Metal materials and components of compression-sealed glass hermetic seals

Abstract

The present invention provides a metal material particularly suitable for components of compression-sealed glass hermetic seals, which offers high reliability in bonding with sealing glass, enables the conduction of large currents even with small diameters, realizes lead pins that generate little heat during energization, and allows for appropriate compression of the sealing glass and lead pins in the plate surface direction, while also enabling the realization of a stem base with high reliability in bonding with sealing glass and excellent heat dissipation performance in the plate thickness direction. [Solution] The [Cr and / or Mo]-Cu composite has a metallic structure in which a Cr phase and / or Mo phase are dispersed in a Cu matrix. This [Cr and / or Mo]-Cu composite is a diameter-reduced and drawn material of a powder metallurgy molded body. When the cross-sectional structure is observed with an optical microscope, it has a cross-sectional structure in the direction of stretching in which layered or linear Cr phases and / or Mo phases are dispersed in the Cu matrix, and a cross-sectional structure perpendicular to stretching in which flaky, small-piece, or granular Cr phases and / or Mo phases are dispersed in the Cu matrix.

Description

Technical Field

[0001] The present invention relates to a metal material composed of a [Cr or / and Mo]-Cu composite having a specific metal structure, and components (lead pins, stem bases) of a compression-sealed glass hermetic seal using this metal material, etc.

Background Art

[0002] A glass hermetic seal is a seal in which a metal lead pin is hermetically sealed through glass (sealing material) in an insertion hole penetrating a metal stem base, and is used, for example, when supplying current to an electrical device or element housed in an airtight container or deriving a signal from an electrical device or element to the outside. Specific examples include seals provided in airtight terminals and semiconductor laser devices.

[0003] Glass hermetic seals are of the alignment seal (sealing) type and the compression seal (sealing) type. Among these, in the alignment seal type, the metal stem base, metal lead pin, and sealing glass are made of materials having substantially the same coefficient of thermal expansion so that the shrinkage difference between the metal stem base, metal lead pin, and sealing glass hardly occurs, and the lead pin is chemically sealed through an oxide film of the metal formed at the interface between the metal and the sealing glass. On the other hand, the compression seal type utilizes the difference in the coefficient of thermal expansion between the stem base (metal) and the sealing glass, and mechanically seals the lead pin by applying a compressive stress to the sealing glass and the lead pin from the stem base side. When the glass is heated and melted in a state where the lead pin and the glass are set in the insertion hole of the stem base and then cooled and solidified, the stem base compresses the sealing glass and the lead pin due to the difference in the shrinkage amount between the stem base and the sealing glass, and mechanically seals the lead pin.

[0004] Conventionally, the material combination for this compression-sealed type typically involves using carbon steel such as SC or SPC for the stem base, Ni-Fe alloys such as 50% Ni-Fe alloy or Kovar for the lead pins, and soda-based glass for the sealing glass (for example, Patent Document 1). In addition to the above, stainless steel (SUS410, SUS430, SUH446, etc.) may be used for the lead pins, and stainless steel (SUS304, SUS410, etc.) or chromium steel may be used for the stem base. Because this compression-sealed glass hermetic seal can utilize relatively inexpensive materials, it has been widely used in hermetic terminals and semiconductor laser devices.

[0005] Generally, in semiconductor laser devices equipped with compression-sealed glass hermetic seals, when a semiconductor laser element that generates a large amount of heat is mounted, carbon steel is used for the stem base because it has a higher thermal conductivity and is less expensive than materials such as Kovar. If heat dissipation is insufficient with only this stem base material, the semiconductor laser element is mounted on the upper surface of the stem base via a laser element holder with heat dissipation capabilities (a block-shaped heat sink protruding from the upper surface of the stem base) (for example, Patent Documents 2 and 3). Typically, this laser element holder is made of a material such as Cu, which has a high thermal conductivity from the viewpoint of heat dissipation. [Prior art documents] [Patent Documents]

[0006] [Patent Document 1] Japanese Patent Publication No. 2008-27679 [Patent Document 2] Japanese Patent Application Publication No. 8-242041 [Patent Document 3] Japanese Patent Publication No. 2016-29718 [Overview of the project] [Problems that the invention aims to solve]

[0007] The lead pins and stem bases, which are components (parts) of compression-sealed glass hermetic seals, have the following technical challenges: First, regarding lead pins, if the difference in thermal expansion between the lead pin and the sealing glass is large in the axial direction, the axial shear stress generated at the interface between the lead pin and the sealing glass will be large. For example, Kovar (thermal expansion coefficient: 5.3 × 10⁻⁶) -6 The thermal expansion coefficient is 7.6 × 10⁻⁶ (K). -6 / K sealing glass (FN-13W, manufactured by Nippon Electric Glass Co., Ltd.) is used, but 2×10 -6 A difference in thermal expansion coefficient of approximately 1 / K occurs. This leads to problems such as reduced reliability of the joint between the lead pin and the sealing glass, including the risk of cracking in the sealing glass due to fatigue caused by repeated temperature increases and decreases during use. Furthermore, if the lead pin has low axial electrical conductivity, the amount of heat generated during current flow increases, making it unsuitable for applications involving high currents.

[0008] While some Ni-Fe alloys and certain stainless steels, among the materials conventionally used for lead pins, exhibit relatively small differences in thermal expansion with the sealing glass in the axial direction, all conventionally used materials have low axial electrical conductivity and cannot address the aforementioned challenges. In particular, electric compressors for EVs and HEVs have recently been designed to handle high currents, and the lead pins of hermetic terminals (hermetic terminals equipped with compression-sealed glass hermetic seals) used for power connection terminals are required to generate sufficiently low heat even when high currents are passed through them. However, the conventional lead pins mentioned above cannot satisfy this requirement. Furthermore, "copper core pins with a copper cladding around a 50% Ni-Fe core" have been used as lead pins that can reduce heat generation when high currents are passed through them, but there are limits to the reduction in heat generation. Moreover, as electric compressors continue to handle higher currents, the pin diameter will increase, making it impossible to meet the demand for miniaturization of automotive parts.

[0009] If the electrical conductivity of the lead pins is low, power consumption at the lead pins increases, placing a greater load on the onboard battery. EVs require even higher currents, and existing materials, including copper core pins, cannot accommodate the lead pin diameter used in hermetically sealed terminals (e.g., φ3.2mm), necessitating an even larger lead pin diameter. However, if four times the current were to flow, the lead pin diameter would need to be φ6.4mm, which would create problems with the weight reduction and miniaturization of automotive parts, and would also quadruple the material cost of the lead pins, posing a significant cost issue. As described above, the material required for lead pins is one that has a relatively small axial thermal expansion coefficient, preferably one that is as close as possible to the thermal expansion coefficient of the sealing glass, and also has the highest possible axial electrical conductivity. However, no metal material has been known to satisfy such requirements.

[0010] Next, regarding the stem base, since it is necessary to mechanically seal the sealing glass and lead pins by compressing them, the thermal expansion coefficient in the plate plane direction must be somewhat larger than that of the sealing glass. On the other hand, similar to the relationship between the lead pins and sealing glass mentioned earlier, if the difference in thermal expansion with the sealing glass is large in the plate thickness direction, the shear stress in the plate thickness direction that occurs at the interface between the stem base and the sealing glass will increase. This leads to problems such as reduced reliability of the bond between the stem base and the sealing glass, including the risk of cracks forming in the sealing glass due to fatigue caused by repeated temperature increases and decreases during use. Furthermore, in the case of semiconductor laser devices, if the heat generated from the semiconductor laser element is not properly dissipated through the stem base, problems such as a decrease in the output and lifespan of the laser element will occur.

[0011] Conventional stem bases require compression of the sealing glass and lead pins, necessitating the use of materials with a coefficient of thermal expansion somewhat greater than that of the sealing glass (such as carbon steel). This inevitably leads to a large difference in thermal expansion between the stem base and the sealing glass in the thickness direction, resulting in increased shear stress in the thickness direction at the interface between the stem base and the sealing glass, and thus reducing the reliability of the bond between the stem base and the sealing glass. Furthermore, the materials used for stem bases (such as carbon steel) all have low thermal conductivity, making it difficult to adequately dissipate the heat generated from the semiconductor laser element. Consequently, conventional semiconductor laser devices suffer from insufficient heat dissipation, which can easily lead to problems such as reduced laser element output and shorter lifespan, and also hinders their ability to handle the increasing power output and performance of semiconductor laser devices. As described above, the stem base material needs to have a coefficient of thermal expansion in the plane direction that is somewhat greater than the coefficient of thermal expansion of the sealing glass, while having a relatively small coefficient of thermal expansion in the thickness direction, and having a coefficient of thermal expansion in the thickness direction that is as close as possible to that of the sealing glass; in other words, it is desirable that the difference in thermal expansion with the sealing glass in the thickness direction be as small as possible. Furthermore, the stem base material is required to have the highest possible thermal conductivity in the thickness direction. However, no metal material has been known to satisfy such requirements to date.

[0012] The present invention has been made to solve the problems of the prior art described above, and its purpose is to provide a metal material that is particularly suitable for lead pins and stem bases of compression-sealed glass hermetic seals, and that can satisfy the following requirements: (i) it can realize lead pins with a relatively small axial thermal expansion coefficient and high axial electrical conductivity; (ii) it can realize stem bases that have a plate-plane thermal expansion coefficient to the extent required for stem bases, a relatively small plate-thickness thermal expansion coefficient and high plate-thickness thermal conductivity; and (iii) it can adjust the axial thermal expansion coefficient of the lead pins and the plate-thickness thermal expansion coefficient of the stem base to match the thermal expansion coefficient of the sealing glass used, bringing them closer to the thermal expansion coefficient of the sealing glass.

[0013] Furthermore, other objects of the present invention are (I) to provide a lead pin for a compression-sealed glass hermetic seal using the above-mentioned metal material, which has high reliability in bonding with the sealing glass, can conduct large currents even with a small diameter, and generates little heat when energized; and (II) to provide a stem base for a compression-sealed glass hermetic seal using the above-mentioned metal material, which can appropriately compress the sealing glass and lead pin in the plate surface direction, has high reliability in bonding with the sealing glass, and also has excellent heat dissipation performance in the plate thickness direction. Furthermore, another object of the present invention is to provide an airtight terminal using the above-mentioned metal material for the lead pin, and an electric compressor using this airtight terminal. Furthermore, another object of the present invention is to provide a semiconductor laser apparatus using the above-mentioned metal material for lead pins and / or stem bases. [Means for solving the problem]

[0014] As a result of repeated studies to solve the above problems, the inventors of the present invention have obtained the following findings and have developed a novel metal material and products using the same according to the present invention. (i) A metal material obtained by reducing the diameter of a material consisting of a [Cr and / or Mo]-Cu composite obtained by powder metallurgy is subjected to a reduction in surface area (diameter reduction stretching) to stretch it into a rod or wire shape (i.e., a [Cr and / or Mo]-Cu composite that is a diameter reduction stretched material of a powder metallurgy molded body) has a metallic structure in which the Cr phase and / or Mo phase are dispersed in the Cu matrix. When the cross-sectional structure is observed with an optical microscope, it has a cross-sectional structure in the stretching direction (axial direction) in which layered or linear Cr phases and / or Mo phases are dispersed in the Cu matrix, and a cross-sectional structure perpendicular to the stretching direction (radial direction) in which flaky, small, or granular Cr phases and / or Mo phases are dispersed in the Cu matrix. Conventionally, rolled Cr-Cu composite sheets (rolled into a sheet shape with a flat roll) are known, but the cross-sectional structure of the above metal material is completely different from the cross-sectional structure of these rolled Cr-Cu composite sheets.

[0015] (ii) Metal materials having the above-described cross-sectional structure in the stretching direction and perpendicular to the stretching direction ([Cr and / or Mo]-Cu composites, which are diameter-reduced stretched materials for powder metallurgy molded products) have unique properties (characteristics) that differ from metal materials conventionally used for lead pins and stem bases of compression-sealed glass hermetic seals, or for other conductive components. Specifically, these metal materials have a thermal expansion coefficient in the stretching direction < thermal expansion coefficient perpendicular to the stretching direction, a relatively small thermal expansion coefficient in the stretching direction, an isotropic thermal expansion coefficient perpendicular to the stretching direction, and high electrical conductivity and thermal conductivity in the stretching direction. Furthermore, those with further optimized properties can have a thermal expansion coefficient in the stretching direction close to that of sealing glass, and have significantly higher electrical conductivity in the stretching direction compared to Ni-Fe alloys widely used for lead pins, and significantly higher thermal conductivity in the stretching direction compared to carbon steel widely used for stem bases.

[0016] Therefore, a rod-shaped or wire-shaped metal material (a [Cr and / or Mo]-Cu composite, which is a diameter-reduced drawn material for powder metallurgy molded bodies) with the above-mentioned stretching direction as the axial direction and the direction perpendicular to the stretching direction as the radial direction has an axial thermal expansion coefficient < radial thermal expansion coefficient, a relatively small axial thermal expansion coefficient, an isotropic radial thermal expansion coefficient, and high axial electrical conductivity. Furthermore, among these, those with further optimized properties can have an axial thermal expansion coefficient close to that of sealing glass, and have significantly higher axial electrical conductivity compared to Ni-Fe alloys, which are widely used for lead pins. Furthermore, a plate-shaped metal material (a [Cr and / or Mo]-Cu composite, which is a diameter-reduced drawn material for powder metallurgy molded bodies) with the stretching direction as the thickness direction and the stretching direction as the surface direction has a thermal expansion coefficient in the surface direction that is sufficient for a stem base, and has a relatively small thermal expansion coefficient in the thickness direction, an isotropic thermal expansion coefficient in the surface direction, and high thermal conductivity in the thickness direction. Moreover, a material with further optimized properties can have a thermal expansion coefficient in the thickness direction that is close to that of sealing glass, and has significantly higher thermal conductivity in the thickness direction compared to carbon steel and other materials widely used for stem bases.

[0017] Furthermore, a key feature of this metallic material is that the magnitude of the thermal expansion coefficient in the stretching direction can be changed (adjusted) by selecting the blending ratio (content) of Cr and / or Mo in the [Cr and / or Mo]-Cu composite and the reduction ratio during diameter reduction stretching of the material. In other words, the magnitude of the axial thermal expansion coefficient can be changed (adjusted) for rod-shaped or wire-shaped metallic materials, and the magnitude of the thermal expansion coefficient in the thickness direction can be changed (adjusted) for plate-shaped metallic materials. As a result, the axial thermal expansion coefficient of the lead pin and the thickness direction thermal expansion coefficient of the stem base can be brought as close as possible to the thermal expansion coefficient of the sealing glass, thereby maximizing the reliability of the bond between the lead pin and stem base and the sealing glass, which is a challenge for compression-sealed glass hermetic seals. In addition, the magnitude of the electrical conductivity and thermal conductivity in the stretching direction of this metallic material changes depending on the magnitude of the reduction ratio during diameter reduction stretching, with the electrical conductivity and thermal conductivity in the stretching direction increasing as the reduction ratio increases. In other words, the larger the reduction ratio, the greater the axial electrical conductivity of rod-shaped or wire-shaped metal materials, and the greater the thermal conductivity in the thickness direction of plate-shaped metal materials. Therefore, by changing the reduction ratio, the axial electrical conductivity or the thermal conductivity in the thickness direction can be appropriately adjusted depending on the application of the metal material. Therefore, with regard to compression-sealed glass hermetic seal applications, the former rod-shaped or wire-shaped metal material is very suitable for lead pins, and the latter plate-shaped metal material is very suitable for stem bases, and can be said to highly satisfy the various properties required for lead pins and stem bases as described above. Such metal materials are completely unknown to the public and are novel metal materials created by the present invention.

[0018] (iii) This metal material can be manufactured relatively easily by reducing the diameter of a material made of a [Cr and / or Mo]-Cu composite (powder metallurgy molded body) obtained through a process of sintering powder raw materials, and then reducing the diameter of that material by a reduction in surface area (reducing the diameter and stretching process) to make it into a rod or wire shape. Here, the rod or wire metal material described above can be manufactured by the reduction in surface area (reducing the diameter and stretching process) alone, and the plate-shaped metal material described above can be manufactured by cutting the rod or wire material obtained by the reduction in surface area (reducing the diameter and stretching process) in the radial direction, and cutting out a plate material with the axial direction of the material as the plate thickness direction and the radial direction as the plate surface direction.

[0019] This invention is based on the above findings and is summarized as follows. [1] Consists of a [Cr or / and Mo]-Cu composite having a metallic structure in which a Cr phase or / and a Mo phase is dispersed in a Cu matrix, The [Cr and / or Mo]-Cu composite is a diameter-reduced and drawn material for powder metallurgy molded bodies, and is a metallic material characterized by having a cross-sectional structure in the direction of stretching in which layered or linear Cr phases and / or Mo phases are dispersed in the Cu matrix, and a cross-sectional structure perpendicular to stretching in which flaky, small-piece, or granular Cr phases and / or Mo phases are dispersed in the Cu matrix, as observed with an optical microscope. [2] In the metal material described in [1] above, the average coefficient of thermal expansion in the stretching direction from 30°C to 450°C is 7.0 to 12.0 × 10 -6 The mean coefficient of thermal expansion perpendicular to the extension direction from 30°C to 450°C is 18.0 × 10⁻¹⁰ / K. -6 A metallic material characterized by having a temperature of 0.150°C or less and having the following characteristics: [average thermal expansion coefficient in the stretching direction from 30°C to 450°C] < [average thermal expansion coefficient in the direction perpendicular to stretching from 30°C to 450°C].

[0020] [3] In the metallic material described in [1] or [2] above, the electrical conductivity in the stretching direction is 20.0 × 10 6 A metallic material characterized by having a thermal conductivity of S / m or higher or 180 W / m·K or higher. [4] A metallic material in any of the above [1] to [3], characterized in that the [Cr and / or Mo]-Cu composite has a total content of Cr and / or Mo of 35 to 60 mass%. [5] A metal material characterized by being a rod-shaped or wire-shaped metal material in any of the above [1] to [4], wherein the stretching direction is the axial direction and the direction perpendicular to the stretching direction is the radial direction. [6] A metal material characterized by being a plate-shaped metal material in which the stretching direction is the thickness direction and the direction perpendicular to the stretching direction is the surface direction, according to any of the metal materials in [1] to [4] above.

[0021] [7] A method for manufacturing any of the metal materials described in [1] to [4] above, A process (A) to obtain a material for surface reduction processing consisting of a [Cr and / or Mo]-Cu composite through a process of sintering powder raw materials, A method for manufacturing a metal material, characterized by comprising a step (B) of reducing the diameter of the material obtained in step (A) by reducing the surface area and stretching it into a rod or wire shape. [8] A method for manufacturing a metal material, wherein step (B) is a step of finishing drawing the material, in the manufacturing method of [7] above. [9] A method for manufacturing a metal material, characterized in that the manufacturing method according to [7] or [8] further comprises a step (C) of grinding or polishing the surface of the rod-shaped or wire-shaped material obtained in step (B) (however, this includes the rod-shaped or wire-shaped material obtained in step (B) cut to a predetermined length).

[10] A method for manufacturing a metal material, characterized in that the manufacturing method according to [7] or [8] above further comprises a step (D) of cutting the rod-shaped or wire-shaped material obtained in step (B) in the radial direction, and cutting out a plate material in which the axial direction of the material is the plate thickness direction and the radial direction is the plate surface direction.

[11] A method for manufacturing a metal material, characterized in that the manufacturing method of [9] above further comprises a step (D) of cutting the rod-shaped or wire-shaped material that has undergone step (C) in the radial direction, and cutting out a plate material in which the axial direction of the material is the plate thickness direction and the radial direction is the plate surface direction.

[0022]

[12] A rod-shaped or wire-shaped metal material for lead pins constituting a compression-sealed glass hermetic seal, consisting of a [Cr or / and Mo]-Cu composite having a metal structure in which Cr phase or / and Mo phase is dispersed in a Cu matrix, The [Cr or / and Mo]-Cu composite is a reduced-diameter drawn material of a powder metallurgy compact. When observing the cross-sectional structure with an optical microscope, it has an axial cross-sectional structure in which layered or linear Cr phase or / and Mo phase is dispersed in the Cu matrix, and a radial cross-sectional structure in which flaky, small flaky or granular Cr phase or / and Mo phase is dispersed in the Cu matrix. It is a metal material for lead pins of a compression-sealed glass hermetic seal.

[0023]

[13] In the metal material of

[12] above, the axial average thermal expansion coefficient from 30 °C to 450 °C is 7.0~12.0×10 -6 / K, the radial average thermal expansion coefficient from 30 °C to 450 °C is 18.0×10 -6 / K or less, and [axial average thermal expansion coefficient from 30 °C to 450 °C] < [radial average thermal expansion coefficient from 30 °C to 450 °C]. It is a metal material for lead pins of a compression-sealed glass hermetic seal.

[14] In the metal material of

[12] or

[13] above, the electrical conductivity in the axial direction is 20.0×10 6 S / m or more. It is a metal material for lead pins of a compression-sealed glass hermetic seal.

[15] In any of the metal materials of

[12] ~

[14] above, the [Cr or / and Mo]-Cu composite has a total content of Cr or / and Mo of 35~60 mass%. It is a metal material for lead pins of a compression-sealed glass hermetic seal.

[0024]

[16] A plate-shaped metal material for a stem base constituting a compression-sealed glass hermetic seal, consisting of a [Cr or / and Mo]-Cu composite having a metal structure in which Cr phase or / and Mo phase is dispersed in a Cu matrix, The [Cr and / or Mo]-Cu composite is a diameter-reduced and drawn material for powder metallurgy molded articles, characterized in that, when observed in cross-sectional view with an optical microscope, it has a cross-sectional structure in the thickness direction in which layered or linear Cr phases and / or Mo phases are dispersed in the Cu matrix, and a cross-sectional structure parallel to the plate surface in which flaky, small-piece, or granular Cr phases and / or Mo phases are dispersed in the Cu matrix, and is a metallic material for the stem base of a compression-sealed glass hermetic seal.

[0025]

[17] In the metal material described in

[16] above, the average thermal expansion coefficient in the thickness direction from 30°C to 450°C is 7.0 to 12.0 × 10 -6 The mean coefficient of thermal expansion in the direction of the plate surface from 30°C to 450°C is 18.0 × 10⁻¹⁰ / K. -6 A metal material for the stem base of a compression-sealed glass hermetic seal, characterized in that it is less than or equal to / K and [average thermal expansion coefficient in the thickness direction from 30°C to 450°C] < [average thermal expansion coefficient in the surface direction from 30°C to 450°C].

[18] A metal material for the stem base of a compression-sealed glass hermetic seal, characterized in that the thermal conductivity in the thickness direction of the metal material of

[16] or

[17] is 180 W / m·K or more.

[19] A metal material for the stem base of a compression-sealed glass hermetic seal, characterized in that, in any of the metal materials of

[16] to

[18] above, the [Cr and / or Mo]-Cu composite has a total Cr and / or Mo content of 35 to 60 mass%.

[0026]

[20] Lead pins comprising a compression-sealed glass hermetic seal, It consists of a [Cr or / and Mo]-Cu composite having a metallic structure in which a Cr phase or / and a Mo phase is dispersed in a Cu matrix. The [Cr and / or Mo]-Cu composite is a diameter-reduced stretchable material for powder metallurgy molded articles, and is characterized in that, when the cross-sectional structure is observed with an optical microscope, it has an axial cross-sectional structure in which layered or linear Cr phases and / or Mo phases are dispersed in the Cu matrix, and a radial cross-sectional structure in which flaky, small-piece, or granular Cr phases and / or Mo phases are dispersed in the Cu matrix, as a lead pin for a compression-sealed glass hermetic seal.

[0027]

[21] In the lead pin described in

[20] above, the average axial thermal expansion coefficient from 30°C to 450°C is 7.0 to 12.0 × 10 -6 The mean radial thermal expansion coefficient is 18.0 × 10⁻¹⁰ / K, from 30°C to 450°C. -6 A lead pin for a compression-sealed glass hermetic seal, characterized by having a temperature of 0.0 / K or less and [average axial thermal expansion coefficient from 30°C to 450°C] < [average radial thermal expansion coefficient from 30°C to 450°C].

[22] In the lead pins of

[20] or

[21] above, the axial electrical conductivity is 20.0 × 10 6 Lead pins for compression-sealed glass hermetic seals, characterized by having a density of S / m or greater.

[23] A lead pin for a compression-sealed glass hermetic seal, wherein in any of the lead pins of

[20] to

[22] above, the [Cr and / or Mo]-Cu composite is characterized in that the total content of Cr and / or Mo is 35 to 60 mass%.

[0028]

[24] A plate-shaped stem base comprising a compression-sealed glass hermetic seal, It consists of a [Cr or / and Mo]-Cu composite having a metallic structure in which a Cr phase or / and a Mo phase is dispersed in a Cu matrix. The [Cr and / or Mo]-Cu composite is a diameter-reduced stretchable material for powder metallurgy molded articles, characterized in that, when observed in cross-sectional view with an optical microscope, it has a cross-sectional structure in the thickness direction in which layered or linear Cr phases and / or Mo phases are dispersed in the Cu matrix, and a cross-sectional structure parallel to the plate surface in which flaky, small-piece, or granular Cr phases and / or Mo phases are dispersed in the Cu matrix, forming a stem base for a compression-sealed glass hermetic seal.

[0029]

[25] In the stem base described in

[24] above, the average coefficient of thermal expansion in the thickness direction from 30°C to 450°C is 7.0 to 12.0 × 10 -6 The mean coefficient of thermal expansion in the direction of the plate surface from 30°C to 450°C is 18.0 × 10⁻¹⁰ / K. -6 A stem base for a compression-sealed glass hermetic seal, characterized in that it is less than or equal to / K and [average thermal expansion coefficient in the thickness direction from 30°C to 450°C] < [average thermal expansion coefficient in the surface direction from 30°C to 450°C].

[26] A stem base for a compression-sealed glass hermetic seal, characterized in that the thermal conductivity in the thickness direction of the plate is 180 W / m·K or more, in the stem base of

[24] or

[25] above.

[27] A stem base for a compression-sealed glass hermetic seal, characterized in that, in any of the stem bases of

[24] to

[26] above, the [Cr and / or Mo]-Cu composite has a total Cr and / or Mo content of 35 to 60 mass%.

[0030]

[28] In a compression-sealed hermetic terminal, The lead pin is made of a [Cr or / and Mo]-Cu composite having a metallic structure in which a Cr phase or / and a Mo phase is dispersed in a Cu matrix. The [Cr and / or Mo]-Cu composite is a diameter-reduced and drawn material for powder metallurgy molded bodies, and is characterized in that, when the cross-sectional structure is observed with an optical microscope, it has an axial cross-sectional structure in which layered or linear Cr phases and / or Mo phases are dispersed in the Cu matrix, and a radial cross-sectional structure in which flaky, small-piece, or granular Cr phases and / or Mo phases are dispersed in the Cu matrix.

[29] In the airtight terminal described in

[28] above, the lead pin has an average axial thermal expansion coefficient of 7.0 to 12.0 × 10 from 30°C to 450°C. -6 The mean radial thermal expansion coefficient is 18.0 × 10⁻¹⁰ / K, from 30°C to 450°C. -6 An airtight terminal characterized by having a temperature of 0.5K or less and [average axial thermal expansion coefficient from 30°C to 450°C] < [average radial thermal expansion coefficient from 30°C to 450°C].

[0031]

[30] In the hermetically sealed terminal described in

[28] or

[29] above, the lead pin has an axial electrical conductivity of 20.0 × 10 6 A sealed terminal characterized by having a density of S / m or greater.

[31] An airtight terminal in any of the above

[28] to

[30] , characterized in that the [Cr and / or Mo]-Cu composite has a total content of Cr and / or Mo of 35 to 60 mass%.

[32] An electric compressor characterized by being equipped with the airtight terminals described in

[28] or

[29] above.

[33] An electric compressor characterized by being equipped with the airtight terminals described in

[30] or

[31] above.

[0032]

[34] The plate-like stem base is made of a [Cr or / and Mo]-Cu composite having a metallic structure in which a Cr phase or / and a Mo phase is dispersed in a Cu matrix, The [Cr and / or Mo]-Cu composite is a diameter-reduced and drawn material for powder metallurgy molded bodies, and is characterized in that, when the cross-sectional structure is observed with an optical microscope, it has a cross-sectional structure in the thickness direction in which layered or linear Cr phases and / or Mo phases are dispersed in the Cu matrix, and a cross-sectional structure parallel to the plate surface in which flaky, small-piece, or granular Cr phases and / or Mo phases are dispersed in the Cu matrix.

[35] In the semiconductor laser apparatus described in

[34] above, the stem base has an average thermal expansion coefficient in the thickness direction from 30°C to 450°C of 7.0 to 12.0 × 10 -6 The mean coefficient of thermal expansion in the direction of the plate surface from 30°C to 450°C is 18.0 × 10⁻¹⁰ / K. -6A semiconductor laser device characterized by having a temperature of 0.5K or less and [average thermal expansion coefficient in the thickness direction from 30°C to 450°C] < [average thermal expansion coefficient in the surface direction from 30°C to 450°C].

[0033]

[36] The semiconductor laser apparatus according to

[34] or

[35] above, characterized in that the stem base has a thermal conductivity of 180 W / m·K or more in the plate thickness direction.

[37] A semiconductor laser apparatus in any of the above

[34] to

[36] , characterized in that the [Cr and / or Mo]-Cu composite has a total content of Cr and / or Mo of 35 to 60 mass%.

[38] The lead pin is made of a [Cr or / and Mo]-Cu composite having a metallic structure in which a Cr phase or / and a Mo phase is dispersed in a Cu matrix. The [Cr and / or Mo]-Cu composite is a diameter-reduced and drawn material for powder metallurgy molded bodies, and is characterized in that, when the cross-sectional structure is observed with an optical microscope, it has an axial cross-sectional structure in which layered or linear Cr phases and / or Mo phases are dispersed in the Cu matrix, and a radial cross-sectional structure in which flaky, small-piece, or granular Cr phases and / or Mo phases are dispersed in the Cu matrix.

[0034]

[39] In the semiconductor laser apparatus described in

[38] above, the lead pins have an average axial thermal expansion coefficient of 7.0 to 12.0 × 10 from 30°C to 450°C. -6 The mean radial thermal expansion coefficient is 18.0 × 10⁻¹⁰ / K, from 30°C to 450°C. -6 A semiconductor laser device characterized by having a temperature of 0.5K or less and [average axial thermal expansion coefficient from 30°C to 450°C] < [average radial thermal expansion coefficient from 30°C to 450°C].

[40] In the semiconductor laser apparatus described in

[38] or

[39] above, the lead pin has an axial electrical conductivity of 20.0 × 10 6 A semiconductor laser device characterized by having a density of S / m or higher.

[41] A semiconductor laser apparatus in any of the above

[38] to

[40] , characterized in that the [Cr and / or Mo]-Cu composite has a total content of Cr and / or Mo of 35 to 60 mass%.

[0035]

[42] The plate-shaped stem base and lead pins are made of a [Cr or / and Mo]-Cu composite having a metallic structure in which a Cr phase or / and a Mo phase is dispersed in a Cu matrix. The [Cr and / or Mo]-Cu composite constituting the plate-shaped stem base is a diameter-reduced stretched material for powder metallurgy molded products, and when the cross-sectional structure is observed with an optical microscope, it has a cross-sectional structure in the thickness direction in which layered or linear Cr phases and / or Mo phases are dispersed in the Cu matrix, and a cross-sectional structure parallel to the plate surface in which flaky, small-piece, or granular Cr phases and / or Mo phases are dispersed in the Cu matrix. The [Cr and / or Mo]-Cu composite constituting the lead pin is a diameter-reduced and drawn material for a powder metallurgy molded body, and is characterized in that, when the cross-sectional structure is observed with an optical microscope, it has an axial cross-sectional structure in which layered or linear Cr phases and / or Mo phases are dispersed in the Cu matrix, and a radial cross-sectional structure in which flaky, small-piece, or granular Cr phases and / or Mo phases are dispersed in the Cu matrix.

[0036]

[43] In the semiconductor laser apparatus described in

[42] above, The aforementioned stem base has an average thermal expansion coefficient in the thickness direction of the plate from 30°C to 450°C of 7.0 to 12.0 × 10 -6 The mean coefficient of thermal expansion in the direction of the plate surface from 30°C to 450°C is 18.0 × 10⁻¹⁰ / K. -6 The temperature is less than or equal to / K, and the average thermal expansion coefficient in the thickness direction from 30°C to 450°C is less than the average thermal expansion coefficient in the surface direction from 30°C to 450°C. The lead pin has an average axial thermal expansion coefficient of 7.0 to 12.0 × 10⁻¹⁰ from 30°C to 450°C. -6 The mean radial thermal expansion coefficient is 18.0 × 10⁻¹⁰ / K, from 30°C to 450°C. -6A semiconductor laser device characterized by having a temperature of 0.5K or less and [average axial thermal expansion coefficient from 30°C to 450°C] < [average radial thermal expansion coefficient from 30°C to 450°C].

[0037]

[44] In the semiconductor laser apparatus described in

[42] or

[43] above, The aforementioned stem base has a thermal conductivity of 180 W / m·K or more in the thickness direction. The aforementioned lead pin has an axial electrical conductivity of 20.0 × 10 6 A semiconductor laser device that specifies a speed of S / m or higher.

[45] A semiconductor laser apparatus in any of the above

[42] to

[44] , characterized in that the [Cr and / or Mo]-Cu composite constituting the stem base and the lead pin has a total Cr and / or Mo content of 35 to 60 mass%.

[46] A semiconductor laser apparatus characterized in that a compression-sealed glass hermetic seal is formed in any of the semiconductor laser apparatuses described in

[34] to

[45] above, wherein the stem base and / or the lead pins are constituent members. [Effects of the Invention]

[0038] <Metal material of the present invention> The metal material of the present invention (a [Cr and / or Mo]-Cu composite, which is a diameter-reduced drawing material for powder metallurgy molded bodies) has a thermal expansion coefficient in the drawing direction < thermal expansion coefficient in the direction perpendicular to the drawing direction, a relatively small thermal expansion coefficient in the drawing direction, an isotropic thermal expansion coefficient in the direction perpendicular to the drawing direction, and high electrical conductivity and thermal conductivity in the drawing direction. Furthermore, a material with further optimized properties can have a thermal expansion coefficient in the drawing direction close to that of sealing glass, and has significantly higher electrical conductivity in the drawing direction compared to Ni-Fe alloys and other materials widely used in conventional lead pins, and significantly higher thermal conductivity in the drawing direction compared to carbon steel and other materials widely used in conventional stem bases.

[0039] Therefore, a rod-shaped or wire-shaped metal material (a [Cr and / or Mo]-Cu composite, which is a diameter-reduced drawn material for powder metallurgy molded bodies) with the above-mentioned stretching direction as the axial direction and the direction perpendicular to the stretching direction as the radial direction has an axial thermal expansion coefficient < radial thermal expansion coefficient, a relatively small axial thermal expansion coefficient, an isotropic radial thermal expansion coefficient, and high axial electrical conductivity. Furthermore, among these, those with further optimized properties can have an axial thermal expansion coefficient close to that of sealing glass, and have significantly higher axial electrical conductivity compared to Ni-Fe alloys and other materials widely used in conventional lead pins. Furthermore, a plate-shaped metal material (a [Cr and / or Mo]-Cu composite, which is a diameter-reduced drawn material of a powder metallurgy molded body) with the stretching direction as the thickness direction and the direction perpendicular to the stretching direction as the surface direction has a thermal expansion coefficient in the surface direction that is sufficient for a stem base, and has a relatively small thermal expansion coefficient in the thickness direction, an isotropic thermal expansion coefficient in the surface direction, and high thermal conductivity in the thickness direction. Moreover, a material with further optimized properties can have a thermal expansion coefficient in the thickness direction that is close to that of sealing glass, and has significantly higher thermal conductivity in the thickness direction compared to carbon steel and other materials that are commonly used for stem bases.

[0040] Furthermore, the above-mentioned metal material of the present invention can have its coefficient of thermal expansion in the stretching direction changed (adjusted) by selecting the blending ratio (content) of Cr and / or Mo in the [Cr and Mo]-Cu composite and the reduction ratio during diameter reduction stretching of the material. That is, the coefficient of thermal expansion in the axial direction can be changed (adjusted) for rod-shaped or wire-shaped metal materials, and the coefficient of thermal expansion in the thickness direction can be changed (adjusted) for plate-shaped metal materials. As a result, the coefficient of thermal expansion in the axial direction of the lead pin and the coefficient of thermal expansion in the thickness direction of the stem base can be brought as close as possible to the coefficient of thermal expansion of the sealing glass, thereby maximizing the reliability of the bond between the lead pin and stem base and the sealing glass, which is a challenge for compression-sealed glass hermetic seals. Furthermore, the above-mentioned metal material of the present invention exhibits varying electrical conductivity and thermal conductivity in the stretching direction depending on the reduction ratio during diameter reduction stretching. As the reduction ratio increases, both the electrical conductivity and thermal conductivity in the stretching direction increase. In other words, as the reduction ratio increases, the axial electrical conductivity increases for rod-shaped or wire-shaped metal materials, and the thickness-direction thermal conductivity increases for plate-shaped metal materials. Therefore, by changing the reduction ratio, the axial electrical conductivity or thickness-direction thermal conductivity can be appropriately adjusted according to the application of the metal material.

[0041] Therefore, in compression-sealed glass hermetic seal applications, the linear or rod-shaped metal material of the present invention is a very suitable metal material for lead pins, providing high reliability of bonding with the sealing glass, enabling high current conduction even with a small diameter, and realizing lead pins with low heat generation during energization. Similarly, the plate-shaped metal material of the present invention is a very suitable metal material for stem bases, enabling appropriate compression of the sealing glass and lead pins in the plate surface direction, providing high reliability of bonding with the sealing glass, and realizing a stem base with excellent heat dissipation performance in the plate thickness direction. Furthermore, the manufacturing method of the present invention makes it possible to manufacture the above-mentioned metal materials appropriately and efficiently.

[0042] <Members and devices of the present invention> The lead pins of the present invention have an axial thermal expansion coefficient < radial thermal expansion coefficient, a relatively small axial thermal expansion coefficient, an isotropic radial thermal expansion coefficient, and high axial electrical conductivity. Furthermore, those with further optimized properties can have an axial thermal expansion coefficient close to that of the sealing glass, and have significantly higher axial electrical conductivity compared to conventional lead pins such as Ni-Fe alloys. Moreover, the magnitude of the axial thermal expansion coefficient of the lead pins of the present invention can be adjusted by selecting the blending ratio (content) of Cr and / or Mo in the [Cr and Mo]-Cu composite and the reduction ratio when the material is stretched to reduce its diameter, thereby bringing the axial thermal expansion coefficient of the lead pin as close as possible to that of the sealing glass. In addition, the axial electrical conductivity of the lead pins of the present invention increases as the reduction ratio when the material is stretched to reduce its diameter increases, so the axial electrical conductivity can be adjusted according to the application equipment. Therefore, the lead pin of the present invention can improve the reliability of bonding with sealing glass, and even with a small diameter, it can conduct high currents and reduce the amount of heat generated when energized. For example, it can adequately accommodate the further increase in current and miniaturization of electric compressors for automobiles.

[0043] Furthermore, the stem base of the present invention has a thermal expansion coefficient in the plane direction required for mechanically sealing the sealing glass and lead pin by compression, and has a thermal expansion coefficient in the thickness direction < thermal expansion coefficient in the plane direction, with a relatively small thermal expansion coefficient in the thickness direction, an isotropic thermal expansion coefficient in the plane direction, and high thermal conductivity in the thickness direction. Moreover, a further optimized version can have a thermal expansion coefficient in the thickness direction close to that of the sealing glass, and has significantly higher thermal conductivity in the thickness direction compared to carbon steel and other materials widely used in conventional stem bases. Furthermore, the present invention allows for adjustment of the thermal expansion coefficient in the thickness direction of the stem base by selecting the blending ratio (content) of Cr and / or Mo in the [Cr and Mo]-Cu composite and the reduction ratio when the material is stretched to reduce its diameter, thereby bringing the thermal expansion coefficient in the thickness direction of the stem base as close as possible to that of the sealing glass. In addition, the stem base of the present invention exhibits increased thermal conductivity in the thickness direction as the reduction ratio during diameter reduction and stretching increases, allowing for adjustment of the thermal conductivity in the thickness direction depending on the application equipment. Therefore, the stem base of the present invention can appropriately compress the sealing glass and lead pins in the plate surface direction, and can improve the reliability of bonding with the sealing glass. Moreover, it also has excellent heat dissipation performance in the plate thickness direction, so it can improve the heat dissipation performance of semiconductor laser devices, for example, and can adequately accommodate the increased power output and performance of semiconductor laser devices.

[0044] Furthermore, the airtight terminal of the present invention using the above-mentioned lead pin, and the electric compressor of the present invention using this airtight terminal, can each enjoy the effects of the metal material and lead pin of the present invention described above. Therefore, depending on the capacity of the electric compressor, it is possible to realize a very compact airtight terminal by reducing the diameter of the lead pin. Furthermore, the semiconductor laser apparatus of the present invention using the above-mentioned lead pins and / or stem base can enjoy the effects of the metal material and lead pins and / or stem base of the present invention described above. [Brief explanation of the drawing]

[0045] [Figure 1]The images show, for one embodiment of the present invention, a linear metal material (φ1.2 mm wire made of a 50 mass% Cr-Cu composite), an SEM image of the material surface (left image), and magnified images of the cross-sectional structure in the stretching direction (axial direction) and the cross-sectional structure perpendicular to the stretching direction (radial direction) observed with an optical microscope (magnification 120x) (right image) and a magnified image of the cross-sectional structure in the stretching direction (radial direction) (center image). [Figure 2] These are magnified photographs of the microstructure in the rolling direction and perpendicular to the rolling direction, observed with an optical microscope, of a metallic material (rolled sheet material of 50 mass% Cr-Cu composite) obtained by rolling a 50 mass% Cr-Cu fused body (a Cr sintered body into which Cu is dissolved) into a plate shape using a flat roll. [Figure 3] Figure 3(a) is a schematic representation of a compression-sealed glass hermetic seal, with Figure 3(a) being a plan view and Figure 3(b) being a cross-sectional view along line AA in Figure 3(a). [Figure 4] Figure 4(a) schematically shows a lead pin made of the metal material of the present invention, and Figure 4(b) schematically shows a stem base made of the metal material of the present invention. In Figure 4(a), the upper part shows a radial cross-section of the lead pin, and the lower part shows an axial cross-section. In Figure 4(b), the upper part shows a cross-section of the stem base in the direction of the plate surface, and the lower part shows a cross-section in the direction of the plate thickness. [Figure 5] Figure 5(A) is a schematic diagram of a compression-sealed glass hermetic seal used to examine the bonding reliability when the metal material of the present invention is used in the "lead pin of a compression-sealed glass hermetic seal equipped in an airtight terminal" (a conceptual diagram showing the dimensions and thermal expansion coefficient of the constituent members, compressive stress inside the seal, etc.). Figure 5(A) is a schematic longitudinal section of the entire seal, Figure 5(B) is a schematic plan view of the same, and Figure 5(C) is a schematic plan view of the sealing glass. [Figure 6] Figure 6(A) is a schematic diagram of a compression-sealed glass hermetic seal used to examine the bonding reliability when the metal material of the present invention is used in the "lead pin of a compression-sealed glass hermetic seal equipped in an airtight terminal" (a conceptual diagram showing the dimensions and thermal expansion coefficient of the constituent members, compressive stress inside the seal, etc.). Figure 6(B) is a schematic longitudinal section of the entire seal, Figure 6(C) is a schematic plan view of the housing (stem base) and sealing glass, and Figure 6(A) is a schematic plan view of the sealing glass and lead pin. [Figure 7] Figure 7(A) is a schematic diagram of a compression-sealed glass hermetic seal used to examine the bonding reliability when the metal material of the present invention is used in the "lead pins of a compression-sealed glass hermetic seal equipped in a semiconductor laser device" (a conceptual diagram showing the dimensions and thermal expansion coefficient of the constituent members, compressive stress inside the seal, etc.). Figure 7(A) is a schematic longitudinal cross-section of the entire seal, and Figure 7(B) is a schematic plan view of the same. [Figure 8] Figure 8(A) is a schematic diagram of a compression-sealed glass hermetic seal used to examine the bonding reliability when the metal material of the present invention is used in the lead pins and housing (stem base) of a compression-sealed glass hermetic seal equipped in a semiconductor laser device. Figure 8(B) is a schematic diagram of the overall vertical cross-section of the seal, and Figure 8(B) is a schematic plan view of the same. [Modes for carrying out the invention]

[0046] <Basic composition of the metal material of the present invention> The metallic material of the present invention consists of a [Cr or / and Mo]-Cu composite having a metallic structure in which a Cr phase and / or a Mo phase is dispersed in a Cu matrix. This [Cr or / and Mo]-Cu composite is a diameter-reduced stretched material for powder metallurgy molded bodies, and is characterized in that, when the cross-sectional structure is observed with an optical microscope (for example, at 120x magnification), it has a cross-sectional structure in the stretching direction in which layered or linear Cr phases and / or Mo phases are dispersed in the Cu matrix, and a cross-sectional structure perpendicular to the stretching direction in which flaky, small-piece, or granular Cr phases and / or Mo phases are dispersed in the Cu matrix. Herein, in the present invention, the [Cr and / or Mo]-Cu composite refers to a Cr-Cu composite having a metallic structure in which the Cr phase is dispersed in a Cu matrix, a Mo-Cu composite having a metallic structure in which the Mo phase is dispersed in a Cu matrix, and a Cr·Mo-Cu composite having a metallic structure in which the Cr phase and the Mo phase are dispersed in a Cu matrix.

[0047] Furthermore, in the present invention, a powder metallurgy molded body refers to a molded body obtained by applying the powder metallurgy method, and therefore includes molded bodies obtained in step (A) of the manufacturing method described later, for example, (i) those obtained through a step (a1) of sintering a molded body (compacted powder) of powder raw materials and a step (a2) of subjecting this sintered body to Cu fusion and / or densification treatment, and (ii) those obtained through a step of discharge plasma sintering (SPS sintering) or hot press sintering of powder raw materials. Furthermore, a diameter-reduced and stretched material of a powder metallurgy molded body refers to a material obtained by reducing the diameter and stretching the powder metallurgy molded body as described above by reducing the surface area (diameter-reducing and stretching process). Furthermore, in the present invention, "layered or linear Cr phase and / or Mo phase dispersed in a Cu matrix" includes the case where both "layered Cr phase and / or Mo phase" and "linear Cr phase and / or Mo phase" are dispersed (mixed) in the Cu matrix. Similarly, "flake-like, small-piece-like, or granular Cr phase and / or Mo phase dispersed in a Cu matrix" includes the case where two or more of the following are dispersed (mixed) in the Cu matrix: "flake-like Cr phase and / or Mo phase", "small-piece-like Cr phase and / or Mo phase", and "granular Cr phase and / or Mo phase".

[0048] The main forms (specific forms) of the metal material of the present invention include (1) a rod-shaped or wire-shaped metal material with the stretching direction as the axial direction and the direction perpendicular to the stretching direction as the radial direction, and (2) a plate-shaped metal material with the stretching direction as the thickness direction and the direction perpendicular to the stretching direction as the surface direction. For example, (1) can be used as a material for lead pins of compression-sealed glass hermetic seals, and (2) can be used as a material for stem bases of compression-sealed glass hermetic seals. Here, in the present invention, when we refer to "rod-shaped or wire-shaped metal material," "rod-shaped or wire-shaped material," "rod-shaped or wire-shaped base material," or "(a material) being stretched to reduce its diameter into a rod-shaped or wire-shaped form," "rod-shaped" means "rod-like material," and similarly, "wire-shaped" means "wire-like material." The radial cross-sectional shape of the rod-shaped or wire-shaped metal material in (1) above is not particularly limited, but is usually circular or polygonal (for example, hexagonal, octagonal, or hexagonal cross-sections). There is no strict distinction between rod-shaped material (rod material) and wire-shaped material (wire material), but generally, wire material (wire material) refers to material that can be wound up, while rod-shaped material (rod material) refers to material that cannot be wound up. Also, the planar (plate surface) shape of the plate-shaped metal material in (2) above is not particularly limited, but is usually circular, elliptical, or polygonal (for example, hexagonal, octagonal, or hexagonal cross-sections).

[0049] The metal material of the present invention is obtained by reducing the diameter of a material consisting of a [Cr and / or Mo]-Cu composite (powder metallurgy molded body) obtained through a process of sintering powder raw materials, and then reducing the diameter of the material by stretching it into a rod or wire shape. As a result, Cr particles and / or Mo particles dispersed in the Cu matrix are stretched into an elongated needle-like or rod-like shape in the stretching direction, creating a Cr phase and / or Mo phase, which has the characteristic cross-sectional structure in the stretching direction and perpendicular to the stretching direction as described above. Furthermore, a [Cr and / or Mo]-Cu composite having such a characteristic cross-sectional structure in the stretching direction and perpendicular to the stretching direction has unique properties as described later, particularly properties suitable for lead pins and stem bases of compression-sealed glass hermetic seals, and such a metal material ([Cr and / or Mo]-Cu composite) has not been known conventionally.

[0050] Figure 1 shows an SEM image of the surface of a linear metal material (φ1.2 mm wire made of a 50 mass% Cr-Cu composite), which is one embodiment of the present invention (left image), and magnified images of the cross-sectional structure in the stretching direction (axial direction) and the stretching direction perpendicular to the stretching direction (radial direction) observed with an optical microscope (magnification 120x) (right image) (center image). In these cross-sectional structures in the stretching direction and the direction perpendicular to the stretching direction (axial and radial directions), the darker areas are the Cr phase dispersed in the Cu matrix (lighter areas). The manufacturing conditions for this metal material were as follows: a prismatic material for surface reduction (thickness 9 mm) was subjected to surface reduction (diameter reduction stretching) by swaging and subsequent combined roll rolling, and then further surface reduction (diameter reduction stretching) was performed by roller die drawing (CRD) to obtain an outer diameter of φ1.2 mm.

[0051] As described above, this metallic material is made by reducing the surface area (reducing the diameter and stretching) of a Cr-Cu composite (powder metallurgy molded body) obtained by powder metallurgy, and then stretching it into a rod or linear shape. As a result, the Cr particles dispersed in the Cu matrix of the above material (powder metallurgy molded body) are stretched into a long, thin shape like a needle or rod (not a "flat" shape like the rolled plate material in Figure 2, which will be described later), resulting in the cross-sectional structure shown in Figure 1. Specifically, the cross-sectional structure in the stretching direction (axial direction) observed with an optical microscope is the Cr phase that has been stretched into the needle or rod shape, so layered or linear Cr phases are dispersed in the Cu matrix. These layered (which can also be described as "strip-shaped") or linear Cr phases exist in a state that extends long along the stretching direction (axial direction) of the material, and usually a mixture of layered and thin linear structures with a certain width is present. Of these, the layered structures with a certain width are thought to be Cr phases formed when multiple adjacent Cr particles are stretched and coalesced, for the reasons described below. In the axial (stretching direction) cross-sectional structure of Figure 1, the Cr phase consists of both layered structures with a certain width and thin linear structures, both distributed in the Cu matrix in a state where they are stretched in the axial direction of the material. On the other hand, the radial (perpendicular to stretching) cross-sectional structure observed with an optical microscope is a cross-section of the needle-shaped or rod-shaped Cr phase, resulting in a dispersion of flaky, small-piece, or granular Cr phase within the Cu matrix. Typically, the Cr phase in this cross-sectional structure consists of a mixture of flaky, small-piece, and granular structures. Here, the reason why the Cr phase in the cross-section perpendicular to the stretching direction appears as flaky or small pieces is thought to be because when the material (powder metallurgy molded body) is stretched to a reduced diameter, the Cr particles are elongated into needle-like or rod-like shapes, causing density variations in the distribution of the Cr phase perpendicular to the stretching direction, resulting in some Cr phases coming into close proximity, contacting, or accreting together. In the cross-sectional structure perpendicular to the stretching direction (radial direction) shown in Figure 1, fine Cr phase (flaky, small piece-like, or granular Cr phase) is relatively uniformly dispersed in the Cu matrix. This flaky, small piece-like, or granular Cr phase is, as described above, the cross-section perpendicular to the stretching direction (radial direction) of the Cr phase that has been elongated into needle-like or rod-like shapes.

[0052] Figure 1 shows the cross-sectional structure in the stretching direction and perpendicular to the stretching direction (axial and radial directions) of a linear metal material made of a Cr-Cu composite (φ1.2 mm wire made of 50 mass% Cr-Cu composite), which is one embodiment of the present invention. However, the metal materials of the present invention made of Mo-Cu composite and Cr·Mo-Cu composite will have similar cross-sectional structures in the stretching direction and perpendicular to the stretching direction (axial and radial directions). Furthermore, the cross-sectional structure (cross-sectional structure in the thickness direction and cross-sectional structure parallel to the plate surface) of plate materials cut radially from rod-shaped or linear metal materials of the present invention will have a similar form.

[0053] For comparison, Figure 2 shows the microstructure in the rolling direction and perpendicular to the rolling direction as observed with an optical microscope for a 50 mass%Cr-Cu composite sheet roll, i.e., a 50 mass%Cr-Cu fused body (a Cr sintered body into which Cu is dissolved) rolled into a sheet using a flat roll. In the case of this Cr-Cu composite sheet roll, there is no significant difference between the microstructure in the rolling direction and perpendicular to the rolling direction. In both the rolling direction and perpendicular to the rolling direction, the Cr phase is dispersed in the Cu matrix in a pseudo-network pattern at a reduction ratio of 75%, while at a reduction ratio of 98%, the Cr phase, stretched in one direction, is dispersed in the Cu matrix in a flattened (pseudo-fibrous) manner. Comparing this with Figure 2, it can be seen that the material of the present invention shown in Figure 1 has a very distinctive microstructure in the stretching direction and perpendicular to the stretching direction (axial and radial directions). In particular, regarding the cross-sectional structure perpendicular to the stretching direction, the rolled plate material in Figure 2 has a form in which the Cr phase is thinly stretched in a flattened (pseudo-fibrous) shape, whereas the material of the present invention in Figure 1 has a form in which the Cr phase is dispersed in a flaky, small-piece, or granular shape (the cross-sectional shape perpendicular to the stretching direction of the Cr phase, which is elongated in a needle-like or rod-like shape in the stretching direction), exhibiting a completely different form.

[0054] Here, the Cr-Cu composite sheet rolled material shown in Figure 2 was developed for use as a heat sink for bonding semiconductors and ceramics with low thermal expansion coefficients between the sheet surface. Due to the cross-sectional structure described above, the thermal expansion coefficient in the sheet surface direction (rolling direction and direction perpendicular to rolling) is small, while the thermal expansion coefficient in the sheet thickness direction is large. Therefore, if a shaft body with the rolling direction as the axial direction is cut from this sheet rolled material and used as a lead pin for a compression-sealed glass hermetic seal, the thermal expansion coefficient in the radial direction of the pin will be anisotropic. This results in a large difference in thermal expansion between the lead pin and the sealing glass in one direction of the cross-section in the radial direction of the pin, leading to cracks in the sealing glass and other issues, resulting in insufficient bonding reliability. Furthermore, if the above sheet rolled material is used as a stem base for a compression-sealed glass hermetic seal, the low thermal expansion coefficient in the sheet surface direction results in low compressive stress on the sealing glass in the radial direction, while the high thermal expansion coefficient in the sheet thickness direction results in high interfacial shear stress with the sealing glass in the sheet thickness direction. Therefore, insufficient bonding reliability cannot be obtained. Furthermore, the Cr phase, which has a lower thermal conductivity than the Cu phase and is flattened by rolling, obstructs heat flow in the thickness direction of the sheet, resulting in low thermal conductivity in the thickness direction and problems with heat dissipation. In contrast, the metal material of the present invention and the metal components composed thereof (particularly the lead pins and stem bases of compression-sealed glass hermetic seals) have unique properties (characteristics) that are completely different from conventionally known metal materials, as will be explained later in "Characteristics of the Metal Material of the Present Invention," etc. These characteristics are particularly suitable for lead pins and stem bases, and do not cause any of the problems seen in the rolled Cr-Cu composite sheet material (Figure 2) mentioned above.

[0055] Figure 3 schematically shows a compression-sealed glass hermetic seal in which the metal material of the present invention is used as the material for lead pins and stem bases, where Figure 3(a) is a plan view and Figure 3(b) is a cross-sectional view along line AA in Figure 3(a). This compression-sealed glass hermetic seal consists of a stem base 1, lead pins 2, sealing glass 3, etc., and is a seal in which the lead pins 2 are airtightly sealed through an insertion hole 4 that penetrates the stem base 1 via the sealing glass 3 (sealing material). Lead pins are also sometimes called leads, metal pins, pins, or feedthroughs. Conventionally, materials such as Fe-Ni alloy, Kovar, and stainless steel (SUS410, SUS430, SUH446, etc.) have been used. The lead pins made of the metal material of the present invention can replace these conventional products and exhibit superior performance compared to them. The stem base, also known as the housing, stem, base, or metal eyelet, has traditionally been made from materials such as carbon steel (SC material, SPC material, etc.), stainless steel (SUS304, SUS410, etc.), and chromium steel. The stem base made from the metal material of the present invention can replace these conventional products and exhibits superior performance compared to them.

[0056] Here, the lead pin and stem base, which are made of the metal material of the present invention, will be described in detail later, but will be briefly explained below. Figure 4(a) schematically shows a lead pin made of the metal material of the present invention, and Figure 4(b) schematically shows a stem base made of the metal material of the present invention. The upper part of Figure 4(a) schematically shows a radial cross-section of the lead pin, and the lower part shows an axial cross-section. The upper part of Figure 4(b) schematically shows a cross-section in the direction of the plate surface (cross-section parallel to the plate surface), and the lower part shows a cross-section in the direction of the plate thickness of the stem base. These drawings schematically show cross-sections of the Cr phase and / or Mo phase generated by stretching Cr particles and / or Mo particles dispersed in a Cu matrix into a needle-like or rod-like shape in the stretching direction.

[0057] In the axial cross-section of Figure 4(a) (bottom view) and the thickness-direction cross-section of Figure 4(b) (bottom view), the short linear elements represent "layered or linear Cr phase and / or Mo phase" dispersed in the Cu matrix, corresponding to the cross-sectional structure in the photograph on the right side of Figure 1. Furthermore, in the radial cross-section of Figure 4(a) (top view) and the plane-direction cross-section of Figure 4(b) (top view), the dot-like elements represent "flake-like, small-piece-like, or granular Cr phase and / or Mo phase" dispersed in the Cu matrix, corresponding to the cross-sectional structure in the photograph in the center of Figure 1. The lead pin shown in Figure 4(a) is made of the metal material of the present invention described above, and is composed of a rod-shaped or wire-shaped metal material whose stretching direction is axial and whose stretching direction is radial. Typically, a lead pin (pin base material) is obtained by cutting a rod-shaped or wire-shaped metal material to an appropriate length and cutting out a pin-shaped member. On the other hand, the stem base in Figure 4(b) is made of the metal material of the present invention described above, which is a plate-shaped metal material whose stretching direction is the thickness direction and whose stretching direction is perpendicular to the surface direction. Typically, a rod-shaped or wire-shaped metal material is cut radially to an appropriate thickness (i.e., the material is sliced ​​into rings) to cut out a plate material, which is then processed into a stem base.

[0058] <Properties of the metallic material of the present invention> Next, the properties of the metal material of the present invention will be explained using examples such as its application to the lead pins and stem base of a compression-sealed glass hermetic seal. The metal material of the present invention has a cross-sectional structure in the stretching direction and perpendicular to the stretching direction as described above, and therefore has unique properties (characteristics) that differ from conventional metal materials used in lead pins and stem bases of compression-sealed glass hermetic seals, or other conductive members. Specifically, this metal material (a [Cr and / or Mo]-Cu composite, which is a diameter-reduced stretched material for powder metallurgy molded bodies) has a thermal expansion coefficient in the stretching direction < thermal expansion coefficient perpendicular to the stretching direction, meaning that the thermal expansion coefficient in the stretching direction is relatively small, and it also has high electrical conductivity and thermal conductivity in the stretching direction. Among these, those whose properties have been further optimized as described later can have a thermal expansion coefficient in the stretching direction close to that of sealing glass, and have significantly higher electrical conductivity in the stretching direction compared to Ni-Fe alloys widely used for lead pins, and significantly higher thermal conductivity in the stretching direction compared to carbon steel widely used for stem bases. Furthermore, the metal material of the present invention is a diameter-reduced drawn material of a powder metallurgy molded body, and has the cross-sectional structure in the direction of stretching and the direction perpendicular to stretching as described above. Therefore, its coefficient of thermal expansion perpendicular to stretching is the same in any direction perpendicular to stretching, and its coefficient of thermal expansion perpendicular to stretching is isotropic.

[0059] Therefore, a rod-shaped or wire-shaped metal material (a [Cr and / or Mo]-Cu composite, which is a diameter-reduced drawn material for powder metallurgy molded bodies) with the above-mentioned stretching direction as the axial direction and the direction perpendicular to the stretching direction as the radial direction has an axial thermal expansion coefficient < radial thermal expansion coefficient, a relatively small axial thermal expansion coefficient, an isotropic radial thermal expansion coefficient, and high axial electrical conductivity. Among these, those with further optimized properties, as described later, can have an axial thermal expansion coefficient close to that of sealing glass, and have significantly higher axial electrical conductivity compared to Ni-Fe alloys and the like, which are widely used for lead pins. Furthermore, a plate-shaped metal material (a [Cr and / or Mo]-Cu composite, which is a diameter-reduced drawn material for powder metallurgy molded bodies) with the stretching direction as the thickness direction and the direction perpendicular to the stretching direction as the surface direction has a thermal expansion coefficient in the surface direction that is sufficient for a stem base, and has a relatively small thermal expansion coefficient in the thickness direction, an isotropic thermal expansion coefficient in the surface direction, and high thermal conductivity in the thickness direction. Among these, those with further optimized properties, as described later, can have a thermal expansion coefficient in the thickness direction close to that of sealing glass, and have significantly higher thermal conductivity in the thickness direction compared to carbon steel and other materials widely used for stem bases. As described in the examples below, the metal materials of the present invention (examples of invention) all have a coefficient of thermal expansion perpendicular to the extension (radial) direction > coefficient of thermal expansion in the extension (axial) direction, and have a relatively low coefficient of thermal expansion in the extension (axial) direction, close to the coefficient of thermal expansion of sealing glass (however, the coefficient of thermal expansion differs depending on the type of glass). Furthermore, the metal materials of the present invention (examples of invention) have a significantly higher axial electrical conductivity compared to 50.5 mass% Ni-Fe (comparative example of No. 30), which is widely used in conventional lead pins, and also have a significantly higher thermal conductivity compared to carbon steel, which is widely used in conventional stem bases, which has a thermal conductivity of about 40-60 W / m·K.

[0060] As described above, the metal materials of the present invention generally possess characteristics not found in conventional metal materials, such as "thermal expansion coefficient in the stretching direction < thermal expansion coefficient in the direction perpendicular to stretching, relatively small thermal expansion coefficient in the stretching direction, isotropic thermal expansion coefficient in the direction perpendicular to stretching, and high electrical conductivity and thermal conductivity in the stretching direction." Furthermore, they have the following significant features. First, the magnitude of the thermal expansion coefficient in the stretching direction can be changed (adjusted) by selecting the blending ratio (content) of Cr and / or Mo in the [Cr and Mo]-Cu composite and the reduction ratio when the material is stretched to reduce its diameter. In other words, the magnitude of the axial thermal expansion coefficient can be changed (adjusted) for rod-shaped or wire-shaped metal materials, and the magnitude of the thermal expansion coefficient in the thickness direction can be changed (adjusted) for plate-shaped metal materials. Specifically, if the reduction ratio of the material during diameter reduction and stretching is the same, the higher the proportion of Cr and / or Mo, and if the proportions of Cr and / or Mo are the same, the higher the reduction ratio of the material during diameter reduction and stretching (up to about 97%), the lower the coefficient of thermal expansion in the stretching direction. To illustrate this using the examples described later, for example, in the examples, metal materials No. 5, 10, 15, and 20 (inventive examples) are made of Cr-Cu composites with a reduction ratio of 90.3% and different proportions of Cr, and the coefficient of axial thermal expansion is lower as the proportion of Cr increases. Also, metal materials No. 24 and 29 (inventive examples) are made of Mo-Cu composites with a reduction ratio of 97.6% and different proportions of Mo, and metal materials No. 37 and 39 (inventive examples) are made of Mo-Cu composites with a reduction ratio of 80% and different proportions of Mo, and in all cases, the coefficient of axial thermal expansion is lower as the proportion of Mo increases. On the other hand, for example, metal materials No. 7 to 12 (inventive examples) consist of Cr-Cu composites with a Cr content of 45 mass% and different reduction ratios, and metal materials No. 26 to 29 (inventive examples) consist of Mo-Cu composites with a Mo content of 40 mass% and different reduction ratios. In both cases, the axial thermal expansion coefficient decreases as the reduction ratio increases.Therefore, the axial thermal expansion coefficient of the lead pin and the thickness-direction thermal expansion coefficient of the stem base can be brought as close as possible to the thermal expansion coefficient of the sealing glass, thereby maximizing the reliability of the joint between the lead pin and stem base and the sealing glass, which is a challenge for compression-sealed glass hermetic seals. In particular, as will be described later, it is preferable that the values ​​of τ1 / P1 (=[thickness-direction compressive shear stress τ1 acting from the stem base to the sealing glass interface] / [radial compressive stress P1 from the stem base to the sealing glass]) and τ3 / P2 (=[axial compressive shear stress τ3 acting from the lead pin to the sealing glass interface] / [radial compressive stress P2 from the sealing glass to the lead pin]) are positive and as small as possible, as this increases the reliability of the joint between the stem base and lead pin and the sealing glass. It is possible to adjust the thickness-direction thermal expansion coefficient of the stem base and the axial thermal expansion coefficient of the lead pin (bringing them closer to the thermal expansion coefficient of the sealing glass) so that τ1 / P1 and τ3 / P2 are such.

[0061] Furthermore, the electrical conductivity and thermal conductivity in the stretching direction of this metal material change depending on the reduction ratio during diameter reduction stretching. If the blending ratio of Cr and / or Mo is the same, the electrical conductivity and thermal conductivity in the stretching direction increase as the reduction ratio increases up to about 97% during diameter reduction stretching. In other words, the larger the reduction ratio, the greater the axial electrical conductivity for rod-shaped or wire-shaped metal materials, and the greater the thermal conductivity in the thickness direction for plate-shaped metal materials. For example, looking at the metal materials No. 7 to 12 (inventive examples with a Cr blending ratio of 45 mass%) and No. 26 to 29 (inventive examples with a Mo blending ratio of 40 mass%) mentioned above, the greater the reduction ratio, the greater the electrical conductivity and thermal conductivity in the stretching direction. Therefore, by changing the reduction ratio, the axial electrical conductivity or the thermal conductivity in the thickness direction can be appropriately adjusted according to the application of the metal material. As is clear from the examples, the tensile electrical conductivity and tensile thermal conductivity also change depending on the component composition of the metal material (the proportion of Cr and / or Mo), and the lower the proportion of Cr and / or Mo, the higher the tensile electrical conductivity and tensile thermal conductivity.

[0062] Therefore, with regard to compression-sealed glass hermetic seal applications, the linear or rod-shaped metal material of the present invention is very suitable for lead pins, and the plate-shaped metal material of the present invention is very suitable for stem bases. Furthermore, this plate-shaped metal material has a certain level of thermal expansion coefficient in the plate surface direction, and the thermal expansion coefficient in the thickness direction is less than the thermal expansion coefficient in the plate surface direction. Moreover, by selecting the blending ratio (content) of Cr and / or Mo and the reduction ratio when the material is stretched to reduce its diameter, the magnitude of the thermal expansion coefficient in the thickness direction can be adjusted and optimized. In particular, it can highly satisfy the thermal expansion characteristics required for stem bases (the thermal expansion coefficient in the plate surface direction is somewhat higher than the thermal expansion coefficient of the sealing glass, and the thermal expansion coefficient in the thickness direction is as close as possible to the thermal expansion coefficient of the sealing glass). On the other hand, by increasing the reduction ratio when stretched to reduce its diameter, the thermal conductivity in the thickness direction can be increased, and the heat dissipation required for stem bases can be highly satisfied.

[0063] Here, regarding the thermal properties of the metallic material of the present invention, as described above, the reason why the thermal expansion coefficient in the stretching direction is smaller than that in the direction perpendicular to stretching is thought to be because the expansion of Cu in the stretching direction is suppressed by the shear stress at the interface between the Cr phase and / or Mo phase, which has been stretched into a needle-like or rod-like shape by diameter reduction stretching, and Cu. However, since the range affected by the shear stress of one Cr phase and / or Mo phase in the cross section perpendicular to stretching is limited, the higher the density of the Cr phase and / or Mo phase in the cross section perpendicular to stretching, that is, the higher the blending ratio (content) of Cr and / or Mo, the smaller the thermal expansion coefficient in the stretching direction tends to be. Also, the longer the stretched length of the Cr phase and / or Mo phase in the stretching direction, the greater the shear stress. Therefore, as will be described later, if the reduction ratio when manufacturing the metallic material of the present invention is large, the stretched length of the Cr phase and / or Mo phase in the stretching direction becomes longer, and the thermal expansion coefficient in the stretching direction becomes smaller. In other words, the larger the reduction ratio, the smaller the thermal expansion coefficient in the stretching direction tends to be. Furthermore, the thermal expansion coefficient perpendicular to the stretching direction tends to increase with increasing reduction in area ratio. This is because a larger reduction in area ratio results in smaller diameters of the Cr phase and / or Mo phase in the direction perpendicular to the stretching direction, thus reducing the restraining force on Cu in that direction. From the above, it can be seen that the thermal expansion coefficients in the stretching direction and perpendicular to the stretching direction can be adjusted by selecting the blending ratio (content) of Cr and / or Mo and the reduction in area ratio when the material is stretched to reduce its diameter. Furthermore, the reason why the electrical conductivity and thermal conductivity in the stretching direction increase with increasing area reduction is thought to be that, as the area reduction increases, the Cu phase is also stretched in the stretching direction by the Cr phase and / or Mo phase that are stretched in the stretching direction, and as a result, current and heat flow preferentially in the stretching direction.

[0064] <Preferred conditions for the metallic material of the present invention> The properties of the metal material of the present invention are as described above: thermal expansion coefficient in the stretching direction < thermal expansion coefficient perpendicular to stretching, relatively small thermal expansion coefficient in the stretching direction, isotropic thermal expansion coefficient perpendicular to stretching, high electrical conductivity in the stretching direction, and high thermal conductivity in the stretching direction. However, for optimal thermal properties, the average thermal expansion coefficient in the stretching direction from 30°C to 450°C is 7.0 to 12.0 × 10⁻⁶. -6The mean coefficient of thermal expansion perpendicular to the extension direction from 30°C to 450°C is 18.0 × 10⁻¹⁰ / K. -6 It is preferable that the temperature is less than or equal to / K and that [average thermal expansion coefficient in the stretching direction from 30°C to 450°C] < [average thermal expansion coefficient in the direction perpendicular to stretching from 30°C to 450°C].

[0065] The average coefficient of thermal expansion in the stretching direction from 30°C to 450°C is 7.0 to 12.0 × 10⁻⁶. -6 A value of / K is particularly effective in obtaining the effects described above. That is, if the average thermal expansion coefficient in the stretching direction is within the above range, it will be close to the thermal expansion coefficient of the sealing glass, which is preferable because it makes it easier to obtain bonding reliability with the sealing glass. Furthermore, the thermal expansion coefficient in the stretching direction can be appropriately adjusted (selected) within the above range depending on the thermal expansion coefficient of the sealing glass used. As mentioned earlier, the average thermal expansion coefficient in the stretching direction can be adjusted by changing the component composition of the metal material (the blending ratio of Cr or / and Mo) and the reduction ratio when the material is stretched to reduce its diameter. Furthermore, regarding the characteristic thermal properties of the metal material of the present invention, namely that the thermal expansion coefficient perpendicular to the extension direction is greater than the thermal expansion coefficient in the extension direction, in the examples (inventive examples) described later, the difference between the average thermal expansion coefficient in the extension direction (axial direction) from 30°C to 450°C and the average thermal expansion coefficient perpendicular to the extension direction (radial direction) from 30°C to 450°C is 2.0 × 10⁻⁶. -6 It is above / K.

[0066] The reason for using the average thermal expansion coefficient from 30°C to 450°C as the average thermal expansion coefficient in the stretching direction and the direction perpendicular to stretching is as follows: Sealing glass is used with a glass transition temperature (Tg) in the range of approximately 410 to 560°C. However, since the volume of sealing glass is determined at a temperature around the glass transition temperature - 30°C, the volume of sealing glass with a glass transition temperature of approximately 410 to 560°C is determined at a temperature of approximately 380 to 530°C. However, since the average thermal expansion coefficient in this temperature range does not change significantly with temperature, 450°C, which is approximately the midpoint of 380 to 530°C, is used as a representative temperature, and the "average thermal expansion coefficient from 30°C to 450°C" is used.

[0067] Furthermore, the metal material of the present invention has an optimal property of having an electrical conductivity of 20.0 × 10 in the stretching direction.6 Preferably, the thermal conductivity in the stretching direction is 180 W / m·K or higher, or the electrical conductivity in the stretching direction is 20.0 × 10 6 If the thermal conductivity in the extension direction is 180 W / m·K or higher, it is particularly effective in obtaining the effects described above. 6 When "S / m or more" is replaced with volume resistivity, which is the reciprocal of electrical conductivity, it becomes "volume resistivity of 5.0 μΩ·cm or less". In terms of volume resistivity, it is preferable that the volume resistivity in the stretching direction (and the axial volume resistivity described later) be 5.0 μΩ·cm or less. High electrical conductivity in the stretching direction is a particularly useful property for lead pins, but if the electrical conductivity in the stretching direction (axial direction for rod-shaped or wire-shaped metal materials) is 20.0 × 10⁻¹⁰ 6 A level of S / m or higher represents a significantly higher axial electrical conductivity compared to conventional Ni-Fe alloys widely used in lead pins. This allows for the conduction of large currents even in small-diameter lead pins, and significantly reduces the amount of heat generated during current flow. As shown in the examples described later, the axial electrical conductivity of 50.5 mass% Ni-Fe (comparative example of No. 30), which is conventionally used in lead pins, is 2.81 × 10⁻¹⁰. 6 While the electrical conductivity in the stretching direction (axial direction) of the metal material of the present invention is an order of magnitude larger than that, it can be seen that a significantly higher electrical conductivity can be obtained.

[0068] Furthermore, while high thermal conductivity in the stretching direction is a particularly useful characteristic for stem bases, a thermal conductivity of 180 W / m·K or higher in the stretching direction (or thickness direction in the case of plate-shaped metal materials) is significantly higher than that of carbon steel and other materials commonly used in conventional stem bases, resulting in particularly high heat dissipation characteristics in the thickness direction of the stem base. While the thermal conductivity of carbon steel conventionally used in stem bases is around 40-60 W / m·K, as shown in the examples described later, the thermal conductivity of the metal material of the present invention in the stretching direction is several times higher, demonstrating that significantly higher thermal conductivity in the stretching direction is achieved. As mentioned earlier, the electrical conductivity and thermal conductivity of metallic materials in the stretching direction can also be adjusted by selecting the component composition of the metallic material (the proportion of Cr and / or Mo) and the reduction ratio when the material is stretched to reduce its diameter.

[0069] Here, the properties of the metallic material of the present invention are determined as follows. The thermal expansion coefficients in the stretching direction and the direction perpendicular to the stretching direction are measured using a push-rod type displacement detection method. The average thermal expansion coefficients in the stretching direction and the direction perpendicular to the stretching direction from 30°C to 450°C are calculated by measuring the thermal expansion coefficients in the stretching direction and the direction perpendicular to the stretching direction, respectively, using the push-rod type displacement detection method, determining the difference in elongation between 30°C and 450°C, and dividing that value by the temperature difference of 420°C (= 450°C - 30°C). Furthermore, the electrical conductivity in the stretching direction is measured using a commercially available electrical resistance measuring device with the DC four-terminal method (measurement temperature: room temperature, atmosphere: air). Furthermore, since the thermal conductivity in the stretching direction (thermal conductivity at room temperature) cannot be measured directly due to the small diameter of the metal material, it is calculated from the electrical conductivity based on the Wiedemann-Franz law. That is, the ratio of the thermal conductivity to the electrical conductivity of a metal is equal to the product of the absolute temperature T and a constant L (Lorentz constant) that does not depend on the type of metal (thermal conductivity κ / electrical conductivity σ = LT L: 2.44 × 10⁻¹⁴). -8 WΩK -2 Therefore, the thermal conductivity in the stretching direction can be calculated from the electrical conductivity in the stretching direction.

[0070] The metallic material of the present invention has the characteristic cross-sectional structure in the stretching direction and perpendicular to the stretching direction as shown in Figure 1, and therefore possesses the unique properties (characteristics) described above. Therefore, the content (mixing ratio) of Cr and / or Mo in the [Cr and Mo]-Cu composite constituting the metallic material of the present invention is not particularly limited, however, a total Cr and / or Mo content of 35 to 60 mass% is particularly effective in obtaining the thermal properties described above. This is because, when the total Cr and / or Mo content decreases, the restraining force of Cu by the Cr phase and / or Mo phase decreases, making it difficult to reduce the thermal expansion coefficient of the material, especially the thermal expansion coefficient in the stretching direction. On the other hand, when the total Cr and / or Mo content increases, the workability of the material decreases, making it difficult to perform surface reduction processing (diameter reduction stretching) into a rod or wire shape, and also making it difficult to increase the electrical conductivity in the stretching direction and the thermal conductivity in the stretching direction.

[0071] In the metallic material of the present invention, when comparing Cr (Cr phase) and Mo (Mo phase) blended with Cu, there is a tendency that (i) Cr improves the processability (rollability, etc.) of the material compared to Mo, (ii) Mo makes it easier to achieve higher electrical conductivity in the stretching direction than Cr, and (iii) Mo makes it easier to achieve lower thermal expansion coefficient in the stretching direction than Cr (the tendencies of (ii) and (iii) above can also be confirmed in the examples described later). Therefore, for example, in a Cr·Mo-Cu composite, the thermal properties can be balanced by adjusting the content and ratio of Cr and Mo according to the required thermal properties, thereby obtaining optimal thermal properties.

[0072] <Method for manufacturing the metal material of the present invention> Next, the method for producing the metal material of the present invention will be described. The metal material of the present invention can generally be manufactured by reducing the surface area (reducing the diameter of the material) of a [Cr and / or Mo]-Cu composite (powder metallurgy molded body) obtained through a process of sintering powder raw materials, and then reducing the diameter of the material to make it a rod or wire shape. The rod or wire shape produced through such a series of processes (the [Cr and / or Mo]-Cu composite, which is the diameter-reduced and drawn material of the powder metallurgy molded body) will have a structure in which the Cr phase and / or Mo phase are elongated in the axial direction (longitudinal direction) within the Cu matrix, as described above. That is, it will have a cross-sectional structure in the direction of stretching (axial direction) in which layered or linear Cr phases and / or Mo phases are dispersed within the Cu matrix, and a cross-sectional structure in the direction perpendicular to stretching (radial direction) in which flake-like, small-piece-like, or granular Cr phases and / or Mo phases are dispersed within the Cu matrix.

[0073] The following describes preferred methods for manufacturing the metal material of the present invention. This manufacturing method comprises a step (A) of obtaining a material for surface reduction processing consisting of a [Cr and / or Mo]-Cu composite through a step of sintering powder raw materials, and a step (B) of reducing the surface area (reducing diameter stretching) of the material obtained in step (A) to reduce the diameter and stretch it into a rod or wire shape. As will be described later, process (A) also includes cases where the powder raw material is subjected to Cu fusion or densification treatment after sintering, or where the powder raw material is subjected to discharge plasma sintering or hot press sintering.

[0074] In process (A), material for surface reduction can be obtained in various ways, but the basic ways are (i) and (ii) below. Each way should be carried out according to conventional methods. (i) A material for surface reduction made of a [Cr and / or Mo]-Cu composite is obtained by (a1) sintering a molded body (compacted powder) of powder raw materials to make a sintered body, and (a2) subjecting this sintered body to Cu fusion and / or densification treatment. (ii) A material for surface reduction is obtained by subjecting the powder raw material to a process of discharge plasma sintering (SPS sintering) or hot press sintering, which consists of a [Cr and / or Mo]-Cu composite. In the embodiment of (i) above, in step (a1), powder raw material is filled into a mold and molded according to a conventional method, and the molded body (compacted powder) is sintered in a predetermined atmosphere to form a sintered body. Next, in step (a2), at least one of Cu immersion and densification treatment is performed on the sintered body to make it a material for surface reduction processing.

[0075] In the Cu infusion process for sintered bodies, for example, a Cu plate or Cu powder for Cu infusion may be placed on a molded body made from powder raw materials, and it may first be heated to the sintering temperature to sinter it, and then the temperature may be raised to the Cu infusion temperature to carry out the Cu infusion. It is preferable to perform surface grinding (for example, surface grinding using a milling machine or grinding wheel) on the Cu infused body obtained in this process in order to remove any excess pure Cu remaining on the surface. Densification treatment aims to densify a porous sintered body. There are no specific restrictions on the type of treatment, but typical examples include hot extrusion, HIP treatment, hot pressing, and plasma discharge treatment (SPS treatment), and one or more of these can be performed. If the sintered body is not subjected to Cu infiltration, it is preferable to perform this densification treatment to densify the sintered body. On the other hand, the sintered body can be densified by Cu infiltration, and the above-mentioned densification treatment may be performed after this Cu infiltration. In HIP (Hot Isostatic Pressing), one of the densification processes, the sintered body is pressurized (hydrostatically) and heated in a pressure vessel using an inert gas as the pressure medium. In hot press processing, the sintered body is heated and pressurized in a mold. In plasma discharge processing (SPS processing), the sintered body is heated and pressurized in a mold using pulsed current.

[0076] In the embodiment of (ii) above, a dense sintered body is obtained by discharge plasma sintering (SPS sintering) or hot press sintering, and can be used as is as a material for surface reduction processing. In discharge plasma sintering, powdered raw materials packed into a mold are sintered by pulsed current heating while under pressure. In contrast, in hot press sintering, powdered raw materials are placed in a mold and sintered by heating and applying pressure. Therefore, specific embodiments of process (A) include, for example, (a) to (d) below. However, it is not limited to these.

[0077] (a) A material for surface reduction is obtained by molding Cr powder and / or Mo powder, or by molding a mixed powder of Cr powder and / or Mo powder and Cu powder, sintering the molded body to form a sintered body, and then dissolving Cu into the sintered body to obtain a material for surface reduction consisting of a [Cr and / or Mo]-Cu composite. (i) A mixed powder of Cr powder and / or Mo powder and Cu powder is molded, and this molded body is sintered to form a sintered body. This sintered body is then subjected to one of the following densification treatments: hot extrusion, HIP treatment, hot press treatment, or discharge plasma treatment (SPS treatment) to obtain a material for surface reduction made of a [Cr and / or Mo]-Cu composite. (c) A material for surface reduction made of a [Cr or / and Mo]-Cu composite is obtained by molding Cr powder and / or Mo powder, or by molding a mixed powder of Cr powder and / or Mo powder and Cu powder, sintering the molded body to make a sintered body, dissolving Cu into the sintered body, and then applying one of the following densification treatments: hot extrusion, HIP treatment, hot press treatment, or discharge plasma treatment (SPS treatment). (e) A material for surface reduction is obtained by discharging plasma sintering or hot press sintering a mixed powder of Cr powder and / or Mo powder and Cu powder, consisting of a [Cr and / or Mo]-Cu composite. The material obtained in process (A) for surface reduction is typically a round bar or a square bar (e.g., a polygonal cross-section).

[0078] Process (B) can be any process as long as the material can be reduced in diameter and stretched into a rod or wire shape by reducing its surface area (diameter reduction stretching). For example, it can be carried out by combining one or more of the following processes: roll rolling, swaging, and hot extrusion. Furthermore, a finish drawing process (wire drawing) may be performed afterward. Roll rolling can be performed using methods such as grooved roll rolling and combined roll rolling. Grooved roll rolling involves reducing the surface area (reducing diameter and stretching) of a material (round bar, square bar, etc.) into a rod or linear shape using grooved rolling rolls. Combined roll rolling involves reducing the surface area (reducing diameter and stretching) of a material (round bar, square bar, etc.) into a rod or linear shape using grooved rolling rolls with multiple stands (e.g., 20 stands or more). Swaging is a type of compression process (cold forging) in which a die is used to compress the material radially, reducing its outer diameter and extending its length (reducing diameter and extending). For example, the material is compressed while the die is rotated, and its length is extended (reducing diameter and extending). In hot extrusion, the material is placed in a container and extruded through the die holes by a ram.

[0079] When performing a finish drawing process (wire drawing), it is usually done as the final surface reduction process (diameter reduction and stretching). However, for example, since the material for the stem base has a large diameter, this finish drawing process may not be performed. In drawing processes, known processing methods such as simple drawing (wet method, dry method) and roller die drawing (CRD) can be used. There are no particular restrictions on the total reduction ratio of the material in process (B), but if the reduction ratio is too small, it becomes difficult to obtain the microstructure of the metal material of the present invention, so it is desirable that the total reduction ratio of the material in process (B) be 60% or more. Furthermore, there is no particular upper limit on the total reduction ratio of the material in process (B), but there is a practical upper limit depending on the blending ratio of Cr and / or Mo and the manufacturing equipment (processing means for reduction). Here, the reduction ratio (percentage of reduction in cross-sectional area) can be calculated as follows: if the radial cross-sectional area of ​​the material before the reduction process in step (B) is a, and the radial cross-sectional area of ​​the material after the process in step (B) is b, then the reduction ratio (%) = [(ab) / a] × 100.

[0080] The surface of the rod-shaped or wire-shaped metal material obtained in process (B) may have scratches or irregularities due to the surface reduction (diameter reduction and stretching) process in process (B). Depending on the degree of such scratches or irregularities, a gap may form between the material and the sealing glass, for example, in the case of lead pin applications, potentially impairing the sealing state. Furthermore, it may be necessary to further improve the dimensional accuracy of the outer diameter of the material obtained in process (B). For this reason, in the manufacturing method of the present invention, a further process (C) may be performed as needed, primarily for the purpose of eliminating the scratches or irregularities on the material surface or improving the dimensional accuracy, in which the surface of the rod-shaped or wire-shaped metal material obtained in process (B) may be ground or polished. This process (C) may be performed on the rod-shaped or wire-shaped metal material (raw material) as obtained in process (B), or on the rod-shaped or wire-shaped material obtained in process (B) that has been cut to a predetermined length, for example, cut for use as a lead pin. There are no particular restrictions on the method of grinding or polishing the material surface in this step (C), but since it deals with relatively small-diameter rod-shaped or wire-shaped materials, it is preferable to use centerless grinding and polishing. While rod-shaped or wire-shaped metal materials used for lead pins and the like can be obtained by the above process (B) or process (B) + process (C) alone, to obtain plate-shaped metal materials used for stem bases and the like, an additional process (D) is performed in which the rod-shaped or wire-shaped material obtained in the above process (B) or process (B) + process (C) (usually rod-shaped material) is cut radially, and a plate material is cut out with the axial direction of the material being the thickness direction and the radial direction being the surface direction. In other words, in this process (D), the above rod-shaped or wire-shaped material is cut radially to form plate-shaped sections, thereby obtaining plate-shaped metal materials.

[0081] <Components and devices utilizing the metal material of the present invention> [Reed pin stem base for compression-sealed glass hermetic seals] Next, the lead pin and stem base for the compression-sealed glass hermetic seal of the present invention will be described. Here, lead pins generally have a surface treatment coating such as nickel plating on the surface of the pin substrate (pin body), and stem bases have a surface treatment coating such as nickel plating on the surface of the plate-shaped base substrate (base body). However, in this invention, when we refer to "lead pin" and "stem base," we mean the "pin substrate" and "base substrate" excluding such surface treatment coatings. The same applies to the inventions relating to airtight terminals, electric compressors, and semiconductor laser devices described later.

[0082] First, the lead pin of the present invention is a lead pin that constitutes a compression-sealed glass hermetic seal, and is made of the metal material of the present invention as described above, and consists of a rod-shaped or linear body with the direction of extension of the metal material (axial direction in the case of the rod-shaped or linear metal material described above) as the axial direction and the direction perpendicular to extension (radial direction in the case of the rod-shaped or linear metal material described above) as the radial direction (see Figure 4(a)). Therefore, this lead pin consists of a [Cr or / and Mo]-Cu composite having a metallic structure in which a Cr phase and / or Mo phase is dispersed in a Cu matrix, and this [Cr or / and Mo]-Cu composite is a diameter-reduced drawing material for a powder metallurgy molded body, and when the cross-sectional structure is observed with an optical microscope (for example, at a magnification of 120x), it has an axial cross-sectional structure in which layered or linear Cr phases and / or Mo phases are dispersed in a Cu matrix, and a radial cross-sectional structure in which flaky, small-piece, or granular Cr phases and / or Mo phases are dispersed in a Cu matrix. The axial and radial cross-sectional structure is as previously described for the metallic material of the present invention (see Figure 1).

[0083] Conventionally, lead pins have been made of Fe-Ni alloy, Kovar, stainless steel, etc., but the lead pin of the present invention can replace these conventional products and exhibits superior performance compared to them. Generally, lead pins that make up a compression-sealed glass hermetic seal are required to have (i) a relatively small axial thermal expansion coefficient and be as close as possible to that of the sealing glass in order to ensure reliable bonding with the sealing glass, and (ii) the ability to conduct large currents even with a small diameter and to generate little heat when energized, i.e., high axial electrical conductivity. The lead pins of the present invention have an axial thermal expansion coefficient less than the radial thermal expansion coefficient, a relatively small axial thermal expansion coefficient, an isotropic radial thermal expansion coefficient, and high axial electrical conductivity. Furthermore, those with further optimized properties as described below can have an axial thermal expansion coefficient close to that of sealing glass, and have significantly higher axial electrical conductivity compared to Ni-Fe alloys and other materials widely used in lead pins. Furthermore, a major feature of the lead pin of the present invention is that the magnitude of the axial thermal expansion coefficient can be changed (adjusted) by selecting the blending ratio (content) of Cr and / or Mo in the [Cr and / or Mo]-Cu composite and the reduction ratio of the material when it is stretched to reduce its diameter. As a result, the axial thermal expansion coefficient of the lead pin can be brought as close as possible to the thermal expansion coefficient of the sealing glass, thereby maximizing the reliability of the bond between the lead pin and the sealing glass, which is a challenge for compression-sealed glass hermetic seals. In addition, the axial electrical conductivity of the lead pin of the present invention increases as the reduction ratio of the material when it is stretched to reduce its diameter increases, so the axial electrical conductivity can be adjusted according to the application equipment.

[0084] The lead pin of the present invention has an average axial thermal expansion coefficient of 7.0 to 12.0 × 10⁻¹⁰ from 30°C to 450°C. -6 The mean radial thermal expansion coefficient is 18.0 × 10⁻¹⁰ / K, from 30°C to 450°C. -6 It is preferable that the thermal conductivity is less than or equal to / K, and that the average axial thermal expansion coefficient from 30°C to 450°C is less than the average radial thermal expansion coefficient from 30°C to 450°C. Furthermore, the axial electrical conductivity is 20.0 × 10⁻⁶. 6 It is preferable that the coefficient of radial thermal expansion of the lead pin is 18.0 × 10⁻⁶. -6 If the temperature is below / K, the lead pin can receive compressive stress from the sealing glass (see "Reference Examples" in Tables 1 and 3 below), so there is no particular problem. However, if the difference between the thermal expansion coefficient of the sealing glass and the lead pin is too large, the compressive force from the sealing glass will be small, which is not desirable. Therefore, the relationship with the thermal expansion coefficient of the sealing glass should be 15.0 × 10⁻⁶. -6 A value of / K or lower may be preferable in some cases. Furthermore, the [Cr and / or Mo]-Cu composite preferably has a total Cr and / or Mo content of 35-60 mass%.

[0085] The reasons why the above-described properties and compositional conditions are preferable are as previously stated regarding the metal material of the present invention. The diameter of the lead pin varies depending on the glass hermetic seal being used, but it is usually around φ0.1 to 6 mm. These lead pins (pin base materials) can be manufactured by cutting the rod-shaped or wire-shaped metal material of the present invention described above to a predetermined length. Typically, lead pins are subjected to surface treatment such as nickel plating. Furthermore, the characteristics of the lead pins of the present invention are also measured by a method similar to the method for measuring the characteristics of the metal material of the present invention, as described above. As described above, the lead pin of the present invention has high reliability in bonding with the sealing glass, and Even with a small diameter, it is possible to conduct high currents, and the amount of heat generated during energization can be reduced. For example, it can adequately accommodate further increases in current and miniaturization of electric compressors for automobiles.

[0086] Furthermore, the stem base of the present invention is a stem base constituting a compression-sealed glass hermetic seal, and is composed of the metal material of the present invention as described above, and consists of a plate-like body in which the stretching direction of the metal material (in the case of the plate-like metal material described above, the plate thickness direction) is the plate thickness direction and the direction perpendicular to the stretching (in the case of the plate-like metal material described above, the plate surface direction) is the plate surface direction (see Figure 4(b)). Therefore, this stem base consists of a [Cr or / and Mo]-Cu composite having a metallic structure in which a Cr phase and / or Mo phase is dispersed in a Cu matrix, and this [Cr or / and Mo]-Cu composite is a diameter-reduced drawing material for a powder metallurgy molded body, and when the cross-sectional structure is observed with an optical microscope (for example, at 120x magnification), it has a cross-sectional structure in the thickness direction in which layered or linear Cr phases and / or Mo phases are dispersed in a Cu matrix, and a cross-sectional structure parallel to the plate surface in which flaky, small-piece, or granular Cr phases and / or Mo phases are dispersed in a Cu matrix. The cross-sectional structure in the thickness direction and surface direction of this plate is as previously described for the metal material of the present invention (see Figure 1).

[0087] Conventionally, stem bases have been made of carbon steel or stainless steel, but the stem base of the present invention can replace these conventional products and exhibits superior performance compared to them. The stem base constituting a compression-sealed glass hermetic seal requires that (i) it have a coefficient of thermal expansion in the plane direction that allows for compression of the sealing glass and lead pins, and that its coefficient of thermal expansion in the thickness direction be relatively small and as close as possible to that of the sealing glass in order to ensure bonding reliability with the sealing glass, and (ii) in the case of a stem base for semiconductor laser equipment, etc., it is required to have a high thermal conductivity in the thickness direction in order to improve heat dissipation.

[0088] The stem base of the present invention has a thermal expansion coefficient in the plane direction necessary for compressing the sealing glass and lead pins, and has a thermal expansion coefficient in the thickness direction < thermal expansion coefficient in the plane direction, with a relatively small thermal expansion coefficient in the thickness direction, an isotropic thermal expansion coefficient in the plane direction, and high thermal conductivity in the thickness direction. Furthermore, among these, those with further optimized properties as described below can have a thermal expansion coefficient in the thickness direction close to that of the sealing glass, and have significantly higher thermal conductivity in the thickness direction compared to carbon steel and other materials widely used for stem bases. Furthermore, a major feature of the stem base of the present invention is the advantage that the magnitude of the thermal expansion coefficient in the thickness direction can be changed (adjusted) by selecting the blending ratio (content) of Cr and / or Mo in the [Cr and / or Mo]-Cu composite and the reduction ratio of the material when it is stretched to reduce its diameter. As a result, the thermal expansion coefficient in the thickness direction of the stem base can be brought as close as possible to the thermal expansion coefficient of the sealing glass, thereby maximizing the reliability of the bond between the stem base and the sealing glass, which is a challenge for compression-sealed glass hermetic seals. In addition, since the thermal conductivity in the thickness direction of the stem base of the present invention increases as the reduction ratio of the material when it is stretched to reduce its diameter increases, the thermal conductivity in the thickness direction can also be adjusted according to the application equipment.

[0089] The stem base of the present invention has an average thermal expansion coefficient in the thickness direction of the plate from 30°C to 450°C of 7.0 to 12.0 × 10⁻¹⁰ -6 The mean coefficient of thermal expansion in the direction of the plate surface from 30°C to 450°C is 18.0 × 10⁻¹⁰ / K. -6 It is preferable that the thermal conductivity in the thickness direction is 180 W / m·K or less, and that the average thermal expansion coefficient in the thickness direction from 30°C to 450°C is less than or equal to [average thermal expansion coefficient in the surface direction from 30°C to 450°C], and that the thermal conductivity in the thickness direction is 180 W / m·K or more. In the case of a stem base, since the sealing glass and lead pins need to be compressed in the surface direction, it is preferable that the thermal expansion coefficient in the surface direction be somewhat large, and from this viewpoint, 13.0 × 10 -6 It is preferable that the value is 1 / K or higher. Furthermore, the [Cr and / or Mo]-Cu composite preferably has a total Cr and / or Mo content of 35-60 mass%. The reasons why the above-described properties and compositional conditions are preferable are as previously stated regarding the metal material of the present invention.

[0090] Compression-sealed glass hermetic seals typically have a multi-pin structure, and the stem base comes in various shapes, such as circular and rectangular. For example, airtight terminals for electric compressors have a 3-pin structure, and the stem base is shaped like a running track. In the case of semiconductor laser devices, they also typically have a multi-pin structure, and the stem base comes in various shapes, such as circular and rectangular. This plate-shaped stem base can be manufactured by processing the plate-shaped metal material of the present invention described above. This plate-shaped metal material can be obtained by cutting a rod-shaped or wire-shaped material obtained by a reduction in surface area (reduced diameter stretching) in the radial direction, and cutting out a plate material with the axial direction of the material being the thickness direction and the radial direction being the surface direction. In this case, if the reduction in surface area (reduced diameter stretching) is performed by hot extrusion, a rod-shaped material with a cross-sectional shape like a running track can be obtained, and by cutting this rod-shaped material in the radial direction, a plate-shaped metal material close to the shape of the stem base itself can be obtained. Typically, the stem base is subjected to a surface treatment such as Ni plating. Furthermore, the properties of the stem base of the present invention are also measured by a method similar to the method for measuring the properties of the metal material of the present invention, as described above.

[0091] As described above, the stem base of the present invention can appropriately compress the sealing glass and lead pins in the plate surface direction, has high bonding reliability with the sealing glass, and also has excellent heat dissipation performance in the plate thickness direction. This allows for improved heat dissipation performance in semiconductor laser devices, for example, and can adequately accommodate the increased power output and performance of semiconductor laser devices. Furthermore, while the plate surface thermal expansion coefficient of the stem base needs to be somewhat larger than the thermal expansion coefficient of the sealing glass in order to impart compressive force to the sealing glass, it is desirable that the plate thickness thermal expansion coefficient be as close as possible to the thermal expansion coefficient of the sealing glass in order to ensure bonding reliability with the sealing glass. The stem base of the present invention has a certain level of plate surface thermal expansion coefficient, and plate thickness thermal expansion coefficient < plate surface thermal expansion coefficient. Moreover, the magnitude of the plate thickness thermal expansion coefficient can be adjusted by selecting the blending ratio (content) of Cr and / or Mo and the reduction ratio when the material is stretched to reduce its diameter, thereby optimizing the plate thickness thermal expansion coefficient. In particular, it can highly satisfy the thermal expansion characteristics required of a stem base. On the other hand, by increasing the reduction ratio during diameter reduction and stretching, the thermal conductivity in the thickness direction can be increased, thereby highly satisfying the heat dissipation requirements for the stem base.

[0092] [Airtight terminals and electric compressor] The hermetic terminal of the present invention is a compression-sealed hermetic terminal equipped with the lead pin described above. Accordingly, the lead pin is made of a [Cr or / and Mo]-Cu composite having a metallic structure in which a Cr phase and / or Mo phase is dispersed in a Cu matrix, and this [Cr or / and Mo]-Cu composite is a diameter-reduced stretched material for a powder metallurgy molded body, and when the cross-sectional structure is observed with an optical microscope (for example, at 120x magnification), it is characterized by having an axial cross-sectional structure in which layered or linear Cr phases and / or Mo phases are dispersed in a Cu matrix, and a radial cross-sectional structure in which flaky, small-piece, or granular Cr phases and / or Mo phases are dispersed in a Cu matrix. The details of the lead pins on this hermetically sealed terminal are as previously explained in the sections on "metal materials" and "lead pins." Furthermore, the electric compressor of the present invention is an electric compressor equipped with an airtight terminal. Therefore, the airtight terminal of the present invention, and the electric compressor of the present invention equipped with this airtight terminal, can each enjoy the effects of the metal material and lead pin of the present invention described above.

[0093] [Semiconductor laser equipment] The semiconductor laser apparatus of the present invention is a semiconductor laser apparatus equipped with the stem base and / or lead pins described above, and therefore has any of the following forms (1) to (3). (1) The plate-shaped stem base is made of a [Cr or / and Mo]-Cu composite having a metallic structure in which a Cr phase and / or Mo phase is dispersed in a Cu matrix, and this [Cr or / and Mo]-Cu composite is a diameter-reduced stretched material for a powder metallurgy molded body, and when the cross-sectional structure is observed with an optical microscope (e.g., 120x magnification), it has a cross-sectional structure in the thickness direction in which layered or linear Cr phases and / or Mo phases are dispersed in the Cu matrix, and a cross-sectional structure parallel to the plate surface in which flaky, small-piece, or granular Cr phases and / or Mo phases are dispersed in the Cu matrix (semiconductor laser device of the first embodiment of the present invention). (2) The lead pin is made of a [Cr or / and Mo]-Cu composite having a metallic structure in which a Cr phase or / and a Mo phase is dispersed in a Cu matrix, and this [Cr or / and Mo]-Cu composite is a diameter-reduced stretched material of a powder metallurgy molded body, and when the cross-sectional structure is observed with an optical microscope (for example, at 120x magnification), it has an axial cross-sectional structure in which layered or linear Cr phases or / and Mo phases are dispersed in a Cu matrix, and a radial cross-sectional structure in which flaky, small-piece or granular Cr phases or / and Mo phases are dispersed in a Cu matrix (second embodiment of the semiconductor laser device of the present invention).

[0094] (3) The plate-shaped stem base and lead pin are made of a [Cr or / and Mo]-Cu composite having a metallic structure in which a Cr phase and / or Mo phase are dispersed in a Cu matrix. The [Cr and / or Mo]-Cu composite constituting the plate-shaped stem base is a diameter-reduced stretched material for a powder metallurgy molded body, and when the cross-sectional structure is observed with an optical microscope (e.g., 120x magnification), it has a cross-sectional structure in the thickness direction in which layered or linear Cr phases and / or Mo phases are dispersed in the Cu matrix, and a cross-sectional structure parallel to the plate surface in which flaky, small-piece, or granular Cr phases and / or Mo phases are dispersed in the Cu matrix. The [Cr and / or Mo]-Cu composite constituting the lead pin is a diameter-reduced and drawn material for a powder metallurgy molded body, and when the cross-sectional structure is observed with an optical microscope (e.g., 120x magnification), it has an axial cross-sectional structure in which layered or linear Cr phases and / or Mo phases are dispersed in the Cu matrix, and a radial cross-sectional structure in which flaky, small-piece, or granular Cr phases and / or Mo phases are dispersed in the Cu matrix (third embodiment of the present invention, semiconductor laser device).

[0095] The semiconductor laser device of the present invention is not limited to one equipped with a compression-sealed glass hermetic seal, but typically a compression-sealed glass hermetic seal is formed with the stem base and / or the lead pins as constituent members. Details of the lead pins and / or stem bases of the semiconductor laser devices described in (1) to (3) above are as previously explained in the sections on "metallic material," "lead pins," and "stem base." Therefore, the semiconductor laser devices described in (1) to (3) above can each benefit from the effects of the metal material, lead pins, and stem base of the present invention described above. Furthermore, the semiconductor laser apparatus described in (3) above is particularly preferred because it is equipped with the lead pins and stem base of the present invention described above, thereby providing the highest reliability in bonding between the sealing glass and the lead pins and stem base. [Other components] Conventionally, no axial material with a low axial thermal expansion coefficient and high axial electrical conductivity, nor any plate-shaped material with a low thermal expansion coefficient in the thickness direction and high thermal conductivity in the thickness direction, has been known. The metal material of the present invention can be used in various applications as a material with such properties. For example, it can be used in conductive members or heat sinks that are joined with other low thermal expansion materials.

[0096] <Study on the bonding reliability of the metal material of the present invention> Next, the bonding reliability when the metal material of the present invention is used as a component (lead pin, stem base) of a compression-sealed glass hermetic seal is examined based on material mechanics, and the results are shown below. In the following description, the stem base will be referred to as the "housing." Also, in the following description (including Tables 1 to 4), "%" in relation to the material composition means "mass%." First, we investigated the application of the metal material of the present invention to the lead pins of a compression-sealed glass hermetic seal provided in an airtight terminal. Specifically, we examined the bonding reliability of a compression-sealed glass hermetic seal composed of a housing made of carbon steel S45C, a sealing glass made of ST-4W (glass cord, manufactured by Nippon Electric Glass Co., Ltd.), and a lead pin made of the linear metal material of the present invention (wire made of a 55% Cr-Cu composite) using a simplified concentric cylindrical material mechanics approach.

[0097] Figures 5 and 6 are schematic diagrams (conceptual diagrams showing the dimensions and thermal expansion coefficients of the constituent members, compressive stress within the seal, etc.) of the compression-sealed glass hermetic seal used in this study. Figure 5(A) is a schematic longitudinal section of the entire seal, Figure 5(B) is a schematic plan view of the same, and Figure 5(C) is a schematic plan view of the sealing glass. Figure 6(A) is a schematic longitudinal section of the entire seal, Figure 6(B) is a schematic plan view of the housing and sealing glass, and Figure 6(C) is a schematic plan view of the sealing glass and lead pin. The numerical values ​​shown in Figures 5 and 6 represent the average thermal expansion coefficients of each component constituting the seal. For convenience of explanation, the metal material of the present invention constituting the lead pin will be referred to as "55%Cr-Cu material" in the following explanation. Because the thermal expansion coefficient of the housing (carbon steel S45C) is greater than that of the sealing glass, the outer radial surface (circumferential surface) of the sealing glass is subjected to a compressive stress P1 from the inner radial surface (inner circumferential surface) of the housing while the sealing glass is cooling from hardening to room temperature.

[0098] The volume of the sealing glass is determined around [glass transition point - 30°C] relative to the glass transition point where it is fully hardened (the glass transition point of ST-4W mentioned above: 460°C), and at 30°C, the volume is reduced due to thermal expansion. The calculated outer radius R2' of the sealing glass (radius at the outer surface of the sealing glass) is larger than the inner radius R2 of the housing (radius at the inner surface of the housing) due to housing contraction, but it matches the inner radius R2 due to the compressive stress P1 during sealing (see Toshiba Glass Technical Report 26, "On Glass Distortion"). As a result (with constant volume), the inner radius of the sealing glass (radius at the inner surface of the sealing glass) is displaced inward by υ2 (due to compressive strain from the compressive stress P1) to become R3''. The compressive stress P1 acting from the housing to the sealing glass can be predicted by calculating the displacement difference υ2 as a "thick-walled cylinder subjected to external pressure" in the principles of material mechanics.

[0099] The radial thermal expansion coefficient of the 55%Cr-Cu material that makes up the lead pin is greater than that of the sealing glass. Therefore, as the sealing glass hardens and cools to room temperature, the lead pin shrinks more radially than the sealing glass, resulting in a calculated gap δ3 (the difference between the calculated inner radius R3' of the sealing glass and the calculated outer radius R3 of the lead pin). If the displacement υ2 toward the inner diameter of the sealing glass is greater than this gap δ3, that is, if R3'' (=R3'-υ2) becomes smaller than R3, then no gap will form at the interface between the sealing glass and the lead pin, potentially achieving reliable bonding. In this case, the displacement difference υ3 between R3 and R3'' causes the lead pin to experience a compressive stress P2 from the sealing glass. That is, the sealing glass receives a compressive stress P1 from the housing on its outer radial surface, while simultaneously exerting a compressive stress P2 on the lead pin from its inner radial surface. This compressive stress P2 can be predicted by calculating it from the displacement difference υ3 as a "combined cylinder" in mechanics of materials.

[0100] The reliability of the bond between the sealing glass, housing, and lead pins can be considered as follows: Since the difference in thermal expansion between the housing (carbon steel S45C) and the sealing glass is equally large in the thickness direction (height direction in the drawing; the same applies hereafter), shear stress is generated in the thickness direction at the interface between the housing and the sealing glass during sealing. However, since this combination is commonly used, it is unlikely that delamination will immediately occur. This is because compressive strain remains in the sealing glass during sealing, but the shear stress at the glass interface in the thickness direction caused by this residual strain is on the compression side, where the glass has high strength, and the stress is also relieved by the compressive stress P1 (interface adhesion stress) in the radial direction. When the temperature rises in the operating environment, the shear stress at the glass interface in the thickness direction becomes on the tensile side, where the glass has weaker properties, but it is thought that the residual compressive strain of the glass can relieve this tensile stress. However, under more severe operating environments, problems with bonding reliability may occur. Furthermore, a combination of Kovar lead pins and FN-13W (glass cord, manufactured by Nippon Electric Glass Co., Ltd.) sealing glass is also commonly used, but the lead pins are 2 × 10⁻¹⁰⁻¹ -6 The thermal expansion coefficient is low, around 1 / K, and the difference in thermal expansion between the lead pin and the sealing glass causes undesirable tensile strain in the sealing glass. Therefore, due to the material properties, the bonding reliability of this combination cannot be said to be sufficient.

[0101] On the other hand, the bonding reliability on the inner radial surface side of the sealing glass can be considered as follows. Calculations show that the compressive stress P2 from the inner radial surface of the sealing glass to the outer radial surface of the lead pin tends to be smaller than the compressive stress P1 from the housing to the outer radial surface of the sealing glass. Therefore, if the axial thermal expansion coefficient of the lead pin is larger than that of the sealing glass, similar to the housing, compressive strain will remain in the sealing glass in the thickness direction, similar to the housing, but the bonding reliability on the inner radial surface of the sealing glass tends to be lower than that on the outer radial surface of the sealing glass. However, the 55%Cr-Cu material constituting the lead pin has a smaller axial thermal expansion coefficient than carbon steel, and if the difference in thermal expansion with the sealing glass is small, bonding reliability can be obtained by the interfacial adhesion stress (compressive stress P2) between the sealing glass and the lead pin.

[0102] Furthermore, it is necessary to consider the compressive shear stress τ acting on the sealing glass interface in the axial direction of the lead pin and the thickness direction of the housing, and the balance between this compressive shear stress τ and the compressive stresses P1 and P2 in the radial direction of the sealing glass. If the thermal expansion coefficient of the housing in the plate surface direction and the radial thermal expansion coefficient of the lead pin are greater than the thermal expansion coefficient of the sealing glass, the sealing glass will receive a favorable compressive strain after cooling. However, if the temperature rises and falls repeatedly, it will be affected by compression and tension, and the joint reliability may decrease due to shear stress strain fatigue caused by the difference in thermal expansion coefficients between the thickness direction of the housing, the axial direction of the lead pin, and the sealing glass. For this reason, it is preferable that the thermal expansion coefficients of the housing in the thickness direction, the axial thermal expansion coefficient of the lead pin, and the thermal expansion coefficient of the sealing glass are as small as possible on the compression side of the sealing glass, while it is preferable that the compressive stresses P1 and P2 in the radial direction of the sealing glass be large. Therefore, it can be said that the joint reliability between the lead pin and housing and the sealing glass is high when the values ​​of τ / P1 and τ / P2 are positive and small (however, it is not a problem even if they are negative as long as they are sufficiently small). In the case of lead pins, comparing 55%Cr-Cu material and 50.5%Ni-Fe material, the compressive stress P2 for 55%Cr-Cu material is about 91% of that of 50.5%Ni-Fe material and about 88% of that of copper core pins. However, because the difference in thermal expansion coefficient with the sealing glass in the axial direction is small for 55%Cr-Cu material, the τ / P2 is about 86% lower than that of 50.5%Ni-Fe material and about 93% lower than that of copper core pins, resulting in higher bonding reliability. Even if the 55%Cr-Cu material has the characteristic that [average axial thermal expansion coefficient from 30°C to 450°C] < [average radial thermal expansion coefficient from 30°C to 450°C], compressive stress can be obtained from the sealing glass in the radial direction, and axial bonding reliability can be obtained.

[0103] The following shows the results of calculating the displacement differences υ2, υ3 and compressive stresses P1, P2 mentioned above, the thickness-direction shear stress τ1 from the housing to the sealing glass interface, the axial shear stress τ3 from the lead pin to the sealing glass interface, and τ1 / P1 and τ3 / P2. The physical properties of each material used in this calculation will be described later. Note that in the calculations below, the numbers enclosed in brackets [ ] below a specific value are those of the conventional 50.5% Ni-Fe (axial average thermal expansion coefficient (30-450℃): 10.3 × 10) used for lead pins. -6 This is the case when using / K).

[0104] ●The dimensional changes of the housing (carbon steel), sealing glass, and lead pins (55% Cr-Cu material) from 430°C to 30°C are shown below. In Figures 5 and 6, if R1 = 8 mm, R2 = 3 mm, and R3 = 1.6 mm, the dimensions at 430°C and 30°C are as follows. <At 430℃> • Housing inner radius = Sealing glass outer radius = R² * (1 + α¹ * (430℃ - 30℃)) = 3.018318 mm • Inner radius of sealing glass = Outer radius of lead pin = R3 * (1 + α3 * (430℃ - 30℃)) = 1.609219mm [1.607981mm] <At 30℃> • Housing outer radius = 8mm = R1 • Housing inner radius = Sealed glass outer radius = 3mm = R2 • Calculated outer radius of the sealing glass: R2' = 3.018318 * (1 - α2 * (430℃ - 30℃)) = 3.006848 mm →The sealing glass is compressed to 3 mm and subjected to a compressive stress equal to its displacement difference of υ². • Calculated inner radius of the sealing glass: R3' = 1.609219 * (1 - α3 * (430℃ - 30℃)) = 1.603104 mm [1.6001870mm] Lead pin outer radius = 1.6 mm = R3 →δ3=1.603104-1.6=0.003104mm [0.001870mm]

[0105] ●The volume of the sealing glass is determined near the [glass transition temperature -30°C], and at 30°C, it shrinks due to thermal expansion. While the calculated volume of the sealing glass and the volume after sealing remain constant, assuming the thickness of the sealing glass does not change, At 30°C, the calculated surface area of ​​the sealing glass is as follows: R2'=3.006848mm, R3'=1.603104mm → 20.33mm 2 The outer radius of the sealing glass is 3 mm. The inner radius of the sealing glass is R3” = 1.590222 mm (υ² = 0.012882 mm). [1.588978mm] [0.012892mm] ● The compressive stress P1 from the housing due to the displacement υ2 on the inner diameter side of the sealing glass is calculated using the following formula.

number

[0106] ●The compressive stress P2 is as follows: • If lead pins are not present, the inner radius of the sealing glass is R3” = R3' - υ² = 1.590222mm ·R3>R3”→ R3-R3”=υ3=0.00978mm [0.01102mm] →The lead pin is subjected to compressive stress P2 from the sealing glass by υ3. ●The compressive stress P2 from the sealing glass to the lead pin is calculated using the following formula.

number

[0107] ●The thickness-direction compressive shear stress τ1 acting from the housing to the sealing glass interface and the [thickness-direction compressive shear stress τ1 acting from the housing to the sealing glass interface] / [radial compressive stress P1 from the housing to the sealing glass] are calculated as follows. In Figures 5 and 6, if R1 = 8 mm, R2 = 3 mm, R3 = 1.6 mm, and the housing thickness T1 = 6 mm, the dimensions at 430°C and 30°C are as follows. <At 430℃> Carbon steel thickness = sealing glass thickness; T1' = 6 * (1 + α1 * (430℃ - 30℃)) = 6.036636 mm <At 30℃> Sealing glass thickness; T2' = T1' * (1 - α2 * (430℃ - 30℃)) = 6.013697 mm

[0108] →Compressive strain ε=(T2'-T1) / T1 from the housing to the sealing glass after cooling =0.002283 Compressive stress: Pt1 = Glass modulus * ε = 0.15523 GPa = 155.23 MPa [155.23MPa] Compressive force: Ft1 = Pt1 * π * R2 2 =4389N [4389N] The thickness-direction compressive shear stress τ1 acting from the housing to the sealing glass interface is as follows: τ1 = Ft1 / (π*2*R2*T1) = 38.81 MPa [38.81 MPa] →Therefore, the [thickness-direction compressive shear stress τ1 acting from the housing to the sealing glass interface] / [radial-direction compressive stress P1 from the housing to the sealing glass] is as follows: τ1 / P1 = 0.1960 [0.1955]

[0109] ●The axial compressive shear stress τ3 acting from the lead pin to the sealing glass interface and the [axial compressive shear stress τ3 acting from the lead pin to the sealing glass interface] / [radial compressive stress P2 from the sealing glass to the lead pin] are calculated as follows. <At 30℃> Thickness of the lead pin in contact with the sealing glass; T3' = T1' * (1 - α3 (430℃ - 30℃)) = 6.013455 mm [6.01177mm] →Compressive strain ε=(T2'-T3') / T3' from the sealing glass to the lead pin after cooling =0.000040 Compressive stress: Pt3 = Glass modulus * ε = 0.002730 GPa = 2.730 MPa [21.85MPa] Compression force: Ft3 = Pt1 * π * R3 2 =21.96N [175.7N]

[0110] The axial compressive shear stress τ3 acting from the lead pin to the sealing glass interface is as follows: τ3 = Ft3 / (π*2*R3*T1) = 0.363MPa [2.908MPa] Therefore, the axial compressive shear stress τ3 acting from the lead pin to the sealing glass interface / the radial compressive stress P2 from the sealing glass to the lead pin is as follows: τ3 / P2 = 0.0039 [0.0285]

[0111] The above calculations were performed when the lead pins were made of the 55%Cr-Cu material of the present invention, the housing of carbon steel S45C, and the sealing glass of ST-4W (glass cord, manufactured by Nippon Electric Glass Co., Ltd.). However, similar calculations were performed when the lead pins, housing, and sealing glass were made of other materials. Specifically, the lead pins used were the 45%Cr-Cu material, 60%Mo-Cu material, and 35%Mo-Cu material, all of which are metal materials of the present invention, as well as the comparative materials 50.5%Ni-Fe material, SUS430, copper core pin, and 29%Ni-17%Co-Fe material. The calculation results are shown in Tables 1 to 3 along with the calculation results described above. In Tables 1 to 3, "equivalent to the inventive example" refers to a case where the lead pins use the metal material of the present invention, and "equivalent to the comparative example" refers to a case where the lead pins use a material other than the metal material of the present invention. Note that the "Reference Examples" in Tables 1 and 3, which use 35% Mo-Cu material (the metal material of the present invention) for the lead pins, have a radial average thermal expansion coefficient of approximately 18.0 × 10⁻⁶. -6 This was included to show that the lead pins can be subjected to compressive stress from the sealing glass if the temperature is below / K.

[0112] The physical properties of each material used in the calculations in Tables 1 to 3 are as follows. (1) Housing • Carbon steel S45C Average thermal expansion coefficient α1 (20-500℃): 14.2 × 10 -6 / K Young's modulus E1: 205 GPa Poisson's ratio ν1:0.25 SUS304 Average thermal expansion coefficient α1 (0-538℃): 18.8 × 10⁻⁶ -6 / K Young's modulus E1: 193 GPa Poisson's ratio ν1:0.3 SUS430 Average thermal expansion coefficient α1 (0-538℃): 11.7 × 10⁻⁶ -6 / K Young's modulus E1: 200 GPa Poisson's ratio ν1:0.27

[0113] (2) Lead pin ·55%Cr-Cu material (area reduction rate: 96.8%) mean radial thermal expansion coefficient α3 (30-450℃): 13.4 × 10 -6 / K Average axial thermal expansion coefficient (30-450°C): 9.6 × 10⁻⁶ -6 / K Young's modulus E3: 206 GPa Poisson's ratio ν3:0.25 ·45%Cr-Cu material (area reduction rate: 75.0%) mean radial thermal expansion coefficient α3 (30-450℃): 15.2 × 10 -6 / K Average axial thermal expansion coefficient (30-450°C): 10.7 × 10 -6 / K Young's modulus E3: 198 GPa Poisson's ratio ν³:0.26 ·60%Mo-Cu material (area reduction rate: 80.0%) mean radial thermal expansion coefficient α3 (30-450℃): 13.4 × 10 -6 / K Average axial thermal expansion coefficient (30-450°C): 7.6 × 10⁻⁶ -6 / K Young's modulus E3: 242 GPa Poisson's ratio ν³:0.33 ·35%Mo-Cu material (area reduction rate: 97.6%) mean radial thermal expansion coefficient α3 (30-450℃): 17.7 × 10 -6 / K Average axial thermal expansion coefficient (30-450°C): 9.3 × 10⁻⁶ -6 / K Young's modulus E3: 188 GPa Poisson's ratio ν³:0.33

[0114] 50.5% Ni-Fe material mean radial thermal expansion coefficient α3 (30-450℃): 11.6 × 10 -6 / K Average axial thermal expansion coefficient (30-450℃): 10.3 × 10 -6 / K Young's modulus E3: 162 GPa Poisson's ratio ν³:0.30 SUS430 mean radial thermal expansion coefficient α3 (30-450℃): 11.3 × 10 -6 / K Average axial thermal expansion coefficient (30-450°C): 11.3 × 10⁻⁶ -6 / K Young's modulus E3: 200 GPa Poisson's ratio ν³:0.27 • Copper core pin mean radial thermal expansion coefficient α3 (30-450℃): 11.1 × 10 -6 / K Average axial thermal expansion coefficient (30-450°C): 11.1 × 10⁻⁶ -6 / K Young's modulus E3: 157 GPa Poisson's ratio ν³:0.31 • 29% Ni-17% Co-Fe material (Kovar) mean radial thermal expansion coefficient α3 (30-450℃): 5.3 × 10 -6 / K Average axial thermal expansion coefficient (30-450℃): 5.3 × 10⁻⁶ -6 / K Young's modulus E3: 152 GPa Poisson's ratio ν³:0.3

[0115] (3) Sealing glass • ST-4W (Glass cord, manufactured by Nippon Electric Glass Co., Ltd.) Average thermal expansion coefficient α² (30-380℃): 9.5 × 10⁻⁶ -6 / K Glass transition temperature Tg: 460℃ Young's modulus E2: 68 GPa Poisson's ratio ν²: 0.21 • FN-13W (glass cord, manufactured by Nippon Electric Glass Co., Ltd.) Average thermal expansion coefficient α² (30-380℃): 7.6 × 10⁻⁶ -6 / K Glass transition temperature Tg: 510℃ Young's modulus E2: 57 GPa Poisson's ratio ν²: 0.22 • SG354 (Glass cord, manufactured by AGC Corporation) Average thermal expansion coefficient α² (50-350℃): 10.7 × 10⁻⁶-6 / K Glass transition temperature Tg: 567℃ Young's modulus E2: 68 GPa Poisson's ratio ν²: 0.21

[0116] [Table 1]

[0117] [Table 2]

[0118] [Table 3]

[0119] The calculation results in Tables 1 to 3 indicate that when the lead pin uses the metal material of the present invention (corresponding to the example of the invention), a compressive pressure P2 from the sealing glass to the lead pin is obtained, and τ3 / P2 is sufficiently low, thus achieving the necessary bonding reliability. In particular, as shown in Tables 2 and 3, by almost matching the average axial thermal expansion coefficient of the lead pin with the average thermal expansion coefficient of the sealing glass, the shear stress generated between the lead pin and the sealing glass can be reduced to almost zero, thereby maximizing bonding reliability. On the other hand, the comparative example in Table 3 uses a commonly used combination of Kovar lead pins and FN-13W (glass cord, manufactured by Nippon Electric Glass Co., Ltd.) sealing glass, but as mentioned earlier, the lead pins are 2 × 10⁻¹⁰⁻¹ -6 Because the thermal expansion coefficient is low by approximately / K, the value of τ3 / P2 is a negative 0.44, which indicates an undesirable tensile strain for sealing glass. This numerical result also indicates that the bonding reliability is not sufficient.

[0120] Next, we considered the application of the metal material of the present invention to the housing (stem base) of a compression-sealed glass hermetic seal used in semiconductor laser devices, with the expectation of improving the heat dissipation of the housing (stem base). Similar to the case of hermetic terminals, we considered a simplified concentric cylindrical shape (R1=4.5mm, R2=0.6mm, housing thickness T=1.5mm) as shown in Figures 7 and 8. Here, the sealing glass was made of ST-4W (glass cord, manufactured by Nippon Electric Glass Co., Ltd.), the lead pins were made of the linear metal material of the present invention (wire material of 55%Cr-Cu composite), and the housing was made of carbon steel and the plate-shaped metal material of the present invention (plate material of 55%Cr-Cu composite), and the same calculations as in Tables 1 to 3 above were performed. For comparison, the same calculations were also performed when the housing was made of carbon steel, the lead pins were made of 50.5%Ni-Fe material, and the sealing glass was made of ST-4W (glass cord, manufactured by Nippon Electric Glass Co., Ltd.). The calculation results are shown in Table 4. In Table 4, "equivalent to the inventive example" refers to a case where the lead pin and / or housing uses the metal material of the present invention, and "equivalent to the comparative example" refers to a case where the lead pin and housing use materials other than the metal material of the present invention. The physical properties of each material used in the calculations in Table 4 are the same as those used in the calculations in Tables 1 to 3.

[0121] [Table 4]

[0122] Figures 7 and 8 are schematic diagrams (conceptual diagrams showing the dimensions and thermal expansion coefficients of the constituent members, compressive stress within the seal, etc.) of the compression-sealed glass hermetic seal provided in the semiconductor laser device used in this study. Figure 7 is a schematic diagram of a compression-sealed glass hermetic seal in which the housing (stem base) is made of carbon steel, the sealing glass is made of ST-4W (glass cord, manufactured by Nippon Electric Glass Co., Ltd.), and the lead pins are made of the linear metal material of the present invention (wire material of 55% Cr-Cu composite). Figure 7(A) is a schematic longitudinal section of the entire seal, and Figure 7(B) is a schematic plan view of the same. Figure 8 is a schematic diagram of a compression-sealed glass hermetic seal in which the housing (stem base) is made of the plate-shaped metal material of the present invention (55%Cr-Cu composite plate), the lead pins are made of the linear metal material of the present invention (55%Cr-Cu composite wire), and the sealing glass is made of ST-4W (glass cord, manufactured by Nippon Electric Glass Co., Ltd.). Figure 8(A) is a schematic longitudinal section of the entire seal, and Figure 8(B) is a schematic plan view of the same. In Figures 7 and 8, the numerical values ​​indicated in the figures are the average thermal expansion coefficients of each component constituting the seal. For convenience of explanation, in the following explanation, the lead pins and housing (stem base) made of the materials of the present invention will be referred to as "Cr-Cu material lead pins" and "Cr-Cu material housing," respectively. Also, the housing (stem base) made of carbon steel will be referred to as "carbon steel housing."

[0123] Because the thermal expansion coefficient of the Cr-Cu housing in the radial direction (plate surface direction) is greater than that of the sealing glass, a compressive stress P1 is generated in the radial direction from the Cr-Cu housing to the sealing glass while the sealing glass is cooling to room temperature after it has hardened. The Cr-Cu housing has a lower coefficient of thermal expansion in the height (thickness) direction than the carbon steel housing and is close to the coefficient of thermal expansion of the sealing glass. Therefore, the shear stress generated at the height (thickness) interface between the housing and the sealing glass is reduced, and it is believed that higher bonding reliability can be obtained compared to the carbon steel housing.

[0124] As explained earlier, the more positive and smaller the values ​​of τ1 / P1 and τ3 / P2 are (however, negative values ​​are acceptable if they are sufficiently small), the higher the reliability of the joint between the housing and the sealing glass, and the reliability of the joint between the lead pin and the sealing glass. The calculation results show that the Cr-Cu lead pin has a smaller difference in axial thermal expansion coefficient with the sealing glass, resulting in a lower τ3 / P2 than the comparative 50.5% Ni-Fe material and higher joint reliability. Furthermore, the Cr-Cu housing has a smaller thermal expansion coefficient in the thickness direction, and the difference in thermal expansion coefficient in the thickness direction with the sealing glass is small, resulting in a larger decrease in τ1 / P1 than carbon steel and thus higher joint reliability.

[0125] Regarding housing materials to replace carbon steel, the application of press-formed Cr-Cu / Cu clad rolled material (rolled sheet material) was initially considered. However, while rolled sheet material has a small coefficient of thermal expansion in the sheet direction, it has a large coefficient of thermal expansion in the thickness direction. As a result, compressive stress in the radial direction of the housing tends to be small, and interfacial shear stress in the thickness direction tends to be high, and calculations suggest that the joint reliability will be lower than that of carbon steel. In contrast, the Cr-Cu housing of the present invention provides compressive stress in the radial (sheet direction) direction similar to that of carbon steel housing, while reducing interfacial shear stress in the height (thickness) direction and having high heat dissipation in the height (thickness) direction. Therefore, it is considered optimal as a housing for semiconductor laser modules. Furthermore, regarding the application of the Cr-Cu housing and Cr-Cu lead pins of the present invention to semiconductor laser modules, in addition to the combination of Cr-Cu housing and Cr-Cu lead pins, other configurations may be used as appropriate depending on the application, such as a combination of Cr-Cu housing and 52% Ni-Fe lead pins, or a combination of carbon steel housing and Cr-Cu lead pins. For example, the combination of Cr-Cu housing and 50.5% Ni-Fe lead pins (No. 4 in Table 4) has higher bonding reliability than the conventionally used combination of carbon steel housing and 50.5% Ni-Fe lead pins (No. 2 in Table 4), and the combination of carbon steel housing and Cr-Cu lead pins (No. 1 in Table 4) has higher bonding reliability than the combination of carbon steel housing and 50.5% Ni-Fe lead pins (No. 2 in Table 4), so such configurations are also effective. [Examples]

[0126] The materials of the present invention (rod-shaped or wire-shaped metal materials) were manufactured under the manufacturing conditions shown below, and their properties were measured. For comparison, a material consisting of a [Cr and / or Mo]-Cu composite that had not undergone surface reduction (diameter reduction stretching) (0% surface reduction), pure Cu material, 50.5% Ni-Fe material, and copper core pins (50% Ni-Fe with copper cladding in the center) were used as test materials, and their properties were measured in the same manner as above. The results, along with the composition (density) and manufacturing conditions (surface reduction) of the metal materials, are shown in Tables 5 and 6. In the description of this example (including Tables 5 and 6), "%" in relation to the material composition means "mass%". Here, the metal materials in this embodiment are all in the form of a rod or wire, and are therefore referred to as the axial and radial directions. However, in the material of the present invention, the axial direction is the stretching direction, and the radial direction is the direction perpendicular to the stretching direction. The rod-shaped or wire-shaped metal material of the present invention can be used as is as the material for a lead pin, but the plate-shaped metal material cut radially from the rod-shaped metal material (a plate material in which the axial direction of the rod-shaped metal material is the thickness direction and the radial direction is the surface direction) can be used as is as the material for a stem base.

[0127] Furthermore, although not explicitly shown in Tables 5 and 6, the material of the present invention has a cross-sectional structure as shown in Figure 1, that is, when the cross-sectional structure is observed with an optical microscope, it has a cross-sectional structure in the stretching direction (axial direction) in which layered or linear Cr phases and / or Mo phases are dispersed in the Cu matrix, and a cross-sectional structure perpendicular to the stretching direction (radial direction) in which flaky, small-piece, or granular Cr phases and / or Mo phases are dispersed in the Cu matrix. In contrast, the comparative material, a [Cr and / or Mo]-Cu composite material that has not undergone surface reduction processing (diameter reduction stretching processing) (surface reduction ratio 0%), naturally does not have such a characteristic cross-sectional structure, but rather a cross-sectional structure like the "soaked body cross-section" in Figure 2.

[0128] (1) Production of material for surface reduction processing Cr powder and / or Mo powder were placed in a mold and pressure-molded, or a mixed powder of Cr powder and / or Mo powder and Cu powder in a predetermined ratio was placed in a mold and pressure-molded to obtain a compact. A pure Cu plate was placed on top of this compact and sintered and Cu fusion was performed in a reducing atmosphere. Specifically, sintering (1000°C, 600 minutes) was performed first to obtain a sintered body, and then the temperature was increased to melt the pure Cu plate, and Cu fusion (1200°C, holding time 180 minutes) was performed to impregnate the sintered body with this Cu to obtain a [Cr and / or Mo]-Cu composite. Using a milling machine, the Cu remaining on the surface of the [Cr and / or Mo]-Cu composite was cut off and the shape was refined to obtain a material (rod-shaped material) for surface reduction of a predetermined size.

[0129] (2) Fabrication of the material of the present invention by surface reduction (diameter reduction stretching) (2.1) Examples No. 1-29, 36-47 A material for surface reduction, shaped into a 16-sided prism (20.7 mm in diameter) by milling, was subjected to surface reduction (diameter reduction and stretching) to an outer diameter of φ3.7 mm by swaging and subsequent combined roll rolling. Further surface reduction (diameter reduction and stretching) was performed using a two-stage roller die drawing (CRD) process to obtain the material of the present invention with an outer diameter of φ3.2 mm. (2.2) Cases of Examples No. 32 to 35 A material for surface reduction, shaped into an octagonal prism (50 mm in diameter) by milling, is then subjected to surface reduction (diameter reduction and stretching) to an outer diameter of φ15 mm by groove roll rolling and subsequent swaging. This is followed by surface reduction (diameter reduction and stretching) to a 3.7 mm thick prism (octagonal in diameter) by combined roll rolling. Finally, a finish drawing process consisting of roller die drawing (CRD) and simple drawing (wet cold drawing) is performed to further reduce the surface size (diameter reduction and stretching), resulting in the material of the present invention with an outer diameter of φ3.2 mm. (3) Measurement of characteristics For each test material, the axial and radial thermal expansion coefficients, axial electrical conductivity (and volume resistivity), and axial thermal conductivity were determined using the measurement and calculation methods described earlier. For the measurement of axial electrical conductivity (and volume resistivity), an "Electrical Resistivity Measuring Device TER-2000RH Special Type" manufactured by Advance Engineering was used. Furthermore, for samples with the same material composition but different reduction ratios, material for the other samples was taken during the reduction process of the sample with the largest reduction ratio, processed into φ3.2 mm samples using centerless grinding, and used for each measurement.

[0130] According to Tables 5 and 6, the metal material of the present invention has a certain level of radial thermal expansion coefficient, while its axial thermal expansion coefficient is considerably smaller than its radial thermal expansion coefficient, and the sealing glass of compression-sealed glass hermetic seals (typically 8-11 × 10) -6It can be seen that the thermal expansion coefficient can be made close to that of the sealing glass. For example, as can be seen from the examples of the present invention such as "No. 5, 10, 15, 20", "No. 24, 29", "No. 37, 39", "No. 7~12", and "No. 26~29", the metal material of the present invention can adjust the magnitude of the axial (stretching direction) thermal expansion coefficient by selecting the blending ratio (content) of Cr and / or Mo and the reduction ratio when the material is stretched to reduce its diameter. In this way, the axial (stretching direction) thermal expansion coefficient can be made as close as possible to the thermal expansion coefficient of the sealing glass to that of the sealing glass. Furthermore, it can be seen that the metal material of the present invention has a significantly higher axial electrical conductivity compared to conventional lead pin materials such as 50.5% Ni-Fe and copper core pins, and also has a significantly higher axial thermal conductivity (thermal conductivity in the thickness direction in the case of plate-shaped metal materials; the same applies hereinafter) compared to conventional stem base materials such as carbon steel (thermal conductivity: approximately 40~60 W / m·K). Furthermore, as can be seen from, for example, "No. 7-12" and "No. 26-29," which are examples of the present invention, the metal material of the present invention can change its axial electrical conductivity and axial thermal conductivity not only by changing the component composition but also by changing the reduction ratio during diameter reduction stretching. Therefore, the axial electrical conductivity and axial thermal conductivity can be adjusted according to the application equipment.

[0131] From the above points, it can be understood that when the metal material of the present invention is used as the material for the lead pins of a compression-sealed glass hermetic seal, it is possible to obtain lead pins that have high bonding reliability with the sealing glass and, despite their small diameter, generate little heat when energized with a large current. Furthermore, when the metal material of the present invention is used as the material for the stem base of a compression-sealed glass hermetic seal, that is, when the metal material is in the shape of a plate with its stretching direction in the thickness direction and its stretching direction perpendicular to the plate surface direction, it can be understood that a stem base can be obtained that allows for appropriate compression of the sealing glass and lead pins in the plate surface direction, has high bonding reliability with the sealing glass, and also exhibits excellent heat dissipation performance in the thickness direction.

[0132] [Table 5]

[0133] [Table 6] [Industrial applicability]

[0134] The metal material of the present invention has a coefficient of thermal expansion in the stretching direction < coefficient of thermal expansion perpendicular to the stretching direction, a relatively small coefficient of thermal expansion in the stretching direction, isotropic coefficient of thermal expansion perpendicular to the stretching direction, and high electrical conductivity and thermal conductivity in the stretching direction. Furthermore, the magnitude of the coefficient of thermal expansion in the stretching direction can be adjusted by selecting the blending ratio of Cr and / or Mo and the reduction ratio when the material is stretched to reduce its diameter, and the magnitude of the electrical conductivity and thermal conductivity in the stretching direction can be changed by the magnitude of the reduction ratio when the material is stretched to reduce its diameter. Conventionally, no metal material with such properties has been known. The metal material of the present invention can be used as a material for lead pins and stem bases of compression-sealed glass hermetic seals used in hermetic terminals and semiconductor laser devices, and is particularly suitable as such a material. However, it can also be used as, for example, an axial material having a low axial thermal expansion coefficient and high axial electrical conductivity, or a plate material having a low thermal expansion coefficient in the thickness direction and high thermal conductivity in the thickness direction. For example, it can be used in conductive members and heat sinks that are joined with other low thermal expansion materials. [Explanation of symbols]

[0135] 1 Stem base 2 lead pins 3. Sealing glass 4 Through holes

Claims

1. It consists of a [Cr or / and Mo]-Cu composite having a metallic structure in which a Cr phase and / or Mo phase are dispersed in a Cu matrix. The [Cr and / or Mo]-Cu composite is a diameter-reduced stretched material for powder metallurgy molded articles, and is a metallic material characterized by having a cross-sectional structure in the stretching direction in which layered or linear Cr phases and / or Mo phases are dispersed in the Cu matrix, and a cross-sectional structure perpendicular to the stretching direction in which flaky, small-piece, or granular Cr phases and / or Mo phases are dispersed in the Cu matrix, when observed in cross-sectional structure with an optical microscope.

2. The average coefficient of thermal expansion in the stretching direction from 30°C to 450°C is 7.0 to 12.0 × 10⁻⁶. －６ The average thermal expansion coefficient perpendicular to the extension direction from 30°C to 450°C is 18.0 × 10⁻¹⁰ / K. －６ The metallic material according to claim 1, characterized in that it is less than or equal to / K and [average thermal expansion coefficient in the stretching direction from 30°C to 450°C] < [average thermal expansion coefficient in the direction perpendicular to stretching from 30°C to 450°C].

3. Electrical conductivity in the stretching direction is 20.0 × 10⁻⁶ ６ The metallic material according to claim 1 or 2, characterized in that it has a thermal conductivity of S / m or more or 180 W / m·K or more.

4. The metallic material according to claim 1, characterized in that the [Cr and / or Mo]-Cu composite has a total Cr and / or Mo content of 35 to 60 mass%.

5. The metal material according to claim 1, characterized in that it is a rod-shaped or wire-shaped metal material with the stretching direction as the axial direction and the stretching direction perpendicular to the radial direction.

6. The metal material according to claim 1, characterized in that the stretching direction is the thickness direction and the direction perpendicular to the stretching is the surface direction.

7. A method for producing the metal material described in claim 1, A process (A) to obtain a material for surface reduction processing consisting of a [Cr and / or Mo]-Cu composite through a process of sintering powder raw materials, A method for manufacturing a metal material, characterized by comprising a step (B) of reducing the diameter of the material obtained in step (A) by reducing the surface area and stretching it into a rod or wire shape.

8. The method for manufacturing a metal material according to claim 7, characterized in that step (B) includes a step of finishing drawing the material.

9. Furthermore, the method for manufacturing a metal material according to claim 7 or 8, characterized by having a step (C) of grinding or polishing the surface of the rod-shaped or wire-shaped material obtained in step (B) (however, including the rod-shaped or wire-shaped material obtained in step (B) cut to a predetermined length).

10. Furthermore, the method for manufacturing a metal material according to claim 7 or 8, further comprising a step (D) of cutting the rod-shaped or wire-shaped material obtained in step (B) in the radial direction, thereby cutting out a plate material in which the axial direction of the material is the plate thickness direction and the radial direction is the plate surface direction.

11. Furthermore, the method for manufacturing a metal material according to claim 9, characterized by further comprising a step (D) of cutting the rod-shaped or wire-shaped material that has undergone step (C) in the radial direction, thereby cutting out a plate material in which the axial direction of the material is the plate thickness direction and the radial direction is the plate surface direction.

12. A rod-shaped or wire-shaped metal material for lead pins constituting a compression-sealed glass hermetic seal, It consists of a [Cr or / and Mo]-Cu composite having a metallic structure in which a Cr phase and / or Mo phase are dispersed in a Cu matrix. The [Cr and / or Mo]-Cu composite is a diameter-reduced stretchable material for powder metallurgy molded articles, and is characterized by having an axial cross-sectional structure in which layered or linear Cr phases and / or Mo phases are dispersed in the Cu matrix, and a radial cross-sectional structure in which flaky, small-piece, or granular Cr phases and / or Mo phases are dispersed in the Cu matrix, as observed under an optical microscope, and is a metallic material for lead pins of compression-sealed glass hermetic seals.

13. The average axial thermal expansion coefficient from 30°C to 450°C is 7.0 to 12.0 × 10⁻⁶. －６ The mean radial thermal expansion coefficient from 30°C to 450°C is 18.0 × 10⁻⁶ / K. －６ A metal material for a lead pin of a compression-sealed glass hermetic seal according to claim 12, characterized in that it is less than or equal to / K and [average axial thermal expansion coefficient from 30°C to 450°C] < [average radial thermal expansion coefficient from 30°C to 450°C].

14. The axial electrical conductivity is 20.0 × 10 ６ A metal material for lead pins of a compression-sealed glass hermetic seal according to claim 12 or 13, characterized in that it is S / m or greater.

15. The [Cr and / or Mo]-Cu composite is characterized in that the total content of Cr and / or Mo is 35 to 60 mass%, as a metal material for lead pins of a compression-sealed glass hermetic seal according to claim 12.

16. A plate-shaped metal material for the stem base constituting a compression-sealed glass hermetic seal, It consists of a [Cr or / and Mo]-Cu composite having a metallic structure in which a Cr phase and / or Mo phase are dispersed in a Cu matrix. The [Cr and / or Mo]-Cu composite is a diameter-reduced stretched material for powder metallurgy molded articles, and is characterized in that, when the cross-sectional structure is observed with an optical microscope, it has a cross-sectional structure in the thickness direction in which layered or linear Cr phases and / or Mo phases are dispersed in the Cu matrix, and a cross-sectional structure parallel to the plate surface in which flaky, small-piece, or granular Cr phases and / or Mo phases are dispersed in the Cu matrix, and is a metallic material for the stem base of a compression-sealed glass hermetic seal.

17. The average coefficient of thermal expansion in the thickness direction from 30°C to 450°C is 7.0 to 12.0 × 10⁻⁶. －６ The average coefficient of thermal expansion in the direction of the plate surface from 30°C to 450°C is 18.0 × 10⁻¹⁰ / K. －６ A metal material for the stem base of a compression-sealed glass hermetic seal according to claim 16, characterized in that it is less than or equal to / K and [average thermal expansion coefficient in the thickness direction from 30°C to 450°C] < [average thermal expansion coefficient in the surface direction from 30°C to 450°C].

18. A metal material for the stem base of a compression-sealed glass hermetic seal according to claim 16 or 17, characterized in that the thermal conductivity in the thickness direction is 180 W / m·K or more.

19. The [Cr and / or Mo]-Cu composite is characterized in that the total content of Cr and / or Mo is 35 to 60 mass%, as a metallic material for the stem base of a compression-sealed glass hermetic seal according to claim 16.

20. A plate-shaped stem base that constitutes a compression-sealed glass hermetic seal, It consists of a [Cr or / and Mo]-Cu composite having a metallic structure in which a Cr phase and / or Mo phase are dispersed in a Cu matrix. The [Cr and / or Mo]-Cu composite is a diameter-reduced stretching material for powder metallurgy molded articles, and is characterized in that, when the cross-sectional structure is observed with an optical microscope, it has a cross-sectional structure in the thickness direction in which layered or linear Cr phases and / or Mo phases are dispersed in the Cu matrix, and a cross-sectional structure parallel to the plate surface in which flaky, small-piece, or granular Cr phases and / or Mo phases are dispersed in the Cu matrix, forming a stem base for a compression-sealed glass hermetic seal.

21. The average thermal expansion coefficient in the plate thickness direction from 30°C to 450°C is 7.0 to 12.0×10 －６ / K, the average thermal expansion coefficient in the plate surface direction from 30°C to 450°C is 18.0×10 －６ / K or less, and [the average thermal expansion coefficient in the plate thickness direction from 30°C to 450°C] < [the average thermal expansion coefficient in the plate surface direction from 30°C to 450°C], and the stem base of the compression-sealed glass hermetic seal according to claim 20.

22. A stem base for a compression-sealed glass hermetic seal according to claim 20 or 21, characterized in that the thermal conductivity in the thickness direction of the plate is 180 W / m·K or more.

23. The stem base of a compression-sealed glass hermetic seal according to claim 20, characterized in that the [Cr and / or Mo]-Cu composite has a total Cr and / or Mo content of 35 to 60 mass%.

24. The plate-shaped stem base is made of a [Cr or / and Mo]-Cu composite having a metallic structure in which a Cr phase and / or Mo phase are dispersed in a Cu matrix. The [Cr and / or Mo]-Cu composite is a diameter-reduced and stretched material for powder metallurgy molded articles, and is characterized in that, when the cross-sectional structure is observed with an optical microscope, it has a cross-sectional structure in the thickness direction in which layered or linear Cr phases and / or Mo phases are dispersed in the Cu matrix, and a cross-sectional structure parallel to the plate surface in which flaky, small-piece, or granular Cr phases and / or Mo phases are dispersed in the Cu matrix.

25. The aforementioned stem base has an average thermal expansion coefficient in the thickness direction of the plate from 30°C to 450°C of 7.0 to 12.0 × 10 －６ The average coefficient of thermal expansion in the direction of the plate surface from 30°C to 450°C is 18.0 × 10⁻¹⁰ / K. －６ The semiconductor laser apparatus according to claim 24, characterized in that the temperature is less than or equal to / K and [average thermal expansion coefficient in the thickness direction from 30°C to 450°C] < [average thermal expansion coefficient in the surface direction from 30°C to 450°C].

26. The semiconductor laser apparatus according to claim 24 or 25, characterized in that the stem base has a thermal conductivity of 180 W / m·K or more in the thickness direction.

27. The semiconductor laser apparatus according to claim 24, characterized in that the [Cr and / or Mo]-Cu composite has a total Cr and / or Mo content of 35 to 60 mass%.

28. The lead pin is made of a [Cr or / and Mo]-Cu composite having a metallic structure in which a Cr phase and / or Mo phase are dispersed in a Cu matrix. The [Cr and / or Mo]-Cu composite is a diameter-reducing and stretching material for powder metallurgy molded bodies, and is characterized in that, when the cross-sectional structure is observed with an optical microscope, it has an axial cross-sectional structure in which layered or linear Cr phases and / or Mo phases are dispersed in the Cu matrix, and a radial cross-sectional structure in which flaky, small-piece, or granular Cr phases and / or Mo phases are dispersed in the Cu matrix.

29. The lead pin has an average axial thermal expansion coefficient of 7.0 to 12.0 × 10⁻¹⁰ from 30°C to 450°C. －６ The mean radial thermal expansion coefficient from 30°C to 450°C is 18.0 × 10⁻⁶ / K. －６ The semiconductor laser apparatus according to claim 28, characterized in that the temperature is less than or equal to / K and the average axial thermal expansion coefficient from 30°C to 450°C is less than the average radial thermal expansion coefficient from 30°C to 450°C.

30. The aforementioned lead pin has an axial electrical conductivity of 20.0 × 10 ６ The semiconductor laser apparatus according to claim 28 or 29, characterized in that it is S / m or greater.

31. The semiconductor laser apparatus according to claim 28, characterized in that the [Cr and / or Mo]-Cu composite has a total Cr and / or Mo content of 35 to 60 mass%.

32. The plate-shaped stem base and lead pins are made of a [Cr or / and Mo]-Cu composite having a metallic structure in which a Cr phase and / or Mo phase are dispersed in a Cu matrix. The [Cr and / or Mo]-Cu composite constituting the plate-shaped stem base is a diameter-reduced stretched material for powder metallurgy molded products, and when the cross-sectional structure is observed with an optical microscope, it has a cross-sectional structure in the thickness direction in which layered or linear Cr phases and / or Mo phases are dispersed in the Cu matrix, and a cross-sectional structure parallel to the plate surface in which flaky, small-piece, or granular Cr phases and / or Mo phases are dispersed in the Cu matrix. The [Cr and / or Mo]-Cu composite constituting the lead pin is a diameter-reduced and drawn material for a powder metallurgy molded body, and is characterized in that, when the cross-sectional structure is observed with an optical microscope, it has an axial cross-sectional structure in which layered or linear Cr phases and / or Mo phases are dispersed in the Cu matrix, and a radial cross-sectional structure in which flaky, small-piece, or granular Cr phases and / or Mo phases are dispersed in the Cu matrix.

33. The aforementioned stem base has an average thermal expansion coefficient in the thickness direction of the plate from 30°C to 450°C of 7.0 to 12.0 × 10 －６ The average coefficient of thermal expansion in the direction of the plate surface from 30°C to 450°C is 18.0 × 10⁻¹⁰ / K. －６ The temperature is less than or equal to / K, and the average thermal expansion coefficient in the thickness direction from 30°C to 450°C is less than the average thermal expansion coefficient in the surface direction from 30°C to 450°C. The lead pin has an average axial thermal expansion coefficient of 7.0 to 12.0 × 10⁻¹⁰ from 30°C to 450°C. －６ The mean radial thermal expansion coefficient from 30°C to 450°C is 18.0 × 10⁻⁶ / K. －６ The semiconductor laser apparatus according to claim 32, characterized in that the temperature is less than or equal to / K and the average axial thermal expansion coefficient from 30°C to 450°C is less than the average radial thermal expansion coefficient from 30°C to 450°C.

34. The aforementioned stem base has a thermal conductivity of 180 W / m·K or more in the thickness direction. The aforementioned lead pin has an axial electrical conductivity of 20.0 × 10 ６ A semiconductor laser apparatus according to claim 32 or 33, characterized in that it is S / m or greater.

35. The semiconductor laser apparatus according to claim 32, characterized in that the [Cr and / or Mo]-Cu composite constituting the stem base and the lead pin has a total Cr and / or Mo content of 35 to 60 mass%.

36. The semiconductor laser apparatus according to any one of 24, 28, or 32, characterized in that a compression-sealed glass hermetic seal is formed with the stem base and / or the lead pin as constituent members.

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