METHOD FOR JOINING ELECTRONIC PART USING A JOINING SILVER SHEET

Abstract

A method for joining an electronic part, comprising: inserting a joining silver sheet between an electronic part and a substrate, to which the electronic part is to be joined; and heating them to the temperature range of T.sub.A ( C.) or higher and T.sub.B ( C.) or lower, under application of a pressure to the electronic part and the substrate to make a contact surface pressure of the electronic part and the silver sheet of from 0.5 to 3 MPa. The joining silver sheet comprises silver particles having a particle diameter of from 1 to 250 nm integrated by sintering, and has a capability of further undergoing sintering on heating and retaining the silver sheet at a temperature range of T.sub.A ( C.) or higher and T.sub.B ( C.) or lower satisfying the following expression (1): 270T.sub.A<T.sub.B350.

Claims

1-6. (canceled)

7. A method for joining an electronic part, comprising: inserting a joining silver sheet between an electronic part and a substrate, to which the electronic part is to be joined; and heating them to the temperature range of T.sub.A ( C.) or higher and T.sub.B ( C.) or lower, under application of a pressure to the electronic part and the substrate to make a contact surface pressure of the electronic part and the silver sheet of from 0.5 to 3 MPa, wherein the joining silver sheet comprises silver particles having a particle diameter of from 1 to 250 nm integrated by sintering, and has a capability of further undergoing sintering on heating and retaining the silver sheet at a temperature range of T.sub.A ( C.) or higher and T.sub.B ( C.) or lower satisfying the following expression (1):
270T.sub.A<T.sub.B350.

8. The method for joining an electronic part according to claim 7, wherein both surfaces of the joining silver sheet each have an arithmetic average surface roughness Ra of 0.10 m or less.

9. The method for joining an electronic part according to claim 7, wherein the joining silver sheet has a thickness of from 10 to 120 m in terms of a thickness measured with a flat head micrometer.

10. The method for joining an electronic part according to claim 7, wherein the joining silver sheet has a projected shape viewed in a thickness direction that shows a pattern formed by printing.

Description

BRIEF DESCRIPTION OF DRAWINGS

[0023] FIG. 1 is an SEM micrograph of the surface of the silver sheet obtained in Example 1.

[0024] FIG. 2 is an SEM micrograph of the surface of the silver sheet obtained in Example 5.

[0025] FIG. 3 is an SEM micrograph of the surface of the silver sheet obtained in Example 6.

[0026] FIG. 4 is an SEM micrograph of the surface of the silver sheet obtained in Example 7.

[0027] FIG. 5 is an SEM micrograph of the surface of the silver sheet obtained in Example 8.

[0028] FIG. 6 is an SEM micrograph of the surface of the silver coated film after the preliminary heat treatment obtained in Comparative Example 1.

[0029] FIG. 7 is an SEM micrograph of the surface of the silver coated film after the preliminary heat treatment obtained in Comparative Example 2.

[0030] FIG. 8 is an SEM micrograph of the surface of the silver sheet obtained after subjecting the silver sheet obtained in Example 1 to a heating test under conditions of a pressure of 1 MPa and a temperature of 300 C. for 5 minutes.

[0031] FIG. 9 is TG-DTA curves of a silver paste capable of being applied to the invention (the silver paste A in Example).

DESCRIPTION OF EMBODIMENTS

[0032] The silver sheet of the invention is inserted between members to be joined, and joins the members to be joined disposed on both sides thereof by utilizing solid phase diffusion of the silver sheet, which occurs on heating to the temperature range of T.sub.A ( C.) or higher and T.sub.B ( C.) or lower satisfying the following expression (1).

270T.sub.A<T.sub.B350(1)

[0033] The silver sheet has such a feature that the pressure to be applied thereto may be as low as approximately from 0.5 to 3 MPa irrespective of the use of solid phase diffusion.

[0034] The silver sheet according to the invention is a sintered sheet formed by sintering silver powder. The silver sheet achieves joining under such a low pressure as described above since the silver sheet has the capability of further undergoing sintering at the temperature T.sub.3 ( C.) on joining, which is within the temperature range of T.sub.A ( C.) or higher and T.sub.B ( C.) or lower. In other words, the sintering that is performed in the step of production of the silver sheet is terminated in an incomplete state. The silver sheet in this state has many voids thereinside. The sintering further proceeds at the heating temperature on joining, and thus the shape and the amount of the voids are largely changed only by applying a low pressure, thereby promoting active migration (diffusion) of silver atoms. Consequently, a joined portion where the members to be joined on the both sides are tightly joined to each other is provided thereby.

[0035] Whether or not the silver sheet has the capability of further undergoing sintering may be confirmed by subjecting the silver sheet to an experiment of heating to the temperature range of T.sub.A ( C.) or higher and T.sub.B ( C.) or lower satisfying the expression (1), as described above.

[0036] For providing a high joining strength stably in the case where members are joined under a low pressure, it is effective to reduce the surface roughness of the sheet. As a result of various investigations, the arithmetic average surface roughness Ra is desirably 0.10 m or less for both the front and back surfaces of the sheet. The silver sheet that has Ra of 0.10 m or less may be obtained by a pressure in the pressurized baking described later of 8 MPa or higher.

[0037] The thickness of the silver sheet is preferably from 10 to 120 m in terms of a thickness measured with a flat head micrometer. For providing a high joining strength stably, it is effective to ensure the thickness of the sheet of 10 m or more. The thickness is more preferably 20 m or more. Even though the thickness is 120 m or more, the effect of enhancing the stability of the joining strength may be saturated, and thus it is uneconomical. The thickness is more preferably 100 m or less, and further preferably 50 m or less.

Raw Material Silver Powder

[0038] Silver powder as a raw material of the silver sheet is preferably constituted by silver particles having a particle diameter of from 1 to 250 nm. Silver powder formed of such fine particles undergoes a sintering phenomenon at a low temperature lower than 250 C., and is significantly useful for providing a silver sheet, in which the sintering is terminated in an incomplete state, i.e., a silver sheet having the capability of further undergoing sintering. In total consideration of the handleability, the cost, the temperature capable of starting sintering, and the like, silver powder having an average particle diameter of from 20 to 120 m is more practically used. The particle diameter herein means the diameter of the longest part (major axis) of the particle. The shape of the particles is more preferably a spherical shape.

[0039] The raw material silver powder used may be coated with an organic protective material. The organic protective material preferably remains until the silver powder is subjected to the pressurized baking for producing the silver sheet. Accordingly, during the process until the silver powder is subjected to the pressurized baking, the organic protective material may be volatilized to some extent but preferably does not completely disappear. More specifically, the remaining ratio of the organic protective material (in terms of ratio with respect to the total mass of the initial organic protective material) is preferably 30% or more at the time when the preliminary heat treatment is completed. Examples of the organic protective material include a fatty acid, such as sorbic acid, hexanoic acid, butanoic acid and malic acid. The production method itself of the raw material silver powder is not particularly limited, and silver powder produced by a known method may be used.

Silver Paste

[0040] A dispersion medium and the silver powder are mixed to form a silver paste. At this time, an additive may be added thereto for such purposes as control of the viscosity and the like. As a result of detailed investigations by the inventors, it has been found that it is significantly important for enabling the formation of the silver sheet through pressurized baking at a low temperature that the substances constituting the dispersion medium are sufficiently removed through volatilization before the pressurized baking on producing the silver sheet. In other words, when the pressurized baking is performed in such a state that a large amount of dispersion medium is present around the silver particles, the sintering phenomenon occurring among the silver particles adjacent to each other is inhibited, which makes difficult the production of the sheet. However, it has been found that in the case where the pressurized baking is performed in such a state that the dispersion medium is sufficiently removed, the silver sheet can be constituted even at the baking temperature that is lower than 250 C., and preferably lower than 200 C.

[0041] For sufficiently removing the dispersion medium before performing the sintering at a baking temperature lower than 250 C., and preferably lower than 200 C., it is necessary to use as the dispersion medium such a substance that undergoes volatilization by a heat treatment at a low temperature, at which the sintering does not occur. However, even after the dispersion medium has been sufficiently removed, the surfaces of the respective silver particles are preferably coated with the organic protective material until being subjected to the pressurized baking. Accordingly, the substance that is used as the dispersion medium may be a substance having such a property that volatilization thereof proceeds by a heat treatment at a low temperature, at which the organic protective material of the silver particles remains. Specifically, such a dispersion medium is preferably used that has a 25% volatilization temperature T.sub.25 ( C.) defined by the aforementioned item (A) in a temperature range of 200 C. or lower. A dispersion medium having T.sub.25 in a temperature range exceeding 200 C. is difficult to be sufficiently removed through volatilization in a low temperature range, in which the sintering does not occur. T.sub.25 is preferably in a temperature range of 100 C. or higher. When T.sub.25 is lower than 100 C., the substance is liable to be volatilized under a storing environment, and the storage management of the silver paste is necessarily strictly performed.

[0042] Examples of the dispersion medium that has a 25% volatilization temperature T.sub.25 ( C.) in a range of 200 C. or lower, and more preferably 100 C. or higher and 200 C. or lower, include 2-ethyl-1,3-hexanediol. Examples of the additive that is added to the paste for controlling the viscosity and the like include an organic substance such as 2-butoxyethoxyacetic acid and 2-methoxyethoxyacetic acid. The content of the additive in the paste is preferably 2.0% by mass or less, and more preferably 1.0% by mass or less.

Coating on Substrate

[0043] The silver paste is coated on a substrate to form a coated film. The substrate used may be a material, from which the silver sheet thus formed may be released off. Examples thereof applied include a glass substrate and an alumina substrate, having good smoothness. Depending on purposes, a substrate having a curved surface and a substrate having an uneven surface may also be used. The thickness of the coated film may be controlled to make the thickness of the silver sheet obtained after the pressurized baking within the prescribed range (described above). In consideration of the arrangement of electronic parts to be joined, the silver paste may be coated in a patterned shape by printing.

Preliminary Heat Treatment

[0044] Before subjecting to the pressurized baking, the coated film thus coated on the substrate is heated to provide a coated film, in which the dispersion medium has been sufficiently volatilized. This heat treatment in the description herein is referred to as a preliminary heat treatment. The preliminary heat treatment is performed in a temperature range, in which the volatilization of the dispersion medium proceeds, and the sintering of the silver particles does not occur. From the standpoint of the promotion of volatilization of the dispersion medium, it is effective to use a heating temperature that is the 25% volatilization temperature T.sub.25 ( C.) or higher. When the heating temperature is lower than that temperature, a prolonged period of time may be required for the sufficient volatilization of the dispersion medium to impair the productivity, or the sufficient volatilization of the dispersion medium may be impossible. From the standpoint of preventing the sintering of the silver particles from occurring, the suitable temperature may be selected from a range of 200 C. or lower in the case where no pressure is applied. In the case where the average particle diameter of the silver powder used is large as exceeding, for example, 120 nm, the temperature causing no sintering may be easily selected from a temperature range exceeding 200 C. The preliminary heat treatment temperature is preferably in a range of 250 C. or lower. When the temperature is higher than the range, the sintering is liable to occur partially. If the sintering occurs in the stage of the preliminary heat treatment, it may be difficult to produce a stable sheet by the pressurized baking.

[0045] The dispersion medium is preferably removed as much as possible before the pressurized baking, but may remain slightly as far as the sheet can be formed by the pressurized baking. The conditions (including the retention temperature and the retention time) of the preliminary heat treatment capable of forming the sheet may be determined in advance by experiments depending on the kinds of the raw material silver powder and the additives, the conditions in the pressurized baking as the subsequent step, and the like. In the case where the period of time of the preliminary heat treatment for removing the dispersion medium through volatilization is too short, a large amount of organic substances derived from the dispersion medium may remain, which may make difficult the formation of the sheet, in some cases. In the case where the dispersion medium is 2-ethyl-1,3-hexanediol, for example, a suitable preliminary heat treatment condition may be found in ranges of a heating temperature of from 130 to 170 C. and a heating time of from 5 to 30 minutes.

Pressurized Baking

[0046] The coated film of the silver paste, from which the substances of the dispersion medium have been sufficiently removed through volatilization after the preliminary heat treatment, is subjected to baking in a state where a pressure is applied to the surface thereof, thereby providing the silver sheet. The pressure may be applied in such a manner that the coated film is held from both sides thereof with a pair of materials that are not joined to the silver sheet in nature, such as a glass material or a ceramic material. The material for holding the coated film from one side may be the substrate having the silver paste coated thereon as it is.

[0047] The pressure is preferably in a range of from 5 to 35 MPa, and more preferably in a range of from 8 to 35 MPa. The silver sheet that has high smoothness may be obtained by increasing the pressure. The silver sheet that has an arithmetic average surface roughness Ra of 0.10 m or less on the surface thereof is significantly useful for providing a high joining strength between the members to be joined. A pressure of 8 MPa or higher may facilitate the production of the silver sheet having Ra of 0.10 m or less. On the other hand, an excessively increased pressure is not preferred since the process load of the pressurized baking may be increased thereby. As a result of various investigations, the pressure is preferably set in a range of 35 MPa or lower, and may be managed in a range of 25 MPa or lower, or 20 MPa or lower.

[0048] In the pressurized baking, the sintering among the silver particles is terminated in an incomplete state, thereby providing the silver sheet. In the case where the temperature of the pressurized baking is excessively higher than the temperature capable of starting the sintering of the raw material silver powder used, it may be difficult to terminate the sintering in an incomplete state, thereby failing to produce stably the silver sheet having the capability of further undergoing sintering. As a result of various investigations, the temperature of the pressurized baking is preferably 250 C. or lower in the case where the raw material silver powder used is constituted by silver particles having a particle diameter of 250 nm or less. In the case where the raw material silver powder having an average particle diameter of 120 nm or less, in particular, the temperature may be 200 C. or lower. The sintering may be liable to occur due to the pressure applied, and thus there are cases where the pressurized baking can be achieved at a temperature that is equivalent to or lower than the preliminary heat treatment temperature.

[0049] In general, the suitable conditions may be determined for the heating temperature of the pressurized baking within a range of from 170 to 250 C., and more preferably from 170 to 220 C., and for the heating time within a range of from 3 to 30 minutes, and more preferably from 3 to 10 minutes.

Joining with Silver Sheet

[0050] The silver sheet thus obtained above is inserted between members to be joined, and undergoes solid phase diffusion by heating to a prescribed joining temperature in a state where a prescribed pressure is applied, thereby exhibiting the function as a joining material.

[0051] The joining is performed within a temperature range of T.sub.A ( C.) or higher and T.sub.B ( C.) or lower satisfying the following expression (1). The temperature range of T.sub.A ( C.) or higher and T.sub.B ( C.) or lower means the temperature range where the sintering of the silver sheet may further proceed, as described above.

270T.sub.A<T.sub.B350(1)

[0052] The pressure applied on joining may be in a range of from 0.5 to 3 MPa, and more preferably in a range of from 0.8 to 2 MPa. In the case where joining through solid phase diffusion is performed with an ordinary joining material in the form of a sheet at a low temperature, for example, of approximately from 270 to 350 C., a high pressure of 10 MPa or higher has been required. The application of such a high pressure to an electronic part and the like is not preferred, and there has been frequently limitation in the purposes of the method. The silver sheet according to the invention causes the solid phase diffusion by utilizing the capability of further undergoing sintering, and thus enables the joining under a considerably low pressure. The heating time at the temperature range of T.sub.A ( C.) or higher and T.sub.B (C) or lower on joining may be determined in a range of from 3 to 30 minutes, and more preferably in a range of from 3 to 15 minutes.

Example

[0053] Silver particle-aggregated dry powder made of spherical silver particles having an average primary particle diameter of approximately 100 nm coated with sorbic acid which is an organic protective material was prepared as raw material silver powder. The amount of metallic silver contained in the silver powder was 99.2% by mass. 2-Butoxyethoxyacetic acid was prepared as an additive for controlling the viscosity and the thixotropy. Octanediol (2-ethyl-1,3-hexanediol) was prepared as a dispersion medium.

[0054] 90.5 g of the raw material silver powder (containing 89.776 g of metallic silver), 0.95 g of the additive, and 8.55 g of the dispersion medium were mixed and then kneaded with a kneading-degassing machine (V-mini 300, produced by EME Corporation) under conditions of a revolution of 1,400 rpm and a rotation of 700 rpm, and the resulting kneaded product was subjected to a three-roll kneader (22851 Norderstedt, EXAKT Apparatebau GmbH & Co.) while controlling the gap by from 5 to 10 passes, thereby providing a silver paste. The silver paste was designated as a silver paste A.

[0055] For comparison, silver particle-aggregated dry powder made of spherical silver particles having an average primary particle diameter of approximately 0.8 m coated with oleic acid as an organic protective material was prepared as raw material silver powder. The amount of metallic silver contained in the silver powder was 99.62% by mass. 90.5 g of the raw material silver powder (containing 90.156 g of metallic silver), 0.95 g of the additive, and 8.55 g of the dispersion medium were mixed, and then a silver paste was provided in the same manner as above. The silver paste was designated as a silver paste B.

[0056] One of the silver pastes was coated on a substrate formed of flat plate glass through a metallic mask to a 13 mm square with a thickness of 70 m by manual printing using a metallic squeegee, and subjected to a preliminary heat treatment in the air under the conditions shown in Tables 1 and 2. The preliminary heat treatment was a two-stage heat treatment with different temperature levels, except for some examples. The temperature T.sub.1 ( C.) of the preliminary heat treatment shown in Tables 1 and 2 means the treatment temperature corresponding to the temperature range that is the 25% volatilization temperature T.sub.25 ( C.) or higher and causes no sintering of the silver particles of the treatment temperatures employed in the preliminary heat treatment. The hyphen shown in the column for T.sub.1 means that the preliminary heat treatment at the treatment temperature corresponding to the temperature range that is the 25% volatilization temperature T.sub.25 ( C.) or higher and causes no sintering of the silver particles was not performed. The coated film having been subjected to the preliminary heat treatment was held from both side thereof with a pair of flat plate glass to make a state where a pressure was applied thereto, and subjected to pressurized baking under the conditions shown in Tables 1 and 2. After completing the pressurized baking, the pair of flat plate glass was removed, and the surface roughness Ra of the surface of the coated film after the pressurized baking was measured. The results are shown in Tables 1 and 2.

[0057] In the column Evaluation of sheet formation in Tables 1 and 2, the cases where sintering of the silver particles was observed after the pressurized baking, and the coated film was not broken after releasing from the flat plate glass are shown by , and the other cases are shown by x. In the example where a sheet was capable of being formed, the silver sheet thus formed was taken out, and Ra was also measured for the surface thereof opposite to the surface having been measured for Ra above. As a result, Ra thus measured was substantially the same as Ra on the side shown in Table 1.

[0058] In the example where a sheet was capable of being formed, a specimen cut out from the silver sheet thus obtained was held with a pair of flat plate glass to make a state where a pressure of 1 MPa was applied thereto, and subjected to a heating test of retaining at 300 C. in the air for 5 minutes, and the SEM micrographs at a magnification of 30,000 before and after the heating test were compared to each other. As a result, an apparent change in shape of the voids was observed in all the silver sheets, and thus it was confirmed that the silver sheets had the capability of undergoing further sintering.

[0059] A silicon chip having a thickness of 0.3 mm (12.5 mm square) and a copper plate having a thickness of 1 mm (30 mm square) were prepared as members to be joined. The surfaces of these materials had been subjected to silver plating. In the example where a sheet was capable of being formed, the silver sheet was inserted between the members to be joined, and subjected to the joining test under the conditions shown in Table 1. The both ends of the copper plate of the resulting joined assembly were held with pinchers, and the copper plate was bent at the center part of the 30 mm square by approximately 900. Thereafter, the shape of the copper plate was restored to the initial shape. The area ratio of the silicon chip that remained on the copper plate thus restored to the initial shape was measured and evaluated for the joining strength by the following standard. The evaluation of or better was designated as passed.

: The area ratio of the remaining silicon chip was 100%.
: The area ratio of the remaining silicon chip was 80% or more and less than 100%.
x: The area ratio of the remaining silicon chip was less than 80%.

[0060] For reference, FIGS. 1 to 5 show the SEM micrographs of the surfaces of the silver sheets of some of Examples. FIGS. 6 and 7 show the SEM micrographs of the surface of the coated film after the pressurized baking of some of Comparative Examples, where a sheet was not formed. The corresponding figure numbers of the SEM micrographs were shown in Tables 1 and 2. FIG. 8 shows the SEM micrograph of the surface of the sheet after subjecting the silver sheet of Example 1 to a heating test at 300 C. in the air for 5 minutes under application of a pressure of 1 MPa. FIG. 9 shows the TG-DTA curves of the silver paste A where the silver paste is heated from ambient temperature (25 C.) to 500 C. at 10 C. per minute in the air or a nitrogen atmosphere. The silver paste A has a content of the dispersion medium of 8.55% by mass, and thus the amount of the dispersion medium having been volatilized when the weight reduction rate of the dispersion medium (%) in the expression (2) is 25% is 8.55(25/100)2.14 g per 100 g of the silver paste. In the TG curve in FIG. 9, it is considered that the weight change in the range of 170 C. or lower substantially corresponds to the volatilization of the dispersion medium, and therefore it is apparent that the 25% volatilization temperature T.sub.25 of the silver paste A is in a range between 100 C. and 150 C.

TABLE-US-00001 TABLE 1 Preliminary heat treatment Pressurized baking First Second Heating Kind of stage stage condition Example silver Temp. Time Temp. Time T.sub.1 Pressure Temp. T.sub.2 Time No. paste ( C.) (min) ( C.) (min) ( C.) (MPa) C.) (min) Example 1 A 100 10 150 10 150 20 180 5 Example 2 A 100 10 150 10 150 20 180 5 Example 3 A 100 10 150 10 150 30 180 5 Example 4 A 100 10 150 10 150 30 180 5 Example 5 A 150 10 150 20 180 5 Example 6 A 150 10 100 10 150 20 180 5 Example 7 A 100 10 150 10 150 10 180 5 Example 8 A 100 10 150 10 150 5 180 5 Coated film after pressurized baking Joining test Evaluation Heating of condition Evaluation Example Ra sheet SEM Pressure Temp. T.sub.3 Time of joining No. (m) formation micrograph (MPa) ( C.) (min) strength Example 1 0.059 FIG. 1 2 300 5 Example 2 0.058 1 300 5 Example 3 0.059 2 300 5 Example 4 0.062 1 300 5 Example 5 0.061 FIG. 2 1 300 5 Example 6 0.063 FIG. 3 1 300 5 Example 7 0.071 FIG. 4 1 300 5 Example 8 0.279 FIG. 5 1 300 5

TABLE-US-00002 TABLE 2 Preliminary heat treatment Pressurized baking First Second Heating Kind of stage stage condition silver Temp. Time Temp, Time T.sub.1 Pressure Temp. T.sub.2 Time Example No. paste ( C.) (min) ( C.) (min) ( C.) (MPa) ( C.) (min) Comparative A 100 10 10 180 5 Example 1 Comparative A 100 10 20 180 5 Example 2 Comparative A 100 10 150 10 150 Example 3 Comparative A 100 10 Example 4 Comparative B 100 10 150 10 150 20 180 5 Example 5 Comparative B 100 10 150 10 150 30 180 5 Example 6 Coated film after pressurized baking Joining test Evaluation Heating of condition Evaluation Ra sheet SEM Pressure Temp. T.sub.3 Time of joining Example No. (m) formation micrograph (MPa) ( C.) (min) strength Comparative 0.421 X FIG. 6 Example 1 Comparative 0.406 X FIG. 7 Example 2 Comparative 0.486 X Example 3 Comparative 0.482 X Example 4 Comparative 6.338 X Example 5 Comparative 5.458 X Example 6

[0061] In Examples, the preliminary heat treatment was performed at the temperature T.sub.1 ( C.) that was the 25% volatilization temperature T.sub.25 ( C.) or higher and caused no sintering of the silver particles. It is considered that the dispersion medium in the paste was substantially removed through volatilization by the preliminary heat treatment. As a result, the sheet was able to be formed. It is also considered that most of the organic protective material on the surface of the silver particles and the organic substance as the additive were substantially removed through volatilization at the heat baking temperature T.sub.2 ( C.). The silver sheets thus obtained were determined to have the capability of further undergoing sintering. It was confirmed that the silver sheet can be used for diffusion joining at a low pressure. It was also confirmed that the enhancement of the smoothness on the surface of the silver sheet was effective for providing a high joining strength (comparison between Example 8 and the other Examples).

[0062] In Comparative Examples 1 and 2, on the other hand, the preliminary heat treatment at a temperature that was the 25% volatilization temperature T.sub.25 ( C.) or higher was not performed, and thus the dispersion medium in the paste was insufficiently removed through volatilization, thereby failing to form a sheet by the pressurized baking. In Comparative Examples 3 and 4, the pressurized baking was not performed, thereby failing to form a sheet. In Comparative Examples 5 and 6, raw material silver powder formed of silver particles having a particle diameter exceeding 250 nm was used, and thus the sintering did not proceed at the pressurized baking temperature according to the invention, thereby failing to form a sheet.