を有する保護剤を使用することが好ましく、低温焼結した場合においてより低い体積抵抗率を発現する高導電性を付加することができる。 Specific examples of the functional group contained in the protective agent of the present invention include a thiol group, an alkylthio group, an alkenylthio group, a carboxy group, an amino group, a hydroxy group, a phosphoric acid group, a phosphoric acid ester group, a sulfonic acid group, and an aromatic group. The family group is mentioned. Dispersion stability can be added to the fine particles by using a protective agent having these functional groups.
Among them, it is preferable to use a protective agent having an alkylthio group, an alkenylthio group, a phosphoric acid ester group, an amino group and a hydroxy group, and adds high conductivity that exhibits lower volume resistivity when sintered at low temperature. be able to.
　保護剤に、カルボキシル基を有する低分子量の化合物を用いる場合、具体例として以下の物質を用いることができる。
　例えば、蟻酸、酢酸、プロピオン酸、酪酸、吉草酸、カプロン酸、エナント酸、カプリル酸、ペラルゴン酸、カプリン酸、ラウリン酸、ミリスチン酸、パルミチン酸、マルガリン酸、ステアリン酸、ベヘン酸、オレイン酸、パルミトオレイン酸、エイコセン酸、エルカ酸、ネルボン酸、リシノール酸、シュウ酸、マロン酸、コハク酸、グルタル酸、アジピン酸、ピメリン酸、スベリン酸、アゼライン酸、セバシン酸、ジグリコール酸、マレイン酸、イタコン酸、安息香酸、Ｎ－オレイルサルコシン、Ｎ－カルボベンゾキシ－４－アミノ酪酸、ｐ－クマル酸、３－（４－ヒドロキシフェニル）プロピオン酸、３－ヒドロキシミリスチン酸、２－ヒドロキシパルミチン酸、２－ヒドロキシイコサン酸、２－ヒドロキシドコサン酸、２－ヒドロキシトリコサン酸、２－ヒドロキシテトラコサン酸、３－ヒドロキシカプロン酸、３－ヒドロキシオクタン酸、３－ヒドロキシノナン酸、３－ヒドロキシデカン酸、３－ヒドロキシウンデカン酸、３－ヒドロキシドデカン酸、３－ヒドロキシトリデカン酸、３－ヒドロキシテトラデカン酸、３－ヒドロキシヘキサデカン酸、３－ヒドロキシヘプタデカン酸、３－ヒドロキシオクタデカン酸、１５－ヒドロキシペンタデカン酸、１７－ヒドロキシヘプタデカン酸、１５－ヒドロキシペンタデカン酸、１７－ヒドロキシヘプタデカン酸、ラウロイルサルコシン、６－アミノヘキサン酸、２－ベンゾイル安息香酸、１２－ヒドロキシステアリン酸、１２－ヒドロキシペンタデカン酸、２－ヒドロキシパルミチン酸、３－ヒドロキシデカン酸、１５－ヒドロキシペンタデカン酸、ラウロイルサルコシン、６－アミノヘキサン酸、Ｎ－（ｔｅｒｔ－ブトキシカルボニル）－６－アミノヘキサン酸、［２－（２－メトキシエトキシ）エトキシ］酢酸、Ｎ－カルボベンゾキシ－β－アラニン等を例示することができる。また、多量体を形成する化合物であれば、これらの二量体及び三量体から六量体までの多量体を用いても良い。また、１又は２以上のカルボン酸を任意の割合で組み合わせて用いることもできる。 When a low molecular weight compound having a carboxyl group is used as the protective agent, the following substances can be used as specific examples.
For example, formic acid, acetic acid, propionic acid, butyric acid, valeric acid, caproic acid, enanthic acid, capric acid, pelargonic acid, caproic acid, lauric acid, myristic acid, palmitic acid, margaric acid, stearic acid, bechenic acid, oleic acid, Palmitooleic acid, eicosenoic acid, erucic acid, nervonic acid, ricinoleic acid, oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, pimelli acid, suberic acid, azelaic acid, sebacic acid, diglycolic acid, maleic acid , Itaconic acid, benzoic acid, N-oleyl sarcosin, N-carbobenzoxi-4-aminobutyric acid, p-coumaric acid, 3- (4-hydroxyphenyl) propionic acid, 3-hydroxymyristic acid, 2-hydroxypalmitic acid , 2-Hydroxyicosanoic acid, 2-Hydroxydokosanoic acid, 2-Hydroxytricosanoic acid, 2-Hydroxytetracosanoic acid, 3-Hydroxycaproic acid, 3-Hydroxyoctanoic acid, 3-Hydroxynonanoic acid, 3-Hydroxy Decanoic acid, 3-hydroxyundecanoic acid, 3-hydroxydodecanoic acid, 3-hydroxytridecanoic acid, 3-hydroxytetradecanoic acid, 3-hydroxyhexadecanoic acid, 3-hydroxyheptadecanoic acid, 3-hydroxyoctadecanoic acid, 15-hydroxy Pentadecanoic acid, 17-hydroxyheptadecanoic acid, 15-hydroxypentadecanoic acid, 17-hydroxyheptadecanoic acid, lauroyl sarcosin, 6-aminocaproic acid, 2-benzoyl benzoic acid, 12-hydroxystearic acid, 12-hydroxypentadecanoic acid, 2-Hydroxypalmitic acid, 3-hydroxydecanoic acid, 15-hydroxypentadecanoic acid, lauroyl sarcosin, 6-aminocaproic acid, N- (tert-butoxycarbonyl) -6-aminocaproic acid, [2- (2-methoxyethoxy) ) Ethoxy] acetic acid, N-carbobenzoxi-β-alanine and the like can be exemplified. Further, as long as it is a compound forming a multimer, these dimers and multimers from a trimer to a hexamer may be used. Further, 1 or 2 or more carboxylic acids can be used in combination at any ratio.
　保護剤に、アミノ基を有する低分子量の化合物を用いる場合、具体例として以下の物質を用いることができる。
例えば、２－メトキシエチルアミン、２－エトキシエチルアミン、２－イソプロポキシエチルアミン、３－メトキシプロピルアミン、３－エトキシプロピルアミン、３－イソプロポキシプロピルアミン、３－（２－エチルヘキシルオキシ）プロピルアミン、Ｎ－メチルエチレンジアミン、Ｎ－エチルエチレンジアミン、Ｎ－イソプロピルエチレンジアミン、Ｎ－メチル－１，３－プロパンジアミン、３－イソプロピルアミノプロピルアミン、Ｎ，Ｎ－ジメチルエチレンジアミン、Ｎ，Ｎ－ジエチルエチレンジアミン、Ｎ，Ｎ－ジメチル－１，３－プロパンジアミン、Ｎ，Ｎ－ジエチル－１，３－プロパンジアミン、Ｎ－（３－アミノプロピル）モルホリン、Ｎ－（ｔｅｒｔ－ブトキシカルボニル）－１，４－ジアミノブタン、Ｎ－（ｔｅｒｔ－ブトキシカルボニル）－１，５－ジアミノペンタン、Ｎ－（ｔｅｒｔ－ブトキシカルボニル）－１，６－ジアミノヘキサン、２－（アミノエチルアミノ）エタノール、２－（アミノエトキシ）エタノール、３－（２－ヒドロキシエチルアミノ）プロピルアミン、Ｎ－（２－ヒドロキシプロピル）エチレンジアミン、Ｎ－（３－アミノプロピル）ジエタノールアミン等を例示することができる。この他に、アミン類として第二級アミン化合物、又は、第三級アミン化合物も併用することができる。 When a low molecular weight compound having an amino group is used as the protective agent, the following substances can be used as specific examples.
For example, 2-methoxyethylamine, 2-ethoxyethylamine, 2-isopropoxyethylamine, 3-methoxypropylamine, 3-ethoxypropylamine, 3-isopropoxypropylamine, 3- (2-ethylhexyloxy) propylamine, N- Methylethylenediamine, N-ethylethylenediamine, N-isopropylethylenediamine, N-methyl-1,3-propanediamine, 3-isopropylaminopropylamine, N, N-dimethylethylenediamine, N, N-diethylethylenediamine, N, N-dimethyl -1,3-propanediamine, N, N-diethyl-1,3-propanediamine, N- (3-aminopropyl) morpholine, N- (tert-butoxycarbonyl) -1,4-diaminobutane, N- ( tert-butoxycarbonyl) -1,5-diaminopentane, N- (tert-butoxycarbonyl) -1,6-diaminohexane, 2- (aminoethylamino) ethanol, 2- (aminoethoxy) ethanol, 3- (2) Examples thereof include -hydroxyethylamino) propylamine, N- (2-hydroxypropyl) ethylenediamine, and N- (3-aminopropyl) diethanolamine. In addition, secondary amine compounds or tertiary amine compounds can also be used in combination as amines.
　本発明の保護剤に、高分子量の保護剤を用いる場合、選択可能な分子構造としては、分散媒との親和性を有する任意の分子構造を採用することができる。例えば、分散媒がアルコール類や水などの極性溶媒である場合においては、炭素数８～２００のポリエチレンオキシド構造を含む有機化合物を好適に用いることができ、炭素数８～１００のポリエチレンオキシド構造を含む有機化合物をより好適に用いることができる。
当該保護剤のポリエチレンオキシド部位は、沸点が２５０℃以下のアルコール系溶媒との親和性に優れることから、金属微粒子の凝集を強く抑制でき、金属微粒子の高分散することができる。これにより、金属微粒子が高密度に充填されている状態となり、加熱処理による保護剤及び溶媒の分解除去に伴うボイド発生が起きず、高密度充填が可能となる。 When a high molecular weight protective agent is used as the protective agent of the present invention, any molecular structure having an affinity for the dispersion medium can be adopted as the selectable molecular structure. For example, when the dispersion medium is a polar solvent such as alcohols or water, an organic compound containing a polyethylene oxide structure having 8 to 200 carbon atoms can be preferably used, and a polyethylene oxide structure having 8 to 100 carbon atoms can be preferably used. The containing organic compound can be used more preferably.
Since the polyethylene oxide moiety of the protective agent has excellent affinity with an alcohol solvent having a boiling point of 250 ° C. or lower, aggregation of metal fine particles can be strongly suppressed, and metal fine particles can be highly dispersed. As a result, the metal fine particles are packed at a high density, and voids are not generated due to the decomposition and removal of the protective agent and the solvent by the heat treatment, and the high density filling is possible.
　本発明で用いられる炭素数８～２００のポリエチレンオキシド構造を含む有機化合物を含有する金属微粒子（有機化合物と金属微粒子の複合体）の例として、特許第４７８４８４７号公報、特開２０１３－６０６３７号公報又は特許第５０７７７２８号公報に記載の金属微粒子が挙げられ、これらに記載の方法で合成することができる。これらは、チオエーテル型（Ｒ－Ｓ－Ｒ’）有機化合物が金属微粒子表面に対して適切な親和吸着効果と、加熱による迅速な脱離性を有することが特徴となっており、低温融着特性を示す金属微粒子として開発されている。 As examples of metal fine particles (composite of organic compound and metal fine particles) containing an organic compound containing a polyethylene oxide structure having 8 to 200 carbon atoms used in the present invention, Japanese Patent No. 4784847 and Japanese Patent Application Laid-Open No. 2013-60637 Alternatively, the metal fine particles described in Japanese Patent No. 5077728 can be mentioned, and can be synthesized by the method described therein. These are characterized in that the thioether type (RSR') organic compound has an appropriate affinity adsorption effect on the surface of metal fine particles and a rapid desorption property by heating, and has low temperature fusion characteristics. It has been developed as a metal fine particle showing.
　他の例として、特開２０１０－２０９４２１号公報に記載のチオエーテル骨格を有する高分子化合物（チオエーテル型有機化合物）のうち、炭素数８～２００のポリエチレンオキシド部位を有する高分子化合物が複合した金属微粒子、さらには、特許第４６９７３５６号公報に記載のチオエーテル骨格を有しリン酸エステル基を有する高分子化合物のうち、炭素数８～２００のポリエチレンオキシド部位を有する高分子化合物が複合した金属微粒子などが挙げられる。これらのポリエチレンオキシド構造を含む高分子化合物の製造は、これら公報に記載の方法に従い行うことができる。
また、本発明においてこれらのポリエチレンオキシド構造を含むリン酸エステル型有機化合物は、チオエーテル骨格を有しリン酸エステル基をも有しており、これらの基を有することにより、金属微粒子表面に対して適切な親和吸着効果と、加熱による迅速な脱離性を付加することができる。 As another example, among the polymer compounds having a thioether skeleton (thioether type organic compound) described in JP-A-2010-209421, metal fine particles in which a polymer compound having a polyethylene oxide moiety having 8 to 200 carbon atoms is composited. Further, among the polymer compounds having a thioether skeleton and having a phosphoric acid ester group described in Japanese Patent No. 4697356, metal fine particles in which a polymer compound having a polyethylene oxide moiety having 8 to 200 carbon atoms is composited are included. Can be mentioned. The polymer compound containing these polyethylene oxide structures can be produced according to the methods described in these publications.
Further, in the present invention, the phosphoric acid ester type organic compound containing these polyethylene oxide structures has a thioether skeleton and also has a phosphoric acid ester group, and by having these groups, the surface of the metal fine particles is subjected to. Appropriate affinity adsorption effect and rapid desorption by heating can be added.
　ペースト中の保護剤濃度は、特に制限されるものではないが、焼結時の金属微粒子同士の融着のし易さ、導電性及び接合強度の向上の観点から１５％以下の範囲が好適であり、より好ましくは、１０％以下の範囲である。 The concentration of the protective agent in the paste is not particularly limited, but is preferably in the range of 15% or less from the viewpoint of easy fusion of metal fine particles during sintering, conductivity and improvement of bonding strength. Yes, more preferably in the range of 10% or less.
＜ペーストの製造方法＞
　本発明に係るペーストは、少なくとも金属微粒子と、保護剤と、から構成される。本発明に係るペーストは、金属微粒子表面を保護剤により保護することで作製できる。ペーストの作製は、任意の方法を採用することができる。
　例えば、湿式法として化学還元法の他に熱分解法、電気化学法や、乾式法としてガス中蒸発法、スパッタ法を採用することもできる。 <Paste manufacturing method>
The paste according to the present invention is composed of at least metal fine particles and a protective agent. The paste according to the present invention can be produced by protecting the surface of metal fine particles with a protective agent. Any method can be adopted for the preparation of the paste.
For example, in addition to the chemical reduction method, the thermal decomposition method and the electrochemical method can be adopted as the wet method, and the evaporation method in gas and the sputtering method can be adopted as the dry method.
　本発明の効果を説明するため、保護剤として炭素数８～２００のポリエチレンオキシド構造を含む有機化合物を使用した際のペーストの製造方法について説明する。
　前記製造方法の具体例を示すにあたり、金属種を銅及び／又は銀とした場合について記述する。
　炭素数８～２００のポリエチレンオキシド構造を含む有機化合物が複合した金属微粒子は、チオエーテル型有機化合物の存在下で、２価の銅イオン化合物又は１価の銀イオン化合物を溶媒と混合する工程と、銅イオン又は銀イオンを還元する工程と組み合わせることで容易に作製することが可能である。 In order to explain the effect of the present invention, a method for producing a paste when an organic compound containing a polyethylene oxide structure having 8 to 200 carbon atoms is used as a protective agent will be described.
In showing a specific example of the manufacturing method, a case where the metal type is copper and / or silver will be described.
The metal fine particles in which an organic compound containing a polyethylene oxide structure having 8 to 200 carbon atoms is composited are prepared by mixing a divalent copper ion compound or a monovalent silver ion compound with a solvent in the presence of a thioether type organic compound. It can be easily produced by combining with a step of reducing copper ions or silver ions.
　２価の銅イオン化合物としては、一般に入手可能な銅化合物が利用可能であり、硫酸塩、硝酸塩、カルボン酸塩、炭酸塩、塩化物、アセチルアセトナート錯体等を用いることができる。０価の銅微粒子との複合体を得る場合には、２価の化合物や、１価の化合物から製造してもよく、水分や結晶水を有していても良い。
　２価の銅イオン化合物として具体的には、ＣｕＳＯ４、Ｃｕ（ＮＯ３）２、Ｃｕ（ＯＡｃ）２、Ｃｕ（ＣＨ３ＣＨ２ＣＯＯ）２、Ｃｕ（ＨＣＯＯ）２、ＣｕＣＯ３、ＣｕＣｌ２、Ｃｕ２Ｏ、Ｃ５Ｈ７ＣｕＯ２、及びそれらの水和物等を使用することができる。また、前記塩類を加熱し、又は、塩基性雰囲気に曝す等により得られる塩基性塩たとえばＣｕ（ＯＡｃ）２・ＣｕＯ、Ｃｕ（ＯＡｃ）２・２ＣｕＯ、Ｃｕ２Ｃｌ（ＯＨ）３等を好適に用いることができる。
　これら塩基性塩は、反応系内で調製してもよいし、反応系外で別途調製したものを使用してもよい。また、アンモニアやアミン化合物を加えて錯体形成し、溶解度を確保してから還元に用いる一般的な方法も適用できる。 As the divalent copper ion compound, a generally available copper compound can be used, and sulfates, nitrates, carboxylates, carbonates, chlorides, acetylacetonate complexes and the like can be used. When a complex with zero-valent copper fine particles is obtained, it may be produced from a divalent compound or a monovalent compound, or may have water or water of crystallization.
Specifically, as the divalent copper ion compound, CuSO 4 , Cu (NO 3 ) 2 , Cu (OAc) 2 , Cu (CH 3 CH 2 COO) 2 , Cu (HCOO) 2 , CuCO 3 , CuCl 2 , Cu 2 O, C 5 H 7 CuO 2 , and their hydrates and the like can be used. Also, heating the salt, or a basic salt e.g. Cu (OAc) 2 · CuO obtained by such exposure to a basic atmosphere, Cu (OAc) 2 · 2CuO , Cu 2 Cl (OH) 3 or the like suitably the Can be used.
These basic salts may be prepared in the reaction system, or may be prepared separately outside the reaction system. Further, a general method of adding ammonia or an amine compound to form a complex to secure solubility and then using it for reduction can also be applied.
　１価の銀イオン化合物としては、一般的に入手可能な銀化合物が利用可能であり、硝酸銀、酸化銀、酢酸銀、フッ化銀、銀アセチルアセトナート、安息香酸銀、炭酸銀、クエン酸銀、銀ヘキサフルオロフォスフェート、乳酸銀、亜硝酸銀、ペンタフルオロプロピオン酸銀、それらの水和物等が挙げられ、取り扱い容易性、工業的入手容易性の観点から、硝酸銀または酸化銀を用いることが好ましい。 As the monovalent silver ion compound, generally available silver compounds can be used, such as silver nitrate, silver oxide, silver acetate, silver fluoride, silver acetylacetonate, silver benzoate, silver carbonate, and silver citrate. , Silver hexafluorophosphate, silver lactate, silver nitrite, silver pentafluoropropionate, hydrates thereof, etc., and silver nitrate or silver oxide can be used from the viewpoint of ease of handling and industrial availability. preferable.
　これらの銅及び／又は銀イオン化合物を、予めチオエーテル型有機化合物を溶解又は分散した溶媒に溶解、または混合する。このとき用いることができる溶媒としては、使用する有機化合物の構造にもよるが、エタノール、エチレングリコール、ジエチレングリコール、グリセリン等のアルコール類、水、アセトン等の極性溶媒、及び、それらの混合物が好適に用いることができる。なかでも、水－エチレングリコール混合物が特に好ましい。 These copper and / or silver ion compounds are dissolved or mixed in a solvent in which a thioether type organic compound is dissolved or dispersed in advance. The solvent that can be used at this time depends on the structure of the organic compound used, but alcohols such as ethanol, ethylene glycol, diethylene glycol and glycerin, polar solvents such as water and acetone, and mixtures thereof are preferable. Can be used. Of these, a water-ethylene glycol mixture is particularly preferred.
　チオエーテル型有機化合物の各種溶媒中における濃度としては、引き続き行なう還元反応の制御が容易になる点から、０．３～１０％の範囲に調整することが好ましい The concentration of the thioether-type organic compound in various solvents is preferably adjusted to the range of 0.3 to 10% from the viewpoint of facilitating the control of the subsequent reduction reaction.
　上記で調整した溶媒中に、銅及び／又は銀イオン化合物を、一括又は分割して添加し、混合する。難溶性溶媒を使用する場合には、予め少量の良溶媒に溶解させ、溶媒中に添加しても良い。 Copper and / or silver ion compounds are added collectively or separately to the solvent prepared above and mixed. When a poorly soluble solvent is used, it may be dissolved in a small amount of a good solvent in advance and added to the solvent.
　混合するチオエーテル型有機化合物と銅及び／又は銀イオン化合物の配合割合としては、反応溶媒中でのチオエーテル型有機化合物の保護能力に応じて適宜選択することができる。銅及び／又は銀イオン化合物１ｍｏｌ当たりチオエーテル型有機化合物として１ｍｍｏｌ～３０ｍｍｏｌの範囲で調製し、特に１５～３０ｍｍｏｌの範囲で用いることが好ましい。ここで、ポリエチレンオキシド構造を含むリン酸エステル型有機化合物を用いても同様に行うことができ、銅及び／又は銀イオン化合物１ｍｏｌあたりの有機化合物の使用量も前記と同様である。 The mixing ratio of the thioether-type organic compound to be mixed with the copper and / or silver ion compound can be appropriately selected according to the protective ability of the thioether-type organic compound in the reaction solvent. The thioether-type organic compound per 1 mol of the copper and / or silver ion compound is prepared in the range of 1 mmol to 30 mmol, and is particularly preferably used in the range of 15 to 30 mmol. Here, the same can be carried out by using a phosphoric acid ester type organic compound containing a polyethylene oxide structure, and the amount of the organic compound used per 1 mol of the copper and / or silver ion compound is also the same as described above.
　引き続き、銅及び／又は銀イオンの還元反応を各種還元剤により行なう。還元剤としては、ヒドラジン化合物、ヒドロキシルアミンおよびその誘導体、金属水素化物、ホスフィン酸塩類、アルデヒド類、エンジオール類、ヒドロキシケトン類など、氷冷温から８０℃以下の温度で銅及び／又は銀の還元反応を進行させることができるため、好適に用いることができる。 Subsequently, the reduction reaction of copper and / or silver ions is carried out with various reducing agents. Reducing agents include hydrazine compounds, hydroxylamines and derivatives thereof, metal hydrides, phosphinates, aldehydes, endiols, hydroxyketones, etc., and reduction of copper and / or silver at a temperature of 80 ° C. or lower from ice-cold temperature. Since the reaction can proceed, it can be preferably used.
　銅イオンの還元にはヒドラジン水和物、非対称ジメチルヒドラジン、ヒドロキシルアミン水溶液、水素化ホウ素ナトリウムなどの還元剤が好適である。これらの還元剤は、銅化合物を０価まで還元することができ、２価および１価の銅化合物を還元銅とし、有機化合物とナノ銅粒子との複合体を製造する場合に適している。 For the reduction of copper ions, reducing agents such as hydrazine hydrate, unsymmetrical dimethylhydrazine, aqueous hydroxylamine solution, and sodium borohydride are suitable. These reducing agents can reduce copper compounds to 0 valence, and are suitable for producing a composite of an organic compound and nano-copper particles by using divalent and monovalent copper compounds as reduced copper.
　還元反応の条件は、原料として用いる銅化合物、還元剤の種類、錯化の有無、溶媒、チオエーテル型有機化合物の種類に応じ、適宜設定することができる。例えば、水系溶媒で酢酸銅（ＩＩ）を水素化ホウ素ナトリウムで還元する場合には、氷冷程度の温度でも０価のナノ銅粒子が調製できる。一方、ヒドラジンを用いる場合には、室温では反応が遅く、６０℃程度に加熱してはじめて円滑な還元反応が起こる。またエチレングリコール／水系で酢酸銅を還元する場合には、６０℃で２時間程度の反応時間を要する。これら還元反応の結果、有機化合物と銅系微粒子との複合体を含む反応混合物が得られる。 The conditions of the reduction reaction can be appropriately set according to the copper compound used as a raw material, the type of reducing agent, the presence or absence of complexation, the solvent, and the type of the thioether type organic compound. For example, when copper (II) acetate is reduced with sodium borohydride in an aqueous solvent, zero-valent nanocopper particles can be prepared even at an ice-cooled temperature. On the other hand, when hydrazine is used, the reaction is slow at room temperature, and a smooth reduction reaction occurs only after heating to about 60 ° C. When reducing copper acetate in an ethylene glycol / aqueous system, a reaction time of about 2 hours is required at 60 ° C. As a result of these reduction reactions, a reaction mixture containing a complex of an organic compound and copper-based fine particles is obtained.
　このように調製した銅微粒子は、保護剤の効果により水分を完全に除去して乾燥体粉末とした後に、再び溶媒に分散させた場合にも乾燥前と同じように高分散させることが可能である。 The copper fine particles prepared in this way can be highly dispersed in the same manner as before drying even when the moisture is completely removed by the effect of the protective agent to obtain a dried body powder and then dispersed in the solvent again. is there.
　還元反応後は、必要に応じて金属化合物残渣、還元試薬残渣、余剰のポリエチレンオキシド構造を含む有機化合物等を除く工程が設けられる。複合体の精製は、再沈殿、遠心沈降または限外濾過などにより行うことができ、得られた複合体を含む反応混合物を水、エタノール、アセトンおよびこれらの混合物によって洗浄することで、前述の不純物を洗い流すことができる。 After the reduction reaction, a step of removing metal compound residue, reducing reagent residue, organic compound containing excess polyethylene oxide structure, etc. is provided as necessary. Purification of the complex can be carried out by reprecipitation, centrifugal sedimentation, ultrafiltration, etc., and the above-mentioned impurities are obtained by washing the reaction mixture containing the obtained complex with water, ethanol, acetone and a mixture thereof. Can be washed away.
　本発明に係るペーストは、本発明の効果を損なわせない範囲において、樹脂等のバインダー成分、乾燥防止剤、消泡剤、基材への密着付与剤、酸化防止剤、皮膜形成促進のための各種触媒、シリコーン系界面活性剤、フッ素系界面活性剤の様な各種界面活性剤、レベリング剤、離型促進剤等を助剤として添加することができる。 The paste according to the present invention is used for binder components such as resins, antidrying agents, antifoaming agents, adhesion imparting agents to substrates, antioxidants, and for promoting film formation, as long as the effects of the present invention are not impaired. Various catalysts, various surfactants such as silicone-based surfactants and fluorine-based surfactants, leveling agents, mold release accelerators and the like can be added as auxiliary agents.
　本発明に係るペースト中の金属微粒子の濃度は、後述する分散媒を添加することにより任意の濃度に調整することができる。分散媒は、ペースト合成時に添加することもできるし、合成後に添加することもできる。
　ペースト中の金属微粒子の濃度は、特に制限されるものではないが、ペーストの流動性及び開口部分への充填性能を考慮すると４０以上９５％未満の範囲が好ましく、より好ましくは６０～９０％の範囲である。 The concentration of the metal fine particles in the paste according to the present invention can be adjusted to an arbitrary concentration by adding a dispersion medium described later. The dispersion medium can be added at the time of paste synthesis or after synthesis.
The concentration of the metal fine particles in the paste is not particularly limited, but is preferably in the range of 40 or more and less than 95%, more preferably 60 to 90%, in consideration of the fluidity of the paste and the filling performance in the opening portion. The range.
＜分散媒＞
　本発明の金属微粒子と保護剤を含有するペーストには、発明の効果を損なわない範囲において分散媒となる水又は溶剤を添加することができる。分散媒は、基材への濡れ性付与や、ペースト中の金属微粒子の濃度を調整することを目的として添加できる。本発明で使用できる分散媒としては、焼結後にピラー内部に分散媒が残留しないことが望ましく、沸点２５０℃以下の化合物又は混合物を用いることが好ましい。 <Dispersion medium>
Water or a solvent as a dispersion medium can be added to the paste containing the metal fine particles and the protective agent of the present invention as long as the effects of the present invention are not impaired. The dispersion medium can be added for the purpose of imparting wettability to the base material and adjusting the concentration of metal fine particles in the paste. As the dispersion medium that can be used in the present invention, it is desirable that the dispersion medium does not remain inside the pillars after sintering, and it is preferable to use a compound or mixture having a boiling point of 250 ° C. or lower.
　分散媒は、沸点が２５０℃以下の化合物であれば、特に制限されることはなく、水又は／及び有機溶剤を分散媒として用いることが可能である。前記分散媒は、金属微粒子を凝集させない良分散媒を用いることが、均一な粒子径を有するペーストを製造する上で好ましい。 The dispersion medium is not particularly limited as long as it is a compound having a boiling point of 250 ° C. or lower, and water and / or an organic solvent can be used as the dispersion medium. As the dispersion medium, it is preferable to use a good dispersion medium that does not agglomerate metal fine particles in order to produce a paste having a uniform particle size.
　以下に、好適に用いることができる有機溶剤について例示列挙する。 The following are examples of organic solvents that can be preferably used.
　例えば、水酸基を含む有機溶剤としては、水、メタノール、エタノール、１－プロパノール、イソプロパノール、１－ブタノール、イソブタノール、ｓｅｃ－ブタノール、ｔｅｒｔ－ブタノール、アミルアルコール、ｔｅｒｔ－アミルアルコール、１－ヘキサノール、シクロヘキサノール、ベンジルアルコール、２－エチル－１－ブタノール、１－ヘプタノール、１－オクタノール、４－メチル－２－ペンタノール、ネオペンチルグリコール、プロピオニトリル、エチレングリコール、プロピレングリコール、１，３－ブタンジオール、１，４－ブタンジオール、２，３－ブタンジオール、イソブチレングリコール、２，２－ジメチル－１，３－ブタンジオール、２－メチル－１，３－ペンタンジオール、２－メチル－２，４－ペンタンジオール、ジエチレングリコール、トリエチレングリコール、テトラエチレングリコール、１，５－ペンタンジオール、２，４－ペンタンジオール、ジプロピレングリコール、２，５－ヘキサンジオール、グリセリン、ジエチレングリコールモノブチルエーテル、エチレングリコールモノベンジルエーテル、エチレングリコールモノエチルエーテル、エチレングリコールモノメチルエーテル、エチレングリコールモノフェニルエーテル、プロピレングリコールジメチルエーテル、ポリエチレングリコール、ポリプロピレングリコールなどを例示することができる。中でも、１－ブタノール、エタノール、１－プロパノール、エチレングリコール、グリセリン、水を好適に用いることができる。 For example, examples of the organic solvent containing a hydroxyl group include water, methanol, ethanol, 1-propanol, isopropanol, 1-butanol, isobutanol, sec-butanol, tert-butanol, amyl alcohol, tert-amyl alcohol, 1-hexanol, and cyclo. Hexanol, benzyl alcohol, 2-ethyl-1-butanol, 1-heptanol, 1-octanol, 4-methyl-2-pentanol, neopentyl glycol, propionitrile, ethylene glycol, propylene glycol, 1,3-butanediol , 1,4-Butanediol, 2,3-Butanediol, Isobutylene Glycol, 2,2-dimethyl-1,3-Butanediol, 2-Methyl-1,3-Pentanediol, 2-Methyl-2,4- Pentandiol, diethylene glycol, triethylene glycol, tetraethylene glycol, 1,5-pentanediol, 2,4-pentanediol, dipropylene glycol, 2,5-hexanediol, glycerin, diethylene glycol monobutyl ether, ethylene glycol monobenzyl ether, Examples thereof include ethylene glycol monoethyl ether, ethylene glycol monomethyl ether, ethylene glycol monophenyl ether, propylene glycol dimethyl ether, polyethylene glycol, and polypropylene glycol. Among them, 1-butanol, ethanol, 1-propanol, ethylene glycol, glycerin, and water can be preferably used.
　その他、水酸基を含まない有機溶剤として、アセトン、シクロペンタノン、シクロヘキサノン、アセトフェノン、アクリロニトリル、プロピオニトリル、ｎ－ブチロニトリル、イソブチロニトリル、γ－ブチロラクトン、ε－カプロラクト、プロピオラクトン、炭酸－２，３－ブチレン、炭酸エチレン、炭酸１，２－エチレン、炭酸ジメチル、炭酸エチレン、マロン酸ジメチル、乳酸エチル、安息香酸メチル、サリチル酸メチル、二酢酸エチレングリコール、ε－カプロラクタム、ジメチルスルホキシド、Ｎ，Ｎ－ジメチルホルムアミド、Ｎ，Ｎ－ジメチルアセトアミド、Ｎ－メチルホルムアミド、Ｎ－メチルアセトアミド、Ｎ－エチルアセトアミド、Ｎ，Ｎ－ジエチルホルムアミド、ホルムアミド、ピロリジン、１－メチル－２－ピロリジノン、ヘキサメチルリン酸トリアミド、ナフタレン、ケロシンを用いることができる。 Other organic solvents that do not contain hydroxyl groups include acetone, cyclopentanone, cyclohexanone, acetamide, acrylonitrile, propionitrile, n-butyronitrile, isobutyronitrile, γ-butyrolactone, ε-caprolacto, propiolactone, and carbon dioxide-2. , 3-butylene, ethylene carbonate, 1,2-ethylene carbonate, dimethyl carbonate, ethylene carbonate, dimethyl malonate, ethyl lactate, methyl benzoate, methyl salicylate, ethylene glycol diacetate, ε-caprolactam, dimethylsulfoxide, N, N -Dimethylformamide, N, N-dimethylacetamide, N-methylformamide, N-methylacetamide, N-ethylacetamide, N, N-diethylformamide, formamide, pyrrolidine, 1-methyl-2-pyrrolidinone, hexamethylphosphate triamide , Naphthalene, kerosine can be used.
（混合物の沸点測定方法）
　複数の溶媒を組み合わせた混合溶媒を分散媒として用いる場合、前記混合溶媒の沸点は、ＪＩＳ　Ｋ２２３３－１９８９「自動車用非鉱油系ブレーキ液」７．１に規定する「平衡還流沸点試験方法」に準じて測定することができる。 (Method of measuring boiling point of mixture)
When a mixed solvent in which a plurality of solvents are combined is used as the dispersion medium, the boiling point of the mixed solvent conforms to the "equilibrium reflux boiling point test method" specified in JIS K2233-1989 "Non-mineral oil-based brake fluid for automobiles" 7.1. Can be measured.
＜ピラー（Ａ）＞
　本発明におけるピラーは本発明の効果を奏する範囲において、その形状、径等について特に制限されるものではない。本発明のピラーは、チップ接合が安定となることから柱形状であることが好ましく、更に好ましくは略円柱状形状、特に好ましくは円柱形状である。また、本発明のピラーの径はチップ接合工程が効率的になることから、ピラー底面の径（後述）が１００μｍ以下であることが好ましく、更に好ましくは５０μｍ以下、特に好ましくは３０μｍ以下である。 <Pillar (A)>
The pillars in the present invention are not particularly limited in shape, diameter, etc. as long as the effects of the present invention are exhibited. The pillar of the present invention preferably has a columnar shape because the tip bonding is stable, more preferably a substantially columnar shape, and particularly preferably a columnar shape. Further, the diameter of the pillar of the present invention is preferably 100 μm or less, more preferably 50 μm or less, and particularly preferably 30 μm or less, because the chip joining step becomes efficient.
　本発明におけるピラーの形成方法については、特に制限されるものではないが、埋め込み方法によりピラーを形成する方法について、以下詳しく説明する。
　埋め込み方法によりピラーを形成するためには、電極部を有する基板上にレジスト層を形成し、レジスト層に開口部分を複数有するパターン（鋳型）を形成し、レジスト層の開口部分にペーストを充填し、焼結することでピラー（Ａ）を簡便に作製することができる。 The method for forming pillars in the present invention is not particularly limited, but a method for forming pillars by an embedding method will be described in detail below.
In order to form pillars by the embedding method, a resist layer is formed on a substrate having an electrode portion, a pattern (mold) having a plurality of openings is formed in the resist layer, and a paste is filled in the openings of the resist layer. The pillar (A) can be easily produced by sintering.
（電極を有する基板の材料）
　電極を有する基板の材料について、特に制限はなく、金属、セラミック、シリコン、樹脂、及びこれらの複合材料等を用いることができる。 (Material of substrate with electrodes)
The material of the substrate having the electrodes is not particularly limited, and metals, ceramics, silicon, resins, composite materials thereof and the like can be used.
（レジスト層の形成）
　開口部分を有するレジスト層を、電極を有する基板上に作製するのは、公知の手法を採用することができる。使用する樹脂の材料は、開口部分を有する所望のパターンの鋳型を製造することができれば特に制限されるものではない。例えば、フォトレジスト（ｐｈｏｔｏ－ｒｅｓｉｓｔ）、ポリイミド、エポキシ、エポキシモールディングコンパウンド（ｅｐｏｘｙ－ｍｏｌｄｉｎｇ　ｃｏｍｐｏｕｎｄ：ＥＭＣ）など、各種ドライフィルムを用いることができる。レジスト層は、ピラー（Ａ）形成後、又は導電性ピラー形成後に除去しても良いし、永久膜として残存させておくこともできる。永久膜として用いる場合には、樹脂膜を剥離する工程を削減することができるという利点がある。 (Formation of resist layer)
A known method can be adopted for forming a resist layer having an opening portion on a substrate having an electrode. The resin material used is not particularly limited as long as a mold having a desired pattern having an opening can be produced. For example, various dry films such as photoresist (photo-resist), polyimide, epoxy, and epoxy molding compound (EMC) can be used. The resist layer may be removed after the pillar (A) is formed or the conductive pillar is formed, or may be left as a permanent film. When used as a permanent film, there is an advantage that the step of peeling the resin film can be reduced.
（ペーストの充填）
　レジスト開口部分へのペースト充填方法としては、特に制限されるものではなく、スキージ、ドクターブレード、ディスペンサ、インクジェット、プレス注入、真空印刷、加圧による押込み等を用いることができる。 (Paste filling)
The method of filling the paste opening into the resist opening is not particularly limited, and squeegee, doctor blade, dispenser, inkjet, press injection, vacuum printing, pressing by pressurization, or the like can be used.
　例えば、スキージを用いて開口部分にペーストを充填する方法を採用した場合、スキージ素材についての制限はなく、プラスチック、ウレタンゴム、その他ゴム、セラミック、金属製等のスキージを用いることができる。スキージの厚さ、長さについても特に制限されるものではない。塗布時の押し込みは、レジスト層の開口部分パターンを破損させない程度の印圧で行うことができる。また、メタルマスクやスクリーン印刷用のマスクを使用してもよい。 For example, when the method of filling the opening with the paste using a squeegee is adopted, there are no restrictions on the squeegee material, and a squeegee made of plastic, urethane rubber, other rubber, ceramic, metal, etc. can be used. The thickness and length of the squeegee are not particularly limited. The pressing during coating can be performed with a printing pressure that does not damage the opening pattern of the resist layer. Further, a metal mask or a mask for screen printing may be used.
　酸化しやすい金属微粒子を材料に用いてピラーを作製する場合には、不活性ガス雰囲気下又は還元性ガス雰囲気下で、鋳型へのペースト充填操作を行うことができる。 When making pillars using metal fine particles that are easily oxidized as a material, the paste filling operation in the mold can be performed in an inert gas atmosphere or a reducing gas atmosphere.
　作製するピラーの形状については、特に制限はなく、ピラーの先端部に接合層を設けることができれば特に制限はないが、円柱や、多角柱形状が好適である。 The shape of the pillar to be produced is not particularly limited, and there is no particular limitation as long as a bonding layer can be provided at the tip of the pillar, but a cylinder or a polygonal pillar shape is preferable.
（ピラーの焼結）
　本発明に係るペーストは、金属微粒子が融着する温度にまで加熱をすることで、粒子間で融着が生じ、導電性が発現する。金属微粒子が融着する温度は、使用する金属種、保護剤や溶媒種によって異なる。金属微粒子が融着する温度は、熱重量分析（ＴＧ－ＤＴＡ）や示差走査熱量計（ＤＳＣ）を用いて測定することができる。 (Sintering of pillars)
When the paste according to the present invention is heated to a temperature at which the metal fine particles are fused, fusion occurs between the particles and conductivity is exhibited. The temperature at which the metal fine particles are fused depends on the metal type used, the protective agent and the solvent type. The temperature at which the metal fine particles are fused can be measured using a thermogravimetric analysis (TG-DTA) or a differential scanning calorimetry (DSC).
　ピラーの導電性及び接合強度について十分な値が得られる範囲であれば、焼成温度及び焼成時間に特に制限されるものではないが、好ましくは、焼成温度が１５０～３５０℃かつ焼成時間が１～６０分間の範囲である。より好ましくは、焼成温度が２００～２５０℃以下かつ焼成時間が５～１５分間、の範囲である。本発明に係るペーストを使用すれば、短時間焼成を行った場合であっても十分な性能を発揮することができる。
　また、必要に応じて、低温で溶媒を揮発させる仮焼成を行った後、１５０～３５０℃の範囲で本焼成を行う等の、温度プロファイルを用いて焼成を行うこともできる。
　金属微粒子を焼結させる焼成方法としては金属微粒子の融着が生じる限りにおいて特に制限されるものではなく、ホットプレートや熱風オーブンをはじめとする熱による焼成や可視光、赤外光又はレーザー光の照射、フラッシュランプ、水素ガスをはじめとするプラズマ処理を用いても良い。 The firing temperature and firing time are not particularly limited as long as sufficient values can be obtained for the conductivity and bonding strength of the pillars, but preferably, the firing temperature is 150 to 350 ° C. and the firing time is 1 to 1. The range is 60 minutes. More preferably, the firing temperature is in the range of 200 to 250 ° C. or less and the firing time is in the range of 5 to 15 minutes. If the paste according to the present invention is used, sufficient performance can be exhibited even when baking is performed for a short time.
Further, if necessary, it is also possible to perform firing using a temperature profile, such as performing a temporary firing in which the solvent is volatilized at a low temperature and then performing a main firing in the range of 150 to 350 ° C.
The firing method for sintering the metal fine particles is not particularly limited as long as the metal fine particles are fused, and the firing method by heat such as a hot plate or a hot air oven, visible light, infrared light, or laser light is used. Plasma treatment such as irradiation, flash lamp, and hydrogen gas may be used.
　焼結時に使用するガス種については特に制限はない。金属微粒子に貴金属を用いる場合には、窒素ガスやアルゴンガスなどの不活性ガス環境下に限らず大気中での焼結も可能である。金属微粒子に卑金属を用いる場合、窒素ガスやアルゴンガスをはじめとする不活性ガスを用いることが好ましい。また、金属微粒子に卑金属を用いる場合には、水素を含有したフォーミングガスを使用しても良いし、蟻酸などの還元成分を添加したガスを用いても良い。 There are no particular restrictions on the gas type used during sintering. When a noble metal is used as the metal fine particles, sintering is possible not only in an inert gas environment such as nitrogen gas or argon gas but also in the atmosphere. When a base metal is used for the metal fine particles, it is preferable to use an inert gas such as nitrogen gas or argon gas. When a base metal is used for the metal fine particles, a forming gas containing hydrogen may be used, or a gas to which a reducing component such as formic acid is added may be used.
　本発明のペーストをレジスト層に設けた開口部分に充填し、ペーストを焼結することより、保護剤、溶媒等が蒸発し、また融着により体積が減少した結果、断面上部の形状が凹型のカップ形状になる。このカップ形状は、（１）ピラーと接合層との接合面積を増加させることができるためピラーの接合強度を増加させる効果がある。また、（２）トップチップとボトムチップの線膨張係数が異なる場合、加熱・冷却のサイクルにより電極基板に対して水平方向に歪が生じるが、歪方向と同一方向に接合層／ピラー界面が存在しないためピラーの接合強度を増加させる効果がある。これにより密着性及びダイシェア試験時の接合強度が飛躍的に向上する効果が得られる。この効果は、メッキ法で作製した導電性ピラーでは実現し得ないものである。 By filling the openings provided in the resist layer with the paste of the present invention and sintering the paste, the protective agent, solvent, etc. evaporate, and as a result of the volume being reduced by fusion, the shape of the upper part of the cross section is concave. It becomes a cup shape. This cup shape has the effect of increasing the bonding strength of the pillars because (1) the bonding area between the pillars and the bonding layer can be increased. (2) When the linear expansion coefficients of the top chip and the bottom chip are different, distortion occurs in the horizontal direction with respect to the electrode substrate due to the heating / cooling cycle, but the bonding layer / pillar interface exists in the same direction as the strain direction. This has the effect of increasing the joint strength of the pillars. As a result, the effect of dramatically improving the adhesion and the joint strength at the time of the die shear test can be obtained. This effect cannot be realized by the conductive pillars produced by the plating method.
　作製したピラーは、鋳型に細密充填された銅粒子が融着したものであり、空隙を有する構造をしていることから、バルク金属とは異なり、熱膨張率の差から生じる基材間の応力を緩和できるという効果を有する。そのため、冷熱衝撃試験をはじめとする環境試験時の耐久性が向上するとともに、接合強度が向上する効果を有する。 Unlike bulk metals, the prepared pillars are made by fusing copper particles that are finely packed in a mold and have a structure with voids. Therefore, unlike bulk metals, the stress between the base materials caused by the difference in the coefficient of thermal expansion Has the effect of being able to alleviate. Therefore, it has the effect of improving the durability during environmental tests such as the thermal shock test and improving the joint strength.
＜導電性ピラーの作製＞
　本発明に係る導電性ピラー（Ｂ）は、上記方法により作製したピラー（Ａ）の少なくとも一方の先端部に接合層を形成することにより作製することができる（図１）。
本発明に係る導電性ピラー（Ｃ）も、導電性ピラー（Ｂ）と同様にして作製することができる。導電性ピラー（Ｃ）は、ピラー（Ａ）と、接合層と、の界面に金属間化合物層を有している点が導電性ピラー（Ｂ）と異なる。図２に導電性ピラー（Ｂ）と（Ｃ）の違いを示した。図２Ａは、作製した導電性ピラーの上面図の模式図を示すものである。図２Ｂ及びＣは、図２Ａの破線で示す断面での断面図の模式図である。
以下、各構成について詳しく述べる。 <Manufacturing conductive pillars>
The conductive pillar (B) according to the present invention can be produced by forming a bonding layer at at least one tip of the pillar (A) produced by the above method (FIG. 1).
The conductive pillar (C) according to the present invention can also be manufactured in the same manner as the conductive pillar (B). The conductive pillar (C) is different from the conductive pillar (B) in that it has an intermetallic compound layer at the interface between the pillar (A) and the bonding layer. FIG. 2 shows the difference between the conductive pillars (B) and (C). FIG. 2A shows a schematic view of a top view of the manufactured conductive pillar. 2B and 2C are schematic cross-sectional views taken along the cross section shown by the broken line in FIG. 2A.
Each configuration will be described in detail below.
＜接合層＞
　本発明に係る接合層の材料としては、Ａｕ、Ａｇ、Ｃｕ、Ｓｎ、Ｎｉ、はんだ合金等を用いることができ、単一の成分のみで構成されていても、複数の成分から構成されていてもよい。
　本発明に係る接合層の材料としては、はんだ合金をより好適に用いることができる。はんだ合金としては、Ｓｎ－Ａｇ合金、Ｓｎ－Ｐｂ合金、Ｓｎ－Ｂｉ合金、Ｓｎ－Ｚｎ合金、Ｓｎ－Ｓｂ合金、Ｓｎ－Ｂｉ合金、Ｓｎ－Ｉｎ合金、Ｓｎ－Ｃｕ合金、ＳｎにＡｕ、Ａｇ、Ｂｉ、Ｉｎ及びＣｕからなる群より選ばれる２つの元素を添加した合金等を用いることができる。また、はんだ合金には、Ｓｎ以外にも一般的な接合目的で利用される金属または合金を用いることができる、使用することもできる。 <Joint layer>
As the material of the bonding layer according to the present invention, Au, Ag, Cu, Sn, Ni, a solder alloy and the like can be used, and even if it is composed of only a single component, it is composed of a plurality of components. May be good.
A solder alloy can be more preferably used as the material of the bonding layer according to the present invention. As the solder alloy, Sn—Ag alloy, Sn—Pb alloy, Sn—Bi alloy, Sn—Zn alloy, Sn—Sb alloy, Sn—Bi alloy, Sn—In alloy, Sn—Cu alloy, Sn with Au, Ag. , Bi, In and Cu, and alloys to which two elements selected from the group are added can be used. Further, as the solder alloy, a metal or alloy used for general bonding purposes can be used in addition to Sn, and it can also be used.
　本発明に係る接合層の材料としては、溶剤及び／又はフラックス成分を含まない材料をより好適に用いることができる。
　接合層材料に溶剤やフラックス成分が含まれている場合、溶融時やリフロー時にガス化して接合層中にボイドとなって残留するおそれがあり、接合強度の低下を生じさせる。 As the material of the bonding layer according to the present invention, a material containing no solvent and / or flux component can be more preferably used.
If the bonding layer material contains a solvent or a flux component, it may be gasified during melting or reflowing and remain as voids in the bonding layer, resulting in a decrease in bonding strength.
　本発明にかかる接合層を形成する方法は、金属微粒子からなるピラーの少なくとも一方の先端部に接合層を形成することができれば特に限定されない。例えば、電解メッキによりバンプを形成する方法、ステンシルマスク法・ドライフィルム法などの印刷法、ボールマウント法、蒸着法、ＩＭＳ法等によってピラー先端部に供給されたはんだを溶融（リフロー）することにより形成できる。
　中でも、接合層材料を溶融させた状態で、ピラー先端部に接合層を作製でき、かつ、溶剤やフラックス成分を必要としないことからＩＭＳ法をより好適に用いることができる。 The method for forming the bonding layer according to the present invention is not particularly limited as long as the bonding layer can be formed at at least one tip of a pillar made of metal fine particles. For example, by forming bumps by electroplating, printing methods such as stencil mask method and dry film method, ball mounting method, thin film deposition method, IMS method, etc., by melting (reflowing) the solder supplied to the tip of the pillar. Can be formed.
Above all, the IMS method can be more preferably used because the bonding layer can be produced at the tip of the pillar in the state where the bonding layer material is melted and no solvent or flux component is required.
　接合層の構造は特に限定されるものではなく、二種以上の接合層の材料が積層された多層構造としてもよい。接合層は、金属微粒子からなるピラーの少なくとも一方の先端部に形成される。 The structure of the bonding layer is not particularly limited, and a multilayer structure in which two or more types of bonding layer materials are laminated may be used. The bonding layer is formed at the tip of at least one of the pillars made of fine metal particles.
＜金属間化合物層＞
　本発明に係る金属間化合物層は、ピラー（Ａ）と、接合層と、の間に形成される合金層のことを示している。金属間化合物の組成及びその比率については特に限定されるものではなく、金属種、焼結条件により合金の組成比率は変化する。
　金属間化合物層は、接合材料がピラー（Ａ）内部へ、ピラー（Ａ）の金属が接合材料内部へ、相互に拡散することにより形成される。
　金属微粒子ペーストから作製されるピラーは、金属微粒子から構成されており、多孔質構造を有する。当該構造は、金属微粒子が焼結により融着した場合であっても、維持される。
　作製されたピラーに接合層を設ける際、溶融した接合材料が、多孔質構造を有するピラー（Ａ）の細孔内部へと含侵する。含侵した接合材料は、金属微粒子と金属間化合物を形成する。
　多孔質構造を有する材料は、その比表面積の大きさゆえ、バルク金属と比較して、素早く、また、均一な金属間化合物層を形成できる。
　この金属間化合物層は、接合層とピラー（Ａ）との界面に形成され、導電性ピラーの接合強度を向上させる。加えて、この金属間化合物層は図２Ｃ及び図４に示すように電極基板と平行に存在せず、凹型形状をしている。この凹型形状が、ダイシェア試験に対する強度を向上させている。 <Intermetallic compound layer>
The intermetallic compound layer according to the present invention indicates an alloy layer formed between the pillar (A) and the bonding layer. The composition of the intermetallic compound and its ratio are not particularly limited, and the composition ratio of the alloy varies depending on the metal type and the sintering conditions.
The intermetallic compound layer is formed by mutually diffusing the bonding material into the pillar (A) and the metal of the pillar (A) into the bonding material.
Pillars made from metal fine particle paste are composed of metal fine particles and have a porous structure. The structure is maintained even when the metal fine particles are fused by sintering.
When the bonding layer is provided on the produced pillar, the molten bonding material invades the inside of the pores of the pillar (A) having a porous structure. The impregnated bonding material forms intermetallic compounds with fine metal particles.
A material having a porous structure can form a uniform intermetallic compound layer more quickly than a bulk metal because of its large specific surface area.
This intermetallic compound layer is formed at the interface between the bonding layer and the pillar (A), and improves the bonding strength of the conductive pillar. In addition, as shown in FIGS. 2C and 4, the intermetallic compound layer does not exist in parallel with the electrode substrate and has a concave shape. This concave shape improves the strength against the die shear test.
＜導電性ピラー（Ｂ、Ｃ）の形状、径及びアスペクト比の算出方法＞
（導電性ピラーの形状）
　導電性ピラー（Ｂ）又は（Ｃ）の形状について、導電性ピラーはチップ間を接合できれば、特に制限されるものではないが、導電性を損なわないために、円柱、三角柱、又は多角柱形状を好適に用いることができる。 <Calculation method of shape, diameter and aspect ratio of conductive pillars (B, C)>
(Shape of conductive pillar)
Regarding the shape of the conductive pillars (B) or (C), the conductive pillars are not particularly limited as long as the chips can be joined, but in order not to impair the conductivity, a cylindrical, triangular prism, or polygonal prism shape is used. It can be preferably used.
（導電性ピラーの径の算出方法）
　本発明の導電性ピラーの径は、以下のとおりにして算出することができる。
導電性ピラーが円柱形状であって、ピラー（Ａ）と電極基板との接続面が円であるときは、ピラー底面の形状である「円」の直径を導電性ピラーの径として算出することができる。
　導電性ピラーが三角柱形状であって、ピラー（Ａ）と電極基板との接続面が三角形であるときは、ピラー底面の形状である「三角形」の高さを導電性ピラーの径として算出することができる。
　導電性ピラーが多角柱形状であって、ピラー（Ａ）と電極基板との接続面が多角形であるとき（三角形を除く）は、ピラー底面の形状である「多角形」の対角線のうち最も長い線の長さを導電性ピラーの径として算出することができる。 (Method of calculating the diameter of conductive pillars)
The diameter of the conductive pillar of the present invention can be calculated as follows.
When the conductive pillar has a cylindrical shape and the connecting surface between the pillar (A) and the electrode substrate is a circle, the diameter of the "circle" which is the shape of the bottom surface of the pillar can be calculated as the diameter of the conductive pillar. it can.
When the conductive pillar has a triangular prism shape and the connecting surface between the pillar (A) and the electrode substrate is triangular, the height of the "triangle" which is the shape of the bottom surface of the pillar should be calculated as the diameter of the conductive pillar. Can be done.
When the conductive pillar has a polygonal pillar shape and the connecting surface between the pillar (A) and the electrode substrate is polygonal (excluding triangles), the most diagonal line of the "polygon" which is the shape of the bottom surface of the pillar. The length of the long wire can be calculated as the diameter of the conductive pillar.
（導電性ピラーのアスペクト比の算出方法）
　導電性ピラーのアスペクト比について、特に制限されるものではないが、アスペクト比０．５以上の導電性ピラーを好適に用いることができる。
　導電性ピラーが円柱形状であって、ピラー（Ａ）と電極基板との接続面が円であるときのアスペクト比は、
［アスペクト比］＝［導電性ピラーの高さ］／［円の直径］
　導電性ピラーが三角柱形状であって、ピラー（Ａ）と電極基板との接続面が三角形であるときのアスペクト比は、
［アスペクト比］＝［導電性ピラーの高さ］／［三角形の高さ］
　導電性ピラーが多角柱形状であって、ピラー（Ａ）と電極基板との接続面が多角形であるときのアスペクト比は、
［アスペクト比］＝［導電性ピラーの高さ］／［多角形の対角線のうち最も長い線の長さ］
で算出することができる。
　「導電性ピラーの高さ」とは、接合層を含んだ高さをいい、ピラー（Ａ）と電極基板との接続面から垂直方向に伸ばした線のうち、最も長い長線の長さを採用する。 (Calculation method of aspect ratio of conductive pillars)
The aspect ratio of the conductive pillar is not particularly limited, but a conductive pillar having an aspect ratio of 0.5 or more can be preferably used.
The aspect ratio when the conductive pillar has a cylindrical shape and the connecting surface between the pillar (A) and the electrode substrate is circular is
[Aspect ratio] = [Height of conductive pillars] / [Diameter of circle]
The aspect ratio when the conductive pillar has a triangular prism shape and the connecting surface between the pillar (A) and the electrode substrate is triangular is
[Aspect ratio] = [Height of conductive pillar] / [Height of triangle]
The aspect ratio when the conductive pillar has a polygonal prism shape and the connecting surface between the pillar (A) and the electrode substrate is polygonal is
[Aspect ratio] = [Height of conductive pillar] / [Length of the longest diagonal line of polygon]
Can be calculated with.
The "height of the conductive pillar" means the height including the bonding layer, and the length of the longest long wire among the lines extending in the vertical direction from the connection surface between the pillar (A) and the electrode substrate is adopted. To do.
＜レジスト層の剥離＞
　導電性ピラー作製後、ピラー作製の際に鋳型として用いたレジスト層を除去してもよい。鋳型に用いたレジスト層を基板上から除去するためには、公知の手法を用いることができる。
　レジスト層を除去せずに永久膜として残存させておくこともできる。永久膜とする場合には、樹脂膜を剥離する工程を削減することができるという利点がある。 <Peeling of resist layer>
After the conductive pillars are manufactured, the resist layer used as a mold in the pillars may be removed. A known method can be used to remove the resist layer used for the mold from the substrate.
It is also possible to leave the resist layer as a permanent film without removing it. When a permanent film is used, there is an advantage that the step of peeling the resin film can be reduced.
　本発明の導電性ピラーは、フリップチップ実装をはじめとする種々の電子部品・デバイスの実装用端子として用いることができる（図３）。 The conductive pillar of the present invention can be used as a mounting terminal for various electronic components / devices including flip chip mounting (Fig. 3).
　以下、実施例により本発明を具体的に説明する。ここで「％」は、特に指定がない限り「質量パーセント濃度」である。 Hereinafter, the present invention will be specifically described with reference to Examples. Here, "%" is a "mass percent concentration" unless otherwise specified.
（合成例１）
＜分散体の合成＞
　酢酸銅（ＩＩ）一水和物（３．００ｇ、１５．０ｍｍｏｌ）（東京化成工業社製）、エチル３－（３－（メトキシ（ポリエトキシ）エトキシ）－２－ヒドロキシプロピルスルファニル）プロピオナート〔ポリエチレングリコールメチルグリシジルエーテル（ポリエチレングリコール鎖の分子量２０００（炭素数９１））への３－メルカプトプロピオン酸エチルの付加化合物〕（０．４５１ｇ）、およびエチレングリコール（１０ｍＬ）（関東化学社製）からなる混合物に、窒素を５０ｍＬ／分の流量で吹き込みながら加熱し、１２５℃で２時間通気攪拌して脱気した。この混合物を室温に戻し、ヒドラジン水和物（１．５０ｇ、３０．０ｍｍｏｌ）（東京化成工業社製）を水７ｍＬで希釈した溶液を、シリンジポンプを用いてゆっくり滴下した。約１／４量を２時間かけてゆっくり滴下し、ここで一旦滴下を停止し、２時間攪拌して発泡が沈静化するのを確認した後、残量を更に１時間かけて滴下した。得られた褐色の溶液を６０℃に昇温して、さらに２時間攪拌し、還元反応を終結させた。 (Synthesis Example 1)
<Synthesis of dispersion>
Copper (II) acetate monohydrate (3.00 g, 15.0 mmol) (manufactured by Tokyo Kasei Kogyo Co., Ltd.), ethyl 3- (3- (methoxy (polyethoxy) ethoxy) -2-hydroxypropylsulfanyl) propionate [polyethylene glycol] In a mixture consisting of methyl glycidyl ether (addition compound of ethyl 3-mercaptopropionate to polyethylene glycol chain molecular weight 2000 (carbon number 91)) (0.451 g) and ethylene glycol (10 mL) (manufactured by Kanto Chemical Co., Ltd.) , Nitrogen was heated while being blown at a flow rate of 50 mL / min, and aerated and stirred at 125 ° C. for 2 hours to degas. The mixture was returned to room temperature, and a solution of hydrazine hydrate (1.50 g, 30.0 mmol) (manufactured by Tokyo Chemical Industry Co., Ltd.) diluted with 7 mL of water was slowly added dropwise using a syringe pump. About 1/4 of the amount was slowly added dropwise over 2 hours, the addition was stopped once, and the mixture was stirred for 2 hours to confirm that the foaming had subsided, and then the remaining amount was further added down over 1 hour. The temperature of the obtained brown solution was raised to 60 ° C., and the mixture was further stirred for 2 hours to terminate the reduction reaction.
　つづいて、この反応混合物をダイセン・メンブレン・システムズ社製の中空糸型限外濾過膜モジュール（ＨＩＴ－１－ＦＵＳ１５８２、１４５ｃｍ２、分画分子量１５万）中に循環させ、滲出する濾液と同量の０．１％ヒドラジン水和物水溶液を加えながら、限外濾過モジュールからの濾液が約５００ｍＬとなるまで循環させて精製した。０．１％ヒドラジン水和物水溶液の供給を止め、そのまま限外濾過法により濃縮すると、２．８５ｇのチオエーテル型有機化合物と銅微粒子との複合体の水分散液が得られた。水分散液中の不揮発物含量は１６％であった。 Subsequently, this reaction mixture is circulated in a hollow fiber type ultrafiltration membrane module (HIT-1-FUS1582, 145 cm 2 , fractional molecular weight 150,000) manufactured by Daisen Membrane Systems, Inc., and the same amount as the exuding filtrate. While adding a 0.1% aqueous solution of hydrazine hydrate, the mixture was circulated and purified until the filtrate from the ultrafiltration module became about 500 mL. When the supply of the 0.1% hydrazine hydrate aqueous solution was stopped and concentrated by the ultrafiltration method as it was, an aqueous dispersion of 2.85 g of a complex of a thioether type organic compound and copper fine particles was obtained. The non-volatile content in the aqueous dispersion was 16%.
＜ペーストの調製＞
　上記の水分散液５ｍＬをそれぞれ５０ｍＬ三口フラスコに封入し、ウォーターバスを用いて４０℃に加温を行いながら、減圧下、窒素を５ｍＬ／分の流速で流すことで、水を完全に除去し、銅微粒子複合体乾燥粉末１．０ｇを得た。
　得られた乾燥粉末に窒素バブリングしたエチレングリコールを添加した。添加後、乳鉢で１０分間混合することで金属微粒子含有率７０％のペーストを作製した。また、表面張力を調整するためにフッ素系レベリング剤ＭＥＧＡＦＡＣＥ（ＤＩＣ社製）を添加した。 <Preparation of paste>
Water is completely removed by encapsulating 5 mL of each of the above aqueous dispersions in a 50 mL three-necked flask and flowing nitrogen at a flow rate of 5 mL / min under reduced pressure while heating to 40 ° C. using a water bath. , 1.0 g of dry powder of copper fine particle composite was obtained.
Nitrogen bubbling ethylene glycol was added to the obtained dry powder. After the addition, the paste was mixed in a mortar for 10 minutes to prepare a paste having a metal fine particle content of 70%. In addition, a fluorine-based leveling agent MEGAFACE (manufactured by DIC Corporation) was added to adjust the surface tension.
＜熱重量分析（ＴＧ－ＤＴＡ）による重量減少率の測定＞
　合成した銅微粒子複合体乾燥粉末２～２５ｍｇを熱重量分析用アルミパンに精密にはかり、ＥＸＳＴＡＲ　ＴＧ／ＤＴＡ６３００型示差熱重量分析装置（エスアイアイ・ナノテクノロジー株式会社製）に載せ、不活性ガス雰囲気下において、室温～６００℃まで毎分１０℃の割合で昇温して、１００℃～６００℃の重量減少率を測定した。前記重量減少率より有機物の含有率を計算した。 <Measurement of weight loss rate by thermogravimetric analysis (TG-DTA)>
Precisely weigh 2 to 25 mg of the synthesized dry powder of copper fine particle composite on an aluminum pan for thermogravimetric analysis and place it on an EXSTAR TG / DTA6300 type differential thermal weight analyzer (manufactured by SII Nanotechnology Co., Ltd.) to create an inert gas atmosphere. Underneath, the temperature was raised from room temperature to 600 ° C. at a rate of 10 ° C. The organic matter content was calculated from the weight loss rate.
　ＴＧ－ＤＴＡ測定による重量減少より、得られた銅微粒子には３％のポリエチレンオキシド構造を含む有機物が存在することを確認した。 From the weight reduction by TG-DTA measurement, it was confirmed that the obtained copper fine particles contained an organic substance containing a 3% polyethylene oxide structure.
＜平均一次粒子径の測定＞
　平均一次粒子径は、透過型電子顕微鏡（ＴＥＭ）観察により測定した。作製した金属微粒子を、良溶媒（水、テルピネオール、１－ブタノール又はエチレングリコール）で１００倍に希釈し、その希釈液を、カーボン膜被覆グリッド上にキャストし、乾燥させ、透過型電子顕微鏡（装置：ＴＥＭＪＥＭ－１４００（ＪＥＯＬ製）、加速電圧：１２０ｋＶ）にて観察した。
　平均一次粒子径は、得られたＴＥＭ像の中から無作為に微粒子を２００個抽出し、それぞれの面積を求め、真球に換算したときの粒子径を個数基準として算出した値を採用した。 <Measurement of average primary particle size>
The average primary particle size was measured by transmission electron microscopy (TEM) observation. The prepared metal fine particles are diluted 100-fold with a good solvent (water, terpineol, 1-butanol or ethylene glycol), and the diluted solution is cast on a carbon film-coated grid, dried, and subjected to a transmission electron microscope (equipment). : TEMJEM-1400 (manufactured by JEOL), acceleration voltage: 120 kV).
For the average primary particle size, 200 fine particles were randomly extracted from the obtained TEM image, the area of each fine particle was calculated, and the value calculated based on the number of particle size when converted into a true sphere was adopted.
　得られた銅微粒子を透過型電子顕微鏡（ＴＥＭ）により観察すると、得られた銅微粒子の平均一次粒子径は２０ｎｍであった。 When the obtained copper fine particles were observed with a transmission electron microscope (TEM), the average primary particle diameter of the obtained copper fine particles was 20 nm.
（合成例２）
＜分散体の合成＞
　硝酸銅（東京化成工業社製）５．６ｇ、保護剤としてオクチルアミン（東京化成工業社製）９．２ｇ、リノール酸（東京化成工業社製）２．１ｇをトリメチルペンタン（東京化成工業社製）１Ｌに加え、攪拌混合し溶解した。この混合溶液に、０．０１ｍｏｌ／Ｌの水素化ホウ素ナトリウム（東京化成工業社製）を含むプロパノール（東京化成工業社製）溶液１Ｌを１時間かけて滴下し銅を還元した。さらに、３時間攪拌して黒色の液体を得た。得られた黒色の液体をエバポレーターによって濃縮した後、これにメタノール２Ｌを加えて褐色の沈殿物を生成させた後、吸引ろ過により沈殿物を回収した。生成した沈殿物をトリメチルペンタンに再分散させ、ろ過した後、乾燥させて、銅微粒子を黒色の固体として、銅微粒子乾燥粉末１．０ｇを得た。 (Synthesis Example 2)
<Synthesis of dispersion>
Copper nitrate (manufactured by Tokyo Kasei Kogyo Co., Ltd.) 5.6 g, octylamine (manufactured by Tokyo Kasei Kogyo Co., Ltd.) 9.2 g as a protective agent, linoleic acid (manufactured by Tokyo Kasei Kogyo Co., Ltd.) 2.1 g, trimethylpentane (manufactured by Tokyo Chemical Industry Co., Ltd.) ) Add to 1 L, stir and mix to dissolve. To this mixed solution, 1 L of a propanol (manufactured by Tokyo Chemical Industry Co., Ltd.) solution containing 0.01 mol / L sodium borohydride (manufactured by Tokyo Chemical Industry Co., Ltd.) was added dropwise over 1 hour to reduce copper. Further, the mixture was stirred for 3 hours to obtain a black liquid. The obtained black liquid was concentrated by an evaporator, and then 2 L of methanol was added thereto to form a brown precipitate, and then the precipitate was collected by suction filtration. The produced precipitate was redispersed in trimethylpentane, filtered, and then dried to obtain 1.0 g of dry copper fine particle powder as a black solid.
＜ペーストの調製＞
　得られた乾燥粉末に窒素バブリングしたテルピネオール（和光純薬工業製）を添加した。添加後、乳鉢で１０分間混合することで金属微粒子含有率７０％のペーストを作製した。また、表面張力を調整するためにフッ素系レベリング剤ＭＥＧＡＦＡＣＥ（ＤＩＣ社製）を添加した。 <Preparation of paste>
Nitrogen bubbling terpineol (manufactured by Wako Pure Chemical Industries, Ltd.) was added to the obtained dry powder. After the addition, the paste was mixed in a mortar for 10 minutes to prepare a paste having a metal fine particle content of 70%. In addition, a fluorine-based leveling agent MEGAFACE (manufactured by DIC Corporation) was added to adjust the surface tension.
＜熱重量分析（ＴＧ－ＤＴＡ）による重量減少率の測定＞
　合成例１記載の方法と同様にして、ＴＧ－ＤＴＡによる重量減少率の測定を行った。ＴＧ－ＤＴＡ測定による重量減少より、得られた銅微粒子には２．２％の有機物が存在していたことを確認した。 <Measurement of weight loss rate by thermogravimetric analysis (TG-DTA)>
The weight loss rate was measured by TG-DTA in the same manner as in the method described in Synthesis Example 1. From the weight reduction by TG-DTA measurement, it was confirmed that 2.2% of organic matter was present in the obtained copper fine particles.
＜平均一次粒子径の測定＞
　合成例１記載の方法と同様にして、平均一次粒子径の測定を行った。得られた微粒子を透過型電子顕微鏡（ＴＥＭ）により観察すると、微粒子の平均一次粒子径は６ｎｍであった。 <Measurement of average primary particle size>
The average primary particle size was measured in the same manner as described in Synthesis Example 1. When the obtained fine particles were observed with a transmission electron microscope (TEM), the average primary particle size of the fine particles was 6 nm.
（合成例３）
＜分散体の合成＞
　アルゴンガス雰囲気下で１Ｌフラスコに、Ｎ，Ｎ－ジメチルエチレンジアミン（東京化成工業社製）１５３．２ｇ（１．７３８ｍｏｌ）、３－（２－エチルヘキシルオキシ）プロピルアミン（東京化成工業社製）３２５．６ｇ（１．７３８ｍｏｌ）を添加後、この混合液の内温が３０℃になるまでオイルバスで加熱攪拌した。加熱攪拌下、シュウ酸銀（松田産業社製）３５．２ｇ（０．１１６ｍｏｌ）を添加して、内温が４０℃になるまで加熱攪拌した。１時間加熱攪拌を維持した後、フラスコ上部を開放し、オイルバスを９５℃まで昇温した。シュウ酸銀とアミンの熱分解により反応液が９０－９７℃まで上昇することを確認後、フラスコをオイルバスから外し、アルゴンガス雰囲気下で反応液の内温が４０℃以下になるまで冷却し、銀微粒子分散体を得た。
　過剰なアミンを銀微粒子分散体から除去するために、Ｎ－ヘキサン（関東化学社製）によりデカンテーションを実施し、銀微粒子分散体を洗浄した。デカンテーション後、銀微粒子分散体約２２ｇを得た。 (Synthesis Example 3)
<Synthesis of dispersion>
In a 1 L flask under an argon gas atmosphere, 153.2 g (1.738 mol) of N, N-dimethylethylenediamine (manufactured by Tokyo Chemical Industry Co., Ltd.), 3- (2-ethylhexyloxy) propylamine (manufactured by Tokyo Chemical Industry Co., Ltd.) 325. After adding 6 g (1.738 mol), the mixture was heated and stirred in an oil bath until the internal temperature of the mixed solution reached 30 ° C. Under heating and stirring, 35.2 g (0.116 mol) of silver oxalate (manufactured by Matsuda Sangyo Co., Ltd.) was added, and the mixture was heated and stirred until the internal temperature reached 40 ° C. After maintaining heating and stirring for 1 hour, the upper part of the flask was opened and the temperature of the oil bath was raised to 95 ° C. After confirming that the reaction solution rises to 90-97 ° C. due to thermal decomposition of silver oxalate and amine, remove the flask from the oil bath and cool the reaction solution in an argon gas atmosphere until the internal temperature of the reaction solution drops to 40 ° C. or lower. , Silver fine particle dispersion was obtained.
In order to remove excess amine from the silver fine particle dispersion, decantation was carried out with N-hexane (manufactured by Kanto Chemical Co., Inc.) to wash the silver fine particle dispersion. After decantation, about 22 g of a silver fine particle dispersion was obtained.
＜ペーストの調製＞
　上記合成により得られた銀微粒子分散体に、銀に対して２．０％になるように、リシノール酸（東京化成工業社製）を加えた１－ブタノール（関東化学社製）混合液を、銀濃度が７０％になるように添加した。０．５時間程度攪拌し、深い青色のペーストを得た。また、表面張力を調整するためにフッ素系レベリング剤ＭＥＧＡＦＡＣＥを添加した。 <Preparation of paste>
A mixed solution of 1-butanol (manufactured by Kanto Chemical Co., Inc.) in which ricinoleic acid (manufactured by Tokyo Chemical Industry Co., Ltd.) was added to the silver fine particle dispersion obtained by the above synthesis so as to be 2.0% with respect to silver. It was added so that the silver concentration became 70%. Stirring for about 0.5 hour gave a deep blue paste. In addition, a fluorine-based leveling agent MEGAFACE was added to adjust the surface tension.
＜熱重量分析（ＴＧ－ＤＴＡ）による重量減少率の測定＞
　合成例１記載の方法と同様にして、ＴＧ－ＤＴＡによる重量減少率の測定を行った。ＴＧ－ＤＴＡ測定による重量減少より、得られた銀微粒子には４．１％の有機物が存在していたことを確認した。 <Measurement of weight loss rate by thermogravimetric analysis (TG-DTA)>
The weight loss rate was measured by TG-DTA in the same manner as in the method described in Synthesis Example 1. From the weight reduction by TG-DTA measurement, it was confirmed that 4.1% of organic matter was present in the obtained silver fine particles.
＜平均一次粒子径の測定＞
　合成例１記載の方法と同様にして、平均一次粒子径の測定を行った。得られた銀微粒子を透過型電子顕微鏡（ＴＥＭ）により観察すると、銀微粒子の平均一次粒子径は１７ｎｍであった。 <Measurement of average primary particle size>
The average primary particle size was measured in the same manner as described in Synthesis Example 1. When the obtained silver fine particles were observed with a transmission electron microscope (TEM), the average primary particle size of the silver fine particles was 17 nm.
（合成例４）
＜分散体の合成＞
　末端にｐ－トルエンスルホニルオキシ基を有するメトキシポリエチレングリコール化合物５．３９ｇ（２．５ｍｍｏｌ）、分岐状ポリエチレンイミン（アルドリッチ社製、分子量２５，０００）を２０．０ｇ（０．８ｍｍｏｌ）、炭酸カリウム０．０７ｇ及びＮ，Ｎ－ジメチルアセトアミド１００ｍｌを、窒素雰囲気下、１００℃で６時間攪拌した。得られた反応混合物に酢酸エチルとヘキサンの混合溶液（Ｖ／Ｖ＝１／２）３００ｍｌを加え、室温で強力攪拌した後、生成物の固形物を濾過した。その固形物を酢酸エチルとヘキサンの混合溶液（Ｖ／Ｖ＝１／２）１００ｍｌを用いて２回繰り返し洗浄した後、減圧乾燥して、分岐状ポリエチレンイミンにポリエチレングリコールが結合した高分子化合物の固体を２４．４ｇ得た。 (Synthesis Example 4)
<Synthesis of dispersion>
5.39 g (2.5 mmol) of a methoxypolyethylene glycol compound having a p-toluenesulfonyloxy group at the end, 20.0 g (0.8 mmol) of branched polyethyleneimine (manufactured by Aldrich, molecular weight 25,000), 0 potassium carbonate .07 g and 100 ml of N, N-dimethylacetamide were stirred at 100 ° C. for 6 hours under a nitrogen atmosphere. 300 ml of a mixed solution of ethyl acetate and hexane (V / V = 1/2) was added to the obtained reaction mixture, and the mixture was vigorously stirred at room temperature, and then the solid product was filtered. The solid was repeatedly washed twice with 100 ml of a mixed solution of ethyl acetate and hexane (V / V = 1/2), and then dried under reduced pressure to obtain a polymer compound in which polyethylene glycol was bound to branched polyethyleneimine. 24.4 g of solid was obtained.
　得られた高分子化合物を０．５９２ｇ用いた水溶液１３８．８ｇに酸化銀１０．０ｇを加えて２５℃で３０分間攪拌した。引き続き、ジメチルエタノールアミン４６．０ｇを攪拌しながら徐々に加えたところ、反応溶液は褐色に変わり、若干発熱したが、そのまま放置して２５℃で３０分間攪拌した。その後、１０％アスコルビン酸水溶液１５．２ｇを攪拌しながら徐々に加えた。その温度を保ちながらさらに２０時間攪拌を続けて、褐色の分散体を得た。 10.0 g of silver oxide was added to 138.8 g of an aqueous solution using 0.592 g of the obtained polymer compound, and the mixture was stirred at 25 ° C. for 30 minutes. Subsequently, when 46.0 g of dimethylethanolamine was gradually added with stirring, the reaction solution turned brown and slightly generated heat, but the reaction solution was left as it was and stirred at 25 ° C. for 30 minutes. Then, 15.2 g of a 10% aqueous ascorbic acid solution was gradually added with stirring. Stirring was continued for another 20 hours while maintaining the temperature to obtain a brown dispersion.
＜ペーストの調製＞
　上記合成により得られた銀微粒子分散体に、銀に対して２．０％になるように、リシノール酸（東京化成工業社製）を加えた１－ブタノール（関東化学社製）混合液を、銀濃度が７０％になるように添加した。０．５時間程度攪拌し、深い青色のペーストを得た。また、表面張力を調整するためにフッ素系レベリング剤ＭＥＧＡＦＡＣＥを添加した。 <Preparation of paste>
A mixed solution of 1-butanol (manufactured by Kanto Chemical Co., Inc.) in which ricinoleic acid (manufactured by Tokyo Chemical Industry Co., Ltd.) was added to the silver fine particle dispersion obtained by the above synthesis so as to be 2.0% with respect to silver. It was added so that the silver concentration became 70%. Stirring for about 0.5 hour gave a deep blue paste. In addition, a fluorine-based leveling agent MEGAFACE was added to adjust the surface tension.
＜熱重量分析（ＴＧ－ＤＴＡ）による重量減少率の測定＞
　合成例１記載の方法と同様にして、ＴＧ－ＤＴＡによる重量減少率の測定を行った。ＴＧ－ＤＴＡ測定による重量減少より、得られた銀微粒子には１．８％の有機物が存在していたことを確認した。 <Measurement of weight loss rate by thermogravimetric analysis (TG-DTA)>
The weight loss rate was measured by TG-DTA in the same manner as in the method described in Synthesis Example 1. From the weight reduction by TG-DTA measurement, it was confirmed that 1.8% of organic matter was present in the obtained silver fine particles.
＜平均一次粒子径の測定＞
　合成例１記載の方法と同様にして、平均一次粒子径の測定を行った。得られた銀微粒子を透過型電子顕微鏡（ＴＥＭ）により観察すると、銀微粒子の平均一次粒子径は２５ｎｍであった。 <Measurement of average primary particle size>
The average primary particle size was measured in the same manner as described in Synthesis Example 1. When the obtained silver fine particles were observed with a transmission electron microscope (TEM), the average primary particle size of the silver fine particles was 25 nm.
（合成例５）
＜ペーストの調整＞
　本合成例のペーストは、銅粉末（三井金属鉱山（株）製　１１００Ｙ　Ｄ５０：１．１μｍ）を８．２６ｇと、ＴＥＧＯ（登録商標）ＶＡＲＩＰＬＵＳＳＫ（エボニックデグサジャパン（株）製）を０．１９０ｇと、ＤＩＳＰＥＲ　ＢＹＫ－１１１（ビックケミー社製　リン酸基含有ポリマー）を０．０５ｇと、ＴＲＩＸＥＮＥ　ＢＩ　７９９２（バクセンデン社製）を０．６６０ｇと、デナコ－ル（登録商標）ＥＸ－３２１（ナガセケムテックス（株）製）を０．２０７ｇと、ハイソルブ（登録商標）ＭＴＥＭ（東邦化学工業（株）製）を０．２６０ｇと、ジエチレングリコールモノブチルエーテルアセテートを０．３２３ｇと、及び、Ｕ－ＣＡＴ　ＳＡ　１０２（サンアプロ（株）製）を０．０５０ｇと、をオートマチックフーバーマーラー（（株）安田精機製作所製）を用いて混合し、分散させることにより作製した。 (Synthesis Example 5)
<Paste adjustment>
The paste of this synthetic example is 8.26 g of copper powder (1100Y D50: 1.1 μm manufactured by Mitsui Metal Mine Co., Ltd.) and 0.190 g of TEGO (registered trademark) VARIPLUSSK (manufactured by Evonik Degussa Japan Co., Ltd.). , DISPER BYK-111 (Bick Chemie's phosphate group-containing polymer) 0.05 g, TRIXENE BI 7992 (Baxenden's) 0.660 g, and Denacol® EX-321 (Nagase Chemtex (registered trademark) (Manufactured by Co., Ltd.) 0.207 g, High Solve (registered trademark) MTEM (manufactured by Toho Kagaku Kogyo Co., Ltd.) 0.260 g, Diethylene glycol monobutyl ether acetate 0.323 g, and U-CAT SA 102 (Sun Appro) (Manufactured by Yasuda Seiki Co., Ltd.) was mixed with 0.050 g using an automatic Hoover Marler (manufactured by Yasuda Seiki Seisakusho Co., Ltd.) and dispersed.
＜ペーストの調製＞
　その後、得られたペーストにジエチレングリコールモノブチルエーテルアセテートを添加し、乳鉢で混合することで金属微粒子含有率を７０％に調製した。 <Preparation of paste>
Then, diethylene glycol monobutyl ether acetate was added to the obtained paste and mixed in a mortar to adjust the metal fine particle content to 70%.
＜平均一次粒子径の測定＞
　合成例１記載の方法と同様にして、平均一次粒子径の測定を行った。購入した銅微粒子粉末を透過型電子顕微鏡（ＴＥＭ）により観察すると、銅微粒子の平均一次粒子径は１．２μｍであった。 <Measurement of average primary particle size>
The average primary particle size was measured in the same manner as described in Synthesis Example 1. When the purchased copper fine particle powder was observed with a transmission electron microscope (TEM), the average primary particle size of the copper fine particles was 1.2 μm.
（実施例１）
＜導電性ピラーの作製＞
（電極基板及び鋳型の作製）
　実験に用いた電極基板の作製方法を述べる。ピラーの基板への接合状態を観察するため、以下の手順で基板を作製した。
　Ａｌ製電極が設けられた４インチのシリコンウエハー上に、Ｔｉ（厚さ５０ｎｍ）をスパッタした後、Ｃｕ（２５０ｎｍ）をスパッタし、電極基板を作製した。
　スパッタをしたシリコン基板に最終膜厚が３０μｍになるようにレジスト樹脂を塗布し、パターニングした。レジストパターンの形状は円柱形状であり、開口部分の直径は３０μｍであり、開口部分の深さは３０μｍであった。アスペクト比は、１．０となるようにデザインした。 (Example 1)
<Manufacturing conductive pillars>
(Preparation of electrode substrate and mold)
The method of manufacturing the electrode substrate used in the experiment will be described. In order to observe the state of the pillars bonded to the substrate, the substrate was prepared by the following procedure.
Ti (thickness 50 nm) was sputtered on a 4-inch silicon wafer provided with an Al electrode, and then Cu (250 nm) was sputtered to prepare an electrode substrate.
A resist resin was applied to the sputtered silicon substrate so that the final film thickness was 30 μm, and patterning was performed. The shape of the resist pattern was a cylindrical shape, the diameter of the opening portion was 30 μm, and the depth of the opening portion was 30 μm. The aspect ratio was designed to be 1.0.
（ピラー形成）
　ピラーの形成は、調整したペーストを作製した電極基板に設けたレジスト開口部分に埋め込み、焼結することにより作製した。
　ペーストの充填は、スクリーン印刷用のウレタンゴムスキージを用いて行った。印刷は手刷りで行い、印刷用マスクは使用しなかった。充填時の送印速度約１０ｍｍ／ｓとした。
　合成例１に記載した方法で作製したペーストを、ウレタンスキージにより直径３０μｍの開口部分に充填した。 (Pillar formation)
The pillars were formed by embedding the adjusted paste in a resist opening provided in the prepared electrode substrate and sintering the paste.
The paste was filled using a urethane rubber squeegee for screen printing. Printing was done by hand and no printing mask was used. The printing speed at the time of filling was about 10 mm / s.
The paste prepared by the method described in Synthesis Example 1 was filled in an opening portion having a diameter of 30 μm with a urethane squeegee.
（焼結）
　焼結は、ペーストを開口部分に充填した後、蟻酸蒸気を含んだ窒素ガス雰囲気下において２５０℃で１０分間行った。焼結は、ホットプレートを用いて行った。 (Sintered)
Sintering was performed at 250 ° C. for 10 minutes in a nitrogen gas atmosphere containing formic acid vapor after filling the openings with the paste. Sintering was performed using a hot plate.
（接合層の作製）
　本実施例における接合層の作製には、ＩＭＳ（Ｉｎｊｅｃｔｉｏｎ　Ｍｏｌｄｅｄ　Ｓｏｌｄｅｒｉｎｇ）工法を使用した（特開２０１５－１０６６１７）。溶融はんだを保持するリザーバから、溶融はんだを射出し、ピラーを有するレジスト開口部分へ直接溶融はんだを供給した。はんだ合金は、ＳＡＣ３０５を使用した。これにより、はんだ合金から成る接合層をピラー先端部に作製した。ピラー先端部で固化したはんだ合金は、レジスト層との表面エネルギー差によりその頭部が凸曲面状に盛り上がった形状を示した（図１）。 (Preparation of bonding layer)
An IMS (Injection Molded Soldering) method was used to prepare the bonding layer in this example (Japanese Patent Laid-Open No. 2015-106617). The molten solder was ejected from the reservoir holding the molten solder, and the molten solder was directly supplied to the resist opening having the pillars. SAC305 was used as the solder alloy. As a result, a bonding layer made of a solder alloy was produced at the tip of the pillar. The solder alloy solidified at the tip of the pillar showed a shape in which the head portion was raised in a convex curved surface shape due to the difference in surface energy from the resist layer (FIG. 1).
（実施例２）
＜導電性ピラーの作製＞
（電極基板及び鋳型の作製）
　実施例１記載の方法と同様にして、電極基板の作製を行った。 (Example 2)
<Manufacturing conductive pillars>
(Preparation of electrode substrate and mold)
An electrode substrate was produced in the same manner as in the method described in Example 1.
（ピラー形成）
　合成例２に記載した方法で作製したペーストを用いて、実施例１記載の方法と同様にして、ピラーの形成を行った。 (Pillar formation)
Pillars were formed in the same manner as in Example 1 using the paste prepared by the method described in Synthesis Example 2.
（焼結）
　実施例１記載の方法と同様にして、ペーストの焼結を行った。 (Sintered)
The paste was sintered in the same manner as described in Example 1.
（接合層の作製）
　実施例１記載の方法と同様にして、接合層の作製を行った。 (Preparation of bonding layer)
A bonding layer was prepared in the same manner as described in Example 1.
（実施例３）
＜導電性ピラーの作製＞
（電極基板及び鋳型の作製）
　実施例１記載の方法と同様にして、電極基板の作製を行った。 (Example 3)
<Manufacturing conductive pillars>
(Preparation of electrode substrate and mold)
An electrode substrate was produced in the same manner as in the method described in Example 1.
（ピラー形成）
　合成例３に記載した方法で作製したペーストを用いて、実施例１記載の方法と同様にして、ピラーの形成を行った。 (Pillar formation)
Pillars were formed in the same manner as in Example 1 using the paste prepared by the method described in Synthesis Example 3.
（焼結）
　実施例１記載の方法と同様にして、ペーストの焼結を行った。 (Sintered)
The paste was sintered in the same manner as described in Example 1.
（接合層の作製）
　実施例１記載の方法と同様にして、接合層の作製を行った。 (Preparation of bonding layer)
A bonding layer was prepared in the same manner as described in Example 1.
（実施例４）
＜導電性ピラーの作製＞
（電極基板及び鋳型の作製）
　実施例１記載の方法と同様にして、電極基板の作製を行った。 (Example 4)
<Manufacturing conductive pillars>
(Preparation of electrode substrate and mold)
An electrode substrate was produced in the same manner as in the method described in Example 1.
（ピラー形成）
　合成例４に記載した方法で作製したペーストを用いて、実施例１記載の方法と同様にして、ピラーの形成を行った。 (Pillar formation)
Pillars were formed in the same manner as in Example 1 using the paste prepared by the method described in Synthesis Example 4.
（焼結）
　実施例１記載の方法と同様にして、ペーストの焼結を行った。 (Sintered)
The paste was sintered in the same manner as described in Example 1.
（接合層の作製）
　実施例１記載の方法と同様にして、接合層の作製を行った。 (Preparation of bonding layer)
A bonding layer was prepared in the same manner as described in Example 1.
（実施例５）
＜導電性ピラーの作製＞
（電極基板及び鋳型の作製）
　実験に用いた電極基板は、以下の手順で作製した。
　４インチのシリコンウエハー上に設けられたＡｌ製電極基板上に、Ｎｉ層を設け、その上にＡｕを無電解メッキ法により４μｍの厚さで積層させた電極基板を作製した。作製した電極基板を本実験に用いた。
　Ａｕ電極を有するシリコン基板に最終膜厚が３０μｍになるようにレジスト樹脂を塗布し、パターニングした。レジストパターンの形状は円柱形状であり、開口部分の直径は３０μｍであり、開口部分の深さは３０μｍであった。アスペクト比は、１．０となるようにデザインした。 (Example 5)
<Manufacturing conductive pillars>
(Preparation of electrode substrate and mold)
The electrode substrate used in the experiment was prepared by the following procedure.
An electrode substrate was prepared by providing a Ni layer on an Al electrode substrate provided on a 4-inch silicon wafer and laminating Au on the Al electrode substrate to a thickness of 4 μm by an electroless plating method. The prepared electrode substrate was used in this experiment.
A resist resin was applied to a silicon substrate having an Au electrode so that the final film thickness was 30 μm, and patterning was performed. The shape of the resist pattern was a cylindrical shape, the diameter of the opening portion was 30 μm, and the depth of the opening portion was 30 μm. The aspect ratio was designed to be 1.0.
（ピラー形成）
　合成例１に記載した方法で作製したペーストを用いて、実施例１記載の方法と同様にして、ピラーの形成を行った。 (Pillar formation)
Pillars were formed in the same manner as in Example 1 using the paste prepared by the method described in Synthesis Example 1.
（焼結）
　実施例１記載の方法と同様にして、ペーストの焼結を行った。 (Sintered)
The paste was sintered in the same manner as described in Example 1.
（接合層の作製）
　実施例１記載の方法と同様にして、接合層の作製を行った。 (Preparation of bonding layer)
A bonding layer was prepared in the same manner as described in Example 1.
（比較例１）
＜導電性ピラーの作製＞
（電極基板及び鋳型の作製）
　実施例１記載の方法と同様にして、電極基板の作製を行った。 (Comparative Example 1)
<Manufacturing conductive pillars>
(Preparation of electrode substrate and mold)
An electrode substrate was produced in the same manner as in the method described in Example 1.
（ピラー形成）
　合成例５に記載した方法で作製したペーストを用いて、実施例１記載の方法と同様にして、ピラーの形成を行った。 (Pillar formation)
Pillars were formed in the same manner as in Example 1 using the paste prepared by the method described in Synthesis Example 5.
（焼結）
　焼結は、ペーストを開口部分に充填した後、蟻酸蒸気を含んだ窒素ガス雰囲気下において１８０℃で３０分間行った。焼結は、ホットプレートを用いて行った。 (Sintered)
Sintering was performed at 180 ° C. for 30 minutes in a nitrogen gas atmosphere containing formic acid vapor after filling the openings with the paste. Sintering was performed using a hot plate.
（接合層の作製）
　実施例１記載の方法と同様にして、接合層の作製を行った。 (Preparation of bonding layer)
A bonding layer was prepared in the same manner as described in Example 1.
（比較例２）
＜導電性ピラーの作製＞
（電極基板及び鋳型の作製）
　実施例１記載の方法と同様にして、電極基板の作製を行った。 (Comparative Example 2)
<Manufacturing conductive pillars>
(Preparation of electrode substrate and mold)
An electrode substrate was produced in the same manner as in the method described in Example 1.
（導電性ピラーの作製）
　本実施例におけるピラーの作製には、ＩＭＳ（Ｉｎｊｅｃｔｉｏｎ　Ｍｏｌｄｅｄ　Ｓｏｌｄｅｒｉｎｇ）工法を使用した（特開２０１５－１０６６１７）。溶融はんだを保持するリザーバから、溶融はんだを射出し、レジスト開口部分へ直接溶融はんだを供給した。はんだ合金は、ＳＡＣ３０５を使用した。これにより、はんだ合金のみから成る導電性ピラーを作製した。固化したはんだ合金は、レジスト層との表面エネルギー差によりその頭部が凸曲面状に盛り上がった形状を示した。 (Making conductive pillars)
An IMS (Injection Molded Soldering) method was used to prepare the pillars in this example (Japanese Patent Laid-Open No. 2015-106617). The molten solder was injected from the reservoir holding the molten solder, and the molten solder was directly supplied to the resist opening. SAC305 was used as the solder alloy. As a result, a conductive pillar made of only a solder alloy was produced. The solidified solder alloy showed a shape in which its head was raised in a convex curved surface shape due to the difference in surface energy from the resist layer.
（参考例１）
＜導電性ピラーの作製＞
（電極基板の作製）
　実験に用いた電極基板の作製方法を述べる。ピラーの基板への接合状態を観察するため、以下の手順で基板を作製した。
　４インチのシリコンウエハー上に、Ｔｉ（厚さ５０ｎｍ）をスパッタした後、電解メッキをするためのシード層としてＣｕ（２５０ｎｍ）をスパッタした電極基板を作製し、実験に用いた。
　スパッタをしたシリコン基板に最終膜厚が３０μｍになるようにレジスト樹脂を塗布し、パターニングした。レジストパターンの形状は円柱形状であり、開口部分の直径は３０μｍであり、開口部分の深さは３０μｍであった。アスペクト比は、１．０となるようにデザインした。 (Reference example 1)
<Manufacturing conductive pillars>
(Preparation of electrode substrate)
The method of manufacturing the electrode substrate used in the experiment will be described. In order to observe the state of the pillars bonded to the substrate, the substrate was prepared by the following procedure.
An electrode substrate sputtered with Cu (250 nm) as a seed layer for electrolytic plating after sputtering Ti (thickness 50 nm) on a 4-inch silicon wafer was prepared and used in an experiment.
A resist resin was applied to the sputtered silicon substrate so that the final film thickness was 30 μm, and patterning was performed. The shape of the resist pattern was a cylindrical shape, the diameter of the opening portion was 30 μm, and the depth of the opening portion was 30 μm. The aspect ratio was designed to be 1.0.
（メッキピラーの作製）
　作製した電極基板を５ｗｔ％硫酸に浸漬し、シード層の酸化被膜を除去する前処理を行った。前処理の後、硫酸銅・５水和物６５ｇ／Ｌ、硫酸１７０ｇ／Ｌ、塩化ナトリウム７０ｍｇ／Ｌからなる銅メッキ液を調整した。銅メッキ液に、作製した電極基板を浸漬させ、分極した。レジスト層のパターン開口部分の露出したカソード電極面に銅メッキを行い、ピラーを作製した。作製したピラーは円柱状であり、ピラー高さは２０ｕｍであった。 (Making plated pillars)
The prepared electrode substrate was immersed in 5 wt% sulfuric acid to perform a pretreatment for removing the oxide film of the seed layer. After the pretreatment, a copper plating solution consisting of 65 g / L of copper sulfate pentahydrate, 170 g / L of sulfuric acid, and 70 mg / L of sodium chloride was prepared. The prepared electrode substrate was immersed in a copper plating solution and polarized. The exposed cathode electrode surface of the pattern opening portion of the resist layer was plated with copper to prepare pillars. The prepared pillar was columnar, and the pillar height was 20 um.
（接合層の作製）
　実施例１記載の方法と同様にして、接合層の作製を行った。 (Preparation of bonding layer)
A bonding layer was prepared in the same manner as described in Example 1.
＜導電性ピラーの評価＞
（接合強度の測定）
　接合強度の測定は、ＪＩＳ　Ｚ－０３９１８－５：２００３「鉛フリーはんだ試験方法」に記載の方法で、上記の接合試験片にせん断力を付加し、接合強度を測定した。試験条件は、高さを電極基板より７μｍ、スピードを２００μｍ／ｓで実施した。測定したピラーは、円柱形状のものを使用した。導電性ピラーの直径は７５μｍであり、高さは約３０μｍであった。 <Evaluation of conductive pillars>
(Measurement of joint strength)
The joint strength was measured by applying a shear force to the above-mentioned joint test piece by the method described in JIS Z-03918-5: 2003 "Lead-free solder test method" to measure the joint strength. The test conditions were a height of 7 μm from the electrode substrate and a speed of 200 μm / s. The pillars measured were cylindrical. The diameter of the conductive pillar was 75 μm and the height was about 30 μm.
　実施例及び参考例に記載した導電性ピラーの接合強度測定を実施した。
ペーストの充填又はメッキ法によりレジスト開口部分にピラーを形成し、ＩＭＳ法によりピラー先端部に接続層であるＳＡＣ３０５を形成し、導電性ピラーを得た。作製した導電性ピラーは、ピラーの高さ（金属微粒子層）が１５～２０μｍ、金属間化合物層が１～５μｍ、接合層が５～１５μｍ程度であった。
　レジスト薄膜を除去し、接合強度測定を行った。得られた接合強度測定の結果を表１に示した。 The joint strength of the conductive pillars described in Examples and Reference Examples was measured.
Pillars were formed in the resist opening portion by a paste filling or plating method, and SAC305, which is a connecting layer, was formed at the tip of the pillars by the IMS method to obtain a conductive pillar. The prepared conductive pillar had a pillar height (metal fine particle layer) of about 15 to 20 μm, an intermetallic compound layer of 1 to 5 μm, and a bonding layer of about 5 to 15 μm.
The resist thin film was removed and the bonding strength was measured. The results of the obtained joint strength measurement are shown in Table 1.
（観察・評価）
　評価基準について、測定は７箇所行った。評価は、測定した値の最高値を用いた。評価基準は、以下のとおりとした。
◎：作製した導電性ピラーのシェア強度の最高値が１５０ＭＰａ以上であることを示す。
○：作製した導電性ピラーのシェア強度の最高値が８０ＭＰａ以上であることを示す。
△：作製した導電性ピラーのシェア強度の最高値が５０ＭＰａ以上であることを示す。
×：作製した導電性ピラーのシェア強度の最高値が５０ＭＰａ未満であることを示す。 (Observation / evaluation)
Regarding the evaluation criteria, the measurement was performed at 7 points. For the evaluation, the highest value of the measured values was used. The evaluation criteria were as follows.
⊚: Indicates that the maximum value of the shear strength of the produced conductive pillar is 150 MPa or more.
◯: Indicates that the maximum value of the shear strength of the produced conductive pillar is 80 MPa or more.
Δ: Indicates that the maximum value of the shear strength of the produced conductive pillar is 50 MPa or more.
X: Indicates that the maximum value of the shear strength of the produced conductive pillar is less than 50 MPa.
Figure JPOXMLDOC01-appb-T000001
Figure JPOXMLDOC01-appb-T000001
　実施例１から５で作製したピラーは、比較例のものと比較して良好な接合強度を示した。中でも、合成例１により作製した銅ペーストを用いて作製した導電性ピラーは非常に良好な結果を示した。特に、電極基板をＡｕにより作製した導電性ピラーは、参考例１に記載した銅メッキピラーと同程度の良好なシェア強度を示した。これは、電極基板表面が酸化の影響を受けず、電極と導電性ピラーとの接合が強固になったものと考えられる。
　したがって、電極基板表面の酸化被膜を除去すると、実施例１から５においても参考例１記載の接合強度と同程度に向上すると考えられ、本発明に係る金属微粒子からなる導電性ピラーは産業上利用できることを示している。 The pillars prepared in Examples 1 to 5 showed good bonding strength as compared with those of Comparative Example. Among them, the conductive pillars prepared by using the copper paste prepared in Synthesis Example 1 showed very good results. In particular, the conductive pillar in which the electrode substrate was made of Au showed a good share strength comparable to that of the copper-plated pillar described in Reference Example 1. It is considered that this is because the surface of the electrode substrate was not affected by oxidation and the bonding between the electrode and the conductive pillar was strengthened.
Therefore, it is considered that removing the oxide film on the surface of the electrode substrate improves the bonding strength to the same extent as that described in Reference Example 1 in Examples 1 to 5, and the conductive pillar made of metal fine particles according to the present invention is industrially used. It shows that it can be done.
＜導電性ピラーの電気抵抗測定＞
　作製した導電性ピラーを有するトップＳｉチップと銅製電極基板を有するボトムＳｉチップとを接合し、導電性ピラーの電気抵抗を４端子測定により測定した。測定に使用した導電性ピラーの直径は４０μｍの円柱形状であり、チップアッセンブリ後の導電性ピラーの高さは２５μｍであった。抵抗値の測定は、８０個又は８２個の導電性ピラーを直列に接合し、電気抵抗を測定することにより行った（図３、図４）。
　測定は、８０個又は８２個の導電性ピラーが直列に接続された配線を１６箇所測定した。測定により得られた抵抗値をもとに、導電性ピラー１個あたりの抵抗値を算出した。測定により得られた、それら抵抗値の平均値を表２に示す。 <Measurement of electrical resistance of conductive pillars>
The prepared top Si chip having a conductive pillar and the bottom Si chip having a copper electrode substrate were joined, and the electric resistance of the conductive pillar was measured by 4-terminal measurement. The diameter of the conductive pillar used for the measurement was a cylindrical shape of 40 μm, and the height of the conductive pillar after chip assembly was 25 μm. The resistance value was measured by joining 80 or 82 conductive pillars in series and measuring the electrical resistance (FIGS. 3 and 4).
For the measurement, 16 wirings in which 80 or 82 conductive pillars were connected in series were measured. Based on the resistance value obtained by the measurement, the resistance value per conductive pillar was calculated. Table 2 shows the average value of these resistance values obtained by the measurement.
Figure JPOXMLDOC01-appb-T000002
Figure JPOXMLDOC01-appb-T000002
　実施例１から５で作製したピラーは、比較例のものと比較して良好な抵抗値すなわち導電性を示した。中でも、合成例１により作製した銅ペーストを用いて作製した導電性ピラーは非常に良好な結果を示した。比較例２のＳＡＣ３０５と比較しても、１／１０から１／５程度の抵抗値であり、実用に十分耐えうるものである。また、今回の導電性評価は８０個又は８２個の導電性ピラーを直列で接合し、導電性の評価を行ったが、本測定方法が可能なことから、本発明の導電性ピラーは欠けや欠落等の欠陥が少なく、良好な歩留りのものである。なお、比較例１は断線のため測定ができなかった。 The pillars produced in Examples 1 to 5 showed a good resistance value, that is, conductivity as compared with those of Comparative Example. Among them, the conductive pillars prepared by using the copper paste prepared in Synthesis Example 1 showed very good results. Even when compared with SAC305 of Comparative Example 2, the resistance value is about 1/10 to 1/5, which is sufficiently durable for practical use. Further, in the present conductivity evaluation, 80 or 82 conductive pillars were joined in series to evaluate the conductivity, but since this measurement method is possible, the conductive pillars of the present invention are chipped. It has few defects such as chips and has a good yield. In Comparative Example 1, measurement could not be performed due to disconnection.
　本発明の導電性ピラーは優れたシェア強度、導電性を有しており、フリップチップ実装用端子をはじめとする種々の電子部品・デバイス実装用端子として用いることができる。また、本発明の導電性ピラーはエッチング工程やメッキ工程を伴わず製造することもできるため、製造時の環境負荷が小さく、更には微細な構造とすることができる。 The conductive pillar of the present invention has excellent shear strength and conductivity, and can be used as a terminal for mounting various electronic components and devices including a terminal for mounting a flip chip. Further, since the conductive pillar of the present invention can be manufactured without an etching step or a plating step, the environmental load at the time of manufacturing is small, and a fine structure can be obtained.
１１　基板、１２　電極、１３　ピラー（Ａ）、１４　接合層、
２Ａ１　基板、２Ａ２　電極、２Ａ３　導電性ピラー（Ｂ又はＣ）、
２Ｂ１　基板、２Ｂ２　電極、２Ｂ３　ピラー（Ａ）、２Ｂ４　接合層
２Ｃ１　基板、２Ｃ２　電極、２Ｃ３　ピラー（Ａ）、２Ｃ４　接合層、２Ｃ５　金属間化合物層
３１　基板、３２　電極、３３　ピラー（Ａ）、３４　金属間化合物層、３５　接合層、３６　電極、３７　アンダーフィル、３８　基板、３９　導電配線

  11 substrates, 12 electrodes, 13 pillars (A), 14 bonding layers,
2A1 substrate, 2A2 electrode, 2A3 conductive pillar (B or C),
2B1 substrate, 2B2 electrode, 2B3 pillar (A), 2B4 junction layer 2C1 substrate, 2C2 electrode, 2C3 pillar (A), 2C4 junction layer, 2C5 intermetallic compound layer 31 substrate, 32 electrodes, 33 pillars (A), 34 metals Intermetallic layer, 35 junction layer, 36 electrodes, 37 underfills, 38 substrates, 39 conductive wiring

Claims (8)

  1. 　粒子径が１μｍ未満の金属微粒子と、保護剤と、を含有するペーストを焼結して作製したピラー（Ａ）と、接合層と、を有することを特徴とする導電性ピラー（Ｂ）。 A conductive pillar (B) having a pillar (A) produced by sintering a paste containing metal fine particles having a particle diameter of less than 1 μm and a protective agent, and a bonding layer.
  2. 　ピラー（Ａ）に含まれる保護剤が、アミノ基、カルボニル基、チオール基、アルキルチオ基、アルケニルチオ基、チオエーテル基、リン酸基のうち少なくとも一種以上の官能基を有し、かつ、分子量が５００以上の化合物であることを特徴とする請求項１記載の導電性ピラー（Ｂ）。 The protective agent contained in the pillar (A) has at least one functional group among amino group, carbonyl group, thiol group, alkylthio group, alkenylthio group, thioether group and phosphoric acid group, and has a molecular weight of 500. The conductive pillar (B) according to claim 1, further comprising the above compound.
  3. 　ピラー（Ａ）に含まれる保護剤が、炭素数８～２００のポリエチレンオキシド構造を含む有機化合物であることを特徴とする請求項１又は２記載の導電性ピラー（Ｂ）。 The conductive pillar (B) according to claim 1 or 2, wherein the protective agent contained in the pillar (A) is an organic compound containing a polyethylene oxide structure having 8 to 200 carbon atoms.
  4. 　ピラー（Ａ）と、接合層と、の間に金属間化合物層を有することを特徴とする請求項１から３のいずれか記載の導電性ピラー。 The conductive pillar according to any one of claims 1 to 3, wherein an intermetallic compound layer is provided between the pillar (A) and the bonding layer.
  5. 　接合層が、スズ、鉛、銀、銅又はこれらの内から選択される１種以上の金属を含有する合金であることを特徴とする請求項１から４のいずれか記載の導電性ピラー。 The conductive pillar according to any one of claims 1 to 4, wherein the bonding layer is an alloy containing tin, lead, silver, copper or one or more metals selected from these.
  6. 　粒子径が１μｍ未満の金属微粒子が、銀または銅から選択される１種以上の金属であることを特徴とする請求項１から５のいずれか記載の導電性ピラー。 The conductive pillar according to any one of claims 1 to 5, wherein the metal fine particles having a particle diameter of less than 1 μm are one or more metals selected from silver or copper.
  7. 　導電性ピラーのアスペクト比が０．５以上であることを特徴とする請求項１から６のいずれか記載の導電性ピラー。 The conductive pillar according to any one of claims 1 to 6, wherein the conductive pillar has an aspect ratio of 0.5 or more.
  8. 　フリップチップ実装用端子である請求項１から７のいずれか記載の導電性ピラー。

     
          The conductive pillar according to any one of claims 1 to 7, which is a terminal for mounting a flip chip.
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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2014111800A (en) * 2012-12-05 2014-06-19 Nippon Handa Kk Pasty metal particulate composition, method for manufacturing solid metal or solid metal alloy, method for joining metallic members, method for manufacturing print wire board, and method for manufacturing bump for connecting electric circuits
US9859241B1 (en) * 2016-09-01 2018-01-02 International Business Machines Corporation Method of forming a solder bump structure

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2014111800A (en) * 2012-12-05 2014-06-19 Nippon Handa Kk Pasty metal particulate composition, method for manufacturing solid metal or solid metal alloy, method for joining metallic members, method for manufacturing print wire board, and method for manufacturing bump for connecting electric circuits
US9859241B1 (en) * 2016-09-01 2018-01-02 International Business Machines Corporation Method of forming a solder bump structure

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