JP2015032806A - Alloy via paste and method of manufacturing wiring board using alloy via paste - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a multilayer wiring board capable of responding to the need for lead-free.SOLUTION: In a wiring board having a via hole conductor, the via hole conductor includes a metal portion and a resin portion. The metal portion has a first metal region, a second metal region and a third metal region, where copper particles forming an aggregate form a surface contact part by coming into surface contact with each other, and at least a part of the second metal region is in contact with the first metal region, in the alloy via paste for wiring board. The alloy via paste has any one or more of liquid components of at least copper particles having a first reactive adsorption layer on the surface, Sn-Bi solder particles having a second reactive adsorption layer on the surface, and a liquid reactive resin or liquid organic solvent.

Description

  The present invention relates to an alloy via paste and a method for manufacturing a wiring board using the alloy via paste. More specifically, the present invention relates to lowering the resistance of via-hole conductors and improving connection reliability.

  Conventionally, a multilayer wiring board obtained by interlayer connection between two wirings three-dimensionally formed on an insulating resin layer is known. As such an interlayer connection method, a via-hole conductor is known which is formed by filling a hole formed in an insulating resin layer with a conductive paste. A via-hole conductor in which metal particles containing copper (Cu) are filled instead of the conductive paste and these metal particles are fixed with an intermetallic compound is also known.

  Specifically, for example, Patent Document 1 below discloses a via-hole conductor having a matrix domain structure in which domains composed of a plurality of Cu particles are interspersed in a matrix of CuSn compounds.

  Further, for example, Patent Document 2 below discloses a sinterable composition used for forming a via-hole conductor, which includes a high-melting-point particle phase material containing Cu and a low-melting-point material selected from metals such as tin (Sn) or a tin alloy. We are disclosing things. Such sinterable compositions are compositions that are sintered in the presence of a liquid phase or a transient liquid phase.

  Further, for example, Patent Document 3 below discloses that the outer periphery of a copper particle is obtained by heating a conductive paste containing tin-bismuth (Sn-Bi) -based metal particles and copper particles at a temperature equal to or higher than the melting point of the Sn-Bi-based metal particles. Discloses a via-hole conductor material in which an alloy layer having a solid phase temperature of 250 ° C. or higher is formed. Such a via-hole conductor material has a high connection reliability since the interlayer connection is performed by joining the alloy layers having a solid phase temperature of 250 ° C. or higher, and the alloy layer does not melt even in a heat cycle test or a reflow resistance test. It is described that it can be obtained.

  Further, for example, Patent Document 4 below discloses a multilayer wiring board provided with a via-hole conductor containing copper and tin in a proportion of 80 to 97% by weight and bismuth in a proportion of 3 to 20% by weight.

  In response to such conventional problems, the inventors have developed a wiring board using an alloy via, a manufacturing method of the wiring board, a via paste, and the like, as disclosed in Patent Document 5.

  The present invention aims to further improve Patent Document 5.

  On the other hand, as a conventional copper paste of pressure welding system, Patent Document 6 discloses a conductive paste containing conductive powder, a curable resin, a curing agent, and a reactive diluent, and the curable resin is a dimer acid type epoxy. A conductive paste containing a resin, the content of the curing agent being less than 0.3% by mass, and the reactive diluent containing a higher alcohol glycidyl ether has been proposed.

  However, such a conventional pressure contact type conductive paste mainly composed of copper cannot produce the alloy via paste aimed by the inventors in Patent Document 5.

  Moreover, in patent document 7, in the copper paste used for conductor formation of the printed wiring board which consists of an organic vehicle and copper powder, the said copper powder performs surface treatment with a carboxylic acid containing organic solvent, and uses a wind circulator for agglomerated particles. A copper paste that has been pulverized and a printed wiring board that includes a conductor formed using the copper paste have been proposed.

  However, such a conventional pressure contact type conductive paste mainly composed of copper cannot produce the alloy via paste aimed by the inventors in Patent Document 5.

  Further, Patent Document 8 proposes an alloy-based via paste, but the via paste contains a large amount of 2 to 60% by volume of a flux component and a crosslinking agent. Therefore, there is a possibility that a flux component, a crosslinking agent, or the like, which is an insulating material, inhibits the alloy reaction and affects via resistance.

JP 2000-49460 A Japanese Patent Laid-Open No. 10-7933 JP 2002-94242 A JP 2002-290052 A Japanese Patent No. 4795488 JP 2011-29204 A Japanese Patent No. 423333 US Pat. No. 5,948,533

  The via-hole conductor disclosed in Patent Document 1 will be described in detail with reference to FIG. FIG. 29 is a schematic cross-sectional view of a connection portion between the wiring 1 and the via-hole conductor 2 of the multilayer wiring board disclosed in Patent Document 1.

In the schematic cross-sectional view of FIG. 29, the via-hole conductor 2 is in contact with the wiring 1 formed on the surface of the multilayer wiring board. The via-hole conductor 2 includes a matrix containing an intermetallic compound 4 such as Cu ₃ Sn or Cu ₆ Sn ₅ and a copper-containing powder 3 scattered as domains in the matrix containing the intermetallic compound 4. In this via-hole conductor 2, a matrix domain structure is formed by setting the weight ratio represented by Sn / (Cu + Sn) in the range of 0.25 to 0.75.

  However, such a via-hole conductor 2 has a problem that voids and cracks (5 in FIG. 29) are likely to occur in the thermal shock test.

Such voids and cracks are caused by CuSn such as Cu ₃ Sn, Cu ₆ Sn _5, etc. when Cu is diffused into the Sn—Bi-based metal particles when the via-hole conductor 2 receives heat in a thermal shock test or reflow treatment, for example. It corresponds to a crack caused by the formation of a compound. In addition, such voids include Cu ₃ Sn, which is an intermetallic compound of Cu and Sn contained in a Cu—Sn diffusion bonding portion formed at the interface between Cu and Sn, and is used in various reliability tests. This is also caused by the fact that internal stress is generated in the via-hole conductor 2 by changing to Cu ₆ Sn ₅ by heating.

  In addition, the sinterable composition disclosed in Patent Document 2 is sintered in the presence or absence of a transient liquid phase, which occurs during, for example, a hot press for laminating a prepreg. It is a composition. Since such a sinterable composition contains Cu, Sn, and lead (Pb), it has been difficult to cope with the Pb-free requirement that is required from the market.

  In addition, since such a sinterable composition has a high temperature at 180 ° C. to 325 ° C. at the time of hot pressing, an insulating resin layer (glass epoxy resin) obtained by impregnating a general glass fiber with an epoxy resin. It was difficult to apply to a layer).

  In the via hole conductor material disclosed in Patent Document 3, the resistance value of the alloy layer formed on the surface layer of the Cu particles is high. Therefore, it becomes a high resistance value compared to a connection resistance value obtained only by contact between Cu particles or between Ag particles like a general conductive paste containing Cu particles, silver (Ag) powder or the like. There was a problem.

  Further, the via hole conductor disclosed in Patent Document 4 also has a problem that the resistance value of the alloy layer formed on the surface layer of Cu particles is high and a sufficiently low resistance interlayer connection cannot be obtained, as will be described later. It was.

  The present invention relates to a multilayer wiring board having a low resistance via-hole conductor having high connection reliability for interlayer connection between two wirings three-dimensionally formed on an insulating resin layer, which is lead-free An object of the present invention is to provide a multilayer wiring board that can cope with the above.

  One aspect of the present invention is at least one insulating resin layer, a first wiring disposed on the first surface of the insulating resin layer, a second wiring disposed on the second surface of the insulating resin layer, A wiring board having a via-hole conductor for electrically connecting the first wiring and the second wiring provided so as to penetrate the insulating resin layer, the via-hole conductor being a metal portion and a resin A first metal region including a combination of copper particles forming a path for electrically connecting the first wiring and the second wiring, and a tin, tin-copper alloy, And a second metal region mainly composed of at least one metal selected from the group consisting of tin and copper intermetallic compounds, and a third metal region mainly composed of bismuth in contact with the second metal region. And the copper particles forming the combined body are in surface contact with each other. The surface contact portion is thereby formed, and at least a part of the second metal region is an alloy via paste for a wiring board in contact with the first metal region, and at least the first reactive adsorption on the surface Alloy via paste having the copper particles having a layer, the Sn-Bi solder particles having a second reactive adsorption layer on the surface, and one or more liquid components of a liquid reactive resin or a liquid organic solvent It is.

  In another aspect of the present invention, at least the copper particles having a first reactive adsorption layer on the surface, the Sn-Bi solder particles having a second reactive adsorption layer on the surface, and a liquid reactive resin or One or more liquid components of a liquid organic solvent, and an alloy via paste having a copper particle content in the range of 30 to 90% by mass, the copper (Cu) in the copper particles and the The weight ratio (Cu / Sn) to tin (Sn) in the tin-bismuth solder particles is in the range of 1.59 to 21.43, and the first reactive adsorption layer and the second reactive adsorption layer are Both are alloy via pastes containing carboxylic acid, and are useful for the production of the wiring board according to claim 1.

  Another aspect of the present invention is a method of manufacturing a wiring board using the alloy via paste according to claim 1, wherein the first step of covering the surface of the insulating resin sheet with a protective film, and the protective film A second step of drilling the insulating resin sheet to form a through hole, and the through hole includes copper particles, tin-bismuth solder particles and a thermosetting resin, and the content ratio of the copper particles is The weight ratio (Cu / Sn) of copper (Cu) in the copper particles and tin (Sn) in the tin-bismuth solder particles is 1.59 to 21.43. A third step of filling the via paste, and a protruding portion formed by protruding a part of the via paste from the through hole by peeling the protective film after the third step. The fourth step to be exposed and covering the protrusion As described above, the fifth step of disposing a metal foil on at least one surface of the insulating resin sheet, and press-bonding the metal foil to the surface of the insulating resin sheet and passing the via paste through the protrusions to the tin-bismuth solder particles A sixth step of forming a bonded body of copper particles having a surface contact portion formed by surface contact between the copper particles by compressing at a temperature lower than the eutectic temperature; And a seventh step of heating the via paste at a temperature equal to or higher than the eutectic temperature of the tin-bismuth solder particles.

  The objects, features, aspects and advantages of the present invention will become more apparent from the following detailed description and the accompanying drawings.

  According to the present invention, a low-resistance conductive path is formed by a combination of copper particles having a surface contact portion formed by surface contact between copper particles contained in via-hole conductors formed on a wiring board. Thus, interlayer connection with a low resistance value is realized.

  Further, the copper particle bonded body, the first metal region containing the copper particle bonded body, the second metal region, or the third metal region in contact with the second metal region, surrounded by the resin portion, tin -Increasing the reliability of these metal parts by interspersing bismuth-based solder particles.

(A) is a schematic cross-sectional view of the multilayer wiring board 11 in the first embodiment, and (B) is an enlarged schematic cross-sectional view of the vicinity of the via-hole conductor 14 in FIG. 1 (A). Explanatory drawing for demonstrating that the coupling | bonding body 17a of the copper particle formed when the many copper particles 7 in 1st embodiment mutually surface-contacted becomes the conduction path 23 between the wirings 12. FIG. Schematic cross-sectional view for explaining a via-hole conductor when Cu / Sn is smaller than 1.59 Process sectional drawing for demonstrating an example of the manufacturing method of the multilayer wiring board 11 in 1st embodiment Process sectional drawing following FIG. 4 for explaining an example of the manufacturing method of the multilayer wiring board 11 Process sectional drawing following FIG. 5 for explaining an example of the manufacturing method of the multilayer wiring board 11 Sectional schematic diagram for demonstrating a mode when compressing the via paste 28 with which the through-hole of the resin sheet 25 in 1st embodiment was filled. (A) is a schematic cross-sectional view of the multilayer wiring board 111 in the second embodiment, and (B) is an enlarged schematic cross-sectional view in the vicinity of the via-hole conductor 14 in FIG. 8 (A). Process sectional drawing for demonstrating an example of the manufacturing method of the multilayer wiring board 111 Process sectional drawing following FIG. 9 for explaining an example of the manufacturing method of the multilayer wiring board 111 Process sectional drawing following FIG. 10 for explaining an example of the manufacturing method of the multilayer wiring board 111 Sectional schematic diagram for demonstrating a mode when the via paste 28 with which the through-hole 27 of the prepreg 125 was filled in 2nd embodiment is compressed. The graph which shows resistance value (1via / mohm) with respect to the weight ratio of Cu / Sn in the via-hole conductor obtained in Example 1 (A) is an electron microscope (SEM) photograph of 3000 times the cross section of the via conductor of the multilayer wiring board obtained in the example, and (B) is a trace diagram thereof. (A) is a SEM photograph of 6000 times the cross section of the via-hole conductor of the multilayer wiring board obtained in Example 1, and (B) is a trace view thereof. (A) is the SEM photograph of the cross section of the via-hole conductor of the multilayer wiring board obtained in Example 1, (B) is the trace figure. (A) is a figure when mapping of Cu element of the SEM photograph of FIG. 15, (B) is the trace figure. (A) is the figure when Sn element mapping of the SEM photograph of FIG. 15 is performed, (B) is the trace figure. (A) is a figure when mapping of Bi element of the SEM photograph of FIG. 15, (B) is the trace figure. The graph which compared the resistance value of the via-hole conductor obtained from the electrically conductive paste of patent document 4 known conventionally, and the via-hole conductor which concerns on this invention Paste No. SEM photograph of the cross section of the via-hole conductor of the multilayer wiring board obtained in 6 and its trace figure Sectional drawing explaining an example of the manufacturing method of the wiring board using an alloy via paste Sectional drawing which expands and demonstrates the mode inside an alloy via paste when the sample shown in FIG. 22 is pressurized and heated Sectional drawing which shows a mode that the cured resin layer was formed in the surface of the press-contact body of several processed copper particles and processed solder particles (A) and (B) are schematic views showing an example of a curing reaction between an epoxy resin (an example of an epoxy resin is dimer acid diglycidyl ester) and a reactive resin contained in a liquid component. Schematic diagram showing how a reactive adsorption layer having a carboxyl group is formed on the surface of a pressed body of a plurality of treated copper particles and treated solder particles Sectional drawing which shows an example of the cured resin layer which the reactive adsorption layer which has a carboxyl group, and a part of reactive resin added to the liquid component reacted and formed The graph which shows an example of the viscosity change at the time of leaving to room temperature (25 degreeC) of the alloy via paste which the inventors made as an experiment Schematic cross-sectional view for explaining a cross section of a conventional via conductor

[First embodiment]
FIG. 1A is a schematic cross-sectional view of a multilayer wiring board 11 provided with a via-hole conductor 14 of the present embodiment. FIG. 1B is an enlarged schematic cross-sectional view of the vicinity of the via-hole conductor 14 in the multilayer wiring board 11 of FIG.

  As shown in FIG. 1A, in the multilayer wiring board 11, a plurality of wirings 12 formed of a metal foil such as a copper foil three-dimensionally formed on the insulating resin layer 13 penetrates the insulating resin layer 13. The via-hole conductor 14 is electrically connected to the interlayer.

  FIG. 1B is an enlarged schematic cross-sectional view near the via-hole conductor 14. In FIG. 1B, 12 (12a, 12b) is a wiring, 13 is an insulating resin layer, and 14 is a via-hole conductor. The via-hole conductor 14 includes a metal portion 15 and a resin portion 16.

  As the insulating resin layer 13, a conventionally known insulating layer of a multilayer wiring board is used without particular limitation. In the present embodiment, a laminated heat resistant resin sheet in which a cured resin layer 13b is laminated on both surfaces of the heat resistant resin sheet 13a is used.

  The metal portion 15 includes a first metal region 17 formed from the Cu particles 7 and a main component of at least one metal selected from the group consisting of tin, a tin-copper alloy, and a tin-copper intermetallic compound. A two-metal region 18 and a third metal region 19 containing Bi as a main component are included.

  Furthermore, the fourth metal region 22 which is an unreacted tin-bismuth solder particle is included. Tin-bismuth-based solder particles that are the fourth metal region are surrounded by the resin portion 16 and are scattered. At least a part of the Cu particles 7 are contact-bonded via the surface contact portions 20 that are in direct surface contact with each other, thereby forming a bonded body 17a of copper particles in a portion indicated by a broken line. The combined body 17a functions as a low-resistance conductive path that electrically connects the upper wiring 12a and the lower wiring 12b.

  The average particle diameter of the Cu particles 7 is preferably 0.1 to 20 μm, more preferably 1 to 10 μm. When the average particle diameter of the Cu particles 7 is too small, it is difficult to form a surface contact portion in the via-hole conductor 14 as will be described later, and the conduction resistance tends to increase because the number of contact points increases.

  On the other hand, when the average particle diameter of the Cu particles 7 is too large, the conduction resistance is increased by making it difficult to increase the filling rate when trying to form a via-hole conductor 14 having a small diameter such as 30 to 150 μmφ. Tend. In particular, in the case of a fine via-hole conductor having a maximum diameter of 30 to 150 μm, the average particle diameter of the copper particles is preferably in the range of 3 to 10 μm.

  The purity of the Cu particles 7 is preferably 90% by mass or more, and more preferably 99% by mass or more. The Cu particles 7 become softer as the copper purity is higher. Therefore, since it becomes easy to be crushed in the pressurization process mentioned below, when a plurality of Cu particles 7 contact each other, Cu particles 7 are easily deformed, thereby increasing a contact area between Cu particles 7. Moreover, when purity is high, it is preferable also from the point that the resistance value of the Cu particle 7 becomes lower.

  Here, the surface contact between the copper particles is not in contact with the degree to which the copper particles touch each other, but is deformed to each other until being compressed and compressed and plastically deformed, and as a result, between the copper particles. A state where the contact is spread and adjacent copper particles are in contact with each other on the surface. Thus, even after releasing compressive stress, a surface contact part between copper particles is hold | maintained by deform | transforming and making it contact | adhere until each copper particle mutually plastically deforms.

  The average particle diameter of the Cu particles 7 and the surface contact portion 20 where the Cu particles 7 are in surface contact with each other, after filling the formed multilayer wiring board with resin, polish the cross section of the via-hole conductor 14 (if necessary) The sample prepared by using a fine processing means such as Focused ION BEAM) is confirmed and measured by observing the sample using a scanning electron microscope (SEM).

  A large number of Cu particles 7 come into contact with each other to form a combined body 17a, thereby forming a low-resistance conductive path between the wiring 12a and the wiring 12b. By forming such a combined body 17a, the connection resistance between the wiring 12a and the wiring 12b can be lowered.

  In addition, in the via-hole conductor 14, a large number of Cu particles 7 are not regularly arranged but randomly contacted as shown in FIG. 1B, thereby forming a low-resistance coupling body 17 a having a complicated network. It is preferable that When the coupling body 17a forms such a network, the reliability of electrical connection can be improved.

  Moreover, it is preferable that the position where many Cu particles 7 are in surface contact is also random. By bringing the Cu particles 7 into surface contact at random positions, the stress generated inside the via-hole conductor 14 when receiving heat and the external force applied from the outside can be dispersed by the deformation.

  The ratio of the Cu particles 7 contained in the via-hole conductor 14 is preferably 20 to 90% by mass, and more preferably 40 to 70% by mass. When the ratio of the Cu particles 7 is too low, the reliability of the electrical connection as a conduction path of the combined body 17a formed by a large number of Cu particles 7 being in surface contact with each other tends to decrease. If too large, the resistance value tends to fluctuate in the reliability test.

  As shown in FIG. 1B, at least a part of the second metal region 18 mainly composed of at least one metal selected from the group consisting of tin, a tin-copper alloy, and a tin-copper intermetallic compound is formed. It is formed so as to contact the surface of the first metal region 17. In this way, the second metal region 18 is formed on the surface of the first metal region 17, whereby the first metal region 17 is reinforced. Moreover, it is preferable that at least a part of the second metal region 18 covers the surface contact portion 20 which is a portion where the copper particles 7 are in surface contact with each other. By forming the second metal region 18 so as to straddle the surface contact portion 20 in this way, the contact state of the surface contact portion 20 is further reinforced.

The second metal region 18 contains at least one metal selected from the group consisting of tin, a tin-copper alloy, and a tin-copper intermetallic compound as a main component. Specifically, for example, a metal containing Sn alone, Cu ₆ Sn ₅ , Cu ₃ Sn or the like is included as a main component. Moreover, as a remaining component, you may contain other metal elements, such as Bi and Cu, in the range which does not impair the effect of this invention, specifically, 10 mass% or less, for example.

  Further, in the metal portion 15, as shown in FIG. 1B, the third metal region 19 containing Bi as a main component is not in contact with the Cu particles 7 but in contact with the second metal region 18. Preferably it is present. When the third metal region 19 is present in the via-hole conductor 14 so as not to contact the Cu particles 7, the third metal region 19 does not lower the conductivity of the first metal region 17.

  The third metal region 19 contains Bi as a main component. Further, the third metal region 19 includes, as a remaining component, an alloy of Bi and Sn or an intermetallic compound in a range that does not impair the effects of the present invention, specifically, for example, in a range of 20% by mass or less. But you can.

  In addition, since the 2nd metal area | region 18 and the 3rd metal area | region 19 have mutually contact | connected, both usually contain both Bi and Sn. In this case, the second metal region 18 has a higher Sn concentration than the third metal region 19, and the third metal region 19 has a higher Bi concentration than the second metal region 18. In addition, the interface between the second metal region 18 and the third metal region 19 is preferably unclear rather than clear. When the interface is unclear, it is possible to suppress stress concentration on the interface even under heating conditions such as a thermal shock test.

  Further, in the via-hole conductor 14, fourth metal regions 22 that are tin-bismuth solder particles are surrounded by the resin portions 16 and are scattered. The tin-bismuth-based solder particles that are the fourth metal region are unreacted tin-bismuth-based solder particles that did not react with other components in the manufacturing process as described later. Such tin-bismuth-based solder particles are scattered so as to be surrounded by the resin portion 16 so as not to come into contact with the bonded body of copper particles, and thus do not hinder the formation of a conduction path.

  In this manner, unreacted tin-bismuth solder particles are scattered around the first metal region, the second metal region, or the third metal region in contact with the second metal region including the bonded body of copper particles. Thus, the oxidation resistance of the metal portions of the via hole conductors in the first metal region, the second metal region, and the third metal region is improved, or the adverse effect due to moisture remaining or entering the wiring substrate is reduced.

  In addition, in this way, a part of the tin-bismuth solder particles is encapsulated in a resin as a part of a metal part contributing to electrical conduction between the via-hole conductor and the wiring board and electrically insulated. The first metal region, the second metal region, or the third metal region in contact with the second metal region, etc., or via-hole conductors containing the copper particle combination It is possible to improve the oxidation resistance, or to reduce the influence of moisture remaining inside the wiring board or entering the inside of the wiring board while being used.

  The via-hole conductor in a state where the tin-bismuth solder particles scattered in these resins are reduced by functional groups such as amines and hydroxyl groups contained in the resin and the surface thereof is clean (or reduced). By interspersing with the metal material that constitutes the wiring board, it remains slightly in the interior of the wiring board (or enters from the outside) during the post-process of the wiring board or when the completed wiring board is used at the customer site. This is considered to be because it becomes a trap (catcher or sacrificial part) for moisture and oxidizing components, and the influence of moisture and the influence of oxidation can be suppressed.

  In order to suppress the influence of such moisture and oxidation, it is desirable that the average particle size of the tin-bismuth solder particles scattered in the via-hole conductor is not more than the average particle size of the copper particles. This means that even if large tin-bismuth solder particles are scattered in the resin so as to exceed the average particle diameter of the copper particles, a specific surface area that functions as a trap or the like or a uniform distribution degree cannot be obtained. This is because there are cases.

  For this purpose, the average particle size of the tin-bismuth solder particles contained in the via paste (particularly the liquid via paste before forming the via-hole conductor through the steps of compression, heating, etc.) The average particle diameter of the copper particles contained in the via paste is less than or equal to the average particle diameter, which is useful depending on the application (for example, further improvement in reliability, narrowing of the via, or reduction in diameter).

  Thus, the metal portion 15 constituting the via-hole conductor 14 is at least one metal selected from the group consisting of the first metal region 17 made of the copper particles 7, tin, a tin-copper alloy, and a tin-copper intermetallic compound. A second metal region 18 mainly containing bismuth, a third metal region 19 mainly containing bismuth, and a fourth metal region 22 mainly containing tin-bismuth solder particles. In addition, it is preferable that the weight ratio (Cu / Sn) of Cu and Sn of the metal part 15 is in the range of 1.59 to 21.43. The significance of this Cu / Sn ratio will be described in detail later.

  On the other hand, the resin part 16 which comprises the via-hole conductor 14 consists of hardened | cured material of curable resin. The curable resin is not particularly limited, and specifically, for example, a cured product of an epoxy resin is particularly preferable from the viewpoint of excellent heat resistance and a low coefficient of linear expansion.

  The ratio of the resin portion 16 in the via-hole conductor 14 is preferably 0.1 to 50% by mass, and more preferably 0.5 to 40% by mass. When the ratio of the resin portion 16 is too high, the resistance value tends to be high, and when it is too low, it tends to be difficult to prepare the conductive paste during manufacturing.

  Next, the effect | action of the via-hole conductor 14 in the multilayer wiring board 11 is typically demonstrated with reference to FIG.

  FIG. 2 is an explanatory diagram focusing on the conduction path 23 of one combined body 17a formed by contacting a large number of Cu particles 7 with each other. For convenience, the resin portion 16 and the like are not shown. Furthermore, 21 is a virtual spring shown for convenience in order to explain the operation of the via-hole conductor 14.

  As shown in FIG. 2, the combined body 17a formed by the surface contact of a large number of Cu particles 7 with each other at random becomes a conduction path 23 for electrically connecting the wiring 12a and the wiring 12b to each other. . In the surface contact portion 20 where the Cu particles 7 are in contact with each other, the second metal region 18 is preferably formed so as to cover the surface contact portion 20 and straddle the surface contact portion 20. .

  When an internal stress is generated inside the multilayer wiring board 11, a force is applied to the inside of the multilayer wiring board 11 as indicated by an arrow 33a. Such internal stress is generated, for example, due to a difference in coefficient of thermal expansion of materials constituting each element during solder reflow or thermal shock test.

  Such outward force may be caused by deformation of the highly flexible Cu particles 7 itself, elastic deformation of the bonded body 17a formed by contacting the Cu particles 7 or contact positions of the Cu particles 7. Is mitigated by a slight shift. At this time, since the hardness of the second metal region 18 is harder than the hardness of the Cu particles 7, the second metal region 18 tries to resist deformation of the combined body 17 a, particularly deformation of the surface contact portion 20. Therefore, when the combined body 17a tries to follow the deformation without limitation, the second metal region 18 is not deformed until the surface contact portion 20 between the Cu particles 7 is separated in order to restrict the deformation to a certain extent. .

  This is because, when the combined body 17a formed by contacting the Cu particles 7 is likened to a spring, when a certain amount of force is applied to the combined body 17a, the spring extends to a certain extent but follows the deformation. However, when the deformation is likely to be further increased, the deformation of the combined body 17 a is restricted by the hard second metal region 18. This also has the same effect when an inward force as shown by the arrow 33b is applied to the multilayer wiring board 11. Thus, the reliability of the electrical connection can be ensured by restricting the deformation of the combined body 17a with respect to the force in any direction of the external force and the internal force as if the spring 21.

  Next, in order to describe an example of a method for manufacturing the multilayer wiring board 11 as described above, each manufacturing process will be described in detail with reference to the drawings.

  In the manufacturing method of the present embodiment, first, as shown in FIG. 4A, protective films 26 are bonded to both surfaces of the resin sheet 25. In the present embodiment, a resin sheet made of a laminate in which uncured resin layers 25a are laminated on both surfaces of the heat resistant resin sheet 13a is used as the resin sheet 25. When such a resin sheet 25 is used, a thin multilayer wiring board can be obtained as compared with a multilayer wiring board obtained by using a prepreg as will be described later.

  Specifically, for example, it is possible to form an insulating resin layer having sufficient insulation even with a thickness of 15 μm or less, and even a thickness of 6 μm or less. The uncured resin layer 25a bonds the metal foil and the formed wiring.

  The heat-resistant resin sheet 13a is not particularly limited as long as it is a resin sheet that can withstand the soldering temperature. Specific examples thereof include a sheet made of polyimide, liquid crystal polymer, polyether ether ketone, or the like. Among these, a polyimide sheet is particularly preferable.

  The thickness of the heat resistant resin sheet 13a is preferably 1 to 100 μm, more preferably 3 to 75 μm, and particularly preferably 7.5 to 60 μm.

  Examples of the uncured resin layer 25a include an uncured adhesive layer made of an epoxy resin or the like. Further, the thickness per one side of the uncured resin layer 25a is preferably 1 to 30 [mu] m, and more preferably 5 to 10 [mu] m, in terms of contributing to thinning of the multilayer wiring board.

  Various resin films are used as the protective film. Specific examples thereof include resin films such as PET (polyethylene terephthalate) and PEN (polyethylene naphthalate). The thickness of the resin film is preferably 0.5 to 50 μm, and more preferably 1 to 30 μm. In the case of such a thickness, as will be described later, a protrusion made of a sufficiently high via paste can be exposed by peeling off the protective film.

  Examples of the method of bonding the protective film 26 to the resin sheet 25 include a method of directly bonding using the surface tackiness of the surface of the uncured resin layer 25a.

  Next, as shown in FIG. 4B, a through hole 27 is formed by perforating the resin sheet 25 provided with the protective film 26 from the outside of the protective film 26. For drilling, various methods such as drilling using a drill as well as non-contact processing methods such as carbon dioxide laser and YAG laser are used. The diameter of the through hole is 10 to 500 μm, and further about 50 to 300 μm.

  Next, as shown in FIG. 4C, the via paste 28 is fully filled in the through hole 27. The via paste 28 contains Cu particles, Sn—Bi solder particles containing Sn and Bi, and a curable resin component such as an epoxy resin.

  The average particle size of the Cu particles is preferably 0.1 to 20 μm, more preferably 1 to 10 μm. When the average particle size of the Cu particles 7 is too small, it is difficult to form a surface contact portion as will be described later in the via-hole conductor, and the conduction resistance tends to increase because the number of contact points increases. On the other hand, when the average particle diameter of the Cu particles is too large, the conduction resistance tends to increase due to the difficulty in increasing the filling factor when trying to form a via-hole conductor 14 having a small diameter such as 30 to 150 μmφ. There is. In particular, in the case of a fine via-hole conductor having a maximum diameter of 30 to 150 μm, the average particle diameter of the copper particles is preferably in the range of 3 to 10 μm.

  Moreover, the particle shape of Cu particle | grains is not specifically limited. Specifically, for example, a spherical shape, a flat shape, a polygonal shape, a scale shape, a flake shape, or a shape having a protrusion on the surface can be given. Moreover, a primary particle may be sufficient and the secondary particle may be formed.

  The Sn—Bi solder particles are not particularly limited as long as they are solder particles containing Sn and Bi. The Sn—Bi solder particles can change the eutectic temperature (melting point) to about 138 ° C. to 232 ° C. by changing the composition ratio or adding various elements. Furthermore, wettability, fluidity, and the like can be improved by adding indium (In), silver (Ag), zinc (Zn), or the like. Among these, Sn-58Bi solder, which is a lead-free solder in consideration of environmental problems with a low eutectic temperature of 138 ° C., is particularly preferable.

  The average particle diameter of the Sn—Bi solder particles is preferably 0.1 to 20 μm, and more preferably 2 to 15 μm. If the average particle size of the Sn—Bi solder particles is too small, the specific surface area tends to be large and the surface oxide film ratio tends to be large, making it difficult to melt. On the other hand, when the average particle diameter of the Sn—Bi solder particles is too large, the filling property to the via holes tends to be lowered.

  In addition, it is desirable that the average particle diameter of the Sn—Bi solder particles covered with a plurality of resins dispersed in the via-hole conductor is approximately the same as or smaller than the average particle diameter of the Cu particles. Specifically, it is preferably 0.3 to 1.0 times, more preferably 0.5 to 0.8 times the average particle size of the copper particles. Leaving Sn-Bi solder particles in a state of being covered with resin, which is the same size or smaller than the average particle size of Cu particles, contributes to cost reduction of via paste. This is because there are cases where steps such as classification of Sn—Bi solder can be omitted.

  In the via paste of the present embodiment, it is desirable that the tin-bismuth solder particles contain particles having a particle size that is equal to or smaller than the average particle size of the copper particles. By including tin-bismuth solder particles having an average particle size of copper particles or less in the via paste, the fourth metal region can be reliably formed.

  Further, in the via paste, the particle size of the tin-bismuth solder particles for forming the fourth metal region is equal to or less than the average particle size of the copper particles, specifically 2/3 or less of the average particle size, and further 1 / 2 or less is preferable. This is because when such small solder particles are sandwiched between copper particles, the epoxy resin sandwiched between the copper particles can be easily driven out effectively. This is because, when tin-bismuth solder particles having an average particle size of copper particles or less are sandwiched between the copper particles, the solder particles are as if they are movable pushers (or syringes) in a cylinder (or syringe) constituting a syringe. This is because it may function as a plunger or a gasket attached to the tip of the pusher.

  And so that the sandwiched solder particles push the epoxy resin filled in the syringe out of the syringe, the epoxy resin sandwiched in the gap between the copper particles is easy to move out of the gap between the copper particles. is there. Further, in the via paste, when the particle size of the tin-bismuth solder particles is less than the average particle size of the copper particles, the copper particles are formed on the surface contact portion at the time of compression and surface contact formation between the copper particles. Tin-bismuth solder is unlikely to remain in the gaps between them, and it is difficult to affect the formation of surface contact.

  The average particle diameter of the particles may be determined by selecting one having a high measurement accuracy (further repeatability) from among the number average diameter, length average, area average diameter, volume average diameter, and the like. As the particle diameter, a mode diameter or a median diameter (sometimes referred to as d50) is used. In addition, as a particle size measuring method, a commercially available laser diffraction scattering method, a Coulter type particle size distribution measuring device, or a cross section of a sample may be photographed with an SEM and obtained by calculation based on the image data.

  Specific examples of epoxy resins that are preferable curable resin components include, for example, glycidyl ether type epoxy resins, alicyclic epoxy resins, glycidyl amine type epoxy resins, glycidyl ester type epoxy resins, or other modified epoxy resins. Can do.

  Moreover, you may mix | blend a hardening | curing agent in combination with an epoxy resin. The type of the curing agent is not particularly limited, but it is particularly preferable to use a curing agent containing an amine compound having at least one hydroxyl group in the molecule. Such a curing agent acts as a curing catalyst for the epoxy resin, and also reduces the contact resistance at the time of bonding by reducing the oxide film present on the surface of the Cu particles and Sn-Bi solder particles. It is preferable from the point of having. Among these, an amine compound having a boiling point higher than the eutectic temperature of the Sn—Bi solder particles is particularly preferable because of its particularly high effect of reducing the contact resistance during bonding.

  Specific examples of such amine compounds include, for example, 2-methylaminoethanol (boiling point 160 ° C), N, N-diethylethanolamine (boiling point 162 ° C), N, N-dibutylethanolamine (boiling point 229 ° C), N-methylethanolamine (boiling point 160 ° C), N-methyldiethanolamine (boiling point 247 ° C), N-ethylethanolamine (boiling point 169 ° C), N-butylethanolamine (boiling point 195 ° C), diisopropanolamine (boiling point 249 ° C) ), N, N-diethylisopropanolamine (boiling point 125.8 ° C.), 2,2′-dimethylaminoethanol (boiling point 135 ° C.), triethanolamine and the like (boiling point 208 ° C.).

  The via paste is prepared by mixing Cu particles, Sn—Bi solder particles containing Sn and Bi, and a curable resin component such as an epoxy resin. Specifically, for example, it is prepared by adding Cu particles and Sn-Bi solder particles to a resin varnish containing an epoxy resin, a curing agent, and a predetermined amount of organic solvent, and mixing with a planetary mixer or the like. .

  The blending ratio of the curable resin component to the total amount of the metal component including the Cu particles and the Sn-Bi solder particles is in the range of 0.3 to 30% by mass, and further 3 to 20% by mass. It is preferable from the viewpoint of obtaining a low resistance value and ensuring sufficient workability.

  Moreover, as a content rate of Cu particle | grains in a metal component, it is preferable to make it contain so that the weight ratio (Cu / Sn) of Cu and Sn may become the range of 1.59-21.43. The reason for this will be described in detail later. Therefore, for example, when Sn-58Bi solder particles are used as Sn-Bi solder particles, the content ratio of Cu particles to the total amount of Cu particles and Sn-58Bi solder particles is 40 to 90% by mass, Furthermore, it is preferable that it is 55.8-65.5 mass%.

  The via paste filling method is not particularly limited. Specifically, for example, a method such as screen printing is used. In the manufacturing method of the present embodiment, when the via paste is filled in the through holes, a part of the via paste 28 is formed on the resin sheet 25 when the protective film 26 is peeled after the filling step. It is necessary to fill an amount protruding from the through hole 27 formed in the resin sheet 25 so that the protruding portion protrudes from the through hole 27.

  Next, as shown in FIG. 4D, the protective film 26 is peeled off from the surface of the resin sheet 25, thereby causing a part of the via paste 28 to protrude as the protruding portion 29 from the through hole 27. Although the height h of the protrusion part 29 is based also on the thickness of a protective film, it is 0.5-50 micrometers, for example, Furthermore, it is preferable that it is 1-30 micrometers. When the height of the protruding portion 29 is too high, it is not preferable because the paste may overflow around the through-holes 27 on the surface of the resin sheet 25 in the press-bonding step described later, and the surface smoothness may be lost. When too much, there exists a tendency for a pressure not to fully be transmitted to the via paste with which it filled in the crimping | compression-bonding process mentioned later.

  Next, as shown to FIG. 5 (A), the copper foil 30 is arrange | positioned on the resin sheet 25, and it presses in the direction shown by the arrow. Thereby, the insulating resin layer 13 is formed by integrating the resin sheet 25 and the copper foil 30 as shown in FIG.

  In this case, since a force is applied to the protrusion 29 through the copper foil 30 at the beginning of pressing, the via paste 28 filled in the through hole 27 is compressed with a high pressure. Thereby, the space | interval of several Cu particle | grains 7 contained in the via paste 28 is narrowed, Cu particle | grains 7 mutually deform | transform and surface-contact.

  The pressing condition is not particularly limited, but a condition in which the mold temperature is set from room temperature (20 ° C.) to a temperature lower than the eutectic temperature of the Sn—Bi solder particles is preferable. Moreover, in this press process, in order to advance hardening of the uncured resin layer 25a, you may use the heating press heated to the temperature required in order to advance hardening.

  Here, a state when the via paste 28 having the protrusion 29 is compressed will be described in detail with reference to FIG.

  FIG. 7 is a schematic cross-sectional view around the through hole 27 of the resin sheet 25 filled with the via paste 28. FIG. 7A shows before compression, and FIG. 7B shows after compression.

  As shown in FIG. 7A, by pressing the protruding portion 29 protruding from the through hole 27 formed in the resin sheet 25 through the copper foil 30, the through hole 27 is formed as shown in FIG. The filled via paste 28 is compressed. A part of the curable resin component 32 may be extruded onto the surface of the resin sheet 25 due to the pressurization during the compression. As a result, the density of the Cu particles 7 and the Sn—Bi solder particles 31 filled in the through holes 27 is increased.

  The Cu particles 7 can be brought into surface contact with each other by appropriately selecting the content ratio of the Cu particles 7, the particle diameter of the Cu particles 7, and the particle diameter of the Sn—Bi solder particles 31. In the compression, initially, the Cu particles 7 are in point contact with each other, and thereafter are crushed as the pressure increases, and are deformed and brought into surface contact to form a surface contact portion. Thus, when many Cu particles 7 are in surface contact with each other, a combined body 17a for electrically connecting the upper layer wiring and the lower layer wiring in a low resistance state is formed. In this step, a bonded body 17a in which the copper particles 7 in the via paste 28 are in contact with each other through the surface contact portion 20 is formed.

  It is desirable to pressurize and compress the via paste 28 by pressing the copper foil 30 to the resin sheet 25 and applying a predetermined pressure to the protruding portion 29 of the via paste 28 via the copper foil 30. By doing so, the copper particles 7 are brought into surface contact with each other, and the first metal region 17 including the combined body 17a of the copper particles 7 is formed. In order to bring the copper particles 7 into surface contact, it is desirable to compress and compress the copper particles 7 until they are plastically deformed. In this crimping step, it is effective to heat (or start heating) as necessary. This is because it is useful to perform a heating step following the crimping step.

  Furthermore, it is useful to heat a part of the Sn—Bi solder particles by heating at a predetermined temperature while maintaining the pressure-bonded state. By heating and dissolving the solder particles in a state where the crimped state is maintained, it is possible to prevent the dissolved solder or the like from entering the surface contact portion between the copper particles. Therefore, it is useful to provide a heating process as part of the crimping process. Moreover, by starting heating in the crimping process, the total time of the crimping process and the heating process can be shortened, and productivity can be increased.

  This compression is preferably performed at a temperature not lower than room temperature (20 ° C.) and lower than the melting temperature (or eutectic temperature) of the tin-bismuth solder particles in the via paste 28. By performing compression in this temperature range, the alloying reaction of tin-bismuth solder can be suppressed during the compression process.

  The compressed via paste is heated while maintaining the compression. The heating is made higher than the melting temperature (or eutectic temperature) of the tin-bismuth solder used.

  For example, a part of the Sn-Bi solder particles is melted in the temperature range from the eutectic temperature of the Sn-Bi solder particles to the eutectic temperature + 10 ° C or lower, and then the eutectic temperature + 20 ° C to 300 ° C. By heating to a temperature range of 2%, the surface of the bonded body of the copper particles excluding the surface contact portion is mainly composed of at least one of tin, a tin-copper alloy, and an intermetallic compound of tin and copper. It is desirable to form a metal region. Furthermore, it is useful to set these as one process with continuous pressure bonding and heating. In one continuous process, the formation reaction of each metal region can be stabilized, and the structure of the via itself can be stabilized.

  The bonded body 17 a is formed by compression, and the via paste 28 is gradually heated to a temperature equal to or higher than the eutectic temperature of the Sn—Bi solder particles 31. By this heating, a part of the Sn—Bi solder particles 31 melts at a composition ratio that melts at that temperature. And the 2nd metal area | region 18 which has a tin, a tin-copper alloy, and / or a tin-copper intermetallic compound as a main component is formed in the surface and circumference | surroundings of Cu particle | grains 7 or the coupling body 17a.

In this case, the surface contact portion 20 where the Cu particles 7 are in surface contact with each other is preferably covered so as to straddle the second metal region 18. When the Cu particles 7 and the melted Sn—Bi solder particles 31 come into contact with each other, Sn in the Sn—Bi solder particles 31 reacts with Cu in the Cu particles 7 to form Cu ₆ Sn ₅ or Cu _3. A Sn-Cu compound layer (intermetallic compound) containing Sn and a second metal region 18 mainly composed of a tin-copper alloy are formed. On the other hand, the Sn—Bi-based solder particles 31 continue to maintain a molten state while being supplemented with Sn from the internal Sn phase, and the remaining Bi precipitates, whereby the third metal region 19 containing Bi as a main component is formed. It is formed. As a result, a via-hole conductor 14 having a structure as shown in FIG. Further, a part of the Sn—Bi solder particles 31 is surrounded by the curable resin component 32 and is scattered to form the fourth metal region 22.

  Then, the surface of the fourth metal region is reduced by the activator (for example, amine-based additive) surrounded by the curable resin component 32 and added to the via paste, and the activated fourth metal region is surrounded by the periphery of the via-hole conductor. To be scattered. Then, the fourth metal region surrounded by the thermosetting resin component 32 scattered around the via-hole conductor is caused to function as a trap (or a catcher) for moisture entering from the outside or the like, or an oxidizing component. Increase the reliability of via-hole conductors. This is because the tin-bismuth-based solder particles forming the fourth metal region are affected before the via-hole conductor is affected by moisture entering from the outside or an oxidizing component.

  More specifically, the Cu particles 7 densified as described above come into contact with each other by compression. In the compression, the Cu particles 7 are first brought into point contact with each other, and then are crushed as the pressure increases, and are deformed and brought into surface contact to form a surface contact portion. Thus, when many Cu particles 7 are in surface contact with each other, a combined body 17a for electrically connecting the upper layer wiring and the lower layer wiring in a low resistance state is formed.

  Further, since the surface contact portion is not covered with the Sn—Bi solder particles 31, it is possible to form a combined body 17 a in which the Cu particles 7 are brought into direct contact with each other. As a result, the electric resistance of the formed conduction path can be reduced. And when it heats in this state and reaches the eutectic temperature or higher of the Sn-Bi solder particles 31, the Sn-Bi solder particles 31 begin to partially melt. The composition of the solder to be melted is determined by the temperature, and Sn that is difficult to melt at the temperature at the time of heating remains as an Sn solid phase body.

  Further, when Cu particles 7 come into contact with the molten solder and the surface thereof is wetted by the melted Sn-Bi solder, the mutual diffusion of Cu and Sn proceeds at the interface of the wet part, and the Sn-Cu compound layer Etc. are formed.

  Thus, the 2nd metal area | region 18 produces | generates so that the surface except the surface contact part of Cu particle | grains 7 may be contacted. A part of the second metal region 18 is formed so as to straddle the surface contact portion.

  When a part of the second metal region 18 is coated so as to straddle the surface contact portion, the surface contact portion is reinforced and becomes a conductive path having excellent elasticity. Then, Sn in the melted solder decreases due to the further formation of the Sn—Cu compound layer and the like and the mutual diffusion. Since the reduced Sn in the molten solder is compensated from the Sn solid layer, the molten state continues to be maintained. Further, when Sn decreases and the ratio of Sn and Bi becomes larger than that of Sn-57Bi, Bi begins to segregate, and a second metal region is formed as a solid phase body containing bismuth as a main component.

  As well-known solder materials that melt at a relatively low temperature range, there are Sn—Pb solder, Sn—In solder, Sn—Bi solder, and the like. Of these materials, In is expensive and Pb is considered to have a high environmental load. On the other hand, the eutectic temperature of Sn-Bi solder is lower than a general solder reflow temperature when surface-mounting an electronic component.

  Therefore, when only Sn-Bi solder is used as the via hole conductor of the circuit board as a single unit, the via resistance may change due to remelting of the solder of the via hole conductor during solder reflow.

  On the other hand, when the via paste of this embodiment is used, Sn of the Sn—Bi solder particles reacts with the surface of the Cu particles to reduce the Sn concentration from the Sn—Bi solder particles. By passing through the cooling step, Bi precipitates and a third metal region is generated.

  In addition, by allowing the third metal region to be deposited in this manner, the solder of the via-hole conductor is not easily remelted even when subjected to solder reflow. As a result, the resistance value hardly changes even after the solder reflow. Further, a part of the Sn—Bi solder particles 31 is surrounded by the curable resin component 32 and is scattered to form the fourth metal region 22.

  Then, the fourth metal region 22 surrounded by the thermosetting resin component 32 scattered around the via-hole conductor is caused to function as a trap (or a catcher) for moisture entering from the outside, an oxidizing component, or the like. Therefore, the reliability of the via-hole conductor is increased.

  The temperature for heating the compressed via paste 28 is not particularly limited as long as it is a temperature equal to or higher than the eutectic temperature of the Sn—Bi solder particles 31 and does not decompose the constituent components of the resin sheet 25. Specifically, for example, when Sn-58Bi solder particles are used as the Sn—Bi solder particles, the temperature is preferably in the range of about 150 to 250 ° C., more preferably about 160 to 230 ° C.

  At this time, the curable resin component contained in the via paste 28 can be cured by appropriately selecting the temperature.

  In this way, the via-hole conductor 14 is formed for interlayer connection between the upper layer wiring and the lower layer wiring.

  In the present embodiment, the content ratio of the Cu particles in the metal component contained in the via paste 28 is such that the weight ratio of Cu and Sn (Cu / Sn) is in the range of 1.59 to 21.43 as described above. It is preferable to contain so that it may become. The reason for this will be described below.

  FIG. 3 is a schematic cross-sectional view showing an example of a via-hole conductor when Cu / Sn is smaller than 1.59.

  As shown in FIG. 3, when the ratio of Cu / Sn is smaller than 1.59, the ratio of Cu in the via-hole conductor is reduced, and a large number of Cu particles 7 are difficult to come into surface contact with each other. There is a tendency to exist so as to be scattered in a matrix made of intermetallic compound 4.

In this case, since a large number of Cu particles 7 are hardly bound by the hard intermetallic compound 4, the via-hole conductor itself tends to be in a hard state with low spring property. Compared to the Cu particles 7, the intermetallic compound 4 such as Cu ₆ Sn ₅ and Cu ₃ Sn is hard and hardly deformed. According to the inventors research, Vickers hardness is about 343Kg / mm ² at about 378Kg ^/ mm 2, _Cu 3 Sn in _Cu 6 Sn _5, significantly higher than 117 kg / mm ² for Cu.

  Since the Cu particles 7 and the intermetallic compound 4 have different coefficients of thermal expansion, internal stress due to the difference in coefficient of thermal expansion occurs during solder reflow, and as a result, cracks and voids 24 are likely to occur.

  Further, when the Cu / Sn weight ratio is less than 1.59, voids are likely to occur. An important cause of the generation of such voids is Kirkendall void due to Kirkendall effect due to contact diffusion between Sn and Cu. Kirkendall voids are likely to occur at the interface between the surface of the Cu particles and Sn or an alloy containing Sn filled in the gap between the Cu particles.

  As shown in FIG. 3, when cracks or voids 24 exist at the interface between the Cu particles 7 and the intermetallic compound 4, the cracks and voids 24 tend to propagate and spread easily. When a Kirkendall void occurs, the Kirkendall void also tends to propagate and easily spread. In particular, when the diameter of the via-hole conductor is small, the cracks and voids 24 tend to cause cohesive failure of the intermetallic compound 4 and further breakage of the via-hole conductor. When such cohesive failure or interface failure occurs inside the via hole conductor, the electrical resistance of the via portion increases, which affects the reliability of the via portion.

  On the other hand, the case where the ratio of Cu / Sn is 1.59 or more will be schematically described with reference to FIGS.

  When the ratio of Cu / Sn is 1.59 or more, as shown in FIG. 1B, the second metal region 18 included in the metal portion 15 has a surface contact portion 20 where a large number of Cu particles 7 are in surface contact with each other. The surface of the Cu particles 7 is physically protected.

  Arrows 33 a and 33 b shown in FIG. 2 indicate external forces applied to the via-hole conductor 14 and internal stresses generated in the via-hole conductor 14. When an external force as indicated by an arrow 33a or an internal stress indicated by an arrow 33b is applied to the via-hole conductor 14, the force is relaxed by the deformation of the flexible Cu particles 7.

  Moreover, even if a crack occurs in the second metal region 18, a large number of Cu particles 7 are in surface contact with each other, so that a conduction path by the combined body 17 a is sufficiently secured, and electrical characteristics and reliability are ensured. Does not significantly affect sex.

  As shown in FIG. 1B, since the entire metal portion 15 is elastically protected by the resin portion 16, the deformation is further suppressed within a certain range. Therefore, cohesive failure and interface failure are less likely to occur.

  When Cu / Sn is 1.59 or more, the second metal region 18 is easily formed so as to straddle the surface contact portion 20. And when Cu / Sn is 1.59 or more, Kirkendall void does not occur in the interior of Sn—Bi solder particles filled in the gap between Cu particles or in the interface thereof, but in the second metal. It tends to occur on the region 18 side. Kirkendall voids generated in the second metal region 18 are unlikely to affect the reliability and electrical characteristics of the via-hole conductor 14. This is because electrical conduction is sufficiently ensured by contact between the Cu particles 7.

  Next, as shown in FIG. 5C, wirings 12a and 12b are formed. The wirings 12a and 12b are formed by forming a photoresist film on the surface of the copper foil 30 bonded to the surface layer, patterning by selective exposure through a photomask, developing, and etching. After the foil is selectively removed, it can be formed by removing the photoresist film or the like. For the formation of the photoresist film, a liquid resist or a dry film may be used.

  By such a process, a wiring substrate 41 having a circuit formed on both surfaces where the upper layer wiring 12a and the lower layer wiring 12b are interlayer-connected through the via-hole conductor 14 is obtained. By further multilayering such a wiring substrate 41, a multilayer wiring substrate 11 in which a plurality of layers of circuits as shown in FIG. A method of multilayering the wiring board 41 will be described with reference to FIG.

  First, as shown in FIG. 6A, protrusions 29 made of via paste 28 similar to those obtained in FIG. 4D are formed on both surfaces of the wiring board 41 obtained as described above. A resin sheet 25 is disposed.

  Furthermore, the copper foil 30 is arrange | positioned on each outer surface of each resin sheet 25, and a laminated body is formed. And this laminated body is inserted | pinched between a press metal mold | die, and a laminated body as shown in FIG.6 (B) is obtained by pressing and heating on the conditions as mentioned above. Then, a new wiring 42 is formed by using the photo process as described above. By further repeating such a multilayering process, a multilayer wiring board 11 is obtained as shown in FIG.

[Second Embodiment]
In the second embodiment, in the production of the multilayer wiring substrate 11 of the first embodiment, a so-called uncured state obtained by impregnating a fiber sheet with a resin varnish instead of the resin sheet 25 and then drying it, or An example using the semi-cured state (B-stage) prepreg 125 will be described. In addition, since it is the same as that of 1st embodiment except having used the prepreg 125 instead of the resin sheet 25, the same code | symbol is shown about the common part. Detailed descriptions of the same matters as in the first embodiment are omitted.

  FIG. 8A is a schematic cross-sectional view of the multilayer wiring board 111 of the present embodiment.

  FIG. 8B is an enlarged schematic cross-sectional view of the vicinity of the via-hole conductor 14 in the multilayer wiring board 111 of FIG.

  In FIG. 8, 12 (12a, 12b) is a wiring, 113 is an insulating resin layer, and 14 is a via-hole conductor. The via-hole conductor 14 includes a metal portion 15 and a resin portion 16. The insulating resin layer 113 is made of a fiber-containing resin sheet in which a fiber sheet 113a is impregnated with a cured resin 113b.

  The metal portion 15 includes a first metal region 17 formed from the Cu particles 7 and a main component of at least one metal selected from the group consisting of tin, a tin-copper alloy, and a tin-copper intermetallic compound. It includes a bimetallic region 18, a third metallic region 19 containing Bi as a main component, and a fourth metallic region 22 that is a tin-bismuth-based particle.

  At least a part of the Cu particles 7 are in surface contact with each other to form a bonded body 17a of copper particles included in a region indicated by a broken line. The combined body 17a functions as a low-resistance conductive path that electrically connects the upper wiring 12a and the lower wiring 12b.

  Next, in order to describe an example of a method for manufacturing the multilayer wiring board 111 as described above, each manufacturing process will be described in detail with reference to FIGS.

  In the manufacturing method of the present embodiment, first, as shown in FIG. 9A, the protective film 26 is bonded to both surfaces of the prepreg 125 in an uncured state or a semi-cured state (B-stage).

  As the prepreg 125, for example, a so-called uncured or semi-cured (B-stage) prepreg obtained by impregnating a fiber base material with a thermosetting resin varnish and drying is preferably used. The fiber substrate may be a woven fabric or a non-woven fabric. Specific examples thereof include glass fiber cloth such as glass cloth, glass paper, and glass mat, and also, for example, organic fiber cloth made of kraft paper, linter paper, natural fiber cloth, and aramid fiber. Moreover, an epoxy resin etc. are mentioned as a resin component contained in a resin varnish. The resin varnish may further contain an inorganic filler or the like.

  As the protective film 26, the thing similar to what was demonstrated in 1st embodiment is used. As a method of bonding the protective film 26 to the prepreg 125, when the surface of the prepreg 125 has tackiness, a method of bonding by the tackiness can be mentioned.

  Next, as shown in FIG. 9 (B), a through-hole 27 is formed by perforating the prepreg 125 provided with the protective film 26 from the outside of the protective film 26. For drilling, various methods such as drilling using a drill as well as non-contact processing methods such as carbon dioxide laser and YAG laser are used. As a diameter of a through-hole, 10-500 micrometers, Furthermore, about 50-300 micrometers is mentioned.

  Next, as shown in FIG. 9C, the via paste 28 is fully filled in the through hole 27. The via paste 28 contains Cu particles, Sn—Bi solder particles containing Sn and Bi, and a curable resin component such as an epoxy resin. The via paste 28 is the same as that described in the first embodiment.

  Next, as shown in FIG. 9D, by peeling off the protective film 26 from the surface of the prepreg 125, a part of the via paste 28 is projected as a projecting portion 29 from the through hole 27 formed in the prepreg 125. . Although the height h of the protrusion part 29 is based also on the thickness of a protective film, it is 0.5-50 micrometers, for example, Furthermore, it is preferable that it is 1-30 micrometers. When the height of the protruding portion is too high, it is not preferable because the paste may overflow on the surface of the prepreg 125 around the through-hole 27 in the press-bonding process described later, and the surface smoothness may be lowered. In some cases, there is a tendency that the pressure is not sufficiently transmitted to the via paste filled in the crimping process described later.

  Next, as shown in FIG. 10A, the copper foil 30 is disposed on both surfaces of the prepreg 125 and pressed in the direction indicated by the arrow. Thereby, as shown in FIG. 10B, the prepreg 125 and the copper foil 30 are integrated to form the insulating resin layer 113. In this case, since a force is applied to the protrusion 29 through the copper foil 30 at the beginning of the press, the via paste 28 filled in the through hole of the prepreg 125 is compressed with a high force. Thereby, the space | interval of several Cu particle | grains 7 contained in the via paste 28 is narrowed, and Cu particle | grains 7 contact.

  The pressing condition is not particularly limited, but a condition in which the mold temperature is set from room temperature (20 ° C.) to a temperature lower than the eutectic temperature of the Sn—Bi solder particles is preferable.

  Here, the manner in which the via paste 28 having the protruding portions 29 filled in the through holes of the prepreg 125 is compressed will be described in detail with reference to FIG.

  FIG. 12 is a schematic cross-sectional view around the through hole 27 of the prepreg 125 filled with the via paste 28. 12A shows before compression, and FIG. 12B shows after compression. Reference numeral 113 a denotes a fiber base material included in the prepreg 125.

  As shown in FIG. 12 (A), the projecting portion 29 projecting from the through hole 27 formed in the prepreg 125 is pressed through the copper foil 30 to fill the through hole 27 as shown in FIG. 12 (B). The via paste 28 is compressed. A part of the curable resin component 32 permeates into the prepreg 125 due to the pressurization during the compression. As a result, the density of the Cu particles 7 and the Sn—Bi solder particles 31 filled in the through holes 27 is increased.

  And Cu particles 7 densified in this way contact each other. In the compression, the Cu particles 7 are initially brought into point contact with each other, and thereafter are crushed as the pressure increases, and are deformed and brought into surface contact to form a surface contact portion.

  Thus, when many Cu particles 7 are in surface contact with each other, a combined body for electrically connecting the upper layer wiring and the lower layer wiring in a low resistance state is formed. In this way, the via-hole conductor 14 is formed for interlayer connection between the upper layer wiring and the lower layer wiring.

  Next, as shown in FIG. 10C, wirings 12 (12a, 12b) are formed. The wiring 12 is formed by forming a photoresist film on the surface of the copper foil 30 bonded to the surface layer, patterning by selective exposure through a photomask, developing, and etching the copper foil other than the wiring portion. After the selective removal, it can be formed by removing the photoresist film or the like. For the formation of the photoresist film, a liquid resist or a dry film may be used.

  By such a process, a wiring substrate 141 having a circuit formed on both surfaces in which the upper layer wiring 12a and the lower layer wiring 12b are interlayer-connected through the via-hole conductor 14 is obtained. By further multilayering such a wiring substrate 141, a multilayer wiring substrate 111 in which a plurality of layers of circuits are connected in layers can be obtained. A method of further multilayering the wiring board 141 will be described with reference to FIG.

  First, as shown in FIG. 11A, protrusions 29 made of via paste 28 similar to those obtained in FIG. 9D are formed on both surfaces of the wiring board 141 obtained as described above. The prepreg 125 which has is arrange | positioned.

  Furthermore, the copper foil 30 is arrange | positioned on each outer surface of each prepreg 125, and a laminated body is formed. And this laminated body is inserted | pinched between a press metal mold | die, and a laminated body as shown in FIG.11 (B) is obtained by pressing and heating on the conditions as mentioned above. Then, a new wiring 42 is formed by using the photo process as described above. By repeating such a multilayering process, a multilayer wiring board 111 as shown in FIG. 11C is obtained.

  Next, the present invention will be described more specifically with reference to examples. The scope of the present invention is not construed as being limited in any way by the contents of this embodiment.

  First, the raw materials used in this example will be described together below.

Cu particles: 1100Y made by Mitsui Kinzoku Co., Ltd. with an average particle diameter of 5 μm
Sn-Bi solder particles: Sn42-Bi58, average particle size 5 μm, eutectic temperature 138 ° C., manufactured by Yamaishi Metal Co., Ltd. Epoxy resin: jeR871 manufactured by Japan Epoxy Resin Co., Ltd.
・ Curing agent 1: 2-methylaminoethanol, boiling point 160 ° C., manufactured by Nippon Emulsifier Co., Ltd. Curing agent 3: 2,2′-dimethylaminoethanol, boiling point 135 ° C.
・ Resin sheet: 500 mm long × 500 mm wide, 75 μm thick polyimide film laminated with uncured epoxy resin layer of 12.5 μm thickness ・ Protective film: 25 μm thick PET sheet ・ Copper foil (25 μm thickness)
(Adjustment of via paste)
Via paste was prepared by blending Cu particles, Sn42-Bi58 solder particles, an epoxy resin, and a curing agent in the blending ratio described in [Table 1] and mixing with a planetary mixer.
(Manufacture of multilayer wiring boards)
A protective film was bonded to both surfaces of the resin sheet. Then, 100 or more holes having a diameter of 150 μm were drilled from the outside of the resin sheet bonded with the protective film with a laser.

  Next, the prepared via paste was fully filled in the through holes. And the protrusion part in which a part of via paste protruded from the through-hole was exposed by peeling the protective film of both surfaces.

Next, copper foil was arrange | positioned so that a protrusion part might be covered on both surfaces of the resin sheet. And the laminated body with the resin sheet with which the copper foil was arrange | positioned through a release paper on the lower mold | type of a pair of metal mold | die of a heating press, and it is 60 from the normal temperature 25 degreeC to the maximum temperature 220 degreeC. The temperature was raised in minutes and 220 ° C. was kept for 60 minutes, and then cooled to room temperature over 60 minutes. The press pressure was 3 MPa. In this way, a multilayer wiring board was obtained.
(Evaluation)
<Resistance test>
The resistance value of 100 via-hole conductors formed on the obtained multilayer wiring board was measured by a four-terminal method. Then, 100 average resistance values and maximum resistance values were obtained. A case where the maximum resistance value was less than 2 mΩ was determined as A, a case where the maximum resistance value was 2 to 3 mΩ was determined as B, and a case where the maximum resistance value was greater than 3 mΩ was determined as C. When the maximum resistance value is small, it can be said that the standard deviation σ of the resistance value is also small.
<Peel test>
The adhesion of the via-hole conductor when the copper foil on the surface of the obtained multilayer wiring board was peeled (or destroyed) was examined. At this time, it was judged as A when it was not peeled, B when it was difficult to peel, and C when peeled easily.
<Initial resistance value>
The connection resistance value of 100 via holes formed in the multilayer wiring board was measured by the 4-terminal method. In addition, as an initial resistance value, 1 A or less was determined as A, 1 Ω or less and 1 Ω exceeding 1 Ω were mixed as B, and all exceeding 1 Ω were determined as C.
<Connection reliability>
A heat cycle test of 500 cycles of the multilayer wiring board for which the initial resistance value was measured was performed, and when the rate of change with respect to the initial resistance value was 10% or less, A was exceeded and 10% was judged as B.

  The results are shown in [Table 1]. Moreover, the graph which plotted the average resistance value with respect to the mass ratio of Cu / Sn is shown in FIG.

  From the graph of FIG. 13, it can be seen that the Cu / Sn weight ratio is drastically decreased from around 1.59, and from around 3. This is presumably because the ratio of low-resistance Cu particles that are in surface contact with each other increases as the ratio of Cu particles increases.

  That is, it is considered that there is almost no metal having a higher resistance value than Cu between adjacent Cu particles. And as shown in the SEM photograph mentioned later, when the weight ratio of Cu / Sn was 1.59 or more, it was confirmed that excess Sn42-Bi58 solder particles were surrounded by the epoxy resin. .

  Then, the fourth metal region surrounded by the thermosetting resin component 32 scattered around the via-hole conductor is caused to function as a trap (or a catcher) for moisture entering from the outside or the like, or an oxidizing component. It seems that the reliability of via-hole conductors is improved.

  This is because the tin-bismuth-based solder particles forming the fourth metal region are affected before the via-hole conductor is affected by moisture entering from the outside of the wiring board or the like, or by an oxidizing component.

  In other words, it is considered that when the resistance value is less than Cu / Sn 1.59 where the resistance value increases abruptly, a metal having a high resistance value is interposed between many Cu particles 7.

  Further, from [Table 1], when the ratio of Sn42-58Bi particles is 60% by mass or less, the average resistance value and the maximum resistance value are 3 mΩ or less, and when 44.2% by mass or less, the value is extremely small, 2 mΩ or less. It turns out that it becomes.

  However, it is understood that exfoliation is likely to occur when Sn42-58Bi particles are not contained. On the other hand, it can be seen that exfoliation hardly occurs as the proportion of Sn42-58Bi particles increases.

  It can also be seen that both low resistance and high reliability can be achieved when the ratio of Sn42-58Bi particles is in the range of 10 to 60% by mass. When the ratio of Sn42-58Bi particles is too low, the second metal region existing around the surface contact portion where the Cu particles are in contact with each other is reduced, resulting in insufficient connection reliability.

  On the other hand, when the proportion of the Sn42-58Bi particles is too high, the second metal region is excessively increased, so that the surface contact portion where the Cu particles are in contact with each other decreases, and the resistance value tends to increase.

  Also, paste No. When the multilayer wiring boards obtained using 7 to 9 are compared, paste No. 7 whose boiling point of the curing agent is higher than the eutectic temperature 138 ° C. of Sn42-58Bi particles. 7, no. In the case of 8, it can be seen that the balance of resistance reduction and high reliability is more excellent. When the boiling point is low, the oxide layer on the surface of the solder is reduced, and the volatilization of the curing agent starts before melting, so that the metal part area becomes small, which causes a problem in connection reliability of the via hole. The boiling point of the curing agent is desirably 300 ° C. or lower. When it is higher than 300 ° C., the curing agent becomes special and may affect the reactivity.

  Here, typically, paste No. 1 according to the present invention is used. 14 to 15 show an electron microscope (SEM) photograph of a cross-section of the via conductor of the multilayer wiring board obtained using 6 and a trace view thereof. Note that FIG. 14 is 3000 times and FIG. 15 is 6000 times, and shows an SEM photograph (A) and a trace view (B) thereof, respectively. FIG. 16 shows an SEM photograph and a trace view of a cross section of a via conductor used in EPMA (Electron Probe Micro Analyzer).

  14 to 16, it can be seen that the obtained via-hole conductor is highly filled with a large number of Cu particles 7 and is in surface contact with each other to form the surface contact portion 20. Thereby, it turns out that a conduction path with a low resistance value is formed. Further, the surface of the surface contact portion 20 or the copper particle 7 or the second metal region 18 mainly composed of tin (Sn), a tin-copper intermetallic compound, or a tin-copper alloy so as to straddle the surface contact portion 20. It can be seen that is formed.

  Moreover, it turns out that the 3rd metal area | region 19 which has Bi with a high resistance value as a main component is not substantially in contact with Cu particle | grains. In this third metal region, it seems that Sn in the Sn42-58Bi particles formed an alloy (for example, an intermetallic compound) with Cu on the surface of the Cu particles 7, so that a high concentration of Bi was precipitated.

  Also, paste No. FIG. 21 shows another SEM photograph of the cross-section of the via-hole conductor of the multilayer wiring board obtained using No. 6. FIG. 21A is a cross-sectional SEM photograph, and FIG. 21B is a trace view thereof. In the obtained SEM photograph, it can be seen that the via-hole conductor is highly filled with a large number of Cu particles 7 and is in surface contact with each other to form the surface contact portion 20 and form the first metal region 17. Thereby, it turns out that a conduction path with a low resistance value is formed.

  Further, the surface of the surface contact portion 20 or the copper particle 7 or the second metal region 18 mainly composed of tin (Sn), a tin-copper intermetallic compound, or a tin-copper alloy so as to straddle the surface contact portion 20. It can be seen that is formed. Moreover, it turns out that the 3rd metal area | region 19 which has Bi with a high resistance value as a main component is not substantially in contact with Cu particle | grains.

  In this third metal region, it seems that Sn in the Sn42-58Bi particles formed an alloy (for example, an intermetallic compound) with Cu on the surface of the Cu particles 7, so that a high concentration of Bi was precipitated. Further, the Sn42-58Bi particles, which are the fourth metal regions 22 that did not contribute to the formation of the second metal regions, do not exist inside the conduction path formed by the surface contact of the Cu particles, but exist independently in the gap. You can see that As a result, even if the Sn-Bi particles remain as they are without forming the second metal region due to a local deviation in the ratio of Cu particles to Sn-Bi particles, the initial resistance value and reliability are not adversely affected. Both are considered to provide good via connection.

  As described above, the via hole conductor is mainly composed of the Cu particles 7 (or the first metal region 17), and the Sn42-58Bi particles added to increase the strength of the surface contact portion 20 constituting the first metal region 17 are included in the Sn42-58Bi particles. It is desirable to leave the surplus component, that is, the component that did not contribute to the configuration of the second metal region 18 and the third metal region 19 as the fourth metal region 22 in a state that does not affect the via hole conductor.

  The surplus component in the Sn42-58Bi particles added as described above, that is, the component that did not contribute to the configuration of the second metal region 18 or the third metal region 19 is used as the fourth metal region 22 in the via-hole conductor. By leaving it in an unaffected state, the effects of variations in paste composition (within lot, between lots) or precipitation of paste (for example, specific gravity difference of metal particles, etc.) can be reduced. Alternatively, it is possible to stabilize the quality of the via portion between lots or between varieties. This contributes a sufficient amount of Sn42-58Bi particles necessary for the formation of the via-hole conductor to the structure of the second metal region 18 and the third metal region 19, and replaces the Sn42-58Bi particles corresponding to the surplus that did not contribute to the reaction with resin. This is to prevent the via hole characteristics from being affected by being divided by the resin or scattered in the resin sea. In this way, by preliminarily containing Sn42-58Bi particles in the paste so as to be more than the amount that contributes to the reaction, the effect of suppressing paste variation or via-hole conductor variation can be obtained.

  In addition, the total amount (for example, weight) of Sn-Bi existing as the fourth metal region is not more than the total amount (for example, weight) of Sn-Bi that contributed to the formation of the second and third metal regions, and further not more than 50%. Is desirable. This is because when the total amount (for example, weight) of Sn-Bi existing as the fourth metal region is larger than the total amount (for example, weight) of Sn-Bi that contributed to the formation of the second and third metal regions, a stable via-hole conductor May affect the formation of

  FIG. 17 shows an image (A) when the SEM image of FIG. 16 is mapped with Cu element by EPMA and a trace view (B) thereof.

  17 (A) and 17 (B), it can be seen that a large number of Cu particles are present at high density and randomly in the obtained via-hole conductor. Moreover, it turns out that many Cu particles are electrically connected by surface contact directly.

  FIG. 18 shows a Sn element mapping image (A) using the SEM image of FIG. 16 and a trace diagram (B) thereof.

  18A and 18B, it can be seen that the second metal region is formed on the surface of the surface contact portion where a large number of Cu particles are in direct contact with each other so as to straddle the surface contact portion.

  In FIG. 18, it seems that most of the surface of the Cu particles is covered with the second metal region. However, since the epoxy resin permeates in EPMA, not only the Sn element on the surface of the observation surface but also the Sn element on the base is detected. Therefore, actually, the second metal region does not cover most of the surface of the Cu particles, but exists so as to straddle the surface and further the surface contact portion. This can also be seen from the SEM images shown in FIGS. According to such a structure, the stress generated in the relatively hard second metal region is absorbed by the soft Cu particles. Therefore, it is suppressed that the crack generated in the second metal region propagates and spreads.

  Further, FIG. 19 shows a mapping image (A) of the Bi element using the SEM image of FIG. 16 and a trace diagram (B) thereof.

  From FIG. 19, it can be seen that Bi exists so that the third metal region does not come into contact with the Cu particles. From this, it can be seen that Bi having a high resistance value does not affect the conduction path formed by the contact of the Cu particles.

  Next, the particle diameters of Cu particles and Sn—Bi solder particles were examined. Specifically, paste No. 1 in Example 1 except that the Cu particles having the average particle diameter described in [Table 2] and Sn42-Bi58 solder particles were blended. In the same manner as in No. 6, Cu particles: Sn—Bi solder particles = 60: 40 were added, and paste No. 13-23 were prepared.

  And the multilayer wiring board was obtained like Example 1, and the initial stage resistance value and connection reliability were evaluated. The connection reliability was determined as A when the rate of change with respect to the initial resistance value was 10% or less, B as exceeding 10%, and C as exceeding 30%.

  According to [Table 2], it is preferable that the Cu particles and the Sn-Bi solder particles have the same average particle diameter of 5 μm or less. If the thickness exceeds 5 μm, Sn-Bi solder particles are interposed between the Cu particles and the surface contact portion is hardly formed. When the particle diameters of the Cu particles and the Sn-Bi solder particles are different, the paste No. in [Table 2] is used. As shown in 20 to 23, when Sn-Bi solder particles have an average particle size larger than that of Cu particles, good results in terms of both initial resistance and reliability cannot be obtained.

  This is presumably because Sn-Bi solder particles are contained in the conductive path formed during pressurization. On the other hand, paste No. in [Table 2]. As shown in 6 and 16 to 19, when the average particle diameter of the Sn—Bi solder particles is smaller than that of the Cu particles, good results are obtained in both initial resistance and reliability.

This is because the Sn-Bi solder particles are smaller than the Cu particles, so the Cu particles come into contact with each other at the time of compression, and it becomes easy to form a surface contact portion. Therefore, the Sn-Bi solder particles are difficult to contact with the Cu particles. This is considered to be because a conductive path having a smaller electric resistance was formed.
[Comparison with conventional technology]
Next, the result of comparing the resistance value of the via-hole conductor of the multilayer wiring board of the above-described embodiment and the resistance value of the via-hole conductor according to Patent Document 4 described above will be described.

  FIG. 20 is a graph comparing the resistance value of the via-hole conductor of the multilayer wiring board of the example and the resistance value of the via-hole conductor of the multilayer wiring board according to Patent Document 4.

  In FIG. 20, the horizontal axis (X-axis) represents the content ratio of bismuth contained in the via-hole conductor in mass%. The vertical axis (Y-axis) represents the resistance value of the via-hole conductor as a relative value (relative value where the lowest resistance value is 1).

  The line I in FIG. 20 shows the change in resistance value, which is the result of [Table 1] of Example 1, as a relative value.

  On the other hand, the line II in FIG. 20 shows the change in resistance value in (Sn-2Ag-0.5Cu-20Bi) in [Table 1] of Patent Document 4 as a relative value. The line III in FIG. 20 shows the change in resistance value in (Sn-2Ag-0.5Cu-15Bi) in [Table 1] of Patent Document 4 as a relative value.

  In addition, a line IV in FIG. 20 indicates a change in resistance value in (Sn-58Bi) in [Table 1] of Patent Document 4 as a relative value.

  From FIG. 20, it can be seen that in the case of the via-hole conductor of the multilayer wiring board of the present embodiment indicated by the line I, the via-hole resistance hardly increases even if the content ratio of bismuth contained in the via-hole conductor increases. This is because, in the via-hole conductor of the multilayer wiring board of the present embodiment, copper particles are in direct surface contact with each other to form a combined body made of copper particles, and this combined body electrically connects a plurality of wirings. It can be said that. Therefore, even if the content ratio of bismuth increases, the resistance value hardly increases.

  On the other hand, in the case of the via-hole conductor of the multilayer wiring board of [Table 1] of Patent Document 4 indicated by lines II, III, and IV, the via-hole resistance increases rapidly as the content ratio of bismuth contained in the via-hole conductor increases. You can see that This seems to be because in the via-hole conductor of the multilayer wiring board of Patent Document 4, the copper particles are electrically connected to each other through a high-resistance metal component. This is presumably because paragraph number [0015] of Patent Document 4 “involves a metal component dissolved in the connection”. That is, it is considered that as the content ratio of bismuth increases, the thickness of the high-resistance metal component existing between the copper particles increases.

  As described above, in the case of the via-hole conductor of the multilayer wiring board of the present embodiment, the copper particles form a combined body that is in contact with each other via a surface contact portion that is a portion in surface contact with each other, Since this combined body electrically connects a plurality of wirings, even if the content ratio of bismuth in the via-hole conductor is increased, the via-hole resistance hardly increases rapidly, so that the low resistance is maintained.

[Third embodiment]
In the third embodiment, further improvements of the above-described first embodiment and the via paste used for manufacturing the wiring substrate and the wiring substrate described in the second embodiment will be described.

  The alloy via paste 51 described in the third embodiment is a further improvement of the via paste 28 described in the first embodiment and the second embodiment.

  An example of an alloy via paste described in the third embodiment and a method of manufacturing a wiring board using the alloy via paste will be described with reference to FIGS.

  FIG. 22 is a cross-sectional view illustrating an example of a method for manufacturing a wiring board using an alloy via paste, and corresponds to, for example, the above-described FIG.

  In FIG. 22, 51 is an alloy via paste, 52 is a liquid component, 53 is treated copper particles, 54 is treated solder particles, 55 is a first reactive adsorption layer, 56 is a second reactive adsorption layer, and 57 is a reaction. The adsorptive adsorption layer 58 is a prepreg resin.

  As shown in FIG. 22, the alloy via paste 51 includes at least treated copper particles 53 having a first reactive adsorption layer 55 on the surface and treated solder particles 54 having a second reactive adsorption layer 56 on the surface. And a liquid component 52 composed of at least one of a liquid reactive resin or a liquid organic solvent.

  Here, it is useful that the first reactive adsorption layer 55 and the second reactive adsorption layer 56 are both carboxylic acids. The first reactive adsorption layer 55 and the second reactive adsorption layer 56 may be the same carboxylic acid or may be separate carboxylic acids.

  Here, the liquid component 52 is liquid at room temperature (for example, at 25 ° C.) and is reactive epoxy resin or the like, or an organic solvent that is liquid at room temperature (for example at 25 ° C.). Useful. As the organic solvent, for example, BCA (butyl carbitol acetate) or the like does not react with the reactive adsorption layer 57, and is useful for adjusting the viscosity of the alloy via paste. In the liquid component 52, the reactive liquid resin is a functional group (for example, carboxyl group) included in the reactive adsorption layer 57 including the first reactive adsorption layer 55 and the second reactive adsorption layer 56. Carboxylic acid having a group or amine having an amino group or the like, and in the present invention, a primary amine in which the number of substituted hydrogen atoms of ammonia is one and two secondary amines. Those having three (including tertiary amines and the like) are useful.

  A member constituting such a reactive adsorption layer can cause a curing reaction with an epoxy resin (for example, dimer acid glycidyl ester resin).

  The reactive adsorption layer 57 including the first reactive adsorption layer 55, the second reactive adsorption layer 56, and the like, and the resin material that undergoes a curing reaction are included in the alloy via paste 51 as part of the liquid component 52. However, the prepreg resin 58 constituting a part of the prepreg may be used.

  Here, the prepreg is a glass fiber impregnated with an uncured or semi-cured epoxy resin or the like, and this uncured or semi-cured epoxy resin may be used as the prepreg resin 58 shown in FIG. . Then, as shown in FIG. 22, when the prepreg resin 58 is pressurized and heated through the copper foils 30 installed on both sides, the prepreg resin 58 is liquefied (or softened) and reacts in the alloy via paste 51. It is also useful to undergo a curing reaction with the adsorption layer 57.

  FIG. 23 is an enlarged cross-sectional view illustrating the inside of the alloy via paste when the sample shown in FIG. 22 is pressurized and heated. As shown in FIG. 23, the plurality of processed copper particles 53 are partly deformed by being pressurized and compressed with each other, and are in surface contact via the surface contact portion 20. Further, the processed solder particles 54 and the processed copper particles 53 are deformed and brought into close contact with each other by being partly pressurized and compressed. And the reactive adsorption layer 57 is formed in the surface of the press-contact body (the number is not provided) of the some processed copper particle 53 and the processed solder particle 54 as shown in FIG.

  As shown in FIG. 23, a part of the reactive resin 59 contained in the liquid component 52 causes the reactive adsorption layer 57 to undergo a curing reaction as indicated by an arrow. The reactive resin 59 may be an epoxy resin that has been added to the alloy via paste 51. The reactive resin 59 may be an uncured or semi-cured epoxy resin contained in a prepreg (not shown) surrounding the alloy via paste 51.

  FIG. 24 is a cross-sectional view showing a state in which a cured resin layer 60 is formed on the surface of a pressed body (not assigned a number) of a plurality of processed copper particles 53 and processed solder particles 54.

  The cured resin layer 60 shown in FIG. 24 is obtained by curing reaction of the reactive adsorption layer 57 and a part of the reactive resin 59 contained in the liquid component 52. Alternatively, the cured resin layer 60 is an uncured or semi-cured epoxy resin contained in the reactive adsorption layer 57 and the prepreg (not shown), and the alloy via paste 51 is pressurized and heated. It may be liquefied and diffused in the alloy via paste.

  25A and 25B show an epoxy resin (an example of an epoxy resin is a dimer acid diglycidyl ester, but other reactive resins may be used) and a reactive resin contained in a liquid component. It is a schematic diagram which shows an example of hardening reaction with.

  In FIG. 25 (A), as a reactive resin which reacts with the reactive adsorption layer 57, it is a schematic diagram which shows an example of an epoxy resin (for example, dimer acid diglycidyl ester) with a chemical formula. The carboxylic acid that forms the reactive adsorption layer 57 may be monocarboxylic acid, tricarboxylic acid, or the like in addition to dicarboxylic acid.

  FIG. 25B is a schematic diagram that illustrates, using chemical formulas, how the reactive resin 59 and the reactive adsorption layer 57 undergo a curing reaction to form the curable resin layer 60.

  FIG. 26 is a schematic view showing a state in which a reactive adsorption layer 57 having a carboxyl group is formed on the surface of a pressed body (not assigned a number) of a plurality of processed copper particles 53 and processed solder particles 54. FIG. As shown by the arrows in FIG. 26, the reactive adsorption layer 57 having a carboxyl group and the reactive resin 59 added to the liquid component 52 (the reactive resin 59 may be the prepreg resin 58). A part reacts to form a cured resin layer 60.

  FIG. 27 shows a reactive adsorption layer 57 having a carboxyl group and a part of the reactive resin 59 added to the liquid component 52 (the reactive resin 59 may be the prepreg resin 58). It is sectional drawing which shows an example of the cured resin layer 60 formed by reaction. As shown in FIG. 27, the treated copper particles 53 and the treated solder particles 54 are held in a thin film of the cured resin layer 60 in a state where they are pressed against each other, whereby the treated copper particles 53 and the treated solder particles 54 are treated. Alloying with the solder particles 54 (or preparation of an intermetallic compound) is facilitated because the alloying reaction is protected by a thin film of the cured resin layer 60. Further, since the surfaces of the treated copper particles 53 and the treated solder particles 54 are protected by the reactive adsorption layer 57, even in a paste state, the holes may be filled as via paste and heated and pressurized. Both are useful to be able to prevent oxidation of the metal surface.

  In FIG. 27, it is also useful to use a prepreg resin 58 or a cured product of the prepreg resin 58 around the cured resin layer 60.

  23, 24, 26, 27, etc., although the alloying reaction (or intermetallic compound formation reaction) between the treated copper particles 53 and the treated solder particles 54 is not shown, these alloying reactions This is because the curing reaction between the reactive adsorption layer 57 and the reactive resin 59 proceeds simultaneously (or with a time difference). Thus, in one heating and pressurizing step, the alloying reaction (or intermetallic compound formation reaction) with the treated solder particles 54 and the reactive adsorption layer 57 provided on the surfaces of the copper particles and the solder particles It is useful to perform a curing reaction. This is because the reactive adsorption layer provided on the surface of the treated copper particles 53 and the treated solder particles 54 prevents oxidation of the copper particles and the solder particles, and further an alloying reaction with the treated solder particles 54. This is because it functions as a kind of flux component (or activator) during (or intermetallic compound formation reaction).

  In addition, as a reactive adsorption layer formed on a copper particle or a solder particle, what melt | dissolved commercially available carboxylic acid in the organic solvent etc., and apply | coated and dried on the surface of a copper particle or a solder particle can be used. Here, as the carboxylic acid, the carboxylic acid described in Japanese Patent No. 423333 can be used.

For example, as the carboxylic acid used in the reactive adsorption layer 57 of the present invention, saturated fatty acids and unsaturated fatty acids can be used. For example, as the saturated fatty acid, enanthic acid (C ₆ H ₁₃ COOH), caprylic acid (C ₇ H ₁₅ COOH), pelargonic acid (C ₈ H ₁₇ COOH), capric acid (C ₉ H ₁₉ COOH), undecylic acid ( C ₁₀ H ₂₁ COOH), lauric acid _{(C 11} H 23 COOH), tridecyl acid _{(C 12} H 25 COOH), myristic acid _{(C 13} H 27 COOH), pentadecyl acid _{(C 14} H 29 COOH), palmitic acid ( C ₁₅ H ₃₁ COOH), heptadecyl acid (C ₁₆ H ₃₃ COOH), stearic acid (C ₁₇ H ₃₅ COOH), nonadecanoic acid (C ₁₈ H ₃₇ COOH), arachidic acid (C ₁₉ H ₃₉ COOH), behenic acid ( C ₂₁ H ₄₃ COOH) or a mixture of two or more You can.

For example, as the unsaturated fatty acid as the carboxylic acid used in the reactive adsorption layer 57 of the present invention, acrylic acid (CH ₂ ═CHCOOH), crotonic acid (CH ₃ CH═CHCOOH), isocrotonic acid (CH ₃ CH═CHCOOH) ), Undecylenic acid (CH ₂ ═CH (CH ₂ ) ₉ COOH), oleic acid (C ₁₇ H ₃₃ COOH), elaidic acid (CH ₃ (CH ₂ ) ₇ CH═CH (CH ₂ ) ₇ COOH), cetoleic acid (CH ₃ (CH ₂ ) ₉ CH═CH (CH ₂ ) ₉ COOH), brassic acid (C ₂₁ H ₄₁ COOH), erucic acid (C ₂₁ H ₄₁ COOH), sorbic acid (C ₅ H ₇ COOH), linole acid _{(C 17} H 31 COOH), linolenic acid _{(C 17} H 29 COOH), arachidonic acid _(C 13 _{H 31 C} It can be used as a mixture or one or more of OH).

  Further, as shown in the third embodiment, by using the reactive adsorption layer 57, the curing agent described in the second embodiment (for example, 2-methylaminoethanol constituting the curing agent 1 or the curing agent 2 is configured. The amount of amino adduct curing agent (solid matter) and 2,2′-dimethylaminoethanol constituting the curing agent 3 added to the paste can be greatly reduced. Thus, as shown in the third embodiment, by using the reactive adsorption layer 57, the ratio of the curing agent in the via paste can be greatly reduced.

  For example, in the case of the second embodiment, the total of copper particles and solder particles in the via paste is 90% by weight, the remaining solvent and resin components are 10% by weight (that is, 1.3% by weight is solid matter, 8.7%). The total amount was 10% by weight of the liquid material by weight. On the other hand, when the reactive adsorption layer 57 is used as in the third embodiment, the total amount of copper particles and solder particles in the via paste can be 90% by weight, and the remaining 10% by weight can be all liquid. In this way, as in the third embodiment, a reactive member is adsorbed very thinly on the surface of the metal powder in advance, so that all the components other than the metal powder component are liquid reactive resin or liquid organic solvent. Even in the case of an alloy via paste having a high metal content, it is possible to further reduce the viscosity and enhance the filling property for small diameter vias. Furthermore, the viscosity change (for example, pot life) accompanying a change with time can be suppressed.

  FIG. 28 is a graph showing an example of a viscosity change when the alloy via paste prototyped by the inventors is left at room temperature (25 ° C.). In FIG. 28, the X-axis is the number of days left at room temperature (25 ° C.) (unit is days), and the Y-axis is the relative viscosity (change in viscosity when the initial viscosity is 1). Viscosity measurement was evaluated at a shear rate of (1 / s). In FIG. 28, the alloy via paste as a comparative product is obtained by adding a curing agent (amino alcohol) to the via paste as shown in FIGS. 7A and 12A. The alloy via paste as an invention product is one in which carboxylic acid is adsorbed on the surface of copper particles or solder particles, and this carboxylic acid is used as a reactive adsorption layer 57 as shown in FIGS. In the invention, no curing agent (amino alcohol) is added to the via paste. As shown in FIG. 28, in the comparative product (with a curing agent), the viscosity increases 2.5 times when the number of days to stand is 3 days, but no change in viscosity is observed in the invention product (without the curing agent). (Within measurement error range). Furthermore, as shown in FIG. 28, in the comparative product (with the curing agent), the viscosity increases to nearly 3.5 times when the standing time is 5 days, but in the invention product (without the curing agent), the viscosity change is observed. Not within measurement error range.

  As shown in FIG. 28, in the alloy via paste, it is desirable that carboxylic acid is adsorbed on the surfaces of copper particles and solder particles and this carboxylic acid is used as the reactive adsorption layer 57 so that no curing agent is added. I understand. JP-A-2011-29204 proposes that the content of the curing agent in the conductive paste is 0.3% by mass or less, but the curing agent in the conductive paste is 0.3% by mass or less, or is cured. When the agent is 0% by mass, the cured resin layer 60 that thinly covers the surface of the metal powder as shown in FIGS. 24 and 27 is not formed, so that a part of the metal powder moves or flows in the prepreg. Therefore, the effect of promoting the alloying reaction cannot be expected.

  Further, as shown in the third embodiment, by using the reactive adsorption layer 57, compared with the case described in the second embodiment, the absolute amount of the curing agent or activator in the paste is 1 mass in the alloy paste. % Or less, further 0.5% by mass or less, and further 0.1% by mass or less, but this is the third embodiment as shown in FIGS. 24 and 27 described above. Thus, the cured resin layer 60 that thinly covers the surface of the metal powder of the embodiment is formed to promote the alloying reaction.

  In particular, the total proportion of the first reactive adsorption layer and the second reactive adsorption layer in the alloy via paste is 1% by mass or less, further 0.5% by mass or less, and 0.3% by mass or less. It is desirable.

  This is because both the first reactive adsorption layer and the second reactive adsorption layer contain carboxylic acid and are adsorbed on the surfaces of copper particles and solder particles. This is because the curing effect can be exhibited even if the ratio is 1% by mass or less, further 0.5% by mass or less, 0.3% by mass or less, and further 0.1% by mass or less.

  The amount of the liquid reactive resin (for example, epoxy resin) contained in the alloy via paste is 1% by mass or less, further 0.1% by mass or less, and further 0% by mass (that is, the liquid reaction in the alloy via paste). It is also possible that the resin is not included. This is because even when the alloy via paste contains little or no liquid reactive resin, it is an uncured or semi-cured resin contained in the prepreg, or a curing agent contained in the prepreg. This is because both can be used for the alloy via paste side.

  In addition, it is useful that the first reactive adsorption layer and the second reactive adsorption layer are both organic acids containing carboxylic acid. By using both the first reactive adsorption layer and the second reactive adsorption layer as carboxylic acids or organic acids containing a carboxyl group, the first reactive adsorption layer and the second reactive adsorption layer are a kind. It can be used as a “flux” component of the alloy, and the effect of promoting the alloying reaction of the alloy via paste can be obtained.

  When both the first reactive adsorption layer and the second reactive adsorption layer are utilized as a kind of “flux” component, it is assumed that these members are adsorbed on the surfaces of copper particles and solder particles. It is easy to express the “flux effect”.

  As these “flux” components, the proportion in the alloy paste is 1% by mass or less, more preferably 0.5% by mass or less, 0.3% by mass or less, and further 0.1% by mass or less. is there. This is because when the “via flux component” is included in the alloy via paste in an amount of 1.0 mass% or more, it is considered that the residual portion that did not contribute as “flux” may affect reliability and the like. is there.

  Thus, by using both the first reactive adsorption layer and the second reactive adsorption layer as a kind of “flux” component, the liquid reactive resin is not contained in the alloy via paste. Also, the alloying reaction of the alloy via can be promoted.

  For example, in the case of the second embodiment, the entire resin portion 16 has been cured, but by using the third embodiment, for example, the metal portion 15 constituting the via-hole conductor 14 as shown in FIG. As shown in FIG. 24 and FIG. 27 described above, the relationship between the resin portion 16 and the cured resin layer 60 formed thinly around the metal portion can be greatly reduced.

  As shown in FIG. 27, the resin portion 16 constituting the via-hole conductor 14 is divided into a cured resin layer 60 caused by the reactive adsorption layer 57 and a prepreg resin 58 (or a cured product of the prepreg resin 58) included in the prepreg. May be included.

  In FIG. 27, the metal portion 15 constituting the via-hole conductor 14 is illustrated as a pressure contact body between the processed copper particles 53 and the processed solder particles 54, but the processed copper particles 53 and the processed solder particles 54 It goes without saying that the pressure contact body is heated to become the first metal region 17, the second metal region 18, the third metal region 19, and the fourth metal region 22, as shown in FIG.

  The cured resin layer 60 does not need to be completely cured at the time of alloying. Even during curing, the alloying reaction can be promoted because it functions as an antioxidant layer, an active layer, or a flux layer.

  In addition, when the fourth metal regions 22 made of Sn—Bi solder particles are scattered in the vias, the solder particles contained in the alloy via paste 51 to be the fourth metal regions 22 are made to pass through the second reactive adsorption layer 56. By using the treated solder particles 54 subjected to the surface treatment, the solder particles can be stabilized in the resin.

  As a result, even if the semiconductor substrate is mounted on the wiring board manufactured using the alloy via paste of the present invention and then reflow heating is performed, the via portion does not change. Even if the solder particles scattered as the fourth metal region 22 are redissolved at the reflow temperature, the remelted solder particles are separated from the cured resin layer 60 as shown in FIG. This is because the resin layer made of a cured product such as the prepreg resin 58 is protected by a double resin layer.

  For example, as shown in FIG. 23, FIG. 24, and FIG. 27, Sn-Bi solder particles that did not contribute to the alloy reaction are treated solder particles 54 that are surface-treated with the second reactive adsorption layer 56, The fourth metal region 22 may be interspersed in the resin.

  Note that the treated solder particles 54 surface-treated with the reactive adsorption layer 57 that did not contribute to the alloy reaction shown in FIGS. 23, 24, and 27 may be copper particles that did not contribute to the alloy reaction. For example, the treated solder particles 54 shown in FIG. 23, FIG. 24, and FIG. 27 are treated with copper particles that have not contributed to the alloy reaction (that is, the treated copper particles 53 surface-treated with the first reactive adsorption layer 55). By doing so, the resin may be interspersed as the fifth metal region.

  The copper particles scattered as the fifth metal region in the resin are protected by a double resin layer of a cured resin layer 60 and a resin layer made of a cured product such as a prepreg resin 58, as shown in FIG. Therefore, it does not affect the reliability of the via part.

  According to the present invention, it is possible to further reduce the cost, size, function, and reliability of a multilayer wiring board used for a mobile phone or the like. Also, from the via paste side, by proposing an optimum material for forming a via paste with a reduced diameter via paste, it contributes to the miniaturization and high reliability of the multilayer wiring board.

2,14 Via-hole conductor 4 Intermetallic compound 5,24 Void or crack 7 Copper particle 11,111 Multilayer wiring board 12 (12a, 12b), 42 Wiring 13,113 Insulating resin layer 13a Heat resistant resin sheet 13b Cured resin layer 15 Metal Part 16 Resin part 17 First metal region 17a Combined Cu particles 18 Second metal region 19 Third metal region 20 Surface contact portion 21 Virtual spring 22 Fourth metal region 25 Resin sheet 25a Uncured resin layer 26 Protective film 27 Through hole 28 Via paste 29 Protruding portion 30 Copper foil 31 Sn-Bi solder particles 32 Curable resin component 41, 141 Wiring board 51 Alloy via paste 52 Liquid component 53 Treated copper particles 54 Treated solder particles 55 First reactivity Adsorption layer 56 Second reactive adsorption layer 57 Reactive adsorption layer 58 Prepreg resin 9 reactive resin 60-cured resin layer 113a fiber sheet 125 prepreg

Claims (9)

At least one insulating resin layer, a first wiring disposed on the first surface of the insulating resin layer, a second wiring disposed on the second surface of the insulating resin layer, and the insulating resin layer are penetrated. A wiring board having a via-hole conductor for electrically connecting the first wiring and the second wiring provided as described above,
The via-hole conductor includes a metal part and a resin part,
The metal portion includes a first metal region including a combination of copper particles that forms a path for electrically connecting the first wiring and the second wiring;
A second metal region mainly composed of at least one metal selected from the group consisting of tin, a tin-copper alloy, and a tin-copper intermetallic compound;
A third metal region mainly composed of bismuth in contact with the second metal region, and the copper particles forming the combined body are in surface contact with each other to form a surface contact portion;
An alloy via paste for a wiring board in which at least a part of the second metal region is in contact with the first metal region,
At least the copper particles having a first reactive adsorption layer on the surface;
The Sn-Bi solder particles having a second reactive adsorption layer on the surface;
An alloy via paste having at least one liquid component of a liquid reactive resin or a liquid organic solvent. The content ratio of the copper particles is in the range of 30 to 90% by mass,
The weight ratio (Cu / Sn) of copper (Cu) in the copper particles and tin (Sn) in the Sn—Bi solder particles is in the range of 1.59 to 21.43,
The alloy via paste according to claim 1, wherein both the first reactive adsorption layer and the second reactive adsorption layer contain carboxylic acid. The alloy via paste according to claim 1, wherein a maximum diameter of the via-hole conductor is in a range of 30 to 150 µm, and an average particle diameter of the copper particles is in a range of 3 to 10 µm. 2. The alloy via paste according to claim 1, wherein the Sn—Bi solder particles contain particles having an average particle size of the copper particles or less. 2. The alloy via paste according to claim 1, wherein a content ratio of the copper particles with respect to a total amount of the copper particles and the Sn—Bi solder particles is 40 to 90 mass%. The liquid reactive resin is an epoxy resin,
2. The alloy via paste according to claim 1, wherein a total ratio of the first reactive adsorption layer and the second reactive adsorption layer in the alloy via paste is 1% by mass or less. The alloy according to claim 1, wherein the first reactive adsorption layer and the second reactive adsorption layer both undergo a curing reaction with an uncured resin or a semi-cured resin contained in a prepreg constituting the wiring board. Via paste. 2. The alloy via paste according to claim 1, wherein the first reactive adsorption layer and the second reactive adsorption layer both undergo a curing reaction with a liquid reactive resin contained in the alloy via paste. A method of manufacturing a wiring board using the alloy via paste according to claim 1,
A first step of covering the surface of the insulating resin sheet with a protective film;
A second step of perforating the insulating resin sheet through the protective film to form a through hole;
The through hole contains copper particles, Sn-Bi solder particles, and a thermosetting resin, and the content ratio of the copper particles is in the range of 30 to 90% by mass, and the copper (Cu) in the copper particles and the A third step of filling via paste, wherein the weight ratio (Cu / Sn) to tin (Sn) in the Sn—Bi solder particles is in the range of 1.59 to 21.43;
After the third step, a fourth step of exposing the protruding portion formed by protruding a part of the via paste from the through hole by peeling off the protective film;
A fifth step of disposing a metal foil on at least one surface of the insulating resin sheet so as to cover the protruding portion;
The copper particles are brought into surface contact with each other by compressing the metal foil to the surface of the insulating resin sheet and compressing the via paste through the protrusion at a temperature lower than the eutectic temperature of the Sn-Bi solder particles. A sixth step of forming a bonded body of copper particles having a surface contact portion formed by
After the sixth step, a seventh step of heating the via paste at a temperature equal to or higher than the eutectic temperature of the Sn—Bi solder particles, and a method of manufacturing a wiring board using an alloy via paste.