JP2014179473A - Method for manufacturing ceramic substrate and conductor material - Google Patents

Abstract

PROBLEM TO BE SOLVED: To suppress silver from diffusing from a conductor material during burning in a step of manufacturing a wiring circuit which uses a silver-based conductor material.SOLUTION: A method for manufacturing a ceramic substrate comprises the steps of: preparing a green sheet which is an unburned ceramic substrate (step S10); manufacturing a conductor paste added with a transition metal material including hydrogen atoms discharged during burning as an unburned silver-based conductor material (step S20); configuring an unburned laminate by laminating the green sheet in which a wiring pattern is formed using the conductor paste (step S30); and acquiring an LTCC substrate by burning the unburned laminate at a low temperature (step S40).

Description

  The present invention relates to a wiring board using a silver-based conductor material.

  As a wiring board using a silver-based conductive material, a low-temperature fired ceramic multilayer board (hereinafter also referred to as “LTCC board”. “LTCC” is an abbreviation for Low Temperature Co-fired Ceramics) is known. The LTCC substrate is usually manufactured by arranging an unsintered silver-based conductor material on a green sheet, which is an unsintered ceramic substrate, to produce a wiring pattern, and laminating and firing a plurality of the green sheets.

  By the way, in the manufacturing process of the wiring board which used not only the LTCC board | substrate but the silver-type conductor material, there existed a problem that the silver in a conductor material would diffuse in a board | substrate during baking. When the silver in the conductive material diffuses into the substrate, there are problems such as voids called voids between the wiring pattern formed by the conductor and the substrate, and deformation and discoloration of the substrate. Conventionally, in a manufacturing technique of a wiring board using a silver-based conductor material, a technique for suppressing the occurrence of defects due to silver diffusion during firing has been proposed (Patent Documents 1-12 below).

Japanese Patent No. 3528037 Japanese Patent No. 3121822 JP-A-6-20516 Japanese Patent Laid-Open No. 9-246722 JP 2003-162962 A JP 2008-288076 A Japanese Patent Publication No. 7-19964 JP-A-10-338546 JP-A-11-217260 JP 2007-81321 A JP 2002-80274 A JP 2007-81324 A

  In Patent Document 1, by adding a metal that forms an oxide more easily than silver at the firing temperature to the conductive material, the oxidation of silver during firing is suppressed, and silver diffuses into the glass ceramic insulating material. To suppress. Further, in Patent Document 2, glass having a softening point higher than that of the glass in the substrate material is added to the conductor paste, and the glass added to the conductor paste during firing is reacted with silver. Suppresses the diffusion of silver into the material. However, in the techniques of Patent Documents 1 and 2, there is a possibility that the resistance of the conductor is increased by the glass containing oxide or silver generated in the conductor.

  In Patent Document 3, a conductor composition that is contained in a conductor composition and that is promoted by silver diffusion during firing by a sintering control agent (chromium or chromium compound) that delays the sintering of a low-temperature fired substrate, The shrinkage of the low-temperature fired substrate at the interface with the low-temperature fired substrate is suppressed. However, in the technique of Patent Document 3, the diffusion of silver itself from the conductor material during firing is not suppressed. In addition, the conductor resistance may increase due to the sintering control agent remaining in the conductor composition. Furthermore, due to the influence of the sintering control agent that has moved to the interface between the conductor composition and the low-temperature fired substrate, the properties of the interface may differ from other parts of the substrate, which may cause problems such as a decrease in strength. .

  In Patent Document 4, glass powder that softens and melts prior to the glass powder in the glass ceramic material of the substrate during firing to the conductor paste and forms a film around the conductor wiring is added to the conductor paste. The conductive metal is prevented from diffusing into the substrate. However, in the technique of Patent Document 4, the resistance of the conductor may increase due to the glass powder remaining in the conductor. Moreover, the property of the said site | part may differ from the other site | part of a board | substrate by the film formed around the conductor wiring during baking.

  In Patent Document 5, by disposing a transition metal, a platinum group metal, or an oxide thereof on a silver electrode, silver ions are prevented from diffusing into a glass substrate or a dielectric layer during firing. However, in the technique of Patent Document 5, since the occurrence of oxidation of silver during firing is not suppressed, diffusion from silver conductor material cannot be sufficiently suppressed.

  In Patent Document 6, a thermally decomposable alkali metal compound is contained in the conductor paste for low-temperature fired substrate, and the diffusion of silver to the green sheet is suppressed in the decomposed product of the alkali metal compound during firing. However, in the technique of Patent Document 6, since the alkali metal decomposed in the conductor material is diffused into the green sheet during firing, the alkali metal may reduce the insulating property of the substrate.

In Patent Document 7, silver is suppressed from diffusing from a conductor to the ceramic insulating layer during firing by containing silver in the ceramic insulating layer. In Patent Document 8, CuO is introduced into glass ceramics, and electrons are imparted from CuO to silver during firing, thereby suppressing silver in the inner layer conductor from diffusing into the glass ceramics. In Patent Document 9, CeO ₂ is contained in the glass powder in the glass ceramic, thereby suppressing the diffusion of silver as the inner layer conductor. In patent document 10, the difference in the thermal contraction behavior around the inner conductor is eliminated by dissolving silver in the glass component of the glass ceramic layer.

  However, if a substance for suppressing the diffusion of silver is added to the substrate material as in the technique of Patent Documents 7 to 10, the substance may reduce the insulating properties of the substrate after baking. . Moreover, the shrinkage | contraction rate of the board | substrate by baking changes with the said substance, and the detachment | leave of a board | substrate and a conductor may be accelerated | stimulated. Furthermore, the addition of the substance to the substrate material may increase the manufacturing cost of the substrate.

  In Patent Document 11, the dielectric substrate coated with a conductive paste containing silver is subjected to a conductive treatment by performing an oxygen concentration controlled atmosphere or a mixed gas atmosphere of nitrogen, nitrogen, and hydrogen. Suppresses the diffusion of silver from the paste. In Patent Document 12, during firing, before the temperature reaches the softening point of the glass component contained in the glass ceramic green sheet, the firing atmosphere is switched to a non-oxidizing atmosphere such as a nitrogen atmosphere, so that Suppresses diffusion. However, if the firing is performed in an atmosphere other than the atmosphere as in the techniques of Patent Documents 11 and 12, the cost in the firing process may increase significantly.

  As described above, in the manufacturing technique of the wiring board using the silver-based conductor material, there is still room for improvement in suppressing the occurrence of defects due to silver diffusion during firing. Therefore, it has been desired to suppress the occurrence of silver diffusion during firing by a method different from the above-described prior art. In addition, in the manufacturing technology of wiring boards using silver-based conductor materials, it has been conventional to reduce the size and simplification of manufacturing equipment, improve usability, or simplify and simplify manufacturing processes, reduce costs, and save resources. It was hoped that

  The present invention has been made to solve the above-described problems, and can be realized as the following forms.

[1] According to one aspect of the present invention, there is provided a method for manufacturing a ceramic substrate on which a silver-based conductor is disposed. The manufacturing method of this embodiment includes a firing step in which an unsintered material of a silver-based conductor is disposed in an unsintered ceramic layer and fired, and the unsintered material of the silver-based conductor includes hydrogen atoms released during firing. It contains a transition metal material. According to the manufacturing method of this embodiment, oxygen present in the vicinity of the silver-based conductor material can be consumed by hydrogen released from the conductor material during firing, and oxidation of silver contained in the conductor material is suppressed, and the ceramic layer Diffusion of silver into is suppressed.

[2] In the manufacturing method of the above aspect, the transition metal material may have a hydrogen atom release temperature lower than a softening temperature of glass contained in the unfired ceramic layer. According to the manufacturing method of this embodiment, in the firing step, hydrogen can be released from the unfired material of the silver-based conductor before the glass contained in the unfired ceramic layer is softened. Therefore, the oxidation of silver during firing can be more reliably suppressed, and the diffusion of silver into the ceramic layer is suppressed. In addition, the glass contained in the unfired ceramic layer usually occupies a content of about 30 to 60% by weight of the entire unfired ceramic layer.

[3] In the manufacturing method of the above aspect, the metal constituting the transition metal material may be titanium. According to the manufacturing method of this embodiment, silver diffusion in the ceramic substrate can be suppressed.

[4] In the manufacturing method of the above aspect, the metal constituting the transition metal material may be palladium or a silver-palladium alloy. According to the manufacturing method of this embodiment, silver diffusion in the ceramic substrate can be suppressed.

[5] According to another aspect of the present invention, there is provided a conductor material that forms electrodes arranged on a ceramic substrate and is fired simultaneously with the unfired ceramic substrate. This form of conductor material contains: an unsintered silver-based conductor; and a transition metal material with hydrogen atoms released during firing. According to the conductor material of this form, it can suppress that silver which is a conductor component diffuses in a ceramic substrate in a baking process.

  A plurality of constituent elements of each aspect of the present invention described above are not indispensable, and some or all of the effects described in the present specification are to be solved to solve part or all of the above-described problems. In order to achieve the above, it is possible to appropriately change, delete, replace with another new component, and partially delete the limited contents of some of the plurality of components. In order to solve part or all of the above-described problems or to achieve part or all of the effects described in this specification, technical features included in one embodiment of the present invention described above. A part or all of the technical features included in the other aspects of the present invention described above may be combined to form an independent form of the present invention.

  The present invention can be realized in various forms other than the above manufacturing method and conductor material. For example, it can be realized in the form of a ceramic substrate manufactured by the above-described manufacturing method, a ceramic substrate manufactured using the above-mentioned conductor material, a ceramic substrate manufacturing apparatus, or the like. The present invention can also be realized in the form of a computer program that realizes the above manufacturing method or manufacturing device control method, a non-temporary recording medium that records the computer program, or the like.

Schematic which shows the structure of a LTCC board | substrate. Explanatory drawing which shows the procedure of the manufacturing process of a LTCC board | substrate. Explanatory drawing which shows the table | surface which put together the manufacturing conditions for every sample as an Example or a comparative example, and evaluation of the sinterability of each sample. Explanatory drawing which shows the table | surface which put together the manufacturing conditions and sinterability evaluation of the sample as an Example or a comparative example. Explanatory view showing an SEM image showing the difference in the change in the composition of the ceramic material with or without the addition of TiH ₂ for conductive materials. Explanatory view showing an image showing the difference in the change in the composition of the ceramic material with or without the addition of TiH ₂ for conductive materials.

A. Embodiment:
FIG. 1 is a schematic view showing a configuration of an LTCC substrate 10 as an embodiment of the present invention. The LTCC substrate 10 is a circuit substrate used for a high-frequency module or IC package used in a computer, a communication device, or the like. The LTCC substrate 10 has a multilayer structure in which a plurality of ceramic insulating layers 1 on which wiring patterns are formed are laminated. The wiring pattern includes the via electrode 2, the inner layer electrode 3, and the exterior electrode 4. The ceramic insulating layer 1 is produced by low-temperature firing at 1000 ° C. or lower. Each ceramic insulating layer 1 is formed with a through hole (so-called via) for arranging the via electrode 2.

  The via electrode 2 is an electrode disposed in a via provided in each ceramic insulating layer 1 described above. The via electrode 2 is electrically connected to the wiring pattern formed on both surfaces of each ceramic insulating layer 1 and functions as a conductive path in the thickness direction of each ceramic insulating layer 1 in the LTCC substrate 10. The inner layer electrode 3 is an electrode constituting a wiring pattern arranged between the ceramic insulating layers 1, and the exterior electrode 4 is an electrode constituting a wiring pattern arranged on the outermost surface of the LTCC substrate 10. In this embodiment, each electrode 2-4 is comprised by the silver-type conductor material which has silver as a main component. In the present specification, the “main component” means a material component occupying a content of 50% by weight or more of the entire mixture. In addition, although the resistor etc. which are connected to the exterior electrode 4 are arrange | positioned at the outermost surface of the LTCC board | substrate 10, the illustration and detailed description are abbreviate | omitted.

  FIG. 2 is a flowchart showing the procedure of the manufacturing process of the LTCC substrate. The LTCC substrate is manufactured by simultaneously firing an unfired ceramic layer and an unfired silver-based conductor material at a low temperature (for example, 1000 ° C. or less). In step S10, a green sheet that is an unfired ceramic layer is prepared. The green sheet is produced by forming a ceramic slurry obtained by mixing glass powder, an inorganic filler, a binder component, a plasticizer, and a solvent into a sheet by a doctor blade method or the like.

In step S20, a conductor paste that is an unsintered material of a silver-based conductor constituting the electrodes 2 to 4 is prepared. The conductive paste is produced by mixing a silver-based material powder, which is a conductive component, a resin, and an organic solvent. In the present embodiment, a transition metal material including hydrogen atoms is further added to the conductor paste. This transition metal material functions as a reducing agent that releases hydrogen during firing. In addition, as a transition metal material provided with a hydrogen atom, for example, a hydride of titanium such as titanium dihydride (TiH ₂ ), or a hydride of palladium or silver palladium alloy may be used.

  In step S30, the conductive paste is placed on a green sheet to produce a wiring pattern. Specifically, vias are formed in the green sheet by punching, and the vias are filled with a conductive paste. Further, a conductor paste is printed on each surface of the green sheet by a screen printing method or the like. After the wiring pattern is formed on the green sheet, an unfired laminated body in which the green sheets are laminated is configured. In step S40, the unfired laminate is fired at a temperature of about 750 to 950 ° C., for example. Thereafter, a resistor or the like connected to the exterior electrode 4 is disposed, and the LTCC substrate 10 is completed.

  Here, as described above, the conductive material of the present embodiment uses a silver-based material as a conductive component. In general, in the firing process of a wiring board using a silver-based conductor material, it is known that the state of the substrate material in the vicinity of the conductor changes due to the diffusion of silver from the conductor material, causing various problems. It has been. Specifically, there is a possibility that the insulating property of the substrate is lowered by silver diffused in the substrate material. Further, the composition of the substrate material in the vicinity of the conductor may change due to the diffusion of silver, which may cause local discoloration of the substrate and a decrease in local strength of the substrate. In addition, the progress of firing shrinkage only in the vicinity of the conductor may be promoted, and a void may be generated between the wiring pattern and the substrate, or the substrate may be deformed in the vicinity of the wiring pattern.

  However, in the manufacturing process of this embodiment, hydrogen is released from the transition metal material added to the conductor paste during firing. For this reason, oxygen present in the vicinity of the region where the conductor paste is arranged is consumed by the reaction with the hydrogen, so that oxidation of silver contained in the conductor paste is suppressed. Therefore, the diffusion of silver from the conductor paste into the green sheet is suppressed, and the occurrence of defects in the ceramic insulating layer due to the diffusion of silver is suppressed.

  3 and 4 are explanatory diagrams showing tables summarizing the manufacturing conditions and the evaluation of sinterability of samples as examples or comparative examples of the present invention prepared by the inventors of the present invention. The inventor of the present invention provides samples T1 to T3 of LTCC substrates having via electrodes as examples of the present invention, and samples T4 and T5 of LTCC substrates having via electrodes as comparative examples of the present invention. It produced (FIG. 3). In addition, the inventor of the present invention provides a sample T6 of an LTCC substrate having an inner layer electrode as an embodiment of the present invention, and samples T7 and T8 of an LTCC substrate having an inner layer electrode as a comparative example of the present invention. It produced (FIG. 4). Specific production conditions for each of the samples T1 to T8 are as follows.

<Green sheet>
Green sheets of samples T1 to T8 were produced as follows.
1. material:
(1) Glass powder: borosilicate glass powder mainly composed of silicon oxide (SiO ₂ ), aluminum oxide (Al ₂ O ₃ ) and boron oxide (B ₂ O ₃ ) (2) Inorganic filler: alumina powder (average Particle size 2μm, specific surface area 1.0m ² / g)
(3) Binder component: Acrylic binder (4) Plastic content: Dioctyl phthalate (DOP)
(5) Solvent: Methyl ethyl ketone (MEK)

2. Manufacturing method:
(1) A borosilicate glass powder and an alumina powder were weighed so as to have a weight ratio of 50:50 (total amount: 1 kg) and put into an alumina pot.
(2) An acrylic resin (120 g) and MEK and DOP (amount capable of securing a desired slurry viscosity and sheet strength) were further charged into an alumina pot.
(3) The above materials put in an alumina pot were mixed for 5 hours to obtain a ceramic slurry.
(4) Using the ceramic slurry, a green sheet having a thickness of 0.15 mm was produced by a doctor blade method.

<Conductor paste>
The conductor paste for each sample T1-T8 was produced with the following materials.
(1) Conductive component: Silver (2) Resin, organic solvent, etc .: A general material used for producing a conductive paste was used at a general blending ratio.
(3) Transition metal material:
(3.1) 0.05%, 0.10%, 0.50%, and 0.10% by weight of TiH ₂ were added to the conductor pastes for samples T1 to T3 and T6, respectively.
(3.2) No transition metal material was added to the conductor paste for samples T4 and T7.
(3.3) Titanium oxide (TiO ₂ ) was added by 0.10% by weight to each of the conductor pastes for samples T5 and T8.

<Preparation and firing of unfired laminate>
(1) A green sheet on which a wiring pattern including a via electrode and an inner layer electrode was formed by the above-mentioned conductor paste was laminated to produce an unfired laminated body of each sample T1 to T8. In addition, the restraint sheet | seat (thickness 0.30mm) for suppressing shrinkage | contraction of a ceramic insulating layer was arrange | positioned in the outermost layer of a non-baking laminated body. The constraining sheet was produced by the same method as the above green sheet except that alumina powder was used as the ceramic raw material powder.
(2) The unfired laminates of the samples T1 to T8 were fired at a firing temperature of about 850 ° C.

<Sinterability evaluation>
About each sample T1-T8, the cross-section grinding | polishing surface of the formation part of a via electrode or an inner layer electrode was evaluated by structure | tissue observation.
1. discoloration:
(1) Via electrode:
In the vicinity of the via electrode formed by the conductive paste to which TiH ₂ was added, the ceramic insulating layer was hardly discolored due to silver diffusion (samples T1 to T3).
In the vicinity of the via electrode formed by the conductor paste to which the transition metal material was not added or the conductor paste to which TiO ₂ was added, many local discolorations of the ceramic insulating layer due to silver diffusion occurred (Sample T4). , T5).
(2) Inner layer electrode:
In the vicinity of the inner layer electrode formed by the conductor paste to which TiH ₂ was added, the ceramic insulating layer was hardly discolored due to silver diffusion (sample T6).
In the vicinity of the inner layer electrode formed by the conductor paste to which the transition metal material was not added or the conductor paste to which TiO ₂ was added, many local discolorations of the ceramic insulating layer due to silver diffusion occurred (Sample T7). , T8).

2. Defects due to shrinkage mismatch:
(1) Via electrode:
In the vicinity of the via electrode formed by the conductive paste to which TiH ₂ was added, there was no local deformation of the ceramic insulating layer caused by the fact that the baking shrinkage only in the vicinity of the electrode was promoted by the diffusion of silver. Samples T1-T3).
In the vicinity of the via electrode formed by the conductive paste to which the transition metal material was not added, a void was generated (sample T4). Further, in the vicinity of the via electrode formed of the conductive paste to which TiO ₂ is added, a protrusion (push-up) is formed along with the void, and the ceramic insulating layer is locally increased in thickness around the via electrode. It was. This protrusion is caused by the solidification of the ceramic material around the via electrode being accelerated by the diffusion of silver from the conductor material, and the contraction amount being smaller than the other part.
(2) Inner layer electrode:
In the vicinity of the inner layer electrode formed by the conductive paste to which TiH ₂ was added, local deformation of the ceramic insulating layer due to silver diffusion did not occur (Sample T6).
In the vicinity of the inner layer electrode formed by the conductor paste to which the transition metal material is not added or the conductor paste to which TiO ₂ is added, the firing contraction of the inner layer electrode and the firing contraction of the ceramic material in the vicinity of the inner layer electrode start. The warp of the ceramic insulating layer due to the timing shift occurred (samples T7 and T8).

FIG. 5 is an explanatory view showing a scanning electron microscope (SEM) image showing the difference in the composition change of the ceramic material depending on whether or not TiH ₂ is added to the conductor material. The inventor of the present invention produces an unfired LTCC substrate sample using a conductive material to which TiH ₂ is added and an unfired LTCC substrate sample using a conductor material to which no TiH ₂ is added. did. In the firing step, when the firing temperature reached 750 ° C., each sample was taken out of the furnace, and a cross-sectional polished surface in the vicinity of the via electrode of each sample was photographed. In the sample using the conductive material to which TiH ₂ was added, no void was generated in the vicinity of the via electrode (SEM image on the left side of the paper), but in the sample using the conductive material to which no TiH ₂ was added, the vicinity of the via electrode was used. There was a void (SEM image on the right side of the paper).

FIG. 6 is an explanatory view showing an image showing a difference in the composition change of the ceramic material depending on whether or not TiH ₂ is added to the conductor material. Each of the two SEM images in the upper part of FIG. 6 is a photograph of a cross-sectional polished surface in the vicinity of the inner layer electrode of the two samples in the course of firing described in FIG. Each of the lower two images in FIG. 6 is a mapping image showing a composition distribution created based on the upper SEM image. In a sample of an unfired LTCC substrate manufactured using a conductive material to which TiH ₂ was added, there was little silver diffusion near the inner layer electrode, and local densification occurred in the ceramic insulating layer (left side of the paper) ). In a sample of an unfired LTCC substrate manufactured using a conductor material to which no TiH ₂ was added, silver diffusion was large in the vicinity of the inner layer electrode, and local densification occurred in the ceramic insulating layer (paper surface). Right).

Note that the local densification in the ceramic insulating layer is caused by the fact that silver diffused from the conductive material to the site in the vicinity of the electrode takes in a part of the composition of the ceramic material around the site and crystallizes. . The strength is improved at a site where such local densification occurs, but the strength is reduced at a site where a part of the composition of the surrounding ceramic material is removed. That is, the occurrence of local densification in the ceramic insulating layer causes an increase in strength non-uniformity of the ceramic insulating layer. However, by using a conductive material to which TiH ₂ is added, local densification in the ceramic insulating layer is suppressed.

  As described above, according to the manufacturing process of this embodiment, oxygen existing in the vicinity of the conductor material is consumed by hydrogen atoms released from the transition metal material contained in the silver-based conductor material during firing. Therefore, the diffusion of silver from the conductor material during firing is suppressed. Therefore, the occurrence of defects in the ceramic insulating layer due to the diffusion of silver during firing in the LTCC substrate is suppressed.

B. Variations:
B1. Modification 1:
In each of the above embodiments, titanium hydride or palladium or silver palladium alloy hydride is used as the transition metal material having hydrogen atoms added to the silver-based conductor material. However, the transition metal material having hydrogen atoms added to the silver-based conductor material is not limited to titanium hydride or palladium or silver palladium alloy hydride. The transition metal material having hydrogen atoms added to the silver-based conductor material may be any transition metal material that releases hydrogen atoms during firing. For example, zirconium hydride (ZrH ₂ ) and other hydrogen storage alloys It may be. In addition, as a transition metal material provided with the hydrogen atom added to a silver-type conductor material, it is desirable that the discharge | release temperature of a hydrogen atom is lower than the softening temperature of the glass contained in a green sheet. If the hydrogen atom release temperature is lower than the softening temperature of the glass contained in the green sheet, hydrogen will be released before the firing shrinkage of the glass contained in the green sheet during firing. Can be more reliably suppressed.

B2. Modification 2:
In the said embodiment, the silver-type conductor material which added the transition metal compound which discharge | releases a hydrogen atom during baking was used in the manufacturing process of the LTCC board | substrate. However, not only the manufacturing process of the LTCC substrate, but also a silver-based conductor material to which a transition metal compound that releases hydrogen atoms during firing is added may be used in the manufacturing process of various wiring substrates. That is, the present invention is not limited to the manufacturing process of the LTCC substrate, but can be applied to manufacturing processes of various wiring boards using a silver-based conductor material.

  The present invention is not limited to the above-described embodiments, examples, and modifications, and can be realized with various configurations without departing from the spirit thereof. For example, the technical features in the embodiments, examples, and modifications corresponding to the technical features in each embodiment described in the summary section of the invention are to solve some or all of the above-described problems, or In order to achieve part or all of the above effects, replacement or combination can be performed as appropriate. Further, if the technical feature is not described as essential in the present specification, it can be deleted as appropriate.

DESCRIPTION OF SYMBOLS 1 ... Ceramic insulating layer 2 ... Via electrode 3 ... Inner layer electrode 4 ... Exterior electrode 10 ... LTCC board | substrate

Claims (5)

In the method of manufacturing a ceramic substrate on which silver-based conductors are arranged,
It comprises a firing step of placing and firing the unfired material of the silver-based conductor in the unfired ceramic layer,
The method for producing a non-fired material of the silver-based conductor contains a transition metal material having hydrogen atoms released during firing. The manufacturing method according to claim 1,
The transition metal material is a manufacturing method in which a release temperature of hydrogen atoms is lower than a softening temperature of glass contained in the green ceramic layer. The manufacturing method according to claim 1 or 2,
The manufacturing method whose metal which comprises the said transition metal material is titanium. The manufacturing method according to claim 1 or 2,
The metal which comprises the said transition metal material is a manufacturing method which is palladium or a silver palladium alloy. A conductive material that forms electrodes arranged on a ceramic substrate and is fired simultaneously with the unfired ceramic substrate,
Unsintered silver-based conductor,
A transition metal material comprising hydrogen atoms released during firing;
A conductor material comprising: a conductor material.

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