Method for manufacturing a conductive bilayer-attached substrate and a conductive bilayer-attached substrate, and, method for manufacturing a conductive bilayer-attached wiring substrate and a conductive bilayer-attached wiring substrate

Abstract

The purpose is to provide a method for manufacturing a conductive bias-attached substrate that can exhibit a sufficiently low connection resistance value even after wiring is formed, and the resulting wiring substrate can have excellent connection reliability. A method for manufacturing a conductive substrate has a process S1 of preparing a metal sintered body attachment substrate having a substrate having a hole that is opened on one or both sides of a main surface and a metal sintered body having a porous structure provided inside the hole, wherein the metal sintered body is exposed at the opening of the hole, and a process S2 of providing a resin containing a photosensitive resin composition or a cured product thereof in the metal sintered body of the metal sintered body attachment substrate. The method for manufacturing a conductive substrate attached to a substrate according to the present invention is also useful as a technology for reducing the environmental burden caused by plating.

Description

Technology Field

[0001] The present invention relates to a method for manufacturing a conductive bilayer-attached substrate and a conductive bilayer-attached substrate, and a method for manufacturing a conductive bilayer-attached wiring substrate and a conductive bilayer-attached wiring substrate. Background Technology

[0002] Recently, 3D packaging technology is attracting attention for the miniaturization, high functionality, and integration of electronic devices or components, in which silicon substrates arranged above and below are electrically connected by interposing electrodes called Through-Silicon Via (TSV) on a silicon substrate, and semiconductor chips are stacked at high density in the vertical direction (height direction). In addition, a method of electrically connecting glass substrates arranged above and below by interposing electrodes called Through-Glass Via (TGV) using a glass substrate instead of a silicon substrate is also attracting attention.

[0003] As a method for forming through-electrodes, for example, Patent Document 1 discloses a method for manufacturing a semiconductor device having a silicon through-electrode, comprising a process of plating copper on a non-through-electrode formed on a silicon substrate by electroplating using a specific copper plating solution. However, this method has a problem in terms of productivity because the working time is long due to the need to perform plating while suppressing the environmental burden caused by plating and the deposition rate of the copper film.

[0004] As another method, a copper conductor is formed in a through hole by filling a copper conductor paste containing copper powder, glass powder, organic vehicle, etc., into a through hole of a heat-resistant substrate and firing it (e.g., Patent Document 2 below, etc.).

[0005] In addition, the following patent document 3 proposes a method for manufacturing a substrate having a silicon through-electrode by forming a copper sintered body having a porous structure on a through-bias formed on a silicon substrate, impregnating the copper sintered body with a curable resin composition, and further performing a resin curing process. Prior art literature

[0006] Patent Document 1: Japanese Published Patent Application No. 2019-16712 Patent Document 2: Japanese Published Patent Application No. 2010-108917 Patent Document 3: Japanese Patent Application No. 7226531 The problem to be solved

[0007] Recently, as silicon or glass substrates have been miniaturized to accommodate the miniaturization of electronic devices or components, the inner diameter of through-holes has also been minimized. Consequently, it has become necessary to form conductive biases that possess sufficient conductivity even within such through-holes. Furthermore, wiring may be additionally provided on the surface of the substrate where the conductive biases are formed through plating or the like; in such cases as well, it is required to exhibit a sufficiently low contact resistance value.

[0008] In addition, recently, as signal speeds increase, substrates become smaller, and power consumption decreases due to reduced transmission distances, there is a demand for even greater improvement in connection reliability compared to conventional methods. Under these circumstances, a conductive bias-attached substrate (wiring board) having the above-mentioned wiring formed thereon is required to have excellent conductivity, and in addition, to possess excellent characteristics such that the connection resistance value does not rise even when subjected to temperature changes (hereinafter also referred to as "connection reliability").

[0009] Accordingly, the present invention aims to provide a method for manufacturing a conductive bias-attached substrate that can exhibit a sufficiently low connection resistance value even after wiring is formed, and the resulting wiring substrate that has excellent connection reliability, a conductive bias-attached substrate, a method for manufacturing a conductive bias-attached wiring substrate having excellent connection reliability, and a conductive bias-attached wiring substrate. means of solving the problem

[0010] One aspect of the present invention relates to a method for manufacturing a conductive bio-attached substrate as follows.

[0011] [1] A method for manufacturing a conductive bio-attached substrate comprising: a process S1 of preparing a metal sintered body attached substrate having a hole that is opened on one or both sides of the main body and a metal sintered body having a porous structure provided inside the hole, wherein the metal sintered body is exposed at the opening of the hole; and a process S2 of providing a resin containing a photosensitive resin composition or a cured product thereof in the metal sintered body of the metal sintered body attached substrate.

[0012] [2] A method for manufacturing a conductive bias-attached substrate as described in [1], wherein in the above process S2, the metal sintered body is provided with the resin-containing portion and the resin-non-containing portion that does not contain the resin composition or the cured product thereof, such that the resin-containing portion is located on the opening side.

[0013] [3] A method for manufacturing a conductive bio-attached substrate as described in [1] or [2], wherein the above process S2 comprises a process S2-1a in which a negative-type photosensitive resin composition is impregnated in at least a portion of the metal sintered body by laminating a negative-type photosensitive resin composition on a film on the surface of the metal sintered body attached substrate, and a process S2-2a in which, after the above process S2-1a, the negative-type photosensitive resin composition on the film is removed by a developing process to expose the metal sintered body having the resin-containing portion containing the negative-type photosensitive resin composition at the opening of the hole.

[0014] [4] A method for manufacturing a conductive bio-attached substrate as described in [3], wherein the above process S2 further comprises, after the above process S2-2a, a process S2-3a for curing the negative-type photosensitive resin composition contained in the resin-containing portion.

[0015] [5] A method for manufacturing a conductive bio-attached substrate as described in [4], wherein the above process S2 further comprises, after the above process S2-3a, a process S2-4a for desmearing at least the exposed surface of the metal sintered body.

[0016] [6] A method for manufacturing a conductive bio-attached substrate as described in [1] or [2], wherein the above process S2 comprises a process S2-1b in which a liquid negative-type photosensitive resin composition is applied to the surface of the metal sintered body attached substrate to impregnate at least a portion of the metal sintered body with the negative-type photosensitive resin composition, and after the above process S2-1b, a process S2-2b in which the coating of the liquid negative-type photosensitive resin composition is removed by a developing process to expose the metal sintered body having the resin-containing portion containing the negative-type photosensitive resin composition at the opening of the hole.

[0017] [7] A method for manufacturing a conductive bio-attached substrate as described in [6], wherein the above process S2 further comprises, after the above process S2-2b, a process S2-3b for curing the negative-type photosensitive resin composition contained in the resin-containing portion.

[0018] [8] A method for manufacturing a conductive bio-attached substrate as described in [7], wherein the above process S2 further comprises, after the above process S2-3b, a process S2-4b in which at least the exposed surface of the metal sintered body is desmeared.

[0019] [9] A method for manufacturing a conductive bio-attached substrate as described in [1] or [2], wherein the above process S2 impregnates at least a portion of the metal sintered body with a positive photosensitive resin composition by applying a liquid positive photosensitive resin composition to the surface of the metal sintered body substrate or by laminating a film-shaped positive photosensitive resin composition, and after the above process S2-1c, removes the coating of the liquid positive photosensitive resin composition or the film-shaped positive photosensitive resin composition by exposure and development treatment, thereby exposing the metal sintered body having the resin-containing portion containing the positive photosensitive resin composition to the opening of the hole.

[0020]

[10] A method for manufacturing a conductive bio-attached substrate as described in [9], wherein the positive photosensitive resin composition comprises a thermosetting component, and the process S2 further comprises, after the process S2-2c, a process S2-3c for thermosetting the positive photosensitive resin composition contained in the resin-containing portion.

[0021]

[11] A method for manufacturing a conductive bio-attached substrate as described in

[10] , wherein the above process S2 further comprises, after the above process S2-3c, a process S2-4c of desmearing treatment on at least the exposed surface of the metal sintered body.

[0022] According to the method for manufacturing a conductive bias-attached substrate described in [1], a conductive bias-attached substrate with excellent connection reliability can be obtained, which exhibits a sufficiently low connection resistance value even after wiring is formed. The inventors of the present invention speculate as follows regarding the reason for such effects. First, since the conductive bias is formed by a metal sintered body having a porous structure, stress relaxation is obtained, making it easier to obtain an effect that suppresses cracking of the material around the metal sintered body. On the other hand, the metal sintered body having a porous structure is susceptible to adverse effects such as oxidation caused by the penetration of agents used during wiring formation (e.g., oxidation of the metal sintered body due to the penetration of an aqueous solution). In contrast, it can be assumed that the above adverse effects could be sufficiently mitigated by providing a resin-containing portion in the metal sintered body in the method described in [1]. In addition, the method described in Patent Document 3 above can contain a cured product of a curable resin composition in a copper sintered body having a porous structure, but it has been made clear by the inventors' investigation that the conductivity resistance increases after reliability testing under stricter conditions because the cured resin product tends to remain on the surface of the copper sintered body, which inhibits the precipitation of an electrolytic copper plating film during the subsequent wiring formation process. In contrast, the method described in [1] is based on the knowledge that when a photosensitive resin composition is used, the resin composition on the surface of the metal sintered body can be removed by a corresponding developing process while leaving the resin composition within the metal sintered body.

[0023] Another aspect of the present invention relates to a method for manufacturing a wiring board with a conductive bias attached thereto.

[0024]

[12] A method for manufacturing a conductive wire substrate having a process S3 for forming wiring electrically connected to the conductive wire on a conductive wire substrate obtained by any one of [1] to

[11] .

[0025] Another aspect of the present invention relates to the following conductive bias-attached substrate or conductive bias-attached wiring substrate.

[0026]

[13] A substrate having a through hole and a conductive bias provided within the through hole, wherein the conductive bias comprises a metal sintered body having a porous structure, and

[0027] A conductive biodetector attached substrate comprising a metal sintered body, the above-mentioned metal sintered body comprising a resin-containing portion containing a photosensitive resin composition or a cured product thereof.

[0028]

[14] A conductive substrate described in

[13] , wherein the metal sintered body further comprises a resin-free portion that does not contain a resin composition or a cured product thereof, and the resin-free portion is located on the opening side of the through hole of the metal sintered body.

[0029]

[15] A conductive bilayer attachment substrate as described in

[13] or

[14] , and a conductive bilayer attachment wiring substrate having wiring provided on the conductive bilayer attachment substrate that is electrically connected to said conductive bilayer. Effects of the invention

[0030] According to the present invention, a method for manufacturing a conductive bias-attached substrate that can exhibit a sufficiently low connection resistance value even after wiring is formed, and the resulting wiring substrate can have excellent connection reliability, a conductive bias-attached substrate, and a method for manufacturing a conductive bias-attached wiring substrate having excellent connection reliability and a conductive bias-attached wiring substrate can be provided.

[0031] The method for manufacturing a conductive bio-attached substrate and the conductive bio-attached substrate of the present invention are also useful as a technology for reducing environmental burden caused by plating. Brief explanation of the drawing

[0032] FIG. 1 is a schematic diagram showing an example of a method for manufacturing a conductive bio-attached substrate according to the present embodiment. FIG. 2 is a schematic diagram showing an example of a method for manufacturing a conductive substrate attached to a substrate according to the present embodiment. FIG. 3 is a schematic diagram showing an example of a method for manufacturing a conductive substrate attached to a substrate according to the present embodiment. FIG. 4 is a schematic diagram showing an example of a method for manufacturing a conductive substrate attached to a substrate according to the present embodiment. FIG. 5 is a schematic diagram showing an example of a method for manufacturing a conductive bio-attached substrate according to the present embodiment. FIG. 6 is a schematic diagram showing an example of a method for manufacturing a conductive bio-attached substrate according to the present embodiment. FIG. 7 is a schematic diagram showing an example of a method for manufacturing a wiring board with a conductive bias attached according to the present embodiment. Figure 8 is a schematic diagram showing a test specimen. Specific details for implementing the invention

[0033] Hereinafter, embodiments for carrying out the present invention will be described in detail with reference to the drawings. The present invention is not limited to the following embodiments. In addition, identical or substantial parts in the drawings are denoted by the same reference numerals, and redundant descriptions are omitted.

[0034] Method for manufacturing a substrate with a challenged substrate attached

[0035] The method for manufacturing a conductive bias-attached substrate of the present embodiment comprises: a step S1 of preparing a metal sintered body-attached substrate having a substrate having a hole that is opened on one or both sides of a main surface and a metal sintered body having a porous structure provided inside the hole, wherein the metal sintered body is exposed at the opening of the hole; and a step S2 of providing a resin-containing portion comprising a photosensitive resin composition or a cured product thereof in the metal sintered body of the metal sintered body-attached substrate.

[0036] [Process S1]

[0037] Process S1 may include: process a, which prepares a substrate having a hole and provides a metal paste portion containing metal particles and a volatile solvent to cover the surface of at least the periphery of the hole while filling the interior of the hole; process b, which heats the metal paste portion to remove a portion of the volatile solvent; process c, which removes a portion of the metal paste portion after heating so that the surface is exposed, thereby forming a metal sintered body precursor containing the remainder of the metal particles and the volatile solvent having a flattened exposed surface inside the hole; and process d, which sinters the metal sintered body precursor to form a metal sintered body having a porous structure.

[0038] FIGS. 1 to 3 are schematic diagrams illustrating an example of process S1. FIG. 1 shows an example of a substrate used in the method for manufacturing a conductive bio-attached substrate. Hereinafter, the method for manufacturing a conductive bio-attached substrate according to the present embodiment will be described with reference to these figures. Furthermore, since the present embodiment exemplifies a case where the metal paste includes the copper particles described above as metal particles, the copper particles, the copper layer, and the copper sintered body can be replaced with metal particles, the metal layer, and the metal sintered body, respectively.

[0039] [Process a]

[0040] Examples of substrates having holes prepared in this process include organic substrates, silicon substrates, glass substrates, ceramic substrates, printed circuit boards, semiconductor package substrates, etc. The silicon substrate may be a substrate made of polycrystalline silicon or a rectangular silicon substrate made of polycrystalline silicon. The holes may be through holes or non-through holes. In the present embodiment, for example, as shown in FIG. 1 (a), a silicon wafer (1) having through holes (30) and a silicon substrate (40) having a metal film (2) provided on the wall of the through holes and on the surface of the silicon wafer (1) may be prepared. The through holes (30) pass through both main surfaces of the silicon substrate (40). Although the following description is given as an example of a case where a conductive wire is provided on the silicon substrate (40), the silicon wafer may be replaced with another insulating substrate.

[0041] The thickness of the silicon wafer (1) may be 100 μm or more, 200 μm or more, or 300 μm or more from the perspective of suppressing warping of the substrate after sintering, and may be 800 μm or less, 300 μm or less, 200 μm or less, or 100 μm or less from the perspective of making the substrate lighter and more densified. Also, when using a polycrystalline silicon substrate, the thickness may be 0.05 to 2 mm, 0.1 mm to 1.5 mm, or 0.2 to 1 mm.

[0042] The upper limit of the hole diameter of the through hole (30) may be 200 μm or less, 100 μm or less, or 60 μm or less from the perspective of promoting high density of the obtained semiconductor device, and the lower limit of the hole diameter of the through hole (30) is not particularly limited, but may be 10 μm or more, 20 μm or more, 30 μm or more, or 50 μm or more.

[0043] The ratio of depth to hole diameter of the through hole (30) [(depth) / (hole diameter)] may be 0.5 to 40, 1 to 20, or 2 to 10.

[0044] The number of through holes (30) provided in the silicon substrate (40) is, in order to promote high density of the obtained semiconductor device, 1 cm of the main surface of the substrate. 2 There may be 100 or more, 200 or more, or 300 or more.

[0045] The metal film (2) may be provided on both main surfaces of the silicon wafer (1) and on the wall of the through hole (30), or on at least one main surface of the silicon wafer (1) and on the wall of the through hole (30), or only on the wall of the through hole (30), or not provided at all. In the embodiment shown in FIG. 1 (a), the silicon substrate (40) has a metal film (2) on both main surfaces of the silicon wafer (1) and on the wall of the through hole (30).

[0046] Examples of metal films (2) include titanium, nickel, chromium, copper, aluminum, palladium, platinum, and gold. In terms of adhesion, it is preferable that the metal film (2) be a film formed by layering titanium, nickel, and copper in this order. Adhesion is improved by oxidizing the surface of the silicon wafer (1) to form silicon oxide and forming a titanium layer on the silicon oxide. In addition, by providing a nickel layer on the titanium layer and a copper layer thereon, the diffusion of copper into the silicon wafer (1) can be suppressed compared to the case where a copper layer is provided directly on the titanium layer. Furthermore, by providing a copper layer on the surface, the adhesion between the copper layer and the copper particles in the metal paste is improved, thereby improving reliability.

[0047] In addition, as shown in FIG. 1 (b), when preparing a silicon substrate (41) having a non-through hole (31) as a hole, a conductive bias, which is a through electrode, can be formed by grinding the side opposite to the side where the non-through hole (31) of the silicon substrate is opened after process a, process b, process c, or process d. Examples of grinding methods include mechanical polishing and chemical mechanical polishing.

[0048] The metal paste portion (3) can be prepared by, for example, by directly applying a metal paste containing metal particles and a volatile solvent onto a silicon substrate (40), or by producing a film coated with metal paste in advance and pressing it onto the substrate.

[0049] Methods for applying or filling metal paste include, for example, printing methods such as screen printing, inkjet printing, intaglio printing, flatbed printing, offset printing, and flexographic printing, or printing methods combining these methods, spin coating, dip, roll, squeegee, and press methods. Among these methods, screen printing or squeegee methods that directly fill the substrate under a vacuum atmosphere, and vacuum press methods that press a film coated with metal paste in advance under a vacuum atmosphere are preferred.

[0050] The content of metal particles in the metal paste of the present embodiment may be 95.0 mass% or more, 95.2 mass% or more, 95.5 mass% or more, 95.7 mass% or more, or 96 mass% or more based on the total amount of the metal paste, 98 mass% or less, 97 mass% or less, or 96.5 mass% or less, or 95.0 to 98 mass%, 95.2 to 97 mass%, or 95.7 to 96.5 mass%.

[0051] Examples of metal particles include particles of nickel, silver, copper, gold, palladium, platinum, solder, etc. The metal particles may include multiple metals, such as silver-coated copper particles. When the metal paste contains copper particles, it becomes easier to obtain a substrate having sufficient conductivity and a conductor that is resistant to rising even when subjected to temperature changes, and a through electrode having sufficient conductivity and excellent connection reliability.

[0052] In the present embodiment, the metal particles may include a first metal particle having a volume average particle size of 0.8 μm or more and a second metal particle having a volume average particle size of 0.5 μm or less.

[0053] In addition, in this specification, the volume average particle size of a particle (hereinafter referred to as "average particle size") means the 50% volume average particle size (D50). When determining the volume average particle size of a metal particle, it can be obtained by a method such as measuring the metal particle, which is the raw material, dispersed in a dispersion medium such as water or alcohol using a laser diffraction and scattering particle size distribution measuring device.

[0054] The first metal particle and the second metal particle may be copper particles for the sake of low resistance, securing ion migration resistance, and ease of forming wiring. The present embodiment will be described in detail with respect to the case where the first metal particle is a copper particle (hereinafter referred to as the "first copper particle") and the second metal particle is a copper particle (hereinafter referred to as the "second copper particle").

[0055] (First copper particle)

[0056] The average particle size of the first copper particle may be 0.8 μm or more, 1.0 μm or more, 2.0 μm or more, or 3.0 μm or more from the perspective of improving the sintering density within the holes of the substrate (e.g., through holes or non-through holes) and suppressing voids and cracks occurring within the holes; it may be 10 μm or less, 8.0 μm or less, 5.0 μm or less, or 4.0 μm or less from the perspective of suppressing particle clogging in micro-buyers with an inner diameter of 100 μm or less and improving filling properties; and it may be 0.8 μm to 4.0 μm, 1.0 μm to 3.5 μm, or 1.2 μm to 3.0 μm from the perspective of suppressing voids and cracks and suppressing particle clogging in micro-buyers. The ratio (DC1 / DH) of the average particle size DC1 of the first copper particle and the inner diameter DH of the hole may be 0.01 or more, 0.03 or more, or 0.04 or more from the perspective of suppressing particle clogging in the micro-buffer and improving filling ability, and may be 0.15 or less, 0.1 or less, or 0.05 or less from the perspective of suppressing voids and cracks by reducing shrinkage due to sintering. Also, from the above perspective, the ratio (DC1 / DH) may be 0.01 to 0.15 or 0.03 to 0.1.

[0057] The shape of the first copper particle may be, for example, spherical, massive, needle-shaped, flat (flaked), or approximately spherical. The first metal particle may be an aggregate of copper particles having these shapes. The metal paste of the present embodiment may include spherical copper particles as the first copper particle from the perspective of reducing the step difference between the formed conductive bias portion and the substrate surface and suppressing fluctuations in contact resistance even after a reliability test (e.g., a temperature cycle test).

[0058] In order to improve the printability of the metal paste, the first copper particles may have a content ratio of particles with an aspect ratio of 2 or less, such as spherical particles, of 40 mass% or more, 50 mass% or more, 60 mass% or more, 80 mass% or more, or 100 mass%, or may be 40 to 90 mass%, 50 to 80 mass%, or 60 to 70 mass%. In addition, the aspect ratio (major axis / minor axis) of the particles can be obtained, for example, by observing an SEM image of the particles and measuring the major axis and minor axis (e.g., thickness).

[0059] In addition, the metal paste of the present embodiment may include flake-shaped copper particles as the first copper particles to suppress voids and cracks by reducing shrinkage due to sintering, and may also include spherical copper particles and flake-shaped copper particles to suppress voids and cracks by reducing shrinkage due to sintering, while improving the filling ability for micro-buffers by lowering the viscosity of the metal paste. When spherical copper particles and flake-shaped copper particles are used in combination, their mass ratio (spherical copper particles) / (flake-shaped copper particles) may be 1 to 9, 1.2 to 2.5, or 1.4 to 4.

[0060] The flake copper particles may have an aspect ratio of 1.5 or more, 2 or more, or 3 or more.

[0061] When spherical copper particles with an aspect ratio of 2 or less and flake-shaped copper particles with an aspect ratio greater than 2 are used in combination, their mass ratio (spherical copper particles) / (flake-shaped copper particles) may be 0.6 to 9, 1.0 to 4.0, or 1.5 to 2.4.

[0062] The first copper particles may be produced by chemical reduction, atomization, electrolysis, grinding, plasma rotary electrode, uniform droplet spraying, heat treatment, etc., and may be wet copper powder or atomized copper powder from the view that it is easy to obtain a uniform diameter and the dispersibility of the metal paste is improved.

[0063] The first copper particles may include wet copper powder. In this case, it becomes easier to obtain a conductive bias with excellent conductivity. This effect can be thought to be obtained by the characteristic that wet copper powder is easy to bond with copper particles blended as the second metal. The wet copper powder may have a D90 / D50 ratio of 1.5 or less.

[0064] In addition, the copper particles may contain wet copper powder and atomized copper powder. In this case, it is easy to improve the printability of the metal paste and to reduce the step difference between the formed conductive bias portion and the substrate surface, thereby suppressing fluctuations in contact resistance even after reliability testing (e.g., temperature cycle testing). The following is presumed as the reason for obtaining such effects. That is, it is thought that because wet copper powder with a uniform particle size that is easy to bond with the second copper particles and atomized copper powder with a wide particle size distribution coexist, the wet copper powder bonds between the atomized copper powder and also bonds with the second copper particles, thereby enabling the formation of a robust sintered body with a densely packed structure, and the suppression of the occurrence of voids or cracks and the suppression of concave portions by suppressing shrinkage during sintering. Atomized copper powder may have a D90 / D50 of 1.6 or higher, 1.7 or higher, or 1.8 or higher.

[0065] When the first copper particle contains wet copper powder and atomized copper powder, the content ratio of the wet copper powder may be greater than 0 parts by mass and less than 100 parts by mass, or 20 to 80 parts by mass, with respect to 100 parts by mass of the total amount of wet copper powder and atomized copper powder.

[0066] As the first copper particle, commercially available ones can be used. Commercially available first-grade copper particles include, for example, 1050Y (manufactured by Mitsui Kinzoku Co., Ltd., trade name, average particle size (D50): 0.81μm, D90: 1.1μm, spherical, wet copper powder), 1100Y (manufactured by Mitsui Kinzoku Co., Ltd., trade name, average particle size (D50): 1.1μm, D90: 1.6μm, spherical, wet copper powder), 1200Y (manufactured by Mitsui Kinzoku Co., Ltd., trade name, average particle size (D50): 2.1μm, D90: 3.1μm, spherical, wet copper powder), 1300Y (manufactured by Mitsui Kinzoku Co., Ltd., trade name, average particle size (D50): 3.5μm, D90: 5μm, spherical, wet copper powder), and 1100YP (manufactured by Mitsui Kinzoku Co., Ltd., trade name, average Particle size (D50): 1.4μm, D90: 2.3μm, flattened, wet copper powder), 1200YP (Made by Mitsui Kinzoku Co., Ltd., trade name, average particle size (D50): 3.1μm, D90: 5.3μm, flattened, wet copper powder), MA-C02K (Made by Mitsui Kinzoku Co., Ltd., trade name, average particle size (D50): 1.8μm, D90: 3.6μm, spherical, atomized copper powder), MA-C025K (Made by Mitsui Kinzoku Co., Ltd., trade name, average particle size (D50): 2.4μm, D90: 5.2μm, spherical, atomized copper powder), MA-C03K (Made by Mitsui Kinzoku Co., Ltd., trade name, average particle size (D50): 3.4μm, D90: 6.3μm, Examples include spherical and atomized copper powder.

[0067] The first copper particles may be treated with a surface treatment agent for the sake of dispersion stability and oxidation resistance. The surface treatment agent may be removed during wiring formation (when the copper particles are sintered). Examples of such surface treatment agents include aliphatic carboxylic acids such as palmitic acid, stearic acid, arachidic acid, and oleic acid; aromatic carboxylic acids such as terephthalic acid, pyromellitic acid, and o-phenoxybenzoic acid; aliphatic alcohols such as cetyl alcohol, stearyl alcohol, isobornylcyclohexanol, and tetraethylene glycol; aromatic alcohols such as p-phenylphenol; alkylamines such as octylamine, dodecylamine, and stearylamine; aliphatic nitriles such as stearonitrile and decaine nitrile; silane coupling agents such as alkylalkoxysilane; and polymer treatment agents such as polyethylene glycol, polyvinyl alcohol, polyvinylpyrrolidone, and silicon oligomer. The surface treatment agent may be used as a single type or in combination of two or more types.

[0068] The throughput of the surface treatment agent may be an amount of one molecular layer or more on the particle surface. Such throughput of the surface treatment agent varies depending on the specific surface area of ​​the first copper particle, the molecular weight of the surface treatment agent, and the minimum coverage area of ​​the surface treatment agent. The throughput of the surface treatment agent is typically 0.001 mass% or more.

[0069] The throughput of the surface treatment agent is the number of molecular layers (n) attached to the surface of the first copper particle and the specific surface area (A) of the first copper particle. p )(unit m 2 / g) and the molecular weight of the surface treatment agent (M s )(unit g / mol) and the minimum coverage area of ​​the surface treatment agent (S S )(unit m 2 / item) and, Avogadro's number (N A )(6.02×10 23 It can be calculated from (units). Specifically, the throughput of the surface treatment agent is the throughput of the surface treatment agent (mass%) = {(n × A p× M s ) / (S S× NA +n×A p× M s It is calculated according to the formula )}×100%.

[0070] The specific surface area of ​​the first copper particle can be calculated by measuring the dried copper particle using the BET specific surface area measurement method. The minimum coating area of ​​the surface treatment agent is 2.05 × 10⁻⁶ when the surface treatment agent is a straight-chain saturated fatty acid. -19 m 2 / 1 molecule. For other surface treatment agents, they can be measured, for example, by calculation from a molecular model or by the method described in "Chemistry and Education" (Katsuhiro Ueda, Sumio Inafuku, Iwao Mori, 40(2), 1992, pp. 114-117). An example of a quantitative method for surface treatment agents is shown. Surface treatment agents can be identified by thermal degassing of dry powder from which the dispersion medium has been removed from a metal paste, and gas chromatograph mass spectrometry can be used to determine the number of carbon atoms and molecular weight of the surface treatment agent. The carbon fraction ratio of the surface treatment agent can be analyzed by carbon fraction analysis. As a carbon fraction analysis method, for example, the combustion / infrared absorption method in a high-frequency induction furnace can be used. From the number of carbon atoms, molecular weight, and carbon fraction ratio of the identified surface treatment agent, the amount of the surface treatment agent can be calculated using the above formula.

[0071] (Second copper particle)

[0072] The average particle size of the second copper particles may be 0.5 μm or less, 0.4 μm or less, 0.3 μm or less, or 0.2 μm or less from the perspective of sinterability, and may be 0.01 μm or more, 0.03 μm or more, 0.05 μm or more, 0.08 μm or more, or 0.1 μm or more from the perspective of suppressing synthesis costs, good dispersibility, and suppressing the amount of surface treatment agent used, and may be 0.1 μm to 0.3 μm, 0.12 μm to 0.28 μm, or 0.15 μm to 0.25 μm from the perspective of obtaining sinterability at low temperatures and good dispersibility in paste.

[0073] The second copper particle can act as a copper particle that appropriately joins the first copper particles. Additionally, the second copper particle has superior sinterability compared to the first copper particle and can have a function that promotes the sintering of the copper particles. For example, compared to the case where the first copper particle is used alone, it becomes possible to sinter the copper particles at a lower temperature.

[0074] The second copper particles may be wet copper powder produced by a chemical reduction method.

[0075] The shape of the second copper particle may be, for example, spherical, massive, needle-shaped, flat (flaked), or approximately spherical. The second copper particle may be an aggregate of copper particles having these shapes. From the perspective of dispersibility and packing properties, the shape of the second copper particle may be spherical, approximately spherical, or flat (flaked), and from the perspective of combustibility and mixability with the first copper particle, it may be spherical or approximately spherical.

[0076] The aspect ratio of the second copper particle may be 5 or less, 4 or less, or 3 or less in terms of dispersibility, packing ability, and mixability with the first copper particle.

[0077] As for the second copper particles, synthesized or commercially available ones may be used. Examples of commercially available second copper particles include CH0200L1 (manufactured by Mitsui Kinzoku Co., Ltd., trade name, average particle size (D50): 200 nm, spherical) and Tn-Cu100 (manufactured by Taiyo Nissan Co., Ltd., average particle size (D50): 120 nm, spherical).

[0078] The second copper particles may be treated with a specific surface treatment agent. Examples of specific surface treatment agents include organic acids having 8 to 16 carbon atoms. As organic acids having 8 to 16 carbon atoms, for example, caprylic acid, methylhepteic acid, ethylhexaneic acid, propylpenteic acid, pellagonic acid, methylocteneic acid, ethylhepteic acid, propylhexaneic acid, capric acid, methylnoneneic acid, ethylocteneic acid, propylhepteic acid, butylhexaneic acid, undecaenic acid, methyldecaenic acid, ethylnoneneic acid, propylocteneic acid, butylhepteic acid, lauric acid, methylundecaeic acid, ethyldecaenic acid, propylnoneneic acid, butylocteneic acid, pentylhepteic acid, tridecaenic acid, methyldodecaenic acid, ethylundecaeic acid, propyldecaenic acid, butylnoneneic acid, pentylocteneic acid, myristic acid, methyltridecaenic acid, ethyldodecaenic acid, propylundecaeic acid, Butyldecaenic acid, pentylnoneneic acid, hexylocteneic acid, pentadecaeic acid, methyltetradecaenic acid, ethyl tridecaenic acid, propyldodecaenic acid, butylundecaeic acid, pentyldecaenic acid, hexylnoneneic acid, palmitic acid, methylpentadecaeic acid, ethyltetradecaenic acid, propyl tridecaenic acid, butyldodecaenic acid, pentylundecaeic acid, hexyldecaenic acid, heptylnoneneic acid, methylcyclohexanecarboxylic acid, ethylcyclohexanecarboxylic acid, propylcyclohexanecarboxylic acid, butylcyclohexanecarboxylic acid, pentylcyclohexanecarboxylic acid, hexylcyclohexanecarboxylic acid, heptylcyclohexanecarboxylic acid, octylcyclohexanecarboxylic acid, nonylcyclohexanecarboxylic acid Examples include saturated fatty acids such as octene, nonene, methylnonene, decenoic acid, undeceneic acid, dodecenoic acid, tridecenoic acid, tetradecenoic acid, myristoleic acid, pentadeceneic acid, hexadecenoic acid, palmitoleic acid, sapienic acid, etc.; and aromatic carboxylic acids such as terephthalic acid, pyromellitic acid, o-phenoxybenzoic acid, methylbenzoic acid, ethylbenzoic acid, propylbenzoic acid, butylbenzoic acid, pentylbenzoic acid, hexylbenzoic acid, heptylbenzoic acid, octylbenzoic acid, nonylbenzoic acid, etc. As for organic acids, one type may be used alone, or two or more types may be used in combination.By combining such an organic acid with the second copper particles, it is possible to achieve both the dispersibility of the second copper particles and the detachability of the organic acid during sintering.

[0079] The amount of surface treatment agent used may be an amount in which one to three molecular layers are attached to the surface of the second copper particle. The amount of surface treatment agent used may be 0.07 mass% or more, 0.10 mass% or more, or 0.2 mass% or more, or 2.1 mass% or less, 1.6 mass% or less, or 1.1 mass% or less. The amount of surface treatment of the second copper particle can be calculated by the method described above for the first copper particle. The same applies to the specific surface area, the molecular weight of the surface treatment agent, and the minimum coating area of ​​the surface treatment agent.

[0080] The content of the second metal particles in the metal paste is 50 mass% or less based on the total amount of metal particles from the perspective of connection reliability, and may be 10 to 50 mass% or 20 to 40 mass% from the perspective of lowering the sintering temperature to improve adhesion with the underlying metal layer, reducing the porosity of the sintered body, suppressing shrinkage during sintering, and suppressing the occurrence of cracks.

[0081] The total content of the first copper particles and the second copper particles in the metal paste may be 100 parts by mass, 85 to 99.5 parts by mass, 90 to 99 parts by mass, or 95 to 98 parts by mass, when the total mass of the metal particles is 100 parts by mass.

[0082] The content of the first copper particle and the second copper particle, respectively, may be 50 to 90 parts by mass and 50 to 10 parts by mass for a total of 100 parts by mass of the first copper particle and the second copper particle, 55 to 85 parts by mass and 45 to 15 parts by mass, or 60 to 80 parts by mass and 40 to 20 parts by mass.

[0083] The metal paste of the present embodiment may contain copper particles and metal particles other than copper particles (hereinafter also referred to as "other metal particles"). In this case, the other metal particles may be nickel particles, silver particles, gold particles, palladium particles, platinum particles, or solder particles. One or more of these may be included. The average particle size of the other metal particles may be 0.01 μm or more, 0.03 μm or more, or 0.05 μm or more, or 5 μm or less, 3.0 μm or less, or 2.0 μm or less. The average particle size of the solder particles may be 1.0 μm or more, 1.5 μm or more, 2.0 μm or more, 3.0 μm or more, or 4.0 μm or more, or 15 μm or less, 10 μm or less, 8.0 μm or less, or 5.0 μm or less.

[0084] The content of other metal particles may be 5 parts by mass or less, 3 parts by mass or less, 1 part by mass or less, or 0.8 parts by mass or less, when the total mass of copper particles is 100 parts by mass. The metal paste of the present embodiment may not include solder particles as other metal particles.

[0085] [Volatile Solvents]

[0086] As volatile solvents, for example, monohydric and polyhydric alcohols such as pentanol, hexanol, heptanol, octanol, decanol, ethylene glycol, diethylene glycol, propylene glycol, butylene glycol (1,3-butanediol, etc.), α-terpineol, and isobornylcyclohexanol (MTPH); Ethylene glycol butyl ether, ethylene glycol phenyl ether, diethylene glycol methyl ether, diethylene glycol ethyl ether (ethyl carbitol), diethylene glycol butyl ether (diethylene glycol mono-n-butyl ether, etc.), diethylene glycol isobutyl ether, diethylene glycol hexyl ether, triethylene glycol methyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol dibutyl ether, diethylene glycol butyl methyl ether, diethylene glycol isopropyl methyl ether, triethylene glycol dimethyl ether, triethylene glycol butyl methyl ether, propylene glycol propyl ether, dipropylene glycol methyl ether, dipropylene glycol ethyl ether, dipropylene glycol propyl ether, dipropylene glycol butyl ether, dipropylene glycol dimethyl ether, Ethers such as tripropylene glycol methyl ether and tripropylene glycol dimethyl ether; esters such as dimethyl phthalate, ethylene glycol ethyl ether acetate, ethylene glycol butyl ether acetate, propylene glycol diacetate, diethylene glycol ethyl ether acetate, diethylene glycol butyl ether acetate, dipropylene glycol methyl ether acetate (DPMA), ethyl lactate, butyl lactate, γ-butyrolactone, and propylene carbonate; acid amides such as N-methyl-2-pyrrolidone, N,N-dimethylacetamide, and N,N-dimethylformamide; aliphatic hydrocarbons such as cyclohexane, octane, nonene, decaine, and undecaine; aromatic hydrocarbons such as benzene, toluene, and xylene; and mercaptans having alkyl groups having 1 to 18 carbon atoms. Examples include mercaptans having a cycloalkyl group having 5 to 7 carbon atoms.Examples of mercaptans having an alkyl group having 1 to 18 carbon atoms include ethyl mercaptan, n-propyl mercaptan, i-propyl mercaptan, n-butyl mercaptan, i-butyl mercaptan, t-butyl mercaptan, pentyl mercaptan, hexyl mercaptan, and dodecyl mercaptan. Examples of mercaptans having a cycloalkyl group having 5 to 7 carbon atoms include cyclopentyl mercaptan, cyclohexyl mercaptan, and cycloheptyl mercaptan. One type of volatile solvent may be used alone, or two or more types may be used in combination.

[0087] The metal paste of the present embodiment may include, for the sake of printability and suppressing volume shrinkage before and after firing the metal sintered body precursor (for example, between process c of forming the metal sintered body precursor and process d of firing the metal sintered body precursor), a volatile solvent having a vapor pressure of 4 Pa ​​or more and 30 Pa or less at 20°C (hereinafter also referred to as a "high vapor pressure solvent"). The high vapor pressure solvent may be used as a single type or in combination of two or more types.

[0088] Examples of high vapor pressure solvents include α-terpineol, 1,3-butanediol, ethyl carbitol, propylene glycol diacetate, etc.

[0089] The metal paste of the present embodiment may include, from the viewpoint of suppressing powdering due to drying caused by solvent volatilization during printing or paste production, a volatile solvent having a vapor pressure of less than 4 Pa ​​at 20°C (hereinafter also referred to as a "low vapor pressure solvent"). The low vapor pressure solvent may be used as a single type or in combination of two or more types.

[0090] Examples of low vapor pressure solvents include isobornylcyclohexanol (MTPH), dimethyl phthalate, and diethylene glycol mono-n-butyl ether.

[0091] In order to achieve both printability and suppress volume shrinkage before and after firing the metal sintered body precursor (for example, between process c of forming the metal sintered body precursor and process d of firing the metal sintered body precursor), thereby suppressing voids or cracks, the metal paste of the present embodiment may include a high vapor pressure solvent and a low vapor pressure solvent. In this case, the high vapor pressure solvent and the low vapor pressure solvent may each be used as a single type or in combination of two or more types. The content ratio of the high vapor pressure solvent and the low vapor pressure solvent may be such that the mass ratio [high vapor pressure solvent / low vapor pressure solvent] is 20 / 80 to 80 / 20 or 30 / 70 to 70 / 30.

[0092] The content of the volatile solvent in the metal paste of the present embodiment may be 2 mass% or more, 3 mass% or more, or 3.5 mass% or more based on the total mass of the metal paste, 5 mass% or less, 4.8 mass% or less, 4.5 mass% or less, 4.3 mass% or less, or 4 mass% or less, or 2 to 5 mass%, 3 to 4.8 mass%, or 3.5 to 4.5 mass%.

[0093] The metal paste of the present embodiment may include a resin component such as epoxy resin. The metal paste of the present embodiment may have a resin component content of 10 mass% or less, or 5 mass% or less, and may not include a resin component.

[0094] The metal paste can be prepared by mixing metal particles, such as the copper particles described above, and any component (such as additives) in the volatile solvent described above. After mixing each component, a stirring treatment may be performed. The maximum diameter of the dispersion may be adjusted by a classification operation. In addition, means such as a 3-roll kneader, planetary mixer, etc., may be used for mixing each component.

[0095] When the metal paste comprises the first copper particles and the second particles described above, the second copper particles, a surface treatment agent, and a dispersion medium may be mixed in advance and a dispersion treatment performed to prepare a dispersion of the second copper particles, and additionally, the first copper particles, other metal particles if necessary, and any additives may be mixed to prepare the mixture. By following this procedure, the dispersibility of the second copper particles is improved, and the mixing ability with the first copper particles is improved, thereby further enhancing the performance of the metal paste. Aggregates may be removed by providing the dispersion of the second copper particles to a classification operation.

[0096] The metal paste of the present embodiment may have a viscosity of 100 to 600 Pa·s or 150 to 400 Pa·s at 25°C from the perspective of printability. The viscosity of the metal paste is measured using a micro spiral viscometer PCU-02V (Malcolm Inc., product name) under conditions of rotation speed: 10 rpm and temperature: 25°C.

[0097] In the case of using a film coated with metal paste in advance, as shown in FIG. 2 (a) to (c), the metal paste portion (3) can be prepared by, for example, by producing a metal particle film having a metal particle containing a metal paste containing metal particles and a volatile solvent on a support film (7), and pressing the metal particle film onto a substrate.

[0098] Examples of support films (7) include polyimide film, polyethylene naphthalate film, and polyethylene terephthalate film. The thickness of the support film may be 20 to 200 μm, 25 to 175 μm, or 30 to 150 μm, in terms of workability for forming a metal particle-containing layer by coating.

[0099] The composition of the metal particles and volatile solvent in the metal particle-containing layer can be appropriately set so as to satisfy the conditions of the metal paste of the present embodiment described above. The thickness of the metal particle-containing layer can be set so that the metal paste can be sufficiently filled into the through holes or non-through holes, and may be 100 μm or less. From the perspective of making it easier to ensure sufficient filling of the through holes or non-through holes, the thickness of the metal particle-containing layer may be 30 μm or more, 40 μm or more, or 50 μm or more.

[0100] In the metal particle-containing layer, from the perspective of suppressing the occurrence of voids in through holes or non-through holes, the curvature (difference in elevation) on the surface opposite to the support film may be 20 μm or less, or 10 μm or less. By reducing the curvature (difference in elevation), when the metal particle film is compressed to fill the metal particle composition into the holes of the gas, it becomes easier to simultaneously fill the numerous through holes or non-through holes present in the gas, thereby making it easier to reduce through holes or non-through holes that are completely unfilled or through holes or non-through holes where partial voids occur. In addition, the evaluation of the curvature (difference in elevation) can be measured by a non-contact method using a laser displacement meter, etc.

[0101] The metal particle film described above can be produced by applying the metal paste of the present embodiment described above onto a support film to form a metal particle-containing layer having a metal particle concentration of 95.0 mass% or more, or by applying a metal paste in which the content of the volatile solvent in the metal paste is increased (for example, increased to an amount such that the metal particle concentration is less than 94.0 mass%), and drying the coating film to form a metal particle-containing layer having a metal particle concentration of 95.0 mass% or more.

[0102] Methods for applying metal paste include, for example, screen printing, transfer printing, offset printing, jet printing, dispenser, jet dispenser, needle dispenser, comma coater, slit coater, die coater, gravure coater, slit coat, relief printing, intaglio printing, gravure printing, stencil printing, soft lithography, bar coat, applicator, particle deposition method, spray coater, spin coater, dip coater, etc.

[0103] In terms of workability of application and uniformity of coating film thickness, a metal paste can be applied onto a support film by screen printing.

[0104] The thickness of the coating film may be 1 μm or more, 2 μm or more, 3 μm or more, 5 μm or more, 10 μm or more, 15 μm or more, or 20 μm or more, or 300 μm or less, 250 μm or less, 200 μm or less, 150 μm or less, 120 μm or less, 100 μm or less, 80 μm or less, or 50 μm or less.

[0105] The process of drying the coating film to form a metal particle-containing layer can be carried out at room temperature or at a temperature of room temperature to 100°C or lower, and the atmosphere may be in the atmosphere or in nitrogen.

[0106] In process a, the metal particle film described above is pressed against a silicon substrate (40) so that the metal particle-containing layer (3p) of the metal particle film contacts the silicon substrate (40), and a metal paste is filled into the through hole (30) of the silicon substrate (40). In this case, for example, as shown in FIG. 2 (b), the metal particle film and the silicon substrate (40) can be pressed by clamping them from above and below using a pressure jig (A). The pressure jig (A) is not particularly limited, but may be commercially available or may be manufactured using a metal member having a flat portion. For example, a pressure jig having two or more of the above metal members can press the metal particle film against the silicon substrate by clamping the metal particle film and the silicon substrate between the metal members arranged so that their flat portions face each other. The pressure jig (A) may have a mechanism for adjusting the pressure applied to the metal particle film and the silicon substrate. A spring or the like may be used as the pressure adjustment means. In this embodiment, a vacuum press method may be used in which the press is performed under a vacuum atmosphere.

[0107] The conditions for pressing may be, for example, at a temperature of room temperature to 50°C or lower, and regarding the atmosphere, it may be in a vacuum, in the atmosphere, or in nitrogen. For the purpose of reducing voids, the metal particle film may be pressed onto the silicon substrate after maintaining a vacuum of 1000 Pa or less, or a vacuum of 200 Pa or less. When pressing the metal particle film onto the silicon substrate, the pressure of the pressing jig may be a pressure within a range where the silicon wafer does not crack, for example, 0.01 MPa or more, 0.1 MPa or more, or 1 MPa or more.

[0108] The metal paste portion (3) may cover the surface of at least the periphery of the hole of the substrate while filling the inside of the hole, but as shown in FIG. 2 (b) and (c), the metal paste portion may protrude from the opening of the through hole (VP0 in FIG. 2 (a)) located on the side opposite to the side where the metal particle film of the substrate is pressed, and cover the surface of the periphery of the hole.

[0109] [Process b]

[0110] In this process, the metal paste portion is heated to remove a portion of the volatile solvent, or to rephrase, to leave a portion of the volatile solvent. Additionally, when using the above-mentioned metal particle film, the metal paste portion may be heated after peeling off the support film.

[0111] Heating can be achieved using, for example, a hot plate, a hot air dryer, a hot air furnace, a nitrogen dryer, an infrared dryer, an infrared furnace, a far-infrared furnace, a microwave heating device, a laser heating device, an electronic heating device, a heater heating device, a steam furnace, a hot plate press device, etc.

[0112] The heating atmosphere may be an atmosphere of air, an oxygen-free atmosphere such as nitrogen and noble gases, or a reducing atmosphere such as hydrogen and formic acid. In the case of an atmosphere, copper particles are prone to oxidation when the heating temperature exceeds 100°C, but if the metal paste part contains the high vapor pressure solvent described above as a volatile solvent, a portion of the volatile solvent can be removed at a temperature of less than 100°C, 95°C or lower, or 90°C or lower. In addition, if the metal paste part does not contain a high vapor pressure solvent as a volatile solvent, for example, only contains the low vapor pressure solvent described above, oxidation of copper particles can be suppressed while removing a portion of the volatile solvent by heating to 110°C or higher, 130°C or higher, or 150°C or higher in an oxygen-free atmosphere or a reducing atmosphere.

[0113] In the case where the metal paste part contains a high vapor pressure solvent, the heating temperature may be 70°C or higher and less than 100°C, or 80°C or higher and less than 95°C, from the perspective of inhibiting oxidation of copper particles, and the heating time may be 5 to 60 minutes, or 10 to 30 minutes, from the perspective of inhibiting oxidation of copper particles.

[0114] In addition, from the perspective of suppressing volume shrinkage before and after firing the metal sintered body precursor (for example, between process c of forming the metal sintered body precursor and process d of firing the metal sintered body precursor) and suppressing voids or cracks, the metal paste portion may be heated so that the concentration of metal particles is 96 mass% or more, 97.5 mass% or more, or 98 mass% or more.

[0115] [Process c]

[0116] In this process, as shown in FIG. 3 (a) to (d), the metal paste portion (3a) after heating obtained in process b is flattened (or smoothed) while removing the metal paste covering the surface of the substrate and filling the hole with metal paste. By doing so, a metal sintered precursor (3b) containing metal particles and a remainder of volatile solvent can be formed inside the hole (through hole (30)) having a flattened exposed surface VP1 (Fig. 3 (d)).

[0117] The removal of the metal paste portion can be performed using a rubber squeegee (42), for example, as shown in FIG. 3 (b) and (d). This allows a portion of the metal paste portion (metal paste covering the surface of the substrate and metal paste protruding from the holes) to be removed so that the surface (SP0) of the substrate (40) and the exposed surface (VP1) of the metal sintered precursor (3b) form the same surface. Another method may be removal using a metal squeegee such as SUS.

[0118] The step difference between the surface (SP0) of the substrate (40) and the exposed surface (VP1) of the metal sintered precursor (3b) may be 5 μm or less in the direction perpendicular to the surface of the substrate, or 3 μm or less. Also, the average step difference calculated by the following method may be within the above range.

[0119] (Average height difference)

[0120] An image of a cross-section passing through the center of a hole (buyer) is acquired, and by binarizing the cross-sectional image, the cross-sectional area Sa enclosed by the inner wall of the hole (buyer), the exposed surface of the metal sintered precursor, and the opening surface of the hole (buyer) is obtained, and the average step difference is calculated by dividing this by the gap Wa of the inner wall of the hole.

[0121] [Process d]

[0122] In this process, the metal sintered body precursor (3b) formed in process c is sintered. This allows for the formation of a metal sintered body having a porous structure. The porosity of the metal sintered body may be 10% or less, 1.0 to 6.5%, or 1.5 to 5.0%, from the perspective of suppressing the absorption of the chemical solution into the metal sintered body and improving reliability when immersed in a chemical solution such as a resist stripping solution or plating pretreatment in a subsequent process. If the metal sintered body is made of copper, the porosity of the copper sintered body may be within the above ranges. The porosity can be obtained by the method described in the example.

[0123] Sintering can be performed by heat treatment. For the heat treatment, heating means such as a hot plate, hot air dryer, hot air furnace, nitrogen dryer, infrared dryer, infrared furnace, far-infrared furnace, microwave heating device, laser heating device, electronic heating device, heater heating device, steam furnace, etc., may be used.

[0124] The atmosphere during firing may be an oxygen-free atmosphere for the purpose of inhibiting oxidation of the copper sintered body, or a reducing atmosphere for the purpose of removing surface oxides from copper particles in the metal sintered body precursor. Examples of an oxygen-free atmosphere include the introduction of oxygen-free gases such as nitrogen or noble gases, or under vacuum. Examples of a reducing atmosphere include pure carbon dioxide, a mixed gas of hydrogen and nitrogen represented by a forming gas, nitrogen containing formic acid, a mixed gas of hydrogen and noble gases, or a noble gas containing formic acid. When sintering the metal sintered body precursor by heating without pressurization, it is sufficient to use pure carbon dioxide or a mixed gas of hydrogen and nitrogen represented by a forming gas, and pure carbon dioxide is preferred. By heating in pure carbon dioxide, it becomes possible to lower, for example, the sintering temperature of the copper particles. When using pure gas, even if the thickness of the substrate is 600 μm and the diameter of the through hole (30) is 10 μm, the gas reaches the center of the through hole (30), making it easier to obtain a metal body containing a copper sintered body.

[0125] The maximum temperature reached during heat treatment may be 150°C or higher, 350°C or lower, 300°C or lower, or 260°C or lower, from the perspective of reducing heat damage to each component and improving yield. If the maximum temperature reached is 150°C or higher, the maximum temperature holding time is 60 minutes or less, and sintering tends to proceed sufficiently. The maximum temperature holding time may be 1 minute or more, 60 minutes or less, 40 minutes or less, or 30 minutes or less, from the perspective of volatilizing all volatile solvents and improving yield.

[0126] In the present embodiment, by using the metal paste of the present embodiment, sintering can be performed at a low temperature of 300°C or lower, 200°C or lower, or 150°C or lower in an atmosphere containing formic acid gas, and firing can be performed at 100 to 300°C, 100 to 200°C, or 100 to 150°C. Even in this case, a conductive bias with excellent conductivity and connection reliability can be formed.

[0127] The firing of the metal sintered precursor may be performed without pressure or under pressure. In the latter case, under an atmosphere containing pure nitrogen gas, the pressure may be 0.05 MPa or more, 0.1 MPa or more, or 0.3 MPa or more, or 20 MPa or less, 15 MPa or less, or 10 MPa or less. Also, under an atmosphere containing nitrogen gas, the pressure may be 1 MPa or more, or 3 MPa or more, or 20 MPa or less, 15 MPa or less, or 10 MPa or less.

[0128] By setting the pressure to 0.05 MPa or more when using pure oxygen gas and 1 MPa or more when using nitrogen gas, it becomes easier to suppress the occurrence of voids in the conductive bias formed in the center of the through hole (30), and it becomes easier to obtain a conductive bias with good conductivity. Also, by setting the pressure above the lower limit value, when the silicon substrate (40) has a metal film (2), it becomes easier to improve the bonding strength between the metal film (2) and the conductive bias.

[0129] In addition, if the pressure received during firing is within the above range, a special pressurizing device is unnecessary, so the yield is not impaired, and the reduction of voids, bonding strength, and connection reliability can be further improved. As a method of applying pressure to a silicon substrate having a metal sintered body precursor formed in a through hole, examples include placing a weight, applying pressure using a pressurizing device, or applying pressure using a fixed jig for applying pressure.

[0130] In the case where the metal sintered body is a copper sintered body, the proportion of copper elements among the elements excluding light elements among the constituent elements may be 95 mass% or more, 97 mass% or more, 98 mass% or more, or 100 mass%. If the above proportion of copper elements in the copper sintered body is within the above range, the formation of intermetallic compounds or the precipitation of heterogeneous elements into the grain boundaries of the metallic copper can be suppressed, and the properties of the metallic copper constituting the copper sintered body tend to become more robust, making it easier to obtain even better connection reliability.

[0131] In process d, the metal sintered precursor has an exposed surface (VP1) that is flat and has a sufficiently small step difference with the surface of the substrate, and also has a composition that is difficult to shrink in volume by sintering, so the step difference between the surface (SP0) of the substrate (40) and the exposed surface (VP2) of the conductive biaser (3c) can be sufficiently small.

[0132] The step difference (or the concave portion of the conductive bias (3c)) between the surface (SP0) of the substrate (40) and the exposed surface (VP2) of the conductive bias (3c) may be 5 μm or less in the direction perpendicular to the surface of the substrate, or 3 μm or less. In addition, the average step difference calculated by the following method may be within the above range.

[0133] (Average height difference)

[0134] An image of a cross-section passing through the center of the hole (buyer) is acquired, and by binarizing the cross-sectional image, the cross-sectional area Sb enclosed by the inner wall of the hole (buyer), the exposed surface of the conductive buyer, and the opening surface of the hole (buyer) is obtained, and the average step difference is calculated by dividing this by the gap Wb of the inner wall of the hole.

[0135] By going through the above-described processes a to d, a metal sintered body attachment substrate (50) having a metal sintered body (3c) having a porous structure (32) provided within a through hole (30) of a silicon substrate (40) can be obtained. Since the exposed surface of the metal sintered body on the metal sintered body attachment substrate (50) is flat (smooth) and the step difference with the surface (SP0) of the substrate (40) is sufficiently small, wiring can be easily formed and a sufficiently low contact resistance value can be exhibited even after wiring is formed.

[0136] In addition, a metal film may be further formed on the surface of the metal sintered body attached substrate (50) obtained through the above-described processes a to d. Examples of metal films include titanium, nickel, chromium, copper, aluminum, palladium, platinum, and gold. For the sake of adhesion and subsequent etching processes, the metal film is preferably copper. The metal film can be formed by plating or sputtering, but sputtering is more preferable. In this case, reliability can be improved by preventing the penetration of the chemical solution into the copper sintered body having a porous structure during the resist formation process, plating process, resist removal process, and etching process described in the following section, thereby suppressing oxidation of the copper sintered body.

[0137] [Process S2]

[0138] In process S2, a resin-containing portion comprising a photosensitive resin composition or a cured product thereof is provided on the metal sintered body of the substrate to which the metal sintered body is attached. Additionally, the resin-containing portion and a resin-non-containing portion that does not contain the resin composition or the cured product thereof may be provided on the metal sintered body such that the resin-containing portion is located on the opening side. In this case, while suppressing the increase in the contact resistance value caused by the resin-containing portion, adverse effects caused by the penetration of agents, etc., during the wiring formation in the subsequent process can be prevented.

[0139] The photosensitive resin composition may be capable of forming a predetermined pattern by exposure and development, and may be a negative type or a positive type.

[0140] As a method for providing a resin-containing portion comprising a photosensitive resin composition in a metal sintered body, examples include laminating a film-shaped photosensitive resin composition or applying a liquid-shaped photosensitive resin composition. When providing a resin-containing portion comprising a cured product of a photosensitive resin composition in a metal sintered body, the photosensitive resin composition may be cured after providing the resin-containing portion comprising the photosensitive resin composition. In this case, the photosensitive resin composition may include a thermosetting component and be capable of thermosetting.

[0141] Process S2 may include process S2-1a (see FIG. 4 (a) and (b)), in which a negative-type photosensitive resin composition (80) on a film is laminated onto the surface of a substrate to which a metal sintered body is attached, thereby impregnating at least a portion of the metal sintered body (3c) with the negative-type photosensitive resin composition; and process S2-2a (see FIG. 4 (c)), in which, after process S2-1a, the negative-type photosensitive resin composition on the film is removed by a developing process, thereby exposing the metal sintered body (3c) having a resin-containing portion containing the negative-type photosensitive resin composition (34a) at the opening of the hole.

[0142] The negative-type photosensitive resin composition on the film may use a dry film resist such as a photocurable dry film resist and a thermosetting dry film resist, and commercial products such as RD-1619 (manufactured by Resonac Co., Ltd., product name), HM-4035 (manufactured by Resonac Co., Ltd., product name), HM-4056 (manufactured by Resonac Co., Ltd., product name), TMMF NA1000 (manufactured by Tokyo Oka Kogyo Co., Ltd., product name), and PSR-800 AUS SR-1 (manufactured by Taiyo Ink Seizo Co., Ltd., product name) may be used.

[0143] As a method for laminating a negative-type photosensitive resin composition on a film, methods such as a roll laminator, a laminator, or a press can be used.

[0144] The pressure may be 0.1 MPa or more, 0.4 MPa or more, or 1 MPa or more, from the perspective of facilitating the impregnation of the photosensitive resin composition into the metal sintered body. The upper limit of the pressure may be 10 MPa or less, from the perspective of minimizing the effect on the substrate.

[0145] Laminating while heating is possible in order to facilitate the impregnation of the photosensitive resin composition into the metal sintered body. The heating temperature is not particularly limited as long as it is within a range where the photosensitive resin composition is not cured, and may be 50°C to 100°C or 70°C to 90°C.

[0146] In order to facilitate the impregnation of the photosensitive resin composition into the metal sintered body, the negative-type photosensitive resin composition on the film may be laminated after maintaining a vacuum of 1000 Pa or less, or a vacuum of 200 Pa or less.

[0147] The depth of impregnating the metal sintered body with a photosensitive resin composition may be 0.2% or more, 0.5% or more, or 1% or more with respect to the total length in the thickness direction of the substrate of the metal sintered body from the perspective of connection reliability, and the distance from the exposed surface of the metal sintered body may be 1 μm or more, 2 μm or more, or 3 μm or more.

[0148] In process S2-2a, a developing treatment corresponding to the photosensitive resin composition may be performed. As a developing solution, for example, an alkaline aqueous solution in which an alkaline compound such as sodium carbonate, sodium hydroxide, potassium hydroxide, tetramethylammonium hydroxide, or choline is dissolved in water to a concentration of about 1 to 10 mass%, or an alkaline aqueous solution such as ammonia water, may be used. Examples of developing methods include shower developing, spray developing, immersion developing, and puddle developing.

[0149] After passing through process S2-2a, a conductive bias-attached substrate (51a) is obtained (see (c) of FIG. 4).

[0150] Process S2 may further include process S2-3a for curing a negative-type photosensitive resin composition contained in a resin-containing portion after process S2-2a.

[0151] In the case of photocuring, as the active light used for exposure, for example, a light source using a g-line stepper; ultraviolet light source using a low-pressure mercury lamp, a high-pressure mercury lamp, a metal halide lamp, an i-line stepper, etc.; an electron beam; a laser beam, etc. may be used. The amount of exposure is appropriately selected according to the light source used, the thickness of the impregnated photosensitive resin composition, etc.

[0152] If the negative-type photosensitive resin composition includes a thermosetting component, it may be thermosetting.

[0153] Process S2 may further include process S2-4a, which performs a desmearing treatment on at least the exposed surface of the metal sintered body after S2-3a.

[0154] Examples of desmearing treatments include plasma cleaning and treatment with a desmearing solution containing permanganate and a caustic composition (e.g., alkali metal hydroxide).

[0155] In another embodiment, process S2 may include process S2-1b (see FIG. 5 (a)) of impregnating at least a portion of the metal sintered body (3c) with a negative-type photosensitive resin composition by applying a liquid negative-type photosensitive resin composition (82) to the surface of a substrate attached to the metal sintered body, and process S2-2b (see FIG. 5 (b)) of removing the film of the liquid negative-type photosensitive resin composition by a developing process after process S2-1b, thereby exposing the metal sintered body (3c) having a resin-containing portion containing the negative-type photosensitive resin composition (34b) at the opening of the hole.

[0156] For the liquid negative-type photosensitive composition, commercially available products such as PSR-4000 G24K / CA-40 G24 (manufactured by Taiyo Ink Seizo Co., Ltd., product name), TER-20HF (manufactured by Taiyo Ink Seizo Co., Ltd., product name), and TMMR NA1000PM (manufactured by Tokyo Oka Kogyo Co., Ltd., product name) may be used.

[0157] Examples of methods for applying a liquid negative-type photosensitive composition include screen printing, transfer printing, offset printing, jet printing, dispenser, jet dispenser, needle dispenser, comma coater, slit coater, die coater, gravure coater, slit coat, relief printing, intaglio printing, gravure printing, stencil printing, soft lithography, bar coat, applicator, particle deposition method, spray coater, spin coater, dip coater, etc. From the perspective of workability of application and uniformity of film thickness, application may be performed by screen printing or spin coating.

[0158] The depth at which the photosensitive resin composition is impregnated into the metal sintered body, and the method for developing the film of the liquid negative-type photosensitive resin composition may be the same as the above-described process S2-1a and process S2-2a.

[0159] After passing through process S2-2b, a conductive bias-attached substrate (51b) is obtained (see Fig. 5 (b)).

[0160] In addition, after process S2-2b, process S2-3b may be performed to cure the negative-type photosensitive resin composition included in the resin-containing portion, in the same manner as the above-described processes S2-3a and S2-4a, and after process S2-3b, process S2-4b may be performed to desmear treatment on at least the exposed surface of the metal sintered body.

[0161] In another embodiment, process S2 may include process S2-1c (see FIG. 6 (a)), in which a positive photosensitive resin composition is impregnated into at least a portion of the metal sintered body by applying a liquid positive photosensitive resin composition to the surface of a substrate attached to the metal sintered body or by laminating a film-shaped positive photosensitive resin composition; and process S2-2c (see FIG. 6 (b) and (c)), in which, after process S2-1c, a coating of the liquid positive photosensitive resin composition or a film-shaped positive photosensitive resin composition is removed by exposure and development treatment to expose the metal sintered body having a resin-containing portion containing the positive photosensitive resin composition at the opening of the hole.

[0162] For the positive type photosensitive composition, commercially available products such as AH-3000 (Resonnac Co., Ltd., product name), AR-5100 (Resonnac Co., Ltd., product name), and OFPR-8600 (Tokyo Oka High School Co., Ltd., product name) may be used.

[0163] For the application of the photosensitive composition and the lamination of the photosensitive composition, the above-described method may be used.

[0164] The depth at which the photosensitive resin composition is impregnated into the metal sintered body may be the same as that of the above-described process S2-1a.

[0165] The exposure in process S2-2c may utilize, for example, a light beam using a g-line stepper as a light source; ultraviolet rays using a low-pressure mercury lamp, a high-pressure mercury lamp, a metal halide lamp, an i-line stepper as a light source; an electron beam; a laser beam, etc. The amount of exposure is appropriately selected according to the light source used, the thickness of the impregnated photosensitive resin composition, etc.

[0166] Regarding the method for developing a coating film of a liquid positive-type photosensitive resin composition or a film-type positive-type photosensitive resin composition, it may be the same as the process S2-2a described above.

[0167] After passing through process S2-2c, a conductive bias-attached substrate (51c) is obtained (see (c) of FIG. 5).

[0168] In addition, if the positive type photosensitive resin composition includes a thermosetting component, after process S2-2c, process S2-3c may be performed to thermosetting the positive type photosensitive resin composition included in the resin-containing portion. In addition, after process S2-3c, process S2-4c may be performed to desmear at least on the exposed surface of the metal sintered body, in the same manner as process S2-4a described above.

[0169] Method for manufacturing a wiring board with a challenged wire attached

[0170] The method for manufacturing a conductive bias-attached wiring board of the present embodiment comprises a process S3 of forming wiring electrically connected to a conductive bias on a conductive bias-attached substrate obtained by the method for manufacturing a conductive bias-attached substrate of the present embodiment.

[0171] Process S3 may have a resist forming process, a plating process, a resist removal process and an etching process as described below.

[0172] <Resist Formation Process>

[0173] In the resist formation process, for example, as shown in FIG. 7 (a) and (b), a negative-type photosensitive dry film (8) for an etching resist is laminated on the main surface of a silicon substrate (40) and a conductive bias, and then a photomask that transmits light in a wiring shape is superimposed and exposed with ultraviolet light, and the unexposed area is removed with a developer to form an etching resist (8a).

[0174] Methods for forming an etching resist (8a) other than those mentioned above include, for example, a method of silk screen printing a resist ink, or a method of laminating a dry film resist with a laminator.

[0175] In the case where the conductive bias-attached substrate is obtained through process S2 having process S2-1a and process S2-2a, an etching resist (8a) may be formed by irradiating a negative-type photosensitive resin composition on a film in the shape of wiring before process S2-2a.

[0176] <Plating Process>

[0177] In the plating process, for example, as shown in (c) of FIG. 7, wiring (9) can be formed in the opening of the etching resist (8a) by methods such as electroplating or electroless plating.

[0178] <Resist Removal Process>

[0179] In the resist removal process, the etching resist (8a) can be removed by a method such as a wet process using an alkaline aqueous solution, or an organic solvent-based solution such as an organic amine-based solution such as TMAH and a ketone-based solution such as acetone, as shown in FIG. 7 (d), or by a dry process such as plasma or ozone.

[0180] <Etching Process>

[0181] In the etching process, the metal film (2) in the portion not covered by the wiring (9) can be removed by etching. In this embodiment, a portion of the metal film (2) provided on both main surfaces of the silicon wafer (1) is removed by etching.

[0182] Examples of etching methods include using chemical etching solutions used in ordinary wiring boards, such as a solution of copper(II) chloride and hydrochloric acid, a solution of ferric chloride, a solution of sulfuric acid and hydrogen peroxide, and an ammonium persulfate solution.

[0183] By the above process e, a conductive wire board (52) with a conductive bias attached, as shown in (e) of FIG. 7, can be obtained.

[0184] In addition, in the method described above, a process may be provided to remove at least a portion of a conductive material, such as a sintered body of metal paste or a metal film (2), remaining on the main surface of the silicon substrate (40) before process e.

[0185] Means for removing conductors include chemical polishing, mechanical polishing, chemical-mechanical polishing, fly-cutting, and plasma treatment. Fly-cutting refers to cutting and flattening using a surface planer.

[0186] According to the method for manufacturing a conductive bias-attached wiring board of the present embodiment, by providing wiring on the conductive bias-attached wiring board of the present embodiment, a conductive bias-attached wiring board having excellent connection reliability and exhibiting a sufficiently low connection resistance value can be obtained.

[0187] <Challenge Buyer Attachment Substrate>

[0188] The conductive bias attachment substrate of the present embodiment comprises a substrate having a through hole and a conductive bias provided within the through hole, wherein the conductive bias comprises a metal sintered body having a porous structure, and the metal sintered body comprises a resin containing portion that includes a photosensitive resin composition or a cured product thereof.

[0189] The conductive bias-attached substrate of the present embodiment can be obtained by the manufacturing method of the conductive bias-attached substrate of the present embodiment described above.

[0190] <Challenge Buyer Attached Wiring Board>

[0191] The conductive bias attachment wiring board of the present embodiment comprises the conductive bias attachment board of the present embodiment and wiring provided on the conductive bias attachment board that is electrically connected to the conductive bias.

[0192] The conductive bias-attached wiring board of the present embodiment can be obtained by the manufacturing method of the conductive bias-attached wiring board of the present embodiment described above, and can have excellent connection reliability while exhibiting a sufficiently low connection resistance value.

[0193] Examples

[0194] The present invention will be explained more specifically below through examples and comparative examples, but the present invention is not limited to the following examples.

[0195] [Preparation of Metal Paste]

[0196] (Jojeye A~J)

[0197] Metal pastes were prepared by mixing the raw materials shown below in the ratios shown in Tables 1 and 2 using 3 rolls.

[0198] <First Copper Particle>

[0199] (Wet copper powder)

[0200] Spherical copper particles W1: 1050Y (Made by Mitsui Kinzoku Kogyo Co., Ltd., average particle size (D50): 0.81μm, spherical)

[0201] Spherical copper particles W4: 1300Y (Made by Mitsui Kinzoku Kogyo Co., Ltd., average particle size (D50): 3.5μm, spherical)

[0202] Flat copper particles W2: 1200YP (Made by Mitsui Kinzoku Kogyo Co., Ltd., average particle size (D50): 3.1μm, flat)

[0203] (Atomized copper powder)

[0204] Spherical copper particles A2: MA-C025K (Made by Mitsui Kinzoku Kogyo Co., Ltd., average particle size (D50): 2.4μm, spherical)

[0205] Second copper particle

[0206] Spherical copper particles W5: CH0200L1 (Made by Mitsui Kinzoku Kogyo Co., Ltd., average particle size (D50): 200 nm, spherical)

[0207] Solder particles

[0208] Solder particle 1: SnBi58 solder STC-3 (Made by Mitsui Kinzoku Kogyo Co., Ltd., average particle size (D50): 4.1μm, spherical)

[0209] Solder particles 2: Sn96.5Ag3Cu0.5 solder STC-3 (manufactured by Mitsui Kinzoku Kogyo Co., Ltd., average particle size (D50): 4.1μm, spherical)

[0210] Nickel particles

[0211] Nickel Particle 1: Nickel nanoparticles (Made by EM Japan, average particle size (D50): 0.1μm, spherical)

[0212] Nickel Particle 2: Nickel particles (Made by METAL FOIL & POWDERS MFG CO., Average particle size (D50): 3.0μm, Spherical)

[0213] Silver particles

[0214] Silver Particle 1: OS Silver Fine Particles (Manufactured by Osaka Soda Co., Ltd., Average Particle Size (D50): 0.2μm, Spherical)

[0215] Silver Particle 2: NP-AG-15 (Made by EM Japan, Average particle size (D50): 3μm, Spherical)

[0216] Silver particle 3: AgC-271B (Manufactured by Fukuda Kinzoku Hakufun High School Co., Ltd., average particle size (D50): 2.1μm, flat)

[0217] Silver-coated copper particles

[0218] Silver-coated copper particles 1: 10% Ag coated Cu-HWQ5μm (Manufactured by Fukuda Kinzoku Hakufun Kogyo Co., Ltd., average particle size (D50): 5.9μm, spherical)

[0219] Silver-coated copper particles 2: 10% Ag coat 2L3 (Manufactured by Fukuda Kinzoku Hakufun Kogyo Co., Ltd., average particle size (D50): 10.9μm, flat)

[0220] <Resin Components>

[0221] Resin R1: A mixture of "KFA-2000" (manufactured by Kogaku Kogyo Co., Ltd., an acrylic binder) as an organic binder and a mixture of carbitol and terpineol as organic solvents (mass ratio of carbitol to terpineol in the mixture [carbitol:terpineol] = 1:1) in a mass ratio of 1:2.

[0222] Volatile solvents

[0223] (High vapor pressure solvent: vapor pressure at 20℃ of 4 Pa ​​or more and 30 Pa or less)

[0224] α-terpineol: Manufactured by Fujifilm Wako Junyaku Co., Ltd., vapor pressure at 20°C 6.5 Pa

[0225] (Low vapor pressure solvent: vapor pressure of less than 4 Pa ​​at 20°C)

[0226] Isobornylcyclohexanol: Manufactured by Nippon Terpen Kagaku High School, trade name "Tersolve MTPH", vapor pressure at 20°C 0.004 Pa

[0227] Diethylene glycol mono-n-butyl ether: Manufactured by Showa Chemical Co., Ltd., vapor pressure at 20°C 1.3 Pa

[0228] [Table 1]

[0229]

[0230] [Table 2]

[0231]

[0232] [Fabrication of glass substrates with challenge buyer attachments]

[0233] (Examples 1–32 and Comparative Examples 1–9)

[0234] A glass substrate with a challenge buyer attached was manufactured in the following order.

[0235] Preparation of glass substrate

[0236] A glass substrate "D263Teco" (manufactured by SCHOTT, trade name, material: borosilicate glass, average linear thermal expansion coefficient α: 7.2×10⁻⁶) having through holes, wherein a titanium layer (thickness 100 nm) and a copper layer (thickness 300 nm) are formed in this order on both main surfaces and on the walls of the through holes. -6 K-1) was prepared. In addition, the glass substrate has a diameter of 6 inches and a thickness of 300 μm, and the titanium layer and copper layer above are formed sequentially by sputtering. Substrates with through holes having hole diameters (Bier diameters) of 50, 90, 150, and 200 μm were each prepared.

[0237] Production of Metal Particle Films

[0238] By a screen printing machine, the metal paste of Preparation Example A prepared above was printed on a PET film with a thickness of 100 μm using a screen printing plate (line diameter: 23 μm, mesh count: 400, eye size: 41 μm, space ratio: 41 μm) with an 8-inch φ size (circular shape with a diameter of 20 cm), and a metal particle film having a metal particle-containing layer was obtained.

[0239] Formation of Metal Sintered Body

[0240] Using a lamination device VJ-35 (manufactured by Ayumi High School Co., Ltd.), a metal particle film was laminated onto a glass substrate from the metal particle-containing layer side, and the laminate was vacuum pressed at room temperature at a pressure of 3 MPa to fill the through hole with metal paste. At this time, the metal paste was protruded on the side opposite to the side of the glass substrate where the metal particle film was laminated.

[0241] Next, the PET film peeled off from the above laminate was dried in the atmosphere at 90°C for 10 minutes. In addition, the concentration (mass%) of metal particles in the metal paste portion before and after drying was 95.7 mass% and 97.8 mass%, respectively.

[0242] With respect to the laminate after drying, as shown in FIGS. 3 (a) to (d), the metal paste on the main surface of the side where the metal particle film of the glass substrate is laminated is removed using a rubber squeegee, and subsequently, the metal paste protruding to the side opposite to the side where the metal particle film of the glass substrate is laminated is removed using a rubber squeegee.

[0243] Next, a glass substrate in which a metal sintered body precursor was formed within a through hole by the above-described process was placed in a tube furnace (AVC Co., Ltd.), and argon gas was flowed at a rate of 1 L / min to replace the air inside the tube furnace with argon gas. Subsequently, hydrogen gas was flowed at a rate of 300 mL / min, the temperature was raised to 300°C over 10 minutes, and a sintering treatment was performed at 300°C for 60 minutes to sinter the metal sintered body precursor. Afterward, argon gas was flowed at a rate of 0.3 L / min to cool the substrate, and the substrate was removed into the air at a temperature of 50°C or lower to obtain a glass substrate with a metal sintered body attached.

[0244] For the glass substrate with the metal sintered body attached as above, the porosity of the metal sintered body was evaluated according to the following method.

[0245] (Porosity of metal sintered body)

[0246] A glass substrate with a metal sintered body attached, which had undergone mechanical polishing, was cut in the thickness direction, and the cross-section of the central part of the metal sintered body on the glass substrate was exposed by a focused ion beam and observed. When observing the cross-section of the central part of the through hole in the glass substrate, a range of ±5 μm in the thickness direction of the glass substrate and ±5 μm in the direction perpendicular to the thickness direction of the glass substrate was observed from the center of the through hole. The focused ion beam processing observation device used was the MI4050 (manufactured by Hitachi High Technologies Co., Ltd.). For observation, a scanning electron microscope S-3700N (manufactured by Hitachi High Technologies Co., Ltd.) was used, and a cross-sectional image of the metal sintered body (a square with sides of approximately 10 μm) was captured at a magnification of 5000x. Five observation points were set. The obtained cross-sectional image was binarized using image analysis software (Adobe Photoshop Elements) to separate the sintered copper portion from the porous portion. For each of the five observation points, the ratio of the area of ​​the porous portion to the total area of ​​the cross-section of the metal sintered body was calculated and this was defined as the porosity. The average value of the porosity of the five observation points was defined as the porosity of the metal sintered body. For observation, a scanning electron microscope S-3700N (manufactured by Hitachi High Technologies Co., Ltd.) was used, and a cross-sectional image (a square with sides of approximately 10 μm) of the metal sintered body was captured at a magnification of 5000x.

[0247] [Fabrication of Wiring Boards]

[0248] (Examples 1-4)

[0249] On a glass substrate with a metal sintered body attached (butter diameter: 50, 90, 150, 200 μm) prepared in the same manner as above, a conductive bit having a resin-containing portion containing a photosensitive resin composition was formed in the following order, and wiring was additionally formed to obtain a wiring substrate and evaluated.

[0250] A dry film resist layer was formed on the surface of the glass substrate with the metal sintered body attached obtained above by laminating a UV-curing type etching resist dry film "RD-1619" (manufactured by Resonac Co., Ltd., trade name) (photosensitive resin composition F1) by atmospheric pressure lamination under conditions of a roll pressure of 0.4 MPa, a processing temperature of 120°C, and a conveying speed of 1.0 m / s. Next, the dry film resist layer was exposed to 55 mJ / cm² using a direct exposure machine "DE-1UH" (manufactured by Bayer Mechanics Co., Ltd., part number). 2 Under the conditions, exposure was performed in a predetermined pattern. After 1 minute, a Post Exposure Bake (PEB) treatment was performed at 70°C for 1 minute, and subsequently, a treatment was performed at 30°C for 70 seconds at a spray pressure of 0.17 MPa using a developer solution of 1% sodium carbonate, and a resist pattern was formed by removing residue by oxygen plasma treatment. After performing surface treatment with an etching treatment (ammonium persulfate: 100 g / L, RT, for 30 seconds) and an aqueous sulfuric acid solution (100 g / L, RT, for 30 seconds), electroplating was performed on the resist openings. Subsequently, by stripping the resist and etching the seed layer to form wiring having a wiring pattern of 300 μm × 600 μm, a test specimen (55) (wiring substrate) as shown in FIG. 8 was obtained. In addition, the wiring pattern was finished so that the thickness was about 10 μm after etching the seed layer. In the test specimen (55), a conductive bias formed in a through hole is electrically connected by wiring provided on the surface of the substrate.

[0251] (Examples 5-8)

[0252] A wiring board was obtained and evaluated in the same manner as in Examples 1 to 4, except that the roll pressure of the dry film "RD-1619" was changed to 1.0 MPa.

[0253] (Examples 9–12)

[0254] A wiring board was obtained and evaluated in the same manner as in Examples 1 to 4, except that the roll pressure of the dry film "RD-1619" was changed to 3.0 MPa.

[0255] (Examples 13–16)

[0256] On a glass substrate with a metal sintered body attached (butter diameter: 50, 90, 150, 200 μm) prepared in the same manner as above, a conductive bit having a resin-containing portion containing a cured product of a photosensitive resin composition was formed in the following order, and wiring was additionally formed to obtain a wiring substrate and evaluated.

[0257] A dry film resist layer was formed on the surface of the metal sintered body-attached glass substrate obtained above by laminating a photosensitive film type TMMF NA1000 (manufactured by Tokyo Oka Kogyo Co., Ltd., trade name) (photosensitive resin composition F2) by atmospheric pressure lamination under conditions of roll pressure 1.0 MPa, processing temperature 120°C, and conveying speed 1.0 m / s. Next, PEB treatment was performed at 80°C for 5 minutes, and subsequently, the dry film resist layer formed on the glass substrate surface was peeled off over the entire surface by using PEGMEA (developer) at a spray pressure of 0.17 MPa and 30°C for 1 minute. Subsequently, heat treatment was performed at 200°C for 2 minutes to cure the photosensitive resin composition (TMMF NA1000) impregnated in the porous portion of the copper sintered body. In addition, residues of the photosensitive resin composition and its cured product remaining on the surface of the copper sintered body were removed by oxygen plasma treatment.

[0258] [Wire Formation Process A]

[0259] A dry film resist layer was formed on the surface of the conductive Beyer-attached glass substrate obtained above by laminating a UV-curable etching resist dry film "RD-1619" (manufactured by Resonac Co., Ltd., trade name) by atmospheric pressure lamination under conditions of a roll pressure of 0.4 MPa, a processing temperature of 120°C, and a conveying speed of 1.0 m / s. Next, the dry film resist layer was exposed to 55 mJ / cm² using a direct exposure machine "DE-1UH" (manufactured by Beyer Mechanics Co., Ltd., part number). 2 Under the conditions, exposure was performed in a predetermined pattern. After 1 minute, PEB treatment was performed at 70°C for 1 minute, and subsequently, a resist pattern was formed by using a developer solution of 1% sodium carbonate, spraying pressure of 0.17 MPa, and treatment at 30°C for 70 seconds, and removing residue by oxygen plasma treatment. Subsequently, electroplating was performed on the resist opening, and then the resist was peeled off and the seed layer was etched to form wiring having a wiring pattern of 300 μm × 600 μm, thereby obtaining a test specimen (55) (wiring substrate) as shown in FIG. 8. In addition, the wiring pattern was finished so that the thickness was about 10 μm after the etching of the seed layer. In the test specimen (55), a conductive bias formed in a through hole is electrically connected by wiring provided on the surface of the substrate.

[0260] (Examples 17-20)

[0261] On a glass substrate with a metal sintered body attached (butter diameter: 50, 90, 150, 200 μm) prepared in the same manner as above, a conductive bit having a resin-containing portion containing a cured product of a photosensitive resin composition was formed in the following order, and wiring was additionally formed to obtain a wiring substrate and evaluated.

[0262] On the surface of the metal-sintered glass substrate obtained above, a developing type dry film solder resist PSR-800 AUS SR-1 (manufactured by Taiyo Ink Seizo Co., Ltd., trade name) (photosensitive resin composition F3) was laminated using a vacuum laminate MVLP series (manufactured by Nihon Seikosho Co., Ltd., trade name) under conditions of 100°C, 0.5 MPa, and a cycle time of 30 seconds, after a vacuum degree of 3 hPa and a cycle time of 30 seconds. Subsequently, a press treatment was performed under conditions of 80°C, 0.8 MPa, and a cycle time of 60 seconds. Next, a developing treatment was performed with a 1 mass% sodium carbonate solution under conditions of 30°C, a spray pressure of 0.15 MPa, and 1 minute, and a water rinse was performed under conditions of 25°C, a spray pressure of 0.10 MPa, and 1 minute. The dry film resist layer formed on the surface of the glass substrate was peeled off over the entire surface. Next, post-curing was performed at 150°C for 60 minutes to cure the photosensitive resin composition (PSR-800 AUS SR-1) impregnated in the porous portion of the copper sintered body. Additionally, residual photosensitive resin composition and the cured product remaining on the surface of the copper sintered body were removed by oxygen plasma treatment.

[0263] A wiring was formed on the surface of the conductive bias-attached glass substrate obtained above in the same manner as the wiring formation process A, and a test specimen (55) (wiring substrate) as shown in FIG. 8 was obtained.

[0264] (Examples 21–24)

[0265] On a glass substrate with a metal sintered body attached (butter diameter: 50, 90, 150, 200 μm) prepared in the same manner as above, a conductive bit having a resin-containing portion containing a cured product of a photosensitive resin composition was formed in the following order, and wiring was additionally formed to obtain a wiring substrate and evaluated.

[0266] On the surface of the metal-sintered glass substrate obtained above, a developing-type screen printing solder resist PSR-4000 G24K / CA-40 G24 (manufactured by Taiyo Ink Seizo Co., Ltd., trade name) (photosensitive resin composition L1) was printed on one side using a screen printer to a thickness of approximately 20 μm. After performing a preliminary drying at 80°C for 30 minutes, the opposite side was printed in the same way using a screen printer to a thickness of approximately 20 μm, and a preliminary drying was performed at 80°C for 30 minutes. Subsequently, a developing treatment was performed with a 1 mass% sodium carbonate solution at 30°C, a spray pressure of 0.15 MPa, and for 1 minute, followed by rinsing with water at 25°C, a spray pressure of 0.10 MPa, and for 1 minute. The solder resist layer formed on the surface of the glass substrate was peeled off over the entire surface. Next, post-curing was performed at 150°C for 60 minutes to cure the photosensitive resin composition (PSR-4000 G24K / CA-40 G24) impregnated in the porous portion of the copper sintered body. Additionally, residual photosensitive resin composition and the cured product remaining on the surface of the copper sintered body were removed by oxygen plasma treatment.

[0267] A wiring was formed on the surface of the conductive bias-attached glass substrate obtained above in the same manner as the wiring formation process A, and a test specimen (55) (wiring substrate) as shown in FIG. 8 was obtained.

[0268] (Examples 25-28)

[0269] On a glass substrate with a metal sintered body attached (butter diameter: 50, 90, 150, 200 μm) prepared in the same manner as above, a conductive bit having a resin-containing portion containing a cured product of a photosensitive resin composition was formed in the following order, and wiring was additionally formed to obtain a wiring substrate and evaluated.

[0270] On the surface of the metal-sintered glass substrate obtained above, positive-type photosensitive resin AH-3000 (Resonac Co., Ltd., trade name) (photosensitive resin composition L2) was coated on one side by spin coating at 1000 rpm for 5 seconds and 2000 rpm for 20 seconds to achieve a thickness of approximately 5 μm. After pre-drying at 120°C for 150 seconds, the opposite side was treated in the same manner by spin coating at 1000 rpm for 5 seconds and 2000 rpm for 20 seconds to achieve a thickness of approximately 5 μm. A vertical exposure machine "DE-1UH" (Bayer Mechanics Co., Ltd., part number) was used at 500 mJ / cm² 2 Under the conditions, the entire surface of both sides of the substrate was exposed. Subsequently, a positive-type photosensitive resin composition layer formed on the surface of the glass substrate was peeled off over the entire surface by using 2.38%-TMAH (developer) and performing treatment at 30°C for 1 minute at a spray pressure of 0.17 MPa. Then, heat treatment was performed at 230°C for 60 minutes to cure the positive-type photosensitive resin composition (AH-3000) impregnated in the porous portion of the copper sintered body. In addition, residual photosensitive resin composition and the cured product remaining on the surface of the copper sintered body were removed by oxygen plasma treatment.

[0271] A wiring was formed on the surface of the conductive bias-attached glass substrate obtained above in the same manner as the wiring formation process A, and a test specimen (55) (wiring substrate) as shown in FIG. 8 was obtained.

[0272] (Examples 29–32)

[0273] On a glass substrate with a metal sintered body attached (butter diameter: 50, 90, 150, 200 μm) prepared in the same manner as above, a conductive bit having a resin-containing portion containing a cured product of a photosensitive resin composition was formed in the following order, and wiring was additionally formed to obtain a wiring substrate and evaluated.

[0274] On the surface of the conductive bias-attached glass substrate obtained above, positive-type photosensitive resin AH-3000 (Resonac Co., Ltd., trade name) (photosensitive resin composition L2) was coated on one side by spin coating at 1000 rpm / 5 seconds to a thickness of approximately 20 μm. Afterward, the surface was vacuum-evacuated to a vacuum level of 3 hPa, and the positive-type photosensitive resin composition (AH-3000) was impregnated into the porous portion of the copper sintered body. Pre-drying was performed at 120°C for 150 seconds. In the same way, the opposite side was treated by spin coating at 1000 rpm / 5 seconds to a thickness of approximately 20 μm. Afterward, the surface was vacuum-evacuated to a vacuum level of 3 hPa, and the positive-type photosensitive resin composition (AH-3000) was impregnated into the porous portion of the copper sintered body. In addition, pre-drying was performed at 120°C for 150 seconds. A vertical exposure machine "DE-1UH" (manufactured by Bayer Mechanics Co., Ltd., part number) was used at 500 mJ / cm² 2 Under the conditions, the entire surface of both sides of the substrate was exposed. Subsequently, a positive-type photosensitive resin composition layer formed on the surface of the glass substrate was peeled off over the entire surface by using 2.38%-TMAH (developer) and performing treatment at 30°C for 1 minute at a spray pressure of 0.17 MPa. Then, heat treatment was performed at 230°C for 60 minutes to cure the positive-type photosensitive resin composition (AH-3000) impregnated in the porous portion of the copper sintered body. In addition, residual photosensitive resin composition and the cured product remaining on the surface of the copper sintered body were removed by oxygen plasma treatment.

[0275] A wiring was formed on the surface of the conductive bias-attached glass substrate obtained above in the same manner as the wiring formation process A, and a test specimen (55) (wiring substrate) as shown in FIG. 8 was obtained.

[0276] (Comparative Examples 1–4)

[0277] A wiring substrate was obtained and evaluated in the same manner as in Examples 1 to 4, except that the roll pressure of the dry film "RD-1619" was changed to 0.1 MPa and the processing time in the etching process was set to 5 minutes.

[0278] (Comparative Examples 5~8)

[0279] On a glass substrate with a metal sintered body attached (butter diameter: 50, 90, 150, 200 μm) manufactured in the same manner as above, a conductive bit having a resin-containing portion containing a cured product of a thermosetting resin composition was formed in the following order, and wiring was additionally formed to obtain a wiring substrate and evaluated.

[0280] A curable resin composition as described below was applied to one side of the glass substrate with the metal sintered body attached obtained above using a roll coater. Subsequently, the glass substrate with the metal sintered body attached was placed in a container, and the inside of the container was vacuumed to a gauge pressure of 100 kPa. The glass substrate with the metal sintered body attached was maintained in a vacuum state for 10 minutes, and then the glass substrate with the metal sintered body attached was removed from the container. It was confirmed that the curable resin composition was impregnated into the copper sintered body with the through hole, and that the curable resin composition had reached the side opposite to the side of the copper sintered body with the through hole where the curable resin composition was applied. The curable resin composition remaining on the surface of the glass substrate with the metal sintered body attached was removed with a rubber spatula. Subsequently, the application and removal of the curable resin composition were performed on the side opposite to the side where the curable resin composition was applied, in the same manner as above.

[0281] [Curable resin composition]

[0282] YDF-170 (manufactured by Toto Kasei Co., Ltd., trade name, bisphenol F type epoxy resin, epoxy equivalent = 170): 95 parts by mass

[0283] 2PZ-CN (manufactured by Shikoku Kasei Co., Ltd., trade name, imidazole compound): 5 parts by mass

[0284] A glass substrate with a metal sintered body attached, in which a curable resin composition was impregnated into a copper sintered body, was maintained at 180°C for 1 hour in a nitrogen atmosphere to obtain a conductive biodetector attached glass substrate having a through electrode. Subsequently, oxygen plasma treatment was performed for 5 minutes to remove the curable resin composition and the cured product remaining on the biodetector surface.

[0285] (Comparative Example 9)

[0286] A glass substrate with a metal sintered body attached was prepared in the same manner as above, except that a glass substrate (byer diameter: 90 μm) and the metal paste of Preparation Example J were used, and the porosity was measured. In addition, the concentration (mass%) of metal particles in the metal paste portion before and after drying was 94.7 mass% and 96.0 mass%, respectively.

[0287] A wiring board was obtained in the same manner as in Example 1, except that the metal sintered body attached glass substrate prepared above was used, and the evaluation was performed.

[0288] [Impregnation depth of photosensitive resin composition into porous portion of metal sintered body]

[0289] The cross-section of the conductive bias of a glass substrate with a conductive bias attached was exposed by cross-section polishing, and the surface was cleaned by ion milling to observe the cross-section. Using a scanning electron microscope S-3700N (manufactured by Hitachi High Technologies Co., Ltd.), the impregnation depth of the photosensitive resin composition (or its cured product) into the porous portion was measured. The distance from the bias surface to the porous portion was measured at 10 locations, and the average value was taken as the impregnation depth.

[0290] [Evaluation of Wiring Boards]

[0291] For the test specimen obtained above, the initial resistance value, connection reliability, and the concave portion of the wiring pattern surface formed on the conductive wire were evaluated according to the following method.

[0292] <Initial Resistance Value>

[0293] As the initial resistance value of the test specimen (55) (wiring board), the resistance value of 1000 connected by the buyer was measured. Based on this connection resistance value, the initial resistance value was evaluated according to the following judgment criteria.

[0294] (Number of Buyers)

[0295] 1000

[0296] (Judgment Criteria)

[0297] A: Resistance value less than 6Ω

[0298] B: Resistance value 6Ω or more and less than 10Ω

[0299] C: Resistance value 10Ω or more and less than 20Ω

[0300] D: Resistance value 20Ω or more and less than 50Ω

[0301] E: Resistance value is 50Ω or higher

[0302] <Connection Reliability - Temperature Cycle Test>

[0303] A test specimen (55) (wiring board) was set in a temperature cycle tester (TSA-72SE-W, manufactured by Espect Co., Ltd.), and a temperature cycle connection reliability test was performed under the following conditions: low temperature side: -55℃, 15 minutes; room temperature: 2 minutes; high temperature side: 125℃, 15 minutes; defrosting cycle: automatic; number of cycles: 50, 100, 300, 500, 1000 cycles. For each test specimen that had undergone the number of cycles, the resistance value of the above number of connected wires was measured. Based on this connection resistance value, the connection reliability was evaluated according to the following judgment criteria.

[0304] (Judgment Criteria)

[0305] A: Rate of change in resistance is less than 1% of the initial resistance value

[0306] B: Rate of change in resistance is 1% or more and less than 3% relative to the initial resistance value

[0307] C: Rate of change in resistance is 3% or more and less than 5% relative to the initial resistance value

[0308] D: Rate of change in resistance is 5% or more and less than 10% of the initial resistance value

[0309] E: Rate of change in resistance is 10% or more and less than 20% of the initial resistance value

[0310] F: Rate of change in resistance is 20% or more relative to the initial resistance value

[0311] G: Continuity failure occurred

[0312] <Connection Reliability -150℃>

[0313] A test specimen (55) was set in a high-temperature bath (precision thermostat DH612, manufactured by Yamato Kagaku Co., Ltd.) and a high-temperature storage test was performed by leaving it at 150°C for 50, 100, 300, and 500 hours. For each test specimen that had passed through each time, the resistance value of the above number of connected wires was measured. Based on this connection resistance value, the connection reliability was evaluated according to the following judgment criteria.

[0314] (Judgment Criteria)

[0315] A: Rate of change in resistance is less than 1% of the initial resistance value

[0316] B: Rate of change in resistance is 1% or more and less than 3% relative to the initial resistance value

[0317] C: Rate of change in resistance is 3% or more and less than 5% relative to the initial resistance value

[0318] D: Rate of change in resistance is 5% or more and less than 10% of the initial resistance value

[0319] E: Rate of change in resistance is 10% or more and less than 20% of the initial resistance value

[0320] F: Rate of change in resistance is 20% or more relative to the initial resistance value

[0321] G: Continuity failure occurred

[0322] <Connection Reliability -200℃>

[0323] A test specimen (55) was set in a high-temperature bath (precision thermostat DH612, manufactured by Yamato Kagaku Co., Ltd.) and a high-temperature storage test was performed by leaving it at 200°C for 50, 100, 300, and 500 hours. For each test specimen that had passed through each time, the resistance value of the above number of connected wires was measured. Based on this connection resistance value, the connection reliability was evaluated according to the following judgment criteria.

[0324] (Judgment Criteria)

[0325] A: Rate of change in resistance is less than 1% of the initial resistance value

[0326] B: Rate of change in resistance is 1% or more and less than 3% relative to the initial resistance value

[0327] C: Rate of change in resistance is 3% or more and less than 5% relative to the initial resistance value

[0328] D: Rate of change in resistance is 5% or more and less than 10% of the initial resistance value

[0329] E: Rate of change in resistance is 10% or more and less than 20% of the initial resistance value

[0330] F: Rate of change in resistance is 20% or more relative to the initial resistance value

[0331] G: Continuity failure occurred

[0332] <Recess on the surface of the wiring pattern formed on the challenge buyer>

[0333] The surface of the wiring pattern formed on the conductive bilayer of the test specimen (55) (wiring board) was observed for 30 conductive bilayers using a digital microscope (VHX-6000, manufactured by Keyence), and the deepest point was measured, and the average value was taken as the concave part of the wiring pattern surface.

[0334] (Judgment Criteria)

[0335] A: The average value of the average step difference is less than 2μm

[0336] B: Average value of average step difference is 2μm or more and less than 4μm

[0337] C: Average value of average step height is 4μm or more and less than 6μm

[0338] D: Average value of average step difference is 6μm or more and less than 8μm

[0339] E: Average value of average step difference is 8μm or more

[0340] [Table 3]

[0341]

[0342] [Table 4]

[0343]

[0344] [Table 5]

[0345]

[0346] [Table 6]

[0347]

[0348] [Table 7]

[0349]

[0350] (Examples 33–43)

[0351] A glass substrate with a metal sintered body attached was prepared in the same manner as in Examples 1 to 4, except that the metal paste of Preparation Example B was used, and the porosity was measured. In addition, the concentration (mass%) of metal particles in the metal paste portion before and after drying was 95.7 mass% and 97.8 mass%, respectively.

[0352] A wiring board was obtained in the same manner as in Examples 1 to 4, except that a glass substrate with a metal sintered body attached, prepared as above, was used, and the evaluation was performed.

[0353] (Example 37)

[0354] A glass substrate with a metal sintered body attached was prepared in the same manner as in Example 3, except that the metal paste of Preparation Example C was used, and the porosity was measured. In addition, the concentration (mass%) of metal particles in the metal paste portion before and after drying was 95.7 mass% and 97.8 mass%, respectively.

[0355] A wiring board was obtained using the metal sintered glass substrate prepared above, in the same manner as in Example 3, except that the roll pressure of the dry film "RD-1619" was changed to 3 MPa, and the evaluation was performed.

[0356] (Example 38)

[0357] A glass substrate with a metal sintered body attached was prepared in the same manner as in Example 3, except that the metal paste of Preparation Example D was used, and the porosity was measured. In addition, the concentration (mass%) of metal particles in the metal paste portion before and after drying was 95.7 mass% and 97.8 mass%, respectively.

[0358] A wiring board was obtained using the metal sintered glass substrate prepared above, in the same manner as in Example 3, except that the roll pressure of the dry film "RD-1619" was changed to 3 MPa, and the evaluation was performed.

[0359] (Example 39)

[0360] A glass substrate with a metal sintered body attached was prepared in the same manner as in Example 3, except that the metal paste of Preparation Example E was used, and the porosity was measured. In addition, the concentration (mass%) of metal particles in the metal paste portion before and after drying was 95.7 mass% and 97.8 mass%, respectively.

[0361] A wiring board was obtained in the same manner as in Example 3, except that the metal sintered body attached glass substrate prepared above was used, and the evaluation was performed.

[0362] (Example 40)

[0363] A glass substrate with a metal sintered body attached was prepared in the same manner as in Example 3, except that the metal paste of Preparation Example F was used, and the porosity was measured. In addition, the concentration (mass%) of metal particles in the metal paste portion before and after drying was 95.7 mass% and 97.8 mass%, respectively.

[0364] A wiring board was obtained in the same manner as in Example 3, except that the metal sintered body attached glass substrate prepared above was used, and the evaluation was performed.

[0365] (Example 41)

[0366] A glass substrate having a metal sintered precursor formed in a through hole was obtained by performing the same procedure as in Example 3, except that the metal paste of Preparation Example G was used. Subsequently, this glass substrate was placed in a tube furnace (AVC Co., Ltd.), heated to 300°C over 10 minutes under atmospheric conditions, and sintered by performing a sintering treatment at 300°C for 60 minutes. Afterward, the glass substrate was cooled by flowing argon gas at a flow rate of 0.3 L / min and removed into air at 50°C or lower to obtain a glass substrate with a metal sintered body attached. In addition, the concentration (mass%) of metal particles in the metal paste portion before and after drying was 95.7 mass% and 97.8 mass%, respectively.

[0367] A wiring board was obtained in the same manner as in Example 3, except that the metal sintered body attached glass substrate prepared above was used, and the evaluation was performed.

[0368] (Example 42)

[0369] A glass substrate with a metal sintered body attached was prepared in the same manner as in Example 3, except that the metal paste of Preparation Example H was used, and the porosity was measured. In addition, the concentration (mass%) of metal particles in the metal paste portion before and after drying was 95.7 mass% and 97.8 mass%, respectively.

[0370] A wiring board was obtained in the same manner as in Example 3, except that the metal sintered body attached glass substrate prepared above was used, and the evaluation was performed.

[0371] (Example 43)

[0372] A glass substrate with a metal sintered body attached was prepared in the same manner as in Example 3, except that the metal paste of Preparation Example 1 was used, and the porosity was measured. In addition, the concentration (mass%) of metal particles in the metal paste portion before and after drying was 95.7 mass% and 97.8 mass%, respectively.

[0373] A wiring board was obtained in the same manner as in Example 3, except that the metal sintered body attached glass substrate prepared above was used, and the evaluation was performed.

[0374] (Comparative Example 10)

[0375] A glass substrate with a metal sintered body attached was prepared in the same manner as in Example 41.

[0376] A wiring substrate was obtained and evaluated in the same manner as in Example 3, except that the metal sintered glass substrate prepared above was used, the roll pressure of the dry film "RD-1619" was changed to 0.1 MPa, and the processing time for the etching treatment was set to 5 minutes.

[0377] [Table 8]

[0378]

[0379] [Table 9]

[0380]

[0381] [Fabrication of Silicon Substrates with Challenge Buyer Attachment]

[0382] (Examples 44~47)

[0383] A silicon substrate with a challenge buyer attached was fabricated in the following order.

[0384] <Preparation of Silicon Substrate>

[0385] A silicon substrate was prepared having through holes, wherein a titanium layer, a nickel layer, and a copper layer were formed in this order on both main surfaces and on the walls of the through holes. Additionally, silicon substrates were prepared having a diameter of 6 inches and a thickness of 300 μm, wherein a titanium layer, a nickel layer, and a copper layer were formed by sequential sputtering, and through holes with hole diameters (Bier diameters) of 50, 90, 150, and 200 μm were provided.

[0386] Production of Metal Particle Films

[0387] By a screen printing machine, the metal paste of Preparation Example A prepared above was printed on a PET film with a thickness of 100 μm using a screen printing plate (line diameter: 23 μm, mesh count: 400, eye size: 41 μm, space ratio: 41 μm) with an 8-inch φ size (circular shape with a diameter of 20 cm), and a metal particle film having a metal particle-containing layer was obtained.

[0388] Formation of Metal Sintered Body

[0389] Using a bonding device VJ-35 (manufactured by Ayumi High School Co., Ltd.), a metal particle film was bonded to a silicon substrate from the metal particle-containing layer side, and the laminate was vacuum pressed at room temperature at a pressure of 3 MPa to fill the through hole with metal paste. At this time, the metal paste was extruded to the side opposite to the side of the silicon substrate where the metal particle film was bonded.

[0390] Next, the PET film peeled off from the above laminate was dried in the atmosphere at 90°C for 10 minutes. In addition, the concentration (mass%) of metal particles in the metal paste portion before and after drying was 95.7 mass% and 97.8 mass%, respectively.

[0391] With respect to the laminate after drying, as shown in FIGS. 3 (a) to (d), the metal paste on the main surface of the side where the metal particle film of the silicon substrate is laminated is removed using a rubber squeegee, and subsequently, the metal paste protruding to the side opposite to the side where the metal particle film of the silicon substrate is laminated is removed using a rubber squeegee.

[0392] Next, a silicon substrate having a metal sintered precursor formed in a through hole by the above-described process was placed in a tube furnace (AVC Co., Ltd.), and argon gas was flowed at a rate of 1 L / min to replace the air inside the tube furnace with argon gas. Subsequently, hydrogen gas was flowed at a rate of 300 mL / min, the temperature was raised to 300°C over 10 minutes, and a sintering treatment was performed at 300°C for 60 minutes to sinter the metal sintered precursor. Afterward, argon gas was flowed at a rate of 0.3 L / min to cool the substrate, and the substrate was removed into the air at a temperature of 50°C or lower to obtain a silicon substrate with a metal sintered body attached.

[0393] For the silicon substrate with the metal sintered body attached as above, the porosity of the metal sintered body was evaluated according to the above method.

[0394] Using the silicon substrate with the metal sintered body obtained above, a wiring substrate was obtained in the same manner as in Examples 1 to 4, except that the roll pressure of the dry film "RD-1619" was changed to 3 MPa, and the evaluation was performed.

[0395] [Fabrication of Organic Substrates with Challenge Bias Attachment]

[0396] (Examples 48~50)

[0397] An organic substrate with a challenger attached was fabricated in the following steps.

[0398] <Preparation of Organic Substrate>

[0399] A high-Tg glass epoxy multilayer material MCL-E-679F(J) (Resonac Co., Ltd.) with a plate thickness of 300 μm and 1 μm copper foil laminated on both sides was prepared, and through holes with hole diameters (bayer diameters) of 90, 150, and 200 μm were provided. A copper plating film with a thickness of 0.5 μm was formed on the inside of the bay by electroless copper plating.

[0400] Using the above organic substrate, an organic substrate with a metal sintered body attached was obtained by following the same method as the above method for producing a silicon substrate with a metal sintered body attached, except that the temperature was raised to 225°C in 10 minutes and a sintering treatment was performed at 225°C for 60 minutes. For the obtained organic substrate with a metal sintered body attached, the porosity of the metal sintered body was evaluated according to the above method.

[0401] Using the organic substrate with the metal sintered body attached obtained above, a wiring substrate was obtained in the same manner as in Examples 2 to 4, except that the roll pressure of the dry film "RD-1619" was changed to 3 MPa, and the evaluation was performed.

[0402] [Table 10]

[0403]

[0404] It was confirmed that, according to the conductive bias-attached substrate of the example, a wiring board having excellent connection reliability and exhibiting a sufficiently low connection resistance value can be obtained.

[0405] In addition, regarding the wiring boards prepared in Examples 1 and 29, a cross-section of the central part of the conductive beam was exposed by a focused ion beam using a focused ion beam and observed using a focused ion beam observation device (manufactured by Hitachi High Technologies Co., Ltd., product name: MI4050), and the following findings were obtained.

[0406] In the wiring board produced in Example 1, the photosensitive resin composition was not impregnated in the central part of the conductive bias, and voids were visible between the copper particles, but no deterioration was observed due to the absorption of aqueous solutions used in the formation of electrolytic copper plating films. In addition, in the wiring board produced in Example 29, the photosensitive resin composition was impregnated in the central part of the conductive bias as well, and no voids were visible between the copper particles.

[0407] As such, the conductive bias-attached substrate of the example can be thought to have achieved both good wiring formation and suppression of absorption of aqueous solutions by impregnating it with a photosensitive resin composition, thereby removing the resin composition from the surface of the metal sintered body through a developing process while leaving the resin composition within the metal sintered body. Explanation of the symbols

[0408] 1… silicon wafer 2… metal film 3… metal paste part 3b… Metal sintered body precursor 3c… Challenge Buyer 3p… metal particle containing layer 7… Support film 8a… Etching resist 9… wiring 30… penetrating hole 31… Non-penetrating hole 32… Porous structure 34a, 34b, 34c… Resin composition 40, 41… silicon substrate 42… rubber squeegee 50… Challenge Buyer Attached Substrate 52… Challenge Buyer Attached Wiring Board 55… Test piece 80, 82, 84… Photosensitive resin composition A… pressure jig

Claims

Claim 1 A method for manufacturing a conductive bio-attached substrate, comprising: a step S1 of preparing a metal sintered body attached substrate having a substrate having a hole that is opened on one or both sides of the main surface and a metal sintered body having a porous structure provided inside the hole, wherein the metal sintered body is exposed at the opening of the hole; and a step S2 of providing a resin-containing portion comprising a photosensitive resin composition or a cured product thereof in the metal sintered body of the metal sintered body attached substrate. Claim 2 A method for manufacturing a conductive bias-attached substrate according to claim 1, wherein in the process S2, the resin-containing portion and the resin-non-containing portion not containing the resin composition or the cured product thereof are arranged in the metal sintered body such that the resin-containing portion is located on the opening side. Claim 3 A method for manufacturing a conductive bio-attached substrate according to claim 1, wherein the process S2 comprises: a process S2-1a of impregnating at least a portion of the metal sintered body with a negative-type photosensitive resin composition by laminating a film-type negative-type photosensitive resin composition on the surface of the metal sintered body-attached substrate; and a process S2-2a of removing the film-type negative-type photosensitive resin composition by a developing process after the process S2-1a, thereby exposing the metal sintered body having the resin-containing portion containing the negative-type photosensitive resin composition at the opening of the hole. Claim 4 A method for manufacturing a conductive bio-attached substrate according to claim 3, wherein the process S2 further comprises a process S2-3a for curing the negative-type photosensitive resin composition included in the resin-containing portion after the process S2-2a. Claim 5 A method for manufacturing a conductive bio-attached substrate according to claim 4, wherein the process S2 further comprises a process S2-4a of performing a desmear treatment on at least the exposed surface of the metal sintered body after the process S2-3a. Claim 6 A method for manufacturing a conductive bio-attached substrate according to claim 1, wherein the process S2 comprises: a process S2-1b of impregnating at least a portion of the metal sintered body with a negative-type photosensitive resin composition by applying a liquid negative-type photosensitive resin composition to the surface of the metal sintered body-attached substrate; and a process S2-2b of removing the film of the liquid negative-type photosensitive resin composition by a developing treatment after the process S2-1b, thereby exposing the metal sintered body having the resin-containing portion containing the negative-type photosensitive resin composition at the opening of the hole. Claim 7 A method for manufacturing a conductive bio-attached substrate according to claim 6, wherein the process S2 further comprises, after the process S2-2b, a process S2-3b for curing the negative-type photosensitive resin composition contained in the resin-containing portion. Claim 8 A method for manufacturing a conductive bio-attached substrate according to claim 7, wherein the process S2 further comprises a process S2-4b of performing a desmearing treatment on at least the exposed surface of the metal sintered body after the process S2-3b. Claim 9 A method for manufacturing a conductive bio-attached substrate according to claim 1, wherein the process S2 comprises: a process S2-1c of impregnating at least a portion of the metal sintered body with a positive-type photosensitive resin composition by applying a liquid positive-type photosensitive resin composition to the surface of the metal sintered body-attached substrate or by laminating a film-type positive-type photosensitive resin composition; and, after the process S2-1c, a process S2-2c of removing the coating of the liquid positive-type photosensitive resin composition or the film-type positive-type photosensitive resin composition by exposure and development treatment to expose the metal sintered body having the resin-containing portion containing the positive-type photosensitive resin composition at the opening of the hole. Claim 10 A method for manufacturing a conductive bio-attached substrate according to claim 9, wherein the positive-type photosensitive resin composition comprises a thermosetting component, and the process S2 further comprises, after the process S2-2c, a process S2-3c for thermosetting the positive-type photosensitive resin composition included in the resin-containing portion. Claim 11 A method for manufacturing a conductive bio-attached substrate according to claim 10, wherein the process S2 further comprises a process S2-4c of performing a desmearing treatment on at least the exposed surface of the metal sintered body after the process S2-3c. Claim 12 A method for manufacturing a conductive bilayer-attached wiring substrate, comprising a process S3 for forming wiring electrically connected to the conductive bilayer on a conductive bilayer-attached substrate obtained by the method described in any one of claims 1 to 11. Claim 13 A conductive biodetector substrate having a through hole and a conductive biodetector provided within the through hole, wherein the conductive biodetector comprises a metal sintered body having a porous structure, and the metal sintered body comprises a resin containing portion that includes a photosensitive resin composition or a cured product thereof. Claim 14 A conductive biodetector attachment substrate according to claim 13, wherein the metal sintered body further comprises a resin-free portion that does not include a resin composition or a cured product thereof, and the resin-containing portion is located on the opening side of the through hole of the metal sintered body. Claim 15 A conductive bilayer-attached wiring substrate having a conductive bilayer-attached substrate as described in claim 13 or claim 14, and wiring provided on the conductive bilayer-attached substrate that is electrically connected to the conductive bilayer.

Images