Metallic materials and components of compression-sealed glass hermetic seals

Abstract

The present invention provides a metal material that is particularly suitable for use as a component of a compression-sealed glass hermetic seal, that has high bonding reliability with the sealing glass, that allows a large current to pass through it even with a small diameter, that can realize a lead pin that generates little heat when current is passed through it, that can appropriately compress the sealing glass and lead pin in the plate surface direction, that has high bonding reliability with the sealing glass, and that can realize a stem base that has excellent heat dissipation performance in the plate thickness direction. [Solution] The composite consists of a [Cr and / or Mo]-Cu composite having a metal structure in which Cr phases and / or Mo phases are dispersed in a Cu matrix. This [Cr and / or Mo]-Cu composite is a diameter-reduced, elongated powder metallurgy compact, and when cross-sectionally observed with an optical microscope, it has a cross-sectional structure in the elongation direction in which lamellar or linear Cr phases and / or Mo phases are dispersed in the Cu matrix, and a cross-sectional structure perpendicular to the elongation direction in which flake-like, small platelet-like, or granular Cr phases and / or Mo phases are dispersed in the Cu matrix.

Description

[Technical Field]

[0001] The present invention relates to a metallic material consisting of a [Cr and / or Mo]-Cu composite with a specific metal structure, and to components (lead pins, stem bases) of compression-sealed glass hermetic seals that utilize this metallic material. [Background technology]

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

[0003] Glass hermetic seals come in two types: matched and compression. The matched seal uses a metal stem base, metal lead pins, and sealing glass with similar thermal expansion coefficients to minimize differential shrinkage between them. The lead pins are chemically sealed via a metal oxide film formed at the interface between the metal and sealing glass. On the other hand, the compression seal utilizes the difference in thermal expansion coefficients between the stem base (metal) and sealing glass to apply compressive stress to the sealing glass and lead pins from the stem base side, mechanically sealing the lead pins. The lead pins and glass are placed in the stem base through-holes, and the glass is heated and melted. When the glass is then cooled and solidified, the stem base compresses the sealing glass and lead pins due to the difference in shrinkage between the stem base and sealing glass, mechanically sealing the lead pins.

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

[0005] Generally, in a semiconductor laser device equipped with a compression-sealed glass hermetic seal, when a semiconductor laser element that generates a large amount of heat is mounted, the stem base is made of carbon steel, which has a higher thermal conductivity and is also cheaper than materials such as Kovar. If the material of the stem base alone is insufficient for heat dissipation, the semiconductor laser element is mounted on the top surface of the stem base via a laser element holder (a block-shaped heat sink protruding from the top surface of the stem base) that has a heat dissipation function (e.g., Patent Documents 2 and 3). Typically, this laser element holder is made of Cu or other materials with high thermal conductivity from the perspective of heat dissipation. [Prior art documents] [Patent documents]

[0006] [Patent Document 1] Japanese Patent Application Laid-Open No. 2008-27679 [Patent Document 2] Japanese Patent Application Publication No. 8-242041 [Patent Document 3] Japanese Patent Application Laid-Open No. 2016-29718 Summary of the Invention [Problem to be solved by the invention]

[0007] The lead pins and stem bases, which are components of the compression-sealed glass hermetic seal, have the following technical challenges: First, for the lead pin, if the difference in thermal expansion between the lead pin and the sealing glass in the axial direction is large, the axial shear stress occurring at the interface between the lead pin and the sealing glass will be large. For example, in the case of Kovar (thermal expansion coefficient: 5.3 × 10 -6 / K) has a thermal expansion coefficient of 7.6×10 -6 / K sealing glass (FN-13W, Nippon Electric Glass Co., Ltd.) is used, but 2 × 10 -6 / K. This causes a thermal expansion coefficient difference of about 1 / K. This can lead to problems such as fatigue caused by repeated temperature increases and decreases during use, which can lead to cracks in the sealing glass, reducing the reliability of the bond between the lead pin and the sealing glass. Furthermore, if the lead pin has low axial electrical conductivity, it generates a large amount of heat when electricity is passed through it, making it unusable for applications that carry large currents.

[0008] Among the materials traditionally used for lead pins, Ni-Fe alloys and some stainless steels have relatively small axial thermal expansion differences with the sealing glass. However, all of the materials used for conventional lead pins have low axial electrical conductivity, making them unable to address the issues mentioned above. In particular, electric compressors for EVs and HEVs have become increasingly high-current in recent years. The lead pins of their power connection terminals (airtight terminals with compression-sealed glass hermetic seals) are required to generate sufficiently low heat even when subjected to high currents. However, the conventional lead pins mentioned above cannot meet this requirement. Furthermore, copper-core pins with a 50% Ni-Fe core clad in copper are used to reduce heat generation during high currents, but there are limits to how much heat can be reduced. Furthermore, as electric compressors continue to carry higher currents, the pin diameters will increase, making it impossible to meet the demand for smaller automotive components.

[0009] If the electrical conductivity of the lead pin is low, the power consumption at the lead pin increases, placing a greater strain on the onboard battery. Even higher currents are required for electric vehicles, and existing materials, including copper-core pins, cannot handle the lead pin diameter (e.g., φ3.2 mm) used in airtight terminals, so the lead pin diameter must be made even larger. However, if four times the current current is to be passed through, the lead pin diameter would be φ6.4 mm, which would not only create problems for reducing the weight and size of automotive parts, but would also create a cost problem as the material cost of the lead pin would increase fourfold. As described above, the material for the lead pin is required to have a relatively small axial thermal expansion coefficient, preferably an axial thermal expansion coefficient as close as possible to the thermal expansion coefficient of the sealing glass, and also to have as high an axial electrical conductivity as possible, but to date no metal material that can satisfy these requirements has been known.

[0010] Next, the stem base must compress the sealing glass and lead pins to mechanically seal them. Therefore, its thermal expansion coefficient in the plate surface direction must be somewhat greater than that of the sealing glass. However, similar to the relationship between the lead pins and sealing glass described above, if the thermal expansion difference between the stem base and the sealing glass in the plate thickness direction is large, the shear stress in the plate thickness direction at the interface between the stem base and the sealing glass increases. This can lead to problems such as cracks in the sealing glass due to fatigue caused by repeated temperature fluctuations during use, reducing the reliability of the bond between the stem base and the sealing glass. Furthermore, in the case of semiconductor laser devices, if the heat generated by the semiconductor laser element is not properly dissipated through the stem base, problems such as reduced output and lifespan of the laser element can occur.

[0011] Conventional stem bases are made of materials (such as carbon steel) with a thermal expansion coefficient somewhat greater than that of the sealing glass, due to the need to compress the sealing glass and lead pins. This inevitably results in 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, 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 them unable to adequately dissipate heat generated by semiconductor laser elements. As a result, conventional semiconductor laser devices have insufficient heat dissipation performance, which can lead to problems such as reduced laser element output and lifespan, and are unable to keep up with the increasing power and performance of semiconductor laser devices. As described above, the stem base material must have a thermal expansion coefficient in the plate plane direction that is somewhat larger than that of the sealing glass, while the thermal expansion coefficient in the plate thickness direction must be relatively small and as close as possible to that of the sealing glass. In other words, it is desirable that the difference in thermal expansion between the stem base material and the sealing glass in the plate thickness direction be as small as possible. Furthermore, the stem base material must have as high a thermal conductivity in the plate thickness direction as possible. However, no metal material that can meet these requirements has been known to date.

[0012] The present invention has been made to solve the problems of the prior art as 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 is possible to realize lead pins with a relatively small axial thermal expansion coefficient and high axial electrical conductivity; (ii) it is possible to realize a stem base with a thermal expansion coefficient in the plate surface direction required for a stem base, a relatively small thermal expansion coefficient in the plate thickness direction, and high thermal conductivity in the plate thickness direction; and (iii) it is possible to adjust the axial thermal expansion coefficient of the lead pin and the plate thickness direction thermal expansion coefficient of the stem base to match the thermal expansion coefficient of the sealing glass to be used, so that they can be made close to the thermal expansion coefficient of the sealing glass, and a method for manufacturing the metal material.

[0013] 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 bonding reliability with the sealing glass, is capable of carrying a large current even with a small diameter, and generates little heat when current is passed through it, 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 bonding reliability with the sealing glass, and also has excellent heat dissipation performance in the plate thickness direction. Another object of the present invention is to provide an airtight terminal using the above 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 device in which the above-mentioned metal material is used for the lead pins and / or stem base. [Means for solving the problem]

[0014] The present inventors have conducted extensive research to solve the above problems, and as a result have come to the following realization, which has led to the development of a novel metal material according to the present invention and a product using the same. (i) Metallic materials obtained by reducing the area of ​​a [Cr and / or Mo]-Cu composite material obtained by powder metallurgy and then reducing and elongating it into a rod or wire shape (i.e., [Cr and / or Mo]-Cu composites that are elongated powder metallurgical compacts) have a metallic structure in which Cr and / or Mo phases are dispersed in a Cu matrix. However, when cross-sectionally observed with an optical microscope, they have a cross-sectional structure in the elongation direction (axial direction) in which lamellar or linear Cr and / or Mo phases are dispersed in the Cu matrix, and a cross-sectional structure in the transverse direction (radial direction) in which flake-like, small-plate-like, or granular Cr and / or Mo phases are dispersed in the Cu matrix. While rolled Cr-Cu composite sheets (rolled into sheets using flat rolls) have been known, the cross-sectional structure of these metallic materials is completely different from that of the rolled Cr-Cu composite sheets.

[0015] (ii) The metallic material with the above-described cross-sectional structure in the stretch direction and transverse to the stretch direction (the [Cr and / or Mo]-Cu composite, which is a diameter-reduced and drawn powder metallurgical compact) has unique properties (characteristics) that are different from those of metallic materials conventionally used for lead pins and stem bases of compression-sealed glass hermetic seals, or for other conductive components. Specifically, this metallic material has a thermal expansion coefficient in the stretch direction that is less than that in the transverse direction, a relatively small thermal expansion coefficient in the stretch direction, an isotropic thermal expansion coefficient in the transverse direction, and high electrical and thermal conductivities in the stretch direction. Furthermore, among these metallic materials, those with further optimized properties can have a thermal expansion coefficient in the stretch direction close to that of sealing glass. Furthermore, they have significantly higher electrical conductivities in the stretch direction than Ni-Fe alloys, which are commonly used for lead pins, and significantly higher thermal conductivities in the stretch direction than carbon steels, which are commonly used for stem bases.

[0016] Therefore, rod- or wire-shaped metal materials ([Cr and / or Mo]-Cu composites that are diameter-reduced and drawn powder metallurgical compacts) with the above-mentioned drawing direction as the axial direction and the direction perpendicular to the drawing direction as the radial direction have a coefficient of thermal expansion that is less than the radial coefficient, a relatively small coefficient of axial thermal expansion, an isotropic coefficient of radial thermal expansion, and high axial electrical conductivity. Furthermore, among these, those with further optimized properties can have an axial coefficient of thermal expansion close to that of sealing glass, and have significantly higher axial electrical conductivity than 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 and drawn powder metallurgical compact) with the above-mentioned stretching direction as the thickness direction and the direction perpendicular to the stretching as the plate surface direction, has a thermal expansion coefficient in the plate surface direction required for a stem base, and the thermal expansion coefficient in the plate surface direction is relatively small, isotropic, and has high thermal conductivity in the plate thickness direction, so that the thermal expansion coefficient in the plate thickness direction is less than the thermal expansion coefficient in the plate surface direction. Furthermore, among these materials, those with further optimized properties can have a thermal expansion coefficient in the plate thickness direction close to that of sealing glass, and also have a thermal conductivity in the plate thickness direction that is significantly higher than that of carbon steel, which is widely used for stem bases.

[0017] Furthermore, a key feature of this metal material is that its thermal expansion coefficient in the elongation direction can be adjusted by selecting the Cr and / or Mo content in the [Cr and / or Mo]-Cu composite and the area reduction rate during elongation (diameter reduction). In other words, the axial thermal expansion coefficient of rod- or wire-shaped metal materials can be adjusted, while the thickness-direction thermal expansion coefficient of plate-shaped metal materials can be adjusted. This allows the axial thermal expansion coefficient of the lead pin and the thickness-direction thermal expansion coefficient of the stem base to be as close as possible to the thermal expansion coefficient of the sealing glass. This maximizes the reliability of the joint between the lead pin and stem base and the sealing glass, a key issue in compression-sealed glass hermetic seals. Furthermore, the electrical conductivity and thermal conductivity in the elongation direction of this metal material change depending on the area reduction rate during elongation (diameter reduction). The greater the area reduction rate, the greater the electrical conductivity and thermal conductivity in the elongation direction. In other words, the greater the reduction in area, the greater the axial electrical conductivity of rod-shaped or wire-shaped metal materials, and the greater the thermal conductivity through the plate thickness of plate-shaped metal materials. Therefore, by changing the reduction in area, it is possible to appropriately adjust the axial electrical conductivity or the thermal conductivity through the plate thickness depending on the application of the metal material. Therefore, in terms of applications for compression-sealed glass hermetic seals, the former rod- or wire-shaped metal material is extremely suitable for lead pins, and the latter plate-shaped metal material is extremely suitable for stem bases, and it can be said that they highly satisfy the various properties required for lead pins and stem bases as described above. Such metal materials were completely unknown in the past and are novel metal materials invented by the present invention.

[0018] (iii) This metallic material can be produced relatively easily by subjecting a raw material consisting of a [Cr and / or Mo]-Cu composite (powder metallurgy compact) obtained through a process of sintering a powder raw material to area reduction (diameter-reducing and elongating), thereby reducing and elongating it into a rod or wire shape. Here, the rod-shaped or wire-shaped metallic material described above can be produced simply by the area-reducing process (diameter-reducing and elongating), and the plate-shaped metallic material described above can be produced by cutting the rod-shaped or wire-shaped raw material obtained by the area-reducing process (diameter-reducing and elongating) in the radial direction, and cutting out a plate material with the axial direction of the raw material as the plate thickness direction and the radial direction as the plate surface direction.

[0019] The present invention was made based on these findings and has the following gist. [1] 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, drawn material of a powder metallurgy compact, and when observed through an optical microscope, it has a cross-sectional structure in the drawing direction in which lamellar or linear Cr and / or Mo phases are dispersed in a Cu matrix, and a cross-sectional structure perpendicular to the drawing direction in which flake-like, small-platelet-like, or granular Cr and / or Mo phases are dispersed in a Cu matrix. [2] In the metal material described in [1] above, the average thermal expansion coefficient in the stretching direction from 30°C to 450°C is 7.0 to 12.0 × 10 -6 / K, and the average thermal expansion coefficient in the direction perpendicular to the stretching direction from 30°C to 450°C is 18.0×10 -6 / K or less, and the average thermal expansion coefficient in the stretching direction from 30°C to 450°C is less than the average thermal expansion coefficient in the direction perpendicular to the stretching direction from 30°C to 450°C.

[0020] [3] In the metal material described in [1] or [2] above, the electrical conductivity in the stretching direction is 20.0 × 10 6 A metallic material characterized by a thermal conductivity of 180 W / m·K or more. [4] In the metallic material according to any one of [1] to [3] 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%. [5] The metal material according to any one of [1] to [4] above, characterized in that it is a rod-shaped or wire-shaped metal material with the extension direction as the axial direction and the direction perpendicular to the extension as the radial direction. [6] The metal material according to any one of the above [1] to [4], characterized in that it is a plate-shaped metal material in which the stretching direction is the plate thickness direction and the direction perpendicular to the stretching is the plate surface direction.

[0021] [7] A method for producing a metal material according to any one of [1] to [4] above, A step (A) of obtaining a material for surface reduction processing comprising a [Cr and / or Mo]-Cu composite through a step of sintering the powder raw material; The method for producing a metal material comprises a step (B) of reducing the area of ​​the raw material obtained in the step (A) and elongating it into a rod or wire shape by reducing the diameter. [8] The method for producing a metallic material according to the above [7], wherein the step (B) comprises a step of subjecting the raw material to finish drawing. [9] A method for producing a metal material according to the above [7] or [8], further comprising a step (C) of grinding or polishing the surface of the rod-shaped or wire-shaped material obtained in step (B) (including the rod-shaped or wire-shaped material obtained in step (B) cut to a predetermined length).

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

[11] The manufacturing method of the above [9], further comprising a step (D) of cutting the rod-shaped or wire-shaped material that has undergone the step (C) in the radial direction to cut 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.

[0022]

[12] A rod-shaped or wire-shaped metal material for a lead pin that constitutes a compression-sealed glass hermetic seal, It consists of a [Cr and / or Mo]-Cu composite having a metal 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 drawn material of a powder metallurgy compact, and when observed through a cross-sectional microscope, is characterized by having an axial cross-sectional structure in which lamellar or linear Cr and / or Mo phases are dispersed in a Cu matrix, and a radial cross-sectional structure in which flake-like, small platelet-like, or granular Cr and / or Mo phases are dispersed in a Cu matrix. This metallic material is for use in lead pins of compression-sealed glass hermetic seals.

[0023]

[13] In the metallic material described in

[12] above, the average axial thermal expansion coefficient from 30°C to 450°C is 7.0 to 12.0 × 10 -6 / K, and the radial average thermal expansion coefficient from 30°C to 450°C is 18.0×10 -6 / K or less, 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.

[14] In the metallic material described in

[12] or

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

[15] A metal material for a lead pin of a compression-sealed glass hermetic seal, characterized in that in the metal material of any of

[12] to

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

[0024]

[16] A plate-shaped metal material for a stem base that constitutes a compression-sealed glass hermetic seal, It consists of a [Cr and / or Mo]-Cu composite having a metal 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 drawn material of a powder metallurgy compact, and when observed through an optical microscope, it has a cross-sectional structure in the thickness direction in which lamellar or linear Cr and / or Mo phases are dispersed in the Cu matrix, and a cross-sectional structure parallel to the plate surface in which flake-like, small-plate-like, or granular Cr and / or Mo phases are dispersed in the Cu matrix, making it 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 / K, and the average thermal expansion coefficient in the plate direction from 30°C to 450°C is 18.0×10 -6 / K or less, 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 plane direction from 30°C to 450°C.

[18] A metal material for a stem base of a compression-sealed glass hermetic seal according to

[16] or

[17] above, characterized in that the thermal conductivity in the thickness direction is 180 W / m·K or more.

[19] A metal material for a stem base of a compression-sealed glass hermetic seal, wherein the [Cr and / or Mo]-Cu composite in any of the metal materials

[16] to

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

[0026]

[20] A lead pin that constitutes a compression-sealed glass hermetic seal, It consists of a [Cr and / or Mo]-Cu composite having a metal 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 drawn material of a powder metallurgical compact, and when cross-sectionally observed with an optical microscope, it has an axial cross-sectional structure in which lamellar or linear Cr and / or Mo phases are dispersed in a Cu matrix, and a radial cross-sectional structure in which flake-like, small platelet-like, or granular Cr and / or Mo phases are dispersed in a Cu matrix, which is a lead pin for a compression-sealed glass hermetic seal.

[0027]

[21] For the lead pin of

[20] above, the average axial thermal expansion coefficient from 30°C to 450°C is 7.0 to 12.0 × 10 -6 / K, and the radial average thermal expansion coefficient from 30°C to 450°C is 18.0×10 -6 / K or less, 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.

[22] In the lead pin of

[20] or

[21] above, the electrical conductivity in the axial direction is 20.0 × 10 6 A lead pin of a compression-sealed glass hermetic seal, characterized in that it has a resistance of S / m or more.

[23] A lead pin for a compression-sealed glass hermetic seal according to any one of the above

[20] to

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

[0028]

[24] A plate-shaped stem base that constitutes a compression-sealed glass hermetic seal, It consists of a [Cr and / or Mo]-Cu composite having a metal 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 drawn material of a powder metallurgical compact, and when observed through an optical microscope, it has a cross-sectional structure in the thickness direction in which layered or linear Cr and / or Mo phases are dispersed in the Cu matrix, and a cross-sectional structure parallel to the plate surface in which flake-like, small-plate-like, or granular Cr and / or Mo phases are dispersed in the Cu matrix, making it a stem base for a compression-sealed glass hermetic seal.

[0029]

[25] In the stem base of

[24] above, the average thermal expansion coefficient in the thickness direction from 30°C to 450°C is 7.0 to 12.0 × 10 -6 / K, and the average thermal expansion coefficient in the plate direction from 30°C to 450°C is 18.0×10 -6 / K or less, 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 plane direction from 30°C to 450°C.

[26] A stem base for a compression-sealed glass hermetic seal according to the above

[24] or

[25] , characterized in that the thermal conductivity in the thickness direction is 180 W / m·K or more.

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

[24] to

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

[0030]

[28] In a compression-sealed hermetic terminal, the lead pin is made of a [Cr and / or Mo]-Cu composite having a metal structure in which a Cr phase and / or Mo phase is dispersed in a Cu matrix; The [Cr and / or Mo]-Cu composite is a diameter-reduced and stretched material of a powder metallurgical compact, and when observed through an optical microscope, it has an axial cross-sectional structure in which layered or linear Cr and / or Mo phases are dispersed in a Cu matrix, and a radial cross-sectional structure in which flake-like, small-piece-like, or granular Cr and / or Mo phases are dispersed in a Cu matrix.

[29] In the airtight terminal of

[28] , the lead pin has an axial average thermal expansion coefficient of 7.0 to 12.0 × 10 from 30 ° C to 450 ° C. -6 / K, and the radial average thermal expansion coefficient from 30°C to 450°C is 18.0×10 -6 / 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].

[0031]

[30] In the airtight terminal of the above

[28] or

[29] , the lead pin has an axial electrical conductivity of 20.0 × 10 6 An airtight terminal characterized by a resistance of S / m or more.

[31] In the hermetic terminal according to any one of the above

[28] to

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

[32] An electric compressor comprising the airtight terminal of

[28] or

[29] above.

[33] An electric compressor comprising the airtight terminal of

[30] or

[31] above.

[0032]

[34] The plate-shaped stem base is made of a [Cr and / or Mo]-Cu composite having a metal 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 drawn material of a powder metallurgical compact, and when cross-sectionally observed with an optical microscope, it has a cross-sectional structure in the thickness direction in which layered or linear Cr and / or Mo phases are dispersed in a Cu matrix, and a cross-sectional structure parallel to the plate surface in which flake-like, small-plate-like, or granular Cr and / or Mo phases are dispersed in a Cu matrix, making it a semiconductor laser device.

[35] In the semiconductor laser device of

[34] , 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 / K, and the average thermal expansion coefficient in the plate direction from 30°C to 450°C is 18.0×10 -6 / K or less, 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 plane direction from 30°C to 450°C.

[0033]

[36] The semiconductor laser device according to

[34] or

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

[37] In the semiconductor laser device of any one of

[34] to

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

[38] The lead pin is made of a [Cr and / or Mo]-Cu composite having a metal 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 of a powder metallurgical compact, and when cross-sectionally observed with an optical microscope, it has an axial cross-sectional structure in which layered or linear Cr and / or Mo phases are dispersed in a Cu matrix, and a radial cross-sectional structure in which flake-like, small platelet-like, or granular Cr and / or Mo phases are dispersed in a Cu matrix, resulting in a semiconductor laser device.

[0034]

[39] In the semiconductor laser device of

[38] above, the lead pin has an axial average thermal expansion coefficient of 7.0 to 12.0 × 10 from 30 ° C to 450 ° C. -6 / K, and the radial average thermal expansion coefficient from 30°C to 450°C is 18.0×10 -6 / 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].

[40] In the semiconductor laser device according to the above

[38] or

[39] , the lead pin has an axial electrical conductivity of 20.0×10 6 A semiconductor laser device characterized by a saturation of 1.5 S / m or more.

[41] In the semiconductor laser device of any one of the above

[38] to

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

[0035]

[42] The plate-shaped stem base and lead pin are made of a [Cr and / or Mo]-Cu composite having a metal structure in which Cr phase and / or Mo phase are dispersed in a Cu matrix; The [Cr and / or Mo]-Cu composite constituting the plate-like stem base is a diameter-reduced and elongated material of a powder metallurgical compact, and when observed in cross section with an optical microscope, has a cross section in the thickness direction in which lamellar or linear Cr phases and / or Mo phases are dispersed in a Cu matrix, and a cross section parallel to the plate surface in which flake-like, small-plate-like or granular Cr phases and / or Mo phases are dispersed in a Cu matrix, The [Cr and / or Mo]-Cu composite constituting the lead pin is a diameter-reduced and drawn material of a powder metallurgical compact, and when cross-sectionally observed with an optical microscope, has an axial cross-sectional structure in which layered or linear Cr and / or Mo phases are dispersed in a Cu matrix, and a radial cross-sectional structure in which flake-like, small platelet-like, or granular Cr and / or Mo phases are dispersed in a Cu matrix, making it a semiconductor laser device.

[0036]

[43] In the semiconductor laser device of

[42] 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 / K, and the average thermal expansion coefficient in the plate direction from 30°C to 450°C is 18.0×10 -6 / K or less, and [average thermal expansion coefficient in the thickness direction from 30 ° C to 450 ° C] < [average thermal expansion coefficient in the plate surface direction from 30 ° C to 450 ° C], The lead pin has an axial average thermal expansion coefficient of 7.0 to 12.0 × 10 over the temperature range of 30 to 450 °C. -6 / K, and the radial average thermal expansion coefficient from 30°C to 450°C is 18.0×10 -6 / 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].

[0037]

[44] In the semiconductor laser device according to

[42] or

[43] above, The stem base has a thermal conductivity in the thickness direction of 180 W / m K or more, The lead pin has an axial electrical conductivity of 20.0×10 6 A semiconductor laser device having a luminance of 1.5 S / m or more.

[45] In the semiconductor laser device of any one of

[42] to

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

[46] In the semiconductor laser device of any one of

[34] to

[45] above, a compression-sealed glass hermetic seal is formed with the stem base and / or the lead pin as constituent members. [Effects of the Invention]

[0038] <Metallic material of the present invention> The metallic material of the present invention (a [Cr and / or Mo]-Cu composite, which is a diameter-reduced and drawn powder metallurgical compact) has a thermal expansion coefficient in the drawing direction that is less than that 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, among these metallic materials, those with further optimized properties can have a thermal expansion coefficient in the drawing direction close to that of sealing glass, and have a significantly higher electrical conductivity in the drawing direction than Ni-Fe alloys and the like, which are commonly used in conventional lead pins, and a significantly higher thermal conductivity in the drawing direction than carbon steel and the like, which are commonly used in conventional stem bases.

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

[0040] Furthermore, the thermal expansion coefficient of the metal material of the present invention can be changed (adjusted) in the drawing direction by selecting the blending ratio (content) of Cr and / or Mo in the [Cr and / or Mo]-Cu composite and the area reduction rate during diameter reduction and drawing of the material by area reduction (diameter reduction and drawing). That is, the axial thermal expansion coefficient of a rod-shaped or wire-shaped metal material can be changed (adjusted), and the thickness-wise thermal expansion coefficient of a plate-shaped metal material can be changed (adjusted). This allows the axial thermal expansion coefficient of the lead pin and the thickness-wise thermal expansion coefficient of the stem base to be as close as possible to the thermal expansion coefficient of the sealing glass, thereby maximizing the reliability of the connection between the lead pin and stem base and the sealing glass, which is an issue in compression-sealed glass hermetic seals. Furthermore, in the metal material of the present invention, the magnitude of the electrical conductivity and thermal conductivity in the stretching direction changes depending on the area reduction rate during diameter reduction stretching, and the greater the area reduction rate, the greater the electrical conductivity and thermal conductivity in the stretching direction. That is, the greater the area reduction rate, the greater the axial electrical conductivity in rod-shaped or wire-shaped metal materials, and the greater the thermal conductivity in the thickness direction in plate-shaped metal materials. Therefore, by changing the area reduction rate, it is possible to appropriately adjust the axial electrical conductivity or the thermal conductivity in the thickness direction depending on the application of the metal material.

[0041] Therefore, in applications for compression-sealed glass hermetic seals, the wire- or rod-shaped metal material of the present invention is an extremely suitable metal material for lead pins, enabling the realization of lead pins that have high bonding reliability with the sealing glass, are capable of carrying large currents even with a small diameter, and generate little heat when current is applied.Similarly, the plate-shaped metal material of the present invention is an extremely suitable metal material for stem bases, enabling the realization of stem bases that can appropriately compress the sealing glass and lead pins in the plate surface direction, have high bonding reliability with the sealing glass, and also have excellent heat dissipation performance in the plate thickness direction. Furthermore, according to the manufacturing method of the present invention, the above-mentioned metal material can be manufactured appropriately and efficiently.

[0042] <Components and devices of the present invention> The lead pins of the present invention have a relatively small axial thermal expansion coefficient (axial thermal expansion coefficient < radial thermal expansion coefficient), an isotropic radial thermal expansion coefficient, and high axial electrical conductivity. Furthermore, among these lead pins, those with further optimized properties can achieve an axial thermal expansion coefficient close to that of sealing glass and have significantly higher axial electrical conductivity than Ni-Fe alloys, which have been widely used in conventional lead pins. Furthermore, the magnitude of the axial thermal expansion coefficient of the lead pins of the present invention can be adjusted by selecting the Cr and / or Mo content in the [Cr and / or Mo]-Cu composite and the area reduction rate during diameter reduction and elongation of the material, thereby making 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 with increasing area reduction rate during diameter reduction and elongation, so that the axial electrical conductivity can be adjusted depending on the application equipment, etc. Therefore, the lead pin of the present invention can improve the bonding reliability with the sealing glass, and can carry a large current even with a small diameter, and can reduce the amount of heat generated when current is passed through it. This makes it fully compatible with the ever-increasing current and miniaturization of electric compressors for automobiles, for example.

[0043] The stem base of the present invention has a thermal expansion coefficient in the in-plane direction required for compressing and mechanically sealing the sealing glass and lead pins, and has a thermal expansion coefficient in the thickness direction that is less than that in the in-plane direction, a relatively small thermal expansion coefficient in the thickness direction, an isotropic thermal expansion coefficient in the in-plane direction, and a high thermal conductivity in the thickness direction. Furthermore, among these stem bases, those with further optimized properties can have a thermal expansion coefficient in the thickness direction close to that of the sealing glass, and have a thermal conductivity in the thickness direction that is significantly higher than that of carbon steel, which has been widely used in stem bases in the past. Furthermore, the thermal expansion coefficient in the thickness direction of the stem base of the present invention can be adjusted by selecting the Cr and / or Mo content (content) of the [Cr and / or Mo]-Cu composite and the area reduction rate during diameter reduction and elongation of the material, thereby making the thermal expansion coefficient of the stem base as close as possible to that of the sealing glass. In addition, the thermal conductivity in the thickness direction of the stem base of the present invention increases as the area reduction rate during diameter reduction and elongation increases, so the thermal conductivity in the thickness direction can be adjusted depending on the application equipment, etc. 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 bonding reliability with the sealing glass. Moreover, because it has excellent heat dissipation performance in the plate thickness direction, it can improve the heat dissipation performance of, for example, semiconductor laser devices and fully respond to the increasing power and performance of semiconductor laser devices.

[0044] Furthermore, the airtight terminal of the present invention using the lead pin and the electric compressor of the present invention using this airtight terminal can respectively 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 device of the present invention using the above-mentioned lead pins and / or stem base can enjoy the effects of the above-mentioned metal material and lead pins and / or stem base of the present invention. [Brief explanation of the drawings]

[0045] [Figure 1]This figure shows an SEM image (left photo) of the surface of a wire-shaped metal material (φ1.2 mm wire made of a 50 mass% Cr-Cu composite) that is one example of the present invention, as well as an enlarged photograph (right photo) of the cross-sectional structure in the stretching direction (axial direction) and an enlarged photograph (center photo) of the cross-sectional structure in the direction perpendicular to the stretching direction (radial direction) observed with an optical microscope (magnification 120x). [Figure 2] These are enlarged photographs of the cross-sectional structure in the rolling direction and the cross-sectional structure perpendicular to the rolling direction, observed with an optical microscope, of a metal material (rolled plate material of 50 mass% Cr-Cu composite) obtained by infiltrating Cu into a Cr sintered body and rolling it into a plate using a flat roll. [Figure 3] 3A and 3B are schematic diagrams showing a compression-sealing type glass hermetic seal, with FIG. 3A being a plan view and FIG. 3B being a cross-sectional view taken along line AA in FIG. 3A. [Figure 4] Figure 4(a) is a schematic diagram of a lead pin made of the metal material of the present invention, and Figure 4(b) is a schematic diagram of a stem base made of the metal material of the present invention. The upper figure in Figure 4(a) shows a radial cross section of the lead pin, and the lower figure shows an axial cross section. The upper figure in Figure 4(b) shows a plate surface cross section of the stem base, and the lower figure shows a plate thickness cross section. [Figure 5] 5A and 5B are schematic diagrams 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 provided in an airtight terminal" (conceptual diagrams showing the dimensions and thermal expansion coefficients of the constituent parts, the compressive stress within the seal, etc.), where FIG. 5A is a schematic vertical cross-sectional view of the entire seal, FIG. 5B is a schematic plan view of the same, and FIG. 5C is a schematic plan view of the sealing glass. [Figure 6] 6A and 6B are schematic diagrams (conceptual diagrams showing the dimensions and thermal expansion coefficients of the constituent parts, the compressive stress within the seal, etc.) of a compression-sealed glass hermetic seal used to examine the bonding reliability when the metal material of the present invention is used for the "lead pin of a compression-sealed glass hermetic seal provided in an airtight terminal." Figure 6A is a schematic vertical cross-sectional view of the entire seal, Figure 6B is a schematic plan view of the housing (stem base) and sealing glass, and Figure 6C is a schematic plan view of the sealing glass and lead pin. [Figure 7] 7A and 7B are schematic diagrams (conceptual diagrams showing the dimensions and thermal expansion coefficients of the constituent parts, compressive stress within the seal, etc.) of a compression-sealed glass hermetic seal used to examine the bonding reliability when the metal material of the present invention is used for the "lead pin of a compression-sealed glass hermetic seal provided in a semiconductor laser device." Figure 7A is a schematic longitudinal cross-sectional view of the entire seal, and Figure 7B is a schematic plan view of the same. [Figure 8] 8A and 8B are schematic diagrams (conceptual diagrams showing the dimensions and thermal expansion coefficients of the constituent parts, compressive stress within the seal, etc.) 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 provided in a semiconductor laser device." Figure 8A is a schematic longitudinal cross-sectional view of the entire seal, and Figure 8B is a schematic plan view of the same. DETAILED DESCRIPTION OF THE INVENTION

[0046] <Basic structure of the metal material of the present invention> The metallic material of the present invention comprises a [Cr and / or Mo]-Cu composite having a metallic structure in which a Cr phase and / or Mo phase is dispersed in a Cu matrix. This [Cr and / or Mo]-Cu composite is a diameter-reduced, drawn material of a powder metallurgy compact, and when cross-sectionally observed with an optical microscope (for example, at 120x magnification), it is characterized by having a cross-sectional structure in the drawing direction in which lamellar or linear Cr phase and / or Mo phase are dispersed in the Cu matrix, and a cross-sectional structure in the direction perpendicular to the drawing direction in which flake-like, small platelet-like, or granular Cr phase and / or Mo phase are dispersed in the Cu matrix. In the present invention, the term "Cr and / or Mo" refers to a Cr-Cu composite having a metal structure in which a Cr phase is dispersed in a Cu matrix, a Mo-Cu composite having a metal structure in which a Mo phase is dispersed in a Cu matrix, and a Cr·Mo-Cu composite having a metal structure in which a Cr phase and a Mo phase are dispersed in a Cu matrix.

[0047] In the present invention, the term "powder metallurgy compact" refers to a compact obtained by applying a powder metallurgy method, and therefore includes compacts obtained in step (A) of the manufacturing method described below, such as (i) a compact obtained by step (a1) of sintering a compact (green compact) of powder raw materials to form a sintered compact, and step (a2) of subjecting the sintered compact to Cu infiltration and / or densification treatment, and (ii) a compact obtained by subjecting the powder raw materials to spark plasma sintering (SPS sintering) or hot press sintering. Furthermore, the term "diameter-reduced and elongated material of powder metallurgy compact" refers to a material obtained by reducing and elongating the powder metallurgy compact described above through area-reducing processing (diameter-reducing and elongating processing). In the present invention, "a lamellar or linear Cr phase and / or Mo phase is dispersed in a Cu matrix" includes the case where both a "lamellar Cr phase and / or Mo phase" and a "linear Cr phase and / or Mo phase" are dispersed (mixed) in the Cu matrix. Similarly, "a flake-like, small platelet-like, or granular Cr phase and / or Mo phase is dispersed in a Cu matrix" includes the case where two or more of a "flake-like Cr phase and / or Mo phase," a "small platelet-like Cr phase and / or Mo phase," and a "granular Cr phase and / or Mo phase" are dispersed (mixed) in the Cu matrix.

[0048] The main forms (specific forms) of the metallic material of the present invention include (1) a rod-shaped or wire-shaped metallic material in which the stretching direction is the axial direction and the direction perpendicular to the stretching is the radial direction, and (2) a plate-shaped metallic material in which the stretching direction is the plate thickness direction and the direction perpendicular to the stretching is the plate surface direction. For example, the above (1) can be used as a material for lead pins of compression-sealed glass hermetic seals, and the above (2) can be used as a material for stem bases of compression-sealed glass hermetic seals. In the present invention, when referring to "rod-shaped or wire-shaped metal material," "rod-shaped or wire-shaped material," "rod-shaped or wire-shaped raw material," or "(the material) is reduced in diameter and drawn into a rod or wire shape," "rod-shaped" means "rod-shaped," and similarly, "wire-shaped" means "wire-shaped." The radial cross-sectional shape of the rod-shaped or wire-shaped metal material (1) above is not particularly limited, but is usually a circle or a polygon (e.g., a hexagon, octagon, or hexagon). While there is no strict distinction between rod-shaped materials (rods) and wire-shaped materials (wire rods), generally, wire-shaped materials (wire rods) refer to materials that can be wound, while rod-shaped materials (rods) refer to materials that cannot be wound. The planar (plate surface) shape of the plate-shaped metal material (2) above is also not particularly limited, but is usually a circle, ellipse, or polygon (e.g., a hexagon, octagon, or hexagon).

[0049] The metallic material of the present invention is obtained by subjecting a raw material consisting of a [Cr and / or Mo]-Cu composite (powder metallurgy compact) obtained through a sintering process of powder raw materials to area reduction (diameter-reducing and elongation processing), thereby reducing and elongating the composite into a rod or wire shape. As a result, Cr and / or Mo phases are formed in which Cr and / or Mo particles dispersed in a Cu matrix are elongated into needle-like or rod-like shapes in the elongation direction, resulting in the characteristic cross-sectional structure in the elongation direction and transverse to the elongation direction as described above. Furthermore, a [Cr and / or Mo]-Cu composite having such a characteristic cross-sectional structure in the elongation direction and transverse to the elongation direction has unique properties, as described below, particularly properties suitable for lead pins and stem bases of compression-sealed glass hermetic seals. Such a metallic material (a [Cr and / or Mo]-Cu composite) has not been previously known.

[0050] Figure 1 shows an SEM image (left photo) of the surface of a wire-shaped metal material (a φ1.2 mm wire made of a 50 mass% Cr-Cu composite) that is one example of the present invention, along with an optical microscope (magnification 120x) enlarged photographs of the cross-sectional structure in the stretching direction (axial direction) (right photo) and the cross-sectional structure in the direction perpendicular to the stretching direction (radial direction) (center photo). In the stretching direction and transverse direction (axial and radial directions) cross-sectional structure, the dark areas represent Cr phases dispersed in the Cu matrix (light areas). The manufacturing conditions for this metal material were as follows: a rectangular prism-shaped blank (9 mm in diameter) for area reduction was subjected to swaging followed by combined roll rolling for area reduction (diameter reduction and elongation), and then finish drawing (CRD) to reduce the area (diameter reduction and elongation) to an outer diameter of φ1.2 mm.

[0051] This metallic material is a material obtained by reducing the area of ​​a Cr-Cu composite (powder metallurgy compact) obtained by powder metallurgy as described above, and then reducing and elongating it into a rod or wire shape. Therefore, the Cr particles dispersed in the Cu matrix of the material (powder metallurgy compact) are elongated into needle-like or rod-like shapes (not the "flat" shapes of the plate-rolled material shown in FIG. 2 ). As a result, the cross-sectional structure shown in FIG. 1 is obtained. Specifically, the cross-sectional structure in the elongation direction (axial direction) observed with an optical microscope is a cross-section of the elongated needle-like or rod-like Cr phase in the elongation direction, resulting in a layered or linear Cr phase dispersed in the Cu matrix. This layered (also referred to as "band-like") or linear Cr phase exists in an elongated state along the elongation direction (axial direction) of the material, and typically includes a mixture of layered Cr phases with a certain width and thin linear Cr phases. Among these, the layered structures with a certain width are considered to be Cr phases formed by the elongation and coalescence of multiple adjacent Cr particles for the reasons described below. Even in the cross-sectional structure in the elongation direction (axial direction) of the material shown in Figure 1, the Cr phases are a mixture of layered structures with a certain width and thin linear structures elongated in the elongation direction (axial direction) of the material, and dispersed in the Cu matrix. On the other hand, in the cross-sectional structure in the direction perpendicular to the elongation direction (radial direction) observed with an optical microscope, the above-mentioned needle- or rod-shaped elongated Cr phases are cross-sectioned in the direction perpendicular to the elongation direction, resulting in the dispersion of thin, small, or granular Cr phases in the Cu matrix. Usually, the Cr phase in this cross-sectional structure is a mixture of thin, small, and granular Cr phases. The reason why the Cr phase appears flake-like or small in the cross section perpendicular to the stretching direction is thought to be that when the raw material (powder metallurgy compact) is stretched to elongate needle- or rod-like shapes by radial reduction, the Cr phase distribution in the stretching direction becomes uneven, causing some Cr phase particles to approach, contact, or coalesce. Even in the cross section structure perpendicular to the stretching direction (radial direction) in Figure 1, fine Cr phases (flake-like, flake-like, or granular Cr phases) are relatively uniformly dispersed in the Cu matrix. The Cr phases that appear flake-like, flake-like, or granular are the cross sections perpendicular to the stretching direction (radial direction) of the Cr phases that have been elongated to elongate needle- or rod-like shapes, as described above.

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

[0053] For comparison, Fig. 2 shows the cross-sectional structures in the rolling direction and transverse to the rolling direction observed with an optical microscope for a rolled sheet of a 50 mass% Cr-Cu composite, i.e., a metallic material obtained by infiltrating a Cr sintered body with Cu and rolling it into a sheet using a flat roll. In the case of this rolled sheet of Cr-Cu composite, there was no significant difference between the cross-sectional structures in the rolling direction and transverse to the rolling direction. In both the rolling direction and transverse to the rolling direction, the 75% reduction exhibited a Cr phase dispersed in a quasi-mesh structure within the Cu matrix, while the 98% reduction exhibited a unidirectionally elongated Cr phase dispersed in a flattened (quasi-fibrous) structure within the Cu matrix. Comparing this to Fig. 2 reveals that the material of the present invention shown in Fig. 1 has a very distinctive cross-sectional structure in the stretching direction and transverse to the stretching direction (axial and radial directions). In particular, with regard to the cross-sectional structure perpendicular to the stretching direction, the plate-rolled material in FIG. 2 has a morphology in which the Cr phase is thinly elongated into a flat shape (quasi-fibrous shape), whereas the material of the present invention in FIG. 1 has a morphology in which the Cr phase is dispersed in the form of fine flakes, small pieces, or particles (cross-sectional shape perpendicular to the stretching direction of the Cr phase that is elongated into a needle-like or rod-like shape in the stretching direction), and thus presents a completely different morphology.

[0054] The Cr-Cu composite rolled sheet shown in Figure 2 was developed for use in heat sinks to be bonded between semiconductors or ceramics with low thermal expansion coefficients. Due to the cross-sectional structure described above, the thermal expansion coefficient in the in-plane direction (rolling direction and direction perpendicular to the rolling direction) is small, but the thermal expansion coefficient in the thickness direction is large. Therefore, when a shaft with the rolling direction as the axial direction is cut from this rolled sheet and used as a lead pin for a compression-sealed glass hermetic seal, the thermal expansion coefficient in the pin's radial direction becomes anisotropic. This results in a large difference in thermal expansion between the lead pin and the sealing glass in one direction of the pin's radial cross section, leading to cracks in the sealing glass and other problems that result in insufficient bonding reliability. Furthermore, when the rolled sheet is used as a stem base for a compression-sealed glass hermetic seal, the small thermal expansion coefficient in the in-plane direction results in small compressive stress in the sealing glass in the radial direction, while the large thermal expansion coefficient in the thickness direction results in high interfacial shear stress with the sealing glass in the thickness direction. This results in insufficient bonding reliability. Furthermore, the Cr phase has a lower thermal conductivity than the Cu phase and is flattened by rolling, blocking the heat flow in the thickness direction of the plate, resulting in low thermal conductivity in the thickness direction and problems with heat dissipation. In contrast, the metallic material of the present invention and the metallic components (particularly the lead pins and stem bases of compression-sealed glass hermetic seals) made from it have unique properties (characteristics) that are completely different from those of conventionally known metallic materials, as will be explained later in the section entitled "Characteristics of the metallic material of the present invention." These properties are particularly suitable for lead pins and stem bases, and do not present any of the problems seen with the above-mentioned Cr-Cu composite sheet rolled material (Figure 2).

[0055] FIG. 3 is a schematic diagram showing a compression-sealed glass hermetic seal in which the metal material of the present invention is used as the material for the lead pin or stem base, where FIG. 3(a) is a plan view and FIG. 3(b) is a cross-sectional view taken along line AA in FIG. 3(a). This compression-sealed glass hermetic seal is composed of a stem base 1, a lead pin 2, sealing glass 3, etc., and is a seal in which the lead pin 2 is airtightly sealed in an insertion hole 4 formed through the stem base 1 via the sealing glass 3 (sealing material). Lead pins are also called leads, metal pins, pins, feedthroughs, etc., and have traditionally been made from materials such as Fe-Ni alloys, Kovar, stainless steel (SUS410, SUS430, SUH446, etc.), etc. The lead pins made from the metal material of the present invention can be used as a substitute for these conventional products, and exhibit superior performance compared to them. Stem bases are sometimes called housings, stems, bases, metal eyelets, etc., and are conventionally made of carbon steel (SC material, SPC material, etc.), stainless steel (SUS304, SUS410, etc.), chrome steel, etc. The stem base made of the metal material of the present invention can be a substitute for these conventional products and exhibits superior performance compared to them.

[0056] The lead pin and stem base made of the metal material of the present invention will be described in detail later, but will be briefly explained below. Figure 4(a) is a schematic diagram of a lead pin made of the metallic material of the present invention, and Figure 4(b) is a schematic diagram of a stem base made of the metallic material of the present invention. The upper and lower figures of Figure 4(a) are schematic diagrams of the radial and axial cross sections of the lead pin, respectively. The upper and lower figures of Figure 4(b) are schematic diagrams of the plate-surface and thickness-direction cross sections of the stem base, respectively. These figures are schematic diagrams of cross sections of the Cr and / or Mo phases formed when Cr and / or Mo particles dispersed in a Cu matrix are stretched into elongated needle- or rod-like shapes in the stretching direction.

[0057] In the axial cross section (bottom) of Figure 4(a) and the thickness direction cross section (bottom) of Figure 4(b), the short lines represent "layered or linear Cr and / or Mo phases" dispersed in the Cu matrix, which corresponds to the cross-sectional structure in the photograph on the right side of Figure 1. In addition, in the radial cross section (top) of Figure 4(a) and the plate surface cross section (top) of Figure 4(b), the dots represent "flake-like, small platelet-like, or granular Cr and / or Mo phases" dispersed in the Cu matrix, which corresponds to the cross-sectional structure in the center photograph of Figure 1. 4(a) is the above-mentioned metal material of the present invention, and is made of a rod-shaped or wire-shaped metal material whose extension direction is the axial direction and whose direction perpendicular to the extension is the radial direction. Usually, the lead pin (pin base material) is obtained by cutting the rod-shaped or wire-shaped metal material to an appropriate length to cut out the pin-shaped member. On the other hand, the stem base in Fig. 4(b) is the above-mentioned metal material of the present invention, and is made of a plate-shaped metal material with its extension direction as the plate thickness direction and the direction perpendicular to the extension as the plate surface direction. Usually, a rod-shaped or wire-shaped metal material is cut in the radial direction to an appropriate thickness (i.e., the material is cut into rings) to cut out a plate material, which is then processed into a stem base.

[0058] <Characteristics of the metal material of the present invention> Next, the properties of the metal material of the present invention will be explained using examples in which it is applied to lead pins and stem bases of a compression-sealed glass hermetic seal. Because the metallic material of the present invention has the above-described cross-sectional structure in the stretch direction and transverse to the stretch direction, it has unique properties (characteristics) that are different from those of metallic materials conventionally used for lead pins and stem bases of compression-sealed glass hermetic seals, or for other conductive components. Specifically, this metallic material (a [Cr and / or Mo]-Cu composite, which is a diameter-reduced and stretched powder metallurgy compact) has a thermal expansion coefficient in the stretch direction that is less than that in the transverse direction, a relatively small thermal expansion coefficient in the stretch direction, and high electrical conductivity and thermal conductivity in the stretch direction. Among these, those with further optimized properties, as described below, can achieve a thermal expansion coefficient in the stretch direction close to that of sealing glass. Furthermore, they have significantly higher electrical conductivity in the stretch direction than Ni-Fe alloys, which are commonly used for lead pins, and significantly higher thermal conductivity in the stretch direction than carbon steels, which are commonly used for stem bases. Furthermore, the metallic material of the present invention is a diameter-reduced, drawn material of a powder metallurgical compact, and has the cross-sectional structure in the drawing direction and transverse to the drawing direction as described above, so that the thermal expansion coefficient in the direction perpendicular to the drawing direction is the same in all directions perpendicular to the drawing direction, and the thermal expansion coefficient in the direction perpendicular to the drawing direction is isotropic.

[0059] Therefore, a rod- or wire-shaped metal material (a [Cr and / or Mo]-Cu composite that is a diameter-reduced and drawn powder metallurgical compact) with the extension direction as its axial direction and the direction perpendicular to the extension as its radial direction has an axial thermal expansion coefficient less than its 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 below, can have an axial thermal expansion coefficient close to that of sealing glass, and also have a significantly higher axial electrical conductivity than 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 and drawn powder metallurgical compact) with the above-mentioned stretching direction as the thickness direction and the direction perpendicular to the stretching as the plate surface direction has a thermal expansion coefficient in the plate surface direction required for a stem base, and the thermal expansion coefficient in the plate surface direction is smaller than the thermal expansion coefficient in the plate surface direction, is relatively small in the thickness direction, is isotropic in the plate surface direction, and has high thermal conductivity in the plate thickness direction. Among these, those with further optimized properties, as described below, can have a thermal expansion coefficient in the plate thickness direction close to that of sealing glass, and also have a thermal conductivity in the plate thickness direction that is significantly higher than that of carbon steel, which is widely used for stem bases. According to the examples described below, the thermal expansion coefficient of the metal materials (invention examples) of the present invention in the direction perpendicular to the stretching (diameter) is greater than the thermal expansion coefficient in the stretching (axial) direction, and is a relatively low thermal expansion coefficient in the stretching (axial) direction that is close to the thermal expansion coefficient of the sealing glass (however, the thermal expansion coefficient varies depending on the type of glass). Furthermore, the axial electrical conductivity of the metal materials (invention examples) of the present invention is significantly higher than that of 50.5 mass% Ni-Fe (Comparative Example No. 30), which is widely used in conventional lead pins, and is also significantly higher than the thermal conductivity of carbon steel, which is widely used in conventional stem bases, which is approximately 40 to 60 W / m K.

[0060] As described above, the metallic material of the present invention generally possesses properties not found in conventional metallic materials, namely, "thermal expansion coefficient in the stretching direction < thermal expansion coefficient in the direction perpendicular to the stretching direction, relatively small thermal expansion coefficient in the stretching direction, isotropic thermal expansion coefficient in the direction perpendicular to the stretching direction, and high electrical conductivity and thermal conductivity in the stretching direction." Furthermore, it has the following significant features. First, the magnitude of the thermal expansion coefficient in the stretching direction of this metallic material 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 area reduction rate during diameter reduction and stretching of the material. That is, the magnitude of the axial thermal expansion coefficient of a rod-shaped or wire-shaped metallic material, and the magnitude of the thermal expansion coefficient through the thickness of a plate-shaped metallic material can be changed (adjusted). Specifically, for a given area reduction ratio during diameter-reducing stretching, the higher the Cr and / or Mo content, the smaller the thermal expansion coefficient in the stretching direction. Also, for a given area reduction ratio during diameter-reducing stretching, the larger the area reduction ratio (up to about 97%). This can be explained using the examples described below. For example, metal materials Nos. 5, 10, 15, and 20 (invention examples) are made of Cr-Cu composites with different Cr content ratios and an area reduction ratio of 90.3%, but the axial thermal expansion coefficient decreases with increasing Cr content. Metal materials Nos. 24 and 29 (invention examples) are made of Mo-Cu composites with different Mo content ratios and an area reduction ratio of 97.6%, and metal materials Nos. 37 and 39 (invention examples) are made of Mo-Cu composites with different Mo content ratios and an area reduction ratio of 80%, but the axial thermal expansion coefficient decreases with increasing Mo content. On the other hand, for example, metal materials Nos. 7 to 12 (invention examples) are made of Cr-Cu composites with a Cr content of 45 mass% and different area reduction rates, and metal materials Nos. 26 to 29 (invention examples) are made of Mo-Cu composites with a Mo content of 40 mass% and different area reduction rates, but in all cases the axial thermal expansion coefficient decreases as the area reduction rate increases.This allows the axial thermal expansion coefficient of the lead pin and the thickness-wise thermal expansion coefficient of the stem base to be as close as possible to the thermal expansion coefficient of the sealing glass, thereby maximizing the bonding reliability between the lead pin and stem base and the sealing glass, which is an issue in compression-sealed glass hermetic seals. In particular, as will be described later, it is preferable for the values ​​of τ1 / P1 (= [compressive shear stress in the thickness direction τ1 acting from the stem base to the sealing glass interface] / [compressive stress in the radial direction P1 from the stem base to the sealing glass]) and τ3 / P2 (= [compressive shear stress in the axial direction τ3 acting from the lead pin to the sealing glass interface] / [compressive stress in the radial direction P2 from the sealing glass to the lead pin]) to be positive and as small as possible, as this increases the bonding reliability between the stem base and the lead pin and the sealing glass. It is possible to adjust the thickness-wise thermal expansion coefficient of the stem base and the axial thermal expansion coefficient of the lead pin (to approach the thermal expansion coefficient of the sealing glass) to achieve such τ1 / P1 and τ3 / P2.

[0061] Furthermore, the electrical conductivity and thermal conductivity in the stretching direction of this metal material change depending on the area reduction rate during diameter reduction stretching. For the same Cr and / or Mo content, the electrical conductivity and thermal conductivity in the stretching direction increase with increasing area reduction rate up to approximately 97% during diameter reduction stretching. In other words, the greater the area reduction rate, the greater the axial electrical conductivity of rod-shaped or wire-shaped metal materials, and the greater the thermal conductivity through the plate-shaped metal materials. For example, looking at the metal materials Nos. 7 to 12 (inventive examples with a Cr content of 45% by mass) and Nos. 26 to 29 (inventive examples with a Mo content of 40% by mass) listed above, the electrical conductivity and thermal conductivity in the stretching direction increase with increasing area reduction rate. Therefore, by changing the area reduction rate, the axial electrical conductivity or the thermal conductivity through the plate-thickness direction can be appropriately adjusted depending on the application of the metal material. As is clear from the examples, the electrical conductivity and thermal conductivity in the stretching direction also vary depending on the component composition of the metal material (the blending ratio of Cr and / or Mo), and the lower the blending ratio of Cr and / or Mo, the greater the electrical conductivity and thermal conductivity in the stretching direction.

[0062] Therefore, in terms of applications for compression-sealed glass hermetic seals, the wire- or rod-shaped metal material of the present invention is highly suitable for lead pins, and the plate-shaped metal material of the present invention is highly suitable for stem bases. Furthermore, this plate-shaped metal material has a certain level of thermal expansion coefficient in the in-plane direction, and its thermal expansion coefficient in the thickness direction is less than that in the in-plane direction. Furthermore, the magnitude of the thermal expansion coefficient in the thickness direction can be adjusted and optimized by selecting the Cr and / or Mo content and the area reduction rate during diameter reduction and elongation of the material. Therefore, the thermal expansion characteristics required for stem bases (i.e., the thermal expansion coefficient in the in-plane direction is somewhat higher than that of the sealing glass, and the thermal expansion coefficient in the thickness direction is as close as possible to that of the sealing glass) can be highly satisfied. On the other hand, by increasing the area reduction rate during diameter reduction and elongation, the thermal conductivity in the thickness direction can be increased, thereby highly satisfying the heat dissipation required for stem bases.

[0063] Regarding the thermal properties of the metallic material of the present invention, the thermal expansion coefficient in the stretching direction is smaller than that in the direction perpendicular to the stretching direction, as described above. This is thought to be due to the shear stress at the interface between the Cr and / or Mo phases elongated into needle- or rod-like shapes by the diameter-reducing stretching process and the Cu, which suppresses the expansion of Cu in the stretching direction. However, since the range of the shear stress of a single Cr and / or Mo phase in the cross section perpendicular to the stretching direction is limited, the thermal expansion coefficient in the stretching direction tends to be smaller when the density of the Cr and / or Mo phases in the cross section perpendicular to the stretching direction is higher, i.e., when the Cr and / or Mo phases have a higher blending ratio (content) of Cr and / or Mo. Furthermore, since the shear stress increases as the elongation length of the Cr and / or Mo phases in the stretching direction increases, as described below, a larger reduction in area during the production of the metallic material of the present invention increases the elongation length of the Cr and / or Mo phases in the stretching direction, resulting in a smaller thermal expansion coefficient in the stretching direction. In other words, the larger the reduction in area, the smaller the thermal expansion coefficient in the stretching direction tends to be. The thermal expansion coefficient in the direction perpendicular to the stretching direction tends to increase as the area reduction rate increases. This is because the larger the area reduction rate, the smaller the diameter of the Cr and / or Mo phases in the direction perpendicular to the stretching direction, and the smaller the binding force of Cu in the direction perpendicular to the stretching direction. From the above, it can be seen that the thermal expansion coefficient in the stretching direction and the direction perpendicular to the stretching direction can be adjusted by selecting the Cr and / or Mo compounding ratio (content) and the area reduction rate when the material is stretched. Furthermore, the greater the area reduction ratio, the greater the electrical conductivity and thermal conductivity in the stretching direction. This is thought to be because, as the area reduction ratio increases, the Cr phase and / or Mo phase stretched in the stretching direction causes the structure of the Cu phase to also be stretched in the stretching direction, and electric current and heat flow preferentially in the stretching direction.

[0064] <Preferable conditions for the metal material of the present invention> As described above, the properties of the metal material of the present invention are that the thermal expansion coefficient in the stretching direction is smaller than the thermal expansion coefficient in the direction perpendicular to the stretching direction, the thermal expansion coefficient in the stretching direction is relatively small, the thermal expansion coefficient in the direction perpendicular to the stretching direction is isotropic, the electrical conductivity in the stretching direction is high, and the thermal conductivity in the stretching direction is high. However, the optimum thermal properties are that the average thermal expansion coefficient in the stretching direction from 30°C to 450°C is 7.0 to 12.0 × 10 -6 / K, and the average thermal expansion coefficient in the direction perpendicular to the stretching direction from 30°C to 450°C is 18.0×10 -6 / K or less, and it is preferable that [average thermal expansion coefficient in the stretching direction from 30°C to 450°C]<[average thermal expansion coefficient in the direction perpendicular to the stretching direction from 30°C to 450°C].

[0065] Average thermal expansion coefficient in the stretching direction from 30℃ to 450℃ is 7.0 to 12.0×10 -6 / K is particularly effective in achieving the above-mentioned effects. That is, if the average thermal expansion coefficient in the stretching direction is within the above range, it is close to the thermal expansion coefficient of the sealing glass, which is preferable because it makes it easier to achieve 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 above, 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 and / or Mo) or the area reduction rate when the material is stretched to reduce its diameter. Regarding the point that the thermal expansion coefficient in the direction perpendicular to the stretching direction is greater than the thermal expansion coefficient in the stretching direction, which is a characteristic of the thermal properties of the metal material of the present invention, in the examples (invention examples) described later, the difference between the [average thermal expansion coefficient in the stretching direction (axial direction) from 30°C to 450°C] and the [average thermal expansion coefficient in the direction perpendicular to the stretching direction (radial direction) from 30°C to 450°C] is 2.0 × 10 -6 / K or higher.

[0066] The reason why the average thermal expansion coefficient in the stretching direction and the direction perpendicular to the stretching direction is defined as the average thermal expansion coefficient from 30°C to 450°C is as follows: Sealing glass with a glass transition point (Tg) in the range of approximately 410 to 560°C is used, and the volume of sealing glass is determined at a temperature approximately 30°C below the glass transition point, so sealing glass with a glass transition point of approximately 410 to 560°C will have its volume 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 depending on the temperature, 450°C, which is approximately the midpoint between 380 and 530°C, is used as a representative value, and the "average thermal expansion coefficient from 30°C to 450°C" is defined.

[0067] Furthermore, the metal material of the present invention has an optimum property of electrical conductivity in the stretching direction of 20.0×106 It is preferable that the thermal conductivity in the stretching direction is 180 W / m K or more. The electrical conductivity in the stretching direction is 20.0×10 6 It is particularly effective to obtain the above-mentioned effects if the thermal conductivity in the stretching direction is 180 W / m K or more. 6 If "S / m or more" is substituted for volume resistivity, which is the reciprocal of electrical conductivity, it becomes "volume resistivity of 5.0 μΩ·cm or less." Therefore, in terms of volume resistivity, it is preferable that the volume resistivity in the stretching direction (this also applies to the volume resistivity in the axial direction, which will be described later) be 5.0 μΩ·cm or less. High electrical conductivity in the extension direction is a particularly useful property for lead pins, but if the electrical conductivity in the extension direction (axial direction for rod-shaped or wire-shaped metal materials) is 20.0 × 10 6 A level of S / m or more is a significantly higher electrical conductivity in the extension direction than Ni-Fe alloys, which have been widely used in conventional lead pins, and even small-diameter lead pins can be used to pass a large current, with the effect of significantly reducing the amount of heat generated during current passage. As will be shown in the examples below, the electrical conductivity in the extension direction (axial direction) of 50.5 mass% Ni-Fe (Comparative Example No. 30), which has been conventionally used in lead pins, is 2.81 × 10 6 S / m, whereas the electrical conductivity in the stretching direction (axial direction) of the metal material of the present invention is one order of magnitude larger than that, and it is clear that a significantly higher electrical conductivity can be obtained.

[0068] Furthermore, high thermal conductivity in the stretching direction is a particularly useful property for stem bases, and a thermal conductivity of 180 W / m·K or more in the stretching direction (thickness direction for plate-shaped metal materials) is significantly higher than the thermal conductivity in the stretching direction of carbon steel, which has been widely used in conventional stem bases, and provides particularly high heat dissipation properties in the thickness direction of the stem base. While the thermal conductivity of carbon steel, which has been used in conventional stem bases, is approximately 40 to 60 W / m·K, as shown in the examples below, the thermal conductivity in the stretching direction of the metal material of the present invention is several times higher than that, demonstrating a significantly higher thermal conductivity in the stretching direction. As mentioned above, the electrical conductivity and thermal conductivity of the metal material in the stretching direction can also be adjusted by selecting the component composition of the metal material (the blending ratio of Cr and / or Mo) and the area reduction rate when the material is stretched.

[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 displacement detection method, and 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 using the push rod displacement detection method, finding the difference in the amount of elongation at 30°C and 450°C, and dividing this value by the temperature difference of 420°C (= 450°C - 30°C). The electrical conductivity in the stretching direction is measured by a DC four-terminal method (measurement temperature: room temperature, atmosphere: air) using a commercially available electrical resistance measuring device. In addition, the thermal conductivity in the stretching direction (thermal conductivity at room temperature) cannot be measured due to the small diameter of the metal material, so it is calculated from the electrical conductivity based on the Wiedemann-Franz law. In other words, 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 is independent of the type of metal (thermal conductivity κ / electrical conductivity σ = L T L: 2.44 × 10 -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 unique properties (characteristics) described above due to its characteristic cross-sectional structure in the stretch direction and transverse to the stretch direction, as shown in Figure 1. While the Cr and / or Mo content (compounding ratio) of the [Cr and / or Mo]-Cu composite constituting the metallic material of the present invention is not particularly limited, a Cr and / or Mo content of 35 to 60 mass% in total is particularly effective for achieving the thermal properties described above. This is because a low Cr and / or Mo content (total) reduces the restraining force of the Cr and / or Mo phases on Cu, making it difficult to reduce the thermal expansion coefficient of the material, particularly the thermal expansion coefficient in the stretch direction. On the other hand, a high Cr and / or Mo content (total) reduces the workability of the material (raw material), making it difficult to reduce the area (diameter-reducing stretching) into a rod or wire shape, and also makes it difficult to increase the electrical conductivity in the stretch direction and the thermal conductivity in the stretch direction.

[0071] When comparing the Cr (Cr phase) and Mo (Mo phase) that are added to Cu in the metallic material of the present invention, there are the following tendencies: (i) Cr provides better workability (rollability, etc.) than Mo, (ii) Mo is more likely to increase electrical conductivity in the elongation direction than Cr, and (iii) Mo is more likely to reduce the thermal expansion coefficient in the elongation direction than Cr (the above tendencies of (ii) and (iii) can be confirmed in the examples described below). Therefore, for example, in a Cr·Mo-Cu composite, the thermal properties can be balanced and optimally optimized by adjusting the contents and ratios of Cr and Mo depending on the required thermal properties.

[0072] <Method of manufacturing a metal material according to the present invention> Next, the method for producing the metallic material of the present invention will be described. The metallic material of the present invention can generally be produced by subjecting a raw material consisting of a [Cr and / or Mo]-Cu composite (powder metallurgy compact) obtained through a process of sintering powder raw materials to area-reducing processing (diameter-reducing and elongating processing) and then elongating it into a rod or wire shape. The rod-shaped or wire-shaped material (the [Cr and / or Mo]-Cu composite, which is a diameter-reducing and elongated powder metallurgy compact) produced through this series of processes has the above-mentioned structure in which the Cr and / or Mo phases in the Cu matrix are elongated in the axial direction (longitudinal direction) into needle-like or rod-like elongated shapes, i.e., a cross-sectional structure in the elongation direction (axial direction) in which lamellar or linear Cr and / or Mo phases are dispersed in the Cu matrix, and a cross-sectional structure in the direction perpendicular to the elongation direction (radial direction) in which flake-like, small-platelet-like, or granular Cr and / or Mo phases are dispersed in the Cu matrix.

[0073] A preferred method for producing the metallic material of the present invention will now be described. This manufacturing method includes step (A) of sintering a powder raw material to obtain a material for area reduction processing consisting of a [Cr and / or Mo]-Cu composite, and step (B) of reducing the area of ​​the material obtained in step (A) (diameter reduction and elongation processing) to reduce the diameter and elongate it into a rod or wire shape. As will be described later, step (A) also includes Cu infiltration or densification treatment after sintering the powder raw material, and spark plasma sintering or hot press sintering of the powder raw material.

[0074] In step (A), the material for area reduction can be obtained in various ways, but the basic ways include the following (i) and (ii). Each way may be carried out according to a conventional method. (i) A material for surface reduction processing consisting of a [Cr and / or Mo]-Cu composite is obtained through a process (a1) of sintering a compact (pressed powder) of powder raw material to form a sintered body, and a process (a2) of subjecting this sintered body to Cu infiltration and / or densification treatment. (ii) By subjecting the powder raw material to a spark plasma sintering (SPS sintering) or hot press sintering process, a material for surface reduction processing consisting of a [Cr and / or Mo]-Cu composite is obtained. In the above embodiment (i), in step (a1), the powder raw material is filled into a mold and molded in a conventional manner, and the molded body (green compact) is sintered in a predetermined atmosphere to form a sintered body. Next, in step (a2), the sintered body is subjected to at least one of Cu infiltration and densification treatment to prepare a material for area reduction processing.

[0075] In the Cu infiltration of a sintered body, for example, a Cu plate or Cu powder for Cu infiltration may be placed on a compact of powder raw material, and the compact may be first heated to a sintering temperature to sinter, and then the temperature may be raised to the Cu infiltration temperature to perform Cu infiltration. Note that the Cu infiltration body obtained in this process is preferably subjected to surface grinding (for example, surface grinding using a milling machine or grinding wheel) to remove excess pure Cu remaining on the surface. The densification treatment is intended to densify a porous sintered body. There are no particular limitations on the type of treatment, but typical examples include hot extrusion, HIP treatment, hot pressing, and spark plasma treatment (SPS treatment), and one or more of these can be performed. When 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, but the densification treatment described above may be performed after this Cu infiltration. In HIP (hot isostatic pressing), a densification process, the sintered body is pressurized (hydrostatically) and heated in a pressure vessel using an inert gas as the pressure medium. In hot pressing, the sintered body is pressurized while being heated in a mold. In spark plasma processing (SPS), the sintered body is pressurized while being heated by pulse current in a mold.

[0076] In the above embodiment (ii), a dense sintered body can be obtained by spark plasma sintering (SPS sintering) or hot press sintering, and can be used as is as a material for area reduction processing. In spark plasma sintering, powder raw materials are filled into a mold and sintered by pulse current heating while being pressurized, while in hot press sintering, powder raw materials are placed in a mold and sintered while being heated and pressurized. Therefore, specific embodiments of step (A) include, for example, the following (A) to (D), but are not limited to these.

[0077] (a) Cr powder and / or Mo powder are molded, or a mixture of Cr powder and / or Mo powder and Cu powder is molded, and this molded body is sintered to form a sintered body, which is then infiltrated with Cu to obtain a material for surface reduction processing made of a [Cr and / or Mo]-Cu composite. (a) A mixed powder of Cr powder or / and 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 a densification treatment, such as hot extrusion, HIP treatment, hot pressing, or spark plasma treatment (SPS treatment), to obtain a material for area reduction processing consisting of a [Cr and / or Mo]-Cu composite. (c) Cr powder and / or Mo powder is molded, or a mixture of Cr powder and / or Mo powder and Cu powder is molded, and this molded body is sintered to form a sintered body. Cu is infiltrated into this sintered body, and then a densification treatment is performed using one of hot extrusion, HIP treatment, hot pressing, and spark plasma treatment (SPS treatment), to obtain a material for area reduction processing made of a [Cr and / or Mo]-Cu composite. (d) A mixed powder of Cr powder or / and Mo powder and Cu powder is subjected to spark plasma sintering or hot press sintering to obtain a material for surface reduction processing made of a [Cr and / or Mo]-Cu composite. The material for area reduction obtained in step (A) is usually a round bar or a square bar (for example, having a polygonal cross section).

[0078] In step (B), any processing method can be used as long as it is possible to reduce the area of ​​the material (diameter-reducing and drawing processing) and draw it into a rod or wire shape. For example, it can be performed by combining one or more of roll rolling, swaging, and hot extrusion, and further, it may be possible to perform finish drawing (wire drawing) afterwards. Rolling can be, for example, grooved roll rolling or combined roll rolling. Grooved roll rolling is a process in which a material (round bar, square bar, etc.) is reduced in area (diameter-reducing and elongating) into a rod or wire shape using grooved rolls. Combined roll rolling is a process in which a material (round bar, square bar, etc.) is reduced in area (diameter-reducing and elongating) into a rod or wire shape using grooved rolls with multiple stands (for example, 20 stands or more). Swaging is a type of compression process (cold forging) in which a die is used to crush a material in the radial direction, reducing the outer diameter and extending the length (diameter reduction and extension). For example, the die is rotated to squeeze the material and extend the length (diameter reduction and extension). In hot extrusion, the material is placed in a container and a ram pushes the material through a die hole.

[0079] When finish drawing (wire drawing) is performed, it is usually performed as a final area reduction process (diameter reduction and elongation process). However, for example, the material for the stem base has a large diameter, so this finish drawing process may not be performed. In the drawing process, known processes such as simple drawing (wet process, dry process) and roller die drawing (CRD) can be used. Although there is no particular restriction on the total area reduction rate of the material in step (B), if the area reduction rate is too small, it becomes difficult to obtain the structure of the metallic material of the present invention, so the total area reduction rate of the material in step (B) is preferably 60% or more. Also, although there is no particular upper limit on the total area reduction rate of the material in step (B), there is a practical upper limit depending on the compounding ratio of Cr and / or Mo, the manufacturing equipment (processing means for area reduction), etc. Here, the area reduction rate (cross-sectional area reduction rate) is calculated as follows: Area reduction rate (%) = [(ab) / a] × 100, where a is the radial cross-sectional area of ​​the material before the area reduction process in step (B) and b is the radial cross-sectional area of ​​the material after the process (B).

[0080] The surface of the rod-shaped or wire-shaped metal material obtained in step (B) may develop scratches or irregularities due to the area-reducing process (diameter-reducing and elongating process). Depending on the extent of these scratches or irregularities, gaps may form between the material and the sealing glass, potentially impairing the sealing performance, for example, when used as a lead pin. Furthermore, it may be necessary to further improve the dimensional accuracy of the outer diameter of the material obtained in step (B). Therefore, the manufacturing method of the present invention may optionally include a step (C) of grinding or polishing the surface of the rod-shaped or wire-shaped metal material obtained in step (B) as a further step primarily aimed at eliminating the above-mentioned scratches or irregularities on the material surface or improving the dimensional accuracy. This step (C) may be performed on the rod-shaped or wire-shaped metal material (raw material) obtained in step (B) as is, or may be performed on a material obtained by cutting the rod-shaped or wire-shaped material obtained in step (B) to a predetermined length, for example, a piece cut for use as a lead pin. There are no particular restrictions on the method for grinding or polishing the material surface in this step (C), but since the material to be ground is a rod-shaped or wire-shaped material with a relatively small diameter, it is preferable to use centerless grinding and polishing. Rod-shaped or wire-shaped metal material to be used for lead pins and the like can be obtained by only the above step (B) or the above step (B) + step (C), but when obtaining a plate-shaped metal material to be used for stem bases and the like, a further step (D) is carried out in which the rod-shaped or wire-shaped material (usually a rod-shaped material) obtained by the above step (B) or the above step (B) + step (C) is cut radially to cut 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. That is, in this step (D), the rod-shaped or wire-shaped material is cut radially to form round slices into plates, thereby obtaining a plate-shaped metal material.

[0081] <Components and devices using the metal material of the present invention> [Compression-sealed glass hermetic seal lead pin and stem base] Next, the lead pin and stem base for the compression-sealing type glass hermetic seal of the present invention will be described. Generally, the lead pin has a surface treatment film such as Ni plating on the surface of the pin substrate (pin body), and the stem base has a surface treatment film such as Ni plating on the surface of the plate-shaped base substrate (base body), but in this invention, the terms "lead pin" and "stem base" refer to the "pin substrate" and "base substrate" excluding such surface treatment film. The same applies to the inventions relating to the airtight terminal, electric compressor, and semiconductor laser device described below.

[0082] First, the lead pin of the present invention is a lead pin constituting a compression-sealed glass hermetic seal, and is made of the metallic material of the present invention described above. It is a rod-shaped or wire-shaped body whose axial direction is the stretching direction of the metallic material (the axial direction in the case of the rod-shaped or wire-shaped metallic material described above) and whose radial direction is the direction perpendicular to the stretching direction (the radial direction in the case of the rod-shaped or wire-shaped metallic material described above) (see FIG. 4(a)). Therefore, this lead pin is made of a [Cr and / or Mo]-Cu composite having a metallic structure in which Cr and / or Mo phases are dispersed in a Cu matrix. This [Cr and / or Mo]-Cu composite is a diameter-reduced and drawn material of a powder metallurgy compact. When cross-sectionally observed with an optical microscope (e.g., 120x magnification), it has an axial cross-sectional structure in which lamellar or wire-shaped Cr and / or Mo phases are dispersed in a Cu matrix, and a radial cross-sectional structure in which flake-like, small-platelet-like, or granular Cr and / or Mo phases are dispersed in the Cu matrix. This axial and radial cross-sectional structure is as explained above with respect to the metallic material of the present invention (see FIG. 1).

[0083] Conventionally, Fe-Ni alloy, Kovar, stainless steel, etc. have been used for lead pins, but the lead pin of the present invention can be used as a substitute for these conventional products and exhibits superior performance compared to them. Generally, the lead pins that make up a compression-sealed glass hermetic seal are required to have the following characteristics: (i) a relatively small axial thermal expansion coefficient and be as close as possible to the sealing glass to ensure reliable bonding with the sealing glass; and (ii) be able to carry a large current despite their small diameter and generate little heat when current is passed through them, i.e., have high axial electrical conductivity. The lead pins of the present invention have a relatively small axial thermal expansion coefficient (axial thermal expansion coefficient < radial thermal expansion coefficient), an isotropic radial thermal expansion coefficient, and high axial electrical conductivity. Furthermore, among these lead pins, those with further optimized properties as described below can achieve an axial thermal expansion coefficient close to that of sealing glass, and also have significantly higher axial electrical conductivity than Ni-Fe alloys, which are widely used for 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 area reduction rate during diameter reduction and elongation of the material. This allows the axial thermal expansion coefficient of the lead pin to be as close as possible to the thermal expansion coefficient of the sealing glass, maximizing the bonding reliability between the lead pin and the sealing glass, which is an issue for compression-sealed glass hermetic seals. In addition, the axial electrical conductivity of the lead pin of the present invention increases as the area reduction rate during diameter reduction and elongation increases, so the axial electrical conductivity can be adjusted depending on the application equipment, etc.

[0084] The lead pin of the present invention has an average axial thermal expansion coefficient of 7.0 to 12.0 × 10 over the temperature range of 30 to 450 °C. -6 / K, and the radial average thermal expansion coefficient from 30°C to 450°C is 18.0×10 -6 / K or less, and it is preferable 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. In addition, the electrical conductivity in the axial direction is 20.0×10 6 The average radial thermal expansion coefficient of the lead pin is preferably 18.0×10 S / m or more. -6 / K or less, it is considered possible for the lead pin to 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 in coefficient of thermal expansion between the lead pin and the sealing glass is too large, the compressive force from the sealing glass will be small, which is not desirable. Therefore, it is recommended to set the coefficient of thermal expansion between the lead pin and the sealing glass to 15.0 × 10 -6 / K or less may be preferred. Furthermore, the [Cr and / or Mo]-Cu composite preferably has a total Cr and / or Mo content of 35 to 60 mass %.

[0085] The reasons why the above-mentioned properties and composition conditions are preferable are as explained above with respect to the metallic material of the present invention. The diameter of the lead pin varies depending on the glass hermetic seal to be used, but is usually about φ0.1 to 6 mm. The lead pin (pin substrate) can be manufactured by cutting the rod-shaped or wire-shaped metal material of the present invention described above to a predetermined length. Usually, the lead pin is subjected to a surface treatment such as Ni plating. The characteristics of the lead pin of the present invention are also measured by a method similar to the method for measuring the characteristics of the metallic material of the present invention, as explained above. As described above, the lead pin of the present invention has high bonding reliability with the sealing glass, and Even with a small diameter, it is possible to pass a large current and reduce the amount of heat generated when electricity is passed through it. For example, it can fully accommodate the increasing current and miniaturization of electric compressors for automobiles.

[0086] The stem base of the present invention is a stem base constituting a compression-sealed glass hermetic seal, and is made of the metallic material of the present invention described above. It is a plate-shaped body with the thickness direction of the metallic material (the thickness direction in the case of the above-mentioned plate-shaped metallic material) and the transverse direction of the stretching (the plate surface direction in the case of the above-mentioned plate-shaped metallic material) as the plate surface direction (see FIG. 4(b)). Therefore, this stem base is made of a [Cr and / or Mo]-Cu composite having a metallic structure in which Cr and / or Mo phases are dispersed in a Cu matrix. This [Cr and / or Mo]-Cu composite is a diameter-reduced, drawn material of a powder metallurgy compact. When observed through an optical microscope (e.g., at a magnification of 120 times), it has a thickness-direction cross-sectional structure in which lamellar or linear Cr and / or Mo phases are dispersed in a Cu matrix, and a cross-sectional structure parallel to the plate surface in which flake-like, small-platelet-like, or granular Cr and / or Mo phases are dispersed in the Cu matrix. This cross-sectional structure in the thickness direction and the plane direction is as explained above with respect to the metallic material of the present invention (see FIG. 1).

[0087] Conventionally, carbon steel or stainless steel has been used for stem bases, but the stem base of the present invention can be used as a substitute for these conventional products and exhibits superior performance compared to them. The stem base that constitutes the compression-sealed glass hermetic seal is required to have (i) a coefficient of thermal expansion in the plate surface direction that can compress the sealing glass and lead pins, and to have a relatively small coefficient of thermal expansion in the plate thickness direction and be as close as possible to the sealing glass in order to ensure reliable bonding with the sealing glass, and (ii) in the case of a stem base for a semiconductor laser device, etc., to have a high thermal conductivity in the plate thickness direction in order to improve heat dissipation.

[0088] The stem base of the present invention has a thermal expansion coefficient in the in-plane direction necessary to compress the sealing glass and lead pins, and has a thermal expansion coefficient in the thickness direction that is smaller than the thermal expansion coefficient in the in-plane direction, a relatively small thermal expansion coefficient in the thickness direction, an isotropic thermal expansion coefficient in the in-plane direction, and a high thermal conductivity in the thickness direction. Furthermore, among these, those whose properties are further optimized as described below can have a thermal expansion coefficient in the thickness direction close to that of the sealing glass, and also have a thermal conductivity in the thickness direction that is significantly higher than that of carbon steel, which is widely used for stem bases. Furthermore, a major feature of the stem base of the present invention is that the thermal expansion coefficient through the thickness direction can be changed (adjusted) by selecting the Cr and / or Mo content of the [Cr and / or Mo]-Cu composite and the area reduction rate during diameter reduction and elongation of the material. This allows the thermal expansion coefficient of the stem base through the thickness direction to be as close as possible to the thermal expansion coefficient of the sealing glass, maximizing the reliability of the bond between the stem base and the sealing glass, which is an issue in compression-sealed glass hermetic seals. In addition, the thermal conductivity through the thickness direction of the stem base of the present invention increases as the area reduction rate during diameter reduction and elongation increases, so the thermal conductivity through the thickness direction can be adjusted depending on the application equipment, etc.

[0089] The stem base of the present invention has an average thermal expansion coefficient in the thickness direction from 30°C to 450°C of 7.0 to 12.0 × 10 -6 / K, and the average thermal expansion coefficient in the plate direction from 30°C to 450°C is 18.0×10 -6 / K or less, and it is preferable that 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 plane direction from 30°C to 450°C, and the thermal conductivity in the thickness direction is preferably 180 W / m K or more. In the case of a stem base, since it is necessary to compress the sealing glass and lead pins in the plane direction, it is preferable that the thermal expansion coefficient in the plane direction is somewhat large. From this point of view, -6 / K or more is preferable. Furthermore, the [Cr and / or Mo]-Cu composite preferably has a total Cr and / or Mo content of 35 to 60 mass %. The reasons why the above-mentioned properties and composition conditions are preferable are as explained above with respect to the metallic material of the present invention.

[0090] Compression-sealed glass hermetic seals typically have a multi-pin structure, with stem bases of various shapes, including circular and rectangular. For example, airtight terminals for electric compressors have a three-pin structure and stem bases shaped like trucks. Semiconductor laser devices also typically have a multi-pin structure, with stem bases of various shapes, including circular and rectangular. This plate-shaped stem base can be manufactured by processing the plate-shaped metal material of the present invention described above. As mentioned above, this plate-shaped metal material can be obtained by radially cutting a rod-shaped or wire-shaped material obtained by area-reduction processing (diameter-reducing and stretching processing) 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. In this case, if the area-reduction processing (diameter-reducing and stretching processing) is performed by hot extrusion, a rod-shaped material with a cross-sectional shape similar to that of a track and field truck can be obtained. By cutting this rod-shaped material radially, a plate-shaped metal material similar in shape to the stem base itself can be obtained. Typically, the stem base is subjected to a surface treatment such as Ni plating. 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 metallic material of the present invention, as explained above.

[0091] As described above, the stem base of the present invention can appropriately compress the sealing glass and lead pins in the in-plane direction, has high bonding reliability with the sealing glass, and also has excellent heat dissipation performance in the thickness direction. This improves the heat dissipation performance of, for example, semiconductor laser devices, and can fully accommodate the increasing power and performance of semiconductor laser devices. Furthermore, while the stem base's thermal expansion coefficient in the in-plane direction must be somewhat greater than that of the sealing glass to apply a compressive force to the sealing glass, it is desirable that the thermal expansion coefficient in the thickness direction be as close as possible to that of the sealing glass to ensure bonding reliability. The stem base of the present invention has a constant in-plane thermal expansion coefficient, but its thickness direction thermal expansion coefficient is smaller than that of the sealing glass. Furthermore, the magnitude of the thickness direction thermal expansion coefficient can be adjusted and optimized by selecting the Cr and / or Mo compounding ratio (content) and the area reduction rate during diameter reduction and elongation of the material, thereby achieving a high degree of thermal expansion characteristics required of a stem base. On the other hand, by increasing the area reduction rate during diameter reduction and elongation, the thermal conductivity in the plate thickness direction can be increased, and the heat dissipation required for the stem base can be highly satisfied.

[0092] [Airtight terminal and electric compressor] The hermetic terminal of the present invention is a compression-sealed hermetic terminal equipped with the lead pin described above. Therefore, the lead pin is made of a [Cr and / or Mo]-Cu composite having a metal structure in which a Cr phase and / or Mo phase is dispersed in a Cu matrix. This [Cr and / or Mo]-Cu composite is a diameter-reduced and drawn powder metallurgy compact, and when observed through an optical microscope (for example, at 120x magnification), it is characterized by having an axial cross-sectional structure in which lamellar or linear Cr and / or Mo phases are dispersed in the Cu matrix, and a radial cross-sectional structure in which flake-like, small-platelet-like, or granular Cr and / or Mo phases are dispersed in the Cu matrix. The details of the lead pins provided in this airtight terminal are as explained above in relation to the "metal material" and "lead pins." The electric compressor of the present invention is an electric compressor equipped with the airtight terminal. Therefore, the airtight terminal of the present invention and the electric compressor of the present invention equipped with this airtight terminal can respectively enjoy the effects of the metal material and lead pin of the present invention described above.

[0093] [Semiconductor laser device] The semiconductor laser device of the present invention is a semiconductor laser device including the stem base and / or lead pins described above, and therefore has any one 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 metal structure in which Cr phases and / or Mo phases are dispersed in a Cu matrix, and this [Cr or / and Mo]-Cu composite is a diameter-reduced, drawn material of a powder metallurgy compact. When the cross-sectional structure is observed with an optical microscope (for example, at a magnification of 120x), 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 flake-like, small-plate-like, or granular Cr phases and / or Mo phases are dispersed in the Cu matrix (a semiconductor laser device of the first embodiment of the present invention). (2) The lead pin is made of a [Cr and / or Mo]-Cu composite having a metal structure in which Cr phases and / or Mo phases are dispersed in a Cu matrix, and this [Cr and / or Mo]-Cu composite is a diameter-reduced and drawn material of a powder metallurgy compact, 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 and / or Mo phases are dispersed in the Cu matrix, and a radial cross-sectional structure in which flake-like, small platelet-like, or granular Cr phases and / or Mo phases are dispersed in the Cu matrix (a semiconductor laser device of a second embodiment of the present invention).

[0094] (3) The plate-shaped stem base and lead pin are made of a [Cr and / or Mo]-Cu composite having a metal 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-like stem base is a diameter-reduced, elongated material of a powder metallurgical compact, and when cross-sectionally observed with an optical microscope (for example, at a magnification of 120 times), has a cross-sectional structure in the plate thickness direction in which lamellar 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 flake-like, small-plate-like, or granular Cr phases and / or Mo phases are dispersed in a Cu matrix, The [Cr and / or Mo]-Cu composite constituting the lead pin is a diameter-reduced and drawn material of a powder metallurgical compact, and when cross-sectionally observed with an optical microscope (for example, at 120x magnification), it has an axial cross-sectional structure in which layered or linear Cr and / or Mo phases are dispersed in a Cu matrix, and a radial cross-sectional structure in which flake-like, small-platelet-like, or granular Cr and / or Mo phases are dispersed in a Cu matrix (a semiconductor laser device according to a third embodiment of the present invention).

[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 using the stem base and / or the lead pin as constituent members. The details of the lead pins and / or stem bases provided in the semiconductor laser devices (1) to (3) above are as explained above for the "metal material," "lead pins," and "stem base." Therefore, the semiconductor laser devices (1) to (3) above can each enjoy the effects of the metal material, lead pin, and stem base of the present invention. Furthermore, the semiconductor laser device of (3) above is particularly preferable because it includes the lead pins and stem base of the present invention described above, and therefore the reliability of the bonding between the sealing glass and the lead pins and stem base is the highest. [Other materials] Conventionally, no shaft-shaped material has been known that has a low axial thermal expansion coefficient and high axial electrical conductivity, and no plate-shaped material has been known that has a low thickness-direction thermal expansion coefficient and high thickness-direction thermal conductivity. As a material with such properties, the metallic material of the present invention can be used in a variety of applications, such as conductive members and heat sinks that are joined to other low-thermal expansion materials.

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

[0097] 5 and 6 are schematic diagrams of the compression-sealed glass hermetic seal used in this study (conceptual diagrams showing the dimensions and thermal expansion coefficients of the constituent parts, the compressive stress within the seal, etc.), with FIG. 5(A) being a schematic longitudinal cross-sectional view of the entire seal, FIG. 5(B) being a schematic plan view of the same, and FIG. 5(C) being a schematic plan view of the sealing glass. Also, FIG. 6(A) is a schematic longitudinal cross-sectional view of the entire seal, FIG. 6(B) is a schematic plan view of the housing and sealing glass, and FIG. 6(C) is a schematic plan view of the sealing glass and lead pin. The numerical values ​​shown in FIGS. 5 and 6 are the average thermal expansion coefficients of the components that make up the seal. For ease of explanation, the metal material of the present invention that makes up the lead pin will be referred to as "55% Cr-Cu material" in the following description. Because the thermal expansion coefficient of the housing (carbon steel S45C) is greater than that of the sealing glass, the outer radial surface (outer periphery) of the sealing glass receives compressive stress P1 from the inner radial surface (inner periphery) of the housing while the sealing glass cools to room temperature after hardening.

[0098] The volume of the sealing glass is determined at approximately [glass transition point - 30°C] relative to the glass transition point where it completely hardens (the glass transition point of the above ST-4W: 460°C), and at 30°C it shrinks in volume due to the coefficient of thermal expansion. The calculated outer radius of the sealing glass R2' (radius at the outer surface of the sealing glass) is larger than the inner radius R2 (radius at the inner surface of the housing) due to housing shrinkage, but it matches the inner radius R2 of the housing due to the compressive stress P1 during sealing (see Toshiba Glass Technical Report 26, "On Glass Distortion"). The inner radius of the sealing glass (radius at the inner surface of the sealing glass) is displaced by υ2 toward the inner diameter (due to compressive strain caused by compressive stress P1) to become R3". The compressive stress P1 acting on the sealing glass from the housing can be predicted by calculating the displacement difference υ2 as a "thick-walled cylinder subjected to external pressure" in 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, so after the sealing glass hardens and cools to room temperature, the lead pin contracts more radially than the sealing glass, resulting in a calculated gap δ3 (the difference between the calculated inner radius of the sealing glass R3' and the calculated outer radius of the lead pin R3). If the displacement υ2 of the sealing glass toward the inner diameter is greater than this gap δ3, in other words, if R3" (= R3' - υ2) is smaller than R3, then no gap will occur at the interface between the sealing glass and the lead pin, and there is a possibility of achieving reliable bonding. In this case, the lead pin will be subjected to compressive stress P2 from the sealing glass due to the displacement difference υ3 between R3 and R3". In other words, the sealing glass will be subjected to compressive stress P1 on its outer radial surface from the housing, while the sealing glass will apply compressive stress P2 to the lead pin from its inner radial surface. This compressive stress P2 can be predicted by calculating the displacement difference υ3 as a "combined cylinder" in material mechanics.

[0100] The reliability of the bonding between the sealing glass and the housing and between the sealing glass and the lead pins is considered as follows. Because the difference in thermal expansion between the housing (carbon steel S45C) and the sealing glass is large in the thickness direction (height direction in the drawing, same below), shear stress occurs in the thickness direction at the interface between the housing and the sealing glass during sealing. However, because this combination is commonly used, it is unlikely that immediate interfacial delamination will occur. This is because compressive strain remains in the sealing glass during sealing. The shear stress at the glass interface in the thickness direction caused by this residual strain is on the compressive side, which is a characteristic of glass that is strong, and is also relieved by the radial compressive stress P1 (interfacial adhesion stress). When the temperature rises in the operating environment, the shear stress at the glass interface in the thickness direction becomes on the tensile side, which is a characteristic of glass that is weak. However, the residual compressive strain in the glass is thought to be able to relieve this tensile stress. However, under more severe operating conditions, there is a possibility that problems with joint reliability may arise. Furthermore, a commonly used combination of Kovar lead pins and FN-13W (glass cord, manufactured by Nippon Electric Glass Co., Ltd.) sealing glass is 2×10 times stronger than the sealing glass. -6 The difference in thermal expansion between the lead pin and the sealing glass causes undesirable tensile strain in the sealing glass. Therefore, in terms of material properties, this combination does not provide sufficient bonding reliability.

[0101] On the other hand, the bonding reliability on the inner radial surface of the sealing glass can be considered as follows. Calculation results 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 greater than that of the sealing glass, just like the housing, compressive strain will remain in the sealing glass in the thickness direction, just like the housing, but the bonding reliability will tend to be lower at the inner radial surface of the sealing glass than at the outer radial surface of the sealing glass. However, the 55% Cr-Cu material that makes up 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, it is thought that bonding reliability can be achieved 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 lead pin axial direction and the housing thickness direction, and the balance between this compressive shear stress τ and the compressive stresses P1 and P2 in the sealing glass radial direction. If the thermal expansion coefficient of the housing in the plate-face direction and the lead pin radial direction is greater than that of the sealing glass, the sealing glass will undergo compressive strain that is favorable for glass after cooling. However, repeated temperature increases and decreases will affect the sealing glass with compression and tension. The difference in the thermal expansion coefficients between the housing thickness direction, the lead pin axial direction, and the sealing glass may cause shear stress fatigue, which may reduce joint reliability. For this reason, it is preferable that the thermal expansion coefficients of the housing in the thickness direction, the lead pin axial direction, and the sealing glass be as close as possible to the compressive side of the sealing glass. Meanwhile, it is preferable that the compressive stresses P1 and P2 in the sealing glass radial direction are large. Therefore, the smaller the values ​​of τ / P1 and τ / P2 are (although negative values ​​are acceptable as long as they are sufficiently small), the higher the joint reliability between the lead pin and the housing and the sealing glass. In the case of lead pins, when comparing 55% Cr-Cu material with 50.5% Ni-Fe material, the compressive stress P2 of the 55% Cr-Cu material is about 91% of that of the 50.5% Ni-Fe material and about 88% of that of the copper-core pin, but the 55% Cr-Cu material, which has a smaller difference in the thermal expansion coefficient from the sealing glass in the axial direction, has a τ / P2 that is about 86% lower than that of the 50.5% Ni-Fe material and about 93% lower than that of the copper-core pin, resulting in higher joint reliability. Even though the 55%Cr-Cu material has the characteristic 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 when used as a lead pin, it can obtain compressive stress from the sealing glass in the radial direction and also ensure joint reliability in the axial direction.

[0103] The calculation results for the above-mentioned displacement differences υ2, υ3 and compressive stresses P1, P2, the thickness direction shear stress τ1 from the housing to the sealing glass interface, the axial direction shear stress τ3 from the lead pin to the sealing glass interface, τ1 / P1 and τ3 / P2 are shown below. The physical properties of each material used in this calculation will be described later. In the calculations below, the values ​​enclosed in brackets [ ] below specific values ​​are those obtained when the lead pin is made of a conventional 50.5% Ni-Fe alloy (average axial thermal expansion coefficient (30-450°C): 10.3 x 10 -6 / K).

[0104] ●The dimensional changes of the housing (carbon steel), sealing glass, and lead pin (55% Cr-Cu material) from 430℃ to 30℃ are shown below. In Figures 5 and 6, when R1 = 8 mm, R2 = 3 mm, and R3 = 1.6 mm, the dimensions at temperatures of 430°C and 30°C are as follows. <At 430℃> · Housing inner radius = Sealing glass outer radius = R2*(1+α1*(430℃-30℃)) =3.018318mm · Sealing glass inner radius = lead pin outer radius = R3*(1+α3*(430℃-30℃)) =1.609219mm [1.607981mm] <At 30℃> Housing outer radius = 8mm = R1 ·Inner radius of housing = Outer radius of sealing glass = 3mm = R2 Calculated outer radius of sealing glass: R2' = 3.018318 * (1 - α2 * (430℃ - 30℃)) =3.006848mm → The sealing glass is compressed to 3 mm and is subjected to a compressive stress of υ2, the difference in displacement. Calculated inner radius of sealing glass: R3'=1.609219*(1-α3*(430℃-30℃)) =1.603104mm [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 point - 30°C, and at 30°C it shrinks due to the thermal expansion coefficient. The calculated volume of the sealing glass and the volume after sealing are constant, but assuming that 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. Inner radius of the sealing glass: 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 there are no lead pins, the inner radius of the sealing glass: R3" = R3'-υ2 =1.590222mm ·R3>R3”→ R3-R3”=υ3=0.00978mm [0.01102mm] → The lead pin receives compressive stress P2 from the sealing glass due to 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 on the interface from the housing to the sealing glass and [thickness direction compressive shear stress τ1 acting on the interface from the housing to the sealing glass] / [radial compressive stress P1 from the housing to the sealing glass] are calculated as follows. In Figures 5 and 6, when R1 = 8 mm, R2 = 3 mm, R3 = 1.6 mm, and the housing thickness T1 = 6 mm, the dimensions at temperatures of 430°C and 30°C are as follows. <At 430℃> Carbon steel thickness = sealing glass thickness; T1' = 6 * (1 + α1 * (430℃ - 30℃)) =6.036636mm <At 30℃> Sealing glass thickness: T2' = T1' * (1 - α2 * (430℃ - 30℃)) = 6.013697 mm

[0108] → Compressive strain ε from the housing to the sealing glass after cooling = (T2'-T1) / T1 =0.002283 Compressive stress: Pt1 = glass elastic modulus * ε = 0.15523 GPa = 155.23 MPa [155.23MPa] Compression force: Ft1=Pt1*π*R2 2 =4389N [4389N] The compressive shear stress τ1 in the thickness direction acting from the housing to the sealing glass interface is given by: τ1=Ft1 / (π*2*R2*T1)=38.81MPa [38.81MPa] →Therefore, [compressive shear stress τ1 in the thickness direction acting on the interface from the housing to the sealing glass] / [compressive stress P1 in the radial direction 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 [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 lead pin in contact with sealing glass: T3' = T1' * (1 - α3 (430℃ - 30℃)) =6.013455mm [6.01177mm] → Compressive strain ε from the sealing glass to the lead pin after cooling = (T2'-T3') / T3' =0.000040 Compressive stress: Pt3 = glass elastic 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 given by: τ3=Ft3 / (π*2*R3*T1)=0.363MPa [2.908MPa] →Therefore, [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] is as follows: τ3 / P2=0.0039 [0.0285]

[0111] The above calculations were performed for cases where the lead pins were made of the 55% Cr-Cu material of the present invention, the housing was made of carbon steel S45C, and the sealing glass was made of ST-4W (glass cord, manufactured by Nippon Electric Glass Co., Ltd.). However, similar calculations were also performed for cases where the lead pins, housing, and sealing glass were made of other materials. Specifically, the lead pins were made of the metal materials of the present invention: 45% Cr-Cu, 60% Mo-Cu, and 35% Mo-Cu, as well as comparative materials: 50.5% Ni-Fe, SUS430, copper core pins, and 29% Ni-17% Co-Fe. The calculation results are shown in Tables 1 to 3, along with the above-mentioned calculation results. In Tables 1 to 3, "Examples equivalent to the present invention" refers to cases where the lead pins were made of the metal material of the present invention, and "Comparative Examples" refers to cases where the lead pins were made of a material other than the metal material of the present invention. In the "Reference Examples" in Tables 1 and 3, in which 35% Mo-Cu material (the metal material of the present invention) was used for the lead pin, the average radial thermal expansion coefficient of the lead pin was approximately 18.0 × 10 -6 This is stated to show that the lead pin can receive compressive stress from the sealing glass if the temperature is 1000 K or less.

[0112] The physical properties of the materials 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: 205GPa Poisson's ratio ν1:0.25 SUS304 Average thermal expansion coefficient α1 (0-538℃): 18.8×10 -6 / K Young's modulus E1: 193GPa Poisson's ratio ν1:0.3 SUS430 Average thermal expansion coefficient α1 (0-538℃): 11.7×10 -6 / K Young's modulus E1: 200GPa Poisson's ratio ν1:0.27

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

[0114] 50.5% Ni-Fe material Radial average 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: 162GPa Poisson's ratio ν3:0.30 SUS430 Radial average thermal expansion coefficient α3 (30-450℃): 11.3×10 -6 / K Average axial thermal expansion coefficient (30-450℃): 11.3×10 -6 / K Young's modulus E3: 200GPa Poisson's ratio ν3:0.27 Copper core pin Radial average thermal expansion coefficient α3 (30-450℃): 11.1×10 -6 / K Average axial thermal expansion coefficient (30-450℃): 11.1×10 -6 / K Young's modulus E3: 157GPa Poisson's ratio ν3:0.31 29%Ni-17%Co-Fe material (Kovar) Radial average thermal expansion coefficient α3 (30-450℃): 5.3×10 -6 / K Average axial thermal expansion coefficient (30-450℃): 5.3×10 -6 / K Young's modulus E3: 152GPa 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 / K Glass transition temperature Tg: 460℃ Young's modulus E2: 68GPa 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 / K Glass transition temperature Tg: 510℃ Young's modulus E2: 57GPa Poisson's ratio ν2:0.22 SG354 (glass cord, manufactured by AGC) Average thermal expansion coefficient α2 (50-350℃): 10.7×10-6 / K Glass transition temperature Tg: 567℃ Young's modulus E2: 68GPa Poisson's ratio ν2:0.21

[0116] [Table 1]

[0117] [Table 2]

[0118] [Table 3]

[0119] From the calculation results in Tables 1 to 3, it can be determined that when the metal material of the present invention is used for the lead pin (corresponding to the invention example), a compressive pressure P2 from the sealing glass to the lead pin is obtained, and τ3 / P2 is sufficiently low, so that the required bonding reliability is obtained. In particular, as shown in Tables 2 and 3, by roughly matching the average axial thermal expansion coefficient of the lead pin to 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, making it possible to maximize bonding reliability. On the other hand, the comparative example in Table 3 is a commonly used combination of Kovar lead pins and FN-13W sealing glass (glass cord, manufactured by Nippon Electric Glass Co., Ltd.). As mentioned above, the lead pins are 2 x 10 times thinner than the sealing glass. -6 / K, the value of τ3 / P2 is minus 0.44, which means tensile strain that is undesirable for sealing glass, and it can be seen that the numerical results show that the bonding reliability is not sufficient.

[0120] Next, we investigated the application of the metal material of the present invention to the housing (stem base) of a compression-sealed glass hermetic seal provided in a semiconductor laser device, with the hope of improving the heat dissipation of the housing (stem base). As with the hermetic terminal, we conducted the investigation using a simplified concentric cylindrical shape (R1 = 4.5 mm, R2 = 0.6 mm, housing thickness T = 1.5 mm) 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 pin was made of the wire-shaped metal material of the present invention (55% Cr-Cu composite wire), and the housing was made of carbon steel. Calculations similar to those in Tables 1 to 3 were performed for the cases where the housing was made of a plate-shaped metal material of the present invention (55% Cr-Cu composite plate). For comparison, we also performed similar calculations for the case where the housing was made of carbon steel, the lead pin was 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 invention examples" refers to cases where the metal material of the present invention is used for the lead pins and / or housing, and "equivalent to comparative examples" refers to cases where a material other than the metal material of the present invention is used for the lead pins and housing. The physical property values ​​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] 7 and 8 are schematic diagrams of the compression-sealed glass hermetic seal provided in the semiconductor laser device used in this study (conceptual diagrams showing the dimensions and thermal expansion coefficients of the constituent parts, the compressive stress within the seal, etc.) Fig. 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 pin is made of the linear metal material of the present invention (55% Cr-Cu composite wire), Fig. 7(A) is a schematic vertical cross-sectional view of the entire seal, and Fig. 7(B) is a schematic plan view of the same. FIG. 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 pin is made of the wire-shaped metal material of the present invention (55% Cr-Cu composite wire), and the sealing glass is ST-4W (glass cord, manufactured by Nippon Electric Glass Co., Ltd.). FIG. 8(A) is a schematic longitudinal cross-sectional view of the entire seal, and FIG. 8(B) is a schematic plan view of the same. In FIGS. 7 and 8, the numerical values ​​shown in the figures are the average thermal expansion coefficients of the components constituting the seal. For ease of explanation, in the following description, the lead pin and housing (stem base) made of the material of the present invention will be referred to as the "Cr-Cu lead pin" and the "Cr-Cu housing," respectively. Furthermore, the housing (stem base) made of carbon steel will be referred to as the "carbon steel housing."

[0123] The thermal expansion coefficient of the Cr-Cu housing in the radial direction (towards the plate surface) is greater than that of the sealing glass, so compressive stress P1 is generated in the radial direction from the Cr-Cu housing to the sealing glass while the sealing glass cools to room temperature after hardening. The thermal expansion coefficient of the Cr-Cu housing in the height (thickness) direction is smaller than that of the carbon steel housing and is closer to that of the sealing glass. This reduces the shear stress that occurs at the interface between the housing and the sealing glass in the height (thickness) direction, which is thought to result in higher joint reliability than with a carbon steel housing.

[0124] As explained earlier, the smaller the values ​​of τ1 / P1 and τ3 / P2 are (although negative values ​​are acceptable as long as they are sufficiently small), the higher the reliability of the bond between the housing and sealing glass, and between the lead pin and sealing glass. Calculation results show that the Cr-Cu lead pin has a lower τ3 / P2 than the comparative 50.5% Ni-Fe material, due to its small difference in the axial thermal expansion coefficient from the sealing glass, resulting in higher bond reliability. Furthermore, the Cr-Cu housing has a smaller thermal expansion coefficient in the thickness direction, and a smaller difference in the thermal expansion coefficient from the sealing glass in the thickness direction, resulting in a greater decrease in τ1 / P1 than carbon steel, resulting in high bond reliability.

[0125] Regarding the housing material to replace carbon steel, we initially considered using pressed Cr-Cu / Cu clad rolled material (rolled plate material). However, because rolled plate material has a small coefficient of thermal expansion in the plate plane direction but a large coefficient of thermal expansion in the thickness direction, the housing tends to have low compressive stress in the radial direction and high interfacial shear stress in the thickness direction, which is thought to result in lower joint reliability than carbon steel. In contrast, the Cr-Cu housing of the present invention achieves the same radial (plate plane) compressive stress as a carbon steel housing, but has low interfacial shear stress in the height (thickness) direction and high heat dissipation in the height (thickness) direction, making it ideal for a housing for semiconductor laser modules. In addition, when applying the Cr-Cu housing and Cr-Cu lead pins of the present invention to semiconductor laser modules, not only the combination of a Cr-Cu housing and a Cr-Cu lead pin can be used, but also other suitable configurations may be used depending on the application, such as a combination of a Cr-Cu housing and a 52% Ni-Fe lead pin, or a combination of a carbon steel housing and a Cr-Cu lead pin. For example, the combination of a Cr-Cu housing and a 50.5% Ni-Fe lead pin (No. 4 in Table 4) has higher joint reliability than the conventional combination of a carbon steel housing and a 50.5% Ni-Fe lead pin (No. 2 in Table 4), and the combination of a carbon steel housing and a Cr-Cu lead pin (No. 1 in Table 4) has higher joint reliability than the conventional combination of a carbon steel housing and a 50.5% Ni-Fe lead pin (No. 2 in Table 4), and such configurations are also effective. [Example]

[0126] The materials of the present invention (metallic rods or wires) were manufactured under the manufacturing conditions shown below, and their properties were measured. Furthermore, as comparative materials, a material consisting of a [Cr and / or Mo]-Cu composite that had not been subjected to area reduction (diameter-reducing elongation) (area reduction rate: 0%), a pure Cu material, a 50.5% Ni-Fe material, and a copper core pin (a 50% Ni-Fe core clad with copper) were used as test materials, and their properties were measured in the same manner as above. The results are shown in Tables 5 and 6, along with the configuration (composition, density) and manufacturing conditions (area reduction rate) of the metallic materials. In the description of this example (including Tables 5 and 6), "%" in relation to the composition of the material means "mass%." Here, since the metal materials in this example are all rod-shaped or wire-shaped, they are referred to as axial and radial directions, but for the material of the present invention, the axial direction is the extension direction and the radial direction is the direction perpendicular to the extension. The rod-shaped or wire-shaped metal material of the present invention can be used as is as a material for lead pins, but a plate-shaped metal material cut out by cutting the rod-shaped metal material in the radial direction (a plate material with the axial direction of the rod-shaped metal material as the plate thickness direction and the radial direction as the plate surface direction) can be used as is as a material for a stem base.

[0127] Although not shown in Tables 5 and 6, the materials of the present invention have a cross-sectional structure as shown in Fig. 1, i.e., when observed with an optical microscope, they have a cross-sectional structure in the stretching direction (axial direction) in which lamellar or linear Cr and / or Mo phases are dispersed in a Cu matrix, and a cross-sectional structure in the transverse direction (radial direction) in which flake-like, small-sized, or granular Cr and / or Mo phases are dispersed in a Cu matrix. In contrast, a comparative material made of a [Cr and / or Mo]-Cu composite that has not been subjected to area reduction (diameter-reducing elongation) (area reduction rate: 0%) naturally does not have such a characteristic cross-sectional structure, but rather has a cross-sectional structure similar to the "infiltrant cross section" in Fig. 2.

[0128] (1) Production of materials for surface reduction processing Cr and / or Mo powders were placed in a mold and pressed, or a mixture of Cr and / or Mo powders and Cu powders in a specified ratio was placed in a mold and pressed to form a compact. A pure Cu plate was placed on top of this compact, and sintering and Cu infiltration were performed in a reducing atmosphere. Specifically, the compact was first sintered (1000°C, 600 minutes) to form a sintered compact. The temperature was then raised to melt the pure Cu plate, and the Cu was impregnated into the sintered compact through Cu infiltration (1200°C, 180 minutes). A milling machine was used to remove the remaining Cu from the surface of the [Cr and / or Mo]-Cu composite, and the shape was adjusted to obtain a rod-shaped blank of the specified size for surface reduction processing.

[0129] (2) Manufacturing of the material of the present invention by area reduction processing (diameter reduction and elongation processing) (2.1) Examples 1 to 29, 36 to 47 The material for area reduction, which had been milled to a hexagonal cross-section prism shape (thickness 20.7 mm), was then swaged and subsequently combined roll rolled to reduce the area to φ3.7 mm (diameter reduction and elongation), and further reduced the area (diameter reduction and elongation) by a finishing drawing process consisting of a two-stage roller die drawing (CRD) to obtain the material of the present invention with an outer diameter of φ3.2 mm. (2.2) Examples 32 to 35 The material for area reduction, which had been milled to an octagonal cross-section prism shape (thickness 50 mm), was reduced in area (diameter reduction and elongation) to an outer diameter of φ15 mm by grooved roll rolling and subsequent swaging, and then reduced in area (diameter reduction and elongation) to a prism shape (octagonal cross-section) with a thickness of 3.7 mm by combined roll rolling.Furthermore, a finishing drawing process consisting of roller die drawing (CRD) and simple drawing (cold wire drawing using a wet method) was performed to reduce in area (diameter reduction and elongation), 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 above. The axial electrical conductivity (and volume resistivity) was measured using an Advance Riko Electrical Resistance Measuring Device TER-2000RH Special Model. In addition, for samples with the same material composition but different area reduction rates, material for the other samples was collected during the area reduction process of the sample with the largest area reduction rate, and this was processed into a φ3.2 mm sample by centerless grinding and used for each measurement.

[0130] According to Tables 5 and 6, the metallic material of the present invention has a certain level of radial thermal expansion coefficient, while the axial thermal expansion coefficient is considerably smaller than the radial thermal expansion coefficient, and is therefore comparable to the sealing glass (usually 8 to 11 × 10 -6It can be seen that the thermal expansion coefficient can be adjusted to be close to that of the sealing glass (approximately 1 / K). For example, as can be seen from examples such as "Nos. 5, 10, 15, 20," "Nos. 24, 29," "Nos. 37, 39," "Nos. 7 to 12," and "Nos. 26 to 29," the magnitude of the axial (extension direction) thermal expansion coefficient of the metal material of the present invention can be adjusted by selecting the Cr and / or Mo content and the area reduction rate during diameter reduction and elongation of the material. This allows the axial (extension direction) thermal expansion coefficient to be adjusted to match the thermal expansion coefficient of the sealing glass as closely as possible. Furthermore, the metal material of the present invention has a significantly higher axial electrical conductivity than conventional lead pin materials such as 50.5% Ni-Fe and copper-core pins. It also has a significantly higher axial thermal conductivity (or, in the case of plate-shaped metal materials, the thermal conductivity through the plate thickness; the same applies below) than conventional stem base materials such as carbon steel (thermal conductivity: approximately 40 to 60 W / m K). Furthermore, as can be seen from examples such as "Nos. 7 to 12" and "Nos. 26 to 29" of the present invention, the axial electrical conductivity and axial thermal conductivity of the metal material of the present invention can be changed not only by changing the component composition but also by changing the area reduction rate during diameter reduction and elongation, and therefore the axial electrical conductivity and axial thermal conductivity can be adjusted depending on the application equipment, etc.

[0131] From the above, it can be seen that when the metallic material of the present invention is used as the material for the lead pin of a compression-sealed glass hermetic seal, it is possible to obtain a lead pin that has high bonding reliability with the sealing glass and that generates little heat when a large current is passed through it, even though it is small in diameter.Furthermore, when the metallic material of the present invention is used as the material for the stem base of a compression-sealed glass hermetic seal, that is, when it is made into a plate-shaped metal material with its extension direction in the plate thickness direction and the direction perpendicular to the extension in the plate surface direction, it is possible to obtain a stem base that can appropriately compress the sealing glass and lead pin 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.

[0132] [Table 5]

[0133] [Table 6] [Industrial Applicability]

[0134] The metallic material of the present invention has a thermal expansion coefficient in the stretching direction that is less than that in the direction perpendicular to the stretching direction, a relatively small thermal expansion coefficient in the stretching direction, an isotropic thermal expansion coefficient in the direction perpendicular to the stretching direction, and high electrical conductivity and thermal conductivity in the stretching direction. Furthermore, the thermal expansion coefficient in the stretching direction can be adjusted by selecting the Cr and / or Mo content and the area reduction rate during diameter reduction and stretching of the material, and the electrical conductivity and thermal conductivity in the stretching direction can be changed depending on the area reduction rate during diameter reduction and stretching. This characteristic is not known in the past. The metallic material of the present invention is particularly suitable for use as a material for hermetic terminals and lead pins and stem bases of compression-sealed glass hermetic seals in semiconductor laser devices. It can also be used, for example, as a shaft-shaped material with a low axial thermal expansion coefficient and high axial electrical conductivity, or as a plate-shaped material with a low thickness-direction thermal expansion coefficient and high thickness-direction thermal conductivity. For example, it can be used in conductive members and heat sinks joined to other low-thermal-expansion materials. [Explanation of symbols]

[0135] 1 stem base 2 lead pins 3 Sealing glass 4 Insertion hole

Claims

1. The composite is a [Cr and / or Mo]-Cu composite having a metal 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, drawn material of a powder metallurgy compact, and is a metallic material characterized by having, when observed in cross section with an optical microscope, a cross-sectional structure in the drawing direction in which lamellar or linear Cr phases and / or Mo phases are dispersed in a Cu matrix, and a cross-sectional structure in the direction perpendicular to the drawing direction in which flake-like, small platelet-like, or granular Cr phases and / or Mo phases are dispersed in a Cu matrix.

2. Average thermal expansion coefficient in the stretching direction from 30°C to 450°C is 7.0 to 12.0 x 10 －６ / K, and the average thermal expansion coefficient in the direction perpendicular to the stretching direction from 30°C to 450°C is 18.0 x 10 －６ / K or less, and the average thermal expansion coefficient in the stretching direction from 30°C to 450°C is less than the average thermal expansion coefficient in the direction perpendicular to the stretching direction from 30°C to 450°C.

3. Electrical conductivity in the stretching direction is 20.0 × 10 ６ 3. The metallic material according to claim 1, wherein the metallic material has a viscosity of 1000 psi or more and a thermal conductivity of 180 W / m·K or more.

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

5. 2. The metallic material according to claim 1, which is a rod-shaped or wire-shaped metallic material having an axial direction in the stretching direction and a radial direction in the direction perpendicular to the stretching direction.

6. 2. The metallic material according to claim 1, wherein the metallic material is in the form of a plate, the stretching direction being the thickness direction and the direction perpendicular to the stretching being the plate surface direction.

7. 10. A method for producing the metallic material according to claim 1, comprising: A step (A) of obtaining a material for surface reduction processing comprising a [Cr and / or Mo]-Cu composite through a step of sintering a powder raw material; The method for producing a metal material is characterized by further comprising a step (B) of reducing the area of ​​the raw material obtained in the step (A) and elongating it into a rod or wire shape by reducing its diameter.

8. 8. The method for manufacturing a metallic material according to claim 7, wherein the step (B) comprises a step of subjecting the raw material to finish drawing.

9. 9. The method for producing a metal material according to claim 7 or 8, further comprising a step (C) of grinding or polishing the surface of the rod-shaped or wire-shaped material obtained in step (B) (including the rod-shaped or wire-shaped material obtained in step (B) cut to a predetermined length).

10. 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 to cut 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.

11. The method for manufacturing a metal material according to claim 9, further comprising a step (D) of cutting the rod-shaped or wire-shaped material that has undergone step (C) in the radial direction to cut 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.

12. A rod-shaped or wire-shaped metal material for a lead pin that constitutes a compression-sealed glass hermetic seal, The composite is a [Cr and / or Mo]-Cu composite having a metal 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 drawn material of a powder metallurgy compact, and when cross-sectionally observed with an optical microscope, has an axial cross-sectional structure in which lamellar or linear Cr phases and / or Mo phases are dispersed in a Cu matrix, and a radial cross-sectional structure in which flake-like, small-piece-like, or granular Cr phases and / or Mo phases are dispersed in a Cu matrix, which is a metallic material for a lead pin of a compression-sealed glass hermetic seal.

13. Average axial thermal expansion coefficient from 30°C to 450°C is 7.0 to 12.0 x 10 －６ / K, and the average radial thermal expansion coefficient from 30°C to 450°C is 18.0 × 10 －６ / K or less, 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.

14. Axial electrical conductivity is 20.0 x 10 ６ 14. The metallic material for a lead pin of a compression-sealing type glass hermetic seal according to claim 12 or 13, having a hardness of 0.5 S / m or more.

15. The metallic material for a lead pin of a compression-sealed glass hermetic seal according to claim 12, wherein the [Cr and / or Mo]-Cu composite has a total content of 35 to 60 mass% of Cr and / or Mo.

16. A plate-shaped metal material for a stem base that constitutes a compression-sealed glass hermetic seal, The composite is a [Cr and / or Mo]-Cu composite having a metal 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 drawn material of a powder metallurgy compact, and when cross-sectionally observed with an optical microscope, has a cross-sectional structure in the thickness direction in which lamellar 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 flake-like, small-piece-like, or granular Cr phases and / or Mo phases are dispersed in the Cu matrix, making it a metallic material for a stem base of a compression-sealed glass hermetic seal.

17. Average thermal expansion coefficient in the thickness direction from 30°C to 450°C is 7.0 to 12.0 x 10 －６ / K, and 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 thickness direction from 30°C to 450°C is less than the average thermal expansion coefficient in the plane direction from 30°C to 450°C.

18. 18. The metallic material for a stem base of a compression-sealing type 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 metallic material for a stem base of a compression-sealed glass hermetic seal according to claim 16, wherein the [Cr and / or Mo]-Cu composite has a total content of 35 to 60 mass% of Cr and / or Mo.

20. A plate-shaped stem base that constitutes a compression-sealed glass hermetic seal, The composite is a [Cr and / or Mo]-Cu composite having a metal 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 drawn material of a powder metallurgy compact, and when cross-sectionally observed with an optical microscope, it has a cross-sectional structure in the thickness direction in which lamellar 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 flake-like, small-piece-like, or granular Cr phases and / or Mo phases are dispersed in a Cu matrix, which is a stem base for a compression-sealed glass hermetic seal.

21. Average thermal expansion coefficient in the thickness direction from 30°C to 450°C is 7.0 to 12.0 x 10 －６ / K, and 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 thickness direction from 30°C to 450°C is less than the average thermal expansion coefficient in the plane direction from 30°C to 450°C.

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

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

24. 21. The stem base of a compression-sealed glass hermetic seal according to claim 20, wherein the surface of the base body made of the [Cr and / or Mo]--Cu composite has a surface treatment film.

25. the plate-shaped stem base is made of a [Cr and / or Mo]-Cu composite having a metal 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 of a powder metallurgy compact, and when cross-sectionally observed with an optical microscope, has a cross-sectional structure in the thickness direction in which lamellar 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 flake-like, small-plate-like, or granular Cr phases and / or Mo phases are dispersed in a Cu matrix, for a semiconductor laser device.

26. 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 x 10 －６ / K, and 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 thickness direction from 30°C to 450°C is less than the average thermal expansion coefficient in the plane direction from 30°C to 450°C.

27. 27. The semiconductor laser device according to claim 25, wherein the stem base has a thermal conductivity of 180 W / m·K or more in the thickness direction.

28. 26. The semiconductor laser device according to claim 25, wherein the [Cr and / or Mo]--Cu composite has a total content of Cr and / or Mo of 35 to 60 mass %.

29. 26. The semiconductor laser device according to claim 25, wherein the stem base has a surface treatment film on the surface of the base body made of the [Cr and / or Mo]--Cu composite.

30. the lead pin is made of a [Cr and / or Mo]-Cu composite having a metal structure in which a Cr phase and / or Mo phase is dispersed in a Cu matrix; The [Cr and / or Mo]-Cu composite is a diameter-reduced and stretched material of a powder metallurgy compact, and when cross-sectionally observed with an optical microscope, has an axial cross-sectional structure in which lamellar or linear Cr phases and / or Mo phases are dispersed in a Cu matrix, and a radial cross-sectional structure in which flake-like, small platelet-like, or granular Cr phases and / or Mo phases are dispersed in a Cu matrix. This semiconductor laser device is characterized by the above.

31. The lead pin has an axial average thermal expansion coefficient of 7.0 to 12.0×10 from 30° C. to 450° C. －６ / K, and the average radial thermal expansion coefficient from 30°C to 450°C is 18.0 × 10 －６ / 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].

32. The lead pin has an axial electrical conductivity of 20.0×10 ６ 32. The semiconductor laser device according to claim 30, wherein the refractive index is S / m or more.

33. 31. The semiconductor laser device according to claim 30, wherein the [Cr and / or Mo]--Cu composite has a total content of Cr and / or Mo of 35 to 60 mass %.

34. 31. The semiconductor laser device according to claim 30, wherein the lead pin has a surface treatment film on the surface of the pin body made of the [Cr and / or Mo]--Cu composite.

35. The plate-shaped stem base and the lead pin are made of a [Cr and / or Mo]-Cu composite having a metal 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-like stem base is a diameter-reduced and drawn material of a powder metallurgical compact, and when observed in cross section with an optical microscope, has a cross-sectional structure in the plate thickness direction in which lamellar 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 flake-like, small-piece-like or granular Cr phases and / or Mo phases are dispersed in a Cu matrix, The [Cr and / or Mo]-Cu composite constituting the lead pin is a diameter-reduced and drawn material of a powder metallurgy compact, and when cross-sectionally observed with an optical microscope, has an axial cross-sectional structure in which lamellar or linear Cr phases and / or Mo phases are dispersed in a Cu matrix, and a radial cross-sectional structure in which flake-like, small platelet-like, or granular Cr phases and / or Mo phases are dispersed in a Cu matrix, resulting in a semiconductor laser device.

36. 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 x 10 －６ / K, and 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 [average thermal expansion coefficient in the thickness direction from 30 ° C. to 450 ° C.] < [average thermal expansion coefficient in the plate surface direction from 30 ° C. to 450 ° C.], The lead pin has an axial average thermal expansion coefficient of 7.0 to 12.0×10 from 30° C. to 450° C. －６ / K, and the average radial thermal expansion coefficient from 30°C to 450°C is 18.0 × 10 －６ / 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].

37. The stem base has a thermal conductivity in the thickness direction of 180 W / m·K or more, The lead pin has an axial electrical conductivity of 20.0×10 ６ 37. The semiconductor laser device according to claim 35, wherein the refractive index is S / m or more.

38. The semiconductor laser device of claim 35, wherein the [Cr or / and Mo]-Cu composite constituting the stem base and the lead pin has a total Cr or / and Mo content of 35 to 60 mass%.

39. The semiconductor laser device of claim 35, wherein the stem base and / or the lead pin have a surface treatment coating on the surface of the base body and / or the pin body made of the [Cr or / and Mo]-Cu composite.

40. 36. The semiconductor laser device according to claim 25, wherein a compression-sealed glass hermetic seal is formed with the stem base as a constituent member.

41. A semiconductor laser device as described in claim 30 or 35, characterized in that a compression-sealed glass hermetic seal is formed using the lead pin as a constituent member.

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